TWI454525B - High decay composition - Google Patents

Description

High attenuation composition

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

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

In order to increase the attenuation performance so that the hysteresis loss when the vibration is applied is made large and the energy of the vibration is efficiently and rapidly attenuated, the high attenuation member is usually caused by the carbon contained in the elastomer (elastomer) A filler such as black or cerium oxide or a highly attenuating composition such as a tackifier such as rosin or petroleum resin is formed (for example, refer to Patent Document 1 to Patent Document 3).

However, with these previously high attenuation compositions, the attenuation performance of the high attenuation component cannot be sufficiently improved. In order to further improve the attenuation performance of the high-attenuation member compared with the current state, for example, a method of further increasing the content ratio of the filler or the like is considered, but a high-attenuation composition containing a large amount of a filler or an adhesive has a decrease in workability, thereby It has become difficult to carry out the problem of kneading or forming the high-attenuation composition into the three-dimensional shape in order to manufacture a high-attenuation member having a desired three-dimensional shape.

In particular, when the high-attenuation member is mass-produced at the factory level, the decrease in the workability is a cause of lowering the productivity of the high-attenuation member, increasing the energy consumption required for production, and increasing the production cost. Not ideal.

Therefore, the high-attenuation composition contains a hindered phenol-based compound as an attenuating imparting agent, and the hindered phenol-based compound is used together with a filler such as cerium oxide or a rosin as described above. Thereby, the attenuation performance is improved (for example, refer to Patent Document 4 to Patent Document 7, etc.).

[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 No. 3661180

[Patent Document 7] Japanese Patent No. 3675216

However, in order to further increase the attenuation performance as compared with the current situation and increase the content ratio of the hindered phenol-based compound, there is a problem that the hindered phenol-based compound becomes easy to bloom on the surface of the high-attenuating member. (bloom).

It is an object of the present invention to provide a high attenuation composition, said high attenuation The composition-reducing material can maintain good workability, and can produce a high-attenuation member which is more excellent in attenuation performance than the current state without causing problems such as blooming.

The present invention is a high-attenuation composition comprising: a base polymer; and 100 parts by weight or more and 180 parts by weight or less of cerium oxide and 3 parts by weight per 100 parts by weight of the base polymer. 50 parts by weight or less of the rosin derivative, 0.1 parts by weight or more and 10 parts by weight or less of the imidazole-based compound, and 0.1 parts by weight or more and 20 parts by weight or less of the hindered phenol-based compound, wherein the imidazole-based compound is selected from the group consisting of imidazole, 1, 2 - dimethylimidazole, 2-ethyl-4-methyl-imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-methylimidazole, 2-111 At least one selected from the group consisting of alkylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.

According to the present invention, since the specific imidazole compound is further contained in the cerium oxide, the rosin derivative, and the hindered phenol compound, the content ratio of the cerium oxide, the rosin derivative, and the hindered phenol compound may not be increased. The attenuation performance of the high-attenuation member formed using the high-attenuation composition is further improved as compared with the current situation without causing a decrease in workability of the high-attenuation composition or causing problems such as blooming.

Further, according to the present invention, the cerium oxide, the rosin derivative, the imidazole compound, and the hindered phenol compound are each adjusted to a content within the predetermined content ratio, and the compound having a different type is contained. The degree of freedom in the design of the attenuation performance of the high attenuation component can be increased, thereby facilitating the consideration of the attenuation performance in the design of the high attenuation component.

The base polymer can be used: it can be derived from cerium oxide and rosin. Any of various base polymers which exhibit high attenuation properties by the imidazole compound and the hindered phenol compound.

However, in particular, if it is considered to form a high-attenuating member which can reduce the temperature dependence of the attenuation performance and exhibit stable attenuation performance over a wide temperature range, the base polymer is preferably selected from natural rubber and isoprene. At least one of a group consisting of a diene rubber and a butadiene rubber, wherein the natural rubber, the isoprene rubber, and the butadiene rubber do not have a polar group, and therefore the temperature dependence of properties such as rigidity near room temperature small.

As the imidazole-based compound, any of the various specific imidazole-based compounds having the following functions among the various compounds having an imidazole ring in the molecule can be used: the high-attenuation composition containing the ceria, the rosin derivative, and the hindered phenol compound can be improved. The attenuation performance of the high attenuation component. However, in consideration of further improving the attenuation performance of the high attenuation member, the imidazole compound is preferably imidazole.

Preferably, the high attenuation composition further contains magnesium acetate and an amine-based anti-aging agent. By containing the two components, the attenuation performance of the high attenuation component can be further improved.

The high-attenuation composition can be prepared by blending and kneading the components in an appropriate order. Preferably, the high-attenuation composition of the present invention is prepared by the following steps: first adding a rosin derivative, an imidazole compound, and a hindered phenol-based compound to the base polymer, kneading, and then adding cerium oxide for kneading .

