JPH0441542A - Vibration energy absorbing material - Google Patents

Abstract

PURPOSE:To keep a high loss factor over a wide temp. range and prevent bleeding by compounding a polyvinyl chloride resin, a petroleum resin, and a plasticizer. CONSTITUTION:100 pts.wt. polyvinyl chloride resin, 3-200 pts.wt. petroleum resin having a number-average mol.wt. of 500-1500 and a total content of indene and styrene of at least 50%, the styren content being higher than that of indene, 5-200 pts.wt. plasticizer comprising a phthalic ester of formula I (wherein R1 and R2 are each a 3-8C monocyclic hydrocarbon group) (e.g. dicyclohexyl phthalate) or/and a phosphoric ester of formula II (wherein R3 to R5, are each a 6-9C arom. monocyclic hydrocarbon group) (e.g. trixylenyl phosphate), and, if necessary, an inorg. filler, a flame retardant, a flaky filler, etc., are compounded, kneaded, and formed into a sheet at about 140 deg.C.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention improves operational response speed, measurement accuracy, and sound quality by controlling vibration in the fields of various transportation equipment, precision electronic equipment, audio equipment, etc. The present invention relates to a polyvinyl chloride resin composition that has excellent vibration energy absorption performance and is used for the purpose of vibration energy absorption.

[Prior Art] Conventionally, butylcomb has been most commonly used as a vibration energy absorbing material. Recently, polynorbornene and special urethane elastomers have been attracting attention as they are considered to have higher performance. The primary evaluation of these vibration energy absorbing materials is performed using the storage modulus (E') and loss coefficient (Tan δ = loss modulus (E-)/storage modulus (E)) determined by measuring the material's viscoelasticity. .

The performance as a vibration energy absorbing material is better if the loss coefficient is larger, and the storage coefficient has an optimum value depending on the form in which it is used. These two factors are usually highly temperature dependent. That is, the storage modulus gradually decreases as the temperature increases, and usually decreases rapidly from a temperature range exceeding the glass transition point. Further, the loss coefficient shows the highest value in the temperature range exceeding the glass transition point, but generally tends to decrease in the temperature range around that point.

Therefore, the standard required for such vibration energy absorbing materials has traditionally been that the material has a high loss coefficient in the temperature range in which it is used.

On the other hand, the storage modulus can be adjusted within a considerable range by adding inorganic or metal fillers, softeners, rubber, etc., so it has been possible to adjust it to the optimum value. Therefore, butyl rubber, polynorbornene, special urethane elastomers, etc. exhibit excellent loss coefficient values of tan δ-1, 4, 2, s, and 1.3, respectively. However, these materials have difficulty in processability and moldability, and their range of use has been limited.

Recent demands for higher performance and higher quality of various transportation equipment, including precision electronic equipment and automobiles, have never stopped, and the loss coefficient value is not only large in a specific temperature range, but also in a wide temperature range, that is, room temperature. Depending on the application, it is desired to maintain a high Tan δ value from -20°C to around 100°C.

By the way, polyvinyl chloride resin has a long history as one of the five major general-purpose resins, and not only is it economical, but most molding methods have been established. Moreover, it has advantages such as being an amorphous resin and being easily combined with inorganic/metal fillers and softeners.

The loss coefficient of polyvinyl chloride alone is approximately 1.1 at around 90°C.
If 100 parts by weight of di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP), a typical plasticizer, is added to 100 parts by weight of polyvinyl chloride resin, the loss coefficient will have a peak value of The temperature drops to around 5°C and the peak value drops to about 0.7. This phenomenon was understood to be natural when one considers that different molecules are mixed into the single molecular chain of polyvinyl chloride, resulting in a broadening of the relaxation time distribution. However, as a result of our recent studies, we found that when a very limited type of plasticizer, represented by dicyclohexyl phthalate (hereinafter abbreviated as DCHP), is added to polyvinyl chloride, the peak temperature of the loss factor decreases or the peak value is 1
．． It was found that the value increased to about 6. However, this DCHP has a fatal drawback that it will bleed if added in large amounts or even in small amounts mixed with DOP or the like. Furthermore, the peak loss factor value of 1°6 is also a slightly lower value compared to polynorbornene.

Further, its temperature dependence is large, and the temperature range in which the loss coefficient maintains a value of 05 or more is about 30°C.

