JP4423167B2 - Damping agent and damping material - Google Patents

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 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

  Among 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 conventional circumstances, and an object thereof is to provide an attenuating agent and an attenuating material that can impart attenuating properties and can suppress odors. It is in.

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. , 4,4'-bis (alpha, alpha-dimethylbenzyl) diphenylamine, p-(p-toluenesulfonyl amido) diphenylamine,及 beauty N, N'-hexane-1,6-diyl bis [3- (3,5 The gist is that it contains at least one selected from di-tert-butyl-4-hydroxyphenyl) propionamide] as an active ingredient.

The invention according to claim 2 is an attenuating agent that is used in admixture with polyoxymethylene and imparts attenuating property to the polyoxymethylene, and includes 4,4′-bis ( containing at least one selected from α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, and 2,2′-methylenebis (4-ethyl-6-tert-butylphenol); It is summarized that it contains N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] as an active ingredient.

  The invention according to claim 3 is the damping agent according to claim 1 or 2, wherein the active ingredient is 3 to 40% by mass with respect to the total mass of the polyoxymethylene and the active ingredient. The gist is to be mixed with the polyoxymethylene so as to obtain a mass ratio.

The damping material of the invention described in claim 4 is a damping material containing polyoxymethylene and a damping component that imparts damping properties to the polyoxymethylene, wherein the damping component is 4,4'-bis (alpha, alpha-dimethylbenzyl) diphenylamine, p-(p-toluenesulfonyl amido) diphenylamine,及 beauty N, N'-hexane-1,6-diyl bis [3- (3,5-di And -tert-butyl-4-hydroxyphenyl) propionamide].

The invention according to claim 5 is an attenuating material containing polyoxymethylene and an attenuating component that imparts attenuating property to the polyoxymethylene, and the first attenuating component is 4, Contains at least one selected from 4'-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, and 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) And N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] as the second attenuating component. This is the gist.

  The invention according to claim 6 is the damping material according to claim 4 or 5, wherein the damping component is 3 to 40 masses with respect to the total mass of the polyoxymethylene and the damping component. % Content.

  According to this invention, while being able to provide attenuation, an odor 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.

  Attenuating agents are 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol). And at least one selected from N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] as an active ingredient.

  As an active ingredient of this attenuating agent, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine is NOCLAK (trade name) CD (Ouchi Shinsei Chemical Industry ( Etc.) can be used. As p- (p-toluenesulfonylamide) diphenylamine, which is an active ingredient of this attenuating agent, NOCRACK (trade name) TD (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), which is a commercial product of resin additives, etc. Can be used. 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), which is an active ingredient of this attenuating agent, is NOCLACK (trade name) NS-5 (Ouchi, a commercially available additive for resin). Shinsei Chemical Industry Co., Ltd.) can be used. N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], which is an active ingredient of this attenuating agent, is added for resin Irganox (trade name) 1098 (manufactured by Ciba Specialty Chemicals Co., Ltd.), which is a commercially available agent, can be used.

  The damping property-imparting agent contains the first active ingredient and the second active ingredient from the viewpoint of further exhibiting the damping performance in a temperature range from a temperature near room temperature to a high temperature side, for example, 10 ° C. to 60 ° C. It is preferable to contain. The first active ingredient is 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, and 2,2′-methylenebis (4-ethyl-6-tert- Butylphenol). The second active ingredient is N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide].

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 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% by mass, the damping performance can be exhibited while maintaining the appearance of the damping material well. Further, when the mass ratio is less than 3 mass%, it is difficult to provide excellent damping performance. On the other hand, if it exceeds 40% by mass, the attenuating material may be whitened or the surface thereof may become sticky.

  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 by utilizing 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 damping material contains polyoxymethylene and a damping component that imparts damping properties to the polyoxymethylene. This attenuating component is 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol). ), And N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide].

  The damping material contains a first damping component and a second damping property from the viewpoint of further exhibiting damping performance in a temperature range from a temperature near room temperature to a high temperature side, for example, 10 ° C. to 60 ° C. It is preferable to contain an imparting component. The first attenuating component is 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, and 2,2′-methylenebis (4-ethyl-6- tert-butylphenol). The second attenuating component is N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide].

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 material can be applied as a damping material that absorbs vibration energy in the fields of automobiles, interior materials, building materials, home appliances, electronic devices, industrial machine parts, 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 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 loss tangent peak that appears when the attenuating agent is blended exists in a temperature range of 0 ° C. to 60 ° C., for example. The peak value of the loss tangent is preferably 0.05 or more, more preferably 0.08 or more, when the excitation frequency is 10 Hz, from the viewpoint that excellent attenuation performance can be exhibited.

