KR101780829B1 - High damping composition - Google Patents

Abstract

It is an object of the present invention to provide a high-damping composition which is capable of forming a high-damping member having excellent damping performance and low temperature dependency such as rigidity and having stable characteristics in a wide temperature range, and also having excellent workability.
The high damping composition of the present invention is produced by mixing at least one liquid homopolymer selected from the group consisting of a liquid isoprene rubber and a liquid butadiene rubber into a diene rubber as a base polymer, silica and / or carbon black as a filler, 31 parts by mass or more per part.

Description

[0001] HIGH DAMPING COMPOSITION [0002]

The present invention relates to a high-damping composition as a raw material for a high-damping member that relaxes or absorbs the transmission of vibrational energy.

In order to mitigate or absorb vibration energy transmission in a wide range of fields, such as buildings such as buildings and bridges, industrial machinery, aircraft, automobiles, railway vehicles, computers and their peripheral devices, household electric appliances, A high-damping member including rubber or the like as a base polymer is used for vibration isolation, vibration control (vibration damping), and vibration control.

The high damping member includes the base polymer in order to increase damping performance by increasing hysteresis loss when vibration is applied, that is, to enable efficient and rapid attenuation of energy of the vibration, and loss tangent (tan? Is generally formed by a high-damping composition which is adjusted such that the peak of the high-attenuation member enters the use temperature region of the high-attenuating member.

The high-damping composition is formed into a predetermined three-dimensional shape, and when the base polymer is rubber, the high-damping member is formed by vulcanization.

A diene rubber is suitably used as the base polymer. Since the glass transition temperature of the diene rubber does not exist near room temperature (2 ° C to 35 ° C), the temperature dependency such as rigidity at the room temperature, which is the most common use temperature range, is reduced, There is an advantage that a high-damping member can be formed.

As the high-damping composition, silica and silane compound (silylating agent) are added as a damping property-imparting agent to a base polymer such as the diene-based rubber and kneaded to react the silica with a silane compound (Patent Document 1 Reference).

However, such a conventional high-damping composition can not sufficiently enhance the damping performance of the high-damping member.

It is conceivable to further increase the mixing ratio of silica in order to further increase the damping performance of the high damping member. However, a high-damping composition containing a large amount of silica has a problem in that the viscosity at the time of kneading is increased and the workability is lowered so that the high-damping composition is kneaded or molded into the three- There is a problem that it is not easy.

Therefore, studies have been made to incorporate a liquid rubber as a component for lowering the rigidity of the base polymer and lowering the viscosity at the time of kneading of the high-damping composition, thereby imparting good processability to the high-damping composition (see, for example, Patent Documents 2, 3 Reference).

However, depending on the kind and the blending ratio of the liquid rubber, the temperature dependency such as the rigidity of the high-damping member becomes large, and a problem arises that a high-damping member having stable rigidity in a wide temperature range can not be formed.

Patent Document 1: JP-A-7-41603 Patent Document 2: JP-A-2009-30016 Patent Document 3: Japanese Patent Application Laid-Open No. 11-68850

An object of the present invention is to provide a high-damping composition which is capable of forming a high-damping member having excellent damping performance and low temperature dependency such as rigidity and stable characteristics in a wide temperature range, and also having excellent processability.

The inventors of the present invention first examined the kind of liquid rubber.

As a result, when a liquid homopolymer such as liquid isoprene rubber (liquid IR) or liquid butadiene rubber (liquid BR) is selectively used as the liquid rubber, liquid styrene butadiene rubber (liquid SBR), liquid acrylonitrile butadiene rubber Liquid phase NBR) or the like is used, the temperature dependency such as rigidity of the high-damping member can be remarkably reduced.

Therefore, the mixing ratio of the liquid homopolymer was further investigated, and the present invention was completed.

That is, the present invention relates to a diene rubber as a base polymer,

At least one liquid homopolymer selected from the group consisting of a liquid isoprene rubber and a liquid butadiene rubber, and

At least one filler selected from the group consisting of silica and carbon black

As a high-damping composition,

Wherein the compounding ratio of the liquid homopolymer per 100 parts by mass of the diene rubber is 31 parts by mass or more.

In the present invention, the blending ratio of the liquid homopolymer per 100 parts by mass of the diene rubber is limited to not less than 31 parts by mass. When the amount is less than the above range, the stiffness of the base polymer is lowered due to the blending of the liquid homopolymer This is because an effect of imparting good workability to the high-damping composition can not be obtained by lowering the viscosity at the time of kneading the damping composition.

