JPH0434499B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a material that has excellent workability in deep drawing, bending, etc., and has extremely high vibration damping properties. 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 is progressing on vibration-absorbing materials that have vibration-absorbing ability themselves. It is used as a structural member. In addition, noise from parts around the engine, especially the oil pan, is a major source of noise in automobiles, and it has become necessary to reduce this noise. Conventionally, such damping materials include vinyl acetate-ethylene copolymer (Japanese Patent Publication No. 45-35662), vinyl acetate-ethyl acrylate copolymer grafted with a mixture of styrene and acrylonitrile (special patent). Fillers such as calcium carbonate in laminated structures and bitumens with intermediate layers of resin compositions mainly composed of carboxylic acid-modified polyolefin resins (Japanese Patent Application Laid-open No. 59-80454) There are known materials with added . 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. The fact is that it has disadvantages such as poor deep drawing and bending workability with mechanical presses due to low heat resistance, and poor heat resistance, so it has difficulties in secondary workability as a vibration damping metal plate. 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 detachment 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, a 180° bending process called hemming is carried out to process the edges of vibration-damping metal plates, but such severe processing can cause severe waving and wrinkles on the metal plate surface, making it difficult to put it into practical use. It had become unbearable. In view of these problems, the present invention provides deep drawing,
The object of the present invention is to provide a highly vibration-damping material that has excellent workability such as 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 consisting of two metal plates with a damping layer made of thermoplastic resin sandwiched between them. and the temperature of the resin is 20℃
The elongation rate is 30% or more and the peak temperature of the loss coefficient (tan δ) is in the range of 0°C to 130°C, and
At least 1 whose adhesive strength with the metal plate is 3 kg/cm or more in a peeling test at 20°C and 180°C.
The present invention was achieved by discovering that the vibration damping material, which is a resin composition (A) that is a mixture of various polyester resins and polyolefin resins, has excellent workability, heat resistance, and high vibration absorption performance. did. The present invention will be explained in detail below. The elongation rate at the temperature of 20℃ used in the present invention is
The peak temperature of the loss coefficient (tanδ) is 0 at 30% or more.
℃ to 130℃, and the adhesive strength with the metal plate was 3 in a 180° peeling test at a temperature of 20℃.
For polyester resins with a weight of Kg/cm or more,
It consists of a dicarboxylic acid component of which at least 40 mol% is terephthalic acid and a diol component, and dicarboxylic acid components other than the above-mentioned terephthalic acid include resin acids having 2 to 20 carbon atoms such as azelaic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid. Aromatic dicarboxylic acids such as dicarboxylic acid, isophthalic acid, and naphthalene dicarboxylic acid, or alicyclic dicarboxylic acids such as dichlorohexane dicarboxylic acid, singly or as a mixture; diol components such as ethylene glycol, 1,3-propanediol, 1,4 −
butanediol, 1,6-hexanediol,
Polymerized with resinous glycols such as 1,10-decanediol, neopentyl glycol, 1,4-dichlorohexanediol, 2-ethyl-2-butyl-1,3-propanediol, and alicyclic glycols alone or in mixtures. It is a resin. Among these, polyester copolymers consisting of terephthalic acid residues, ethylene glycol residues and 1,4-cyclohexanediol residues are preferred, and 1,4-cyclohexane copolymers are particularly preferred compared to ethylene glycol residues. Amorphous polyester copolymer resin with many dimethanol residues (e.g. Eastman Kodak KODAR〓 PETG
6763), and polyester resins synthesized from terephthalic acid, isophthalic acid, and 1,4-cyclohexanedimethanol (e.g. Eastman
Kodar PCTA resin A-150 (Kodak, Inc.) is also a particularly preferred resin. Also, among thermoplastic high molecular weight polyester resins, amorphous polyester resins [for example, Toyobo Vylon 200 (Tg 67℃), 〓103 (Tg 47℃),
〓290 (Tg87℃), 〓300 (Tg7℃), 〓500 (Tg4
℃), 〓600 (Tg 46℃), 〓GK130 (Tg 10℃)] also have extremely high loss coefficients (tan δ) due to Tg, and correspondingly high loss coefficients (η), making them particularly preferable resins. Polyester resins that are also crystalline, e.g.
