JPH02117957A - Polyamide-imade resin composition - Google Patents
Polyamide-imade resin compositionInfo
- Publication number
- JPH02117957A JPH02117957A JP63271440A JP27144088A JPH02117957A JP H02117957 A JPH02117957 A JP H02117957A JP 63271440 A JP63271440 A JP 63271440A JP 27144088 A JP27144088 A JP 27144088A JP H02117957 A JPH02117957 A JP H02117957A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- pref
- imide resin
- antioxidant
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 17
- 239000004962 Polyamide-imide Substances 0.000 claims abstract description 36
- 229920002312 polyamide-imide Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 21
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 11
- 150000003951 lactams Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 4
- 239000002798 polar solvent Substances 0.000 claims abstract description 4
- 229920006122 polyamide resin Polymers 0.000 claims 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012778 molding material Substances 0.000 abstract description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009757 thermoplastic moulding Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Polymers C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- -1 γ -butyl lactone Chemical class 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- SSMSBSWKLKKXGG-UHFFFAOYSA-N 1-(2-chlorophenyl)-2-isopropylaminoethanol Chemical compound CC(C)NCC(O)C1=CC=CC=C1Cl SSMSBSWKLKKXGG-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- WFGHUOGOUOTVBO-UHFFFAOYSA-N 2,6-dipropylaniline Chemical compound CCCC1=CC=CC(CCC)=C1N WFGHUOGOUOTVBO-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- LAUFNCOGSGXOMA-UHFFFAOYSA-N 2-butyl-4-(5-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound C1=C(O)C(CCCC)=CC(SC=2C(=CC(O)=C(CCCC)C=2)C)=C1C LAUFNCOGSGXOMA-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- BGWNOSDEHSHFFI-UHFFFAOYSA-N 2-tert-butyl-4-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methylsulfanylmethyl]-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CSCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 BGWNOSDEHSHFFI-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- MPKIZIGHGVKHDY-UHFFFAOYSA-N 2-tert-butyl-5-methylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1O MPKIZIGHGVKHDY-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- PXUAIMCBQXEGKY-UHFFFAOYSA-N 3,4,5-trifluoro-6-(2,3,4,5,6-pentafluorophenyl)benzene-1,2-diamine Chemical group FC1=C(F)C(N)=C(N)C(C=2C(=C(F)C(F)=C(F)C=2F)F)=C1F PXUAIMCBQXEGKY-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- ILKGEOVHANZEFC-UHFFFAOYSA-N 4-ethoxybenzenesulfonamide Chemical compound CCOC1=CC=C(S(N)(=O)=O)C=C1 ILKGEOVHANZEFC-UHFFFAOYSA-N 0.000 description 1
- IPDXWXPSCKSIII-UHFFFAOYSA-N 4-propan-2-ylbenzene-1,3-diamine Chemical compound CC(C)C1=CC=C(N)C=C1N IPDXWXPSCKSIII-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000270666 Testudines Species 0.000 description 1
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- RRZCFXQTVDJDGF-UHFFFAOYSA-N dodecyl 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC RRZCFXQTVDJDGF-UHFFFAOYSA-N 0.000 description 1
- LRMJAFKKJLRDLE-UHFFFAOYSA-N dotarizine Chemical compound O1CCOC1(C=1C=CC=CC=1)CCCN(CC1)CCN1C(C=1C=CC=CC=1)C1=CC=CC=C1 LRMJAFKKJLRDLE-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OHQOKJPHNPUMLN-UHFFFAOYSA-N n,n'-diphenylmethanediamine Chemical compound C=1C=CC=CC=1NCNC1=CC=CC=C1 OHQOKJPHNPUMLN-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】 (産業上の利用分野) 本発明はポリアミドイミド樹脂組成物に関し。[Detailed description of the invention] (Industrial application field) The present invention relates to polyamideimide resin compositions.
さらに詳しくは1機械強度、溶融流動性および経済性に
優れたポリアミドイミド樹脂組成物に関する。More specifically, the present invention relates to a polyamide-imide resin composition having excellent mechanical strength, melt fluidity, and economical efficiency.
