Resin composition, molded body, multilayer structure, and method for producing multilayer structure

Abstract

The present invention provides a resin composition which contains: a modified hydrogenated product (A) of a block copolymer that comprises a polymer block (A-1) having a structural unit that is derived from an aromatic vinyl compound and a polymer block (A-2) having a structural unit that is derived from a conjugated diene compound; and a resin (B). With respect to this resin composition, the modified hydrogenated product (A) has at least one functional group that is selected from the group consisting of a carboxy group, an amino group, a hydroxy group and a group derived from an acid anhydride, while having a vinyl bond content in the polymer block (A-2) of 50% by mole to 99% by mole; the resin (B) is composed of at least one substance that is selected from the group consisting of an acrylic block copolymer and a thermoplastic polyurethane resin; the mass ratio (A) / (B) of the modified hydrogenated product (A) to the resin (B) is 90 / 10 to 10 / 90; and the melt flow rate as determined at a temperature of 230°C under a load of 21 N in accordance with JIS K7210 (2014) is 5g / 10 minutes or more.

Description

Resin composition, molded article, laminated structure, and method for manufacturing laminated structure

[0001] The present invention relates to a resin composition, a molded article, a laminated structure, and a method for producing a laminated structure.

[0002] It is known that block copolymers having a styrene-based polymer block and a conjugated diene-based polymer block and hydrogenated products thereof are thermoplastic, easily moldable, and can be used as compatibilizers. It is also known that some of the block copolymers and / or hydrogenated products thereof exhibit melt adhesion to synthetic resins and metals when blended with a polyurethane-based block copolymer having a specific addition polymerization-based polymer block and a polyurethane block composed of a polyurethane elastomer to form a resin composition (see, for example, Patent Documents 1 to 3).

[0003] Furthermore, in order to further improve the adhesive strength to synthetic resins and metals, improvements have been made to resin compositions containing the above-mentioned block copolymers and / or hydrogenated products thereof. One of the improvement methods is, for example, a technique of using modified polymers in which the above-mentioned block copolymers and / or hydrogenated products thereof are modified to introduce reactive functional groups (e.g., Patent Documents 4 to 6).

[0004] Japanese Patent Application Laid-Open No. 11-302495 Japanese Patent Application Laid-Open No. 2003-041089 Japanese Patent Application Laid-Open No. 2004-346109 Japanese Patent Application Laid-Open No. 2018-024776 Japanese Patent Application Laid-Open No. 2021-181561 International Publication No. 2021 / 215255

[0005] Techniques using modified polymers, such as those described in Patent Documents 4 to 6, have shown improved adhesive strength to highly polar synthetic resins and metals. However, as the fields of use of block copolymers or their hydrogenated products expand, further improvements in adhesive strength are desired to make them suitable for a variety of applications. In addition, excellent physical properties, such as flexibility, tensile properties, and moldability, required for plastic materials are also desirable. For example, in overmolding by injection molding, it is not easy to achieve excellent adhesive strength to both metals and synthetic resins. Specifically, the resin composition disclosed in Patent Document 4 requires injection molding at a high temperature, such as 260°C, as described in the Examples, in order to exhibit excellent adhesive strength. However, injection molding at such a high temperature may result in a decrease in physical properties such as tensile elongation and color. On the other hand, when conventional resin compositions are injection molded at temperatures lower than 260°C (e.g., around 230°C) to exhibit excellent tensile properties such as tensile elongation, adhesive strength may be reduced. In this situation, resin compositions containing the block copolymers and / or their hydrogenated products are desired to achieve both excellent adhesive strength and tensile properties such as tensile elongation.

[0006] Therefore, an object of the present invention is to provide a resin composition having excellent tensile properties and strong adhesive strength to synthetic resins, metals, etc., a molded article, a laminated structure, and a method for producing a laminated structure.

[0007] As a result of intensive research to solve the above problems, the present inventors have conceived the following invention and found that the above problems can be solved.

[0008] [1] A resin composition comprising: a modified hydrogenated product (A) of a block copolymer including a polymer block (A-1) having structural units derived from an aromatic vinyl compound and a polymer block (A-2) having structural units derived from a conjugated diene compound; and a resin (B), wherein the modified hydrogenated product (A) has at least one functional group selected from the group consisting of a carboxy group, an amino group, a hydroxy group, and a group derived from an acid anhydride, and the vinyl bond content of the polymer block (A-2) is 50 to 99 mol %; the resin (B) is at least one selected from the group consisting of an acrylic block copolymer and a thermoplastic polyurethane resin; the mass ratio (A) / (B) of the modified hydrogenated product (A) to the resin (B) is 90 / 10 to 10 / 90; and the melt flow rate measured in accordance with JIS K7210:2014 at a temperature of 230°C and a load of 21 N is 5 g / 10 min or more. [2] The resin composition according to [1] above, further comprising a hydrogenated block copolymer (C) having a polymer block (C-1) containing structural units derived from an aromatic vinyl compound and a polymer block (C-2) containing structural units derived from a conjugated diene compound. [3] The resin composition according to [2] above, wherein the vinyl bond content of the polymer block (C-2) is 1 to 85 mol %. [4] The resin composition according to [2] or [3] above, wherein the hydrogenation rate of carbon-carbon double bonds in the polymer block (C-2) is 80 to 100 mol %. [5] The resin composition according to any one of [2] to [4] above, wherein the conjugated diene compound in the polymer block (C-2) contains at least one selected from the group consisting of isoprene, butadiene, and farnesene. [6] The resin composition according to any one of [2] to [5] above, wherein the content of the polymer block (C-1) in the hydrogenated block copolymer (C) is 5 to 70 mass %. [7] The resin composition according to any one of claims 1 to 6, wherein the content of the functional group relative to the modified hydrogenated product (A) is 0.10 to 5.00 phr. [8] The resin composition according to any one of [1] to [7], wherein the hydrogenation rate of carbon-carbon double bonds in the polymer block (A-2) is 80 to 100 mol %.[9] The resin composition according to any one of [1] to [8] above, wherein the polymer block (A-2) contains structural units derived from isoprene in an amount of 30% by mass or more.

[10] The resin composition according to any one of [1] to [9] above, wherein the conjugated diene compound in the polymer block (A-2) contains isoprene and butadiene.

[11] The resin composition according to any one of [1] to

[10] above, wherein the modified hydrogenated product (A) contains the polymer block (A-1) in an amount of 5 to 40% by mass.

[12] The resin composition according to any one of [2] to [6] above, wherein a softener is contained in an amount of 5 to 200 parts by mass per 100 parts by mass of the hydrogenated block copolymer (C).

[13] The resin composition according to

[12] above, wherein the softener is at least one selected from the group consisting of paraffinic process oil, naphthenic process oil, and aromatic process oil.

[14] A molded article containing the resin composition according to any one of [1] to

[13] above.

[15] A laminated structure having a layer formed from the resin composition according to any one of [1] to

[13] above, and a layer formed from a material other than the resin composition.

[16] The laminated structure according to

[15] above, wherein the other material is at least one selected from the group consisting of synthetic resins and metals.

[17] A method for producing the laminated structure according to

[15] or

[16] above, comprising injection insert molding the resin composition into a layer formed from a material other than the resin composition.

[0009] According to the present invention, it is possible to provide a resin composition, a molded article, a laminated structure, and a method for producing a laminated structure, which have excellent tensile properties and strong adhesive strength to synthetic resins, metals, etc.

[0010] The following description is based on an example of an embodiment of the present invention. However, the embodiment described below is merely an example for embodying the technical concept of the present invention, and the present invention is not limited to the following description. Furthermore, although preferred embodiments are shown in this specification, a combination of two or more of the individual preferred embodiments is also a preferred embodiment. When there are several numerical ranges for matters shown as numerical ranges, the lower limit and upper limit can be selectively combined to form a preferred embodiment. Note that, in this specification, when a numerical range is described as "XX to YY," it means "XX or more and YY or less." In this specification, "(meth)acrylonitrile" means "acrylonitrile or methacrylonitrile." Furthermore, "(meth)acrylic" means "acrylic or methacrylic."

[0011] The resin composition of this embodiment contains a modified hydrogenated product (A) and a resin (B). The present inventors conducted extensive research into formulations for achieving excellent tensile properties and adhesive strength in a resin composition. As a result, the present inventors found that it is effective for the modified hydrogenated product (A) to contain a polymer block (A-2) having a specific vinyl bond content. In addition, they found that it is effective for the resin composition to contain at least one resin (B) selected from the group consisting of acrylic block copolymers and thermoplastic polyurethane resins, and for the resin composition to exhibit a specific melt flow rate.

[0012] Some conventional resin compositions require molding temperatures of about 260°C or higher to obtain sufficient adhesive strength during injection molding. However, some resin compositions undergo thermal degradation at high temperatures of about 260°C or higher. For example, thermal degradation can cause a decrease in tensile elongation and a change in hue, which can reduce their value as plastic materials. On the other hand, when the above-mentioned resin compositions are injection molded at low temperatures (about 230°C), which are less likely to cause a decrease in tensile elongation or a change in hue, sufficient adhesive strength cannot be obtained, and the original purpose cannot be achieved. The resin composition of this embodiment can exhibit strong adhesive strength even when injection molded at low temperatures (for example, about 230°C). The reason for this is not necessarily clear, but one possible factor is that the modified hydrogenated product (A) having a reactive functional group contains a polymer block (A-2) having a specific vinyl bond content. The resin composition of this embodiment contains the modified hydrogenated product (A) containing the polymer block (A-2) and the resin (B), and it is presumed that the functional groups contained in the modified hydrogenated product (A) are present in large amounts on the surface of a molded article of the resin composition, thereby improving adhesive strength through an anchoring effect. The presence of large amounts of the functional groups on the surface of a molded article of the resin composition is thus thought to be due to favorable effects of the vinyl bond content of the polymer block (A-2) and the inclusion of the resin (B). Furthermore, the resin composition of this embodiment exhibits a specific melt flow rate and can exhibit strong adhesive strength even when injection molded under low-temperature conditions, and therefore is thought to be able to exhibit excellent tensile elongation and suppress change in hue.

[0013] <Resin Composition> [Modified Hydrogenated Product (A)] The modified hydrogenated product (A) 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 modified hydrogenated product (A) may be used alone or in combination of two or more types.

[0014] <Polymer Block (A-1)> The polymer block (A-1) contains structural units derived from an aromatic vinyl compound. From the viewpoint of mechanical strength, the lower limit of the content of structural units derived from an aromatic vinyl compound in 100 mol% of the polymer block (A-1) is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 100 mol%. The upper limit of the content of structural units derived from an aromatic vinyl compound in 100 mol% of the polymer block (A-1) may be 100 mol% or less, less than 100 mol%, or 99 mol% or less, as long as the effects of the present invention are not impaired.

[0015] Examples of aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m o-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-t-butylstyrene, m-t-butylstyrene, p-t-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, indene, vinylnaphthalene, N-vinylcarbazole, etc. 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, the aromatic vinyl compound is preferably styrene, α-methylstyrene, or p-methylstyrene, and more preferably styrene.

[0016] [Monomers Other Than Aromatic Vinyl Compounds] As long as the objects and effects of the present invention are not impaired, the polymer block (A-1) may contain structural units derived from unsaturated monomers other than aromatic vinyl compounds (hereinafter, sometimes referred to as "other unsaturated monomer units"). Alternatively, the polymer block (A-1) may contain no other unsaturated monomer units. From the viewpoint of mechanical strength, the upper limit of the content of other unsaturated monomer units in 100 mol% of the polymer block (A-1) is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, still more preferably 5 mol% or less, and particularly preferably 0 mol%. The lower limit of the content of other unsaturated monomer units in 100 mol% of the polymer block (A-1) may be more than 0 mol% or may be 1 mol% or more, as long as the effects of the present invention are not impaired.

[0017] Examples of the other unsaturated monomer include at least one selected from the group consisting of butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, etc. When the polymer block (A-1) contains other unsaturated monomer units, the bonding form is not particularly limited and may be either random or tapered.

[0018] The modified hydrogenated product (A) may have at least one polymer block (A-1). When the modified hydrogenated product (A) has two or more polymer blocks (A-1), the polymer blocks (A-1) may be the same or different. In this specification, "different polymer blocks" means that the polymer blocks are different in 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 the respective monomer units and the form of copolymerization (random, gradient, block).

[0019] (Weight Average Molecular Weight of Polymer Block (A-1)) The weight average molecular weight (Mw) of the polymer block (A-1) is preferably 1,000 to 40,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 20,000, and even more preferably 4,000 to 15,000, of at least one polymer block (A-1) among the polymer blocks (A-1) contained in the modified hydrogenated product (A). When the modified hydrogenated product (A) contains at least one polymer block (A-1) having a weight average molecular weight within the above range, the mechanical strength of the resin composition is further improved, and the moldability is also likely to be excellent. In this specification, the weight average molecular weight is the weight average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the Examples.

[0020] (Content of polymer block (A-1)) The upper limit of the content of polymer block (A-1) in 100% by mass of modified hydrogenated product (A) is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 20% by mass or less, and even more preferably 15% by mass or less. If the content of polymer block (A-1) is 40% by mass or less, the resin composition is more likely to exhibit excellent adhesive strength, which is preferable. Furthermore, the lower limit of the content of polymer block (A-1) in 100% by mass of modified hydrogenated product (A) is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 10% by mass or more. If the content of polymer block (A-1) is 5% by mass or more, the resin composition is more likely to exhibit excellent tensile properties, which is preferable. In this specification, the content of each polymer block in the block copolymer is １ The value is determined by H-NMR measurement. The detailed measurement method can be the same as that described in the Examples.

[0021] <Polymer Block (A-2)> [Conjugated Diene Compound] The polymer block (A-2) contains structural units derived from a conjugated diene compound. From the viewpoint of the tensile properties and adhesive strength of the resin composition, the lower limit of the content of structural units derived from a conjugated diene compound in 100 mol% of the polymer block (A-2) is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably 100 mol%. The upper limit of the content of structural units derived from a conjugated diene compound in 100 mol% of the polymer block (A-2) may be 100 mol% or less, less than 100 mol%, or 99 mol% or less, as long as the effects of the present invention are not impaired.

[0022] Examples of conjugated diene compounds include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, farnesene, myrcene, and chloroprene. These conjugated diene compounds may be used alone or in combination of two or more. In particular, from the viewpoint of achieving excellent tensile properties and adhesive strength in the resin composition, the conjugated diene compound in the polymer block (A-2) preferably contains at least isoprene, and preferably contains, for example, isoprene, or isoprene and butadiene. Furthermore, from the viewpoint of making it easier for the resin composition to exhibit excellent tensile properties and adhesive strength, the lower limit of the content of the structural unit derived from isoprene in 100% by mass of polymer block (A-2) is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, and still more preferably 50% by mass or more, and may be 100% by mass.

[0023] When isoprene and butadiene are used in combination, the blending ratio [isoprene / butadiene] (mass ratio) thereof is not particularly limited, but is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, even more preferably 40 / 60 to 70 / 30, and still more preferably 45 / 55 to 65 / 35. When expressed as a molar ratio, the blending 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 still more preferably 45 / 55 to 55 / 45.

[0024] [Monomers Other Than Conjugated Diene Compounds] As long as the objectives and effects of the present invention are not impaired, the polymer block (A-2) may contain structural units derived from polymerizable monomers other than conjugated diene compounds, or may not contain such structural units. From the viewpoint of the mechanical strength of the resin composition, the upper limit of the content of structural units derived from other polymerizable monomers in 100 mol% of the polymer block (A-2) is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, still more preferably 5 mol% or less, and particularly preferably 0 mol%. The lower limit of the content of structural units derived from other polymerizable monomers in the polymer block (A-2) may be more than 0 mol% or may be 1 mol% or more, as long as the effects of the present invention are not impaired.

[0025] Preferred examples of other polymerizable monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-t-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 modified hydrogenated product (A) is required to have at least one polymer block (A-2). When the modified hydrogenated product (A) has two or more polymer blocks (A-2), the polymer blocks (A-2) may be the same or different.

