JP3151945B2 - Polyvinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used in various fields of transportation equipment, precision electronic equipment, audio equipment and the like for controlling vibrations to improve an operation response speed, a measurement accuracy, and a sound quality. The present invention relates to a polyvinyl chloride resin composition having excellent vibration energy-absorbing performance.

[0002]

2. Description of the Related Art Conventionally, butyl rubber is most often used as a vibration energy absorbing material. Also, recently, polynorbornene and special urethane-based elastomers have been found to have higher performance and have attracted attention.

[0003] The primary evaluation of these vibration energy-absorbing materials is based on storage elastic modulus (E ') and loss coefficient (tan δ = loss elastic modulus (E ") / obtained by measuring the viscoelasticity of the material.
(Storage modulus (E ')).

[0004] In order to design as a vibration energy absorbing material, there is an optimum value as the loss coefficient increases and the storage elastic modulus depends on the form used.

[0005] 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, as a standard conventionally required for such a vibration energy absorbing material, first, it has to have a high loss coefficient in a temperature range where the material is used.

On the other hand, the storage elastic modulus can be adjusted to an optimum value by adding an inorganic or metal filler, a softening agent, rubber, or the like, so that the value can be adjusted within a considerable range. . Therefore, butyl rubber, polynorbornene, special urethane-based elastomers, and the like have a maximum loss coefficient of tan δ = 1.4, 2..
It shows an excellent value of 8,1.3. However, these materials have difficulties in workability and formability, and their use range is limited.

[0008] Further, polyvinyl chloride resin has a long history as one of the five major general-purpose resins, and most molding methods have been established in addition to economic efficiency. In addition, it is advantageous in that it is an amorphous resin, and that it can be easily compounded with an inorganic / metal filler or a softener.

The loss factor of polyvinyl chloride alone has a peak value of about 1.1 at around 90 ° C. However, a typical plasticizer such as di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP) is added to 100 parts by weight of the resin.
If 00 parts by weight are added, the peak temperature of the loss coefficient becomes about 5 ° C., and the peak value is reduced 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 review,
It has been found that when very few types of plasticizers and oligomers are added to polyvinyl chloride, the peak temperature of the loss factor decreases but the peak value increases to about 2.0.
However, if the peak temperature of the loss coefficient of the composition obtained here is compounded around room temperature, which is a general use temperature range,
The resulting composition has a problem that it emits an unpleasant odor due to the influence of the plasticizer and oligomer used here and also deteriorates the weather resistance.

[0010]

SUMMARY OF THE INVENTION The present invention reduces the odor while taking advantage of the characteristics of polyvinyl chloride resin,
An object of the present invention is to provide a polyvinyl chloride resin composition having excellent weather resistance and vibration energy-absorbing performance.

[0011]

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies and as a result have completed the present invention.

That is, in the present invention, 5-200 parts by weight of a phthalic acid ester represented by the following general formula (1) is added to 100 parts by weight of a polyvinyl chloride resin, and a phthalic acid ester represented by the following general formula (2) 5 to 200 parts by weight of a polyvinyl chloride resin composition and the resin composition, wherein 100 parts by weight of the polyvinyl chloride resin is hydrogenated rosin resin or / and alicyclic hydrogenation. The present invention relates to a polyvinyl chloride resin composition containing 3 to 100 parts by weight of a petroleum resin.

[0013]

Embedded image

[0014]

Embedded image Furthermore, the present invention relates to a vibration energy absorbing material comprising these compositions. Hereinafter, the details will be described.

The polyvinyl chloride resin used in the present invention is a random copolymer of at least one of vinyl chloride homopolymer resin, chlorinated vinyl chloride resin, and all monomers copolymerizable with vinyl chloride monomer. A vinyl chloride copolymer resin (for example, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.) obtained by polymerization or block copolymerization, such as a single product of these resins or a mixture of two or more thereof.

[0016] The phthalic acid ester having the structural formula (1) is _a compound R 1, _{R 2} consists of monocyclic hydrocarbon of _C 3 -C _8, R 1, _{R 2} are different and the same And the hydrogen on the ring may be substituted with another substituent. Specifically, dicyclohexyl phthalate (DC
HP), dimethylcyclohexyl phthalate, diphenyl phthalate and the like, but dicyclohexyl phthalate is preferably used. From the viewpoint of processability and economy, the amount of addition is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin.
The amount is preferably not less than 100 parts by weight and not more than 100 parts by weight.

