JPH0559241A - Vibration-absorbing material - Google Patents

Abstract

PURPOSE:To provide the title material which can be easily colored in various colors and has a high loss factor. CONSTITUTION:The title material is prepd. by compounding 100 pts.wt. polyvinyl chloride resin with 3-20 pts.wt. hydrogenated petroleum resin and 5-200 pts.wt. plasticizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is used in various fields such as transportation equipment, precision electronic equipment, and acoustic equipment for the purpose of improving the reaction speed and measurement accuracy and the sound quality by controlling vibration. The present invention relates to a polyvinyl chloride resin composition having excellent vibration energy absorption performance.

[0002]

2. Description of the Related Art Conventionally, butyl rubber has been most often used as a vibration energy absorbing material. Recently, polynorbornene and special urethane elastomers have been found to have higher performance, and have been attracting attention. The primary evaluation of these vibration energy-absorbing materials is the storage elastic modulus (E ′) and loss coefficient (tan δ = loss elastic modulus (E ″) / storage elastic modulus (E ′)) obtained by viscoelasticity measurement of the material. Done.

For designing a vibration energy absorbing material, the larger the loss coefficient is, and the storage elastic modulus has an optimum value depending on the form used. These two
The two factors are usually highly temperature dependent. That is, the storage elastic modulus gradually decreases as the temperature rises, and usually sharply decreases from the 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 before and after that.

Therefore, conventionally, the standard required for such a vibration energy absorbing material has been to have a high loss coefficient in the temperature range in which the material is used. On the other hand, the storage elastic modulus can be adjusted to an optimum value because the value can be adjusted in a considerable range by adding an inorganic or metallic filler, a softening agent, or rubber. Therefore, butyl rubber, polynorbornene, and special urethane elastomer have excellent loss coefficients of tan δ = 1.4, 2.8, and 1.3, respectively. However, these materials were difficult to process and form, and their use range was limited.

The demand for higher performance and higher quality of various transportation equipment such as precision electronic equipment and automobiles is unavoidable, and not only the value of the loss coefficient is large in a specific temperature range but also a wide temperature range. That is, it is desired to maintain a high tan δ value from room temperature to around 60 ° C., or from −20 ° C. to around 100 ° C. depending on the application.

By the way, polyvinyl chloride resin has a long history as one of the five general-purpose resins, and most molding methods have been established as well as economical efficiency. Moreover, it is an amorphous resin and has the advantage that it can be easily compounded with an inorganic / metal filler or a softening agent. The loss factor of polyvinyl chloride alone has a peak value of about 1.1 at around 90 ° C., but a typical plasticizer for this is di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP). When 100 parts by weight of polyvinyl chloride resin is added to 100 parts by weight of the polyvinyl chloride resin, the peak temperature of the loss factor is around 5 ° C. and the peak value is about 0.7.
It will fall to the extent. It was understood that this phenomenon should be understood if heterogeneous molecules were mixed in the polyvinyl chloride single molecular chain, and as a result, the relaxation time distribution was broadened. However, as a result of our recent studies, when the plasticizer and petroleum resin of a very limited kind are added to polyvinyl chloride, the peak temperature of the loss coefficient is lowered, but the peak value is about 2.0. Was found to rise. However, the composition obtained here is colored brown as compared with a usual soft polyvinyl chloride composition, and there is a problem that coloring by a pigment, a dye or the like is hindered.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an excellent vibration energy absorbing material which has a high loss coefficient while taking advantage of the characteristics of polyvinyl chloride resin and which does not hinder pigment coloring. To do.

[0008]

SUMMARY OF THE INVENTION In view of the above-mentioned current situation, the inventors of the present invention have made extensive studies, and as a result, completed the present invention.

That is, a polyvinyl chloride resin, a hydrogenated petroleum resin, and a plasticizer are used.
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 a hydrogenated petroleum resin and 5 parts by weight or more and 200 parts by weight or less of a plasticizer per 0 parts by weight.

The details will be described below.

The polyvinyl chloride resin used in the present invention includes vinyl chloride homopolymers, vinyl acetate, copolymers with ethylene and graft polymers with polyurethane, which can be generally recognized as polyvinyl chloride resins. Indicates.

