JP5577600B2 - EPDM composition - Google Patents
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- JP5577600B2 JP5577600B2 JP2009022167A JP2009022167A JP5577600B2 JP 5577600 B2 JP5577600 B2 JP 5577600B2 JP 2009022167 A JP2009022167 A JP 2009022167A JP 2009022167 A JP2009022167 A JP 2009022167A JP 5577600 B2 JP5577600 B2 JP 5577600B2
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- 229920002943 EPDM rubber Polymers 0.000 title claims description 22
- 239000000203 mixture Substances 0.000 title claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 29
- 239000000460 chlorine Substances 0.000 claims description 29
- 229910052801 chlorine Inorganic materials 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 230000006835 compression Effects 0.000 claims description 12
- 238000007906 compression Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000001451 organic peroxides Chemical class 0.000 claims description 9
- 239000003566 sealing material Substances 0.000 claims description 8
- 239000012778 molding material Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000010419 fine particle Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000000565 sealant Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004073 vulcanization Methods 0.000 description 17
- 229920001971 elastomer Polymers 0.000 description 12
- 238000007789 sealing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000010866 blackwater Substances 0.000 description 2
- -1 butyl peroxy Chemical group 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- 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
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-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
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical group CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- PMAAOHONJPSASX-UHFFFAOYSA-N 2-butylperoxypropan-2-ylbenzene Chemical group CCCCOOC(C)(C)C1=CC=CC=C1 PMAAOHONJPSASX-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010721 machine oil Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000001057 purple pigment Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Gasket Seals (AREA)
Description
本発明は、EPDM組成物に関する。さらに詳しくは、塩素含有水溶液接触シール材の加硫成形材料等として有効に用いられるEPDM組成物に関する。 The present invention relates to EPDM compositions. More specifically, the present invention relates to an EPDM composition that is effectively used as a vulcanization molding material for a chlorine-containing aqueous solution contact sealing material.
エチレン・プロピレン共重合ゴム(EPM)またはエチレン・プロピレン・ジエン共重合ゴム(EPDM)であるエチレン・プロピレン系共重合ゴムは、それら本来が有するすぐれた耐熱性、低温特性、耐水性などにより、耐熱性あるいは耐水性のシール材の加硫成形材料等として幅広く用いられている(特許文献１参照)。 Ethylene / propylene copolymer rubber (EPM) or ethylene / propylene / diene copolymer rubber (EPDM) is an ethylene / propylene copolymer rubber that has excellent heat resistance, low temperature characteristics, and water resistance. It is widely used as a vulcanization molding material for water-resistant or water-resistant sealing materials (see Patent Document 1).
しかるに近年にあっては、水周り関連、例えばガス給湯器、電気温水器、エコキュート等の普及による水の高温化、あるいは水質悪化が原因となる塩素による殺菌力強化に伴う残留塩素の高濃度化などにより、従来のエチレン・プロピレン系共重合ゴム組成物では、耐水性、耐塩素水性、シール性など、特にシール性が不足するという新たな問題が提起されている。 However, in recent years, the concentration of residual chlorine has increased due to the increase in water temperature due to the spread of water heaters, such as gas water heaters, electric water heaters, eco-cutes, etc. As a result, the conventional ethylene / propylene copolymer rubber composition has been posed with a new problem that the sealing properties such as water resistance, chlorine water resistance, and sealing properties are particularly insufficient.
より具体的には、カーボンブラックの脱落により黒水化、ゴム表面の面荒れ、膨潤によるシール不具合、耐圧縮永久歪特性の低下によるシール性の悪化などが挙げられる。 More specifically, black water is removed by dropping off the carbon black, the surface of the rubber is rough, a sealing failure is caused by swelling, and a sealing property is deteriorated due to a decrease in compression set characteristics.
本発明の目的は、耐熱性、シール性、耐塩素水性にすぐれ、特に高温・高濃度(塩素濃度200ppm以上)の塩素含有水溶液接触シール材の加硫成形材料等として有効に用いられるEPDM組成物を提供することにある。 An object of the present invention is an EPDM composition that is excellent in heat resistance, sealing properties, and chlorine water resistance, and that is effectively used as a vulcanization molding material for contact seal materials containing chlorine at a high temperature and high concentration (chlorine concentration of 200 ppm or more) . Is to provide.