(従来の技術)
従来、安価なポリアミドイミド樹脂の製造法としては次
の二つの方法が知られている。(Prior Art) Conventionally, the following two methods are known as methods for producing inexpensive polyamide-imide resins.
(1)インシアネート法:例えばトリメリット酸無水物
トジフェニルメタン−4,47−ジイソシアネートとを
反応させる方法(例えば特公昭44−19274号公報
、時開°昭54−44719号公報1%開昭50−70
452号公報、4!開昭57−125220号公報)。(1) Incyanate method: For example, a method in which trimellitic anhydride is reacted with diphenylmethane-4,47-diisocyanate (for example, Japanese Patent Publication No. 44-19274, Publication No. 44719/1989, 1% -70
Publication No. 452, 4! Publication No. 57-125220).
(2) アミン法:例えばトリメリット酸無水物と芳
香族ジアミンとを反応させる方法(例えば、特公昭49
−4077号公報9%開昭57−14622号公報、特
開昭52−104596号公報)。(2) Amine method: For example, a method in which trimellitic anhydride and aromatic diamine are reacted (for example,
-4077, 9%, 1984-14622, JP-A-52-104596).
しかしながら、これらの方法で得られるポリアミドイミ
ド樹脂によっては9通常の成形条件である空気雰囲気下
、高温の成形において著しく酸化劣化し機械強度の弱い
成形品しか得られないこと。However, depending on the polyamide-imide resin obtained by these methods, 9 they undergo significant oxidative deterioration during molding at high temperatures in an air atmosphere, which is the usual molding condition, and only molded products with weak mechanical strength can be obtained.
またこの樹脂は溶融流動性も不十分であり、実用化が困
難であった。This resin also had insufficient melt fluidity, making it difficult to put it into practical use.
(発明が解決しようとする課題) 本発明の目的は、前記従来技術の欠点を除去し。(Problem to be solved by the invention) The object of the present invention is to eliminate the drawbacks of the prior art.
機械強度、溶融流動性および経済性に優れたポリアミド
イミド樹脂組成物を提供することにある。An object of the present invention is to provide a polyamide-imide resin composition having excellent mechanical strength, melt fluidity, and economical efficiency.
(l!題を解決するための手段)
本発明は、トリメリット酸無水物まtはその誘導体(1
)および芳香族ジアミン([I)ま九は芳香族ジイソシ
アネート(■)、必要によりさらにジカルボン酸CIt
/)および/またはラクタム(Vlを極性溶媒中で1反
応させて得られるポリアミドイミド樹脂に酸化防止剤■
)を添加してなるポリアミドイミド樹脂組成物に関する
。(l! Means for Solving the Problem) The present invention provides trimellitic anhydride or its derivatives (l!
) and aromatic diamine ([I) and aromatic diisocyanate (■), if necessary further dicarboxylic acid CIt
/) and/or lactam (Vl) in a polar solvent.
) is added to a polyamideimide resin composition.
本発明に用いられるトリメリット酸無水物またはその誘
導体(1)としては、好ましくはトリメリット酸無水物
が用いられ、トリメリット酸無水物の誘導体としては、
トリメリット酸またはトリメリット酸無水物とアルコー
ルとのエステル化物等。As trimellitic anhydride or its derivative (1) used in the present invention, trimellitic anhydride is preferably used, and as the trimellitic anhydride derivative,
Esterified products of trimellitic acid or trimellitic anhydride and alcohol, etc.
例えばトリメリット酸無水物のメタノールハーフエステ
ル化物等が挙げられる。For example, a methanol half ester of trimellitic anhydride may be used.
本発明に用いられる芳香族ジアミン(II)としては。As the aromatic diamine (II) used in the present invention.
例、t ハm−フェニレンジアミ/l p−フェニレン
ジアミン、4.4’−ジアミノジフェニルプロパン。Examples, t ha m-phenylenediamine/l p-phenylenediamine, 4,4'-diaminodiphenylpropane.
