TW201302889A - High decay composition - Google Patents

Abstract

A novel high decay composition is provided for fabricating a high decay part having a high decay property and that a decrease in modulus of elasticity is small when a large deformation is applied. A high decay composition, wherein 3 to 50 parts by mass of a rosin derivative with an acid value of 155 mgKOH/g or more, 100 to 180 parts by mass of silica, 0.1 to 10 parts by mass of imidazole compound and 0.1 to 20 parts by mass of hindered phenol compound are blended into 100 parts by mass of base polymer.

Description

High attenuation composition

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

For example, high-attenuation components are used in a wide range of fields such as buildings such as high-rise buildings or bridges, industrial machinery, aircraft, automobiles, rail vehicles, computers or peripheral devices, household appliances, and even automobile tires. By using the high-attenuation member, the transmission of vibration energy can be alleviated and absorbed, that is, vibration-free, vibration-proof, vibration-proof, vibration-proof, and the like.

The high attenuation member is formed of a high attenuation composition containing natural rubber or the like as a base polymer. The high-attenuation member is configured to be capable of increasing the hysteresis loss when vibration is applied, so that the vibration energy is efficiently and rapidly attenuated, that is, the attenuation performance is improved, and carbon black, ruthenium dioxide, etc. are usually formulated. An inorganic filler, an adhesive such as rosin or petroleum resin, and the like (for example, refer to Patent Document 1 to Patent Document 3).

However, the attenuation properties of the high attenuation component cannot be sufficiently improved by the previously high attenuation compositions. In order to further improve the attenuation performance of the high-attenuation member compared with the current state, it is considered to further increase the blending ratio of the inorganic filler or the adhesive or the like.

However, there is a problem in that the processability of a high-attenuation composition in which a large amount of an inorganic filler or an adhesive is formulated is lowered, and the high-attenuation composition is kneaded in order to manufacture a high-attenuation member having a desired three-dimensional shape. Or the operation of forming into the three-dimensional shape is not easy.

In particular, in the case of mass production of high-attenuation members at the factory level, the low workability is such that the productivity of the high-attenuation members is largely reduced, the energy required for production is increased, and the production cost is increased. The reason is therefore not ideal.

Therefore, in order to improve the attenuation performance without lowering the workability, Patent Document 4 has studied a method of blending an attenuating imparting agent having two or more polar groups in a base polymer having a polar side chain.

However, the glass transition temperature Tg of the base polymer having a polar side chain equal to the base polymer having a polar group in the molecule is usually present at room temperature (3 ° C to 35 ° C), and thus the use of the base polymer is used. The high-attenuation member formed by the high-attenuation composition tends to have a temperature dependency of characteristics such as rigidity particularly in the vicinity of the room temperature which is the most usual use temperature region.

Patent Document 5 discloses a method of formulating cerium oxide and an attenuating imparting agent having two or more polar groups in a base polymer having no polar side chain. According to this configuration, it is possible to maintain good attenuation performance by using cerium oxide in combination, and by using a base polymer having no polar group as a base polymer, the temperature dependency of properties near room temperature can be made small.

However, in order to increase the attenuation performance and increase the blending ratio of the attenuating imparting agent as compared with the current situation, there is a problem that the attenuating imparting agent becomes easy to bloom on the surface of the high-attenuating member. (bloom).

Patent Document 6 studies a method of further improving the attenuation performance by using a rosin derivative having a specific softening point as an attenuating imparting agent.

However, in order to further increase the attenuation performance and increase the blending ratio of the rosin derivative as compared with the current situation, there arises a problem that the adhesiveness is too high and the workability of the highly attenuating composition is lowered.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-2014

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-63425

[Patent Document 3] Japanese Patent Laid-Open No. Hei 7-41603

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-44813

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-138053

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-189604

The high-attenuation composition described in Patent Literatures 1 to 6 has various problems as described above. However, by appropriately adjusting the blending ratio of each component, etc., it is possible to achieve a certain degree at the same time. High attenuation performance and good processability.

However, the high-attenuation member formed using the above-described high-attenuation composition is liable to be generated by the so-called Mullins' effect, which is reduced in the modulus of elasticity after application of a large deformation, and cannot be fully utilized as a high Attenuating the desired performance of the component, and thus there are situations in which various problems arise.

For example, if the damper for earthquake-proof and vibration-damping of a building is subjected to large deformation and the modulus of elasticity is lowered, there is a possibility that the energy of the earthquake cannot be reliably prevented from being transmitted to the building. Therefore, in order to ensure desired performance in addition to the reduction in the modulus of elasticity, there is a problem that the design of a product such as a damper for vibration is complicated.

