TW201311824A - High-damping composition - Google Patents

Abstract

A high damping composition is provided, which not only can form a high damping component having excellent damping property, toughness etc with lower temperature dependency, and therefore stability in a wide temperature range, but has excellent workability. The high damping composition is formed by adding a liquid homopolymer to a dienic rubber as a matrix polymer and a silica and/or a carbon black as a filler. The liquid homopolymer is 31 parts by mass in each 100 parts by mass of the dienic rubber. The liquid homopolymer is at least one selected from the group consisting of a liquid isoprene rubber and a liquid butadiene rubber.

Description

High attenuation composition

The present invention relates to a high-attenuation composition which is a raw material for a high-attenuation member that mitigates and absorbs the transmission of vibration energy.

For example, in areas such as high-rise buildings or bridges, industrial machinery, aircraft, automobiles, rail vehicles, computers or peripheral devices, household appliances, and even automotive tires, in order to alleviate and absorb the transmission of vibrational energy. That is, in order to perform vibration-free, vibration-proof, vibration-damping, vibration-proof, etc., a high-attenuation member containing rubber or the like as a base polymer is used.

The high-attenuation member improves the attenuation performance in order to increase the hysteresis loss when the vibration is applied, that is, the vibration energy is efficiently and rapidly attenuated, usually by including the above-mentioned base polymer, and the loss tangent The peak of tan δ is adjusted to form a high attenuation composition entering the temperature range of use of the high attenuation member.

The high-attenuation member is formed by forming the above-described high-attenuation composition into a predetermined three-dimensional shape and vulcanizing the base polymer when it is a rubber.

A diene rubber can be suitably used as the base polymer. The above diene rubber has an advantage that the glass transition temperature does not exist in the vicinity of room temperature (2 ° C to 35 ° C), so that the temperature dependency of the rigidity in the vicinity of the room temperature in the most general use temperature region is changed. Small, high attenuation members that exhibit stable characteristics over a wide temperature range.

It is known that a high-attenuation composition is prepared by adding a cerium oxide and a decane compound (a sulfonating agent) as an attenuating agent to a base polymer such as the above-mentioned diene rubber, and kneading the cerium oxide and a decane compound to prepare a mixture. A high attenuation composition or the like (refer to Patent Document 1, etc.).

However, in the prior high attenuation composition, the attenuation performance of the high attenuation member is not sufficiently improved.

In order to further improve the attenuation performance of the high-attenuation member, it is considered that the proportion of the cerium oxide is further increased. However, the high-attenuation composition in which a large amount of cerium oxide is formulated has a problem that the viscosity at the time of kneading is increased, the workability is lowered, and the above-mentioned high-attenuation composition for producing a high-attenuation member having a desired three-dimensional shape is kneaded, It is not easy to form the above-described three-dimensional shape.

Therefore, for example, it has been studied to prepare a liquid rubber as a component which lowers the rigidity of the base polymer and lowers the viscosity at the time of kneading of the high-attenuation composition, thereby imparting good workability to the high-attenuation composition (for example, refer to Patent Document 2) , Patent Document 3, etc.).

However, there is a problem in that the temperature dependence of the rigidity of the high-attenuation member or the like is increased depending on the type or the proportion of the liquid rubber, and it is not possible to form a high-attenuation member having stable rigidity in a wide temperature range.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 7-41603

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-30016

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2011-68850

SUMMARY OF THE INVENTION An object of the present invention is to provide a high-attenuation member having the following properties: not only a high-attenuation member which is excellent in attenuation performance but also has low temperature dependency such as rigidity and stable characteristics over a wide temperature range, and is processed. Excellent also.

The inventors first studied the types of liquid rubber.

As a result, it has been found that when a liquid homopolymer such as liquid isoprene rubber (liquid IR) or liquid butadiene rubber (liquid BR) is used as the liquid rubber, the liquid is used. Depending on the case of a liquid homopolymer such as styrene butadiene rubber (liquid SBR) or liquid acrylonitrile butadiene rubber (liquid NBR), temperature dependence of rigidity such as high attenuation member can be achieved. Drastically reduced.

Therefore, as a result of further research on the blending ratio of the above liquid homopolymer, the present invention has been completed.

That is, the present invention is a high-attenuation composition in which at least 1 selected from the group consisting of liquid isoprene rubber and liquid butadiene rubber is formulated in a diene rubber as a base polymer. a high-attenuation composition comprising a liquid homopolymer and at least one filler selected from the group consisting of cerium oxide and carbon black, wherein the high-attenuation composition is characterized in that the liquid is The blending ratio of the polymer per 100 parts by mass of the diene rubber is 31 parts by mass or more.

