JP4796385B2 - Damping agent - Google Patents

Description

The present invention relates to a damping-imparting agent to impart damping to the resin material.

Conventionally, compounds having a benzotriazole group or the like are known as damping components that impart damping properties such as damping properties to resin materials (see Patent Document 1). This kind of attenuating component is used by being mixed with a molten resin material. This damping property imparting component is a component that imparts the performance of damping the vibration energy, that is, the damping property, for example, by converting the vibration energy into heat energy.
International Publication No. 97/42844 Pamphlet

  The attenuating component described in the background art may be thermally decomposed depending on the melting temperature of the resin material and the frictional heat at the time of kneading. As described above, when the damping component is thermally decomposed, for example, in a molded product obtained from the damping material, there is a problem in that it becomes difficult to exhibit the damping property according to the blending amount of the damping component. .

This invention is made | formed in view of such the conventional situation, The objective is to provide the attenuation | damping property imparting agent which can fully exhibit attenuation | damping performance by having heat resistance.

In order to achieve the above object, the damping agent according to the first aspect of the present invention is used by mixing with a resin material, thereby imparting damping property to the resin material. The gist is that the resin material is a polyamide and contains an alkali metal salt of a mercapto-s-triazine compound as an active ingredient.

The invention described in 請 Motomeko 2, in the attenuation-imparting agent according to claim 1, based on the total weight of the resin material and the active ingredient, the active ingredient is the weight ratio of 1 to 30 wt% Thus, the gist is to be mixed with the resin material.

  According to the present invention, the damping performance can be sufficiently exhibited by having heat resistance.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The damping property imparting agent is used by being mixed with a resin material and imparts damping property to the resin material. This attenuating agent expresses a function of converting energy (excluding light energy and electrical energy) such as vibration energy, impact energy, and sound energy into heat energy in the resin material. That is, the damping property imparting agent imparts a damping property that attenuates energy propagated from the outside to the resin material.

  This attenuating agent contains a triazine compound as an active ingredient. Examples of the triazine compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2 , 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazin-2-yl] -5-[(octyl) oxy] -phenol, 2- [4-{(2-hydroxy-3-n-dodecyloxypropyl) oxy} -2-hydroxyphenyl]- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-{(2-hydroxy-3-n-tridodecyloxypropyl) oxy} -2-hydroxyphenyl] -4,6-bis (2 4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2′-hydroxyphenyl) -6-aryl-1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, and alkali metal salts of mercapto-s-triazine compounds.

  The mercapto-s-triazine compound is a compound in which a mercapto group is bonded to at least one carbon atom at the 2-position, 4-position, and 6-position in the s-triazine (that is, 1,3,5-triazine). . And the alkali metal salt of a mercapto-s-triazine compound is comprised by the mercapto group couple | bonded with the carbon atom of s-triazine forming alkali metal salt. When a mercapto group is bonded to at least two carbon atoms selected from the 2nd, 4th, and 6th positions in the s-triazine, at least one mercapto group is a plurality of mercapto groups. What is necessary is just to form the alkali metal salt.

  Examples of the mercapto-s-triazine compound include 2,4,6-trimercapto-s-triazine or 2,4-dimercapto-s-triazine. Examples of the alkali metal atom constituting the mercapto group and the alkali metal salt include lithium, sodium, and potassium. The alkali metal salt of the mercapto-s-triazine compound may be used alone or in combination of two or more. The alkali metal salt of the mercapto-s-triazine compound may be blended as an anhydride or a hydrate.

  The triazine compound is preferably an alkali metal salt of a mercapto-s-triazine compound, more preferably a sodium salt of 2,4,6-trimercapto-s-triazine, more preferably 2,4,6-trimercapto- Monosodium salt of s-triazine. In addition, as a monosodium salt of 2,4,6-trimercapto-s-triazine, for example, commercially available product Sunthiol (registered trademark) N-1 (manufactured by Sankyo Kasei Co., Ltd.) may be used. it can. In addition, as the trisodium salt of 2,4,6-trimercapto-s-triazine, for example, commercially available product Sunthiol (registered trademark) NW (manufactured by Sankyo Kasei Co., Ltd.) can be used. it can.

This attenuating agent can contain a filler, a flame retardant, a corrosion inhibitor, a colorant, an antistatic agent, a wetting agent, and the like as necessary in addition to the active ingredient.
The content of the active ingredient in the attenuating agent is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and most preferably the total amount as the active ingredient. Attenuating agent. When the content of the active ingredient is 50% by mass or more, the amount of the attenuating agent added to the resin material can be reduced, so that the handling property of the attenuating agent is improved.

