JP2004099753A - Manufacturing method of hydrogenated nitrile butadiene rubber composition - Google Patents
Manufacturing method of hydrogenated nitrile butadiene rubber composition Download PDFInfo
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- JP2004099753A JP2004099753A JP2002263779A JP2002263779A JP2004099753A JP 2004099753 A JP2004099753 A JP 2004099753A JP 2002263779 A JP2002263779 A JP 2002263779A JP 2002263779 A JP2002263779 A JP 2002263779A JP 2004099753 A JP2004099753 A JP 2004099753A
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- Prior art keywords
- butadiene rubber
- hydrogenated nitrile
- nitrile butadiene
- rubber composition
- rubber
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Links
- 229920000459 Nitrile rubber Polymers 0.000 title claims abstract description 32
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000004073 vulcanization Methods 0.000 claims abstract description 11
- 150000001451 organic peroxides Chemical class 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 229910052743 krypton Inorganic materials 0.000 claims 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052704 radon Inorganic materials 0.000 claims 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims 1
- 229910052724 xenon Inorganic materials 0.000 claims 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 11
- 230000006835 compression Effects 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 229920001971 elastomer Polymers 0.000 description 13
- 239000005060 rubber Substances 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000002825 nitriles Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 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
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000019809 paraffin wax Nutrition 0.000 description 1
- 238000010060 peroxide vulcanization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】
【産業上の利用分野】
本発明は、水素化ニトリルブタジエンゴムの成形方法に関する。さらに詳しくは、耐熱性、機械的強度（常態物性）、耐圧縮永久歪性に優れた加硫物を与え得る水素化ニトリルブタジエンゴムの製造方法に関する。
【０００２】
【従来の技術】
【特許文献１】特開平０９−３２４６号公報
水素化ニトリルブタジエンゴムは耐熱性、耐圧縮永久歪性、耐燃料油性に優れるため、Ｏリング、ガスケット、パッキンなどのシール材として、エンジン周りに多く使用されている。しかしながら、近年の高性能化、小型化、軽量化などに伴う高温化により、従来の水素化ニトリルブタジエンゴム組成物では耐熱性、耐圧縮永久歪性が不足するという新たな問題が提起されている。
一般的に行われているような空気中での二次加硫では機械的強度（常態物性）が低下し、耐圧縮永久歪性については満足し得ないという問題点が見られた。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、水素化ニトリルブタジエンゴムが本来有する機械的強度（加硫物性）や耐油性を殆んど損なうことなく、それらの状態物性、耐熱性、耐圧縮永久歪性を同時に改善せしめた有機過酸化物加硫系の水素化ニトリルブタジエンゴム組成物の製造方法を提供することにある。
【０００４】
【課題を解決するための手段】
かかる本発明の目的は、水素化ニトリルブタジエンゴムに対して、有機過酸化物を水素化ニトリルブタジエンゴム１００重量部当り、１〜２０重量部好ましくは３〜１０重量部の割合で含有してなる水素化ニトリルブタジエンゴム組成物を成形する際、不活性ガス雰囲気下、温度１５０℃〜２００℃、時間３０分〜２４時間の条件で二次加硫を行うことによって達成される。
【０００５】
【発明の実施の形態】
本発明に用いられる水素化ニトリルブタジエンゴムとは白金またはロジウム触媒などの金属によりニトリルブタジエンゴムを水素化して得られる。
