JPS6189842A - High vibration-damping material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a material that is excellent in processability such as deep drawing and bending, and has extremely high vibration damping properties.

BACKGROUND ART In recent years, the impact of noise from transportation such as automobiles, trains, and vehicles, as well as noise and vibration from factories and construction sites, on surrounding residents is increasing day by day, and has become a major social problem.

As a means of solving this problem, research and development of vibration-absorbing materials in which the material itself has vibration-absorbing ability is progressing. It is used as a structural member such as

Further, as a source of noise in automobiles, there is a large amount of noise coming from parts around the engine, especially the oil pan, and there is a need to reduce this noise.

Conventionally, such vibration damping materials include vinyl acetate-ethyl acrylate copolymer (Japanese Patent Publication No. 1985-85662).
, a copolymer in which a mixture of styrene and acrylonitrile is grafted onto a copolymer of hynylacetate and ethylene (Japanese Patent Publication No. 17064-1983), a resin composition mainly composed of a carboxylic acid-modified polyolefin resin (Japanese Patent Publication No. 1706-1983), 80
Laminated structures with a composition such as No. 454) as an intermediate layer, and materials in which bitumen is added with a filler such as calcium carbonate are known.

However, when these are made into a laminated structure with a metal plate, although they have vibration absorption ability in a specific temperature range, the adhesion with the metal plate is insufficient, and the elastic modulus of the intermediate layer composition is insufficient. It has drawbacks such as poor deep drawing and bending workability when used with a mechanical press, and poor heat resistance, and has difficulties in secondary workability as a vibration damping metal plate. The reality is that it is.

The disadvantages of the workability of conventional vibration-damping metal plates using mechanical presses, etc. include, for example, during deep drawing, the edge of the metal plate may shift, or in severe cases, the two stacked upper and lower metal plates may become vibration-damping. In addition to the problem of separation from the elastic resin layer and opening, the low elasticity of the resin layer also causes waving on the surface of the molded product and wrinkles on the curved corner surfaces.

In addition, 180° bending, known as hemming, is performed on the edges of vibration-damping metal plates, but in such severe processing, the waving and wrinkling of the metal plate surface are even worse. Unfortunately, it was not suitable for practical use.

SUMMARY OF THE INVENTION In view of these problems, the present invention aims to provide a highly vibration-damping material that has excellent processability such as deep drawing and bending, and has excellent vibration-damping performance.

As a result of extensive research in order to provide such an excellent high vibration damping material, the present inventors have developed a vibration damping material composed of two metal plates with a damping layer made of thermoplastic resin sandwiched between them. The resin has an elongation rate of 80% or more at a temperature of 20°C and a peak temperature of loss coefficient (tan δ) of IO°C to 1
The reed is within the range of 30℃, and the adhesive strength with the metal plate is ζH.
3kg/c in 180° peeling test at 20°C
The vibration-damping material (5), which is a mixture of at least one type of polyester resin or Holie Nute/L' thread resin and polyolefin tree manure, has excellent processability, heat resistance and high The present invention was achieved by discovering that it also has vibration absorption performance.

The present invention will be explained in detail below. The elongation rate at the temperature of 20°C used in the present invention is 30%.
With the above, the peak temperature of the loss coefficient (tan δ) is Jo℃ ~
The adhesive strength with the metal plate was 3 ky/3 in a 180' peeling test at a temperature of 20°C.
The polyester resin having a molecular weight of at least 40% by mole is terephthalic acid and dicarboxylic acid components, and the dicarboxylic acid components other than terephthalic acid include azefinic acid, sebacic acid, and adipic acid. , carbon number 2 or more, such as dodecanedicarboxylic acid
20 fatty acid dicarboxylic acids, aromatic dicarboxylic acids such as isophthalic acid and naphthalene dicarboxylic acid, or alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, singly or in mixtures; as diol components, ethylene glycol, 1,3-propanediol, 1 .4-butanediol, 1,6-hexanedio-~, 1.10-decanediol, neopentyl glycol, 1,4-cyclohexanediol, 2-ethyl IL/-2-buty/L'-1,
It is a resin polymerized from aliphatic glycol such as 8-propanediol or alicyclic glycol alone or in a mixture.

