TW201116580A - High decay composition - Google Patents

Abstract

Provided is a high decay composition which can maintain well processability and manufacture a high decay portion having excellent decay ability compared to status quo without causing problems such as generation of bloom. The high decay composition of this invention includes: base polymer, a silicon oxide of 100 to 180 parts by weight per base polymer of 100 parts by weight, a rosin derivative of 3 to 50 parts by weight per base polymer of 100 parts by weight, an imidazole compound of 0.1 to 10 parts by weight per base polymer of 100 parts by weight and a hindered phenol compound of 0.1 to 20 parts by weight per base polymer of 100 parts by weight.

Description

201116580 VI. Description of the Invention: [Technical Field] The present invention relates to a high-attenuation composition which is a raw material for a high-attenuation member which mitigates and absorbs the transmission of vibration energy. [Prior Art] For example, in buildings such as high-rise buildings or bridges, industrial machinery, aircraft, automobiles, rail vehicles, computers or peripheral devices, household appliances, and even automobile tires, in order to ease and absorb The transmission of vibration energy, that is, vibration-free, vibration-proof, vibration-damping, anti-vibration, etc., uses a high-attenuation member containing a rubber knee or the like as a base polymer. In order to improve the attenuation performance so that the hysteresis loss (hysteresis lGSS) when the vibration is applied is increased, the energy scale of the vibration is good and fast.

However, the high attenuation portion cannot sufficiently increase the attenuation performance of the high attenuation member and the attenuation performance of the member by the previously high attenuation components. The current situation is further improved, a proportional method, etc., but for example, it is considered to further increase the high-attenuation member of the filler, etc., which has a high attenuation of the filling shoulder or the adhesive of 3, and the following operations are performed. Correct

Or forming into the three-dimensional shape 201116580, especially in the case of mass production of high-attenuating parts at the factory level, the low workability is to reduce the productivity of the high-attenuating parts, and increase the energy consumption required for production. In addition, the reason for the increase in production costs is not ideal. Therefore, the following studies have been conducted: the high-attenuation composition contains a hindered I-based compound as an attenuating imparting agent, and the hindered compound is mixed with a filler such as a dioxic cut or a pine (four). In this way, the performance of the city is improved. (For example, refer to Patent Document 4 to Patent Document; [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-2014 [Patent Document 2] Japan [Patent Document 3] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 366118 No. [Patent Document 6] Japanese Patent No. 366118 No. [Patent Document 7] Japanese Patent No. 36752丨6 [Disclosed to the Invention] When the attenuation performance is increased and the content ratio of the hindered compound is increased, there is a problem that the hindered phenol compound becomes easy to bloom on the surface of the high-attenuation member. It is an object of the present invention to provide a High attenuation The high-attenuation composition of the object can maintain good processability, and does not cause problems such as blooming, and the high-attenuation member which is superior in attenuation performance compared with the current state is produced in 201116580. The present invention is a high-attenuation composition. The high-attenuation composition contains: a base polymer; and 100 parts by weight or more and 180 parts by weight or less of the total amount of the base polymer, and 3 parts by weight or more and 50 parts by weight or less per 1 part by weight of the base polymer. a rosin derivative, 01 parts by weight or more and 1 part by weight or less of the imidazole-based compound, and 1 part by weight or more and 20 parts by weight or less of the hindered phenol-based compound. According to the present invention, the cerium oxide, the rosin derivative, and the hindered phenol are used. Further, the imidazole-based compound is contained in the compound, and the content ratio of the cerium oxide, the rosin derivative, and the hindered phenol-based preparation is not increased, so that the processability of the high-attenuating composition is not lowered or the blooming is caused. It is problematic to further improve the attenuation performance of the high attenuation member formed using the high attenuation composition as compared with the current situation. According to the invention, the cerium oxide, the rosin derivative, the imidazole-based compound, and the hindered phenol-based compound are each adjusted to a content within the predetermined content ratio, and the compound having a different type is contained, thereby attenuating The freedom of design of the attenuation performance of the component is improved, which facilitates the consideration of the attenuation performance in the design of the high-attenuation component. The base polymer can be used: it can contain the compound of the sulphur dioxide, the rosin derivative L and the complex Any kind of various basic polymers that have a high attenuation performance. However, especially consider the formation of high-attenuation parts that can reduce the attenuation performance and the temperature dependence, which is stable in the wide range. , the base polymer is preferably selected from the group consisting of natural rubber, isodecene 201116580 rubber and Ding Er Zai, at least the species, the natural rubber, the isoprene rubber and the butadiene rubber are not Since it has a polar group, the temperature dependence of characteristics such as rigidity near room temperature is small. As the sodium salivation compound, any of the various (four) shirts and compounds of the various functions of the cyanidinal ring in the molecule can be used: the high attenuation of the dream containing the oxidized dream, the rosin enchantment and the sirolimus compound can be improved. , the attenuation performance of the high attenuation component composed of the object. However, if the attenuation performance of the high-attenuation component is considered to be improved, the Miva-based compound car is good. 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 member can be further improved. The highly attenuating 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, the base polymer towel is firstly added with a rosin-derivative compound and a kneaded mixture, and then kneaded with a hardened oxidizing agent. Further, a rosin derivative, an imidazole compound, a hindered phenol compound, and a part of cerium oxide may be first added to the base polymer to be kneaded, and then the remainder of the cerium oxide may be added and kneaded. Thereby, the rosin derivative n-derivative and the hindered lanthanide compound can be kneaded with cerium oxide in a state of being sufficiently dispersed in the base polymer. Therefore, the respective components can be further effectively functioned. The attenuation performance of the high attenuation component is further improved. 201116580 When the high-attenuation composition is used as a forming material to form a building damping damper as an attenuating member, the number of the shock dampers included in the I: building can be reduced. . Further, since the temperature dependence 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. [Effects of the Invention] By the present invention, it is possible to provide a high-attenuation composition which can maintain good processability without causing blooming and the like, and exhibits attenuation performance as compared with the current state. More excellent high attenuation components. The above and other objects, features, and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] The high-attenuation composition of the present invention contains: a base polymer; and a phase = 10 parts by weight or more of cerium oxide, 3 parts by weight or more and 50 parts by weight per 100 parts by weight of the base polymer. The following base polymerization in each of the following components: 0.1 part by weight or more and 1 part by weight or less of the imidazole-based compound and 0.1 part by weight or more and 20 parts by weight or less of the hindered phenol-based compound 45 / oxygen The material can be used: any of various base polymers which can be subjected to a high attenuation property by containing a ruthenium hydride, a rosin derivative, an imidazole compound, and a hindered phenol compound, wherein the ruthenium is a rubber. Examples of the rubber include natural rubber, isoprene phthalene rubber, styrene butadiene rubber, norbornene rubber, 6-ene 201116580, ethylene propylene diene rubber, butyl rubber, and functional butyl. One or two or more kinds of rubber, 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 butyl rubber.

