JP2006022220A - Fuel-oil resistant rubber composition and vulcanized rubber - Google Patents
Fuel-oil resistant rubber composition and vulcanized rubber Download PDFInfo
- Publication number
- JP2006022220A JP2006022220A JP2004201865A JP2004201865A JP2006022220A JP 2006022220 A JP2006022220 A JP 2006022220A JP 2004201865 A JP2004201865 A JP 2004201865A JP 2004201865 A JP2004201865 A JP 2004201865A JP 2006022220 A JP2006022220 A JP 2006022220A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- mass
- conjugated diene
- unsaturated nitrile
- fuel oil
- 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 149
- 239000005060 rubber Substances 0.000 title claims abstract description 149
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 239000000295 fuel oil Substances 0.000 title claims abstract description 80
- 239000004636 vulcanized rubber Substances 0.000 title claims abstract description 57
- 150000002825 nitriles Chemical class 0.000 claims abstract description 101
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 20
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229920003244 diene elastomer Polymers 0.000 claims description 75
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 48
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- 125000003700 epoxy group Chemical group 0.000 claims description 28
- 238000012360 testing method Methods 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 11
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 11
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 11
- 239000005642 Oleic acid Substances 0.000 claims description 11
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 11
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 11
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- 238000000465 moulding Methods 0.000 claims description 6
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- 229930195729 fatty acid Natural products 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000012779 reinforcing material Substances 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 16
- 230000006835 compression Effects 0.000 abstract description 12
- 238000007906 compression Methods 0.000 abstract description 12
- 239000000178 monomer Substances 0.000 description 87
- -1 and among these Chemical compound 0.000 description 55
- 229940048053 acrylate Drugs 0.000 description 26
- 238000000034 method Methods 0.000 description 24
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- 238000002156 mixing Methods 0.000 description 21
- 229920000459 Nitrile rubber Polymers 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
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- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000006229 carbon black Substances 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
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- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 229940114077 acrylic acid Drugs 0.000 description 6
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 150000004671 saturated fatty acids Chemical class 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
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- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
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- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
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- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
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- GQWNEBHACPGBIG-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-[2-(1,3-benzothiazol-2-ylsulfanylamino)ethoxy]ethanamine Chemical compound C1=CC=C2SC(SNCCOCCNSC=3SC4=CC=CC=C4N=3)=NC2=C1 GQWNEBHACPGBIG-UHFFFAOYSA-N 0.000 description 1
- ILSQBBRAYMWZLQ-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-propan-2-ylpropan-2-amine Chemical compound C1=CC=C2SC(SN(C(C)C)C(C)C)=NC2=C1 ILSQBBRAYMWZLQ-UHFFFAOYSA-N 0.000 description 1
- GFSJJVJWCAMZEV-UHFFFAOYSA-N n-(4-anilinophenyl)-2-methylprop-2-enamide Chemical compound C1=CC(NC(=O)C(=C)C)=CC=C1NC1=CC=CC=C1 GFSJJVJWCAMZEV-UHFFFAOYSA-N 0.000 description 1
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- LPXPSTWBTULMJE-UHFFFAOYSA-N n-phenylbutan-1-imine Chemical compound CCCC=NC1=CC=CC=C1 LPXPSTWBTULMJE-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- BQHTWZRFOSRCCH-UHFFFAOYSA-L nickel(2+);dicarbamodithioate Chemical compound [Ni+2].NC([S-])=S.NC([S-])=S BQHTWZRFOSRCCH-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000008159 sesame oil Substances 0.000 description 1
- 235000011803 sesame oil Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical class [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 229940052367 sulfur,colloidal Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- WXBXVVIUZANZAU-CMDGGOBGSA-N trans-2-decenoic acid Chemical compound CCCCCCC\C=C\C(O)=O WXBXVVIUZANZAU-CMDGGOBGSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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- 239000011701 zinc Substances 0.000 description 1
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- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
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- 150000003752 zinc compounds Chemical class 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
- NEYNBSGIXOOZGZ-UHFFFAOYSA-L zinc;butoxymethanedithioate Chemical compound [Zn+2].CCCCOC([S-])=S.CCCCOC([S-])=S NEYNBSGIXOOZGZ-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Rigid Pipes And Flexible Pipes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、耐燃料油性ゴム組成物及び加硫ゴムに関し、更に詳しくは、耐燃料油性及び加工性に優れ、更に圧縮永久歪みの小さい加硫ゴムとすることができる耐燃料油性ゴム組成物及びその耐燃料油性ゴム組成物を加硫してなる加硫ゴムに関する。 The present invention relates to a fuel oil-resistant rubber composition and a vulcanized rubber. More specifically, the present invention relates to a fuel oil-resistant rubber composition that is excellent in fuel oil resistance and processability and can be made into a vulcanized rubber having a small compression set. The present invention relates to a vulcanized rubber obtained by vulcanizing the fuel oil-resistant rubber composition.
自動車等の内燃機関を用いる機械においては、燃料を燃料タンクから燃焼部まで移送する手段として、ゴムホースが一般的に使用されている。このようなゴムホースには、NBR(ニトリルブタジエンゴム)やHNBR(水添ニトリルブタジエンゴム)等の耐燃料油性に優れた原料が使用されている。NBR等の原料ゴムをホースにするときには、原料ゴムと各種配合剤を混合、混練してゴム組成物を作製し、それをホース状に加工し、その後に加硫してホース状の加硫ゴム(ホース状成形体)とする。これを製品として使用すると、燃料油によりゴム中からゴム薬品等が抽出され、抽出物が析出し、燃料油を汚染したり、フィルターの詰まりがある等、内燃機関に悪影響を及ぼすことがあるという問題を生じることがあった(例えば、非特許文献1,2参照)。
本発明は、上述の従来技術の問題に鑑みなされたものであり、耐燃料油性及び加工性に優れ、更に圧縮永久歪みの小さい加硫ゴムとすることができる耐燃料油性ゴム組成物及びその耐燃料油性ゴム組成物を加硫してなり、燃料油への抽出物の少ない加硫ゴムを提供することを目的とする。 The present invention has been made in view of the above-mentioned problems of the prior art, and is a fuel oil-resistant rubber composition that is excellent in fuel oil resistance and processability and that can be made into a vulcanized rubber having a small compression set, and its resistance. An object of the present invention is to provide a vulcanized rubber obtained by vulcanizing a fuel oil rubber composition and having a small amount of extract to fuel oil.
上記目的を達成するため、本発明によって以下の耐燃料油性ゴム組成物及び加硫ゴムが提供される。 In order to achieve the above object, the present invention provides the following fuel oil resistant rubber composition and vulcanized rubber.
[1] α,β−不飽和ニトリル・共役ジエン系ゴム、及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムを含有する原料ゴム100質量部と、炭素数8〜30の高級不飽和脂肪酸又はその金属塩0.1〜10質量部とを含有する耐燃料油性ゴム組成物。 [1] 100 parts by mass of raw rubber containing α, β-unsaturated nitrile / conjugated diene rubber and / or partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber, and having 8 to 30 carbon atoms A fuel oil-resistant rubber composition containing a higher unsaturated fatty acid or a metal salt thereof in an amount of 0.1 to 10 parts by mass.
[2] 前記高級不飽和脂肪酸がオレイン酸である[1]に記載の耐燃料油性ゴム組成物。 [2] The fuel oil-resistant rubber composition according to [1], wherein the higher unsaturated fatty acid is oleic acid.
[3] アクリル系ゴムを更に含有する[1]又は[2]に記載の耐燃料油性ゴム組成物。 [3] The fuel oil resistant rubber composition according to [1] or [2], further comprising an acrylic rubber.
[4] 前記アクリル系ゴムが、エポキシ基を0.01〜1.5mmol/g含有するエポキシ基含有アクリル系ゴムであり、前記α,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムが、カルボキシル基を0.02〜2.5mmol/g含有するカルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムである[3]に記載の耐燃料油性ゴム組成物。 [4] The acrylic rubber is an epoxy group-containing acrylic rubber containing 0.01 to 1.5 mmol / g of an epoxy group, and the α, β-unsaturated nitrile / conjugated diene rubber and / or partial hydrogen. The α, β-unsaturated nitrile / conjugated diene rubber is a carboxyl group-containing unsaturated nitrile / conjugated diene rubber and / or carboxyl group-containing partially hydrogenated non-hydrogenated monomer containing 0.02-2.5 mmol / g of carboxyl groups. The fuel oil resistant rubber composition according to [3], which is a saturated nitrile / conjugated diene rubber.
[5] 補強材、可塑剤、架硫剤及び加硫助剤を更に含有する[1]〜[4]のいずれかに記載の耐燃料油性ゴム組成物。 [5] The fuel oil-resistant rubber composition according to any one of [1] to [4], further comprising a reinforcing material, a plasticizer, a crosslinking agent, and a vulcanization aid.
[6] 所定の抽出試験による沈殿物の体積が0.1ml以下である[1]〜[5]のいずれかに記載の耐燃料油性ゴム組成物。 [6] The fuel oil resistant rubber composition according to any one of [1] to [5], wherein the volume of the precipitate by a predetermined extraction test is 0.1 ml or less.
[7] [1]〜[6]のいずれかに記載の耐燃料油性ゴム組成物が加硫されてなる加硫ゴム。 [7] A vulcanized rubber obtained by vulcanizing the fuel oil-resistant rubber composition according to any one of [1] to [6].
[8] [1]〜[6]のいずれかに記載の耐燃料油性ゴム組成物が成形されてなる成形体。 [8] A molded article obtained by molding the fuel oil-resistant rubber composition according to any one of [1] to [6].
[9] [1]〜[6]のいずれかに記載の耐燃料油性ゴム組成物がホース状に成形され、加硫されてなるホース状成形体。 [9] A hose-like molded body obtained by molding the fuel oil-resistant rubber composition according to any one of [1] to [6] into a hose shape and vulcanizing it.
本発明の耐燃料油性ゴム組成物によれば、所定の不飽和ニトリル・共役ジエン系ゴムに、炭素数8〜30の高級不飽和脂肪酸又はその金属塩が所定量添加することで、加硫ゴムにして燃料油に接触させたときに、燃料油中の析出物(抽出されて燃料油中で析出する物質)が非常に少ない。 According to the fuel oil-resistant rubber composition of the present invention, a predetermined amount of a higher unsaturated fatty acid having 8 to 30 carbon atoms or a metal salt thereof is added to a predetermined unsaturated nitrile / conjugated diene rubber, whereby a vulcanized rubber is obtained. When the fuel oil is brought into contact with the fuel oil, there are very few precipitates in the fuel oil (substances extracted and deposited in the fuel oil).
本発明の加硫ゴムは、加工性が良好で圧縮永久歪みが小さい。 The vulcanized rubber of the present invention has good processability and small compression set.
以下、本発明を実施するための最良の形態(以下、「実施の形態」ということがある)を具体的に説明するが、本発明は以下の実施の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、適宜設計の変更、改良等が加えられることが理解されるべきである。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the best mode for carrying out the present invention (hereinafter sometimes referred to as “embodiment”) will be specifically described, but the present invention is not limited to the following embodiment, It should be understood that design changes, improvements, and the like can be made as appropriate based on ordinary knowledge of those skilled in the art without departing from the spirit of the invention.
本発明の耐燃料油性ゴム組成物の一の実施の形態は、α,β−不飽和ニトリル・共役ジエン系ゴム、及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムを含有する原料ゴム100質量部と、炭素数8〜30の高級不飽和脂肪酸又はその金属塩0.1〜5質量部とを含有するものである。「α,β−不飽和ニトリル・共役ジエン系ゴム、及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムを含有する原料ゴム」とは、「α,β−不飽和ニトリル・共役ジエン系ゴム、部分水素化α,β−不飽和ニトリル・共役ジエン系ゴム、又はこれらの両方を合わせたものを含有する原料ゴム」ということを意味する。 One embodiment of the fuel oil resistant rubber composition of the present invention contains α, β-unsaturated nitrile / conjugated diene rubber and / or partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber. Containing 100 parts by mass of raw rubber and 0.1 to 5 parts by mass of a higher unsaturated fatty acid having 8 to 30 carbon atoms or a metal salt thereof. “Rubber raw material containing α, β-unsaturated nitrile / conjugated diene rubber and / or partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber” means “α, β-unsaturated nitrile / It means “a raw rubber containing a conjugated diene rubber, a partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber, or a combination of both”.
上記高級不飽和脂肪酸等の炭素数は、8〜30であり、好ましくは10〜25であり、更に好ましくは16〜20である。炭素数が、8より少ないと、粘度が低くなるため、混練、加工時に潤滑油的な加工助剤としての役割を果たさず、原料ゴムと各種配合物との混合物が混練機等の装置に粘着するという問題がある。上記炭素数が30より大きいと、粘度が高く流動性が低下するため混練、加工を効率的に行うことができないという問題がある。 Carbon number, such as the said higher unsaturated fatty acid, is 8-30, Preferably it is 10-25, More preferably, it is 16-20. When the number of carbon atoms is less than 8, the viscosity becomes low, so that it does not serve as a lubricating oil processing aid during kneading and processing, and the mixture of raw rubber and various blends adheres to a kneader or other device. There is a problem of doing. When the number of carbon atoms is larger than 30, there is a problem that kneading and processing cannot be performed efficiently because of high viscosity and low fluidity.
上記高級不飽和脂肪酸等の配合割合は、原料ゴム100質量部に対して0.1〜10質量部であり、好ましくは0.1〜5質量部であり、更に好ましくは0.2〜3質量部である。0.1質量部より少ないと、高級不飽和脂肪酸等の量が少ないため、原料ゴムと各種配合物との混合物が混練機等の装置に粘着するという問題がある。10質量部より多いと、加硫ゴムにしたときの物性が低下するという問題がある。 The blending ratio of the above-mentioned higher unsaturated fatty acid is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the raw rubber. Part. If the amount is less than 0.1 parts by mass, the amount of higher unsaturated fatty acids and the like is small, so there is a problem that the mixture of the raw rubber and various blends sticks to an apparatus such as a kneader. When the amount is more than 10 parts by mass, there is a problem that the physical properties when vulcanized rubber is reduced.
上記高級不飽和脂肪酸等における炭素数8〜30の高級不飽和脂肪酸としては、デセン酸、オレイン酸、エルシン酸、リノール酸、リノレン酸、アラキドン酸、エイコサペンタエン酸、リシノール酸等を挙げることができる。これらの中でも、オレイン酸が、混練等を行うときの上記混合物の装置への粘着を防止し、加硫ゴムとしたものを燃料油に接触させたときに抽出物が析出することを防止すると共に、加硫ゴムとしたものの圧縮永久歪みを小さくするという観点から好ましい。 Examples of the higher unsaturated fatty acid having 8 to 30 carbon atoms in the higher unsaturated fatty acid include decenoic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, ricinoleic acid and the like. . Among these, oleic acid prevents the mixture from adhering to the apparatus when kneading and the like, and prevents the extract from precipitating when the vulcanized rubber is brought into contact with fuel oil. From the viewpoint of reducing the compression set of the vulcanized rubber.
