Laminate

Abstract

This laminate comprises a substrate (X) and an adhesive layer (Y) that is adjacent to the substrate (X), wherein the substrate (X) includes rubber, and the adhesive layer (Y) includes a hydrogenated block copolymer (A) obtained by hydrogenating a block copolymer (P) containing a polymer block (a) which contains a structural unit derived from an aromatic vinyl compound and a polymer block (b) which contains a structural unit derived from a conjugated diene compound.

Description

Laminate

[0001] This invention relates to a laminate.

[0002] Generally, rubber is a material with high elongation and high modulus of elasticity, and in order to take advantage of these characteristics and make it practical, it is often laminated with other materials to form a laminate. In order to fully exhibit the excellent physical properties of rubber, it is necessary to firmly bond the rubber to the other materials. However, because rubber is a low surface energy material, the adhesive strength between rubber and the general adhesives and sealants used when forming laminates is weak. For this reason, methods to improve the adhesive strength between adhesives and sealants and rubber have been investigated. For example, Patent Document 1 describes a molded rubber product laminated with an adhesive having a primer, and it is stated that this molded rubber product can be bonded to parts such as automobiles, refrigerators, and door frames.

[0003] Special Publication No. 2001-525481

[0004] Conventionally, acrylic foam tape has been used to laminate a rubber-containing substrate with other materials such as plastics to form a laminate. However, due to poor adhesion between the acrylic foam tape and the rubber-containing substrate, it was necessary to surface treat the substrate, such as applying a primer, before bonding the acrylic foam tape. However, the above method is complicated and the adhesive strength is insufficient, so improvement has been sought. The present invention has been made in view of the above circumstances and aims to provide a laminate that exhibits excellent adhesion between the rubber-containing substrate and the adhesive layer without requiring a primer treatment on the surface of the substrate.

[0005] As a result of diligent research by the inventors, we discovered that the above problem can be solved by having a specific hydrogenated block copolymer in the adhesive layer, leading to the present invention.

[0006] In other words, the present invention is as follows: [1] A laminate having a base material (X) and an adhesive layer (Y) adjacent to the base material (X), wherein the base material (X) contains rubber, and the adhesive layer (Y) contains a hydrogenated block copolymer (A) obtained by hydrogenating a block copolymer (P) which includes a polymer block (a) containing structural units derived from an aromatic vinyl compound and a polymer block (b) containing structural units derived from a conjugated diene compound. [2] The laminate according to [1], having a base material (X), the adhesive layer (Y), and a base material (Z) containing a polar resin in this order. [3] The laminate according to [1] or [2], wherein the rubber contains crosslinked rubber. [4] The laminate according to [3], wherein the content of the crosslinked rubber in 100% by mass of the base material (X) is 10 to 100% by mass. [5] The laminate according to any one of [1] to [4], wherein the rubber contains ethylene propylene rubber. [6] The laminate according to any one of [1] to [5], wherein the conjugated diene compound is at least one selected from butadiene and isoprene. [7] The laminate according to any one of [1] to [6], wherein the content of the hydrogenated block copolymer (A) in 100% by mass of the adhesive layer (Y) is 25 to 100% by mass. [8] The laminate according to any one of [1] to [7], wherein the hydrogenation rate of the carbon-carbon double bond in the polymer block (b) is 50 to 100 mol%. [9] The laminate according to any one of [1] to [8], wherein the weight-average molecular weight (Mw) of the hydrogenated block copolymer (A) is 40,000 to 500,000.

[10] A method for producing the laminate according to [1] to [9], comprising the step (I) of forming the adhesive layer (Y) on the surface of the substrate (X).

[11] A method for manufacturing the laminate according to

[10] , comprising the following steps (I-2) or (I-3): Step (I-2): A step of forming an adhesive layer (Y) on the surface of the substrate (X) by co-extruding the substrate (X) and the adhesive layer (Y); Step (I-3): A step of forming an adhesive layer (Y) on the surface of the substrate (X) by hot-melt coating the substrate (X) with the hydrogenated block copolymer (A) or a composition containing the hydrogenated block copolymer (A);

[12] A laminate for weatherstrips, comprising the laminate according to [1] to [9] above.

[0007] According to the present invention, it is possible to provide a laminate that exhibits excellent adhesion between a rubber-containing substrate and an adhesive layer, even without applying a primer treatment to the surface of the substrate.

[0008] The following description is based on an example of an embodiment of the present invention. However, the embodiments shown below are illustrative examples for realizing the technical concept of the present invention, and the present invention is not limited to the following description. In this specification, preferred forms of embodiments are shown, but combinations of two or more individual preferred forms are also preferred forms. If there are several numerical ranges for matters indicated by numerical ranges, a preferred form can be obtained by selectively combining their lower and upper limits. Also, when a numerical range is described as "XX to YY", it means "XX or more and YY or less". In this specification, "weight-average molecular weight (Mw)" is the weight-average molecular weight (Mw) on a standard polystyrene basis obtained by gel permeation chromatography (GPC) measurement, and more specifically, the value measured according to the method described in the Examples. In this specification, "molecular weight distribution (Mw / Mn)" is the value obtained from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) on a standard polystyrene basis obtained by gel permeation chromatography (GPC) measurement, and more specifically, the value measured according to the method described in the Examples.

[0009] [Laminate] The laminate of this embodiment is a laminate having a base material (X) and an adhesive layer (Y) adjacent to the base material (X), wherein the base material (X) contains rubber, and the adhesive layer (Y) contains a hydrogenated block copolymer (A) obtained by hydrogenating a block copolymer (P) which includes a polymer block (a) containing structural units derived from an aromatic vinyl compound and a polymer block (b) containing structural units derived from a conjugated diene compound.

[0010] <Substrate (X)> The substrate (X) in this embodiment contains rubber. Examples of rubber include synthetic rubber and natural rubber (NR). Examples of synthetic rubber include those containing thermosetting rubber. Examples of synthetic rubber include styrene-butadiene rubber (SBR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene propylene rubber (EPDM), butyl rubber (IIR), chlorobutyl rubber (CIIR), acrylic rubber (ACM), silicone rubber (Q), fluororubber (FKM), butadiene rubber (BR), epoxidized butadiene rubber (EBR), epichlorohydrin rubber (CO,CEO), urethane rubber (U), polysulfide rubber (T), and olefin-based thermoplastic elastomers (TPO) containing thermosetting rubber. Examples of olefin-based thermoplastic elastomers (TPO) containing thermosetting rubber include those in which polyolefin is used as the hard segment and rubber components such as ethylene propylene rubber are used as the soft segment. Examples of nitrile rubber include modified nitrile rubbers such as hydrogenated nitrile rubber, carboxyl-modified nitrile rubber, silicone-modified nitrile rubber, maleic acid-modified nitrile rubber, and hydroxyl-modified nitrile rubber, or those obtained by hydrogenating these; and acrylonitrile-butadiene-isoprene copolymers in which part of the butadiene is replaced with isoprene. Hydrogenated nitrile rubber (H-NBR) is sometimes called hydrogenated nitrile rubber or hydrogenated acrylonitrile-butadiene rubber. Hydrogenated nitrile rubber can be obtained by hydrogenating the double bonds contained in nitrile rubber. Examples of natural rubber include natural rubber (NR), as well as modified natural rubbers such as epoxidized natural rubber (ENR), methyl methacrylate (MMA) graft polymerized natural rubber, hydrogenated natural rubber, and deproteinized natural rubber. Among these, at least one selected from the group consisting of ethylene propylene rubber (EPDM), styrene-butadiene rubber (SBR), butyl rubber (IIR), and butadiene rubber (BR) is preferred from the viewpoint of adhesion to the adhesive layer (Y), and ethylene propylene rubber (EPDM) is more preferred.

[0011] The base material (X) may contain one type of rubber alone, or two or more types. Furthermore, the rubber may be rubber without a crosslinking structure, crosslinked rubber having a crosslinking structure, or a mixture of both rubber without a crosslinking structure and crosslinked rubber. From the viewpoint of heat resistance, it is preferable that the rubber contains crosslinked rubber. Examples of crosslinked rubber include chloroprene rubber, butyl rubber, and ethylene propylene rubber. Among these, ethylene propylene rubber is preferred from the viewpoint of adhesion to the adhesive layer (Y).