In the present invention, the proportion of the liquid homopolymer in each of 100 parts by mass of the diene rubber is limited to 31 parts by mass or more, because if it is less than the above range, the liquid solution can not be obtained by blending the liquid. The viscosity of the base polymer by the polymer is lowered to lower the viscosity of the high-attenuation composition during kneading, thereby imparting good workability to the highly attenuating composition.

According to the present invention, at least one of the above two kinds of liquid homopolymers is selectively used as the liquid rubber, and the blending ratio is set within the above range, whereby the following high-attenuation composition can be provided: It is possible to form a high-attenuation member which is excellent in attenuation performance, has low temperature dependency such as rigidity, and has stable characteristics over a wide temperature range, and is excellent in workability.

However, it is considered to further improve the attenuation performance of the high-attenuation member, and to form a high-attenuation member which makes the temperature dependency of rigidity and the like smaller and has stable characteristics over a wider temperature range, or further improves the processing of the high-attenuation composition. The ratio of the filler to the diene rubber per 100 parts by mass is preferably 125 parts by mass or more, 180 parts by mass or less, and the total amount of the liquid homopolymer per 100 parts by mass of the filler. The blending ratio is 25 parts by mass or more and 60 parts by mass or less.

In addition, when a high-attenuation member having stable characteristics in a wider temperature range is formed in consideration of a lower temperature dependency such as rigidity, the high-attenuation composition is preferably a grease having high temperature dependency such as hardness. The cycloolefin resin or the alicyclic hydrocarbon resin is contained in an amount of 25 parts by mass or less per 100 parts by mass of the diene rubber and the alicyclic hydrocarbon resin.

The cerium oxide in the above filler is preferably cerium oxide having a BET specific surface area of 120 m ² /g or more and 300 m ² /g or less. By using cerium oxide having a BET specific surface area within the above range, the attenuation performance of the high-attenuation member can be further improved without affecting the range of the processability of the high-attenuation composition.

It is preferable to use butadiene rubber alone or a butadiene rubber together with natural rubber as the above diene rubber. Since the butadiene rubber has a small temperature dependency such as rigidity in the diene rubber, the temperature dependency of the rigidity of the high attenuation member can be further reduced, and it can be formed in a wider temperature range. Characteristic high attenuation component.

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

When the high-attenuation composition of the present invention is used as a forming material to form a damping damper for a building as a high-attenuating member, the damping damper can be reduced to one building due to excellent attenuation performance. The number of the above-mentioned shock dampers incorporated in the object. Further, since the temperature dependency such as rigidity is small, the damper can be provided even in the vicinity of a wall other than a building having a large temperature difference.

[Effects of the Invention]

According to the present invention, it is possible to provide a high-attenuation member which is excellent in attenuation performance and which has low temperature dependency such as rigidity and stable characteristics over a wide temperature range, and the height is high. The workability of the attenuating composition is also excellent.

The present invention is a high-attenuation composition which is formulated with a liquid homopolymer in a diene rubber as a base polymer, and is selected from the group consisting of liquid isoprene rubber and liquid butadiene rubber. At least one of the fillers and the filler are selected from the group consisting of at least one of a group consisting of cerium oxide and carbon black, and the high-attenuating composition is characterized by the liquid homopolymer The blending ratio per 100 parts by mass of the diene rubber is 31 parts by mass or more.

<Diene rubber>

The diene rubber may, for example, be one or more selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, and styrene butadiene rubber.

The above diene rubber has the advantage that the glass transition temperature does not exist in the vicinity of room temperature (2 ° C to 35 ° C) as described above, so that the rigidity in the vicinity of the room temperature in the most general use temperature region is the same. The temperature dependence becomes small, and a high attenuation member which exhibits stable characteristics in a wide temperature range can be formed.

As the above diene rubber, it is preferred to use butadiene rubber alone or in combination with natural rubber. Since the temperature dependence of the rigidity of the butadiene rubber in the diene rubber is also small, the temperature dependency of the rigidity of the high attenuation member and the like can be further reduced, and the formation can be more stable in a wide temperature range. Characteristic high attenuation component. In particular, it is preferred to use butadiene rubber alone to maximize the above effects.

However, according to the present invention, the liquid homopolymer is blended in the above ratio as a liquid rubber, whereby the temperature dependency of the rigidity of the high-attenuating member can be made small as described above, and therefore, even if it is used alone, natural Rubber or a butadiene rubber is used as a diene rubber, and a high attenuation member having a sufficiently small temperature dependency can be formed.

Further, when a general-purpose natural rubber is used as the diene rubber, the productivity of the high-attenuation composition or the high-attenuation member can be improved, and the production cost can be lowered.