Toyobo Byron〓〓〓30P (Tg-28℃), same〓
GM900 (Tg-20℃), GM400 (Tg 19℃), GM990 (Tg-20℃), GV100 (Tg 52℃)
GV700 (Tg 54°C) is also a preferable resin because it has a high loss coefficient (η) and is flat over a wide temperature range. The mixture of the above thermoplastic high molecular weight polyester resins also has favorable physical properties. In the case of this mixture, a combination of amorphous polyester resin and crystalline polyester resin can also be used. This polyester resin alone has excellent adhesion to metal plates, and is a material with excellent workability and vibration damping properties, but in particular, in order to increase the adhesive strength with metal plates and improve press workability, It is desirable to mix a modified polyolefin resin which has excellent adhesion to metal plates. Examples of the polyolefin resin include α-olefin-glycidyl methacrylate copolymer or α-olefin-glycidyl methacrylate-vinyl acetate copolymer, and the glycidyl methacrylate content in this copolymer is preferably 0.5 to 20% by weight. The vinyl acetate content is 0 to 20% by weight, preferably 1 to 10% by weight. By setting the content of glycidyl methacrylate and vinyl acetate in the copolymer within this range, it is possible to have excellent adhesion to a metal plate and good press workability. The above α-olefin-glycidyl methacrylate copolymer or α-olefin-glycidyl methacrylate-vinyl acetate copolymer is added in an amount of 20 to 150 parts per 100 parts by weight of the polyester copolymer resin.
Parts by weight. A film is made using such a mixture,
Create a sandwich structure plate by sandwiching it between copper plates,
When we measured the loss coefficient (η), which is vibration damping performance, we found that mixtures generally have the disadvantage that the peak height is lower than that of a single substance, but the polyester resin and polyoffine resin of the present invention It was found that the mixture maintains high damping performance without any change in peak height. In addition, when used as a resin layer according to the present invention,
From the viewpoint of easy processability in the normal temperature range and high vibration damping properties in the applicable temperature range, a resin composition (A) whose peak temperature of the loss coefficient (tan δ) due to the glass transition point (Tg) is in the applicable temperature range is selected. When used, it was found that extremely excellent vibration damping performance could be obtained. The applicable temperature range here refers to the temperature range in which vibration damping performance is required. For example, in the case of automobile engine parts, high vibration damping performance is achieved in the temperature range of 50 to 130°C, centered around 80 to 90°C. It would be good if it could be maintained. In addition, in order to obtain high vibration damping performance, the peak value of the loss coefficient (tanδ) must be 0.8 or more.