[0012] The rubber content in 100% by mass of the base material (X) is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 20% by mass or more, from the viewpoint of vibration damping properties, etc. From the viewpoint of moldability, flexibility, etc., it is preferably 100% by mass or less, more preferably 95% by mass or less, even more preferably 85% by mass or less, even more preferably 75% by mass or less, and even more preferably 55% by mass or less. The rubber content in 100% by mass of the base material (X) is preferably 3 to 100% by mass, more preferably 5 to 95% by mass, even more preferably 10 to 85% by mass, even more preferably 10 to 75% by mass, and even more preferably 20 to 55% by mass. Furthermore, the rubber content in 100% by mass of the base material (X) may be 5 to 100% by mass, 10 to 100% by mass, 20 to 100% by mass, or 50 to 100% by mass.

[0013] In one embodiment of the present invention, when the rubber contains crosslinked rubber, the content of crosslinked rubber in 100% by mass of the base material (X) is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of moldability, flexibility, etc. From the viewpoint of vibration damping, etc., it is preferably 100% by mass or less, more preferably 75% by mass or less, and even more preferably 55% by mass or less. The content of crosslinked rubber in 100% by mass of the base material (X) is preferably 3 to 100% by mass, more preferably 5 to 75% by mass, and even more preferably 10 to 55% by mass. In another embodiment of the present invention, when the rubber contains crosslinked rubber, the content of crosslinked rubber in 100% by mass of the base material (X) is 10 to 100% by mass, from the viewpoint of moldability, flexibility, etc. The content of crosslinked rubber in 100% by mass of the base material (X) may be 20 to 100% by mass, or 50 to 100% by mass.

[0014] The base material (X) may or may not contain components other than rubber. Examples of components other than rubber include fillers, foaming agents, softeners, accelerators, stearic acid, vulcanizing agents, crosslinking agents, and anti-aging agents. From the viewpoint of moldability and flexibility, the content of components other than rubber in 100% by mass of base material (X) is preferably 5% by mass or more, more preferably 15% by mass or more, even more preferably 25% by mass or more, or 45% by mass or more. From the viewpoint of vibration damping, it is preferably 97% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and even more preferably 80% by mass or less. The content of components other than rubber in 100% by mass of base material (X) is preferably 5 to 97% by mass, more preferably 15 to 95% by mass, even more preferably 25 to 90% by mass, and even more preferably 45 to 80% by mass.

[0015] The thickness of the substrate (X) is not particularly limited. From the viewpoint of further increasing the interlayer adhesion between the substrate (X) and the adhesive layer (Y), it is preferably 0.1 mm or more, more preferably 0.3 mm or more, even more preferably 0.5 mm or more, preferably 4 mm or less, more preferably 3 mm or less, and even more preferably 2.5 mm or less. The thickness of the substrate (X) is preferably 0.1 to 4 mm, more preferably 0.3 to 3 mm, and even more preferably 0.5 to 2.5 mm. The thickness of the substrate (X) in this specification is a value measured with a micrometer, and more specifically, it is a value obtained by the method described in the examples described later.

[0016] <Adhesive Layer (Y)> In this embodiment, the adhesive layer (Y) contains a hydrogenated block copolymer (A) obtained by hydrogenating a block copolymer (P) which includes a polymer block (a) containing structural units derived from an aromatic vinyl compound and a polymer block (b) containing structural units derived from a conjugated diene compound. Because the adhesive layer (Y) contains a hydrogenated block copolymer (A), the substrate (X) and the adhesive layer (Y) exhibit excellent adhesion even without applying a primer treatment to the surface of the substrate (X). The details of the reason for this are unclear, but it is thought that because the hydrogenated block copolymer (A) contained in the adhesive layer (Y) is obtained by hydrogenating a block copolymer (P) which includes a polymer block (a) containing structural units derived from an aromatic vinyl compound and a polymer block (b) containing structural units derived from a conjugated diene compound, the polarity of the rubber contained in the substrate (X) and the adhesive layer (Y) become similar, resulting in high adhesive strength between the substrate (X) and the adhesive layer (Y). Furthermore, the adhesive layer (Y) is flexible because it contains a hydrogenated block copolymer (A), and its ability to easily wet and spread across the surface of the substrate (X) is also considered to be one of the factors contributing to the high adhesive strength.

[0017] ≪Hydrogenated Block Copolymer (A)≫ In this embodiment, the hydrogenated block copolymer (A) is obtained by hydrogenating a block copolymer (P) which includes a polymer block (a) containing structural units derived from an aromatic vinyl compound and a polymer block (b) containing structural units derived from a conjugated diene compound.

[0018] The weight-average molecular weight (Mw) of the hydrogenated block copolymer (A) is preferably 40,000 or more, more preferably 60,000 or more, and even more preferably 80,000 or more, from the viewpoint of further improving the adhesion of the adhesive layer (Y), and preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less, from the viewpoint of flexibility and adhesiveness. The weight-average molecular weight (Mw) of the hydrogenated block copolymer (A) is preferably 40,000 to 500,000, more preferably 60,000 to 400,000, and even more preferably 80,000 to 300,000.

[0019] The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (A) is preferably 1.00 or higher, preferably 4.00 or lower, more preferably 3.00 or lower, even more preferably 2.00 or lower, even more preferably 1.50 or lower, even more preferably 1.25 or lower, and even more preferably 1.10 or lower. The molecular weight distribution (Mw / Mn) of the hydrogenated block copolymer (A) is preferably 1.00 to 4.00, more preferably 1.00 to 3.00, even more preferably 1.00 to 2.00, even more preferably 1.00 to 1.50, even more preferably 1.00 to 1.25, and even more preferably 1.00 to 1.10. When the molecular weight distribution is within the above range, the viscosity variation of the hydrogenated block copolymer (A) is small, making it easy to handle.

[0020] The content of hydrogenated block copolymer (A) in 100% by mass of the adhesive layer (Y) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, from the viewpoint of further improving the adhesion of the adhesive layer (Y). From the viewpoint of flexibility, it is preferably 100% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. The content of hydrogenated block copolymer (A) in 100% by mass of the adhesive layer (Y) is preferably 25 to 100% by mass, more preferably 25 to 75% by mass, even more preferably 30 to 70% by mass, and even more preferably 35 to 65% by mass.

[0021] <Block Copolymer (P)> The block copolymer (P) in this embodiment includes a polymer block (a) containing structural units derived from an aromatic vinyl compound and a polymer block (b) containing structural units derived from a conjugated diene compound.

[0022] (Polymer block (a)) Polymer block (a) contains structural units derived from aromatic vinyl compounds. Examples of aromatic vinyl compounds that constitute polymer block (a) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. These aromatic vinyl compounds may be used individually or in combination of two or more. Among these, at least one selected from the group consisting of styrene, α-methylstyrene, and 4-methylstyrene is preferred, with styrene being more preferred.

[0023] The content of structural units derived from the aromatic vinyl compound in 100% by mass of polymer block (a) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and may be 100% by mass. The content of structural units derived from the aromatic vinyl compound in 100% by mass of polymer block (a) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 85 to 100% by mass, even more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.

[0024] As long as it does not hinder the objectives and effects of the present invention, polymer block (a) may or may not contain structural units derived from compounds other than aromatic vinyl compounds. Examples of such other compounds include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, and the like. When polymer block (a) contains structural units derived from such other compounds, the bonding configuration is not particularly limited and may be random or tapered. The content of structural units derived from the above other compounds in 100% by mass of polymer block (a) is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, and may be 0% by mass. The content of structural units derived from the above-mentioned other compounds in 100% by mass of polymer block (a) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, even more preferably 0 to 15% by mass, even more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass.

[0025] The weight-average molecular weight (Mw) of polymer block (a) is preferably 2,000 or more, more preferably 2,500 or more, and even more preferably 3,000 or more, from the viewpoint of further improving the adhesion of the adhesive layer (Y), and preferably 50,000 or less, more preferably 30,000 or less, and even more preferably 10,000 or less, from the viewpoint of flexibility. The weight-average molecular weight (Mw) of polymer block (a) is preferably 2,000 to 50,000, more preferably 2,500 to 30,000, and even more preferably 3,000 to 10,000.

[0026] The block copolymer (P) may have at least one polymer block (a). When the block copolymer (P) has two or more polymer blocks (a), these polymer blocks (a) may be the same or different. When a plurality of polymer blocks (a) contained in the block copolymer (P) are different, when the polymer block (a) has one type of structural unit, it means that at least one of the weight average molecular weight (Mw) and stereoregularity of the structural unit constituting the polymer block (a) is different. When the polymer block (a) has a plurality of types of structural units, it means that at least one of the ratio of each structural unit and the copolymerization form (random, tapered, block) is different. From the viewpoints of flexibility, moldability, weather resistance, vibration damping property, handleability, etc., the block copolymer (P) preferably has two polymer blocks (a), and these polymer blocks (a) are preferably the same.

