KR900000972B1 - Vibration-damping resin composition - Google Patents

Abstract

A damping resin compsn. comprises 10-95 wt.% a noncrystalline thermoplastic resin (A) and 90-5 wt.% a crystalline thermoplastic resin (B). (A) is a non-crystalline polymer with low glass transition point, and has max. tan delta above 0.5, in the frequency range 0.1-2000 Hz, at -50-150≰C. (B) is a crystalline polymer whose m.p. is higher than the glass transition point of (A) and has a rigidity above 1x108 dyne/cm2 at temp. and frequency at which (A) shows max. tan delta.

Description

Vibration Resistant Resin Composition

1 is a curve diagram showing the vibration damping property (η) of a composite steel sheet using a polyvinyl acetate-polypropylene-based composition according to temperature change.

2 is a curve diagram showing the stiffness (G ^* ) and tan δ of the composition of the same system as in FIG. 1 according to temperature change.

3 is a curve diagram showing the vibration damping property (η) of a composite steel sheet using a composition in which polyvinyl acetate is mixed with low density polyethylene or ethylene-vinyl acetate copolymer according to temperature change.

4 is a curve showing the vibration damping properties of a composite steel sheet using a composition in which polypropylene or high density polyethylene is mixed with polystyrene according to temperature change.

5 is a curve showing the vibration damping property (η) of a composite steel sheet using a composition in which polypropylene is mixed with a styrene-acrylic acid ester copolymer according to temperature change.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition excellent in vibration damping properties, and more particularly to a vibration damping resin composition useful as a vibration damping layer of a composite metal plate for vibration damping.

Recently, due to the development of transportation facilities and the proximity of factories and residential areas, noise and vibration generated by various automobiles, machines, and devices have become a problem in health and environmental preservation of local communities, and the countermeasures are urgent.

In particular, noise reduction is greatly desired in parts around engines such as oil pens and engine covers that block engine sounds of automobiles, home appliances, and metal processing machines. As one of the noise countermeasures, the use of a vibration damping composite metal sheet, such as a vibration damping composite steel sheet, is used to damp vibration by internal friction caused by shear deformation of the viscous material in the middle layer of the composite metal sheet. Is used in the form surrounding the noise source.

Therefore, in addition to being used in the form of a plate, the vibration damping composite metal sheet is molded into a desired shape by bending, inserting, or the like. As a material used for the intermediate | middle layer of the vibration damping composite metal plate, various polymers, such as vinyl acetate resin and a vinyl chloride resin, thermoplastic resins, such as a vinyl acetate ethylene copolymer and an acrylonitrile styrene copolymer, and compositions with these and a plasticizer, or Thermosetting resins, such as a urethane resin and an epoxy resin, have been used.

Moreover, the resin composition which mixed two or more types of resin is also proposed. As a resin composition, for example, Japanese Unexamined Patent Application Publication No. 54-1354 discloses a composition in which a viscoelastic polymer such as polyurethane is mixed with an ethylene- (meth) acrylic acid copolymer or an acid copolymer such as ionoma, and Japanese Patent Application No. 54-1354. In Publication 59-80454, there is disclosed a composition in which an amorphous polymer is blended with a crystalline polyolefin modified with an unsaturated carboxylic acid or an anhydride thereof.

As also disclosed in Japanese Patent Application Laid-Open No. 57-167360, a water dispersion of a composition made of a styrene-acrylic acid ester copolymer and a flaky inorganic powder is also proposed.

Viscoelastic material, which has been used as an intermediate layer to provide vibration damping to a composite metal sheet for vibration damping, has a temperature that indicates the maximum value of its tan loss tangent than the glass transition point of the material. At high temperatures, the stiffness ratio of the viscoelastic material used at that temperature is drastically lowered, and the damping property (η) as the vibration damping composite metal sheet is not necessarily sufficiently exhibited (the laminate of the same material as the vibration damping composite metal sheet). In order to have high vibration damping, it is necessary to have a high vibration damping capacity of the viscoelastic material itself used as an intermediate layer and a high degree of stiffness of the viscoelastic material, so that the vibration damping performance is not sufficiently exhibited in a region with low rigidity), especially at a high temperature. There was a problem of sharply falling.

In addition, even when two or more kinds of resins are mixed and used as described above, the glass transition point of the composition is lowered because of compatibility between the resins, and it is not always necessary to abuse the vibration damping property at the high temperature side.

Moreover, the vibration damping property, the bending process, the tightening process, etc. of the vibration damping composite metal plate using the damping resin composition do not necessarily improve workability. Therefore, the appearance of the damping resin composition useful for the damping layer of the vibration damping composite metal plate which is excellent in damping property and workability, and also excellent in mechanical strength is anticipated.

Here, in order to help the understanding of the present invention, the tangent loss tangent, the stiffness (G`), the damping property (η), and the relationship between them will be described in detail.

First, tanδ represents a tangent when the acquaintance (deviation) of the phase is set to δ when the response is delayed when a stimulus such as vibration is applied to the material. Since the vibration stress is proportional to the vibration deformation, the elastic modulus (E) is expressed in the following complex form when the stress is a function of deformation (bending).

E ^* = E` + iE ^*

Here, E ^* is called a complex elastic modulus, E` of the real part is called a dynamic modulus or storage modulus, and E ＂of an imaginary part is called a loss modulus or a dynamic loss rate.

E 'is a term indicating a measure of energy stored by a given elastic modulus as a normal elastic modulus, and E' is a late response due to a viscous behavior when a strain is applied to a material, causing a phase shift and dissipation of energy. An attenuation type representing the measure of the rate at which

인 식으로 표시된다.And tanδ is tanδ =

Recognized.

As shown above, as tan δ increases, the vibration absorption capacity of the polymer material increases.

Second, with respect to the stiffness (storage shear modulus: Storago Shear Modulus, G`), the complex shear modulus is expressed by the formula G <sup>*</sup> LG <sup>*</sup> = G` + iG ＂as described in tanδ of the first term.

Where G 'is the storage shear modulus and G' is the loss shear modulus. The stiffness ratio referred to in the present invention is a general shear modulus corresponding to G` (storage shear modulus), which is represented by the following formula.

에서 γ는 전단응력, δ는 어긋남(변형)양을 나타낸다.G '=

Where γ is the shear stress and δ is the amount of deviation (strain).

인 식으로 나타낸다.Again, the relationship between G` and tanδ is tanδ =

It is represented by the formula.

