Laminate and method for manufacturing a laminate

Abstract

A laminate having a layer (I) having an acrylic resin as a main component, a layer (II) having a polyolefin resin as a main component, and an adhesive layer (III) that is provided between the layer having an acrylic resin as a main component and the layer having a polyolefin resin as a main component, the adhesive layer (III) being produced using an adhesive agent component having, as a main component, a hydrogenated conjugated diene block copolymer that has two or more polymer blocks selected from the group consisting of polymer blocks (A) having vinyl aromatic monomer units as a main component, polymer blocks (B) having conjugated diene monomer units as a main component, and polymer blocks (C) having both vinyl aromatic monomer units and conjugated diene monomer units, the hydrogenated conjugated diene block copolymer being such that unsaturated bonds in the conjugated diene monomer units are hydrogenated, and the hydrogenated conjugated diene block copolymer meeting prescribed conditions.

Description

[Technical Field]

[0001] The present invention relates to a laminate and a method for manufacturing a laminate. [Background technology]

[0002] Conventionally, laminates have been proposed as molded articles with excellent design, transparency, and decorative properties, having a base made of polyolefin resin such as polypropylene resin and an acrylic resin layer with excellent appearance, from the viewpoint of moldability and low cost. For example, Patent Document 1 proposes a laminate comprising a substrate mainly composed of polypropylene resin and thermoplastic resin, a sealing layer, and an acrylic resin layer.

[0003] On the other hand, polyolefin resins and acrylic resins have the problem of being difficult to bond together in terms of solubility parameters, etc. To address this problem, laminates using solvent-based adhesives such as acrylic adhesives and urethane adhesives have been proposed. However, from the perspective of reducing VOCs (volatile organic compounds), there is a growing demand for lamination molding technologies that do not use organic solvents. For example, Patent Document 2 proposes a laminate of a polypropylene resin substrate and an acrylic resin layer, wherein an adhesive layer containing a polypropylene resin as a non-solvent adhesive is provided on a substrate made of polypropylene resin. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2021-181232 [Patent Document 2] Japanese Patent Publication No. 2013-14027 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the laminate disclosed in Patent Document 2 still has the problem that there is room for improvement in terms of adhesive strength.

[0006] Therefore, the present invention aims to provide a laminate that does not use organic solvents, has a good appearance, and has high adhesive strength. [Means for solving the problem]

[0007] The present inventors conducted diligent studies to solve the problems of the above-mentioned prior art and, as a result, discovered that by providing an adhesive layer mainly composed of a hydrogenated conjugated diene block copolymer having a specific structure, or by incorporating a hydrogenated conjugated diene block copolymer as an adhesive component into the polyolefin resin layer, it is possible to form a laminate with a good appearance and high adhesive strength without using organic solvents, thus completing the present invention. In other words, the present invention is as follows.

[0008] [1] A layer (I) mainly composed of acrylic resin, A layer (II) mainly composed of polyolefin resin, An adhesive layer (III) is provided between the acrylic resin-based layer and the polyolefin resin-based layer, A laminate having, The aforementioned adhesive layer (III) The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer, comprising two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having both vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. A laminate in which the hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less. [2] The hydrogenated conjugated diene block copolymer is Satisfying the above conditions (i), (iii), and (iv), The laminate described in [1] above. [3] The hydrogenated conjugated diene block copolymer is Satisfying the above conditions (ii), (iii), and (iv), The laminate described in [1] above. [4] The hydrogenated conjugated diene block copolymer is The above conditions (i) and (ii) are met, and the above condition (iv) is not met, Furthermore, the following conditions (v) must be met: The laminate described in [1] above. <Condition (v)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is less than 25% by mass. [5] The hydrogenated conjugated diene block copolymer satisfies condition (i), and the polar groups of the hydrogenated conjugated diene block copolymer are At least one selected from the group consisting of an acid anhydride group, an amino group, a dicarboxyl group, a carboxyl group, an epoxy group, and an oxetanyl group. The laminate according to any one of the above [1] to [4]. [6] The polar group of the hydrogenated conjugated diene block copolymer is an amino group. The laminate described in [5] above. [7] The hydrogenation rate of the hydrogenated conjugated diene block copolymer is 90% or less. The laminate according to any one of the above [1] to [6]. [8] The thickness of the aforementioned acrylic resin-based layer (I) is 1.5 mm or less. The laminate according to any one of the above [1] to [7]. [9] The hydrogenated conjugated diene block copolymer satisfies the above condition (iv), The laminate according to any one of [1] to [3] or [5] to [8] above.

[10] A method for manufacturing a laminate as described in [1] above, A step of laminating the acrylic resin-based layer (I) and the adhesive layer (III) so that they are in contact, A step of laminating the polyolefin resin-based layer (II) such that the adhesive layer (III) and the polyolefin resin-based layer (II) are in contact, It has, A method for manufacturing laminates.

[11] The thickness of the aforementioned acrylic resin-based layer (I) is 1.5 mm or less. The method for manufacturing the laminate described in

[10] above.

[12] In the process of laminating the acrylic resin-based layer (I) and the adhesive layer (III), The acrylic resin-based layer (I) and the adhesive layer (III) are laminated in a molten state. A method for manufacturing a laminate according to

[10] or

[11] above.

[13] In the process of laminating the aforementioned polyolefin resin-based layer (II), A laminate having the acrylic resin-based layer (I) and the adhesive layer (III) is mounted in a mold. The polyolefin resin is poured into the mold in a molten state. A method for manufacturing a laminate according to any one of the above

[10] to

[12] .

[14] A layer (I) mainly composed of acrylic resin, A layer (IV) containing polyolefin resin and adhesive components, A laminate having, The amounts of the polyolefin resin and adhesive component are in a mass ratio of polyolefin resin / adhesive component = 30 / 70 to 95 / 5. The aforementioned adhesive component The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer having two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. A laminate in which the hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

[15] The laminate according to

[14] , wherein the hydrogenated conjugated diene block copolymer satisfies the conditions (i), (iii), and (iv).

[16] The laminate according to

[14] , wherein the hydrogenated conjugated diene block copolymer satisfies the conditions (ii), (iii), and (iv).

[17] The hydrogenated conjugated diene block copolymer is The above conditions (i) and (ii) are met, and the above condition (iv) is not met, Furthermore, the laminate described in

[14] that satisfies the above condition (v). <Condition (v)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is less than 25% by mass.

[18] The hydrogenated conjugated diene block copolymer satisfies condition (i), and the polar groups of the hydrogenated conjugated diene block copolymer are The laminate according to

[14] or

[15] , wherein at least one is selected from the group consisting of an acid anhydride group, an amino group, a dicarboxyl group, a carboxyl group, an epoxy group, and an oxetanyl group. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a laminate that does not use organic solvents, has a good appearance, and has high adhesive strength. [Modes for carrying out the invention]

[0010] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. The following embodiments are illustrative examples for explaining the present invention and are not intended to limit the present invention to the following content. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0011] [Laminate] The laminate of this embodiment has the following two forms, which will be described as the laminate of the first embodiment and the laminate of the second embodiment, respectively. The laminate of the first embodiment is A layer (I) mainly composed of acrylic resin (hereinafter sometimes referred to as layer (I)), A layer (II) mainly composed of polyolefin resin (hereinafter sometimes referred to as layer (II)), An adhesive layer (III) (hereinafter sometimes referred to as layer (III)) is provided between the acrylic resin-based layer and the polyolefin resin-based layer, It is a laminate that has the following characteristics. The aforementioned adhesive layer (III) The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer, comprising two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having both vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. The hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

[0012] The laminate of the first embodiment has an adhesive layer (III) consisting of an adhesive component as a single layer, which allows the stress during impact to be dispersed by the highly flexible hydrogenated conjugated diene block copolymer, resulting in high impact resistance for the laminate as a whole.

[0013] The laminate of the second embodiment is A layer (I) mainly composed of acrylic resin, A layer (IV) containing polyolefin resin and adhesive components (hereinafter sometimes referred to as layer (IV)), It is a laminate that has the following characteristics. The amounts of the polyolefin resin and adhesive component are in a mass ratio of polyolefin resin / adhesive component = 30 / 70 to 95 / 5. The aforementioned adhesive component The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer having two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. The hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

[0014] The laminate of the second embodiment has a layer (I) mainly composed of an acrylic resin and a layer (IV) containing a polyolefin resin and an adhesive component. Layer (IV) is a form in which an adhesive component is included in layer (II), which is mainly composed of polyolefin resin and constitutes the laminate of the first embodiment described above. According to the laminate of the second embodiment, the mixing of adhesive components into the acrylic resin-based layer (I) is suppressed, resulting in a better appearance.

[0015] The laminate of the first embodiment and the laminate of the second embodiment are similar in that they have a layer (I) mainly composed of an acrylic resin and a layer mainly composed of a polyolefin resin, and that a specific hydrogenated conjugated diene block copolymer is the main component of the adhesive. The laminate of the first embodiment has an independent adhesive layer (III). On the other hand, the laminate of the second embodiment has a layer (IV) containing an adhesive component and a polyolefin resin. While the laminate of the first embodiment exhibits excellent impact resistance, the hydrogenated conjugated diene block copolymer of the adhesive layer (III) slightly melts with the acrylic resin-based layer (I) during the molding of the laminate, resulting in a tendency for its appearance to be inferior to that of the laminate of the second embodiment. Therefore, it is preferable to select the embodiment according to the application, whether impact resistance is required or good appearance is necessary.

[0016] (Layer (I)) The laminates of the first and second embodiments have a layer (I) mainly composed of an acrylic resin. By using acrylic resin as the main material, a laminate with excellent appearance can be obtained. Here, "primarily composed of acrylic resin" means that acrylic resin accounts for 30% or more of the total mass of layer (I) by 100%, preferably 40% or more by mass, more preferably 50% or more by mass, and even more preferably 60% or more by mass. The acrylic resin is not limited to the following, but examples include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, methyl methacrylate-butyl methacrylate copolymer, and methyl methacrylate-styrene copolymer. Furthermore, as the acrylic resin, a mixed resin of the above-mentioned acrylic resin and thermoplastic polyurethane resin, a mixed resin of the above-mentioned acrylic resin and acrylic rubber, etc., can be used. The acrylic resin-based layer (I) may contain, as necessary, general additives other than the acrylic resin, such as stabilizers, lubricants, processing aids, impact-absorbing aids, fillers, colorants, matting agents, and UV absorbers. In such cases, the acrylic resin content in layer (I) shall be calculated based on the total content of the mixed material. Examples of the aforementioned acrylic resins include commercially available products such as Acrypet (manufactured by Mitsubishi Rayon Co., Ltd.), Sumipex (manufactured by Sumitomo Chemical Co., Ltd.), and Delpet (manufactured by Asahi Kasei Corporation).

[0017] (Layer (II)) The laminate of the first embodiment has a layer (II) mainly composed of polyolefin resin. The polyolefin resin-based layer (II) mainly consists of polyolefin resins other than the hydrogenated conjugated diene block copolymers described later. Here, "primarily composed of polyolefin resin" means that polyolefin resin accounts for 30% or more by mass of 100% by mass of the entire layer (II), preferably 40% or more by mass, more preferably 50% or more by mass, and even more preferably 60% or more by mass. The layer (II) of the laminate in the first embodiment shall not contain the adhesive component described later.

[0018] (Layer(IV)) The laminate of the second embodiment has a layer (IV) containing a polyolefin resin and an adhesive component. Layer (IV) contains polyolefin resins other than the hydrogenated conjugated diene block copolymer described later, and adhesive components described later. In layer (IV), the amounts of polyolefin resin and adhesive components are in mass ratio, with polyolefin resin / adhesive component = 30 / 70 to 95 / 5. The preferred morphology of the polyolefin resin is the same for both layer (II) and layer (IV).

[0019] <Polyolefin resin> The polyolefin resin used in layers (II) and (IV) is not limited to the following, but examples include polyethylene resin and polypropylene resin. Examples of polyethylene resins include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and copolymers of ethylene and α-olefins having 3 to 8 carbon atoms. When the polyethylene resin is a copolymer of ethylene and α-olefins having 3 to 8 carbon atoms, examples of α-olefins in the copolymer include propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Examples of polypropylene resins include propylene homopolymers synthesized using a Ziegler-Natta type catalyst, and copolymers of random or block propylene with α-olefins. In the case of copolymers of propylene and α-olefins, the proportion of α-olefin is preferably 30% by mass or less, and more preferably 35% by mass or less, based on 100% by mass of the polypropylene resin. Specifically, polypropylene resins include propylene homopolymers and copolymers of propylene and α-olefins having 2 to 8 carbon atoms (hereinafter also referred to as "propylene-based resins"). When the polypropylene resin is a copolymer of propylene and α-olefins having 2 to 8 carbon atoms, examples of α-olefins in the copolymer include ethylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. These polyolefin resins can be synthesized by conventionally known methods. From the viewpoint of heat resistance (heat aging resistance) and moldability, polypropylene resin is preferred as the polyolefin resin.

