JP2876751B2 - Polyvinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention controls vibration in various fields such as transportation equipment, precision electronic equipment, and audio equipment, thereby improving operation response speed and measurement accuracy, and improving 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.

[Conventional technology]

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 usually sharply decreases from a temperature range 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.

For example, polyvinyl chloride can arbitrarily change the temperature dependence of the loss factor by changing the blend with a plasticizer represented by di-2-ethylhexyl phthalate (DOP).

However, the loss coefficient of both rubber and polyvinyl chloride has a temperature dependency, and the vibration absorption performance can be exhibited only in a specific narrow temperature range.

On the other hand, in recent years, there has been a demand for a material having a small fluctuation in vibration absorption performance in a wide temperature range.

[Problems to be solved by the invention]

An object of the present invention is to provide a vibration energy absorbing material that maintains a high loss coefficient over a wide temperature range while taking advantage of the characteristics of a polyvinyl chloride resin.

[Means for solving the problem]

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

That is, the weight ratio of polyvinyl chloride to polyurethane is 8 /
With respect to 100 parts by weight of the composite consisting of 2 to 4/6, the following (i)
5 to 200 parts by weight of a phthalate having a structure of 5 to 200 parts by weight of a phosphate having a structure of the following (ii):
The present invention also relates to a polyvinyl chloride resin composition comprising 3 to 200 parts by weight of a petroleum resin and a vibration energy absorbing material comprising the present composition.

 Hereinafter, the details will be described.

The polyvinyl chloride resin used in the present invention is a random copolymer or block copolymer with 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 obtained by polymerization (eg, vinyl acetate-vinyl chloride copolymer, ethylene-vinyl chloride copolymer, etc.), which is a single product or a mixture of two or more of the above resins.

The polyurethane used in the present invention has a hydroxyl group at both ends of, for example, polyester-based polyol, polyether-based polyol, polycarbonate-based polyol, vinyl-based polyol, diene-based polyol, castor oil-based polyol, silicone-based polyol and polyolefin-based polyol. Examples thereof include a product obtained by reacting a long-chain polyol with a polyisocyanate such as tolylene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate, and a thermoplastic polyurethane urethane elastomer.

The composite according to the present invention is obtained by blending polyvinyl chloride and polyurethane, or graft-polymerizing at least one of vinyl chloride and all monomers copolymerizable with vinyl chloride to the polyol. A vinyl chloride-urethane copolymer obtained by reacting the above-mentioned polyisocyanate with a polymer, and a blend of a vinyl chloride-urethane copolymer and polyvinyl chloride and / or polyurethane at a predetermined ratio. Among them, vinyl chloride
A blend of a urethane copolymer and polyvinyl chloride is preferred.

A composite comprising polyvinyl chloride and polyurethane in a weight ratio of 8/2 to 4/6 is used. More preferably, by using the composite having a weight ratio of 8/2 to 5/5, a high loss coefficient can be maintained in a wide temperature range. If the weight ratio is more than 8/2, the temperature dependence of the loss coefficient of the present composition is significantly increased. On the other hand, when the polyvinyl chloride content is less than 4/6 by weight, the loss factor of the present composition becomes smaller.

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 (DMCHP), diphenyl phthalate (DPP) and the like, preferably dicyclohexyl phthalate. The addition amount is desirably 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the composite, from the viewpoint of processability and economy. Frequency of 10Hz for polyvinyl chloride alone
When the dynamic viscoelasticity is measured at about 90 ° C, the maximum value of tanδ is 1.1
Indicates that the temperature is about 30 ° C.
In the range of 80 ° C., the maximum value of tan δ is about 1.4 to 1.8.
This phenomenon is understood from the teaching of relaxation phenomenology that the state of the inside of the material has become more uniform and the distribution of relaxation times has narrowed, but why such a specific phthalate ester is particularly excellent is Unknown.

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.

