JPH04342710A - Thermoplastic elastomer and its production - Google Patents
Thermoplastic elastomer and its productionInfo
- Publication number
- JPH04342710A JPH04342710A JP11612591A JP11612591A JPH04342710A JP H04342710 A JPH04342710 A JP H04342710A JP 11612591 A JP11612591 A JP 11612591A JP 11612591 A JP11612591 A JP 11612591A JP H04342710 A JPH04342710 A JP H04342710A
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- parts
- unsubstituted
- formula
- 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.)
- Pending
Links
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229920000800 acrylic rubber Polymers 0.000 claims abstract description 42
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 42
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 19
- 230000009477 glass transition Effects 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims description 105
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- -1 Acrylic acid glycol ester Chemical class 0.000 claims description 21
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 21
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 abstract description 15
- 239000000806 elastomer Substances 0.000 abstract description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 29
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 17
- 239000003921 oil Substances 0.000 description 15
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 14
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 13
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 3
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 3
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 2
- LHEKBWMWMVRJMO-UHFFFAOYSA-N 3-methoxypropyl prop-2-enoate Chemical compound COCCCOC(=O)C=C LHEKBWMWMVRJMO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- IAXXETNIOYFMLW-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) 2-methylprop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C(=C)C)CC1C2(C)C IAXXETNIOYFMLW-UHFFFAOYSA-N 0.000 description 1
- VYPRXWXGLLURNB-UHFFFAOYSA-N (5-methyl-2-propan-2-ylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(C)C1CCC(C)CC1OC(=O)C(C)=C VYPRXWXGLLURNB-UHFFFAOYSA-N 0.000 description 1
- LNOKVKHZEYOLIQ-UHFFFAOYSA-N 1-(2,6-diethylphenyl)pyrrole-2,5-dione Chemical compound CCC1=CC=CC(CC)=C1N1C(=O)C=CC1=O LNOKVKHZEYOLIQ-UHFFFAOYSA-N 0.000 description 1
- VMDQUQBEIFMAIC-UHFFFAOYSA-N 1-(2,6-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(C)=C1N1C(=O)C=CC1=O VMDQUQBEIFMAIC-UHFFFAOYSA-N 0.000 description 1
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 description 1
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 1
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- 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
- CDZAAIHWZYWBSS-UHFFFAOYSA-N 2-bromoethyl prop-2-enoate Chemical compound BrCCOC(=O)C=C CDZAAIHWZYWBSS-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
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- UACBZRBYLSMNGV-UHFFFAOYSA-N 3-ethoxypropyl prop-2-enoate Chemical compound CCOCCCOC(=O)C=C UACBZRBYLSMNGV-UHFFFAOYSA-N 0.000 description 1
- LKUOJDGRNKVVFF-UHFFFAOYSA-N 4-(2,5-dioxopyrrol-1-yl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N1C(=O)C=CC1=O LKUOJDGRNKVVFF-UHFFFAOYSA-N 0.000 description 1
- GAKWESOCALHOKH-UHFFFAOYSA-N 4-methoxybutyl prop-2-enoate Chemical compound COCCCCOC(=O)C=C GAKWESOCALHOKH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910004878 Na2S2O4 Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 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
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000002245 particle Substances 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- HEKQWIORQJRILW-UHFFFAOYSA-N tetrakis(prop-2-enyl) benzene-1,2,4,5-tetracarboxylate Chemical compound C=CCOC(=O)C1=CC(C(=O)OCC=C)=C(C(=O)OCC=C)C=C1C(=O)OCC=C HEKQWIORQJRILW-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、架橋アクリルゴム成分
およびメタクリル酸エステルとマレイミド類との共重合
体樹脂成分から成る耐熱性と耐油性に優れ、かつ耐寒性
にも優れた新規な熱可塑性エラストマー及びその製造方
法に関する。[Industrial Application Field] The present invention is a novel thermoplastic material that has excellent heat resistance, oil resistance, and cold resistance, and is composed of a crosslinked acrylic rubber component and a copolymer resin component of methacrylic acid ester and maleimides. This invention relates to an elastomer and its manufacturing method.
【０００２】0002
【従来の技術】熱可塑性エラストマーは、使用温度範囲
内ではゴム弾性を示すが、いわゆる加硫ゴムとは異なり
、高温においては溶融成形が可能な高分子素材である。
すなわち、熱可塑性エラストマーは、加硫ゴムと熱可塑
性樹脂の双方の性質を備えており、その特徴を生かして
近年著しく需要が増大したため大量に生産されるように
なった。このような熱可塑性エラストマーは、各種のも
のが市販されており、一般に、その化学構造もしくは構
成成分の組成に基づいて、オレフィン系、スチレン系、
塩化ビニル系、ウレタン系、エステル系、アミド系など
に分類されている。このような熱可塑性エラストマーは
加硫ゴムに比較してトータルコストが安価なことから、
市場にて高温でしかも油脂類と接触するおそれのある所
に使用されてきた加硫ゴム製品等に代えて使用したいと
いう要請がある。しかしながら、従来の熱可塑性エラス
トマーは耐熱性をある程度備えているが、耐油性に乏し
かったり（例えば、オレフィン系）、耐油性に優れてい
るが耐熱性に乏しかったり（例えば、塩化ビニル系、ウ
レタン系）、あるいは、硬い領域では耐熱性および耐油
性に優れているが、加硫ゴム的な柔らかさの領域では耐
油性や耐熱性が著しく低下してしまう（例えばエステル
系、アミド系）などの問題があり、上記要請に応えるこ
とができなかった。BACKGROUND OF THE INVENTION Thermoplastic elastomers exhibit rubber elasticity within the operating temperature range, but unlike so-called vulcanized rubber, they are polymeric materials that can be melt-molded at high temperatures. That is, thermoplastic elastomers have the properties of both vulcanized rubber and thermoplastic resins, and by taking advantage of these characteristics, demand has increased significantly in recent years and they have been produced in large quantities. Various types of such thermoplastic elastomers are commercially available, and generally, based on their chemical structure or composition of constituent components, they are olefin-based, styrene-based,
It is classified into vinyl chloride type, urethane type, ester type, amide type, etc. Since the total cost of such thermoplastic elastomers is lower than that of vulcanized rubber,
There is a demand for use in place of vulcanized rubber products, etc., which have been used in the market at high temperatures and where there is a risk of contact with oils and fats. However, conventional thermoplastic elastomers have some degree of heat resistance but poor oil resistance (e.g., olefin type), or have excellent oil resistance but poor heat resistance (e.g., vinyl chloride type, urethane type). ), or have excellent heat and oil resistance in the hard region, but have a significant drop in oil and heat resistance in the soft region of vulcanized rubber (e.g. ester-based, amide-based). Therefore, we were unable to respond to the above request.
【０００３】一方、アクリル酸のアルキルエステルと、
加硫工程で架橋点を提供する少量のモノマー（例えば、
クロロエチルビニルエーテル、エチリデンノルボルネン
など）との共重合体はアクリルゴムとして公知であり、
これらはロール等を用いて、架橋剤等と混練し、架橋さ
せて実用に供されている。また、マレイミド類をメタク
リル酸メチルと共重合させることにより得られた共重合
体は、メタクリル酸メチルの単独重合体よりも耐熱性に
優れていることも特公昭４３−９７５３号公報により公
知である。さらに、メタクリル酸メチルとマレイミド類
との共重合体の耐衝撃性を改良するために、該共重合体
にアクリルゴムを配合した組成物もまた公知である（例
えば特公昭４３−９７５３号および特開昭６２−１３２
９１１号各公報）。しかしながら、これら公知の方法に
おいてはアクリルゴムの含有量が少ないこともあって、
軟らかい領域のものでは耐熱性と耐油性を兼ね備えたも
のが得られていない。また、特開昭６２−１３２９１１
号公報には、アクリルゴムの含量が５０％を超えると、
メタクリル酸メチルとマレイミド類とを共重合させるこ
とが困難となり、しかもそれによって生成した重合体組
成物は耐熱性の劣ったものであることが記載されている
。さらに、特開昭６２−２０９１１３号公報には、メタ
クリル酸メチル、Ｎ‐置換マレイミド、アクリル酸アル
キルエステルおよび二官能性モノマーからなる混合物を
重合させることにより、ポリアクリル酸アルキルエステ
ルに基づくガラス転移温度と、メタクリル酸メチルとＮ
‐置換マレイミドとの共重合体に基づくガラス転移温度
とを備えたインターポリマーが生成することが開示され
ている。このインターポリマーのポリアクリル酸エステ
ル成分に相当する重合体部分は、ＧＰＣにより分子量が
測定でき、その値が１５〜５０万でなければならないと
述べられていることから、このポリアクリル酸エステル
成分は溶媒に可溶であって架橋されていない重合体であ
ることが明白である。従って、前記従来技術においては
、架橋アクリルゴム成分及びメタクリル酸エステルとマ
レイミド類との共重合体成分とからなる耐熱性および耐
油性を兼ね備えた熱可塑性エラストマーを何ら認識して
いないし、また、それを示唆するものでもなかった。On the other hand, an alkyl ester of acrylic acid,
Small amounts of monomers that provide crosslinking points during the vulcanization process (e.g.
Copolymers with chloroethyl vinyl ether, ethylidene norbornene, etc.) are known as acrylic rubbers.
These are kneaded with a crosslinking agent and the like using a roll or the like, and then crosslinked for practical use. It is also known from Japanese Patent Publication No. 43-9753 that copolymers obtained by copolymerizing maleimides with methyl methacrylate have better heat resistance than homopolymers of methyl methacrylate. . Furthermore, in order to improve the impact resistance of a copolymer of methyl methacrylate and maleimides, compositions in which acrylic rubber is blended with the copolymer are also known (for example, Japanese Patent Publication No. 43-9753 and Kaisho 62-132
911 publications). However, in these known methods, the content of acrylic rubber is small,
In the soft range, it has not been possible to obtain a product that has both heat resistance and oil resistance. Also, JP-A-62-132911
The publication states that if the content of acrylic rubber exceeds 50%,
It is described that it is difficult to copolymerize methyl methacrylate and maleimides, and the resulting polymer composition has poor heat resistance. Furthermore, JP-A-62-209113 discloses that by polymerizing a mixture consisting of methyl methacrylate, N-substituted maleimide, acrylic acid alkyl ester, and a difunctional monomer, the glass transition temperature based on polyacrylic acid alkyl ester is obtained. and methyl methacrylate and N
- glass transition temperature based on copolymers with substituted maleimides. The molecular weight of the polymer portion corresponding to the polyacrylic ester component of this interpolymer can be measured by GPC, and it is stated that the value must be between 150,000 and 500,000. It is clear that the polymer is soluble in the solvent and is not crosslinked. Therefore, in the prior art, there is no recognition of a thermoplastic elastomer having both heat resistance and oil resistance, which is composed of a crosslinked acrylic rubber component and a copolymer component of a methacrylic acid ester and a maleimide. It wasn't even suggested.