[0020] The polyolefin resin used in layers (II) and (IV) has a melt flow rate (MFR) of typically 1.0 to 1000 g / 10 min, preferably 5.0 to 100 g / 10 min. A polyolefin resin MFR of 1.0 g / 10 min or higher tends to improve the moldability (fluidity) of layers (II) and (IV). It also tends to suppress deterioration of the molded product's appearance (flow marks). The polyolefin resins used in layers (II) and (IV) may be used individually or in combination of two or more types.

[0021] Furthermore, from the viewpoint of improving the impact resistance, hardness, and fluidity of the layers, layers (II) and (IV) may contain an olefin-based elastomer. The olefin-based elastomer is, for example, a copolymer of ethylene and / or propylene, as listed above as a polyolefin resin, and an α-olefin having 3 to 8 carbon atoms, wherein the proportion of α-olefin is greater than or equal to the aforementioned preferred proportion. Specifically, the proportion of α-olefin is 30% by mass or more, preferably more than 30% by mass, more preferably 35% by mass or more, and more preferably 40% by mass or more, based on 100% by mass of the total olefin-based elastomer. When the proportion of α-olefin is within the above range, the olefin-based elastomer tends to have low rigidity, which can improve the impact resistance of the laminate of this embodiment.

[0022] (Adhesive layer (III)) The laminate of the first embodiment has an adhesive layer (III) made of an adhesive component between the layer (I) and layer (II) described above.

[0023] (Layer (IV) containing polyolefin resin and adhesive components) The laminate of the second embodiment has a layer (IV) containing the polyolefin resin and adhesive component described above.

[0024] In the laminate of the first embodiment, the adhesive layer (III) is an independent layer consisting mainly of an adhesive component comprising a hydrogenated conjugated diene block copolymer, which will be described later. Here, "primarily composed of hydrogenated conjugated diene block copolymer" means that the content of the hydrogenated conjugated diene block copolymer in the adhesive component is 50% by mass or more, and other components may be included in a range that does not impair the appearance and adhesive strength. From the viewpoint of the aforementioned adhesive strength and appearance, the content of hydrogenated conjugated diene block copolymer in the adhesive component is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more.

[0025] In the laminate of the second embodiment, layer (IV) contains the aforementioned polyolefin resin and the adhesive component described later. The mass ratio of polyolefin resin to adhesive component is polyolefin resin / adhesive component = 30 / 70 to 95 / 5, preferably 35 / 65 to 95 / 5, more preferably 40 / 60 to 95 / 5, even more preferably 45 / 55 to 95 / 5, even more preferably 50 / 50 to 95 / 5, and even more preferably 60 / 40 to 90 / 10. The content of hydrogenated conjugated diene block copolymer in the adhesive component is the same as in the case of adhesive layer (III) described above.

[0026] <Adhesive components> In both the first and second embodiments, the adhesive component comprises a hydrogenated conjugated diene block copolymer having two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. The hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv). The composition of polymer block (A), polymer block (B), and polymer block (C) will be described later.

[0027] Condition (i): The hydrogenated conjugated diene block copolymer has polar groups. Condition (ii): The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound (hereinafter also simply referred to as "unit (a)") and units derived from 1,4-bonds (hereinafter also simply referred to as "unit (b)"), and the content of unit (a) is 50% or more (vinyl bond amount) when the content of the conjugated diene monomer units is taken as 100%. Condition (iii): The hydrogenated conjugated diene block copolymer has at least one polymer block (C). Condition (iv): The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

[0028] The laminate of this embodiment exhibits high adhesive strength because the adhesive component has high compatibility with acrylic resin and polyolefin resin. While it might seem simple to include a hydrogenated conjugated diene block copolymer with similar solubility parameters (sp values) to both resins in the adhesive component, acrylic resins have higher solubility parameters (sp values) than polyolefin resins. To bond layers (I) and (II) primarily composed of resins with different solubility parameters, the hydrogenated conjugated diene block copolymer included in the adhesive component must have a polymer backbone compatible with both resins.

[0029] In order to improve compatibility with acrylic resins, it is preferable that the hydrogenated conjugated diene block copolymer satisfies conditions (i) and / or (iii) and / or (iv) in terms of solubility parameters (sp value).

[0030] The hydrogenated conjugated diene block copolymer preferably satisfies condition (ii) and / or condition (iii) and / or condition (iv) in order to improve compatibility with the polyolefin resin.

[0031] Therefore, if the hydrogenated conjugated diene block copolymer satisfies two or more of the above conditions (i) to (iv), it will have high compatibility with layer (I) and layer (II), and in particular, will have excellent compatibility with polyolefin resin in terms of solubility parameters. Therefore, whether the configuration includes an adhesive layer (III) which is a single layer of adhesive components, or a layer (IV) which includes polyolefin resin and adhesive components, a laminate with high adhesive strength can be obtained without impairing the appearance of the acrylic resin-based layer (I). The adhesive components may include other adhesive components besides hydrogenated conjugated diene block copolymers, to the extent that they do not impair the appearance or adhesive strength.

[0032] As described in condition (i) above, the presence of polar groups in the hydrogenated conjugated diene block copolymer used as an adhesive component improves the sp value of the hydrogenated conjugated diene block copolymer. This improves the compatibility and reactivity between the acrylic resin in layer (I) and the hydrogenated conjugated diene block copolymer.

[0033] Vinyl aromatic compounds are known to have a higher sp value than conjugated diene compounds. Therefore, as in condition (iv) above, when the content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less, the hydrogenated conjugated diene block copolymer exhibits excellent compatibility with layer (I) and layer (II). By having a vinyl aromatic monomer unit content of 25% by mass or more in the hydrogenated conjugated diene block copolymer, the sp value of the hydrogenated conjugated diene block copolymer becomes sufficiently high, resulting in improved compatibility with the acrylic resin-based layer (I) and sufficient adhesive strength. By limiting the content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer to 80% by mass or less, it is possible to suppress the sp value from becoming too high, improving compatibility with the polyolefin resin-based layer (II) and obtaining sufficient adhesive strength. In the above condition (iv), the content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is preferably 30 to 75% by mass, more preferably 35 to 70% by mass, even more preferably 40 to 70% by mass, even more preferably 45 to 70% by mass, even more preferably 50 to 70% by mass, and particularly preferably 55 to 70% by mass. The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer can be controlled within the above numerical range by adjusting the amount of vinyl aromatic compound added and the polymerization time during the polymerization process.

[0034] Furthermore, from the viewpoint of obtaining sufficient adhesive strength, it is preferable that the hydrogenated conjugated diene block copolymer has at least one polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, as in condition (iii) above. This results in excellent compatibility between the hydrogenated conjugated diene block copolymer and layers (I) and (II), thereby improving adhesive strength.

[0035] Furthermore, unit (a) (hereinafter sometimes referred to as vinyl bond) is known to have superior compatibility with polyolefin resin compared to unit (b). Therefore, the hydrogenated conjugated diene block copolymer has improved compatibility with the polyolefin resin of layer (II) and improved adhesive strength due to having a vinyl bond content of 50% or more. The amount of vinyl bonded in the hydrogenated conjugated diene block copolymer before hydrogenation is preferably 55% or more, more preferably 60% or more, even more preferably 65% ​​or more, even more preferably 67% or more, and even more preferably 70% or more. The amount of vinyl bonding can be measured by the method described in the examples below, and as described later, it can be controlled to the above numerical range by using a vinyl bonding amount adjusting agent (vinylizing agent).

[0036] Furthermore, in the hydrogenated conjugated diene block copolymers within the adhesive components, the unsaturated bonds derived from the conjugated diene compound are hydrogenated. By hydrogenating the conjugated diene monomer units, which have excellent compatibility with the polyolefin resin in layer (II), the sp value difference between polymer block (B) and polymer block (C) of the hydrogenated conjugated diene block polymer and the polyolefin resin becomes smaller, improving the compatibility between the hydrogenated conjugated diene block copolymer and layer (II). Furthermore, hydrogenation reduces the number of thermally unstable unsaturated bonds, which tends to improve heat aging resistance, weather resistance, and mold contamination resistance (properties that prevent mold contamination). From the above perspective, the hydrogenation rate is preferably 80% or more, more preferably 83% or more, and even more preferably 85% or more. Furthermore, as will be described later, from the viewpoint of heat cycle resistance and hot water resistance of the laminate of this embodiment, it is preferable that the hydrogenation rate of the hydrogenated conjugated diene block copolymer be 90% or less. This case will be described later. The hydrogenation rate of hydrogenated conjugated diene block copolymers can be measured using nuclear magnetic resonance (NMR) or the like, and specifically, it can be measured by the method described in the examples. Furthermore, the hydrogenation rate can be controlled to the above numerical range by, for example, adjusting the amount of hydrogen reacted during the hydrogenation reaction.

[0037] When the tanδ peak temperature in the viscoelasticity measurement of the adhesive component is located at the ambient temperature of use of the laminate in this embodiment, a laminate with excellent vibration damping and noise reduction properties tends to be obtained. When the hydrogenated conjugated diene block copolymer contained in the adhesive component satisfies conditions (iii) and (iv) above, the tanδ peak temperature of the hydrogenated conjugated diene block copolymer tends to be 0°C or higher. Furthermore, when condition (i) above is satisfied, high adhesive strength is exhibited, which tends to contribute to improved vibration damping properties. From the above-mentioned perspective, hydrogenated conjugated diene block copolymers tend to yield laminates that have excellent vibration damping properties, adhesive strength, and impact resistance at room temperature, as well as a good appearance, when conditions (i), (iii), and (iv) are met.

[0038] When the hydrogenated conjugated diene block copolymer used as an adhesive component satisfies the above condition (i), decomposition products derived from the modifier used to bond polar groups to the hydrogenated conjugated diene block copolymer tend to volatilize during molding, leading to mold contamination and deterioration of the working environment. When the hydrogenated conjugated diene block copolymer satisfies condition (i) above, it is preferable that the amount of unreacted modifier is small, from the viewpoint of suppressing decomposition products derived from the modifier and improving molding cycleability and working environment. The amount of unreacted modifier is preferably 0.2% by mass or less, more preferably 0.15% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less, relative to the hydrogenated conjugated diene block copolymer after the modification process. Similarly, from the viewpoint of suppressing mold contamination, it is preferable that the reaction rate between the hydrogenated conjugated diene block copolymer and the modifier described later is high. Preferred methods for attaching polar groups to hydrogenated conjugated diene block copolymers include introducing them by using polymerization initiators having predetermined functional groups that will become polar groups (as described later), polymerizing unsaturated monomers having each functional group, forming functional groups at the living terminus, and adding a modifying agent having a functional group. Polar groups are not limited to the following, but examples include acid anhydride groups, amino groups, dicarboxyl groups, carboxyl groups, epoxy groups, and oxetanyl groups. From the viewpoint of the reaction rate mentioned above, amino groups and epoxy groups are preferred, and amino groups are more preferred from the viewpoint of being able to easily set the amount of unreacted denaturant to be small by controlling the amount added.

[0039] In contrast, when hydrogenated conjugated diene block copolymers satisfy conditions (ii), (iii), and (iv), decomposition of the hydrogenated conjugated diene block copolymer is less likely to occur, and the volatilization of decomposition products is low, thus ensuring excellent molding cycleability and working environment.

[0040] When the operating temperature of the laminate of this embodiment is low (below 0°C), it is preferable to use an adhesive component with high flexibility. The high flexibility of the adhesive component allows for stress distribution even at low temperatures, and the laminate of this embodiment tends to exhibit high impact resistance. From the above perspective, when a hydrogenated conjugated diene block copolymer satisfies conditions (i), (ii), and (v) below, the refractive index of the acrylic resin and the hydrogenated conjugated diene block copolymer tend to become close, and the laminate of this embodiment tends to have high transparency, and a laminate with excellent impact resistance and adhesive strength at low temperatures is obtained. Condition (v): The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is less than 25% by mass. In the above condition (v), the content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is preferably 20% by mass or less, more preferably 17% by mass or less, even more preferably 15% by mass or less, and even more preferably 13% by mass or less. The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer can be controlled within the above numerical range by adjusting the amount of vinyl aromatic compound added and the polymerization time during the polymerization process.