However, in the series of the combination of the butadiene rubber and the natural rubber, the mixing ratio of the two rubbers is not particularly limited, but the effect of lowering the temperature dependency of the rigidity of the high-attenuating member is further improved. The proportion of the butadiene rubber in the total amount of the rubber is preferably 30% by mass or more.

<filler>

The filler is at least one selected from the group consisting of cerium oxide and carbon black.

(cerium oxide)

As the cerium oxide, any of the wet cerium oxide and the dry cerium oxide classified according to the production method thereof can be used. Further, as the cerium oxide, in order to improve the function of the filler as a filler and to improve the attenuation performance of the high-attenuation member, it is preferable that the BET specific surface area is 100 m ² /g or more and 120 m ² /g or more. More preferably, it is 200 m ² /g or more of cerium oxide; preferably 400 m ² /g or less, 300 m ² /g or less, and particularly preferably cerium oxide of 250 m ² /g or less. The BET specific surface area is expressed by, for example, a rapid surface area measuring device SA-1000 manufactured by Shibata Chemical Instruments Industrial Co., Ltd., and is measured by a gas phase adsorption method using nitrogen gas as an adsorption gas. .

The above-mentioned ceria is, for example, NipSil KQ [BET specific surface area: about 230 m ² /g] manufactured by Tosoh Silica Corporation.

(carbon black)

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

In particular, carbon black is preferably used as the carbon black, and a carbon black having a large particle diameter such as FEF or GPE is preferable as the carbon black is considered to have a high reinforcing property while maintaining a good reinforcing effect.

(mixing ratio of filler)

The blending ratio of the filler is preferably 125 parts by mass or more, particularly preferably 135 parts by mass or more, preferably 180 parts by mass or less, 160 parts by mass or less, and particularly preferably 140, per 100 parts by mass of the diene rubber. Below the mass.

When the blending ratio of the filler is less than the above range, there is a possibility that the effect of imparting good attenuation performance to the high-attenuation member due to the blending agent cannot be obtained.

On the other hand, when it exceeds the above range, even if the liquid homopolymer is blended in the above ratio, the rigidity at the time of kneading of the highly attenuating composition is too high, and the workability of the high-attenuating member is lowered.

Further, when only one of cerium oxide or carbon black is used alone as a filler, the blending ratio is a blending ratio of cerium oxide or carbon black; and when two or more of the above cerium oxide or carbon black are used as a filler The blending ratio is the total blending ratio of the above.

When cerium oxide and carbon black are used in combination as a filler, it is preferable to use cerium oxide which functions as a damping property imparting agent, and carbon black is used as a filler to set the mixing ratio of both.

Specifically, for example, the blending ratio of cerium oxide is preferably 120 parts by mass or more, particularly preferably 130 parts by mass or more, preferably 175 parts by mass or less, per 100 parts by mass of the diene rubber. Below the mass part, it is particularly preferably 135 parts by mass or less. Further, the blending ratio of the carbon black is preferably set to the remainder of the blending ratio of the above-mentioned cerium oxide from the blending ratio of the filler described above.

<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 Kuraplene (registered trademark) LIR-30, LIR-50, and the like manufactured by Kuraray Co., Ltd., Japan. Further, examples of the liquid BR include Kuraplene LBR-300, LBR-305, and LBR-307 manufactured by Kuraray Co., Ltd., Japan.

In particular, liquid IR is preferred from the viewpoint of attenuation performance.

The compounding ratio of the liquid homopolymer is required to be 31 parts by mass or more per 100 parts by mass of the diene rubber and the liquid homopolymer.

The reason is that when the blending ratio is less than the above range, the rigidity of the base polymer is lowered by blending the liquid homopolymer, and the viscosity at the time of kneading of the high-attenuating composition is lowered, thereby giving the high Attenuates the effect of the composition's good attenuation properties.

According to the present invention, at least one of the above two kinds of liquid homopolymers is selectively used as the liquid rubber, and the blending ratio is set within the above range, whereby the following high-attenuation composition can be provided: It is possible to form a high-attenuation member which is excellent in attenuation performance, has low temperature dependency such as rigidity, and has stable characteristics over a wide temperature range, and is excellent in workability.

However, when the blending ratio is too large, regardless of the selective use of the liquid homopolymer, the temperature dependency of rigidity and the like becomes large, and there is a high attenuation member which cannot be formed in a wide temperature range and has stable characteristics. . Further, the rigidity of the base polymer is too low, which hinders the temperature rise during the kneading. As a result, it takes a long time for the kneading of the high-attenuating composition, and the workability is rather lowered.

