TWI764079B - Shock Damper - Google Patents

Abstract

The present invention provides a damping damper that has low temperature dependence of attenuation characteristics, exhibits high attenuation, and can satisfy maintenance of attenuation for long-period seismic activity. A shock-absorbing damper 1, comprising a viscoelastic body 2 sandwiched between two metal plates 4 and 5, the viscoelastic body 2 is set as a viscoelastic body comprising a rubber composition, and the rubber composition contains : A polymer component containing the following (A) component as a main component and the following (B) component; and the following (C) component. (A) Styrenic elastomer. (B) An ethylene-propylene-diene monomer terpolymer having a higher Muni viscosity at 100° C. than the aforementioned (A) component. (C) Surface-treated silica surface-treated with a silane coupling agent represented by the following general formula (1).

Description

shock absorber

The present invention relates to a shock-absorbing damper, and in particular, to a shock-absorbing damper suitable for shock-absorbing or anti-seismic applications in the fields of civil engineering and construction.

Regarding the vibration-absorbing devices or anti-seismic devices in the fields of civil engineering and construction, especially the shock-absorbing dampers used in large buildings such as bridges and buildings, in order to absorb vibrational energy (vibrational energy) caused by earthquakes, etc. In addition to the performance of damping performance as an element of the mechanical structure of the shock absorbing damper, high damping is required to be achieved by the viscoelastic body (rubber material) used in the shock absorbing damper.

In addition, the 2016 Ministry of Land, Infrastructure, Transport and Tourism Guidelines also describe a shock absorber that does not degrade the damping properties of shaking with a long convergence time in response to long-period seismic activity (convergence time of 600 seconds) in high-rise buildings. demand continues to increase.

The viscoelastic body used in the conventional shock absorber mainly uses a viscoelastic body mainly composed of a styrene-isoprene-styrene (SIS) copolymer (for example, refer to Patent Document 1). and Patent Document 2). In addition, for SIS copolymers, in order to exhibit friction attenuation, low-viscosity ethylene-propylene-diene monomer terpolymers (low-viscosity EPDM (ethylene-propylene-diene) monomeric terpolymers (low-viscosity EPDM (ethylene propylene glycol), which are easy to cause frictional attenuation by blending a large amount of diene) are also being studied. propylene diene monomer)), or high filling of small particle size fillers such as silica or calcium carbonate. [Prior Art Literature]

[Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 2014-227521 [Patent Document 2] Japanese Patent Laid-Open No. 2015-183110

[Problems to be Solved by Invention] Incorporation of low viscosity EPDM in SIS copolymers as described exhibits high attenuation by the breakdown of cohesion of the low viscosity EPDM upon shear. Therefore, it is difficult to maintain the damping property against shaking with a long convergence time, and the low-viscosity EPDM blended as described above has a problem that the damping property fluctuates (deterioration of temperature dependence) due to the operating temperature easily. In addition, even if the SIS copolymer is filled with a high amount of filler and exhibits frictional attenuation, it is difficult to maintain the damping property against shaking with a long convergence time.

That is, with regard to the damper, the demand for short-term high attenuation peculiar to large earthquakes has been studied, but the actual situation is that the absorption energy (ΔW) required to maintain the attenuation of long-period seismic activity for a long time has not been Do adequate research.

The present invention has been made in view of such a situation, and an object of the present invention is to provide a damping damper which has low temperature dependence of attenuation characteristics, exhibits high attenuation, and can satisfy maintenance of attenuation for long-period seismic activity. [Technical means to solve the problem]

（所述通式（1）中，R₁ 表示碳數6～20的烷基、末端為苯基的碳數6～20的烷基，R₂ 、R₃ 表示R₁ 的碳數以下的碳數的烷基、或者碳數1～3的烷氧基，X表示碳數1～3的烷氧基。） [2]根據[1]所述的減震阻尼器，其中所述橡膠組合物中的（A）成分與（B）成分的混合比例以重量比計為（A）：（B）=95：5～50：50的範圍。 [3]根據[1]或[2]所述的減震阻尼器，其中所述橡膠組合物中的所述表面處理二氧化矽（C）的含有比例相對於所述聚合物成分的總量100重量份而為5重量份～100重量份的範圍。 [4]根據[1]至[3]中任一項所述的減震阻尼器，其中所述橡膠組合物中的包含所述表面處理二氧化矽（C）的所有二氧化矽的含有比例相對於所述聚合物成分的總量100重量份而為5重量份～100重量份。 [5]根據[1]至[4]中任一項所述的減震阻尼器，其中所述苯乙烯系彈性體（A）的100℃下的慕尼黏度為5～35。 [6]根據[1]至[5]中任一項所述的減震阻尼器，其中所述乙烯-丙烯-二烯單體三元共聚物（B）的100℃下的慕尼黏度為30～100。 [7]根據[1]至[6]中任一項所述的減震阻尼器，其中所述苯乙烯系彈性體（A）為苯乙烯-異戊二烯-苯乙烯共聚物。 [8]根據[1]至[7]中任一項所述的減震阻尼器，為用於高樓大廈的減震阻尼器。In order to achieve the said objective, this invention makes the following [1]-[8] the summary. [1] A vibration damper comprising, as its constituent member, a viscoelastic body comprising a rubber composition containing a polymer component having the following (A) component as a main component and Contains the following (B) component; and the following (C) component. (A) Styrenic elastomer. (B) An ethylene-propylene-diene monomer terpolymer having a higher Muni viscosity at 100° C. than the aforementioned (A) component. (C) Surface-treated silica surface-treated with a silane coupling agent represented by the following general formula (1). [hua 1]