[0041] When the hydrogenated conjugated diene block copolymer used as an adhesive component satisfies condition (i), the polar group is preferably at least one selected from the group consisting of acid anhydride groups, amino groups, dicarboxyl groups, carboxyl groups, epoxy groups, and oxetanyl groups, as described above, in terms of compatibility with the acrylic resin-based layer (I) mentioned above. More preferably, it is at least one selected from the group consisting of acid anhydride groups, amino groups, dicarboxyl groups, and carboxyl groups. Hydrogenated conjugated diene block copolymers tend to have affinity and / or reactivity with acrylic resins, resulting in laminates with high adhesive strength, because they possess at least one polar group selected from the group described above. Affinity refers to the possibility of generating at least one intermolecular force selected from the group consisting of interionic interactions, hydrogen bonds, dipole interactions, and van der Waals forces between each component. Reactivity means that the polar groups of each component have covalent bonding properties. When polar groups react with each other, for example, when the OH group of a carboxyl group is eliminated, the original polar group changes or disappears, but if a covalent bond is formed as a result, the polar groups are included in the definition of "reactivity". From the viewpoint of adhesion, it is preferable that the material has affinity and reactivity, and from the viewpoint of reactivity, it is preferable that the polar group of the hydrogenated conjugated diene block copolymer is an amino group.

[0042] The amount of polar groups in the hydrogenated conjugated diene block copolymer is not particularly limited, but from the viewpoint of compatibility with the acrylic resin-based layer (I), it is preferably 0.01% by mass or more relative to the entire hydrogenated conjugated diene block copolymer. More preferably it is 0.05% by mass or more, and even more preferably 0.10% by mass or more. The amount of polar groups in the hydrogenated conjugated diene block copolymer is preferably 20% by mass or less, from the viewpoint of mold contamination and working environment conditions mentioned above. The amount of polar groups in a hydrogenated conjugated diene block copolymer can be controlled within the above numerical range by adjusting the reaction conditions with the compound used to form these polar groups during the manufacturing process of the hydrogenated conjugated diene block copolymer, such as the amount of compound added, the reaction temperature, and the reaction time.

[0043] In recent years, when decorative laminates are used as materials for automotive interiors and exteriors, there is a growing demand for high adhesion (heat cycle resistance, hot water resistance) not only at room temperature but also across a wide temperature range and in high-temperature, high-humidity environments. In order to ensure sufficient heat cycle resistance and hot water resistance, it is preferable that the adhesive component used in layer (III) has polar groups that are reactive with the aforementioned acrylic resin. When layer (I) is thin, in order for the laminate of this embodiment to have sufficient heat cycle resistance and / or hot water resistance, high compatibility between the hydrogenated conjugated diene block copolymer and the acrylic resin is required not only near the interface between layer (I) and layer (III), but also near the outer layer. However, if the hydrogenated conjugated diene block copolymer and the acrylic resin are compatible near the outer layer, it tends to impair the appearance and reduce the adhesion to layer (II). In view of these problems, and from the viewpoint of obtaining sufficient heat cycle resistance and / or hot water resistance, an amino group is preferred as the polar group of the hydrogenated conjugated diene copolymer from the viewpoint of its reactivity with acrylic resin.

[0044] Furthermore, in order to increase the covalent bonds between the acrylic resin of layer (I) and the hydrogenated conjugated diene block copolymer of layer (III), and to improve the heat cycle resistance and hot water resistance of the laminate of this embodiment, the hydrogenation rate of the hydrogenated conjugated diene block copolymer is preferably 90% or less, more preferably 88% or less, even more preferably 86% or less, and even more preferably 85% or less. Generally, acrylic resins have unsaturated bonds that exhibit radical reactivity due to side reactions during polymerization. When the hydrogenation rate of the hydrogenated conjugated diene block copolymer is 90% or less, the unsaturated bonds derived from the conjugated diene remaining unhydrogenated in the hydrogenated conjugated diene block copolymer and the unsaturated bonds of the acrylic resin undergo a radical reaction during the manufacturing of the laminate, forming covalent bonds. As a result, the laminate of this embodiment tends to have improved heat cycle resistance and hot water resistance.

[0045] On the other hand, it is preferable to avoid leaving too many unsaturated bonds in the hydrogenated conjugated diene block copolymer, from the viewpoint of preventing gelation and suppressing mold contamination. Furthermore, reducing the amount of unreacted denaturing agent tends to suppress mold contamination. The lower limit of the hydrogenation rate of the hydrogenated conjugated diene block copolymer is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more, from the viewpoint of suppressing the deterioration of the appearance of the laminate of this embodiment due to crosslinking between hydrogenated conjugated diene block copolymers, as described above. Generally, it is known that the amount of unsaturated bonds in a hydrogenated conjugated diene block copolymer with a hydrogenation rate of 50% or more is greater than the amount of unsaturated bonds in the acrylic resin produced by the side reaction, and by having a hydrogenation rate of 50% to 90% of the hydrogenated conjugated diene block copolymer, the heat cycle resistance, hot water resistance, heat aging resistance, weather resistance, appearance, and mold contamination resistance of the laminate of this embodiment described above tend to be satisfied. In other words, from the viewpoint of heat cycle resistance, hot water resistance, weather resistance, appearance, and mold contamination, it is preferable that the hydrogenated conjugated diene copolymer has amino groups, more preferably the hydrogenation rate of the hydrogenated conjugated diene block copolymer having amino groups is 50% to 90%, more preferably 60% to 90%, even more preferably 70% to 90%, even more preferably 70% to 88%, even more preferably 70% to 86%, and particularly preferably 70% to 85%.

[0046] Furthermore, decorative laminates used as materials for automotive interiors and exteriors require weight reduction from the standpoint of fuel efficiency, and there is a tendency to require thinner layers (I), which are mainly composed of acrylic resin and serve as decorative layers. From the above viewpoint, the thickness of the layer (I) is preferably 1.5 mm or less, more preferably 1.0 mm or less, even more preferably 0.7 mm or less, even more preferably 0.5 mm or less, and even more preferably 0.3 mm or less. When the thickness of layer (I) is thin, specifically 1.5 mm or less, from the viewpoint of productivity of the laminate of this embodiment, it is preferable to manufacture a laminate of at least two layers in which layers (I) and layer (III) are in contact, and then laminate it onto layer (II) to obtain the laminate of this embodiment. From the viewpoint of the handling of the laminate of at least two layers including layers (I) and layer (III), the content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer used in layer (III) is preferably 25% by mass or more, more preferably 27% by mass or more, even more preferably 30% by mass or more, and even more preferably 33% by mass or more. By having a vinyl aromatic monomer unit content of 25% by mass or more in the hydrogenated conjugated diene block copolymer, the stickiness of layer (III) can be suppressed, resulting in good winding and / or unwinding properties of the laminate containing at least two layers, including layer (I) and layer (III), and generally providing excellent handling. The upper limit of the content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, even more preferably 60% by mass or less, and particularly preferably 55% by mass or less, from the viewpoint of compatibility with layer (II).

[0047] [Detailed composition of hydrogenated conjugated diene block copolymer] The conjugated diene compounds that make up hydrogenated conjugated diene block copolymers used as adhesive components are diolefins having one pair of conjugated double bonds. The hydrogenated conjugated diene block copolymer has two or more polymer blocks selected from the group consisting of the polymer blocks (A) to (C) below. (A) Polymer block mainly composed of vinyl aromatic monomer units (polymer block (A)) (B) Polymer block mainly composed of conjugated diene monomer units (polymer block (B)) (C) Polymer block having vinyl aromatic monomer units and conjugated diene monomer units (Polymer block (C))

[0048] The polymer block (A) mainly composed of vinyl aromatic monomer units shall have a vinyl aromatic monomer unit content of 80% by mass or more. The vinyl aromatic compounds used to form vinyl aromatic monomer units are not limited to the following, but include, for example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferred from the viewpoint of availability and productivity, and styrene is more preferred. The polymer block (A) may be composed of one type of vinyl aromatic monomer unit, or it may be composed of two or more types of vinyl aromatic monomer units. From the viewpoint of the strength of the laminate, the content of vinyl aromatic monomer units in the polymer block (A) should be more than 95% by mass, preferably 100% by mass (no other compounds are intentionally added).

[0049] Polymer block (B) mainly composed of conjugated diene monomer units shall have a conjugated diene monomer unit content of 80% by mass or more. The conjugated diene compound used to form the conjugated diene monomer unit is a diolefin having a pair of conjugated double bonds. Examples of diolefins, but not limited to the following, include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, and farnesene. Among these, 1,3-butadiene and isoprene are preferred from the viewpoint of availability and productivity. The polymer block (B) may be composed of one type of conjugated diene monomer unit, or it may be composed of two or more types of conjugated diene monomer units. From the viewpoint of impact resistance of the laminate, the content of conjugated diene monomer units in the polymer block (B) should be more than 95% by mass, preferably 100% by mass (no other compounds are intentionally added). Furthermore, to the extent that the appearance and / or adhesive strength of the laminate is not impaired, the hydrogenated conjugated diene block copolymer may also contain polymer blocks (D) consisting of compounds copolymerizable with vinyl aromatic monomer units and / or conjugated diene monomer units, other than vinyl aromatic monomer units and / or conjugated diene monomer units.

[0050] The vinyl aromatic compound and conjugated diene compound used to form the vinyl aromatic monomer units and conjugated diene monomer units contained in the polymer block (C) having the conjugated diene monomer units and vinyl aromatic monomer units may be any compound that can be used in polymer block (A) and polymer block (B). There are no particular limitations on the distribution of vinyl aromatic monomer units in polymer block (C). The vinyl aromatic monomer units in polymer block (C) may be uniformly distributed or tapered. Furthermore, there may be multiple portions where vinyl aromatic monomer units are uniformly distributed and / or tapered, and there may be multiple segments with different vinyl aromatic monomer unit content. From the viewpoint of compatibility mentioned above, the polymer block (C) has a mass ratio of vinyl aromatic monomer units to conjugated diene monomer units of 5 / 95 to 95 / 5, preferably 10 / 90 to 90 / 10, and more preferably 15 / 85 to 85 / 15. This allows polymer block (C) to be clearly distinguished from polymer block (A) and polymer block (B).

[0051] In hydrogenated conjugated diene block copolymers used as adhesive components, other compounds copolymerizable with conjugated diene compounds and vinyl aromatic compounds can also be used. The structure of the hydrogenated conjugated diene-based block copolymer is not particularly limited, and examples thereof include those having a structure represented by the following formula. In the following formula, the description of the polar group is omitted.

[0052] (b-c) n , c-(b-c) n , b-(c-b) n , (b-c) m -X, (c-b) m , [(b-c) n m , [(c-b) n m , [c-(b-c) n m , [b-(c-b) n m , [(b-c) n -b] m , [(c-b) n -c] m , (a-b) n , b-(a-b) n , a-(b-a) n , (a-b) m -X, (b-a) m , [(a-b) n m , [(b-a) n m , [b-(a-b) n m , [a-(b-a) n m , [(a-b) n -a] m , [(b-a) n -b] m , (a-c) n , c-(a-c) n , a-(c-a) n , (a-c) m -X, (c-a) m , [(a-c) n m , [(c-a) n m , [c-(a-c)​​​​​​​​​​n ] m -X、[a-(c-a) n ] m -X、[(a-c) n -a] m -X、[(c-a) n -c] m -X、 c-(b-a) n 、c-(a-b) n 、 c-(a-b-a) n 、c-(b-a-b) n 、 a-c-(b-a) n 、a-c-(a-b) n 、 a-c-(b-a) n -b、[(a-b-c) n ] m -X、 [a-(b-c) n ] m -X、[(a-b) n -c] m -X、 [(a-b-a) n -c] m -X、 [(b-a-b) n -c] m -X、[(c-b-a) n ] m -X、 [c-(b-a)n] m -X、[c-(a-b-a) n ] m -X、[c-(b-a-b) n ] m -X a-(b-c) n 、a-(c-b) n 、 a-(c-b-c) n 、a-(b-c-b) n 、 c-a-(b-c) n 、c-a-(c-b) n 、 c-a-(b-c) n -b、[(c-b-a) n ] m -X、 [c-(b-a) n ] m -X、[(c-b) n -a] m -X、 [(c-b-c) n -a] m -X、 [(b-c-b) n -a] m -X、[(a-b-c) n ] m -X、 [a-(b-c) n ] m -X、[a-(c-b-c) n ] m -X、[a-(b-c-b) n ] m -X b-(a-c) n 、b-(c-a) n 、 b-(c-a-c) n 、b-(a-c-a) n 、 c-b-(a-c) n 、c-b-(c-a) n 、 c-b-(a-c) n -a、[(c-a-b) n ] m -X、 [c-(a-b) n ] m -X、[(c-a) n -b] m -X、 [(c-a-c) n -b] m -X、 [(b-c-b) n -b] m -X、[(b-a-c) n ] m -X、 [b-(a-c) n ] m -X、[b-(c-a-c) n ] m -X、[b-(a-c-a) n ] m -X

[0053] In each of the above general formulas, a represents polymer block (A), b represents polymer block (B), and c represents polymer block (C). n is an integer greater than or equal to 1, preferably an integer between 1 and 5. m is an integer greater than or equal to 2, preferably an integer between 2 and 11. X represents a residue of a coupling agent or a residue of a polyfunctional initiator. Hydrogenated conjugated diene block copolymers are preferably polymers whose basic structure is represented in particular by the structural formulas ab, aba, and abab.