On the other hand, according to the present invention, it is possible to selectively use at least one liquid homopolymer of the two liquid rubber as the liquid rubber, and to set the mixing ratio within the above range, the damping performance is excellent and the temperature dependency It becomes possible to form a high-damping member having a stable characteristic over a wide temperature range, and it is also possible to provide a high-damping composition excellent in workability.

It is also possible to further improve the damping performance of the high damping member, to further reduce the temperature dependency such as rigidity, to form a high damping member having stable characteristics over a wider temperature range, The blending ratio per 100 parts by mass of the diene rubber of the filler is not less than 125 parts by mass and not more than 180 parts by mass and the compounding ratio per 100 parts by mass of the total amount of the filler of the liquid homopolymer is not less than 25 parts by mass and not more than 60 parts by mass Or less.

Further, considering that the temperature dependency of rigidity or the like is further reduced to form a high damping member having stable characteristics in a wider temperature range, the high damping composition does not contain an alicyclic hydrocarbon resin having a high temperature dependency such as hardness , The blend ratio thereof is preferably 25 parts by mass or less per 100 parts by mass of the diene rubber.

The silica in the filler is preferably silica having a BET specific surface area of 120 m 2 / g or more and 300 m 2 / g or less. By using the silica having a BET specific surface area within the above range, the attenuation performance of the high-damping member can be further improved by the combination of the range not affecting the workability of the high-damping composition.

As the diene rubber, it is preferable to use the butadiene rubber alone, or the butadiene rubber and the natural rubber in combination. Since the butadiene rubber has a small temperature dependence such as rigidity among the diene rubbers, the temperature dependency such as the rigidity of the high damping member is further reduced, and a highly damped member having more stable characteristics over a wide temperature range can be formed.

As the diene rubber, a general purpose natural rubber may be used alone. In this case, the productivity of the high-damping composition or the high-damping member can be improved and the production cost can be lowered.

When the damper for seismic control of a building as a high damping member is formed by using the high damping composition of the present invention as a forming material, since the damper for earthquake control has excellent damping performance, the damper for seismic control embedded in one building The quantity can be reduced. In addition, since the temperature dependency such as rigidity is small, the damper can be installed in the vicinity of the outer wall of a building having a large temperature difference, for example.

According to the present invention, it is possible to provide a high-damping composition which is excellent in damping performance, has a low temperature dependence such as rigidity, can form a high-damping member having stable characteristics in a wide temperature range, and has excellent processability.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an exploded perspective view of a specimen as a model of the highly damped member, which is prepared for evaluating damping performance of a high damping member including a high damping composition of an embodiment and a comparative example of the present invention.
Figs. 2 (a) and 2 (b) are views for explaining the outline of a tester for displacing the specimen to determine the relationship between the displacement and the load. Fig.
3 is a graph showing an example of a hysteresis loop showing a relationship between a displacement and a load obtained by displacing a specimen using the tester.

The present invention relates to a diene rubber as a base polymer,

At least one liquid homopolymer selected from the group consisting of a liquid isoprene rubber and a liquid butadiene rubber,

At least one filler selected from the group consisting of silica and carbon black

As a high-damping composition,

Wherein the compounding ratio of the liquid homopolymer per 100 parts by mass of the diene rubber is 31 parts by mass or more.

<Diene rubber>

Examples of the diene rubber include at least one of natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, and the like.

As described above, since the glass transition temperature does not exist near the room temperature (2 ° C to 35 ° C), the diene rubber reduces temperature dependency such as rigidity at the room temperature, which is the most common use temperature region, It is possible to form a high-damping member exhibiting stable characteristics.

As the diene rubber, it is preferable to use the butadiene rubber alone, or the butadiene rubber and the natural rubber in combination. Since the butadiene rubber has a small temperature dependency such as stiffness among the diene rubbers, the temperature dependency such as the rigidity of the high damping member is further reduced, and a highly damped member having more stable characteristics in a wide temperature range can be formed. Particularly, it is preferable to use the butadiene rubber alone to maximize the above effects.

However, according to the present invention, since the temperature dependency such as rigidity of the high-damping member can be reduced by mixing the liquid homopolymer as the liquid rubber at the above-mentioned ratio, the natural rubber can be used alone , Or even when used in combination with butadiene rubber, it is possible to form a highly damped member having a sufficiently low temperature dependency.

Thereafter, when a general-purpose natural rubber is used as the diene-based rubber, the productivity of the high-damping composition and the high-damping member may be improved and the production cost may be lowered.

The proportion of the two rubbers in the combination of the butadiene rubber and the natural rubber is not particularly limited, but the proportion of the butadiene rubber in the total amount of the two rubbers is preferably 30 mass% or more, It is preferable in further improving the effect of reducing dependency.

<Filler>

As the filler, at least one selected from the group consisting of silica and carbon black is used.