Furthermore, it is also possible to first add a rosin derivative, an imidazole compound, a hindered phenol compound, and a part of cerium oxide to the base polymer. The mixture is kneaded, and then the remainder of the cerium oxide is added for kneading.

In this way, the rosin derivative, the imidazole compound, and the hindered phenol compound can be kneaded with cerium oxide in a state of being sufficiently dispersed in the base polymer, so that each of the components can be further effectively functioned. The attenuation performance of the high attenuation component is further improved.

When the high-attenuation composition is used as a forming material to form a building damping damper as a high-attenuating member, the number of the shock-absorbing dampers incorporated in one building can be reduced. . Further, since the temperature dependency is small, the shock damper can be provided even in the vicinity of the outer wall of a building having a large temperature difference, for example.

According to the present invention, it is possible to provide a high-attenuation composition which can maintain good workability and which can produce a high-attenuation member which is more excellent in attenuation performance than the current state without causing problems such as blooming.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The high-attenuation composition of the present invention contains: a base polymer; and rosin derived from 100 parts by weight or more and 180 parts by weight or less per 100 parts by weight of the base polymer, and 3 parts by weight or more and 50 parts by weight or less or less of rosin. 0.1 parts by weight or more and 10 parts by weight or less of the imidazole-based compound, and 0.1 parts by weight or more and 20 parts by weight or less of the hindered phenol-based compound.

The base polymer in each of the components can be used: by containing dioxin Any of various base polymers which exhibit high attenuation properties by hydrazine, rosin derivatives, imidazole compounds and hindered phenol compounds, among which 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 it is considered to provide a high-attenuating member which can reduce the temperature dependency of the attenuation performance and exhibit stable attenuation performance over a wide temperature range, it is preferable that the rubber is selected from natural rubber and isoprene rubber. And at least one rubber of the group consisting of butadiene rubber.

Two or more kinds of rubbers may be used in combination. However, in consideration of simplifying the composition of the high-attenuation composition, improving the productivity of the high-attenuation composition and the high-attenuation member, and further reducing the production cost, it is preferred to use either one alone.

As the cerium oxide, any of wet cerium oxide or dry cerium oxide classified according to the production method thereof can be used. Further, in consideration of an effect of improving the damping performance of the high-attenuating member by functioning as a filler, the cerium oxide preferably has a BET specific surface area of from 100 m ² /g to 400 m ² /g, particularly preferably 200 m ^{2 .} /g~250m ² /g. The BET specific surface area can be expressed, for example, by using a rapid surface area measuring device SA-1000 manufactured by Shibata Chemical Instruments Co., Ltd., or the like, using a gas phase adsorption method using nitrogen gas as an adsorption gas.

The content of cerium oxide must be relative to every 100 parts by weight of the basis The polymer is 100 parts by weight or more and 180 parts by weight or less. When the content ratio is less than 100 parts by weight, the effect of improving the attenuation performance of the high-attenuation member due to the inclusion of cerium oxide cannot be obtained. Further, in the case where the content exceeds 180 parts by weight, the processability 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 at the time of large deformation.

Further, in consideration of further improving the attenuation performance of the high-attenuation member, the content ratio of the cerium oxide is preferably 135 parts by weight or more in the above range.

Examples of the rosin derivative include 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 functioning as a binder to attenuate the high-attenuating member. Various derivatives of the effect of improving performance.

The softening point of the rosin derivative is preferably 120 ° C or higher, preferably 180 ° C or lower, and particularly preferably 160 ° C or lower.

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 said range, workability falls, and it becomes difficult to carry out the operation|movement which mix|blends each component, and the high- The high-attenuation composition is kneaded or shaped into an arbitrary shape.

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

Examples of the rosin derivative include MSR-4 (softening point: 127 ° C), DS-130 (softening point: 135 ° C), and AD-130 (softening) in the HARIESTER series manufactured by Harima Chemical Co., Ltd. Point: 135 ° C), DS-816 (softening point: 148 ° C), DS-822 (softening point: 172 ° C), 145P (softening point: 138 ° C) in the HARIMACK series manufactured by Harima Chemical Co., Ltd. One type or two or more types of 135 GN (softening point: 139 ° C) and AS-5 (softening point: 165 ° C).

The content ratio of the rosin derivative must be 3 parts by weight or more and 50 parts by weight or less per 100 parts by weight of the base polymer. When the content ratio is less than 3 parts by weight, the effect of improving the attenuation performance of the high-attenuation member due to the inclusion of the rosin derivative cannot be obtained. In addition, when the content exceeds 50 parts by weight, the adhesiveness due to the rosin derivative is increased to deteriorate the workability, and it becomes impossible to perform the following operations: kneading the components in order to prepare a highly attenuating composition. The high-attenuation composition is kneaded or formed into an arbitrary shape in order to manufacture a highly attenuating member.

