JP7364671B2 - laminate - Google Patents

Description

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

Some block copolymers and their hydrogenated products, which have 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, have vibration damping properties. It is already known that some materials have this property, and have been used as vibration damping materials. In addition, the block copolymers and their hydrogenated products have various physical properties such as sound insulation, heat resistance, impact resistance, and adhesive properties in addition to vibration damping properties. It is conceivable that it can be used for various purposes.
For example, in order to improve mechanical properties such as vibration damping, flexibility, heat resistance, tensile strength, and impact resistance, we use styrene-based compounds, isoprene, butadiene, etc. whose tan δ peak temperature and vinyl bond content have been specified. Hydrogenated block copolymers with conjugated diene compounds have been disclosed (see, for example, Patent Documents 1 to 4).

On the other hand, a surface protection film, for example, is known as a laminate including a base material layer and a layer having adhesive strength (adhesive layer). It is known to form an adhesive layer in a surface protection film using an adhesive composition containing a styrene elastomer and a tackifier resin (see, for example, Patent Documents 5 and 6).

JP2002-284830A International Publication No. 2000/015680 Japanese Patent Application Publication No. 2006-117879 Japanese Patent Application Publication No. 2010-053319 Japanese Patent Application Publication No. 5-194923 Japanese Patent Application Publication No. 2010-126711

The above-mentioned block copolymers and their hydrogenated products can have physical properties such as adhesive properties in addition to vibration damping properties, so they are required for laminates that exhibit vibration damping properties and have adhesive properties. Laminated bodies that have both physical properties are being studied.
Although improvements have been made to further improve the vibration damping properties, it has been difficult to further improve various physical properties such as vibration damping properties and adhesive properties in a well-balanced manner. Physical properties required of a laminate having adhesive properties include, in addition to adhesive strength, suppression of adhesive residue (a phenomenon in which a portion of the adhesive layer remains on an adherend). Furthermore, some adherends that use laminates such as surface protection films get hot during use, such as electrical appliances, and adherends that are installed outdoors or used outdoors. When the temperature rises, the adhesion holding power of the adhesive layer decreases, and the laminate may easily peel off. There is a need for adhesive strength that can withstand such temperature changes in the adherend and the environment in which it is used.

Accordingly, the present invention provides a laminate that includes an adhesive layer and a base material layer that can impart vibration damping properties to an adherend and that is resistant to peeling off and resistant to adhesive residue even at high temperatures.

As a result of intensive studies to solve the above problems, the present inventors came up with the following invention and found that the problems could 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 ii of the adhesive layer is 1.1 or more,
A laminate in which at least one layer among the base 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 the following in its main chain.

（上記式（Ｘ）中、Ｒ^１～Ｒ^３は、それぞれ独立に水素原子又は炭素数１～１１の炭化水素基を示し、複数あるＲ^１～Ｒ^３はそれぞれ同一でも異なってもよい。）

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

According to the present invention, it is possible to provide a laminate including an adhesive layer and a base material layer that can impart vibration damping properties to an adherend and that are difficult to peel off and do not easily leave adhesive residue even at high temperatures.

The laminate of the present invention is 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 ii of the adhesive layer is 1.1 or more,
It is characterized in that at least one layer among the base material layer and the adhesive layer contains the following block copolymer or its hydrogenated product.
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 formula (X). It has a structural unit containing one or more alicyclic skeletons (X) represented by the following in its main chain.
The base material layer and adhesive layer, as well as the block copolymer and its hydrogenated product contained in the laminate will be explained below.

≪Block copolymers and their hydrogenated products≫
In an embodiment of the present invention (hereinafter sometimes referred to as "this embodiment"), the block copolymer or its hydrogenated product is contained in at least one of the base layer and the adhesive layer. good. By containing a block copolymer or its hydrogenated product, vibration damping properties and adhesive properties can be imparted to the laminate. 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 properties and mechanical properties.
The polymer block (A) contains more than 70 mol% of structural units derived from aromatic vinyl compounds (hereinafter sometimes abbreviated as "aromatic vinyl compound units"). From the viewpoint of mechanical properties, it is more preferably 80 mol% or more, still more preferably 90 mol% or more, even more preferably 95 mol% or more, and particularly preferably substantially 100 mol%. .

Examples of the aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α -Methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p- Methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2 , 4-dimethylstyrene, 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 include styrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with silyl groups, indene, vinylnaphthalene, and N-vinylcarbazole. These aromatic vinyl compounds may be used alone or in combination of two or more. Among these, from the viewpoint of production cost and physical property balance, styrene, α-methylstyrene, p-methylstyrene, and mixtures thereof are preferred, and styrene is more preferred.

Unless it interferes with the purpose and effects of the present invention, the polymer block (A) may be a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter referred to as "other unsaturated monomer unit"). ) may be contained in the polymer block (A), preferably 30 mol% or less, more preferably less than 20 mol%, even more preferably less than 15 mol%, even more preferably It is less than 10 mol%, even more preferably less than 5 mol%, particularly preferably 0 mol%.
Examples of the other unsaturated monomers 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-menthene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, and the like. When the polymer block (A) contains the other unsaturated monomer units, the bonding form is not particularly limited and may be either random or tapered.

The block copolymer only needs to have at least one of the polymer blocks (A). When the block copolymer has two or more polymer blocks (A), these polymer blocks (A) may be the same or different. In addition, in this specification, "the polymer blocks are different" refers to the monomer units constituting the polymer blocks, the weight average molecular weight, the stereoregularity, and when the polymer blocks have multiple monomer units, the ratio and co-existence of each monomer unit. It means that at least one of the polymerization forms (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) included 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, mechanical strength is further improved and moldability is also excellent.
Note that the weight average molecular weight is a weight average molecular weight in terms of standard polystyrene determined 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, even more preferably 16% by mass or less, and 14% by mass or less. % or less is particularly preferable. When the content is 50% by mass or less, a block copolymer or a hydrogenated product thereof can be obtained which has appropriate flexibility and excellent vibration damping properties without reducing the tan δ peak top strength. Further, the lower limit is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 6% by mass or more. If the amount is 1% by mass or more, the block copolymer or its hydrogenated product can have mechanical properties and moldability suitable for various uses in laminates.
The content of the polymer block (A) in the block copolymer is a value determined by ¹ H-NMR measurement, and more specifically, a value determined 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) in its main chain. (hereinafter sometimes abbreviated as "alicyclic skeleton-containing unit"). Moreover, 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 sometimes abbreviated as "conjugated diene unit").
The total amount of alicyclic skeleton-containing units and conjugated diene units in the polymer block (B) is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably is 90 mol% or more, and particularly preferably substantially 100 mol%.
When the block copolymer has two or more polymer blocks (B), these polymer blocks (B) may be the same or different.

In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different. The hydrocarbon group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably 1 (ie, methyl group). Moreover, the above-mentioned hydrocarbon group may be a straight chain or branched chain, and may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and alicyclic skeleton (X) formation, it is particularly preferable that R ¹ to R ³ are each independently a hydrogen atom or a methyl group.
Note that when the block copolymer is hydrogenated, the vinyl group in the above formula (X) may be hydrogenated. Therefore, the meaning of the alicyclic skeleton (X) in the hydrogenated product also includes a skeleton in which the vinyl group in the above formula (X) is hydrogenated.

The polymer block (B) is a structural unit derived from a conjugated diene compound, and the alicyclic skeleton (X) is derived from the conjugated diene compound. The alicyclic skeleton (X) is produced by anionic polymerization of a conjugated diene compound by the method described below. 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 becomes smaller, the glass transition temperature increases, and the tan δ at around room temperature decreases. The peak top strength is improved, and excellent vibration damping properties can be exhibited.

The above conjugated diene compounds include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene. , 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octatriene, farnesene, myrcene and chloroprene. . Among these, butadiene, isoprene, or a combination of butadiene and isoprene is preferred.

When butadiene and isoprene are used together, there is no particular restriction on their blending ratio [isoprene/butadiene] (mass ratio), but preferably 5/95 to 95/5, more preferably 10/90 to 90/10, More preferably 40/60 to 70/30, particularly preferably 45/55 to 65/35. In addition, when the mixing ratio [isoprene/butadiene] is expressed as a 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, especially Preferably it is 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 explained.
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 a preferred embodiment of the block copolymer or its hydrogenated product, the polymer block (B) has one type of alicyclic skeleton (X) in which R ¹ to R ³ are hydrogen atoms in the main chain. Examples include those having a structural unit containing the following.

