JP2015183110A - High attenuation rubber composition for vibration control damper and vibration control damper using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high attenuation rubber composition for a vibration control damper that can enhance the attenuation property without causing such problems as reduction in elastic modulus, deterioration in temperature dependency and deterioration in processability and to provide a vibration control damper that is produced by using the high attenuation rubber composition for a vibration control damper.SOLUTION: The high attenuation rubber composition for a vibration control damper is composed mainly of a component (A) as given below, contains a component (B) and a component (C) as given below and is free from a crosslinking agent component. The vibration control damper is produced by using a cured product of the high attenuation rubber composition for a vibration control damper as a constitutional member. The component (A) is a styrene-isoprene-styrene block copolymer; the component (B) is a peptizing agent belonging to either one of an aromatic mercaptan-based peptizing agent, an aromatic disulfide-based one, an aromatic mercaptan metal-based one and their mixture-based one; and the component (C) is a filler subjected to hydrophobization treatment.

Description

  The present invention relates to a high-damping rubber composition, and more particularly, to a high-damping rubber composition for a damping damper suitable for applications such as damping and seismic isolation in the building field, and a damping damper using the same. Is.

  Seismic control devices and seismic isolation devices in the building field are used for the purpose of suppressing vibrations on buildings from vibrations caused by earthquakes and winds, traffic vibrations caused by running large vehicles, and the like. In recent years, as rubber compositions used for such applications, liquid polymers are added to thermoplastic elastomers such as styrene-isoprene-styrene block polymers (SIS) to develop damping performance, and SIS, etc. A thermoplastic elastomer that is highly filled with a small particle size filler such as silica or calcium carbonate to develop friction damping has been developed (see Patent Documents 1 and 2).

  By the way, in the development of seismic dampers for buildings, in order to absorb the energy of a large earthquake, high attenuation of high strain by rubber material is an essential characteristic. In recent years, especially after the Great East Japan Earthquake, there have been many small and medium-sized earthquakes, and the need for high-attenuation materials has become even higher in order to respond to earthquakes that shake long and greatly, such as long-period earthquakes observed in high-rise buildings. (Especially rental buildings, condominiums, etc.).

JP-A-2005-239813 JP 2006-8859 A

  However, there is a concern about deterioration of temperature dependency and reduction of elastic modulus in the technique for imparting viscous damping using a liquid polymer or the like as described above to improve the damping. Moreover, in the method of expressing friction damping by high filling with a small particle size filler, the friction damping effect is enhanced by the high filling, but there is a concern about deterioration of workability.

  The present invention has been made in view of such circumstances, and a damping damper that can improve damping without causing problems such as a decrease in elastic modulus, deterioration in temperature dependency, and deterioration in workability. An object of the present invention is to provide a high-damping rubber composition for use and a damping damper using the rubber composition.

In order to achieve the above object, the present invention comprises the following (A) as a main component, the following (B) and (C) components, and a high damping for a damping damper that does not include a crosslinking agent component: The rubber composition is a first gist. Moreover, this invention makes the 2nd summary the damping damper which uses the hardening body of the said high damping rubber composition for damping dampers as a structural member.
(A) Styrene-isoprene-styrene block polymer.
(B) A peptizer belonging to any one of an aromatic mercaptan series, an aromatic disulfide series, an aromatic mercaptan metal series, and a mixed system thereof.
(C) Filler that has been hydrophobized.

  That is, the present inventors have intensively studied to solve the above problems. In the course of that research, styrene-isoprene-styrene block polymer (A) was used as the polymer for the high damping rubber composition for damping dampers, and the crosslinking agent components (crosslinking agents and vulcanization accelerators) were used to obtain damping properties. Recalling that the above polymer is used in combination with a predetermined peptizer (B) and a hydrophobized filler (C). The peptizer is usually used as a peptizer for diene rubber, and the present inventors make it act to increase the damping property of the styrene-isoprene-styrene block polymer (A). Used for that purpose. Furthermore, as described above, when a peptizer and a hydrophobized filler are combined, even if the filler is not highly filled (the amount of the filler is not changed), the elastic modulus decreases little and is attenuated. It has been found that a remarkable improvement effect of sex can be obtained. Since such operational effects can be obtained, it has been found that various problems that have occurred in the conventional attenuation method can be solved by the above-described blending composition, and the intended purpose can be achieved, and the present invention has been achieved. .