The rubber may be used in combination of two or more kinds. 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. The cerium oxide can be any of the wet dioxins such as the dry oxidizing dream classified according to the manufacturing method thereof. Further, in consideration of the effect of improving the attenuation performance of the Weiqian high-attenuating material as a filler, the oxygen-cutting is preferably a BET specific surface area of the contact m2/g~_, and the gas phase is represented by the use of nitrogen as an adsorption gas. 2. It is necessary to obtain the basis for each 100 parts by weight of the base:: parts by weight; the attenuation of the parts to be reduced (4) When the amount of the weight of the parts is more than 180 parts by weight, It has become difficult to mass produce two bodies at the factory level: 201116580 ? high attenuation components. Further, although the member can be formed at a trial level, but the formed high-attenuation member is hard and hard to be deformed, there arises a problem that it is easily broken particularly at the time of large deformation. In addition, in the case of considering the attenuation performance of the ruthenium attenuating member, the content of the dioxin is in the range of parts of the rosin derivative, for example, rosin and a polyhydric alcohol (such as glycerin) or a rosin-modified malayan compound. (4) The tree as a constituent component has various derivatives which have an effect of giving a high attenuation material attenuating month bk. The softening point of the rosin derivative is preferably 12 Å or more, preferably 180 ° C or less, particularly preferably 16 Å < t or less. When the softening point is less than the above range, the 虞H surface in which the effect of improving the attenuation performance of the high-attenuation member is not sufficiently obtained is obtained. When the range is exceeded, the additive property is lowered, and it becomes difficult to perform the following operations. Then, in order to modulate a high-attenuation object, each component is kneaded 'the high-attenuation component is kneaded for manufacturing a high-attenuation member' or formed into an arbitrary shape. Further, the softening point can be represented by a value measured by a softening point test method (ring and ball method) described in Japanese Industrial Standard JIS K2207 1996 "Petroleum Bitumen". Examples of the rosin derivative include MSR-4 (softening point: 127 ° C) and DS-130 (softening point: 135. (:), AD- in the HARIESTER series manufactured by Harima Chemical Co., Ltd. 130 (softening point: 201116580 135 °C), DS-816 (softening point: 148 °C), DS-822 (softening point: 172 °C), 145P in the HARIMACK series manufactured by Harima Chemical Co., Ltd. Softening point: 138 ° C), 135 GN (softening point: 139. (:), AS-5 (softening point: 165 ° C), etc., one or more. The proportion of rosin derivatives must be relative to each 1 part by weight of the base polymer is 3 parts by weight or more and 50 parts by weight or less. 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, and the workability is lowered, so that it is impossible to perform the following operations: mixing the components in order to prepare a highly attenuating composition. In order to manufacture high attenuation components Further, the composition is kneaded or formed into an arbitrary shape. Further, in consideration of further improving the attenuation performance of the attenuating member, the content ratio of the rosin derivative is preferably 1 part by weight in the above range. In the above-mentioned imidazole-based compound, for example, various imidazole compounds having the following functions in the various dimers of the imidazole ring in the molecule can be used: the high-attenuation composition of the coated cerium oxide, the rosin derivative, and the hindered phenol compound can be improved. Attenuation performance of the high-attenuation member constituting the imidazole-based compound, for example, imidazole, i, 2, dimethyl hydrazine, 2, ethyl decyl-imidazole, benzyl-2-methylimidazole, 1 -Benzyl-2-(meth)-based 7-seat, 2-mercaptoimidazole, 2-undecylimidazole, 2-heptadecylmiamide, phenylmimetom, 2-phenylindoleimidazole, etc. One or more of them. 11 201116580 Considering the effect of improving the attenuation performance of the damper attenuating part, it is preferable that (four), bismuth base material, and 12 曱 曱 base type miso, the best one is α米β sits.