また、本実施の形態の耐燃料油性ゴム組成物中には、上記高級不飽和脂肪酸等以外にステアリン酸、パルミチン酸、ミリスチン酸等の飽和脂肪酸が含まれていてもよいが、飽和脂肪酸の含有量は、上記高級不飽和脂肪酸等と飽和脂肪酸との合計量に対して30質量%以下であることが好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが特に好ましい。 In addition, the fuel oil-resistant rubber composition of the present embodiment may contain saturated fatty acids such as stearic acid, palmitic acid, and myristic acid in addition to the above-mentioned higher unsaturated fatty acids. The amount is preferably 30% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total amount of the above-mentioned higher unsaturated fatty acid and the like and saturated fatty acid. .
上記高級不飽和脂肪酸等における炭素数8〜30の高級不飽和脂肪酸の金属塩としては、上記炭素数8〜30の高級不飽和脂肪酸の亜鉛塩、ナトリウム塩、カリウム塩、カルシウム塩等を挙げることができる。これらの中でも、亜鉛塩及びナトリウム塩が好ましい。 Examples of the metal salt of the higher unsaturated fatty acid having 8 to 30 carbon atoms in the higher unsaturated fatty acid and the like include zinc salts, sodium salts, potassium salts, calcium salts and the like of the higher unsaturated fatty acid having 8 to 30 carbon atoms. Can do. Of these, zinc salts and sodium salts are preferred.
本実施の形態の耐燃料油性ゴム組成物は、上述のように加硫助剤として酸化亜鉛を含有する場合に、特に加硫ゴムとしたときに燃料油に析出され難いという効果を発揮する。 The fuel oil-resistant rubber composition of the present embodiment exhibits an effect that it is difficult to be precipitated in fuel oil particularly when vulcanized rubber is contained when zinc oxide is contained as a vulcanization aid as described above.
本実施の形態の耐燃料油性ゴム組成物において、α,β−不飽和ニトリル・共役ジエン系ゴムは、α,β−不飽和ニトリル単量体に由来する構造単位(a1)15〜60質量%、共役ジエン単量体に由来する構造単位(a2)40〜85質量%、これらの単量体と共重合可能な他の単量体に由来する構造単位(a3)0〜20質量%を含有することが好ましい((a1)+(a2)+(a3)=100質量%)。 In the fuel oil-resistant rubber composition of the present embodiment, the α, β-unsaturated nitrile / conjugated diene rubber is a structural unit (a1) derived from an α, β-unsaturated nitrile monomer of 15 to 60% by mass. , 40 to 85% by mass of the structural unit (a2) derived from the conjugated diene monomer, and 0 to 20% by mass of the structural unit (a3) derived from another monomer copolymerizable with these monomers It is preferable ((a1) + (a2) + (a3) = 100% by mass).
α,β−不飽和ニトリル単量体に由来する構造単位(a1)は、20〜55質量%であることが好ましく、30〜50質量%であることが更に好ましい。15質量%未満では、加硫ゴムの耐燃料油性が劣る傾向にあり、60質量%を超えると、硬度が高くなり、ゴムらしさがなくなる傾向にある。 The structural unit (a1) derived from the α, β-unsaturated nitrile monomer is preferably 20 to 55% by mass, and more preferably 30 to 50% by mass. If it is less than 15% by mass, the fuel oil resistance of the vulcanized rubber tends to be inferior. If it exceeds 60% by mass, the hardness tends to be high and the rubber-like property tends to be lost.
α,β−不飽和ニトリル単量体としては、アクリロニトリル、メタクリロニトリル、エタクリロニトリル、α−クロロアクリロニトリル、α−フルオロアクリロニトリル等が挙げられ、これらの中でも特にアクリロニトリルが好ましい。これらは、1種単独であるいは2種以上組み合わせて用いることができる。 Examples of the α, β-unsaturated nitrile monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-fluoroacrylonitrile, and among these, acrylonitrile is particularly preferable. These can be used singly or in combination of two or more.
共役ジエン単量体に由来する構造単位(a2)は、45〜80質量%であることが好ましく、50〜70質量%であることが更に好ましい。40質量%未満では、加硫ゴムの硬度が高くなり、ゴムらしさがなくなる傾向にある。85質量%を超えると、耐燃料油性が劣る傾向にある。 The structural unit (a2) derived from the conjugated diene monomer is preferably 45 to 80% by mass, and more preferably 50 to 70% by mass. If it is less than 40% by mass, the hardness of the vulcanized rubber tends to be high and the rubberiness tends to be lost. If it exceeds 85% by mass, the fuel oil resistance tends to be inferior.
共役ジエン単量体としては、1,3−ブタジエン、イソプレン(2−メチル−1,3−ブタジエン)、2,3−ジメチル−1,3−ブタジエン、クロロプレン(2−クロロ−1,3−ブタジエン)等が挙げられ、これらの中でも特に1,3−ブタジエンが好ましい。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Conjugated diene monomers include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, chloroprene (2-chloro-1,3-butadiene) Among these, 1,3-butadiene is particularly preferable. These can be used alone or in combination of two or more.
上述のように、α,β−不飽和ニトリル・共役ジエン系ゴムは、上記α,β−不飽和ニトリル及び共役ジエンと共重合可能な他の単量体に由来する構造単位(a3)を含有してもよい。上記他の単量体としては、非共役環状ポリエン、下記一般式(1)で表される化合物、芳香族ビニル系単量体、アミド化合物、(メタ)アクリル酸シクロアルキルエステル、脂環族又は芳香族のアルコールの(メタ)アクリル酸エステル、アミノ基、シアノ基、ヒドロキシル基等の官能基を有する(メタ)アクリル酸アルキルエステル、不飽和カルボン酸と低級飽和アルコールとのエステル、酢酸ビニル、塩化ビニル、塩化ビニリデン等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 As described above, the α, β-unsaturated nitrile / conjugated diene rubber contains the structural unit (a3) derived from the α, β-unsaturated nitrile and another monomer copolymerizable with the conjugated diene. May be. Examples of the other monomer include a non-conjugated cyclic polyene, a compound represented by the following general formula (1), an aromatic vinyl monomer, an amide compound, a (meth) acrylic acid cycloalkyl ester, an alicyclic group, (Meth) acrylic acid ester of aromatic alcohol, (meth) acrylic acid alkyl ester having functional group such as amino group, cyano group, hydroxyl group, ester of unsaturated carboxylic acid and lower saturated alcohol, vinyl acetate, chloride Examples include vinyl and vinylidene chloride. These can be used alone or in combination of two or more.
上記一般式(1)において、X1は水素原子又はメチル基を表す。nは0〜10の整数である。 In the general formula (1), X 1 represents a hydrogen atom or a methyl group. n is an integer of 0-10.
上記非共役環状ポリエンとしては、5−エチリデン−2−ノルボルネン、ジシクロペンタジエン、5−プロピリデン−2−ノルボルネン、5−ビニル−2−ノルボルネン、2,5−ノルボルナジエン、1,4−シクロヘキサジエン、1,4−シクロオクタジエン、1,5−シクロオクタジエン、5−メチレン−2−ノルボルネン、5−ビニル−2−ノルボルネン、5−(2−プロペニル)−2−ノルボルネン、5−(3−ブテニル)−2−ノルボルネン、5−(1−メチル−2−プロペニル)−2−ノルボルネン、5−(4−ペンテニル)−2−ノルボルネン、5−(1−メチル−3−ブテニル)−2−ノルボルネン、5−(5−ヘキセニル)−2−ノルボルネン、5−(1−メチル−4−ペンテニル)−2−ノルボルネン、5−(2,3−ジメチル−3−ブテニル)−2−ノルボルネン、5−(2−エチル−3−ブテニル)−2−ノルボルネン、5−(6−ヘプテニル)−2−ノルボルネン、5−(3−メチル−5−ヘキセニル)−2−ノルボルネン、5−(3,4−ジメチル−4−ペンテニル)−2−ノルボルネン、5−(3−エチル−4−ペンテニル)−2−ノルボルネン、5−(7−オクテニル)−2−ノルボルネン、5−(2−メチル−6−ヘプテニル)−2−ノルボルネン、5−(1,2−ジメチル−5−ヘキセシル)−2−ノルボルネン、5−(5−エチル−5−ヘキセニル)−2−ノルボルネン、5−(1,2,3−トリメチル−4−ペンテニル)−2−ノルボルネン等が挙げられる。これらは、1種単独であるいは2種以上組み合わせて用いることができる。 Examples of the non-conjugated cyclic polyene include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, , 4-cyclooctadiene, 1,5-cyclooctadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) 2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5 -(5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2,3- Methyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) 2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene , 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (1,2-dimethyl-5-hexyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene , 5- (1,2,3-trimethyl-4-pentenyl) -2-norbornene and the like. These can be used singly or in combination of two or more.
上記一般式(1)で表される化合物は、不飽和カルボン酸のジヒドロジシクロペンタジエニルオキシエチル基含有エステルであり、式中、好ましいnは、1又は2である。上記一般式(1)で表される化合物としては、ジヒドロジシクロペンタジエニルオキシエチレン等と(メタ)アクリル酸等の不飽和カルボン酸とのエステル反応により合成される。その例としては、(メタ)アクリル酸ジヒドロジシクロペンタジエニル、(メタ)アクリル酸ジヒドロジシクロペンタジエニルオキシエチル、(メタ)アクリル酸ジヒドロジシクロペンタジエニルオキシオキシジエチル等が挙げられる。これらは、1種単独であるいは2種以上組み合わせて用いることができる。 The compound represented by the general formula (1) is a dihydrodicyclopentadienyloxyethyl group-containing ester of an unsaturated carboxylic acid. In the formula, preferable n is 1 or 2. The compound represented by the general formula (1) is synthesized by an ester reaction between dihydrodicyclopentadienyloxyethylene or the like and an unsaturated carboxylic acid such as (meth) acrylic acid. Examples thereof include dihydrodicyclopentadienyl (meth) acrylate, dihydrodicyclopentadienyloxyethyl (meth) acrylate, dihydrodicyclopentadienyloxyoxydiethyl (meth) acrylate, and the like. These can be used singly or in combination of two or more.
上記芳香族ビニル系単量体としては、スチレン、2−メチルスチレン、3−メチルスチレン、4−メチルスチレン、α−メチルスチレン、2,4−ジメチルスチレン、2,4−ジイソプロピルスチレン、4−tert−ブチルスチレン、tert−ブトキシスチレン、ビニルトルエン、ビニルナフタレン、ハロゲン化スチレン等が挙げられる。 Examples of the aromatic vinyl monomer include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert. -Butyl styrene, tert-butoxy styrene, vinyl toluene, vinyl naphthalene, halogenated styrene and the like.
上記アミド化合物としては、アクリルアミド、N−メチロールアクリルアミド、N−(4−アニリノフェニル)アクリルアミド、N−(4−アニリノフェニル)メタクリルアミド等が挙げられる。 Examples of the amide compound include acrylamide, N-methylolacrylamide, N- (4-anilinophenyl) acrylamide, and N- (4-anilinophenyl) methacrylamide.
上記(メタ)アクリル酸シクロアルキルエステルとしては、(メタ)アクリル酸シクロへキシル等が挙げられる。 Examples of the (meth) acrylic acid cycloalkyl ester include cyclohexyl (meth) acrylate.
上記芳香族アルコールの(メタ)アクリル酸エステルとしては、(メタ)アクリル酸ベンジル等が挙げられる。 Examples of the (meth) acrylic acid ester of the aromatic alcohol include benzyl (meth) acrylate.
上記アミノ基を有する(メタ)アクリル酸エステルとしては、(メタ)アクリル酸ジメチルアミノメチル、(メタ)アクリル酸ジエチルアミノメチル、(メタ)アクリル酸2−ジメチルアミノエチル、(メタ)アクリル酸2−ジエチルアミノエチル、(メタ)アクリル酸2−(ジ−n−プロピルアミノ)エチル、(メタ)アクリル酸2−ジメチルアミノプロピル、(メタ)アクリル酸2−ジエチルアミノプロピル、(メタ)アクリル酸2−(ジ−n−プロピルアミノ)プロピル、(メタ)アクリル酸3−ジメチルアミノプロピル、(メタ)アクリル酸3−ジエチルアミノプロピル、(メタ)アクリル酸3−(ジ−n−プロピルアミノ)プロピル等が挙げられる。 Examples of the (meth) acrylic acid ester having an amino group include dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, and 2-diethylamino (meth) acrylate. Ethyl, (meth) acrylic acid 2- (di-n-propylamino) ethyl, (meth) acrylic acid 2-dimethylaminopropyl, (meth) acrylic acid 2-diethylaminopropyl, (meth) acrylic acid 2- (di- n-propylamino) propyl, (meth) acrylic acid 3-dimethylaminopropyl, (meth) acrylic acid 3-diethylaminopropyl, (meth) acrylic acid 3- (di-n-propylamino) propyl, and the like.
上記シアノ基を有する(メタ)アクリル酸アルキルエステルとしては、(メタ)アクリル酸シアノメチル、(メタ)アクリル酸1−シアノエチル、(メタ)アクリル酸2−シアノエチル、(メタ)アクリル酸1−シアノプロピル、(メタ)アクリル酸2−シアノプロピル、(メタ)アクリル酸3−シアノプロピル、(メタ)アクリル酸4−シアノブチル、(メタ)アクリル酸6−シアノヘキシル、(メタ)アクリル酸2−エチル−6−シアノヘキシル、(メタ)アクリル酸8−シアノオクチル等が挙げられる。 Examples of the (meth) acrylic acid alkyl ester having a cyano group include cyanomethyl (meth) acrylate, 1-cyanoethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, 1-cyanopropyl (meth) acrylate, (Meth) acrylic acid 2-cyanopropyl, (meth) acrylic acid 3-cyanopropyl, (meth) acrylic acid 4-cyanobutyl, (meth) acrylic acid 6-cyanohexyl, (meth) acrylic acid 2-ethyl-6- And cyanohexyl and 8-cyanooctyl (meth) acrylate.
上記ヒドロキシル基を有する(メタ)アクリル酸エステルとしては、(メタ)アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピル、(メタ)アクリル酸3−ヒドロキシプロピル、(メタ)アクリル酸2−ヒドロキシブチル、(メタ)アクリル酸3−ヒドロキシブチル、(メタ)アクリル酸4−ヒドロキシブチル等のヒドロキシアルキル(メタ)アクリル酸類、及びポリエチレングリコール、ポリプロピレングリコール等のポリアルキレングリコール(アルキレングリコールの単位数は、例えば、2〜23)のモノ(メタ)アクリル酸エステル類等が挙げられる。 Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxybutyl, hydroxyalkyl (meth) acrylic acids such as 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyalkylene glycols such as polyethylene glycol and polypropylene glycol (number of units of alkylene glycol) Is, for example, 2-23) mono (meth) acrylic acid esters.
