WO2020235660A1

WO2020235660A1 - Laminate

Info

Publication number: WO2020235660A1
Application number: PCT/JP2020/020205
Authority: WO
Inventors: 星哉清水; 泰史千田
Original assignee: 株式会社クラレ
Priority date: 2019-05-22
Filing date: 2020-05-22
Publication date: 2020-11-26
Also published as: JP7364671B2; JPWO2020235660A1; TW202110920A

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

Laminate

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

Block copolymers having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound and their hydrogenated products have vibration damping properties. It is already known that some of them have, and have been used as damping materials. In addition, the block copolymer and its hydrogenated additive may have physical properties such as sound insulation, heat resistance, impact resistance, and adhesiveness in addition to vibration damping properties, and there are various types. It is conceivable that it can be used for various purposes.
For example, styrene compounds and isoprene, butadiene, etc., whose peak temperature of tan δ and vinyl bond amount are specified in order to improve mechanical properties such as vibration damping, flexibility, heat resistance, tensile strength and impact resistance. Hydrogenated block copolymers with conjugated diene compounds are disclosed (see, for example, Patent Documents 1 to 4).

On the other hand, as a laminate containing a base material layer and a layer having adhesive strength (adhesive layer), for example, a surface protective film is known. It is known that the pressure-sensitive adhesive layer in the surface protective film is formed by using a pressure-sensitive adhesive composition containing a styrene-based elastomer and a pressure-sensitive adhesive resin (see, for example, Patent Documents 5 and 6).

Japanese Unexamined Patent Publication No. 2002-284830 International Publication No. 2000/015680 Japanese Unexamined Patent Publication No. 2006-117879 Japanese Unexamined Patent Publication No. 2010-0533319 Japanese Unexamined Patent Publication No. 5-194923 JP-A-2010-126711

Since the block copolymer and its hydrogenated additive may have physical properties such as adhesiveness in addition to vibration damping property, they are required for a laminate having adhesiveness while exhibiting vibration damping property. A laminated body having physical properties is being studied.
Although improvements have been made to further improve the vibration damping property, it has been difficult to further improve various physical properties such as vibration damping property and adhesiveness in a well-balanced manner. In addition to the adhesive strength, the physical properties required for the laminate having adhesiveness include suppression of adhesive residue (a phenomenon in which a part of the adhesive layer remains on the adherend). Further, some adherends that use a laminate such as a surface protective film become hot during use of electrical appliances, etc., and adherends that are installed outdoors or adherents that are used outdoors. As the temperature rises, the adhesive holding force of the adhesive layer decreases, and the laminated body may easily come off. Adhesive strength that can withstand such changes in the temperature of the adherend and the usage environment is required.

Therefore, the present invention provides a laminate including an adhesive layer and a base material layer, which can impart vibration damping properties to the adherend and are difficult to peel off and leave adhesive residue even at a high temperature.

As a result of diligent studies to solve the above problems, the present inventors have conceived the following inventions and found that the problems can be solved.
That is, the present invention is as follows.

A laminate having a base material layer and an adhesive layer,
The ratio [i / ii] of the shore A hardness i of the base material layer to the shore A hardness i of the adhesive layer is 1.1 or more.
A laminate in which at least one of the base material layer and the adhesive layer contains the following block copolymer or a hydrogenated product thereof.
The block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound and has the following formula (X). It has a structural unit containing one or more alicyclic skeletons (X) represented by (X) in the main chain.

(In the above formula (X), R ¹ to R ³ 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.)

According to the present invention, it is possible to provide a laminate including an adhesive layer and a base material layer, which can impart vibration damping properties to an adherend and are difficult to peel off and leave adhesive residue even at a high temperature.

The laminate of the present invention is a laminate having a base material layer and an adhesive layer, and is a laminate.
The ratio [i / ii] of the shore A hardness i of the base material layer to the shore A hardness i 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 a hydrogenated product thereof.
The block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound, and the formula (X). It has a structural unit containing one or more alicyclic skeletons (X) represented by (X) in the main chain.
The base material layer and the adhesive layer contained in the laminate, the block copolymer and its hydrogenated material will be described below.

≪Block copolymer and its hydrogenated additive≫
In the embodiment of the present invention (hereinafter, may be referred to as "the present embodiment"), if the block copolymer or its hydrogenated product is contained in at least one of the base material layer and the adhesive layer. Good. By containing a block copolymer or a hydrogenated additive thereof, vibration damping and adhesiveness can be imparted to the laminate, but depending on various uses of the laminate, one of the base material layer and the adhesive layer, or Both can contain block copolymers or hydrogenated products thereof.

[Polymer block (A)]
The polymer block (A) constituting the block copolymer preferably has a structural unit derived from an aromatic vinyl compound used as a monomer from the viewpoint of vibration damping and mechanical properties.
The polymer block (A) contains more than 70 mol% of a structural unit derived from an aromatic vinyl compound (hereinafter, may be abbreviated as “aromatic vinyl compound unit”) in the polymer block (A). 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 100 mol% or more. ..

Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, and α. -Methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p- Methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2 , 4-Dimethylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m- Chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α- Chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, ot-butylstyrene, m -T-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromomethyl Examples thereof include styrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, inden, vinylnaphthalene, N-vinylcarbazole and the like. These aromatic vinyl compounds may be used alone or in combination of two or more. Among them, styrene, α-methylstyrene, p-methylstyrene, and a mixture thereof are preferable, and styrene is more preferable, from the viewpoint of production cost and physical property balance.

The polymer block (A) is a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter, “other unsaturated monomer unit”” as long as it does not interfere with the object and effect of the present invention. It may be abbreviated as), 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%, still more preferably. It is less than 10 mol%, more preferably less than 5 mol%, and particularly preferably 0 mol%.
Examples of the other unsaturated monomer include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, β-pinene, 8, At least one selected from the group consisting of 9-p-mentene, dipentene, methylenenorbornene, 2-methylene tetrahydrofuran and the like can be mentioned. When the polymer block (A) contains the other unsaturated monomer unit, the bonding form is not particularly limited and may be random or tapered.

The block copolymer may have at least one of the polymer blocks (A). When 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 polymer block is different" means the monomer unit constituting the polymer block, the weight average molecular weight, the stereoregularity, and the ratio of each monomer unit when having a plurality of monomer units. It means that at least one of the forms of polymerization (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) contained in the block copolymer is , Preferably 3,000 to 60,000, more preferably 4,000 to 50,000. When 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.
The weight average molecular weight is a standard polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) measurement.

(Content of polymer block (A))
The content of the polymer block (A) in the block copolymer is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 16% by mass or less, and 14% by mass. It is particularly preferable that it is% or less. If it is 50% by mass or less, it can be a block copolymer having appropriate flexibility and excellent vibration damping property without lowering the tan δ peak top strength or a hydrogenated additive thereof. The lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 6% by mass or more. If it is 1% by mass or more, it can be a block copolymer having mechanical properties and molding processability suitable for various uses of the laminate or a hydrogenated additive thereof.
The content of the polymer block (A) in the block copolymer is a value obtained by ^{1 1} H-NMR measurement, and more specifically, a value measured according to the method described in Examples.

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

In the above formula (X), R ¹ to R ³ 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 from each other. The hydrocarbon group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 (that is, a methyl group). Further, the hydrocarbon group may be a straight chain or a branched chain, or may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and formation of the alicyclic skeleton (X), it is particularly preferable that R ¹ to R ³ are independently hydrogen atoms or methyl groups, respectively.
When the block copolymer is hydrogenated, the vinyl group in the above formula (X) can be hydrogenated. Therefore, the meaning of the alicyclic skeleton (X) in the hydrogenated additive also includes the skeleton in which the vinyl group in the above formula (X) is hydrogenated.

The polymer block (B) is a structural unit derived from the conjugated diene compound, and the alicyclic skeleton (X) is derived from the conjugated diene compound. The alicyclic skeleton (X) is produced by anionic polymerization of a conjugated diene compound by a method described later, and at least one alicyclic skeleton (X) is the main alicyclic skeleton-containing unit depending on the conjugated diene compound used. Included in the chain. Since the alicyclic skeleton (X) is incorporated into the main chain of the structural unit contained in the polymer block (B), the molecular motion is reduced and the glass transition temperature rises, so that tan δ at around room temperature The peak top strength is improved, and excellent vibration damping properties can be exhibited.

Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1,3-pentadiene. , 1,3-Hexadiene, 1,3-octadien, 1,3-cyclohexadiene, 2-methyl-1,3-octadene, 1,3,7-octatriene, farnesene, milsen, chloroprene and the like. .. Of these, butadiene, isoprene, or a combination of butadiene and isoprene is preferable.

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

As a specific example, an alicyclic skeleton (X) 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 the following combination of substituents (i) is produced. That is, in this case, the alicyclic skeleton (X) is only an alicyclic skeleton in which R ¹ to R ³ are hydrogen atoms at the same time. Therefore, as an example of a preferred embodiment of the block copolymer or its hydrogenated product, the polymer block (B) has one alicyclic skeleton (X) in which R ¹ to R ³ are hydrogen atoms at the same time as the main chain. Examples include those having a structural unit contained in.

When isoprene is used alone as the conjugated diene compound, two types of alicyclic skeletons (X) having a combination of the following substituents (v) and (vi) are mainly produced.
When butadiene and isoprene are used in combination as the conjugated diene compound, six types of alicyclic skeletons (X) having a combination of the following substituents (i) to (vi) are mainly produced.
(I): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom (ii): R ¹ = hydrogen atom, R ² = methyl group, R ³ = hydrogen atom (iii): R ¹ = hydrogen Atomic, R ² = hydrogen atom, R ³ = methyl group (iv): R ¹ = methyl group, R ² = hydrogen atom, R ³ = hydrogen atom (v): R ¹ = methyl group, R ² = methyl group, R ³ = hydrogen atom (vi): R ¹ = methyl group, R ² = hydrogen atom, R ³ = methyl group

In the above formula (X), at least one alicyclic skeleton in the polymer block (B) from the viewpoint that the molecular motion becomes smaller and the vibration damping property is further improved by having a substituent which is a hydrocarbon group. (X) is preferably an alicyclic skeleton (X') in which at least one of R ¹ to R ³ is a hydrocarbon group having 1 to 11 carbon atoms. Among them, the alicyclic skeleton can be efficiently generated from the conjugated diene compound, and the hydrocarbon group in the alicyclic skeleton (X') is a methyl group from the viewpoint of the balance between vibration damping property and mechanical properties. Is more preferable.
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 alicyclic skeletons that are not hydrogen atoms at the same time. That is, it is more preferable that the polymer block (B) has a structural unit containing at least one of the alicyclic skeletons having a combination of the substituents (ii) to (vi) in the main chain. ..

