JP4915718B2 - Damping material and its manufacturing method - Google Patents

Description

  The present invention relates to a vibration damping material and a method for manufacturing the same, and more particularly to a vibration damping material that exhibits excellent performance as a restraint type and a non-restraint type damping material and a method for producing the same.

  As a material for reducing vibration and noise of a structure made of a metal plate such as a steel plate or an aluminum alloy plate or engineering plastic (engineering plastic material), a damping material made of a polymer material is known.

  Damping materials are largely divided into the non-restraining type that is used by sticking to the surface of a plate made of steel plate, etc., and the constraining type that is sandwiched between two plates such as a steel plate and used as part of the structure. In each case, the loss coefficient (tan δ) representing the vibration damping performance of the polymer material takes advantage of the characteristic that becomes maximum near the glass transition temperature (Tg) of the polymer material.

  The glass transition temperature is generally measured by an experiment on a time scale of about seconds or minutes (corresponding to about 1/60 to 1 Hz in terms of vibration frequency), but the experiment is performed with a shorter time scale. The apparent Tg becomes high at a vibration frequency of about 1 Hz or more. In the vibration method adopted as one of the Tg measurement methods, the dynamic elastic modulus is measured as a temperature at which the dynamic elastic modulus rapidly decreases in the dynamic elastic modulus-temperature curve. The coefficient takes a maximum value. The vibration damping peak is thought to be related to the fact that the structure of the polymer is partially relaxed and the atomic groups and small molecular chain segments can move, and this phenomenon occurs near Tg. The peak temperature of the loss coefficient (tan δ) at 1 varies depending on the frequency.

That is, the normal glass transition temperature (Tg) is measured as the temperature at which the loss factor (tan δ) is maximized in the vibration test in the range of 1/60 to 1 Hz, but the loss coefficient (tan δ) is measured in the vibration test exceeding 1 Hz. The temperature showing the peak shifts to the high temperature side. Therefore, in the present invention, the temperature at which the loss coefficient (tan δ) exhibits a peak is hereinafter referred to as “T _S ” to distinguish it from normal “Tg”.

Incidentally, the damping performance that is exhibited due to the viscoelastic characteristics of the polymer material is not uniquely determined by the Tg of the polymer material, but the temperature T that exhibits the maximum loss coefficient (tan δ) according to the frequency. It depends on _S. Also, the environmental temperature at which the structure is installed does not always coincide with the T _{S of the} polymer material used as the damping material, and it is satisfactory if the planned T _S and the actual operating environmental temperature are different. Damping performance is not demonstrated.

Therefore, in order to cope with such problems, a blended resin prepared by blending a plurality of polymer materials having different T _S so as to exhibit vibration damping performance in a wide temperature range has been proposed. For example, in Patent Documents 1 and 2, when blending two or more polyester resins having a molecular weight of 10,000 or more and a specific gravity of 0.06 to 0.15 to form a micro phase separation structure, The loss factor (tan δ) can be increased over a wide temperature range, and the adhesiveness and moldability can be improved. Furthermore, if a curing agent is added to these to form a thermosetting polyester, the adhesiveness can be further improved. At the same time, it has been clarified that the heat resistance is also improved.

In addition, regarding the viscoelastic characteristics of the damping material suitable for the restraint type damping material represented by the damping steel plate, for example, according to Patent Document 3, the elastic modulus (Young's modulus) of an elastic plate such as a steel plate is E. Then, the shear elastic modulus of the damping material sandwiched between the elastic plates (in this document, represented by the complex shear elastic modulus G = G ₁ + jG ₂ , j is an imaginary unit) is “10 ⁻⁶ E ≦ (G ₁ , G ₂ ) ≦ 10 ⁻⁴ E ”and“ 0.5 ≦ (G ₂ / G ₁ = tan δ) ≦ 3.0 ”are appropriate ranges for improving the overall damping performance. It is described that there is.

In fact, when a steel plate is used as an elastic plate, “2 × 10 ¹¹ Pa” is substituted for the elastic modulus E, and “2 × 10 ⁵ Pa ≦ (G ₁ , G ₂ ) ≦ 2 × 10 ⁷ Pa”. When the range is an Al alloy plate, “7 × 10 ¹⁰ Pa” is substituted for the elastic modulus E, and the range of “7 × 10 ⁴ Pa ≦ (G ₁ , G ₂ ) ≦ 2 × 10 ⁶ Pa”. Is described as an appropriate range of the elastic modulus of each damping material.

  In the above Patent Documents 1 and 2, by adjusting the structure and molecular weight of the polyester resin to be combined, or by further using a curing agent in combination with a thermosetting type, it exhibits vibration damping performance in a wide temperature range and has adhesiveness and It has been shown that heat resistance can be increased. However, in the system other than the exemplified resin, the design guidelines from the viewpoint of what kind of polymer materials should be mixed and in what ratio, including the selection criteria for specific polymer materials. It has not been revealed.

Further, in order to utilize the technique disclosed in Patent Document 3, the shear elastic modulus G ₁ (hereinafter referred to as rigidity: μ) and loss factor (tan δ) (= G ₂ / G ₁ ) of a commercially available adhesive are set to a frequency of 10 Hz. When actually examined in the range of 10 to 10 KHz and the temperature of 20 to 80 ° C., it was found that many of the adhesives deviated from the appropriate range described in Patent Document 3.

Therefore, in order to exhibit excellent vibration damping performance as a damping material, whether it is a restraining type or an unconstraining type, it is necessary to clarify the selection criteria as a resin material for giving damping performance.
Japanese Patent No. 2613502 JP 2003-221696 JP-A-4-160249

  The present invention has been made by paying attention to the above-described circumstances, and its purpose is to exhibit excellent vibration damping capability in a wide temperature range as a restraining type and non-constraining type damping material. It is an object of the present invention to provide a damping material capable of exhibiting a stable and excellent damping performance under various usage environments by clarifying selection criteria for resin materials.

  The vibration damping material according to the present invention that has solved the above problems is a vibration damping material used as a constraining or non-constraining vibration damping material. Is an ellipsoidal particle made of different materials, and in the case of a constrained type, the ratio of the length in the rotational axis direction to the length in the rotational axis direction when the shape of the particle is assumed to be a spheroid (aspect ratio; ω ) In the range of 0.01 to 0.1 is dispersed in an island shape, and in the case of an unconstrained type, an elliptical particle having an aspect ratio (ω) of 1 or less Is characterized by being dispersed in islands.

The ratio of the damping material according to the present invention, the shear modulus of the base material (hereinafter, referred to as the shear modulus mu _M) shear modulus of the ellipsoidal particles to (hereinafter, referred to as the modulus of rigidity mu _I) ( Hereinafter, the stiffness ratio μ _I / μ _M ) is preferably in the range of 0.02 to 0.3 for the constrained type, and preferably 1 or less for the unconstrained type. In any case, the temperature T _{S at} which the loss coefficient of the ellipsoidal particles dispersed in the island shape becomes maximum is lower than the temperature T _{S at} which the loss coefficient of the base material becomes maximum. Moreover, as the ellipsoidal particles, a vibration damping material in which a plurality of types of particles having different T _S are dispersed is preferable because it exhibits a high loss factor stably over a wide temperature range.

  When the damping material of the present invention is used as a damping material for a constrained damping material, a polyurethane-based shape memory polymer material is preferably used as the base material and the material of the ellipsoidal particles. When used as a damping material for a constrained damping material, polyolefin is used as the base material, polyester is used as the material for the ellipsoidal particles, or polypropylene is used as the base material, and polythene is used as the material for the ellipsoidal particles. It is preferred to use isobutylene.

