JP2021161276A - Rubber composition for vibration control damper and manufacturing method thereof, as well as vibration control damper - Google Patents

Abstract

To provide a rubber composition for vibration control damper which exhibits high attenuation and is excellent in stability to repetitive deformation and vibration and its manufacturing method, as well as a vibration control damper.SOLUTION: A rubber composition for a vibration control damper comprises a polymer component comprising the following (A) and the following (B) and (C) components, and has a content of the following (D) components relative to 100 pts.mass of the (A) component of 5 pts.mass or smaller, and by the rubber composition for vibration control damper, the problem is solved. (A) A polymer comprising styrene isoprene styrene block polymer as a main component. (B) Silica having BET specific surface area of 350 m2/g or smaller. (C) Calcium carbonate. (D) At least one selected from the group consisting of organic radical scavengers and processing aids.SELECTED DRAWING: None

Description

The present invention relates to a rubber composition for a seismic damping damper, a method for manufacturing the same, and a seismic damping damper. It is related to things, their manufacturing methods, and vibration control dampers.

Vibration control devices and seismic isolation devices in the civil engineering and construction fields, especially vibration control dampers used in large buildings such as bridges and buildings, suppress vibrations caused by earthquakes and winds, and traffic vibrations caused by the running of large vehicles. In addition to exhibiting seismic control performance by the mechanical structural elements of the seismic control damper, it is required to achieve high damping by the viscous elastic body (rubber material) used in the seismic control damper. ..

As the viscoelastic body used in the conventional vibration damping damper, a viscoelastic body containing a styrene-isoprene-styrene copolymer as a main component is mainly used (see, for example, Patent Documents 1 and 2).
Further, in order to develop frictional damping with the styrene-isoprene-styrene copolymer, a low-viscosity ethylene-propylene-diene monomer ternary copolymer having a large amount of diene and prone to frictional damping may be blended, or silica or High filling of small particle size fillers such as calcium carbonate is also being considered.

Japanese Unexamined Patent Publication No. 2014-227521 Japanese Unexamined Patent Publication No. 2015-183110

In order to absorb the energy of a large earthquake, it is essential to increase the high strain and high attenuation of the viscoelastic body. In recent years, many small and medium-sized earthquakes have occurred after the Great East Japan Earthquake, and there is an increasing need for characteristic stabilization against repeated deformations that are repeated many times, such as long-period earthquakes observed in high-rise buildings. There is.

Furthermore, it is also important to improve the stability of the viscoelastic body against repeated deformation when it is continuously vibrated many times due to low strain assuming a typhoon, small and medium-sized earthquakes, and medium strain assuming a long-period earthquake. be. Further, in the viscoelastic body, it is required to stabilize the characteristics at the time of repeated deformation without causing a decrease in elastic modulus and damping property and without changing the amount of filler added.

That is, the conventional method for improving the damping property of the viscoelastic body includes imparting frictional damping by increasing the filling of the filler, but the polymer and the filler are broken during repeated deformation and vibration as described above. This is because there is a problem that cracks are generated due to (peeling) and breakage of filler agglomerates, causing deterioration of characteristics.

INDUSTRIAL APPLICABILITY The present invention has been made in view of such circumstances, and provides a rubber composition for a vibration damping damper, a method for producing the same, and a vibration damping damper, which exhibits high damping property and is excellent in stability against repeated deformation and vibration. Is the purpose.

The present inventors have conducted extensive research to solve the above problems. In the process of the research, the composition of the conventional rubber composition for seismic dampers, such as improving durability by adding an anti-aging agent, was reviewed, and in the present invention, styrene-isoprene-styrene block polymer is used as the main component. It was recalled that the stability against repeated deformation was improved by suppressing the addition of radical trapping agents such as antiaging agents, cross-linking agents, and cross-linking accelerators, and processing aids as much as possible to the polymer components. That is, when there is a radical scavenger as described above, when a radical is generated by breaking the polymer chain during kneading of the rubber composition, the radical scavenger and the radical are bonded, so that it is difficult to bond with the OH group on the silica surface. As a result, the degree of dispersion of silica decreases. Further, when the above-mentioned processing aid is present, it becomes slippery during kneading and the dispersity of silica and the like decreases. On the other hand, when the amount of radical scavenger or processing aid is small, the active group of silica binds to the radical of the polymer, so that the dispersibility of silica can be achieved and cracks occur between the polymer and silica even when vibrated. It becomes difficult and the stability against repeated deformation and vibration is improved. Further, in the present invention, ^{silica having a BET specific surface area of 350 m 2} / g or less is used as a filler together with calcium carbonate, and the damping property and the rigidity are adjusted, and the silica and the polymer as described above are used. We have found that the intended purpose can be achieved because the binding is further improved, and arrived at the present invention.