  The attenuating agent is used as a mixture with molten polyoxymethylene. At this time, the attenuating agent is 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, 2,2′-methylenebis (4-ethyl-6- tert-butylphenol) and at least one selected from N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] as an active ingredient is doing. Therefore, since thermal decomposition of the attenuating agent is suppressed, odor during mixing can be suppressed.

  The obtained damping material is presumed to be able to convert vibration energy or the like 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) Attenuating agent of this embodiment is 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, 2,2′-methylenebis (4-ethyl). -6-tert-butylphenol) and at least one selected from N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] is effective. Contains as a component. Therefore, thermal decomposition of the attenuating agent accompanying heat melting of polyoxymethylene is suppressed, and as a result, odor during mixing can be suppressed. Therefore, it is possible to impart attenuation to polyoxymethylene and to suppress odor.

  (2) The attenuating agent preferably contains a first active ingredient and a second active ingredient. When configured in this manner, the loss tangent peak expressed by the first active ingredient can be shifted to the high temperature side by the second active ingredient. Therefore, it is possible to provide an attenuating agent that can exhibit attenuation performance in a temperature range from a temperature near room temperature to a high temperature side, for example, 10 ° C. to 60 ° C.

  (3) It is preferable that an attenuation imparting agent is mixed with polyoxymethylene so that an active ingredient may be a 3-40 mass% mass ratio with respect to the total mass of polyoxymethylene and an active ingredient. In this case, high attenuation can be imparted while maintaining an excellent appearance of the resulting attenuation material.

  (4) The attenuating material of this embodiment includes polyoxymethylene, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, 2 as an attenuating component. , 2'-methylenebis (4-ethyl-6-tert-butylphenol), and N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propion And at least one selected from amide]. 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.

  (5) The damping material preferably contains a first damping component and a second damping component. In this case, the same effect as the effect described in the above (2) can be obtained.

  (6) 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 the above (3) can be obtained.

  (7) In this attenuating material, it is preferable that the peak temperature of the loss tangent exists in a temperature range of 10 ° C to 60 ° C. In this case, the damping material can sufficiently exhibit the damping performance in the application used in this temperature range.

Next, the technical idea that can be grasped from the above embodiment will be described below.
(A) The damping material according to any one of claims 4 to 6, wherein a peak of loss tangent (tan δ) measured by dynamic viscoelasticity exists in a temperature range of 10 ° C to 60 ° C.

  (B) The damping material according to any one of claims 4 to 6 and (a), wherein a peak value of the loss tangent (tan δ) is 0.05 or more.

Next, the embodiment will be described more specifically with reference to examples , reference examples, and comparative examples.
(Examples 1-5, Examples 7-16, and Reference Example 6 )
By mixing a polyoxymethylene copolymer (co-POM, Delrin (trade name) 460NC010, manufactured by DuPont Co., Ltd.) and an attenuating agent comprising the attenuating components shown in Tables 1 and 2, a damping material is obtained. Prepared. The co-POM and the attenuating agent were mixed by melt-kneading the co-POM at a heating temperature of 190 ° C. for 20 minutes using a mixing roll machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). . Table 1 and Table 2 show the blending amount (mass%) of each example.

(Comparative Examples 1-3)
As shown in Table 1, Comparative Example 1 is a single co-POM. Comparative Example 2 and Comparative Example 3 were respectively an attenuation imparting agent composed of N, N-dicyclohexylbenzothiazyl-2-sulfenamide (DCHBSA), and 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole (2HPMB) was used in the same manner as in each Example except that an attenuating agent was prepared. It is a thing.

<Evaluation>
The following (a) to (c) were evaluated for the damping material of each example. These evaluation results are also shown in Tables 1 and 2.

(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 device (RSA-II: manufactured by Rheometric Co., Ltd.) while vibrating each test piece. 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及び表２中の減衰性付与成分を示す略号は以下の成分を示す。

The abbreviations showing the attenuation imparting components in Table 1 and Table 2 indicate the following components.

