JPH11181308A - High damping material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high damping material composition capable of showing a high tan δ for a long time. SOLUTION: This composition is prepared by compounding, as a damping additive, a basic substance having not less than two bases selected from among a secondary amine, a tertiary amine, and a nitrogen contg. heterocyclic in a molecule, and, at need an acidic substance having regulating function of its basicity, into a base polymer having a polar side chain such as chlorinated polyethylene, etc., and compounding a nonionic surfactant, e.g. a polyethylene glycol, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-attenuation material composition, and more particularly, to a vibration-absorbing or sound-absorbing material 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, and the like. The present invention relates to a high damping material composition as a vibration material and a soundproofing material.

[0002]

2. Description of the Related Art A polymer material as a high damping material composition of this type exhibits a typical viscoelastic behavior.
When the material minute portion vibrates for some reason, a complex sinusoidal strain (ε ^* ) is generated in each material minute portion, thereby generating a complex sinusoidal stress (σ ^* ). Complex elastic modulus
(E ^* ) is the ratio of these as shown in the following equation. Complex modulus of elasticity (E ^* ) = complex sinusoidal stress (σ ^* ) / complex sinusoidal strain (ε ^* )

The real part of this complex elastic modulus (E ^* ) is defined as the storage elastic modulus (E ') relating to the elastic properties of the material, and the imaginary part thereof is the loss elasticity relating to the viscous properties of the material. The loss tangent (tan δ) is defined as the coefficient (E ″).
As shown in the following equation, these ratios are obtained. Loss tangent (tan δ) = loss elastic modulus (E ″) / storage elastic modulus (E ′)

The loss tangent (hereinafter simply referred to as “tan δ”) is one of the factors that determine soundproofing / damping characteristics. The higher this value, the more the mechanical energy is absorbed or released as electric or thermal energy. Thus, it is known to exhibit mechanical properties such as excellent sound absorbing properties and vibration damping properties. Conventionally, the value determined as tan δ of a high attenuation material composition is 0.1.
5 or more.

As a high attenuation 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, and a filler (mica agent, etc.)
And a plasticizer added thereto and obtained through a predetermined manufacturing process. The value of tan δ of this polymer composite material was 0.3 when various rubber materials were used as the base polymer.
About 1.0, and about 1.0 when a polymer resin material is used.
About 2.0.

[0006] The present applicant has also proposed, as a high attenuation material composition exhibiting tan δ satisfying the above-mentioned required characteristics, chlorinated polyethylene which is a base polymer having a polar side chain, various basic substances such as N, Compounding N-dicyclohexylbenzothiazyl-2-sulfenamide and the like,
A material obtained by subjecting this to heat treatment and molding has already been proposed. Among these materials, tan δ is 2.
Some are above zero.

[0007] These high attenuation compositions generally have their tan δ lowered with the passage of time. However, the present applicant has added various basic substances such as N-cyclohexyl to chlorinated polyethylene which is a base polymer having a polar side chain. Benzothiazyl-2-sulfenamide and the like,
A material obtained by mixing an acidic substance such as 2,3-benzotriazole and passing through a predetermined process has been proposed. Some of these materials have a reduction rate of 10% or less.

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

[0009]

However, N, N-
A material containing a basic substance such as dicyclohexylbenzothiazyl-2-sulfenamide is tan δ immediately after molding.
Is very high, but its value decreases due to aging.

[0010] The reason is that if the compounded basic substance is a powdery substance, it will crystallize over time, and if the compounded basic substance is a liquid substance, the domain will be changed over time. It is conceivable that they are formed to deteriorate the dispersibility, or to diffuse to cause a bloom phenomenon.

Further, N-cyclohexylbenzothiazyl- is added to the above-mentioned base polymer such as chlorinated polyethylene.
A basic substance of 2-sulfenamide is blended, and
A compound containing an acidic substance such as 2,3-benzotriazole has a small change with time, but cannot exhibit high attenuation since the original tan δ is not so high.

Further, the provision of the constraining layer on the surface of the damping material is effective to some extent in suppressing the temporal change of the material exhibiting tan δ that barely satisfies the required characteristics. It is not very effective in suppressing aging.