かかる本発明の目的は、EPDM100重量部当りBET比表面積(ASTM D1993-03準拠)が30〜110m2/gで、pHが9.0以下の微粒子状シリカ15〜70重量部、ビニル基含有シランカップリング剤0.5〜5重量部、有機過酸化物1〜8重量部および多官能性不飽和化合物共架橋剤0.5〜5重量部を含有し、カーボンブラックを含有しない、塩素濃度200ppm以上の塩素含有水溶液接触シール材の加硫成形材料として用いられるEPDM組成物によって達成される。 The object of the present invention is to provide 15 to 70 parts by weight of fine particle silica having a BET specific surface area (according to ASTM D1993-03) of 30 to 110 m 2 / g and a pH of 9.0 or less per 100 parts by weight of EPDM, and a vinyl group-containing silane coupling. Contains 0.5 to 5 parts by weight of an agent, 1 to 8 parts by weight of an organic peroxide and 0.5 to 5 parts by weight of a polyfunctional unsaturated compound co-crosslinking agent , does not contain carbon black, and comes into contact with a chlorine-containing aqueous solution having a chlorine concentration of 200 ppm or more This is achieved by an EPDM composition used as a vulcanization molding material for a sealing material.
本発明に係るEPDM組成物から加硫成形して得られたシール材、例えばOリング、Dリング、Xリング、ガスケット、パッキン等は、耐熱性、シール性、耐塩素水性にすぐれ、特に高温・高濃度(塩素濃度200ppm以上)の塩素含有水溶液接触シール材として、例えばガス給湯器、電気温水器、エコキュート等の水周り関連の器具シール材として有効に用いられる。 Seal materials obtained by vulcanization molding from the EPDM composition according to the present invention, such as O-rings, D-rings, X-rings, gaskets, packings, etc., are excellent in heat resistance, sealing properties, and chlorine water resistance, especially at high temperatures. As a chlorine-containing aqueous solution contact sealing material with a high concentration (chlorine concentration of 200 ppm or more) , for example, it is effectively used as a water-related device sealing material such as a gas water heater, an electric water heater, and Ecocute.
本出願人は先に、エチレン・プロピレン系共重合ゴム100重量部当り、比表面積が50〜200m2/gのホワイトカーボン20〜80重量部および有機過酸化物1〜8重量部を含有するエチレン・プロピレン系共重合ゴム組成物を提案しており、該組成物はシール材の成形材料として、具体的にはハイドロフルオロカーボンまたはそれに適用可能な冷凍機油(ポリアルキレングリコール、ポリカーボネート等)に接触するシール材の成形材料として、さらに具体的にはエアコン用スクイーズパッキンの成形材料として用いられるとされているが、高温・高濃度の塩素含有水溶液接触シール材として用いることは意図されていない(特許文献２参照)。 The present applicant has previously described ethylene containing 20 to 80 parts by weight of white carbon having a specific surface area of 50 to 200 m 2 / g and 1 to 8 parts by weight of organic peroxide per 100 parts by weight of ethylene / propylene copolymer rubber. Propylene-based copolymer rubber composition has been proposed, and the composition is a seal material in contact with hydrofluorocarbon or a refrigerating machine oil (polyalkylene glycol, polycarbonate, etc.) applicable to it as a molding material for the seal material. More specifically, it is said to be used as a molding material for a squeeze packing for an air conditioner, but is not intended to be used as a high - temperature , high-concentration chlorine-containing aqueous solution contact sealing material (Patent Document 2). reference).
