JP2011068758A - Rubber composition for vulcanization for producing molded component directly contacting with biodiesel fuel - Google Patents
Rubber composition for vulcanization for producing molded component directly contacting with biodiesel fuel Download PDFInfo
- Publication number
- JP2011068758A JP2011068758A JP2009220507A JP2009220507A JP2011068758A JP 2011068758 A JP2011068758 A JP 2011068758A JP 2009220507 A JP2009220507 A JP 2009220507A JP 2009220507 A JP2009220507 A JP 2009220507A JP 2011068758 A JP2011068758 A JP 2011068758A
- Authority
- JP
- Japan
- Prior art keywords
- vulcanizing agent
- vulcanization
- rubber composition
- rubber
- dimercaptotriazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 50
- 239000005060 rubber Substances 0.000 title claims abstract description 50
- 239000003225 biodiesel Substances 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 238000004073 vulcanization Methods 0.000 title claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 16
- 150000001879 copper Chemical class 0.000 claims abstract description 13
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 12
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 5
- 150000002736 metal compounds Chemical group 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 4
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims description 3
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 claims description 2
- YFBUDXNMBTUSOC-UHFFFAOYSA-N 1,4-dihydroquinoxaline-2,3-dithione Chemical group C1=CC=C2NC(=S)C(=S)NC2=C1 YFBUDXNMBTUSOC-UHFFFAOYSA-N 0.000 claims description 2
- QOMSTRJEWDASHF-UHFFFAOYSA-N 2-(cyclohexylamino)-6-sulfanyl-1,3-dihydrotriazine-4-thione Chemical compound N1C(S)=CC(=S)NN1NC1CCCCC1 QOMSTRJEWDASHF-UHFFFAOYSA-N 0.000 claims description 2
- HXCOSFGSSXUTEZ-UHFFFAOYSA-N 2-(dibutylamino)-6-sulfanyl-1,3-dihydrotriazine-4-thione Chemical compound CCCCN(CCCC)N1NC(S)=CC(=S)N1 HXCOSFGSSXUTEZ-UHFFFAOYSA-N 0.000 claims description 2
- WZOCKHCXCJYKTM-UHFFFAOYSA-N 2-(diethylamino)-6-sulfanyl-1,3-dihydrotriazine-4-thione Chemical compound CCN(CC)N1NC(S)=CC(=S)N1 WZOCKHCXCJYKTM-UHFFFAOYSA-N 0.000 claims description 2
- CDJBUGDCQMHTSX-UHFFFAOYSA-N 2-(hexylamino)-6-sulfanyl-1,3-dihydrotriazine-4-thione Chemical compound CCCCCCNN1NC(S)=CC(=S)N1 CDJBUGDCQMHTSX-UHFFFAOYSA-N 0.000 claims description 2
- YFGKDYFYYPZZLE-UHFFFAOYSA-N 2-anilino-6-sulfanyl-1,3-dihydrotriazine-4-thione Chemical compound N1C(S)=CC(=S)NN1NC1=CC=CC=C1 YFGKDYFYYPZZLE-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 claims description 2
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 claims description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 2
- LSAUHWRNBBMZIC-UHFFFAOYSA-N 4-sulfanyl-1h-triazine-6-thione Chemical compound SC1=CC(=S)NN=N1 LSAUHWRNBBMZIC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000004636 vulcanized rubber Substances 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- -1 dithiocarbamic acid copper salt Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 239000003760 tallow Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 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 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 229910001701 hydrotalcite Inorganic materials 0.000 description 4
- 229960001545 hydrotalcite Drugs 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- 235000012245 magnesium oxide Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- 235000015278 beef Nutrition 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005561 epichlorohydrin homopolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 2
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 2
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 229940114930 potassium stearate Drugs 0.000 description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 2
- 229960001860 salicylate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
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- 229940114926 stearate Drugs 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-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
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- PAZJFXNRVLDLFO-UHFFFAOYSA-N 4-sulfanylmorpholine Chemical class SN1CCOCC1 PAZJFXNRVLDLFO-UHFFFAOYSA-N 0.000 description 1
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- 239000004135 Bone phosphate Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- REDUMNSTOASOGZ-UHFFFAOYSA-N [Sn].P(O)(O)O Chemical compound [Sn].P(O)(O)O REDUMNSTOASOGZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 description 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 description 1
- HOGZQCHCQNNPNS-UHFFFAOYSA-L copper;n-ethyl-n-phenylcarbamodithioate Chemical compound [Cu+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 HOGZQCHCQNNPNS-UHFFFAOYSA-L 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- OCWMFVJKFWXKNZ-UHFFFAOYSA-L lead(2+);oxygen(2-);sulfate Chemical compound [O-2].[O-2].[O-2].[Pb+2].[Pb+2].[Pb+2].[Pb+2].[O-]S([O-])(=O)=O OCWMFVJKFWXKNZ-UHFFFAOYSA-L 0.000 description 1
- YJOMWQQKPKLUBO-UHFFFAOYSA-L lead(2+);phthalate Chemical compound [Pb+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O YJOMWQQKPKLUBO-UHFFFAOYSA-L 0.000 description 1
- UMKARVFXJJITLN-UHFFFAOYSA-N lead;phosphorous acid Chemical compound [Pb].OP(O)O UMKARVFXJJITLN-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 240000004308 marijuana Species 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Chemical class 0.000 description 1
- 229920005989 resin Chemical class 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical class CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、耐バイオディーゼル性の改良されたエピハロヒドリン系ゴムをベースとする加硫用ゴム組成物および同組成物を加硫してなる加硫ゴム材料に関する。 The present invention relates to a rubber composition for vulcanization based on an epihalohydrin rubber having improved biodiesel resistance and a vulcanized rubber material obtained by vulcanizing the composition.
エピクロルヒドリン系ゴム材料はその耐熱性、耐油性、耐オゾン性等を活かして、自動車用途では燃料ホースやエアー系ホース、チューブ材料として幅広く使用されている。しかしながら、近年におけるカーボンニュートラルの考えや、石油燃料枯渇問題、ＣＯ２排出規制等により植物油や動物油由来のバイオディーゼル燃料が燃料油として使用されたり、既存の軽油に混合されたりしている。 Epichlorohydrin rubber materials are widely used as fuel hoses, air hoses, and tube materials in automotive applications, taking advantage of their heat resistance, oil resistance, ozone resistance, and the like. However, biodiesel fuel derived from vegetable oil or animal oil has been used as fuel oil or mixed with existing light oil due to the idea of carbon neutral in recent years, the problem of exhaustion of petroleum fuel, CO 2 emission regulations, and the like.