The content ratio of the azole compound is required to be G. 1 part by weight or more and 1 part by weight or less per 1 part by weight of the base polymer. If the content is contained in the amount of 0.1 t, the effect of attenuating the high-attenuation member cannot be obtained. In addition, when the content ratio exceeds 10 parts by weight, coking is caused to cause workability to be lowered, and it becomes impossible to perform the following operations: kneading each component in order to modulate a highly attenuating composition, in order to manufacture high The aging member and the riding attenuating composition are kneaded or shaped 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 i parts by weight or more in the above range, preferably It is 5 parts by weight or less.

As the hindered phenol-based compound, any of various hindered phenol-based compounds which function as follows: * the interaction with the base of the dioxent surface recorded in the molecule, and the ceria is led by the base polymer The affinity and complexity of each component of the organic system are improved, and the attenuation performance of the high-attenuation member of the money is further improved. The hindered compound is preferably a hindered phenol compound having two or more of the above-mentioned warp groups, particularly a bisphenol-based anti-aging agent, a polyphenol 2 anti-aging agent, a thio-double expectant anti-aging agent, One or two or more kinds of anti-aging agents such as anti-aging agents such as a stilbene-based anti-aging agent are preferred.哥12 201116580 m in the double (four) anti-aging class such as the extinction of the base of the burning, 2,2, methylene bis (4 butyl phenol), 2,2, · methylene bis (4) ethyl Monobutyl 雔 "6 Ί Ί 其 其 其 P η η η η η 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Benzene), 3,9,2 π bis (3_f -6-6-milyl)_1,1·-methylethyl>2, 仏1G•tetraoxygen ==cyclobutyl The reaction product or the like is bis-butyl-4-hydroxyphenyl)propionate], etc. (5, - - 2 - 6 - S aging agent, for example, 4,4 thio bis (3) ·Methyl shout, J ^ 雔 flute 4,4, bis (3,5_ di-t-butyl pin base) thio-salt-thio bis (6_t-butyl. o-to-be), etc. The base of the compounding agent may, for example, be 2,5 bis tributyl phthalocyanine or mono-t-butylpentyl hydroquinone or the like, or two kinds of hydrazines. It is equivalent to 2 parts by weight or less per 100 parts by weight of the two parts of the product. If the content is less than 2g parts by weight, the attenuation property of the high-attenuating member can not be obtained. Moreover, more than 20 parts by weight. Situation There is the following t, · The $_ compound of the over-the-counter is easy to bloom on the surface of the parts of the garment reduction as described above. Your company 0, the company also considers the attenuation of the high-attenuation material to improve the step-by-step The content ratio of the compound is preferably 1 part or more in the above range. To 13 201116580 The 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 property of the high-attenuation member can be further improved. The magnesium acetate in the compound can be obtained by using an aqueous solution obtained by reacting acetic acid with magnesium oxide or magnesium carbonate, and Any one of the anhydrous salts obtained by heating and dehydrating the tetrahydrate salt, in particular, a magnesium oxide, tetrahydrate salt, which is required to be produced in a small number of steps and which is inexpensive, preferably contains a ratio of acetic acid to the tetrahydrate salt. In the case of the above, it is preferably 1 part by weight or more and 2 parts by weight or less per 100 parts by weight of the base polymer. If the content ratio is less than 01 parts by weight, there is no improvement in the attenuation performance of the high attenuation member. Further, in the case of more than 20 parts by weight, an excessive amount of magnesium acetate becomes easy to bloom on the surface of the high-attenuating member. Further, the amine-based anti-aging agent may, for example, be phenyl _ 丨 _ naphthalene. Amine, octylation-based alkylation of diphenylamine, sharp-hearted, ... dimethylbenzyl)diphenylamine, p-(p-toluenesulfonylguanidino)diphenylamine , N,N,-di-2-naphthyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N-phenyl-N,-isopropyl-p-phenylenediamine, N -Phenyl-indole, _(1,3·dimethylbutyl)_p-phenylenediamine, N-phenyl-indole·(3-methylpropenyloxy-2-yl-propyl) One or two or more kinds of aromatic secondary amine-based anti-aging agents such as p-phenylenediamine. It is preferable to contain the amine-based anti-aging agent in a ratio of 2 times the amount of magnesium acetate and 2 parts by weight or less per 1 part by weight of the base compound. When the ratio of the right content is less than the amount of magnesium acetate, the base polymer 201116580, in the case of rubber, has a slower vulcanization rate of the high-attenuation composition and a decrease in the productivity of the high-pressure-reduction component. Further, in the case where the content exceeds twice the amount of cerium acetate or exceeds 2 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 high-attenuation composition of the present invention may further contain a stone-smelting compound in addition to the above components. The zephyr compound can be exemplified by the formula (a): [Chemical 1]

R2 R1-Si-R3 (8) In the formula j, at least one of R1, R2, 尺3 and R4 represents a silk group.