[0027] The weight average molecular weight (Mw) of the polymer block (a) can be determined by measuring the sampled liquid each time the polymerization of each polymer block ends in the production process. For example, when synthesizing a triblock copolymer having an a1-b-a2 structure by sequentially polymerizing a1, b, and a2 in this order, the weight average molecular weight (Mw) of the first polymer block (a1) can be determined by subjecting the liquid sampled when the polymerization of the polymer block (a1) ends to GPC measurement. Further, the weight average molecular weight (Mw) of the polymer block (a2) is obtained by subjecting the liquid sampled when the polymerization of the polymer block (a2) ends to GPC measurement to obtain the weight average molecular weight (Mw) of the triblock copolymer having an a1-b-a2 structure, and subtracting the weight average molecular weight (Mw) of the diblock copolymer having an a1-b structure from that value.

[0028] (Polymer block (b)) The polymer block (b) contains a structural unit derived from a conjugated diene compound. Examples of the conjugated diene compound constituting the polymer block (b) include butadiene, isoprene, 2,3-dimethylbutadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, myrcene, farnesene, chloroprene, and the like. These may be used alone or in combination of two or more. Among these, at least one conjugated diene compound selected from butadiene, isoprene, myrcene, and farnesene is preferable, at least one conjugated diene compound selected from butadiene and isoprene is more preferable, and isoprene is even more preferable.

[0029] The farnesene used as the conjugated diene compound may be either α-farnesene or β-farnesene represented by the following formula (I). From the viewpoint of the ease of production of the hydrogenated block copolymer (A), it is preferable to use β-farnesene. Note that α-farnesene and β-farnesene may be used in combination.

[0030]

[0031] From the viewpoint of further improving the adhesiveness of the adhesive layer (Y), the weight average molecular weight (Mw) of the polymer block (b) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 50,000 or more, and even more preferably 75,000 or more. From the viewpoint of flexibility, it is preferably 1,500,000 or less, more preferably 500,000 or less, still more preferably 350,000 or less. The weight average molecular weight (Mw) of the polymer block (a) is preferably 5,000 to 1,500,000, more preferably 10,000 to 500,000, still more preferably 50,000 to 350,000, and 75,000 to 180,000.

[0032] The weight-average molecular weight (Mw) of polymer block (b) can be determined by measuring a sampled solution each time polymerization of each polymer block is completed during the manufacturing process. For example, when synthesizing a triblock copolymer having an a1-b-a2 structure by sequentially polymerizing a1, b, and a2 in that order, the weight-average molecular weight (Mw) of polymer block (b) can be determined by measuring the sampled solution at the end of polymerization of polymer block (b) using GPC to determine the weight-average molecular weight (Mw) of the diblock copolymer with the a1-b structure, and then subtracting the weight-average molecular weight (Mw) of polymer block a1 from that value.

[0033] Hydrogenated block copolymer (A) can be obtained by hydrogenating the carbon-carbon double bonds in polymer block (b) contained in block copolymer (P). From the viewpoint of flexibility, the hydrogenation rate of the carbon-carbon double bonds in polymer block (b) is preferably 50 to 100 mol%, more preferably 70 to 100 mol%, and even more preferably 85 to 100 mol%. Note that the hydrogenation rate is determined by the relationship between block copolymer (P) and hydrogenated block copolymer (A) after hydrogenation. 1 It can be calculated by measuring H-NMR. The hydrogenation rate described above is measured by the method described in the examples.

[0034] The content of structural units derived from the above conjugated diene compound in 100% by mass of polymer block (b) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass. The content of structural units derived from the above conjugated diene compound in 100% by mass of polymer block (b) is preferably 60 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass.

[0035] (polymer block (c)) The block copolymer (P) may contain polymer block (a) and polymer block (b), as well as polymer block (c) composed of other monomers, as long as it does not hinder the effects of the present invention. Other monomers include, for example, unsaturated hydrocarbon compounds such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene; and functional group-containing unsaturated compounds such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, vinyl acetate, and methyl vinyl ether. These may be used individually or in combination of two or more. The content of polymer blocks (c) in 100% by mass of block copolymer (P) is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and may be 0% by mass. The content of polymer blocks (c) in 100% by mass of block copolymer (P) is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, and even more preferably 0 to 30% by mass.

[0036] (Mass ratio of polymer block (a) to polymer block (b)) Taking the total content of polymer block (a) and polymer block (b) in the block copolymer (P) as 100, the mass ratio of polymer block (a) to polymer block (b) [(a) / (b)] is preferably 1 / 99 to 50 / 50. If the content of polymer block (a) is above the lower limit, a hydrogenated block copolymer with excellent flexibility and better adhesion can be obtained. On the other hand, if the content of polymer block (a) is below the upper limit, the moldability is excellent. From this viewpoint, the mass ratio of polymer block (a) to polymer block (b) [(a) / (b)] is preferably 5 / 95 to 40 / 60, more preferably 8 / 92 to 30 / 70, and even more preferably 10 / 90 to 25 / 75.

[0037] (Bonding configuration of block copolymer (P)) Hydrogenated block copolymer (A) is a hydrogenated block copolymer (P) containing at least one polymer block (a) and one polymer block (b), and is preferably a hydrogenated block copolymer (P) containing two or more polymer blocks (a) and one or more polymer blocks (b). The bonding configuration of polymer blocks (a) and polymer blocks (b) is not particularly limited and may be linear, branched, radial, or a combination of two or more thereof. Among these, a configuration in which each block is bonded linearly is preferred, and when polymer block (a) is represented as a and polymer block (b) as b, (a-b) ｌ a-(b-a) ｍ or b - (a - b) ｎA bonding configuration represented by [b-a-b-a-b] is preferred. Hereinafter, l, m, and n each independently represent an integer of 1 or more. From the viewpoint of flexibility, moldability, and handling, a tetrablock copolymer represented by [b-a-b-a-b] and a triblock copolymer represented by [a-b-a] are preferred as the bonding configuration. Furthermore, when the block copolymer (P) has two or more polymer blocks (a) or two or more polymer blocks (b), each polymer block may contain the same structural units or different structural units. In addition, the weight-average molecular weight of the structural units constituting each polymer block may be the same or different. For example, in the two polymer blocks (a) of the triblock copolymer represented by [a-b-a], the aromatic vinyl compounds may be of the same type or different.

[0038] (Amount of vinyl bonding in block copolymer (P)) From the viewpoint of adhesion and vibration damping, the amount of vinyl bonding in block copolymer (P) is preferably 5 mol% or more, more preferably 20 mol% or more, even more preferably 40 mol% or more, even more preferably 45 mol% or more, preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 80 mol% or less. The amount of vinyl bonding in block copolymer (P) is preferably 5 to 95 mol%, more preferably 20 to 90 mol%, even more preferably 40 to 90 mol%, and even more preferably 45 to 80 mol%. When the conjugated diene compound is other than farnesene, the amount of vinyl bonding in block copolymer (P) means the total mole percent of structural units derived from the conjugated diene compound that are bonded by 1,2-bonds and 3,4-bonds, relative to 100 mol% of the total structural units constituting the block copolymer (P). Furthermore, when the conjugated diene compound is other than farnesene, the amount of vinyl bonds in the block copolymer (P) refers to the total mole percent of structural units derived from the conjugated diene compound that are bonded by means other than 1,4-bonds, relative to 100 mole percent of the total structural units constituting the block copolymer (P). When the conjugated diene compound is farnesene, the amount of vinyl bonds in the block copolymer (P) refers to the total mole percent of structural units derived from farnesene that are bonded by 3,13-bonds, relative to 100 mole percent of the total structural units constituting the block copolymer (P). Furthermore, when the conjugated diene compound is farnesene, the amount of vinyl bonds in the block copolymer (P) refers to the total mole percent of structural units derived from farnesene that are bonded by means other than 1,13-bonds, relative to 100 mole percent of the total structural units constituting the block copolymer (P). In other words, in this specification, "vinyl bond" means a 1,2-bond derived from butadiene when the conjugated diene compound is butadiene, a 1,2-bond and a 3,4-bond derived from isoprene when the conjugated diene compound is isoprene, and a 1,2-bond and a 3,13-bond when the conjugated diene compound is farnesene. Furthermore, "amount of vinyl bond" means the content (mol%) of structural units derived from the conjugated diene compound derived from the vinyl bond in 100 mol% of the total amount of monomer units constituting the block copolymer (P).The amount of vinyl bond in the above block copolymer (P) is measured by the method described in the examples.