しかしながら、これらのバイオディーゼル燃料は通常の軽油と比べてゴムの膨潤・劣化を激しくする傾向があった。（非特許文献１参照） However, these biodiesel fuels tended to intensify the swelling and deterioration of rubber as compared with ordinary light oil. (See Non-Patent Document 1)
このため、ホース、チューブ用途ではさらに耐熱・耐油性に優れたフッ素系ゴムまたはフッ素系樹種を内層材とした構成のホースが開発されてきた。（特許文献１参照） For this reason, for hoses and tubes, hoses having a structure in which a fluorine rubber or a fluorine tree species having excellent heat resistance and oil resistance are used as an inner layer material have been developed. (See Patent Document 1)
しかしながら、一般的にフッ素系ゴムは非常に高価であり、またフッ素樹脂ではシール性を確保することが難しく、それらの解消のために耐油性に優れたゴムであるエピクロルヒドリン系ゴムの耐バイオディーゼル性の向上が求められてきた。 However, in general, fluorinated rubber is very expensive, and it is difficult to ensure sealability with fluororesin, and the biodiesel resistance of epichlorohydrin rubber, which is a rubber with excellent oil resistance to solve these problems Improvement has been demanded.
本発明は耐バイオディーゼル性に優れたエピハロヒドリン系ゴムを提供することを目的とする。 An object of the present invention is to provide an epihalohydrin rubber excellent in biodiesel resistance.
本発明者らは、上記課題を解決すべく種々検討を重ねたところ、エピハロヒドリン系ゴム、加硫剤、受酸剤を含有する加硫用ゴム組成物において、ジチオカルバミン酸の銅塩を配合することにより耐バイオディーゼル性が向上することを見出し、本発明を完成するに至った。 As a result of various studies to solve the above problems, the present inventors have formulated a copper salt of dithiocarbamic acid in a rubber composition for vulcanization containing an epihalohydrin rubber, a vulcanizing agent, and an acid acceptor. As a result, it was found that biodiesel resistance was improved, and the present invention was completed.
本発明はすなわち、（ａ）エピハロヒドリン系ゴムの１００重量部に対し、（ｂ）ジチオカルバミン酸の銅塩０．０１〜０．５重量部を含有し、（ｃ）受酸剤、および（ｄ）加硫剤を含有することを特徴とする、バイオディーゼル燃料と直接接触する成型部品を製造するための加硫用ゴム組成物、加硫ゴム材料、ならびに自動車用ゴム部品に関する。 That is, the present invention contains (b) 0.01 to 0.5 parts by weight of a copper salt of (b) dithiocarbamic acid with respect to 100 parts by weight of (a) epihalohydrin rubber, (c) an acid acceptor, and (d) The present invention relates to a rubber composition for vulcanization, a vulcanized rubber material, and an automotive rubber part for producing a molded part in direct contact with biodiesel fuel, characterized by containing a vulcanizing agent.
本発明により、エピハロヒドリン系ゴムをベースとした耐バイオディーゼル性の改良された加硫用ゴム組成物およびその加硫ゴム材料を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, a rubber composition for vulcanization having improved biodiesel resistance based on an epihalohydrin rubber and a vulcanized rubber material thereof can be provided.
以下、本発明につき詳細に説明する。本発明の加硫用ゴム組成物は、加硫前のゴム組成物を指し、少なくともエピハロヒドリン系ゴム、ジチオカルバミン酸の銅塩、受酸剤、加硫剤を含有する。 Hereinafter, the present invention will be described in detail. The rubber composition for vulcanization of the present invention refers to a rubber composition before vulcanization, and contains at least an epihalohydrin rubber, a copper salt of dithiocarbamic acid, an acid acceptor, and a vulcanizer.
本発明における（ａ）エピハロヒドリン系ゴムとは、エピハロヒドリン単独重合体またはエピハロヒドリンと共重合可能な他のエポキシド、例えばエチレンオキサイド、プロピレンオキサイド、アリルグリシジルエーテル等との共重合体をいう。これらを例示すれば、エピクロルヒドリン単独重合体、エピブロムヒドリン単独重合体、エピクロルヒドリン−エチレンオキサイド共重合体、エピブロムヒドリン−エチレンオキサイド共重合体、エピクロルヒドリン−プロピレンオキサイド共重合体、エピブロムヒドリン−プロピレンオキサイド共重合体、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体、エピブロムヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体、エピクロルヒドリン−エチレンオキサイド−プロピレンオキサイド−アリルグリシジルエーテル四元共重合体、エピブロムヒドリン−エチレンオキサイド−プロピレンオキサイド−アリルグリシジルエーテル四元共重合体等を挙げることができる。好ましくはエピクロルヒドリン単独重合体、エピクロルヒドリン−エチレンオキサイド共重合体、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体等のエピクロルヒドリン系重合体であり、さらに好ましくはエピクロルヒドリン−エチレンオキサイド共重合体、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体である。 The (a) epihalohydrin rubber in the present invention means an epihalohydrin homopolymer or a copolymer with other epoxides copolymerizable with epihalohydrin such as ethylene oxide, propylene oxide, allyl glycidyl ether and the like. For example, epichlorohydrin homopolymer, epibromohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epibromohydrin-ethylene oxide copolymer, epichlorohydrin-propylene oxide copolymer, epibromohydrin -Propylene oxide copolymer, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epibromohydrin-ethylene oxide-allyl glycidyl ether terpolymer, epichlorohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymer Examples thereof include quaternary copolymers, epibromohydrin-ethylene oxide-propylene oxide-allyl glycidyl ether quaternary copolymers, and the like. Preferred are epichlorohydrin homopolymers, epichlorohydrin-ethylene oxide copolymers, epichlorohydrin-based polymers such as epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymers, and more preferably epichlorohydrin-ethylene oxide copolymers, epichlorohydrin- Ethylene oxide-allyl glycidyl ether terpolymer.
