JP4240765B2 - Rubber vulcanizing agent and rubber composition containing the same - Google Patents
Rubber vulcanizing agent and rubber composition containing the same Download PDFInfo
- Publication number
- JP4240765B2 JP4240765B2 JP2000189748A JP2000189748A JP4240765B2 JP 4240765 B2 JP4240765 B2 JP 4240765B2 JP 2000189748 A JP2000189748 A JP 2000189748A JP 2000189748 A JP2000189748 A JP 2000189748A JP 4240765 B2 JP4240765 B2 JP 4240765B2
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- Japan
- Prior art keywords
- rubber
- group
- thiirane
- weight
- rubber composition
- 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.)
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- 229920001971 elastomer Polymers 0.000 title claims description 88
- 239000005060 rubber Substances 0.000 title claims description 88
- 239000003795 chemical substances by application Substances 0.000 title claims description 78
- 239000000203 mixture Substances 0.000 title claims description 39
- 238000004073 vulcanization Methods 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 45
- 125000001730 thiiranyl group Chemical group 0.000 claims description 42
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical group C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 claims description 36
- 238000007142 ring opening reaction Methods 0.000 claims description 31
- 125000006239 protecting group Chemical group 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 7
- 229960002447 thiram Drugs 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical group [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 238000013040 rubber vulcanization Methods 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000012039 electrophile Substances 0.000 claims description 3
- 239000012038 nucleophile Substances 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- -1 thiyl ions Chemical class 0.000 description 28
- 230000032683 aging Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000704 physical effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920000768 polyamine Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 235000021355 Stearic acid Nutrition 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 125000000466 oxiranyl group Chemical group 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RFDIBSNFDIXDCJ-UHFFFAOYSA-N 1,3-bis[2-[(2-methylpropan-2-yl)oxy]propan-2-yl]benzene Chemical compound CC(C)(C)OC(C)(C)C1=CC=CC(C(C)(C)OC(C)(C)C)=C1 RFDIBSNFDIXDCJ-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UBFVINIUSMPAIQ-UHFFFAOYSA-N [S].C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 Chemical compound [S].C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 UBFVINIUSMPAIQ-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- FWWQKRXKHIRPJY-UHFFFAOYSA-N octadecanal Chemical compound CCCCCCCCCCCCCCCCCC=O FWWQKRXKHIRPJY-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229940116357 potassium thiocyanate Drugs 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- 238000010059 sulfur vulcanization Methods 0.000 description 2
- 150000003553 thiiranes Chemical group 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- UBJQBODUWBODEG-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine boric acid Chemical compound B(O)(O)O.C1(=C(C=CC=C1)NC(=N)NC1=C(C=CC=C1)C)C UBJQBODUWBODEG-UHFFFAOYSA-N 0.000 description 1
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
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- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- NSPJNIDYTSSIIY-UHFFFAOYSA-N methoxy(methoxymethoxy)methane Chemical compound COCOCOC NSPJNIDYTSSIIY-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical group 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- YBWDGMRGVSOLPG-UHFFFAOYSA-N n'-acetyl-2,2,2-trifluoroacetohydrazide Chemical compound CC(=O)NNC(=O)C(F)(F)F YBWDGMRGVSOLPG-UHFFFAOYSA-N 0.000 description 1
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- QMHNQZGXPNCMCO-UHFFFAOYSA-N n,n-dimethylhexan-1-amine Chemical compound CCCCCCN(C)C QMHNQZGXPNCMCO-UHFFFAOYSA-N 0.000 description 1
- 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
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- WEYVCQFUGFRXOM-UHFFFAOYSA-N perazine Chemical compound C1CN(C)CCN1CCCN1C2=CC=CC=C2SC2=CC=CC=C21 WEYVCQFUGFRXOM-UHFFFAOYSA-N 0.000 description 1
- 229960002195 perazine Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- NCNISYUOWMIOPI-UHFFFAOYSA-N propane-1,1-dithiol Chemical compound CCC(S)S NCNISYUOWMIOPI-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 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
- FGTJJHCZWOVVNH-UHFFFAOYSA-N tert-butyl-[tert-butyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)O[Si](C)(C)C(C)(C)C FGTJJHCZWOVVNH-UHFFFAOYSA-N 0.000 description 1
- KJTULOVPMGUBJS-UHFFFAOYSA-N tert-butyl-[tert-butyl(diphenyl)silyl]oxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C(C)(C)C)O[Si](C(C)(C)C)(C=1C=CC=CC=1)C1=CC=CC=C1 KJTULOVPMGUBJS-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 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