[0054] The weight-average molecular weight (Mw) (hereinafter also referred to as "Mw") of the hydrogenated conjugated diene block copolymer used as an adhesive component is preferably 35,000 to 600,000, more preferably 40,000 to 400,000, and even more preferably 45,000 to 300,000, from the viewpoint of mechanical strength, impact resistance, abrasion resistance, compatibility, and moldability of the laminate of this embodiment. The weight-average molecular weight (Mw) of hydrogenated conjugated diene block copolymers is determined based on the molecular weight of the peaks in the chromatogram obtained by gel permeation chromatography (GPC), using a calibration curve (created using the peak molecular weight of standard polystyrene) derived from measurements of commercially available standard polystyrene. The molecular weight distribution of hydrogenated conjugated diene block copolymers before modification can also be determined by GPC measurements, and the molecular weight distribution is the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn). The molecular weight distribution of a single peak measured by GPC of a hydrogenated conjugated diene block copolymer is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.5 or less. The weight-average molecular weight and molecular weight distribution of hydrogenated conjugated diene block copolymers can be controlled within the above numerical range by adjusting polymerization conditions such as the amount of monomer added, the timing of addition, the polymerization temperature, and the polymerization time.

[0055] [Method for producing hydrogenated conjugated diene block copolymers] The hydrogenated conjugated diene block copolymer used as the adhesive component of the laminate in this embodiment is not limited to the following, but can be produced, for example, by polymerizing a conjugated diene compound and a vinyl aromatic compound in an organic solvent using an organoalkali metal compound as a polymerization initiator to obtain a block copolymer, followed by a hydrogenation reaction and, if necessary, a modification reaction. The hydrogenation and denaturation reactions may occur in either order or reverse order.

[0056] The polymerization method may be batch polymerization, continuous polymerization, or a combination of both. The polymerization temperature is generally 0 to 180°C, preferably 20 to 160°C, and more preferably 30 to 150°C. The polymerization time varies depending on the target conjugated diene block copolymer, but is usually within 48 hours, with 0.1 to 10 hours being preferred. From the viewpoint of obtaining a conjugated diene polymer with a narrow molecular weight distribution and high strength, 0.5 to 5 hours is more preferable. The atmosphere of the polymerization system is not particularly limited, as long as it is within a pressure range sufficient to maintain nitrogen and solvent in the liquid phase. It is preferable that the polymerization system does not contain impurities that inactivate the polymerization initiator and the living polymer, such as water, oxygen, or carbon dioxide.

[0057] Examples of organic solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane; alicyclic hydrocarbons such as cyclohexane, cycloheptane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, xylene, toluene, and ethylbenzene.

[0058] As the organoalkali metal compound used as a polymerization initiator, organolithium compounds are preferred. Examples of organolithium compounds include organomonolithium compounds, organodilithium compounds, and organopolithium compounds. Examples of organolithium compounds include, but are not limited to, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, hexamethylenedisitium, butadienyllithium, isopropenyldilinium, and lithium piperidide. When an organolithium compound containing nitrogen, such as lithium piperidide, is used as a polymerization initiator, an amino group-modified conjugated diene block copolymer is obtained in which the NHx atom group has X=0. These polymerization initiators may be used individually or in combination of two or more. Among these, n-butyllithium, sec-butyllithium, and lithium piperidide are preferred from the viewpoint of polymerization activity. The amount of organoalkali metal compound used as a polymerization initiator depends on the molecular weight of the target conjugated diene block copolymer, but is generally preferably in the range of 0.01 to 1.5 pF (parts by mass per 100 parts by mass of monomer), more preferably in the range of 0.02 to 0.3 pF, and even more preferably in the range of 0.05 to 0.2 pF.

[0059] The amount of vinyl bonds in a conjugated diene block copolymer can be controlled by using a Lewis base, such as an ether or amine, as a vinyl bond modifier (hereinafter referred to as a vinylizing agent). Furthermore, the amount of vinylizing agent used can be adjusted according to the desired amount of vinyl bonding. Examples of vinylizing agents include, but are not limited to, ether compounds and tertiary amine compounds. Examples of ether compounds include linear ether compounds and cyclic ether compounds. Examples of linear ether compounds include, but are not limited to, dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, and other ethylene glycol dialkyl ether compounds, as well as diethylene glycol dialkyl ether compounds, such as diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and other diethylene glycol dialkyl ether compounds. Furthermore, examples of cyclic ether compounds include, but are not limited to, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis(2-oxolanyl)propane, and alkyl ethers of furfuryl alcohol. Examples of tertiary amine compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N,N,N',N”,N”-pentamethylethylenetriamine, N,N'-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, and bis[2-(N,N-dimethylamino)ethyl]ether. These may be used individually or in combination of two or more types. As tertiary amine compounds, compounds having two amine groups are preferred. Furthermore, among these, those having a structure that exhibits intramolecular symmetry are more preferred, and N,N,N',N'-tetramethylethylenediamine, bis[2-(N,N-dimethylamino)ethyl] ether, and 1,2-dipiperidinoethane are even more preferred.

[0060] In the manufacturing process of conjugated diene block copolymers, polymerization can be carried out using a conjugated diene compound and a vinyl aromatic compound in the presence of the aforementioned vinylizing agent, organolithium compound, and alkali metal alkoxide. Here, alkali metal alkoxides are compounds represented by the general formula MOR (where M is an alkali metal and R is an alkyl group). By coexisting with alkali metal alkoxides in the polymerization process, it is possible to control the amount of vinyl bonds, molecular weight distribution, polymerization rate, and blocking rate. From the viewpoint of high vinyl bond content, narrow molecular weight distribution, high polymerization rate, and high blocking ratio, sodium or potassium is preferred as the alkali metal in alkali metal alkoxides. Examples of alkali metal alkoxides include, but are not limited to, sodium alkoxides, lithium alkoxides, and potassium alkoxides having an alkyl group with 2 to 12 carbon atoms. Preferably, sodium alkoxides or potassium alkoxides having an alkyl group with 3 to 6 carbon atoms are preferred, and more preferably, sodium t-butoxide, sodium t-pentoxide, potassium t-butoxide, and potassium t-pentoxide. Among these, sodium alkoxides, specifically sodium-t-butoxide and sodium-t-pentoxide, are even more preferred.

[0061] The method for hydrogenating the unsaturated bonds derived from the conjugated diene monomer units in a conjugated diene block copolymer is not particularly limited. For example, by supplying hydrogen to the conjugated diene block copolymer obtained in the polymerization step in the presence of a hydrogenation catalyst and performing hydrogenation, a hydrogenated conjugated diene block copolymer can be obtained in which the double bond residues of the conjugated diene monomer units are hydrogenated. The hydrogenation rate can be controlled, for example, by adjusting the amount of catalyst used during hydrogenation, and the hydrogenation rate can be controlled, for example, by adjusting the amount of catalyst, hydrogen feed rate, pressure, and temperature during hydrogenation. The hydrogenation reaction step is preferably carried out after the block copolymer formation reaction has stopped.

[0062] When a hydrogenated conjugated diene block copolymer has a polar group, that is, when condition (i) above is satisfied, it is preferable that at least one polar group selected from the group consisting of acid anhydride groups, amino groups, dicarboxyl groups, carboxyl groups, epoxy groups, and oxetanyl groups is bonded to it. The method for introducing the polar group into the conjugated diene block copolymer is not particularly limited and includes methods such as introducing it using a polymerization initiator having predetermined functional groups that constitute the polar group, polymerizing unsaturated monomers having each functional group, and adding a modifying agent that forms or contains a functional group at the living terminus. The aforementioned "denaturing agent" is not limited to the following, but examples include aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbaryl acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid, and aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid. Other examples include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and ε-caprolactam.

[0063] Other methods for introducing polar groups into conjugated diene block copolymers include, for example, reacting a conjugated diene block copolymer with an organoalkali metal compound such as an organolithium compound (metallation reaction), and then adding a functional modifier to the polymer to which the organoalkali metal has been added.

[0064] Another method for introducing polar groups is, for example, a manufacturing method in which a functional group is directly grafted onto an unmodified conjugated diene block copolymer. Methods for graft addition include reacting a radical initiator with a conjugated diene block copolymer and the modifier in a solution containing these; reacting a radical initiator with a conjugated diene block copolymer and the modifier under heating and melting conditions; or reacting a compound containing a conjugated diene block copolymer and the modifier under heating and melting conditions without a radical initiator. Methods for reacting the components include melting and kneading each component using common mixers such as Banbury mixers, single-screw extruders, twin-screw extruders, conneaders, and multi-screw extruders. Preferably, from the viewpoint of cost and production stability, a method using a single-screw, twin-screw, or multi-screw extruder is preferred, and more preferably, a method using a twin-screw extruder is preferred. During the reaction process, the ingredients may be dry-blended and added all at once, or each ingredient may be fed separately, or the same ingredient may be added in stages. The rotational speed of the screw is preferably 50 to 400 rpm, more preferably 100 to 350 rpm, from the viewpoint of uniformly applying the modifying agent, and preferably 150 to 300 rpm from the viewpoint of preventing resin degradation due to shear and ensuring uniform application. The mixing temperature is preferably 100°C to 350°C, from the viewpoint of being the temperature at which the conjugated diene block copolymer melts and the temperature at which radicals are generated from the radical initiator. More preferably, the temperature is 120°C to 300°C, and even more preferably 150°C to 250°C, from the viewpoint of controlling the amount of addition and suppressing resin degradation due to heat. To suppress the deactivation of radical-active species by oxygen, it is preferable to perform melt kneading under an inert gas such as nitrogen.

[0065] Examples of radical initiators, though not limited to the following, include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. Preferably, they have a half-life temperature of 1 minute in the kneading temperature range, and more preferably, a half-life temperature of 1 minute in the range of 150°C to 250°C. Such radical initiators are not limited to the following, but include, for example, 1,1-di(t-hexylperoxy)cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(4,4-di-(t-butylperoxy)cyclohexyl)propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylauric acid, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, and 2,5-dimethyl-2,5-di(benzoylperoxy) Examples include xane, t-butyl peroxyacetate, 2,2-di-(t-butylperoxy)butane, t-butyl peroxybenzoate, n-butyl-4,4-di-(t-butylperoxy)valerate, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-methane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexine, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. In particular, from the viewpoint of compatibility with conjugated diene block copolymers, di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3 are preferred. In particular, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexine are more preferred.

[0066] Furthermore, other methods for introducing polar groups into conjugated diene block copolymers include secondary modification, which involves reacting the primary modified conjugated diene block copolymer obtained by the aforementioned method with an atomic group having a functional group. Examples of polar group combinations include amino group and dicarboxyl group, acid anhydride group and amino group, hydroxyl group; isocyanate group and hydroxyl group, carboxyl group and amino group, acid anhydride group and hydroxyl group, silanol group and hydroxyl group, and epoxy group and carboxyl group. However, from the viewpoint of reactivity, the combinations of amino group and dicarboxyl group, acid anhydride group and amino group, silanol group and hydroxyl group, dicarboxyl group and amino group, and epoxy group and carboxyl group are preferred, and even more preferred are the combinations of amino group and dicarboxyl group, and acid anhydride group and amino group.

