JPS63218752A - Acrylate elastomer vulcanizable composition - Google Patents
Acrylate elastomer vulcanizable compositionInfo
- Publication number
- JPS63218752A JPS63218752A JP5240087A JP5240087A JPS63218752A JP S63218752 A JPS63218752 A JP S63218752A JP 5240087 A JP5240087 A JP 5240087A JP 5240087 A JP5240087 A JP 5240087A JP S63218752 A JPS63218752 A JP S63218752A
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- epoxy group
- vulcanization
- elastomer
- acid
- 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 38
- 239000000806 elastomer Substances 0.000 title claims abstract description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 31
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 11
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 31
- -1 guanidine compound Chemical class 0.000 abstract description 14
- 238000007906 compression Methods 0.000 abstract description 9
- 230000006835 compression Effects 0.000 abstract description 9
- 239000012744 reinforcing agent Substances 0.000 abstract description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 abstract description 2
- 229920006228 ethylene acrylate copolymer Polymers 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- ZFLIKDUSUDBGCD-UHFFFAOYSA-N parabanic acid Chemical compound O=C1NC(=O)C(=O)N1 ZFLIKDUSUDBGCD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 abstract 2
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 150000002357 guanidines Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 241001441571 Hiodontidae Species 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- HIMXGTXNXJYFGB-UHFFFAOYSA-N alloxan Chemical compound O=C1NC(=O)C(=O)C(=O)N1 HIMXGTXNXJYFGB-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000012990 dithiocarbamate Substances 0.000 description 2
- 150000004659 dithiocarbamates Chemical class 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- NIIBEFULKZQXKX-UHFFFAOYSA-N 1-carbamoyl-3-(methylcarbamoyl)urea Chemical compound CNC(=O)NC(=O)NC(N)=O NIIBEFULKZQXKX-UHFFFAOYSA-N 0.000 description 1
- HILAYQUKKYWPJW-UHFFFAOYSA-N 1-dodecylguanidine Chemical compound CCCCCCCCCCCCN=C(N)N HILAYQUKKYWPJW-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- HZMXJTJBSWOCQB-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl prop-2-enoate Chemical compound COCCOCCOC(=O)C=C HZMXJTJBSWOCQB-UHFFFAOYSA-N 0.000 description 1
- LQZDDWKUQKQXGC-UHFFFAOYSA-N 2-(2-methylprop-2-enoxymethyl)oxirane Chemical compound CC(=C)COCC1CO1 LQZDDWKUQKQXGC-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- MBEVSMZJMIQVBG-UHFFFAOYSA-N 2-(hydroxymethyl)guanidine Chemical compound NC(N)=NCO MBEVSMZJMIQVBG-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- QVZBVVSVFLIPER-UHFFFAOYSA-N 3-(carbamoylcarbamoyl)-1,1-diethylurea Chemical compound CCN(CC)C(=O)NC(=O)NC(N)=O QVZBVVSVFLIPER-UHFFFAOYSA-N 0.000 description 1
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- HRRVLSKRYVIEPR-UHFFFAOYSA-N 6-hydroxy-5-nitroso-1H-pyrimidine-2,4-dione Chemical compound OC1=NC(O)=C(N=O)C(O)=N1 HRRVLSKRYVIEPR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- DVICWXUADSCSLL-DDEWRDOISA-N Alloxanthin/Tetradehydrozeaxanthin/(Cynthiaxanthin)/(Pectenoxanthin) Chemical compound C([C@H](O)CC=1C)C(C)(C)C=1C#CC(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)C#CC1=C(C)C[C@@H](O)CC1(C)C DVICWXUADSCSLL-DDEWRDOISA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 description 1
- SQSPRWMERUQXNE-UHFFFAOYSA-N Guanylurea Chemical compound NC(=N)NC(N)=O SQSPRWMERUQXNE-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- DVICWXUADSCSLL-GUPSQEAKSA-N all-trans-Alloxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C#CC1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C#CC2=C(C)CC(O)CC2(C)C DVICWXUADSCSLL-GUPSQEAKSA-N 0.000 description 1
- UFRRRMXNFIGHPC-CPZJCIGYSA-N alloxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C#CC1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC#CC2=C(C)CC(O)CC2(C)C UFRRRMXNFIGHPC-CPZJCIGYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229960002319 barbital Drugs 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- ZUKSLMGYYPZZJD-UHFFFAOYSA-N ethenimine Chemical class C=C=N ZUKSLMGYYPZZJD-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 235000012631 food intake Nutrition 0.000 description 1
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- SINFYWWJOCXYFD-UHFFFAOYSA-N methoxymethyl prop-2-enoate Chemical compound COCOC(=O)C=C SINFYWWJOCXYFD-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
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- RVQZQLYGXXOJIM-UHFFFAOYSA-N tetrauret Chemical compound NC(=O)NC(=O)NC(=O)NC(N)=O RVQZQLYGXXOJIM-UHFFFAOYSA-N 0.000 description 1
- QGVNJRROSLYGKF-UHFFFAOYSA-N thiobarbital Chemical compound CCC1(CC)C(=O)NC(=S)NC1=O QGVNJRROSLYGKF-UHFFFAOYSA-N 0.000 description 1
- WNVQBUHCOYRLPA-UHFFFAOYSA-N triuret Chemical compound NC(=O)NC(=O)NC(N)=O WNVQBUHCOYRLPA-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はエポキシ基含有アクリレート系エラストマー加
硫組成物に関するものであり、更に詳しくは、すぐれた
スコーチ安定性を有し、しかも機械的特性、耐熱老化性
、圧縮永久ひずみ性などの性能にすぐれたエポキシ基含
有アクリレート系エラストマー加硫組成物に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an epoxy group-containing acrylate elastomer vulcanized composition, and more specifically, it has excellent scorch stability, mechanical properties, This invention relates to an epoxy group-containing acrylate elastomer vulcanized composition that has excellent properties such as heat aging resistance and compression set properties.
