JP3177654B2 - Vibration energy absorber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention improves operation response speed and measurement accuracy and improves sound quality by controlling vibration in the fields of various transportation equipment, precision electronic equipment, and audio equipment. The present invention relates to a vibration energy absorber composed of a polyvinyl chloride resin composition having excellent vibration energy absorption performance and used for the purpose of causing vibration energy absorption.

[Prior Art] Conventionally, butyl rubber is most often used as a vibration energy absorbing material. Recently, polynorbornene, special urethane-based elastomers, and the like have been found to have higher performance and have been attracting attention. The primary evaluation of these vibration energy absorbing materials is made by the storage elastic modulus (E ') and the loss coefficient (Tan δ = loss elastic modulus (E ") / storage elastic modulus (E')) obtained by measuring the viscoelasticity of the material. You.

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

Therefore, conventionally, as a criterion required for such a vibration energy absorbing material, first, a material having a high loss coefficient in a temperature range in which the material is used has been used.

On the other hand, the storage modulus can be adjusted to an optimum value because the value can be adjusted within a considerable range by adding an inorganic or metal filler, a softening agent, rubber, or the like. Therefore, butyl rubber, polynorbornene, special urethane-based elastomers, and the like have excellent values of the loss coefficient of tan δ = 1.4, 2.8, 1.3 at maximum. However, these materials have difficulties in workability and formability, and their use range is limited.

The demand for higher performance and higher quality of various types of transportation equipment such as precision electronic devices and automobiles has never stopped, and the loss coefficient is not only large in a specific temperature range but also in a wide temperature range, that is, room temperature. It is desired to maintain a high Tan δ value from −20 ° C. to about 100 ° C. depending on the application from to about 60 ° C.

By the way, polyvinyl chloride resin has a long history as one of the five large general-purpose resins, and most molding methods have been established as well as economical. Moreover, being an amorphous resin,
It has advantages such as easy compounding with inorganic / metal fillers and softeners. The loss factor of polyvinyl chloride alone is
It has a peak value of about 1.1 at around 90 ° C., and 100 parts by weight of a typical plasticizer, di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP), is added to 100 parts by weight of the polyvinyl chloride resin. And the peak temperature of the loss coefficient drops to about 5 ° C., and the peak value also drops to about 0.7. This phenomenon was naturally understood when it is considered that heterogeneous molecules are mixed in a single molecular chain of polyvinyl chloride, and as a result, the distribution of relaxation time is widened. However, as a result of our recent studies, 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 coefficient decreases, but the peak value is 1 .
It was found to rise to around 6. But this D
CHP has a fatal disadvantage that it bleeds when added in a large amount or mixed with a small amount such as DOP. Furthermore, the value of the peak value of the loss coefficient of 1.6 is slightly lower than that of polynorbornene. Further, its temperature dependence is large, and the temperature range in which the loss coefficient maintains a value of 0.5 or more is about 30 ° C.

[Problems to be Solved by the Invention] The present invention takes advantage of the characteristics of polyvinyl chloride resin, has a high loss coefficient, or maintains a relatively high loss coefficient in a wide temperature range, and suppresses bleeding phenomenon. The purpose is to provide materials.

[Means for Solving the Problems] The gist of the present invention consists of a polyvinyl chloride resin, a petroleum resin and a plasticizer, and a total of 50 wt% of an indene component and a styrene component per 100 parts by weight of the polyvinyl chloride resin. % Or more, and the number average molecular weight is 500 or more and 1500
The present invention relates to a vibration energy absorbing material containing the following petroleum resin in an amount of 3 to 200 parts by weight and a plasticizer in an amount of 5 to 200 parts by weight.

 Hereinafter, the details will be described.

The polyvinyl chloride resin used in the present invention is generally a vinyl chloride resin such as a vinyl chloride homopolymer, a copolymer with vinyl acetate, ethylene, an ethylene / vinyl acetate copolymer, or a graft polymer with polyurethane. It shows what can be recognized as a resin.

