JPH09295382A - Vibration-damping laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vibration-damping laminate which shows a high vibration-damping performance over an extensive temperature range and further, shows high secondary working performances and also a high degree of freedom for molding. SOLUTION: In a vibration-damping laminate consisting of a base material and a vibration-damping layer laminated together, a layer formed of a vibration- damping composition containing a block copolymer A and an inorganic filler B is used as the vibration-damping layer. Further, a fiber-reinforced thermoplastic resin sheet containing 30-85vol.% of continuous fiber aligned almost evenly in one-way direction is used as the base material. The block copolymer A is a block copolymer with a number average molecular weight of 30000-300000 constituted of a block (a) containing a vinyl aromatic compound and a block (b) containing isoprene.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a laminate having excellent vibration damping performance.

[0002]

2. Description of the Related Art In recent years, the problems of noise and vibration have become a major social problem due to the development of transportation such as automobiles.
Low vibration and low noise are also progressing inside automobiles.
Further, in offices and general households, there is a strong demand for lowering vibration and noise of office appliances such as printers, household electric appliances such as washing machines, refrigerators and vacuum cleaners.

Conventionally, various springs such as leaf springs, coil springs, air springs, etc., and anti-vibration rubbers have been used in order to reduce vibrations and noises generated by vibrating objects (vibrators) such as automobiles and various electric appliances as described above. Etc. are mounted on a vibrating body. In this case, springs, anti-vibration rubber and the like block the transmission of vibrations, that is, reduce the degree of vibrations and noises generated by vibration isolation.

However, since the types of sources of vibrations and noises and the mechanisms of vibrations and noises are diversified, it has become impossible to cope with the conventional vibration damping means.

Therefore, recently, vibration itself has been suppressed (vibration suppression). When damping, basically a viscoelastic material (eg NR, II) capable of converting vibration energy into heat energy is used.
The vibration itself is absorbed by a vibration damping material formed of a vibration damping composition containing a rubber material such as R or SBR or an audible substance) and converted into thermal energy by absorbing the vibration energy of the vibrating body. It has been deterred. Here, the damping material is generally classified into an unconstrained damping material and a restrained damping material.

The former non-restraint type vibration damping material is generally formed by molding a viscoelastic material into a sheet, and is used by being attached to a vibrating body with an adhesive or the like. In this case, the viscoelastic material is exposed on the surface.

The latter restraint type vibration damping material is a layer (vibration damping layer) containing a viscoelastic material laminated on a base material made of a material having a high elastic modulus. The viscoelastic material-containing layer) is used by being attached to the surface of the vibrating body with an adhesive or the like.
Therefore, the viscoelastic material-containing layer is sandwiched, that is, constrained between the vibrating body and the base material. In this way, in the restraint type damping material, the base material functions as a restraining layer that restrains the damping layer. Examples of such a base material (constraint layer) include a metal plate (for example, cold rolled steel plate, zinc-based plated steel plate, stainless plate, aluminum plate, etc.), hard plastics (for example, polyvinyl chloride, polyethylene terephthalate, etc.), or A plate or sheet made of a thermosetting resin (for example, epoxy resin, unsaturated polyester resin, etc.) has been conventionally used. Since such a constrained type damping material can obtain higher damping performance than the non-constrained type damping material even if the damping layer (viscoelastic material layer) is thinner, the constrained type damping material has recently been used. It is increasing.

However, all of the viscoelastic materials such as rubber materials and retentive substances used for the conventional restraint type vibration damping material have a narrow temperature range exhibiting the vibration damping performance, and particularly the vibration damping performance in the high temperature region. There was a problem that was insufficient. Further, when the vibration damping material is composed of a rubber material among the viscoelastic materials, there is a problem that a vulcanization operation that requires a great deal of labor and time after molding the vibration damping material is indispensable. When the damping material is formed, there is a problem that flexibility at low temperatures becomes insufficient.

In order to solve this problem, a vinyl aromatic compound-containing block having a predetermined molecular weight range, a 3,4-bond and 1,2 in the predetermined molecular weight range are used instead of the conventional viscoelastic material.
A block copolymer having a total number of bond contents (hereinafter, abbreviated as vinyl bond content) of 40% or more and an isoprene-containing block and having a number average molecular weight of 30,000 to 300,000 or a hydrogenated product thereof. It has been proposed to use it as an elastic material (JP-A-2-102212).
Japanese Patent Laid-Open No. 3-43244). This viscoelastic material exhibits high vibration damping performance and good flexibility in a wide temperature range without performing a vulcanization operation.

[0010]

However, when the block copolymer or hydrogenated product thereof as described above is used as the viscoelastic material of the constraining type vibration damping material, the constraining type damping material has a wide temperature range. Although it is possible to impart high vibration damping performance and good flexibility in, even in a constrained vibration damping material using such a block copolymer or a hydrogenated product thereof, as described below, There was a problem that satisfactory workability (for example, cutting workability, bending workability, drawing workability, etc.) could not be obtained when the damping material was applied.