(Amount of vinyl bond in polymer block (B))
When the structural unit constituting the polymer block (B) is any of an isoprene unit, a butadiene unit, and a mixture unit of isoprene and butadiene, isoprene and butadiene other than the bonded form forming the alicyclic skeleton (X). In the case of butadiene, 1,2-bond and 1,4-bond are taken, and in the case of isoprene, 1,2-bond, 3,4-bond and 1,4-bond are taken. Can be done.

In the block copolymer and its hydrogenated product, the content of the 3,4-bonding unit and the 1,2-bonding unit in the polymer block (B) (hereinafter, may be simply referred to as "vinyl bond amount"). The total of.) Is preferably 55 to 95 mol%, more preferably 63 to 95 mol%, and further preferably 70 to 95 mol%. Within 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 Examples.
When the polymer block (B) is composed only of butadiene, the above-mentioned "contents of 3,4-bonding unit and 1,2-bonding unit" is "content of 1,2-bonding unit". And apply.

(Alicyclic skeleton (X) content)
The polymer block (B) may contain a structural unit containing an alicyclic skeleton (X) in the main chain, but it exhibits a better anti-vibration effect and has a viscous adhesive force even at high temperatures. The polymer block (B) preferably contains 1 mol% or more of the alicyclic skeleton (X), more preferably 1.1 mol% or more, and further preferably 1.1 mol% or more, from the viewpoint of facilitating the suppression of the decrease in the amount. Is 1.4 mol% 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. Is. The upper limit of the content of the alicyclic skeleton (X) in the polymer block (B) is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of productivity, 40 mol. % Or less, preferably 30 mol% or less, 20 mol% or less, or 18 mol% or less.
From the viewpoint of further improving the vibration damping property, it is more preferable that the polymer block (B) contains 1 mol% or more of the alicyclic skeleton (X'), and more preferably 1.3 mol% or more. , More preferably 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 alicyclic skeleton (X).

More specifically, when isoprene is used as the conjugated diene compound, when butadiene is used, or when butadiene and isoprene are used in combination, the alicyclic skeleton content in each case is as follows.
When isoprene is used as the conjugated diene compound, when one or more alicyclic skeletons (X') having a combination of the substituents (v) and (vi) are present in the polymer block (B). The total content of these compounds is preferably 1 mol% or more from the viewpoint of exhibiting a more excellent anti-vibration effect and easily suppressing a decrease in adhesive strength even at high temperatures, preferably 1.5 mol%. More preferably, it is more preferably 2 mol% or more, further preferably 3 mol% or more, and 4 mol% or more from the viewpoint of obtaining an excellent anti-vibration effect in a wide temperature range. Is particularly preferable. Further, the upper limit of the total content when isoprene is used is the same as the upper limit of the content of the alicyclic skeleton (X).

When butadiene is used as the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (B) when it is present is 5 mol% or more, which is more excellent vibration damping. It is preferable from the viewpoint of exhibiting a sexual effect and easily suppressing a decrease in adhesive strength even at a high temperature, more preferably 10 mol% or more, further preferably 15 mol% or more, and 20 mol% or more. It is even more preferably 25 mol% or more, and particularly preferably 30 mol% or more. The upper limit of the content when butadiene is used is the same as the upper limit of the content of the alicyclic skeleton (X).

When butadiene and isoprene are used in combination as a conjugated diene compound, an alicyclic skeleton having a combination of the substituents (ii), (iii), (v), and (vi) in the polymer block (B). When one or more kinds of (X') are present, the total content thereof is 1 mol% or more to exhibit a more excellent anti-vibration effect and suppress a decrease in adhesive strength even at a high temperature. From the viewpoint of facilitation, it is preferably 2 mol% or more, more preferably 5 mol% or more, further preferably 8 mol% or more, and further preferably 13 mol% or more. preferable. The upper limit of the total content when butadiene and isoprene are used in combination is the same as the upper limit of the content of the alicyclic skeleton (X).
Further, when butadiene and isoprene are used in combination as a conjugated diene compound, one alicyclic skeleton (X) having a combination of the substituents (i) to (vi) described above is contained in the polymer block (B). When the above is present, the total content thereof is preferably 1 mol% or more from the viewpoint of exhibiting a more excellent anti-vibration effect and easily suppressing a decrease in adhesive strength even at high temperatures. It is more preferably mol% or more. The upper limit of the total content when butadiene and isoprene are used in combination is the same as the upper limit of the content of the alicyclic skeleton (X).

The content of the alicyclic skeleton (X) (including (X')) contained in the block copolymer or its hydrogenated product was determined by ¹³ C-NMR measurement of the block copolymer. It is a value obtained from the integrated value derived from the alicyclic skeleton (X) in B), and more specifically, it is a value measured according to the method described in Examples.

Further, the block copolymer or its hydrogenated product contains a vinyl group and a main chain bonded to the alicyclic skeleton (X) when the hydrogenation rate of the polymer block (B) is 0 mol% or more and less than 50 mol%. It is possible to specify the molar content ratio with the vinyl group bonded to.
For example, in the alicyclic skeleton (X') having a combination of the substituents (ii), (iii), (v), and (vi), the vinyl group terminal bonded to the alicyclic skeleton (X'). The chemical shift of the carbon atom ((a) of the following chemical formula) in ¹³ C-NMR appears in the vicinity of 107 to 110 ppm, and the ¹³ C of the carbon atom at the terminal of the vinyl group bonded to the main chain ((b) of the following chemical formula). -Chemical shift in NMR appears around 110-116 ppm. When the hydrogenation rate is 0 to 40 mol%, the peak area ratio [peak area of chemical shift value 107 to 110 ppm] / [peak area of chemical shift value 110 to 116 ppm] measured by ¹³ C-NMR is usually The area ratio is preferably 0.01 to 1.50, more preferably 0.01 to 1.00, still more preferably, from the viewpoint of being in the range of 0.01 to 3.00 and exhibiting more excellent vibration damping properties. Is 0.01 to 0.50, more preferably 0.01 to 0.20.

Also, the hydrogenated product, ¹³ but ^C-NMR peaks derived from the carbon atom on the alicyclic skeleton (X) in the measurement is hardly observed, the substituent R ³ is a hydrocarbon group having 1 to 11 carbon atoms Yes, a peak derived from a carbon atom on the alicyclic skeleton (X) that binds to a branched alkyl group derived from a vinyl group having R ³ can be observed.
Accordingly, when the hydrogenation rate of the polymer block for hydrogenated product (B) is 50 to 99 mol%, alicyclic skeleton (X) above that bind to a branched alkyl group derived from a vinyl group having the R ³ It is also possible to specify the molar ratio of the carbon atom contained in the carbon atom to the carbon atom 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 atom on the alicyclic skeleton (X) bonded to the isoprene group ((c) of the following chemical formula). It appears in the chemical shift around 50.0 ~ 52.0ppm in ¹³ C-NMR of ¹³ chemical shift in C-NMR of the carbon atoms on the main chain bonded isoprene group (the following chemical formula (d)) is It appears around 43.0-45.0 ppm. When the hydrogenation rate is 40 to 99 mol%, the peak area ratio measured by ¹³ C-NMR [peak area of chemical shift value 50.0 to 52.0 ppm] / [chemical shift value 43.0 to 45]. The peak area of .0 ppm is usually in the range of 0.01 to 3.00, and the area ratio is preferably in the range of 0.01 to 1.50, more preferably from the viewpoint of exhibiting better vibration damping properties. The range is 0.01 to 1.00, more preferably 0.01 to 0.50, and even more preferably 0.01 to 0.25.
The 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 blocks (B) contained in the block copolymer is preferably 15,000 in the state before hydrogenation from the viewpoint of vibration damping and molding processability when forming a laminate. It is from 800,000, more preferably 50,000 to 700,000, still more preferably 70,000 to 600,000, particularly preferably 90,000 to 500,000, and most preferably 130,000 to 450. It is 000.

(Other structural units)
The polymer block (B) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound as long as it does not interfere with the object and effect of the present invention. In this case, the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound in the polymer block (B) is preferably less than 50 mol%, more preferably less than 30 mol%, and further. It is preferably less than 20 mol%, more preferably less than 10 mol%, and particularly preferably 0 mol%.
Examples of the other polymerizable monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, and N. -Aromatic vinyl compounds such as vinylcarbazole, vinylnaphthalene and vinylanthracene, as well as methyl methacrylate, methylvinyl ether, β-pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylene tetrahydrofuran, 1,3- At least one compound selected from the group consisting of cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadien and the like is preferably mentioned.
The block copolymer may have at least one of the above-mentioned polymer blocks (B). When 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 for producing a block copolymer, for example, a polymer block having a structural unit containing the alicyclic skeleton (X) in a main chain by polymerizing one or more kinds of conjugated diene compounds as monomers by an anionic polymerization method. (B) is formed, the monomer of the polymer block (A) is added, and if necessary, the monomer of the polymer block (A) and the conjugated diene compound are sequentially added to obtain a block copolymer. be able to.
As a method for producing an alicyclic skeleton by the above anion polymerization method, a known technique can be used (see, for example, US Pat. No. 3,966691). The alicyclic skeleton is formed at the end of the polymer due to the depletion of the monomer, and the polymerization can be restarted from the alicyclic skeleton by sequentially adding the monomer to the terminal. Therefore, the presence or absence of formation of the alicyclic skeleton and its content can be adjusted by the sequential addition time of the monomers, the polymerization temperature, the type and addition amount of the catalyst, the combination of the monomer and the catalyst, and the like. Further, in the anionic polymerization method, an anionic polymerization initiator, a solvent, and if necessary, a Lewis base can be used.

