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

Abstract

Provided is a silicone composition for a vibration damper, which exhibits a small change in viscosity due to a change in temperature, exhibits high damping even in a high-temperature environment with a small amount, further has excellent load resistance, excellent close contact, and excellent workability, a viscous fluid for a vibration damper, and a vibration damper. The problem is solved by a silicone composition for a vibration damper, which contains the following (A) and (B) as main components and contains the following (C) to (E): (A) a linear two-terminal vinyl-modified silicone; (B) a branched silicone; (C) a platinum catalyst; (D) a retarder; and (E) a chain extender.

Description

Technical Field

[0001] This invention relates to silicone compositions for vibration dampers, viscous fluids for vibration dampers, and vibration dampers. More specifically, it relates to silicone compositions for vibration dampers, viscous fluids for vibration dampers, and vibration dampers suitable for vibration reduction, seismic isolation, and other applications in the civil and building fields. Background Technology

[0002] Vibration damping devices and seismic isolation devices used in the civil engineering and construction fields, especially in large buildings such as bridges and skyscrapers, are used to suppress vibrations caused by earthquakes, wind, traffic vibrations caused by the movement of large vehicles, etc.

[0003] In order to absorb the energy of a large earthquake, high attenuation of high strain is necessary. However, many small and medium-sized earthquakes also occur after a large earthquake. For long-period earthquakes such as those observed in high-rise buildings, the need for characteristic stabilization is increasing for the repeated deformation caused by the aforementioned small and medium-sized earthquakes.

[0004] Viscoelastic dampers, viscous dampers, oil dampers, and steel dampers are among the main types of dampers used for such applications. Among them, viscous dampers have a large attenuation force and excellent repeatability, and they only have a viscous term, so they are simple to design and are widely used in large facilities such as high-rise buildings.

[0005] The viscous body used in the aforementioned viscous damper is typically a viscous body using, for example, a polybutene-based material such as polyisobutylene (see, for example, Patent Document 1).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2018-132104 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] However, polybutene-based materials exhibit significant temperature dependence. Therefore, to achieve high attenuation performance at high temperatures (above 30°C), the amount of polybutene-based material used in viscous dampers needs to be increased. Consequently, when using polybutene-based materials as the viscous body in viscous dampers, the equipment needs to be scaled up accordingly to increase the amount of polybutene used.

[0011] Furthermore, polybutene-based materials are highly temperature-dependent. Therefore, when filling vibration damping devices such as shock absorber walls with polybutene-based materials, it is impossible to fill them without temporarily heating them to 130–170°C to reduce the viscosity of the polybutene-based materials. This also presents the problem of wasting time and effort on heating during construction.

[0012] Therefore, the inventors of this invention have studied the use of silicone, which has low temperature dependence, as a material for the aforementioned adhesive.

[0013] However, when silicone is used in viscous dampers, the "low strength" and "high non-adhesiveness" characteristic of silicone become weaknesses such as poor load-bearing capacity and reduced vibration damping performance during vibration due to the forced low bonding of the metal components constituting the damper. Therefore, there is room for further research in this regard.

[0014] The present invention was made in view of the following circumstances, and its object is to provide a silicone composition for vibration damping dampers, a viscous fluid for vibration damping dampers, and a vibration damping damper, which exhibits low viscosity change due to temperature changes, high attenuation even at high temperature environments, and further has excellent load resistance, excellent adhesion, and excellent workability.

[0015] means for solving problems

[0016] The inventors of this invention conducted repeated and in-depth research to solve the aforementioned problems. During this research, a viscous damper was used as the vibration damping mechanism, as described above, and silicone, which has low temperature dependence, was investigated as the viscous material. Furthermore, various experiments and studies were repeatedly conducted to develop a viscous material that exhibits low viscosity change due to temperature variations, high attenuation even at high temperatures with small amounts, and further demonstrates excellent load-bearing capacity, excellent adhesion, and excellent workability.

[0017] As a result, a silicone composition containing, and using in combination with, a linear, two-terminated vinyl-modified silicone (A) and a branched silicone (B) as the main components, a platinum catalyst (C), a retarder (D), and a chain extender (E), was developed as the viscous material. The silicone composition developed herein, as its polymerization reaction (viscous fluidization) proceeds, as... Figure 3 As shown, the branched silicone (Figure 12) of (B) coexists with the linear silicone (Figure 11) whose molecular weight has been increased through the polymerization reaction (two-dimensional crosslinking reaction) of (A) and (E). Furthermore, it was found that the branched silicone 12, through its molecular structure, readily entangles with the linear silicone 11. This entanglement improves the load-bearing capacity, a weakness of silicone. Moreover, the combined use of the branched silicone 12 contributes to an increase in polymer ends that enhance adhesion, thereby improving adhesion.