本出願人はまた、EPDMへの有機過酸化物促入れ工程において、粉塵が舞う不具合がなく、かつ促入れ時間が短縮され、さらにはマスターバッチ自体の加工性にもすぐれた有機過酸化物マスターバッチとして、有機過酸化物20〜60重量％、EPDM10〜15重量％および窒素BET法での比表面積が50〜130m2/gで、かつ平均二次粒子径が10〜20μmのシリカ10〜50重量％を含有してなるマスターバッチを提案しているが、この提案ではマスターバッチの調製にとどまっている(特許文献３参照)。 The present applicant has also found that an organic peroxide master that has no defects that cause dust in the process of urging organic peroxide into EPDM, that the accelerating time is shortened, and that the master batch itself is excellent in workability. As a batch, 10 to 50 wt% organic peroxide, 10 to 15 wt% EPDM, and 10 to 50 wt% silica with a specific surface area of 50 to 130 m 2 / g in nitrogen BET method and an average secondary particle size of 10 to 20 μm A masterbatch containing% by weight is proposed, but this proposal is limited to the preparation of the masterbatch (see Patent Document 3).
ポリマーとしては、耐熱性、耐水性、耐圧縮永久歪特性の点から、5-エチリデン-2-ノルボルネン(ENB)、ジシクロペンタジエン、1,4-ヘキサジエン等の任意のジエンを共重合させたEPDMが用いられる。ポリマー中にジエン成分を含まないEPMでは、耐熱性や耐水性にはすぐれているが、EPDMと比較して加硫速度が遅く、生産性に劣るばかりではなく、耐圧縮永久歪特性の点でも劣っている(後記比較例１０参照)。 As a polymer, EPDM copolymerized with any diene such as 5-ethylidene-2-norbornene (ENB), dicyclopentadiene, 1,4-hexadiene from the viewpoint of heat resistance, water resistance and compression set resistance. Is used. EPM that does not contain a diene component in the polymer is excellent in heat resistance and water resistance, but has a slower vulcanization speed and lower productivity than EPDM, as well as in terms of compression set resistance. Inferior (see Comparative Example 10 below).
補強材としては、一般的に用いられているカーボンブラックを用いるとそれの脱落により黒水化が生ずるので好ましくなく、微粒子状のシリカSiO2・nH2Oが用いられる。微粒子状のシリカとしては、BET比表面積(ASTM D-1993-03準拠)が30〜110m 2 /gであり、pHが9.0以下、好ましくは5.0〜8.5のものが、EPDM100重量部当り約15〜70重量部、好ましくは約20〜60重量部の割合で用いられる。 As the reinforcing material, if carbon black which is generally used is used, it is not preferable because black water is generated due to dropping off, and particulate silica SiO 2 · nH 2 O is used. The fine particle silica has a BET specific surface area (according to ASTM D- 1993-03 ) of 30 to 110 m 2 / g and a pH of 9.0 or less, preferably 5.0 to 8.5, about 15 to 100 parts by weight of EPDM. It is used in a proportion of 70 parts by weight, preferably about 20-60 parts by weight.
比表面積がこれよりも大きいシリカを用いると、ゴムコンパウンドの粘度上昇により混練加工性が悪化傾向となるばかりではなく、耐熱性、耐圧縮永久歪特性、耐塩素水性も悪化傾向となる(比較例１参照)。一方、これよりも小さい比表面積のシリカを用いると、補強性が低下するばかりではなく、耐熱性、耐塩素水性も低下するようになる(比較例３〜４参照)。また、比表面積が規定された範囲内にあっても、pH(2重量％水溶液として測定)が9.0を超えるシリカを用いると、耐塩素水性が悪化するようになる(比較例２参照)。 When silica with a specific surface area larger than this is used, not only kneading processability tends to deteriorate due to an increase in the viscosity of the rubber compound, but heat resistance, compression set resistance, and chlorine water resistance also tend to deteriorate (Comparative Example). 1). On the other hand, when silica having a specific surface area smaller than this is used, not only the reinforcing property is lowered, but also the heat resistance and the chlorine water resistance are lowered (see Comparative Examples 3 to 4). Even if the specific surface area is within the specified range, the use of silica having a pH (measured as a 2% by weight aqueous solution) of more than 9.0 will deteriorate the chlorine-resistant water resistance (see Comparative Example 2).