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel high-attenuation composition which can produce a high-attenuation member having high attenuation performance and having a small decrease in elastic modulus after application of a large deformation.

The present invention is a high-attenuation composition characterized in that, in 100 parts by mass of the base polymer, 3 parts by mass or more and 50 parts by mass or less of a rosin derivative having an acid value of 155 mgKOH/g or more, and 100 parts by mass or more are contained. 0.1 parts by mass or more and 10 parts by mass or less of the imidazole-based compound, and 0.1 part by mass or more and 20 parts by mass or less of the hindered phenol-based compound.

According to the study by the inventors, by using a rosin derivative, a cerium oxide, an imidazole compound, and a hindered phenol-based compound in combination, the compounding ratio of the components can be increased without increasing the composition of the high-attenuating composition. The processability is lowered to cause problems such as blooming, and the attenuation performance of the high-attenuation member formed using the high-attenuation composition is further improved as compared with the current situation.

Further, as a rosin derivative, by using a rosin derivative having an acid value of 155 mgKOH/g or more, it is understood from the results of the examples and comparative examples described later that the decrease in the elastic modulus after application of a large deformation can be suppressed. Therefore, for example, a damper for vibration damping or the like can be simplified as a design for securing a desired performance.

Further, as the rosin derivative, the cerium oxide, the imidazole-based compound, and the hindered phenol-based compound, the compounding of the various types can be adjusted by adjusting the blending ratio within the predetermined range, so that the attenuation performance of the high-attenuating member can be freely designed. The degree of improvement is therefore advantageous in considering the attenuation performance in the design of high attenuation components.

As the base polymer, various base polymers which can exhibit high attenuation performance by blending a rosin derivative, a cerium oxide, an imidazole compound, and a hindered phenol compound can be used arbitrarily.

In particular, it is preferable to form a high-attenuating member which exhibits stable attenuation performance even in a wide temperature range, in particular, the base polymer is preferably selected from the following At least one of the group consisting of a compound: a natural rubber, an isoprene rubber, and a butadiene rubber having a small temperature dependency of properties such as rigidity which does not have a polar group and is near room temperature.

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, even if a large deformation occurs due to an earthquake, the elastic modulus is not large. The degree is lowered, so that the energy of the earthquake can be surely prevented from being transmitted to the building. Moreover, it is therefore also possible to simplify the design of the damping damper to ensure the desired performance.

[Effects of the Invention]

By the present invention, it is possible to provide a novel high-attenuation composition which can produce a high-attenuation member having high attenuation performance and having a small decrease in elastic modulus after application of a large deformation.

The present invention is a high-attenuation composition characterized in that, in 100 parts by mass of the base polymer, 3 parts by mass or more and 50 parts by mass or less of a rosin derivative having an acid value of 155 mgKOH/g or more, and 100 parts by mass or more are contained. 0.1 parts by mass or more and 10 parts by mass or less of the imidazole-based compound, and 0.1 part by mass or more and 20 parts by mass or less of the hindered phenol-based compound.

(base polymer)

As the base polymer, various base polymers which can exhibit high attenuation performance by blending a rosin derivative, a cerium oxide, an imidazole compound, and a hindered phenol compound can be used arbitrarily, and among them, rubber is preferred.

Examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, norbornene rubber, ethylene propylene rubber, ethylene propylene diene rubber, butyl rubber, and halogenated butyl rubber. One or more of chloroprene rubber, acrylonitrile butadiene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, and polysulfide rubber.

In particular, if a high attenuation member exhibiting stable attenuation performance over a wide temperature range is provided in consideration of reducing the temperature dependency of the attenuation performance, it is preferable that the rubber is selected from natural rubber, isoprene rubber, And at least one rubber of the group consisting of butadiene rubber.

Two or more types of rubber may be used in combination. However, if the composition of the high-attenuation composition is simplified and the productivity of the high-attenuation composition and the high-attenuation member is improved, and the production cost is further reduced, it is preferable to use any one alone. Kind.

(rosin derivative)

The rosin derivative can be, for example, a resin containing rosin as a constituent component such as an ester of rosin and a polyhydric alcohol (such as glycerin) or a rosin-modified maleic acid resin, and has a function as a binder to cause high attenuation. Among the various derivatives which have an effect of improving the attenuation performance of the member, those having an acid value of 155 mgKOH/g or more are selected and used. Thereby, the decrease in the elastic modulus after the application of the large deformation can be suppressed. The reason for this is that once a large deformation is applied, although the cerium oxide or the imidazole compound is separated from the weak combination of the rosin derivative, the interaction of the rosin derivative having an acid value within the range is immediately recombined. The elastic modulus is easily restored.

