TW202110920A - Laminate - Google Patents

Abstract

This laminate has a base material layer and an adhesive layer, wherein the ratio [i/ii] of the Shore A hardness i of the base material layer with respect to the Shore A hardness ii of the adhesive layer is 1.1 or more, and at least one of the base material layer and the adhesive layer contains a block copolymer or a hydrogenated product thereof. The block copolymer includes a polymeric block (A) and a polymeric block (B), wherein the polymeric block (B) has a structural unit that is derived from a conjugated diene compound and that includes, in a main chain, at least one alicyclic backbone (X) represented by formula (X).

Description

Layered body

The present invention relates to a laminate including a substrate layer and an adhesive layer.

Among the block copolymers having polymer blocks containing structural units derived from aromatic vinyl compounds, and polymer blocks containing structural units derived from conjugated diene compounds, and their hydrogenated products are known Vibration damping person, and can be used as a vibration damping material. In addition, the above-mentioned block copolymers and their hydrogenated products are considered to have physical properties such as sound insulation, heat resistance, impact resistance, and adhesive properties in addition to vibration damping properties, and can be used in various applications. . For example, a hydrogenated block copolymer of a styrene-based compound and a conjugated diene compound such as isoprene or butadiene has been disclosed for the purpose of improving vibration resistance, flexibility, heat resistance, tensile strength, and impact resistance. It is excellent in mechanical properties such as properties, and the peak temperature of tanδ and the vinyl bond amount are specified (for example, refer to Patent Documents 1 to 4).

On the other hand, as a laminate including a substrate layer and an adhesive layer (adhesive layer), for example, a surface protective film is known. It is known to use an adhesive composition containing a styrene-based elastomer and an adhesion-imparting resin to form an adhesive layer in a surface protective film (for example, refer to Patent Documents 5 and 6). [Prior Technical Literature] [Patent Literature]

Patent Document 1 　 JP 2002-284830 A Patent Document 2 "International Publication No. 2000/015680 Patent Document 3 　 JP 2006-117879 A Patent Document 4 　 JP 2010-053319 A Patent Document 5 　 Japanese Patent Laid-Open No. 5-194923 Patent Document 6 　 JP 2010-126711 A

[The problem to be solved by the invention]

The above-mentioned block copolymers and their hydrogenated products have physical properties such as adhesiveness in addition to vibration damping properties. Therefore, a laminate is being explored that exhibits vibration damping properties and possesses the physical properties required for laminates with adhesive properties. . Regarding the aforementioned vibration damping properties, although improvements are being made to make them more excellent, it is difficult to further improve various physical properties such as vibration damping properties and adhesive properties in a well-balanced manner. In addition, the physical properties required for an adhesive layered body include the suppression of adhesive residue (a phenomenon in which a part of the adhesive layer remains on the adherend) in addition to the adhesive force. Furthermore, among the bonded bodies that use laminates such as surface protection films, there are those that heat up during use of electrical products, etc., and the bonded bodies that are installed outdoors or the bonded bodies used outdoors may be affected by the As the temperature rises, the adhesion holding power of the adhesive layer decreases, and the laminate may easily peel off. We are pursuing the adhesive force that can withstand the temperature changes of the bonded body and the use environment.

Therefore, the present invention provides a laminated body including an adhesive layer and a base layer, which can impart vibration damping properties to the adherend, and is not easy to peel off even at high temperatures and is not easy to produce glue residue. [Means used to solve the problem]

As a result of intensive research in order to solve the above-mentioned problem, the present inventors considered the following invention and found that the problem can be solved. That is, the present invention is as follows.

A laminated body, which is a laminated body having a substrate layer and an adhesive layer, The ratio [i/ii] of the Shore A hardness i of the substrate layer to the Shore A hardness ii of the adhesive layer is 1.1 or more, At least one of the base material layer and the adhesive layer contains the following block copolymer or its hydrogenated product. The aforementioned block copolymer contains a polymer block (A) and a polymer block (B). The aforementioned polymer block (B) is a structural unit derived from a conjugated diene compound and has the following formula in the main chain: (X) One or more structural units of alicyclic skeleton (X) shown in (X).

(上述式(X)中，R¹ ~R³ 各自獨立地表示氫原子或碳數1~11的烴基，複數個R¹ ~R³ 各自可相同或不同。) [發明效果]

(In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different.) [Effects of the invention]

According to the present invention, there is provided a laminated body including an adhesive layer and a base layer, which can impart vibration damping properties to an adherend, and is not easy to peel off even at a high temperature, and is not easy to generate glue residue.

[Forms used to implement the invention]

The laminate of the present invention is a laminate having a substrate layer and an adhesive layer, It is characterized in that the ratio [i/ii] of the Shore A hardness i of the base layer to the Shore A hardness ii of the adhesive layer is 1.1 or more, At least one of the base layer and the adhesive layer contains the following block copolymer or its hydrogenated product. The aforementioned block copolymer contains a polymer block (A) and a polymer block (B). The aforementioned polymer block (B) is a structural unit derived from a conjugated diene compound, and has a main chain containing the aforementioned formula (X) One or more structural units of alicyclic skeleton (X) shown in (X). Hereinafter, the base material layer and the adhesion layer contained in the laminate, the block copolymer and its hydrogenated product will be described.

"Block copolymers and their hydrogenated products" In the embodiment of the present invention (hereinafter, sometimes referred to as "this embodiment"), the block copolymer or its hydrogenated product may be contained in at least one of the base layer and the adhesion layer. By containing the block copolymer or its hydrogenated product, it is possible to impart vibration damping and adhesive properties to the laminate. However, it is possible to include a block in one or both of the base layer or the adhesive layer according to the various uses of the laminate. Copolymer or its hydrogenated product.

[Polymer block (A)] From the viewpoint of vibration damping properties and mechanical properties, the polymer block (A) constituting the block copolymer preferably has a structural unit derived from an aromatic vinyl compound used as a monomer. The polymer block (A) preferably contains more than 70 mol% of the structural unit derived from the aromatic vinyl compound in the polymer block (A) (hereinafter, sometimes referred to as "aromatic vinyl compound unit"). ") From the viewpoint of mechanical properties, it is more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and particularly preferably substantially 100 mol%.

Examples of the above-mentioned aromatic vinyl compounds include: styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6- Dimethylstyrene, 2,4-Dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β -Methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2 ,6-Dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene Methyl styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro- M-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorobenzene Ethylene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-di Chlorostyrene, o-tertiary butyl styrene, m-tertiary butyl styrene, p-tertiary butyl styrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, o Chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted by silyl groups , Indene, vinyl naphthalene, N-vinyl carbazole, etc. One kind of these aromatic vinyl compounds may be used alone, or two or more kinds may be used. Among them, from the viewpoint of the balance of production cost and physical properties, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

烯、二戊烯、亞甲基降莰烯、2-亞甲基四氫呋喃等之群組中的至少1種。聚合物嵌段(A)含有該其他不飽和單體單元之情形的結合形態無特別限制，可為隨機、錐狀之任一者。As long as the purpose and effects of the present invention are not hindered, the polymer block (A) may also contain structural units derived from other unsaturated monomers other than aromatic vinyl compounds (hereinafter, sometimes referred to as "other unsaturated monomers"Unit"), but in the polymer block (A), it is preferably 30 mol% or less, more preferably less than 20 mol%, still more preferably less than 15 mol%, and more preferably less than 10 mol% , And more preferably less than 5 mol%, particularly preferably 0 mol%. Examples of the other unsaturated monomers include those selected from butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, Isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-pair

At least one of the group consisting of ene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, and the like. When the polymer block (A) contains the other unsaturated monomer unit, the bonding form is not particularly limited, and it may be random or tapered.

The block copolymer only needs to have at least one of the aforementioned polymer block (A). In the case where the block copolymer has two or more polymer blocks (A), the polymer blocks (A) may be the same or different. In addition, in this specification, the term "different polymer blocks" means the monomer units constituting the polymer blocks, the weight average molecular weight, the stereoisomerism, and each of the monomer units in the case of having plural monomer units. At least one of the ratio of monomer units and the form of copolymerization (random, gradient, block) is different.

(Weight average molecular weight) The weight average molecular weight (Mw) of the polymer block (A) is not particularly limited, but the weight average molecular weight of at least one polymer block (A) among the polymer blocks (A) possessed by the block copolymer It is preferably 3,000 to 60,000, more preferably 4,000 to 50,000. Since the block copolymer has at least one polymer block (A) having a weight average molecular weight within the above range, the mechanical strength is further improved, and the molding processability is also excellent. In addition, the weight average molecular weight is a weight average molecular weight in terms of standard polystyrene obtained by gel permeation chromatography (GPC) measurement.

(Content of polymer block (A)) The content of polymer block (A) in the block copolymer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 16% by mass or less , Particularly preferably 14% by mass or less. If it is 50% by mass or less, it has appropriate flexibility, and can be a block copolymer or its hydrogenated product having excellent vibration damping properties without reducing the tanδ peak top strength. In addition, the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 6% by mass or more. If it is 1% by mass or more, it can be a block copolymer or its hydrogenated product having better mechanical properties and moldability in various applications of the laminate. In addition, the content of the polymer block (A) in the block copolymer is ^{a value obtained by 1} H-NMR measurement, and more specifically, a value measured according to the method described in the examples.

[Polymer block (B)] The polymer block (B) constituting the block copolymer is a structural unit derived from a conjugated diene compound, and has an alicyclic skeleton (X) containing one or more types represented by the following formula (X) in the main chain The structural unit (hereinafter, sometimes abbreviated as "alicyclic skeleton-containing unit"). In addition, the polymer block (B) may also contain a structural unit derived from a conjugated diene compound (hereinafter, sometimes simply referred to as "conjugated diene unit") that does not contain an alicyclic skeleton (X). The total of the alicyclic skeleton-containing unit and the conjugated diene unit in the polymer block (B) is preferably 50 mol% or more from the viewpoint of exhibiting excellent vibration damping properties, and more preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably substantially 100 mol%. When there are two or more polymer blocks (B) in the block copolymer, the polymer blocks (B) may be the same or different.

In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different. The carbon number of the above-mentioned hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 (that is, methyl). In addition, the above-mentioned hydrocarbon group may be a straight chain or a branched chain, and may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and formation of the alicyclic skeleton (X), R ¹ to R ^{3 are} particularly preferably each independently a hydrogen atom or a methyl group. In addition, in the case of a hydrogenated block copolymer, the vinyl group in the above formula (X) can be hydrogenated. Therefore, in the meaning of the alicyclic skeleton (X) in the hydride, the skeleton in which the vinyl group in the above formula (X) is hydrogenated is also included.

The polymer block (B) is a structural unit derived from a conjugated diene compound, and the alicyclic skeleton (X) is derived from the conjugated diene compound. The alicyclic skeleton (X) is produced by the method described later using anionic polymerization of a conjugated diene compound, but depending on the conjugated diene compound used, the main chain of the unit containing the alicyclic skeleton contains at least 1 Kind of alicyclic skeleton (X). With the alicyclic skeleton (X) incorporated into the main chain of the structural unit contained in the polymer block (B), the glass transition temperature rises due to the decrease of molecular motion, and the peak top strength of tanδ near room temperature Improved, can show excellent vibration damping performance.

Examples of the above-mentioned conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene Diene, 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, bacteriochlorene, myrcene and chloroprene, etc. Among them, butadiene, isoprene, or a combination of butadiene and isoprene is preferred.

In the case where butadiene and isoprene are used in combination, the blending ratio [isoprene/butadiene] (mass ratio) is not particularly limited, but it is preferably 5/95 to 95/5, It is more preferably 10/90 to 90/10, still more preferably 40/60 to 70/30, particularly preferably 45/55 to 65/35. In addition, if the mixing ratio [isoprene/butadiene] is expressed in molar ratio, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, and still more preferably 40/ 60～70/30, particularly preferably 45/55～55/45.