[0026] (Amount of vinyl bonds in polymer block (A-2)) In the modified hydrogenated product (A), for example, when the structural units constituting the polymer block (A-2) are either isoprene units or mixed units of isoprene and butadiene, the bonding forms of the isoprene and butadiene can be 1,2-bonds or 1,4-bonds in the case of butadiene, and 1,2-bonds, 3,4-bonds, or 1,4-bonds in the case of isoprene. Only one type of these bonding forms may be present, or two or more types may be present. Of these, 1,2-bonds and 3,4-bonds are considered to be vinyl bond units, and the content ratio of vinyl bond units is considered to be the vinyl bond content. In this case, the content ratio of vinyl bond units to the total amount of structural units derived from isoprene and / or butadiene is considered to be the vinyl bond content. Furthermore, in the modified hydrogenated product (A), for example, when the structural units constituting the polymer block (A-2) contain β-farnesene units, the β-farnesene can have 1,2-bonds, 1,13-bonds, or 3,13-bonds. Only one type of these bond forms may be present, or two or more types may be present. Of these, 1,2-bonds and 3,13-bonds are considered to be vinyl bond units, and in this case, the vinyl bond content is the ratio of the vinyl bond units to the total amount of structural units derived from β-farnesene. In the modified hydrogenated product (A), for example, when the structural units constituting the polymer block (A-2) contain isoprene units and / or butadiene units and β-farnesene units, the vinyl bond content is the sum of the ratio of the vinyl bond units to the total amount of structural units derived from isoprene and / or butadiene and the ratio of the vinyl bond units to the total amount of structural units derived from β-farnesene.

[0027] The vinyl bond content of the polymer block (A-2) is 50 to 99 mol%. When the vinyl bond content of the polymer block (A-2) is 50 mol% or more, strong adhesive strength can be exerted to both synthetic resins and metals. On the other hand, when the vinyl bond content of the polymer block (A-2) is 99 mol% or less, the resin composition has flexibility and can exert excellent tensile properties. From the viewpoint of adhesive strength, the lower limit of the vinyl bond content is preferably 55 mol% or more, more preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, still more preferably 72 mol% or more, and even more preferably 75 mol% or more. Furthermore, from the viewpoint of flexibility and tensile properties, the upper limit of the vinyl bond content is preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 88 mol% or less, and still more preferably 85 mol% or less.

[0028] In the present specification, the vinyl bond content is measured according to the method described in the Examples. １ It is a value calculated by H-NMR measurement. In the present embodiment, the vinyl bond content can be adjusted, for example, by adjusting the type and addition amount of a Lewis base used as a co-catalyst (vinylating agent) during polymerization.

[0029] (Weight Average Molecular Weight of Polymer Block (A-2)) The weight average molecular weight (Mw) of at least one polymer block (A-2) among the polymer blocks (A-2) contained in the modified hydrogenated product (A) is preferably 50,000 to 600,000, more preferably 60,000 to 500,000, even more preferably 80,000 to 400,000, and still more preferably 100,000 to 300,000. When the modified hydrogenated product (A) has at least one polymer block (A-2) having a weight average molecular weight within the above range, the tensile properties are further improved, and the resin composition is more likely to exhibit excellent adhesive strength.

[0030] (Content of Polymer Block (A-2)) The upper limit of the content of polymer block (A-2) in 100% by mass of the modified hydrogenated product (A) is preferably 95% by mass or less, more preferably 92% by mass or less, and even more preferably 90% by mass or less. If the content of polymer block (A-2) in 100% by mass of the modified hydrogenated product (A) is 95% by mass or less, it is preferable because the resin composition can more easily obtain excellent mechanical strength and moldability. Furthermore, the lower limit of the content of polymer block (A-2) in the modified hydrogenated product (A) is preferably 60% by mass or more, more preferably 70% 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 polymer block (A-2) in 100% by mass of the modified hydrogenated product (A) is 60% by mass or more, it is preferable because the resin composition can more easily exhibit excellent adhesive strength.

[0031] (Hydrogenation Rate of Polymer Block (A-2)) From the viewpoint of the heat resistance and weather resistance of the resin composition, the lower limit of the hydrogenation rate of carbon-carbon double bonds in the polymer block (A-2) is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 88 mol% or more, and still more preferably 90 mol% or more. There is no particular limitation on the upper limit of the hydrogenation rate, and it may be 100 mol% or less, 99.9 mol% or less, or 99.5 mol% or less. In this specification, the hydrogenation rate refers to the content of carbon-carbon double bonds in structural units derived from a conjugated diene compound in a polymer block, calculated by the ratio of the content of carbon-carbon double bonds in the structural units derived from a conjugated diene compound in the polymer block before and after hydrogenation. １ The hydrogenation rate can be calculated by H-NMR measurement. Specifically, it is calculated by the following formula: Hydrogenation rate (mol %) of modified hydrogenated product (A) before modification = {1 - (number of moles of carbon-carbon double bonds contained per mole of modified hydrogenated product (A) before modification) / (number of moles of carbon-carbon double bonds contained per mole of modified hydrogenated product (A) before modification before hydrogenation)} × 100 More specifically, the hydrogenation rate is measured according to the method described in the Examples.

[0032] (Bonding Mode Between Polymer Block (A-1) and Polymer Block (A-2)) The bonding mode of the modified hydrogenated product (A) is not limited as long as the polymer block (A-1) and the polymer block (A-2) are bonded together, and may be linear, branched, radial, or a combination of two or more of these. Among these, the bonding mode between the polymer block (A-1) and the polymer block (A-2) is preferably linear. The bonding mode may be, for example, a diblock copolymer represented by A-B, a triblock copolymer represented by A-B-A or B-A-B, a tetrablock copolymer represented by A-B-A-B, a pentablock copolymer represented by A-B-A-B-A or B-A-B-A-B, or a copolymer (A-B) ｎ Examples of the A-B-A type triblock copolymer include a styrene-hydrogenated butadiene / isoprene-styrene copolymer, a styrene-hydrogenated butadiene-styrene copolymer, and a styrene-hydrogenated isoprene-styrene copolymer.

[0033] Here, in the present specification, when polymer blocks of the same type are linearly bonded via a bifunctional coupling agent or the like, the entirety of the bonded polymer blocks is treated as a single polymer block. Accordingly, including the above examples, polymer blocks that should strictly be expressed as Y-Z-Y (Z represents a coupling residue) are expressed as Y as a whole, unless it is particularly necessary to distinguish them from a single polymer block Y. In the present 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 A-B-Z-B-A (Z represents a coupling agent residue) is expressed as A-B-A and is treated as an example of a triblock copolymer.

[0034] (Content of polymer blocks (A-1) and (A-2)) The modified hydrogenated product (A) may contain polymer blocks other than the polymer blocks (A-1) and (A-2), as long as the purpose and effects of the present invention are not hindered, or may not contain such other polymer blocks. In 100% by mass of the modified hydrogenated product (A), the lower limit of 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. A content of 90% by mass or more is preferred because the resin composition is more likely to exhibit excellent mechanical strength, moldability, and adhesive strength. In the modified hydrogenated product (A), the upper limit of the total content of the polymer blocks (A-1) and (A-2) is preferably 100% by mass or less.

[0035] <Functional Group> The modified hydrogenated product (A) has at least one functional group selected from the group consisting of a carboxy group, an amino group, a hydroxy group, and a group derived from an acid anhydride. By including the modified hydrogenated product (A) having the functional group, the resin composition of this embodiment can exhibit strong adhesive strength to synthetic resins and metals. Examples of the acid anhydride-derived group include a group derived from maleic anhydride. Here, the "maleic anhydride-derived group" refers to a group having a structure in which one of the carbon atoms that constituted the double bond of the maleic anhydride ring becomes a bond. From the viewpoint of the adhesive strength of the resin composition, particularly the adhesive strength to metals, the functional group possessed by the modified hydrogenated product (A) is preferably at least one functional group selected from the group consisting of a carboxy group and a group derived from an acid anhydride, and more preferably a group derived from an acid anhydride. Furthermore, the modified hydrogenated product (A) preferably has the above-mentioned functional group in its side chain, and more preferably has the above-mentioned functional group in the side chain of the polymer block (A-2), thereby improving the adhesive strength of the resin composition of this embodiment. The method for producing the modified hydrogenated product (A) is specifically described below.

[0036] The lower limit of the content of the functional group in the modified hydrogenated product (A) is preferably 0.10 phr or more, more preferably 0.15 phr or more, even more preferably 0.20 phr or more, and even more preferably 0.30 phr or more. The upper limit of the content of the functional group in the modified hydrogenated product (A) is preferably 5.00 phr or less, more preferably 4.00 phr or less, even more preferably 3.00 phr or less, even more preferably 2.00 phr or less, even more preferably 1.50 phr or less, and even more preferably 1.00 phr or less, and may even be 0.90 phr or less. When the content of the functional group in the modified hydrogenated product (A) is within the above range, the adhesive strength of the resin composition containing the modified hydrogenated product (A) can be easily improved, and the tensile properties can be more excellent, which is preferable. When the content of the functional group in the modified hydrogenated product (A) is below the upper limit of the above range, gelation can be suppressed, which is preferable. The content of functional groups (phr) refers to the parts by mass of functional groups relative to 100 parts by mass of the modified hydrogenated product (A). The content of functional groups in the modified hydrogenated product (A) can be calculated by neutralization titration. As described above, in a preferred embodiment, the functional group possessed by the modified hydrogenated product (A) is at least one functional group selected from the group consisting of a carboxy group and a group derived from an acid anhydride. More specifically, the content of functional groups relative to the modified hydrogenated product (A) is measured according to the method described in the Examples.

[0037] <Method for Producing Modified Hydrogenated Product (A)> The modified hydrogenated product (A) can be produced by first using at least an aromatic vinyl compound and a conjugated diene compound as monomers, polymerizing them to form a block copolymer, and then, before or after hydrogenating the block copolymer, subjecting it to a modification reaction using a modifier.

[0038] (Polymerization Reaction) The polymerization reaction can be carried out by, for example, a solution polymerization method, an emulsion polymerization method, a solid-phase polymerization method, or the like. Among these, the solution polymerization method is preferred, and known methods such as ionic polymerization methods such as anionic polymerization and cationic polymerization, and radical polymerization methods 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 the reaction.

[0039] Examples of organolithium compounds that can be used as anionic polymerization initiators include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium. Examples of dilithium compounds that can be used as anionic polymerization initiators include naphthalene dilithium and dilithiohexylbenzene. Examples of coupling agents include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenyl benzoate, tetramethoxysilane, methyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 3-glycidyloxypropyltriethoxysilane. The amounts of these anionic polymerization initiators and coupling agents used are determined appropriately depending on the desired weight-average molecular weight of the modified hydrogenated product (A). Usually, an anionic polymerization initiator such as an organolithium compound or a dilithium compound is preferably used in a proportion of 0.01 to 0.2 parts by mass per 100 parts by mass of the total of the monomers such as the aromatic vinyl compound and the conjugated diene compound used in the polymerization, and when a coupling agent is used, it is preferably used in a proportion of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the monomers.

[0040] 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, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. The polymerization reaction is usually carried out at a temperature of 0 to 100°C, preferably 10 to 70°C, for 0.5 to 50 hours, preferably 1 to 30 hours.

[0041] Furthermore, the vinyl bond content can be increased by adding a Lewis base as a co-catalyst during polymerization of a conjugated diene compound. Examples of usable Lewis bases 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, 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 dialkyl sodium cyclohexanolate, and sodium or potassium salts of alicyclic alcohols, such as sodium mentholate. Among the above Lewis bases, tetrahydrofuran and DTHFP are preferred from the viewpoint of ease of controlling the vinyl bond content. Furthermore, it is more preferable to use DTHFP because it can provide a high vinyl bond content, it is easy to achieve a high hydrogenation rate without using an excessive amount of a hydrogenation catalyst, and it can achieve both better tensile properties and adhesive strength. These Lewis bases can be used alone or in combination of two or more.

[0042] The amount of Lewis base added is determined arbitrarily depending on the extent to which the amount of vinyl bonds in the polymer block (A-2) is controlled. Therefore, although there is no strict limitation on the amount of Lewis base added, it is preferable to use it in the range of usually 0.1 to 1,000 mol, preferably 1 to 100 mol, per gram atom of lithium contained in the organolithium compound or dilithium compound used as a polymerization initiator. After polymerization is 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.

[0043] (Hydrogenation) A hydrogenated block copolymer can be obtained by hydrogenating the block copolymer obtained in the above step. When hydrogenating a block copolymer, a hydrogenation reaction (hydrogenation reaction) is carried out in an inert organic solvent in the presence of a hydrogenation catalyst. The hydrogenation reaction hydrogenates the carbon-carbon double bonds derived from the conjugated diene compound in the polymer block (A-2) of the block copolymer, resulting in a hydrogenated block copolymer. 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. The hydrogenation reaction can be carried out at a reaction temperature of about 20 to 250°C, preferably 50 to 180°C, and more preferably 70 to 180°C. The hydrogenation reaction can be carried out for a reaction time of typically 0.1 to 100 hours, preferably 1 to 50 hours. Examples of hydrogenation catalysts 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 organolithium compound, or the like; and metallocene catalysts. Among these, from the viewpoint of easily suppressing nuclear hydrogenation of aromatic rings, Ziegler catalysts are preferred, more preferably Ziegler catalysts consisting of a combination of a transition metal compound with an alkylaluminum compound, and even more preferably Ziegler catalysts consisting of a combination of a nickel compound with an alkylaluminum compound (Al / Ni-based Ziegler catalysts). The hydrogenated product of the block copolymer obtained in this manner can be obtained by pouring the polymerization reaction solution into methanol or the like to precipitate the product, followed by heating or drying under reduced pressure, or by pouring the polymerization reaction solution into hot water with steam, subjecting the product to so-called steam stripping in which the solvent is removed azeotropically, followed by heating or drying under reduced pressure.

[0044] (Modification Reaction) The above-mentioned functional group can be introduced into the block copolymer before or after hydrogenation to produce the modified hydrogenated product (A). When the functional group is introduced by a radical reaction, from the viewpoint of reaction control, it is preferable to hydrogenate the block copolymer to form a hydrogenated product and then introduce the specific functional group. The reaction of modifying the hydrogenated product by introducing the above-mentioned functional group (hereinafter sometimes referred to as the "modification reaction") can be carried out by a known method.

[0045] The modification reaction can be carried out, for example, by dissolving the hydrogenated block copolymer in an organic solvent, adding various modifiers capable of adding the above-mentioned functional groups, and reacting at about 50 to 300°C for about 0.5 to 10 hours. Alternatively, the modification reaction can be carried out, for example, by moltenizing the hydrogenated block copolymer using an extruder or the like without using a solvent, and then adding various modifiers. In this case, the modification reaction temperature is typically above the glass transition temperature of the hydrogenated block copolymer but not exceeding 400°C, preferably 90 to 350°C, and more preferably 100 to 300°C. The modification reaction time is typically about 0.5 to 10 minutes. It is preferable to add a radical initiator when carrying out the modification reaction in a molten state, and an antioxidant may also be added to suppress side reactions. A radical initiator may also be added in the reaction to modify the block copolymer by introducing the above-mentioned functional groups before hydrogenating the block copolymer.

[0046] The modification reaction is preferably carried out by the latter method of modification in a molten state, from the viewpoint of improving workability and thermal stability. That is, a preferred embodiment of the method for producing the modified hydrogenated product (A) comprises the steps of hydrogenating the block copolymer to form a hydrogenated product, and then introducing at least one functional group selected from the group consisting of a carboxy group, an amino group, a hydroxy group, and a group derived from an acid anhydride into the hydrogenated product in a molten state using a radical initiator.

