JPH08176352A - Damping elastic body composition - Google Patents

Abstract

PURPOSE: To obtain a composition capable of stably maintaining excellent vibration damping performances when used at a temperature within a range as wide as -30 to +100 deg.C. CONSTITUTION: This damping elastic body composition or a damping sheet comprises 1-98wt.% thermoplastic elastomer which is a thermoplastic polyester elastomer, etc., having >=100 deg.C softening point with 1-98wt.% rubber and 1-98wt.% synthetic resin that is a polyamide or polybutylene terephthalate having 30-100 deg.C glass transition temperature and is obtained by kneading the components at a ratio so as to provide 100wt.% sum total thereof and molding the resultant kneaded mixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vibration-damping elastic body composition and a vibration-damping sheet used as a vibration-damping elastic body for suppressing vibrations of machinery, buildings and the like.

[0002]

2. Description of the Related Art Generally, as a cushioning member used for suppressing vibration generated from vehicles, buildings, machines, etc., that is, as a damping material, epoxy resin, urethane resin, resin such as polyvinyl chloride, thermoplastic elastomer, rubber, Asphalt is known.

Such damping materials are roughly classified into those mainly made of semi-solid bituminous material such as asphalt, or those made mainly of rubber, plastic and the like.

The former, which is mainly made of bituminous material, has an advantage that it can be manufactured at low cost, but on the other hand, it requires a large amount of filler and needs to be thickened in order to obtain effective vibration damping performance. Therefore, the weight and volume are increased, and the demand for weight reduction, especially as automobile parts, is not met.

The latter vibration-damping material mainly made of rubber, plastic or the like can meet the demand for weight reduction as compared with the former.

[0006]

However, the vibration-damping material whose main raw material is rubber, plastic or the like does not have stable vibration-damping performance depending on the ambient temperature, and especially when it is used as a vehicle part such as an automobile, There is a problem that the required vibration damping performance cannot be stably maintained in a wide range of operating environment temperature range of −30 ° C. to 100 ° C.

Here, the damping performance of the damping material can be evaluated by a loss coefficient: tan δ (δ is a loss angle), and in an elastic body made of a single substance, the loss coefficient: tan is usually used.
δ shows a peak value at the glass transition point (T _g ), and effective vibration damping performance can be obtained only near this temperature.

In rubber, T _g (NBR below room temperature)
At -47 ° C (AN 20% by weight) to -22 ° C (AN 45% by weight), and about -58 ° C in a general-purpose SBR).
For plastic, for example, for polyethylene, it is -68.
A thermosetting resin after curing at ℃ has a T _g above room temperature, and a damping material made of a single material can obtain effective damping performance only near the T _{g of} each material. .

Conventionally, a material obtained by blending rubber and resin has been proposed as a vibration damping material. In this case, depending on the selection of rubber and resin, the temperature is around room temperature or -10 ° C to 60 ° C.
The vibration damping performance can be maintained in a temperature range of about a certain degree.

However, when it is used for automobiles, the temperature range required from the use site and the environmental conditions is as wide as -30 ° C to 100 ° C, and the temperature at which conventional damping materials exhibit damping properties. Due to the narrow range, the desired function could not be achieved.

Therefore, as a result of intensive studies, the inventors of the present application have maintained high vibration damping performance in a wider temperature range by blending three or more components of thermoplastic elastomer, rubber and synthetic resin. In order to make it possible to do so, we have created a completely new vibration damping material that exerts a sufficient function not only in automobile applications but also in any application. However, at this time, the organic polymer material is a multi-component system of three or more components, and the combination of the polymer material components that can be blended is limited due to the difference in melting temperature and melt viscosity of each component.

An object of the present invention is to solve the above-mentioned problems and to provide a vibration-damping elastic composition as a temperature range for use environment.
Even when a wide temperature range such as 30 ° C. to 100 ° C. is set, the intended vibration damping performance can be stably maintained.

[0013]

In order to solve the above problems, in the present invention, a thermoplastic elastomer having a softening point of 100 ° C. or higher, rubber, and a glass transition point of 30 to 1 are used.
This is a vibration-damping elastic body composition in which a synthetic resin at 00 ° C. is an essential component.