<Silica>

As the medium silica, any of wet process silica and dry process silica classified according to the production method may be used. Considering that the silica has a BET specific surface area of at least 100 m 2 / g, more preferably at least 120 m 2 / g, particularly at least 200 m 2 / g, in view of improving the effect of improving the damping performance of the high- And is preferably not more than 400 m 2 / g, more preferably not more than 300 m 2 / g, particularly preferably not more than 250 m 2 / g. The BET specific surface area is represented by a value measured by a vapor-phase adsorption method using nitrogen gas as the adsorbing gas, using, for example, a rapid surface measurement apparatus SA-1000 manufactured by Shibata Kagaku Kai Kogyo Co.,

Examples of the silica include NipSil (Nipil) KQ (BET specific surface area: about 230 m 2 / g) manufactured by Tosoh Silica Co., Ltd. and the like.

<Carbon black>

As the carbon black, one kind or two or more kinds of carbon black which can function as a filler among various carbon black classified according to the production method and the like can be used.

Among them, carbon black having a relatively large particle diameter such as FEF and GPF is preferable as the carbon black in consideration of imparting high workability to the high-damping composition while maintaining a good reinforcing effect.

&Lt; Mixing ratio of filler &

The mixing ratio of the filler is preferably not less than 125 parts by mass, particularly not less than 135 parts by mass, and not more than 180 parts by mass, particularly not more than 160 parts by mass, particularly not more than 140 parts by mass, per 100 parts by mass of the diene rubber.

If the mixing ratio of the filler is less than the above range, there is a fear that the effect of imparting a good damping performance to the high damping member due to the compounding of the filler may not be obtained.

On the other hand, if it exceeds the above range, for example, even if the liquid homopolymer is blended at the above ratio, the rigidity at the time of kneading the high-damping composition becomes too high, and the workability of the high damping member may be deteriorated.

The compounding ratio is the compounding ratio when only one type of silica or carbon black is used as the filler, and when two or more kinds of the silica or carbon black are used in combination, the compounding ratio is the total.

When silica and carbon black are used in combination as the filler, it is preferable to set the mixing ratio of silica serving as a damping property-imparting agent and carbon black as species.

Specifically, for example, the blending ratio of silica is preferably 120 parts by mass or more, particularly 130 parts by mass or more, and more preferably 175 parts by mass or less, especially 155 parts by mass or less, particularly 135 parts by mass or less per 100 parts by mass of the diene rubber . Further, it is preferable that the blend ratio of the carbon black is set to the balance excluding the compounding ratio of the above silica filler from the blend ratio of the above-mentioned filler.

<Liquid Homopolymer>

As the liquid homopolymer, at least one selected from the group consisting of liquid IR and liquid BR is used.

Examples of the liquid IR include Kurafren (registered trademark) LIR-30 and LIR-50 manufactured by Kuraray Co., Ltd. Examples of the liquid phase BR include Kuraprene LBR-300, LBR-305 and LBR-307 manufactured by Kuraray Co., Ltd.

Particularly in terms of damping performance, liquid IR is preferred.

The mixing ratio of the liquid homopolymer should be at least 31 parts by mass per 100 parts by mass of the diene rubber.

When the blend ratio is less than the above range, the stiffness of the base polymer due to the blending of the liquid homopolymer is lowered, and the viscosity at the time of kneading the high-attenuating composition is lowered, whereby the effect of imparting good workability to the high- It is because there is not.

On the other hand, according to the present invention, it is possible to selectively use at least one liquid homopolymer of the two liquid rubber as the liquid rubber, and to set the mixing ratio within the above range, the damping performance is excellent and the temperature dependency It becomes possible to form a high-damping member having a stable characteristic over a wide temperature range, and it is also possible to provide a high-damping composition excellent in workability.

In addition, when the compounding ratio is excessively large, temperature dependence such as rigidity becomes large, although a liquid homopolymer is selectively used, and there is a possibility that a high-damping member having stable characteristics in a wide temperature range can not be formed. In addition, the stiffness of the base polymer is too low to prevent the temperature rise at the time of kneading, and as a result, it takes a long time to knead the high-damping composition, which may lower the workability.

Therefore, the blending ratio of the liquid homopolymer is preferably 82 parts by mass or less per 100 parts by mass of the diene rubber even within the above range.

In view of further improving these effects, the blending ratio of the liquid homopolymer is preferably 35 parts by mass or more, particularly preferably 50 parts by mass or more, more preferably 80 parts by mass or less, per 100 parts by mass of the diene rubber, , Particularly preferably not more than 60 parts by mass.

