JP2006104299A - Damping property-imparting agent and damping material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a damping property-imparting agent which can not only impart a damping property but also suppress odors at the time of mixing, and a damping material. <P>SOLUTION: The damping property-imparting agent comprises as an effective ingredient 3,9-bisä2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane. The damping property-imparting agent is used as a mixture with a polyoxymethylene. The damping material comprises the polyoxymethylene and 3,9-bisä2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane as the damping property-imparting components. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an attenuating agent that imparts attenuating properties to polyoxymethylene and an attenuating material that exhibits attenuating properties.

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 a damping property that attenuates vibration energy, for example, by converting vibration energy into heat energy.
International Publication No. 97/42844 Pamphlet

  Incidentally, among the resin materials, polyoxymethylene (POM) is known as an engineering plastic having excellent mechanical properties. However, when the damping property-imparting component described in Patent Document 1 is mixed with the polyoxymethylene in a molten state, there is a problem that an odor based on the thermal decomposition of the damping property-generating component is generated.

  The present invention has been made in view of such a conventional situation, and an object thereof is to provide an attenuating agent and an attenuating material capable of imparting attenuating properties and suppressing odors during mixing. It is to provide.

  In order to achieve the above object, the damping agent of the invention described in claim 1 is used by mixing with polyoxymethylene, and is a damping agent that imparts damping to the polyoxymethylene. 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxa The gist is to contain spiro [5,5] undecane as an active ingredient.

  The attenuation-imparting agent of the invention according to claim 2 is the mass ratio of 3 to 40% by mass of the active ingredient based on the total mass of the polyoxymethylene and the active ingredient in the invention of claim 1. The gist is to be mixed with the polyoxymethylene.

  The damping material of the invention according to claim 3 is a damping material containing polyoxymethylene and a damping component that imparts damping properties to the polyoxymethylene, wherein the damping component is 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] It is summarized as being undecane.

  The damping material of the invention according to claim 4 is the invention according to claim 3, wherein the damping component is contained in an amount of 3 to 40% by mass with respect to the total mass of the polyoxymethylene and the damping component. The gist is that

  ADVANTAGE OF THE INVENTION According to this invention, while being able to provide attenuation, the odor at the time of mixing can be suppressed.

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

  The attenuating agent is 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8. , 10-tetraoxaspiro [5,5] undecane as an active ingredient.

  As the attenuating agent, Adekastab (trade name) AO-80 (manufactured by Asahi Denka Kogyo Co., Ltd.) and Sumilizer (trade name) GA-80 (Sumitomo Chemical Co., Ltd.), which are commercially available additives for resin, are used. Can be used.

  The blending amount of the attenuating agent with respect to polyoxymethylene is a mass ratio of the active ingredient to the total mass of polyoxymethylene and the active ingredient, preferably 3 to 40% by mass, more preferably 4 to 35% by mass, and still more preferably. It is 5-30 mass%. When the mass ratio is 3 to 40 mass%, the damping performance can be exhibited while maintaining the toughness of polyoxymethylene. Further, when the mass ratio is less than 3 mass%, it is difficult to provide excellent damping performance. On the other hand, when it exceeds 40 mass%, the moldability of the attenuating material may be deteriorated or the brittleness of the attenuating material may be increased.

  Polyoxymethylene (POM), also called polyacetal, is a crystalline engineering plastic that is excellent in wear resistance, toughness, chemical resistance, and the like. This polyoxymethylene is used in a wide range of fields such as the electric / electronic field, the automobile field, the industrial machine field, and the building field, taking advantage of its characteristics.

  Polyoxymethylene herein includes homopolymers and copolymers (co-POM). Examples of the polyoxymethylene copolymer include a copolymer of oxymethylene and oxyethylene. Polyoxymethylene homopolymers and copolymers may be used alone or in a blend of homopolymers and copolymers.

  For mixing the polyoxymethylene and the attenuating agent, a known mixer such as a dissolver, Banbury mixer, planetary mixer, Glen mill, kneader or the like can be used.

  The resulting attenuating material is polyoxymethylene and 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5] as an attenuating component that imparts attenuating properties to the polyoxymethylene. -Methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane. This attenuating material can contain a filler, a flame retardant, a corrosion inhibitor, a colorant, an antistatic agent, a wetting agent, and the like as other components as required.

  The damping material is applied to, for example, automobiles, interior materials, building materials, home appliances, and the like as vibration damping materials that absorb vibration energy, and can be applied to vibration-damped locations such as motors. 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 bonding the vibration damping layer side to an application location.