That is, the gist of the present invention is the following [1] to [8].
[1] The polymer component composed of the following (A) and the following components (B) and (C) are contained, and the total content of the following component (D) with respect to 100 parts by weight of the component (A) is A rubber composition for a vibration damping damper having 5 parts by weight or less, wherein the rubber composition satisfies the following conditions (X).
(A) A polymer containing styrene-isoprene-styrene block polymer as a main component.
(B) Silica having a BET specific surface area of 350 m ² / g or less.
(C) Calcium carbonate.
(D) At least one selected from the group consisting of organic radical scavengers and processing aids.
(X) ΔG'represented by the following formula (I) is 8 or less.
ΔG'= G'2 / G'1 …… (I)
[In the formula (I), G'1 is the storage elastic modulus of the unvulcanized rubber composition at a frequency of 11 Hz and a runout angle of 0.28% and 40 ° C., and G'2 is a frequency of 11 Hz and a runout angle. The storage elastic modulus of the unvulcanized rubber composition at 50% and 40 ° C. is shown. ]
[2] The amount of styrene-isoprene diblock in the styrene-isoprene-styrene block polymer of the component (A) above is 50 to 95% by weight, and the amount of styrene is 10 to 30% by weight, according to [1]. Rubber composition for vibration damping dampers.
[3] The rubber composition for a vibration damping damper according to [1] or [2], wherein the Mooney viscosity of the component (A) at 100 ° C. is 10 to 50.
[4] The rubber composition for a vibration damping damper according to any one of [1] to [3], wherein the amount of DBA adsorbed by the component (B) is 10 to 350 mmol / kg.
[5] The rubber composition for a vibration damping damper according to any one of [1] to [4], wherein the component (B) is at least one selected from dimethylsilyl-treated silica and trimethylsilyl-treated silica.
[6] The method for producing a rubber composition for a vibration damping damper according to any one of [1] to [5], wherein 40 to 80% by weight of the component (A) and 50 of the component (B). For a vibration damping damper, which comprises a first kneading step of preparing a master batch consisting of only ~ 100% by weight and a second kneading step of adding all the remaining materials to the master batch and kneading the master batch. A method for producing a rubber composition.
[7] A vibration damping damper characterized in that a viscoelastic body made of the rubber composition for a vibration damping damper according to any one of [1] to [5] is used as a constituent member thereof.
[8] The vibration damping damper according to [7], which is a vibration damping damper for high-rise buildings.

In addition, ΔG'represented by the above formula (I) is an index for evaluating the cohesiveness of the filler, as described in JP-A-2006-47070, and ΔG'is The smaller the value, the higher the dispersity of the filler.

From the above, the rubber composition for a vibration damping damper of the present invention can exhibit high damping property and excellent stability against repeated deformation and vibration.
Further, the method for producing a rubber composition for a vibration damping damper of the present invention can efficiently produce a special rubber composition exhibiting the above-mentioned performance.
As described above, the vibration damping damper of the present invention having the viscoelastic body made of the rubber composition as a constituent member exhibits high damping property and is excellent in stability against repeated deformation and vibration. .. Therefore, it can exhibit excellent performance as a vibration control damper used for large buildings such as high-rise buildings and bridges.

It is a front view which shows an example of a vibration control damper. It is sectional drawing which shows an example of the said vibration control damper. It is sectional drawing which shows the other example of the said vibration control damper. It is a schematic diagram which shows the installation state of the said vibration control damper. It is a schematic diagram of the apparatus used to perform the evaluation method of a dynamic shear property. It is a graph which shows the load-strain loop curve.

Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to this embodiment.

The rubber composition for a vibration damping damper of the present invention contains the following polymer component (A) and the following (B) and (C) components, and the following (A) component with respect to 100 parts by weight (A). D) A rubber composition for a vibration damping damper in which the total content of the components is 5 parts by weight or less, and the rubber composition satisfies the following condition (X).
(A) A polymer containing styrene-isoprene-styrene block polymer (SIS) as a main component.
(B) Silica having a BET specific surface area of 350 m ² / g or less.
(C) Calcium carbonate.
(D) At least one selected from the group consisting of organic radical scavengers and processing aids.
(X) ΔG'represented by the following formula (I) is 8 or less.
ΔG'= G'2 / G'1 …… (I)
[In the formula (I), G'1 is the storage elastic modulus of the unvulcanized rubber composition at a frequency of 11 Hz and a runout angle of 0.28% and 40 ° C., and G'2 is a frequency of 11 Hz and a runout angle. The storage elastic modulus of the unvulcanized rubber composition at 50% and 40 ° C. is shown. ]