As a specific example, the alicyclic skeleton (X) that is mainly produced when butadiene, isoprene, or both butadiene and isoprene is used as the conjugated diene compound will be described. When butadiene is used alone as the conjugated diene compound, an alicyclic skeleton (X) having a combination of the following substituents (i) is produced. That is, in this case, the alicyclic skeleton (X) becomes only the alicyclic skeleton in which R ¹ to R ³ are hydrogen atoms at the same time. Therefore, as an example of a preferred aspect of the block copolymer or its hydrogenated product, the polymer block (B) has the following structural unit: ^{a resin containing R 1} to R ³ in the main chain and at the same time being a hydrogen atom Cyclic skeleton (X).

In addition, when isoprene is used alone as the conjugated diene compound, an alicyclic skeleton (X) having two combinations of the following substituents (v) and (vi) is mainly produced. In addition, when butadiene and isoprene are used in combination as a conjugated diene compound, an alicyclic skeleton (X) having six combinations of the following substituents (i) to (vi) is mainly produced. (i): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom (ii): R ¹ = hydrogen atom, R ² = methyl, R ³ = hydrogen atom (iii): R ¹ = hydrogen Atom, R ² = hydrogen atom, R ³ = methyl (iv): R ¹ = methyl, R ² = hydrogen atom, R ³ = hydrogen atom (v): R ¹ = methyl, R ² = methyl, R ³ = hydrogen atom (vi): R ¹ = methyl, R ² = hydrogen atom, R ³ = methyl

In the above formula (X), from the viewpoint that the molecular motion becomes smaller and the vibration damping property is further improved by having a substituent that is a hydrocarbon group, at least one alicyclic ring in the polymer block (B) The formula skeleton (X) is preferably an alicyclic skeleton (X'), ^{and at least one of the above-mentioned R 1} to R ³ is a hydrocarbon group having 1 to 11 carbon atoms. Among them, it is more preferable that the hydrocarbon group in the alicyclic skeleton (X') is a methyl group from the viewpoint of efficiently generating an alicyclic skeleton from a conjugated diene compound, vibration damping properties, and mechanical properties. . In particular, it is more preferable that R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and R ¹ to R ^{3 are} not at the same time an alicyclic skeleton of a hydrogen atom. That is, the polymer block (B) more preferably has the following structural unit: any one or more of the alicyclic skeletons having the combination of the above-mentioned substituents (ii) to (vi) are contained in the main chain.

(Vinyl bonding amount of polymer block (B)) When the structural unit constituting the polymer block (B) is any one of isoprene units, butadiene units, isoprene and butadiene mixture units, the aforementioned alicyclic skeleton is formed The bonding morphology of isoprene and butadiene other than the bonding morphology of (X) can be 1,2-bonding or 1,4-bonding in the case of butadiene. In the case of diene, it can be 1,2-bonded, 3,4-bonded, or 1,4-bonded.

In the block copolymer and its hydrogenated substances, the content of 3,4-bonded units and 1,2-bonded units in the polymer block (B) (hereinafter, sometimes only referred to as "vinyl-bonded The total amount") is preferably 55 to 95 mol%, more preferably 63 to 95 mol%, and still more preferably 70 to 95 mol%. As long as it is in the above range, excellent vibration damping properties can be exhibited. Here, the vinyl bond amount is a ^{value calculated by 1} H-NMR measurement according to the method described in the examples. In addition, when the polymer block (B) is composed only of butadiene, the aforementioned "content of 3,4-bonding unit and 1,2-bonding unit" is replaced with "1,2- The content of bonding unit" is applied.

(Alicyclic skeleton (X) content) In the polymer block (B), as long as the structural unit containing the alicyclic skeleton (X) is contained in the main chain, it is easy to suppress the viscosity even at high temperatures due to the effect of exhibiting more excellent vibration damping properties. From the viewpoint of the reduction of the subsequent force, the polymer block (B) preferably contains 1 mol% or more of the alicyclic skeleton (X), more preferably 1.1 mol% or more, and still more preferably 1.4 mol%. Ear% or more, more preferably 1.8 mol% or more, still more preferably 4 mol% or more, still more preferably 10 mol% or more, and particularly preferably 13 mol% or more. In addition, the upper limit of the content of the alicyclic skeleton (X) in the polymer block (B) is not particularly limited as long as it is within a range that does not impair the effects of the present invention, but from the viewpoint of productivity, it is preferably 40 mol% or less, 30 mol% or less, 20 mol% or less, or 18 mol% or less. From the viewpoint of further improving the vibration damping properties, the polymer block (B) preferably contains 1 mol% or more of the above-mentioned alicyclic skeleton (X'), and still more preferably 1.3 mol% or more. More preferably, it is 1.6 mol% or more. The upper limit of the content of the alicyclic skeleton (X') is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

More specifically, as the conjugated diene compound, when isoprene is used, when butadiene is used, or when butadiene and isoprene are used in combination, the content of alicyclic skeleton in each case The line is as follows. In the case of using isoprene as the conjugated diene compound, in the polymer block (B), an alicyclic skeleton (X') having a combination of the aforementioned substituents (v) and (vi) exists When one or more types are used, the total content of them is preferably 1 mol% or more from the viewpoint of exhibiting a more excellent vibration damping effect and easily suppressing the decrease in adhesive force even at high temperatures. It is preferably 1.5 mol% or more, and from the viewpoint of obtaining excellent vibration damping effects in a wide temperature range, it is still more preferably 2 mol% or more, still more preferably 3 mol% or more, and particularly preferably 4 More than mol%. In addition, the upper limit of the total content in the case of using isoprene is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

In the case of using butadiene as the conjugated diene compound, when the alicyclic skeleton (X) is present in the polymer block (B), its content is determined by the effect of exhibiting more excellent vibration damping properties, From the viewpoint of easily suppressing the decrease in adhesive force even at high temperatures, it is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 15 mol% or more, and still more preferably 20 mol% Ear% or more, more preferably 25 mol% or more, particularly preferably 30 mol% or more. In addition, the upper limit of the content in the case of using butadiene is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

In the case where butadiene and isoprene are used in combination as the conjugated diene compound, the polymer block (B) has the aforementioned substituents (ii), (iii), (v), and (vi) When there is more than one kind of alicyclic skeleton (X') in the combination of, the total content of the same is from the viewpoint of exhibiting a more excellent vibration damping effect and easily suppressing the decrease in adhesive force even at high temperatures , Preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 5 mol% or more, still more preferably 8 mol% or more, and still more preferably 13 mol% or more. The upper limit of the total content in the case of using butadiene and isoprene in combination is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X). In addition, in the case where butadiene and isoprene are used in combination as the conjugated diene compound, in the polymer block (B), an alicyclic formula having a combination of the aforementioned substituents (i) to (vi) When there is more than one type of skeleton (X), the total content of them is preferably 1 mol from the viewpoint of exhibiting a more excellent vibration damping effect and easily suppressing the decrease in adhesive force even at high temperatures % Or more, more preferably 5 mol% or more. The upper limit of the total content in the case of using butadiene and isoprene in combination is the same as the upper limit of the content of the aforementioned alicyclic skeleton (X).

In addition, the content of the alicyclic skeleton (X) (including (X')) contained in the block copolymer or its hydrogenated product is ^{determined by the 13} C-NMR measurement of the block copolymer and derived from the polymer block ( The value obtained by the integral value of the alicyclic skeleton (X) in B) is, in more detail, the value measured according to the method described in the examples.

In addition, when the hydrogenation rate of the block copolymer or its hydrogenated product in the polymer block (B) is 0 mol% or more and less than 50 mol%, it can be confirmed that the alicyclic skeleton (X) has been bonded The molar ratio between the vinyl group and the vinyl group bonded to the main chain. For example, in an alicyclic skeleton (X') having a combination of substituents (ii), (iii), (v), and (vi), the alicyclic skeleton (X') has been bonded The chemical shift system of the vinyl terminal carbon atom ((a) of the following chemical formula) in ¹³ C-NMR appears in the vicinity of 107~110 ppm, and the vinyl terminal carbon atom that has been bonded to the main chain (the following chemical formula (b)) ^{The chemical shift in 13} C-NMR is around 110-116 ppm. Moreover, when the hydrogenation rate is 0-40 mol%, ^{the peak area ratio measured by 13} C-NMR [peak area with chemical shift value of 107-110 ppm]/[peak area with chemical shift value of 110-116 ppm] usually becomes In the range of 0.01 to 3.00, from the viewpoint of exhibiting more excellent vibration damping properties, the area is preferably 0.01 to 1.50, more preferably 0.01 to 1.00, and even more preferable is 0.01 to 0.50, and still more preferable The system becomes 0.01 to 0.20.

In addition, for the hydride, ^{almost no peak derived from the carbon atom on the alicyclic skeleton (X) was observed in the 13} C-NMR measurement, but the peak derived from the alicyclic skeleton bonded to the branched alkyl group was observed. The peak of the carbon atom on (X), the branched alkyl group is derived from a ^{vinyl group having a substituent R 3} , and the R ³ is a hydrocarbon group having 1 to 11 carbon atoms. From this, regarding the hydrogenated product, even when the hydrogenation rate of the polymer block (B) is 50 to 99 mol%, the above-mentioned alicyclic type bonded to the branched alkyl group ^{derived from the vinyl group having R 3 can also be determined} The molar ratio of the carbon atoms on the skeleton (X) and the carbon atoms on the main chain bonded to the branched alkyl group derived from the vinyl group.

For example, in the alicyclic skeleton (X) having a combination of the substituents (iii) and (vi), the carbon atoms on the alicyclic skeleton (X) bonded to the isoprenyl group (below The chemical shift of the chemical formula (c)) in ¹³ C-NMR appears in the vicinity of 50.0～52.0ppm, and the carbon atom on the main chain bonded to the isoprenyl group ((d) in the following chemical formula) is at ¹³ The chemical shift system in C-NMR appears in the vicinity of 43.0-45.0ppm. In addition, when the hydrogenation rate is 40 to 99 mol%, ^{the peak area ratio measured by 13} C-NMR [peak area with a chemical shift value of 50.0-52.0 ppm]/[peak area with a chemical shift value of 43.0-45.0 ppm] It is usually in the range of 0.01 to 3.00. From the viewpoint of exhibiting more excellent vibration damping properties, the area is preferably in the range of 0.01 to 1.50, more preferably in the range of 0.01 to 1.00, and still more preferably in the range of 0.01 The range of -0.50 is more preferably 0.01-0.25. In addition, the above-mentioned peak area ratio can be measured in more detail according to the method described in Examples.

(Weight average molecular weight) The total weight average molecular weight of the polymer block (B) of the block copolymer is preferably in the state before hydrogenation from the viewpoints of vibration damping properties and molding processability when forming a laminate. 15,000 to 800,000, more preferably 50,000 to 700,000, still more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, most preferably 130,000 to 450,000.

烯、二戊烯、亞甲基降莰烯、2-亞甲基四氫呋喃、1,3-環戊二烯、1,3-環己二烯、1,3-環庚二烯、1,3-環辛二烯等之群組的至少1種化合物。 嵌段共聚物只要具有至少1個前述聚合物嵌段(B)即可。在嵌段共聚物具有2個以上的聚合物嵌段(B)之情形中，該等聚合物嵌段(B)可相同亦可不同。(Other structural units) The polymer block (B) may contain structural units derived from other polymerizable monomers other than the aforementioned conjugated diene compound as long as it does not interfere with the purpose and effects of the present invention. In this case, in the polymer block (B), the content of structural units derived from polymerizable monomers other than the conjugated diene compound is preferably less than 50 mol%, more preferably less than 30 mol% , More preferably less than 20 mol%, more preferably less than 10 mol%, particularly preferably 0 mol%. As the other polymerizable monomers, for example, selected from the group consisting of styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tertiary butyl Aromatic vinyl compounds such as styrene, 2,4-dimethylstyrene, N-vinylcarbazole, vinyl naphthalene and vinyl anthracene, as well as methyl methacrylate, methyl vinyl ether, β-pine Ene, 8,9-pair

Ene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3 -At least one compound of the group of cyclooctadiene and the like. The block copolymer only needs to have at least one of the aforementioned polymer block (B). In the case where the block copolymer has two or more polymer blocks (B), the polymer blocks (B) may be the same or different.