Alternatively, (A) 1 to 98% by weight of a thermoplastic elastomer having a softening point of 100 ° C. or higher, and (B) rubbers 1 to 9
8% by weight, (C) 1 to 98% by weight of a synthetic resin having a glass transition point of 30 to 100 ° C., and (A), (B) and (C) in a total amount of 100% by weight. The vibration-damping elastic body composition is obtained by molding.

In the above vibration-damping elastic body composition, it is preferable to employ polyamide or polybutylene terephthalate as the synthetic resin having a glass transition point of 30 to 100 ° C.

[0016]

The vibration-damping elastic composition according to the present invention comprises a thermoplastic elastomer having a predetermined softening temperature, rubber and a synthetic resin as essential components, and the above-mentioned three types of components are evenly mixed at a specific temperature. Loss coefficient of tan δ disappears, that is, the peak of the tan δ value of the composite elastic body is broadened on the temperature axis, and the tan δ value has a high level, and the operating environment temperature range is −30 ° C. to 100 ° C.
When such a wide temperature range is set, desired vibration damping performance can be stably exhibited at least in that temperature range.

[0017]

EXAMPLES As the thermoplastic elastomer having a softening point of 100 ° C. or higher used in the present invention, a known thermoplastic elastomer may be used.
A mixture of two or more species can be used.
Specific examples of such thermoplastic elastomers include thermoplastic polyester elastomers, styrene-butadiene block copolymers, styrene-isoprene block copolymers, or hydrogenated products thereof, thermoplastic polyurethane elastomers, thermoplastic chloroolefin elastomers. , A thermoplastic polyamide elastomer, a composition containing polypropylene / ethylene-propylene copolymer rubber as a main component, or a dynamically crosslinked composition thereof, a composition containing polypropylene / acrylonitrile-butadiene copolymer rubber as a main component, or a dynamic composition thereof Crosslinking composition, polypropylene /
Composition based on styrene-butadiene block copolymer, or dynamically crosslinked composition thereof, polypropylene /
Composition based on styrene-isoprene block copolymer, or dynamically cross-linked composition thereof, polypropylene /
Styrene-butadiene block copolymer hydrogenated composition as the main component, or dynamically crosslinked composition thereof, polypropylene / styrene-isoprene block copolymer hydrogenated composition as the main component, or dynamic thereof Examples include cross-linking compositions.

A more preferred thermoplastic elastomer is a thermoplastic polyester elastomer.

The thermoplastic elastomer used in the present invention is a block copolymer comprising a high melting point polyester segment and a low melting point polymer segment, and the high melting point polyester segment is composed of polyester having a melting point of 150 ° C. or higher. . The low-melting point polymer segment described above shows a substantially amorphous state in the polyester block copolymer, the upper limit of the melting point or softening point when measured only in that segment is not particularly limited. Although not limited, it is generally preferably 130 ° C. or lower, and more preferably 100 ° C. or lower.

The polyester constituting the high melting point polyester segment is a polyester composed of a dicarboxylic acid residue as described below and a residue of an aliphatic or alicyclic diol, or two or more kinds of dicarboxylic acid or two kinds. Copolyesters using the above diols, or polyesters derived from oxyacids such as p- (β-hydroxyethoxy) benzoic acid and p-oxybenzoic acid and residues thereof, polylactones such as polyvivalolactone, 1, Polyetherester consisting of residues of aromatic ether dicarboxylic acid such as 2-bis (4,4′-dicarboxydimethylphenoxy) ethane and di (4′-carboxydiphenoxy) ethane and diol residue, and further dicarboxylic acid Copolyesters that combine oxyacids, diols, etc. To obtain favorable results.

Here, the dicarboxylic acid and the aliphatic, alicyclic or aromatic diol applied as the constituent components of the polyester are listed below. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bibenzoic acid, bis (p-carboxyphenyl) methane, 4, An aromatic dicarboxylic acid such as 4-sulfonyldibenzoic acid, or 1,
Examples thereof include alicyclic dicarboxylic acids such as 4-cyclohexanedilbonic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid and dimer acid.

Examples of the aliphatic diol include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyltrimethylene glycol, hexamethylene glycol, neopentyl glycol and decamethylene glycol. To be

Examples of the alicyclic diol include 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and tricyclodecanedimethanol.