【０００４】一方、本発明者らは、架橋アクリルゴム成
分及びメタクリル酸エステルとマレイミド類との共重合
体成分とからなる熱可塑性エラストマー（特願平２−４
２７７４号明細書）、並びに、架橋アクリルゴム粒子製
造工程と該粒子の存在下にメタクリル酸エステルとマレ
イミド類との共重合体を製造することを骨子とする該熱
可塑性エラストマーの製造法（特願平２−４２７７４号
、同２−４２７７５号、同２−１０２１３８号各明細書
）について提案して来た。On the other hand, the present inventors have developed a thermoplastic elastomer comprising a crosslinked acrylic rubber component and a copolymer component of methacrylic acid ester and maleimides (Japanese Patent Application No. 2-4)
No. 2774), as well as a method for producing the thermoplastic elastomer (patent application We have proposed the specifications of Hei 2-42774, Hei 2-42775, and Hei 2-102138.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
の提案においては、目的とする耐熱性と耐油性を兼ね備
えた熱可塑性エラストマーを製造することはできるもの
の、耐寒性に乏しく、より一層の改良が必要であった。
かかる状況から、油脂類と接触するおそれがある所に使
用されてきた加硫ゴム製品の代替品として、高い温度領
域では勿論のこと、比較的低い温度領域においても耐熱
性と耐油性を保ちながら優れた耐寒性を兼ね備えており
、かつ成形性の良好な新しい熱可塑性エラストマー及び
その製造方法を提供されることが望まれていた。[Problem to be solved by the invention] However, although these proposals can produce thermoplastic elastomers that have both the desired heat resistance and oil resistance, they have poor cold resistance and require further improvement. Met. Under these circumstances, as a substitute for vulcanized rubber products that have been used in places where there is a risk of contact with oils and fats, we have developed a new product that maintains heat resistance and oil resistance not only in high temperature ranges but also in relatively low temperature ranges. It has been desired to provide a new thermoplastic elastomer that has excellent cold resistance and good moldability, and a method for producing the same.
【０００６】[0006]
【課題を解決するための手段】〔発明の概要〕本発明者
らは上記課題に鑑みて鋭意研究を重ねた結果、アクリル
ゴムが有する高い耐熱老化温度と良好な耐油性、並びに
長鎖アルキル基またはアルコキシアルキル基を有するア
クリル酸エステルの良好な耐寒特性を生かし、かつメタ
クリル酸エステルとマレイミド類との共重合体が有する
高い耐熱老化温度および優れた耐油性を組み合せるべく
、特定のモノマー成分を組み合せ、特定の重合の態様を
とってその重合体の生成割合を特定な量比に調節するこ
とによって前記本発明の課題を解決することができる熱
可塑性エラストマーが得られるとの知見を得て本発明を
完成するに至った。[Means for Solving the Problems] [Summary of the Invention] In view of the above problems, the present inventors have conducted extensive research and have found that acrylic rubber has a high heat aging temperature and good oil resistance, as well as long-chain alkyl groups. Alternatively, in order to take advantage of the good cold resistance properties of acrylic esters having alkoxyalkyl groups, and to combine the high heat aging temperature and excellent oil resistance of copolymers of methacrylic esters and maleimides, specific monomer components may be added. The present invention has been made based on the knowledge that a thermoplastic elastomer that can solve the problems of the present invention can be obtained by combining a specific polymerization mode and adjusting the production ratio of the polymer to a specific quantitative ratio. The invention was completed.
【０００７】すなわち、本発明の第１番目の発明である
熱可塑性エラストマーは、下記成分（ａ）５５〜９５重
量部と成分（ｂ）４５〜５重量部（成分（ａ）と成分（
ｂ）の和は１００重量部）からなるものである。
成分（ａ）
一般式ＣＨ２＝ＣＨＣＯＯＲ１（式中のＲ１は炭素数１
〜１２の非置換または置換のアルキル基を表わす。）で
表わされるアクリル酸アルキルエステルモノマー成分（
Ｉ）５〜９５重量％と、一般式ＣＨ２＝ＣＨＣＯＯ（Ｃ
Ｈ２）ｎＯＲ２（式中のｎは１〜１０の整数、Ｒ２は炭
素数１〜１２の非置換または置換のアルキル基を表わす
。）で表わされるアクリル酸グリコールエステルモノマ
ー成分（ＩＩ）９５〜５重量％とからなる共重合体であ
って、ガラス転移温度が−２０℃以下の架橋アクリルゴ
ムからなるゴム成分。
成分（ｂ）
一般式ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＲ３（式中のＲ３は
炭素数１〜１２の非置換または置換のアルキル基もしく
は脂環式炭化水素残基を表わす。）で表わされるメタク
リル酸エステルモノマー成分（ＩＩＩ）５〜９５重量％
と、一般式That is, the thermoplastic elastomer which is the first invention of the present invention consists of the following components (a) 55 to 95 parts by weight and component (b) 45 to 5 parts by weight (component (a) and component (
The sum of b) is 100 parts by weight). Component (a) General formula CH2=CHCOOR1 (R1 in the formula has 1 carbon number
~12 unsubstituted or substituted alkyl groups. ) acrylic acid alkyl ester monomer component (
I) 5-95% by weight and the general formula CH2=CHCOO(C
H2) Acrylic acid glycol ester monomer component (II) represented by nOR2 (in the formula, n is an integer of 1 to 10, and R2 represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms) 95 to 5 weight %, a rubber component made of crosslinked acrylic rubber and having a glass transition temperature of -20°C or less. Component (b) Methacrylic acid ester represented by the general formula CH2=C(CH3)COOR3 (R3 in the formula represents an unsubstituted or substituted alkyl group or alicyclic hydrocarbon residue having 1 to 12 carbon atoms) Monomer component (III) 5-95% by weight
and the general formula
【化３】
（式中のＲ４は水素原子、炭素数１〜１２の非置換また
は置換のアルキル基、脂環式炭化水素残基、あるいは、
非置換または置換のフェニル基を表わす。）で表わされ
るマレイミド類モノマー成分（ＩＶ）９５〜５重量％と
から成る共重合体であって、ガラス転移温度が１１０℃
以上の樹脂成分。また、本発明の第２番目の発明である
熱可塑性エラストマーの製造方法は、エチレン性不飽和
結合を分子中に２個以上有する多官能性モノマーの共存
下に、一般式ＣＨ２＝ＣＨＣＯＯＲ１（式中のＲ１は炭
素数１〜１２の非置換または置換のアルキル基を表わす
）で表わされるアクリル酸アルキルエステルモノマー成
分（Ｉ）５〜９５重量％と、一般式ＣＨ２＝ＣＨＣＯＯ
（ＣＨ２）ｎＯＲ２（式中のｎは１〜１０の整数、Ｒ２
は炭素数１〜１２の非置換または置換のアルキル基を表
わす）で表わされるアクリル酸グリコールエステルモノ
マー成分（ＩＩ）９５〜５重量％とを共重合させて得ら
れたガラス転移温度が−２０℃以下の架橋アクリルゴム
からなるゴム成分（成分（ａ））を最終重合体組成物１
００重量部に対して５５〜９５重量部の割合で生成させ
た後、これに一般式ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＲ３（
式中のＲ３は炭素数１〜１２の非置換または置換アルキ
ル基もしくは脂環式炭化水素残基を表わす）で表わされ
るメタクリル酸エステルモノマー成分（ＩＩＩ）５〜９
５％と一般式[Formula 3] (R4 in the formula is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon residue, or
Represents an unsubstituted or substituted phenyl group. ) and 95 to 5% by weight of a maleimide monomer component (IV) having a glass transition temperature of 110°C.
The above resin components. In addition, the method for producing a thermoplastic elastomer, which is the second invention of the present invention, uses a polyfunctional monomer having the general formula CH2=CHCOOR1 (in the formula (R1 represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms) 5 to 95% by weight of the acrylic acid alkyl ester monomer component (I) represented by the general formula CH2=CHCOO
(CH2)nOR2 (n in the formula is an integer of 1 to 10, R2
represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms) and a glass transition temperature of -20°C. A rubber component (component (a)) consisting of the following crosslinked acrylic rubber was added to final polymer composition 1.
00 parts by weight, and then the general formula CH2=C(CH3)COOR3(
(R3 in the formula represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms or an alicyclic hydrocarbon residue) methacrylic acid ester monomer component (III) 5 to 9
5% and general formula
【化４】
（式中のＲ４は水素原子、炭素数１〜１２の非置換また
は置換アルキル基、脂環式炭化水素残基あるいは非置換
または置換のフェニル基を表わす）で表わされるマレイ
ミド類モノマー成分（ＩＶ）９５〜５重量％を加えて更
に共重合させて、ガラス転移温度が１１０℃以上のメタ
クリル酸エステルモノマー成分（ＩＩＩ）とマレイミド
類モノマー成分（ＩＶ）との共重合体の樹脂成分（成分
（ｂ））を最終重合体組成物１００重量部に対して４５
〜５重量部の割合で生成させることを特徴とするもので
ある。embedded image (R4 in the formula represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon residue, or an unsubstituted or substituted phenyl group) A resin component of a copolymer of a methacrylic acid ester monomer component (III) and a maleimide monomer component (IV) having a glass transition temperature of 110° C. or higher by adding 95 to 5% by weight of component (IV) and further copolymerizing it. (component (b)) at 45 parts by weight per 100 parts by weight of the final polymer composition.
It is characterized by being produced in a proportion of ~5 parts by weight.
【０００８】〔発明の具体的説明〕
〔Ｉ〕熱可塑性エラストマー
（１） 構成成分
本発明の熱可塑性エラストマーは、下記に示す成分（ａ
）の架橋アクリルゴムからなるゴム成分と成分（ｂ）の
樹脂成分とから基本的に構成されたものである。
（ａ） 成分（ａ）
本発明の熱可塑性エラストマーを構成する成分（ａ）と
しては、ガラス転移温度が−２０℃以下、好ましくは−
２５℃以下であり、メチルエチルケトンの沸点下で３時
間攪拌した後、分離、乾燥して測定したゲル分率が一般
に７０％以上、好ましくは８０％以上、特に好ましくは
９０％以上である架橋アクリルゴムよりなるゴム成分で
ある。[Specific Description of the Invention] [I] Thermoplastic Elastomer (1) Constituent Components The thermoplastic elastomer of the present invention contains the following components (a).