  The compounding amount of the attenuating agent with respect to the resin material is a mass ratio of the active ingredient to the total mass of the resin material and the active ingredient, preferably 1 to 30% by mass, more preferably 1.5 to 20% by mass, and still more preferably. 2 to 10% by mass. When this mass ratio is less than 1 mass%, it is difficult to obtain excellent damping performance. On the other hand, if it exceeds 30% by mass, the moldability and mechanical properties may not be sufficiently obtained.

  It does not specifically limit as a resin material with which this attenuation | damping property imparting agent is mix | blended, A well-known general purpose plastic and engineering plastic can be used. General-purpose plastics include polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetate, polymethyl methacrylate, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / Methacrylic acid copolymer, ethylene / methacrylic acid ester copolymer, acrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene resin copolymer, and the like. Examples of the ethylene / acrylic acid ester copolymer include an ethylene / methyl acrylate copolymer and an ethylene / ethyl acrylate copolymer. Examples of the ethylene / methacrylic acid ester copolymer include an ethylene / methyl methacrylate copolymer and an ethylene / ethyl methacrylate copolymer. Examples of the engineering plastic include polyamide, polyester, polyacetal, polyester elastomer, and various liquid crystal polymers. A single kind of resin material may be used, or a plurality of kinds may be blended. Among these resin materials, when an engineering plastic having a melting temperature higher than that of a general-purpose resin is generally employed, the effect of the attenuating agent can be sufficiently obtained. Particularly, the effect of the attenuating agent can be remarkably obtained by using this attenuating agent by mixing it with polyamide.

  Polyamides are classified into crystalline polyamides and amorphous polyamides. Specific examples of the crystalline polyamide include, for example, polyamide 46, polyamide 66, polyamide 610, polyamide 1010, polyamide 1012, polyamide 612, polyamide 6, polyamide 11, polyamide 12, polyamide 6T66, polyamide MXD6, crystalline semi-aromatic polyamide, and the like. And polyamides thereof. Crystalline semi-aromatic polyamide refers to a polyamide having a repeating unit composed of a part derived from an aromatic carboxylic acid and a part derived from an aliphatic diamine. Specific examples of the amorphous polyamide include a polyamide having a repeating unit composed of a part derived from an aromatic carboxylic acid and a part derived from an aliphatic diamine. Examples of the aromatic carboxylic acid include terephthalic acid and its derivatives, isophthalic acid and its derivatives, and the like. Examples of the aliphatic diamine include hexamethylene diamine, tetramethylene diamine, and 2,5-dimethylhexamethylene diamine. These polyamides may be used alone or in a blend of two or more.

  The attenuating material contains a resin material as a base material and an attenuating component that imparts attenuating property to the resin material. This attenuating component is the above-described triazine compound. The resin material described above is used as the resin material. The blending amount of the damping property-imparting component with respect to the resin material is a mass ratio of the damping property imparting component to the total mass of the resin material and the damping property imparting component, preferably 1 to 30% by mass, more preferably 1.5 to 20% by mass. More preferably, it is 2 to 10% by mass.

This attenuating material may contain a filler, a flame retardant, a corrosion inhibitor, a colorant, an antistatic agent, a wetting agent, and the like as components other than the attenuating component.
The damping performance of this damping material is confirmed by the loss tangent (tan δ) measured by dynamic viscoelasticity. That is, the higher the loss tangent value, the better the damping performance. The value of the loss tangent depends on the temperature, and the loss tangent has a peak value at a predetermined temperature (peak temperature). In the attenuating material containing the polyamide as the resin material and the attenuating component, a loss tangent peak appears near room temperature (for example, 0 ° C. to 40 ° C.). For this reason, if the damping material which uses polyamide as a base material is applied as the material of the molded product used near room temperature, the damping performance can be sufficiently exhibited. In particular, the damping material containing polyamide 6 and 2,4,6-trimercapto-s-triazine sodium salt is suitable for use near room temperature.