When the mixing ratio of the filler is within the range of 125 parts by mass or more and 180 parts by mass or less per 100 parts by mass of the diene rubber as described above, the mixing ratio of the liquid polymer is preferably 25 parts by mass or more per 100 parts by mass of the total amount of the filler , Particularly 35 parts by mass or more, particularly preferably 40 parts by mass or more, more preferably 60 parts by mass or less, particularly preferably 45 parts by mass or less.

This further improves the workability of the high-damping composition, further improves the damping performance of the high-damping member, further reduces the temperature dependency such as rigidity and forms a high-damping member having stable characteristics over a wider temperature range can do.

<Alicyclic hydrocarbon resin>

The alicyclic hydrocarbon resin functions to lower the rigidity of the base polymer together with the liquid homopolymer and lower the viscosity at the time of kneading the high-damping composition, thereby imparting good workability to the high-damping composition. Particularly when the blending ratio of the liquid homopolymer is small or not in the above range, it is effective to blend the alicyclic hydrocarbon resin to assist the processability of the high-damping composition.

However, since the alicyclic hydrocarbon resin has a large temperature dependency such as hardness, when a large amount of the alicyclic hydrocarbon resin is blended, the temperature dependency such as rigidity becomes large, and there is a fear that a high-damping member having stable characteristics in a wide temperature range can not be formed.

Therefore, even if the high-damping composition basically does not contain or contains alicyclic hydrocarbon resin, it is preferable that the blend ratio thereof is 25 parts by mass or less, particularly 10 parts by mass or less, per 100 parts by mass of the diene rubber.

Examples of the alicyclic hydrocarbon resin include dicyclopentadiene-based petroleum resins.

Examples of the dicyclopentadiene-based petroleum resin include Marukaetsu (registered trademark) M-890A (softening point: 105 ° C) manufactured by Maruzen Sekiyu Kagaku Co., Ltd. and the like.

&Lt; Other components >

In the high-damping composition of the present invention, a crosslinking component or the like for crosslinking the diene rubber may be further blended in an appropriate ratio.

As the crosslinking component, various crosslinking components capable of crosslinking the diene rubber can be used. It is particularly preferable to use a crosslinking component of sulfur vulcanizing system. Examples of the crosslinking component of the sulfur vulcanization system include a combination of a vulcanizing agent, a vulcanization promoting agent and a vulcanization promoting assistant. It is preferable to combine a vulcanizing agent, a vulcanization promoting agent and a vulcanization promoting assistant which do not cause a problem that the rubber elasticity of the high-damping member increases and the damping performance is lowered.

Examples of the vulcanizing agent include sulfur and sulfur-containing organic compounds. Sulfur is particularly preferred.

Examples of the vulcanization accelerator include sulfenamide-based vulcanization accelerators and thiuram-based vulcanization accelerators. Since the mechanism of promoting the vulcanization is different depending on the kind of the vulcanization accelerator, it is preferable to use two or more kinds of vulcanization accelerator in combination.

As the sulfenamide-based vulcanization accelerator, there may be mentioned, for example, Norseller (registered trademark) NS [N-tert-butyl-2-benzothiazolylsulfenamide] manufactured by Ouchi Shinko Chemical Industry Co., Examples of the thiuram-based vulcanization accelerator include Roceller-TBT (tetrabutylthiuram disulfide) manufactured by Ouchi Shinko Chemical Industries, Ltd. and the like.

Examples of the vulcanization accelerating auxiliary include zincification and stearic acid. It is usually preferable to use the two as a vulcanization accelerator.

The mixing ratio of the vulcanizing agent, the vulcanization accelerating agent and the vulcanization accelerating assistant may be appropriately adjusted according to the characteristics such as different damping performance and rigidity depending on the use of the high-damping member.

Various additives such as a silane compound, a coumarone indene resin, and an anti-aging agent may be further added to the high-damping composition of the present invention, if necessary, in an appropriate ratio.

Examples of the silane compound include various silane compounds represented by the formula (a) and capable of functioning as a dispersing agent for silica such as a silane coupling agent and a silylating agent.

In the above formula, at least one of R ¹ , R ² , R ³ and R ⁴ represents an alkoxy group. Provided that R ¹ , R ² , R ³ and R ⁴ are not simultaneously an alkoxy group, and the other represents an alkyl group or an aryl group.

Particularly preferred are alkoxysilanes such as hexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane and diphenyldimethoxysilane.

Examples of the silane compound include KBE-103 (phenyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The compounding ratio of the silane compound is not particularly limited, but is preferably 5 parts by mass or more, and more preferably 20 parts by mass or less, per 100 parts by mass of the silica.