Examples of the organolithium compound that can be used as a polymerization initiator for anionic polymerization in the above method include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium. Examples of the dilithium compound that can be used as the polymerization initiator include naphthalenedilithium and dilithiohexylbenzene.
Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenyl benzoate and the like.
The amount of these polymerization initiators and coupling agents used is appropriately determined by the desired weight average molecular weight of the block copolymer and its hydrogenated product. Usually, the initiator such as an alkyllithium compound or a dilithium compound is 0.01 to 0.2 parts by mass per 100 parts by mass of the monomer of the polymer block (A) used for polymerization and the monomer such as a conjugated diene compound. 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 monomers.

The solvent is not particularly limited as long as it does not adversely affect the anion polymerization reaction. For example, aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane and n-pentane; aromatic hydrocarbons such as benzene, toluene and xylene. And so on. 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.

Further, by a method of adding a Lewis base as a co-catalyst at the time of polymerization of the conjugated diene compound, the content of the alicyclic skeleton (X) in the polymer block (B), 3,4-bonds and 1,2 -The content of the bond can be increased.
Examples of Lewis bases that can be used include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane (DTHP); ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc. Glycol ethers such as tetraethylene glycol dimethyl ether; amines such as triethylamine, N, N, N', N'-tetramethylenediamine, N, N, N', N'-tetramethylethylenediamine (TMEDA), N-methylmorpholin. Classes: sodium or potassium salts of aliphatic alcohols such as sodium t-butylate, sodium t-amylate or sodium isopentylate, or dialkyl sodium cyclohexanolate, eg, sodium alicyclic alcohols such as sodium mentrate or Metal salts such as potassium salts; and the like. These Lewis bases can be used alone or in combination of two or more.

The amount of the Lewis base added includes how much the content of the alicyclic skeleton (X) is controlled, and the structural unit in which the polymer block (B) is particularly derived from isoprene and / or butadiene. In the case, it is determined by how much the vinyl bond amount of the isoprene unit and / or the butadiene unit constituting the polymer block (B) is controlled. Therefore, the amount of Lewis base added is not strictly limited, but is usually 0.1 to 1,000 mol per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as the polymerization initiator. It is preferably used in the range of 1 to 100 mol.

The average feed rate of the conjugated diene compound (hereinafter, may be referred to as “average diene feed rate”) is 150 kg / h or less per mol of the active terminal from the viewpoint of increasing the content of the alicyclic skeleton (X). Is preferable, 110 kg / h or less is more preferable, 55 kg / h or less is further preferable, 45 kg / h or less, 30 kg / h or less, or 22 kg / h or less. From the viewpoint of increasing productivity, the lower limit is preferably 1 kg / h or more, more preferably 3 kg / h or more, further preferably 5 kg / h or more, and may be 7 kg / h or more per mole of the active terminal. It may be 10 kg / h or more, or 15 kg / h or more.

After the polymerization is carried out by the above method, a block copolymer can be obtained by adding an active hydrogen compound such as alcohols, carboxylic acids and water to stop the polymerization reaction.

(Hydrogenated food)
When the block copolymer obtained by the above production method is used as a hydrogenated additive, a hydrogenation reaction (hydrogenation reaction) is carried out in the presence of a hydrogenation catalyst in an inert organic solvent. By 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, and the block copolymer can be hydrogenated.
In the hydrogenation reaction, the hydrogen pressure is about 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa, and the reaction temperature is about 20 to 250 ° C., preferably 50 to 180 ° C., more preferably. Can be carried out at 70 to 180 ° C. and a reaction time of usually about 0.1 to 100 hours, preferably 1 to 50 hours.
Examples of the hydrogenation catalyst include Raney nickel; a heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a single substance such as carbon, alumina, or diatomaceous earth; a transition metal compound, an alkylaluminum compound, or an alkyllithium. A transition metal catalyst composed of a combination with a compound or the like; a metallocene catalyst or the like can be mentioned.

The hydrogenated product thus obtained is coagulated by pouring the polymerization reaction solution into methanol or the like and then heated or dried under reduced pressure, or the polymerization reaction solution is poured into hot water together with steam and the solvent is azeotropically heated. It can be obtained by subjecting it to so-called steam stripping, which is then removed by heating, or by drying under reduced pressure.

Whether to use the block copolymer or the hydrogenated product can be specified according to the performance desired in various uses of the laminate. Similarly, the hydrogenation rate of the carbon-carbon double bond in the polymer block (B) when used as a hydrogenated additive depends on the performance desired in various uses of the laminate. Can be identified.
For example, the higher the hydrogenation rate of the hydrogenated product, the more the hydrogenated product can be obtained with improved heat resistance and weather resistance. The hydrogenation rate can be, 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, and 80 mol% or more and 99 mol% or less.

Therefore, it may be a block copolymer or a hydrogenated product thereof in which the hydrogenation rate of the polymer block (B) is 0 mol% or more (that is, including the case of unhydrogenation) and less than 50 mol%. Further, the polymer block (B) may be a hydrogenated product having a hydrogenation rate of 50 to 99 mol%.
The hydrogenation rate is the content of carbon-carbon double bonds in the conjugated diene compound in the polymer block (B) and the structural unit derived from the alicyclic skeleton (X), which is ¹ H after hydrogenation. -It is a value obtained by NMR measurement, and more specifically, it is a value measured according to the method described in Examples.

(Combination mode of polymer block (A) and polymer block (B))
As long as the polymer block (A) and the polymer block (B) are bonded to each other, the block copolymer is not limited in its bonding form, and is linear, branched, radial, or two of these. Any of the above-mentioned combined modes may be used. Above all, the bonding form of the polymer block (A) and the polymer block (B) is preferably linear, and as an example, the polymer block (A) is A and the polymer block (B) is. When represented by B, the diblock copolymer represented by AB, the triblock copolymer represented by ABA or BAB, and the tetra represented by ABAB. Block copolymer, pentablock copolymer represented by ABABA or BABAB, (AB) nZ type copolymer (Z is the coupling agent residue) A group is represented, and n represents an integer of 3 or more) and the like. Of these, linear triblock copolymers or diblock copolymers are preferable, and ABA type triblock copolymers are preferably used from the viewpoints of flexibility, ease of production, and the like.
Specific examples of the ABA type triblock copolymer include a styrene-butadiene / isoprene-styrene copolymer. Above all, it is preferable that at least one of the base material layer and the adhesive layer contains at least a styrene-hydrogenated butadiene / isoprene-styrene copolymer as a hydrogenated additive of the block copolymer.

Here, in the present specification, when the same type of polymer blocks are linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer blocks are treated as one polymer block. Is done. In accordance with this, the polymer block, which should be strictly described as YZZ (Z represents a coupling residue), including the above examples, needs to be particularly distinguished from the single polymer block Y. Except in some cases, it is displayed as Y as a whole. In the present specification, since this type of polymer block containing the coupling agent residue is treated as described above, for example, it contains the coupling agent residue and is strictly ABZBA ( The block copolymer that should be described as (Z represents a coupling agent residue) is described as ABA and is treated as an example of a triblock copolymer.

(Contents of polymer blocks (A) and (B))
The block copolymer may contain a polymer block composed of a monomer other than the polymer blocks (A) and (B) as long as it does not interfere with the object and effect of the present invention. However, the total content of the polymer block (A) and the polymer block (B) is preferably 90% by mass or more, more preferably 95% by mass or more, and substantially 100% by mass. Is particularly preferable. When it is 90% by mass or more, it is excellent in vibration damping and molding processability, it is easy to suppress a decrease in adhesive strength even at a high temperature, and it is a block copolymer or a hydrogenated product thereof that can be suitably used for a laminate. can do.

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

[Tanδ]
(Peak top temperature and intensity of tan δ)
tan δ (tangent loss) is the ratio of loss elastic modulus / storage elastic modulus at a frequency of 1 Hz in dynamic viscous bullet measurement, and the peak top temperature and intensity of tan δ greatly contribute to vibration damping and other physical properties. Here, the peak top intensity of tan δ is the value of tan δ when the peak of tan δ is maximized. The peak top temperature of tan δ is the temperature at which the peak of tan δ is maximized.

In the present specification, the peak top temperature and intensity of tan δ of the block copolymer or its hydrogenated product are such that the block copolymer or its hydrogenated product is pressurized at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes to obtain a thickness of 1. A 0.0 mm single-layer sheet is prepared, the single-layer sheet is cut into a disk shape, and this is measured as a test piece. The measurement conditions are, in accordance with JIS K 7244-10 (2005), 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.
The peak top temperature and tan δ intensity of the block copolymer or its hydrogenated product are more specifically measured values according to the method described in Examples.

The block copolymer or its hydrogenated product can have a peak top intensity of tan δ of 1.0 or more according to the above measurement. Some of the higher ones are 1.5 or more, and even 1.9 or more. The higher the peak top strength of tan δ, the better the physical properties such as vibration damping at that temperature, and if it is 1.0 or more, sufficient vibration damping can be obtained in an actual use environment.
Further, the block copolymer or its hydrogenated additive has a peak top temperature of tan δ of preferably −50 ° C. or higher, more preferably −40 ° C. or higher, still more preferably −30 ° C. or higher, and even more preferably −25 ° C. It is the above, and it may be 0 degreeC or more. The upper limit of the peak top temperature of tan δ may be 50 ° C. or lower, 40 ° C. or lower, or 35 ° C. or lower as long as the effect of the present invention is not impaired. Good. The range of the peak top temperature of tan δ is, for example, preferably -50 to 50 ° C, more preferably -40 to 40 ° C, still more preferably -30 to 30 ° C, and even more preferably -25 to 25 ° C. .. When the peak top temperature of tan δ is −50 ° C. or higher, sufficient vibration damping property can be obtained in an actual use environment, and when it is 50 ° C. or lower, desirable adhesiveness is exhibited when used in an adhesive layer. can do.