Further, when used as a damping material for an unconstrained damping material, as a further component in the base material, a ratio of the rigidity μ _H to the rigidity μ _M of the base material (stiffness ratio: (μ _H / μ _M ) is 7 or more and the hard particles having an aspect ratio of 1.0 or less are dispersed, the loss factor as a damping material is increased and the rigidity of the composite resin as a whole is increased. This is preferable because the damping performance for the non-constrained damping material can be further enhanced.

  Still another configuration of the present invention is a method for manufacturing a sheet-shaped damping material for a constrained damping material having the above-described characteristics, and a substantially spherical shape made of a material different from the matrix in the matrix. When a composite resin in which resin particles are dispersed is processed into a sheet-like vibration-damping material, the thickness reduction rate is reduced in the process until the sheet-like vibration-damping material with the target thickness is obtained. It is characterized in that it is controlled within the range of 0.01 to 1.0.

  In addition, as a method of manufacturing a sheet-shaped damping material for an unconstrained damping material having the above characteristics, a composite in which substantially spherical resin particles made of a material different from the matrix are dispersed in the matrix. When a resin is used and the composite resin is processed into a sheet shape to obtain a damping material, the thickness reduction rate is 0.01 to 1.0 in the process until the sheet-like damping material having the target thickness is obtained. It has the feature in controlling to the range.

In order to obtain a sea / island structure in which island-like particles are dispersed in a sea component (matrix), the difference in solubility parameter between the base material and the island-like particles is preferably 1 [MPa] ^0.5 or more.

  When manufacturing the sheet-like damping material for the unconstrained damping material, the biaxial stretching method is used simultaneously or sequentially to follow the stretching of the base resin in the longitudinal and lateral directions. It is preferable to employ a method of stretching the resin particles into a flat plate shape.

According to the present invention, resin particles having an aspect ratio in a specific range are dispersed as island components in the sea component constituting the matrix, so that the temperature is high at any of the sea component T _S and the island component T _S. It is possible to provide a damping material for a constrained or unconstrained damping material that has a loss coefficient and exhibits excellent vibration damping capability in a wide temperature range at low cost.

  As described above, Patent Documents 1 and 2 disclose that a specific resin such as a polyester resin can improve the vibration damping performance in a wide temperature range by adjusting the structure and molecular weight of the resin used in combination, and can also improve adhesion and molding processing. There is a statement that the property can be improved.

  However, the specific selection criteria for the elastic modulus of the polymer material constituting the resin, including the resin material specifically used, and the elastic modulus of the polymer material used in combination therewith are It has not been revealed. Therefore, in systems other than those specifically shown, what kind of polymer material should be selected based on what criteria, and what ratio should be blended is determined by experiment each time. It must be determined by trial and error.

In addition, as described in Patent Document 3 disclosed above, the rigidity modulus μ and the loss factor (tan δ) of a commercially available adhesive having excellent adhesiveness are in a frequency range (10 Hz to 10 kHz) and a temperature range (about 20 to 80 ° C.), for example, are as follows, and are considered to be an appropriate shear elastic modulus range when a steel plate is used as the elastic plate described in Patent Document 3. “2 × 10 ⁵ Pa ≦ (μ) ≦ 2 × 10 ⁷ Pa” and a range of “0.5 ≦ tan δ ≦ 3.0” or an appropriate shear elastic modulus range when an Al alloy plate is used. It is considered that “7 × 10 ⁴ Pa ≦ (μ) ≦ 7 × 10 ⁶ Pa” and compared with the range of “0.5 ≦ tan δ ≦ 3.0”, most of the adhesives are out of the appropriate range. .

1) When the main agent is an epoxy resin and the curing agent is polyamide:
Type A: μ = 4 × 10 ⁸ to 2 × 10 ⁹ Pa, tan δ = 0.04 to 0.4
Type B; μ = 1 × 10 ⁸ to 2 × 10 ⁸ Pa, tan δ = 0.1 to 0.8
2) When the main agent is an epoxy resin and the curing agent is a modified silicone:
μ = 2 × 10 ^{7 to} 3 × 10 ⁸ Pa, tan δ = 0.1 to 0.3
3) When the main agent is 48% epoxy resin + 45% calcium carbonate and the curing agent is 55% modified silicone + 40% calcium carbonate:
μ = 1 × 10 ⁷ to 2 × 10 ⁸ Pa, tan δ = 0.1 to 0.3
4) When the main agent and curing agent are modified acrylates:
μ = 1 × 10 ⁸ to 8 × 10 ⁸ Pa, tan δ = 0.1 to 0.3
5) In case of polyurethane resin (1 liquid type):
Type A: μ = 1 × 10 ⁶ to 1 × 10 ⁷ Pa, tan δ = 0.3 to 0.6
Type B; μ = 9 × 10 ⁵ to 1 × 10 ⁷ Pa, tan δ = 0.3 to 0.5
6) For polyolefin resins:
μ = 1 × 10 ⁷ to 2 × 10 ⁸ Pa, tan δ = 0.3 to 0.5
7) For chloroprene rubber:
μ = 5 × 10 ⁵ to 1 × 10 ⁶ Pa, tan δ = 0.1 to 0.2
Therefore, the present inventors reviewed the conventional improvement direction of “strengthening the adhesiveness based on a vibration damping resin having a high vibration damping ability”, and used an adhesive having excellent adhesion but poor vibration damping. We selected it as a base resin (sometimes called a matrix or base material) and thought that it would be possible to achieve both adhesiveness and vibration control by combining a resin with excellent vibration control performance. I have been researching along the way.

As a result, the seawater (matrix) is used as the adhesive, and a composite resin with a so-called sea / island structure in which resin materials with vibration-damping performance are dispersed in islands ensures excellent adhesion. However, I thought that the damping performance could be improved. As a result of investigations based on these ideas, the rigidity (μ _M ) of the resin that constitutes the sea (hereinafter sometimes referred to as sea-like resin or sea component) and the resin that constitutes the island (hereinafter referred to as island-like resin) Or a ratio of rigidity (μ _I ) of the island component) (μ _I / μ _M : hereinafter referred to as rigidity ratio) is 0.1 to 2, more preferably 0.1 to 0.6, It has been found that a high loss factor can be obtained as a composite resin-based vibration damping material by selecting and compounding the sea / island constituent resin so that it is more preferably in the range of 0.1 to 0.4. It is carried out.

By the way, when a preferable value of the rigidity ratio required for the constrained vibration damping material when using a steel plate as the elastic plate is obtained, for example, 1 kHz when the polyolefin resin is selected as the sea-like resin constituting the composite resin. The ratio of the macroscopic rigidity (μ _All ) of the composite resin as a whole to the rigidity (μ _M ) of the polyolefin resin constituting the sea-like resin, ie, the rigidity ratio “0.05 ≦ (μ _All / μ _M ) ≦ 0.5”, and the macroscopic loss factor of the entire composite resin is “0.5 ≦ (tan δ _All ) ≦ 3.0” as described above. A preferred value. However, as shown in FIG. 1 (in the case where the shape of the island-shaped particles is spherical, the volume content (f) of the island-shaped particles is 30%, and the loss factor tan δ _M of the sea-shaped resin is 0.5), as it is, Although the macroscopic loss factor (tan δ _All ) as the composite resin can be increased to, for example, 0.9 or more, “0.05 ≦ μ _All / μ _M ” which is a preferable rigidity ratio ratio as the composite resin vibration damping material ≦ 0.5 ”is not satisfied.

