TWI548686B - High decay composition - Google Patents
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- TWI548686B TWI548686B TW101133354A TW101133354A TWI548686B TW I548686 B TWI548686 B TW I548686B TW 101133354 A TW101133354 A TW 101133354A TW 101133354 A TW101133354 A TW 101133354A TW I548686 B TWI548686 B TW I548686B
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/04—Oxygen-containing compounds
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F15/00—Suppression of vibrations in systems; Means or arrangements for avoiding or reducing out-of-balance forces, e.g. due to motion
- F16F15/02—Suppression of vibrations of non-rotating, e.g. reciprocating systems; Suppression of vibrations of rotating systems by use of members not moving with the rotating systems
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Description
本發明是有關於一種成為高衰減構件的基材的高衰減組成物,上述高衰減構件緩和或吸收振動能量的傳遞。 The present invention relates to a highly attenuating composition of a substrate that is a high attenuation member that mitigates or absorbs the transmission of vibrational energy.
於例如高樓或橋樑等建築物、產業機械、飛機、汽車、鐵路車輛、電腦或其周邊設備類、家用電氣設備類、進而汽車用輪胎等廣泛的領域中,使用高衰減構件。藉由使用上述高衰減構件,可緩和或吸收振動能量的傳遞,也就是可實現免震、制震、制振、防振等。 High-attenuation members are used in a wide range of fields such as buildings such as high-rise buildings or bridges, industrial machinery, airplanes, automobiles, railway vehicles, computers or peripheral equipment, household electrical equipment, and automotive tires. By using the above-mentioned high-attenuation member, the transmission of vibration energy can be alleviated or absorbed, that is, vibration-proof, vibration-proof, vibration-proof, anti-vibration, and the like can be realized.
上述高衰減構件是藉由含有天然橡膠等作為基質聚合物的高衰減組成物來形成。於上述高衰減組成物中,為了提高衰減性能、即增大施加振動時的遲滯損耗(hysteresis loss)而使上述振動的能量高效地迅速衰減的性能,通常調配碳黑、二氧化矽等無機填充劑或松香、石油樹脂等增黏劑等(例如參照專利文獻1~專利文獻3等)。 The above high attenuation member is formed by a high attenuation composition containing a natural rubber or the like as a matrix polymer. In the above high-attenuation composition, in order to improve the attenuation performance, that is, to increase the hysteresis loss when vibration is applied, the energy of the vibration is rapidly and efficiently attenuated, and inorganic filling such as carbon black or cerium oxide is usually formulated. For example, a tackifier such as rosin or petroleum resin (for example, refer to Patent Document 1 to Patent Document 3).
然而,該些先前的高衰減組成物無法使高衰減構件的衰減性能充分提高。為了使高衰減構件的衰減性能較現狀進一步提高,考慮到進一步增加無機填充劑或增黏劑等的調配比例等。 However, these prior high attenuation compositions are unable to substantially increase the attenuation performance of the high attenuation members. In order to further improve the attenuation performance of the high-attenuation member, it is considered to further increase the blending ratio of the inorganic filler, the tackifier, and the like.
但是,調配有大量的無機填充劑或增黏劑的高衰減組成物有以下問題:加工性下降,為了製造具有所需立體形狀的高衰減構件而混練上述高衰減組成物、或成形加工為上述立體形狀並不容易。 However, a highly attenuating composition having a large amount of an inorganic filler or a tackifier has a problem that the workability is lowered, the high-attenuation composition is kneaded in order to produce a high-attenuation member having a desired three-dimensional shape, or the forming process is as described above. The three-dimensional shape is not easy.
尤其於以工場水準對高衰減構件進行量產的情形時,上述低加工性導致高衰減構件的生產性大幅下降,使生產所需要的能量增大,進而使生產成本高漲,故並不理想。 In particular, when the high-attenuation member is mass-produced at the factory level, the low workability causes a decrease in the productivity of the high-attenuation member, increases the energy required for production, and further increases the production cost, which is not preferable.
因此,為了於不使加工性下降的情況下提高衰減性能,於專利文獻4中已研究:於具有極性側鏈的基質聚合物中,調配具有2個以上的極性基的衰減性賦予劑等。 Therefore, in order to improve the attenuation performance without deteriorating the workability, it has been studied in Patent Document 4 to prepare an attenuating imparting agent having two or more polar groups in a matrix polymer having a polar side chain.
然而,上述具有極性側鏈者等在分子中具有極性基的基質聚合物由於通常玻璃轉移溫度Tg存在於室溫(3℃~35℃)附近,故使用含有上述基質聚合物的高衰減組成物形成的高衰減構件有以下傾向:於作為最通常使用的溫度範圍的上述室溫附近,特別是剛性等特性的溫度依存性變大。 However, the above-mentioned matrix polymer having a polar group in a polar side chain or the like has a glass transition temperature Tg which is usually present at room temperature (3 ° C to 35 ° C), so that a high attenuation composition containing the above matrix polymer is used. The formed high-attenuation member tends to have a temperature dependency of characteristics such as rigidity in the vicinity of the room temperature which is the most commonly used temperature range.
於專利文獻5中已研究:於不具有極性側鏈的基質聚合物中,調配二氧化矽及具有2個以上的極性基的衰減性賦予劑等。根據該構成,可藉由併用二氧化矽而維持良好的衰減性能,並且藉由使用不具有極性基者作為基質聚合物而減小特性於室溫附近的溫度依存性。 In Patent Document 5, it has been studied to prepare cerium oxide, an attenuating imparting agent having two or more polar groups, and the like in a matrix polymer having no polar side chain. According to this configuration, it is possible to maintain good attenuation performance by using cerium oxide in combination, and to reduce the temperature dependence of the property around room temperature by using a matrix polymer which does not have a polar group.
然而,於為了使衰減性能較現狀進一步提高而使上述衰減性賦予劑的調配比例增加的情形時,有上述衰減性賦予劑容易於高衰減構件的表面上起霜(bloom)的問題。 However, when the blending ratio of the above-described attenuating imparting agent is increased in order to further improve the damping performance, the above-described attenuating imparting agent is likely to cause blooming on the surface of the high-attenuating member.
於專利文獻6中已研究:藉由使用具有特定軟化點的松香衍生物作為衰減性賦予劑,而進一步提高衰減性能。 It has been studied in Patent Document 6 that the attenuation property is further improved by using a rosin derivative having a specific softening point as an attenuating imparting agent.
然而,於為了使衰減性能較現狀進一步提高而使松香衍生物的調配比例增加的情形時,有黏著性變得過高而高 衰減組成物的加工性下降的問題。 However, in the case where the blending ratio of the rosin derivative is increased in order to further improve the attenuation performance, the adhesiveness becomes too high and high. The problem of attenuating the workability of the composition is reduced.
進而,專利文獻7中已研究:藉由以預定比例將松香衍生物、咪唑及受阻酚類併用,而進一步提高衰減性能。 Further, in Patent Document 7, it has been studied to further improve the attenuation performance by using a rosin derivative, an imidazole, and a hindered phenol in combination at a predetermined ratio.