It basically consists of a rubber component made of crosslinked acrylic rubber () and a resin component (b). (a) Component (a) Component (a) constituting the thermoplastic elastomer of the present invention has a glass transition temperature of -20°C or lower, preferably -
A crosslinked acrylic rubber having a gel fraction of generally 70% or more, preferably 80% or more, particularly preferably 90% or more, at a temperature of 25°C or less, after stirring for 3 hours at the boiling point of methyl ethyl ketone, followed by separation and drying. It is a rubber component consisting of
【０００９】アクリル酸アルキルエステルモノマー成分
（Ｉ）
このような成分（ａ）を構成する一方のモノマー成分（
Ｉ）は、一般式ＣＨ２＝ＣＨＣＯＯＲ１で表わされるア
クリル酸アルキルエステルであり、該式中のＲ１は炭素
数が１〜１２、好ましくは２〜１０、特に好ましくは２
〜８の非置換または置換アルキル基である。これらは単
独でもよく、２種以上併用してもよい。このようなモノ
マー成分（Ｉ）の具体例としては、アクリル酸メチル、
アクリル酸エチル、アクリル酸ｎ‐プロピル、アクリル
酸ｉ‐プロピル、アクリル酸ｎ‐ブチル、アクリル酸ｉ
‐ブチル、アクリル酸ｔ‐ブチル、アクリル酸ｎ‐アミ
ル、アクリル酸ｎ‐ヘキシル、アクリル酸２‐エチルヘ
キシル、アクリル酸ｎ‐オクチル、アクリル酸ｎ‐ドデ
シル、アクリル酸２‐ヒドロキシエチル、アクリル酸２
‐ヒドロキシプロピル、アクリル酸２‐クロロエチル、
アクリル酸２‐ブロモエチル、アクリル酸２‐シアノエ
チル、アクリル酸グリシジル等を挙げることができ、こ
れらの中で好ましいものとしては、アクリル酸エチル、
アクリル酸ｎ‐プロピル、アクリル酸ｉ‐プロピル、ア
クリル酸ｎ‐ブチル、アクリル酸ｉ‐ブチル、アクリル
酸ｎ‐アミル、アクリル酸ｎ‐ヘキシル、アクリル酸２
‐エチルヘキシル、アクリル酸ｎ‐オクチル、アクリル
酸２‐ヒドロキシエチル、アクリル酸２‐ヒドロキシプ
ロピル、アクリル酸２‐クロロエチルであり、特に好ま
しいのはアクリル酸エチル、アクリル酸ｎ‐プロピル、
アクリル酸ｎ‐ブチル、アクリル酸ｎ‐アミル、アクリ
ル酸ｎ‐オクチル、アクリル酸２‐ヒドロキシエチルで
ある。Acrylic acid alkyl ester monomer component (I) One of the monomer components constituting such component (a) (
I) is an acrylic acid alkyl ester represented by the general formula CH2=CHCOOR1, in which R1 has 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, particularly preferably 2
~8 unsubstituted or substituted alkyl groups. These may be used alone or in combination of two or more. Specific examples of such monomer component (I) include methyl acrylate,
Ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-acrylate
-Butyl, t-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-dodecyl acrylate, 2-hydroxyethyl acrylate, 2-acrylate
-Hydroxypropyl, 2-chloroethyl acrylate,
Examples include 2-bromoethyl acrylate, 2-cyanoethyl acrylate, and glycidyl acrylate. Among these, preferred are ethyl acrylate,
n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, acrylic acid 2
-ethylhexyl, n-octyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-chloroethyl acrylate, and particularly preferred are ethyl acrylate, n-propyl acrylate,
These are n-butyl acrylate, n-amyl acrylate, n-octyl acrylate, and 2-hydroxyethyl acrylate.
【００１０】アクリル酸グリコールエステルモノマー成
分（ＩＩ）
成分（ａ）を構成するもう一つのモノマー成分（ＩＩ）
は一般式ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）ｎＯＲ２で表わ
されるアクリル酸グリコールエステルである。ここでｎ
は１〜１０の整数であり、好ましくは２〜８、特に好ま
しくは２〜４であり、Ｒ２は炭素数１〜１２、好ましく
は１〜５、特に好ましくは１〜３の非置換または置換ア
ルキル基である。これらは単独でもよく、２種以上併用
してもよい。このようなモノマー成分（ＩＩ）の好まし
い具体例としては、アクリル酸２‐メトキシエチル、ア
クリル酸３‐メトキシプロピル、アクリル酸４‐メトキ
シブチル、アクリル酸２‐エトキシエチル、アクリル酸
３‐エトキシプロピルなどであり、特に好ましいのはア
クリル酸２‐メトキシエチル、アクリル酸３‐メトキシ
プロピル、アクリル酸２‐エトキシエチルである。Acrylic acid glycol ester monomer component (II) Another monomer component (II) constituting component (a)
is an acrylic acid glycol ester represented by the general formula CH2=CHCOO(CH2)nOR2. where n
is an integer of 1 to 10, preferably 2 to 8, particularly preferably 2 to 4, and R2 is unsubstituted or substituted alkyl having 1 to 12 carbon atoms, preferably 1 to 5 carbon atoms, particularly preferably 1 to 3 carbon atoms. It is the basis. These may be used alone or in combination of two or more. Preferred specific examples of such monomer component (II) include 2-methoxyethyl acrylate, 3-methoxypropyl acrylate, 4-methoxybutyl acrylate, 2-ethoxyethyl acrylate, and 3-ethoxypropyl acrylate. Especially preferred are 2-methoxyethyl acrylate, 3-methoxypropyl acrylate, and 2-ethoxyethyl acrylate.
【００１１】多官能性モノマー
上記成分（ａ）の共重合体を架橋アクリルゴムとするた
めに多官能性モノマーが使用される。ここで使用する多
官能性モノマーとしては、分子中にアクリル酸エステル
と共重合し得るエチレン性不飽和結合を２個以上有する
化合物である。このような多官能性モノマーの具体例と
しては、ジビニルベンゼン、ジビニルトルエン、ジオー
ル類のジアクリル酸あるいはジメタクリル酸エステル（
該ジオールの例としては、エチレングリコール、ジエチ
レングリコール、テトラエチレングリコール、１，４‐
ブタンジオール、１，６‐ヘキサンジオール、プロピレ
ングリコール、１，４‐シクロヘキサンジオール、１，
４‐ジメチロールシクロヘキサンなどを挙げることがで
きる。）、アクリル酸アリル、メタクリル酸アリル、ジ
カルボン酸のジアリルエステル（該ジカルボン酸の例と
しては、マレイン酸、フマル酸、フタル酸、アジピン酸
、コハク酸などを挙げることができる。）等の二官能性
モノマー、あるいは、トリビニルトルエン、トリオール
のトリアクリル酸あるいはトリメタクリル酸エステル（
該トリオールの例としては、グリセリン、トリメチロー
ルプロパンなどを挙げることができる。）、ペンタエリ
スリトールトリアクリレート、トリアリルシアヌレート
、トリアリルイソシアヌレート、トリアリルトリメリテ
ートなどのトリカルボン酸のトリアリルエステル等の三
官能性モノマー、あるいはテトラメチロールメタンなど
テトラオールのテトラアクリル酸またはテトラメタクリ
ル酸エステル、ピロメリット酸テトラアリル等のテトラ
カルボン酸のテトラアリルエステル等の四官能性モノマ
ー、あるいはジペンタエリスリトールヘキサアクリレー
ト等の六官能性モノマー等を挙げることができる。これ
ら多官能性モノマーの中では三官能性モノマーおよび四
官能性モノマーが好ましく、特に三官能性モノマーが好
ましい。これらの多官能性モノマーは単独でも２種以上
併用してもよい。Polyfunctional Monomer A polyfunctional monomer is used to form the copolymer of component (a) into a crosslinked acrylic rubber. The polyfunctional monomer used here is a compound having two or more ethylenically unsaturated bonds in its molecule that can be copolymerized with an acrylic ester. Specific examples of such polyfunctional monomers include divinylbenzene, divinyltoluene, and diacrylic or dimethacrylic esters of diols (
Examples of such diols include ethylene glycol, diethylene glycol, tetraethylene glycol, 1,4-
Butanediol, 1,6-hexanediol, propylene glycol, 1,4-cyclohexanediol, 1,
Examples include 4-dimethylolcyclohexane. ), allyl acrylate, allyl methacrylate, diallyl ester of dicarboxylic acid (examples of the dicarboxylic acid include maleic acid, fumaric acid, phthalic acid, adipic acid, succinic acid, etc.). triacrylic acid or trimethacrylic acid ester of trivinyltoluene, triol (
Examples of the triol include glycerin, trimethylolpropane, and the like. ), trifunctional monomers such as triallyl esters of tricarboxylic acids such as pentaerythritol triacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, or tetraacrylic acid or tetraols such as tetramethylolmethane. Examples include tetrafunctional monomers such as methacrylic acid esters and tetraallyl esters of tetracarboxylic acids such as tetraallyl pyromellitate, and hexafunctional monomers such as dipentaerythritol hexaacrylate. Among these polyfunctional monomers, trifunctional monomers and tetrafunctional monomers are preferred, and trifunctional monomers are particularly preferred. These polyfunctional monomers may be used alone or in combination of two or more.
【００１２】任意モノマー
上記必須成分のアクリル酸アルキルエステルモノマー成
分（Ｉ）とアクリル酸グリコールエステルモノマー成分
（ＩＩ）と多官能性モノマー成分以外に、任意成分とし
て、上記モノマー成分（Ｉ）またはモノマー成分（ＩＩ
）と共重合可能な単量体例えば、２‐クロロエチルビニ
ルエーテル、アリルグリシジルエーテル、エチリデンノ
ルボルネン、アクリル酸、メタクリル酸、マレイン酸、
グリシジルメタクリレート等を本発明の効果を著しく損
なわない範囲、好適には１０重量％以下の量で併用する
ことができる。Optional monomers In addition to the above-mentioned essential acrylic acid alkyl ester monomer component (I), acrylic acid glycol ester monomer component (II) and polyfunctional monomer component, the above-mentioned monomer component (I) or monomer component can be used as an optional component. (II
), such as 2-chloroethyl vinyl ether, allyl glycidyl ether, ethylidene norbornene, acrylic acid, methacrylic acid, maleic acid,
Glycidyl methacrylate and the like may be used together in an amount that does not significantly impair the effects of the present invention, preferably in an amount of 10% by weight or less.
【００１３】量 比
該成分（ａ）中のアクリル酸アルキルエステルモノマー
成分（Ｉ）は５〜９５重量％、好ましくは５〜８０重量
％で、アクリル酸グリコールエステルモノマー成分（Ｉ
Ｉ）は９５〜５重量％、好ましくは９５〜２０重量％で
あり、上記多官能性モノマーは、生成するアクリルゴム
のゲル分率が７０％以上、好ましくは８０％以上、特に
好ましくは９０％以上となるようにアクリル酸エステル
であるモノマー（Ｉ）とモノマー（ＩＩ）の和１００重
量部に対して通常０．０１〜１０重量部、好ましくは０
．１〜７重量部、特に好ましくは０．２〜５重量部添加
する。この量は多官能性モノマーの種類によって最適量
が異なり、通常重合し得るエチレン性不飽和結合の数が
多くなるほど少量でよい。多官能性モノマーの量が０．
０１重量部未満ではゲル分率を７０％以上にするのが困
難であり、また１０重量部を越えると生成重合体のゴム
弾性が乏しくなったり、熱可塑性エラストマーの成形性
が著しく低下するなどのため好ましくない。Amount Ratio The acrylic acid alkyl ester monomer component (I) in the component (a) is 5 to 95% by weight, preferably 5 to 80% by weight, and the acrylic acid glycol ester monomer component (I) is 5 to 95% by weight, preferably 5 to 80% by weight.
I) is 95 to 5% by weight, preferably 95 to 20% by weight, and the polyfunctional monomer is used so that the gel fraction of the resulting acrylic rubber is 70% or more, preferably 80% or more, particularly preferably 90%. To achieve the above, it is usually 0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight, preferably 0.
