JP2913487B2 - Polyvinyl chloride resin composition - Google Patents

Description

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

[Prior 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. The primary evaluation of these vibration energy absorbing materials is made by the storage modulus (E ') and the loss coefficient (tan δ = loss modulus (E ") / storage modulus (E')) obtained by measuring the viscoelasticity of the material. You.

In order to design as a vibration energy absorbing material, the larger the loss coefficient is, the more 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, as a standard conventionally 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 elastic 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 loss coefficients 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.

On the other hand, polyvinyl chloride resin has a long history as one of the five major general-purpose resins, and most molding methods have been established with economic efficiency. Moreover, it is an amorphous resin,
It has advantages such as easy compounding with metal fillers and softeners.

The loss coefficient of polyvinyl chloride alone has a peak value of about 1.1 around 90 ° C. However, when 100 parts by weight of DOP, which is a typical plasticizer, is added to 100 parts by weight of the resin, the peak temperature of the loss coefficient is about 5 ° C., and the peak value is about 0.4%.
It drops to about 7. It was understood that this phenomenon would result in a broader distribution of relaxation times as a result of the incorporation of heterogeneous molecules into the single molecular chain of polyvinyl chloride. However, as a result of our recent studies, the addition of a very limited type of plasticizer, such as dicyclohexyl phthalate, to polyvinyl chloride lowers the peak temperature of the loss coefficient and increases the peak value by 1.6%.
To the extent that it has been found. However, this dicyclohexyl phthalate is used alone in polyvinyl chloride.
Even if it is added in an amount of 70 wt% or more or 30 wt% or less, there is a fatal defect that bleeding occurs when mixed with DOP or the like.

[Problems to be Solved by the Invention] The present invention provides a polyvinyl chloride resin composition having excellent vibration energy absorption performance, which does not cause a bleed phenomenon even when dicyclohexyl phthalate is added, while taking advantage of the features of the polyvinyl chloride resin. The purpose is to provide.

[Means for Solving the Problems] The gist of the present invention is to provide a polyvinyl chloride resin and a phthalic ester having the following structure (i) and the following (i)
The present invention relates to a polyvinyl chloride resin composition comprising a phosphate ester having the structure of i), and a vibration energy absorbing material comprising the present composition.

R ₁ , R ₂ : monocyclic hydrocarbon R _{2 to} R ₅ : aromatic monocyclic hydrocarbon The details will be described below.

The polyvinyl chloride resin used in the present invention is generally a polyvinyl chloride homopolymer, a copolymer with vinyl acetate, ethylene, a graft copolymer with ethylene / vinyl acetate copolymer or polyurethane, etc. What can be recognized as a system resin is shown.

The phthalate having a structure of the general formula (i) is
R ₁ and R ₂ are compounds comprising C _{3 to} C ₈ monocyclic hydrocarbons. R ₁ and R ₂ may be the same or different, and hydrogen on the ring may be substituted with another substituent.

Specific examples include dicyclohexyl phthalate (DCHP), dimethylcyclohexyl phthalate, diphenyl phthalate (DPP) and the like, with dicyclohexyl phthalate being preferred. The addition amount is desirably from 5 to 200 parts by weight, preferably from 10 to 100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin from the viewpoint of processability and economy. In the case of polyvinyl chloride alone, when the dynamic viscoelasticity is measured at a frequency of 10 Hz, the maximum value of tanδ at about 90 ° C. shows 1.1, but depending on the amount of addition in this range, tanδ at a temperature of about 30 ° C. to 80 ° C. Indicates a maximum value of about 1.4 to 1.8. According to the theory of relaxation phenomena, it is understood that the uniformity of the state inside the material has progressed and the distribution of the relaxation time has narrowed, but it is unknown why such a specific phthalate ester is specifically superior It is.

The phosphate having the structure represented by the general formula (ii) is a compound in which R ₂ is a C _{6 to} C ₉ aromatic monocyclic hydrocarbon. R _{3 to} R ₅ may be the same or different, and hydrogen on the ring may be substituted with another substituent.