  Thus, the high damping rubber composition for a vibration damper of the present invention comprises a styrene-isoprene-styrene block polymer (A) as a main component, a predetermined peptizer (B), and a hydrophobized filler ( C) and a crosslinking agent component are not included, so that the damping property can be improved without causing problems such as a decrease in elastic modulus, deterioration in temperature dependency, and deterioration in workability. Due to such characteristics, it is possible to exert an excellent function as a material for a vibration control damper for a high-rise building.

It is a schematic diagram for demonstrating the evaluation method of a dynamic shear characteristic. It is a graph which shows a load-distortion loop curve.

  Next, embodiments of the present invention will be described in detail.

  The high damping rubber composition for a vibration damper of the present invention (hereinafter abbreviated as “high damping rubber composition”) is mainly composed of styrene-isoprene-styrene block polymer (A), and contains a predetermined peptizer ( It contains B) and the hydrophobized filler (C) and does not contain a crosslinking agent component (crosslinking agent or vulcanization accelerator). Here, the “main component” of the high-attenuation rubber composition is one that greatly affects the characteristics of the high-attenuation rubber composition, and accounts for 50% by weight or more of the entire high-attenuation rubber composition. means. Further, from the viewpoint of enhancing the damping property, the high damping rubber composition of the present invention does not contain a crosslinking agent component as described above.

  As described above, styrene-isoprene-styrene block polymer (SIS) is used for the polymer of the high damping rubber composition of the present invention as shown in (A) above. Styrene-butadiene-styrene block polymer (SBS), styrene-isobutylene-styrene block polymer (SIBS) and the like may be contained in a proportion of 10% by weight or less of the whole polymer.

  In the SIS (component A), the diblock amount of styrene-isoprene (content of the SI diblock component) is 50 to 95 wt% (particularly 55 to 80 wt%), and the styrene amount is 10 to 30 wt%. % (Especially 15 to 25% by weight) is preferable from the viewpoint of attenuation.

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

  On the other hand, as the peptizer (B) used together with the component (A), a peptizer belonging to any one of an aromatic mercaptan-based, aromatic disulfide-based, aromatic mercaptan metal-based and mixed system thereof is used. It is done. Specific examples of the aromatic disulfide peptizer include dibenzamide diphenyl disulfide. Specific examples of the aromatic mercaptan metal-based peptizer include zinc salts of benzamidothiophenol. And these are used individually or in combination of 2 or more types. Among these, dibenzamide diphenyl disulfide is preferable from the viewpoint of increasing the attenuation of SIS.

  And the ratio of the peptizer (B) to 100 parts by weight (hereinafter, abbreviated as “part”) of the polymer of the high damping rubber composition according to the present invention is preferably in the range of 0.025 to 0.3 part, Especially preferably, it is the range of 0.05-0.25 part. That is, if the proportion of the peptizer (B) is too small, the desired damping characteristics cannot be obtained, and conversely if too large, the elastic modulus may be lowered.

  As the hydrophobized filler (C) used together with the components (A) and (B), for example, a hydrophobized filler such as wet silica, dry silica, and calcium carbonate is used. These may be used alone or in combination of two or more.

  Examples of the hydrophobizing agent for the filler surface include dimethylsilane such as silicone oil, hexamethyldisilazane, octylsilane, dimethyldichlorosilane, trimethylsilane, monomethyltrichlorosilane, fatty acid (stearic acid) and the like. It is done.

  In particular, among the hydrophobized fillers (C), dimethylsilyl-treated fillers and trimethylsilyl-treated fillers that are surface-treated with dimethylsilane or trimethylsilane are preferable from the viewpoint of damping properties.

In addition, the hydrophobized filler (C) preferably has a BET specific surface area of 300 m ² / g or less and a DBA adsorption amount of 30 mmol / kg or less, particularly preferably BET, from the viewpoint of attenuation. The specific surface area is in the range of 100 to 200 m ² / g and the DBA adsorption amount is 20 mmol / kg or less. In the present invention, the BET specific surface area of the filler is, for example, determined by using a mixed gas (N ₂ : 70%, He: 30%) as an adsorbed gas after degassing the sample at 200 ° C. for 15 minutes. It can be measured by a specific surface area measuring device (Micro Data Corp., 4232-II). The DBA adsorption amount can be measured from the amount of dibutylamine (DBA) adsorbed on the unreacted silanol groups on the silica surface.