As the diol containing an aromatic group, xylylene glycol, bis (p-hydroxy) diphenyl,
Bis (p-hydroxyphenyl) propane, 2,2-bis "4- (2-hydroxyhetoxy) phenyl" propane, 1,1-bis "4- (2-hydroxyhetoxy) phenyl" cyclohexane and the like can be mentioned. .

The constituent components of the low melting point polymer segment are listed below. That is, polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxytetramethylene glycol, and mixtures thereof, copolymerized polyether glycols obtained by copolymerizing these polyether constituent components, or having 2 to 2 carbon atoms. A polyester comprising 12 aliphatic or alicyclic dicarboxylic acids and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms (for example, polyethylene adipate, polytetramethylene adipate, polyethylene sebacate, polyneopentyl sebacate). , Polytetramethylene dodecanoate, polytetramethylene azelate, polyhexamethylene azelate, poly-ε-caprolactone, and other aliphatic polyesters and two aliphatic dicarboxylic acids or two glycols can be used. Mention may be made of aliphatic copolyesters, etc.). Also,
It may be a polyester polyether block copolymer obtained by combining the above aliphatic polyester and an aliphatic polyether.

The thermoplastic polyester elastomer composed of such a high melting point polyester segment and a low melting point polymer segment can be copolymerized by a known method for polymerizing a high molecular compound.

In this case, a preferable polymerization method is as follows: aromatic dicarboxylic acid or its dimethyl ester and a low-melting segment-forming diol in the presence of a catalyst of about 150.
Method of obtaining a thermoplastic elastomer by heating to ~ 260 ° C to carry out an esterification reaction or a transesterification reaction, and then carrying out a polycondensation reaction while removing excess low-molecular diol under vacuum, a high-melting polyester previously adjusted Segment-forming prepolymer and low-melting polymer A segment-forming prepolymer is mixed with a bifunctional chain extender that reacts with the end groups of those prepolymers, and after the reaction, the system is kept under high vacuum. A method for obtaining a thermoplastic polyester elastomer by removing volatile components,
Examples thereof include a method in which a high-melting-point polyester having a high degree of polymerization and a lactone are heated and mixed, and a transesterification reaction is performed while ring-opening polymerization of the lactone to obtain a thermoplastic polyester elastomer.

The composition ratio of the high melting point crystalline segment and the low melting point polymer segment in the thermoplastic polyester elastomer is preferably in the range of 95/5 to 5/95 by weight ratio, more preferably 70/30. From 30/7
It is in the range of 0.

The low melting point segment has a molecular weight (weight average molecular weight, hereinafter simply referred to as molecular weight) of 400 to 6000.
Are preferred. The reason is that if the molecular weight is less than the predetermined value, the crystallinity of the high melting point segment is impaired and the elastic recovery rate decreases, so this is not desirable, and if the molecular weight exceeds the predetermined range, the poly (tetramethylene oxide) glycol itself becomes crystalline. This is because the low temperature characteristics are deteriorated due to the deterioration of the compatibility.

As the thermoplastic polyester elastomer, one having a softening point of 100 ° C. or higher is adopted. This is because a low softening point of less than 100 degrees is not preferable because it causes a problem of "drip" when the temperature of the adherend and the ambient temperature rise.

The rubber component used in the present invention may be one kind or a mixture of two or more kinds of various synthetic rubbers or natural rubbers, and may be vulcanized or unvulcanized. Specific examples include those classified into the following groups (a) to (g).

(A) Nonpolar diene rubbers such as natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber and hydrogenated products thereof.

(B) Polar diene rubbers such as acrylonitrile-butadiene copolymer rubber, (meth) acrylic acid ester-butadiene copolymer rubber, (meth) acrylic acid ester-acrylonitrile-butadiene copolymer rubber and the like. Hydrogenated product.

(C) (meth) acrylic ester rubber,
(Meth) acrylic acid ester- (meth) acrylic acid copolymer rubber, (meth) acrylic acid-acrylonitrile copolymer rubber, (meth) acrylic acid ester-ethylene copolymer rubber, (meth) acrylic acid ester-ethylene- (meth )
A so-called acrylic rubber whose main component is a (meth) acrylic acid ester such as an acrylic acid copolymer rubber.

