TWI575007B - High decay composition - Google Patents
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- TWI575007B TWI575007B TW101111855A TW101111855A TWI575007B TW I575007 B TWI575007 B TW I575007B TW 101111855 A TW101111855 A TW 101111855A TW 101111855 A TW101111855 A TW 101111855A TW I575007 B TWI575007 B TW I575007B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
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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高衰減組成物,所述高衰減組成物成為緩和、吸收振動能量之傳遞的高衰減部件之原料。The present invention relates to a high attenuation composition which is a raw material for a high attenuation component that mitigates and absorbs the transmission of vibrational energy.
例如於高樓或橋樑等建築物、工業機械、航空器、汽車、軌道車輛、電腦或其周邊裝置類、家用電器類、甚至汽車用輪胎等範圍廣泛之領域中使用高衰減部件。藉由使用所述高衰減部件,可緩和、吸收振動能量之傳遞,亦即進行免震、制震、制振、防振等。For example, high-attenuation components are used in a wide range of fields such as buildings such as high-rise buildings or bridges, industrial machinery, aircraft, automobiles, rail vehicles, computers or peripheral devices, household appliances, and even automobile tires. By using the high-attenuation member, the transmission of vibration energy can be alleviated and absorbed, that is, vibration-free, vibration-proof, vibration-proof, vibration-proof, and the like.
所述高衰減部件由包含天然橡膠等作為基礎聚合物之高衰減組成物而形成。所述高衰減部件為了能夠使施加振動時之遲滯損耗(hysteresis loss)變大而使所述振動能量效率良好且快速地衰減之性能,亦即衰減性能提高,通常調配碳黑、二氧化矽等無機填充劑或松香、石油樹脂等賦黏劑等(例如參照專利文獻1~專利文獻3等)。The high attenuation member is formed of a high attenuation composition containing natural rubber or the like as a base polymer. The high-attenuation member is configured to be capable of increasing the hysteresis loss when vibration is applied, so that the vibration energy is efficiently and rapidly attenuated, that is, the attenuation performance is improved, and carbon black, ruthenium dioxide, etc. are usually formulated. An inorganic filler, an adhesive such as rosin or petroleum resin, and the like (for example, refer to Patent Document 1 to Patent Document 3).
然而,藉由該些先前高衰減組成物無法使高衰減部件之衰減性能充分提高。為了使高衰減部件之衰減性能與現狀相比進一步提高,考慮使無機填充劑或賦黏劑等之調配比例進一步增加等。However, the attenuation properties of the high attenuation component cannot be sufficiently improved by the previously high attenuation compositions. In order to further improve the attenuation performance of the high-attenuation member compared with the current state, it is considered to further increase the blending ratio of the inorganic filler or the adhesive or the like.
然而存在如下之問題:調配有大量之無機填充劑或賦黏劑之高衰減組成物之加工性降低,為了製造具有所期望之立體形狀的高衰減部件而對所述高衰減組成物進行混練、或者成形加工為所述立體形狀之操作並不容易。However, there is a problem in that the processability of a high-attenuation composition in which a large amount of an inorganic filler or an adhesive is formulated is lowered, and the high-attenuation composition is kneaded in order to manufacture a high-attenuation member having a desired three-dimensional shape. Or the operation of forming into the three-dimensional shape is not easy.
特別是於以工場級別大量生產高衰減部件之情形時,所述加工性之低下成為使高衰減部件之生產性大程度地降低、使生產所需之能量增大、另外使生產成本暴增的原因,因此並不理想。In particular, in the case of mass production of high-attenuation members at the factory level, the low workability is such that the productivity of the high-attenuation members is largely reduced, the energy required for production is increased, and the production cost is increased. The reason is therefore not ideal.
因此,為了並不降低加工性地使衰減性能提高,於專利文獻4中研究了於具有極性側鏈之基礎聚合物中調配具有2個以上極性基的衰減性賦予劑等之方法。Therefore, in order to improve the attenuation performance without lowering the workability, Patent Document 4 has studied a method of blending an attenuating imparting agent having two or more polar groups in a base polymer having a polar side chain.
然而,所述具有極性側鏈之基礎聚合物等於分子中具有極性基之基礎聚合物之玻璃轉移溫度Tg通常存在於室溫(3℃~35℃)附近,因此使用包含所述基礎聚合物之高衰減組成物而形成的高衰減部件存在如下之傾向:於作為最通常之使用溫度區域之所述室溫附近中,特別是剛性等特性之溫度依存性變大。However, the glass transition temperature Tg of the base polymer having a polar side chain equal to the base polymer having a polar group in the molecule is usually present at room temperature (3 ° C to 35 ° C), and thus the use of the base polymer is used. The high-attenuation member formed by the high-attenuation composition tends to have a temperature dependency of characteristics such as rigidity particularly in the vicinity of the room temperature which is the most usual use temperature region.
於專利文獻5中,研究了於不具極性側鏈之基礎聚合物中調配二氧化矽與具有2個以上極性基之衰減性賦予劑等的方法。根據該構成,可藉由併用二氧化矽而維持良好之衰減性能,且藉由使用不具極性基之基礎聚合物而作為基礎聚合物,可使於室溫附近之特性之溫度依存性變小。Patent Document 5 discloses a method of formulating cerium oxide and an attenuating imparting agent having two or more polar groups in a base polymer having no polar side chain. According to this configuration, it is possible to maintain good attenuation performance by using cerium oxide in combination, and by using a base polymer having no polar group as a base polymer, the temperature dependency of properties near room temperature can be made small.
然而,為了與現狀相比進一步使衰減性能提高而使所述衰減性賦予劑之調配比例增加之情形時,存在如下之問題:所述衰減性賦予劑變得容易於高衰減部件之表面起霜(bloom)。However, in order to increase the attenuation performance and increase the blending ratio of the attenuating imparting agent as compared with the current situation, there is a problem that the attenuating imparting agent becomes easy to bloom on the surface of the high-attenuating member. (bloom).
於專利文獻6中,研究了藉由使用具有特定之軟化點的松香衍生物作為衰減性賦予劑,而使衰減性能進一步提高之方法。Patent Document 6 studies a method of further improving the attenuation performance by using a rosin derivative having a specific softening point as an attenuating imparting agent.
然而,為了與現狀相比進一步使衰減性能提高而使松香衍生物之調配比例增加之情形時,產生如下之問題:黏著性過於變高而造成高衰減組成物之加工性降低。However, in order to further increase the attenuation performance and increase the blending ratio of the rosin derivative as compared with the current situation, there arises a problem that the adhesiveness is too high and the workability of the highly attenuating composition is lowered.
[先前技術文獻][Previous Technical Literature]
[專利文獻][Patent Literature]
[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
藉由所述專利文獻1~專利文獻6中所記載之高衰減組成物,存在如上所述那樣產生各種問題之虞,但藉由適度調整各成分之調配比例等,可同時實現某種程度之高的衰減性能與良好之加工性。The high-attenuation composition described in Patent Literatures 1 to 6 has various problems as described above. However, by appropriately adjusting the blending ratio of each component, etc., it is possible to achieve a certain degree at the same time. High attenuation performance and good processability.
然而,使用所述先前之高衰減組成物而形成的高衰減部件均變得容易產生於施加大的變形後彈性模數降低之所謂之馬林斯效應(Mullins’effect),無法充分發揮作為高衰減部件之所期望之性能,因此存在產生各種問題之情形。However, the high-attenuation member formed using the above-described high-attenuation composition is liable to be generated by the so-called Mullins' effect, which is reduced in the modulus of elasticity after application of a large deformation, and cannot be fully utilized as a high Attenuating the desired performance of the component, and thus there are situations in which various problems arise.
例如若擔負建築物之免震、制震的制震用阻尼器等產生大的變形而彈性模數降低,則存在變得無法確實地防止地震之能量傳遞至建築物之虞。因此,為了除考慮該彈性模數之降低以外亦確保所期望之性能,存在作為制震用阻尼器等製品之設計變複雜之問題。For example, if the damper for earthquake-proof and vibration-damping of a building is subjected to large deformation and the modulus of elasticity is lowered, there is a possibility that the energy of the earthquake cannot be reliably prevented from being transmitted to the building. Therefore, in order to ensure desired performance in addition to the reduction in the modulus of elasticity, there is a problem that the design of a product such as a damper for vibration is complicated.
本發明之目的在於提供一種新穎之高衰減組成物,其可製造具有高的衰減性能、且於施加大的變形後的彈性模數之降低小的高衰減部件。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel high-attenuation composition which can produce a high-attenuation member having high attenuation performance and having a small decrease in elastic modulus after application of a large deformation.
本發明是一種高衰減組成物,其特徵在於:於100質量份基礎聚合物中調配有3質量份以上50質量份以下之酸值為155 mgKOH/g以上之松香衍生物、100質量份以上180質量份以下之二氧化矽、0.1質量份以上10質量份以下之咪唑系化合物、及0.1質量份以上20質量份以下之受阻酚系化合物。The present invention is a high-attenuation composition characterized in that, in 100 parts by mass of the base polymer, 3 parts by mass or more and 50 parts by mass or less of a rosin derivative having an acid value of 155 mgKOH/g or more, and 100 parts by mass or more are contained. 0.1 parts by mass or more and 10 parts by mass or less of the imidazole-based compound, and 0.1 part by mass or more and 20 parts by mass or less of the hindered phenol-based compound.
根據發明者之研究,藉由併用松香衍生物、二氧化矽、咪唑系化合物、及受阻酚系化合物,可並不使所述各成分之調配比例增加,因此並不產生使高衰減組成物之加工性降低而產生起霜等問題,而是使使用所述高衰減組成物而形成之高衰減部件之衰減性能較現狀更進一步提高。According to the study by the inventors, by using a rosin derivative, a cerium oxide, an imidazole compound, and a hindered phenol-based compound in combination, the compounding ratio of the components can be increased without increasing the composition of the high-attenuating composition. The processability is lowered to cause problems such as blooming, and the attenuation performance of the high-attenuation member formed using the high-attenuation composition is further improved as compared with the current situation.