(In the general formula (1), R ₁ represents an alkyl group having 6 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms with a phenyl terminal at the end, and R ₂ and R ₃ represent carbons having a carbon number less than or equal to that of R ₁ . a number of alkyl groups, or an alkoxy group having 1 to 3 carbon atoms, and X represents an alkoxy group having 1 to 3 carbon atoms.) [2] The shock absorber according to [1], wherein the rubber composition Among them, the mixing ratio of (A) component and (B) component is in the range of (A):(B)=95:5 to 50:50 in terms of weight ratio. [3] The shock absorption damper according to [1] or [2], wherein the content ratio of the surface-treated silica (C) in the rubber composition is relative to the total amount of the polymer component 100 parts by weight, but in the range of 5 parts by weight to 100 parts by weight. [4] The shock absorption damper according to any one of [1] to [3], wherein the content ratio of all silicas including the surface-treated silica (C) in the rubber composition It is 5 to 100 parts by weight with respect to 100 parts by weight of the total amount of the polymer components. [5] The shock damper according to any one of [1] to [4], wherein the styrene-based elastomer (A) has a Mooney viscosity at 100° C. of 5 to 35. [6] The shock absorption damper according to any one of [1] to [5], wherein the ethylene-propylene-diene monomer terpolymer (B) has a Mooney viscosity at 100° C. of 30 to 100. [7] The shock absorption damper according to any one of [1] to [6], wherein the styrene-based elastomer (A) is a styrene-isoprene-styrene copolymer. [8] The shock-absorbing damper according to any one of [1] to [7], which is a shock-absorbing damper for high-rise buildings.

That is, the inventors of the present invention have made intensive studies in order to solve the above-mentioned problems. In the research process, as the material of the viscoelastic body, which is a component of the shock absorption damper, a styrene-based elastomer such as SIS copolymer is used as the main polymer, and the Muni viscosity at 100°C is higher than the above-mentioned Ethylene-propylene-diene monomer terpolymer (EPDM) with higher styrene-based elastomer is used in combination with the styrene-based elastomer, and further contains a silane coupling agent represented by the general formula (1). Surface-treated silica is surface-treated. As a result, low temperature dependence of attenuation characteristics can be achieved while maintaining high attenuation properties, and aggregation of polymers or fillers is not easily broken during shearing. As a result, it was found that it is easy to maintain for a long time. The absorbed energy (ΔW) required to attenuate long-period seismic activity, thus completing the present invention.

In addition, the alkoxy group X represented by the general formula (1) is hydrolyzed by moisture in the air during the surface treatment of silica to become a hydroxyl group, and hydrogen-bonded or hydrogen-bonded to the hydroxyl group on the surface of silica The dehydration reaction progresses and ether linkage progresses, whereby the surface-treated silica surface-treated with the silane coupling agent represented by the general formula (1) is constituted. Therefore, as shown in FIG. 7 , the surface-treated silica has a long-chain alkyl group (long-chain alkyl group 31 ) represented by R ₁ of the general formula (1) on the surface of the silica 32 . Moreover, as shown in FIG. 7 , the long-chain alkyl groups 31 on the surface of the silica 32 interact with each other, so that the aggregation of the polymer or filler is difficult to be destroyed during shearing, imparting plasticity, and it is easy to recover even if it is subjected to long-period seismic activity. In the original state, it is considered that the absorbed energy (ΔW) required to attenuate long-period seismic activity is more likely to be maintained for a long period of time than when the conventional surface-treated silica is used. Because of the good dispersibility of existing surface-treated silica, most of the silane coupling agents having only an alkyl group with a small carbon number (for example, trimethyl) are used for surface treatment. Suitable for short-term high attenuation. However, since the interaction between the general alkyl groups is weak, it is considered that the maintenance of the attenuation property for long-period seismic activity cannot be satisfied.

[Effect of invention] The vibration damper of the present invention includes, as its constituent member, a viscoelastic body comprising a rubber composition containing a polymer component, the styrene-based elastomer (A) as a main component, and a EPDM (B) having a higher Mooney viscosity at 100° C. for the styrene-based elastomer (A); and the surface-treated silica (C) component, using the silane coupling agent represented by the general formula (1) Surface treated. Therefore, the temperature dependence of the attenuation characteristics is low, high attenuation is exhibited, and the maintenance of the attenuation for long-period seismic activity can be satisfied. Therefore, it can exhibit excellent performance as a shock absorber for large buildings such as tall buildings and bridges.

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

The vibration damper of the present invention includes, as its constituent member, a viscoelastic body comprising a rubber composition containing a polymer component, the following (A) component as a main component, and the following (B) ) ingredient; and ingredient (C) below. (A) Styrenic elastomer. (B) EPDM having a higher Munich viscosity at 100°C than the above-mentioned (A) component. (C) Surface-treated silica surface-treated with a silane coupling agent represented by the following general formula (1).