- 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
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ゴム用加硫剤およびそれを含むゴム組成物に関し、更に詳しくは、加硫ゴムの老化後の諸物性を損わず、早期加硫による焼けや加硫戻りを抑制することができ、また耐リバージョン性及び耐老化性を改良することができる、ゴム用加硫剤およびそれを含むゴム組成物に関する。
【０００２】
【従来の技術】
従来、ゴムポリマー同士を架橋するときに生成するポリサルファイド結合は、その結合力が弱く、ゴムの加硫中に結合が切れて加硫戻りが発生したり、加硫後もゴム中のポリサルファイド結合が切れやすいため、老化後の破断強度や伸び等のゴムの諸物性が低下してしまうという問題があった。また、チオール基（ＳＨ−）を有する加硫剤は、ジエン系ゴムと高い反応性を示すことが知られており、ゴムの加硫を早めることができるが、逆に反応性が高すぎて、ゴム混練中に加硫が進んでしまう、いわゆる焼けを発生してしまうという問題があった。
【０００３】
【発明が解決しようとする課題】
従って、本発明の目的は、加硫ゴムの老化後の諸物性を損わず、早期加硫による焼けや加硫戻りを抑制することができるゴム用加硫剤およびそれを含むゴム組成物を提供することにある。
【０００４】
本発明の他の目的は、耐リバージョン性及び耐老化性を改良することができるゴム用加硫剤およびそれを含むゴム組成物を提供することにある。
【０００５】
【課題を解決するための手段】
本発明によれば、１分子中に少なくとも２つのチイラン基を有する化合物を含んでなるゴム用加硫剤が提供される。
【０００６】
本発明によれば、また、ゴムに、１分子中に少なくとも２つのチイラン基を有する化合物とチイラン環開環剤とを配合して成るゴム組成物が提供される。
【０００７】
本発明によれば、更に、ゴム１００重量部に対し、前記前記チイラン基を有する化合物０．１〜３０重量部及び前記チイラン環開環剤０．１〜３０重量部を配合してなるゴム組成物が提供される。
【０００８】
本発明によれば、更にまた、ゴム１００重量部に対して、１分子中に少なくとも２つのチイラン基を有する化合物０．１〜３０重量部、スルフェンアミド系および／又はスルフェンイミド系加硫促進剤０．１〜３０重量部並びに硫黄０．０１〜５重量部配合してなるゴム組成物が提供される。
【０００９】
本発明に従えば、更に上記ゴム組成物に、有機脂肪酸０．５重量部以下及び／又は金属酸化物０．５〜３０重量部を更に配合したゴム組成物が提供される。
【００１０】
【発明の実施の形態】
本発明のゴム用加硫剤は、下記式で示されるチイラン基（エピスルフィド基）を１分子中に２個又はそれ以上有する化合物（以下、チイラン基含有化合物ともいう）であり、チイラン基は以下の構造を有する基である。
【００１１】
【化１】
本発明者らは、１分子中に少なくとも２つのチイラン基を有する化合物と、求核剤、求電子剤またはこれらの官能基が保護された化合物等のチイラン環開環剤をゴム中に配合することにより、チイラン基含有化合物が加硫剤として作用することを見出した。即ち、加熱によってチイラン基含有化合物とチイラン環開環剤とが反応し、チイル（もしくはチオレート）イオン又はラジカルが発生し、これによってゴムが架橋される。このように、チイラン基含有化合物は、加熱前は加硫剤として働かず、加熱中にチイラン基から発生したチイルイオン又はラジカルとゴムポリマーとが反応して架橋が行われる潜在性加硫剤である。従って、チイラン基含有化合物の使用により加硫前の焼けが抑制されるとともに、加硫中は加硫速度の速い加硫剤となる。また、加硫によって生成した架橋結合は、モノスルフィド結合であり、ポリサルファイド結合のように、容易に切れることはなく、加硫戻りや加硫ゴムの老化後の破断強度や伸び等のゴムの諸物性の低下も抑えることができるのである。
【００１３】
本発明者らは、更に、硫黄を加えることにより、モジュラスが向上することを見い出し、また、金属酸化物がチイラン基と開環剤との反応を促進することを見い出した。また、ステアリン酸などの有機脂肪酸はチイラン基とチイラン開環剤との反応を阻害する傾向にあるため、その配合量を極力少なくするか、又は配合しない方が好ましい。
【００１４】
本発明において使用するチイラン基含有化合物を得るには、例えば、下記式で示されるオキシラン環を分子中に少なくとも２つ有するエポキシ化合物のオキシラン環の全部又は一部をチイラン環に置換して分子中に少なくとも２つのチイラン環が存在する化合物に転化することができる。
【００１５】
【化２】
本発明において使用するチイラン基含有化合物を得るために用いられるエポキシ化合物は、例えば、下記式（ａ）、（ｂ）、（ｄ）、（ｅ）又は（ｆ）において、置換基Ｙが全てオキシラン環である化合物や、下記式（ｃ）において、Ｚが酸素原子である化合物である。また、ｎは、０又は０以上の数である。
【００１７】
【化３】
【化４】
また、これらのエポキシ化合物は、分子内の水素原子又はその他の基がハロゲン原子で置換されたものであってもよい。例えば、下記式（ｇ）：
【００２０】
【化５】
（式中、Ｈalはハロゲン原子を示す）
で表される化合物であってもよい。ハロゲン原子としては、臭素、塩素、フッ素等が挙げられる。
【００２２】
本発明において、チイラン基含有化合物は、前記式（ａ）、（ｂ）、（ｃ）、（ｄ）、（ｅ）、（ｆ）、又は（ｇ）において、Ｙの少なくとも２つが、チイラン環であり、チイラン環以外のＹはオキシラン環である化合物、又はＺの少なくとも１つがＳであり、他のＺがＯである化合物である。
【００２３】
このチイラン基含有化合物の具体例として、下記式で表されるものが挙げられる。下記のそれぞれの式において、Ｙの少なくとも２つがチイラン環であり、チイラン環以外のＹはオキシラン環である化合物、又はＺの少なくとも１つがＳであり、他のＺがＯである化合物である。また、ｎは、０以上の数である。
【００２４】
【化６】
【化７】
【化８】
【化９】
このチイラン基含有化合物の製造は、エポキシ化合物と、チイラン化剤（エピスルフィド化剤）とを、極性溶媒中で、強攪拌下に反応させる方法にしたがって、行うことができる。用いられるチイラン化剤としては、例えば、チオシアン酸カリウム（ＫＳＣＮ）、チオ尿素等が挙げられる。
【００２９】
極性溶媒としては、例えば、メタノール、エタノール、アセトン、水、またはこれらの混合溶媒等を用いることができる。特に、チイラン化率が１００％、すなわち、オキシラン環／チイラン環の含有割合が０／１００の化合物（Ａ）を得るためには、溶媒としてアセトンを用いるのが好ましい。
【００３０】
反応は、通常、１０〜３５℃の温度範囲、例えば室温で、１０〜４０時間程度、例えば２０時間程度の反応時間で行うことができる。また、反応の雰囲気は、空気中でもよいし、窒素等の不活性ガス雰囲気中でもよい。反応温度を上げることにより、反応速度を増大させ、反応時間をさらに短縮することができるが、１００℃を超えるとチイラン環の副反応が起こるおそれがあるために好ましくない。
【００３１】
本発明に従えば、前記チイラン基含有化合物は、ゴム１００重量部に対し、好ましくは０．１〜３０重量部、更に好ましくは１〜１５重量部配合する。この配合量が０．１重量部未満では、架橋密度が低くなり、３０重量部を超えると加硫後にチイラン基含有化合物やその反応物がゴム表面に移行（ブリード）するおそれがあるので好ましくない。
【００３２】
本発明において使用されるチイラン環開環剤としては、特に限定されないが、求核剤、求電子剤またはこれらの官能基を保護基で保護した化合物などのようにチイラン環と反応してチイルイオン又はラジカルを発生する作用を有する化合物を用いることができる。なお、例えば、水酸基（−ＯＨ）のように、１分子中に求核性を示す部位（−Ｈ）と、求電子性を示す部位（−Ｏ−）とを両方備えた化合物であってもよい。求核性や求電子性を示す部位（官能基）を、適当な有機基によって保護させて保護基とすることにより、熱等の刺激によって、保護基を求核基や求電子基に戻すようにして、潜在性のチイラン環開環剤とすることができる。具体的には、水酸基、メルカプト基、アミノ基、カルボキシル基、アルデヒド基およびカルボニル基のα位に結合した水素基または上記と同様にこれらの保護基からなる群から選ばれた少なくとも一種を有する化合物であるのが、反応速度が速いという点で好ましい。また、チイラン環開環剤が、ゴム用加硫促進剤や老化防止剤であってもよく、エポキシ樹脂系接着剤の硬化剤として使用されるものを用いることもできる。
【００３３】
本発明に用いられるチイラン環開環剤としては、アルコール類、アミン類、酸又は酸無水物系化合物、アルデヒド類、カルボニル基のα位に結合した水素基を有する化合物、塩基性活性水素化合物、イミダゾール類、チオール類、フェノール樹脂、ユリア樹脂、メラミン樹脂、イソシアネート系化合物、潜在性硬化剤、紫外線硬化剤等が挙げられる。
【００３４】
アルコール類の具体例として、メタノール、エタノール、ブタノール、プロパノール、ヘキサノール、ステアリルアルコール、ヘキサンジオール、プロパンジオール等の脂肪族アルコール；フェノール、ｐ−メチルフェノール、ビスフェノールＡ、ビスフェノールＦ等の芳香族アルコールを挙げることができる。
【００３５】
アミン類の具体例として、メチルアミン、エチルアミン、ブチルアミン、プロピルアミン、ヘキシルアミン、ステアリルアミン等の脂肪族単官能アルコール；エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ヘキサメチレンジアミン、イミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、１，３，６−トリスアミノメチルヘキサン等のポリアミン；トリメチルヘキサメチレンジアミン、ポリエーテルジアミン、ジエチルアミノプロピルアミン等のポリメチレンジアミン；フェニルアミン、ｐ−メチルアミン等の芳香族単官能アミン；メンセンジアミン（ＭＤＡ）、イソフォロンジアミン（ＩＰＤＡ）、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、Ｎ−アミノエチルピペラジン（Ｎ−ＡＥＰ）、ジアミノジシクロヘキシルメタン、ビスアミノメチルシクロヘキサン、３，９−ビス（３−アミノプロピル）−２，４，８，１０−テトラオキサスピロ（５．５）ウンデカン等の環状脂肪族ポリアミン；メタキシリレンジアミン等の芳香環を含む脂肪族ポリアミン、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルフォン、ジアミノジエチルジフェニルメタン等の芳香族ポリアミン、また、３，９−ビス（３−アミノプロピル）−２，４，８，１０−テトラスピロ〔５．５〕ウンデカン等が挙げられる。また、アミンアダクト（ポリアミンエポキシ樹脂アダクト）、ポリアミン−エチレンオキシドアダクト、ポリアミン−プロピレンオキシドアダクト、シアノエチル化ポリアミン、脂肪族ポリアミンとケトンとの反応物であるケチミン；直鎖状ジアミン、テトラメチルグアニジン、トリエタノールアミン、ピペリジン、ピリジン、ベンジルジメチルアミン、ピコリン、２−（ジメチルアミノメチル）フェノール、ジメチルシクロヘキシルアミン、ジメチルベンジルアミン、ジメチルヘキシルアミン、ジメチルアミノフェノール、ジメチルアミノｐ−クレゾール、Ｎ，Ｎ' −ジメチルピペラジン、ピペリジン、１，４−ジアザジシクロ（２，２，２）オクタン、２，４，６−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）ウンデセン−１等の第二アミン類又は第三アミン類など、あるいはダイマー酸とジエチレントリアミン、トリエチレンテトラミン等のポリアミンとを反応させてなる液体ポリアミドなどが挙げられる。