The petroleum resin used in the present invention is obtained by polymerizing leave olefins mixed state of C ₅ -C _9. However, the addition of petroleum resin greatly increases the maximum value of the loss coefficient, but the degree of the effect varies considerably depending on the structure and the molecular weight. That is, as the petroleum resin are those containing indene and styrene C ₉ components above 50 wt%, more ratio of indene and styrene better accounted styrene more than half desirable. The number average molecular weight is 500 or more1
500 or less. Outside these ranges, the value of the loss factor decreases.

The addition amount is preferably 3 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. If the amount is less than 3 parts by weight, the loss coefficient is not so much improved, and if it exceeds 200 parts by weight, the processability is extremely deteriorated.

On the other hand, petroleum resins certainly exhibit an excellent effect of improving the loss coefficient, but the effect differs greatly depending on the type of the plasticizer added as the third component. In other words, the plasticizer to be added as the third component used in the present invention also has good compatibility when mixed with polyvinyl chloride. be able to. For example, a phthalic acid ester having the following structure (i) (R ₁ and R ₂ are monocyclic hydrocarbons composed of C _{3 to} C ₈ ) have a maximum loss coefficient of 1.4 to 1.8 even when they are mixed alone with a polyvinyl chloride resin.

As such compounds, specifically, DCHP, dimethylcyclohexyl phthalate, diphenyl phthalate (DP
P) and the like.

A phosphate ester having the following structure (ii): (R _{3 to} R ₅ are aromatic monocyclic hydrocarbons composed of C _{6 to} C ₉ ) have a maximum loss coefficient of 0.8 to 1.3 even when used alone and mixed with a polyvinyl chloride resin.

Specifically, tricresyl phosphate (TCP), trixylenyl phosphate (TXP) and the like can be mentioned.

These compounds having the structures (i) and (ii) can be used alone or in combination of two or more.

Particularly, the phthalic acid ester used in the present invention has a drawback that the temperature range showing the maximum loss coefficient is not easily lowered to the room temperature range most frequently used as a vibration energy absorbing material even if a considerable amount is added because the plasticizing efficiency is low, This disadvantage can be compensated for by using a phosphate ester in combination.

Further, the phthalic acid ester used in the present invention has a disadvantage that it easily bleeds after molding, but it is advantageous that bleeding can be suppressed by adding a petroleum resin and a phosphoric acid ester.

The amount of these plasticizers to be added cannot be specified unconditionally 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 addition amount is less than 5 parts by weight, the improvement of the loss coefficient cannot be expected much. On the other hand, if it is added in excess of 200 parts by weight, stickiness becomes severe due to bleeding of the plasticizer, which is not preferred.

Examples of the vibration energy absorbing material according to the present invention include inorganic fillers such as calcium carbonate and talc which are usually added to polyvinyl chloride resin, flame retardants such as antimony trioxide and zinc borate, mica and graphite. Representative flake fillers and the like can be added as needed.

NBR (acrylonitrile-butadiene rubber) EVA which is usually used for modifying polyvinyl chloride resin if necessary
(Ethylene-vinyl acetate copolymer), acrylic resin and the like. Further, it can be blended with a coumarone resin, a xylene resin or the like often used as a vibration energy absorbing material.

The vibration energy absorbing material according to the present invention can be freely formed and processed by a conventional method of forming and processing polyvinyl chloride resin such as calendering, extrusion, injection molding, foam molding and compression molding.

Further, the vibration energy absorbing material obtained by the present invention can be used in combination with other materials such as a metal material such as a stainless steel plate and an aluminum plate, wood, an inorganic material and the like.

EXAMPLES Hereinafter, the present invention will be described with reference to Examples.