However, R, R2, R3 and R4 are not alkoxy groups at the same time, and represent other alkyl groups or aryl groups. A decane compound such as a decane coupling agent or a decylating agent represented by J, which can function as a dispersing agent for cerium oxide. In particular, an alkoxy decane such as a hexyl methoxy group, a phenyl trimethoxy group or a phenyl triethoxy group = a dimethoxy decane or two or more kinds thereof is preferred. The content ratio of the decane compound is preferably 5 parts by weight or more and 25 parts by weight or less per 1 part by weight of the cerium oxide. * The high-attenuation composition of the present invention may further contain a reinforcing agent other than the rosin derivative such as petroleum resin or cedar. The content ratio of the other additives may be appropriately set depending on the content ratio of the rosin derivative or the attenuation characteristics of the high attenuation portion 15 201116580. In the case where the base polymer is rubber, the high-attenuation composition of the present invention may contain a vulcanizing agent, a vulcanization accelerator, a vulcanization, a feed, and a fresh additive in a suitable ratio. Further, in the high-attenuation composition, other anti-aging agents other than New Zealand and (4) may be contained in a suitable ratio. Further, in the southern sag composition of the present invention, for example, carbon black, carbonic acid scale-filled woven silk rubber, oil 4 softener or the like may be appropriately contained. The high-attenuation composition of the present invention can be prepared by mixing the components in a suitable order, using 'any kneading machine', and forming the shape into a shape by attenuating the composition, and in the base polymerization (4) / In the case of sulphide L, the southern sag component with the specified attenuation characteristics is produced. "如通* Use kneading machine (5) Qiu Xin. In a closed-type kneading machine, the base polymer is aged for 1 minute to 2 minutes = a, ation), and the next step is to continue the mastication, and the cerium oxide, rosin derivative, and imidazole compound are added once or separately. The hindered phenolic compound and other ingredients are then 'mixed' and then mixed to prepare the composition. Preferably, the high-attenuation composition is prepared by first adding a rosin derivative, an imidazole-based compound to the base polymer, and blocking the compound to be kneaded, and then adding the wheat dioxide and other components. Mix and practice. For example, using a closed kneader, the base polymer is enthalpy for 2 minutes, and the amount of the rosin derivative, the imidazole compound, and the hindered phenolic compound is first mixed. The high-attenuation composition is prepared by injecting cerium oxide and other remaining components in a fraction or less and then further kneading. In this way, the rosin derivative, the sodium sulphate compound, and the age-restricted person can be sufficiently immersed in the base polymer to be immersed in the cerium oxide, so that the components can be effectively and step by step. Function ^ Improve the attenuation performance of high attenuation components. Further, when a rosin derivative or the like is added to the base polymer, it is added in an amount of 5 parts by weight to 10,000 parts by weight per weight of the base polymer, and a small amount of oxidized granules to the right is added together with the rosin derivative or the like. Base hybrid towel. g卩, can also be based on the base = derivative compounds, and the resistance of the two to be mixed = and then add the remainder of the oxidation of the Huanhuan; the division of the season: eight things plus rosin derivatives, sodium salivary compounds and the resistance of the resistance Shooting two t' and then adding other components of the dioxin; the machine is equal to containing magnesium acetate and amine lanthanum, and the Kunming compound and the rosin derivative are the same, in the system, the two bases can be polymerized. In addition, the fish dioxin and cerium oxide may be added to the substrate more previously. /, - 矽 and the like are subsequently added to the base polymerization, and the high-attenuation member formed by the high-attenuation & formation of the present invention is used in the example 17 201116580, and the shock-absorbing damper incorporated in the base towel of the building such as the building is listed. In the structure of building ^, the damper for damping (vibration), suspension bridge or diagonal bridge, etc., vibration-proof components, etc. Electric thieves (4), anti-vibration parts such as wire electrical appliances, and tire treads for automobile tires. According to the present invention, by adjusting the type of the magnet dioxide, the perfume derivative, the imidazole compound, and the hindered phenol compound, and the composition and ratio thereof, the above-mentioned various uses can be obtained. High attenuation component with excellent attenuation 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 in one building. The number of damping dampers built into the object. Further, since the temperature dependence 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. [Examples] 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 ± rc 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, cerium oxide [Nipsil KQ manufactured by TOSOH SILICA CORPORATION] 150 parts by weight of 'rosin derivative [rosin] was formulated. Modified maleic acid resin, softening point is 139 ° C, 201116580

HARIMACK 135GN manufactured by Harima Chemical Co., Ltd.] 1 part by weight, 1,2-dimethylimidazole as an imidazole compound [1,2DMZ manufactured by Shikoku Chemical Industry Co., Ltd.], 2.5 parts by weight, and as a hindered phenol 4,4'·Butylene bis(3-methyl-6-tert-butylphenol) of the compound [NOCRAC (registered trademark) NS-30 manufactured by Ouchi Emerging Chemical Industry Co., Ltd.] 2.5 篁, Further, each component shown in the following Table 1 was kneaded by a closed kneader to prepare a highly attenuating composition. [Table 1] Table 1 Ingredient I Stupid diethoxy saponin-cyclopentane-suppressor; 5 oil thank gram - 25----- ....1 grass 咔 resin 25 ' 1 〇 ~- benzoimidazole Anti-aging 剤~2~~ 瓯-based anti-aging agent-2--- 5% oil treatment powder sulfur 1.58 sulfinamide-based thinning accelerator 1 ~ - thiuram vulcanization accelerator 0?7 ~ zinc oxide 2 kinds - '~~'~~4--- Stearic acid I - Carbon black 3 - Liquid polyisoprene rubber ~~'~~~-- The components in Table 1 are as follows. Phenyl triethoxy zexi: KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.

Dicyclopentadiene petroleum resin: The softening point is 1〇5. (: 'MARUKALYNCUR (registered trademark) manufactured by Maruzen Petrochemical Co., Ltd. M890A Kasuga resin: softening point is 90 °C, ESCURON (registered trademark) G-90 benzoimidazole-resistant Aging agent: 2-mercaptobenzimidazole, Ouchi Shinsei 201116580

NOCRAC MB manufactured by Industrial Co., Ltd.

