JPH10138365A - Laminated damping steel material of unconstrained type - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a product which is light-weighted, easy to be worked, and has excellent vibration energy absorbing performance comparing with the laminated damping steel material of constrained type by a method wherein an active constituent increasing the dipole moment in parent material is compounded into the parent material constituting the vibration damping material. SOLUTION: In order to develope most efficiently absorbing performance of vibration energy in a use temperature range, a high polymer such as polyvinyl chloride, polyethylene, etc., which has a glass transition temperature in the use temperature range is used as a parent material. Then, an active constituent which increases a dipole moment in the parent material is that in which the dipole moment of that itself, or a constituent wherein though the dipole moment of that itself is small, the dipole moment of the parent material is increased by blending that. The dipole moment of the parent material is increased by blending this active constituent, and energy absorbing performance can be increased by restoring action of the dipole when vibration energy is transmitted thereby.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an automobile, an interior material,
The present invention relates to an unconstrained vibration damping material that is applied to a place where vibration occurs, such as a building material and a home appliance, and absorbs the energy of the vibration.

[0002]

2. Description of the Related Art Conventionally, viscoelastic polymers such as rubbers, plastics and asphalts have been mainly used as damping materials. Further, there are two types of conventional vibration damping materials: a non-restrained damping material and a restrained damping material. An unconstrained damping material absorbs vibration energy by the expansion and contraction of a viscoelastic layer (polymer layer) caused by the deformation of a substrate such as an iron plate due to the excitation stress, and also by the friction inside the polymer. is there.

However, as shown in FIG. 6, it is difficult for this unconstrained vibration damping material to have a vibration energy absorption performance, for example, a loss factor (Loss Factor: η) of 0.1 or more. If required, increase the thickness or use a constrained damping material in which both sides of the viscoelastic layer (polymer layer) are fixed at two interfaces between the substrate and the constraining layer, such as a damping steel plate. You either did.

However, in the case of an unconstrained type vibration damping material having a large thickness, there is a limit to what can improve the absorbing performance of vibration energy to a certain extent, and furthermore, the material can be cut or bent in accordance with the size or shape of an applied portion. This makes it difficult to perform such a process, and furthermore, the damping material itself becomes heavy and bulky, so that it is not easy to attach the damping material to an applied portion.

On the other hand, when a constrained vibration damping material is used, since the substrate and the constraining layer are provided on both sides of the viscoelastic layer (polymer layer), the material becomes heavy and requires a lot of work, and the cost is high. Become.

The inventors of the present invention have conducted intensive studies on an unconstrained damping material having excellent vibration energy absorbing performance in order to solve such a technical problem. As a result, the amount of dipole moment in the damping material has been studied. Has a deep relationship with the vibration energy absorption performance of the unconstrained damping material,
By adding a specific component, the amount of dipole moment in the unconstrained damping material can be increased, and thereby the vibration energy absorption performance of the unconstrained damping material can be dramatically improved. I found it.

[0007] The present invention has been made based on the above findings, and is a non-restraint which is lightweight, thin, easy to process, and has excellent vibration energy absorption performance comparable to a restraint type vibration damping material. The main purpose is to provide a mold damping material.

Another object of the present invention is to provide a non-restraint type vibration damping material exhibiting good vibration energy absorption performance in a use temperature range.

Still another object of the present invention is to provide an unrestrained damping material exhibiting excellent vibration energy absorbing performance in a wide temperature range.

[0010]

In order to achieve the above object, according to the first aspect of the present invention, an active ingredient for increasing the amount of dipole moment in the base material is added to the base material constituting the vibration damping material. The gist of the present invention is a non-restraint type vibration damper characterized by being made.

The invention according to claim 2 is characterized in that the base material is made of a polar polymer selected from polyvinyl chloride, chlorinated polyethylene, acrylic rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, and chloroprene rubber. The non-restraint type vibration damping material is the gist.