Example 1 Polyvinyl chloride resin (Ryuron TH-1000) [manufactured by Tosoh Corporation] 100 parts by weight, the total amount of indene and styrene accounts for 70% by weight or more, and the composition ratio of indene and styrene is 2: 3. Of petroleum resin (petocol LX) [manufactured by Tosoh Corporation] 47 parts by weight, dicyclohexyl phthalate (DCHP) as a phthalate ester “Osaka Organic Chemicals Co., Ltd.
70 parts by weight, OG-756 as a stabilizer [Mizusawa Chemical Co., Ltd.] 5 parts by weight, antimony trioxide (Atox-S) as a flame retardant [Nippon Seimitsu Co., Ltd.] 7 parts by weight And kneaded with a roll at a temperature of 140 ° C. for about 5 minutes to a thickness of 0.2 mm.
Sheet was obtained.

Example 2 Polyvinyl chloride resin (Ryuron TH-1000) [manufactured by Tosoh Corporation] 87 parts by weight, ethylene-vinyl chloride copolymer (Ryuron E-2800) [manufactured by Tosoh Corporation] 13 parts by weight, 30 parts by weight of petroleum resin (Petokol LX-T) [Tosoh Corporation] with a total composition ratio of indene and styrene occupying 80 wt% or more and a composition ratio of indene and styrene of 1: 5, phosphate ester Trixylenyl phosphate (TXP) [manufactured by Daihachi Chemical Co., Ltd.] 70 parts by weight, OG-756 as a stabilizer [Mizusawa Chemical Co., Ltd.] 5 parts by weight, antimony trioxide (Atox-S) as a flame retardant 7) [Nippon Seiko Co., Ltd.] was mixed and roll kneaded at a temperature of 140 ° C. for about 5 minutes to obtain a sheet having a thickness of 0.2 mm.

Example 3 Polyvinyl chloride resin (Ryuron TH-1000) [manufactured by Tosoh Corporation] 87 parts by weight, ethylene-vinyl chloride copolymer resin (Ryuron E-2800) [manufactured by Tosoh Corporation] 13
Parts by weight, petroleum resin (Petokol LX-T) [manufactured by Tosoh Corporation] 39 parts by weight, dicyclohexyl phthalate (DCHP) as a phthalate ester [manufactured by Osaka Organic Chemicals Ltd.] 70 parts by weight, and di-2- 7.5 parts by weight of ethylhexyl phthalate (DOP, Vinylizer 80) [manufactured by Kao Corporation], 27.5 parts by weight of trixylenyl phosphate (TXP) as a phosphate ester [manufactured by Daihachi Chemical Co., Ltd.], OG- as a stabilizer 756 [manufactured by Mizusawa Chemical Co., Ltd.] 5 parts by weight, antimony trioxide (Atox-S) as a flame retardant [manufactured by Nippon Seiko Co., Ltd.] 7 parts by weight, calcium carbonate (whiten P-) as an inorganic filler 30) [Shiraishi Calcium Co., Ltd.]
Was mixed with 40 parts by weight of mica (Szolite Mica 150-S) [manufactured by Kuraray Co., Ltd.], and roll-kneaded at 140 ° C. for about 5 minutes to obtain a sheet having a thickness of 0.2 mm.

Example 4 Ethylene-vinyl chloride copolymer resin (Ryuron E-28)
00), 100 parts by weight of Tosoh Corporation, 40 parts by weight of petroleum resin (petocol LX-HS), and 70 parts by weight of dicyclohexyl phthalate (DCHP) [manufactured by Osaka Organic Chemicals Ltd.] as a phthalate ester Part, Trixylenyl phosphate (TXP) as phosphoric ester [manufactured by Daihachi Chemical Co., Ltd.]
70 parts by weight, 3 parts by weight of OG-756 [manufactured by Mizusawa Chemical Co., Ltd.] as a stabilizer, and 7 parts by weight of antimony trioxide (Atox-S) [manufactured by Nippon Seiko Co., Ltd.] as a flame retardant. , Zinc borate (zinc volite 2335) [UNITED STATES BORA
X & CHEMICAL CORPORATION], 25 parts by weight of calcium carbonate (Whiteton P-30) [manufactured by Shiraishi Calcium Co., Ltd.] as an inorganic filler, mica (4k) [manufactured by Shiraishi Industry Co., Ltd.] Was mixed with a roll at a temperature of 140 ° C. for about 5 minutes to obtain a sheet having a thickness of 0.2 mm.