Specifically, tricresyl phosphate (TCP), trixylenyl phosphate (TXP) and the like can be mentioned. In particular, trixylenyl phosphate also has an excellent feature that the maximum value of tan δ is maintained at about 1.1 even when added alone to the polyvinyl chloride resin.

The addition amount of the phosphate ester 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 from the viewpoint of processability and economy. The bleeding phenomenon of the phthalic acid ester can be significantly suppressed by adding 5 parts by weight or more of the phosphoric acid ester.

By adjusting the amount of the phthalic acid ester and the phosphoric acid ester, the present composition can set the temperature at which tan δ shows the maximum value in a wide range from room temperature to about 80 ° C., and the value also keeps 1.2 or more. Therefore, it can be said that it is extremely useful as a vibration energy absorbing material.

Further, the bleeding phenomenon of the phthalic acid ester can be suppressed by the effect of the phosphoric acid ester, and the excellent characteristics of the polyvinyl chloride resin are maintained. Accordingly, the composition of the present invention can be used to obtain a molded article having an arbitrary shape by a processing method such as calendering, compression molding, injection molding or the like in which polyvinyl chloride resin is usually used.

Further, the resin composition according to the present invention includes a filler such as calcium carbonate, talc, mica graphite and the like, and a flame retardant such as antimony trioxide, which are used in ordinary polyvinyl chloride;
Further, a plasticizer or the like can be added. In addition, polymer materials such as polyvinyl acetate, ethylene-vinyl acetate copolymer, and acrylonitrile-butadiene rubber, which are commonly used for general modification of polyvinyl chloride resin, or coumarone resin, xylene resin, etc. It is also possible to blend with a polymer material which is supposed to be present.

The vibration-absorbing material according to the present invention is used for the purpose of suppressing vibration by directly affixing it to a severely vibrating part such as an automobile or industrial equipment, or for preventing the propagation of vibration from the floor by using the leg of precision equipment. You.

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

Example 1 100 parts by weight of an ethylene / vinyl chloride copolymer resin (Ryuron E-2200) [manufactured by Tosoh Corporation] and 40 parts by weight of TXP (trixylenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd.] , DCHP
(Dicyclohexyl phthalate) [Osaka Organic Chemical Co., Ltd.
Manufactured), 2 parts by weight of barium stearate as a heat stabilizer, and 1 part by weight of zinc stearate were mixed and formed into a sheet by a roll forming machine. The roll sheet was formed into a flat sheet having a thickness of 1 mm by a press molding machine, and the dynamic viscoelasticity was evaluated by a dynamic viscoelasticity measuring device (Ryovibron manufactured by Orientec Co., Ltd.).

Example 2 100 parts by weight of vinyl chloride resin (Ryuron paste R-725) [manufactured by Tosoh Corporation], 100 parts by weight of TXP (trixylenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd.], DCHP
(Dicyclohexyl phthalate) [Osaka Organic Chemical Co., Ltd.
60 parts by weight and 2 parts by weight of AC-113 [made by Adeka Argus Chemical Co., Ltd.] as a heat stabilizer, and antimony trioxide (Atox-S) [made by Nippon Seimitsu Co., Ltd.] 2 as a flame retardant
The parts by weight were mixed, a flat sheet having a thickness of 1 mm was formed by a press molding machine, and the dynamic viscoelasticity was measured under the same conditions as in Example 1.

Example 3 Of the composition of Example 1, 35 parts by weight of TXP (trixylenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd.], DCHP (dicyclohexyl phthalate) [manufactured by Osaka Organic Chemical Co., Ltd.]
Changed to 15 parts by weight, polyester-based plasticizer (ADEKA SIZER PN-77) [Adeka Argus Chemical Co., Ltd.] 15
A sheet was prepared according to Example 1 by adding parts by weight, and dynamic viscoelasticity was measured.

