JP5256014B2 - High damping rubber composition - Google Patents
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- JP5256014B2 JP5256014B2 JP2008329245A JP2008329245A JP5256014B2 JP 5256014 B2 JP5256014 B2 JP 5256014B2 JP 2008329245 A JP2008329245 A JP 2008329245A JP 2008329245 A JP2008329245 A JP 2008329245A JP 5256014 B2 JP5256014 B2 JP 5256014B2
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- 238000013016 damping Methods 0.000 title claims description 49
- 229920001971 elastomer Polymers 0.000 title claims description 49
- 239000005060 rubber Substances 0.000 title claims description 49
- 239000000203 mixture Substances 0.000 title claims description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 34
- 239000011347 resin Substances 0.000 claims description 34
- 239000006229 carbon black Substances 0.000 claims description 29
- 229920005555 halobutyl Polymers 0.000 claims description 29
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 27
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 27
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 27
- 125000002723 alicyclic group Chemical group 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000004132 cross linking Methods 0.000 claims description 16
- 229920005549 butyl rubber Polymers 0.000 claims description 9
- 229920005556 chlorobutyl Polymers 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 238000006757 chemical reactions by type Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229920005557 bromobutyl Polymers 0.000 claims description 4
- 230000006835 compression Effects 0.000 description 24
- 238000007906 compression Methods 0.000 description 24
- 238000004073 vulcanization Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000003712 anti-aging effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000002238 attenuated effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- -1 Chlorobutyl Chemical group 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000008117 stearic acid Substances 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Vibration Prevention Devices (AREA)
- Springs (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、振動吸収材料等の用途に適した高減衰ゴム組成物に関するものであり、詳しくは、コンピューターのハードディスクの制振ダンパー、洗濯機等の一般家電製品の制振ダンパー、自動車用制振材、建築・住宅分野における制震,制振,免震等の用途に好適な高減衰ゴム組成物に関するものである。 The present invention relates to a highly damped rubber composition suitable for applications such as vibration absorbing materials, and more specifically, damping dampers for computer hard disks, damping dampers for general household electrical appliances such as washing machines, and damping for automobiles. The present invention relates to a high-damping rubber composition suitable for applications such as vibration control, vibration control and seismic isolation in the field of materials and construction / housing.
一般に、コンピューターのハードディスクの制振ダンパー、洗濯機等の一般家電製品の制振ダンパー、自動車用制振材、建築・住宅分野における建築用制震壁,制震(制振)ダンパー等の制震(制振)装置および免震装置の用途には、振動エネルギーを効率よく吸収する高減衰ゴム組成物からなるゴム材が用いられる。そして、上記高減衰ゴム組成物には、従来から、ブチル系ゴム組成物が用いられている(特許文献1参照)。
通常、上記のような用途における高減衰材は、圧縮された場合の変形量が大きく、また、荷重を受ける部位に対しては使用上制限を受けやすい。例えば、免震構造体のように、地震のエネルギーを吸収するものでは、高減衰化は必須特性であるとともに、建造物の荷重を受け続ける場合に圧縮方向への変形(へたり)が重要な問題となる。また、一般家電製品においても、振動を低減する為に高減衰材が使用され、これが常時の荷重を受ける部品である場合、その部品に対して、高減衰化と圧縮永久歪み特性は背反特性となっている。 Usually, the high damping material in the above-described applications has a large amount of deformation when compressed, and a part subjected to a load is likely to be restricted in use. For example, in structures that absorb earthquake energy, such as seismic isolation structures, high attenuation is an essential characteristic, and deformation (sagging) in the compression direction is important when continuing to receive building loads. It becomes a problem. Also, in general home appliances, a high damping material is used to reduce vibration, and when this is a part that receives a constant load, the high damping and compression set characteristics are contradictory to the part. It has become.
しかしながら、ブチル系ゴムは、本来、圧縮永久歪みが良くない。特に、高温領域では、へたりが生じやすい傾向にある。 However, butyl rubber is inherently not good in compression set. In particular, sag tends to occur easily in a high temperature region.
一方、ゴムに、樹脂(粘着付与剤)を添加し、その樹脂の塑性変形により振動エネルギーを吸収して減衰性を出す手法も提案されている。しかし、単純に樹脂を多く添加すると、圧縮変形後に元にもどらず、へたりが大きくなる傾向がある。また、ゴムに、カーボンブラック,シリカ等の充填材を多量に配合し、その充填材同士の摩擦により減衰性を出す手法も提案されている。この手法では、へたりは少ないが、しかし、ゴム組成物を調製する際の混練時に、その摩擦による発熱によりゴム焼けが生じ、加工性の悪化を引き起こす懸念があるため、充填材の多量配合により減衰性を出すにしても限界がある。 On the other hand, there has also been proposed a method in which a resin (tackifier) is added to rubber and the vibrational energy is absorbed by plastic deformation of the resin to produce a damping property. However, when a large amount of resin is simply added, it does not return to the original state after compression deformation, and the sag tends to increase. In addition, a method has been proposed in which a large amount of filler such as carbon black and silica is blended with rubber and the damping is obtained by friction between the fillers. In this method, there is little sag, however, there is a concern that heat generation due to friction may occur during kneading when preparing a rubber composition, which may cause deterioration of workability. There is a limit even if attenuating is given.
本発明は、このような事情に鑑みなされたもので、高減衰で、かつ、低温から高温領域の圧縮永久歪みが小さい高減衰ゴム組成物の提供をその目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a highly damped rubber composition having high damping and low compression set from low temperature to high temperature.
