JPH0116853B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention is applicable to a wide range of fields such as automobiles, railway vehicles, architecture, industrial machinery and transportation equipment, household appliances and office office automation equipment, aircraft and ships, etc., which vibrate and generate noise. It can be applied to structural members in the temperature range of °C and can be applied by adhesion with adhesives, pressure-sensitive adhesives, or direct attachment by heat fusing or melt bonding with organic solvents, and provides excellent vibration damping. This article relates to a vinyl chloride resin vibration damping material that exhibits excellent performance. [Prior art] Conventionally, asphalt-based damping materials used near room temperature, and vinyl chloride resin damping materials that can be used near room temperature or relatively high temperature regions up to 80°C, such as nitrile butadiene rubber and vinyl chloride. A vibration damping material made of resin or vinyl chloride copolymer, coumarone resin, plasticizer and filler was published in Japanese Patent Application Laid-Open No. 135122/1983.
The publication also describes a vibration damping material made of vinyl chloride resin or vinyl chloride copolymer, polymethyl methacrylate resin, plasticizer and filler in JP-A-58-39828.
They are disclosed in the respective publications. [Problems to be solved by the invention] Among the above-mentioned damping materials, the asphalt-based damping material has a low maximum value of damping performance (represented by loss modulus E'') and maintains its damping performance. The temperature range is narrow, and the damping performance deteriorates significantly especially in the relatively high temperature range of 40℃ or higher.Furthermore, it has drawbacks such as being brittle and cracking in the winter and becoming sticky in the summer. .Also, the above-mentioned JP-A-Sho
Although the damping material described in Publication No. 53-135122 has a relatively high maximum value of loss modulus E'', the temperature range in which it maintains damping performance is rather narrow, and the damping performance deteriorates particularly at high temperatures. On the other hand, the damping material described in JP-A No. 58-39828 has a relatively high maximum value of loss modulus E'', but the temperature at which it maintains its damping performance is extremely low. The region is rather narrow, and the damping performance deteriorates particularly on the high temperature side.Furthermore, in order to obtain damping performance near room temperature, a large amount of plasticizer must be added, and plasticizer migration and environmental This causes problems such as contamination. [Means for Solving the Problems] The present invention has been made by focusing on the above-mentioned problems. The present invention aims to provide a vinyl chloride resin-based vibration damping material, which is composed of a specific amount of plasticizer and a specific amount of a filler, and which provides various viscoelastic properties depending on the ratio of these components. That is, in the present invention, the blending ratio of vinyl chloride resin or vinyl chloride copolymer and thermoplastic polyurethane is in the range of 95:5 to 40:60, and 0.5 to 35 parts by weight of coumarone resin is added to 100 parts by weight of the total weight. The filler is contained in an amount of 50 to 450 parts by weight per 100 parts by weight of the organic binder.
A vinyl chloride resin vibration damping material is characterized in that 1 to 45 parts by weight of a plasticizer is added to 100 parts by weight of the total weight of vinyl chloride resin or vinyl chloride copolymer and thermoplastic polyurethane. Therefore, the blending ratio of organic binder and filler is 50 to 450 parts by weight, preferably 70 to 400 parts by weight, per 100 parts by weight of organic binder, which is less than 50 parts by weight. If the amount exceeds 450 parts by weight, not only will the vibration damping performance not improve any further, but the workability of mixing and molding will be impaired, and the porosity will increase, resulting in a decrease in mechanical strength. , which may cause problems in practice. In addition, the blending ratio of PVC and PUR is 95:5 to 40:
60, preferably in the range of 92:8 to 50:50, because if PUR is low beyond this range, the temperature range in which damping performance is maintained is narrow, and beyond this range, PUR is high. The temperature range in which excellent vibration damping performance is obtained is too low.
When PUR is increased within this range, the temperature at which the damping performance reaches its maximum shifts from the high temperature side to the low temperature side and becomes wider than the temperature range where the damping performance is maintained. This has the effect of suppressing the decline. Furthermore, PUR has better weather resistance than nitrile butadiene rubber, and has better weather resistance than the vibration damping material disclosed in JP-A-53-135122. The reason why we decided to add 1 to 45 parts by weight, preferably 5 to 40 parts by weight of plasticizer to 100 parts by weight of the total weight of PVC and PUR is that if it is less than 1 part by weight, the increase in the loss modulus E'' will be small. The improvement in vibration damping performance is not sufficient, and the effect of widening the temperature range in which vibration damping performance is maintained is small.Additionally, if it exceeds 45 parts by weight, the temperature range in which excellent vibration damping performance is achieved goes too far to the low temperature side, and plasticization occurs. Problems such as plasticizer migration and environmental pollution occur.If the amount of plasticizer is increased within this range, the temperature at which vibration damping performance reaches its maximum will shift from the high temperature side to the low temperature side, and the maximum value of the loss modulus E'' will occur. As a result, the temperature range in which damping performance is maintained becomes wider. In the present invention, coumaron resin is blended as an organic binder in addition to PVC and PUR, and the coumaron resin is mixed in an amount of 0.5 to 33 parts by weight, preferably 1 to 13 parts by weight, per 100 parts by weight of the total weight of PVC and PUR. The reason why we decided to add less than 0.5 parts by weight is that vibration damping performance is not sufficiently improved and has little effect in widening the temperature range in which vibration damping performance is maintained.