[0039] The block copolymer (P) may be an unmodified block copolymer (P) or a modified block copolymer (P) in which a functional group has been introduced into the block copolymer (P). Examples of functional groups that can be introduced include amino groups, alkoxysilyl groups, hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, mercapto groups, isocyanate groups, chloro groups, and acid anhydrides.

[0040] <Method for producing hydrogenated block copolymer (A)> Hydrogenated block copolymer (A) can be suitably produced, for example, by a polymerization step of obtaining block copolymer (P) by anionic polymerization, and a step of hydrogenating the carbon-carbon double bonds in the polymer block (b) in the block copolymer (P).

[0041] (Polymerization Process) The block copolymer (P) can be produced by solution polymerization or by the methods described in Japanese Patent Publication No. 2012-502135 and Japanese Patent Publication No. 2012-502136. Solution polymerization is preferred, and known methods such as ionic polymerization such as anionic polymerization and cationic polymerization, and radical polymerization can be applied. Anionic polymerization is preferred. In the anionic polymerization method, an aromatic vinyl compound, farnesene, a conjugated diene other than farnesene, etc., are sequentially added in the presence of a solvent, an anionic polymerization initiator, and optionally a Lewis base to obtain the block copolymer (P). Examples of anionic polymerization initiators include compounds containing alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; and lanthanide rare earth metals such as lanthanum and neodymium. Alkali metals and compounds containing alkali metals are preferred, and organic alkali metal compounds are more preferred.

[0042] Examples of the aforementioned organoalkali metal compounds include organolithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium, stilbenithium, dilithithiomethane, dilithionaphthalene, 1,4-dilithiobutane, 1,4-dilithio-2-ethylcyclohexane, and 1,3,5-trilithiobenzene; sodium naphthalene, potassium naphthalene, etc. Among these, organolithium compounds are preferred, with n-butyllithium and sec-butyllithium being more preferred, and sec-butyllithium being even more preferred. The organoalkali metal compounds may also be reacted with secondary amines such as diisopropylamine, dibutylamine, dihexylamine, and dibenzylamine to be used as organoalkali metal amides. The amount of organoalkali metal compound used in polymerization varies depending on the molecular weight of the block copolymer (P), but is usually in the range of 0.01 to 3% by mass relative to the total amount of aromatic vinyl compounds and conjugated diene compounds.

[0043] There are no particular restrictions on the solvent as long as it does not adversely affect the anionic polymerization reaction. Examples include saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, and isooctane; saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. These may be used individually or in combination of two or more. There are no particular restrictions on the amount of solvent used.

[0044] Lewis bases play a role in controlling the microstructure of structural units derived from conjugated diene compounds. Examples of Lewis bases include ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol diethyl ether, and ditetrahydrofurylpropane; pyridine; tertiary amines such as N,N,N',N'-tetramethylethylenediamine and trimethylamine; alkali metal alkoxides such as potassium t-butoxide; and phosphine compounds. When using Lewis bases, the amount is usually preferably in the range of 0.01 to 1000 molar equivalents per mole of anionic polymerization initiator.

[0045] The polymerization reaction temperature is typically -80 to 150°C, preferably 0 to 100°C, and more preferably 10 to 90°C. The polymerization reaction can be carried out in batches or continuously. Block copolymers (P) can be produced by continuously or intermittently supplying each monomer to the polymerization reaction solution so that the amounts of aromatic vinyl compounds and conjugated diene compounds in the polymerization reaction system are within a specific range, or by sequentially polymerizing each monomer in the polymerization reaction solution so that they are in a specific ratio. The polymerization reaction can be stopped by adding an alcohol such as methanol or isopropanol as a polymerization stopper. The resulting polymerization reaction solution can be poured into a poor solvent such as methanol to precipitate the block copolymer (P), or the polymerization reaction solution can be washed with water, separated, and then dried to isolate the block copolymer (P).

[0046] In this polymerization step, an unmodified block copolymer (P) may be obtained as described above, but a modified block copolymer (P) may also be obtained by introducing functional groups into the block copolymer (P) before the hydrogenation step described later. Examples of functional groups that can be introduced include amino groups, alkoxysilyl groups, hydroxyl groups, epoxy groups, carboxyl groups, carbonyl groups, mercapto groups, isocyanate groups, chloro groups, acid anhydrides, and the like. Methods for modifying the block copolymer (P) include, for example, adding a modifying agent that can react with the polymerization active end, such as tin tetrachloride, tetrachlorosilane, dichlorodimethylsilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-bisaminomethylcyclohexane, 2,4-tolidylenediisocyanate, 4,4'-bis(diethylamino)benzophenone, N-vinylpyrrolidone, or other modifying agents described in Japanese Patent Application Publication No. 2011-132298, before adding a polymerization inhibitor. Alternatively, the copolymer can be grafted with maleic anhydride or the like. The functional group may be introduced at the polymerization end or side chain of the block copolymer (P). The functional group may be used individually or in combination of two or more. The amount of the modifying agent is usually preferably in the range of 0.01 to 10 molar equivalents relative to the anionic polymerization initiator.

[0047] (Hydrogenation Step) A hydrogenated block copolymer (A) can be obtained by subjecting the block copolymer (P) obtained by the above method or a modified block copolymer (P) to a hydrogenation step. A known method can be used for hydrogenation. For example, a hydrogenation reaction can be carried out by adding a Ziegler catalyst; a nickel, platinum, palladium, ruthenium, or rhodium metal catalyst supported on carbon, silica, diatomaceous earth, etc.; or an organometallic complex having cobalt, nickel, palladium, rhodium, or ruthenium metal to a solution obtained by dissolving the block copolymer (P) in a solvent that does not affect the hydrogenation reaction, as a hydrogenation catalyst. In the hydrogenation step, the hydrogenation reaction may be carried out by adding the hydrogenation catalyst to a polymerization reaction solution containing the block copolymer (P) obtained by the above method for producing the block copolymer (P). Palladium carbon, in which palladium is supported on carbon, is preferred as the hydrogenation catalyst. In the hydrogenation reaction, the hydrogen pressure is preferably 0.1 to 20 MPa, the reaction temperature is preferably 100 to 200°C, and the reaction time is preferably 1 to 20 hours.

[0048] <<Tackifier>> The adhesive layer (Y) in this embodiment may or may not contain a tackifier. From the viewpoint of further improving adhesion, it is preferable to include a tackifier. Examples of tackifiers include rosin-based tackifying resins, terpene-based tackifying resins, hydrocarbon-based tackifying resins, styrene-based tackifying resins, and acrylic-based tackifying resins. Among these, from the viewpoint of further improving adhesion, rosin-based tackifying resins, terpene-based tackifying resins, and hydrocarbon-based tackifying resins are preferred, and hydrocarbon-based tackifying resins are more preferred. The tackifier may be used alone, or two or more may be used in combination.

[0049] Examples of rosin-based tackifying resins include unmodified rosin (raw rosin) such as gum rosin, wood rosin, and tall oil rosin; modified rosin obtained by hydrogenation, disproportionation, polymerization, etc. (hydrogenated rosin, disproportionated rosin, polymerized rosin, and other chemically modified rosin; the same applies hereinafter); and various other rosin derivatives. Examples of the above rosin derivatives include rosin esters such as those obtained by esterifying unmodified rosin with alcohols (i.e., rosin esters) and modified rosin with alcohols (i.e., modified rosin esters); unsaturated fatty acid modified rosins obtained by modifying unmodified rosin or modified rosin with unsaturated fatty acids; unsaturated fatty acid modified rosin esters obtained by modifying rosin esters with unsaturated fatty acids; rosin alcohols obtained by reducing the carboxyl groups in unmodified rosin, modified rosin, unsaturated fatty acid modified rosins, or unsaturated fatty acid modified rosin esters; metal salts of rosins (especially rosin esters) such as unmodified rosin, modified rosin, and various rosin derivatives; and rosinphenol resins obtained by adding phenol to rosins (unmodified rosin, modified rosin, various rosin derivatives, etc.) with an acid catalyst and then thermal polymerization.

[0050] Examples of terpene-based tackifying resins include terpene resins such as α-pinene polymers, β-pinene polymers, and dipentene polymers; and modified terpene resins obtained by modifying these terpene resins (phenol modification, aromatic modification, hydrogenation modification, hydrocarbon modification, etc.). Examples of the above-mentioned modified terpene resins include terpene phenol resins, aromatically modified terpene resins (e.g., styrene terpene resins), and hydrogenated terpene resins.

