JP2009249484A - Rubber composition for vibration-proof rubber and vibration-proof rubber - Google Patents
Rubber composition for vibration-proof rubber and vibration-proof rubber Download PDFInfo
- Publication number
- JP2009249484A JP2009249484A JP2008098438A JP2008098438A JP2009249484A JP 2009249484 A JP2009249484 A JP 2009249484A JP 2008098438 A JP2008098438 A JP 2008098438A JP 2008098438 A JP2008098438 A JP 2008098438A JP 2009249484 A JP2009249484 A JP 2009249484A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- vibration
- compound
- proof
- rubber composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 141
- 239000005060 rubber Substances 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- -1 thiazole compound Chemical class 0.000 claims abstract description 21
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 20
- 229920001194 natural rubber Polymers 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 229920003051 synthetic elastomer Polymers 0.000 claims abstract description 12
- 239000005061 synthetic rubber Substances 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 11
- 238000004073 vulcanization Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 230000007774 longterm Effects 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000004636 vulcanized rubber Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 14
- 230000003712 anti-aging effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 229960002447 thiram Drugs 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 230000006835 compression Effects 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- OFHMODDLBXETIK-UHFFFAOYSA-N methyl 2,3-dichloropropanoate Chemical compound COC(=O)C(Cl)CCl OFHMODDLBXETIK-UHFFFAOYSA-N 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- VLDHWMAJBNWALQ-UHFFFAOYSA-N sodium;3h-1,3-benzothiazole-2-thione Chemical compound [Na+].C1=CC=C2SC(S)=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-N 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Vibration Prevention Devices (AREA)
- Springs (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、防振ゴム用ゴム組成物及び防振ゴムに関し、特に自動車用エンジンマウント等の防振部材として好適に用いることができる防振ゴム用ゴム組成物及びこれを用いた防振ゴムに関するものである。 TECHNICAL FIELD The present invention relates to a rubber composition for vibration proof rubber and vibration proof rubber, and more particularly to a rubber composition for vibration proof rubber that can be suitably used as a vibration proof member for an engine mount for automobiles, and a vibration proof rubber using the same. Is.
一般に、自動車にはエンジンや車体の振動を吸収し、乗り心地を向上し、騒音を防止するための防振ゴムが用いられている。特に、自動車のエンジンルームや排気系等に使用されるエンジンマウント等の防振ゴムでは、近年のエンジンの高出力化等に伴い、高い耐熱性を要求されるようになってきている。 In general, an anti-vibration rubber is used for an automobile to absorb vibrations of an engine and a vehicle body, improve riding comfort, and prevent noise. In particular, anti-vibration rubbers such as engine mounts used in engine rooms and exhaust systems of automobiles are required to have high heat resistance with the recent increase in engine output.
従来、防振ゴムのゴム成分としては、天然ゴム、又は天然ゴムとジエン系合成ゴムとのブレンドが一般に用いられており、これらのゴム成分を含むゴム組成物の加硫ゴムの耐熱性を向上する技術としては、ゴム組成物中の硫黄量を減らし加硫促進剤を多く配合して加硫する技術（ＥＶ方式（ＥＶ；Ｅｆｆｉｃｉｅｎｔ Ｖｕｌｃａｎｉｚａｔｉｏｎ））が知られている。 Conventionally, natural rubber or a blend of natural rubber and diene synthetic rubber has been generally used as the rubber component of the vibration-proof rubber, and the heat resistance of the vulcanized rubber of the rubber composition containing these rubber components is improved. As a technique for reducing the amount of sulfur in the rubber composition, a technique for vulcanizing by adding a large amount of a vulcanization accelerator (EV method (EV; Efficient Vulcanization)) is known.
しかし、上記のようにゴム組成物中の硫黄量や加硫促進剤の配合量を最適化し、例えばモノスルフィド結合による架橋形態を多くすることにより加硫ゴムの耐熱性の向上を図る場合、耐熱性はある程度改善するが、防振ゴムの要求特性の一つである耐久性が劣るという難点がある。 However, as described above, when the amount of sulfur in the rubber composition and the amount of the vulcanization accelerator are optimized, for example, when the heat resistance of the vulcanized rubber is improved by increasing the number of crosslinking forms due to monosulfide bonds, Although the performance is improved to some extent, there is a drawback that durability, which is one of the required characteristics of the vibration-proof rubber, is inferior.
また防振ゴムでは、動倍率（動バネ定数／静バネ定数）等の振動特性が、新品時（初期）において良好であることのみならず、長期間使用後においても良好に確保される必要がある。つまり、防振ゴムでは、熱劣化等による悪化を抑制することにより、振動特性の変化率を低減することも重要となる。 In addition, with vibration-proof rubber, vibration characteristics such as dynamic magnification (dynamic spring constant / static spring constant) need to be ensured not only when it is new (initial stage) but also after a long period of use. is there. That is, in the vibration-proof rubber, it is also important to reduce the rate of change of vibration characteristics by suppressing deterioration due to thermal deterioration or the like.
下記特許文献１〜２では、硫黄の含有量を制限しつつ、加硫促進剤としてチアゾール化合物を含有するゴム組成物、あるいはチアゾール化合物とスルフェンアミド化合物とチウラム化合物とを含有するゴム組成物により、加硫ゴムの耐熱性を向上しつつ、振動特性や耐久性等をバランス良く向上することができる点が記載されている。しかしながら、これらのゴム組成物の加硫ゴムでは、耐熱性や、初期の振動特性及び耐久性等については、ある程度バランスのとれた良好な結果を示すものの、長時間使用後における振動特性の変化率が大きいことが判明した。このように、従来の加硫促進剤の組み合わせによっては、防振ゴムの耐熱性を向上しつつ、振動特性や耐久性等をバランス良く向上し、かつ長時間使用後における振動特性の変化率を低減することは困難であった。
本発明の目的は、耐熱性を向上しつつ、長時間使用後における振動特性の変化率を低減した防振ゴム用ゴム組成物及びこれを用いて得られる防振ゴムを提供することにある。 An object of the present invention is to provide a rubber composition for an anti-vibration rubber having improved heat resistance and a reduced rate of change in vibration characteristics after long-term use, and an anti-vibration rubber obtained using the rubber composition.