Examples of the coumarone indene resin include various coumarone indene resins that contain a polymer of coumarone and indene and have a relatively low molecular weight of about 1000 or less in average molecular weight and can function as a softener.

As the coumarone indene resin, for example, Nitto Resin (registered trademark) KUMARON G-90 (average molecular weight: 770, softening point: 90 占 폚, acid value: 1.0 KOH mg / g or less, manufactured by Nitto Kagaku Co., , A hydroxyl value of 25 KOH mg / g, a bromine number of 11 g / 100 g, and a molecular weight of 10 g / 100 g, g, 100 g of V-120S (average molecular weight: 960, average molecular weight: 960, softening point: 120 캜, acid value: 1.0 KOH mg / g or less, hydroxyl value: 30 KOH mg / , Softening point: 120 占 폚, acid value: 1.0 KOH mg / g or less, hydroxyl value: 30 KOH mg / g, bromine value 7 g / 100 g].

The mixing ratio of the coumaroneindene resin is not particularly limited, but is preferably 5 parts by mass or more, and more preferably 20 parts by mass or less, per 100 parts by mass of the diene rubber.

As the anti-aging agent, for example, one kind or two or more kinds of various antioxidants such as benzimidazole type, quinone type, polyphenol type and amine type can be mentioned. In particular, it is preferable to use a benzimidazole-based antioxidant and a quinone-based antioxidant in combination.

Examples of the benzimidazole antioxidant include Nocrack (registered trademark) MB [2-mercaptobenzimidazole] manufactured by Ouchi Shinko Chemical Industry Co., Ltd., and the like. Examples of the quinone antioxidant include Antizene FR (aromatic ketone-amine condensate) manufactured by Marui Chemical Co., Ltd. and the like.

The mixing ratio of the two antioxidants is not particularly limited, but the benzimidazole antioxidant is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or less, per 100 parts by mass of the diene rubber. The quinone antioxidant is preferably 0.5 part by mass or more, more preferably 5 parts by mass or less, per 100 parts by mass of the diene rubber.

Examples of the high-damping member that can be manufactured using the high-damping composition of the present invention include an anti-vibration damper built in the foundation of a building such as a building, a damper for seismic control (vibration control) embedded in the structure of the building, Vibration-controlling members of cables such as cable-stayed girder bridges, vibration-proof members such as industrial machines and aircraft, automobiles, and railroad cars, vibration-proof members such as computers and their peripheral devices, household electric appliances, And the like.

According to the present invention, it is possible to obtain a high-damping member having excellent damping performance suitable for each of the above-mentioned uses by adjusting the kinds and combinations and blending ratios of the diene rubber, silica, liquid rubber, alicyclic hydrocarbon resin and various other components have.

In particular, when the damper for seismic control of a building as a high-damping member is formed by using the high-damping composition of the present invention as a forming material, since the damper for seismic control has excellent damping performance, The quantity can be reduced. Further, since the temperature dependency of stiffness and the like is small, the damper can be installed in the vicinity of the outer wall of a building having a large temperature difference, for example.

[Example]

&Lt; Example 1 >

(Preparation of high-damping composition)

60 parts by mass of a liquid IR (LIR-50, manufactured by Kuraray Co., Ltd.) as a liquid homopolymer, 100 parts by mass of a natural rubber (SMR (Standard Malaysian Rubber) -CV60) 135 parts by mass of NipSil (Nipil) KQ, manufactured by Nippon Pneumatic Mfg. Co., Ltd.) and 3 parts by mass of carbon black (FEF, manufactured by Tokai Carbon Co., Ltd.) and the components shown in the following Table 1 were mixed, And kneaded to prepare a high-damping composition.

The compounding ratio of the liquid IR was 60 parts by mass per 100 parts by mass of the diene rubber, and 43.5 parts by mass per 100 parts by mass of the total amount of the silica and carbon black as fillers.

ingredient Mass part Silane compound 23 Benzimidazole type antioxidant 2 A quinone antioxidant 2 Two kinds of zinc oxide 4 Stearic acid One Coumarone indene resin 10 5% oil treated powder sulfur 1.58 Sulfenamide type vulcanization accelerator One Tiuram-based vulcanization accelerator 0.7

Each component in the table is as follows.

Silane compound: phenyltriethoxysilane, KBE-103 (product of Shin-Etsu Chemical Co., Ltd.)

Benzimidazole antioxidant: 2-mercaptobenzimidazole, Norcrack MB manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.

Quinone antioxidant: Antigen FR (manufactured by Maruyishikagakuhin Co., Ltd.)

Two kinds of zinc oxide: Manufactured by Mitsui Kinzoku Kogyo Co., Ltd.