(A) Component: 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, Nocrack (trade name) CD, manufactured by Ouchi Shinsei Chemical Co., Ltd. (B) Component: p- (p-toluenesulfonylamide) ) Diphenylamine, Nocrack (trade name) TD, manufactured by Ouchi Shinsei Chemical Co., Ltd. (C) Component: 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), Nocrack (trade name) NS-5 , Manufactured by Ouchi Shinsei Chemical Co., Ltd. (D) Component: N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], Irganox (trade name) 1098, as is clear from the Ciba Specialty Chemicals Co., Ltd. Table 1 and the results shown in Table 2, evaluation sintering of examples and the reference example 6 (a) odor Since it is good, odor upon mixing with polyoxymethylene and damping imparting agent (kneading) is suppressed. Furthermore, since the odor at the time of mixing is suppressed, the odor is also suppressed when the obtained damping material is molded. Further, as shown in FIGS. 1 and 2, in each Example, a loss tangent (tan δ) peak appears in the temperature range of 0 ° 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 each example and reference example 6 is given attenuation. In addition, the peak value (* 1) and peak temperature (* 2) of Comparative Example 1 shown in Table 1 are peaks based on the change in the polymer structure accompanying heating, and this peak is also determined by the addition of the attenuating agent. Although it is higher, the present specification focuses on a peak that appears in the temperature range of 0 ° C to 60 ° C.

In addition, as is apparent from shown to result in Table 1, in Examples 1-5 and Reference Example 6, the value of loss tangent (tan [delta) at 10 ° C. and 20 ° C., higher than the value of Comparative Example 1 . From this, it can be seen that in Examples 1 to 5 and Reference Example 6, the attenuation performance near room temperature (for example, a temperature range of 0 ° C. to 20 ° C.) is sufficiently exhibited. In Example 7, since the loss tangent peak appears at 56 ° C., which is higher than the temperature near room temperature, it can be seen that the damping performance is sufficiently exhibited in the temperature region near 56 ° C. .

  On the other hand, in Examples 8 to 16, a first attenuation imparting component and a second attenuation imparting component are contained. Therefore, it can be seen that the loss tangent peak in Examples 8 to 16 appears on the higher temperature side than the loss tangent peak in Examples 1 to 6. From this, it can be seen that in Examples 8 to 16, the damping performance is sufficiently exhibited in the temperature range from the temperature near room temperature to the high temperature side.

In each Example and Reference Example 6 , good results were obtained for (c) toughness. Furthermore, with respect to Example 4, in Examples 1 to 3 , Example 5 , Reference Example 6, and Examples 7 to 16, good results were obtained for (b) appearance. From these results, it is suggested that good results can be obtained for both (b) appearance and (c) toughness when the amount of the active ingredient (attenuating component) is less than 50% by mass.

In contrast to the evaluation results of each Example and Reference Example 6 , in Comparative Examples 2 and 3, since the conventional attenuating agent is blended, (a) the odor evaluation result is slightly poor or defective, and the conventional attenuating property is obtained. It can be seen that the imparted component generates an odor based on thermal decomposition.

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 and loss tangent in the dynamic viscoelasticity measurement of Example 3, Example 4, and Comparative Example 1. FIG.

Claims (6)

An attenuating agent used in admixture with polyoxymethylene and imparting attenuating property to the polyoxymethylene, comprising 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluene) sulfonylamido) diphenylamine,及 beauty N, as active ingredient, at least one selected from N'- hexane-1,6-diyl bis [3- (3,5-di -tert- butyl-4-hydroxyphenyl) propionamide] An attenuating agent characterized by comprising. An attenuating agent that is used in admixture with polyoxymethylene and imparts attenuating property to the polyoxymethylene, and includes 4,4′-bis (α, α-dimethylbenzyl) diphenylamine as a first active ingredient, It contains at least one selected from p- (p-toluenesulfonylamido) diphenylamine and 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), and N, N'- as the second active ingredient hexane-1,6-diyl bis衰性imparting agent reduced-you characterized by containing a [3- (3,5-di -tert- butyl-4-hydroxyphenyl) propionamide]. The polyoxymethylene 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. Attenuating agent. An attenuating material containing polyoxymethylene and an attenuating component for imparting attenuating property to the polyoxymethylene, wherein the attenuating component is 4,4′-bis (α, α-dimethylbenzyl) ) diphenylamine, p-(p-toluenesulfonyl amido) diphenylamine,及 beauty N, N'-hexane-1,6-diyl bis [3- (3,5-di -tert- butyl-4-hydroxyphenyl) propionamide] A damping material characterized in that it is at least one selected from the group consisting of An attenuating material containing polyoxymethylene and an attenuating component for imparting attenuating property to the polyoxymethylene, wherein 4,4'-bis (α, α- And at least one selected from dimethylbenzyl) diphenylamine, p- (p-toluenesulfonylamido) diphenylamine, and 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), and imparting second damping property N as a component, N'- 1,6-diyl bis reduced you characterized by containing a [3- (3,5-di -tert- butyl-4-hydroxyphenyl) propionamide]衰性material. The damping material according to claim 4 or 5, wherein the damping component is contained in an amount of 3 to 40% by mass with respect to a total mass of the polyoxymethylene and the damping component.

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