The phthalic acid ester having the structure of the general formula (2) is a monocyclic hydrocarbon in which R ₃ is a C _{3 to} C ₈ ,
R ₄ is a compound composed of an alkyl group having a C _{1 to} C ₆ carbon chain. Specific examples include butyl benzyl phthalate, ethyl benzyl phthalate, butyl hexahydrobenzyl phthalate, and the like, with butyl benzyl phthalate being preferred. The addition amount is preferably 5 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 100 parts by weight of the polyvinyl chloride resin from the viewpoint of processability and economy.

The hydrogenated rosin-based resin in the present invention is dehydrogenated by the transfer of hydrogen between molecules of gum rosin, wood rosin, tall oil rosin (hereinafter referred to as rosin) fatty acid whose main component is abietic acid, and is stable. Rosin obtained by the reaction of generating dehydroabietic acid having an aromatic ring and hydrogenated dihydroabietic acid, polymerized rosin containing dimer of rosin as a main component, rosin as methyl alcohol, glycerin, pentaerythritol Rosin ester or the like esterified by the above reaction with hydrogen gas in the presence of a catalyst. These include various types including modified products, but hydrogenated rosin esters are preferred in view of weather resistance, and esters based on tetrahydroabietic acid are particularly preferred.

[0019] Nuclear water aromatic petroleum resin a C ₉ fraction was cationically polymerized in aluminum or BF ₃ catalysts chloride containing alicyclic hydrogenated petroleum styrenes naphtha cracked oil and resin or indene It is classified into two types: an additive and a hydrogenated product of a dicyclopentadiene-based thermal polymer, and a nuclear hydrogenated product of an aromatic petroleum resin is particularly preferred. The hydrogenation rate of the unsaturated bond is preferably 80 to 99%, particularly preferably 80 to 90%, in consideration of the weather resistance of the petroleum resin and the compatibility with the polyvinyl chloride resin.
Is preferred.

The hydrogenated rosin resin and / or alicyclic hydrogenated petroleum resin is added in an amount of 3 to 100 parts by weight based on 100 parts by weight of the polyvinyl chloride resin from the viewpoint of processability and economy. Parts by weight, preferably 5 parts by weight or more and 5 parts by weight or more.
0 parts by weight or less.

When the phthalic acid ester represented by the general formula (1) used in the present invention is used alone, the loss factor is greatly improved. However, this phthalate ester has poor plasticizing efficiency, has difficulty in exhibiting a high loss factor near room temperature, and has a drawback that it easily bleeds after molding. To solve this drawback without reducing the loss factor, we have previously found certain phosphate ester and petroleum resin combinations. However, the combined use of these causes generation of off-flavors and reduction of weather resistance. The use of the phthalic acid ester represented by the general formula (2), a hydrogenated rosin-based resin, or an alicyclic petroleum resin used in the present invention in combination with the phthalic ester of the general formula (1) causes generation of off-flavor and weather resistance. It has now been found that the loss factor can be significantly improved without any decrease.

The polyvinyl chloride resin composition according to the present invention contains DOP and dioctyl sebacate (D) which are usually added to the polyvinyl chloride resin to such an extent that the performance is not deteriorated.
OS) and the like, inorganic fillers such as calcium carbonate and talc, flame retardants such as antimony trioxide and zinc borate, and vibration energy absorbers such as mica and graphite. Flaky fillers and the like can be added as needed.

The polyvinyl chloride resin composition according to the present invention can be freely formed by a conventional method such as calendering, extrusion, injection molding, foam molding, compression molding, etc. be able to.

The vibration energy obtained by the present invention
Absorbents are used for supporting members of equipment such as precision electronic equipment and precision measuring equipment, etc., whose accuracy may be affected by vibration, fixing members such as packing and gaskets, laminated members and chassis of audio equipment, etc. it can. It is also used to control vibration by attaching it directly to highly vibrating parts such as automobiles and industrial equipment.It is also used on the legs of precision equipment to prevent vibration transmission from the floor. It can be used in combination with other materials such as a metal material such as an aluminum plate, wood, an inorganic material, and the like.