This is undesirable because it lowers the E''. In the present invention, it is preferable to use a flake-like filler as the filler.Flake-like fillers have the effect of increasing the loss modulus E'' and are suitable for use as fillers for damping materials. It is very good as a filler material, and it is preferable to contain this flake-like filler material in an amount of 50% or more of the total weight of the filler material.If it is particularly necessary to increase the loss modulus E'', the total amount of the filler material should be It is effective to make it into a flake-like filler.PVC, that is, vinyl chloride resin and vinyl chloride copolymer, may be any commercially available products, but resins for paste processing are particularly preferred.As the vinyl chloride copolymer, For example, there is vinyl chloride vinyl acetate copolymer. PUR (thermoplastic polyurethane resin) is compatible with vinyl chloride resin or vinyl chloride copolymer, and is suitable for vinyl chloride resin or vinyl chloride copolymer blends. Commercially available plasticizers may be used. Plasticizers may be ester plasticizers commonly used for vinyl chloride resins or vinyl chloride copolymers, such as phthalate esters, such as DOP (di-2-ethylhexyl phthalate), acipate esters, etc. ,
For example, DOA (di-2-ethylhexyl adipate), sebacic acid ester, for example DOS (di-2-ethylhexyl adipate),
-ethylhexyl sebacate), phosphate ester,
For example, TCP (tricresyl phosphate). Coumaron resin is used in rubber, paint, ink,
It is mainly used as a softener, plasticizer, and adhesion improver in various formulations in the field of adhesives and sealants, and is a copolymerized resin or modified resin containing coumaron, indene, and styrene as main components. Filling materials include, for example, flaky fillers such as natural mica, synthetic mica, graphite, glass flakes, ferrite, clay, talc, vermiculite, montmorillonite, stainless steel flakes, aluminum flakes, and nickel flakes;
Fibrous fillers such as glass fiber, carbon fiber, asbestos, glass beads, calcium carbonate, silica, silica sand, kiln ash, cement, dolomite,
Particulate fillers such as micro hollow bodies (glass balloons, glass balloons, etc.), iron powder, lead powder, copper powder, aluminum powder, etc., and one or more selected from these are used. Ru. Of these fillers, it goes without saying that flake-like fillers will be effective if applied as previously proposed by the present applicant in Japanese Patent Application No. 181075-1983. It's a good thing. Further, stabilizers, lubricants, ultraviolet absorbers, antioxidants, flame retardants, colorants, antistatic agents, antifungal agents, and the like may be added as necessary. [Function] With the above-described configuration, the present invention can freely control the temperature at which the damping performance reaches its maximum within the range of approximately room temperature to 70°C, and moreover, the maximum value of the damping performance is high and the damping performance is maintained. The temperature range is wide, and the adhesive strength with the base material, for example, a steel plate, is also very good, making it ideal for application to the above-mentioned structural members. [Example] Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Example 1 Zeon 121 (Nippon Zeon Co., Ltd.) was used as a vinyl chloride resin.
), Pandik T-5265 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) as a thermoplastic polyurethane resin, Nippon Steel Kumaron G-90 (manufactured by Nippon Steel Chemical Industries, Ltd.) as a coumaron resin, and DOP (manufactured by Kishida Chemical Co., Ltd.) as a plasticizer. Manufactured by: G
2-ethylhexyl phthalate), as a stabilizer
DLF (manufactured by Sakai Chemical Industry Co., Ltd.: dibasic lead phthalate),
In Example 1, CD stearate and Ba stearate (manufactured by Kishida Chemical Co., Ltd.) were used as stabilizers and lubricants, and flaky Susolite Mica 40S (manufactured by Kuraray Co., Ltd.) was used as a filler, as shown in Table 1. Mix the composition as shown in a ribbon blender (or Henschel mixer), then knead with a calendar roll for 5 to 10 minutes at 170 to 180°C, draw it out into a sheet, and press-form it into a sheet with a thickness of about 1.5 mm. This was used as a vibration damping material specimen. Press molding conditions are press temperature 180℃, mold and sample heating time 5 minutes,
Press time and pressure: 3 minutes x 100 Kg/cm ² , cooling time and pressure: 5 minutes x 100 Kg/cm ² . Examples 2 to 4 and Comparative Examples 1 to 5, 8 to 12 With the ingredients as described in Table 1, Example 1
A specimen was prepared in the same manner as described above. In addition to those mentioned above in Example 1, the ingredients include Zeon 103EP (manufactured by Nippon Zeon Co., Ltd.), Bandex T-5000 (manufactured by Dainippon Ink and Chemicals Co., Ltd.),
Kumaron resins include Nippon Steel Kumaron, V-120 (manufactured by Nippon Steel Chemical Industry Co., Ltd.), and flaky Suzolite Milo.
150S (manufactured by Kuraray Co., Ltd.), chopped strand ECSO6-350 (made by Central Glass Co., Ltd.), which is glass fiber
), calcium carbonate S-LITE1200 (manufactured by Nitto Kaika Kogyo Co., Ltd.), and silica sand (manufactured by Misato Silica Co., Ltd.) were used. Comparative Examples 6 and 7 Commercially available asphalt-based vibration damping materials (manufactured by Hitachi Chemical Co., Ltd.) and vinyl chloride resin-based vibration damping materials (manufactured by Bridgestone Corporation) were used as test specimens, respectively.