Further, in consideration of further improving the attenuation performance of the high-attenuation member, the content ratio of the rosin derivative is preferably 10 parts by weight or more in the above range.

The imidazole-based compound may, for example, be an imidazole compound having an imidazole ring in the molecule and capable of improving the attenuation performance of a high-attenuation member composed of a highly attenuating composition comprising a cerium oxide, a rosin derivative, and a hindered phenol-based compound. And the aforementioned imidazole-based compound is selected from the group consisting of imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl-imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- At least one of the group consisting of phenylimidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole .

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 view of the effect of improving the attenuation performance of the high-attenuating member, imidazole, 2-methylimidazole, and 1,2-dimethylimidazole are preferred, and among them, imidazole is preferred.

The content ratio of the imidazole-based compound must be 0.1 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the base polymer. If the content ratio is less than 0.1 part by weight, the effect of improving the attenuation performance of the high attenuation member cannot be obtained. In addition, when the content exceeds 10 parts by weight, coking tends to occur and workability is lowered, so that it becomes impossible to perform kneading of components in order to modulate a high-attenuation composition, in order to manufacture high attenuation. The high-attenuation composition is kneaded by a member or formed into an arbitrary shape.

Further, in consideration of maintaining good workability of the high-attenuation composition and further improving the attenuation performance of the high-attenuation member, the content ratio of the imidazole-based compound is preferably 1 part by weight or more, preferably 1 part by weight or more. It is 5 parts by weight or less.

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 a hindered phenol-based compound having two or more of the hydroxyl groups, particularly a bisphenol-based anti-aging agent, a polyphenol-based anti-aging agent, a thiobisphenol-based anti-aging agent, and a pair. One or two or more kinds of anti-aging agents such as an anti-aging agent such as a benzenediol-based anti-aging agent are preferred.

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-toluene 1, 3-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, p-cresol and dicyclopentadiene One or two or more kinds of the base 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 content ratio of the hindered phenol-based compound must be 0.1 parts by weight or more and 20 parts by weight or less per 100 parts by weight of the base polymer. If the content ratio is less than 0.1 part by weight, the effect of improving the attenuation performance of the high attenuation member cannot be obtained. Further, in the case of more than 20 parts by weight, there is a problem that an excessively hindered phenol-based compound easily blooms on the surface of the high-attenuating member as explained above.

In addition, when the attenuation performance of the high-attenuation member is further increased, the content ratio of the hindered phenol-based compound is preferably 1 part by weight or more in the above range.

The high-attenuation composition of the present invention may further contain magnesium acetate and an amine-based anti-aging agent in addition to the respective components. By containing the two components, the attenuation performance of the high attenuation component can be further improved.

The magnesium acetate in the compound may be any of a tetrahydrate salt obtained by an aqueous solution obtained by reacting acetic acid with magnesium oxide or magnesium carbonate, and an anhydrous salt obtained by heating and dehydrating the tetrahydrate salt, in particular The number of steps required to manufacture is small and inexpensive magnesium acetate. Tetrahydrate is preferred.

The content ratio of magnesium acetate is preferably 0.1 part by weight or more and 20 parts by weight or less per 100 parts by weight of the base polymer in the case of the tetrahydrate salt. When the content ratio is less than 0.1 parts by weight, the effect of improving the attenuation performance of the high-attenuation member cannot be obtained. Further, in the case of more than 20 parts by weight, an excessive amount of magnesium acetate becomes easy to cause blooming on the surface of the high-attenuating member.

Further, examples of the amine-based anti-aging agent include alkylated diphenylamines such as N-phenyl-1-naphthylamine and octylated diphenyl groups, and 4,4'-bis(α,α-dimethyl group. Benzyl) Phenylamine, p-(p-toluenesulfonylguanidino)diphenylamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine , N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N' One or two or more kinds of aromatic secondary amine-based anti-aging agents such as (3-methylpropenyloxy-2-hydroxypropyl)-p-phenylenediamine.

It is preferable to contain the amine-based anti-aging agent in an amount of 1 to 2 times the amount of magnesium acetate and 20 parts by weight or less per 100 parts by weight of the base polymer.

When the content ratio is less than 1 time of the amount of magnesium acetate, when the base polymer is rubber, the vulcanization rate of the high-attenuation composition is slow, and the productivity of the high-attenuation member is lowered. Further, when the content exceeds twice the amount of magnesium acetate or exceeds 20 parts by weight, an excessive amount of the amine-based anti-aging agent becomes liable to cause blooming on the surface of the high-attenuating member.

The highly attenuating composition of the present invention may further contain a decane compound in addition to the respective components. The decane compound can be exemplified by the formula (a):

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

The various decane compounds which can function as a dispersing agent for cerium oxide, such as a decane coupling agent or a decylating agent. In particular, one or two or more kinds of alkoxydecanes such as hexyltrimethoxydecane, phenyltrimethoxynonane, phenyltriethoxydecane, and diphenyldimethoxydecane are preferred.