Further, as the acid value of the rosin derivative, in consideration of further suppressing the decrease in the elastic modulus after application of a large deformation, it is preferably 160 mgKOH/g or more, and particularly preferably 220 mgKOH/g in the above range. the above. Further, if the acid value of the rosin derivative is too high, the polarity becomes too high and it becomes difficult to be fused to the base polymer. Therefore, it is preferably 330 mgKOH/g or less, and particularly preferably 300 mgKOH in the above range. /g below.

Further, the softening point of the rosin derivative is preferably 80 ° C or more and 140 ° C or less.

When the softening point is less than the above range, the effect of improving the attenuation performance of the high-attenuation member cannot be sufficiently obtained. On the other hand, when it exceeds the above range, there is a possibility that the workability is lowered, the components are kneaded in order to prepare a highly attenuating composition, and the high-attenuation member is kneaded for producing a high-attenuation member, or The operation of forming into an arbitrary shape becomes not easy.

In addition, the softening point is represented by the value measured by the softening point test method (ring and ball method) described in Japanese Industrial Standard JIS K2207-1996 "Petroleum Bitumen".

The rosin derivative is, for example, KR-85 in the PINECRYSTAL (registered trademark) series manufactured by Arakawa Chemical Industries Co., Ltd. (acid value: 165 mgKOH/g to 175 mgKOH/g, softening point: 80 ° C to 87) °C), KR-612 (acid value: 160 mgKOH/g to 175 mgKOH/g, softening point: 80 °C to 90 °C), KR-614 (acid value: 170 mgKOH/g to 180 mgKOH/g, softening point One or two or more kinds of KE-604 (acid value: 230 mgKOH/g to 245 mgKOH/g, softening point: 122 to 134 °C).

Particularly, in view of the acid value and the softening point, KR-612 and KE-604 are preferred among the rosin derivatives.

The blending ratio of the rosin derivative must be 3 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the base polymer.

When the blending ratio is less than 3 parts by mass, the effect of improving the damping performance of the high-attenuating member due to the blending of the rosin derivative cannot be obtained. Further, in the case of more than 50 parts by mass, the adhesiveness of the rosin derivative is increased to cause a decrease in workability, and it becomes impossible to carry out the following operations: mixing the components for the purpose of blending the high-attenuating composition, for the purpose of manufacturing The high-attenuation member is kneaded with a high attenuation member or formed into an arbitrary shape.

In addition, as the blending ratio of the rosin derivative, in consideration of further improving the attenuation performance of the high-attenuating member, it is preferably 10 parts by mass or more in the above range. Further, in consideration of reducing the decrease in the elastic modulus after the application of the large deformation as much as possible, it is preferably 20 parts by mass or less in the above range.

(cerium oxide)

As the cerium oxide, any of the wet type cerium oxide and the dry type cerium oxide classified according to the production method thereof can be used. Further, as the cerium oxide, it is preferable to use an BET specific surface area of 100 m ² /g or more, particularly 200 m ² /g, in order to improve the function of the filler as a filler and to improve the attenuation performance of the high-attenuating member. In the above, it is preferred to use a BET specific surface area of 400 m ² /g or less, particularly 250 m ² /g or less.

The BET specific surface area is represented by a value measured by a vapor phase adsorption method using, for example, a rapid surface area measuring device SA-1000 manufactured by Shibata Chemical Instruments Industrial Co., Ltd., or the like, using nitrogen as an adsorption gas.

For example, one or two or more of NipSil (registered trademark) KQ, VN3, AQ, and ER manufactured by Tosoh Silica Corporation may be mentioned.

The blending ratio of the cerium oxide must be 100 parts by mass or more and 180 parts by mass or less per 100 parts by mass of the base polymer.

If the blending ratio is less than 100 parts by mass, the effect of improving the damping performance of the high-attenuating member due to the blending of cerium oxide cannot be obtained. Further, in the case of more than 180 parts by mass, the effect of blending the specific rosin derivative to reduce the decrease in the modulus of elasticity after applying a large deformation cannot be obtained.

Further, in the case of more than 180 parts by mass, there is a case where the workability of the high-attenuation composition is lowered, and in particular, it becomes difficult to mass-produce a high-attenuation member having a desired three-dimensional shape at the factory level. Further, although a small number of high-attenuation members can be formed at a trial level, the formed high-attenuation members are hard and hard to be deformed, and thus have a problem that they are easily broken particularly in the case of large deformation.

In addition, as the mixing ratio of the cerium oxide, in consideration of further improving the attenuation performance of the high-attenuating member, it is preferably 135 parts by mass or more in the above range. Further, in consideration of reducing the decrease in the elastic modulus after the application of the large deformation as much as possible, it is preferably 150 parts by mass or less in the above range.