．． It is added in an amount of 1 to 7 parts by weight, particularly preferably 0.2 to 5 parts by weight. The optimum amount differs depending on the type of polyfunctional monomer, and usually the smaller the amount is, the greater the number of ethylenically unsaturated bonds that can be polymerized. The amount of polyfunctional monomer is 0.
If the amount is less than 1 part by weight, it is difficult to achieve a gel fraction of 70% or more, and if it exceeds 10 parts by weight, the resulting polymer may have poor rubber elasticity or the moldability of the thermoplastic elastomer may be significantly reduced. Therefore, it is undesirable.
【００１４】（ｂ） 成分（ｂ）
本発明の熱可塑性エラストマーを構成するもう一つの成
分（ｂ）は、ガラス転移温度が１１０℃以上、好ましく
は１３０℃以上、特に好ましくは１４０℃以上のメタク
リル酸エステルとマレイミド類との共重合体の樹脂成分
である。
メタクリル酸エステルモノマー成分（ＩＩＩ）成分（ｂ
）を構成するモノマー成分（ＩＩＩ）は一般式ＣＨ２＝
Ｃ（ＣＨ３）ＣＯＯＲ３で表わされるメタクリル酸エス
テルである。ここでＲ３は炭素数１〜１２、好ましくは
１〜１０、特に好ましくは１〜６の非置換または置換ア
ルキル基もしくは脂環式炭化水素残基である。これらは
単独でもよく、２種以上併用してもよい。このようなメ
タクリル酸エステルの具体例としては、メタクリル酸メ
チル、メタクリル酸エチル、メタクリル酸ブチル、メタ
クリル酸イソボルニル、メタクリル酸シクロヘキシル、
メタクリル酸ボルニル、メタクリル酸アダマンチル、メ
タクリル酸メンチルなどを挙げることができる。
これらの中ではメタクリル酸メチル、メタクリル酸イソ
ボルニルが好ましく、特にメタクリル酸メチルが好まし
い。(b) Component (b) Another component (b) constituting the thermoplastic elastomer of the present invention is methacrylate having a glass transition temperature of 110°C or higher, preferably 130°C or higher, particularly preferably 140°C or higher. It is a resin component of a copolymer of acid ester and maleimide. Methacrylic acid ester monomer component (III) component (b)
The monomer component (III) constituting ) has the general formula CH2=
It is a methacrylic acid ester represented by C(CH3)COOR3. Here, R3 is an unsubstituted or substituted alkyl group or an alicyclic hydrocarbon residue having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. These may be used alone or in combination of two or more. Specific examples of such methacrylate esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate,
Examples include bornyl methacrylate, adamantyl methacrylate, and menthyl methacrylate. Among these, methyl methacrylate and isobornyl methacrylate are preferred, and methyl methacrylate is particularly preferred.
【００１５】マレイミド類モノマー成分（ＩＶ）成分（
ｂ）を構成するもう一つのモノマー成分（ＩＶ）は、一
般式Maleimide monomer component (IV) component (
Another monomer component (IV) constituting b) has the general formula
【化５】
で表わされるマレイミド類である。ここでＲ４は水素原
子または炭素数１〜１２、好ましくは１〜１０、特に好
ましくは１〜８の非置換または置換アルキル基、脂環式
炭化水素残基もしくは非置換または置換フェニル基を表
わす。このようなマレイミド類としては、マレイミドお
よびそのＮ‐置換体であり、具体的には、マレイミド、
Ｎ‐メチルマレイミド、Ｎ‐フェニルマレイミド、Ｎ‐
（２‐メチルフェニル）マレイミド、Ｎ‐（２‐クロロ
フェニル）マレイミド、Ｎ‐（２，６‐ジメチルフェニ
ル）マレイミド、Ｎ‐（２，６‐ジエチルフェニル）マ
レイミド、Ｎ‐（４‐ヒドロキシフェニル）マレイミド
、Ｎ‐（４‐カルボキシフェニル）マレイミド、Ｎ‐シ
クロヘキシルマレイミド等を挙げることができる。これ
らマレイミド類の中ではＮ‐フェニルマレイミドおよび
Ｎ‐シクロヘキシルマレイミドが好ましく、特にＮ‐シ
クロヘキシルマレイミドが好ましい。これらは単独でも
２種以上併用してもよい。It is a maleimide represented by the following formula. Here, R4 represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms, an alicyclic hydrocarbon residue, or an unsubstituted or substituted phenyl group. Such maleimides include maleimide and its N-substituted derivatives, specifically maleimide,
N-methylmaleimide, N-phenylmaleimide, N-
(2-methylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-(4-hydroxyphenyl)maleimide , N-(4-carboxyphenyl)maleimide, N-cyclohexylmaleimide, and the like. Among these maleimides, N-phenylmaleimide and N-cyclohexylmaleimide are preferred, and N-cyclohexylmaleimide is particularly preferred. These may be used alone or in combination of two or more.
【００１６】任意モノマー
上記必須成分のメタクリル酸エステルモノマー成分（Ｉ
ＩＩ）とマレイミド類モノマー成分（ＩＶ）以外に、任
意成分として上記モノマー成分（ＩＩＩ）またはモノマ
ー成分（ＩＶ）と共重合可能な他の単量体、例えば、ス
チレン、メタクリル酸、アクリロニトリル等を本発明の
効果が著しく損なわれない範囲、好適には２０重量％以
内の量で共重合しても良い。Optional monomer The above essential methacrylic acid ester monomer component (I
In addition to II) and the maleimide monomer component (IV), other monomers copolymerizable with the monomer component (III) or monomer component (IV), such as styrene, methacrylic acid, acrylonitrile, etc., may be optionally added. Copolymerization may be carried out within a range that does not significantly impair the effects of the invention, preferably within 20% by weight.
【００１７】量 比
さらに、成分（ｂ）中のメタクリル酸エステルモノマー
成分（ＩＩＩ）は５〜９５重量％、好ましくは２０〜８
０重量％であり、マレイミド類モノマー成分（ＩＶ）９
５〜５重量％、好ましくは８０〜２０重量％である。Further, the amount of methacrylic acid ester monomer component (III) in component (b) is 5 to 95% by weight, preferably 20 to 8% by weight.
0% by weight, maleimides monomer component (IV) 9
5 to 5% by weight, preferably 80 to 20% by weight.
【００１８】（ｃ） 付加的成分（ｃ）前記本発明の熱
可塑性エラストマーを実用に供するに際しては、本発明
の効果を著しく損わない範囲内で以下に示すような付加
的成分を加えることができる。このような付加的成分と
しては、例えば、ポリアミド樹脂、ポリエステル樹脂、
ポリフェニレンエーテル樹脂、ポリオキシメチレン樹脂
、ポリカーボネート樹脂、ポリフェニレンスルフィド樹
脂、アクリル樹脂、ＡＢＳ樹脂、スチレン・マレイミド
樹脂等の極性の大きい樹脂、無機フィラー、具体的には
シリカ、アルミナ、チタニア、酸化亜鉛、酸化マグネシ
ウムなどの金属酸化物、炭酸カルシウム、カオリン、マ
イカ、タルク、石綿、珪酸カルシウム、珪酸アルミニウ
ム等の珪酸塩、チタン酸カリウム、炭化ホウ素などの各
種ウイスカー、カーボンブラック等の各種顔料ないし着
色剤、酸化ないしは劣化防止剤等を挙げることができる
。(c) Additional components (c) When putting the thermoplastic elastomer of the present invention into practical use, the following additional components may be added to the extent that the effects of the present invention are not significantly impaired. can. Such additional components include, for example, polyamide resins, polyester resins,
Highly polar resins such as polyphenylene ether resin, polyoxymethylene resin, polycarbonate resin, polyphenylene sulfide resin, acrylic resin, ABS resin, styrene/maleimide resin, inorganic fillers, specifically silica, alumina, titania, zinc oxide, oxide Metal oxides such as magnesium, calcium carbonate, kaolin, mica, talc, asbestos, silicates such as calcium silicate, aluminum silicate, various whiskers such as potassium titanate, boron carbide, various pigments or colorants such as carbon black, oxidation Alternatively, deterioration inhibitors and the like can be mentioned.
【００１９】（２） 量 比
本発明の熱可塑性エラストマーは、前記成分（ａ）およ
び成分（ｂ）から基本的になるもので、必要により付加
的成分（ｃ）などが加えられたものであり、これら構成
成分の配合量が本発明においては重要である。上記成分
（ａ）と成分（ｂ）の和が１００重量部とした際の両者
の配合量は成分（ａ）が５５〜９５重量部、好ましくは
５５〜９０重量部、特に好ましくは６０〜８５重量部で
あり、成分（ｂ）が４５〜５重量部、好ましくは４５〜
１０重量部、特に好ましくは４０〜１５重量部である。
また、上記必須構成成分以外に任意成分として配合され
る付加的成分（ｃ）は、本発明の効果を著しく損わない
範囲以下の量、例えば５０重量％未満、好ましくは３０
重量％以下、特に好ましくは２０重量％以下の量で配合
することができる。(2) Amount Ratio The thermoplastic elastomer of the present invention basically consists of the above-mentioned components (a) and (b), with additional components (c) etc. added as necessary. The blending amounts of these components are important in the present invention. When the sum of component (a) and component (b) is 100 parts by weight, the blending amount of both components is 55 to 95 parts by weight, preferably 55 to 90 parts by weight, particularly preferably 60 to 85 parts by weight. parts by weight, and component (b) is 45 to 5 parts by weight, preferably 45 to 5 parts by weight.
It is 10 parts by weight, particularly preferably 40 to 15 parts by weight. Further, the amount of the additional component (c) added as an optional component in addition to the above-mentioned essential components is within the range that does not significantly impair the effects of the present invention, for example, less than 50% by weight, preferably 30% by weight or less.
It can be blended in an amount of up to 20% by weight, particularly preferably up to 20% by weight.
【００２０】（３） 物 性
このような熱可塑性エラストマーは、架橋アクリルゴム
（成分（ａ））がゴム的性質を備えていることから熱可
塑性エラストマー全体からみるとソフトセグメント部分
を形成している。このような架橋アクリルゴム（成分（
ａ））はガラス転移温度が−２０℃以下、好ましくは−
２５℃以下、のものである。また、このような架橋アク
リルゴム（成分（ａ））はゲル分率が７０％以上、好ま
しくは８０％以上、特に好ましくは９０％〜１００％程
度に架橋されている。さらに、該熱可塑性エラストマー
はＪＩＳ Ｎｏ． ３油に１２５℃、７２時間浸漬し
た時の体積膨脹率（ΔＶ）が１５０％以下、更に好まし
くは１００％以下、特に好ましくは６０％以下であると
の性質を備えたものが好ましい。(3) Physical properties In such a thermoplastic elastomer, since the crosslinked acrylic rubber (component (a)) has rubber-like properties, it forms a soft segment portion when viewed from the thermoplastic elastomer as a whole. . Such cross-linked acrylic rubber (component (
a)) has a glass transition temperature of -20°C or lower, preferably -
The temperature is 25°C or lower. Further, such crosslinked acrylic rubber (component (a)) is crosslinked to a gel fraction of 70% or more, preferably 80% or more, particularly preferably about 90% to 100%. Furthermore, the thermoplastic elastomer conforms to JIS No. Preferably, the material has a volumetric expansion rate (ΔV) of 150% or less, more preferably 100% or less, particularly preferably 60% or less when immersed in 3 oil at 125° C. for 72 hours.
