JP3468073B2 - High damping material composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-damping material composition, and more particularly, to a vibration-damping control device applied to a sound insulation wall of an acoustic room, a sound insulation partition of a building structure, a sound insulation wall of a vehicle, or the like. The present invention relates to a high damping material composition as a vibration and soundproof material.

[0002]

2. Description of the Related Art A polymeric material as a high damping material composition of this kind exhibits typical viscoelastic behavior.
When the material minute portions vibrate for some reason, a complex sine strain (ε ^* ) is generated in each material minute portion, which causes a complex sine stress (σ ^* ). Complex elastic modulus
(E ^* ) is a ratio of these as shown in the following equation. Complex elastic modulus (E ^* ) = complex sine stress (σ ^* ) / complex sine strain (ε ^* )

The real part of the complex elastic coefficient (E ^* ) is defined as the storage elastic coefficient (E ') related to the elastic property of the material, and the imaginary part thereof is the loss elastic property related to the viscous property of the material. It is defined as the coefficient (E ″). The loss tangent (tan δ) is
As shown in the following formula, these ratios are taken. Loss tangent (tan δ) = loss elastic modulus (E ″) / storage elastic modulus (E ′)

This loss tangent (hereinafter simply referred to as "tan δ") is one of the factors that determine the soundproofing / damping characteristics, and the higher this value is, the more mechanical energy is absorbed or released as electric or thermal energy. Then, it is known that it exhibits excellent mechanical properties such as sound absorbing property and vibration damping property. Conventionally, the value calculated as tan δ of a high damping material composition is 0.
It is 5 or more.

As a high damping material composition satisfying the conventional required characteristics, for example, a polymer composite material is known. This polymer-based composite material uses a polymer alloy or a polymer compound having a polymer network structure (IPN technology) as a base polymer, on which a filler (mica agent, etc.) is added.
It was obtained through a predetermined manufacturing process after adding a plasticizer. The value of tan δ of this polymer composite material is 0.3 when various rubber materials are used as the base polymer.
~ 1.0, when using a polymeric resin material, 1.0
It is about 2.0.

Further, the applicant of the present invention, as a high-damping material composition which expresses tan δ satisfying the above-mentioned required characteristics, has added various basic substances such as N, N, to chlorinated polyethylene which is a base polymer having a polar side chain. N-dicyclohexylbenzothiazyl-2-sulfenamide and the like are blended,
Materials obtained by subjecting this to heat treatment and molding have already been proposed. Among these materials, tan δ is 2.
Some are over zero.

The tan δ of these high-damping compositions generally decreases with time. However, the applicant has found that chlorinated polyethylene, which is a base polymer having a polar side chain, is added to various basic substances such as N-cyclohexyl. Benzothiazyl-2-sulfenamide and the like are added, and 1,
It proposes a material obtained by mixing an acidic substance such as 2,3-benzotriazole and the like and performing a predetermined process. Some of these materials have a reduction rate of 10% or less.

Japanese Patent Application No. 9-215746 discloses a method of suppressing the aging by providing a constraining layer on the surface of the material to suppress the bleeding phenomenon.

[0009]

However, the above-mentioned base polymer such as chlorinated polyethylene is added with N, N-.
A material containing a basic substance such as dicyclohexylbenzothiazyl-2-sulfenamide has a tan δ immediately after molding.
Is very high, but its value decreases with time.

The reason for this is that when the compounded basic substance is a powdery substance, it is crystallized by aging, and when the compounded basic substance is a liquid substance, the domains are changed by aging. It is conceivable that, when formed, the dispersibility is deteriorated, or that it is diffused to cause a bloom phenomenon.

Further, the above-mentioned base polymer such as chlorinated polyethylene is added to N-cyclohexylbenzothiazyl-
Add a basic substance of 2-sulfenamide,
A compound containing an acidic substance such as 2,3-benzotriazole does not exhibit a high damping property because the original tan δ is not so high although the change with time is small.

Further, providing a constraining layer on the surface of the damping material is effective to some extent in suppressing the change with time of a material exhibiting a tan δ that barely satisfies the required characteristics, but of a material exhibiting a very high tan δ. There is not much effect in suppressing the change over time.

