JP2022059825A - Vibration damping material, method for manufacturing vibration damping material, laminate, and vibration damping property improvement method - Google Patents

Abstract

To provide a vibration damping material which is excellent in vibration damping property and light-weight property and enables easy manufacture of a constraint type laminate, a method for manufacturing the same, and a laminate using the same.SOLUTION: A vibration damping material 100 has a vibration damping layer (AL) and a constraint layer (BL) laminated on the vibration damping layer (AL), in which the vibration damping layer (AL) is composed of a thermoplastic resin composition (AC) containing a block copolymer (A) having a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) containing a structural unit derived from a conjugated diene compound, and the constraint layer (BL) is composed of a thermoplastic resin composition (BC).SELECTED DRAWING: Figure 1

Description

The present invention relates to a vibration damping material, a method for manufacturing a vibration damping material, a laminate, and a method for improving vibration damping properties.

As a method of improving the vibration damping property of a steel sheet, a method of pasting an elastomer material having a high vibration damping property is known.
However, when a vibration-damping layer made of a vibration-damping elastomer is attached to a steel sheet to form a so-called "unrestrained" vibration-damping steel sheet, the thickness of the vibration-damping layer should be at least in order to exhibit high vibration-damping properties. It should be at least twice as large as the steel plate. Therefore, the non-restraint type vibration damping steel sheet has a problem that if it is attempted to secure sufficient vibration damping property, problems such as an increase in thickness, an increase in weight, and an increase in material price are likely to occur. Further, since the damping layer is exposed, there is a problem that it is difficult to increase the heat resistance. For these reasons, the types of products and technical fields that can be applied to unrestrained vibration damping steel sheets are limited.
On the other hand, as a method of improving the vibration damping property of the steel sheet even if the thickness of the vibration damping layer is thin, a so-called "constraint" is provided by attaching a restraint layer to the vibration damping layer side of the non-restraint type vibration damping steel sheet. It is known to be a "mold" damping steel sheet.

For example, Patent Document 1 describes a vibration-damping film for a constrained vibration-damping steel sheet containing a resin layer made of a block copolymer of a vinyl aromatic compound and a conjugated diene compound or a hydrogenated product thereof. Patent Document 1 describes that steel plates are attached to both sides of the vibration damping film.

The restraint type vibration damping steel sheet is preferable from the viewpoint of suppressing the weight increase of the vibration damping layer because the vibration damping layer can exhibit the vibration damping property even if the thickness of the vibration damping layer is about 1/10 of that of the steel plate or the restraining layer. However, if a steel plate is used as the restraining layer, the laminate has a structure of "steel plate / vibration damping layer / steel plate", and the weight of the entire laminate tends to increase. For this reason, there arises a problem that it becomes difficult to manufacture the laminated body and the weight of the product to which the restrictive damping steel plate is applied tends to increase.

Patent Document 2 describes a restraint layer, a first viscoelastic layer laminated on the restraint layer having a glass transition point at 0 ° C. or higher, and a glass transition point below 0 ° C. laminated on the first viscoelastic layer. A sticking type vibration damping material including a second viscoelastic layer having the above is described. In Patent Document 2, the second viscoelastic layer of this adhesive type vibration damping material is used by being attached to stainless steel or the like, and as a restraining layer, a glass cloth, a resin-impregnated glass cloth, a metal foil, or a synthetic resin is used. It is described that non-woven fabric, carbon fiber and the like can be mentioned.

Japanese Unexamined Patent Publication No. 2000-238193 Japanese Unexamined Patent Publication No. 2013-18242

Since the adhesive type damping material described in Patent Document 2 uses a fibrous material or a metal foil as a restraining layer, it is lighter than the restraining type damping steel sheet described in Patent Document 1. It is advantageous in that. However, if the restraining layer is made of a material as described in Patent Document 2, it is difficult to obtain sufficient rigidity, so that the required vibration damping property may not be ensured. Further, when a special material such as glass cloth is used, there is a problem that it becomes difficult to manufacture a vibration damping material by coextrusion, heat fusion, or the like.
As described above, there is room for improvement in the damping material for obtaining the restraining type vibration damping laminated body, the vibration damping property and the light weight are excellent, and the restraining type laminated body can be easily obtained. There is a demand for new damping materials.

Therefore, an object of the present invention is to provide a vibration damping material which is excellent in vibration damping property and light weight and can easily obtain a restraint type laminated body, a method for manufacturing the same, and a laminated body using the same. There is something in it.

The present inventors have heat containing a block copolymer (A) having a polymer block containing a structural unit derived from an aromatic vinyl compound and a polymer block containing a structural unit derived from a conjugated diene compound. It is possible to solve the above-mentioned problems by using the plastic resin composition as the vibration damping layer and using the thermoplastic resin composition having predetermined physical properties as the restraining layer and setting the thickness of each of the above layers to a predetermined relationship. We have found and completed the present invention.

（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。）
［７］前記脂環式骨格（Ｘ）において、前記Ｒ^１～Ｒ^３のうち少なくとも１つがメチル基である脂環式骨格（Ｘ’）を含む、上記［６］に記載の制振材。
［８］前記重合体ブロック（Ａ－２）中に前記脂環式骨格（Ｘ）又は（Ｘ’）を１モル％以上含有する、上記［６］又は［７］に記載の制振材。
［９］熱可塑性組成物（ＡＣ）の、ＪＩＳ Ｋ７２４４－４（１９９９年）に準じて、歪み量０．２％、周波数１０Ｈｚの条件で引張振動による動的粘弾性試験を行うことで測定される２０℃における引張貯蔵弾性率Ｅ’（ＡＣ）が１００ＭＰａ以下である、上記［１］～［８］のいずれか一つに記載の制振材。
［１０］熱可塑性組成物（ＡＣ）の、ＪＩＳ Ｋ７２４４－４（１９９９年）に準じて、歪み量０．２％、周波数１０Ｈｚの条件で引張振動による動的粘弾性試験を行うことで測定される２０℃における損失正接ｔａｎδが０．３以上である、上記［１］～［９］のいずれか一つに記載の制振材。
［１１］制振層（ＡＬ）の厚さＨ（ＡＬ）が０．３ｍｍ以下である、上記［１］～［１０］のいずれか一つに記載の制振材。
［１２］熱可塑性樹脂組成物（ＢＣ）の、ＪＩＳ Ｋ７２４４－４（１９９９年）に準じて、歪み量０．２％、周波数１０Ｈｚの条件で引張振動による動的粘弾性試験を行うことで測定される２０℃における引張貯蔵弾性率Ｅ’（ＢＣ）が１，０００ＭＰａ以上である、上記［１］～［１１］のいずれか一つに記載の制振材。
［１３］ＪＩＳ Ｋ７２４４－４（１９９９年）に準じて、歪み量０．２％、周波数１０Ｈｚの条件で引張振動による動的粘弾性試験を行うことで測定される２０℃における熱可塑性樹脂組成物（ＢＣ）の損失弾性率Ｅ’’（ＢＣ）が１０ＭＰａ以上である、上記［１］～［１２］のいずれか一つに記載の制振材。
［１４］熱可塑性樹脂組成物（ＢＣ）がオレフィン系樹脂及びポリアミド樹脂のうち少なくとも一方を含む、上記［１］～［１３］のいずれか一つに記載の制振材。
［１５］拘束層（ＢＬ）の厚さＨ（ＢＬ）が０．４ｍｍ以上である、上記［１］～［１４］のいずれか一つに記載の制振材。
［１６］それぞれ、ＪＩＳ Ｋ７２４４－４（１９９９年）に準じて、歪み量０．２％、周波数１０Ｈｚの条件で引張振動による動的粘弾性試験を行うことで測定される２０℃における、熱可塑性組成物（ＡＣ）の引張貯蔵弾性率Ｅ’（ＡＣ）及び熱可塑性組成物（ＢＣ）の引張貯蔵弾性率Ｅ’（ＢＣ）が、Ｅ’（ＢＣ）／Ｅ’（ＡＣ）≧５０の関係を満たす、上記［１］～［１５］のいずれか一つに記載の制振材。
［１７］制振層（ＡＬ）の厚さＨ（ＡＬ）に対する拘束層（ＢＬ）の厚さＨ（ＢＬ）の比Ｈ（ＢＬ）／Ｈ（ＡＬ）が８～１００である、上記［１］～［１６］のいずれか一つに記載の制振材。
［１８］制振層（ＡＬ）が拘束層（ＢＬ）とともに共押出しされた層である、上記［１］～［１７］のいずれか一つに記載の制振材。
［１９］制振層（ＡＬ）と拘束層（ＢＬ）とを熱融着してなる、上記［１］～［１７］のいずれか一つに記載の制振材。
［２０］上記［１］～［１９］のいずれか一つに記載の制振材の製造方法であって、制振層（ＡＬ）と拘束層（ＢＬ）とを共押出して形成することにより前記制振材を製造する、制振材の製造方法。
［２１］上記［１］～［１９］のいずれか一つに記載の制振材の製造方法であって、制振層（ＡＬ）と拘束層（ＢＬ）をそれぞれ成形した後に積層して熱融着することにより前記制振材を製造する、制振材の製造方法。
［２２］上記［１］～［１９］のいずれか一つに記載の制振材と、該制振材に積層された金属板とを含む、積層体。
［２３］上記［１］～［１９］のいずれか一つに記載の制振材を金属板に貼付して前記金属板の制振性を高める、制振性向上方法。 The present invention relates to the following [1] to [23].
[1] A vibration damping material including a vibration damping layer (AL) and a restraining layer (BL) laminated on the vibration damping layer (AL).
The anti-vibration layer (AL) comprises a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) containing a structural unit derived from a conjugated diene compound. It is composed of a thermoplastic resin composition (AC) containing the block copolymer (A) having the block copolymer (A).
The restraint layer (BL) is made of a thermoplastic resin composition (BC), and the restraint layer (BL) is made of a thermoplastic resin composition (BC).
A damping material that satisfies the following conditions (1) to (3).
(1) The glass transition temperature of the thermoplastic resin composition (AC) is −40 to + 30 ° C.
(2) At least one of the glass transition temperature and the melting point of the thermoplastic resin composition (BC) is 100 ° C. or higher.
(3) The ratio H (BL) / H (AL) of the thickness H (BL) of the restraint layer (BL) to the thickness H (AL) of the vibration damping layer (AL) is 3 to 200.
[2] The vibration damping material according to the above [1], wherein the glass transition temperature of the block copolymer (A) is −40 to + 30 ° C.
[3] The vibration damping material according to the above [1] or [2], wherein the content of the polymer block (A-1) in the block copolymer (A) is 22% by mass or less.
[4] The vibration damping material according to any one of the above [1] to [3], wherein the block copolymer (A) has a weight average molecular weight of 30,000 to 200,000.
[5] The block copolymer (A) is a hydrogenated additive, and the hydrogenation rate of the polymer block (A-2) is 85 mol% or more, any one of the above [1] to [4]. Anti-vibration material described in.
[6] The polymer block (A-2) in the block copolymer (A) has a structural unit having one or more alicyclic skeletons (X) represented by the following formula (X) in the main chain. The damping material according to any one of the above [1] to [5].

