KR880000856B1 - Vibration damping material - Google Patents

Abstract

The vibration damping material is prepared by hardening the compound of epoxy resin (100 wt.%), R-OCH2-CHOCH2 (5-45 wt.% RiCnH2n+1 n=1- 18, integer), polyamide resin (200-500 wt.%) and loading material. Epoxy resin has 200-1000 molecular weight, 10-500 expoxy-equivalent, fluidity at room temp. or 100≰C and 1-300 poise viscosity at 25≰C. Polyamide resin has 100-800 amine-equivalent, fluidity at room temp. or 100≰C and 3-200 poise. The loading material is one of carbon fiber, graphite or ferrite.

Description

Vibration damping material

1 and 2 are diagrams for explaining the relationship between the frequency and vibration damping characteristics of Examples 1-3 and Comparative Examples 1-6, respectively.

3 and 4 illustrate the relationship between the frequency and vibration damping characteristics of Examples 10-11 and Comparative Examples 9-13, respectively.

5 is a diagram for explaining the relationship between the frequency and vibration damping characteristics of the first and sixteenth embodiments.

6 is a diagram for explaining the relationship between the frequencies and vibration damping characteristics of the tenth and seventeenth embodiments.

The present invention relates to a vibration damping material, and more particularly, to a ballast tank, a fuel storage tank of a ship, or to a region which is a source of vibration, such as an engine room or a pump room of a ship or an automobile. 진동 着) or vibration damping material used to apply.

(Prior Art)

The vibration damping material controls the solid sound generated from the vibration plate by converting the vibration energy into thermal energy. ② It prevents fatigue and destruction of materials by vibration. ③ Sounds the sound of air delivery. And the like. Therefore, ships, automobiles, engine rooms, and other vibration generating areas are widely used in the field of attenuating solid sound or vibration of devices such as computers, agricultural machines, air conditioners, hoppers, and shooters.

As such a vibration damping material, not only vibration damping characteristics but also characteristics such as workability and heat resistance when sticking to water and oil resistant curved surfaces are required.

Conventionally, Japanese Patent Laid-Open Nos. 58-23426 and 23427 have been proposed as a known technique for producing this kind of damping material. Based on such epoxy resin, a large amount of a polyamide resin for imparting flexibility of the resin and a soft particle or inorganic filler for imparting vibration damping performance are blended.

However, it has been found that these techniques have the following problems. ① Insufficient vibration attenuation in low frequency range below 1,500Hz. (2) Polyamide resins were formulated to provide flexibility, but at the same time a large amount of filler was added, resulting in high hardness and poor workability. ③ When the composition is kneaded, the viscosity becomes high, and when it is injected into the molding machine after kneading, the workability is poor, and it is easy to include air, so that the molded article after molding hardening has a lot of bubbles.

The present invention improves this problem of the prior art, has excellent vibration damping characteristics in the wide range from low frequency to high frequency, and has sufficient workability to adhere to or apply to curved surfaces, has low viscosity of kneaded material, and It is to provide a vibration damping material capable of improving workability.

This problem is overcome by the following configuration of the present invention.

(A) an epoxy resin having fluidity at room temperature to 100 ° C, and (B) R-OCH ₂ -CH-CH ₂

(n=1~22의 정수) R₁: C_nH_2n+1(n=0~22의 정수)로 표시되는 화합물 [I]과, (C)상온 내지 100℃에서 유동성을 갖는 폴리아미드수지로 이루어지는 수지조성물과, (D)탄소섬유, 흑연, 페라이트로 부터 선택된 적어도 1종의 충전재,로 이루어지는 혼합조성물을 경화시켜서 이루어지는 진동 감쇠재이다. 이와 같은 감쇠재의 수지 조성물로서는 에폭시수지 100중량부에 대하여 화합물 [I]5내지 45중량부, 폴리아미드수지 100 내지 800 중량부 배합시킨 것이 바람직하게 선택되지만 또한 경화제나 경화촉매등을 첨가한 것도 사용된다.Provided that R is C _n H _{2n + 1} or

(integer of _{n = 1 ~ 22) R 1} : C n H 2n + 1 the polyamide resin and the compound [I] represented by (n = 0 ~ 22 integer), (C) having fluidity at ordinary temperature to 100 ℃ It is a vibration damping material which hardens the resin composition which consists of these, and the mixed composition which consists of (D) at least 1 sort (s) of filler selected from carbon fiber, graphite, and ferrite. As a resin composition of such a damping material, what mix | blends compound [I] 5-45 weight part and polyamide resin 100-800 weight part with respect to 100 weight part of epoxy resins is preferable, but what added the hardening | curing agent, a curing catalyst, etc. is also used. do.