（所述通式（1）中，R₁ 表示碳數6～20的烷基、末端為苯基的碳數6～20的烷基，R₂ 、R₃ 表示R₁ 的碳數以下的碳數的烷基、或者碳數1～3的烷氧基，X表示碳數1～3的烷氧基。）[hua 2]

(In the general formula (1), R ₁ represents an alkyl group having 6 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms with a phenyl terminal at the end, and R ₂ and R ₃ represent carbons having a carbon number less than or equal to that of R ₁ . number of alkyl groups, or alkoxy groups with 1 to 3 carbon atoms, and X represents an alkoxy group with 1 to 3 carbon atoms.)

Here, the "main component" of the polymer component refers to 50% by weight or more of the total amount of the polymer component (including the liquid polymer described later as an optional material). In addition, as mentioned above, what used together (A) component and (B) component can be used for the polymer component of the said rubber composition. Furthermore, it is desirable that the polymer component contains only the components (A) and (B) from the viewpoints of temperature dependence and attenuation.

《Styrenic Elastomer (A)》 Examples of the styrene-based elastomer include block copolymers having a soft segment as a diene block (diene polymer part) and a hard segment as a styrene block (styrene polymer part) Wait. The diene block may be a block having a random structure of styrene and diene.

Specific examples of the styrene-based elastomer include styrene-butadiene (SB) copolymers and styrene-butadiene-styrene (SBS) copolymers , 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 - Styrene-ethylene-propylene-styrene (SEPS) copolymers, hydrogenated said respective copolymers, and the like. These can be used alone or in combination of two or more. Among them, the SIS copolymer is preferred from the viewpoint of temperature dependence.

The Munich viscosity at 100° C. of the styrene-based elastomer is preferably in the range of 5 to 35, and more preferably in the range of 10 to 30. Furthermore, in the present invention, it is necessary to use the Munich viscosity smaller than that of EPDM (B). The Munich viscosity of the styrene-based elastomer is a value measured at a test temperature of 100° C. in accordance with Japanese Industrial Standards (JIS) K6300-1 (2001).

In addition, the amount of the diblock component of the styrene-based elastomer (for example, the amount of the styrene-isoprene diblock component in the case of the SIS copolymer) is preferably 5% by weight to 90% by weight, more The range of 10 to 80 weight% is preferable. When the amount of the diblock component is set as such, the desired shear elastic modulus can be easily obtained, and high attenuation characteristics, low temperature dependence, and the like can be obtained. In addition, the said amount of the diblock component is a value measured by gel permeation chromatography (gel permeation chromatography, GPC).

In addition, the amount of styrene in the styrene-based elastomer is preferably in the range of 1% by weight to 60% by weight, and more preferably in the range of 10% by weight to 40% by weight. If it is such a styrene amount, it will become more excellent in the point of shear elasticity coefficient. In addition, the said amount of styrene is the value measured by the nuclear magnetic resonance apparatus (nuclear magnetic resonance, NMR).

"EPDM (B)" As the EPDM, an EPDM having a higher Muni viscosity at 100° C. than the styrene-based elastomer can be used. Such EPDM has high strength and can help to improve the retention rate of absorbed energy. The Munich viscosity at 100° C. of the EPDM is preferably in the range of 30 to 100, more preferably in the range of 35 to 85. In addition, the Munich viscosity of the EPDM is a value measured at a test temperature of 100° C. in accordance with JIS K6300-1 (2001).

From the viewpoint of temperature dependence, the ethylene content of the EPDM is preferably 5% by weight to 60% by weight, more preferably 10% by weight to 40% by weight.

In addition, from the viewpoint of attenuation properties, the diene content of the EPDM is preferably 3% by weight to 25% by weight, more preferably 5% by weight to 15% by weight.

In addition, as the diene-based monomer (third component) of the EPDM, a diene-based monomer having 5 to 20 carbon atoms is preferable, and specific examples thereof include 1,4-pentadiene and 1,4-hexane. Diene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, 1,4-octadiene, 1,4-cyclohexadiene, cyclooctadiene, diolefin Cyclopentadiene (dicyclopentadiene, DCP), 5-ethylidene-2-norbornene (5-ethylidene-2-norbornene, ENB), 5-butylene-2-norbornene, 2-methylallyl base-5-norbornene, 2-isopropenyl-5-norbornene, etc. Among these diene-based monomers (third component), dicyclopentadiene (DCP) and 5-ethylidene-2-norbornene (ENB) are preferred.

The mixing ratio of the styrene-based elastomer (A) and the EPDM (B) in the rubber composition is preferably in the range of (A):(B)=95:5 to 50:50 in terms of weight ratio, more preferably (A):(B)=90:10-55:45 range, more preferably (A):(B)=85:15-60:40 range. By setting the mixing ratio as such, it becomes more excellent in terms of satisfying high attenuation characteristics, low temperature dependence, and maintenance of attenuation properties for long-period seismic activity.

"Surface Treatment Silica (C)" As the surface-treated silica, silica that has been surface-treated with a silane coupling agent represented by the following general formula (1) can be used.