（従来の技術及び発明が解決しようとする問題点）アク
リレート系エラストマーは、耐熱性、耐油性、耐候性な
どがすぐれたエラストマーとして知られている。しかし
、主鎖に二重結合をもたないため、架橋点としてエポキ
シ基、カルメキシル基、活性塩素基などを含有させたア
クリレート系エラストマーが実用に供されている。(Prior Art and Problems to be Solved by the Invention) Acrylate elastomers are known as elastomers with excellent heat resistance, oil resistance, weather resistance, etc. However, since the main chain does not have a double bond, acrylate elastomers containing epoxy groups, carmexyl groups, active chlorine groups, etc. as crosslinking points are in practical use.
従来よシ、エポキシ基を含有するアクリレート系エラス
トマーの加硫系としては、ポリアミン、ジアミンカーバ
メート、有機カルビン酸アンモニウム、ジチオカルバミ
ン酸塩などが一般的に使用されている。しかしながら、
ポリアミンやジアミンカーバメート類を用い九場合は早
期加硫に対する安定性に欠けるため、混線加工工程でス
コーチし易いという欠点がある。ま几、有機カルＲ／酸
アンモニウムやジチオカルバミン酸塩類を用いた場合は
早期加硫に対する安定性はすぐれる反面、長時間の後加
硫を施こしても良好な圧縮永久ひずみ性が得られにくい
という欠点がある。Conventionally, polyamines, diamine carbamates, organic ammonium carbates, dithiocarbamates, and the like are generally used as vulcanization systems for acrylate elastomers containing epoxy groups. however,
When polyamines or diamine carbamates are used, they lack stability against early vulcanization, and have the disadvantage of being susceptible to scorch during the cross-wire processing. When using organic cal-R/ammonium acids or dithiocarbamates, stability against early vulcanization is excellent, but it is difficult to obtain good compression set properties even after long-term post-vulcanization. There is a drawback.
これらの欠点を改良するための加硫方法は櫨々提案され
ており、例えば特開昭５７−１７７０４４号公報、およ
び特開昭５７−１７７０４５号公報には、エポキシ基含
有アクリレート系ニジストマーに対シクアニジン系化合
物、およびグアニジン系化合物とイオウ、イオウ系化合
物を用いる加硫系が開示されている。しかしこれらの加
硫系は早期加硫に対する安定性はすぐれるものの、圧縮
永久ひずみ性が劣るという欠点がみられる。Vulcanization methods to improve these drawbacks have been proposed one after another. For example, in JP-A-57-177044 and JP-A-57-177045, vulcanization methods for cycuanidine-containing epoxy group-containing acrylate nidistomers have been proposed. vulcanization systems using guanidine-based compounds, sulfur, and sulfur-based compounds. However, although these vulcanization systems have excellent stability against early vulcanization, they have the disadvantage of poor compression set properties.
本発明者等は、これらの欠点全改良すべく種々の加硫系
について鋭意検討を重ねた結果、エポキシ基含有アクリ
レート系エラストマーに対し、分子中に特定の結合を有
する低分子有機化合物とグアニジン系化合物を加硫系と
して用層ることにより、すぐれたスコーチ安定性を有し
、しかも機械的特性、耐熱老化性、圧縮永久ひずみ性な
どにすぐれた加硫物が得られることを見い出し、本発明
の完成に到ったものである。As a result of intensive studies on various vulcanization systems in order to improve all of these drawbacks, the present inventors have determined that acrylate elastomers containing epoxy groups can be cured using low-molecular-weight organic compounds with specific bonds in the molecule and guanidine-based vulcanization systems. It has been discovered that by layering a compound as a vulcanization system, a vulcanizate with excellent scorch stability, as well as excellent mechanical properties, heat aging resistance, compression set properties, etc., can be obtained, and the present invention has been made. has been completed.