Furthermore, when isoprene is used alone as the conjugated diene compound, two types of alicyclic skeletons (X) having the following combinations of substituents (v) and (vi) are mainly produced.
Furthermore, when butadiene and isoprene are used together as a conjugated diene compound, six types of alicyclic skeletons (X) having the following combinations of 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 atom, 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) has a substituent that is a hydrocarbon group, thereby reducing molecular motion and further improving vibration damping properties. (X) is preferably an alicyclic skeleton (X') in which at least one of the above R ¹ to R ³ is a hydrocarbon group having 1 to 11 carbon atoms. Among them, the hydrocarbon group in the alicyclic skeleton (X') is a methyl group, since it is possible to efficiently generate an alicyclic skeleton from a conjugated diene compound, and from the viewpoint of a balance between vibration damping properties and mechanical properties. It 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 that R ¹ to R ³ are also an alicyclic skeleton that is not a hydrogen atom. That is, it is more preferable that the polymer block (B) has a structural unit whose main chain includes any one or more of the alicyclic skeletons having a combination of substituents (ii) to (vi) above. .

(Amount of vinyl bonds in polymer block (B))
When the structural units constituting the polymer block (B) are isoprene units, butadiene units, or mixture units of isoprene and butadiene, isoprene and butadiene in a bond form other than that forming the alicyclic skeleton (X) are used. The respective bond forms are 1,2-bonds and 1,4-bonds in the case of butadiene, and 1,2-bonds, 3,4-bonds, and 1,4-bonds in the case of isoprene. I can do it.

In block copolymers and their hydrogenated products, the content of 3,4-bond units and 1,2-bond units in the polymer block (B) (hereinafter sometimes simply referred to as "vinyl bond amount") ) is preferably 55 to 95 mol%, more preferably 63 to 95 mol%, even more preferably 70 to 95 mol%. In the above range, excellent vibration damping properties can be exhibited.
Here, the vinyl bond amount is a value calculated by ¹ H-NMR measurement according to the method described in Examples.
In addition, when the polymer block (B) consists only of butadiene, the above-mentioned "content of 3,4-bond units and 1,2-bond units" refers to "content of 1,2-bond units". It should be read and applied as follows.

(Alicyclic skeleton (X) content)
It is sufficient that the polymer block (B) contains a structural unit containing an alicyclic skeleton (X) in its main chain, but it exhibits a superior vibration damping effect and maintains adhesive strength even at high temperatures. From the viewpoint of easily suppressing the decrease in , it is preferable that the polymer block (B) contains the alicyclic skeleton (X) in an amount of 1 mol % or more, more preferably 1.1 mol % or more, and still more preferably is 1.4 mol% or more, even more preferably 1.8 mol% or more, even more preferably 4 mol% or more, even more preferably 10 mol% or more, particularly preferably 13 mol% or more. It is. Further, 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, it is 40 mol. % or less, and may be 30 mol% or less, 20 mol% or less, or 18 mol% or less.
Furthermore, from the viewpoint of improving vibration damping properties, it is more preferable that the alicyclic skeleton (X') is contained in the polymer block (B) in an amount of 1 mol% or more, and even more preferably 1.3 mol% or more. , and even 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 using isoprene as the conjugated diene compound, when using butadiene, or when using butadiene and isoprene together, the alicyclic skeleton content in each case is as follows.
When isoprene is used as a conjugated diene compound, when one or more alicyclic skeletons (X') having a combination of the substituents (v) and (vi) above are present in the polymer block (B). The total content of these is preferably 1.5 mol% or more from the viewpoint of achieving better vibration damping effects and easily suppressing the decrease in adhesive strength even at high temperatures. The content is more preferably 2 mol% or more, even more preferably 3 mol% or more, and even more preferably 4 mol% or more from the viewpoint of obtaining excellent vibration damping effects in a wide temperature range. It is particularly preferable that Further, when isoprene is used, the upper limit of the total content is the same as the upper limit of the content of the alicyclic skeleton (X).

When butadiene is used as the conjugated diene compound, when the alicyclic skeleton (X) is present in the polymer block (B), the content thereof is 5 mol% or more for better vibration damping. The content is preferably 10 mol% or more, even more preferably 15 mol% or more, and 20 mol% or more. It is even more preferable that the amount is 25 mol% or more, even more preferably that it is 30 mol% or more. Moreover, the upper limit of the content in the case of using butadiene is the same as the upper limit of the content of the alicyclic skeleton (X).

When butadiene and isoprene are used together as a conjugated diene compound, an alicyclic skeleton having a combination of substituents (ii), (iii), (v), and (vi) in the polymer block (B). When one or more types of (X') are present, their total content should be 1 mol% or more to achieve better vibration damping effects and to suppress the decline in adhesive strength even at high temperatures. It is preferable from the viewpoint of making it easier, more preferably 2 mol% or more, even more preferably 5 mol% or more, even more preferably 8 mol% or more, even more preferably 13 mol% or more. preferable. The upper limit of the total content when butadiene and isoprene are used together is the same as the upper limit of the content of the alicyclic skeleton (X).
In addition, when butadiene and isoprene are used together as the conjugated diene compound, one type of alicyclic skeleton (X) having a combination of the substituents (i) to (vi) above is present in the polymer block (B). When more than 5% of these are present, the total content thereof is preferably 1 mol% or more from the viewpoint of achieving better vibration damping effects and easily suppressing the decrease in adhesive strength even at high temperatures. More preferably, it is mol% or more. The upper limit of the total content when butadiene and isoprene are used together 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 is determined by ¹³ C-NMR measurement of the block copolymer. It is a value determined from the integral value derived from the alicyclic skeleton (X) in B), and more specifically, it is a value measured according to the method described in Examples.

In addition, when the hydrogenation rate of the block copolymer or its hydrogenated product is 0 mol% or more and less than 50 mol% of the polymer block (B), the vinyl group bonded to the alicyclic skeleton (X) and the main chain The molar ratio of the vinyl groups bonded to the vinyl group can be specified.
For example, in an alicyclic skeleton (X') having a combination of substituents (ii), (iii), (v), and (vi), the vinyl group bonded to the alicyclic skeleton (X') The chemical shift in ^13C -NMR of the carbon atom ((a) in the chemical formula below) appears around 107 to 110 ppm, and the chemical shift in the 13C-NMR of the carbon atom at the end of the vinyl group bonded to the main chain ((b) in the chemical formula below) appears at around ¹⁰⁷ to 110 ppm. -The chemical shift in NMR appears around 110 to 116 ppm. When the hydrogenation rate is 0 to 40 mol%, the peak area ratio measured by ¹³ C-NMR [peak area with chemical shift value 107 to 110 ppm]/[peak area with chemical shift value 110 to 116 ppm] is usually The area ratio is preferably in the range of 0.01 to 3.00, and from the viewpoint of achieving better vibration damping properties, the area ratio is preferably 0.01 to 1.50, more preferably 0.01 to 1.00, and even more preferably is from 0.01 to 0.50, more preferably from 0.01 to 0.20.

Regarding hydrogenated products, in ¹³ C-NMR measurements, almost no peaks derived from carbon atoms on the alicyclic skeleton (X) are observed, but when the substituent R ³ is a hydrocarbon group having 1 to 11 carbon atoms, A peak derived from the carbon atom on the alicyclic skeleton (X) bonded to the branched alkyl group derived from the vinyl group having R ³ can be observed.
As a result, when the hydrogenation rate of the polymer block (B) is 50 to 99 mol% for the hydrogenated product, the alicyclic skeleton (X) bonded to the branched alkyl group derived from the vinyl group having R ³ is It is also possible to specify the molar ratio of carbon atoms on the main chain bonded to the branched alkyl group derived from the vinyl group.

