JP2014001337A - High damping composition and earthquake-proof damper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high damping composition that can form a high damping member subject that has especially excellent damping performance as an earthquake-proof damper or the like of an architectural structure, in which temperature dependency of the damping performance is small, and durability is also excellent when large deformation is repeated by earthquake or the like; and the earthquake-proof damper of the architectural structure or the like that includes the high damping member subject comprising the high damping composition.SOLUTION: A high damping composition combines an S-EP diblock copolymer, and an S-IB-S triblock copolymer as a basis polymer, and blends 10-80 pts.mass of a non-aroma plasticizer and 5-60 pts.mass of dry silica based on 100 pts.mass of the two block copolymers. A earthquake-proof damper combines a high damping member subject comprising the high damping composition and a steel member subject.

Description

  The present invention relates to a high damping composition that becomes a high damping member that relaxes or absorbs transmission of vibration energy, and a damping damper that includes the high damping member made of the high damping composition. is there.

For example, high-attenuation members are used in a wide range of fields such as buildings such as buildings and bridges, industrial machines, aircraft, automobiles, railway vehicles, computers and peripheral equipment, household electrical equipment, and automobile tires. By using the high damping member, transmission of vibration energy can be relaxed or absorbed, that is, seismic isolation, vibration control, vibration control, vibration isolation, etc. can be performed.
The high damping member is formed by a high damping composition including various base polymers.

For example, a block copolymer (isobutylene block copolymer) of a polymer block (S) having an aromatic vinyl compound as a constituent monomer and a polymer block (IB) having isobutylene as a constituent monomer is Since it is expected that the structure can form a high damping member having excellent damping performance, practical application of the high damping composition as a base polymer has been studied.
In particular, the S-IB diblock copolymer having a structure in which the polymer block (S) and the polymer block (IB) are connected one block at a time is excellent in damping performance. However, when the S-IB diblock copolymer is used alone as a base polymer, there is a problem that the molding processability of the high attenuation composition is low.

In addition, the high attenuation member formed using the high attenuation composition has a small amount of elongation until cutting when a tensile stress is applied, that is, the elongation at the time of cutting is small, so that it is greatly deformed particularly when an earthquake or the like occurs. There is also a problem that it is not suitable as a damper for vibration control of buildings that need to be done.
Therefore, another polymer excellent in molding processability, having a large elongation at break and having excellent compatibility with the S-IB diblock copolymer, together with the S-IB diblock copolymer, has a high damping composition. Use as a base polymer of a product has been studied (see, for example, Patent Documents 1 to 3).

  Examples of the other polymer include an S-IB-S triblock copolymer [having a structure in which one polymer block (IB) is sandwiched between two polymer blocks (S)]. The S-IB-S triblock copolymer is not as high in damping performance as the S-IB diblock copolymer, but has excellent moldability than the S-IB diblock copolymer and has an elongation at break. Since it is large and is constituted by the same polymer block (S) (IB), it is excellent in compatibility with the S-IB diblock copolymer.

WO 01/74964 A1 JP-A-11-263896 JP 2000-119478 A

In the combined use system of the S-IB diblock copolymer and the S-IB-S triblock copolymer, the damping performance, molding processability, and elongation at break to some extent are adjusted by adjusting the blending ratio of both. It is possible to balance.
However, by simply adjusting the blending ratio by using both in combination, it is not possible to give the high damping member high damping performance that can be sufficiently used as, for example, a vibration damper for a building. Further, the combined system has a problem that the attenuation performance changes depending on the temperature, that is, the so-called temperature dependency is large. Therefore, the inventor further examined the types and combinations of block copolymers.

  As a result, instead of the S-IB diblock copolymer, the polymer block (S) and the polymer block (EP) having ethylene / propylene as a structural unit are connected one block at a time. -EP diblock copolymer, when the S-EP diblock copolymer is used in combination with the S-IB-S triblock copolymer, while maintaining the damping performance of the high damping member at a good level, We found that the temperature dependence of the damping performance can be greatly reduced.

  However, according to the inventor's study, the combined system of the S-EP diblock copolymer and the S-IB-S triblock copolymer still has durability when repeated large deformation due to, for example, an earthquake or the like. It was insufficient. In addition, although it has been possible to maintain the damping performance at a certain level even in the current state as described above, it has become clear that there is room for further improvement of the damping performance as compared with the current state.

  The object of the present invention is to provide particularly excellent damping performance as a damping damper for buildings, etc., and also has low temperature dependence of the damping performance, and also durability when large deformation is repeated due to an earthquake or the like. An object of the present invention is to provide a high-damping composition capable of forming an excellent high-damping member and a damper for vibration control of a building or the like provided with a high-damping member made of the high-damping composition.

The present invention provides a base polymer
(1) an S-EP diblock copolymer of a polymer block (S) containing an aromatic vinyl compound as a constituent monomer and a polymer block (EP) containing ethylene / propylene as a constituent unit;
(2) S-IB-S triblock copolymer of the polymer block (S) and the polymer block (IB) having isobutylene as a structural unit,
Together with the two block copolymers of
10 parts by mass or more and 80 parts by mass or less of non-aromatic plasticizer and 5 parts by mass or more and 60 parts by mass or less of dry silica are blended per 100 parts by mass of the total amount of the two types of block copolymers. And a highly attenuated composition.