（所述通式（1）中，R₁ 表示碳數6～20的烷基、末端為苯基的碳數6～20的烷基，R₂ 、R₃ 表示R₁ 的碳數以下的碳數的烷基、或者碳數1～3的烷氧基，X表示碳數1～3的烷氧基。）[hua 3]

(In the general formula (1), R ₁ represents an alkyl group having 6 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms with a phenyl terminal at the end, and R ₂ and R ₃ represent carbons having a carbon number less than or equal to that of R ₁ . number of alkyl groups, or alkoxy groups with 1 to 3 carbon atoms, and X represents an alkoxy group with 1 to 3 carbon atoms.)

Regarding the silane coupling agent represented by the general formula (1), the number of carbon atoms in R ₁ needs to be 6 to 20 as described above, and preferably in the range of 8 to 16. By specifying in this manner, maintenance of damping properties for long-period seismicity can be satisfied. In addition, regarding the silane coupling agent represented by the general formula (1), as described above, R ₂ and R ₃ need to be an alkyl group having a carbon number less than the carbon number of R ₁ , or an alkyl group having 1 to 3 carbon atoms. alkoxy. Therefore, when R ₂ and R ₃ are alkyl groups, the carbon numbers of R ₂ and R ₃ can be in the range of 1 to 20, but preferably the carbon numbers of R ₂ and R ₃ are in the range of 1 to 6, and more The range of 1-3 is preferable. That is, the reason for this is that the reactivity with silicon dioxide is further improved by regulating the carbon numbers of R ₂ and R ₃ to be small in the above-described manner, and favorable surface treatment can be performed on silicon dioxide. In addition, when R ₂ and R ₃ are alkoxy groups having 1 to 3 carbon atoms, the reactivity with silica is also improved, and favorable surface treatment can be performed on silica. In addition, R ₂ and R ₃ may be the same or different.

Regarding the silane coupling agent represented by the general formula (1), X specifically includes alkoxy groups such as a methoxy group and an ethoxy group. In addition, the alkoxy group X is hydrolyzed by moisture in the air during the surface treatment of silica to become a hydroxyl group, and the hydroxyl group on the surface of the silica undergoes hydrogen bonding or dehydration reaction to be ether-bonded. Thereby, the silica (surface-treated silica) surface-treated with the silane coupling agent represented by the said general formula (1) is comprised. Thus, by the hydrolysis of the alkoxy group X, an alcohol (methanol, ethanol, etc.) can be released.

As the material of the surface-treated silica, that is, silica, for example, wet silica, dry silica, colloidal silica, and the like can be used. Moreover, these can be used individually or in combination of 2 or more types. Among them, wet silica can be preferably used from the viewpoint of reaction control of the silica surface treatment using the silane coupling agent represented by the general formula (1). Here, in the silica, methanol, isopropanol, ethylene glycol, ethyl acetate, methyl ethyl ketone, toluene, etc. are generally used as the dispersion liquid, among which ethyl acetate, methyl ethyl The base ketone can be preferably used because there is no fear of inhibiting the silica surface treatment reaction by the silane coupling agent represented by the general formula (1). In addition, the surface treatment is performed by, for example, dispersing silica in the dispersion liquid containing the silane coupling agent represented by the general formula (1).

In addition, from the viewpoint of the effect of improving the attenuation property, the primary particle diameter of the silica before the surface treatment is preferably 5 nm to 100 nm, more preferably 5 nm to 50 nm. Furthermore, the primary particle size is observed by using a scanning electron microscope (SEM) device and/or a transmission electron microscope (TEM) device after sampling the sample with a microtome. and measured.

From the viewpoints of the bonding property of the silane coupling agent to the surface of the silica and the improvement of the dispersibility of the silica, the surface-treated silica (C) is preferably prepared before the rubber composition is prepared. The surface treatment of silica is performed in advance using the silane coupling agent represented by the general formula (1). In addition, as a method for mixing the surface-treated silica with the polymer component, for example, after drying the surface-treated silica, it may be kneaded with the polymer component, or the surface-treated silica may be dried. Previously, the polymer components were dissolved and mixed in the organic solvent (methanol, isopropanol, ethylene glycol, ethyl acetate, methyl ethyl ketone, toluene, etc., which are dispersions of silica).

Moreover, the content ratio of the surface-treated silica (C) in the rubber composition is preferably in the range of 5 parts by weight to 100 parts by weight with respect to 100 parts by weight of the total amount of the polymer components, and more The range of 10 to 80 parts by weight is preferable, and the range of 15 to 60 parts by weight is more preferable. That is, by setting such a ratio, it is possible to further satisfy the maintenance of the damping property for long-period seismic activity.

Furthermore, when preparing the rubber composition, the silane coupling agent represented by the general formula (1) and silicon dioxide can also be separately added to react in the rubber composition to form the surface-treated dioxide. Silicon (C).

In addition, when silica other than the surface-treated silica (C) is used in combination with the rubber composition (including silica and the like that have not been surface-treated), the total amount of the polymer component is 100 parts by weight, the content ratio of all silica including the surface-treated silica (C) in the rubber composition is preferably 5 parts by weight to 100 parts by weight, more preferably 5 parts by weight to 50 parts by weight The range of parts by weight is more preferably in the range of 10 parts by weight to 45 parts by weight.