Therefore, as a further improvement measure, the macroscopic rigidity as a composite resin-based vibration damping material was adjusted by dispersing spherical bubbles in a volume content of 30% in addition to the island-shaped resin in the sea-shaped resin. However, FIG. 2 (the shape of the island-shaped particles is spherical, the volume content f of the island-shaped particles is 30%, the loss factor tanδ _M of the sea-like resin is 0.5, the pores are spherical and the volume content is 30%. As shown in FIG. 5), the macroscopic loss coefficient (tan δ _All ) of the composite resin as a whole including pores is further increased, and the rigidity ratio is also in a preferable range “0.05 ≦ (μ _All / μ _M ) ≦ 0.5 ”.

  However, in order to obtain such a modification effect, an operation such as additional blending of a pyrolytic foaming agent and uniform dispersion and then heat foaming is required, which causes an increase in cost.

Further, taking a polyurethane memory-based shape memory polymer (hereinafter abbreviated as SMP) as an example, 30 T _S is contained in a base material (sea resin) made of SMP with T _S adjusted to 70 ° C. Spherical SMP particles adjusted to 50 ° C. were dispersed at a volume content of 50% to obtain a polymer composite material, and a macroscopic loss factor (tan δ _All ) was obtained. patent literature ( "Japan Society of mechanical Engineers" No.03-11, material mechanics division Annual conference Proceedings, pp. 130-132, 2003, September 24-26, 2009) as disclosed as the, of the base material T _S It was found that the loss coefficient (tan δ _All ) can take a maximum value in the vicinity of 30 ° C., which is the T _S of the SMP particles dispersed as island-shaped resin, in addition to around 70 ° C. [see FIG. 3].

However, the value of the macroscopic loss coefficient (tan δ _All ) at 30 ° C., which is the T _S of the SMP particles blended as the island component, is the macroscopic loss coefficient at 70 ° C., which is the T _S of the base material that is the sea component. Not only does it significantly decrease compared to the value of (tan δ _All ), but the macroscopic loss factor (tan δ _All ) in the temperature range of 35-60 ° C is also poor. Therefore, instead of dispersing one kind of SMP particles, when four kinds of SMP particles having T _{S in} the vicinity of 30 ° C., 40 ° C., 50 ° C., and 60 ° C. are uniformly dispersed in the base material, 35 is obtained. The value of the macroscopic loss factor (tan δ _All ) in the temperature range of ˜60 ° C. could be smoothed to some extent [see FIG. 3]. However, the averaged value is clearly lower than the value of 70 ° C., which is the T _S of the base material, and 30 ° C., which is one of the T _S of the composite SMP particles. It is not possible to obtain a damping material that exhibits excellent damping performance.

  As described above, the present inventors have investigated the ratio of the rigidity of the resin constituting the sea component of the composite resin damping material phase-separated into the sea / island structure and the resin constituting the island component in the previous research. By optimizing (rigidity ratio), for example, it is possible to secure the adhesive strength and appropriate rigidity and loss factor necessary for damping materials used as damping materials such as damping steel plates, and wide loss factors It has been clarified that it can be increased to some extent in the temperature region, and further, if appropriate bubbles coexist in the composite resin, the rigidity can be further improved and the loss factor can be further increased. However, in order to obtain a satisfactory level of loss factor as a composite resin, it is necessary to take measures for improving rigidity by mixing bubbles as described above, and the manufacturing process is complicated and expensive, and is achieved in a wide temperature range. The loss factor that can be obtained is not always a satisfactory value, and further improvement is required to put this technology into practical use.

  Under these technical backgrounds, the present inventors have been made for the purpose of further improvement and practical application of the improved technique as described above.

By the way, in the previous researches, the present inventors have made investigations on the assumption that the shape of the resin particles dispersed as island components in the base material (sea component) is substantially spherical. However, it is thought that the macroscopic loss factor (tan δ _All ) of the composite resin as a whole can be increased by changing the shape of the resin particles dispersed as island components. I came.

Then, the first target constrained damping material, the rotational radial length when in a matrix having a different T _S is the base material, was assumed its shape spheroid comprising a SMP polyurethane resin Of a composite resin in which 50% by volume of polyurethane resin-based SMP particles having different ratios of the length in the rotation axis direction to the thickness (aspect ratio; ω) are dispersed by volume content (tan δ _All) ). The results are shown in FIG.

4, the vertical axis represents macroscopic loss factor of the whole composite resin (tan [delta _All), the abscissa temperature; indicates (T ° C.), 70 ° C. The T _S of the base material (sea component), as the island component The T _S of the SMP particles to be dispersed was set to 30 ° C., and the aspect ratio (ω) of the SMP particles was changed in the range of 0.001 to 1.0. 4, the broken line matrix alone SMP particles T _S is 70 ° C. indicates a loss factor which is not distributed.

  In the present invention, the aspect ratio means that the shape of the particle is a spheroid, as shown in FIG. 5 (in FIG. 5, the aspect ratio (ω) is 1 or more for convenience of explanation). The ratio of the length in the rotational axis [ie, the length of the rotational axis] (a × ω) to the length in the radial direction [ie, the diameter of the ellipsoid (a)] (a × ω), that is, (a × ω / a = ω ), And the smaller the aspect ratio (ω), the shorter the rotation axis length (a × ω) with respect to the ellipsoid diameter (a), for example, extremely flat like hemoglobin or coin. It means that it is a disk-like particle, and the larger the aspect ratio (ω), the longer (a × ω) relative to (a), for example, it means fibrous. .

As is clear from FIG. 4, when the aspect ratio (ω) of the SMP particles dispersed as the island component is 1.0 (that is, spherical), the entire composite resin combined with the SMP particles is macroscopic at 70 ° C. The loss factor (tan δ _All ) hardly decreases. However, as the aspect ratio of the SMP particles is reduced, although the macroscopic loss factor at 70 ℃ (tanδ _All) decreases, it is understood that the macroscopic loss factor at 30 ℃ (tanδ _All) increases rapidly. Furthermore, it can be seen that when the aspect ratio (ω) of the SMP particles is in the range of 0.01 to 0.1, the macroscopic loss coefficient (tan δ _All ) values at the measurement temperatures of 30 ° C. and 70 ° C. are substantially equal.

Figure 6 shows the viscoelastic properties of the experimental polyurethane shape memory polymer used in (SMP), rigidity in the T _S of the SMP (mu) is 234 (MPa), loss factor (tan [delta) is zero. 892, Poisson's ratio (ν) is 0.46. Further, at a temperature 40 ° C. lower than T _{S of the} SMP, the rigidity (μ) is 717 (MPa), the loss factor (tan δ) is 0.028, the Poisson's ratio (ν) is 0.38, and is lower than T _S. The rigidity (μ) at a temperature higher by 40 ° C. is 5.5 (MPa), the loss factor (tan δ) is 0.123, and the Poisson's ratio (ν) is 0.5. Therefore, the rigidity ratio (μ _I / μ _M ) of the SMP particles to the base material at 30 ° C. is 0.326 (= 234/717), the loss factor (tan δ _M ) of the base material is 0.028, The loss factor (tan δ _I ) is 0.892. On the other hand, the rigidity ratio (μ _I / μ _M ) of SMP particles to the base material at 70 ° C. is 0.0235 (= 5.5 / 234), the loss factor (tan δ _M ) of the base material is 0.892, and SMP particles The loss coefficient (tan δ _I ) is 0.123.