【００２１】〔ＩＩ〕熱可塑性エラストマーの製造（１
） 製造方法
本発明の熱可塑性エラストマーを製造するための方法と
しては本発明の目的が達成される上記組成の熱可塑性エ
ラストマーが得られるならばどのような方法で製造した
ものであっても良いが、好適には次に示すような■〜■
の方法を挙げることができる。■ 多官能性モノマー
の存在下に前記アクリル酸アルキルエステルモノマー成
分（Ｉ）とアクリル酸グリコールエステルモノマー成分
（ＩＩ）とを共重合させて得られた未架橋アクリルゴム
を架橋させた後に粉砕し、得られた成分（ａ）を、成分
（ｂ）であるメタクリル酸エステル・マレイミド類共重
合体と溶融混練する方法、■ アクリル酸アルキルエ
ステルモノマー成分（Ｉ）とアクリル酸グリコールエス
テルモノマー成分（ＩＩ）とを共重合させて得られた未
架橋アクリルゴムとメタクリル酸エステル・マレイミド
類共重合体（成分ｂ）とを、前記未架橋アクリルゴムが
選択的に架橋する架橋剤と共に溶融混練する方法、■
多官能性モノマーの共存下に、アクリル酸アルキルエ
ステルモノマー成分（Ｉ）とアクリル酸グリコールエス
テルモノマー成分（ＩＩ）とを共重合させて、該アクリ
ル酸アルキルエステルモノマー成分（Ｉ）とアクリル酸
グリコールエステルモノマー成分（ＩＩ）の共重合反応
と同時に多官能性モノマーによる架橋反応を行なった後
、その反応生成物（成分ａ）にメタクリル酸エステルモ
ノマー成分（ＩＩＩ）とマレイミド類モノマー成分（Ｉ
Ｖ）を加えて更に重合させる方法、などを挙げることが
できる。これらの方法の中では、モノマー成分（Ｉ）と
モノマー成分（ＩＩ）との共重合と同時に架橋させる前
記■の方法が生成する架橋アクリルゴム（成分ａ）の粒
子径を小さくできるので特に好適である。[II] Production of thermoplastic elastomer (1)
) Production method The thermoplastic elastomer of the present invention may be produced by any method as long as it can obtain a thermoplastic elastomer having the above composition that achieves the object of the present invention. , preferably the following ■～■
The following methods can be mentioned. (2) Crosslinking the uncrosslinked acrylic rubber obtained by copolymerizing the acrylic acid alkyl ester monomer component (I) and the acrylic acid glycol ester monomer component (II) in the presence of a polyfunctional monomer, and then pulverizing it; A method of melt-kneading the obtained component (a) with the methacrylic acid ester/maleimide copolymer which is component (b), ■ acrylic acid alkyl ester monomer component (I) and acrylic acid glycol ester monomer component (II) A method of melt-kneading an uncrosslinked acrylic rubber obtained by copolymerizing and a methacrylic acid ester/maleimide copolymer (component b) with a crosslinking agent that selectively crosslinks the uncrosslinked acrylic rubber,
In the presence of a polyfunctional monomer, acrylic acid alkyl ester monomer component (I) and acrylic acid glycol ester monomer component (II) are copolymerized to form the acrylic acid alkyl ester monomer component (I) and acrylic acid glycol ester. After carrying out a crosslinking reaction using a polyfunctional monomer simultaneously with the copolymerization reaction of monomer component (II), the reaction product (component a) is mixed with methacrylic acid ester monomer component (III) and maleimide monomer component (I).
Examples include a method of adding V) and further polymerizing. Among these methods, method (2) above, in which the monomer component (I) and the monomer component (II) are copolymerized and crosslinked simultaneously, is particularly preferred because the particle size of the crosslinked acrylic rubber (component a) produced can be made small. be.
【００２２】（２） 製造手段
これらの方法の具体的な手段の一例として、上記■の方
法について以下に詳述する。この■の方法は、少なくと
も架橋アクリルゴム（成分（ａ））の製造工程（第１工
程）と、該成分（ａ）の共存下でメタクリル酸エステル
とマレイミド類とを共重合させて得られた樹脂（成分（
ｂ））を製造する工程（第２工程）とから基本的に構成
されてなる方法である。(2) Production Means As a specific example of these methods, method (2) above will be described in detail below. This method (2) includes at least the step (first step) of producing a crosslinked acrylic rubber (component (a)) and the copolymerization of a methacrylic acid ester and a maleimide in the coexistence of the component (a). Resin (component)
This method basically consists of the step of manufacturing b)) (second step).
【００２３】（ａ） 第１工程（架橋アクリルゴム（成
分（ａ））の製造）
この第１工程においては、エチレン性不飽和結合を分子
中に２個以上有する多官能性モノマーの共存下にラジカ
ル開始剤を用いて、前記アクリル酸アルキルエステルモ
ノマー成分（Ｉ）５〜９５重量％とアクリル酸グリコー
ルエステルモノマー成分（ＩＩ）９５〜５重量％とを共
重合させて架橋アクリルゴム（成分（ａ））を製造する
工程である。この第１工程での重合は、アクリル酸アル
キルエステル、アクリル酸グリコールエステルおよび後
記多官能性モノマーをラジカル開始剤の存在下、水媒体
中での懸濁あるいは乳化重合法を採用することができる
が、生成物の熱可塑エラストマーとしての物性の点で乳
化重合法を採用する方が好ましい。前記重合に用いられ
るラジカル開始剤としては、公知のものが使用でき、具
体的には過硫酸カリウム、過硫酸アンモニウムなどの無
機過酸化物；ｐ‐メンタンハイドロパーオキサイド、キ
ュメンハイドロパーオキサイド、過酸化ベンゾイルなど
の有機過酸化物；アゾビスイソブチロニトリル等のアゾ
化合物；これらの過酸化物、アゾ化合物並びに第二鉄塩
等の酸化性物質とアンモニア、アミン類、ナトリウムホ
ルムアルデヒドスルホキシレート、ナトリウムハイドロ
サルファイト、アスコルビン酸等の還元性物質とを組み
合わせたいわゆるレドックス開始剤等を挙げることがで
きる。また、その使用量はアクリル酸エステル（モノマ
ー成分（Ｉ）とモノマー成分（ＩＩ）の和）１００重量
部に対して一般に０．００１〜５重量部、好ましくは０
．００５〜１重量部の範囲内である。重合は、前記の通
り懸濁或いは乳化重合法によるのが好ましく、その条件
としては、例えば、乳化重合の場合、両アクリル酸エス
テル１００重量部（モノマー成分（Ｉ）とモノマー成分
（ＩＩ）との和）に対して、上記の多官能性モノマーと
ラジカル開始剤及び水５０〜５００重量部、好ましくは
１００〜３００重量部、高級アルキル硫酸ナトリウムな
どの乳化剤を０．１〜１５重量部、好ましくは０．５〜
１０重量部、硫酸ナトリウムなどの乳化安定剤を０〜５
重量部加えて、通常０〜１００℃、好ましくは０〜５０
℃で１〜１０時間程度重合する。アクリル酸エステル、
多官能性モノマーあるいは開始剤は一括してチャージし
てもよく、分割して、あるいは連続的にチャージしても
よい。この工程では前述のようにこれらモノマー成分（
Ｉ）とモノマー成分（ＩＩ）と共重合可能な単量体を存
在させることもできる。(a) First step (manufacture of crosslinked acrylic rubber (component (a))) In this first step, in the coexistence of a polyfunctional monomer having two or more ethylenically unsaturated bonds in the molecule, Using a radical initiator, 5 to 95% by weight of the acrylic acid alkyl ester monomer component (I) and 95 to 5% by weight of the acrylic acid glycol ester monomer component (II) are copolymerized to form a crosslinked acrylic rubber (component (a). )). The polymerization in the first step can be carried out by suspension or emulsion polymerization of an acrylic acid alkyl ester, an acrylic acid glycol ester, and the polyfunctional monomer described below in an aqueous medium in the presence of a radical initiator. From the viewpoint of the physical properties of the product as a thermoplastic elastomer, it is preferable to employ the emulsion polymerization method. As the radical initiator used in the polymerization, known ones can be used, specifically inorganic peroxides such as potassium persulfate and ammonium persulfate; p-menthane hydroperoxide, cumene hydroperoxide, and benzoyl peroxide. organic peroxides such as; azo compounds such as azobisisobutyronitrile; oxidizing substances such as these peroxides, azo compounds, and ferric salts, and ammonia, amines, sodium formaldehyde sulfoxylate, sodium hydro Examples include so-called redox initiators in combination with reducing substances such as sulfite and ascorbic acid. Further, the amount used is generally 0.001 to 5 parts by weight, preferably 0.
．． It is within the range of 0.005 to 1 part by weight. As mentioned above, the polymerization is preferably carried out by suspension or emulsion polymerization, and the conditions include, for example, in the case of emulsion polymerization, 100 parts by weight of both acrylic esters (monomer component (I) and monomer component (II)) 50 to 500 parts by weight, preferably 100 to 300 parts by weight, of the above polyfunctional monomer, radical initiator and water, and 0.1 to 15 parts by weight, preferably 0.1 to 15 parts by weight, of an emulsifier such as sodium higher alkyl sulfate. 0.5～
10 parts by weight, 0 to 5 parts of emulsion stabilizer such as sodium sulfate
In addition to parts by weight, usually 0 to 100°C, preferably 0 to 50°C
Polymerize at ℃ for about 1 to 10 hours. acrylic ester,
The polyfunctional monomer or initiator may be charged all at once, dividedly, or continuously. In this step, as mentioned above, these monomer components (
Monomers copolymerizable with I) and monomer component (II) can also be present.
【００２４】（ｂ） 第２工程（メタクリル酸エステル
とマレイミド類との共重合体樹脂（成分（ｂ））の製造
）第１工程で生成した成分（ａ）の共存下に成分（ｂ）
を生成させて成分（ａ）と成分（ｂ）とからなる本発明
の熱可塑性エラストマーを製造するための工程である。
すなわち、第１工程で生成した架橋アクリルゴム（成分
（ａ））、好ましくは乳化重合で生成した成分（ａ）に
前記モノマー成分（ＩＩＩ）５〜９５重量％とモノマー
成分（ＩＶ）９５〜５重量％（モノマー成分（ＩＩＩ）
とモノマー成分（ＩＶ）との和は１００重量％）を加え
てさらに共重合を行う工程である。また、前記メタクリ
ル酸エステルモノマー成分（ＩＩＩ）とマレイミド類モ
ノマー成分との量比は、生成する共重合体のガラス転移
温度が１１０℃以上、好ましくは１３０℃以上、特に好
ましくは１４０℃以上となるように決められる。すなわ
ちメタクリル酸エステルモノマー成分（ＩＩＩ）を一般
に９５〜５重量％、好ましくは８０〜２０重量％、マレ
イミド類モノマー成分（ＩＶ）を一般に５〜９５重量％
、好ましくは２０〜８０重量％の割合で使用する。該共
重合体中のマレイミド類単量体単位の含有量が増すほど
ガラス転移温度が上昇する。従ってマレイミド類が上記
範囲未満では共重合体のガラス転移温度および耐熱性の
向上効果が少なく、一方、上記範囲を越えると成形性が
著しく悪化してくるので好ましくない。(b) Second step (Production of copolymer resin (component (b)) of methacrylic acid ester and maleimides) Component (b) is added in the coexistence of component (a) produced in the first step.