On the surface of the polymer material, molecular motion becomes active because the ends are concentrated, and the low molecules dispersed therein are easier to crystallize than other places, and the crystal or the crystal formed first is formed. Crystal nuclei continue to grow. Therefore, if a constraining layer is provided on the surface, a change with time can be suppressed to some extent. However, since crystals are formed from the unconstrained parts, there is actually only an effect of delaying the change over time, so as long as the basic material composition has not changed, the change over time 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 the components of the damping material in which a basic substance and, if necessary, an acidic substance are blended in a base polymer having a polar side chain, and to provide a high tan δ for a long time. It is an object of the present invention to provide a high attenuation material composition capable of exhibiting the following.

[0015]

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

Preferred examples of the "base polymer having a polar side chain" include rubber, thermoplastic elastomer, and resin. 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-acryl rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, epichlorohydrin-ethylene oxide rubber, methyl silicone rubber, vinyl Suitable examples include methyl silicone rubber, phenyl-methyl silicone rubber, silicon fluoride rubber, and fluorine rubber.

The "thermoplastic elastomer material" includes 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. Elastomers are preferred.

Further, the "resin material" includes polyvinyl chloride, chlorinated polypropylene, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl fluoride, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, and styrene. Acrylonitrile copolymer, acrylonitrile-butadiene-styrene terpolymer, vinyl chloride-vinyl acetate copolymer, acryl-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" includes a basic substance containing two or more bases selected from a secondary amine, a tertiary amine and a nitrogen-containing heterocyclic ring in one molecule, for example, a sulfenamide-based substance. Additives, thiazole additives, thiuram additives, guanidine additives, benzotriazole additives, dithiocarbamate additives, pigments, pyridine additives, lubricating oil additives, epoxy resin curing accelerators, urethane Suitable examples include a catalyst, an isocyanuric acid derivative, a hindered amine-based additive, and the like.

In this case, the "sulfenamide-based additive" includes N-cyclohexylbenzothiazyl-2
-Sulfenamide, N-tert-butylbenzothiazyl-2-sulfenamide, N-oxydiethylenebenzothiazyl-2-sulfenamide, N, N-dicyclohexylbenzothiazyl-2-sulfenamide and the like. It is mentioned as a suitable thing.

Examples of the "thiazole-based additive" include 2-
Suitable examples include (N, N-diethylthiocarbamoylthio) benzothiazole, 2- (4′-morpholinodithio) benzothiazole and the like, and “thiuram-based additives” include tetraethylthiuram disulfide, tetrabutylthiuram Disulfide and the like are preferred. As the “guanidine-based additive”,
Suitable examples include 1,3-diphenylguanidine and di-O-tolylguanidine.

The "benzotriazole-based additive" includes an ultraviolet absorber, 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 inhibitor, (1,2,3
-Benzotriazolyl-1-methyl) (1,2,4-triazolyl-1-methyl) -2-ethylhexylamine, N, N'-bis (benzotriazolylmethyl) -diaminohexane, light stabilizer Certain 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.

Suitable examples of the "dithiocarbamate-based additive" include zinc dibutyldithiocarbamate, tellurium diethyldithiocarbamate, and the like, and "pigments" include 4,4 ', 4 "-trisdimethylamino acid. Triphenylmethane, 2,2 '-(1,2-ethenediyl) bis (5-methylbenzoxazole)
And dicyclohexyl phthalate are preferred. As the “pyridine additive”, a blend of 2,2-dithiodioiridine is preferred.

Preferred examples of the "lubricating oil additive" include methylene bis (dibutyldithiocarbamate) and the preferred epoxy resin curing accelerator includes 2,4,6-tri (dimethylaminomethyl) phenol. .

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

Examples of the "isocyanuric acid derivative" include triallyl isocyanurate, tris- (2-hydroxyethyl) isocyanurate, trimethallyl isocyanurate, and tris- (2,3-dibromopropyl) which are unsaturated resin crosslinking agents. ) Isocyanurate and the like. As the "hindered amine-based 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)
Preferred examples include condensates with diethanol.

As the “acidic substance”, an acidic inorganic compound, as long as the basicity of the basic substance can be adjusted,
Both acidic organic compounds can be applied. In the present invention,
Thiazole-based acidic organic compound 2 whose performance has been particularly confirmed
-Mercaptobenzothiazole is preferred.