Therefore, the loss coefficient of the base material and the SMP particles employed in the 70 ° C. is T _S of 30 ° C. and the base material is a T _S of SMP particles, the aspect ratio of the SMP particles (omega), for the particles of the base material Macroscopic loss factor (tan δ _All ) as a polymer composite material when the rigidity ratio (μ _I / μ _M ) is changed variously, and the rigidity ratio of the composite material to the base material (μ _All / μ _The effect on _M ) was investigated. The results are shown in FIGS.

In these figures, the loss factor (tan δ _M ) of the base material at 30 ° C., which is T _S of the SMP particles, is 0.01, the Poisson's ratio (ν _M ) is 0.4, and the loss factor (tan δ _I ) of the SMP particles is 1.0, Poisson's ratio (ν _I ) is 0.45; loss factor (tan δ _M ) of the base material at 70 ° C. which is Ts of the base material is 1.0, Poisson's ratio (ν _M ) is 0.45, SMP The particle loss coefficient (tan δ _I ) is 0.1, the Poisson's ratio (ν _I ) is 0.50; the SMP particle content (f) is 50% by volume. FIG. 7 shows the case where the measurement temperature is 30 ° C. which is T _S of the SMP particles, FIGS. 8 and 9 show the case where the measurement temperature is 70 ° C. which is T _S of the base material, and FIG. It is the figure which expanded the range whose _I / micro _M is 0-0.1.

From FIG. 7, at 30 ° C., which is the T _S of the SMP particle, the aspect ratio (ω) of the particle is 0.1 or less (that is, log ω ≦ −1), and the rigidity ratio of the particle to the base material (μ _I / Μ _M ) is 0.3 or less, the macroscopic loss factor (tan δ _All ) of the composite material is 0.5 or more, and the rigidity ratio (μ _All / μ _M ) of the composite material to the base material is 0. .5 or less.

Also from Figure 8 and 9, at the 70 ° C. is T _S of the base material, the aspect ratio of the SMP particles (omega) is 0.01 or more (i.e., log .OMEGA ≧ -2), modulus of rigidity against the base material of the SMP particles When the ratio (μ _I / μ _M ) is 0.02 or more, the macroscopic loss factor (tan δ _All ) as the composite material is 0.5 or more, and the rigidity ratio of the composite material to the base material (μ _All / μ _M ) is 0.05 or more.

Also from these results, the rigidity ratio (μ _I / μ _M ) of the island-shaped resin particles relative to the base material is set in the range of 0.02 to 0.3, and the aspect ratio (ω) of the island-shaped resin particles is 0. It can be seen that by setting the value within the range of .01 to 0.1, an appropriate range of viscoelastic properties required for the damping material can be secured as a composite resin when used as a damping material.

Further, FIG. 10 shows an example of a composite resin that exhibits the above-described experimental results and is a further improvement derived from the experimental results confirmed in FIG. That is, in the example of FIG. 10, five types of resin particles having an aspect ratio (ω) of 0.01 are used together with SMP particles having different T _S , and these are used as a sea state composed of SMP having T _S of 70 ° C. In the resin, 50% by volume of the total content (f) is blended. According to this example, the loss factor (tan δ _All ) can be increased on the average over a wide temperature range from 35 ° C. to 70 ° C. .

When combined different plural kinds of island-shaped resin particles T _S in having an aspect ratio of the proper range as described above Figure 10, the damping material is obtained which exhibits stable and excellent damping performance over a wide temperature range I can confirm that.

  In the above, the examination result about the viscoelastic property calculated | required by the composite resin used as a restraint type damping material was demonstrated. In this case, the thickness of the composite resin used as the constrained vibration damping material is very thin, about 100 μm at most. That is, when the shear modulus (rigidity) of the composite resin is (μ), the shear displacement is (d), the resin layer thickness is (t), and the adhesion area between the composite resin and the constraining metal plate is (A), The relationship between the shear force (F) acting on the resin layer and the shear displacement (d) can be expressed by “F = μAd / t”. As the composite resin thickness (t) decreases, “μA / “t” increases. For this reason, the composite resin layer may be thin, but the thin resin layer must provide vibration attenuation for the metal plate that is relatively thick compared to the composite resin layer, so a high loss factor is required for the composite resin layer. It is done.

  If the composite resin layer has too high shear rigidity, the composite resin layer does not undergo shear deformation, and the three-layer laminate is deformed like a single plate. The loss factor of the damping material as a whole is small. Conversely, if the rigidity of the composite resin layer is too small, the energy sharing ratio due to the distortion of the composite resin layer is lowered, so that the loss coefficient of the entire damping material is also lowered. Thus, there exists an optimum range for the shear elastic modulus (rigidity) of the composite resin layer. In other words, the rigidity (μ) and loss factor (tan δ) of the composite resin used for the constraining type damping material have a suitable range for more effectively increasing the loss factor of the constraining type damping material as a whole. It is known that the preferable rigidity (μ) of the composite resin when the constrained metal plate is steel or aluminum alloy is 0.07 to 20 MPa, and the preferable loss factor (tan δ) is 0.5 to 3. The image of the composite resin conforming to such a preferable range may be a so-called “sticky” viscous substance in the boundary region between the solid and the liquid.

  Next, the examination result about the composite resin used as an unrestrained type damping material is described.

  Unconstrained damping material is a damping material with a structure in which damping resin or the like is bonded (laminated) to one or both sides of a rigid plate such as a steel plate or aluminum alloy plate as a base material. The two-layer type in which the composite resin layer is formed only will be described as follows.

The loss coefficient of the entire two-layer composite vibration damping material is referred to as a composite loss coefficient, and the ratio (tan δ / tan δ _R ) of this composite loss coefficient (tan δ) to the loss coefficient (tan δ _R ) of the damping resin alone, There is a relationship as shown in FIG. 11 between the thickness ratio (d ₂ / d ₁ ) and the Young's modulus ratio (a = E ₂ / E ₁ ) of the vibration-damping resin layer to the base material. In the region where the thickness ratio (d ₂ / d ₁ ) of the resin layer is 40 or less, the composite loss coefficient (tan δ) increases as the Young's modulus ratio (a) increases. Therefore, in order to increase the composite loss factor as a two-layer composite damping material with the thinest damping resin layer as much as possible, the Young's modulus ratio (a) should be increased, that is, the Young's modulus (E ₂ ) of the damping resin should be increased. It is. However, since the rigidity of general polymer materials suddenly decreases in the temperature range above T _S , considering this, T _S of the base material (matrix) constituting the composite resin-based vibration damping material is the operating temperature range. It is necessary to set higher.

  The general thickness of the damping resin material used as the unconstrained damping material is about 1 to several times the base material thickness. When the base material thickness is 1 mm, the damping resin layer The thickness is 1 mm to several mm.

For example, the thickness ratio (d ₂ / d ₁ ) of the damping resin layer to the base material of the unconstrained damping material is 1, and the base material is an aluminum alloy plate (Young's modulus E ₁ = 7 × 10 ¹⁰ Pa). If the vibration resin is polypropylene (Young's modulus E ₂ = 1 × 10 ⁹ Pa), the Young's modulus ratio (a = E ₂ / E ₁ ) is about 0.01 (= 10 ⁻² ) from FIG. The ratio of the composite loss factor (tan δ) of the entire unconstrained damping material to the loss factor (tan δ _R ) of the damping resin alone is about 0.1. If the operating temperature is set to 20 ° C. and a polypropylene whose T _S is sufficiently higher than 20 ° C. is selected as the base material, its loss factor (tan δ _R ) is about 0.1, so the composite loss factor is It is about 0.01 and does not satisfy the value of 0.05 or more which is the minimum loss coefficient generally evaluated as a vibration damping material. However, when the thickness ratio (d ₂ / d ₁ ) of the damping resin layer to the base material is increased to 3, the composite loss coefficient ratio increases to 0.6 as shown in FIG. It will increase to 06, and will show a vibration damping performance at a practical level.