（問題解決の手段）
すなわち、本発明は、エポキシ基含有アクリレート系エ
ラストマーに、（１）分子中に原子を表わす。）を２個
以上有する有機化合物と。(Means for Solving the Problem) That is, the present invention provides an epoxy group-containing acrylate elastomer with (1) atoms in the molecule. ) with two or more organic compounds.
（２）グアニジン系化合物を配合して成るアクリレート
系エラストマー加硫組性物を提供するものである。(2) The present invention provides a vulcanized acrylate elastomer compound containing a guanidine compound.
本発明において用いられるエポキシ基を含有するアクリ
レート系エラストマーは、架橋点としてのエポキシ基含
有単量体を通常０．１〜１０重童％。The epoxy group-containing acrylate elastomer used in the present invention usually contains 0.1 to 10 weight percent of the epoxy group-containing monomer as a crosslinking point.
好ましくは０．５〜３重量ちとアルキルおよびアルコキ
シアルキルアクリレートの中から選ばれた少なくとも一
種の単量体３０〜９９．９重量％、ならびにこれらの単
量体と共重合可能な共重合性末端ビニルまたはビニリデ
ン基を有する少なくとも一種の単菫体Ｏ〜７０重童うと
を公知の重合法により共重合させることによシ得られる
エラストマーである。Preferably 0.5 to 3% by weight of at least one monomer selected from alkyl and alkoxyalkyl acrylates, and a copolymerizable terminal vinyl copolymerizable with these monomers. Alternatively, it is an elastomer obtained by copolymerizing at least one type of monopolymer 0 to 70 polymers having a vinylidene group by a known polymerization method.
架橋点と°して用いらｎるエポキシ基含有単重体の例と
しては、グリシジルアクリレート、グリシジルメタアク
リレート、ビニルグリシジルエーテル、アリルグリシジ
ルエーテル、メタリルグリシジルエーテルなどが挙げら
れるが、特にこれらの中ではグリシノルアクリレート、
グリシジルメタアクリレートが好ましい。Examples of the epoxy group-containing monomer used as a crosslinking point include glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, and methallyl glycidyl ether. glycinol acrylate,
Glycidyl methacrylate is preferred.
エポキシ基含有単量体と共重合可能なアルキルアクリレ
ートの例としては、メチルアクリレート、エチルアクリ
レート、グロビルアクリレート、ブチルアクリレート、
２−エチルへキシルアクリレート、ｎ−オクチルアクリ
レートなどのアルキル基が１〜８個の炭素原子を有する
アルキルアクリレートが挙げられる。アルコキシアルキ
ルアクリレートの例としては、メトキシメチルアクリレ
ート、メトキシエチルアクリレート、エトキシエチルア
クリレート、ブトキシエチルアクリレート、メトキシエ
トキシエチルアクリレートナトのフルコキシ基ならびに
アルキレン基がそれぞｎ１〜４個の炭素原子を有するア
ルコキシアルキルアクリレートが挙げられる。Examples of alkyl acrylates copolymerizable with epoxy group-containing monomers include methyl acrylate, ethyl acrylate, globyl acrylate, butyl acrylate,
Examples include alkyl acrylates in which the alkyl group has 1 to 8 carbon atoms, such as 2-ethylhexyl acrylate and n-octyl acrylate. Examples of alkoxyalkyl acrylates include methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, methoxyethoxyethyl acrylate, and alkoxyalkyl acrylates in which the flukoxy group and the alkylene group each have n1 to 4 carbon atoms. can be mentioned.