The epoxy resin used in the present invention is a main ingredient, and exhibits fluidity at room temperature to 100 ° C, has a viscosity at 25 ° C of 1 to 300 poises, an epoxy equivalent of 10 to 500, and a molecular weight of 200 to 1000.

Such epoxy resins include, for example, Epicoat 828, 827, 834, 807 (manufactured by Jean-Sire Chemical K.K.).

As for the vibration damping material which belongs to this invention, it is especially important that the compound represented by Formula [I] mentioned above is mix | blended. This compound acts as an agent for improving flexibility and processability in molding.

The flexibility achieved by this compound exerts an extremely effective effect on vibration damping by synergistic effects with fillers such as graphite and ferrite.

In this formula, R ₁ may be coordinating to any position, but coordinating at position 5.6 is usually used, and a viscosity of 0.5 to 50 centipoise, an epoxy equivalent of 80 to 400 and a molecular weight of 80 to 400 is appropriate at 25 ° C.

Such compounds include methylglycidyl ether, butylglycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, hexadecyl Glycidyl ether, octadecyl glycidyl ether, eicosyl glycidyl ether, phenyl glycidyl ether or t-butylphenyl glycidyl ether.

The polyamide resin used in this invention is used as a hardening | curing agent and a flexibility provision agent, Comprising: It is suitable that the viscosity in 25 degreeC is 3-2,000 poise and the amine value is about 100-800. As such an amide resin, for example, Domide # 225-X, # 215-X, # 225 (Kami KKK), Vasamide 930, 115 (Genera Mills KKK), EPON-V15 (Sier) KK 製).

The compounding quantity of compound [I] with respect to an epoxy resin is 5 to 45 weight part with respect to 100 weight part of former, It is good to set it as 10-25 weight part more preferably.

When the compounding quantity of compound [I] is less than 5 weight part, the hardness of a molded article will become large too much, and also the viscosity at the time of mixing at the time of compounding a large amount of filler becomes high, and workability and workability tend to deteriorate. When it exceeds 45 parts by weight, it tends to be excessively softened and sufficient mechanical properties are not obtained.

The compounding quantity of the polyamide resin with respect to an epoxy resin is 100-800 weight part with respect to 100 weight part of former, Preferably it is the range of 200-500 weight part. When the blending amount of the polyamide resin is less than 100 parts by weight, the hardness of the obtained molded article tends to be excessive. On the contrary, when it exceeds 800 parts by weight, the hardness becomes excessively soft, and sufficient mechanical properties may not be obtained. .

In the present invention, the polyamide resin acts as a curing agent for the epoxy resin, but it is also preferable to shorten the curing time and to fully advance the curing of the obtained molded article. In that case, a curing agent generally used for the epoxy resin is used.

As such a curing agent, aliphatic amines such as triethyltetramine, furopanolamine, aminoethylethanolamine, aromatic amines such as P-phenylenediamine, tris (dimethylamino) methylphenol, benzylmethylamine, or phthalic anhydride, maleic anhydride You may use carboxylic acid, such as. These addition amount can be freely changed according to the required characteristics, but in the case of using primary and secondary amines, it is better to determine the addition amount by the following equation.

Equivalent of amine =

Co., Ltd. A compounding amount with respect to 100 weight part of epoxy resins.

On the other hand, in the case of acid anhydride, the addition amount can be calculated | required by following Formula.

Phr = C ×

Equivalent weight of acid anhydride

C: 0.85 (most acid anhydride), 0.6 (chlorine-containing acid anhydride), 1.0 (when tertiary amine is used as a promoter)

In addition, what acts as a catalyst, such as a tertiary amine, is not calculated | required by calculation, and an appropriate amount is calculated | required from various tests.