For example, in an alicyclic skeleton (X) having a combination of substituents (iii) and (vi) above, the carbon atom on the alicyclic skeleton (X) bonded to the isoprene group ((c) in the following chemical formula) The chemical shift in ¹³ C-NMR appears around 50.0 to 52.0 ppm, and the chemical shift in ¹³ C-NMR of the carbon atom on the main chain bonded to the isoprene group ((d) in the chemical formula below) is It appears around 43.0 to 45.0 ppm. When the hydrogenation rate is 40 to 99 mol%, the peak area ratio measured by ¹³ C-NMR [peak area with chemical shift value 50.0 to 52.0 ppm]/[chemical shift value 43.0 to 45 .0 ppm peak area] is usually in the range of 0.01 to 3.00, and from the viewpoint of achieving better vibration damping properties, the area ratio is preferably in the range of 0.01 to 1.50, more preferably The range is from 0.01 to 1.00, more preferably from 0.01 to 0.50, even more preferably from 0.01 to 0.25.
Note that 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) included in the block copolymer is preferably 15,000 in the state before hydrogenation from the viewpoint of vibration damping properties and moldability when forming a laminate. ~800,000, more preferably 50,000~700,000, still more preferably 70,000~600,000, particularly preferably 90,000~500,000, most preferably 130,000~450 ,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 purpose and effects of the present invention. In this case, in the polymer block (B), the content of structural units derived from polymerizable monomers other than the conjugated diene compound is preferably less than 50 mol%, more preferably less than 30 mol%, and Preferably it is less than 20 mol%, even more preferably less than 10 mol%, particularly preferably 0 mol%.
Examples of the other polymerizable monomers include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, N - Aromatic vinyl compounds such as vinylcarbazole, vinylnaphthalene and vinylanthracene, as well as methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-p-menthene, dipentene, methylenenorbornene, 2-methylenetetrahydrofuran, 1,3- Preferred examples include at least one compound selected from the group consisting of cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, and the like.
The block copolymer should just have at least one of the above polymer blocks (B). When the block copolymer has two or more polymer blocks (B), these 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 the main chain can be produced by polymerizing one or more conjugated diene compounds as monomers by an anionic polymerization method. A block copolymer is obtained by forming (B), adding the monomer of the polymer block (A), and, if necessary, sequentially adding the monomer of the polymer block (A) and a conjugated diene compound. be able to.
A known technique can be used to generate the alicyclic skeleton by the anionic polymerization method (see, for example, US Pat. No. 3,966,691). An alicyclic skeleton is formed at the end of the polymer due to monomer depletion, and by sequentially adding further monomers to this, polymerization can be restarted from the alicyclic skeleton. Therefore, whether or not the alicyclic skeleton is produced and its content can be adjusted by controlling the sequential addition time of monomers, the polymerization temperature, the type and amount of catalyst added, the combination of monomer and 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 organolithium compounds that can be used as polymerization initiators for anionic polymerization in the above method include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, and the like. Further, examples of dilithium compounds that can be used as a polymerization initiator include naphthalene dilithium, dilithiohexylbenzene, and the like.
Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, and phenyl benzoate.
The amounts of these polymerization initiators and coupling agents to be used are appropriately determined depending on 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 used in an amount of 0.01 to 0.2 parts by mass per 100 parts by mass of the total monomers such as the monomers and conjugated diene compounds of the polymer block (A) used for polymerization. When a coupling agent is used, it is preferably used in a proportion of 0.001 to 0.8 parts by mass per 100 parts by mass of the monomers.

There are no particular restrictions on the solvent as long as it does not adversely affect the anionic polymerization reaction, and examples include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; aromatic hydrocarbons such as benzene, toluene, and xylene. etc. Further, 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.

In addition, by adding a Lewis base as a cocatalyst during the polymerization of a conjugated diene compound, the content of the alicyclic skeleton (X), 3,4-bonds and 1,2 - The content of bonds can be increased.
Examples of Lewis bases that can be used include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and 2,2-di(2-tetrahydrofuryl)propane (DTHFP); ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, Glycol ethers such as tetraethylene glycol dimethyl ether; amines such as triethylamine, N,N,N',N'-tetramethylenediamine, N,N,N',N'-tetramethylethylenediamine (TMEDA), N-methylmorpholine, etc. sodium or potassium salts of aliphatic alcohols such as sodium t-butyrate, sodium t-amylate or sodium isopentylate, or sodium or potassium salts of aliphatic alcohols such as dialkyl sodium cyclohexanolate, e.g. sodium mentolate; Examples include metal salts such as potassium salts. These Lewis bases can be used alone or in combination of two or more.

The amount of Lewis base added depends on how much the content of the alicyclic skeleton (X) is controlled, and whether the polymer block (B) contains a structural unit derived from isoprene and/or butadiene. In this case, it is determined by how much the amount of vinyl bonds in the isoprene units and/or butadiene units constituting the polymer block (B) is controlled. Therefore, there is no strict limit to the amount of Lewis base added, but it is usually 0.1 to 1,000 mol per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as a polymerization initiator. It is preferable to use the amount within the range of 1 to 100 mol.

The average feed rate of the conjugated diene compound (hereinafter sometimes referred to as "average diene feed rate") is 150 kg/h or less per mole of 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 even more preferable, may be 45 kg/h or less, may be 30 kg/h or less, or may be 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, even more preferably 5 kg/h or more, and may be 7 kg/h or more, per mole of active terminal. It may be 10 kg/h or more, or it may be 15 kg/h or more.

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

(Hydrogen additive)
When the block copolymer obtained by the above production method is used as a hydrogenated product, a hydrogenation reaction (hydrogenation reaction) is performed in an inert organic solvent in the presence of a hydrogenation catalyst. 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 a hydrogenated product of the block copolymer can be obtained.
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 The reaction can be carried out at a temperature of 70 to 180°C and a reaction time of usually about 0.1 to 100 hours, preferably 1 to 50 hours.
Hydrogenation catalysts include, for example, Raney nickel; heterogeneous catalysts in which metals such as Pt, Pd, Ru, Rh, and Ni are supported on carbon, alumina, diatomaceous earth, etc.; transition metal compounds, alkyl aluminum compounds, and alkyl lithium compounds. Examples include Ziegler catalysts in combination with compounds; metallocene catalysts, and the like.

The hydrogenated product thus obtained can be solidified by pouring the polymerization reaction solution into methanol, etc., and then drying by heating or under reduced pressure, or by pouring the polymerization reaction solution into hot water with steam to remove the solvent by azeotropic distillation. It can be obtained by performing so-called steam stripping, which removes it by heating, or drying under reduced pressure.

Whether the above block copolymer or hydrogenated material is used can be determined depending on the performance desired in various uses of the laminate. Similarly, the degree of hydrogenation of the carbon-carbon double bonds in the polymer block (B) when used as a hydrogenated product depends on the performance desired in various uses of the laminate. can be specified.
For example, the higher the hydrogenation rate of the hydrogenated product, the higher the heat resistance and weather resistance of the hydrogenated product. 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, or 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 unhydrogenated cases) or less than 50 mol%, Further, a hydrogenated product having a hydrogenation rate of 50 to 99 mol% of the polymer block (B) may be used.
The above hydrogenation rate refers to the content of carbon-carbon double bonds in the structural units derived from the conjugated diene compound and the alicyclic skeleton (X) in the polymer block (B) to ¹ H after hydrogenation. - This is a value determined by NMR measurement, more specifically a value measured according to the method described in Examples.

(Bonding mode of polymer block (A) and polymer block (B))
The block copolymer is not limited in the form of bonding as long as the polymer block (A) and the polymer block (B) are bonded, and may be linear, branched, radial, or two of these. Any combination of the above combinations may be used. Among these, it is preferable that the bonding form between the polymer block (A) and the polymer block (B) is linear, and examples thereof include A for the polymer block (A) and A for the polymer block (B). When represented by B, diblock copolymer shown by AB, triblock copolymer shown by ABA or BAB, tetrablock copolymer shown by ABAB Block copolymer, pentablock copolymer represented by A-B-A-B-A or B-A-B-A-B, (A-B)nZ type copolymer (Z is the coupling agent residue) group, and n represents an integer of 3 or more). Among these, linear triblock copolymers or diblock copolymers are preferred, and ABA type triblock copolymers are preferably used from the viewpoint of flexibility, ease of production, and the like.
A specific example of the ABA type triblock copolymer is a styrene-butadiene/isoprene-styrene copolymer. Among these, at least one of the base layer and the adhesive layer preferably contains at least a styrene-hydrogenated butadiene/isoprene-styrene copolymer as a hydrogenated block copolymer.

Here, in this specification, when polymer blocks of the same type are linearly bonded via a bifunctional coupling agent, the entire bonded polymer block is treated as one polymer block. It will be done. Accordingly, including the above example, the polymer block that should originally be strictly written as Y-Z-Y (Z represents a coupling residue) needs to be particularly distinguished from a single polymer block Y. Except in certain cases, Y is displayed as a whole. In this specification, this type of polymer block containing a coupling agent residue is treated as described above, so, for example, a polymer block containing a coupling agent residue and strictly speaking A-B-Z-B-A ( A block copolymer to be written as ABA (Z represents a coupling agent residue) is treated as an example of a triblock copolymer.

(Content 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 purpose and effects 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. It is particularly preferable that If it is 90% by mass or more, the block copolymer or its hydrogenated product has excellent vibration damping properties and moldability, and can easily suppress a decrease in adhesive strength even at high temperatures, and can be suitably used for laminates. can do.

(Weight average molecular weight)
The weight average molecular weight (Mw) of the block copolymer and its hydrogenated product determined by gel permeation chromatography in terms of standard polystyrene 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, most preferably 130,000 to 450,000. If the weight average molecular weight of the block copolymer and its hydrogenated product is 15,000 or more, heat resistance will be high, and if it is 800,000 or less, moldability and processability will be good.