【００３６】
環状脂肪族ポリアミン化合物の具体例としては、メンセンジアミン（ＭＤＡ）、イソフォロンジアミン（ＩＰＤＡ）、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、Ｎ−アミノエチルピペラジン（Ｎ−ＡＥＰ）等、その変性体である、３−アミノメチル−３，５，５−トリメチルシクロヘキシルアミン・ビスフェノールＡジグリシジルエーテル付加物等が挙げられる。
【００３７】
酸又は酸無水物系化合物の具体例として、酢酸、プロピオン酸、パルミチン酸、ステアリン酸等の芳香族単官能カルボン酸；安息香酸、ｐ−メチル安息香酸等の芳香族単官能カルボン酸；アジピン酸、アゼライン酸、デカンジカルボン酸等のポリカルボン酸、無水フタル酸、無水トリメリット酸、エチレングリコールビス（アンヒドロトリメリテート）、グリセロールトリス（アンドロトリメリテート）、無水ピロメリット酸、３，３' ，４，４' −ベンゾフェノンテトラカルボン酸無水物等の芳香族酸無水物、無水マレイン酸、無水コハク酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、無水メチルナジック酸、アルケニル無水コハク酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、メチルシクロヘキセンテトラカルボン酸無水物、無水メチルハイミック酸、トリアルキルテトラヒドロ無水フタル酸、ポリ（フェニルヘキサデカン二酸）無水物等の環状脂肪族酸無水物、ポリアジピン酸無水物、ポリアゼライン酸無水物、ポリセバシン酸無水物、ドデセニル無水コハク酸、ポリ（エチルオクタデカン二酸）無水物等の脂肪族酸無水物、クロレンド酸無水物、テトラブロム無水フタル酸、無水ヘット酸等のハロゲン化酸無水物などが挙げられる。
【００３８】
アルデヒド類の具体例としては、アセトアルデヒド、プロピオンアルデヒド、ステアリルアルデヒド、プロパンジアルデヒド、ベンゼンジアルデヒド等の脂肪族アルデヒド；ベンズアルデヒド、ｐ−メチルベンズアルデヒド等の芳香族アルデヒドなどが挙げられる。
【００３９】
カルボニル基のα位に結合した水素基を有する化合物の具体例としては、マロン酸ジメチル、マロン酸ジエチルなどが挙げられる。
【００４０】
塩基性活性水素化合物の具体例としては、ジシアンジアミド、有機酸ジヒドラジドなどが挙げられる。
【００４１】
イミダゾール類の具体例としては、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−フェニルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、２−メチルイミダゾリウム・イソシアヌレート、２，４−ジアミノ−６−〔２−メチルイミダゾリン−（１）〕−エチル−Ｓ−トリアジン、２，４−ジアミノ−６−〔２−エチル−４−メチルイミダゾリン−（１）〕−エチル−Ｓ−トリアジン等が挙げられる。
【００４２】
チオール類の具体例としては、エタンチオール、プロパンチオール、エタンジチオール、プロパンジチオール、チオグリコール酸、チオ酢酸、ベンゼンチオール、ベンゼンジチオール、２，２' −ビスメルカプトエチルエーテルの部分エポキシ付加物、ペンタエリスリトールテトラチオグリコレート、ジペンタエリスリトールヘキサチオグリコレート、トリメチロールプロパンドリチオグリコレート等のチオグリコール酸のエステル、末端にメルカプト基を有するポリスルフィドゴム等などが挙げられる。
【００４３】
イソシアネート系化合物の具体例としては、トルエンジイソシアネート、ヘキサメチレンジイソシアネート、キシレンジイソシアネート等のイソシアネート化合物、イソシアネート基を、フェノール、アルコール、カプロラクタム等と反応させてマスクしてなるブロックイソシアネート化合物などが挙げられる。
【００４４】
チイラン環開環剤として使用するゴム用加硫促進剤としては、チウラム系、ジチオカルバミン酸塩系、スルフェンアミド系、チアゾール系、キサントゲン酸塩系、チオウレア系、グアニジン系等を挙げることができる。具体的には、ニッケルジブチルジチオカルバメート、ジメチ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第２鉄、ジブチルジチオカルバミン酸亜鉛、ブチルキサントゲン酸亜鉛、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、２−メルカプトベンゾチアゾール、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、ジペンタメチレンチウラムテトラスルフィド、ジベンゾチアジルジスルフィド、２−メルカプトベンゾチアゾール亜鉛、２−（４，４' −モルフォリノジチオ）ベンゾチアゾール、Ｎ，Ｎ−ジエチルチオカルバモイル−２−ベンゾチアゾリルスルフィド、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−ｔ−ブチル−２−ベンゾチアジ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' −ジシクロヘキシル−２−ベンゾチアゾリルスルフェンアミド、１，３−ジフェニルグアニジン、ジ−ｏ−トルイルグアニジン、ジカテコールボレートのジ−ｏ−トルイルグアニジン塩、ヘキサメチレンテトラミン、ジアルキルジチオフォスフェート亜鉛、Ｎ−ｔ−ブチル−２−ベンゾチアジルスルフェンアミド、Ｎ−ブチルアルデヒドとアニリンの反応生成物、Ｎ，Ｎ' −ジフェニルチオ尿素、トリメチルチオ尿素等が挙げられる。なかでも、スルフェンアミド系加硫促進剤として、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、Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド、Ｎ，Ｎ' −ジシクロヘキシル−２−ベンゾチアジルスルフェンアミド、チウラム系加硫促進剤として、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、２−メルカプトベンゾチアゾール、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、ジペンタメチレンチウラムテトラスルフィドを用いるのが好ましい。
【００４５】
チイラン環開環剤として使用する老化防止剤としては、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２，２−メチレンビス４−メチル−６−ｔ−ブチルフェノール、モノα−メチル−ベンジルフェノール、ジα−メチル−ベンジルフェノール、トリα−メチル−ベンジルフェノール、２−メルカプトベンズイミダゾール、２−メルカプトメチルベンズイミダゾール、ジラウリルジチオプロピオネート、Ｎ−フェニル−Ｎ' −１，3 −ジメチルブチル−ｐ−フェニレンジアミン、Ｎ，Ｎ' −ジフェニル−ｐ−フェニレンジアミン、Ｎ−フェニル−Ｎ' −イソプロピル−ｐ−フェニレンジアミン、６−エトキシ−１，２−ジヒドロ−２，２，４−トリメチルキノリン、ポリ（２，２，４−トリメチル−１，２−ジヒドロキノリン）、オクチル化ジフェニルアミン、ジフェニルアミンとアセトンの反応物、Ｎ，Ｎ' −ジ−２−ナフチル−ｐ−フェニレンジアミン、混合ジアリール−ｐ−フェニレンジアミン、Ｎ−（３−メタクリロイルオキシ−２−ヒドロキシプロピル）−Ｎ' −フェニル−ｐ−フェニレンジアミン、特殊ワックス等を挙げることができる。
【００４６】
チイラン環開環剤がアルコール類の場合には、その水酸基を保護した保護基としては、メチルエーテル、トリフェニルメチルエーテル、ベンジルエーテル、トリメチルシリルエーテル、ｔ−ブチルジメチルシリルエーテル、ｔ−ブチルジフェニルシリルエーテル、テトラヒドロピラニルエーテル、２−メトキシエトキシメチルエーテル、メトキシメチルエーテル等を含むエーテル型保護基；アセトニド（イソプロピリデンアセタール）等を含むアセタール型保護基；アセチル、ベンゾイル、ｐ−ニトロフェノキシカルボニル等を含むエステル型保護基を挙げることができる。さらに、チイラン環開環剤がエノールの場合には、その水酸基を保護した保護基としては、シリルエノールエーテルを挙げることができる。
【００４７】
また、チイラン環開環剤がアミン類の場合には、アミノ基を保護した保護基としては、アセトアミド、トリフルオロアセトアミド、ベンズアミド等を含むアミド型保護基：フタルイミド等を含むイミド型保護基：ベンジルウレタン、ｔ−ブトキシウレタン等を含むウレタン型保護基：ベンジル等を含むアルキル型保護基：ｐ−トルエンスルホンアミド等を含むスルホンアミド型保護基；アミノ基とステアリン酸等の脂肪族カルボン酸との塩、アミノ基と安息香酸等の芳香族カルボン酸との塩を挙げることができる。
【００４８】
また、チイラン環開環剤がカルボン酸の場合には、カルボキシル基を保護した保護基としては、メチルエステル、ｔ−ブチルエステル、ベンジルエステル、トリフェニルメチルエステル等のエステル型保護基；カルボキシル基とステアリルアミン等の脂肪族アミンとの塩、カルボキシル基とアニリン等の芳香族アミンとの塩を挙げることができる。
【００４９】
また、チイラン環開環剤がカルボニル基のα位に結合した水素基を有する化合物の場合には、カルボニル基のα位に結合した水素基を保護した保護基としては、ホルミル基、ジチオアセタール基を挙げることができる。
【００５０】
また、チイラン環開環剤がチオール類の場合には、チオール基を保護した保護基としては、チオエーテル、ベンジルチオエーテル、チオエステル、ベンゾイルチオエステル、チオカルバメート、チオール基とステアリルアミン等の脂肪族アミンとの塩、チオール基と芳香族アミンとの塩を挙げることができる。
【００５１】
本発明に従えば、チイラン環開環剤は、ゴム１００重量部に対し、好ましくは０．１〜３０重量部、更に好ましくは１〜１５重量部配合する。この配合量が１重量部未満では、加硫が進行しにくくなり、３０重量部を超えると加硫後にチイラン環開環剤やその反応物がゴム表面に移行（ブリード）するおそれがあるので好ましくない。
【００５２】
本発明に従えば、前記チイラン基含有化合物及びチイラン環開環剤としてのスルフェンアミド系及び／又はスルフェンイミド系加硫促進剤に加えて、硫黄及び／又は金属酸化物を使用することができる。硫黄はゴムの加硫に使用されている任意の硫黄を用いることができる。硫黄の配合量はゴム１００重量部当り０．０１〜５重量部、好ましくは０．１〜３重量部である。この配合量が少な過ぎると架橋密度が低くなり、強度が低くなってしまうので好ましくなく、逆に多過ぎると架橋密度が高くなりすぎて、かたくなってしまうので好ましくない。