Among cholera, polyester copolymers consisting of terephthalic acid residues, ethylene glycol residues, and 1,4-cyclohexanediol residues are preferred, and 1,4-cyclohexane dimeta is particularly preferred compared to ethylene glycol residues. Amorphous polyester copolymer resins with many tool residues (e.g. Eastman Kodak KODA
ROPETG6768), and also polyester resins synthesized from terephthalic acid, iso-7-μ acid and 1,4-cyclohexane dimetatool (e.g. Eastm
An Kodak company, Kodar PCTA resin A-1
50) is also a particularly preferred resin.

Also, among thermoplastic high molecular weight polyester resins, amorphous polyester resins [e.g. Toyobo Pylon≠2
00 (Tf67℃), +108 (Tr47C), +2
90 (T17℃), +800 (TV7℃), +500 (
Tr4℃), +600 CT147℃), +GK180
(Trio℃)] (loss coefficient based on T2 (
tan δ) is extremely high, and accordingly the loss coefficient (η)
It is a particularly preferred resin because of its high performance.

A mixture of the above resins also has favorable physical properties.O This polyester resin alone has excellent adhesion to metal plates, and is a material with excellent workability and vibration damping properties.
In particular, in order to increase the adhesive strength with the metal plate and improve the press workability, it is desirable to mix K with a modified polyolefin resin that has excellent adhesiveness with the metal plate.

Examples of this polyolefin resin include α-olefin-clycidyl methacrylate copolymer or α-olefin-glycidyl methacrylate-vinyl acetate copolymer, and the glycidyl methacrylate content in this copolymer is 0.5 to 5. ZOX<amount% preferably 1 to 15
The vinyl acetate content is θ~20% by weight, preferably 1-10% by weight.

The above α-olefin-glycidyl methacrylate copolymer or α-olefin-glycidyl methacrylate
Vinyl acetate μ copolymer is polyester copolymer resin 1
It is possible to mix 1 to 900 parts by weight, particularly preferably 20 to 150 parts by weight, with respect to 00 parts by weight. When we sandwiched the plates to create a sandwich structure and measured the loss coefficient (η), which is the vibration damping performance, we found that mixtures generally have the disadvantage of having a lower peak height than a single substance; It was found that the mixture of polyester resin and polyolefin resin of the invention maintains high vibration damping performance without changing the response peak height.

In addition, when used as the resin layer of the present invention, from the viewpoint of easy processability in the room temperature range and high vibration damping properties in the applicable temperature range, the loss coefficient (tan) due to the glass transition temperature (Tri) is
It has been found that extremely excellent vibration damping performance can be obtained by using resin bait composition λ) whose peak temperature of δ) is within the applicable temperature range. This refers to a temperature range, and for example, in the case of automobile engine parts, high vibration damping performance may be maintained in a temperature range of 50 to 130°C, with a focus on 80 to 90°C.

In addition, in order to obtain high vibration damping performance, the loss coefficient (tanδ)
It is necessary that the peak value of is 0.8 or more, and in this case, it has been found that a particularly preferable performance with a loss coefficient (η) of 0.5 or more as a vibration damping material can be obtained.

A resin composition having the above-mentioned good physical properties is the driving force behind the resin composition of the present invention.

If the film thickness of the resin composition (5) is 30μ or more, vibration damping performance will be good, but in order to have good workability such as bending and drawing, it is preferably 100μ or less,
Most preferably, it is 30μ or more and 60μ or less.

As a manufacturing method for the damping material of the present invention, any method such as a normal patch method or a continuous heat press method can be applied.

For example, there is a method of interposing the resin composition between two metal plates and bonding them under heat.0 adhesion is generally 150~
It is carried out at 260°C.

The vibration damping material of the present invention can be particularly used to prevent noise and vibration generated by automobiles. In this case, the source of automobile noise and vibration is the engine parts, and the main source of noise and vibration is the oil pan. It is.

When the material of the present invention was applied to an oil pan for a medium-sized diesel engine, it was found that it was possible to reduce I noise by 8 dB at a location approximately 1 m away from the engine.

In addition, it has been found that applying it to car body materials, especially floor panels, is highly effective in preventing noise and vibration from entering the car.
It is desirable to apply it to electrical parts, especially to materials for covers for motors or ballasts.