(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 from each other.)
[7] The vibration damping material according to the above [6], wherein the alicyclic skeleton (X) contains an alicyclic skeleton (X') in which at least one of R ¹ to R ³ is a methyl group.
[8] The vibration damping material according to the above [6] or [7], wherein the polymer block (A-2) contains 1 mol% or more of the alicyclic skeleton (X) or (X').
[9] The thermoplastic composition (AC) was measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7244-4 (1999). The vibration damping material according to any one of the above [1] to [8], wherein the tensile storage elastic modulus E'(AC) at 20 ° C. is 100 MPa or less.
[10] Measured by performing a dynamic viscoelasticity test of a thermoplastic composition (AC) by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7244-4 (1999). The vibration damping material according to any one of the above [1] to [9], wherein the loss positive contact tan δ at 20 ° C. is 0.3 or more.
[11] The vibration damping material according to any one of the above [1] to [10], wherein the thickness H (AL) of the vibration damping layer (AL) is 0.3 mm or less.
[12] Measured by performing a dynamic viscoelasticity test of a thermoplastic resin composition (BC) by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The vibration damping material according to any one of the above [1] to [11], wherein the tensile storage elastic modulus E'(BC) at 20 ° C. is 1,000 MPa or more.
[13] A thermoplastic resin composition at 20 ° C. measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7244-4 (1999). The vibration damping material according to any one of the above [1] to [12], wherein the loss elastic modulus E'' (BC) of (BC) is 10 MPa or more.
[14] The vibration damping material according to any one of the above [1] to [13], wherein the thermoplastic resin composition (BC) contains at least one of an olefin resin and a polyamide resin.
[15] The damping material according to any one of the above [1] to [14], wherein the thickness H (BL) of the restraint layer (BL) is 0.4 mm or more.
[16] Thermoplasticity at 20 ° C. measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz, respectively, according to JIS K7244-4 (1999). The relationship between the tensile storage elastic modulus E'(AC) of the composition (AC) and the tensile storage elastic modulus E'(BC) of the thermoplastic composition (BC) is E'(BC) / E'(AC) ≥ 50. The vibration damping material according to any one of the above [1] to [15], which satisfies the above conditions.
[17] The ratio H (BL) / H (AL) of the thickness H (BL) of the restraining layer (BL) to the thickness H (AL) of the damping layer (AL) is 8 to 100, as described above [1]. ] To [16]. The damping material according to any one of.
[18] The vibration damping material according to any one of the above [1] to [17], wherein the vibration damping layer (AL) is a layer co-extruded together with the restraining layer (BL).
[19] The vibration damping material according to any one of the above [1] to [17], which is formed by heat-sealing the vibration damping layer (AL) and the restraining layer (BL).
[20] The method for producing a damping material according to any one of the above [1] to [19], wherein the damping layer (AL) and the restraining layer (BL) are coextruded to form the damping material. A method for manufacturing a vibration damping material, which manufactures the vibration damping material.
[21] The method for manufacturing a vibration damping material according to any one of the above [1] to [19], in which the vibration damping layer (AL) and the restraining layer (BL) are respectively molded and then laminated to generate heat. A method for manufacturing a vibration damping material, which manufactures the vibration damping material by fusing.
[22] A laminated body including the vibration damping material according to any one of the above [1] to [19] and a metal plate laminated on the vibration damping material.
[23] A method for improving vibration damping property, wherein the vibration damping material according to any one of the above [1] to [19] is attached to a metal plate to improve the vibration damping property of the metal plate.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a vibration damping material which is excellent in vibration damping property and light weight and can easily obtain a restraint type laminated body, a method for producing the same, and a laminated body using the same.

It is a schematic cross-sectional view which shows an example of a vibration damping material and a laminated body. It is a schematic sectional drawing which shows the other example of a vibration damping material and a laminated body.

Hereinafter, embodiments of the present invention will be described.
Aspects in which the matters described in the present specification are arbitrarily selected or arbitrarily combined are also included in the present invention.
In the present specification, the preferred provisions can be arbitrarily selected, and it can be said that the combination of the preferred provisions is more preferable.
In the present specification, the description "XX to YY" means "XX or more and YY or less".
In the present specification, the lower limit value and the upper limit value described in stages can be independently combined with respect to a preferable numerical range (for example, a range such as content). For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to form "10 to 60". You can also.

[Damping material]
The vibration damping material according to the embodiment of the present invention is a vibration damping material including a vibration damping layer (AL) and a restraining layer (BL) laminated on the vibration damping layer (AL).
The anti-vibration layer (AL) comprises a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) containing a structural unit derived from a conjugated diene compound. It is composed of a thermoplastic resin composition (AC) containing the block copolymer (A) having the block copolymer (A).
The restraint layer (BL) is made of a thermoplastic resin composition (BC), and the restraint layer (BL) is made of a thermoplastic resin composition (BC).
The following conditions (1) to (3) are satisfied.
(1) The glass transition temperature of the thermoplastic resin composition (AC) is −40 to + 30 ° C.
(2) At least one of the glass transition temperature and the melting point of the thermoplastic resin composition (BC) is 100 ° C. or higher.
(3) The ratio H (BL) / H (AL) of the thickness H (BL) of the restraint layer (BL) to the thickness H (AL) of the vibration damping layer (AL) is 3 to 200.

By satisfying the condition (1), the thermoplastic resin composition (AC) has appropriate viscoelastic properties (for example, tensile storage elastic modulus and loss tangent), so that the vibration damping layer (AL) has high vibration damping properties. Express.
Further, by satisfying the condition (2), the thermoplastic resin composition (BC) generally has good mechanical properties (for example, tensile storage elastic modulus and loss elastic modulus), so that the mechanical properties of the restraint layer (BL) are improved. It gets higher.
Further, by satisfying the condition (3), the restraint layer (BL) becomes sufficiently thicker than the vibration damping layer (AL), and is lightweight but has sufficient rigidity.
Therefore, by satisfying the above conditions (1) to (3), the vibration damping material can be made excellent in vibration damping property and light weight, and the vibration damping material can be attached to a metal plate such as a steel plate. , A restraint type laminate having a structure of "metal plate / vibration damping layer (AL) / restraint layer (BL)" having excellent vibration damping properties and light weight can be easily produced.

FIG. 1 is a schematic cross-sectional view showing an example of a damping material and a laminated body. Further, FIG. 2 is a schematic cross-sectional view showing another example of the damping material and the laminated body. An example of a specific configuration of the damping material and the laminated body will be described with reference to FIGS. 1 and 2. The present invention is not limited to those shown in FIGS. 1 and 2.
The vibration damping material 100 shown in FIG. 1A includes a vibration damping layer (AL) and a restraining layer (BL) laminated on the vibration damping layer (AL).
By attaching the surface of the vibration damping material 100 opposite to the restraining layer (BL) (that is, the vibration damping layer (AL)) to a metal plate such as a steel plate which is an object, "metal plate / damping layer". It is possible to obtain a restraint type laminated body having a structure of "(AL) / restraint layer (BL)".
Since the restraining layer (BL) is made of the thermoplastic resin composition (BC), it can be a lightweight damping material. Further, since the vibration damping material is lightweight, the production of the laminated body becomes easier as compared with the production of the restrictive type vibration damping steel plate having the structure of "steel plate / vibration damping layer / steel plate".

The laminated body 200 shown in FIG. 1 (B) includes the vibration damping material 100 shown in FIG. 1 (A) and the metal plate 10.
As described above, the laminated body 200 is obtained by attaching the surface (that is, the vibration damping layer (AL)) opposite to the restraining layer (BL) of the vibration damping material 100 to the metal plate 10.
Since the laminated body 200 has a restraint type structure of "metal plate / vibration damping layer (AL) / restraint layer (BL)", it has high vibration damping properties. In addition, since the restraint layer (BL) is made of the thermoplastic resin composition (BC), the laminated body is lighter than the vibration-damping steel plate having the structure of "steel plate / vibration-damping layer / steel plate". Can be.

The vibration damping material according to the embodiment of the present invention may have a structure in which a restraining layer (BL) and a vibration damping layer (AL) are repeatedly laminated.
The damping material 101 shown in FIG. 2A has a first damping layer (BL1), a first damping layer (AL1), a second damping layer (BL2), and a second damping layer (AL2). , And the third restraint layer has a structure laminated in this order.
By attaching the first restraining layer (BL1) or the third restraining layer (BL3) of the vibration damping material 101 to a metal plate such as a steel plate which is an object, "metal plate / restraining layer (BL1) / damping". It is possible to obtain a constrained laminate having a structure of "vibration layer (AL1) / restraint layer (BL2) / vibration damping layer (AL2) / restraint layer (BL3)".
One of the first restraint layer (BL1) and the third restraint layer (BL3) located on the outermost side may have a structure in which one is omitted. In this case, the first vibration damping layer (AL1) or the third vibration damping layer (AL3) located on the outermost side may be attached to the metal plate 10.
The damping material may have a structure in which the restraining layer (BL) and the damping layer (AL) are repeatedly laminated three or more times.
By forming the damping material with a structure in which a restraining layer (BL) and a damping layer (AL) are repeatedly laminated, the vibration damping property and mechanical strength of the damping material can be improved, and the number of repetitions of stacking can be changed. This makes it possible to adjust the vibration damping property and mechanical strength of the damping material.

The laminated body 201 shown in FIG. 2B includes the damping material 101 shown in FIG. 2A and the metal plate 10.
The laminated body 201 is obtained by attaching the first restraining layer (BL1) of the vibration damping material 101 to the metal plate 10. As described above, the third restraint layer (BL3) may be attached to the metal plate 10.
Since the laminated body 201 has a structure in which the restraint layer (BL) and the vibration damping layer (AL) are repeatedly laminated, it becomes easier to improve the vibration damping property. Further, since the restraint layer (BL) is made of the thermoplastic resin composition (BC) and the repeating unit composed of the restraint layer (BL) and the vibration damping layer (AL) can be made lighter, the laminated body can be made lightweight. Vibration damping can be improved while suppressing weight increase.

The damping material may be provided with a protective layer. Specifically, at least one surface of the surface of the damping layer (AL) and the restraining layer (BL) of the damping material 100 of FIG. 1, the restraining layer (BL1) and the restraining layer of the damping material 101 of FIG. A protective layer may be provided on at least one surface of (BL3). By providing the protective layer, it is possible to protect the vibration damping layer (AL) and the restraining layer (BL) of the vibration damping material before being attached to the metal plate from the external environment and external objects. Of the above protective layers, the protective layer located on the side surface to be attached to the metal plate may be peeled off and removed before being attached to the metal plate. Further, among the above-mentioned protective layers, the protective layer located on the surface on the side to be attached to the metal plate may be peeled off and removed at any timing before, at the time of attachment, or after attachment to the metal plate.
Hereinafter, each layer constituting the damping material and the laminated body will be specifically described.

<Damping layer (AL)>
The vibration damping layer (AL) comprises a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) containing a structural unit derived from a conjugated diene compound. It comprises a thermoplastic resin composition (AC) containing the block copolymer (A) having.
The vibration damping layer (AL) is a layer having a function of imparting vibration damping property in a restraint type laminated body obtained by attaching a vibration damping material to a metal plate. Further, the vibration damping layer (AL) is a layer made of a material different from the restraining layer (BL) and having at least a higher vibration damping property than the restraining layer (BL).

The thermoplastic resin composition (AC) constituting the vibration damping layer (AL) may be composed of the block copolymer (A) alone, or may be composed of only the block copolymer (A) and other resin components. However, it may contain various additives in addition to these resin components. The components other than the resin component that can be contained in the thermoplastic resin composition (AC) will be described later.

The thickness H (AL) of the vibration damping layer (AL) is preferably 0.3 mm or less, more preferably 0.25 mm or less, still more preferably 0.15 mm or less, and more preferably 0.15 mm or less, from the viewpoint of the mechanical properties of the laminated body. From the viewpoint of ensuring sufficient vibration damping properties, it is preferably 0.01 mm or more, more preferably 0.02 mm or more, still more preferably 0.03 mm or more. In other words, the thickness H (AL) of the vibration damping layer (AL) is preferably 0.01 to 0.3 mm from the viewpoint of achieving both the vibration damping property and the mechanical characteristics of the laminated body.

The damping layer (AL) can be a coextruded layer together with the restraining layer (BL), as will be described later.
Further, as will be described later, the vibration damping layer (AL) and the restraining layer (BL) may be heat-sealed.