エピクロルヒドリン−エチレンオキサイド共重合体、エピクロルヒドリン−エチレンオキサイド−アリルグリシジルエーテル三元共重合体の場合、それら共重合割合は、例えば、エピクロルヒドリン５ｍｏｌ〜９５ｍｏｌ％、好ましくは１０ｍｏｌ％〜７５ｍｏｌ％、さらに好ましくは１０〜６５ｍｏｌ％、エチレンオキサイド５ｍｏｌ％〜９５ｍｏｌ％、好ましくは２５ｍｏｌ％〜９０ｍｏｌ％、さらに好ましくは３５ｍｏｌ％〜９０ｍｏｌ％、アリルグリシジルエーテル０ｍｏｌ％〜１０ｍｏｌ％、好ましくは１ｍｏｌ％〜８ｍｏｌ％、さらに好ましくは１ｍｏｌ％〜７ｍｏｌ％である。 これら単独重合体または共重合体の分子量は特に制限されないが、通常ムーニー粘度表示でＭＬ１＋４（１００℃）＝３０〜１５０程度である。 In the case of epichlorohydrin-ethylene oxide copolymer and epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer, the copolymerization ratio is, for example, epichlorohydrin 5 mol to 95 mol%, preferably 10 mol% to 75 mol%, more preferably 10 ~ 65 mol%, ethylene oxide 5 mol%-95 mol%, preferably 25 mol%-90 mol%, more preferably 35 mol%-90 mol%, allyl glycidyl ether 0 mol%-10 mol%, preferably 1 mol%-8 mol%, more preferably 1 mol % To 7 mol%. The molecular weight of these homopolymers or copolymers is not particularly limited, but is usually about ML 1 + 4 (100 ° C.) = 30 to 150 in terms of Mooney viscosity.
また、本発明中の（ｂ）ジチオカルバミン酸の銅塩とは、一般的にはジエン系ゴムの加硫促進剤として用いられているものであるが、本発明の組成物においては老化防止剤としての作用を示す。ジチオカルバミン酸の銅塩の例としてはジメチルジチオカルバミン酸銅、ジエチルジチオカルバミン酸銅、ジブチルジチオカルバミン酸銅、Ｎ−エチル−Ｎ−フェニルジチオカルバミン酸銅、Ｎ−ペンタメチレンジチオカルバミン酸銅、ジベンジルジチオカルバミン酸銅等を例示することができる。前記ジチオカルバミン酸の銅塩は、アルキルジチオカルバミン酸の銅塩であることが更に好ましく、前記アルキルジチオカルバミン酸の銅塩は、ジアルキルジチオカルバミン酸の銅塩であることが特に好ましい。なお、アルキル基の炭素数は１〜１０であることが好ましい。 In addition, the (b) dithiocarbamic acid copper salt in the present invention is generally used as a vulcanization accelerator for diene rubbers, but as an anti-aging agent in the composition of the present invention. The effect of Examples of copper salts of dithiocarbamic acid include copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dibutyldithiocarbamate, copper N-ethyl-N-phenyldithiocarbamate, copper N-pentamethylenedithiocarbamate, copper dibenzyldithiocarbamate, etc. It can be illustrated. The copper salt of dithiocarbamic acid is more preferably a copper salt of alkyldithiocarbamic acid, and the copper salt of alkyldithiocarbamic acid is particularly preferably a copper salt of dialkyldithiocarbamic acid. In addition, it is preferable that carbon number of an alkyl group is 1-10.
これらジチオカルバミン酸の銅塩の配合割合はエピハロヒドリン系ゴム１００重量部に対して０．０１〜０．５重量部、好ましくは０．０２〜０．４重量部、さらに好ましくは０．０５〜０．３重量部である。この配合量がこの範囲未満であると耐バイオディーゼル性を改良する効果が少なく、また、多量に配合することは経済上好ましくない。 The blending ratio of the copper salt of dithiocarbamic acid is 0.01 to 0.5 parts by weight, preferably 0.02 to 0.4 parts by weight, more preferably 0.05 to 0.00 parts by weight based on 100 parts by weight of the epihalohydrin rubber. 3 parts by weight. If the blending amount is less than this range, the effect of improving the biodiesel resistance is small, and blending a large amount is not economically preferable.
本発明で用いられる（ｃ）受酸剤としては、公知の受酸剤を使用できるが、好ましくは金属化合物および／または無機マイクロポーラス・クリスタルである。金属化合物としては、周期表第II族（２族および１２族）金属の酸化物、水酸化物、炭酸塩、カルボン酸塩、ケイ酸塩、ホウ酸塩、亜リン酸塩、周期表III族（３族および１３族）金属の酸化物、水酸化物、カルボン酸塩、ケイ酸塩、硫酸塩、硝酸塩、リン酸塩、周期表第IV族（４族および１４族）金属の酸化物、塩基性炭酸塩、塩基性カルボン酸塩、塩基性亜リン酸塩、塩基性亜硫酸塩、三塩基性硫酸塩等の金属化合物が挙げられる。 As the (c) acid acceptor used in the present invention, a known acid acceptor can be used, and a metal compound and / or an inorganic microporous crystal is preferable. Examples of metal compounds include Group II (Group 2 and Group 12) metal oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites, and Group III of the Periodic Table. (Group 3 and Group 13) metal oxides, hydroxides, carboxylates, silicates, sulfates, nitrates, phosphates, periodic table Group IV (Groups 4 and 14) metal oxides, Examples thereof include metal compounds such as basic carbonates, basic carboxylates, basic phosphites, basic sulfites, and tribasic sulfates.
前記金属化合物の具体例としては、マグネシア、水酸化マグネシウム、水酸化アルミニウム、水酸化バリウム、炭酸ナトリウム、炭酸マグネシウム、炭酸バリウム、生石灰、消石灰、炭酸カルシウム、ケイ酸カルシウム、ステアリン酸カルシウム、ステアリン酸亜鉛、フタル酸カルシウム、亜リン酸カルシウム、亜鉛華、酸化錫、リサージ、鉛丹、鉛白、二塩基性フタル酸鉛、二塩基性炭酸鉛、ステアリン酸錫、塩基性亜リン酸鉛、塩基性亜リン酸錫、塩基性亜硫酸鉛、三塩基性硫酸鉛等を挙げることができ、炭酸ナトリウム、マグネシア、水酸化マグネシウム、生石灰、消石灰、ケイ酸カルシウム、亜鉛華などが好ましい。 Specific examples of the metal compound include magnesia, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, Calcium phthalate, calcium phosphite, zinc white, tin oxide, lisage, red lead, lead white, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic phosphorous acid Tin, basic lead sulfite, tribasic lead sulfate and the like can be mentioned, and sodium carbonate, magnesia, magnesium hydroxide, quicklime, slaked lime, calcium silicate, zinc white and the like are preferable.