  And the ratio of the said hydrophobized filler (C) with respect to 100 parts of polymers of the high attenuation | damping rubber composition which concerns on this invention has the preferable range of 10-200 parts, Most preferably, it is the range of 20-70 parts. is there. That is, if the proportion of the filler (C) is too small, desired damping characteristics cannot be obtained, and conversely if too large, the workability may be deteriorated.

  In addition to the above components (A) to (C), the highly attenuated rubber composition of the present invention includes calcium carbonate (not hydrophobized), liquid polymer, natural asphalt, tackifier, and plasticizer. An anti-aging agent or the like may be appropriately blended as necessary.

  The highly damped rubber composition of the present invention uses, for example, the above components (A) to (C), and other components as necessary, using a kneader, a planetary mixer, a mixing roll, a twin-screw agitator, etc. And kneading. Then, the high damping rubber composition is heated to a melting temperature or higher, melted, poured into a mold, allowed to cool and molded into a predetermined shape, and used as a product of a high damping rubber composition. Can do. And the damping damper can be produced by using the product (cured body) of this highly damped rubber composition as a constituent member.

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

  First, prior to the examples and comparative examples, the following materials were prepared.

[SIS (A1)]
Made by Nippon Zeon Co., Ltd., Quintac 3520 (SI diblock component content: 78 wt%, styrene content: 15 wt%)

[SIS (A2)]
Made by Nippon Zeon Co., Ltd., Quintac 3433N (SI diblock component content: 56% by weight, styrene content: 16% by weight)

[SIS (A3)]
Made by Nippon Zeon Co., Ltd., Quintac 3270 (SI diblock component content: 67% by weight, styrene content: 24% by weight)

[SIBS]
SIBSTAR 102T (SI diblock component content: 0% by weight, styrene content: 15% by weight) manufactured by Kaneka Corporation

[Crushing agent (B1)]
Nouchitizer SD (dibenzamide diphenyl disulfide content: 25% by weight) manufactured by Ouchi Shinsei Chemical Co., Ltd.

[Fatty acid-treated calcium carbonate]
Shiraishi Calcium Co.

[Untreated silica]
Tosoh Silica Co., Ltd., Nipsil ER

[Hydrophobicized silica (C1)]
Development product manufactured by Tosoh Silica Co., Ltd. (wet silica hydrophobized with silicone oil based on the method disclosed in JP 2004-196847 A, BET specific surface area 103 m ² / g, DBA adsorption amount 5 mmol / kg)

[Hydrophobicized silica (C2)]
Development product manufactured by Tosoh Silica Co., Ltd. (wet silica hydrophobized with silicone oil based on the method disclosed in JP 2004-196847 A, BET specific surface area 134 m ² / g, DBA adsorption 19 mmol / kg)

[Hydrophobicized silica (C3)]
Development product manufactured by Tosoh Silica Co., Ltd. (wet silica hydrophobized with silicone oil based on the method disclosed in JP 2004-196847 A, BET specific surface area 128 m ² / g, DBA adsorption 31 mmol / kg)

[Hydrophobicized silica (C4)]
Product developed by Tosoh Silica Co., Ltd. (wet silica hydrophobized with silicone oil based on the method disclosed in JP 2004-196847 A, BET specific surface area 144 m ² / g, DBA adsorption amount 78 mmol / kg)

[Sulfur (crosslinking agent)]
Tsurumi Chemical Co., Ltd.

[Vulcanization accelerator]
Sulfenamide vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd., Noxeller CZ-G)

[Examples 1-9, Comparative Examples 1-5]
The components shown in Tables 1 to 3 below were blended in the proportions shown in the same table, and these were kneaded with a kneader to prepare a target rubber composition.

  Using the rubber compositions of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the following criteria. These results are also shown in Tables 1 to 3 above.