4.4′−ジアミノジフェニルメタン、4.4’−ジア
ミノジフェニルスルフィド、4.4’−ジアミノジフェ
ニルスルホン、4.4’−ジアミノジフェニルエーテル
、1.5−ジアミノナフタレン、3.3’−ジアミノジ
フェニル、亀3′−ジメトキシベンジジン、1.3−ジ
アミノ−4−イソプロピルベンゼン、キシリρル
フジアミン。4./−ジアミノターフェニル、4゜4′
−ジアミノクォーターフェニル、1.4−ビス(p−ア
ミノフェノキシ)ペンゼア、4.4’−Cビス−(p−
アミノフェノキシ)〕ジフェニルスルホン、4.4’−
[ビス−(p−アミノフェキシ)]ビフェニル、λ2−
ビス(4−(4−アミノフェノキシ)フェニル〕プロパ
ン、42−ビス〔4−(4−アミノフェノキシ)フェニ
ル〕へキサフルオロプロパン、4.4’−ジアミノベン
ゾフェノン。4.4'-diaminodiphenylmethane, 4.4'-diaminodiphenyl sulfide, 4.4'-diaminodiphenylsulfone, 4.4'-diaminodiphenyl ether, 1.5-diaminonaphthalene, 3.3'-diaminodiphenyl, turtle 3'-dimethoxybenzidine, 1,3-diamino-4-isopropylbenzene, xylylphurfudiamine. 4. /-diaminoterphenyl, 4°4'
-diaminoquaterphenyl, 1,4-bis(p-aminophenoxy)penzea, 4.4'-Cbis-(p-
aminophenoxy)] diphenylsulfone, 4.4'-
[bis-(p-aminophexy)]biphenyl, λ2-
Bis(4-(4-aminophenoxy)phenyl)propane, 42-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diaminobenzophenone.
ベンジジン−2,3,5,6−チトラメチルーp−フェ
ニレ/ジアミン、ジアミノトルエン、テトラフルオロフ
ェニレンジアミン、ジアミノオクタフルオロビフェニル
、4.4’−メチレンビス(2,6−ジメ+/L、7:
IJン)、 4.4’−メチレンビス(λ6−ジニチル
アニリン)、4.4’−メチレンビス(2,6〜ジプロ
ピルアニリン)、4.4’−メチレンビス(2−メチル
−6−二チルアニリン)等が挙げられる。Benzidine-2,3,5,6-titramethyl-p-phenyle/diamine, diaminotoluene, tetrafluorophenylendiamine, diaminooctafluorobiphenyl, 4,4'-methylenebis(2,6-dime+/L, 7:
IJn), 4.4'-methylenebis(λ6-dinitylaniline), 4.4'-methylenebis(2,6-dipropylaniline), 4.4'-methylenebis(2-methyl-6-ditylaniline) etc.
これらの化合物のうち、特に経済性と酸化防止剤の添加
効果を考慮すると1分子中に酸化され易い基、たとえば
アルキル基、アルキレン基、アルキレン基をもつ化合物
、具体的には、4.4’−ジアミノジフェニルメタン、
4.4’−メチレンビス(λ6−シメチルアニリン)、
4.4’−メチレンビス−(46−ジニチルアニリン)
等のアルキル基の付加したメチレンビスアニリン、2.
2−ビス〔4−(4−アミノフェノキシ)フェニル〕プ
ロパンを用いることが好ましい。Among these compounds, especially considering economic efficiency and the effect of adding antioxidants, compounds having a group that is easily oxidized in one molecule, such as an alkyl group, an alkylene group, or an alkylene group, specifically, 4.4' -diaminodiphenylmethane,
4.4'-methylenebis(λ6-dimethylaniline),
4.4'-methylenebis-(46-dinithylaniline)
Methylenebisaniline with an alkyl group added, such as 2.
Preference is given to using 2-bis[4-(4-aminophenoxy)phenyl]propane.
芳香族ジイソシアネートとしては9例えば上記したジア
ミンをホスゲンまたは塩化チオニルと反応させて得られ
る芳香族ジインシアネートが用いられる。経済性と酸化
防止剤の効果を考慮すると分子中に酸化され易い基、な
とえばアルキル基。As the aromatic diisocyanate, for example, an aromatic diincyanate obtained by reacting the above diamine with phosgene or thionyl chloride is used. Considering economic efficiency and the effect of antioxidants, groups that are easily oxidized in the molecule, such as alkyl groups.