また、上記不飽和カルボン酸と低級飽和アルコールとのエステルにおいて用いられる不飽和カルボン酸としては、メタクリル酸、イタコン酸、フマル酸、マレイン酸等が挙げられる。 Examples of the unsaturated carboxylic acid used in the ester of the unsaturated carboxylic acid and the lower saturated alcohol include methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.
尚、上記他の単量体として例示した中で、加硫性の点から、非共役環状ポリエン及び一般式(1)で表される化合物が特に好ましい。 In addition, among the examples of the other monomer, a non-conjugated cyclic polyene and a compound represented by the general formula (1) are particularly preferable from the viewpoint of vulcanizability.
本実施の形態の耐燃料油性ゴム組成物において、α,β−不飽和ニトリル・共役ジエン系ゴムは、部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムであってもよく、また、これらの両方が混在していてもよい。部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムは、α,β−不飽和ニトリル・共役ジエン系ゴム中の炭素−炭素二重結合を部分的に(選択的に)水素化したものである。 In the fuel oil resistant rubber composition of the present embodiment, the α, β-unsaturated nitrile / conjugated diene rubber may be a partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber, Both of these may be mixed. Partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber is a partially (selectively) hydrogenated carbon-carbon double bond in an α, β-unsaturated nitrile / conjugated diene rubber. It is.
上述した本実施の形態のα,β−不飽和ニトリル・共役ジエン系ゴムを構成する構造単位(a3)の含有量は、全構造単位量を100質量%とした場合、0〜20質量%であることが好ましいが、0〜10質量%であることが更に好ましい。 The content of the structural unit (a3) constituting the α, β-unsaturated nitrile / conjugated diene rubber of the present embodiment described above is 0 to 20% by mass when the total structural unit amount is 100% by mass. Although it is preferable, it is still more preferable that it is 0-10 mass%.
上記α,β−不飽和ニトリル・共役ジエン系ゴムのムーニー粘度[ML1+4(100℃)]は10〜200であることが好ましく、30〜100であることが更に好ましい。上記ムーニー粘度が小さすぎると、加硫ゴムの強度が低下する傾向にあり、一方、大きすぎると、混練時の加工性が劣る場合がある。 The Mooney viscosity [ML 1 + 4 (100 ° C.)] of the α, β-unsaturated nitrile / conjugated diene rubber is preferably 10 to 200, and more preferably 30 to 100. If the Mooney viscosity is too small, the strength of the vulcanized rubber tends to decrease. On the other hand, if the Mooney viscosity is too large, the workability during kneading may be inferior.
本実施の形態の耐燃料油性ゴム組成物に含有される原料ゴムには、上述したα,β−不飽和ニトリル・共役ジエン系ゴム等以外に、他のゴム成分を含有してもよい。他のゴム成分としては、天然ゴム、ブタジエンゴム、イソプレンゴム、クロロプレンゴム、スチレン−ブタジエン共重合ゴム、ブタジエン・イソプレン共重合ゴム、ブタジエン・スチレン・イソプレン共重合ゴム、ブチルゴム等が挙げられる。これら他のゴム成分の含有割合は、上記α,β−不飽和ニトリル・共役ジエン系ゴム等100質量部に対して、好ましくは0〜30質量部、更に好ましくは0〜10質量部、特に好ましくは0〜5質量部である。 In addition to the α, β-unsaturated nitrile / conjugated diene rubber and the like described above, the raw rubber contained in the fuel oil-resistant rubber composition of the present embodiment may contain other rubber components. Examples of other rubber components include natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene copolymer rubber, butadiene / isoprene copolymer rubber, butadiene / styrene / isoprene copolymer rubber, and butyl rubber. The content of these other rubber components is preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, particularly preferably 100 parts by mass of the α, β-unsaturated nitrile / conjugated diene rubber and the like. Is 0-5 parts by mass.
上記α,β−不飽和ニトリル・共役ジエン系ゴムの製造方法は、上記構造単位(a1)、(a2)及び(a3)のそれぞれを形成することとなる上記各単量体を、好ましくはラジカル重合開始剤の存在下で共重合することにより得ることができる。 In the method for producing the α, β-unsaturated nitrile / conjugated diene rubber, the monomers that form the structural units (a1), (a2), and (a3) are preferably radicals. It can be obtained by copolymerization in the presence of a polymerization initiator.
上記単量体を含む混合物を、ラジカル重合開始剤の存在下で共重合する具体的方法を以下に示す。 A specific method for copolymerizing the mixture containing the monomer in the presence of a radical polymerization initiator is shown below.
ラジカル重合開始剤としては、アゾビスイソブチロニトリル等のアゾ化合物、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、tert−ブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、パラメンタンヒドロパーオキサイド、ジ−tert−ブチルパーオキサイド、ジクミルパーオキサイド等の有機過酸化物、過硫酸カリウム等の無機過酸化物、及びこれら過酸化物と硫酸第一鉄とを組み合わせたレドックス系触媒等が挙げられる。これらのラジカル重合開始剤は、1種単独であるいは2種以上を組み合わせて用いてもよい。 Examples of the radical polymerization initiator include azo compounds such as azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, di-tert-butyl peroxy Examples thereof include organic peroxides such as oxide and dicumyl peroxide, inorganic peroxides such as potassium persulfate, and redox catalysts obtained by combining these peroxides with ferrous sulfate. These radical polymerization initiators may be used alone or in combination of two or more.
上記ラジカル重合開始剤の使用量としては、単量体の全量100質量部に対し、通常、0.001〜2質量部である。重合方法としては塊状重合、溶液重合、懸濁重合、乳化重合等の公知の方法が可能であるが、乳化重合が特に好ましい。 As the usage-amount of the said radical polymerization initiator, it is 0.001-2 mass parts normally with respect to 100 mass parts of whole quantity of a monomer. As the polymerization method, known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used, and emulsion polymerization is particularly preferable.
乳化重合に使用する乳化剤としては、アニオン系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、両性界面活性剤等が挙げられる。また、フッ素系の界面活性剤を使用することもできる。これらの乳化剤は、1種のみを用いてもよいし、2種以上を併用することもできる。通常、アニオン系界面活性剤が多用され、例えば、炭素数10以上の長鎖脂肪酸塩、ロジン酸塩等が用いられる。具体的には、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、オレイン酸、ステアリン酸のカリウム塩及び又はナトリウム塩等が挙げられる。 Examples of the emulsifier used for emulsion polymerization include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Moreover, a fluorine-type surfactant can also be used. These emulsifiers may use only 1 type and can also use 2 or more types together. Usually, anionic surfactants are frequently used. For example, long chain fatty acid salts having 10 or more carbon atoms, rosin acid salts and the like are used. Specific examples include capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, and potassium and / or sodium salts of stearic acid.
共重合ゴムの分子量を調節するために連鎖移動剤を使用することもできる。この連鎖移動剤としては、tert−ドデシルメルカプタン、n−ドデシルメルカプタン等のアルキルメルカプタン、四塩化炭素、チオグリコール類、ジテルペン、ターピノーレン、γ−テルピネン類等を使用することができる。 A chain transfer agent can also be used to adjust the molecular weight of the copolymer rubber. As this chain transfer agent, alkyl mercaptans such as tert-dodecyl mercaptan and n-dodecyl mercaptan, carbon tetrachloride, thioglycols, diterpenes, terpinolene, γ-terpinenes and the like can be used.
上記α,β−不飽和ニトリル・共役ジエン系ゴムの製造において、単量体、乳化剤、ラジカル重合開始剤及び連鎖移動剤等は、反応容器に全量を一括して投入して重合を開始してもよいし、反応継続時に連続的あるいは間欠的に追加し、添加してもよい。この重合は、酸素を除去した反応器を用いて、通常、0〜100℃で、好ましくは0〜80℃の重合温度で行う。反応途中で、原料の添加法、温度、攪拌等の製造条件等を適宜に変更することもできる。重合方式は連続式でもよいし、回分式であってもよい。 In the production of the above α, β-unsaturated nitrile / conjugated diene rubber, monomers, emulsifiers, radical polymerization initiators, chain transfer agents, etc. are charged all at once into the reaction vessel to initiate polymerization. Alternatively, it may be added continuously or intermittently during the reaction. This polymerization is usually carried out at a polymerization temperature of 0 to 100 ° C., preferably 0 to 80 ° C., using a reactor from which oxygen has been removed. During the reaction, the raw material addition method, temperature, production conditions such as stirring, etc. can be appropriately changed. The polymerization method may be a continuous method or a batch method.
重合時間は、通常、0.01〜30時間程度で、所定の重合転化率に達した時点で、重合停止剤を添加する等によって重合を停止する。重合停止剤としては、ヒドロキシルアミン、N,N−ジエチルヒドロキシルアミン等のアミン化合物、ヒドロキノン等のキノン化合物等が用いられる。 The polymerization time is usually about 0.01 to 30 hours, and when the predetermined polymerization conversion rate is reached, the polymerization is stopped by adding a polymerization terminator or the like. As the polymerization terminator, amine compounds such as hydroxylamine and N, N-diethylhydroxylamine, quinone compounds such as hydroquinone, and the like are used.
重合停止後、得られた乳化液(ラテックス)から、必要に応じて水蒸気蒸留等の方法により未反応単量体を除去し、その後、塩化ナトリウム、塩化カルシウム、塩化カリウム等の塩、又は塩酸、硝酸、硫酸等の酸を添加し、共重合ゴムを凝固せしめ、水洗、乾燥することにより目的とする共重合ゴムが得られる。 After the polymerization is stopped, the unreacted monomer is removed from the obtained emulsion (latex) by a method such as steam distillation, if necessary, and then a salt such as sodium chloride, calcium chloride, potassium chloride, or hydrochloric acid, By adding an acid such as nitric acid or sulfuric acid, the copolymer rubber is coagulated, washed with water and dried to obtain the desired copolymer rubber.
部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムは、公知の方法、例えば特開昭58−17103号公報又は特開昭59−117501号公報に記載の方法で得ることができる。 The partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber can be obtained by a known method, for example, the method described in JP-A-58-17103 or JP-A-59-117501.
本発明の耐燃料油性ゴム組成物において、α,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムは、カルボキシル基を含有するカルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムであってもよい。ここで、「カルボキシル基」は、「−COOH」及び/又は「−COO-」を意味する。 In the fuel oil-resistant rubber composition of the present invention, the α, β-unsaturated nitrile / conjugated diene rubber and / or the partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber is a carboxyl group containing a carboxyl group. It may be a contained unsaturated nitrile / conjugated diene rubber and / or a carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene rubber. Here, the “carboxyl group” means “—COOH” and / or “—COO − ”.
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムは、上述した実施の形態のα,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴム1分子にカルボキシル基を少なくとも1つ有するものであれば特に限定されない。カルボキシル基の含有量は、0.02〜2.5mmol/gが好ましく、0.04〜2mmol/gが更に好ましく、0.08〜1mmol/gが特に好ましい。カルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムは、α,β−不飽和ニトリル単量体に由来する構造単位(a1)15〜60質量%、共役ジエン単量体に由来する構造単位(a2)40〜85質量%、これらの単量体と共重合可能な他の単量体に由来する構造単位(a3)0〜20質量%を含有することが好ましい((a1)+(a2)+(a3)=100質量%)。 The carboxyl group-containing unsaturated nitrile / conjugated diene rubber and / or the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene rubber is the α, β-unsaturated nitrile / conjugated diene rubber of the above-described embodiment and There is no particular limitation as long as it has at least one carboxyl group per molecule of partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber. The content of the carboxyl group is preferably 0.02 to 2.5 mmol / g, more preferably 0.04 to 2 mmol / g, and particularly preferably 0.08 to 1 mmol / g. The carboxyl group-containing unsaturated nitrile / conjugated diene rubber and / or the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene rubber is a structural unit (a1) 15 to 15 derived from an α, β-unsaturated nitrile monomer. 60 mass%, structural unit derived from conjugated diene monomer (a2) 40-85 mass%, structural unit derived from other monomer copolymerizable with these monomers (a3) 0-20 mass % ((A1) + (a2) + (a3) = 100% by mass).
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムは、α,β−不飽和ニトリル単量体と、共役ジエン単量体と、カルボキシル基を有する単量体と、を含む単量体を用いた重合等によって、これらの各単量体に由来する構造単位を有する重合体(ゴム)であってもよいし、α,β−不飽和ニトリル単量体及び共役ジエン単量体の少なくとも一方にカルボキシル基を有する単量体を含む単量体を用いて得られるゴムであってもよい。カルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムは、上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムを、上述した部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムを製造する場合の部分水素化の方法で、部分水素化することにより得ることもできる。 As the carboxyl group-containing unsaturated nitrile / conjugated diene rubber, a monomer containing an α, β-unsaturated nitrile monomer, a conjugated diene monomer, and a monomer having a carboxyl group was used. A polymer (rubber) having a structural unit derived from each of these monomers may be obtained by polymerization or the like, and at least one of an α, β-unsaturated nitrile monomer and a conjugated diene monomer may be carboxylated. The rubber | gum obtained using the monomer containing the monomer which has group may be sufficient. Carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene rubber is the above-mentioned partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber produced from the above carboxyl group-containing unsaturated nitrile / conjugated diene rubber. It can also be obtained by partial hydrogenation by the method of partial hydrogenation.
本実施の形態の耐燃料油性ゴム組成物において、上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムとしては、α,β−不飽和ニトリル単量体に由来する構造単位(b1)15〜60質量%と、共役ジエン単量体に由来する構造単位(b2)39.8〜65質量%と、カルボキシル基を有する単量体に由来する構造単位(b3)0.2〜20質量%と、上記単量体と共重合可能な他の単量体に由来する構造単位(b4)0〜20質量%と、を含有〔但し、(b1)+(b2)+(b3)+(b4)=100質量%〕するものであることが好ましい。 In the fuel oil resistant rubber composition of the present embodiment, the carboxyl group-containing unsaturated nitrile / conjugated diene rubber and / or the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene rubber may be α, β-unsaturated. The structural unit (b1) derived from a saturated nitrile monomer (15 to 60% by mass), the structural unit (b2) derived from a conjugated diene monomer (39.8 to 65% by mass), and a monomer having a carboxyl group Containing 0.2 to 20% by mass of the derived structural unit (b3) and 0 to 20% by mass of the structural unit (b4) derived from another monomer copolymerizable with the above monomer [provided that (B1) + (b2) + (b3) + (b4) = 100% by mass]].
上記α,β−不飽和ニトリル単量体としては、上記α,β−不飽和ニトリル・共役ジエン系ゴムの説明において例示した化合物が挙げられ、これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the α, β-unsaturated nitrile monomer include the compounds exemplified in the description of the α, β-unsaturated nitrile / conjugated diene rubber, and these may be used alone or in combination of two or more. Can be used.