(D) So-called hydrin rubber represented by epichlorohydrin alone or a copolymer rubber with ethylene oxide.

(E) Halogenated rubbers such as chloroprene rubber, chlorinated polyethylene rubber, chlorosulphonated polyethylene rubber, chlorinated butyl rubber, brominated butyl rubber and chlorinated ethylene-propylene rubber.

(F) So-called ethylene-propylene rubber such as ethylene-propylene copolymer rubber and crosslinkable third component copolymer rubber such as ethylene-propylene and ethylidene norbornene.

(G) In addition, general synthetic rubbers such as so-called polysulfide rubber, chlorophosphazene rubber, urethane rubber, ethylene-vinyl acetate copolymer rubber, polyethylene oxide rubber, silicone rubber, fluororubber, etc. is there.

More preferable rubbers are the above-mentioned polar diene rubbers and hydrogenated products thereof, acrylic rubbers, hydrin rubbers, urethane rubbers, and chlorophosphazene rubbers. Silicone rubber and fluororubber can be preferably used because they have low solubility parameters but have oil resistance.

The vibration-damping elastic body composition of the present invention can be obtained by simply blending the thermoplastic elastomer, rubber and synthetic resin, but may be subjected to dynamic crosslinking. Dynamic cross-linking refers to W. of Uniroyal. M. Fi
Scher et al. and A. of Monsanto. Y. Cor
It is a method developed by an et al., and refers to a process of blending rubber in a matrix of a thermoplastic resin, highly kneading the rubber while kneading with a cross-linking agent, and finely dispersing the rubber.

As the cross-linking agent used in such dynamic cross-linking, a peroxide, a resin cross-linking agent, which is usually used in rubber,
Sulfur etc. can be used.

As a dynamic crosslinking method, various extruders, Banbury mixers, kneaders, and a combination of these can be used to obtain the above-mentioned components by kneading, but when productivity is taken into consideration, Most preferably, it is produced continuously using a twin-screw extruder. Therefore, the extruder is preferably a long axis type having a length L / diameter D = 30 or more.

In the present invention, the dispersed particles in the vibration-damping viscoelastic composition are preferably dispersed with an average particle size of 50 μm or less. In particular, the rubber used in the present invention is preferably dispersed and mixed in a matrix component, and the average particle size thereof is preferably 50 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.
μm or less. If the dispersed particle size of the rubber component is large, sufficient vibration damping properties may not be obtained.

In the present invention, 100 or more dispersed particles were extracted in a random visual field observed with an electron microscope, and the average value of them was taken as the average particle diameter. For non-spherical particles, the diameter was taken as the circular area.

A so-called compatibilizer can be used in order to sufficiently disperse the rubber component in the matrix component and to strengthen the interface to further improve the performance.

The compatibilizing agent is roughly classified into one that does not involve a chemical reaction and one that involves no chemical reaction. The above is generally applied to block copolymers and graft copolymers and exhibits so-called emulsifying action. The latter includes a type having a functional group at the polymer terminal or side chain and a polymer macromer having a polymerizing group at the polymer terminal.

Specific examples of the compatibilizer include ethylene / glycidyl methacrylate copolymer-polymethyl methacrylate graft polymer, ethylene / glycidyl methacrylate copolymer-acrylonitrile / styrene copolymer graft polymer, ethylene / glycidyl methacrylate copolymer. -Polystyrene graft polymer, ethylene / ethyl acrylate copolymer-Polymethyl methacrylate graft polymer, ethylene / ethyl acrylate copolymer-Polyacrylonitrile graft polymer,
Ethylene / ethyl acrylate copolymer-polystyrene graft polymer, ethylene / vinyl acetate copolymer-polymethyl methacrylate graft polymer, ethylene /
Vinyl acetate copolymer-polyacrylonitrile graft polymer, ethylene / vinyl acetate copolymer-polystyrene graft polymer, polypropylene-polyacrylonitrile graft polymer, polypropylene-polystyrene graft polymer, polypropylene-polystyrene graft polymer, polyethylene-polymethylmethacrylate graft polymer , Polyethylene-polyacrylonitrile graft polymer, polyethylene-polystyrene graft polymer, epoxy-modified polystyrene-polymethyl methacrylate graft polymer, polybutylene terephthalate-polystyrene graft polymer, acid-modified acrylic-polymethyl methacrylate graft polymer, acid-modified acrylic-polystyrene Graft polymer, polystyrene-polymethy Methacrylate graft polymer,
Examples thereof include polystyrene-polyethylene graft polymer, polystyrene-polybutadiene graft polymer, polystyrene-polyacrylonitrile block copolymer, polystyrene-polybutyl acrylate block copolymer and the like.

