TWI844186B - Silicone composition for vibration damper, viscous fluid for vibration damper, and vibration damper - Google Patents

Abstract

The present invention provides a silicone composition for a vibration damper, a viscous fluid for a vibration damper, and a vibration damper that has little viscosity change due to temperature change, can exhibit high attenuation even in a high temperature environment with a small amount, and has excellent load resistance, adhesion, and workability. The problem is solved by a silicone composition for a vibration damper that has the following (A) and (B) as main components and contains the following (C) to (E): (A) linear two-terminal vinyl-modified silicone; (B) branched silicone; (C) platinum catalyst; (D) retarder; (E) chain extender.

Description

Silicone composition for vibration damper, viscous fluid for vibration damper, and vibration damper

The present invention relates to a silicone composition for a vibration damper, a viscous fluid for a vibration damper, and a vibration damper. Specifically, the present invention relates to a silicone composition for a vibration damper, a viscous fluid for a vibration damper, and a vibration damper suitable for vibration reduction or earthquake resistance in the fields of civil engineering and construction.

Seismic devices or earthquake-resistant devices in the fields of civil engineering and construction, especially seismic dampers used in large buildings such as bridges and buildings, are used to suppress vibrations caused by earthquakes or wind, traffic vibrations caused by the movement of large vehicles, etc. In order to absorb the energy of a large earthquake, high attenuation of high strain is required, but small and medium earthquakes often occur after a large earthquake. For multiple continuous repeated deformations caused by these small and medium earthquakes, such as long-term earthquakes observed in high-rise buildings, the demand for characteristic stabilization is also increasing. As the mechanism of the shock absorbing damper used for this purpose, viscoelastic damper, viscous damper, hydraulic damper, steel damper, etc. can be listed as the main mechanisms. Among them, the viscous damper has a large attenuation force and excellent repeatability, and only has a viscosity term, so the design is simple, and it is widely introduced in large facilities such as high-rise buildings.

As the viscous body used in the viscous damper, a polybutylene-based material such as polyisobutylene is generally used (for example, refer to Patent Document 1). [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2018-132104

[Problems to be solved by the invention] However, polybutene-based materials have a large temperature dependence, so in order to obtain high attenuation in a high temperature environment (above 30°C), it is necessary to increase the amount of polybutene-based materials used in the viscous damper. Therefore, when using polybutene-based materials as the viscous body of the viscous damper, it is necessary to increase the amount of polybutene-based materials used, making the device larger.

In addition, since polybutene-based materials have a high temperature dependency, when filling a vibration-absorbing damper such as a vibration-absorbing wall with polybutene-based materials, filling cannot be performed without temporarily heating the material to 130°C to 170°C to reduce the viscosity of the polybutene-based materials. Thus, there is also a problem that heating is laborious during construction.

Therefore, the inventors and others studied the use of silicone with low temperature dependence as the material of the viscous body. However, regarding the "low strength" and "high non-adhesiveness" that are the characteristics of silicone, when silicone is used in a viscous damper, it becomes a weakness that the load resistance is weak and the shock absorption performance during excitation is greatly reduced due to the low close contact with the metal parts constituting the damper. Therefore, there is room for further research in this regard.

The present invention is made in view of such a situation, and its purpose is to provide a silicone composition for a vibration damper, a viscous fluid for a vibration damper, and a vibration damper that has little viscosity change caused by temperature change, can exhibit high attenuation with a small amount even in a high temperature environment, and has excellent load resistance, adhesion, and construction properties. [Means for solving the problem]

The inventors of the present invention have repeatedly made efforts to solve the above-mentioned problems. In the process of their research, they studied the following contents: as described above, a viscous damper is used as the shock absorbing mechanism of the shock absorbing damper, and silicone with low temperature dependence is used as its viscous material. In addition, in order to make a viscous material with less viscosity change caused by temperature change, high attenuation can be shown in a small amount even in a high temperature environment, and excellent load resistance, adhesion, and construction performance, various experiments and studies were repeatedly conducted. As a result, a silicone composition was developed as the viscous material, which contains a main component of a linear two-terminal vinyl-modified silicone (A) and a branched silicone (B), a platinum catalyst (C), a delay agent (D), and a chain extender (E). As the polymerization reaction (viscous fluidization) of the silicone composition developed in the present invention proceeds, as shown in FIG3, a linear silicone (11 in the figure) with a high molecular weight obtained by the polymerization reaction (two-dimensional crosslinking reaction) of (A) and (E) and a branched silicone (12 in the figure) of (B) coexist. Furthermore, it was found that the branched silicone 12 can easily be entangled with the straight chain silicone 11 due to its molecular structure, and the entanglement can improve the load resistance, which is the weakness of silicone. Furthermore, by using the branched silicone 12 in combination, the polymer ends that contribute to the adhesion are increased, thereby improving the adhesion. Furthermore, the viscous fluid (viscous fluid for shock absorbers) containing the silicone composition shows a viscosity more than twice that of the previous viscous fluid using polybutene-based materials, achieving high attenuation, and can significantly reduce temperature dependence compared to polybutene-based materials, so the desired purpose can be achieved as a result.