For example, when a metal is used as a material for the base material (constraint layer), it is difficult to cut the damping material because of its generally high hardness, and a large amount of heat is generated when cutting. Therefore, there is a problem that the viscoelastic material forming the vibration damping layer is apt to be deformed or deteriorated, and further, if excessive bending or drawing is performed, the base material (constraint layer) and the vibration damping layer are separated from each other. When hard plastics is used as the material of the base material, it is easy to break when cutting the damping material, and bending and drawing to obtain a three-dimensional shape are possible. There is a problem that the dimensions are likely to change due to the heat of time. Furthermore, when a thermosetting resin is used as a material for the base material, the damping material can be cut, but bending and drawing to obtain a three-dimensional shape are impossible. There's a problem.

As described above, as long as the conventional base material (constraint layer) is applied to the constraining type vibration damping material, the vibration damping material can be used for physical properties such as appearance quality, strength and rigidity, or dimensional stability. It was difficult to obtain a molded product having excellent properties, and the degree of freedom in molding into a desired three-dimensional shape was low.

The present invention has a vibration-damping layer which exhibits high vibration-damping performance and flexibility in a wide temperature range without performing a vulcanization operation, is excellent in processability, has a high degree of freedom in molding, and has an external appearance. An object of the present invention is to provide a constrained type vibration damping material that can obtain a molded product excellent in quality, physical performance and dimensional stability.

[0014]

Means for Solving the Problems The present inventor has constructed a damping layer from a specific block copolymer comprising a vinyl aromatic compound-containing block and an isoprene-containing block and processed it as a base material (constraint layer). The inventors have found that the above-mentioned object can be achieved by using a specific fiber-reinforced thermoplastic sheet which has excellent properties and dimensional stability and also has excellent three-dimensional processability, and has completed the present invention.

That is, the present invention provides a vibration damping laminate in which a substrate and a vibration damping layer are laminated: the vibration damping layer contains a block copolymer (A) and an inorganic filler (B). A block copolymer (A), which is a layer formed from a vibration damping composition
30 to 100 parts by weight of the inorganic filler (B) with respect to 100 parts by weight.
The block copolymer (A) has a number average molecular weight of 30,000 composed of a vinyl aromatic compound-containing block (a) and an isoprene-containing block (b).
Is a block copolymer of 3 to 300,000 or a hydrogenated product thereof, and the vinyl aromatic compound-containing block (a) has a number average molecular weight of 25 formed from a vinyl aromatic monomer.
The block (b) containing isoprene is formed from isoprene or an isoprene-butadiene mixture and has a number average molecular weight of 10,000.
To 200,000 and a vinyl bond content of 40% or more; and a fiber in which the base material contains 30 to 85% by volume of continuous fibers arranged in one direction substantially uniformly. Provided is a vibration damping laminate which is a reinforced thermoplastic resin sheet.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

The vibration damping laminate of the present invention has a structure in which at least one base material having a function of supporting and restraining the vibration damping layer and at least one vibration damping layer are laminated. Specific examples of the structure include a structure in which one damping layer is laminated on one surface of the base material and each one surface is exposed, and a structure in which both surfaces of one damping layer are sandwiched by the base material. .

In the present invention, the vibration damping layer is a layer formed from a vibration damping composition containing the block copolymer (A) and the inorganic filler (B).

Here, the block copolymer (A) is a copolymer composed of the vinyl aromatic compound-containing block (a) and the isoprene-containing block (b) or a hydrogenated product thereof.

The hydrogenated product is obtained by adding hydrogen to the double bond of the isoprene-containing block (b) in the copolymer composed of the vinyl aromatic compound-containing block (a) and the isoprene-containing block (b). Is added, the heat resistance and weather resistance are improved as compared with the copolymer before hydrogenation. Therefore, it can be preferably used when the vibration-damping laminate containing the block copolymer (A) is required to have heat resistance and weather resistance. In this case, the hydrogenation rate is not particularly limited, but is at least 50%, preferably 70% or more in order to improve the heat resistance and weather resistance of the vibration damping laminate.

The vinyl aromatic compound-containing block (a) constituting the block copolymer (A) is styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene. , 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and other vinyl aromatic monomers having a number average molecular weight of 250.
It is a block of 0 to 40,000. When the number average molecular weight of the vinyl aromatic compound-containing block (a) is less than 2500, the mechanical properties of the block copolymer (A) are deteriorated,
If it exceeds 000, the melt viscosity of the block copolymer (A) becomes too high, and the moldability of the vibration damping composition deteriorates, which is not preferable.

If the content of the vinyl aromatic compound-containing block (a) in the block copolymer (A) is too small, the mechanical properties of the block copolymer (A) will be insufficient, and conversely if it is too large. Since the melt viscosity of the block copolymer (A) is significantly increased, the processability is lowered, and the vibration damping performance of the block copolymer (A) is also lowered.
It is 50% by weight, more preferably 10 to 40% by weight.

The isoprene-containing block (b) constituting the block copolymer (A) is formed from isoprene or an isoprene-butadiene mixture and has a number average molecular weight of 10,000 to 200,000 and a vinyl bond content of 40% or more. It is a certain block.

The reason why isoprene is used as an essential constituent monomer in the block (b) is to allow the block copolymer (A) to exhibit vibration damping performance in a practical temperature range of about 0 ° C to 50 ° C. . That is, when a block formed from another monomer without using isoprene is used instead of this block (b) (for example, when a butadiene homopolymer block is used), a 1,2-bond is temporarily used. Even if the content is increased, the temperature at which the block copolymer (A) exhibits vibration damping performance is less than 0 ° C., which is not practical.

