JPH0247508B2 - SEISHINTORYO - Google Patents

Description

[Detailed description of the invention]

The present invention provides a novel vibration damping paint that has high vibration damping properties over a significantly wide range of operating temperatures ranging from 70°C to higher temperatures, and at the same time has excellent corrosion resistance and workability. The present applicant has already found that a paint mainly composed of an unsaturated polyester resin with a heat distortion temperature of 35 to 80°C and a scale-like inorganic substance has a significantly greater effect in preventing noise caused by vibration, so-called vibration damping paint. completed the invention of (Japanese Unexamined Patent Publication No. 57-65759) Further, thermosetting synthetic resins other than unsaturated polyester resins may be used singly or in combination with a plurality of thermosetting synthetic resins having different heat distortion temperatures in the cured state including unsaturated polyester resins. 100 parts by weight of a thermosetting resin or a plurality of thermoplastic resins that have their heat distortion temperature adjusted in a cured state with a curing agent, plasticizer, thermoplastic resin, etc., and an inorganic filler.
They have also completed the invention of a damping paint containing 10 to 200 parts by weight as a main component and having a heat deformation temperature of 30 to 120°C in a cured state. (Unexamined Japanese Patent Publication No. 57-
(No. 139154) The present inventors have further continued their research on vibration damping paints, and have created a book that has an even better damping effect than the previous application, has a wider temperature range, and has a significantly wider range of applications. This led to the completion of the invention,
The present invention is a thermosetting resin with a heat distortion temperature of 70 to 160°C.
This product provides a vibration damping paint in which 100 parts by weight of a scale-like inorganic material is mixed with a powder filler of 0.1-50% by weight based on the scale-like inorganic material, and the scale is added to a thermosetting synthetic resin. A higher vibration damping effect can be obtained compared to the use of a single inorganic substance or an inorganic powder alone, and it also has vibration damping properties over a significantly wide range of temperatures from room temperature to around 160°C, as well as being oil resistant and water resistant. It has excellent resistance to environmentally corrosive liquids and gases, such as water resistance and salt water resistance, and is also excellent in terms of paintability with sprays and the like. The vibration damping paint of the present invention can be applied to (a) parts around engines such as engine covers, oil pans, cylinder covers, air cleaners, timing gear covers, baffle plates, heat covers, etc. (b) parts around blowers such as fan casings, blades, ducts, etc. (c) Vehicle parts such as vehicle floors, walls, roofs, collector covers, machine covers, etc. (d) Ship parts such as walls and ceilings of ship cabins and machine rooms, (e) Conveyor covers, building ceilings, walls, and elevator walls. It is effective for use in many applications such as doors, casings for weak electrical products, covers, flue ducts, hot air ducts, etc. It is especially effective when used in noisy locations where the environment has temperature changes over time. In the present invention, the heat distortion temperature of the thermosetting resin is
Expressed as temperature measured with final coating in cured state according to ASTM D-648-72. In addition, the damping characteristics are loss coefficients (〓) measured based on the forced vibration resonance method (Oberst method) described in Automobile Technology Vol. 23, August issue (1969), page 807.
By showing the relationship that is proportional to the damping characteristics, the length
A coated steel plate obtained by coating one side of a cold-rolled steel plate measuring 400 mm and width 40 mm so that the coating film thickness when dry is approximately 2.5 mm (approximately 50 g basis weight per steel plate of the above dimensions) and curing. As a test piece, the loss coefficient (〓comb) as a composite was measured at each measurement temperature based on the above-mentioned forced vibration method (Oberst method), and vibration damping characteristics were shown. Thermosetting resins with a heat distortion temperature of 70 used in the present invention include (a) unsaturated dicarboxylic acids or polycondensation products of unsaturated dicarboxylic acids and saturated dicarboxylic acids with polyhydric alcohols, and modified vinyl ester resins. unsaturated polyester resins such as those dissolved in monomers such as styrene monomer or vinyl toluene; (b) condensates of epichlorohydrin and bisphenol with ethylene oxide bonds bonded with amines Epoxy resin, which is commonly used in products. (c) A urethane resin made of an isocyanate and a hydroxy compound, which may be used alone or in combination, and have a heat deformation temperature adjusted to a range of 70 to 160°C. If the heat distortion temperature of the final coating film in the cured state is less than 70°C, the vibration damping temperature range shifts to the low temperature side, resulting in a decrease in vibration damping performance in the high temperature range, which is detrimental to each of the above-mentioned uses of the present invention. is insufficient as a vibration damping paint. In addition, if the heat distortion temperature exceeds 160℃, 160℃
Although it is possible to provide vibration damping performance in the above-mentioned high temperature range, the vibration damping paint of the present invention does not have heat resistance above 160°C (based on ordinary temperatures), so it has poor durability. Cannot be used. In addition, in order to adjust the heat deformation temperature of the thermosetting resin, a thermoplastic resin such as an acrylic resin or a plasticizer such as dioctyl phthalate can be added. It is also possible to add a heat resistance improver such as hindered phenols or phosphoric esters to prevent thermal deterioration. The scale-like inorganic substance which is another important component of the present invention is preferably mica or graphite, but there are no particular limitations as long as it is an inorganic scale-like substance. Regarding the particle size, an average particle size of about 300 microns is preferable from several tens of microns. If the particle size becomes too coarse, the coating workability will be poor, and the surface of the coating will be rough and the appearance will be poor. In addition, as the powder filler, carbon powder,
Thermosetting resin powders such as silica sand, talc, calcium carbonate, magnesium carbonate, aluminum powder, copper powder, glass powder, titanium oxide powder, phenol resin powder, melamine resin powder, urethane resin powder, wood powder, and these powders The body may be used alone or in combination. The amount of scale-like inorganic material used is 100% of the thermosetting resin.
10 to 200 parts by weight of the powder filler is further mixed in an amount of 0.1 to 50 weight percent of the scale-like inorganic material. In any case where the scale-like inorganic material and the powder filler are added in amounts outside the above ranges, the adhesion to the object to be coated decreases, resulting in peeling of the coating film after long-term use, and also deteriorating the properties of the coating material. Furthermore, the preferred mixing ratio for vibration damping performance is to add 25 to 50 parts by weight of the scale-like inorganic material to 100 parts by weight of the thermosetting resin, and to add 10 to 40 parts by weight of the powder filler to this scale-like inorganic material. be. Next, the present invention will be explained by the present invention. Example 1 Paint was adjusted according to the compounding ratio shown in Table 1, and a pressure-feed air spray gun (diameter 2.5 mm, air pressure 5 kg/
cm ² ) to one side of a cold-rolled steel plate with a thickness of 0.8 mm, a length of 400 mm, and a width of 40 mm so that the dry coating thickness is approximately 2.5 mm (approx. 50
g), and was cured at room temperature for about 4 hours. Figure 1 shows the results of measuring the loss coefficient (〓comb) of the composite body using the thus obtained coated steel plate as a test piece according to the forced damping resonance method (Oberst method) at each measurement temperature. show.