本発明者らは、上記課題を解決すべく鋭意検討した結果、以下に示す防振ゴム用ゴム組成物により上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the rubber composition for vibration-proof rubber shown below, and have completed the present invention.
すなわち、本発明に係る防振ゴム用ゴム組成物は、天然ゴム、又は天然ゴムとジエン系合成ゴムとのブレンドを主成分とするゴム成分を含有する防振ゴム用ゴム組成物において、前記ゴム成分１００重量部に対して、０．１〜１重量部の硫黄と、下記一般式（１）で表されるスルフェンイミド化合物と、チアゾール化合物とを含有することを特徴とする。
（式中、Ｒは炭素数１〜１８の直鎖アルキル基、分岐鎖アルキル基、脂環族炭化水素基、又は芳香族炭化水素基を表す）。
That is, the rubber composition for vibration-proof rubber according to the present invention is the rubber composition for vibration-proof rubber containing a rubber component whose main component is natural rubber or a blend of natural rubber and diene synthetic rubber. It contains 0.1 to 1 part by weight of sulfur, a sulfenimide compound represented by the following general formula (1), and a thiazole compound with respect to 100 parts by weight of the component.
(In the formula, R represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group).
本発明に係る防振ゴム用ゴム組成物は、加硫促進剤として、上記スルフェンイミド化合物と、チアゾール化合物とを含有することにより、防振ゴムの耐熱性を向上しつつ、初期振動特性や耐久性、さらには耐ヘタリ性をバランス良く向上し、かつ長時間使用後における振動特性の変化率、特に高温環境下での長時間使用後においても、振動特性の変化率を低減することができる。 The rubber composition for vibration-proof rubber according to the present invention contains the sulfenimide compound and the thiazole compound as a vulcanization accelerator, thereby improving the heat resistance of the vibration-proof rubber, the initial vibration characteristics and Durability and even sag resistance are improved in a well-balanced manner, and the change rate of vibration characteristics after long-time use, especially after long-time use under high temperature environment, can be reduced. .
さらに、ゴム成分１００重量部に対して、０．１〜１重量部の硫黄を含有するため、防振ゴムのゴム強度を良好に確保しつつ、耐熱性及び耐ヘタリ性が向上する。また、本発明に係る防振ゴム用ゴム組成物は、天然ゴム、又は天然ゴムとジエン系合成ゴムとのブレンドを主成分とするゴム成分を含有する。かかるゴム成分を含有する防振ゴム用ゴム組成物の加硫ゴムは、動倍率が低くなり、かつ繰り返し変形に対する抵抗性が高くなる。 Furthermore, since 0.1 to 1 part by weight of sulfur is contained with respect to 100 parts by weight of the rubber component, the heat resistance and the settling resistance are improved while ensuring the rubber strength of the vibration-proof rubber well. The rubber composition for vibration-proof rubber according to the present invention contains a rubber component whose main component is natural rubber or a blend of natural rubber and diene synthetic rubber. The vulcanized rubber of the rubber composition for an anti-vibration rubber containing such a rubber component has a low dynamic magnification and a high resistance to repeated deformation.
上記において、前記スルフェンイミド化合物と、前記チアゾール化合物とを、重量比にて（スルフェンイミド化合物）／（チアゾール化合物）＝１／４〜４／１の範囲内で含有することが好ましい。かかる防振ゴム用ゴム組成物によれば、特に防振ゴムの耐熱性を向上しつつ、長時間使用後における振動特性の変化率をさらに低減することができる。 In the above, it is preferable to contain the said sulfenimide compound and the said thiazole compound in the range of (sulfenimide compound) / (thiazole compound) = 1/4-4/1 by weight ratio. According to such a rubber composition for an anti-vibration rubber, it is possible to further reduce the rate of change in vibration characteristics after long-time use while improving the heat resistance of the anti-vibration rubber.
本発明に係る防振ゴムは、上記防振ゴム用ゴム組成物を使用し、加硫、成形して得られるものであることを特徴とする。かかる防振ゴムは、耐熱性を向上しつつ、初期振動特性や耐久性、さらには耐ヘタリ性をバランス良く向上し、かつ長時間使用後における振動特性の変化率を低減した防振ゴムであることから、特にエンジンマウント、トーショナルダンパー、ボディマウント、キャップマウント、メンバーマウント、ストラットマウント、マフラーマウント等の自動車用防振ゴムとして好適に用いることができる。 The vibration-proof rubber according to the present invention is obtained by vulcanization and molding using the rubber composition for vibration-proof rubber. Such an anti-vibration rubber is an anti-vibration rubber that improves the initial vibration characteristics and durability, and further improves the anti-vibration property in a well-balanced manner while improving the heat resistance, and reduces the rate of change in vibration characteristics after long-term use. Therefore, it can be suitably used particularly as an anti-vibration rubber for automobiles such as engine mounts, torsional dampers, body mounts, cap mounts, member mounts, strut mounts, and muffler mounts.