エポキシ基含有単量体と共重合可能な末端ビニルおよび
ビニリデン基を有する単量体の例としては、酢酸ビニル
、プロピオン酸ビニル、酪酸ビニルなどのビニルエステ
ル；エテレ／、プロピレン、ｌ−ブテンなどのα−モノ
オレフィン；メチルビニルケトン、エチルビニルケトン
などのビニルケトン；スチレン、α−メチルスチレン、
ビニルトルエンなどのビニル芳香族化合物；ビニルエテ
ルエーテル、アリルメチルエーテルなどのビニルエーテ
ル；アクリロニトリル、メタアクリレートリルなどのビ
ニルおよび？二すデンニトリル；２−ヒドロキシエチル
アクリレート、４ヒドロキシブチルアクリレートなどの
水酸基を有するビニル単量体；２−シアノエチルアクリ
レート、３−ンアノグロビルアクリレート、４−７アノ
プチルアクリレートなどのシアノ置換ビニル単量体；ア
クリルアミド、メタクリルアミｌ−”、 Ｎ−メチロー
ルアクリルアミドなどのビニルおよびビニリデンアミド
；メチルメタアクリレート、エチルメタアクリレート、
ブチルメタアクリレートなどのビニリデンアクリレート
：ｆタジエン、イングレンなどの共役ジエンなどが挙げ
られ、これらの単量体はアルキルまたはアルコキシアル
キルアクリレートと１種または２種以上を組み合わせて
用いることかできる。Examples of monomers having terminal vinyl and vinylidene groups that can be copolymerized with epoxy group-containing monomers include vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate; α-monoolefin; vinyl ketones such as methyl vinyl ketone and ethyl vinyl ketone; styrene, α-methylstyrene,
Vinyl aromatic compounds such as vinyl toluene; vinyl ethers such as vinyl ether ether and allyl methyl ether; vinyl and ? Didennitrile; vinyl monomers with hydroxyl groups such as 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate; cyano-substituted vinyl monomers such as 2-cyanoethyl acrylate, 3-anoglobyl acrylate, and 4-7-anoptyl acrylate vinyl and vinylidene amides such as acrylamide, methacrylamide, N-methylol acrylamide; methyl methacrylate, ethyl methacrylate,
Examples include vinylidene acrylate such as butyl methacrylate; conjugated dienes such as f-tadiene and ingrene; these monomers can be used alone or in combination with an alkyl or alkoxyalkyl acrylate.
エポキシ基を含有するアクリレート系エラストマーの例
としては、エポキシ基含有アクリレート共重合体ニジス
トマー、エポキシ基含有エチレン−アクリレート共重合
体エラストマー、エポキシ基含有エチレン−酢酸ビニル
−アクリレート共重合体エラストマー、エポキシ基含有
アクＩ）シー）−アクリロニトリル共重合体ニジストマ
ー、エポキシ基含有アクリレート−酢酸ビニル−アクリ
ロニトリル共重合体エラストマー、エポキシ基含有アク
リレート−ブタジェン−アクリロニトリル共重合体エラ
ストマーなどが挙げられるが、特にこれらのエラストマ
ーに制限されるものではない。Examples of acrylate elastomers containing epoxy groups include epoxy group-containing acrylate copolymer elastomers, epoxy group-containing ethylene-acrylate copolymer elastomers, epoxy group-containing ethylene-vinyl acetate-acrylate copolymer elastomers, and epoxy group-containing ethylene-vinyl acetate-acrylate copolymer elastomers. Examples include acrylonitrile copolymer elastomer, epoxy group-containing acrylate-vinyl acetate-acrylonitrile copolymer elastomer, and epoxy group-containing acrylate-butadiene-acrylonitrile copolymer elastomer, but are particularly limited to these elastomers. It is not something that will be done.
本発明で加硫剤として使用される分子中に又は硫黄原子
を表わす）ｆｔ２個以上有する有機化合物は該結合を有
する複素環式化合物、芳香族化合物及び鎖状の尿素誘導
体である。又、該結合が２個以上とは該結合が独立して
２個以上存在するＨＹＨＸ
単位として２個以上含まれる場合が含まれる。さらに、
該結合は複素環化合物の置換基として環外に存在しても
良い。又該結合中のＸとＹは同一でも、異なってもよい
。Organic compounds having two or more ft (representing sulfur atoms) in the molecule used as a vulcanizing agent in the present invention include heterocyclic compounds, aromatic compounds, and chain urea derivatives having such a bond. Furthermore, the phrase "two or more bonds" includes a case where two or more bonds are included as HYHX units in which two or more bonds exist independently. moreover,
The bond may exist outside the ring as a substituent of the heterocyclic compound. Further, X and Y in the bond may be the same or different.