【００５３】
本発明に従った前記ゴム組成物には、ゴム１００重量部当り金属酸化物（例えば酸化亜鉛、酸化アルミニウム、酸化カルシウム、酸化チタン、酸化第二鉄、酸化第二銅、酸化マグネシウム、炭酸亜鉛、一酸化鉛、酸化鉛、炭酸鉛及び水酸化カルシウム）を好ましくは０．５〜３０重量部、更に好ましくは１〜１０重量部を配合することができる。金属酸化物の配合量が少な過ぎるとチイランとチイラン開環剤との反応を促進できないので好ましくなく、逆に多過ぎるとゴム物性が低下してしまうので好ましくない。
【００５４】
本発明に従ったゴム組成物には、従来からゴム組成物に加硫促進助剤として汎用されているステアリン酸、パルミチン酸、ラウリン酸、ミリスチン酸、オレイン酸、ベヘニン酸及びイソステアリン酸のような有機脂肪酸を配合すると、チイラン基とチイラン環開環剤との反応を阻害する傾向にあるため、その配合量を極力少なくするか又は配合しないのが好ましい。従って、本発明における有機脂肪酸の配合量はゴム１００重量部当り０．５重量部以下、好ましくは０〜０．１重量部とするのが好ましい。
【００５５】
本発明に使用するゴムは特に限定されないが、従来から各種ゴム組成物に一般的に配合されている任意のゴム、例えば天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）、スチレンブタジエン共重合体ゴム（ＳＢＲ）、ポリブタジエンゴム（ＢＲ）、アクリロニトリルブタジエン共重合体ゴム（ＮＢＲ）、ブチルゴム（ＩｌＲ）、クロロプレンゴム、エチレンプロピレン共重合体ゴム、エチレン−プロピレンジエン共重合体ゴム等をあげることができる。これらのゴムは単独又は任意のブレンドとして使用することができる。
【００５６】
本発明のゴム組成物は、ゴム工業で通常使用される配合剤を必要に応じて配合することができる。配合剤としては、例えば、カーボンブラック・シリカ等の充填剤、加硫促進剤、加硫活性化剤、老化防止剤、可塑剤、軟化剤等が挙げられ、それぞれ必要量配合することができる。
【００５７】
本発明の加硫剤およびそれを含むゴム組成物は、タイヤ、ホース、コンベヤベルト、ゴムシート、防舷材、防振ゴム、ローラー、ライニング、ゴム引布、シール材、手袋等各種ゴム製品に使用することができるが、特にタイヤ用ゴム組成物として好適に用いることができる。
【００５８】
【実施例】
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことは言うまでもない。
【００５９】
加硫剤１の合成
チオシアン酸カリウム７７４．４ｇ（８モル）を溶解させたエタノール４５０ミリリットルと水６４５ミリリットルの混合溶媒に、ネオペンチル−ジグリシジルエーテル（東都化成株式会社製、ＰＧ２０２）９９０ｇ（６．７８モル）を加え、室温で１２時間激しく撹拌した後、上層を分離後、下層を水洗し、硫酸マグネシウムで乾燥し、減圧乾燥することによりオキシラン環がチイラン環に変換された下記式に示す加硫剤１を得た。ＮＭＲ分析よりチイラン化率は１００％であることを確認した。
【００６０】
【化１０】
加硫剤２の合成
ネオペンチル−ジグリシジルエーテルの代わりに、ビスフェノールＦのグリシジルエーテルを用いて、加硫剤１と同様の製法にて、オキシラン環がチイラン環に変換された下記式に示す加硫剤２を得た。ＮＭＲ分析よりチイラン化率は１００％であることを確認した。
【００６２】
【化１１】
加硫剤３の合成
ネオペンチル−ジグリシジルエーテルの代わりに、水素添加ビスフェノールＡのグリシジルエーテルを用いて、加硫剤１と同様の製法にて、オキシラン環がチイラン環に変換された下記式に示す加硫剤３を得た。ＮＭＲ分析よりチイラン化率は１００％であることを確認した。
【００６４】
【化１２】
実施例１〜４及び比較例１〜５
上記で得られた加硫剤１〜３および各種加硫促進剤を配合した下記表Ｉに示す配合のゴム組成物を製造し、以下のレオメータ特性を測定した。加硫は、比較例５は１６０℃×６０分、それ以外は１５０℃×３０分の条件で行い、以下の破断強度、破断伸びを１００℃、４８時間の老化前後にて測定し、その保持率（老化後／老化前）を求めた。
【００６６】
なお、例えば加硫剤１と加硫促進剤ＣＺとの反応及びその後の架橋反応は模式的に記載すれば以下の通りである。
【００６７】
【化１３】
レオメータ特性
ＪｌＳ Ｋ６３００に基づき１５０℃にて９５％加硫度に達する時間（分）を測定し、Ｔ９５とした。Ｔ９５が小さいほど加硫速度が速い。また、レオメータのトルクが、そのピークから３％および５％低下した時間（分）をそれぞれＴ−３、Ｔ−５とした。Ｔ−３およびＴ−５が小さいほど加硫戻りが小さく、トルクのピークが認められなかったものは、加硫戻りが発生していないので、「なし」と明記した。
【００６９】
破断強度（ＭＰａ）
ＪＩＳＫ６２５１に準拠して測定した。
破断伸び（％）
ＪＩＳＫ６２５１に準拠して測定した。
【００７０】
【表１】
上記配合剤は、以下のものを使用した。
ＩＲ：Ｎｉｐｏｌ ＩＲ−２２００、日本ゼオン（株）製ポリイソプレンゴム
カーボンブラック：ＨＡＦ級カーボンブラック
亜鉛華：酸化亜鉛３号
ステアリン酸：工業用ステアリン酸
老化防止剤：Ｎ−フェニル−Ｎ' −（１，３−ジメチルブチル）−ｐ−フェニレンジアミン
硫黄：５％油処理硫黄
加硫促進剤CZ：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
加硫促進剤NS：Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド
加硫促進剤TT：テトラメチルチウラムジスルフィド
有機過酸化物：１，３−ビス−（ｔ−ブチル−オキシイソプロピル）ベンゼン
【００７２】
表Ｉより、硫黄配合の比較例１〜３のゴムは、加硫戻りが発生し、加硫ゴムの老化前後の物性の保持率が小さくなってしまった。また、硫黄を用いなかった比較例４、５のゴムは、加硫速度（Ｔ−９５）が遅いうえに、加硫後の破断伸びが劣っていた。それに対して、チイラン基含有化合物である加硫剤１〜３およびチイラン環開環剤であるゴム用加硫促進剤を配合した実施例１〜４のゴム組成物は、加硫戻りがなく、加硫ゴムの老化後の物性の保持率と加硫速度のバランスの優れたゴムであるという結果が得られた。
【００７３】
実施例５〜９
次に、加硫剤２および他の各種加硫促進剤を配合した下記表IIに示す配合のゴム組成物を上記の実施例１と同様に製造して、評価し、上記実施例と同様の良好な結果が得られた。
【００７４】
【表２】
上記の加硫促進剤は、以下のものを使用し、他の配合剤は実施例２と同様のものを使用した。
加硫促進剤TBBS：Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド
加硫促進剤DCBS：Ｎ，Ｎ' −ジシクロヘキシル-2- ベンゾチアゾリルスルフェンアミド
加硫促進剤TMTD：テトラメチルチウラムジスルフィド
加硫促進剤TMTM：テトラメチルチウラムモノスルフィド
加硫促進剤TRA ：ジペンタメチレンチウラムテトラスルフィド
【００７６】
実施例１０〜１３及び比較例６〜７
前記加硫剤１および加硫促進剤NSを配合した下記表III に示す配合のゴム組成物を製造し、以下のレオメータ特性を測定した。加硫は、１５０℃×３０分の条件で行い、加硫物の１００％モジュラス及び３００％モジュラス並びに破断強度及び破断伸びを１００℃×４８時間の老化前後にて測定し、その保持率（老化後／老化前）を求めた。結果を表III に示す。
【００７７】
レオメータ特性：前記の通り
１００％及び３００％モジュラス：ＪＩＳ Ｋ６２５１によって１００％及び３００％伸長時のモジュラスを測定した
破断強度及び伸び：前記の通り
オーバーキュア物性：１５０℃×６０分の条件で加硫したゴムの物性
老化後の物性：加硫サンプルを１００℃で４８時間老化させた後の物性
【００７８】
【表３】
表III に示した配合剤は以下の通りである
ＮＲ：天然ゴムＲＳＳ＃１
カーボンブラック：ＨＡＦ級カーボンブラック
亜鉛華：酸化亜鉛３号
ステアリン酸：工業用ステアリン酸
老化防止剤：Ｎ−フェニル−Ｎ' −（１，３−ジメチルブチル）−ｐ−フェニレンジアミン
硫黄：５％油処理硫黄
加硫促進剤CZ：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
加硫促進剤NS：Ｎ−ｔ−ブチル−２−ベンゾチアゾリルスルフェンアミド
【００８０】
表III の結果から明らかなように、硫黄で加硫した場合、レオメータ特性（Ｔ−３，Ｔ−５）より加硫もどりを起こしている。また、老化保持率も大きい一方加硫剤１を用いた場合には、加硫もどりを起こさず老化保持率も１００％に近い。すなわち加硫剤１の方が硫黄よりも加硫特性及び老化特性に優れている。
【００８１】
【発明の効果】
本発明に従って、１分子中に少なくとも２つのチイラン基を有する化合物からなるゴム用加硫剤をチイラン環開環剤と共にゴムに配合することによって、加硫ゴムの老化後の諸物性を損わずまたは改良し、早期加硫による焼けや加硫戻りを抑制することができ、しかも加硫速度の速いゴム組成物を得ることができる。また、本発明に従って、更に、硫黄を加えることによりモジュラスが向上し、また金属酸化物によってチイラン基と開環剤との反応を促進することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber vulcanizing agent and a rubber composition including the rubber vulcanizing agent. More specifically, the present invention can suppress burning and vulcanization return due to early vulcanization without impairing physical properties of the vulcanized rubber after aging. The present invention relates to a rubber vulcanizing agent and a rubber composition containing the same, which are capable of improving reversion resistance and aging resistance.
[0002]
[Prior art]