The gist of the invention according to claim 3 is that an unconstrained vibration damping material characterized in that the base material is made of a polymer having a glass transition point in a use temperature range.

According to a fourth aspect of the present invention, the active ingredient is the base material 1.
The gist of the present invention is a non-restraint type vibration damper characterized by being blended in a ratio of 101 to 500 parts by weight with respect to 00 parts by weight.

According to a fifth aspect of the present invention, there is provided an unconstrained vibration damping material characterized in that the active ingredient is at least one compound selected from compounds containing a mercaptobenzothiazyl group. Abstract.

According to a sixth aspect of the present invention, there is provided an unconstrained vibration damping material characterized in that the compound containing a mercaptobenzothiazine group is N, N-dicyclohexylbenzothiazyl-2-sulfenamide. Abstract.

According to a seventh aspect of the invention, there is provided an unconstrained vibration damper characterized in that the compound containing a mercaptobenzothiazine group is 2-mercaptobenzothiazole.

The gist of the invention described in claim 8 is that the non-restraint type vibration damping material is characterized in that the compound containing a mercaptobenzothiazine group is dibenzothiazyl sulfide.

According to a ninth aspect of the present invention, there is provided an unconstrained vibration damping material characterized in that the active ingredient is one or more selected from compounds having a benzotriazole group. did.

The invention according to claim 10 is that the compound having a benzotriazole group is 2- {2'-hydroxy-
The gist of the present invention is an unconstrained vibration damping material characterized by being 3 '-(3 ", 4", 5 ", 6" tetrahydrophthalimidemethyl) -5'-methylphenyl} -benzotriazole. .

The invention according to claim 11 is a compound according to claim 11, wherein the compound having a benzotriazole group is 2- {2'-hydroxy-
The gist of the present invention is an unconstrained vibration damping material characterized by 5'-methylphenyl} -benzotriazole.

According to a twelfth aspect of the present invention, the compound having a benzotriazole group is 2- {2'-hydroxy-
The gist of the present invention is an unconstrained vibration damping material characterized by 3'-t-butyl-5'-methylphenyl} -5-chlorobenzotriazole.

According to a thirteenth aspect of the present invention, the compound having a benzotriazole group is 2- {2'-hydroxy-
The gist of the present invention is an unconstrained vibration damping material characterized by 3 ', 5'-di-t-butylphenyl} -5-chlorobenzotriazole.

According to a fourteenth aspect of the present invention, there is provided an unconstrained vibration damping material characterized in that the active ingredient is at least one compound selected from compounds having a diphenyl acrylate group. did.

According to a fifteenth aspect of the present invention, the compound having a diphenylacrylate group is ethyl-2-cyano-3,
The gist of the present invention is an unrestrained damping material characterized by being 3-di-phenyl acrylate.

The invention according to claim 16 is characterized in that at least two or more active components having different glass transition points are blended in the base material, and the temperature range in which the vibration damping property is exhibited is expanded. The non-restraint type damping material to be used is the gist.

According to a seventeenth aspect of the present invention, at a frequency of 110H
The gist of the present invention is a non-constrained vibration damper characterized by having a dielectric loss factor of 50 or more in z.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the non-restraint type vibration damping material of the present invention will be described in detail. The non-constrained vibration damping material of the present invention is obtained by blending an active component that increases the amount of dipole moment into a base material that constitutes the vibration damping material.

First, the relationship between the amount of dipole moment and the ability to absorb vibration energy will be described. FIG. 1 shows an arrangement state of the dipoles 12 inside the base material 11 before the vibration energy is transmitted. It can be said that the arrangement state of the dipole 12 is in a stable state. However, the transmission of the vibration energy causes a displacement in the dipole 12 existing inside the base material 11, and as shown in FIG.
Each dipole 12 inside 1 will be placed in an unstable state, and each dipole 12 will try to return to a stable state as shown in FIG.