複素環式化合物としてはパラバン酸、アロキサン、アロ
キサンチン、アロキサン−５−オキシム、バルビッル酸
、５−ヒドロキシバルビッル酸、５−ペンデルバルビッ
ル酸、５−アミノバルビッル酸、５−ヒドロ中ジイミノ
バルビッル酸、５．５−ジエチルバルビッル酸、５−エ
チル−５−７エニルパルピツル酸、５−（１−メチルブ
チル）−５−（アリル）バルビッル酸、 ５．５−ノア
リルパルビツル酸、インシアヌル酸、擬尿酸など及びこ
れらの化合物の一〇−の酸素原子を硫黄原子で置換した
もの、２，４−ジチオバルビッル酸、２−チオバルビッ
ル酸などが挙げられる。Heterocyclic compounds include parabanic acid, alloxan, alloxanthin, alloxan-5-oxime, barbylic acid, 5-hydroxybarbic acid, 5-pendelbarbic acid, 5-aminobarbic acid, 5-hydro diimino Barbic acid, 5.5-diethylbarbituric acid, 5-ethyl-5-7enylparpituric acid, 5-(1-methylbutyl)-5-(allyl)barbituric acid, 5.5-noallylparbituric acid Examples include acids such as incyanuric acid, pseudouric acid, and compounds in which the 10-oxygen atom of these compounds is replaced with a sulfur atom, 2,4-dithiobarbital acid, 2-thiobarbital acid, and the like.
芳香族化合物としてはピロメリト酸ジイミド、メリト酸
トリイミド、１，４．５．８−ナフタルノイミドなど及
びこれらの対応のチオイミドが挙げられる。Examples of the aromatic compound include pyromellitic acid diimide, mellitic acid triimide, 1,4.5.8-naphthalinoimide, and their corresponding thioimides.
尿素誘導体としてはトリウレット、ｌ−メチルトリウレ
ット、１．１−ジエチルトリウレット、テトラウレット
など及びこれらの対応のチオウレットが挙げられる。Examples of urea derivatives include triuret, 1-methyltriuret, 1,1-diethyltriuret, tetrauret, and their corresponding thiourets.
これらの化合物はエポキシ基含有エラストマーの重合反
応時もしくは重合終了時に添加混合することができ、あ
るいは通常ゴム工業界で用いる混線機により該エラスト
マーに補強剤などの他の配合剤と併わせて添加混合する
ことができる。These compounds can be added and mixed during the polymerization reaction of the epoxy group-containing elastomer or at the end of the polymerization, or they can be added and mixed to the elastomer along with other compounding agents such as reinforcing agents using a mixer commonly used in the rubber industry. can do.
これらの化合物の使用量は該エラストマー１００重量部
当り通常０．１〜１０重量部であり、加硫速度、加硫物
の機械的特性、圧縮永久ひずみ性などの面から、それぞ
れ好ましい範囲として上記範囲から選択される。０．１
重量部未満では架橋密度が低く、実用的な加硫物とは成
シ得ない。一方１０重量部を超えて用いると加硫速度が
著しく遅くなり実用に供し得る加硫物は得られない。好
ましくは０．２〜５重量部である。The amount of these compounds used is usually 0.1 to 10 parts by weight per 100 parts by weight of the elastomer, and from the viewpoint of vulcanization rate, mechanical properties of the vulcanizate, compression set property, etc., the preferred ranges are as follows. selected from a range. 0.1
If the amount is less than 1 part by weight, the crosslinking density will be low and a practical vulcanizate cannot be obtained. On the other hand, if more than 10 parts by weight is used, the vulcanization rate becomes extremely slow and a vulcanizate that can be put to practical use cannot be obtained. Preferably it is 0.2 to 5 parts by weight.
本発明で上記化合物と併用するグアニジン系化合物の例
としてはグアニジノ、アミノダアニジン、１．１，３．
３−テトラメチルグアニジン、ｎ−ドデシルグアニジン
、ｌ、６−シグアニジノヘキサン、メチロールグアニジ
ン、ジメテロールダアニジン、グアニル尿素、ビグアニ
ド、ｌ−７エニルグアニジン、１．３−ジフェニルグア
ニシン、１．３−シー０−）リルダアニゾン、トリフェ
ニルダアニジン、１−ｏ−トリルビグアニド、ニーベン
ゾルー２，３−ジメチルダアニジン、シアングアニジン
などが具体的なものとして挙げられる。Examples of guanidine compounds used in combination with the above compounds in the present invention include guanidino, aminodanidine, 1.1, 3.
3-tetramethylguanidine, n-dodecylguanidine, l,6-cyguanidinohexane, methylolguanidine, dimeteroldaanidine, guanylurea, biguanide, l-7enylguanidine, 1.3-diphenylguanidine, 1.3 Specific examples thereof include lyldaanizone, triphenyldaanidine, 1-o-tolylbiguanide, nibenzo-2,3-dimethyldaanidine, and cyanoguanidine.
