JPS6342946B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a vibration damping paint that can be used in a significantly wide range of temperatures and has excellent vibration damping properties and corrosion resistance. [Prior Art] The present inventor has already discovered that a paint containing as main components an unsaturated polyester resin with a heat distortion temperature of 35 to 80°C and a scale-like inorganic substance has a remarkable damping effect in preventing noise caused by vibration. He made a great discovery and completed the invention of vibration damping paint. (Patent Application No. 55-141319) [Problem to be solved by the invention] One of the causes of noise generation due to vibration is that this vibration is transmitted to a planar structure and the planar structure vibrates. It is thought that this is due to the formation of a so-called diaphragm. In order to make this planar structure less likely to vibrate, it has been proposed to install a damping material on its surface. However, these damping materials have the following drawbacks. (a) The damping effect is small. (b) The temperature range in which vibration damping effects can be expected is limited to around room temperature. (c) The adhesion of the damping material to the structure is weak. (d) The durability of the damping material is low, and cracking, falling off, swelling due to water, and deterioration occur due to long-term use. (e) The vibration damping material has a high viscosity and is difficult to handle. Various proposals have been made to solve these drawbacks, but at present there is no material that satisfies all of these drawbacks. [Means for solving the problem] The present inventor further used various thermosetting resins other than unsaturated polyester resins, and carefully investigated the relationship between the heat distortion temperature of the final coating film and the vibration damping properties of the coating material. As a result of research, we have completed the present invention. That is, the present invention is a method of producing thermosetting resins of the same type or different types that have different heat deformation temperatures in the cured state, or that are cured by mixing these curing agents, plasticizers, thermoplastic resins, etc. The heat deformation in the cured state contains as main components 100 parts by weight of a plurality of mixable thermosetting resins of the same type or different types and 10 to 200 parts by weight of an inorganic filler, the heat deformation temperature of which is adjusted. Temperature 30-120
It is characterized by what it did to ℃. The field of use of the vibration damping paint of the present invention is, for example, (a) engine-related parts such as engine covers, engine room floorboards, oil pans, conductor plates, and fuel tanks; (b) marine vessels such as bridges, ship walls, and sonar domes. (c) Vehicle parts such as vehicle floors, walls, roofs, collector covers, machine covers, etc.; (d) Fan surroundings such as fan casings, fan blades, duct walls, etc.; (e) Other structures such as iron bridges; Snow covers for elevated lines, conveyor covers, soundproof walls, building floors, walls, ceilings, roofs, elevator doors, walls, boiler covers, office machine covers, refrigerators, air conditioners,
It is effective in many applications such as washing machines. The heat distortion temperature of the thermosetting resin in the present invention is
Expressed as temperature measured with final coating in cured state according to ASTMD-648-72. The vibration damping characteristics are shown in Automotive Technology Vol. 23, August issue (1969).
Oberst
By showing a relationship in which the loss coefficient (η) measured based on the
Coating was applied to one side of a 40 mm cold-rolled steel plate so that the film thickness when dry was approximately 2 mm (approximately 50 g of coating weight per steel plate with the above dimensions).The coated steel plate obtained by hardening was used as a test piece. The above forced vibration method (Oberst method)
The loss coefficient (ηcomb) of the composite was measured at each measurement temperature based on the vibration damping characteristics. When the heat distortion temperature of the final coating film in the cured state of the thermosetting resin of the present invention exceeds 120°C,
For example, the damping performance is good in a fairly high temperature range of 150℃ or higher, but the damping effect in the temperature range from room temperature to 100℃, especially in the low temperature range, is hardly expected, and the final coating film in the cured state is When the heat distortion temperature is less than 30°C, the damping temperature range shifts to the lower temperature side, and the damping performance in a relatively high temperature range such as 60 to 100°C decreases, which is not suitable for each of the above-mentioned uses of the present invention. It is insufficient as a vibration damping paint. Further, as the inorganic filler which is one of the main components of the present invention, mica, graphite, glass fiber, glass flakes, and asbestos are suitable, but there are no particular limitations as long as the filler is an inorganic filler, such as talc,
Silica sand, ceramics, clay, iron oxide or a combination thereof may be used. As mentioned above, the amount of the inorganic filler added is preferably 10 to 200 parts by weight per 100 parts by weight of the thermosetting resin; if it is less than 10 parts by weight, the vibration damping properties of the coating film will be insufficient. If the amount exceeds 200 parts by weight, the adhesion of the coating film decreases, peeling of the coating film occurs after long-term use, and the fluidity of the coating material decreases, causing deterioration of the coating properties and surface condition of the coating film, which is undesirable. The most preferred range of use is 25 to 80 parts by weight of the inorganic filler per 100 parts by weight of the thermosetting resin. Next, the present invention will be explained in detail. According to the research of the present invention, () for the same type of thermosetting resin mixture. By changing the mixing ratio of epoxy resin (trade name Epicote 828 manufactured by Ciel Chemical Co., Ltd.) and epoxy resin (Epicote 871 manufactured by Ciel Chemical Co., Ltd.) with different heat distortion temperatures.
When cured with TTA (triethylenetetramine), the heat distortion temperatures of these mixed resins are as shown in Table 1.