(imidazole compound)

Examples of the imidazole-based compound include various imidazole compounds having the following functions among various compounds having an imidazole ring in the molecule: a high-yield composition composed of a cerium oxide, a rosin derivative, and a hindered phenol compound can be improved. Attenuation characteristics of the attenuation component.

Examples of the imidazole-based compound include imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl-imidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-benzene. One or two or more kinds of imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

Particularly, in terms of an effect of improving the attenuation performance of the high-attenuating member, imidazole, 2-methylimidazole, and 1,2-dimethylimidazole are preferable, and among them, imidazole is most preferable.

The blending ratio of the imidazole-based compound must be 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the base polymer.

If the blending ratio is less than 0.1 part by mass, the effect of improving the damping performance of the high-attenuating member cannot be obtained. Further, when it exceeds 10 parts by mass, coking tends to occur and workability is lowered, so that it becomes impossible to knead each component in order to modulate a highly attenuating composition, in order to manufacture a highly attenuating member. The highly attenuating composition is kneaded or shaped into an arbitrary shape.

In addition, in order to maintain good workability of the high-attenuation composition and to further improve the attenuation performance of the high-attenuation member, the blending ratio of the imidazole-based compound is preferably 0.3 parts by mass or more in the above range. Below the mass.

(hindered phenolic compound)

As the hindered phenol-based compound, any of various hindered phenol-based compounds which function as the organic group headed by the base polymer due to the interaction of the hydroxyl group in the molecule with the hydroxyl group on the surface of the ceria can be used. The affinity and compatibility of the components are improved, and the attenuation performance of the high-attenuation member is further improved.

The hindered phenol-based compound is preferably the above-mentioned various hindered phenol-based compounds having two or more hydroxyl groups, and particularly preferably a bisphenol-based anti-aging agent, a polyphenol-based anti-aging agent, and a thiobisphenol-based anti-aging agent. One or two or more kinds of anti-aging agents such as a hydroquinone-based anti-aging agent.

The bisphenol-based anti-aging agent in the compound may, for example, be 1,1-bis(3-hydroxyphenyl)cyclohexane or 2,2'-methylenebis(4-methyl-6-tributyl). Phenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)]- P-cresol, 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-- Phenylpropionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, p-cresol and dicyclopentadiene One or two or more kinds of the butylation reaction product.

Examples of the polyphenol-based anti-aging agent include tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].

Examples of the thiobisphenol-based anti-aging agent include 4,4-thiobis(3-methyl-6-tert-butylphenol) and 4,4'-bis(3,5-di-t-butyl group. One or more of -4-hydroxybenzyl) sulfide and 4,4'-thiobis(6-tert-butyl-o-cresol).

Further, examples of the hydroquinone-based anti-aging agent include one or two of 2,5-di-t-butyl hydroquinone and 2,5-di-t-butylpentyl hydroquinone. More than one species.

The blending ratio of the hindered phenol-based compound must be 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the base polymer.

If the blending ratio is less than 0.1 part by mass, the effect of improving the damping performance of the high-attenuating member cannot be obtained. Further, in the case of more than 20 parts by mass, there is a problem that an excessively hindered phenol-based compound becomes easy to bloom on the surface of the high-attenuating member as explained above.

In addition, the blending ratio of the hindered phenol-based compound is preferably 1 part by mass or more, and particularly preferably 2.5 parts by mass or more in the above range, in consideration of further improving the attenuation performance of the high-attenuating member.

(other)

In the high-attenuation composition of the present invention, a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerating aid, or the like may be further blended in a suitable ratio to vulcanize the deproteinized natural rubber, or a decane compound or a softener. Various additives such as tackifiers and other anti-aging agents other than hindered phenols.

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

[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 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, and is preferably 5 parts by mass or more and 25 parts by mass or less per 100 parts by mass of the cerium oxide.

The softening agent may be one or more selected from the group consisting of a coumarone-indene resin and a liquid rubber.

In addition, examples of the coumarone-indene resin include various coumarone-indene resins which mainly contain a polymer of coumarone and hydrazine, a relatively low molecular weight having an average molecular weight of about 1,000 or less, and a function as a softening agent.

The coumarone-indene resin is, for example, Nitto Resin (registered trademark) coumarone G-90 manufactured by Nippon Paint Chemical Co., Ltd. [average molecular weight: 770, softening point: 90 ° C, acid value: 1.0 KOH mg/g. Hereinafter, the hydroxyl value is 25 KOHmg/g, the bromine number is 9 g/100 g], G-100N [the average molecular weight is 730, the softening point is 100 ° C, the acid value is 1.0 KOH mg/g or less, and the hydroxyl value is 25 KOH mg/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] And V-120S [one or two or more kinds of an average molecular weight of 950, a softening point of 120 ° C, an acid value of 1.0 KOHmg/g or less, a hydroxyl value of 30 KOHmg/g, and a bromine number of 7 g/100 g].