[0018] Furthermore, the viscous fluid formed from the aforementioned silicone composition (viscous fluid for vibration dampers) exhibits a viscosity more than twice that of conventional viscous fluids using polybutene-based materials, achieving high attenuation, and significantly reducing temperature dependence compared to polybutene-based materials, thus achieving the desired purpose.

[0019] However, the main point of the present invention is as follows [1] to

[12] .

[0020] [1] A silicone composition for a vibration damper, wherein the silicone composition for a vibration damper is mainly composed of the following (A) and (B) and contains the following (C) to (E):

[0021] (A) Straight-chain, two-terminated vinyl-modified silicone;

[0022] (B) Branched silicone;

[0023] (C) Platinum catalyst;

[0024] (D) Delaying agent;

[0025] (E) Chain extender.

[0026] [2] The silicone composition for vibration damping devices according to [1], wherein (B) is a reaction product of a crosslinking agent having three or more hydrogenated silane groups in one molecule and a linear two-terminal vinyl-modified silicone.

[0027] [3] According to the silicone composition for vibration damping devices described in [2], the ratio (a:b) of the mass a of (A) to the mass b of the linear two-terminal vinyl-modified silicone constituting (B) is a:b = 95:5 to 10:90.

[0028] [4] The silicone composition for vibration damping according to any one of [1] to [3], wherein the viscosity of (A) at 30°C is 2000 to 100000 mPa·s.

[0029] [5] The silicone composition for vibration damping according to any one of [2] to [4], wherein the linear two-terminal vinyl-modified silicone constituting (B) has a viscosity of 2000 to 100000 mPa·s at 30°C.

[0030] [6] The silicone composition for vibration damping according to any one of [1] to [5], wherein the proportion of (C) is 0.00003 to 0.003 parts by mass relative to 100 parts by mass of (A).

[0031] [7] A silicone composition for a vibration damper according to any one of [1] to [6], wherein the proportion of (D) is 0.01 to 1 part by mass relative to 100 parts by mass of (A).

[0032] [8] A silicone composition for a vibration damper according to any one of [1] to [7], wherein the molar ratio of (E) to (A) in the silicone composition for a vibration damper is 0.01 to 4.

[0033] [9] A viscous fluid for a vibration damper, wherein the viscous fluid for a vibration damper is formed by polymerizing the silicone composition for a vibration damper described in any one of [1] to [8].

[0034]

[10] According to [9], the viscous fluid for the damper has a viscosity of 6000 to 150000 Pa·s at 30°C.

[0035]

[11] A vibration damper, wherein the vibration damper is formed by filling with a viscous fluid as described in [9] or

[10] .

[0036]

[12] According to the vibration damper described in

[11] , wherein the vibration damper is a vibration damping wall.

[0037] Invention Effects

[0038] As can be seen from the above, the silicone composition for shock absorbers of the present invention can be used as a material of viscous fluid with excellent performance, which exhibits excellent viscosity change due to temperature change, high attenuation even at high temperature, and excellent load resistance and adhesion.

[0039] Furthermore, the silicone composition for vibration dampers of the present invention reacts even at room temperature, thus allowing it to be filled into vibration dampers such as damping walls at a low viscosity, and to achieve high molecular weight within the damper at room temperature. Moreover, since the filling process does not require temporary heating to reduce viscosity, it is advantageous during construction.

[0040] Furthermore, the vibration damper of the present invention is filled with the aforementioned viscous fluid, and even a small amount of it can exhibit high attenuation. Therefore, compared with conventional viscous dampers using polybutene-based materials, it can be miniaturized. In addition, the variation in attenuation caused by temperature changes is small (especially the reduction in attenuation at high temperatures is suppressed), thus it can perform excellently as a vibration damper. Attached Figure Description

[0041] Figure 1 This is a three-dimensional diagram schematically representing an example of a vibration-damping wall.

[0042] Figure 2 This is a three-dimensional diagram showing the state of the aforementioned shock-absorbing wall before assembly.

[0043] Figure 3 It is an illustrative diagram that schematically represents the dispersion of the polymer.

[0044] Explanation of reference numerals in the attached figures

[0045] 1: Vibration-damping wall;

[0046] 2: Hanging wall;

[0047] 3: Erect the wall;

[0048] 4: Silicone composition. Detailed Implementation

[0049] Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to these embodiments.

[0050] Furthermore, when expressed as "X~Y" (where X and Y are arbitrary numbers) in this invention, unless otherwise specified, it includes the meaning of "more than X and less than Y" as well as "preferably greater than X" or "preferably less than Y".

[0051] Furthermore, when expressed as "X or more" (where X is any number) or "Y or less" (where Y is any number), it also implies an intention to "preferably be greater than X" or "preferably be less than Y".

[0052] The vibration damping silicone composition of the present invention (hereinafter referred to as "the silicone composition") is a silicone composition with the following (A) and (B) as main components and containing the following (C) to (E):

[0053] (A) Straight-chain, two-terminated vinyl-modified silicone;

[0054] (B) Branched silicone;

[0055] (C) Platinum catalyst;

[0056] (D) Delaying agent;

[0057] (E) Chain extender.

