JP2001040221A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which has an excellent vibration energy-absorbing ability and is useful for transportation equipment, precision electronic equipment, acoustic equipment, and so on, by compounding a specific thermoplastic resin with a condensed polycyclic compound and/or a ring aggregate which comprise the specific number of rings (systems). SOLUTION: This thermoplastic resin composition comprises 100 pts.wt. of a thermoplastic resin such as a polyamide or a polyacetal and 5 to 100 pts.wt. of a condensed polycyclic compound and/or a ring aggregate which comprise three or more rings (systems), (for example, acenaphthene), except anthrone- based compounds and fluorene-based compounds. The composition may further be compounded with a plasticizer such as DOP, an inorganic filler such as calcium carbonate, a flame retardant such as antimony trioxide, a flaky filler such as mica, and so on.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is to improve operation response speed and measurement accuracy by controlling vibration in the fields of various transportation equipment, precision electronic equipment, audio equipment and the like.
The present invention relates to a thermoplastic resin composition used for the purpose of improving sound quality and having excellent vibration energy absorption 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 to determine the storage elastic modulus (E ') and the loss coefficient (tan δ = loss elastic modulus (E ") /
In order to design as a vibration energy absorbing material made with storage elastic modulus (E '), the larger the loss coefficient is, the more the storage elastic modulus has an optimum value depending on the used form.

[0004] 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 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 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, etc. have a maximum loss coefficient of tan δ = 1.4, 2..
It shows an excellent value of 8,1.3. However, these materials have difficulty in workability and moldability, and their use range is limited.

On the other hand, a thermoplastic resin, which is one of the plastics classified according to their behavior at the time of heating, occupies the widest part of the plastic. When this thermoplastic resin is used as a vibrational energy absorbing material, the loss coefficient shows a high value in the glass transition region caused by micro-Brownian motion generated in the amorphous region of the resin, and this region is generally used. I do.

Further, the temperature range in which the material is used is generally around room temperature. However, with most thermoplastic resins alone, the glass transition region is located in a temperature range higher than room temperature.
Further, for example, polypropylene or the like having a glass transition region near room temperature is a crystalline resin, and therefore has few amorphous parts. Therefore, the value of the loss coefficient in the glass transition region is smaller than that of the amorphous resin.

Therefore, it is necessary to shift the glass transition region to a lower temperature side by using an additive such as a plasticizer in most thermoplastic resins. Polyvinyl chloride is one of the thermoplastic resins for which such a technique has been established. The loss coefficient of polyvinyl chloride alone has a peak value of about 1.1 around 90 ° C. However, when 70 parts by weight of di-2-ethylhexyl phthalate (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 20 ° C., and the peak value also becomes about 20 ° C. It will be reduced to about 0.6.

[0010] Even if the same operation is applied to other resins, the loss coefficient tends to decrease, and a method of increasing the loss coefficient of the thermoplastic resin is desired.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition having excellent vibrational energy absorbing properties while utilizing the characteristics of the thermoplastic resin.

[0012]

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, the present invention relates to a condensed polyolefin comprising three or more rings per 100 parts by weight of a thermoplastic resin having a composition of two or more of hydrogen, carbon, nitrogen, oxygen and sulfur. The present invention relates to a cyclic compound and / or a thermoplastic resin composition comprising 5 to 100 parts by weight of a ring assembly comprising three or more ring systems. Further, the present invention relates to a vibration energy absorbing material comprising these compositions.

The details will be described below.

[0015] The thermoplastic resin used in the present invention refers to any resin having a property of retaining its external shape even after removing its external force after being softened and deformed by heating. For example, polyethylene, polyolefin represented by polypropylene, acrylic resin, styrene resin, polyvinyl alcohol, polyethylene terephthalate, polyamide,
Polyacetal, polycarbonate, modified polyphenylene oxide, polyester such as polybutylene terephthalate, polysulfone, polyether sulfone, polyarylene sulfide represented by polyphenylene sulfide, polyarylate, polyamideimide, polyetherimide, polyetheretherketone, polyimide, liquid crystal Polyester, thermoplastic polyurethane, etc., and these are single products or mixtures of two or more.