However, the present invention takes the following [1] to [12] as its main purpose. [1] A silicone composition for a vibration damper, comprising the following (A) and (B) as main components, and containing the following (C) to (E). (A) Straight-chain silicone modified with vinyl groups at both ends. (B) Branched silicone. (C) Platinum catalyst. (D) Retardant. (E) Chain extender. [2] A silicone composition for a vibration damper as described in [1], wherein the (B) is a reaction product of a crosslinking agent having three or more silane groups in one molecule and a straight-chain silicone modified with vinyl groups at both ends. [3] The silicone composition for a vibration damper as described in [2], wherein the ratio (a:b) of the mass a of (A) to the mass b of the linear vinyl-modified silicone constituting (B) is a:b=95:5 to 10:90. [4] The silicone composition for a vibration damper as described in any one of [1] to [3], wherein the viscosity of (A) at 30°C is 2000 mPa·s to 100000 mPa·s. [5] The silicone composition for a vibration damper as described in any one of [2] to [4], wherein the viscosity of the linear vinyl-modified silicone constituting (B) at 30°C is 2000 mPa·s to 100000 mPa·s. [6] The silicone composition for a vibration damper as described in any one of [1] to [5], wherein the content ratio of the (C) is 0.00003 mass parts to 0.003 mass parts relative to 100 mass parts of the (A). [7] The silicone composition for a vibration damper as described in any one of [1] to [6], wherein the content ratio of the (D) is 0.01 mass parts to 1 mass parts relative to 100 mass parts of the (A). [8] The silicone composition for a vibration damper as described in any one of [1] to [7], wherein the molar ratio of the (E) to the (A) in the silicone composition for a vibration damper is 0.01 to 4. [9] A viscous fluid for a shock absorber is formed by polymerizing a silicone composition for a shock absorber as described in any one of [1] to [8]. [10] The viscous fluid for a shock absorber as described in [9] has a viscosity of 6000 Pa·s to 150000 Pa·s at 30°C. [11] A shock absorber is filled with the viscous fluid for a shock absorber as described in [9] or [10]. [12] The shock absorber as described in [11] is a shock absorbing wall. [Effect of the invention]

According to the above, the silicone composition for the vibration damper of the present invention can exert excellent performance as a material of a viscous fluid with little viscosity change caused by temperature change, high attenuation even in a high temperature environment with a small amount, and excellent load resistance and adhesion. In addition, since the silicone composition for the vibration damper of the present invention also reacts at room temperature, it can be filled into the vibration damper such as the vibration damper wall in a low viscosity state, and high molecular weight can be obtained at room temperature in the vibration damper. Moreover, during the filling, there is no need to temporarily heat to reduce the viscosity before filling, so it is advantageous during construction. Furthermore, the vibration damper of the present invention is a damper filled with the viscous fluid, and can exhibit high attenuation even with a small amount of filling, so it can be miniaturized compared to the previous viscous damper using polybutylene-based materials. In addition, the attenuation changes caused by temperature changes are small (especially the reduction in attenuation in a high temperature environment is suppressed), so it can demonstrate excellent performance as a vibration damper.

Next, the implementation of the present invention is described in detail. However, the present invention is not limited to this implementation. Furthermore, when "X to Y" (X and Y are arbitrary numbers) is expressed in the present invention, unless otherwise specified, the meaning of "preferably greater than X" or "preferably less than Y" is also included on the basis of the meaning of "greater than X and less than Y". In addition, when "greater than X" (X is an arbitrary number) or "less than Y" (Y is an arbitrary number) is expressed, the intention of the subject matter of "preferably greater than X" or "preferably less than Y" is also included.

The silicone composition for a vibration damper of the present invention (hereinafter referred to as "the present silicone composition") is a silicone composition having the following (A) and (B) as main components and containing the following (C) to (E). (A) Straight-chain dual-terminal vinyl-modified silicone. (B) Branched silicone. (C) Platinum catalyst. (D) Delay agent. (E) Chain extender.

Here, the so-called "(A) and (B) as main components" means that the total mass of (A) and (B) accounts for more than 90 mass% relative to the total mass of (A) to (E) as essential components of the silicone composition, and preferably accounts for 92 mass% to 98 mass%, and more preferably 94 mass% to 97 mass%. In addition, when the branched silicone of (B) is synthesized using a straight-chain two-terminal vinyl-modified silicone, the straight-chain two-terminal vinyl-modified silicone as its material is not included in the (A).

The structural materials of this silicone composition are described in detail below.

《Linear-type dual-terminal vinyl-modified silicone (A)》 As the linear-type dual-terminal vinyl-modified silicone (A), silicone having a linear molecular structure and vinyl groups at both ends thereof can be used. For example, a vinyl-modified silicone represented by the following general formula (1) can be used.

[Chemistry 1]

In the general formula (1), n is preferably an integer of 50 to 5000, more preferably an integer of 80 to 4000, and further preferably an integer of 100 to 3000. That is, if the value of n is too small, the reaction becomes too fast, and if the value of n is too large, the reaction becomes too slow.