[專利文獻1]日本專利特開2003-2014號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-2014
[專利文獻2]日本專利特開2007-63425號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-63425
[專利文獻3]日本專利特開平7-41603號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 7-41603
[專利文獻4]日本專利特開2000-44813號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-44813
[專利文獻5]日本專利特開2009-138053號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-138053
[專利文獻6]日本專利特開2010-189604號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2010-189604
[專利文獻7]日本專利特開2011-116931號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2011-116931
根據上述專利文獻1~專利文獻7中記載的高衰減組成物,雖然可能如上述般產生各種問題,但可藉由適度調整各成分的調配比例等,而兼具某種程度的高衰減性能與良好的加工性。 According to the high-attenuation composition described in the above-mentioned Patent Documents 1 to 7, various problems may occur as described above, but it is possible to have a certain degree of high attenuation performance by appropriately adjusting the blending ratio of each component and the like. Good processability.
然而,使用上述先前的高衰減組成物而形成的高衰減構件均容易產生馬林斯效應(Mullins' effect),即施加大幅變形後的彈性模數下降,無法充分發揮作為高衰減構件的所需性能,故有時產生各種問題。 However, the high-attenuation members formed using the above-described high-attenuation composition are likely to have a Mullins effect, that is, a decrease in the elastic modulus after application of a large deformation, and it is not possible to fully exert the requirements as a high-attenuation member. Performance, so sometimes it causes various problems.
例如若發揮建築物的免震、制震功能的制震用阻尼器等大幅變形而彈性模數下降,則可能無法可靠地防止地震的能量傳至建築物。因此有以下問題:為了在考慮該彈性模數的下降的基礎上確保所需性能,作為制震用阻尼器等 產品的設計變複雜。 For example, if the damper for earthquake-damping, which is a vibration-proof and shock-proof function of a building, is largely deformed and the modulus of elasticity is lowered, it may be impossible to reliably prevent the energy of the earthquake from being transmitted to the building. Therefore, there is a problem in that, in order to ensure the required performance on the basis of considering the decrease in the elastic modulus, it is used as a damping device for shocks, etc. The design of the product becomes complicated.
本發明的目的在於提供一種新穎的高衰減組成物,其可製造具有高衰減性能、而且施加大幅變形後的彈性模數的下降小的高衰減構件。 SUMMARY OF THE INVENTION An object of the present invention is to provide a novel high-attenuation member which can produce a high-attenuation member having high attenuation performance and having a small decrease in elastic modulus after application of a large deformation.
本發明是一種高衰減組成物,其特徵在於:於具有由過氧化物引起的交聯性的基質聚合物100質量份中,調配有100質量份以上且170質量份以下的二氧化矽、及0.5質量份以上且3質量份以下的作為交聯劑的有機過氧化物。 The present invention is a high-attenuation composition in which 100 parts by mass or more and 170 parts by mass or less of cerium oxide are blended in 100 parts by mass of a matrix polymer having crosslinkability by a peroxide, and 0.5 part by mass or more and 3 parts by mass or less of the organic peroxide as a crosslinking agent.
上文所說明的先前的高衰減組成物均是以使用硫黃作為交聯劑的硫黃硫化為中心而研究組成等。 The previous high-attenuation compositions described above are studied on the basis of sulfur vulcanization using sulfur as a crosslinking agent, and the like.
相對於此,若藉由使用上述預定量的有機過氧化物作為交聯劑的過氧化物交聯代替上述硫黃硫化,來使以上述預定比例調配有二氧化矽的高衰減組成物進行交聯,則由於交聯結構與硫黃硫化的情形不同,故交聯後的高衰減構件如後述的實例、比較例的結果所明示般,可維持高衰減性能,而且可抑制施加大幅變形後的彈性模數的下降。 On the other hand, if the above-described sulfur vulcanization is used instead of the above-described sulfur vulcanization by using the above-described predetermined amount of the organic peroxide as a crosslinking agent, the high-attenuation composition in which the above-mentioned predetermined ratio is prepared with ceria is subjected to the crosslinking. Since the crosslinked structure is different from the sulfur vulcanization, the high-attenuation member after cross-linking can maintain high attenuation performance as well as the results of the examples and comparative examples described later, and can suppress the elasticity after application of large deformation. The decline in modulus.
因此,例如若為制震用阻尼器等,則可簡化作為用以確保所需性能的產品的設計。 Therefore, for example, if it is a damper for vibration damping or the like, the design as a product for ensuring desired performance can be simplified.
基質聚合物可使用具有由過氧化物引起的交聯性的各種基質聚合物。 As the matrix polymer, various matrix polymers having crosslinkability caused by peroxides can be used.
然而,特別是若考慮到形成使衰減性能的溫度依存性小、於廣的溫度範圍內可發揮穩定的衰減性能的高衰減構 件,上述基質聚合物較佳為選自由天然橡膠、異戊二烯橡膠及丁二烯橡膠所組成的組群中的至少一種,該些橡膠由於不具有極性基,故剛性等特性於室溫附近的溫度依存性小。 However, in particular, it is considered that a high attenuation structure which exhibits stable temperature attenuation in a wide temperature range and a high attenuation structure which exhibits stable attenuation performance in a wide temperature range is considered. Preferably, the matrix polymer is at least one selected from the group consisting of natural rubber, isoprene rubber and butadiene rubber, and the rubber has characteristics such as rigidity at room temperature because it does not have a polar group. The nearby temperature dependence is small.
於使用上述本發明的高衰減組成物作為形成材料,來形成作為高衰減構件的建築物的制震用阻尼器的情形時,由於即便發生地震而大幅變形,其彈性模數亦不會大幅下降,故能可靠地防止上述地震的能量傳至建築物。另外,因此亦可簡化用以確保所需性能的制震用阻尼器的設計。 When the high-attenuation composition of the present invention is used as a forming material to form a shock damper for a building which is a high-attenuation member, the elastic modulus does not significantly decrease because the earthquake is greatly deformed even if an earthquake occurs. Therefore, it is possible to reliably prevent the energy of the above earthquake from being transmitted to the building. In addition, the design of the damping damper to ensure the required performance can also be simplified.
根據本發明,可提供一種新穎的高衰減組成物,其可製造具有高衰減性能、而且施加大幅變形後的彈性模數的下降小的高衰減構件。 According to the present invention, it is possible to provide a novel high-attenuation member which can produce a high-attenuation member having high attenuation performance and having a small drop in elastic modulus after application of a large deformation.
本發明是一種高衰減組成物,其特徵在於:於具有由過氧化物引起的交聯性的基質聚合物100質量份中,調配有100質量份以上且170質量份以下的二氧化矽、及0.5質量份以上且3質量份以下的作為交聯劑的有機過氧化物。 The present invention is a high-attenuation composition in which 100 parts by mass or more and 170 parts by mass or less of cerium oxide are blended in 100 parts by mass of a matrix polymer having crosslinkability by a peroxide, and 0.5 part by mass or more and 3 parts by mass or less of the organic peroxide as a crosslinking agent.
基質聚合物可任意使用具有由過氧化物引起的交聯性的各種基質聚合物,其中較佳為橡膠。 As the matrix polymer, various matrix polymers having crosslinkability caused by peroxide can be arbitrarily used, and among them, rubber is preferred.