With respect to such a specific resin composition, it is essential in the present invention to mix at least one kind of specific filler selected from carbon fibers, graphite, and ferides. In the present invention, the presence of the compound [I] in these mixed species organically combines the respective functions, achieves the damping effect while satisfying the flexibility, it can exhibit excellent characteristics.

Among the fillers in the present invention, graphite and feride have a large vibration damping effect, and therefore, it is preferable to configure this as a main body.

Although carbon fiber also has a large damping effect, it is especially reinforcing, and it is preferable to use it in addition to graphite and ferrite.

It is preferable that the graphite used for this invention is 3-70 aspect ratio (aspect ratio) defined by following Formula.

Aspect ratio (AR) =

D: diameter of flake

When the aspect ratio exceeds 70, the wetness to the resin to be mixed deteriorates, and therefore, it is difficult to blend in a large amount.

The ferrite used in the present invention is a magnetic material composed mainly of _{Fe 2 O 3, Fe 2 O} 3 other MnO, CaO, ZnO, CdO, Al 2 O 3 , etc. on the particle amount, or a thin film containing a metal oxide as a trace amount of Powder. Specific gravity varies depending on the content of metal oxides other than Fe ₂ O _3, but those in the range of 2.45 to 2.70 are usually used. This ferrite is generally used for magnetic tapes for high-performance recording. Although there are soft magnetic and ferromagnetic ones, the object of the present invention can be achieved by using any of them.

The size of the ferrite particles should be about the size of the particle passing through a sieve of 60 mesh (by the Tyler standard).

Such ferrites include HP-A, KH-R, and KH-D (K.K.K.).

If the size of the ferrite particles is less than 60 mesh, the ferrite powder becomes bulky, which makes it difficult to make a large amount and uniformly. Therefore, sufficient damping characteristics are not obtained.

The carbon fiber used in the present invention is preferably a fiber length of 10 to 1000 µ, but more preferably 30 to 500 µ.

Such filler is blended at least 30 parts by weight, preferably 40 parts by weight or more, based on 100 parts by weight of the resin composition. If it is less than 30 parts by weight, the deterioration of vibration damping characteristics is large, which is not preferable.

Vibration damping characteristics vary somewhat depending on the type of filler, but preferably 40 parts by weight or more for graphite or carbon fiber and 50 parts by weight or more for ferrite.

The damping characteristics are improved to such an extent that the amount of the filler blended is large. In the case of blending as much as possible, 120 parts by weight of graphite or carbon fiber and 190 parts by weight of ferrite can be blended, but from the point of hardness and workability of the molded product, the former is about 100 parts by weight and the latter is about 150 parts by weight. The maximum compounding amount of is selected.

As mentioned above, these fillers may be used alone or in combination. However, as the best mode of the present invention, it is preferable to mainly select one selected from graphite or ferrite.

Such a filler can select graphite or carbon fiber when a lightweight vibration damping material is desired, and ferrite can be selected when a relatively heavy material is desired.

Since the vibration damping material according to the present invention is constituted as described above, it can exhibit extremely excellent vibration damping characteristics in all areas from low frequency to high frequency, and it is hardened by an aster-hardness meter (type C method) at 20 ° C. As 40-95 thing can be obtained reliably, workability and workability can also be extremely favorable.

In addition, the use of graphite and / or carbon fiber according to the present invention can have a density of 1.05 to 1.65, and there is an advantage in workability to a certain light weight.

In the present invention, inorganic fillers such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, paraffin, zinc oxide, flame retardants such as aluminum embrittlement, and mica and silica sand may be added within a range that does not impair the characteristics of the vibration damping material.

In this invention, a vibration damping material can be obtained by inject | pouring and hardening the said component into the molding machine from which the required shape is obtained under the heating of room temperature-100 degreeC as needed.

The present invention is of the same configuration as described above, and has excellent vibration damping characteristics in a wide band from low frequency to high frequency, and also has sufficient performance to be affixed to a curved surface and lowers the viscosity of the kneaded product. Workability in the molding machine can be further improved.