Specific examples include tricresyl phosphate (TCP), trixylenyl phosphate (TXP) and the like. 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 desirably 5 to 200 parts by weight, and more desirably 10 to 100 parts by weight, per 100 parts by weight of the composite from the viewpoint of processability and economy. The bleeding phenomenon of the phthalic acid ester can be remarkably suppressed by adding 5 parts by weight or more of the phosphoric acid ester.

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 composition and the molecular weight. Preferably those containing indene and styrene C ₉ components above 50 wt% as Shinawachi petroleum resin, more ratio between indene and styrene better accounted styrene more than half desirable. The number average molecular weight is 500
It is more preferable that the number be not less than 1500 and not more than 1500. Outside these ranges, the value of the loss factor decreases.

The addition 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 100 parts by weight of the composite. If the amount is less than 3 parts by weight, the loss factor does not improve much, and the workability of the addition exceeding 200 parts by weight is extremely deteriorated.

Further, the phthalic acid ester used in the present invention has a drawback that it easily bleeds after shaping, but the petroleum resin and the phosphoric acid ester also have the advantage of obtaining an effect of suppressing bleeding.

The polyvinyl chloride resin composition according to the present invention contains a plasticizer such as DOP, dioctyl sebacate (DOS) usually added to a polyvinyl chloride resin, a trimellitate ester usually added to a polyurethane resin, calcium carbonate, and the like. Add as necessary inorganic fillers such as talc, flame retardants such as antimony trioxide and trizinc borate, and flake-like fillers often used for vibration energy absorbers such as mica and graphite. can do.

If necessary, NBR (acrylonitrile-butadiene rubber), EV
It can be blended with A (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 polyvinyl chloride resin composition according to the present invention can be freely formed and processed by a conventional method of forming and processing a polyvinyl chloride resin such as calendering, extrusion, injection molding, foam molding, and compression molding. it can.

Further, the vibration energy absorbing material obtained according to 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.

〔Example〕

Hereinafter, the present invention will be described using examples, but the present invention is not limited to these examples.

(Example 1) Ethylene-vinyl chloride copolymer (Ryuron E-2800,
30 parts by weight of Tosoh Corporation, 70 parts by weight of a vinyl chloride-urethane copolymer (polyvinyl chloride / polyurethane = 50/50), and dicyclohexyl phthalate as a phthalic acid ester (DCHP, manufactured by Osaka Organic Chemical Co., Ltd.) 20 Parts by weight, di-2-
15 parts by weight of ethylhexyl phthalate (DOP, manufactured by Kao Corporation), trixylenyl phosphate (TXP, Daihachi Chemical Co., Ltd.)
25 parts by weight, petroleum resin (Petcoal LX-HS, manufactured by Tosoh Corporation) 40 parts by weight, OG-756 (manufactured by Mizusawa Chemical Co., Ltd.) as a stabilizer 1 part by weight, liquid barium zinc-based stabilizer (6226, Akishima Chemical Co., Ltd.) 1 part by weight, phosphite stabilizer (4342, Akishima Chemical Co., Ltd.) 0.6 part by weight, antimony trioxide (ATOX-S, Nippon Seiko Co., Ltd.) as a flame retardant Made)
7 parts by weight were mixed and roll-kneaded at a temperature of 160 ° C. for 5 minutes to obtain a target composition.

(Example 2) In Example 1, the ethylene-vinyl chloride copolymer pair was replaced with 40
The same system was mixed except that the weight ratio of the vinyl chloride-urethane copolymer was changed to 60 parts by weight, and the mixture was roll-kneaded at a temperature of 165 ° C. for about 5 minutes to obtain a target composition.

(Example 3) In Example 1, the ethylene-vinyl chloride copolymer was replaced with 25
Parts by weight, 75 parts by weight of a vinyl chloride-urethane copolymer, 10 parts by weight of dicyclohexyl phthalate, and 20 parts by weight of trixylenyl phosphate were mixed in exactly the same system, and the mixture was heated at a temperature of 160 ° C. for about 5 minutes. Roll kneading was performed to obtain the desired composition.