[0051] Examples of hydrocarbon-based tackifying resins include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, aliphatic / aromatic copolymer (C5 / C9) petroleum resins, hydrogenated versions thereof (e.g., alicyclic petroleum resins obtained by hydrogenating aromatic petroleum resins (alicyclic saturated hydrocarbon resins)), various modified versions thereof (e.g., maleic anhydride modified versions), coumarone resins, indencoumarone resins, and various other hydrocarbon-based resins. Examples of aliphatic (C5) petroleum resins include amorphous polyalphaolefins. Examples of amorphous polyalphaolefins include ethylene homopolymers, propylene homopolymers, ethylene / propylene copolymers, ethylene / butene copolymers, and propylene / butene copolymers. Examples of product names include "Alcon P-100," "Alcon P-125," and "Alcon P-140" (all manufactured by Arakawa Chemical Industries, Ltd.). The hydrocarbon-based tackifying resin is preferably at least one selected from aliphatic (C5) petroleum resins and alicyclic saturated hydrocarbon resins, and more preferably an alicyclic saturated hydrocarbon resin.

[0052] Examples of styrene-based tackifying resins include styrene homopolymers, α-methylstyrene homopolymers, α-methylstyrene / styrene copolymers, styrene / aliphatic copolymers, α-methylstyrene / styrene / aliphatic copolymers, C9 petroleum resins, C5 / C9 petroleum resins, phenol-modified styrene resins, and hydrogenated versions thereof.

[0053] Examples of acrylic tackifying resins include acrylic tackifying resins based on acrylic polymers (homopolymers or copolymers) that use one or more alkyl (meth)acrylate esters as monomer components. Specific examples of alkyl (meth)acrylate esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, and (meth) Examples of C1-20 alkyl esters of (meth)acrylate include nonyl acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. The above acrylic polymer may optionally contain units corresponding to other monomer components copolymerizable with the above alkyl (meth)acrylate.

[0054] The content of the tackifier in 100% by mass of the adhesive layer (Y) is preferably 20% by mass or more, more preferably 25% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of exhibiting excellent adhesive strength, and preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, from the viewpoint of the adhesion of the adhesive layer (Y). The content of the tackifier in 100% by mass of the adhesive layer (Y) is preferably 20 to 70% by mass, more preferably 25 to 60% by mass, and even more preferably 30 to 50% by mass.

[0055] <<Softening Agent>> In the present embodiment, the adhesive layer (Y) may or may not contain a softening agent. From the viewpoint of further improving adhesiveness, it is preferable to contain a softening agent.As the softening agent, for example, petroleum-based process oils such as paraffinic process oil, naphthenic process oil, and aromatic process oil; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; vegetable oil-based softening agents such as peanut oil and rosin; softening agents derived from biomass; liquid paraffin; liquid co-oligomers of ethylene and α-olefin, liquid polybutene, liquid polybutadiene, liquid polyisoprene, liquid polyisoprene / butadiene copolymer, liquid styrene / butadiene copolymer, liquid styrene / isoprene copolymer, and other synthetic softening agents can be mentioned. Among these, petroleum-based process oils such as paraffinic process oil, naphthenic process oil, and aromatic process oil are preferable, and paraffinic process oil is more preferable. Also, as the softening agent, it is also preferable to use a recycled softening agent made from used softening agent as a raw material, and it is not particularly limited, but for example, product names: "RECOR-M 4875" and "TudasSol M 70" (both manufactured by H&R Co., Ltd.) etc. can be mentioned. The softening agent may be used alone or in combination of two or more.

[0056] As the above-mentioned softening agent derived from biomass, compounds represented by the following general formula (1), compounds represented by the following general formula (2), etc. can be preferably mentioned. These may be used alone or in combination of two or more. As products of softening agents derived from biomass, for example, product name: VIVA-B-FIX10227 (manufactured by H&R Co., Ltd., a mixture containing the structure represented by the following general formula (1)) can be mentioned.

[0057]

[0058] However, in general formula (1), n １ to n ３ are each independently 1 or 3, and R １ to R ６ are each independently a hydrogen atom or an unsubstituted hydrocarbon group, and the total number of carbon atoms of R １ and R ２ is 14, and R ３and R ４ The total number of carbon atoms is 14, R ５ and R ６ The total number of carbon atoms is 14, R １ ~R ６ It may have a branched structure.

[0059]

[0060] However, in general formula (2), n ４ and n ５ Each of these is independently either 1 or 3, and R ７ ~R １０ Each is independently a hydrogen atom or an unsubstituted hydrocarbon group, and R ７ and R ８ The total number of carbon atoms is 14, R ９ and R １０ The total number of carbon atoms is 14, R ７ ~R １０ It may have a branched structure.

[0061] The content of the softener in 100% by mass of the adhesive layer (Y) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of further improving adhesion, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of storage stability. The content of the softener in 100% by mass of the adhesive layer (Y) is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, and even more preferably 15 to 30% by mass.

[0062] <Anti-aging agent (antioxidant)> The adhesive layer (Y) in this embodiment may or may not contain an anti-aging agent. From the viewpoint of heat resistance and storage stability, it is preferable to include an anti-aging agent. Examples of anti-aging agents include amine-ketone compounds, imidazole compounds, amine compounds, phenolic compounds, sulfuric compounds, and phosphorus compounds. Among these, phenolic compounds are preferred. The anti-aging agent may be used alone or in combination of two or more types.

[0063] The content of the antioxidant in 100% by mass of the adhesive layer (Y) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more, from the viewpoint of heat resistance and storage stability, and preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, from the viewpoint of adhesiveness. The content of the antioxidant in 100% by mass of the adhesive layer (Y) is preferably 0.001 to 5% by mass, more preferably 0.01 to 5% by mass, even more preferably 0.02 to 1% by mass, and even more preferably 0.05 to 0.5% by mass.

[0064] <<Other Components>> The adhesive layer (Y) may or may not contain other components besides the hydrogenated block copolymer (A), tackifier, and softener. Examples of other components include polymers other than the hydrogenated block copolymer (A), plasticizers, antioxidants, inorganic fillers, lubricants, light stabilizers, processing aids, colorants such as pigments and dyes, flame retardants, antistatic agents, matting agents, silicone oils, antiblocking agents, UV absorbers, mold release agents, foaming agents, antibacterial agents, antifungal agents, fragrances, etc. These other components may be used individually or in combination of two or more. The content of other components in the adhesive layer (Y) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and may be 0% by mass. The content of other components in the adhesive layer (Y) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 3% by mass.

[0065] The thickness of the adhesive layer (Y) is not particularly limited, but from the viewpoint of further increasing the interlayer adhesion between the substrate (X) and the adhesive layer (Y), it is preferably 0.05 mm or more, more preferably 0.1 mm or more, even more preferably 0.3 mm or more, preferably 4 mm or less, more preferably 3 mm or less, and even more preferably 2.5 mm or less. The thickness of the adhesive layer (Y) is preferably 0.05 to 4 mm, more preferably 0.1 to 3 mm, and even more preferably 0.3 to 2.5 mm.

[0066] <Substrate (Z)> The laminate of this embodiment may have a substrate (Z) containing a polar resin. In this case, from the viewpoint of obtaining a laminate with excellent adhesion between the rubber and the adhesive layer, it is preferable that the laminate has a substrate (X), the adhesive layer (Y), and a substrate (Z) containing a polar resin in this order. The adhesive layer (Y) can also adhere well to the substrate (Z) containing a polar resin.

[0067] Examples of polar resins include poly(meth)acrylic acid ester resins, polyurethane resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene sulfide resins, (meth)acrylonitrile-butadiene-styrene resins (ABS), (meth)acrylonitrile-styrene resins, (meth)acrylic acid ester-butadiene-styrene resins, (meth)acrylic acid ester-styrene resins, butadiene-styrene resins, epoxy resins, phenolic resins, diallyl phthalate resins, polyimide resins, melamine resins, polyacetal resins (POM), polysulfone resins, polyethersulfone resins, polyetherimide resins, polyphenylene ether resins, polyarylate resins, polyetheretherketone resins, polystyrene resins, and syndiotactic polystyrene resins. These resins may be used individually or in combination of two or more. As the polar resin, at least one selected from poly(meth)acrylic acid ester resins and polyurethane resins is preferred. Examples of poly(meth)acrylic acid ester resins include polymethyl methacrylate resin. Among these, polymethyl methacrylate resin is preferred from the viewpoint of adhesion to the adhesive layer (Y). Furthermore, the substrate (Z) containing the polar resin may be surface-treated. Examples of such surface treatments include plating. The metal used in the plating process is not particularly limited, but examples include chromium, nickel, and zinc.