前記無機マイクロポーラス・クリスタルとは、結晶性の多孔体を意味し、無定型の多孔体、例えばシリカゲル、アルミナ等とは明瞭に区別できるものである。このような無機マイクロポーラス・クリスタルの例としては、ゼオライト類、アルミノホスフェート型モレキュラーシーブ、層状ケイ酸塩、合成ハイドロタルサイト、チタン酸アルカリ金属塩等が挙げられる。特に好ましい受酸剤としては、合成ハイドロタルサイトが挙げられる。 The inorganic microporous crystal means a crystalline porous body and can be clearly distinguished from amorphous porous bodies such as silica gel and alumina. Examples of such inorganic microporous crystals include zeolites, aluminophosphate type molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates and the like. A particularly preferred acid acceptor is synthetic hydrotalcite.
前記ゼオライト類は、天然ゼオライトの外、Ａ型、Ｘ型、Ｙ型の合成ゼオライト、ソーダライト類、天然ないしは合成モルデナイト、ＺＳＭ−５などの各種ゼオライトおよびこれらの金属置換体であり、これらは単独で用いても２種以上の組み合わせで用いても良い。また金属置換体の金属はナトリウムであることが多い。ゼオライト類としては酸受容能が大きいものが好ましく、Ａ型ゼオライトが好ましい。 The zeolites are natural zeolite, A-type, X-type, Y-type synthetic zeolite, sodalite, natural or synthetic mordenite, various zeolites such as ZSM-5, and metal substitutes thereof. It may be used in combination of two or more. Further, the metal of the metal substitution product is often sodium. As the zeolite, those having a large acid-accepting ability are preferable, and A-type zeolite is preferable.
前記合成ハイドロタルサイトは下記一般式（１）で表される。
ＭｇＸＺｎＹＡｌＺ（ＯＨ）（２（Ｘ+Ｙ）+３Ｚ−２）ＣＯ３・ｗＨ２Ｏ （１）
［式中、ｘとｙはそれぞれｘ＋ｙ＝１〜１０の関係を有する０〜１０の実数、ｚは１〜５の実数、ｗは０〜１０の実数をそれぞれ示す。］
The synthetic hydrotalcite is represented by the following general formula (1).
Mg X Zn Y Al Z (OH ) (2 (X + Y) + 3Z-2) CO 3 · wH 2 O (1)
[Wherein, x and y are 0 to 10 real numbers having a relationship of x + y = 1 to 10, z is a real number of 1 to 5, and w is a real number of 0 to 10, respectively. ]
前記一般式（１）で表されるハイドロタルサイト類の例として、Ｍｇ４.５Ａｌ２（ＯＨ）１３ＣＯ３・３．５Ｈ２Ｏ、Ｍｇ４.５Ａｌ２（ＯＨ）１３ＣＯ３、Ｍｇ４Ａｌ２（ＯＨ）１２ＣＯ３・３．５Ｈ２Ｏ、Ｍｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ、Ｍｇ５Ａｌ２（ＯＨ）１４ＣＯ３・４Ｈ２Ｏ、Ｍｇ３Ａｌ２（ＯＨ）１０ＣＯ３・１．７Ｈ２Ｏ、Ｍｇ３ＺｎＡｌ２（ＯＨ）１２ＣＯ３・３．５Ｈ２Ｏ、Ｍｇ３ＺｎＡｌ２（ＯＨ）１２ＣＯ３等を挙げることができる。 Examples of the hydrotalcites represented by the general formula (1) include Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 , Mg 4 Al 2 (OH) 12 CO 3 .3.5H 2 O, Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, Mg 5 Al 2 (OH) 14 CO 3 .4H 2 O, Mg 3 Al 2 (OH) 10 CO 3 · 1.7H 2 O, Mg 3 ZnAl 2 (OH) 12 CO 3 · 3.5H 2 O, can be cited Mg 3 ZnAl 2 (OH) 12 CO 3 and the like.
前記（ｃ）受酸剤の配合量は、（ａ）エピハロヒドリン系ゴム１００重量部に対して好ましくは０．２〜５０重量部、更に好ましくは０．５〜５０重量部、特に１〜２０重量部である。これらの範囲であれば、十分に架橋し、且つ加硫物が剛直になりすぎることがなく、エピハロヒドリン系ゴム加硫物として通常期待される物性が得られるため好ましい。 The amount of the (c) acid acceptor is preferably 0.2 to 50 parts by weight, more preferably 0.5 to 50 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight of the (a) epihalohydrin rubber. Part. If it is in these ranges, it will be fully crosslinked and the vulcanizate will not be too rigid, and the physical properties normally expected as an epihalohydrin rubber vulcanizate will be obtained, which is preferable.
本発明の（ｄ）加硫剤としては、キノキサリン系加硫剤、チオウレア系加硫剤、トリアジン系加硫剤、ビスフェノール系加硫剤からなる群より選択される少なくとも１種が使用される。 As the vulcanizing agent (d) of the present invention, at least one selected from the group consisting of quinoxaline vulcanizing agents, thiourea vulcanizing agents, triazine vulcanizing agents, and bisphenol vulcanizing agents is used.
前記キノキサリン系加硫剤としては、２，３−ジメルカプトキノキサリン、キノキサリン−２，３−ジチオカーボネート、６−メチルキノキサリン−２，３−ジチオカーボネート、５，８−ジメチルキノキサリン−２，３−ジチカーボネート等が挙げられ、好ましくは６−メチルキノキサリン−２，３−ジチオカーボネートである。 Examples of the quinoxaline vulcanizing agent include 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithio. Examples thereof include carbonates, and 6-methylquinoxaline-2,3-dithiocarbonate is preferable.
前記チオウレア系加硫剤としては、２−メルカプトイミダゾリン（エチレンチオウレア）、１，３−ジエチルチオウレア、１，３−ジブチルチオウレア、トリメチルチオウレア等が挙げられ、好ましくは、２−メルカプトイミダゾリン（エチレンチオウレア）である。 Examples of the thiourea vulcanizing agent include 2-mercaptoimidazoline (ethylene thiourea), 1,3-diethylthiourea, 1,3-dibutylthiourea, trimethylthiourea, and the like, and preferably 2-mercaptoimidazoline (ethylene thiourea). It is.