また、シリカがこれ以上の配合割合で用いられると、ゴムコンパウンドの粘度上昇によって混練が困難となり、混練できても得られる加硫成形品は硬くなり、一方これよりも少ない割合で用いられると、強度、耐塩素水性の改善効果が得られない(比較例５〜６参照)。 Further, when silica is used at a higher blending ratio, kneading becomes difficult due to an increase in the viscosity of the rubber compound, and the vulcanized molded product obtained even if kneaded can be hardened, whereas when used at a smaller ratio, The effect of improving strength and chlorine water resistance cannot be obtained (see Comparative Examples 5 to 6).
シランカップリング剤としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニル基含有アルコキシシランが用いられる。 Examples of the silane coupling agent include vinyl trimethoxysilane, vinyl group-containing alkoxysilanes such as vinyltriethoxysilane used.
シランカップリング剤は、EPDM100重量部当り約0.5〜5重量部、好ましくは約0.5〜2重量部の割合で用いられる。この使用割合がこれよりも少ないと、耐圧縮永久歪特性や耐塩素水性が劣るようになり(比較例９参照)、一方これよりも多く使用しても、耐圧縮永久歪特性は向上せず、生地のスコーチやコストアップの問題を生ずる。 The silane coupling agent is used at a ratio of about 0.5 to 5 parts by weight, preferably about 0.5 to 2 parts by weight per 100 parts by weight of EPDM. If the ratio is less than this, the compression set resistance and chlorine water resistance are inferior (see Comparative Example 9). On the other hand, using more than this does not improve the compression set resistance. , Causing problems of scorch of fabric and cost increase.
加硫剤としては、有機過酸化物、例えば第3ブチルパーオキサイド、ジクミルパーオキサイド、第3ブチルクミルパーオキサイド、1,1-ジ(第3ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、2,5-ジメチル-2,5-ジ(第3ブチルパーオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(第3ブチルパーオキシ)ヘキシン-3、1,3-ジ(第3ブチルパーオキシイソプロピル)ベンゼン、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、第3ブチルパーオキシベンゾエート、第3ブチルパーオキシイソプロピルカーボネート、n-ブチル-4,4-ジ(第3ブチルパーオキシ)バレレート等が用いられる。 Examples of vulcanizing agents include organic peroxides such as tertiary butyl peroxide, dicumyl peroxide, tertiary butyl cumyl peroxide, 1,1-di (tertiary butyl peroxy) -3,3,5-trimethyl. Cyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-di ( Tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, n-butyl-4,4- Di (tertiary butyl peroxy) valerate or the like is used.
これらの有機過酸化物は、EPDM100重量部当り約1〜8重量部、好ましくは約2〜7重量部の割合で用いられる。これ以下の配合割合では、十分な架橋密度が得られず、耐熱性や耐圧縮永久歪特性、耐塩素水性が劣るようになり、一方これ以上の割合で用いられると、発泡により加硫成形品が得られなくなる(比較例７〜８参照)。また、加硫系を硫黄系にした場合には、圧縮永久歪の値が非常に悪くなり、長期のシール性に問題が生じるようになる(比較例１１参照)。 These organic peroxides are used in a ratio of about 1 to 8 parts by weight, preferably about 2 to 7 parts by weight, per 100 parts by weight of EPDM. If the blending ratio is less than this, a sufficient crosslinking density cannot be obtained, and the heat resistance, compression set resistance and chlorine water resistance become poor. Cannot be obtained (see Comparative Examples 7 to 8). In addition, when the vulcanization system is a sulfur system, the compression set value becomes very bad, and a problem arises in long-term sealing properties (see Comparative Example 11).