In addition, the viscosity of the linear two-terminal vinyl-modified silicone (A) at 30°C is preferably 400 mPa·s to 5000000 mPa·s. Moreover, the viscosity is more preferably 500 mPa·s to 4000000 mPa·s, and further preferably 1000 mPa·s to 1000000 mPa·s. That is, if the viscosity is as described above, the attenuation characteristics will be further improved. Furthermore, the viscosity is a value measured at a measurement temperature of 30°C using a rotational rheometer (manufactured by TA Instruments, ARES-G2).

《Branched silicone (B)》 The branched silicone (B) is not particularly limited, and is preferably a reaction product of a crosslinking agent having three or more silyl groups in one molecule and a linear two-terminal vinyl-modified silicone. Here, as the linear two-terminal vinyl-modified silicone used as the structural material of the branched silicone (B), the same as the above (A) can be preferably used. Therefore, the vinyl-modified silicone represented by the following general formula (1) can be preferably used.

[Chemistry 2]

In the general formula (1), n is preferably an integer of 50 to 5000, more preferably an integer of 80 to 4000, and further preferably an integer of 100 to 3000. That is, if the value of n is too small, the reaction becomes too fast, and if the value of n is too large, the reaction becomes too slow.

In addition, the viscosity of the linear two-terminal vinyl-modified silicone used as the structural material of the branched silicone (B) at 30°C is preferably 400 mPa·s to 5000000 mPa·s. Moreover, the viscosity is more preferably 500 mPa·s to 4000000 mPa·s, and further preferably 1000 mPa·s to 1000000 mPa·s. That is, if the viscosity is as described above, the attenuation characteristics will be further improved. Furthermore, the viscosity is a value measured at a measurement temperature of 30°C using a rotational rheometer (manufactured by TA Instruments, ARES-G2).

Next, as a crosslinking agent used as a structural material of the branched silicone (B), a crosslinking agent having three or more silyl groups in one molecule can be used as described above. As such a crosslinking agent, for example, a compound having a silyl group at one end or both ends of its molecular chain and having a silyl group in the molecular chain, or a compound having no silyl group at the molecular chain end and having only three or more silyl groups in the molecular chain can be listed. Here, as a compound having no silyl group at the molecular chain end and having only three or more silyl groups in the molecular chain, for example, a compound represented by the following general formula (2) can be used. In the following general formula (2), n and m are arbitrary integers.

[Chemistry 3]

The silyl content of the crosslinking agent is preferably in the range of 0.015 mmol/g to 0.4 mmol/g, and more preferably in the range of 0.02 mmol/g to 0.11 mmol/g.

As the crosslinking agent as described above, KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., Crosslinker 100 manufactured by Evonik Co., Ltd., and the like can be preferably used among commercially available ones.

Furthermore, the molar ratio of the crosslinking agent to the linear vinyl-modified silicone used as the structural material of the branched silicone (B) is preferably 0.01 to 4, and more preferably 0.01 to 3. By reacting the crosslinking agent at such a ratio, the desired branched silicone (B) can be obtained well.

Furthermore, the crosslinking agent having three or more silanol groups in one molecule, the linear two-terminal vinyl-modified silicone, the platinum catalyst, the delay agent, etc. are usually mixed and stirred at 5°C to 35°C using a blade stirrer, a kneader, a planetary mixer, a mixing roll, a twin-screw stirrer, etc., to obtain the branched silicone (B) by reacting. Here, the platinum catalyst is not particularly limited, and the same platinum catalyst as the essential component of the silicone composition (C) can be preferably used. In addition, the retarder is not particularly limited, and the same retarder (D) as the essential component of the silicone composition can be preferably used. Furthermore, the ratio of the platinum catalyst when obtaining the branched silicone (B) is preferably 0.00003 to 0.005 parts by mass, and more preferably 0.00009 to 0.003 parts by mass, relative to 100 parts by mass of the linear vinyl-modified silicone at both ends. In addition, the ratio of the retarder when obtaining the branched silicone (B) is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.5 parts by mass, relative to 100 parts by mass of the linear two-terminal vinyl-modified silicone.

The viscosity of the branched silicone (B) obtained in the above manner at 30°C is preferably 400 mPa·s to 5000000 mPa·s. Moreover, the viscosity is more preferably 500 mPa·s to 4000000 mPa·s, and further preferably 1000 mPa·s to 1000000 mPa·s. That is, if the viscosity is as described above, the attenuation characteristics will be further improved. Furthermore, the viscosity is a value measured at a measurement temperature of 30°C using a rotational rheometer (manufactured by TA Instruments, ARES-G2).

Furthermore, in the present silicone composition, the ratio (a:b) of the mass a of the linear vinyl-modified silicone (A) (excluding the linear vinyl-modified silicone constituting the branched silicone (B). The same shall apply hereinafter) to the mass b of the linear vinyl-modified silicone constituting the branched silicone (B) is preferably in the range of a:b=95:5 to 10:90, more preferably in the range of a:b=90:10 to 15:85, and further preferably in the range of a:b=80:20 to 20:80. In order to obtain excellent results in both load resistance and adhesion required of the present silicone composition, it is desirable to blend (A) and (B) in such a range.