上述橡膠例如可列舉以下橡膠中的一種或兩種以上:天然橡膠、異戊二烯橡膠、丁二烯橡膠、苯乙烯丁二烯橡 膠、降冰片烯橡膠、乙烯丙烯橡膠、乙烯丙烯二烯橡膠、丁基橡膠、鹵化丁基橡膠、氯丁二烯橡膠、丙烯腈丁二烯橡膠、表氯醇橡膠、氯磺化聚乙烯、聚硫橡膠等。 The rubber may, for example, be one or more of the following rubbers: natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber Glue, norbornene rubber, ethylene propylene rubber, ethylene propylene diene rubber, butyl rubber, halogenated butyl rubber, chloroprene rubber, acrylonitrile butadiene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, Polysulfide rubber, etc.
特別是考慮到提供使衰減性能的溫度依存性小而於廣的溫度範圍內表現出穩定的衰減性能的高衰減構件,上述中較佳為選自由天然橡膠、異戊二烯橡膠及丁二烯橡膠所組成的組群中的至少一種橡膠。 In particular, it is preferable to provide a high-attenuation member which exhibits a low temperature dependency of attenuation performance and exhibits stable attenuation performance over a wide temperature range, and is preferably selected from natural rubber, isoprene rubber and butadiene. At least one rubber of the group consisting of rubber.
橡膠亦可併用兩種以上,但若考慮到簡化高衰減組成物的組成而提高上述高衰減組成物及高衰減構件的生產性、進而降低生產成本,較佳為單獨使用任一種。 Two or more kinds of rubbers may be used in combination. However, it is preferable to use either one alone, in order to improve the composition of the high-attenuation composition and improve the productivity of the high-attenuation composition and the high-attenuation member, and further reduce the production cost.
二氧化矽可使用根據其製法而分類的濕式法二氧化矽、乾式法二氧化矽的任一種。另外,若考慮到提高作為填充劑發揮功能而使高衰減構件的衰減性能提高的效果,則二氧化矽較佳為使用布厄特(Brunauer-Emmett-Teller,BET)比表面積為100m2/g以上、特別是200m2/g以上者,且較佳為使用BET比表面積為400m2/g以下、特別是250m2/g以下者。 As the cerium oxide, any of wet-process cerium oxide and dry-process cerium oxide classified according to the production method thereof can be used. Further, in view of the effect of improving the attenuation performance of the high-attenuation member by functioning as a filler, it is preferable to use a Brunauer-Emmett-Teller (BET) specific surface area of 100 m 2 /g. above, in particular 200m 2 / g or more, and preferably using a BET specific surface area of 400m 2 / g or less, particularly 250m 2 / g or less persons.
BET比表面積例如是用以下的值表示:使用柴田化學器械工業(股)製造的迅速表面積測定裝置SA-1000等,藉由使用氮氣作為吸附氣體的氣相吸附法進行測定所得的值。 The BET specific surface area is represented by, for example, a value obtained by a vapor phase adsorption method using a nitrogen gas as an adsorption gas using a rapid surface area measuring device SA-1000 manufactured by Shibata Chemical Instruments Co., Ltd., or the like.
上述二氧化矽例如可列舉東曹二氧化矽(股)製造的Nipsil(註冊商標)KQ、Nipsil VN3、Nipsil AQ、Nipsil ER 等的一種或兩種以上。 Examples of the above-mentioned cerium oxide include Nipsil (registered trademark) KQ, Nipsil VN3, Nipsil AQ, and Nipsil ER manufactured by Tosoh Ceria. One or two or more.
相對於基質聚合物每100質量份,二氧化矽的調配比例必須為100質量份以上且170質量份以下。 The compounding ratio of cerium oxide must be 100 parts by mass or more and 170 parts by mass or less per 100 parts by mass of the matrix polymer.
若調配比例小於上述範圍,則無法獲得藉由調配二氧化矽而使高衰減構件的衰減性能提高的效果。 If the blending ratio is less than the above range, the effect of improving the damping performance of the high-attenuation member by blending ceria is not obtained.
另一方面,於超過上述範圍的情形時,藉由過氧化物交聯的交聯後的高衰減構件無法獲得以下效果:減小高衰減構件於施加大幅變形後的彈性模數的下降。另外,亦有以下傾向:高衰減組成物的加工性下降,特別是以工場水準大量生產具有所需立體形狀的高衰減構件變困難。進而,雖然能以試製水準形成少數的高衰減構件,但亦可能所形成的高衰減構件變硬且難以變形,特別於反覆施加大幅變形時容易被破壞。 On the other hand, when it exceeds the above range, the cross-linked high-attenuation member by peroxide crosslinking cannot obtain the effect of reducing the decrease in the elastic modulus of the high-attenuating member after the application of the large deformation. In addition, there is also a tendency that the workability of the high-attenuation composition is lowered, and it is particularly difficult to mass-produce a high-attenuation member having a desired three-dimensional shape at a factory level. Further, although a small number of high-attenuation members can be formed at the trial production level, the high-attenuation members formed may be hard and difficult to be deformed, and are particularly likely to be broken when a large deformation is repeatedly applied.
再者,若考慮到使高衰減構件的衰減性能進一步提高,則二氧化矽的調配比例較佳為於上述範圍內亦為135質量份以上。另外,若考慮到儘可能減小高衰減構件於施加大幅變形後的彈性模數的下降、使高衰減組成物的加工性提高、及防止反覆施加大幅變形時的高衰減構件的破壞,則較佳為於上述範圍內亦為150質量份以下。 In addition, in consideration of further improving the attenuation performance of the high-attenuation member, the proportion of the cerium oxide is preferably 135 parts by mass or more in the above range. Further, in consideration of minimizing the decrease in the elastic modulus of the high-attenuation member after the application of the large deformation, the improvement of the workability of the high-attenuation composition, and the prevention of the destruction of the high-attenuation member when the large deformation is repeatedly applied, Preferably, it is 150 parts by mass or less in the above range.
作為交聯劑的有機過氧化物例如可列舉以下化合物中的一種或兩種以上:過氧化二苯甲醯、二異丙苯基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、α,α'-二(第三丁基過氧化)二異丙基苯、第三丁基異丙苯基過氧化物、二 -第三己基過氧化物、二-第三丁基過氧化物、2,5-二甲基-2,5-雙(第三丁基過氧化)-3-己炔、1,1-二(第三己基過氧化)環己烷、1,1-二(第三丁基過氧化)環己烷、正丁基-4,4-二(第三丁基過氧化)戊酸酯、2,5-二甲基-2,5-二(苯甲醯基過氧化)己烷、過氧化苯甲酸第三己酯、過氧化苯甲酸第三丁酯等。 The organic peroxide as the crosslinking agent may, for example, be one or more of the following compounds: benzamidine peroxide, dicumyl peroxide, 2,5-dimethyl-2,5- Di(t-butylperoxy)hexane, α,α'-di(t-butylperoxy)diisopropylbenzene, tert-butylcumyl peroxide, two - a third hexyl peroxide, a di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexyne, 1,1-di (Third hexyl peroxide) cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, n-butyl-4,4-di(t-butylperoxy)valerate, 2 , 5-dimethyl-2,5-di(benzimidyl peroxy)hexane, third hexyl peroxybenzoate, tert-butyl peroxybenzoate, and the like.
其中,例如適合使用日油(股)製造的Percumyl(註冊商標)D[二異丙苯基過氧化物]、Peroxa(註冊商標)25B[2,5-二甲基-2,5-二(第三丁基過氧化)己烷]等。 Among them, for example, Percumyl (registered trademark) D [diisopropylphenyl peroxide] manufactured by Nippon Oil Co., Ltd., Peroxa (registered trademark) 25B [2,5-dimethyl-2,5-di ( Tertiary butyl peroxy) hexane] and the like.