In the present invention under these trends, the damping resin design unconstrained vibration damping material, select the relatively high T _S resin as the resin constituting the matrix, while the matrix resin, constrained described above as with the resin for damping material, by dispersing the island component a different resin particles T _S as a means for increasing the loss factor, excellent damping performance shows 0.1 or more in the composite loss factor It is also intended to develop a composite resin for vibration control that exhibits

Now, assuming that the use temperature is 20 ° C., the Ts of the resin particles dispersed in the base material is set to 20 ° C., and polypropylene (see FIG. 21) whose Ts is sufficiently higher than 20 ° C. is used as the base material. Think about the case. Assuming that the macroscopic Young's modulus does not decrease due to the dispersion of the resin particles, and the base material is a steel plate or an aluminum plate, the Young's modulus ratio (E ₂ / E ₁ ) is about 5 × 10 ⁻³ (= 1 × 10 ⁹ / since the ^{20 × 10 11) ~1.4 × 10} -2 (= 1 × 10 9/7 × 10 10), the thickness ratio of damping resin to the base material (d ₂ / d ₁₎ is "1. When the thickness ratio (d ₂ / d ₁ ) is “2.0”, the composite loss factor is the damping factor. It is about 0.2 to 0.4 times that of the vibration resin. Therefore, in order to set the composite loss coefficient to “0.1 or more” when the plate thickness ratio is “1.0”, the macroscopic loss coefficient (tan δ _All ) of the entire vibration-damping composite resin is about 1 to 1. When the thickness ratio is set to 2 and the plate thickness ratio is “2”, it is understood that the macroscopic loss coefficient (tan δ _All ) of the entire vibration-damping composite resin needs to be set to about 0.25 to 0.5. .

Therefore, when resin particles having an aspect ratio (ω) of “0.01”, “0.1”, “1.0” are used, the loss coefficient (tan δ _I ) of the resin particles is set to 0 to 5.0. The rigidity ratio (μ _I / μ _M ) of the resin particles to the base material is changed in the range of 0.001 to 1000, and the macroscopic loss factor (tan δ _All ) of the composite resin as a whole and the composite to the base material The Young's modulus ratio (E _All / E _M ) of the resin was obtained, and the conditions under which the macroscopic loss factor (tan δ _All ) was 0.25 or more were examined.

The relationship between the macroscopic loss factor (tan δ _All ) and the Young's modulus ratio (E _All / E _M ) of the vibration-damping composite resin as a whole, and the volume content (f _I ) of the island-shaped particles being 0.3 (30% 12) (when the aspect ratio ω of the island-shaped particles is 0.01), FIG. 13 (when the aspect ratio (ω) of the island-shaped particles is 0.1), and FIG. 14 (of the resin particles). (When the aspect ratio (ω) is 1.0).

As is clear from these figures, as the aspect ratio (ω) of the resin particles decreases, the value of the macroscopic loss factor (tan δ _All ) of the composite resin as a whole increases. When ω = 0.01, When the loss coefficient (tan δ _I ) of the resin particles is 0.3 or more and ω = 0.1, the loss coefficient (tan δ _I ) of the resin particles is 0.5 or more, and when ω = 1.0, the loss of the resin particles It can be seen that the coefficient (tan δ _I ) is 0.7 or more, and the macroscopic loss coefficient (tan δ _All ) of the composite resin as a whole is 0.25 or more.

Based on this result, the loss coefficient (tan δ _I ) of the resin particles is fixed to 0.3 or 0.7, and the aspect ratio (ω) of the resin particles is 0.001 to 1000 (log ω = −3 to 3). Similarly, the macroscopic loss coefficient (tan δ _All ) and Young's modulus ratio (E _All / E _M ) of the composite resin as a whole were determined.

The results are as shown in FIGS. 15 and 16, and when the loss coefficient (tan δ _I ) of the resin particles is 0.3 (FIG. 15), ω is 0.01 (log ω = −2) or less, and the rigidity is When the ratio (μ _I / μ _M ) is 0.04 or less, and when the loss factor (tan δ _I ) of the resin particles is 0.7 (FIG. 16), ω is 1.0 (log ω = 0) In the following, when the rigidity ratio (μ _I / μ _M ) is 10 or less, the macroscopic loss coefficient of the composite resin as a whole is 0.25 or more. It can be seen that a macroscopic loss factor of 1 or more can be achieved with a sheet thickness ratio (d ₂ / d ₁ ) of 1-2 (see FIG. 11).

However, from FIGS. 15 and 16, even when the loss factor (tan δ _I ) of the resin particles is 0.3 or 0.7, the rigidity ratio (μ _l / μ _M ) is 1 or less and the aspect ratio (ω) is 1. When the following resin particles are dispersed, the Young's modulus ratio (E _All / E _M ) of the composite resin with respect to the base material is 1 or less. It is assumed that the base material is a steel plate or an aluminum plate, and the Young's modulus ratio is 5 × 10 ^{−3 to} 1.4 × 10 ⁻² ”.

Therefore, in the state where the resin particles are dispersed, hard particles (for example, glass, mica, aluminum hydroxide, magnesium hydroxide, shirasu balloon, carbon black, fullerene) having a tenfold rigidity relative to the resin base material. , Carbon nanotube, titanium oxide filler, etc.), the loss factor (tan δ _All ) of the composite resin as a whole and the Young's modulus ratio (E _All / E _M ) of the composite resin as a whole to the base material It was determined when the aspect ratio (ω _II ) of the hard particles was changed to 0.1, 1.0 and 10.0. The filler may also serve as a filler for making the composite resin flame-retardant.

The results are as shown in FIGS. 17, 18, and 19. When ω _II is 1 or less, the rigidity ratio (μ _I / μ _M ) of the resin particles to the base material is 1 or less and the aspect ratio (ω _I ) is 1. Even when resin particles of 0.0 or less are dispersed, the Young's modulus ratio (E _All / E _M ) of the entire composite resin to the base material is set to 1 or more without losing the loss coefficient (tan δ _All ) of the entire composite resin. You can see that it can be set. However, when the aspect ratio (ω _II ) of the hard particles increases to 10, the Young's modulus ratio (E _All / E _M ) increases, but the macroscopic loss factor (tan δ _All ) has a worst value of about 1/2. Decrease to a degree.

Therefore, the aspect ratio (ω _I ) of the resin particles is fixed to 0.1, the rigidity ratio (μ _I / μ _M ) is fixed to 0.2, and the loss factor (tan δ _I ) is fixed to 0.7, and the aspect ratio of the hard particles is fixed. (Ω _II ) and the rigidity ratio (μ _II / μ _M ) with respect to the base material are continuously changed, and the loss factor (tan δ _All ) and Young's modulus ratio (E _All / E _M ) of the composite resin as a whole As a result, the result of FIG. 20 was obtained. From this figure, if the rigidity ratio (μ _II / μ _M ) is 7 or more and the aspect ratio (ω _II ) of hard particles is 1 or less at 20 ° C., the loss factor (tan δ _All ) of the composite resin as a whole is maintained. It can be seen that the Young's modulus ratio (E _All / E _M ) can be increased to 1.0 or more, that is, the macroscopic Young's modulus can be increased to be equal to or higher than that of the base material while increasing or decreasing.