To describe the thermoplastic resin in more detail, for example, the styrene resin used in the present invention is a resin obtained by polymerizing a styrene monomer alone, compounding a synthetic rubber, or copolymerizing with another monomer. It is.
For example, butadiene-styrene rubber (SBR) and isoprene-styrene block copolymer (SIS) are compounded with synthetic rubber, and styrene acrylonitrile copolymer (AS) is mixed with other monomer. Resin or SAN), styrene methyl methacrylate, acrylonitrile-butadiene styrene copolymer (ABS), and the like, and a single product or a mixture of two or more thereof is used.

The polyarylene sulfide resin used in the present invention is a polymer whose repeating unit is represented by the general formula (Ar-S). Here, (Ar-S) is specifically
Examples include those composed of the following structural units.

[0018]

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(Wherein R is an alkyl group, phenyl group, nitro group, carboxyl group, nitrile group, amino group, alkoxyl group, hydroxyl group or sulfone group. In the formula, X is methylene, ethylene, isopropyl , An ether, a sulfone, a ketone, an amide, and an imino group.) One or more of such polyarylene sulfide resins can be used. However, particularly preferred are polyphenylene sulfide resins. Polyphenylene sulfide resin is

[0020]

Embedded image

The structure having a repeating unit represented by
Other components may be copolymerized as long as they are contained at 0 mol% or more.

Polyarylene sulfide resins are generally known from JP-B-44-2761, JP-B-45-3368, US Pat. No. 3,274,165, and JP-B-46-272.
No. 55, there is a polymer having a relatively small molecular weight, and a polymer having an essentially linear and relatively high molecular weight represented by Japanese Patent Publication No. 52-12240,
The former polymer can be used by increasing the degree of polymerization by heating in an oxygen atmosphere or in the presence of a crosslinking agent such as a peroxide. It is also possible to use a polymer in which the polymer has been modified with an amino group, a carboxyl group, a hydroxyl group, or the like, or a polymer which has been subjected to post-treatment such as deionized water treatment, hot water treatment, and acid treatment.

The melt viscosity of the polyarylene sulfide resin suitable for use in the present invention is not particularly limited as long as a molded article can be obtained.
Those having 0 poise are preferred. Particularly preferably 150 to 4
500 poise. Here, those having a poise of less than 100 poises have disadvantages in mechanical properties, and those having a viscosity of more than 30,000 poises are not preferable because resin molding is difficult. 300 temperature using a Koka type flow tester
It is a value measured at a shear rate of 100 sec ^-1 under a pressure of 10 kg at a temperature of 10 ° C. ).

The acrylic resin used in the present invention is obtained by polymerizing an acrylic monomer indicating acrylic acid, methacrylic acid, and their esters singly or by copolymerizing with another monomer. Further, it is a synthetic resin having a methacrylo group, that is, a compound having an α-methyl acrylo group, in particular, methyl methacrylate as a main raw material. Examples of the form in which methyl methacrylate is polymerized include bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization, but there is no particular problem with polymers obtained by any polymerization method. The degree of polymerization is not particularly limited as long as it is suitable for the intended use. Preferably, the polymer has a melt flow rate (230 ° C., 3.8 kg, I condition) of 1 to 30 g / min. Specifically, polymethyl methacrylate (PMMA), polymethyl acrylate (PMA), polyethyl methacrylate (PEMA) and the like can be mentioned, and a single product or a mixture of two or more thereof is used.

The polyolefin resins used in the present invention include α, such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene and 3-methyl-1-butene. Olefin homopolymers, and copolymers of two or more comonomers, and furthermore, copolymers of α-olefins and other copolymerizable monomers such as vinyl acetate and derivatives thereof,
Alternatively, any of the above-mentioned polymers, or a blend with another thermoplastic resin, a block copolymer, or any polyolefin such as a graft copolymer may be used. Copolymers with monomers are preferred.

The polycarbonate used in the present invention is a polyester of carbonic acid and a polyhydric alcohol or a polyhydric phenol, particularly a reaction product of bisphenol A and phosgene using a phosgene method (or a solvent method), or a transesterification method. A typical example is a polycondensation product of a transesterification reaction between bisphenol A and diphenyl carbonate at high temperature and reduced pressure. The molecular weight is preferably 20,000 or more in consideration of use as a structural material.

The polyacetal used in the present invention is a crystalline thermoplastic resin having a polyether structure in which the molecular main chain is constituted by repeating a methylene group and oxygen. Further, a copolymer in which ethylene oxide, 1,3-dioxolane, or another cyclic ether is added in the ring-opening polymerization of trioxane can also be used.