(Thermoplastic Resin Composition (AC))
The thermoplastic resin composition (AC) constituting the vibration damping layer (AL) contains a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound. It contains a block copolymer (A) having a polymer block (A-2) to be used.
The thermoplastic resin composition (AC) is a composition of a different type from the thermoplastic resin composition (BC), and has at least higher vibration damping property than the thermoplastic resin composition (BC). The thermoplastic resin composition (AC) may be composed of the block copolymer (A) alone, or may contain a resin component other than the block copolymer (A). Resin components other than the block copolymer (A) will be described later.
As specified in the above condition (1), the glass transition temperature Tg of the thermoplastic resin composition (AC) is −40 to + 30 ° C.
When the Tg of the thermoplastic resin composition (AC) is in the above range, the thermoplastic resin composition (AC) has appropriate viscoelastic properties (for example, tensile storage elastic modulus and loss tangent). Therefore, the vibration damping layer (AL) exhibits high vibration damping properties.
The Tg of the thermoplastic resin composition (AC) is preferably −35 to + 25 ° C., more preferably −30 to + 20 ° C., still more preferably −20 to + 15 ° C. from the viewpoint of facilitating the securing of appropriate viscoelastic properties. Is. Further, from the viewpoint of improving the vibration damping property at a high temperature, the temperature is preferably −10 to + 30 ° C, more preferably −5 to + 30 ° C, and further preferably 0 to + 30 ° C.
The glass transition temperature of the thermoplastic resin composition (AC) is, for example, the vinyl bond amount of the conjugated diene of the polymer block (A-2) in the block copolymer (A) contained in the thermoplastic resin composition (AC). Can be set to the above range by controlling the value to an appropriate value.
In the present specification, the Tg of the thermoplastic resin composition (AC) is the temperature at which the baseline shift occurs in the DSC curve created by using a differential scanning calorimeter (DSC). In particular, it is measured by the method described in the examples. Even when the thermoplastic resin composition (AC) contains an infusible additive among the additives described later, the temperature measured by the above method is defined as Tg of the thermoplastic resin composition (AC).

The thermoplastic resin composition (AC) is measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999) 20. The tensile storage elastic modulus E'(AC) at ° C. is preferably 800 MPa or less, more preferably 300 MPa or less, still more preferably 100 MPa or less, particularly preferably 50 MPa or less, and a laminated body, from the viewpoint of ensuring vibration damping. From the viewpoint of improving the mechanical properties of the above, it is preferably 1 MPa or more, more preferably 3 MPa or more, and further preferably 5 MPa or more. In other words, the tensile storage elastic modulus E'(AC) of the thermoplastic resin composition (AC) is preferably 1 to 800 MPa.
The tensile storage elastic modulus E'of the thermoplastic resin composition (AC) is, for example, the content of the polymer block (A-1) in the block copolymer (A) contained in the thermoplastic resin composition (AC). By controlling to an appropriate value, the above range can be obtained.

20 ° C. of the thermoplastic composition (AC) measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The loss tangent tan δ in the above is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, particularly preferably 0.4 or more, and the dynamics, from the viewpoint of ensuring vibration damping. From the viewpoint of achieving both physical properties and vibration damping properties, it is preferably 3.0 or less, more preferably 2.5 or less, and further preferably 2.0 or less. In other words, the tan δ of the thermoplastic resin composition (AC) is preferably 0.1 to 3.0.

The tensile storage elastic modulus E'and tan δ of the thermoplastic resin composition (AC) can be in the above ranges, for example, by setting the Tg of the thermoplastic resin composition (AC) to the above range. ..

Next, the components of the block copolymer (A) contained in the thermoplastic resin composition (AC), the physical properties of the block copolymer (A), the method for producing the block copolymer (A), and the like will be described in detail. ..

(Block Copolymer (A))
The block copolymer (A) is a block copolymer having a polymer block (A-1) and a polymer block (A-2), and is preferably a hydrogenated additive of the block copolymer. In the present specification, the hydrogenated block copolymer may also be referred to as "hydrogenated block copolymer".
The block copolymer (A) contained in the thermoplastic resin composition (AC) is a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a structural unit derived from a conjugated diene compound. It has a polymer block (A-2) containing.

The block copolymer (A) or its hydrogenated Tg is preferably −40 to + 30 ° C., more preferably −35 to + 25 ° C., and even more preferably −, from the viewpoint of facilitating the development of appropriate viscoelastic properties. It is 30 to + 20 ° C, more preferably −20 to + 15 ° C. Further, from the viewpoint of improving the vibration damping property at a high temperature, the temperature is preferably −10 to + 30 ° C, more preferably −5 to + 30 ° C, and further preferably 0 to + 30 ° C.
The Tg of the block copolymer (A) or its hydrogenated product is, for example, by controlling the vinyl bond amount of the conjugated diene of the polymer block (A-2) in the block copolymer (A) to an appropriate value. , Can be in the above range.

(Polymer block (A-1))
The polymer block (A-1) contains a structural unit derived from an aromatic vinyl compound (hereinafter, may be abbreviated as “aromatic vinyl compound unit”), and is preferably 70 mol from the viewpoint of mechanical properties. %, More preferably 80 mol% or more, still more preferably 85 mol% or more, still more preferably 90 mol% or more, particularly preferably 95 mol% or more, and may be substantially 100 mol%.

Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, and 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, mt-butylstyrene, pt-butylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-bromo Examples thereof include methylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, styrene derivatives substituted with a silyl group, inden, vinylnaphthalene and the like. These aromatic vinyl compounds may be used alone or in combination of two or more. Among them, styrene, α-methylstyrene, p-methylstyrene, and a mixture thereof are preferable, and styrene is more preferable, from the viewpoint of manufacturing cost and physical property balance.

However, the polymer block (A-1) is a structural unit derived from an unsaturated monomer other than the aromatic vinyl compound (hereinafter, “other unsaturated monomer”, as long as it does not interfere with the object and effect of the present invention. It may be contained in a proportion of less than 30 mol%) (which may be abbreviated as "polymer unit"). Examples of the other unsaturated monomer include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutylene, methyl methacrylate, methyl vinyl ether, N-vinylcarbazole, and β. Included is at least one selected from the group consisting of -pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylenetetrakane and the like. When the polymer block (A-1) contains the other unsaturated monomer unit, the bonding form is not particularly limited and may be random or tapered.
The content of the structural unit derived from the other unsaturated monomer in the polymer block (A-1) is preferably 10 mol% or less, more preferably 5 mol% or less, still more preferably 0 mol%. ..

The block copolymer (A) may have at least one of the above-mentioned polymer blocks (A-1). When the block copolymer (A) has two or more polymer blocks (A-1), the polymer blocks (A-1) may be the same or different. In addition, in this specification, "the polymer block is different" means the monomer unit constituting the polymer block, the weight average molecular weight, the stereoregularity, and the ratio and the copolymer of each monomer unit when having a plurality of monomer units. It means that at least one of the forms of polymerization (random, gradient, block) is different.
The block copolymer (A) preferably has two polymer blocks (A-1).

The weight average molecular weight (Mw) of the polymer block (A-1) is not particularly limited, but at least one polymer block among the polymer blocks (A-1) contained in the block copolymer (A). The weight average molecular weight of (A-1) is preferably 3,000 to 60,000, more preferably 4,000 to 50,000. When the block copolymer (A) has at least one polymer block (A-1) having a weight average molecular weight within the above range, the mechanical strength is further improved and the film formability is also excellent.

In addition, all the "weight average molecular weights" described in this specification and claims are standard polystyrene-equivalent weight average molecular weights obtained by gel permeation chromatography (GPC) measurement, and detailed measurement methods are described in Examples. You can follow the method described. The weight average molecular weight of each polymer block possessed by the block copolymer (A) can be determined by measuring the sampled liquid each time the polymerization of each polymer block is completed in the manufacturing process. Further, for example, when two types of polymer blocks (A-1) are represented by "A1" and "A2" and one type of polymer block (A-2) is represented by "B", A1-B-A2. In the case of a triblock copolymer having a structure, the weight average molecular weights of the polymer block "A1" and the polymer block "B" are obtained by the above method, and they are subtracted from the weight average molecular weight of the block copolymer. , The weight average molecular weight of the polymer block "A2" can be obtained. As another method, in the case of the triblock copolymer having the above A1-B-A2 structure, the total weight average molecular weight of the polymer blocks "A1" and "A2" is the weight average of the block copolymer. Calculated from the molecular weight and the total content of the polymer blocks "A1" and "A2" confirmed by ¹ H-NMR measurement, and the weight average molecular weight of the first deactivated polymer block "A1" is calculated by GPC measurement. By subtracting this, the weight average molecular weight of the polymer block "A2" can also be obtained.

The content of the polymer block (A-1) in the block copolymer (A) (in the case of having a plurality of polymer blocks (A-1), the total content thereof) is preferable from the viewpoint of vibration damping. Is 22% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less, and from the viewpoint of mechanical properties, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably. It is 7% by mass or more. In other words, the content of the polymer block (A-1) in the block copolymer (A) is preferably 3 to 22% by mass.
The content of the polymer block (A-1) in the block copolymer (A) is a value obtained by ¹ H-NMR measurement, and more specifically, a value measured according to the method described in Examples. be.

(Polymer block (A-2))
The polymer block (A-2) contains a structural unit derived from the conjugated diene compound (hereinafter, may be abbreviated as “conjugated diene compound unit”). From the viewpoint of vibration damping and thermal stability, the content of the conjugated diene compound unit of the polymer block (A-2) is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 65 mol%. Above, more preferably 80 mol% or more, particularly preferably 90 mol% or more, and most preferably substantially 100 mol% is contained.
The above-mentioned "conjugated diene compound unit" may be a structural unit derived from one kind of conjugated diene compound or a structural unit derived from two or more kinds of conjugated diene compounds.

The conjugated diene compound preferably contains isoprene, or isoprene and butadiene, from the viewpoint of achieving both excellent vibration damping properties and thermal stability. Further, as the conjugated diene compound, a conjugated diene compound other than isoprene and butadiene may be contained as described later. On the other hand, from the viewpoint of facilitating the development of excellent vibration damping properties and thermal stability, the content of isoprene in the conjugated diene compound is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass. % Or more, more preferably 55% by mass or more, still more preferably 75% by mass or more, particularly preferably 100% by mass, that is, it is particularly preferable to use isoprene as the conjugated diene compound.

When the conjugated diene compound is a mixture of butadiene and isoprene, the mixing ratio [isoprene / butadiene] (mass ratio) is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 5/95. It is ~ 95/5, more preferably 10/90 to 90/10, still more preferably 40/60 to 70/30, and particularly preferably 45/55 to 65/35. When the mixing ratio [isoprene / butadiene] is shown in molar ratio, it is preferably 5/95 to 95/5, more preferably 10/90 to 90/10, still more preferably 40/60 to 70/30, and particularly. It is preferably 45/55 to 55/45.

Examples of the conjugated diene compound include hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, myrcene and the like, in addition to the above-mentioned isoprene and butadiene. The conjugated diene compound may be used alone or in combination of two or more.

Further, the polymer block (A-2) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound, as long as it does not interfere with the object and effect of the present invention. In this case, the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound in the polymer block (A-2) is preferably less than 70 mol%, more preferably less than 50 mol%. , More preferably less than 35 mol%, particularly preferably less than 20 mol%. The lower limit of the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound is not particularly limited, but may be 0 mol% or 5 mol%. It may be 10 mol%.

Examples of the other polymerizable monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, and vinyl. Aromatic vinyl compounds such as naphthalene and vinylanthracene, as well as methyl methacrylate, methylvinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylenetetrakelate, 1,3- Preferred are at least one compound selected from the group consisting of cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene and the like. Of these, styrene, α-methylstyrene, and p-methylstyrene are preferable, and styrene is more preferable.

Further, the block copolymer (A) may have at least one polymer block (A-2). When the block copolymer (A) has two or more polymer blocks (A-2), the polymer blocks (A-2) may be the same or different. When the polymer block (A-2) has two or more structural units, the bonding form thereof is random, tapered, completely alternating, partially blocked, blocked, or two or more of them. It may consist of a combination.

The binding form of the conjugated diene compound is not particularly limited as long as the object and effect of the present invention are not impaired. For example, when the structural unit constituting the polymer block (A-2) is any one of an isoprene unit and a mixture unit of isoprene and butadiene, the bonding form of isoprene and butadiene is 1, in the case of butadiene. In the case of 2-bond, 1,4-bond, and isoprene, 1,2-bond, 3,4-bond, and 1,4-bond vinyl bonds can be taken. Only one of these binding forms may be present, or two or more thereof may be present.