  Next, when considering the production of a composite resin damping material for an unconstrained damping material with a working temperature range of 20 to 80 ° C., for example, as shown in FIG. 21, a temperature range of 20 to 80 ° C. In the frequency range of 100 Hz to 5 kHz [log (f) of the right vertical axis in the figure is 2 to 3.7], a polypropylene having a relatively high Young's modulus exceeding 1 GPa is used as a base material. As shown in FIGS. 22 and 23, an example will be described in which two types of polyester particles (1) having a Ts of 20 ° C. in the frequency region and polyester particles (2) having a Ts of 80 ° C. are dispersed and combined.

  21 to 23, the vertical axis on the right side is the log value of the vibration frequency (f), and the vertical axis on the left side is the log value of the Young's modulus E and the loss coefficient (tan δ). ● The line that appears due to the continuation of dots indicates the change in loss factor (tan δ) due to the temperature of each resin, and the line that appears due to the continuation of ■ points indicates the change in Young's modulus (E) due to the temperature of each resin. .

As shown in FIG. 21, the polypropylene used as the sea component (base material; matrix) has a temperature range of 20 to 80 ° C., 100 Hz to 5 kHz [2-3.7 on the vertical axis log (f) in the figure], and Young's modulus. (E) shows a high value exceeding 1 GPa, and the polyester particles (1) and (2) used as island components have intermediate frequencies in the same frequency range as described above, as shown in FIGS. Resin that exhibits the maximum loss factor at 20 ° C. or 80 ° C. at 1000 Hz [1 kHz: log (f) = 3 on the vertical axis] (ie, T _S is 20 ° C. or 80 ° C.).

  From these viscoelastic curves of FIGS. 21 to 23, when the frequency is 1 kHz [1000 Hz, that is, the log (f) value is 3], Young's modulus (E) and rigidity modulus (μ) of each resin at 20 ° C. and 80 ° C. Then, the loss coefficient (tan δ) is obtained as shown in Table 1. The Poisson's ratio (ν) shown in the table is a value obtained by another method. The rigidity was determined from the relationship [μ = E / {2 (1 + ν)} from Young's modulus and Poisson's ratio.

Then, in the polypropylene constituting the base material (matrix), different T _S above two polyester particles constituting the resin particles (1), and be dispersed respectively 30% by volume (2), the aspect of the resin particles When the ratio (ω) is changed, the aspect ratios (ω _I ) and (ω _II ) of the polyester particles (1) and (2) blended as island components are the macroscopic loss factor (tan δ _All ) And Young's modulus ratio (E _All / E _M ).

From Table 1, the rigidity ratio (μ _I / μ _M ) and (μ _II / μ _M ) of the resin particles (polyester particles) (1) and (2) with respect to the base material (polypropylene) when the temperature is 20 ° C. The rigidity ratios (μ _I / μ _M ) and (μ _II / μ _M ) when the temperature is 80 ° C. are 0.03 and 0.16. Therefore, the composite resin as a whole when the aspect ratios (ω _I ) and (ω _II ) of the polyester particles (1) and (2) are changed are fixed to the values of the rigidity ratio and loss coefficient shown in Table 1. When the macroscopic loss coefficient (tan δ _All ) and Young's modulus ratio (E _All / E _M ) were obtained, the results shown in FIGS. 24 and 25 were obtained.

As is clear from FIG. 24, at 20 ° C., the rigidity and loss factor of the polyester particles (2) are almost the same as those of the base material, so there is no influence of the aspect ratio (ω _II ) of the particles (2). When the aspect ratio (ω _I ) of the particles (1) is 0.6 or less, the loss factor (tan δ _All ) is 0.25 or more. As is clear from FIG. 25, when the aspect ratio (ω _II ) of the polyester particles (2) is about 1 or less at 80 ° C., the loss coefficient (tan δ _All ) is 0.25 or more. That is, if the aspect ratios (ω _I ) and (ω _II ) of the polyester particles (1) and (2) are each 1 or less, the loss coefficient (tan δ _All ) is 0.25 or more, and the unconstrained vibration damping material As a whole, it can be seen that a loss factor of 0.1 or more can be achieved with a plate thickness ratio (d ₂ / d ₁ ) of 1-2.

However, the Young's modulus ratio (E _All / E _M ) decreases to a minimum of 0.35. That is, since the macroscopic Young's modulus is reduced to 35% of the base material, it is assumed that the macroscopic Young's modulus does not decrease due to the dispersion of the resin particles. If the material is a steel plate or an aluminum plate, the Young's modulus ratio is 5 × 10 ^{−3 to} 1.4 × 10 ⁻² ”.

Therefore, in the state where the polyester particles (1) and (2) are dispersed, the hard resin (3) as described above, which has a ten times higher rigidity than the base material, is additionally dispersed as a whole composite resin. Loss coefficient (tan δ _All ) and Young's modulus ratio (E _All / E _M ), and the aspect ratio (ω _III ) of the hard particles (3) were changed to 0.1, 1.0 and 10.0, respectively. As a result, the results of FIGS. 26 to 31 were obtained.

As is apparent from these figures, when the aspect ratio (ω _III ) of the hard particles (3) is “0.1”, the loss of the entire composite resin is less than when the hard particles (3) are not dispersed. The coefficient (tan δ _All ) increases about twice, the Young's modulus ratio (E _All / E _M ) also increases to about 0.85, and the aspect ratio (ω _III ) of the hard particles (3) is “1. When “0”, the Young's modulus ratio (E _All / E _M ) increases to about 0.75 while maintaining the loss factor (tan δ _All ) of the entire composite resin when the hard particles (3) are not dispersed. I understand. However, when the aspect ratio (ω _III ) of the hard particles (3) is “10.0”, the Young's modulus ratio (E _All / E _M ) when the hard particles (3) are not dispersed is about 1.2 or more. However, the loss factor (tan δ _All ) of the composite resin as a whole decreases to about ½ at worst.

Therefore, the aspect ratios (ω _I ) and (ω _II ) of the resin particles (1) and (2) are fixed to “0.1”, respectively, and the aspect ratio (ω _III ) of the hard particles (3) and the base material When the rigidity ratio (μ _III / μ _M ) was changed and the loss factor (tan δ _All ) and Young's modulus ratio (E _All / E _M ) of the composite resin as a whole were examined, the results shown in FIGS. became. As is apparent from this figure, when hard particles having a rigidity ratio (μ _III / μ _M ) of 7 or more and an aspect ratio (ω _III ) of 1 or less at 20 ° C. and 80 ° C. are combined, the composite resin as a whole It can be seen that the Young's modulus ratio (E _All / E _M ) can be set to 1.0 or more and the macroscopic Young's modulus can be increased to be equal to or higher than that of the base material while maintaining or increasing the loss coefficient (tan δ _All ).

From the above results, when the present invention is put into practical use as a composite resin for an unconstrained damping material, two or more kinds of resin particles having an aspect ratio (ω) of 1 or less are used in combination as an island component. Furthermore, by using hard particles having a rigidity ratio to the base material of 7 or more and an aspect ratio of 1.0 or less, preferably about 30% by volume or more, while ensuring a sufficient Young's modulus as a whole composite resin A composite resin damping material having a high loss factor (tan δ _All ) can be obtained.