The polyurethane used in the present invention has a urethane bond in the molecule, and is mainly produced by a reaction between a diisocyanate and a polyhydroxy compound (polyol). For example, examples of diisocyanates include tolylene diisocyanate (TDI), diphenylmethane-4,4′-diisocyanate (MDI), 1,5-naphthalenediisocyanate, and the like. In addition, there is no problem even if a polyisocyanate, an isocyanate regenerated product, a non-yellowing isocyanate, or the like is used. On the other hand, examples of the polyhydroxy compound include polyesters and polyethers whose molecular terminals end with -OH.

The modified polyphenylene oxide used in the present invention is prepared by synthesizing 2,6-xylenol from methanol and phenol, and using this as a raw material, polyphenylene oxide is produced by an oxidative polymerization method using an amine copper complex salt as a catalyst. This is further modified with polystyrene.

The polyester used in the present invention is also called a saturated polyester and is a linear thermoplastic polymer having an ester bond in the main chain, and does not contain an unsaturated bond involved in curing in the molecule. Since it can be synthesized by polycondensation of a dibasic acid and glycol, a wide variety of saturated polyesters can be produced, but especially for use as a molding material, polyethylene terephthalate, polybutylene terephthalate, polyarylate (polycondensation of bisphenol A with phthalic acids) Is preferred. Examples of the polymerization method include a dimethyl terephthalate method and a direct polymerization method, but are not particularly limited.

The polyamide used in the present invention is a polymer synthetic resin having an acid amide bond, and various kinds of amide groups and organic acid groups can be produced. For example, those obtained by heat polymerization of lactam or aminocarboxylic acid, and linear aliphatic polyamides obtained by polycondensation of diamine and dicarboxylic acid are typical examples.
Polyamide 11, polyamide 66, polyamide 610,
Polyamide 612 and the like. In addition, there are amorphous transparent polyamides produced from terephthalic acid and trimethylhexamethylenediamine, and the like, but the polyamide used in the present invention is not limited to these.

Among these thermoplastic resins, those having nitrogen, oxygen, sulfur and aromatic ring in the composition are preferable.
Although the reason for this is not clear, it is thought that the presence of these specific elements or structures has higher polarity, so that some interaction with the additives used in the present invention acts to enhance the vibration energy absorption performance. Can be

On the other hand, the improvement of the vibration energy absorbing performance according to the present invention is mainly attributable to the improvement of the loss coefficient of the glass transition region caused by the micro-Brownian motion occurring in the amorphous region of the resin. Among them, the resin belonging to the amorphous resin can obtain a higher effect.
However, the thermoplastic resin used in the present invention is not limited to this description.

The condensed polycyclic compound used in the present invention is a condensed polycyclic hydrocarbon or a condensed heterocyclic compound composed of three or more rings. There is no problem with any configuration 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 (single or condensed ring) directly bonded by a single bond or a double bond, and includes the number of such direct ring bonds. Means one less than the number of ring systems present. The ring system may be a cyclic hydrocarbon system or a heterocyclic system.
Although there is no problem with any configuration as long as it has three or more ring systems, it is particularly preferable to have many ring systems.

These condensed polycyclic compounds and ring assemblies (hereinafter collectively referred to as cyclic products) include those having 1 to 4 carbon atoms among the alkyl groups, a hydroxyl group, an oxo group, a carboxyl group,
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 substance is compounded with the thermoplastic resin, it is necessary to bring the cyclic substance into a sufficiently dispersed state.
Therefore, it is desirable that the melting point of the ring is lower than the processing temperature of the thermoplastic resin. For example, condensed polycyclic compounds include acenaphthylene, acenaphthene, phenanthrene, 9-
Phenantrol, fluorene, anthrone, 9-fluorenone, perhydrofluorene, benzophenanthrene, 9-anthracenemethanol, 9,10-dihydroanthracene, pyrene, 1,2-benzopyrene, dibenzophenanthrene, dibenzosuberane, a terpene composed of three or more rings , Steroids, alkaloids, dibenzofuran, xanthene, 9-xanthenol, xanthone,
Acridine, dibenzothiophene, phenanthridine,
1,4-benzoquinone, 7,8-benzoquinoline, 1,
Examples include 10-phenanthroline, phenanthine, phenoxazine, thianthrene and the like. As a ring set,
1,2-diphenylbenzene, 1,3-diphenylbenzene, 1,3,5-triphenylbenzene, 1,2,2
3,4-tetraphenyl-1,3-cyclopentadiene, 2,2: 6 ′, 2 ″ -terpyridine and the like.