The content ratio of the decane compound is preferably 5 parts by weight or more and 25 parts by weight or less per 100 parts by weight of the cerium oxide.

The high-attenuation composition of the present invention may further contain a tackifier other than a rosin derivative such as a petroleum resin or a scented scented resin. The content ratio of the other tackifier can be appropriately set depending on the content ratio of the rosin derivative or the attenuation characteristics of the high attenuation member.

When the base polymer is a rubber, the high-attenuation composition of the present invention may contain additives such as a vulcanizing agent, a vulcanization accelerator, and a vulcanization accelerating aid in a suitable ratio. Further, the high-attenuation composition may contain an anti-aging agent other than the hindered phenol-based or amine-based compound in an appropriate ratio.

Further, in the high-attenuation composition of the present invention, a filler such as carbon black or calcium carbonate or a softener such as liquid rubber or oil may be contained in an appropriate ratio.

The high-attenuation composition of the present invention can be prepared by arranging the components in a suitable order and kneading using any kneading machine; and forming the high-attenuation composition into a desired shape, and The base polymer is vulcanized in the case of rubber to produce a high attenuation member having a prescribed attenuation characteristic.

For example, a closed kneader such as a kneader is usually used to carry out the smelting of the base polymer for about 1 minute to 2 minutes. (Mastication), on the other hand, continues to carry out the mastication, and the cerium oxide, the rosin derivative, the imidazole compound, the hindered phenol compound, and other components are added in one or a few times, and then further kneaded to prepare a highly attenuating composition.

Preferably, the high-attenuation composition is prepared by first adding a rosin derivative, an imidazole compound, and a hindered phenol-based compound to the base polymer, followed by kneading, and then adding ceria and other components. Mix and practice.

For example, the base polymer is subjected to mastication for about 1 minute to 2 minutes using a closed kneader, and the next step is to continue the mastication. First, a rosin derivative, an imidazole compound, and a hindered phenol compound are added for kneading, followed by a single pass or The cerium oxide and other remaining components are added in fractions, and then further kneaded to prepare a highly attenuating composition.

In this way, the rosin derivative, the imidazole compound, and the hindered phenol compound can be kneaded with cerium oxide in a state of being sufficiently dispersed in the base polymer, so that each of the components can be further effectively functioned. The attenuation performance of the high attenuation component is further improved.

Further, when a rosin derivative or the like is added to the base polymer, for example, if it is 5 parts by weight to 10 parts by weight per 100 parts by weight of the base polymer, a small amount of cerium oxide may be used together with the rosin derivative or the like. Together with the first addition to the base polymer. In other words, a rosin derivative, an imidazole compound, a hindered phenol compound, and a part of cerium oxide may be first added to the base polymer and kneaded, and then the remaining portion of the cerium oxide may be added and kneaded.

Further, a kneaded product obtained by kneading a rosin derivative, an imidazole compound, and a hindered phenol compound may be temporarily taken out from the kneading machine, and then a predetermined amount of the kneaded material may be reintroduced into a closed kneader or the like. Then, other components of cerium oxide are added and kneaded.

In a system comprising magnesium acetate and an amine-based anti-aging agent, the two components may be added to the base polymer together with the rosin derivative or the like, or may be added together with the cerium oxide or the like. Add to the base polymer.

The high-attenuation member which can be formed by using the high-attenuation composition of the present invention includes, for example, a vibration-damping damper built in the foundation of a building such as a high-rise building, and a shock-absorbing (vibration) built-in in the structure of the building. Damping components for cables such as dampers, suspension bridges, or diagonal bridges, anti-vibration components for industrial machinery or aircraft, automobiles, rail vehicles, etc., computer or peripheral devices thereof, or anti-vibration components for household appliances, and Tire surface for automobile tires, etc.

According to the present invention, by adjusting the types, combinations, and content ratios of the cerium oxide, the rosin derivative, the imidazole compound, and the hindered phenol compound within the above range, excellent attenuation suitable for the various uses can be obtained. High attenuation components for performance.

In particular, when the high-attenuation composition of the present invention is used to form a shock damper incorporated in a structure of a building, the shock damper is excellent in vibration attenuation performance, and thus can be reduced to one. The number of damping dampers built into the building. Further, since the temperature dependency is small, the shock damper can be provided even in the vicinity of a wall other than a building having a large temperature difference.

[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 ± 1 ° C and a relative humidity of 55 ± 1% unless otherwise specified.