  According to the present invention, instead of the conventional S-IB diblock copolymer, the S-EP diblock copolymer of the above (1) is used as the base polymer, In combination with the S-IB-S triblock copolymer of the above (2), and by blending dry silica in the above proportion with respect to the total amount of the two types of block copolymers, Attenuation performance can be greatly improved compared to the current situation, and the temperature dependence of the attenuation performance can be made much smaller than before.

  That is, the equivalent damping constant Heq at 20 ° C. obtained by dynamic viscoelasticity measurement with a frequency of 0.1 Hz and a shear strain rate of 100% is set to 0.25 or more to greatly improve the damping performance, and equivalent shear at 0 ° C. The ratio Geq0 / Geq20 between the elastic modulus Geq0 and the equivalent shear elastic modulus Geq20 at 20 ° C. is set to 2.5 or less, and the temperature dependence of the damping performance can be greatly reduced.

Further, according to the present invention, by further blending a non-aromatic plasticizer with the two types of block copolymers and dry silica, and by defining the blending ratio of the non-aromatic plasticizer within the above range. Gives the high damping member good flexibility and resilience, improves the durability of the high damping member when repeated large deformations due to earthquakes, etc. Can be prevented. In other words, the elongation at break _Eb measured in accordance with the test method defined in Japanese Industrial Standards JIS K6251 _{: 2010} “Vulcanized Rubber and Thermoplastic Rubber—How to Obtain Tensile Properties” is 400% or more, and the durability is improved. It can be greatly improved.

In the present invention, the dry silica content is limited to 5 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the total amount of the two types of block copolymers as described above.
That is, when the blending ratio is less than the above range, the effect of improving the damping performance of the high damping member by blending the dry silica cannot be obtained.

On the other hand, when the blending ratio exceeds the above range, excessive dry silica is not evenly dispersed in the highly attenuated composition, and the distribution is biased. For example, when large deformation is repeated due to earthquakes or the like The durability of the high damping member is reduced.
On the other hand, when the blending ratio of the dry silica is within the above range, the entire amount of the dry silica can be evenly dispersed in the high attenuation composition without reducing the durability of the high attenuation member. The attenuation performance can be greatly improved compared to the current situation.

Silica is limited to dry silica for the following reasons.
That is, instead of dry silica, when wet silica produced by, for example, a precipitation method, a gel method, a sol-gel method or the like is used, the wet silica has a large number of pores unlike dry silica, and particles Since the specific surface area per diameter is large and the dispersibility with respect to the two types of block copolymers is poor, even if the wet silica is blended in the above proportion, the entire amount is evenly dispersed in the highly attenuated composition. However, the distribution is biased, and the durability of the high-attenuation member is reduced when large deformation is repeated due to, for example, an earthquake.

  On the other hand, when dry silica is selectively used as silica, the dry silica has a small specific surface area per particle diameter as compared with wet silica, has good dispersibility with respect to the two types of block copolymers, and When blended at a ratio of 1, it can be evenly dispersed in the high attenuation composition as described above, so that the attenuation performance is greatly improved compared to the current situation without reducing the durability of the high attenuation member. It becomes possible to do.

In the present invention, the blending ratio of the non-aromatic plasticizer is limited to 10 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the total amount of the two block copolymers as described above. Depending on the reason.
That is, when the blending ratio is less than the above range, by adding the non-aromatic plasticizer, the high-damping member described above is imparted with good flexibility and resilience, and large deformation is repeated due to an earthquake or the like. In this case, the effect of improving the durability of the high attenuation member cannot be obtained.

On the other hand, when the blending ratio exceeds the above range, excess non-aromatic plasticizer bleeds to the surface of the high damping member, and, for example, the high damping member and the high damping member constitute a damping damper. When bonding to a steel member or the like, poor adhesion or the like occurs, and there arises a problem that a damping damper or the like in which the high damping member and the steel member or the like are firmly bonded and integrated cannot be configured.
On the other hand, when the blending ratio of the non-aromatic plasticizer is within the above range, the high attenuation member is provided with good flexibility and resilience without causing the bleeding, and the durability of the high attenuation member is increased. It becomes possible to improve the property.

In the present invention, among various plasticizers, a plasticizer in which the mass ratio of components derived from an aromatic compound calculated from the results of NMR measurement is 35% by mass or less is defined as the “non-aromatic plasticizer”. I decided to.
In this invention, the said effect is acquired by mix | blending the said non-aromatic plasticizer selectively in the said ratio from various plasticizers.

On the other hand, even if the plasticizer other than the non-aromatic type (aromatic plasticizer) having a mass ratio of more than 35% by mass is blended in the above ratio, the same effect cannot be obtained. That is, the elongation _Eb during cutting is less than 400%, and the effect of improving the durability cannot be obtained.
In addition, when an aroma plasticizer is blended instead of a non-aromatic plasticizer, there is a problem that the temperature dependency of the damping performance increases.

Examples of the non-aromatic plasticizer include at least one selected from the group consisting of polyisobutylene, polybutene, paraffinic oil, and hydrogenated liquid polyisoprene.
The molecular weight of the S-IB-S triblock copolymer is preferably 50,000 or more and preferably 1,000,000 or less in terms of weight average molecular weight Mw.

When the weight average molecular weight Mw is less than the above range, the elongation at the time of cutting of the high damping member becomes small, which may make it unsuitable for use as, for example, a vibration damper. Moreover, when it exceeds the said range, there exists a possibility that the molding workability of a high attenuation | damping composition may fall.
The dry silica preferably has a BET specific surface area of 50 m ² / g or more.
If the BET specific surface area is less than the above range, the equivalent damping constant of the high damping member may be lowered, that is, the damping performance may be lowered.