前記トリアジン系加硫剤としては、２，４，６−トリメルカプト−１，３，５−トリアジン、２−ヘキシルアミノ−４，６−ジメルカプトトリアジン、２−ジエチルアミノ−４，６−ジメルカプトトリアジン、２−シクロヘキシルアミノ−４，６−ジメルカプトトリアジン、２−ジブチルアミノ−４，６−ジメルカプトトリアジン、２−アニリノ−４，６−ジメルカプトトリアジン、２−フェニルアミノ−４，６−ジメルカプトトリアジン等を挙げられ、好ましくは２，４，６−トリメルカプト−１，３，５−トリアジンである。 Examples of the triazine vulcanizing agent include 2,4,6-trimercapto-1,3,5-triazine, 2-hexylamino-4,6-dimercaptotriazine, and 2-diethylamino-4,6-dimercaptotriazine. 2-cyclohexylamino-4,6-dimercaptotriazine, 2-dibutylamino-4,6-dimercaptotriazine, 2-anilino-4,6-dimercaptotriazine, 2-phenylamino-4,6-dimercapto Examples include triazine, and 2,4,6-trimercapto-1,3,5-triazine is preferable.
前記ビスフェノール系加硫剤としては、ビスフェノールＡＦ、ビスフェノールＳ等が挙げられる。 Examples of the bisphenol vulcanizing agent include bisphenol AF and bisphenol S.
これらの加硫剤は本発明の効果をそこなわない限り、２種以上を併用しても良い。 These vulcanizing agents may be used in combination of two or more unless the effects of the present invention are impaired.
前記（ｃ）加硫剤の配合量は、（ａ）エピハロヒドリン系ゴム１００重量部に対して０．１〜１０重量部、好ましくは０．３〜５重量部である。これらの範囲であれば、十分に架橋し、且つ加硫物が剛直になりすぎることがなく、エピハロヒドリン系ゴム加硫物として通常期待される物性が得られるため好ましい。 The blending amount of the (c) vulcanizing agent is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the (a) epihalohydrin rubber. If it is in these ranges, it will be fully crosslinked and the vulcanizate will not be too rigid, and the physical properties normally expected as an epihalohydrin rubber vulcanizate will be obtained, which is preferable.
また、本発明においては、通常これらの加硫剤と共に使用される公知の加硫促進剤、遅延剤等を用いることができる。 Moreover, in this invention, the well-known vulcanization accelerator, retarder, etc. which are normally used with these vulcanizing agents can be used.
本発明に用いられる前記加硫促進剤としては、例えば、硫黄、モルホリンスルフィド類、アミン類、アミンの弱酸塩類、塩基性シリカ、四級アンモニウム塩類、四級ホスホニウム塩類、脂肪酸のアルカリ金属塩、チウラムスフィド類、多官能ビニル化合物、メルカプトベンゾチアゾール類、スルフェンアミド類、ジメチオカーバメート類等を挙げることができる。キノキサリン系加硫剤を本発明の組成物に適用した場合の特に好ましい促進剤として１, ８−ジアザビシクロ（５, ４, ０）ウンデセン−７（以下ＤＢＵと略）塩、１, ５−ジアザビシクロ（４, ３, ０）ノネン−５（以下ＤＢＮと略）塩、塩基性シリカ、脂肪酸のアルカリ金属塩が挙げられる。 Examples of the vulcanization accelerator used in the present invention include sulfur, morpholine sulfides, amines, weak acid salts of amines, basic silica, quaternary ammonium salts, quaternary phosphonium salts, alkali metal salts of fatty acids, thiuram. Examples thereof include sfides, polyfunctional vinyl compounds, mercaptobenzothiazoles, sulfenamides, and dimethiocarbamates. As a particularly preferred accelerator when a quinoxaline vulcanizing agent is applied to the composition of the present invention, a 1,8-diazabicyclo (5,4,0) undecene-7 (hereinafter abbreviated as DBU) salt, 1,5-diazabicyclo ( 4, 3, 0) Nonene-5 (hereinafter abbreviated as DBN) salt, basic silica, and alkali metal salt of fatty acid.
前記ＤＢＵ塩としては、ＤＢＵ−炭酸塩、ＤＢＵ−ステアリン酸塩、ＤＢＵ−２−エチルヘキシル酸塩、ＤＢＵ−安息香酸塩、ＤＢＵ−サリチル酸塩、ＤＢＵ−３−ヒドロキシ−２−ナフトエ酸塩、ＤＢＵ−フェノール樹脂塩、ＤＢＵ−２−メルカプトベンゾチアゾール塩、ＤＢＵ−２−メルカプトベンズイミダゾール塩等が挙げられる。また、前記ＤＢＮ塩としては、ＤＢＮ−炭酸塩、ＤＢＮ−ステアリン酸塩、ＤＢＮ−２−エチルヘキシル酸塩、ＤＢＮ−安息香酸塩、ＤＢＮ−サリチル酸塩、ＤＢＮ−３−ヒドロキシ−２−ナフトエ酸塩、ＤＢＮ−フェノール樹脂塩、ＤＢＮ−２−メルカプトベンゾチアゾール塩、ＤＢＮ−２−メルカプトベンズイミダゾール塩等が挙げられる。これらＤＢＵ塩および／またはＤＢＮ塩を促進剤として用いた場合の配合量は、（ａ）エピハロヒドリン系ゴム１００重量部に対して０．１〜５重量部が好ましく、より好ましくは、０．５〜３重量部である。 Examples of the DBU salt include DBU-carbonate, DBU-stearate, DBU-2-ethylhexylate, DBU-benzoate, DBU-salicylate, DBU-3-hydroxy-2-naphthoate, DBU- Examples thereof include phenol resin salts, DBU-2-mercaptobenzothiazole salts, DBU-2-mercaptobenzimidazole salts, and the like. Examples of the DBN salt include DBN-carbonate, DBN-stearate, DBN-2-ethylhexylate, DBN-benzoate, DBN-salicylate, DBN-3-hydroxy-2-naphthoate, Examples thereof include DBN-phenol resin salt, DBN-2-mercaptobenzothiazole salt, DBN-2-mercaptobenzimidazole salt and the like. The amount of the DBU salt and / or DBN salt used as an accelerator is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 100 parts by weight per 100 parts by weight of (a) epihalohydrin rubber. 3 parts by weight.