上記α,β−不飽和ニトリル単量体に由来する構造単位(b1)の含有量は、全構造単位量を100質量%とした場合、上述のように15〜60質量%が好ましく、20〜50質量%が更に好ましく、35〜50質量%が特に好ましい。この構造単位(b1)の含有量が15質量%未満では、加硫ゴムとしたときの耐燃料油性が劣る傾向にあり、一方、60質量%を超えると、加硫ゴムとしたときの硬度が高くなり、ゴムらしさがなくなる傾向にある。 The content of the structural unit (b1) derived from the α, β-unsaturated nitrile monomer is preferably 15 to 60% by mass as described above when the total structural unit amount is 100% by mass, and preferably 20 to 20%. 50 mass% is still more preferable, and 35-50 mass% is especially preferable. When the content of the structural unit (b1) is less than 15% by mass, the fuel oil resistance tends to be inferior when the vulcanized rubber is used. On the other hand, when the content exceeds 60% by mass, the hardness when the vulcanized rubber is used is low. It tends to be high and lose rubberiness.
上記共役ジエン単量体としては、上記α,β−不飽和ニトリル・共役ジエン系ゴムの説明において例示した化合物が挙げられ、これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the conjugated diene monomer include the compounds exemplified in the description of the α, β-unsaturated nitrile / conjugated diene rubber, and these can be used singly or in combination of two or more. .
上記共役ジエン単量体に由来する構造単位(b2)の含有量は、全構造単位量を100質量%とした場合、好ましくは39.8〜65質量%、更に好ましくは42〜60質量%、特に好ましくは42〜50質量%である。この構造単位(b2)の含有量が39.8質量%未満では、加硫ゴムとしたときの硬度が高くなり、ゴムらしさがなくなる傾向にあり、一方、65質量%を超えると、加硫ゴムとしたときの耐燃料油性が劣る傾向にある。 The content of the structural unit (b2) derived from the conjugated diene monomer is preferably 39.8 to 65% by mass, more preferably 42 to 60% by mass, when the total structural unit amount is 100% by mass. Especially preferably, it is 42-50 mass%. If the content of the structural unit (b2) is less than 39.8% by mass, the hardness of the vulcanized rubber tends to be high and the rubber-like property tends to be lost. The fuel oil resistance tends to be inferior.
上記カルボキシル基を有する単量体としては、不飽和カルボン酸(そのモノエステルを含む)等が挙げられる。この不飽和カルボン酸としては、アクリル酸、メタクリル酸、クロトン酸、ケイ皮酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸、テトラコン酸等の不飽和カルボン酸類;マレイン酸モノメチル、マレイン酸モノエチル、イタコン酸モノメチル、イタコン酸モノエチル、フタル酸モノヒドロキシレンアクリレート、ヘキサヒドロフタル酸モノ−2−アクリロイルオキシエチル、ヘキサヒドロフタル酸モノ−2−メタクリロイルオキシエチル、フタル酸、こはく酸、アジピン酸等の非重合性多価カルボン酸とアリルアルコール、メタリルアルコール、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート等のヒドロキシル基含有不飽和化合物とのモノエステル等の遊離カルボキシル基含有エステル類等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the monomer having a carboxyl group include unsaturated carboxylic acids (including monoesters thereof). Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, tetraconic acid and the like; monomethyl maleate; , Monoethyl maleate, monomethyl itaconate, monoethyl itaconate, monohydroxylene phthalate, mono-2-acryloyloxyethyl hexahydrophthalate, mono-2-methacryloyloxyethyl hexahydrophthalate, phthalic acid, succinic acid, A free carboxyl group-containing ester such as a monoester of a non-polymerizable polyvalent carboxylic acid such as adipic acid and a hydroxyl group-containing unsaturated compound such as allyl alcohol, methallyl alcohol, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. Le, and the like can be mentioned. These can be used alone or in combination of two or more.
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムを構成する構造単位(b3)の含有量は、全構造単位量を100質量%とした場合、好ましくは0.2〜20質量%、更に好ましくは0.2〜10質量%、特に好ましくは0.2〜7質量%である。この構造単位(b3)の含有量が0.2質量%未満では、加硫ゴムとしたときの耐オゾン性が不十分となる傾向にあり、一方、20質量%を超えると、加硫ゴムとしたときの圧縮永久歪みが悪化する傾向にある。 The content of the structural unit (b3) constituting the carboxyl group-containing unsaturated nitrile / conjugated diene rubber is preferably 0.2 to 20% by mass, more preferably 100% by mass when the total structural unit amount is 100% by mass. It is 0.2-10 mass%, Most preferably, it is 0.2-7 mass%. When the content of the structural unit (b3) is less than 0.2% by mass, ozone resistance when used as a vulcanized rubber tends to be insufficient. On the other hand, when the content exceeds 20% by mass, the vulcanized rubber and The compression set at the time tends to deteriorate.
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムが、上記構造単位(b1)、(b2)及び(b3)から構成される場合、これらの含有割合(b1)/(b2)/(b3)の組み合わせは、これらの合計を100質量%とした場合、上述のように15〜60質量%/39.8〜65質量%/0.2〜20質量%であることが好ましく、27〜59.6質量%/40〜63質量%/0.4〜10質量%であることが更に好ましく、33〜54.6質量%/45〜60質量%/0.4〜7質量%であることが特に好ましい。 When the carboxyl group-containing unsaturated nitrile / conjugated diene rubber is composed of the structural units (b1), (b2) and (b3), the content ratio (b1) / (b2) / (b3) The combination is preferably 15 to 60% by mass / 39.8 to 65% by mass / 0.2 to 20% by mass, and 27 to 59.6% as described above, when the total of these is 100% by mass. It is more preferable that it is mass% / 40-63 mass% / 0.4-10 mass%, and it is especially preferable that it is 33-54.6 mass% / 45-60 mass% / 0.4-7 mass%. .
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムは、上記構造単位(b1)、(b2)及び(b3)に加え、上記α,β−不飽和ニトリル単量体、共役ジエン単量体及びカルボキシル基を含有する単量体と共重合可能な他の単量体に由来する構造単位(b4)を含有していてもよい。上記他の単量体としては、(メタ)アクリル酸アルキルエステル、芳香族ビニル系単量体等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 In addition to the structural units (b1), (b2) and (b3), the carboxyl group-containing unsaturated nitrile / conjugated diene rubber contains the α, β-unsaturated nitrile monomer, conjugated diene monomer and carboxyl. A structural unit (b4) derived from another monomer copolymerizable with the group-containing monomer may be contained. As said other monomer, (meth) acrylic-acid alkylester, an aromatic vinyl-type monomer, etc. are mentioned. These can be used alone or in combination of two or more.
上記(メタ)アクリル酸アルキルエステル及び芳香族ビニル系単量体としては、上記α,β−不飽和ニトリル・共役ジエン系ゴムの説明において例示した化合物が挙げられ、これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the (meth) acrylic acid alkyl ester and the aromatic vinyl monomer include the compounds exemplified in the description of the α, β-unsaturated nitrile / conjugated diene rubber, and these may be used alone or in combination. Two or more kinds can be used in combination.
尚、上記芳香族ビニル系単量体は、アミノ基、ヒドロキシル基等の官能基を有する化合物であってもよい。アミノ基を有する芳香族ビニル系単量体としては、N,N−ジメチル−p−アミノスチレン、N,N−ジエチル−p−アミノスチレン、ジメチル(p−ビニルベンジル)アミン、ジエチル(p−ビニルベンジル)アミン、ジメチル(p−ビニルフェネチル)アミン、ジエチル(p−ビニルフェネチル)アミン、ジメチル(p−ビニルベンジルオキシメチル)アミン、ジメチル[2−(p−ビニルベンジルオキシ)エチル]アミン、ジエチル(p−ビニルベンジルオキシメチル)アミン、ジエチル[2−(p−ビニルベンジルオキシ)エチル]アミン、ジメチル(p−ビニルフェネチルオキシメチル)アミン、ジメチル[2−(p−ビニルフェネチルオキシ)エチル]アミン、ジエチル(p−ビニルフェネチルオキシメチル)アミン、ジエチル[2−(p−ビニルフェネチルオキシ)エチル]アミン、2−ビニルピリジン、3−ビニルピリジン、4−ビニルピリジン等が挙げられる。 The aromatic vinyl monomer may be a compound having a functional group such as an amino group or a hydroxyl group. Examples of the aromatic vinyl monomer having an amino group include N, N-dimethyl-p-aminostyrene, N, N-diethyl-p-aminostyrene, dimethyl (p-vinylbenzyl) amine, and diethyl (p-vinyl). Benzyl) amine, dimethyl (p-vinylphenethyl) amine, diethyl (p-vinylphenethyl) amine, dimethyl (p-vinylbenzyloxymethyl) amine, dimethyl [2- (p-vinylbenzyloxy) ethyl] amine, diethyl ( p-vinylbenzyloxymethyl) amine, diethyl [2- (p-vinylbenzyloxy) ethyl] amine, dimethyl (p-vinylphenethyloxymethyl) amine, dimethyl [2- (p-vinylphenethyloxy) ethyl] amine, Diethyl (p-vinylphenethyloxymethyl) amine, diethyl 2- (p-vinyl phenethyl oxy) ethyl] amine, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, and the like.
ヒドロキシル基を有する芳香族ビニル系単量体としては、o−ヒドロキシスチレン、m−ヒドロキシスチレン、p−ヒドロキシスチレン、o−ヒドロキシ−α−メチルスチレン、m−ヒドロキシ−α−メチルスチレン、p−ヒドロキシ−α−メチルスチレン、p−ビニルベンジルアルコール等が挙げられる。 Examples of the aromatic vinyl monomer having a hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, and p-hydroxy. -Α-methylstyrene, p-vinylbenzyl alcohol and the like.
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムを構成する構造単位(b4)の含有量は、全構造単位量を100質量%とした場合、0〜20質量%が好ましく、0〜15質量%が更に好ましく、0〜10質量%が特に好ましい。この構造単位(b4)の含有量が20質量%を超えると、加硫ゴムとしたときの耐オゾン性が劣る傾向にある。 The content of the structural unit (b4) constituting the carboxyl group-containing unsaturated nitrile / conjugated diene rubber is preferably 0 to 20% by mass, and preferably 0 to 15% by mass when the total structural unit amount is 100% by mass. Is more preferable, and 0 to 10% by mass is particularly preferable. When the content of the structural unit (b4) exceeds 20% by mass, ozone resistance when used as a vulcanized rubber tends to be inferior.
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び上記カルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムのムーニー粘度[ML1+4(100℃)]は10〜200が好ましく、40〜100が更に好ましい。上記ムーニー粘度が小さすぎると、加硫ゴムとしたときの強度が低下する傾向にあり、一方、大きすぎると、混練時の加工性が劣る場合がある。 The Mooney viscosity [ML 1 + 4 (100 ° C.)] of the carboxyl group-containing unsaturated nitrile / conjugated diene rubber and the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene rubber is preferably 10-200, preferably 40- 100 is more preferable. If the Mooney viscosity is too small, the strength of the vulcanized rubber tends to decrease. On the other hand, if the Mooney viscosity is too large, the workability during kneading may be inferior.
上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムの製造方法は、上記所定の単量体を用い、上記α,β−不飽和ニトリル・共役ジエン系ゴムの製造方法と同様とすることができる。そして、上記カルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴムの製造方法は、上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴムを、上記製造方法により製造した後に部分水素化することにより得ることができる。 The method for producing the carboxyl group-containing unsaturated nitrile / conjugated diene rubber can be the same as the method for producing the α, β-unsaturated nitrile / conjugated diene rubber using the predetermined monomer. The method for producing the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene rubber is obtained by partially hydrogenating the carboxyl group-containing unsaturated nitrile / conjugated diene rubber produced by the production method. be able to.
本発明の耐燃料油性ゴム組成物に含有される原料ゴムとしては、更にアクリル系ゴムも含有されることが好ましい。この場合、アクリル系ゴム(A)と、α,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴム(B)とを合わせたものが原料ゴム中に含有されることになる。これらの含有割合(A)/(B)は、これらの合計を100質量%とした場合、好ましくは(5〜80質量%)/(20〜95質量%)、更に好ましくは(30〜60質量%)/(40〜70質量%)、特に好ましくは(35〜55質量%)/(45〜65質量%)である。上記アクリル系ゴム(A)の含有割合が多すぎると、加硫ゴムとしたときの強度が低下する傾向にあり、一方、少なすぎると、加硫ゴムとしたときの耐オゾン性が必要な場合に不十分となる傾向にある。 The raw rubber contained in the fuel oil resistant rubber composition of the present invention preferably further contains acrylic rubber. In this case, a combination of acrylic rubber (A) and α, β-unsaturated nitrile / conjugated diene rubber and / or partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber (B) It will be contained in the raw rubber. These content ratios (A) / (B) are preferably (5 to 80% by mass) / (20 to 95% by mass), more preferably (30 to 60% by mass) when the total of these contents is 100% by mass. %) / (40 to 70% by mass), particularly preferably (35 to 55% by mass) / (45 to 65% by mass). If the acrylic rubber (A) content is too high, the strength of the vulcanized rubber tends to decrease. On the other hand, if the content is too low, ozone resistance when the vulcanized rubber is used is required. Tend to be insufficient.
アクリル系ゴムの種類としては特に限定されるものではなく、アクリル酸エステル単量体、不飽和ニトリル単量体、架橋点として、塩素含有単量体、非共役ジエン単量体、カルボキシル基含有単量体等を重合させたものを好適に使用することができる。これらの単量体は、1種単独であるいは2種以上を組み合わせて用いることができる。また、これら単量体等と共重合可能な他の単量体を更に加えて重合してもよい。 The type of acrylic rubber is not particularly limited, and acrylic acid ester monomers, unsaturated nitrile monomers, crosslinking points include chlorine-containing monomers, non-conjugated diene monomers, carboxyl group-containing monomers. What polymerized a monomer etc. can be used conveniently. These monomers can be used alone or in combination of two or more. Moreover, you may superpose | polymerize by adding the other monomer copolymerizable with these monomers.
上記アクリル系ゴムとしては、不飽和エポキシ単量体を更に加えて重合したエポキシ基含有アクリル系ゴムが好ましい。以下、エポキシ基含有アクリル系ゴムについて更に説明する。 As the acrylic rubber, an epoxy group-containing acrylic rubber polymerized by further adding an unsaturated epoxy monomer is preferable. Hereinafter, the epoxy group-containing acrylic rubber will be further described.