アルキレン基、アルキリデン基をもつ化合物、具体的に
は4.4′−ジフェニルメタンジイソシアネー)、4.
4’−メチレンビス(λ6−シメチルフエニルイソシア
ネート)、4.4’−メチレンビス(スロージエチルフ
ェニルイソシアネート)等のアルキル基の付加したメチ
レンビスフェニルイソシアネート、2.2−ビス[4−
(4−インシアネートフェノキシ)フェニル〕プロパン
を用いることが好ましい。Compounds having an alkylene group or an alkylidene group, specifically 4,4'-diphenylmethane diisocyanate), 4.
Methylenebisphenylisocyanate with an alkyl group such as 4'-methylenebis(λ6-simethylphenyl isocyanate), 4.4'-methylenebis(slow-diethylphenylisocyanate), 2.2-bis[4-
Preferably, (4-incyanatophenoxy)phenyl]propane is used.
本発明方法においては、所望によりトリメリット酸無水
物またはその誘導体+1)および芳香族ジアミン(II
)または芳香族ジイソシアネート(DIIK加えて。In the method of the present invention, if desired, trimellitic anhydride or its derivative +1) and aromatic diamine (II
) or aromatic diisocyanates (in addition to DIIK).
ジカルボン酸(IV)および/またはラクタム(V)を
用いるが1本発明において必要に応じて用いられるジカ
ルボン酸N)としては9例えばコハク酸、アジピン酸、
セバシン酸、ドデカンジカルボン酸、イソフタル酸、テ
レフタル酸等が挙げられる。これらの化合物のうち耐熱
性、樹脂の溶解性を考慮すると、イノフタル酸を用いる
ことが好ましい。Dicarboxylic acids (IV) and/or lactams (V) are used; examples of dicarboxylic acids (N) used as needed in the present invention include succinic acid, adipic acid,
Examples include sebacic acid, dodecanedicarboxylic acid, isophthalic acid, and terephthalic acid. Among these compounds, inophthalic acid is preferably used in consideration of heat resistance and solubility of the resin.
本発明において必要に応じて用いられるラクタム閏とし
ては、一般式。The lactams used as necessary in the present invention are of the general formula.
HN −□ CO
\ /
(Cth) n
(式中、nは2〜20の整数を表わす)のラクタムが用
いられ、好壕しくはε−カプロラクタムが用いられる。A lactam of HN-□CO\/(Cth)n (in the formula, n represents an integer of 2 to 20) is used, and preferably ε-caprolactam is used.
本発明方法において、ジカルボン酸(IV)とラクタム
(■)の2成分を必要に応じて特定の割合で併用するこ
とKよす、−)カルボン酸とラクタムのそれぞれ単独成
分で変性したものでは得られない高度な溶融流動性が得
られる。In the method of the present invention, it is possible to use two components, dicarboxylic acid (IV) and lactam (■), in a specific ratio as necessary. A high degree of melt fluidity is obtained.
ジカルボン酸(間の混合割合は、溶融流動性や耐熱性の
点から。Dicarboxylic acids (The mixing ratio between them is determined from the viewpoint of melt fluidity and heat resistance.
(モル比)(mはトリメリット酸無水物またはその誘導
体である)が好普しく、特KO,08〜0.15(モル
比)が好ましい。(molar ratio) (m is trimellitic anhydride or a derivative thereof) is preferable, and especially KO, 08 to 0.15 (molar ratio) is preferable.
ラクタム(Vlの混合割合は、溶融流動性や耐熱性の点
の)ら
(モル比)が好ましく1%KO,10〜0.18(モル
比)が好ましい。The mixing ratio of lactam (Vl) is preferably 1% KO (molar ratio) from the viewpoint of melt fluidity and heat resistance, and preferably 10 to 0.18 (molar ratio).
ま、た本発明方法においては、酸成分((り十債))と
アミン成分(Ill、 tたはイソシアネート成分(I
II)との使用割合は、 (Ill(It/)K対する
([[lまたはfull)をほぼ等モルとなるように用
いることが好ましく、特K(モル比)が好ましい。Furthermore, in the method of the present invention, an acid component ((RIJUKON)) and an amine component (Ill, t) or an isocyanate component (I
II) is preferably used so that the ratio of (Ill(It/)K to ([[l or full) is approximately equimolar, and particularly K (molar ratio) is preferable.