One of these cyclic materials or a mixture of two or more thereof is compounded with a thermoplastic resin.

From the viewpoint of processability and economy, the amount of the cyclic material added is 5 to 100 parts by weight, and more than 15 to 50 parts by weight, based on 100 parts by weight of the thermoplastic resin. Is desirable.

The thermoplastic resin composition according to the present invention contains a plasticizer such as DOP, dioctyl sebacate (DOS), calcium carbonate, talc, etc., which are usually added to the thermoplastic resin to such an extent that the performance is not extremely reduced. It is possible to add inorganic fillers such as representatives, flame retardants such as antimony trioxide and zinc borate, and flake-like fillers often used for vibration energy absorbers such as mica and graphite as necessary. it can.

Further, it can be blended with a coumarone resin, a xylene resin or the like often used as a vibration energy absorbing material. However, the boiling point of these additives must be lower than the processing temperature of the thermoplastic resin.

The thermoplastic resin composition of the present invention is obtained by dry blending a thermoplastic resin and a condensed polycyclic compound or a ring assembly, or by heat-melting blending with a roll, extruder, Banbury mixer, or the like. Calendering, extrusion,
It can be formed freely by a technique such as injection molding, foam molding, compression molding and the like.

The vibration energy absorbing material obtained according to the present invention can be used as a support member for equipment such as precision electronic equipment and precision measurement equipment whose vibration may affect its accuracy, a fixing member such as a packing gasket, and an acoustic equipment. It can be used for laminated members and chassis etc. 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.

[0044]

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

Example 1 100 parts by weight of polystyrene (GP-1, manufactured by Denki Kagaku Kogyo KK) as a styrene resin and 1 part by weight of Irganox 1010 (manufactured by Nippon Ciba Geigy) as an antioxidant were added to Laboplastomill ( 17 at Toyo Seiki Co., Ltd.
The mixture was melt-kneaded at 0 ° C., further added with 20 parts by weight of pyrene as a condensed polycyclic compound, and kneaded for 5 minutes to obtain a target composition.

Example 2 In Example 1, dibenzofuran 20 was used instead of pyrene.
The desired composition was obtained by exactly the same operation except that parts by weight were used.

Example 3 A target composition was obtained in the same manner as in Example 1 except that 20 parts by weight of anthrone was used instead of pyrene.

Example 4 The same procedure as in Example 1 was repeated, except that the amount of pyrene was changed to 60 parts by weight, to obtain a target composition.

Example 5 A styrene-butadiene-styrene block copolymer (Europur) was used in Example 1 instead of polystyrene.
eneSOL T162 (manufactured by ANIC) except that 100 parts by weight were used to obtain the target composition by exactly the same operation.

Example 6 An acrylonitrile-butadiene-styrene copolymer (Diapet A) was used in Example 1 instead of polystyrene.
Except for using 100 parts by weight of BS1001, manufactured by Mitsubishi Rayon Co., Ltd., exactly the same system was mixed and kneaded at 200 ° C. to obtain a target composition.

Example 7 In Example 5, dibenzofuran 20 was used instead of pyrene.
The desired composition was obtained by exactly the same operation except that parts by weight were used.

Example 8 In Example 6, dibenzofuran 20 was used instead of pyrene.
The desired composition was obtained by exactly the same operation except that parts by weight were used.

Comparative Example 1 A target composition was obtained in exactly the same manner as in Example 1, except that 20 parts by weight of 2-methylnaphthalene was used instead of pyrene.

Comparative Example 2 A target composition was obtained in exactly the same manner as in Example 5, except that 20 parts by weight of 2-methylnaphthalene was used instead of pyrene.

Example 9 In Example 1, 1,3 was used as a ring set instead of pyrene.
A target composition was obtained by exactly the same operation except that 20 parts by weight of diphenylbenzene was used.

Example 10 A target composition was obtained by exactly the same operation as in Example 1 except that 20 parts by weight of 1,3,5-triphenylbenzene was used instead of pyrene.

