JPH0565382A - Polyvinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having an excellent ability to absorb vibration energy by mixing a polyvinyl chloride resin with a specified condensed polycyclic compound or a ring assembly consisting of specified ring systems. CONSTITUTION:The objective resin composition is obtained by mixing 100 pts.wt. polyvinyl chloride resin with 5-100 pts.wt. condensed polycyclic compound consisting of at least three rings and/or ring assembly consisting of at least three ring systems. The polyvinyl chloride resin is a vinyl chloride homopolymer resin, a chlorinated vinyl chloride resin, or a vinyl chloride copolymer resin comprising a random or block copolymer of vinyl chloride with at least one monomer copolymerizable therewith and it is used along or as a mixture of at least two of these. Although any of the condensed polycyclic compounds having at least three rings may be used, those having a larger number of rings are preferable. Although any of the ring assemblies consisting of at least three ring systems may be used, those having a larger number of ring systems are preferable.

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. Further, 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 ") / determined by viscoelasticity measurement of the material.
Storage modulus (E ')).

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 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 elastomers have maximum loss factors of tan δ = 1.4, 2.
It shows an excellent value of 81.3. However, these materials were difficult to process and form, and their use range was limited.

Further, polyvinyl chloride resin has a long history as one of the five major general-purpose resins, and most molding methods have been established as well as economical efficiency. In addition, it has advantages such as being an amorphous resin and being easily compounded with an inorganic / metal filler or a softening agent. The loss coefficient of polyvinyl chloride alone has a peak value of about 1.1 at around 90 ° C. However, if 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 becomes about 5 ° C., and the peak value becomes about 0.7. Will fall.

This value is too low as compared with the above-mentioned rubber elastomer. Therefore, a thermoplastic resin having a high loss factor, which is excellent in processability and economy, is being demanded.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polyvinyl chloride resin composition having excellent vibration energy absorption performance while taking advantage of the characteristics of the polyvinyl chloride resin.

[0011]

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, the present invention provides a fused polycyclic compound having 3 or more rings and / or a ring assembly having 3 or more ring systems per 100 parts by weight of a polyvinyl chloride resin.
To 100 parts by weight of polyvinyl chloride resin composition.

Further, 5 to 100 of a fused polycyclic compound having 3 or more rings and / or a ring assembly having 3 or more ring systems per 100 parts by weight of the polyvinyl chloride resin is used.
Parts by weight, 5 to 200 parts by weight of the phthalic acid ester represented by the following general formula (1), and 5 to 200 parts by weight of the phosphoric acid ester represented by the following general formula (2) in 100 parts by weight of the polyvinyl chloride resin. And a polyvinyl chloride resin composition comprising the same, wherein the polyvinyl chloride resin composition comprises 3 to 200 parts by weight of a petroleum resin with respect to 100 parts by weight of the polyvinyl chloride resin. Regarding

[0014]

[Chemical 3]

[0015]

[Chemical 4] R < ₁ >, R < ₂ >: Monocyclic hydrocarbon R < ₃ > -R < ₅ >: Aromatic monocyclic hydrocarbon Furthermore, it is related with the vibration energy-absorbing material which consists of these compositions.

The details will be described below.

The polyvinyl chloride resin used in the present invention is a vinyl chloride homopolymer resin, a chlorinated vinyl chloride resin,
Vinyl chloride copolymer resin obtained by random copolymerization or block copolymerization with one or more of all monomers copolymerizable with vinyl chloride monomer (for example, vinyl acetate-vinyl chloride copolymer, ethylene- Vinyl chloride copolymer etc.)
The resin is a single product or a mixture of two or more kinds.

The condensed polycyclic compound used in the present invention is a condensed polycyclic hydrocarbon or condensed heterocyclic compound composed of three or more rings. There is no problem with any structure as long as it has three or more rings, but it is particularly preferable that the number of rings is large.

On the other hand, the ring assembly used in the present invention includes three or more ring systems (monocycle or condensed ring) directly bonded by a single bond or a double bond, and includes the number of such direct ring bonds. One less than the number of existing ring systems. The ring system may be a cyclic hydrocarbon system or a heterocyclic ring system.
There is no problem with any structure as long as it has three or more ring systems, but it is particularly preferable that there are many ring systems.