(Maximum width of temperature range where tan δ is 1.0 or more)
Further, the block copolymer or its hydrogenated product has a series of temperature ranges in which tan δ at −70 to 100 ° C. measured under the above measurement conditions is 1.0 or more, and the maximum width of the temperature range is preferably 1.0. It is 12 ° C. or higher, more preferably 13 ° C. or higher, still more preferably 15 ° C. or higher, and even more preferably 17 ° C. or higher.
As described above, in the structural unit of the polymer block (B), the alicyclic skeleton (X) is incorporated in the main chain, and since it can have a higher vinyl bond amount, the molecular motion becomes smaller, so that the glass The transition temperature rises, and the glass transition becomes gentle with respect to temperature changes. As a result, the temperature range in which the tan δ of the block copolymer or its hydrogenated product is 1 or more becomes wide, and it becomes possible to exhibit vibration damping properties in a wide temperature range. When the maximum width of the temperature region in which tan δ is 1.0 or more is 12 ° C. or higher, and further, 13 ° C. or higher, better vibration damping properties can be obtained in an actual use environment. Further, the maximum width of the temperature region has no particular upper limit, but for example, from the viewpoint of productivity, the upper limit may be 35 ° C, 30 ° C, or 25 ° C. May be good.

≪Base material layer≫
The base material layer can contain the above-mentioned block copolymer or a hydrogenated additive thereof from the viewpoint of being suitable for further improving the vibration damping property of the adherend.
The content of the block copolymer or its hydrogenated material in the base material layer is preferably 1 to 100% by mass. From the viewpoint of further improving the vibration damping property of the adherend, the content of the block copolymer or its hydrogenated material in the base material layer is more preferably 3% by mass or more, still more preferably 5% by mass or more. More preferably, it is 10% by mass or more. The upper limit of the content is not particularly limited as long as the effect of the present invention is not impaired, but it is different from other resins that can be used as the material of the base material layer described later while maintaining the strength of the laminate. From the viewpoint of easy compatibility, 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. Hereinafter, it is even more preferably 40% by mass or less, and may be 30% by mass or less and 25% by mass or less.

[Non-alicyclic skeletal block copolymer and its hydrogenated product]
From the viewpoint of performance as a laminate, the base material layer contains a polymer block (A) and a polymer block (B) similar to the above-mentioned block copolymer or its hydrogenated additive, and the polymer. A block copolymer in which the block (B) does not have a structural unit containing an alicyclic skeleton represented by the above formula (X) in the main chain or a hydrogenated product thereof (hereinafter, "non-alicyclic skeleton block together" It may be referred to as "polymer or hydrogenated product thereof").
The non-alicyclic skeleton block copolymer and its hydrogenated additive do not have a structural unit in which the alicyclic skeleton represented by the formula (X) is contained in the main chain of the polymer block (B). , The same as the block copolymer described above or a hydrogenated product thereof.

[Other resins]
From the viewpoint of performance as a laminate and economic efficiency, a resin other than the above-mentioned block copolymer or its hydrogenated additive (hereinafter, may be referred to as “other resin”) is used as the base material layer. It is preferably used as a material for the base material layer.

(Olefin resin)
As the other resin, an olefin resin is preferable from the viewpoint of performance as a laminate and economic efficiency. Examples of the olefin resin include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylene such as homopolypropylene, block polypropylene, and random polypropylene; homopolymers or copolymers of α-olefin. Examples include polypropylene and / or a copolymer of ethylene and α-olefin. Examples of the α-olefin include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-. Examples thereof include α-olefins having 20 or less carbon atoms such as octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and one or two of these. The above can be used. Further, a modified olefin resin obtained by modifying these olefin resins with maleic acid or the like can also be used.
Among these olefin resins, polypropylene is preferable from the viewpoint of being suitable for obtaining a laminate having high compatibility with the above-mentioned block copolymer or its hydrogenated product and having excellent transparency.
More specifically, as an example of a preferred embodiment of the present embodiment, an olefin resin and a block copolymer or a hydrogenated product thereof can be used as the other resin in the base material layer. Above all, it is preferable to use an olefin resin and a hydrogenated block copolymer. Since the compatibility between the olefin resin and the hydrogenated additive is good, it is easy to maintain the better transparency of the base material layer.

(Resin other than olefin resin)
Further, as the other resin, a resin other than the olefin resin may be used.
Resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer sulfide, styrene-butadiene rubber, styrene-isoprene rubber, nitrile rubber, butyl rubber, natural rubber, and ethylene-vinyl acetate copolymer. , Ethylene- (meth) acrylate copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer metal ion cross-linked resin (ionomer) ), Polystyrene resin such as polystyrene, AS resin, ABS resin, polyphenylene ether resin, polyamide resin such as nylon 6 and nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyurethane resin, polyoxymethylene homo. Examples include polymers, acetal resins such as polyoxymethylene copolymers, acrylic resins such as polymethyl methacrylate-based resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl chloride-vinyl acetate copolymers. Be done.

Further, as the material of the base material, from the viewpoint of performance as a laminate and economic efficiency, preferably, a block copolymer or a combination of a hydrogenated additive thereof and another resin, and a non-alicyclic skeleton block co-weight. Examples thereof include coalescence and a combination of a hydrogenated product thereof and another resin, and more preferably a block copolymer or a hydrogenated product thereof from the viewpoint of obtaining performance and economic efficiency as a laminate and better vibration damping properties. It is a combination with other resins.
The structure of the base material layer may be one layer or may be a multi-layer structure of two or more layers. When it is composed of two or more layers, two or more kinds of resins having different materials may be used.

[Content]
The content of the non-alicyclic skeleton block copolymer and its hydrogenated material in the base material layer is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 5% by mass or more, from the viewpoint of the 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 hydrogen additive in the base material layer is not particularly limited as long as the effect of the present invention is not impaired, and may be 100% by mass. From the viewpoint of economy, it is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

The content of the other resin in the base material layer is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably, from the viewpoint of performance as a laminate and economic efficiency. Is 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more. On the other hand, the upper limit of the content of the other resin in the base material layer is not particularly limited as long as the effect of the present invention is not impaired, and may be 100% by mass. When the coalescence or its hydrogenated material is contained, it is preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass, from the viewpoint of further improving the vibration damping property of the adherend. It is as follows.

The ratio of the content of the block copolymer or its hydrogen additive to other resin in the base material layer is the content of the block copolymer or its hydrogen additive when the total content thereof is 100% by mass. Is preferably 1 to 99% by mass, more preferably 1 to 90% by mass, still more preferably 1 to 80% by mass, still more preferably 1 to 70% by mass, still more preferably 1 to 60% by mass, still more preferably. Is 1 to 50% by mass, more preferably 1 to 40% by mass, and may be 1 to 30% by mass, and 1 to 25% by mass.
As an example of a preferred embodiment of the present embodiment, when the other resin is an olefin resin, the content ratio of the block copolymer or its hydrogenated additive is 1 to 99% by mass, and the olefin resin is used. The content of the block copolymer is 99 to 1% by mass, and a more preferable embodiment is the same as the ratio of the content of the block copolymer or its hydrogenated additive to other resins.
As an example of a more preferable embodiment of the present 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. It is by mass%, and a more preferable embodiment is the same as the ratio of the content of the block copolymer or its hydrogenated additive to other resins.

Further, as an example of a preferred embodiment of the present embodiment, when the material of the base material layer is a non-alicyclic skeleton block copolymer or a combination of a hydrogenated additive thereof and another resin, the non-alicyclic skeleton block co-weight is used. As for the ratio of the content of the coalescence or its hydrogenated product to other resin, the content of the non-alicyclic skeletal block copolymer or its hydrogenated product is preferable, assuming that the total content thereof is 100% by mass. 1 to 99% by mass, more preferably 1 to 90% by mass, still more preferably 1 to 80% by mass, still more preferably 1 to 70% by mass, still more preferably 1 to 60% by mass, still more preferably 1 to 1 to It is 50% by mass, more preferably 1 to 40% by mass.
The total content of the block copolymer or its hydrogenated material in the base material layer, the non-alicyclic skeleton block copolymer and its hydrogenated material, and other resins is preferably 90% by mass or more, more preferably. Is 95% by mass or more, and may be 100% by mass.

[Additive]
Further, the base material layer in the present embodiment does not prevent the inclusion of the tackifier resin described later as long as the effect of the present invention is not impaired. However, since the base material layer has adhesiveness, the performance as a base material may be impaired, and there is a possibility that unnecessary adhesiveness may be exhibited in the base material. The content of the tackifier resin in the base material layer is preferably less than 1% by mass, and the base material layer is substantially free of the tackifier resin (content of the tackifier resin is 0% by mass). May be good.
Additives may be further added to the base material layer, if necessary, as long as the object of the present invention is not impaired. Examples of the additive include a cross-linking agent (isocyanate-based cross-linking agent, epoxy-based cross-linking agent, metal chelate-based cross-linking agent, aziridine-based cross-linking agent, amine resin, etc.), heat stabilizer, light stabilizer, ultraviolet absorber, infrared absorber. , Antioxidant, Lubricating agent, Coloring agent, Antistatic agent, Flame retardant, Water repellent, Waterproofing agent, Hydrophilicity imparting agent, Conductivity imparting agent, Thermal conductivity imparting agent, Electromagnetic wave shielding imparting agent, Translucency adjustment Agent, fluorescent agent, slidability imparting agent, transparency imparting agent, antiblocking agent, metal inactivating agent, antibacterial agent, crystal nucleating agent, crack inhibitor, ozone deterioration inhibitor, rodent inhibitor, dispersant, Thickeners, light-resistant agents, weather-resistant agents, copper damage inhibitors, reinforcing agents, mold-proofing agents, macrocyclic molecules (cyclodextrin, calix array, kukurubituriru, etc.), adhesives other than the tackifier resin (acrylic adhesives, etc.) ) Etc. can be mentioned. The content of the additive is preferably 10 parts by mass or less, more preferably 5 parts by mass or less per 100 parts by mass of the resin component for the above-mentioned base material layer, from the viewpoint of suppressing bleeding from the base material layer.

≪Adhesive layer≫
In addition to the block copolymer or its hydrogenated additive, the pressure-sensitive adhesive layer in the present embodiment preferably contains a pressure-imparting resin from the viewpoint of increasing the pressure-sensitive adhesive strength of the laminate and maintaining the pressure-sensitive adhesive strength even at high temperatures.