Furthermore, in the rubber composition, the surface-treated silica (C) tends to exist in the styrene-based elastomer (A), and as a result, the damping property becomes excellent.

In addition, a filler other than silica, a liquid polymer, an adhesion imparting agent, a plasticizer, an anti-aging agent, etc. may be appropriately blended in the rubber composition as necessary.

Examples of fillers other than the silica include calcium carbonate, talc, carbon black, carbon fibers, and carbon nanotubes, and these may be used alone or in combination of two or more.

As the calcium carbonate, it is particularly preferable to use stearic acid-treated calcium carbonate, rosin-acid-treated calcium carbonate, lignin-treated calcium carbonate, Fatty acid quaternary ammonium salt treatment of calcium carbonate, etc.

The content ratio of calcium carbonate or talc in the rubber composition is preferably 5 to 100 parts by weight, more preferably 10 parts by weight, relative to 100 parts by weight of the total amount of polymer components in the rubber composition ~80 parts by weight range. With such a content ratio, the damping characteristics can be further improved while maintaining the temperature dependence of rigidity well. In addition, the content ratio of other fillers (carbon black, carbon fiber, carbon nanotube, etc.) is preferably 1 to 50 parts by weight relative to 100 parts by weight of the total amount of polymer components in the rubber composition, and more Preferably it is the range of 2 weight part - 20 weight part.

Moreover, as a liquid polymer suitably mix|blended with the said rubber composition, liquid isoprene rubber (liquid IR (isoprene rubber)), liquid butadiene rubber (liquid BR (butadiene rubber), for example rubber)), liquid styrene butadiene rubber (liquid SBR (styrene butadiene rubber)), liquid styrene-isoprene rubber (liquid SI (styrene-isoprene)), liquid styrene-ethylene / Propylene rubber (liquid SEP (styrene ethylene propylene)), liquid isoprene-butadiene rubber (liquid IR-BR (isoprene rubber-butadiene rubber)), etc. These can be used alone or in combination of two or more. The liquid polymer preferably has a glass transition point (Tg) of -55°C or lower, and particularly preferably has a glass transition point (Tg) of -60°C or lower. In addition, the said glass transition point (Tg) is the value calculated|required by the differential scanning calorimetry (differential scanning calorimetry, DSC) measurement method (differential scanning calorimetry).

The content ratio of the liquid polymer in the rubber composition is preferably 5 parts by weight to 40 parts by weight, more preferably 10 parts by weight relative to 100 parts by weight of the total amount of the polymer components in the rubber composition ~40 parts by weight range.

Adhesion imparting agents suitably formulated in the rubber composition are used for the purpose of improving attenuation properties or adhesion, and for example, hydrogenated alicyclic hydrocarbon resins, coumarone resins, rosin, rosin esters, ketone resins, Cyclopentadiene resin, maleic acid resin, epoxy resin, urea resin, melamine resin, etc. These can be used alone or in combination of two or more.

Examples of antiaging agents that can be suitably formulated in the rubber composition include aromatic secondary amine antiaging agents, special wax antiaging agents, amine-ketone antiaging agents, phenolic antiaging agents, and imidazoles. Anti-aging agent, etc. These can be used alone or in combination of two or more.

The rubber composition can be kneaded with the components (A) to (C), as well as other components as needed, by using, for example, a kneader, a planetary mixer, a mixing roll, a twin-shaft screw mixer, or the like. and obtained. Then, the rubber composition is heated to a melting temperature or higher to be melted, poured into a mold frame, left to cool, and molded into a predetermined shape, thereby producing a viscoelasticity component of the damper of the present invention. body.

The viscoelastic body is an unvulcanized viscoelastic body, and its shear elasticity coefficient is preferably 0.15 N/mm ² or more, more preferably 0.2 under the conditions of a shear strain rate of 200%, a frequency of 0.5 Hz, and a temperature of 20 °C The range of N/mm ² to 0.35 N/mm ² is more preferably the range of 0.23 N/mm ² to 0.3 N/mm ² .

In addition, the shear elasticity coefficient of the said viscoelastic body is measured as follows using the apparatus shown in FIG. 5, for example. That is, after applying a two-liquid adhesive for rubber to a predetermined portion of the two pieces of metal fittings 22 (the adjoining portion of the sample 21 ) that have been sandblasted, the viscoelastic body forming adhesive is sandwiched between the metal fittings 22 . the rubber composition and dried. This is subjected to hot press molding for a predetermined time (for example, 10 minutes at 100° C.) to prepare a sample 21 . Then, the apparatus was excited in the direction of the arrow, and the dynamic shear characteristics were evaluated based on the load-strain loop curve shown in FIG. 6 . That is, in the above-mentioned apparatus, a vibration exciter, an input signal oscillator, and an output signal processor were used, and under the conditions (shear strain rate: 200% (200% relative to the sample thickness), frequency ( f): 0.5 Hz, measurement temperature: 20°C), excitation is given, and the following formula (α) is obtained from the analysis of the shear strain value (δ) and the load value (Qd) for the excitation time. The equivalent rigidity (Ke) is obtained, and the shear elastic coefficient (Ge) is obtained according to the following formula (β). In addition, in the following formula, S represents the area of a sample, and D represents the thickness of a sample. Equivalent rigidity: Ke(N/mm)=Qd/δ...(α) Shear elastic coefficient: Ge(N/mm ² )=Ke÷S/D...(β)