On the surface of the polymer material, the molecular motion becomes active due to the concentration of the terminals, and the low molecules dispersed therein are most easily crystallized as compared with other places. Crystal nuclei grow further. Therefore, if a constraining layer is provided on the surface, the change over time can be suppressed to some extent. However, since crystals are formed from the unconstrained part, there is actually only an effect of delaying the aging, so as long as the basic material composition has not changed, aging will eventually occur. There is no substitute. That is, it is necessary to review the fundamental material composition in addition to providing the constraining layer.

The problem to be solved by the present invention is to improve the dispersibility of a compounding component of a damping material in which a basic substance having a polar side chain is mixed with a basic substance and, if necessary, an acidic substance, and to obtain a high tan δ for a long period of time. It is to provide a high damping material composition capable of expressing.

[0015]

In order to solve this problem, the high damping material composition of the present invention comprises a base polymer having a polar side chain, a secondary amine, a tertiary amine and a nitrogen-containing heterocycle. The gist of the present invention is to mix a basic substance containing two or more selected bases in one molecule and an acidic substance as necessary, and a surfactant to this.

Suitable examples of the "base polymer having a polar side chain" include rubber, thermoplastic elastomer, resin and the like. In this case, as the "rubber material", natural rubber, modified natural rubber, grafted natural rubber, cyclized natural rubber, chlorinated natural rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, Nitrile rubber / vinyl chloride resin blend, nitrile rubber / EPD
M rubber blend, butyl rubber, brominated butyl rubber, chlorinated butyl rubber, ethylene-vinyl acetate rubber, acrylic rubber, ethylene-acrylic rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, epichlorohydrin-ethylene oxide rubber, methyl silicone rubber, vinyl- Methyl silicone rubber, phenyl-methyl silicone rubber, fluorosilicone rubber, fluororubber and the like are mentioned as suitable ones.

As the "thermoplastic elastomer material", polystyrene-based thermoplastic elastomer, polyvinyl chloride-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic Elastomers are preferred.

Further, as the "resin material", polyvinyl chloride, chlorinated polypropylene, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl fluoride, polyvinylidene fluoride, polyacrylonitrile, polymethylmethacrylate, styrene.・ Acrylonitrile copolymer, acrylonitrile / butadiene / styrene terpolymer, vinyl chloride / vinyl acetate copolymer, acrylic / vinyl chloride graft copolymer, ethylene / vinyl chloride copolymer, ethylene /
Suitable examples include vinyl alcohol and chlorinated vinyl chloride.

On the other hand, the "basic substance" is a basic substance containing two or more bases selected from secondary amines, tertiary amines and nitrogen-containing heterocycles in one molecule, for example, sulfenamide compounds. Additive, thiazole-based additive, thiuram-based additive, guanidine-based additive, benzotriazole-based additive, dithiocarbamate-based additive, pigment, pyridine-based additive, lubricating oil additive, epoxy resin curing accelerator, urethane Suitable examples include catalysts, isocyanuric acid derivatives, hindered amine additives and the like.

In this case, the "sulfenamide-based additive" is N-cyclohexylbenzothiazyl-2.
-Sulfenamide, N-tert-butylbenzothiazyl-2-sulfenamide, N-oxydiethylenebenzothiazyl-2-sulfenamide, N, N-dicyclohexylbenzothiazyl-2-sulfenamide, etc. It can be mentioned as a suitable one.

As the "thiazole type additive", 2-
(N, N-diethylthiocarbamoylthio) benzothiazole, 2- (4'-morpholinodithio) benzothiazole and the like can be mentioned as preferable examples. In addition, "thiuram-based additives" include tetraethylthiuram disulfide and tetrabutylthiuram. Disulfide etc. are mentioned as a suitable thing. As "guanidine-based additives",
Suitable examples include 1,3-diphenylguanidine and di-O-tolylguanidine.

The "benzotriazole-based additive" is a UV absorber such as 2- (2-hydroxy-3).
-(3,4,5,6-tetra-hydrophthalimido-methyl) -5-methylphenyl) -benzotriazole,
1- [N, N-bis (2-ethyl-hexyl) aminomethyl] benzotriazole which is a rust preventive, (1,2,3
-Benzotriazolyl-1-methyl) (1,2,4-triazolyl-1-methyl) -2-ethylhexylamine, N, N'-bis (benzotriazolylmethyl) -diaminohexane, a light stabilizer 2,2'-methylenebis {4- (1,1,3,3-tetramethylbutyl) -6
-6 [(2H-benzotriazol-2-yl) phenyl]}, N, N-bis (benzotriazolemethyl)-
2-ethylhexylamine, N, N-bis (benzotriazolemethyl) -laurylamine, 1- (2-ethylhexylaminomethyl) -benzotriazole, 1- (laurylaminomethyl) -benzotriazole, 1- (morpholinomethyl) -benzo Suitable examples include triazole and the like.