According to the present invention, the polyamide resin and curing agent of the resin composition (C), the curing catalyst and the other (A) and (B) can be separated and used as a two-liquid type.

In this case, the above two kinds of composition liquids may be uniformly mixed for 5 to 10 minutes in a high viscosity fluid mixer (for example, Mixta MCP-type 3 manufactured by Mixta Industrial Co., Ltd.), and then used as a part type. In such a two-liquid type, the damping material of the present invention can be easily constructed in a place having a complicated shape.

As such two liquid types, the following three types are enumerated by adding the filler (D).

① (A) + (B) / (C) + (D) ② (A) + (B) + (D) / (C) ③ (A) + (B) + (D) / (C) + ( D)

In addition, a hardening | curing agent and a hardening catalyst are added and mix | blended with (C).

The present invention is characterized in that there is no change in performance even when formed from the state of such a two-liquid type.

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

EXAMPLE

The vibration damping property in an Example says what was measured by the following method.

Vibration analysis device was cured by placing a 16mm-thick vibration damping material cut into a size capable of obtaining a predetermined resonance frequency on a steel plate having a thickness of 8mm with a two-component epoxy adhesive and leaving it for 24 hours to cure the adhesive. The vibration damping waveform is measured by CF-910, and the vibration damping characteristic (C / Cc) is obtained by the following equation.

a. Decay Rate

b. Effective Decay Rate

De = Do-D _B ... … … … dB / sec

c. Percent Critical Damping

…………%C / Cc =

… … … … %

Wherein F: sample adhesive disc or a rectangular plate characteristic frequency, N: number of computationally taken cycle, A _1: N maximum amplitude, A ₂ of: N minimum amplitude, Do of: the decay rate of the test adhesive sheet, D _B: Attenuation Rate of Original Disc

[Example 1, Comparative Examples 1 and 2]

The composition shown in Table-1 is mixed uniformly and quietly using the high viscosity mixing yarn, without foaming as much as possible under 80 degreeC heating.

Next, the obtained mixture was injected into a plate forming machine and then cured to obtain a 16 mm thick damping material.

Table 1-1 shows the hardness of the vibration damping material, the fluidity during transfer to the molding machine, and the presence of bubbles on the surface of the molded article.

TABLE 1

Note 1) Graphite: Aspect ratio 10

2) Hardness: measured with Asuka hardness tester (type C) (20 ℃)

3) Liquidity: By visual observation ×. Poor, O… Good

4) Numbers in the table indicate parts by weight.

As is clear from Table 1, when the ratio of polyamide resin is increased to lower the hardness as in Comparative Example 2, the hardness reaches the target level, but as shown in FIG. 1, the vibration damping characteristics are deteriorated. .

Moreover, since the viscosity after mixing becomes high, the comparative example 2 has the defect that workability | operativity is bad at the time of liquid-liquid pouring into a molding machine, and also there are many bubbles of surface, and there are many surface bubbles of the plate-shaped vibration damping material obtained after molding.

On the other hand, in Comparative Example 1, since the hardness is extremely high, the workability is extremely bad and the surface bubbles also have many defects. On the other hand, Example 1 which satisfies the present invention was found to be extremely excellent in certain characteristics such as hardness, fluidity and bubbles as well as vibration damping characteristics.

[Examples 2 and 3 Comparative Examples 3 to 6]

Using the composition shown in Table 2, the plate-shaped vibration damping material of 16 mm thickness was produced in the same procedure as Example 1.

As in Example 1, vibration damping characteristics were measured and shown in FIG. 2. In addition, the density is shown in Table-2.

TABLE 2

Note: 1) Graphite: Aspect Ratio 10

2) Carbon fiber: 100μ fiber length

Embodiments 2 and 3 satisfying the present invention have almost equally good vibration damping properties and light weight in the entire band of low frequency to high frequency. On the other hand, Comparative Examples 3 to 6 have relatively low damping characteristics as compared with Examples 2 and 3, and further, vibration damping characteristics in the low frequency region of 2000 Hz or less are significantly lower. It also has a high density.