<Example 1>

In 100 parts by weight of a natural rubber [SMR (Standard Malaysian Rubber)-CV60] as a base polymer, 150 parts by weight of a cerium oxide [Nipsil KQ manufactured by TOSOH SILICA CORPORATION], a rosin derivative [rosin-modified maleic acid] was formulated. 10 parts by weight of resin, softening point of 139 ° C, HARIMACK 135GN manufactured by Harima Chemical Co., Ltd., 1,2-dimethylimidazole as imidazole compound [1,2DMZ manufactured by Shikoku Chemical Industry Co., Ltd.] 2.5 Parts by weight, and 4,4'-butylene bis(3-methyl-6-tert-butylphenol) as a hindered phenolic compound [NOCRAC (registered trademark) NS- manufactured by Ouchi Shinko Chemical Industry Co., Ltd. 30] 2.5 parts by weight and each component shown in the following Table 1 were 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: softening point is 105 ° C, MARUKA LYNCUR (registered trademark) M890A manufactured by Maruzen Petrochemical Co., Ltd.

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

Sulfonamide-based vulcanization accelerator: N-tert-butyl-2-benzoquinazolylsulfinamide, 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.

The mixing step is: firstly, using a closed kneading machine, the natural rubber as the base polymer is subjected to mastication for about 1 minute to 2 minutes, and secondly, the mastication is continued, and the fraction is put into the other than the natural rubber. The composition is further kneaded for about 10 minutes to 40 minutes to obtain a highly attenuating composition.

<Example 2~Example 4>

The content ratio of cerium oxide to 100 parts by weight of the natural rubber as the base polymer was set to 100 parts by weight (Example 2), 135 parts by weight (Example 3), 180 parts by weight (Example 4), and phenyl group was used. The content ratio of triethoxydecane to cerium oxide is the same as in Example 1 (cerium oxide: phenyltriethoxydecane = 150:25), and will be relative to 100 parts by weight of the base polymer. The content ratio of the phenyltriethoxydecane was set to 16.7 parts by weight (Example 2), 22.5 parts by weight (Example 3), and 30 parts by weight (Example 4), except that it was prepared in the same manner as in Example 1. High attenuation composition.

<Comparative Example 1>

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 contained.

<Comparative Example 2, Comparative Example 3>

The content ratio of cerium oxide to 100 parts by weight of the natural rubber as the base polymer was 80 parts by weight (Comparative Example 2) and 190 parts by weight (Comparative Example 3), and phenyltriethoxydecane was made to be relatively Oxide The content ratio of the phenyltriethoxydecane per 100 parts by weight of the base polymer is the same as in the case of Example 1 (cerium oxide: phenyltriethoxydecane = 150:25). A high attenuation composition was prepared in the same manner as in Example 1 except that the amount was 13.3 parts by weight (Comparative Example 2) and 31.7 parts by weight (Comparative Example 3).

<Attenuation characteristic evaluation>

(production of test body)

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

(displacement test)

Two test bodies 3 are prepared as shown in FIG. 2( a ), and the two test bodies 3 are 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 central fixing jig 4 is bolted to the upper fixed 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 placed. The state is strain-deformed in a direction orthogonal to the lamination direction of the test body 3, and secondly, in this state, the movable disk 8 is displaced in the direction of the fixed arm 6 as indicated by a hollow arrow in the figure. In the opposite direction, the state returns to the state shown in FIG. 2( a ), and the above operation is taken as one cycle, and the disk 1 in the test body 3 is subjected to repeated strain deformation, that is, vibration is caused. In the case of the hysteresis loop H (see FIG. 3), the hysteresis loop H indicates the relationship between the displacement amount (mm) and the load (N) in which the disc 1 is displaced in the direction orthogonal to the lamination direction of the test body 3.

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 such 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% or 300% 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 straight line L1 indicated by the thick solid line in the thus obtained graph is obtained. The slope Keq (N/mm), from the slope Keq (N/mm), the thickness T (mm) of the circular plate 1, and the cross-sectional area A (mm ² ) of the circular plate 1, according to the formula (1):

The equivalent shear elastic modulus Geq (N/mm ² ) was obtained. Further, as for the equivalent shear modulus Geq (N / mm ^2), the offset amount is determined shear modulus equivalent Geq100 (N / mm ²⁾ of 100%, with an offset of The equivalent shear modulus Geq300 (N/mm ² ) at 300%.

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 The straight line L1, the horizontal axis of the graph, and the surface area of the region surrounded by the perpendicular line L2 perpendicular to the horizontal axis from the intersection of the straight line L1 and the hysteresis loop H are expressed by the formula (2):

The equivalent decay constant Heq is obtained. Further, as for the equivalent attenuation constant Heq, the equivalent attenuation constant Heq100 at the time when the offset is 100% and the equivalent attenuation constant Heq300 when the offset is 300% are obtained. Among them, the larger the equivalent decay constant Heq100, the more excellent the attenuation performance of the test body 3 can be determined. In the case of the examples and the comparative examples, the case where the equivalent decay constant Heq was 0.38 or more was evaluated as good in the attenuation performance, and the case where the equivalent decay constant Heq was less than 0.38 was evaluated as the deterioration in the attenuation performance.