In addition, ΔG'represented by the above formula (I) is an index for evaluating the cohesiveness of the filler, as described in JP-A-2006-47070, and ΔG'is The smaller the value, the higher the dispersity of the filler. Then, in the present invention, as shown in the condition (X) above, ΔG'is 8 or less, preferably ΔG'is in the range of 0 to 8, and more preferably ΔG'is in the range of 0 to 7.5. Is.
Further, G'1 and G'2 can be measured by, for example, a rubber processing tester, a curast meter, a dynamic viscoelasticity measurement, or the like. More specifically, it is measured by RPA2000 manufactured by Alpha Technology.

Further, in the rubber composition for a vibration damping damper of the present invention, only the polymer (A) containing styrene-isoprene-styrene block polymer (SIS) as a main component is used as the polymer component thereof.
Here, the "main component" means that it occupies a ratio exceeding 50% by weight of the polymer component, preferably 80% by weight or more of the polymer component, and more preferably 90% by weight or more of the polymer component. Indicates that. The purpose is to include the case where the polymer component is composed of only styrene-isoprene-styrene block polymer (SIS).
Further, in the rubber composition for a vibration damping damper of the present invention, the total content of the organic radical scavenger and the processing aid which are the components (D) is 5% by weight with respect to 100 parts by weight of the polymer (A). It is necessary to make it less than or equal to a part. The content of the component (D) with respect to 100 parts by weight of the polymer (A) is preferably in the range of 0 to 4.5 parts by weight, more preferably 0 to 4 parts by weight, and most preferably the component (D) is not added. It is to include. By doing so, the stability against repeated deformation can be further improved.

Here, the organic radical scavenger as the component (D) means a substance that functions as a radical scavenger in the rubber composition for a vibration damping damper, and corresponds to, for example, a cross-linking agent, a cross-linking accelerator, and an anti-aging agent. There are things to do. The rubber composition for a seismic damper of the present invention preferably does not contain a cross-linking agent or a cross-linking accelerator, and when an anti-aging agent is blended within the above range, for example. , Aromatic secondary amine-based anti-aging agent, special wax-based anti-aging agent, amine-ketone-based anti-aging agent, phenol-based anti-aging agent, imidazole-based anti-aging agent, etc. are used alone or in combination of two or more. It is possible.
Further, the processing aid as the component (D) means a processing aid that functions as a processing aid in the rubber composition for a vibration damping damper, and when the processing aid is blended within the above range, for example. , Stearic acid, paraffin wax, polyethylene, peptizer and the like can be used alone or in combination of two or more.

<< Polymer (A) >>
As described above, the SIS accounts for more than 50% by weight of the polymer (A), preferably 80% by weight or more of the polymer (A), and more preferably 90% by weight or more of the polymer (A). However, it consists of SIS. Then, the polymer (A) may be composed of only SIS.
Also, if necessary, in combination with SIS, ethylene-propylene-diene monomer ternary copolymer (EPDM), acrylic rubber, urethane rubber, styrene-butadiene-styrene block polymer (SBS), styrene-isobutylene-styrene block polymer. (SIBS), styrene-butadiene (SB) copolymer, styrene-isoprene (SI) copolymer, styrene-isoprene-styrene (SIS) copolymer, styrene-ethylene-butylene (SEB) copolymer, styrene- Ethylene-butylene-styrene (SEBS) copolymer, styrene-ethylene-propylene (SEP) copolymer, styrene-ethylene-propylene-styrene (SEPS) copolymer, hydrogenated above copolymers, ethylene- Propropylene copolymer (EPR), butadiene rubber (BR), isoprene rubber (IR), styrene-butadiene rubber (SBR), liquid isoprene rubber (liquid IR), liquid butadiene rubber (liquid BR), liquid styrene-butadiene rubber ( Liquid SBR), liquid styrene-isoprene rubber (liquid SI), liquid styrene-ethylene-propylene rubber (liquid SEP), liquid isoprene-butadiene rubber (liquid IR-BR), etc., alone or in combination of two or more. May be good. Since the content of these polymers needs to be less than SIS, it is less than 50% by weight of the polymer (A), preferably 20% by weight or less of the polymer (A), and more preferably 10% by weight of the polymer (A). % Or less.
Further, as described above, when EPDM, acrylic rubber, urethane rubber or the like is used in combination with SIS, the damping characteristics become more excellent.

The amount of styrene-isoprene diblock in the above SIS is preferably in the range of 50 to 95% by weight, more preferably in the range of 60 to 90% by weight. With such a diblock amount, it becomes easy to obtain a desired shear modulus, and it becomes more excellent in obtaining high damping characteristics and the like.
The amount of diblock is a value measured by gel permeation chromatography (GPC).