This is a step for producing the thermoplastic elastomer of the present invention consisting of component (a) and component (b). That is, 5 to 95% by weight of the monomer component (III) and 95 to 5% by weight of the monomer component (IV) are added to the crosslinked acrylic rubber (component (a)) produced in the first step, preferably component (a) produced by emulsion polymerization. Weight % (monomer component (III)
and monomer component (IV) (the sum of which is 100% by weight) is further copolymerized. Furthermore, the quantitative ratio of the methacrylic acid ester monomer component (III) to the maleimide monomer component is such that the glass transition temperature of the resulting copolymer is 110°C or higher, preferably 130°C or higher, particularly preferably 140°C or higher. It can be determined as follows. That is, the methacrylic acid ester monomer component (III) is generally 95 to 5% by weight, preferably 80 to 20% by weight, and the maleimide monomer component (IV) is generally 5 to 95% by weight.
, preferably in a proportion of 20 to 80% by weight. The glass transition temperature increases as the content of maleimide monomer units in the copolymer increases. Therefore, if the maleimide content is less than the above range, the effect of improving the glass transition temperature and heat resistance of the copolymer will be small, while if it exceeds the above range, the moldability will be markedly deteriorated, which is not preferable.
【００２５】該共重合は、前記第１工程の架橋アクリル
ゴムと同様な方法で行うことができ、例えば、ラジカル
開始剤の存在下、トルエン、キシレンなどの有機溶媒中
で行なう溶液重合法、水媒体中での懸濁あるいは乳化重
合法、また媒体を使用せずに共重合を行なう無溶媒バル
ク重合法などを採用することができる。しかし、前記の
第１工程の好ましい態様との関連においては、次のよう
な方法を採ることが好ましい。すなわち、前記の架橋ア
クリルゴム成分（ａ）の重合工程（第１工程）において
、未反応モノマーが通常１０重量％以下、好ましくは５
重量％以下になった時点で、モノマー成分（ＩＩＩ）と
モノマー成分（ＩＶ）および必要によりメルカプタン類
、α‐メチルスチレンダイマー等の分子量調節剤をモノ
マー成分（ＩＩＩ）とモノマー成分（ＩＶ）の和１００
重量部に対して０．００１〜１０重量部、好ましくは０
．０１〜５重量部をそれぞれ加えて更に重合を続ける。
この第２工程においては、該共重合体の量が第１工程で
製造した架橋アクリルゴム５５〜９５重量部に対して４
５〜５重量部、好ましくは架橋アクリルゴム６０〜８５
重量部に対して４０〜１５重量部（両者合わせて１００
重量部）となるように重合する。架橋アクリルゴムが少
なすぎると柔軟性が乏しくなり、一方、多すぎると成形
性が悪くなって好ましくない。ここで生成するメタクリ
ル酸エステル・マレイミド類共重合体樹脂（成分ｂ）は
、メタクリル酸エステルとマレイミド類との共重合体の
他に、この重合方法で生成する架橋アクリルゴムへグラ
フト重合したグラフト共重合体をも包含するものである
。このグラフト共重合体は好適には、熱可塑性エラスト
マー全体中の２０重量％以下である。なお、このような
グラフト共重合体を含むものの方が良好な物性値を示す
ことができる。The copolymerization can be carried out in the same manner as the crosslinked acrylic rubber in the first step, for example, a solution polymerization method carried out in an organic solvent such as toluene or xylene in the presence of a radical initiator; A suspension or emulsion polymerization method in a medium, a solvent-free bulk polymerization method in which copolymerization is performed without using a medium, etc. can be employed. However, in relation to the preferred embodiment of the first step, it is preferable to adopt the following method. That is, in the polymerization step (first step) of the crosslinked acrylic rubber component (a), the amount of unreacted monomer is usually 10% by weight or less, preferably 5% by weight.
When the weight percentage is below, add monomer component (III) and monomer component (IV) and, if necessary, a molecular weight regulator such as mercaptans and α-methylstyrene dimer to the sum of monomer component (III) and monomer component (IV). 100
0.001 to 10 parts by weight, preferably 0
．． Polymerization is further continued by adding 01 to 5 parts by weight, respectively. In this second step, the amount of the copolymer is 4 parts by weight based on 55 to 95 parts by weight of the crosslinked acrylic rubber produced in the first step.
5 to 5 parts by weight, preferably 60 to 85 parts by weight of crosslinked acrylic rubber
40 to 15 parts by weight (total of 100 parts by weight)
(parts by weight). If the amount of crosslinked acrylic rubber is too small, the flexibility will be poor, while if it is too large, the moldability will be poor, which is not preferable. The methacrylic acid ester/maleimide copolymer resin (component b) produced here is a copolymer of methacrylic acid ester and maleimides, as well as a graft copolymer that is graft-polymerized to the crosslinked acrylic rubber produced by this polymerization method. It also includes polymers. The graft copolymer is preferably present at less than 20% by weight of the total thermoplastic elastomer. Note that those containing such a graft copolymer can exhibit better physical property values.
【００２６】この第２工程では、必要に応じて水、乳化
剤、ラジカル開始剤等を追加してもよい。またメタクリ
ル酸エステル、マレイミド類、乳化剤、ラジカル開始剤
、分子量調節剤ならびに水等は一括チャージしてもよい
し、分割あるいは連続してチャージしてもよい。好まし
い方法は、メタクリル酸エステルとマレイミド類および
分子量調節剤からなる混合物と、ラジカル開始剤を個別
に分割あるいは連続してチャージする方法である。この
第２工程の重合温度は通常５０〜１２０℃、好ましくは
６０〜１００℃である。重合時間は通常１〜１２時間、
好ましくは３〜１０時間程度である。[0026] In this second step, water, an emulsifier, a radical initiator, etc. may be added as necessary. Further, methacrylic esters, maleimides, emulsifiers, radical initiators, molecular weight regulators, water, etc. may be charged all at once, or may be charged in portions or continuously. A preferred method is to charge a mixture of a methacrylic acid ester, a maleimide, and a molecular weight regulator, and a radical initiator separately or continuously. The polymerization temperature in this second step is usually 50 to 120°C, preferably 60 to 100°C. Polymerization time is usually 1 to 12 hours,
Preferably it is about 3 to 10 hours.
【００２７】（ｃ） 生成物の回収
生成物の回収方法としてはこの種重合法で通常採用され
る公知の方法を採用することができる。例えば、第２工
程の重合が終了した後、この反応混合物を攪拌下、食塩
、塩化カルシウム、塩化マグネシウム、硫酸マグネシウ
ム、硫酸アルミニウムなどの無機塩類の水溶液に投入し
て生成重合体組成物を主として含有する組成物を凝集さ
せる。これを濾過、洗浄後、乾燥して目的の熱可塑性エ
ラストマーを得る。(c) Recovery of product As a method for recovering the product, any known method commonly employed in this type of polymerization method can be employed. For example, after the second step of polymerization is completed, the reaction mixture is poured into an aqueous solution of inorganic salts such as common salt, calcium chloride, magnesium chloride, magnesium sulfate, and aluminum sulfate under stirring to obtain a polymer composition mainly containing the resulting polymer composition. agglomerate the composition. This is filtered, washed, and dried to obtain the desired thermoplastic elastomer.
【００２８】[0028]
【実施例】以下に示す実施例および比較例によって本発
明を更に具体的に説明する。なお、これら実験例中の「
部」は重量部を意味する。また、本発明の実施例および
比較例におけるゲル分率および物性の測定方法は次に示
す通りである。
ゲル分率
架橋アクリルゴム（成分ａ）約１グラム（精秤値をＡグ
ラムとする）にメチルエチルケトン３００ｍｌを加え、
メチルエチルケトンの沸点下で３時間加熱攪拌した後、
遠心分離機を用いて不溶部を分離、乾燥する。この不溶
部の乾燥重量をＢグラムとすれば、ゲル分率はゲル分率
（％）＝（Ｂ／Ａ）×１００
として計算した。
物性測定用テストピースの成形
プレス成形機を用いて、２００℃で成形した。
硬 度
ＪＩＳ−Ｋ６３０１−Ａ法に従って測定した。
圧縮永久歪
ＪＩＳ−Ｋ６３０１に従い、１００℃で２２時間後の残
留歪を測定した。
引張強度および伸び
ＪＩＳ−Ｋ６３０１に従って測定した。
耐油性
ＪＩＳ−Ｋ６３０１に従い、ＪＩＳ−Ｎｏ． ３油に１
２５℃で７２時間浸漬したときの体積膨潤率（ΔＶ）を
測定した。
ガラス転移温度
粘弾性測定法により測定した。すなわち、レオメトリッ
クス社製メカニカルスペクトロメーターＲＭＳ６０５型
機を用い、周波数１Ｈｚ（２πｒａｄ ／ｓｅｃ ）、
昇温速度１℃／Ｍｉｎ にて測定したｔａｎ δのピー
ク温度をガラス転移温度とした。EXAMPLES The present invention will be explained in more detail with reference to the following examples and comparative examples. In addition, in these experimental examples, “
"Parts" means parts by weight. Furthermore, the methods for measuring gel fraction and physical properties in Examples and Comparative Examples of the present invention are as follows. Add 300 ml of methyl ethyl ketone to about 1 gram of gel fraction crosslinked acrylic rubber (component a) (accurate weighing value is A gram),
After heating and stirring for 3 hours under the boiling point of methyl ethyl ketone,
Separate and dry the insoluble part using a centrifuge. Assuming that the dry weight of this insoluble portion is B grams, the gel fraction was calculated as gel fraction (%)=(B/A)×100. Molding was performed at 200° C. using a press molding machine for forming test pieces for measuring physical properties. Hardness was measured according to JIS-K6301-A method. The residual strain after 22 hours at 100° C. was measured according to compression set JIS-K6301. Tensile strength and elongation were measured according to JIS-K6301. Oil resistance According to JIS-K6301, JIS-No. 3 parts oil to 1 part
The volumetric swelling ratio (ΔV) was measured after immersion at 25° C. for 72 hours. Measured by glass transition temperature viscoelasticity measurement method. That is, using a mechanical spectrometer RMS605 manufactured by Rheometrics, the frequency was 1 Hz (2πrad/sec),
The peak temperature of tan δ measured at a heating rate of 1° C./Min was defined as the glass transition temperature.