（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。）
上記炭化水素基の炭素数は、好ましくは炭素数１～５であり、より好ましくは１～３であり、更に好ましくは１（すなわち、メチル基）である。
また、上記炭化水素基は、直鎖又は分岐鎖であってもよく、飽和又は不飽和炭化水素基であってもよい。物性及び脂環式骨格（Ｘ）形成の観点から、Ｒ^１～Ｒ^３は、それぞれ独立に水素原子又はメチル基であることが特に好ましい。 The polymer block (A-2) is a structural unit derived from a conjugated diene compound, and contains one or more alicyclic skeletons (X) represented by the following formula (X) in the main chain. You may have.

(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 from each other.)
The hydrocarbon group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and further preferably 1 (that is, a methyl group).
Further, the hydrocarbon group may be a linear or branched chain, or may be a saturated or unsaturated hydrocarbon group. From the viewpoint of physical properties and formation of the alicyclic skeleton (X), it is particularly preferable that R ¹ to R ³ are independently hydrogen atoms or methyl groups, respectively.

From the viewpoint of improving vibration damping property, the alicyclic skeleton (X) may contain an alicyclic skeleton (X') in which at least one of R ¹ to R ³ is a methyl group.

From the viewpoint of improving vibration damping, the content of the alicyclic skeleton (X) or (X') in the polymer block (A-2) is preferably 1 mol% or more, more preferably 1.1 mol. % Or more, more preferably 1.4 mol% or more, still more preferably 1.8 mol% or more, still more preferably 4 mol% or more, still more preferably 10 mol% or more, particularly preferably 13 mol% or more. be. The upper limit of the content of the alicyclic skeleton (X) or (X') in the polymerization block (A-2) is not particularly limited as long as the effect of the present invention is not impaired, but the productivity is limited. From the viewpoint of the above, it is preferably 40 mol% or less, 30 mol% or less, 20 mol% or less, and 18 mol% or less. In other words, the content of the alicyclic skeleton (X) or (X') in the polymer block (A-2) is preferably 1 to 40 mol%.

As will be described later, the alicyclic skeleton (X) is produced by anionic polymerization of a conjugated diene compound, and at least one alicyclic skeleton (X) is an alicyclic skeleton-containing unit depending on the conjugated diene compound used. Introduced to the main chain. Since the alicyclic skeleton (X) is incorporated in the main chain of the structural unit contained in the polymer block (A-2), the molecular motion is reduced and the glass transition temperature rises, and tan δ near room temperature. The peak top intensity of is increased, and it becomes easy to develop excellent vibration damping properties.

As a specific example, an alicyclic skeleton (X) mainly produced when butadiene, isoprene, or a combination of butadiene and isoprene is used as the conjugated diene compound will be described.
When butadiene is used alone as the conjugated diene compound, an alicyclic skeleton (X) having the following combination of substituents (i) is produced. That is, in this case, the alicyclic skeleton (X) is only an alicyclic skeleton in which R ¹ to R ³ are hydrogen atoms at the same time. Therefore, the polymer block (A-2) has a structural unit having one kind of alicyclic skeleton (X) in which R ¹ to R ³ are hydrogen atoms at the same time in the main chain, or a block copolymer or hydrogen thereof. Additives can be obtained.
When isoprene is used alone as the conjugated diene compound, two kinds of alicyclic skeletons (X) having the following combinations of substituents (v) and (vi) are mainly produced.
When butadiene and isoprene are used in combination as the conjugated diene compound, six kinds 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 Atomic, R ² = Hydrogen atom, R ³ = Methyl group (iv): R ¹ = Methyl group, R ² = Hydrogen atom, R ³ = Hydrogen atom (v): R ¹ = Methyl group, R ² = Methyl group, R ³ = hydrogen atom (vi): R ¹ = methyl group, R ² = hydrogen atom, R ³ = methyl group

In particular, it is more preferable that R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and R ¹ to R ³ are alicyclic skeletons that are not hydrogen atoms at the same time. That is, the polymer block (A-2) may have a structural unit containing at least one of the alicyclic skeletons having the combination of the substituents (ii) to (vi) above in the main chain. More preferred.

When the block copolymer (A) is hydrogenated, the vinyl group in the above formula (X) can be hydrogenated to form a hydrogenated product. Therefore, the meaning of the alicyclic skeleton (X) in the hydrogenated substance also includes the skeleton in which the vinyl group in the above formula (X) is hydrogenated.
The content of the alicyclic skeleton (X) contained in the block copolymer (A) or its hydrogenated additive was determined by measuring the block copolymer (A) with ¹³ C-NMR. -2) It is a value obtained from the integrated value derived from the alicyclic skeleton (X) in.

(Amount of vinyl bond in polymer block (A-2))
When the structural unit constituting the polymer block (A-2) is any one of an isoprene unit and a mixture unit of isoprene and butadiene, the bonding form of isoprene and butadiene is 1,2- in the case of butadiene. Bonds and 1,4-bonds can be taken, and in the case of isoprene, 1,2-bonds, 3,4-bonds and 1,4-bonds can be taken.
In the block copolymer (A), the total content of the 3,4-bonding unit and the 1,2-bonding unit (that is, the vinyl bond amount) in the polymer block (A-2) is the vibration damping property. From the viewpoint, it is preferably 35 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, still more preferably 60 mol% or more. Further, although not particularly limited, the upper limit of the vinyl bond amount in the polymer block (A-2) may be 95 mol%, 92 mol%, or 90. It may be mol%. In other words, the amount of vinyl bond in the polymer block (A-2) is preferably 35 to 95 mol%. Here, the vinyl bond amount is a value calculated by ¹ H-NMR measurement according to the method described in Examples.

The total weight average molecular weight of the polymer block (A-2) contained in the block copolymer (A) is preferably 15,000 to 800,000 in the state before hydrogenation from the viewpoint of vibration damping and the like. It is more preferably 20,000 to 400,000, still more preferably 20,000 to 300,000, particularly preferably 30,000 to 300,000, and most preferably 40,000 to 300,000.

The polymer block (A-2) may contain a structural unit derived from a polymerizable monomer other than the conjugated diene compound as long as it does not interfere with the object and effect of the present invention. In this case, the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound in the polymer block (A-2) is preferably 70 mol% or less, more preferably 50 mol% or less. Below, it is more preferably 35 mol% or less, and particularly preferably 20 mol% or less. The lower limit of the content of the structural unit derived from the polymerizable monomer other than the conjugated diene compound is not particularly limited, but may be 0 mol% or 5 mol%. It may be 10 mol%.
Examples of the other polymerizable monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pt-butylstyrene, 2,4-dimethylstyrene, and vinyl. Aromatic vinyl compounds such as naphthalene and vinylanthracene, as well as methyl methacrylate, methylvinyl ether, N-vinylcarbazole, β-pinene, 8,9-p-mentene, dipentene, methylenenorbornene, 2-methylenetetrakelate, 1,3- Preferred are at least one compound selected from the group consisting of cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene and the like. Of these, styrene, α-methylstyrene, and p-methylstyrene are preferable, and styrene is more preferable.
When the polymer block (A-2) contains a structural unit derived from a polymerizable monomer other than the conjugated diene compound, the bonding form thereof is not particularly limited and may be random or tapered. However, random is preferable.

The block copolymer (A) may have at least one of the above-mentioned polymer blocks (A-2). When the block copolymer (A) has two or more polymer blocks (A-2), the polymer blocks (A-2) may be the same or different.
The block copolymer (A) preferably has only one of the above-mentioned polymer blocks (A-2).

In the block copolymer (A) contained in the thermoplastic resin composition (AC), it is desirable that the polymer block (A-2) does not contain a structural unit derived from an aromatic vinyl compound. If the polymer block (A-2) contains a structural unit derived from an aromatic vinyl compound, the vibration damping property may decrease.

(Combination mode of polymer block (A-1) and polymer block (A-2))
As long as the polymer block (A-1) and the polymer block (A-2) are bonded to each other, the block copolymer (A) is not limited in its bonding form, and is linear, branched, or linear. It can be either radial or a combination of two or more of these. Above all, the bonding form of the polymer block (A-1) and the polymer block (A-2) is preferably linear, and as an example, the polymer block (A-1) is designated as "A". Further, when the polymer block (A-2) is represented by "B", the diblock copolymer represented by AB or the triblock copolymer represented by ABA or BAB is used. , ABAB, tetrablock copolymers, ABABA or BABAB, pentablock copolymers, (AB). Examples thereof include nX-type copolymers (X represents a coupling agent residue and n represents an integer of 3 or more). Of these, linear triblock copolymers or diblock copolymers are preferable, and ABA type triblock copolymers are preferably used from the viewpoints of flexibility, ease of production, and the like.
Here, in the present specification, when the same type of polymer block is linearly bonded via a bifunctional coupling agent or the like, the entire bonded polymer block is treated as one polymer block. Is done. Accordingly, including the above examples, the polymer block, which should be strictly described as Y-XY (where X represents a coupling residue), needs to be particularly distinguished from the single polymer block Y. Except in certain cases, it is displayed as Y as a whole. In the present specification, since this kind of polymer block containing a coupling agent residue is treated as described above, for example, it contains a coupling agent residue, and strictly speaking, ABXXBA ( The block copolymer to be described as (X represents a coupling agent residue) is described as ABA and is treated as an example of a triblock copolymer.

The block copolymer (A) is preferably a hydrogenated agent. The hydrogenation rate of the polymer block (A-2) is preferably 85 mol% or more. That is, it is preferable that 85 mol% or more of the carbon-carbon double bond of the polymer block (A-2) is hydrogenated.
When the hydrogenation rate of the polymer block (A-2) is high, it is excellent in vibration damping property, heat resistance and weather resistance in a wide range of temperatures. From the same viewpoint, the hydrogenation rate of the polymer block (A-2) is more preferably 87 mol% or more, more preferably 88 mol% or more, still more preferably 89 mol% or more, and particularly preferably 90 mol% or more. Is. The value may be referred to as a hydrogenation rate (hydrogenation rate). The upper limit of the hydrogenation rate is not particularly limited, but the upper limit may be 99 mol% or 98 mol%. In other words, the hydrogenation rate of the block copolymer (A-2) is preferably 85 to 99 mol%.
The hydrogenation rate is determined by measuring the content of carbon-carbon double bonds in the structural unit derived from the conjugated diene compound in the polymer block (A-2) by ¹ H-NMR measurement after hydrogenation. More specifically, it is a value measured according to the method described in Examples.

(Weight average molecular weight (Mw) of block copolymer (A))
The weight average molecular weight (Mw) obtained in terms of standard polystyrene by gel permeation chromatography of the block copolymer (A) or its hydrogenated product is preferably 20,000 to 500, from the viewpoint of heat resistance and moldability. It is 000, more preferably 25,000 to 400,000, still more preferably 28,000 to 350,000, particularly preferably 29,000 to 300,000, and most preferably 30,000 to 200,000.
The weight average molecular weight of the block copolymer (A) or its hydrogenated product can be in the above range, for example, by adjusting the amount of the monomer with respect to the polymerization initiator.

The block copolymer (A) has a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, or an epoxy group at the molecular chain and / or at the end of the molecule as long as the object and effect of the present invention are not impaired. It may have one kind or two or more kinds, or may have no functional group.

If the peak top temperature of tan δ of the block copolymer (A) or its hydrogenated product measured according to JIS K 7244-4 (1999) is -50 ° C or higher, it is sufficient in an actual use environment. A good vibration damping property can be obtained, and if the temperature is + 50 ° C. or lower, it is easy to secure the flexibility required as a vibration damping material.
Further, the peak top intensity of tan δ measured according to JIS K 7244-4 (1999) of the block copolymer (A) or its hydrogenated product is such that the larger the value, the more the vibration damping property at the temperature. It shows that it is excellent in physical properties, and if it is 1.0 or more, sufficient vibration damping property can be obtained in an actual use environment. The peak top intensity of the tan δ is preferably 1.0 or more, more preferably 1.5 or more, and further preferably 1.9 or more.
The peak top intensity of tan δ is the value of tan δ when the peak of tan δ is maximized. The peak top temperature of tan δ is the temperature at which the peak of tan δ becomes maximum. The peak top temperature of tan δ and the peak top intensity of tan δ of the block copolymer (A) or a hydrogenated product thereof are specifically measured by the method described in Examples. In order to keep these values in the above range, for example, adjusting the ratio of isoprene as the monomer for constituting the polymer block (A-2) can be mentioned.