《Platinum Catalyst (C)》 As the platinum catalyst (C) to be formulated in the silicone composition, for example, platinum-olefin complex, chloroplatinic acid, platinum alone, solid platinum supported on a carrier (alumina, silica, carbon black, etc.), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-phosphite complex, etc. can be used alone or in combination of two or more. In addition, the platinum catalyst (C) can also be used in a solvent such as xylene and toluene. Among such substances, SIP6830 manufactured by Gelest can be cited as a commercial product.

Moreover, the content ratio of the platinum catalyst (C) is preferably 0.00003 to 0.003 parts by mass, more preferably 0.00006 to 0.0027 parts by mass, and further preferably 0.00009 to 0.0024 parts by mass relative to 100 parts by mass of the linear two-terminal vinyl-modified silicone (A). That is, by suppressing the content of the platinum catalyst (C) within such a range, the polymerization reaction of the silicone composition (polymerization reaction of component (A) and component (E)) can be suppressed from proceeding rapidly while the polymerization reaction can be fully carried out, thereby suppressing the deviation of the viscosity of the polymer, thereby obtaining the desired viscosity (desired high attenuation). Furthermore, the content ratio of the platinum catalyst (C) is defined as the amount of the platinum catalyst itself excluding the above-mentioned solvents such as xylene and toluene.

《Delay agent (D)》 As the delay agent (D), for example, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, an organic peroxide, etc. can be used alone or in combination of two or more.

Specific examples of the aliphatic unsaturated bond-containing compound include alcohols containing aliphatic unsaturated bonds such as acetylene alcohol and 1-ethynyl-1-cyclohexanol, and maleic acid esters such as maleic anhydride and dimethyl maleate.

In addition, specific examples of the organic phosphorus compound include triorganic phosphines, diorganic phosphines, organic phosphines, triorganic phosphites, and the like.

In addition, specific examples of the organic sulfur compound include organic mercaptans, diorganic sulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.

In addition, specific examples of the nitrogen-containing compound include N,N,N',N'-tetramethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, N,N-dibutyl-1,3-propylenediamine, N,N-dimethyl-1,3-propylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N-dibutyl-1,4-butylenediamine, and 2,2'-bipyridine.

In addition, specific examples of the tin-based compound include stannous halogenide dihydrate and stannous carboxylate.

In addition, specific examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl perbenzoate, and the like.

Furthermore, among the various delay agents, compounds containing an aliphatic unsaturated bond are preferred from the viewpoint of versatility, alcohols containing an aliphatic unsaturated bond are more preferred, and acetylene alcohol is particularly preferred.

Furthermore, the content ratio of the retarder (D) is preferably 0.01 to 1 part by mass, and more preferably 0.05 to 0.5 parts by mass, relative to 100 parts by mass of the linear vinyl-modified silicone (A). That is, by adding the retarder (D) within the above range, the polymerization reaction of the linear vinyl-modified silicone (A) and the chain extender (E) can be suppressed from proceeding rapidly, and the viscosity of the polymer can be suppressed from deviating, thereby obtaining the desired viscosity (desired high attenuation).

《Chain extender (E)》 As the chain extender (E), for example, there can be cited low molecular weight compounds having silane groups (Si-H groups) at both ends of the molecular chain as represented by the following general formula (3).

[Chemistry 4]

In the general formula (3), n is preferably an integer of 1 to 100, more preferably an integer of 1 to 90, and further preferably an integer of 1 to 80. That is, if the value of n is too small, the reaction becomes too fast, and if the value of n is too large, the reaction becomes too slow.

Furthermore, in the present silicone composition, the molar ratio of the chain extender (E) relative to the linear vinyl-modified silicone (A) is preferably 0.01 to 4, and more preferably 0.1 to 2. That is, the reason is that the desired viscosity can be obtained by mixing the linear vinyl-modified silicone (A) and the chain extender (E) in the above-mentioned ratio.

《Other ingredients》 In addition to the above-mentioned components (A) to (E), various additives such as fillers, liquid polymers other than silicone, defoamers, rheology control agents, internal adhesives, coupling agents, etc. can be added to the silicone composition as needed within the scope that does not impair the effects of the present invention.

Examples of the filler include carbon black, silica, talc, calcium carbonate, carbon fiber, carbon nanotube, etc. These may be used alone or in combination of two or more.

The content ratio of the filler appropriately formulated into the silicone composition is preferably in the range of 1 to 100 parts by mass, and more preferably in the range of 5 to 50 parts by mass, relative to 100 parts by mass of the linear two-terminal vinyl-modified silicone (A). If it is such a content ratio, the attenuation characteristics will be further improved.

Examples of liquid polymers other than silicone include 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. These may be used alone or in combination of two or more.

