Laminate and method for manufacturing a laminate

Abstract

The hydrogenated block copolymer composition for the surface exhibits high abrasion resistance and mechanical properties, while also providing a laminate that shows high adhesive strength even when laminated with an olefin-based resin for the substrate at low temperatures. [Solution] At least two types of hydrogenated block copolymers (a) and hydrogenated block copolymers (b), an olefin resin (c-1), a thermoplastic resin (d), a softening agent (e), A hydrogenated block copolymer composition containing, and an olefin resin for the base material (c-2), A laminate of [something].

Description

Technical Field

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

Background Art

[0002] In recent years, automated driving and mobility services have attracted attention as new directions for automobiles. Due to this trend, the performance required for automotive parts such as automotive interior materials has also changed. For example, with the advancement of automated driving, automobiles are expected to have a stronger meaning as living spaces. Therefore, as a space creation that allows passengers to spend more comfortably, the sophistication of the interior and the diversification of interior design have progressed. As a result, the resin composition used as the material for automotive interior materials requires a molding appearance that can achieve a finer design and a tactile feeling that gives a more luxurious impression than before. Also, from the perspective of mobility services, it is considered that with the penetration of car-sharing, the long life and cleanliness of automobiles will be required. Therefore, the number of times automotive parts such as automotive interior materials are cleaned has increased compared to the past, and the resin composition used as the material requires mechanical properties such as higher abrasion resistance and higher tensile strength. As described above, due to the penetration of automated driving and mobility services, in recent years, the resin composition is required to have a better molding appearance than conventional products, a tactile feeling that gives a luxurious impression, and excellent abrasion resistance.

[0003] Furthermore, when manufacturing a laminate using a thermoplastic resin applied to automotive parts by injection molding, usually two-color molding is used. However, in order to manufacture the laminate with more general-purpose equipment, insert molding is effective, and the demand for a resin composition suitable for such insert molding is increasing. In order to manufacture a laminate by insert molding, it is necessary that the thermoplastic resin for the base material and the resin composition for the skin have a high adhesive strength. Due to these high adhesive strengths, the resin composition for the skin can be laminated in a state where the temperature of the thermoplastic resin for the base material is low.

[0004] Conventionally, thermoplastic elastomer compositions containing hydrogenated block copolymers composed of conjugated diene compounds and vinyl aromatic compounds, olefin resins, and softeners have been proposed as resin materials for automotive parts (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-193339 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] However, conventionally proposed thermoplastic elastomer compositions still have a problem: when the thermoplastic resin used as the base material is at a low temperature, the adhesive strength between the two is low, making them unsuitable for insert molding.

[0007] Therefore, the present invention aims to provide a laminate in which the resin composition for the surface exhibits high abrasion resistance and mechanical properties, while also exhibiting high adhesive strength even when laminated with a thermoplastic resin for the substrate at low temperatures. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the problems of the prior art described above, and have found that in a laminate of a hydrogenated block copolymer composition containing at least two types of hydrogenated block copolymers, an olefin resin, a thermoplastic resin, and a softener, and an olefin resin for a base material, by specifying the structure of the hydrogenated block copolymer contained in the hydrogenated block copolymer composition to an appropriate range and mixing it in an appropriate blending ratio, the hydrogenated block copolymer composition for the surface exhibits high abrasion resistance and mechanical properties, and also exhibits high adhesive strength even when laminated with an olefin resin for a base material at low temperatures, thus completing the present invention. In other words, the present invention is as follows.

[0009] [1] At least two types of hydrogenated block copolymers (a) and hydrogenated block copolymers (b), Olefin resin (c-1) and Thermoplastic resin (d) and Softener (e), A hydrogenated block copolymer composition containing, Olefin resin for base material (c-2), It is a laminated body, A laminate that satisfies the following conditions (1) to (6). <Condition (1)>: The hydrogenated block copolymer (a) and the hydrogenated block copolymer (b) are hydrogenated block copolymers containing vinyl aromatic monomer units and conjugated diene monomer units. <Condition (2)>: The hydrogenated block copolymer (a) comprises a hydrogenated copolymer block (A1) and a hydrogenated copolymer block (A2), wherein the hydrogenated copolymer block (A1) consists of vinyl aromatic monomer units and conjugated diene monomer units, with a vinyl aromatic monomer unit content of 40 to 80% by mass, and the hydrogenated copolymer block (A2) mainly consists of vinyl aromatic monomer units, with a hydrogenated copolymer block (A2) content of 15% by mass or more and 35% by mass or less in the hydrogenated block copolymer (a). <Condition (3)>: The hydrogenated block copolymer (b) comprises a hydrogenated copolymer block (B1) and a hydrogenated copolymer block (B2). The hydrogenated copolymer block (B1) consists of vinyl aromatic monomer units and conjugated diene monomer units, with a vinyl aromatic monomer unit content of 20 to 60% by mass. The hydrogenated copolymer block (B2) mainly consists of conjugated diene monomer units, and the content of the hydrogenated copolymer block (B2) in the hydrogenated block copolymer (b) is 10% by mass or more and 60% by mass or less. The hydrogenated copolymer block (b) also contains a polymer block (B3) mainly consisting of at least one vinyl aromatic monomer unit. <Condition (4)>: The hydrogenated block copolymer (a) has a total vinyl aromatic monomer unit content of 40 to 80% by mass, and the hydrogenated block copolymer (b) has a total vinyl aromatic monomer unit content of 15 to 45% by mass. <Condition (5)>: The mass ratio (a) / (b) of the content of hydrogenated copolymer block (a) to the content of hydrogenated copolymer block (b) in the hydrogenated block copolymer composition is 50 / 50 to 90 / 10. <Condition (6)>: The content of components (a) to (e) in the hydrogenated block copolymer composition is as follows. Total content of hydrogenated block copolymer (a) and hydrogenated block copolymer (b): 3% by mass or more and 95% by mass or less Olefin resin (c-1): 1% by mass or more and 42% by mass or less Thermoplastic resin (d): 1% by mass 60% by mass or less Softener (e): 1% by mass or more, 65% by mass or less [2] The amount of vinyl bond in the hydrogenated copolymer block (B2) is 40 to 85% by mass. The laminate described in [1] above. [3] The olefin resin (c-1) comprises at least one type of polypropylene resin. The laminate described in [1] or [2] above. [4] The aforementioned laminate, A laminate for automotive parts, selected from the group consisting of side moldings, grommets, shift knobs, weatherstrips, window frames and their sealing materials, instrument panels, assist grips, steering wheels, shift levers, consoles, armrests, headrests, and door panels, as described in any one of [1] to [3] above. [5] A method for manufacturing a laminate according to any one of the above [1] to [4], The olefin resin (c-2) for the base material is placed in the mold of the injection molding machine, and then the hydrogenated block copolymer composition is laminated and injection molding is performed. A method for manufacturing laminates. 〔6〕 A step of laminating the hydrogenated block copolymer composition on the olefin resin (c-2) for the base material and performing injection molding is performed by setting the temperature of the olefin resin for the base material installed in the mold of an injection molding machine to 60° C. or lower. The method for producing a laminate according to the above [5].

Advantages of the Invention

[0010] According to the present invention, a laminate having high adhesive strength can be obtained even when a hydrogenated block copolymer composition for the skin layer is laminated with an olefin resin for the base material at a low temperature while exhibiting high wear resistance and mechanical properties.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the following present embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be variously modified and implemented within the scope of its gist.

[0012] 〔Laminate〕 The laminate of the present embodiment is at least two types of hydrogenated block copolymers (a) and hydrogenated block copolymers (b), an olefin resin (c-1), a thermoplastic resin (d), a softening agent (e), and a hydrogenated block copolymer composition containing the same, and an olefin resin (c-2) for the base material, which is a laminate satisfying the following conditions (1) to (6). Satisfies the following conditions (1) to (6). <Condition (1)>: The hydrogenated block copolymer (a) and the hydrogenated block copolymer (b) are hydrogenated products of block copolymers containing vinyl aromatic monomer units and conjugated diene monomer units. <Condition (2)>:​The hydrogenated block copolymer (a) comprises a hydrogenated copolymer block (A1) and a hydrogenated copolymer block (A2), wherein the hydrogenated copolymer block (A1) consists of vinyl aromatic monomer units and conjugated diene monomer units, with a vinyl aromatic monomer unit content of 40 to 80% by mass, and the hydrogenated copolymer block (A2) mainly consists of vinyl aromatic monomer units, with a hydrogenated copolymer block (A2) content of 15% by mass or more and 35% by mass or less in the hydrogenated block copolymer (a). <Condition (3)>: The hydrogenated block copolymer (b) comprises a hydrogenated copolymer block (B1) and a hydrogenated copolymer block (B2). The hydrogenated copolymer block (B1) consists of vinyl aromatic monomer units and conjugated diene monomer units, with a vinyl aromatic monomer unit content of 20 to 60% by mass. The hydrogenated copolymer block (B2) mainly consists of conjugated diene monomer units, and the content of the hydrogenated copolymer block (B2) in the hydrogenated block copolymer (b) is 10% by mass or more and 60% by mass or less. The hydrogenated copolymer block (b) also contains a polymer block (B3) mainly consisting of at least one vinyl aromatic monomer unit. <Condition (4)>: The hydrogenated block copolymer (a) has a total vinyl aromatic monomer unit content of 40 to 80% by mass, and the hydrogenated block copolymer (b) has a total vinyl aromatic monomer unit content of 15 to 45% by mass. <Condition (5)>: The mass ratio (a) / (b) of the content of hydrogenated copolymer block (a) to the content of hydrogenated copolymer block (b) in the hydrogenated block copolymer composition is 50 / 50 to 90 / 10. <Condition (6)>: The content of components (a) to (e) in the hydrogenated block copolymer composition is as follows. Total content of hydrogenated block copolymer (a) and hydrogenated block copolymer (b): 3% by mass or more and 95% by mass or less Olefin resin (c-1): 1% by mass or more and 42% by mass or less Thermoplastic resin (d): 1% by mass 60% by mass or less Softener (e): 1% by mass or more, 65% by mass or less

[0013] According to the above configuration, a laminate can be obtained in which the resin composition for the surface exhibits high abrasion resistance and mechanical properties, while also exhibiting high adhesive strength even when laminated with a base resin at a low temperature.