  When the resin material is a thermoplastic resin, this attenuating material is obtained by mixing an attenuating agent (attenuating component) with a molten resin material. Further, when the resin material is a thermosetting resin, this attenuating material can be obtained by mixing an attenuating agent (attenuating component) with the resin material before curing. For mixing the resin material and the attenuating agent (attenuating component), a known mixer such as a dissolver, a Banbury mixer, a planetary mixer, a glen mill, or a kneader can be used. If vibration energy propagates to the damping material from the outside, for example, it is presumed that the vibration energy is converted into thermal energy by friction between the molecular chain of the resin material and the molecule of the triazine compound. In this way, the energy is converted in the attenuating material, so that the attenuating material exhibits the attenuating property.

  This attenuating material can be used as a molded product that exhibits attenuating properties, for example, in the fields of automobiles, interior materials, building materials, home appliances, electronic devices, industrial machine parts, and the like. In addition, this attenuating material is a molded article that absorbs impact energy, such as sports equipment such as shoes, gloves, various armor, grips, headgear, medical equipment such as casts, mats, supporters, wall materials, flooring materials, and fences. It can be applied to building materials such as, various cushioning materials, various interior materials and the like.

  When this damping material is used as a damping material, it can be used as an unconstrained damping sheet by forming the damping material into a sheet shape. The unconstrained vibration damping sheet is used in a state where one side surface of the vibration damping sheet is not restrained by being bonded to an application location. When this damping material is used as a damping material, a damping sheet obtained by molding the damping material into a sheet shape is used as a damping layer, and the damping layer is constrained on the surface of the damping layer. A constraining vibration damping sheet can be obtained by bonding a constraining layer for the purpose. Examples of the constraining layer include metal foils such as aluminum and lead, films formed from synthetic resins such as polyethylene and polyester, and nonwoven fabrics. This constrained vibration damping sheet is used in a state where both surfaces of the vibration damping layer are constrained by being bonded to an application location.

The effects exhibited by this embodiment will be described below.
(1) The attenuation imparting agent contains an alkali metal salt of a triazine compound as an active ingredient. This active ingredient sufficiently expresses the function of converting energy such as vibration energy into heat energy in the resin material. Therefore, this damping property imparting agent can impart damping properties to the resin material. For example, when a thermoplastic resin is employed as the resin material, if a resin material in which an attenuation imparting agent is blended is melt-kneaded and then molded, a molded product imparted with attenuation can be obtained. Further, for example, when a thermosetting resin is employed as the resin material, a molded product with a damping property can be obtained by mixing the damping material with the resin material before curing and then curing the resin material. It will be.

  Furthermore, since the effective component of the damping agent is excellent in heat resistance, it is effective when mixing a resin material and a damping agent or molding a resin material containing a damping agent. Thermal decomposition of the components will be suppressed. That is, the attenuation performance according to the blending amount of the attenuation imparting agent is easily exhibited, so that the attenuation performance can be sufficiently exhibited.

  (2) When the attenuating agent is used in combination with polyamide, the resulting attenuating material exhibits a loss tangent peak near room temperature (for example, 0 ° C. to 40 ° C.). For this reason, if this damping property imparting agent is applied to a molded product that uses polyamide as a base material and is used near room temperature, the damping performance can be sufficiently exerted. In particular, the damping agent containing an alkali metal salt of a mercapto-s-triazine compound, preferably a sodium salt of 2,4,6-trimercapto-s-triazine, more preferably a monosodium salt as an active ingredient is polyamide 6 By being used in combination with the material, a damping material suitable for use near room temperature can be obtained.

  (3) The attenuation imparting agent is blended so that the active ingredient is 1 to 30% by mass with respect to the total mass of the resin material and the active ingredient, thereby improving the moldability and mechanical characteristics of the resin material itself. Attenuation can be exhibited while maintaining.

  In particular, the damping agent containing an alkali metal salt of a mercapto-s-triazine compound, preferably a sodium salt of 2,4,6-trimercapto-s-triazine, more preferably a monosodium salt as an active ingredient is polyamide 6 By being used as a mixture, even if the active ingredient with respect to the total mass is 10% by mass or less, a sufficient attenuation can be imparted. As a result, the formability and mechanical properties of the polyamide 6 alone and the damping property can be exhibited in a balanced manner.

  (4) The attenuating material contains a resin material as a base material and a triazine compound as an attenuating component. As a result of sufficiently exhibiting the function of converting energy such as vibration energy into heat energy in the resin material, the damping material imparts damping properties to the damping material.