These condensed polycyclic compounds and ring aggregates (hereinafter collectively referred to as cyclic compounds) have alkyl groups having 1 to 4 carbon atoms, hydroxyl groups, oxo groups, carboxyl groups,
A functional group such as an amino group, a cyano group, a nitro group and a halogen group may be bonded to the ring.

Further, since the cyclic compound is compounded with the polyvinyl chloride resin, it is necessary to reach a sufficiently dispersed state. Therefore, it is desirable that the melting point of the cyclic substance is lower than the processing temperature of the polyvinyl chloride resin. For example, as the condensed polycyclic compound, acenaphthylene, acenaphthene, phenanthrene, 9-phenanthrole, fluorene, anthrone, 9-fluorenone, perhydrofluorene, benzophenanthrene, 9-anthracene methanol,
9,10-dihydroanthracene, pyrene, 1,2-benzopyrene, dibenzophenanthrene, dibenzosuberane, terpenes consisting of 3 or more rings, steroids, alkaloids, dibenzofuran, xanthene, 9-xanthenol, xanthone, acridine, dibenzothiophene,
Examples include phenanthridine, 1,4-benzoquinone, 7,8-benzoquinoline, 1,10-phenanthroline, phenazine, phenoxazine, thianthrene and the like.
As the ring assembly, 1,2-diphenylbenzene, 1,3
-Diphenylbenzene, 1,3,5-triphenylbenzene, 1,2,3,4-tetraphenyl-1,3-cyclopentadiene, 2,2: 6 ', 2 "-terpyridine and the like.

One kind or a mixture of two or more kinds of these cyclic materials is compounded with the polyvinyl chloride resin.

From the viewpoint of processability and economic efficiency, the total amount of cyclic compounds added is 5 parts by weight or more and 100 parts by weight or less, and more than 15 parts by weight and 50 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. Less than or equal to part is desirable.

When polyvinyl chloride alone is used, the frequency is 10H.
When the dynamic viscoelasticity is measured by z, the maximum value of tan δ is 1.1 at about 90 ° C., but the maximum value of tan δ is 1 in the temperature range of about 20 ° C. to 85 ° C. depending on the addition amount in this range. .2
Shows about 2.5. According to the theory of relaxation phenomenology, this phenomenon is understood to be due to the homogenization of the state inside the material and the narrowing of the relaxation time distribution, but it is unclear why such a particular ring is uniquely superior. Is.

On the other hand, since these cyclic substances are very expensive as compared with general plasticizers, there is a problem in using them as plasticizers. Furthermore, the present invention provides the above resin composition with a phthalate represented by the general formula (1) and a general formula (2).
It is a polyvinyl chloride resin composition obtained by adding a phosphoric acid ester represented by or a petroleum resin together with these phthalic acid ester and phosphoric acid ester, but this reduces the vibration absorption performance of the resin composition. It is possible to manipulate the glass transition point to any temperature without causing it.

The phthalic acid ester having the structure of the general formula (1) is a compound in which R ₁ and R ₂ are C _{3 to} C ₆ monocyclic hydrocarbons. R1 and R2 may be the same or different, and hydrogen on the ring may be substituted with another substituent. Specific examples thereof include dicyclohexyl phthalate (DCHP), dimethyl cyclohexyl phthalate and diphenyl phthalate, and dicyclohexyl phthalate is preferably used. From the viewpoint of processability and economic efficiency, the amount of addition is 5 parts by weight or more and 200 parts by weight or less, and more preferably 1 part by weight with respect to 100 parts by weight of the polyvinyl chloride resin.
It is preferably 0 part by weight or more and 100 parts by weight or less.

The phosphoric acid ester having the structure of the general formula (2) is a compound in which R ₃ is a C _{6 to} C ₉ aromatic monocyclic hydrocarbon. R _{3 to} R ₅ may be the same or different, and the hydrogen on the ring may be substituted with another substituent. Specifically, tricresyl phosphate (TCP),
Examples thereof include trixylenyl phosphate (TXP), and preferably trixylenyl phosphate is used. From the viewpoint of processability and economic efficiency, the amount of addition is 5 parts by weight or more and 200 parts by weight or more per 100 parts by weight of polyvinyl chloride resin.
It is preferably not more than 10 parts by weight, more preferably not less than 10 parts by weight and not more than 100 parts by weight.