Suitable examples of the "dithiocarbamate-based additive" include zinc dibutyldithiocarbamate and tellurium diethyldithiocarbamate, and the "pigment" includes 4,4 ', 4 "-trisdimethylamino. Triphenylmethane, 2,2 '-(1,2-ethenediyl) bis (5-methylbenzoxazole)
And dicyclohexyl phthalate are preferable, and as the "pyridine-based additive", a blend of 2,2-dithiodioyridine and the like are preferable.

As the "lubricating oil additive", methylene bis (dibutyldithiocarbamate) and as the "epoxy resin curing accelerator", 2,4,6-tri (dimethylaminomethyl) phenol is preferable. .

Furthermore, as the "urethane catalyst", dimorpholine ether, N, N ', N "-tris (dimethylaminopropyl) hexahydro-S-triazine,
Suitable examples include N, N, N-tris (3-dimethylaminopropyl) amine and N-methyl-N, N-bis (3-dimethylaminopropyl) amine.

Examples of the "isocyanuric acid derivative" include triallyl isocyanurate, tris- (2-hydroxyethyl) isocyanurate, trimetaallyl isocyanurate and tris- (2,3-dibromopropyl) which are unsaturated resin crosslinking agents. ) Suitable examples include isocyanurate. As a "hindered amine additive",
1,2,2,6,6-pentamethyl-4-biperidyl /
Tridecyl 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 2,
2,6,6-tetramethyl-4-piperidinol and β,
β, β ', β'-tetramethyl-3,9- (2,4,
8,10-Tetraoxaspiro [5,5] undecane)
A suitable product is a condensate with diethanol.

As the "acidic substance", an acidic inorganic compound, as long as it can adjust the basicity of the basic substance,
Either acidic organic compound can be applied. In the present invention,
A thiazole-based acidic organic compound whose performance has been confirmed 2
-Mercaptobenzothiazole is mentioned as a suitable one.

By blending a basic substance, tan
The optimum tan δ is expressed by increasing δ or adjusting the basicity of the basic substance.

The "surfactant" includes cation type and anion type, but nonionic type is preferable. As the nonionic one, a hydroxyl group such as polyethylene glycol, polypropylene glycol or triol, a carboxyl group, a carbonyl group, an aliphatic compound having an ester bond or an ether bond, or an aliphatic amine derived from these aliphatic compounds or Nonionic surfactants such as aliphatic carboxylic acids may be mentioned.

By incorporating a nonionic surfactant, crystallization of the basic substance is prevented, and domain formation is prevented, so that the dispersibility of the basic substance and the acidic substance in the base polymer is improved. It is a thing.

The blending amount of the "nonionic surfactant" is 20 to 50 when an aliphatic compound having a hydroxyl group such as polyethylene glycol, polypropylene glycol or triol, a carboxyl group, a carbonyl group, an ester bond or an ether bond is used. % By weight, aliphatic amines or aliphatic carboxylic acids in the range 20-100% by weight.

This is because if the amount of the surfactant added is less than this range, high damping performance is not exhibited, and if it is more than this range, problems such as poor workability of the material occur. When polyethylene glycol is used, if its molecular weight is in the range of 1,000 to 10,000, it is dispersed appropriately in the polymer chain of the base polymer.

According to the high damping material composition having the above-mentioned constitution, not only a high tan δ is expressed, but also the crystallization of the basic substance and the formation of domains are prevented by the addition of the nonionic surfactant. Because this high tan δ
Expression can be maintained for a long period of time.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. First, each of the examples of the present invention was made with various material compositions, which will be described below. In the following description, "wt%" means 100 wt% of base polymer.
It means the weight% of the compounding ingredient with respect to.

First, Table 1 shows the material composition of the products of the present invention (Examples 1 to 4) in which chlorinated polyethylene is used as a base polymer and a basic substance, an acidic substance and a nonionic surfactant are blended therein. And tan δ measurement results.