而且,作為松香衍生物,藉由選擇使用酸值為155 mgKOH/g以上之松香衍生物,根據後述之實例、比較例之結果可知,亦可抑制施加大的變形後之彈性模數降低。因此,若為例如制震用阻尼器等,可使作為用以確保所期望之性能之製品的設計簡略化。Further, as a rosin derivative, by using a rosin derivative having an acid value of 155 mgKOH/g or more, it is understood from the results of the examples and comparative examples described later that the decrease in the elastic modulus after application of a large deformation can be suppressed. Therefore, for example, a damper for vibration damping or the like can be simplified as a design for securing a desired performance.
而且,作為松香衍生物、二氧化矽、咪唑系化合物、及受阻酚系化合物,藉由於所述預定範圍內調整調配比例而調配各個種類不同之化合物,可使高衰減部件之衰減性能設計之自由度提高,因此有利於將衰減性能考慮至高衰減部件之設計中。Further, as the rosin derivative, the cerium oxide, the imidazole-based compound, and the hindered phenol-based compound, the compounding of the various types can be adjusted by adjusting the blending ratio within the predetermined range, so that the attenuation performance of the high-attenuating member can be freely designed. The degree of improvement is therefore advantageous in considering the attenuation performance in the design of high attenuation components.
作為基礎聚合物,可任意使用能夠藉由調配松香衍生物、二氧化矽、咪唑系化合物、及受阻酚系化合物而發揮高的衰減性能之各種基礎聚合物。As the base polymer, various base polymers which can exhibit high attenuation performance by blending a rosin derivative, a cerium oxide, an imidazole compound, and a hindered phenol compound can be used arbitrarily.
其中,若考慮特別是使衰減性能之溫度依存性變小,形成即使於廣之溫度範圍內亦可發揮穩定之衰減性能的高衰減部件,則所述基礎聚合物較佳的是選自由如下之化合物所構成之群組之至少1種:不具極性基而於室溫附近之剛性等特性之溫度依存性小的天然橡膠、異戊二烯橡膠、及丁二烯橡膠。In particular, it is preferable to form a high-attenuating member which exhibits stable attenuation performance even in a wide temperature range, in particular, the base polymer is preferably selected from the following At least one of the group consisting of a compound: a natural rubber, an isoprene rubber, and a butadiene rubber having a small temperature dependency of properties such as rigidity which does not have a polar group and is near room temperature.
於使用所述本發明之高衰減組成物作為形成材料,形成作為高衰減部件之建築物之制震用阻尼器之情形時,即使由於發生地震而產生大的變形,彈性模數亦不會大程度地降低,因此可確實地防止所述地震之能量傳遞至建築物。而且,因此亦可使用以確保所期望之性能的制震用阻尼器之設計簡略化。When the high-attenuation composition of the present invention is used as a forming material to form a damping damper for a building as a high-attenuating member, even if a large deformation occurs due to an earthquake, the elastic modulus is not large. The degree is lowered, so that the energy of the earthquake can be surely prevented from being transmitted to the building. Moreover, it is therefore also possible to simplify the design of the damping damper to ensure the desired performance.
[發明的效果][Effects of the Invention]
藉由本發明可提供一種新穎之高衰減組成物,其可製造具有高的衰減性能、且於施加大的變形後的彈性模數之降低小的高衰減部件。By the present invention, it is possible to provide a novel high-attenuation composition which can produce a high-attenuation member having high attenuation performance and having a small decrease in elastic modulus after application of a large deformation.
本發明是一種高衰減組成物,其特徵在於:於100質量份基礎聚合物中調配有3質量份以上50質量份以下之酸值為155 mgKOH/g以上之松香衍生物、100質量份以上180質量份以下之二氧化矽、0.1質量份以上10質量份以下之咪唑系化合物、及0.1質量份以上20質量份以下之受阻酚系化合物。The present invention is a high-attenuation composition characterized in that, in 100 parts by mass of the base polymer, 3 parts by mass or more and 50 parts by mass or less of a rosin derivative having an acid value of 155 mgKOH/g or more, and 100 parts by mass or more are contained. 0.1 parts by mass or more and 10 parts by mass or less of the imidazole-based compound, and 0.1 part by mass or more and 20 parts by mass or less of the hindered phenol-based compound.
(基礎聚合物)(base polymer)
作為基礎聚合物,可任意使用能夠藉由調配松香衍生物、二氧化矽、咪唑系化合物、及受阻酚系化合物而發揮高的衰減性能的各種基礎聚合物,其中較佳的是橡膠。As the base polymer, various base polymers which can exhibit high attenuation performance by blending a rosin derivative, a cerium oxide, an imidazole compound, and a hindered phenol compound can be used arbitrarily, and among them, rubber is preferred.
所述橡膠例如可列舉天然橡膠、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、多硫橡膠等之1種或2種以上。Examples of the rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, norbornene rubber, ethylene propylene rubber, ethylene propylene diene rubber, butyl rubber, and halogenated butyl rubber. One or more of chloroprene rubber, acrylonitrile butadiene rubber, epichlorohydrin rubber, chlorosulfonated polyethylene, and polysulfide rubber.
特別是若考慮減小衰減性能之溫度依存性而提供於廣溫度範圍內顯示出穩定之衰減性能的高衰減部件,則所述橡膠中較佳的是選自由天然橡膠、異戊二烯橡膠、及丁二烯橡膠所構成之群組之至少1種橡膠。In particular, if a high attenuation member exhibiting stable attenuation performance over a wide temperature range is provided in consideration of reducing the temperature dependency of the attenuation performance, it is preferable that the rubber is selected from natural rubber, isoprene rubber, And at least one rubber of the group consisting of butadiene rubber.
橡膠亦可併用2種以上,但若考慮使高衰減組成物之組成簡略化而提高所述高衰減組成物以及高衰減部件之生產性,進一步減低生產成本,則較佳的是單獨使用任意1種。Two or more types of rubber may be used in combination. However, if the composition of the high-attenuation composition is simplified and the productivity of the high-attenuation composition and the high-attenuation member is improved, and the production cost is further reduced, it is preferable to use any one alone. Kind.
(松香衍生物)(rosin derivative)
作為松香衍生物,例如可自松香與多元醇(丙三醇等)之酯或松香改質馬來酸樹脂等包含松香作為構成成分之樹脂、且具有發揮作為賦黏劑之功能而使高衰減部件之衰減性能提高的效果之各種衍生物中,選擇酸值為155 mgKOH/g以上者而使用。藉此可抑制施加大的變形後的彈性模數之降低。其原因在於:一旦施加大的變形,則雖然二氧化矽或咪唑化合物與松香衍生物的弱結合而分離,但酸值為所述範圍內之松香衍生物之相互作用多之部分立即再結合而使彈性模數容易地回復。The rosin derivative can be, for example, a resin containing rosin as a constituent component such as an ester of rosin and a polyhydric alcohol (such as glycerin) or a rosin-modified maleic acid resin, and has a function as a binder to cause high attenuation. Among the various derivatives which have an effect of improving the attenuation performance of the member, those having an acid value of 155 mgKOH/g or more are selected and used. Thereby, the decrease in the elastic modulus after the application of the large deformation can be suppressed. The reason for this is that once a large deformation is applied, although the cerium oxide or the imidazole compound is separated from the weak combination of the rosin derivative, the interaction of the rosin derivative having an acid value within the range is immediately recombined. The elastic modulus is easily restored.
另外,作為松香衍生物之酸值,若考慮進一步抑制施加大的變形後之彈性模數之降低,則於所述範圍內較佳的是160 mgKOH/g以上,特佳的是220 mgKOH/g以上。而且,松香衍生物之酸值若過高則極性過於變高,變得難以溶合於基礎聚合物中,因此於所述範圍內較佳的是330 mgKOH/g以下,特佳的是300 mgKOH/g以下。Further, as the acid value of the rosin derivative, in consideration of further suppressing the decrease in the elastic modulus after application of a large deformation, it is preferably 160 mgKOH/g or more, and particularly preferably 220 mgKOH/g in the above range. the above. Further, if the acid value of the rosin derivative is too high, the polarity becomes too high and it becomes difficult to be fused to the base polymer. Therefore, it is preferably 330 mgKOH/g or less, and particularly preferably 300 mgKOH in the above range. /g below.
而且,松香衍生物之軟化點較佳的是80℃以上、140℃以下。Further, the softening point of the rosin derivative is preferably 80 ° C or more and 140 ° C or less.
若軟化點不足所述範圍,則存在無法充分獲得使高衰減部件之衰減性能提高的效果之虞。另一方面,若超過所述範圍,則存在如下之虞:加工性降低,為了調製高衰減組成物而對各成分進行混練、為了製造高衰減部件而對所述高衰減組成物進行混練、或者成形加工為任意形狀之操作變得不容易。When the softening point is less than the above range, the effect of improving the attenuation performance of the high-attenuation member cannot be sufficiently obtained. On the other hand, when it exceeds the above range, there is a possibility that the workability is lowered, the components are kneaded in order to prepare a highly attenuating composition, and the high-attenuation member is kneaded for producing a high-attenuation member, or The operation of forming into an arbitrary shape becomes not easy.
另外,軟化點是用藉由日本工業標準JIS K2207-1996「石油瀝青」中所記載之軟化點試驗方法(環球法)而測定之值所表示。In addition, the softening point is represented by the value measured by the softening point test method (ring and ball method) described in Japanese Industrial Standard JIS K2207-1996 "Petroleum Bitumen".