Here, FIG. 1 shows an example of the damper of the present invention. In the figure, 1 denotes a shock absorber, 2 denotes a viscoelastic body, and 4 and 5 denotes a metal plate. Then, as shown in the figure, the viscoelastic body 2 is bonded in a state of being sandwiched between two metal plates 4 and 5 . FIG. 2 is a cross-sectional view (a cross-sectional view taken along the line AA′ in FIG. 1 ) showing an example of the damper. FIG. 2 shows that the viscoelastic body 2 in the shock-absorbing damper is a single-layer structure. FIG. 3 is a cross-sectional view (a cross-sectional view taken along the line AA′ in FIG. 1 ) showing another example of the shock absorber. FIG. 3 shows that the viscoelastic body 2 in the shock-absorbing damper is a double-layer structure.

Next, FIG. 4 shows an installation example (an example) of the above-mentioned damper 1 . In the figure, 1 denotes a shock absorber, 2 denotes a viscoelastic body, 4 and 5 denotes a metal plate, 6 denotes a bolt, 7 and 8 denotes a panel, 10 denotes a beam, and 11 denotes a base. As shown in the figure, the metal plate 4 and the metal plate 5 of the damper 1 are attached to the panel 7 and the panel 8 by bolts 6, respectively. In addition, in order to realize damping between the beam 10 and the base 11 , the viscoelastic body 2 sandwiched between the metal plate 4 and the metal plate 5 functions.

The vibration damper of the present invention is not particularly limited to the shape described above, and can exhibit excellent functions as a vibration damper for civil engineering, a vibration damper for construction, a vibration damper for home appliances or electronic equipment, and the like. Among them, a more excellent function can be exhibited as a vibration damper used in large buildings such as bridges and buildings, especially as a vibration damper for high-rise buildings. [Example]

Next, an Example is demonstrated together with a comparative example. However, the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded.

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

[SIS] Made by ZEON Co., Ltd., Quintac 3520 (Mune viscosity at 100°C: 23, styrene-isoprene diblock content: 78 wt %, styrene content: 15 wt % %)

[EPDM(i)] Mitsui Chemicals Corporation, Mitsui EPT X-4010M (Munich viscosity at 100°C: 8)

[EPDM(ii)] Mitsui Chemicals Co., Ltd., Mitsui EPT 4045M (Munich viscosity at 100°C: 45)

[EPDM(iii)] Mitsui Chemicals Co., Ltd., Mitsui EPT 9090M (Munich viscosity at 100°C: 81)

[Calcium Carbonate] Calcium carbonate surface-treated with stearic acid (manufactured by Shiraishi Calcium Co., Ltd., Bai Yanhua CC)

〔talc〕 Made by Nippon Talc, MS-P

[Untreated silica] Silica without surface treatment (manufactured by Tosoh Silica Co., Ltd., Nipsil VN3)

[Surface treated silica (i)] Silicon dioxide surface-treated with a silane coupling agent represented by the following formula (2) (Aerosil RX200, manufactured by Japan Aerosil Co., Ltd.)

[hua 4]

[Surface treated silica (ii)] Silicon dioxide surface-treated with a silane coupling agent represented by the following formula (3) (manufactured by Aerosil, Japan, Aerosil R805)

[hua 5]

[Surface treated silica (iii)] Silicon dioxide surface-treated with a silane coupling agent represented by the following formula (4)

[hua 6]

Furthermore, the surface-treated silica (iii) was stirred by using a Henschel Mixer (manufactured by Tosoh Silica Co., Ltd., Nipsil VN3), and slowly added The silane coupling agent represented by the formula (4) (Dynasylan 9116, manufactured by Evonik Japan) was subjected to surface treatment with silica, and then dried in an oven at 150°C. to make.

[Carbon Black] Made by Tokai Carbon, Seast S

[Liquid polymer] Manufactured by Kuraray Company, Kuraprene LIR-310

[Example 1 to Example 10, Comparative Example 1 to Comparative Example 5] Each component shown in Table 1 and Table 2 described later was blended at the ratio shown in the table, and these were kneaded with a kneader to prepare a target rubber composition.

Using the rubber compositions of Examples and Comparative Examples obtained as described above, evaluation of each characteristic was performed according to the following criteria. These results are collectively shown in Table 1 and Table 2 to be described later.