[Table] As a result, a damping paint with high performance in a wide temperature range from 60℃ to 160℃ was obtained. Example 2 A paint was prepared according to the formulation shown in Table 2, a test piece was prepared in the same manner as in Example 1, and the loss coefficient (〓comb) as a composite was determined according to the forced vibration resonance method (Oberst method). The results of measurements at each measurement temperature are shown in FIGS. 2 and 3.

【table】

[Table] From the results shown in Figure 2, it can be seen that vibration damping paints containing graphite scales mixed with 0.1 to 50% by weight of carbon have higher vibration damping performance than those containing no carbon. Example 3 The paint was adjusted according to the formulation shown in Table 3, a test piece was prepared by troweling, and the loss coefficient (〓comb) as a composite was measured at each measurement temperature according to the Oberst method. are shown in Figs. 4 and 5.

[Table] Results from Table 3 As in the case of the unsaturated polyester resin in Example 1, at the appropriate mixing ratio of graphite and carbon, vibration damping performance was higher than when graphite scales were used alone. was gotten. Example 4 A paint was prepared according to the formulation shown in Table 4, a test piece was created by coating it, and the loss coefficient (〓comb) as a composite was measured at each measurement temperature according to the Oberst method. It is shown in Table 5.

【table】

【table】

[Table] From the results in Table 5, it was found that by adding an appropriate amount of carbon (HF) to mica, a product with a high vibration damping effect could be obtained. Example 5 A paint was prepared according to the formulation shown in Table 6, a test piece was prepared using an air spray gun, and Oberst
Loss factor (〓comb) as a complex according to the law
Table 7 shows the results of measurements for each measurement temperature.