[Production method] (Block copolymer) As a method of producing a block copolymer, for example, one or more conjugated diene compounds are used as monomers and polymerized by an anionic polymerization method, thereby forming an alicyclic skeleton (X) containing the aforementioned alicyclic skeleton in the main chain. In the polymer block (B) of the structural unit, the monomers of the polymer block (A) are added, and the monomers and conjugated diene compounds of the polymer block (A) are further added successively according to the needs, so that the Obtain a block copolymer. The method for generating an alicyclic skeleton by the above-mentioned anionic polymerization method can use a well-known technique (for example, refer to the specification of US Patent No. 3,966,691). The alicyclic skeleton is formed at the end of the polymer by depletion of monomers, and by further adding monomers to it successively, the polymerization can be restarted from the alicyclic skeleton. Therefore, the presence or absence and content of the alicyclic skeleton can be adjusted according to the successive addition time of the monomers, the polymerization temperature, or the type and amount of the catalyst, the combination of the monomer and the catalyst, and the like. In addition, in the anionic polymerization method, an anionic polymerization initiator, a solvent, and a Lewis base as required can be used.

In the above method, the organolithium compound that can be used as a polymerization initiator for anionic polymerization includes, for example, methyl lithium, ethyl lithium, n-butyl lithium, secondary butyl lithium, tertiary butyl lithium, and pentyl lithium. Base lithium and so on. In addition, examples of dilithium compounds that can be used as a polymerization initiator include naphthalene dilithium, dilithium hexylbenzene, and the like. As a coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenyl benzoate, etc. are mentioned, for example. The usage amount of these polymerization initiators and coupling agents can be appropriately determined according to the desired weight average molecular weight of the block copolymer and its hydrogenated product. Generally speaking, the initiator such as alkyl lithium compound and dilithium compound is preferably based on the total mass of the monomers such as the polymer block (A) and the conjugated diene compound used in the polymerization per 100 mass The part is used in a ratio of 0.01 to 0.2 parts by mass, and when a coupling agent is used, it is preferably used in a ratio of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the aforementioned monomers.

The solvent is not particularly limited as long as it does not adversely affect the anionic polymerization reaction. Examples include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; aromatics such as benzene, toluene, and xylene. Hydrocarbon etc. In addition, the polymerization reaction is usually carried out at a temperature of 0 to 100°C, preferably 10 to 70°C, for 0.5 to 50 hours, preferably 1 to 30 hours.

啉等胺類；三級丁酸鈉、三級戊醇鈉或異戊醇鈉等脂肪族醇的鈉或鉀鹽、或者二烷基環己醇鈉、例如如薄荷醇鈉(sodium mentholate)般的脂環式醇的鈉或鉀鹽等金屬鹽等。此等路易斯鹼可使用單獨一種或組合二種以上而使用。In addition, by adding a Lewis base as a co-catalyst during the polymerization of the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (B) can be increased, and the content of 3,4- The content of bonding and 1,2-bonding. Usable Lewis bases include, for example, ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, 2,2-bis(2-tetrahydrofuryl)propane (DTHFP); ethylene glycol dimethyl ether, diethylene glycol Dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and other glycol ethers; triethylamine, N,N,N',N'-tetramethylene diamine, N,N, N',N'-tetramethylethylenediamine (TMEDA), N-methyl

Amines such as morpholines; sodium or potassium salts of aliphatic alcohols such as sodium tertiary butyrate, sodium tertiary amylate or sodium isoamylate, or sodium dialkylcyclohexanol, such as sodium mentholate Metal salts such as sodium or potassium salt of the alicyclic alcohol. These Lewis bases can be used alone or in combination of two or more.

The amount of Lewis base added depends on how much the content of the alicyclic skeleton (X) is controlled, and the polymer block (B) specifically contains a structure derived from isoprene and/or butadiene In the case of the unit, it is determined how much the vinyl bonding amount of the isoprene unit and/or butadiene unit constituting the polymer block (B) is controlled. Therefore, the amount of Lewis base added is not strictly limited, but it is usually 0.1 to 1,000 moles per 1 gram atom of the lithium contained in the alkyl lithium compound or dilithium compound used as the polymerization initiator. The ears are preferably used in the range of 1-100 mol.

The average feed rate of the conjugated diene compound (hereinafter, sometimes referred to as the "average diene feed rate"), from the viewpoint of increasing the content of the alicyclic skeleton (X), per 1 mole of active end , Preferably 150kg/h or less, more preferably 110kg/h or less, still more preferably 55kg/h or less, 45kg/h or less, 30kg/h or less, or 22kg/h or less. From the viewpoint of improving productivity, the lower limit is per 1 mole of active end, preferably 1 kg/h or more, more preferably 3 kg/h or more, still more preferably 5 kg/h or more, and may also be 7 kg/ h or more, may be 10kg/h or more, or 15kg/h or more.

After polymerization by the above method, active hydrogen compounds such as alcohols, carboxylic acids, and water are added to stop the polymerization reaction, thereby obtaining a block copolymer.

(Hydride) When the block copolymer obtained by the above-mentioned production method is used as a hydrogenated product, a hydrogenation reaction is carried out in the presence of a hydrogenation catalyst in an inert organic solvent. Through the hydrogenation reaction, the carbon-carbon double bond derived from the conjugated diene compound in the polymer block (B) in the block copolymer is hydrogenated to become a hydrogenated product of the block copolymer. For the hydrogenation reaction, the hydrogen pressure can be set at about 0.1-20 MPa, preferably 0.5-15 MPa, more preferably 0.5-5 MPa, and the reaction temperature may be set at about 20-250°C, preferably 50-180°C, more preferably 70 -180°C, and the reaction time is usually about 0.1 to 100 hours, preferably 1 to 50 hours. Examples of hydrogenation catalysts include Reich's nickel; heterogeneous catalysts in which metals such as Pt, Pd, Ru, Rh, and Ni are supported on monomers such as carbon, alumina, and diatomaceous earth; and include transition metal compounds and Ziegler-based catalysts, metallocene-based catalysts, etc., which are combinations of alkyl aluminum compounds, alkyl lithium compounds, etc.

The hydride obtained in this way can be coagulated by injecting the polymerization reaction liquid into methanol or the like, and then dried under heating or reduced pressure, or it can be mixed with the solvent by pouring the polymerization reaction liquid and steam into hot water. The so-called steam stripping, which is removed by boiling, is obtained by heating or drying under reduced pressure.

It is possible to specify whether to use the above-mentioned block copolymer or hydrogenated product according to the desired performance in various applications of the laminate. Similarly, it is possible to specify how much the hydrogenation rate of the carbon-carbon double bond in the polymer block (B) when it is made into a hydrogenated product in accordance with the performance desired in various applications of the laminate. For example, the higher the hydrogenation rate of the hydride, the higher the heat resistance and weather resistance. The hydrogenation rate can be set to, for example, 50 mol% or more and 99 mol% or less, 60 mol% or more and 99 mol% or less, 70 mol% or more and 99 mol% or less, 80 mol% or more, and Below 99 mol%.

Therefore, it can be a block copolymer or its hydrogenated product with a hydrogenation rate of the polymer block (B) of 0 mol% or more (that is, including the case where it is not hydrogenated) and less than 50 mol%, and also It can be a hydrogenated product with a hydrogenation rate of 50-99 mol% of the polymer block (B). In addition, the above-mentioned hydrogenation rate is based on the content of the carbon-carbon double bond in the structural unit derived from the conjugated diene compound and the alicyclic skeleton (X) in the polymer block (B) by ¹ H- after hydrogenation. The value obtained by the NMR measurement is, more specifically, the value measured according to the method described in the examples.

(Combination style of polymer block (A) and polymer block (B)) The block copolymer is not limited as long as the polymer block (A) and the polymer block (B) can be combined. The combination can be linear, branched, radial, or a combination of two or more of these Combine any of the styles. Among them, the combination of the polymer block (A) and the polymer block (B) is preferably linear. As an example, A represents the polymer block (A) and B represents the polymer block. (B) In the case of (B), the diblock copolymer represented by AB, the triblock copolymer represented by ABA or BAB, the tetrablock copolymer represented by ABAB, the five represented by ABABA or BABAB Block copolymers, (AB) nZ type copolymers (Z represents a coupling agent residue, n represents an integer of 3 or more), and the like. Among them, a linear triblock copolymer or a diblock copolymer is preferred. From the viewpoints of flexibility and ease of production, it is preferred to use an A-B-A type triblock copolymer. As an A-B-A type triblock copolymer, specifically, styrene-butadiene/isoprene-styrene copolymer is mentioned. Among them, at least one of the base layer and the adhesion layer is preferably a hydrogenated product containing at least a styrene-hydrogenated butadiene/isoprene-styrene copolymer as a block copolymer.

Herein, in this specification, when the same type of polymer blocks are combined linearly via a difunctional coupling agent or the like, the entire combined polymer blocks are regarded as one polymer block. Accordingly, including the above-mentioned examples, the polymer block that should be strictly labeled as YZY (Z represents the coupling residue), except for the case where it is necessary to distinguish it from the separate polymer block Y, is represented as a whole. Is Y. In this specification, since such a polymer block containing a coupling agent residue is considered as described above, for example, a polymer block containing a coupling agent residue and strictly speaking should be marked as ABZBA (Z represents a coupling agent residue) The block copolymer system is labeled ABA and is regarded as an example of a triblock copolymer.

(Content of polymer blocks (A) and (B)) In the block copolymer, as long as it does not interfere with the purpose and effects of the present invention, it may also contain polymer blocks composed of other monomers other than the aforementioned polymer blocks (A) and (B), but the aforementioned polymerization The total content of the polymer block (A) and the aforementioned polymer block (B) is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably substantially 100% by mass. As long as it is 90% by mass or more, it can be made to have excellent vibration damping properties and molding processability, and it is easy to suppress the decrease in adhesive force even at high temperatures, and it can be suitably used for the block copolymer or its hydrogenated product of the laminate.

(Weight average molecular weight) The weight average molecular weight (Mw) of the block copolymer and its hydrogenated product obtained by gel permeation chromatography in terms of standard polystyrene is preferably 15,000-800,000, more preferably 50,000-700,000, More preferably, it is 60,000 to 600,000, more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450,000. As long as the weight average molecular weight of the block copolymer and its hydrogenated product is 15,000 or more, the heat resistance becomes high, and as long as it is 800,000 or less, the moldability and processability become good.

[tanδ] (Peak top temperature and intensity of tanδ) Tanδ (loss tangent) is the ratio of loss modulus/storage modulus at a frequency of 1 Hz in dynamic viscoelastic measurement. The peak top temperature and strength of tanδ greatly contribute to vibration damping and other physical properties. Here, the peak top intensity of tanδ refers to the value of tanδ when the peak of tanδ becomes the maximum. In addition, the peak top temperature of tanδ refers to the temperature at which the peak of tanδ becomes the maximum.

In this specification, the peak top temperature and strength of the tanδ of the block copolymer or its hydrogenated product are made by pressing the block copolymer or its hydrogenated product at a temperature of 230°C and a pressure of 10 MPa for 3 minutes to produce a unit with a thickness of 1.0 mm. For the layered piece, the single-layered piece was cut into a disc shape, and this was used as a test piece for measurement. The measurement conditions are based on JIS K 7244-10 (2005), with a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 100°C, and a heating rate of 3°C/min. In addition, the peak top temperature and tanδ intensity of the block copolymer or its hydrogenated product are, more specifically, values measured according to the method described in the examples.