[0068] The base material (Z) may contain only a polar resin, or it may contain resins other than polar resins and other components, or it may not contain any of them. From the viewpoint of adhesion to the adhesive layer (Y), the content of polar resin in 100% by mass of base material (Z) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and may be 100% by mass. The content of polar resin in 100% by mass of base material (Z) is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.

[0069] The thickness of the substrate (Z) is not particularly limited, but from the viewpoint of further increasing the interlayer adhesion between the substrate (Z) and the adhesive layer (Y), it is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 3000 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. Preferably 1 to 3000 μm, more preferably 5 to 200 μm, and even more preferably 10 to 100 μm. The thickness of the substrate (Z) in this specification is a value measured with a micrometer, and more specifically, it is a value obtained by the method described in the examples below.

[0070] The laminate of this embodiment only needs to have a base material (X) and an adhesive layer (Y) adjacent to the base material (X). Therefore, the laminate of this embodiment may consist only of the base material (X) and the adhesive layer (Y), or it may be a laminate containing the base material (X), the adhesive layer (Y), and other layers in that order. The other layer may be the base material (Z), or it may be something other than the base material (Z). The layer other than the base material (Z) is preferably a layer that does not contain polar resins, and examples include resins other than polar resins, inorganic materials, paper, metal, cloth, etc. As for cloth, there are no particular limitations, but examples include nonwoven fabrics, woven fabrics, knitted fabrics, etc. As for paper, examples include release paper, which is paper that has been treated with a release agent. Specifically, a laminate containing the base material (X), adhesive layer (Y), and release paper in that order is provided. In this case, since the adhesive layer (Y) is protected by release paper, when adhering a substrate (Z) or the like to the adhesive layer (Y), the release paper can be peeled off immediately before adhesion to effectively adhere the adhesive layer (Y) to the substrate (Z). Also, in the case of a laminate containing a substrate (X), an adhesive layer (Y), and a substrate (Z) in this order, other layers may be included between the adhesive layer (Y) and the substrate (Z), and the adhesive layer (Y) and the substrate (Z) may be adjacent to each other. From the viewpoint of adhesion, it is preferable that the laminate contains the substrate (X), the adhesive layer (Y), and the substrate (Z) in this order, and that each layer is adjacent to each other. The thickness of the laminate is not particularly limited, but from the viewpoint of further increasing the interlayer adhesion strength of each layer, it is preferably 0.1 mm or more, more preferably 0.3 mm or more, even more preferably 0.5 mm or more, preferably 8 mm or less, more preferably 6 mm or less, and even more preferably 5 mm or less. The thickness of the laminate is preferably 0.1 to 8 mm, more preferably 0.3 to 6 mm, and even more preferably 0.5 to 5 mm. The thickness of the laminate in this specification is a value measured with a micrometer, and more specifically, it is a value obtained by the method described in the examples described later.

[0071] [Method for Manufacturing a Laminate] The method for manufacturing the laminate according to this embodiment preferably includes a step (I) of forming an adhesive layer (Y) on the surface of a base material (X). By forming an adhesive layer (Y) on the surface of the base material (X), a laminate can be made having a base material (X) and an adhesive layer (Y) adjacent to the base material (X). In step (I), it is sufficient that an adhesive layer (Y) can be formed on the surface of the base material (X), and a known method can be used for this.

[0072] From the viewpoint of efficiently obtaining the effects of the present invention, step (I) is preferably at least one of the following steps (I-1) to (I-3). Step (I-1): A step of bonding a molded body containing the hydrogenated block copolymer (A) to the surface of the substrate (X) to form an adhesive layer (Y) on the surface of the substrate (X). Step (I-2): A step of co-extruding the substrate (X) and the adhesive layer (Y) to form an adhesive layer (Y) on the surface of the substrate (X). Step (I-3): A step of hot-melt coating the substrate (X) with the hydrogenated block copolymer (A) or a composition containing the hydrogenated block copolymer (A) to form an adhesive layer (Y) on the surface of the substrate (X). Furthermore, from the viewpoint of efficiently obtaining the effects of the present invention, the manufacturing method of the laminate of this embodiment is preferably at least one of the first manufacturing method having step (I-1), the second manufacturing method having step (I-2), and the third manufacturing method having step (I-3), and more preferably a manufacturing method having step (I-2) or step (I-3).

[0073] <First Manufacturing Method> The first manufacturing method of the laminate of this embodiment includes a step (I-1) of bonding a molded body containing a hydrogenated block copolymer (A) to the surface of a substrate (X) to form an adhesive layer (Y) on the surface of the substrate (X). In the first manufacturing method, before step (I-1), first, a hydrogenated block copolymer (A) or a composition containing a hydrogenated block copolymer (A) is molded into a molded body. Known methods can be used as the molding method, such as extrusion molding, press molding, calendering, injection molding, etc. The shape of the molded body can be a sheet, a film, etc. From the viewpoint of adhesion to the substrate (X), the molded body is preferably in the form of a sheet. The method of molding into a sheet is preferably press molding, and more preferably compression press molding. The composition containing a hydrogenated block copolymer (A) may contain the above-mentioned tackifier, softener, antioxidant, and other components. The content of hydrogenated block copolymer (A) in the composition containing hydrogenated block copolymer (A) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, from the viewpoint of further improving the adhesion of the adhesive layer (Y), and preferably 100% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less, from the viewpoint of flexibility. That is, the content of hydrogenated block copolymer (A) in the composition is preferably 25 to 100% by mass, more preferably 25 to 75% by mass, even more preferably 30 to 70% by mass, and even more preferably 35 to 65% by mass.

[0074] The following are the conditions for forming a hydrogenated block copolymer (A) or a composition containing hydrogenated block copolymer (A) into a sheet by press molding. The temperature for forming the sheet by press molding is not particularly limited, but is preferably 100 to 120°C. The pressure for forming the sheet by press molding is not particularly limited, but is preferably 1 to 3 MPa / cm². 2 The time required to form the material into a sheet by press molding is not particularly limited, but is preferably 1 to 5 minutes.

[0075] Next, a molded body containing a hydrogenated block copolymer (A) is bonded to the surface of the substrate (X) to form an adhesive layer (Y) on the surface of the substrate (X). In other words, the substrate (X) and the molded body are laminated. From the viewpoint of achieving stronger adhesion between the substrate (X) and the adhesive layer (Y), the lamination method is preferably press molding, and more preferably compression press molding. The temperature when laminating the substrate (X) and the adhesive layer (Y) by press molding is not particularly limited, but is preferably 100 to 120°C. The pressure when laminating the substrate (X) and the adhesive layer (Y) by press molding is not particularly limited, but is preferably 1 to 3 MPa / cm². 2 The pressing time when laminating the substrate (X) and the adhesive layer (Y) by press molding is not particularly limited, but is preferably 1 to 5 minutes.

[0076] When manufacturing a laminate further comprising a base material (Z), it is preferable to laminate the base material (Z) on the side of the adhesive layer (Y) opposite to the side of the adhesive layer (Y) that is in contact with the base material (X) after step (I-1). Methods for laminating the base material (Z) include injection molding the base material (Z) onto the adhesive layer (Y), and press molding the base material (Z) onto the adhesive layer (Y). There are no particular limitations on the injection molding method for the base material (Z) onto the adhesive layer (Y), but it is preferable to set the mold temperature to preferably 190 to 360°C, more preferably 200 to 330°C, and the cylinder temperature for injecting the resin constituting the base material (Z) to preferably 40 to 160°C, more preferably 45 to 150°C when injection molding is performed. There are no particular restrictions on the method of press-molding the substrate (Z) onto the adhesive layer (Y), however, after laminating the substrate (Z) onto the adhesive layer (Y), the temperature is preferably 100 to 220°C, more preferably 120 to 200°C, and the load is preferably 10 to 100 kgf / cm 2 More preferably 10 to 50 kgf / cm² 2 More preferably 15 to 40 kgf / cm² 2 The adhesive layer (Y) and the substrate (Z) can be bonded together by compressing them, preferably for 1 to 10 minutes, and more preferably for 1 to 5 minutes.