Specific examples of the rubber component include the aforementioned styrene-butadiene block copolymer, styrene-butadiene block copolymer hydrogenated product, styrene-isoprene block copolymer, styrene-isoprene block copolymer hydrogenated product and the like. May also be used as a compatibilizer.

Commercially available compatibilizers are listed by trade name as NOF Corporation: MODEVA A, Toagosei Chemical Industry Co., Ltd .: RE.
A typical example is SEDA (R) GP100.

The preferred compatibilizing agent varies depending on the type of rubber component used, but particularly preferred is a compatibilizing agent having an epoxy group or a carboxy group capable of directly reacting with the matrix component.

In order to sufficiently finely disperse the rubber in the matrix component and to make it compatible, there is a method of using a rubber component modified with a compound having an appropriate functional group, in addition to the method of using the compatibilizing agent described above. Preferred functional groups are epoxy groups and carboxy groups.

The method for modifying the rubber is not limited, but as a general method for modifying the rubber, a monomer such as glycidyl methacrylate, glycidyl methyl methacrylate, maleic anhydride, or phthalic acid is used with an organic peroxide compound as an initiator. This is a method of grafting to rubber.

The modification may be carried out either before mixing the matrix and the rubber component, at the same time as mixing both components, or at the same time as mixing both components and dynamically crosslinking.

A plasticizer may be added to the vibration-damping elastic composition of the present invention in order to further improve flexibility and processability.

The plasticizer used is a process oil or a softening agent for mineral oil rubber called extension oil, dioctyl phthalate, dibutyl phthalate, diethyl phthalate, butyl benzyl phthalate,
Phthalates such as di-2-ethylhexyl phthalate, diisodecyl phthalate, diundecyl phthalate, diisononyl phthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimethyl phosphate, tributoxyethyl phosphate, tris -Chloroethyl phosphate, tris-dichloropropyl phosphate, condensed phosphoric acid ester, triphenyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, trilauryl phosphate, tricetyl phosphate, Phosphoric acid such as tristearyl phosphate and trioleyl phosphate Sterimes, trimellitic acid octyl ester, trimellitic acid isononyl ester, trimellitic acid isodecyl ester, and other trimellitic acid esters, dipentaerythritol esters, dioctyl adipate, dimethyl adipate, di-2-ethylhexyl adipate, diisobutyl Fatty acid esters such as adipate, dibutyl adipate, diisodecyl adipate, dibutyl diglycol adipate, di-2-ethylhexyl azelate, dioctyl azelate, dioctyl sebacate, di-2-ethylhexyl sebacate, methylacetyl ricinolate, pyromellitic acid Pyromellitic acid esters such as octyl ester, epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid alkyl ester (for example, epoxidized fat Acid octyl ester) and other epoxy plasticizers, adipic acid ether ester, polyether ester, polyether and other polyether plasticizers. These plasticizers may be used alone or in combination of two or more. it can.

When the above-mentioned plasticizer is used in the vibration-damping elastic body composition of the present invention, phthalic acid esters, phosphoric acid esters, epoxy-based plasticizers, polyether-based plasticizers and the like are preferable from the viewpoint of bleeding property. , And more preferably phthalic acid esters and polyether plasticizers. The plasticizer may be added before or after the addition of the crosslinking agent,
Further, a part may be added before crosslinking and the rest may be added after crosslinking.

Further, by blending a liquid rubber such as liquid NBR, liquid acrylic rubber or liquid polybutadiene rubber, workability and flexibility can be further improved.