[0047] Modifiers capable of adding the functional groups include vinylbenzyl diethylamine, vinylbenzyl dimethylamine, 1-glycidyl-4-(2-pyridyl)piperazine, 1-glycidyl-4-phenylpiperazine, 1-glycidyl-4-methylpiperazine, 1-glycidyl-4-methylhomopiperazine, 1-glycidylhexamethyleneimine, tetraglycidyl-1,3-bisaminomethylcyclohexane, 1-dodecanol, cetanol (cetyl alcohol), stearyl alcohol, oleyl alcohol, and the like. Unsaturated carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, and itaconic anhydride can also be used as modifiers. Furthermore, modifiers capable of adding the functional groups may be selected from those described in JP 2011-132298 A. The modifiers can be used alone or in combination of two or more.

[0048] The amount of the modifier to be added may be determined appropriately so as to obtain the desired content of the functional group. 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 block copolymer or its hydrogenated product.

[0049] As the radical initiator, organic peroxides or organic peresters such as dialkyl peroxides, diacyl peroxides, peroxyesters, peroxyketals, dialkyl peroxides, and hydroperoxides can be used. 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. In the modification reaction, the amount of radical initiator added can be determined appropriately depending on the combination of the block copolymer or its hydrogenated product with the modifier. The amount of radical initiator added is typically 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 block copolymer or its hydrogenated product.

[0050] <Melt Flow Rate of Modified Hydrogenated Product (A)> The modified hydrogenated product (A) has a melt flow rate, measured in accordance with JIS K 7210:2014 at a temperature of 230°C and a load of 21 N, of preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, and even more preferably 10 g / 10 min or more. The upper limit of the melt flow rate of the modified hydrogenated product (A) is preferably 30 g / 10 min or less, more preferably 26 g / 10 min or less, and even more preferably 23 g / 10 min or less. When the melt flow rate of the modified hydrogenated product (A) is within the above numerical range, the resin composition has excellent moldability and even more excellent tensile properties.

[0051] <Weight-average molecular weight of modified hydrogenated product (A)> From the viewpoint of the mechanical strength of the resin composition, the lower limit of the weight-average molecular weight of the modified hydrogenated product (A) is preferably 50,000 or more, more preferably 80,000 or more, even more preferably 100,000 or more, and still more preferably 130,000 or more. From the viewpoint of the moldability and adhesive strength of the resin composition, the upper limit of the weight-average molecular weight of the modified hydrogenated product (A) is preferably 400,000 or less, more preferably 350,000 or less, even more preferably 300,000 or less, and still more preferably 200,000 or less.

[0052] <Tan δ Peak Top Intensity and Peak Top Temperature of Modified Hydrogenated Product (A)> The modified hydrogenated product (A) preferably has a tan δ peak top intensity of 1.0 to 3.0, measured in accordance with JIS K 7244-10:2005 under conditions of a strain of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to +120°C, and a heating rate of 3°C / min. In this embodiment, the tan δ peak top intensity can be 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 having a thickness of 1.0 mm, and then cutting the single-layer sheet into a disk-shaped test piece. In this embodiment, there are no particular limitations on the device for measuring tan δ, but the test can be performed using a rotational rheometer "ARES-G2" (manufactured by TA Instruments) or the like, with the test piece sandwiched between flat plates having a diameter of 8 mm. More details are as described in the Examples.

[0053] The modified hydrogenated product (A) preferably has a lower limit of the tan δ peak top intensity of 1.0 or more, and in some cases even has a higher limit of 1.5 or more, or even 1.9 or more. The upper limit of the tan δ peak top intensity is not particularly limited and may be 3.0 or less, 2.5 or less, or 2.3 or less. The higher the tan δ peak top intensity, the more excellent the physical properties such as vibration damping at that temperature.

[0054] The tan δ peak top temperature of the modified hydrogenated product (A) is determined by the same method as the tan δ peak top intensity. Furthermore, the lower limit of the tan δ peak top temperature of the modified hydrogenated product (A) is preferably −25°C or higher, more preferably −10°C or higher, and even more preferably 0°C or higher. The upper limit of the tan δ peak top temperature may be within a range that does not impair the effects of the present invention, and may be +40°C or lower, or may be +35°C or lower. If the tan δ peak top temperature of the modified hydrogenated product (A) is within the above range, the resin composition is likely to have better adhesive strength and tensile properties, which is preferable. The tan δ peak top intensity and peak top temperature can be controlled by optimizing the selection and content ratio of the monomers used in the modified hydrogenated product (A), suitably adjusting the vinyl bond amount, or other methods.

[0055] <Glass Transition Temperature of Modified Hydrogenated Product (A)> The glass transition temperature of the modified hydrogenated product (A) is preferably −30 to +40° C., more preferably −20 to +30° C., and even more preferably −5 to +25° C. If the glass transition temperature of the modified hydrogenated product (A) is within the above range, the resin composition is likely to have better adhesive strength and tensile properties, which is preferable. In this specification, the glass transition temperature is a value measured using a differential scanning calorimeter (DSC) measuring device.

[0056] [Resin (B)] Resin (B) is at least one selected from the group consisting of acrylic block copolymers and thermoplastic polyurethane resins. By using at least one selected from the group consisting of acrylic block copolymers and thermoplastic polyurethane resins as resin (B), the resin composition of this embodiment can exhibit stronger adhesive strength to synthetic resins, metals, etc. When the resin composition contains an acrylic block copolymer, it is preferable to use an acrylic block copolymer, as this resin composition has significantly better adhesive strength to metals.

[0057] <Acrylic Block Copolymer> The acrylic block copolymer is a copolymer having a plurality of polymer blocks each containing a structural unit derived from a (meth)acrylic acid ester. Among the acrylic block copolymers, an acrylic block copolymer having a polymer block (D1) containing a structural unit derived from an acrylic acid ester and a polymer block (E1) containing a structural unit derived from a methacrylic acid ester is preferred from the viewpoints of flexibility, weather resistance, and adhesive strength.

[0058] [Polymer Block (D1)] The polymer block (D1) contains a structural unit derived from an acrylic acid ester. Such an acrylic acid ester is represented by the general formula CH ２ =CH-COOR １ (X) (In formula (X), R １ represents an organic group having 1 to 3 carbon atoms) (hereinafter referred to as "acrylic acid ester (d-1)"), ２ =CH-COOR ２ (Y) (wherein R ２ represents an organic group having 4 to 12 carbon atoms) (hereinafter referred to as "acrylic acid ester (d-2)"), and other acrylic acid esters.

[0059] The above R １ Examples of the organic group having 1 to 3 carbon atoms represented by the formula (d-1) include alkyl groups having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group; and organic groups containing an element other than carbon, such as oxygen, and having a total of 1 to 3 carbon atoms, such as a methoxyethyl group, a hydroxyethyl group, an aminoethyl group, and a glycidyl group. Examples of the acrylic acid ester (d-1) include acrylic acid esters having no functional group, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, and n-propyl acrylate; and acrylic acid esters having a functional group, such as 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-aminoethyl acrylate, and glycidyl acrylate.

[0060] The above R ２Examples of the organic group having 4 to 12 carbon atoms represented by the formula (I) include alkyl groups having 4 to 12 carbon atoms, such as a butyl group, an amyl group (pentyl group), a hexyl group, a cyclohexyl group, an ethylhexyl group, an octyl group, a decyl group, an isobornyl group, and a lauryl group; aromatic ring groups having 6 to 12 carbon atoms, such as a phenyl group and a benzyl group; and organic groups having a total of 4 to 12 carbon atoms and containing an element other than carbon, such as oxygen, such as an ethoxyethyl group, a tetrahydrofurfuryl group, a diethylaminoethyl group, and a phenoxyethyl group. Examples of such acrylic acid esters (d-2) include acrylic acid esters having no functional group, such as n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, isobornyl acrylate, lauryl acrylate, cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate; and acrylic acid esters having a functional group, such as 2-ethoxyethyl acrylate, 2-(diethylamino)ethyl acrylate, tetrahydrofurfuryl acrylate, and 2-phenoxyethyl acrylate.

[0061] Examples of acrylic esters other than the acrylic ester (d-1) and the acrylic ester (d-2) include acrylic esters having no functional group, such as octadecyl acrylate.

[0062] Among the acrylic acid esters (d-1), from the viewpoint of flexibility of the resulting resin composition, acrylic acid esters having no functional group are preferred, methyl acrylate and ethyl acrylate are more preferred, and methyl acrylate is even more preferred.

[0063] (d-1) / (D1) The proportion of the acrylic acid ester (d-1) contained in the polymer block (D1), [(d-1) / (D1)], is preferably 10 to 100 mass%, more preferably 30 to 100 mass%, and even more preferably 50 to 100 mass%. The proportion of the acrylic acid ester (d-1) contained in the polymer block (D1) may be 100 mass%. By being in the above range, the molding processability of the resin composition of this embodiment is improved. The contents of the acrylic acid ester (d-1) and polymer block (D1) are １ It can be determined by H-NMR, specifically by the method described in the Examples.

[0064] Among the acrylic acid esters (d-2), acrylic acid esters having no functional group are preferred, since they result in clearer phase separation between the polymer block (D1) and the polymer block (E1), and therefore exhibit high cohesive strength when formed into a resin composition, more preferred are alkyl acrylates having an alkyl group having 4 to 12 carbon atoms, and even more preferred are n-butyl acrylate and 2-ethylhexyl acrylate. Furthermore, n-butyl acrylate is more preferred, since the resulting resin composition exhibits stable durability over a wide temperature range.

[0065] The acrylic acid ester may be used alone or in combination of two or more thereof. The lower limit of the content of the structural unit derived from the acrylic acid ester in 100% by mass of the polymer block (D1) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass.

[0066] Among the above acrylic acid esters, at least one selected from the group consisting of acrylic acid ester (d-1) and acrylic acid ester (d-2) is preferred, from the viewpoints of increasing the compatibility between the acrylic block copolymer and the modified hydrogenated product (A) and exhibiting stable adhesive strength and moldability.

[0067] In one preferred embodiment, the acrylic acid ester used in the polymer block (D1) contains at least one selected from acrylic acid esters (d-1) and at least one selected from acrylic acid esters (d-2). In this case, the mass ratio (d-1) / (d-2) of the structural units derived from the acrylic acid ester (d-1) to the structural units derived from the acrylic acid ester (d-2) is preferably 90 / 10 to 10 / 90, more preferably 80 / 20 to 20 / 80, even more preferably 70 / 30 to 30 / 70, and even more preferably 60 / 40 to 40 / 60.

[0068] When the ratio (d-1) / (d-2) is in the above range, the compatibility between the acrylic block copolymer and the modified hydrogenated product (A) is improved, and stable adhesive strength and moldability are easily achieved. The mass ratio of the acrylic acid ester (d-1) to the acrylic acid ester (d-2) is １ It can be determined by H-NMR measurement.

[0069] Examples of the combination of the acrylic acid ester (d-1) and the acrylic acid ester (d-2) used in the polymer block (D1) include methyl acrylate / n-butyl acrylate. In this case, the acrylic acid ester (d-1) and the acrylic acid ester (d-2) used should be such that the difference in solubility parameter between the acrylic acid ester (d-1) and the acrylic acid ester (d-2) is 0.3 to 2.5 (MPa). １／２ The solubility parameter can be calculated by the method described in "POLYMER HANDBOOK Fourth Edition", VII, pp. 675-714 (published by Wiley Interscience in 1999) and "Polymer Engineering and Science", 1974, Vol. 14, pp. 147-154. When the acrylic block copolymer contains two or more polymer blocks (D1), the combinations of acrylic acid esters that constitute these polymer blocks (D1) may be the same or different.

[0070] When the polymer block (D1) is a copolymer containing both acrylic acid ester (d-1) units and acrylic acid ester (d-2) units, it may be a random copolymer of the acrylic acid ester (d-1) and the acrylic acid ester (d-2), a block copolymer, or a gradient copolymer, although a random copolymer is usually preferred. When the acrylic block copolymer contains two or more polymer blocks (D1), the structures of the polymer blocks (D1) may be the same or different. The lower limit of the proportion of the total units of the acrylic acid esters (d-1) and (d-2) contained in the polymer block (D1) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on 100% by mass of the polymer block (D1), and may even be 100% by mass.

[0071] The glass transition temperature of the polymer block (D1) is preferably −100 to +30° C., more preferably −80 to +10° C., even more preferably −70 to 0° C., and most preferably −60 to −10° C. When the glass transition temperature is within the above range, the resin composition of the present embodiment tends to have excellent adhesive strength at room temperature.

[0072] [Polymer Block (E1)] The polymer block (E1) contains a structural unit derived from a methacrylic acid ester. Examples of such methacrylic acid esters include methacrylic acid esters having no functional group, such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, isobornyl methacrylate, phenyl methacrylate, and benzyl methacrylate; and methacrylic acid esters having a functional group, such as methoxyethyl methacrylate, ethoxyethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate.

[0073] Among these, from the viewpoint of improving the heat resistance and durability of the resulting resin composition, polymer block (E1) is preferably a methacrylic acid ester having no functional group, and more preferably methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, phenyl methacrylate, or benzyl methacrylate. Methyl methacrylate is even more preferred as polymer block (E1) from the viewpoint of more clearly separating the phases between polymer block (D1) and polymer block (E1) and improving the mechanical strength of the resulting resin composition. Polymer block (E1) may be composed of one or more of these methacrylic acid esters. Furthermore, the acrylic block copolymer preferably has two or more polymer blocks (E1) from the viewpoint of further enhancing mechanical strength. In this case, the polymer blocks (E1) may be the same or different.

[0074] The peak top molecular weight (Mp) of the polymer block (E1) is not particularly limited, but is preferably in the range of 1,000 to 50,000, and more preferably in the range of 2,000 to 30,000. When the Mp of the polymer block (E1) is within the above range, there is no risk of the resulting acrylic block copolymer having insufficient cohesive strength, and the melt viscosity of the resulting acrylic block copolymer does not become too high, which tends to improve productivity when producing the resin composition. Note that Mp is the molecular weight at the apex of the peak in the differential molecular weight distribution curve obtained by GPC measurement. The lower limit of the content of the structural unit derived from a methacrylic acid ester in 100% by mass of the polymer block (E1) is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may even be 100% by mass.

[0075] The glass transition temperature of the polymer block (E1) is preferably 80 to 140° C., more preferably 90 to 130° C., and even more preferably 100 to 120° C. When the glass transition temperature is within the above range, the polymer block (E1) acts as a physical pseudo-crosslinking point at the normal use temperature of the resulting resin composition, and the resulting resin composition is likely to have excellent adhesive strength, durability, and heat resistance.

[0076] The polymer block (D1) may contain structural units derived from methacrylic acid esters, provided that the effects of the present invention are not impaired. Furthermore, the polymer block (E1) may contain structural units derived from acrylic acid esters, provided that the effects of the present invention are not impaired. Furthermore, if necessary, structural units derived from monomers other than (meth)acrylic acid esters may be contained. Examples of such other monomers include vinyl monomers having a carboxyl group, such as (meth)acrylic acid, crotonic acid, maleic acid, and fumaric acid; aromatic vinyl monomers, such as styrene, α-methylstyrene, p-methylstyrene, and m-methylstyrene; conjugated diene monomers, such as butadiene and isoprene; olefin monomers, such as ethylene, propylene, isobutene, and octene; lactone monomers, such as ε-caprolactone and valerolactone; (meth)acrylamide, (meth)acrylonitrile, maleic anhydride, vinyl acetate, vinyl chloride, and vinylidene chloride. When the above-mentioned monomer is used, the amount of the above-mentioned monomer is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the monomers used in each polymer block in the acrylic block copolymer.

[0077] The acrylic block copolymer may contain other polymer blocks, if necessary, in addition to the polymer block (D1) and the polymer block (E1). Examples of such other polymer blocks include polymer blocks or copolymer blocks containing structural units derived from monomers such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, acrylonitrile, methacrylonitrile, ethylene, propylene, isobutene, butadiene, isoprene, octene, vinyl acetate, maleic anhydride, vinyl chloride, and vinylidene chloride; and polymer blocks composed of polyethylene terephthalate, polylactic acid, polyurethane, and polydimethylsiloxane. The other polymer blocks also include hydrogenated products of polymer blocks containing structural units derived from conjugated diene compounds such as butadiene and isoprene.