[0036]

[Table 1]

In the products of the present invention (Examples 1 to 4), chlorinated polyethylene (manufactured by Showa Denko KK: trade name "Eraslen 401A") was used as a base polymer, and 2-mercaptobenzothiazole (large) was used as an acidic substance. Uchikagaku Kogyo Co., Ltd .: trade name "NOXCELLER MP", N-cyclohexyl-2-benzothiazylsulfenamide as a basic substance (Sanshin Chemical Industry Co., Ltd .: trade name "SANCELLER CZ" -P ") is further compounded with a nonionic surfactant as a compounding ingredient, and it is produced by a predetermined process.

The products of the present invention (Examples 1 and 2) contain polyethylene glycol as a blending component as a nonionic surfactant. That is, Example 1 was a polyethylene glycol having a molecular weight of 4000 as a surfactant (manufactured by Sanyo Chemical Co., Ltd .: trade name "PEG4000"), and Example 2 was a polyethylene glycol having a molecular weight of 6000 as a surfactant (manufactured by Sanyo Kasei Co., Ltd.). : Trade name "PEG6000") is used as a compounding ingredient.

The products of the present invention (Examples 3 to 4) contain a nonionic surfactant of an aliphatic amine and an aliphatic carboxylic acid as a compounding ingredient. Example 3 is a substance containing an aliphatic amine (manufactured by Shinko Giken Co., Ltd .: trade name "Bloom St"
upper H. ER ”), a substance containing an aliphatic carboxylic acid in Example 4 (manufactured by Shinko Giken Co., Ltd .: trade name“ Blo ”).
om Stopper HR ") as a compounding ingredient.

Next, the process for producing the products of the present invention (Examples 1 to 4) and the comparative product will be described. First, 100% by weight of the above-mentioned base polymer (chlorinated polyethylene), 38% by weight of an acidic substance (2-mercaptobenzothiazole) in Example 1, 38% by weight of Example 2, 63% by weight of Example 3, 63% by weight was added to Example 4 and 62% by weight of the basic substance (N-cyclohexyl-2-benzothiazylsulfenamide) was used in Example 1, 62% by weight in Example 2 and 100% in Example 3. %, 100% in Example 4
20% by weight of each of the nonionic surfactants in Examples 1 to 4 is added.

Then, this is kneaded with two rolls at room temperature for about 15 to 20 minutes. Next, this kneaded material is heated by a heat press in a predetermined mold to a temperature of 20 ° C. or lower than the melting point of the additive.
Melt press-molding is performed at a high temperature of ℃ for about 10 minutes. Furthermore, under the temperature condition of 0 ° C., 130 kgf / cm ²
The surface pressure is applied to perform cold press molding to obtain a 2 mm sheet.

Next, Table 2 shows the material composition and tan δ of Comparative Examples 1 to 3 which are comparative products for evaluating Examples 1 to 4.
It shows the measurement results of.

[0043]

[Table 2]

In Comparative Example 1, 100% by weight of Erasulene 401A as a base polymer, 38% by weight of Noxceller MP as an acidic substance, and Sancella C as a basic substance.
62% by weight of Z-G was blended, and no surfactant was blended.

In Comparative Example 2, 100% by weight of Erasulene 401A as a base polymer and PEG4000 as a nonionic surfactant were blended, and an acidic substance and a basic substance were not blended.

In Comparative Example 3, 100% by weight of Erasulene 401A was used as the base polymer, 63% by weight of Noxceller MP was used as the acidic substance, and Sanceller C was used as the basic substance.
Z-G is blended in 100% by weight, and no nonionic surfactant is blended. The preparation of the samples of Comparative Products 1 to 3 is the same as that of Examples 1 to 4.

Next, the tan δ peak value and its peak temperature were measured for the products of the present invention (Examples 1 to 4) and (Comparative Examples 1 to 3). For this measurement, a spectrometer manufactured by Rheology Co., Ltd. was used, and the measurement conditions were a strain of 0.05% (constant) and a frequency of 15 Hz (constant).

First, the measurement results of Examples 1 to 4 will be described. First, the measurement results of Example 1 are evaluated with respect to Comparative Example 1 by the presence or absence of a nonionic surfactant (PEG4000). Regarding the tan δ peak value immediately after molding, Example 1 obtained an excellent value of 1.93.
The value of Comparative Example 1 immediately after molding was 1.74, which was not bad, although not as high as that of Example 1, and a large difference did not appear immediately after molding.