[0058] Here, "main components of (A) and (B)" means that, relative to the total mass of (A) to (E) which are essential components of this silicone composition, the total mass of (A) and (B) accounts for more than 90% by mass, preferably 92 to 98% by mass, and more preferably 94 to 97% by mass.

[0059] Furthermore, in the case where the branched silicone in (B) above is a branched silicone synthesized using a straight-chain, two-terminal vinyl-modified silicone, the straight-chain, two-terminal vinyl-modified silicone used as its material is not included in (A) above.

[0060] The constituent materials of this silicone composition are described in detail below.

[0061] Linear-chain, two-terminated vinyl-modified silicone (A)

[0062] As a linear, two-terminal vinyl-modified silicone (A), a silicone exhibiting a linear molecular structure and having vinyl groups at both ends is used. For example, a vinyl-modified silicone represented by the following general formula (1) can be used.

[0063]

Chemistry 1

[0064]

[0065] In the above general formula (1), n ​​is preferably an integer from 50 to 5000, more preferably an integer from 80 to 4000, and even more preferably an integer from 100 to 3000. That is, this is because 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.

[0066] Furthermore, the viscosity of the aforementioned linear, two-terminated vinyl-modified silicone (A) at 30°C is preferably 400–5,000,000 mPa·s. More preferably, it is 500–4,000,000 mPa·s, and even more preferably 1,000–1,000,000 mPa·s. That is, exhibiting such a viscosity further enhances the attenuation characteristics. Moreover, the viscosity was measured using a rotational rheometer (TA Instruments, ARES-G2) at a measurement temperature of 30°C.

[0067] Branched Silicone (B)

[0068] As a branched silicone (B), there are no particular limitations, but it is preferred to use a crosslinking agent having three or more hydrogenated silanes in one molecule and a reactant of a straight-chain, two-terminal vinyl-modified silicone.

[0069] Here, the linear-chain, two-terminated vinyl-modified silicone used as a constituent material of the aforementioned branched silicone (B) is preferably the same linear-chain, two-terminated vinyl-modified silicone as that used in (A) above. Therefore, it is preferable to use a vinyl-modified silicone represented by the following general formula (1).

[0070]

Chemistry 2

[0071]

[0072] In the above general formula (1), n ​​is preferably an integer from 50 to 5000, more preferably an integer from 80 to 4000, and even more preferably an integer from 100 to 3000. That is, this is because 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.

[0073] Furthermore, the viscosity of the linear, two-terminated vinyl-modified silicone used as a constituent material of the aforementioned branched silicone (B) at 30°C is preferably 400–5,000,000 mPa·s. More preferably, the viscosity is 500–4,000,000 mPa·s, and even more preferably 1,000–1,000,000 mPa·s. That is, exhibiting such a viscosity further enhances the attenuation characteristics. Moreover, the viscosity was measured using a rotational rheometer (TA Instruments, ARES-G2) at a measurement temperature of 30°C.

[0074] Next, as a crosslinking agent used as a constituent material of the aforementioned branched silicone (B), as described above, a crosslinking agent having three or more hydrogenated silanes in one molecule is used. Examples of such crosslinking agents include compounds having hydrogenated silanes at one or both ends of their molecular chain and having hydrogenated silanes in the molecular chain, and compounds that do not have hydrogenated silanes at the ends of their molecular chains but only have three or more hydrogenated silanes in the molecular chain.

[0075] Here, as a compound that does not have a silyl group at the end of the molecular chain but has 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.

[0076]

Transformation 3

[0077]

[0078] The amount of hydrogenated silane in the above crosslinking agent is preferably in the range of 0.015 to 0.4 mmol / g, more preferably in the range of 0.02 to 0.11 mmol / g.

[0079] As for the aforementioned crosslinking agent, commercially available crosslinking agents are preferably KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., or Crosslinker 100 manufactured by Evonik Co., Ltd.

[0080] Furthermore, the molar ratio of the crosslinking agent to the linear two-terminal vinyl-modified silicone used as a constituent material of the branched silicone (B) is preferably 0.01 to 4, more preferably 0.01 to 3.

[0081] By reacting the above crosslinking agent in this proportion, the desired branched silicone (B) can be obtained well.

[0082] In addition, the aforementioned branched silicone (B) can usually be obtained by mixing and stirring a crosslinking agent having three or more hydrogenated silanes in one molecule, a linear dual-terminal vinyl modified silicone, and other platinum catalysts, retarders, etc., in an atmosphere of 5 to 35°C using a blade mixer, kneader, planetary mixer, mixing roller, twin-screw mixer, etc., thereby causing them to react.

[0083] Here, there is no particular limitation on the platinum catalyst used, but it is preferable to use the same platinum catalyst (C) that is an essential component of this silicone composition. Similarly, there is no particular limitation on the retarder used, but it is preferable to use the same retarder (D) that is an essential component of this silicone composition.