[0078] The acrylic block copolymer is preferably represented by the following general formula, where D1 represents the polymer block (D1), D1' represents a polymer block having a structure different from that of the polymer block (D1) (excluding the polymer block (E1)), and E1 represents the polymer block (E1): (E1-D1) ｎ (E1-D1) ｎ -E1 D1- (E1-D1) ｎ (E1-D1) ｎ -D1' (E1-D1) ｎ -Z (D1-E1) ｎ -Z In the above general formula, n is an integer of 1 to 30, Z represents a coupling site (a coupling site after a coupling agent reacts with a polymer terminal to form a chemical bond, and "-" represents a bond of each polymer block). When a plurality of D1 and E1 are contained in the above general formula, they may be polymer blocks of the same structure or polymer blocks of different structures. Here, "different structures" means structures in which at least one of the monomer units constituting the polymer block, molecular weight, molecular weight distribution, stereoregularity, and, when a plurality of monomer units are present, the ratio of the respective monomer units and the copolymerization form (random, gradient, block) is different. The value of n is preferably 1 to 15, more preferably 1 to 8, and even more preferably 1 to 4. Among the above structures, (E1-D1) is preferred from the viewpoint of achieving superior mechanical strength of the resin composition. ｎ , (E1-D1) ｎ -E1, D1- (E1-D1) ｎ , (E1-D1) ｎ A linear block copolymer represented by -D1' is preferred, a diblock copolymer represented by E1-D1, a triblock copolymer represented by E1-D1-D1', and a triblock copolymer represented by E1-D1-E1 having blocks in the order of polymer block (E1), the polymer block (D1), and the polymer block (E1) are more preferred, and a triblock copolymer represented by E1-D1-E1 is even more preferred.

[0079] The peak top molecular weight (Mp) of the acrylic block copolymer is preferably 50,000 to 250,000. In particular, from the viewpoint of improving the fluidity of the resin composition, the Mp is more preferably 55,000 to 230,000, even more preferably 60,000 to 220,000, even more preferably 60,000 to 200,000, and particularly preferably 60,000 to 150,000.

[0080] The molecular weight distribution (Mw / Mn) of the acrylic block copolymer is preferably 1.00 to 1.40. From the viewpoint of excellent mechanical strength when formed into a resin composition, Mw / Mn is more preferably 1.00 to 1.35, even more preferably 1.00 to 1.30, even more preferably 1.00 to 1.25, and particularly preferably 1.00 to 1.20. The peak top molecular weight (Mp), number average molecular weight (Mn), and weight average molecular weight (Mw) of the acrylic block copolymer are values ​​determined by gel permeation chromatography in terms of standard polystyrene, and the molecular weight distribution (Mw / Mn) is a value calculated from the above Mw and Mn values.

[0081] The mass ratio [(E1) / (D1)] of the content of polymer block (E1) to the content of polymer block (D1) in the acrylic block copolymer is preferably 10 / 90 to 55 / 45, more preferably 15 / 85 to 55 / 45, even more preferably 20 / 80 to 53 / 47, and particularly preferably 25 / 75 to 52 / 48. １ It can be determined by H-NMR, specifically by the method described in the Examples.

[0082] [Method for Producing Acrylic Block Copolymer] The method for producing the acrylic block copolymer is not particularly limited as long as a polymer satisfying the above-mentioned conditions can be obtained, and a method based on a known technique can be adopted. Generally, a method for obtaining a block copolymer having a narrow molecular weight distribution is a method of living polymerization of monomers that become structural units. Examples of such living polymerization techniques include a method of living polymerization using an organic rare earth metal complex as a polymerization initiator (see JP-A-06-093060), a method of living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral acid salt such as an alkali metal or alkaline earth metal salt (see JP-A-05-507737), a method of living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see JP-A-11-335432), and atom transfer radical polymerization (ATRP) (see Macromolecular Chemistry and Physics, 2000, Vol. 201, pp. 1108-1114).

[0083] Among the above-mentioned production methods, the method of living anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound is preferred because the resulting block copolymer has high transparency, the amount of residual monomer is small, odor is suppressed, and the generation of bubbles can be suppressed when molding the resin composition. It is also preferred because the molecular structure of the polymer block (E1) becomes highly syndiotactic, which has the effect of enhancing the heat resistance of the resin composition.

[0084] Commercially available acrylic block copolymers may be used, and specific examples include "CLARITY (registered trademark)" (product name) manufactured by Kuraray Co., Ltd. and "NANOSTRENGTH (registered trademark)" (product name) manufactured by Arkema K.K.

[0085] <Thermoplastic polyurethane resin> The thermoplastic polyurethane resin can be, for example, a thermoplastic polyurethane obtained by reacting a polymeric diol, an organic diisocyanate, and a chain extender. The polymeric diol used to form the thermoplastic polyurethane resin preferably has a number average molecular weight of 1,000 to 6,000. This allows for the production of a resin composition with excellent mechanical strength, heat resistance, and the like. Here, the number average molecular weight of the polymeric diol referred to in this specification is the number average molecular weight calculated based on the hydroxyl value measured by SITE in accordance with JIS K 1557-1:2007.

[0086] Examples of polymer diols used in producing the thermoplastic polyurethane resin include polyester diols, polyether diols, polyester ether diols, polycarbonate diols, polyester polycarbonate diols, etc. These polymer diols may be used alone or in combination of two or more.

[0087] Examples of the polyester diol used in producing the thermoplastic polyurethane resin include polyester diols obtained by reacting at least one dicarboxylic acid component selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and esters thereof with a low-molecular-weight diol, and polyester diols obtained by ring-opening polymerization of lactone. More specifically, examples of the polyester diol include polyester diols obtained by polycondensation reaction of at least one selected from the group consisting of aliphatic dicarboxylic acids having 6 to 12 carbon atoms, such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, and orthophthalic acid, and esters thereof, with at least one aliphatic diol having 2 to 10 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, and 2-methyl-1,8-octanediol; polycaprolactone diol, and polyvalerolactone diol.

[0088] Examples of the polyether diol used in the production of the thermoplastic polyurethane resin include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Examples of the polycarbonate diol used in the production of the thermoplastic polyurethane resin include polycarbonate diols obtained by reacting at least one aliphatic diol such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, etc. with a carbonate ester such as diphenyl carbonate or alkyl carbonate, or with phosgene.

[0089] The organic diisocyanate used in producing the thermoplastic polyurethane resin is not particularly limited, but is preferably at least one selected from the group consisting of aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates having a molecular weight of not more than 500. Specific examples of the organic diisocyanate include 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate (4,4'-dicyclohexylmethane diisocyanate), isophorone diisocyanate, and hexamethylene diisocyanate, and among these, 4,4'-diphenylmethane diisocyanate is preferred.

[0090] The chain extender used in the production of thermoplastic polyurethane resins can be any of the chain extenders conventionally used in the production of thermoplastic polyurethane resins, and the type is not particularly limited. Among these, at least one chain extender selected from the group consisting of aliphatic diols, alicyclic diols, and aromatic diols is preferred. Specific examples of chain extenders include diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanediol, and 1,4-bis(β-hydroxyethoxy)benzene. Among these, aliphatic diols having 2 to 6 carbon atoms are preferred, and 1,4-butanediol is more preferred. These chain extenders may be used alone or in combination of two or more.

[0091] The thermoplastic polyurethane resin is preferably a thermoplastic polyurethane resin obtained by reacting a polymer diol, a chain extender, and an organic diisocyanate such that the ratio of the number of moles of the polymer diol to the number of moles of the chain extender is 1:0.2 to 8, and the ratio of the total number of moles of the polymer diol and the chain extender to the number of moles of the organic diisocyanate is 1:0.98 to 1.04. This prevents a sudden increase in melt viscosity during melt molding such as extrusion molding or injection molding of the resin composition of this embodiment, allowing for the smooth production of desired molded articles, laminate structures, and other products, and further improves the heat resistance of the resulting products.

[0092] The thermoplastic polyurethane resin preferably has a hardness (Type A hardness; measured at 25°C) of 55 to 95. When the thermoplastic polyurethane resin has a hardness of 55 or more, molded articles, laminate structures, and other products obtained from the resin composition have good mechanical strength. When the thermoplastic polyurethane resin has a hardness of 95 or less, molded articles, laminate structures, and other products obtained from the resin composition have high flexibility.

[0093] The method for producing the thermoplastic polyurethane resin is not particularly limited, and the resin may be produced by either a prepolymer method or a one-shot method using the above-mentioned polymeric diol, organic diisocyanate, and chain extender, utilizing a known urethane reaction. Among these, melt polymerization in the substantial absence of a solvent is preferred, and continuous melt polymerization using a multi-screw extruder is particularly preferred.

[0094] As the thermoplastic polyurethane resin, commercially available products may be used, and specific examples include "Elastollan (registered trademark)" (trade name) manufactured by BASF Polyurethane Elastomers Co., Ltd., "Miractollan (registered trademark)" (trade name) manufactured by Nippon Miractoran Co., Ltd., "Rezamin P" (trade name) manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., and "Eufine (registered trademark) P" (trade name) manufactured by Asahi Glass Co., Ltd.

[0095] [Hydrogenated Block Copolymer (C)] From the viewpoint of easily adjusting hardness while maintaining excellent tensile properties and strong adhesive strength, the resin composition of this embodiment preferably contains a hydrogenated block copolymer (C). The hydrogenated block copolymer (C) has a polymer block (C-1) containing structural units derived from an aromatic vinyl compound and a polymer block (C-2) containing structural units derived from a conjugated diene compound. Furthermore, the hydrogenated block copolymer (C) and the modified hydrogenated product (A) are different types of resin. The hydrogenated block copolymer (C) preferably does not contain a carboxy group, an amino group, a hydroxy group, or a group derived from an acid anhydride. The hydrogenated block copolymer (C) may contain any one of an epoxy group, a silanol group, an aldehyde group, a carbonyl group, a nitro group, a cyano group, and an ether bond. The hydrogenated block copolymer (C) may be used alone or in combination of two or more types.

[0096] <Polymer Block (C-1)> [Aromatic Vinyl Compound] The polymer block (C-1) contains structural units derived from an aromatic vinyl compound. The structural units constituting the polymer block (C-1), the content ratio of the structural units, and the types of compounds from which the structural units are derived are the same as those for the polymer block (A-1) described above.

[0097] (Weight Average Molecular Weight of Polymer Block (C-1)) The weight average molecular weight (Mw) of the polymer block (C-1) is not particularly limited, but the weight average molecular weight of at least one polymer block (C-1) among the polymer blocks (C-1) contained in the hydrogenated block copolymer (C) is preferably 3,000 to 80,000, more preferably 4,000 to 70,000, even more preferably 5,000 to 60,000, and still more preferably 6,000 to 50,000. When the hydrogenated block copolymer (C) contains at least one polymer block (C-1) having a weight average molecular weight within the above range, the mechanical strength of the resin composition is further improved and the moldability is also likely to be excellent.

[0098] (Content of Polymer Block (C-1)) The upper limit of the content of polymer block (C-1) in 100% by mass of hydrogenated block copolymer (C) is preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less. If the content of polymer block (C-1) is 70% by mass or less, the resin composition is more likely to exhibit appropriate flexibility, which is preferable. Furthermore, the lower limit of the content of polymer block (C-1) in 100% by mass of hydrogenated block copolymer (C) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. If the content of polymer block (C-1) is 5% by mass or more, the mechanical strength, such as tensile elongation, of the resin composition is more likely to be improved, which is preferable.

[0099] <Polymer Block (C-2)> [Conjugated Diene Compound] The polymer block (C-2) contains structural units derived from a conjugated diene compound. The structural units constituting the polymer block (C-2), the content ratio of the structural units, and the types of compounds from which the structural units are derived are the same as those for the polymer block (A-2) described above.

[0100] On the other hand, from the viewpoint of the balance between production costs and physical properties, the conjugated diene compound in the polymer block (C-2) is preferably at least one selected from the group consisting of isoprene, butadiene, and farnesene.

[0101] When isoprene and butadiene are used in combination, the blending ratio [isoprene / butadiene] (mass ratio) thereof is not particularly limited, but is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, even more preferably 40 / 60 to 70 / 30, and still more preferably 45 / 55 to 65 / 35. The blending ratio [isoprene / butadiene] expressed as a molar ratio is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, more preferably 20 / 80 to 80 / 20, even more preferably 30 / 70 to 70 / 30, even more preferably 40 / 60 to 70 / 30, and still more preferably 45 / 55 to 55 / 45.

[0102] (Amount of Vinyl Bonds in Polymer Block (C-2)) There are no particular limitations on the bonding form of the conjugated diene compound, as long as the effects of the present invention are not impaired. In the hydrogenated block copolymer (C), for example, when the structural units constituting the polymer block (C-2) are either isoprene units or mixed units of isoprene and butadiene, the bonding forms of the isoprene and butadiene can be 1,2-bonds or 1,4-bonds in the case of butadiene, and 1,2-bonds, 3,4-bonds, or 1,4-bonds in the case of isoprene. Only one type of these bonding forms may be present, or two or more types may be present. Of these, 1,2-bonds and 3,4-bonds are considered to be vinyl bond units, and the content ratio of vinyl bond units is considered to be the vinyl bond content. In this case, the content ratio of vinyl bond units to the total amount of structural units derived from isoprene and / or butadiene is considered to be the vinyl bond content. Furthermore, in the hydrogenated block copolymer (C), for example, when the structural unit constituting the polymer block (C-2) is a β-farnesene unit, it can have a 1,2-bond, a 1,13-bond, or a 3,13-bond. Only one type of these bond forms may be present, or two or more types may be present. Of these, the 1,2-bond and the 3,13-bond are considered to be vinyl bond units, and the content ratio of the vinyl bond units is considered to be the vinyl bond amount. In this case, the content ratio of the vinyl bond units to the total amount of structural units derived from β-farnesene is considered to be the vinyl bond amount. In the modified hydrogenated product (A), for example, when the structural units constituting the polymer block (C-2) include an isoprene unit and / or a butadiene unit and a β-farnesene unit, the vinyl bond amount is considered to be the sum of the content ratio of the vinyl bond units to the total amount of structural units derived from isoprene and / or butadiene and the content ratio of the vinyl bond units to the total amount of structural units derived from β-farnesene.

[0103] The lower limit of the vinyl bond content in the polymer block (C-2) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and even more preferably 6 mol% or more. A lower limit of 1 mol% or more of the vinyl bond content in the polymer block (C-2) is preferred because the resin composition is more likely to exhibit excellent tensile properties. The upper limit of the vinyl bond content in the polymer block (C-2) is preferably 85 mol% or less, more preferably 75 mol% or less, even more preferably 65 mol% or less, even more preferably 55 mol% or less, and particularly preferably 45 mol% or less. When emphasis is placed on achieving excellent adhesive strength by improving the flexibility of the resin composition and improving adhesion to the adherend, the upper limit of the vinyl bond content in the polymer block (C-2) is more particularly preferably 35 mol% or less, even more particularly preferably 30 mol% or less, and most preferably 25 mol% or less. A vinyl bond content of 85 mol% or less in the polymer block (C-2) is preferred because the resin composition is more likely to exhibit excellent flexibility.

[0104] The hydrogenated block copolymer (C) may be used alone or in combination of two or more. For example, when a molded article made from the resin composition of this embodiment is used in a low-temperature environment or when high impact resistance is required for the molded article, it is preferable to use at least one hydrogenated block copolymer (C) containing a polymer block (C-2) having a low vinyl bond content. The vinyl bond content in the polymer block (C-2) having a low vinyl bond content is preferably 1 to 30 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 10 mol%.

