JPS63297458A - Silicone polymer based vibration damping material - Google Patents

Abstract

PURPOSE:To obtain the titled vibration damping material, having excellent vibration damping performance within a wide temperature region and durability at high temperatures and suitable for automobiles, railway vehicles, etc., by using a silicone polymer as a matrix polymer and blending a specific amount of a filler, etc. CONSTITUTION:A silicone polymer based composition obtained by blending 100pts.wt. silicone polymer with (A) 25-500pts.wt, preferably 40-400pts.wt. filler (e.g. natural mica, synthetic mica or graphite) and preferably further (B) 0.1-10pts.wt., preferably 0.2-5pts.wt. coupling agent (e.g. gamma- chloropropyltrimethoxysilane). The above-mentioned vibration damping material has extremely improved vibration damping performance at ordinary temperature-100 deg.C and can be used in parts for use at high temperatures, such as parts heated to about 250 deg.C.

Description

Detailed Description of the Invention [Industrial Application Fields] The present invention can be applied to structural members that vibrate and generate noise in the fields of automobiles, railway vehicles, industrial machinery, transportation equipment, etc. The present invention relates to a silicone resin vibration damping material that can be directly bonded by heating and pressing, exhibits excellent vibration damping performance in a temperature range of room temperature to 100°C, and is particularly usable for structural members at temperatures up to 250°C.

[Prior Art] Conventionally, asphalt-based damping materials that are used at around room temperature are well known, and vinyl chloride resin-based damping materials, which can be applied at around room temperature or in medium-high temperature ranges up to 80°C, are particularly well known. Publication No. 53-135122, Japanese Patent Publication No. 58-398
These are disclosed in Japanese Patent Application Laid-open No. 28 and Japanese Patent Application Laid-open No. 61-192751, respectively.

In addition, as a damping material suitable for relatively high temperature regions, a heat-resistant damping material composition comprising a mixture of a thermosetting resin, a rubber-like substance, a thermoplastic resin, and a scale-like inorganic filler has been published in Japanese Patent Publication No. 54-8497. It is disclosed in the publication No.

[Problems to be Solved by the Invention] Among the above-mentioned vibration damping materials, asphalt-based damping materials have a significant decrease in their allocation performance in the medium to high temperature range of 40°C or higher, and when the temperature reaches 150°C or higher, they soften or melt. It cannot be applied to structural members that are exposed to temperatures of up to 250° C.

In addition, the above-mentioned Japanese Patent Application Laid-Open No. 53-135122, Japanese Patent Application Laid-open No. 5
The damping materials described in JP-A No. 8-39828 and JP-A No. 61-192751 have damping performance in the medium to high temperature range of approximately room temperature to around 80°C, but gradually deteriorate or decompose at temperatures above 120°C. up to 250
It cannot be used for structural members that are exposed to temperatures as high as ℃.

Furthermore, although the heat-resistant damping material disclosed in the above-mentioned Japanese Patent Publication No. 54-8497 has damping performance in the medium to high temperature range from room temperature to around 100°C, it gradually deteriorates or decomposes when the temperature exceeds 15Q'C. , cannot be applied to structural members that are exposed to temperatures of up to 250°C.

In this way, there are various conventional damping materials that have damping performance in the temperature range from room temperature to 100°C, but the maximum damping performance is 250°C.
There was no one that could be applied to structural members that can reach temperatures as high as ℃.

On the other hand, vibration damping materials whose matrix is made of engineering plastics such as polyphenylene sulfide, polyether ether ketone, etc., which can be used at high temperatures around 250°C, can also be considered; It has almost no vibration damping performance in the temperature range.

As described above, the present invention has excellent vibration damping performance in the temperature range from room temperature to 100°C, and can also be applied to structural members that can be heated up to 250°C, which is difficult to achieve with conventional vibration damping materials. The purpose is to solve a problem.

[Means for Solving the Problems] As a result of intensive studies on the above-mentioned problems, the present inventors have found that when silicone resin is used as the matrix resin, vibration damping performance specifically at room temperature to around 100°C, maximum 25
The present invention was achieved by discovering that it has heat resistance performance at 0°C.

That is, the present invention is a silicone resin vibration damping material characterized by containing 25 to 500 parts by weight of filler per 100 parts by weight of silicone resin.

In the present invention, the amount of filler to silicone resin is in the range of 25 to 500 parts by weight, more preferably 40 to 400 parts by weight, based on 100 parts by weight of silicone resin. If the amount is too low, the damping performance will deteriorate and the temperature range in which damping performance is maintained will be narrowed, and if it is more than this, not only will the vibration allocation performance not improve much, but it will also impair the workability of mixing and molding. is not preferable because the porosity becomes high and the mechanical strength decreases, which may cause practical problems.

In the present invention, silicone resin is used as the matrix resin.

In general, there are various types of silicone such as oil, resin, and rubber, but in the present invention, silicone resin is used. Silicone rubber is also a material with excellent heat resistance, but its vibration distribution performance is low and it is not preferred for use as a vibration damping material as the object of the present invention.