Anti-aging agent: Antigen FR manufactured by Jushi Chemicals Co., Ltd. 5% oil-treated powder sulfur: vulcanizing agent, Tsurumi Chemical Industry Co., Ltd. sulfinamide-based vulcanization accelerator: N-t-butyl -2- 幷 幷 thiazolylsulfinamide, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

NOCCELER (registered trademark) NS

秋lam-based vulcanization accelerator: NOCCELER TBT-N manufactured by Ouchi Shinko Chemical Industry Co., Ltd. 2 kinds of zinc oxide: Mitsui Metals Mining Co., Ltd. manufactures stearic acid: "Tsubaki" made by Nippon Oil Co., Ltd. : Diablack (registered by Mitsubishi Chemical Corporation)

Trademark) G Liquid polyisoprene rubber: softener, LIR50 manufactured by Kuramoto Co., Ltd. The procedure of kneading is: first use a closed kneading machine, the natural rubber shaft as the base polymer for 1 minute ~ 2 minutes After the practice of the left and right, the next step is to continue the mastication - the fractional investment in addition to the other components of the rubber, and then proceed to the mixing of 1G minutes to 4Q minutes to obtain a high attenuation composition. <Example 2 to Example 4> The content ratio of the natural rubber as the base polymer to the ruthenium dioxide was set to 1 part by weight (Example 2), 135 weight 20 201116580 parts (example) 3), 180 parts by weight (Example 4) and the ratio of the content of phenyltriethoxysulfonium to cerium oxide was the same as in Example 1 (the dioxide dioxide: phenyltriethoxydecane = 15 〇: In the manner of 25), the content ratio of the phenyltriethoxysilane of the base polymer per 1 part by weight is set to 16.7 parts by weight (Example 2), 22.5 parts by weight (Example 3), 30. Parts by weight (Example 4) were prepared in the same manner as in Example 而 to prepare a high-attenuation composition. <Comparative Example 1>

The high-attenuation composition was prepared in the same manner as in the real m 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 the natural rubber as the base polymer to the ruthenium dioxide was set to 80 parts by weight (Comparative Example 2) and 19 〇 weight injury (for Comparative Example 2) Ratio (4) 3) and the ratio of phenyl triethoxy 7 to the side of the cerium oxide and the side of the example 1 (dioxotomy: stupid triethoxylate and 150 - square ί, will be relative to each (10) The content ratio of the base-ethyl lactyl-wet in the weight-based base polymer was set to 13 cases 2) and 3 parts by weight (▲ Comparative Example 3), and was prepared in the same manner as in the above. Shangnong reduced the composition. <Evaluation of attenuation characteristics> (Production of test body) The high attenuation of the modulation in the examples and the comparative examples was formed into a sheet shape and then pressed, and a circular plate was produced as shown in Fig. 1! (^5 is a groove diameter of 25 jobs) 'On both sides of the front and back of the disc 1 respectively: 21 201116580 Adhesive and laminated 6 mm x vertical 44 44 rectangular rectangular plate 2' - surface Pressurization in the direction of the delamination layer-surface heating to the enamel, vulcanization of the high-attenuation composition forming the circular plate 1, and vulcanization of the circular plate i and the steel plate 2, and production of a model for the high-attenuation member Test body 3. (displacement test)

Two test bodies 3 were prepared as shown in Fig. 2 (8), and the two test bodies 3 were fixed to one central fixing jig 4 by bolts (bGit) via the steel plates 2, and the plugs were fixed. Fixing each of the left and right fixed fixtures 5 on each of the two sides. Then, ^ 嫱 = 4, and the bolts are fixed to the test arm 6 (not shown) via the joint 7; and the clamps 5 are fixed to the left and right sides, The bolt is fixed to the movable plate 8 on the lower side of the testing machine by bolts. In this state, as shown by the hollow arrow of the money, the direction of the fixed arm 6 can be lifted as shown by the hollow arrow, as shown in the figure. The circular plate i in the square 3 shown in (8) is set to be laminated with the test body 3.

The state of the upper strain deformation, and secondly from this state, if the direction phase ==, the movable disk 8 is displaced and lowered in the opposite direction to the fixed arm 6, and returns to the FIG. 2 of FIG. 2, which is late. = table: the hysteresis loop of the circle (the relationship between the displacement direction (_) and the load (8) of the t-measurement measured by the stacking direction of the reference body 3 is the same as the operation of the load of 3 cycles. The value of the third time is 22 201116580 and the amount of shift in the direction perpendicular to the lamination direction of the two steel sheets 2 of the missing disc is 1% of the thickness of the disc 1 or The maximum displacement amount is set by the method of 3〇〇%. Next, the maximum displacement point in the hysteresis loop 所示 shown in Fig. 3 obtained by the measurement is connected to the minimum displacement point, and the resulting map is obtained. The slope Keq (N/mm) of the straight line Li indicated by the thick solid line, the slope Keq (N/mm), the thickness τ (mm) of the circular plate 1, and the cross-sectional area A (mm2) of the circular plate 1. According to formula (1): • [number 1]