[0067] As a primary modification, the aforementioned method can be used to bond epoxy groups, acid anhydride groups, and hydroxyl groups to the conjugated diene block copolymer, and as a modifying agent, the aforementioned modifying agent, epoxy group-containing polymerizable compounds, etc. As a primary modification, the aforementioned method can be used to bond silanol groups to conjugated diene block copolymers. Examples of modifying agents include bis-(3-triethoxysilylpropyl)-tetrasulfan, bis-(3-triethoxysilylpropyl)-disulfan, ethoxysiloxane oligomers, epoxy group-containing polymerizable compounds, and hydrolysates of compounds having alkoxysilane groups as mentioned above in relation to epoxy group-containing polymerizable compounds. As a primary modification, the method of attaching amino groups to the conjugated diene block copolymer is as described above, and as a modification agent, for example, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone, 1-methyl-3-ethyl-2-imidazolidinone, 1-methyl-3-propyl Examples include pyr-2-imidazolidinone, 1-methyl-3-butyl-2-imidazolidinone, 1-methyl-3-(2-methoxyethyl)-2-imidazolidinone, 1-methyl-3-(2-ethoxyethyl)-2-imidazolidinone, 1,3-di-(2-ethoxyethyl)-2-imidazolidinone, 1,3-dimethylethylenethiourea, N,N'-diethylpropyleneurea, and N-methyl-N'-ethylpropyleneurea. Examples of denaturing agents include 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, 1-ethyl-2-pyrrolidone, 1-propyl-2-pyrrolidone, 1-butyl-2-pyrrolidone, 1-isopropyl-2-pyrrolidone, 1,5-dimethyl-2-pyrrolidone, 1-methoxymethyl-2-pyrrolidone, 1-methyl-2-piperidone, 1,4-dimethyl-2-piperidone, 1-ethyl-2-piperidone, 1-isopropyl-2-piperidone, and 1-isopropyl-5,5-dimethyl-2-piperidone.

[0068] The above-mentioned method can be used to bond a primary modified conjugated diene polymer to which an amino group has been bonded with a secondary modifying agent. Examples of modifying agents include aliphatic carboxylic acids such as maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carbaryl acid, cyclohexanedicarboxylic acid, and cyclopentanedicarboxylic acid, and aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and pyromellitic acid. Other examples include maleic anhydride, itaconic anhydride, pyromellitic anhydride, cis-4-cyclohexane-1,2-dicarboxylic acid anhydride, 1,2,4,5-benzenetetracarboxylic acid dianhydride, and 5-(2,5-dioxytetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride. There are no particular restrictions on the shape of the resulting conjugated diene block copolymer containing polar groups, but examples include pellets, sheets, strands, and chips. Alternatively, it can be directly molded after melt kneading.

[0069] [Method for manufacturing laminates] The laminate of this embodiment is a laminate consisting of two or three or more layers, each containing the above-described layers and components, and can be manufactured using a wide range of known methods. The method for manufacturing the laminate is not limited, and various conventionally known methods can be employed. Since the laminate of this embodiment has good adhesion, a laminate with good adhesion can be obtained by the following molding method without performing dry lamination using organic solvents or the like. Examples of molding methods include co-extrusion, in which individual molten resins melted in an extruder are supplied to a multi-layer die and layered within the die to form inflation films, T-die films, sheets, pipes, etc., and co-injection molding, in which individual molten resins are injected into the same mold with a time lag. Furthermore, extrusion lamination molding can also be employed, in which a resin film constituting one of the layers is pre-formed, and the other layers are melt-extruded onto it. Furthermore, the resin films that make up each layer can be molded in advance, and then heat can be applied to fuse these layers together to create a laminate.

[0070] After obtaining a laminate using the molding method described above, it can also be stretched to produce a stretched laminate. The stretched laminate may or may not be heat-set. If heat-set is not performed, the stretched laminate will shrink when heated afterward, releasing the stress, and can therefore be used as a shrink film. Furthermore, these can be subjected to secondary processing such as vacuum forming or pressure forming to form deep-drawn containers and the like.

[0071] Furthermore, if the laminate has an adhesive layer (III), the adhesive layer (layer (III)) may be applied to both sides of the adherends (layer (I) and layer (II)) beforehand, and then the adherends may be laminated and bonded. To ensure strong adhesion, the laminate may be pressurized, and the pressurization may be applied to the entire laminate or only to the portion with the adhesive layer. The pressurization method is not particularly limited, and the pressure is also not particularly limited, as long as it is not so high that the adhesive layer deforms significantly.

[0072] The shape of the laminate is not limited and may be any shape, such as a flat surface like a film, sheet, or plate, or a pipe, bag, or irregular shape.

[0073] The laminate of this embodiment may have layers other than the acrylic resin-based layer (I), the polyolefin resin-based layer (II), the adhesive layer (III), and the layer containing polyolefin resin and adhesive components (IV) (hereinafter sometimes referred to as "other layers"). The materials that make up the other layers are not limited and may be not only resin layers but also metal layers. The materials of the other resin layers constituting the laminate are not limited, and examples include polyolefin resins (excluding those included in layer (II)); polyphenylene ether resins; polyamide resins such as nylon 6, nylon 66, and nylon 11; polyester resins such as polyethylene terephthalate and polybutylene terephthalate (excluding those included in component (A)); (meth)acrylic resins such as polymethyl methacrylate resins; styrene resins such as polystyrene; and various thermoplastic elastomers.

[0074] Furthermore, various additives can be incorporated into each layer of the laminate, as long as they do not interfere with the effects of the present invention. Examples of additives include various heat stabilizers, antioxidants, UV absorbers, light stabilizers, anti-aging agents, nucleating agents, plasticizers, impact modifiers, compatibilizers, defoamers, thickeners, crosslinking agents, surfactants, lubricants, mold release agents, anti-blocking agents, processing aids, antistatic agents, flame retardants, flame retardant aids, fillers, colorants, etc. These additives may be used individually or in any combination and ratio of two or more types. Examples of heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, and alkali metal halides. Flame retardants are broadly classified into halogen-based and non-halogen-based flame retardants, with non-halogen-based flame retardants being preferable from an environmental perspective. Examples of non-halogen-based flame retardants include phosphorus-based flame retardants, hydrated metal compound (aluminum hydroxide, magnesium hydroxide) flame retardants, nitrogen-containing compound (melamine-based, guanidine-based) flame retardants, and inorganic compound (borate, molybdenum compound) flame retardants. Fillers are broadly classified into organic and inorganic fillers. Organic fillers include naturally derived polymers such as starch, cellulose microparticles, wood flour, soybean pulp, rice husks, and wheat bran, as well as modified versions thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminosilicate, magnesium silicate, glass balloons, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, and carbon fiber.

[0075] Furthermore, if the laminate of this embodiment has a layer (IV) containing an adhesive component and a polyolefin resin, the resin composition containing the polyolefin resin and the adhesive component can be obtained by mixing the above-mentioned components in predetermined proportions. There are no particular restrictions on the mixing method as long as the raw material components are uniformly dispersed. That is, by mixing the above-mentioned raw material components simultaneously or in any order, a resin composition in which each component is uniformly dispersed can be obtained. For more uniform mixing and dispersion, it is preferable to melt-mix a predetermined amount of the above-mentioned raw material components. For example, the raw material components of the resin composition may be mixed in any order and then heated, or all the raw material components may be mixed while melting them sequentially, or the raw materials may be appropriately blended (dry-blended) and melt-mixed during molding when manufacturing the target molded article. The mixing method and conditions are not particularly limited as long as each raw material component is uniformly mixed. However, from the viewpoint of productivity, it is preferable to mix the raw materials using a tumbler blender, V-blender, ribbon blender, Henschel mixer, etc., and then melt-knead the mixture using a continuous kneader such as a single-screw extruder or twin-screw extruder, or a batch-type kneader such as a mill roll, Banbury mixer, or pressure kneader. The manufacturing conditions when producing resin compositions using these methods are not limited and can be set as appropriate using well-known conditions. The temperature during melt-mixing should be such that at least one of the raw material components is in a melted state. However, a temperature at which all components used are melted is usually selected, and this can generally be done at 150-250°C.

[0076] (Preferred form of method for manufacturing laminates) In this embodiment, the following method is particularly preferred for manufacturing the laminate. In other words, a method for producing a laminate having a layer (I) mainly composed of an acrylic resin, a layer (II) mainly composed of a polyolefin resin, and an adhesive layer (III) provided between layer (I) and layer (II) is preferably a production method that includes the steps of laminating layer (I) and layer (III) so that they are in contact to obtain a laminate of at least two layers, and laminating layer (II) so that layer (III) of the at least two-layer laminate is in contact with layer (II). This manufacturing method is suitable when layer (I) is a thin layer with a thickness of 1.5 mm or less.

[0077] Furthermore, from the viewpoint of obtaining a laminate with excellent appearance, heat cycle resistance and / or hot water resistance, it is preferable that in the process of laminating layer (I) and layer (III), layer (I) and layer (III) are laminated in a molten state and then cooled. The molding method is not particularly limited, but one example is a molding method in which individual molten resins melted in an extruder are supplied to a multilayer die and laminated within the die to form an inflation film, T-die film, etc.

[0078] Furthermore, from the standpoint of productivity, in the step of obtaining a laminate of at least two layers in which layer (I) and layer (III) of the laminate are in contact, and further laminating layer (II) onto the laminate, the step of mounting the at least two laminates onto a mold, pouring the polyolefin resin constituting layer (II) into the mold in a molten state, and laminating it by cooling may be performed to obtain the laminate of the desired embodiment. [Examples]

[0079] The present invention will be described in detail below with reference to specific examples and comparative examples, but the present invention is not limited in any way by the following examples and comparative examples.

[0080] The structure of the hydrogenated conjugated diene block copolymer used as the adhesive component in the examples and comparative examples, the method for measuring its physical properties, and the method for evaluating the laminate are shown below.

[0081] [Evaluation of the structure, physical properties, and laminates of hydrogenated conjugated diene block copolymers] The structure and properties of hydrogenated conjugated diene polymers are measured below. ((1) Amount of vinyl bond in hydrogenated conjugated diene block copolymer) The amount of vinyl bond relative to 100 ml of the total conjugated diene monomer units in a hydrogenated conjugated diene block copolymer is determined using a hydrogenated conjugated diene block copolymer in a proton nuclear magnetic resonance ( 1 Measured by 1H-NMR. The measurement instrument used was an ECS400 (manufactured by JEOL), the solvent was deuterated chloroform, the sample concentration was 50 mg / mL, the observation frequency was 400 MHz, tetramethylsilane was used as the chemical shift reference, the pulse delay was 2.904 seconds, the number of scans was 64, the pulse width was 45°, and the measurement temperature was 26°C. The amount of vinyl bonds was calculated by first determining the integral value per H for each bond type from the integral values ​​of the signals attributed to 1,4-bonds and 1,2-bonds, and then calculating the ratio of 1,4-bonds to 1,2-bonds.

[0082] ((2) Hydrogenation rate of unsaturated bonds in conjugated diene monomer units of hydrogenated conjugated diene block copolymers) The hydrogenation rate of hydrogenated conjugated diene copolymers is determined using hydrogenated conjugated diene copolymers in proton nuclear magnetic resonance ( 1 Measured by 1H-NMR. The measurement conditions and the method for processing the measurement data were the same as in (1) above. The hydrogenation rate was determined by calculating the integral value of the signals originating from the remaining double bonds at 4.5–5.5 ppm and the signals originating from the hydrogenated conjugated diene, and then calculating the ratio between the two.

[0083] ((3) Content of vinyl aromatic monomer units in hydrogenated conjugated diene block copolymer (hereinafter also referred to as "styrene content")) The content of vinyl aromatic monomer units is determined using hydrogenated conjugated diene block copolymers and proton nuclear magnetic resonance ( 1 The measurement was performed using the 1H-NMR method. The measurement was performed using an ECS400 (manufactured by JEOL), with deuterated chloroform as the solvent, a sample concentration of 50 mg / mL, an observation frequency of 400 MHz, tetramethylsilane as the chemical shift reference, a pulse delay of 2.904 seconds, 64 scans, a pulse width of 45°, and a measurement temperature of 26°C. The styrene content was calculated using the integrated total styrene aromatic signal in the spectrum at 6.2–7.5 ppm. Furthermore, the styrene content was also confirmed by calculating the content of vinyl aromatic monomer units for each polymer sampled at each step of the polymerization process of the conjugated diene block copolymer before hydrogenation.