[0084] Furthermore, the proportion of the platinum catalyst used to obtain the branched silicone (B) is preferably 0.00003 to 0.005 parts by mass relative to 100 parts by mass of the straight-chain, two-terminal vinyl-modified silicone, and more preferably 0.00009 to 0.003 parts by mass.

[0085] Furthermore, the proportion of the retarder used to obtain the branched silicone (B) is preferably 0.01 to 1 part by mass relative to 100 parts by mass of the linear two-terminal vinyl-modified silicone, and more preferably 0.05 to 0.5 parts by mass.

[0086] The branched silicone (B) obtained in this way preferably has a viscosity of 400 to 5,000,000 mPa·s at 30°C. More preferably, the viscosity is 500 to 4,000,000 mPa·s, and even more preferably 1,000 to 1,000,000 mPa·s. That is, if such a viscosity is exhibited, the decay characteristics are further improved. Furthermore, the above viscosity was measured using a rotational rheometer (manufactured by TA Instruments, ARES-G2) at a measurement temperature of 30°C.

[0087] Furthermore, in this silicone composition, the ratio (a:b) of the mass a of the linear-chain, two-terminated vinyl-modified silicone (A) (excluding the linear-chain, two-terminated vinyl-modified silicone constituting the branched silicone (B), hereinafter the same) to the mass b of the linear-chain, two-terminated vinyl-modified silicone constituting the branched silicone (B) is preferably in the range of a:b = 95:5 to 10:90, more preferably a:b = 90:10 to 15:85, and even more preferably a:b = 80:20 to 20:80. From the viewpoint of obtaining excellent results in both load-bearing capacity and adhesion required by this silicone composition, it is preferable to combine (A) and (B) in such a range.

[0088] Platinum Catalysts (C)

[0089] As the platinum catalyst (C) used in this silicone composition, for example, two or more platinum-olefin complexes, chloroplatinic acid, elemental platinum, substances with solid platinum supported on a support (alumina, silica, carbon black, etc.), platinum-vinylsiloxane complexes, platinum-phosphine complexes, platinum-phosphite complexes, etc., can be used alone or in combination.

[0090] Alternatively, the platinum catalyst (C) described above can also be a platinum catalyst dissolved in solvents such as xylene or toluene. Commercially available examples of such platinum catalysts include SIP6830 manufactured by Gelest.

[0091] Furthermore, relative to 100 parts by mass of the aforementioned linear, two-terminated vinyl-modified silicone (A), the content of the aforementioned platinum catalyst (C) is preferably 0.00003 to 0.003 parts by mass, more preferably 0.00006 to 0.0027 parts by mass, and even more preferably in the range of 0.00009 to 0.0024 parts by mass. That is, by controlling the content of the platinum catalyst (C) within such a range, the polymerization reaction of this silicone composition (polymerization reaction of component (A) and component (E)) can be suppressed from proceeding rapidly, while the polymerization reaction can be carried out sufficiently, the viscosity unevenness of the polymer can be suppressed, and the desired viscosity (desired high attenuation) can be obtained.

[0092] Furthermore, the specified proportion of the platinum catalyst (C) refers to the amount of the platinum catalyst itself, excluding solvents such as xylene and toluene as described above.

[0093] Delaying Agent (D)

[0094] As the aforementioned retarder (D), for example, two or more compounds containing aliphatic unsaturated bonds, organophosphorus compounds, organosulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, etc., can be used alone or in combination.

[0095] Specifically, examples of compounds containing aliphatic unsaturated bonds include alcohols such as ethynyl alcohol and 1-ethynyl-1-cyclohexynyl alcohol, as well as maleic anhydride, maleic acid esters such as dimethyl maleate, etc.

[0096] In addition, as for the aforementioned organophosphorus compounds, specifically, triorganophosphorus compounds, diorganophosphorus compounds, organophosphorus compounds, and triorganophosphites can be listed.

[0097] In addition, the aforementioned organosulfur compounds specifically include organothiols, diorganosulfur compounds, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, etc.

[0098] In addition, specific examples of the nitrogen-containing compounds mentioned above include N,N,N',N'-tetramethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dibutylethylenediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethyl-1,3-propanediamine, N,N,N',N'-tetraethylethylenediamine, N,N-dibutyl-1,4-butanediamine, and 2,2'-bipyridine.

[0099] In addition, as examples of the aforementioned tin compounds, stannous halide dihydrate and stannous carboxylate can be listed.

[0100] In addition, examples of the aforementioned organic peroxides include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl peroxide.

[0101] Furthermore, among the aforementioned delay agents, from a general viewpoint, compounds containing aliphatic unsaturated bonds are preferred, alcohols containing aliphatic unsaturated bonds are more preferred, and ethynyl alcohols are particularly preferred.