Geq=^-XT- A (1) The equivalent shear elastic modulus Geq (N/mm2) is obtained. Further, as for the equivalent shear elastic modulus Geq (N/mm 2 ), the equivalent shear elastic modulus Geql00 (N/mm 2 ) at the offset of 100% and the offset of 300% are obtained. The equivalent shear modulus of the time is Geq3 〇〇 (N/mm2). Moreover, 'the amount of absorbed energy AW (expressed by the total surface area of φ, 咿 ring 由) represented by the slanted 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, are expressed according to the formula (2): [Number 2 ] 砀=丄X鍟W (2) Find the equivalent decay constant Heq. Further, as for the equivalent decay constant Heq', the equivalent decay constants H when the offset amount is 1% is obtained are 1〇〇, 23 201116580, and the equivalent decay constant Heq300 when the offset is 300%. Among them, the larger the equivalent decay constant HeqlOO, 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 not in Table 2. [Table 2] Table 2 Comparative Example 1 Comparative Example 2 Example 2 Example 3 Example 1 Example 4 Comparison '3_ parts by weight of cerium oxide 135 80 100 135 150 180 190 Rosin derivative 10 10 10 10 10 10 10 MM 11 Sitting compound - 2.5 2.5 2.5 2.5 2.5 2.5 Hindered Phenolic Compound - 2.5 2.5 2.5 2.5 2.5 2.5 Characteristics GeqlOO 0.48 0.34 0.39 0.48 0.55 0.71 0.75 HeqlOO 0.37 0.32 0.38 0.43 0.45 0.48 0.50 Geq300 0.22 0.15 0.15 0.17 0.19 0.26 Destruction Heq300 0.33 0.31 0.34 0.42 0.41 0.41

Comparing the results of Comparative Example 1 of Table 2 with the results of Examples 1 to 4, it is understood 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 is equivalent. The attenuation constant Heq100 is less than 0.38 and the attenuation performance is not sufficient. In contrast, the high attenuation component formed by the high attenuation composition of Examples 1 to 4 which is the constitution of the present invention is used, and the equivalent attenuation constant Heq100 is 〇38 or more and excellent attenuation performance. Therefore, it has been confirmed that the ruthenium dioxide, the rosin derivative, the imidazole compound, and the hindered phenol compound are contained in the base polymer in a predetermined content ratio, whereby a high-performance thing capable of forming excellent attenuation performance can be obtained. 201116580 Reduced component's high attenuation composition. Further, comparing the results of Comparative Example 2 with Examples 1 to 4, it is understood 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 is used. The formed high attenuation component 'equivalent attenuation constant Heq100 is less than 0.38 and the attenuation performance is not sufficient. Therefore, it was confirmed that the content of cerium oxide must be 10 parts by weight or more per 1 part by weight of the base polymer. g and 'Comparing the results of Comparative Example 3 with Examples 1 to 4, it is understood that the high attenuation of Comparative Example 3 containing more than 18 parts by weight per 1 part by weight of the base polymer is used. The high-attenuation member formed by the composition is broken when the offset is large by 300%. 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 the cerium oxide in the range is preferably 135 parts by weight or more per 1 part by weight of the base polymer. % <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) and 3 parts by weight (Example 5). A high-attenuation composition was prepared in the same manner as in Example 1 except that 20 parts by weight (Example 6), 30 parts by weight (Example 7), and 50 parts by weight (Example 8) were used. &lt;Comparative Example 5&gt; When the content ratio of the rosin derivative to the base polymer of 25 201116580 natural rubber is 55 parts by weight, the adhesiveness is too strong, and it is not possible to knead the mixture of the respective components to prepare High attenuation 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 of the example 1 are shown together in Table 3. [Table 3] Table 3 --1 Comparative Example 4 tin 5 Example 1 Example 6 Example 7 Example 8 Parts by weight of cerium oxide 150 150 150 150 150 150 Rosin derivative 2 3 10 20 30 50 2 S Imidazole compound 2.5 2.5 2.5 2.5 2.5 2.5 — Obstructed compound 2.5 2.5 2.5 2.5 2.5 2,5 No modulation characteristics GeqlOO 0.49 0.50 0.55 0.55 0.63 0.83~~ HeqlOO 0.37 0.39 0.45 0.47 0.48 0.49 ~ Geq300 0.19 0.19 0.19 0.18 0.21 0.21 Heq300 0.37 0.38 0.41 0.43 0.44 0.45 Comparing the results of Comparative Example 4 of Table 3 with the results of Example 1, Examples 5 to 8, it is understood that the use of the rosin derivative is contained in a range of less than 3 parts by weight per 1 part by weight of the base polymer. The high-attenuation member formed by the high-attenuation composition of Comparative Example 4 had an equivalent decay constant Heq100 of less than 〇38 and the attenuation performance was insufficient. 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 'Comparative Example 5 containing a rosin derivative with respect to more than 50 parts by weight per 100 parts by weight of the base polymer, as explained above The nature is too high to modulate the high attenuation composition. Therefore, it can be confirmed that the content ratio of the rosin 26 201116580 must be 50 parts by weight or less per part by weight of the base polymer. &gt; In addition, the results of Example 1, Example 5 to Example 8 are compared, and the content ratio of the rosin derivative is preferably within the range of 1 〇 per 100 parts by weight of the base polymer. More than one. &lt;Example 9 to Example 12, Comparative Example 6&gt; The content ratio of the mimicry compound to the basis weight of the base polymer was set to 5 parts by weight (Comparative Example 6), 〇3 weight Amounts (Example 9), 1 part by weight (Example 1), 5 parts by weight (Example 11), 10 parts by weight (Example 丨 2) were prepared in the same manner as in Example 1 except that the high-attenuation composition was prepared. . &lt;Comparative Example 7&gt; When the content ratio of the flavor compound to the natural rubber of the base polymer is 13 parts by weight, the coking of the mixture of the components is coked during the kneading of the mixture of the components, so that the high yield is abandoned. Attenuation of the modulation of the composition. Therefore, the high-attenuation compositions of the respective examples and comparative examples except Comparative Example 7 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 4. [Table 4] Table 4 Comparative Example 6 Example 9 Example 10 Example 1 Example 11 Example 12 Comparative Example 7 Parts by weight of cerium oxide 150 150 150 150 150 150 150 Rosin derivative 10 10 10 10 10 10 10 Imidazole compound 0.05 0.3 1 2.5 5 10 13 Hindered Phenolic Compound 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Characteristics GeqlOO 0.48 0.49 0.52 0.55 0.58 0.62 Cannot be modulated HeqlOO 0.37 0.41 0.46 0.45 0.43 0.41 Geq300 0.18 0.19 0.20 0.19 0.24 0.30 Heq300 0.39 0.40 0.40 0.41 0.37 0.33 27 201116580 Comparing Comparative Example 6 with Example 1 and the results of Examples 9 to 12, it is understood that a comparative example containing a taste compound in a range of less than 1 part by weight per 100 parts by weight of the base polymer is used. The high attenuation component formed by the high attenuation composition of 6 has an equivalent attenuation constant HeqlOO of less than 0.38 and the attenuation performance is not sufficient. Therefore, it was confirmed that the content of the imidazole compound must be 0.1 part by weight or more based on (8) parts by weight of the base polymer per hydrazine.