Furthermore, for this purpose, it is desirable to apply it to building materials such as room partitions, wall materials, and floor materials, and it has also been found that it is useful for preventing noise pollution when applied to rain shutters or aluminum sash doors.

In addition, noise from engines or generators used in road construction is generally high, and application to these components is also a desirable application.In addition, the noise from bicycles, motorcycles, etc. as general means of transportation is To prevent this, good results can be obtained by using it as a brake member for braking or a chain member for driving.

In addition, as a means of public transportation, railways4 (using it for dual-use flooring and wall materials are also highly effective in preventing noise pollution.

The present invention will be specifically explained below with reference to examples, but these are merely illustrative and the present invention is not limited thereto. The elastic modulus and loss coefficient (tan δ) were measured using Toyo Baldwin Rheopybron (110 Hz), and the elongation rate was determined at a tensile rate of 200 fi/min. The loss coefficient (η), which represents the vibration absorption ability of the damping material, is Measurements were made using forced vibration using the mechanical impedance method (central vibration) at a frequency of 1000 Hz and a temperature of 20 to 130°C. ◇The adhesion to steel plates in the adhesion test was determined by cold-rolled steel plates (0.8 mm)/
The resin composition (50μ)/cold rolled steel plate (0,8111
The workability was evaluated using the configuration shown in Figures 1 and 2. The mold shown in the figure was used to test the bending and drawing processability, and evaluation of cracking, peeling, wrinkles, etc. Figure 1 (Al is a cross-sectional view of the bending test mold. In the figure, 1.2.l is a mold member, 4 is a spacer, and 5 is a sample. Also, 2R.

5R etc. indicate curvature. FIG. 1(b) is a perspective view of a molded product subjected to an unbending process. In the same figure, parts A, B,
Part 0 indicates the evaluation observation part, respectively. Figure 2 fat is a cross-sectional view of the draw 9 workability test mold. In the figure, 1.2.3.4.5 indicates a mold member, and 6 indicates a sample. Further, 5R is the curvature, and 50φ and 56φ are the diameters of the corresponding parts.

In the figure, 1 indicates wrinkles at part A, 2 indicates wrinkles at the flange, and 3 indicates the observation areas for evaluation of the plate surface.
tman Kodak Kodar@PETG 676
8) using an inflation die (caliber 150
M) The tubular body was taken using an inflation device equipped with a T-equipment at a take-up speed of 7.0 m/min, a prower, and a tube reel No. 2.0, with a fold diameter of 470 t and a thickness as shown in Table 1. A film having a thickness of 1c50μ was obtained.

Using the obtained film, it was hot-pressed (280°C, 5 minutes, 80 kq/i) between cold-rolled steel plates with a 0.8 fin thickness, and its adhesion, workability, and vibration absorption properties were measured. are shown in Tables 2 to 4 and FIG.

FIG. 3 is a diagram showing the relationship between temperature and loss coefficient (η) of the damping material.

Example 2 PCTA polyester resin (Eastman Koda
Using an inflation device equipped with an inflation die (caliber 1500), the tubular body was taken up at a taking-up speed of 7.0 m for 7 minutes and a blow-up pressure of No. 2.0. A film having a fold diameter of 470 mm and a thickness of 50 μm as shown in Table 1 was obtained.

Using the obtained film, heat and press (280°C, 5 minutes, 30ky/m) between 0.8 fi thick cold rolled steel plates.
L adhesion, workability and vibration absorption were measured.

The results are shown in Tables 2 to 4 and Figure 3.
〇Example 3 Amorphous copolymerized polyethylene terephthalate tree Q'p (
Eastman Kodak Kodaro PETG
6763) 70% by weight, manufactured by Sumitomo Chemical Industries, polyolefin resin [ethylene glycidyl methacrylate]
Vinyl acetate copolymer] 30% by weight was mixed in a Henschel mixer, and the mixture was heated to 30 fin diameter at 230°C.
After kneading it in an extruder, it was made into a paste.

Using this pellet, the tubular body was taken up and folded using an inflation device equipped with an inflation die (caliber 150 fl) at a taking-up speed of 7.0 m/min, a prower, and a derecition number 2.0. A film having a diameter of 470 knots and a thickness of 50 μm as shown in Table 1 was obtained.