The vibration-damping elastic composition of the present invention contains fillers such as calcium carbonate, calcium silicate, clay, kaolin, talc, silica, diatomaceous earth and mica powder as long as the processability is not impaired. , Asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, carbon black, carbon fiber, etc., or colorants such as carbon black, ultramarine blue, titanium oxide, zinc white, red iron oxide, Navy blue, azo pigments, nitrone pigments, lake pigments, phthalocyanine pigments and the like can be added.

Furthermore, it is usual to add various kinds of stabilizers such as antiaging agents, light stabilizers and ultraviolet absorbers in combination.

Specific examples of the above antiaging agents include phenyl-α-naphthylamine (PAN), octyldiphenylamine, N, N'-diphenyl-p-phenylenediamine (DPPD), N, N'-di-β-naphthyl. -P-
Phenylenediamine (DNPD), N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine (IPPD), N, N'- Diallyl-p-
Phenylenediamine, phenothiazine derivative, diallyl-p-phenylenediamine mixture, alkylated phenylenediamine, 4,4'-α, α- (dimethylbenzyl)
Diphenylamine, p, p-toluenesulfonylaminodiphenylamine, N-phenyl-N '-(3-methacryloyloxy-2-hydropropyl) -p-phenylenediamine, diallylphenylenediamine mixture, diallyl-p-phenylenediamine mixture, N -(1-methylheptyl) -N'-phenyl-p-phenylenediamine, amine anti-aging agents such as diphenylamine derivatives, 2-2 mercaptobenzimidazole (MBI),
Zinc salt of 2-mercaptobenzothiazole (ZnMB
I), zinc salt of 2-mercaptomethylbenzimidazole, tributylthiourea, 2-mercaptomethylbenzimidazole, imidazole antiaging agent such as 1,3-bis (dimethylaminopropyl) -2-thiourea, 2,5-di -T-amyl hydroquinone (DAH
Q), 2,5-di-t-butylhydroquinone (DBH
Q), 4,4'-hydroxydiphenylcyclohexane, 2,2'-methylenebis (4-methyl-6-t-butylphenol) (MBMTB), 2,6-di-t-butyl-4-methylphenol, 4, 4'-thio-bis (6-t-butyl-3-methylphenol), styrenate phenol, 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), 2,6-di- t-
Butyl-4-ethylphenol, bis (3,5-di-t
-Butyl-4-hydroxybenzyl) sulfide, phenol derivatives such as phenol derivatives and bisphenol derivatives, reaction products of acetone and diphenylamine (ADPAL), reaction products of diphenylamine, aniline and acetone, 2,2,4- Trimethyl-1,2-
Polymer of dihydroquinoline (TMDQ), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (ETMDQ), reaction product of amine and ketone, di-lauryl-thiopropionate, nickel dibutyl. -Dithiocarbamate-based antioxidants such as dithiocarbanate (NiDBC), nickel diethyl-dithiocarbamate, nickel dimethyl-dithiocarbamate, nickel dimethyl-dithiocarbamate, and antioxidants such as tri (nonylated phenyl) phosphate.

Tri (nonylphenyl) phosphite, triphenylphosphite, diphenylisodecylphosphite, trioctadecylphosphite, tridecylphosphite, thiodipropionic acid, dilaurylthiodipropionate, distearylthiodipropionate , Dimyristyl thiodipropionate, distearyl β, β
-Secondary anti-aging agents such as thiodibutyrate.

Specific examples of the light stabilizer and the ultraviolet absorber include 4-t-butylphenyl salicylate, 2,4-dihydroxybenzophenone and 2,2'-dihydroxy-.
4-methoxybenzophenone, ethyl-2-cyano-
3,3'-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate,
2 (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2
′ -Hydroxy-3,5′-di-t-butylphenyl)
Benzotriazole, 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, 2-hydroxy-
5-chlorobenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2 (2'-hydroxy-4-octoxyphenyl) benzotriazole, monoglycol salicylate, oxalic acid amide, Examples include phenyl salicylate and 2,2 ', 4,4'-tetrahydroxybenzophenone.