The content ratio of the liquid polymer appropriately formulated into the silicone composition is preferably in the range of 1 to 100 parts by mass, and more preferably in the range of 5 to 50 parts by mass, relative to 100 parts by mass of the linear two-terminal vinyl-modified silicone (A). If it is such a content ratio, the attenuation characteristics will be further improved.

For example, the silicone composition can be prepared by kneading and stirring the components (A) to (E) and other components as needed at 5°C to 35°C using a blade stirrer, kneader, planetary mixer, mixing roll, twin-screw stirrer, etc. Furthermore, the branched silicone (B) is preferably pre-synthesized by the method described above and then added together with the components (A), (C) to (E), etc. The silicone composition obtained in the above manner reacts (becomes highly molecular) even at room temperature (5°C to 35°C) and becomes a viscous fluid. Therefore, it can be filled into a vibration damper such as a vibration damper wall in a low viscosity state immediately after the above preparation, and the molecular weight can be increased at room temperature in the vibration damper. Moreover, when performing the above filling, there is no need for the previous work of temporarily heating to reduce the viscosity and then filling, which is advantageous during construction. In addition, the silicone composition prepared as described above will not be highly molecular (will not become a viscous fluid) for about 12 hours immediately after the above preparation, depending on the temperature. Therefore, in this case, the silicone composition prepared in advance can also be transported to the construction site for use. Furthermore, the silicone composition is placed in an environment of 5°C to 35°C for 1 hour to 24 hours, and the polymerization reaction (two-dimensional crosslinking reaction) of component (A) and component (E) is completed and the molecular weight is increased, thereby becoming a viscous fluid (viscous fluid for shock absorbers. hereinafter referred to as "this viscous fluid").

Here, the viscosity of the viscous fluid at 30°C is preferably 6000 Pa·s to 100000 Pa·s. Moreover, the viscosity is more preferably 6500 Pa·s to 80000 Pa·s, and further preferably 7000 Pa·s to 60000 Pa·s. That is, if the viscosity is as described above, the attenuation characteristics will be further improved. Furthermore, the viscosity is a value measured at a measurement temperature of 30°C using a rotational rheometer (manufactured by TA Instruments, ARES-G2).

In addition, the weight average molecular weight (Mw) of the polymerization product of the components (A) and (E) in the present viscous fluid is preferably 80,000 to 2,000,000, and more preferably 100,000 to 1,800,000. That is, if the weight average molecular weight is as described above, the attenuation characteristics will be further improved. In addition, from the viewpoint of more effectively exerting the effects of the present invention, the molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymerization product is preferably 1.5 to 40, and more preferably 2 to 30. The weight average molecular weight (Mw) is the weight average molecular weight converted from the standard polystyrene molecular weight, and is measured by using three columns in series: Shodex GPC KF-806L (exclusion cutoff molecular weight: 2×10 ⁷ , separation range: 100 to 2×10 ⁷ , theoretical number of steps: 10,000 steps/column, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 μm) in a high performance liquid chromatography (manufactured by Waters Corporation, “Waters 2695 (main body)” and “Waters 2414 (detector)”). In addition, the number average molecular weight (Mn) is also measured by the same method, and the molecular weight distribution of the polymerization product is calculated from the number average molecular weight (Mn) and the weight average molecular weight (Mw) (weight average molecular weight (Mw)/number average molecular weight (Mn)).

Furthermore, as a vibration-absorbing damper filled with the present viscous fluid prepared as described above (hereinafter referred to as "the present vibration-absorbing damper"), for example, there can be cited the vibration-absorbing wall shown in FIG. 1 .

FIG1 is a perspective view schematically showing an example of a vibration-absorbing wall. The vibration-absorbing wall 1 shown in the figure is formed by filling the gap between the hanging wall 2 and the standing wall 3 with the viscous fluid. The hanging wall 2 includes one or more plates that are fixed to the frame of the building structure of the upper layer and hang down and are separated from the frame of the building structure of the lower layer. The standing wall 3 includes a plurality of plates that are fixed to the frame of the building structure of the lower layer in parallel with the hanging wall 2 and stand up in a manner surrounding the hanging wall 2 and are separated from the frame of the building structure of the upper layer. Furthermore, in the case of the shock-absorbing wall 1 of the structure shown in FIG1 , from the perspective of the manufacturing steps of the shock-absorbing wall 1 , it is preferable to fill the gap between the hanging wall 2 and the standing wall 3 with the silicone composition and then perform a polymerization reaction to produce the viscous fluid.

As a material constituting the hanging wall 2 and the standing wall 3 in the shock-absorbing wall 1, a fiber-reinforced resin sheet can be used in addition to a steel sheet. As the fiber-reinforced resin sheet, for example, a resin sheet can be used which uses a thermosetting resin such as an unsaturated polyester resin, an epoxy resin, or a thermoplastic resin such as a polyamide, a polypropylene, or an acrylonitrile-butadiene-styrene (ABS) resin as a base resin, and in which glass fibers, carbon fibers, boron fibers, alumina fibers, amide fibers, etc. are dispersed.