Stearic acid: "Tsubaki" manufactured by Nichiyu Co.,

Coumarone indene resin: softening point 90 占 폚, AESCULON (registered trademark) G-90 manufactured by Nitto Kagaku Co., Ltd.

5% Oil-treated powder Sulfur: Vulcanizing agent, manufactured by Tsurumi Kagaku Kogyo Co., Ltd.

Sulfene amide-based vulcanization accelerator: N-tert-butyl-2-benzothiazolyl sulfenamide, Nosella (registered trademark) NS manufactured by Ouchi Shinko Kagaku Kogyo Co.,

Touram type vulcanization accelerator: tetrabutyl thiuram disulfide, Noserler TBT-N manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.

&Lt; Example 2 >

A high-damping composition was prepared in the same manner as in Example 1 except that 100 parts by mass of butadiene rubber (UBEPOL (registered trademark) BR150L, manufactured by Ube Industries, Ltd.) was used as the diene rubber.

The compounding ratio of the liquid IR was 60 parts by mass per 100 parts by mass of the diene rubber, and 43.5 parts by mass per 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Example 3 >

Except that 70 parts by mass of a natural rubber (SMR (Standard Malaysian Rubber) -CV60) and 30 parts by mass of a butadiene rubber (UBEPOL (registered trademark) BR150L, manufactured by Ube Chemical Industries, Ltd.) In the same manner, a high-damping composition was prepared.

The compounding ratio of the liquid IR was 60 parts by mass per 100 parts by mass of the diene rubber, and 43.5 parts by mass per 100 parts by mass of the total amount of the silica and carbon black as fillers.

<Example 4>

100 parts by mass of butadiene rubber (UBEPOL (registered trademark) BR150L manufactured by Ube Chemical Industries, Ltd.) was used as the diene rubber, and 60 parts by mass of Liquid-phase BR (LBR-300, manufactured by Kuraray Co., A high-damping composition was prepared in the same manner as in Example 1. &lt; tb &gt; &lt; TABLE &gt;

The mixing ratio of the liquid BR was 60 parts by mass per 100 parts by mass of the diene rubber, and 43.5 parts by mass per 100 parts by mass of the total amount of silica and carbon black as fillers.

&Lt; Example 5 >

10 parts by weight of a dicyclopentadiene-based petroleum resin (Marukaetsu Yukagaku Marukaetsu M-890A (softening point: 105 占 폚) as an alicyclic hydrocarbon resin with a mixing ratio of liquid IR of 50 parts by mass, ] Was prepared in the same manner as in Example 1, except that 10 parts by mass of [

The compounding ratio of the liquid IR was 50 parts by mass per 100 parts by mass of the diene rubber, and 36.2 parts by mass with 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Example 6 >

A high damping composition was prepared in the same manner as in Example 5 except that the mixing ratio of the liquid IR was 35 parts by mass and the blending ratio of the dicyclopentadiene petroleum resin was 25 parts by mass.

The mixing ratio of the liquid IR was 35 parts by mass per 100 parts by mass of the diene rubber, and 25.4 parts by mass with 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Example 7 >

A high damping composition was prepared in the same manner as in Example 5 except that the blending ratio of the liquid IR was 60 parts by mass and the blending ratio of the dicyclopentadiene petroleum resin was 25 parts by mass.

The compounding ratio of the liquid IR was 60 parts by mass per 100 parts by mass of the diene rubber, and 43.5 parts by mass per 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Example 8 >

A high damping composition was prepared in the same manner as in Example 5 except that the blending ratio of the liquid IR was 80 parts by mass and the blending ratio of the dicyclopentadiene petroleum resin was 25 parts by mass.

The mixing ratio of the liquid IR was 80 parts by mass per 100 parts by mass of the diene rubber, and 58 parts by mass per 100 parts by mass of the total amount of silica and carbon black as fillers.

&Lt; Example 9 >

Except that 60 parts by mass of a liquid phase BR (LBR-300, manufactured by Kuraray Co., Ltd.) as a liquid homopolymer was blended and the mixing ratio of the dicyclopentadiene petroleum resin was changed to 25 parts by mass. A composition was prepared.

The mixing ratio of the liquid BR was 60 parts by mass per 100 parts by mass of the diene rubber, and 43.5 parts by mass per 100 parts by mass of the total amount of silica and carbon black as fillers.

&Lt; Comparative Example 1 &

A high damping composition was prepared in the same manner as in Example 5 except that the mixing ratio of the liquid IR was 15 parts by mass and the blending ratio of the dicyclopentadiene petroleum resin was 25 parts by mass.