By adding a basic substance, tan
When δ increases or the basicity of the basic substance is adjusted, an optimal tan δ is expressed.

As the "surfactant", there are a cationic type and an anionic type, but a nonionic type is preferable. Examples of the nonionic one include 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 the aliphatic compound or Nonionic surfactants such as aliphatic carboxylic acids are included.

The incorporation of a nonionic surfactant prevents the crystallization of the basic substance and prevents the domain formation, thereby improving the dispersibility of the basic substance and the acidic substance in the base polymer. Things.

The amount of the "nonionic surfactant" is from 20 to 50 when an aliphatic compound having a hydroxyl group, carboxyl group, carbonyl group, ester bond or ether bond such as polyethylene glycol, polypropylene glycol or triol is used. % Of the aliphatic amine or aliphatic carboxylic acid ranges from 20 to 100% by weight.

If the amount of the surfactant is less than this range, no high damping performance is exhibited. If the amount is more than this range, problems such as deterioration of 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 appropriately dispersed in the polymer chain of the base polymer.

According to the high-attenuation material composition having the above structure, not only a high tan δ is developed, but also the crystallization of a basic substance and the formation of domains are prevented by the addition of a nonionic surfactant. Tanδ
Can be maintained over a long period of time.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail. First, each of the examples of the present invention was manufactured with various material compositions, which will be described. In the following description, “% by weight” means 100% by weight of the base polymer.
Means the weight% of the compounding component 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 was used as a base polymer, and a basic substance, an acidic substance and a nonionic surfactant were blended into the chlorinated polyethylene. And tan δ measurement results.

[0036]

[Table 1]

The products of the present invention (Examples 1 to 4) used chlorinated polyethylene (manufactured by Showa Denko KK, trade name "Eraslen 401A") as a base polymer, and 2-mercaptobenzothiazole (a large product) as an acidic substance. Uchikagaku Kogyo Co., Ltd .: trade name “Noxeller MP”) and N-cyclohexyl-2-benzothiazylsulfenamide (manufactured by Sanshin Chemical Co., Ltd .: trade name “Suncellar CZ”) as a basic substance. -P ") and a nonionic surfactant as a compounding component, and prepared by a predetermined process.

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

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

Next, the steps of manufacturing the product of the present invention (Examples 1 to 4) and the comparative product will be described. First, an acidic substance (2-mercaptobenzothiazole) was used in Example 1 at 38% by weight, Example 2 at 38% by weight, Example 3 at 63% by weight with respect to 100% by weight of the base polymer (chlorinated polyethylene) described above. 63% by weight was added to Example 4, and the basic substance (N-cyclohexyl-2-benzothiazylsulfenamide) was 62% by weight in Example 1, 62% by weight in Example 2, and 100% in Example 3. % By weight, 100% by weight in Example 4.
The nonionic surfactant is blended in each of Examples 1 to 4 by 20% by weight.

The mixture is kneaded at room temperature for about 15 to 20 minutes with two rolls. Next, the kneaded material is heated in a predetermined mold by a hot press machine at a temperature of 20 ° C.
Melt press molding is performed at a high temperature for about 10 minutes. Under a temperature condition of 0 ° C., 130 kgf / cm ²
And press-formed by cooling to form 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.
5 shows the measurement results.

[0043]

[Table 2]

In Comparative Example 1, 100% by weight of Eraslene 401A was used as a base polymer, 38% by weight of Noxeller MP as an acidic substance, and Suncellar C as a basic substance.
Z-G is blended at 62% by weight, and no surfactant is blended.

Comparative Example 2 contains 100% by weight of Eraslen 401A as a base polymer and PEG 4000 as a nonionic surfactant, and contains no acidic substance or basic substance.

In Comparative Example 3, 100% by weight of Eraslene 401A was used as a base polymer, 63% by weight of Noxeller MP as an acidic substance, and Suncellar C as a basic substance.
It contains 100% by weight of Z-G and contains no nonionic surfactant. The adjustment of the samples of the comparative products 1 to 3 is the same as that of the examples 1 to 4.