The above results are shown in Table 2.

Comparing the results of Comparative Example 1 of Table 2 with the results of Examples 1 to 4, it was found that a high-attenuation member formed of the high-attenuation composition of Comparative Example 1 containing no imidazole-based compound and containing no hindered phenol-based compound was equivalent. The attenuation constant Heq100 is less than 0.38 and the attenuation performance is not sufficient. In contrast, the high attenuation members formed by the high attenuation compositions of Examples 1 to 4 which are constituents of the present invention are used, and the equivalent attenuation constant Heq100 is 0.38. Above and excellent in attenuation performance.

Therefore, it has been confirmed that the base polymer contains cerium oxide, a rosin derivative, an imidazole compound, and a hindered phenol compound in a predetermined content ratio, whereby a high-attenuation member excellent in attenuation performance can be obtained. High attenuation composition.

Further, comparing the results of Comparative Example 2 with Examples 1 to 4, it was found that the high-attenuation composition of Comparative Example 2 containing cerium oxide in a range of less than 100 parts by weight per 100 parts by weight of the base polymer was used. The formed high attenuation component has an equivalent attenuation constant Heq100 of less than 0.38 and insufficient attenuation performance. Therefore, it was confirmed that the content of cerium oxide must be 100 parts by weight or more per 100 parts by weight of the base polymer.

Further, comparing the results of Comparative Example 3 with Examples 1 to 4, it was found that a high-attenuation composition of Comparative Example 3 containing cerium oxide in an amount of more than 180 parts by weight per 100 parts by weight of the base polymer was used. The high attenuation component is destroyed when the offset is 300% large. Therefore, it was confirmed that the content of cerium oxide must be 180 parts by weight or less per 100 parts by weight of the base polymer.

Further, by comparing the results of Examples 1 to 4, it was confirmed that the content ratio of cerium oxide is preferably 135 parts by weight or more per 100 parts by weight of the base polymer in the above range.

<Example 5 to Example 8, Comparative Example 4>

The content ratio of the rosin derivative to 100 parts by weight of the natural rubber as the base polymer was 2 parts by weight (Comparative Example 4), 3 parts by weight (Example 5), 20 parts by weight (Example 6), and 30 parts by weight. (Example 7), 50 parts by weight (Example 8), except that the high-attenuation composition was prepared in the same manner as in Example 1.

<Comparative Example 5>

When the content ratio of the rosin derivative to 100 parts by weight of the natural rubber as the base polymer is 55 parts by weight, the adhesion is too strong, and the mixture of the respective components cannot be kneaded to prepare a highly attenuating composition.

Therefore, each of the high-attenuation compositions of the examples and the comparative examples except Comparative Example 5 was subjected to the respective tests described above to evaluate the characteristics. The results are shown together with the results of Example 1 in Table 3.

Comparing the results of Comparative Example 4 of Table 3 with the results of Example 1, Example 5 to Example 8, it is understood that the use of Comparative Example 4 containing a rosin derivative in a range of less than 3 parts by weight per 100 parts by weight of the base polymer is used. The high attenuation member formed by the attenuating composition has an equivalent attenuation constant Heq100 of less than 0.38 and insufficient attenuation performance. Therefore, it was confirmed that the content ratio of the rosin derivative must be 3 parts by weight or more per 100 parts by weight of the base polymer.

Further, Comparative Example 5 was compared with the results of Example 1, Example 5 to Example 8, and Comparative Example 5 containing a rosin derivative per 100 parts by weight of the base polymer in excess of 50 parts by weight, adhered as described above. The sex is too high to modulate the high attenuation composition. Therefore, it was confirmed that the content ratio of the rosin derivative must be 50 parts by weight or less per 100 parts by weight of the base polymer.

Further, by comparing the results of Example 1, Example 5 to Example 8, it was confirmed that the content ratio of the rosin derivative is preferably 10 parts by weight or more per 100 parts by weight of the base polymer in the above range.

<Example 9 to Example 12, Comparative Example 6>

The content ratio of the imidazole compound to 100 parts by weight of the natural rubber as the base polymer was 0.05 parts by weight (Comparative Example 6), 0.3 parts by weight (Example 9), 1 part by weight (Example 10), and 5 parts by weight. (Example 11), 10 parts by weight (Example 12), except that the high-attenuation composition was prepared in the same manner as in Example 1.

<Comparative Example 7>

When the content ratio of the imidazole compound to 100 parts by weight of the natural rubber as the base polymer is 13 parts by weight, the mixture of the components is Coking occurs when the material is mixed, thus abandoning the modulation of the highly attenuating composition.

Therefore, each of the high-attenuation compositions of the examples and the comparative examples except Comparative Example 7 was subjected to the respective tests described above to evaluate the characteristics. The results are shown together with the results of Example 1 in Table 4.