上記エポキシ基含有アクリル系ゴムは、1分子にエポキシ基を少なくとも1つ有するものであれば特に限定されるものではない。そしてエポキシ基を0.01〜1.5mmol/g含有することが好ましい。このエポキシ基の含有量は、更に好ましくは0.02〜1mmol/g、特に好ましくは0.02〜0.6mmol/gである。この含有量が0.01mmol/g未満では、本発明の耐燃料油性ゴム組成物を用いて得られる加硫ゴムの強度が不十分となる傾向にあり、一方、1.5mmol/gを超えると、加硫ゴムの圧縮永久歪みが大きくなる場合がある。上記エポキシ基含有アクリル系ゴムは、アクリル酸アルキルエステル、アクリル酸アルコキシアルキルエステル等のアクリル系単量体と、エポキシ基を有する単量体とを含む単量体を用いた重合等によって、各単量体に由来し且つエポキシ基を有する構造単位を有するアクリル系ゴムであってもよいし、エポキシ基を有するアクリル系単量体を含む単量体を用いた重合等によって、各単量体に由来し且つエポキシ基を有する構造単位を有するアクリル系ゴムであってもよい。 The epoxy group-containing acrylic rubber is not particularly limited as long as it has at least one epoxy group per molecule. And it is preferable to contain 0.01-1.5 mmol / g of epoxy groups. The content of this epoxy group is more preferably 0.02 to 1 mmol / g, particularly preferably 0.02 to 0.6 mmol / g. When the content is less than 0.01 mmol / g, the strength of the vulcanized rubber obtained using the fuel-resistant oil-resistant rubber composition of the present invention tends to be insufficient, whereas when it exceeds 1.5 mmol / g. In some cases, the compression set of the vulcanized rubber increases. The epoxy group-containing acrylic rubber is produced by polymerization using a monomer containing an acrylic monomer such as an acrylic acid alkyl ester or an acrylic acid alkoxyalkyl ester and a monomer having an epoxy group. It may be an acrylic rubber having a structural unit derived from a monomer and having an epoxy group, or by polymerization using a monomer containing an acrylic monomer having an epoxy group, etc. It may be an acrylic rubber having a structural unit derived from and having an epoxy group.
上記エポキシ基含有アクリル系ゴムとしては、アクリル酸アルキルエステル及びアクリル酸アルコキシアルキルエステルから選ばれる少なくとも1種の単量体に由来する構造単位(c1)20〜99.8質量%と、不飽和エポキシ単量体に由来し且つエポキシ基を有する構造単位(c2)0.2〜20質量%と、不飽和ニトリル単量体に由来する構造単位(c3)0〜60質量%と、上記単量体と共重合可能な他の単量体に由来する構造単位(c4)0〜20質量%と、を含有〔但し、(c1)+(c2)+(c3)+(c4)=100質量%〕するエポキシ基含有アクリル系ゴムが好ましい。 Examples of the epoxy group-containing acrylic rubber include 20 to 99.8% by mass of a structural unit (c1) derived from at least one monomer selected from alkyl acrylates and alkoxyalkyl acrylates, and unsaturated epoxy. 0.2 to 20% by mass of a structural unit (c2) derived from a monomer and having an epoxy group, 0 to 60% by mass of a structural unit (c3) derived from an unsaturated nitrile monomer, and the above monomer And 0 to 20% by mass of a structural unit (c4) derived from another monomer copolymerizable with (wherein (c1) + (c2) + (c3) + (c4) = 100% by mass) An epoxy group-containing acrylic rubber is preferred.
上記アクリル酸アルキルエステルとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸n−プロピル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸n−ペンチル、アクリル酸イソアミル、アクリル酸n−ヘキシル、アクリル酸2−メチルペンチル、アクリル酸n−オクチル、アクリル酸2−エチルヘキシル、アクリル酸n−デシル、アクリル酸n−ドデシル、アクリル酸n−オクタデシル等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, acrylic acid Examples include 2-methylpentyl, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, and the like. These can be used alone or in combination of two or more.
上記アクリル酸アルコキシアルキルエステルとしては、アクリル酸2−メトキシエチル、アクリル酸2−エトキシエチル、アクリル酸2−(n−プロポキシ)エチル、アクリル酸2−(n−ブトキシ)エチル、アクリル酸3−メトキシプロピル、アクリル酸3−エトキシプロピル、アクリル酸2−(n−プロポキシ)プロピル、アクリル酸2−(n−ブトキシ)プロピル等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the alkoxyalkyl acrylate include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, and 3-methoxy acrylate. Examples include propyl, 3-ethoxypropyl acrylate, 2- (n-propoxy) propyl acrylate, 2- (n-butoxy) propyl acrylate, and the like. These can be used alone or in combination of two or more.
上記エポキシ含有アクリル系ゴムを構成する構造単位(c1)の含有量は、全構造単位量を100質量%とした場合、好ましくは20〜99.8質量%、更に好ましくは25〜90質量%、特に好ましくは30〜85質量%である。この構造単位(c1)の含有量が20質量%未満では、加硫ゴムとしたときの硬度が高くなり、ゴムらしさがなくなる傾向にあり、一方、99.8質量%を超えると、加硫ゴムとしたときの強度が低下する傾向にある。 The content of the structural unit (c1) constituting the epoxy-containing acrylic rubber is preferably 20 to 99.8% by mass, more preferably 25 to 90% by mass, when the total structural unit amount is 100% by mass. Especially preferably, it is 30-85 mass%. If the content of the structural unit (c1) is less than 20% by mass, the hardness when made into a vulcanized rubber tends to be high and the rubber-like property tends to be lost. There is a tendency for the strength to decrease.
上記不飽和エポキシ単量体としては、(メタ)アクリル酸グリシジル、(メタ)アクリル酸3,4−オキシシクロヘキシル、ビニルグリシジルエーテル、アリルグリシジルエーテル、メタクリルグリシジルエーテル等が挙げられる。これらは、1種単独であるいは2種以上組み合わせて用いることができる。 Examples of the unsaturated epoxy monomer include glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, allyl glycidyl ether, and methacryl glycidyl ether. These can be used singly or in combination of two or more.
上記エポキシ含有アクリル系ゴムを構成する構造単位(c2)の含有量は、全構造単位量を100質量%とした場合、0.2〜20質量%、好ましくは0.4〜15質量%、更に好ましくは0.5〜10質量%である。この構造単位(c2)の含有量が0.2質量%未満では、加硫ゴムとしたときの強度が不十分となる傾向にあり、一方、20質量%を超えると、加硫ゴムとしたときの圧縮永久歪みが大きくなる場合がある。尚、上記構造単位(c2)におけるエポキシ基の含有量は特に限定されない。 The content of the structural unit (c2) constituting the epoxy-containing acrylic rubber is 0.2 to 20% by mass, preferably 0.4 to 15% by mass, when the total structural unit amount is 100% by mass. Preferably it is 0.5-10 mass%. When the content of the structural unit (c2) is less than 0.2% by mass, the strength when vulcanized rubber tends to be insufficient. On the other hand, when the content exceeds 20% by mass, the vulcanized rubber is obtained. In some cases, the compression set becomes large. In addition, content of the epoxy group in the said structural unit (c2) is not specifically limited.
上記エポキシ含有アクリル系ゴムが、上記構造単位(c1)及び(c2)から構成される場合、これらの好ましい含有割合(c1)/(c2)の組み合わせは、これらの合計を100質量%とした場合、好ましくは(80〜99.8質量%)/(0.2〜20質量%)であり、更に好ましくは(85〜99.6質量%)/(0.4〜15質量%)である。 When the said epoxy-containing acrylic rubber is comprised from the said structural unit (c1) and (c2), when these preferable content rate (c1) / (c2) combination makes these total 100 mass% The ratio is preferably (80 to 99.8% by mass) / (0.2 to 20% by mass), and more preferably (85 to 99.6% by mass) / (0.4 to 15% by mass).
上記エポキシ含有アクリル系ゴムは、上記構造単位(c1)及び(c2)に加え、上記アクリル酸アルキルエステル及びアクリル酸アルコキシアルキルエステルと共重合可能な不飽和ニトリル単量体に由来する構造単位(c3)を含有していてもよい。 In addition to the structural units (c1) and (c2), the epoxy-containing acrylic rubber is a structural unit (c3) derived from an unsaturated nitrile monomer copolymerizable with the alkyl acrylate and alkoxyalkyl acrylate. ) May be contained.
上記不飽和ニトリル単量体としては、上述したα,β−不飽和ニトリル・共役ジエン系ゴムの説明において例示したα,β−不飽和ニトリル単量体が挙げられ、これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the unsaturated nitrile monomer include the α, β-unsaturated nitrile monomers exemplified in the description of the α, β-unsaturated nitrile / conjugated diene rubber described above, and these may be used alone. Or it can use combining 2 or more types.
上記エポキシ含有アクリル系ゴムを構成する構造単位(c3)の含有量は、全構造単位量を100質量%とした場合、好ましくは0.5〜60質量%、更に好ましくは5〜40質量%、特に好ましくは10〜30質量%である。この構造単位(c2)の含有量が60質量%を超えると、加硫ゴムとしたときの硬度が高くなり、ゴムらしさがなくなる傾向にある。 The content of the structural unit (c3) constituting the epoxy-containing acrylic rubber is preferably 0.5 to 60% by mass, more preferably 5 to 40% by mass, when the total structural unit amount is 100% by mass. Especially preferably, it is 10-30 mass%. If the content of the structural unit (c2) exceeds 60% by mass, the hardness of the vulcanized rubber tends to be high and the rubber-like property tends to be lost.
上記エポキシ含有アクリル系ゴムが、上記構造単位(c1)、(c2)及び(c3)から構成される場合、これらの含有割合(c1)/(c2)/(c3)の組み合わせは、これらの合計を100質量%とした場合、好ましくは(20〜99.3質量%)/(0.2〜20質量%)/(0.5〜60質量%)であり、更に好ましくは(40〜84.6質量%)/(0.4〜20質量%)/(15〜40質量%)、特に好ましくは(60〜89.6質量%)/(0.4〜10質量%)/(10〜30質量%)である。 When the epoxy-containing acrylic rubber is composed of the structural units (c1), (c2) and (c3), the combination of these content ratios (c1) / (c2) / (c3) is the sum of these Is preferably (20 to 99.3 mass%) / (0.2 to 20 mass%) / (0.5 to 60 mass%), more preferably (40 to 84. mass%). 6 mass%) / (0.4-20 mass%) / (15-40 mass%), particularly preferably (60-89.6 mass%) / (0.4-10 mass%) / (10-30 Mass%).
尚、上記エポキシ含有アクリル系ゴムは、上記構造単位(c1)、(c2)及び(c3)に加え、上記アクリル酸アルキルエステル、アクリル酸アルコキシアルキルエステル、不飽和ニトリル単量体及び不飽和エポキシ単量体と共重合可能な他の単量体に由来する構造単位(c4)を更に含有していてもよい。 In addition to the structural units (c1), (c2), and (c3), the epoxy-containing acrylic rubber includes the acrylic acid alkyl ester, acrylic acid alkoxyalkyl ester, unsaturated nitrile monomer, and unsaturated epoxy monomer. It may further contain a structural unit (c4) derived from another monomer copolymerizable with the monomer.
上記他の単量体としては、上述したα,β−不飽和ニトリル・共役ジエン系ゴムの説明において例示した他の単量体が挙げられ、これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the other monomer include other monomers exemplified in the description of the α, β-unsaturated nitrile / conjugated diene rubber described above, and these may be used alone or in combination of two or more. Can be used.
上記エポキシ含有アクリル系ゴムを構成する構造単位(c4)の含有量は、全構造単位量を100質量%とした場合、好ましくは0.1〜20質量%、更に好ましくは0.2〜15質量%、特に好ましくは0.2〜7質量%である。この構造単位(c4)の含有量が20質量%を超えると、混練時の加工性が劣る場合がある。 The content of the structural unit (c4) constituting the epoxy-containing acrylic rubber is preferably 0.1 to 20% by mass, more preferably 0.2 to 15% by mass when the total structural unit amount is 100% by mass. %, Particularly preferably 0.2 to 7% by mass. When the content of the structural unit (c4) exceeds 20% by mass, workability during kneading may be inferior.
上記エポキシ含有アクリル系ゴムのムーニー粘度[ML1+4(100℃)]は10〜200であり、好ましくは20〜100である。上記ムーニー粘度が小さすぎると、加硫ゴムとしたときの強度が低下する傾向にあり、一方、大きすぎると、混練時の加工性が劣る場合がある。 The Mooney viscosity [ML 1 + 4 (100 ° C.)] of the epoxy-containing acrylic rubber is 10 to 200, preferably 20 to 100. If the Mooney viscosity is too small, the strength of the vulcanized rubber tends to decrease. On the other hand, if the Mooney viscosity is too large, the workability during kneading may be inferior.
上記エポキシ含有アクリル系ゴムの製造方法は、所定の単量体を用い、上述したα,β−不飽和ニトリル・共役ジエン系ゴムの製造方法と同様とすることができる。 The method for producing the epoxy-containing acrylic rubber can be the same as the method for producing the α, β-unsaturated nitrile / conjugated diene rubber described above using a predetermined monomer.
本発明の耐燃料油性ゴム組成物は、上記エポキシ基含有アクリル系ゴム(C)と、上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴム(D)とを原料ゴムとして含有することが好ましい。 The fuel oil resistant rubber composition of the present invention comprises the epoxy group-containing acrylic rubber (C), the carboxyl group-containing unsaturated nitrile / conjugated diene rubber and / or the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene. The base rubber (D) is preferably contained as a raw rubber.
これらの含有割合(C)/(D)は、これらの合計を100質量%とした場合、好ましくは(5〜80質量%)/(20〜95質量%)、更に好ましくは(10〜60質量%)/(40〜90質量%)、特に好ましくは(30〜55質量%)/(45〜70質量%)である。上記エポキシ基含有アクリル系ゴム(C)の含有割合が多すぎると、加硫ゴムとしたときの強度が低下する傾向にあり、一方、少なすぎると、加硫ゴムとしたときの耐オゾン性が必要な場合に不十分となる傾向にある。 These content ratios (C) / (D) are preferably (5 to 80% by mass) / (20 to 95% by mass), more preferably (10 to 60% by mass) when the total of these is 100% by mass. %) / (40 to 90% by mass), particularly preferably (30 to 55% by mass) / (45 to 70% by mass). If the content of the epoxy group-containing acrylic rubber (C) is too large, the strength when vulcanized rubber tends to decrease. On the other hand, if too small, the ozone resistance when vulcanized rubber is obtained. It tends to be inadequate when necessary.
本発明の耐燃料油性ゴム組成物は、上記エポキシ基含有アクリル系ゴム(C)と、上記カルボキシル基含有不飽和ニトリル・共役ジエン系ゴム及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴム(D)とを原料ゴムとして含有する場合に、これ以外に、他のゴム成分を含有してもよい。他のゴム成分としては、上記α,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴムが原料ゴム中に含有される場合の上記説明において挙げた他のゴム成分とすることが好ましい。 The fuel oil resistant rubber composition of the present invention comprises the epoxy group-containing acrylic rubber (C), the carboxyl group-containing unsaturated nitrile / conjugated diene rubber and / or the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene. When the rubber system (D) is contained as a raw rubber, other rubber components may be contained in addition to this. As the other rubber component, the above description in the case where the raw rubber contains the α, β-unsaturated nitrile / conjugated diene rubber and / or the partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber. It is preferable to use other rubber components mentioned in the above.