[0084] (4) Weight-average molecular weight of hydrogenated conjugated diene block copolymers The weight-average molecular weight of hydrogenated conjugated diene block copolymers was measured using GPC [instrument: HLC8220 (Tosoh Corporation), column: TSKgelSUPER-HZM-N (4.6 mm × 30 cm)]. The procedure was carried out using tetrahydrofuran as the solvent. The weight-average molecular weight was determined from the molecular weight of the peaks in the chromatogram, using a calibration curve (created using the peak molecular weight of standard polystyrene) derived from measurements of commercially available standard polystyrene. In cases where there are multiple peaks in the chromatogram, the weight-average molecular weight was determined from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram).

[0085] ((5) Modification rate of amino group-modified hydrogenated conjugated diene block copolymers) Applying the property that modified components are adsorbed onto a GPC column packed with silica gel, the ratio of hydrogenated conjugated diene block copolymer to standard polystyrene in the chromatogram measured in (5) above was compared with the ratio of hydrogenated conjugated diene block copolymer to standard polystyrene in the chromatogram measured using a silica column GPC [instrument: LC-10 (Shimadzu Corporation), column: Zorbax (DuPont)]. The amount adsorbed onto the silica column was measured from the difference between these ratios, and this ratio was defined as the modification rate. The denaturation rate was calculated as the percentage (%) of molecules whose terminal end is an amino group of a specific structure, using the following formula.

[0086]

number

[0087] a: Area of ​​total polymer measured using polystyrene gel (PLgel) (%) b: Area (%) of low molecular weight internal standard PS measured on polystyrene gel (PLgel) c: Total polymer area (%) measured using a silica-based column (Zorbax) d: Area (%) of low molecular weight internal standard PS measured with silica column (Zorbax)

[0088] (6) Modification rate of hydrogenated conjugated diene block copolymers modified with maleic anhydride) The maleic anhydride-modified hydrogenated conjugated diene block copolymer was dissolved in toluene and titrated with a methanol solution of sodium methoxide with a factor of 1 ± 0.05 to calculate the factor.

[0089] The evaluation of the properties of the laminate is described below. ((7) Adhesiveness (adhesive strength)) Examples 1-31 and Comparative Examples 1-12 involved leaving the laminates (described later) undisturbed for 24 hours at a temperature of 25°C and 50% humidity. Then, a 1 cm wide cut was made in the polypropylene resin-based layer (II) or the layer (IV) containing polypropylene resin and adhesive components (described later), and a peel test was performed using a tensile testing machine to remove a section of 10 cm or more. The adhesive strength (N / m) was calculated from the resulting stress. A higher adhesive strength indicates superior adhesion. Examples 32-40 and Comparative Examples 13-15 were evaluated using a grid test in accordance with JIS K 5400. After the laminates described later were left standing for 24 hours at a temperature of 25°C and a humidity of 50%, a 1 mm layer was measured on the acrylic resin-based layer (I) side, reaching the adhesive layer (III). 2 One hundred notches were made in the corners. Cellophane tape (registered trademark, Nichiban Co., Ltd., CT28) was pressed onto the notches with a finger to adhere to the acrylic resin-based layer (I), and then peeled off. A survival rate of 100% was defined as the acrylic resin-based layer (I) remaining intact in all of the 100 corners, and was evaluated according to the following criteria. ◎: Survival rate 95% or more ○: Survival rate 80% or more △: Survival rate over 50% ×: Survival rate 50% or less

[0090] (8) Impact resistance A laminate (100 mm x 100 mm) was kept at 23°C (room temperature) or -30°C for 24 hours or more. Then, 2 cm from each of the four sides of the laminate was fixed, and a steel ball with a mass of 1.04 kg was dropped onto the laminate from heights of 1.0 m and 0.5 m. The laminate was then evaluated according to the criteria shown below. ○: The steel ball does not penetrate, and no fragments scatter. △: The steel ball penetrates, but the shattered fragments do not scatter. ×: The steel ball penetrates, and the shattered fragments scatter.

[0091] (9) Vibration damping properties In accordance with JIS K 7391, the loss coefficient of the laminate at room temperature was calculated using the cantilever beam method and the half-width method. The excitation method used was steady-state excitation with a non-contact electromagnetic vibrator. The obtained loss coefficients were evaluated according to the following criteria. ○: 0.020 or higher ×: Less than 0.020

[0092] ((10) Appearance) The acrylic resin-based layer (I) of the laminate was visually observed, and its appearance was evaluated according to the following criteria. ◎: No cloudiness. ○: Slightly cloudy. △: A small amount of air bubbles are present (no cloudiness or slight cloudiness). ×: The liquid is cloudy and / or contains a large amount of bubbles.

[0093] ((11) Mold contamination) In the process of fabricating the laminate described later, the molds were visually observed during 20 consecutive fabrication cycles, and their appearance was evaluated according to the following criteria. ○: No mold contamination. △: There is slight mold contamination. ×: There is mold contamination.

[0094] ((12) Heat cycle resistance) The laminate described later was subjected to a heat cycle test consisting of 100 cycles, with each cycle being -40°C / 15 minutes and 80°C / 15 minutes, and then returned to room temperature. Thereafter, the adhesion (adhesion strength) was evaluated using a grid test in accordance with JIS K 5400, following the same procedure as in (7) above. The remaining rate obtained in (7) above and the remaining rate obtained in the grid test after the heat cycle test were compared, and the rate of decrease in adhesion strength after the heat cycle test was evaluated according to the following criteria. ◎: 5% or less ○: 15% or less △: Less than 30% ×: 30% or more

[0095] ((13) Hot water resistance) The laminated material, described later, was immersed in 40°C hot water for 24 hours, after which it was removed and the moisture was wiped off. Subsequently, the adhesion (adhesive strength) was evaluated using a grid test in accordance with JIS K 5400, following the same procedure as in (7) above. The rate of remaining material obtained in (7) above was compared with the rate of remaining material obtained in the grid test after hot water immersion, and the rate of decrease in adhesive strength after hot water immersion was evaluated according to the following criteria. ◎: 5% or less ○: 15% or less △: Less than 30% ×: 30% or more

[0096] ((14) Retractability) In the two-layer films described later in Examples 32-40 and Comparative Examples 13-35, which consist of a layer (I) mainly composed of acrylic resin and a layer (III) mainly composed of polyolefin resin, co-extrusion molding was performed using a multilayer T-die extruder described later, and after winding, the unwinding properties were evaluated according to the following criteria. ○: Retractable ×: Cannot be extended

[0097] [Hydrogenated conjugated diene block copolymer] (Denaturant) The following compounds were used as modifying agents for the production of hydrogenated conjugated diene block copolymers. Maleic anhydride (manufactured by Fuso Chemical Industries Co., Ltd.) 1,3-Dimethyl-2-imidazolidinone (all manufactured by Tokyo Chemical Industry Co., Ltd.)

[0098] (Preparation of hydrogenated catalyst) A hydrogenation catalyst for the hydrogenation reaction of hydrogenated conjugated diene copolymers was prepared by the following method. In a nitrogen-purged reaction vessel, 1 L of dried and purified cyclohexane was added, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and while stirring thoroughly, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the reaction was carried out at room temperature for about 3 days to obtain a hydrogenated catalyst.

[0099] (Production of hydrogenated conjugated diene block copolymers) A hydrogenated conjugated diene block copolymer was prepared using a vinyl aromatic compound and a conjugated diene as described below. The physical properties are shown in Tables 1 to 3. In Tables 1 to 3, under "Structure," A represents a polymer block (A) mainly composed of vinyl aromatic monomer units, B represents a polymer block (B) mainly composed of conjugated diene monomer units, and C represents a polymer block (C) having both vinyl aromatic monomer units and conjugated diene monomer units.

[0100] <Preparation of hydrogenated conjugated diene block copolymer (1)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added. Next, 0.14 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 0.25 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 70°C for 30 minutes. Next, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added, and polymerization was carried out at 70°C for 15 minutes. Subsequently, methanol was added to stop the polymerization reaction and obtain a conjugated diene copolymer. Next, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene copolymer at a concentration of 70 ppm (based on Ti) per 100 parts by mass of the conjugated diene copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (1). The hydrogenated conjugated diene block copolymer (1) obtained as described above has a styrene content of 30% by mass and a weight-average molecular weight of 7.1 × 10⁻⁶ 4 The vinyl bond content was 35%, and the hydrogenation rate was 98%. The hydrogenated conjugated diene block copolymer (1) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (1)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (1)-M was titrated under the conditions described above. The denaturation rate was 1.1% by mass.

[0101] <Hydrogenated conjugated diene block copolymer (2)> The procedure was the same as for hydrogenated conjugated diene block copolymer (1), except that 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added at a rate of 1.1 moles per mole of n-butyllithium before adding methanol, the reaction was carried out at 70°C for 15 minutes, and methanol was added after the reaction was complete. The terminal amine-modified hydrogenated conjugated diene block copolymer (2) obtained as described above has a styrene content of 30% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶4 The vinyl bond content was 35%, the modification rate was 80% (0.80 modification groups per polymerization chain), and the hydrogenation rate was 74%.

[0102] <Preparation of hydrogenated conjugated diene block copolymer (3)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene was added. Next, 0.041 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 0.16 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 45 parts by mass of styrene and 35 parts by mass of butadiene was added and polymerized at 70°C for 45 minutes. Next, 0.5 moles of ethyl benzoate were added to 1 mole of n-butyllithium, and the reaction was carried out at 70°C for 10 minutes. Methanol was then added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (3). The hydrogenated conjugated diene block copolymer (3) obtained as described above has a styrene content of 65% by mass and a weight-average molecular weight of 19.0 × 10⁻⁶. 4 The vinyl bond content was 25%, and the hydrogenation rate was 98%. The hydrogenated conjugated diene-based block copolymer (3) obtained as described above was mixed with maleic anhydride and a peroxide (Perhexa 25B, manufactured by NOF Corporation), and then supplied to a twin-screw extruder with the temperature set at 150 to 210 °C throughout the entire length of the extruder and compounded to obtain a maleic anhydride-modified hydrogenated conjugated diene-based block copolymer (3)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene-based block copolymer (3)-M was titrated under the aforementioned conditions. The modification rate was 0.5% by mass.

[0103] <Preparation of Hydrogenated Conjugated Diene-based Block Copolymer (4)> Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 6.0 parts by mass of styrene was charged. Next, 0.073 parts by mass of n-butyllithium was added per 100 parts by mass of all monomers, and 0.5 mol of tetramethylethylenediamine (TMEDA) was added per 1 mol of n-butyllithium, and polymerization was carried out at 70 °C for 15 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 8.0 parts by mass of styrene and 80 parts by mass of butadiene was added, and polymerization was carried out at 70 °C for 45 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 6.0 parts by mass of styrene was added, and polymerization was carried out at 70 °C for 15 minutes. Then, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene-based block copolymer obtained as described above at 70 ppm on a Ti basis per 100 parts by mass of the conjugated diene-based block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of eighty °C for about 1.5 hours. Next, 0.25 parts by mass of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer per 100 parts by mass of the hydrogenated conjugated diene-based block copolymer to obtain a hydrogenated conjugated diene-based block copolymer (4). The hydrogenated conjugated diene block copolymer (4) obtained as described above has a styrene content of 20% by mass and a weight-average molecular weight of 14.0 × 10⁻⁶. 4 The vinyl bond content was 45%, and the hydrogenation rate was 98%. The hydrogenated conjugated diene block copolymer (4) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (4)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (4)-M was titrated under the conditions described above. The denaturation rate was 0.8% by mass.

[0104] <Preparation of hydrogenated conjugated diene block copolymer (5)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added. Next, 0.062 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 1.5 moles of tetramethylethylenediamine (TMEDA) was added per mole of n-butyllithium, and polymerization was carried out at 60°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 5 parts by mass of styrene and 80 parts by mass of butadiene was added and polymerized at 60°C for 45 minutes. Next, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added, and polymerization was carried out at 60°C for 15 minutes. Afterward, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (5). The hydrogenated conjugated diene block copolymer (5) obtained as described above has a styrene content of 20% by mass and a weight-average molecular weight of 15.0 × 10⁻⁶. 4 The vinyl bond content was 71%, and the hydrogenation rate was 98%.

[0105] <Preparation of hydrogenated conjugated diene block copolymer (6)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added. Next, 0.062 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 1.5 moles of tetramethylethylenediamine (TMEDA) was added per mole of n-butyllithium, and polymerization was carried out at 60°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene and 65 parts by mass of butadiene was added and polymerized at 60°C for 45 minutes. Next, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added, and polymerization was carried out at 60°C for 15 minutes. Afterward, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (6). The hydrogenated conjugated diene block copolymer (6) obtained as described above has a styrene content of 35% by mass and a weight-average molecular weight of 15.0 × 10⁻⁶. 4 The vinyl bond content was 70%, and the hydrogenation rate was 98%.