However, looking at these values after two weeks, a big difference appears. Therefore, these differences will be compared using the tan δ reduction rate in the table. By the way, the tan δ reduction rate is (tan δ reduction rate (%)) =
{(Value of tan δ immediately after molding)-(tan after aging)
The value of δ} / (the value of tan δ immediately after molding) × 100.

Although the tan δ reduction rate of Example 1 was extremely low at 7.3% and maintained its damping performance, the tan δ reduction rate of Comparative Example 1 was 30.5%, and its damping performance was greatly reduced. I got it.

Further, looking at the relationship between temperature and tan δ in FIG. 1, the peak temperature of Example 1 was 26.2 ° C., which was close to room temperature, and showed a high tan δ in the temperature range around that. However, in Comparative Example 1, not only is it 33.5 ° C. away from room temperature, but tan δ is also low.

That is, it is shown that the damping material having the composition of Example 1 can exhibit a high damping property in the room temperature environment where it is most frequently used. From the comparison between Example 1 and Comparative Example 1, it was also found that the blending of the nonionic surfactant (PEG4000) suppressed the change over time.

Further, in order to evaluate Example 1, in comparison with Comparative Example 2 in which a basic substance and an acidic substance are not blended, it is clear from FIG. 2 that Comparative Example 2 has a tan δ peak value. It can be seen that it is remarkably low as compared with Example 1 and is obviously unsuitable for use as a damping material, and it is needless to see its change with time.

Next, the molecular weight of PEG of Example 1 was adjusted to 400
Comparing Example 2 in which 0 to 6000 was changed with Comparative Example 1 in which PEG was not mixed, tan δ immediately after molding was compared.
The peak value is good in both Example 2 and Comparative Example 1, but a remarkable difference appears in the tan δ peak value after 2 weeks. That is, looking at the tan δ reduction rate, Comparative Example 1
Is 30.5% as described above, whereas in Example 2 the value is as low as 11.4%. That is, Example 2 shows that the damping property can be maintained over time.

Looking at the relationship between tan δ and temperature in FIG. 3, since Example 2 can develop a high tan δ in a temperature range closer to the room temperature environment than Comparative Example 1, a high attenuation is achieved in the room temperature environment for a long period of time. It can be said that this is a material composition that exhibits properties.

Next, "Bloom Stopper HR" used in Example 3 as the nonionic surfactant and "Bloom Stopper HE" in Example 4 were used.
The sample using “N” was compared with the sample of Comparative Example 3 in which such a surfactant was not used. First, regarding the tan δ peak value immediately after molding, Comparative Example 3 has a relatively high value of 2.15, but Example 3 has a high value of 2.84 and Example 4 has a high value of 2.58. Indicated.

Regarding the change over time (after one month), the tan δ reduction rate of Comparative Example 3 was 32.6%, whereas the tan δ reduction rate of Example 3 was 22.5%. 4 was 5.4%, which was low in all cases.

The value of 22.5% in Example 3 is slightly high, but since the original tan δ is extremely high, a decrease rate of this level has no effect on the damping property. Further, the value of 5.4% in Example 4 can be said to be a value at which the damping property immediately after molding can be maintained almost as it is.

From the above, evaluation and comprehensive evaluation of each measurement result are shown for Examples 1 to 4 and Comparative Examples 1 to 3, but Examples 1 to 4 are extremely good as a comprehensive evaluation.
Mark) was obtained. In particular, among them, Example 4 is remarkable in terms of height of peak value and little change with time,
Although it seems that the material has the highest practicality as a high-damping material, it is desirable to use different materials because of the balance with the operating environment temperature.

As described above, the present embodiment was described in order. In short, the high damping material composition according to the present embodiment has a base polymer, a secondary amine, a tertiary amine and a nitrogen-containing complex as a damping additive. Since a basic substance containing two or more bases selected from a ring in one molecule is mixed with an acidic substance for adjusting the basicity, and a nonionic surfactant is further added, the base is In the state where the organic substance has a basicity showing high tan δ, it exhibits good dispersibility without crystallization or formation of domains, so that high tan δ can be expressed for a long period of time. Furthermore, according to this example, since the correlation between the peak temperature of each example and the glass transition temperature of each compounding component is recognized, the one having the desired temperature characteristics can be obtained.