The mixing ratio of the liquid IR was 15 parts by mass per 100 parts by mass of the diene rubber, and 10.9 parts by mass per 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Comparative Example 2 &

A high damping composition was prepared in the same manner as in Example 5 except that the blending ratio of the liquid IR was 25 parts by mass and the blending ratio of the dicyclopentadiene petroleum resin was 35 parts by mass.

The compounding ratio of the liquid IR was 25 parts by mass per 100 parts by mass of the diene rubber, and 18.1 parts by mass with 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Comparative Example 3 &

Except that 35 parts by mass of a liquid SBR (RICON (registered trademark) 100 manufactured by Satomarc Corporation), which is a liquid phase copolymer, was used in place of the liquid IR, and the mixing ratio of the dicyclopentadiene petroleum resin was changed to 25 parts by mass To prepare a high-damping composition.

The mixing ratio of the liquid SBR was 35 parts by mass per 100 parts by mass of the diene rubber and 25.4 parts by mass per 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Comparative Example 4 &

Except that 35 parts by mass of liquid NBR (Nipol (registered trademark) 1312, manufactured by Nippon Zeon Co., Ltd.) as a liquid phase copolymer instead of liquid IR was used and the blending ratio of dicyclopentadiene petroleum resin was changed to 25 parts by mass, A high-damping composition was prepared.

The mixing ratio of the liquid NBR was 35 parts by mass per 100 parts by mass of the diene rubber, and 25.4 parts by mass with 100 parts by mass of the total amount of the silica and carbon black as fillers.

&Lt; Processability evaluation &

Each of the components constituting the high-damping composition of each of the examples and comparative examples was kneaded by using an airtight kneader as described above to evaluate the processability when the high-damping composition was prepared according to the following criteria.

?: It was possible to knead with the kneading time equivalent to that of Example 6. Workability is good.

×: The internal / external kneading time was required to be about 2% of that in Example 6. Poor processability.

<Attenuation characteristic test>

(Preparation of test body)

The high damping composition prepared in Examples, Comparative Examples and Conventional Examples was extruded into a sheet form and then punched to manufacture a disk 1 (5 mm in diameter × 25 mm in diameter) as shown in FIG. 1, 1) having a thickness of 6 mm, a length of 44 mm, and a width of 44 mm was superposed on both sides of the front and back surfaces of the panel 1 with a vulcanized adhesive interposed therebetween to form an original plate 1 And the original plate 1 was vulcanized and bonded to the two steel plates 2 to prepare a specimen 3 for evaluating the damping characteristics as a model of the high attenuation member.

(Displacement test)

Two test pieces 3 are prepared as shown in Fig. 2 (a), and the two test pieces 3 are bolted to one central fixing jig 4 via one steel plate 2 One of the left and right fixing jigs 5 was fastened to the other steel plate 2 of each test body 3 with bolts. Then, the center fixing jig 4 is bolted to a fixing arm 6 on the upper side of a testing machine (not shown) through a joint 7, and two left and right fixing jigs 5 are fixed to the lower side movable table 8 with a bolt through a joint 9.

Next, in this state, the movable plate 8 is displaced so as to push up the movable arm 6 in the direction of the fixed arm 6 as shown by white arrows in the figure, The movable bar 8 is deformed in the direction orthogonal to the stacking direction of the test piece 3 as shown in Fig. And the operation of returning to the state shown in Fig. 2 (a) is set as one cycle. When the disk 1 of the test piece 3 is repeatedly deformed or vibrated A hysteresis loop H (see Fig. 3) showing the relationship between the displacement (mm) of the disk 1 in the direction perpendicular to the stacking direction of the test piece 3 and the load N was obtained.

The measurement is carried out for 3 cycles under the environment of a temperature of 23 캜 to obtain the third value. The maximum amount of displacement was set such that the amount of displacement of the two steel plates 2 sandwiching the original plate 1 in the direction perpendicular to the stacking direction was 100% of the thickness of the original plate 1.

(Keq (N / mm)) of a straight line L ₁ indicated by a solid line in the figure, which connects the maximum displacement point and the minimum displacement point in the hysteresis loop H shown in Fig. 3 obtained by the above measurement, (1) from the slope Keq (N / mm), the thickness T (mm) of the disk 1 and the cross sectional area A (mm ² ) of the disk 1, And the modulus of elasticity (Geq ₂₃ (N / mm ² )) was obtained.

In addition, the amount of absorbed energy? W expressed by the entire surface area of the hysteresis loop H shown by the oblique line in FIG. 3 and the straight line L ₁ shown by the dotted line in FIG. 3, the horizontal line and the straight line L ₁ of the graph, and the hysteresis loop (Heq ₂₃ ) was obtained from the elastic strain energy W expressed by the surface area of the area surrounded by the water line L ₂ that descended to the abscissa from the point of intersection with the intersection point H of the center of gravity D ₁ . As the equivalent attenuation constant (Heq ₂₃ ) increases, the test body 3 can judge that the attenuation performance is excellent. Here, Heq ₂₃ is evaluated as poor damping performance that is less than the attenuation performance good, 0.25 or more 0.25.