The amount of styrene in the SIS is preferably 10 to 30% by weight, more preferably 13 to 25% by weight. Such an amount of styrene makes it more excellent in terms of shear modulus.
The amount of styrene is a value measured by a nuclear magnetic resonance apparatus (NMR).

Further, the number average molecular weight (Mn) of the SIS is preferably in the range of 100,000 to 200,000, more preferably in the range of 100,000 to 150,000. That is, such a small molecular weight is preferable from the viewpoint of damping property.
The number average molecular weight (Mn) is a value measured according to gel permeation chromatography (GPC).

The Mooney viscosity of the polymer (A) at 100 ° C. is preferably 10 to 50, more preferably 13 to 40, from the viewpoint of improving the dispersibility of the filler and effectively solving the problems of the present invention. The range.
The Mooney viscosity of the polymer (A) is a value measured at a test temperature of 100 ° C. according to JIS K6300-1 (2001).

<< Silica (B) >>
As the silica (B), silica having a BET specific surface area of 350 m ² / g or less is used from the viewpoint of solving the problem of the present invention. The BET specific surface area of the silica ^{is preferably 80 to 320 m 2} / g, more preferably 100 to 300 m ² / g.
The BET specific surface area of the silica is, for example, a BET specific surface area measuring device using a _{mixed gas (N 2} : 70%, He: 30%) as an adsorbed gas after degassing the sample at 200 ° C. for 15 minutes. (Manufactured by Microdata Co., Ltd., 4232-II) can be measured.
The amount of DBA adsorbed on the silica (B) is preferably 10 to 350 mmol / kg, more preferably 20 to 300 mmol / kg, from the viewpoint of solving the problem of the present invention.
The amount of DBA adsorbed can be measured from the amount of dibutylamine (DBA) adsorbed on the unreacted silanol groups on the silica surface.

The silica (B) is not particularly limited as long as it has a BET specific surface area of 350 m ² / g or less as described above, and for example, wet silica, dry silica, colloidal silica, or the like can be used alone. Alternatively, two or more types are used together.

Further, the surface of the silica (B) is coated with silicone oil, dimethylsilane such as hexamethyldisilazane, octylsilane, dimethyldichlorosilane, trimethylsilane, monomethyltrichlorosilane, fatty acid (stearic acid) and the like, if necessary. Hydrophobization treatment is applied. These hydrophobized silicas and silicas not subjected to such surface treatments are used alone or in combination of two or more.

In particular, among the above-mentioned hydrophobized silicas, dimethylsilyl-treated silica and trimethylsilyl-treated silica surface-treated with dimethylsilane or trimethylsilane are preferable from the viewpoint of attenuation.

The content ratio of the silica (B) in the rubber composition for the vibration damping damper of the present invention is 10 to 200 parts by weight with respect to 100 parts by weight of the polymer (A) from the viewpoint of solving the problem of the present invention. It is preferably in the range of 20 to 150 parts by weight, more preferably in the range of 30 to 100 parts by weight.

《Calcium carbonate (C)》
As the calcium carbonate (C), for example, calcium carbonate that has not been surface-treated or calcium carbonate that has been surface-treated can be used. Of these, it is preferable to use stearic acid-treated calcium carbonate, logonic acid-treated calcium carbonate, lignin-treated calcium carbonate, fatty acid quaternary ammonium salt-treated calcium carbonate, or the like from the viewpoint of further improving the damping characteristics. More preferably, it is a quaternary ammonium salt-treated calcium carbonate, a loginate-treated calcium carbonate, or a lignin-treated calcium carbonate.
The above-mentioned various calcium carbonates may be used alone or in combination of two or more.

The content ratio of calcium carbonate (C) in the rubber composition for vibration damping damper of the present invention is 10 to 200 weight by weight with respect to 100 parts by weight of the polymer (A) from the viewpoint of solving the problem of the present invention. The range is preferably in the range of parts, more preferably in the range of 20 to 150 parts by weight, still more preferably in the range of 30 to 100 parts by weight.

If necessary, a filler (other filler) other than the above, a tackifier, a plasticizer, or the like may be appropriately added to the rubber composition for the vibration damping damper of the present invention.

Examples of the other fillers include talc, carbon black, carbon fibers, carbon nanotubes, and the like, and these are used alone or in combination of two or more.

The content ratio of the other filler appropriately blended in the rubber composition for a vibration damping damper of the present invention is preferably in the range of 1 to 50 parts by weight with respect to 100 parts by weight of the polymer (A). More preferably, it is in the range of 5 to 40 parts by weight. With such a content ratio, the damping characteristics are further improved.