Example 11 The same procedure as in Example 6 was repeated, except that 20 parts by weight of 1,3-diphenylbenzene was used instead of pyrene, to obtain a target composition.

Comparative Example 3 A target composition was obtained in exactly the same manner as in Example 1, except that 20 parts by weight of biphenyl having two rings was used instead of pyrene.

Comparative Example 4 A target composition was obtained in the same manner as in Example 1 except that 20 parts by weight of p-hydroxybiphenyl was used instead of pyrene.

Comparative Example 5 A target composition was obtained in exactly the same manner as in Example 5 except that 20 parts by weight of p-hydroxybiphenyl was used instead of pyrene.

Example 12 100 parts by weight of polyphenylene sulfide resin (Ryton P-4, manufactured by Philips Petroleum Co.) and 20 parts by weight of phenanthrene as a condensed polycyclic compound were used in Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.). The mixture was melt-kneaded at 300 ° C. for 5 minutes to obtain a target composition.

Example 13 Polyphenylene sulfide resin (Sastile GS-
40, 100 parts by weight, manufactured by Tohsosa Steel Co., Ltd.) and 5 parts by weight of 1,4-diphenylbenzene as a ring assembly were melt-kneaded in the same manner as in Example 12 to obtain the desired composition.

Example 14 A target composition was obtained in the same manner as in Example 13 except that 25 parts by weight of anthraquinone was used instead of 1,4-diphenylbenzene.

Comparative Example 6 Only the polyphenylene sulfide resin used in Example 12 was melt-kneaded in the same manner as in Example 12 to obtain a target composition.

Comparative Example 7 Only the polyphenylene sulfide resin used in Example 13 was melt-kneaded in the same manner as in Example 13 to obtain a target composition.

Example 15 Polymethyl methacrylate (VS-
100, Rohm & Haas Co. ) 100 parts by weight,
As a condensed polycyclic compound, 20 parts by weight of pyrene was melt-kneaded at 180 ° C. for 5 minutes in a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) to obtain a target composition.

Example 16 In Example 15, instead of pyrene, 1,
A target composition was obtained by exactly the same operation except that 20 parts by weight of 2-diphenylbenzene was used.

Example 17 The same procedure as in Example 16 was repeated except that 20 parts by weight of 1,3-diphenylbenzene was used instead of 1,2-diphenylbenzene, to obtain a target composition.

Comparative Example 8 Only the polymethyl methacrylate used in Example 15 was melt-kneaded in the same manner as in Example 15 to obtain a target composition.

Comparative Example 9 A target composition was obtained in exactly the same manner as in Example 15, except that 20 parts by weight of 2-methylnaphthalene was used instead of pyrene.

Example 18 100 parts by weight of high-density polyethylene (Nipolon Hard 7300A, manufactured by Tosoh Corporation) and 20 parts by weight of phenanthrene as a condensed polycyclic compound were used at 180 ° C. in a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.). The mixture was melt-kneaded for 5 minutes to obtain the desired composition.

Example 19 A target composition was obtained in exactly the same manner as in Example 18, except that 20 parts by weight of 1,3-diphenylbenzene was used as a ring assembly instead of phenanthrene.

Comparative Example 10 A target composition was obtained in the same manner as in Example 18 except that 20 parts by weight of 2-methylnaphthalene was used instead of phenanthrene.

Comparative Example 11 A target composition was obtained in the same manner as in Example 19 except that 20 parts by weight of biphenyl was used instead of 1,3-diphenylbenzene.

Example 20 Polypropylene (J-7030B, manufactured by Chisso Corporation) 1
00 parts by weight and 20 parts by weight of pyrene as a condensed polycyclic compound were subjected to a temperature of 180 ° C. using a Labo Plastomill (produced by Toyo Seiki Co., Ltd.)
For 5 minutes to obtain the desired composition.

Example 21 A target composition was obtained in the same manner as in Example 20, except that 20 parts by weight of 1,3-diphenylbenzene was used instead of pyrene.

Comparative Example 12 A target composition was obtained in the same manner as in Example 20, except that 20 parts by weight of 2-methylnaphthalene was used instead of pyrene.

Comparative Example 13 A target composition was obtained in exactly the same manner as in Example 21, except that 20 parts by weight of biphenyl was used instead of 1,3-diphenylbenzene.