Comparing the results of Comparative Example 6 of Table 4 with those of Example 1, Example 9 to Example 12, it was found that the use of Comparative Example 6 containing an imidazole-based compound in a range of less than 0.1 part by weight per 100 parts by weight of the base polymer was used. The high attenuation member formed by the attenuating composition has an equivalent attenuation constant Heq100 of less than 0.38 and insufficient attenuation performance. Therefore, it was confirmed that the content ratio of the imidazole-based compound must be 0.1 part by weight or more per 100 parts by weight of the base polymer.

Further, Comparative Example 7 was compared with the results of Example 1, Example 9 to Example 12, and Comparative Example 7 containing an imidazole-based compound per 100 parts by weight of the base polymer and more than 10 parts by weight, as described above, was as easy as described above. Coking occurs and the high attenuation composition cannot be modulated. Therefore, it was confirmed that the content ratio of the imidazole-based compound must be 10 parts by weight or less per 100 parts by weight of the base polymer.

Further, by comparing the results of Example 1, Example 9 to Example 12, it was confirmed that the content ratio of the imidazole-based compound within the above range is preferably 1 part by weight or more and 5 parts by weight per 100 parts by weight of the base polymer. The following.

<Example 13 to Example 16, Comparative Example 8>

The content ratio of the hindered phenol compound to 100 parts by weight of the natural rubber as the base polymer was 0.05 parts by weight (Comparative Example 8), 0.3 parts by weight (Example 13), 1 part by weight (Example 14), and 10 parts by weight. The high-attenuation composition was prepared in the same manner as in Example 1 except for the portion (Example 15) and 20 parts by weight (Example 16).

<Comparative Example 9>

When the content ratio of the hindered phenol-based compound to the natural rubber as the base polymer of 100 parts by weight is 23 parts by weight, blooming occurs on the surface of the high-attenuating member.

The high-attenuation compositions of the respective examples and comparative examples were subjected to the respective tests described above to evaluate the characteristics. The results are shown together with the results of Example 1 in Table 5.

Comparing the results of Comparative Example 8 of Table 5 with the results of Example 1, Example 13 to Example 16, it was found that Comparative Example 8 containing a hindered phenol-based compound in a range of less than 0.1 part by weight per 100 parts by weight of the base polymer was used. The high attenuation component formed by the high attenuation composition has an equivalent attenuation constant Heq100 of less than 0.38 and insufficient attenuation performance. Therefore, it was confirmed that the content ratio of the hindered phenol-based compound must be 0.1 part by weight or more per 100 parts by weight of the base polymer.

Further, Comparative Example 9 was compared with the results of Example 1, Example 13 to Example 16, and Comparative Example 9 containing a hindered phenol-based compound per 100 parts by weight of the base polymer in excess of 20 parts by weight, as explained above Produces blooming. Therefore, it was confirmed that the content ratio of the hindered phenol-based compound must be 20 parts by weight or less per 100 parts by weight of the base polymer.

<Example 17>

A high-attenuation composition was prepared in the same manner as in Example 1 except that the imidazole (manufactured by Nippon Synthetic Chemical Co., Ltd.) was used in the same amount as the imidazole-based compound.

<Example 18>

Further, 2.5 parts by weight of magnesium acetate ‧ tetrahydrate [manufactured by Kishida Chemical Co., Ltd.] and N-phenyl-N'-(1,3-dimethylbutyl)-p-benzene as an amine-based anti-aging agent are further added. A high-attenuation composition was prepared in the same manner as in Example 1 except that 5 parts by weight of a diamine [NOCRAC 6C manufactured by Ouchi Shinko Chemical Co., Ltd.) was used.

<Example 19>

The same components were used in the same ratio as used in Example 1, and the high-attenuation composition was prepared in the following procedure.

That is, the natural rubber as the base polymer is subjected to mastication for about 1 minute to 2 minutes using a closed kneader, and the rosin derivative, the imidazole compound, the hindered phenol compound, and the dioxide are further introduced while continuing the mastication. One part of the crucible (10 parts by weight per 100 parts by weight of the natural rubber) was further kneaded for about 1 minute to 2 minutes, and then the kneaded material was temporarily taken out to the outside of the closed kneader.

Next, the predetermined amount of the kneaded material is measured, and the closed kneading machine is again used for the mastication for about 1 minute to 2 minutes, and the next step is to continue the mastication while the remaining portion of the ceria is added in fractions (relative to the weight per 100 weight). The natural rubber was 140 parts by weight) and the components shown in Table 1, and further kneaded for about 10 minutes to 40 minutes to obtain a highly attenuating composition.

The high-attenuation compositions of the respective examples were subjected to the respective tests described above to evaluate the characteristics. The results are shown together with the results of Example 1 in Table 6.