Furthermore, the specific structure of the shock-absorbing wall 1 may be as follows: bolt holes (not shown) are provided at prescribed intervals along the horizontal and vertical directions of the shock-absorbing wall 1 to connect the hanging wall 2 and the standing wall 3, gap adjusting bolts for maintaining the gap between the two walls are inserted into the bolt holes of the two walls, which are screwed together with nuts, and the size of the gap between the two walls is adjusted according to the screwing length of the gap adjusting bolts on the nuts.

In addition, the filling of the silicone composition into the shock-absorbing wall 1 can be carried out before the hanging wall 2 is built on the upright wall 3 or after the hanging wall 2 is built on the upright wall 3, and the method is not particularly limited. As the filling method before construction, there are, for example, the following methods: a method of installing a long inlet pipe from the upper part of the upright wall 3 into the wall to flow and fill the silicone composition, a method of providing multiple injection ports (not shown) at the lower part of the upright wall 3, and using a pump such as a grouting injection machine to fill the silicone composition from the injection ports, etc. By these methods, as shown in FIG. 2, after the filling of the silicone composition (silicone composition 4) in the upright wall 3 is completed, the hanging wall 2 is built in the upright wall 3, and the polymerization reaction of the silicone composition 4 is completed (becoming a viscous fluid), thereby completing the shock-absorbing wall 1. Furthermore, regarding the timing of filling, the silicone composition 4 can be filled in advance and carried to the construction site, or the silicone composition 4 is prepared and filled at the construction site. In addition, when the silicone composition 4 is filled after the vertical wall 2 is built on the vertical wall 3, it is better to use a method of setting an injection port at the bottom of the vertical wall 3 and injecting.

The present seismic damper is not limited to the seismic damper of the shape shown in the figure, and various shapes of seismic dampers can be listed as long as the present silicone composition or the present viscous fluid is used. Moreover, the present seismic damper can play an excellent role as a seismic damper for civil engineering, construction, home appliances or electronic equipment, etc. Among them, as a seismic damper used in large buildings such as bridges or buildings, especially as a seismic damper for high-rise buildings, it can play a more excellent role. [Example]

Next, embodiments are described together with comparative examples. However, the present invention is not limited to these embodiments as long as it does not exceed the gist of the present invention.

First, before the Examples and Comparative Examples, the following materials were prepared. Note that the values shown for the following materials are values measured based on the above-mentioned measurement methods.

[Silicone modified with vinyl groups at both ends (i)] Silicone modified with vinyl groups at both ends and n=100 to 300 represented by the following general formula (1) (Polymer VS 2000 (viscosity at 30°C: 2000 mPa·s), manufactured by Evonik)

[Chemistry 5]

[Silicone modified with vinyl groups at both ends (ii)] Silicone modified with vinyl groups at both ends and having n=500 to 800 represented by the general formula (1) (Polymer VS 10000 (viscosity at 30°C: 10000 mPa·s), manufactured by Evonik)

[Silicone modified with vinyl groups at both ends (iii)] Silicone modified with vinyl groups at both ends and having n=1100 to 1400 represented by the general formula (1) (Polymer VS 65000 (viscosity at 30°C: 65000 mPa·s), manufactured by Evonik)

[Silicone modified with vinyl groups at both ends (iv)] Silicone modified with vinyl groups at both ends and having n=1350 to 1650 represented by the general formula (1) (Polymer VS 100000 (viscosity at 30°C: 100000 mPa·s), manufactured by Evonik)

[Platinum Catalyst] SIP6830, manufactured by Gelest

[Delay agent] Acetylene alcohol (Surfynol 61, manufactured by Nissin Chemical Industries, Ltd.)

[Chain extender] Chain extender represented by the following general formula (3) with n=1 to 18 (DMS-H11, manufactured by Evonik)

[Chemistry 6]

[Crosslinking agent (i)] Crosslinking agent represented by the following general formula (2) with a silyl group content of 7 mmol/g (KF-9901, manufactured by Shin-Etsu Chemical Co., Ltd.)

[Chemistry 7]

[Crosslinker (ii)] Crosslinker represented by the general formula (2) with a silane group content of 8 mmol/g (crosslinker 100, manufactured by Evonik)

[Example 1 to Example 11, Comparative Example 1, Comparative Example 2] First, the materials shown in Table 1 below were mixed in the proportions shown in the table, and stirred with a blade stirrer at 30°C to cause a crosslinking reaction, thereby obtaining branched silicone (I) to branched silicone (V). In addition, the amount of the crosslinking agent shown in Table 1 below is recorded as the molar ratio of the crosslinking agent to the silicone modified with vinyl groups at both ends. In addition, the proportion of the platinum catalyst shown in Table 1 below represents the content ratio of the platinum catalyst itself after removing the solvent etc. contained in the agent (SIP6830). In addition, the viscosity of branched silicone (I) to branched silicone (V) shown in Table 1 below is the value measured at 30°C based on the above-mentioned measurement method.