Example 22 Ethylene-vinyl acetate copolymer (Ultracene 634,
100 parts by weight (manufactured by Tosoh Corporation) and 20 parts by weight of phenanthrene as a condensed polycyclic compound were melt-kneaded at 100 ° C. for 5 minutes using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) to obtain a target composition. .

Example 23 A target composition was obtained in the same manner as in Example 22 except that 20 parts by weight of 1,3-diphenylbenzene was used as a ring assembly instead of phenanthrene.

Comparative Example 14 A target composition was obtained in the same manner as in Example 22 except that 20 parts by weight of 2-methylnaphthalene was used instead of phenanthrene.

Comparative Example 15 A target composition was obtained in exactly the same manner as in Example 23 except that 20 parts by weight of biphenyl was used instead of 1,3-diphenylbenzene.

Example 24 Laboplastomill (manufactured by Toyo Seiki Co., Ltd.) was used in which 100 parts by weight of polycarbonate (Panlite K-1300, manufactured by Teijin Limited) and 20 parts by weight of pyrene as a condensed polycyclic compound were used.
At 280 ° C. for 5 minutes to obtain a target composition.

Comparative Example 16 A target composition was obtained in exactly the same manner as in Example 24 except that 20 parts by weight of 2-methylnaphthalene was used instead of pyrene.

Example 25 100 parts by weight of polyacetal (Duracon GC-25, manufactured by Polyplastics) were melted and kneaded at 200 ° C. in a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.), and pyrene was used as a condensed polycyclic compound. 20 parts by weight were added and kneaded for 5 minutes to obtain a target composition.

Example 26 The same procedure as in Example 25 was carried out except that the amount of pyrene was changed to 40 parts by weight, to obtain a target composition.

Example 27 A target composition was obtained in exactly the same manner as in Example 25 except that 20 parts by weight of 1,3-diphenylbenzene was used instead of pyrene.

Comparative Example 17 Only the polyacetal used in Example 25 was melt-kneaded in the same manner as in Example 25.

Comparative Example 18 A target composition was obtained in exactly the same manner as in Example 25 except that 20 parts by weight of biphenyl was used instead of pyrene.

Example 28 Polyarylate (U-100, manufactured by Unitika Ltd.) 10
0 parts by weight and 20 parts by weight of decacyclene as a condensed polycyclic compound were added to 30 parts by Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.).
The mixture was melt-kneaded at 0 ° C. for 5 minutes to obtain a target composition.

Comparative Example 19 Only the polyarylate used in Example 28 was melt-kneaded by the same operation.

Example 29 100 parts by weight of a thermoplastic polyurethane (9X05, manufactured by Elastol Nippon), pyrene 10 as a condensed polycyclic compound
A part by weight was roll-kneaded at a temperature of 185 ° C. for 5 minutes to obtain a target composition.

Example 30 The same system as in Example 29 was used except that 10 parts by weight of 1,3-diphenylbenzene was used instead of pyrene, and the mixture was roll-kneaded at a temperature of 185 ° C. for 5 minutes. I got something.

Example 31 The same procedure as in Example 29 was carried out except that pyrene was used in an amount of 25 parts by weight to obtain a target composition.

Comparative Example 20 Only the thermoplastic polyurethane used in Example 29 was roll-kneaded at a temperature of 185 ° C. for 5 minutes to obtain a target composition.

Comparative Example 21 A target composition was obtained in the same manner as in Example 29 except that 10 parts by weight of 2-methylnaphthalene was used instead of pyrene.

Comparative Example 22 A target composition was obtained in exactly the same manner as in Example 29 except that 10 parts by weight of biphenyl, a ring assembly composed of two rings, was used in place of pyrene.

Example 32 Modified polyphenylene oxide (Noryl SE1-GFN)
3, 100 parts by weight of General Electric Co., Ltd.) and 20 parts by weight of pyrene as a condensed polycyclic compound are melt-kneaded at 300 ° C. for 5 minutes in a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.). I got something.

Example 33 In Example 32, instead of pyrene, 1,
A target composition was obtained by exactly the same operation except that 20 parts by weight of 4-diphenylbenzene was used.

Comparative Example 23 Only the modified polyphenylene oxide used in Example 32 was melt-kneaded by the same operation.

Comparative Example 24 A target composition was obtained in the same manner as in Example 32 except that 20 parts by weight of p-hydroxybiphenyl was used instead of pyrene.