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

However, in consideration of the above-described effects, the liquid homopolymer is preferably contained in an amount of 35 parts by mass or more per 100 parts by mass of the diene rubber, even if it is within the above range. It is preferably 50 parts by mass or more; preferably 80 parts by mass or less, and particularly preferably 60 parts by mass or less.

In addition, when the proportion of the filler is 100 parts by mass or more per 100 parts by mass of the diene rubber, and the filler is in the range of 180 parts by mass or less, the proportion of the liquid homopolymer is preferably per The total amount of the 100 parts by mass of the filler is 25 parts by mass or more, 35 parts by mass or more, particularly preferably 40 parts by mass or more, more preferably 60 parts by mass or less, and particularly preferably 45 parts by mass or less.

In this way, while further improving the workability of the high-attenuation composition, the attenuation performance of the high-attenuation member is further improved, and the temperature dependency such as rigidity is further reduced, so that it can be formed in a wider temperature range and is stable. Characteristic high attenuation component.

<Cycloaliphatic hydrocarbon resin>

The alicyclic hydrocarbon resin is used to lower the rigidity of the liquid homopolymer and the base polymer, to lower the viscosity during kneading of the high-attenuation composition, and to provide good workability to the high-attenuation composition. In particular, when the mixing ratio of the liquid homopolymer is small even in the above range, it is effective to blend the above-mentioned alicyclic hydrocarbon resin in terms of the workability of the highly attenuating composition.

However, since the temperature dependence of hardness and the like of the alicyclic hydrocarbon resin is large, the temperature dependency of rigidity and the like is increased when a large amount is blended, and there is a high attenuation member which cannot be formed in a wide temperature range and has stable characteristics. Hey.

Therefore, the high-attenuation composition contains substantially no alicyclic hydrocarbon resin, and even if it contains an alicyclic hydrocarbon resin, the blending ratio is preferably 25 mass per 100 parts by mass of the diene rubber and the alicyclic hydrocarbon resin. The amount is preferably 10 parts by mass or less.

The alicyclic hydrocarbon resin may, for example, be a dicyclopentadiene petroleum resin.

The above-mentioned dicyclopentadiene-based petroleum resin is, for example, Maruka Rez (registered trademark) M-890A (softening point: 105 ° C) manufactured by Maruzen Petrochemical Co., Ltd., and the like.

<Other ingredients>

In the highly attenuating 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. Particularly preferred is the use of a sulfur vulcanizing system crosslinking component. The sulfur vulcanization crosslinking component may be a combination of a vulcanizing agent, a vulcanization accelerator, and a vulcanization accelerating aid. It is particularly preferable to combine a vulcanizing agent, a vulcanization accelerator, and a vulcanization accelerating aid which are difficult to cause a problem in which the deterioration of the rubber elasticity of the high-attenuating member is lowered.

Examples of the vulcanizing agent include sulfur or a sulfur-containing organic compound. Particularly good is sulfur.

Examples of the vulcanization accelerator include a sulfinamide-based vulcanization accelerator and a thiuram-based vulcanization accelerator. Since the vulcanization accelerator has a different mechanism for promoting vulcanization depending on the type, it is preferred to use two or more kinds in combination.

In the sulfinamide-based vulcanization accelerator, for example, Nocceler (registered trademark) NS [N-t-butyl-2-benzothiazolylsulfinamide] manufactured by Ouchi Shinko Chemical Co., Ltd., and the like can be cited. Further, examples of the thiuram vulcanization accelerator include Nocceler TBT (tetrabutyl thiuram disulfide) manufactured by Ouchi Shinko Chemical Industry Co., Ltd., and the like.

Examples of the vulcanization accelerating aid include zinc white, stearic acid, and the like. It is generally preferred to use both as a vulcanization accelerating aid.

The blending ratio of the vulcanizing agent, the vulcanization accelerator, and the vulcanization accelerating aid may be appropriately adjusted depending on characteristics such as attenuation performance or rigidity which are different depending on the use of the high-attenuating member or the like.

In the high-attenuation composition of the present invention, various additives such as a decane compound, a sucrose-tank resin, and an anti-aging agent may be further blended in an appropriate ratio as needed.

In addition, examples of the decane compound include various decane compounds which can function as a dispersing agent of cerium oxide such as a decane coupling agent or a decylating agent represented by the formula (a).

[Chemical 1]

[wherein, at least one of R ¹ , R ² , R ³ and R ⁴ represents an alkoxy group. Wherein R ¹ , R ² , R ³ and R ⁴ are not simultaneously alkoxy groups, and the others represent an alkyl group or an aryl group].

Particularly preferred are alkoxydecanes such as hexyltrimethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, and diphenyldimethoxydecane.

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

The blending ratio of the decane compound is not particularly limited, but is preferably 5 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the cerium oxide.