[0014] (Hydrogenated block copolymer composition) The laminate in this embodiment is a laminate of a hydrogenated block copolymer composition and an olefin resin (c-1) for the base material. The hydrogenated block copolymer composition contains at least two types of hydrogenated block copolymers (a) and hydrogenated block copolymer (b), an olefin resin (c-1), a thermoplastic resin (d), and a softening agent (e).

[0015] <Hydrogenated block copolymers (a) and (b)> The hydrogenated block copolymers (a) and (b) used in the hydrogenated block copolymer composition in the laminate of this embodiment are hydrogenated block copolymers containing vinyl aromatic monomer units and conjugated diene monomer units (condition (1) above).

[0016] [Vinyl aromatic monomer unit] Examples of vinyl aromatic compounds that form vinyl aromatic monomer units include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N,N-dimethyl-p-aminoethylstyrene, and N,N-diethyl-p-aminoethylstyrene. In particular, styrene is preferred from the viewpoint of balancing cost and the mechanical strength of the hydrogenated block copolymer composition containing hydrogenated block copolymers (a) and (b). These may be used individually or in combination of two or more types.

[0017] [Conjugated diene monomer units] A conjugated diene monomer unit is a monomer unit derived from a diolefin that has one pair of conjugated double bonds. Examples of such diolefins include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, and 1,3-hexadiene. In particular, 1,3-butadiene and isoprene are preferred from the viewpoint of balancing good moldability and mechanical strength. These may be used individually or in combination of two or more types.

[0018] In this specification, "mainly" in the composition of a hydrogenated block copolymer means that the proportion of a predetermined monomer unit in a predetermined polymer block is 85% by mass or more, preferably 90% by mass or more, and more preferably 95% by mass or more. Furthermore, since the content of vinyl aromatic monomer units in (A1) is 40-80% by mass and the content of vinyl aromatic monomer units in (B1) is 20-60% by mass, the hydrogenated copolymer blocks (A1) and (B1) can be clearly distinguished from the polymer blocks (A2) and (B2).

[0019] [Hydrogenated copolymer block (A1)] The hydrogenated block copolymer (a) used in the hydrogenated block copolymer composition in the laminate of this embodiment contains at least one hydrogenated copolymer block (A1) consisting of a vinyl aromatic monomer unit and a conjugated diene monomer unit. The content of vinyl aromatic monomer units in the hydrogenated copolymer block (A1) is 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more. When the content of vinyl aromatic monomer units in the hydrogenated copolymer block (A1) is 40% by mass or more, the hydrogenated block copolymer composition in the laminate of this embodiment tends to exhibit good abrasion resistance. Furthermore, when the content is 50% by mass or more, even higher abrasion resistance is exhibited, making it suitable for applications with more stringent abrasion resistance requirements, such as applications in automotive interior materials where thinner molded bodies are required, or applications in automotive interior materials where long-term appearance maintenance is required when subjected to higher loads or friction from coarser fabrics, such as denim fabric which is coarser than cotton fabric like Kanakin No. 3, under conditions simulating passenger use.

[0020] The content of vinyl aromatic monomer units in the hydrogenated copolymer block (A1) is 80% by mass or less, preferably 75% by mass or less, and more preferably 70% by mass or less. If the content of vinyl aromatic monomer units in the hydrogenated copolymer block (A1) is 80% by mass or less, the hydrogenated block copolymer composition in the laminate in this embodiment exhibits good heat resistance and can be used in applications where heat resistance is a critical requirement, such as in automotive interior materials, where thinner molded articles are required, or where long-term use or use at higher temperatures requires the maintenance of the material's texture (texture) and shape (resistance to deformation due to heat).

[0021] The content of vinyl aromatic monomer units in the hydrogenated copolymer block (A1) can be measured using nuclear magnetic resonance (NMR) spectrometers (as described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981), hereafter referred to as the "NMR method"), with the block copolymer before hydrogenation and the hydrogenated block copolymer after hydrogenation as samples. Furthermore, the content of vinyl aromatic monomer units in the hydrogenated copolymer block (A1) can be controlled within the above numerical range by adjusting the amount of vinyl aromatic compound and conjugated diene added to the polymerization reactor, the reaction temperature, etc.

[0022] [Polymer block mainly composed of vinyl aromatic monomer units (A2)] The hydrogenated block copolymer (a) used in the hydrogenated block copolymer composition in the laminate in this embodiment contains at least one polymer block (A2) mainly composed of vinyl aromatic monomer units. This tends to prevent pellet blocking. Furthermore, the hydrogenated block copolymer (a) contains 15% by mass or more of polymer block (A2), preferably 20% by mass or more, and more preferably 25% by mass or more. When the content of polymer blocks (A2) mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer (a) is 15% by mass or more, the blocking resistance of the pellets of the hydrogenated block copolymer (a) is improved, and the laminate of this embodiment tends to exhibit excellent abrasion resistance and heat resistance.

[0023] When pellets of hydrogenated block copolymer (a) exhibit good blocking resistance, blocking tends to be less likely to occur during transport under conditions such as longer transport times, higher loads, and harsh temperature environments (e.g., regions with high ambient temperatures or extreme temperature fluctuations), which is expected to facilitate pellet weighing and blending during compound molding. Furthermore, since the amount of anti-tack agent can be reduced, it is expected to have effects such as avoiding equipment contamination, reducing environmental impact, and suppressing unexpected deterioration of physical properties, such as a decrease in transparency and mechanical strength. If the hydrogenated block copolymer composition in the laminate of this embodiment exhibits good abrasion resistance, it can be used in applications requiring more stringent abrasion resistance, such as in automotive materials. For example, when used as a material for thinner molded bodies or more complex / larger molded bodies than general molded bodies in automotive interior materials, the material's appearance can be expected to be maintained at a level comparable to the general molded bodies described above, even after longer periods of use. Furthermore, when used in automotive interior materials, even when subjected to higher loads or friction from coarser fabrics, such as denim fabric which has a coarser weave than cotton fabric like Kanakin No. 3, the material's appearance can be expected to be maintained for a long period of time, assuming conditions during vehicle use.

[0024] Furthermore, the hydrogenated block copolymer (a) has a polymer block (A2) content of 35% by mass or less, preferably 33% by mass or less, and more preferably 31% by mass or less. When the content of polymer blocks (A2) mainly composed of vinyl aromatic monomer units in the hydrogenated block copolymer (a) is 35% by mass or less, the hydrogenated block copolymer composition in the laminate in this embodiment tends to exhibit good heat resistance, and when it is 31% by mass or less, it tends to exhibit even better heat resistance.

[0025] The content of polymer blocks (A2) in hydrogenated block copolymer (a) can be measured by nuclear magnetic resonance (NMR) or the like. Furthermore, the content of polymer block (A2) in hydrogenated block copolymer (a) can be controlled within the above numerical range mainly by adjusting the amount of vinyl aromatic compound added to the polymerization reactor, the reaction temperature, and the reaction time.

[0026] [Hydrogenated copolymer block (B1)] The hydrogenated block copolymer (b) used in the hydrogenated block copolymer composition in the laminate in this embodiment contains at least one hydrogenated copolymer block (B1) consisting of a vinyl aromatic monomer unit and a conjugated diene monomer unit. The content of vinyl aromatic monomer units in the hydrogenated copolymer block (B1) is 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more. When the content of vinyl aromatic monomer units in the hydrogenated copolymer block (B1) is 20% by mass or more, the hydrogenated block copolymer composition in the laminate of this embodiment tends to exhibit good abrasion resistance. Furthermore, when it is 30% by mass or more, even higher abrasion resistance is exhibited, making it suitable for applications with more stringent abrasion resistance requirements, such as applications in automotive interior materials where thinner molded bodies are required, or applications in automotive interior materials where long-term appearance maintenance is required when subjected to higher loads or friction from coarser fabrics, such as denim fabric which is coarser than cotton fabric like Kanakin No. 3, under conditions simulating passenger use.