上記の目的を達成するために、本発明の高減衰ゴム組成物は、下記の(A)を主成分とし、下記の(B),(C)および(E)成分を含有するという構成をとる。
(A)ハロゲン化ブチルゴム。
(B)軟化点が60〜150℃の範囲内の、非極性の脂環族飽和炭化水素樹脂。
(C)(A)により架橋反応が活性化される樹脂架橋反応型アルキルフェノール・ホルムアルデヒド樹脂。
(E)窒素吸着比表面積が60m2/g以下のカーボンブラック。
In order to achieve the above object, the highly attenuated rubber composition of the present invention has the following (A) as a main component and contains the following (B), (C) and (E) components. .
(A) Halogenated butyl rubber.
(B) A nonpolar alicyclic saturated hydrocarbon resin having a softening point in the range of 60 to 150 ° C.
(C) Resin crosslinking reaction type alkylphenol -formaldehyde resin whose crosslinking reaction is activated by (A).
(E) Carbon black having a nitrogen adsorption specific surface area of 60 m 2 / g or less.
すなわち、本発明者は、前記課題を解決するため鋭意研究を重ねた。その研究の過程で、加硫速度が速く、架橋密度が良好なハロゲン化ブチルゴム(塩素化ブチルゴム,臭素化ブチルゴム等)をポリマーとして採用することを想起した。そして、このポリマーに、へたりを出さずに高減衰性を発現するため実験を重ねた結果、軟化点が特定範囲内の非極性の脂環族飽和炭化水素樹脂を添加すると良好になることを突き止めた。すなわち、上記脂環族飽和炭化水素樹脂は、その塑性変形による高減衰性の発現とともに、上記ポリマーとの相溶性が良好であるため、ミクロ分散化されやすく、しかも、圧縮永久歪みに対してマトリックスであるポリマーの特性を悪化させ難いといった性能を示すことから、このような結果になったと考えられる。そして、上記ポリマーと樹脂との架橋剤として、ハロゲン化ブチルゴムにより架橋反応が活性化される樹脂架橋反応型アルキルフェノール・ホルムアルデヒド樹脂を用いることにより、その加硫体は、低温から高温の圧縮永久歪みが良好になることを見いだし、本発明に到達した。 That is, the present inventor has intensively studied to solve the above problems. In the course of that research, we recalled the use of halogenated butyl rubber (chlorinated butyl rubber, brominated butyl rubber, etc.) as a polymer with a fast vulcanization rate and good crosslink density. And, as a result of repeated experiments to develop high attenuation without causing sag in this polymer, it has been found that the addition of a non-polar alicyclic saturated hydrocarbon resin having a softening point within a specific range is good. I found it. That is, the alicyclic saturated hydrocarbon resin has a high damping property due to its plastic deformation and good compatibility with the polymer, so that it is easy to be microdispersed, and moreover a matrix against compression set. It is thought that this result was obtained because it showed the performance that it was difficult to deteriorate the properties of the polymer. By using a resin cross-linking reaction type alkylphenol / formaldehyde resin whose cross-linking reaction is activated by halogenated butyl rubber as a cross-linking agent between the polymer and the resin, the vulcanizate has a compression set from a low temperature to a high temperature. It has been found to be good and the present invention has been reached.
本発明において、従来の硫黄加硫系ではなく、上記のように反応型アルキルフェノール・ホルムアルデヒド樹脂による樹脂架橋系を選定することにより、低温から高温の圧縮永久歪みが良好になる理由は、S−S結合よりも樹脂架橋のほうが耐熱性が良好で(S−S結合は、高温圧縮により切れやすいため、へたりが発生しやすい)、また、低温時においても、架橋構造の違いから、樹脂架橋のほうが耐圧縮永久歪み性が良好であり、さらにその分散性による樹脂架橋鎖の均一性も好条件として影響しているためと推測される。なお、上記の反応型アルキルフェノール・ホルムアルデヒド樹脂による樹脂架橋は、ハロゲン化ポリマーおよびハロゲン化金属により活性化されるため、本発明においてハロゲン化物は必須である。 In the present invention, the reason why the permanent compression set from low temperature to high temperature is improved by selecting a resin crosslinking system using a reactive alkylphenol / formaldehyde resin as described above, instead of the conventional sulfur vulcanization system, is SS The resin cross-linking has better heat resistance than the bond (SS bond is easy to break due to high-temperature compression, and sag is likely to occur). This is presumably because the compression set resistance is better, and the uniformity of the resin cross-linked chain due to its dispersibility is also affected as a favorable condition. In addition, since the resin crosslinking by the reactive alkylphenol / formaldehyde resin is activated by a halogenated polymer and a metal halide, a halide is essential in the present invention.
このように、本発明の高減衰ゴム組成物は、ハロゲン化ブチルゴムに、軟化点が特定範囲内の非極性の脂環族飽和炭化水素樹脂と、ハロゲン化ブチルゴムにより架橋反応が活性化される樹脂架橋反応型アルキルフェノール・ホルムアルデヒド樹脂と、特定のカーボンブラックとを含有するものである。そのため、高減衰で、かつ、低温から高温領域の圧縮永久歪みが小さいといった性能を発揮することができる。また、本発明の高減衰ゴム組成物からなる部材は、架橋密度が良好であり、耐熱性にも優れ、高温でのへたりが生じにくい。そして、本発明の高減衰ゴム組成物は、コンピューターのハードディスクの制振ダンパー、洗濯機等の一般家電製品の制振ダンパー、自動車用制振材、建築・住宅分野における建築用制震壁,制震(制振)ダンパー等の制震(制振)装置および免震装置の用途に有利に用いることができる。 As described above, the high-damping rubber composition of the present invention includes a halogenated butyl rubber, a nonpolar alicyclic saturated hydrocarbon resin having a softening point within a specific range, and a resin whose crosslinking reaction is activated by the halogenated butyl rubber. It contains a crosslinking reaction type alkylphenol -formaldehyde resin and specific carbon black. Therefore, it is possible to exhibit the performance of high attenuation and low compression set from low temperature to high temperature. In addition, the member made of the highly damped rubber composition of the present invention has a good crosslink density, excellent heat resistance, and does not easily sag at high temperatures. The high-damping rubber composition of the present invention includes a vibration damper for a hard disk of a computer, a vibration damper for a general household electric appliance such as a washing machine, a vibration damping material for an automobile, a building damping wall for building / housing, The present invention can be advantageously used for seismic control devices such as seismic (vibration control) dampers and seismic isolation devices.