[Adhesive-imparting resin]
Examples of the tackifying resin include kumaron resins such as kumaron / inden resin; phenol-based resins such as pt-butylphenol / acetylene resin, phenol / formaldehyde resin, terpen / phenol resin, polyterpene resin, xylene / formaldehyde resin, and terpen-based resins. Resin: Petroleum resin such as aromatic petroleum resin, aliphatic petroleum resin, alicyclic petroleum resin, aromatic petroleum resin, modified alicyclic petroleum resin; rosin pentaerythritol ester, rosin glycerol ester, etc. Rosin-based resins such as rosin esters, hydrogenated rosins, methyl esters of hydrogenated rosins, pentaerythritol esters of polymerized rosins, hydrogenated rosin esters, refractory rosin-based resins, polymerized rosins, cured rosins, and special rosin esters. And so on. Among them, an alicyclic saturated hydrocarbon resin can be preferably used as the tackifier resin. Examples of the alicyclic saturated hydrocarbon resin include those obtained by hydrogenating an aromatic petroleum resin, and for example, a commercially available product such as the “Arcon” series manufactured by Arakawa Chemical Industry Co., Ltd. may be used. These tackifier resins may be used alone or in combination of two or more. From the viewpoint of reducing the adhesive residue of the obtained pressure-sensitive adhesive layer and improving heat resistance and weather resistance, it is preferable to use a hydrogenated pressure-sensitive adhesive resin.
The softening point of the tackifier resin is preferably 85 to 160 ° C, more preferably 100 to 150 ° C, and even more preferably 105 to 145 ° C. When the softening point of the tackifying resin is 85 ° C. or higher, it becomes easy to suppress a decrease in the adhesive holding power at a high temperature (about 60 ° C.), and when it is 160 ° C. or lower, the molding processability of the composition constituting the adhesive layer is improved. It is good.

[Content]
The content of the above-mentioned block copolymer or its hydrogenated material in the adhesive layer may be 100% by mass, but is preferably 1 to 80% by mass from the viewpoint of vibration damping property of the laminate and adhesive strength at high temperature. ..
Further, the content of the block copolymer or its hydrogenated material in the adhesive layer is more preferably 5% by mass or more, still more preferably 10% by mass or more, from the viewpoint of further improving the vibration damping property of the laminated body. .. On the other hand, the content of the block copolymer or its hydrogenated product in the adhesive layer is more preferably 70% by mass or less, still more preferably 60% by mass, from the viewpoint of economy and making it easier to maintain the adhesive force at high temperature. % Or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.

The content of the tackifier resin in the pressure-sensitive adhesive layer is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 15% by mass, from the viewpoint of the adhesive strength of the pressure-sensitive adhesive layer. That is all. On the other hand, the content of the tackifier resin in the pressure-sensitive adhesive layer is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, from the viewpoint of reducing the adhesive residue of the pressure-sensitive adhesive layer.

[Non-alicyclic skeletal block copolymer and its hydrogenated product]
Further, as the resin component constituting the adhesive layer, it is preferable to use the above-mentioned non-alicyclic skeleton block copolymer or a hydrogenated additive thereof from the viewpoint of performance as a laminated body.
The content of the non-alicyclic skeleton block copolymer or its hydrogenated additive in the adhesive layer is preferably 10% by mass or more, more preferably 20% by mass, from the viewpoint of reducing the adhesive residue of the adhesive layer and the adhesive strength of the adhesive layer. % Or more, more preferably 30% by mass or more, still more preferably 40% by mass or more. On the other hand, the upper limit of the content of the non-alicyclic skeleton block copolymer and its hydrogen additive in the adhesive layer is not particularly limited as long as the effect of the present invention is not impaired, and may be 100% by mass, but is economical. From the viewpoint of properties, it is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less.

[Other resin components]
(Olefin resin)
An olefin resin may be used as a resin component constituting the adhesive layer as long as the object of the present invention is not impaired.
Examples of the olefin resin include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylene such as homopolypropylene, block polypropylene, and random polypropylene; homopolymers or copolymers of α-olefin. Examples include polypropylene and / or a copolymer of ethylene and α-olefin. Examples of the α-olefin include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 1-. Examples thereof include α-olefins having 20 or less carbon atoms such as octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and one or two of these. The above can be used. Further, a modified olefin resin obtained by modifying these olefin resins with maleic acid or the like can also be used.

(Resin other than olefin resin)
Further, a resin other than the above-mentioned olefin resin may be used as the resin component constituting the adhesive layer as long as the object of the present invention is not impaired.
Resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer sulfide, styrene-butadiene rubber, styrene-isoprene rubber, nitrile rubber, butyl rubber, natural rubber, and ethylene-vinyl acetate copolymer. , Ethylene- (meth) acrylate copolymer, ethylene-ethyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer metal ion cross-linked resin (ionomer) ), Polystyrene resin such as polystyrene, AS resin, ABS resin, polyphenylene ether resin, polyamide resin such as nylon 6 and nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyurethane resin, polyoxymethylene homo. Examples include polymers, acetal resins such as polyoxymethylene copolymers, acrylic resins such as polymethyl methacrylate-based resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, and ethylene-vinyl chloride-vinyl acetate copolymers. Be done.

(Additive)
A plasticizer or a filler may be added to the adhesive layer as needed, as long as the object of the present invention is not impaired.
Examples of the plasticizer include paraffin-based, naphthen-based, and aromatic process oils; phthalic acid derivatives such as dioctylphthalate and dibutylphthalate; white oil; mineral oils; liquid copolymers of ethylene and α-olefins; liquid paraffins; Polybutene; low molecular weight polyisobutylene; liquid polydiene such as liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene / butadiene copolymer, liquid styrene / butadiene copolymer, liquid styrene / isoprene copolymer, and hydrogenated products thereof. Be done.
Examples of the filler include talc, mica, calcium silicate, glass, glass flakes, glass beads, hollow spheres of glass, glass fibers, calcium carbonate, magnesium carbonate, zinc carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide. , Calcium hydroxide, zinc borate, dosonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, silica alumina, diatomaceous soil, wollastonite, zeolite, boehmite, sodium aluminosilicate, magnesium silicate, graphene, barium carbonate , Silicon nitride, aluminum hydroxide, boron nitride, potassium titanate, aluminum silicate (kaolin, clay, pyrophyllite, bentonite), magnesium silicate (atapulsite), aluminum borate, calcium sulfate, magnesium sulfate, alumina, titanium oxide , Iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, carbon nanotubes, graphite, carbon fiber, activated charcoal, hollow spheres of carbon, calcium titanate, lead zirconate titanate, carbonized Inorganic fillers such as silicon; organic fillers such as wood powder and starch; organic pigments and the like can be mentioned. These fillers may be used alone or in combination of two or more.
Further, other additives may be further added to the adhesive layer as needed, as long as the object of the present invention is not impaired. Examples of the additive include a cross-linking agent (isocyanate-based cross-linking agent, epoxy-based cross-linking agent, metal chelate-based cross-linking agent, aziridine-based cross-linking agent, amine resin, etc.), heat stabilizer, light stabilizer, ultraviolet absorber, infrared absorber. , Antioxidant, Lubricating agent, Coloring agent, Antistatic agent, Flame retardant, Water repellent, Waterproofing agent, Hydrophilicity imparting agent, Conductivity imparting agent, Thermal conductivity imparting agent, Electromagnetic wave shielding imparting agent, Translucency adjustment Agent, fluorescent agent, slidability imparting agent, transparency imparting agent, antiblocking agent, metal inactivating agent, antibacterial agent, crystal nucleating agent, crack inhibitor, ozone deterioration inhibitor, rodent inhibitor, dispersant, Thickeners, light-resistant agents, weather-resistant agents, copper damage inhibitors, reinforcing agents, mold-proofing agents, macrocyclic molecules (cyclodextrin, calix array, kukurubituriru, etc.), adhesives other than the tackifier resin (acrylic adhesives, etc.) ) Etc. can be mentioned.
On the other hand, from the viewpoint of maximizing the effect of the present invention, the content of each of the plasticizer, the filler and the additive in the adhesive layer is preferably 10% by mass or less, more preferably 5% by mass or less. More preferably, it is by mass or less. If these contents are 10% by mass or less, it is considered that the behavior of tan δ strength, which will be described later, is hardly affected.

≪Manufacturing method of laminated body≫
The method for producing the above-mentioned laminate is not particularly limited, and for example, (1) a coextrusion molding method in which a composition constituting a base material layer and a composition constituting an adhesive layer are coextruded by a multi-layer T-die extruder or the like, (2). ) A method of applying a composition constituting an adhesive layer to a molded base material layer, (3) a compression molding method of laminating a molded base material layer and a composition constituting an adhesive layer by compression molding and the like. ..

The composition constituting the base material layer and the composition constituting the adhesive layer can be produced by melt-kneading, respectively.
In the melt kneading, the components to be blended in each layer are mixed by using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender, or after the mixing, a uniaxial or biaxial extruder is used. , Kneader or the like may be used for melt kneading. The temperature at the time of melt-kneading can be appropriately set, but is usually 150 to 300 ° C, preferably 160 to 250 ° C.
Each composition constituting the obtained base material layer and adhesive layer is preferably pelletized from the viewpoint of easily producing the laminate by extrusion molding.

When the laminate is produced by the coating method of (2) above, a solution is prepared by dissolving the composition constituting the adhesive layer in an organic solvent, and this solution is applied to the molded base material layer. By drying, a laminated body can be preferably obtained. This organic solvent is not particularly limited as long as it is a solvent capable of dissolving the composition constituting the adhesive layer. Examples of the solvent include cyclohexane, methylcyclohexane, n-hexane, n-heptane, benzene, toluene, toluene-ethanol mixed solvent, xylene, ethylbenzene, tetrahydrofuran and the like. These solvents may be used alone or in combination of two or more. Toluene, a toluene-ethanol mixed solvent, xylene, and ethylbenzene are preferable from the viewpoints of ease of coating, easy preparation of a solution, and easy drying.
The concentration of the resin component in the solution is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30 from the viewpoint of ease of coating, easy production of the solution, and easy drying. It is mass%.