[0077] <Second Manufacturing Method> The second manufacturing method for the laminate of this embodiment includes a step (I-2) in which the base material (X) and the adhesive layer (Y) are formed by co-extrusion. By co-extruding the base material (X) and the adhesive layer (Y) in step (I-2), the base material (X) and the adhesive layer (Y) can be bonded more firmly. Furthermore, co-extrusion can also reduce the number of steps.

[0078] In step (I-2), a base material (X) and a hydrogenated block copolymer (A) or a composition containing hydrogenated block copolymer (A) are co-extruded to form a laminate having a base material (X) and an adhesive layer (Y) adjacent to the base material (X). The composition containing hydrogenated block copolymer (A) may also contain the above-mentioned tackifiers, softeners, anti-aging agents, and other components. From the viewpoint of further improving the adhesion of the adhesive layer (Y), the content of hydrogenated block copolymer (A) in the composition containing hydrogenated block copolymer (A) is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, and from the viewpoint of flexibility, it is preferably 100% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. That is, the content of hydrogenated block copolymer (A) in the composition is preferably 25 to 100% by mass, more preferably 25 to 75% by mass, even more preferably 30 to 70% by mass, and even more preferably 35 to 65% by mass.

[0079] There are no particular restrictions on the co-extrusion method, but methods using film-forming equipment such as a T-die extruder or an inflation molding machine are examples. When co-extruding, the barrel temperature on the substrate (X) side is preferably set to 150 to 250°C. Furthermore, when T-die extrusion is performed, the T-die temperature is more preferably 130 to 230°C.

[0080] When manufacturing a laminate further having a base material (Z), it is preferable to laminate the base material (Z) on the side of the adhesive layer (Y) opposite to the side in contact with the base material (X) after step (I-2). The method for laminating the base material (Z) is the same as the method for the first manufacturing method described above, and the preferred embodiments are also the same.

[0081] <Third Manufacturing Method> The third manufacturing method of the laminate of this embodiment includes a step (I-3) of hot-melt coating of the hydrogenated block copolymer (A) or a composition containing the hydrogenated block copolymer (A). In step (I-3), by hot-melt coating of the hydrogenated block copolymer (A) or a composition containing the hydrogenated block copolymer (A), the substrate (X) and the adhesive layer (Y) can be bonded more firmly.

[0082] In step (I-3), the hydrogenated block copolymer (A) or a composition containing the hydrogenated block copolymer (A) is applied to the surface of the substrate (X) by hot-melt coating. After applying the composition, the material is cooled to room temperature to form a laminate having the substrate (X) and an adhesive layer (Y) adjacent to the substrate (X). The composition used in step (I-3) can be the same as the composition used in step (I).

[0083] One method of hot-melt coating is to use a heat-resistant material such as polyethylene terephthalate or a flat plate or roll such as a steel belt as a support, and then coat the composition onto a substrate (X) using a bar coater, roll coater, die coater, comma coater, etc.

[0084] When manufacturing a laminate further having a base material (Z), it is preferable to laminate the base material (Z) on the side of the adhesive layer (Y) opposite to the side in contact with the base material (X) after step (I-3). The method for laminating the base material (Z) is the same as the method for the first manufacturing method described above, and the preferred embodiments are also the same.

[0085] [Applications of the Laminate] The laminate of this embodiment can be used for various applications. The adhesive layer (Y) of the laminate of this embodiment has excellent adhesion to a rubber-containing substrate (X), and is therefore suitable for use as a weatherstrip, automotive interior parts, electronic equipment, medical equipment, building materials, and packaging materials. More preferably, it is used as a weatherstrip laminate. Furthermore, the laminate of this embodiment can also be used as a weatherstrip.

[0086] The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these.

[0087] [Synthesis of Hydrogenated Block Copolymer (A)] The physical properties of block copolymer (A) obtained in the production example were measured or evaluated by the following method.

[0088] <Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn)> The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polymer block (a) and hydrogenated block copolymer (A) in polystyrene equivalent were determined by gel permeation chromatography (GPC) measurement under the following conditions. (GPC measurement device and measurement conditions) ・Device: GPC device "HLC-8020" (manufactured by Tosoh Corporation) ・Separation column: "TSKgel GMHXL", "G4000HX L", and "G5000HXL" manufactured by Tosoh Corporation were connected in series. ・Eluent: Tetrahydrofuran ・Eluent flow rate: 0.7 mL / min ・Sample concentration: 5 mg / 10 mL ・Column temperature: 40°C ・Detector: Differential refractive index (RI) detector ・Calibration curve: Created using standard polystyrene

[0089] <Hydrogenation Rate> In each production example, the block copolymer before hydrogenation (P) and the block copolymer after hydrogenation (hydrogenated block copolymer (A)) were dissolved in deuterated chloroform solvent and heated at 30°C using Bruker Japan Co., Ltd.'s "AVANCE 400 Nanobay". 1 ¹H-NMR was measured. The hydrogenation rate of polymer block (b) in hydrogenated block copolymer (A) was calculated from the proton peaks of carbon-carbon double bonds appearing at 4.5–6.0 ppm in the obtained spectrum using the following formula: Hydrogenation rate = {1 - (number of moles of carbon-carbon double bonds per mole of block copolymer after hydrogenation) / (number of moles of carbon-carbon double bonds per mole of block copolymer before hydrogenation)} × 100 (mol%)

[0090] <Vinyl Bonding Amount> The block copolymers before hydrogenation were each dissolved in deuterated chloroform solvent, and Bruker Japan Co., Ltd.'s "AVANCE 400 Nanobay" was used. 1¹H-NMR was measured. The amount of vinyl bonding (total content of 3,4-bonding units and 1,2-bonding units) was calculated from the ratio of the peak areas of the total peak area of ​​structural units derived from isoprene and / or butadiene, and the peak areas corresponding to the 3,4-bonding units and 1,2-bonding units in structural units derived from isoprene, the 1,2-bonding units in structural units derived from butadiene, or, in the case of structural units derived from a mixture of isoprene and butadiene, the peak areas corresponding to each of the aforementioned bonding units.

[0091] <Production Example 1: Production of Hydrogenated Block Copolymer (A-1)> In a nitrogen-purged and dried pressure vessel, 62.4 kg of cyclohexane was charged as the solvent, and 0.0868 kg of a cyclohexane solution of sec-butyllithium at a concentration of 10.5% by mass was charged as an anionic polymerization initiator (effective amount of sec-butyllithium added: 9.1 g). After raising the temperature inside the pressure vessel to 50°C, 1.16 kg of styrene (1) was added and polymerization was carried out for 1 hour. At a vessel temperature of 50°C, 0.359 kg of tetrahydrofuran was added, and 8.70 kg of isoprene was added over 5 hours and polymerization was carried out for 2 hours. Further polymerization was carried out by adding 1.16 kg of styrene (2) and polymerization was carried out for 1 hour to obtain a reaction solution containing polystyrene-polyisoprene-polystyrene triblock copolymer. To this reaction solution, a Ziegler-type hydrogenation catalyst formed from nickel octyolate and trimethylaluminum was added under a hydrogen atmosphere, and the reaction was carried out for 5 hours under conditions of hydrogen pressure of 1 MPa and 80°C. After allowing the reaction solution to cool and release pressure, the catalyst was removed by washing with water, and the mixture was vacuum-dried to obtain a hydrogenated polystyrene-polyisoprene-polystyrene triblock copolymer (A-1) (hereinafter referred to as "hydrogenated block copolymer (A-1)"). The physical properties of the obtained hydrogenated block copolymer (A-1) were measured. The results are shown in Table 1.

[0092] <Production Examples 2-4: Production of Hydrogenated Block Copolymers (A-2) to (A-4)> Hydrogenated block copolymers (A-2) to (A-4) were obtained in the same manner as in Production Example 1, except that the formulations were as shown in Table 1 below. The above physical properties were measured for the obtained hydrogenated block copolymers (A-2) to (A-4). The results are shown in Table 1.