Third, with respect to vibration damping property (loss factor η), vibration damping is expressed as η as a display amount representing the automatic damping ability of the metal sheet for vibration damping. The loss coefficient η is expressed by the formula n = ΔE / 2πE when the vibration energy initially possessed by the vibration system is E and the energy dissipated as vibration / cycle is ΔE.

The inventors of the present invention used a composition in which a crystalline thermoplastic resin incompatible with a viscoelastic material conventionally used as a vibration damping intermediate layer was used. It was found that it is effective to maintain the stiffness ratio of the composition at a temperature exhibiting more effectively on the side and showing the maximum δ of the viscoelastic material by adding a crystalline thermoplastic resin.

That is, the composition of the first state of the present invention is 10-95% by weight of the amorphous thermoplastic polymer (a) below and the crystalline thermoplastic polymer (b) below which is not compatible with each other with the polymer (a). It is an amorphous polymer having a lower glass transition point, and having a tan δ maximum of 0.5 or more in a temperature of -50 to 150 ° C. and a frequency of 0.1-20000 Hz, and the crystalline thermoplastic polymer (b) is an amorphous thermoplastic polymer ( It is a crystalline polymer having a melting point higher than the glass transition point of a) and an amorphous thermoplastic polymer (a) having a stiffness of 1 × 10 ⁸ dyne / cm ² or more at a temperature and frequency exhibiting a maximum value of tan δ.

The composition of the second state of the present invention comprises 10-90% by weight of the amorphous heat-transportable polymer (a) shown in the first state and the crystalline thermoplastic polymer shown in the first state incompatible with the polymer (a) ( b) 90 = 10% by weight, at least one of the monomers constituting the amorphous polymer (a) is at least 0.5% by weight relative to the total amount of the polymer (a) is a vibration damping property copolymerized to the crystalline polymer (b) Resin composition.

The composition in the second state is very excellent in mechanical strength, for example, tensile property and stretchability, and when used as a composite metal sheet, moldability is excellent.

In the composition shown in the second state, a polymer (A) derived from an acrylic ester and a vinyl aromatic monomer as the amorphous thermoplastic polymer (a), and a crystalline polyolefin (B) as the crystalline thermoplastic polymer (b) Selecting and using the damping resin composition by the combination of a polymer (A) and a polymer (B) for a composite metal plate becomes excellent not only in damping property but especially workability and mechanical strength.

In the damping composite metal sheet using the damping resin composition of the present invention, it is necessary that the damping property (η) is 0.05 or more and preferably 0.1 or more at an environmental temperature of 0-150 ° C. and a noise frequency of 20-20000 Hz of a noise generating source. .

Therefore, the amorphous thermoplastic polymer (a) used in the compositions of the first and second states of the present invention has a maximum value of tanδ of 0.5 or more, preferably 1.0 or more at a temperature of -50 to 150 ° C and a frequency of 0.1-20000 Hz. There is a need.

As such an amorphous polymer (a), various polymers described in JP-A 53-42069 can be used as a polymer or copolymer having a high vibration damping effect. For example, a vinyl ester type such as polyvinyl acetate Styrene polymers such as polymers, polyvinyl butyral and polystyrene, thermoplastic rubbers such as polyisobutylene, vinyl halide polymers such as polyvinyl chloride, and acrylic polymers such as polymethyl methacrylate.

Of these, vinyl ester, styrene, and acrylic polymers or copolymers are preferable, and copolymers of styrene monomers and acrylic monomers are particularly preferable.

As the polymer (a), two or more kinds of these amorphous resins may be combined, or as long as they give the necessary tan δ, the presence or absence of compatibility between the polymers in combination thereof is not a problem.

In the first and second states of the present invention, the crystalline thermoplastic polymer (b) blended with the polymer (a) is incompatible with the polymer (a), and the temperature and frequency at which the polymer (a) exhibits a tan δ maximum. The stiffness (G`) of the polymer (b) at is 1 × 10 ⁸ dyne / cm ² or more, preferably 5 × 10 ⁸ dyne / cm ² or more, more preferably 6 × 10 ⁸ dyne / cm ² or more Will be used.

Incompatibility in this invention means that when a polymer (a) and a polymer (b) measured dynamic viscoelasticity in the state of a composition, they respectively independently show a tan-delta maximum value.

When the polymer (a) and the polymer (b) are compatible, the composition exhibits a tan δ maximum at a single temperature, and the stiffness of the composition is significantly lowered at that temperature, and the vibration damping properties of the vibration damping composite metal sheet may not be sufficiently exhibited. There is.

In the composition of the present invention, the stiffness of the amorphous polymer (a) alone at a temperature exhibiting a tan δ maximum drops significantly, so that a crystalline polymer having a high stiffness at that temperature is required to maintain the high stiffness of the composition. It is necessary to mix | blend (b), and for this purpose, it is necessary for the polymer (b) to be incompatible with the polymer (a), and its melting point is higher than the glass transition point of the polymer (a).

In the case of the composite metal plate, the maximum value of η is shown at a temperature higher than the temperature indicating the tan δ maximum value of the resin used in the intermediate layer. Therefore, if the melting point of the polymer (b) is close to the glass transition point of the polymer (a), the polymer (a (B) softens or melts the resin in the composition at a temperature at which η of the composite metal sheet is expressed by tanδ, thereby significantly reducing the rigidity of the composition, thereby sufficiently exhibiting the damping property (η) of the vibration damping composite metal sheet. There is a risk of not being.

Therefore, the melting point of the polymer (b) is preferably 30 ° C or more, more preferably 50 ° C or more, higher than the glass transition point of the polymer (a).

The polymer (b) to be blended in the present invention may use a plurality of resins in combination. Examples of the crystalline polymer (b) include crystalline polyolefin resins such as crystalline α-olefin resins such as polyethylene and polypropylene, polyamides, and polyesters. Among them, crystalline α-olefin resins are preferable, and high-density polyethylene and polypropylene or higher higher α-olefin polymers having a high melting point are particularly preferable.

A very preferred combination of the amorphous thermoplastic polymer (a) and the crystalline thermoplastic polymer (b) is crystalline ethylene as polymer (b) using a vinyl ester, styrene or acrylic polymer or copolymer as polymer (a). It is the case of using a system or a propylene polymer.

The compounding quantity of the amorphous polymer (a) in the damping resin composition of this invention is 10-95 weight% in the composition of a 1st state, Preferably it is 20-90 weight%, More preferably, it is 30-80 weight% to be. In addition, in the composition of the second state of the present invention, the content of the polymer (a) is 10-90% by weight, preferably 20-70% by weight, more preferably 30-60% by weight.