From the results of Example 1 and Example 17 of Table 6, it is understood that the attenuation performance of the high-attenuation member can be improved by using imidazole as the imidazole-based compound. Further, from the results of Example 1 and Example 18, it is understood that the attenuation property of the high-attenuating member can be improved by further containing magnesium acetate and an amine-based anti-aging agent in the high-attenuation composition. Further, as a result of the results of the examples 1 and 19, it is understood that the rosin derivative or the like is first added to the base polymer and kneaded, and then cerium oxide or the like is added and kneaded, whereby the attenuation performance of the high-attenuation member can be improved.

<Example 20 to Example 23, Comparative Example 10>

The content ratio of imidazole to 100 parts by weight of the natural rubber as the base polymer was set to 0.05 parts by weight (Comparative Example 10), 0.3 parts by weight (Example 20), 1 part by weight (Example 21), and 5 parts by weight (Example) 22), 10 parts by weight (Example 23), except that the high-attenuation composition was prepared in the same manner as in Example 17.

<Comparative Example 11>

When the content ratio of the imidazole to 100 parts by weight of the natural rubber as the base polymer is 13 parts by weight, coking occurs when the mixture of the components is kneaded, and thus the preparation of the highly attenuating composition is discarded.

Therefore, each of the high-attenuation compositions of the examples and the comparative examples except Comparative Example 11 was subjected to the respective tests described above to evaluate the characteristics. The results are shown together with the results of Example 17 in Table 7.

[Table 7] Table 7

Comparing the results of Comparative Example 10 and Example 17, Example 20 to Example 23 of Table 7 with the results of Table 4 above, it can be seen that although the equivalent decay constant Heq100 is improved overall, it is used in relation to 100 parts by weight. The high-attenuating member formed of the high-attenuation composition of Comparative Example 10 containing the imidazole in the range of less than 0.1 part by weight of the base polymer is compared with the example 17 and the examples 20 to 23 in which the content ratio is set to 0.1 part by weight or more. The equivalent decay constant Heq100 is low and the attenuation performance is not sufficient. Therefore, it was confirmed that the content ratio of imidazole must be 0.1 part by weight or more per 100 parts by weight of the base polymer.

Further, comparing the results of Comparative Example 11 with Example 17, Example 20 to Example 23, it is understood that Comparative Example 11 containing imidazole in an amount of more than 10 parts by weight per 100 parts by weight of the base polymer is easily produced as described above. Coking does not modulate high attenuation compositions. Therefore, it was confirmed that the content ratio of imidazole must be 10 parts by weight or less per 100 parts by weight of the base polymer.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. Protection The scope is subject to the definition of the scope of the patent application attached.

1‧‧‧ round plate

2‧‧‧ steel plate

3‧‧‧Test body

4‧‧‧Central Fixture

Fixed fixture around 5‧‧

6‧‧‧Fixed Arm

7, 9‧‧‧ joints

8‧‧‧ movable plate

L1‧‧‧ Straight line

L2‧‧‧ vertical line

Keq‧‧‧ slope

△W‧‧‧Amount of absorbed energy

W‧‧‧elastic strain energy

H‧‧‧ Hysteresis loop

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

(a) and (b) of FIG. 2 are schematic views for explaining 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 in which the relationship between the displacement amount and the load obtained by displacing the test body using the test machine.

1‧‧‧ round plate

2‧‧‧ steel plate

3‧‧‧Test body

Claims (7)

A high-attenuation composition, characterized in that the high-attenuation composition contains: a base polymer; and 100 parts by weight or more and 180 parts by weight or less of cerium oxide and 3 parts by weight per 100 parts by weight of the base polymer. 50 parts by weight or less of the rosin derivative, 0.1 parts by weight or more and 10 parts by weight or less of the imidazole-based compound, and 0.1 parts by weight or more and 20 parts by weight or less of the hindered phenol-based compound, wherein the imidazole-based compound is selected from the group consisting of imidazole, 1, 2 - dimethylimidazole, 2-ethyl-4-methyl-imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-methylimidazole, 2-111 At least one selected from the group consisting of alkylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. The high-attenuation composition according to claim 1, wherein the base polymer is at least one selected from the group consisting of natural rubber, isoprene rubber, and butadiene rubber. The high attenuation composition of claim 1 or 2, wherein the imidazole compound is imidazole. The high-attenuation composition according to claim 1 or 2, further comprising magnesium acetate and an amine-based anti-aging agent. The high-attenuation composition according to the first or second aspect of the patent application is prepared by the following steps: first adding a rosin derivative, an imidazole compound, and a hindered phenol compound to the base polymer, and kneading Then, the cerium oxide is added and kneaded. The high-attenuation composition according to claim 5, wherein a rosin derivative, an imidazole compound, and a first one are added to the base polymer. The phenol-based compound and one part of the cerium oxide are kneaded, and then the remaining portion of the cerium oxide is added and kneaded. A high-attenuation composition as described in claim 1 or 2, which is used as a material for forming a damper for building vibration.