相對於基質聚合物每100質量份,有機過氧化物的調配比例必須為0.5質量份以上且3質量份以下。 The compounding ratio of the organic peroxide must be 0.5 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the matrix polymer.
若調配比例小於上述範圍,藉由過氧化物交聯的交聯後的高衰減構件無法獲得以下效果:減小高衰減構件於施加大幅變形後的彈性模數的下降。另外,若反覆施加大幅變形,則亦可能高衰減構件雖然一開始追隨於所施加的變形而變形,但因少許次數的變形而被破壞。 If the blending ratio is less than the above range, the cross-linked high-attenuation member by peroxide crosslinking cannot achieve the following effect: the decrease in the elastic modulus of the high-attenuating member after application of the large deformation is reduced. Further, if a large deformation is repeatedly applied, the high attenuation member may be deformed at the beginning of the deformation accompanying the applied deformation, but may be broken by a small number of deformations.
另一方面,於超過上述範圍的情形時,交聯後的高衰減構件變硬且難以變形,高衰減構件的衰減性能下降。另外,若反覆施加大幅變形,則亦可能高衰減構件因極少次數的變形而被破壞。 On the other hand, when it exceeds the above range, the cross-linked high-attenuation member becomes hard and hard to be deformed, and the attenuation performance of the high-attenuation member is lowered. Further, if a large deformation is repeatedly applied, the high attenuation member may be broken by a very small number of deformations.
再者,若考慮到儘可能減小交聯後的高衰減構件於施加大幅變形後的彈性模數的下降、及防止反覆施加大幅變形時的破壞,則有機過氧化物的調配比例較佳為於上述範圍內亦為1質量份以上。另外,若考慮到進一步提高上述高衰減構件的衰減性能、及防止反覆施加大幅變形時的破 壞,則較佳為於上述範圍內亦為2質量份以下。 Further, in consideration of minimizing the decrease in the modulus of elasticity of the high-attenuating member after the cross-linking as much as possible after the application of the large-scale deformation, and the prevention of the destruction when the large-scale deformation is repeatedly applied, the compounding ratio of the organic peroxide is preferably It is also 1 part by mass or more in the above range. In addition, it is considered that the attenuation performance of the high-attenuation member is further improved, and the breakage is prevented from being repeatedly applied. The amount of the film is preferably 2 parts by mass or less in the above range.
於本發明的高衰減組成物中,亦可進一步以適當的比例調配二氧化矽以外的其他填充劑、矽烷化合物、軟化劑、增黏劑、抗老化劑等各種添加劑。 In the highly attenuating composition of the present invention, various additives such as a filler other than cerium oxide, a decane compound, a softening agent, a tackifier, and an anti-aging agent may be further blended in an appropriate ratio.
上述其他填充劑例如可列舉碳黑或碳酸鈣等。 Examples of the other fillers include carbon black or calcium carbonate.
其中,碳黑可列舉:根據其製造方法等而分類的各種碳黑中,可作為填充劑發揮功能的碳黑的一種或兩種以上。 Among the carbon blacks classified according to the production method and the like, one or two or more kinds of carbon blacks that function as a filler can be used.
碳黑的調配比例並無特別限定,相對於基質聚合物每100質量份,較佳為1質量份以上且5質量份以下。 The blending ratio of the carbon black is not particularly limited, and is preferably 1 part by mass or more and 5 parts by mass or less per 100 parts by mass of the matrix polymer.
另外,碳酸鈣可任意使用:根據其製造方法等而分類的合成碳酸鈣、重質碳酸鈣等中,可作為填充劑發揮功能的粉末狀的碳酸鈣。另外,碳酸鈣亦可使用為了提高對基質聚合物等的親和性、分散性等而實施了表面處理者。 Further, calcium carbonate can be used arbitrarily: powdered calcium carbonate which functions as a filler in synthetic calcium carbonate, heavy calcium carbonate or the like classified according to the production method and the like. Further, the surface treatment may be carried out in order to increase the affinity for the matrix polymer or the like, the dispersibility, and the like.
矽烷化合物可列舉以式(a)所表示的矽烷偶合劑或矽烷化劑等、作為二氧化矽的分散劑發揮功能的各種矽烷化合物:
[式中,R1、R2、R3及R4中的至少一個表示烷氧基。其中,R1、R2、R3及R4不同時為烷氧基,其他表示烷基或芳基]。 [wherein, at least one of R 1 , R 2 , R 3 and R 4 represents an alkoxy group. Wherein R 1 , R 2 , R 3 and R 4 are not alkoxy at the same time, and the others represent an alkyl group or an aryl group].
特佳為己基三甲氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二苯基二甲氧基矽烷等烷氧基矽烷。 Particularly preferred are alkoxydecanes such as hexyltrimethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, and diphenyldimethoxydecane.
上述矽烷化合物例如可列舉信越化學工業(股)製造的KBE-103(苯基三乙氧基矽烷)等。 Examples of the above decane compound include KBE-103 (phenyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
矽烷化合物的調配比例並無特別限定,相對於二氧化矽每100質量份,較佳為5質量份以上,且較佳為25質量份以下。 The blending ratio of the decane compound is not particularly limited, and is preferably 5 parts by mass or more, and preferably 25 parts by mass or less per 100 parts by mass of the cerium oxide.
軟化劑可列舉香豆酮-茚樹脂、液狀橡膠等的一種或兩種以上。 The softener may be one or more selected from the group consisting of a coumarone-indene resin and a liquid rubber.
其中,香豆酮-茚樹脂可列舉:主要包含香豆酮與茚的聚合物、平均分子量為1000以下左右的分子量相對較低、且可作為軟化劑發揮功能的各種香豆酮-茚樹脂。 Among them, the coumarone-indene resin may be a coumarone-indene resin which mainly contains a polymer of coumarone and hydrazine, has a relatively low molecular weight of about 1000 or less, and functions as a softening agent.
上述香豆酮-茚樹脂例如可列舉以下產品中的一種或兩種以上:日塗化學(股)製造的Nitto Resin(註冊商標)Coumarone G-90[平均分子量:770,軟化點:90℃,酸值:1.0KOH mg/g以下,羥基值:25KOH mg/g,溴值:9g/100g]、G-100N[平均分子量:730,軟化點:100℃,酸值:1.0KOH mg/g以下,羥基值:25KOH mg/g,溴值:11g/100g]、V-120[平均分子量:960,軟化點:120℃,酸值:1.0KOH mg/g以下,羥基值:30KOH mg/g,溴值:6g/100g]、V-120S[平均分子量:950,軟化點:120℃,酸值:1.0KOH mg/g以下,羥基值:30KOH mg/g,溴值:7g/100g]等。 The above-mentioned coumarone-indene resin may, for example, be one or more of the following products: Nitto Resin (registered trademark) Coumarone G-90 manufactured by Nippon Chemical Co., Ltd. (average molecular weight: 770, softening point: 90 ° C, Acid value: 1.0 KOH mg/g or less, hydroxyl value: 25 KOH mg/g, bromine value: 9 g/100 g], G-100N [average molecular weight: 730, softening point: 100 ° C, acid value: 1.0 KOH mg/g or less , hydroxyl value: 25 KOH mg / g, bromine value: 11 g / 100 g], V-120 [average molecular weight: 960, softening point: 120 ° C, acid value: 1.0 KOH mg / g or less, hydroxyl value: 30 KOH mg / g, Bromine number: 6g/100g], V-120S [average molecular weight: 950, softening point: 120 ° C, acid value: 1.0 KOH Below mg/g, hydroxyl value: 30 KOH mg/g, bromine value: 7 g/100 g], and the like.