[0027] The content of vinyl aromatic monomer units in the hydrogenated copolymer block (B1) is 60% by mass or less, preferably 58% by mass or less, and more preferably 55% by mass or less. When the content of vinyl aromatic monomer units in the hydrogenated copolymer block (B1) is 60% by mass or less, the laminate of this embodiment exhibits good heat resistance and can be used in applications where heat resistance is a critical requirement, such as in automotive interior materials, where thinner molded articles are required, or in applications where long-term use or use at higher temperatures requires the maintenance of the material's texture (texture) and shape (resistance to deformation due to heat) over a long period.

[0028] The content of vinyl aromatic monomer units in the hydrogenated copolymer block (B1) can be measured by NMR using samples of the block copolymer before hydrogenation and the hydrogenated block copolymer after hydrogenation. Furthermore, the content of vinyl aromatic monomer units in the hydrogenated copolymer block (B1) can be controlled to the above numerical range by adjusting the amount of vinyl aromatic compound and conjugated diene added to the polymerization reactor, the reaction temperature, etc.

[0029] [Hydrogenated polymer block mainly composed of conjugated diene monomer units (B2)] The hydrogenated block copolymer (b) used in the hydrogenated block copolymer composition in the laminate of this embodiment contains one or more hydrogenated polymer blocks (B2) mainly composed of conjugated diene monomer units. Furthermore, the hydrogenated block copolymer (b) contains 10% by mass or more of a hydrogenated polymer block (B2) mainly composed of conjugated diene monomer units, preferably 20% by mass or more, and more preferably 30% by mass or more. When the hydrogenated block copolymer (b) contains 20% by mass or more of hydrogenated polymer blocks (B2) mainly composed of conjugated diene monomer units, the compatibility of the hydrogenated block copolymer composition in the laminate of this embodiment with the polyolefin resin (c-1) and thermoplastic resin (d) described later is improved, the interfacial strength is further enhanced, abrasion resistance, scratch resistance and low-temperature properties are improved, and the adhesive strength between the substrate olefin resin (c-2) and the hydrogenated block copolymer composition in the laminate of this embodiment tends to improve.

[0030] Furthermore, the hydrogenated block copolymer (b) contains 60% by mass or less of a hydrogenated polymer block (B2) mainly composed of conjugated diene monomer units, preferably 55% by mass or less, and more preferably 50% by mass or less. When the content of hydrogenated polymer blocks (B2) mainly composed of conjugated diene monomer units in hydrogenated block copolymer (b) is 60% by mass or less, the blocking resistance of the pellets of hydrogenated copolymer block (b) tends to be good.

[0031] The content of hydrogenated polymer blocks (B2) mainly composed of conjugated diene monomer units in hydrogenated block copolymer (b) can be measured by NMR spectroscopy using the block copolymer before hydrogenation and the hydrogenated block copolymer after hydrogenation as samples. Furthermore, the hydrogenated copolymer block (B2) content in hydrogenated block copolymer (b) can be controlled within the above numerical range by adjusting the amount of conjugated diene added to the polymerization reactor, the reaction temperature, etc.

[0032] The amount of vinyl bond in the hydrogenated copolymer block (B2) is preferably 40 to 85% by mass, from the viewpoint of improving the adhesive strength between the hydrogenated block copolymer composition and the polyolefin resin for the substrate. More preferably, it is 50 to 85% by mass, and even more preferably 60 to 85% by mass. The amount of vinyl bond in the hydrogenated copolymer block (B2) can be controlled to the above numerical range by using a modifier such as a tertiary amine compound or ether compound, as described later.

[0033] [Polymer block mainly composed of vinyl aromatic monomer units (B3)] The hydrogenated block copolymer (b) used in the hydrogenated block copolymer composition in the laminate in this embodiment contains at least one polymer block (B3) mainly composed of vinyl aromatic monomer units. This tends to prevent pellet blocking.

[0034] [Total vinyl aromatic compound content] The hydrogenated block copolymer (a) has a total vinyl aromatic monomer unit content of 40% by mass or more and 80% by mass or less, preferably 50% by mass or more and 80% by mass or less, and more preferably 60% by mass or more and 80% by mass or less. When the total vinyl aromatic monomer unit content in the hydrogenated block copolymer (a) is 40% by mass or more, the abrasion resistance of the hydrogenated block copolymer composition tends to be good. Good abrasion resistance allows it to be used in applications where more stringent abrasion resistance is required, such as in automotive materials. For example, in automotive interior materials, even when molding thinner walls or more complex / large molded bodies, and even after long-term use, the material's appearance can be expected to be maintained at a level comparable to the general molded bodies described above. Furthermore, even when subjected to higher loads or abrasion by coarser fabrics, such as denim fabric which is coarser than cotton fabric like Kanakin No. 3, as is assumed during vehicle use, the material's appearance can be expected to be maintained for a long period of time.

[0035] The hydrogenated block copolymer (b) has a total vinyl aromatic compound monomer unit content of 15% by mass or more and 45% by mass or less, preferably 20% by mass or more and 45% by mass or less, and more preferably 25% by mass or more and 45% by mass or less. When the total vinyl aromatic compound monomer unit content is 45% by mass or less, the adhesive strength between the hydrogenated block copolymer composition and the olefin resin for the substrate (c-2) tends to improve. Improved adhesive strength allows lamination not only in two-color molding but also in insert molding and other applications where the substrate resin temperature is low, thereby broadening the molding window for injection molding.

[0036] [Mass ratio of hydrogenated block copolymer content (a) and (b) in the hydrogenated block copolymer composition] The hydrogenated block copolymer composition in the laminate of this embodiment contains at least two types of hydrogenated block copolymers (a) and (b). The mass ratio (a) / (b) of the hydrogenated block copolymers (a) and (b) is 50 / 50 to 90 / 10, preferably 60 / 40 to 90 / 10, and more preferably 70 / 30 to 90 / 10. When (a) / (b) is within the appropriate range described above, the adhesive strength between the hydrogenated block copolymer composition and the olefin resin for the substrate (c-2) tends to improve.

[0037] [Weight-average molecular weight of hydrogenated block copolymers (a) and (b)] The hydrogenated block copolymers (a) and (b) used in the hydrogenated block copolymer composition constituting the laminate of this embodiment have a weight-average molecular weight (Mw) of 20,000 or more, more preferably 3 or more, and even more preferably 50,000 or more, from the viewpoint of obtaining extrudeability during pellet production of hydrogenated block copolymers (a) and (b) and good mechanical strength in the foam of this embodiment. The upper limit is preferably 300,000 or less, more preferably 200,000 or less, and even more preferably 150,000 or less. When the weight-average molecular weight (Mw) is 300,000 or less, the hydrogenated block copolymers (a) and (b) tend to melt more easily during pellet production (extrusion molding), the strands become more stable, and the extrusion moldability tends to improve. The weight-average molecular weights of the hydrogenated block copolymers (a) and (b) in this embodiment are determined by measuring them using gel permeation chromatography (GPC) and using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from measurements of commercially available standard polystyrene.

[0038] [Hydrogenation rate of double bonds in conjugated diene monomer units in hydrogenated block copolymers (a) and (b)] From the viewpoint of obtaining good weather resistance, the hydrogenation rate of the double bonds of the conjugated diene monomer units in the hydrogenated block copolymers (a) and (b) used in the laminate of this embodiment is preferably 20% or more, more preferably 50% or more, and even more preferably 92% or more. In particular, for automotive interior applications, where high abrasion resistance and weather resistance are required, a hydrogenation rate of 92% or higher is preferable. The hydrogenation rate of the double bonds of the conjugated diene monomer units in hydrogenated block copolymers (a) and (b) can be controlled within the above numerical range by adjusting the amount of hydrogenation. The hydrogenation rate of hydrogenated block copolymer (i) can be measured using a nuclear magnetic resonance spectrometer (NMR) or the like.

[0039] The hydrogenated block copolymers (a) and (b) used in the laminate of this embodiment may be modified hydrogenated block copolymers in which atomic groups having predetermined functional groups are bonded. Furthermore, when hydrogenated block copolymers (a) and (b) are modified hydrogenated block copolymers, they may also be secondary modified block copolymers. In this specification, "secondary modification" is a term characterized by the manufacturing method, where the first step of bonding functional groups to the block copolymer is called primary modification, and the step of reacting those functional groups with other compounds is called secondary modification. For example, a typical manufacturing method involves polymerizing in solution, then reacting the primary modified product, which is obtained by reacting a modifying agent (e.g., an amine) at the polymerization termination end, with another compound (e.g., maleic acid) in an extruder to produce a secondary modified product.

[0040] <Method for producing hydrogenated block copolymers (a) and (b)> The hydrogenated block copolymers (a) and (b) used in the laminate of this embodiment, which are block copolymers in their state before hydrogenation, can be obtained, for example, by performing living anionic polymerization of a vinyl aromatic compound and a conjugated diene compound in a hydrocarbon solvent using a polymerization initiator such as an organoalkali metal compound.