Further, by carrying out the measurement under the temperature of 0 ℃ environment to obtain the equivalent shear modulus ^{_{(Geq 0 (N / ㎜ 2}} )), non-(Geq with Geq ₂₃ (N / ㎜ ²⁾ in the previous 23 ℃ ₀ / Geq ₂₃ ) was obtained and the temperature dependency of the stiffness was evaluated according to the following criteria.

?: The ratio (Geq ₀ / Geq ₂₃ ) was 1.8 or less. Temperature dependency small.

X: ratio (Geq ₀ / Geq ₂₃ ) exceeded 1.8. High temperature dependence.

The results are shown in Tables 2 to 4.

From the results of Examples 1 to 9, Comparative Example 3 and Comparative Example 4 of Tables 2 to 4, it was found that liquid-phase homopolymers liquid IR and liquid BR were used as the liquid rubber, and liquid SBR and liquid NBR The temperature dependency such as the rigidity of the high damping member can be reduced.

However, from the results of Examples 1 to 9, Comparative Examples 1 and 2, in order to improve the damping performance of the high-damping member and reduce the temperature dependency such as rigidity while maintaining good processability, It was found that the blend ratio was required to be 31 parts by mass or more per 100 parts by mass of the diene rubber.

From the results of Examples 1, 5 and 6 to 8, in order to further improve the above effects, the mixing ratio of the liquid homopolymer is preferably 35 mass% or less per 100 mass parts of the diene rubber More preferably not less than 50 parts by mass, particularly preferably not more than 82 parts by mass, especially not more than 80 parts by mass, particularly preferably not more than 60 parts by mass, more preferably not less than 25 parts by mass, per 100 parts by mass of the total amount of the filler, More preferably not less than 40 parts by mass, more preferably not more than 60 parts by mass, particularly preferably not more than 45 parts by mass.

From the results of Example 1, Example 5, Example 6, and Comparative Example 2, in order to further improve the above effect, the mixing ratio of the dicyclopentadiene-based petroleum resin as the alicyclic hydrocarbon resin was set to 0 part by mass, It is preferable that no pendant hydrocarbon resin be blended, and when blended, it is preferable that the content is 25 parts by mass or less per 100 parts by mass of the diene rubber.

From the results of Example 2, Example 4, and Examples 7 and 9, it can be seen that almost the same effects can be obtained as the liquid homopolymer in both liquid IR and liquid BR, but liquid IR is particularly preferable And it was found.

From the results of Examples 1 to 3, it was found that it is preferable to use the butadiene rubber alone or in combination with natural rubber as the diene rubber in order to further improve the above effects. However, although it is not clear from the table, when the general-purpose natural rubber is used singly as the diene rubber, the productivity of the high-damping composition and the high-damping member can be improved and the production cost can be lowered.

1: Disc
2: Steel plate
3:
4: Center fixing jig
5: Left and right fixing jig
6: Fixed arm
7: Joint
8:
9: Joint
H: Hysteresis Loop
L ₁ : straight line
L ₂ : Repair
Keq: slope
W: Energy
ΔW: absorbed energy amount

Claims (7)

Based rubber selected from the group consisting of natural rubber and butadiene rubber,
At least one liquid homopolymer selected from the group consisting of a liquid isoprene rubber and a liquid butadiene rubber, and
At least one filler selected from the group consisting of silica and carbon black
As a high-damping composition,
The mixing ratio of the filler per 100 parts by mass of the diene rubber is not less than 125 parts by mass and not more than 180 parts by mass,
The mixing ratio of the liquid homopolymer per 100 parts by mass of the diene rubber is preferably not less than 35 parts by mass and not more than 80 parts by mass,
The blending ratio per 100 parts by mass of the total amount of the filler of the liquid homopolymer is not less than 35 parts by mass and not more than 60 parts by mass,
Wherein the high-damping composition contains no alicyclic hydrocarbon resin. delete delete The high-damping composition according to claim 1, wherein the silica is a silica having a BET specific surface area of 120 m 2 / g or more and 300 m 2 / g or less. The high-damping composition according to claim 1, wherein the diene rubber is a butadiene rubber alone or a combination of a butadiene rubber and a natural rubber. The high-damping composition according to claim 1, wherein natural rubber is used alone as the diene-based rubber. The high-damping composition according to claim 1, which is used as a material for forming a damper for seismic control of a building.

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