[Table 1] (Mass) Branched silicone (I) (II) (III) (IV) (V) Silicone modified with vinyl groups at both ends (i) 100 - - - - Silicone modified with vinyl groups at both ends (ii) - 100 - - - Silicone modified with vinyl groups at both ends (iii) - - 100 - - Silicone modified with vinyl groups at both ends (IV) - - - 100 100 Platinum Catalyst 0.02 0.02 0.02 0.02 0.02 Delay agent 0.1 0.1 0.1 0.1 0.1 Crosslinking agent (i) ※1 0.6 0.6 0.6 0.6 - Crosslinking agent (ii) ※1 - - - - 0.6 Viscosity [Pa·s] 2 10 65 100 100 ※1: The amount of crosslinking agent is expressed as the molar ratio of crosslinking agent to the amount of vinyl-modified silicone at both ends.

Next, the above materials and the branched silicone (I) to branched silicone (V) shown in Table 1 are mixed in the ratios shown in Tables 2 and 3 described below, and stirred with a blade stirrer at 30°C to prepare silicone compositions of the embodiments and comparative examples. Furthermore, the amount of the chain extender (E) mixed shown in Tables 2 and 3 described below is recorded as the molar ratio of the chain extender (E) to the silicone (A) with vinyl groups at both ends. In addition, the content ratio of the platinum catalyst (C) shown in Tables 2 and 3 described below represents the content ratio of the platinum catalyst itself after removing the solvent etc. contained in the reagent (SIP6830).

Then, the following properties were measured using the silicone compositions of the examples and comparative examples, and evaluated according to the following criteria. These results are shown together in Tables 2 and 3 described below.

"Viscosity" After the prepared silicone composition was polymerized at 30°C for one day, the viscosity was measured at a measurement temperature of 30°C using a rotational rheometer (manufactured by TA Instruments, ARES-G2).

《Temperature dependence》 After the prepared silicone composition was polymerized at 30°C for one day, the viscosity was measured at a measurement temperature of 10°C using a rotational rheometer (ARES-G2 manufactured by TA Instruments). Then, the above measurement was also performed at a measurement temperature of 30°C, and "viscosity at a measurement temperature of 10°C/viscosity at a measurement temperature of 30°C" was calculated.

《Dynamic elastic coefficient》 After the prepared silicone composition was polymerized at 30°C for one day, the viscoelasticity was measured at 30°C using a rotational rheometer (ARES-G2, manufactured by TA Instruments) to determine the maximum value of the dynamic elastic coefficient at that time.

《Adhesion》 Prepare a circular plate-shaped metal fitting with a diameter of 30 mm and a thickness of 2 mm, and a metal fitting with a square of 50 mm, and fill the prepared silicone composition with a thickness of 1 mm in a manner of sandwiching between the two metal fittings, and leave it at 30°C for one day to promote the polymerization reaction of the silicone composition. After that, use a dynamometer (manufactured by Imada, a popular mechanical dynamometer) to stretch the two metal fittings in the peeling direction. Then, visually evaluate the peeled surface of the metal fitting after peeling according to the following criteria. ○: Material damage of the polymerization reaction product of the silicone composition is confirmed on more than 50% of the peeled surface. ×: Interface peeling is confirmed, or when the peeling area is less than 50%, the material of the polymerization reaction product of the silicone composition is destroyed.

<Comprehensive evaluation> Regarding the results of the above-mentioned measurements, those that satisfy all the requirements such as viscosity of 6000 Pa·s to 100000 Pa·s, temperature dependence of 2 or less, dynamic elastic coefficient of 5000 Pa or more, and adhesion evaluation of "○" are given a comprehensive evaluation of "○", and those that do not satisfy any of these requirements are given a comprehensive evaluation of "×".

[Table 2] (Mass) Embodiment 1 2 3 4 5 6 7 A Silicone modified with vinyl groups at both ends (i) 95 95 40 - - - - Silicone modified with vinyl groups at both ends (ii) - - - 40 - - - Silicone modified with vinyl groups at both ends (iii) - - - - 40 - - Silicone modified with vinyl groups at both ends (IV) - - - - - 40 40 B Branched silicone (I) 5.036 - 60.432 - - - - Branched silicone (II) - - - - 60.432 - - Branched silicone (III) - - - 60.432 - - - Branched silicone (IV) - 5.036 - - - 60.432 - Branched silicone (V) - - - - - - 60.432 C Platinum Catalyst 0.019 0.019 0.008 0.008 0.008 0.008 0.008 D Delay agent 0.095 0.095 0.04 0.04 0.04 0.04 0.04 E Chain extender ※2 (0.95) (0.95) (0.4) (0.4) (0.4) (0.4) (0.4) Viscosity [Pa·s] 40000 42000 39000 40000 41000 41000 39000 Temperature dependence 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Dynamic elastic coefficient [Pa] 5100 5200 5500 5500 5500 5600 5600 Adhesion ○ ○ ○ ○ ○ ○ ○ Comprehensive evaluation ○ ○ ○ ○ ○ ○ ○ ※2: The amount of chain extender (E) is expressed as the molar ratio of (E) to (A).