[Problems to be Solved by the Invention] The present invention utilizes the characteristics of polyvinyl chloride resin, has a high loss coefficient, or maintains a relatively high loss coefficient over a wide temperature range, and suppresses the bleed phenomenon to absorb vibration energy. The purpose is to provide materials.

[Means for Solving the Problems] The gist of the present invention is that polyvinyl chloride resin,
Made of petroleum resin and plasticizer, polyvinyl chloride resin 1
The present invention relates to a vibration energy absorbing material containing 3 parts by weight or more and 200 parts by weight or less of petroleum resin per 00 type hot section.

The details will be explained below.

In addition to vinyl chloride homopolymers, the polyvinyl chloride resins used in the present invention are generally polyvinyl chloride-based resins such as vinyl acetate, copolymers with ethylene, ethylene/vinyl acetate copolymers, and kraft polymers with polyurethane. Indicates what can be recognized as a resin.

The petroleum resin used in the present invention is obtained by polymerizing C6 to C7 olefins in a mixed state. However, although the maximum value of the loss factor is greatly improved by adding petroleum resin, the degree of this effect varies considerably depending on the composition and molecular weight. That is, it is preferable that the petroleum resin contains 50 wt 90 or more of indene and styrene, which are C9 components, and more preferably, the ratio of indene to styrene is such that styrene accounts for half or more. Further, it is preferable that the number average molecular weight is 500 or more and 1500 or less. Outside these ranges, the value of the loss coefficient decreases.

The amount added is preferably 3 parts by weight or more and 200 parts by weight or less, more preferably 10 parts by weight or more and 100 parts by weight or less, based on 100 parts by weight of the polyvinyl chloride resin. If it is less than 3 parts by weight, the loss factor will not improve much, and if it is added in excess of 200 parts by weight, processability will be extremely deteriorated.

On the other hand, petroleum resins do exhibit excellent effects in improving the loss factor, but the effects vary greatly depending on the type of plasticizer added as the third component. In other words, it is desired that the plasticizer added as the third component used in the present invention be selected from a type that has good compatibility when mixed with polyvinyl chloride, or in other words, a type that has a large loss coefficient. be able to. For example, a phthalate ester having the structure (i) below (R, R2 is a monocyclic hydrocarbon consisting of C3 to C8) has a maximum loss coefficient even when mixed alone with polyvinyl chloride resin. 1.4 to 1.8.

Specific examples of such compounds include DCH and P.

Examples include dimethyl chlorohequine phthalate and diphenyl phthalate (DPP).

In addition, phosphoric acid ester R30-P-OR4Nj) having the following structure (jf) (R3 to R1 are aromatic monocyclic hydrocarbons consisting of C6 to C9) was mixed alone with polyvinyl chloride resin. Even in this case, the maximum value of the loss coefficient is 0.8 to 1.3.

Specific examples include tricresyl phosphate (TCP) and tricylenyl phosphate (TXP).

These compounds having structures (i) and (ij) can be used alone or in a mixture of two or more.

In particular, the phthalate ester used in the present invention has a poor plasticizing efficiency, so even if a considerable amount is added, is there a drawback that it is difficult to reduce the temperature to the temperature range where it shows the maximum loss coefficient or the room temperature range where it is most often used as a vibration energy absorbing material? This drawback can be compensated for by using a phosphoric acid ester in combination.

Furthermore, the phthalate ester used in the present invention has the disadvantage that it tends to bleed after molding, but it has the advantage that bleeding can be suppressed by adding petroleum resin and phosphate ester.

The amount of these two types of ester plasticizers to be added cannot be absolutely specified depending on the application, but it is appropriate that the total amount is 5 parts by weight or more and 200 parts by weight or less based on 100 parts by weight of the vinyl chloride resin. If the amount added is less than 5 parts by weight, no significant improvement in the loss factor can be expected.

If more than 200 parts by weight is added, the plasticizer bleeds out and becomes stiff, which is not very preferable.

The vibrational energy absorbing material according to the invention includes calcium carbonate, which is commonly added to polyvinyl chloride resin.

Inorganic fillers such as talc, flame retardants such as antimony trioxide and zinc borate, and flake fillers such as mica and graphite may be added as necessary.