When the phthalate ester of the general formula (1) is used alone, a bleeding phenomenon occurs, but the bleeding phenomenon can be remarkably suppressed by adding 5 parts by weight or more of the phosphate ester of the general formula (2). it can.

In such a composition, by adjusting the blending amount of phthalic acid ester and phosphoric acid ester, tan
Since the temperature at which δ has the maximum value can be set in a wide range from room temperature to about 80 ° C. and the value can be maintained at 1.2 or more, it can be said to be extremely useful as a vibration energy absorbing material.

Further, by combining a petroleum resin in addition to the phthalic acid ester and the phosphoric acid ester, it becomes possible to further increase the loss coefficient.

The petroleum resin used in the present invention is C _{5 to} C
It is obtained by polymerizing the olefin of _{9 in} a mixed state. However, the addition of petroleum resin improves the maximum value of the loss coefficient, but the degree of its effect varies considerably depending on the composition and the molecular weight. That is, preferably those containing more than 50% by weight of indene and styrene C ₉ components as petroleum resin, more ratio between indene and styrene is preferably styrene more than half of the total amount. The number average molecular weight is preferably 500 or more and 1500 or less. If the value is out of these ranges, the value of loss factor may decrease. The addition amount is 3 parts by weight or more and 200 parts by weight or less based on 100 parts by weight of the polyvinyl chloride resin,
Further, it is preferably 10 parts by weight or more and 100 parts by weight or less.
If it is less than 3 parts by weight, the loss factor does not improve so much and
If it is added in an amount of more than 0 parts by weight, workability will be extremely reduced.

The polyvinyl chloride resin composition according to the present invention contains DOP and dioctyl sebum which are usually added to the polyvinyl chloride resin to the extent that the performance thereof is not extremely deteriorated.
Good for plasticizers such as DOS, inorganic fillers such as calcium carbonate and talc, flame retardants such as antimony trioxide and zinc borate, and vibration energy absorbing materials such as mica and graphite. The flaky filler used and the like can be added if necessary.

If necessary, it may be blended with NBR (acrylonitrile-butadiene rubber), EVA (ethylene-vinyl acetate copolymer), acrylic resin and the like which are usually used for modifying polyvinyl chloride resin. Further, it can be blended with coumarone resin, xylene resin, etc., which are often used as vibration energy absorbers.

The polyvinyl chloride resin composition according to the present invention can be freely processed by conventional methods such as calendar processing, extrusion processing, injection molding, foam molding, compression molding and the like for molding polyvinyl chloride resin. be able to.

Further, the vibration energy obtained by the present invention
Absorbing materials are used for supporting members of equipment such as precision electronic equipment and precision measuring equipment whose accuracy is affected by vibration, fixing members such as packing and gaskets, laminated members such as audio equipment and chassis. it can. In addition, it is used to suppress vibration by directly attaching it to areas with severe vibration such as automobiles and industrial equipment, and to prevent the propagation of vibration from the floor by using it on the legs of precision equipment. It can also be used in combination with other materials such as wood and inorganic materials including metal materials such as aluminum plates.

[0036]

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 (Leuron E-280
100 parts by weight of Toso Co., Ltd., 20 parts by weight of phenanthrene as a condensed polycyclic compound, and OG- as a stabilizer.
5 parts by weight of 756 (manufactured by Mizusawa Chemical Co., Ltd.) and antimony trioxide as a flame retardant (ATOX-S, manufactured by NSK Ltd.)
7 parts by weight were mixed and roll-kneaded at a temperature of 170 ° C. for 5 minutes to obtain a target composition.

Example 2 Pyrene 20 was used in place of phenanthrene in Example 1.
Mix exactly the same system except that parts by weight are used and the temperature is 17
The mixture was rolled and kneaded at 0 ° C for 5 minutes to obtain a desired composition.

Example 3 The same system as in Example 1 except that 20 parts by weight of fluorene was used in place of phenanthrene was mixed, and the mixture was roll-kneaded at a temperature of 170 ° C. for 5 minutes to obtain a desired composition. ..

Example 4 The same system as in Example 1 was mixed except that 20 parts by weight of anthrone was used instead of phenanthrene, and the mixture was roll-kneaded at a temperature of 170 ° C. for 5 minutes to obtain a desired composition. ..