本発明に係る防振ゴム用ゴム組成物においては、ゴム成分として天然ゴム単独、又は天然ゴムとジエン系合成ゴムとのブレンドが使用される。天然ゴムとジエン系合成ゴムとをブレンドする場合、ジエン系合成ゴムとしては、ポリイソプレンゴム（ＩＲ）、ポリブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、及びアクリルニトリルブタジエンゴム（ＮＢＲ）等が挙げられる。かかるジエン系合成ゴムの重合方法やミクロ構造は限定されず、これらのうちの１種又は２種以上を天然ゴムにブレンドして使用することができる。 In the rubber composition for vibration-proof rubber according to the present invention, natural rubber alone or a blend of natural rubber and diene synthetic rubber is used as the rubber component. When blending natural rubber and diene synthetic rubber, the diene synthetic rubber includes polyisoprene rubber (IR), polybutadiene rubber (BR), styrene butadiene rubber (SBR), butyl rubber (IIR), and acrylonitrile butadiene rubber. (NBR) and the like. The polymerization method and microstructure of such a diene-based synthetic rubber are not limited, and one or more of these can be used by blending with natural rubber.
天然ゴムとジエン系合成ゴムとをブレンドする場合、そのブレンド比は特に限定されるものではないが、天然ゴムが有する耐疲労性能を維持するため、天然ゴムをゴム成分中、５０重量％以上含有することが好ましく、９０重量％以上含有することがより好ましい。なお、天然ゴム及びジエン系合成ゴムに加えて、ゴム成分として使用可能なゴムとしては、例えば、エチレンプロピレンゴム（ＥＰＭ）等のオレフィン系ゴム、臭素化ブチルゴム（Ｂｒ−ＩＩＲ）等のハロゲン化ブチルゴム、その他ポリウレタンゴム、アクリルゴム、フッ素ゴム、シリコンゴム、及びクロロスルホン化ポリエチレン等を含めた合成ゴム類等が挙げられる。 When natural rubber and diene synthetic rubber are blended, the blend ratio is not particularly limited, but natural rubber is contained in the rubber component in an amount of 50% by weight or more in order to maintain the fatigue resistance of natural rubber. It is preferable to contain 90% by weight or more. In addition to natural rubber and diene synthetic rubber, examples of rubber that can be used as a rubber component include olefin rubber such as ethylene propylene rubber (EPM) and halogenated butyl rubber such as brominated butyl rubber (Br-IIR). And other synthetic rubbers including polyurethane rubber, acrylic rubber, fluoro rubber, silicon rubber, chlorosulfonated polyethylene, and the like.
硫黄は通常のゴム用硫黄であればよく、例えば粉末硫黄、沈降硫黄、不溶性硫黄、高分散性硫黄等を用いることができる。本発明に係る防振ゴム用ゴム組成物における硫黄の含有量は、ゴム成分１００重量部に対して０．１〜１重量部である。硫黄の含有量が０．１重量部未満であると、加硫ゴムの架橋密度が不足してゴム強度等が低下し、１重量部を超えると、特に耐熱性及び耐ヘタリ性の両方が悪化する。加硫ゴムのゴム強度を良好に確保し、耐熱性と耐ヘタリ性をより向上するためには、硫黄の含有量がゴム成分１００重量部に対して０．１〜０．９重量部であることが好ましく、０．２〜０．６重量部であることがより好ましい。 Sulfur should just be normal sulfur for rubber | gum, For example, powder sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur etc. can be used. The sulfur content in the rubber composition for vibration-proof rubber according to the present invention is 0.1 to 1 part by weight with respect to 100 parts by weight of the rubber component. If the sulfur content is less than 0.1 parts by weight, the crosslinking density of the vulcanized rubber will be insufficient, resulting in a decrease in rubber strength and the like. To do. In order to ensure good rubber strength of the vulcanized rubber and to further improve the heat resistance and sag resistance, the sulfur content is 0.1 to 0.9 parts by weight with respect to 100 parts by weight of the rubber component. It is preferably 0.2 to 0.6 parts by weight.
本発明に係る防振ゴム用ゴム組成物は、加硫促進剤として、下記一般式（１）で表されるスルフェンイミド化合物と、チアゾール化合物とを含有する。
（式中、Ｒは炭素数１〜１８の直鎖アルキル基、分岐鎖アルキル基、脂環族炭化水素基、又は芳香族炭化水素基を表す）。
The rubber composition for vibration-proof rubber according to the present invention contains a sulfenimide compound represented by the following general formula (1) and a thiazole compound as a vulcanization accelerator.
(In the formula, R represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group).
上記スルフェンイミド化合物としては、ゴム組成物中での分散性、加硫促進効果及び加硫ゴムとして長時間使用した場合の振動特性の変化率を考慮した場合、置換基ＲがＮ−ｔｅｒｔ−ブチル基であるＮ−ｔｅｒｔ−ブチル−２−ベンゾチアゾールスルフェンイミド、置換基ＲがＮ−シクロヘキシル基であるＮ−シクロヘキシル−２−ベンゾチアゾールスルフェンイミド、及び置換基ＲがＮ−フェニル基であるＮ−フェニル−２−ベンゾチアゾールスルフェンイミドが好ましく、Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾールスルフェンイミドがより好ましい。かかるスルフェンイミド化合物は、市販品も好適に使用可能であり、例えばＮ−ｔｅｒｔ−ブチル−２−ベンゾチアゾールスルフェンイミド（「ＳＡＮＴＯＣＵＲＥ ＴＢＳＩ」、ＦＬＥＸＳＹＳ社製）が挙げられる。スルフェンイミド化合物の含有量は、ゴム成分１００重量部に対して０．５〜５重量部が好ましく、１〜３重量部がより好ましい。 As the sulfenimide compound, when considering the dispersibility in the rubber composition, the effect of vulcanization acceleration, and the rate of change in vibration characteristics when used as a vulcanized rubber for a long time, the substituent R is N-tert- N-tert-butyl-2-benzothiazole sulfenimide which is a butyl group, N-cyclohexyl-2-benzothiazole sulfenimide where the substituent R is an N-cyclohexyl group, and the substituent R is an N-phenyl group Some N-phenyl-2-benzothiazole sulfenimides are preferred, and N-tert-butyl-2-benzothiazole sulfenimide is more preferred. A commercially available product can be suitably used as the sulfenimide compound, and examples thereof include N-tert-butyl-2-benzothiazole sulfenimide (“SANTOCURE TBSI”, manufactured by FLEXSYS). 0.5-5 weight part is preferable with respect to 100 weight part of rubber components, and, as for content of a sulfenimide compound, 1-3 weight part is more preferable.