Note in the above, and to it the unconstrained damping material two polyesters particles having different T _S as a has been described when used in combination as the resin particles has been described as an example for the constrained damping material in FIG. 10 Similarly, even if the unconstrained, by a combination of three or more kinds of resin particles having different T _S, it is possible to obtain a composite resin exhibiting a more stable loss factor as unconstrained.

  In the above description, a steel plate or an aluminum alloy plate is used as the metal plate to be combined with the vibration-damping resin material. However, the type of the metal plate is not limited to these, and other iron-based alloy plates such as stainless steel, Other non-ferrous metal plates such as Ti alloy plates, various surface-treated metal plates obtained by applying various surface coating treatments and plating treatments to them, and hard resin plates such as engineering plastics can be used. .

  In addition, as a damping resin material, when used as a restraint type damping material, a polyurethane resin having relatively low rigidity and excellent viscoelasticity is optimal, and it is also used for an unconstrained damping material. In this case, a polyolefin resin having a relatively high rigidity, more specifically, polypropylene is preferable as the base material resin constituting the sea component, and polyester or polyisobutylene is preferable as the ellipsoidal particles constituting the island component. This is an example, but of course there is no reason to limit this, and if it has the above-mentioned suitable viscoelastic properties, synthesis of polyolefin resin, silicone resin, polyamide resin, acrylate resin, chloroprene, butadiene, etc. Rubber, etc., or various modified resins and blended resins that are modified with epoxy resin, etc., can be arbitrarily selected and used. .

  In addition, the combination of the sea-like resin and the island-like resin is also free, and as shown in the above-described example of the drawing, not only the combination of the same type and different Ts but also the combination of two or more different types of resins can be used. It can be used in combination as a resin and / or an island resin.

  In addition, the adjustment of the aspect ratio as the island-shaped resin particles may be performed by using ellipsoidal particles whose aspect ratio has been adjusted in advance as the resin particles to be mixed when composited as the damping resin material. More preferably, a composite resin in which substantially spherical island-shaped resin particles are blended in a sea-like resin is used, and this is sandwiched between metal plates through an extrusion / stretching machine, or one side thereof. Or, before bonding to both sides, adjust the dimensions of the die provided at the exit of the extruder, the feeding speed of the stretching device, the stretching or reduction ratio, etc., or the preheating roll attached to the extruder / molding machine. By adjusting the surface temperature and the like, the thickness reduction rate from the die outlet to the extruder outlet is controlled within the range of 0.01 to 1.0, more preferably 0.01 to 0.1 in the case of the restraint type. And unconstrained In the case of 1.0, more preferably in the range of 0.01 to 0.1, thereby forming the island component by crushing the island-shaped resin particles in the composite resin layer in the rolling direction. In this method, resin particles are adjusted to ellipsoidal particles having an aspect ratio in an appropriate range.

At this time, the ratio (μ _I / μ _M ) of the rigidity (μ _I ) of the island-shaped resin particles to the rigidity (μ _M ) of the base material in the composite resin, In the range of 0.3, and in the case of the unconstrained type, it is “1 or less”, more preferably in the range of “0.01 to 1.0”. It can be concentrated on the island-shaped resin particles, and even if the original island-shaped resin particles are substantially spherical, it can be easily changed to ellipsoidal particles having a suitable aspect ratio by adjusting the rolling reduction ratio. preferable.

  At this time, it is preferable to employ a biaxial stretching method so that the island-shaped component is stretched in a flat plate shape following the stretching of the base material (matrix resin) in the longitudinal direction and the lateral direction. As the biaxial stretching method, either simultaneous biaxial stretching or sequential biaxial stretching may be employed. Of course, the aspect ratio of the resin particles may be lowered by a method such as heating or rolling after sandwiching the metal plates in a sandwich shape or bonding them to one or both surfaces thereof.

Further, in order to promote the formation of sea / island structure phase separation between the sea-like resin constituting the base material and the resin particles constituting the island component, the difference in solubility parameter (SP value) between the sea-like resin and the island-like particles is 1 [MPa] It is good to set it as ^0.5 or more.