[tanδ]
(Tanδ peak top temperature and intensity)
Tan δ (loss tangent) is the ratio of loss modulus/storage modulus at a frequency of 1 Hz in dynamic viscoelastic measurement, and the peak top temperature and intensity of tan δ greatly contribute to damping properties 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 at its maximum. Further, the peak top temperature of tan δ is the temperature at which the peak of tan δ is at its maximum.

In this specification, the peak top temperature and intensity of tan δ of the block copolymer or its hydrogenated product are determined by pressurizing the block copolymer or its hydrogenated product at a temperature of 230° C. and a pressure of 10 MPa for 3 minutes to obtain a thickness of 1 A single-layer sheet with a thickness of 0.0 mm is prepared, the single-layer sheet is cut into a disk shape, and this is used as a test piece for measurement. The measurement conditions were a strain amount of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 100°C, and a temperature increase rate of 3°C/min in accordance with JIS K 7244-10 (2005).
In addition, the peak top temperature and tan δ intensity of the block copolymer or its hydrogenated product are values measured in more detail according to the method described in the 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 values are 1.5 or higher, and even 1.9 or higher. The higher the peak top intensity of tan δ, the better the physical properties such as vibration damping properties at that temperature, and if it is 1.0 or more, sufficient vibration damping properties can be obtained in the actual use environment.
In addition, the block copolymer or its hydrogenated product has a tan δ peak top temperature of preferably -50°C or higher, more preferably -40°C or higher, still more preferably -30°C or higher, even more preferably -25°C. or more, and may be 0°C or more. Further, the upper limit of the peak top temperature of tan δ may be within a range that does not impair the effects of the present invention, and may be 50°C or lower, 40°C or lower, or 35°C or lower. 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, even more preferably -25 to 25°C. . If the peak top temperature of tan δ is -50°C or higher, sufficient vibration damping properties can be obtained in the actual usage environment, and if it is 50°C or lower, desirable adhesiveness can be achieved when used in an adhesive layer. can do.

(Maximum width of temperature range where tan δ is 1.0 or more)
In addition, the block copolymer or its hydrogenated product has a series of temperature ranges in which tan δ is 1.0 or more at -70 to 100°C measured under the above measurement conditions, and the maximum width of the temperature range is preferably The temperature is 12°C or higher, more preferably 13°C or higher, even more preferably 15°C or higher, even more preferably 17°C or higher.
As mentioned above, the alicyclic skeleton (X) is incorporated into the main chain in the structural unit of the polymer block (B), and it can have a higher amount of vinyl bonds, which reduces molecular movement and makes glass The transition temperature increases, and the glass transition becomes gentler with respect to temperature changes. This widens the temperature range in which the block copolymer or its hydrogenated product exhibits tan δ of 1 or more, making it possible to exhibit damping properties over a wide temperature range. If the maximum width of the temperature range in which tan δ is 1.0 or more is 12° C. or more, more preferably 13° C. or more, better vibration damping properties can be obtained in the actual usage environment. Further, there is no particular upper limit for the maximum width of the temperature range, but for example, from the viewpoint of productivity, the upper limit may be 35°C, 30°C, or 25°C. Good too.

≪Base material layer≫
The base material layer can contain the above-mentioned block copolymer or its hydrogenated product from the viewpoint of being suitable for further improving the vibration damping properties of the adherend.
The content of the block copolymer or its hydrogenated product in the base layer is preferably 1 to 100% by mass. From the viewpoint of further improving the vibration damping properties of the adherend, the content of the block copolymer or its hydrogenated substance in the base material layer is more preferably 3% by mass or more, still more preferably 5% by mass or more, and more preferably More preferably, it is 10% by mass or more. The upper limit of the content is not particularly limited as long as it does not impair the effects of the present invention, but while maintaining the strength of the laminate, it can be used as a material for the base layer described below From the viewpoint of good compatibility, more preferably 90% by mass or less, still more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass. The content is more preferably 40% by mass or less, and may be 30% by mass or less, or 25% by mass or less.

[Non-alicyclic skeleton 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 product, and A block copolymer in which the block (B) does not have a structural unit containing an alicyclic skeleton in the main chain represented by the above formula (X) or a hydrogenated product thereof (hereinafter referred to as a "non-alicyclic skeleton block copolymer") (sometimes referred to as "polymer or its hydrogenated product").
The above-mentioned non-alicyclic skeleton block copolymers and hydrogenated products thereof are different from each other except that the polymer block (B) does not have a structural unit containing an alicyclic skeleton represented by formula (X) in its main chain. , the same as the above-mentioned block copolymer or its hydrogenated product.

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

(Olefin resin)
The other resin mentioned above is preferably an olefin resin from the viewpoint of performance as a laminate and economical efficiency. Examples of olefin resins include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene; homopolymers or copolymers of α-olefins; ; Examples include copolymers of propylene and/or ethylene and α-olefins. 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- 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 are mentioned, and one or two of these The above can be used. Furthermore, modified olefin resins obtained by modifying these olefin resins with maleic acid or the like can also be used.
Among these olefin resins, polypropylene is preferred because it has high compatibility with the above-mentioned block copolymer or its hydrogenated product and is suitable for obtaining a laminate with excellent transparency.
More specifically, as an example of a preferred embodiment of this 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. Among these, it is preferable to use a hydrogenated product of an olefin resin and a block copolymer. Since the olefin resin and the hydrogenated material have good compatibility, it is easy to maintain excellent transparency of the base layer.

(Resin other than olefin resin)
Further, as the other resin, resins other than the olefin resins described above may be used.
Resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer vulcanizate, styrene-butadiene rubber, styrene-isoprene rubber, nitrile rubber, butyl rubber, natural rubber, 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 crosslinked resin (ionomer) ), styrene resins such as polystyrene, AS resins, ABS resins, polyphenylene ether resins, polyamide resins such as nylon 6 and nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyurethane resins, polyoxymethylene homo Polymers, acetal resins such as polyoxymethylene copolymers, acrylic resins such as polymethyl methacrylate resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl chloride-vinyl acetate copolymers, etc. It will be done.

In addition, from the viewpoint of performance and economy as a laminate, the material for the base layer is preferably a block copolymer or a combination of its hydrogenated product and another resin, or a non-alicyclic skeleton block copolymer. Examples include combinations of copolymers and hydrogenated products thereof with other resins, and from the viewpoint of obtaining performance and economic efficiency as a laminate and better vibration damping properties, combinations of block copolymers or hydrogenated products thereof are more preferable. It is a combination with other resins.
The structure of the base material layer may be a single layer or a multilayer structure of two or more layers. In the case of two or more layers, two or more types of resins of different materials may be used.

[Content]
From the viewpoint of performance as a laminate, 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, and even more preferably It is 10% by mass or more. On the other hand, the upper limit of the content of the non-alicyclic skeleton block copolymer and its hydrogenated substance in the base material layer is not particularly limited and may be 100% by mass as long as it does not impair the effects of the present invention. From the viewpoint of economy, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

The content of other resins 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, and even more preferably from the viewpoint of performance and economic efficiency as a laminate. is 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more. On the other hand, the upper limit of the content of the above-mentioned other resins in the base material layer is not particularly limited as long as it does not impair the effects of the present invention, and may be 100% by mass. In the case of containing coalescence or its hydrogenated substance, from the viewpoint of further improving the vibration damping properties of the adherend, it is preferably 97% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass. It is as follows.

In the base material layer, the content ratio of the block copolymer or its hydrogenated product and other resin is the content of the block copolymer or its hydrogenated product, assuming that their total content is 100% by mass. is preferably 1 to 99% by mass, more preferably 1 to 90% by mass, even more preferably 1 to 80% by mass, even more preferably 1 to 70% by mass, even more preferably 1 to 60% by mass, even more preferably is 1 to 50% by weight, more preferably 1 to 40% by weight, and may also be 1 to 30% by weight, or 1 to 25% by weight.
As an example of a preferred embodiment of this embodiment, when the other resin is an olefin resin, the above content ratio is such that the content of the block copolymer or its hydrogenated product is 1 to 99% by mass, and the olefin resin The content is 99 to 1% by mass, and a more preferable embodiment is the same as the content ratio of the block copolymer or its hydrogenated product and other resin.
As an example of a more preferable aspect of this embodiment, when the other resin is polypropylene, the content of the block copolymer or its hydrogenated product is 1 to 99% by mass, and the content of polypropylene is 99 to 1% by mass. It is mass %, and a more preferable embodiment is the same as the content ratio of the block copolymer or its hydrogenated product and other resin.