The blending ratio of the coumarone-indene resin is not particularly limited, and is preferably 5 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the deproteinized natural rubber.

Further, examples of the liquid rubber include various rubbers which are liquid at room temperature (3 to 35 ° C). The liquid rubber may, for example, be one or more selected from the group consisting of liquid polyisoprene rubber, liquid nitrile rubber (liquid NBR), and liquid styrene butadiene rubber (liquid SBR).

Among them, preferred is a liquid polyisoprene rubber. Examples of the liquid polyisoprene rubber include Kuraplene (registered trademark) LIR-50 manufactured by Kuraray Co., Ltd., and the like.

The blending ratio of the liquid polyisoprene rubber is not particularly limited, and is preferably 5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the deproteinized natural rubber.

Examples of the tackifier include petroleum resins and the like. Further, the petroleum resin is, for example, Maruka Lyncur (registered trademark) M890A (dicyclopentadiene petroleum resin, softening point: 105 ° C) manufactured by Maruzen Petrochemical Co., Ltd., and the like.

The blending ratio of the petroleum resin is not particularly limited, and is preferably 3 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the deproteinized natural 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, and it is preferred that the benzimidazole-based anti-aging agent is 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the deproteinized natural rubber. Moreover, it is preferable that the lanthanide 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 deproteinized natural rubber.

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 kind, it is preferred to use the two together.

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 oxide and stearic acid. 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 rubber hardness which are different depending on the use of the high-attenuating member.

The high-attenuation composition of the present invention can produce a high-attenuation member having a predetermined attenuation performance by arranging the components by kneading using any kneading machine, and shaping the high-attenuation composition. The desired three-dimensional shape is used to vulcanize the deproteinized natural rubber.

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

According to the present invention, by adjusting the kinds of the ceria, the rosin derivative, the imidazole compound, and the hindered phenol compound in the above range, and the combination and blending ratio thereof, excellent attenuation suitable for each of the above uses can be obtained. High attenuation components for performance.

In particular, in the case of using the high-attenuation composition of the present invention to form a shock damper incorporated in a structure of a building, the vibration damping performance of the shock damper is excellent, and after a large deformation is applied Since the reduction in the modulus of elasticity is small, the design of the article for ensuring the desired performance can be simplified, and the number of the dampers for damping provided in one building can be reduced.

[Example]

The preparation and test of the high-attenuation composition in the following examples and comparative examples were carried out in an environment of a temperature of 20 ° C and a relative humidity of 55%, unless otherwise specified.

<Example 1>

In 100 parts by mass of natural rubber (SMR (Standard Malaysian Rubber)-CV60] as a base polymer:

* cerium oxide [NipSil KQ manufactured by Tosoh Silica Corporation] 135 parts by mass,

* Rosin derivative [modified rosin derivative, acid value: 230 mgKOH/g to 245 mgKOH/g, softening point: 122 °C to 134 °C, PINECRYSTAL (registered trademark) KE-604 manufactured by Arakawa Chemical Industry Co., Ltd.] 10 parts by mass,

* Imidazole as an imidazole compound [manufactured by Nippon Synthetic Chemical Co., Ltd.] 2.5 parts by mass, and

* 4,4'-butylene bis(3-methyl-6-tert-butylphenol) as a hindered phenolic compound [Nocrac (registered trademark) NS-30 manufactured by Ouchi Shinko Chemical Co., Ltd.) 2.5 Parts by mass

Each component shown in the following Table 1 was kneaded using a closed kneader to prepare a highly attenuating composition.

The components in Table 1 are as follows.

Phenyltriethoxydecane: KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.

Dicyclopentadiene-based petroleum resin: Maruka Lyncur (registered trademark) M890A, manufactured by Maruzen Petrochemical Co., Ltd., softening point: 105 °C

Coumarone resin: Softening point is 90 ° C, Escuron (registered trademark) G-90 manufactured by Nissin 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.

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: Nocceler TBT-N manufactured by Ou Nei Xin Chemical Industry Co., Ltd.

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

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

Carbon Black: Diablack (registered trademark) G manufactured by Mitsubishi Chemical Corporation

Liquid polyisoprene rubber: softener, LIR50 manufactured by Kuraray Co., Ltd.

<Example 2>

The modified rosin derivative (PINECRYSTAL (registered trademark) KE-612 manufactured by Arakawa Chemical Industries Co., Ltd.) is used as a modified rosin derivative with an acid value of 160 mgKOH/g to 175 mgKOH/g and a softening point of 80 °C to 90 °C. A high-attenuation composition was prepared in the same manner as in Example 1 except that the rosin derivative was used.