特に、上記各成分に加え、酸化亜鉛を含有すると、本発明の高減衰ゴム組成物は、より架橋密度が良好となる。 In particular, when zinc oxide is contained in addition to the above components, the highly attenuated rubber composition of the present invention has a better crosslinking density.
本発明では、上記特定のカーボンブラックとして、窒素吸着比表面積が60m2/g以下のカーボンブラックを用いていることから、加硫によりポリマー(A成分)と上記カーボンブラックとの間に摩擦が発生し、減衰性が向上するため、その減衰向上した分、脂環族飽和炭化水素樹脂(B成分)を減量することができ、温度依存性を良好にすることができる。また、このようにして脂環族飽和炭化水素樹脂(B成分)を減量することにより、練り加工性および成型加工性も良好となる。さらに、その高減衰ゴム組成物の加硫体の粘着性も低下し、べたつきが少なくなることにより、金型粘着が少なくなり、扱いやすくなる。 In the present invention, since carbon black having a nitrogen adsorption specific surface area of 60 m 2 / g or less is used as the specific carbon black , friction occurs between the polymer (component A) and the carbon black by vulcanization. Since the damping property is improved, the amount of the alicyclic saturated hydrocarbon resin (component B) can be reduced by the amount of the damping improvement, and the temperature dependency can be improved. In addition, by reducing the amount of the alicyclic saturated hydrocarbon resin (component B) in this way, kneadability and moldability are also improved. Furthermore, the adhesiveness of the vulcanizate of the highly damped rubber composition is also reduced and the stickiness is reduced, so that the mold adhesion is reduced and the handling becomes easy.
また、上記ハロゲン化ブチルゴムに、レギュラーブチルゴムを45重量%未満の割合で含有すると、ハロゲン化ブチルゴムの加硫速度に起因する、ゴム練り時の焼けが解消され、本発明の高減衰ゴム組成物のポットライフが、より長くなる。 Further, when the regular butyl rubber is contained in the halogenated butyl rubber in a proportion of less than 45% by weight, the burning at the time of rubber kneading due to the vulcanization rate of the halogenated butyl rubber is eliminated, and the high attenuation rubber composition of the present invention is used. The pot life is longer.
つぎに、本発明の実施の形態を詳しく説明する。 Next, embodiments of the present invention will be described in detail.
本発明の高減衰ゴム組成物は、ハロゲン化ブチルゴム(A成分)を主成分とし、非極性の脂環族飽和炭化水素樹脂(B成分)と、ハロゲン化ブチルゴムにより架橋反応が活性化される樹脂架橋反応型アルキルフェノール・ホルムアルデヒド樹脂(C成分)(以下、単に「反応型アルキルフェノール・ホルムアルデヒド樹脂」と略す。)と、窒素吸着比表面積が60m2/g以下のカーボンブラック(E成分)とを含有するものである。なお、本発明において、上記「主成分」とは、組成物の特性に大きな影響を与えるもののことであり、通常は、全体の55重量%以上を意味する。また、本発明において、上記「非極性」とは、「極性を有する」の対語であり、全く極性を有しないことを意味するものではない。 The high-damping rubber composition of the present invention comprises a halogenated butyl rubber (component A) as a main component, a nonpolar alicyclic saturated hydrocarbon resin (component B) and a resin whose crosslinking reaction is activated by the halogenated butyl rubber. Contains a cross-linking reaction type alkylphenol / formaldehyde resin (component C) (hereinafter simply referred to as “reaction type alkylphenol / formaldehyde resin”) and carbon black (component E) having a nitrogen adsorption specific surface area of 60 m 2 / g or less. Is. In the present invention, the above “main component” means a material that greatly affects the properties of the composition, and usually means 55% by weight or more of the whole. Further, in the present invention, the above “nonpolar” is a counter word of “having polarity” and does not mean having no polarity at all.
上記A成分のハロゲン化ブチルゴムとしては、好ましくは、塩素化ブチルゴム(Cl−IIR)や臭素化ブチルゴム(Br−IIR)が用いられる。そして、これらのハロゲン化ブチルゴムは、単独であるいは二種以上併せて用いられる。 As the A component halogenated butyl rubber, chlorinated butyl rubber (Cl-IIR) or brominated butyl rubber (Br-IIR) is preferably used. These halogenated butyl rubbers are used alone or in combination of two or more.
なお、上記ハロゲン化ブチルゴムに、レギュラーブチルゴムを45重量%未満の割合で含有すると、ハロゲン化ブチルゴムの加硫速度に起因する、ゴム練り時の焼けが解消され、本発明の高減衰ゴム組成物のポットライフがより長くなるため、好ましい。 In addition, when the regular butyl rubber is contained in the halogenated butyl rubber in a proportion of less than 45% by weight, the burning at the time of rubber kneading due to the vulcanization rate of the halogenated butyl rubber is eliminated, and the high attenuation rubber composition of the present invention is used. This is preferable because the pot life becomes longer.
