JPS6123648A - Heat-resistant damping material - Google Patents

Abstract

PURPOSE:A heat-resistant damping material which has excellent flexibility at ordinary temperatures, excellent vibration-damping properties at high temperatures, and good fit to a mold, prepared by mixing an organic binder consisting of a thermosetting resin, a rubbery substance, and a bituminous substance with an inorganic filler. CONSTITUTION:A thermosetting resin (a) (e.g. an epoxy resin) and a rubbery substance (b) (e.g. a thermoplastic polyurethane elastomer) are mixed in a weight ratio, a/b, of 0.1-5, and the mixture is mixed with 5-60wt% (of component A) bituminous substance (c) (e.g. blown asphalt) to give an organic binder (A). 30- 450pts.wt. inorganic filler (B) (e.g. flaky mica having an aspect ratio of 10 or higher) is added to 100pts.wt. component A, and the mixture is kneaded to give a heat-resistance damping material.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is applicable to a wide range of fields such as automobiles, general and railway vehicles, ships, pattern devices, architecture, air conditioning equipment, and home appliances at a temperature of approximately 40°C to 120°C during use. The present invention relates to a heat-resistant vibration damping material that can be applied to structural members that vibrate and generate noise at relatively high temperatures. More specifically, it is a sheet-like damping material that is flexible at room temperature and can exhibit damping performance at relatively high temperatures after being heat-treated, such as for use on automobile mufflers. It can be applied with high adhesion to complex structural members such as air conditioning equipment in kitchens, industrial household appliances, etc., and suppresses vibrations of the structural members at relatively high temperatures, thereby preventing damage caused by vibration. The present invention relates to a heat-resistant vibration damping material that reduces noise caused by noise.

(Prior Art) In recent years, with the enrichment of social life, there has been a strong desire to reduce noise and vibration, which is one way of improving the environment, and various vibration damping materials have been used.

For example, asphalt-based vibration damping materials are used as vibration damping materials that are attached to car bodies to reduce vibration and noise, but the applicable temperature range is narrow and the temperature during use is 40°C or higher. The vibration damping performance deteriorated significantly at high temperatures, and the adhesive strength with the steel plate was also poor.

Therefore, several damping materials have been proposed that attempt to improve damping performance in the relatively medium temperature or relatively high temperature range of approximately 0° C. to 60° C. For example, as an allocation material suitable for a relatively medium temperature range, JP-A No. 58
It is disclosed in Japanese Patent No.-39828. Furthermore, thermosetting resins,
A heat-resistant vibration damping material composition comprising a mixture of a comb-like substance, a thermoplastic resin, and a scale-like inorganic filler was published in Japanese Patent Publication No. 54-849.
It is disclosed in Publication No. 7.

(Problems to be Solved by the Invention) However, in the conventionally known damping materials that are pasted on the surfaces of structural members in the relatively medium to relatively high temperature range, even in the relatively high temperature range, At the high temperature side of ℃~120℃, the vibration damping performance often decreases and becomes insufficient.In order to improve this, if we want to have heat resistance at high temperatures and maintain excellent damping performance, it is necessary to Even if damping is not flexible at room temperature and damping performance is improved at the relatively high temperature, there is a temperature at which sufficient damping performance is achieved. In some cases, the area becomes narrower, and in other cases, partial improvement appears on both the room temperature side and the high temperature side of the relatively high temperature area.In the end, the improvement in damping performance can be averaged over a wide range of temperatures. It was not something that could be achieved stably, and even if it was put into practical use, it was not fully satisfactory or could be called a success.

Furthermore, the 7-piece splitting material has disadvantages such as being too flexible, or in extreme cases becoming too sticky, causing blocks to accumulate together, and reducing workability due to stickiness, etc. There were too many things.

It is very talented, has good mold conformability for complex structural members, (2
On the other hand, there is a desire for a heat-resistant vibration damping material that provides good adhesive strength and is relatively inexpensive, but a satisfactory material has not yet been obtained.