When an isoprene-butadiene mixture is used in combination, the content of isoprene in the mixture is 40% by weight so that the block copolymer (A) can exhibit vibration damping performance at 0 ° C. or higher. % Or more is preferable. In this case, the form of the isoprene-containing block (b) may be random, block or tapered.

Such isoprene-containing block (b)
Has a number average molecular weight of 10,000 to 200 as described above.
000. When the number average molecular weight of the isoprene-containing block (b) is less than 10,000, the block copolymer (A)
Of the block copolymer (A) is deteriorated, and the workability of the vibration damping composition is deteriorated.

The vinyl bond content of the isoprene-containing block (b) is 40% or more as described above.
In this case, the vinyl bond content may be 100%. When the vinyl bond content is less than 40%, the vibration damping performance of the block copolymer (A) is insufficient in a normal operating temperature range, which is not preferable.

In order to set the vinyl bond content to 40% or more, a Lewis base may be used as a cocatalyst when the isoprene-containing block (b) is formed by polymerization. This point will be described later.

When the content of the isoprene-containing block (b) in the block copolymer (A) is too small, the vibration damping performance of the block copolymer (A) is deteriorated and the processability is also deteriorated. If it is too much, the mechanical properties of the block copolymer (A) deteriorate, so the content is preferably 50 to 95% by weight, more preferably 60 to 90% by weight.

The block copolymer (A) composed of the vinyl aromatic compound-containing block (a) and the isoprene-containing block (b) as described above has a number average molecular weight of 30,000 to 300,000, preferably 80,000.
~ 200,000. When the number average molecular weight of the block copolymer (A) is less than 30,000, the mechanical properties of the vibration damping composition containing the block copolymer (A) are deteriorated, which is not preferable, and when it exceeds 300,000, the vibration damping composition is obtained. It is not preferable because the workability of is decreased.

As the block form of the block copolymer (A), the aromatic vinyl compound-containing block (a) is represented by a, the isoprene-containing block (b) is represented by b, and a coupling agent (for example, dihaloalkane) is used. , A dihaloaryl, an ester and the like ordinary residue) are represented by X, a (ba) _n , (ab) _n , (a
b) _m- X etc. can be mentioned. Here, n is an integer of 1 or more and m is an integer of 3 or more. Of these, a
Most preferred is the block form of -ba.

The block copolymer (A) described above is
For example, it can be produced by the following methods (1) to (3): (1) A vinyl aromatic monomer is polymerized in the presence of an alkyllithium compound as a polymerization initiator, and then isoprene or an isoprene-butadiene mixture. (2) The vinyl aromatic monomer is polymerized in the presence of an alkyllithium compound as a polymerization initiator, and then isoprene or an isoprene-butadiene mixture is polymerized, followed by coupling with a coupling agent. Ringing method; and (3) a method of polymerizing isoprene or an isoprene-butadiene mixture in the presence of a dilithium compound as a polymerization initiator, and then sequentially polymerizing a vinyl aromatic monomer.

Examples of the alkyllithium compound used in the above production methods (1) and (2) include alkyllithium compounds having an alkyl residue having 1 to 10 carbon atoms. Among them, methyl lithium, ethyl lithium, pentyl lithium, and butyl lithium can be preferably used.

Examples of the coupling agent used in the production method (2) include dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene, ethyl acetate and phenyl benzoate.

Examples of the dilithium compound used in the production method (3) include naphthalenedilithium and dilithiohexylbenzene.

In the production methods (1) to (3), the amount of the polymerization initiator or the coupling agent used is determined by the molecular weight of the block copolymer (A) and the like, but it is usually used for the polymerization. The amount is about 0.01 to 0.2 part by weight in the case of the polymerization initiator and about 0.04 to 0.8 part by weight in the case of the coupling agent, relative to 100 parts by weight of all the monomers.

When the block copolymer (A) having the block form of (ab) _m -X is produced, in the production method (2), for example, butyltrichlorosilicon or butyltrichlorosilicon is used as the coupling agent. Tin, carbon tetrachloride, silicon tetrachloride, tin tetrachloride, divinylbenzene, tolylene diisocyanate, etc. may be used.

In the above production methods (1) to (3), the vinyl bond content of the isoprene-containing block (b) is 40%.
In order to achieve the content of at least%, a Lewis base may be used as a vinylating agent during the polymerization of isoprene or isoprene-butadiene mixture as described above. Examples of such Lewis bases are ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine, N, N, N ', N'-tetramethylethylenediamine (TMEDA). And amine compounds such as N-methylmorpholine. The amount of these Lewis bases used is about 0.1 to 1000 mol times the mol number of lithium as the polymerization initiator.

In the above production methods (1) to (3), in order to facilitate the control of the reaction rate during the polymerization reaction, the polymerization is carried out in an organic solvent inert to the polymerization initiator. It is preferable to carry out the reaction. As such an organic solvent, an aliphatic hydrocarbon having 6 to 12 carbon atoms such as hexane or heptane; an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane; or an aromatic hydrocarbon such as benzene or toluene is preferably used. can do.

In the above manufacturing methods (1) to (3),
The polymerization reaction is usually carried out in the temperature range of 0 to 80 ° C. for 0.5 to 5
It takes place at 0 hours.