At this time, energy is consumed. Through the displacement of the dipole inside the base material 11 and the energy consumption due to the restoring action of the dipole,
It is considered that vibration energy is absorbed.

From the vibration damping mechanism, it is considered that the larger the amount of the dipole moment inside the base material 11 as shown in FIGS. 1 and 2, the higher the damping property of the base material 11. Can be For this reason, it is very useful to use a component having a large dipole moment inside the molecule as a component constituting the base material in order to ensure higher vibration energy absorption performance.

A polar polymer having a large dipole moment in the molecule is exemplified by a polar polymer. As the polar polymer, specifically, polyvinyl chloride, chlorinated polyethylene, acrylic rubber (ACR),
Examples include acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), and chloroprene rubber (CR). These polar polymers are also excellent in mechanical strength and workability.

Further, the non-restraint type vibration damping material of the present invention can be used for automobiles,
Since it is applied in a wide range of fields such as interior materials, building materials, and home electric appliances, it may vibrate at the temperature at the time of use at the place where the vibration occurs (hereinafter referred to as the use temperature range; specifically, -20 ° C to 40 ° C). Making the most of the energy damping property is one of the important factors in applying the non-restraint type damping material.

In the non-constrained vibration damping material of the present invention, a polymer having a glass transition point in the operating temperature range is used as the base material so that the vibration energy absorbing performance is best exhibited in the operating temperature range. Has been proposed. As the polymer having a glass transition point in the temperature range of use, specifically, polyvinyl chloride, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyvinylidene fluoride, polyisoprene, polystyrene, styrene- Polymers such as butadiene-acrylonitrile copolymer, styrene-acrylonitrile copolymer, and di-2-
Ethylhexyl phthalate (DOP), dibutyl phthalate (DBP), diisononyl phthalate (DINP)
A polymer having a glass transition point (Tg) shifted to an operating temperature range of -20 ° C to 40 ° C by adding a plasticizer such as -20 ° C to 40 ° C or a polymer itself having an operating temperature of -20 ° C to 40 ° C Rubber (AC) having a glass transition point (Tg) in the
R), acrylonitrile-butadiene rubber (NBR),
Styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber (NR), isoprene rubber (I
R), chloroprene rubber (CR), and polymers such as chlorinated polyethylene.

When selecting the components constituting the base material, the amount of the dipole moment inside the molecule and the operating temperature range, as well as the application and use form of the unconstrained damping material, are selected. It is also desirable to consider handling, moldability, availability, temperature performance (heat resistance and cold resistance), weather resistance, price, and the like.

The active component is a component that dramatically increases the amount of dipole moment in the base material. The active component itself has a large dipole moment, or the active component itself has a small dipole moment. But,
A component that can dramatically increase the amount of dipole moment in the base material by blending the active component.

For example, under a predetermined temperature condition and a magnitude of vibration energy, the amount of the dipole moment generated in the base material 11 can be adjusted by adding an active component to the base material 11 as shown in FIG. It will be increased by a factor of 3 or 10 below. Along with this, it is considered that the energy consumption due to the restoring action of the dipole when the vibration energy is transmitted will also increase drastically, resulting in an absorption performance far exceeding the prediction.

Examples of the active ingredient that induces such an effect include N, N-dicyclohexylbenzothiazyl-
2-sulfenamide (DCHBSA), 2-mercaptobenzothiazole (MBT), dibenzothiazyl sulfide (MBTS), N-cyclohexylbenzothiazyl-2-sulfenamide (CBS), N-tert-
Butylbenzothiazyl-2-sulfenamide (BB
S), a compound containing a mercaptobenzothiazyl group such as N-oxydiethylenebenzothiazyl-2-sulfenamide (OBS), N, N-diisopropylbenzothiazyl-2-sulfenamide (DPBS),