Examples of the scented sputum-indene resin include various polymers which mainly contain a polymer of sorghum and strontium, a low molecular weight having an average molecular weight of about 1,000 or less, and which can function as a softening agent. .

For example, Nitto Resin (registered trademark) Kasuga 哢 G-90 manufactured by Nippon Paint Chemical Co., Ltd. (average molecular weight: 770, softening point: 90 ° C, acid value: 1.0 KOH mg/g or less) , hydroxyl value of 25 KOHmg / g, bromine number of 9 g / 100 g], G-100N [average molecular weight of 730, softening point of 100 ° C, acid value of 1.0 KOHmg / g or less, hydroxyl value of 25 KOHmg / g , bromine number 11 g / 100 g], V-120 [average molecular weight of 960, softening point of 120 ° C, acid value of 1.0 KOHmg / g or less, hydroxyl value of 30 KOHmg / g, bromine value of 6 g / 100 g], V-120S [average molecular weight of 950, softening point of 120 ° C, acid value of 1.0 KOHmg / g or less, hydroxyl value of 30 KOHmg / g, bromine value of 7 g / 100 g], etc. More than one species.

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

The anti-aging agent may, for example, be one or more of various anti-aging agents such as benzimidazole-based, anthraquinone-based, polyphenol-based, and amine-based. It is particularly preferred to use a benzimidazole-based anti-aging agent in combination with a lanthanide anti-aging agent.

Among them, the benzimidazole-based anti-aging agent is, for example, Nocrac (registered trademark) MB [2-mercaptobenzimidazole] manufactured by Ouchi Shinko Chemical Co., Ltd., and the like. Further, examples of the lanthanide anti-aging agent include Antigen FR [aromatic ketone-amine condensate] manufactured by Maruishi Chemicals Co., Ltd., and the like.

The blending ratio of the two anti-aging agents is not particularly limited, but it is preferably 0.5 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the diene rubber and the benzimidazole-based anti-aging agent. Moreover, it is preferable that the lanthanoid anti-aging agent is 0.5 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the diene rubber.

Examples of the high-attenuation member which can be produced by using the high-attenuation composition of the present invention include a vibration-damping damper incorporated in a foundation of a building such as a high-rise building, and a shock-proof built in a structure of a building. (Vibration) Damping members for cables such as dampers, suspension bridges or diagonal bridges, anti-vibration members for industrial machinery or aircraft, automobiles, rail vehicles, etc., computers or peripheral devices, or household appliances, etc. Anti-vibration members, tire surfaces for automobile tires, etc.

According to the present invention, by adjusting the type, combination, and blending ratio of the above diene rubber, cerium oxide, liquid rubber, alicyclic hydrocarbon resin, and other various components, it is possible to obtain an excellent one suitable for each of the above uses. High attenuation component for attenuation performance.

In particular, when the high-attenuation composition of the present invention is used as a forming material to form a shock damper for a building as a high-attenuation member, the damping device for the shock-damping device has excellent attenuation performance, and thus can be reduced to one building. The number of the above-mentioned shock dampers incorporated in the object. Further, since the temperature dependency such as rigidity is small, the damper can be provided even in the vicinity of a wall other than a building having a large temperature difference.

[Example]

<Example 1>

(modulation of high attenuation composition)

A liquid IR as a liquid homopolymer is prepared in 100 parts by mass of a natural rubber [SMR (Standard Malaysian Rubber)-CV60] as a base polymer [LIR-50 manufactured by Nippon Kuraray Co., Ltd.] 60 parts by mass of cerium oxide as a filler [NipSil KQ manufactured by Tosoh Silica Corporation] 135 parts by mass, carbon black [FEF, SEAST SQ manufactured by Tokaicarbon Co., Ltd.), 3 parts by mass, and as shown in Table 1 below. Each component was kneaded using a closed kneader to prepare a high attenuation composition.

The ratio of the liquid IR is 60 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 43.5 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

The components in the table are as follows.

Decane compound: phenyl triethoxy decane, KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.

Benzimidazole-based anti-aging agent: 2-mercaptobenzimidazole, Nocrac MB manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

Anti-aging agent: Antigen FR manufactured by Maruishi Chemical Co., Ltd.

2 kinds of zinc oxide: manufactured by Mitsui Metal Mining Co., Ltd.

Stearic acid: "Tsubaki" manufactured by Nippon Oil Co., Ltd.

Kasuga 哢-茚 resin: softening point is 90 ° C, ESCURON (registered trademark) G-90 manufactured by Nippon Chemical Co., Ltd.

5% oil treated powder sulfur: vulcanizing agent, manufactured by Tsurumi Chemical Industry Co., Ltd.