一般に水素化ニトリルブタジエンゴムは、結合アクリロニトリル量が１５〜５０重量％、また、アクリロニトリルとブタジエンとの共重合ゴムまたはそこに更にエチレン性不飽和化合物を共重合させた３元共重合ゴムであるニトリルブタジエンゴムを水素添加したものである。
水素添加量の尺度として用いられるヨウ素価は１〜７０ ｇ／１００ｇ、ムーニー粘度ＭＬ１＋４＠１００℃：４０〜１６０の範囲の水素化ニトリルブタジエンゴムが一般的に用いられる。
本発明に用いられる有機過酸化物としては、ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシル）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシル）ヘキシン、１，３−ビス（ｔ−ブチルパーオキシル−イソ−プロピル）ベンゼンなどが一般的に用いられる。かかる有機過酸化物は、水素化ニトリルブタジエンゴム１００重量部当り１〜２０重量部好ましくは３〜１０重量部の割合で用いられる。有機過酸化物の配合量がこれ以下では、十分なる架橋密度の加硫物が得られず、一方これ以上の割合で用いられると、発泡して加硫成形できなかったり、あるいはそれが可能であってもゴム弾性や伸びが低下するようになる。尚、これらの過酸化物は２種類以上併用しても良い。
【０００６】
本発明に用いられるゴム組成物は、通常ゴムに用いられる配合剤を任意に配合することができる。例えば、充填剤としては、カーボンブラック、ホワイトカーボン等が用いられる。
カーボンブラックとしては、例えばオイルを不完全燃焼させて製造されるファーネスブラック、天然ガスを熱分解させて製造されるサーマルブラック等の一般に用いられているカーボンブラック等が用いられる。
ホワイトカーボン（補強性シリカ）としては、ハロゲン化けい酸または有機けい素化合物の熱分解法やけい砂を加熱還元し、気化したＳｉＯを空気酸化する方法などで製造される乾式法ホワイトカーボン、けい酸ナトリウムの熱分解法などで製造される湿式法ホワイトカーボンなどである。これらは一般にゴム工業用として上市されている市販品をそのまま用いることができる。シリカ、クレー、タルク、炭酸カルシウム、珪藻土、石英粉末などの白色充填剤系、可塑剤、老化防止剤、顔料、亜鉛華、シランカップリング剤、共架橋剤などを任意に配合することもできる。
【０００７】
組成物中には、以上の必須成分以外に、トリアリル（イソ）シアヌレート、トリメチロールプロパントリ（メタ）アクリレート、トリアリルトリメリテート、Ｎ，Ｎ′−ｍ−フェニレンビスマレイミド等の多官能性不飽和化合物を配合する事ができる。多官能性不飽和化合物は２種類以上併用しても良い。
この他、タルク、クレー、グラファイト、けい酸カルシウム等の充填剤、ステアリン酸、パルミチン酸、パラフィンワックス等の加工助剤、酸化亜鉛、酸化マグネシウム等の受酸剤、老化防止剤、可塑剤などゴム工業で一般的に用いられている各種配合剤が適宜添加されて用いられる。
本発明のゴム組成物の調製法は特に限定はなく、前記成分を添加してバンバリーミキサー、ニーダー、ロールなどの通常の混練機によって混合することにより調製することができる。
【０００８】
このようにして得られるゴム組成物は、１５０℃〜２３０℃程度の温度で約３０秒から２０分の条件で一次加硫を行うことができる。
成形方法としては、コンプレッション、インジェクション成形、トランスファー成形などがある。一次加硫後、請求項１、請求項２記載の方法・条件にて二次加硫を行うことにより、それらの状態物性、耐熱性および耐圧縮永久歪性を同時に改善せしめたゴム加硫物が得られる。
【０００９】
【発明の説明及び実施】
以下に実施例を挙げて本発明を説明するが、本発明はかかる実施例に限定されるものではない。
【００１０】
【実施例、比較例】
表１に示した配合処方でポリマー及び配合剤をニーダーまたはオープンロールにより混練りし、混練物について、１７０℃で１３分間プレス加硫、続いて１５０℃×４時間と１８０℃×２時間の２条件について、空気または窒素雰囲気中にて二次加硫を行った。
ついでＪＩＳ規格に基づき各加硫物の常態物性を測定し、その結果を併せて表１および表２に示した。ただし、圧縮永久歪の測定には試験片としてＪＩＳＰ２５Ｏリングを用いた。
【００１１】
【表１】
【表２】
【発明の効果】
かくして本発明によれば、有機過酸化物を水素化ニトリルブタジエンゴム１００重量部当り、１〜２０重量部好ましくは３〜１０重量部の割合で含有してなる有機過酸化物加硫系の水素化ニトリルブタジエンゴム組成物を１５０℃〜２３０℃程度の温度で約３０秒から２０分の条件で一次加硫後、請求項１、請求項２記載の方法・条件にて二次加硫を行うことにより、それの状態物性、耐熱性および耐圧縮永久歪性を同時に改善することができる。
従って、本発明に係る水素化ＮＢＲ組成物は、〜１５０℃といった温度条件下で使用されるシール部品、例えばＯリング、ガスケット、パッキン、オイルシール等の成形材料として有効に用いられる。
また、これらの製造方法は水素化ニトリルブタジエンゴム以外の有機化酸化物を用いて加硫可能な全てのゴム、エチレンプロピレンゴム、エチレンプロピレン系共重合ゴム、ブチルゴム、アクリロニトリルブタジエンゴム、シリコーンゴム、フロロシリコーンゴム、フッ素ゴム、ウレタンゴム、スチレンブタジエンゴム、ブタジエンゴム、イソプレンゴム、クロロプレンゴム、ジエン系ゴム、エチレン−酢ビ共重合体、塩素化ポリエチレン、ポリエチレン等に適用可能である。[0001]
[Industrial application fields]
The present invention relates to a method for molding hydrogenated nitrile butadiene rubber. More specifically, the present invention relates to a method for producing a hydrogenated nitrile butadiene rubber capable of providing a vulcanizate having excellent heat resistance, mechanical strength (normal physical properties), and compression set resistance.