[0041] [Hydroxide solvents] Examples of hydrocarbon 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 methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.

[0042] [Polymerization initiator] Polymerization initiators are not particularly limited, but examples include organoalkali metal compounds such as aliphatic hydrocarbon alkali metal compounds, aromatic hydrocarbon alkali metal compounds, and organic aminoalkali metal compounds, which are known to have anionic polymerization activity with respect to vinyl aromatic compounds and conjugated dienes. The organoalkali metal compounds are not limited to the following, but for example, aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms are preferred, and compounds containing one lithium atom per molecule, dilithium compounds, trilithium compounds, and tetralithium compounds containing multiple lithium atoms per molecule can be applied. Specifically, examples include reaction products of n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene and sec-butyllithium, and reaction products of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene. Furthermore, organoalkali metal compounds disclosed in, for example, U.S. Patent No. 5,708,092, UK Patent No. 2,241,239, and U.S. Patent No. 5,527,753 can also be applied.

[0043] [Adjusting agent] When copolymerizing a vinyl aromatic compound and a conjugated diene using an organoalkali metal compound as a polymerization initiator, the content of vinyl bonds (1,2-bonds or 3,4-bonds) originating from the conjugated diene incorporated into the polymer, as well as the random copolymerization properties of the vinyl aromatic compound and the conjugated diene, can be adjusted by using a predetermined modifier. Examples of such modifying agents include, but are not limited to, tertiary amine compounds, ether compounds, and metal alkoxide compounds. The adjusting agent may be used alone or in combination of two or more types.

[0044] Examples of tertiary amine compounds include, but are not limited to, compounds represented by the general formula: R1R2R3N (where R1, R2, and R3 represent hydrocarbon groups having 1 to 20 carbon atoms or hydrocarbon groups having a tertiary amino group). Specifically, examples include 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, and N,N'-dioctyl-p-phenylenediamine.

[0045] The ether compounds are not limited to those listed below, but examples 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. 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.

[0046] Examples of metal alkoxide compounds include, but are not limited to, sodium t-pentoxide, sodium t-butoxide, potassium t-pentoxide, and potassium t-butoxide.

[0047] [Polymerization method] Conventional known methods can be applied as methods for polymerizing vinyl aromatic compounds and conjugated dienes using organoalkali metal compounds as polymerization initiators. The following are some examples, but the method may be batch polymerization, continuous polymerization, or a combination thereof. Batch polymerization is particularly preferred for obtaining copolymers with excellent heat resistance. The polymerization temperature is preferably between 0°C and 180°C, and more preferably between 30°C and 150°C. The polymerization time varies depending on the conditions, but is usually within 48 hours, and preferably between 0.1 and 10 hours. Furthermore, an inert gas atmosphere such as nitrogen gas is preferred as the atmosphere for the polymerization system. The polymerization pressure should be set to a pressure range that can maintain the monomer and solvent in the liquid phase within the above temperature range, and is not particularly limited. Furthermore, it is preferable to take care to prevent the polymerization system from containing impurities that would deactivate the catalyst and living polymer, such as water, oxygen, or carbon dioxide.

[0048] Furthermore, at the end of the polymerization process described above, a coupling reaction may be carried out by adding the necessary amount of a coupling agent with two or more functionalities. Known bifunctional coupling agents can be used, and are not limited to the following, but include alkoxysilane compounds such as trimethoxysilane, triethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, trichloromethoxysilane, and trichloroethoxysilane; dihalogen compounds such as dichloroethane, dibromoethane, dimethyldichlorosilane, and dimethyldibromosilane; and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates. Furthermore, while not particularly limited, conventionally known polyfunctional coupling agents with three or more functions can be used, examples include polyalcohols with three or more functions, epoxidized soybean oil, diglycidylbisphenol A, and polyvalent epoxy compounds such as 1,3-bis(N-N'-diglycidylaminomethyl)cyclohexane; general formula R4-nSiX n Silicon halide compounds represented by (where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer from 3 to 4), such as methylsilyl trichloride, t-butylsilyl trichloride, silicon tetrachloride, and their brominateds; general formula R4-nSnX n Examples of tin halogen compounds represented by (where R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer from 3 to 4) include polyvalent halogen compounds such as methyltin trichloride, t-butyltin trichloride, and tin tetrachloride. Dimethyl carbonate and diethyl carbonate may also be used.

[0049] [Modification process] The hydrogenated block copolymers (a) and (b) used in the laminate of this embodiment may be modified block copolymers to which atomic groups having functional groups are bonded. It is preferable to bond the atomic groups having functional groups as a step before the hydrogenation step described later. The aforementioned "atomic group having a functional group" is not limited to the following, but examples include atomic groups containing at least one functional group selected from hydroxyl group, carboxyl group, carbonyl group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, isothiocyanate group, silicon halide group, silanol group, alkoxysilicon group, tin halide group, boronic acid group, boron-containing group, boronic acid base, alkoxytin group, phenyltin group, etc. In particular, atomic groups having at least one functional group selected from hydroxyl group, epoxy group, amino group, silanol group, and alkoxysilane group are preferred. The aforementioned "atomic group having a functional group" can be bonded by a denaturing agent. Examples of denaturing agents include, but are not limited to, tetraglycidylmetoxylendiamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxybenzophenone, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and N-methylpyrrolidone.

[0050] Modified block copolymers are not particularly limited, but can be obtained, for example, by anionic living polymerization using a polymerization initiator having a functional group or an unsaturated monomer having a functional group, by forming a functional group at the living end, or by adding a modifying agent containing a functional group. Other methods for obtaining modified block copolymers include reacting a block copolymer with an organolithium compound or other organolalkali metal compound (metallation reaction), and then adding a functional modifier to the block polymer to which the organolalkali metal has been added. However, in the latter method, a modified hydrogenated block copolymer can also be produced by first obtaining a hydrogenated block copolymer, then subjecting it to a metallation reaction, and finally reacting it with a modifying agent. The temperature at which the denaturation reaction is carried out is preferably 0 to 150°C, and more preferably 20 to 120°C. The time required for the denaturation reaction varies depending on other conditions, but is preferably within 24 hours, and more preferably 0.1 to 10 hours. Depending on the type of denaturing agent used, amino groups may generally be converted into organometallic salts at the stage of reaction with the denaturing agent. In such cases, they can be converted back to amino groups by treatment with a compound containing active hydrogen, such as water or alcohol. Furthermore, in such modified block copolymers, some unmodified block copolymers may be present within the modified block copolymer.

[0051] Furthermore, the modified block copolymer described above may be a secondary modified block copolymer. A secondary modified block copolymer is obtained by reacting a modified block copolymer with a secondary modifying agent that is reactive with the functional groups of the modified block copolymer. The secondary modifying agent is not particularly limited, but examples include a modifying agent having a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group, and having at least two of these functional groups. However, if the functional group is an acid anhydride group, it may have only one acid anhydride group.

[0052] As described above, when reacting a modified block copolymer with a secondary modifier, the amount of secondary modifier used per equivalent of functional groups bonded to the modified block copolymer is preferably 0.3 to 10 moles, more preferably 0.4 to 5 moles, and even more preferably 0.5 to 4 moles. The method for reacting the modified block copolymer with the secondary modifier is not particularly limited and any known method can be applied. For example, this could be the melt-kneading method described later, or a method in which each component is dissolved or dispersed in a solvent and mixed before reaction. It is preferable to carry out these secondary modifications after the hydrogenation step.

[0053] Suitable secondary modifiers include, but are not limited to, maleic anhydride, pyromellitic anhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, and bis-(3-triethoxysilylpropyl)-tetrasulfan.

[0054] Furthermore, the hydrogenated block copolymers (a) and (b) used in the laminate of this embodiment can be modified block copolymers graft-modified with α,β-unsaturated carboxylic acids or their derivatives, such as their anhydrides, esterifieds, amidateds, or imidateds. Examples of α,β-unsaturated carboxylic acids or their derivatives include, but are not limited to, maleic anhydride, maleimide anhydride, acrylic acid or its esters, methacrylic acid or its esters, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid or its anhydride. The amount of α,β-unsaturated carboxylic acid or its derivative added is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of hydrogenated block copolymer (a) and (b). The reaction temperature for graft modification is preferably 100 to 300°C, and more preferably 120 to 280°C. The method for graft modification is not particularly limited, but for example, the method described in Japanese Patent Publication No. 62-79211 can be applied.