上記B成分の脂環族飽和炭化水素樹脂は、水酸基,カルボキシル基等の極性基を有しないものが用いられる。そして、上記脂環族飽和炭化水素樹脂としては、重量平均分子量が300〜4000の範囲のもので、軟化点が60〜150℃(好ましくは90〜140℃)の範囲のものが選定される。これらは、単独であるいは二種以上併せて用いられる。なお、上記特定の脂環族飽和炭化水素樹脂は、市販のものでは、アルコンP90、アルコンP140(ともに荒川化学工業社製)が好ましく用いられる。
As the B component alicyclic saturated hydrocarbon resin, those having no polar groups such as hydroxyl groups and carboxyl groups are used. Then, as the alicyclic saturated hydrocarbon resin, one Weight average molecular weight ranging from 300 to 4000, is selected in the range of the softening point of 60 to 150 ° C. (preferably 90 to 140 ° C.) . These may be used alone or in combination of two or more. As the specific alicyclic saturated hydrocarbon resin, commercially available products are preferably Alcon P90 and Alcon P140 (both manufactured by Arakawa Chemical Industries).
上記特定の脂環族飽和炭化水素樹脂(B成分)の配合量は、ハロゲン化ブチルゴム(A成分)100重量部(以下、「部」と略す)に対して5〜60部の範囲に設定することが好ましく、より好ましくは、15〜40部の範囲である。すなわち、この範囲内であると、圧縮永久歪みが、より良好になるからである。なお、上記特定の脂環族飽和炭化水素樹脂(B成分)の配合量が下限未満であると、圧高減衰性の効果が不充分となる。逆に、上記特定の脂環族飽和炭化水素樹脂(B成分)の配合量が上限を超えた場合、粘着性が強くなり、練り込み加工性が悪化する傾向がみられるようになる。 The blending amount of the specific alicyclic saturated hydrocarbon resin (component B) is set in the range of 5 to 60 parts with respect to 100 parts by weight (hereinafter referred to as “part”) of the halogenated butyl rubber (component A). Preferably, it is the range of 15-40 parts. That is, if it is within this range, the compression set becomes better. In addition, if the blending amount of the specific alicyclic saturated hydrocarbon resin (component B) is less than the lower limit, the effect of the high-damping property becomes insufficient. On the contrary, when the compounding amount of the specific alicyclic saturated hydrocarbon resin (component B) exceeds the upper limit, the tackiness becomes strong and the kneading processability tends to be deteriorated.
上記C成分の反応型アルキルフェノール・ホルムアルデヒド樹脂としては、例えば、田岡化学工業製の臭素化アルキルフェノール・ホルムアルデヒド縮合体(タッキロール250)、アルキルフェノール・ホルムアルデヒド縮合体(タッキロール201)等があげられる。これらは、単独であるいは二種以上併せて用いられる。 Examples of the reactive alkylphenol -formaldehyde resin of component C include brominated alkylphenol-formaldehyde condensate (Tacicol 250) and alkylphenol-formaldehyde condensate (Tacicol 201) manufactured by Taoka Chemical Industries. These may be used alone or in combination of two or more.
上記反応型アルキルフェノール・ホルムアルデヒド樹脂(C成分)の配合量は、ハロゲン化ブチルゴム(A成分)100部に対して、2〜20部の範囲に設定することが好ましく、より好ましくは、3〜15部の範囲である。すなわち、上記反応型アルキルフェノール・ホルムアルデヒド樹脂(C成分)の配合量が下限未満であると、架橋反応性が悪くなる傾向がみられ、逆に反応型アルキルフェノール・ホルムアルデヒド樹脂(C成分)の配合量が多すぎると、ゴム物性(破断伸び)が低下する傾向がみられるからである。 The compounding amount of the reactive alkylphenol / formaldehyde resin (component C) is preferably set in the range of 2 to 20 parts, more preferably 3 to 15 parts, relative to 100 parts of the halogenated butyl rubber (component A). Range. That is, when the amount of the reactive alkylphenol / formaldehyde resin (C component) is less than the lower limit, the crosslinking reactivity tends to deteriorate, and conversely, the amount of the reactive alkylphenol / formaldehyde resin (C component) is reduced. This is because if the amount is too large, the rubber properties (elongation at break) tend to decrease.
上記(A)〜(C)成分に加え、酸化亜鉛(D成分)を含有すると、本発明の高減衰ゴム組成物は、より架橋密度が良好となるため、好ましい。 When zinc oxide (component D) is contained in addition to the components (A) to (C), the highly attenuated rubber composition of the present invention is preferable because the crosslink density becomes better.
上記酸化亜鉛(D成分)の配合量は、架橋密度を良好にするため、ハロゲン化ブチルゴム(A成分)100部に対して、1〜15部の範囲に設定することが好ましく、より好ましくは、3〜10部の範囲である。 The blending amount of the zinc oxide (D component) is preferably set in the range of 1 to 15 parts, more preferably, with respect to 100 parts of the halogenated butyl rubber (component A) in order to improve the crosslinking density. It is in the range of 3 to 10 parts.
なお、本発明の高減衰ゴム組成物においては、上記各成分とともに、カーボンブラック,シリカ等の充填材、加硫促進剤、加硫助剤、老化防止剤、可塑剤等を必要に応じて適宜に配合することも可能である。 In the high damping rubber composition of the present invention, a filler such as carbon black and silica, a vulcanization accelerator, a vulcanization aid, an anti-aging agent, a plasticizer, and the like are appropriately combined with the above components as necessary. It is also possible to blend in.