The present invention is a vibration damper comprising the high damping member made of the high damping composition of the present invention and a steel member.
Since the high damping member is excellent in damping performance as described above, such a damper for vibration control can be miniaturized or reduced in the number incorporated in one building, and even if a large deformation is repeatedly applied due to the occurrence of an earthquake. Since the damping performance is not greatly deteriorated, it is possible to reliably prevent the energy of the earthquake and the aftershocks generated thereafter from being transmitted to the building.

  In addition, since the temperature dependence of the damping performance can be reduced, for example, the damping damper can be installed near the outer wall of a building having a large temperature difference, and the degree of freedom in designing the damping performance by the damping damper. Can also be increased.

  According to the present invention, it has a particularly excellent damping performance as a damping damper for buildings, etc., and the temperature dependence of the damping performance is small, and also durability when a large deformation is repeated due to an earthquake or the like. It is possible to provide a high-damping composition capable of forming an excellent high-damping member and a damper for vibration control of a building or the like provided with a high-damping member made of the high-damping composition.

It is a disassembled perspective view which decomposes | disassembles and shows the test body as a model of the said high attenuation member produced in order to evaluate the attenuation performance of the high attenuation member which consists of a high attenuation composition of this invention. FIGS. 4A and 4B are diagrams for explaining the outline of a testing machine for displacing the test body and obtaining the relationship between the displacement and the load. It is a graph which shows an example of the hysteresis loop which shows the relationship between the displacement amount and a load calculated | required by displacing a test body using the said testing machine.

<< High damping composition >>
The present invention provides a base polymer
(1) an S-EP diblock copolymer of a polymer block (S) containing an aromatic vinyl compound as a constituent monomer and a polymer block (EP) containing ethylene / propylene as a constituent unit;
(2) S-IB-S triblock copolymer of the polymer block (S) and the polymer block (IB) having isobutylene as a structural unit,
Together with the two block copolymers of
10 parts by mass or more and 80 parts by mass or less of non-aromatic plasticizer and 5 parts by mass or more and 60 parts by mass or less of dry silica are blended per 100 parts by mass of the total amount of the two types of block copolymers. And a highly attenuated composition.

<Base polymer>
As the base polymer, two types of block copolymers (1) S-EP diblock copolymer and (2) S-IB-S triblock copolymer are used in combination as described above.
In the both block copolymers, examples of the aromatic vinyl compound used as the basis of the polymer block (S) include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl- o-methylstyrene, β-methyl-m-methylstyrene, β-methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4 -Dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-chlorostyrene, m-chlorostyrene , P-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-chlorostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro -O-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4,6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2, 4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, o- Methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, o-butyl Examples thereof include one or more of lomomethylstyrene, m-bromomethylstyrene, p-bromomethylstyrene, a styrene derivative substituted with a silyl group, indene, and vinylnaphthalene. Styrene is particularly preferable.

The polymer block (S) may contain a monomer other than the aromatic vinyl compound, or may not contain the other monomer.
Examples of such other monomers include one or more of isobutylene, aliphatic olefins, dienes, vinyl ethers, β-pinene, and the like.
When the polymer block (S) contains another monomer, the proportion of the aromatic vinyl compound in the total amount of all monomers constituting the polymer block (S) is 60% by mass or more, particularly It is preferable that it is 80 mass% or more.

Further, the polymer block (IB) may contain a monomer other than isobutylene or may not contain the other monomer. Similarly, the polymer block (EP) may contain other monomers other than ethylene and propylene, or may not contain the other monomers.
Examples of such other monomers include one or more of the above aromatic vinyl compounds, aliphatic olefins, dienes, vinyl ethers, β-pinene, and the like.

When the polymer block (IB) contains other monomers, the proportion of isobutylene in the total amount of all monomers constituting the polymer block (IB) is 60% by mass or more, particularly 80% by mass or more. Is preferred.
When the polymer block (EP) contains other monomers, the ratio of ethylene / propylene in the total amount of all monomers constituting the polymer block (EP) is 60% by mass or more, particularly 80%. It is preferable that it is at least mass%.

Examples of the aliphatic olefins include ethylene, propylene, 1-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, hexene, cyclohexene, 4-methyl-1-pentene, vinylcyclohexane, and octene. , And one or more of norbornene and the like.
Examples of the dienes include one or more of butadiene, isoprene, hexadiene, cyclopentadiene, cyclohexadiene, dicyclopentadiene, divinylbenzene, ethylidene norbornene, and the like.

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, methyl propenyl ether, and ethyl propenyl ether. Or 2 or more types are mentioned.

(S-EP diblock copolymer)
The S-EP diblock copolymer has a structure in which the polymer block (S) and the polymer block (EP) are connected one block at a time.
The copolymer ratio of both polymer blocks (S) (EP) in the S-EP diblock copolymer is that of the polymer block (S) in the total amount of both polymer blocks (S) (EP). Expressed as a ratio, it is preferably 2% by mass or more, particularly preferably 5% by mass or more, particularly preferably 15% by mass or more, and more preferably 80% by mass or less, particularly preferably 60% by mass or less, particularly preferably 40% by mass or less.