(Example 4) In Example 1, 50 ethylene-vinyl chloride copolymers were used.
The same system was mixed except that the vinyl chloride-urethane copolymer was changed to 50 parts by weight and the mixture was roll-kneaded at a temperature of 165 ° C. for about 5 minutes to obtain a desired composition.

(Example 5) Instead of the ethylene-vinyl chloride copolymer in Example 1, a polyvinyl chloride resin (TH-1000, manufactured by Tosoh Corporation)
The same system as above was mixed except for using, and roll-kneaded at a temperature of 160 ° C for about 5 minutes to obtain a target composition.

(Example 6) Except that 70 parts by weight of dicyclohexyl phthalate and 70 parts by weight of trixylenyl phosphate were used in Example 1, exactly the same system was mixed, and the mixture was kneaded in a roll at a temperature of 165 ° C for about 5 minutes to obtain a desired composition. I got something.

(Example 7) In Example 1, the ethylene-vinyl chloride copolymer was replaced with 0.
Parts by weight, except that the vinyl chloride-urethane copolymer was changed to 100 parts by weight, and the same system was mixed.
Roll kneading was carried out for a minute to obtain the desired composition.

(Example 8) Instead of the ethylene-vinyl chloride copolymer in Example 1, a polyvinyl chloride resin (TH-1000, manufactured by Tosoh Corporation)
Mix exactly the same system except that 50 parts by weight of a blend of 50 parts by weight of a polyurethane elastomer (Paraprene 25SM, manufactured by Nippon Polyurethane Industry Co., Ltd.) instead of the vinyl chloride-urethane copolymer is used. At about 5
Roll kneading was carried out for a minute to obtain the desired composition.

(Comparative Example 1) In Example 1, the ethylene-vinyl chloride copolymer was replaced with 80
The same system was mixed except that the vinyl chloride-urethane copolymer was changed to 20 parts by weight, and the mixture was roll-kneaded at a temperature of 170 ° C. for about 5 minutes to obtain a target composition.

(Comparative Example 2) Except for using a blend of 30 parts by weight of a polyvinyl chloride resin and 70 parts by weight of a polyurethane elastomer in Example 8, the same system was mixed, and a temperature of about
Roll kneading was carried out for a minute to obtain the desired composition.

[Evaluation of loss coefficient (tan δ)] Loss at a heating rate of 2 ° C / min and a measurement frequency of 10 Hz using a viscoelastic analyzer RSAII (manufactured by Rheometrics Far East), which is a measuring device based on a non-resonant forced vibration method. The coefficient was measured. Table 1 shows the temperature range where the loss coefficient is 0.6 or more.

[Effects of the Invention] As is apparent from the above description, according to the present invention, polyvinyl chloride and polyurethane are compounded at a specific ratio, and further, specific phthalate and phosphate esters are compounded with petroleum resin. As a result, a vibration energy absorber maintaining a high loss coefficient over a wide temperature range can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification symbol FI // (C08K 5/00 5:12 5: 523) (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 27 / 06 C08L 57/02 C08L 75/04-75/16

Claims (2)

(57) [Claims] 1. A weight ratio of polyvinyl chloride to polyurethane of 8 /
With respect to 100 parts by weight of the composite consisting of 2 to 4/6, the following (i)
5 to 200 parts by weight of a phthalate having a structure of 5 to 200 parts by weight of a phosphate having a structure of the following (ii):
And a polyvinyl chloride resin composition comprising 3 to 200 parts by weight of a petroleum resin. Where R ¹ and R ² are monocyclic hydrocarbons However, R ^{3 to} R ^{5 are} aromatic monocyclic hydrocarbons. 2. A vibration energy absorbing material comprising the composition according to item (1).