  This attenuating material is an impact absorbing material that absorbs impact energy, for example, sports equipment such as shoes, gloves, various armor, grips, headgear, medical equipment such as casts, mats, supporters, wall materials, floor materials, fences, etc. It can be applied to building materials, various cushioning materials, various interior materials and the like. When this attenuating material is used as a shock absorbing material, it can be used as a shock absorbing sheet by forming the attenuating material into a sheet shape. This shock absorbing sheet is used by being bonded to an application location.

  The damping performance of this damping material is confirmed by the loss tangent (tan δ) measured by dynamic viscoelasticity. In this attenuating material, the peak temperature of loss tangent expressed by the addition of the attenuating agent is in the temperature range of 20 ° C to 60 ° C. The peak value of the loss tangent existing in this temperature range is preferably 0.05 or more, more preferably 0.08 when the excitation frequency is 10 Hz, from the viewpoint that excellent damping performance can be exhibited. That's it.

  The attenuating agent is used as a mixture with molten polyoxymethylene. At this time, this attenuating agent is 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2. , 4,8,10-tetraoxaspiro [5,5] undecane as an active ingredient. Therefore, since thermal decomposition of the attenuating agent is suppressed, odor during mixing can be suppressed.

  The obtained damping material is presumed that vibration energy and the like can be converted into thermal energy by friction between the molecular chain of polyoxymethylene and the molecule of the active ingredient. Therefore, it is considered that this attenuating agent can impart attenuating property to the resin material.

The effects exhibited by this embodiment will be described below.
(1) The attenuation-imparting agent of this embodiment is 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl. } -2,4,8,10-tetraoxaspiro [5,5] undecane is contained as an active ingredient. Therefore, thermal decomposition of the attenuating agent accompanying heat melting of polyoxymethylene is suppressed, and as a result, odor during mixing can be suppressed. Accordingly, it is possible to impart attenuation to the polyoxymethylene and to suppress odor during mixing.

  (2) The attenuating agent is preferably mixed with polyoxymethylene so that the active ingredient is in a mass ratio of 3 to 40% by mass with respect to the total mass of polyoxymethylene and the active ingredient. In this case, high attenuation can be imparted while maintaining the characteristics of polyoxymethylene.

  (3) The attenuating material of this embodiment includes polyoxymethylene and 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) as an attenuating component. Propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane. According to this configuration, the damping performance can be exhibited and at the time of manufacturing the damping material by mixing the polyoxymethylene in a molten state and the damping imparting component, and the obtained damping material Odor based on thermal decomposition of the attenuating component can be suppressed during the molding process of forming.

  (4) The attenuating material preferably contains 3 to 40% by mass of the attenuating component with respect to the total mass of the polyoxymethylene and the attenuating component. In this case, the same effect as the effect described in (2) is obtained.

  (5) In this attenuating material, the peak temperature of the loss tangent is in the range of 20 ° C to 60 ° C. Therefore, the attenuation material can sufficiently exhibit its attenuation performance by being applied to an application used near room temperature.

Next, the technical idea that can be grasped from the above embodiment will be described below.
(A) The damping material according to claim 3 or 4, wherein a peak of loss tangent (tan δ) measured by dynamic viscoelasticity exists in a temperature range of 20 ° C to 60 ° C.

  (B) The attenuating material according to (a) above, wherein a peak value of the loss tangent (tan δ) in a temperature range of 20 ° C. to 60 ° C. is 0.05 or more.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
(Examples 1-5)
Polyoxymethylene copolymer (co-POM, Delrin (trade name) 460NC010, manufactured by DuPont) and 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) Propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane (Adekastab (trade name) AO-80 (Asahi Denka Kogyo Co., Ltd.) The mixing of the co-POM and the attenuating agent was performed using a mixing roll machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) at a heating temperature of 190 ° C. This was carried out by melt-kneading co-POM under the conditions of 20 minutes, and the blending amount (mass%) of each example is shown in Table 1.

(Comparative Examples 1-3)
Comparative example 1 is co-POM simple substance. In Comparative Examples 2 and 3, N, N-dicyclohexylbenzothiazyl-2-sulfenamide (DCHBSA) and 2- [2′-hydroxy-3 ′-(3 ″, Attenuating materials were prepared in the same manner as in the examples except that 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole (2HPMB) was used.

<Evaluation>
The following (a) to (c) were evaluated for the damping material of each example. These evaluation results are also shown in Table 1.

(A) Odor About the odor at the time of kneading | mixing by a mixing roll machine, five testers performed sensory evaluation about the odor. Good if all 5 responded as odorless (○) Slightly poor (△) that 1 or more of 4 responded that no more than 5 responded odor, and all 5 responded that there was odor It was determined to be defective (x).