上記カーボンブラックとしては、種々のグレードのカーボンブラックが、単独であるいは二種以上併せて用いられるが、本発明においては、窒素吸着比表面積が60m2/g以下のカーボンブラック(E成分)を必須で含有する。これにより、加硫によりポリマー(A成分)と上記カーボンブラックとの間に摩擦が発生し、減衰性が向上するため、その減衰向上した分、脂環族飽和炭化水素樹脂(B成分)を減量することができる。すなわち、脂肪族飽和炭化水素樹脂の多量添加は、減衰向上に繋がる反面、温度依存性が悪化してしまう問題があったが、上記特定のカーボンブラックを含有することにより、脂肪族飽和炭化水素樹脂の多量添加を行わずに済むため、温度依存性を良好にすることができ、好ましい。また、このようにして脂環族飽和炭化水素樹脂(B成分)を減量することにより、ゴム組成物およびその加硫物の粘着性(べたつき)が抑制されるため、練り加工性および成型加工性も良好となる。さらに、その高減衰ゴム組成物の加硫体の粘着性も低下し、べたつきが少なくなることにより、金型粘着が少なくなり、扱い易くなる。上記カーボンブラックの窒素吸着比表面積は、上記観点から、好ましくは9〜30m2/gの範囲である。なお、上記窒素吸着比表面積は、JIS K 6217に規定されており、単位重量当たりの窒素吸着比表面積(m2/g)を意味する。 As the carbon black, various grades of carbon black may be used alone or in combination of two or more. In the present invention, carbon black (component E) having a nitrogen adsorption specific surface area of 60 m 2 / g or less is essential. in containing. As a result , vulcanization generates friction between the polymer (component A) and the carbon black, and the damping is improved. Therefore, the amount of the alicyclic saturated hydrocarbon resin (component B) is reduced by the amount of the improved damping. can do. That is, the addition of a large amount of an aliphatic saturated hydrocarbon resin leads to an improvement in attenuation, but there is a problem that the temperature dependency deteriorates. By containing the specific carbon black, the aliphatic saturated hydrocarbon resin Since it is not necessary to add a large amount of, temperature dependency can be improved, which is preferable. Further, by reducing the amount of the alicyclic saturated hydrocarbon resin (component B) in this way, the tackiness (stickiness) of the rubber composition and its vulcanizate is suppressed. Will also be good. Furthermore, the adhesiveness of the vulcanizate of the highly damped rubber composition is also reduced and the stickiness is reduced, so that the mold adhesion is reduced and the handling becomes easy. From the above viewpoint, the nitrogen adsorption specific surface area of the carbon black is preferably in the range of 9 to 30 m 2 / g. In addition, the said nitrogen adsorption specific surface area is prescribed | regulated to JISK6217, and means the nitrogen adsorption specific surface area (m < 2 > / g) per unit weight.
窒素吸着比表面積が60m2 /g以下のカーボンブラック(E成分)としては、例えば、MT級,SRF級,MAF−HS級,FT級,GPF級,FEF級,MAF級といった種々のグレードのカーボンブラックがあげられる。なお、窒素吸着比表面積が60m2 /gより大きいカーボンブラックには、例えば、HAF級,ISAF級,SAF級といったグレードのカーボンブラックがある。 Examples of carbon black (component E) having a nitrogen adsorption specific surface area of 60 m 2 / g or less include various grades of carbon such as MT, SRF, MAF-HS, FT, GPF, FEF, and MAF. Black is raised. The carbon black having a nitrogen adsorption specific surface area larger than 60 m 2 / g includes, for example, grades of carbon black such as HAF class, ISAF class, and SAF class.
上記カーボンブラックの配合量は、ハロゲン化ブチルゴム(A成分)100部に対して、50〜150部の範囲に設定することが好ましく、より好ましくは、50〜120部の範囲である。なお、上記カーボンブラックの配合量が上限を超えると、粘度が上昇し、加工性が悪化する等の問題が生じるようになる。 The blending amount of the carbon black is preferably set in the range of 50 to 150 parts, more preferably in the range of 50 to 120 parts with respect to 100 parts of the halogenated butyl rubber (component A). In addition, when the compounding quantity of the said carbon black exceeds an upper limit, problems will arise, such as a viscosity rising and workability worsening.
そして、窒素吸着比表面積が60m2 /g以下のカーボンブラック(E成分)を配合する場合、前記特定の脂環族飽和炭化水素樹脂(B成分)の配合量は、ハロゲン化ブチルゴム(A成分)100部に対して、3〜50部の範囲にまで減量することができる。すなわち、このように少量であっても、先に述べたような脂環族飽和炭化水素樹脂(B成分)による高減衰性の効果を充分発揮することができるからである。 When carbon black (component E) having a nitrogen adsorption specific surface area of 60 m 2 / g or less is blended, the blending amount of the specific alicyclic saturated hydrocarbon resin (component B) is halogenated butyl rubber (component A). The amount can be reduced to a range of 3 to 50 parts per 100 parts. That is, even with such a small amount, it is possible to sufficiently exhibit the effect of high attenuation by the alicyclic saturated hydrocarbon resin (component B) as described above.
上記加硫助剤としては、例えば、ステアリン酸、不飽和脂肪酸亜鉛等があげられる。これらは単独であるいは二種以上併せて用いられる。 Examples of the vulcanization aid include stearic acid and unsaturated fatty acid zinc. These may be used alone or in combination of two or more.
また、上記加硫助剤の配合量は、上記ハロゲン化ブチルゴム(A成分)100部に対して、1〜25部の範囲が好ましく、特に好ましくは2〜10部の範囲である。 The amount of the vulcanization aid is preferably in the range of 1 to 25 parts, particularly preferably in the range of 2 to 10 parts, with respect to 100 parts of the halogenated butyl rubber (component A).
上記老化防止剤としては、例えば、カルバメート系老化防止剤、フェニレンジアミン系老化防止剤、フェノール系老化防止剤、ジフェニルアミン系老化防止剤、キノリン系老化防止剤、イミダゾール系老化防止剤、ワックス類等があげられる。これらは単独であるいは二種以上併せて用いられる。 Examples of the anti-aging agent include carbamate-based anti-aging agents, phenylenediamine-based anti-aging agents, phenol-based anti-aging agents, diphenylamine-based anti-aging agents, quinoline-based anti-aging agents, imidazole-based anti-aging agents, and waxes. can give. These may be used alone or in combination of two or more.