これら他のゴム成分の含有割合は、上記エポキシ基含有アクリル系ゴム(C)及び上記カルボキシル基含有不飽和ニトリル・共役ジエン系共重合体及び/又はカルボキシル基含有部分水素化不飽和ニトリル・共役ジエン系ゴム(D)の合計100質量部に対して、好ましくは0〜30質量部、更に好ましくは0〜10質量部、特に好ましくは0〜5質量部である。 The content of these other rubber components is as follows: the epoxy group-containing acrylic rubber (C) and the carboxyl group-containing unsaturated nitrile / conjugated diene copolymer and / or the carboxyl group-containing partially hydrogenated unsaturated nitrile / conjugated diene. Preferably it is 0-30 mass parts with respect to a total of 100 mass parts of a system rubber (D), More preferably, it is 0-10 mass parts, Most preferably, it is 0-5 mass parts.
本発明の耐燃料油性ゴム組成物は、補強剤、充填剤、可塑剤、加硫剤、加硫助剤(加硫促進剤)、軟化剤、老化防止剤、紫外線吸収剤、難燃剤、防菌・防かび剤、着色剤等の添加剤を含有したものとすることもできる。加硫助剤としては、亜鉛華、活性亜鉛華、表面処理亜鉛華、複合亜鉛華、複合活性亜鉛華等の酸化亜鉛含有物を1種単独で、あるいは2種以上を組み合わせて用いることができる。 The fuel oil resistant rubber composition of the present invention comprises a reinforcing agent, a filler, a plasticizer, a vulcanizing agent, a vulcanizing aid (vulcanization accelerator), a softening agent, an anti-aging agent, an ultraviolet absorber, a flame retardant, It can also contain additives such as fungi, fungicides and coloring agents. As the vulcanization aid, zinc oxide-containing materials such as zinc white, activated zinc white, surface-treated zinc white, composite zinc white, and composite active zinc white can be used alone or in combination of two or more. .
上記補強剤としては、カーボンブラック、シリカ、水酸化アルミニウム、アルミナ等が挙げられる。これらのうち、カーボンブラックが好ましい。また、これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the reinforcing agent include carbon black, silica, aluminum hydroxide, and alumina. Of these, carbon black is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
上記カーボンブラックとしては、SAFカーボンブラック、ISAFカーボンブラック、HAFカーボンブラック、FEFカーボンブラック、GPFカーボンブラック、SRFカーボンブラック、FTカーボンブラック、MTカーボンブラック、アセチレンカーボンブラック、ケッチェンブラック等が挙げられる。 Examples of the carbon black include SAF carbon black, ISAF carbon black, HAF carbon black, FEF carbon black, GPF carbon black, SRF carbon black, FT carbon black, MT carbon black, acetylene carbon black, and ketjen black.
上記補強剤の配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは5〜200質量部、更に好ましくは10〜100質量部、特に好ましくは20〜80質量部である。 The compounding amount of the reinforcing agent is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and particularly preferably 20 to 80 parts by mass with respect to 100 parts by mass in total of the raw rubber in the fuel oil resistant rubber composition. Part by mass.
上記充填剤としては、重質炭酸カルシウム、軽微性炭酸カルシウム、極微細活性化炭酸カルシウム、特殊炭酸カルシウム、塩基性炭酸マグネシウム、カオリンクレー、焼成クレー、パイロフライトクレー、シラン処理クレー、合成ケイ酸カルシウム、合成ケイ酸マグネシウム、合成ケイ酸アルミニウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、カオリン、セリサイト、タルク、微粉タルク、ウォラスナイト、ゼオライト、ゾーノトナイト、アスベスト、PMF(Processed Mineral Fiber)、胡粉、セピオライト、チタン酸カリウム、エレスタダイト、石膏繊維、ガラスバルン、シリカバルン、ハイドロタルサイト、フライアシュバルン、シラスバルン、カーボン系バルン、硫酸バリウム、硫酸アルミニウム、硫酸カルシウム、二硫化モリブデン等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the filler include heavy calcium carbonate, light calcium carbonate, ultrafine activated calcium carbonate, special calcium carbonate, basic magnesium carbonate, kaolin clay, calcined clay, pyroflight clay, silane-treated clay, and synthetic calcium silicate. , Synthetic magnesium silicate, Synthetic aluminum silicate, Magnesium carbonate, Magnesium hydroxide, Magnesium oxide, Kaolin, Sericite, Talc, Fine talc, Wollastonite, Zeolite, Zonotonite, Asbestos, PMF (Processed Mineral Fiber), Pepper powder, Sepiolite , Potassium titanate, elastadite, gypsum fiber, glass balun, silica balun, hydrotalcite, fly ash balun, shirasu balun, carbon balun, barium sulfate, sulfuric acid Luminium, calcium sulfate, molybdenum disulfide and the like can be mentioned. These can be used alone or in combination of two or more.
上記充填剤の配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは0〜200質量部、更に好ましくは0〜100質量部、特に好ましくは0〜50質量部である。 The blending amount of the filler is preferably 0 to 200 parts by mass, more preferably 0 to 100 parts by mass, and particularly preferably 0 to 50 parts by mass with respect to 100 parts by mass in total of the raw rubber in the fuel oil resistant rubber composition. Part by mass.
上記可塑剤としては、ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジイソブチルフタレート、ジオクチルフタレート、ブチルオクチルフタレート、ジ−(2−エチルヘキシル)フタレート、ジイソオクチルフタレート、ジイソデシルフタレート等のフタル酸エステル類、ジメチルアジペート、ジイソブチルアジペート、ジ−(2−エチルヘキシル)アジペート、ジイソオクチルアジペート、ジイソデシルアジペート、オクチルデシルアジペート、ジ−(2−エチルヘキシル)アゼレート、ジイソオクチルアゼレート、ジイソブチルアゼレート、ジブチルセバケート、ジ−(2−エチルヘキシル)セバケート、ジイソオクチルセバケート等の脂肪酸エステル類、トリメリット酸イソデシルエステル、トリメリット酸オクチルエステル、トリメリット酸n−オクチルエステル、トリメリット酸系イソノニルエステル等のトリメリット酸エステル類の他、ジ−(2−エチルヘキシル)フマレート、ジエチレングリコールモノオレート、グリセリルモノリシノレート、トリラウリルホスフェート、トリステアリルホスフェート、トリ−(2−エチルヘキシル)ホスフェート、エポキシ化大豆油、ポリエーテルエステル等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the plasticizer include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, diisodecyl phthalate, and dimethyl adipate. , Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- Fatty acid esters such as (2-ethylhexyl) sebacate and diisooctyl sebacate, trimellitic acid isodecyl ester, trimellitic acid octyl In addition to trimellitic esters such as esters, trimellitic acid n-octyl ester, trimellitic isononyl ester, di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinoleate, trilauryl phosphate, trilauryl phosphate Examples include stearyl phosphate, tri- (2-ethylhexyl) phosphate, epoxidized soybean oil, and polyether ester. These can be used alone or in combination of two or more.
上記可塑剤の配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは0〜80質量部、更に好ましくは10〜60質量部である。 The blending amount of the plasticizer is preferably 0 to 80 parts by mass, and more preferably 10 to 60 parts by mass with respect to 100 parts by mass in total of the raw rubber in the fuel oil resistant rubber composition.
上記加硫剤としては、硫黄、有機過酸化物等が挙げられるが、硫黄が好ましい。この硫黄としては、粉末硫黄、沈降硫黄、コロイド硫黄、表面処理硫黄、不溶性硫黄等が挙げられる。 Examples of the vulcanizing agent include sulfur and organic peroxides, and sulfur is preferred. Examples of the sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur and the like.
上記加硫剤として、硫黄を用いる場合のその配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは0.05〜5質量部、更に好ましくは0.1〜3質量部、特に好ましくは0.2〜1質量部である。 When sulfur is used as the vulcanizing agent, the blending amount thereof is preferably 0.05 to 5 parts by mass, more preferably 0.005 parts by mass with respect to 100 parts by mass in total of the raw rubber in the fuel oil resistant rubber composition. 1 to 3 parts by mass, particularly preferably 0.2 to 1 part by mass.
また、上記加硫剤としては、上述した酸化亜鉛に加えて以下の化合物を用いることができる。例えば、N−シクロヘキシル−2−ベンゾチアゾリルスルフェンアミド、N−オキシジエチレン−2−ベンゾチアゾリルスルフェンアミド、N,N−ジイソプロピル−2−ベンゾチアゾリルスルフェンアミド等のスルフェンアミド系化合物;2−メルカプトベンゾチアゾール、2−(2’,4’−ジニトロフェニル)メルカプトベンゾチアゾール、2−(4’−モルホリノジチオ)ベンゾチアゾール、ジベンゾチアジルジスルフィド等のチアゾ−ル系化合物;ジフェニルグアニジン、ジオルソトリルグアニジン、ジオルソニトリルグアニジン、オルソニトリルバイグアナイド、ジフェニルグアニジンフタレート等のグアニジン化合物;アセトアルデヒド−アニリン反応物、ブチルアルデヒド−アニリン縮合物、ヘキサメチレンテトラミン、アセトアルデヒドアンモニア等のアルデヒドアミン又はアルデヒド−アンモニア系化合物;2−メルカプトイミダゾリン等のイミダゾリン系化合物;チオカルバニリド、ジエチルチオユリア、ジブチルチオユリア、トリメチルチオユリア、ジオルソトリルチオユリア等のチオユリア系化合物;テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、テトラオクチルチウラムジスルフィド、ペンタメチレンチウラムテトラスルフィド等のチウラム系化合物;ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジ−n−ブチルジチオカルバミン酸亜鉛、エチルフェニルジチオカルバミン酸亜鉛、ブチルフェニルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸ナトリウム、ジメチルジチオカルバミン酸セレン、ジメチルジチオカルバミン酸テルル等のジチオ酸塩系化合物;ジブチルキサントゲン酸亜鉛等のザンテート系化合物;炭酸亜鉛等の無機系亜鉛化合物等を1種単独で、あるいは2種以上を組み合わせて用いることができる。上記加硫助剤は、いずれの加硫剤を使用する場合にも添加することができるが、硫黄を加硫剤とする場合により効果的である。 In addition to the above-described zinc oxide, the following compounds can be used as the vulcanizing agent. For example, sulfenamide compounds such as N-cyclohexyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N, N-diisopropyl-2-benzothiazolylsulfenamide A thiazol compound such as 2-mercaptobenzothiazole, 2- (2 ′, 4′-dinitrophenyl) mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole, dibenzothiazyl disulfide; diphenylguanidine, Guanidine compounds such as diorthotolylguanidine, diorthonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reaction product, butyraldehyde-aniline condensate, hexamethylenetetramine, a Aldehyde amines such as toaldehyde ammonia or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; Thiuram compounds such as methyl thiuram monosulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, tetraoctyl thiuram disulfide, pentamethylene thiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, di-n-butyl Zinc dithiocarbamate, zinc ethylphenyldithiocarbamate, butylphenyldithiocarbamate Dithioate compounds such as lead, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium dimethyldithiocarbamate; xanthates such as zinc dibutylxanthate; inorganic zinc compounds such as zinc carbonate alone, or Two or more kinds can be used in combination. The vulcanization aid can be added when any vulcanizing agent is used, but is more effective when sulfur is used as the vulcanizing agent.
また、上記有機過酸化物としては、t−ブチルハイドロパーオキサイド、1,1,3,3−テトラメチルブチルハイドロパーオキサイド、p−メンタンハイドロパーオキサイド、クメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、2,5−ジメチルヘキサン−2,5−ジハイドロパーオキサイド、1,1−ジ−t−ブチルパーオキシ−3,3,5−トリメチルシクロヘキサン、ジ−t−ブチルパーオキサイド、t−ブチルクミルパーオキサイド、ジクミルパーオキサイド、1,1−ビス(t−ブチルパーオキシ)シクロドデカン、2,2−ビス(t−ブチルパーオキシ)オクタン、1,1−ジ−t−ブチルパーオキシシクロヘキサン、2,5−ジメチル−2,5−ジ−(t−ブチルパーオキシ)ヘキサン、2,5−ジメチル−2,5−ジ−(t−ブチルパーオキシ)ヘキシン、1,3ビス(t−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、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、n−ブチル−4,4−ビス(t−ブチルパーオキシ)バレレート、ベイゾイルパーオキサイド、m−トルイルパーオキサイド、p−クロロベンゾイルパーオキサイド、2,4−ジクロロベンゾイルパーオキサイド、t−ブチルパーオキシイソブチレート、t−ブチルパーオキシ−2−エチルヘキサノエート、t−ブチルパーオキシベンゾエート、t−ブチルパーオキシ−イソプロピルカーボナート、t−ブチルパーオキシアリルカーボナート等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the organic peroxide include t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, di-t-butylperoxide, t-butylcumylper Oxide, dicumyl peroxide, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) octane, 1,1-di-t-butylperoxycyclohexane, 2 , 5-Dimethyl-2,5-di- (t-butylperoxy) hexane, 2 5-dimethyl-2,5-di- (t-butylperoxy) hexyne, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di- (benzoylperoxy) ) Hexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, bazoyl peroxide, m- Toluyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t -Butyl peroxy-isopropyl carbonate, t-butyl peroxyallyl carbonate, etc. That. These can be used alone or in combination of two or more.
上記加硫剤として、有機過酸化物を用いる場合のその配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは0.2〜10質量部、更に好ましくは0.3〜7質量部である。 When the organic peroxide is used as the vulcanizing agent, the blending amount is preferably 0.2 to 10 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the raw rubber in the fuel oil resistant rubber composition. Is 0.3 to 7 parts by mass.
また、エポキシ基含有アクリル系ゴムを架橋するために、例えば、酸無水物、カルボン酸塩等の架橋剤を用いることもできる。これらは、それぞれ、1種単独で、あるいは2種以上を組み合わせて用いることができる。 In order to crosslink the epoxy group-containing acrylic rubber, for example, a crosslinking agent such as an acid anhydride or a carboxylate can be used. These can be used singly or in combination of two or more.
上記酸無水物としては、無水フタル酸、メチルテトラハイドロフタル酸、メチルヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸等が挙げられる。また、上記カルボン酸塩は、モノカルボン酸の塩(金属塩、アンモニウム塩等)であってもよいし、ジカルボン酸の塩(金属塩、アンモニウム塩等)であってもよい。更には、ポリカルボン酸の塩(金属塩、アンモニウム塩等)であってもよい。金属塩とする場合の金属元素は、亜鉛、マグネシウム等が挙げられる。従って、このカルボン酸塩としては、メタクリル酸亜鉛、メタクリル酸マグネシウム、ジメタクリル亜鉛等が挙げられる。 Examples of the acid anhydride include phthalic anhydride, methyltetrahydrophthalic acid, methylhexahydrophthalic anhydride, and tetrahydrophthalic anhydride. The carboxylate may be a monocarboxylic acid salt (metal salt, ammonium salt, etc.) or a dicarboxylic acid salt (metal salt, ammonium salt, etc.). Further, it may be a salt of a polycarboxylic acid (metal salt, ammonium salt, etc.). Examples of the metal element in the case of forming a metal salt include zinc and magnesium. Accordingly, examples of the carboxylate include zinc methacrylate, magnesium methacrylate, and zinc dimethacrylate.