(Means for solving the problems) The present invention has been made by focusing on the above-mentioned problems,
The aim is to provide a heat-resistant allocating material that can fully meet the demands of the past.

That is, in a damping material mainly composed of an organic binder containing a thermosetting resin, a rubbery substance, and a bituminous substance as essential components, and an inorganic filler, the inorganic filler is added to 100 parts by weight of the organic binder. 30 to 4
The bituminous substance is contained in 100 parts by weight of the organic binder, and the bituminous substance is contained in 5 to 60 parts by weight, and the weight ratio of the thermosetting resin and the rubbery substance is 1:0.1 to 1.
The organic binder contains a thermosetting resin, a rubbery substance, and a bituminous substance as essential components, and the viscoelasticity varies depending on the blending ratio of these three components. The blending ratio of these three components plays an important role in maintaining the vibration damping effect required in the target temperature range.

First, the #blue substance is 5 parts by weight in 100 parts by weight of the organic binder.
-60 parts by weight, preferably 10 to 55 parts by weight, is included in the device.If it is outside this range and exceeds 60 parts by weight, the distribution effect at high temperatures will not be obtained, and if it is less than 5 parts by weight, the distribution effect will not be obtained. It is not possible to widen the temperature range obtained, and even if the temperature is within the range of 5 to 60 parts by weight, the price can be reduced at 55 to 60 parts by weight, but depending on the environment, it may become tired easily. Since it is difficult to obtain a sufficiently wide temperature range that satisfies the vibration damping effect with 5 to IO weight percent, a range of 10 to 5 parts by weight is preferable.

Next, the thermosetting resin and the rubbery substance are mixed in a weight ratio of I: 0.1 to summer: 5, preferably I: within the range of the weight of the organic binder minus the weight of the bituminous material. It is blended in a range of 0.2 to 1;3. The mixing ratio of the thermosetting resin and the rubbery substance affects the distribution performance in the high temperature range after heat curing, but if the ratio exceeds the above range and the amount of the rubbery substance is too much, the control The temperature range in which the oscillation effect is obtained becomes too high and deviates from the temperature range in which the damping effect is required, and therefore the width of the temperature range in which the desired oscillation effect is obtained becomes narrow; If the amount of thermosetting resin is small and the amount of rubbery material is large, the temperature range in which a damping effect is obtained becomes too low and deviates from the temperature range in which a damping effect is required.

Further, when blending the thermosetting resin, it is convenient to use a liquid one. Liquid thermosetting resin acts as a plasticizer for the mixture of rubbery material and bituminous material, and since rubbery material is inherently flexible, a mixture of these three components can be used as a conventional asphalt-based damping material. The organic binder makes it more flexible at room temperature than a material with a large amount of bituminous material mixed with a small amount of rubbery material, such as wood, and it can be used even on areas with complex irregularities such as floors - copper plates. It can be easily molded.

Furthermore, compared to conventional asphalt-based vibration damping materials in which the organic binder is a mixture of bituminous material and rubbery material, the organic and elegant interlayer of the heat-resistant damping material of the present invention also has a thermosetting material. Since the resin contains its curing agent and catalyst, for example, the paint baking process (140-160℃,
30 minutes), the adhesive strength with the steel plate becomes stronger.