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

[Additive]
Moreover, the base material layer in this embodiment does not prevent the inclusion of a tackifier resin, which will be described later, within a range that does not impair the effects of the present invention. However, if the base material layer has adhesive properties, its performance as a base material may be impaired, and there is a risk that the base material may develop unnecessary adhesive properties. The content of the tackifier resin in the base layer is preferably less than 1% by mass, and the base layer is substantially free of tackifier resin (the content of the tackifier resin is 0% by mass). Good too.
If necessary, additives may be further added to the base material layer within a range that does not impair the purpose of the present invention. Examples of additives include crosslinking agents (isocyanate crosslinking agents, epoxy crosslinking agents, metal chelate crosslinking agents, aziridine crosslinking agents, amine resins, etc.), heat stabilizers, light stabilizers, ultraviolet absorbers, infrared absorbers. , antioxidant, lubricant, coloring agent, antistatic agent, flame retardant, water repellent, waterproofing agent, hydrophilic agent, conductivity agent, thermal conductivity agent, electromagnetic shielding agent, translucency adjustment agent, fluorescent agent, sliding property agent, transparency agent, anti-blocking agent, metal deactivator, antibacterial agent, crystal nucleating agent, crack inhibitor, ozone deterioration inhibitor, rodent repellent, dispersant, Thickeners, light stabilizers, weathering agents, copper damage inhibitors, reinforcing agents, fungicides, macrocyclic molecules (cyclodextrin, calixarene, cucurbituril, etc.), adhesives other than the above tackifying resins (acrylic adhesives, etc.) ) etc. From the viewpoint of suppressing bleeding from the base layer, 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 base layer.

≪Adhesive layer≫
The adhesive layer in this embodiment preferably contains a tackifying resin in addition to the above-mentioned block copolymer or its hydrogenated product from the viewpoint of increasing the adhesive force of the laminate and maintaining the adhesive force even at high temperatures.

[Tackifying resin]
Examples of tackifying resins include coumaron resins such as coumaron/indene resin; phenolic resins and terpene resins such as pt-butylphenol/acetylene resin, phenol/formaldehyde resin, terpene/phenol resin, polyterpene resin, xylene/formaldehyde resin, etc. Resins: Petroleum resins such as aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, modified alicyclic petroleum resins; pentaerythritol ester of rosin, glycerol ester of rosin, etc. Rosin resins such as rosin esters, hydrogenated rosin, methyl ester of hydrogenated rosin, pentaerythritol ester of polymerized rosin, hydrogenated rosin ester, high melting point ester resin, polymerized rosin, hardened rosin, special rosin ester, etc. Examples include. Among them, an alicyclic saturated hydrocarbon resin can be suitably used as the tackifying resin. Examples of the alicyclic saturated hydrocarbon resin include hydrogenated aromatic petroleum resins; for example, commercially available products such as the "Alcon" series manufactured by Arakawa Chemical Industries, Ltd. may be used. These tackifier resins may be used alone or in combination of two or more. Note that from the viewpoint of reducing adhesive residue and improving heat resistance and weather resistance of the resulting adhesive layer, it is preferable to use a hydrogenated tackifying resin.
The softening point of the tackifier resin is preferably 85 to 160°C, more preferably 100 to 150°C, even more preferably 105 to 145°C. If the softening point of the tackifier resin is 85°C or higher, it will be easier to suppress the decrease in adhesive holding power at high temperatures (approximately 60°C), and if it is 160°C or lower, the molding processability of the composition constituting the adhesive layer will be reduced. In good condition.

[Content]
The content of the above-mentioned block copolymer or its hydrogenated material in the adhesive layer may be 100% by mass, but from the viewpoint of the vibration damping properties of the laminate and the adhesive strength at high temperatures, it is preferably 1 to 80% by mass. .
Further, the content of the block copolymer or its hydrogenated substance in the adhesive layer is preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of improving the vibration damping properties of the laminate. . On the other hand, the above-mentioned content of the block copolymer or its hydrogenated substance in the adhesive layer is preferably 70% by mass or less, and even more preferably 60% by mass, from the viewpoint of economic efficiency and making it easier to maintain adhesive strength at high temperatures. % or less, more preferably 50% by mass or less, even more preferably 40% by mass or less.

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

[Non-alicyclic skeleton block copolymer and its hydrogenated product]
Further, as the resin component constituting the adhesive layer, from the viewpoint of performance as a laminate, it is preferable to use the above-mentioned non-alicyclic skeleton block copolymer or its hydrogenated product.
The content of the non-alicyclic skeleton block copolymer or its hydrogenated substance in the adhesive layer is preferably 10% by mass or more, more preferably 20% by mass, from the viewpoint of reducing adhesive residue in the adhesive layer and increasing the adhesive strength of the adhesive layer. % or more, more preferably 30% by mass or more, even 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 hydrogenated substance in the adhesive layer is not particularly limited and may be 100% by mass as long as it does not impair the effects of the present invention. From the viewpoint of properties, the content is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less.

[Other resin components]
(Olefin resin)
An olefin resin may be used as the resin component constituting the adhesive layer within a range that does not impair the purpose of the present invention.
Examples of olefin resins include polyethylenes such as high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene; polypropylenes such as homopolypropylene, block polypropylene, and random polypropylene; homopolymers or copolymers of α-olefins; ; Examples include copolymers of propylene and/or ethylene and α-olefins. 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- 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 are mentioned, and one or two of these The above can be used. Furthermore, modified olefin resins obtained by modifying these olefin resins with maleic acid or the like can also be used.

(Resin other than olefin resin)
Moreover, resins other than the above-mentioned olefin resins may be used as the resin component constituting the adhesive layer within a range that does not impair the object of the present invention.
Resins other than olefin resins include polyisoprene, polybutadiene, ethylene-propylene-diene copolymer vulcanizate, styrene-butadiene rubber, styrene-isoprene rubber, nitrile rubber, butyl rubber, natural rubber, 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 crosslinked resin (ionomer) ), styrene resins such as polystyrene, AS resins, ABS resins, polyphenylene ether resins, polyamide resins such as nylon 6 and nylon 66, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyurethane resins, polyoxymethylene homo Polymers, acetal resins such as polyoxymethylene copolymers, acrylic resins such as polymethyl methacrylate resins, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, ethylene-vinyl chloride-vinyl acetate copolymers, etc. It will be done.

(Additive)
If necessary, a plasticizer or filler may be added to the adhesive layer within a range that does not impair the purpose of the present invention.
Examples of plasticizers include paraffinic, naphthenic, and aromatic process oils; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; white oil; mineral oil; liquid cooligomer of ethylene and α-olefin; liquid paraffin; Polybutene; Low molecular weight polyisobutylene; Examples include liquid polydienes such as liquid polybutadiene, liquid polyisoprene, liquid polyisoprene/butadiene copolymer, liquid styrene/butadiene copolymer, liquid styrene/isoprene copolymer, and their hydrogenated products. It will be done.
Examples of fillers include talc, mica, calcium silicate, glass, glass flakes, glass beads, glass hollow spheres, glass fibers, calcium carbonate, magnesium carbonate, zinc carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide. , calcium hydroxide, zinc borate, dawsonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, silica alumina, diatomaceous earth, wollastonite, zeolite, boehmite, sodium aluminosilicate, magnesium silicate, graphene, barium carbonate , silicon nitride, aluminum nitride, boron nitride, potassium titanate, aluminum silicate (kaolin, clay, pyrophyllite, bentonite), magnesium silicate (attapulgite), 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 carbon, carbon hollow sphere, calcium titanate, lead zirconate titanate, carbonized Examples include inorganic fillers such as silicon; organic fillers such as wood flour and starch; and organic pigments. 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 necessary within a range that does not impair the purpose of the present invention. Examples of additives include crosslinking agents (isocyanate crosslinking agents, epoxy crosslinking agents, metal chelate crosslinking agents, aziridine crosslinking agents, amine resins, etc.), heat stabilizers, light stabilizers, ultraviolet absorbers, infrared absorbers. , antioxidant, lubricant, coloring agent, antistatic agent, flame retardant, water repellent, waterproofing agent, hydrophilic agent, conductivity agent, thermal conductivity agent, electromagnetic shielding agent, translucency adjustment agent, fluorescent agent, sliding property agent, transparency agent, anti-blocking agent, metal deactivator, antibacterial agent, crystal nucleating agent, crack inhibitor, ozone deterioration inhibitor, rodent repellent, dispersant, Thickeners, light stabilizers, weathering agents, copper damage inhibitors, reinforcing agents, fungicides, macrocyclic molecules (cyclodextrin, calixarene, cucurbituril, etc.), adhesives other than the above tackifying resins (acrylic adhesives, etc.) ) etc.
On the other hand, from the viewpoint of maximizing the effects of the present invention, the content of each of the plasticizer, filler, and additive in the adhesive layer is preferably 10% by mass or less, more preferably 5% by mass or less, and 2% by mass or less. It is more preferably less than % by mass. If the content of these is 10% by mass or less, it is considered that there is little influence on the behavior of tan δ strength, which will be described later.