Sulfoamide-based vulcanization accelerator: N-t-butyl-2-benzothiazolylsulfinamide, Nocceler (registered trademark) NS manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

Qiulan vulcanization accelerator: tetrabutyl thiuram disulfide, Nocceler TBT-N manufactured by Ou Nei Xin Chemical Industry Co., Ltd.

<Example 2>

A high-attenuation 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 ratio of the liquid IR is 60 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 43.5 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Example 3>

70 parts by mass of natural rubber [SMR (Standard Malaysian Rubber)-CV60] and 30 parts by mass of butadiene rubber [UBEPOL (registered trademark) BR150L manufactured by Ube Industries, Ltd.) were used as the diene rubber. Example 1 was carried out in the same manner to modulate the high attenuation composition.

The ratio of the liquid IR is 60 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 43.5 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Example 4>

100 parts by mass of butadiene rubber [UBEPOL (registered trademark) BR150L manufactured by Ube Industries, Ltd.) was used as the diene rubber, and the liquid BR (LBR-300 manufactured by Kuraray Co., Ltd.) was blended with 60 mass. A high-attenuation composition was prepared in the same manner as in Example 1 except that the liquid homopolymer was used as a liquid homopolymer.

The ratio of the liquid BR is 60 parts by mass per 100 parts by mass of the diene rubber, and the liquid BR is 43.5 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Example 5>

The blending ratio of the liquid IR is 50 parts by mass, and a dicyclopentadiene-based petroleum resin (Maruka Rez (registered trademark) M-890A (softening point: 105 ° C) manufactured by Maruzen Petrochemical Co., Ltd.) is prepared. A high-attenuation composition was prepared in the same manner as in Example 1 except for the mass.

The ratio of the liquid IR is 50 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 36.2 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Example 6>

The high-attenuation composition was prepared in the same manner as in Example 5 except that the blending ratio of the liquid IR was 35 parts by mass, and the blending ratio of the dicyclopentadiene-based petroleum resin was changed to 25 parts by mass.

The ratio of the liquid IR is 35 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 25.4 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Example 7>

The high-attenuation 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-based petroleum resin was changed to 25 parts by mass.

The ratio of the liquid IR is 60 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 43.5 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Example 8>

The high-attenuation 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-based petroleum resin was changed to 25 parts by mass.

The ratio of the liquid IR is 80 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 58 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Example 9>

60 parts by mass of liquid BR (LBR-300 manufactured by Kuraray Co., Ltd.) was used as a liquid homopolymer, and the blending ratio of the dicyclopentadiene-based petroleum resin was 25 parts by mass, and Example 5 was carried out in the same manner to modulate the high attenuation composition.

The ratio of the liquid BR is 60 parts by mass per 100 parts by mass of the diene rubber, and the liquid BR is 43.5 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Comparative Example 1>

The high-attenuation composition was prepared in the same manner as in Example 5 except that the blending ratio of the liquid IR was 15 parts by mass, and the blending ratio of the dicyclopentadiene-based petroleum resin was changed to 25 parts by mass.

The ratio of the liquid IR is 15 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 10.9 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Comparative Example 2>

The high-attenuation composition was prepared in the same manner as in Example 5 except that the blending ratio of the liquid IR was changed to 25 parts by mass, and the blending ratio of the dicyclopentadiene-based petroleum resin was changed to 35 parts by mass.

The liquid IR ratio is 25 parts by mass per 100 parts by mass of the diene rubber, and the liquid IR is 18.1 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Comparative Example 3>

35 parts by mass of the liquid SBR (RICON (registered trademark) 100 manufactured by Sartomer Co., Ltd.) was substituted for the liquid IR, and the blending ratio of the dicyclopentadiene petroleum resin was 25 parts by mass. The high attenuation composition was prepared in the same manner as in Example 5 except that it was carried out.

The ratio of the liquid SBR is 35 parts by mass per 100 parts by mass of the diene rubber, and the liquid SBR is 25.4 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Comparative Example 4>

35 parts by mass of a liquid NBR (Nipol (registered trademark) 1312 manufactured by Zeon Co., Ltd.) was substituted for liquid IR, and the blending ratio of the dicyclopentadiene petroleum resin was set to 25 parts by mass. Other than the above, the high attenuation composition was prepared in the same manner as in Example 5.

The ratio of the liquid NBR is 35 parts by mass per 100 parts by mass of the diene rubber, and the liquid SBR is 25.4 parts by mass per 100 parts by mass of the total amount of the cerium oxide and the carbon black as a filler. .

<Processability Evaluation>

The workability in the case where the components of the high-attenuation composition constituting each of the above examples and the comparative examples were kneaded and the high-attenuation composition was prepared by using the closed kneading machine as described above was evaluated.