The block copolymer or its hydrogenated product has a peak top intensity of 1.0 or more that can be tan δ by the above measurement. Among the higher ones, it is 1.5 or more, and some of them are 1.9 or more. The higher the peak top strength of tanδ, the better the physical properties such as vibration damping properties at temperature. If it is 1.0 or more, sufficient vibration damping properties can be obtained under actual use environments. In addition, the peak top temperature of the tanδ of the block copolymer or its hydrogenated product is preferably -50°C or higher, more preferably -40°C or higher, still more preferably -30°C or higher, and still more preferably -25°C or higher. It can be above 0°C. In addition, the upper limit of the peak top temperature of tanδ may be a range that does not impair the effects of the present invention, and may be 50°C or lower, 40°C or lower, or 35°C or lower. The range of the peak top temperature of tanδ is, for example, preferably -50 to 50°C, more preferably -40 to 40°C, still more preferably -30 to 30°C, and still more preferably -25 to 25°C. As long as the peak top temperature of tanδ is -50°C or higher, sufficient vibration damping properties can be obtained in an actual use environment, and if it is 50°C or lower, the desired adhesiveness can be exhibited when used in an adhesive layer.

(tanδ becomes the maximum width of the temperature range above 1.0) In addition, the block copolymer or its hydrogenated product has a continuous temperature range in which the tanδ at -70 to 100°C measured by the above measurement conditions becomes 1.0 or more. The maximum width of the temperature range is preferably 12°C or more, and more It is preferably 13°C or higher, more preferably 15°C or higher, and still more preferably 17°C or higher. As mentioned above, in the structural unit of the polymer block (B), the aforementioned alicyclic skeleton (X) is incorporated into the main chain, and the molecular motion becomes smaller due to the higher vinyl bonding amount, so the glass transfer The temperature will rise, and the glass transition will be gentler with respect to the temperature change. Thereby, the temperature range in which the tanδ of the block copolymer or its hydrogenated product is 1 or more is widened, and it becomes possible to exhibit vibration damping properties in a wide temperature range. As long as the maximum width of the temperature range where the tan δ becomes 1.0 or more is 12° C. or more, or even 13° C. or more, more excellent vibration damping properties can be obtained in an actual use environment. In addition, there is no particular upper limit for the maximum width of the temperature range, but from the viewpoint of productivity, for example, the upper limit may be 35°C, 30°C, or 25°C.

≪Substrate layer≫ From the viewpoint of being suitable for improving the vibration damping properties of the adherend, the base layer may contain the above-mentioned block copolymer or its hydrogenated product. The content of the block copolymer or its hydrogenated product in the substrate layer is preferably 1 to 100% by mass. From the viewpoint that it is easy to further improve the vibration damping properties of the adherend, the content of the block copolymer or its hydrogenated product in the base layer is more preferably 3% by mass or more, and still more preferably 5% by mass or more, and More preferably, it is 10% by mass or more. In addition, the upper limit of the content is not particularly limited as long as it is within a range that does not impair the effects of the present invention. However, it maintains the strength of the laminate and is easily compatible with other resins that can be used as the material of the base layer described later. In other words, it is more preferably 90% by mass or less, still more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less, and still more preferably 40 The mass% or less may also be 30 mass% or less and 25 mass% or less.

[Non-alicyclic skeleton block copolymer and its hydrogenated products] From the standpoint of performance as a laminate, the base layer contains the same polymer block (A) and polymer block (B) as the block copolymer or its hydrogenated product, and may also contain the same The polymer block (B) does not have a block copolymer or its hydrogenated product (hereinafter, sometimes referred to as "non-alicyclic Formula backbone block copolymer or its hydrogenated product"). The above-mentioned non-alicyclic skeleton block copolymers and their hydrogenated products are combined with the above-mentioned block copolymers, except that the polymer block (B) does not have a structural unit containing an alicyclic skeleton represented by formula (X) in the main chain. The segment copolymer or its hydrogenated product is the same.

[Other resins] In the base material layer, from the viewpoint of performance as a laminate and economical efficiency, it is preferable to use a resin other than the above-mentioned block copolymer or its hydrogenated product (hereinafter, sometimes referred to as "other resin") Use the material as the base layer.

(Olefin resin) From the viewpoint of performance as a laminate and economical efficiency, the above-mentioned other resin is preferably an olefin resin. Examples of olefin resins include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene; Single polymer or copolymer of α-olefin; propylene and/or copolymer of ethylene and α-olefin, etc. As the above-mentioned α-olefins, for example, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eicosene and other α-olefins with a carbon number of 20 or less. One or two or more of these can be used. In addition, modified olefin resins in which these olefin resins are modified by maleic acid or the like can also be used. Among these olefin resins, polypropylene is preferred from the viewpoint of high compatibility with the above-mentioned block copolymer or its hydrogenated product and suitable for obtaining a laminate having excellent transparency. More specifically, as an example of a preferable aspect of the present embodiment, in the base material layer, the other resin described above may be an olefin resin, a block copolymer, or a hydrogenated product thereof. Among them, it is preferable to use a hydrogenated product of an olefin resin and a block copolymer. Since the olefin resin has good compatibility with the above-mentioned hydrogenated compound, it is easy to maintain more excellent transparency of the base layer.

(Resin other than olefin resin) In addition, as the other resin described above, resins other than the above-mentioned olefin resin can be used. Examples of resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer sulfide, styrene-butadiene rubber, styrene-isoprene rubber, and nitrile Rubber, butyl rubber, natural rubber, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylate copolymer, ethylene-ethyl(meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer, Metal ion cross-linked resins of ethylene-(meth)acrylic acid copolymers (ionomers), polystyrene, AS resins, ABS resins and other styrene resins, polyphenylene ether resins, nylon 6, nylon 66 Polyamide resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyurethane resins, polyoxymethylene homopolymers, polyoxymethylene copolymers, etc. Acrylic resins such as aldehyde resins and polymethyl methacrylate resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl chloride-vinyl acetate copolymers, and the like.

In addition, as the material of the base material layer, from the viewpoint of performance as a laminate and economical efficiency, it is preferable to include: a combination of a block copolymer or its hydrogenated product and other resins, and a non-alicyclic skeleton The combination of a block copolymer and its hydrogenated product and other resins is more preferably a block copolymer or its hydrogenated product and other resins from the viewpoints of performance as a laminate, economic efficiency, and obtaining more excellent vibration damping properties The combination. The structure of the substrate layer may be a single layer, or a multilayer structure of two or more layers. When two or more layers are included, two or more resins with different materials can also be used.

[content] The content of the non-alicyclic skeleton block copolymer and its hydrogenated product in the base layer is preferably 1% by mass or more, more preferably 5% by mass or more, from the viewpoint of performance as a laminate It is 10% by mass or more. On the other hand, the upper limit of the content of the non-alicyclic skeleton block copolymer and its hydrogenated product in the base layer is not particularly limited as long as it does not impair the effects of the present invention, and may be 100% by mass. However, from the viewpoint of economic efficiency, it is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.

The content of other resins in the substrate layer is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, from the standpoint of performance and economy as a laminate It is preferably 40% by mass or more, still more preferably 50% by mass or more, and still more preferably 60% by mass or more. On the other hand, the upper limit of the content of the above-mentioned other resins in the base layer is not particularly limited as long as it does not impair the effects of the present invention. It may be 100% by mass. However, when the base layer contains the above In the case of a block copolymer or its hydrogenated product, from the viewpoint of easily improving the vibration damping properties of the adherend, it is preferably 97% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass %the following.

In the base layer, the ratio of the content of the block copolymer or its hydrogenated product to other resins, if the total content of these is 100% by mass, the content of the block copolymer or its hydrogenated product is preferably 1 to 99 mass%, more preferably 1 to 90 mass%, still more preferably 1 to 80 mass%, still more preferably 1 to 70 mass%, still more preferably 1 to 60 mass%, still more preferably 1 to 50% by mass, more preferably 1-40% by mass, or 1-30% by mass, or 1-25% by mass. As an example of a preferable aspect of this embodiment, when the other resin is an olefin resin, the ratio of the above content is that the content of the block copolymer or its hydrogenated product is 1 to 99% by mass, and the content of the olefin resin is 99 to 99%. 1% by mass, and more preferably the same as the ratio of the content of the block copolymer or its hydrogenated product and other resins. As an example of a more preferable aspect of this embodiment, when the other resin is polypropylene, the content of the block copolymer or its hydrogenated product is 1 to 99% by mass, and the content of polypropylene is 99 to 1% by mass, and more The preferred aspect is the same as the ratio of the content of the block copolymer or its hydrogenated product to other resins.

In addition, as an example of a preferable aspect of this embodiment, when the material of the base layer is a non-alicyclic skeleton block copolymer or a combination of its hydrogenated product and other resins, the non-alicyclic skeleton block copolymer The ratio of the content of its hydrogenated product to other resins, if the total content of these is set to 100% by mass, the content of the non-alicyclic skeleton block copolymer or its hydrogenated product is preferably 1 to 99% by mass , More preferably 1 to 90 mass%, still more preferably 1 to 80 mass%, still more preferably 1 to 70 mass%, still more preferably 1 to 60 mass%, still more preferably 1 to 50 mass%, and More preferably, it is 1-40% by mass. The total content of the block copolymer or its hydrogenated product, non-alicyclic skeleton block copolymer and its hydrogenated product, and other resins in the base layer is preferably 90% by mass or more, more preferably 95% by mass The above may be 100% by mass.

[additive] In addition, the base material layer in the present embodiment does not impede the inclusion of the adhesion-imparting resin described later in the range that does not impair the effects of the present invention. However, due to the adhesiveness of the base material layer, the performance as a base material is impaired, and there is a risk of undesirable adhesion to the base material. Therefore, the adhesion imparting resin in the base material layer The content of is preferably less than 1% by mass, and the base material layer may be substantially free of adhesion-imparting resin (the content of adhesion-imparting resin is 0% by mass). In the base material layer, in a range that does not impair the purpose of the present invention, further additives may be added as needed. Examples of additives include cross-linking agents (isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, acridine-based cross-linking agents, amine resins, etc.), heat stabilizers, and light stabilizers. Agent, ultraviolet absorber, infrared absorber, antioxidant, lubricant, coloring agent, antistatic agent, flame retardant, water repellent, water repellent, hydrophilicity imparting agent, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave Barrier property imparting agent, light transmittance modifier, fluorescent agent, slip property imparting agent, transparency imparting agent, anti-blocking agent, metal inertizer, antibacterial agent, crystal nucleating agent, tortoise Crack preventive agent, ozone deterioration preventive agent, rodent inhibitor, dispersant, tackifier, light stabilizer, weathering agent, copper damage preventive agent, reinforcing agent, antifungal agent, macrocyclic molecule (cyclodextrin, calixarene, Cucurbituril (cucurbituril, etc.), adhesives (acrylic adhesives, etc.) other than the aforementioned adhesion-imparting resin. The content of the additive is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less per 100 parts by mass of the above-mentioned resin component for the base layer from the viewpoint of suppressing bleeding from the substrate layer.

≪Adhesive layer≫ In addition to the above-mentioned block copolymer or its hydrogenated product, the adhesion layer in this embodiment preferably contains an adhesion-imparting resin from the viewpoint of improving the adhesion of the laminate and maintaining the adhesion even at high temperatures.