所述松香衍生物例如可列舉均為荒川化學工業股份有限公司製造之PINECRYSTAL(註冊商標)系列中之KR-85(酸值為165 mgKOH/g~175 mgKOH/g、軟化點為80℃~87℃)、KR-612(酸值為160 mgKOH/g~175 mgKOH/g、軟化點為80℃~90℃)、KR-614(酸值為170 mgKOH/g~180 mgKOH/g、軟化點為84℃~94℃)、KE-604(酸值為230 mgKOH/g~245 mgKOH/g、軟化點為122℃~134℃)等之1種或2種以上。The rosin derivative is, for example, KR-85 in the PINECRYSTAL (registered trademark) series manufactured by Arakawa Chemical Industries Co., Ltd. (acid value: 165 mgKOH/g to 175 mgKOH/g, softening point: 80 ° C to 87) °C), KR-612 (acid value: 160 mgKOH/g to 175 mgKOH/g, softening point: 80 °C to 90 °C), KR-614 (acid value: 170 mgKOH/g to 180 mgKOH/g, softening point One or two or more kinds of KE-604 (acid value: 230 mgKOH/g to 245 mgKOH/g, softening point: 122 to 134 °C).
特別是若考慮酸值與軟化點,則所述松香衍生物中較佳的是KR-612、KE-604。Particularly, in view of the acid value and the softening point, KR-612 and KE-604 are preferred among the rosin derivatives.
松香衍生物之調配比例必須是相對於每100質量份基礎聚合物為3質量份以上、50質量份以下。The blending ratio of the rosin derivative must be 3 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the base polymer.
若調配比例不足3質量份,則無法獲得調配松香衍生物而所帶來之使高衰減部件之衰減性能提高的效果。而且,於超過50質量份之情形時,松香衍生物所帶來之黏著性增大而造成加工性降低,變得無法進行如下操作:為了調配高衰減組成物而對各成分進行混練,為了製造高衰減部件而對所述高衰減組成物進行混練,或者成形加工為任意形狀。When the blending ratio is less than 3 parts by mass, the effect of improving the damping performance of the high-attenuating member due to the blending of the rosin derivative cannot be obtained. Further, in the case of more than 50 parts by mass, the adhesiveness of the rosin derivative is increased to cause a decrease in workability, and it becomes impossible to carry out the following operations: mixing the components for the purpose of blending the high-attenuating composition, for the purpose of manufacturing The high-attenuation member is kneaded with a high attenuation member or formed into an arbitrary shape.
另外,作為松香衍生物之調配比例,若考慮使高衰減部件之衰減性能進一步提高,則於所述範圍內較佳的是10質量份以上。而且,若考慮使施加大的變形後之彈性模數之降低儘可能地減少,則於所述範圍內較佳的是20質量份以下。In addition, as the blending ratio of the rosin derivative, in consideration of further improving the attenuation performance of the high-attenuating member, it is preferably 10 parts by mass or more in the above range. Further, in consideration of reducing the decrease in the elastic modulus after the application of the large deformation as much as possible, it is preferably 20 parts by mass or less in the above range.
(二氧化矽)(cerium oxide)
二氧化矽可使用根據其製法而分類之濕式法二氧化矽、乾式法二氧化矽之任意種。而且,作為二氧化矽,若考慮提高作為填充劑發揮功能而使高衰減部件之衰減性能提高的效果,較佳的是使用BET比表面積為100 m2/g以上、特別是200 m2/g以上者,且較佳的是使用BET比表面積為400 m2/g以下、特別是250 m2/g以下者。As the cerium oxide, any of the wet type cerium oxide and the dry type cerium oxide classified according to the production method thereof can be used. Further, as the cerium oxide, it is preferable to use an BET specific surface area of 100 m 2 /g or more, particularly 200 m 2 /g, in order to improve the function of the filler as a filler and to improve the attenuation performance of the high-attenuating member. In the above, it is preferred to use a BET specific surface area of 400 m 2 /g or less, particularly 250 m 2 /g or less.
BET比表面積是以藉由氣相吸附法所測定之值而表示,所述氣相吸附法使用例如柴田化學器械工業股份有限公司製造之迅速表面積測定裝置SA-1000等,使用氮氣作為吸附氣體。The BET specific surface area is represented by a value measured by a vapor phase adsorption method using, for example, a rapid surface area measuring device SA-1000 manufactured by Shibata Chemical Instruments Industrial Co., Ltd., or the like, using nitrogen as an adsorption gas.
所述二氧化矽例如可列舉Tosoh Silica Corporation製造之NipSil(註冊商標)KQ、VN3、AQ、ER等之1種或2種以上。For example, one or two or more of NipSil (registered trademark) KQ, VN3, AQ, and ER manufactured by Tosoh Silica Corporation may be mentioned.
二氧化矽之調配比例必須是相對於每100質量份基礎聚合物為100質量份以上、180質量份以下。The blending ratio of the cerium oxide must be 100 parts by mass or more and 180 parts by mass or less per 100 parts by mass of the base polymer.
若調配比例不足100質量份,則無法獲得調配二氧化矽所帶來之使高衰減部件之衰減性能提高的效果。而且,於超過180質量份之情形時,無法獲得調配所述特定松香衍生物而帶來之使施加大的變形後之彈性模數之降低變小之效果。If the blending ratio is less than 100 parts by mass, the effect of improving the damping performance of the high-attenuating member due to the blending of cerium oxide cannot be obtained. Further, in the case of more than 180 parts by mass, the effect of blending the specific rosin derivative to reduce the decrease in the modulus of elasticity after applying a large deformation cannot be obtained.
而且,於超過180質量份之情形時存在如下之情形:高衰減組成物之加工性降低,特別是變得難以以工場級別而大量生產具有所期望之立體形狀的高衰減部件。而且,雖然可以試製級別而形成少量之高衰減部件,但所形成之高衰減部件硬且難以變形,因此產生如下之問題:特別是於大的變形時容易被破壞。Further, in the case of more than 180 parts by mass, there is a case where the workability of the high-attenuation composition is lowered, and in particular, it becomes difficult to mass-produce a high-attenuation member having a desired three-dimensional shape at the factory level. Further, although a small number of high-attenuation members can be formed at a trial level, the formed high-attenuation members are hard and hard to be deformed, and thus have a problem that they are easily broken particularly in the case of large deformation.
另外,作為二氧化矽之調配比例,若考慮使高衰減部件之衰減性能進一步提高,則於所述範圍內較佳的是135質量份以上。而且,若考慮使施加大的變形後之彈性模數之降低儘可能地減小,則於所述範圍內較佳的是150質量份以下。In addition, as the mixing ratio of the cerium oxide, in consideration of further improving the attenuation performance of the high-attenuating member, it is preferably 135 parts by mass or more in the above range. Further, in consideration of reducing the decrease in the elastic modulus after the application of the large deformation as much as possible, it is preferably 150 parts by mass or less in the above range.
(咪唑系化合物)(imidazole compound)
咪唑系化合物例如可列舉分子中具有咪唑環之各種化合物中的具有如下功能的各種咪唑系化合物:可提高由包含二氧化矽、松香衍生物及受阻酚系化合物之高衰減組成物所構成之高衰減部件的衰減性能。Examples of the imidazole-based compound include various imidazole compounds having the following functions among various compounds having an imidazole ring in the molecule: a high-yield composition composed of a cerium oxide, a rosin derivative, and a hindered phenol compound can be improved. Attenuation characteristics of the attenuation component.
所述咪唑系化合物例如可列舉咪唑、1,2-二甲基咪唑、2-乙基-4-甲基-咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等之1種或2種以上。Examples of the imidazole-based compound include imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl-imidazole, 1-benzyl-2-methylimidazole, and 1-benzyl-2-benzene. One or two or more kinds of imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole.
特別是於使高衰減部件之衰減性能提高的效果之方面而言,較佳的是咪唑、2-甲基咪唑、1,2-二甲基咪唑,其中最佳的是咪唑。Particularly, in terms of an effect of improving the attenuation performance of the high-attenuating member, imidazole, 2-methylimidazole, and 1,2-dimethylimidazole are preferable, and among them, imidazole is most preferable.
咪唑系化合物之調配比例必須是相對於每100質量份基礎聚合物為0.1質量份以上、10質量份以下。The blending ratio of the imidazole-based compound must be 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the base polymer.
若調配比例不足0.1質量份,則無法獲得使高衰減部件之衰減性能提高的效果。而且,於超過10質量份之情形時,變得容易產生焦化而造成加工性降低,從而變得無法進行如下之操作:為了調製高衰減組成物而對各成分進行混練,為了製造高衰減部件而對所述高衰減組成物進行混練,或者成形加工為任意形狀。If the blending ratio is less than 0.1 part by mass, the effect of improving the damping performance of the high-attenuating member cannot be obtained. Further, when it exceeds 10 parts by mass, coking tends to occur and workability is lowered, so that it becomes impossible to knead each component in order to modulate a highly attenuating composition, in order to manufacture a highly attenuating member. The highly attenuating composition is kneaded or shaped into an arbitrary shape.
另外,作為咪唑系化合物之調配比例,若考慮維持高衰減組成物之良好之加工性,且使高衰減部件之衰減性能進一步提高,則於所述範圍內較佳的是0.3質量份以上、5質量份以下。In addition, in order to maintain good workability of the high-attenuation composition and to further improve the attenuation performance of the high-attenuation member, the blending ratio of the imidazole-based compound is preferably 0.3 parts by mass or more in the above range. Below the mass.
(受阻酚系化合物)(hindered phenolic compound)
受阻酚系化合物可使用起到如下作用之各種受阻酚系化合物之任意種:由於分子中之羥基與二氧化矽表面之羥基相互作用,而使所述二氧化矽對於以基礎聚合物為首之有機系各成分的親和性、相溶性提高,且使高衰減部件之衰減性能進一步提高。As the hindered phenol-based compound, any of various hindered phenol-based compounds which function as the organic group headed by the base polymer due to the interaction of the hydroxyl group in the molecule with the hydroxyl group on the surface of the ceria can be used. The affinity and compatibility of the components are improved, and the attenuation performance of the high-attenuation member is further improved.