The thermosetting resin that can be used in the present invention is one or more selected from the group consisting of epoxy resin, polyester resin, phenol resin, allyl phthalate resin, polyurethane resin, urea resin, and melamine resin. Rubbery substances include synthetic rubbers, thermoplastic resins, and thermoplastic elastomers, such as polybutadiene (RR), styrene-6-butadiene copolymer, etc.
)+7 Acrylonitrile-butadiene copolymer (NB
MnR), methacrylate-resistant butadiene
), chloroprene rubber (OR), imprene rubber (]:
RR, butyl rubber (AER), acrylic rubber (AR)
, Thiokol rubber, vinyl acetate and its rubber, acid-modified product, ethylene-vinyl acetate copolymer (P2VA), Nisder acrylate resin, vinyl chloride and vinyl chloride-based copolymer containing plasticizer, ethylene-propylene copolymer (EPR, EPDM), ethylene Q acrylate copolymer (EEA), various thermoplastic nyelastomers (polyurethane, polystyrene, polyolefin, polyester, vinyl chloride, butyl rubber kraft polyethylene, l,2-bolybutadiene) /, trans-1,4-polystyrene, ethylene-α-olefin copolymer, ionomer, thermoplastic NBFt, etc.), and one or more selected from the group consisting of
Bituminous substance haasphalt (straight bone asphalt,
It is possible to use one or more types selected from the group consisting of (brown, 7sphalt, etc.) and cool, respectively, or in combination.

It is generally well known that vibration damping performance is improved when an inorganic filler is blended with an organic binder, and the present invention utilizes various well-known inorganic fillers.

For example, flaky fillers such as graphite, natural mica, synthetic mica, glass flakes, stainless steel flakes, aluminum flakes, nickel flakes, ferrite, leukemia, talc, vermiculite, and montmorillonite, fibers such as glass fiber, carbon fiber, and asbestos. Consists of particulate fillers such as glass peas, calcium carbonate, silica, silica sand, kiln ash, cement, dolomite, micro hollow bodies (shirasu balloons, shirasu balloons, etc.), aluminum hydroxide, carunium sulfate, barium sulfate, etc. Examples include one or more selected from the group.

The amount of the inorganic filler is 30 to 450 parts by weight, preferably 1°, ~', based on 100 parts by weight of the organic binder.
°°There are 76 items containing 8″″1 in the storage area of the important scenic area, and 3
If it is less than 0 parts by weight, the damping performance will be low, and if it exceeds 450 parts by weight, not only will the damping performance not improve any further, but the workability of mixing and molding will be impaired, and the porosity will increase, so the mechanical strength will be reduced. This may cause a problem in practical use. Further, if the amount is 50 to 400 parts by weight, the filler function can be fully exhibited.

Furthermore, among the inorganic fillers, flake light-containing fillers (hereinafter referred to as flakes) are effective in improving vibration damping performance, and in particular, they were proposed by the present inventor in Japanese Patent Application No. 57-18+075. As shown, this flake surface is oriented at 0°±300 with respect to the surface of the distribution material sheet, preferably at f±1.
The allocation performance can be further improved by controlling the orientation in the f direction and dispersing it. In this case, it is easier and more effective to use flakes with an aspect ratio (flake diameter/flake thickness) of 10 or more, preferably 25 or more.

In addition, the curing agent and catalyst for the thermosetting resin can be appropriately selected from those generally conventionally used for each thermosetting resin, but the flexibility of the damping material sheet at room temperature In order to maintain the properties for a long period of time, it is preferable to use a heat curing type curing agent or catalyst.

(Effects of the Invention) As mentioned above, the heat-resistant damping material of the present invention improves and overcomes the drawbacks in heat resistance of conventionally known damping materials, and has a heat resistance of approximately 40°C or higher and 18°C or lower. In addition to exhibiting and maintaining excellent vibration damping performance at relatively high temperatures,
It can stably improve overall vibration damping performance over a wider temperature range than conventional heat-resistant damping materials, and has better flexibility at room temperature, making it suitable for steel plate parts with complex uneven shapes. It conforms well to molds, can be bonded at the same time as it is cured by heat treatment, and does not cause problems such as reduced workability. It has various advantages, and is particularly useful as a heat-resistant allocating material for automobiles. It is suitable.
゛The heat-resistant damping material of the present invention can be used either in a non-constraint type composed of a substrate and a damping material, or in a constrained type composed of a substrate, a damping material and a constraint plate. In particular, it is preferable to use it in an unrestricted type.