また、加硫特性を向上させるため、有機過酸化物と共に、トリアリルシアヌレート、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クリレート、N,N′-m-フェニレンジマレイミド等の共架橋剤(多官能性不飽和化合物)を約0.5〜5重量部の範囲で併用することが好ましく、共架橋剤が用いられない場合には、加硫速度の低下により生産効率の悪化や、加硫が十分に行われないことから、ジエン成分中の二重結合が多く残り、耐塩素水性や耐圧縮永久歪特性の悪化などの問題が生じることがある。 In addition to organic peroxides, co-crosslinking agents such as triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, N, N'-m-phenylene dimaleimide (polyfunctional) In the range of about 0.5 to 5 parts by weight, and when a co-crosslinking agent is not used, production efficiency is deteriorated due to a decrease in the vulcanization rate, and vulcanization is sufficiently performed. In other words, a large number of double bonds remain in the diene component, which may cause problems such as deterioration in chlorine water resistance and compression set resistance.
組成物中には、以上の各成分以外に、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2価金属の酸化物または水酸化物、ハイドロタルサイトなどの受酸剤、可塑剤、老化防止剤など、ゴム工業で一般的に用いられている配合剤が、物性を損ねない範囲で適宜添加されて用いられる。 In addition to the above components, the composition includes processing aids such as stearic acid, palmitic acid, paraffin wax, oxides or hydroxides of divalent metals such as zinc oxide and magnesium oxide, hydrotalcite, etc. A compounding agent generally used in the rubber industry, such as an acid acceptor, a plasticizer, and an anti-aging agent, is appropriately added and used as long as the physical properties are not impaired.
ゴム組成物の調製は、インターミックス、ニーダ、バンバリーミキサ等の混練機またはオープンロールなどを用いて混練することによって行われ、それの加硫は加硫プレス、圧縮成形機、射出成形機等を用いて、一般に約150〜220℃に約1〜60分間程度加熱することによって行われる。さらに必要に応じて、約120〜200℃で約1〜24時間オーブン加硫(二次加硫)することも行われる。 The rubber composition is prepared by kneading using a kneader such as an intermix, kneader, Banbury mixer or an open roll, and the vulcanization is performed using a vulcanizing press, compression molding machine, injection molding machine, etc. In general, it is carried out by heating to about 150 to 220 ° C. for about 1 to 60 minutes. Further, if necessary, oven vulcanization (secondary vulcanization) is also performed at about 120 to 200 ° C. for about 1 to 24 hours.
次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
実施例１
EPDM(JSR製品EP33；エチレン含量52重量％、ENB含量8.1重量％) 100重量部
シリカ(東ソーシリカ製品ニップシールE74P； 35 〃
BET比表面積30〜50m2/g、pH6〜8)
紫色顔料(レジノカラー工業製品NST-5944) 1.6 〃
酸化亜鉛 5.0 〃
ステアリン酸 0.5 〃
老化防止剤(ペンタエリスリチル-テトラキス〔3-(3,5-ジ 1.5 〃
第3ブチル-4-ヒドロキシフェニル)プロピオネート〕)
老化防止剤(2-メルカプトベンツイミダゾール) 1.0 〃
ビニル系シランカップリング剤(モメンティブ製品A172) 1.0 〃
パラフィン系プロセスオイル(出光興産製品PW380) 5.0 〃
トリアリルイソシアヌレート(日本化成製品タイク) 1.0 〃
ジクミルパーオキサイド 3.0 〃
以上の各成分の内、ジクミルパーオキサイドおよびトリアリルイソシアヌレートを除く各成分を加圧ニーダで混練した後、ゴムコンパウンドを排出し、オープンロールを用いてジクミルパーオキサイドおよびトリアリルイソシアヌレートを混合し、EPDM組成物を調製した。
Example 1
EPDM (JSR product EP33; ethylene content 52% by weight, ENB content 8.1% by weight) 100 parts by weight Silica (Tosoh silica product nip seal E74P; 35 〃
(BET specific surface area 30-50m 2 / g, pH 6-8)
Purple pigment (Resino color industrial product NST-5944) 1.6 〃
Zinc oxide 5.0 〃
Stearic acid 0.5 〃
Anti-aging agent (pentaerythrityl-tetrakis [3- (3,5-di 1.5 〃
Tert-butyl-4-hydroxyphenyl) propionate])
Anti-aging agent (2-mercaptobenzimidazole) 1.0 〃
Vinyl silane coupling agent (momentive product A172) 1.0 〃
Paraffinic process oil (Idemitsu Kosan product PW380) 5.0 〃
Triallyl isocyanurate (Nippon Kasei products Thaike) 1.0 〃
Dicumyl peroxide 3.0 〃
Among the above components, each component except dicumyl peroxide and triallyl isocyanurate is kneaded with a pressure kneader, then the rubber compound is discharged, and dicumyl peroxide and triallyl isocyanurate are used using an open roll. Mixed to prepare an EPDM composition.