また、上記老化防止剤の配合量は、上記ハロゲン化ブチルゴム(A成分)100部に対して、1〜10部の範囲が好ましく、特に好ましくは2〜5部の範囲である。 The blending amount of the anti-aging agent is preferably in the range of 1 to 10 parts, particularly preferably in the range of 2 to 5 parts with respect to 100 parts of the halogenated butyl rubber (component A).
上記可塑剤としては、硬度の調整等を目的とするものであり、例えば、フタル酸ジオクチル(DOP),フタル酸ジ−n−ブチル(DBP)等のフタル酸系可塑剤、ジブチルカルビトールアジペート,ジオクチルアジペート(DOA)等のアジピン酸系可塑剤、セバシン酸ジオクチル(DOS),セバシン酸ジブチル(DBS)等のセバシン酸系可塑剤といった合成可塑剤や、ナフテン系オイル,パラフィン系オイル,アロマオイル等の鉱物油があげられる。これらは単独であるいは二種以上併せて用いられる。 The plasticizer is for the purpose of adjusting hardness and the like. For example, phthalic acid plasticizers such as dioctyl phthalate (DOP) and di-n-butyl phthalate (DBP), dibutyl carbitol adipate, Synthetic plasticizers such as adipic acid plasticizers such as dioctyl adipate (DOA), sebacic acid plasticizers such as dioctyl sebacate (DOS), dibutyl sebacate (DBS), naphthenic oils, paraffinic oils, aroma oils, etc. Mineral oil. These may be used alone or in combination of two or more.
また、上記可塑剤の配合量は、上記ハロゲン化ブチルゴム(A成分)100部に対して、1〜50部の範囲が好ましく、特に好ましくは3〜30部の範囲である。 The amount of the plasticizer is preferably in the range of 1 to 50 parts, particularly preferably in the range of 3 to 30 parts with respect to 100 parts of the halogenated butyl rubber (component A).
本発明の高減衰ゴム組成物は、例えば、つぎのようにして調製することができる。すなわち、上記ハロゲン化ブチルゴム(A成分)と、非極性の脂環族飽和炭化水素樹脂(B成分)と、窒素吸着比表面積が60m2/g以下のカーボンブラック(E成分)等の充填材,酸化亜鉛等の加硫助剤,老化防止剤,可塑剤等を適宜に配合し、これらをバンバリーミキサー等を用いて、90〜140℃で、3〜5分間程度混練を行う。つぎに、これに、反応型アルキルフェノール・ホルムアルデヒド樹脂(C成分),加硫促進剤等を適宜に配合し、オープンロールを用いて、所定条件(例えば、50℃×5分間)で混練することにより、高減衰ゴム組成物を作製する。なお、このようにして得られた高減衰ゴム組成物を、高温(150〜170℃)で5〜30分間、加硫することにより、目的とする高減衰ゴム(部材)を得ることができる。 The high damping rubber composition of the present invention can be prepared, for example, as follows. That is, a filler such as the halogenated butyl rubber (component A), a nonpolar alicyclic saturated hydrocarbon resin (component B), carbon black (component E) having a nitrogen adsorption specific surface area of 60 m 2 / g or less, Vulcanizing aids such as zinc oxide, anti-aging agents, plasticizers and the like are appropriately blended, and these are kneaded at 90 to 140 ° C. for about 3 to 5 minutes using a Banbury mixer or the like. Next, a reaction type alkylphenol / formaldehyde resin (component C), a vulcanization accelerator, and the like are appropriately blended in this, and kneaded using an open roll under predetermined conditions (for example, 50 ° C. × 5 minutes). A high damping rubber composition is prepared. The intended high damping rubber (member) can be obtained by vulcanizing the high damping rubber composition thus obtained at a high temperature (150 to 170 ° C.) for 5 to 30 minutes.
本発明の高減衰ゴム組成物は、例えば、コンピューターのハードディスクの制振ダンパー、洗濯機等の一般家電製品の制振ダンパー、自動車用制振材、建築・住宅分野における建築用制震壁,制震ダンパー等の高減衰材料として、好適に用いられる。 The high damping rubber composition of the present invention includes, for example, a vibration damper for a hard disk of a computer, a vibration damper for a general household electric appliance such as a washing machine, a vibration damping material for an automobile, a building damping wall for a building / housing field, It is preferably used as a high damping material such as a seismic damper.
つぎに、実施例について比較例と併せて説明する。ただし、本発明は、これら実施例に限定されるものではない。 Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.
まず、実施例および比較例に先立ち、下記に示す材料を準備した。 First, prior to the examples and comparative examples, the following materials were prepared.
〔塩素化ブチルゴム〕
クロロブチル1066、JSR社製
[Chlorinated butyl rubber]
Chlorobutyl 1066, manufactured by JSR
〔レギュラーブチルゴム〕
ブチル365、JSR社製
[Regular butyl rubber]
Butyl 365, manufactured by JSR
〔脂環族飽和炭化水素樹脂(i) 〕
アルコンP140(極性基不含、軟化点140℃)、荒川化学工業社製
(Alicyclic saturated hydrocarbon resin (i))
Alcon P140 (polar group-free, softening point 140 ° C), manufactured by Arakawa Chemical Industries
〔脂環族飽和炭化水素樹脂(ii)〕
アルコンP90(極性基不含、軟化点90℃)、荒川化学工業社製
(Alicyclic saturated hydrocarbon resin (ii))
Alcon P90 (polar group-free, softening point 90 ° C), manufactured by Arakawa Chemical Industries
〔脂環族飽和炭化水素樹脂(iii) 〕
KR1842(水酸基含有)、荒川化学工業社製
(Alicyclic saturated hydrocarbon resin (iii))
KR1842 (containing hydroxyl group), manufactured by Arakawa Chemical Industries
〔非反応樹脂〕
タッキロール101(非反応型アルキルフェノール・ホルムアルデヒド樹脂)、田岡化学工業社製
[Non-reactive resin]
Tackolol 101 (non-reactive alkylphenol / formaldehyde resin), manufactured by Taoka Chemical Co., Ltd.