The hydrogenated petroleum resin used in the present invention means styrene, α-methylstyrene, vinyltoluene, vinylxylene, indene, methylindene, ethylindene, pentene, hexene and butadiene which are commonly used as raw materials for petroleum resins. , Cyclopentadiene, dicyclopentadiene, octadiene, and other olefins, boiling point -20 to 28 containing one or more diolefins as a polymerization component
So-called petroleum resin obtained by polymerization of naphtha cracked oil at 0 ° C. is mixed with hydrogen in the presence of known hydrogenation catalysts such as nickel-diatomaceous earth, Raney-nickel, platinum oxide, Raney-cobalt, Hydrogen is obtained by reducing unsaturated bonds in petroleum resin to saturated bonds or reducing aromatic hydrocarbons to alicyclic hydrocarbons. At this time, although the degree of coloring of the hydrogenated petroleum resin obtained varies depending on the degree of hydrogenation, it is 700 cm as measured by infrared absorption spectrum.
It is preferable that the hydrogenation rate calculated from the absorbance of ^-1 is 70% or more.

The maximum value of the loss coefficient is greatly improved by the addition of petroleum resin, but the degree of the effect is considerably different depending on the composition and the molecular weight. That is, preferably those containing indene and styrene C ₉ component 50% by weight or more as the petroleum resin, more ratio between indene and styrene those occupied styrene more than half desirable. Also,
The molecular weight thereof is preferably 500 or more and 1500 or less. If the value is out of these ranges, the value of loss factor decreases.

Polyvinyl chloride resin 10 is added.
The amount 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 with respect to 0 parts by weight. If it is less than 3 parts by weight, the loss coefficient is not so improved, and if it is added in excess of 200 parts by weight, the workability is extremely deteriorated.

On the other hand, the hydrogenated petroleum resin certainly exhibits an excellent effect in improving the loss coefficient, but the effect greatly differs depending on the kind of the plasticizer added as the third component. That is, the plasticizer added as the third component used in the present invention also has good compatibility when mixed with polyvinyl chloride, in other words, a much larger effect is desired when selected from the types having a large loss coefficient. be able to. For example, a phthalate ester having the following structure (1)

[0016]

[Chemical 1] (R ₁ and R ₂ are monocyclic hydrocarbons composed of C _{3 to} C ₈ ) has a maximum loss coefficient of 1.4 to 1.8 even when mixed alone with a polyvinyl chloride resin.

Specific examples of such compounds include dicyclohexyl phthalate, dimethyl cyclohexyl phthalate and diphenyl phthalate.

Further, a phosphoric acid ester having the following structure (2)

[0019]

[Chemical 2] (R _{3 to} R ₅ are aromatic monocyclic hydrocarbons composed of C _{6 to} C ₉ ) has a maximum loss coefficient of 0.8 to 1.3 even when mixed alone with a polyvinyl chloride resin. Show.

Specific examples include tricresyl phosphate and trixylenyl phosphate.

The compounds having the structures (1) and (2) can be used alone or in admixture of two or more.

In particular, since the phthalate ester used in the present invention has poor plasticization efficiency, even if a considerable amount of it is added, the temperature range exhibiting the maximum loss coefficient is unlikely to fall to the room temperature range most used as the vibration energy absorber. Although it has drawbacks
This defect can be compensated by using a phosphate ester together.

Further, the phthalic acid ester used in the present invention has a drawback that it is easily bleed after molding,
It is an advantage that the addition of hydrogenated petroleum resin and phosphoric acid ester can suppress bleeding.

The amount of these two types of ester plasticizers to be added cannot be unconditionally specified depending on the use, 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, the loss coefficient cannot be improved so much. On the other hand, when it is added in an amount of more than 200 parts by weight, the tackiness becomes severe due to the bleeding of the plasticizer, which is not preferable.

The vibration energy absorbing material according to the present invention comprises:
Inorganic fillers such as calcium carbonate and talc that are usually added to polyvinyl chloride resins, flame retardants such as antimony trioxide and zinc borate, and flaky fillers such as mica and graphite. Etc. can be added as needed.

If desired, it may be blended with acrylonitrile-butadiene rubber, ethylene vinyl acetate copolymer, acrylic resin, etc., which are usually used for modifying polyvinyl chloride resins.

The vibration energy absorbing material according to the present invention is a calendar which is a conventional molding method of polyvinyl chloride resin.
It can be freely molded by a method such as processing, extrusion processing, injection molding, foam molding, compression molding and the like.