<Example 3>

The same amount of rosin modified special synthetic resin (HARIMACK AS-5 manufactured by Harima Chemical Co., Ltd.) with an acid value of 185 mgKOH/g to 210 mgKOH/g and a softening point of 155 °C to 165 °C is formulated as a rosin derivative. A high attenuation composition was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 1>

A rosin-modified maleic acid resin (trade name: HARIMACK 135GN manufactured by Harima Chemical Co., Ltd.) having an acid value of 32 mgKOH/g to 38 mgKOH/g and a softening point of 130 °C to 140 °C is formulated as a rosin derivative. A high-attenuation composition was prepared in the same manner as in Example 1 except that the imidazole-based compound and the hindered phenol-based compound were not prepared.

<Comparative Example 2>

A rosin-modified maleic acid resin (trade name: HARIMACK 135GN manufactured by Harima Chemical Co., Ltd.) having an acid value of 32 mgKOH/g to 38 mgKOH/g and a softening point of 130 °C to 140 °C is formulated as a rosin derivative. The high attenuation composition was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 3>

A maleic acid resin (Marukido (registered trademark) No. 32 manufactured by Arakawa Chemical Industries Co., Ltd.) having an acid value of 140 mg KOH/g or less and a softening point of 130 ° C to 140 ° C is used in place of the rosin derivative. Otherwise, the high attenuation composition was prepared in the same manner as in Example 1.

<Comparative Example 4>

The same amount of rosin modified special synthetic resin (HARIESTER MSR-4 manufactured by Harima Chemical Co., Ltd.) with an acid value of 120 mgKOH/g to 150 mgKOH/g and a softening point of 120 °C to 135 °C is formulated as a rosin derivative. A high attenuation composition was prepared in the same manner as in Example 1 except for the above.

<Attenuation characteristic test>

(production of test body)

The high-attenuation composition prepared in the examples and the comparative examples was extruded into a thin plate shape and then pressed, and a circular plate 1 (thickness: 5 mm × diameter: 25 mm) was produced as shown in Fig. 1, on the surface of the circular plate 1. A rectangular flat plate-shaped steel plate 2 having a thickness of 6 mm × a length of 44 mm × a width of 44 mm is laminated on both sides of the back by a vulcanizing adhesive, and heated to 150 ° C while being pressurized in the lamination direction to form a circular plate 1 The high-attenuation composition was vulcanized, and the disk 1 and the two steel sheets 2 were vulcanized, and a test body 3 for evaluation of attenuation characteristics as a model of a high-attenuation member was produced.

(displacement test)

Two test bodies 3 were prepared as shown in Fig. 2 (a), and the two test bodies 3 were fixed to one central fixing jig 4 by bolts via one of the steel plates 2, and One of the left and right fixing jigs 5 is fixed to the other steel plate 2 of each of the test bodies 3 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 above via the joint 9. The movable plate 8 on the lower side of the test machine.

Next, in this state, as shown by the hollow arrow in the figure, the movable disk 8 is displaced and lifted in the direction of the fixed arm 6, and as shown in Fig. 2(b), the circular plate 1 in the test body 3 is set. In a deformed state in which the strain is deformed in a direction orthogonal to the lamination direction of the test body 3, secondly, from the deformed state, the movable disk 8 is displaced in the direction of the fixed arm 6 as indicated by a hollow arrow in the figure. When the direction is reversed, the state shown in FIG. 2(a) is returned, and the above operation is performed as one cycle, and the disk 1 in the test body 3 is deformed by strain and deformation, 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 performed by performing the above operation 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 disc 1 in the direction orthogonal to the lamination direction is 100% of the thickness of the disc 1.

Next, the maximum displacement point in the hysteresis loop H shown in Fig. 3 obtained by the 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 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 (N/mm ² ) was obtained. Further, the equivalent shear elastic modulus Geq (N/mm ² ) of each of the examples and the comparative examples when the equivalent shear elastic modulus Geq (N/mm ² ) in Comparative Example 1 was set to 100 was determined. relative value.

Moreover, 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 straight line L ₁ , the horizontal axis of the graph, the surface area of the region surrounded by the perpendicular line L ₂ perpendicular to the horizontal axis from 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 is obtained. The larger the equivalent decay constant Heq, the more excellent the attenuation performance of the test body 3 can be determined.

Here, the relative value of the equivalent decay constant Heq of each of the examples and the comparative examples when the equivalent decay constant Heq in Comparative Example 1 is set to 100 is obtained, and the case where the relative value is 105 or more is evaluated as good. The case of less than 105 was evaluated as bad.