Example 5 100 parts by weight of a polyvinyl chloride-polyurethane graft resin (Dominus K-800F) (manufactured by Tosoh Corporation), 40 parts by weight of a petroleum resin (Petokol LX-T), and dicyclohexyl phthalate as a phthalate ester ( DCHP) [Osaka Organic Chemicals Co., Ltd.] 30 parts by weight, liquid barium zinc-based stabilizer as stabilizer (6227) [Akishima Chemical Co., Ltd.]
1.0 parts by weight, granular barium zinc-based stabilizer (6226)
2.6 parts by weight of [Akishima Chemical Co., Ltd.], 0.6 parts by weight of phosphite stabilizer (4342) [Akishima Chemical Co., Ltd.], and 50 parts by weight of regenerated butyl rubber are mixed at 140 ° C. for about 5 parts. Roll kneading was performed for 2 minutes to obtain a sheet having a thickness of 0.2 mm.

Comparative Example 1 Ethylene-vinyl chloride copolymer resin (Ryuron E-28)
00) [Tosoh Corporation] 100 parts by weight, 100 parts by weight of di-2-ethylhexyl phthalate (DOP vinylizer 80) [Kao Corporation] as a phthalic acid ester, and OG-756 [Mizusawa] as a stabilizer 6 parts by weight) and 7 parts by weight of antimony trioxide (Atox-S) [manufactured by Nippon Seimitsu Co., Ltd.] as a flame retardant and roll kneading at 140 ° C. for about 5 minutes. Then, a sheet having a thickness of 0.2 mm was obtained.

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

Comparative Example 3 Except for removing the petroleum resin in the composition of Example 3, the same system was mixed and roll-kneaded at a temperature of 140 ° C. for about 5 minutes to obtain a sheet having a thickness of 0.2 mm.

[Evaluation of loss coefficient (tan δ)] Using a viscoelastic analyzer RSA II [Rheometrics Far East Co., Ltd.] which is a measuring device based on the non-resonant forced vibration method, at a heating rate of 2 ° C./min., Measuring frequency of 10 Hz. Thus, the maximum value of the loss coefficient (tan δ) and the temperature region where the loss coefficient is 0.5 or more were measured. Table 1 shows the results. In all of Examples 1, 2, 3, and 4, a high value of tan δ> 1.5 was recorded, and a temperature range showing a value of tan δ ≧ 0.5 also reached about 30 ° C. or more. In Example 5, the peak value of tan δ is as low as 0.89, but the temperature range showing the value of tan δ ≧ 0.5 is over 50 ° C. On the other hand, the comparative example containing no petroleum resin
Is low, and the temperature range showing tan δ ≧ 0.5 is 30 ° C
Is below.

[Effects of the Invention] As is clear from the above description, according to the present invention, tan δ is obtained by compounding a polyvinyl chloride resin with a specific petroleum resin and further with a specific plasticizer such as a phthalate ester and a phosphate ester. The peak value of
A temperature range showing a value of δ ≧ 0.5 can be widened to 50 ° C. or more, and a vibration energy absorber having a suppressed bleed phenomenon can be obtained.

Continuation of front page (56) References JP-A-52-33935 (JP, A) JP-A-62-158777 (JP, A) JP-A-62-270646 (JP, A) JP-A-1-263147 (JP) JP-A-4-15245 (JP, A) JP-A-63-156051 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/06 C08L 57/02

Claims (1)

(57) [Claims] Claims: 1. A polyvinyl chloride resin, a petroleum resin, and a plasticizer, and per 100 parts by weight of the polyvinyl chloride resin,
Contain at least 50wt% of indene component and styrene component in total,
A petroleum resin having a number average molecular weight of 500 or more and 1500 or less and 3 to 200 parts by weight, and a plasticizer of 5 to 200 parts by weight.
A vibration energy absorbing material comprising not more than parts by weight.