Example 5 An exactly identical system was mixed except that 20 parts by weight of dibenzofuran was used in place of phenanthrene in Example 1,
The mixture was rolled and kneaded at a temperature of 160 ° C. for 5 minutes to obtain a desired composition.

Example 6 Exactly the same system as in Example 1 except that 80 parts by weight of phenanthrene was used was mixed and roll-kneaded at a temperature of 170 ° C. for 5 minutes to obtain a desired composition.

Comparative Example 1 The same system as in Example 1 was mixed except that 20 parts by weight of 2-methylnaphthalene, which is a condensed polycyclic compound having two rings, was used in place of phenanthrene, and the temperature was raised to 160 ° C. Roll kneading for 5 minutes to obtain the desired composition.

Comparative Example 2 Decalin 2 was used instead of phenanthrene in Example 1.
Mix exactly the same system except that 0 parts by weight is used and the temperature is 1
Roll kneading was carried out at 60 ° C. for 5 minutes to obtain a desired composition.

Example 7 In place of phenanthrene in Example 1, exactly the same system was mixed except that 20 parts by weight of 1,2-diphenylbenzene was used as a ring assembly, and roll kneading was carried out at a temperature of 170 ° C. for 5 minutes. Then, the intended composition was obtained.

Example 8 1,3,5 instead of phenanthrene in Example 1
-Exactly the same system except that 20 parts by weight of triphenylbenzene was used was mixed and roll-kneaded at a temperature of 170 ° C for 5 minutes to obtain an intended composition.

Example 9 The same system as in Example 7 was mixed except that 1,2-diphenylbenzene was changed to 80 parts by weight, and the temperature was 170 ° C.
The mixture was rolled and kneaded for 5 minutes to obtain the desired composition. Comparative Example 3 The same system as in Example 1 was mixed except that 20 parts by weight of biphenyl, which is a ring assembly consisting of two rings, was used in place of phenanthrene, and the mixture was mixed at a temperature of 170 ° C. for 5 minutes.
And kneaded to obtain the desired composition.

Comparative Example 4 The same composition as in Example 1 was mixed except that 20 parts by weight of p-hydroxybiphenyl was used in place of phenanthrene, and the mixture was roll-kneaded at a temperature of 170 ° C. for 5 minutes to obtain the desired composition. Got

Example 10 In Example 1, 35 parts by weight of dicyclohexyl phthalate (DCHP, manufactured by Osaka Organic Chemical Co., Ltd.) and trixylenyl phosphate (TXP, Daihachi Chemical Industry Co., Ltd.) were further added. 40 parts by weight was added and the mixture was roll-kneaded at a temperature of 160 ° C. for 5 minutes to obtain a target composition.

Example 11 Vinyl chloride-urethane graft polymerization resin (Dominus K-
800F, Tosoh Co., Ltd.) 100 parts by weight, 1,3-diphenylbenzene 20 parts by weight as a ring assembly, dicyclohexyl phthalate (DCHP, Osaka Organic Chemical Co., Ltd.)
20 parts by weight of trixylenyl phosphate (TXP,
10 parts by weight of Daihachi Chemical Industry Co., Ltd., and 1 part by weight of a liquid barium zinc-based stabilizer (6227, manufactured by Akishima Chemical Co., Ltd.) as a heat stabilizer, and a granular barium zinc-based stabilizer (6226, 6226, Akishima Chemical Co., Ltd.) 2.6 parts by weight, phosphite ester stabilizer (4342, Akishima Chemical Co., Ltd.)
6 parts by weight were mixed and roll-kneaded at a temperature of 150 ° C. for 5 minutes to obtain a desired composition.

Comparative Example 5 In the composition of Example 10, 40 parts by weight of di-2-ethylhexyl phthalate (Vinizer 80, manufactured by Kao Corporation) was used instead of trixylenyl phosphate. The target composition was obtained by exactly the same operation except the above.