When a laminate is produced by the coextrusion molding method of (1) above, the composition constituting the base material layer and the composition constituting the adhesive layer are melt-plasticized using different extruders, and each pellet is combined with each pellet. To do. After that, each pellet is merged and multilayered by a feed block die provided at the tip of the extruder, extruded, and then taken out in the form of a film, so that it can be suitably manufactured.
When a laminate is produced by the compression molding method of (3) above, the composition constituting the pellet-shaped or sheet-shaped adhesive layer is laminated on the molded base material, compression-molded while heating, and then cooled. Can be more preferably obtained.

When the composition constituting the adhesive layer is a hot melt type, the composition is heated and melted by heating and melting using an applicator for hot melt similar to the conventional one, applied to the base material layer, and then cooled. As a result, a laminated body can be preferably obtained.

An example of the combination of the composition constituting the base material layer and the composition constituting the adhesive layer in the laminate is shown. The above combination is, for example, when the above-mentioned block copolymer or its hydrogenated product is represented by <1> and the non-alicyclic skeletal block copolymer or its hydrogenated product is represented by <2>, for example.
A laminate in which the composition constituting the base material layer contains an olefin resin and <1> and / or <2>, and the composition constituting the pressure-sensitive adhesive layer contains a tackifier resin and <1> and / or <2>. Body (however, at least one of the base material layer and the adhesive layer contains <1>);
A laminate in which the composition constituting the base material layer contains an olefin resin and <1> and / or <2>, and the composition constituting the pressure-sensitive adhesive layer contains a tackifier resin and <1>;
A laminate in which the composition constituting the base material layer contains the olefin resin and <1> and / or <2>, and the composition constituting the pressure-sensitive adhesive layer contains the tackifier resin and <2> (however, the base material). At least one of the layers and the adhesive layer contains <1>);
A laminate in which the composition constituting the base material layer contains an olefin resin and <1>, and the composition constituting the pressure-sensitive adhesive layer contains a tackifier resin and <1> and / or <2>;
A laminate in which the composition constituting the base material layer contains an olefin resin and <2>, and the composition constituting the pressure-sensitive adhesive layer contains a tackifier resin and <1> and / or <2> (however, the base material). At least one of the layers and the adhesive layer contains <1>);
Can be mentioned. The present embodiment is not limited to the combination of the composition constituting the base material layer and the composition constituting the adhesive layer. Specific embodiments of <1>, <2>, the olefin resin, and the tackifier resin in the composition constituting the base material layer and the composition constituting the adhesive layer are the specific embodiments described above for each. Is similar to. Further, the composition constituting the base material layer and the composition constituting the adhesive layer may each contain the above-mentioned additives.

≪Physical properties of each layer and laminate≫
[Hardness ratio [i / ii]]
In the present embodiment, the ratio [i / ii] of the shore A hardness i of the base material layer to the shore A hardness i of the adhesive layer is 1.1 or more. When the shore A hardness ratio [i / ii] is less than 1.1, the function of the base material layer as a support for the adhesive layer is impaired, the adhesive layer becomes difficult to fix to the base material layer, and various laminated bodies are formed. Inconvenience occurs when it is used for various purposes. The above ratio [i / ii] varies depending on the application, but is preferably 1.2 or more, more preferably 1.2 or more, from the viewpoint that the adhesive layer can be fixed to the base material layer and the laminate can be easily attached and peeled off. It is 1.3 or more. Further, the upper limit of the above ratio [i / ii] is different depending on the application and cannot be unconditionally specified, but can be, for example, 3.3 or less.

[hardness]
The shore A hardness i of the base material layer is not limited as long as the hardness ratio [i / ii] can be satisfied. On the other hand, the shore A hardness i of the base material layer is preferably 60 to 100, more preferably 60 to 100, from the viewpoint that the performance as the base material layer can be suitably shown and the laminate can be easily attached and peeled off. Is 70 to 98.
The shore A hardness ii of the adhesive layer is not limited as long as the hardness ratio [i / ii] can be satisfied. On the other hand, the shore A hardness ii of the adhesive layer is preferably 30 to 80, from the viewpoints of adhesiveness to the base material layer, resistance to adhesive residue, and ease of attachment and peeling to the adherend. It is preferably 40 to 70.
The Shore A hardness is a value measured in more detail according to the method described in Examples.

[Storage modulus of adhesive layer]
In the present embodiment, the ratio of the storage elastic modulus E'(23 ° C.) at 23 ° C. to the storage elastic modulus E'(60 ° C.) of the adhesive layer at 60 ° C. [E'(23 ° C.) / E'(60 ° C.) )] Is preferably 2 or more.
In the present embodiment, the pressure-sensitive adhesive layer contains the above-mentioned block copolymer or a hydrogenated product thereof, so that the ratio of storage elastic modulus [E'(23 ° C.) / E'(60 ° C.)] is 2 or more. It will be easier to achieve. Generally, the adhesive strength decreases as the temperature rises, but in the present embodiment, if the ratio of storage elastic modulus [E'(23 ° C.) / E'(60 ° C.)] is 2 or more, 23 ° C. to 60 ° C. The degree of decrease in peel strength with respect to ° C is small, and the peeling tends to be difficult even at high temperatures and adhesive residue is unlikely to occur.
In the present embodiment, the ratio of the storage elastic modulus of the pressure-sensitive adhesive layer [E'(23 ° C.) / E'(60 ° C.)] is the composition of the pressure-sensitive adhesive layer (the above-mentioned pressure-sensitive resin, the above-mentioned block copolymer or its own. By adjusting the hydrogen additive, the above-mentioned non-alicyclic skeleton block copolymer and its hydrogen additive, and the types and contents of other resin components), 2.5 or more, and further 3.0 or more. It is also possible to.
The storage elastic modulus is a value measured in more detail according to the method described in Examples.

[Tanδ strength]
The above-mentioned block copolymer or hydrogenated product thereof can exhibit excellent vibration damping properties. Therefore, when the base material layer contains a block copolymer or a hydrogenated product thereof, the tan δ strength of the base material layer can be preferably 0.05 or more, more preferably 0.10 or more at a temperature of 23 ° C. At a temperature of 40 ° C., it can be preferably 0.05 or more, more preferably 0.10 or more, and at a temperature of 60 ° C., it can be preferably 0.05 or more, more preferably 0.10 or more.
When the adhesive layer contains a block copolymer or a hydrogenated additive thereof, the tan δ strength of the adhesive layer is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0 at a temperature of 23 ° C. It can be .18 or higher, preferably 0.10 or higher, more preferably 0.15 or higher, even more preferably 0.18 or higher, even more preferably 0.25 or higher at a temperature of 40 ° C. at a temperature of 60 ° C. It can be preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0.18 or more.
Further, the loss coefficient of the adherend to which the laminate is attached is preferably 0.05 or more, more preferably 0.10 or more, still more preferably 0, as compared with the loss coefficient of the adherend to which the laminate is not attached. It can be expected to grow by .15 or more. In particular, when the block copolymer or its hydrogen additive is contained in both the base material layer and the adhesive layer, the loss coefficient of the adherend to which the laminate is attached is the loss coefficient of the adherend to which the laminate is not attached. In comparison, it can be expected to be preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0.20 or more.
The tan δ intensity is a value measured in more detail according to the method described in Examples.

[Peeling strength]
In the present embodiment, the peel strength of the laminate is based on JIS Z 0237 (2009) by using an acrylic resin plate as an adherend and laminating the adhesive layer of the laminate so that the adherend is in contact with the adherend. The 180-degree peel strength measured in the above can be preferably 5.0 N / 25 mm or more, more preferably 6.0 N / 25 mm or more at the measurement temperature of 23 ° C. Further, the peel strength under the same conditions can be preferably 2.0 N / 25 mm or more, more preferably 2.5 N / 25 mm or more at the measurement temperature of 60 ° C. Generally, the adhesive strength decreases as the temperature rises, but in the present embodiment, one or both of the base material layer and the adhesive layer contains the above-mentioned block copolymer or its hydrogenated additive, and the content thereof is suitable. The above adhesive strength can be easily achieved by adjusting the adhesive strength to a certain range.
Further, in the present embodiment, the ratio of the peeling strength at 60 ° C. to the peeling strength at 23 ° C. of the laminated body can be 0.3 or more, further 0.4 or more. The peel strength ratio can be easily achieved by adjusting the composition of the pressure-sensitive adhesive layer (the above-mentioned block copolymer or its hydrogenated additive, the above-mentioned pressure-sensitive resin and the type and content of any component).
The peel strength is a value measured in more detail according to the method described in Examples.

≪Layer dimensions≫
The thickness of the adhesive layer constituting the laminate of the present embodiment is not particularly limited, but is usually preferably 1 μm or more and 200 μm or less, more preferably 5 μm or more and 150 μm or less, and 5 μm or more and 100 μm or less. Is even more preferable.
On the other hand, the thickness of the base material layer is not particularly limited and may be specified according to the use of the laminated body. However, in order to preferably exert the adhesive strength of the adhesive layer, 500 μm or less is preferable, and 200 μm or less is more preferable. , 100 μm or less is more preferable. The thickness of the base material layer is usually 5 μm or more.

≪Use≫
In this embodiment, the laminate can be used for various purposes.
Applications include, for example, an adhesive containing a laminate, and examples of the adhesive include a pressure-sensitive adhesive. In addition, an adhesive tape, an adhesive sheet, and a surface protective film containing the pressure-sensitive adhesive can be mentioned.