香豆酮-茚樹脂的調配比例並無特別限定,相對於基質聚合物每100質量份,較佳為5質量份以上,且較佳為50質量份以下。 The blending ratio of the coumarone-indene resin is not particularly limited, and is preferably 5 parts by mass or more, and preferably 50 parts by mass or less per 100 parts by mass of the matrix polymer.
另外,液狀橡膠可列舉於室溫(3℃~35℃)下呈液狀的各種橡膠。上述液狀橡膠例如可列舉:液狀聚異戊二烯橡膠、液狀腈橡膠(液狀NBR)、液狀苯乙烯丁二烯橡膠(液狀SBR)等的一種或兩種以上。 Further, examples of the liquid rubber include various rubbers which are liquid at room temperature (3 ° C to 35 ° C). The liquid rubber may, for example, be one or more selected from the group consisting of liquid polyisoprene rubber, liquid nitrile rubber (liquid NBR), and liquid styrene butadiene rubber (liquid SBR).
其中,較佳為液狀聚異戊二烯橡膠。上述液狀聚異戊二烯橡膠例如可列舉可樂麗(股)製造的Kuraprene(註冊商標)LIR-50等。 Among them, a liquid polyisoprene rubber is preferred. Examples of the liquid polyisoprene rubber include Kuraprene (registered trademark) LIR-50 manufactured by Kuraray Co., Ltd., and the like.
液狀聚異戊二烯橡膠的調配比例並無特別限定,相對於基質聚合物每100質量份,較佳為5質量份以上,且較佳為80質量份以下。 The mixing ratio of the liquid polyisoprene rubber is not particularly limited, and is preferably 5 parts by mass or more, and preferably 80 parts by mass or less per 100 parts by mass of the matrix polymer.
增黏劑例如可列舉石油樹脂等。另外,石油樹脂例如較佳為丸善石油化學(股)製造的Marukarez(註冊商標)M890A[二環戊二烯系石油樹脂,軟化點:105℃]等。 Examples of the tackifier include petroleum resins and the like. Further, the petroleum resin is, for example, Marukarez (registered trademark) M890A [dicyclopentadiene petroleum resin, softening point: 105 ° C] manufactured by Maruzen Petrochemical Co., Ltd., and the like.
上述石油樹脂的調配比例並無特別限定,相對於基質聚合物每100質量份,較佳為3質量份以上,且較佳為50質量份以下。 The blending ratio of the above-mentioned petroleum resin is not particularly limited, and is preferably 3 parts by mass or more, and preferably 50 parts by mass or less per 100 parts by mass of the matrix polymer.
抗老化劑例如可列舉:苯并咪唑系、醌系、多酚系、胺系等的各種抗老化劑的一種或兩種以上。特佳為併用苯并咪唑系抗老化劑與醌系抗老化劑。 The anti-aging agent may, for example, be one or more of various anti-aging agents such as benzimidazole-based, anthraquinone-based, polyphenol-based, and amine-based. It is particularly preferred to use a benzimidazole-based anti-aging agent and a lanthanide anti-aging agent.
其中,苯并咪唑系抗老化劑例如可列舉大內新興化學 工業(股)製造的Nocrac(註冊商標)MB[2-巰基苯并咪唑]等。另外,醌系抗老化劑例如可列舉丸石化學品(股)製造的Antigen FR[芳香族酮-胺縮合物]等。 Among them, benzimidazole-based anti-aging agents can be exemplified by Ouchi Shining Chemical Nocrac (registered trademark) MB [2-mercaptobenzimidazole] manufactured by Industrial Co., Ltd., and the like. Further, examples of the lanthanide anti-aging agent include Antigen FR [aromatic ketone-amine condensate] produced by a peony chemical (stock).
兩抗老化劑的調配比例並無特別限定,相對於基質聚合物每100質量份,苯并咪唑系抗老化劑較佳為0.5質量份以上,且較佳為5質量份以下。另外,相對於基質聚合物每100質量份,醌系抗老化劑較佳為0.5質量份以上,且較佳為5質量份以下。 The compounding ratio of the two anti-aging agents is not particularly limited, and the benzimidazole-based anti-aging agent is preferably 0.5 parts by mass or more, and preferably 5 parts by mass or less per 100 parts by mass of the matrix polymer. Further, the lanthanide anti-aging agent is preferably 0.5 parts by mass or more, and preferably 5 parts by mass or less per 100 parts by mass of the matrix polymer.
本發明的高衰減組成物是使用任意的混練機將上述各成分混練而製備,藉由將上述高衰減組成物成形加工為所需立體形狀並使基質聚合物進行過氧化物交聯,而製造具有預定衰減性能的高衰減構件。 The high-attenuation composition of the present invention is prepared by kneading the above components using an arbitrary kneading machine, and is produced by molding the high-attenuation composition into a desired three-dimensional shape and subjecting the matrix polymer to peroxide crosslinking. A high attenuation member with predetermined attenuation properties.
可使用本發明的高衰減組成物製造的高衰減構件例如可列舉:組入至高樓等建築物的根基中的免震用阻尼器,組入至建築物的構造中的制震(制振)用阻尼器,吊橋或斜拉橋等的纜線(cable)的制振構件,產業機械或飛機、汽車、鐵路車輛等的防振構件,電腦或其周邊設備類、或家用電氣設備類等的防振構件,進而汽車用輪胎的胎面(tread)等。 The high-attenuation member which can be produced by using the high-attenuation composition of the present invention is, for example, a vibration-damping damper incorporated in the foundation of a building such as a high-rise building, and the vibration-damping (vibration) incorporated in the structure of the building. Damping members for cables such as dampers, suspension bridges or cable-stayed bridges, anti-vibration members for industrial machinery or aircraft, automobiles, railway vehicles, etc., computers or their peripheral equipment, or household electrical equipment, etc. An anti-vibration member, and further a tread of an automobile tire.
根據本發明,於上述範圍內調整上述基質聚合物、二氧化矽及有機過氧化物的種類與其組合及調配比例,藉此可獲得適於上述各用途的具有優異衰減性能的高衰減構件。 According to the present invention, the types, combinations, and blending ratios of the above-mentioned matrix polymer, cerium oxide, and organic peroxide are adjusted within the above range, whereby a high-attenuating member having excellent attenuation properties suitable for each of the above applications can be obtained.
特別於使用本發明的高衰減組成物形成組入至建築物 的構造中的制震用阻尼器的情形時,由於上述制震用阻尼器對振動的衰減性能優異,且施加大幅變形時的彈性模數的下降小,故可簡化作為用以確保所需性能的產品的設計,而且可減少組入至一個建築物中的制震用阻尼器的數量。 Particularly formed using the high attenuation composition of the present invention to form a building into a building In the case of the damper for vibration control in the above-described structure, since the damper for shock absorbing is excellent in vibration damping performance and the drop in the modulus of elasticity when the large deformation is applied is small, it can be simplified to ensure the required performance. The design of the product and the number of shock dampers incorporated into a building can be reduced.