In this case, it was found that particularly favorable performance as a vibration damping material with a loss coefficient (η) of 0.5 or more can be obtained. A resin composition having the above-mentioned good physical properties is the resin composition (A) of the present invention. If the film thickness of the resin composition (A) is 30μ or more, vibration damping performance is good, but in order to have good workability such as bending and drawing, it is preferably 100μ or less, and most preferably 30μ or more 60μ
The following is desirable. As a method for producing the damping material of the present invention, any conventional batch method or continuous heat press method can be used. For example, there is a method of interposing the resin composition between two metal plates and bonding them under heat and pressure. Bonding is generally carried out at 150-260°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 sources of noise and vibration in automobiles are engine parts, of which the oil pan is the main source. When the material of the present invention was applied to an oil pan for a diesel engine of a medium-sized truck, it was found that noise could be reduced by 3 dB at a location approximately 1 m away from the engine. In addition, it was found that application to vehicle body materials, particularly dart panels and floor panels, is highly effective in preventing noise and vibrations entering the vehicle interior. Next, to prevent noise and vibration in homes or offices, it is desirable to apply it to electrical parts, and it is particularly desirable to apply it 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 road construction engines or generators is generally considered to have a high noise level, and it is also preferable to apply the present invention to these components. Further, in order to prevent noise from automobiles, motorcycles, etc. as general means of transportation, good effects can be obtained when used as a brake member for braking or a chain member for driving. Furthermore, its use in flooring and wall materials for railway vehicles as a means of public transportation is also highly effective in preventing noise pollution. EXAMPLES 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. In the examples, the elastic modulus and loss coefficient (tan δ) of the film were measured using a Toyo Baldwin Rheovibron (110 Hz), and the elongation rate was determined at a tensile speed of 200 mm/min. Loss coefficient (η) that represents the vibration absorption ability of damping material
was measured using forced vibration using the mechanical impedance method (central excitation) at a frequency of 1000Hz and a temperature of 20 to 130℃. The adhesion properties of the steel plate in the adhesion test were determined under the conditions of 190℃, 5 minutes, and 30Kg/cm ² with the composition of cold rolled steel plate (0.8 mm) / the resin composition (50μ) / cold rolled steel plate (0.8 mm). It was bonded and evaluated at an angle of 180° and a pulling speed of 50 mm/min. For workability, using the molds shown in FIGS. 1 and 2, bending back and drawing workability were tested, and slippage, peeling, wrinkles, etc. were evaluated. FIG. 1a is a cross-sectional view of the bending test mold. In the figure, 1, 2, and 3 are mold members, 4 is a spacer, and 5 is a sample. Further, 2R, 5R, etc. indicate curvature. FIG. 1b is a perspective view of a molded product tested by unbending. In the same figure, A part, B part
Sections and C sections indicate evaluation observation sections, respectively. FIG. 2a is a cross-sectional view of the drawability test mold. In the figure, 1, 2, 3, 4, and 5 indicate mold members, and 6 indicates a sample. Also, 5R is curvature, 50φ,
56φ indicates the diameter of the corresponding part. FIG. 2b is a perspective view of a molded product tested for drawability. In the same figure, 1 indicates the wrinkles at part A, 2 indicates the flange wrinkles, and 3 indicates the evaluation observed portions of the plate slippage. Comparative Example 1 Amorphous copolymerized polyethylene terephthalate resin (Eastman Kodak Kodar PETG 6763)
Using an inflation die (caliber 150mm)
The tubular body was collected using an inflation device equipped with
A film of 50μ was obtained. Using the obtained film, heat and press (230℃, 5 minutes, 30Kg/cm ² ) between 0.8mm thick cold rolled steel plates.
The adhesion, processability and vibration absorption properties were measured. The results 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. Comparative Example 2 PCTA polyester resin (Eastman Kodak)
Using Kodar PCTA A-150), the tubular body was collected using an inflation device equipped with an inflation die (diameter 150 mm) at a take-up speed of 7.0 m/min.
Picked up under the conditions of blowout presio 2.0, folded diameter 470
A film having a thickness of 50 μm as shown in Table 1 was obtained. Using the obtained film, heat and press (230℃, 5 minutes, 30Kg/cm ² ) between 0.8mm thick cold rolled steel plates.
The adhesion, processability and vibration absorption properties were measured. The results 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 1 Amorphous copolymerized polyethylene terephthalate resin (Eastman Kodak Kodar PETG 6763)
70% by weight, produced by Sumitomo Chemical Industries, 30% by weight of polyolefin resin [ethylene-glycidyl methacrylate-vinyl acetate copolymer] were mixed in a Henschel mixer, and the mixture was heated to 230°C.
The mixture was kneaded using a φ extruder and then pelletized. Using this pellet, the tubular body was taken up using an inflation device equipped with an inflation die (diameter 150 mm) at a take-up speed of 7.0 m/min and a blow-out ratio of 2.0, with a fold diameter of 470 mm and a thickness of A film having a thickness of 50μ was obtained as shown in Table 1. Using the obtained film, heat and press (230℃, 5 minutes, 30Kg/cm ² ) between 0.8mm thick cold rolled steel plates.