前記塩基性シリカとは、ｐＨが９〜１３のナトリウムを含有するシリカであり、前記塩基性シリカを促進剤として用いる場合、（ａ）エピハロヒドリン系ゴム１００重量部に対して２〜３０重量部が好ましく、より好ましくは５〜２０重量部である。 The basic silica is silica containing sodium having a pH of 9 to 13, and when the basic silica is used as an accelerator, 2 to 30 parts by weight per 100 parts by weight of (a) epihalohydrin rubber is used. Preferably, it is 5 to 20 parts by weight.
前記脂肪酸のアルカリ金属塩とは、高級脂肪酸、樹脂酸、ナフテン酸などのアルカリ金属塩（好ましくはナトリウム塩、カリウム塩）を挙げることができ、より好ましくは炭素数６以上の高級脂肪酸のアルカリ金属塩である。更に具体的には、半硬化牛脂脂肪酸、ステアリン酸、オレイン酸、セバシン酸、ひまし油等のナトリウム塩、カリウム塩が挙げられる。好ましい塩として、半硬化牛脂脂肪酸のナトリウム塩、ステアリン酸ナトリウム、半硬化牛脂脂肪酸のカリウム塩、ステアリン酸カリウムが挙げられ、さらに好ましくはステアリン酸ナトリウム及び／又はステアリン酸カリウムが挙げられる。特に、半硬化牛脂脂肪酸のナトリウム塩、ステアリン酸ナトリウム等のナトリウム塩を使用する場合は保存安定性が良好であり好ましい。これら脂肪酸のアルカリ金属塩を促進剤として用いた場合、（ａ）エピハロヒドリン系ゴム１００重量部に対して、０．２〜１０重量部が好ましく、より好ましくは０．５〜７重量部である。 Examples of the alkali metal salts of fatty acids include alkali metal salts (preferably sodium salts and potassium salts) such as higher fatty acids, resin acids, and naphthenic acids, and more preferably alkali metals of higher fatty acids having 6 or more carbon atoms. Salt. More specifically, examples include sodium salts and potassium salts such as semi-cured beef tallow fatty acid, stearic acid, oleic acid, sebacic acid, and castor oil. Preferable salts include sodium salt of semi-cured tallow fatty acid, sodium stearate, potassium salt of semi-cured tallow fatty acid, and potassium stearate, and more preferably sodium stearate and / or potassium stearate. In particular, when a sodium salt of semi-cured beef tallow fatty acid or a sodium salt such as sodium stearate is used, the storage stability is good and preferable. When these alkali metal salts of fatty acids are used as an accelerator, the amount is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of (a) epihalohydrin rubber.
また、本発明に用いられる前記遅延剤としてはＮ−シクロヘキシルチオフタルイミド、無水フタル酸、有機亜鉛化合物、酸性シリカ等を挙げることができ、遅延剤の配合量は、（ａ）エピハロヒドリン系ゴム１００重量部に対して０〜１０重量部が好ましく、より好ましくは０．１〜５重量部である。 Examples of the retarder used in the present invention include N-cyclohexylthiophthalimide, phthalic anhydride, an organic zinc compound, acidic silica and the like. The blending amount of the retarder is (a) 100 weight of epihalohydrin rubber. 0-10 weight part is preferable with respect to a part, More preferably, it is 0.1-5 weight part.
本発明に用いられる未加硫エピハロヒドリン系ゴム組成物には、当該技術分野において
通常使用される各種配合剤、例えば老化防止剤、充填剤、補強剤、可塑剤、加工助剤、顔料、難燃剤等を任意に配合することができる。
The unvulcanized epihalohydrin rubber composition used in the present invention includes various compounding agents commonly used in the technical field, such as anti-aging agents, fillers, reinforcing agents, plasticizers, processing aids, pigments, flame retardants. Etc. can be arbitrarily blended.
本発明による加硫用ゴム組成物を製造するには、従来ポリマー加工の分野において用いられている任意の混合手段、例えばミキシングロール、バンバリーミキサー、各種ニーダー類等を用いることができる。本発明の加硫ゴム材料は、本発明の加硫用ゴム組成物を通常１００〜３００℃に加熱することで得られる。加硫時間は温度により異なるが、通常０．５〜３００分の間である。加硫成型の方法としては、金型による圧縮成型、射出成型、スチーム缶、エアーバス、赤外線或いはマイクロウェーブによる加熱等任意の方法を用いることができる。 In order to produce the rubber composition for vulcanization according to the present invention, any mixing means conventionally used in the field of polymer processing, for example, a mixing roll, a Banbury mixer, various kneaders and the like can be used. The vulcanized rubber material of the present invention is usually obtained by heating the vulcanized rubber composition of the present invention to 100 to 300 ° C. The vulcanization time varies depending on the temperature, but is usually between 0.5 and 300 minutes. As a method of vulcanization molding, any method such as compression molding using a mold, injection molding, a steam can, an air bath, infrared rays, or heating by microwaves can be used.
本発明の加硫用ゴム組成物が接触するバイオディーゼルとしては、特に限定されるものではないが、一般的に例示すると、菜種油、パーム油、オリーブ油、ひまわり油、大豆油、コメ油、ヘンプ・オイル（大麻油）などの植物油、魚油や豚脂、牛脂などの獣脂及び廃食用油などをメチルエステル化したものなどが挙げられ、さらに具体的に例示するとＣｎＨｍＣＯＯＣＨ３で表される炭素数８〜２４の高級脂肪酸のメチルエステルが挙げられる。これらの脂肪酸メチルエステルと従来の軽油とを任意に混合されたものもバイオディーゼルとして用いることができる。脂肪酸メチルエステルと従来の軽油との混合されたバイオディーゼルは、バイオディーゼル全体の０．１ｖｏｌ％以上の脂肪酸メチルエステルを含むものであり、一般的には５ｖｏｌ％以上の脂肪酸メチルエステルを含むものが例示される。 The biodiesel to which the rubber composition for vulcanization of the present invention comes into contact is not particularly limited, but generally exemplified are rapeseed oil, palm oil, olive oil, sunflower oil, soybean oil, rice oil, hemp Examples include vegetable oils such as oil (cannabis oil), tallows such as fish oil, pork tallow, and beef tallow, and waste edible oils, and the like. More specifically, CnHmCOOCH 3 represents a carbon number of 8 to 8 24 methyl esters of higher fatty acids. Those obtained by arbitrarily mixing these fatty acid methyl esters and conventional light oil can also be used as biodiesel. Biodiesel mixed with fatty acid methyl ester and conventional light oil contains 0.1 vol% or more fatty acid methyl ester of the whole biodiesel, and generally contains 5 vol% or more fatty acid methyl ester. Illustrated.