The type of silicone resin is not particularly limited, and various types can be used, and those commercially available as varnish prepared by dissolving silicone resin (solid content) in an organic solvent can be suitably used. There is a material called silicone gel that uses silicone resin, but this material has extremely low mechanical strength and cannot be used as a vibration damping material as the object of the present invention.

In the present invention, it is more preferable to add a coupling agent, and by adding this coupling agent, it is possible to prevent as much as possible the deterioration of vibration damping performance over time due to use at high temperatures. The amount of the coupling agent added is 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the silicone resin.

If the amount of the coupling agent is less than this, it will not sufficiently contribute to suppressing the deterioration of the allocation performance under high temperature exposure, and even if it is added in a larger amount, there will be no effect commensurate with the amount added. It is not preferable to use a large amount of these expensive coupling agents because it increases the cost.

Coupling agents are additives that chemically bond organic materials and inorganic materials together, or that improve affinity through chemical reactions and improve the functionality of composite materials, and various types can be used. , especially silane coupling agents,
Titanate coupling agents are preferred. Silane coupling agents are often used to improve the mechanical strength, adhesion, and stabilize electrical properties of composite materials, while titanate coupling agents are used to improve the dispersibility of inorganic fillers and increase the These coupling agents are often used for purposes such as lowering the filling ratio, lowering the viscosity of inorganic filler formulations, improving processability, and improving impact strength.
This is the first discovery that it has the effect of suppressing the deterioration of vibration allocation performance when heated for a long period of time at a temperature of ~250°C and maintaining high vibration damping performance.

Various fillers can be used in the present invention, such as natural mica, synthetic mica, graphite, glass flakes, ferrite, clay, talc, vermiculite, montmorillonite, stainless steel flakes,
Flaky fillers such as aluminum flakes and nickel flakes, glass fibers, carbon fibers, aramid fibers,
Fibrous fillers such as asbestos, glass peas, calcium carbonate, silica, silica sand, kiln ash, cement, dolomite, micro hollow glass balloons, shirasu balloons, etc.)
,! It is a particulate filler such as powder, lead powder, copper powder, aluminum powder, etc., and one or more of these are used. Among these, flake fillers are particularly excellent fillers that can improve the allocation performance.

As a coupling agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. can be used. More specifically, as a silane coupling agent, T-chloropropyltrimethoxysilane, vinyltriethoxysilane, etc. can be used. Silane, vinyltrimethoxysilane, β
-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, T-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, T
-aminopropyltriethoxysilane, mercaptoethyltriethoxysilane, vinyltriacetoxysilane,
Examples include γ-methacryloxypropyltri(2-methoxyethoxy)silane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and the like.

Titanate coupling agents include isopropyl triisostearoyl titanate, tetra-n-butyl titanate, tetraoctylene glycol titanate, tris (dioctyl pyrophosphate) ethylene titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopro and lutris (dioctyl pyrophosphate) ) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra (
2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyl tri(N-aminoethylaminoethyl) Titanate, isopropyl tri(dioctyl phosphate) titanate, etc. Furthermore, examples of aluminum-based coupling agents include acetalkoxyaluminum diisopropylate.

The vibration damping material of the present invention is manufactured by thoroughly mixing a silicone resin (preferably using a varnish dissolved in an organic solvent), a filler, and in some cases a silicone curing catalyst and a camping agent, and applying the mixture to a substrate by coating or other means. It is coated, dried, peeled off from the substrate, and in some cases multiple sheets are stacked and hot pressed to form a molded body. Alternatively, it may be applied directly to the material to be applied, heated, and bonded. Conditions such as drying, heating temperature, time, etc. at this time are appropriately selected depending on required vibration damping performance, mechanical strength, etc.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 TSR102 manufactured by Toshiba Silicone@ as silicone resin
to 100 parts by weight (based on solid content, the remainder being 82 parts by weight of xylene), flake Sujirite Mica 200S (Kuraray, average particle size 80μ) was added as a filler.
After adding 102 parts by weight of
It was dried for a period of time to evaporate the solvent to obtain a silicone mica prepreg sheet with a thickness of about 500 μm. Four of these prepreg sheets were stacked and press-molded to form a damping material specimen. Press molding conditions are: press temperature 180°C, mold and sample preheating time 5 minutes, press time 35 minutes, press pressure 100 kir/cnl, cooling time and pressure 5 minutes x
100 kg/-.

The damping performance of this damping material at 25°C, 50°C, and 100°C was evaluated. The evaluation was performed by measuring the mechanical loss coefficient (tan δ) at a frequency of 11011z using a non-resonant forced elongation type dynamic viscoelasticity measuring device.

The results are shown in Table 2.

Examples 2 to 9 Specimens were prepared in the same manner as in Example 1, except that the compositions shown in Table 1 were used, and the mechanical loss coefficients were measured. The results are shown in Table 2.