[0055] [Hydrogenation reaction process] The hydrogenated block copolymers (a) and (b) used in the laminate of this embodiment are obtained by subjecting the non-hydrogenated, unmodified or modified block copolymer, as described above, to a hydrogenation reaction using a predetermined hydrogenation catalyst. Examples of hydrogenation catalysts include, but are not limited to, the following: (1) supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc.; (2) so-called Ziegler-type hydrogenation catalysts using organic acid salts of Ni, Co, Fe, Cr, etc. or transition metal salts such as acetylacetone salts and reducing agents such as organoaluminum; and (3) homogeneous hydrogenation catalysts such as so-called organometallic complexes such as organometallic compounds of Ti, Ru, Rh, and Zr. Furthermore, while not limited to the following, hydrogenated catalysts can also be used, for example, those described in Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-37970, Japanese Patent Publication No. 1-53851, and Japanese Patent Publication No. 2-9041. Suitable hydrogenation catalysts include titanocene compounds, reducing organometallic compounds, or mixtures thereof. The titanocene compounds are not limited to those listed below, but for example, compounds described in Japanese Patent Publication No. 8-109219 can be used. Specifically, examples include compounds having at least one ligand with a (substituted) cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Reducing organometallic compounds include, but are not limited to, organolithium and other organoalkali metal compounds, organomagnesium compounds, organoaluminum compounds, organoboron compounds, or organozinc compounds.

[0056] Let's explain hydrogenation reactions. The reaction temperature is generally preferably in the range of 0 to 200°C, and more preferably in the range of 30 to 150°C. The hydrogen pressure used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and even more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually preferably 3 minutes to 10 hours, and more preferably 10 minutes to 5 hours. The hydrogenation reaction may be carried out as a batch process, a continuous process, or a combination of both. It is preferable to remove catalyst residue from the solution of the hydrogenated block copolymer obtained via the hydrogenation reaction, as needed, and separate the hydrogenated block copolymer from the solution. The separation method is not limited to the following, but examples include: adding a polar solvent that is a poor solvent for hydrogenation-modified copolymers, such as acetone or alcohol, to the reaction solution after hydrogenation to precipitate and recover the polymer; immersing the reaction solution in hot water under stirring and removing the solvent by steam stripping to recover the polymer; or directly heating the polymer solution to remove the solvent by distillation.

[0057] Furthermore, the hydrogenated block copolymers (a) and (b) used in the laminate of this embodiment may be supplemented with various stabilizers such as phenolic stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers, and amine-based stabilizers.

[0058] <Olefin resin (c-1)> The hydrogenated block copolymer composition constituting the laminate of this embodiment contains an olefin resin (c-1). The olefin resin (c-1) used in the laminate of this embodiment is not limited to the following, but examples include homopolymers of α-olefins such as polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, and 1-octene. In addition, random copolymers or block copolymers consisting of combinations of olefins selected from ethylene, propylene, butene, pentene, hexene, octene, etc. are also included. Specifically, examples include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, propylene-1-hexene-ethylene copolymer, and propylene-1-octene-ethylene copolymer, as well as ethylene and / or propylene-α-olefin copolymers. Furthermore, copolymers with ethylene and / or propylene also include copolymers with other unsaturated monomers other than the α-olefins mentioned above. The copolymers with the aforementioned other unsaturated monomers are not limited to the following, but include, for example, copolymers of ethylene and / or propylene with unsaturated organic acids or their derivatives such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, arylmaleimide, and alkylmaleimide; copolymers of ethylene and / or propylene with vinyl esters such as vinyl acetate; and further, copolymers of ethylene and / or propylene with non-conjugated dienes such as dicyclopentadiene, 4-ethylidene-2-norbornene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. From the viewpoint of economic efficiency and ensuring good compatibility in the hydrogenated block copolymer composition constituting the foam of this embodiment, the olefin resin (c-1) preferably contains at least one type of polypropylene resin.

[0059] Furthermore, the olefin resin (c-1) may be modified with a predetermined functional group. The functional groups are not particularly limited, but examples include epoxy groups, carboxyl groups, acid anhydride groups, hydroxyl groups, and the like. The following compounds are examples of functional group-containing compounds or modifiers used to modify olefin resins (c-1), although they are not particularly limited. Examples include unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether, as well as unsaturated organic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, and itaconic anhydride. Other examples, though not particularly limited, include ionomers and chlorinated polyolefins.

[0060] From the viewpoint of economic efficiency and ensuring good compatibility in the hydrogenated block copolymer composition constituting the laminate of this embodiment, the olefin resin (c-1) is preferably a polypropylene resin such as a polypropylene homopolymer, ethylene-propylene random copolymer, or block copolymer. The olefin resin (c-1) may consist of only one type of material, or it may be a combination of two or more types.

[0061] <Thermoplastic resin (d)> The hydrogenated block copolymer composition constituting the laminate of this embodiment contains a thermoplastic resin (d). Examples of thermoplastic resin (d) include, but are not limited to, block copolymers of conjugated diene compounds and vinyl aromatic compounds and their hydrogenated products (however, different from the hydrogenated block copolymers (a) and (b) described above), polymers of the vinyl aromatic compounds, copolymer resins of the vinyl aromatic compounds with other vinyl monomers, such as ethylene, propylene, butylene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid esters such as acrylic acid and methyl acrylate, methacrylic acid esters such as methacrylic acid and methyl methacrylate, copolymer resins with acrylonitrile, methacrylonitrile, etc., rubber-modified styrene resins (HIPS), acrylonitrile-butadiene-styrene copolymer resins (ABS), methacrylic acid ester-butadiene-styrene copolymer resins (MBS), and the like.

[0062] Furthermore, thermoplastic resins (d) include, for example, polymers of acrylic acid and its esters or amides, polyacrylate resins, polymers of acrylonitrile and / or methacrylonitrile, nitrile resins which are copolymers of these acrylonitrile monomers with other copolymerizable monomers containing 50% by mass or more, polyamide resins such as nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, nylon-6·nylon-12 copolymer, polyester resins, thermoplastic polyurethane resins, and poly-4,4'-dioxydiphenyl-2,2'-propane. Examples include polycarbonate polymers such as polycarbonates, thermoplastic polysulfones such as polyethersulfone and polyallylsulfone, polyoxymethylene resins, polyphenylene ether resins such as poly(2,6-dimethyl-1,4-phenylene) ether, polyphenylene sulfide resins such as polyphenylene sulfide and poly4,4'-diphenylene sulfide, polyarylate resins, polyetherketone polymers or copolymers, polyketone resins, fluorine resins, polyoxybenzoyl polymers, polyimide resins, and polybutadiene resins such as 1,2-polybutadiene and transpolybutadiene.

[0063] Of these thermoplastic resins (d), styrene-based resins such as polystyrene and rubber-modified styrene-based resins, polyamide-based resins, polyester-based resins, and polycarbonate-based resins are particularly preferred. The number-average molecular weight of these thermoplastic resins (d) is generally 1000 or more, preferably 5000 to 5 million, and more preferably 10,000 to 1 million.

[0064] <Softener (e)> The hydrogenated block copolymer composition constituting the laminate of this embodiment contains a softening agent (e). The softener (e) is preferably a rubber softener that softens the hydrogenated block copolymer composition and imparts processability. Examples of rubber softeners include, but are not limited to, mineral oils and liquid or low molecular weight synthetic softeners, with naphthenic and / or paraffinic process oils or extender oils being preferred. Mineral oil-based rubber softeners are mixtures of aromatic rings, naphthenic rings, and paraffinic chains. Those in which the number of carbon atoms in the paraffinic chain accounts for 50% or more of the total carbon atoms are called paraffinic, those in which the number of carbon atoms in the naphthenic ring accounts for 30-45% are called naphthenic, and those in which the number of aromatic carbon atoms exceeds 30% are called aromatic. The hydrogenated block copolymer composition constituting the laminate of this embodiment may use a synthetic softener (e) as the softener, and is not limited to the following, but for example, polybutene, low molecular weight polybutadiene, liquid paraffin, etc. can be used. Among these, the above-mentioned mineral oil-based rubber softener is preferred.

[0065] When high heat resistance and mechanical properties are required for the hydrogenated block copolymer composition constituting the laminate of this embodiment, the mineral oil-based rubber softener used preferably has a kinematic viscosity at 40°C of 60 cst or more, and more preferably 120 cst or more. Rubber softeners may be used individually or in combination of two or more types.

[0066] <Content of components (a) to (e) in the hydrogenated block copolymer composition> The content of components (a) to (e) in the hydrogenated block copolymer composition constituting the laminate of this embodiment is described below. The total content of hydrogenated block copolymers (a) and (b) is 3% by mass or more and 95% by mass or less, preferably 5% by mass or more and 70% by mass or less, more preferably 7% by mass or more and 60% by mass or less, and even more preferably 9% by mass or more and 50% by mass or less. When the total content of hydrogenated block copolymers (a) and (b) in the hydrogenated block copolymer composition is within the above range, there is a tendency to obtain improved heat insulation, excellent moldability, and wear resistance. The content of olefin resin (c-1) is 1% by mass or more and 42% by mass or less, preferably 3% by mass or more and 38% by mass or less, more preferably 6% by mass or more and 34% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less. When the olefin resin (c-1) content falls within the above range, a good balance between flexibility and heat resistance tends to be achieved. The content of thermoplastic resin (d) is 1% by mass or more and 60% by mass or less, preferably 3% by mass or more and 50% by mass or less, more preferably 6% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 30% by mass or less. When the content of thermoplastic resin (d) is within the above range, there is a tendency for a good balance of flexibility, moldability, and toughness to be achieved. The content of softener (e) is 1% by mass or more and 65% by mass or less, preferably 5% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 55% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less. When the content of softener (e) is within the above range, a good balance between foaming properties, flexibility, and moldability tends to be achieved.