[0002]
[Prior art]
[Patent Document 1] Japanese Patent Application Laid-Open No. 09-3246 Hydrogenated nitrile butadiene rubber is excellent in heat resistance, compression set resistance, and fuel oil resistance. Therefore, it is often used as a sealing material for O-rings, gaskets, packings, etc. in use. However, due to high temperatures accompanying recent high performance, miniaturization, weight reduction, etc., new problems have been raised that conventional hydrogenated nitrile butadiene rubber compositions lack heat resistance and compression set resistance. .
In general, secondary vulcanization in air has a problem that the mechanical strength (normal physical properties) is lowered and the compression set resistance cannot be satisfied.
[0003]
[Problems to be solved by the invention]
The object of the present invention is to improve the physical properties, heat resistance, and compression set resistance at the same time without substantially impairing the mechanical strength (vulcanized physical properties) and oil resistance inherent in hydrogenated nitrile butadiene rubber. Another object of the present invention is to provide a method for producing an organic peroxide vulcanized hydrogenated nitrile butadiene rubber composition.
[0004]
[Means for Solving the Problems]
The object of the present invention is to contain an organic peroxide in a proportion of 1 to 20 parts by weight, preferably 3 to 10 parts by weight per 100 parts by weight of the hydrogenated nitrile butadiene rubber, relative to the hydrogenated nitrile butadiene rubber. When the hydrogenated nitrile butadiene rubber composition is molded, secondary vulcanization is performed under conditions of a temperature of 150 ° C. to 200 ° C. and a time of 30 minutes to 24 hours in an inert gas atmosphere.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The hydrogenated nitrile butadiene rubber used in the present invention is obtained by hydrogenating nitrile butadiene rubber with a metal such as platinum or rhodium catalyst.
Generally, hydrogenated nitrile butadiene rubber is a nitrile which has a bound acrylonitrile amount of 15 to 50% by weight and is a terpolymer rubber obtained by copolymerizing acrylonitrile and butadiene or further copolymerizing an ethylenically unsaturated compound therewith. This is a hydrogenated butadiene rubber.
A hydrogenated nitrile butadiene rubber having an iodine value of 1 to 70 g / 100 g and Mooney viscosity ML1 + 4 @ 100 ° C .: 40 to 160 is generally used as a measure of the amount of hydrogenation.
Examples of the organic peroxide used in the present invention include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxyl) hexane, 2,5-dimethyl-2,5-di (t -Butylperoxyl) hexyne, 1,3-bis (t-butylperoxyl-iso-propyl) benzene and the like are generally used. Such organic peroxide is used in a proportion of 1 to 20 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the hydrogenated nitrile butadiene rubber. If the amount of the organic peroxide is less than this, a vulcanizate having a sufficient crosslinking density cannot be obtained. On the other hand, if it is used in a proportion higher than this, it cannot foam or cannot be vulcanized. Even if it exists, rubber elasticity and elongation come to fall. Two or more of these peroxides may be used in combination.