[Table] However, 0.7 phr (parts by weight relative to 100 parts of resin) of DMP (tris dimethylaminomethylphenol) was added as a curing accelerator. The heat distortion temperature is 30 to 120℃ depending on the formulation in Table 1.
The loss coefficient (ηcomb) is ηcomb=0.06 or more at a temperature of 0 to 140°C, and the vibration damping property is large. In this case, of course, 10 to 200 parts by weight of the inorganic filler was added to 100 parts by weight of the epoxy resin. In the following studies, unless otherwise specified, 100 to 200 parts by weight of an inorganic filler was added to 100 parts by weight of synthetic resin.
Parts by weight are added. It can also be achieved by mixing an unsaturated polyester resin with a heat distortion temperature of 30 to 120°C and an unsaturated polyester resin with a heat distortion temperature of 20 to 250°C in a desired ratio as shown in Table 2. .

[Table] () When mixing different types of thermosetting resins. In the mixture systems shown in Table 3, the heat distortion temperature can be adjusted to 30℃ to 120℃ even for mixtures of unsaturated polyester resin and epoxy resin, or mixtures of unsaturated polyester resin and polyurethane resin. , also in this case, ηcomb=0.06 or more, and the damping effect is exhibited. In Example ○C (Table 7) described later, the heat distortion temperature of the mixture is 35°C, and in ○I, the heat distortion temperature is 50°C. The heat distortion temperature can also be adjusted to 30 to 120°C by mixing a thermoplastic resin with a thermosetting resin.
For example, add vinyl acetate and vinyl persate copolymer (heat distortion temperature 0°C) to 100 parts of unsaturated polyester resin (isophthalic acid type, heat distortion temperature 45°C).
When 20 parts by weight are mixed, the heat distortion temperature of the mixture is
You can get one at 32℃.

【table】

〔Example〕

Next, the present invention will be explained with reference to Examples. Example 1 (using epoxy resin alone)

[Table] Using a paint with the composition ratio shown in Table 4, the dry coating thickness on one side of a cold-rolled steel plate was approximately the same by troweling.
It was coated to a thickness of 2.5 mm, and ηcomb was measured at each temperature. The results are shown by the curve in Figure 1A. (All drawings are semi-logarithmic graphs.) Example 2 (Two types of epoxy resin systems, types of curing agents, or systems using diluents and plasticizers together)

[Table] Paints having the composition ratios shown in Table 5 were prepared, and the ηcomb at each temperature was measured and illustrated in FIGS. 2 to 4. Example 3 (When unsaturated polyester resins with different heat distortion temperatures are mixed)

[Table] Each paint having the composition ratio shown in Table 6 was prepared, and the ηcomb at each temperature was measured and shown in FIGS. 5 and 6. Example 4 (When mixing different types of thermosetting resins)

【table】

[Table] Each paint having the composition ratio shown in Table 7 was prepared, and the ηcomb at each temperature was measured and shown in FIG. Example 5 (When using thermosetting resin and thermoplastic resin together)

【table】

[Table] The coating thickness of the paint was 2.5 mm, and the measurement results of ηcomb are shown in Figure 7-1. Comparative Example 1 A putty-like paint containing 100 phr of vinyl acetate emulsion, 250 phr of mica, and 50 phr of mica was troweled onto one side of a cold-rolled steel plate to a dry thickness of approximately 2 mm, and the results of measuring ηcomb at each temperature are shown below. Figure 1A
It is shown by the curve. ηcomb is 0.06 or more in the range of 0 to 30℃,
The damping effect above 30°C is small, so it cannot be applied to applications that require effectiveness at high temperatures, such as automobile-related parts. In addition, when this sample was exposed outdoors for one month, the paint film blistered, some parts fell off, and there were places where the steel plate had rusted considerably, making it extremely difficult to use it for outdoor use. It's not a thing. Indeed, the heat distortion temperature of this coating film when dry was 23°C. Comparative examples 2, 3, 4

〔Effect of the invention〕

As is clear from the above Examples and Comparative Examples, the paint of the present invention, which has a heat distortion temperature in the range of 30 to 120°C, has an ηcomb of 0.06 or more in the range of 0 to 140°C, and exhibits an excellent vibration damping effect. . Furthermore, the present invention can be used with thermosetting resins other than those mentioned above, such as phenol-based, urea-based, silicone-based, or furan-based synthetic resins, alone or with the addition of plasticizers, curing agents, and other additives, or with the addition of thermoplastic resins. When the heat distortion temperature is adjusted to 30 to 120℃ by arbitrarily mixing ηcomb to 0.06 in the range of 0 to 140℃
This provides an excellent vibration damping effect.

[Brief explanation of the drawing]

FIG. 1 is an illustration of the value of ηcomb at each temperature of the damping paint of the present invention in Example 1. 2nd, 3rd,
FIG. 4 is an illustration of the value of ηcomb at each temperature of the damping paint of the present invention in Example 2. 5 and 6 are illustrations of the value of ηcomb at each temperature of the damping paint of the present invention in Example 3. FIG. 7 shows the value of ηcomb at each temperature of the damping paint of the present invention in Example 4. I, ha, ni, ho, he, to, chi, ri, nu, ru,
Wo, Wa, Ka, Yo, Ta, Re, So, Tsu, Ne, Na, La,
M, U, I, and NO respectively indicate the curves of ηcomb at each temperature.

Claims (1)

[Claims] 1 Multiple thermosetting resins of the same type or different types that have different heat deformation temperatures in the cured state, or mixtures of these with curing agents, plasticizers, thermoplastic resins, etc. 100 parts by weight of the plurality of thermosetting resins of the same or different types that can be mixed and whose deformation temperature has been adjusted and 10 parts by weight of an inorganic filler.
200 parts by weight as a main component, and has a heat deformation temperature of 30 to 120°C in a cured state.