Moreover, the hot melt adhesive is mentioned as the said adhesive.
The hot melt adhesives include, for example, disposable diapers, adult incontinence products, sanitary napkins, bed pads, first aid bonds, surgical drapes, single-sided tapes, double-sided tapes, transfer tapes, labels, plastic sheets, non-woven sheets, paper sheets. For use in articles with thick paper, books, filters, or packaging;
Use in gasket sealants (especially in the fields of automobiles, electrical parts, technical lighting);
Use in the manufacture of resealable trays of multilayer films;
Use in articles containing materials for mailing containers;
Anti-vibration material, cushioning material, shock absorber, low-resilience material, fall-prevention material, seismic isolation material, seismic isolation material, or vibration-damping material (preferably sound deadening material, more preferably damping or sound deadening material mat, pad in the automobile industry. , Sheets and tapes);
Use in electronic devices (especially LCD displays, LED displays, touch screens, or flexible thin film solar cells);
Use in percutaneous drug delivery systems;
Couplings between pipes (preferably cooling coils), electronic components (preferably light emitting elements, computer equipment, mobile phones, tablets, touch screens, automotive technology hi-fi systems, and audio systems), solar-heated thermal pipes and water tanks. Department, fuel cell and wind turbine, computer chip manufacturing, optical device, battery, housing, cooler, heat exchange device, wire, cable, heating wire, refrigerator, dishwasher, air conditioner, accumulator, transformer, laser equipment, functionality Use in clothing, car seats, medical equipment, fire protection, electric motors, planes, and trains;
Use in filaments of 3D printing materials, injection sealants or molding sealants to seal heat-generating devices;
Use for joining articles with substrates made of wood, metal, polymer plastics, glass and textiles; use for joining to the outer surface in water towers; glazing in the manufacture of footwear or in the manufacture of windows Use as a compound, in the manufacture of doors and building panels, or in the manufacture of portable devices and displays;
Bookbinding, wood bonding, flat lamination, flexible packaging, profile wrapping, edge banding, textile lamination, low pressure molding, and use in shoes;
Use in the manufacture of bonded fabrics / fabrics for books, packaging films, rigid panels, furniture, windows, footwear, automobile headlights, automobile trims or garments;
Use in decorative films;
Can be mentioned.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Block copolymers and hydrogenated products>
The method for evaluating the physical properties of the block copolymer or hydrogenated product obtained in the production example described later is shown below.
(1) Content of polymer block (A) ¹ H-NMR measurement by dissolving the block copolymer before hydrogenation in CDCl ₃ [Equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 ° C.], and the content of the polymer block (A) was calculated from the ratio of the peak intensity derived from styrene and the peak intensity derived from diene.

(2) Weight average molecular weight (Mw)
The polystyrene-equivalent weight average molecular weight (Mw) of the hydrogenated block copolymer was determined by gel permeation chromatography (GPC) measurement under the following conditions.
(GPC measuring device and measuring conditions)
-Device: GPC device "HLC-8020" (manufactured by Tosoh Corporation)
Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Toso Co., Ltd. were connected in series.
-Eluent: tetrahydrofuran-Eluent flow rate: 0.7 mL / min
-Sample concentration: 5 mg / 10 mL
-Column temperature: 40 ° C
-Detector: Differential refractive index (RI) detector-Calibration curve: Created using standard polystyrene

(3) Hydrogenation rate in the polymer block (B) ¹ Calculated from the ratio of the peak area derived from the residual olefin of isoprene and / or butadiene to the peak area derived from ethylene, propylene and / or butylene by H-NMR measurement. ..
-Device: Nuclear magnetic resonance device "ADVANCE 400 Nano bay" (manufactured by Bruker)
-Solvent: CDCl ₃

(4) Amount of vinyl bond in polymer block (B) ¹ H-NMR measurement by dissolving the block copolymer before hydrogenation in CDCl ₃ [Equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature : 30 ° C.]. The total peak area of structural units derived from isoprene and / or butadiene, and 3,4-bonding units and 1,2-bonding units in isoprene structural units, 1,2-bonding units in butadiene structural units, or isoprene and butadiene. In the case of structural units derived from the mixture, the vinyl bond amount (total content of 3,4-bonding unit and 1,2-bonding unit) was calculated from the ratio of the peak areas corresponding to each of the binding units.

(5) using 10mmNMR tube block copolymer 600mg and Cr _(acac) 3 40 mg of the content water before hydrogenation of the polymer block (B) an alicyclic skeleton (X) in was dissolved in CDCl ₃ 4 mL Quantitative ¹³ C-NMR measurement (pulse program: zgig, Inverse gated 1H decoupling method) [Equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 ° C.], and block the polymer by the following method. The contents of each of the alicyclic skeletons X, X1 and X2 in (B) were calculated.
In Table 3, X, X1 and X2 show the following alicyclic skeletons.
X: Alicyclic skeleton having a combination of the following (i) to (vi) substituents X1: Alicyclic skeleton having a combination of the following (i) and (iv) substituents X2: Below (ii), ( iii) Alicyclic skeleton with a combination of substituents (iv), (v), (iv): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Bd + Bd)
(Ii): R ¹ = hydrogen atom, R ² = methyl group, R ³ = hydrogen atom; (1,2Bd + 1,2Ip)
(Iii): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = methyl group; (1,2Bd + 3,4Ip)
(Iv): R ¹ = methyl group, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Ip + Bd)
(V): R ¹ = methyl group, R ² = methyl group, R ³ = hydrogen atom; (1,2Ip + 1,2Ip)
(Vi): R ¹ = methyl group, R ² = hydrogen atom, R ³ = methyl group; (1,2Ip + 3,4Ip)

[Calculation method]
The structure derived from each peak is shown in Table 1-1. Assuming that the integrated values of the peaks are a to g, the integrated values of each structure are as shown in Table 1-2, and the contents of X, X1 and X2 are (a + g−c) / (a + b + cd + e /, respectively). 2 + 2f), (g-c) / (a + b + cd + e / 2 + 2f), a / (a + b + cd + e / 2 + 2f).

(6) ¹³ C-NMR Peak Area Ratio For the hydrogenated products of Production Example 1 and Comparative Production Example 1, the quantitative ¹³ C-NMR measurement [Equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 ° C., solvent: CDCl ₃ ] was performed to calculate the peak area ratio [peak area of chemical shift value 50.0 to 52.0 ppm] / [peak area of chemical shift value 43.0 to 45.0 ppm].

(7) Peak top temperature of tan δ, peak top strength, maximum width of temperature region where tan δ is 1.0 or more, tan δ strength at 20 ° C and 30 ° C or less Hydrogenated block copolymer for measurement Was pressurized at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes to prepare a single-layer sheet having a thickness of 1.0 mm. The single-layer sheet was cut into a disk shape and used as a test sheet.
For the measurement, based on JIS K 7244-10 (2005), as a parallel plate vibration rheometer, a distortion control type dynamic viscoelastic device "ARES-G2" with a disk diameter of 8 mm (TA Instruments) Ment Japan Co., Ltd.) was used.
The test sheet completely fills the gap between the two flat plates, and with a strain amount of 0.1%, the test sheet is vibrated at a frequency of 1 Hz, and a constant temperature of 3 ° C./min is applied from −70 ° C. to 100 ° C. The temperature rose quickly. The temperature of the test sheet and the disk was maintained until there was no change in the measured values of shear loss elastic modulus and shear storage elastic modulus, and the maximum value (peak top intensity) of the peak intensity of tan δ and the maximum value were obtained. The temperature (peak top temperature) was determined. Further, the maximum width of the temperature region where tan δ is 1.0 or more, and the tan δ intensity at 20 ° C. and 30 ° C. were determined. The larger the value, the better the vibration damping property.

[Manufacturing Example 1]
Production of Hydrogen Additive (H-TPE-1) 87 g (sec) of sec-butyllithium cyclohexane solution containing 50 kg of cyclohexane as a solvent and 10.5% by mass of anionic polymerization initiator in a pressure-resistant container that has been replaced with nitrogen and dried. -Substantial addition amount of butyllithium: 9.1 g) was charged.
After raising the temperature inside the pressure-resistant container to 50 ° C., 1.0 kg of styrene (1) is added and polymerized for 1 hour. At the temperature inside the container at 50 ° C., 2,2-di (2-tetrahydrofuryl) propane (2-tetrahydrofuryl) propane as a Lewis base ( 63 g of DTHP) was added, and a mixture of 8.16 kg of isoprene and 6.48 kg of butadiene was added at the average diene feed rate shown in Table 2 over 5 hours and then polymerized for 2 hours, and 1.0 kg of styrene (2) was further added. In addition, it was polymerized for 1 hour to obtain a reaction solution containing a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer.
A Ziegler-based hydrogenation catalyst formed of nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the reaction was carried out under the conditions of a hydrogen pressure of 1 MPa and 80 ° C. for 5 hours. After allowing the reaction solution to cool and pressurize, the catalyst is removed by washing with water and vacuum dried to obtain a hydrogenated product of a polystyrene-poly (isoprene / butadiene) -polystyrene triblock copolymer (hereinafter, H). -Sometimes referred to as TPE-1) was obtained.
Table 2 shows each raw material and the amount used thereof. The results of the physical property evaluation are shown in Table 3.

[Manufacturing Example 2]
Production of hydrogenated additive (H-TPE-2) Block copolymer hydrogen in the same manner as in Production Example 1 except that the components, their amounts used, and the reaction conditions were changed as shown in Table 2. An additive (H-TPE-2) was produced. The results of the physical property evaluation are shown in Table 3.
[Manufacturing Example 3]
Production of hydrogenated additive (H-TPE-3) Hydrogen in block copolymer in the same manner as in Production Example 1 except that each component, the amount used thereof, and the reaction conditions were changed as shown in Table 2. An additive (H-TPE-3) was produced. The results of the physical property evaluation are shown in Table 3.
[Manufacturing Example 4]
Production of hydrogenated additive (H-TPE-4) Block copolymer hydrogen in the same manner as in Production Example 1 except that the components, their amounts used, and the reaction conditions were changed as shown in Table 2. An additive (H-TPE-4) was produced. The results of the physical property evaluation are shown in Table 3.

[Comparative Manufacturing Example 1]
Production of Hydrogenated Additive (H-TPE-1') The block copolymer was prepared in the same manner as in Production Example 1 except that the components, their amounts used, and the reaction conditions were changed as shown in Table 2. A hydrogenated product (H-TPE-1') was produced. The results of the physical property evaluation are shown in Table 3.

The hydrogenated block copolymers of Production Examples 1 to 4 have a peak top intensity of tan δ of 1.0 or more, and a peak top temperature of tan δ in a wide temperature range. Therefore, they are widely used as vibration damping materials. It can be said that it is suitable for. In particular, as compared with Comparative Production Examples 1, it can be seen that Production Examples 1 to 4 have relatively high tan δ strengths at 20 ° C. and 30 ° C., and are excellent in vibration damping properties near room temperature.