Further, 'Comparative Example 7 was compared with the results of Example 1, Example 9 to Example 12', Comparative Example 7 containing an imidazole-based compound with respect to more than 1 part by weight per 1 part by weight of the base polymer, as in the foregoing It is explained that coking is easily generated and the high attenuation composition cannot be modulated. Therefore, it has been confirmed that the content ratio of the imidazole-based compound must be 10 parts by weight or less per 1 part by weight of the base polymer. Further, the results of Example 1, Example 9 to Example 12 are compared. It is confirmed that the content ratio of the imidazole-based compound is preferably in the range of 丨 by weight or more per 1 GG by weight of the base polymer. , the following. To (7)

&lt;Example 13 to Example 16, Comparative Example 8&gt; The content ratio of the hindered lanthanide compound to the weight of the base poly 03 of 1 part by weight was (10) 4 parts (Comparative Example 8) • $injury (example) 13), 1 part by weight (Example 14), 1 part by weight, part by weight, i Example 16) 'In addition to the above, the phase-reducing composition was prepared in the same manner as in Example 1. <Comparative Example 9> 28 201116580 When the content ratio of the hindered phenol compound to 100 parts by weight of the natural rubber as the base polymer is 23 parts by weight, blooming occurs on the surface of the high-attenuation 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 the examples in Table 5. [Table 5] Table 5 Comparative Example 8 Example 13 Example 14 Example 1 Example 15 Example 16 Comparative Example 9 i parts parts cerium oxide 150 150 150 150 150 150 150 rosin derivative 10 10 10 10 10 10 10 flavor salivary compound 2.5 2.5 2.5 2.5 2.5 2 5 2 5 Hindered Phenolic Compound 0.05 0.3 1 2.5 10 20 23 Characteristics GeqlOO 0.49 0.52 0.54 0.55 0.55 0.56 0.56 HeqlOO 0.37 0.39 0.42 0.45 0.46 0.47 0.47 Geq300 0.17 0.18 0.19 0.19 0.19 0.19 0.19 Heq300 0.35 0.38 0.41 0.41 0.41 0.41 0.41 Comparing the results of Comparative Example 8 of Table 5 with the results of Example 1, Example 13 to Example 16, it is understood that the use of the hindered phenol-based compound in a range of less than 0.1 part by weight per 1 part by weight of the base polymer is used. The high attenuation member formed by the high attenuation composition of Comparative Example 8 had 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 compound must be 0.1 part by weight or more per 1 part 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 Produced 29 201116580 Raw frost. Therefore, it was confirmed that the content of the hindered phenol-based compound must be 20 parts by weight or less per 100 parts by weight of the base polymer. &lt;Example 17&gt; In the same manner as in Example 1, except that imidazole [manufactured by Nippon Synthetic Chemical Co., Ltd.] was used instead of 1,2-dimercaptoimidazole in the same amount, the preparation was carried out in the same manner as in Example 1. Attenuate the composition. &lt;Example 18&gt; Further, 2.5 parts by weight of acetic acid tetrahydrate (manufactured by Kishida Chemical Co., Ltd.) and N-phenyl-N,-(l,3-dimethylbutyl) as an amine-based anti-aging agent were further added. A high-attenuation composition was prepared in the same manner as in Example 1 except that 5 parts by weight of p-phenylenediamine (NOCRAC6C manufactured by Ouchi Shinko Chemical Co., Ltd.) was used. &lt;Example 19&gt; The same components were used in the same ratio as used in Example 1 to modulate the high-attenuation composition in the following procedure. That is, the natural rubber used as the base polymer is subjected to mastication for about 1 minute to 2 minutes using a closed kneader, and then the mastication-surface introduction of the rosin derivative, the imidazole compound, the hindered phenol compound, and the second One part of the cerium oxide (1 part 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, 'measure the specified amount of the kneaded material and use the closed kneading machine again for 1 minute to 2 minutes, and then continue to carry out 30 201116580. The refining side is divided into two parts. The natural rubber is used as the replenishment part. (relative to each of the pre-existing and then step-by-step H) minutes ~ each of the reduced compositions shown in 3 of Table 1. The knives and clocks were mixed and the results were obtained. The characteristics of the high attenuation of the various examples were evaluated. The results of each of the 4^6] and /, and the results of Example 1 are shown in Table 6.