By adjusting the ratio of the polymer block (S) within the above range, the chain lengths of both the polymer blocks (S) (EP) are balanced, and the high attenuation member as the S-EP diblock copolymer is obtained. The effect of imparting good damping performance can be exhibited well.
The ratio of ethylene and propylene in the polymer block (EP) is not particularly limited, but is preferably about 50:50. For example, since the polymer block (EP) in the S-EP diblock copolymer manufactured by Kraton Polymers below is constituted by hydrogenating isoprene, the ratio of ethylene to propylene is about 50:50.

  Examples of the S-EP diblock copolymer include, but are not limited to, for example, Kraton (registered trademark) G1701E (styrene content ratio, which is a styrene-ethylene / propylene diblock copolymer manufactured by Kraton Polymers Co., Ltd.). : 35% by mass), G1701H (styrene content: 37% by mass), G1701M (styrene content: 37% by mass) and the like.

(S-IB-S triblock copolymer)
The S-IB-S triblock copolymer has a structure in which one polymer block (IB) is sandwiched between two polymer blocks (S).
In the S-IB-S triblock copolymer, the copolymer ratio of both polymer blocks (S) (IB) is the polymer block (S) in the total amount of both polymer blocks (S) (IB). ), It is preferably 2% by mass or more, especially 5% by mass or more, particularly preferably 15% by mass or more, more preferably 80% by mass or less, particularly preferably 60% by mass or less, and particularly preferably 40% by mass or less.

  By adjusting the ratio of the polymer block (S) within the above range, the chain lengths of both polymer blocks (S) and (IB) are balanced, and high attenuation as an S-IB-S triblock copolymer is achieved. In addition to imparting good moldability to the composition, the effect of increasing the elongation at break of the high-damping member can be exhibited well. Also, good compatibility with the S-IB diblock copolymer can be imparted.

The molecular weight of the S-IB-S triblock copolymer is preferably 50,000 or more and preferably 1,000,000 or less in terms of weight average molecular weight Mw.
When the weight average molecular weight Mw is less than the above range, the elongation at the time of cutting of the high damping member becomes small, which may make it unsuitable for use as, for example, a vibration damper. Moreover, when it exceeds the said range, there exists a possibility that the molding workability of a high attenuation | damping composition may fall.

The S-IB-S triblock copolymer can be produced, for example, by the synthesis methods described in Patent Documents 1 and 2.
Examples of the S-IB-S triblock copolymer include, but are not limited to, SIBSTAR (registered trademark) 062T, 072T, and 102T, which are styrene-isobutylene-styrene triblock copolymers manufactured by Kaneka Corporation. Etc.

(Mixing ratio)
The blending ratio of the two types of block copolymers is 10% by mass or more, particularly 15% by mass, expressed as a ratio of the S-IB-S triblock copolymer in the total amount of the two types of block copolymers. The above is preferable, and it is preferably 60% by mass or less, particularly preferably 40% by mass or less.
When the amount of S-IB-S triblock copolymer is less than the above range, the effect of imparting good moldability to the high attenuation composition and the effect of increasing the elongation at cutting of the high attenuation member are sufficiently obtained. There is a risk of not being able to.

On the other hand, when there are more S-IB-S triblock copolymers than the said range, there exists a possibility that the temperature dependence of damping performance cannot fully be made small.
On the other hand, by defining the ratio of the S-IB-S triblock copolymer within the above range, the temperature dependence of the damping performance is maintained while maintaining the damping performance of the high damping member at a good level. Can be much smaller than

<Dry silica>
As dry silica, for example, combustion method silica produced by reacting silicon chloride such as silicon tetrachloride in a gas phase reaction in an oxygen / hydrogen flame, so-called fumed silica, or by-product during production of metallic silicon One type or two or more types such as silica fume as a product may be mentioned.
The dry silica preferably has a BET specific surface area of 50 m ² / g or more.

If the BET specific surface area is less than the above range, the equivalent damping constant of the high damping member may be lowered, that is, the damping performance may be lowered.
In addition, the upper limit of a BET specific surface area is not specifically limited, The thing of about 500 m < ² > / g which is a general upper limit of the specific surface area of a dry-type silica can be used.
Examples of the dry silica include Aerosil (registered trademark) 90 [BET specific surface area: 90 ± 15 m ² / g], 130 [BET specific surface area: 130 ± 15 m ² / g], 150 [BET] manufactured by Nippon Aerosil Co., Ltd. The specific surface area: 150 ± ^15m 2 / g], 200 [BET specific surface area: 200 ± ^25m 2 / g], 255 [BET specific surface area: 255 ± ^25m 2 / g], 300 [BET specific surface area: 300 ± ^{30 m} 2 / g] hydrophilic fumed silica such as 380 [BET specific surface area: 380 ± 30 m ² / g], or hydrophobic fumed silica obtained by hydrophobizing the hydrophilic fumed silica with a trimethylsilyl group or the like, for example, Aerosil RX200 [BET specific surface area: 140 ± ^25m 2 / g], RX300 [BET specific surface area: 210 ± ^20m 2 / g] one etc. 2 or more, and the like.

The blending ratio of dry silica is limited to 5 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the total amount of the two types of block copolymers.
When the blending ratio is less than the above range, the effect of improving the damping performance of the high damping member by blending the dry silica cannot be obtained.
On the other hand, when the blending ratio exceeds the above range, excessive dry silica is not evenly dispersed in the highly attenuated composition, and the distribution is biased, for example, when large deformation is repeated due to earthquakes or the like. The durability of the high damping member is reduced.