これらのグアニジン系化合物は１種または２種以上を併
せて用いることができ、エポキシ基含有アクリシート系
エラストマー１００］ｉ：Ｉｉ部に対し通常０．１〜ｌ
Ｏ重量部の割合で用いられる。これらの化合物のエポキ
シ基含有アクリレート系エラストマーに対する使用割合
は、加硫速度、加硫物の機械的特性、圧縮永久ひずみ性
などの面から上記範囲内でそれぞれ好ましい範囲として
選択されるものであシ、０．１重量部未満では加硫がほ
とんど進行せず一方、１０重量部を超えて用いた場合は
加硫速度が早くなり、加工安定性が損なわれる。These guanidine compounds can be used alone or in combination of two or more, and are usually used in an amount of 0.1 to 1 to 100]i:Ii parts of the epoxy group-containing acrylate elastomer.
It is used in a proportion of 0 parts by weight. The ratio of these compounds to the epoxy group-containing acrylate elastomer is selected as a preferable range from the viewpoint of vulcanization rate, mechanical properties of the vulcanizate, compression set properties, etc. If the amount is less than 0.1 part by weight, vulcanization will hardly proceed, whereas if it is used in excess of 10 parts by weight, the vulcanization rate will increase and processing stability will be impaired.
好ましくは０．１〜５重量部である。Preferably it is 0.1 to 5 parts by weight.
本発明の２１Ｉ７Ｗｃ組成物はエポキシ基含有アクリレ
ート系エラストマーにこれらの加硫系ならびに通常１９
人工業界で用いられて＾る補強剤、充填剤、可塑剤、安
定剤、加工助剤などをロール、・ヤンパリーなどの通常
の混線機によって混合することによって調製される。該
組成物は目的に厄じ良形状に成形し加硫工程を経て最終
製品とされる。The 21I7Wc composition of the present invention is an epoxy group-containing acrylate elastomer with these vulcanization systems and usually 19
It is prepared by mixing reinforcing agents, fillers, plasticizers, stabilizers, processing aids, etc. used in the artificial industry using a conventional mixer such as a roll or rampery. The composition is molded into a desired shape and subjected to a vulcanization process to form a final product.
加硫は通常１２０ｔｌ：以上の温度で行なわれ、好まし
くは１５０℃〜２２０’Ｃ楊度の温度で１〜３０分間行
なわれ、後加硫は１５０℃〜２００℃程度の温度で１〜
２４時間糧度行なわれる。Vulcanization is usually carried out at a temperature of 120 tl or more, preferably at a temperature of 150°C to 220'C for 1 to 30 minutes, and post-vulcanization is carried out at a temperature of about 150°C to 200°C for 1 to 30 minutes.
Food intake is carried out 24 hours a day.
本発明の加硫系によって得られるエポキシ基含有アクリ
レート系エラストマーの加硫物は耐熱老化性、耐油性、
圧縮永久ひずみ性などの緒特性がすぐれるため、これら
の性能を利用して各種クール材（がスケット、Ｏ−リン
グ、バクキング、オイルシール）、各種ホース類、ベル
ト類などの用途に広く有効に用いることができる。The vulcanizate of the epoxy group-containing acrylate elastomer obtained by the vulcanization system of the present invention has heat aging resistance, oil resistance,
Because of its excellent properties such as compression set, it can be widely used for various cooling materials (sketches, O-rings, backing, oil seals), various hoses, belts, etc. Can be used.
（実施例） 以下に実施例により本発明を具体的に説明する。(Example) The present invention will be specifically explained below using Examples.
なおチおよび部数は重量基準である。Note that numbers and parts are based on weight.
実施例１゜
通常の乳化重合法によって合成したエポキシ基含有アク
リレートエラストマーＣＣ−ＮＭＲ化学シフトから求め
た組成Ｃ％）：エテルアクリレート４８、７ 、ブチル
アクリレート３１、メトキンエチルアクリレート１９、
グリ７ノルメタアクリ１／−ト１．３］１００部、ステ
アリン酸１部、ＷｉＡＦカーメンブラック（東海カーフ
１ζン社夷品ジースト１１６）６０部、アミン系老化防
止剤（ユニロイヤル社製品ナウガード４４５ ） ２部
、および第１表に示される各種配合剤の所定１を６イン
チロールで混練し配合物を調製した。Example 1 Epoxy group-containing acrylate elastomer synthesized by conventional emulsion polymerization method Composition determined from CC-NMR chemical shift (C%): Ether acrylate 48,7, Butyl acrylate 31, Metquin ethyl acrylate 19,
Gly7normethacrylic 1/-t 1.3] 100 parts, stearic acid 1 part, WiAF Carmen Black (Tokai Calf 1 Zeon Co., Ltd. product Geast 116) 60 parts, amine anti-aging agent (Uniroyal Co. product Naugard 445) 2 and predetermined 1 of various compounding agents shown in Table 1 were kneaded using a 6-inch roll to prepare a compound.