以下、本発明を実施例、比較例、参考例により具体的に説明する。但し、本発明はその要旨を逸脱しない限り以下の実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, Comparative Examples, and Reference Examples. However, the present invention is not limited to the following examples without departing from the gist thereof.
実施例で使用した配合剤は下記の通りである。
・エピハロヒドリン系ゴム−１：エピクロルヒドリン−エチレンオキシド共重合体
ダイソー社製 「エピクロマーＣ」
・エピハロヒドリン系ゴム−２：エピクロルヒドリン単独重合体
ダイソー社製 「エピクロマーＨ」
・エピハロヒドリン系ゴム−３：エピクロルヒドリン−エチレンオキシド−アリルグリシジルエーテル共重合体
ダイソー社製 「エピクロマーＣＧ-１０５」
・カーボンブラック：東海カーボン社製 「シーストＳＯ」
・可塑剤：旭電化工業社製 「アデカサイザーＲＳ−１０７」
・滑剤：花王社製 「スプレンダーＲ−３００」
・有機ニッケル系老化防止剤：ジブチルジチオカルバミン酸ニッケル
大内新興化学工業社製 「ノクラックＮＢＣ」
・ジチオカルバミン酸の銅塩：ジメチルジチオカルバミン酸銅
大内新興化学工業社製 「ノクセラーＴＴＣｕ」
・ベンツイミダゾール系老化防止剤：２−メルカプトベンツイミダゾール
大内新興化学工業社製 「ノクラックＭＢ」
・受酸剤 マグネシア：酸化マグネシウム 協和化学工業社製 「キョーワマグ１５０」
・受酸剤 ハイドロタルサイト：合成ハイドロタルサイト 協和化学工業社製 「ＤＨＴ−４Ａ」
・受酸剤 炭酸カルシウム：白石工業社製 「炭酸カルシウム赤玉印」
・促進剤 ＤＢＵ塩：ＤＢＵのフェノール樹脂塩 ダイソー社製 「Ｐ−１５２」
・促進剤 ＴＳ： テトラメチルチウラムモノスルフィド 大内新興化学工業社製 「ノクセラーＴＳ」
・遅延剤 ＰＶＩ：Ｎ−シクロヘキシルチオフタルイミド
大内新興化学工業社製 「リターダーＣＴＰ」
・遅延剤 ＺｎＰＤＣ：Ｎ−ペンタメチレンジチオカルバミン酸亜鉛
大内新興化学工業社製 「ノクセラーＺＰ」
・遅延剤 ＣＺ：大内新興化学工業社製 「ノクセラーＣＺ」
・キノキサリン系加硫剤：６−メチルキノキサリン−２，３−ジチオカーボネート
ダイソー社製 「ダイソネットＸＬ−２１Ｓ」
・トリアジン系加硫剤：トリメルカプト-ｓ-トリアジン ダイソー社製 「ＯＦ−１００」
・加硫剤 ＥＴＵ：エチレンチオウレア 川口化学工業社製 「アクセル２２Ｓ」
The compounding agents used in the examples are as follows.
Epihalohydrin rubber-1: Epichlorohydrin-ethylene oxide copolymer "Epichromer C" manufactured by Daiso Corporation
-Epihalohydrin rubber-2: Epichlorohydrin homopolymer "Epichromer H" manufactured by Daiso Corporation
Epihalohydrin rubber-3: Epichlorohydrin-ethylene oxide-allyl glycidyl ether copolymer "Epichromer CG-105" manufactured by Daiso Corporation
・ Carbon black: “Seast SO” manufactured by Tokai Carbon
Plasticizer: “Adekasizer RS-107” manufactured by Asahi Denka Kogyo Co., Ltd.
・ Lubricant: “Splendor R-300” manufactured by Kao Corporation
・ Organic nickel-based anti-aging agent: Nickel dibutyldithiocarbamate “NOCRACK NBC” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
-Copper salt of dithiocarbamic acid: Copper dimethyldithiocarbamate "Noxeller TTCu" manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Benzimidazole anti-aging agent: 2-mercaptobenzimidazole “NOCRACK MB” manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Acid acceptor magnesia: Magnesium oxide “Kyowa Mag 150” manufactured by Kyowa Chemical Industry Co., Ltd.
・ Acid-accepting agent Hydrotalcite: Synthetic hydrotalcite “DHT-4A” manufactured by Kyowa Chemical Industry Co., Ltd.
・ Acid-accepting agent Calcium carbonate: Shiraishi Kogyo Co., Ltd.
-Accelerator DBU salt: phenol resin salt of DBU "P-152" manufactured by Daiso Corporation
・ Accelerator TS: Tetramethylthiuram monosulfide “Noxeller TS” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
・ Latering agent PVI: N-cyclohexylthiophthalimide "Retarder CTP" manufactured by Ouchi Shinsei Chemical Co., Ltd.
-Delay agent ZnPDC: Zinc N-pentamethylenedithiocarbamate "Noxeller ZP" manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Retarder CZ: “Noxeller CZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.
・ Quinoxaline-based vulcanizing agent: 6-methylquinoxaline-2,3-dithiocarbonate “Daisonette XL-21S” manufactured by Daiso Corporation
-Triazine vulcanizing agent: Trimercapto-s-triazine "OF-100" manufactured by Daiso Corporation
・ Vulcanizing agent ETU: Ethylenethiourea “Axel 22S” manufactured by Kawaguchi Chemical Co., Ltd.