[0067] <Additives> In addition to components (a), (b), (c-1), (d), and (e) mentioned above, any additives may be added to the hydrogenated block copolymer composition constituting the laminate of this embodiment as needed. There are no particular restrictions on the type of additive, as long as it is one that is commonly used in the formulation of thermoplastic resins and rubbery polymers. As additives, there are no particular restrictions as long as they are commonly used in the formulation of thermoplastic resins and rubbery polymers, such as fillers, lubricants, release agents, plasticizers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, flame retardants, antistatic agents, reinforcing agents, and colorants.

[0068] Examples of fillers include, but are not limited to, inorganic fillers such as silica, talc, mica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate, and barium sulfate, as well as organic fillers such as carbon black. Examples of lubricants, though not limited to the following, include stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylenebisstearoamide. Examples of plasticizers include, but are not limited to, organic polysiloxanes and mineral oil. Antioxidants include, but are not limited to, hindered phenol antioxidants. Examples of heat stabilizers include, but are not limited to, phosphorus-based, sulfur-based, and amine-based heat stabilizers. Examples of light stabilizers include, but are not limited to, hindered amine-based light stabilizers. Examples of UV absorbers include, but are not limited to, benzotriazole-based UV absorbers. Examples of reinforcing agents include, but are not limited to, organic fibers, glass fibers, carbon fibers, and metal whiskers. Examples of colorants include, but are not limited to, titanium dioxide, iron oxide, and carbon black. Other examples include those listed in "Rubber and Plastic Compounding Chemicals" (edited by Rubber Digest Co., Ltd.).

[0069] (Method for producing hydrogenated block copolymer composition) The hydrogenated block copolymer composition constituting the laminate of this embodiment can be produced by conventionally known methods. The method for producing the thermoplastic composition of this embodiment is not limited to the following, but for example, a method of melt-kneading each component (hydrogenated block copolymer (a) and (b), olefin resin (c-1), thermoplastic resin (d), softener (e), and other additives as needed) using a mixer such as a Banbury mixer, single-screw extruder, twin-screw extruder, Conida, or multi-screw extruder, or a method of dissolving or dispersing each component and then heating to remove the solvent may be used. In particular, the melt-kneading method using an extruder is preferred from the viewpoint of productivity and good kneading performance. The shape of the hydrogenated block copolymer composition is not limited to the following, but can be any shape, such as pellets, sheets, strands, or chips. Alternatively, molded articles may be produced directly after melt kneading. The hydrogenated block copolymer composition described in this embodiment may be foamed after injection molding using conventionally known techniques such as the core-back method.

[0070] (Olefin resin for base materials (c-2)) The laminate of this embodiment is a laminate of the above-described hydrogenated block copolymer composition and an olefin resin (c-2) for the base material. The olefin resin (c-2) for the substrate used in the laminate of this embodiment is not limited to the following, but examples include homopolymers of α-olefins such as polyethylene (PE), polypropylene (PP), 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, and 1-octene. Other examples include random copolymers or block copolymers made of combinations of olefins selected from ethylene, propylene, butene, pentene, hexene, octene, etc. Specifically, examples include ethylene-propylene copolymer, ethylene-1-butene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-4-methyl-1-pentene copolymer, ethylene-propylene-1-butene copolymer, propylene-1-hexene-ethylene copolymer, and propylene-1-octene-ethylene copolymer, as well as ethylene and / or propylene-α-olefin copolymers. Furthermore, copolymers with ethylene and / or propylene also include copolymers with other unsaturated monomers other than the α-olefins mentioned above. The copolymers with the aforementioned other unsaturated monomers are not limited to the following, but include, for example, copolymers of ethylene and / or propylene with unsaturated organic acids or their derivatives such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, methyl acrylate, methyl methacrylate, maleic anhydride, arylmaleimide, and alkylmaleimide; copolymers of ethylene and / or propylene with vinyl esters such as vinyl acetate; and further, copolymers of ethylene and / or propylene with non-conjugated dienes such as dicyclopentadiene, 4-ethylidene-2-norbornene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. From an economic standpoint, the olefin resin (c-2) for the base material preferably contains at least one type of polypropylene resin.

[0071] Furthermore, the olefin resin (c-2) may be modified with a predetermined functional group. The functional groups are not particularly limited, but examples include epoxy groups, carboxyl groups, acid anhydride groups, hydroxyl groups, and the like. The following compounds are examples of functional group-containing compounds or modifiers used to modify olefin resins (c-2), although they are not particularly limited. Examples include unsaturated epoxides such as glycidyl methacrylate, glycidyl acrylate, vinyl glycidyl ether, and allyl glycidyl ether, as well as unsaturated organic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, allyl succinic acid, maleic anhydride, fumaric anhydride, and itaconic anhydride. Other examples, though not particularly limited, include ionomers and chlorinated polyolefins.

[0072] The olefin resin for the base material (c-2) may contain inorganic and organic fillers to increase rigidity. Examples of inorganic and organic fillers, though not limited to those listed below, include glass fibers, talc, calcium carbonate, mica, carbon black, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, silica, titanium dioxide, wood powder, polyamide fibers, and cellulose nanofibers. Glass fibers and talc are preferred because they exhibit high reinforcing effects due to their high rigidity and high aspect ratio.

[0073] (Applications of laminates) The laminate of this embodiment can be used, for example, in automotive parts, food packaging materials, medical devices, home appliance components, electronic device components, building materials, industrial parts, household goods, toy materials, footwear materials, textile materials, and the like. Examples of automotive parts include, but are not limited to, side moldings, grommets, shift knobs, weatherstrips, window frames and their sealing materials, instrument panels, assist grips, steering wheels, shift levers, consoles, armrests, headrests, and door panels. Examples of medical devices include, but are not limited to, medical tubes, medical hoses, catheters, blood bags, infusion bags, platelet storage bags, and hemodialysis bags. Building materials include, but are not limited to, wall materials, floor materials, etc. Other examples, though not particularly limited, include industrial hoses, food hoses, vacuum cleaner hoses, electric cooling packings, various covering materials for electric wires and other applications, grip covering materials, and soft dolls. The laminate of this embodiment may be subjected to processes such as foaming, powdering, stretching, bonding, printing, painting, and plating as appropriate.

[0074] (Method of manufacturing a laminate) The laminate of this embodiment is manufactured by laminating the above-described hydrogenated block copolymer composition onto an olefin resin (c-2) for the base material, which has been pre-installed in the mold of an injection molding machine, and then performing injection molding. The temperature of the olefin resin (c-2) for the base material is preferably 20°C to 60°C, more preferably 25°C to 50°C, and even more preferably 30°C to 40°C. When the temperature of the olefin resin (c-2) for the base material is 60°C or lower, the mold release properties tend to be good. When the temperature of the olefin resin (c-2) for the base material is 20°C or higher, the adhesive strength between the olefin resin (c-2) for the base material and the hydrogenated block copolymer composition tends to be excellent. Furthermore, the injection temperature of the hydrogenated block copolymer composition is preferably 180°C to 260°C, more preferably 190°C to 250°C, and even more preferably 200°C to 240°C. When the injection temperature of the hydrogenated block copolymer composition is 180°C or higher, excellent adhesive strength tends to be obtained between the olefin resin (c-2) for the substrate and the hydrogenated block copolymer composition. When the injection temperature of the hydrogenated block copolymer composition is 260°C or lower, degradation of the hydrogenated block copolymer composition can be prevented.

[0075] (Methods for reusing laminated materials) The laminate of the hydrogenated block copolymer composition of this embodiment and the polyolefin resin (c-2) for the base material described above can be mechanically crushed and reused. The crushed laminate can be reused by melt-kneading it again to form pellets. Alternatively, the crushed laminate may be used in addition to polypropylene, polyethylene, polymethyl methacrylate, polyacrylonitrile, polymethacrylonitrile rubber-modified styrene resin (HIPS), acrylonitrile-butadiene-styrene copolymer resin (ABS), and methacrylate ester-butadiene-styrene copolymer resin (MBS). Polypropylene and polyethylene are particularly preferred. Examples of materials that can be reused after crushing include automotive parts (automotive interior materials, automotive exterior materials), medical device materials, various containers such as food packaging containers, home appliances, industrial parts, and toys. [Examples]

[0076] 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. The methods for measuring and evaluating the physical properties applied to the examples and comparative examples are described below.

[0077] The hydrogenated block copolymer (a) and hydrogenated block copolymer (b), which are components of the hydrogenated block copolymer compositions used in the laminates of the examples and comparative examples, were structurally identified and their physical properties were measured as follows.

[0078] [Method for measuring the structure of hydrogenated block copolymers] ((1) Content of total vinyl aromatic monomer units (styrene) in hydrogenated block copolymers (a) and (b)) Using hydrogenated block copolymers, the total vinyl aromatic monomer (styrene) content was measured using an ultraviolet spectrophotometer (Shimadzu Corporation, UV-2450).