[table 3] (Mass) Embodiment Comparison Example 8 9 10 11 1 2 A Silicone modified with vinyl groups at both ends (i) 10 - - - - - Silicone modified with vinyl groups at both ends (ii) - 10 - - 100 - Silicone modified with vinyl groups at both ends (iii) - - 10 - - - Silicone modified with vinyl groups at both ends (IV) - - - 10 - - B Branched silicone (I) 90.648 - - - - - Branched silicone (II) - - 90.648 - - 100.72 Branched silicone (III) - 90.648 - - - - Branched silicone (IV) - - - 90.648 - - Branched silicone (V) - - - - - - C Platinum Catalyst 0.002 0.002 0.002 0.002 0.02 - D Delay agent 0.01 0.01 0.01 0.01 0.1 - E Chain extender ※2 (0.1) (0.1) (0.1) (0.1) (1) - Viscosity [Pa·s] 45000 40000 38000 40000 40000 40000 Temperature dependence 1.8 1.8 1.8 1.8 1.8 1.8 Dynamic elastic coefficient [Pa] 5700 5800 5700 5900 4500 3000 Adhesion ○ ○ ○ ○ × ○ Comprehensive evaluation ○ ○ ○ ○ × × ※2: The amount of chain extender (E) is expressed as the molar ratio of (E) to (A).

From the results in Table 2 and Table 3, it can be seen that the samples of the examples have high attenuation properties because the viscosity of the viscous fluid after the polymerization reaction is completed is high (6000 Pa·s to 100000 Pa·s), and further, because the temperature dependence of the viscous fluid is also low, the viscosity change caused by temperature change is small. In addition, the samples of the examples all show high dynamic elastic coefficients and good adhesion.

In contrast, the sample of Comparative Example 1 did not contain branched silicone, so the results did not show the expected dynamic elastic coefficient and could not obtain close adhesion. The sample of Comparative Example 2 was only branched silicone and did not contain straight-chain silicone, but the results of this sample also did not show the expected dynamic elastic coefficient. [Industrial Applicability]

The silicone composition for vibration dampers and the viscous fluid for vibration dampers of the present invention can exert excellent functions by being used in vibration dampers for civil engineering, construction, home appliances or electronic equipment, etc. Among them, by being used in vibration dampers used in large buildings such as bridges or buildings, especially vibration dampers for high-rise buildings, they can exert more excellent functions. In addition, the silicone composition for vibration dampers or viscous fluid for vibration dampers of the present invention, such as vibration damping walls for buildings or vibration-resistant devices, vibration damping materials or shock absorbing materials for home appliances or electronic equipment, and vibration damping materials or shock absorbing materials for automobiles can also be used as vibration dampers of the present invention.

1: Shock-absorbing wall 2: Vertical wall 3: Vertical wall 4: Silicone composition 11: Straight chain silicone 12: Branched silicone

FIG1 is a perspective view schematically showing an example of a vibration-absorbing wall. FIG2 is a perspective view showing the vibration-absorbing wall before assembly. FIG3 is an explanatory view schematically showing the dispersion state of a polymer.

2: Hang down the wall

3: Set up the wall

4: Silicone composition

Claims (11)

A silicone composition for a vibration damper, which has the following components (A) and (B) as main components, and contains the following components (C) to (E): (A) linear silicone modified with vinyl groups at both ends; (B) branched silicone; (C) platinum catalyst; (D) delay agent; (E) chain extender, wherein the component (B) is a reaction product of a crosslinking agent having three or more silane groups in one molecule and linear silicone modified with vinyl groups at both ends. The silicone composition for vibration dampers as described in claim 1, wherein the ratio (a:b) of the mass a of the component (A) to the mass b of the linear vinyl-modified silicone constituting the component (B) is a:b=95:5~10:90. The silicone composition for a vibration damper as described in claim 1 or claim 2, wherein the viscosity of the component (A) at 30°C is 2000mPa.s to 100000mPa.s. The silicone composition for a vibration damper as described in claim 1 or claim 2, wherein the linear vinyl-modified silicone constituting the component (B) has a viscosity of 2000mPa.s to 100000mPa.s at 30°C. The silicone composition for a vibration damper as described in claim 1 or claim 2, wherein the content ratio of the component (C) is 0.00003 parts by mass to 0.003 parts by mass relative to 100 parts by mass of the component (A). The silicone composition for a vibration damper as described in claim 1 or claim 2, wherein the content ratio of the component (D) is 0.01 to 1 part by mass relative to 100 parts by mass of the component (A). The silicone composition for a vibration damper as described in claim 1 or claim 2, wherein the molar ratio of the component (E) to the component (A) in the silicone composition for a vibration damper is 0.01 to 4. A viscous fluid for a vibration damper is formed by polymerizing a silicone composition for a vibration damper as described in any one of claim 1 to claim 7. The viscous fluid for the shock absorber as described in claim 8 has a viscosity of 6000 Pa. s to 150000 Pa. s at 30°C. A vibration damper is filled with a viscous fluid for vibration dampers as described in claim 8 or claim 9. The vibration-absorbing damper as described in claim 10 is a vibration-absorbing wall.