Conventionally, the polysulfide bond produced when the rubber polymers are cross-linked has a weak bonding force, and the bond breaks during vulcanization of the rubber and reversion occurs, or the polysulfide bond in the rubber remains after vulcanization. Since it is easy to cut, there was a problem that various physical properties of the rubber such as breaking strength and elongation after aging deteriorated. Moreover, it is known that the vulcanizing agent having a thiol group (SH-) has high reactivity with the diene rubber, and can accelerate the vulcanization of the rubber, but the reactivity is too high. However, there is a problem that so-called burning occurs because vulcanization proceeds during rubber kneading.
[0003]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a rubber vulcanizing agent and a rubber composition containing the same that can suppress burning and vulcanization reversion due to early vulcanization without impairing physical properties of the vulcanized rubber after aging. It is to provide.
[0004]
Another object of the present invention is to provide a rubber vulcanizing agent capable of improving reversion resistance and aging resistance and a rubber composition containing the same.
[0005]
[Means for Solving the Problems]
According to the present invention, there is provided a rubber vulcanizing agent comprising a compound having at least two thiirane groups in one molecule.
[0006]
According to the present invention, there is also provided a rubber composition comprising a rubber compounded with a compound having at least two thiirane groups in one molecule and a thiirane ring-opening agent.
[0007]
According to the present invention, a rubber composition obtained by further blending 0.1 to 30 parts by weight of the thiirane group-containing compound and 0.1 to 30 parts by weight of the thiirane ring-opening agent with respect to 100 parts by weight of rubber. Things are provided.
[0008]
According to the present invention, furthermore, 0.1 to 30 parts by weight of a compound having at least two thiirane groups in one molecule, sulfenamide-based and / or sulfenimide-based vulcanization with respect to 100 parts by weight of rubber. A rubber composition comprising 0.1 to 30 parts by weight of an accelerator and 0.01 to 5 parts by weight of sulfur is provided.
[0009]
According to this invention, the rubber composition which further mix | blended 0.5 weight part or less of organic fatty acids and / or 0.5-30 weight part of metal oxides with the said rubber composition is provided.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The rubber vulcanizing agent of the present invention is a compound having two or more thiirane groups (episulfide groups) represented by the following formula in one molecule (hereinafter also referred to as a thiirane group-containing compound). A group having the structure:
[0011]
[Chemical 1]
The present inventors compound a rubber having at least two thiirane groups in one molecule and a thiirane ring-opening agent such as a nucleophile, an electrophile or a compound in which these functional groups are protected. Thus, it was found that the thiirane group-containing compound acts as a vulcanizing agent. That is, the thiirane group-containing compound and the thiirane ring-opening agent react with each other by heating to generate thiyl (or thiolate) ions or radicals, thereby crosslinking the rubber. Thus, the thiirane group-containing compound is a latent vulcanizing agent that does not act as a vulcanizing agent before heating, and is crosslinked by reacting thiyl ions or radicals generated from thiirane groups with the rubber polymer during heating. . Therefore, the use of the thiirane group-containing compound suppresses burning before vulcanization and provides a vulcanizing agent having a high vulcanization speed during vulcanization. In addition, the cross-linked bond formed by vulcanization is a monosulfide bond and does not break easily like a polysulfide bond, and various rubber properties such as rupture strength and elongation after vulcanization and aging of vulcanized rubber. The decrease in physical properties can also be suppressed.
[0013]
The present inventors have further found that the modulus is improved by adding sulfur, and that the metal oxide promotes the reaction between the thiirane group and the ring-opening agent. In addition, since organic fatty acids such as stearic acid tend to inhibit the reaction between the thiirane group and the thiirane ring-opening agent, it is preferable to reduce the blending amount as much as possible or not.
[0014]
In order to obtain a thiirane group-containing compound used in the present invention, for example, all or part of the oxirane ring of an epoxy compound having at least two oxirane rings represented by the following formula in the molecule is substituted with a thiirane ring. In which at least two thiirane rings are present.
[0015]
[Chemical formula 2]
The epoxy compound used to obtain the thiirane group-containing compound used in the present invention is, for example, in the following formula (a), (b), (d), (e) or (f), wherein all substituents Y are oxirane. A compound that is a ring or a compound in which Z is an oxygen atom in the following formula (c). N is 0 or a number of 0 or more.