[0102] Furthermore, relative to 100 parts by mass of the aforementioned linear two-terminated vinyl-modified silicone (A), the content of the aforementioned retarder (D) is preferably 0.01 to 1 part by mass, more preferably in the range of 0.05 to 0.5 parts by mass. That is, by adding the retarder (D) within the above range, the rapid polymerization reaction between the linear two-terminated vinyl-modified silicone (A) and the chain extender (E) can be suppressed, the viscosity deviation of the polymer can be suppressed, and the desired viscosity (desired high attenuation) can be obtained.

[0103] Chain extender (E)

[0104] As the chain extender (E) mentioned above, for example, low molecular weight compounds with hydrogenated silane (Si-H groups) at both ends of the molecular chain, as shown in the following general formula (3), can be listed.

[0105]

Chemistry 4

[0106]

[0107] In the above general formula (3), n is preferably an integer from 1 to 100, more preferably an integer from 1 to 90, and even more preferably an integer from 1 to 80. That is, this is because 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.

[0108] Furthermore, in this silicone composition, the molar ratio of the chain extender (E) to the linear two-terminated vinyl-modified silicone (A) is preferably 0.01 to 4, more preferably 0.1 to 2.

[0109] That is, by combining the above-mentioned linear two-terminal vinyl-modified silicone (A) and chain extender (E) in the proportions described above, the desired viscosity can be obtained.

[0110] Other Ingredients

[0111] In addition to the components (A) to (E) above, various additives such as fillers, liquid polymers other than silicone, defoamers, rheology control agents, internal binders, and coupling agents may be added to this silicone composition as needed, without impairing the effects of the present invention.

[0112] Examples of fillers mentioned above include carbon black, silica, talc, calcium carbonate, carbon fiber, and carbon nanotubes. These can be used alone or in combination of two or more.

[0113] Relative to 100 parts by weight of the above-mentioned linear two-terminated vinyl-modified silicone (A), the content of the filler appropriately incorporated into this silicone composition is preferably in the range of 1 to 100 parts by weight, more preferably in the range of 5 to 50 parts by weight. With such a content ratio, the attenuation characteristics are further improved.

[0114] Other liquid polymers besides silicone mentioned above include, for example, 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), and liquid isoprene-butadiene rubber (liquid IR-BR), which can be used alone or in combination with two or more.

[0115] Relative to 100 parts by weight of the above-mentioned linear, two-terminated vinyl-modified silicone (A), the content of the above-mentioned liquid polymer appropriately incorporated into this silicone composition is preferably in the range of 1 to 100 parts by weight, more preferably in the range of 5 to 50 parts by weight. With such a content ratio, the attenuation characteristics are further improved.

[0116] This silicone composition can be prepared, for example, by mixing and stirring the above-mentioned components (A) to (E) and other components as needed under an atmosphere of 5 to 35°C using a blade mixer, kneader, planetary mixer, mixing roller, twin-screw mixer, etc. Furthermore, the branched silicone of (B) is preferably added together with the above-mentioned components (A), (C) to (E) after being pre-synthesized by the method described above.

[0117] The silicone composition obtained in this way reacts (increases molecular weight) even at room temperature (5–35°C) to form a viscous fluid. Therefore, it can be filled into vibration damping devices such as shock absorber walls in its freshly prepared, low-viscosity state, and then undergo molecular weight increase within the damping device at room temperature. Moreover, the filling process does not require the previously necessary temporary heating to reduce viscosity, which is advantageous during construction.

[0118] In addition, the silicone composition prepared as described above will not undergo high molecular weight (not form a viscous fluid) for about 12 hours after preparation, depending on the temperature. Therefore, in this case, the pre-prepared silicone composition can also be transported to the construction site for use.

[0119] Furthermore, by allowing the above-mentioned silicone composition to stand at 5–35°C for 1–24 hours, the polymerization reaction (two-dimensional crosslinking reaction) of component (A) and component (E) is completed, thereby increasing the molecular weight and forming a viscous fluid (viscous fluid for vibration dampers. Hereinafter referred to as "this viscous fluid").

[0120] Here, the viscosity of this viscous fluid at 30°C is preferably 6000–100000 Pa·s. More preferably, it is 6500–80000 Pa·s, and even more preferably 7000–60000 Pa·s. That is, if such a viscosity is exhibited, the attenuation characteristics are further improved. Furthermore, the above viscosity is a value measured using a rotational rheometer (TA Instruments, ARES-G2) at a measurement temperature of 30°C.

[0121] Furthermore, the weight-average molecular weight (Mw) of the polymerization reactant of components (A) and (E) in this viscous fluid is preferably 80,000 to 2,000,000, more preferably 100,000 to 1,800,000. That is, if the weight-average molecular weight is as described above, the attenuation characteristics are further improved.

[0122] Furthermore, from the viewpoint of more effectively utilizing the effects of the present invention, the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the above-mentioned polymeric reactants is preferably 1.5 to 40, more preferably 2 to 30.