The vibration damping property (η) of the composite metal sheet for vibration damping which used the resin composition of this invention for the intermediate | middle layer needs 0.05 or more, preferably 0.1 or more from a vibration damping effect, and the compounding quantity of a polymer (a) also in all said states When less than the lower limit value indicated above, the polymer (a) lowers the tan δ of the composition, and as a result, the η of the composite metal plate using the lower part may be lowered, and thus, sufficient vibration damping performance may not be obtained. The workability of the composite steel sheet is lowered.

The compounding quantity of the crystalline polymer (b) in the resin composition of this invention is 90-5 weight%, Preferably it is 80-10 weight%, More preferably, in the composition of a 1st state according to the compounding quantity of the said polymer (a). The following is 70-20% by weight.

Moreover, in the composition of the 2nd state of this invention, the compounding quantity of a polymer (b) is 90-10 weight%, Preferably it is 80-30 weight%, More preferably, 70- Depending on the compounding quantity of the said polymer (a). 40 wt%.

In all the compositions of the first and second states, when the blending amount of the polymer (b) is less than the lower limit indicated above, the rigidity of the composition is insufficient, and the? And the workability of the vibration damping composite metal plate using the composition are lowered. .

On the other hand, when the compounding quantity of a polymer (b) exceeds each upper limit shown above, since the maximum value of tan-delta falls with the polymer (a) in the composition of all states, (eta) of the vibration damping composite metal plate using this composition also falls.

In the composition of the second state of the present invention, at least one of the monomers constituting the amorphous thermoplastic polymer (a) is copolymerized (graft copolymerization or block copolymerization) to the crystalline thermoplastic polymer (b). The copolymerization amount is at least 0.5% by weight, preferably at least 1% by weight, more preferably at least 3% by weight of the total amount of the polymer (a). When the amount of copolymerization is equal to or greater than the above amount, the mechanical strength of the composition, for example, the tensile property and the elongation property is improved, and the molding processability in bending, tightening, etc. of the vibration damping composite metal pin using the composition is further improved.

Compositions of the first and second states of the present invention are obtained by melt kneading or solution mixing amorphous polymer (a) and crystalline polymer (b), wherein the composition of the second state is block copolymerization or graft. It is preferable to obtain in the form of copolymerization. Examples of such a copolymer include ethylene-vinyl acetate block copolymer polypropylene-vinyl acetate graft copolymer. Moreover, the form of a copolymer and the technique of simple kneading can also be used in combination.

As a method of block or graft copolymerization, for example, as described in Japanese Patent Application Laid-Open No. 59-27934, copolymerization of polymer (a) to polymer (b) using polyperoxide of amorphous polymer (a) A method of producing a copolymer by reacting a polymer (a) and a functional group introduced into the polymer (b) described in Japanese Patent Application Laid-Open No. 58-198529, and also described in Japanese Patent Application Laid-Open No. 58-53003 Various block or graft copolymerization methods can be used, such as the method of the aqueous suspension graft copolymerization of a resin and a vinyl monomer.

In the vibration damping resin composition according to the second aspect of the present invention, a polymer (A) derived from an acrylic ester and a vinyl aromatic monomer, in particular, is a crystalline polyolefin as the amorphous thermoplastic polymer (a). The composition obtained by selecting (B) is particularly useful for the vibration damping layer of the composite metal plate for vibration damping, which has excellent vibration damping, mechanical strength, and workability because it is particularly excellent in workability and mechanical properties such as tensile property and stretchability. It becomes a vibration damping resin composition.

The polymer (A) derived from the acrylic acid ester and the vinyl aromatic monomer includes not only the copolymer consisting of both monomers but also acrylic acid ester and / or vinyl aromatic monomer copolymerized with the polyolefin.

As acrylic ester, it is an alkyl ester of acrylic acid or methacrylic acid, For example, C1-C18 alkyl ester of (meth) acrylic acid, 2-alkoxyethyl ester of (meth) acrylic acid, and diethylene glycol mono of (meth) acrylic acid Alkyl esters; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, Nonyl acrylate, isononyl acrylate, decyl acrylate, undecyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monobutyl ether acrylate, linarool acrylate ( linalool), methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylate Isobutyl, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, nonyl methacrylate, isonyl methacrylate, methacrylic acid Decyl, undecyl methacrylate, lautyl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like can be used.

Preferred examples include n- or isoalkyl esters of 1 to 4 carbon atoms of acrylic acid, alkyl esters of 5 to 18 carbon atoms of acrylic acid, 2-alkoxyethyl esters of 1 to 4 carbon atoms of acrylic acid, and diethylene glycol monos having 1 to 4 carbon atoms of acrylic acid. Alkyl ether ester, methacrylic acid n-butyl, methacrylic acid alkyl ester of 5 to 18 carbon atoms.

More preferred examples are n-butyl acrylate, 2-ethylhexyl acrylate, linaro acrylate, isononyl acrylate, 2-butoxyethyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl methacrylate and tridecyl methacrylate. .

Moreover, as a vinyl aromatic monomer, styrene, a hexyl substituted styrene, for example, methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, chloro styrene, alpha substituted styrene, for example, (alpha) -methylstyrene, (alpha) ethyl styrene, etc. are mentioned. Can be used. Preferred examples are styrene, 4-methylstyrene and α-methylstyrene, and more preferred examples are styrene.

The purpose of copolymerizing the acrylic ester and the vinyl aromatic monomer in the present invention is to change the glass transition point of the copolymer of both copolymers from the glass transition point of the acrylic ester homopolymer to the glass transition point of the vinyl aromatic homopolymer as the composition is changed in various ways. This is because a range of temperature and frequency at which the vibration damping property of the vibration suppressing composite metal sheet is exerted freely can be set to a desirable region.

Usually, acrylic ester homopolymers have a lower glass transition point compared to vinyl aromatic homopolymers, but for the purposes of the present invention, acrylic ester homopolymers have a glass transition point as low as possible than vinyl aromatic homopolymers in a wide temperature range. It is preferable in that it can control the glass transition point of both copolymers.

As a manufacturing method of the copolymer which consists only of an acrylate ester and a vinyl aromatic monomer, random polymerization methods, such as normal solution polymerization, emulsion polymerization, and suspension polymerization, are suitable. The copolymer obtained may use 2 or more types together.