[0106] <Preparation of hydrogenated conjugated diene block copolymer (7)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 22.5 parts by mass of styrene was added. Next, 0.079 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 1.5 moles of tetramethylethylenediamine (TMEDA) was added per mole of n-butyllithium, and polymerization was carried out at 60°C for 20 minutes. Next, a cyclohexane solution (20% by mass) containing 55 parts by mass of butadiene was added and polymerization was carried out at 60°C for 35 minutes. Next, a cyclohexane solution (20% by mass) containing 22.5 parts by mass of styrene was added, and polymerization was carried out at 60°C for 20 minutes. Afterward, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (7). The hydrogenated conjugated diene block copolymer (7) obtained as described above has a styrene content of 45% by mass and a weight-average molecular weight of 11.0 × 10⁻⁶. 4 The vinyl bond content was 71%, and the hydrogenation rate was 98%.

[0107] <Preparation of hydrogenated conjugated diene block copolymer (8)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added. Next, 0.066 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 1.5 moles of tetramethylethylenediamine (TMEDA) was added per mole of n-butyllithium, and polymerization was carried out at 60°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 85 parts by mass of butadiene was added and polymerization was carried out at 60°C for 60 minutes. Next, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added, and polymerization was carried out at 60°C for 15 minutes. Afterward, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (8). The hydrogenated conjugated diene block copolymer (8) obtained as described above has a styrene content of 15% by mass and a weight-average molecular weight of 16.0 × 10⁻⁶. 4 The vinyl bond content was 70%, and the hydrogenation rate was 98%. After mixing the hydrogenated conjugated diene block copolymer (8) obtained as described above with maleic anhydride, the mixture was supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (8)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (8)-M was titrated under the conditions described above. The denaturation rate was 0.8% by mass.

[0108] <Preparation of Hydrogenated Conjugated Dienic Block Copolymer (9)> Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirring device and a jacket. First, a cyclohexane solution (concentration 20% by mass) containing 15 parts by mass of styrene was charged. Next, 0.066 parts by mass of n-butyllithium was added per 100 parts by mass of all monomers, and 1.5 mol of tetramethylethylenediamine (TMEDA) was added per 1 mol of n-butyllithium, and polymerization was carried out at 60 °C for 20 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 70 parts by mass of butadiene was added, and polymerization was carried out at 60 °C for 50 minutes. Next, a cyclohexane solution (concentration 20% by mass) containing 7.5 parts by mass of styrene was added, and polymerization was carried out at 60 °C for 20 minutes. Then, methanol was added to stop the polymerization reaction. Next, to the conjugated diene block copolymer obtained as described above, the hydrogenation catalyst prepared as described above was added at 70 ppm on a Ti basis per 100 parts by mass of the conjugated diene block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 80 °C for about 1.5 hours. Next, as a stabilizer, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added at 0.25 parts by mass per 100 parts by mass of the hydrogenated conjugated diene block copolymer. The hydrogenated conjugated diene block copolymer obtained as described above had a styrene content of 30% by mass, a weight average molecular weight of 16.1×10 4 , a vinyl bond content of 70%, and a hydrogenation rate of 98%. After mixing the hydrogenated conjugated diene block copolymer obtained as described above and maleic anhydride, it was supplied to a twin-screw extruder with the temperature setting throughout the length of the extruder being 150 - 210 °C and compounded to obtain a maleic anhydride-modified hydrogenated conjugated diene block copolymer (9)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (9)-M was titrated under the aforementioned conditions, and the modification rate was 0.7% by mass.

[0109] <Preparation of hydrogenated conjugated diene block copolymer (10)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added. Next, 0.15 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 0.27 moles of tetramethylethylenediamine (TMEDA) was added per mole of n-butyllithium, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 85 parts by mass of butadiene was added and polymerization was carried out at 60°C for 50 minutes. Next, a cyclohexane solution (20% by mass) containing 7.5 parts by mass of styrene was added, and polymerization was carried out at 70°C for 15 minutes. Afterward, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain the hydrogenated conjugated diene block copolymer (10). The hydrogenated conjugated diene block copolymer (10) obtained as described above has a styrene content of 15% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶. 4 The vinyl bond content was 35%, and the hydrogenation rate was 98%. The hydrogenated conjugated diene block copolymer (10) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (10)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (10)-M was titrated under the conditions described above. The denaturation rate was 1.2% by mass.

[0110] <Preparation of hydrogenated conjugated diene block copolymer (11)> The procedure was the same as for hydrogenated conjugated diene block copolymer (10), except that 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added at a rate of 1.1 moles per mole of n-butyllithium before adding methanol, the reaction was carried out at 70°C for 15 minutes, and methanol was added after the reaction was complete. The terminal amine-modified conjugated diene block copolymer (11) obtained as described above has a styrene content of 15% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶ 4 The vinyl bond content was 35%, the modification rate was 80% by mass (0.80 modification groups per polymerization chain), and the hydrogenation rate was 75%.

[0111] <Preparation of hydrogenated conjugated diene block copolymer (12)> The procedure was the same as for hydrogenated conjugated diene block copolymer (3), except that 0.90 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium. The resulting hydrogenated conjugated diene block copolymer (12) had a styrene content of 65% by mass and a weight-average molecular weight of 19.1 × 10⁻⁶. 4 The vinyl bond content was 54%, and the hydrogenation rate was 98%.

[0112] <Preparation of hydrogenated conjugated diene block copolymer (13)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 50 parts by mass of styrene was added. Next, 0.041 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 0.90 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium, and polymerization was carried out at 70°C for 30 minutes. Next, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene and 35 parts by mass of butadiene was added and polymerized at 70°C for 35 minutes. Next, 0.5 moles of ethyl benzoate were added to 1 mole of n-butyllithium, and the reaction was carried out at 70°C for 10 minutes. Methanol was then added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, as a stabilizer, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added per 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain the hydrogenated conjugated diene block copolymer (13). The hydrogenated conjugated diene block copolymer (13) obtained as described above has a styrene content of 65% by mass and a weight-average molecular weight of 19.0 × 10⁻⁶. 4 The vinyl bond content was 55%, and the hydrogenation rate was 98%.

[0113] <Preparation of hydrogenated conjugated diene block copolymer (14)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 37.5 parts by mass of styrene was added. Next, 0.14 parts by mass of n-butyllithium were added per 100 parts by mass of the total monomer, and 0.25 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium, and polymerization was carried out at 70°C for 35 minutes. Next, a cyclohexane solution (20% by mass) containing 25 parts by mass of butadiene was added and polymerization was carried out at 70°C for 20 minutes. Next, a cyclohexane solution (20% by mass) containing 37.5 parts by mass of styrene was added, and polymerization was carried out at 70°C for 35 minutes. Subsequently, methanol was added to stop the polymerization reaction, yielding a conjugated diene block copolymer. Next, the hydrogenation catalyst prepared as described above was added to the obtained conjugated diene block copolymer at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene copolymer, and the hydrogenation reaction was carried out for approximately 1.5 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, as a stabilizer, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added per 100 parts by mass of the hydrogenated conjugated diene block copolymer. The hydrogenated conjugated diene block copolymer obtained as described above has a styrene content of 30% by mass and a weight-average molecular weight of 7.1 × 10⁻⁶. 4 The vinyl bond content was 35%, and the hydrogenation rate was 98%. The hydrogenated conjugated diene block copolymer obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (14-M). The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (14-M) was titrated under the conditions described above. The denaturation rate was 1.1% by mass.

[0114] <Preparation of hydrogenated conjugated diene block copolymer (15)> The procedure was the same as for hydrogenated conjugated diene block copolymer (3), except that 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added at a rate of 1.1 moles per mole of n-butyllithium before adding methanol, the reaction was carried out at 70°C for 15 minutes, and methanol was added after the reaction was complete. The terminal amine-modified conjugated diene block copolymer (15) obtained as described above has a styrene content of 65% by mass and a weight-average molecular weight of 18.9 × 10⁻⁶. 4 The vinyl bond content was 26%, the modification rate was 80% by mass (0.80 modification groups per polymerization chain), and the hydrogenation rate was 82%.

[0115] <Preparation of hydrogenated conjugated diene block copolymer (16)> Except for setting the hydrogenation reaction time to 0.75 hours, the same procedure as for hydrogenated conjugated diene block copolymer (1) was performed to obtain hydrogenated conjugated diene block copolymer (16). The hydrogenated conjugated diene block copolymer (16) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (16)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (16)-M was titrated under the conditions described above. The denaturation rate was 0.5% by mass. The terminal maleic anhydride-modified conjugated diene block copolymer (16)-M obtained as described above has a styrene content of 30% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶. 4 The vinyl bond content was 36%, and the hydrogenation rate was 45%.

[0116] <Preparation of hydrogenated conjugated diene block copolymer (17)> Except for setting the hydrogenation reaction time to 1 hour, the same procedure as for hydrogenated conjugated diene block copolymer (1) was performed to obtain hydrogenated conjugated diene block copolymer (17). The hydrogenated conjugated diene block copolymer (17) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (17)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (17)-M was titrated under the conditions described above. The denaturation rate was 0.8% by mass. The terminal amine-modified conjugated diene block copolymer (17)-M obtained as described above has a styrene content of 30% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶. 4 The vinyl bond content was 35%, and the hydrogenation rate was 88%.

[0117] <Preparation of hydrogenated conjugated diene block copolymer (18)> Except for setting the hydrogenation reaction time to 1 hour, the same procedure as for hydrogenated conjugated diene block copolymer (3) was performed to obtain hydrogenated conjugated diene block copolymer (18). The hydrogenated conjugated diene block copolymer (18) obtained as described above was mixed with maleic anhydride and peroxide (Perhexa 25B, manufactured by NOF Corporation). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-210°C throughout the entire length of the extruder, and compounded to obtain maleic anhydride-modified hydrogenated conjugated diene block copolymer (18)-M. The obtained maleic anhydride-modified hydrogenated conjugated diene block copolymer (18)-M was titrated under the conditions described above. The denaturation rate was 0.8% by mass. The terminal amine-modified conjugated diene block copolymer (18)-M obtained as described above has a styrene content of 65% by mass and a weight-average molecular weight of 18.9 × 10⁻⁶. 4 The vinyl bond content was 26%, and the hydrogenation rate was 82%.

[0118] <Preparation of hydrogenated conjugated diene block copolymer (19)> Before adding methanol, 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added at a rate of 1.1 moles per mole of n-butyllithium, and the reaction was carried out at 70°C for 15 minutes. After the reaction was complete, methanol was added, and the procedure was carried out in the same manner as for the hydrogenated conjugated diene block copolymer (9), except that the maleic anhydride modification step was omitted. The terminal amine-modified conjugated diene block copolymer (19) obtained as described above has a styrene content of 30% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶ 4 The vinyl bond content was 70%, the modification rate was 80% by mass (0.80 modification groups per polymerization chain), and the hydrogenation rate was 88%.

[0119] <Preparation of hydrogenated conjugated diene block copolymer (20)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass concentration) containing 20 parts by mass of butadiene was added. Next, 0.068 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 0.30 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 20 parts by mass of styrene and 60 parts by mass of butadiene was added and polymerized at 70°C for 45 minutes. Next, 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added at a rate of 1.1 moles per mole of n-butyllithium, and the mixture was reacted at 70°C for 15 minutes. Subsequently, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (based on Ti) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.0 hour at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (20). The hydrogenated conjugated diene block copolymer (20) obtained as described above has a styrene content of 20% by mass and a weight-average molecular weight of 15.0 × 10⁻⁶. 4 The vinyl bond content was 35%, and the hydrogenation rate was 85%.

[0120] <Preparation of hydrogenated conjugated diene block copolymer (21)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass concentration) containing 10 parts by mass of styrene was added. Next, 0.068 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 0.68 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 80 parts by mass of butadiene was added and polymerization was carried out at 70°C for 45 minutes. Next, a cyclohexane solution (20% by mass) containing 10 parts by mass of styrene was added and polymerization was carried out at 70°C for 15 minutes. Next, 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added at a rate of 1.1 moles per mole of n-butyllithium, and the mixture was reacted at 70°C for 15 minutes. Subsequently, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (based on Ti) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.0 hour at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (21). The hydrogenated conjugated diene block copolymer (21) obtained as described above has a styrene content of 20% by mass and a weight-average molecular weight of 15.0 × 10⁻⁶. 4 The vinyl bond content was 55%, and the hydrogenation rate was 84%.