[0105] (Weight Average Molecular Weight of Polymer Block (C-2)) The weight average molecular weight (Mw) of the polymer block (C-2) is determined by gel permeation chromatography (GPC). The weight average molecular weight (Mw) of the polymer block (C-2) is preferably 30,000 to 600,000, more preferably 40,000 to 500,000, even more preferably 45,000 to 450,000, and still more preferably 50,000 to 400,000, among the polymer blocks (C-2) contained in the hydrogenated block copolymer (C). When the hydrogenated block copolymer (C) contains at least one polymer block (C-2) having a weight average molecular weight within the above range, the tensile properties of the resin composition are further improved and the adhesive strength is also likely to be excellent, which is preferable.

[0106] (Content of Polymer Block (C-2)) The upper limit of the content of polymer block (C-2) in 100% by mass of hydrogenated block copolymer (C) is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. If the content of polymer block (C-2) is 95% by mass or less, the resin composition is likely to exhibit excellent mechanical strength and moldability, which is preferable. Furthermore, the lower limit of the content of polymer block (C-2) in 100% by mass of hydrogenated block copolymer (C) is preferably 30% by mass or more, more preferably 45% by mass or more, even more preferably 60% by mass or more, and even more preferably 70% by mass or more. If the content of polymer block (C-2) is 30% by mass or more, the resin composition is likely to exhibit excellent flexibility, which is preferable.

[0107] (Hydrogenation Rate of Polymer Block (C-2)) From the viewpoint of the heat resistance and weather resistance of the resin composition, the lower limit of the hydrogenation rate of carbon-carbon double bonds in the polymer block (C-2) is preferably 80 mol% or more, more preferably 85 mol% or more, even more preferably 88 mol% or more, and still more preferably 90 mol% or more. There is no particular restriction on the upper limit of the hydrogenation rate, and it may be 100 mol% or less, 99.9 mol% or less, or 99.5 mol% or less. The hydrogenation rate of carbon-carbon double bonds in the polymer block (C-2) is determined by the difference between the polymer block before and after hydrogenation. １ The hydrogenation rate can be calculated by H-NMR measurement. Specifically, it can be calculated by the following formula: Hydrogenation rate (mol %) of hydrogenated block copolymer (C) = {1 - (number of moles of carbon-carbon double bonds contained per mole of hydrogenated block copolymer (C)) / (number of moles of carbon-carbon double bonds contained per mole of hydrogenated block copolymer (C) before hydrogenation)} × 100

[0108] (Bonding Mode Between Polymer Block (C-1) and Polymer Block (C-2)) The bonding mode between polymer block (C-1) and polymer block (C-2) is the same as the bonding mode between polymer block (A-1) and polymer block (A-2) described above.

[0109] (Content of polymer blocks (C-1) and (C-2)) The hydrogenated block copolymer (C) may contain polymer blocks other than the polymer blocks (C-1) and (C-2), as long as the purpose and effects of the present invention are not hindered, or may not contain such polymer blocks. In 100% by mass of the hydrogenated block copolymer (C), the lower limit of the total content of the polymer blocks (C-1) and (C-2) is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably substantially 100% by mass. A content of 90% by mass or more is preferred because the resin composition is likely to have excellent mechanical strength and moldability. In the hydrogenated block copolymer (C), the upper limit of the total content of the polymer blocks (C-1) and (C-2) is preferably 100% by mass or less.

[0110] <Method for producing hydrogenated block copolymer (C)> The hydrogenated block copolymer (C) can be produced by using at least an aromatic vinyl compound and a conjugated diene compound as monomers, polymerizing the resulting block copolymer, and then hydrogenating the resulting block copolymer. The block copolymer can be produced by the same method as the method for producing the block copolymer in the method for producing the modified hydrogenated product (A) described above. The hydrogenation method is also the same as the hydrogenation method in the method for producing the modified hydrogenated product (A) described above.

[0111] <Weight Average Molecular Weight of Hydrogenated Block Copolymer (C)> From the viewpoint of the mechanical strength of the resin composition, the lower limit of the weight average molecular weight of the hydrogenated block copolymer (C) is preferably 50,000 or more, more preferably 60,000 or more, even more preferably 70,000 or more, and still more preferably 100,000 or more. From the viewpoint of the moldability of the resin composition, the upper limit of the weight average molecular weight of the hydrogenated block copolymer (C) is preferably 500,000 or less, more preferably 450,000 or less, and even more preferably 400,000 or less.

[0112] <Tan δ Peak Top Intensity and Peak Top Temperature of Hydrogenated Block Copolymer (C)> The hydrogenated block copolymer (C) preferably has a tan δ peak top intensity of 0.05 to 3.0, measured in accordance with JIS K 7244-10: 2005 under conditions of a strain of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to +120° C., and a heating rate of 3° C. / min. The tan δ peak top intensity of the hydrogenated block copolymer (C) can be measured in the same manner as in the method for the modified hydrogenated product (A).

[0113] The hydrogenated block copolymer (C) has a tan δ peak top intensity of 0.3 or more, 1.0 or more, or even 2.0 or more, as measured above. The upper limit of the tan δ peak top intensity is not particularly limited and may be 2.5 or less. The higher the tan δ peak top intensity, the more excellent the physical properties, such as vibration damping properties, at that temperature.

[0114] The hydrogenated block copolymer (C) has a lower limit of the tan δ peak top temperature of preferably −65°C or higher, more preferably −60°C or higher, and even more preferably −55°C or higher. The upper limit of the tan δ peak top temperature may be within a range that does not impair the effects of the present invention, and may be +20°C or lower, or may be +10°C or lower. It is preferable that the tan δ peak top temperature of the hydrogenated block copolymer (C) be within the above range, because it becomes easier for the resin composition to obtain sufficient adhesive strength and tensile properties under actual use conditions. The tan δ peak top intensity and peak top temperature of the hydrogenated block copolymer (C) can be controlled by optimizing the selection and content ratio of the monomers used in the hydrogenated block copolymer (C), suitably adjusting the vinyl bond amount, or other methods.

[0115] <Glass Transition Temperature of Hydrogenated Block Copolymer (C)> The glass transition temperature of the hydrogenated block copolymer (C) is preferably −70 to +20° C., more preferably −65 to +10° C., and even more preferably −60 to +5° C. If the glass transition temperature of the hydrogenated block copolymer (C) is within the above range, it is preferable because the resin composition can more easily obtain sufficient adhesive strength and tensile properties under actual use environments.

[0116] [Content of Each Component] The mass ratio (A) / (B) of the modified hydrogenated product (A) and the resin (B) is 90 / 10 to 10 / 90. When the mass ratio (A) / (B) is within the above range, both the tensile properties and adhesive strength are excellent. From the viewpoint of easily exhibiting even better tensile properties and strong adhesive strength, the mass ratio (A) / (B) is more preferably 80 / 20 to 10 / 90, even more preferably 70 / 30 to 10 / 90, still more preferably 60 / 40 to 10 / 90, and even more preferably 55 / 45 to 10 / 90.

[0117] When the resin composition of this embodiment contains the hydrogenated block copolymer (C), from the viewpoint of easily exhibiting even stronger adhesive strength, the lower limit of the content of the hydrogenated block copolymer (C) per 100 parts by mass of the modified hydrogenated product (A) is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 70 parts by mass or more. Furthermore, when the resin composition of this embodiment contains the hydrogenated block copolymer (C), from the viewpoint of easily exhibiting even better tensile properties, the upper limit of the content of the hydrogenated block copolymer (C) per 100 parts by mass of the modified hydrogenated product (A) is preferably 1000 parts by mass or less, more preferably 800 parts by mass or less, and even more preferably 700 parts by mass or less.

[0118] When the resin composition of this embodiment contains hydrogenated block copolymer (C), from the viewpoint of easily exhibiting even stronger adhesive strength, the lower limit of the content of hydrogenated block copolymer (C) per 100 parts by mass of resin (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 40 parts by mass or more. Furthermore, when the resin composition of this embodiment contains hydrogenated block copolymer (C), from the viewpoint of easily exhibiting even better tensile properties, the upper limit of the content of hydrogenated block copolymer (C) per 100 parts by mass of resin (B) is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 150 parts by mass or less.

[0119] From the viewpoint that the resin composition tends to exhibit even stronger adhesive strength, the lower limit of the content of the modified hydrogenated product (A) in 100% by mass of the resin composition is preferably 5% by mass or more, more preferably 8% by mass or more, and even more preferably 12% by mass or more. Furthermore, from the viewpoint of obtaining both stable and good adhesive strength and tensile properties, the upper limit of the content of the modified hydrogenated product (A) in 100% by mass of the resin composition is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0120] When the hydrogenated block copolymer (C) and the softener described below are not included, the total content of the modified hydrogenated product (A) and the resin (B) in 100% by mass of the resin composition is preferably 95% by mass or more, more preferably 99% by mass or more, and even more preferably 99.5% by mass or more, and the upper limit may be 100% by mass or less. When the softener described below is not included, the total content of the modified hydrogenated product (A), the resin (B), and the hydrogenated block copolymer (C) in 100% by mass of the resin composition is preferably 95% by mass or more, more preferably 99% by mass or more, and even more preferably 99.5% by mass or more, and the upper limit may be 100% by mass or less. When the softener described below is included, the total content of the modified hydrogenated product (A), the resin (B), the hydrogenated block copolymer (C), and the softener in 100% by mass of the resin composition is preferably 95% by mass or more, more preferably 99% by mass or more, and even more preferably 99.5% by mass or more, and the upper limit may be 100% by mass or less.

[0121] [Softener] The resin composition of this embodiment may not contain a softener. On the other hand, from the viewpoint of making it easier for the resin composition to exhibit excellent moldability and flexibility, the resin composition of this embodiment may contain a softener. A softener is preferably used when the resin composition contains the hydrogenated block copolymer (C). A softener may be used when the resin composition does not contain the hydrogenated block copolymer (C). As the softener, softeners generally used in rubber and plastics can be used. Examples of softeners include paraffinic, naphthenic, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; liquid co-oligomers of ethylene and α-olefins; liquid paraffin; polybutene; and low-molecular-weight polyisobutylene. From the viewpoint of compatibility between the modified hydrogenated product (A) and the resin (B) or compatibility between both the modified hydrogenated product (A) and the hydrogenated block copolymer (C) and the resin (B), the softener is preferably at least one selected from the group consisting of paraffinic process oil, naphthenic process oil, and aromatic process oil.

[0122] When the resin composition contains the hydrogenated block copolymer (C) and a softener, from the viewpoint of the moldability of the resin composition, the lower limit of the content of the softener is preferably 5 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, and still more preferably 80 parts by mass or more, per 100 parts by mass of the hydrogenated block copolymer (C). Furthermore, from the viewpoint of avoiding bleed-out of the softener from the resin composition, the upper limit of the content of the softener is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 120 parts by mass or less, per 100 parts by mass of the hydrogenated block copolymer (C).

[0123] [Additives] The resin composition of this embodiment may contain additives as long as the effects of the present invention are not impaired. Specifically, additives may be contained in addition to the modified hydrogenated product (A) and resin (B). Additives may be contained in addition to the modified hydrogenated product (A), resin (B), and hydrogenated block copolymer (C). Additives may be contained in addition to the modified hydrogenated product (A), resin (B), and softener. Additives may be contained in addition to the modified hydrogenated product (A), resin (B), hydrogenated block copolymer (C), and softener. Examples of additives include thermoplastic polymers other than the modified hydrogenated product (A), resin (B), and hydrogenated block copolymer (C), antioxidants, inorganic fillers, tackifying resins, light stabilizers, processing aids, flame retardants, antistatic agents, matting agents, antiblocking agents, UV absorbers, release agents, foaming agents, antibacterial agents, antifungal agents, fragrances, and colorants such as pigments and dyes. The additives may be used alone or in combination of two or more.

[0124] <Antioxidant> The resin composition of this embodiment preferably further contains an antioxidant. Examples of antioxidants include hindered phenol-based, phosphorus-based, lactone-based, and hydroxyl-based antioxidants. Among these, hindered phenol-based antioxidants are preferred. When an antioxidant is contained, the content of the antioxidant is preferably within a range that does not cause coloration when the resin composition is melt-kneaded. The content of the antioxidant is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total content of the modified hydrogenated product (A), resin (B), and hydrogenated block copolymer (C). Note that when the resin composition of this embodiment does not contain the hydrogenated block copolymer (C), the content of the antioxidant is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total content of the modified hydrogenated product (A) and resin (B).

[0125] [Method for Producing Resin Composition] The resin composition of this embodiment may be produced by any method capable of mixing the modified hydrogenated product (A) and resin (B), the hydrogenated block copolymer (C) that can be used as needed, the softener, and the additives, and any known means may be used. For example, the resin composition may be produced by mixing the components of the resin composition using a mixer such as a Henschel mixer, V-blender, ribbon blender, tumbler blender, or conical blender. After mixing, the resin composition may be melt-kneaded at about 80 to 350°C using a kneader such as a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, or roll mixer. The melt-kneading method is preferred from the viewpoint of easily compatibilizing the components of the resin composition.

[0126] [Melt flow rate of resin composition] The resin composition has a melt flow rate of 5 g / 10 min or more, measured in accordance with JIS K 7210:2014 at a temperature of 230 ° C. and a load of 21 N. If the resin composition has a melt flow rate of 5 g / 10 min or more, the resin composition tends to have flexibility, excellent tensile properties, and excellent adhesive strength. The resin composition also has good moldability. From the viewpoint of achieving even better tensile properties and adhesive strength, the lower limit of the melt flow rate of the resin composition is preferably 10 g / 10 min or more, more preferably 20 g / 10 min or more, and even more preferably 30 g / 10 min or more. From the viewpoint of tensile properties and moldability, the upper limit of the melt flow rate of the resin composition is preferably 200 g / 10 min or less, more preferably 150 g / 10 min or less, and even more preferably 100 g / 10 min or less. Preferred examples of methods for adjusting the melt flow rate of the resin composition to fall within the above range include a method of appropriately setting the blending amounts of the modified hydrogenated product (A) and resin (B), and the hydrogenated block copolymer (C) used as needed, a method of adjusting the degree of polymerization of each resin component used in the resin composition, and a method of adjusting the type of monomer used in each resin component.

[0127] [Tensile Breaking Elongation] The tensile breaking elongation of the resin composition of this embodiment, measured in accordance with ISO 37:2017, is preferably 220 to 800%, more preferably 300 to 800%, even more preferably 400 to 750%, and even more preferably 500 to 700%. If the tensile breaking elongation of the resin composition is within the above numerical range, it is preferable because the adhesive strength is even better. The tensile breaking elongation can be measured according to the method described in the examples.

[0128] [Tensile Break Strength] The lower limit of the tensile break strength of the resin composition of this embodiment measured in accordance with ISO 37:2017 is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, and even more preferably 2.0 MPa or more. The upper limit of the tensile break strength of the resin composition of this embodiment is not particularly limited, but may be, for example, 200 MPa or less. If the tensile break strength of the resin composition is within the above numerical range, it is preferable because the adhesive strength is even more excellent. The tensile break strength can be measured according to the method described in the examples.

[0129] [Peel Strength] The peel strength of the resin composition of this embodiment, measured in accordance with JIS K 6854-2:1999, is preferably 5 N / 25 mm or more, more preferably 10 N / 25 mm or more, and even more preferably 15 N / 25 mm or more. The upper limit of the tensile strength of the resin composition of this embodiment is not particularly limited, but may be, for example, 200 N / 25 mm or less. It is preferable that the peel strength of the resin composition is within the above numerical range, since this is an adhesive strength that can withstand practical use. The peel strength can be measured according to the method described in the examples.

[0130] The resin composition according to the present embodiment preferably has a peel strength of 5 N / 25 mm or more against synthetic resin. The resin composition according to the present embodiment preferably has a peel strength of 3 N / 25 mm or more against aluminum as a metal, more preferably 5 N / 25 mm or more. The resin composition according to the present embodiment preferably has a peel strength of 3 N / 25 mm or more against SUS as a metal, more preferably 5 N / 25 mm or more.