The temperature indicating the maximum value may be appropriately selected so as to match the use temperature of the vibration damping composite metal sheet, but the proportion of acrylic acid ester in this derived polymer is generally 5-95% by weight. In addition, the polymer may be further copolymerized with a small amount of another monomer as the third component, for example, 30 wt% or less, if necessary. For example, in order to make adhesiveness with a metal plate favorable, it is a preferable example to copolymerize the monomer which has a carboxyl group, an epoxy group, a hydroxyl group, etc ..

The crystalline polyolefin (B) used with the polymer (A) is an α-olefin such as ethylene, propylene, butene-1, pentene-1,3-methylbutene-1, hexene-1,4-methylpentene-1 and the like. Or a copolymer of two or more of these copolymers or other monomers containing these α-oletin as main components, for example, low density polyethylene, high density polyethylene, isotropic polypropylene, ethylene / propylene copolymer, ethylene Butene-1 copolymer, ethylene octene-1 copolymer, propylene butene-1 copolymer, polybutene-1, poly4-methylpentene-1, etc., and high density polyethylene and a propylene polymer are preferable in terms of rigidity and heat resistance. In particular, a propylene polymer is preferable.

Polymers (A) derived from acrylic esters and vinylaromatic monomers also include copolymerization components copolymerized with crystalline polyolefins (B).

That is, although crystalline polyolefin (B) may use 2 or more types together, at least one part was copolymerized with the acrylic ester, the vinyl aromatic monomer, or both. As described in the case of the composition of the said 2nd state, the polymerization amount is 0.5 weight% or more, Preferably it is 1 weight% or more, More preferably, it is 3 weight% or more of the total amount of a polymer (A). If this copolymerization with respect to a crystalline polyolefin (B) is more than the said quantity, the mechanical strength of the obtained composition will become more excellent and the moldability of the composite metal plate using this composition will become more excellent.

The composition obtained from the polymer (A) and the crystalline polyolefin (B) may be obtained by kneading these components by a conventional training method, but from the viewpoint of ease of bending, tightening and manufacturing of the composite metal sheet for vibration damping, Very preferred is a modified product in which a crystalline polyolefin and a predetermined amount of acrylic ester and a vinyl aromatic monomer are suspended or in solution or melt in the depth suspension system under graft or block copolymerization conditions.

The composition of this invention can mix | blend various additives, a plasticizer, a filler, an elastomer, etc. in the range which does not impair the objective of this invention. The plasticizer has the effect of controlling the vibration damping temperature range of the composite metal sheet for vibration damping by shifting the temperature representing the tan δ maximum value of the composition to the low temperature side, and at the same time, giving the composition adhesiveness to improve adhesion to the metal sheet and softening the composition. It is useful in that it improves. In addition, the filler has an effect of maintaining a high stiffness at a temperature exhibiting a tan δ maximum value of the composition, and thus has an improvement effect of η. In order to improve physical properties, it is preferable to mix | blend ethylene butadiene block copolymer or its water addition with ethylene propylene rubber etc. as an elastomer.

The composition of the present invention may be blended with various conductive fillers such as carbon black, metal fibers, and the like to give conductivity for the purpose of improving the weldability and paintability of the vibration damping composite metal sheet. In order to improve flame retardancy, various flame retardants, such as antimony trioxide and aluminum hydroxide, can also be mix | blended.

In addition, the composition of the present invention is useful for modifying to impart a carboxyl group, an epoxy group, a hydroxyl group, or the like in order to improve adhesion to a metal plate, and may be used after crosslinking.

Such modification can be made to an arbitrary process for obtaining the composition of the present invention. For example, in the case of a composition consisting of a combination of a polymer (A) and a crystalline polyolefin (B), it is derived from a crystalline polyolefin (B) or an acrylic ester and a vinyl aromatic monomer, to which a carboxyl group, an epoxy group, a hydroxyl group, or the like has been previously given. Methods of blending the polymer (A), copolymerizing at least one of acrylic esters and vinylaromatic monomers to crystalline polyolefins, imparting the polar group, and methods of imparting the polar group after obtaining the composition of the present invention. Can be mentioned.

The composition of the present invention more preferably has a stiffness of 8 × 10 ⁸ dyne / cm ² or more as the composition at a temperature at which the polymer (a) exhibits a tan δ maximum.

The vibration damping composite steel sheet obtained by laminating the vibration damping resin composition of the present invention with a metal plate, in particular a steel sheet, exhibits good vibration damping performance up to a higher temperature than when the polymer (a) used in the present invention is used alone in an intermediate layer. In the case where only polymer (a) is used in the intermediate layer, the stiffness ratio (G`) decreases rapidly at a temperature exhibiting the tan δ maximum value even though tan δ is high, whereas it does not have sufficient vibration damping property (η) as a composite steel sheet. Since the composition of the present invention has a small decrease in the stiffness ratio (G`) at a temperature exhibiting the maximum value of tan δ due to the polymer (a), even when tan δ as the composition is slightly reduced, it effectively acts on the damping property (η) of the composite steel sheet. In some cases, higher vibration damping resistance (η) is obtained than a composite steel sheet using polymer (a) alone.

In addition, since resin (b) used by this invention has a crystalline thing, it can select the thing with high melting | fusing point, and the agent which shows vibration damping property in a higher temperature range using what has a maximum value of tan-delta as a polymer (a) is used. An intrinsic resin composition can be obtained.

Since the resin composition of the present invention is used in a composite steel sheet and has a high stiffness at a temperature exhibiting damping property, it is advantageous in strength as a structural agent, and at the same time, such a composition has a high stiffness at room temperature, thus bending of a composite steel sheet using the composition of the present invention. The moldability of processing and tightening is also good, and the polymer (a) and the resin (b) have a good dispersion through the copolymer and are excellent in mechanical strength.

As a result, the composition of the present invention can achieve a high balance in vibration damping property, adhesiveness, and mechanical strength. Therefore, the composite steel sheet for vibration damping using the resin composition of the present invention has a balance of vibration damping property, tightening and bending workability. It will be markedly superior to the.

Various well-known methods are used to manufacture the composite metal plate for vibration damping using the composition of this invention. For example, a method of applying a composition as a solution between metal plates, drying, and thermally compressing, molding the composition into a film, sandwiching the metal plates, and laminating by press or hot roller, or the composition There exists a method of extruding and laminating | stacking a film form in a molten state between metal plates.

In addition, in the lamination with the metal plate, the modified polyolefin modified from an unsaturated carboxylic acid or anhydride thereof, or after surface treatment such as corona treatment or flame treatment of the film-like composition is carried out using an adhesive agent. The metal plate may be faced with each other, and various surface treatments such as chemical treatment may be performed on the surface of the metal plate in advance.