[0121] <Preparation of hydrogenated conjugated diene block copolymer (22)> Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and a jacket. First, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added. Next, 0.14 parts by mass of n-butyllithium was added per 100 parts by mass of the total monomer, and 0.23 moles of tetramethylethylenediamine (TMEDA) were added per mole of n-butyllithium, and polymerization was carried out at 70°C for 15 minutes. Next, a cyclohexane solution (20% by mass) containing 70 parts by mass of butadiene was added and polymerization was carried out at 70°C for 40 minutes. Next, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added and polymerization was carried out at 70°C for 15 minutes. Next, 1,3-dimethyl-2-imidazolidinone (hereinafter also abbreviated as "DMI") was added at a rate of 1.1 moles per mole of n-butyllithium, and the mixture was reacted at 70°C for 15 minutes. Subsequently, methanol was added to stop the polymerization reaction. Next, the hydrogenation catalyst prepared as described above was added to the conjugated diene block copolymer obtained as described above at a concentration of 70 ppm (Ti-based) per 100 parts by mass of the conjugated diene block copolymer, and the hydrogenation reaction was carried out for approximately 1.2 hours at a hydrogen pressure of 0.7 MPa and a temperature of 80°C. Next, 0.25 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the hydrogenated conjugated diene block copolymer to obtain hydrogenated conjugated diene block copolymer (22). The hydrogenated conjugated diene block copolymer (22) obtained as described above has a styrene content of 30% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶ 4 The vinyl bond content was 35%, and the hydrogenation rate was 94%.

[0122] <Preparation of hydrogenated conjugated diene block copolymer (23)> The procedure was the same as for hydrogenated conjugated diene block copolymer (22), except that the hydrogenation reaction time was set to 1.2 hours. The hydrogenated conjugated diene block copolymer (23) obtained as described above had a styrene content of 30% by mass and a weight-average molecular weight of 7.0 × 10⁻⁶. 4 The vinyl bond content was 35%, and the hydrogenation rate was 65%.

[0123] (Manufacturing of polypropylene resin compositions) Conjugated diene copolymers (1) to (23), and (1)-M, (3)-M, (4)-M, (8)-M, (9)-M, (10)-M, (16)-M, (17)-M, and (18)-M were mixed with polypropylene resin (PL500A, manufactured by Sun Allomer Co., Ltd.) to obtain a mixture (polypropylene / conjugated diene copolymer = 80 / 20). The mixture was then supplied to a twin-screw extruder with the temperature set to 150-220°C over the entire length of the extruder. After the resulting strand was cooled, it was cut into pellets to obtain pellets of the polypropylene resin composition.

[0124] [Manufacturing of laminates (Examples 1-40, Comparative Examples 1-15)] (Manufacturing of laminates (Examples 1-18, Comparative Examples 1-6)) A laminate with a three-layer structure consisting of layer (I), layer (II), and layer (III) was manufactured. First, each of the hydrogenated conjugated diene block copolymers was press-molded at 200°C to produce a hydrogenated conjugated diene block copolymer sheet (thickness: 0.5 mm). Next, a hydrogenated conjugated diene block copolymer sheet was laminated between a 2 mm thick flat plate made of acrylic resin (Delpet 80N, manufactured by Asahi Kasei Corporation) and a 2 mm thick flat plate made of polypropylene resin (PL500A, manufactured by Sun Allomer Co., Ltd.). The laminate was then heated and compressed (200°C) in a mold (4.5 mm thick) with the same shape as the flat plates to produce a laminate.

[0125] (Manufacturing of laminates (Examples 19-31, Comparative Examples 7-12)) A laminate with a two-layer structure was manufactured, consisting of layer (I) and layer (IV) containing polyolefin resin and adhesive components. First, a 2 mm thick flat plate made of acrylic resin was attached to the mold of an injection molding machine, and the polypropylene resin composition was injected at a cylinder temperature of 200°C to produce the laminate.

[0126] (Manufacturing of laminates (Examples 32-40, Comparative Examples 13-15)) A two-layer film (layer (I) approximately 30 μm, layer (III) 10 μm) in contact with layer (I) and layer (III) was co-extruded using a multilayer T-die extruder under the following conditions: extrusion temperature (layer (I): 230°C, layer (III): 200°C) and die temperature (230°C). Next, the two-layer film was attached to a mold (flat plate, temperature 50°C) of an injection molding machine, and the polypropylene resin was injected at a cylinder temperature of 200°C to laminate layer (II) and produce a laminate.

[0127] [Examples 1-18], [Comparative Examples 1-6] A three-layer laminate was prepared, consisting of layer (I): acrylic resin and layer (II): polypropylene resin, with the adhesive component as a single layer (layer (III)). The properties of this laminate were then evaluated.

[0128] [Examples 19-31], [Comparative Examples 7-12] A two-layer laminate consisting of a polypropylene resin composition layer (layer (IV)) and an acrylic resin layer (layer (I)) was prepared by mixing an adhesive component with polypropylene resin, and the properties of this laminate were evaluated.

[0129] [Examples 32-40], [Comparative Examples 13-15] A three-layer laminate was prepared, with the adhesive component as a single layer (layer (III)), consisting of layer (I): 30 μm of acrylic resin, and layer (II): polypropylene resin. The properties of this laminate were then evaluated.

[0130] The structures and properties of hydrogenated conjugated diene block copolymers (1) to (23) are shown in Tables 1 to 3 below.

[0131] [Table 1]

[0132] [Table 2]

[0133] [Table 3]

[0134] The properties of the three-layer laminate are evaluated in Tables 4 and 5 below. Comparative Examples 3 and 4, which used hydrogenated conjugated diene copolymers (8) and (10), did not show adhesion between layer (I) and layer (II), and no laminate was obtained.

[0135] [Table 4]

[0136] [Table 5]

[0137] The evaluation results of a two-layer laminate consisting of a polypropylene resin composition layer (layer (IV)) in which an adhesive component is mixed with polypropylene resin and an acrylic resin layer (layer (I)) are shown in Tables 6 and 7 below. Comparative Examples 9 and 10, which used hydrogenated conjugated diene copolymers (8) and (10), did not show adhesion between layer (I) and layer (IV), and no laminate was obtained.

[0138] [Table 6]

[0139] [Table 7]

[0140] The evaluation results for a three-layer laminate consisting of a single adhesive layer (layer (III)), layer (I): acrylic resin, and layer (II): polypropylene resin are shown in Tables 8 and 9 below.

[0141] [Table 8]

[0142] [Table 9]

[0143] Examples 1-40 and Comparative Examples 1-15 clearly demonstrate that the laminate of the present invention exhibits excellent adhesive strength and appearance.

[0144] This application is based on Japanese Patent Application No. 2022-092456, filed with the Japan Patent Office on June 7, 2022, the contents of which are incorporated herein by reference. [Industrial applicability]

[0145] The laminate of the present invention achieves both sufficient adhesive strength and appearance, and has industrial applicability as a decorative molded body for vehicle components, electronic devices such as televisions, and containers.

Claims

1. A layer (I) mainly composed of an acrylic resin, A layer (II) mainly composed of polyolefin resin, An adhesive layer (III) is provided between the acrylic resin-based layer and the polyolefin resin-based layer, A laminate having, The aforementioned adhesive layer (III) The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer, comprising two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. A laminate in which the hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv), and also satisfies the following conditions (i), (iii), and (iv). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

2. A layer (I) mainly composed of an acrylic resin, A layer (II) mainly composed of polyolefin resin, An adhesive layer (III) is provided between the acrylic resin-based layer and the polyolefin resin-based layer, A laminate having, The aforementioned adhesive layer (III) The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer, comprising two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. A laminate in which the hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv), and also satisfies the following conditions (ii), (iii), and (iv). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

3. A layer (I) mainly composed of an acrylic resin, A layer (II) mainly composed of polyolefin resin, An adhesive layer (III) is provided between the acrylic resin-based layer and the polyolefin resin-based layer, A laminate having, The aforementioned adhesive layer (III) The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer, comprising two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. A laminate in which the hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv), and satisfies condition (i) and condition (ii), does not satisfy condition (iv), and also satisfies condition (v). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less. <Condition (v)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is less than 25% by mass.

4. A layer (I) mainly composed of an acrylic resin, A layer (II) mainly composed of polyolefin resin, An adhesive layer (III) is provided between the acrylic resin-based layer and the polyolefin resin-based layer, A laminate having, The aforementioned adhesive layer (III) The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer, comprising two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. The hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv), and satisfies condition (i) below, and the polar groups of the hydrogenated conjugated diene block copolymer are A laminate comprising at least one selected from the group consisting of an acid anhydride group, an amino group, a dicarboxyl group, a carboxyl group, an epoxy group, and an oxetanyl group. <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

5. The polar group of the hydrogenated conjugated diene block copolymer is an amino group. The laminate according to claim 4.

6. The hydrogenation rate of the hydrogenated conjugated diene block copolymer is 90% or less. The laminate according to claim 5.

7. The thickness of the acrylic resin-based layer (I) is 1.5 mm or less. The laminate according to any one of claims 1 to 6.

8. The hydrogenated conjugated diene block copolymer satisfies the above condition (iv), The laminate according to claim 6.

9. A method for manufacturing a laminate according to any one of claims 1 to 4, A step of laminating the acrylic resin-based layer (I) and the adhesive layer (III) so that they are in contact, The process includes a step of laminating the polyolefin resin-based layer (II) such that the adhesive layer (III) and the polyolefin resin-based layer (II) are in contact. A method for manufacturing laminates.

10. The thickness of the aforementioned acrylic resin-based layer (I) is 1.5 mm or less. A method for manufacturing a laminate according to claim 9.

11. In the process of laminating the acrylic resin-based layer (I) and the adhesive layer (III), The acrylic resin-based layer (I) and the adhesive layer (III) are laminated in a molten state. A method for manufacturing a laminate according to claim 9.

12. In the process of laminating the aforementioned polyolefin resin-based layer (II), A laminate having the acrylic resin-based layer (I) and the adhesive layer (III) is mounted in a mold. The polyolefin resin is poured into the mold in a molten state. A method for manufacturing a laminate according to claim 9.

13. A layer (I) mainly composed of acrylic resin, A laminate having a layer (IV) containing a polyolefin resin and an adhesive component, The amounts of the polyolefin resin and adhesive component are in a mass ratio of polyolefin resin / adhesive component = 30 / 70 to 95 / 5. The aforementioned adhesive component The adhesive component mainly consists of a hydrogenated conjugated diene block copolymer, comprising two or more polymer blocks selected from the group consisting of a polymer block (A) mainly composed of vinyl aromatic monomer units, a polymer block (B) mainly composed of conjugated diene monomer units, and a polymer block (C) having vinyl aromatic monomer units and conjugated diene monomer units, wherein the unsaturated bonds of the conjugated diene monomer units are hydrogenated. A laminate in which the hydrogenated conjugated diene block copolymer satisfies two or more of the following conditions (i) to (iv). <Condition (i)> The hydrogenated conjugated diene block copolymer has polar groups. <Condition (ii)> The hydrogenated conjugated diene block copolymer, prior to hydrogenation, contains units (a) derived from 1,2-bonds and / or 3,4-bonds of the conjugated diene compound and units (b) derived from 1,4-bonds, and when the total content of the conjugated diene monomer units is taken as 100%, the content of units (a) derived from 1,2-bonds and / or 3,4-bonds is 50% or more. <Condition (iii)> The hydrogenated conjugated diene block copolymer has at least one polymer block (C). <Condition (iv)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is 25% by mass or more and 80% by mass or less.

14. The hydrogenated conjugated diene block copolymer satisfies the above conditions (i), (iii), and (iv), The laminate according to claim 13.

15. The hydrogenated conjugated diene block copolymer satisfies the above conditions (ii), (iii), and (iv), The laminate according to claim 13.

16. The hydrogenated conjugated diene block copolymer is The above conditions (i) and (ii) are satisfied, the above condition (iv) is not satisfied, and the above condition (v) is also satisfied, The laminate according to claim 13. <Condition (v)> The content of vinyl aromatic monomer units in the hydrogenated conjugated diene block copolymer is less than 25% by mass.

17. The hydrogenated conjugated diene block copolymer satisfies condition (i), and the polar groups of the hydrogenated conjugated diene block copolymer are At least one selected from the group consisting of an acid anhydride group, an amino group, a dicarboxyl group, a carboxyl group, an epoxy group, and an oxetanyl group. The laminate according to claim 13.

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