[0123] Furthermore, the weight-average molecular weight (Mw) mentioned above is a weight-average molecular weight converted from standard polystyrene molecular weight, obtained by using three columns in series in high-performance liquid chromatography (Waters Corporation, “Waters 2695 (body)” and “Waters 2414 (detector)”): Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10⁻⁶). 7 Separation range: 100~2×10 7 The theoretical grade is 10,000 / piece, the filler material is styrene-divinylbenzene copolymer, and the filler particle size is 10 μm. The number-average molecular weight (Mn) was also determined using the same method. Based on the number-average molecular weight (Mn) and weight-average molecular weight (Mw) mentioned above, the molecular weight distribution of the polymer (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) was calculated.

[0124] Furthermore, examples of vibration damping devices (hereinafter referred to as "this vibration damping device") made by filling the viscous fluid prepared as described above can be cited as follows: Figure 1 The vibration damping wall shown is an example.

[0125] Figure 1 This is a perspective view schematically illustrating an example of a damping wall. Furthermore, the damping wall 1 shown is formed by filling the gap between a hanging wall 2 and a raised wall 3 with this viscous fluid. The hanging wall 2 is fixed to the frame of the upper building structure and hangs down, consisting of one or more plates separate from the frame of the lower building structure. The raised wall 3 is fixed to the frame of the lower building structure in a manner parallel to the hanging wall 2 and stands upright, surrounding the hanging wall 2, consisting of multiple plates separate from the frame of the upper building structure.

[0126] In addition, Figure 1 In the case of the damping wall 1 with the structure shown, from the viewpoint of the manufacturing process of the damping wall 1, it is preferable to fill the gap between the hanging wall 2 and the standing wall 3 with this silicone composition and then carry it to a polymerization reaction to produce a viscous fluid.

[0127] In addition to steel plates, fiber-reinforced resin boards can also be used as materials for the vertical wall 2 and vertical wall 3 constituting the aforementioned shock-absorbing wall 1. For example, fiber-reinforced resin boards can be made by using thermosetting resins such as unsaturated polyester resin and epoxy resin, thermoplastic resins such as polyamide, polypropylene, and ABS resin as matrix resins, and dispersing glass fibers, carbon fibers, boron fibers, alumina fibers, amide fibers, etc., therein.

[0128] Furthermore, as a specific structure of the aforementioned shock-absorbing wall 1, bolt holes (not shown) passing through the vertical wall 2 and the vertical wall 3 can be opened at predetermined intervals along the horizontal and vertical directions of the shock-absorbing wall 1. A gap adjustment bolt that maintains the gap between the two walls is inserted into the bolt holes of the two walls and engaged with a nut, thereby allowing the size of the gap between the two walls to be adjusted according to the engagement length of the gap adjustment bolt with the nut.

[0129] Furthermore, the filling of the silicone composition into the aforementioned shock-absorbing wall 1 can be performed before or after the vertical wall 2 is installed into the vertical wall 3, and the method is not particularly limited. As a filling method before installation, for example, there is a method of installing a long inflow pipe from the upper part of the vertical wall 3 into the wall to allow the silicone composition to flow in and fill, or a method of providing multiple injection ports (not shown) at the lower part of the vertical wall 3 and filling the silicone composition from the injection ports using a pump such as a grouting machine.

[0130] Through these methods, such as Figure 2 As shown, after the silicone composition (silicone composition 4) is filled into the upright wall 3, the drop wall 2 is built into the upright wall 3 to complete the polymerization reaction of the silicone composition 4 (forming a viscous fluid), thereby completing the shock-absorbing wall 1.

[0131] Furthermore, regarding the timing of filling, the silicone composition 4 can be pre-filled and transported to the construction site, or the silicone composition 4 can be prepared and filled at the construction site, etc., and can be carried out at any time.

[0132] In addition, when the drooping wall 2 is built into the upright wall 3 and then filled with silicone composition 4, it is preferable to use a method of providing an injection port at the bottom of the upright wall 3 for injection.

[0133] This vibration damper is not limited to the shape shown in the above figure. Any vibration damper that uses this silicone composition or this viscous fluid can be used, and various shapes can be listed.

[0134] Moreover, this vibration damper can perform excellent functions as a vibration damper for civil engineering, building construction, household appliances, and electronic equipment.

[0135] Among them, as a vibration damper used in large buildings such as bridges and skyscrapers, especially as a vibration damper for high-rise buildings, it can perform better functions.

[0136]

Example

[0137] Next, the embodiments will be described together with comparative examples. However, the present invention is not limited to these embodiments without departing from its spirit.

[0138] First, before the examples and comparative examples, the materials shown below are prepared. Furthermore, the values ​​shown for the materials below are based on values ​​measured using the methods described above.