○: The kneading can be performed in the same kneading time as in the case of Example 6. Good processability.

×: A kneading time of about 20% or more compared with Example 6 is required. Poor processing.

<Attenuation characteristic test>

(production of test body)

The high-attenuation composition prepared in the examples, the comparative examples, and the previous examples was extruded into a thin plate shape and then pressed, and as shown in FIG. 1, a circular plate 1 (thickness 5 mm × diameter 25 mm) was produced, and the circular plate 1 was formed. The two sides of the back surface are respectively laminated with a rectangular flat plate-shaped steel plate 2 having a thickness of 6 mm × a length of 44 mm × a width of 44 mm via a vulcanization adhesive, and heated to 150 ° C while being pressed in the lamination direction to form a circle. The high-attenuation composition of the plate 1 was vulcanized, and the disk 1 and the two steel plates 2 were vulcanized, and a test body 3 for evaluation of the attenuation characteristics as a model of the high-attenuation member was produced.

(displacement test)

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

Next, in this state, as shown by the hollow arrow in the figure, the movable disk 8 is displaced in the direction of the fixed arm 6, and as shown in Fig. 2(b), the circle in the test body 3 is used. The plate 1 is in a state of being strain-deformed in a direction orthogonal to the lamination direction of the test body 3, and secondly from this state, as shown by a hollow arrow in the figure, the movable disk 8 is oriented opposite to the fixed arm 6. When the direction is pulled down, the displacement is returned to the state shown in FIG. 2( a ), and the above operation is performed as one cycle, and the disk 1 in the test body 3 is deformed and deformed, even when it is vibrated. The hysteresis loop H (see FIG. 3) indicates the relationship between the displacement amount (mm) of the disc 1 in the direction orthogonal to the lamination direction of the test body 3 and the load (N).

The measurement was carried out in an environment of a temperature of 23 ° C, and the above operation was carried out for 3 cycles to obtain the third value. In addition, the maximum displacement amount is set so that the amount of shift of the two steel sheets 2 that sandwich the circular plate 1 in the direction orthogonal to the laminated direction is 100% of the thickness of the circular plate 1.

Next, the maximum displacement point in the hysteresis loop H shown in FIG. 3 obtained by the above measurement is connected to the minimum displacement point, and the slope Keq of the straight line L ₁ indicated by the thick solid line in the figure is obtained. /mm), from the above slope Keq (N / mm), the thickness T (mm) of the circular plate 1, the cross-sectional area A (mm ² ) of the circular plate 1, according to the formula (1):

[Math 1]

The equivalent shear elastic modulus Geq ₂₃ (N/mm ² ) was obtained.

Further, the amount of absorbed energy ΔW (indicated by the total surface area of the hysteresis loop H) indicated by the oblique line in Fig. 3, and the elastic strain energy W represented by the square grid line in Fig. 3 (by the above-mentioned straight line L) _1. The horizontal axis of the graph, represented by the surface area of the region surrounded by the perpendicular line L ₂ perpendicular to the intersection of the straight line L ₁ and the hysteresis loop H, according to the formula (2):

[Math 2]

The equivalent decay constant Heq _{23 is obtained} . The larger the equivalent decay constant Heq ₂₃ is, the more excellent the attenuation performance of the test body 3 can be determined. Here, the case where the Heq ₂₃ is 0.25 or more is evaluated as the attenuation performance is good, and the case where the eq is less than 0.25 is evaluated as the deterioration of the attenuation performance.

Further, the above measurement was carried out in an environment at a temperature of 0 ° C to obtain an equivalent shear elastic modulus Geq ₀ (N/mm ² ), and the Geq ₂₃ (N/mm) at 23 ° C as described above was determined. ² ) The ratio of Geq ₀ /Geq ₂₃ and the temperature dependence of rigidity was evaluated based on the following criteria.

○: The ratio Geq ₀ /Geq ₂₃ is 1.8 or less. Temperature dependence is small.

×: The ratio Geq ₀ /Geq ₂₃ exceeds 1.8. Temperature dependence is large.

The above results are shown in Tables 2 to 4.

According to the results of Examples 1 to 9 of Comparative Tables 2 to 4, Comparative Example 3, and Comparative Example 4, it was found that a liquid homopolymer, liquid IR, liquid BR, was used as the liquid rubber, and liquid copolymerization was used. In the case of the liquid SBR or the liquid NBR, the temperature dependency of the rigidity of the high attenuation member or the like can be made small.