≪Method for manufacturing laminate≫
The method for producing the above laminate is not particularly limited, and includes, for example, (1) coextrusion molding of the composition constituting the base layer and the composition constituting the adhesive layer using a multilayer T-die extruder, etc.; ) A method of coating a molded base material layer with a composition constituting an adhesive layer, and (3) a compression molding method of laminating a molded base material layer and a composition constituting an adhesive layer by compression molding. .

The composition constituting the base material layer and the composition constituting the adhesive layer can be manufactured by melt-kneading each.
For melt kneading, the components to be mixed in each layer are mixed using a mixer such as a Henschel mixer, V blender, ribbon blender, tumbler blender, conical blender, etc., or after mixing, the components are mixed using a single screw or twin screw extruder. The mixture may be melted and kneaded using a kneader or the like. The temperature during melt-kneading can be set as appropriate, but is usually 150 to 300°C, preferably 160 to 250°C.
Each of the compositions constituting the obtained base material layer and adhesive layer is preferably pelletized from the viewpoint of easily producing a laminate by extrusion molding.

When manufacturing a laminate using the coating method described in (2) above, a solution is prepared by dissolving the composition constituting the adhesive layer in an organic solvent, and after applying this solution to the molded base material layer, By drying, a laminate can be suitably obtained. This organic solvent is not particularly limited as long as it can dissolve the composition constituting the adhesive layer. Examples of the solvent include cyclohexane, methylcyclohexane, n-hexane, n-heptane, benzene, toluene, a toluene-ethanol mixed solvent, xylene, ethylbenzene, and tetrahydrofuran. These solvents may be used alone or in combination of two or more. From the viewpoint of ease of coating, ease of solution production, and ease of drying, toluene, a toluene-ethanol mixed solvent, xylene, and ethylbenzene are preferred.
The concentration of the resin component in the solution is preferably 5 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 5 to 30% by mass, from the viewpoint of ease of coating, ease of manufacturing the solution, and ease of drying. Mass%.

When producing a laminate using the coextrusion method described in (1) above, the composition constituting the base layer and the composition constituting the adhesive layer are melted and plasticized using different extruders, and each pellet is do. Thereafter, the pellets can be suitably manufactured by combining and extruding the pellets into multiple layers using a feed block die provided at the tip of the extruder, and then taking them off into a film.
When manufacturing a laminate using the compression molding method described in (3) above, the composition constituting the adhesive layer in pellet or sheet form is layered on the molded base material, compression molded while heating, and then cooled. It can be obtained more preferably.

When the composition constituting the adhesive layer is a hot melt type, the composition is melted by heating and applied to the base layer using a conventional hot melt applicator, and then cooled. By doing so, a laminate can be suitably obtained.

An example of a combination of a composition constituting a base material layer and a composition constituting an adhesive layer in a 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 skeleton block copolymer or its hydrogenated product is represented by <2>.
A laminate in which the composition forming the base layer contains an olefin resin and <1> and/or <2>, and the composition forming the adhesive layer contains a tackifying resin and <1> and/or <2>. body (however, at least one layer among the base material layer and the adhesive layer contains <1>);
A laminate in which the composition forming the base layer contains an olefin resin and <1> and/or <2>, and the composition forming the adhesive layer contains a tackifier resin and <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 adhesive layer contains a tackifying resin and <2> (however, if the composition at least one layer of the layer and the adhesive layer contains <1>);
A laminate in which the composition forming the base layer contains an olefin resin and <1>, and the composition forming the adhesive layer contains a tackifying 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 adhesive layer contains a tackifying resin and <1> and/or <2> (however, if the base material at least one layer of the layer and the adhesive layer contains <1>);
can be mentioned. This embodiment is not limited to the combination of the composition constituting the base layer and the composition constituting the adhesive layer. Specific aspects of each of <1>, <2>, olefin resin, and tackifying resin in the composition constituting the base material layer and the composition constituting the adhesive layer are the specific aspects described above for each. It is similar to Further, the composition constituting the base 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 this embodiment, the ratio [i/ii] of the Shore A hardness i of the base material layer to the Shore A hardness ii of the adhesive layer is 1.1 or more. If 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 will be impaired, and the adhesive layer will be difficult to fix to the base material layer, making it difficult for the laminate to be used in various ways. Inconveniences arise when used for purposes. The above ratio [i/ii] has a preferable value that differs depending on the application, but from the viewpoint of being able to fix the adhesive layer to the base material layer and making it easy to apply and peel off the laminate, it is preferably 1.2 or more, more preferably It is 1.3 or more. Furthermore, the upper limit of the ratio [i/ii] cannot be unconditionally defined because it varies depending on the application, but it can be set to 3.3 or less, for example.

[hardness]
The Shore A hardness i of the base 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 is 70-98.
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, from the viewpoint of adhesion with the base material layer, difficulty in leaving adhesive residue, and ease of attachment and peeling to adherends, the Shore A hardness II of the adhesive layer is preferably 30 to 80, more preferably 30 to 80. Preferably it is 40-70.
Note that the Shore A hardness is a value measured in more detail according to the method described in Examples.

[Storage modulus of adhesive layer]
In this embodiment, the ratio 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 [E'(23°C)/E' (60°C) )] is preferably 2 or more.
In this embodiment, the adhesive layer contains the above-mentioned block copolymer or its hydrogenated product, so that the storage modulus ratio [E'(23°C)/E'(60°C)] is 2 or more. easier to achieve. In general, adhesive strength decreases as the temperature increases, but in this embodiment, if the storage modulus ratio [E'(23°C)/E'(60°C)] is 2 or more, The degree of deterioration in peel strength over temperature is reduced, and it tends to be difficult to peel off and leave adhesive residue even at high temperatures.
In the present embodiment, the storage modulus ratio [E'(23°C)/E'(60°C)] of the adhesive layer is determined by the composition of the adhesive layer (the above-mentioned tackifier resin, the above-mentioned block copolymer, or the like). 2.5 or more, or even 3.0 or more, by adjusting the types and contents of hydrogenated substances, the above-mentioned non-alicyclic skeleton block copolymers and their hydrogenated substances, and other resin components. It is also possible to do this.
In addition, the storage elastic modulus is a value measured in more detail according to the method described in Examples.

[tanδ intensity]
The above-mentioned block copolymer or its hydrogenated product can exhibit excellent vibration damping properties. Therefore, when the base layer contains a block copolymer or a hydrogenated product thereof, the tan δ strength of the base 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 preferably be 0.05 or more, more preferably 0.10 or more.
Further, when the adhesive layer contains a block copolymer or a hydrogenated product thereof, the tan δ strength of the adhesive layer is preferably 0.10 or more, more preferably 0.15 or more, and even more preferably 0. .18 or more, preferably 0.10 or more, more preferably 0.15 or more, even more preferably 0.18 or more, even more preferably 0.25 or more at a temperature of 60°C, and at a temperature of 60°C Preferably it is 0.10 or more, more preferably 0.15 or more, and still more preferably 0.18 or more.
Furthermore, the loss coefficient of the adherend to which the laminate is attached is preferably 0.05 or more, more preferably 0.10 or more, and even more preferably 0. It can be expected that it will become larger than .15. In particular, when both the base layer and the adhesive layer contain a block copolymer or its hydrogenated product, the loss coefficient of the adherend to which the laminate is attached is the same as that of the adherend to which the laminate is not attached. In comparison, it can be expected to increase preferably by 0.10 or more, more preferably by 0.15 or more, and still more preferably by 0.20 or more.
Note that the tan δ intensity is a value measured in more detail according to the method described in Examples.

[Peel strength]
In this embodiment, the peel strength of the laminate is determined based on JIS Z 0237 (2009) by using an acrylic resin plate as an adherend and bonding the laminate so that the adhesive layer and the adherend are in contact with each other. The 180 degree peel strength measured at a measurement temperature of 23° C. is preferably 5.0 N/25 mm or more, more preferably 6.0 N/25 mm or more. 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 a measurement temperature of 60°C. Generally, the adhesive strength decreases as the temperature increases, but in this embodiment, one or both of the base material layer and the adhesive layer contains the above-mentioned block copolymer or its hydrogenated product, and the content is adjusted to a suitable value. By adjusting the adhesive strength within a certain range, it becomes easier to achieve the above-mentioned adhesive strength.
Further, in the present embodiment, the ratio of the peel strength at 60° C. to the peel strength at 23° C. of the laminate can be 0.3 or more, and even 0.4 or more. The peel strength ratio can be easily achieved by particularly adjusting the composition of the adhesive layer (the type and content of the above-mentioned block copolymer or its hydrogenated product, the above-mentioned tackifier resin, and optional components).
In addition, the peel strength is a value measured in more detail according to the method described in Examples.