[0139] [Two-terminal vinyl-modified silicone (i)]

[0140] The following general formula (1) shows a two-terminal vinyl-modified silicone with n = 100 to 300 (Polymer VS 2000 (viscosity at 30°C: 2000 mPa·s), manufactured by Evonik).

[0141]

Transformation 5

[0142]

[0143] [Two-terminal vinyl-modified silicone (ii)]

[0144] The two-terminal vinyl-modified silicone (Polymer VS 10000 (viscosity at 30°C: 10000 mPa·s), manufactured by Evonik) with n = 500 to 800 as shown in the above general formula (1)

[0145] [Two-terminal vinyl-modified silicone (iii)]

[0146] The two-terminal vinyl-modified silicone (Polymer VS65000 (viscosity at 30°C: 65000 mPa·s), manufactured by Evonik) with n = 1100 to 1400 as shown in the above general formula (1) represents an N=1100 to 1400 N= ...

[0147] [Two-terminal vinyl-modified silicone (iv)]

[0148] The two-terminal vinyl-modified silicone (Polymer VS100000 (viscosity at 30°C: 100000 mPa·s), manufactured by Evonik) with n = 1350 to 1650 as shown in the above general formula (1) represents an N=1350 to 1650 N=1650 N=1350.

[0149] [Platinum catalyst]

[0150] SIP6830, manufactured by Gelest.

[0151] [Delaying agent]

[0152] Surfynol 61 (manufactured by Nissin Chemical Industries, Ltd.)

[0153] [Chain extender]

[0154] The chain extender (DMS-H11, manufactured by Evonik) with n = 1 to 18 as shown in the following general formula (3)

[0155]

Transformation 6

[0156]

[0157] [Cross-linking agent (i)]

[0158] The crosslinking agent (KF-9901, manufactured by Shin-Etsu Chemical Co., Ltd.) with a hydrogenated silane content of 7 mmol / g is shown in the following general formula (2).

[0159]

Transformation 7

[0160]

[0161] [Cross-linking agent (ii)]

[0162] The crosslinking agent (Crosslinker100, manufactured by Evonik) with a hydrogenated silane content of 8 mmol / g is shown in the above general formula (2).

[0163] [Examples 1-11, Comparative Examples 1 and 2]

[0164] First, the materials shown in Table 1 below are mixed in the proportions shown in the table and stirred in an atmosphere of 30°C using a blade mixer to carry out a cross-linking reaction, thereby obtaining branched silicone (I) to (V).

[0165] Furthermore, the amounts of crosslinking agents shown in Table 1 below are recorded as the molar ratio of the crosslinking agent to the two-terminal vinyl-modified silicone. Additionally, the proportions of platinum catalyst shown in Table 1 below represent the proportion of the platinum catalyst itself after removing solvents and other contaminants contained in the reagent (SIP6830).

[0166] In addition, the viscosities of branched silicones (I) to (V) shown in Table 1 below are values ​​measured at 30°C using the above-described method.

[0167] Table 1

[0168] (parts by weight)

[0169]

[0170] ※1: The amount of crosslinking agent is recorded as the molar ratio of the crosslinking agent to the two end vinyl-modified silicones.

[0171] Next, the above-mentioned materials and the branched silicones (I) to (V) shown in Table 1 were mixed according to the proportions shown in Tables 2 and 3 below, and stirred by a blade mixer under an atmosphere of 30°C to prepare the silicone compositions of the examples and comparative examples.

[0172] Furthermore, the amounts of chain extender (E) shown in Tables 2 and 3 below are recorded as the molar ratio of chain extender (E) to the two-terminated vinyl-modified silicone (A). Additionally, the proportions of platinum catalyst (C) shown in Tables 2 and 3 below represent the proportions of the platinum catalyst itself after removing solvents and other contaminants from the reagent (SIP6830).

[0173] Then, using the silicone compositions of the examples and comparative examples, the following properties were measured and evaluated according to the following criteria. The results are shown together in Tables 2 and 3 described below.

[0174] Viscosity

[0175] After the silicone composition prepared above was subjected to a polymerization reaction at 30°C for 1 day, the viscosity was measured using a rotational rheometer (TA Instruments, ARES-G2) at a measurement temperature of 30°C.

[0176] Temperature Dependence

[0177] After the silicone composition prepared above was polymerized at 30°C for 1 day, its viscosity was measured using a rotational rheometer (TA Instruments, ARES-G2) at a measurement temperature of 10°C. Then, the above measurement was also performed at a measurement temperature of 30°C, and the ratio of "viscosity at measurement temperature of 10°C / viscosity at measurement temperature of 30°C" was calculated.

[0178] Dynamic elastic modulus

[0179] After the silicone composition prepared above was subjected to a polymerization reaction at 30°C for 1 day, the viscoelasticity was measured at 30°C using a rotational rheometer (TA Instruments, ARES-G2) to determine the maximum value of the dynamic elastic modulus at this time.