[0079] ((2) Hydrogenation rate of double bonds in the conjugated diene monomer units of hydrogenated block copolymers (a) and (b)) Using hydrogenated block copolymers, the hydrogenation rate of double bonds in conjugated diene monomer units was measured using a nuclear magnetic resonance spectrometer (ECS400, JEOL RESONANCE).

[0080] ((3) Content of polymer block A2 in hydrogenated block copolymer (a)) Using hydrogenated block copolymers, the content of polymer block A2, which mainly consists of vinyl aromatic monomer units, was measured using nuclear magnetic resonance (NMR) spectroscopy (as described in Y. Tanaka, et al., RUBBER CHEMISTRY and TECHNOLOGY 54, 685 (1981); hereafter referred to as "NMR method").

[0081] (4) Content of hydrogenated copolymer blocks A1 and B1 in hydrogenated block copolymers (a) and (b) The content of hydrogenated copolymer block A1 is, The calculation was performed using the formula: 100 - (Content of hydrogenated copolymer block A2 in hydrogenated block copolymer (a)). The content of hydrogenated copolymer block B1 is, The calculation was performed using the formula: 100 - (Content of hydrogenated copolymer block B2 in hydrogenated block copolymer (b) + polymer block B3). Note that B3 was calculated using the same method as A2. The content of B2 was calculated from the monomer feed composition of the polymerization process.

[0082] ((5) Amount of vinyl bond in hydrogenated copolymer block (B2)) Using hydrogenated block copolymer (b), the amount of vinyl bonds in hydrogenated copolymer block (B2), which mainly consists of conjugated diene monomer units, was measured using nuclear magnetic resonance (NMR). The amount of vinyl bonds in the conjugated diene monomer units of hydrogenated copolymer block (B2) in hydrogenated block copolymer (b) was determined by the ratio of the total area of ​​1,2-bonds and 3,4-bonds to the total area of ​​all peaks related to conjugated diene monomer units (proportion of 1,2-bonds and 3,4-bonds, and 1,4-bonds) obtained by NMR measurement.

[0083] ((6) Content of vinyl aromatic monomer units in hydrogenated copolymer blocks A1 and B1 constituting hydrogenated block copolymers (a) and (b)) The vinyl aromatic monomer unit content in hydrogenated copolymer blocks A1 and B1 relative to the total hydrogenated copolymers (a) and (b) was calculated from the difference between the total vinyl aromatic monomer unit content in hydrogenated block copolymers (a) and (b) measured in (1) above and the content of polymer blocks (A2) and (B3) mainly composed of vinyl aromatic monomer units in hydrogenated block copolymers (a) and (b) measured in (3) above. Furthermore, the vinyl aromatic monomer unit content in hydrogenated copolymer blocks (A1) and (B1) was calculated from the ratio of the content of hydrogenated copolymer blocks (A1) and (B1) in hydrogenated block copolymers (a) and (b) measured in (4) above. Furthermore, polymer block (B2) was defined as having a conjugated diene monomer unit content of 100% by mass.

[0084] [Method for measuring the physical properties of hydrogenated block copolymer compositions] The hydrogenated block copolymer compositions used in the laminates of the examples and comparative examples were subjected to the following physical property measurements.

[0085] ((1) Adhesion strength between hydrogenated block copolymer composition and polyolefin resin for substrate (c-2)) The adhesive strength between the hydrogenated block copolymer composition and the polyolefin resin (c-2) for the substrate was measured by a 90-degree peel test using the laminates of the examples and comparative examples. A 10 mm wide cut was made on the side of the laminate facing the hydrogenated block copolymer composition, and several centimeters of the end of the cut were peeled off beforehand. At the peeled portion, the layer made of the hydrogenated block copolymer composition and the layer made of the base material polyolefin resin (c-2) were separately fixed to the chuck of a tensile testing machine [MinebeaMitsumi Inc., TGE-500N (product name)]. A layer consisting of a hydrogenated block copolymer composition and a layer consisting of a base polyolefin resin (c-2) were separated by pulling them at 300 mm / min in a 90° direction. The tensile force applied during separation was defined as the adhesive strength (N / cm) of the laminate between the hydrogenated block copolymer composition and the base polyolefin resin (c-2), and was evaluated according to the following evaluation criteria. A result of ○ was considered a pass. <Adhesive Strength Evaluation Criteria> 〇:20N / cm or more ×: Less than 20 N / cm

[0086] ((2) Abrasion resistance of hydrogenated block copolymer composition) Using a JSPS-type friction tester (AB-301, manufactured by Tester Industries Co., Ltd.), the textured surface of the laminate obtained by injection molding was rubbed with Kanakin No. 3 cotton friction cloth under a load of 500g. The abrasion resistance was evaluated according to the following criteria based on the amount of mass loss after friction, with a score of △ or higher being considered acceptable. <Evaluation Criteria> ○: Mass loss is less than 50 mg after 1000 friction cycles. △: After 1000 friction cycles, the mass loss is between 50 mg and 150 mg. ×: After 1000 friction cycles, the mass loss is between 150 mg and 250 mg.

[0087] (3) Tensile strength of hydrogenated block copolymer composition In accordance with JIS K6251, tensile tests were conducted using a tensile testing machine (Minebea, TG-5kN) at 23°C, with a No. 3 dumbbell and a crosshead speed of 500 mm / min. The tensile strength was evaluated according to the following criteria, with a score of △ or higher being considered acceptable. <Evaluation Criteria> ○: Tensile strength of 10 MPa or more △: Tensile strength between 7 MPa and less than 10 MPa ×: Tensile strength less than 7 MPa

[0088] [Production of hydrogenated block copolymers (a) and (b) constituting the hydrogenated block copolymer composition] (Preparation of hydrogenated catalyst) In the examples and comparative examples described later, the hydrogenation catalysts used to produce hydrogenated block copolymers (a) and (b) were prepared by the following method. A reaction vessel equipped with a stirring device was purged with nitrogen, and 1 liter of dried and purified cyclohexane was charged into it. Next, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added. While stirring thoroughly, an n-hexane solution containing 200 mmol of trimethylaluminum was added, and the mixture was reacted at room temperature for approximately 3 days. This yielded a hydrogenation catalyst.

[0089] (Manufacturing Example 1: Hydrogenated Block Copolymer (a)-1) Batch polymerization was carried out using a tank-type reactor (internal volume 10L) equipped with a stirring device and jacket. First, a cyclohexane solution (20% by mass concentration) containing 15 parts by mass of styrene was added. Next, 0.107 parts by mass of n-butyllithium were added per 100 parts by mass of the total monomer, and 0.9 moles of N,N,N',N'-tetramethylethylenediamine (hereinafter referred to as "TMEDA") were added per mole of n-butyllithium, and polymerization was carried out at 65°C for 1 hour. Next, a cyclohexane solution (20% by mass) containing 29 parts by mass of butadiene and 41 parts by mass of styrene was added, and polymerization was carried out at 80°C for 2 hours. Finally, a cyclohexane solution (20% by mass) containing 15 parts by mass of styrene was added, and polymerization was carried out at 65°C for 1 hour. After that, methanol was added to stop the polymerization reaction. The block copolymer obtained as described above had a styrene content of 71% by mass, a polystyrene block content of 30% by mass, a vinyl bond content of 22% by mass, and a weight-average molecular weight of 60,000. Furthermore, the hydrogenation catalyst prepared as described above was added to the obtained block copolymer at a concentration of 100 ppm (Ti-based) per 100 parts by mass of the block copolymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.7 MPa and a temperature of 65°C. Next, 0.3 parts by mass of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as a stabilizer to 100 parts by mass of the block copolymer to obtain hydrogenated block copolymer (a)-1. The hydrogenation rate of the obtained hydrogenated block copolymer (a)-1 was 98%. Other physical properties are shown in Table 1.

[0090] (Manufacturing Example 2: Hydrogenated Block Copolymer (b-1)) Hydrogenated block copolymer (b)-1 was prepared by adjusting the polymerization method and hydrogenation conditions in the method for producing hydrogenated block copolymer (a)-1 described above. The physical properties of these copolymers are shown in Table 2 below.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Production of Hydrogenated Block Copolymer Compositions] A hydrogenated block copolymer composition was prepared using the above-mentioned hydrogenated block copolymer (a-1), hydrogenated block copolymer (b-1), and the following components (c-1), (d), and (e).

[0094] (Olefin resin (c-1)) <Component (c-1)> Olefin-based resin: Polypropylene resin, PM801A (manufactured by Sun Allomer Co., Ltd.)

[0095] (Thermoplastic resin (d)) <Ingredient (d)> Thermoplastic resin: Styrene-based thermoplastic elastomer, N504 (manufactured by Nippon Elastomer Co., Ltd.)

[0096] (Softener (e)) <Ingredient (e)> Softener: Paraffin oil, PW-90 (manufactured by Idemitsu Kosan Co., Ltd.)