When the block copolymer (A) is a hydrogenated product of a block copolymer composed of a vinyl aromatic compound-containing block (a) and an isoprene-containing block (b), this hydrogen is used. The additive can be obtained by subjecting a block copolymer composed of the vinyl aromatic compound-containing block (a) and the isoprene-containing block (b) to a known hydrogenation reaction. For example, it can be obtained by reacting a block copolymer dissolved in a solvent inert to the hydrogenation catalyst with molecular hydrogen in the presence of a known hydrogenation catalyst. Here, as the hydrogenation catalyst, a Raney nickel catalyst, a heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, or Ni is supported on a carrier such as carbon, alumina, or diatom, a transition metal and an alkylaluminum compound, or the like A Ziegler-based catalyst composed of a combination can be used. As other conditions for the hydrogenation reaction, the hydrogen pressure is usually from atmospheric pressure to 200 Kg / cm ² , the reaction temperature is from room temperature to 250 ° C., and the reaction time is from 0.1 to 100 hours.

The method for separating the block copolymer (A) from the reaction solution after the polymerization reaction or after the hydrogenation reaction is not particularly limited, and for example, the block copolymer (A) may be added to the polymerization reaction solution or the hydrogenation reaction solution. The block copolymer (A) can be obtained by solidifying the block copolymer (A) by adding a poor solvent (for example, methanol) to the polymer (A), and then heating or drying under reduced pressure. Alternatively, it can be obtained by pouring the polymerization reaction liquid or the hydrogenation reaction liquid into boiling water to azeotropically remove the solvent, and then heating or drying under reduced pressure.

Next, the inorganic filler (B) which is another component of the vibration damping composition for forming the vibration damping layer will be described.

Here, the inorganic filler (B) has a function of improving the damping performance of the damping layer. As such an inorganic filler (B), those generally added to rubber and plastics have been preferably used, and specific examples thereof include mica, graphite, clay, talc, carbon black, Examples thereof include silica, wollastonite, calcium carbonate, barium sulfate and the like. The inorganic filler (B) may be used alone or in combination of two or more kinds. In this case, the shape of the inorganic filler (B) may be spherical, scale-like, needle-like, or amorphous, but scale-like fillers are preferable in the sense that the vibration-damping performance of the vibration-damping layer is enhanced.

The compounding ratio of the block copolymer (A) and the inorganic filler (B) in the vibration damping composition is 30 parts by weight of the inorganic filler (B) based on 100 parts by weight of the block copolymer (A).
To 1000 parts by weight, preferably 60 to 900 parts by weight. If the amount of the inorganic filler (B) is less than 30 parts by weight with respect to 100 parts by weight of the block copolymer (A), the effect of improving the damping performance of the damping layer cannot be sufficiently obtained, and conversely. 1
If it exceeds 000 parts by weight, it becomes difficult to mix with the block copolymer (A), the flexibility of the damping layer becomes insufficient, and further, the adhesive strength when the damping layer and the constraining layer are laminated is increased. descend.

The damping composition used in the present invention, in addition to the above block copolymer (A) and inorganic filler (B), imparts sufficient flexibility to the damping layer. For that purpose, it is preferable to add a softening agent (C) if necessary. As such a softening agent (C), a known softening agent can be appropriately selected and used, and for example, dioctyl phthalate (DOP), dioctyl adipate (DOA), process oil, liquid polyisoprene or hydrogen thereof. Examples thereof include additives, liquid polybutadiene, liquid polybutene, and polyisobutylene.

If the blending amount of the softening agent (C) in the vibration damping composition is too large, the vibration damping performance of the vibration damping composition deteriorates. Therefore, it is 300 per 100 parts by weight of the block copolymer (A).
It is preferable that the content be not more than part by weight.

In the vibration damping laminate of the present invention, the block copolymer (A), the inorganic filler (B) and the softening agent are added to the vibration damping composition as long as the effects of the present invention are not impaired. In addition to (C), other materials may be blended and used. For example, a styrene-butadiene block copolymer or a hydrogenated product thereof, a styrene-isoprene block copolymer having a vinyl bond content of the isoprene-containing block of less than 40% or a hydrogenated product thereof, an ethylene-propylene copolymer, an ethylene- Ethylene-based copolymers such as butylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer; natural rubber,
Synthetic polyisoprene, polybutadiene, styrene-butadiene copolymer, butyl rubber, EPDM, polynorbornene, polyolefins such as polyethylene and polypropylene; tackifying resins, asphalt and the like can be further added to the vibration damping composition. The blending amount of these other materials is preferably about 30 parts by weight or less based on 100 parts by weight of the block copolymer (A).

Further, known additives are added to the vibration damping composition.
For example, an antioxidant, a colorant, an ultraviolet absorber, a lubricant, and a flame retardant can be added if necessary.

The vibration-damping composition described above is kneaded and extruded with the block copolymer (A) and the inorganic filler (B) and, if necessary, the softening agent (C) and other additives. The vibration-damping layer is processed by kneading with a machine and molding into a sheet with an extrusion molding machine, an injection molding machine, a press molding machine, a calender molding machine, or the like.

Next, the substrate (constraint layer) of the vibration damping laminate of the present invention will be described.

In the present invention, a fiber-reinforced thermoplastic resin sheet having excellent workability and dimensional stability as a base material (constraint layer) and excellent three-dimensional processability is obtained, which is substantially uniform in one direction. A fiber containing 30 to 85% by volume of aligned and continuous fibers is used.