(Margins below) Table 1 Note: Silicone resin A TSRI manufactured by Toshiba Silicone
02 pieces 5%, balance xylene) B 5H4280 manufactured by Toray Silicone ■ (%)
) The catalyst is Toshiba silicone ■1lCR1 for actual W2~7
4 (amine type) 〃 〃 In 8.9, Nipper BG made by Nichio Rakumoe-sei (stampened benzoyl) Flake A is ■ Suzolite Mica 32511K made by Kuraray (average particle weight μ)
〃B 20O3(〃
(Capital) μ) Coupling agent A Nippon Unicar m<
^-186 (β-(3,4 epoxycyclohexyl) ethyltrimethoxysilane) Coupling agent B Ajinomoto-1lKR-23BS (
Bis(dioctylpyrophosphate)oxyacetate titanate) Table 2 (hereinafter referred to as Umbrella-White-).

1, (1,1 1・1 1-" Comparative Example 1.2 Polyvinyl chloride resin (Nippon Zeon ■
Using Zeon 121) manufactured by Zeon Co., Ltd., 5 parts by weight of DLF (dibasic lead phthalate manufactured by Sakai Chemical Industry Co., Ltd.) as a stabilizer and C stearic acid as a stabilizer and lubricant per 100 parts by weight.
d. Ba stearate was 1 part by weight each, 102 parts by weight of Sugilite mica, the same as in Example 1, was added as a filler and mixed with a ribbon blender, and then kneaded with a calendar roll at 170 to 180 ° C. for 10 minutes. Comparative Example 1), which is molded into a sheet and used as a specimen for vibration damping material. In addition, epoxy resin (Epicoat 828:
Using 100 parts by weight of Yuka Shell Epoxy (manufactured by Yuka Shell Epoxy ■), 100 parts by weight of thermoplastic polyurethane elastomer (Pandex T-5000P: Dainippon Ink & Chemicals @il) as a rubbery substance and curing of the epoxy resin. Acid anhydride (IN-22007 Hitachi Chemical fl 1 ml) and tertiary acid anhydride (S-CURE
661: manufactured by Kayaku Nury Co., Ltd.) were added to an organic binder with 80 parts by weight and 10 parts by weight, respectively, and 102 parts by weight of Suzolite and Squid, the same as in Example 1, were added as fillers, kneaded at 60 to 70°C for 20 minutes, and then calendered. Formed into a sheet with a thickness of approximately 1.5 mm using a roll, and then heated to a temperature of 14
It was heated and cured at 0 to 160°C for 30 minutes to prepare a vibration damping material specimen (Comparative Example 2). When these specimens were heated at 250° C. for 10 hours, those of Comparative Example 1 did not retain their original shape, and those of Comparative Example 2 showed slight discoloration, large weight loss, and significant decomposition.

Comparative Example 3.4 Polyphenylene sulfide (
Rydon P-4 (manufactured by Phillips Petroleum ■) was used, and 102 parts by weight of Sugilite mica, the same as in Example 1, was added as a filler to 100 parts by weight. A pellet was manufactured using an injection molding machine to a thickness of about 1. It was formed into a rectangular shape of 5n+m and used as a specimen of a vibration damping material. The cylinder temperature was 310°C and the mold temperature was 140°C (Comparative Example 3). Silicone rubber (SH850LTV: )-manufactured by Resilicone ■ was used as the matrix resin. 5H850LTV was prepared by mixing liquids A and B at a weight ratio of 1:l, adding 50 parts by weight of Suzolyte Myroku, the same as in Example 1, as a filler to 100 parts by weight, and mixing with a mixing roll machine at room temperature for 20 minutes. After kneading, the mixture was formed into a sheet with a thickness of about 1.5 mm, and then heated and cured at about 100° C. for 30 minutes to obtain a vibration damping material specimen (Comparative Example 4). This specimen was heated at 250° C. for 10 hours, but there was no change in appearance or weight loss in Comparative Examples 3 and 4.

However, when the allocation performance of this product at around room temperature before heating was measured as a mechanical loss coefficient (tan δ) using the above-mentioned device, it was found to be insufficient as shown below.

tan δ Comparative example 3 Comparative example 4 25℃ 0.020 0.18 '50℃
0.020 0.15100℃ 0.0
34 0.13 Example 10 The specimens of Examples 1 and 2 were heated at 250° C. for 10 hours, but there was no change in appearance or weight loss. Also, 2
When the vibration allocation performance of the specimen was measured after heating at 00°C for 2 hours, as shown below, the vibration damping performance of Example 1 was slightly lower than that before heating, but the vibration damping performance was sufficient. was maintained. On the other hand, in Example 2, almost no deterioration in damping performance was observed.

tanδ Example 1 Example 2 25℃ 0.28 0.5150℃ 0
．． 61 0.72100 'CO, 580, 58 ℃ Effects of the invention] The vibration damping material of the present invention has extremely excellent vibration distribution performance at room temperature to 100 ℃, and has excellent durability at high temperatures, especially at 250 ℃
Since it can be used in parts that are used at extremely high temperatures, it can be widely used in various fields such as automobiles, railway vehicles, and industrial machinery.

Claims (2)

[Claims] (1) A silicone resin vibration damping material containing 25 to 500 parts by weight of a filler per 100 parts by weight of a silicone resin. (2) The silicone resin vibration damping material according to claim 1, which contains 0.1 to 10 parts by weight of a coupling agent per 100 parts by weight of silicone resin.