[Examples 4-7, Comparative Examples 7, 8]

Each composition shown in Table 3 was implemented in the same procedure as Example 1, and the vibration damping material of 16 mm thickness was obtained. The hardness of this vibration damping material was measured by an Asuka-hardness meter (type C), and also made of 100 ψ steel madeel and wound around the vibration damping material to evaluate the flexibility, and to prevent cracking in the vibration damping material. It was. The evaluation results are shown in Table-3.

TABLE 3

Note: 1) Graphite: Aspect Ratio 10

2) Carbon fiber: 100μ fiber length

Comparative Examples 7, 8, in which butylglycidyl ether or octadecylglycidyl ether are not blended, have a hardness of 98, which is extremely hard, and lacks flexibility, so that the practice is extremely poor.

On the other hand, Examples 4 to 7 satisfying the present invention have a hardness of 73 to 75, which may be sufficient flexibility and excellent performance.

Example 8

After the plate-shaped vibration damping materials obtained in Examples 2 and 3 were immersed in distilled water and diesel oil at 20 to 25 ° C. for 48 hours, the vibration damping materials were measured at the frequencies shown in Table-4 for each sample. In addition, about the sample before a process, it measured similarly and the result is shown in Table-4.

TABLE 4

As is clear from Table-4, the vibration damping material satisfying the present invention did not show any difference in the characteristics of the vibration damping material before and after distilled water and diesel oil immersion.

Example 9

Each composition shown in Table-5 was implemented in the same procedure as Example 1, and the vibration damping material of 16 mm was created.

The evaluation results are shown in Table-5.

As is clear from Table-5, Nos. 3 to 7 and Nos. 11 to 15 satisfying the present invention have excellent vibration damping characteristics, can hold a suitable path, and the performance is extremely good.

TABLE 5

Example 10, Comparative Examples 9 and 10

The composition shown in Table 6 is mixed as quietly and uniformly as possible without mixing of bubbles as much as possible under 80 ° C heating using a high viscosity mixing yarn.

Next, the obtained mixture was injected into a plate molding machine and cured to obtain a vibration damping material having a thickness of 16 mm.

Table 6 shows the hardness of the vibration damping material, the fluidity when transferring to the molding machine, and the presence of bubbles on the surface of the molded article.

As is clear from Table 6, when the ratio of polyamide resin is increased to soften the hardness as in Comparative Example 10, the hardness reaches the target level, but the vibration damping characteristics deteriorate as shown in FIG. There is this. In Comparative Example 10, the viscosity of the mixed liquid is high, so that the workability is poor when transferring to the molding machine, and there are many bubbles in the foam, so that there are many surface bubbles of the plate-shaped vibration damping material obtained after molding.

On the other hand, in Comparative Example 9, since the hardness is extremely large, the workability is extremely bad, and the surface bubbles also have many defects.

On the contrary, Example 10 satisfying the present invention was found to be extremely excellent not only in vibration damping characteristics but also in any characteristics such as hardness, flowability, and bubbles.

TABLE 6

Note: 1) Ferrite: KH-R, particle size 0.50 ~ 0.80μ (ferromagnetic material)

2) Hardness: measured with Asuka hardness tester (type C) (20 ℃)

3) Liquidity: By visual observation, X-Poor, O-Good

4) Numbers in the table indicate parts by weight.

[Example 11, Comparative Examples 11-13]

The composition shown in Table 7 was used and the plate-shaped vibration damping material of 16 mm thickness was created in the same procedure as Example 9. In the same manner as in Example 9, vibration damping characteristics were measured and shown in FIG.

In the eleventh embodiment that satisfies the present invention, vibration attenuation is almost equally good in the whole band of low frequency to high frequency. On the other hand, in Comparative Examples 11 to 13, the attenuation characteristics are generally lower than those of Example 11, and further, the attenuation characteristics in the low frequency region of 2000 Hz or less are remarkably low.

TABLE 7

Note 1) Ferrite: KH-R (利 根 産業 (株) 製)

2) Mica: 100M (山田 工業)

3) Induction: 0.5ψ

4) Numbers in the table indicate parts by weight.