Glass transition point 30 to 10 used in the present invention
As the synthetic resin at 0 ° C., one kind or a mixture of plural kinds of well-known synthetic resins can be used. Specific examples of such synthetic resins include polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT),
Polyacetal, polyamide, epoxy resin, vinylidene fluoride, polysulfone, ethylene-vinyl acetate copolymer (EVA), polyphenylene sulfide (PP
S), polyetheretherketone (PEEK), polyphenylene oxide (PPO), styrene-maleimide copolymer, rubber-modified styrene-maleimide copolymer, styrene-methyl methacrylate copolymer, styrene-maleic anhydride copolymer Examples include polymers and rubber-modified PPO resins.

When the glass transition point of such a synthetic resin is outside the above-mentioned predetermined range, the tan δ value peak of the composition appears discontinuously, which is not preferable. Polyamide, PBT, etc. are mentioned as a preferable synthetic resin with a melting temperature of 170-250 degreeC blended with a composition.

The preferable blending ratio of the above raw materials is
The rubber is 10 to 85% by weight, the synthetic resin is 3 to 50% by weight, and the balance is a thermoplastic elastomer. If the compounding ratio of the rubber is less than the above range, the vibration damping performance at around 0 ° C. is inferior, and if it exceeds the above range, the vibration damping performance is difficult to be exhibited at a low temperature portion or at room temperature or higher. Further, if the blending ratio of the synthetic resin is less than the above range, the vibration damping performance in the high temperature part at room temperature or higher cannot be sufficiently exhibited, and if it exceeds the above range, the composition becomes too hard and the sheet or the like is formed. When processed, it is inferior in flexibility, so that the application site is limited.

From such a tendency, more preferable blending ratios of raw materials are 10 to 85% by weight of rubber and 5 to 3 of synthetic resin.
0% by weight, the balance being thermoplastic elastomer.

To mold the above raw materials into an elastic body, various extruders, rolls, screws, Banbury mixers,
After kneading by using a kneader, it may be extruded from a die or filled in a molding die for molding. A T-die may be used for molding into a sheet. By applying a well-known pressure-sensitive adhesive to the surface of the obtained sheet, a vibration-damping sheet that can be easily attached can be obtained.

In this case, specific examples of the pressure-sensitive adhesive used include urea-based, melamine-based, thermosetting resin-based adhesives,
Resorcinol type, phenol type (water soluble, alcohol soluble, novolac), epoxy type, polyurethane type, polyaromatic type (polyimide, polybenzimidazole), polyester type (alkyd type, unsaturated polyester, diallyl phthalate type, polyester acrylate, Acrylic acid diester), thermoplastic resin system,
Vinyl acetate type (emulsion, solution), polyvinyl alcohol type, polyvinyl acetal type (butyral, acetal, formal), vinyl chloride type, acrylic type (emulsion, solution, reactive type), polyethylene type (PE,
EVA), cellulose (nitrocellulose, cellulose acetate, ethyl cellulose, water-soluble cellulose), ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer, polyamide system, polyisobutylene, polyvinyl ether, elastomer system, chloroprene Rubber type (solution, latex), nitrile rubber type (solution, latex), SBR type, SBS-SIS type, polysulfide type, natural rubber type, chlorinated rubber type, recycled rubber type, butyl rubber type, silicone rubber type (RTV type, (Vulcanized type, pressure-sensitive type), phenolic
Vinyl type, epoxy / phenol type, phenol / chloroprene type, phenol / nitrile type, epoxy / polyamide type, epoxy / polysulfide type, nitrile /
Examples thereof include epoxy type and epoxy / nylon type.

The vibration-damping elastic sheet composition formed into any shape such as the vibration-damping sheet can be widely used for suppressing vibrations of vehicles, buildings, machines and the like. Examples of applications include automobile roofs, bodies, dash panels, door panels, floor panels, bonnets, trunks, oil pans, air spoilers, motors, copiers and printers, computers, CD / LD players, VTs.
OA / AV equipment such as R and speakers, washing machines, refrigerators, building-related products such as hinged doors, and ships and rail cars.

[Examples 1 to 3 and Comparative Examples 1 to 3] The raw materials used in Examples or Comparative Examples are collectively shown below.

The abbreviations used in Table 1 are shown in [].