[Shear Elasticity Coefficient (Ge), Attenuation Constant (he)] The dynamic shear properties of the rubber composition were evaluated using the apparatus shown in FIG. 5 . That is, after applying the two-liquid adhesive for rubber to the predetermined part (the adjoining part of the sample 21 ) of the two pieces of metal fittings 22 (size 140 mm×80 mm, thickness 9 mm) subjected to sandblasting, The rubber compositions of Examples or Comparative Examples were sandwiched between sheet metal fittings 22 and dried. This was subjected to hot press molding at 100° C. for 10 minutes to prepare a sample (size 70 mm×80 mm, thickness 5 mm) 21 . Then, the apparatus was excited in the direction of the arrow, and the dynamic shear characteristics were evaluated based on the load-strain loop curve shown in FIG. 6 . That is, for the above-mentioned device, a vibration exciter (manufactured by Saginomiya Co., Ltd., dynamic servo (DYNAMIC SERVO)), an input signal oscillator (manufactured by Yokogawa Electric Co., Ltd., a synthesized function generator (synthesized function generator) FC320), and an output signal processor (portable FFT analyzer CF-3200, manufactured by ONO SOKKI), which gives the second-wave excitation (shear strain rate: 200% (relative to the sample) during a hypothetical large earthquake thickness: 200%), frequency (f): 0.5 Hz, measurement temperature: 20°C), based on the analysis of the shear strain value (δ) and load value (Qd) with respect to the excitation time, and according to the following The equivalent rigidity (Ke) and the equivalent attenuation coefficient (Ce) are obtained from the equations (1) to (4), and the shear elastic coefficient (Ge) and the attenuation constant (he) are obtained from the values. In the following formula, ω=2πf, W=Keδ ² /2, ΔW represents the area of the load-strain ring (absorbing energy), S represents the area of the sample, and D represents the thickness of the sample. Equivalent rigidity: Ke(N/mm)=Qd/δ...(1) Equivalent attenuation coefficient: Ce(kN·s/m)=△W/πωδ ² ...(2) Attenuation constant: he= △W/4πW (3) Shear elasticity coefficient: Ge (N/mm ² )=Ke÷S/D (4)

[temperature dependence] For the device produced as described above (see FIG. 5 ), the shear elastic coefficient “Ge (10° C.)” at a measurement temperature of 10° C. and the shear at a measurement temperature of 30° C. were measured according to the measurement method described above. The value of the elastic coefficient “Ge (30° C.)” was calculated as the value of “Ge (10° C.)/Ge (30° C.)”, and the temperature dependence was evaluated. That is, the closer the calculated value is to 1, the lower the temperature dependence (low temperature dependence).

[ΔW Retention Rate] For the device produced as described above (refer to FIG. 5 ), in accordance with the measurement method described above, a vibration exciter (manufactured by Saragiya Seisakusho Co., Ltd., dynamic servo (DYNAMIC SERVO)), an input signal oscillator (horizontal Manufactured by River Electric Corporation, synthesized function generator (synthesized function generator) FC320), and output signal processor (manufactured by ONO SOKKI, portable FFT analyzer CF-3200), at frequency (f): 0.5 Hz , Measurement temperature: 20 times of excitation at 20°C. Then, the absorbed energy (ΔW ₂ ) at the second excitation and the absorbed energy at the 20th excitation (ΔW ₂₀ ) were measured, the value of “ΔW ₂₀ /ΔW ₂ ” was calculated, and the value was defined as ΔW Retention rate (%).

[Overview] From the measurement results, the shear elastic coefficient (Ge) is 0.23 or more, the attenuation constant (he) is 0.45 or more, and the value of "Ge (10°C)/Ge (30°C)" as an index of temperature dependence Those satisfying all the conditions of 1.5 or less and ΔW retention rate of 65% or more were evaluated as "○". In addition, it does not meet the evaluation of "○", but the shear elastic coefficient (Ge) is 0.15 or more, the attenuation constant (he) is 0.44 or more, and "Ge (10°C)/Ge ( A value of 1.51 or less and a ΔW retention rate of 60% or more were all satisfied, and were evaluated as “Δ”. In addition, those which did not meet any of the above-mentioned "○" and "△" were evaluated as "x".

[Table 1] (parts by weight) Example 1 2 3 4 5 6 7 8 9 10 SIS 70 70 50 70 70 70 70 70 95 70 EPDM(i) - - - - - - - - - - EPDM(ii) 30 - 50 30 30 30 30 30 5 30 EPDM(iii) - 30 - - - - - - - - calcium carbonate 50 50 50 50 50 50 50 - 50 - talc - - - - - - - 50 - - untreated silica - - - - - 20 - - - - Surface Treatment Silica (i) - - - - - - - - - - Surface Treatment Silica (ii) 30 30 30 30 30 10 - 30 30 50 Surface Treatment Silica (iii) - - - - - - 30 - - - carbon black - - - 2 - - - - - - liquid polymer - - - - 10 - - - - - Shear elasticity coefficient (Ge) [N/mm ² ] 0.25 0.26 0.24 0.25 0.23 0.25 0.19 0.25 0.24 0.30 Attenuation constant (he) 0.46 0.45 0.47 0.46 0.47 0.45 0.45 0.46 0.44 0.50 temperature dependence 1.45 1.43 1.46 1.45 1.43 1.45 1.45 1.45 1.42 1.51 △W retention rate [%] 65 68 68 65 65 65 65 65 66 60 Overview ○ ○ ○ ○ ○ ○ △ ○ △ △

[Table 2] (parts by weight) Comparative example 1 2 3 4 5 SIS 70 40 70 70 100 EPDM(i) 30 - - - - EPDM(ii) - 60 30 30 - EPDM(iii) - - - - - calcium carbonate 50 50 50 50 50 talc - - - - - untreated silica - - 30 - Surface Treatment Silica (i) - - - 30 - Surface Treatment Silica (ii) 30 30 - - 30 Surface Treatment Silica (iii) - - - - - carbon black - - - - - liquid polymer - - - - - Shear elasticity coefficient (Ge) [N/mm ² ] 0.24 0.23 0.25 0.25 0.23 Attenuation constant (he) 0.5 0.5 0.39 0.5 0.39 temperature dependence 1.55 1.5 1.45 1.45 1.41 △W retention rate [%] 55 58 65 50 60 Overview × × × × ×

According to the results in Table 1, the samples of the examples satisfy low temperature dependence, high attenuation characteristics, and also have a high ΔW retention rate, and therefore, good results are obtained in the comprehensive evaluation.