所述受阻酚系化合物較佳的是所述具有2個以上羥基之各種受阻酚系化合物,特佳的是雙酚系抗老化劑、多酚系抗老化劑、硫代雙酚系抗老化劑、對苯二酚系抗老化劑等抗老化劑之1種或2種以上。The hindered phenol-based compound is preferably the above-mentioned various hindered phenol-based compounds having two or more hydroxyl groups, and particularly preferably a bisphenol-based anti-aging agent, a polyphenol-based anti-aging agent, and a thiobisphenol-based anti-aging agent. One or two or more kinds of anti-aging agents such as a hydroquinone-based anti-aging agent.
所述化合物中之雙酚系抗老化劑例如可列舉1,1-雙(3-羥基苯基)環己烷、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、2,2'-亞甲基雙[6-(1-甲基環己基)]-對甲酚、4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)、3,9-雙[2-(3-第三丁基-4-羥基-5-甲基苯基丙醯氧基)-1,1-二甲基乙基]-2,4,8,10-四氧雜螺(5,5)十一烷、對甲酚與二環戊二烯之丁基化反應產物等之1種或2種以上。The bisphenol-based anti-aging agent in the compound may, for example, be 1,1-bis(3-hydroxyphenyl)cyclohexane or 2,2'-methylenebis(4-methyl-6-tributyl). Phenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)]- P-cresol, 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-- Phenylpropionyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane, p-cresol and dicyclopentadiene One or two or more kinds of the butylation reaction product.
多酚系抗老化劑例如可列舉四[亞甲基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]等。Examples of the polyphenol-based anti-aging agent include tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate].
硫代雙酚系抗老化劑例如可列舉4,4-硫代雙(3-甲基-6-第三丁基苯酚)、4,4'-雙(3,5-二-第三丁基-4-羥基苄基)硫醚、4,4'-硫代雙(6-第三丁基-鄰甲酚)等之1種或2種以上。Examples of the thiobisphenol-based anti-aging agent include 4,4-thiobis(3-methyl-6-tert-butylphenol) and 4,4'-bis(3,5-di-t-butyl group. One or more of -4-hydroxybenzyl) sulfide and 4,4'-thiobis(6-tert-butyl-o-cresol).
另外,對苯二酚系抗老化劑例如可列舉2,5-二-第三丁基對苯二酚、2,5-二-第三丁基戊基對苯二酚等之1種或2種以上。Further, examples of the hydroquinone-based anti-aging agent include one or two of 2,5-di-t-butyl hydroquinone and 2,5-di-t-butylpentyl hydroquinone. More than one species.
受阻酚系化合物之調配比例必須是相對於每100質量份基礎聚合物為0.1質量份以上、20質量份以下。The blending ratio of the hindered phenol-based compound must be 0.1 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the base polymer.
若調配比例不足0.1質量份,則不能獲得使高衰減部件之衰減性能提高之效果。而且,於超過20質量份之情形時,存在如下之問題:過量之受阻酚系化合物變得容易如前文所說明那樣在高衰減部件之表面上起霜。If the blending ratio is less than 0.1 part by mass, the effect of improving the damping performance of the high-attenuating member cannot be obtained. Further, in the case of more than 20 parts by mass, there is a problem that an excessively hindered phenol-based compound becomes easy to bloom on the surface of the high-attenuating member as explained above.
另外,作為受阻酚系化合物之調配比例,若考慮使高衰減部件之衰減性能更進一步提高,則較佳的是於所述範圍內為1質量份以上,特佳的是2.5質量份以上。In addition, the blending ratio of the hindered phenol-based compound is preferably 1 part by mass or more, and particularly preferably 2.5 parts by mass or more in the above range, in consideration of further improving the attenuation performance of the high-attenuating member.
(其他)(other)
於本發明之高衰減組成物中,亦可以適宜之比例而進一步調配硫化劑、硫化促進劑、硫化促進助劑等用以使脫蛋白天然橡膠硫化之硫化系添加劑,或矽烷化合物、軟化劑、賦黏劑、受阻酚系以外之其他抗老化劑等各種添加劑。In the high-attenuation composition of the present invention, a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerating aid, or the like may be further blended in a suitable ratio to vulcanize the deproteinized natural rubber, or a decane compound or a softener. Various additives such as tackifiers and other anti-aging agents other than hindered phenols.
其中,作為矽烷化合物,可列舉以式(a)而表示,可作為矽烷偶合劑或矽烷化劑等二氧化矽之分散劑發揮功能之各種矽烷化合物,In addition, examples of the decane compound include various decane compounds which are represented by the formula (a) and which function as a dispersing agent for cerium oxide such as a decane coupling agent or a decylating agent.
[化1][Chemical 1]
[式中,R1、R2、R3、及R4中之至少1個表示烷氧基。其中,R1、R2、R3、及R4並不同時為烷氧基,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 simultaneously alkoxy groups, and the others represent an alkyl group or an aryl group].
特佳的是己基三甲氧基矽烷、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.
所述矽烷化合物例如可列舉信越化學工業股份有限公司製造之KBE-103(苯基三乙氧基矽烷)等。Examples of the decane compound include KBE-103 (phenyltriethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
矽烷化合物之調配比例並無特別限定,較佳的是相對於每100質量份二氧化矽為5質量份以上、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 25 parts by mass or less per 100 parts by mass of the cerium oxide.
作為軟化劑,可列舉香豆酮-茚樹脂、液狀橡膠等之1種或2種以上。The softening agent may be one or more selected from the group consisting of a coumarone-indene resin and a liquid rubber.
其中,作為香豆酮-茚樹脂,可列舉主要包含香豆酮與茚之聚合物、平均分子量為1000以下左右之比較低分子量、可作為軟化劑而發揮功能之各種香豆酮-茚樹脂。In addition, examples of the coumarone-indene resin include various coumarone-indene resins which mainly contain a polymer of coumarone and hydrazine, a relatively low molecular weight having an average molecular weight of about 1,000 or less, and a function as a softening agent.
所述香豆酮-茚樹脂例如可列舉日塗化學股份有限公司製造之Nitto Resin(註冊商標)香豆酮G-90[平均分子量為770、軟化點為90℃、酸值為1.0 KOHmg/g以下、羥值為25 KOHmg/g、溴值9 g/100 g]、G-100N[平均分子量為730、軟化點為100℃、酸值為1.0 KOHmg/g以下、羥值為25 KOHmg/g、溴值11 g/100 g]、V-120[平均分子量為960、軟化點為120℃、酸值為1.0 KOHmg/g以下、羥值為30 KOHmg/g、溴值6 g/100 g]、V-120S[平均分子量為950、軟化點為120℃、酸值為1.0 KOHmg/g以下、羥值為30 KOHmg/g、溴值7 g/100 g]等之1種或2種以上。The coumarone-indene resin is, for example, Nitto Resin (registered trademark) coumarone G-90 manufactured by Nippon Paint Chemical Co., Ltd. [average molecular weight: 770, softening point: 90 ° C, acid value: 1.0 KOH mg/g. Hereinafter, the hydroxyl value is 25 KOHmg/g, the bromine number is 9 g/100 g], G-100N [the average molecular weight is 730, the softening point is 100 ° C, the acid value is 1.0 KOH mg/g or less, and the hydroxyl value is 25 KOH mg/g. , bromine number 11 g / 100 g], V-120 [average molecular weight of 960, softening point of 120 ° C, acid value of 1.0 KOHmg / g or less, hydroxyl value of 30 KOHmg / g, bromine value of 6 g / 100 g] And V-120S [one or two or more kinds of an average molecular weight of 950, a softening point of 120 ° C, an acid value of 1.0 KOHmg/g or less, a hydroxyl value of 30 KOHmg/g, and a bromine number of 7 g/100 g].
香豆酮-茚樹脂之調配比例並無特別限定,較佳的是相對於每100質量份脫蛋白天然橡膠為5質量份以上、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 50 parts by mass or less per 100 parts by mass of the deproteinized natural rubber.
而且,液狀橡膠可列舉於室溫(3℃~35℃)下呈液狀之各種橡膠。所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)等之1種或2種以上。Further, examples of the liquid rubber include various rubbers which are liquid at room temperature (3 to 35 ° C). The liquid rubber may, for example, be one or more selected from the group consisting of liquid polyisoprene rubber, liquid nitrile rubber (liquid NBR), and liquid styrene butadiene rubber (liquid SBR).
其中,較佳的是液狀聚異戊二烯橡膠。所述液狀聚異戊二烯橡膠例如可列舉日本可樂麗公司製造之Kuraplene(註冊商標)LIR-50等。Among them, preferred is a liquid polyisoprene rubber. Examples of the liquid polyisoprene rubber include Kuraplene (registered trademark) LIR-50 manufactured by Kuraray Co., Ltd., and the like.
液狀聚異戊二烯橡膠之調配比例並無特別限定,較佳的是相對於每100質量份脫蛋白天然橡膠為5質量份以上、80質量份以下。The blending ratio of the liquid polyisoprene rubber is not particularly limited, and is preferably 5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the deproteinized natural rubber.
賦黏劑例如可列舉石油樹脂等。而且,石油樹脂例如較佳的是丸善石油化學股份有限公司製造之Maruka Lyncur(註冊商標)M890A[二環戊二烯系石油樹脂、軟化點為105℃]等。Examples of the tackifier include petroleum resins and the like. Further, the petroleum resin is, for example, Maruka Lyncur (registered trademark) M890A (dicyclopentadiene petroleum resin, softening point: 105 ° C) manufactured by Maruzen Petrochemical Co., Ltd., and the like.
所述石油樹脂之調配比例並無特別限定,較佳的是相對於每100質量份脫蛋白天然橡膠為3質量份以上、50質量份以下。The blending ratio of the petroleum resin is not particularly limited, and is preferably 3 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the deproteinized natural rubber.