The adhesion, processability and vibration absorption properties were measured. The results 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. Comparative Example 3 Example 4 in a resin composition mainly composed of a carboxylic acid-modified polyoffine resin disclosed in JP-A-59-80454 was prepared as follows. Melt Train Index 4g/10min linear low-polyethylene (manufactured by CdF Chimie) with maleic anhydride
0.7% by weight and t-butyl peroxylaurate
Add 0.1% by weight and mix with Henschel mixer for 2 hours.
The mixture was mixed for minutes, kneaded using a 30 mm diameter extruder set at 190°C, and then pelletized. This modified polyethylene and melt index
4g/10min linear low density polyethylene (CdF)
(manufactured by Chime), methyl methacrylate polymer as the fifth
They were mixed in the proportions shown in the table, and the mixture was kneaded in a 30 mmφ extruder set at 190°C, and then pelletized. This material was made into a film in the same manner as in Example 1, and the resulting film was heat-pressed between 0.8 mm thick cold-rolled steel plates (230°C, 5 minutes, 30 minutes).
Kg/cm ² ) and the adhesion, workability and vibration absorption properties were measured. The results 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.

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【table】 [Brief explanation of drawings]

FIG. 1a is a cross-sectional view of the bending test mold. FIG. 1b is a perspective view of a molded product tested by unbending. FIG. 2a is a cross-sectional view of the drawability test mold. FIG. 2b is a perspective view of a molded product tested for drawability. FIG. 3 is a diagram showing the relationship between temperature and loss coefficient (η) of the damping material.

Claims (1)

[Scope of Claims] 1. A damping material composed of a damping layer made of thermoplastic resin sandwiched between two metal plates, wherein the resin has a loss coefficient when the elongation rate at a temperature of 20°C is 30% or more. The peak temperature of (tan δ) is in the range of 0°C to 130°C, and the adhesive strength with the metal plate is at 20°C.
3 kg/cm or more in a 180°C peeling test, and the resin contains 70 to 99.5 parts by weight of α-olefin based on 100 parts by weight of at least one type of polyester resin.
A highly damping material which is a resin composition (A) prepared by mixing 20 to 150 parts by weight of a polyolefin resin consisting of 0.5 to 20 parts by weight of glycidyl methacrylate and 0 to 20 parts by weight of vinyl acetate. 2 Claims in which the resin composition (A) of a polyester resin and a polyolefin resin has a loss coefficient (tan δ) whose peak temperature is in the range of 25°C to 115°C, and whose peak value is 0.8 or more. Materials described in paragraph 1. 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. Claim 1 or 2, wherein the polyester resin contains a polyester copolymer resin synthesized from terephthalic acid, isophthalic acid, and 1,4-cyclohexanedimethanol.
Materials listed in section. 6. The material according to claim 1 or 2, wherein the polyester resin is a single or a mixture of amorphous high molecular weight polyester resins. 7 The thickness of the damping layer made of thermoplastic resin is 30 mm or more
The material according to claim 1 or 2, which has a particle size of 60μ or less. 8 A damping material composed of a damping layer made of thermoplastic resin sandwiched between two metal plates, where the resin has an elongation rate of 30% or more at a temperature of 20°C and the peak temperature of the loss coefficient (tan δ) is in the range of 0°C to 130°C, and the adhesive strength with the metal plate is at 20°C.
3 kg/cm or more in a 180°C peeling test, and the resin contains 70 to 99.5 parts by weight of α-olefin based on 100 parts by weight of at least one type of polyester resin.
An engine using a highly damping material which is a resin composition (A) made by mixing 20 to 150 parts by weight of a polyolefin resin consisting of 0.5 to 20 parts by weight of glycidyl methacrylate and 0 to 20 parts by weight of vinyl acetate. parts. 9. The component according to claim 8, wherein the engine component is an oil pan.