(Other resin components)
Examples of the resin component other than the block copolymer (A) that can be contained in the thermoplastic resin composition (AC) constituting the vibration damping layer (AL) include a polyolefin resin, a polyamide resin, a polyester resin, and styrene. Examples thereof include based resins, acrylic resins, polyoxymethylene resins, ABS resins, polyphenylene sulfides, polyphenylene ethers, polyurethane thermoplastic elastomers, polycarbonates, rubber materials and elastomer materials. A resin composition containing any one or more of these can be used.
Further, in the thermoplastic resin composition (AC), as a resin component other than the block copolymer (A), a hydrogenated kumaron-inden resin, a hydrogenated rosin-based resin, as long as the effect of the present invention is not impaired, Hydrophilic resins such as hydrogenated terpene resins and alicyclic hydrogenated petroleum resins; tackifier resins such as aliphatic resins composed of olefins and diolefin polymers; hydrogenated polyisobutylene, hydrogenated polybutadienes, butyl rubbers, polys Other polymers such as isobutylene and polybutene may be included.
When the thermoplastic resin composition (AC) contains a resin component other than the block copolymer (A), the resin component other than the block copolymer (A) in the composition is not particularly limited. The content of the resin is preferably 50% by mass or less. In this case, the content of the block copolymer (A) in the composition is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 80% by mass or more from the viewpoint of vibration damping. Particularly preferably, it is 90% by mass or more, and most preferably 95% by mass or more.

(Additive)
Examples of the components other than the resin component that can be contained in the thermoplastic resin composition (AC) constituting the vibration damping layer (AL) include antioxidants, ultraviolet absorbers, light stabilizers, heat shield materials, and antiblocking agents. , Pigments, dyes, softeners, cross-linking agents, cross-linking aids, cross-linking accelerators, fillers and other additives, but are not particularly limited thereto. These can be used alone or in combination of two or more.

Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like.
As the ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a hindered amine-based ultraviolet absorber, a benzoate-based ultraviolet absorber, and the like, as well as a triazine-based compound, a benzophenone-based compound, a malonic acid ester compound, a oxalic acid anilide compound, and the like can be used.
Examples of the light stabilizer include hindered amine-based light stabilizers.
Examples of the heat-shielding material include heat-shielding particles having a heat-shielding function in resin or glass, and a material containing an organic dye compound having a heat-shielding function. Particles having a heat ray shielding function include, for example, particles of oxides such as tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, tin-doped zinc oxide, and silicon-doped zinc oxide, and LaB ₆ (hexhoylated lanthanum). Examples thereof include particles of an inorganic material having a heat ray shielding function such as particles. Examples of the organic dye compound having a heat ray shielding function include a diimonium dye, an aminium dye, a phthalocyanine dye, an anthraquinone dye, a polymethine dye, a benzenedithiol type ammonium compound, a thiourea derivative, and a thiol metal complex. Can be mentioned.
Examples of the anti-blocking agent include inorganic particles and organic particles. Examples of the inorganic particles include IA, IIA, IVA, VIA, VIA, VIIIA, IB, IIB, IIIB, and IVB element oxides, hydroxides, sulfides, nitrites, and halogens. Compounds, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, boron salts and their hydrous compounds, as well as complex compounds and natural mineral particles centered on them. Can be mentioned. Examples of the organic particles include fluororesins, melamine-based resins, styrene-divinylbenzene copolymers, acrylic resin silicones, and crosslinked products thereof.
Examples of the pigment include organic pigments and inorganic pigments. Examples of the organic pigment include an azo pigment, a quinacridone pigment, a phthalocyanine pigment and the like. Examples of the inorganic pigment include titanium oxide, zinc oxide, zinc sulfide, carbon black, lead pigment, cadmium pigment, cobalt pigment, iron pigment, chromium pigment, ultramarine blue and dark blue.
Examples of dyes include azo, anthraquinone, phthalocyanine, quinacridone, perylene, dioxazine, anthraquinone, indolinone, isoindolino, quinoneimine, triphenylmethane, thiazole, nitro, and nitroso. Dyes can be mentioned.
Examples of the softening agent include hydrocarbon-based oils such as paraffin-based, naphthen-based, and aromatic oils; vegetable oils such as peanut oil and rosin; phosphoric acid esters; low-molecular-weight polyethylene glycol; liquid paraffin; low-molecular-weight polyethylene and ethylene-α-. Known softeners such as hydrocarbon-based synthetic oils such as olefin copolymer oligomers, liquid polybutene, liquid polyisoprene or hydrogenated products thereof, liquid polybutadienes or hydrogenated products thereof can be used. These may be used alone or in combination of two or more.

Examples of the cross-linking agent include radical generators, sulfur and sulfur compounds.
Examples of the radical generator include dialkyl monoperoxides such as dicumyl peroxide, dit-butyl peroxide and t-butyl cumyl peroxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2 , 5-Dimethyl-2,5-di (t-butylperoxy) hexin-3, bis (t-butyldioxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl Diperoxides such as cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerates; diacyl peroxides such as benzoyl peroxides, p-chlorobenzoyl peroxides, 2,4-dichlorobenzoyl peroxides; t-butylperoxybenzoates and the like. Monoacylalkyl peroxides; percarbonates such as t-butylperoxyisopropyl carbonate; organic peroxides such as diacetylperoxides, diacylperoxides such as lauroyl peroxides and the like. These may be used alone or in combination of two or more. Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and dicumyl peroxide are preferable from the viewpoint of reactivity.
Examples of the sulfur compound include sulfur monochloride and sulfur dichloride.
Other phenolic resins such as alkylphenol resin and brominated alkylphenol resin; combinations of p-quinonedioxime and lead dioxide, and p, p'-dibenzoylquinonedioxime and trilead tetroxide are also used as cross-linking agents. can do.

As the cross-linking aid, known cross-linking aids can be used, for example, trimethylolpropanetrimethacrylate, trimethylolpropanetriacrylate, trimellitic acid triallyl ester, 1,2,4-benzenetricarboxylate triallyl. Ester, Triallyl Isocyanurate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene Polyfunctional monomers such as glycol dimethacrylate, divinylbenzene, glycerol dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate; stannous chloride, ferric chloride, organic sulfonic acid, polychloroprene, chlorosulfonated Examples include polyethylene. As the cross-linking aid, one type may be used alone, or two or more types may be used in combination.

Examples of the cross-linking accelerator include thiazoles such as N, N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, and 2- (4-morpholinodithio) benzothiazole; diphenylguanidine and triphenylguanidine. Guanidins such as; aldehyde-amine reactants such as butylaldehyde-aniline reactants, hexamethylenetetramine-acetaldehyde reactants or aldehyde-ammonia reactants; imidazolines such as 2-mercaptoimidazoline; thiocarbanilide, diethylurea, dibutyl Thioureas such as thiourea, trimethylthiourea, diorsotrilthiourea; dibenzothiazyl disulfide; tetramethylthium monosulfide, tetramethylthium disulfide, thiuram monosulfides such as pentamethylene thiuram tetrasulfide or thiuram polysulfides; zinc dimethyldithiocarbamate , Thiocarbamates such as zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, telluryl diethyldithiocarbamate; xanthogenates such as zinc dibutylxanthogenate; zinc flower and the like. The cross-linking accelerator may be used alone or in combination of two or more.

Examples of the filler include talc, clay, mica, calcium silicate, glass, hollow glass sphere, glass fiber, calcium carbonate, magnesium carbonate, basic magnesium carbonate, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, and hoe. Zinc acid, dosonite, ammonium polyphosphate, calcium aluminate, hydrotalcite, silica, diatomaceous earth, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, tin oxide, antimony oxide, barium ferrite, strontium ferrite, carbon black, Inorganic fillers such as graphite, carbon fiber, activated charcoal, carbon hollow spheres, calcium titanate, lead zirconate titanate, silicon carbide, mica, organic fillers such as wood flour and starch, conductivity of carbon black, graphite, carbon nanotubes, etc. Examples thereof include metal fillers such as fillers, silver powders, copper powders, nickel powders, tin powders, copper fibers, stainless steel fibers, aluminum fibers and iron fibers.

The content of the additive contained in the vibration damping layer (AL) is not particularly limited, and can be appropriately adjusted according to the type of the additive and the like. When the vibration damping layer (AL) contains the additive, the content of the additive is, for example, 50% by mass or less, 45% by mass or less, and 30% by mass or less with respect to the total mass of the vibration damping layer (AL). It may be 0.01% by mass or more, 0.1% by mass or more, and 1% by mass or more.

(Method for producing block copolymer (A))
The block copolymer (A) can be produced, for example, by a solution polymerization method, an emulsion polymerization method, a solid phase polymerization method, or the like. Of these, the solution polymerization method is preferable, and for example, known methods such as anionic polymerization method such as anionic polymerization and cationic polymerization, and radical polymerization method can be applied. Of these, the anion polymerization method is preferable. In the anionic polymerization method, at least one selected from the group consisting of an aromatic vinyl compound, a conjugated diene compound and isobutylene is sequentially added in the presence of a solvent, an anionic polymerization initiator and, if necessary, a Lewis base. The block copolymer (A) is obtained, and if necessary, a coupling agent is added and reacted. Further, by hydrogenating the block copolymer (A), a hydrogenated block copolymer can be obtained.

As a method for producing the block copolymer (A), for example, by polymerizing one or more conjugated diene compounds as monomers by an anionic polymerization method, a structural unit containing the above-mentioned alicyclic skeleton (X) in the main chain can be obtained. The polymer block (A-2) to have is formed, the monomer of the polymer block (A-1) is added, and if necessary, the monomer of the polymer block (A-1) and the conjugated diene compound are sequentially added. By doing so, the block copolymer (A) containing the alicyclic skeleton (X) can be obtained.
As a method for producing an alicyclic skeleton by the above anionic polymerization method, a known technique can be used (see, for example, US Pat. No. 3,966691). The alicyclic skeleton is formed at the end of the polymer due to the depletion of the monomer, and the polymerization can be started again from the alicyclic skeleton by sequentially adding the monomer to the terminal. Therefore, the presence or absence of formation of the alicyclic skeleton and its content can be adjusted by the sequential addition time of the monomers, the polymerization temperature, the type and addition amount of the catalyst, the combination of the monomers and the catalyst, and the like. Further, in the anionic polymerization method, an anionic polymerization initiator, a solvent, and if necessary, a Lewis base can be used.

Examples of the organic lithium compound that can be used as a polymerization initiator for anionic polymerization in the above method include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and pentyllithium. Examples of the dilithium compound that can be used as the polymerization initiator include naphthalenedilithium and dilithiohexylbenzene.
Examples of the coupling agent include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, phenylbenzoate and the like.
The amount of these polymerization initiators and coupling agents used is appropriately determined by the desired weight average molecular weight of the target block copolymer (A). Usually, the initiator such as an alkyllithium compound or a dilithium compound is used at a ratio of 0.01 to 0.2 parts by mass per 100 parts by mass of a total of monomers such as an aromatic vinyl compound and a conjugated diene compound used for polymerization. When a coupling agent is used, it is preferably used at a ratio of 0.001 to 0.8 parts by mass per 100 parts by mass of the total of the above-mentioned monomers.

The solvent is not particularly limited as long as it does not adversely affect the anion polymerization reaction. For example, aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane and n-pentane; aromatic hydrocarbons such as benzene, toluene and xylene. And so on. The polymerization reaction is usually carried out at a temperature of 0 to 100 ° C., preferably 10 to 70 ° C. for 0.5 to 50 hours, preferably 1 to 30 hours.