On the other hand, when the dry silica content is within the above range, the entire amount of the dry silica is evenly dispersed in the high attenuation composition, and the attenuation performance is reduced without reducing the durability of the high attenuation member. Can be significantly improved from the current situation.
In consideration of further greatly improving the damping performance while preventing the durability of the high damping member from being lowered, the blending ratio of the dry silica is within the above range. It is preferably 15 parts by mass or more, particularly 30 parts by mass or more per 100 parts by mass of the combined amount.

<Non-aromatic plasticizer>
As described above, as the non-aromatic plasticizer, any of various plasticizers in which the mass ratio of the component derived from the aromatic compound calculated from the NMR measurement result is 35% by mass or less can be used. is there.
Examples of the non-aromatic plasticizer include at least one selected from the group consisting of polyisobutylene, polybutene, paraffinic oil, and hydrogenated liquid polyisoprene. Since none of these plasticizers contains an aromatic compound in the starting material and product, the mass ratio of components derived from the aromatic compound is 35% by mass or less.

In addition, the mass ratio of the component derived from the aromatic compound is calculated by, for example, subjecting the target compound to ring analysis (ndM method) to calculate% CA,% CP and% CN. It can be determined by the ratio of% CA indicating the component derived from the aromatic compound.
Among these, examples of the polyisobutylene include one or more of Tetrax (registered trademark) grade 3T, grade 4T, grade 5T, grade 6T, etc., manufactured by JX Nippon Oil & Energy Corporation.

  As polybutene, for example, Nisseki Polybutene Grade LV-7, Grade LV-50, Grade LV-100, Grade HV-15, Grade HV-35, Grade HV-50, Grade manufactured by JX Nippon Mining & Energy Co., Ltd. 1 type, or 2 or more types, such as HV-100, grade HV-300, grade HV-1900, grade SV-7000, are mentioned.

As the paraffinic oil, various paraffinic oils that are refined from mineral oil (crude oil) and whose base oil is paraffinic can be used. Examples of such paraffinic oils include one or more of Diana (registered trademark) process oils PW-32, PW-90, PW-150, PW-380 manufactured by Idemitsu Kosan Co., Ltd.
Furthermore, examples of the hydrogenated liquid polyisoprene include Claprene (registered trademark) LIR-290 manufactured by Kuraray Co., Ltd.

The blending ratio of the non-aromatic plasticizer is limited to 10 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the total amount of the two types of block copolymers.
If the blending ratio is less than the above range, by adding the non-aromatic plasticizer, the high damping member described above is provided with good flexibility and resilience, and large deformation is repeated due to an earthquake or the like. In this case, the effect of improving the durability of the high attenuation member cannot be obtained.

On the other hand, when the blending ratio exceeds the above range, excess non-aromatic plasticizer bleeds to the surface of the high damping member, and, for example, the high damping member and the high damping member constitute a damping damper. When bonding to a steel member or the like, poor adhesion or the like occurs, and there arises a problem that a damping damper or the like in which the high damping member and the steel member or the like are firmly bonded and integrated cannot be configured.
On the other hand, when the blending ratio of the non-aromatic plasticizer is within the above range, the high attenuation member is provided with good flexibility and resilience without causing the bleeding, and the durability of the high attenuation member is increased. It becomes possible to improve the property.

In consideration of further improving the durability of the high-damping member while preventing bleeding, the blending ratio of the non-aromatic plasticizer is within the above range. It is preferably 20 parts by mass or more, particularly 25 parts by mass or more, more preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less, per 100 parts by mass of the combined amount.
<Attenuation performance evaluation>
The damping performance of the high damping member is evaluated by the magnitude of the equivalent damping constant Heq obtained by the following measurement method. That is, it can be determined that the higher the equivalent attenuation constant Heq, the better the high attenuation member has the attenuation performance. In particular, the equivalent damping constant Heq is preferably 0.25 or more.

(Preparation of test specimen)
A high damping composition for evaluating the properties is extruded into a sheet and then punched to produce a disk 1 (thickness 5 mm × diameter 25 mm). A rectangular plate-shaped steel plate 2 having a thickness of 6 mm × length 44 mm × width 44 mm is stacked and pressed in the laminating direction via an acrylate-based adhesive, whereby the disk 1 is bonded to the two steel plates 2 and is highly attenuated. A test body 3 for evaluating damping performance as a member model is prepared.

(Displacement test)
As shown in FIG. 2 (a), two test bodies 3 are prepared, and the two test bodies 3 are fixed to one central fixing jig 4 with bolts via one steel plate 2. One left and right fixing jig 5 is fixed to the other steel plate 2 of each test body 3 with bolts. The center fixing jig 4 is fixed to the upper fixing arm 6 of the testing machine (not shown) with a bolt via a joint 7, and the two left and right fixing jigs 5 are connected to the lower movable platen of the testing machine. 8 is fixed with a bolt through a joint 9.

  Next, in this state, the movable platen 8 is displaced so as to be pushed up in the direction of the fixed arm 6 as indicated by the white arrow in the figure, and the disk 1 of the test body 3 is moved to the position shown in FIG. As shown in the figure, the test body 3 is strained and deformed in a direction orthogonal to the stacking direction, and from this state, the movable platen 8 is moved in a direction opposite to the direction of the fixed arm 6 as indicated by a white arrow in the figure. The operation of the test body 3 when the disk 1 of the test body 3 is repeatedly distorted or deformed, that is, vibrated, with the operation of displacing it down and returning to the state shown in FIG. A hysteresis loop H (see FIG. 3) indicating the relationship between the displacement (mm) of the disk 1 in the direction perpendicular to the stacking direction and the load (N) is obtained.