チアゾール化合物としては、例えば、２−メルカプトベンゾチアゾール、ジ−２−ベンゾチアゾリルジスルフィド、２−メルカプトベンゾチアゾールの亜鉛塩、２−メルカプトベンゾチアゾールのナトリウム塩、及び２−メルカプトベンゾチアゾールのシクロヘキシルアミン塩等が挙げられる。チアゾール化合物の含有量は、ゴム成分１００重量部に対して０．５〜５重量部が好ましく、１〜３重量部がより好ましい。 Examples of thiazole compounds include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, zinc salt of 2-mercaptobenzothiazole, sodium salt of 2-mercaptobenzothiazole, and cyclohexylamine of 2-mercaptobenzothiazole. Examples include salts. The content of the thiazole compound is preferably 0.5 to 5 parts by weight and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the rubber component.
本発明に係る防振ゴム用ゴム組成物においては、スルフェンイミド化合物と、チアゾール化合物とを、重量比にて（スルフェンイミド化合物）／（チアゾール化合物）＝１／４〜４／１の範囲内で含有することが好ましい。防振ゴムの耐熱性を向上しつつ、長時間使用後における振動特性の変化率をさらに低減するためには、１／３〜３／１であることが特に好ましい。 In the rubber composition for vibration-proof rubber according to the present invention, the sulfenimide compound and the thiazole compound are in a weight ratio of (sulfenimide compound) / (thiazole compound) = 1/4 to 4/1. It is preferable to contain within. In order to further reduce the change rate of vibration characteristics after long-time use while improving the heat resistance of the vibration-proof rubber, it is particularly preferably 1/3 to 3/1.
また、本発明に係る防振ゴム用ゴム組成物においては、加硫促進剤として、上記２成分に加えて、チウラム化合物を更に併用することが好ましい。チウラム化合物は、一般に二次加硫促進剤として使用され、防振ゴムの耐熱性改良効果に優れる。チウラム化合物としては、例えば、テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、ジペンタメチレンチウラムテトラスルフィド、ジペンタメチレンチウラムヘキサスルフィド、及びテトラキス（２−エチルヘキシル）チウラムジスルフィド等が挙げられる。 In the rubber composition for vibration-proof rubber according to the present invention, it is preferable to further use a thiuram compound in addition to the above two components as a vulcanization accelerator. The thiuram compound is generally used as a secondary vulcanization accelerator and is excellent in the heat resistance improvement effect of the vibration-proof rubber. Examples of thiuram compounds include tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, and tetrakis (2-ethylhexyl) thiuram disulfide. Etc.
また、本発明の防振ゴム用ゴム組成物は、上記ゴム成分、硫黄、加硫促進剤と共にカーボンブラック、シリカ、シランカップリング剤、酸化亜鉛、ステアリン酸、加硫促進助剤、加硫遅延剤、有機過酸化物、老化防止剤、ワックスやオイル等の軟化剤、加工助剤等の通常ゴム工業で使用される配合剤を、本発明の効果を損なわない範囲において適宜配合し用いることができる。 Further, the rubber composition for vibration-proof rubber of the present invention comprises the above rubber component, sulfur, vulcanization accelerator, carbon black, silica, silane coupling agent, zinc oxide, stearic acid, vulcanization accelerator, vulcanization delay. Additives, organic peroxides, anti-aging agents, softeners such as wax and oil, compounding agents usually used in the rubber industry, such as processing aids, may be appropriately blended and used as long as the effects of the present invention are not impaired. it can.
カーボンブラックとしては、例えばＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＦＥＦ、ＧＰＦ等が用いられる。カーボンブラックは、加硫後のゴムの硬度、補強性、低発熱性等のゴム特性を調整し得る範囲で使用することができる。カーボンブラックの配合量はゴム成分１００重量部に対して、２０〜１２０重量部の範囲であり、好ましくは３０〜１００重量部であり、より好ましくは３０〜６０重量部である。この配合量が２０重量部未満では、カーボンブラックの補強効果が充分に得られず、１２０重量部を超えると、発熱性、ゴム混合性及び加工時の作業性等が悪化する。 As carbon black, for example, SAF, ISAF, HAF, FEF, GPF and the like are used. Carbon black can be used within a range in which rubber properties such as hardness, reinforcement and low heat build-up of the rubber after vulcanization can be adjusted. The compounding amount of carbon black is in the range of 20 to 120 parts by weight, preferably 30 to 100 parts by weight, and more preferably 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component. If the blending amount is less than 20 parts by weight, the reinforcing effect of carbon black cannot be obtained sufficiently.