Example 12 87 parts by weight of polyvinyl chloride resin (Luron TH-1000, manufactured by Toso Corporation), ethylene-vinyl chloride copolymer (Luron E-2800, manufactured by Toso Corporation) ) Made 13
Parts by weight, petroleum resin (Petcole LX-T, East So-
39 parts by weight, 20 parts by weight of pyrene as a condensed polycyclic compound, dicyclohexyl phthalate (DCHP,
40 parts by weight of Osaka Organic Chemical Co., Ltd., di-2-ethylhexyl phthalate (Vinizer 80, manufactured by Kao Corporation)
7.5 parts by weight of trixylenyl phosphate (TXP,
27.5 parts by weight of Daihachi Chemical Industry Co., Ltd., 5 parts by weight of OG-756 (manufactured by Mizusawa Chemical Co., Ltd.) as a stabilizer, and antimony trioxide (ATOX-S, Nihon Seiko Co., Ltd.) as a flame retardant. )) 7 parts by weight, calcium carbonate (Whiten P-30, manufactured by Shiraishi Calcium Co., Ltd.) 20 as an inorganic filler.
0 parts by weight and 40 parts by weight of mica (Suzolite Mica 150-S, manufactured by Kuraray Co., Ltd.) were mixed, and the mixture was mixed at a temperature of 140 ° C. for 5
Roll-kneading was carried out for a minute to obtain the desired composition.

Example 13 In Example 11, petroleum resin (Petcole L
XT, manufactured by Toso Co., Ltd.) 20 parts by weight, hydrogenated rosin ester (KE-311, manufactured by Arakawa Chemical Industry Co., Ltd.) 10 parts by weight except that the target composition was prepared by the same operation. Got

Comparative Example 6 The same operation as in Example 12 was repeated except that the amount of dicyclohexyl phthalate was changed to 0 part by weight and the amount of di-2-ethylhexyl phthalate was changed to 47.5 parts by weight. The desired composition was obtained. [Evaluation of Loss Factor (tan δ)] The compositions obtained in Examples and Comparative Examples were pressed at 180 ° C. to prepare a sheet having a thickness of 0.2 mm. A viscoelasticity analyzer-RSAI which is a measuring device based on the non-resonance type forced vibration method using this sheet.
The loss coefficient was measured by I (manufactured by Rheometrics Fast) at a temperature rising 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.

[0055]

As is apparent from the above description, according to the present invention, a condensed polycyclic compound composed of a polyvinyl chloride resin and three or more rings, and / or a ring composed of three or more ring systems. A vibration energy absorbing material having a high loss factor can be obtained by compounding the set at a specific ratio.

Furthermore, by adding a specific phthalic acid ester, phosphoric acid ester, and petroleum resin, a vibration energy absorbing material having a high loss coefficient in an arbitrary temperature range can be obtained.

[Table 1]

[Procedure amendment]

[Submission date] October 18, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0054

[Correction method] Change

[Correction content]

Comparative Example 6 The same composition was mixed as in Example 12 except that the amount of dicyclohexyl phthalate was changed to 0 part by weight and the amount of di-2-ethylhexyl phthalate was changed to 47.5 parts by weight. Obtained. [Evaluation of Loss Factor (tan δ)] The compositions obtained in Examples and Comparative Examples were pressed at 180 ° C to prepare a sheet having a thickness of 0.2 mm. Using this sheet, a viscoelasticity analyzer RSAI, which is a measuring device based on the non-resonance type forced vibration method
The loss coefficient was measured by I (Rheometrics Far East Co., Ltd.) at a temperature rising rate of 2 ° C./min and a measurement frequency of 10 Hz. Table 1 shows the peak value of the loss coefficient at this time and the temperature at that time.

[Table 1]

Claims (4)

[Claims] 1. A fused polycyclic compound comprising 3 or more rings and / or 5 to 100 parts by weight of a ring assembly comprising 3 or more rings based on 100 parts by weight of a polyvinyl chloride resin. Polyvinyl chloride resin composition. 2. The polyvinyl chloride resin composition according to claim 1, wherein 5 parts by weight of the phthalate ester represented by the following general formula (1) is added to 100 parts by weight of the polyvinyl chloride resin.
To 200 parts by weight, and a polyvinyl chloride resin composition containing 5 to 200 parts by weight of the phosphoric acid ester represented by the following general formula (2). [Chemical 1] [Chemical 2] R ₁ and R ₂ : monocyclic hydrocarbon R _{3 to} R ₅ : aromatic monocyclic hydrocarbon 3. The polyvinyl chloride resin composition according to claim 2, wherein the petroleum resin is contained in an amount of 3 to 200 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. object. 4. A vibration energy absorbing material comprising the polyvinyl chloride resin composition according to claim 1.