上記軟化剤としては、石油系軟化剤、植物油系軟化剤、サブ等が挙げられる。これらは1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the softener include petroleum softeners, vegetable oil softeners, and subs. These can be used alone or in combination of two or more.
石油系軟化剤としては、アロマティック系、ナフテン系、パラフィン系軟化剤等が挙げられる。植物系軟化剤としては、ひまし油、綿実油、あまに油、なたね油、大豆油、パーム油、やし油、落花生油、木ろう等が挙げられる。サブとしては、黒サブ、白サブ、飴サブ等が挙げられる。 Examples of petroleum softeners include aromatic, naphthenic and paraffinic softeners. Examples of plant softeners include castor oil, cottonseed oil, sesame oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, and wax. Examples of the sub include a black sub, a white sub, and a black sub.
上記軟化剤の配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは0〜50質量部、より好ましくは0〜30質量部、更に好ましくは0〜10質量部である。 The blending amount of the softening agent is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, and further preferably 0 to 10 parts by mass with respect to a total of 100 parts by mass of the raw rubber in the fuel oil resistant rubber composition. Part by mass.
上記老化防止剤としては、例えば、ナフチルアミン系、ジフェニルアミン系、p−フェニレンジアミン系、キノリン系、ヒドロキノン誘導体系、(モノ−、ビス−、トリス−、ポリ−)フェノール系、チオビスフェノール系、ヒンダードフェノール系、亜リン酸エステル系、イミダゾール系、ジチオカルバミン酸ニッケル塩系、リン酸系の老化防止剤等が挙げられる。これらは1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the anti-aging agent include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivative, (mono-, bis-, tris-, poly-) phenol, thiobisphenol, hindered Examples thereof include phenol-based, phosphite-based, imidazole-based, nickel dithiocarbamate, and phosphoric acid-based antioxidants. These can be used alone or in combination of two or more.
上記老化防止剤の配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは0〜10質量部、より好ましくは0〜7質量部、更に好ましくは0〜5質量部である。 The blending amount of the anti-aging agent is preferably 0 to 10 parts by mass, more preferably 0 to 7 parts by mass, and further preferably 0 to 0 parts by mass with respect to a total of 100 parts by mass of the raw rubber in the fuel oil resistant rubber composition. 5 parts by mass.
上記紫外線吸収剤としては、ベンゾフェノン類、ベンゾトリアゾール類、サリチル酸エステル類、金属錯塩類等が挙げられる。これらは、1種単独であるいは2種以上を組み合わせて用いることができる。 Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
上記紫外線吸収剤の配合量は、耐燃料油性ゴム組成物中の原料ゴムの合計100質量部に対して、好ましくは0〜10質量部、より好ましくは0〜7質量部、更に好ましくは0〜5質量部である。 The blending amount of the ultraviolet absorber is preferably 0 to 10 parts by mass, more preferably 0 to 7 parts by mass, and further preferably 0 to 0 parts by mass with respect to a total of 100 parts by mass of the raw rubber in the fuel oil resistant rubber composition. 5 parts by mass.
本発明の耐燃料油性ゴム組成物は、以下に示す所定の抽出試験による沈殿物の体積が、0.1ml以下であることが好ましく、0.05ml以下であることが更に好ましい。 The fuel oil resistant rubber composition of the present invention preferably has a precipitate volume of 0.1 ml or less, more preferably 0.05 ml or less, according to a predetermined extraction test described below.
(抽出試験)
耐燃料油性ゴム組成物をシート状に加工し、160℃、20分の条件でプレス加硫して厚さ2mmのシート状の加硫ゴムを作製する。次に、得られたシート状の加硫ゴムを一辺1cmの正方形に細断してサンプルを作製する。次に、ステンレス管にサンプルを30g入れ、更に試験用燃料油C(トルエン/イソオクタン=50/50(体積比):JIS K6258)を100ml入れる。そして、サンプル及び試験用燃料油Cを40℃とし、その状態でサンプルを試験用燃料油C中に72時間浸漬させる。次に、ステンレス管中の液体(試験用燃料油C及び抽出物)だけを100mlマイヤーフラスコに移し、70℃ホットプレート上で窒素を液面に吹きかけながら全体の体積が約10mlになるまで濃縮する。次に、得られた約10mlの液体(濃縮された、試験用燃料油C及び抽出物)を遠心分離用容器に移して72時間放置する。次に、回転数400rpmで3分間遠心分離して、沈殿物の体積(ml)を確認する。沈殿物の体積は、沈殿物を遠心分離用容器から取り出さずに、遠心分離終了後、遠心分離用容器内に沈殿した状態で測定する。遠心分離用容器は、沈殿物がその底部に沈殿した状態で、沈殿物の体積を測定できるものである。例えば必要な目盛りの付いた管である。
(Extraction test)
The fuel oil-resistant rubber composition is processed into a sheet shape, and press vulcanized at 160 ° C. for 20 minutes to produce a sheet-shaped vulcanized rubber having a thickness of 2 mm. Next, the obtained sheet-like vulcanized rubber is chopped into squares each having a side of 1 cm to produce a sample. Next, 30 g of the sample is put in a stainless steel tube, and 100 ml of test fuel oil C (toluene / isooctane = 50/50 (volume ratio): JIS K6258) is further put. Then, the sample and the test fuel oil C are set to 40 ° C., and the sample is immersed in the test fuel oil C for 72 hours in this state. Next, only the liquid (the test fuel oil C and the extract) in the stainless steel tube is transferred to a 100 ml Meyer flask and concentrated until the total volume is about 10 ml while blowing nitrogen onto the liquid surface on a 70 ° C. hot plate. . Next, about 10 ml of the obtained liquid (concentrated, test fuel oil C and extract) is transferred to a centrifuge container and allowed to stand for 72 hours. Next, the mixture is centrifuged at 400 rpm for 3 minutes to confirm the volume (ml) of the precipitate. The volume of the precipitate is measured in a state where the precipitate is not taken out from the centrifuge container, but is precipitated in the centrifuge container after completion of the centrifugation. The centrifuge container can measure the volume of the precipitate in a state where the precipitate has settled at the bottom thereof. For example, a tube with the necessary scale.
本発明の耐燃料油性ゴム組成物は、例えば、以下のようにして製造することができる。 The fuel oil-resistant rubber composition of the present invention can be produced, for example, as follows.
先ず、α,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴム、アクリル系ゴム、炭素数8〜30の高級不飽和脂肪酸又はその金属塩、カーボンブラック等の補強剤、その他加硫剤以外の配合剤等をバンバリーミキサー等の混練機等により、温度70〜180℃で混練する。その後、混練物を冷却し、硫黄等の加硫剤、加硫助剤(酸化亜鉛)等を、バンバリーミキサー、ミキシングロール等により配合することにより耐燃料油性ゴム組成物を得ることができる。そして、温度130〜200℃で加硫することにより本発明の加硫ゴムを得ることができる。混練後、そのまま成形体とする場合には、上記温度で金型成形、押出成形、射出成形等を適用すればよい。尚、上記α,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴム及び上記アクリル系ゴムは、それぞれが凝固後の固体状態で、上記工程により混合されてもよいし、固体状態とする前の各乳化液(ラテックス)を所定割合で混合し、上記と同様の方法により混合液から重合体成分を凝固することにより得られた、上記α,β−不飽和ニトリル・共役ジエン系ゴム及び/又は部分水素化α,β−不飽和ニトリル・共役ジエン系ゴム及び上記アクリル系ゴムを含む複合体(複合ゴム)を用いて上記混練工程により混合されてもよい。 First, α, β-unsaturated nitrile / conjugated diene rubber and / or partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber, acrylic rubber, higher unsaturated fatty acid having 8 to 30 carbon atoms or metal thereof A reinforcing agent such as salt and carbon black, and other compounding agents other than the vulcanizing agent are kneaded at a temperature of 70 to 180 ° C. by a kneader such as a Banbury mixer. Thereafter, the kneaded product is cooled, and a fuel oil-resistant rubber composition can be obtained by blending a vulcanizing agent such as sulfur, a vulcanizing aid (zinc oxide), etc. with a Banbury mixer, a mixing roll or the like. And the vulcanized rubber of this invention can be obtained by vulcanizing at the temperature of 130-200 degreeC. When the molded body is used as it is after kneading, die molding, extrusion molding, injection molding or the like may be applied at the above temperature. The α, β-unsaturated nitrile / conjugated diene rubber and / or the partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber and the acrylic rubber are each in a solid state after coagulation. It may be mixed by the process, each emulsion before making into a solid state (latex) is mixed at a predetermined ratio, and obtained by coagulating a polymer component from the mixture by the same method as above, α, β-unsaturated nitrile / conjugated diene rubber and / or partially hydrogenated α, β-unsaturated nitrile / conjugated diene rubber and a composite (composite rubber) containing the above acrylic rubber by the kneading step. It may be mixed.
本発明の成形体は、上記耐燃料油性ゴム組成物を用いて押出成形等により、例えばホース状の加硫前の成形体を作製し、加硫前の成形体を加硫して得られたもの、又は金型等で加硫成形して得られたものである。また、本発明の成形体は、オイルクーラーホース、エアーダクトホース、パワーステアリングホース、コントロールホース、インタークーラーホース、トルコンホース、オイルリターンホース、耐熱ホース等のホース(ホース状成形体);自転車チューブ、ゴム管、理化学用ゴムチュービング等のチューブ;o−リング、ガスケット、ゴムライニング等の各種パッキン類として使用することが可能である。 The molded body of the present invention was obtained by, for example, producing a hose-shaped molded body before vulcanization and vulcanizing the molded body before vulcanization by extrusion molding or the like using the fuel oil-resistant rubber composition. Or obtained by vulcanization molding with a mold or the like. In addition, the molded body of the present invention includes an oil cooler hose, an air duct hose, a power steering hose, a control hose, an intercooler hose, a torque converter hose, an oil return hose, a heat resistant hose and the like (hose shaped molded body); a bicycle tube, a rubber It can be used as various packings such as tubes, tubes for physics and chemistry rubber tubing; o-rings, gaskets, rubber linings and the like.
以下、実施例によって本発明を更に具体的に説明するが、本発明は、これらによっていかなる制限を受けるものではない。なお、以下の記載において「部」及び「%」は、特別に規定しない限り質量部及び質量%を示す。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following description, “parts” and “%” indicate parts by mass and mass% unless otherwise specified.
(原料ゴム)
(G1)JSR社製 NBR 商品名N222L(アクリロニトリル単位量=43%、ムーニー粘度[ML1+4(100℃)]=45)
(G2)JSR社製 NBR/PVC 商品名NV72(NBR/PVC=70/30、ムーニー粘度[ML1+4(100℃)]=75)
(G3)NBR/ACM(アクリルゴム)混合ゴム N222L/AREX100=60/40(AREX100:ジエン系アクリルゴム、JSR社の商品名)
(G4)C−NBR/エポキシ基及びジエン含有ANM(C−NBR:カルボキシル基含有NBR、ANM:アクリル酸エステル類とアクリロニトリルとのゴム状共重合体)、C−NBR/エポキシ基及びジエン含有ANM=60/40、カルボキシル基(−COOH)含有量が0.348mmol/g
(Raw material rubber)
(G1) NBR product name N222L manufactured by JSR (acrylonitrile unit amount = 43%, Mooney viscosity [ML 1 + 4 (100 ° C.)] = 45)
(G2) NBR / PVC product name NV72 manufactured by JSR (NBR / PVC = 70/30, Mooney viscosity [ML 1 + 4 (100 ° C.)] = 75)
(G3) NBR / ACM (acrylic rubber) mixed rubber N222L / AREX100 = 60/40 (AREX100: diene acrylic rubber, trade name of JSR)
(G4) C-NBR / epoxy group and diene-containing ANM (C-NBR: carboxyl group-containing NBR, ANM: rubbery copolymer of acrylates and acrylonitrile), C-NBR / epoxy group and diene-containing ANM = 60/40, carboxyl group (—COOH) content is 0.348 mmol / g
上記原料ゴムG4の中で、C−NBRは以下の方法により得たものである。
(C−NBR)
アクリロニトリル45部、ブタジエン52部及びメタクリル酸3部からなる単量体混合物、ラウリル硫酸ナトリウム4部、過硫酸カリウム0.2部及び水200部を窒素置換したステンレス製反応器に仕込み、40℃で重合させた。重合転化率がほぼ80%に達したところで、N,N−ジエチルヒドロキシルアミン0.5部を反応系に添加して共重合反応を停止させた(反応時間8時間)。次いで、反応生成物を含むラテックスに0.25%塩化カルシウム水溶液を添加して共重合ゴムを凝固させた。この凝固物を十分に水洗した後、約90℃で3時間乾燥させることにより、ムーニー粘度[ML1+4(100℃)]が80であり、アクリロニトリル単位量が41%、カルボキシル基含有量が0.348mmol/gであるC−NBR(カルボキシル基含有不飽和ニトリル・共役ジエン系共重合体)を得た。
Among the raw rubber G4, C-NBR is obtained by the following method.
(C-NBR)
A monomer mixture consisting of 45 parts of acrylonitrile, 52 parts of butadiene and 3 parts of methacrylic acid, 4 parts of sodium lauryl sulfate, 0.2 part of potassium persulfate and 200 parts of water were charged into a nitrogen-substituted stainless steel reactor at 40 ° C. Polymerized. When the polymerization conversion reached approximately 80%, 0.5 part of N, N-diethylhydroxylamine was added to the reaction system to stop the copolymerization reaction (reaction time 8 hours). Next, a 0.25% calcium chloride aqueous solution was added to the latex containing the reaction product to coagulate the copolymer rubber. The coagulated product is thoroughly washed with water and then dried at about 90 ° C. for 3 hours, whereby the Mooney viscosity [ML 1 + 4 (100 ° C.)] is 80, the acrylonitrile unit amount is 41%, and the carboxyl group content is C-NBR (carboxyl group-containing unsaturated nitrile / conjugated diene copolymer) of 0.348 mmol / g was obtained.
上記原料ゴムG4の中で、エポキシ基及びジエン含有ANMは以下の方法により得たものである。
(エポキシ基及びジエン含有ANM)
アクリル酸エチル65部、メタクリル酸グリシジル5部、アクリロニトリル25部及びアクリル酸ジヒドロジシクロペンタジエニルオキシエチル5部からなる単量体混合物、ラウリル硫酸ナトリウム4部、過硫酸カリウム0.2部及び水200部を、窒素置換したステンレス製反応器に仕込み、50℃で重合させた。重合転化率がほぼ100%に達したところで、N,N−ジエチルヒドロキシルアミン0.5部を反応系に添加して共重合反応を停止させた(反応時間15時間)。次いで、反応生成物を含むラテックスに0.25%塩化カルシウム水溶液を添加して共重合ゴムを凝固させた。この凝固物を十分に水洗した後、約90℃で3時間乾燥させることにより、ムーニー粘度[ML1+4(100℃)]が70であるエポキシ基及びジエン含有ANMを得た。
Among the raw material rubber G4, the epoxy group and diene-containing ANM are obtained by the following method.