抗老化劑例如可列舉苯并咪唑系、醌系、多酚系、胺系等之各種抗老化劑之1種或2種以上。特佳的是將苯并咪唑系抗老化劑與醌系抗老化劑併用。The anti-aging agent may, for example, be one or more of various anti-aging agents such as benzimidazole-based, anthraquinone-based, polyphenol-based, and amine-based. It is particularly preferred to use a benzimidazole-based anti-aging agent in combination with a lanthanide anti-aging agent.
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份有限公司製造之Nocrac(註冊商標)MB[2-巰基苯并咪唑]等。而且,醌系抗老化劑例如可列舉丸石化學品股份有限公司製造之Antigen FR[芳香族酮-胺縮合物]等。Among them, the benzimidazole-based anti-aging agent is, for example, Nocrac (registered trademark) MB [2-mercaptobenzimidazole] manufactured by Ouchi Shinko Chemical Co., Ltd., and the like. Further, examples of the lanthanide anti-aging agent include Antigen FR [aromatic ketone-amine condensate] manufactured by Maruishi Chemicals Co., Ltd., and the like.
兩種抗老化劑之調配比例並無特別限定,較佳的是苯并咪唑系抗老化劑相對於100質量份脫蛋白天然橡膠中為0.5質量份以上、5質量份以下。而且,較佳的是醌系抗老化劑相對於每100質量份脫蛋白天然橡膠為0.5質量份以上、5質量份以下。The blending ratio of the two anti-aging agents is not particularly limited, and it is preferred that the benzimidazole-based anti-aging agent is 0.5 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the deproteinized natural rubber. Moreover, it is preferable that the lanthanide anti-aging agent is 0.5 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the deproteinized natural rubber.
硫化劑例如可列舉硫或含硫有機化合物等。特佳的是硫。Examples of the vulcanizing agent include sulfur or a sulfur-containing organic compound. Particularly good is sulfur.
硫化促進劑例如可列舉亞磺醯胺系硫化促進劑、秋蘭姆系硫化促進劑等。硫化促進劑根據種類而造成促進硫化之機理不同,因此較佳的是將所述兩者併用。Examples of the vulcanization accelerator include a sulfinamide-based vulcanization accelerator and a thiuram-based vulcanization accelerator. Since the vulcanization accelerator has a different mechanism for promoting vulcanization depending on the kind, it is preferred to use the two together.
其中,亞磺醯胺系硫化促進劑例如可列舉大內新興化學工業股份有限公司製造之Nocceler(註冊商標)NS[N-第三丁基-2-苯并噻唑基亞磺醯胺]等。而且,秋蘭姆系硫化促進劑例如可列舉大內新興化學工業股份有限公司製造之Nocceler TBT[四丁基秋蘭姆二硫化物]等。In the sulfinamide-based vulcanization accelerator, for example, Nocceler (registered trademark) NS [N-t-butyl-2-benzothiazolylsulfinamide] manufactured by Ouchi Shinko Chemical Co., Ltd., and the like can be cited. Further, examples of the thiuram vulcanization accelerator include Nocceler TBT (tetrabutyl thiuram disulfide) manufactured by Ouchi Shinko Chemical Industry Co., Ltd., and the like.
硫化促進助劑例如可列舉鋅華、硬脂酸等。通常較佳的是將兩者併用為硫化促進助劑。Examples of the vulcanization accelerating aid include zinc oxide and stearic acid. It is generally preferred to use both as a vulcanization accelerating aid.
所述硫化劑、硫化促進劑、硫化促進助劑之調配比例根據由於高衰減部件之用途等而不同之衰減性能或橡膠硬度等特性而適宜調整即可。The blending ratio of the vulcanizing agent, the vulcanization accelerator, and the vulcanization accelerating aid may be appropriately adjusted depending on characteristics such as attenuation performance or rubber hardness which are different depending on the use of the high-attenuating member.
本發明之高衰減組成物可藉由如下方式而製造具有預定之衰減性能的高衰減部件:使用任意之混練機而對所述各成分進行混練而進行調製,將所述高衰減組成物成形加工為所期望之立體形狀,且對脫蛋白天然橡膠進行硫化。The high-attenuation composition of the present invention can produce a high-attenuation member having a predetermined attenuation performance by arranging the components by kneading using any kneading machine, and shaping the high-attenuation composition. The desired three-dimensional shape is used to vulcanize the deproteinized natural rubber.
作為可使用本發明之高衰減組成物而製造之高衰減部件,例如可列舉:高樓等建築物之基礎中所內裝之免震用阻尼器、建築物之結構中所內裝之制震(制振)用阻尼器、吊橋或斜張橋等之線纜之制振部件、工業機械或航空器、汽車、軌道車輛等之防振部件、電腦或其周邊裝置類、或家用電器類等之防振部件、以及汽車用輪胎之輪胎面等。Examples of the high-attenuation member which can be produced by using the high-attenuation composition of the present invention include shock-absorbing dampers incorporated in the foundation of a building such as a high-rise building, and shock-proofing built in the structure of a building. (Vibration) Damping parts for cables such as dampers, suspension bridges or diagonal bridges, anti-vibration parts for industrial machinery or aircraft, automobiles, rail vehicles, etc., computers or peripheral devices, or household appliances, etc. Anti-vibration parts, tire surfaces of automobile tires, etc.
根據本發明,藉由於所述範圍內調整所述二氧化矽、松香衍生物、咪唑系化合物、及受阻酚系化合物之種類與其組合及調配比例,可獲得具有適於上述各個用途之優異之衰減性能的高衰減部件。According to the present invention, by adjusting the kinds of the ceria, the rosin derivative, the imidazole compound, and the hindered phenol compound in the above range, and the combination and blending ratio thereof, excellent attenuation suitable for each of the above uses can be obtained. High attenuation components for performance.
特別是使用本發明之高衰減組成物而形成內裝於建築物之結構中之制震用阻尼器之情形時,所述制震用阻尼器之振動之衰減性能優異,且施加大的變形後的彈性模數之降低小,因此可使作為用以確保所期望之性能之製品的設計簡略化,另外可減少於1個建築物中所內裝之制震用阻尼器之數量。In particular, in the case of using the high-attenuation composition of the present invention to form a shock damper incorporated in a structure of a building, the vibration damping performance of the shock damper is excellent, and after a large deformation is applied Since the reduction in the modulus of elasticity is small, the design of the article for ensuring the desired performance can be simplified, and the number of the dampers for damping provided in one building can be reduced.
[實例][Example]
以下之實例、比較例中之高衰減組成物之調製及試驗除了特別記載以外均於溫度為20℃、相對濕度為55%之環境下實施。The preparation and test of the high-attenuation composition in the following examples and comparative examples were carried out in an environment of a temperature of 20 ° C and a relative humidity of 55%, unless otherwise specified.
<實例1><Example 1>
於作為基礎聚合物之天然橡膠[SMR(Standard Malaysian Rubber,標準馬來西亞橡膠)-CV60] 100質量份中調配:In 100 parts by mass of natural rubber (SMR (Standard Malaysian Rubber)-CV60] as a base polymer:
* 二氧化矽[Tosoh Silica Corporation製造之NipSil KQ] 135質量份、* cerium oxide [NipSil KQ manufactured by Tosoh Silica Corporation] 135 parts by mass,
* 松香衍生物[改質松香衍生物、酸值為230 mgKOH/g~245 mgKOH/g、軟化點為122℃~134℃、荒川化學工業股份有限公司製造之PINECRYSTAL(註冊商標)KE-604] 10質量份、* Rosin derivative [modified rosin derivative, acid value: 230 mgKOH/g to 245 mgKOH/g, softening point: 122 °C to 134 °C, PINECRYSTAL (registered trademark) KE-604 manufactured by Arakawa Chemical Industry Co., Ltd.] 10 parts by mass,
* 作為咪唑系化合物之咪唑[日本合成化學工業股份有限公司製造] 2.5質量份、及* Imidazole as an imidazole compound [manufactured by Nippon Synthetic Chemical Co., Ltd.] 2.5 parts by mass, and
* 作為受阻酚系化合物之4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)[大內新興化學工業股份有限公司製造之Nocrac(註冊商標)NS-30] 2.5質量份* 4,4'-butylene bis(3-methyl-6-tert-butylphenol) as a hindered phenolic compound [Nocrac (registered trademark) NS-30 manufactured by Ouchi Shinko Chemical Co., Ltd.) 2.5 Parts by mass
下述表1中所示之各成分,使用密閉式混練機進行混練而調製高衰減組成物。Each component shown in the following Table 1 was kneaded using a closed kneader to prepare a highly attenuating composition.
表1中之各成分如下所示。The components in Table 1 are as follows.
苯基三乙氧基矽烷:信越化學工業股份有限公司製造之KBE-103Phenyltriethoxydecane: KBE-103 manufactured by Shin-Etsu Chemical Co., Ltd.
二環戊二烯系石油樹脂:軟化點為105℃、丸善石油化學股份有限公司製造之Maruka Lyncur(註冊商標)M890ADicyclopentadiene-based petroleum resin: Maruka Lyncur (registered trademark) M890A, manufactured by Maruzen Petrochemical Co., Ltd., softening point: 105 °C
香豆酮樹脂:軟化點為90℃、日塗化學股份有限公司製造之Escuron(註冊商標)G-90Coumarone resin: Softening point is 90 ° C, Escuron (registered trademark) G-90 manufactured by Nissin 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份有限公司製造之Nocrac MBBenzimidazole-based anti-aging agent: 2-mercaptobenzimidazole, Nocrac MB manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
醌系抗老化劑:丸石化學品股份有限公司製造之Antigen FRAnti-aging agent: Antigen FR manufactured by Maruishi Chemical Co., Ltd.
5%油處理粉末硫:硫化劑、鶴見化學工業股份有限公司製造5% oil treated powder sulfur: vulcanizing agent, manufactured by Tsurumi Chemical Industry Co., Ltd.