Since the composition of the present invention can be molded into a film in a molten state, it is possible to simplify the manufacturing process of the composite metal plate for dust removal as compared with the conventional vibration damping material. In addition, the steel sheet thickness of the composite steel sheet for vibration damping is preferably 0.2 mm to 3.2 mm, and the thickness of the composition layer of the present invention is 0.03 mm to 0.5 mm.

EXAMPLE

The present invention according to the following examples will be described, wherein the loss tangent (tan δ) and the stiffness (storage modulus, G ′) of the polymer or its composition are obtained from the measurement of the dynamic viscoelasticity of the sample, and the numerical values differ depending on the measurement method. .

Tan δ and G` in the present invention were measured at 10 Hz by a forced torsional vibration method.

The temperature dependence of tan δ was investigated and its maximum was taken as tan δ max. In addition, the composite steel sheet for vibration damping is formed by molding the vibration damping composition into a film and then sandwiched by two steel sheets having a thickness of 0.8 mm and laminated by compression molding. The thickness of the vibration damping layer is 0.1-0.2 mm except for Example 2. In Example 2, it is 0.5 mm. The η of the vibration damping composite steel sheet is the loss coefficient η measured at 1000 Hz using the resonance response method based on the mechanical impedance. (The loss coefficient is calculated according to the etiology of the resonance curve with respect to the frequency response involvement.) In addition, melting | fusing point of the crystalline resin used for this invention is melt | dissolution end temperature measured by the differential scanning calorimeter (DSC). In addition, 0.5 mm thickness of a composition according to JIS-K-6758. The test piece was measured at a test rate of 50 mm / min, and the polymer (a) content copolymerized to the polymer (b) was vacuum-dried to extract the modified copolymer obtained with boiling methyl ethyl ketone and not with methyl ethyl ketone. The content was quantified by infrared analysis (Examples 6 and 7).

Moreover, in order to measure the monomer copolymerized to a polyolefin (B), the obtained modified propylene ethylene copolymer was melt | dissolved in boiling xylene, what was reprecipitated with acetone was vacuum-dried, and the content of styrene and acrylic acid ester was measured by infrared analysis. (Examples 8 and 9).

Example 1

Polyvinyl acetate having a glass transition point of about 28 ° C. (Wago Junyaku Kogyo Co., Ltd., polymerization degree 1400-1600, hereinafter referred to as PVAc), and polypropylene having a melting point of 167 ° C. (Mitsubishi emulsifier, Mitsubishi noble MH 8, hereinafter simply PP. The composite obtained by kneading at various compounding ratios was sandwiched between two 0.8 mm-thick steel sheets to form a composite steel sheet for vibration damping. The thickness of the composition of the intermediate layer was 0.1-0.2 mm.

The stiffness ratio (G`) of the composition and the 1000 s at 80 ° C of the composite steel sheet at the maximum value (η max) of the vibration damping performance of the obtained various composite steel sheets and the temperature (T η max) indicating the tan η maximum value of the composition. The damping performance (η) is shown in the first table. The temperature change of the damping property ((eta)) is shown in FIG. 1 with respect to some damping steel plates of various compounding ratios.

2 shows the temperature change of G ′ and tan δ at a frequency of 10 Hz for the composition of PVAc alone, PP alone and PVAc: PP = 60: 40 (weight). The tanδ maximum of PVAc and its temperature are 2,6 and 54 ° C., respectively, and the G ′ of PP at 54 ° C. is 2.5 × 10 ⁸ dyne / cm ² . On the other hand, the maximum tan δ of the composition of PVAc is lowered to 0.5, but? Of the damping steel sheet using the same shows better vibration damping property in the high temperature region than that of the PVAc alone as shown in FIG.

TABLE 1

Example 2

45 weight% of PVAc used in Example 1 was mixed with 55 weight% of low density polyethylene (Mitsubishi emulsified product, Eucalton ZC-30, hereinafter referred to as LDPE) at a melting point of 109 ° C, and the composition kneaded was mixed between two 0.8 mm thick steel sheets. It laminated | stacked as the intermediate | middle layer of thickness 0.5mm in order to make a composite steel sheet. 3 shows the damping property (η) at 1000 Hz with respect to the obtained composite steel sheet with temperature. Ηmax of 0.15 was shown at 75 ° C. G ′ at the temperature showing the tan δ maximum value of this composition was 6.8 × 10 ⁸ dyne / cm ² . In addition, the stiffness (G ′) of LDPE at 54 ° C. in which PVAc exhibited a tan δ maximum was 3.9 × 10 ⁸ dyne / cm ² .

Comparative Example 1

50% by weight of PVAc of Example 1 was carried out using a composition containing 50% by weight of an ethylene-vinyl acetate copolymer (Mitsubishi emulsified product, Eucalton-Eva X-700, hereinafter simply referred to as EVA) having a melting point of 75 ° C. A composite steel sheet of 0.5 mm thick intermediate layer was prepared as in Example 2. The damping property (η) at 1000 Hz of the obtained composite steel sheet is shown in FIG. The EVA stiffness at 54 ° C. showing the tanδ maximum of PVAc is not sufficient as 1.0 × 10 ⁸ dyne / cm ² , and the η of the composite steel obtained by the compatibility of EVA is overall low as shown in FIG. 3. The peak of? Due to PVAc is not clear.

Example 3

Polystyrene (Mitsubishi Monsanto, Diarex HF 77, hereinafter simply referred to as PS) having a glass transition point of about 100 ° C and polypropylene (Mitsubishi emulsified product, Mitsubishi Noblen FX 4) having a melting point of 152 ° C Η of the composite steel sheet used is shown in FIG. The maximum tanδ of PS was 3,4 at 109 ° C, and the stiffness of polypropylene at that temperature was 9.8 × 10 ⁸ dyne / cm ² . The maximum value of the vibration damping performance of the obtained composite steel sheet was 0.14 at 120 degreeC, and the rigidity at the temperature which shows the tan-delta maximum value of a composition was 1.8 * 10 <^8> dyne / cm <^2> .

Example 4

Η of the composite plate using high density polyethylene (Mitsubishi emulsified product, Eucalon-HD, BZ 50A, hereinafter HDPE) having a melting point of 133 ° C instead of the polypropylene of Example 3 is shown in FIG. have. The stiffness of HDPE at the tan δ maximum value temperature of 109 ° C. of PS was 0.11 at 120 ° C. as shown in FIG. 4 showing the tan δ maximum value of 5.1 × 10 ⁸ dyne / cm ² .