A benzotriazole in which an azole group is bonded to a benzene ring is used as a mother nucleus, and 2- (2'-hydroxy-3 '-(3 ", 4",
5 ", 6" tetrahydrophthalimidemethyl) -5'-
Methylphenyl} -benzotriazole (2HPMM
B), 2- {2'-hydroxy-5'-methylphenyl} -benzotriazole (2HMPB), 2- {2 '
-Hydroxy-3'-t-butyl-5'-methylphenyl} -5-chlorobenzotriazole (2HBMPC
B), 2- {2'-hydroxy-3 ', 5'-di-t
Compounds having a benzotriazole group, such as -butylphenyl} -5-chlorobenzotriazole (2HDBPCB);

Alternatively, ethyl-2-cyano-3,3-
One or more compounds selected from compounds containing a diphenyl acrylate group such as di-phenyl acrylate can be mentioned.

The amount of the above-mentioned active ingredient to be mixed is as follows:
A ratio of 101 to 500 parts by weight to 00 parts by weight is preferable. For example, when the compounding amount of the active ingredient is less than 101 parts by weight, the effect of compounding the active ingredient to increase the amount of the dipole moment cannot be obtained, and the compounding amount of the active ingredient exceeds 500 parts by weight. May not be sufficiently compatible.

In deciding the active ingredient to be mixed with the base material, it is necessary to consider the easiness of compatibility between the active ingredient and the component constituting the base material, that is, the SP value, and to select the one having a similar value. good.

The amount of the dipole moment varies depending on the types of the components constituting the base material and the active components. Even when the same component is used, the amount of the dipole moment changes depending on the temperature at which the vibration energy is transmitted. In addition, the amount of the dipole moment changes depending on the magnitude of the transmitted vibration energy. Therefore, taking into account the temperature and the magnitude of vibration energy when applied as an unconstrained damping material, the components and active components constituting the base material are adjusted so that the amount of dipole moment becomes the largest at that time. It is desirable to use it selectively.

The active ingredient is not limited to one kind, and two or more kinds can be mixed. Further, in this case, it is also possible to extend at least two or more kinds of active components having different glass transition points into the base material so as to extend the temperature range in which the vibration damping property is exhibited. For example, a combination of DCHP and DCHBSA when polyvinyl chloride is used as a base material, and DC
Combinations of HP, DCHBSA and ECDPA can be mentioned.

Further, in addition to the active ingredient, fillers such as mica scales, glass chips, glass fibers, carbon fibers, calcium carbonate, barite, precipitated barium sulfate, etc., for the purpose of further improving the absorption performance, are contained in the matrix. Will be filled. The filling amount of the filler is preferably 20 to 80% by weight. For example, when the filling amount of the filler is less than 20% by weight, the absorption performance is not sufficiently improved even if the filler is filled, and even if the filling amount of the filler exceeds 80% by weight, Such a disadvantage that the filling cannot be performed or the mechanical strength of the vibration damping material decreases.

The non-restraint type vibration damping material of the present invention can be obtained by blending the components constituting the base material, the active component, and the filler. In this case, a hot roll, a Banbury mixer, a twin-screw kneader A conventionally known apparatus for melt mixing such as an extruder can be used.

As described above, the unconstrained vibration damping material in which the active ingredient is blended with the base material has a remarkable increase in the amount of dipole moment in the base material, and therefore exhibits excellent vibration energy absorbing performance. The amount of the dipole moment in the unconstrained damping material is expressed by AB shown in FIG.
It is expressed as a difference in dielectric constant (ε ′) between the two. That is, the larger the difference in the dielectric constant (ε ′) between AB shown in FIG. 4 is, the larger the amount of the dipole moment is.

FIG. 4 is a graph showing the relationship between the permittivity (ε ′) and the permittivity (ε ″). The permittivity (ε ′) and the permittivity (ε ″) shown in this graph are shown. )
Dielectric loss factor (ε ″) = dielectric constant (ε ′) × dielectric tangent (tan)
δ).