[Adhesive Resin] Examples of the adhesion-imparting resin include: benzofuran resins such as coumarone-indene resin; p-tertiary butylphenol-acetylene resin, phenol-formaldehyde resin, terpene-phenol resin, polyterpene resin, xylene- Phenolic resins and terpene resins such as formaldehyde resins; petroleum resins such as aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, and modified alicyclic petroleum resins; Rosin ester represented by neopentyl erythritol ester of rosin and glyceryl ester of rosin, hydrogenated rosin, methyl ester of hydrogenated rosin, neopentyl erythritol ester of polymerized rosin, hydrogenated rosin ester, high melting point ester resin, polymerized rosin, Rosin-based resins such as hardened rosin and special rosin esters. Among them, as the adhesion-imparting resin, an alicyclic saturated hydrocarbon-based resin can be suitably used. Examples of the alicyclic saturated hydrocarbon-based resin include hydrogenated aromatic petroleum resins, and commercial products such as the "ALCON" series manufactured by Arakawa Chemical Industry Co., Ltd. can also be used. These adhesion-imparting resins may be used alone or in combination of two or more kinds. In addition, from the viewpoints of reducing the residual glue of the obtained adhesive layer and improving the heat resistance and weather resistance, it is preferable to use a hydrogenated adhesive imparting resin. The softening point of the adhesion-imparting resin is preferably 85 to 160°C, more preferably 100 to 150°C, and still more preferably 105 to 145°C. As long as the softening point of the adhesion-imparting resin is 85°C or more, it becomes easy to suppress the decrease in adhesive retention at high temperature (about 60°C), and as long as it is 160°C or less, the molding processability of the composition constituting the adhesive layer is good.

[content] The content of the above-mentioned block copolymer or its hydrogenated product in the adhesive layer may be 100% by mass, but from the viewpoint of the vibration damping properties of the laminate and the adhesive force at high temperatures, it is preferably 1 to 80% by mass. In addition, the above-mentioned content of the block copolymer or its hydrogenated product in the adhesive layer is more preferably 5% by mass or more, and still more preferably 10% by mass or more from the viewpoint of making the laminate more excellent in vibration damping properties. On the other hand, the above-mentioned content of the block copolymer or its hydrogenated product in the adhesive layer is more preferably 70% by mass or less, and still more preferably 60% by mass from the viewpoint of economy and easier maintenance of adhesion at high temperatures. % Or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.

The content of the adhesive imparting resin in the adhesive layer, from the viewpoint of the adhesive force of the adhesive layer, is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 15 Above mass%. On the other hand, the above-mentioned content of the adhesion-imparting resin in the adhesive layer is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less from the viewpoint of reducing residual glue in the adhesive layer .

[Non-alicyclic skeleton block copolymer and its hydrogenated products] In addition, as the resin component constituting the adhesive layer, from the viewpoint of performance as a laminate, it is preferable to use the above-mentioned non-alicyclic skeleton block copolymer or its hydrogenated product. The content of the non-alicyclic skeleton block copolymer or its hydrogenated product in the adhesive layer is preferably 10% by mass or more, and more preferably 20, from the viewpoint of the reduction of the residual glue of the adhesive layer and the adhesive force of the adhesive layer. Mass% or more, more preferably 30 mass% or more, and still more preferably 40 mass% or more. On the other hand, the upper limit of the content of the non-alicyclic skeleton block copolymer and its hydrogenated product in the adhesive layer is not particularly limited within a range that does not impair the effect of the present invention. It can be 100% by mass, but it is economical From the viewpoint of performance, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.

[Other resin components] (Olefin resin) In the range that does not impair the purpose of the present invention, an olefin resin can be used as the resin component constituting the adhesive layer. Examples of olefin resins include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene; Single polymer or copolymer of α-olefin; propylene and/or copolymer of ethylene and α-olefin, etc. As the above-mentioned α-olefins, for example, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eicosene and other α-olefins with a carbon number of 20 or less. One or two or more of these can be used. In addition, modified olefin resins in which these olefin resins are modified by maleic acid or the like can also be used.

(Resin other than olefin resin) Moreover, in the range which does not impair the objective of this invention, resin other than the said olefin resin can be used as a resin component which comprises an adhesive layer. Examples of resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer sulfide, styrene-butadiene rubber, styrene-isoprene rubber, and nitrile Rubber, butyl rubber, natural rubber, ethylene-vinyl acetate copolymer, ethylene-(meth)acrylate copolymer, ethylene-ethyl(meth)acrylate copolymer, ethylene-(meth)acrylic acid copolymer, Metal ion cross-linked resins of ethylene-(meth)acrylic acid copolymers (ionomers), polystyrene, AS resins, ABS resins and other styrene resins, polyphenylene ether resins, nylon 6, nylon 66 Polyamide resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyurethane resins, polyoxymethylene homopolymers, polyoxymethylene copolymers, etc. Acrylic resins such as aldehyde resins and polymethyl methacrylate resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl chloride-vinyl acetate copolymers, and the like.

(additive) In the adhesive layer, plasticizers and fillers can be added as needed within the scope that does not impair the purpose of the present invention. Examples of plasticizers include: paraffin-based, naphthenic-based, and aromatic-based processing oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; minerals Oil; liquid co-oligomer of ethylene and α-olefin; liquid paraffin; polybutene; low molecular weight polyisobutylene; liquid polybutadiene, liquid polyisoprene, liquid polyisoprene/ Liquid polydienes such as butadiene copolymers, liquid styrene/butadiene copolymers, and liquid styrene/isoprene copolymers and their hydrogenated products. Examples of fillers include talc, mica, calcium silicate, glass, glass flakes, glass beads, glass hollow spheres, glass fibers, calcium carbonate, magnesium carbonate, zinc carbonate, basic magnesium carbonate, aluminum hydroxide, Magnesium hydroxide, calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, silica alumina, diatomaceous earth, wollastonite, zeolite, diaspore, aluminum Sodium silicate, magnesium silicate, graphene, barium carbonate, silicon nitride, aluminum nitride, boron nitride, potassium titanate, aluminum silicate (kaolin, clay, pyrophyllite, bentonite), magnesium silicate ( Othepite), aluminum borate, calcium sulfate, magnesium sulfate, aluminum oxide, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, naphthalene Rice carbon tube, graphite, carbon fiber, activated carbon, carbon hollow sphere, calcium titanate, lead zirconate titanate, silicon carbide and other inorganic fillers; wood flour, starch and other organic fillers; organic pigments, etc. These fillers may be used alone, or two or more of them may be used in combination. In addition, in the adhesive layer, other additives may be further added as needed within the scope not to impair the purpose of the present invention. Examples of additives include cross-linking agents (isocyanate-based cross-linking agents, epoxy-based cross-linking agents, metal chelate-based cross-linking agents, acridine-based cross-linking agents, amine resins, etc.), heat stabilizers, and light stabilizers. Agent, ultraviolet absorber, infrared absorber, antioxidant, lubricant, coloring agent, antistatic agent, flame retardant, water repellent, water repellent, hydrophilicity imparting agent, conductivity imparting agent, thermal conductivity imparting agent, electromagnetic wave Barrier imparting agent, light transmittance modifier, fluorescent agent, sliding property imparting agent, transparency imparting agent, anti-adhesion agent, metal inertizer, antibacterial agent, crystal nucleating agent, anti-cracking agent, ozone deterioration Preventive agents, rodent inhibitors, dispersants, tackifiers, lightfasteners, weathering agents, copper damage inhibitors, reinforcing agents, antifungal agents, macrocyclic molecules (cyclodextrin, calixarene, cucurbituril, etc.), the aforementioned Adhesives (acrylic adhesives, etc.) other than the adhesion imparting resin. On the other hand, from the viewpoint of maximizing the effect of the present invention, in the adhesive layer, the respective contents of the plasticizer, filler, and additives are preferably 10% by mass or less, and more preferably 5% by mass or less. Preferably, it is 2% by mass or less. As long as the content is 10% by mass or less, it is considered that it hardly affects the performance of the tanδ strength described later.

≪Method of manufacturing laminated body≫ The manufacturing method of the above-mentioned laminate is not particularly limited, and examples include: (1) The composition of the base layer and the composition of the adhesive layer are caused by a multi-layer T-die (T-DIE) extruder, etc. The co-extrusion method; (2) the method of coating the composition of the adhesive layer on the formed substrate layer; (3) the method of compressing the formed substrate layer and the composition of the adhesive layer Laminated compression molding method, etc.

The composition constituting the base layer and the composition constituting the adhesion layer can be manufactured by melt kneading, respectively. As for melt kneading, as long as the components to be blended in each layer are mixed using a Henschel mixer, V-blender, belt blender, drum blender, cone blender, etc., or After mixing, it is only necessary to perform melt kneading by a uniaxial or biaxial extruder, a kneader, or the like. The temperature during melt kneading can be appropriately set, but is usually 150 to 300°C, preferably 160 to 250°C. From the viewpoint of easily producing a laminate by extrusion molding, the obtained respective compositions constituting the base layer and the adhesive layer are preferably pelletized separately.

In the case of manufacturing a laminate by the coating method of (2) above, the composition constituting the adhesive layer can be dissolved in an organic solvent to prepare a solution, and the solution can be applied to the formed substrate layer and then dried, Appropriately obtain a laminate. The organic solvent is not particularly limited as long as it can dissolve the composition constituting the adhesive layer. As said solvent, cyclohexane, methylcyclohexane, n-hexane, n-heptane, benzene, toluene, toluene-ethanol mixed solvent, xylene, ethylbenzene, tetrahydrofuran etc. are mentioned, for example. These solvents may be used alone, or two or more of them may be used in combination. From the viewpoints of ease of application, ease of solution production, and ease of drying, toluene, a toluene-ethanol mixed solvent, xylene, and ethylbenzene are preferred. The concentration of the resin component in the solution is preferably 5-50% by mass, more preferably 5-40% by mass, and still more preferably 5~ 30% by mass.

In the case of manufacturing a laminate by the co-extrusion molding method of (1) above, the composition constituting the substrate layer and the composition constituting the adhesive layer are respectively melted and plasticized using different extruders to make each Particles. After that, the feed block die that has been installed at the front end of the extruder can be used to merge the pellets into multiple layers and extrude them, and then obtain them in the form of a film, thereby making them suitable for production. In the case of manufacturing a laminate by the compression molding method described in (3) above, a granular or sheet-shaped composition constituting the adhesive layer can be superimposed on a molded substrate, and then compressed and molded while being heated, and then cooled down. Obtain appropriately.

When the composition constituting the adhesive layer is a hot-melt type, the same hot-melt applicator as in the past can be used. After the composition is heated and melted and applied to the base material layer, it is cooled down. Appropriately obtain a laminate.

An example of the combination of the composition constituting the base layer and the composition constituting the adhesive layer in the laminate is disclosed. For the above combination, when the block copolymer or its hydrogenated product is represented by <1>, and the non-alicyclic skeleton block copolymer or its hydrogenated product is represented by <2>, for example: The composition constituting the base layer includes an olefin resin and <1> and/or <2>, and the composition constituting the adhesive layer includes a laminate of an adhesion-imparting resin and <1> and/or <2> (but, the base layer And at least one of the adhesive layers contains <1>); The composition constituting the substrate layer includes an olefin resin and <1> and/or <2>, and the composition constituting the adhesive layer includes a laminate of an adhesion-imparting resin and <1>; The composition constituting the substrate layer includes an olefin resin and <1> and/or <2>, and the composition constituting the adhesive layer includes a laminate of an adhesion-imparting resin and <2> (but at least among the substrate layer and the adhesive layer 1 layer contains <1>); The composition constituting the substrate layer includes an olefin resin and <1>, and the composition constituting the adhesive layer includes an adhesion-imparting resin and a laminate of <1> and/or <2>; The composition constituting the substrate layer includes an olefin resin and <2>, and the composition constituting the adhesive layer includes an adhesion-imparting resin and a laminate of <1> and/or <2> (however, at least among the substrate layer and the adhesive layer 1 layer contains <1>). The present embodiment is not limited to the combination of the composition constituting the base layer and the composition constituting the adhesive layer. The specific aspects of <1>, <2>, olefin resin, and adhesion-imparting resin in the composition constituting the base layer and the composition constituting the adhesion layer are the same as the above-mentioned specific aspects, respectively. In addition, the composition constituting the substrate layer and the composition constituting the adhesive layer may each contain the above-mentioned additives.