[0131] <Molded Articles> The resin composition of this embodiment can be molded into various molded articles using a melt-kneading molding machine. Furthermore, the resin composition of this embodiment can be molded into bales, crumbs, pellets, or the like, and then molded into various molded articles using injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, or the like. From the viewpoint of achieving both better tensile properties and adhesive strength, the molding temperature of the resin composition, specifically, for example, the cylinder temperature of the extruder during injection molding or extrusion molding, is preferably 160 to 250°C, more preferably 180 to 230°C. The cylinder temperature can be set appropriately as long as the effects of the present invention are not excessively impaired. The shape, structure, use, etc. of the molded article containing the resin composition of this embodiment are not particularly limited. On the other hand, the resin composition of this embodiment has excellent tensile properties and strong adhesive strength to synthetic resins, metals, etc., and therefore, the resin composition of this embodiment can be suitably used as part of a laminate structure.

[0132] [Tensile Breaking Elongation] The tensile breaking elongation of a molded article containing the resin composition of this embodiment, measured in accordance with ISO 37:2017, is preferably 220 to 800%, more preferably 300 to 800%, even more preferably 400 to 750%, and even more preferably 500 to 700%. If the tensile breaking elongation of the resin composition is within the above numerical range, it is preferable because the adhesive strength is even better. The tensile breaking elongation can be measured according to the method described in the examples.

[0133] [Tensile Break Strength] The lower limit of the tensile break strength of a molded article containing the resin composition of this embodiment, measured in accordance with ISO 37:2017, is preferably 1.0 MPa or more, more preferably 1.5 MPa or more, and even more preferably 2.0 MPa or more. The upper limit of the tensile break strength of a molded article containing the resin composition of this embodiment is not particularly limited, but may be, for example, 200 MPa or less. If the tensile break strength of a molded article containing the resin composition is within the above numerical range, it is preferable because the adhesive strength is even better. The tensile break strength can be measured according to the method described in the examples.

[0134] [Peel Strength] The peel strength of a molded article containing the resin composition of this embodiment, measured in accordance with JIS K 6854-2:1999, is preferably 5 N / 25 mm or more, more preferably 10 N / 25 mm or more, and even more preferably 15 N / 25 mm or more. The upper limit of the tensile break strength of a molded article containing the resin composition of this embodiment is not particularly limited, but may be, for example, 200 N / 25 mm or less. A peel strength of a molded article containing the resin composition within the above numerical range is preferable because it is an adhesive strength that can withstand practical use. The peel strength can be measured according to the method described in the examples.

[0135] A molded article containing the resin composition of this embodiment preferably has a peel strength of 5 N / 25 mm or more against synthetic resins. The resin composition of this embodiment preferably has a peel strength of 3 N / 25 mm or more against aluminum as a metal, more preferably 5 N / 25 mm or more. The resin composition of this embodiment preferably has a peel strength of 3 N / 25 mm or more against SUS as a metal, more preferably 5 N / 25 mm or more.

[0136] <Laminate Structure> The laminate structure has a layer formed from the resin composition of this embodiment and a layer formed from a material other than the resin composition (hereinafter referred to as "other layer"). The laminate structure may have at least one layer formed from the resin composition and at least one other layer, and may have multiple layers. Furthermore, when the laminate structure has multiple other layers, the multiple other layers may be layers made of the same material or layers made of different materials. The resin composition of this embodiment exhibits strong adhesive strength. Therefore, in the laminate structure, the layer formed from the resin composition of this embodiment is an adhesive layer, and the other layers are adherends. Examples of materials constituting the other layer that will be the adherend include synthetic resins, ceramics, metals, and fabrics. The materials constituting the other layer may be used alone or in combination of two or more. Among these, the material constituting the other layer is preferably at least one selected from the group consisting of synthetic resins and metals.

[0137] Synthetic resins that can be used in the laminate structure of this embodiment include, for example, polyamide resins, polyurethane resins, polyester resins, polycarbonate resins, polyphenylene sulfide resins, polyacrylate resins, polymethacrylate resins, polyether resins, (meth)acrylonitrile-butadiene-styrene resins, (meth)acrylonitrile-styrene resins, (meth)acrylic acid ester-butadiene-styrene resins, (meth)acrylic acid ester-styrene resins, (meth)methyl acrylate-butadiene-styrene resins, epoxy resins, phenolic resins, diallyl phthalate resins, polyimide resins, melamine resins, polyacetal resins, polysulfone resins, polyethersulfone resins, polyetherimide resins, polyphenylene ether resins, polyarylate resins, polyetheretherketone resins, polystyrene resins, rubber-reinforced polystyrene resins, polar resins such as syndiotactic polystyrene resins; and non-polar resins such as polyolefin resins. These synthetic resins may be used alone or in combination of two or more.

[0138] Examples of the polyamide resin include polyamide 6 (PA6) and polyamide 66 (PA66). Examples of the polyolefin resin include polyethylene, polypropylene, polybutene-1, polyhexene-1, poly-3-methyl-butene-1, poly-4-methyl-pentene-1, copolymers of ethylene with one or more α-olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, 6-methyl-1-heptene, isooctene, isooctadiene, decadiene, etc.), ethylene-propylene-diene copolymer (EPDM), ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Additives may be added to the layer formed of the synthetic resin as needed, as long as they do not impair the objectives of the present invention. Examples of the additives include heat stabilizers, light stabilizers, ultraviolet 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, and antibacterial agents.

[0139] The ceramics that can be used in the laminated structure of this embodiment refer to non-metallic inorganic materials, such as metal oxides, metal carbides, and metal nitrides, etc. Examples of such materials include glass, cements, alumina, zirconia, zinc oxide-based ceramics, barium titanate, lead zirconate titanate, silicon carbide, silicon nitride, and ferrites.

[0140] Examples of metals that can be used in the laminate structure of this embodiment include iron, copper, aluminum, magnesium, nickel, chromium, zinc, and alloys containing these metals. The metal that can be used in the laminate structure is preferably at least one selected from aluminum alloys and stainless steel. Furthermore, the metal layer may be a layer having a metal surface formed by plating, such as copper plating, nickel plating, chromium plating, tin plating, zinc plating, platinum plating, gold plating, or silver plating.

[0141] The type of fabric that can be used in the laminate structure of this embodiment is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, felts, nonwoven fabrics, etc. Furthermore, the material of the fabric may be natural fibers, synthetic fibers, or a combination of natural and synthetic fibers. Natural fibers include, but are not particularly limited to, cotton, silk, hemp, wool, etc. Furthermore, synthetic fibers include, for example, polyester fibers, acrylic fibers (polyacrylonitrile), polyurethane fibers, polyamide fibers, polyolefin fibers, and vinylon fibers. Examples of polyamide fibers include nylon 6 and nylon 66. Examples of polyolefin fibers include polyethylene fibers and polypropylene fibers.

[0142] [Method for Producing Laminated Structure] The method for producing the laminated structure of the present invention is not particularly limited, but it is preferable to produce the laminated structure of the present invention by melt lamination molding of the resin composition of the present embodiment with the other materials described above. Examples of such molding methods include injection insert molding, extrusion lamination, coextrusion molding, calendar molding, slush molding, press molding, and melt casting.

[0143] For example, when manufacturing a laminate structure by injection insert molding, an adherend previously formed to a predetermined shape and dimensions is placed in a mold, and the resin composition of the present embodiment is injection molded therein to manufacture the laminate structure. When manufacturing a laminate structure by extrusion lamination, a laminate structure can also be manufactured by directly extruding the molten resin composition of the present embodiment extruded from a die having a predetermined shape attached to an extruder onto the surface or edge of an adherend previously formed to a predetermined shape and dimensions. When manufacturing a laminate structure by co-extrusion molding, a laminate structure can also be manufactured by simultaneously extruding molten resins using two extruders. When manufacturing a laminate structure by calendar molding, a laminate structure can also be manufactured by heat-sealing the resin composition of the present embodiment, which has been melted and rolled with a heated roll and passed through several rolls to be in a molten state, to the surface of an adherend previously formed to a predetermined shape and dimensions. When producing a laminated structure by press molding, a molded article made of the resin composition of the present invention may be previously molded by injection molding or extrusion molding, and the molded article may then be applied to an adherend that has been previously formed to a predetermined shape and dimensions, under heat and pressure using a press molding machine, etc. Such a molding method is particularly suitable when the adherend is made of ceramics or metal.

[0144] As a molding method using melt lamination molding, injection insert molding is preferred. In particular, the laminate structure of this embodiment is preferably produced by a method in which a resin composition is injection insert molded into a layer formed of a material other than the resin composition, and more preferably by a method in which the resin composition is injection insert molded at a resin temperature of 160 to 250°C. The injection molding temperature in the injection insert molding method is preferably 180°C or higher, more preferably 200°C or higher, from the viewpoint of obtaining sufficient adhesive strength. Furthermore, from the viewpoint of achieving both tensile properties and strong adhesive strength and preventing deterioration of the hue of the resin composition due to high temperatures, it is preferably 240°C or lower, more preferably 230°C or lower. In the resin composition of this embodiment, particularly when a thermoplastic polyurethane resin is used as resin (B), the resin composition is prone to changes in hue and deterioration of tensile properties due to high temperatures. Conventionally, resin compositions constituting the adhesive layer required injection insert molding at high temperatures exceeding 250°C to obtain adhesive strength, which was prone to changes in hue and deterioration of tensile properties. On the other hand, when conventional resin compositions are injection-insert molded at temperatures below 250°C, sufficient adhesive strength cannot be obtained. However, the resin composition of this embodiment is preferably injection-molded at a resin temperature of 160 to 250°C, which allows for the resin composition to exhibit strong adhesive strength while suppressing changes in color and deterioration of tensile properties, etc., thereby more significantly demonstrating the effects of the present invention. The resin temperature during injection molding can be set appropriately as long as the effects of the present invention are not excessively impaired.

[0145] When the adherend is a synthetic resin, the two materials can be melted simultaneously and co-extruded or co-injected. Alternatively, one material can be molded in advance and then melt-coated or solution-coated. Other methods include two-color molding and insert molding.

[0146] <Applications> The resin composition of this embodiment can be widely used in a variety of applications. One example is a laminate structure in which the resin composition of this embodiment is adhered to various housing materials. The raw materials for the housing materials generally include synthetic resins, synthetic resins containing glass fibers, and light metals such as aluminum and magnesium alloys. Preferred embodiments of the housing material include housing materials for electronic and electrical devices, office automation equipment, home appliances, sporting goods, power tools, and automotive components. More specifically, preferred embodiments include housings for large displays, notebook computers, mobile phones, personal digital assistants, electronic dictionaries, video cameras, digital still cameras, portable radio cassette players, inverters, and power tools. By adhering the resin composition of this embodiment to these housing materials, it can be used as a laminate structure. In the laminate structure, a layer made of the resin composition of this embodiment is preferably used as an impact absorbing material, a coating material with anti-slip properties, a waterproof material, a decorative material, and the like. In another preferred embodiment, the resin composition of this embodiment is used as a sealant. Examples of the sealant include a sealant for joints in molded bodies and structures to which a transparent member, such as glass, is bonded. Resin members such as polycarbonate and PMMA are also preferably used as the transparent member. Specific examples of joints in molded bodies and structures to which a transparent member is bonded include joints between glass and aluminum sashes in architectural windows, joints between glass and metal openings in automobiles, and joints between glass and metal frames in solar cell modules. The resin composition of this embodiment can be preferably used as a sealant for the above-mentioned joints. In yet another preferred embodiment, the resin composition of this embodiment can be preferably used as a separator for a secondary battery. The separator for the secondary battery is not particularly limited, but preferred examples include separators for secondary batteries used in various information terminal devices such as notebook computers, mobile phones, and video cameras, as well as hybrid vehicles and fuel cell vehicles.

[0147] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. β-Farnesene (purity 97.6% by mass, manufactured by Amyris, Inc.) was purified using 3 Å molecular sieves and distilled under a nitrogen atmosphere to remove hydrocarbon impurities such as zingiberene, bisabolene, farnesene epoxide, farnesol isomers, E,E-farnesol, squalene, ergosterol, and several dimers of farnesene, before being used in the following polymerization.

[0148] <Ingredients> The ingredients used in the examples and comparative examples are as follows. [Modified hydrogenated products (A)] (A1) to (A4): modified hydrogenated products of Production Examples 1-1 to 1-4 described below (A5): maleic anhydride-modified ethylene-butene copolymer (trade name: Tafmer (registered trademark) MH5020, manufactured by Mitsui Chemicals, Inc., modification amount 1.0 phr, melt flow rate 1.2 g / 10 min (catalog value, ASTM D1238, 230°C)) (A6): maleic anhydride-modified polypropylene (trade name: Admer (registered trademark) QF500, manufactured by Mitsui Chemicals, Inc., modification amount 0.8 phr) However, (A4), (A5), and (A6) are for comparative examples. [Resin (B)] (B1): Thermoplastic polyurethane resin (trade name: Elastollan (registered trademark) C80A, manufactured by BASF Japan Ltd., Type A hardness 80) (B2) to (B4): Acrylic block copolymers of Production Examples 2-1 to 2-4 described later [Hydrogenated block copolymer (C)] (C1) to (C5): Hydrogenated block copolymers of Production Examples 3-1 to 3-5 described later [Softener] Softener: Paraffin-based process oil (trade name: Diana Process Oil PW-90, manufactured by Idemitsu Kosan Co., Ltd.) [Antioxidant] Hindered phenol-based antioxidant (trade name: Adeka Stab AO-60, manufactured by ADEKA Corporation)

[0149] <Measurement Methods> The details of each measurement method in the Production Examples are as follows. (1) Content of Polymer Blocks [Modified Hydrogenated Product (A) and Hydrogenated Block Copolymer (C)] The contents of polymer block (A-1) and polymer block (C-1) were measured as follows. The modified hydrogenated product (A) and the hydrogenated block copolymer (C) were each dissolved in CDCl３ Dissolve in １ H-NMR measurement [apparatus: "AVANCE 400 Nanobay" (manufactured by Bruker), measurement temperature: 30°C] was carried out, and the content of the polymer block was calculated from the ratio of the peak area derived from styrene to the peak area derived from isoprene and / or butadiene, or the ratio of the peak area derived from styrene to the peak area derived from farnesene.

[0150] [Resin (B): Acrylic Block Copolymer] The contents of the polymer block (E1) and the polymer block (D1) constituting the acrylic block copolymer are １ The mass ratio (E1) / (D1) was calculated from the calculated contents of polymer block (E1) and polymer block (D1) by H-NMR measurement [apparatus: nuclear magnetic resonance apparatus "JNM-ECX400" (manufactured by JEOL Ltd.), measurement temperature: 30°C, heavy solvent: deuterated chloroform] as follows. １ In the H-NMR spectrum, the signals at around 3.6 ppm and 3.7 ppm correspond to the ester groups (—O—CH ) of the methyl methacrylate units. ３ ), an ester group of a methyl acrylate unit (—O—CH ３ ), and the signal at around 4.0 ppm is attributed to the ester group (—O—CH ) of the n-butyl acrylate unit. ２ -CH ２ -CH ２ -CH ３ ) or an ester group of a 2-ethylhexyl acrylate unit (—O—CH ２ -CH(-CH ２ -CH ３ )-CH ２ -CH ２ -CH ２ -CH ３ The molar ratio of each monomer unit was determined from the ratio of these integral values, and the content of each polymer block was calculated by converting this into a mass ratio based on the molecular weight of the monomer unit.