亞磺醯胺系硫化促進劑:N-第三丁基-2-苯并噻唑基亞磺醯胺、大內新興化學工業股份有限公司製造之Nocceler(註冊商標)NSSulfoamide-based vulcanization accelerator: N-t-butyl-2-benzothiazolylsulfinamide, Nocceler (registered trademark) NS manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
秋蘭姆系硫化促進劑:大內新興化學工業股份有限公司製造之Nocceler TBT-NQiulan vulcanization accelerator: Nocceler TBT-N manufactured by Ou Nei Xin Chemical Industry Co., Ltd.
氧化鋅2種:三井金屬礦業股份有限公司製造2 kinds of zinc oxide: manufactured by Mitsui Metal Mining Co., Ltd.
硬脂酸:日油股份有限公司製造之「Tsubaki」Stearic acid: "Tsubaki" manufactured by Nippon Oil Co., Ltd.
碳黑:三菱化學股份有限公司製造之Diablack(註冊商標)GCarbon Black: Diablack (registered trademark) G manufactured by Mitsubishi Chemical Corporation
液狀聚異戊二烯橡膠:軟化劑、日本可樂麗公司製造之LIR50Liquid polyisoprene rubber: softener, LIR50 manufactured by Kuraray Co., Ltd.
<實例2><Example 2>
調配等量之酸值為160 mgKOH/g~175 mgKOH/g、軟化點為80℃~90℃之改質松香衍生物[荒川化學工業股份有限公司製造之PINECRYSTAL(註冊商標)KE-612]作為松香衍生物,除此以外與實例1同樣地進行而調製高衰減組成物。The modified rosin derivative (PINECRYSTAL (registered trademark) KE-612 manufactured by Arakawa Chemical Industries Co., Ltd.) is used as a modified rosin derivative with an acid value of 160 mgKOH/g to 175 mgKOH/g and a softening point of 80 °C to 90 °C. A high-attenuation composition was prepared in the same manner as in Example 1 except that the rosin derivative was used.
<實例3><Example 3>
調配等量之酸值為185 mgKOH/g~210 mgKOH/g、軟化點為155℃~165℃之松香改質特殊合成樹脂[Harima化成股份有限公司製造之商品名HARIMACK AS-5]作為松香衍生物,除此以外與實例1同樣地進行而調製高衰減組成物。The same amount of rosin modified special synthetic resin (HARIMACK AS-5 manufactured by Harima Chemical Co., Ltd.) with an acid value of 185 mgKOH/g to 210 mgKOH/g and a softening point of 155 °C to 165 °C is formulated as a rosin derivative. A high attenuation composition was prepared in the same manner as in Example 1 except for the above.
<比較例1><Comparative Example 1>
調配等量之酸值為32 mgKOH/g~38 mgKOH/g、軟化點為130℃~140℃之松香改質馬來酸樹脂[Harima化成股份有限公司製造之商品名HARIMACK 135GN]作為松香衍生物,並未調配咪唑系化合物及受阻酚系化合物,除此以外與實例1同樣地進行而調製高衰減組成物。A rosin-modified maleic acid resin (trade name: HARIMACK 135GN manufactured by Harima Chemical Co., Ltd.) having an acid value of 32 mgKOH/g to 38 mgKOH/g and a softening point of 130 °C to 140 °C is formulated as a rosin derivative. A high-attenuation composition was prepared in the same manner as in Example 1 except that the imidazole-based compound and the hindered phenol-based compound were not prepared.
<比較例2><Comparative Example 2>
調配等量之酸值為32 mgKOH/g~38 mgKOH/g、軟化點為130℃~140℃之松香改質馬來酸樹脂[Harima化成股份有限公司製造之商品名HARIMACK 135GN]作為松香衍生物,除此以外與實例1同樣地進行而調製高衰減組成物。A rosin-modified maleic acid resin (trade name: HARIMACK 135GN manufactured by Harima Chemical Co., Ltd.) having an acid value of 32 mgKOH/g to 38 mgKOH/g and a softening point of 130 °C to 140 °C is formulated as a rosin derivative. The high attenuation composition was prepared in the same manner as in Example 1 except for the above.
<比較例3><Comparative Example 3>
調配等量之酸值為140 mgKOH/g以下、軟化點為130℃~140℃之馬來酸樹脂[荒川化學工業股份有限公司製造之Marukido(註冊商標)No.32]而代替松香衍生物,除此以外與實例1同樣地進行而調製高衰減組成物。A maleic acid resin (Marukido (registered trademark) No. 32 manufactured by Arakawa Chemical Industries Co., Ltd.) having an acid value of 140 mg KOH/g or less and a softening point of 130 ° C to 140 ° C is used in place of the rosin derivative. Otherwise, the high attenuation composition was prepared in the same manner as in Example 1.
<比較例4><Comparative Example 4>
調配等量之酸值為120 mgKOH/g~150 mgKOH/g、軟化點為120℃~135℃之松香改質特殊合成樹脂[Harima化成股份有限公司製造之商品名HARIESTER MSR-4]作為松香衍生物,除此以外與實例1同樣地進行而調製高衰減組成物。The same amount of rosin modified special synthetic resin (HARIESTER MSR-4 manufactured by Harima Chemical Co., Ltd.) with an acid value of 120 mgKOH/g to 150 mgKOH/g and a softening point of 120 °C to 135 °C is formulated as a rosin derivative. A high attenuation composition was prepared in the same manner as in Example 1 except for the above.
<衰減特性試驗><Attenuation characteristic test>
(試驗體之製作)(production of test body)
將實例、比較例中所調製之高衰減組成物押出成形為薄板狀後進行衝壓,如圖1所示那樣製作圓板1(厚5 mm×直徑25 mm),於所述圓板1之表背兩個面分別經由硫化接著劑而疊合厚6 mm×縱44 mm×橫44 mm之矩形平板狀之鋼板2,一面於積層方向上進行加壓一面加熱至150℃,使形成圓板1之高衰減組成物硫化且使所述圓板1與2枚鋼板2硫化接著,製作作為高衰減部件之模型的衰減特性評價用試驗體3。The high-attenuation composition prepared in the examples and the comparative examples was extruded into a thin plate shape and then pressed, and a circular plate 1 (thickness: 5 mm × diameter: 25 mm) was produced as shown in Fig. 1, on the surface of the circular plate 1. A rectangular flat plate-shaped steel plate 2 having a thickness of 6 mm × a length of 44 mm × a width of 44 mm is laminated on both sides of the back by a vulcanizing adhesive, and heated to 150 ° C while being pressurized in the lamination direction to form a circular plate 1 The high-attenuation composition was vulcanized, and the disk 1 and the two steel sheets 2 were vulcanized, and a test body 3 for evaluation of attenuation characteristics as a model of a high-attenuation member was produced.
(位移試驗)(displacement test)
如圖2(a)所示那樣準備2個所述試驗體3,將所述2個試驗體3,經由其中一個鋼板2而以螺栓(bolt)固定於1枚中央固定夾具4上,並且於各個試驗體3之另一個鋼板2上以螺栓固定各1枚之左右固定夾具5。繼而,將中央固定夾具4,經由接頭7而以螺栓固定於未圖示之試驗機的上側的固定臂6上;且將2枚之左右固定夾具5,經由接頭9而以螺栓固定於所述試驗機之下側的可動盤8上。Two test bodies 3 were prepared as shown in Fig. 2 (a), and the two test bodies 3 were fixed to one central fixing jig 4 by bolts via one of the steel plates 2, and One of the left and right fixing jigs 5 is fixed to the other steel plate 2 of each of the test bodies 3 by bolts. Then, the center fixing jig 4 is bolted to the upper fixing arm 6 of the testing machine (not shown) via the joint 7, and the two left and right fixing jigs 5 are bolted to the above via the joint 9. The movable plate 8 on the lower side of the test machine.
其次,於該狀態下,如圖中之中空箭頭所示那樣使可動盤8位移而向固定臂6之方向提昇,如圖2(b)所示那樣,將試驗體3中之圓板1設為在與所述試驗體3之積層方向正交之方向上應變變形之變形狀態,其次自該變形狀態,如圖中之中空箭頭所示那樣使可動盤8位移而向與固定臂6之方向相反之方向降低,回復至所述圖2(a)所示之狀態,將上述操作作為1個循環,求出使所述試驗體3中之圓板1反覆應變變形、亦即使其振動時之遲滯環H(參照圖3),所述遲滯環H表示圓板1向與所述試驗體3之積層方向正交之方向的位移量(mm)與負載(N)之關係。Next, in this state, as shown by the hollow arrow in the figure, the movable disk 8 is displaced and lifted in the direction of the fixed arm 6, and as shown in Fig. 2(b), the circular plate 1 in the test body 3 is set. In a deformed state in which the strain is deformed in a direction orthogonal to the lamination direction of the test body 3, secondly, from the deformed state, the movable disk 8 is displaced in the direction of the fixed arm 6 as indicated by a hollow arrow in the figure. When the direction is reversed, the state shown in FIG. 2(a) is returned, and the above operation is performed as one cycle, and the disk 1 in the test body 3 is deformed by strain and deformation, even when it is vibrated. The hysteresis loop H (see FIG. 3) indicates the relationship between the displacement amount (mm) of the disc 1 in the direction orthogonal to the lamination direction of the test body 3 and the load (N).
測定是進行3個循環之所述操作而求出第3次之值。而且,以夾持圓板1之2枚鋼板2的與所述積層方向正交之方向的偏移量成為所述圓板1之厚度的100%之方式設定最大位移量。The measurement was performed by performing the above operation for 3 cycles to obtain the third value. In addition, the maximum displacement amount is set so that the amount of shift of the two steel sheets 2 that sandwich the disc 1 in the direction orthogonal to the lamination direction is 100% of the thickness of the disc 1.