<Measurement of elastic modulus after large deformation>

In the same manner as described above, the maximum displacement amount is set such that the amount of shift in the direction perpendicular to the lamination direction of the two steel sheets 2 that sandwich the disc 1 is set to be 300% of the thickness of the disc 1 . After the round plate 1 was deformed once, the shear elastic modulus Geq' (N/mm ² ) when the offset amount was 100% was obtained in the same manner as described above.

Moreover, according to equation (3):

[Math 3]

The retention rate (%) of the elastic modulus after the large deformation was obtained. The larger the retention ratio, the more the decrease in the elastic modulus of the test body 3 after the application of the large deformation is small.

Therefore, the relative value of the retention ratio of each of the examples and the comparative examples when the retention ratio of Comparative Example 1 was 100 was determined, and the case where the relative value was 100 or more was evaluated as good, and the case where the relative value was less than 100 was evaluated as defective. .

The above results are shown in Table 2.

According to the results of Comparative Example 1 to Comparative Example 4 of Table 2, it was found that the attenuation properties of the high-attenuation member can be improved by using the four compounds of ceria, rosin derivative, imidazole compound, and hindered phenol compound in combination. However, if the acid value of the rosin derivative is less than 155 mgKOH/g, the decrease in the modulus of elasticity after application of a large deformation becomes large.

On the other hand, according to the results of Examples 1 to 3, it is understood that by selecting a rosin derivative having an acid value of 155 mgKOH/g or more as the rosin derivative, good attenuation performance of the high-attenuating member can be maintained, and The decrease in the modulus of elasticity after applying a large deformation becomes small.

Further, as the rosin derivative, those having an acid value of 160 mgKOH/g or more, and particularly preferably 220 mgKOH/g or more are preferably used.

Further, Example 3 using a rosin derivative having a softening point exceeding 140 ° C is required to be long in order to modulate a highly attenuating composition as compared with Example 1, Example 2 using a rosin derivative having a softening point of 140 ° C or less. Time to mix the ingredients. From this, it is understood that the softening point of the rosin derivative is preferably 140 ° C or lower.

<Example 4 to Example 7, Comparative Example 5>

A rosin derivative [modified rosin derivative, an acid value of 230 mgKOH/g to 245 mgKOH/g, a softening point of 122 ° C to 134 ° C, PINECRYSTAL (registered trademark) KE-604 manufactured by Arakawa Chemical Industries Co., Ltd.] The blending ratio was 2 parts by mass (Comparative Example 5), 3 parts by mass (Example 4), 20 parts by mass (Example 5), 30 parts by mass (Example 6), and 50 parts by mass (Example 7). The high attenuation composition was prepared in the same manner as in Example 1.

<Comparative Example 6>

When the blending ratio of the rosin derivative was 55 parts by mass, the adhesiveness was too strong, and it was not possible to knead a mixture of the respective components to prepare a highly attenuating composition.

Therefore, the respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples except Comparative Example 6, and the characteristics were evaluated. The results are shown in Table 3 together with the results of Example 1.

[table 3]

According to the results of Comparative Example 5 of Table 3, it is understood that even in the combined system of the four compounds containing a rosin derivative having an acid value of 155 mgKOH/g or more, the blending ratio of the rosin derivative is less than 3 parts by mass. , the attenuation performance of the high attenuation component cannot be improved. Further, according to the results of Comparative Example 6, when the blending ratio of the rosin derivative exceeds 50 parts by mass, the processability of the highly attenuating composition is lowered.

On the other hand, according to the results of the examples 1 and 4 to 7, it is understood that the processability of the high-attenuation composition can be maintained by setting the proportion of the rosin derivative to 3 parts by mass or more and 50 parts by mass or less. And the attenuation performance of the high attenuation component is improved.

Further, it is also known that the blending ratio of the rosin derivative is preferably 10 parts by mass or more in the above range in order to further improve the attenuation performance of the high-attenuating member; The decrease in the modulus of elasticity is as small as possible, and is preferably 20 parts by mass or less in the above range.

<Example 8 to Example 10, Comparative Example 7, Comparative Example 8>

The blending ratio of cerium oxide was set to 80 parts by mass (Comparative Example 7), 100 parts by mass (Example 8), 150 parts by mass (Example 9), 180 parts by mass (Example 10), and 190 parts by mass (Comparative Example 8) Except for the above, the high attenuation composition was prepared in the same manner as in Example 1.

The respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples to evaluate the characteristics. The results are shown in Table 4 together with the results of Example 1.

According to the results of Comparative Example 7 of Table 4, even in the combination of the above four compounds, if the proportion of the cerium oxide is less than 100 parts by mass, the attenuation performance of the high-attenuating member cannot be improved. Further, according to the results of Comparative Example 8, when the blending ratio of cerium oxide exceeds 180 parts by mass, the decrease in the modulus of elasticity after application of large deformation becomes large.