≪Dimensions of laminate≫
Although there is no particular restriction on the thickness of the adhesive layer constituting the laminate of this embodiment, it is usually preferably 1 μm or more and 200 μm or less, more preferably 5 μm or more and 150 μm or less, and 5 μm or more and 100 μm or less. It is even more preferable.
On the other hand, the thickness of the base material layer is not particularly limited and may be specified depending on the use of the laminate, but in order to suitably exhibit the adhesive force of the adhesive layer, the thickness is preferably 500 μm or less, more preferably 200 μm or less. , more preferably 100 μm or less. Moreover, the thickness of the base material layer is usually 5 μm or more.

≪Applications≫
In this embodiment, the laminate can be used for various purposes.
Applications include, for example, adhesives including laminates, and examples of adhesives include pressure-sensitive adhesives. Also included are adhesive tapes, adhesive sheets, and surface protection films containing the above-mentioned pressure-sensitive adhesives.

Further, examples of the adhesive include hot melt adhesives.
The above-mentioned hot melt adhesives can be used, for example, in 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. , use in articles comprising cardboard, books, filters or packaging;
Use in gasket sealants (especially in the automotive, electrical components and technical lighting sectors);
Use of multilayer films in the manufacture of resealable trays;
Use in articles containing mailing container materials;
Vibration isolating material, cushioning material, shock absorbing material, memory foam material, fall prevention material, seismic isolation material, seismic insulation material, or vibration damping material (preferably sound deadening material, more preferably damping or sound deadening mat, pad in the automotive industry) , sheets and tapes);
Use in electronic devices (in particular LCD displays, LED displays, touch screens or flexible thin film solar cells);
Use in transdermal drug delivery systems;
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), connections between heat pipes and water tanks of solar heating; Department, fuel cells and wind turbines, computer chip manufacturing, optical devices, batteries, housings, coolers, heat exchange devices, wires, cables, heating wires, refrigerators, dishwashers, air conditioning equipment, accumulators, transformers, laser equipment, functionality Use in clothing, car seats, medical equipment, fire protection equipment, electric motors, airplanes, and trains;
Use of filaments of 3D printing materials in potting or molding sealants to seal heat generating devices;
Use for joining articles with substrates formed from wood, metal, polymer plastics, glass and textiles; use for joining to external surfaces, in water towers; glazing in the manufacture of footwear or in the manufacture of windows. Use as compounds, in the manufacture of doors and architectural panels or in the manufacture of portable devices and displays;
Book binding, wood gluing, flat lamination, flexible packaging, profile wrapping, edge banding, textile lamination, low pressure molding, and use in shoes;
Use in the production of bonded fabrics/textiles for books, packaging films, rigid panels, furniture, windows, footwear, car headlights, car trim or clothing;
Use in decorative films;
can be mentioned.

EXAMPLES The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited thereto.

<Block copolymers and hydrogenated substances>
A method for evaluating the physical properties of the block copolymer or hydrogenated product obtained in the production example described below is shown below.
(1) Content of polymer block (A) The block copolymer before hydrogenation was dissolved in CDCl ₃ and measured by ¹ H-NMR [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 weight average molecular weight (Mw) in terms of polystyrene was determined for the hydrogenated block copolymer by gel permeation chromatography (GPC) measurement under the following conditions.
(GPC measurement device and measurement conditions)
・Device: GPC device “HLC-8020” (manufactured by Tosoh Corporation)
- Separation column: "TSKgel GMHXL", "G4000HXL" and "G5000HXL" manufactured by Tosoh Corporation were connected in series.
・Eluent: Tetrahydrofuran ・Eluent flow rate: 0.7mL/min
・Sample concentration: 5mg/10mL
・Column temperature: 40℃
・Detector: Differential refractive index (RI) detector ・Calibration curve: Created using standard polystyrene

(3) Hydrogenation rate in polymer block (B)
It was 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 ¹ H-NMR measurement.
・Device: Nuclear magnetic resonance device “ADVANCE 400 Nano bay” (manufactured by Bruker)
・Solvent: CDCl ₃

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

(5) Content of alicyclic skeleton (X) in polymer block (B) 600 mg of the block copolymer before hydrogenation and 40 mg of Cr(acac) ₃ were dissolved in 4 mL of CDCl ₃ and using a 10 mm NMR tube. Quantitative ^13C -NMR measurement (pulse program: zgig, inverse gated 1H decoupling method) [equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30°C] was carried out, and the polymer block was measured using the following method. The contents of each of the alicyclic skeletons X, X1, and X2 in (B) were calculated.
In addition, in Table 3, X, X1, and X2 represent the following alicyclic skeletons.
X: Alicyclic skeleton having a combination of substituents shown below (i) to (vi) X1: Alicyclic skeleton having a combination of substituents shown below (i), (iv) X2: Below (ii), ( Alicyclic skeleton (i) having a combination of substituents iii), (v), and (iv): R ¹ = hydrogen atom, R ² = hydrogen atom, R ³ = hydrogen atom; (1,2Bd+Bd)
(ii): R ¹ = hydrogen atom, R ² = methyl 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]
Table 1-1 shows each peak and its derived structure. Letting the integral values of each peak be a to g, the integral 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+c−d+e/ 2+2f), (g-c)/(a+b+c-d+e/2+2f), a/(a+b+c-d+e/2+2f).

(6) ¹³ C-NMR peak area ratio The hydrogenated products of Production Example 1 and Comparative Production Example 1 were subjected to the above quantitative ¹³ C-NMR measurement [equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30° C., solvent: CDCl ₃ ], and the peak area ratio [peak area with chemical shift value of 50.0 to 52.0 ppm]/[peak area with chemical shift value of 43.0 to 45.0 ppm] was calculated.

(7) Tan δ peak top temperature, peak top intensity, maximum width of temperature range where tan δ is 1.0 or more, tan δ intensity at 20°C and 30°C For the following measurements, hydrogenated block copolymers was pressed at a temperature of 230° C. and a pressure of 10 MPa for 3 minutes to produce a single layer sheet with a thickness of 1.0 mm. The single-layer sheet was cut into a disk shape, and this was used as a test sheet.
For measurements, a distortion-controlled dynamic viscoelasticity device "ARES-G2" (T.A. Instruments Inc.) with a disk diameter of 8 mm was used as a parallel plate vibration rheometer based on JIS K 7244-10 (2005). (manufactured by Mento Japan) was used.
The gap between the two flat plates was completely filled with the above test sheet, and the above test sheet was vibrated at a frequency of 1Hz with a strain of 0.1%, and the vibration rate was set at a constant rate of 3°C/min from -70°C to 100°C. The temperature rose rapidly. The temperature of the test sheet and disk was maintained until there was no change in the measured values of shear loss modulus and shear storage modulus, and the maximum value of the peak intensity of tan δ (peak top intensity) and the maximum value were obtained. The temperature (peak top temperature) was determined. In addition, the maximum width of the temperature range where tan δ is 1.0 or more and the tan δ strength at 20° C. and 30° C. were determined. The larger the value, the better the vibration damping properties.

[Manufacture example 1]
Production of hydrogenated product (H-TPE-1) In a pressure-resistant container that was purged with nitrogen and dried, 50 kg of cyclohexane was used as a solvent, and 87 g of a cyclohexane solution of sec-butyllithium with a concentration of 10.5% by mass was added as an anionic polymerization initiator (sec - Butyllithium (substantive amount added: 9.1 g) was charged.
After raising the temperature inside the pressure container to 50°C, 1.0 kg of styrene (1) was added and polymerized for 1 hour. At the inside temperature of the container at 50°C, 2,2-di(2-tetrahydrofuryl)propane ( A mixture of 8.16 kg of isoprene and 6.48 kg of butadiene was added over 5 hours at the average diene feed rate shown in Table 2, followed by polymerization for 2 hours, and 1.0 kg of styrene (2) was added. In addition, by polymerizing for 1 hour, a reaction solution containing a polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer was obtained.
A Ziegler hydrogenation catalyst formed from nickel octylate and trimethylaluminum was added to the reaction solution in a hydrogen atmosphere, and the mixture was reacted at a hydrogen pressure of 1 MPa and a temperature of 80° C. for 5 hours. After the reaction solution was allowed to cool and depressurize, the catalyst was removed by washing with water and dried under vacuum to obtain a hydrogenated product of polystyrene-poly(isoprene/butadiene)-polystyrene triblock copolymer (hereinafter referred to as H -TPE-1) was obtained.
Table 2 shows each raw material and its usage amount. Further, the results of the physical property evaluation are shown in Table 3.