Next, the tan δ peak value and the peak temperature of the products of the present invention (Examples 1 to 4) and (Comparative Examples 1 to 3) were measured. 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 based on the presence or absence of a nonionic surfactant (PEG4000). As for the tan δ peak value immediately after molding, Example 1 obtained an excellent value of 1.93.
The value immediately after molding in Comparative Example 1 was not bad as in Example 1, but was not bad at 1.74, and no significant difference appeared immediately after molding.

However, looking at the values after two weeks, a great difference appears. Then, these differences will be compared using the tan δ reduction rate in the table. Incidentally, the tan δ reduction rate is defined as (tan δ reduction rate (%)) =
｛(Value of tan δ immediately after molding) − (tan tan after change with time)
(value of δ)｝ ÷ (value of tan δ immediately after molding) × 100.

The reduction rate of tan δ of Example 1 was extremely low at 7.3%, and the damping performance was maintained. However, the reduction rate of tan δ of Comparative Example 1 was 30.5%, and the damping performance was greatly reduced. I have.

FIG. 1 shows the relationship between temperature and tan δ. The peak temperature in Example 1 is 26.2 ° C., which is close to room temperature, and shows a high tan δ in a temperature range around the temperature. However, Comparative Example 1 is not only at 33.5 ° C., which is far from room temperature, but also has low tan δ.

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

Further, in order to evaluate Example 1, in comparison with Comparative Example 2 in which a basic substance and an acidic substance were not blended, as apparent from FIG. 2, Comparative Example 2 had a tan δ peak value. It is remarkably lower than that of Example 1, and is clearly unsuitable for use as an attenuating material.

Next, the molecular weight of the PEG of Example 1 was set to 400
A comparison between Example 2 in which 0 was changed to 6000 and Comparative Example 1 in which PEG was not blended shows that tan δ immediately after molding was obtained.
The peak values of both Example 2 and Comparative Example 1 are good, but a marked difference appears in the tan δ peak value after two weeks. That is, when viewed in terms of the tan δ reduction rate, Comparative Example 1
Is 30.5% as described above, whereas Example 2 is as low as 11.4%. That is, Example 2 shows that the damping property can be maintained even with the passage of time.

FIG. 3 shows the relationship between tan δ and temperature. In Example 2, higher tan δ can be expressed in a temperature range closer to the room temperature environment than in Comparative Example 1, so that high attenuation can be obtained for a long time in the room temperature environment. It can be said that the material composition has the property.

Next, “Bloom Stopper HR” was used as the nonionic surfactant in Example 3 and “Bloom Stopper HE” in Example 4 was used.
For the sample using "N", the sample of Comparative Example 3 not using such a surfactant was compared. First, as for the value of the tan δ peak value immediately after molding, Comparative Example 3 is 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.

Looking at 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%, and 4 was as low as 5.4%.

Although the value of 22.5% in Example 3 is slightly higher, the original tan δ is extremely high, so that a reduction rate of this degree does not affect the damping property. Further, the value of 5.4% in Example 4 can be said to be a value that can maintain the damping property immediately after molding almost as it is.

From the above, the evaluation of each measurement result and the overall evaluation are shown for Examples 1 to 4 and Comparative Examples 1 to 3, and Examples 1 to 4 are extremely good as the overall evaluation.
Mark) was obtained. Particularly, among them, Example 4 is remarkable in the height of the peak value and the small change with time.
Although it is considered that the material has the highest practicality as a high damping material, it is desirable to use different materials in consideration of the use environment temperature.

The present embodiment has been described above in order. In short, the high-damping material composition according to the present embodiment comprises, as a damping additive, a secondary amine, a tertiary amine and a nitrogen-containing complex in a base polymer. Since a basic substance containing two or more bases selected from a ring in one molecule is mixed with an acidic substance to adjust the degree of basicity, and further mixed with a nonionic surfactant, Since the active substance has a high degree of basicity showing a high tan δ, it does not crystallize or form a domain, and shows good dispersibility, so that a high tan δ can be expressed for a long time. Furthermore, according to the present embodiment, since a correlation is recognized between the peak temperature of each embodiment and the relationship between the glass transition temperatures of the respective components, it is possible to obtain those having the desired temperature characteristics.