得られた各配合物につｈて、ＪＩＳＫ−６３００に従っ
てムーニースコーチタイムを測定した。また各配合物を
１７０℃で２０分間プレス加硫を行った後、１５０℃の
ギヤーオープン中で４時間の後加硫を行った。得られた
各加硫物についてＪＩＳ Ｋ−６３０１に準じて加硫諸
物性を測定した。得られた結果を第２表に示した。The Mooney scorch time of each of the obtained formulations was measured according to JISK-6300. Further, each compound was press-cured at 170°C for 20 minutes, and then post-vulcanized for 4 hours in an open gear at 150°C. Vulcanized physical properties of each of the obtained vulcanizates were measured according to JIS K-6301. The results obtained are shown in Table 2.
第 １ 表
注）加硫剤の略号
ＴＭＧ ： １，１．３．３−テトラメチルグアニ
ジンこれらの結果よｐ本発明の加硫系は従来よシ使用さ
れている加硫系（比較例１１，１２）に比べ、１７０℃
、２０分という短時間のプレス加硫ニオいても加硫物の
機械的特性がすぐれ、更に圧縮永久ひずみもすぐれてい
る。このため後加硫の省略もしくは後加硫時間の大幅燭
縮が可能となることがわかる。また分子中にイミドジカ
ルボニル基１０）の加硫性能は貧弱であることもわかる
。Table 1 Note: Abbreviation of vulcanizing agent TMG: 1,1.3.3-tetramethylguanidine Based on these results, the vulcanizing system of the present invention is the vulcanizing system conventionally used (Comparative Example 11, 12), 170℃
Even after press vulcanization for a short time of 20 minutes, the vulcanized material has excellent mechanical properties and also has excellent compression set. It can be seen that this makes it possible to omit post-vulcanization or significantly shorten the post-vulcanization time. It can also be seen that the vulcanization performance of the imidodicarbonyl group 10) in the molecule is poor.
実施例２
前記のエポキシ基含有アクリレートエラストマー１００
部、ステアリン酸１部、ＭＡＦカーゼンブラック６０部
、アミン系老化防止剤（ユニロイヤル製品ナウガード４
４５）２部および第３表に示される加硫剤の所定量を６
インチロールで混練し配合物を調製した。Example 2 The above epoxy group-containing acrylate elastomer 100
part, stearic acid 1 part, MAF Kazen Black 60 parts, amine anti-aging agent (Uniroyal product Naugard 4
45) Add 2 parts and the specified amount of the vulcanizing agent shown in Table 3 to 6
A blend was prepared by kneading with an inch roll.
得られた各配合物についてムーニースコーチタイムを測
定した。また各配合物を１７０℃で２０分間ｆレス加硫
を行りた後１５０℃のギヤーオープン中で４時間の後加
硫を行った。得られた各加硫物について実施例１と同様
に諸物性を測定した。Mooney scorch time was measured for each of the resulting formulations. Further, each compound was subjected to f-less vulcanization at 170° C. for 20 minutes, and then post-vulcanized at 150° C. for 4 hours in an open gear. Various physical properties of each of the obtained vulcanizates were measured in the same manner as in Example 1.
得られた結果を第４表に示した。The results obtained are shown in Table 4.
これらの結果よりグアニジン系化合物の増量はスコーチ
タイムを早めること、イミドジカル？ニル基含有化合物
を過剰に配合すると加硫速度が遅くなり加硫物の緒特性
が損なわれること、またグアニジン系化合物ま九はイミ
ドジカルゲニル基含有化合物のどちらか一方が欠けると
（比較例２８゜２９）加硫物の緒特性が損なわれること
、がわかる。These results show that increasing the amount of guanidine compounds accelerates the scorch time. If one of the guanidine-based compounds or the imidodicargenyl group-containing compound is lacking (comparative example 28゜29) It can be seen that the properties of the vulcanizate are impaired.
また各種のグアニジン系化合物が本発明の加硫系として
使用できることもわかる。It is also understood that various guanidine compounds can be used as the vulcanization system of the present invention.
実施例３
通常の高圧重合法で合成したエポキシ基含有エチレン−
アクリレート共重合体エラストマー（１３Ｃ−ＮＭＲ化
学シフトから求め九組成％） ：エチレン４０、メチル
アクリレート５８．２、グリシツルメタアクリレ−）１
．８）１００部、ステアリン酸１部、ＭＡＦカー？ンブ
ラック４５部、アミン系老化防止剤（ユニロイヤル製品
ナウガード４４５）２部および第５表に示される加硫剤
の所定量を６インチロールで混練し配合量を調製した。Example 3 Epoxy group-containing ethylene synthesized by ordinary high-pressure polymerization method
Acrylate copolymer elastomer (9 composition % determined from 13C-NMR chemical shift): ethylene 40, methyl acrylate 58.2, glycytyl methacrylate) 1
．． 8) 100 parts, stearic acid 1 part, MAF car? 45 parts of black, 2 parts of an amine anti-aging agent (Naugard 445 manufactured by Uniroyal), and a predetermined amount of the vulcanizing agent shown in Table 5 were kneaded using a 6-inch roll to prepare the blending amount.