The measurement is performed for 3 cycles under the environment of a temperature of 20 ° C. to obtain the third value. The frequency of vibration is 0.1 Hz. The maximum deviation of the two steel plates 2 sandwiching the disc 1 in the direction orthogonal to the stacking direction is set to be 100% expressed as a percentage (shear strain rate) with respect to the thickness of the disc 1. .
Then, connecting the maximum displacement point and the minimum displacement point of the hysteresis loop H shown in FIG. 3 obtained by the measurement, determine the slope Keq (N / mm) of the straight line L ₁ shown by a thick solid line in the figure, the From the inclination Keq (N / mm), the thickness T (mm) of the disc 1, and the cross-sectional area A (mm ² ) of the disc 1, the formula (1):

To obtain the equivalent shear modulus Geq (N / mm ² ).
Also, the absorbed energy amount ΔW represented by the total surface area of the hysteresis loop H shown with diagonal lines in FIG. 3, the straight line L ₁ shown with a mesh line in the figure, and the horizontal axis, and a straight line L ₁ and the hysteresis loop H elastic strain energy W represented by the surface area of the region surrounded by the perpendicular L ₂ grated on the horizontal axis from the intersection of the formula (2):

The equivalent attenuation constant Heq is obtained by
<Evaluation of temperature dependence of damping performance>
The temperature dependence of the damping performance is equivalent to the equivalent shear elastic modulus Geq0 (N / mm ² ) obtained by conducting the same displacement test as described above in an environment of 0 ° C., and the equivalent shear elasticity in the environment of 20 ° C. Evaluation is based on the ratio Geq0 / Geq20 to the ratio Geq20 (N / mm ² ).

That is, it can be determined that the temperature dependence of the damping performance is smaller as the ratio Geq0 / Geq20 is closer to 1. In particular, the ratio Geq0 / Geq20 is preferably 2.5 or less.
<Tensile property evaluation>
A dumbbell-shaped No. 1 test piece defined in Japanese Industrial Standard JIS K6251 _{: 2010} "Vulcanized rubber and thermoplastic rubber-Determination of tensile properties" is prepared using a highly attenuating composition in an environment at a temperature of 20 ° C. Then, using the test piece, a tensile test is performed at a test speed of 300 mm / min in accordance with the test method defined in the same standard to obtain the elongation at break E _b (%).

It can be determined that the elongation at break _Eb is preferably as large as possible as described above. In particular, the elongation at break _Eb is preferably 400% or more.
《High damping member》
As a high damping member that can be formed using the high damping composition of the present invention, for example, a damper for seismic isolation incorporated in the foundation of a building such as a building, or for vibration control (vibration suppression) incorporated in the structure of a building Dampers for cables, suspension members for cables such as suspension bridges and cable-stayed bridges, anti-vibration members for industrial machines, aircraft, automobiles, railway vehicles, etc., anti-vibration members for computers and peripheral devices, or household electrical equipment, Furthermore, treads for automobile tires and the like can be mentioned.

According to the present invention, the types and combinations of the S-EP diblock copolymer, S-IB-S triblock copolymer, non-aromatic plasticizer, and dry silica, and the blending ratio are within the above range. By adjusting, a high attenuation member having excellent attenuation performance suitable for each application can be obtained.
<Seismic damper>
In particular, when a high-damping member made of the high-damping composition of the present invention and a steel member such as a steel plate or a steel pipe are combined to form a damper for damping that is incorporated into the structure of a building, as described above. Since the high damping member has excellent damping performance, it is possible to reduce the size of the damping damper and to reduce the number of built-in damping dampers in a single building. In addition, even if large deformations are repeatedly applied due to the occurrence of an earthquake, the damping performance is greatly reduced. Therefore, it is possible to reliably prevent the energy of the earthquake and the aftershocks that occur thereafter from being transmitted to the building.

  In addition, since the temperature dependence of the damping performance can be reduced, for example, the damping damper can be installed near the outer wall of a building having a large temperature difference, and the degree of freedom in designing the damping performance by the damping damper. Can also be increased.