Table 6

From the example of Table 6 as the imidazole compound, it can be known that the attenuation property of the example is improved by using the taste. (4) The results of the first addition of the anti-aging base polymer 可: [Oxidation" can be carried out 31 201116580 <Example 20 to Example 23, Comparative Example l 〇> The imidazole is 100 parts by weight of the natural rubber as the base polymer The content ratio is set to 5 parts by weight of 〇·〇 (Comparative Example 1 〇), 3. 3 parts by weight (Example 20), 1 part by weight (Example 21), 5 parts by weight (Example 22), 1 〇 by weight (example) 23), except that the high-attenuation composition was prepared in the same manner as in Example π. <Comparative Example 11> The content ratio of imidazole to 100 parts by weight of the natural rubber as the base polymer was set to 13 parts by weight. At the time of mixing, the mixture of the components was coked, and thus the modulation of the high-attenuation composition was abandoned. Therefore, the high-attenuation compositions of the respective examples and comparative examples except Comparative Example 11 were subjected to the tests described above. The characteristics were evaluated. The results are shown together with the results of Example 17 in Table 7. [Table 7] Table 7 Comparative Example 10 Solid hook 20 Example 21 Example 17 House Example 22 Example 23 Comparative Example 11 "Ceria 150 150 150 150 150 150 150 Amount of rosin derivative 10 10 10 10 10 10 10 10 parts of taste &quot;Sit 0.05 0.3 1 2.5 5 10 13 - Party blocker compound 2.5 2.5 2.5 2.5 2.5 2.5 2 5 GeqlOO 0.57 0.58 0.61 0.64 0.69 0 73 Special Μ HeqlOO 0.47 0.48 0.53 0.52 0.49 0.47 Geq300 0.19 0.20 0.21 0.20 0.25 0.31 Heq300 0.41 0.43 0.43 0.44 0.40 0.36 Cannot be prepared The results of Comparative Example 1 and Example 17, Example 2〇 to Example 23 of Table 7 are compared with the results of Table 4 above. : Although the equivalent decay constant HeqlOO is improved as a whole, it is set as a comparative example using a high attenuation group containing material of less than 2011 曰 曰 曰 相对 相对 32 32 每 每 每 曰 曰 。 。 。 。 。 。 。 。 。 。 。 == part, which is lower than the content ratio: constant Heq100 and insufficient attenuation performance. The content of the imidazole to be added must be 0.1 parts by weight or more per 100 parts by weight of the base polymer. Example u and the knot of the example 17, the example 2G ~ the example 23

In the comparative example u which contained the taste saliva with respect to the weight loss per (10) part by weight of the base polymer, it was easy to produce coking as described above, and the high-attenuation composition could not be prepared. Therefore, it can be confirmed that the content ratio of the taste saliva must be (1) by weight or less per (10) parts by weight of the base polymerization i. 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. The scope of protection is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an exploded perspective view showing a test body of a high attenuation member model which is produced as a high-attenuation member for evaluating a high-attenuation member composed of a high-attenuation composition of an example of the present invention and a comparative example. . Fig. 2 (a) and (b) are schematic diagrams for explaining a testing machine for shifting the test body to obtain a relationship between the amount of displacement and the load. Fig. 3 is a graph showing an example of a hysteresis loop in which only the relationship between the amount of shift and the load is obtained by displacing the test body using the tester. 33 201116580 [Explanation of main component symbols] 1 : Disc 2 : Steel plate 3 : Test body 4 : Center fixing jig 5 : Left and right fixing jig 6 : Fixed arm 7 , 9 : Connector 8 : Movable disk L1 : Straight line L2 : Vertical line Keq : Slope AW: the amount of absorbed energy W: elastic strain energy Η: hysteresis loop

Claims (1)

201116580 VII. Patent application scope: 1. A high-attenuation composition characterized in that the high-attenuation composition contains: a base polymer; and 100 parts by weight or more and 180 weights per 10 parts by weight of the base polymer. The following sulphur dioxide derivative, 3 parts by weight or more and 50 parts by weight or less of the rosin derivative, 1 part by weight or more and 1 part by weight or less of the imidazole-based compound, and 1 part by weight or more and 2 parts by weight or less of the hindered phenol a compound. 2. 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. 3. The high attenuation composition of claim 2 or 2, wherein the imidazole compound is imidazole. You ^, such as the high attenuation component described in item 1 or 2 of the Shenqing patent scope, "advanced magnesium acetate and (10), anti-aging agent. B, as described in item 1 or 2 of the patent application scope The high-attenuation composition is added and modulated: firstly, the base polymer is kneaded, and the sputum compound and the compound are subjected to the compounding, and then the cerium oxide is added and kneaded. The high attenuation in the basic item 5 a composition in which the antisense compound is kneaded by: 3 = a fragrant derivative, a compound of the genus and a part of the dioxin + cerium oxide, and then a mixture of 7 and the remaining part is kneaded. It is used to form a material for forming a fine shock damper with a high attenuation composition as described in item 1 or 2. 35