The tackifier, which is appropriately blended in the rubber composition for a vibration damping damper of the present invention, is used for the purpose of improving damping characteristics and adhesiveness, and is, for example, a hydrogenated alicyclic hydrocarbon resin. Kumaron resin, rosin, rosin ester, ketone resin, dicyclopentadiene resin, maleic acid resin, epoxy resin, urea resin, melamine resin and the like are preferably used. These may be used alone or in combination of two or more.

The rubber composition for a vibration damping damper of the present invention contains, for example, the above-mentioned components (A) to (C) and, if necessary, other components, a kneader, a planetary mixer, a mixing roll, and a twin-screw type stirrer. It can be obtained by kneading with or the like.
Further, a first kneading step of preparing a master batch consisting of only 40 to 80% by weight of the component (A) and 50 to 100% by weight of the component (B), and adding all the remaining materials to the master batch. By preparing the rubber composition separately in the second kneading step of kneading, the dispersibility of the component (B) can be further enhanced, and the rubber composition for the vibration damping damper of the present invention can be efficiently produced. It is preferable because it can be used.

Then, the rubber composition for a vibration damping damper of the present invention prepared as described above is heated to a melting temperature or higher to be melted, poured into a mold, allowed to cool, and molded into a predetermined shape. Thereby, a viscoelastic body which is a constituent member of the vibration damping damper of the present invention can be manufactured.

^{The viscoelastic body is unvulcanized, and its shear modulus is 0.1 N / mm 2} or more under the conditions of a shear modulus of 200%, a frequency of 0.33 Hz, and a temperature of 20 ° C. It is preferably in the range of 0.25 to 0.35 N / mm ² , and even more preferably in the range of ^{0.25 to 0.30 N / mm 2.}

The shear modulus of the viscoelastic body is measured as follows using, for example, an apparatus as shown in FIG. That is, after applying the two-component adhesive for rubber to the predetermined positions (adhesive points of the sample 21) of the two blasted metal fittings 22, the rubber composition for forming the viscoelastic body between the metal fittings 22 Place an object and dry it. This is heat press-molded for a predetermined time (for example, at 100 ° C. for 10 minutes) to prepare a sample 21. Then, the device is vibrated in the direction of the arrow to evaluate the dynamic shear characteristics based on the load-strain loop curve shown in FIG. That is, the above-mentioned conditions (shear strain coefficient: 200% (200% with respect to the sample thickness), frequency ( f): 0.33 Hz, measurement temperature: 20 ° C.), and from the analysis of the shear strain value (δ) and the load value (Qd) with respect to the vibration time, they are equivalent according to the following equation (α). The rigidity (Ke) is obtained, and the shear modulus (Ge) is obtained according to the following formula (β). In the following formula, S indicates the area of the sample and D indicates the thickness of the sample.
Equivalent rigidity: Ke (N / mm) = Qd / δ… (α)
Shear modulus: Ge (N / mm ² ) = Ke ÷ S / D… (β)

Here, FIG. 1 shows an example of the vibration control damper of the present invention. In the figure, 1 is a vibration damping damper, 2 is a viscoelastic body, and 4 and 5 are metal plates. Then, the viscoelastic body 2 is adhered as shown in the figure while being sandwiched between the two metal plates 4 and 5.
FIG. 2 is a cross-sectional view (AA'cross-sectional view of FIG. 1) showing an example of the vibration control damper. FIG. 2 shows a viscoelastic body 2 in the vibration damping damper having a single-layer structure.
FIG. 3 is a cross-sectional view (A-A'cross-sectional view of FIG. 1) showing another example of the vibration control damper. FIG. 3 shows a viscoelastic body 2 in the vibration damping damper having a two-layer structure.

Next, FIG. 4 shows an installation example (one example) of the vibration damping damper 1. In the figure, 1 is a vibration damping damper, 2 is a viscoelastic body, 4 and 5 are metal plates, 6 is a bolt, 7 and 8 are panels, 10 is a beam, and 11 is a base. As shown in the figure, the metal plates 4 and 5 of the vibration damping damper 1 are attached to the panels 7 and 8 by bolts 6, respectively. The viscoelastic body 2 sandwiched between the metal plates 4 and 5 is functioning for vibration control between the beam 10 and the base 11.

The vibration damping damper of the present invention is not particularly limited to the one having the above-mentioned shape, and has excellent functions as a vibration damping damper for civil engineering and construction, a vibration damping damper for home appliances and electronic devices, and the like. Can be demonstrated.
In particular, it can exert more excellent functions as a vibration control damper used for large buildings such as bridges and buildings, especially as a vibration control damper for high-rise buildings.