<Example 1>
65 parts by mass of an S-EP diblock copolymer [Clayton (registered trademark) G1701E made by Kraton Polymers, Ltd.] as a base polymer, and an S-IB-S triblock copolymer [Corporation, Inc.] SIBSTAR (registered trademark) 102T manufactured by Kaneka, 35 parts by mass of weight average molecular weight Mw: 100,000], polyisobutylene as a non-aromatic plasticizer [Tetrax manufactured by JX Nippon Mining & Energy Corporation) Trademark) Grade 3T, mass ratio of aromatic compound-derived components: 0 mass%], and dry silica [Aerosil (registered trademark) 200 manufactured by Nippon Aerosil Co., Ltd., BET specific surface area: 200 ± 25 m ² / g] 5 parts by mass were blended and kneaded using a closed kneader to prepare a highly attenuated composition.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of polyisobutylene per 100 parts by weight of the two types of block copolymers was 40 parts by weight, and the blending ratio of dry silica was 5 parts by weight.
<Example 2>
As a non-aromatic plasticizer, instead of the above polyisobutylene, polybutene [Nisseki polybutene grade HV-300 manufactured by JX Nippon Mining & Energy Co., Ltd., mass ratio of components derived from aromatic compounds: 0% by mass A highly attenuated composition was prepared in the same manner as in Example 1 except that 40 parts by mass was blended and the amount of dry silica was 30 parts by mass.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of polybutene per 100 parts by weight of the two types of block copolymers was 40 parts by weight, and the blending ratio of dry silica was 30 parts by weight.
<Example 3>
As a non-aromatic plasticizer, instead of the polyisobutylene, paraffinic oil [Diana (registered trademark) process oil PW-380 manufactured by Idemitsu Kosan Co., Ltd., mass ratio of components derived from aromatic compounds: 0 % By mass] A high-damping composition was prepared in the same manner as in Example 1 except that 40 parts by mass and the amount of dry silica was 60 parts by mass.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of paraffinic oil per 100 parts by weight of the two types of block copolymers was 40 parts by weight, and the blending ratio of dry silica was 60 parts by weight.
<Example 4>
The amount of the S-EP diblock copolymer is 40 parts by mass, the amount of the S-IB-S triblock copolymer is 60 parts by mass, and as a non-aromatic plasticizer, hydrogen is used instead of the polyisobutylene. Addition of liquid polyisoprene [Kuraprene (registered trademark) LIR-290 made by Kuraray Co., Ltd., mass ratio of components derived from aromatic compound: 0 mass%] 30 parts by mass, and the amount of dry silica A highly attenuated composition was prepared in the same manner as in Example 1 except that the amount was 15 parts by mass.

The proportion of the S-IB-S triblock copolymer in the total amount of the two types of block copolymers was 60% by mass. The blending ratio of hydrogenated liquid polyisoprene per 100 parts by weight of the two types of block copolymers was 30 parts by weight, and the blending ratio of dry silica was 15 parts by weight.
<Example 5>
A highly attenuated composition was prepared in the same manner as in Example 4 except that the amount of the S-EP diblock copolymer was 45 parts by mass and the amount of the S-IB-S triblock copolymer was 55 parts by mass. did.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 55% by mass. The blending ratio of hydrogenated liquid polyisoprene per 100 parts by weight of the two types of block copolymers was 30 parts by weight, and the blending ratio of dry silica was 15 parts by weight.
<Comparative example 1>
As a non-aromatic plasticizer, instead of the polyisobutylene, paraffinic oil [Diana (registered trademark) process oil PW-380 manufactured by Idemitsu Kosan Co., Ltd., mass ratio of components derived from aromatic compounds: 0 % By mass] A high-damping composition was prepared in the same manner as in Example 1 except that 20 parts by mass and no dry silica were added.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of paraffinic oil per 100 parts by weight of the two block copolymers was 20 parts by weight, and the blending ratio of dry silica was 0 part by weight.
<Comparative example 2>
As a non-aromatic plasticizer, in place of the polyisobutylene, a hydrogenated liquid polyisoprene [Kuraprene (registered trademark) LIR-290, manufactured by Kuraray Co., Ltd., a mass ratio of components derived from an aromatic compound: 0 mass %] A highly attenuating composition was prepared in the same manner as in Example 1 except that 30 parts by mass and 3 parts by mass of dry silica were added.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of hydrogenated liquid polyisoprene per 100 parts by weight of the two types of block copolymers was 30 parts by weight, and the blending ratio of dry silica was 3 parts by weight.
<Comparative Example 3>
The amount of the S-EP diblock copolymer is 40 parts by mass, the amount of the S-IB-S triblock copolymer is 60 parts by mass, and as a non-aromatic plasticizer, hydrogen is used instead of the polyisobutylene. Addition of liquid polyisoprene [Kuraprene (registered trademark) LIR-290 made by Kuraray Co., Ltd., mass ratio of components derived from aromatic compound: 0 mass%] 30 parts by mass, and the amount of dry silica A highly attenuated composition was prepared in the same manner as in Example 1 except that the amount was 70 parts by mass.

The proportion of the S-IB-S triblock copolymer in the total amount of the two types of block copolymers was 60% by mass. The blending ratio of hydrogenated liquid polyisoprene per 100 parts by weight of the two types of block copolymers was 30 parts by weight, and the blending ratio of dry silica was 70 parts by weight.
<Comparative example 4>
The amount of the S-EP diblock copolymer is 40 parts by mass, the amount of the S-IB-S triblock copolymer is 60 parts by mass, and as a non-aromatic plasticizer, hydrogen is used instead of the polyisobutylene. Addition liquid polyisoprene [Claprene (registered trademark) LIR-290 made by Kuraray Co., Ltd., mass ratio of components derived from aromatic compound: 0 mass%] 5 parts by mass, and the amount of dry silica A highly attenuating composition was prepared in the same manner as in Example 1 except that the amount was 30 parts by mass.