The inventor of the present invention has found through research on an unconstrained damping material that the higher the dielectric loss factor (ε ″) is, the higher the loss coefficient (η) is. That is, there is a correlation between the dielectric loss factor (ε ″) indicating the electronic physical properties of the polymer and the loss coefficient (η) indicating the mechanical properties.

Based on this finding, the dielectric loss factor (ε ″) of the above-described unconstrained vibration damping material was examined.
It was found that the non-constrained vibration damping material having a dielectric loss factor of 50 or more at 10 Hz has a high value of the loss coefficient (η) and has excellent vibration energy absorption performance.

[0050]

【Example】

Example 1 To 9 parts by weight of polyvinyl chloride, 65.0 parts by weight of mica scales (Clarite Mica, 30C, manufactured by Kuraray Co., Ltd.), 13.0 parts by weight of DCHP, and 13.0 parts by weight of DCHBSA were blended. Is put into a roll set at 160 ° C. and kneaded.
The sheet is heated for 180 seconds by being sandwiched between molds heated to a temperature of 0 ° C., and then pressed with a press at a pressure of 80 kg · f / cm ² for 30 seconds to form a sheet to a thickness of 1 mm. The obtained sheet was cut into a size of 67 mm × 9 mm for measuring a loss coefficient,
Use it as a test piece.

Example 2 65.0 parts by weight of mica scales (Clarite Mica, 30C, manufactured by Kuraray Co., Ltd.), 10.4 parts by weight of DCHP, 10.4 parts by weight of DCHBSA, 5.2 parts by weight of ECDPA to 9 parts by weight of polyvinyl chloride The test pieces were obtained in the same manner as in Example 1 except that they were blended in parts by weight.

Comparative Example 50.0 parts by weight of mica scales (Clarite Mica, 30C, manufactured by Kuraray Co., Ltd.) was blended with 50 parts by weight of polyvinyl chloride to which DOP was added. A test piece was obtained.

The dielectric loss factor (ε ″), loss coefficient (η), and elastic tangent (tan δ) of the test pieces of Examples 1 and 2 and Comparative Example were measured. (Tan δ) is measured by a dynamic viscoelasticity measurement test device (Reo Vibron DDV-25FP, manufactured by Orientec Co., Ltd.), and the dielectric loss factor (ε ″) is measured by an impedance / gain phase analyzer 4194A, Yokogawa Hewlett Each measurement was performed using a measurement device manufactured by Packard Co., Ltd. Table 1 shows the measurement results of the dielectric loss tangent (tan δ), the dielectric constant (ε ′) and the dielectric loss factor (ε ″) of each test piece.
FIG. 5 shows the measurement results of the loss coefficient (η).

[0054]

From Table 1 and FIG. 5, the test pieces of Examples 1 and 2 have a vibration energy absorption performance, that is, a loss coefficient (η) of about 5 to 7 times that of the comparative example. That the vibration damping material of the present invention has an excellent vibration energy absorption performance far exceeding the absorption performance of the conventional non-restraint type damping material and comparable to the restrained type damping material. I understand. In addition, the dielectric loss factor (ε ″) of each of the test pieces of Examples 1 and 2 greatly exceeded 50.

[0056]

According to the non-restraint type vibration damping material of the present invention, the active ingredient is blended in the base material constituting the vibration damping material, and the amount of dipole moment in the base material is dramatically increased. As a result, while being lightweight, thin, and easy to process, it exhibits a performance that is 5 to 7 times that of conventional non-constrained damping materials, and has excellent vibration energy absorption comparable to constrained damping materials. Has performance.

In the case of a non-constrained vibration damping material having a dielectric loss factor of 50 or more at a frequency of 110 Hz, the vibration damping material is applied to a place where vibration occurs, such as an automobile, an interior material, a building material, a home appliance, and the like. Demonstrates absorption performance.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a dipole in a base material.