表１および表２に示されるエピハロヒドリン系ゴム組成物をニーダーおよびオープンロールで混練し、厚さ２〜２．３ｍｍの未加硫シートを得た。得られた未加硫ゴムシートを１７０℃で１５分プレス加硫し、２ｍｍ厚の一次加硫物を得た。さらにこれをエア・オーブン中１５０℃で２時間加熱し、二次加硫物を得た。得られた二次加硫物を用い、引張試験（初期物性及び耐油後物性）、硬度試験、耐油性の評価を行った。各評価試験はそれぞれＪＩＳ Ｋ ６２５１、ＪＩＳ Ｋ ６２５８に記載の方法に準じて行った。ただし、試験用油はＪＩＳ Ｋ ２２０４に記載の２号軽油、又はＪＩＳ Ｋ ２２０４に記載の２号軽油と試薬のオレイン酸メチルを容量比で７０ｖｏｌ％／３０ｖｏｌ％に混合したものを用いた。 The epihalohydrin rubber compositions shown in Table 1 and Table 2 were kneaded with a kneader and an open roll to obtain an unvulcanized sheet having a thickness of 2 to 2.3 mm. The obtained unvulcanized rubber sheet was press vulcanized at 170 ° C. for 15 minutes to obtain a primary vulcanizate having a thickness of 2 mm. Further, this was heated in an air oven at 150 ° C. for 2 hours to obtain a secondary vulcanizate. Using the obtained secondary vulcanizate, a tensile test (initial physical properties and physical properties after oil resistance), a hardness test, and oil resistance were evaluated. Each evaluation test was performed according to the method described in JIS K 6251 and JIS K 6258, respectively. However, as the test oil, No. 2 diesel oil described in JIS K 2204 or No. 2 diesel oil described in JIS K 2204 and methyl oleate as a reagent were mixed at a volume ratio of 70 vol% / 30 vol%.
各試験方法より得られた実施例、比較例および参考例の試験結果を表３、４、５に示す。各表中、Ｍ１００はＪＩＳ Ｋ６２５１の引張試験に定める１００％伸び時の引張応力、ＴＢはＪＩＳ Ｋ６２５１の引張試験に定める引張強さ、ＥＢはＪＩＳ Ｋ６２５１の引張試験に定める破断時伸び、ＨＳはＪＩＳ Ｋ６２５３の硬さ試験に定める硬さを意味する。 The test results of Examples, Comparative Examples and Reference Examples obtained from each test method are shown in Tables 3, 4 and 5. In each table, M100 is the tensile stress at 100% elongation defined in the tensile test of JIS K6251, TB is the tensile strength defined in the tensile test of JIS K6251, EB is the elongation at break defined in the tensile test of JIS K6251, and HS is JIS. It means the hardness specified in the hardness test of K6253.
本発明において、耐油性、耐バイオディーゼル性が良好であるとは、耐油試験後の引張強さＴＢが大きいことを言う。
表３は参考までに通常の軽油での評価結果を示す。通常の軽油では実施例と比較例であまり差がなく、同程度の耐油性を示していることが分かる。
表４、表５はバイオディーゼルでの評価結果を示す。表４中の本発明の必須成分であるジチオカルバミン酸の銅塩や老化防止剤を全く含まない組成物である比較例１、一般的な老化防止剤を含む組成物である比較例２、３、４を加硫して得られる加硫物は、耐油試験後の引張強さＴｂが小さく、耐バイオディーゼル性は非常に乏しかった。一方、ジチオカルバミン酸の銅塩を含有する表３中の実施例１〜５の加硫物はいずれも優れた耐バイオディーゼル性を示している。
以上から、耐油性の優れたエピハロヒドリン系ゴムであっても、耐バイオディーゼル性を具備しているわけではないことが明らかであり、優れた耐バイオディーゼル性を有する本発明の加硫物はバイオディーゼル燃料向け用途において非常に有用であることが分かる。
In the present invention, good oil resistance and biodiesel resistance means that the tensile strength TB after the oil resistance test is large.
Table 3 shows the evaluation results with ordinary light oil for reference. It can be seen that ordinary light oil does not differ much between the examples and the comparative examples, and shows the same level of oil resistance.
Tables 4 and 5 show the evaluation results for biodiesel. Comparative Example 1, which is a composition containing no copper salt of dithiocarbamic acid and an antioxidant, which are essential components of the present invention in Table 4, Comparative Examples 2, 3, which are compositions containing a general antioxidant, The vulcanizate obtained by vulcanizing No. 4 had a small tensile strength Tb after the oil resistance test and very poor biodiesel resistance. On the other hand, the vulcanizates of Examples 1 to 5 in Table 3 containing a copper salt of dithiocarbamic acid all showed excellent biodiesel resistance.
From the above, it is clear that even an epihalohydrin rubber having excellent oil resistance does not have biodiesel resistance, and the vulcanizate of the present invention having excellent biodiesel resistance is bio-resistant. It proves very useful in applications for diesel fuel.
本発明の加硫物は、通常エピハロヒドリン系ゴムが使用される分野に広く応用することができる。特に耐バイオディーゼル性を生かした燃料用のホース、エアー系ホースのゴム材料として有用である。 The vulcanizate of the present invention can be widely applied to fields where epihalohydrin rubber is usually used. In particular, it is useful as a rubber material for fuel hoses and air hoses utilizing biodiesel resistance.
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| WO2013051689A1 (en) * | 2011-10-07 | 2013-04-11 | ダイソー株式会社 | Semi-conductive rubber composition |
| WO2015098911A1 (en) * | 2013-12-25 | 2015-07-02 | 日本ゼオン株式会社 | Crosslinking acrylic rubber composition and crosslinked rubber |
| JP2022158464A (en) * | 2021-04-02 | 2022-10-17 | 住友理工株式会社 | Rubber composition, and rubber product and hose using the same |
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| WO2013051689A1 (en) * | 2011-10-07 | 2013-04-11 | ダイソー株式会社 | Semi-conductive rubber composition |
| KR20140077180A (en) * | 2011-10-07 | 2014-06-23 | 다이소 가부시키가이샤 | Semi-conductive rubber composition |
| KR101918614B1 (en) * | 2011-10-07 | 2019-02-08 | 가부시키가이샤 오사카소다 | Semi-conductive rubber composition |
| WO2015098911A1 (en) * | 2013-12-25 | 2015-07-02 | 日本ゼオン株式会社 | Crosslinking acrylic rubber composition and crosslinked rubber |
| JP2022158464A (en) * | 2021-04-02 | 2022-10-17 | 住友理工株式会社 | Rubber composition, and rubber product and hose using the same |
| JP7364615B2 (en) | 2021-04-02 | 2023-10-18 | 住友理工株式会社 | Rubber compositions, rubber products using the same, and hoses |
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