於作為基質聚合物的天然橡膠[標準馬來西亞橡膠(Standard Malaysian Rubber,SMR)-CV60]100質量份中,調配 In 100 parts by mass of natural rubber [Standard Malaysian Rubber (SMR)-CV60] as a matrix polymer, blending
二氧化矽[束曹二氧化矽(股)製造的Nipsil KQ]135質量份、及作為有機過氧化物的二異丙苯基過氧化物[日油(股)製造的Percumyl(註冊商標)D]0.5質量份、以及下述表1所示的各成分,使用密閉式混練機進行混練而製備高衰減組成物。 135 parts by mass of bismuth dioxide [Nipsil KQ] manufactured by Shucao bismuth oxide (share), and dicumyl peroxide as organic peroxide [Percumyl (registered trademark) D manufactured by Nippon Oil Co., Ltd. 0.5 parts by mass and each component shown in the following Table 1 were kneaded using a closed kneader to prepare a highly attenuating composition.
表1中的各成分如下。 The components in Table 1 are as follows.
矽烷化合物:苯基三乙氧基矽烷,信越化學工業(股)製造的KBE-103 Decane compound: phenyl triethoxy decane, KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.
二環戊二烯系石油樹脂:軟化點為105℃,丸善石油化學(股)製造的Marukarez(註冊商標)M890A Dicyclopentadiene-based petroleum resin: softening point is 105 ° C, Marukarez (registered trademark) M890A manufactured by Maruzen Petrochemical Co., Ltd.
香豆酮-茚樹脂:軟化點為90℃,日塗化學(股)製造的Aesculon(註冊商標)G-90 Coumarone-indene resin: softening point of 90 ° C, Aesculon (registered trademark) G-90 manufactured by Nippon Chemical Co., Ltd.
苯并咪唑系抗老化劑:2-巰基苯并咪唑,大內新興化 學工業(股)製造的Nocrac MB Benzimidazole-based anti-aging agent: 2-mercaptobenzimidazole Nocrac MB manufactured by Industrial Industries
醌系抗老化劑:丸石化學品(股)製造的Antigen FR Anti-aging agent: Antigen FR manufactured by Maruishi Chemicals Co., Ltd.
碳黑:三菱化學(股)製造的Diablack(註冊商標)G Carbon Black: Diablack (registered trademark) G manufactured by Mitsubishi Chemical Corporation
液狀聚異戊二烯橡膠:可樂麗(股)製造的LIR50 Liquid polyisoprene rubber: LIR50 manufactured by Kuraray Co., Ltd.
相對於作為基質聚合物的天然橡膠每100質量份,將作為有機過氧化物的二異丙苯基過氧化物的調配比例設定 為0.4質量份(比較例1)、1.5質量份(實例2)、3質量份(實例3)、3.5質量份(比較例2),除此以外,與實例1同樣地製備高衰減組成物。 Setting the ratio of diisopropylphenyl peroxide as an organic peroxide per 100 parts by mass of the natural rubber as the matrix polymer A high attenuation composition was prepared in the same manner as in Example 1 except that 0.4 parts by mass (Comparative Example 1), 1.5 parts by mass (Example 2), 3 parts by mass (Example 3), and 3.5 parts by mass (Comparative Example 2) were used.
作為交聯劑,代替二異丙苯基過氧化物而調配相對於天然橡膠每100質量份而為1.58質量份的5%油處理硫黃,並且進一步調配下述表2所示的硫黃硫化系的各成分,除此以外,與實例1同樣地製備高衰減組成物。 As a crosslinking agent, instead of dicumyl peroxide, 5% oil-treated sulfur was added in an amount of 1.58 parts by mass per 100 parts by mass of the natural rubber, and further sulfur-sulfurization shown in Table 2 below was formulated. A highly attenuating composition was prepared in the same manner as in Example 1 except for the components of the system.
表2中的各成分如下。 The components in Table 2 are as follows.
亞磺醯胺系硫化促進劑:正第三丁基-2-苯并噻唑基亞磺醯胺,大內新興化學工業(股)製造的Nocceler(註冊商標)NS A sulfinamide-based vulcanization accelerator: n-tert-butyl-2-benzothiazolylsulfinamide, Nocceler (registered trademark) NS manufactured by Ouchi New Chemical Industry Co., Ltd.
秋蘭姆系硫化促進劑:大內新興化學工業(股)製造的Nocceler TBT-n Qiulan vulcanization accelerator: Nocceler TBT-n manufactured by Ou Nei Emerging Chemical Industry Co., Ltd.
氧化鋅2種:硫化促進助劑,三井金屬礦業(股)製造 2 kinds of zinc oxide: vulcanization promotion aid, manufacturing of Mitsui Metals Mining Co., Ltd.
硬脂酸:硫化促進助劑,日油(股)製造的「Tsubaki」 Stearic acid: vulcanization accelerator, "Tsubaki" made by Nippon Oil Co., Ltd.
將實例、比較例中製備的高衰減組成物擠出成形為片狀後衝壓,如圖1所示般製作圓板1(厚度5mm×直徑25mm),於上述圓板1的表背兩面上,一面分別經由硫化接著劑重疊厚度6mm×縱44mm×橫44mm的矩形平板狀的鋼板2並於積層方向上加壓,一面加熱至150℃而使形成圓板1的高衰減組成物進行交聯,並且使上述圓板1與兩片鋼板2接著,製作成為高衰減構件的模型的衰減特性評價用的試驗體3。 The high-attenuation composition prepared in the examples and the comparative examples was extrusion-molded into a sheet shape and then punched, and as shown in FIG. 1, a circular plate 1 (thickness: 5 mm × diameter: 25 mm) was produced, on the front and back sides of the above-mentioned circular plate 1, On one side, 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 was superposed on each other and pressurized in the lamination direction, and heated to 150° C. to crosslink the high-attenuation composition forming the disc 1 . Further, the disk 1 and the two steel sheets 2 were placed next to each other to prepare a test body 3 for evaluation of the attenuation characteristics of the model of the high attenuation member.
如圖2(a)所示般準備兩個上述試驗體3,將上述兩個試驗體3經由一側的鋼板2利用螺栓固定於一片中央固定夾具4,並且於各試驗體3的另一鋼板2上,利用螺栓固定各一片左右固定夾具5。繼而,將中央固定夾具4經由接頭7利用螺栓固定於未圖示的試驗機的上側的固定臂6,且將兩片左右固定夾具5經由接頭9利用螺栓固定於上述試驗機的下側的可動盤8。 Two test bodies 3 were prepared as shown in Fig. 2 (a), and the two test pieces 3 were fixed to one piece of the central fixing jig 4 via a steel plate 2 on one side, and another steel plate of each test piece 3 was used. 2, each of the left and right fixing jigs 5 is fixed by bolts. Then, the center fixing jig 4 is fixed to the upper fixing arm 6 of the testing machine (not shown) via the joint 7 by bolts, and the two left and right fixing jigs 5 are fixed to the lower side of the testing machine by bolts via the joint 9. Disk 8.