Next, Examples will be described together with Comparative Examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded.

First, the materials shown below were prepared prior to Examples and Comparative Examples. In addition, each numerical value shown in the material shown below is a value measured based on the said measuring method.

[SIS (i)]
ZEON Corporation, Quintac 3520 (Moony viscosity at 100 ° C., styrene-isoprene diblock amount: 78% by weight, styrene amount: 15% by weight)

[SIS (ii)]
ZEON Corporation, Quintac 3620 (Moony viscosity at 100 ° C., styrene-isoprene diblock amount: 12% by weight, styrene amount: 15% by weight)

[EPDM]
EPDM4021 manufactured by Mitsui Chemicals, Inc. (Moony viscosity at 100 ° C.: 24)

[Processing aid]
Stearic acid (manufactured by NOF, Sakura beads)

[Anti-aging agent]
BASF, Irganox 1010

[Calcium carbonate]
Calcium carbonate surface-treated with stearic acid (manufactured by Shiraishi Calcium, Shiraishi Calcium CC)

[Untreated silica (i)]
Silica without surface treatment (manufactured by Tosoh Silica, Nipseal VN3, BET specific surface area: 218 m ² / g, DBA adsorption amount: 280 mmol / kg)

[Untreated silica (ii)]
Silica without surface treatment (manufactured by Nippon Aerosil Co., Ltd., Aerosil 380, BET specific surface area: 380 m ² / g, DBA adsorption amount: 10 mmol / kg)

[Surface-treated silica (i)]
Silica surface-treated with trimethylsilylating agent (Aerosil RX200, manufactured by Nippon Aerosil Co., Ltd., BET specific surface area: 110 m ² / g, DBA adsorption amount: 10 mmol / kg)

[Examples 1 to 5, Comparative Examples 1 to 5]
Each component shown in Tables 1 and 2 below was blended in the ratio shown in the same table to prepare a target rubber composition.
In addition, except for Comparative Example 4, a masterbatch was prepared (first kneading step), and then the remaining materials were kneaded (second kneading step) to prepare a target rubber composition.
The first kneading step was carried out by adding the total amount of silica to 50% by weight of the total amount of the polymer (SIS, EPDM) and kneading with a kneader at 130 ° C. for 10 minutes. The second kneading step was carried out by adding all the remaining materials to the master batch prepared by the first kneading step and kneading with a kneader at 130 ° C. for 10 minutes.
In Comparative Example 4, a rubber composition was prepared by kneading all the materials with a kneader at 130 ° C. for 20 minutes without preparing the masterbatch as described above.

[ΔG']
With respect to the rubber compositions of Examples and Comparative Examples obtained as described above, the storage elastic modulus (swing angle) of the unvulcanized rubber composition at a frequency of 11 Hz and 40 ° C. by RPA2000 (manufactured by Alpha Technology Co., Ltd.). The storage elastic modulus G'1 at 0.28% and the storage elastic modulus G'2) at a runout angle of 50% were measured. Then, based on the above measurement results, ΔG'represented by the following formula (I) was calculated. The results are also shown in Tables 1 and 2 below.
ΔG'= G'2 / G'1 …… (I)

Then, the following tests (1) to (3) were carried out using the rubber compositions of Examples and Comparative Examples. These results are also shown in Tables 1 and 2 below.

≪Examination (1)≫
The dynamic shearing characteristics of the rubber composition were evaluated using an apparatus as shown in FIG. That is, after applying the two-component adhesive for rubber to the predetermined positions (adhesion points of the sample 21) of the two blasted metal fittings 22 (size 140 mm × 80 mm, thickness 9 mm), the above two metal fittings The rubber composition of Example or Comparative Example was sandwiched between 22 and dried. This was heat press-molded at 100 ° C. for 10 minutes to prepare a sample (size 70 mm × 80 mm, thickness 5 mm) 21. Then, the device was vibrated in the direction of the arrow, and the dynamic shear characteristics were evaluated based on the load-strain loop curve shown in FIG. That is, for the above device, a vibrator (DYNAMIC SERVO manufactured by Washimiya Seisakusho Co., Ltd.), an input signal oscillator (manufactured by Yokogawa Electric Co., Ltd., synthesized function generator FC320), and an output signal processor (Ono Sokki Co., Ltd.) (Manufactured by, portable FFT analyzer CF-3200), vibration (shear distortion rate: 200% (200% with respect to sample thickness), frequency (f): 0.33 Hz, measurement temperature: 20 ° C.) is applied, and from the analysis of the shear distortion value (δ) and the load value (Qd) with respect to the excitation time, the equivalent rigidity (Ke) and the equivalent damping coefficient are according to the following equations (1) to (4). (Ce) was obtained, and the shear stiffness (Ge) and damping constant (he) were obtained from the values. In the equation below, ω = 2πf, W = Keδ 2/2, ΔW is the load - strain loop area (absorbed energy), S is the area of the sample, D is shows the thickness of the sample.
Equivalent rigidity: Ke (N / mm) = Qd / δ ... (1)
Equivalent attenuation coefficient: Ce (kN · s / m) = ΔW / πωδ ² … (2)
Attenuation constant: he = ΔW / 4πW ... (3)
Shear modulus: Ge (N / mm ² ) = Ke ÷ S / D ... (4)