(Examples) Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 Epoxy resin (Ebico) 828 as thermosetting resin
: Made of oil-based shell epoxy), thermoplastic polyurethane-nidistomer (Vandex T-) as a rubbery substance.
5000P: manufactured by Dainippon Ink Chemical Co., Ltd.), asphalt as a bituminous substance (40-60 Straight Asphalt 2 manufactured by Nippon Oil Company), and an acid anhydride (HN-2200: Hitachi Chemical Co., Ltd.) as a curing agent for epoxy resin and a catalyst. An organic binder consisting of a tertiary amine (5-CURFi661: manufactured by Kayaku Nouri ■) and an inorganic filler of mica (Suzoshito mica + 5OS near aspect ratio 65: manufactured by M Kuraray) were mixed into the composition shown in Table 1. mix,
After kneading for 10 to 50 minutes at a temperature of 50 to 160 degrees Celsius, the material was compressed into a sheet with a thickness of about 1.5 fi using a calendar roll to obtain a vibration damping material. 30
The sample was cured by heating for a minute.

Comparative Example 1 As shown in Table 1, Ebico) 828. Pantex T-5
As for 000P, curing agent, and catalyst, the same ones as in Example 1 were used, and the bituminous substances were 80-100 straight asphalt (manufactured by Nippon Oil Co., Ltd.), 7um calcium carbonate (5-
LITE1200 (manufactured by Nitto Funka Kogyo ■) and silica sand (Misato silica sand) were blended, and a sample was prepared in the same manner as in Example 1.

Examples 2 to 9, Comparative Examples 2 to 4 Samples were prepared in the same manner as in Example 1. In addition to the ingredients mentioned above in Example 1 and Comparative Example 1, polylite ao
io (manufactured by Dainippon Ink & Chemicals ■), Styrene Pukujie/Copolymer TR-2000C! (Made from Japanese synthetic rubber)
, Soft vinyl chloride (containing DOP40phr) (manufactured by Central Glass), 10-20A prone asphalt (manufactured by Nippon Oil), ZE4MZ (manufactured by Shikoku Kasei Ltd.), Herb Chill 2 (manufactured by NOF Corporation), Glass fiber (chopped)・Strand 6-inch long ECS O6-350 (manufactured by Central Glass) was used.

Example 1O Mixed with the same composition as Example 2, 70-8
After kneading at 0°C for 20 minutes, compression molding was performed using a calendar roll into a film with a thickness of approximately 150 μm.
Several tens of 50 pyn films are stacked to form a composite, which is compression molded again to form a sheet with a thickness of approximately 1.511111 mm, and the mica flakes are oriented in the C ± 30° direction with respect to the surface of the damping material sheet. A damping material whose orientation was controlled in this manner was obtained, and was cured by heating at 150 to 160° C. for 30 minutes to prepare a sample.

The samples of each of the above Examples and Comparative Examples were measured using a non-resonant forced elongation type dynamic viscoelasticity measuring device Rheopybron DDV-fir-E.
Dynamic viscoelastic behavior was measured using A.

Regarding the results, the relationship between loss modulus E'', which represents vibration damping performance, and temperature at a frequency of 110 Hz is shown in Figure 1-3.

[Brief explanation of the drawing]

FIGS. 1 to 3 compare examples of the present invention and comparative examples using conventional damping materials in terms of damping performance and operating temperature. Note that the numbers of Examples and Comparative Examples correspond to Hx. Temperature (0C) 2MB B deficiency (°shi)

Claims (1)

[Claims] In a damping material mainly composed of an organic binder containing a thermosetting resin, a rubbery substance, and a bituminous substance as essential components and an inorganic filler, the amount of the inorganic filler is 30 to 30 parts by weight per 100 parts by weight of the organic binder. The bituminous substance is contained in 100 parts by weight of the organic binder, and the bituminous substance is contained in 100 parts by weight, and the weight ratio of the thermosetting resin and the rubbery substance is 1:0.1 to 1:5. A heat-resistant vibration damping material characterized by being formulated in the following range.