The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention. For example, although chlorinated polyethylene was used as the base polymer in the above examples, it is essential that the material has a polar side chain, such as ethylene-polyvinyl chloride, ethylene, acetic acid copolymer-polyvinyl chloride, urethane-. In addition to polyvinyl chloride, modified natural rubber, grafted natural rubber, cyclized natural rubber, chlorinated natural rubber, carboxylated nitrile rubber, nitrile rubber / vinyl chloride resin blend, nitrile rubber / EPDM rubber blend, brominated butyl rubber, chlorinated Butyl rubber, ethylene-vinyl acetate rubber, acrylic rubber, ethylene-acrylic rubber, chlorosulfonated polyethylene, epichlorohydrin-ethylene oxide rubber, methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-methyl silicone rubber, fluorosilicone rubber, fluororubber, Polyvinyl chloride Le-based thermoplastic elastomer, polyurethane thermoplastic elastomer,
A base polymer having a polar side chain such as a polyester-based thermoplastic elastomer or a polyamide-based thermoplastic elastomer can be applied.

In addition to the substances used in the above examples, the basic substances are N-tert-butylbenzothiazyl-2.
-Sulfenamide, N-oxydiethylenebenzothiazyl-2-sulfenamide, N, N-dicyclohexylbenzothiazyl-2-sulfenamide, 2- (N,
N-diethylthiocarbamoylthio) benzothiazole, 2- (4'-morpholinodithio) benzothiazole, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, 1,3-diphenylguanidine, di-O-tolylguanidine, 2- (2- Hydroxy-3- (3,4,5,6-tetra-hydrophthalimido-methyl) -5-methylphenyl) -benzotriazole, 1- [N, N-bis (2-ethyl-hexyl) aminomethyl] benzotriazole , (1,2,3-benzotriazolyl-1-methyl) (1,2,4-triazolyl-1-methyl) -2-ethylhexylamine, N,
N'-bis (benzotriazolylmethyl) -diaminohexane, 2,2'-methylenebis {4- (1,1,3,3
3-tetramethylbutyl) -6-6 [(2H-benzotriazol-2-yl) phenyl]}, N, N-bis (benzotriazolemethyl) -2ethylhexylamine, N, N-bis (benzotriazolemethyl) -Laurylamine, 1- (2-ethylhexylaminomethyl)
-Benzotriazole, 1- (laurylaminomethyl)
-Benzotriazole, 1- (morpholinomethyl) -benzotriazole, zinc dibutyldithiocarbamate,
Tellurium diethyldithiocarbamate, 4,4 ', 4 "-
Trisdimethylaminotriphenylmethane, 2,2'-
(1,2-Atenediyl) bis (5-methylbenzoxazole) and dicyclohexyl phthalate, 2,2-
A blend of dithiodioyridine, methylenebis (dibutyldithiocarbamate), 2,4,6-tri (dimethylaminomethyl) phenol, dimorpholine ether,
N, N ', N "-tris (dimethylaminopropyl) hexahydro-S-triazine, N, N, N-tris (3
-Dimethylaminopropyl) amine, N-methyl-N,
N-bis (3-dimethylaminopropyl) amine, triallyl isocyanurate, tris- (2-hydroxyethyl) isocyanurate, trimetaallyl isocyanurate, tris- (2,3-dibromopropyl) isocyanurate, 1,2 , 2,6,6-Pentamethyl-4-biperidyl / tridecyl 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl -4-piperidinol and β, β, β ', β'-tetramethyl-3,9-
A secondary amine such as a condensate of (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol,
Any basic substance containing a tertiary amine and a base such as a nitrogen-containing heterocycle can be applied without any limitation.

Further, as the acidic substance, an acidic organic compound was used in the above-mentioned examples, but since this is used for adjusting the basicity of the blending component, hydrochloric acid may be used as long as it fulfills its function. Inorganic compounds such as can be applied without any limitation. In addition, it is considered that there is no need to add the acidic substance if the basicity of the components is already optimized without adding the acidic substance.

As the nonionic surfactant, polyalkyl ether-carboxylic acid derivative, polyalkyl ether-polyhydric alcohol derivative, polyalkyl ether-polyhydric alcohol-ester derivative, polyalkyl ether, polycarboxylic acid and Examples thereof include derivatives, polyhydric alcohols, and polyhydric alcohol-ester derivatives. Structural formulas of these compounds are shown in Tables 3 and 4. However, R in the table represents an aliphatic derivative, an aromatic derivative or hydrogen.