The thermoplastic resin constituting the fiber-reinforced thermoplastic resin sheet is not particularly limited, and various thermoplastic resins can be used. For example, polypropylene,
Polyolefin resin such as polyethylene, ethylene-propylene copolymer, α-olefin homopolymer or copolymer; polystyrene resin such as styrene or methylstyrene homopolymer or copolymer of these and α-olefin; vinyl chloride homopolymer A polyvinyl chloride resin such as a polymer or a copolymer of the same and an α-olefin can be used. In addition, AS resin, A
BS resin, ASA resin (acrylonitrile / styrene /
Acrylic ester resin), polymethyl methacrylate, nylon, polyacetal, polycarbonate, polyethylene terephthalate, polyphenylene oxide, fluororesin, polyphenylene sulfide, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyimide, polyarylate, etc. can do. Among them, general-purpose polyolefin resins such as polyethylene and polypropylene, polystyrene resins, and polyvinyl chloride resins can be particularly preferably used from the viewpoints of strength, abrasion resistance, price, recycling characteristics and the like.

As the fibers used in the fiber-reinforced thermoplastic resin sheet, known fibers can be used, for example, glass fibers, carbon fibers, aramid fibers,
Silicon carbide fibers and the like can be used. Among these, it is preferable to use glass fiber from the viewpoint of function and economy. The form of such fibers is 3 to 2
From the viewpoint of strength and rigidity of the fiber reinforced thermoplastic resin sheet, it is preferable to use a yarn or roving in which 200 to 12000 5 μm monofilaments are bundled.

When glass fibers are used as the fibers, it is preferable that the surface treatment is performed with a sizing agent in order to bundle the filaments. In addition, surface treatment with a coupling agent is preferable in order to improve the adhesion of the glass fiber to the resin.

Here, as the sizing agent, a known sizing agent which is softened at the melting temperature of the thermoplastic resin of the fiber reinforced thermoplastic resin sheet and does not prevent the thermoplastic resin from impregnating the fiber bundle is used. However, it is preferable to use, for example, a resin containing the same kind of resin as the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet as a main component.

Further, as the coupling agent used for the surface treatment of the glass fiber, a known silane coupling agent, titanium coupling agent, zirconium, depending on the type of the thermoplastic resin of the fiber reinforced thermoplastic resin sheet, is used. It can be appropriately selected from the coupling agents and the like.

For example, when the thermoplastic resin of the fiber reinforced thermoplastic resin sheet is nylon or polycarbonate, the coupling agent is γ-aminopropyl-trimethoxysilane, N- (β-aminoethyl) -γ- Aminopropyl-trimethoxysilane and the like can be preferably used. When the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet is polyethylene terephthalate or polybutylene terephthalate, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, γ
-Glycitoxy-propyltrimethoxysilane, γ-aminopropyl-trimethoxysilane and the like can be preferably used. When the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet is polyethylene or polypropylene, vinyltrimethoxysilane, vinyl-tris-
(2-Methoxyethoxy) silane, γ-methacryloxy-propyltrimethoxysilane and the like can be preferably used. When the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet is polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyarylate or fluororesin, the above-mentioned coupling In addition to the agent, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ
-Chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-aminophenyltriethoxysilane and the like can be used.

In the fiber-reinforced thermoplastic resin sheet formed from the thermoplastic resin and the fibers as described above,
As described above, the fiber content is required to be 30 to 85% by volume, and preferably 30 to 70% by volume. If the content of fibers in the fiber-reinforced thermoplastic resin sheet is less than 30% by volume, the strength and rigidity of the fiber-reinforced thermoplastic resin sheet are insufficient, and if it exceeds 85% by volume, the fibers and the thermoplastic resin are As a result, the strength and rigidity of the fiber-reinforced thermoplastic resin sheet become insufficient.

The thickness of the fiber-reinforced thermoplastic resin sheet constituting the base material (constraint layer) is determined according to the purpose of use of the vibration damping laminate, etc., but is usually about 0.05 to 0.6 mm.
It is.

In the present invention, the base material (constraint layer) may be formed by laminating two or more fiber-reinforced thermoplastic resin sheets for the purpose of improving the mechanical strength of the vibration damping laminate. In this case, it is preferable that the respective fiber reinforced thermoplastic resin sheets are laminated so that the fiber alignment directions of the respective fiber reinforced thermoplastic resin sheets are not in the same direction. That is, with respect to the alignment direction of the fibers of the fiber-reinforced thermoplastic resin sheet of the first layer, the alignment direction of the fibers of the fiber-reinforced thermoplastic resin sheet of the second and subsequent layers is 0 to 180 degrees (provided that 0 and 180 degrees are It is preferable to stack in any direction between (not including). For example, when laminating two layers, it is preferable to rotate the fiber direction of the second layer by 90 degrees with respect to the fiber direction of the first layer.

The fiber-reinforced thermoplastic resin sheet constituting the base material (constraint layer) described above can be manufactured by impregnating a web of fibers or a bundle of fibers aligned in one direction with the thermoplastic resin. it can. For example, it is possible to produce a fiber-reinforced thermoplastic resin sheet by dissolving a thermoplastic resin in a solvent, impregnating the obtained resin solution into a web of fibers or a fiber bundle, and then removing the solvent while defoaming. it can. Alternatively, a fiber-reinforced thermoplastic resin sheet can be produced by directly impregnating a web or fiber bundle of fibers with a heated melt of a thermoplastic resin, defoaming and cooling.