得られた配合物のムーニースコーチタイムを測定後、実
施例１と同様な条件で各加硫物を作成し諸物性値を測定
した。得られた結果を第６表に示した。After measuring the Mooney scorch time of the obtained formulation, each vulcanizate was prepared under the same conditions as in Example 1, and various physical properties were measured. The results obtained are shown in Table 6.
第５表Table 5
Claims (1)
分子中に▲数式、化学式、表等があります▼結合（式中
Ｘ及びＹは酸素原子又は硫黄原子を表わす。）を２個以
上有する有機化合物と、（２）グアニジン系化合物を配
合して成るアクリレート系エラストマー加硫組成物。(1) to the epoxy group-containing acrylate elastomer;
It is made by blending an organic compound with two or more ▲numeric formulas, chemical formulas, tables, etc. in the molecule (in the formula, X and Y represent oxygen atoms or sulfur atoms) and (2) a guanidine-based compound. Acrylate elastomer vulcanized composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5240087A JPH0794588B2 (en) | 1987-03-07 | 1987-03-07 | Acrylate elastomer vulcanizing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5240087A JPH0794588B2 (en) | 1987-03-07 | 1987-03-07 | Acrylate elastomer vulcanizing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63218752A true JPS63218752A (en) | 1988-09-12 |
| JPH0794588B2 JPH0794588B2 (en) | 1995-10-11 |
Family
ID=12913754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5240087A Expired - Fee Related JPH0794588B2 (en) | 1987-03-07 | 1987-03-07 | Acrylate elastomer vulcanizing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0794588B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014505765A (en) * | 2010-12-29 | 2014-03-06 | ランクセス・ドイチュランド・ゲーエムベーハー | Vulcanizable composition based on nitrile rubber containing epoxy groups |
| US9650452B2 (en) | 2010-12-29 | 2017-05-16 | Arlanxeo Deutschland Gmbh | Vulcanizable compositions based on nitrile rubbers containing epoxy groups |
| US9725547B2 (en) | 2011-10-11 | 2017-08-08 | Arlanxeo Deutschland Gmbh | Vulcanisable compositions based on epoxy group-containing nitrile rubbers |
| EP3156426A4 (en) * | 2014-06-10 | 2017-11-08 | Mitsubishi Gas Chemical Company, Inc. | Modified rubber for tyre, rubber composition for tyre using said modified rubber and tyre |
| JP2020503426A (en) * | 2016-12-13 | 2020-01-30 | スリーエム イノベイティブ プロパティズ カンパニー | Epoxy stabilization using substituted barbituric acids |
-
1987
- 1987-03-07 JP JP5240087A patent/JPH0794588B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014505765A (en) * | 2010-12-29 | 2014-03-06 | ランクセス・ドイチュランド・ゲーエムベーハー | Vulcanizable composition based on nitrile rubber containing epoxy groups |
| US9650452B2 (en) | 2010-12-29 | 2017-05-16 | Arlanxeo Deutschland Gmbh | Vulcanizable compositions based on nitrile rubbers containing epoxy groups |
| US9868806B2 (en) | 2010-12-29 | 2018-01-16 | Arlanxeo Deutschland Gmbh | Compositions that can be vulcanized and that are based on nitrile rubbers containing epoxy groups |
| US9725547B2 (en) | 2011-10-11 | 2017-08-08 | Arlanxeo Deutschland Gmbh | Vulcanisable compositions based on epoxy group-containing nitrile rubbers |
| EP3156426A4 (en) * | 2014-06-10 | 2017-11-08 | Mitsubishi Gas Chemical Company, Inc. | Modified rubber for tyre, rubber composition for tyre using said modified rubber and tyre |
| US10465016B2 (en) | 2014-06-10 | 2019-11-05 | Mitsubishi Gas Chemical Company, Inc. | Modified rubber for tire, rubber composition for tire using the same, and tire |
| JP2020503426A (en) * | 2016-12-13 | 2020-01-30 | スリーエム イノベイティブ プロパティズ カンパニー | Epoxy stabilization using substituted barbituric acids |
| US11584823B2 (en) | 2016-12-13 | 2023-02-21 | 3M Innovative Properties Company | Epoxy stabilization using substituted barbituric acids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0794588B2 (en) | 1995-10-11 |
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