B) Using the film, heat pressure is applied between cold rolled steel plates with a thickness of 0.811111! (280℃, 5 minutes, 80 kv
crA) Adhesion, workability and vibration absorption properties were measured and the results are shown in Tables 2 to 4 and Figure 3.
The figure is a diagram showing the relationship between temperature and loss coefficient (1) of damping material.

Comparative Example 1 Example 4 in a resin composition mainly composed of a carboxylic acid-modified polyolefin resin disclosed in JP-A-59-80454 was prepared as follows.

71/) Index 4 P/10 min linear low-temperature polyethylene (manufactured by CdF Chimie) with 0.7% by weight of maleic anhydride and 0 t-butyl peroxylaurate.
．． 1% by weight was added and mixed for 2 minutes using a Hensiel mixer, which was then kneaded using an extruder with a diameter of 30 fins set at 190°C, and then made into pellets.

This modified polyethylene and Melt Index 4 f/1
0 minute linear low density polyethylene (CdF Chimie)
(Company) and methyl methacrylate polymer were mixed in the proportions shown in Table 5, and the mixture was kneaded in an 808φ extruder set at 190°C, and then pelletized.

This material was formed into a film in the same manner as in Examples 1 to 8, and the resulting film was heat-pressed (230°C, 5 minutes, 80 kyicr) between 0.8-thick cold-rolled steel plates.
A) L adhesion, processability and vibration absorption were measured.

The results are shown in Tables 2 to 64 and FIG.

FIG. 3 is a diagram showing the relationship between the temperature and the loss coefficient (?7) of the damping material.

Chapter 1 Table Table 2 'P; 3 tables Table 5

[Brief explanation of the drawing]

Figure 1 (al is a cross-sectional view of the mold for the unbending process test. Figure 1 (bl is a perspective view of the molded product for the unbending process test. Figure 2 (a) is the mold for the drawing 9 workability test. Figure 2 (fb), which is an Ir plane view of 0, is a perspective view of the drawable wipe molded product. Figure 3 is a diagram showing the relationship between temperature and loss coefficient (η) of the damping material. ( a) (tl)Figure 1 (a,) (I)) Temperature (°C) Figure 3

Claims (10)

[Claims] (1) A damping material composed of a damping layer made of thermoplastic resin sandwiched between two metal plates, the resin being at a temperature of 2
When the elongation rate at 0°C is 30% or more, the loss coefficient (tanδ
) has a peak temperature in the range of 0°C to 130°C, and
High vibration damping properties that are at least one type of polyester resin or a resin composition of polyester resin and polyolefin resin (A) whose adhesive strength with a metal plate is 3 kg/cm or more in a 180° peeling test at a temperature of 20 ° C. material. (2) The resin composition (A) of polyester resin or polyester resin and polyolefin resin has a loss coefficient (tan δ) peak temperature of 25°C to 115°C.
The material according to claim 1, which has a peak value of 0.8 or more. (3) The material according to claim 1 or 2, wherein the polyester resin contains a polyester copolymer resin consisting of a terephthalic acid residue, an ethylene glycol residue, and a 1,4-cyclohexanediol residue. . (4) The material according to claim 3, wherein the polyester copolymer resin is an amorphous polyester copolymer resin containing more 1,4-cyclohexanedimethanol residues than ethylene glycol residues. . (5) The material according to claim 1 or 2, wherein the polyester resin contains a polyester copolymer resin synthesized from terephthalic acid, isophthalic acid, and 1,4-cyclohexanedimethanol. (6) The material according to claim 1 or 2, wherein the polyester resin is an amorphous high molecular weight polyester resin alone or in a mixture. (7) The resin composition (A) contains polyester resin 100%
α-olefin 70-99.5% by weight based on parts by weight
, resin compositions 1-90 consisting of 0.5-20% by weight of glycidyl methacrylate and 0-20% by weight of vinyl acetate.
The material according to claim 1 or 2, which is a resin composition obtained by mixing 0 parts by weight. (8) The material according to claim 1 or 2, wherein the damping layer made of a thermoplastic resin has a thickness of 30 μm or more and 60 μm or less. (9) A damping material composed of a damping layer made of a thermoplastic resin sandwiched between two metal plates, the resin being the above-mentioned polyester resin or a resin composition of a polyester resin and a polyolefin resin ( A) Engine parts using the highly damping material. (10) The component according to claim 9, wherein the engine component is an oil pan.