[0017]
[Chemical 3]
[Formula 4]
In addition, these epoxy compounds may be those in which hydrogen atoms or other groups in the molecule are substituted with halogen atoms. For example, the following formula (g):
[0020]
[Chemical formula 5]
(In the formula, Hal represents a halogen atom)
The compound represented by these may be sufficient. Examples of the halogen atom include bromine, chlorine, fluorine and the like.
[0022]
In the present invention, the thiirane group-containing compound is represented by the formula (a), (b), (c), (d), (e), (f), or (g), wherein at least two of Y are thiirane rings. Wherein Y other than the thiirane ring is an oxirane ring, or a compound in which at least one of Z is S and the other Z is O.
[0023]
Specific examples of the thiirane group-containing compound include those represented by the following formula. In each of the following formulas, at least two of Y are thiirane rings, and Y other than the thiirane ring is an oxirane ring, or at least one of Z is S and the other Z is O. N is a number of 0 or more.
[0024]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[Chemical 9]
The thiirane group-containing compound can be produced according to a method in which an epoxy compound and a thiirane agent (episulfide agent) are reacted in a polar solvent under strong stirring. Examples of the thiirane agent used include potassium thiocyanate (KSCN) and thiourea.
[0029]
As the polar solvent, for example, methanol, ethanol, acetone, water, or a mixed solvent thereof can be used. In particular, in order to obtain a compound (A) having a thiirane conversion rate of 100%, that is, an oxirane ring / thiirane ring content ratio of 0/100, it is preferable to use acetone as a solvent.
[0030]
The reaction is usually carried out in a temperature range of 10 to 35 ° C., for example, at room temperature, for a reaction time of about 10 to 40 hours, for example about 20 hours. The reaction atmosphere may be air or an inert gas atmosphere such as nitrogen. By raising the reaction temperature, the reaction rate can be increased and the reaction time can be further shortened. However, if it exceeds 100 ° C., side reactions of the thiirane ring may occur, which is not preferable.
[0031]
According to the present invention, the thiirane group-containing compound is preferably added in an amount of 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of rubber. If the blending amount is less than 0.1 parts by weight, the crosslinking density is low, and if it exceeds 30 parts by weight, the thiirane group-containing compound and its reaction product may migrate (bleed) to the rubber surface after vulcanization. .
[0032]
The thiirane ring-opening agent used in the present invention is not particularly limited, but reacts with a thiirane ring such as a nucleophile, an electrophile or a compound in which these functional groups are protected with a protecting group, A compound having an action of generating radicals can be used. Note that, for example, a compound having both a nucleophilic moiety (-H) and an electrophilic moiety (-O-) in one molecule, such as a hydroxyl group (-OH). Good. By protecting the nucleophilic or electrophilic site (functional group) with an appropriate organic group to make it a protective group, the protective group is returned to the nucleophilic group or electrophilic group by stimulation such as heat. Thus, a latent thiirane ring-opening agent can be obtained. Specifically, a compound having at least one selected from the group consisting of a hydroxyl group, a mercapto group, an amino group, a carboxyl group, an aldehyde group, a hydrogen group bonded to the α-position of the carbonyl group, or these protecting groups as described above It is preferable in that the reaction rate is high. Further, the thiirane ring-opening agent may be a rubber vulcanization accelerator or an anti-aging agent, and those used as a curing agent for an epoxy resin adhesive can also be used.
[0033]
Examples of the thiirane ring-opening agent used in the present invention include alcohols, amines, acid or acid anhydride compounds, aldehydes, compounds having a hydrogen group bonded to the α-position of the carbonyl group, basic active hydrogen compounds, Examples include imidazoles, thiols, phenol resins, urea resins, melamine resins, isocyanate compounds, latent curing agents, and ultraviolet curing agents.
[0034]
Specific examples of alcohols include aliphatic alcohols such as methanol, ethanol, butanol, propanol, hexanol, stearyl alcohol, hexanediol, and propanediol; aromatic alcohols such as phenol, p-methylphenol, bisphenol A, and bisphenol F. be able to.
[0035]
Specific examples of amines include aliphatic monofunctional alcohols such as methylamine, ethylamine, butylamine, propylamine, hexylamine, stearylamine; ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropyl Polyamines such as amine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane; polymethylenediamines such as trimethylhexamethylenediamine, polyetherdiamine, diethylaminopropylamine; phenylamine, p-methylamine, etc. Aromatic monofunctional amines; mensendiamine (MDA), isophoronediamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, N-aminoethyl Cycloaliphatics such as perazine (N-AEP), diaminodicyclohexylmethane, bisaminomethylcyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane Polyamines; aliphatic polyamines containing aromatic rings such as metaxylylenediamine, aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, and 3,9-bis (3-aminopropyl)- 2,4,8,10-tetraspiro [5.5] undecane and the like. Also, amine adducts (polyamine epoxy resin adducts), polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts, cyanoethylated polyamines, ketimines that are reaction products of aliphatic polyamines and ketones; linear diamines, tetramethylguanidine, triethanol Amine, piperidine, pyridine, benzyldimethylamine, picoline, 2- (dimethylaminomethyl) phenol, dimethylcyclohexylamine, dimethylbenzylamine, dimethylhexylamine, dimethylaminophenol, dimethylamino p-cresol, N, N'-dimethylpiperazine Piperidine, 1,4-diazadicyclo (2,2,2) octane, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo Like secondary amines or tertiary amines such as 5,4,0) undecene-1, or dimer acid and diethylenetriamine and liquid polyamides obtained by reacting a polyamine such as triethylene tetramine.
[0036]
Specific examples of the cycloaliphatic polyamine compound include mensendiamine (MDA), isophoronediamine (IPDA), bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine (N-AEP), and the like. Examples thereof include 3-aminomethyl-3,5,5-trimethylcyclohexylamine / bisphenol A diglycidyl ether adduct and the like.
[0037]
Specific examples of acid or acid anhydride compounds include aromatic monofunctional carboxylic acids such as acetic acid, propionic acid, palmitic acid and stearic acid; aromatic monofunctional carboxylic acids such as benzoic acid and p-methylbenzoic acid; adipic acid , Polycarboxylic acids such as azelaic acid and decanedicarboxylic acid, phthalic anhydride, trimellitic anhydride, ethylene glycol bis (anhydro trimellitate), glycerol tris (andro trimellitate), pyromellitic anhydride, 3, 3 ', 4,4'-Aromatic acid anhydrides such as benzophenone tetracarboxylic anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohex Sentetracarboxylic acid anhydride, methylhymic anhydride, trialkyltetrahydrophthalic anhydride, cyclic aliphatic acid anhydrides such as poly (phenylhexadecanedioic acid) anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacin Examples include acid anhydrides, aliphatic acid anhydrides such as dodecenyl succinic anhydride, poly (ethyloctadecanedioic acid) anhydride, halogenated acid anhydrides such as chlorendic acid anhydride, tetrabromophthalic anhydride, and het acid anhydride. .
[0038]
Specific examples of aldehydes include aliphatic aldehydes such as acetaldehyde, propionaldehyde, stearylaldehyde, propanedialdehyde, and benzenedialdehyde; aromatic aldehydes such as benzaldehyde and p-methylbenzaldehyde.
[0039]
Specific examples of the compound having a hydrogen group bonded to the α-position of the carbonyl group include dimethyl malonate and diethyl malonate.
[0040]
Specific examples of the basic active hydrogen compound include dicyandiamide and organic acid dihydrazide.
[0041]
Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1- Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-methylimidazolium isocyanurate, 2,4-diamino-6- [2-methylimidazoline- (1)]-ethyl- S-triazine, 2,4-diamino-6- [2-ethyl-4-methylimidazoline- (1)]-ethyl-S-triazine, and the like.
[0042]
Specific examples of thiols include ethanethiol, propanethiol, ethanedithiol, propanedithiol, thioglycolic acid, thioacetic acid, benzenethiol, benzenedithiol, 2,2′-bismercaptoethyl ether partial epoxy adduct, pentaerythritol Examples thereof include esters of thioglycolic acid such as tetrathioglycolate, dipentaerythritol hexathioglycolate, trimethylolpropane dorithioglycolate, polysulfide rubber having a mercapto group at the terminal, and the like.