Example 5

Synthesis for vibration damping in the same manner as in Example 1 except that styrene-acrylic acid ester copolymer having a glass transition point of about 20 ° C. (styrene content of 50% by weight, a molecular weight of 210,000, hereinafter referred to as SAE) instead of PVAc in Example 1 was used. A steel sheet was obtained. The stiffness ratio (G`) of the composition at the temperature (Ttan delta max) which shows the maximum value (eta max) of the vibration damping performance of the obtained various composite steel sheets, the temperature (Teta max), and the tan delta maximum value of a composition is shown in a 2nd table. The damping property (η) of several damping steel sheets of various mixing ratios is shown in FIG. The tanδ maximum value of SAE and its temperature were 2, 9 and 40 ° C., respectively, and G ′ of PP at 40 ° C. was 3.2 × 10 ⁸ dyne / cm ² .

TABLE 2

Example 6

20 Kg of 50-L autoclave pure water, 0.6 Kg of tricalcium phosphate and 0.06 Kg of sodium dodecyl benzenesulfonate are mixed as a suspending agent to form an aqueous medium, and the maleic anhydride modified propylene having a particle size of 3-4 mm is added thereto. 5 Kg of ethylene copolymer (MFR, 15 g / 10 min, ethylene content 5% by weight, maleic anhydride content 0.4% by weight) (hereinafter referred to as PP (1)) was added and suspended by stirring. Separately, 15 g of benzoyl peroxide was dissolved in 5 Kg of vinyl acetate, and this was added to the preceding suspension, and the temperature in the autoclave was raised to 60 ° C, and the mixture was left at this temperature for 5 hours while being stirred, and vinyl acetate including a polymerization initiator and the like. Was incorporated into propylene-ethylene copolymer particles.

Next, the suspension was heated to 80 ° C., left to stand for 5 hours with stirring at this temperature, polymerized, and further heated to 90 ° C. for 5 hours to complete polymerization. After cooling, the solid content was taken out and washed with water to obtain 10 kg of vinyl acetate-modified propylene-ethylene copolymer particles (copolymer 1). The vinyl acetate content in the obtained modified propylene-ethylene copolymer was 50% by weight. In addition, the graft amount of vinyl acetate was 15 weight%. The tensile drawing strength of this copolymer 1 was 360%, and the tensile drawing strength of the equivalent weight composition of polyvinyl acetate and a maleic anhydride modified propylene ethylene copolymer corresponding to this was only 20%.

Obtained by kneading the mixture of the maleic anhydride-modified propylene-ethylene copolymer (PP (1)) and polyvinyl acetate (PVAc) used in the manufacture of the copolymer 1, the copolymer 1 in various ratios, and again mixing the antioxidant. The composition was sandwiched between two 0.8 mm thick steel sheets to form a composite steel sheet for vibration damping. The composition thickness of the intermediate layer was 0.1-0.2 mm.

The stiffness ratio (G`) of the composition is shown in Table 3 at the maximum value (ηmax), the temperature (Tηmax) at 1000 Hz, and the temperature (Ttanδmax) indicating the maximum tanδ value of the composition of the obtained various composite steel sheets. do. At 10 Hz of PAVc, the maximum value of tan δ and its temperature (T η max) were 2.6 and 55 ° C., respectively, and G ′ of PP (1) at 55 ° C. was 1.9 × 10 ⁸ dyne / cm ² .

TABLE 3

Example 7

Preparation of Copolymer 2

A styrene-modified propylene-ethylene copolymer (copolymer 2) was obtained in the same manner as in the preparation of copolymer 1 except that styrene was used instead of vinyl acetate of copolymer 1. The styrene content of the obtained modified propylene-ethylene copolymer was 50% by weight. The graft amount of styrene was 10% by weight. Tensile stretching force of the copolymer 2 was 90%, and the tensile stretching force of the simple composition of the corresponding polystyrene and maleic anhydride modified propylene / ethylene copolymer was 10%.

[Production Method of Copolymer 3]

N-butyl methacrylate modified propylene-ethylene copolymer (copolymer 3) was obtained in the same manner as in the preparation of copolymer 1 except that n-butyl methacrylate was used instead of vinyl acetate of copolymer 1. The methacrylic acid-n-butyl content of the obtained modified propylene ethylene copolymer was 50% by weight. The graft amount of n-butyl methacrylate was 10% by weight. Tensile stretching strength of the copolymer 3 was 200%, and the tensile stretching force of the simple composition of the corresponding polymethacrylate n-butyl and maleic anhydride modified propylene-ethylene copolymer was 10%.

Copolymer 2 or copolymer 3 were used alone to make a composite steel sheet as in Example 6. The stiffness ratio (G`) of the composition is shown in Table 4 at the maximum value (ηmax) of the vibration damping performance at 1000 Hz of the obtained composite steel sheet, the temperature (Tηmax) and the temperature (Ttanδmax) indicating the tanδ maximum value of the composition. . The maximum tan δ of polystyrene was 3.4 at 110 ° C., and G ′ of PP (1) at that temperature was 1.8 × 10 <sup>8</sup> dyne / cm <sup>2</sup> , and the maximum tan δ of n-butyl polymethacrylate was 50. It was 1.6 in ° C, and G` of PP (1) at that temperature was 1.5 x 10 ⁸ dyne / cm ² .

TABLE 4

Example 8

Preparation of styrene isononyl acrylate copolymer

A 50-liter autoclave pure water 35Kg and a suspension polyvinyl alcohol 320g are mixed to make an aqueous medium, and 180Kg of benzoyl peroxide is added to 10.8Kg of styrene (SM) and 7.2Kg of isononyl acrylate (INA). And stirred to suspend. Nitrogen was introduced into the autoclave to displace the drug with nitrogen, and then the inside of the autoclave was heated to 60 ° C. and left at this temperature for 5 hours with preliminary polymerization. While raising the stirring speed, the inside of the autoclave was heated to 90 ° C. and left at this temperature for 3 hours while stirring to complete the polymerization. After cooling, the contents solid was taken out and washed with water to obtain 17.5 kg of styrene isononyl acrylate copolymer (SAE). The styrene content in the obtained SAE was 60% by weight and the isoninyl acrylate content was 40% by weight.