The vibration energy absorbing material obtained according to the present invention has a high precision in the manufacturing process of a supporting member, an electronic component manufacturing line, etc. in which precision is affected by vibration such as precision electronic equipment and precision measuring equipment. It can be used as a vibration-proof material for required equipment, fixed members such as packing and gaskets, and laminated members such as audio equipment. In addition, it can be attached directly to areas of high vibration such as automobiles and industrial equipment to suppress vibration, or can be used in combination with other materials such as wood and inorganic materials such as metal materials such as stainless steel plates and aluminum plates. it can.

[0029]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 Ethylene-vinyl chloride copolymer resin (Leuron E-2)
800, Toso Co., Ltd.) 100 parts by weight, hydrogenated petroleum resin (Alcon P-100, Arakawa Chemical Industry Co., Ltd.) 2
0 part by weight, 70 parts by weight of dicyclohexyl phthalate as a phthalate ester (DCHP, manufactured by Osaka Organic Chemical Co., Ltd.), trixylenyl phosphate as a phosphate ester (TXP, manufactured by Daihachi Chemical Co., Ltd.) 70 parts by weight, 5 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 Seishaku Co., Ltd.) as a flame retardant were mixed at a temperature of 150. Roll kneading was carried out at ℃ for about 5 minutes to obtain a sheet having a thickness of 0.2 mm. The sheet obtained here was visually white.

Example 2 Instead of the hydrogenated petroleum resin in Example 1, 20 parts by weight of a hydrogenated petroleum resin (Alcon M-100, manufactured by Arakawa Chemical Industry Co., Ltd.) in which some aromatic rings were left was used. The target composition was obtained by exactly the same operation except the above. The sheet obtained here was visually white.

Example 3 100 parts by weight of polyvinyl chloride-polyurethane graft resin (Dominus K-800F, manufactured by Toso Corporation), hydrogenated petroleum resin (Alcon P-100, manufactured by Arakawa Chemical Industry Co., Ltd.) ) 40 parts by weight, dicyclohexyl phthalate as a phthalate ester (DCHP, Osaka Organic Chemical Co., Ltd.)
30 parts by weight, liquid stabilizer barium zinc-based stabilizer (6227, manufactured by Akishima Chemical Co., Ltd.) 1 part by weight, granular barium zinc-based stabilizer (6226, Akishima Chemical Co., Ltd.)
2.6 parts by weight, phosphite ester stabilizer (434
2, 0.6 part by weight of Akishima Chemical Co., Ltd. and 50 parts by weight of regenerated butyl rubber were 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. The sheet obtained here was visually white.

Comparative Example 1 A target composition was obtained by the same procedure as in Example 1 except that the hydrogenated petroleum resin was not added. The sheet obtained here was visually white.

Comparative Example 2 Instead of the hydrogenated petroleum resin in Example 1, an aromatic petroleum resin (Petcole LX-HS, manufactured by Toso Co., Ltd.) 20
The target composition was obtained by the same procedure except that the parts by weight were used. The sheet obtained here was visually brown.

Comparative Example 3 In Example 3, instead of the hydrogenated petroleum resin, an aromatic petroleum resin (Petcole LX-HS, manufactured by Toso Co., Ltd.) 40
The target composition was obtained by the same procedure except that the parts by weight were used. The sheet obtained here was visually brown.

[Evaluation of Loss Coefficient (tan δ)] Example
The sheet of the composition obtained in the comparative example is a measuring device based on the non-resonance type forced vibration method, which is a viscoelasticity analyzer-RSAI.
Using I (Rheometrics Fast), the loss coefficient was measured at a heating rate of 2 ° C./min and a measurement frequency of 10 Hz. Table 1 shows the peak value of the loss coefficient and the temperature at that time.

[0037]

[Table 1]

[0038]

As is apparent from the above description, according to the present invention, by combining a polyvinyl chloride resin with a hydrogenated petroleum resin, and further with a specific phthalate ester and phosphate ester, It is possible to obtain a vibration energy absorbing material which can be easily colored in various colors and has a high loss coefficient.

Claims (1)

[Claims] 1. A polyvinyl chloride resin, a hydrogenated petroleum resin and a plasticizer, wherein the hydrogenated petroleum resin is contained in an amount of 3 parts by weight or more and 200 parts by weight or less and a plasticizer of 5 parts by weight per 100 parts by weight of the polyvinyl chloride resin. A vibration energy absorbing material comprising at least 200 parts by weight.