≪Physical properties of each layer and laminate≫ [Ratio of hardness [i/ii]] In this embodiment, the ratio [i/ii] of the Shore A hardness i of the base layer to the Shore A hardness ii of the adhesive layer is 1.1 or more. If the ratio [i/ii] of the Shore A hardness is less than 1.1, the function of the base layer as a support for the adhesive layer is impaired, and the adhesive layer becomes difficult to be fixed to the base layer. Undesirable conditions may occur when used. The above-mentioned ratio [i/ii] has different values depending on the application, but from the viewpoint that the adhesive layer can be fixed to the substrate layer and the laminate can be easily attached and peeled off, it is preferably 1.2 or more, more preferably It is 1.3 or more. In addition, the upper limit of the above-mentioned ratio [i/ii] differs depending on the application, and therefore cannot be uniformly specified, but it can be set to 3.3 or less, for example.

[hardness] The Shore A hardness i of the substrate layer is not limited as long as it satisfies the hardness ratio [i/ii]. On the other hand, from the viewpoint that the performance as a base layer and the ease of attaching and peeling of the laminate can be appropriately exhibited, the Shore A hardness i of the base layer is preferably 60-100, more preferably It is 70～98. The Shore A hardness ii of the adhesive layer is not limited as long as it satisfies the hardness ratio [i/ii]. On the other hand, from the viewpoints of adhesion to the substrate layer, resistance to adhesive residue, and ease of attaching and peeling to the material to be bonded, the Shore A hardness ii of the adhesive layer is preferably 30 to 80. More preferably, it is 40-70. In addition, the Shaw A hardness, in more detail, is a value measured according to the method described in the examples.

[Storage modulus of adhesive layer] In this embodiment, the ratio of the storage modulus E'(23°C) of the adhesive layer at 23°C to the storage modulus E'(60°C) at 60°C [E'(23°C)/E'(60°C) )], preferably 2 or more. In this embodiment, since the adhesive layer contains the above-mentioned block copolymer or its hydrogenated product, the above-mentioned storage modulus ratio [E'(23°C)/E'(60°C)] easily becomes 2 or more. Generally speaking, the adhesive force decreases as the temperature becomes higher, but in this embodiment, as long as the storage modulus ratio [E'(23°C)/E'(60°C)] is 2 or more, the At 23°C to 60°C, the degree of peel strength decreases, and it tends to be less likely to peel off even at high temperatures and less likely to produce residual glue. In this embodiment, the ratio [E'(23°C)/E'(60°C)] of the above-mentioned storage modulus of the adhesive layer is adjusted by adjusting the composition of the adhesive layer (the above-mentioned adhesion imparting resin, the above-mentioned block copolymerization The type and content of the above-mentioned non-alicyclic skeleton block copolymer and its hydrogenated product, and other resin components), etc., can also be 2.5 or more, or even 3.0 or more. In addition, the storage modulus, in more detail, is a value measured according to the method described in the examples.

[tanδ intensity] The above-mentioned block copolymer or its hydrogenated product can exhibit excellent vibration damping properties. Therefore, when the base layer contains a block copolymer or its hydrogenated product, the tanδ strength of the base layer is preferably at least 0.05 at a temperature of 23°C, more preferably at least 0.10, and preferably at a temperature of 40°C. 0.05 or more, more preferably 0.10 or more, preferably 0.05 or more at a temperature of 60°C, more preferably 0.10 or more. In addition, when the adhesive layer contains a block copolymer or its hydrogenated product, the tanδ strength of the adhesive layer is preferably 0.10 or more at a temperature of 23°C, more preferably 0.15 or more, and still more preferably 0.18 or more, at 40°C The temperature is preferably 0.10 or more, more Canon is 0.15 or more, then Canon is 0.18 or more, and then Canon is 0.25 or more, at a temperature of 60°C, it is preferably 0.10 or more, more Canon is 0.15 or more, and further Canon is 0.18 or more . In addition, the loss factor of the adherend to which the laminated body has been attached is expected to be preferably greater than 0.05, more preferably 0.10 or greater than the loss factor of the adherend to which the laminated body is not attached. Preferably, it becomes larger than 0.15. In particular, when both the base layer and the adhesive layer contain a block copolymer or its hydrogenated product, the loss coefficient of the adherend with the laminated body is compared with that of the adherend without the laminated body. The loss coefficient is expected to be preferably increased by 0.10 or more, more preferably increased by 0.15 or more, and still more preferably increased by 0.20 or more. In addition, the tanδ intensity is, in more detail, a value measured according to the method described in the examples.

[Peel strength] In this embodiment, the peel strength of the laminate is that the acrylic resin board is used as the adherend, and the adhesive layer of the laminate is in contact with the adherend. It is measured in accordance with JIS Z 0237 (2009). The 180-degree peel strength is preferably 5.0N/25mm or more at a measurement temperature of 23°C, and more preferably 6.0N/25mm or more. In addition, the peel strength under the same conditions is preferably 2.0N/25mm or more at a measurement temperature of 60°C, and more preferably 2.5N/25mm or more. Generally speaking, the adhesive force decreases as the temperature becomes higher, but in this embodiment, one or both of the base material layer or the adhesive layer contains the above-mentioned block copolymer or its hydrogenated product, and the The content is adjusted to an appropriate range, etc., thereby making it easier to achieve the above-mentioned adhesive force. Furthermore, in this embodiment, the ratio of the peel strength at 60°C of the laminate to the peel strength at 23°C can also be 0.3 or more, or even 0.4 or more. The ratio of the peeling strength can be easily achieved by adjusting the composition of the adhesive layer (the above-mentioned block copolymer or its hydrogenated product, the above-mentioned type and content of the adhesion-imparting resin and optional components) and the like. In addition, the peel strength, in more detail, is a value measured according to the method described in the examples.

≪The size of the laminated body≫ The thickness of the adhesive layer constituting the laminate of the present embodiment is not particularly limited, but it is usually preferably 1 μm or more and 200 μm or less, more preferably 5 μm or more and 150 μm or less, and still more preferably 5 μm or more and 100 μm or less. On the other hand, the thickness of the substrate layer is not particularly limited, as long as it is specified according to the purpose of the laminate, but in terms of properly exerting the adhesive force of the adhesive layer, it is preferably 500 μm or less, more preferably 200 μm or less , More preferably 100μm or less. In addition, the thickness of the base layer is usually 5 μm or more.

≪Use≫ In this embodiment, the laminate can be used for various applications. The use is, for example, an adhesive containing a laminate, and examples of the adhesive include a pressure-sensitive adhesive. In addition, adhesive tapes, adhesive sheets, and surface protection films containing the above-mentioned pressure-sensitive adhesive can be cited.

Moreover, as said adhesive agent, a hot melt adhesive agent can be mentioned. The above-mentioned hot melt adhesives include, for example: Used in disposable diapers, adult incontinence products, sanitary napkins, mattresses, bandages, surgical drape (surgical drape), single-sided tape, double-sided tape, transfer tape, labels, plastic sheets, non-woven sheets, paper sheets, cardboard, Use in books, filters or articles with packaging; Use in gasket sealants (especially in the fields of automobiles, motor parts, and technical lighting); Use in the manufacture of multi-layer film resealable trays; Use in articles containing materials for mailing containers; In anti-vibration materials, cushioning materials, shock-absorbing materials, low-rebound materials, anti-falling materials, shock-proof materials, shock-proof materials, or vibration-damping materials (preferably sound-absorbing materials, more preferably attenuating or sound-absorbing mats in the automotive industry, Liner, sheet and tape); Use in electronic devices (especially LCD displays, LED displays, touch screens, or flexible thin-film solar cells); Use in transdermal drug delivery systems; Between conduits (preferably cooling coils), electronic parts (preferably light-emitting parts, computer equipment, mobile phones, tablets, touch screens, automotive technology high-fidelity systems, and audio systems), solar heating heat pipes and water tanks Combinations of fuel cells and wind turbines, computer chip manufacturing, optical devices, batteries, cabinets, coolers, heat exchange devices, wires, cables, heating wires, refrigerators, dishwashers, air-conditioning equipment, batteries, transformers , Laser equipment, functional clothing, car seats, medical equipment, fire protection devices, electric motors, airplanes, and trains; Use in filaments of 3D printing materials, sealants or molding sealants for sealing heating devices; The use of joining objects with substrates formed of wood, metal, polymer plastic, glass and textiles; the use of joining to the outside in the water supply tower; as in the manufacture of footwear Or use of glaze in the manufacture of windows, in the manufacture of doors and building panels, or in the manufacture of portable devices and displays; Used in binding, wood bonding, flat lamination, flexible packaging, profile wrapping, edge banding, textile lamination, low-pressure forming, and shoes; Use in the manufacture of books, packaging films, rigid panels, furniture, windows, footwear, car headlights, car trims, or bonded fabrics/fabrics for clothing; Use in decorative film. [Example]

Hereinafter, the present invention will be explained more specifically with examples and comparative examples, but the present invention is not limited to these.

<Block copolymer and hydrogenated product> The physical property evaluation method of the block copolymer or hydrogenated product obtained by the manufacturing example mentioned later is demonstrated below. (1) Content of polymer block (A) The block copolymer before hydrogenation was dissolved in CDCl ₃ and ^{measured by 1} H-NMR [device: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 °C], the content of the polymer block (A) is calculated from the ratio of the peak intensity derived from styrene to the peak intensity derived from diene.

(2) Weight average molecular weight (Mw) According to the gel permeation chromatography (GPC) measurement under the following conditions, the weight average molecular weight (Mw) in terms of polystyrene is calculated for the hydrogenated product of the block copolymer. (GPC measuring device and measuring conditions) ・Device: GPC device "HLC-8020" (manufactured by Tosoh Co., Ltd.) ・Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Co., Ltd. are connected in series. ・Separation liquid: Tetrahydrofuran ・Separate flow rate: 0.7mL/min ・Sample concentration: 5mg/10mL ・Column temperature: 40℃ ・Detector: Differential refractive index (RI) detector ・Calibration line: made using standard polystyrene

(3) The hydrogenation rate in the polymer block (B) was ^{measured by 1} H-NMR, and the peak area of the residual olefin derived from isoprene and/or butadiene was compared with the peak area derived from ethylene, propylene and/or butene. Calculated by the ratio of the peak area.・Device: Nuclear magnetic resonance device "ADVANCE 400 Nano bay" (manufactured by Bruker) ・Solvent: CDCl ₃

(4) Vinyl bonding amount in polymer block (B) The block copolymer before hydrogenation is dissolved in CDCl ₃ and ^{measured by 1} H-NMR [device: "ADVANCE 400 Nano bay" (manufactured by Bruker) , Measurement temperature: 30℃]. From the total peak area of the structural unit derived from isoprene and/or butadiene, and the 3,4-bonding unit, 1,2-bonding unit and butadiene structural unit in the isoprene structural unit In the 1,2-bonding unit, or in the case of a structural unit derived from a mixture of isoprene and butadiene, the ratio of the peak area of each aforementioned bonding unit is calculated, and the vinyl bonding amount is calculated ( The total content of 3,4-bonding unit and 1,2-bonding unit).

(5) The content of the alicyclic skeleton (X) in the polymer block (B). Dissolve 600 mg of the block copolymer before hydrogenation and 40 mg of _{Cr(acac) 3 in 4 mL of CDCl 3} and use a 10 mm NMR tube to quantify ¹³ C-NMR measurement (pulse program: zgig, Inverse gated 1H decoupling method) [device: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C], the polymer block was calculated by the following method ( The content of each of the alicyclic skeleton X, X1, and X2 in B). In addition, in Table 3, X, X1, and X2 represent the following alicyclic skeletons. X: an alicyclic skeleton having a combination of the following (i) to (vi) substituents X1: an alicyclic skeleton having a combination of the following (i) and (iv) substituents X2: having the following (ii), (iii) The alicyclic skeleton (i) of the combination of substituents of (v) and (iv): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Bd+Bd) (ii): R ¹ = hydrogen atom, R ² = methyl, R ³ = hydrogen atom; (1,2Bd+1,2Ip) (iii): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = Methyl; (1,2Bd+3,4Ip) (iv): R ¹ = methyl, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Ip+Bd) (v): R ¹ = methyl , R ² = methyl, R ³ = hydrogen atom; (1,2Ip+1,2Ip) (vi): R ¹ = methyl, R ² = hydrogen atom, R ³ = methyl; (1,2Ip+3 ,4Ip)

[Calculation method] The peaks and their derived structures are disclosed in Table 1-1. If the integral value of each peak is set as a to g, the integral value of each structure becomes as shown in Table 1-2, and the contents of X, X1, and X2 can be expressed as (a+gc)/(a+b+c -d+e/2+2f), (gc)/(a+b+c-d+e/2+2f), a/(a+b+c-d+e/2+2f).