然後,於該狀態下,使可動盤8如圖中空心箭頭所示般以朝固定臂6的方向上壓的方式位移,於試驗體3中使圓板1成為如圖2(b)所示般朝與上述試驗體3的積層方向正交的方向應變變形的狀態,繼而,自該狀態起,使可動盤8如圖中空心箭頭所示般以朝與固定臂6的方向相反的方向下拉的方式位移,回到上述圖2(a)所示的狀態,將上述操作視為1循環,求出於上述試驗體3中使圓板1 反覆應變變形、即振動時的遲滯曲線(hysteresis loop)H(參照圖3),該遲滯曲線H表示與上述試驗體3的積層方向正交的方向上的圓板1的位移量(mm)與負載(N)的關係。 Then, in this state, the movable disk 8 is displaced in the direction of the fixed arm 6 as shown by the hollow arrow in the figure, and the disk 1 is made into the test body 3 as shown in Fig. 2(b). The state in which the strain is deformed in a direction orthogonal to the lamination direction of the test body 3, and then, from this state, the movable disk 8 is pulled downward in a direction opposite to the direction of the fixed arm 6 as indicated by a hollow arrow in the figure. In the state shown in Fig. 2 (a), the above operation is regarded as one cycle, and the disk 1 is obtained in the test body 3 described above. In response to strain deformation, that is, a hysteresis loop H (see FIG. 3) at the time of vibration, the hysteresis curve H indicates the displacement amount (mm) of the circular plate 1 in the direction orthogonal to the lamination direction of the test body 3 described above. Load (N) relationship.
測定時,將上述操作進行3循環而求出第3次的值。另外,最大位移量是以如下方式設定:夾著圓板1的兩片鋼板2的與上述積層方向正交的方向上的偏移量達到上述圓板1的厚度的100%。 At the time of the measurement, the above operation was performed for 3 cycles to obtain the third value. Further, the maximum displacement amount is set such that the amount of shift in the direction orthogonal to the stacking direction of the two steel sheets 2 sandwiching the disk 1 is 100% of the thickness of the disc 1 described above.
繼而,將藉由上述測定而求出的圖3所示的遲滯曲線H中最大位移點與最小位移點連結,求出圖中以粗實線所示的直線L1的傾斜度Keq(N/mm),根據上述傾斜度Keq(N/mm)、圓板1的厚度T(mm)及圓板1的截面積A(mm2),藉由式(1)求出等效剪切彈性模數Geq(N/mm2)。 In turn, the hysteresis curve H by the above-described measurement was shown in FIG. 3 point of maximum displacement and minimum displacement of the connecting point, to obtain a straight line in FIG thick solid line L shown in the inclination of Keq 1 (N / Mm), based on the above-described inclination Keq (N/mm), the thickness T (mm) of the disc 1 and the cross-sectional area A (mm 2 ) of the disc 1, the equivalent shear elastic modulus is obtained by the formula (1) The number is Geq (N/mm 2 ).
繼而,於將先前例1的等效剪切彈性模數Geq(N/mm2)設定為100時,求出各實例、比較例的等效剪切彈性模數Geq(N/mm2)的相對值。 Then, when the equivalent shear elastic modulus Geq (N/mm 2 ) of the previous example 1 was set to 100, the equivalent shear elastic modulus Geq (N/mm 2 ) of each example and the comparative example was determined. relative value.
另外,根據吸收能量△W及彈性應變能量W,藉由式(2)求出等效衰減常數Heq,上述吸收能量△W是於圖3中標註斜線所示,是以遲滯曲線H的總表面積所表示,上 述彈性應變能量W是於該圖中標註網線所示,是以上述直線L1、圖表的橫軸、及自直線L1與遲滯曲線H的交點垂直於上述橫軸的垂線L2所包圍的區域的表面積所表示。 Further, based on the absorbed energy ΔW and the elastic strain energy W, the equivalent decay constant Heq is obtained by the equation (2), and the absorbed energy ΔW is indicated by a hatched line in FIG. 3, and is the total surface area of the hysteresis curve H. It is shown that the elastic strain energy W is indicated by a line drawn in the figure, and is a vertical line L 1 , a horizontal axis of the graph, and a perpendicular line L from the intersection of the straight line L 1 and the hysteresis curve H perpendicular to the horizontal axis. The surface area of the area enclosed by 2 is represented by 2 .
等效衰減常數Heq越大,則可判定試驗體3的衰減性能越優異。 The larger the equivalent decay constant Heq, the more excellent the attenuation performance of the test body 3 can be determined.
於是,將先前例1的等效衰減常數Heq設定為100時,求出各實例、比較例的等效衰減常數Heq的相對值,將上述相對值為95以上者評價為良好,低於95者評價為不良。 Then, when the equivalent decay constant Heq of the previous example 1 is set to 100, the relative value of the equivalent decay constant Heq of each example and the comparative example is obtained, and the relative value of 95 or more is evaluated as good, and less than 95. The evaluation was bad.
以夾著圓板1的兩片鋼板2的與上述積層方向正交的方向上的偏移量達到上述圓板1的厚度的300%的方式設定最大位移量,除此以外,與上述同樣地使上述圓板1進行一次大幅變形後,與上述同樣地求出偏移量為100%時的剪切彈性模數Geq'(N/mm2)。 In the same manner as described above, the maximum displacement amount is set so that the amount of shift in the direction orthogonal to the stacking direction of the two steel sheets 2 of the disc 1 is set to 300% of the thickness of the disc 1 . After the disc 1 was largely deformed once, the shear elastic modulus Geq' (N/mm 2 ) when the offset amount was 100% was obtained in the same manner as described above.
繼而,藉由式(3)求出大幅變形後的彈性模數的保持率(%)。 Then, the retention ratio (%) of the elastic modulus after the large deformation is obtained by the formula (3).
保持率越大,則可判定試驗體3於施加大幅變形後的彈性模數的下降越小。 The larger the retention ratio, the smaller the decrease in the elastic modulus of the test body 3 after the application of the large deformation is determined.
於是,將先前例1的保持率設定為100時,求出各實例、比較例的保持率的相對值,將上述相對值為101以上者評價為良好,將小於101者評價為不良。 Then, when the retention ratio of the previous example 1 was set to 100, the relative value of the retention ratio of each of the examples and the comparative examples was determined, and the relative value of 101 or more was evaluated as good, and the less than 101 was evaluated as defective.
反覆進行上述最大位移量為300%的大幅變形時,觀察圓板1的狀態,按下述基準評價大幅變形時的耐久性。 When the above-described maximum displacement amount was 300%, the state of the disk 1 was observed, and the durability at the time of large deformation was evaluated according to the following criteria.
○:未變化。耐久性良好。 ○: No change. Durable.
×:因5循環以內的大幅變形的反覆而破損。耐久性不良。 ×: It was broken due to the reversal of the large deformation within 5 cycles. Poor durability.
將以上結果示於表3中。 The above results are shown in Table 3.
由表3的實例1~實例3、先前例1的結果可知,藉由使高衰減組成物進行過氧化物交聯代替硫黃硫化,可獲得維持良好的衰減性能、並且施加大幅變形後的彈性模數的下降小、而且反覆施加大幅變形時的耐久性亦優異的高衰減構件。 From the results of Examples 1 to 3 and Table 1 of Table 3, it was found that by subjecting the high-attenuating composition to peroxide crosslinking instead of sulfur vulcanization, it is possible to obtain a good attenuation property and to apply elasticity after being greatly deformed. A high-attenuation member having a small decrease in the modulus and excellent durability in the case of greatly deforming.