本発明に用いられる極性溶媒としては、生成するポリア
ミドイミド樹脂をよく溶解し、沸点がメ
180℃以上のものが好ましく9例えばN−ブチルピロ
リドン、N−エチルピロリドン、N−ブチルピロリドン
、フェノール、クレゾール、キシレノルウスルホランγ
−ブチルラクトン等が挙げらノ
れる。これらの化合物のうちN−メチルピロリド/を用
いることが好ましい。The polar solvent used in the present invention is preferably one that dissolves the resulting polyamide-imide resin well and has a boiling point of 180°C or higher.9 For example, N-butylpyrrolidone, N-ethylpyrrolidone, N-butylpyrrolidone, phenol, cresol , xylenol usulfolane γ
-butyl lactone, etc. Among these compounds, it is preferable to use N-methylpyrrolide/.
本発明において、芳香族ジアミンを用いてポリアミドイ
ミド樹脂を合成する場合は脱水触媒を添加して行うこと
が好ましい。脱水触媒としては。In the present invention, when synthesizing polyamideimide resin using aromatic diamine, it is preferable to add a dehydration catalyst. As a dehydration catalyst.
例えば3価または5価の有機または無機のりん化合物、
−酸化鉛、ホウ酸、無水ホウ酸叫が挙げられる。これら
の化合物のうちりん酸、トリフェニルホスフェート、ホ
ウ酸または無水ホウ酸を用いることが好ましい。For example, trivalent or pentavalent organic or inorganic phosphorus compounds,
- Lead oxide, boric acid, boric anhydride. Among these compounds, it is preferable to use phosphoric acid, triphenyl phosphate, boric acid or boric anhydride.
脱水触媒の使用割合は、酸成分1−+v))に対してO
,1〜10重量%が好ましく1%に1〜5重量%が好ま
しい。The ratio of the dehydration catalyst used is O to the acid component 1-+v)).
, preferably 1 to 10% by weight, and preferably 1 to 5% by weight.
本発明におけるポリアミドイミド樹脂を芳香族ジアミン
を用いて合成する場合は、七ツマ−をまず均一に混合溶
解し170℃に昇温し、脱水を行いながらさらに昇温し
て205℃で重合反応させることが好ましい。When synthesizing the polyamide-imide resin of the present invention using an aromatic diamine, firstly, the 7-mer is uniformly mixed and dissolved, the temperature is raised to 170°C, and the temperature is further raised while dehydrating to carry out a polymerization reaction at 205°C. It is preferable.
この際重合反応は反応系から副生ずる水を留去しながら
進めることが好ましく、必要に応じて少量のトルエン、
キシレン等の脱水促進剤の存在下に、190〜220℃
付近で重合反応を行なうことが好ましい。At this time, it is preferable to proceed with the polymerization reaction while distilling by-product water from the reaction system, and if necessary, a small amount of toluene,
190-220℃ in the presence of a dehydration accelerator such as xylene
It is preferable to carry out the polymerization reaction nearby.
重合濃度は反応初期では40〜5011量チ程度でよく
9反応後期は高@を保持するため65重量%付近に高濃
度化することが好ましい。重合反志終了後、末端基封鎖
剤で末端基を封鎖することができる。末端基を封鎖する
ことにより、成形時の熱安定性が向上する。The polymerization concentration may be about 40 to 5011% in the early stage of the reaction, and in the late stage of the reaction, it is preferable to increase the concentration to around 65% by weight in order to maintain a high @. After the polymerization reaction is completed, the terminal groups can be blocked with an end group blocking agent. By capping the terminal groups, thermal stability during molding is improved.
この際用いられる末端基封鎖剤としては1例えば無水フ
タル酸、安息香酸、無水酢酸、アニリン。Examples of end group blocking agents used in this case include phthalic anhydride, benzoic acid, acetic anhydride, and aniline.
n−ブチルアミン、フェニルイソシアネート等が挙げら
れる。Examples include n-butylamine and phenyl isocyanate.