  Further, since this damping component is excellent in heat resistance, when mixing a resin material and a damping component, or molding a resin material containing a damping agent, the heat of the active component Decomposition will be suppressed. That is, the attenuation performance according to the blending amount of the attenuation imparting agent is easily exhibited, so that the attenuation performance can be sufficiently exhibited.

  (5) Since the damping material contains polyamide and a triazine compound, a peak of loss tangent is exhibited near room temperature (for example, 0 ° C. to 40 ° C.). For this reason, if this damping material is applied to a molded product used near room temperature, the damping performance can be sufficiently exhibited. In particular, a damping material containing polyamide 6 and 2,4,6-trimercapto-s-triazine sodium salt, preferably monosodium salt, is suitable for use near room temperature.

  (6) Attenuating property is maintained while maintaining moldability and mechanical characteristics of the resin material itself by containing 1 to 30% by mass of the attenuating component with respect to the total mass of the resin material and the attenuating component. Can be demonstrated. In particular, an alkali metal salt of a mercapto-s-triazine compound, preferably a sodium salt of 2,4,6-trimercapto-s-triazine, more preferably a monosodium salt is used as a damping component, and polyamide 6 is used as a resin. In the case of a material, even if the damping component with respect to the total mass is 10% by mass or less, the damping property can be sufficiently imparted. As a result, the formability and mechanical properties of the polyamide 6 alone and the damping property can be exhibited in a balanced manner.

In addition, the said embodiment can also be changed and comprised as follows.
-When manufacturing an attenuating material, after manufacturing the masterbatch which mix | blended the attenuating property imparting agent (attenuating property imparting component) with the resin material, you may further dilute the masterbatch with a resin material.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
Example 1
Monosodium salt of 2,4,6-trimercapto-s-triazine (Sunthiol (registered) with respect to 97 parts by mass of polyamide 6 (PA6, Zytel (registered trademark) 21A NC010, manufactured by DuPont) as a resin material A damping material was prepared by blending 3 parts by mass of an attenuating agent comprising only N) (trademark), manufactured by Sankyo Kasei Co., Ltd. Mixing of PA6 and attenuating agent is performed by melt-kneading PA6 at a heating temperature of 220 ° C. for 15 minutes using an MS pressure type kneader (DS1-3 type, manufactured by Moriyama Seisakusho Co., Ltd.). It was.

(Example 2)
An attenuating material was prepared in the same manner as in Example 1 except that the polyamide 6 was changed to 95 parts by mass and the attenuating agent was changed to 5 parts by mass.

(Comparative Example 1)
The polyamide 6 simple substance which does not mix | blend a damping property imparting agent was made into the comparative example 1.
<Measurement of dynamic viscoelasticity>
The damping material obtained in each example was molded into a sheet shape to obtain a sheet material having a thickness of 1 mm. Each sheet material was cut into a size of 35 mm × 5 mm to obtain a test piece for dynamic viscoelasticity measurement. Loss tangent (tan δ) was measured when the temperature of each test piece was continuously increased using a dynamic viscoelasticity measuring apparatus (RSA-II: manufactured by Rheometric Co., Ltd.) while vibrating. The measurement conditions were an excitation frequency of 10 Hz, a measurement temperature range of −20 ° C. to + 160 ° C., and a temperature increase rate of 5 ° C./min. A chart obtained by this measurement is shown in FIG.

<Result>
In each of the examples, the attenuating agent could be mixed with the resin material without generating a strange odor or white smoke due to thermal decomposition of the attenuating component during melt kneading of the resin material. As is clear from the results of FIG. 1, the loss tangent peak value in Example 1 and Example 2 is higher than the peak value of loss tangent in Comparative Example 1, so that attenuation is imparted in each example. You can see that The peak temperature of loss tangent in Example 1 is 23.0 ° C. and the peak value is 0.189, and the peak temperature of loss tangent in Example 2 is 22.7 ° C. and the peak value is 0.212. Thus, in each Example, it turns out that attenuation is exhibited near room temperature.

The graph which shows the relationship between the temperature and loss tangent in a dynamic viscoelasticity measurement.

Claims (2)

A damping property-imparting agent that imparts damping properties to the resin material by being mixed with a resin material,
The resin material is polyamide;
A damping agent comprising an alkali metal salt of a mercapto-s-triazine compound as an active ingredient. Wherein the total mass of the resin material and the active ingredient, as the active ingredient is the weight ratio of 1 to 30 wt%, the attenuation-imparting agent according to claim 1 to be mixed in the resin material.

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