Example 34 Laboplastomill (manufactured by Toyo Seiki Co., Ltd.) was charged with 100 parts by weight of polyethylene terephthalate (ESMO # 5000, manufactured by Kuraray Co., Ltd.) as a thermoplastic polyester and 20 parts by weight of pyrene as a condensed polycyclic compound. And melt-kneaded at 240 ° C. for 10 minutes to obtain a target composition.

Example 35 In Example 34, polybutylene terephthalate (Toughpet N100) was used instead of polyethylene terephthalate.
(0, manufactured by Teijin Limited) except that 100 parts by weight were used to obtain the desired composition.

Comparative Example 25 Only the polyethylene terephthalate used in Example 34 was melt-kneaded by the same operation.

Comparative Example 26 Only the polybutylene terephthalate used in Example 35 was melt-kneaded by the same operation.

Comparative Example 27 A target composition was obtained in the same manner as in Example 34 except that 20 parts by weight of p-hydroxybiphenyl was used instead of pyrene.

Comparative Example 28 A target composition was obtained in the same manner as in Example 35 except that 20 parts by weight of p-hydroxybiphenyl was used instead of pyrene.

Example 36 100 parts by weight of nylon 12 (Rilsan AMNO, manufactured by ATOCHEM) and pyrene 20 as a condensed polycyclic compound
2 parts by weight using Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.)
The mixture was melt-kneaded at 00 ° C. for 10 minutes to obtain a target composition.

Example 37 In Example 36, instead of pyrene, 1,
A target composition was obtained by exactly the same operation except that 20 parts by weight of 3-diphenylbenzene was used.

Comparative Example 29 Only nylon 12 used in Example 36 was melt-kneaded in the same manner as in Example 36.

Comparative Example 30 A target composition was obtained in the same manner as in Example 36 except that 20 parts by weight of 2-methylnaphthalene was used instead of pyrene and the temperature was changed to 180 ° C.

Evaluation of Loss Factor (tan δ) The thermoplastic resin compositions obtained in Examples 1 to 37 and Comparative Examples 1 to 30 were each melted and kneaded at a temperature of 100 kgf / cm for 10 minutes using a press machine set at a temperature at which they were melt-kneaded. The sheet was heated and pressed under the conditions of ² to produce a sheet having a thickness of 1 mm. The compositions of Comparative Examples 27 and 28 were very fragile and could not be formed into sheets. A viscoelastic analyzer RSA which is a measuring device based on the non-resonant type forced vibration method using this sheet
II (manufactured by Rheometrics Far East Co., Ltd.), the loss coefficient was measured at a heating rate of 2 ° C./min and a measurement frequency of 10 Hz. Tables 1 to 13 show the loss coefficient and the temperature at this time.

Table 1 shows polystyrene (Reference Example 1) and styrene-butadiene-
The measured values of the styrene block copolymer (Reference Example 2) and the acrylonitrile-butadiene-styrene copolymer (Reference Example 3) alone are also shown.

[0114]

[Table 1]

[0115]

[Table 2]

[0116]

[Table 3]

[0117]

[Table 4]

[0118]

[Table 5]

[0119]

[Table 6]

[0120]

[Table 7]

[0121]

[Table 8]

[0122]

[Table 9]

[0123]

[Table 10]

[0124]

[Table 11]

[0125]

[Table 12]

[0126]

[Table 13]

[0127]

As is apparent from the above description, according to the present invention, a specific thermoplastic resin and a condensed polycyclic compound comprising three or more rings and / or a ring system comprising three or more ring systems. By compounding the ring assembly at a specific ratio, a vibration energy absorbing material having a high loss coefficient can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 3-223555 (32) Priority date August 9, 1991 (1991.8.9) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 3-235639 (32) Priority date August 23, 1991 (1991.8.23) (33) Priority claim country Japan (JP)

Claims (1)

[Claims] 1. Polyamide, polyacetal, polycarbonate, modified polyphenylene oxide (excluding a diene rubber elastic body in which a double bond in the main chain is hydrogenated),
A condensed polycyclic compound (excluding anthrone-based compounds and fluorene-based compounds) consisting of three or more rings per 100 parts by weight of at least one or more thermoplastic resins selected from the group consisting of polysulfone; and / or A thermoplastic resin composition comprising 5 to 100 parts by weight of a ring assembly comprising at least two ring systems.