[0043]
Specific examples of the isocyanate compound include isocyanate compounds such as toluene diisocyanate, hexamethylene diisocyanate, and xylene diisocyanate, and blocked isocyanate compounds formed by reacting an isocyanate group with phenol, alcohol, caprolactam, and the like.
[0044]
Examples of the vulcanization accelerator for rubber used as the thiirane ring-opening agent include thiuram, dithiocarbamate, sulfenamide, thiazole, xanthate, thiourea, and guanidine. Specifically, nickel dibutyldithiocarbamate, zinc dimethyldithiocarbamate, ferric dimethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc butylxanthate, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, 2-mercaptobenzothiazole, tetraethyl Thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc, 2- (4,4′-morpholinodithio) benzothiazole, N, N-diethylthiocarbamoyl- 2-benzothiazolyl sulfide, N-cyclohexyl-2-benzothiazolylsulfenamide, Nt-butyl-2-benzothiadizolyl Of rufenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N, N′-dicyclohexyl-2-benzothiazolylsulfenamide, 1,3-diphenylguanidine, di-o-toluylguanidine, dicatechol borate Di-o-toluylguanidine salt, hexamethylenetetramine, dialkyldithiophosphate zinc, Nt-butyl-2-benzothiazylsulfenamide, reaction product of N-butyraldehyde and aniline, N, N′-diphenyl Examples include thiourea and trimethylthiourea. Among them, as sulfenamide-based vulcanization accelerators, N-cyclohexyl-2-benzothiazolylsulfenamide, Nt-butyl-2-benzothiazolylsulfenamide, N, N′-dicyclohexyl-2- Benzothiazylsulfenamide, thiuram vulcanization accelerator, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, 2-mercaptobenzothiazole, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide Is preferred.
[0045]
Antiaging agents used as thiirane ring-opening agents include 2,6-di-t-butyl-p-cresol, 2,2-methylenebis-4-methyl-6-t-butylphenol, mono α-methyl-benzylphenol , Di-α-methyl-benzylphenol, tri-α-methyl-benzylphenol, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, dilauryl dithiopropionate, N-phenyl-N′-1,3-dimethylbutyl -P-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline , Poly (2,2,4-trimethyl-1,2-dihydroquinoline), octylated diphe Ruamine, reaction product of diphenylamine and acetone, N, N'-di-2-naphthyl-p-phenylenediamine, mixed diaryl-p-phenylenediamine, N- (3-methacryloyloxy-2-hydroxypropyl) -N'- Examples thereof include phenyl-p-phenylenediamine and special wax.
[0046]
When the thiirane ring-opening agent is an alcohol, the protecting group protecting the hydroxyl group is methyl ether, triphenylmethyl ether, benzyl ether, trimethylsilyl ether, t-butyldimethylsilyl ether, t-butyldiphenylsilyl ether. , Tetrahydropyranyl ether, 2-methoxyethoxymethyl ether, methoxymethyl ether and the like ether type protecting group; acetonide (isopropylidene acetal) and the like acetal type protecting group; acetyl, benzoyl, p-nitrophenoxycarbonyl and the like ester Mention may be made of type protecting groups. Furthermore, when the thiirane ring-opening agent is enol, examples of the protecting group protecting the hydroxyl group include silyl enol ether.
[0047]
When the thiirane ring-opening agent is an amine, the amino group-protected protecting group is an amide-type protecting group containing acetamido, trifluoroacetamide, benzamide, etc .: an imide-type protecting group containing phthalimide, etc .: benzyl Urethane type protecting group including urethane, t-butoxyurethane, etc .: alkyl type protecting group containing benzyl, etc .: sulfonamide type protecting group containing p-toluenesulfonamide, etc .; amino group and aliphatic carboxylic acid such as stearic acid Examples thereof include salts and salts of amino groups and aromatic carboxylic acids such as benzoic acid.
[0048]
Further, when the thiirane ring-opening agent is a carboxylic acid, examples of the protecting group that protects the carboxyl group include ester-type protecting groups such as methyl ester, t-butyl ester, benzyl ester, and triphenylmethyl ester; Examples thereof include salts with aliphatic amines such as stearylamine, and salts with carboxyl groups and aromatic amines such as aniline.
[0049]
In the case where the thiirane ring-opening agent is a compound having a hydrogen group bonded to the α-position of the carbonyl group, the protecting group protecting the hydrogen group bonded to the α-position of the carbonyl group includes a formyl group, a dithioacetal group Can be mentioned.
[0050]
In addition, when the thiirane ring-opening agent is a thiol, the protecting group that protects the thiol group includes thioether, benzylthioether, thioester, benzoylthioester, thiocarbamate, a thiol group and an aliphatic amine such as stearylamine. Mention may be made of salts, salts of thiol groups and aromatic amines.
[0051]
According to the present invention, the thiirane ring-opening agent is preferably added in an amount of 0.1 to 30 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of rubber. If the blending amount is less than 1 part by weight, vulcanization is difficult to proceed. If it exceeds 30 parts by weight, the thiirane ring-opening agent and its reaction product may migrate (bleed) to the rubber surface after vulcanization. Absent.
[0052]
According to the present invention, in addition to the thiirane group-containing compound and the sulfenamide-based and / or sulfenimide-based vulcanization accelerator as the thiirane ring-opening agent, sulfur and / or metal oxide may be used. it can. As the sulfur, any sulfur used for rubber vulcanization can be used. The amount of sulfur is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of rubber. If the blending amount is too small, the crosslinking density is lowered and the strength is lowered, which is not preferable. On the contrary, if the amount is too large, the crosslinking density is too high, which is not preferable.
[0053]
The rubber composition according to the present invention comprises a metal oxide (for example, zinc oxide, aluminum oxide, calcium oxide, titanium oxide, ferric oxide, cupric oxide, magnesium oxide, zinc carbonate per 100 parts by weight of rubber, 0.5 to 30 parts by weight, more preferably 1 to 10 parts by weight of lead monoxide, lead oxide, lead carbonate and calcium hydroxide) can be blended. If the blending amount of the metal oxide is too small, the reaction between thiirane and the thiirane ring-opening agent cannot be promoted, which is not preferred. On the contrary, if the amount is too large, the physical properties of the rubber are lowered.
[0054]
The rubber composition according to the present invention includes stearic acid, palmitic acid, lauric acid, myristic acid, oleic acid, behenic acid, and isostearic acid that have been widely used as vulcanization accelerators in rubber compositions. When an organic fatty acid is blended, the reaction between the thiirane group and the thiirane ring-opening agent tends to be inhibited. Therefore, the blending amount is preferably reduced or not blended as much as possible. Therefore, the blending amount of the organic fatty acid in the present invention is 0.5 parts by weight or less, preferably 0 to 0.1 parts by weight per 100 parts by weight of rubber.
[0055]
The rubber used in the present invention is not particularly limited, but any rubber conventionally blended in various rubber compositions, for example, natural rubber (NR), polyisoprene rubber (IR), styrene butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile butadiene copolymer rubber (NBR), butyl rubber (IlR), chloroprene rubber, ethylene propylene copolymer rubber, ethylene-propylene diene copolymer rubber, and the like. These rubbers can be used alone or as any blend.
[0056]
The rubber composition of this invention can mix | blend the compounding agent normally used in the rubber industry as needed. Examples of the compounding agent include fillers such as carbon black and silica, vulcanization accelerators, vulcanization activators, anti-aging agents, plasticizers, softeners, and the like.
[0057]
The vulcanizing agent of the present invention and a rubber composition containing the vulcanizing agent are applied to various rubber products such as tires, hoses, conveyor belts, rubber sheets, anti-vibration materials, anti-vibration rubbers, rollers, linings, rubberized cloths, sealing materials, and gloves. Although it can be used, it can be suitably used particularly as a rubber composition for tires.