Further, by adding a Lewis base as a co-catalyst (vinyl agent) at the time of polymerization, the content of 3,4-bond and 1,2-bond of the polymer block (A-2) (vinyl bond amount). And the content of the alicyclic skeleton (X) can be increased.
Examples of the Lewis base include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and 2,2-di (2-tetrahydrofuryl) propane (DTHP); ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol. Glycol ethers such as dimethyl ether; amines such as triethylamine, N, N, N', N'-tetramethylenediamine, N, N, N', N'-tetramethylethylenediamine (TMEDA), N-methylmorpholin; sodium Sodium or potassium salts of aliphatic alcohols such as t-butyrate, natrim t-amilate or sodium isopentylate, or dialkyl sodium cyclohexanolates, such as sodium or potassium salts of alicyclic alcohols such as sodium mentrate, etc. Metal salt; etc.
Among the Lewis bases, tetrahydrofuran and DTHP are preferably used from the viewpoint of vibration damping and thermal stability. In addition, it is possible to obtain a high vinyl bond amount, it is easy to achieve a high hydrogenation rate without using an excessive amount of hydrogenation catalyst, and it is possible to realize both excellent vibration damping and thermal stability. Therefore, DTHP. Is more preferable to use.
These Lewis bases can be used alone or in combination of two or more.

The amount of the Lewis base added is the isoprene unit and / or the isoprene unit constituting the polymer block (A-2), especially when the polymer block (A-2) contains a structural unit derived from isoprene and / or butadiene. It is determined by how much the amount of vinyl bond in butadiene units is controlled. Therefore, the amount of Lewis base added is not strictly limited, but is usually 0.1 to 1,000 mol per gram atom of lithium contained in the alkyllithium compound or dilithium compound used as the polymerization initiator. It is preferably used in the range of 1 to 100 mol.
After the polymerization is carried out by the above method, the block copolymer (A) can be obtained by adding an active hydrogen compound such as alcohols, carboxylic acids and water to terminate the polymerization reaction.

After the polymerization is carried out by the above method, an active hydrogen compound such as alcohols, carboxylic acids and water is added to terminate the polymerization reaction. Then, by carrying out a hydrogenation reaction (hydrogenation reaction) in the presence of a hydrogenation catalyst in an inert organic solvent, a hydrogenated copolymer can be obtained. In the hydrogen addition reaction, the hydrogen pressure is 0.1 to 20 MPa, preferably 0.5 to 15 MPa, more preferably 0.5 to 5 MPa, and the reaction temperature is 20 to 250 ° C., preferably 50 to 180 ° C., more preferably 70. It can be carried out at ~ 180 ° C. and a reaction time of usually 0.1 to 100 hours, preferably 1 to 50 hours.
As the hydrogenation catalyst, for example, Raney nickel; a transition metal compound, an alkylaluminum compound, and an alkyl can be used from the viewpoint of carrying out the hydrogenation reaction of the polymer block (A-2) while suppressing the nuclear hydrogenation of the aromatic vinyl compound. A Cheegler-based catalyst composed of a combination with a lithium compound or the like; a metal Raney-based catalyst or the like can be mentioned. From the same viewpoint as described above, the Ziegler-based catalyst is preferable, the Ziegler-based catalyst composed of a combination of a transition metal compound and an alkylaluminum compound is more preferable, and the Ziegler-based catalyst composed of a combination of a nickel compound and an alkylaluminum compound (Al /). Ni-based Ziegler catalyst) is more preferable.

The hydrogenated block copolymer thus obtained is solidified by pouring the polymerization reaction solution into methanol or the like and then heated or dried under reduced pressure, or the polymerization reaction solution is poured into hot water together with steam and used as a solvent. Can be obtained by subjecting so-called steam stripping, which removes the mixture by co-boiling, and then heating or drying under reduced pressure.

(Manufacturing method of thermoplastic resin composition (AC))
When the block copolymer (A) or its hydrogenated product is used alone as the thermoplastic fat composition (AC), the block copolymer (A) obtained by the above-mentioned production method or its hydrogenated product is used alone. Can be used as it is as a thermoplastic resin composition (AC).
When a thermoplastic fat composition (AC) containing a block copolymer (A) or a hydrogenated product thereof and a resin component other than the block copolymer (A) is obtained, the production method is not particularly limited. A known method can be adopted. For example, is it produced by mixing the block copolymer (A) or its hydrogenated additive with other resin components using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender? Or, after mixing the mixture, it can be manufactured by melt-kneading with a uniaxial extruder, a twin-screw extruder, a kneader or the like.
When a block copolymer (A) or a hydrogenated product thereof containing an additive is used as the thermoplastic fat composition (AC), or when the block copolymer (A) or its hydrogenated product and a block copolymer are used. Even when a resin component other than (A) and an additive are contained, the thermoplastic fat composition (AC) can be obtained by mixing these components with the above-mentioned mixer or melt-kneading with the above-mentioned device after mixing. Can be manufactured.

<Restricted layer (BL)>
The restraining layer (BL) is a restraining type laminated body obtained by attaching a damping material to a metal plate, and has a function of imparting appropriate rigidity to the laminated body and assisting the development of vibration damping property by the damping layer. It is a layer to have. Further, the restraint layer (BL) is a layer made of a material different from the vibration damping layer (AL) and having at least a higher tensile storage elastic modulus than the vibration damping layer (AL).
The restraint layer (BL) according to the embodiment of the present invention is made of a thermoplastic resin composition (BC). Since the restraining layer (BL) is made of a thermoplastic resin composition (BC), the damping material is compared with the damping material used for the damping steel plate having the structure of "steel plate / vibration damping layer / steel plate". The weight of the can be reduced.
The thermoplastic resin composition (BC) constituting the restraint layer (BL) may be composed of only a resin component or may contain various additives other than the resin component. The components other than the resin component that can be contained in the thermoplastic resin composition (BC) will be described later.

As specified in the above condition (3), the restraining layer (BL) is the ratio H (BL) of the thickness H (BL) of the restraining layer (BL) to the thickness H (AL) of the damping layer (AL). ) / H (AL) has a thickness of 3 to 200. When the thickness H (BL) of the restraining layer (BL) has the above relationship with the thickness H (AL) of the damping layer (AL), the restraining layer (BL) is compared with the damping layer (AL). It will be thick enough and the damping material will be lightweight yet have sufficient rigidity.
The H (BL) / H (AL) is preferably 5 to 150 from the viewpoint of moldability, more preferably 8 to 100, still more preferably 10 to 60, and further more preferably from the viewpoint of vibration damping. It is preferably 13 to 40.

When the vibration damping material has a structure in which the vibration damping layer (AL) and the restraining layer (BL) are repeatedly laminated, H (BL) in the above H (BL) / H (AL) is a plurality of restraints. It is the total thickness of the layers (BL), and H (AL) is the total thickness of the plurality of damping layers (AL). For example, in the case of the damping material 101 shown in FIG. 2A, H (AL) is the thickness H (AL1) of the first damping layer and the thickness H (AL2) of the second damping layer. The total, that is, H (AL) = H (AL1) + H (AL2). Further, H (BL) is the sum of the thickness H (BL1) of the first restraint layer, the thickness H (BL2) of the second restraint layer, and the thickness H (BL3) of the third restraint layer, that is. , H (BL) = H (BL1) + H (BL2) + H (BL3).
The thicknesses H (AL) and H (BL) control, for example, molding conditions (for example, the amount discharged from the extruder in extrusion molding) when molding the vibration damping layer (AL) and the restraint layer (BL). By doing so, the thickness H (AL) described above and the thickness H (BL) described later can be adjusted, and the above relationship can be obtained.

The thickness H (BL) of the restraint layer (BL) is preferably 0.4 mm or more, preferably 0.6 mm or more, and preferably 0.8 mm or more from the viewpoint of ensuring mechanical strength and vibration damping property. From the viewpoint of preventing the weight and thickness of the damping material from becoming excessively large, it is preferably 5 mm or less, more preferably 4 mm or less, still more preferably 3 mm or less. In other words, the thickness H (BL) of the restraint layer (BL) is preferably 0.4 to 5 mm from the viewpoint of ensuring mechanical strength and vibration damping property.

The restraining layer (BL) can be a layer co-extruded together with the damping layer (AL) from the viewpoint of simplifying the structure of the damping material and facilitating the production of the damping material.
If the restraining layer (BL) is a layer co-extruded together with the damping layer (AL), it is possible to form a damping material in which the damping layer is closely fixed to the restraining layer with the minimum necessary layer, and the damping layer can be formed. The structure of the vibration material can be simplified. Further, it is not necessary to provide another layer for fixing the vibration damping layer to the restraining layer, and the vibration damping material can be easily and quickly manufactured. In addition, since the structure of the damping material is simple, it is easy to exert the vibration damping performance intended for the damping material.

The restraint layer (BL) may be heat-sealed to the vibration damping layer (AL).
If the restraint layer (BL) is heat-sealed to the vibration damping layer (AL), the configuration of the vibration damping material can be simplified as in the case of coextrusion described above, and the intended vibration damping performance can be obtained. It will be easier to demonstrate. Further, it is not necessary to provide an adhesive layer or the like, and the vibration damping material can be easily manufactured.

(Thermoplastic Resin Composition (BC))
The thermoplastic resin composition (BC) is a material that can impart high mechanical properties to the restraint layer (BL). The thermoplastic resin composition (BC) is a composition of a different type from the thermoplastic resin composition (AC), and has at least a high tensile storage elastic modulus as compared with the thermoplastic resin composition (AC). The thermoplastic resin composition (BC) may consist of a single resin or may contain a plurality of specific types of resins.
As specified in the above condition (2), at least one of the glass transition temperature Tg and the melting point Tm of the thermoplastic resin composition (BC) is 100 ° C. or higher.
When the Tg or Tm of the thermoplastic resin composition (BC) is in the above range, the thermoplastic resin composition (BC) generally has good mechanical properties (for example, tensile storage elastic modulus and loss elastic modulus). become. Therefore, the mechanical properties of the restraint layer (BL) can be enhanced.
At least one of the glass transition temperature and the melting point of the thermoplastic resin composition (BC) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 140 ° C. or higher, and more preferably 140 ° C. or higher, from the viewpoint of mechanical strength. From the viewpoint of moldability, it is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, still more preferably 280 ° C. or lower. In other words, at least one of the glass transition temperature and the melting point of the thermoplastic resin composition (BC) is preferably 100 to 350 ° C. from the viewpoint of mechanical strength and moldability.
In the present specification, Tg and Tm of the thermoplastic resin composition (BC) refer to Tg as the temperature at which the baseline shift occurs in the DSC curve created by using a differential scanning calorimeter (DSC), and endothermic heat. The temperature at which the peak is observed is defined as Tm, and specifically, it is measured by the method described in Examples. Even when the thermoplastic resin composition (BC) contains an infusible additive among the additives described later, the temperatures measured by the above method are Tg and Tm of the thermoplastic resin composition (BC).

The thermoplastic resin composition (BC) is measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999) 20. The tensile storage elastic modulus E'(BC) at ° C. is preferably 1,000 MPa or more, more preferably 1,500 MPa or more, still more preferably 2,000 MPa or more, and more preferably 2,000 MPa or more, from the viewpoint of vibration damping of the laminated body. From the viewpoint of processability, it is preferably 100,000 MPa or less, more preferably 50,000 MPa or less, and further preferably 30,000 MPa or less. In other words, the tensile storage elastic modulus E'(BC) is preferably 1,000 to 100,000 MPa from the viewpoint of vibration damping and processability of the laminated body.

A thermoplastic resin composition (BC) at 20 ° C. measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The loss elastic modulus E'' (BC) is preferably 10 MPa or more, more preferably 30 MPa or more, still more preferably 50 MPa or more from the viewpoint of vibration damping of the laminated body, and preferably from the viewpoint of mechanical properties. Is 10,000 MPa or less, more preferably 5,000 MPa or less, still more preferably 1,000 MPa or less. In other words, the loss elastic modulus E ″ (BC) is preferably 10 to 10,000 MPa from the viewpoint of achieving both vibration damping properties and mechanical properties.

Thermoplastic compositions at 20 ° C., respectively, measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The tensile storage elastic modulus E'(AC) of AC) and the tensile storage elastic modulus E'(BC) of the thermoplastic composition (BC) are preferably E'(BC) / from the viewpoint of vibration damping of the laminate. It satisfies the relationship of E'(AC) ≧ 50, more preferably E'(BC) / E'(AC) ≧ 100, still more preferably E'(BC) / E'(AC) ≧ 120, and is a laminated body. From the viewpoint of formability, preferably E'(BC) / E'(AC) ≤ 100,000, more preferably E'(BC) / E'(AC) ≤ 10,000, and even more preferably E'(. The relationship of BC) / E'(AC) ≤ 10,000 is satisfied. In other words, the tensile storage elastic modulus E'(BC) preferably has a relationship of 100,000 ≧ E'(BC) / E'(AC) ≧ 50 from the viewpoint of vibration damping and moldability of the laminate. Meet.