[0065]

[Table 3]

[0066]

[Table 4]

Not limited to the compounds described above, any compound can be applied without any limitation as long as it is a compound capable of exhibiting a nonionic surface-active action.

[0068]

According to the high damping material composition of the present invention, a secondary amine, a tertiary amine and a nitrogen-containing heterocycle are selected as a damping additive to a base polymer having a polar side chain. By blending a basic substance containing two or more bases in one molecule and, if necessary, an acidic substance, a high tan δ is expressed, and further, a surfactant, particularly a nonionic surfactant Since the agent is blended, crystallization of the basic substance or domain formation exhibiting its high damping property is inhibited, whereby the dispersibility of the basic substance is improved and the change over time can be suppressed. .
Therefore, according to the high damping material composition according to the present invention,
It is possible to develop a high tan δ for a long period of time, and it is extremely useful to apply this material to a wide range of fields such as sound insulation walls for acoustic rooms, sound insulation partitions for building structures, and sound insulation walls for vehicles. Also, compounding a surfactant can contribute to lowering manufacturing costs because this material is cheaper than the basic substance that is a damping additive, and its practical possibility is extremely high. There is something.

[Brief description of drawings]

FIG. 1 shows the relationship between temperature and tan δ in the comparison between the high damping material composition according to the present invention (base polymer + basic substance, acidic substance + PEG4000 blended) and a comparative example (base polymer + basic substance, acidic substance blended). It is the figure which showed.

FIG. 2 is likewise a high-damping material composition according to the present invention (base polymer + basic substance, acidic substance + PEG4000 blend) and a comparative example (base polymer + PEG4000 blend).
It is a figure showing the relation between temperature and tan delta in contrast with.

[Fig. 3] Similarly, the temperature and tan δ in the comparison between the high damping material composition according to the present invention (base polymer + basic substance, acidic substance + PEG6000 blended) and the comparative example (base polymer + basic substance, acidic substance blended). It is the figure which showed the relationship of.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI F16F 15/08 F16F 15/08 D G10K 11/162 G10K 11/16 A (56) Reference JP-A-9-12783 (JP, A) JP-A-7-292167 (JP, A) JP-A-2-102208 (JP, A) JP-A-10-60179 (JP, A) International Publication 97/42844 (WO, A1) (58) Field (Int.Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08 F16F 7/00 F16F 15/08 G10K 11/162

Claims (8)