[Manufacture example 2]
Production of hydrogenated product (H-TPE-2) Hydrogen of block copolymer An additive (H-TPE-2) was produced. Further, the results of the physical property evaluation are shown in Table 3.
[Manufacture example 3]
Production of hydrogenated product (H-TPE-3) Hydrogen of block copolymer An additive (H-TPE-3) was produced. Further, the results of the physical property evaluation are shown in Table 3.
[Manufacture example 4]
Production of hydrogenated product (H-TPE-4) Hydrogen of block copolymer An additive (H-TPE-4) was produced. Further, the results of the physical property evaluation are shown in Table 3.

[Comparative production example 1]
Production of hydrogenated product (H-TPE-1') Block copolymer A hydrogenated product (H-TPE-1') was produced. Further, the results of the physical property evaluation are shown in Table 3.

The hydrogenated block copolymers of Production Examples 1 to 4 have a tan δ peak top intensity of 1.0 or more, and the tan δ peak top temperature is shown in a wide temperature range, so they can be used in a wide range of applications as vibration damping materials. It can be said that it is suitable for In particular, when compared with Comparative Production Example 1, it can be seen that Production Examples 1 to 4 have relatively high tan δ strengths at 20°C and 30°C, and have excellent 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 was put into a Brabender (manufactured by Brabender, "Plastograph EC 50cc Mixer") and melted and kneaded for 3 minutes at a cylinder temperature of 240°C and a screw rotation speed of 100 rpm. The composition was press-molded (240° C., 2 minutes) to prepare a sheet (thickness: 1 mm) for the base layer.

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

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

[Evaluation of the physical properties]
A method for evaluating the physical properties of the base layer, adhesive layer, and laminate produced above is shown below.
(Shore A hardness)
Six sheets of the obtained base material layer and adhesive layer were each stacked to form a test piece for hardness measurement with a thickness of 6 mm, and an automatic rubber hardness meter P2-A type (high The Shore A hardness i of the base material layer and the Shore A hardness ii of the adhesive layer were measured using a micrometer (manufactured by Mokunoshi Keiki). The results are shown in Table 4.

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

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

(Peel strength, adhesive residue (23℃))
The obtained laminate was pasted on an extruded acrylic plate (trade name SUMIPEX E, thickness 1.5 mm, manufactured by Sumika Acrylic Sales Co., Ltd.) so that the adhesive layer was in contact with the acrylic resin plate, and cut to a width of 25 mm. The sample was used as a test piece. This test piece was rolled back and forth twice at a speed of 10 mm/min from the base layer side using a 2 kg rubber roller, and then left for 24 hours in an atmosphere of 23±1° C. and 50±5% humidity. Thereafter, in accordance with JIS Z 0237 (2009), the 180 degree peel strength between the laminate and the acrylic resin plate was measured at a peel rate of 300 mm/min using Instron 5566 (manufactured by Instron), It was defined as peel strength (23°C). In addition, it was visually confirmed whether there was any adhesive residue on the adherend after peeling. The results are shown in Table 4.

(Peel strength, adhesive residue (60℃))
After being left in an atmosphere of 23 ± 1°C and humidity 50 ± 5% for 24 hours, and then left in an atmosphere of 60°C for 10 minutes, the peel strength was measured in an atmosphere of 60°C. Peel strength and adhesive residue (60°C) were determined in the same manner as in 23°C). The results are shown in Table 4.

Each component shown in Table 4 is as follows.
・Olefin resin: Homopolypropylene (Novatec PP, manufactured by Nippon Polypropylene Co., Ltd.)
・Tackifier resin: Alcon P-125 (alicyclic saturated hydrocarbon resin, softening point (ring and ball method) 125±5°C, manufactured by Arakawa Chemical Industry Co., Ltd.)

From Table 4, Examples 1, 2, and 4 to 8 containing hydrogenated block copolymers in the base layer had large tan δ strength values in the temperature range of 23 to 60°C, and the adhesive layer In Examples 1 and 3 to 8 containing hydrogenated block copolymers, the tan δ strength of the adhesive layer is large in the temperature range of 23 to 60°C.
Furthermore, in Examples 1 and 3 to 8, the ratio of the storage elastic modulus E' of the adhesive layer [E'(23°C)/E' (60°C)] was higher than that of the laminates of Comparative Examples 1 to 3. Large, 2 or more. As described above, the laminates of Examples 1 and 3 to 8 had a larger ratio of storage modulus at 23°C and 60°C than the comparative example, and the decrease in peel strength from 23°C to 60°C was smaller [ (Peel strength at 60°C)/(Peel strength at 23°C) is large]. Example 2 and Comparative Examples 1 to 3 have the same structure of the adhesive layer, but in Example 2, the drop in peel strength from 23°C to 60°C was smaller than in the laminates of Comparative Examples 1 to 3. . One of the reasons why the drop in peel strength was smaller in Example 2 than in Comparative Examples 1 to 3 was that appropriate flexibility was imparted to the base material layer by containing the hydrogenated block copolymer. This can be mentioned.
Furthermore, the laminates of Examples 1 to 8 did not leave 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 layer and the adhesive layer. It is expected that excellent vibration damping properties can be imparted to the adherend, and it can be seen that it is difficult to peel off even under high temperature conditions and is extremely unlikely to leave adhesive residue.

Although it is not certain, based on the peel strength ratios of Examples 1 and 3 to 8, the adhesive layer containing the block copolymer or its hydrogenated product is softened at high temperature (60°C), resulting in improved adhesion. The adhesive penetrated into the minute irregularities on the surface of the material (acrylic resin board) and acted like an anchor, or the convexities of the minute irregularities on the surface of the adhesive layer bit into the concave parts of the adherend and exerted an elastic tightening force. It is presumed that this suppressed the decrease in adhesive strength between the adhesive layer and the adherend. Furthermore, since the peel strength ratio differed depending on the structure of the base layer even if the structure of the adhesive layer was the same, it is thought that this was influenced by the flexibility of the base layer.
Furthermore, 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. This is considered to be because the block copolymer or its hydrogenated product, which is a constituent component of the base layer in Examples 1, 2, and 4 to 8, has high compatibility with polypropylene.
Therefore, the laminates of Examples 1, 2, and 4 to 8 in this embodiment are useful for applications requiring transparency, for example, as surface protection films for liquid crystal displays and the like.

The laminate of the present invention can impart vibration damping properties to adherends, and is difficult to peel off even at high temperatures and does not leave adhesive residue. It is useful as a protective film, and a surface protection film that prevents dirt and scratches on target products during transportation, storage, and processing.

Claims (21)

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 ii of the adhesive layer is 1.1 or more,
A laminate in which at least one layer among the base 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 (A) is a structural unit derived from aromatic vinyl, and the polymer block (B) is a structural unit derived from isoprene and/or butadiene, the content of the polymer block (A) is 1 to 50% by mass, and the following formula (X ) has a structural unit containing 1.4 to 40 mol% of one or more alicyclic skeletons (X) in the main chain.

(In the above formula (X), R ¹ to R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, and a plurality of R ¹ to R ³ may be the same or different.) The laminate according to claim 1, wherein the content of the block copolymer or its hydrogenated product in the base layer is 1 to 100% by mass. 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. laminate. 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 tackifying resin in the base 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 content of the tackifying resin in the adhesive layer is 1% by mass or more. The alicyclic skeleton (X) of claims 1 to 7 includes 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. The laminate according to any one of the above. 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, comprising at least a styrene-hydrogenated butadiene/isoprene-styrene copolymer as a hydrogenated substance of the block copolymer. The laminate according to any one of claims 1 to 7, wherein R ¹ to R ³ are hydrogen atoms. The laminate according to any one of claims 1 to 11, wherein the polymer block (B) contains 1.8 to 30 mol% of the alicyclic skeleton (X). The laminate according to claim 8 or 9, wherein the polymer block (B) contains 1.6 to 40 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 hydrogenation rate of the polymer block (B) is 50 to 99 mol%. The laminate according to any one of claims 1 to 15, wherein the amount of vinyl bonds in the polymer block (B) is 55 to 95 mol%. In accordance with JIS K 7244-10 (2005), the block copolymer or its hydrogenated product has a strain of 0.1%, a frequency of 1 Hz, a measurement temperature of -70 to 100°C, and a heating rate of 3°C/ The laminate according to any one of claims 1 to 16, wherein there is a series of temperature ranges in which tan δ is 1.0 or more when measured under conditions of 1000 to 3000 ml, and the maximum width of the temperature range 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 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 [E' (23°C)/E' (60°C)] is 2. The laminate according to any one of claims 1 to 20, which is the above.