[Production of Graft Copolymer (1)]

20 Kg of 50 L autoclave pure water, 0.6 Kg of tricalcium phosphate as a suspending agent, and 0.06 Kg of sodium domesylbenzelsulfonate are mixed into an aqueous medium, and a 3-4 mm maleic anhydride modified propylene-ethylene copolymer ( MFR 17g / 10min, ethylene content 5.5% by weight, maleic anhydride content 0.4% by weight) (hereinafter referred to as PP (2)) particles were suspended by stirring. Separately, benzoyl peroxide (BPO) was dissolved in styrene (SM) and isononyl acrylate (INA), added to the preceding suspending agent, and nitrogen was introduced into the autoclave to disintegrate the drug. In addition, the inside of the autoclave was heated to 60 ° C. and left to stir at this temperature for 5 hours, and styrene and isononyl acrylate including a polymerization initiator and the like were incorporated in the PP (2) particles.

Next, the suspension was heated to 80 ° C., left at this temperature for 5 hours with stirring, polymerization was carried out, and again heated to 90 ° C. for 5 hours to complete polymerization. After cooling, the solid content was taken out and washed with water to obtain 10 kg of styrene isononyl acrylate-modified propylene-ethylene copolymer (hereinafter referred to as modified PP) particles. The styrene content, isononyl acrylate content, and their graft air content in the modified PP obtained by changing the injection amount in various ways are shown in Table 5.

TABLE 5

* The graft ratio is the total weight of SM and INA graft relative to the total amount of SM and INA in the modified PP.

Antioxidant was mix | blended with each modified propylene ethylene copolymer particle shown in Table 5, and this was sandwiched between two sheets of 0.8 mm thickness steel sheets, and it was set as the composite steel sheet for a gauge. The thickness of the composition of the intermediate layer was 0.1-0.2 mm.

In Table 6, the maximum value (ηmax), the temperature (Tηmax), the tanδ maximum value (tanδmax) of the composition and the tensile elongation of the vibration damping performance of the obtained various composite steel sheets are shown.

TABLE 6

In addition, the copolymer SAE and maleic anhydride-modified polypropylene (MFR 2g / 10min, maleic anhydride content 0.4 wt%) (hereinafter referred to as PP (3)) obtained in the production of the styrene isononyl acrylate copolymer were referred to in various ratios. Table 7 shows the results of measuring tensile tensile strength of the composition formulated with and added to the antioxidant.

TABLE 7

Example 9

Modified propylene-ethylene copolymer containing styrene isononyl acrylate copolymer (SAE) and maleic anhydride-modified polypropylene (PP (3)) shown in Example 8, and containing 30 wt% SM and 20 wt% INA. (The modified PP No. 4) was mix | blended in various ratios, and the result of having measured tensile tensile strength of the composition like Example 8 using what added antioxidant here is shown in Table 8.

TABLE 8

Example 10

In the preparation of the graft copolymer (1), the maleic anhydride-modified propylene-ethylene copolymer (MFR 4g / 10min, ethylene content 8% by weight, maleic anhydride content 0.4% by weight) instead of PP (2) (hereinafter PP Styrene / Acrylic acid 2-ethylhexyl modified propylene-ethylene copolymer as in Example 8 except that particles were used and 2-methylhexyl acrylate (2-EHA) was used instead of isononyl acrylate. (Hereinafter referred to as modified PP) particles were obtained.

The styrene content, the 2-ethylhexyl acrylate content, and their graft air content in the modified PP obtained by variously changing the injection amounts were as shown in Table 9.

TABLE 9

* Graft ratio is the total graft amount of SM and 2-EHA in% by weight relative to the total amount of SM and 2-EHA in the modified PP.

Example 11

In the same manner as in Example 8, using the modified propylene-ethylene copolymer particles shown in Table 9, the vibration damping performance of the composite steel sheet, the tan δ max and tensile elongation of the composite steel sheet are shown in Table 10. Display.

TABLE 10

Claims (35)