【００２９】実施例１
（１） 第１工程（架橋アクリルゴム（成分ａ）の製造
）イオン交換水１４０部、ドデシルベンゼンスルホン酸
ナトリウム１．４部、ナフタレンスルホン酸ナトリウム
ホルマリン縮合体０．７部、および硫酸ナトリウム０．
２１部を窒素置換した反応器に順次加え、室温下で攪拌
により十分に溶解させた。この系にアクリル酸ブチル（
ＢＡ）５６部、アクリル酸２‐メトキシエチル（ＭＥＡ
）１４部、トリアリルイソシアヌレート（ＴＡＩＣ）０
．７部およびｔ‐ドデシルメルカプタン（ｔ−ＤＭ）０
．０３５部からなる混合液（以下単に「アクリレート混
合物」と略記する。）の十分の一の量を攪拌下に室温で
加えて乳化させた。次いで、反応器を５℃まで冷却し、
エチレンジアミンテトラ酢酸四ナトリウム塩を０．０１
４部、エチレンジアミンテトラ酢酸ナトリウム第二鉄塩
を０．０００３５部とナトリウムハイドロサルファイト
（Ｎａ２Ｓ２Ｏ４）を０．０４部を加えた。上記乳化液
に残りのアクリレート混合物と、過硫酸カリウム（Ｋ２
Ｓ２Ｏ８）０．０３部とイオン交換水１０部とからなる
水溶液をそれぞれ個別の供給ラインから同時に２時間か
けて連続的に供給した。この時反応系内は攪拌下、冷却
しながら５℃に保った。上記アクリレート混合物および
過硫酸カリウム水溶液の供給が終了した後も反応系内の
温度を５℃に保ちながら更に５時間反応を続けた。その
後反応系内の温度を室温まで戻して２時間反応させて、
凝集物が殆ど無く、安定な架橋アクリルゴムのラテック
スを得た。得られた反応混合物をガスクロマトグラフィ
ーで分析したところ、モノマーの反応率は９９％であっ
た。また、生成物のゲル分率は９５％であった。Example 1 (1) First step (manufacture of crosslinked acrylic rubber (component a)) 140 parts of ion-exchanged water, 1.4 parts of sodium dodecylbenzenesulfonate, 0.7 parts of formalin condensate of sodium naphthalenesulfonate. , and sodium sulfate 0.
21 parts were sequentially added to a reactor purged with nitrogen, and sufficiently dissolved by stirring at room temperature. Butyl acrylate (
BA) 56 parts, 2-methoxyethyl acrylate (MEA)
) 14 parts, triallyl isocyanurate (TAIC) 0
．． 7 parts and t-dodecylmercaptan (t-DM) 0
．． A tenth of the mixed solution (hereinafter simply referred to as "acrylate mixture") consisting of 0.035 parts was added at room temperature while stirring to emulsify. The reactor was then cooled to 5°C,
0.01 ethylenediaminetetraacetic acid tetrasodium salt
4 parts, 0.00035 parts of sodium ferric salt of ethylenediaminetetraacetate, and 0.04 parts of sodium hydrosulfite (Na2S2O4) were added. Add the remaining acrylate mixture and potassium persulfate (K2) to the above emulsion.
An aqueous solution consisting of 0.03 parts of S2O8) and 10 parts of ion-exchanged water was simultaneously and continuously supplied from separate supply lines over a period of 2 hours. At this time, the inside of the reaction system was kept at 5°C while being stirred and cooled. Even after the supply of the acrylate mixture and potassium persulfate aqueous solution was completed, the reaction was continued for an additional 5 hours while maintaining the temperature in the reaction system at 5°C. After that, the temperature in the reaction system was returned to room temperature and the reaction was carried out for 2 hours.
A stable crosslinked acrylic rubber latex with almost no aggregates was obtained. When the obtained reaction mixture was analyzed by gas chromatography, the reaction rate of the monomer was 99%. Moreover, the gel fraction of the product was 95%.
【００３０】（２） 第２工程（メタクリル酸エステル
とマレイミド類との共重合体（成分ｂ）の製造）第１工
程の反応で生成したラテックスに、イオン交換水６０部
およびドデシルベンゼンスルホン酸ナトリウム０．３部
をそれぞれ追加した。次いで、この系を７０℃に昇温し
、攪拌しながらメタクリル酸メチル（ＭＭＡ）２１部、
Ｎ‐シクロヘキシルマレイミド（ＣＭＩ）９部および分
子量調節剤としてのα‐メチルスチレンダイマー（α−
ＭＳＤ）０．３部からなる混合液と、１％過硫酸カリウ
ム水溶液１２部とをそれぞれの供給ラインによって同時
に２時間かけてこれらを供給して、架橋アクリルゴムラ
テックスの存在下にＭＭＡとＣＭＩとの共重合を行った
。前記原料混合物および過硫酸カリウム水溶液の供給終
了後、さらに６時間反応を続行した。その時の重合系の
反応温度を７０℃に保った。第２工程のモノマーの反応
率は９７％であった。得られた反応混合液を２０℃に冷
却し、攪拌されている１．５％塩化カルシウム水溶液中
に滴下して反応生成物を塩析した。凝集した生成物を濾
過、水洗し、さらにメタノールで洗浄後、７５℃で真空
乾燥した。この乾燥生成物に酸化防止剤としてのイルガ
ノックス１０１０（商品名）１部を加えて二軸混練機を
用いて１８０℃、５０ｒｐｍ で５分間混練した後、プ
レス成形して物性を測定した。結果を表１に示す。(2) Second step (manufacture of copolymer of methacrylic acid ester and maleimides (component b)) Add 60 parts of ion-exchanged water and sodium dodecylbenzenesulfonate to the latex produced in the reaction of the first step. Added 0.3 parts each. Next, the temperature of this system was raised to 70°C, and while stirring, 21 parts of methyl methacrylate (MMA),
9 parts of N-cyclohexylmaleimide (CMI) and α-methylstyrene dimer (α-
MSD) 0.3 parts of a mixed solution and 12 parts of a 1% potassium persulfate aqueous solution were simultaneously fed over 2 hours through separate feed lines to form MMA and CMI in the presence of the cross-linked acrylic rubber latex. Copolymerization was carried out. After the supply of the raw material mixture and potassium persulfate aqueous solution was completed, the reaction was continued for an additional 6 hours. The reaction temperature of the polymerization system at that time was maintained at 70°C. The reaction rate of the monomer in the second step was 97%. The resulting reaction mixture was cooled to 20° C. and added dropwise to a stirred 1.5% calcium chloride aqueous solution to salt out the reaction product. The aggregated product was filtered, washed with water, further washed with methanol, and then dried in vacuum at 75°C. To this dried product was added 1 part of Irganox 1010 (trade name) as an antioxidant, and the mixture was kneaded for 5 minutes at 180° C. and 50 rpm using a twin-screw kneader, and then press-molded and its physical properties were measured. The results are shown in Table 1.
【００３１】実施例２〜４
第１工程である架橋アクリルゴム（成分ａ）の製造にお
いて、アクリル酸ブチル（ＢＡ）とアクリル酸２‐メト
キシエチル（ＭＥＡ）の量比、および連鎖移動剤として
のｔ−ＤＭの量を変えて実施例１と同じ方法を繰り返し
た。結果を表１に示す。Examples 2 to 4 In the first step of producing crosslinked acrylic rubber (component a), the quantitative ratio of butyl acrylate (BA) to 2-methoxyethyl acrylate (MEA) and the chain transfer agent were adjusted. The same method as in Example 1 was repeated with different amounts of t-DM. The results are shown in Table 1.
【００３２】実施例５〜６
第１工程においてアクリル酸ブチル（ＢＡ）３５部、ア
クリル酸２‐メトキシエチル（ＭＥＡ）３５部を用い、
第２工程においてメタクリル酸エステルとマレイミド類
の種類と量比を変えて実施例１と同じ方法を繰り返した
。 結果を表１に示す。Examples 5 to 6 In the first step, 35 parts of butyl acrylate (BA) and 35 parts of 2-methoxyethyl acrylate (MEA) were used,
In the second step, the same method as in Example 1 was repeated with different types and quantitative ratios of methacrylic acid ester and maleimide. The results are shown in Table 1.
【００３３】実施例７〜９
第１工程において、アクリル酸ブチル（ＢＡ）の代りに
アクリル酸エチル（ＥＡ）を用い、アクリル酸２‐メト
キシエチル（ＭＥＡ）との量比を変え、第２工程でα−
メチルスレンダイマー（α−ＭＳＤ）を０．６部用いて
実施例１と同じ方法を繰り返した。結果を表２に示す。Examples 7 to 9 In the first step, ethyl acrylate (EA) was used instead of butyl acrylate (BA), and the amount ratio with 2-methoxyethyl acrylate (MEA) was changed, and the second step was carried out. α−
The same method as in Example 1 was repeated using 0.6 parts of methylthrene dimer (α-MSD). The results are shown in Table 2.
【００３４】実施例１０
第１工程においてアクリル酸エチル（ＥＡ）３５部とア
クリル酸２‐エトキシエチル（ＥＥＡ）３５部を用い、
第２工程でα−ＭＳＤを０．６部用いて実施例１と同じ
方法を繰り返した。結果を表２に示す。Example 10 In the first step, 35 parts of ethyl acrylate (EA) and 35 parts of 2-ethoxyethyl acrylate (EEA) were used,
The same method as in Example 1 was repeated using 0.6 parts of α-MSD in the second step. The results are shown in Table 2.
【００３５】比較例１
第１工程において、アクリル酸エステルの混合物の代り
にアクリル酸ブチル（ＢＡ）のみ用い、第２工程でα−
ＭＳＤを０．６部用いて実施例１と同じ方法を繰り返し
た。結果を表２に示す。Comparative Example 1 In the first step, only butyl acrylate (BA) was used instead of the mixture of acrylic esters, and in the second step, α-
The same method as in Example 1 was repeated using 0.6 parts of MSD. The results are shown in Table 2.
【００３６】比較例２
第１工程において、アクリル酸エステルの混合物の代り
にアクリル酸エチル（ＥＡ）だけを用い、第２工程でα
−ＭＳＤを０．６部用いて実施例１と同じ方法を繰り返
した。結果を表２に示す。Comparative Example 2 In the first step, only ethyl acrylate (EA) was used instead of the mixture of acrylic esters, and in the second step, α
The same method as in Example 1 was repeated using 0.6 parts of -MSD. The results are shown in Table 2.
【００３７】実施例１１
第１工程においてアクリル酸エステルとしてアクリル酸
ブチル（ＢＡ）４９部、アクリル酸エチル（ＥＡ）１４
部およびアクリル酸２‐メトキシエチル（ＭＥＡ）７部
を用いる外は全て実施例１と同じ方法を繰り返した。結
果を表２に示す。Example 11 In the first step, 49 parts of butyl acrylate (BA) and 14 parts of ethyl acrylate (EA) were used as acrylic esters.
The same procedure as in Example 1 was repeated except that 1 part and 7 parts of 2-methoxyethyl acrylate (MEA) were used. The results are shown in Table 2.