[0006]
In the rubber composition used in the present invention, a compounding agent usually used for rubber can be arbitrarily blended. For example, carbon black, white carbon or the like is used as the filler.
Examples of the carbon black include commonly used carbon black such as furnace black produced by incomplete combustion of oil and thermal black produced by pyrolyzing natural gas.
White carbon (reinforcing silica) includes dry-type white carbon produced by pyrolysis of halogenated silicic acid or organosilicon compounds, heat reduction of silica sand, and air oxidation of vaporized SiO. Wet white carbon produced by thermal decomposition of sodium acid. These can be used as they are in the market for the rubber industry. White filler systems such as silica, clay, talc, calcium carbonate, diatomaceous earth, and quartz powder, plasticizers, anti-aging agents, pigments, zinc white, silane coupling agents, co-crosslinking agents, and the like can be optionally blended.
[0007]
In the composition, in addition to the above essential components, polyfunctional non-functional compounds such as triallyl (iso) cyanurate, trimethylolpropane tri (meth) acrylate, triallyl trimellitate, N, N′-m-phenylenebismaleimide and the like. A saturated compound can be blended. Two or more polyfunctional unsaturated compounds may be used in combination.
In addition, rubber such as fillers such as talc, clay, graphite, calcium silicate, processing aids such as stearic acid, palmitic acid, paraffin wax, acid acceptors such as zinc oxide and magnesium oxide, anti-aging agents, plasticizers, etc. Various compounding agents generally used in industry are appropriately added and used.
The method for preparing the rubber composition of the present invention is not particularly limited, and the rubber composition can be prepared by adding the above components and mixing them with an ordinary kneader such as a Banbury mixer, a kneader, or a roll.
[0008]
The rubber composition thus obtained can be subjected to primary vulcanization at a temperature of about 150 ° C. to 230 ° C. for about 30 seconds to 20 minutes.
Examples of the molding method include compression, injection molding, transfer molding, and the like. After the primary vulcanization, a rubber vulcanizate in which the physical properties, heat resistance and compression set resistance are improved at the same time by performing secondary vulcanization according to the method and conditions described in claims 1 and 2 Is obtained.
[0009]
Description and practice of the invention
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to such examples.
[0010]
[Examples and comparative examples]
The polymer and the compounding agent are kneaded with a kneader or an open roll with the compounding formulation shown in Table 1, and the kneaded product is press vulcanized at 170 ° C. for 13 minutes, followed by 150 ° C. × 4 hours and 180 ° C. × 2 hours 2 Regarding conditions, secondary vulcanization was performed in an air or nitrogen atmosphere.
Next, normal properties of each vulcanizate were measured based on JIS standards, and the results are also shown in Tables 1 and 2. However, a JISP25O ring was used as a test piece for measurement of compression set.
[0011]
[Table 1]
[Table 2]
【The invention's effect】
Thus, according to the present invention, an organic peroxide vulcanization system hydrogen comprising an organic peroxide in an amount of 1 to 20 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of hydrogenated nitrile butadiene rubber. After the primary vulcanization of the nitrile butadiene rubber composition at a temperature of about 150 ° C. to 230 ° C. for about 30 seconds to 20 minutes, secondary vulcanization is performed using the method and conditions of claim 1 and claim 2. As a result, the physical properties, heat resistance and compression set resistance thereof can be improved at the same time.
Therefore, the hydrogenated NBR composition according to the present invention is effectively used as a molding material for seal parts, for example, O-rings, gaskets, packings, oil seals, etc. used under temperature conditions of ˜150 ° C.
In addition, these production methods include all rubbers that can be vulcanized using an organic oxide other than hydrogenated nitrile butadiene rubber, ethylene propylene rubber, ethylene propylene copolymer rubber, butyl rubber, acrylonitrile butadiene rubber, silicone rubber, fluoro It can be applied to silicone rubber, fluorine rubber, urethane rubber, styrene butadiene rubber, butadiene rubber, isoprene rubber, chloroprene rubber, diene rubber, ethylene-vinyl acetate copolymer, chlorinated polyethylene, polyethylene and the like.