(1) Thermoplastic polyester elastomer [TPEE] manufactured by Toray-Dupont: Hytrel (softening point 110 ° C.) (2) Acrylonitrile butadiene rubber [NBR] manufactured by Nippon Synthetic Rubber: JSR NBR (3) Polyamide [PA- 1] Toray: Alamine (glass transition point 47 ° C.) (4) Polyamide [PA-2] Toray: Rilsan (glass transition point 45 ° C.) (5) Polybutylene terephthalate [PBT] Toray: PBT resin (Glass transition point 17.80 ° C.) Raw materials were blended in the blending ratio (parts by weight) shown in Table 1 and the temperature was 230 ° C. with a twin-screw extruder and the screw rotation speed was 50 rp
The mixture was kneaded under the condition of m and extruded with a T-die into a sheet having a thickness of 2 mm. The width of the obtained example or comparative example is 3 m.
The hardness (JIS A) and the vibration damping property test were carried out using a test piece cut into a strip having a length of m and a length of 30 mm. The results are also shown in Table 1, and the results of the vibration damping test are shown in a graph in FIG.

[Vibration Damping Test] A test piece was used as a dynamic viscoelasticity measuring device (manufactured by Rheology Co .:
It was measured using a DVE Rheospectr DVE-V4).

Here, tan δ is the expression tan δ = E ″ (dynamic loss elastic modulus) / E ′ (when a strain (or stress) is observed as a response to the test piece when a cyclic stimulus of 10 Hz is applied. The loss angle in the relationship represented by the dynamic storage elastic modulus is shown.

[0075]

[Table 1]

As is clear from the results of Table 1 and the graph of FIG. 1, the thermoplastic polyester elastomer (TP
Comparative Example 1 consisting of a single component of EE) has a temperature of −40 ° C. to 80 ° C.
The loss angle (tan δ) was low in all test ranges of ° C, and the desired vibration damping performance was not obtained. Further, in Comparative Example 2 composed of a single component of NBR, the loss angle (tan δ) was high only near the glass transition temperature of 0 ° C., and stable vibration damping performance with respect to temperature change was not obtained. Also, TPEE and NBR
In Comparative Example 3 in which the two components consisting of
The vibration damping performance was good only in the vicinity, and good vibration damping performance could not be maintained in the higher temperature region. Also,
In Comparative Example 4 of the mixed two-component system of NBR and polyamide (Tg = ° C.), good vibration damping performance was exhibited at 0 ° C. or higher, but satisfactory vibration damping performance was not obtained at low temperatures.

On the other hand, in Examples 1 to 3 satisfying all the conditions, the loss angle (tan δ) was high in the test range of -40 ° C to 80 ° C, and the desired vibration damping performance was obtained. It was obtained stably.

[0078]

As described above, according to the present invention, since the thermoplastic elastomer having a predetermined softening temperature, the rubber and the synthetic resin are essential components, the peak of the loss coefficient tan δ at a specific temperature is eliminated, and the operating environment is reduced. As a temperature range, -30 ℃ ~
When a wide temperature range such as 100 ° C. is set, there is an advantage that the vibration damping elastic body composition can stably maintain the desired vibration damping performance.

[Brief description of drawings]

FIG. 1 is a chart showing the relationship between test temperature and tan δ in Examples and Comparative Examples.

Claims (5)

[Claims] 1. A vibration-damping elastic body composition comprising, as essential components, a thermoplastic elastomer having a softening point of 100 ° C. or higher, rubber, and a synthetic resin having a glass transition point of 30 to 100 ° C. 2. A synthetic resin 1 having (A) 1 to 98% by weight of a thermoplastic elastomer having a softening point of 100 ° C. or higher, (B) 1 to 98% by weight, and (C) a glass transition point of 30 to 100 ° C.
To 98% by weight, and a vibration-damping elastic body composition obtained by kneading and molding in a composition such that the total amount of (A), (B) and (C) is 100% by weight. 3. The vibration-damping elastic body composition according to claim 1, wherein the synthetic resin having a glass transition point of 30 to 100 ° C. is polyamide or polybutylene terephthalate. 4. The vibration-damping elastic body composition according to any one of claims 1 to 3, wherein the dispersed particles are dispersed in the multi-component in an average particle size of 50 μm or less. Stuff. 5. A vibration damping sheet formed by molding the vibration damping elastic body composition according to claim 1 into a sheet shape.