[0151] (2) Weight-Average Molecular Weight [Modified Hydrogenated Product (A) and Hydrogenated Block Copolymer (C)] The weight-average molecular weights of polymer block (A-1), polymer block (A-2), polymer block (C-1), polymer block (C-2), modified hydrogenated product (A), and hydrogenated block copolymer (C) were measured as follows. The polystyrene-equivalent weight-average molecular weights (Mw) of the modified hydrogenated product (A) and the hydrogenated block copolymer (C) were determined by gel permeation chromatography (GPC) measurement under the conditions below. The weight-average molecular weight (Mw) of each polymer block was determined by measuring a sample taken each time the polymerization of each polymer block was completed in the production process by GPC measurement under the conditions below. <GPC Measurement Apparatus and Measurement Conditions> Apparatus: GPC apparatus "HLC-8020" manufactured by Tosoh Corporation Separation column: Two "TSKgel G4000HX" manufactured by Tosoh Corporation were connected in series. Eluent: tetrahydrofuran Eluent flow rate: 0.7 mL / min Sample concentration: 5 mg / 10 mL Column temperature: 40°C Detector: differential refractive index (RI) detector Calibration curve: prepared using standard polystyrene

[0152] [Resin (B): Acrylic Block Copolymer] The peak top molecular weight (Mp) and molecular weight distribution (Mw / Mn) of the acrylic block copolymer were determined by gel permeation chromatography (GPC) measurement under the following conditions in terms of standard polystyrene. <GPC Measurement Apparatus and Measurement Conditions> Apparatus: GPC apparatus "GPC8020" manufactured by Tosoh Corporation Separation column: "TSKgel GMHXL", "G4000HXL", and "G5000HXL" manufactured by Tosoh Corporation were connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 1.0 mL / min Sample concentration: 5 mg / 10 mL Column temperature: 40°C Detector: "RI-8020" manufactured by Tosoh Corporation Calibration curve: Prepared using standard polystyrene

[0153] (3) Hydrogenation Rate The hydrogenation rates of the modified hydrogenated product (A) and the hydrogenated block copolymer (C) were measured as follows. The modified hydrogenated product (A) before modification and the hydrogenated block copolymer (C) before and after hydrogenation were respectively measured using CDCl ３ Dissolve in １ H-NMR measurement was carried out using an AVANCE 400 Nanobay (manufactured by Bruker), at a measurement temperature of 30°C. The hydrogenation rates of carbon-carbon double bonds in the structural units derived from the conjugated diene compound in the modified hydrogenated product (A) before modification and the hydrogenated block copolymer (C) were calculated from the proton peaks of the carbon-carbon double bonds appearing at 4.5 to 6.0 ppm in the obtained spectra, using the following formula: Hydrogenation rate (mol %) of modified hydrogenated product (A) before modification = {1 - (number of moles of carbon-carbon double bonds contained per mole of modified hydrogenated product (A) before modification) / (number of moles of carbon-carbon double bonds contained per mole of modified hydrogenated product (A) before modification)} x 100 Hydrogenation rate (mol %) of hydrogenated block copolymer (C) = {1 - (number of moles of carbon-carbon double bonds contained per mole of hydrogenated block copolymer (C)) / (number of moles of carbon-carbon double bonds contained per mole of hydrogenated block copolymer (C) before hydrogenation)} x 100 The calculated hydrogenation rate of modified hydrogenated product (A) before modification is shown in Table 2 as "hydrogenation rate (mol %) in polymer block (A-2)." The calculated hydrogenation rate of hydrogenated block copolymer (C) is shown in Table 5 as "hydrogenation rate (mol %) in polymer block (C-2)." Note that the hydrogenation rate does not change before and after modification.

[0154] (4) Vinyl Bond Content The vinyl bond content of the polymer block (A-2) and the polymer block (C-2) was measured as follows. The modified hydrogenated product (A) before hydrogenation and the hydrogenated block copolymer (C) before hydrogenation were each dissolved in CDCl ３ Dissolve in １H-NMR measurement [apparatus: "AVANCE 400 Nanobay" (manufactured by Bruker), measurement temperature: 30°C] was carried out. In the cases of (A1) to (A4), (C1), (C3), and (C4), 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 the 3,4-bond units and 1,2-bond units in the isoprene structural units and the 1,2-bond units in the butadiene structural units to the total peak area of ​​the structural units derived from isoprene and / or butadiene. In the case of (C2), the vinyl bond amount was calculated from the ratio of the peak area corresponding to the 3,13-bond units and 1,2-bond units in β-farnesene to the total peak area of ​​the structural units derived from β-farnesene. In the case of (C5), the amount of vinyl bonds was calculated from the ratio of the peak area corresponding to the 1,2-bond units in the butadiene structural units to the total peak area of ​​the structural units derived from isoprene and / or butadiene, and the ratio of the peak area corresponding to the 3,13-bond units and 1,2-bond units in β-farnesene to the total peak area of ​​the structural units derived from β-farnesene.

[0155] (5) (Melt Flow Rate (MFR)) The flow rate (g / 10 min) of the modified hydrogenated product (A) was measured using a melt indexer at a temperature of 230° C. and a load of 21 N in accordance with JIS K 7210:2014.

[0156] (6) Glass Transition Temperature The glass transition temperatures of the modified hydrogenated product (A) and the hydrogenated block copolymer (C) were measured as follows: Using a DSC measurement device (DSC6200 manufactured by Hitachi High-Tech Science Corporation), measurements were performed in the temperature range of −100° C. to +350° C. at a heating rate of 20° C. / min, and the temperature at the inflection point of the baseline shift due to the glass transition was taken as the glass transition temperature.

[0157] (7) tanδ peak top temperature and tanδ peak top strength The tanδ peak top temperature and tanδ peak top strength of the modified hydrogenated product (A) and the hydrogenated block copolymer (C) were measured as follows. The modified hydrogenated product (A) and the hydrogenated block copolymer (C) were each press-molded using a press molding machine "NF-50T" (manufactured by Shinto Metal Industries Co., Ltd.) at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes to produce a 1.0 mm thick sheet, and the sheet was cut into a disk shape with a diameter of 8 mm to serve as a test piece. As a measuring device, a rotational rheometer "ARES-G2" (manufactured by TA Instruments), which is a distortion-controlled dynamic viscoelasticity device, was used in accordance with JIS K7244-10:2005. The test piece was sandwiched between flat plates with a diameter of 8 mm, and vibration was applied at a strain of 0.1% and a frequency of 1 Hz. The test was performed by increasing the temperature from -70 ° C. to 120 ° C. at a rate of 3 ° C. / min. The temperature at which the maximum peak intensity was obtained (peak top temperature) and the maximum peak intensity of tan δ (peak top intensity) were determined by the above test.

[0158] (8) Amount of maleic anhydride modification (content of functional groups (phr)) 5 g of the modified hydrogenated product (A) was dissolved in 180 ml of toluene, and then 20 ml of ethanol was added. The mixture was titrated with a 0.1 mol / L potassium hydroxide solution, and the amount of modification was calculated using the following formula: Amount of maleic anhydride modification (phr) = Titration amount × 5.611 / Sample amount × 98 × 100 / 56.11 × 1000

[0159] <Production Examples> [Production Example 1-1] Modified Hydrogenated Product (A1) (1) Hydrogenated Block Copolymer A nitrogen-purged, dried pressure-resistant vessel was charged with 50 kg of cyclohexane (solvent) dried over molecular sieves A4 and 0.07 kg of a 10.5 mass% cyclohexane solution of sec-butyllithium as an anionic polymerization initiator (effective amount of sec-butyllithium added: 7.4 g). The pressure-resistant vessel was heated to 50°C, and 1.00 kg of styrene (first addition) was added and polymerized for 60 minutes. The temperature was then lowered to 40°C, and 0.033 kg of 2,2-di(2-tetrahydrofuryl)propane (DTHFP) was added as a Lewis base. A mixture of 8.17 kg of isoprene and 6.49 kg of butadiene was added over 5 hours, followed by polymerization for 2 hours. The temperature was then raised to 50°C, 1.00 kg of styrene (second addition) was added, and polymerization was carried out for 30 minutes. Methanol was then added to terminate the reaction, yielding a reaction solution containing a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer. A Ziegler catalyst (Al / Ni-based Ziegler 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 at a hydrogen pressure of 1 MPa and 80°C. The reaction solution was allowed to cool and the pressure was released, after which the Ziegler catalyst was removed by washing with water and the mixture was vacuum dried to yield a hydrogenated additive of a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer. (2) Modified Hydrogenated Product Using a twin-screw extruder "ZSK26mc" (26 mmφ, L / D=56) manufactured by Coperion under the following extrusion conditions, 10 kg of the hydrogenated product obtained above, 0.01 kg of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B-40, manufactured by NOF Corporation) as a radical initiator, and 0.1 kg of maleic anhydride as a modifier were blended and brought to a molten state, and a modification reaction was carried out to obtain a modified hydrogenated product (A1). The components and the amounts used are shown in Table 1. The results of the physical property evaluations are also shown in Table 2.

[0160] [Production Examples 1-2 to 1-4] Modified hydrogenated products (A2) to (A4) Modified hydrogenated products (A2) to (A4) were obtained in the same manner as in Production Example 1, except that the components and their amounts used were changed as shown in Table 1. The results of the physical property evaluations are shown in Table 2.

[0161] [Production Example 2-1] Acrylic Block Copolymer (B2) (Step 1) 50.0 kg of toluene and 0.0998 kg of 1,2-dimethoxyethane were added to a nitrogen-purged, dried pressure vessel with stirring at room temperature (23°C), followed by 0.820 kg of a toluene solution containing 412 mmol of isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum, and then 0.121 kg of a cyclohexane solution of sec-butyllithium containing 206 mmol of sec-butyllithium. (Step 2) 1.47 kg of methyl methacrylate was then added to the mixture at room temperature with stirring, and stirring was continued for an additional 60 minutes. The reaction solution was initially yellow, but became colorless after stirring for 60 minutes. (Step 3) The internal temperature of the polymerization solution was then cooled to -30°C, and 6.33 kg of n-butyl acrylate was added dropwise over 4 hours with stirring. After completion of the dropwise addition, stirring was continued for an additional 5 minutes at -30°C. (Step 4) 1.20 kg of methyl methacrylate was then added to the mixture, and the mixture was stirred overnight at room temperature. (Step 5) 0.370 kg of methanol was added to terminate the polymerization reaction, and the resulting reaction solution was poured into methanol with stirring to precipitate a white precipitate. The resulting white precipitate was collected and dried to obtain an acrylic block copolymer (B2). The components, their amounts used, and the results of the above-mentioned physical property evaluations are shown in Table 3.

[0162] [Production Examples 2-2 to 2-4] Acrylic block copolymers (B3) and (B4) Acrylic block copolymers (B3), (B4), and (B5) were obtained in the same manner as in Production Example 2-1, except that the components and their amounts used were changed as shown in Table 3. The results of the physical property evaluations are also shown in Table 3.

[0163] [Production Example 3-1] Hydrogenated Block Copolymer (C1) 50 kg of cyclohexane (solvent) dried over molecular sieves A4 and 0.03 kg of a 10.5 mass% cyclohexane solution of sec-butyllithium as an anionic polymerization initiator (effective amount of sec-butyllithium added: 3.2 g) were charged into a nitrogen-purged, dried pressure-resistant vessel. After heating the pressure-resistant vessel to 50 ° C., 1.32 kg of styrene (first addition) was added and polymerized for 60 minutes, followed by the addition of a mixture of 3.44 kg of isoprene and 2.73 kg of butadiene over 5 hours and polymerization for 2 hours. Thereafter, 1.32 kg of styrene (second addition) was added and polymerized for 60 minutes, and methanol was added to terminate the reaction, yielding a reaction solution containing a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer. To the reaction solution, a Ziegler catalyst (Al / Ni-based Ziegler catalyst) formed from nickel octoate and trimethylaluminum was added as a hydrogenation catalyst under a hydrogen atmosphere, and the reaction was carried out for 5 hours at a hydrogen pressure of 1 MPa and 80°C. After allowing the reaction solution to cool and the pressure to be released, the Ziegler catalyst was removed by washing with water, and the mixture was dried in vacuo to obtain a hydrogenated block copolymer (C1) of a polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer. Table 4 shows the components and the amounts used. Table 5 also shows the results of the physical property evaluations.

[0164] [Production Examples 3-2 and 3-3] Hydrogenated Block Copolymers (C2) and (C3) Hydrogenated block copolymers (C2) and (C3) were obtained in the same manner as in Production Example 3-1, except that the components and their amounts used were changed as shown in Table 4. The results of the physical property evaluations are shown in Table 5.

[0165] [Production Example 3-4] Hydrogenated Block Copolymer (C4) Into a nitrogen-purged, dried pressure vessel, 50 kg of cyclohexane (solvent) dried over molecular sieves A4, and 0.10 kg of a cyclohexane solution of sec-butyllithium at a concentration of 10.5% by mass as an anionic polymerization initiator (substantial amount of sec-butyllithium added: 10.5 g) were charged. After heating the pressure vessel to 50 ° C., 1.67 kg of styrene (first time) was added and polymerized for 60 minutes, and then the temperature in the vessel was lowered to 40 ° C., 0.29 kg of tetrahydrofuran was added as a Lewis base, and then 13.33 kg of isoprene was added over 5 hours and polymerized for 2 hours. Thereafter, the temperature was raised to 50 ° C., 1.67 kg of styrene (second time) was added and polymerized for 60 minutes, and methanol was added to stop the reaction, and a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. To the reaction solution, a Ziegler catalyst (Al / Ni-based Ziegler catalyst) formed from nickel octoate and trimethylaluminum was added as a hydrogenation catalyst under a hydrogen atmosphere, and the mixture was allowed to react for 5 hours at a hydrogen pressure of 1 MPa and 80°C. After allowing the reaction solution to cool and the pressure to be released, the Ziegler catalyst was removed by washing with water, and the mixture was dried in vacuo to obtain a hydrogenated block copolymer (C4) of a polystyrene-polyisoprene-polystyrene triblock copolymer. Table 4 shows the components and the amounts used. Table 5 also shows the results of the physical property evaluations.

[0166] [Production Example 3-5] Hydrogenated Block Copolymer (C5) A nitrogen-purged, dried pressure vessel was charged with 50 kg of cyclohexane as a solvent, 227 g of a 10.5% by mass cyclohexane solution of sec-butyllithium as an anionic polymerization initiator (effective amount of sec-butyllithium added: 23.9 g), and 100 g of tetrahydrofuran as a Lewis base. After the temperature inside the pressure vessel was raised to 50°C, 7.4 kg of β-farnesene was added and polymerization was carried out for 2 hours. Subsequently, 3.0 kg of styrene (first addition) was added and polymerization was carried out for 1 hour, and then 4.6 kg of butadiene was added and polymerization was carried out for 1 hour. Subsequently, 100 g of phenyl benzoate was added as a coupling agent to this polymerization reaction solution and the reaction was carried out for 1 hour, thereby obtaining a reaction solution containing a poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer. A Ziegler hydrogenation catalyst formed from nickel octoate 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 allowing the reaction solution to cool and the pressure to be released, the catalyst was removed by washing with water, and the solution was dried in vacuo to obtain a hydrogenated product of poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer (C5). The components and their amounts used are shown in Table 4. The results of the physical property evaluations are also shown in Table 5.

[0167]

[0168]

[0169]

[0170] The symbols in Table 3 are as follows: MMA-nBA-MMA: methyl methacrylate polymer block-n-butyl acrylate polymer block-methyl methacrylate polymer block MMA-(nBA / MA)-MMA: methyl methacrylate polymer block-(n-butyl acrylate / methyl acrylate) copolymer block-methyl methacrylate polymer block

[0171]

[0172]

[0173] Examples 1 to 14 and Comparative Examples 1 to 3 (1) Preparation of Resin Compositions The components and amounts used were as shown in Table 6 or Table 7. The premixed compositions were melt-kneaded using a twin-screw extruder (Coperion's "ZSK26Mc"; number of cylinders: 14) at 230°C and a screw rotation speed of 200 rpm to obtain resin compositions. The physical properties of the resulting resin compositions were evaluated according to the methods described below. The evaluation results are shown in Table 6 or Table 7. (2) Preparation of Laminated Structures Laminated structures were prepared by injection insert molding using the following adherends (length 100 mm x width 35 mm x thickness 1 mm) as insert parts. When the adherend was a synthetic resin, both sides of the adherend were wiped with gauze impregnated with methanol to degrease the adherend, and then air-dried. When the adherend was a metal, both sides of the adherend were washed with a surfactant aqueous solution and distilled water, in that order, and then dried at 100°C. Each adherend pretreated as described above was fixed in a mold using a vacuum line. The resulting resin composition was filled into the mold under conditions of a mold temperature of 50°C and a cylinder temperature of 230°C, and the surface temperature of the adherend was cooled to 50°C to obtain a laminate structure. The adhesive strength (peel strength) of the resin composition of the resulting laminate structure was evaluated according to the following method. The evaluation results are shown in Table 6 or Table 7.