[Table 1] Table 1-2 Table 1-1 structure Integral value Peak (ppm) structure Integral value St df 108～110 X2 a 1,4Ip f 110～113 3,4Ip+1,2Ip+X1 b 3,4Ip+1,2Ip b-(gc) 113～116 1,2Bd c 1.4Bd (e-(df)×4)/2 122～127 1,4Ip+St d 1,2Bd c 127～132 1,4Bd×2+St×4 e X1 gc 132～137 1,4Ip f X2 a 142～145 1,2Bd+X1 g total a+b+c-d+e/2+2f

(6) ^{Peak area ratio of 13} C-NMR For the hydrides of Production Example 1 and Comparative Production Example 1, the above-mentioned quantitative ¹³ C-NMR measurement was performed [device: "ADVANCE 400 Nano bay" (manufactured by Bruker), and measurement temperature: 30°C, solvent: CDCl ₃ ], and calculate the peak area ratio [peak area with a chemical shift value of 50.0-52.0 ppm]/[peak area with a chemical shift value of 43.0-45.0 ppm].

(7) Peak top temperature of tanδ, peak top intensity, the maximum width of the temperature range where tanδ becomes 1.0 or more, and the tanδ intensity at 20°C and 30°C For the following measurement, the hydrogenated product of the block copolymer was pressed at a temperature of 230°C and a pressure of 10 MPa for 3 minutes to produce a single-layer sheet with a thickness of 1.0 mm. This single-layer sheet was cut into a circular plate shape, and this was used as a test piece. In the measurement, based on JIS K 7244-10 (2005), a strain-controlled dynamic viscoelastic device "ARES-G2" (manufactured by TA Instruments Japan Co., Ltd.) with a circular plate diameter of 8 mm was used as a parallel plate vibration rheometer. With the above test piece, the gap between the two plates is completely filled, and the strain is 0.1%. The above test piece is vibrated at a frequency of 1 Hz, and the temperature is raised from -70°C to 100°C at a constant rate of 3°C/min. . Until the measured values of the shear loss modulus and the shear storage modulus do not change, keep the temperature of the test piece and the disc, and obtain the maximum value of the peak intensity of tanδ (peak top intensity) and the temperature at which the maximum value is obtained (Peak top temperature). In addition, the tanδ intensity at 20°C and 30°C, which is the maximum width of the temperature region where tanδ becomes 1.0 or more, is obtained. The larger the value, the better the vibration damping performance.

[Manufacturing Example 1] Manufacturing of hydride (H-TPE-1) In a dry pressure vessel that has been substituted with nitrogen, 50 kg of cyclohexane is filled as a solvent, and 87 g of a cyclohexane solution of secondary butyl lithium with a concentration of 10.5% by mass (the actual amount of secondary butyl lithium added: 9.1 g) As an anionic polymerization initiator. After raising the temperature in the pressure vessel to 50°C, add 1.0 kg of styrene (1) to polymerize for 1 hour, and add 2,2-bis(2-tetrahydrofuryl)propane as the Lewis base at a temperature of 50°C in the vessel (DTHFP) 63g, a mixture of 8.16kg isoprene and 6.48kg butadiene was added using the average diene feed rate shown in Table 2. After 5 hours of addition, it was polymerized for 2 hours, and then styrene was added (2) 1.0 kg was polymerized for 1 hour to obtain a reaction liquid containing a polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer. In this reaction solution, a Chigler-based hydrogenation catalyst composed of nickel octoate and trimethylaluminum was added in a hydrogen gas atmosphere, and the reaction was carried out for 5 hours under the conditions of a hydrogen pressure of 1 MPa and 80°C. After allowing the reaction solution to cool down and releasing the pressure, the catalyst was removed by washing with water and dried in a vacuum, thereby obtaining a polystyrene-poly(isoprene/butadiene)-polystyrene triblock The hydrogenated product of the copolymer (hereinafter, sometimes referred to as H-TPE-1). About each raw material and its usage amount, it is shown in Table 2. In addition, the results of the aforementioned physical property evaluation are shown in Table 3.

[Manufacturing Example 2] Manufacturing of hydride (H-TPE-2) Except for changing the usage amount of each component and the like, and reaction conditions as described in Table 2, the same procedure as in Production Example 1 was carried out to produce a hydrogenated block copolymer (H-TPE-2). In addition, the results of the aforementioned physical property evaluation are shown in Table 3. [Manufacturing Example 3] Manufacturing of hydride (H-TPE-3) Except for changing the usage amount of each component and the like, and the reaction conditions as described in Table 2, the same procedure as in Production Example 1 was carried out to produce a hydrogenated block copolymer (H-TPE-3). In addition, the results of the aforementioned physical property evaluation are shown in Table 3. [Manufacturing Example 4] Manufacturing of hydride (H-TPE-4) Except for changing the usage amount of each component and the like, and reaction conditions as described in Table 2, the same procedure as in Production Example 1 was carried out to produce a hydrogenated block copolymer (H-TPE-4). In addition, the results of the aforementioned physical property evaluation are shown in Table 3.

[Comparative Manufacturing Example 1] Manufacturing of hydride (H-TPE-1’) Except for changing the usage amounts of the components and the like, and the reaction conditions as described in Table 2, the same procedure as in Production Example 1 was carried out to produce a hydrogenated block copolymer (H-TPE-1'). In addition, the results of the aforementioned physical property evaluation are shown in Table 3.

[Table 2] Manufacturing example Comparative manufacturing example 1 2 3 4 1 Hydride of block copolymer H-TPE-1 H-TPE-2 H-TPE-3 H-TPE-4 H-TPE-1' Usage (kg) Cyclohexane 50 50 50 50 50 Secondary butyl lithium (10.5 mass% cyclohexane solution) 0.087 0.081 0.087 0.087 0.166 (A) Styrene (1) 1.0 0.67 0.5 1.0 1.5 Styrene (2) 1.0 0.67 1.5 1.0 1.5 (B) Isoprene 8.16 8.57 8.16 14.64 13.64 Butadiene 6.48 6.74 6.48 0 0 Lewis base DTHFP 0.063 - - 0.032 0 Tetrahydrofuran - 0.33 0.31 - 0 Reaction conditions Diene polymerization temperature (℃) 50 50 40 40 50 Diene feed time (h) 5 5 5 5 5 Average feed rate of diene per 1 mol of active end (kg/h) 20.5 twenty three 20.5 20.5 10.0

[table 3] Manufacturing example Comparative manufacturing example 1 2 3 4 1 Hydrogenated block copolymer used H-TPE-1 H-TPE-2 H-TPE-3 H-TPE-4 H-TPE-1' Structural unit of polymer block (A) St St St St St Components constituting the polymer block (B) Ip/Bd Ip/Bd Ip/Bd Ip Ip The mass ratio of the components constituting the polymer block (B) 55/45 55/45 55/45 100 100 The molar ratio of the components constituting the polymer block (B) 50/50 50/50 50/50 100 100 Polymer structure A/B/A A/B/A A/B/A A/B/A A/B/A Content of polymer block (A) (mass%) 12 8 12 12 18 Weight average molecular weight of hydrogenated block copolymer 167,000 166,000 163,000 150,000 96,000 Hydrogenation rate in polymer block (B) (mol%) 95 92 91 86 99 Vinyl bond amount in polymer block (B) (mol%) 76 60 64 83 4 The content of X1 or X1 hydride in block (B) (mol%) 5 0.2 0.2 0 0 The content of X2 or X2 hydride in block (B) (mol%) 9.9 1.7 1.7 5.2 0 The content of X or X hydride in block (B) (mol%) 14.9 1.9 1.9 5.2 0 ¹³ C-NMR area ratio after hydrogenation [50~52ppm peak area]/[43~45ppm peak area] 0.21 0 0 0 0 Peak top temperature of tanδ (℃) 14.9 -25 -twenty one 31.9 -52.7 Peak top intensity of tanδ 2.24 2.05 2.23 2.20 2.01 Become the maximum range of the temperature zone where tanδ≧1 (℃) 17.9 14 14.6 20.7 8.6 Tanδ intensity at 20℃, 1Hz 1.70 0.07 0.09 0.29 0.03 Tanδ intensity at 30℃, 1Hz 0.81 0.06 0.07 2.03 0.03

The hydrogenated product of the block copolymer of Production Examples 1 to 4 shows a peak top strength of tanδ of 1.0 or more, and a peak top temperature of tanδ in a wide temperature range, so it can be said to be suitable for use as a vibration damping material in a wide range of applications . In particular, when compared with Comparative Production Example 1, it can be seen that in Production Examples 1 to 4, the tanδ strength at 20°C and 30°C is relatively high, and the vibration damping properties near room temperature are excellent.

＜Laminated body＞ [Examples 1 to 8] [Comparative Examples 1 to 3] (Method of making substrate layer) The composition of the substrate layer shown in Table 4 was put into a Brabender (Brabender company, "Plastograph EC 50cc mixer"), and melted and kneaded at a cylinder temperature of 240°C and a screw rotation number of 100 rpm for 3 minutes. The obtained composition was press-formed (240°C, 2 minutes) to produce a sheet (thickness 1 mm) of the base layer.

(Method of making adhesive layer) The composition of the adhesive layer shown in Table 4 was put into a plastic spectrometer (manufactured by Brabender, "Plastograph EC 50cc mixer"), and melted and kneaded at a cylinder temperature of 180°C and a screw rotation number of 100 rpm for 3 minutes. The resulting composition The object was press-formed (180°C, 2 minutes) to produce an adhesive layer sheet (thickness 1 mm).

(Method of making laminate) The pellets with the composition of the substrate layer shown in Table 4 were put into the hopper of the uniaxial extruder "GM30" (manufactured by GM Engineering), and the pellets with the composition of the adhesive layer shown in Table 4 were put into the uniaxial extruder. The feed hopper of "GM25" (manufactured by GM Engineering) uses a multi-manifold die as a T-die, and performs co-extrusion at an extrusion temperature of 220°C to obtain a thickness of 50 μm (base material layer thickness: 35 μm, Adhesive layer thickness: 15μm) laminate.

[Physical Property Evaluation] The physical property evaluation methods of the base material layer, the adhesive layer, and the laminate produced above are disclosed below. (Shore A hardness) The obtained substrate layer and the adhesive layer were superimposed on 6 sheets, respectively, and used as a test piece for hardness measurement with a thickness of 6mm. According to JIS K 6253 (2012), an automatic rubber hardness tester P2-A (manufactured by Polymer Tester) was used. ) To measure the Shore A hardness i of the base layer and the Shore A hardness ii of the adhesive layer. The results are shown in Table 4.

(Storage modulus, tanδ strength (tensile, 10Hz)) The measurement is performed in accordance with JIS K 7244-4 (1999). Specifically, the obtained substrate layer and adhesive layer sheet was cut into a sample with a length of 70 mm × a width of 5 mm × a thickness of 1 mm, and used "DMA242E" (manufactured by NETZSCH) under a frequency of 10 Hz. ℃/minute is increased from -70℃ to 200℃ and measured to determine the tensile storage modulus (E') of the adhesive layer at 23, 60℃, the substrate layer and the adhesive layer at 23, 40, 60 Tanδ intensity in ℃. The results are shown in Table 4.

(HAZE) The HAZE of the obtained laminate was measured with a turbidity/turbidity meter "HR-100" (manufactured by Murakami Color Research Institute Co., Ltd.). The results are shown in Table 4.