〔Effect of the invention〕

Regarding the above measurement results, the relationship between the loss modulus E'', which represents vibration damping performance, and temperature was determined at a frequency of 110Hz.
The effects of the present invention are shown in FIGS. 1 to 3, and some of the effects of the present invention will be explained in comparison with comparative examples. Comparing Example 1 and Comparative Example 2 in FIG. 2, it is found that by adding a plasticizer, the present invention has the same maximum value of loss modulus E'' and its application temperature as when adding thermoplastic polyurethane resin. It can be seen that the amount of plasticizer added has an effect on maintaining vibration damping performance in the desired temperature range. In Fig. 2, comparing Examples 1 and 2 with Comparative Example 3, By adding Coumaron resin, the present invention can control the maximum value of the loss modulus E'' and its application temperature, which means that the thermoplastic polyurethane resin or plasticizer has the maximum loss modulus E''. Contrary to having the effect of shifting the temperature to the low temperature side, Coumaron resin has the effect of shifting the temperature at which the loss modulus E'' is maximum to the high temperature side,
It can be seen that the amount of Cumaron resin added has an effect on maintaining damping performance in a desired temperature range. In addition, in FIG. 2, Examples 1 and 2 and Comparative Example 11,
12, the present invention can increase the maximum value of the loss modulus E'' by adding coumaron resin to the thermoplastic polyurethane resin and the plasticizer, and also increase the spread of the loss modulus E''. This shows that it is possible to obtain an excellent vibration damping material that can be made wider and has even smaller temperature dependence. In Figure 3, Examples 3 and 4 and Comparative Examples 4 and 5
Comparing this with the results suggests that the filler material contributes to vibration damping performance. In other words, flake-like fillers are superior;
It can be seen that the filling rate is an important factor in the present invention because it has an influence and shows an effect. As is clear from comparing Examples 3 and 4 and Comparative Examples 6 and 7 in FIG. Compared to the above, it has a higher maximum value of the loss modulus E'', a wider spread, and less temperature dependence, making it superior.

[Brief explanation of drawings]

1 to 3 compare examples of the present invention and comparative examples including conventional damping materials in terms of damping performance and operating temperature.

Claims (1)

[Claims] 1 The blending ratio of vinyl chloride resin or vinyl chloride copolymer and thermoplastic polyurethane is 95:5 ~
40:60, and 50 to 450 parts by weight of the filler is contained to 100 parts by weight of the organic binder, which is made by adding 0.5 to 35 parts by weight of coumaron resin to 100 parts by weight of the total weight. and 1 to 45 parts by weight of a plasticizer is added to 100 parts by weight of the total weight of vinyl chloride resin or vinyl chloride copolymer and thermoplastic polyurethane.