[0174] Details of the adherends used to prepare the laminated structure are as follows: Polycarbonate (PC) plate: trade name "Iupilon S-3000R", manufactured by Mitsubishi Engineering-Plastics Corporation Acrylonitrile-butadiene-styrene resin (ABS) plate: trade name "Toyolac 700-314", manufactured by Toray Industries, Inc. Nylon 6 (PA6) plate: trade name "UBE Nylon6 1013B", manufactured by Ube Industries, Ltd. Aluminum alloy (AL) plate: material "A5052P"

[0175] <Evaluation Methods> Details of the evaluation methods in the Examples and Comparative Examples are as follows. [Melt Flow Rate (MFR)] For the resin compositions obtained in the Examples and Comparative Examples, the flow rate (g / 10 min) was measured using a melt indexer at a temperature of 230°C and a load of 21 N in accordance with JIS K 7210:2014. Note that in Comparative Example 2, the melt flow rate was less than 0.1 g / 10 min, making measurement difficult, and therefore is indicated as "<0.1" in Table 6.

[0176] [Hardness and Tensile Properties] (1) Sheet Preparation The resin compositions obtained in the Examples and Comparative Examples were injection molded using an injection molding machine (Toshiba Machine Co., Ltd. "EC75SX; 75 ton") under conditions of a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C. to produce sheets measuring 100 mm in length, 35 mm in width, and 2 mm in thickness. (2) Hardness From the sheet obtained above, a dumbbell No. 3 test piece was obtained using a punching blade conforming to JIS K 6251:2010. Three of the obtained test pieces were stacked to a thickness of 6 mm, and values ​​were obtained immediately after measurement (0 seconds), 3 seconds after measurement, and 15 seconds after measurement using the Type A durometer method of JIS K 6253-2:2012. The greater the change in the measured value over time, the easier it is to obtain good flexibility, elasticity, and mechanical strength, and the more likely it is to exhibit strong adhesive strength. (3) Tensile Properties The dumbbell No. 3 test pieces obtained above were measured for 100% modulus, tensile strength at break, and tensile elongation at break in accordance with JIS K 6251: 2010. The higher the measured values ​​for 100% modulus, tensile strength at break, and tensile elongation at break, the more excellent the tensile properties.

[0177] [Adhesion strength (■ Peel strength)] For the laminate structures obtained in the examples and comparative examples, a peel test was carried out using an "Instron 5566" manufactured by Instron Corporation in accordance with JIS K 6854-2:1999 under conditions of a peel angle of 180° and a tensile speed of 200 mm / min, to measure the peel strength. The peel strength was calculated as the average value of a total of four tests. The higher the peel strength value, the higher the adhesive strength to the adherend.

[0178]

[0179]

[0180] In Tables 6 and 7, the "content ratio of component (A)" means the content ratio (mass %) of modified hydrogenated product (A) in 100 mass % of the resin composition.

[0181] In Table 6, comparing Examples 1 to 3 with Comparative Examples 1 to 3, which differ only in the type of modified hydrogenated product (A), it can be seen that Examples 1 to 3 exhibited excellent flexibility and moldability, as well as excellent tensile properties. It can also be seen that Examples 1 to 3 had higher peel strength to aluminum, specifically aluminum alloys, than Comparative Examples 1 to 3. Therefore, it can be seen that Examples 1 to 3 exhibited strong adhesive strength to both synthetic resins and metals even when injection molded at low temperatures of about 230°C. Furthermore, it can be seen from Example 4 that even when two or more hydrogenated block copolymers (C) were used, they exhibited excellent tensile properties and strong adhesive strength to both synthetic resins and metals. In Table 7, it can be seen that Examples 5 to 14 exhibited excellent flexibility and moldability, as well as excellent tensile properties. It can also be seen that Examples 5 to 14 exhibited strong adhesive strength to both synthetic resins and metals even when injection molded at low temperatures of about 230°C. Furthermore, Example 13 shows that excellent tensile properties and strong adhesive strength can be obtained even when two or more hydrogenated block copolymers (C) are used. Furthermore, Example 14 shows that excellent tensile properties and strong adhesive strength can be obtained when the resin composition contains the modified hydrogenated product (A) and the resin (B).

[0182] Examples 15-18 (1) Preparation of Resin Compositions The components and amounts used were as shown in Table 8. The premixed compositions were melt-kneaded using the twin-screw extruder "ZSK26Mc" described above at 230°C and a screw rotation speed of 200 rpm to obtain resin compositions. The physical properties of the resulting resin compositions were evaluated according to the following methods. The evaluation results are shown in Table 8. (2) Preparation of Laminated Structures Laminated structures were produced by injection insert molding using the following adherends (length 100 mm x width 35 mm x thickness 1 mm) as insert parts. The adherends were prepared by pretreatment as described above. Each adherend was fixed in a mold using a vacuum line. The resulting resin compositions were filled into a mold at a mold temperature of 50°C and cylinder temperatures of 230°C and 250°C, respectively, and the surface temperature of the adherend was cooled to 50°C to obtain laminated structures. The adhesive strength (peel strength) of the resin compositions of the resulting laminated structures was evaluated according to the following method. The evaluation results are shown in Table 8.

[0183] Details of the adherends used in producing the laminated structure are as follows: Polycarbonate (PC) plate: trade name "Iupilon S-3000R", manufactured by Mitsubishi Engineering-Plastics Corporation Acrylonitrile-butadiene-styrene resin (ABS) plate: trade name "Toyolac 700-314", manufactured by Toray Industries, Inc. Polypropylene (PP) plate: trade name "Prime Polypro J106G", manufactured by Prime Polymer Co., Ltd. Nylon 6 (PA6) plate: trade name "UBE Nylon6 1013B", manufactured by Ube Industries, Ltd. Aluminum alloy (AL) plate: material "A5052P" Stainless steel (SUS) plate: material "SUS304"

[0184] <Evaluation Methods> Details of the evaluation methods in the Examples and Comparative Examples are as follows: [Melt Flow Rate (MFR)] The flow rate (g / 10 min) was measured using the same method and conditions as those described in the above item [Melt Flow Rate (MFR)].

[0185] [Hardness and Tensile Properties] (1) Sheet Preparation The resin compositions obtained in Examples 15 to 18 were injection molded using the aforementioned injection molding machine "EC75SX" under conditions of a mold temperature of 50°C and cylinder temperatures of 230°C and 250°C, respectively, to produce sheets measuring 100 mm in length, 35 mm in width, and 2 mm in thickness. (2) Hardness From the sheets obtained above, a dumbbell No. 3 test piece was obtained using a punching blade conforming to JIS K 6251:2010. Three of the obtained test pieces were stacked to a thickness of 6 mm, and values ​​were obtained immediately after measurement (0 seconds), 3 seconds after measurement, and 15 seconds after measurement using the Type A durometer method of JIS K 6253-2:2012. (3) Tensile Properties The 100% modulus, tensile strength at break, and tensile elongation at break of the dumbbell No. 3 test pieces obtained above were measured in accordance with JIS K 6251:2010.

[0186] [Adhesion strength (■ Peel strength)] Peel strength was measured for the laminate structures obtained in Examples 15 to 18 by performing a peel test at a peel angle of 180° and a pulling rate of 200 mm / min in accordance with JIS K 6854-2: 1999 using the aforementioned "Instron 5566." The peel strength was calculated as the average value of a total of four tests.

[0187]

[0188] In Table 8, "Content of component (A)" means the content (mass%) of modified hydrogenated product (A) in 100 mass% of the resin composition.

[0189] Table 8 shows that Examples 15 to 18 exhibited sufficient tensile properties and strong adhesive strength to both synthetic resins and metals (e.g., aluminum alloys and stainless steel), and that adhesive strength tended to improve particularly when injection molded at 250° C. Therefore, it can be seen that Examples 15 to 18 exhibited excellent flexibility and moldability, and achieved both excellent tensile properties and strong adhesive strength, regardless of whether injection molding was performed at a temperature of 230° C. or 250° C.

[0190] Examples 19-23 and Comparative Example 4 (1) Preparation of Resin Compositions The components and amounts used were as shown in Table 9. The premixed compositions were melt-kneaded using the twin-screw extruder "ZSK26Mc" described above at 230°C and a screw rotation speed of 200 rpm to obtain resin compositions. The physical properties of the resulting resin compositions were evaluated according to the following methods. The evaluation results are shown in Table 9. (2) Preparation of Laminated Structures Laminated structures were produced by injection insert molding using the following adherends (length 100 mm x width 35 mm x thickness 1 mm) as insert parts. The adherends were prepared by pretreatment as described above. Each adherend was fixed in a mold using a vacuum line. The resulting resin composition was filled into a mold at a mold temperature of 50°C and a cylinder temperature of 230°C, and the surface temperature of the adherend was cooled to 50°C to obtain a laminated structure. The adhesive strength (peel strength) of the resin composition of the resulting laminated structures was evaluated according to the following method. The evaluation results are shown in Table 9.

[0191] Details of the adherends used in producing the laminated structure are as follows: Polycarbonate (PC) plate: trade name "Iupilon S-3000R", manufactured by Mitsubishi Engineering-Plastics Corporation Acrylonitrile-butadiene-styrene resin (ABS) plate: trade name "Toyolac 700-314", manufactured by Toray Industries, Inc. Polypropylene (PP) plate: trade name "Prime Polypro J106G", manufactured by Prime Polymer Co., Ltd. Nylon 6 (PA6) plate: trade name "UBE Nylon6 1013B", manufactured by Ube Industries, Ltd. Aluminum alloy (AL) plate: material "A5052P" Stainless steel (SUS) plate: material "SUS304"

[0192] <Evaluation Methods> Details of the evaluation methods in the Examples and Comparative Examples are as follows: [Melt Flow Rate (MFR)] The flow rate (g / 10 min) was measured using the same method and conditions as those described in the above item [Melt Flow Rate (MFR)].

[0193] [Hardness and Tensile Properties] (1) Sheet Preparation The resin compositions obtained in Examples 19 to 23 and Comparative Example 4 were injection molded using the aforementioned injection molding machine "EC75SX" under conditions of a mold temperature of 50°C and a cylinder temperature of 230°C to produce sheets measuring 100 mm in length, 35 mm in width, and 2 mm in thickness. (2) Hardness From the sheets obtained above, a dumbbell No. 3 test piece was obtained using a punching blade conforming to JIS K 6251:2010. Three of the obtained test pieces were stacked to a thickness of 6 mm, and values ​​were obtained immediately after measurement (0 seconds), 3 seconds after measurement, and 15 seconds after measurement using the Type A durometer method of JIS K 6253-2:2012. (3) Tensile Properties The 100% modulus, tensile strength at break, and tensile elongation at break of the dumbbell No. 3 test pieces obtained above were measured in accordance with JIS K 6251:2010.

[0194] [Adhesion strength (■ Peel strength)] Peel strength was measured for the laminate structures obtained in Examples 19 to 23 and Comparative Example 4 using the aforementioned "Instron 5566" in accordance with JIS K 6854-2: 1999 at a peel angle of 180° and a pulling rate of 200 mm / min. The peel strength was calculated as the average value of a total of four tests.

[0195]

[0196] In Table 9, "Content of component (A)" means the content (mass%) of the modified hydrogenated product (A) in 100 mass% of the resin composition.

[0197] Table 9 shows that Examples 19 to 23 exhibited sufficient tensile properties and strong adhesive strength to both synthetic resins and metals (e.g., aluminum alloys and stainless steel).Comparative Example 4 did not exhibit strong adhesive strength to synthetic resins and metals (especially stainless steel) compared to Examples 19 to 23.

[0198] The resin composition of this embodiment has excellent tensile properties and strong adhesive strength to synthetic resins, metals, etc. Therefore, a laminate structure to which the resin composition of this embodiment is adhered can be used in parts such as shock absorbing materials, covering materials with anti-slip properties, waterproof materials, and decorative materials that are adhered to the housings of large displays, notebook computers, mobile phones, personal digital assistants, electronic dictionaries, video cameras, digital still cameras, portable radio cassette players, inverters, and power tools.

Claims

1. The present invention relates to 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 the polymer block (A-2) is a modified hydrogenated product of a block copolymer, and the polymer block (A-1) has a structural unit derived from an aromatic vinyl compound and the polymer block (A-2) has a structural unit derived from a conjugated diene compound. The modified hydrogenated product of the present invention includes a resin (B), the modified hydrogenated product (A) has at least one functional group selected from the group consisting of a carboxy group, an amino group, a hydroxy group, and a group derived from an acid anhydride, and the vinyl bond amount of the polymer block (A-2) is 50 to 99 mol %, the resin (B) is at least one selected from the group consisting of an acrylic block copolymer and a thermoplastic polyurethane resin, the mass ratio (A) / (B) of the modified hydrogenated product (A) to the resin (B) is 90 / 10 to 10 / 90; The melt flow rate measured in accordance with JIS K7210:2014 at a temperature of 230°C and a load of 21N is 5g / 10min or more. Resin composition.

2. The resin composition according to claim 1, further comprising a hydrogenated block copolymer (C) having a polymer block (C-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (C-2) containing a structural unit derived from a conjugated diene compound.

3. The resin composition according to claim 2, wherein the vinyl bond content of the polymer block (C-2) is 1 to 85 mol %.

4. The resin composition according to claim 2, wherein the hydrogenation rate of carbon-carbon double bonds in the polymer block (C-2) is 80 to 100 mol %.

5. The resin composition according to claim 2, wherein the conjugated diene compound in the polymer block (C-2) contains at least one selected from the group consisting of isoprene, butadiene, and farnesene.

6. The resin composition according to claim 2, wherein the content of the polymer block (C-1) in the hydrogenated block copolymer (C) is 5 to 70 mass%.

7. The resin composition according to claim 1, wherein the content of the functional group in the modified hydrogenated product (A) is 0.10 to 5.00 phr.

8. 2. The resin composition according to claim 1, wherein the hydrogenation rate of carbon-carbon double bonds in the polymer block (A-2) is 80 to 100 mol %.

9. The resin composition according to claim 1, wherein the content of the structural unit derived from isoprene in the polymer block (A-2) is 30% by mass or more.

10. The resin composition according to claim 1, wherein the conjugated diene compound in the polymer block (A-2) contains isoprene and butadiene.

11. The resin composition according to claim 1, wherein the content of the polymer block (A-1) in the modified hydrogenated product (A) is 5 to 40 mass%.

12. The resin composition according to claim 2, further comprising 5 to 200 parts by mass of a softener per 100 parts by mass of the hydrogenated block copolymer (C).

13. The resin composition according to claim 12, wherein the softener is at least one selected from the group consisting of paraffinic process oils, naphthenic process oils, and aromatic process oils.

14. A molded article comprising the resin composition according to any one of claims 1 to 13.

15. A laminated structure having a layer formed from the resin composition according to any one of claims 1 to 13, and a layer formed from a material other than the resin composition.

16. The laminate structure according to claim 15, wherein the other material is at least one selected from the group consisting of synthetic resins and metals.

17. A method for producing the laminated structure according to claim 15, A method for producing a laminated structure, comprising injection insert molding the resin composition into a layer formed of a material other than the resin composition.