このEPDM組成物について、180℃、6分間のプレス加硫および150℃、15時間のオーブン加硫(二次加硫)を行い、テストピース(150×150×2mm)およびOリング(線径3.1mm)を作製した。これらを用い、次の各項目の測定または評価を行った。
常態物性：JIS K6253、6251準拠
また、テストピースの状態を目視で観察し、良好なものを○と評価した
圧縮永久歪：Oリングについて、150℃、70時間の値を測定
空気加熱老化試験：150℃、70時間後の硬さ変化を測定
耐塩素水性試験：塩素濃度200ppmまたは1000ppm、80℃の次亜塩素酸ナトリウム
水溶液中に500時間浸せきした後の硬さ変化および体積変化率を
測定
なお、水溶液は１日毎に液交換を行った
また、浸せき後の状態を目視で観察し、良好なものを○、面荒れ
ありを×と評価
This EPDM composition was subjected to press vulcanization at 180 ° C. for 6 minutes and oven vulcanization (secondary vulcanization) at 150 ° C. for 15 hours, and a test piece (150 × 150 × 2 mm) and an O-ring (wire diameter 3.1) mm). Using these, the following items were measured or evaluated.
Normal physical properties: JIS K6253, 6251 compliant
In addition, the state of the test piece was visually observed, and a good one was evaluated as ○. Compression set: O-ring was measured at 150 ° C for 70 hours. Air heat aging test: Hardness after 150 ° C for 70 hours Chlorine water resistance test: Chlorine concentration 200ppm or 1000ppm, 80 ℃ sodium hypochlorite
Hardness change and volume change rate after immersion in aqueous solution for 500 hours
Measurement
The aqueous solution was changed every day.
Also, visually observe the condition after soaking, ○
Evaluate Yes
実施例２
実施例１において、シリカとして東ソーシリカ製品ニップシールER(BET比表面積70〜110m2/g、pH7.5〜9)30重量部が用いられた。
Example 2
In Example 1, 30 parts by weight of Tosoh silica product nip seal ER ( BET specific surface area 70 to 110 m 2 / g, pH 7.5 to 9) was used as silica.
比較例１
実施例１において、シリカとして東ソーシリカ製品ニップシールLP(BET比表面積170〜220m2/g、pH5.5〜6.5)30重量部が用いられた。混練性には、悪化傾向がみられた。
Comparative Example 1
In Example 1, 30 parts by weight of Tosoh silica product nip seal LP ( BET specific surface area 170-220 m 2 / g, pH 5.5-6.5) was used as silica. There was a tendency for the kneadability to deteriorate.
比較例２
実施例１において、シリカとして塩野義製薬製品カープレックス1120(BET比表面積150m2/g、pH10.6)30重量部が用いられた。
Comparative Example 2
In Example 1, 30 parts by weight of Shionogi Pharmaceutical product Carplex 1120 ( BET specific surface area 150 m 2 / g, pH 10.6) was used as silica.
比較例３
実施例１において、シリカの代りに炭酸カルシウム(白石工業製品白艶華CC；BET比表面積23〜29m2/g、pH8.5〜9.5)が55重量部用いられた。
Comparative Example 3
In Example 1, instead of silica, 55 parts by weight of calcium carbonate (Shiraishi Kogyo Hakucho CC; BET specific surface area 23 to 29 m 2 / g, pH 8.5 to 9.5) was used.