In addition, if necessary, NBR (acrylonitrile-butadiene rubber) E, which is usually used for modifying polyvinyl chloride resin, can be used.
It can also be blended with VA (ethylene-vinyl acetate), a polymer, and acrylic resins. Furthermore, it can be blended with Kumaron resin and Kinren resin, which are often used in vibration energy absorbing materials.

The vibration energy absorbing material according to the present invention can be freely molded and processed using conventional polyvinyl chloride resin molding and processing techniques such as calendering, extrusion, injection ratio molding, one-foam molding, and 11H compression molding.

In addition, the vibration energy absorbing material obtained by the present invention can be applied to wood, including metal materials such as stainless steel plates and aluminum plates,
It can also be used in combination with other materials such as inorganic materials.

[Example] The present invention will be explained below using examples.

Example 1 Polyvinyl chloride resin (Lyuron TH-1000) [
Tosoh Corporation] 100 parts by weight, petroleum resin (Betcol LX) [Tosoh Co., Ltd., 47 parts by weight, dicyclohexyl phthalate (DCH) as a phthalate ester.
P) [170 parts by weight manufactured by Osaka Organic Chemical Co., Ltd., 5 parts by weight of 0G-756 [manufactured by Suikagaku Kagaku Co., Ltd.] as a stabilizer, antimony trioxide (Atotsu-S) as a flame retardant [Nippon Shinko ( Co., Ltd., and kneaded with a roll for about 5 minutes at a temperature of 140° C. to obtain a sheet with a thickness of 0.2.

Example 2 Polyvinyl chloride resin (Lyuron TH-1000) [
Tosoh Corporation] 87 parts by weight, ETHI vinyl chloride copolymer resin (Lyuron E-2800) [Tosoh Corporation] 13 parts by weight, total amount of indene and styrene 8
Petroleum resin (Betcol LX-T) [
30 parts by weight of Co manufactured by Tosoh Corporation, 70 parts by weight of tricylenyl phosphate (TXP) [manufactured by Ohe Kagaku Co., Ltd.] as a ricillin ster, 0G-756 [manufactured by Suiko Kagaku Co., Ltd.] as a stabilizer. 5 parts by weight of antimony trioxide (Atotsu-S) as a flame retardant (parts by weight of core manufactured by Nippon Seiko Co., Ltd.) were mixed and kneaded with rolls at a temperature of 140°C for about 5 minutes to obtain a sheet with a thickness of 0.2 mm. .

Example 3 Polyvinyl chloride resin (Lyuron TH-1000) [
Tosoh Co., Ltd.] 87 parts by weight, Ethiech vinyl chloride copolymer resin (Lyuron E-2800) [Tosoh Co., Ltd.] 13 parts by weight 1 Petroleum resin (Betcol LX-T
) [manufactured by Tosoh Corporation] 39 parts by weight, dicyclohexyl phthalate (DCHP) as a phthalate ester [0 parts by weight of Core manufactured by Osaka Organic Chemical Co., Ltd. and di-2-ethylhexyl phthalate (DOP, Vinicizer 80) ) [manufactured by Kao Corporation] 7.5 parts by weight, triquinrenyl phosphate (TXP) as a phosphoric acid ester [manufactured by Ohe Kagaku Co., Ltd.] 27.5 parts by weight, 0G-756 [as a stabilizer] 35 parts by weight, manufactured by Suikagaku Kagaku Co., Ltd. Antimony trioxide (Atotsux-S) as a flame retardant [parts by weight of core manufactured by Nippon Seiko Co., Ltd., calcium carbonate (Whiten P-1) as an inorganic filler
30) [200 parts by weight of Shiraishi Calcium Co., Ltd.
Mica (Sujirite Mica 150-5) [Kuraray Co., Ltd.
40 parts by weight of the following materials were mixed and kneaded with rolls at a temperature of 140° C. for about 5 minutes to obtain a sheet having a thickness of 0.2++n++.