The thermoplastic resin composition (BC) preferably contains at least one of an olefin resin and a polyamide resin, and more preferably contains an olefin resin, from the viewpoint of moldability and adhesiveness to the vibration damping layer (AL). ..

Examples of the olefin-based resin include polypropylene, polyethylene, polymethylpentene, ethylene-vinyl acetate copolymer, and resins in which a plurality of these are combined.
Examples of the polypropylene include block polypropylene which is a block copolymer with α-olefin such as homopolypropylene and ethylene, and random polypropylene which is a random copolymer with α-olefin such as ethylene.
Examples of the polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, and the like.
Examples of the polymethylpentene include a homopolymer of 4-methyl-1-pentene, a structural unit derived from 4-methyl-1-pentene, and an α-olefin having 2 to 20 carbon atoms (however, 4-methyl-. Examples thereof include copolymers having a structural unit derived from 1-).
The ethylene-vinyl acetate copolymer is not particularly limited as long as it is a resin copolymerized with ethylene using acetic acid as a comonomer, and various vinyl acetate group contents (VA content) can be used.
Further, a homopolymer or copolymer of α-olefin, a copolymer of propylene and / or ethylene and α-olefin, and the like can also be used as the polyolefin resin (B).
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 -Alkenes include α-olefins having 20 or less carbon atoms such as octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene, and one or 2 of these. More than a seed can be used.

Examples of the polyamide resin include polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 11, polyamide 12, polyamide 6/12, polyhexamethylenediamine terephthalamide, polyhexamethylenediamine isophthalamide, and xylene group-containing polyamide. And so on.

(Additive)
Examples of the resin material other than the thermoplastic resin component (BC) that can be contained in the restraint layer (BL) include antioxidants, ultraviolet absorbers, light stabilizers, heat shield materials, antiblocking agents, pigments, dyes, and softeners. Examples thereof include additives such as agents, cross-linking agents, cross-linking aids, and cross-linking accelerators, but the present invention is not particularly limited thereto. These can be used alone or in combination of two or more.
As these additives, those similar to those described in the vibration damping layer (AL) described above can be used.

Further, the restraining layer (BL) is provided with a filler, a reinforcing material, a lubricant, an antistatic agent, a flame retardant, a foaming agent, a water repellent agent, a waterproofing agent, a conductivity imparting agent, a thermal conductivity imparting agent, and an electromagnetic wave shielding property. Additives such as agents, fluorescent agents and antibacterial agents may be contained.
As the filler, the same one as described in the vibration damping layer (AL) described above can be used.
A commercially available resin material in which an additive is mixed with the resin, such as a glass fiber reinforced resin, can also be used as the thermoplastic resin composition (BC).

(Manufacturing method of thermoplastic resin composition (BC))
The method for producing the thermoplastic fat composition (BC) is not particularly limited, and a known method can be adopted. For example, a resin having at least one of Tg and Tm having a temperature of 100 ° C. or higher is mixed alone or a plurality of specific types are mixed using a mixer such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender. It can be manufactured by melting and kneading with a single-screw extruder, a twin-screw extruder, a kneader, or the like after mixing.
When a thermoplastic fat composition (BC) containing a resin and an additive is used, these components are mixed by the above-mentioned mixer, or after mixing, melt-kneaded by the above-mentioned apparatus to make the thermoplastic. A fat composition (BC) can be produced.

<Manufacturing method of damping material>
The vibration damping material preferably coextrudes the vibration damping layer (AL) and the restraining layer (BL) from the viewpoint of facilitating the production of the damping material and simplifying the configuration of the damping material. Manufactured by forming.
Specifically, the thermoplastic resin composition (AC) and the thermoplastic resin composition (BC) are each melted, and if necessary, other components such as additives are added to the Henshell mixer. , V blender, ribbon blender, tumbler blender, conical blender, etc., to be manufactured by mixing, or after mixing, melt-kneaded with a single-screw extruder, twin-screw extruder, kneader, etc. A vibration damping material can be produced by coextruding in layers from an injection molding machine and pressing with a pair of rollers.

In another aspect of the method for manufacturing a vibration damping material, the vibration damping layer (AL) and the restraining layer (BL) are molded and then laminated and heat-sealed to manufacture the vibration damping material.
Specifically, the thermoplastic resin composition (AC) and the thermoplastic resin composition (BC) are each formed into a sheet shape, and then the two are overlapped and pressed by a pair of thermal rollers. A vibration damping material can be produced by thermally melting at least one of them and thermally fusing it to the other.

[Laminate]
The laminated body according to the embodiment of the present invention includes the above-mentioned vibration damping material and a metal plate laminated on the vibration damping material.
As shown in FIG. 1 (A), when the vibration damping material includes only one structure in which the damping layer (AL) and the restraining layer (BL) are laminated, the obtained laminated body is shown in FIG. As shown in (B), the vibration damping material and a metal plate laminated on the surface opposite to the restraining layer (BL) of the damping material are included.
As shown in FIG. 2A, the vibration damping material has a structure in which a plurality of damping layers (AL) and restraining layers (BL) are repeatedly laminated, and restraining layers (constraining layers) are formed on the upper surface and the lower surface. When BL) is located, the obtained laminate has the above-mentioned damping material and a metal plate laminated on the restraining layer (BL) of the damping material, as shown in FIG. 2 (B). include.
When the vibration damping material has a structure in which a plurality of vibration damping layers (AL) and a restraining layer (BL) are repeatedly laminated, and the vibration damping layer (AL) is located on the upper surface or the lower surface. The obtained laminate includes the vibration damping material and a metal plate laminated on the vibration damping layer (AL) of the vibration damping material.

Examples of the metal plate include stainless steel sheets, cold-rolled steel sheets, alloyed galvanized steel sheets, SECC (bonded steel sheets) and the like.

In the laminated body in which the restraining layer (BL) located on the upper surface or the lower surface of the vibration damping material is attached to the metal plate as in the laminated body 201 shown in FIG. 2 (B), the restraining layer (BL) and the metal plate are attached. It is preferable to provide an intermediate layer between the two and the two.
The intermediate layer is formed, for example, by applying an adhesive material or an adhesive material to at least one of the restraint layer (BL) and the metal layer before the restraint layer (BL) is attached to the metal layer. Examples thereof include an adhesive layer and an adhesive layer. Further, by using a metal plate on which an adhesive auxiliary layer or a skin layer is formed, the auxiliary layer or the skin layer may be used as an intermediate layer.
Examples of the intermediate layer include polyvinyl acetal resin, ionomer, ethylene-vinyl acetate copolymer, urethane resin, polyamide resin, acrylic resin and the like. The intermediate layer may contain an adhesive strength adjusting agent such as an alkali metal salt or an alkaline earth metal salt, or a plasticizer.

[Method of improving vibration damping]
The method for improving the vibration damping property according to the embodiment of the present invention is a method for improving the vibration damping property by attaching the vibration damping material to a metal plate to improve the vibration damping property of the metal plate.
Here, when the vibration damping material includes only one structure in which the vibration damping layer (AL) and the restraining layer (BL) are laminated, as shown in FIG. 1 (A), the vibration damping property improving method. In, the surface of the damping material opposite to the restraining layer (BL) (that is, the damping layer (AL)) is attached to the metal plate.
When the vibration damping material is attached to the metal plate, the vibration damping material is placed on the metal plate so that the vibration damping layer (AL) of the vibration damping material is in contact with the surface of the metal plate, and the heat roller is placed. The vibration damping material can be attached to a metal plate by a method such as pressing with a pair of rollers including the above.
When the vibration damping material is attached to the metal plate in this way, it becomes a laminated body having a structure of "restraint layer (BL) / vibration damping layer (AL) / metal plate", and the vibration damping property of the metal plate can be improved. can. Since the restraint layer (BL) is made of the thermoplastic resin composition (BC), it is possible to prevent the weight of the entire laminate from increasing. Since the vibration damping material and the metal plate are directly thermocompression bonded, the structure is simple and it is easy to impart the intended vibration damping property to the obtained laminate.
Further, compared to the method of thermocompression bonding the vibration damping material and the metal plate, the number of layers constituting the laminated body increases, but the method of attaching the vibration damping material to the metal plate via the adhesive layer or the adhesive layer is used. It can also be adopted.
In some cases, the damping layer (AL) and the restraining layer (BL) are repeatedly laminated, and the damping layer (AL) is located on the upper surface or the lower surface of the damping material. , The vibration damping layer (AL) can be placed so as to be in contact with the surface of the metal plate, and the vibration damping material can be attached to the metal plate by the same procedure as described above.

As shown in FIG. 2A, the vibration damping material has a structure in which a plurality of damping layers (AL) and restraint layers (BL) are repeatedly laminated, and restraint layers (constraint layers (AL) and restraint layers (BL) are formed on the upper surface and the lower surface. When BL) is located, an intermediate layer is provided on at least one of the restraint layer (BL) and the metal plate in order to bring them into close contact with each other. A metal plate on which an adhesive auxiliary layer or a skin layer is formed may be prepared in advance, and the metal plate may be used.
Then, the restraining layer (BL) of the vibration damping material is opposed to the surface of the metal plate, both are overlapped via the intermediate layer, and while heating as necessary, they are pressed by a pair of rollers. , The vibration damping material can be attached to a metal plate.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[Manufacturing Example 1]
<Manufacturing of hydrogenated substance TPE-1 of block copolymer (A)>
In a pressure vessel that has been replaced with nitrogen and dried, 50 kg of cyclohexane (solvent) dried with Molecular Sieves A4 and 0.101 kg (sec-butyl) of sec-butyllithium cyclohexane solution having a concentration of 10.5% by mass as an anionic polymerization initiator. Substantial addition amount of lithium: 10.6 g) was charged.
After raising the temperature inside the pressure-resistant container to 50 ° C., 1.7 kg of styrene (1) was added and polymerized for 30 minutes, then the temperature was lowered to 40 ° C., 0.29 kg of tetrahydrofuran (THF) was added, and then isoprene 13. 3 kg was added over 5 hours and polymerized for 1 hour. Then, the temperature is raised to 50 ° C., 1.7 kg of styrene (2) is added and polymerized for 30 minutes, methanol is added to stop the reaction, and a reaction solution containing a polystyrene-polyisoprene-polystyrene triblock copolymer is contained. Got
A Cheegler-based hydrogenation catalyst formed of nickel octylate and trimethylaluminum was added to the reaction solution under a hydrogen atmosphere, and the reaction was carried out under the conditions of a hydrogen pressure of 1 MPa and 80 ° C. for 5 hours. After allowing the reaction solution to cool and pressurize, the catalyst is removed by washing with water and vacuum dried to obtain a hydrogenated product (TPE-1) of a polystyrene-polyisoprene-polystyrene triblock copolymer. rice field.

[Manufacturing Examples 2 to 5]
<Manufacturing of hydrogenated substances TPE-2 to 5 of block copolymer (A)>
Hydrogenated block copolymers TPE-2 to TPE-5 were produced in the same procedure as in Production Example 1 except that the raw materials and the amounts used thereof were shown in Table 1.

<Physical characteristics of hydrogenated block copolymer>
The physical characteristics of the hydrogenated block copolymers TPE-1 to TPE-5 were measured according to the following measuring methods. The results are shown in Table 2.

(Content of polymer block (A-1))
The hydrogenated block copolymer was dissolved in CDCl ₃ and ¹ H-NMR measurement [device: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 ° C.] was performed, and the peak intensity derived from styrene was determined to be heavy. The content of the coalesced block (A-1) was calculated.

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

(Hydrogenation rate of polymer block (A-2))
Hydrogenated block copolymer was dissolved in CDCl ₃ and ¹ H-NMR measurement [equipment: "ADVANCE 400 Nano bay" (manufactured by Bruker), measurement temperature: 30 ° C.] was performed, and it was derived from residual olefin of isoprene or butadiene. The hydrogenation rate was calculated from the peak area and the peak area ratio derived from ethylene, propylene and butylene.