FIG. 2 is a schematic diagram showing a state of a dipole in a base material when vibration energy is transmitted.

FIG. 3 is a schematic diagram showing a state of a dipole in a base material when an active ingredient is blended.

FIG. 4 is a graph showing a relationship between a dielectric constant (ε ′) and a dielectric loss factor (ε ″) of a base material.

FIG. 5 is a graph showing the loss coefficient (η) at each temperature of each test piece of Examples 1 and 2 and Comparative Example.

FIG. 6 is a graph showing a relationship between a loss coefficient and a vibration energy absorption rate of a conventional unconstrained damping material and a constrained damping material.

[Explanation of symbols]

 11 ... base material 12 ... dipole

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 9/02 C08L 9/02 9/06 9/06 11/00 11/00 23/28 23/28 27/06 27/06 101/00 101/00 F16F 15/02 F16F 15/02 Q // B29K 9:00 27:06

Claims (17)

[Claims] 1. An unconstrained vibration damping material characterized in that an active ingredient for increasing the amount of dipole moment in the base material is blended in a base material constituting the vibration damping material. 2. The material according to claim 1, wherein the base material is made of a polar polymer selected from polyvinyl chloride, chlorinated polyethylene, acrylic rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, and chloroprene rubber. The described non-restraint type vibration damping material. 3. An unconstrained vibration damping material according to claim 1, wherein said base material is made of a polymer having a glass transition point in a use temperature range. 4. The non-restraint type vibration damper according to claim 1, wherein the active ingredient is blended in a ratio of 101 to 500 parts by weight with respect to 100 parts by weight of the base material. Wood. 5. The non-binding compound according to claim 1, wherein the active ingredient is one or more compounds selected from a compound containing a mercaptobenzothiazyl group. Mold damping material. 6. The compound containing a mercaptobenzothiazine group, wherein the compound containing N, N-dicyclohexylbenzothiazyl-
6. The compound according to claim 5, which is 2-sulfenamide.
The described non-restraint type vibration damping material. 7. The vibration damping material according to claim 5, wherein the compound containing a mercaptobenzothiazine group is 2-mercaptobenzothiazole. 8. The vibration damping material according to claim 5, wherein the compound containing a mercaptobenzothiazine group is dibenzothiazyl sulfide. 9. The unrestrained system according to claim 1, wherein the active ingredient is one or more selected from compounds having a benzotriazole group. Vibration material. 10. The compound having a benzotriazole group is 2- {2′-hydroxy-3 ′-(3 ″,
4 ", 5", 6 "tetrahydrophthalimidomethyl)-
The non-constrained vibration damping material according to claim 9, which is 5'-methylphenyl} -benzotriazole. 11. The vibration damping material according to claim 9, wherein the compound having a benzotriazole group is 2- {2'-hydroxy-5'-methylphenyl} -benzotriazole. 12. The compound having a benzotriazole group is 2- {2′-hydroxy-3′-t-butyl-
The non-constrained vibration damping material according to claim 9, which is 5'-methylphenyl} -5-chlorobenzotriazole. 13. The compound having a benzotriazole group is 2- {2'-hydroxy-3 ', 5'-di-t.
The non-constrained vibration damping material according to claim 9, which is -butylphenyl} -5-chlorobenzotriazole. 14. The non-restraining system according to claim 1, wherein the active ingredient is one or more compounds selected from compounds having a diphenyl acrylate group. Vibration material. 15. The damping material according to claim 14, wherein the compound having a diphenyl acrylate group is ethyl-2-cyano-3,3-di-phenyl acrylate. 16. The base material according to claim 1, wherein at least two or more active components having different glass transition points are blended in the base material, and the temperature range in which the vibration damping property is exhibited is extended. 15. The non-restraint type vibration damping material according to any one of 15. 17. The non-constrained vibration damping material according to claim 1, wherein the dielectric loss factor at a frequency of 110 Hz is 50 or more.