[0058]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
[0059]
Synthesis of vulcanizing agent 1
To a mixed solvent of 450 ml of ethanol in which 774.4 g (8 mol) of potassium thiocyanate was dissolved and 645 ml of water, 990 g (6.78 mol) of neopentyl-diglycidyl ether (manufactured by Toto Kasei Co., Ltd., PG202) was added, After vigorously stirring at room temperature for 12 hours, the upper layer was separated, the lower layer was washed with water, dried over magnesium sulfate, and dried under reduced pressure to obtain a vulcanizing agent 1 represented by the following formula in which the oxirane ring was converted to a thiirane ring. . From the NMR analysis, it was confirmed that the thiirane conversion rate was 100%.
[0060]
[Chemical Formula 10]
Synthesis of vulcanizing agent 2
Using glycidyl ether of bisphenol F in place of neopentyl-diglycidyl ether, a vulcanizing agent 2 represented by the following formula in which the oxirane ring was converted to a thiirane ring was obtained by the same production method as vulcanizing agent 1. From the NMR analysis, it was confirmed that the thiirane conversion rate was 100%.
[0062]
Embedded image
Synthesis of vulcanizing agent 3
Using glycidyl ether of hydrogenated bisphenol A in place of neopentyl-diglycidyl ether, a vulcanizing agent 3 represented by the following formula obtained by converting the oxirane ring into a thiirane ring by the same production method as vulcanizing agent 1 is obtained. It was. From the NMR analysis, it was confirmed that the thiirane conversion rate was 100%.
[0064]
Embedded image
Examples 1-4 and Comparative Examples 1-5
A rubber composition having the composition shown in Table I below was blended with the vulcanizing agents 1 to 3 obtained above and various vulcanization accelerators, and the following rheometer characteristics were measured. Vulcanization was performed under the conditions of 160 ° C. × 60 minutes in Comparative Example 5 and 150 ° C. × 30 minutes otherwise, and the following breaking strength and breaking elongation were measured before and after aging at 100 ° C. for 48 hours. The rate (after aging / before aging) was determined.
[0066]
For example, the reaction between the vulcanizing agent 1 and the vulcanization accelerator CZ and the subsequent cross-linking reaction can be schematically described as follows.
[0067]
Embedded image
Rheometer characteristics
Based on JlS K6300, the time (minutes) required to reach 95% vulcanization at 150 ° C. was measured and designated T95. The smaller the T95, the faster the vulcanization speed. The time (minutes) when the rheometer torque decreased by 3% and 5% from the peak was defined as T-3 and T-5, respectively. The smaller the T-3 and T-5, the smaller the vulcanization reversion, and the case where no torque peak was observed, the vulcanization reversion did not occur.
[0069]
Breaking strength (MPa)
It measured based on JISK6251.
Elongation at break (%)
It measured based on JISK6251.
[0070]
[Table 1]
The following compounding agents were used.
IR: Nipol IR-2200, polyisoprene rubber manufactured by Nippon Zeon Co., Ltd.
Carbon black: HAF grade carbon black
Zinc flower: Zinc oxide No. 3
Stearic acid: industrial stearic acid
Anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine
Sulfur: 5% oil-treated sulfur
Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazolylsulfenamide
Vulcanization accelerator NS: Nt-butyl-2-benzothiazolylsulfenamide
Vulcanization accelerator TT: Tetramethylthiuram disulfide
Organic peroxide: 1,3-bis- (t-butyl-oxyisopropyl) benzene
[0072]
From Table I, the rubber | gum of Comparative Examples 1-3 of sulfur mixing | blending generate | occur | produced vulcanization | reversion and the retention rate of the physical property before and behind aging of vulcanized rubber became small. Moreover, the rubber | gum of the comparative examples 4 and 5 which did not use sulfur was inferior in the elongation at break after vulcanization in addition to the slow vulcanization | cure speed | rate (T-95). In contrast, the rubber compositions of Examples 1 to 4 blended with vulcanizing agents 1 to 3 which are thiirane group-containing compounds and rubber vulcanization accelerators which are thiirane ring-opening agents have no vulcanization return, The result was that the rubber had excellent balance between the retention of physical properties after aging and the vulcanization speed.
[0073]
Examples 5-9
Next, a rubber composition blended with vulcanizing agent 2 and other various vulcanization accelerators shown in Table II below was produced and evaluated in the same manner as in Example 1, and the same as in the above example. Good results were obtained.
[0074]
[Table 2]
The following vulcanization accelerators were used, and the other compounding agents were the same as in Example 2.
Vulcanization accelerator TBBS: Nt-butyl-2-benzothiazolylsulfenamide
Vulcanization accelerator DCBS: N, N'-dicyclohexyl-2-benzothiazolylsulfenamide
Vulcanization accelerator TMTD: Tetramethylthiuram disulfide
Vulcanization accelerator TMTM: Tetramethylthiuram monosulfide
Vulcanization accelerator TRA: Dipentamethylene thiuram tetrasulfide
[0076]
Examples 10-13 and Comparative Examples 6-7
A rubber composition blended with the vulcanizing agent 1 and vulcanization accelerator NS shown in the following Table III was produced, and the following rheometer characteristics were measured. Vulcanization is carried out under the conditions of 150 ° C. × 30 minutes, and 100% modulus and 300% modulus, breaking strength and breaking elongation of the vulcanized product are measured before and after aging at 100 ° C. × 48 hours, and the retention rate (aging) After / before aging). The results are shown in Table III.
[0077]
Rheometer characteristics: as described above
100% and 300% modulus: Modulus at 100% and 300% elongation was measured according to JIS K6251.
Breaking strength and elongation: as described above
Overcure physical properties: Physical properties of rubber vulcanized under conditions of 150 ° C x 60 minutes
Physical properties after aging: Physical properties after vulcanization sample aging at 100 ° C for 48 hours
[0078]
[Table 3]
The ingredients listed in Table III are as follows:
NR: Natural rubber RSS # 1
Carbon black: HAF grade carbon black
Zinc flower: Zinc oxide No. 3
Stearic acid: industrial stearic acid
Anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine
Sulfur: 5% oil-treated sulfur
Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazolylsulfenamide
Vulcanization accelerator NS: Nt-butyl-2-benzothiazolylsulfenamide
[0080]
As is apparent from the results in Table III, when vulcanized with sulfur, vulcanization is restored due to the rheometer characteristics (T-3, T-5). Moreover, when the aging retention rate is large, when the vulcanizing agent 1 is used, vulcanization does not occur and the aging retention rate is close to 100%. That is, the vulcanizing agent 1 is more excellent in vulcanization characteristics and aging characteristics than sulfur.
[0081]
【The invention's effect】
According to the present invention, by blending a rubber vulcanizing agent comprising a compound having at least two thiirane groups in one molecule with a thiirane ring-opening agent, the physical properties after aging of the vulcanized rubber are not impaired. Alternatively, it is possible to obtain a rubber composition that can suppress burns and vulcanization reversion due to early vulcanization and that has a high vulcanization speed. Further, according to the present invention, the modulus can be further improved by adding sulfur, and the reaction between the thiirane group and the ring-opening agent can be promoted by the metal oxide.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2000189748A JP4240765B2 (en) | 1999-06-29 | 2000-06-20 | Rubber vulcanizing agent and rubber composition containing the same |
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| JP18388499 | 1999-06-29 | ||
| JP11-183884 | 1999-06-29 | ||
| JP2000189748A JP4240765B2 (en) | 1999-06-29 | 2000-06-20 | Rubber vulcanizing agent and rubber composition containing the same |
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| JP4240765B2 true JP4240765B2 (en) | 2009-03-18 |
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| EP1475408B1 (en) * | 2002-02-15 | 2011-04-06 | Bridgestone Corporation | Rubber composition and pneumatic tire made therefrom |
| JP2004204100A (en) * | 2002-12-26 | 2004-07-22 | Bridgestone Corp | Pneumatic tire |
| US7414087B2 (en) | 2003-08-20 | 2008-08-19 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire using the same |
| JP4934971B2 (en) * | 2005-03-07 | 2012-05-23 | Ｊｎｃ株式会社 | Polymerizable liquid crystal compound having cyclic sulfide and polymer thereof |
| JP5944964B2 (en) * | 2014-08-25 | 2016-07-05 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP6597999B2 (en) * | 2015-06-01 | 2019-10-30 | 住友ゴム工業株式会社 | Fender |
| CN119750501B (en) * | 2024-11-22 | 2026-01-02 | 江西理工大学 | A method for preparing sulfur using acetamide-modified guanidine-based aqueous deep eutectic solvent |
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