Examples 12 to 13 and Comparative Example 14

Each composition shown in Table 8 was implemented in the same procedure as Example 9, and the vibration damping material of 16 mm thickness was obtained. The hardness of this vibration damping material was measured with an Asuka hardness tester (type C), and the vibration damping material was wound up using a 100 강제 steel machinrel to evaluate the flexibility, and the vibration damping material was allowed to have no crack.

The evaluation results are shown in Table-8.

Comparative Example 14, in which butylglycidyl ether or octadecylglycidyl ether was not blended, had an extremely high hardness of 99 and had a very poor performance due to lack of flexibility. On the contrary, Examples 12 to 13 satisfying the present invention may have sufficient flexibility as the hardness of 73 to 74 and excellent performance.

TABLE 8

Note 1) Ferrite: HP-A (軟 soft magnetic material) (利 根 産業 (株) 製)

2) Numbers in the table indicate parts by weight.

Example 14

Each composition shown in Table 9 was carried out in the same manner as in Example 9 to obtain a vibration damping having a thickness of 16 mm. The evaluation results are shown in Table-9.

As apparent from Table 9, No. satisfying the present invention. 3 to No. 7 and No. 11 to no. 15 has excellent vibration damping characteristics, and can have an appropriate hardness, so the performance is extremely good.

Example 15

Each composition shown in Table-10 was made a vibration damping material having a thickness of 16mm in the same procedure as in Example 9. The evaluation results are shown in Table 10. As apparent from Table 10, No. satisfying the present invention. 3 ~ No. 6 has excellent vibration damping characteristics and can have a moderate hardness, and the workability is extremely good.

TABLE 9

Note 1) Ferrite: KH-R (利 根 産業 (株) 製)

2) Numbers in the table indicate parts by weight.

TABLE 10

Note 1) Ferrite: KH-R (利 根 産業 (株) 製)

2) Numbers in the table indicate parts by weight.

3) O pass, X fail

[Examples 16-17]

For Example 1 and Example 10, vibration damping materials were formed from the two-liquid type resulting from the following composition.

The two kinds of liquids were uniformly mixed for 5 to 10 minutes in a Mixer MCP-013 type mixer manufactured by Mixta Industrial Co., Ltd. before use, and then molded under the same conditions as in Example 1 using the obtained part-shaped composition.

The vibration damping characteristics of the four kinds of the materials kneaded and molded immediately before use in the two-liquid type, as in Examples 1 and 10 and those formed by the simultaneous kneading, were evaluated. The results are shown in FIGS. 5 and 5.

When it was in the same composition, the simultaneous training type and the two-component type (Examples 1 and 16, 10 and 17) all had the same performance.

Claims (7)

(A) 100 parts by weight of an epoxy resin having fluidity at room temperature to 100 ° C and a viscosity at 25 ° C of 1 to 300 poises, epoxy equivalent of 10 to 500, and molecular weight of 200 to 1000, and (B) R-OCH _2- CH O CH ₂ However, 5 to 45 parts by weight of compound [I] represented by R: C _n H _{2n + 1} (an integer of n = 1 to 18), and (C) have fluidity at room temperature to 100 ° C and have a viscosity at 25 ° C. 3 to 2000 poises, the resin composition consisting of 200 to 500 parts by weight of a polyamide resin having an amine number of about 100 to 800, and (D) at least one filler selected from carbon fiber, graphite and ferrite, Vibration damping material characterized in that. The vibration damping material according to claim 1, wherein the compounding amount of the compound [I] is 10 to 25 parts by weight based on 100 parts by weight of the epoxy resin. The vibration damping material according to claim 1, wherein the resin composition contains a curing agent or a curing catalyst. The vibration damping material according to claim 1, wherein the blending amount of the filler is at least 30 parts by weight based on 100 parts by weight of the resin composition. The vibration damping material according to claim 1, wherein the carbon fiber has 10 to 1000 mu of fibers. The vibration damping material according to claim 1, wherein the graphite has an aspect ratio of 3 to 70. The vibration damping material according to claim 1, wherein the ferrite is 60 mesh or more (by a Tyler standard).

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