老化防止剤としては、ゴム用として通常用いられる、芳香族アミン系老化防止剤、アミン−ケトン系老化防止剤、モノフェノール系老化防止剤、ビスフェノール系老化防止剤、ポリフェノール系老化防止剤、ジチオカルバミン酸塩系老化防止剤、チオウレア系老化防止剤等の老化防止剤を単独、又は適宜混合して使用しても良い。 As an anti-aging agent, an aromatic amine-based anti-aging agent, an amine-ketone-based anti-aging agent, a monophenol-based anti-aging agent, a bisphenol-based anti-aging agent, a polyphenol-based anti-aging agent, dithiocarbamic acid, which are usually used for rubber You may use antiaging agents, such as a salt type anti-aging agent and a thiourea type anti-aging agent, individually or in mixture as appropriate.
本発明の防振ゴム用ゴム組成物は、ゴム成分、硫黄、加硫促進剤、必要に応じて、カーボンブラック、酸化亜鉛、ステアリン酸、加硫促進剤、老化防止剤、ワックス等を、バンバリーミキサー、ニーダー、ロール等の通常のゴム工業において使用される混練機を用いて混練りすることにより得られる。 The rubber composition for vibration-proof rubber of the present invention comprises a rubber component, sulfur, a vulcanization accelerator, and, if necessary, carbon black, zinc oxide, stearic acid, a vulcanization accelerator, an anti-aging agent, a wax, and the like. It can be obtained by kneading using a kneader such as a mixer, kneader, roll or the like used in a normal rubber industry.
また、上記各成分の配合方法は特に限定されず、硫黄、及び加硫促進剤等の加硫系成分以外の配合成分を予め混練してマスターバッチとし、残りの成分を添加してさらに混練する方法、各成分を任意の順序で添加し混練する方法、全成分を同時に添加して混練する方法等のいずれでもよい。 In addition, the blending method of each of the above components is not particularly limited, and blending components other than vulcanization components such as sulfur and a vulcanization accelerator are kneaded in advance to obtain a master batch, and the remaining components are added and further kneaded. Any of a method, a method of adding and kneading each component in an arbitrary order, a method of adding all components simultaneously and kneading may be used.
上記各成分を混練し、成形加工した後、加硫を行うことで、耐熱性を向上しつつ、初期振動特性や耐久性、さらには耐ヘタリ性をバランス良く向上し、かつ長時間使用後における振動特性の変化率を低減した防振ゴムを得ることができる。かかる防振ゴムは、エンジンマウント、トーショナルダンパー、ボディマウント、キャップマウント、メンバーマウント、ストラットマウント、マフラーマウント等の自動車用防振ゴムを始めとして、鉄道車両用防振ゴム、産業機械用防振ゴム、建築用免震ゴム、免震ゴム支承等の防振、免震ゴムに好適に用いることができ、特にエンジンマウント等の耐熱性を必要とする自動車用防振ゴムの構成部材として有用である。 After kneading and molding the above components, vulcanization improves the initial vibration characteristics and durability, and further improves the anti-slip property in a well-balanced manner while improving heat resistance. An anti-vibration rubber having a reduced rate of change in vibration characteristics can be obtained. Such anti-vibration rubber includes anti-vibration rubber for automobiles such as engine mounts, torsional dampers, body mounts, cap mounts, member mounts, strut mounts, muffler mounts, anti-vibration rubbers for railway vehicles, and anti-vibration rubbers for industrial machinery. It can be used suitably for vibration isolation and isolation rubber for rubber, building isolation rubber, and isolation rubber bearings, and is particularly useful as a component of automotive isolation rubber that requires heat resistance such as engine mounts. is there.
以下に、この発明の実施例を記載してより具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
（ゴム組成物の調製）
天然ゴム１００重量部に対して、表１の配合処方に従い、実施例１〜４及び比較例１〜４のゴム組成物を配合し、通常のバンバリーミキサーを用いて混練し、ゴム組成物を調整した。表１に記載の各配合剤を以下に示す。
(Preparation of rubber composition)
According to the formulation of Table 1, the rubber compositions of Examples 1 to 4 and Comparative Examples 1 to 4 are blended with 100 parts by weight of natural rubber and kneaded using a normal Banbury mixer to prepare the rubber composition. did. Each compounding agent described in Table 1 is shown below.
ａ）天然ゴム ＲＳＳ＃３
ｂ）硫黄 ５％オイル処理硫黄
ｃ）加硫促進剤
（Ａ）スルフェンイミド化合物 Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾールスルフェンイミド（「ＳＡＮＴＯＣＵＲＥ ＴＢＳＩ」、ＦＬＥＸＳＹＳ社製）
（Ｂ）チアゾール化合物 ジ−２−ベンゾチアゾリルジスルフィド（「ノクセラーＤＭ−Ｐ（ＤＭ）」、大内新興化学工業社製）
（Ｃ）チウラム化合物 テトラメチルチウラムジスルフィド（「ノクセラーＴＴ−Ｐ（ＴＴ）」、大内新興化学工業社製）
（Ｄ）スルフェンアミド化合物 Ｎ−ｔｅｒｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド（「ノクセラーＮＳ−Ｐ（ＮＳ）」、大内新興化学工業社製）
a) Natural rubber RSS # 3
b) Sulfur 5% oil-treated sulfur c) Vulcanization accelerator (A) Sulfenimide compound N-tert-butyl-2-benzothiazole sulfenimide ("SANTOCURE TBSI", manufactured by FLEXSYS)
(B) Thiazole compound di-2-benzothiazolyl disulfide (“Noxeller DM-P (DM)”, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
(C) Thiuram compound Tetramethylthiuram disulfide ("Noxeller TT-P (TT)", manufactured by Ouchi Shinsei Chemical Co., Ltd.)