(Peeling strength, residual glue (23℃)) On an acrylic extrusion sheet (trade name SUMIPEX E, thickness 1.5mm, manufactured by SUMIKA ACRYL Sales Co., Ltd.), the resulting laminate is attached to the acrylic resin sheet on the adhesive layer, and cut into width The size of 25mm is used as the test piece. Thus, the substrate layer side of the test piece was reciprocated twice at a speed of 10 mm/min using a 2 kg rubber roller, and then left for 24 hours in a gas environment at 23±1°C and a humidity of 50±5%. Thereafter, in accordance with JIS Z 0237 (2009), using INSTRON 5566 (manufactured by INSTRON), the 180-degree peel strength between the laminate and the acrylic resin plate was measured at a peeling speed of 300 mm/min, as the peel strength (23°C). In addition, visually confirm whether there is any residual glue in the adherend after peeling. The results are shown in Table 4.

(Peeling strength, residual glue (60℃)) After leaving for 24 hours in a 23±1°C and 50±5% humidity gas environment, and then placing it in a 60°C gas environment for 10 minutes, measure the peel strength in a 60°C gas environment. Otherwise, it is the same as the above (Peel strength, residual glue (23°C)) was performed in the same manner, and set as peel strength and residual glue (60°C). The results are shown in Table 4.

[Table 4] Example Comparative example 1 2 3 4 5 6 7 8 1 2 3 Substrate layer Composition (parts by mass) Olefin resin 80 80 80 90 70 80 80 80 80 90 70 H-TPE-1 20 20 0 10 30 0 0 0 0 0 0 H-TPE-2 0 0 0 0 0 20 0 0 0 0 0 H-TPE-3 0 0 0 0 0 0 20 0 0 0 0 H-TPE-4 0 0 0 0 0 0 0 20 0 0 0 H-TPE-1' 0 0 20 0 0 0 0 0 20 10 30 Physical properties Shaw A Hardness i 93 93 91 87 87 88 88 88 91 88 86 tanδ intensity (23℃) 0.15 0.15 0.07 0.09 0.19 0.09 0.09 0.07 0.07 0.06 0.07 tanδ intensity (40℃) 0.13 0.13 0.06 0.08 0.17 0.07 0.07 0.12 0.06 0.06 0.06 tanδ intensity (60℃) 0.12 0.12 0.06 0.08 0.13 0.08 0.08 0.08 0.06 0.07 0.07 Adhesive layer Composition (parts by mass) H-TPE-1 20 0 20 20 20 20 20 20 0 0 0 H-TPE-1' 60 80 60 60 60 60 60 60 80 80 80 Adhesion imparting resin 20 20 20 20 20 20 20 20 20 20 20 Physical properties Shaw A hardness ii 54 52 54 54 54 54 54 54 52 52 52 tanδ intensity (23℃) 0.22 0.12 0.22 0.22 0.22 0.22 0.22 0.22 0.12 0.12 0.12 tanδ intensity (40℃) 0.33 0.08 0.33 0.33 0.33 0.33 0.33 0.33 0.08 0.08 0.08 tanδ intensity (60℃) 0.19 0.07 0.19 0.19 0.19 0.19 0.19 0.19 0.07 0.07 0.07 E'(23℃)(MPa) 24.3 6.1 24.3 24.3 24.3 24.3 24.3 24.3 6.1 6.1 6.1 E'(60℃)(MPa) 5.8 5.5 5.8 5.8 5.8 5.8 5.8 5.8 5.5 5.5 5.5 E'(23℃)/E'(60℃) 4.22 1.11 4.22 4.22 4.22 4.22 4.22 4.22 1.11 1.11 1.11 Layered body Physical properties Shaw A hardness ratio [i/ii] 1.72 1.79 1.69 1.61 1.61 1.63 1.63 1.63 1.75 1.70 1.65 HAZE(%) 0.3 0.3 1.1 0.7 0.7 0.5 0.4 0.4 0.8 1.3 3.0 Peel strength (23℃)(N/25mm) 6.4 6.2 8.1 5.4 7.4 5.1 5.2 5.1 6.0 4.2 5.7 Residual glue (23℃) no no no no no no no no no no no Peel strength (60℃)(N/25mm) 3.4 2.8 5 4.7 3.2 3.3 4.4 3.6 2.2 1.7 2.2 Residual glue (60℃) no no no no no no no no no no no Peel strength (60℃)/Peel strength (23℃) 0.53 0.45 0.62 0.87 0.43 0.65 0.85 0.71 0.36 0.40 0.39

The components shown in Table 4 are as follows. ・Olefin resin: Homopolypropylene (NOVATEC-PP, manufactured by Japan Polypropylene Co., Ltd.) ・Adhesive resin: Alcon P-125 (alicyclic saturated hydrocarbon resin, softening point (ring and ball method) 125±5°C, manufactured by Arakawa Chemical Industry Co., Ltd.)

It can be seen from Table 4 that in Examples 1, 2 and 4-8 in which the hydrogenated product of the block copolymer is contained in the base layer, the value of the tanδ intensity of the base layer is large in the temperature range of 23-60°C. In Examples 1 and 3-8 in which the hydrogenated product of the block copolymer is contained in the adhesive layer, the value of the tanδ intensity of the adhesive layer is large in the temperature range of 23-60°C. In addition, compared with the laminates of Comparative Examples 1 to 3, the storage modulus E'ratio [E'(23°C)/E'(60°C)] of the adhesive layers of Examples 1 and 3-8 is larger, which is 2 or more. In this way, the ratio of storage modulus at 23°C to 60°C of the laminates of Examples 1 and 3 to 8 is greater than that of the comparative example, and the peel strength at 23°C to 60°C decreases less [(Peel strength at 60°C )/(Peel strength at 23°C) is large]. Although the structure of the adhesive layer of Example 2 and Comparative Examples 1-3 is the same, compared with the laminated body of Comparative Examples 1-3, the fall of the peeling strength of Example 2 at 23-60 degreeC becomes small. As one of the main reasons for the reduction in the above-mentioned peel strength of Example 2 compared to Comparative Examples 1 to 3, it is possible to cite the fact that the hydrogenated product of the block copolymer is included to impart appropriate flexibility to the base layer. In addition, the laminates of Examples 1 to 8 had no glue residue even at 60°C. Therefore, it can be seen that the laminated system of the embodiment contains a block copolymer or its hydrogenated product in one or both of the substrate layer and the adhesive layer, and the block copolymer or its hydrogenated product has an alicyclic type in the main chain. The structural unit of the skeleton (X) is expected to provide excellent vibration damping properties to the adherend, and it is not easy to peel off even under high temperature conditions, and it is extremely unlikely to produce glue residue.

In addition, although it is not clear, based on the ratio of the peel strength of Examples 1 and 3 to 8, it can be inferred that the adhesive layer containing the block copolymer or its hydrogenated product will be softened at high temperature (60°C). Therefore, the following Under the circumstances, the adhesion between the adhesive layer and the material to be adhered is suppressed: it penetrates into the small irregularities on the surface of the material to be adhered (acrylic resin sheet) and acts like an anchor, or the small irregularities on the surface of the adhesive layer. It fits into the recess of the material to be bonded and exerts an elastic tightening force. In addition, even if the composition of the adhesive layer is the same, the peel strength ratio differs depending on the composition of the base layer, which is considered to be affected by the flexibility of the base layer. Furthermore, compared with the laminates of Example 3 and Comparative Examples 1 to 3, the laminates of Examples 1, 2, and 4 to 8 had lower HAZE and higher transparency. This is considered to be because the constituent components of the base material layers of Examples 1, 2, and 4 to 8, that is, the block copolymer or its hydrogenated product system has high compatibility with polypropylene. Therefore, the laminate systems of Examples 1, 2, and 4 to 8 in this embodiment are useful for applications where transparency is required, for example, as a surface protective film for liquid crystal displays and the like. [Industry Availability]

Since the laminated body of the present invention can impart vibration damping properties to the adherend, it is not easy to peel off even at high temperature and is not easy to generate residual glue, so it is used as an adhesive tape and adhesive sheet, etc., as a surface protection film for electronic devices, etc. , Surface protection film to prevent contamination and damage of the target product during transportation, storage, and processing.

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Claims (21)

A laminate having a substrate layer and an adhesive layer, wherein the ratio [i/ii] of the Shore A hardness i of the substrate layer to the Shore A hardness ii of the adhesive layer is 1.1 or more, At least one of the substrate layer and the aforementioned adhesive layer contains the following block copolymer or its hydrogenated product; the aforementioned block copolymer contains a polymer block (A) and a polymer block (B), and the aforementioned polymer block Paragraph (B) is a structural unit derived from a conjugated diene compound, and has a structural unit containing at least one alicyclic skeleton (X) represented by the following formula (X) in the main chain;

(In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different). The laminate according to claim 1, wherein, in the base material layer, the content of the block copolymer or its hydrogenated product is 1-100% by mass. The laminate of claim 1 or 2, wherein, in the base material layer, the content of the block copolymer or its hydrogenated product is 1 to 99% by mass, and the content of the olefin resin is 99 to 1% by mass. The laminate according to claim 3, wherein the olefin resin is polypropylene. The laminate according to any one of claims 1 to 4, wherein the content of the adhesion-imparting resin in the base material layer is less than 1% by mass. The laminate according to any one of claims 1 to 5, wherein, in the adhesive layer, the content of the block copolymer or its hydrogenated product is 1 to 80% by mass. The laminate according to any one of claims 1 to 6, wherein the content of the adhesion-imparting resin in the adhesive layer is 1% by mass or more. The laminate according to any one of claims 1 to 7, wherein, in the alicyclic skeleton (X) ^{, at least one of the foregoing R 1} to R ³ is a hydrocarbon group with 1 to 11 carbons. Cyclic skeleton (X'). The laminate of claim 8, wherein the hydrocarbon group in the alicyclic skeleton (X') is a methyl group. The laminate according to any one of claims 1 to 9, which contains at least a styrene-hydrogenated butadiene/isoprene-styrene copolymer as the hydrogenated product of the aforementioned block copolymer. The laminate according to any one of claims 1 to 7, wherein the aforementioned R ¹ to R ³ are hydrogen atoms at the same time. The laminate as described in any one of claims 1 to 11, which contains 1 mol% or more of the alicyclic skeleton (X) in the polymer block (B). The laminate of claim 8 or 9, which contains 1 mol% or more of the alicyclic skeleton (X') in the polymer block (B). The laminate according to any one of claims 1 to 13, wherein the hydrogenation rate of the aforementioned polymer block (B) is 0 mol% or more and less than 50 mol%. The laminate according to any one of claims 1 to 13, wherein the hydrogenation rate of the aforementioned polymer block (B) is 50 to 99 mol%. The laminate according to any one of claims 1 to 15, wherein the vinyl bond amount in the polymer block (B) is 55 to 95 mol%. Such as the laminate of any one of claims 1 to 16, wherein the aforementioned block copolymer or its hydrogenated product exists: in accordance with JIS K 7244-10 (2005), the strain amount is 0.1%, the frequency is 1 Hz, and the measurement temperature- The tanδ measured under the conditions of 70 to 100°C and a temperature increase rate of 3°C/min is a continuous temperature range of 1.0 or more; the maximum range of this temperature range is 13°C or more. The laminate according to any one of claims 1 to 17, wherein the aforementioned polymer block (A) contains more than 70 mol% of structural units derived from an aromatic vinyl compound. The laminate of claim 18, wherein the content of the polymer block (A) in the block copolymer is 50% by mass or less. The laminate according to claim 18, wherein the content of the polymer block (A) in the block copolymer is 16% by mass or less. The laminate of any one of claims 1 to 20, wherein the ratio of the storage modulus E'(23°C) of the aforementioned adhesive layer at 23°C to the storage modulus E'(60°C) at 60°C [E'(23°C)/E'(60°C)] is 2 or more.