10-95% by weight of the amorphous thermoplastic polymer (a) and 90-5% by weight of the crystalline thermoplastic polymer (b) which does not correspond to this polymer (a), wherein the amorphous thermoplastic polymer (a) is a crystal It is an amorphous polymer having a glass transition point lower than that of the thermoplastic thermoplastic polymer (b) and having a tan δ maximum of 0.5 or more within a temperature of -50 to 150 ° C. and a frequency of 0.1-20000 Hz, and the crystalline thermoplastic polymer (b) is A crystal having a melting point higher than the glass transition point of the amorphous thermoplastic polymer (a) and having a stiffness of 1 × 10 ⁸ dyne / cm ² or more at a temperature and a frequency at which the amorphous thermoplastic polymer (a) exhibits a tan δ maximum. A damping resin composition characterized in that it is a polymer. The damping resin composition according to claim 1, wherein the amorphous thermoplastic polymer (a) is an amorphous polymer having a tan δ maximum of 1.0 or more at a temperature of -50 to 150 ° C and a frequency of 0.1-20000 Hz. The amorphous thermoplastic polymer (a) is at least one member selected from the group consisting of vinyl ester polymer, polyvinyl butyral, styrene polymer, thermoplastic rubber, halogenated vinyl polymer and acrylic polymer. Vibration-resistant resin composition. The damping resin composition according to claim 1, wherein the amorphous thermoplastic polymer (a) is at least one polymer or copolymer selected from the group consisting of vinyl ester polymers, styrene polymers, and acrylic polymers. The damping resin composition according to claim 4, wherein the amorphous thermoplastic polymer (a) is a copolymer of a styrene monomer and an acrylic monomer. The method of claim 1, wherein the crystalline thermoplastic polymer (b) is characterized in that the amorphous thermoplastic polymer (a) is a crystalline polymer having a stiffness of 5 × 10 ⁸ dyne / cm ² or more at a temperature and frequency exhibiting a tan δ maximum. Anti-vibration resin composition. The method of claim 1, wherein the crystalline thermoplastic polymer (b) is characterized in that the amorphous thermoplastic polymer (a) is a crystalline polymer having a stiffness of 6 × 10 ⁸ dyne / cm ² or more at a temperature and frequency exhibiting a tan δ maximum. Anti-vibration resin composition. The vibration damping resin composition according to claim 1, which is selected from the group consisting of a crystalline α-olefin resin and a crystalline polycondensation resin of the crystalline thermoplastic polymer (b). The vibration damping resin composition according to claim 1, wherein the crystalline thermoplastic polymer (b) is selected from the group consisting of high density polyethylene and polypropylene or higher α-olefin resin. The vibration damping resin composition according to claim 1, comprising 20 to 80% by weight of the amorphous thermoplastic polymer (a) and 80 to 10% by weight of the crystalline thermoplastic polymer (b). The vibration damping resin composition according to claim 1, comprising 30-90 wt% of the crystalline thermoplastic polymer (a) and 70-20 wt% of the crystalline thermoplastic polymer (b). The vibration damping resin composition according to claim 1, wherein the crystalline thermoplastic polymer (b) has a melting point higher by 30 ° C or higher than the glass transition point of the amorphous thermoplastic polymer (a). The vibration damping resin composition according to claim 1, wherein the crystalline thermoplastic polymer (b) has a melting point of 50 ° C or higher than the glass transition point of the amorphous thermoplastic polymer (a). Among the monomers constituting the polymer (a), containing 10-90% by weight of the amorphous thermoplastic polymer (a) and 90-10% by weight of the crystalline thermoplastic polymer (b) which do not correspond to this polymer (as). At least 1 type copolymerizes with the said crystalline thermoplastic polymer (b) at 0.5 weight% or more with respect to the total amount of this polymer (a), where an amorphous thermoplastic polymer (a) is glass lower than a crystalline thermoplastic polymer (b) It is an amorphous polymer having a transition point and having a tan δ maximum of 0.5 or more within a temperature of -50 to 150 ° C. and a frequency of 0.1 to 20000 Hz, and the crystalline thermoplastic polymer (b) is a polymer of the amorphous thermoplastic polymer (a). glass has a melting point higher than the transition point, excessive the amorphous thermoplastic polymer (a) can damping properties, characterized in that the crystalline polymer having a 1 × 100 ⁸ dyne / cm ² or more rigidity at a temperature and a frequency representing the tanδ peak Composition. 15. The damping property according to claim 14, wherein the amorphous thermoplastic polymer (a) is a polymer (A) derived from an acrylate ester and a vinyl aromatic monomer, and the crystalline thermoplastic polymer (b) is a crystalline polyolefin (B). Resin composition. The vibration damping resin composition according to claim 14, wherein the amorphous thermoplastic polymer (a) is an amorphous polymer having a tan δ maximum of 1.0 or more at a temperature of 50 to 150 ° C and a frequency of 0.1 to 20000 Hz. 15. The amorphous thermoplastic polymer (a) is at least one member selected from the group consisting of vinyl ester polymer, polyvinyl butyral, styrene polymer, thermoplastic rubber, vinyl halide polymer and acrylic polymer. Vibration-resistant resin composition. 15. The vibration damping resin composition according to claim 14, wherein the amorphous thermoplastic polymer (a) is at least one polymer or copolymer selected from the group consisting of vinyl ester polymers, styrene polymers and acrylic polymers. The damping resin composition according to claim 14, wherein the amorphous thermoplastic polymer (a) is a copolymerization of a styrene monomer and an acrylic monomer. 16. The acrylic acid ester according to claim 15, wherein the acrylic acid ester is n-butyl acrylate, 2-ethylhexyl acrylate, Tinatool acrylate, isononyl acrylate, 2-butoxyethyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl methacrylate and meta A vibration damping resin composition, characterized in that it is selected from the group consisting of trimethyl methacrylate. 16. The vibration damping resin composition according to claim 15, wherein the vinylaromatic monomer is selected from the group consisting of styrene, 4-methylstyrene and α-methylstyrene. 16. The acrylic acid ester according to claim 15, wherein the acrylic acid ester is n-butyl acrylate, 2-ethylhexyl acrylate, Tinatool acrylate, isononyl acrylate, 2-butoxyethyl acrylate, diethylene glycol monobutyl ether acrylate, lauryl methacrylate and meta And a vinylaromatic monomer is selected from the group consisting of styrene, 4-methylstyrene, and [alpha] -methylstyrene. 15. The crystalline thermoplastic polymer (b) according to claim 14, wherein the crystalline thermoplastic polymer (b) is a crystalline polymer having a stiffness of at least 5x10 ⁸ dyne / cm ² at a temperature and a frequency at which the amorphous thermoplastic polymer (a) exhibits a tan δ maximum. Anti-vibration resin composition. 15. The method of claim 14, wherein the crystalline heat-transportable polymer (b) is characterized in that the amorphous thermoplastic polymer (a) is a crystalline polymer having a stiffness of 6 × 10 ⁸ dyne / cm ² or more at a temperature and frequency exhibiting a tan δ maximum. Vibration-resistant resin composition. 15. The damping resin composition according to claim 14, which is selected from the group consisting of crystalline α-olefin resin and crystalline polycondensation resin of the crystalline thermoplastic polymer (b). 15. The vibration damping resin composition according to claim 14, wherein the crystalline thermoplastic polymer (b) is selected from the group consisting of crystalline high density polyethylene and polypropylene or higher higher alpha-olefin resin. 16. The vibration damping resin composition according to claim 15, wherein the crystalline olefin (B) is selected from the group consisting of high density polyethylene and polypropylene-based polymers. The vibration damping resin composition according to claim 15, wherein the crystalline olefin (B) is a propylene polymer. 15. The vibration damping resin composition according to claim 14, consisting of 20-70 wt% of the amorphous thermoplastic polymer (a) and 80-30 wt% of the crystalline thermoplastic polymer (b). 15. The vibration damping resin composition according to claim 14, comprising 30-60 wt% of the amorphous thermoplastic polymer (a) and 70-40 wt% of the crystalline thermoplastic polymer (b). The damping resin composition according to claim 15, wherein the ratio of the acrylic ester in the polymer (A) derived from the acrylic ester and the vinylaromatic monomer is 5-95% by weight. 15. The method of claim 14, wherein at least one of the monomers constituting the amorphous thermoplastic polymer (a) is copolymerized with the crystalline thermoplastic polymer (b) in an amount of at least 1% by weight based on the total amount of the polymer (a). Vibration-resistant resin composition. 15. The method according to claim 14, wherein at least one of the monomers constituting the amorphous thermoplastic polymer (a) is copolymerized with the crystalline thermoplastic polymer (b) in an amount of at least 3% by weight based on the total amount of the polymer (a). Vibration-resistant resin composition. 15. The vibration damping resin composition according to claim 14, wherein the crystalline thermoplastic polymer (b) has a melting point of 30 DEG C or more higher than the glass transition point of the amorphous thermoplastic polymer (a). 15. The vibration damping resin composition according to claim 14, wherein the crystalline thermoplastic polymer (b) has a melting point of 50 ° C or higher than the glass transition point of the amorphous thermoplastic polymer (a).

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