(D) Sulfenamide compound N-tert-butyl-2-benzothiazolylsulfenamide ("Noxeller NS-P (NS)", manufactured by Ouchi Shinsei Chemical Co., Ltd.)
ｄ）老化防止剤
（Ａ）Ｎ−フェニル−Ｎ’−（１，３−ジメチルブチル）−ｐ−フェニレンジアミン（「ノクラック６Ｃ」、大内新興化学工業社製）
（Ｂ）２，２，４−トリメチル−１，２−ジヒドロキノリン重合体（「ノクラック ２２４」、大内新興化学工業社製）
ｅ）カーボンブラック ＦＥＦ （「シーストＳＯ」、東海カーボン社製）
ｆ）アロマオイル （「プロセスＸ−１４０」、ジャパンエナジー社製）
ｇ）酸化亜鉛 ３号亜鉛華
ｈ）ステアリン酸 工業用ステアリン酸
ｉ）ワックス ミクロクリスタリンワックス
d) Anti-aging agent (A) N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (“NOCRACK 6C”, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
(B) 2,2,4-trimethyl-1,2-dihydroquinoline polymer ("NOCRACK 224", manufactured by Ouchi Shinsei Chemical Co., Ltd.)
e) Carbon Black FEF ("Seast SO", manufactured by Tokai Carbon Co., Ltd.)
f) Aroma oil ("Process X-140", manufactured by Japan Energy)
g) Zinc oxide No. 3 zinc white h) Stearic acid Industrial stearic acid i) Wax Microcrystalline wax
各ゴム組成物については、それぞれの加硫ゴムを作製して特性評価を行った。
（評価）
評価は、各ゴムを所定の金型を使用して１５０℃にて３０分加熱、加硫して得られたゴムについて行った。
About each rubber composition, each vulcanized rubber was produced and the characteristic evaluation was performed.
(Evaluation)
The evaluation was performed on rubber obtained by heating and vulcanizing each rubber at 150 ° C. for 30 minutes using a predetermined mold.
＜初期振動特性＞
５０ｍｍφ×２５ｍｍの加硫ゴムからなるテストピース（新品）について、振動試験機を用いて、静バネ定数（Ｋｓ）と動バネ定数（Ｋｄ）を測定した。静バネ定数は、２０％まで圧縮させた際の応力・変位から算出した（単位はＮ／ｍｍ）。動バネ定数は、１０％圧縮後、周波数１００Ｈｚ、振幅±０．２％で振動させ、ＪＩＳ Ｋ６３９４に記載の計算方法により求めた。動倍率は、上記で得られた静バネ定数に対する動バネ定数の比（Ｋｄ／Ｋｓ）として算出した。評価は比較例１のゴム組成物の加硫ゴムからなるテストピースの動倍率を１００として指数評価した。数値が小さいほど、初期振動特性に優れていることを示す。評価結果を表１に示す。
<Initial vibration characteristics>
For a test piece (new article) made of vulcanized rubber of 50 mmφ × 25 mm, the static spring constant (Ks) and dynamic spring constant (Kd) were measured using a vibration tester. The static spring constant was calculated from the stress and displacement when compressed to 20% (unit: N / mm). The dynamic spring constant was determined by a calculation method described in JIS K6394 after 10% compression, with a frequency of 100 Hz and an amplitude of ± 0.2%. The dynamic magnification was calculated as the ratio (Kd / Ks) of the dynamic spring constant to the static spring constant obtained above. The evaluation was indexed with the dynamic ratio of the test piece made of vulcanized rubber of the rubber composition of Comparative Example 1 as 100. The smaller the value, the better the initial vibration characteristics. The evaluation results are shown in Table 1.
＜振動特性の変化率＞
上述した初期振動特性を算出するのに使用したテストピース（新品）を、１００℃×５００時間熱老化後に動倍率を測定し、新品時の動倍率に対する老化後の動倍率の変化率を算出した。評価は比較例１のゴム組成物の加硫ゴムからなるテストピースの動倍率の変化率を１００として指数評価した。数値が小さいほど、振動特性の変化率が低いことを示す。評価結果を表１に示す。
<Change rate of vibration characteristics>
The test piece (new article) used to calculate the initial vibration characteristics described above was measured for the dynamic magnification after heat aging at 100 ° C. for 500 hours, and the rate of change of the dynamic magnification after aging with respect to the dynamic magnification at the new article was calculated. . The evaluation was made by index evaluation with the rate of change of dynamic magnification of the test piece made of vulcanized rubber of the rubber composition of Comparative Example 1 as 100. The smaller the value, the lower the change rate of vibration characteristics. The evaluation results are shown in Table 1.
＜耐熱性＞
ＪＩＳ Ｋ６２５１に準拠し、熱老化前の引張試験における破断伸びに対する、１００℃×５００時間熱老化後の引張試験における破断伸びの保持率（％）を算出した。評価は比較例１のゴム組成物の加硫ゴムについて算出した破断伸びの保持率を１００として指数評価した。数値が大きいほど、耐熱性に優れていることを示す。評価結果を表１に示す。
<Heat resistance>
Based on JIS K6251, the retention rate (%) of the elongation at break in the tensile test after heat aging at 100 ° C. for 500 hours with respect to the elongation at break in the tensile test before heat aging was calculated. The evaluation was indexed with the retention of elongation at break calculated for the vulcanized rubber of the rubber composition of Comparative Example 1 being 100. It shows that it is excellent in heat resistance, so that a numerical value is large. The evaluation results are shown in Table 1.