(B) Appearance The appearance of the attenuating material of each example was visually confirmed and the surface tackiness was evaluated. Attenuating material with no whitening and tackiness was good (○), whitening and tackiness were confirmed slightly poor (△), and both whitening and tackiness were confirmed Things were judged as bad (x).

(C) Toughness A sheet material having a thickness of 1 mm was obtained by molding the damping material obtained in each example into a sheet shape. Each sheet material was cut into a size of 35 mm × 5 mm, and the sheet material was bent so that one end in the length direction of the cut sheet material was in contact with the other end. At that time, it was determined that the sheet material was elastically deformed and no crack was generated (good), and the sheet material was determined to be defective (x). In addition, since this toughness has good followability with respect to the application site of the damping material, the damping performance of the damping material is easily exhibited.

<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 + 150 ° C., and a temperature increase rate of 5 ° C./min.

表１に示す結果から明らかなように、各実施例では（ａ）臭気の評価結果が良好であるため、ポリオキシメチレンと減衰性付与剤との混合時の臭気が抑制されることがわかる。さらに、図１及び図２に示すように各実施例では、２０℃〜６０℃の温度範囲に損失正接（ｔａｎδ）のピークが発現している。この温度範囲において、比較例１では損失正接（ｔａｎδ）のピークが存在していない。このことから、各実施例では減衰性が付与されていることがわかる。加えて、表１に示すの結果から明らかなように、各実施例の２０℃及び４０℃における損失正接（ｔａｎδ）の値は、比較例１の値よりも高い。このことから、各実施例では常温付近（例えば、２０℃〜４０℃の温度範囲）おける減衰性能が十分に発揮されることがわかる。なお、表１に示す比較例１のピーク値（※１）及びピーク温度（※２）は、加熱に伴う高分子構造の変化に基づくピークであって、このピークも減衰性付与剤の配合によって高くなるが、本明細書では２０℃〜６０℃の温度範囲に発現するピークに着眼している。

As is clear from the results shown in Table 1, it can be seen that in each example, (a) the odor evaluation result is good, so that the odor during mixing of the polyoxymethylene and the attenuating agent is suppressed. Furthermore, as shown in FIGS. 1 and 2, in each of the examples, a loss tangent (tan δ) peak appears in the temperature range of 20 ° C. to 60 ° C. In this temperature range, there is no loss tangent (tan δ) peak in Comparative Example 1. From this, it can be seen that attenuation is imparted in each example. In addition, as is apparent from the results shown in Table 1, the loss tangent (tan δ) values at 20 ° C. and 40 ° C. of each Example are higher than those of Comparative Example 1. From this, it can be seen that in each example, the attenuation performance near normal temperature (for example, a temperature range of 20 ° C. to 40 ° C.) is sufficiently exhibited. In addition, the peak value (* 1) and peak temperature (* 2) of Comparative Example 1 shown in Table 1 are peaks based on a change in the polymer structure accompanying heating, and this peak is also determined by the addition of the attenuating agent. Although it becomes high, the present specification focuses on a peak that appears in a temperature range of 20 ° C to 60 ° C.

  In addition, in Examples 1 to 4 with respect to Example 5, good results were obtained for (b) appearance and (c) toughness. From these results, it is suggested that favorable results can be obtained for (b) appearance and (c) toughness when the blending amount of the active ingredient (attenuating component) is less than 50% by mass.

  In contrast to the evaluation results of each example, in Comparative Examples 2 and 3, since the conventional attenuation imparting agent is blended, the evaluation result of (a) odor is slightly poor or defective, and the heat of the conventional attenuation imparting component It turns out that the odor based on decomposition | disassembly generate | occur | produces.

The graph which shows the relationship between the temperature in the dynamic viscoelasticity measurement of Example 1, Example 2, and Comparative Example 1 and a loss tangent. The graph which shows the relationship between the temperature in the dynamic viscoelasticity measurement of Examples 3-5 and the comparative example 1, and a loss tangent.

Claims (4)

An attenuating agent that is used in combination with polyoxymethylene and imparts attenuating property to the polyoxymethylene, and comprises 3,9-bis {2- [3- (3-t-butyl-4-hydroxy- 5-Methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane as an active ingredient Agent. The attenuating agent according to claim 1, wherein the active ingredient is mixed with the polyoxymethylene so that the active ingredient is in a mass ratio of 3 to 40% by mass with respect to the total mass of the polyoxymethylene and the active ingredient. . An attenuating material containing polyoxymethylene and an attenuating component for imparting attenuating property to the polyoxymethylene, wherein the attenuating component is 3,9-bis {2- [3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane Damping material. The damping material according to claim 3, wherein the damping component is contained in an amount of 3 to 40% by mass with respect to the total mass of the polyoxymethylene and the damping component.

Images