〔カーボンブラック(i) 〕
SRFカーボン(シーストS(窒素吸着比表面積:27m2 /g)、東海カーボン社製)
[Carbon black (i)]
SRF carbon (Sheet S (nitrogen adsorption specific surface area: 27 m 2 / g), manufactured by Tokai Carbon Co., Ltd.)
〔カーボンブラック(ii)〕
MTカーボン(サーマックスN990(窒素吸着比表面積:9m2 /g)、キャンカーブ社製)
(Carbon black (ii))
MT carbon (Thermax N990 (nitrogen adsorption specific surface area: 9 m 2 / g), manufactured by Cancarb)
〔カーボンブラック(iii) 〕
MAF−HSカーボン(シースト116HM(窒素吸着比表面積:56m2 /g)、東海カーボン社製)
[Carbon black (iii)]
MAF-HS carbon (seed 116HM (nitrogen adsorption specific surface area: 56 m 2 / g), manufactured by Tokai Carbon Co., Ltd.)
〔カーボンブラック(iv)〕
HAFカーボン(シースト3(窒素吸着比表面積:79m2 /g)、東海カーボン社製)
(Carbon black (iv))
HAF carbon (Seest 3 (nitrogen adsorption specific surface area: 79 m 2 / g), manufactured by Tokai Carbon Co., Ltd.)
〔亜鉛華〕
酸化亜鉛二種、三井金属鉱業社製
[Zinc flower]
Two types of zinc oxide, manufactured by Mitsui Mining & Mining
〔樹脂加硫剤〕
タッキロール201(反応型アルキルフェノール・ホルムアルデヒド樹脂)、田岡化学工業社製
(Resin vulcanizing agent)
Tactrol 201 (reactive alkylphenol / formaldehyde resin), manufactured by Taoka Chemical Co., Ltd.
〔CZ〕
ノクセラーCZ(スルフェンアミド系加硫促進剤)、大内新興化学社製
[CZ]
Noxeller CZ (sulfenamide vulcanization accelerator), manufactured by Ouchi Shinsei Chemical Co., Ltd.
〔TL〕
アクセルTL(ジチオカルバミン酸系加硫促進剤)、川口化学工業社製
[TL]
Accel TL (dithiocarbamic acid vulcanization accelerator), manufactured by Kawaguchi Chemical Industry Co., Ltd.
〔S〕
硫黄、鶴見化学工業社製
[S]
Sulfur, made by Tsurumi Chemical Co., Ltd.
〔実施例1〕
塩素化ブチルゴム100部と、脂環族飽和炭化水素樹脂(i) 30部と、SRFカーボン53部と、加硫助剤である亜鉛華5部とを配合し、これらをバンバリーミキサーを用いて、90〜140℃で5分間混練を行った。つぎに、これを加硫するため、樹脂加硫剤(反応型アルキルフェノール・ホルムアルデヒド樹脂)5部を配合し、オープンロールを用いて、約50℃で5分間混練することにより、高減衰ゴム組成物を調製した。
[Example 1]
100 parts of chlorinated butyl rubber, 30 parts of alicyclic saturated hydrocarbon resin (i), 53 parts of SRF carbon, and 5 parts of zinc oxide as a vulcanization aid are blended, and these are mixed using a Banbury mixer. Kneading was performed at 90 to 140 ° C. for 5 minutes. Next, in order to vulcanize the rubber composition, 5 parts of a resin vulcanizing agent (reactive alkylphenol / formaldehyde resin) is blended and kneaded at about 50 ° C. for 5 minutes using an open roll to obtain a high damping rubber composition. Was prepared.
〔実施例2〜5、比較例1〜6〕
下記の表1および表2に示すように、各成分の配合量等を変更する以外は、実施例1に準じて、ゴム組成物を調製した。
[Examples 2 to 5 and Comparative Examples 1 to 6 ]
As shown in Table 1 and Table 2 below, a rubber composition was prepared according to Example 1 except that the amount of each component was changed.
このようにして得られた実施例および比較例のゴム組成物を用い、下記の基準に従って、各特性の評価を行った。その結果を、後記の表3および表4に併せて示した。 Using the rubber compositions of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the following criteria. The results are also shown in Table 3 and Table 4 below.
〔圧縮永久歪み〕
上記ゴム組成物をJIS K 6262に準拠した形状とサイズに成形して160℃×45分の条件でプレス加硫し、加硫ゴムテストピースを作製した。そして、このテストピースを、JIS K 6262に準拠し、温度120℃,試験時間24時間,圧縮率25%の条件(表3および表4における「高温」条件)で治具に固定し、その後、上記テストピースを、上記治具から開放して23℃雰囲気下で30分放置した後、その圧縮永久歪みを測定した。また、温度23℃,試験時間24時間,圧縮率25%の条件(表3および表4における「常温」条件)でも、上記と同様に、加硫ゴムテストピースを治具に固定し、その後、上記治具から開放して23℃雰囲気下で30分放置した後の上記テストピースの圧縮永久歪みを測定した。なお、これらの値が双方とも12%以下(好ましくは10%以下)であれば、へたり難く、圧縮永久歪みに優れていることを示す。そのため、後記の表3および表4において、その値が10%以下であるものを○、10%を超えるが12%以下であるものを△、12%を超えるものを×と評価した。
(Compression set)
The rubber composition was molded into a shape and size conforming to JIS K 6262 and press vulcanized under the conditions of 160 ° C. × 45 minutes to produce a vulcanized rubber test piece. And this test piece is fixed to a jig in accordance with JIS K 6262, under conditions of a temperature of 120 ° C., a test time of 24 hours, and a compression ratio of 25% (“high temperature” conditions in Tables 3 and 4), The test piece was released from the jig and allowed to stand at 23 ° C. for 30 minutes, and then its compression set was measured. Also, under the conditions of a temperature of 23 ° C., a test time of 24 hours, and a compression ratio of 25% (the “normal temperature” conditions in Tables 3 and 4), the vulcanized rubber test piece was fixed to the jig in the same manner as above, The compression set of the test piece was measured after being released from the jig and allowed to stand for 30 minutes in a 23 ° C. atmosphere. In addition, if both of these values are 12% or less (preferably 10% or less), it is difficult to sag and indicates excellent compression set. Therefore, in Table 3 and Table 4 below, those having a value of 10% or less were evaluated as ◯, those exceeding 10% but 12% or less were evaluated as Δ, and those exceeding 12% were evaluated as ×.