[0093]

[0094] [Manufacturing of Laminates] The following materials were used to manufacture the laminates. (Adhesive layer) ・Hydrogenated block copolymer (A-1) to (A-4): Hydrogenated block copolymer (A-1) to (A-4) from Production Examples 1 to 4 ・Hydrogenated block copolymer (A-5): Polystyrene-poly(ethylene / butylene)-polystyrene triblock copolymer "KRATON® G1643 V Polymer" (manufactured by Kraton Corporation) ・Unhydrogenated block copolymer (A'-1): Thermoplastic elastomer "Quintac 3421" (unhydrogenated block copolymer of polystyrene and polyisoprene, manufactured by Nippon Zeon Co., Ltd.) ・Tackifier: "Alcon P-100" (hydrocarbon-based tackifier resin, manufactured by Arakawa Chemical Industries, Ltd.) ・Tackifier: "Alcon P-125" (hydrocarbon-based tackifier resin, manufactured by Arakawa Chemical Industries, Ltd.) ・Tackifier: "Alcon P-140" (hydrocarbon-based tackifier resin, manufactured by Arakawa Chemical Industries, Ltd.) - Softener: "Diana Process Oil PW-90" (paraffin-based process oil, manufactured by Idemitsu Kosan Co., Ltd.) - Anti-aging agent: "ADEKA Stab AO-60" (phenol-based compound, manufactured by ADEKA Corporation) (Base material (X)) - Base material (X-1): Ethylene propylene rubber (Akitsu Kogyo Co., Ltd., EPDM sheet) - Base material (X-2): Olefin-based thermoplastic elastomer containing ethylene propylene rubber "EXCELINK® 1703B" (manufactured by ENEOS Material Corporation) (Base material (Z)) - Base material (Z-1): Polymethyl methacrylate resin (Sumika Acrylic Sales Co., Ltd., Sumipex E)

[0095] <Examples 1-10 and Comparative Example 1> (1) Production of the adhesive layer composition The adhesive layer composition was obtained by melt-kneading the composition and amount described in Tables 2 and 3 below at 170-190°C for 1 hour using a tabletop kneader "PBV-0.3" (manufactured by Irie Shokai Co., Ltd.).

[0096] (2) Manufacturing of molded body for adhesive layer The obtained adhesive layer composition is subjected to compression press molding using Shindo Metal Industries Co., Ltd.'s "NF-37HH" machine at 110°C and 2 MPa / cm². 2By compressing and pressing the material under a load for two minutes and then cutting it, a molded body measuring 150 mm in length, 25 mm in width, and 0.8 mm in thickness, which would later become the adhesive layer, was obtained.

[0097] (3) Manufacturing of Laminates In Examples 1 and 4-10, and Comparative Example 1, laminates 1 and 2 were manufactured. In Example 2, laminate 3 was manufactured. In Example 3, laminate 4 was manufactured. (3-1) Manufacturing of Laminate 1 A base material (X-1) measuring 150 mm in length, 30 mm in width, and 1.0 mm in thickness was placed in the compression press molding machine so as to overlap the molded body. The laminated base material (X-1) and the molded body were compressed using the compression press molding machine at 110°C and 2 MPa / cm 2 The substrate (X-1) and the molded body were bonded together by hot press molding under a load of 150 mm in length, 30 mm in width, and 1.8 mm in thickness, thereby obtaining a laminate 1 in which a substrate (X-1) and an adhesive layer were laminated together. The thickness of the substrate (X-1) and the laminate 1 were measured at room temperature (23°C) using a micrometer (manufactured by Mitutoyo Corporation).

[0098] (3-2) Manufacturing of Laminate 2 A PET film (Toyobo Ester® Film E5000, manufactured by Toyobo Co., Ltd.) measuring 200 mm in length, 200 mm in width, and 0.05 mm in thickness was coated with an adhesive layer composition to a thickness of 0.8 mm to obtain a laminate measuring 100 mm in length, 25 mm in width, and 0.85 mm in thickness, in which the PET film and the adhesive layer were laminated. Subsequently, the molded body was attached to a base material (Z-1) measuring 180 mm in length, 50 mm in width, and 1.5 mm in thickness so that they were in contact with each other, and after being rolled down at a speed of 10 mm / min using a 2 kg rubber roller, it was left to stand for 24 hours in an atmosphere of 23 ± 1 °C and 50 ± 5% humidity to obtain a laminate 2 measuring 180 mm in length, 50 mm in width, and 2.35 mm in thickness. The thickness of the base material (Z-1) and laminate 2 were measured at room temperature (23 °C) using a micrometer (manufactured by Mitutoyo Corporation).

[0099] (3-3) Manufacturing of Laminate 3 The obtained adhesive layer composition and the olefin-based thermoplastic elastomer "EXCELINK® 1703B" (manufactured by ENEOS Material Co., Ltd.) were co-extruded using separate unscrew extruders. The adhesive layer (Y) was extruded at 120°C and the olefin-based thermoplastic elastomer at 170°C to obtain a laminate 3 with a length of 150 mm, a width of 25 mm, and a thickness of 2 mm, in which the adhesive layer (Y) and the substrate (X-2) were laminated. The thickness of the substrate (X-2) and the laminate 3 was measured at room temperature (23°C) using a micrometer (manufactured by Mitutoyo Corporation).

[0100] (3-4) Manufacturing of Laminate 4 The obtained adhesive layer composition was added to a hot melt coating machine heated to 180°C and coated to a thickness of 1 mm onto a substrate (X-1) measuring 150 mm in length, 25 mm in width, and 1 mm in thickness to obtain laminate 4. The thickness of the substrate (X-1) was measured at room temperature (23°C) using a micrometer (manufactured by Mitutoyo Corporation).

[0101] <Peel Strength> The method for measuring peel strength was changed depending on the type of substrate, but all tests evaluated adhesion, and the obtained peel strengths are comparable. Laminates 1, 3, and 4, which have substrate (X), were peeled from the substrate (X) to the adhesive layer using "Instron 3345" (manufactured by Instron) at a peeling speed of 200 mm / min, in accordance with the T-type peel test of JIS Z 0237:2009, and the peel strength between the substrate (X) and the adhesive layer was measured. Laminate 2, which has substrate (Z), was peeled from the substrate (Z) to the adhesive layer using "Instron 3345" (manufactured by Instron) at a peeling speed of 200 mm / min, in accordance with the 180-degree peel test of JIS K 6854-3:1999, and the peel strength between the substrate (Z) and the adhesive layer was measured. Tables 2 and 3 show the laminates used for measuring peel strength and the measurement results of peel strength.

[0102]

[0103]

[0104] The results in Tables 2 and 3 show that the laminate of the present invention exhibits excellent adhesion between the substrate (X) and the adhesive layer (Y) even without applying a primer treatment to the surface of the rubber-containing substrate (X). Furthermore, the adhesive layer (Y) also exhibits excellent adhesion to the substrate (Z) containing a polar resin.

Claims

1. A laminate comprising a base material (X) and an adhesive layer (Y) adjacent to the base material (X), wherein the base material (X) contains rubber, and the adhesive layer (Y) contains a hydrogenated block copolymer (A) obtained by hydrogenating a block copolymer (P) which comprises a polymer block (a) containing structural units derived from an aromatic vinyl compound and a polymer block (b) containing structural units derived from a conjugated diene compound.

2. The laminate according to claim 1, comprising a base material (X), the adhesive layer (Y), and a base material (Z) containing a polar resin, in this order.

3. The laminate according to claim 1 or 2, wherein the rubber contains crosslinked rubber.

4. The laminate according to claim 3, wherein the content of the crosslinked rubber in 100% by mass of the base material (X) is 10 to 100% by mass.

5. The laminate according to any one of claims 1 to 4, wherein the rubber contains ethylene propylene rubber.

6. The laminate according to any one of claims 1 to 5, wherein the conjugated diene compound is at least one selected from butadiene and isoprene.

7. The laminate according to any one of claims 1 to 6, wherein the content of the hydrogenated block copolymer (A) in 100% by mass of the adhesive layer (Y) is 25 to 100% by mass.

8. The laminate according to any one of claims 1 to 7, wherein the hydrogenation rate of the carbon-carbon double bonds in the polymer block (b) is 50 to 100 mol%.

9. The laminate according to any one of claims 1 to 8, wherein the weight-average molecular weight (Mw) of the hydrogenated block copolymer (A) is 40,000 to 500,000.

10. A method for manufacturing a laminate according to claims 1 to 9, comprising the step (I) of forming the adhesive layer (Y) on the surface of the substrate (X).

11. A method for manufacturing a laminate according to claim 10, comprising the following steps (I-2) or (I-3): Step (I-2): A step of co-extruding the substrate (X) and the adhesive layer (Y) to form the adhesive layer (Y) on the surface of the substrate (X); Step (I-3): A step of hot-melt coating the substrate (X) with the hydrogenated block copolymer (A) or a composition containing the hydrogenated block copolymer (A) to form the adhesive layer (Y) on the surface of the substrate (X).

12. A laminate for weatherstrips, comprising the laminate described in claims 1 to 9.

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