On the other hand, according to the results of Table 2, the samples of Comparative Examples 1 to 5 did not obtain favorable results in the comprehensive evaluation. That is, in the sample of Comparative Example 1, the EPDM used in combination with the SIS has a lower viscosity than the SIS, and as a result, the ΔW retention rate is poor. In the sample of Comparative Example 2, the EPDM used in combination with the SIS had a high viscosity, but since the content of EPDM was too large, it was found that the ΔW retention rate was poor. In the sample of Comparative Example 3, only untreated silica was used as silica, and the decay constant (he) was out of the required range. In the sample of Comparative Example 4, the trimethylsilyl group-treated silica was used as the surface-treated silica, and as a result, the ΔW retention rate was poor. In the sample of Comparative Example 5, in which EPDM was not used in combination, the decay constant (he) was out of the required range, and as a result, the ΔW retention was slightly inferior. [Industrial Availability]

The damper of the present invention can exhibit excellent functions as a damper for civil engineering, a damper for construction, a damper for home appliances or electronic equipment, and the like. Among them, a more excellent function can be exhibited as a vibration damper used in large buildings such as bridges and buildings, especially as a vibration damper for high-rise buildings. In addition, vibration-absorbing devices or anti-vibration devices such as vibration-damping walls for buildings, shock-absorbing materials or shock-absorbing materials for home appliances or electronic equipment, automobile A shock absorbing material or a shock absorbing material or the like used can also be used as the shock absorbing damper of the present invention.

1: Shock damper 2: Viscoelastic body 4, 5: metal plate 6: Bolts 7, 8: Panel 10: Beams 11: Pedestal 21: Sample 22: Metal fittings 31: long chain alkyl 32: Silica Ke: Equivalent rigidity Qd: load value δ: shear strain value △W: Load-strain ring area (energy absorbed)

FIG. 1 is a front view showing an example of a damper. FIG. 2 is a cross-sectional view showing an example of the damper. 3 is a cross-sectional view showing another example of the shock absorber. FIG. 4 is a schematic diagram showing an installation state of the shock absorber. FIG. 5 is a schematic diagram of an apparatus for performing an evaluation method of dynamic shear characteristics. FIG. 6 is a graph showing a load-strain loop curve. FIG. 7 is an explanatory diagram showing the dispersion state of the surface-treated silica of the present invention.

1: Shock damper

2: Viscoelastic body

4, 5: metal plate

Claims (8)

A vibration damper comprising, as its constituent member, a viscoelastic body comprising a rubber composition containing a polymer component, having the following (A) component as a main component and containing the following (B) component; and the following (C) component, (A) styrene-based elastomer; (B) ethylene-propylene-diene having a higher Mooney viscosity at 100°C than the above-mentioned (A) component Monomer terpolymer; (C) Surface-treated silica surface-treated with a silane coupling agent represented by the following general formula (1);

In the general formula (1), R ₁ represents an alkyl group having 6 to 20 carbon atoms, an alkyl group having 6 to 20 carbon atoms with a phenyl terminal at the end, and R ₂ and R ₃ represent the number of carbon atoms less than or equal to the carbon number of R ₁ . or an alkoxy group having 1 to 3 carbon atoms, X represents an alkoxy group having 1 to 3 carbon atoms. The shock-absorbing damper according to claim 1, wherein the mixing ratio of component (A) and component (B) in the rubber composition is (A):(B)=95: 5 to 50:50 range. The shock-absorbing damper according to claim 1 or claim 2, wherein the content ratio of the surface-treated silica (C) in the rubber composition is relative to the total amount of the polymer component 100 parts by weight, but in the range of 5 parts by weight to 100 parts by weight. The shock absorbing damper according to claim 1 or claim 2, wherein the content ratio of all silica including the surface-treated silica (C) in the rubber composition is relative to the The total amount of the polymer components is 5 to 100 parts by weight based on 100 parts by weight. The shock-absorbing damper according to claim 1 or claim 2, wherein the styrene-based elastomer (A) has a Mooney viscosity at 100° C. of 5 to 35. The shock absorption damper according to claim 1 or claim 2, wherein the ethylene-propylene-diene monomer terpolymer (B) has a Mooney viscosity at 100° C. of 30-100. The shock-absorbing damper according to claim 1 or claim 2, wherein the styrene-based elastomer (A) is a styrene-isoprene-styrene copolymer. The shock-absorbing damper according to item 1 or item 2 of the patent application scope, which is a shock-absorbing damper for high-rise buildings.

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