The present invention is not limited to the above-described embodiment at all, and various modifications can be made without departing from the gist of the present invention. For example, in the above embodiment, chlorinated polyethylene was used as the base polymer. However, any material having a polar side chain may be used, and ethylene-polyvinyl chloride, ethylene-acetic acid copolymer-polyvinyl chloride, urethane- Other than 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-acryl rubber, chlorosulfonated polyethylene, epichlorohydrin-ethylene oxide rubber, methyl silicon rubber, vinyl-methyl silicon rubber, phenyl-methyl silicon rubber, fluorinated silicon rubber, fluorine rubber, PVC Le-based thermoplastic elastomer, polyurethane thermoplastic elastomer,
Base polymers having polar side chains, such as polyester-based thermoplastic elastomers and polyamide-based thermoplastic elastomers, can be used.

[0062] In addition to the basic substances used in the above Examples, 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-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) -benzotriazole, zinc dibutyldithiocarbamate,
Tellurium diethyldithiocarbamate, 4,4 ', 4 "-
Trisdimethylaminotriphenylmethane, 2,2'-
(1,2-ethenediyl) bis (5-methylbenzoxazole) and dicyclohexyl phthalate, 2,2-
A blend of dithiodioiridines, methylene bis (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-
Secondary amines such as condensates with (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol;
Any basic substance containing a base such as a tertiary amine and a nitrogen-containing heterocycle can be used without any limitation.

Further, as the acidic substance, an acidic organic compound was used in the above embodiment. However, since this was used to adjust the basicity of the blended components, hydrochloric acid was used as long as it fulfilled its function. And the like can be applied without any limitation. If the basicity of the components has already been optimized in the state where the acidic substance is not added, it is considered unnecessary to add the components.

The nonionic surfactants include polyalkyl ether-carboxylic acid derivatives, polyalkyl ether-polyhydric alcohol derivatives, polyalkyl ether-polyhydric alcohol-ester derivatives, polyalkyl ethers, polycarboxylic acids, and the like. Derivatives, polyhydric alcohols, polyhydric alcohol-ester derivatives and the like. Tables 3 and 4 show the structural formulas of these compounds. Here, R in the table represents an aliphatic derivative, an aromatic derivative or hydrogen.

[0065]

[Table 3]

[0066]

[Table 4]

The present invention is not limited to the compounds described above, and any compound can be used without any limitation as long as it is a compound capable of exhibiting a nonionic surfactant activity.

[0068]

According to the high damping material composition of the present invention, the base polymer having polar side chains is selected from secondary amines, tertiary amines and nitrogen-containing heterocycles as damping additives. By blending a basic substance containing two or more bases in one molecule and, if necessary, blending an acidic substance, not only a high tan δ is expressed, but also a surfactant, especially a nonionic surfactant Since the compounding agent is added, the crystallization or domain formation of the basic substance exhibiting the 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 attenuation material composition of the present invention,
A high tan δ can be exhibited over a long period of time, and it is extremely useful to apply this material to a wide range of fields such as a sound insulation wall of an acoustic room, a sound insulation partition of a building structure, and a sound insulation wall of a vehicle. In addition, compounding a surfactant can contribute to lower production costs because this material is inexpensive compared to a basic substance that is an attenuating additive, and its practicality is extremely high. There is something.

[Brief description of the drawings]

FIG. 1 shows the relationship between temperature and tan δ in the comparison between a high attenuation material composition according to the present invention (base polymer + basic substance, acidic substance + PEG4000 blend) and a comparative example (base polymer + basic substance, acidic substance blend). FIG.

[FIG. 2] Similarly, a high attenuation material composition according to the present invention (base polymer + basic substance, acidic substance + PEG4000 blend) and a comparative example (base polymer + PEG4000 blend)
FIG. 6 is a diagram showing a relationship between temperature and tan δ in comparison with FIG.