Example 4 Ethylene-vinyl chloride copolymer resin (Lyuron E-28
(DCHP)
70 parts by weight of [manufactured by Osaka Organic Chemical Co., Ltd.], 70 parts by weight of tricylenyl phosphate (TXP) [manufactured by Ohe Kagaku Co., Ltd.] as a phosphoric acid ester, and 0G- as a stabilizer.
3 parts by weight of 756 [manufactured by Suiko Kagaku Co., Ltd.], 7 parts by weight of antimony trioxide (Atotsu-S) [manufactured by Kuchimoto Tateko Co., Ltd.] as a flame retardant, and zinc borate (Cincinporide 23).
35) [UNITED 5TATES BOR
AX & CHEMICAL C0RPORAT
20 parts by weight of ION''J, 25 parts by weight of calcium carbonate (Whitton P-30) manufactured by Shiroishi Calcium Co., Ltd. as an inorganic filler, 10 parts of mica (4k) [manufactured by Shiroishi Kogyo Co., Ltd.] Parts by weight were mixed and roll-kneaded at a temperature of 140° C. for about 5 minutes to obtain a sheet with a thickness of 0.2 m+n.

Example 5 100 parts by weight of polyvinyl chloride-polyurethane graft resin (Dominus Ni-800F) [manufactured by Tosoh Corporation], 40 parts by weight of petroleum resin (Betcol LX-T), dicyclohexyl as phthalate ester Phthalate (DC
HP) [manufactured by Osaka Organic Chemical Co., Ltd.] 30 parts by weight, liquid barium zinc stabilizer (6227) as a stabilizer
[Manufactured by Akishima Chemical Co., Ltd., 31.0 parts by weight, granular barium zinc stabilizer (6226) [Manufactured by Akishima Chemical Co., Ltd.] 2.6 parts by weight, phosphorous ester stabilizer (4342)
[30.6 parts by weight of Akishima Kagaku Co., Ltd. and 50 parts by weight of recycled butyl rubber were mixed and kneaded with rolls at a temperature of 140° C. for about 5 minutes to obtain a sheet with a thickness of 0.2 mm.

Comparative Example 1 Ethylene-vinyl chloride copolymer resin (Lyuron E-28
00) [Manufactured by Tosoh Corporation] 100 parts by weight, di-2-ethylhexyl phthalate (DO
100 parts by weight of P Vinicizer 80) [manufactured by Kao Corporation] and 0G-756 [manufactured by Suikagaku Kagaku Co., Ltd.] as a stabilizer.
6 parts by weight and 7 parts by weight of antimony trioxide (Atox-8) [manufactured by Nippon Seiko Co., Ltd.] as a flame retardant were mixed together and kneaded with rolls at a temperature of 140°C for about 5 minutes to form a mixture with a thickness of 0.2 cm. Got a sheet.

Comparative Example 2 The same system as in Example 2 except that the petroleum resin was removed was mixed and kneaded with rolls at a temperature of 140° C. for about 5 minutes to obtain a sheet with a thickness of 0.2 mm.

Comparative Example 3 The same system as in Example 3 except that the petroleum resin was removed was mixed and kneaded with rolls at a temperature of 140° C. for about 5 minutes to obtain a sheet with a thickness of 0.2 mm.

[Evaluation of loss coefficient (tan δ)] Using a viscoelasticity analyzer R5An [Rheometrics Far East Co., Ltd.], which is a measuring device based on a non-resonant forced vibration method, the heating rate was 2°C/min, 1fFJ.
The maximum value of the loss coefficient (tan δ) and the temperature range in which the loss coefficient was 0.5 or more were measured at a constant frequency of 10 Hz.

The results are shown in Table 1. Example 1. ．． 2 and 3.4 both recorded high values of tan δ> 1.5, and ta
The temperature range showing the value of nδ≧0.5 also extends to about 30° C. or more.

Further, in Example 5, although the peak value of tan δ is as low as 0.89, the temperature range in which the value of tan δ≧(−)5 is shown extends from 50° C. to 50° C. or higher. On the other hand, the comparative example that does not contain Ishiura resin has a low peak value of tan δ, and the temperature range showing the value of [an δ≧05] is also below 30°C.

Table 1 [Effects of the invention] From the above explanation, it is clear that the present invention (i. By increasing the peak value of tan δ to 1.5 or more, or expanding the temperature range in which tan δ ≥ 0.5 to 50°C or more, it is possible to increase the peak value of tan δ to 1.5 or more, and expand the temperature range in which tan δ ≧ 0.5 to 50°C or more. 1 can be provided with a suppressed vibration energy absorber.

Claims (1)

[Claims] (1) A vibration energy absorbing material made of a polyvinyl chloride resin, a petroleum resin, and a plasticizer, and containing 3 parts by weight or more and 200 parts by weight or less of a petroleum resin per 100 parts by weight of the polyvinyl chloride resin.