≪Examination (2)≫
According to the method of the above test (1), a vibrating machine (manufactured by Washimiya Seisakusho, DYNAMIC SERVO), an input signal oscillator (manufactured by Yokogawa Electric Co., Ltd., synthesized function generator FC320), and an output signal processor (Ono). Using a portable FFT analyzer CF-3200) manufactured by Sokki Co., Ltd., a test of 50 vibrations was separately performed at a shear distortion rate of 200%, a frequency (f) of 0.33 Hz, and a measurement temperature of 20 ° C. Then, the shear modulus (Ge _{2 ) at the time of the second excitation and the shear modulus (Ge 50} ) at the time of the 50th excitation at this time are measured, and the values shown in the following equation (II) (II). %) Was calculated. This value was defined as the "Ge change rate of the 2nd to 50th waves".
{(Ge _{2- Ge 50} ) / Ge ₂ } × 100 ……… (II)

The above-mentioned 50 times vibration test was performed, and after 24 hours had passed, the vibration was performed again under the same conditions as above, and the shear modulus (Ge _2' ) at the time of the second vibration was measured. Then, the value (%) shown in the following formula (III) was calculated. This value was defined as the "Ge change rate 24 hours after 50 wave excitation".
{(Ge _{2- Ge 2'} ) / Ge ₂ } × 100 ……… (III)

≪Examination (3)≫
According to the method of the above test (1), a vibrating machine (manufactured by Washimiya Seisakusho, DYNAMIC SERVO), an input signal oscillator (manufactured by Yokogawa Electric Co., Ltd., synthesized function generator FC320), and an output signal processor (Ono). Oscillation assuming a typhoon (shear distortion rate: 50% (50% with respect to sample thickness), frequency (f): 5 Hz, measurement temperature: 20) using a portable FFT analyzer CF-3200 manufactured by Sokki Co., Ltd. A test for imparting ° C.) was conducted separately. Then, the shear modulus (Ge'2 _{) at the time of the second} excitation and the shear modulus (Ge' ₂₅₀₀ ) at the time of the 2500th excitation at this time were measured, and the values shown in the following equation (IV) (IV). %) Was calculated. This value was defined as the "Ge change rate of the 2nd to 2500th waves".
_{{(Ge '2 -Ge' 2500} ) / Ge '2} × 100 ......... (IV)

The above-mentioned 2500 times vibration test was performed, and after 24 hours had passed, the vibration was performed again under the same conditions as above, and the shear modulus (Ge '_2' ) at the time of the second vibration was measured. Then, the value (%) shown in the following formula (V) was calculated. This value was defined as "Ge change rate 24 hours after 2500 wave excitation".
_{{(Ge '2 -Ge' 2} ') / Ge' 2} × 100 ......... (V)

[comprehensive evaluation]
From the measurement results of the above tests (1) to (3), the shear modulus (Ge) is 0.1 N / mm ² or more, the damping constant (he) is 0.35 or more, and the above formula (II) and Those having a Ge change rate of 40 or less shown in (IV) and a Ge change rate of 20 or less shown in the above formulas (III) and (V) were evaluated as “⊚”.
Further, although it does not correspond to the above "◎", the shear modulus (Ge) is 0.1 N / mm ² or more and the damping constant (he) is 0.35 or more based on the measurement results of the above tests (1) to (3). Those having a Ge change rate of 40 or less shown in the above formulas (II) to (V) were evaluated as “◯”.
In addition, although it does not correspond to the above "◎" and "○", the shear modulus (Ge) is 0.1 N / mm ² or more and the damping constant (he) is determined from the measurement results of the above tests (1) to (3). Those having a larger than 0.30 and having a Ge change rate of 40 or less represented by the above formulas (II) to (V) were evaluated as "Δ".
Then, those who did not correspond to any of the above evaluations of "◎", "○" and "Δ" were evaluated as "x".