比較例４
実施例１において、シリカの代りにカオリンクレー(ケンタッキー・テネシィ クレイ社製品ニューロック321；BET比表面積22〜26m2/g、pH7〜8)が50重量部用いられた。
Comparative Example 4
In Example 1, 50 parts by weight of kaolin clay (Kentucky Tennessee Clay product Newlock 321; BET specific surface area of 22 to 26 m 2 / g, pH 7 to 8) was used instead of silica.
比較例５
実施例１において、シリカ量が10重量部に変更された。
Comparative Example 5
In Example 1, the amount of silica was changed to 10 parts by weight.
比較例６
実施例１において、シリカ量が90重量部に変更された。混練性は、悪であった。
Comparative Example 6
In Example 1, the amount of silica was changed to 90 parts by weight. The kneadability was bad.
比較例７
実施例１において、ジクミルパーオキサイド量が0.5重量部に変更された。
Comparative Example 7
In Example 1, the amount of dicumyl peroxide was changed to 0.5 parts by weight.
比較例８
実施例１において、ジクミルパーオキサイド量が9.0重量部に変更された。成形時に発泡し、成形できなかった。
Comparative Example 8
In Example 1, the amount of dicumyl peroxide was changed to 9.0 parts by weight. Foamed during molding and could not be molded.
比較例９
実施例１において、ビニル系シランカップリング剤が用いられなかった。
Comparative Example 9
In Example 1, no vinyl-based silane coupling agent was used.
比較例１０
実施例１において、EPDMの代りにEPM(JSR製品EP11；エチレン含量52重量％)100重量部が用いられ、それのプレス加硫時間が10分間に変更された。
Comparative Example 10
In Example 1, 100 parts by weight of EPM (JSR product EP11; ethylene content 52% by weight) was used instead of EPDM, and its press vulcanization time was changed to 10 minutes.
比較例１１
実施例１において、ジクミルパーオキサイド-トリアリルイソシアヌレートよりなるパーオキサイド加硫系の代りに、硫黄1.5重量部、チウラム系促進剤TMTD 1.0重量部およびチアゾール系促進剤MBT 0.5重量部よりなる硫黄加硫系が用いられた。
Comparative Example 11
In Example 1, instead of the peroxide vulcanization system comprising dicumyl peroxide-triallyl isocyanurate, sulfur comprising 1.5 parts by weight of sulfur, 1.0 part by weight of thiuram accelerator TMTD and 0.5 part by weight of thiazole accelerator MBT A vulcanization system was used.
以上の各実施例および比較例(比較例８を除く)における測定結果または評価結果は、次の表に示される。
表
実施例 比較例
測定・評価項目 １ ２ １ ２ ３ ４ ５ ６ ７ ９ 10 11
常態物性
硬さ (Duro A) 63 64 67 61 60 62 53 97 54 57 60 63
引張強さ (MPa) 13.6 11.6 13.5 9.9 7.6 8.8 4.2 12.3 6.7 11 12 11
伸び (％) 220 260 200 300 280 260 170 40 780 380 280 480
テストピース状態 ○ ○ ○ ○ ○ ○ ○ 高 未加 ○ ○ ○
硬度 硫気味
圧縮永久歪
150℃、70hrs (％) 10 18 20 17 37 26 21 45 58 38 24 88
空気加熱老化試験
硬さ変化(ポイント) 0 +1 +3 +1 +6 +2 +3 +4 +5 +5 0 6
耐塩素水性試験
硬さ変化(ポイント)
塩素200ppm -3 -2 -2 -1 -4 -6 -2 ／ -3 -3 -2 -5
〃 1000ppm -2 -1 -2 -1 -4 -7 -2 ／ -2 -4 -1 -6
体積変化率 (％)
塩素200ppm +0.7 +1.8 +2.8 +6.7 +2.5 +4.9 +4.1 ／ +3.4 +1.3 +1.3 +3.4
〃 1000ppm +1.7 +3.7 +4.8+12.7 +8.8 +8.5 +5.3 ／ +5.7 +2.8 +2.4+10.7
外観
塩素200ppm ○ ○ × × × × × ／ × × ○ ×
〃 1000ppm ○ ○ × × × × × ／ × × ○ ×
The measurement results or evaluation results in the above Examples and Comparative Examples (excluding Comparative Example 8) are shown in the following table.