On the other hand, according to the results of the examples 1 and 8 to 10, it is understood that the attenuation ratio of the high-attenuating member can be improved by setting the proportion of the cerium oxide to 100 parts by mass or more and 180 parts by mass or less. The decrease in the modulus of elasticity after applying a large deformation becomes small.

Further, it is also known that, as a ratio of blending of cerium oxide, in order to further improve the attenuation performance of the high-attenuating member, it is preferably 135 parts by mass or more in the above range; in order to apply a large deformed elastic mold The decrease in the number is as small as possible, and it is preferably 150 parts by mass or less in the range.

<Example 11 to Example 14, Comparative Example 9>

The blending ratio of the imidazole-based compound was 0.05 parts by mass (Comparative Example 9), 0.3 parts by mass (Example 11), 1 part by mass (Example 12), 5 parts by mass (Example 13), and 10 parts by mass (Example 14). The high attenuation composition was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 10>

When the blending ratio of the imidazole-based compound was 13 parts by mass, coking occurred during kneading, and thus it was impossible to prepare a highly attenuating composition.

Therefore, the respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples except Comparative Example 10, and the characteristics were evaluated. The results are shown in Table 5 together with the results of Example 1.

According to the results of the comparative example 9 of the above-mentioned Table 5, even if the compounding ratio of the imidazole-based compound is less than 0.1 part by mass, the attenuation performance of the high-attenuation member cannot be improved. Further, according to the results of Comparative Example 10, when the blending ratio of the imidazole-based compound exceeds 10 parts by mass, the workability of the highly attenuating composition is lowered.

On the other hand, according to the results of the example 1 and the example 14 to the example 14, it is understood that the blending ratio of the imidazole compound is 0.1 parts by mass or more and 10 parts by mass or less, whereby the good processability of the highly attenuating composition can be maintained. Moreover, the attenuation performance of the high attenuation component can be improved.

In addition, it is preferable that the ratio of the imidazole-based compound is 0.3 parts by mass or more and 5 parts by mass or less in the above range in order to further improve the attenuation performance of the high-attenuating member.

<Example 15 to Example 18, Comparative Example 11, Comparative Example 12>

The blending ratio of the hindered phenol-based compound was 0.05 parts by mass (Comparative Example 11), 0.3 parts by mass (Example 15), 1 part by mass (Example 16), 10 parts by mass (Example 17), and 20 parts by mass (Example 18). The high-attenuation composition was prepared in the same manner as in Example 1 except that the amount was 23 parts by mass (Comparative Example 12).

The respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples to evaluate the characteristics. The results are shown in Table 6 together with the results of Example 1.

According to the results of Comparative Example 11 of Table 6, it is understood that the blending ratio of the hindered phenol-based compound is less than 0.1 part by mass, and the attenuation performance of the high-attenuating member cannot be improved even in the combination of the four compounds. In addition, Comparative Example 12 in which the compounding ratio of the hindered phenol-based compound was more than 20 parts by mass was confirmed to have no problem in terms of the characteristics of the watch, but blooming occurred.

On the other hand, according to the results of the example 1 and the examples 15 to 18, it is understood that the ratio of the hindered phenol compound to be 0.1 part by mass or more and 20 parts by mass or less can cause high attenuation without blooming or the like. The attenuation performance of the components is improved.

Further, it is also known that the blending ratio of the hindered phenol-based compound is preferably 1 part by mass or more, particularly 2.5 parts by mass or more in the above range in order to further improve the attenuation performance of the high-attenuating member.

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

1 is an exploded perspective view showing a test body which is a model of the high-attenuation member which is produced by evaluating the attenuation performance of a high-attenuation member including a high-attenuation composition of an example of the present invention and a comparative example.

2(a) and 2(b) are diagrams illustrating the outline of 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 test machine.

1. . . Circular plate

2. . . Steel plate

3. . . Test body

Claims (3)

A high-attenuation composition in which 3 parts by mass or more and 50 parts by mass or less of a rosin derivative having an acid value of 155 mgKOH/g or more, and 100 parts by mass or more and 180 parts by mass or less are blended in 100 parts by mass of the base polymer. The cerium oxide, 0.1 parts by mass or more and 10 parts by mass or less of the imidazole-based compound, and 0.1 parts by mass or more and 20 parts by mass or less of the hindered phenol-based compound. The high-attenuation composition according to claim 1, wherein the base polymer is at least one rubber selected from the group consisting of natural rubber, isoprene rubber, and butadiene rubber. The high-attenuation composition described in the first or second aspect of the patent application is used as a material for forming a damping device for a building.