As a more specific method for producing a fiber-reinforced thermoplastic resin sheet, for example, the method disclosed in JP-A-2-48907 can be mentioned. In this method, the surface of a glass monofilament having a thickness of 13 μm is treated with γ-methacryloxy-propyltrimethoxysilane, and 1800 filaments are bundled into a yarn with a small twist, and the yarn is stretched with a uniform tension of 80 filaments. It is manufactured by arranging in one direction into a bundle, entwining a thermoplastic resin therein, and immersing the resin in a bundle while squeezing the resin with a hot roll.

When a plurality of the above-mentioned fiber-reinforced thermoplastic resin sheets are laminated to form a base material (constraint layer), heating and pressure bonding at a temperature not lower than the melting point of the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet is necessary. Good. The heating temperature and heating time at this time can be appropriately determined according to the type of thermoplastic resin and the number of sheets to be laminated. For example, when four polypropylene-based fiber-reinforced thermoplastic resin sheets having a thickness of 0.2 mm are laminated, usually 170 to 220 ° C.
It may be heated and pressure-bonded for 0.1 to 0.5 minutes. When the pressure during the pressure bonding is too low, deaeration tends to be insufficient, and when the pressure is too high, the linearity of the fibers arranged in one direction tends to be disturbed, so that the pressure is usually 0.1 to 10 kg / cm ² , preferably Is 0.1-5 Kg / cm ² , more preferably 0.1-2 K
g / cm ² .

The vibration-damping laminate of the present invention can be manufactured by laminating the above-mentioned substrate (constraint layer) and the vibration-damping layer. At this time, known methods and apparatuses conventionally used for producing a laminate can be used. For example, when the vibration-damping composition is formed into a sheet by a T-die extruder, the vibration-damping laminate of the present invention can be manufactured by simultaneously heat-fusing and laminating a fiber-reinforced thermoplastic resin sheet. Alternatively, the vibration damping composition of the present invention can be produced by directly laminating the vibration damping composition on the fiber-reinforced thermoplastic resin sheet with a calendar roll. Alternatively, the vibration damping composition may be formed into a sheet by a known method, and the sheet and the fiber-reinforced thermoplastic resin sheet may be laminated by pressure heat press molding to produce the vibration damping laminate of the present invention.

The vibration damping laminate of the present invention can be formed into a three-dimensional shape other than the sheet shape. In this case, the vibration-damping laminate once formed into a sheet is heated to a temperature at which the thermoplastic resin of the fiber-reinforced thermoplastic resin sheet constituting the base material (constraining layer) is softened, and pressure heat press molding, It may be formed into a desired shape by vacuum / pressure forming. As described above, the vibration damping laminate of the present invention has excellent secondary workability.

Further, an adhesive layer can be formed on at least one surface of the vibration damping laminate of the present invention in order to simplify the sticking operation to the vibration body. The adhesive layer can be formed by coating or transferring the adhesive in the manufacturing process of the vibration damping laminate.

As the adhesive, various adhesives may be used as long as sufficient adhesive strength can be secured between the vibration damping layer or the base material (constraint layer) and the vibrating body. Natural rubber adhesives, chloroprene adhesives, styrene elastomer adhesives, acrylic adhesives and the like can be preferably used.

As a method of using the vibration-damping laminate of the present invention, a method of attaching the vibration-damping laminate to the vibration body via an adhesive layer and using the vibration-damping laminate is generally used. In addition, it is also possible to use itself as a vibration-damping panel or a vibration-damping molded product without attaching the vibration-damping laminate to the vibration body.

The vibration-damping laminated body of the present invention described above is a vibration-damping material excellent in vibration-damping performance and excellent in moldability and secondary workability, and can be used for automobiles, vacuum cleaners, washing machines, refrigerators,
Home appliances such as air conditioners, speaker boxes, CD players, audio products such as VCRs, office automation equipment such as word processors, computers, printers, copiers, electric saws, electric drills, machine tools such as chainsaws, flooring materials for walls, walls It can be used in a wide range of fields where it is necessary to prevent the influence of vibration such as materials.

[0071]

The present invention will be specifically described below with reference to examples.

In the following Reference Examples and Examples,
The number average molecular weight of the block or copolymer corresponding to the vinyl aromatic compound-containing block (a), the isoprene-containing block (b) and the block copolymer (A) was calculated as a styrene-equivalent molecular weight by GPC. The vinyl bond content of the block corresponding to the isoprene-containing block (b) was calculated from the ¹ H-NMR spectrum.

Reference Example 1 (Synthesis of Block Copolymer) Cyclohexane as a solvent, n-butyllithium as a polymerization initiator, and TMEDA as a vinylating agent were charged in a pressure resistant reactor substituted with dry nitrogen, and styrene, Polymerization was carried out by adding isoprene and styrene in that order, and styrene having a number average molecular weight of 72,000 was added.
Isoprene-styrene type block copolymer (styrene content 20%; polystyrene block number average molecular weight 67)
00; vinyl bond content 79.9%) was obtained.