From the results in Table 1 above, the sample of the example contains each component specified in the present invention, and the total content of the organic radical scavenger (anti-aging agent) and the processing aid is within the range specified in the present invention. ΔG', which is an index of silica dispersibility, is also 8 or less. Therefore, it can be seen that the shear modulus (Ge) and the damping constant (he) satisfy the above evaluation criteria, and the Ge change rate when the vibration is continuously applied for a long period of time is also suppressed. .. In addition, as described above, the Ge change rate is further reduced when 24 hours have passed after the vibration is continuously applied for a long period of time, so that the shear modulus is also excellent in recovery. Recognize.
From the above, it was found that the sample of the example exhibited high damping property and was excellent in stability against repeated deformation and vibration.

On the other hand, from the results in Table 2 above, in the samples of Comparative Examples 1 to 3, the total content of the organic radical scavenger (anti-aging agent) and the processing aid exceeds the range specified in the present invention. ΔG'also exceeded 8. In particular, since the Ge change rate represented by the above formula (IV) was too large, the result was that the performance required for the present invention could not be obtained. The sample of Comparative Example 4 was not prepared by a masterbatch, and ΔG'was also a value exceeding 8. In particular, since the Ge change rate represented by the above formula (IV) was too large, the result was that the performance required for the present invention could not be obtained. The sample of Comparative Example 5 used silica having a high BET specific surface area (BET specific surface area ^{of more than 350 m 2} / g), although ΔG'was 8 or less, and as a result, the attenuation constant (he) was particularly high. The result was that the performance required for the present invention could not be obtained.

The vibration damping damper of the present invention can exhibit excellent functions as a vibration damping damper for civil engineering and construction, a vibration damping damper for home appliances and electronic devices, and the like. In particular, it can exert more excellent functions as a vibration control damper used for large buildings such as bridges and buildings, especially as a vibration control damper for high-rise buildings.
In addition, vibration damping devices and seismic isolation devices such as vibration damping walls for construction, and vibration damping materials and shock absorbing materials for home appliances and electronic devices, which are equipped with a viscous elastic body which is a component of the vibration damping damper of the present invention. , A vibration damping material for automobiles, a shock absorbing material, and the like can also be used as the vibration damping damper of the present invention.

1 Vibration damping damper 2 Viscoelastic body 4, 5 Metal plate 6 Bolt 7, 8 Panel 10 Beam 11 Base

Claims (8)

It contains the following polymer component (A) and the following (B) and (C) components, and the total content of the following (D) component with respect to 100 parts by weight of the (A) component is 5 parts by weight. The following rubber composition for a vibration damping damper, wherein the rubber composition satisfies the following conditions (X).
(A) A polymer containing styrene-isoprene-styrene block polymer as a main component.
(B) Silica having a BET specific surface area of 350 m ² / g or less.
(C) Calcium carbonate.
(D) At least one selected from the group consisting of organic radical scavengers and processing aids.
(X) ΔG'represented by the following formula (I) is 8 or less.
ΔG'= G'2 / G'1 …… (I)
[In the formula (I), G'1 is the storage elastic modulus of the unvulcanized rubber composition at a frequency of 11 Hz and a runout angle of 0.28% and 40 ° C., and G'2 is a frequency of 11 Hz and a runout angle. The storage elastic modulus of the unvulcanized rubber composition at 50% and 40 ° C. is shown. ] The vibration damping damper according to claim 1, wherein the styrene-isoprene-styrene block polymer of the component (A) has a diblock amount of styrene-isoprene of 50 to 95% by weight and a styrene amount of 10 to 30% by weight. Rubber composition for. The rubber composition for a vibration damping damper according to claim 1 or 2, wherein the Mooney viscosity of the component (A) at 100 ° C. is 10 to 50. The rubber composition for a vibration damping damper according to any one of claims 1 to 3, wherein the amount of DBA adsorbed by the component (B) is 10 to 350 mmol / kg. The rubber composition for a vibration damping damper according to any one of claims 1 to 4, wherein the component (B) is at least one selected from dimethylsilyl-treated silica and trimethylsilyl-treated silica. The method for producing a rubber composition for a vibration damping damper according to any one of claims 1 to 5, wherein 40 to 80% by weight of the component (A) and 50 to 100% by weight of the component (B). A rubber composition for a vibration damping damper, which comprises a first kneading step of preparing a master batch consisting of only%, and a second kneading step of adding all the remaining materials to the master batch and kneading the master batch. Manufacturing method. A vibration damping damper characterized in that a viscoelastic body made of the rubber composition for a vibration damping damper according to any one of claims 1 to 5 is used as a constituent member thereof. The vibration damping damper according to claim 7, which is a vibration damping damper for high-rise buildings.

Images