〔粘弾性特性〕
上記ゴム組成物を160℃×30分の条件でプレス加硫してなるシートを用い、JIS K 6394に準拠し、引張り歪み0.5%,周波数5Hz,測定温度20℃の条件で、粘弾性スペクトロメーター(ユービーエム社製)により損失正接(tanδ)を測定した。なお、tanδの値が0.5以上であれば、減衰性に優れていることを示す。そのため、下記の表3および表4において、「減衰性」の評価として、この基準を満たすものを○、この基準を満たさないものを×と評価した。
(Viscoelastic properties)
Using a sheet obtained by press vulcanizing the rubber composition under the conditions of 160 ° C. × 30 minutes, in accordance with JIS K 6394, under conditions of tensile strain 0.5%, frequency 5 Hz, measurement temperature 20 ° C. Loss tangent (tan δ) was measured with a spectrometer (manufactured by UBM). In addition, if the value of tan δ is 0.5 or more, it indicates that the attenuation is excellent. Therefore, in the following Tables 3 and 4, as evaluation of “attenuation”, those satisfying this criterion were evaluated as “◯”, and those not satisfying this criterion were evaluated as “X”.
上記結果から、実施例品は、常温下であっても高温下であっても、圧縮永久歪みの値が小さく、常温下であっても高温下であっても10%以下の圧縮永久歪みであることから、温度依存によりへたりが生じない(温度依存性に優れている)ことがわかる。また、tanδ(粘弾性特性)の値が、いずれも0.5以上であるため、高減衰であることがわかる。なお、実施例3品のように、ポリマーとして、塩素化ブチルゴムにレギュラーブチルゴムを併用した場合、塩素化ブチルゴムを単独で用いたときよりもゴム組成物のポットライフが長くなった。また、実施例のゴム組成物のポリマーである塩素化ブチルゴムに代えて、臭素化ブチルゴムを用いた場合も、上記実施例と同様、優れた結果が得られた。 From the above results, Example product, even high temperature even in room temperature, compression set value of distortion rather small, less than 10% compression set even in a high temperature even in room temperature and a der Turkey, does not occur sag by temperature dependence (an excellent temperature dependence) can be seen. Moreover, since the values of tan δ (viscoelastic characteristics) are both 0.5 or more, it can be seen that the attenuation is high. As in Example 3, when the regular butyl rubber was used in combination with the chlorinated butyl rubber as the polymer, the pot life of the rubber composition was longer than when the chlorinated butyl rubber was used alone. Further, when brominated butyl rubber was used instead of the chlorinated butyl rubber which is a polymer of the rubber composition of the example, excellent results were obtained as in the above example.
これに対して、比較例1品および比較例2品は、非反応型アルキルフェノール・ホルムアルデヒド樹脂の配合により減衰性を出しているが、圧縮永久ひずみ特性に温度依存がみられる。比較例3品は、減衰性を出すための材料を全く配合しておらず、減衰性が顕著に悪い。比較例4品は、圧縮永久歪みに劣る。比較例5品は、実施例に近い配合組成であるが、その材料である脂環族飽和炭化水素樹脂が、水酸基を含有するものであるため、所望の圧縮永久歪み特性も、減衰性も得られず、実施例に比べ、これらの特性に劣ることがわかる。比較例6品は、実施例1〜5品に比べ、圧縮永久歪み特性に劣ることがわかる。 On the other hand, Comparative Product 1 and Comparative Product 2 exhibit attenuating properties due to the blending of the non-reactive alkylphenol / formaldehyde resin, but show temperature dependence in compression set characteristics. The product of Comparative Example 3 does not contain any material for providing attenuation, and the attenuation is remarkably bad. The product of Comparative Example 4 is inferior in compression set. The product of Comparative Example 5 has a composition similar to that of the Examples, but the alicyclic saturated hydrocarbon resin as the material contains a hydroxyl group, so that desired compression set characteristics and damping properties can be obtained. It is understood that these characteristics are inferior to those of the examples. It turns out that the comparative example 6 goods are inferior to a compression set characteristic compared with Examples 1-5 goods.
Claims (10)
(A)ハロゲン化ブチルゴム。
(B)軟化点が60〜150℃の範囲内の、非極性の脂環族飽和炭化水素樹脂。
(C)(A)により架橋反応が活性化される樹脂架橋反応型アルキルフェノール・ホルムアルデヒド樹脂。
(E)窒素吸着比表面積が60m2/g以下のカーボンブラック。 A high-damping rubber composition comprising the following (A) as a main component and the following (B), (C) and (E) components:
(A) Halogenated butyl rubber.
(B) A nonpolar alicyclic saturated hydrocarbon resin having a softening point in the range of 60 to 150 ° C.
(C) Resin crosslinking reaction type alkylphenol -formaldehyde resin whose crosslinking reaction is activated by (A).
(E) Carbon black having a nitrogen adsorption specific surface area of 60 m 2 / g or less.
(D)酸化亜鉛。 The high-damping rubber composition according to any one of claims 1 to 4, further comprising the following component (D) in addition to the components (A) to (C) and (E).
(D) Zinc oxide.
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