In a constrained vibration damping material using a composite resin in which spherical resin particles are blended in 30% by volume in a resin base material, the rigidity ratio of the island resin particles to the sea resin and the loss factor of the island resin particles are composite resin. It is a graph which shows the influence which acts on the macroscopic loss factor and rigidity ratio as a whole. In a constrained vibration damping material using a composite resin in which 30% by volume of spherical resin particles and 30% by volume of spherical bubbles are contained in a resin base material, the rigidity ratio of island-shaped resin particles to island-shaped resin and the island shape It is a graph which shows the influence which the loss coefficient of a resin particle has on the macroscopic loss coefficient and rigidity ratio as the whole composite resin. In the case of using the Umijo resin alone is a graph showing one and T _S of four different spherical island composite resin of the resin particles in combination of temperature and the relationship between macroscopic loss factor thereto. It is a graph which shows the relationship between the temperature and macroscopic loss factor of the composite resin which used 50 volume% of several island-like resin from which an aspect ratio differs together with sea-like resin. It is explanatory drawing which shows the calculation method of the aspect-ratio of the ellipsoidal particle | grains prescribed | regulated by this invention. It is a figure which shows the viscoelastic characteristic of a polyurethane-type shape memory polymer. In the composite resin of the constrained vibration damping material, the ratio of the rigidity of the island-shaped resin particles to the sea-shaped resin and the aspect ratio of the island-shaped resin particles are the macroscopic loss factor and rigidity at the temperature of 30 ° C. It is a figure which shows the influence which acts on ratio. In the composite resin of the constrained vibration damping material, the ratio of the rigidity of the island-shaped resin particles to the sea-state resin and the aspect ratio of the island-shaped resin particles are the macroscopic loss factor and rigidity at the temperature of 70 ° C. It is a figure which shows the influence which acts on ratio. It is a figure which expands and shows the range whose rigidity ratio in FIG. 8 is 0-0.1. A graph showing the relationship between the macroscopic loss factor and the temperature of a composite resin in which five kinds of island-shaped resin particles having an aspect ratio of 0.01 and different T _S are used in combination with a sea-state resin alone. is there. Graph showing the relationship between damping resin / base plate thickness ratio and macroscopic loss coefficient / damping resin loss coefficient ratio, using the Young's modulus ratio of the damping resin relative to the base plate as a parameter for the unconstrained damping material It is. In the composite resin used as an unconstrained damping material, when the island-shaped resin having an aspect ratio of 0.01 is used, the rigidity ratio of the island-shaped resin particles to the sea-shaped resin and the loss factor of the island-shaped resin particles These are figures which show the influence which it has on the macroscopic loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as the whole composite resin. In the composite resin used as the unconstrained vibration damping material, when the island resin having an aspect ratio of 0.1 is used, the rigidity ratio of the island resin particles to the sea resin and the loss coefficient of the island resin particles are It is a figure which shows the influence which it has on the macroscopic loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as the whole composite resin. In the composite resin used as the unconstrained vibration damping material, when the island resin having an aspect ratio of 1.0 is used, the rigidity ratio of the island resin particles to the sea resin and the loss coefficient of the island resin particles are as follows: It is a figure which shows the influence which it has on the macroscopic loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as the whole composite resin. In the composite resin used as the unconstrained vibration damping material, when the island-shaped resin having a loss factor (tan δ _I ) of 0.3 is used, the ratio of the rigidity of the island-shaped resin particles to the sea-shaped resin and the ratio of the island-shaped resin particles It is a figure which shows the influence which aspect-ratio ((omega)) has on the macroscopic loss factor and Young's modulus ratio in the temperature of 20 degreeC as the whole composite resin. In the composite resin used as the unconstrained vibration damping material, when the island-shaped resin having a loss factor (tan δ _I ) of 0.7 is used, the rigidity ratio of the island-shaped resin particles to the sea-shaped resin and the island-shaped resin particles It is a figure which shows the influence which aspect-ratio ((omega)) has on the macroscopic loss factor and Young's modulus ratio in the temperature of 20 degreeC as the whole composite resin. In a composite resin used as an unconstrained vibration damping material, hard particles having a loss factor of 0.0 and an aspect ratio (ω _II ) of 0.1 are used as a base resin. Effect of the rigidity ratio of the resin particles to the base resin and the aspect ratio (ω _I ) of the resin particles on the macroscopic loss coefficient and Young's modulus ratio at a temperature of 20 ° C. as a whole of the composite resin when combined. FIG. In a composite resin used as an unconstrained vibration damping material, hard particles having a loss factor of 0.0 and an aspect ratio (ω _II ) of 1.0 are used as a base resin. The figure which shows the influence which the rigidity modulus ratio of the resin particle with respect to base material resin and the aspect ratio ((omega) _I ) of this resin particle have on the loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as the whole composite resin at the time of compounding It is. In a composite resin used as an unconstrained damping material, hard particles having a loss factor of 0.0 and an aspect ratio (ω _II ) of 0.0 are the same as resin particles having a loss factor of 0.7 and a base resin. Effect of the rigidity ratio of the resin particles to the base resin and the aspect ratio (ω _I ) of the resin particles on the macroscopic loss coefficient and Young's modulus ratio at a temperature of 20 ° C. as a whole of the composite resin when combined. FIG. In the composite resin used as the unconstrained vibration damping material, the hard particles with respect to the base resin when the hard particles having the loss coefficient of 0.0 and the hard particles having the loss coefficient of 0.0 are combined with the base resin It is a figure which shows the influence which rigidity ratio and the aspect ratio ((omega) _II ) of this hard particle have on the macroscopic loss factor and Young's modulus ratio in the temperature of 20 degreeC as the whole composite resin. It is a figure which shows the viscoelastic property by the temperature and frequency of the polypropylene used as a base material. It is a figure which shows the viscoelastic characteristic by the temperature and frequency of the polyester particle (1) used as an island component. It is a figure which shows the viscoelastic characteristic by the temperature and frequency of the polyester particle (2) used as an island component. In a composite resin used as an unconstrained damping material, when two types of resin particles are added in combination as an island-shaped resin, the aspect ratio of each resin particle is macroscopic at a temperature of 20 ° C. as a whole composite resin. It is a figure which shows the influence which it has on a loss coefficient and a Young's modulus ratio. In a composite resin used as an unconstrained damping material, when two types of resin particles are added in combination as an island-shaped resin, the aspect ratio of each resin particle is macroscopic at a temperature of 80 ° C. for the entire composite resin. It is a figure which shows the influence which it has on a loss coefficient and a Young's modulus ratio. In the composite resin used as the unconstrained vibration damping material, when the hard particles having an aspect ratio of 0.1 are additionally dispersed in addition to the two types of resin particles, the aspect ratio of the two types of resin particles is It is a figure which shows the influence which it has on macroscopic loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as. In the composite resin used as the unconstrained vibration damping material, when the hard particles having an aspect ratio of 0.1 are additionally dispersed in addition to the two types of resin particles, the aspect ratio of the two types of resin particles is It is a figure which shows the influence which it has on macroscopic loss coefficient and Young's modulus ratio in the temperature of 80 degreeC as. In the composite resin used as the unconstrained vibration damping material, when the hard particles having an aspect ratio of 0.1 are additionally dispersed in addition to the two types of resin particles, the aspect ratio of the two types of resin particles is It is a figure which shows the influence which it has on macroscopic loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as. In the composite resin used as the unconstrained vibration damping material, when the hard particles having an aspect ratio of 1.0 are additionally dispersed in addition to the two types of resin particles, the aspect ratio of the two types of resin particles is It is a figure which shows the influence which it has on macroscopic loss coefficient and Young's modulus ratio in the temperature of 80 degreeC as. In the composite resin used as the unconstrained vibration damping material, when the hard particles having an aspect ratio of 1.0 are additionally dispersed in addition to the two types of resin particles, the aspect ratio of the two types of resin particles is It is a figure which shows the influence which it has on macroscopic loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as. In the composite resin used as the unconstrained vibration damping material, when the hard particles having an aspect ratio of 10.0 are additionally dispersed in addition to the two types of resin particles, the aspect ratios of the two types of resin particles are It is a figure which shows the influence which it has on macroscopic loss coefficient and Young's modulus ratio in the temperature of 80 degreeC as. In the composite resin used as the unconstrained vibration damping material, when the hard particles having an aspect ratio of 10.0 are additionally dispersed in addition to the two types of resin particles, the aspect ratios of the two types of resin particles are It is a figure which shows the influence which it has on macroscopic loss coefficient and Young's modulus ratio in the temperature of 20 degreeC as. In the composite resin used as an unconstrained vibration damping material, when hard particles having different aspect ratios are additionally dispersed in addition to two types of resin particles each having an aspect ratio of 0.1, It is a figure which shows the influence which a rigidity factor ratio and the aspect ratio of this hard particle have on the macroscopic loss coefficient and Young's modulus ratio in the temperature of 80 degreeC as the whole composite resin.

Claims (7)

In a base material made of a polymer material , an ellipsoidal particle made of a polymer material having a maximum loss coefficient at 1000 Hz at a temperature lower than the temperature at which the loss coefficient at 1000 Hz of the base material is maximum. The ratio of the length in the rotation axis direction to the length in the rotation axis direction when the particle shape is assumed to be a spheroid (aspect ratio; ω) is in the range of 0.01 to 0.1. Are dispersed in islands , and the ratio of the shear elastic modulus (rigidity) (μ _I ) of the ellipsoidal particles to the shear elastic modulus (rigidity ) (μ _M ) of the base material (μ _I / μ _M ) is in the range of 0.02 to 0.3, a damping material for a constrained damping material. Examples ellipsoidal particles, damping material for constraining vibration damping material according to claim 1, wherein the plurality of different particle-temperature loss factor at 1000Hz is maximized are dispersed. Material before Symbol preform and the ellipsoidal particles, damping material for constraining vibration damping material according to claim 1 or 2 is a shape memory polymer material polyurethane. A method for manufacturing the vibration damping material according to any one of claims 1 to 3 , wherein the base material includes a base material at 1000 Hz at a temperature lower than a temperature at which the loss factor at 1000 Hz is maximum. the loss factor Ri polymeric material Tona that maximizes the ratio of the shear modulus of the base material shear modulus of the polymer material for (modulus) (mu _M) (modulus) (mu _I) (mu _{when I} / mu _M) is using the composite resin particles child substantially spherical dispersed is in the range of 0.02 to 0.3, and processed to give damping material the composite resin into a sheet, A constrained vibration damping material , wherein the particles are crushed by controlling the thickness reduction rate in a range of 0.01 to 0.1 in the process until a sheet-shaped vibration damping material having a target thickness is obtained. For manufacturing sheet-like damping materials. The biaxial stretching method employed for the preparation of a sheet-like damping material, longitudinally, laterally to follow in the matrix resin is stretched A process according to claim 4, extending the previous SL particles children tabular . The manufacturing method of Claim 5 which employ | adopts a simultaneous biaxial stretching method. The manufacturing method of Claim 5 which employ | adopts a sequential biaxial stretching method.

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