其次,將在所述測定所求出之圖3中所示之遲滯環H中的最大位移點與最小位移點連接,求出圖中以粗實線所表示之直線L1之斜率Keq(N/mm),由所述斜率Keq(N/mm)、圓板1之厚度T(mm)、圓板1之截面積A(mm2),根據式(1):Next, the maximum displacement point in the hysteresis loop H shown in Fig. 3 obtained by the measurement is connected to the minimum displacement point, and the slope Keq of the straight line L 1 indicated by the thick solid line in the figure is obtained. /mm), from the slope Keq (N / mm), the thickness T (mm) of the circular plate 1, the cross-sectional area A (mm 2 ) of the circular plate 1, according to the formula (1):
[數學式1][Math 1]
而求出等價剪切彈性模數Geq(N/mm2)。而且,求出將比較例1中之等價剪切彈性模數Geq(N/mm2)設為100時之各實例、比較例之等價剪切彈性模數Geq(N/mm2)之相對值。The equivalent shear elastic modulus Geq (N/mm 2 ) was obtained. Further, the equivalent shear elastic modulus Geq (N/mm 2 ) of each of the examples and the comparative examples when the equivalent shear elastic modulus Geq (N/mm 2 ) in Comparative Example 1 was set to 100 was determined. relative value.
而且,由圖3中畫斜線所表示之吸收能量之量ΔW(以遲滯環H之總表面積所表示)、在圖3中畫方格網線所表示之彈性應變能量W(以由所述直線L1、圖表之橫軸、自直線L1與遲滯環H之交點垂直落下於所述橫軸而成之垂線L2所包圍之區域的表面積所表示),根據式(2):Moreover, the amount of absorbed energy ΔW (indicated by the total surface area of the hysteresis loop H) indicated by the oblique line in Fig. 3, and the elastic strain energy W represented by the square grid line in Fig. 3 (by the straight line L 1 , the horizontal axis of the graph, the surface area of the region surrounded by the perpendicular line L 2 perpendicular to the horizontal axis from the intersection of the straight line L 1 and the hysteresis loop H, according to the formula (2):
[數學式2][Math 2]
而求出等價衰減常數Heq。等價衰減常數Heq越大,越可以判定試驗體3之衰減性能優異。The equivalent decay constant Heq is obtained. The larger the equivalent decay constant Heq, the more excellent the attenuation performance of the test body 3 can be determined.
此處,求出將比較例1中之等價衰減常數Heq設為100時之各實例、比較例之等價衰減常數Heq之相對值,將所述相對值為105以上之情形評價為良好,將不足105之情形評價為不良。Here, the relative value of the equivalent decay constant Heq of each of the examples and the comparative examples when the equivalent decay constant Heq in Comparative Example 1 is set to 100 is obtained, and the case where the relative value is 105 or more is evaluated as good. The case of less than 105 was evaluated as bad.
<大的變形後的彈性模數之測定><Measurement of elastic modulus after large deformation>
以夾持圓板1之2枚鋼板2的與所述積層方向正交之方向的偏移量成為所述圓板1之厚度的300%之方式設定最大位移量,除此以外與上述同樣地進行而使所述圓板1進行1次大的變形後,與上述同樣地進行而求出偏移量為100%時之剪切彈性模數Geq'(N/mm2)。In the same manner as described above, the maximum displacement amount is set such that the amount of shift in the direction perpendicular to the lamination direction of the two steel sheets 2 that sandwich the disc 1 is set to be 300% of the thickness of the disc 1 . After the round plate 1 was deformed once, the shear elastic modulus Geq' (N/mm 2 ) when the offset amount was 100% was obtained in the same manner as described above.
而且,根據式(3):Moreover, according to equation (3):
[數學式3][Math 3]
而求出大的變形後的彈性模數之保持率(%)。保持率越大,越可以判定試驗體3於施加大的變形後的彈性模數之降低小。The retention rate (%) of the elastic modulus after the large deformation was obtained. The larger the retention ratio, the more the decrease in the elastic modulus of the test body 3 after the application of the large deformation is small.
因此,求出將比較例1之保持率設為100時的各實例、比較例之保持率之相對值,將所述相對值為100以上之情形評價為良好,將不足100之情形評價為不良。Therefore, the relative value of the retention ratio of each of the examples and the comparative examples when the retention ratio of Comparative Example 1 was 100 was determined, and the case where the relative value was 100 or more was evaluated as good, and the case where the relative value was less than 100 was evaluated as defective. .
將以上之結果示於表2。The above results are shown in Table 2.
根據表2之比較例1~比較例4之結果可知:藉由併用二氧化矽、松香衍生物、咪唑系化合物、及受阻酚系化合物這4種化合物,雖然可使高衰減部件之衰減性能提高,但若所述松香衍生物之酸值不足155 mgKOH/g,則施加大的變形後的彈性模數之降低變大。According to the results of Comparative Example 1 to Comparative Example 4 of Table 2, it was found that the attenuation properties of the high-attenuation member can be improved by using the four compounds of ceria, rosin derivative, imidazole compound, and hindered phenol compound in combination. However, if the acid value of the rosin derivative is less than 155 mgKOH/g, the decrease in the modulus of elasticity after application of a large deformation becomes large.
相對於此,根據實例1~實例3之結果可知:藉由選擇酸值為155 mgKOH/g以上之松香衍生物作為所述松香衍生物,可維持高衰減部件之良好之衰減性能,且可使施加大的變形後的彈性模數之降低變小。On the other hand, according to the results of Examples 1 to 3, it is understood that by selecting a rosin derivative having an acid value of 155 mgKOH/g or more as the rosin derivative, good attenuation performance of the high-attenuating member can be maintained, and The decrease in the modulus of elasticity after applying a large deformation becomes small.
而且,作為所述松香衍生物,較佳的是使用酸值為所述範圍內且為160 mgKOH/g以上者,特佳的是220 mgKOH/g以上者。Further, as the rosin derivative, those having an acid value of 160 mgKOH/g or more, and particularly preferably 220 mgKOH/g or more are preferably used.
而且,使用軟化點超過140℃之松香衍生物的實例3與所述使用軟化點為140℃以下之松香衍生物的實例1、實例2相比而言,為了調製高衰減組成物而需要長之時間對各成分進行混練。由此可知較佳的是松香衍生物之軟化點為140℃以下。Further, Example 3 using a rosin derivative having a softening point exceeding 140 ° C is required to be long in order to modulate a highly attenuating composition as compared with Example 1, Example 2 using a rosin derivative having a softening point of 140 ° C or less. Time to mix the ingredients. From this, it is understood that the softening point of the rosin derivative is preferably 140 ° C or lower.
<實例4~實例7、比較例5><Example 4 to Example 7, Comparative Example 5>
將松香衍生物[改質松香衍生物、酸值為230 mgKOH/g~245 mgKOH/g、軟化點為122℃~134℃、荒川化學工業股份有限公司製造之PINECRYSTAL(註冊商標)KE-604]之調配比例設為2質量份(比較例5)、3質量份(實例4)、20質量份(實例5)、30質量份(實例6)、及50質量份(實例7),除此以外與實例1同樣地進行而調製高衰減組成物。A rosin derivative [modified rosin derivative, an acid value of 230 mgKOH/g to 245 mgKOH/g, a softening point of 122 ° C to 134 ° C, PINECRYSTAL (registered trademark) KE-604 manufactured by Arakawa Chemical Industries Co., Ltd.] The blending ratio was 2 parts by mass (Comparative Example 5), 3 parts by mass (Example 4), 20 parts by mass (Example 5), 30 parts by mass (Example 6), and 50 parts by mass (Example 7). The high attenuation composition was prepared in the same manner as in Example 1.
<比較例6><Comparative Example 6>
將所述松香衍生物之調配比例設為55質量份,結果黏著性過強,無法對各成分之混合物進行混練而調製高衰減組成物。When the blending ratio of the rosin derivative was 55 parts by mass, the adhesiveness was too strong, and it was not possible to knead a mixture of the respective components to prepare a highly attenuating composition.
因此,對除比較例6之外的各實例、比較例之高衰減組成物進行所述各試驗而評價特性。將其結果與實例1之結果一併示於表3中。Therefore, the respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples except Comparative Example 6, and the characteristics were evaluated. The results are shown in Table 3 together with the results of Example 1.
[表3][table 3]
根據表3之比較例5之結果可知:即使於包含酸值為155 mgKOH/g以上之松香衍生物之所述4種化合物之併用系中,若所述松香衍生物之調配比例不足3質量份,則無法使高衰減部件之衰減性能提高。而且,根據比較例6之結果可知:於所述松香衍生物之調配比例超過50質量份之情形時,高衰減組成物之加工性降低。According to the results of Comparative Example 5 of Table 3, it is understood that even in the combined system of the four compounds containing a rosin derivative having an acid value of 155 mgKOH/g or more, the blending ratio of the rosin derivative is less than 3 parts by mass. , the attenuation performance of the high attenuation component cannot be improved. Further, according to the results of Comparative Example 6, when the blending ratio of the rosin derivative exceeds 50 parts by mass, the processability of the highly attenuating composition is lowered.
相對於此,根據實例1、實例4~實例7之結果可知:藉由使所述松香衍生物之調配比例為3質量份以上、50質量份以下,可維持高衰減組成物之良好之加工性,且使高衰減部件之衰減性能提高。On the other hand, according to the results of the examples 1 and 4 to 7, it is understood that the processability of the high-attenuation composition can be maintained by setting the proportion of the rosin derivative to 3 parts by mass or more and 50 parts by mass or less. And the attenuation performance of the high attenuation component is improved.
而且,亦可知:作為所述松香衍生物之調配比例,為了使高衰減部件之衰減性能更進一步提高,較佳的是於所述範圍內為10質量份以上;為了使施加大的變形後的彈性模數之降低儘可能地變小,較佳的是於所述範圍內為20質量份以下。Further, it is also known that the blending ratio of the rosin derivative is preferably 10 parts by mass or more in the above range in order to further improve the attenuation performance of the high-attenuating member; The decrease in the modulus of elasticity is as small as possible, and is preferably 20 parts by mass or less in the above range.