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

(Peak top temperature and peak top intensity of loss tangent (tan δ))
Measurements were made according to JIS K 7244-4 (1999). Specifically, the obtained hydrogenated block copolymer was pressed at 230 ° C. for 3 minutes to prepare a sheet having a length of 50 mm, a width of 30 mm, and a thickness of 1 mm. This sheet is cut out to a length of 30 mm, a width of 5 mm, and a thickness of 1 mm to prepare a sample, and is measured using a DMA242 manufactured by NETZSCH under the conditions of a measurement temperature of -80 ° C to 100 ° C, a strain amount of 0.2%, and a frequency of 10 Hz. Therefore, the peak top temperature and the peak top intensity of the loss tangent (tan δ) were measured.

[Examples 1 to 10, Comparative Examples 1 to 3]
<Manufacturing of damping material and measurement of its physical properties>
The hydrogenated block copolymer TPE-1TPE-5 was used as a thermoplastic resin composition (AC) for forming a vibration damping layer (AL). In addition, polypropylene (PP) ("E-200GP" manufactured by Prime Polymer Co., Ltd.), glass fiber reinforced polypropylene (GFPP) ("R-300G" manufactured by Prime Polymer Co., Ltd.), glass fiber reinforced 6 nylon (GFPA6) (BASF). Manufactured by "B3EG6") was used as a thermoplastic resin composition (BC) for forming a restraining layer (BL).
Then, in Example 1, the thermoplastic resin composition (AC) for the vibration damping layer (AL) was T. A thermoplastic resin composition (BC) introduced into a die (multi-manifold type: width 500 mm) for a restraint layer (BL) is dispensed at a discharge rate of 80 kg / hour using a vent type single-screw extruder having a screw diameter of 65 mm. Introduced into the T-die under the conditions of.
The molded product co-extruded from the T-die is niped by two metal mirror rolls with one at 50 ° C and the other at 60 ° C, and the damping layer (AL) / restraining layer (BL) (thickness 50 μm / 2000 μm). ), A vibration damping material having a two-layer structure (total thickness 2,050 μm) was produced.
The damping materials of Examples 2 to 10 and Comparative Example 3 were produced by the same procedure as in Example 1 except that the discharge amount of the vent type single-screw extruder was changed as shown in Table 3. In Comparative Examples 1 and 2, the restraint layer (BL) was not provided.

(Glass transition temperature and melting point)
The Tg of the thermoplastic resin composition (AC) and the Tg and Tm of the thermoplastic resin composition (BC) are 10 ° C. from −100 ° C. to 350 ° C. using DSC250 manufactured by TA Instruments. Measured by raising the temperature at / min, the shift position of the baseline of the DSC curve (specifically, the intersection of the midpoint line of the baseline before and after the specific heat change and the DSC curve). It was Tg, and the peak temperature of the heat absorption peak was Tm.

(Loss tangent (tan δ), tensile storage elastic modulus E', loss elastic modulus E'')
The above-mentioned hydrogenated block copolymer for the vibration damping layer (AL) and each thermoplastic resin composition for the restraining layer (BL) are pressed by a press molding apparatus at a temperature of 230 ° C. and a pressure of 10 MPa for 3 minutes. Then, a sheet having a thickness of 1 mm was prepared, and the sheet was cut into a size of 30 mm × 5 mm and used as a test piece.
According to JIS K7424-4 (1999), using the dynamic viscoelastic device "DMA242" (manufactured by NETZSCH), the strain amount is 0 while raising the temperature from -80 ° C to 100 ° C at 3 ° C / min. By performing a dynamic viscoelasticity test in a tensile mode under the conditions of 0.2% and a frequency of 10 Hz, tan δ, tensile storage elastic modulus E', and loss elastic modulus E'' at 20 ° C. were measured.

<Manufacturing of laminated body and measurement of its physical properties>
SECC (bonded steel plate) with a length of 200 mm, a width of 10 mm, and a thickness of 0.8 mm and the sheet-shaped vibration damping material produced above are combined with a vibration damping layer (AL) using Aron Alpha EXTRA manufactured by Toagosei Co., Ltd. By adhering so as to be on the steel plate side, a laminated body having a structure of "restraint layer (BL) / vibration damping layer (AL) / adhesive layer / steel plate" was obtained. However, for Comparative Examples 1 and 2, a non-restraint type laminated body having a structure of "vibration damping layer (AL) / adhesive layer / steel plate" was used. The thickness of the adhesive layer is 0.05 mm.

(Loss coefficient of laminated body)
A contact chip is attached to the center of the laminate prepared above using an adhesive containing α-cyanoacrylate as the main component to prepare a sample, and a loss coefficient measurement system (Brüel & Kjär exciter 4809 type; impedance). Head 8001 type; charge converter 2647A type) was set. Specifically, the steel plate side in the center of the sample was fixed to the tip of the vibration detector built in the impedance head of the vibration device of the above device. Then, by applying vibration to the central part of the sample in the frequency range of 0 to 8,000 Hz, a damping test of the measurement sample is performed by the central vibration method, and the vibration force and the acceleration waveform in the central part are shown. Acceleration signal and was detected. Each sample was measured at a temperature of 20 ° C.
Based on the obtained vibration force and the velocity signal obtained by integrating the acceleration signal, the mechanical impedance of the vibration point (the central part of the laminated body to which vibration was applied) was obtained. Then, an impedance curve obtained with the horizontal axis as the frequency and the vertical axis as the above mechanical impedance is created, and the loss of the laminated body at 20 ° C. from the full width at half maximum of the second peak (2nd mode) counted from the low frequency side. The coefficient was calculated.
The measurement results are shown in Table 3 below.

As is clear from Table 3, the laminates of Examples 1 to 10 have a larger loss coefficient value at 20 ° C. than the laminates of Comparative Examples 1 and 2 having no restraint layer (BL). It can be seen that it has excellent vibration damping properties.
Further, the laminates of Examples 1 to 10 control the laminate of Comparative Example 3, that is, the hydrogenated block copolymer having a Tg lower than −40 ° C. and a tan δ of less than 0.3 at 20 ° C. It can be seen that the value of the loss coefficient at 20 ° C. is larger than that of the laminate used as the vibration layer (AL), and the vibration damping property is excellent.

The vibration damping material and the laminated body of the present invention can be used for a housing for an automobile, various parts mounted on an automobile, a housing thereof, and the like. In addition, various recorders such as TVs, Blu-ray recorders and HDD recorders in the home appliances field, projectors, game machines, digital cameras, home videos, antennas, speakers, electronic dictionaries, IC recorders, FAXs, copy machines, telephones, doorphones, rice cookers. , Microwave oven, oven range, refrigerator, dishwasher, dish dryer, IH cooking heater, hot plate, vacuum cleaner, washing machine, charger, sewing machine, iron, dryer, electric bicycle, air purifier, water purifier, electric toothbrush , Lighting equipment, air conditioners, outdoor units of air conditioners, dehumidifiers, humidifiers, and other various electric products.

AL, AL1, AL2: Vibration damping layer BL, BL1, BL2, BL3: Restraint layer 10: Metal plate 100, 101: Vibration damping material 200, 201: Laminated body

Claims (23)

It is a vibration damping material provided with a vibration damping layer (AL) and a restraining layer (BL) laminated on the vibration damping layer (AL).
The anti-vibration layer (AL) comprises a polymer block (A-1) containing a structural unit derived from an aromatic vinyl compound and a polymer block (A-2) containing a structural unit derived from a conjugated diene compound. It is composed of a thermoplastic resin composition (AC) containing the block copolymer (A) having the block copolymer (A).
The restraint layer (BL) is made of a thermoplastic resin composition (BC), and the restraint layer (BL) is made of a thermoplastic resin composition (BC).
A damping material that satisfies the following conditions (1) to (3).
(1) The glass transition temperature of the thermoplastic resin composition (AC) is −40 to + 30 ° C.
(2) At least one of the glass transition temperature and the melting point of the thermoplastic resin composition (BC) is 100 ° C. or higher.
(3) The ratio H (BL) / H (AL) of the thickness H (BL) of the restraint layer (BL) to the thickness H (AL) of the vibration damping layer (AL) is 3 to 200. The vibration damping material according to claim 1, wherein the glass transition temperature of the block copolymer (A) is −40 to + 30 ° C. The vibration damping material according to claim 1 or 2, wherein the content of the polymer block (A-1) in the block copolymer (A) is 22% by mass or less. The vibration damping material according to any one of claims 1 to 3, wherein the block copolymer (A) has a weight average molecular weight of 30,000 to 200,000. The vibration damping material according to any one of claims 1 to 4, wherein the block copolymer (A) is a hydrogenated agent, and the hydrogenated rate of the polymer block (A-2) is 85 mol% or more. .. Claim 1 in which the polymer block (A-2) in the block copolymer (A) has a structural unit having one or more alicyclic skeletons (X) represented by the following formula (X) in the main chain. The anti-vibration material according to any one of 5 to 5.

(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 from each other.) The vibration damping material according to claim 6, wherein the alicyclic skeleton (X) contains an alicyclic skeleton (X') in which at least one of R ¹ to R ³ is a methyl group. The vibration damping material according to claim 6 or 7, wherein the polymer block (A-2) contains 1 mol% or more of the alicyclic skeleton (X) or (X'). The thermoplastic composition (AC) is measured at 20 ° C. by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The vibration damping material according to any one of claims 1 to 8, wherein the tensile storage elastic modulus E'(AC) is 100 MPa or less. The thermoplastic composition (AC) is measured at 20 ° C. by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The vibration damping material according to any one of claims 1 to 9, wherein the loss tangent tan δ in the above method is 0.3 or more. The vibration damping material according to any one of claims 1 to 10, wherein the thickness H (AL) of the vibration damping layer (AL) is 0.3 mm or less. The thermoplastic resin composition (BC) is measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999) 20. The vibration damping material according to any one of claims 1 to 11, wherein the tensile storage elastic modulus E'(BC) at ° C. is 1,000 MPa or more. Thermoplastic resin composition (BC) at 20 ° C. measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The vibration damping material according to any one of claims 1 to 12, wherein the loss elastic modulus E'' (BC) is 10 MPa or more. The vibration damping material according to any one of claims 1 to 13, wherein the thermoplastic resin composition (BC) contains at least one of an olefin resin and a polyamide resin. The damping material according to any one of claims 1 to 14, wherein the thickness H (BL) of the restraint layer (BL) is 0.4 mm or more. Thermoplastic compositions at 20 ° C., respectively, measured by performing a dynamic viscoelasticity test by tensile vibration under the conditions of a strain amount of 0.2% and a frequency of 10 Hz according to JIS K7424-4 (1999). The tensile storage elastic modulus E'(AC) of AC) and the tensile storage elastic modulus E'(BC) of the thermoplastic composition (BC) satisfy the relationship of E'(BC) / E'(AC) ≥ 50. The vibration damping material according to any one of claims 1 to 15. The ratio H (BL) / H (AL) of the thickness H (BL) of the restraining layer (BL) to the thickness H (AL) of the damping layer (AL) is 8 to 100, according to claims 1 to 16. The damping material according to any one of the items. The vibration damping material according to any one of claims 1 to 17, wherein the vibration damping layer (AL) is a layer co-extruded together with a restraining layer (BL). The vibration damping material according to any one of claims 1 to 17, wherein the vibration damping layer (AL) and the restraining layer (BL) are heat-sealed. The method for manufacturing a vibration damping material according to any one of claims 1 to 19, wherein the vibration damping material is manufactured by coextruding a vibration damping layer (AL) and a restraining layer (BL). How to manufacture damping material. The method for manufacturing a vibration damping material according to any one of claims 1 to 19, wherein the vibration damping layer (AL) and the restraining layer (BL) are molded and then laminated and heat-sealed. A method for manufacturing a damping material, which manufactures a damping material. A laminated body comprising the vibration damping material according to any one of claims 1 to 19 and a metal plate laminated on the vibration damping material. A method for improving vibration damping property, wherein the vibration damping material according to any one of claims 1 to 19 is attached to a metal plate to improve the vibration damping property of the metal plate.

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