[0025]

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

(Examples 1 to 7) Ethylene-vinyl chloride copolymer (Rulon E-2800, manufactured by Tosoh Corporation)
Polyvinyl chloride (Ryuron TH-1000, manufactured by Tosoh Corporation), vinyl chloride-urethane copolymer (Dominas K-800F, manufactured by Tosoh Corporation), dicyclohexyl phthalate (DCHP, manufactured by Osaka Organic Chemical Co., Ltd.), Dimethylcyclohexyl phthalate (EDENOL 344, manufactured by Henkel Hakusui Co., Ltd.), butylbenzyl phthalate (BB
P, manufactured by Daihachi Chemical Industry Co., Ltd.), di-2-ethylhexyl phthalate (Vinicizer 80K, manufactured by Kao Corporation),
Hydrogenated rosin ester (KE-311, manufactured by Arakawa Chemical Industries, Ltd.), alicyclic hydrogenated petroleum resin (ALCON M-9)
0, M-100, manufactured by Arakawa Chemical Industry Co., Ltd.), OG-756 (manufactured by Mizusawa Chemical Co., Ltd.) as a stabilizer, and antimony trioxide (ATOX-S, manufactured by Nippon Seimitsu Co., Ltd.) as a flame retardant. The mixture was mixed at the mixing ratio shown in Table 1, and roll-kneaded at a temperature of 150 ° C. for 5 minutes to obtain a target composition.

(Comparative Examples 1 to 5) In addition to the materials used in the examples, a phosphate ester (tricresyl phosphate.TC)
P, manufactured by Daihachi Chemical Industry Co., Ltd.) and petroleum resin (Ryuron LX-HS, manufactured by Tosoh Corporation) are mixed in the mixing ratio shown in Table 2, and roll-kneaded at a temperature of 150 ° C. for 5 minutes. Was obtained.

[Evaluation of Loss Factor (tan δ)]
The composition obtained in the comparative example was pressed at 180 ° C.
A sheet having a thickness of mm was prepared. Using this sheet, a viscoelastic analyzer RSAII (manufactured by Rheometrics Fast Co., Ltd.), which is a measuring device based on the non-resonant type forced vibration method, heats up at a rate of 2 ° C./min and a measuring frequency of 10 Hz.
Was used to measure the loss factor. Table 3 shows the peak value of the loss coefficient at this time and the temperature at that time.

[Evaluation of Surface Condition] The compositions obtained in Examples and Comparative Examples were pressed at 180 ° C. to produce sheets having a thickness of 2 mm. The sheet was allowed to stand in a constant temperature room at a temperature of 23 ° C. and a humidity of 50%, and the bleeding state of the surface was visually observed. Table 3 shows the results.

[Evaluation of Odor] The compositions obtained in Examples and Comparative Examples were pressed at 180 ° C. to produce sheets having a thickness of 2 mm. By directly smelling the smell of this sheet, the presence or absence of an unusual smell was confirmed. Table 3 shows the results.

[Evaluation of Weather Resistance] The compositions obtained in Examples and Comparative Examples were pressed at 180 ° C. to produce sheets having a thickness of 2 mm. The sheet was attached to a screening and evaluation apparatus (ATLAS-UVCON, manufactured by Toyo Seiki Seisaku-Sho, Ltd.) for ultraviolet light and humidity, and subjected to a total of 200 weather resistance tests at 50 ° C. in a cycle of 8 hours of ultraviolet light exposure to 4 hours of wet exposure. The test was performed for a while, and the change of the sheet surface at that time was observed. Table 3 shows the results.

[0032]

As is apparent from the above description, according to the present invention, a specific phthalic acid ester, or a phthalic acid ester, a hydrogenated rosin-based resin and / or an alicyclic hydrogenated resin are used according to the present invention. By compounding the petroleum resin, a vibration energy absorber having no bad odor and excellent weather resistance can be obtained.

[Table 1]

[Table 2]

[Table 3]

Continuation of the front page (51) Int.Cl. ⁷ identification code FI (C08L 27/06 93:04) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 27/06 E04H 9/02 331 C08L 57:02 C08L 93:04

Claims (3)

(57) [Claims] 1. A phthalic ester represented by the following general formula (1) is added to a polyvinyl chloride resin in an amount of 5 to 100 parts by weight.
A polyvinyl chloride resin composition comprising 200 parts by weight and 5 to 200 parts by weight of a phthalic acid ester represented by the following general formula (2). Embedded image Embedded image R _{1 to} R ₃ : monocyclic hydrocarbon R ₄ : an alkyl group having a C _{1 to} C ₆ carbon chain 2. The polyvinyl chloride resin composition according to claim 1, wherein the hydrogenated rosin resin and / or the alicyclic hydrogenated petroleum resin is used for 100 parts by weight of the polyvinyl chloride resin. Is a polyvinyl chloride resin composition containing 3 to 100 parts by weight. 3. A vibration energy absorbing material comprising the polyvinyl chloride resin composition according to claim 1.