The proportion of the S-IB-S triblock copolymer in the total amount of the two types of block copolymers was 60% by mass. The blending ratio of the hydrogenated liquid polyisoprene per 100 parts by weight of the two types of block copolymers was 5 parts by weight, and the blending ratio of dry silica was 30 parts by weight.
<Comparative Example 5>
As a non-aromatic plasticizer, in place of the polyisobutylene, a hydrogenated liquid polyisoprene [Kuraprene (registered trademark) LIR-290, manufactured by Kuraray Co., Ltd., a mass ratio of components derived from an aromatic compound: 0 mass %] A highly attenuated composition was prepared in the same manner as in Example 1 except that 90 parts by mass and the amount of dry silica was 30 parts by mass.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of hydrogenated liquid polyisoprene per 100 parts by weight of the two types of block copolymers was 90 parts by weight, and the blending ratio of dry silica was 30 parts by weight.
<Comparative Example 6>
In place of the polyisobutylene as a non-aromatic plasticizer, a styrene-based oligomer which is an aromatic plasticizer in which the mass ratio of components derived from aromatic compounds exceeds 35% by mass [Picolastic A-manufactured by Rika Hercules Co., Ltd. 5] A highly attenuated composition was prepared in the same manner as in Example 1 except that 30 parts by mass was blended.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of styrene oligomer per 100 parts by weight of the two types of block copolymers was 30 parts by weight, and the blending ratio of dry silica was 5 parts by weight.
<Comparative Example 7>
As a non-aromatic plasticizer, in place of the polyisobutylene, a hydrogenated liquid polyisoprene [Kuraprene (registered trademark) LIR-290, manufactured by Kuraray Co., Ltd., a mass ratio of components derived from an aromatic compound: 0 mass %] A highly attenuating composition was prepared in the same manner as in Example 1 except that 30 parts by mass and 5 parts by mass of wet silica instead of dry silica were added.

The proportion of the S-IB-S triblock copolymer in the total amount of the two block copolymers was 35% by mass. The blending ratio of hydrogenated liquid polyisoprene per 100 parts by weight of the two types of block copolymers was 30 parts by weight, and the blending ratio of wet silica was 5 parts by weight.
With respect to the high damping compositions prepared in the respective Examples and Comparative Examples, the damping performance evaluation, the temperature dependence evaluation of the damping performance, and the tensile property evaluation described above were performed to evaluate the characteristics.

With respect to the attenuation performance, an equivalent attenuation constant Heq of 0.25 or higher was evaluated as good and a value of less than 0.25 was evaluated as poor. The temperature dependence of the damping performance was evaluated as good when the ratio Geq0 / Geq20 was 2.5 or less, and as poor when the ratio exceeded 2.5. As for the tensile properties, those having an elongation _Eb at cutting of 400% or more were evaluated as good, and those having less than 400% were evaluated as defective.
In Comparative Example 5, because the excess hydrogenated liquid polyisoprene bleeds on the surface of the disk 1 and the specimen 3 which was firmly bonded and integrated with the steel plate 2 could not be formed, the damping performance evaluation, and The temperature dependence of the damping performance was not evaluated.

  The above results are shown in Tables 1 and 2.

  From the results of Examples 1 to 5 and Comparative Examples 1 to 7 in Tables 1 and 2, the base polymer was used in combination with two types of S-EP diblock copolymer and S-IB-S triblock copolymer. By blending 10 parts by mass or more and 80 parts by mass or less of non-aromatic plasticizer and 5 parts by mass or more and 60 parts by mass or less of dry silica per 100 parts by mass of the two types of block copolymers, high attenuation The damping performance of the member is greatly improved compared to the current situation, the temperature dependence of the damping performance is greatly reduced than before, and the high damping member is provided with good flexibility and resilience. It has been found that the durability of the high damping member can be improved when the deformation is repeated.

DESCRIPTION OF SYMBOLS 1 Disc 2 Steel plate 3 Specimen 4 Center fixed jig 5 Left and right fixed jig 6 Fixed arm 7 Joint 8 Movable platen 9 Joint H Hysteresis loop L ₁ Straight line L ₂ perpendicular W Energy ΔW Absorbed energy amount

<Example 1>
65 parts by mass of an S-EP diblock copolymer [Clayton (registered trademark) G1701E made by Kraton Polymers, Ltd.] as a base polymer, and an S-IB-S triblock copolymer [Corporation, Inc.] SIBSTAR (registered trademark) 102T manufactured by Kaneka, 35 mass parts of weight average molecular weight Mw: 120,000 ], polyisobutylene as a non-aromatic plasticizer [Tetrax manufactured by JX Nippon Mining & Energy Co., Ltd. Trademark) Grade 3T, mass ratio of aromatic compound-derived components: 0 mass%], and dry silica [Aerosil (registered trademark) 200 manufactured by Nippon Aerosil Co., Ltd., BET specific surface area: 200 ± 25 m ² / g] 5 parts by mass were blended and kneaded using a closed kneader to prepare a highly attenuated composition.

Claims (5)

As a base polymer,
(1) an S-EP diblock copolymer of a polymer block (S) containing an aromatic vinyl compound as a constituent monomer and a polymer block (EP) containing ethylene / propylene as a constituent unit;
(2) S-IB-S triblock copolymer of the polymer block (S) and the polymer block (IB) having isobutylene as a structural unit,
Together with the two block copolymers of
10 parts by mass or more and 80 parts by mass or less of non-aromatic plasticizer and 5 parts by mass or more and 60 parts by mass or less of dry silica are blended per 100 parts by mass of the total amount of the two types of block copolymers. High damping composition.   The high attenuation composition according to claim 1, wherein the S-IB-S triblock copolymer has a weight average molecular weight Mw of 50,000 or more and 1,000,000 or less.   The highly attenuating composition according to claim 1 or 2, wherein the non-aromatic plasticizer is at least one selected from the group consisting of polyisobutylene, polybutene, paraffinic oil, and hydrogenated liquid polyisoprene. 4. The highly attenuated composition according to claim 1, wherein the dry silica has a BET specific surface area of 50 m ² / g or more.   A damping damper comprising a high damping member made of the high damping composition according to any one of claims 1 to 4 and a steel member.

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