<Laminated body>
[Examples 1 to 8] [Comparative Examples 1 to 3]
(Method for producing base material layer)
The composition of the base material layer shown in Table 4 is obtained after being put into a lavender (manufactured by Brabender, "Plastograph EC 50cc mixer"), melt-kneaded at a cylinder temperature of 240 ° C. and a screw rotation speed of 100 rpm for 3 minutes. The composition was press-molded (240 ° C., 2 minutes) to prepare a sheet (thickness 1 mm) of the base material layer.

(Method of producing adhesive layer)
The composition of the adhesive layer shown in Table 4 was obtained after being put into a lavender (manufactured by Brabender, "Plastograph EC 50cc mixer"), melt-kneaded at a cylinder temperature of 180 ° C. and a screw rotation speed of 100 rpm for 3 minutes. The composition was press-molded (180 ° C. for 2 minutes) to prepare a sheet (thickness 1 mm) of an adhesive layer.

(Method of manufacturing laminate)
Pellets containing the base material layer shown in Table 4 are used in the hopper of the single-screw extruder "GM30" (manufactured by GM Engineering), and pellets containing the adhesive layer shown in Table 4 are used in the single-screw extruder "GM25" (manufactured by GM Engineering). ), And co-extruded using a multi-manifold die as a T-die at an extrusion temperature of 220 ° C. to obtain a laminate having a thickness of 50 μm (base material layer thickness: 35 μm, adhesive layer thickness: 15 μm). ..

[Evaluation of the physical properties]
The method for evaluating the physical properties of the prepared base material layer, adhesive layer and laminated body is shown below.
(Shore A hardness)
Six sheets of the obtained base material layer and six sheets of the adhesive layer were laminated to form a test piece for hardness measurement having a thickness of 6 mm, and an automatic rubber hardness tester P2-A type (high) according to JIS K 6253 (2012). The shore A hardness i of the base material layer and the shore A hardness i of the adhesive layer were measured using a molecular meter). The results are shown in Table 4.

(Storage modulus, tan δ strength (tensile, 10 Hz))
Measurements were made according to JIS K 7244-4 (1999). Specifically, a sheet of the obtained base material layer and adhesive layer cut out to a length of 70 mm, a width of 5 mm, and a thickness of 1 mm was used as a sample, and "DMA242E" (manufactured by NETZSCH) was used under the condition of a frequency of 10 Hz. By measuring by raising the temperature from −70 ° C. to 200 ° C. at 3 ° C./min, the tensile storage elastic modulus (E') of the adhesive layer at 23,60 ° C. and 23,40,60 of the base material layer and the adhesive layer The tan δ intensity at ° C was measured. The results are shown in Table 4.

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

(Peeling strength, adhesive residue (23 ° C))
Attached to an acrylic extruded plate (trade name: Sumipex E, thickness 1.5 mm, manufactured by Sumika Acrylic Sales Co., Ltd.) so that the adhesive layer of the obtained laminate is in contact with the acrylic resin plate, and cut to a width of 25 mm. Was used as a test piece. After rolling back and forth twice at a speed of 10 mm / min using a 2 kg rubber roller from the base material layer side of this test piece, it was left to stand for 24 hours in an atmosphere of 23 ± 1 ° C. and a humidity of 50 ± 5%. Then, 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. The peel strength was set to 23 ° C. In addition, it was visually confirmed whether or not there was adhesive residue on the adherend after peeling. The results are shown in Table 4.

(Peeling strength, adhesive residue (60 ° C))
After leaving for 24 hours in an atmosphere of 23 ± 1 ° C. and humidity of 50 ± 5%, leaving for 10 minutes in an atmosphere of 60 ° C., and then measuring the peel strength in an atmosphere of 60 ° C., the above (peeling strength, adhesive residue (peeling strength, adhesive residue) 23 ° C.)), the peel strength and the adhesive residue (60 ° C.) were set. The results are shown in Table 4.

Each component shown in Table 4 is as follows.
-Olefin resin: Homopolypropylene (Novatec PP, manufactured by Japan Polypropylene Corporation)
-Adhesion-imparting resin: Archon P-125 (alicyclic saturated hydrocarbon resin, softening point (ring ball method) 125 ± 5 ° C, manufactured by Arakawa Chemical Industries, Ltd.)

From Table 4, in Examples 1, 2 and 4 to 8 in which the base material layer contains a hydrogenated block copolymer, the value of the tan δ strength of the base material layer is large in the temperature range of 23 to 60 ° C., and the adhesive layer has a large value. In Examples 1 and 3 to 8 containing the hydrogenated block copolymer, the value of the tan δ strength of the adhesive layer is large in the temperature range of 23 to 60 ° C.
Further, in Examples 1 and 3 to 8, the ratio [E'(23 ° C.) / E'(60 ° C.)] of the storage elastic modulus E'of the adhesive layer is higher than that of the laminated body of Comparative Examples 1 to 3. Large, 2 or more. As described above, in the laminates of Examples 1 and 3 to 8, the ratio of the storage elastic modulus of 23 ° C. and 60 ° C. was larger than that of the comparative example, and the decrease in peel strength from 23 ° C. to 60 ° C. was small [ (Peeling strength at 60 ° C) / (Peeling strength at 23 ° C) is large]. Although the structure of the adhesive layer is the same in Example 2 and Comparative Examples 1 to 3, the decrease in peel strength from 23 ° C. to 60 ° C. in Example 2 is smaller than that in the laminate of Comparative Examples 1 to 3. .. In Example 2, as one of the factors that the decrease in peel strength was smaller than that in Comparative Examples 1 to 3, the base material layer was imparted with appropriate flexibility by containing a hydrogenated block copolymer. Can be mentioned.
Further, the laminates of Examples 1 to 8 have no adhesive residue even at 60 ° C.
Therefore, the laminate of the example contains a block copolymer having a structural unit containing an alicyclic skeleton (X) in the main chain or a hydrogenated product thereof in one or both of the base material layer and the adhesive layer. Therefore, it is expected that excellent vibration damping properties can be imparted to the adherend, and it can be seen that even under high temperature conditions, it is difficult to peel off and adhesive residue is extremely unlikely to occur.

Although it is not certain, from the ratio of the peel strengths of Examples 1 and 3 to 8, the adhesive layer containing the block copolymer or its hydrogenated material is softened at a high temperature (60 ° C.) to be adhered. It penetrated into the minute irregularities on the surface of the material (acrylic resin plate) and acted like an anchor, or the convex parts of the minute irregularities on the surface of the adhesive layer bite into the concave parts of the adherend and an elastic tightening force acted. Therefore, it is presumed that the decrease in the adhesive strength between the adhesive layer and the adherend was suppressed. Further, even if the structure of the adhesive layer is the same, the peel strength ratio differs depending on the structure of the base material layer, and it is considered that this is influenced by the flexibility of the base material layer.
Further, the laminates of Examples 1, 2 and 4 to 8 have lower HAZE and higher transparency than the laminates of Example 3 and Comparative Examples 1 to 3. It is considered that this is because the block copolymer or its hydrogenated additive, which is a constituent component of the base material layers of Examples 1, 2 and 4 to 8, is highly compatible with polypropylene.
Therefore, the laminates of Examples 1, 2 and 4 to 8 in this embodiment are useful as surface protective films for applications requiring transparency, for example, liquid crystal displays.

The laminate of the present invention can impart vibration damping properties to the adherend, and is unlikely to be peeled off and leave adhesive residue even at high temperatures. Therefore, adhesives such as adhesive tapes and adhesive sheets, and surfaces of electronic devices and the like It is useful as a protective film, a surface protective film that prevents stains and scratches on the target product during transportation, storage, and processing.

Claims

A laminate having a base material layer and an adhesive layer,
The ratio [i / ii] of the shore A hardness i of the base material layer to the shore A hardness i of the adhesive layer is 1.1 or more.
A laminate in which at least one of the base material layer and the adhesive layer contains the following block copolymer or a hydrogenated product thereof.
The block copolymer contains a polymer block (A) and a polymer block (B), and the polymer block (B) is a structural unit derived from a conjugated diene compound and has the following formula (X). It has a structural unit containing one or more alicyclic skeletons (X) represented by (X) in the main chain.

(In the above formula (X), R 1 to R 3 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 the content of the block copolymer or its hydrogenated product is 1 to 100% by mass in the base material layer.
The first or second claim, 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. Laminated body.
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 tackifier resin in the base material layer is less than 1% by mass.
The laminate according to any one of claims 1 to 5, wherein the content of the block copolymer or its hydrogenated product in the adhesive layer is 1 to 80% by mass.
The laminate according to any one of claims 1 to 6, wherein the pressure-sensitive adhesive has a content of 1% by mass or more in the pressure-sensitive adhesive layer.
The alicyclic skeleton (X) includes the alicyclic skeleton (X') in which at least one of R 1 to R 3 is a hydrocarbon group having 1 to 11 carbon atoms, according to claims 1 to 7. The laminate according to any one.
The laminate according to 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 a hydrogenated additive of the block copolymer.
The laminate according to any one of claims 1 to 7, wherein R 1 to R 3 are hydrogen atoms at the same time.
The laminate according to 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 according to claim 8 or 9, wherein the polymer block (B) contains 1 mol% or more of the alicyclic skeleton (X').
The laminate according to any one of claims 1 to 13, wherein the hydrogenation rate of the 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 polymer block (B) has a hydrogenation rate of 50 to 99 mol%.
The laminate according to any one of claims 1 to 15, wherein the amount of vinyl bond in the polymer block (B) is 55 to 95 mol%.
The block copolymer or its hydrogenated product conforms to JIS K 7244-10 (2005), has a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of −70 to 100 ° C., and a temperature rise rate of 3 ° C./ The laminate according to any one of claims 1 to 16, wherein there is a series of temperature regions in which tan δ measured under the condition of minutes is 1.0 or more, and the maximum width of the temperature region is 13 ° C. or more.
The laminate according to any one of claims 1 to 17, wherein the polymer block (A) contains more than 70 mol% of structural units derived from an aromatic vinyl compound.
The laminate according to 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 ratio [E'(23 ° C.) / E'(60 ° C.)] of the storage elastic modulus E'(23 ° C.) at 23 ° C. to the storage elastic modulus E'(60 ° C.) at 60 ° C. of the adhesive layer is 2. The laminate according to any one of claims 1 to 20, which is the above.