＜耐ヘタリ性＞
ＪＩＳ Ｋ６２６２に準拠し、圧縮永久歪試験（２５％圧縮、１００℃×５００時間）を行い、圧縮永久歪率（％）を測定した。評価は比較例１のゴム組成物の加硫ゴムについて測定した圧縮永久歪率を１００として指数評価した。数値が小さいほど、耐ヘタリ性に優れていることを示す。評価結果を表１に示す。
<Heat resistance>
In accordance with JIS K6262, a compression set test (25% compression, 100 ° C. × 500 hours) was performed, and the compression set rate (%) was measured. The evaluation was made by index evaluation with the compression set measured for the vulcanized rubber of the rubber composition of Comparative Example 1 as 100. It shows that it is excellent in settling resistance, so that a numerical value is small. The evaluation results are shown in Table 1.
＜耐久性＞
耐久性試験用のテストピースとしては、外径８１ｍｍ、高さ４９ｍｍの薄肉円筒金具の内孔内に、外径１６ｍｍ、高さ７０ｍｍの厚肉円筒金具が、該薄肉円筒金具の軸心に位置するように配置されると共に、それら両円筒金具が、新品の加硫ゴムにて、一体的に連結せしめられてなる構造を有している。また、それらのテストピースにおいて、両円筒金具を連結する加硫ゴムは、長さが３８ｍｍ、両円筒金具を連結する部位の幅が２２ｍｍ、厚肉円筒金具に固着せしめられる部位の幅が３６ｍｍとなるように構成されている。そして、そのような構造のテストピースに対して、初期±１４ｍｍの変位相当の荷重で、３Ｈｚの周波数により一定加振を行ない、加硫ゴムが破断に至るまでの加振回数を測定した。評価は比較例１のゴム組成物の加硫ゴムからなるテストピースの加振回数を１００として指数評価した。数値が大きいほど、耐久性に優れていることを示す。評価結果を表１に示す。
<Durability>
As a test piece for the durability test, a thick cylindrical metal fitting having an outer diameter of 16 mm and a height of 70 mm is positioned at the axial center of the thin cylindrical metal fitting in the inner hole of the thin cylindrical metal fitting having an outer diameter of 81 mm and a height of 49 mm. The two cylindrical fittings have a structure in which they are integrally connected with new vulcanized rubber. In these test pieces, the vulcanized rubber connecting the two cylindrical fittings has a length of 38 mm, the width of the portion connecting the two cylindrical fittings is 22 mm, and the width of the portion fixed to the thick cylindrical fitting is 36 mm. It is comprised so that it may become. The test piece having such a structure was subjected to constant excitation at a frequency of 3 Hz with a load corresponding to an initial displacement of ± 14 mm, and the number of vibrations until the vulcanized rubber was broken was measured. The evaluation was indexed with the number of vibrations of the test piece made of vulcanized rubber of the rubber composition of Comparative Example 1 as 100. It shows that it is excellent in durability, so that a numerical value is large. The evaluation results are shown in Table 1.
＜劣化後耐久性＞
上述した耐久性を算出するのに使用したテストピース（新品）を、１００℃×５００時間熱老化後に上述した方法にて耐久性を測定し、新品時の耐久性を１００とした場合の劣化後の耐久性を比較値として算出した。数値が１００に近いほど、初期の耐久性が劣化後においても保持されていることを示す。評価結果を表１に示す。
<Durability after deterioration>
The test piece (new article) used to calculate the durability mentioned above was measured for durability by the method described above after heat aging at 100 ° C. for 500 hours, and after deterioration when the durability at the time of new article was taken as 100 The durability was calculated as a comparative value. The closer the value is to 100, the more the initial durability is maintained even after deterioration. The evaluation results are shown in Table 1.
表１の結果より、実施例１〜３のゴム組成物の加硫ゴムは、比較例１〜４のゴム組成物の加硫ゴムに比べて、特に耐熱性が向上しており、さらに、長時間使用後における振動特性の変化率、特に高温環境下での長時間使用後においても、振動特性の変化率がかなり低減していることがわかる。また、初期振動特性、耐ヘタリ性、耐久性、及び劣化後耐久性がバランスよく向上していることがわかる。また、実施例４のゴム組成物の加硫ゴムは、比較例１〜４のゴム組成物の加硫ゴムに比べて、特に初期振動特性及び耐久性が向上していることがわかる。 From the results of Table 1, the vulcanized rubbers of the rubber compositions of Examples 1 to 3 have particularly improved heat resistance compared to the vulcanized rubbers of the rubber compositions of Comparative Examples 1 to 4, and It can be seen that the change rate of the vibration characteristics after use for a long time, particularly after the use for a long time in a high temperature environment, the change rate of the vibration characteristics is considerably reduced. In addition, it can be seen that the initial vibration characteristics, the settling resistance, the durability, and the durability after deterioration are improved in a well-balanced manner. In addition, it can be seen that the vulcanized rubber of the rubber composition of Example 4 has particularly improved initial vibration characteristics and durability as compared with the vulcanized rubber of the rubber compositions of Comparative Examples 1 to 4.
Claims (3)
前記ゴム成分１００重量部に対して、０．１〜１重量部の硫黄と、下記一般式（１）で表されるスルフェンイミド化合物と、チアゾール化合物とを含有することを特徴とする防振ゴム用ゴム組成物。
（式中、Ｒは炭素数１〜１８の直鎖アルキル基、分岐鎖アルキル基、脂環族炭化水素基、又は芳香族炭化水素基を表す）。 In the rubber composition for vibration-proof rubber containing a rubber component whose main component is natural rubber or a blend of natural rubber and diene synthetic rubber,
Antivibration comprising 0.1 to 1 part by weight of sulfur, a sulfenimide compound represented by the following general formula (1), and a thiazole compound with respect to 100 parts by weight of the rubber component Rubber composition for rubber.