【００３８】[0038]
【表１】[Table 1]
【００３９】[0039]
【表２】
表１および表２中の略号は以下に示す通りである。
ＢＡ：アクリル酸ｎ‐ブチル
ＥＡ：アクリル酸エチル
ＭＥＡ：アクリル酸２‐メトキシエチルＥＥＡ：アクリ
ル酸２‐エトキシエチルＴＡＩＣ：トリアリルイソシア
ヌレートｔ−ＤＭ：ｔ‐ドデシルメルカプタン
ＭＭＡ：メタクリル酸メチル
ＣＭＩ：Ｎ‐シクロヘキシルマレイミドＰＭＩ：Ｎ‐フ
ェニルマレイミド
α−ＭＳＤ：α‐メチルスチレンダイマー[Table 2] Abbreviations in Tables 1 and 2 are as shown below. BA: n-butyl acrylate EA: ethyl acrylate MEA: 2-methoxyethyl acrylate EEA: 2-ethoxyethyl acrylate TAIC: triallylisocyanurate t-DM: t-dodecyl mercaptan MMA: methyl methacrylate CMI: N -Cyclohexylmaleimide PMI: N-phenylmaleimide α-MSD: α-methylstyrene dimer
【００４０】[0040]
【発明の効果】本発明の架橋アクリルゴム（成分（ａ）
）５５〜９５重量部およびメタクリル酸エステル・マレ
イミド類共重合体樹脂（成分（ｂ））４５〜５重量部か
ら構成される熱可塑性エラストマーは、硬い領域から軟
らかい領域にわたって耐熱性と耐油性、さらに耐寒性に
優れ、かつ成形性に優れたもので工業的に極めて有用な
素材である。[Effect of the invention] The crosslinked acrylic rubber of the present invention (component (a)
) and 45 to 5 parts by weight of a methacrylic acid ester/maleimide copolymer resin (component (b)), the thermoplastic elastomer has heat resistance and oil resistance from hard to soft areas, and It has excellent cold resistance and moldability, making it an extremely useful material industrially.
Claims (2)
ｂ）４５〜５重量部（成分（ａ）と成分（ｂ）の和は１
００重量部）からなる熱可塑性エラストマー。 成分（ａ） 一般式ＣＨ２＝ＣＨＣＯＯＲ１（式中のＲ１は炭素数１
〜１２の非置換または置換のアルキル基を表わす。）で
表わされるアクリル酸アルキルエステルモノマー成分（
Ｉ）５〜９５重量％と、一般式ＣＨ２＝ＣＨＣＯＯ（Ｃ
Ｈ２）ｎＯＲ２（式中のｎは１〜１０の整数、Ｒ２は炭
素数１〜１２の非置換または置換のアルキル基を表わす
。）で表わされるアクリル酸グリコールエステルモノマ
ー成分（ＩＩ）９５〜５重量％とからなる共重合体であ
って、ガラス転移温度が−２０℃以下の架橋アクリルゴ
ムからなるゴム成分。 成分（ｂ） 一般式ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯＲ３（式中のＲ３は
炭素数１〜１２の非置換または置換のアルキル基もしく
は脂環式炭化水素残基を表わす。）で表わされるメタク
リル酸エステルモノマー成分（ＩＩＩ）５〜９５重量％
と、一般式 【化１】 （式中のＲ４は水素原子、炭素数１〜１２の非置換また
は置換のアルキル基、脂環式炭化水素残基、あるいは、
非置換または置換のフェニル基を表わす。）で表わされ
るマレイミド類モノマー成分（ＩＶ）９５〜５重量％と
から成る共重合体であって、ガラス転移温度が１１０℃
以上の樹脂成分。Claim 1: 55 to 95 parts by weight of the following component (a) and the component (
b) 45 to 5 parts by weight (the sum of component (a) and component (b) is 1
00 parts by weight). Component (a) General formula CH2=CHCOOR1 (R1 in the formula has 1 carbon number
~12 unsubstituted or substituted alkyl groups. ) acrylic acid alkyl ester monomer component (
I) 5-95% by weight and the general formula CH2=CHCOO(C
H2) Acrylic acid glycol ester monomer component (II) represented by nOR2 (in the formula, n is an integer of 1 to 10, and R2 represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms) 95 to 5 weight %, a rubber component made of crosslinked acrylic rubber and having a glass transition temperature of -20°C or less. Component (b) Methacrylic acid ester represented by the general formula CH2=C(CH3)COOR3 (R3 in the formula represents an unsubstituted or substituted alkyl group or alicyclic hydrocarbon residue having 1 to 12 carbon atoms) Monomer component (III) 5-95% by weight
and the general formula [Formula 1] (R4 in the formula is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon residue, or
Represents an unsubstituted or substituted phenyl group. ) and 95 to 5% by weight of a maleimide monomer component (IV) having a glass transition temperature of 110°C.
The above resin components.
有する多官能性モノマーの共存下に、一般式ＣＨ２＝Ｃ
ＨＣＯＯＲ１（式中のＲ１は炭素数１〜１２の非置換ま
たは置換のアルキル基を表わす。）で表わされるアクリ
ル酸アルキルエステルモノマー成分（Ｉ）５〜９５重量
％と、一般式ＣＨ２＝ＣＨＣＯＯ（ＣＨ２）ｎＯＲ２（
式中のｎは１〜１０の整数、Ｒ２は炭素数１〜１２の非
置換または置換のアルキル基を表わす）で表わされるア
クリル酸グリコールエステルモノマー成分（ＩＩ）９５
〜５重量％とを共重合させて得られたガラス転移温度が
−２０℃以下の架橋アクリルゴムからなるゴム成分（成
分（ａ））を最終重合体組成物１００重量部に対して５
５〜９５重量部の割合で生成させた後、これに一般式Ｃ
Ｈ２＝Ｃ（ＣＨ３）ＣＯＯＲ３（式中のＲ３は炭素数１
〜１２の非置換または置換アルキル基もしくは脂環式炭
化水素残基を表わす）で表わされるメタクリル酸エステ
ルモノマー成分（ＩＩＩ）５〜９５％と一般式【化２】 （式中のＲ４は水素原子、炭素数１〜１２の非置換また
は置換アルキル基、脂環式炭化水素残基、あるいは非置
換または置換のフェニル基を表わす）で表わされるマレ
イミド類モノマー成分（ＩＶ）９５〜５重量％を加えて
更に共重合させて、ガラス転移温度が１１０℃以上のメ
タクリル酸エステルモノマー成分（ＩＩＩ）とマレイミ
ド類モノマー成分（ＩＶ）との共重合体の樹脂成分（成
分（ｂ））を最終重合体組成物１００重量部に対して４
５〜５重量部の割合で生成させることを特徴とする熱可
塑性エラストマーの製造方法。Claim 2: In the coexistence of a polyfunctional monomer having two or more ethylenically unsaturated bonds in the molecule, a compound of the general formula CH2=C
5 to 95% by weight of the acrylic acid alkyl ester monomer component (I) represented by HCOOR1 (in the formula, R1 represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms) and the general formula CH2=CHCOO (CH2 )nOR2(
Acrylic acid glycol ester monomer component (II) represented by the formula (where n is an integer of 1 to 10 and R2 represents an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms) 95
5% by weight of a rubber component (component (a)) consisting of a crosslinked acrylic rubber with a glass transition temperature of -20°C or less obtained by copolymerizing 5% by weight of
After being produced in a proportion of 5 to 95 parts by weight, the general formula C
H2=C(CH3)COOR3 (R3 in the formula has 1 carbon number
~12 unsubstituted or substituted alkyl groups or alicyclic hydrocarbon residues) and 5 to 95% of the methacrylic acid ester monomer component (III) represented by the general formula [Formula 2] (in which R4 is a hydrogen atom) , an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon residue, or an unsubstituted or substituted phenyl group). The resin component (component (b)) of the copolymer of the methacrylic acid ester monomer component (III) having a glass transition temperature of 110° C. or higher and the maleimide monomer component (IV) is then further copolymerized to form a final polymer composition. 4 per 100 parts by weight
A method for producing a thermoplastic elastomer, characterized in that it is produced in a proportion of 5 to 5 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11612591A JPH04342710A (en) | 1991-05-21 | 1991-05-21 | Thermoplastic elastomer and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11612591A JPH04342710A (en) | 1991-05-21 | 1991-05-21 | Thermoplastic elastomer and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04342710A true JPH04342710A (en) | 1992-11-30 |
Family
ID=14679327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11612591A Pending JPH04342710A (en) | 1991-05-21 | 1991-05-21 | Thermoplastic elastomer and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04342710A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007114108A1 (en) * | 2006-03-31 | 2007-10-11 | Zeon Corporation | Acrylic rubber and process for producing the same |
| JP2021123623A (en) * | 2020-02-03 | 2021-08-30 | 株式会社大阪ソーダ | Crosslinking composition |
-
1991
- 1991-05-21 JP JP11612591A patent/JPH04342710A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007114108A1 (en) * | 2006-03-31 | 2007-10-11 | Zeon Corporation | Acrylic rubber and process for producing the same |
| JP2021123623A (en) * | 2020-02-03 | 2021-08-30 | 株式会社大阪ソーダ | Crosslinking composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5183856A (en) | Thermoplastic elastomer and a process for its production | |
| JP2941485B2 (en) | Thermoplastic resin composition | |
| JPH093142A (en) | Rubber-reinforced vinyl polymer and thermoplastic polymer composition | |
| JPH04342710A (en) | Thermoplastic elastomer and its production | |
| EP1312641A1 (en) | Transparent impact-resistant thermoplastic resin composition | |
| JP3286971B2 (en) | Styrene-based copolymer, thermoplastic resin composition containing the copolymer, and methods for producing them | |
| JPH041217A (en) | Production of thermoplastic elastomer | |
| JPH03244610A (en) | Production of thermoplastic elastomer | |
| JPH06345830A (en) | Production of thermoplastic elastomer | |
| JPH0753831A (en) | Thermoplastic elastomer composition | |
| JPH08333489A (en) | Rubberlike polymer latex for base rubber of rubber-reinforced vinyl polymer, rubber-reinforced vinyl polymer, and thermoplastic polymer composition | |
| JP2699945B2 (en) | Thermoplastic resin composition | |
| JPS6247208B2 (en) | ||
| JPH03244609A (en) | Thermoplastic elastomer and its production | |
| JPH04331218A (en) | Production of thermoplastic elastomer | |
| JPH06345931A (en) | Production of thermoplastic elastomer | |
| JPH04220452A (en) | Thermoplastic resin composition | |
| JP2019014815A (en) | Polymer, graft polymer and thermoplastic resin composition | |
| JP2643343B2 (en) | Method for producing thermoplastic resin | |
| JPH0525225A (en) | Production of thermoplastic elastomer | |
| JPH06199938A (en) | Production of glutarimide copolymer and its intermediate compound | |
| JPS63101462A (en) | Paint resin composition | |
| JPH04146910A (en) | Multilayer graft copolymer | |
| JPH09316138A (en) | Rubbery polymer latex, rubber-reinforced vinyl polymer, and thermoplastic polymer composition | |
| JPS5813649A (en) | Thermoplastic resin composition |