[0180] "Tightness"

[0181] Prepare two metal pieces, one circular (30mm in diameter, 2mm thick) and the other square (50mm in diameter). Fill the space between these two pieces with the prepared silicone composition to a thickness of 1mm. Allow the mixture to stand at 30°C for one day to promote polymerization. Then, stretch the two metal pieces in the peeling direction using a force gauge (IMADA, a common type mechanical force gauge). Finally, visually evaluate the peeled surfaces of the metal pieces according to the following criteria.

[0182] 〇: Material destruction of the polymerized reactants of the above-mentioned silicone composition was confirmed in more than 50% of the peeled surface.

[0183] ×: Material destruction of the above-mentioned silicone composition polymer at the point of interface peeling or less than 50% of the peeled surface.

[0184] <Overall Evaluation>

[0185] Based on the results of the above measurements, samples that fully meet the requirements of viscosity of 6000-100000 Pa·s, temperature dependence of less than 2, dynamic elastic modulus of more than 5000 Pa, and adhesion evaluation of "0" are evaluated as having a comprehensive evaluation of "○", while samples that do not meet any of these requirements are evaluated as having a comprehensive evaluation of "×".

[0186] Table 2 (Parts by weight)

[0187]

[0188] ※2: The amount of chain extender (E) is recorded as the molar ratio of (E) to (A).

[0189] Table 3 (Parts by weight)

[0190]

[0191] ※2: The amount of chain extender (E) is recorded as the molar ratio of (E) to (A).

[0192] As can be seen from the results in Tables 2 and 3 above, the viscosity of the viscous fluids of the samples in the examples after the polymerization reaction is relatively high (6000-100000 Pa·s), thus exhibiting high attenuation. Furthermore, the temperature dependence of the viscous fluids is also low, resulting in smaller viscosity changes caused by temperature variations. Moreover, the samples in the examples all exhibit high dynamic elastic modulus, demonstrating good adhesion.

[0193] In contrast, the sample of Comparative Example 1, lacking branched silicone, failed to exhibit the desired dynamic elastic modulus and could not achieve adhesion. The sample of Comparative Example 2, containing only branched silicone and lacking linear silicone, also failed to exhibit the desired dynamic elastic modulus.

[0194] Industrial applicability

[0195] The silicone composition and viscous fluid for vibration damping devices of the present invention can perform excellent functions when used in vibration damping devices for civil engineering, construction, household appliances, and electronic equipment. In particular, the vibration damping devices used in large structures such as bridges and buildings, and especially those for high-rise buildings, can achieve even better performance.

[0196] In addition, vibration damping devices such as building vibration damping walls, vibration isolation devices, vibration damping materials for home appliances and electronic equipment, shock absorbing materials, vibration damping materials for automobiles, etc., which use the silicone composition for vibration damping dampers and the viscous fluid for vibration damping dampers of the present invention, can also be used as vibration damping devices of the present invention.

Claims

1. A silicone composition for vibration damping devices, wherein, The silicone composition for the vibration damper is mainly composed of (A) and (B) and contains (C) to (E) as follows: (A) Straight-chain, two-terminated vinyl-modified silicone; (B) Branched silicone; (C) Platinum catalyst; (D) Delaying agent; (E) Chain extender, The compound (B) is a reaction product of a crosslinking agent having three or more hydrogenated silanes in the molecular chain but not at the ends of the molecular chain, and a linear two-terminated vinyl-modified silicone. The linear two-terminated vinyl-modified silicone constituting the compound (B) has a viscosity of 2000~100000 mPa·s at 30°C. The ratio of the mass a of (A) to the mass b of the linear, two-terminated vinyl-modified silicone constituting (B) is a∶b=95∶5~10∶90. The chain extender (E) is a compound represented by general formula (3). In general formula (3), n is 1~18. The molar ratio of (E) to (A) in the silicone composition for the vibration damper is 0.1 to 2.

2. The silicone composition for vibration damping devices according to claim 1, wherein, The viscosity of (A) at 30°C is 2000~100000 mPa·s.

3. The silicone composition for vibration dampers according to claim 1 or 2, wherein, The content of (C) is 0.00003 to 0.003 parts by mass relative to 100 parts by mass of (A).

4. The silicone composition for vibration dampers according to claim 1 or 2, wherein, The content of (D) is 0.01 to 1 part by mass relative to 100 parts by mass of (A).

5. A viscous fluid for a vibration damper, wherein, The viscous fluid used in the vibration damper is polymerized from the silicone composition for vibration dampers according to any one of claims 1 to 4.

6. The viscous fluid for the vibration damper according to claim 5, wherein, The viscosity of the viscous fluid used in the vibration damper is 6000~150000 Pa·s at 30℃.

7. A vibration damping device, wherein, The vibration damper is formed by filling it with the viscous fluid of claim 5 or 6.

8. The vibration damping device according to claim 7, wherein, The vibration damper is a vibration damping wall.

Images