(In the formula, R represents a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008098438A JP5248174B2 (en) | 2008-04-04 | 2008-04-04 | Rubber composition for anti-vibration rubber and anti-vibration rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008098438A JP5248174B2 (en) | 2008-04-04 | 2008-04-04 | Rubber composition for anti-vibration rubber and anti-vibration rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009249484A true JP2009249484A (en) | 2009-10-29 |
| JP5248174B2 JP5248174B2 (en) | 2013-07-31 |
Family
ID=41310487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008098438A Active JP5248174B2 (en) | 2008-04-04 | 2008-04-04 | Rubber composition for anti-vibration rubber and anti-vibration rubber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5248174B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011062135A1 (en) * | 2009-11-18 | 2011-05-26 | 株式会社ブリヂストン | Vibration isolating rubber composition and vibration isolating rubber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118788A (en) * | 1995-09-11 | 1997-05-06 | Goodyear Tire & Rubber Co:The | Sulfur-curable rubber containing hydrated thiosulfate |
| JPH10120825A (en) * | 1996-10-16 | 1998-05-12 | Toyo Tire & Rubber Co Ltd | Composition for vibrationproof rubber and vibrationproof rubber |
| JP2002534573A (en) * | 1999-01-12 | 2002-10-15 | ユニロイヤル ケミカル カンパニー インコーポレイテッド | In situ preparation of bis (benzothiazolesulfen) amide in polymer matrix |
| JP2008536964A (en) * | 2005-03-24 | 2008-09-11 | ソシエテ ド テクノロジー ミシュラン | Rubber composition comprising itaconimidomaleimide |
-
2008
- 2008-04-04 JP JP2008098438A patent/JP5248174B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09118788A (en) * | 1995-09-11 | 1997-05-06 | Goodyear Tire & Rubber Co:The | Sulfur-curable rubber containing hydrated thiosulfate |
| JPH10120825A (en) * | 1996-10-16 | 1998-05-12 | Toyo Tire & Rubber Co Ltd | Composition for vibrationproof rubber and vibrationproof rubber |
| JP2002534573A (en) * | 1999-01-12 | 2002-10-15 | ユニロイヤル ケミカル カンパニー インコーポレイテッド | In situ preparation of bis (benzothiazolesulfen) amide in polymer matrix |
| JP2008536964A (en) * | 2005-03-24 | 2008-09-11 | ソシエテ ド テクノロジー ミシュラン | Rubber composition comprising itaconimidomaleimide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011062135A1 (en) * | 2009-11-18 | 2011-05-26 | 株式会社ブリヂストン | Vibration isolating rubber composition and vibration isolating rubber |
| CN102666705A (en) * | 2009-11-18 | 2012-09-12 | 株式会社普利司通 | Vibration isolating rubber composition and vibration isolating rubber |
| CN102666705B (en) * | 2009-11-18 | 2016-04-06 | 株式会社普利司通 | vibration damping rubber composition and vibration-proof rubber |
| US9315656B2 (en) | 2009-11-18 | 2016-04-19 | Bridgestone Corporation | Vibration isolating rubber composition and vibration isolating rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5248174B2 (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6165406B2 (en) | Anti-vibration rubber composition and anti-vibration rubber | |
| JP5420224B2 (en) | Rubber composition for anti-vibration rubber, anti-vibration rubber and method for producing the same | |
| JP6112755B2 (en) | Anti-vibration rubber composition and anti-vibration rubber | |
| JP6369576B2 (en) | Anti-vibration rubber composition and anti-vibration rubber | |
| JP2015021097A (en) | Rubber composition for vibration-proof rubber, and vibration-proof rubber | |
| JP2011111532A (en) | Rubber composition for vibration-proof rubber and vibration-proof rubber | |
| JP5247206B2 (en) | Rubber composition for anti-vibration rubber and anti-vibration rubber | |
| JP5210801B2 (en) | Rubber composition for anti-vibration rubber and anti-vibration rubber | |
| JP5101117B2 (en) | Anti-vibration rubber composition | |
| JP2008007546A (en) | Vibration-insulating rubber composition and vibration-insulating rubber | |
| JP2010111742A (en) | Rubber composition for vibration-proof rubber and vibration-proof rubber | |
| JP2014105236A (en) | Rubber composition for vibration proof rubber and vibration proof rubber | |
| JP2007314697A (en) | Vibration-proof rubber composition and rubber vibration isolator | |
| JP5248174B2 (en) | Rubber composition for anti-vibration rubber and anti-vibration rubber | |
| JP5465317B2 (en) | Anti-vibration rubber composition and anti-vibration rubber using the same | |
| JP2019048959A (en) | Rubber composition for vibration-damping rubber and vibration-damping rubber product | |
| JP5872843B2 (en) | Rubber composition for anti-vibration rubber | |
| JP2003321575A (en) | Rubber composition | |
| JP2011162585A (en) | Rubber composition for vibration-damping rubber, and vibration-damping rubber | |
| JP2017214531A (en) | Rubber composition, rubber composition for vibration-proof rubber products, and vibration-proof rubber product | |
| JP2022052896A (en) | Rubber composition and vibration damping rubber including rubber composition vulcanized | |
| JP2010209285A (en) | Rubber composition for vibration-damping rubber and vibration-damping rubber | |
| JP2011111504A (en) | Rubber composition for vibration-proof rubber and vibration-proof rubber | |
| JP2013151584A (en) | Rubber composition for rubber vibration isolator | |
| JP6105426B2 (en) | Anti-vibration rubber composition and anti-vibration rubber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20101129 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121024 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121026 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121206 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130402 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130410 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5248174 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160419 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |