JPS61181886A - Vibration damper for panel - Google Patents

Abstract

PURPOSE:To provide a vibration damper for a panel exhibiting an excellent vibration damper characteristics over a wide temperature range and having an excellent workability and adhesion, which comprises a composition obtained by mixing an epoxy resin, a specific liquid resin, a curing agent and an inorganic filler in predetermined proportions. CONSTITUTION:A vibration damper for a panel comprising a composition obtained by mixing an epoxy resin, a liquid resin compatible with the epoxy resin and having a methylol group at its terminal, a curing agent, and an inorganic filler in proportions as will be mentioned below. The proportion of the epoxy resin in the composition is 5-75pts.wt. per 100pts.wt. of the total amount of the epoxy resin and liquid resin while the proportion of the inorganic filler in the composition is 30pts.wt. or more per 100pts. of the total amount of the epoxy resin and liquid resin. It is necessary that the liquid resin be compatible with the epoxy resin not only for preventing the lowering in the characteristics due to the separation of the resins but also for plasticizing the epoxy resin. The presence of the terminal methylol group in the liquid resin. The presence of the terminal methylol group in the liquid resin is required to plasticize the epoxy resin.

Description

[Detailed Description of the Invention] (Field of Industrial Application) This invention has excellent distribution characteristics in a wide temperature range from low to high temperatures, has good workability when applied to panels to be distributed, and The present invention relates to a panel allocation material that has excellent adhesion to allocated panels.

(Prior Art) Conventionally, in panel structures such as car bodies such as automobiles and railway vehicles, prime movers such as engines and motors, housings of electrical equipment, and fluid transport ducts, a distribution material has been applied to the panel surface for the purpose of reducing vibration. are in close contact with each other.

Such panel damping materials have a loss coefficient (η) evaluated in a composite system with the damped panel [Noise Countermeasures Handbook,
Edited by Japan Acoustic Materials Association, p. 21], and preferably a large loss coefficient (η) over a wide temperature range. The reason for this is that the object to be damped is not necessarily used in an air-conditioned environment; for example, when considering use in a car panel, in addition to the external environment depending on the season, solar radiation, region, etc.
The temperature of the damped panel changes depending on the internal environment such as exhaust and air conditioning. Such temperature changes generally range from -40°C to 12°C.
It is said that the loss coefficient extends over the range of 0°C, and it is considered ideal to have a dissipating material that has a large loss coefficient in the temperature range of at least about 0°C to 80°C. Further, as the thickness of the damped panel becomes thicker and the thickness of the damping material becomes thinner, the damping effect becomes worse. Therefore, for automobile use, the allocated panel has a maximum thickness of 0.
Since approximately 8f1 is used, it is desired that sufficient allocability can be obtained even with this thickness. Furthermore, when considering the weight of the vehicle, the thickness of the distribution material is preferably 3.5 mm or less.

Furthermore, it is desired that the panel damping material can be easily adhered to the damped panel. For example, when the controlled panel is an automobile floor panel, it has a complex surface shape by adding beads, embossing, and curved surfaces. It is a problem in terms of work that it takes a lot of effort to uniformly adhere the distribution material to the surface of the panel to be distributed.

Conventionally, heat-sealable damping materials have been known for use in automobile floor panels, for example, which are made primarily of asphalt, a thermoplastic material, with fillers and modifiers added. Publication No. 57-119553). In the automobile manufacturing process, because thermosetting paint is used to paint the car body, the car body is heated at a temperature of 140° C. for about 30 minutes in order to harden the paint film.

The asphalt-based damping material utilizes this heat to adhere to the vehicle body panel, and the worker can simply place the damping material sheet temporarily on the damping panel and the sheet will melt due to the heat. , it follows and fuses the complex shape of the damped panel using only its own weight. As described above, the asphalt-based damping material has a self-adhesive property that does not require the use of adhesives, etc., and can be easily adhered to complex damped panels, making it an excellent sounding material in terms of workability.

(Problems to be Solved by the Invention) However, in conventional heat-sealing type vibration damping materials mainly composed of thermoplastic materials, the material must have sufficient fluidity under temperature conditions of 140°C or less. Therefore, the elastic modulus of the damping material decreases significantly at temperatures above 40° C., resulting in the disadvantage that sufficient damping characteristics cannot be obtained at high temperatures. It is a well-known fact that in the case of unrestrained damping materials, good vibration damping properties cannot be obtained unless the damping material not only has a large loss coefficient (tan δ) but also a large elastic modulus. Measures Handbook, edited by Japan Acoustic Materials Association, p. 443].

Therefore, the inventors conducted various studies in order to achieve both excellent vibration damping properties from low to high temperatures and workability equivalent to that of conventional vibration damping materials whose main component is asphalt. We conducted research focusing on adhesive properties. However, a single epoxy resin and a curing agent, multiple epoxy resins and curing agents with different glass transition temperatures (Tg), a mixture of these with a plasticizer added, or a mixture of these with an inorganic filler are not available. However, it was not possible to obtain good vibration damping characteristics over a wide temperature range.

(Means for Solving the Problems) As a result of further research, the inventors discovered an epoxy resin, a liquid resin that is compatible with the epoxy resin and has a terminal group of methylol, and a curing agent. By blending with and inorganic fillers, we can obtain a panel vibration damping material that not only has excellent vibration distribution characteristics in a wide temperature range from low to high temperatures, but also has excellent workability and adhesion to the damped panel. , which solves the above problems.

The epoxy resin used in this invention has an average of one or more reactive epoxy groups per molecule,
They include various types such as bisphenol type, ether ester type, novolak epoxy type, ester type, and cycloaliphatic type, and one type thereof may be used alone or two or more types may be used in combination. Further, these epoxy resins may be either solid or liquid at room temperature.

The liquid resin must be compatible with the epoxy resin and must contain a methylol group as a terminal group. Compatibility with the epoxy resin is necessary not only to prevent deterioration of properties due to separation of the resin, but also to plasticize the epoxy resin. In addition, the terminal methylol group is necessary to facilitate the reaction with the epoxy resin, but it is not necessary that all molecules have a methylol group.Liquid resins with these characteristics can be produced by organic synthesis. Xylene resins, phenol resins, and the like can be manufactured in various types or are industrially mass-produced. These resins are compatible with epoxy resins, and in the industrial manufacturing process, molecules containing molecules with methylol groups at the end groups are simultaneously produced, so special reaction processes and complicated processes such as modification are required. It has the advantage of being easily obtained without requiring Also, when the panel allocation material hardens,
Considering the hygroscopicity of the resin, the low volatile content, and the long-term storage stability of the uncured resin, which can cause undesired foaming, xylene resin is suitable.

For example, xylene resin is an unmodified xylene formaldehyde resin obtained from the reaction of meta-xylene and formaldehyde, and meta-xylene is an oligomer with number average molecules 1i300 to 600 bound by chemical bonds such as methylene, dimethylene ether, acetal, etc. It is. Further, as described above, in the fifth production stage, molecules containing molecules having a methylol group at the terminal group are simultaneously produced.

These liquid resins used in this invention can be used singly or in combination of two or more.

As the curing agent used for curing the epoxy resin and liquid resin, known curing agents for epoxy resins can be used.
It is sufficient to select one that matches the thermal history conditions of the panel allocation material. For example, acid anhydrides, imidazoles, imidacillins, etc. may be used, but considering the long-term storage of the panel allocation material, those that are stable at room temperature and exhibit activity at high temperatures are preferred; Preferred are nitrogen-containing compounds that decompose at elevated temperatures to yield at least one active hydrogen-containing amine. Typical examples include monourea, volurea, hydrazide, and thiourea.A specific example is 3-(p-chlorophenyl).
-1,1-dimethylurea, dicyandiamide, 2,4
-bis(N,N-dimethylcarbamide)toluene, etc., and one or more of these may be used in combination.

Next, as the inorganic filler, mica, graphite, asbestos, talc, glass flakes, glass fiber, clay, calcium carbonate, silica sand, silica, etc. are not particularly limited, and these may be used in combination.

Next, regarding the blending amount of each component, it is necessary that the epoxy resin is contained in 5 parts by weight to 75 parts by weight out of 100 parts by weight of the total amount of epoxy resin and liquid resin. Further, the amount of the curing agent to be blended varies depending on the blending ratio of the epoxy resin to the liquid resin and the type of the curing agent, but the amount that can be easily calculated from the chemical equivalent may be used as a guideline for blending.

Here, if the epoxy resin is less than 5 parts by weight out of 100 parts by weight of the total amount of epoxy resin and liquid resin, the peak of the composite system loss coefficient (η) that occurs on the high temperature side will be too low. The vibration damping characteristics in the low temperature region are poor and the vibration damping characteristics are unsatisfactory and inappropriate, and if the epoxy resin exceeds 75 parts by weight, the peak of the composite loss coefficient (η) that occurs in the low temperature region becomes too low. It is still inappropriate because it makes people think.

Further, the amount of the inorganic filler added is 30 parts by weight or more based on 100 parts by weight of the total amount of the epoxy resin and liquid resin.

The effect of blending an inorganic filler is to increase the elastic modulus of the panel allocation material, and if it is less than 30 parts by weight, it is inappropriate because almost no filling effect is obtained. In addition, the maximum amount of inorganic filler can be easily calculated from the oil absorption amount specified by the type of filler, up to the maximum amount that can be physically mixed, but if it exceeds 350 parts by weight, The upper limit is preferably 350 parts by weight since the adhesion of

The panel distribution material of this invention can be used for the purpose of curing paint films, etc. by simply placing an uncured sheet formed to the desired thickness using an extruder or calendar roll on a panel to be distributed. , the sheet melts using the heat applied to the panel structure, and due to its own weight it follows the shape of the vibration-damped panel, even if it has a complex surface shape, and then the adhesive hardens, making it easy to attach to the vibration-damped panel. It is a panel allocation material with excellent workability and adhesion. If a liquid low-viscosity epoxy resin is used here and the amount of inorganic filler is small, the sheet will become paste-like, and if the uncured sheet is difficult to handle, the sheet may be heated slightly. may be added to perform so-called B-stage processing, or may be directly extruded onto the allocated panel using an extruder or the like.

(Function) In the panel damping material of the present invention, the cured product of the mixture of epoxy resin and liquid resin has two or more loss factors (η) evaluated in the composite system of the allocated panel and the panel allocation material. Because it generates a peak, it exhibits excellent allocation characteristics over a wide temperature range from low to high temperatures. Originally, as for the physical properties after curing of epoxy resin alone, there is one peak of loss coefficient (η) of the composite system in the temperature range of about 100℃ to 170℃, but the practical temperature range of about 0℃ to 80℃ It is unsuitable as a material for splitting material. On the other hand, in the damping material of the present invention, the cured product made by blending liquid resin with epoxy resin is a resin that is compatible with the epoxy resin, so it acts as a plasticizer for the cured epoxy resin product. The composite system loss coefficient (η) of the cured epoxy resin exhibits the characteristics of
It has the effect of lowering the peak of 80°C or below, which is the practical temperature range. Furthermore, the liquid resin reacts with the epoxy resin,
This has the effect of producing another peak of the composite system loss coefficient (η) in the practical temperature range of 0° C. or higher. In other words, the composite system loss coefficient (
There is a peak of η) and a peak of composite loss coefficient (η) due to the reaction between epoxy resin and liquid resin on the low temperature side of 0°C or higher, so that It can exhibit excellent vibration damping characteristics.

(Example) This invention will be explained by the following examples and comparative examples.

The method for evaluating the damping properties of the panel damping material in the example, the shape followability of the panel to be damped having a complicated surface shape, and the adhesion to the damping panel are as follows. ' i Dominant 1 [Control] On one side of a general automobile exterior steel plate with a length of 250 fl, a width of 15 fl, and a thickness of 0.8 fl, an unhardened steel plate of the same length and width and a thickness of 3.5 fl is applied. Place the panel distribution material and then heat it for 30 minutes at 140℃.
Heating is performed for a minute to obtain a test piece for evaluation of allocation characteristics that is sufficiently adhered and hardened. This test piece was measured using the cantilever resonance method to obtain the composite system loss coefficient (η) at the secondary resonance point of bending vibration.
Measure the temperature dependence of

Generally, it is said that it is preferable for the composite system loss coefficient (η) to be 0.05 or more in terms of allocation characteristics.

Quantity method 2 [) ゛ ]As shown in Figure 1, a=50m, b=10m, c, =lQQ w, d
A prototype panel 1 with a length of 290 m and a width of 1.5 m was fabricated as a prototype, and as shown in Fig.
00fl, thickness 3.5cm panel damping material 2 is placed 140
After heating at ℃ for 30 minutes, it is visually confirmed that the panel allocation material follows the bead shape and there is no gap between the panel and the panel.

Method 3 [] As shown in Figure 3, the length is 20 m, the width is 20 m, and the thickness is 3.
A panel distribution material test piece 3 of 5 cranes was prototyped, and it was placed between two steel plates (panels) 40 with a length of 120 cranes, a width (f) of 20 cranes, and a thickness of 0.8 fi, as shown in the figure, d= 20m,
After clamping with e=100m and heating at 140°C for 30 minutes, let it cool to room temperature, and pull it in the direction of the arrow at a pulling speed of 100"/win to form panel distribution material test piece 3.
The shear strength of the interface between the panel 4 and the panel 4 is measured. 10kgf
/cm" or more is excellent, 5kgf/cm" or less is poor, 5~
10kgf/cm! was rated as good.

Large patch epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., product name:
5 parts by weight of "Epicoat 1004") and 95 parts by weight of xylene resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Nicanor HJ") were mixed for 1 hour in a Burberry mixer heated to 150°C to fully dissolve them.

After cooling this to 60°C, 2 parts by weight of dicyandiamide, 3-(p-chlorophenyl)-1,
1,172 parts by weight of 1-dimethyl, and talc (manufactured by Kunimine Kogyo Co., Ltd., trade name: rGTA J) as an inorganic filler.
150 parts by weight was added and kneaded at a temperature of 60° C. for 1 hour. Next, it was formed into a sheet with a thickness of 3.5 mm using a calender roll. The results of evaluating this sheet according to the evaluation methods 1 to 3 described above are shown in Curve 1 in FIG. 4 and Table 1.

In addition, in the following examples and comparative examples, the resin, curing agent,
The mixing method of the inorganic filler and the sheeting method were the same as in Example 1 unless otherwise specified.

In addition, the types of curing agents were dicyandiamide and 3=(p-chlorophenyl)-1,1-, which are the same as those used in Example 1, considering that a sufficient cured product can be obtained by heating at 140°C for 30 minutes. A mixture containing equal parts by weight of dimethylurea was used in the following Examples and Comparative Examples. For example, curing agent 1
When it is described as 0 parts by weight, it indicates that it is a mixture of 5 parts by weight of dicyandiamide and 5 parts by weight of 3-(p-chlorophenyl)-1,1-dimethylurea.

Chitateyu 1 Epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., product name:
Epicoat 828 J) 25 parts by weight, xylene resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Nicanol HHJ7")
5 parts by weight, 6 parts by weight of hardening agent, calcium carbonate as an inorganic filler (manufactured by Nitto Funka Kogyo Co., Ltd., trade name: rNslI 2)
00 J) A panel damping material consisting of 150 parts by weight was obtained. The results of evaluation using evaluation methods 1 to 3 are shown in Curve 2 in FIG. 4 and Table 1.

Imperial Family ■1 Epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., product name:
Epicoat 100IJ) 45 parts by weight, xylene resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Nicanol LLJ)
) 55 parts by weight, 8 parts by weight of curing agent, 100 parts by weight of clay (manufactured by Kunimine Industries Co., Ltd., trade name "Kunimine Clay") as an inorganic filler, mica (manufactured by Kuraray Co., Ltd., trade name "r")
A panel damping material consisting of 50 parts by weight of sUZORITEMICA 60S J) was obtained. The results of evaluation using evaluation methods 1 to 3 are shown in Curve 3 in FIG. 4 and Table 1.

25 parts by weight of epoxy resin ("Epicor" 1001J), 20 parts by weight of epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name "Epicort 871 J"), xylene resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Product name: “Nikanor LJ”
) 55 parts by weight, 8 parts by weight of hardening agent, 100 parts by weight of talc (GTA) as an inorganic filler, glass fiber (Unitika U M Glass Co., Ltd., trade name: rES 25 T J)
A panel allocation agent consisting of 50 parts by weight was obtained. Evaluation method 1-3
The results of the evaluation are shown in Curve 4 in FIG. 4 and Table 1.

50 parts by weight of epoxy resin (Ebiko 104J), 25 parts by weight of xylene resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Nicanol LLLJ), 2 parts by weight of Nicanol H
5 parts by weight, 8 parts by weight of curing agent, talc (as an inorganic filler)
Manufactured by Kunimine Kogyo Co., Ltd., product name rGAT J) 150
A panel damping material consisting of weight parts was obtained. The evaluation results according to evaluation methods 1 to 3 are shown in song vA5 in FIG. 5 and in Table 1.

50 parts by weight of epoxy resin (Epicoat 828 J') and 50 parts by weight of phenol resin (manufactured by Jumin Bakelite Co., Ltd., trade name: rPR-51670J) were heated at 40°C.
After mixing for 30 minutes in a Pan Bali mixer heated and depressurized to 29wHg to remove low-boiling seafood in the phenolic resin,
Return to normal pressure, add 8 parts by weight of a curing agent and 150 parts by weight of talc (rGTA J'') as an inorganic filler, and heat at 40°C.
The mixture was mixed for 1.5 hours. Next, roll the calender roll to a thickness of 3
．． It was molded into a sheet of five cranes. The evaluation results according to evaluation methods 1 to 3 are shown in curve 6 in FIG. 5 and Table 1.

75 parts by weight of epoxy resin (Epicoat 100IJ'), 25 parts by weight of xylene resin (Mikanol LJ),
10 parts by weight of hardening agent, calcium carbonate (as an inorganic filler)
Manufactured by Nitto Funka Kogyo Co., Ltd., product name rNS #400J
A panel allocation material consisting of 150 parts by weight was obtained. Evaluation method 1~
The evaluation results according to No. 3 are shown in song wA7 in FIG. 5 and in Table 1.

Kita l IL 90 parts by weight of epoxy resin (Epicoat 100IJ), 10 parts by weight of xylene resin (Nicanol LJ), 10 parts by weight of curing agent, talc (rGT) as an inorganic filler.
A panel allocation material consisting of 150 parts by weight of AJ) was obtained.

The evaluation results according to evaluation methods 1 to 3 are shown in curve 11 in FIG. 5 and Table 1.

40 parts by weight of Z Toyoko epoxy resin (Epicor 1001J), 60 parts by weight of xylene resin ([Dicanol HJ), 8 parts by weight of curing agent, talc (rGTA J) as an inorganic filler.
) A panel allocation material consisting of 30 parts by weight was obtained. Evaluation method 1
The evaluation results for 3 to 3 are shown in curve 8 in FIG. 6 and in Table 1.

Among the formulations shown in Example 8, the inorganic filler talc (rG
A panel distribution material was obtained by increasing the amount of only TA J) to 250 parts by weight. The evaluation results by evaluation methods 1 to 3 are shown in curve 9 in Figure 6.
and shown in Table 1.

Among the formulations shown in Example 8, the inorganic filler talc (rG
A panel damping material was obtained by increasing the amount of only TA J'') to 350 parts by weight. The evaluation results according to evaluation methods 1. to 3 are shown in the curve IO in FIG. 6 and in Table 1.

1 Comparison ■1 A panel allocation material was obtained from among the formulations shown in Example 8, which did not contain an inorganic filler and was composed of an epoxy resin, a xylene resin, and a hardening agent. The evaluation results according to evaluation methods 1 to 3 are shown in curve 12 in FIG. 6 and Table 1.

Asphalt-based heat-adhesive sheet (manufactured by Japan Tokushu Toyo Co., Ltd., trade name: Melsheet) (thickness: 3.5 m), which is currently widely used as a control material for automobile floor panels. Tests were conducted according to evaluation methods 1 to 3. The results obtained in the 6th
It is shown in curve 13 in the figure and in Table 1.

- Table 1 (Effects of the Invention) The panel vibration damping material of the present invention is composed of an appropriate amount of a mixed resin of an epoxy resin and a liquid resin including one having a methylol group, and a curing agent and an inorganic filler added thereto. As a result, it exhibits good distribution characteristics with a loss coefficient of 0.06 or more over a wide temperature range, that is, a highly practical temperature range of 0°C to 80°C. Furthermore, it has excellent shape followability and adhesion, so it is suitable for the panel to be distributed. The advantage is that installation is easy.

[Brief explanation of drawings]

Figure 1 is a perspective view of the bead-shaped panel used in evaluation method 2. Figure 2 is a perspective view of the panel allocation material temporarily placed on the bead-shaped panel in Figure 1. Figure 3 is the test piece used in evaluation method 3. 4 is a curve diagram showing the allocation characteristics of Examples 1 to 4 according to evaluation method 1, and FIG. 5 is a curve diagram showing the allocation characteristics of Examples 5 to 7 and comparative example 1 according to evaluation method 1. The curve diagram shown in FIG. 6 is a curve diagram showing the damping characteristics of Examples 8 to 10, Comparative Example 2, and Comparative Example 3 according to Evaluation Method 1. 1- Bead shaped panel 2- Panel allocation company policy... Panel damping material test piece 4-- Rope plate or panel Figure 1 Figure 2 Figure 3 Figure 4 Warm skin (DC) Figure 5 Warm A1 (oC Figure 6 Warm skin ('C)

Claims (1)

[Claims] 1. An epoxy resin, and a liquid resin that is compatible with the epoxy resin and whose terminal group is a methylol group;
It is made by mixing a curing agent and an inorganic filler, in which the epoxy resin is 5 to 75 parts by weight out of 100 parts by weight of the epoxy resin and the liquid resin, and the inorganic filler is mixed with the epoxy resin and the liquid resin. 3 for 100 parts by weight of the total amount of resin
A panel vibration damping material comprising a composition containing 0 parts by weight or more.