其中,由實例1~實例3、比較例1、比較例2的結果可知,為了獲得上述效果,必須將有機過氧化物的調配比例設定為相對於基質聚合物每100質量份而為0.5質量份以上且3質量份以下。 In the results of Examples 1 to 3, Comparative Example 1, and Comparative Example 2, in order to obtain the above effects, it is necessary to set the compounding ratio of the organic peroxide to 0.5 parts by mass per 100 parts by mass of the matrix polymer. The above and 3 parts by mass or less.
進而,由實例1~實例3的結果可知,為了進一步提高上述效果,較佳為將有機過氧化物的調配比例於上述範圍內亦設定為基質聚合物每100質量份而為1質量份以上且2質量份以下。 Furthermore, as a result of the results of the examples 1 to 3, it is preferable that the blending ratio of the organic peroxide is within the above range, and the matrix polymer is preferably 1 part by mass or more per 100 parts by mass of the matrix polymer. 2 parts by mass or less.
相對於作為基質聚合物的天然橡膠每100質量份,將二氧化矽的調配比例設定為80質量份(比較例3)、100 質量份(實例4)、150質量份(實例5)、170質量份(實例6)、180質量份(比較例4),除此以外,與實例2同樣地製備高衰減組成物。 The proportion of the cerium oxide is set to 80 parts by mass per 100 parts by mass of the natural rubber as the matrix polymer (Comparative Example 3), 100 A high-attenuation composition was prepared in the same manner as in Example 2 except for the parts (Example 4), 150 parts by mass (Example 5), 170 parts by mass (Example 6), and 180 parts by mass (Comparative Example 4).
再者,比較例4的加工性低,為了製備上述高衰減組成物而混練上述各成分,或將所製備的高衰減組成物成形加工為上述圓板1的立體形狀需要長時間。 Further, in Comparative Example 4, the workability was low, and it took a long time to knead the above-described respective components in order to prepare the above-mentioned high-attenuation composition, or to mold the prepared high-attenuation composition into the three-dimensional shape of the above-mentioned disc 1.
對上述各實例、比較例的高衰減組成物進行上述各試驗而評價特性。 The high-attenuation compositions of the above respective examples and comparative examples were subjected to the above respective tests to evaluate the characteristics.
將結果與實例2的結果一併示於表4中。再者,表中,評價一欄中的Geq、Heq及保持率的數值均如上文所說明般為將先前例1設定為100時的相對值。 The results are shown together with the results of Example 2 in Table 4. Further, in the table, the values of Geq, Heq, and retention ratio in the evaluation column are relative values when the previous example 1 is set to 100 as described above.
由表4的實例2、實例4~實例6、比較例3、比較例4的結果可知,為了對高衰減組成物賦予良好的加工性,以及為了獲得維持良好的衰減性能、並且施加大幅變形後的彈性模數的下降小、而且反覆施加大幅變形時的耐久性亦優異的高衰減構件,必須將二氧化矽的調配比例設定為 相對於基質聚合物每100質量份而為100質量份以上且170質量份以下。 From the results of Example 2, Example 4 to Example 6, Comparative Example 3, and Comparative Example 4 of Table 4, it was found that in order to impart good workability to the high-attenuation composition, and to obtain good attenuation performance and to apply a large deformation, A high-attenuation member having a small decrease in the modulus of elasticity and excellent durability in the case of repeatedly applying a large deformation must set the proportion of cerium oxide to It is 100 parts by mass or more and 170 parts by mass or less per 100 parts by mass of the matrix polymer.
進而,由實例2、實例4~實例6的結果可知,為了進一步提高上述效果,較佳為將二氧化矽的調配比例於上述範圍內亦設定為相對於基質聚合物每100質量份而為135質量份以上且150質量份以下。 Further, as a result of the results of the example 2 and the examples 4 to 6, it is understood that, in order to further improve the above-described effects, it is preferable to set the proportion of the cerium oxide in the above range to be 135 per 100 parts by mass of the matrix polymer. More than the mass part and 150 parts by mass or less.
1‧‧‧圓板 1‧‧‧ round plate
2‧‧‧鋼板 2‧‧‧ steel plate
3‧‧‧試驗體 3‧‧‧Test body
4‧‧‧中央固定夾具 4‧‧‧Central Fixture
5‧‧‧左右固定夾具 Fixed fixture around 5‧‧
6‧‧‧固定臂 6‧‧‧Fixed Arm
7、9‧‧‧接頭 7, 9‧‧‧ joints
8‧‧‧可動盤 8‧‧‧ movable plate
H‧‧‧遲滯曲線 H‧‧‧hysteresis curve
Keq‧‧‧傾斜度 Keq‧‧‧ inclination
L1‧‧‧直線 L 1 ‧‧‧ Straight line
L2‧‧‧垂線 L 2 ‧‧‧ vertical line
W‧‧‧能量 W‧‧‧Energy
△W‧‧‧吸收能量 △W‧‧‧ absorbed energy
圖1是將為了對包含本發明的實例及比較例的高衰減組成物的高衰減構件的衰減性能進行評價而製作的、作為上述高衰減構件的模型的試驗體分解表示的分解立體圖。 1 is an exploded perspective view showing a test body exploded as a model of the high-attenuation member prepared for evaluating the attenuation performance of a high-attenuation member including a high-attenuation composition of Examples and Comparative Examples of the present invention.
圖2(a)、圖2(b)為對用以使上述試驗體位移而求出位移量與負載的關係的試驗機的概略進行說明的圖。 2(a) and 2(b) are diagrams for explaining an outline of a testing machine for determining the relationship between the displacement amount and the load by displacing the test body.
圖3為表示使用上述試驗機使試驗體位移而求出的表示位移量與負載的關係的遲滯曲線的一例的圖表。 3 is a graph showing an example of a hysteresis curve showing a relationship between a displacement amount and a load, which is obtained by displacing a test body using the above-described testing machine.
1‧‧‧圓板 1‧‧‧ round plate
2‧‧‧鋼板 2‧‧‧ steel plate
3‧‧‧試驗體 3‧‧‧Test body
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JP5524804B2 (en) * | 2010-10-21 | 2014-06-18 | 三菱電線工業株式会社 | Rubber composition, crosslinked rubber composition obtained by crosslinking the rubber composition, and sealing member |
US20140191477A1 (en) * | 2011-09-13 | 2014-07-10 | Osamu Kobayashi | Hydrogenated nitrile rubber composition |
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2011
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2012
- 2012-06-28 KR KR1020120069803A patent/KR101930543B1/en active IP Right Grant
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101451006A (en) * | 2007-12-04 | 2009-06-10 | 住友化学株式会社 | Rubber combination and damping material |
TW201116580A (en) * | 2009-11-06 | 2011-05-16 | Sumitomo Rubber Ind | High decay composition |
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JP2013095864A (en) | 2013-05-20 |
KR101930543B1 (en) | 2018-12-18 |
TW201319145A (en) | 2013-05-16 |
KR20130048138A (en) | 2013-05-09 |
CN103087358A (en) | 2013-05-08 |
CN103087358B (en) | 2016-10-05 |
JP5579152B2 (en) | 2014-08-27 |
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