(Epoxy group and diene containing ANM)
Monomer mixture consisting of 65 parts ethyl acrylate, 5 parts glycidyl methacrylate, 25 parts acrylonitrile and 5 parts dihydrodicyclopentadienyloxyethyl acrylate, 4 parts sodium lauryl sulfate, 0.2 parts potassium persulfate and water 200 parts were charged into a stainless steel reactor purged with nitrogen and polymerized at 50 ° C. When the polymerization conversion reached almost 100%, 0.5 part of N, N-diethylhydroxylamine was added to the reaction system to stop the copolymerization reaction (reaction time 15 hours). Next, a 0.25% calcium chloride aqueous solution was added to the latex containing the reaction product to coagulate the copolymer rubber. The coagulated product was thoroughly washed with water and then dried at about 90 ° C. for 3 hours to obtain an epoxy group- and diene-containing ANM having a Mooney viscosity [ML 1 + 4 (100 ° C.)] of 70.
(ゴム組成物の製造及び評価)
(実施例1)
上記原料ゴム(G1)100部、カーボンブラック(商品名「シーストSO」、東海カーボン社製)70部、アジピン酸エーテルエステル系可塑剤(可塑剤)(商品名「アデカサイザーRS107」、旭電化工業社製)30部、亜鉛華(商品名「酸化亜鉛2種」、正同化学社製)5.0部、オレイン酸ナトリウム(商品名「ノンサールON−A」、日本油脂社製)1.0部、及び硫黄(商品名「粉末硫黄」、鶴見化学社製)0.5部を混合し、バンバリーミキサーにて混練した。そして、得られた混合物に更に、加硫促進剤(I)としてテトラエチルチウラムジスルフィド(TETDS)(商品名「ノクセラーTET」、大内新興化学工業社製)1.5部、及び加硫促進剤(II)としてN−シクロヘキシル−2−ベンゾチアゾリルスルフェンアミド(商品名「ノクセラーCZ」、大内新興化学工業社製)1.2部を配合して、直径6インチのロールで練り込み、ゴム組成物(耐燃料油性ゴム組成物)を調製した。得られたゴム組成物を160℃で20分プレス加硫を行うことにより厚さ2mmの加硫ゴムシートを作製し、その物性評価を行った。各原料の配合(質量部)と評価結果を表1に示す。尚、架硫ゴムの評価は下記方法に拠った。また、「バンバリー排出性」は、上記混合物をバンバリーミキサーにて混練・排出するときに、排出時の取り出しが容易であった場合を「良い」とし、取り出しが困難であった場合を「劣る」として評価したものである。また、抽出試験の結果、遠心分離用容器内に沈殿物が沈殿する様子を図1(a)に示す。
(Manufacture and evaluation of rubber composition)
Example 1
100 parts of the above raw rubber (G1), 70 parts of carbon black (trade name “SEAST SO”, manufactured by Tokai Carbon Co., Ltd.), adipate ether ester plasticizer (plasticizer) (trade name “Adekasizer RS107”, Asahi Denka Kogyo 30 parts, zinc white (trade name “Zinc Oxide 2”, manufactured by Shodo Chemical Co., Ltd.) 5.0 parts, sodium oleate (trade name “NONSAR ON-A”, manufactured by NOF Corporation) 1.0 Part and 0.5 part of sulfur (trade name “powder sulfur”, manufactured by Tsurumi Chemical Co., Ltd.) were mixed and kneaded with a Banbury mixer. The resulting mixture was further added with 1.5 parts of tetraethylthiuram disulfide (TETDS) (trade name “Noxeller TET”, manufactured by Ouchi Shinsei Chemical Co., Ltd.) as a vulcanization accelerator (I), and a vulcanization accelerator ( II) N-cyclohexyl-2-benzothiazolylsulfenamide (trade name “Noxeller CZ”, manufactured by Ouchi Shinsei Chemical Co., Ltd.) 1.2 parts is blended and kneaded with a 6 inch diameter roll, and rubber A composition (fuel oil resistant rubber composition) was prepared. The obtained rubber composition was subjected to press vulcanization at 160 ° C. for 20 minutes to produce a vulcanized rubber sheet having a thickness of 2 mm, and its physical properties were evaluated. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results. The evaluation of the vulcanized rubber was based on the following method. In addition, the “Banbury dischargeability” is “good” when the mixture is kneaded and discharged with a Banbury mixer and is easy to be taken out at the time of discharge, and is “poor” when it is difficult to take out the mixture. It is evaluated as. Moreover, a mode that a precipitate precipitates in the centrifuge container as a result of the extraction test is shown in FIG.
(1)引張破断強度:JIS−K6251に準拠して測定した。表1には、強度変化率(TB(MPa))と伸び変化率(EB(%))とを示した。
(2)硬度(Hs):柔軟性の指標としてJIS−K6253に準拠して測定した。
(3)圧縮永久歪み:JIS−K6262に準拠し、100℃、70時間、25%圧縮後の値を測定した。
(4)抽出試験:上述した所定の抽出試験により試験を行った。表1の「抽出試験」では沈殿物の体積(ml)を示している。
(1) Tensile strength at break: measured in accordance with JIS-K6251. Table 1 shows the strength change rate (T B (MPa)) and the elongation change rate (E B (%)).
(2) Hardness (Hs): Measured according to JIS-K6253 as an index of flexibility.
(3) Compression set: Based on JIS-K6262, the value after compression at 100 ° C. for 70 hours and 25% was measured.
(4) Extraction test: The test was performed according to the predetermined extraction test described above. The “extraction test” in Table 1 indicates the volume (ml) of the precipitate.
(実施例2)
オレイン酸ナトリウムに代えてオレイン酸亜鉛(試薬、添川理化学社製)を用いた以外は実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
(Example 2)
A rubber composition was prepared in the same manner as in Example 1 except that zinc oleate (reagent, manufactured by Soekawa Riken) was used in place of sodium oleate, a vulcanized rubber sheet was prepared, and the physical properties were evaluated by the above method. I went there. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(実施例3)
オレイン酸ナトリウムに代えてオレイン酸A(試薬、キシダ化学社製)を用いた以外は実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
Example 3
A rubber composition was prepared in the same manner as in Example 1 except that oleic acid A (reagent, manufactured by Kishida Chemical Co., Ltd.) was used instead of sodium oleate, and a vulcanized rubber sheet was prepared. I went there. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(実施例4)
オレイン酸ナトリウムに代えてオレイン酸B(商品名「EXTRA OLEIN 80」、日本油脂社製)を用いた以外は実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
Example 4
A rubber composition was prepared in the same manner as in Example 1 except that oleic acid B (trade name “EXTRA OLEIN 80”, manufactured by NOF Corporation) was used instead of sodium oleate, and a vulcanized rubber sheet was prepared. The physical properties were evaluated by the above method. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(実施例5)
原料ゴム(G1)に代えて原料ゴム(G2)を用い、カーボンブラックの配合量を70部に代えて50部とした以外は、実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
(Example 5)
A rubber composition was prepared and vulcanized in the same manner as in Example 1 except that the raw rubber (G2) was used instead of the raw rubber (G1), and the compounding amount of carbon black was changed to 50 parts instead of 70 parts. A rubber sheet was prepared and the physical properties were evaluated by the above method. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(実施例6)
原料ゴム(G1)に代えて原料ゴム(G3)を用いた以外は、実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
(Example 6)
A rubber composition was prepared in the same manner as in Example 1 except that the raw rubber (G3) was used instead of the raw rubber (G1), a vulcanized rubber sheet was prepared, and the physical properties were evaluated by the above method. It was. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(実施例7)
原料ゴム(G1)に代えて原料ゴム(G4)を用い、オレイン酸ナトリウムに代えてオレイン酸Aとした以外は、実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
(Example 7)
A rubber composition was prepared in the same manner as in Example 1 except that the raw rubber (G4) was used instead of the raw rubber (G1), and oleic acid A was used instead of sodium oleate, to produce a vulcanized rubber sheet. And the physical property evaluation was performed by the said method. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(比較例1)
オレイン酸ナトリウムを配合しなかった以外は、実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
(Comparative Example 1)
A rubber composition was prepared in the same manner as in Example 1 except that sodium oleate was not blended to produce a vulcanized rubber sheet, and the physical properties were evaluated by the above methods. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(比較例2)
オレイン酸ナトリウムに代えてステアリン酸(商品名「ルナックS−30」、花王社製)を用いた以外は、実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。また、抽出試験の結果、遠心分離用容器内に沈殿物が沈殿する様子を図1(b)に示す。
(Comparative Example 2)
A rubber composition was prepared in the same manner as in Example 1 except that stearic acid (trade name “Lunac S-30”, manufactured by Kao Corporation) was used instead of sodium oleate, and a vulcanized rubber sheet was produced. The physical properties were evaluated by the above method. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results. Moreover, a mode that a deposit precipitates in the centrifuge container as a result of the extraction test is shown in FIG.
(比較例3)
オレイン酸ナトリウムに代えてパルミチン酸(商品名「ルナックP−95」、花王社製)を用いた以外は、実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
(Comparative Example 3)
A rubber composition was prepared in the same manner as in Example 1 except that palmitic acid (trade name “Lunac P-95”, manufactured by Kao Corporation) was used instead of sodium oleate, and a vulcanized rubber sheet was produced. The physical properties were evaluated by the above method. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
(比較例4)
原料ゴム(G1)に代えて原料ゴム(G3)を用い、オレイン酸ナトリウムに代えてステアリン酸とした以外は、実施例1と同様にしてゴム組成物を調製し、加硫ゴムシートを作製し、その物性評価を上記方法にて行った。各原料の配合(質量部)と評価結果を表1に示す。
(Comparative Example 4)
A rubber composition was prepared in the same manner as in Example 1 except that the raw rubber (G3) was used instead of the raw rubber (G1), and stearic acid was used instead of sodium oleate, to prepare a vulcanized rubber sheet. The physical properties were evaluated by the above method. Table 1 shows the blending (parts by mass) of each raw material and the evaluation results.
表1より、実施例1〜7で得られたゴム組成物は、炭素数18の高級不飽和脂肪酸であるオレイン酸又はその金属塩を用いているため、バンバリーミキサーによる混練後の排出性(以下、単に「排出性」という。)がいずれも良好であり、且つ得られた加硫ゴムシートの抽出試験における沈殿物も、いずれも0mlと良好であった。これに対し、比較例1で得られたゴム組成物は、オレイン酸等の加工助剤を全く使用していないため、得られた加硫ゴムシートの抽出試験での沈殿物は0mlであったが、排出性に劣るものであった。また、比較例2〜4で得られたゴム組成物は、炭素数8〜30の高級不飽和脂肪酸を使用せずにステアリン酸等の飽和脂肪酸を用いているため、排出性は良好であったが、得られた加硫ゴムシートの抽出試験での沈殿物が0.5mlと非常に多いものであった。また、実施例1〜4は、オレイン酸又はその金属塩を用いているため、比較例2,3のステアリン酸等の飽和脂肪酸を用いた場合と同様に、比較例1の不飽和脂肪酸や飽和脂肪酸のいずれも使用しなかった場合と比較すると、圧縮永久ひずみが小さく良好な値となっている。 From Table 1, since the rubber compositions obtained in Examples 1 to 7 use oleic acid or a metal salt thereof, which is a higher unsaturated fatty acid having 18 carbon atoms, the dischargeability after kneading with a Banbury mixer (hereinafter referred to as the following) , Simply referred to as “dischargeability”), and the precipitates in the extraction test of the obtained vulcanized rubber sheet were all 0 ml. On the other hand, since the rubber composition obtained in Comparative Example 1 does not use any processing aid such as oleic acid, the amount of precipitate in the extraction test of the obtained vulcanized rubber sheet was 0 ml. However, it was inferior in discharge. Moreover, since the rubber composition obtained in Comparative Examples 2 to 4 uses a saturated fatty acid such as stearic acid without using a higher unsaturated fatty acid having 8 to 30 carbon atoms, the dischargeability is good. However, the amount of precipitates in the extraction test of the obtained vulcanized rubber sheet was as much as 0.5 ml. In addition, since Examples 1 to 4 use oleic acid or a metal salt thereof, similarly to the case of using a saturated fatty acid such as stearic acid of Comparative Examples 2 and 3, the unsaturated fatty acid or saturated of Comparative Example 1 Compared with the case where none of the fatty acids is used, the compression set is small and a good value.
本発明の耐燃料油性ゴム組成物は、耐燃料油性及び加工性に優れ、更に圧縮永久歪みの小さい加硫ゴムとすることができるため、各種成形体に成形し、得られた成形体を燃料油等と接触する部分に好適に使用することができる。例えば、ホース状に成形・加硫しホース状成形体とすることにより、内燃機関等の燃料油供給用ホースとして好適に使用することができる。また、本発明の耐燃料油性ゴム組成物から得られる本発明の成形体は、オイルクーラーホース、エアーダクトホース、パワーステアリングホース、コントロールホース、インタークーラーホース、トルコンホース、オイルリターンホース、耐熱ホース等のホース;自転車チューブ、ゴム管、理化学用ゴムチュービング等のチューブ;o−リング、ガスケット、ゴムライニング等の各種パッキン類として使用することが可能である。 The fuel oil-resistant rubber composition of the present invention is excellent in fuel oil resistance and processability and can be made into a vulcanized rubber having a small compression set, so that it is molded into various molded bodies, and the obtained molded bodies are used as fuel. It can be suitably used for a portion that comes into contact with oil or the like. For example, it can be suitably used as a fuel oil supply hose for an internal combustion engine or the like by forming and vulcanizing it into a hose shape to form a hose-like molded body. Further, the molded article of the present invention obtained from the fuel-resistant oil-resistant rubber composition of the present invention includes an oil cooler hose, an air duct hose, a power steering hose, a control hose, an intercooler hose, a torque converter hose, an oil return hose, a heat resistant hose, etc. Hose; bicycle tube, rubber tube, physicochemical rubber tubing, etc .; can be used as various packings such as o-rings, gaskets, rubber linings.
1…遠心分離用容器、2…沈殿物。 DESCRIPTION OF SYMBOLS 1 ... Container for centrifugation, 2 ... Precipitate.
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CN105218896A (en) * | 2015-11-13 | 2016-01-06 | 金湖县人宇密封件制造有限公司 | Oil resisting rubber |
CN107200880A (en) * | 2017-05-22 | 2017-09-26 | 罗建华 | A kind of O-ring sizing material and preparation method thereof |
JP2020203992A (en) * | 2019-06-18 | 2020-12-24 | 株式会社ブリヂストン | Rubber composition for hoses, and hose |
JP7240266B2 (en) | 2019-06-18 | 2023-03-15 | 株式会社ブリヂストン | Hose rubber composition and hose |
CN113950502A (en) * | 2019-06-26 | 2022-01-18 | 住友理工株式会社 | Oil hose |
CN113950502B (en) * | 2019-06-26 | 2023-05-02 | 住友理工株式会社 | Oil hose |
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