<實例8~實例10、比較例7、比較例8><Example 8 to Example 10, Comparative Example 7, Comparative Example 8>
將二氧化矽之調配比例設為80質量份(比較例7)、100質量份(實例8)、150質量份(實例9)、180質量份(實例10)、及190質量份(比較例8),除此以外與實例1同樣地進行而調製高衰減組成物。The blending ratio of cerium oxide was set to 80 parts by mass (Comparative Example 7), 100 parts by mass (Example 8), 150 parts by mass (Example 9), 180 parts by mass (Example 10), and 190 parts by mass (Comparative Example 8) Except for the above, the high attenuation composition was prepared in the same manner as in Example 1.
對所述各實例、比較例之高衰減組成物進行所述各試驗而評價特性。將其結果與實例1之結果一併示於表4中。The respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples to evaluate the characteristics. The results are shown in Table 4 together with the results of Example 1.
根據表4之比較例7之結果可知:即使於所述4種化合物之併用系中,若二氧化矽之調配比例不足100質量份,則無法使高衰減部件之衰減性能提高。而且,根據比較例8之結果可知:於二氧化矽之調配比例超過180質量份之情形時,施加大的變形後的彈性模數之降低變大。According to the results of Comparative Example 7 of Table 4, even in the combination of the above four compounds, if the proportion of the cerium oxide is less than 100 parts by mass, the attenuation performance of the high-attenuating member cannot be improved. Further, according to the results of Comparative Example 8, when the blending ratio of cerium oxide exceeds 180 parts by mass, the decrease in the modulus of elasticity after application of large deformation becomes large.
相對於此,根據實例1、實例8~實例10之結果可知:藉由使二氧化矽之調配比例為100質量份以上、180質量份以下,可使高衰減部件之衰減性能提高,且可使施加大的變形後的彈性模數之降低變小。On the other hand, according to the results of the examples 1 and 8 to 10, it is understood that the attenuation ratio of the high-attenuating member can be improved by setting the proportion of the cerium oxide to 100 parts by mass or more and 180 parts by mass or less. The decrease in the modulus of elasticity after applying a large deformation becomes small.
而且,亦可知:作為二氧化矽之調配比例,為了使高衰減部件之衰減性能更進一步提高,較佳的是於所述範圍內為135質量份以上;為了使施加大的變形後的彈性模數之降低儘可能變小,較佳的是於所述範圍內為150質量份以下。Further, it is also known that, as a ratio of blending of cerium oxide, in order to further improve the attenuation performance of the high-attenuating member, it is preferably 135 parts by mass or more in the above range; in order to apply a large deformed elastic mold The decrease in the number is as small as possible, and it is preferably 150 parts by mass or less in the range.
<實例11~實例14、比較例9><Example 11 to Example 14, Comparative Example 9>
將咪唑系化合物之調配比例設為0.05質量份(比較例9)、0.3質量份(實例11)、1質量份(實例12)、5質量份(實例13)、及10質量份(實例14),除此以外與實例1同樣地進行而調製高衰減組成物。The blending ratio of the imidazole-based compound was 0.05 parts by mass (Comparative Example 9), 0.3 parts by mass (Example 11), 1 part by mass (Example 12), 5 parts by mass (Example 13), and 10 parts by mass (Example 14). The high attenuation composition was prepared in the same manner as in Example 1 except for the above.
<比較例10><Comparative Example 10>
將所述咪唑系化合物之調配比例設為13質量份,結果於混練時產生焦化,因此無法調製高衰減組成物。When the blending ratio of the imidazole-based compound was 13 parts by mass, coking occurred during kneading, and thus it was impossible to prepare a highly attenuating composition.
因此,對除比較例10之外的各實例、比較例之高衰減組成物進行所述各試驗而評價特性。將其結果與實例1之結果一併示於表5中。Therefore, the respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples except Comparative Example 10, and the characteristics were evaluated. The results are shown in Table 5 together with the results of Example 1.
根據表5之比較例9之結果可知:即使於所述4種化合物之併用系中,若咪唑系化合物之調配比例不足0.1質量份,則無法使高衰減部件之衰減性能提高。而且,根據比較例10之結果可知:於咪唑系化合物之調配比例超過10質量份之情形時,高衰減組成物之加工性降低。According to the results of the comparative example 9 of the above-mentioned Table 5, even if the compounding ratio of the imidazole-based compound is less than 0.1 part by mass, the attenuation performance of the high-attenuation member cannot be improved. Further, according to the results of Comparative Example 10, when the blending ratio of the imidazole-based compound exceeds 10 parts by mass, the workability of the highly attenuating composition is lowered.
相對於此,根據實例1、實例11~實例14之結果可知:藉由將咪唑系化合物之調配比例設為0.1質量份以上、10質量份以下,可維持高衰減組成物之良好之加工性,且可使高衰減部件之衰減性能提高。On the other hand, according to the results of the example 1 and the example 14 to the example 14, it is understood that the blending ratio of the imidazole compound is 0.1 parts by mass or more and 10 parts by mass or less, whereby the good processability of the highly attenuating composition can be maintained. Moreover, the attenuation performance of the high attenuation component can be improved.
而且,亦可知:作為咪唑系化合物之調配比例,為了使高衰減部件之衰減性能更進一步提高,較佳的是於所述範圍內為0.3質量份以上、5質量份以下。In addition, it is preferable that the ratio of the imidazole-based compound is 0.3 parts by mass or more and 5 parts by mass or less in the above range in order to further improve the attenuation performance of the high-attenuating member.
<實例15~實例18、比較例11、比較例12><Example 15 to Example 18, Comparative Example 11, Comparative Example 12>
將受阻酚系化合物之調配比例設為0.05質量份(比較例11)、0.3質量份(實例15)、1質量份(實例16)、10質量份(實例17)、20質量份(實例18)、及23質量份(比較例12),除此以外與實例1同樣地進行而調製高衰減組成物。The blending ratio of the hindered phenol-based compound was 0.05 parts by mass (Comparative Example 11), 0.3 parts by mass (Example 15), 1 part by mass (Example 16), 10 parts by mass (Example 17), and 20 parts by mass (Example 18). The high-attenuation composition was prepared in the same manner as in Example 1 except that the amount was 23 parts by mass (Comparative Example 12).
對所述各實例、比較例之高衰減組成物進行所述各試驗而評價特性。將其結果與實例1之結果一併示於表6中。The respective tests were carried out on the high-attenuation compositions of the respective examples and comparative examples to evaluate the characteristics. The results are shown in Table 6 together with the results of Example 1.
根據表6之比較例11之結果可知:即使於所述4種化合物之併用系中,若受阻酚系化合物之調配比例不足0.1質量份,則無法使高衰減部件之衰減性能提高。而且,可確認受阻酚系化合物之調配比例超過20質量份之比較例12雖然於表之特性方面並不存在問題,但產生起霜。According to the results of Comparative Example 11 of Table 6, it is understood that the blending ratio of the hindered phenol-based compound is less than 0.1 part by mass, and the attenuation performance of the high-attenuating member cannot be improved even in the combination of the four compounds. In addition, Comparative Example 12 in which the compounding ratio of the hindered phenol-based compound was more than 20 parts by mass was confirmed to have no problem in terms of the characteristics of the watch, but blooming occurred.
相對於此,根據實例1、實例15~實例18之結果可知:藉由將受阻酚系化合物之調配比例設為0.1質量份以上、20質量份以下,可並不產生起霜等地使高衰減部件之衰減性能提高。On the other hand, according to the results of the example 1 and the examples 15 to 18, it is understood that the ratio of the hindered phenol compound to be 0.1 part by mass or more and 20 parts by mass or less can cause high attenuation without blooming or the like. The attenuation performance of the components is improved.
而且,亦可知:作為受阻酚系化合物之調配比例,為了使高衰減部件之衰減性能更進一步提高,較佳的是於所述範圍內為1質量份以上、特別是2.5質量份以上。Further, it is also known that the blending ratio of the hindered phenol-based compound is preferably 1 part by mass or more, particularly 2.5 parts by mass or more in the above range in order to further improve the attenuation performance of the high-attenuating member.
1...圓板1. . . Circular plate
2...鋼板2. . . Steel plate
3...試驗體3. . . Test body
4...中央固定夾具4. . . Central fixing fixture
5...左右固定夾具5. . . Left and right fixing fixture
6...固定臂6. . . Fixed arm
7、9...接頭7, 9. . . Connector
8...可動盤8. . . Movable disk
H...遲滯環H. . . Hysteresis loop
Keq...斜率Keq. . . Slope
L1...直線L 1 . . . straight line
L2...垂線L 2 . . . perpendicular
W...能量W. . . energy
ΔW...吸收能量之量ΔW. . . Amount of absorbed energy
圖1是分解表示用以評價包含本發明之實例、比較例的高衰減組成物之高衰減部件之衰減性能而製作的作為所述高衰減部件之模型之試驗體的分解透視圖。1 is an exploded perspective view showing a test body which is a model of the high-attenuation member which is produced by evaluating the attenuation performance of a high-attenuation member including a high-attenuation composition of an example of the present invention and a comparative example.
圖2(a)、圖2(b)是說明用以使所述試驗體位移而求出位移量與負載之關係的試驗機之概略之圖。2(a) and 2(b) are diagrams illustrating the outline of a testing machine for determining the relationship between the displacement amount and the load by displacing the test body.
圖3是表示使用所述試驗機使試驗體位移而求出的表示位移量與負載之關係的遲滯環之一例的圖表。3 is a graph showing an example of a hysteresis loop showing the relationship between the displacement amount and the load, which is obtained by displacing the test body using the test machine.
1...圓板1. . . Circular plate
2...鋼板2. . . Steel plate
3...試驗體3. . . Test body
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