[0097] [Production of hydrogenated block copolymer compositions and laminates] (Example 1) <Manufacturing of Hydrogenated Block Copolymer Compositions> A hydrogenated block copolymer composition was obtained by blending pelletized hydrogenated block copolymer (a)-1, hydrogenated block copolymer (b)-1, olefin resin (c-1), thermoplastic resin (d), and softener (e) in the proportions (parts by mass) shown in Table 3 below, kneading them in a twin-screw extruder (TEX-30), and pelletizing them. The extrusion conditions were a cylinder temperature of 230°C and a screw rotation speed of 300 rpm. Using the obtained hydrogenated block copolymer composition, a 2 mm thick injection-molded sheet was laminated onto a polyolefin resin (containing 90% polypropylene and 10% talc) for the base material under the temperature conditions described in Table 3, thereby obtaining physical property measurement pieces for the adhesive strength between the hydrogenated block copolymer composition and the polyolefin resin (c-2). Furthermore, the obtained hydrogenated block copolymer composition was injection-molded to produce a 2 mm thick injection-molded sheet, and physical property measurement specimens for abrasion resistance and tensile testing of the hydrogenated block copolymer composition were obtained. The results of the physical property measurements are shown in Table 3.

[0098] (Examples 2-4, Comparative Examples 1-3, Reference Example 1) <Manufacturing of Hydrogenated Block Copolymer Compositions> A hydrogenated block copolymer composition was prepared in the same manner as in Example 1, except that each component was changed as shown in Table 3, and its physical properties were measured. The results of the physical property measurements are shown in Table 3.

[0099] (See example 2) <Manufacturing of Hydrogenated Block Copolymer Compositions> Reference Example 2, shown in Table 3, is a hydrogenated block copolymer composition with the same formulation as in Example 1, obtained by repeating the extrusion conditions described above for 3 cycles. Even after repeated extrusion, the physical properties of the hydrogenated block copolymer were equivalent to those of Example 1. This indicates that the hydrogenated block copolymer composition alone and the laminate containing the polyolefin resin (c-2) for the base material have a high potential for recycling.

[0100] (See example 3) <Preparation of mixed composition A> A laminate containing the hydrogenated block copolymer composition obtained in Example 1 (described later) and a polyolefin resin for the base material (containing 90% polypropylene and 10% talc) was pulverized. The mass ratio of the hydrogenated block copolymer composition to the polyolefin resin for the base material constituting the laminate was 1:1.3. The pulverized sample was kneaded and pelletized using a twin-screw extruder (TEX-30) to obtain a mixed composition A of the hydrogenated block copolymer composition alone and the polyolefin resin for the base material (containing 90% polypropylene and 10% talc). The extrusion conditions were a cylinder temperature of 230°C and a screw rotation speed of 300 rpm. The physical property measurements revealed that the breaking strength in the tensile test was 16 MPa, the elongation at break was 360%, and the tensile modulus was 770 MPa. This indicates that it is more flexible and exhibits greater elongation compared to the polyolefin resin used as a base material, as shown in Reference Example 6.

[0101] (See example 4) <Manufacturing of mixed composition B> Furthermore, mixed composition B was obtained by mixing mixed composition A, obtained in the above-mentioned (Reference Example 3), with a base material polyolefin resin (containing 90% polypropylene and 10% talc) in a mass ratio of mixed composition A:base material polyolefin resin = 7:3, and then kneading and pelletizing the mixture using a twin-screw extruder (TEX-30). The physical property measurements revealed that the breaking strength in the tensile test was 17 MPa, the elongation at break was 330%, and the tensile modulus was 1040 MPa. This indicates that it is more flexible and exhibits greater elongation compared to the polyolefin resin used as a base material shown in Reference Example 6.

[0102] (See example 5) <Production of mixed composition C> Furthermore, mixed composition A and a base material polyolefin resin (containing 90% polypropylene and 10% talc) were mixed in a ratio of mixed composition A to base material polyolefin resin of 3:7 (by mass), and the mixture was kneaded and pelletized using a twin-screw extruder (TEX-30) to obtain mixed composition C. The physical property measurements revealed that the breaking strength in the tensile test was 17 MPa, the elongation at break was 80%, and the tensile modulus was 1560 MPa. This indicates that it is more flexible and exhibits greater elongation compared to the polyolefin resin used as a base material, as shown in Reference Example 6.

[0103] It was found that materials obtained by crushing and repelling a laminate containing a hydrogenated block copolymer composition and a polyolefin resin (c-2) for the base material have potential applications in fields such as automotive parts (automotive interior materials, automotive exterior materials), medical device materials, various containers such as food packaging containers, home appliances, industrial parts, and toys.

[0104] [Manufacturing of laminates] (Examples 1-4, Comparative Examples 1-3, Reference Examples 1-2) With the mold temperature controlled to 40°C, a pre-molded injection-molded body of the base polyolefin resin (c-2) was placed inside, and the hydrogenated block copolymer composition was injection-molded by insert molding at a nozzle temperature of 220°C to obtain a laminate of the base polyolefin resin (c-1) and the hydrogenated block copolymer composition. The resulting laminate showed that the hydrogenated block copolymer composition on the surface exhibited excellent abrasion resistance and tensile strength, and that the adhesive strength between the hydrogenated block copolymer composition and the polyolefin resin (c-2) for the substrate was good.

[0105] [Table 3]

[0106] [Table 4] [Industrial applicability]

[0107] The laminate of the present invention has industrial applicability in fields such as automotive parts (automotive interior materials, automotive exterior materials), medical device materials, various containers such as food packaging containers, home appliances, industrial parts, and toys.

Claims

1. At least two types of hydrogenated block copolymers (a) and hydrogenated block copolymers (b), Olefin resin (c-1), Thermoplastic resin (d) and Softener (e), A hydrogenated block copolymer composition containing, Olefin resin for base material (c-2), It is a laminated body, A laminate that satisfies the following conditions (1) to (6). <Condition (1)>: The hydrogenated block copolymer (a) and the hydrogenated block copolymer (b) are hydrogenated products of block copolymers containing vinyl aromatic monomer units and conjugated diene monomer units. <Condition (2)>: The hydrogenated block copolymer (a) comprises a hydrogenated copolymer block (A1) and a hydrogenated copolymer block (A2), wherein the hydrogenated copolymer block (A1) consists of vinyl aromatic monomer units and conjugated diene monomer units, with a vinyl aromatic monomer unit content of 40 to 80% by mass, and the hydrogenated copolymer block (A2) mainly consists of vinyl aromatic monomer units, with a hydrogenated copolymer block (A2) content of 15% by mass or more and 35% by mass or less in the hydrogenated block copolymer (a). <Condition (3)>: The hydrogenated block copolymer (b) comprises a hydrogenated copolymer block (B1) and a hydrogenated copolymer block (B2). The hydrogenated copolymer block (B1) consists of vinyl aromatic monomer units and conjugated diene monomer units, with a vinyl aromatic monomer unit content of 20 to 60% by mass. The hydrogenated copolymer block (B2) mainly consists of conjugated diene monomer units, and the content of the hydrogenated copolymer block (B2) in the hydrogenated block copolymer (b) is 10% by mass or more and 60% by mass or less. The hydrogenated copolymer block (b) also contains a polymer block (B3) mainly consisting of at least one vinyl aromatic monomer unit. <Condition (4)>: The hydrogenated block copolymer (a) has a total vinyl aromatic monomer unit content of 40 to 80% by mass, and the hydrogenated block copolymer (b) has a total vinyl aromatic monomer unit content of 15 to 45% by mass. <Condition (5)>: The mass ratio (a) / (b) of the content of hydrogenated copolymer block (a) to the content of hydrogenated copolymer block (b) in the hydrogenated block copolymer composition is 50 / 50 to 90 / 10. <Condition (6)>: The content of components (a) to (e) in the hydrogenated block copolymer composition is as follows. Total content of hydrogenated block copolymer (a) and hydrogenated block copolymer (b): 3% by mass or more and 95% by mass or less Olefin resin (c-1): 1% by mass or more and 42% by mass or less Thermoplastic resin (d): 1% by mass 60% by mass or less Softener (e): 1% by mass or more and 65% by mass or less

2. The amount of vinyl bond in the hydrogenated copolymer block (B2) is 40 to 85% by mass. The laminate according to claim 1.

3. The olefin resin (c-1) includes at least one type of polypropylene resin. The laminate according to claim 1.

4. The aforementioned laminate, Laminates for automotive parts applications, selected from the group consisting of side moldings, grommets, shift knobs, weatherstrips, window frames and their sealing materials, instrument panels, assist grips, steering wheels, shift levers, consoles, armrests, headrests, and door panels. The laminate according to claim 1.

5. A method for manufacturing a laminate according to any one of claims 1 to 4, The olefin resin (c-2) for the base material is placed in the mold of the injection molding machine, and then the hydrogenated block copolymer composition is laminated and injection molding is performed. A method for manufacturing laminates.

6. The process involves laminating the hydrogenated block copolymer composition onto the olefin resin (c-2) for the base material and then performing injection molding. The process is carried out with the temperature of the olefin resin used as the base material, which is placed inside the mold of the injection molding machine, set to 60°C or lower. A method for manufacturing a laminate according to claim 5.

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