Reference Example 2 (Preparation of vibration damping composition) 100 parts by weight of the block copolymer obtained in Reference Example 1, mica (Clarite mica 150)
S, 50 parts by weight of Kuraray Co., 50 parts by weight of light calcium carbonate (made by Maruo Calcium Co.), 30 parts by weight of synthetic polyisoprene (IR-10, made by Kuraray Co., Ltd.), carbon black (Asahi # 55, Asahi Carbon Co., Ltd. ) 0.5 parts by weight, 0.1 parts by weight of a phenolic antioxidant (Irganox 1010, manufactured by Ciba Geigy), and 1 part by weight of calcium stearate are kneaded in a kneader at a temperature of 180 ° C. for 10 minutes, and then uniaxially extruded. A vibration damping composition in the form of pellets was prepared by molding with a machine.

Reference Example 3 (Preparation of Fiber Reinforced Thermoplastic Resin Sheet (Restriction Layer)) According to the method disclosed in JP-A-2-48907, the surface of a monofilament made of glass and having a thickness of 13 μm was coated with γ-methacryloxy-. Treated with propyltrimethoxysilane, bundled 1800 yarns into a non-twisted yarn, aligned the yarns in one direction while pulling 80 yarns with a uniform tension, entangle polypropylene with the yarn, and heat the polypropylene with a heat roll. While squeezing, the yarn was impregnated to prepare a fiber-reinforced thermoplastic resin sheet having a width of 650 mm. The glass fiber content in this fiber-reinforced thermoplastic resin sheet was 50% by volume.

Reference Example 4 (Preparation of Laminated Body (Constraining Layer) of Plural Fiber Reinforced Thermoplastic Resin Sheets) Two fiber reinforced thermoplastic resin sheets obtained in Reference Example 3 were prepared, and the second fiber reinforced The thermoplastic resin sheet is laminated and adhered so that the fiber direction of the thermoplastic resin sheet is rotated by 90 degrees with respect to the fiber direction of the first fiber-reinforced thermoplastic resin sheet, and is then placed on a heating plate heated to 180 ° C. for 30 minutes. After being contact-heated and pressure-bonded for 2 seconds, a laminate of fiber-reinforced thermoplastic resin sheets was produced by press-cooling at a pressure of 0.2 Kg / cm ^{2 in} a press heated to 70 ° C.

Example 1 Pellets of the vibration damping composition obtained in Reference Example 2 were mixed with 180
A sheet having a thickness of 1 mm was formed at a temperature of 50 ° C. and a pressure of 50 Kg / cm ^{2, and} the sheet was laminated on the fiber-reinforced thermoplastic resin sheet obtained in Reference Example 3 and heated at 170 ° C. and 0.2 K with a heating plate.
After thermocompression bonding at a pressure of g / cm ² for 30 seconds, it was pressed and cooled at 80 ° C. and a pressure of 0.2 Kg / cm ² while pressing to obtain a vibration damping laminate.

With respect to the obtained vibration-damping laminate, the vibration-damping performance and the secondary workability were evaluated as described below. The results obtained are shown in Table 1.

* "Evaluation of damping performance" The loss coefficient was measured by the cantilever resonance method, and the obtained numerical value was used as an index of damping performance. In this case, the higher the value, the better the vibration damping performance.

In the case of a vibration damping laminate having a structure in which a vibration damping layer (damping composition layer) is laminated on one surface of a base material (fiber reinforced thermoplastic resin sheet) which functions as a constraining layer, Width 2
0mm x length 20cm x thickness 1mm cold rolled steel plate,
The one in which the damping layer surface was adhered with a double-sided tape was used as a measurement sample. Further, in the case of a vibration-damping laminate comprising three layers of a base material (fiber-reinforced thermoplastic resin sheet) / damping layer (vibration-damping composition layer) / base material (fiber-reinforced thermoplastic resin sheet), the width is The laminate itself having a size of 20 mm and a length of 20 cm was used as a measurement sample.

* "Evaluation of Secondary Workability" The vibration damping laminate was press-molded (secondary processing) into a cylindrical shape shown in FIG. 1 by using a pair of upper and lower FRP matched dies, and the obtained molded product was obtained. Was visually evaluated.

A specific press molding operation is performed by using a molding machine equipped with a far-infrared heater and a pressing device while first fixing the outer periphery of the vibration damping laminate with a clamp so that the vibration damping laminate does not come from above and below. Heat to 160 ° C for 40 seconds on contact,
Immediately move to the press machine, and the temperature of FRP is 50 ℃.
Molding was performed by a matched mold at a pressure of 5 Kg / cm ² , the clamp was opened at that time, and pressure cooling molding was performed for 60 seconds. This makes the diameter of the recess 10 cm
A cylindrical molded product having a depth of 5 cm was obtained.

Example 2 A vibration damping laminate was obtained in the same manner as in Example 1 except that the laminate of the fiber reinforced thermoplastic resin sheet obtained in Reference Example 4 was used as the substrate.

Regarding the obtained vibration damping laminate, Example 1 was used.
In the same manner as above, the vibration damping performance and the secondary workability were evaluated. The results obtained are shown in Table 1.

Example 3 Pellets of the vibration damping composition obtained in Reference Example 2 were mixed with 180
A sheet having a thickness of 1 mm was formed at a temperature of 50 ° C. and a pressure of 50 Kg / cm ² , and the obtained sheet was sandwiched between the laminated body of the fiber-reinforced thermoplastic resin sheet obtained in Reference Example 4 and heated with a heating platen 17
After thermocompression bonding at 0 ° C. and a pressure of 0.2 Kg / cm ² for 30 seconds, a vibration damping laminate was obtained by pressing and cooling at 80 ° C. and a pressure of 0.2 Kg / cm ² while pressing.