table
Example Comparative Example
Measurement / Evaluation Items 1 2 1 2 3 4 5 6 7 9 10 11
Normal physical properties Hardness (Duro A) 63 64 67 61 60 62 53 97 54 57 60 63
Tensile strength (MPa) 13.6 11.6 13.5 9.9 7.6 8.8 4.2 12.3 6.7 11 12 11
Elongation (%) 220 260 200 300 280 260 170 40 780 380 280 480
Test piece condition ○ ○ ○ ○ ○ ○ ○ High Not applied ○ ○ ○
Hardness Sulfur compression set
150 ° C, 70hrs (%) 10 18 20 17 37 26 21 45 58 38 24 88
Air aging test Hardness change (points) 0 +1 +3 +1 +6 +2 +3 +4 +5 +5 0 6
Chlorine water resistance test Change in hardness (points)
Chlorine 200ppm -3 -2 -2 -1 -4 -6 -2 / -3 -3 -2 -5
〃 1000ppm -2 -1 -2 -1 -4 -7 -2 / -2 -4 -1 -6
Volume change rate (%)
Chlorine 200ppm +0.7 +1.8 +2.8 +6.7 +2.5 +4.9 +4.1 / +3.4 +1.3 +1.3 +3.4
Ppm 1000ppm +1.7 +3.7 + 4.8 + 12.7 +8.8 +8.5 +5.3 / +5.7 +2.8 + 2.4 + 10.7
Appearance Chlorine 200 ppm ○ ○ × × × × × / × × ○ ×
〃 1000ppm ○ ○ × × × × × / × × ○ ×
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009022167A JP5577600B2 (en) | 2009-02-03 | 2009-02-03 | EPDM composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009022167A JP5577600B2 (en) | 2009-02-03 | 2009-02-03 | EPDM composition |
Publications (3)
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|---|---|
| JP2010180260A JP2010180260A (en) | 2010-08-19 |
| JP2010180260A5 JP2010180260A5 (en) | 2013-03-14 |
| JP5577600B2 true JP5577600B2 (en) | 2014-08-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6219268B2 (en) * | 2012-03-30 | 2017-10-25 | 古河電気工業株式会社 | Method for producing heat resistant resin composition, heat resistant resin composition produced by the production method, and molded article using the heat resistant resin composition |
| EP4079793A4 (en) * | 2019-12-20 | 2023-12-20 | NOK Corporation | Rubber composition and vulcanized molded product |
| CN112920515B (en) * | 2021-01-29 | 2023-06-23 | 厦门麦丰密封件有限公司 | Preparation process of EPDM sealing element and product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2872830B2 (en) * | 1991-08-08 | 1999-03-24 | 株式会社キッツ | Butterfly valve rubber seat |
| JP3826457B2 (en) * | 1996-10-24 | 2006-09-27 | チッソ株式会社 | Coated granular material with improved hydrophilicity and method for producing the same |
| JP2004210821A (en) * | 2002-12-26 | 2004-07-29 | Inoac Corp | Chlorine water-resistant rubber composition |
| JP2004210820A (en) * | 2002-12-26 | 2004-07-29 | Inoac Corp | Rubber composition having resistance to chlorine water |
| JP3999162B2 (en) * | 2003-05-23 | 2007-10-31 | 株式会社ニチリン | Rubber composition with excellent chlorine water resistance |
| JP2007296712A (en) * | 2006-04-28 | 2007-11-15 | Inoac Corp | Manufacturing method for rubber product for water service |
| JP2008106131A (en) * | 2006-10-25 | 2008-05-08 | Mitsubishi Cable Ind Ltd | Rubber composition and molded article using the same |
| JP5124131B2 (en) * | 2006-12-20 | 2013-01-23 | ヤマウチ株式会社 | Conductive rubber roller |
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| JP2010180260A (en) | 2010-08-19 |
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