FIG. 3 Similarly, the temperature and tan δ in the comparison between the high attenuation material composition according to the present invention (base polymer + basic substance, acidic substance + PEG 6000 blend) and the comparative example (base polymer + basic substance, acidic substance blend). FIG.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI F16F 15/08 F16F 15/08 D G10K 11/162 G10K 11/16 A

Claims (8)

[Claims] 1. A basic substance containing two or more bases selected from a secondary amine, a tertiary amine and a nitrogen-containing heterocycle in one molecule in a base polymer having a polar side chain, and if necessary, a basic substance. A high-attenuation material composition comprising a surfactant and an acidic substance. 2. The base polymer includes 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-acryl rubber, chlorosulfonated polyethylene, chlorinated polyethylene, chlorinated polypropylene, epichlorohydrin rubber,
Epichlorohydrin-ethylene oxide rubber, methyl silicone rubber, vinyl-methyl silicone rubber, phenyl-
At least one or two or more rubber materials selected from methyl silicone rubber, silicon fluoride rubber, and fluorine rubber;
Or at least one or two or more selected from a polystyrene-based thermoplastic elastomer, a polyvinyl chloride-based thermoplastic elastomer, a polyolefin-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, and a polyamide-based thermoplastic elastomer Thermoplastic elastomeric material, or polyvinyl chloride, chlorinated polypropylene, polyvinylidene chloride,
Polyvinyl acetate, polyvinyl alcohol, polyvinyl fluoride, polyvinylidene fluoride, polyacrylonitrile,
Polymethyl methacrylate, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene terpolymer, vinyl chloride / vinyl acetate copolymer, acrylic / vinyl chloride graft copolymer, ethylene / vinyl chloride copolymer, ethylene The high-attenuation material composition according to claim 1, comprising at least one or two or more 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, N, N-dicyclohexylbenzothiazyl-2-sulfenamide, 2- (N, N-diethylthiocarbamoylthio) benzothiazole, 2-
(4'-morpholinodithio) at least one or two or more thiazole additives selected from benzothiazole, at least one or two or more thiuram additives selected from tetraethylthiuram disulfide and tetrabutylthiuram disulfide , 1,3-diphenylguanidine, di-O-tolylguanidine, at least one or two or more guanidine-based additives, and 2- (2-hydroxy-3- (3,4,4) 5,
6-tetrahydrophthalimide-methyl) -5-methylphenyl) -benzotriazole, 1- which is a rust inhibitor
[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) -2-ethylhexylamine, 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 "-Trisdimethylaminotriphenylmethane, 2,2'-(1,2-ethenediyl) bis (5-methylbenzoxazole)
At least one or two or more pigments selected from a blend of styrene and dicyclohexyl phthalate; a pyridine additive such as 2,2-dithiodipyridine; a lubricating oil additive such as methylene bis (dibutyldithiocarbamate);
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 more urethane catalysts selected from bis (3-dimethylaminopropyl) amine, triallyl isocyanurate as an unsaturated resin crosslinking agent, tris- (2-hydroxyethyl) isocyanurate, trimetaallyl At least one or two or more isocyanuric acid derivatives selected from isocyanurate and tris- (2,3-dibromopropyl) isocyanurate;
2,6,6-pentamethyl-4-biperidyl / tridecyl 1,2,3,4-butanetetracarboxylate,
1,2,3,4-butanetetracarboxylic acid and 2,2,2
6,6-tetramethyl-4-piperidinol and β, β,
β ′, β′-tetramethyl-3,9- (2,4,8,1
At least one or two or more materials selected from at least one or two or more hindered amine additives selected from condensates with 0-tetraoxaspiro [5,5] undecane) diethanol. The high damping material composition according to claim 1 or 2, 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 attenuation material composition according to claim 1, wherein the surfactant is a non-ionic 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 is derived from such an aliphatic compound. The high attenuation material composition according to claim 5, comprising at least one or two or more materials selected from nonionic surfactants such as aliphatic amines and aliphatic carboxylic acids. 7. The compounding amount of the nonionic surfactant is as follows:
20 to 50% by weight in the case of an aliphatic compound having a hydroxyl group, carboxyl group, carbonyl group, ester bond or ether bond such as polyethylene glycol, polypropylene glycol or triol, and a nonionic interface such as aliphatic amine or aliphatic carboxylic acid. 20 to 1 for activator
7. The high attenuation material composition according to claim 6, wherein the amount is in the range of 00% by weight. 8. The high attenuation material composition according to claim 6, wherein the molecular weight of the polyethylene glycol ranges from 1,000 to 10,000.