Claims (3)
前記水素化ニトリルブタジエンゴム組成物を樹脂化インテークマニホールド等のシール、ガスケットに用いることを特徴とした水素化ニトリルブタジエンゴム組成物の製造方法。For hydrogenated nitrile butadiene rubber vulcanized using organic peroxide, secondary vulcanization is performed in an inert gas to form a hydrogenated nitrile butadiene rubber composition,
A method for producing a hydrogenated nitrile butadiene rubber composition, wherein the hydrogenated nitrile butadiene rubber composition is used for a seal or gasket of a resinated intake manifold or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002263779A JP3786636B2 (en) | 2002-09-10 | 2002-09-10 | Method for producing hydrogenated nitrile butadiene rubber composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002263779A JP3786636B2 (en) | 2002-09-10 | 2002-09-10 | Method for producing hydrogenated nitrile butadiene rubber composition |
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| Publication Number | Publication Date |
|---|---|
| JP2004099753A true JP2004099753A (en) | 2004-04-02 |
| JP3786636B2 JP3786636B2 (en) | 2006-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2002263779A Expired - Fee Related JP3786636B2 (en) | 2002-09-10 | 2002-09-10 | Method for producing hydrogenated nitrile butadiene rubber composition |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007094158A1 (en) * | 2006-02-17 | 2007-08-23 | Nok Corporation | Hydrogenated nbr composition |
| WO2007094447A1 (en) * | 2006-02-17 | 2007-08-23 | Nok Corporation | Hydrogenated nbr compositions |
| US20180016423A1 (en) * | 2015-02-16 | 2018-01-18 | Zeon Corporation | Cross-linked rubber product |
| CN108084351A (en) * | 2017-12-15 | 2018-05-29 | 江苏铁科新材料股份有限公司 | Endless-track vehicle bushing rubber material |
| CN113234325A (en) * | 2021-06-08 | 2021-08-10 | 山东非金属材料研究所 | Wide-temperature-range medium-resistant rubber composite material and preparation method thereof |
| CN114203383A (en) * | 2021-12-15 | 2022-03-18 | 大地熊（苏州）磁铁有限公司 | High-temperature-resistant heat-conducting rubber magnet and preparation method thereof |
| CN114736441A (en) * | 2022-05-10 | 2022-07-12 | 山东道恩特种弹性体材料有限公司 | HNBR (hydrogenated nitrile butadiene rubber) rubber compound for dynamic diaphragm sealing element of oil pump |
-
2002
- 2002-09-10 JP JP2002263779A patent/JP3786636B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007094158A1 (en) * | 2006-02-17 | 2007-08-23 | Nok Corporation | Hydrogenated nbr composition |
| WO2007094447A1 (en) * | 2006-02-17 | 2007-08-23 | Nok Corporation | Hydrogenated nbr compositions |
| US7772305B2 (en) | 2006-02-17 | 2010-08-10 | Nok Corporation | Hydrogenated NBR composition |
| JP5141548B2 (en) * | 2006-02-17 | 2013-02-13 | Ｎｏｋ株式会社 | Hydrogenated NBR composition |
| US20180016423A1 (en) * | 2015-02-16 | 2018-01-18 | Zeon Corporation | Cross-linked rubber product |
| US10005895B2 (en) * | 2015-02-16 | 2018-06-26 | Zeon Corporation | Cross-linked rubber product |
| CN108084351A (en) * | 2017-12-15 | 2018-05-29 | 江苏铁科新材料股份有限公司 | Endless-track vehicle bushing rubber material |
| CN113234325A (en) * | 2021-06-08 | 2021-08-10 | 山东非金属材料研究所 | Wide-temperature-range medium-resistant rubber composite material and preparation method thereof |
| CN114203383A (en) * | 2021-12-15 | 2022-03-18 | 大地熊（苏州）磁铁有限公司 | High-temperature-resistant heat-conducting rubber magnet and preparation method thereof |
| CN114736441A (en) * | 2022-05-10 | 2022-07-12 | 山东道恩特种弹性体材料有限公司 | HNBR (hydrogenated nitrile butadiene rubber) rubber compound for dynamic diaphragm sealing element of oil pump |
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