Regarding the obtained vibration damping laminate, Example 1 was used.
In the same manner as above, the vibration damping performance and the secondary workability were evaluated. The results obtained are shown in Table 1.

Comparative Example 1 Pellets of the vibration damping composition obtained in Reference Example 2 were mixed with 180
The sheet was formed into a sheet having a thickness of 1 mm at 50 ° C. and a pressure of 50 kg / cm ² , and the vibration damping performance of the sheet itself was evaluated in the same manner as in Example 1. Table 2 shows the results.

Since the vibration-damping sheet of this comparative example did not have the constraining layer, the shape-retaining property at the time of heating was not sufficient and it could not be applied to a molding machine for evaluation of secondary workability.

Comparative Example 2 A thickness of 0.02 m was used instead of the fiber reinforced thermoplastic resin sheet.
A vibration damping laminate was prepared in the same manner as in Example 1 except that the stainless steel foil of m was used, and the vibration damping performance and the secondary workability were evaluated in the same manner as in Example 1 as described later. . Table 2 shows the obtained results.

Comparative Example 3 A thickness of 0.02 m was used instead of the fiber reinforced thermoplastic resin sheet.
A vibration damping laminate was prepared in the same manner as in Example 3 except that the stainless steel foil of m was used, and the vibration damping performance and the secondary workability were evaluated in the same manner as in Example 1. Table 2 shows the obtained results.
Shown in

(Evaluation Results) As shown in Tables 1 and 2 below, the vibration-damping laminates of Examples 1 to 3 had the vibration-damping sheets of Comparative Example 1 having no base material (constraint layer). It can be seen that the vibration damping performance (loss coefficient) and the secondary workability are superior to those of (1). In addition, the vibration-damping laminates of Examples 1 to 3 were those of Comparative Examples 2 and 3 in which stainless steel foil was used as the base material (constraint layer) instead of the base material (constraint layer) made of the fiber-reinforced thermoplastic resin sheet. It can be seen that the secondary workability is superior to that of the vibration damping laminate.

[0092]

[Table 1]

[0093]

[Table 2] Table 2 Note * 1 Molding was not possible according to the mold, and peeling was observed in a part between the stainless steel foil and the damping layer.

[0094]

EFFECTS OF THE INVENTION According to the present invention, it has a damping layer which exhibits high damping performance and flexibility in a wide temperature range without performing a vulcanization operation, is excellent in processability, and has flexibility in molding. Provided is a vibration-damping laminate capable of obtaining a molded product which is high in appearance quality, physical performance, dimensional stability and the like at the same time.

[Brief description of drawings]

FIG. 1 is a cross-sectional view (FIG. (A)) and a perspective view (FIG. (B)) of a secondary molded product of a vibration damping laminate for evaluating secondary workability of the vibration damping laminate. is there.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Hideo Takamatsu 2-3-10 Nihonbashi, Chuo-ku, Tokyo Kuraray Co., Ltd. (72) Inventor Kazuaki Kata 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo Mitsui Toatsu Inside the Chemical Co., Ltd. (72) Inventor Ichihiro Mitsui Toatsu Chemical Co., Ltd. 1190 Kasamacho, Sakae-ku, Yokohama

Claims (5)

[Claims] 1. A vibration-damping laminate in which a base material and a vibration-damping layer are laminated: the vibration-damping layer contains a block copolymer (A) and an inorganic filler (B). A layer formed from the composition, which contains 30 to 1000 parts by weight of the inorganic filler (B) per 100 parts by weight of the block copolymer (A), and the block copolymer (A) is vinyl. A block copolymer having a number average molecular weight of 30,000 to 300,000 or a hydrogenated product thereof, which is composed of an aromatic compound-containing block (a) and an isoprene-containing block (b), and the vinyl aromatic compound-containing block (a) is Number average molecular weight formed from vinyl aromatic monomer is 2500-4
The block (b) containing isoprene is formed from isoprene or an isoprene-butadiene mixture and has a number average molecular weight of 10,000 to 20.
0000 and the total content of 3,4-bonds and 1,2-bonds is 40% or more; and the substrate has 30 continuous fibers arranged substantially uniformly in one direction. A vibration-damping laminated body, which is a fiber-reinforced thermoplastic resin sheet contained in a proportion of ˜85% by volume. 2. The vibration damping laminate according to claim 1, which further contains a softening agent (C) in an amount of 300 parts by weight or less based on 100 parts by weight of the block copolymer (A). 3. The vibration-damping laminate according to claim 1, wherein the fiber in the fiber-reinforced thermoplastic resin sheet is glass fiber, and the thermoplastic resin is polyolefin resin, polystyrene resin or polyvinyl chloride resin. . 4. The base material is composed of a laminate of two or more fiber-reinforced thermoplastic resin sheets, and is laminated so that the fiber alignment directions of the respective fiber-reinforced thermoplastic resin sheets are not the same. The vibration damping laminate according to any one of claims 1 to 3. 5. The vibration damping laminate according to claim 1, further comprising an adhesive layer formed on at least one surface of the vibration damping laminate.