【table】

[Table] A similar trend was confirmed even when the granular filler was talc or light calcium carbonate. Not only by adding a single powder filler, but also by using a plurality of powder fillers, vibration damping performance can be improved by mixing 0.1 to 50% by weight with respect to the scale-like inorganic material. At the same time, it is effective in expanding the operating temperature range, and the use of a powder filler in combination is also economically advantageous. Example 6 A paint was prepared according to the formulation shown in Table 8, a test piece was prepared using an air spray gun, and the loss coefficient (〓comb) as a composite was determined according to the Oberst method.
Table 9 shows the results of measurements for each measurement temperature.
A damping effect is observed even when organic powder is used alone or in combination.

【table】

[Table] Next, an example of an experiment carried out by the present inventor on the vibration damping properties of scale-like inorganic materials classified into various lengths and powdered materials is shown below. . Commercially available scale-like inorganic materials have a slight particle size distribution because they are classified with a sieve, but this was further classified and the comb of various samples was measured using the scale-like inorganic materials with a specific size as a base. Table 9 shows formulation examples based on graphite of specific sizes, and samples were prepared in the same manner as in each of the above Examples. Table 10 shows each 〓comb.

【table】

[Table] Regarding the size of the shape of the scale-like inorganic material, there is almost no difference in damping performance in the size range of 10μ to 300μ, that is, the size shown in Table 9. On the other hand, when a 0.1μ powder such as carbon is used alone, the performance is inferior, but when a certain mixing ratio of the scale-like inorganic material and the powder filler is used, the damping characteristics are improved. In general, a so-called non-constrained vibration damping structure (Extension
In the case of (type), the vibration damping paint made of a viscoelastic polymer material stretches and deforms against the repeated bending behavior caused by solid vibration of the base material, and has a suppressing effect. This appears as a damping effect. This damping effect increases as the loss modulus (E″) of the damping coating material increases. On the other hand, the loss modulus (E″) is the sum of the material's internal friction (tanδ) and dynamic elastic modulus (E′), that is, E ″=tanδ・
It is represented by E′. By mixing a specific ratio of the powder filler to the scale-like inorganic material, the powder filler is interposed in the gaps between the scale-like inorganic materials oriented and dispersed in the matrix, increasing the dynamic elastic modulus (E'), but the internal There is no loss of friction (tanδ). Therefore, the loss modulus (E″) is improved.On the other hand, by mixing in an excessive amount of powder filler, the dynamic elastic modulus (E′) is only increased, and the internal friction (tanδ) is greatly reduced, resulting in The reason why the scale-like inorganic material alone has a better vibration-damping effect than the powder filler alone is that the interfacial stress between the scale-like material and the polymeric material that is the matrix It is inferred that this is because it acts three-dimensionally and has a restraining force against the deformation of the base material, and has an effect on both internal friction (tan δ) and dynamic elastic modulus (E′). It can be seen that the vibration damping paint of the present invention has extremely excellent physical properties such as corrosion resistance, weather resistance, and resistance to thermal shock as shown in Table 11. According to the formulation shown in Table 2 of Example 2 above. Table 11 shows the results of testing corrosion resistance, weather resistance, etc. on the test pieces.

【table】 [Brief explanation of drawings]

Figure 1 shows the comb value at each temperature of the vibration damping paint of the present invention in Example 1, and Figure 2 shows the carbon addition amount (%) of the vibration damping paint of the present invention in Example 2.
Figure 3 shows the comb value at each temperature of the damping paint of the present invention in Example 2. Figure 4 shows the carbon addition amount (%) of the controlled vibration paint of the present invention in Example 3. Figure 5 shows the comb values of the damping paint of the present invention in Example 3 at various temperatures. 2, 3, 4, 5, 6, 7, 8, 9, 10, 1
1, 12, 13, 14, 15, 18, 19, 2
0, 21, and 22 show the 〓comb curve at each temperature and the 〓comb curve according to the carbon addition amount (%), respectively, according to the present invention.

Claims (1)

[Claims] 1. Mix 100 parts by weight of a thermosetting resin with a heat distortion temperature of 70 to 160°C and 10 to 200 parts by weight of a scale-like inorganic material, and further mix powder filler in an amount of 0.1 to 50 percent by weight based on the scale-like inorganic material. Anti-vibration paint.