Example 4 Vinyl chloride-urethane graft polymer resin (Dominus K-
800F [manufactured by Tosoh Corporation] 100 parts by weight, TXP (trixylenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd.] 10 parts by weight, DCHP (dicyclohexyl phthalate) [manufactured by Osaka Organic Chemicals] 20 A liquid barium zinc-based stabilizer (6227) [manufactured by Akishima Chemical Co., Ltd.]
Parts by weight, 2.6 parts by weight of granular barium zinc-based stabilizer (6226) [Akishima Chemical Co., Ltd.] and 0.6 parts by weight of phosphite ester-based stabilizer (4342) [Akishima Chemical Co., Ltd.] are mixed. A sheet was specially prepared according to Example 1, and the dynamic viscoelasticity was measured.

Comparative Example 1 Of the composition of Example 1, TXP (trixylenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd.] 0 parts by weight, DCHP (dicyclohexyl phthalate) [manufactured by Osaka Organic Chemical Co., Ltd.] 20 parts by weight Then, 30 parts by weight of a polyester plasticizer (ADEKA SIZER PN-77) (manufactured by Adeka Argus Chemical Co., Ltd.) was added, and a sheet was prepared according to Example 1, and the dynamic viscoelasticity was measured.

Comparative Example 2 Of the composition of Example 1, 0 parts by weight of TXP (trixylenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd.] and 20 parts by weight of DCHP (dicyclohexyl phthalate) [manufactured by Osaka Organic Chemical Co., Ltd.] Was added, and 30 parts by weight of DOP (di-2-ethylhexyl phthalate) [manufactured by Kao Corporation] was added. A sheet was prepared according to Example 1, and the dynamic viscoelasticity was measured.

Comparative Example 3 Of the composition in Example 1, 0 parts by weight of TXP (tricilenyl phosphate) [manufactured by Daihachi Chemical Industry Co., Ltd.] and 20 parts by weight of DCHP (dicyclohexyl phthalate) [manufactured by Osaka Organic Chemical Co., Ltd.] Change to DOA (dioctyl adipate)
[Kurokin Chemical Co., Ltd.] 30 parts by weight were added to prepare a sheet according to Example 1, and the dynamic viscoelasticity was measured.

(Evaluation of Loss Factor) The sheets obtained in Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3 were subjected to a dynamic viscoelasticity measurement apparatus (Orientec Co., Ltd., Leo Vibron) to obtain a loss factor ( tan δ) was measured. The measurement was performed at a measurement frequency of 110 Hz and a heating rate of 1 ° C./min. Table 1 shows the maximum value of tan δ and the temperature at that time.

(Evaluation of Bleeding Phenomenon) The sheets obtained in Examples 1, 2, 3, and 4 and Comparative Examples 1, 2, and 3 were left in a constant temperature room at a temperature of 23 ° C. and a humidity of 50%, and the bleeding phenomenon was visually examined. In Table 1, the example in which bleeding was observed was regarded as the period until the bleeding phenomenon was found, and the example in which the bleeding phenomenon was not found even after 6 months was evaluated as "absent".

[Effects of the Invention] As is clear from the above description, by adding a specific phosphate ester and a specific phthalate ester together,
The bleeding phenomenon can be suppressed and a polyvinyl chloride resin composition having a high loss coefficient can be obtained.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-1-163244 (JP, A) JP-A-1-198200 (JP, A) JP-A-3-70758 (JP, A) JP-A-3-163 59055 (JP, A) JP-A-61-37834 (JP, A) JP-A-49-90335 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 27/06 C08L 51 / 00 C08K 5/12 C08K 5/52-5/521

Claims (2)

(57) [Claims] A phthalic acid ester having a structure of the following (i) based on 100 parts by weight of a polyvinyl chloride resin:
Phosphate ester 5 having parts by weight and the following structure (ii):
A polyvinyl chloride resin composition comprising up to 200 parts by weight. R ₁ , R ₂ : monocyclic hydrocarbon R _{3 to} R ₅ : aromatic monocyclic hydrocarbon 2. A vibration energy absorbing material comprising the composition according to item (1).