(57) [Claims] 1. A base polymer having a polar side chain, a basic substance containing two or more bases selected from secondary amines, tertiary amines and nitrogen-containing heterocycles in one molecule and, if necessary, a basic substance. A high-damping material composition comprising a mixture of an acidic substance and a surfactant. 2. The base polymer, natural rubber, modified natural rubber, grafted natural rubber, cyclized natural rubber, chlorinated natural rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, nitrile Rubber / vinyl chloride resin blend, nitrile rubber / EPDM rubber blend, butyl rubber, brominated butyl rubber, chlorinated butyl rubber, ethylene-
Vinyl acetate rubber, acrylic rubber, ethylene-acrylic rubber, chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated polypropylene, epichlorohydrin rubber,
Epichlorohydrin-ethylene oxide rubber, methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-
At least one kind or two or more kinds of rubber materials selected from methyl silicone rubber, fluorosilicone rubber and fluororubber,
Or at least one or two or more selected from polystyrene-based thermoplastic elastomer, polyvinyl chloride-based thermoplastic elastomer, polyolefin-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyamide-based thermoplastic elastomer Thermoplastic elastomer material, or polyvinyl chloride, chlorinated polypropylene, polyvinylidene chloride,
Polyvinyl acetate, polyvinyl alcohol, polyvinyl fluoride, polyvinylidene fluoride, polyacrylonitrile,
Polymethylmethacrylate, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene terpolymer, vinyl chloride / vinyl acetate copolymer, acrylic / vinyl chloride graft copolymer, ethylene / vinyl chloride copolymer, ethylene / The high damping material composition according to claim 1, which is made of at least one kind or two or more kinds of resin materials selected from vinyl alcohol and chlorinated vinyl chloride. 3. The basic substance is N-cyclohexylbenzothiazyl-2-sulfenamide, N-tert.
-Butylbenzothiazyl-2-sulfenamide, N-
At least one or two or more sulfenamide-based additives selected from oxydiethylenebenzothiazyl-2-sulfenamide and N, N-dicyclohexylbenzothiazyl-2-sulfenamide, 2- (N, N-diethylthiocarbamoylthio) benzothiazole, 2-
(4′-morpholinodithio) benzothiazole at least one or two or more thiazole additives, at least one or two or more thiuram additives selected from tetraethylthiuram disulfide and tetrabutylthiuram disulfide. , 3-diphenylguanidine, di-O-tolylguanidine, or at least one or more kinds of guanidine-based additives, and ultraviolet absorber 2- (2-hydroxy-3- (3,4, 5,
6-tetrahydrophthalimido-methyl) -5-methylphenyl) -benzotriazole, a rust inhibitor 1-
[N, N-bis (2-ethylhexyl) aminomethyl]
Benzotriazole, (1,2,3-benzotriazolyl-1-methyl) (1,2,4-triazolyl-1-methyl) -2-ethylhexylamine, N, N'-bis (benzotriazolylmethyl) ) -Diaminohexane, 2,2′-methylenebis {4- (1,1,
3,3-Tetramethylbutyl) -6-6 [(2H-benzotriazol-2-yl) phenyl]}, N, N-bis (benzotriazolemethyl) -2ethylhexylamine, N, N-bis (benzotriazole) Methyl) -laurylamine, 1- (2-ethylhexylaminomethyl) -benzotriazole, 1- (laurylaminomethyl) -benzotriazole, 1- (morpholinomethyl)
At least one or two or more benzotriazole-based additives selected from benzotriazole, at least one or two or more dithiocarbamate-based additives selected from zinc dibutyldithiocarbamate and tellurium diethyldithiocarbamate, 4 , 4 ', 4 "-Trisdimethylaminotriphenylmethane, 2,2'-(1,2-ethenediyl) bis (5-methylbenzoxazole)
And at least one pigment selected from blends of dicyclohexyl phthalate, pyridine-based additives such as 2,2-dithiodiopyridine, lubricating oil additives such as methylenebis (dibutyldithiocarbamate), 2,4
Epoxy resin curing accelerator such as 6-tri (dimethylaminomethyl) phenol, dimorpholine ether, N,
N ', N "-tris (dimethylaminopropyl) hexahydro-S-triazine, N, N, N-tris (3-dimethylaminopropyl) amine, N-methyl-N, N-
At least one or two or more urethane catalysts selected from bis (3-dimethylaminopropyl) amine, unsaturated resin crosslinking agents triallyl isocyanurate, tris- (2-hydroxyethyl) isocyanurate, trimetaallyl Isocyanuric acid, at least one or more isocyanuric acid derivative selected from tris- (2,3-dibromopropyl) isocyanurate, 1,2,
2,6,6-pentamethyl-4-biperidyl / tridecyl 1,2,3,4-butane tetracarboxylate,
1,2,3,4-butanetetracarboxylic acid and 2,2
6,6-tetramethyl-4-piperidinol and β, β,
β ′, β′-tetramethyl-3,9- (2,4,8,1
0-tetraoxaspiro [5,5] undecane) diethanol and at least one selected from a condensate or two or more selected from at least one hindered amine-based additive. A high damping material composition according to claim 1 or 2 characterized. 4. The high attenuation material composition according to claim 1, wherein the acidic substance is a thiazole-based or triazole-based acidic organic compound or an acidic inorganic compound. 5. The high damping material composition according to claim 1, 2, 3 or 4, wherein the surfactant is a nonionic surfactant. 6. The nonionic surfactant is an aliphatic compound having a hydroxyl group such as polyethylene glycol, polypropylene glycol, or triol, a carboxyl group, a carbonyl group, an ester bond or an ether bond, or derived from these aliphatic compounds. The high attenuation material composition according to claim 5, which is composed of at least one kind or two or more kinds of materials selected from nonionic surfactants such as aliphatic amines or aliphatic carboxylic acids. 7. The blending amount of the nonionic surfactant is
20 to 50% by weight in the case of an aliphatic compound having a hydroxyl group such as polyethylene glycol, polypropylene glycol or triol, a carboxyl group, a carbonyl group, an ester bond or an ether bond, a nonionic interface such as an aliphatic amine or an aliphatic carboxylic acid 20 to 1 for activator
High damping material composition according to claim 6, characterized in that it is in the range of 00% by weight. 8. The high damping material composition according to claim 6, wherein the polyethylene glycol has a molecular weight in the range of 1,000 to 10,000.