[Shear modulus (Ge), damping constant (he)]
The dynamic shear characteristics of the rubber composition were evaluated using a sample as shown in FIG. That is, after applying a two-component adhesive for rubber to the metal fitting 2 (size 140 mm × 80 mm, thickness 9 mm) subjected to blasting, the rubber composition of Example or Comparative Example is sandwiched between the metal fittings 2. Drying was performed. This was hot press molded at 100 ° C. for 10 minutes to prepare a sample (size 70 mm × 80 mm, thickness 5 mm) 1. Then, this sample 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, with respect to the above sample, a vibration exciter (manufactured by Kakinomiya Seisakusho, DYNAMIC SERVO), an input signal oscillator (manufactured by Yokogawa Electric, synthesized function generator FC320), and an output signal processor (Ono Sokki Co., Ltd.) Using a portable FFT analyzer CF-3200 manufactured by the company, excitation (shear strain rate: 200% (200% of the sample thickness), frequency (f): 0.33 Hz assuming a second wave during a large earthquake From the analysis of the shear strain value (δ) and the load value (Qd) with respect to the excitation time, the equivalent stiffness (Ke) is determined according to the following formulas (1) to (4). The equivalent damping coefficient (Ce) was determined, and the shear modulus (Ge) and damping constant (he) were determined from the values. In the equation below, ω = 2πf, W = Keδ 2/2, ΔW is the load - shows distortion loop area, S is the area of the sample, D is the thickness of the sample. Then, in the shear modulus (Ge), 0.07 N / mm ² or more was evaluated as ○, and less than 0.07 N / mm ² was evaluated as ×. Further, in the damping constant (he), a value of 0.5 or more was evaluated as ◯, a value of 0.4 or more and less than 0.5 was evaluated as Δ, and a value of less than 0.4 was evaluated as ×.
Equivalent rigidity: Ke (N / mm) = Qd / δ (1)
Equivalent damping coefficient: Ce (kN · s / m) = ΔW / πωδ ² (2)
Attenuation constant: he = ΔW / 4πW (3)
Shear elastic modulus: Ge (N / mm ² ) = Ke ÷ S / D (4)

  From the results of Tables 1 to 3, the samples of the examples have large shear elastic modulus (Ge) and large damping constant (he) in the dynamic shear property evaluation test. It can be seen that the damping characteristics required for the damper are obtained.

  On the other hand, since the sample of Comparative Example 1 does not use a peptizer and uses untreated silica for the filler, the damping constant (he) is small. The sample of Comparative Example 2 uses a peptizer but does not use hydrophobized silica (uses untreated silica), and the sample of Comparative Example 3 uses hydrophobized silica. No peptizer is used. The samples of Comparative Examples 2 and 3 have a higher shear modulus (Ge) and a smaller damping constant (he) than the sample of Example 1. The sample of Comparative Example 4 contains a cross-linking agent component and has a higher shear modulus (Ge) and a smaller damping constant (he) than the sample of Example 1. The sample of Comparative Example 5 does not contain the filler itself, and both the shear modulus (Ge) and the damping constant (he) are small. Therefore, it can be understood that the samples of these comparative examples do not have the damping characteristics required for the seismic damper of the present invention.

  The highly damped rubber composition of the present invention comprises a damping damper for construction and civil engineering, a damping device and a seismic isolation device for a damping wall for construction, a damping damper for home appliances and electronic equipment, It can be used for materials, shock absorbing materials, vibration damping materials for automobiles, shock absorbing materials and the like. In particular, it can exhibit excellent functions as a material for vibration control dampers for high-rise buildings.

Claims (8)

A highly damped rubber composition for a vibration damper, comprising the following (A) as a main component, the following (B) and (C) components, and no crosslinking agent component.
(A) Styrene-isoprene-styrene block polymer.
(B) A peptizer belonging to any one of an aromatic mercaptan series, an aromatic disulfide series, an aromatic mercaptan metal series, and a mixed system thereof.
(C) Filler that has been hydrophobized.   The high damping rubber composition for a vibration damper according to claim 1, wherein the diblock amount of styrene-isoprene in the component (A) is 50 to 95% by weight and the styrene amount is 10 to 30% by weight.   The high damping rubber composition for a vibration damper according to claim 1 or 2, wherein the peptizer of the component (B) is dibenzamide diphenyl disulfide.   The content rate of the filler of said (C) component is the range of 10-200 weight part with respect to 100 weight part of polymers of the said high attenuation | damping rubber composition, The control as described in any one of Claims 1-3. High damping rubber composition for seismic dampers.   The filler of the said (C) component is what hydrophobized at least 1 chosen from the group which consists of a wet silica, a dry-type silica, and a calcium carbonate, As described in any one of Claims 1-4. High damping rubber composition for vibration control damper.   The highly damped rubber composition for a vibration damper according to any one of claims 1 to 5, wherein the filler of the component (C) is at least one of a dimethylsilyl-treated filler and a trimethylsilyl-treated filler. The high damping rubber for a vibration damper according to any one of claims 1 to 6, wherein the filler of the component (C) has a BET specific surface area of 300 m ² / g or less and a DBA adsorption amount of 30 mmol / kg or less. Composition.   A damping damper comprising the cured body of the high damping rubber composition for damping damper according to any one of claims 1 to 7 as a constituent member.

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