Further, according to the results of the examples 1 to 9, the comparative example 1, and the comparative example 2, it is necessary to improve the attenuation performance of the high-attenuation member while maintaining good workability, and to reduce the temperature dependency such as rigidity. The blending ratio of the liquid homopolymer is 31 parts by mass or more per 100 parts by mass of the diene rubber liquid homopolymer.

According to the results of the example 1, the example 5, and the example 6 to the example 8, it is understood that, in order to further enhance the above effects, the proportion of the liquid homopolymer is in the above range, but it is preferably per 100 parts by mass of the diene system. The rubber or liquid homopolymer is 35 parts by mass or more, particularly preferably 50 parts by mass or more, preferably 82 parts by mass or less, 80 parts by mass or less, particularly preferably 60 parts by mass or less, and preferably 100 parts by mass or less. The total amount of the filler is 25 parts by mass or more, 35 parts by mass or more, particularly preferably 40 parts by mass or more, more preferably 60 parts by mass or less, and particularly preferably 45 parts by mass or less.

According to the results of Example 1, Example 5, Example 6, and Comparative Example 2, in order to further enhance the above effects, it is preferred to set the blending ratio of the dicyclopentadiene-based petroleum resin as the alicyclic hydrocarbon resin to 0 parts by mass, that is, when the alicyclic hydrocarbon resin is not blended, and in the case of blending the alicyclic hydrocarbon resin, it is preferably 25 parts by mass per 100 parts by mass of the diene rubber and the alicyclic hydrocarbon resin. the following.

According to the results of Example 2, Example 4, and Examples 7 and 9, it can be seen that although the liquid IR and the liquid BR are substantially equal in effect as a liquid homopolymer, particularly liquid IR is preferable.

Further, according to the results of Examples 1 to 3, in order to further enhance the above effects, it is preferred to use butadiene rubber alone or in combination with natural rubber as the diene rubber. Further, although not apparent from the table, when a general-purpose natural rubber is used alone as the diene rubber, the productivity of the high-attenuation composition or the high-attenuation member can be improved, and the production cost can be lowered.

1. . . Circular plate

2. . . Steel plate

3. . . Test body

4. . . Central fixing fixture

5. . . Left and right fixing fixture

6. . . Fixed arm

7, 9. . . Connector

8. . . Movable disk

H. . . Hysteresis loop

Keq. . . Slope

L ₁ . . . straight line

L ₂ . . . perpendicular

W. . . energy

ΔW. . . Amount of absorbed energy

Fig. 1 is an exploded perspective view showing, in an exploded manner, a test body which is produced as a high-attenuation member model for evaluating the attenuation performance of a high-attenuation member including a high-attenuation composition of an example of the present invention.

2(a) and 2(b) are schematic diagrams illustrating a testing machine for determining the relationship between the displacement amount and the load by displacing the test body.

3 is a graph showing an example of a hysteresis loop showing the relationship between the displacement amount and the load, which is obtained by displacing the test body using the above test machine.

H. . . Hysteresis loop

Keq. . . Slope

L ₁ . . . straight line

L ₂ . . . perpendicular

W. . . energy

ΔW. . . Amount of absorbed energy

Claims (7)

A highly attenuating composition which is formulated with a liquid homopolymer in a diene rubber as a base polymer, and is selected from at least 1 group consisting of liquid isoprene rubber and liquid butadiene rubber. And a filler having a high-attenuation composition selected from at least one of the group consisting of cerium oxide and carbon black, the high-attenuating composition characterized in that the liquid homopolymer is present at every 100 The blending ratio in the part by mass of the diene rubber is 31 parts by mass or more. The high-attenuation composition according to the first aspect of the invention, wherein the filler is contained in an amount of 125 parts by mass or more and 180 parts by mass or less per 100 parts by mass of the diene rubber, and the liquid is The blending ratio of the total amount of the filler to the filler per 100 parts by mass is 25 parts by mass or more and 60 parts by mass or less. The high-attenuation composition according to claim 1 or 2, wherein the alicyclic hydrocarbon resin is not contained, or the alicyclic hydrocarbon resin is blended in a proportion of 100 parts by mass of the diene rubber. The alicyclic hydrocarbon resin is 25 parts by mass or less. The high-attenuation composition according to the first or second aspect of the invention, wherein the cerium oxide is cerium oxide having a BET specific surface area of 120 m ² /g or more and 300 m ² /g or less. The high-attenuation composition according to the first or second aspect of the invention, wherein the butadiene rubber is used alone or the above-described butadiene rubber and natural rubber are used in combination as the diene rubber. The high-attenuation composition according to the first or second aspect of the invention, wherein the natural rubber is used alone as the diene rubber. The high-attenuation composition according to the first or second aspect of the invention, wherein the high-attenuation composition is used as a material for forming a shock damper for a building.