本発明により得られるポリアミドイミド樹脂の還元粘度
(溶媒ニジメチルホルムアミド、試料濃度:0.59/
d/温度30℃で測定)は機械強度の点から0.40
(a//g)以上が好ま17い。Reduced viscosity of polyamideimide resin obtained by the present invention (solvent dimethylformamide, sample concentration: 0.59/
d/measured at a temperature of 30°C) is 0.40 in terms of mechanical strength.
(a//g) or more is preferred.
本発明における酸化防止剤(M)としては例えばハイド
ロキノン、ハイドロキノ/モノメチルエーテル、ス5−
ジーt−ブチルハイドロキノン、2.5−1−アミルハ
イドロキノン、t−ブチルカテコール、スチレン化フェ
ノール、2−1−プチルー4−メチルフェノール、2.
6−ジーt−ブチルフェノール、ポリブチレーテッドビ
スフェノールA。Examples of the antioxidant (M) in the present invention include hydroquinone, hydroquino/monomethyl ether,
Di-t-butylhydroquinone, 2.5-1-amylhydroquinone, t-butylcatechol, styrenated phenol, 2-1-butyl-4-methylphenol, 2.
6-di-t-butylphenol, polybutylated bisphenol A.
4.4’−ジヒドロキシジフェニルスルホン(ビスフェ
ノールS)、ビスフェノールA、チオビスフェノール、
2,4.5−)リヒドロキシブチロフエノン。4.4'-dihydroxydiphenylsulfone (bisphenol S), bisphenol A, thiobisphenol,
2,4.5-)lyhydroxybutyrophenone.
2.6−ジー1−ブチル−4メチルフエノール、4゜6
−ジーt−ブチル−2−メチルフェノール、ブチルヒド
ロキシアニソール、2.2’−メチレンビス(4−メチ
ル−6−t−ブチルフェノール)、4゜4′−メチレン
ビス(26−ジーt−ブチルフェノール)、トリス(2
−メチル−4−ヒドロキシ−5−t−ブチルフェノール
)ブタン、1.&5−)リエチルー2.4.6−トリス
(3,5−ジ−t−ブチル−4−ヒドロキシベンジル)
ベンゼン、テトラキス〔メチレン−(3/、 5/−ジ
−t−ブチル−4−ヒドロキシヒドロシンナメート)〕
メタ/、1゜λ5−トリス(4−1−ブチル−3−ヒド
ロキシ−スロージメチルベンジル)イソシアヌレート。2.6-di-1-butyl-4methylphenol, 4゜6
-di-t-butyl-2-methylphenol, butylhydroxyanisole, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4°4'-methylenebis(26-di-t-butylphenol), tris( 2
-methyl-4-hydroxy-5-t-butylphenol)butane, 1. &5-) Liethyl-2.4.6-tris(3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis [methylene-(3/, 5/-di-t-butyl-4-hydroxyhydrocinnamate)]
meta/, 1°λ5-tris(4-1-butyl-3-hydroxy-slodimethylbenzyl)isocyanurate.
1、&5−トリス(&5−ジーt−ブチルー4−ヒドロ
キシベンジル)イソシアヌレート、 I RGANOX
245、IRGANOX259.IRGANOX565
゜IRGANOXIOIO,IRGANOX1035゜
エルGANOX1076、IRGANOX1081゜I
RGANOX1098.IRGANOX1222゜エル
GANOXI 330.IR,GANOXI 425W
L(以上、チバガイギー社製、商品名)等のフェノール
系酸化防止剤、ジラウリルチオジグロビロネート、シミ
リスチルチオジプロピオネート、ジステアリルチオジグ
ロピオネート、ラウリル・ステアリルチオジプロピオネ
ート、ペンタエリスリトール−テトラキス(3−ラウリ
ルチオプロピオネート)、4.4’−チオビス(3−メ
チル−6−1−ブチルフェノール)、2−2’−チオビ
ス(4−メチル−6−t−ブチルフェノール)、ビス(
3−メチル−4−ヒドロキシ−5−t−ブチルベンジル
)サルファイド、2−メルカプトベンズイミダゾール等
の硫黄系酸化防止剤、トリフェニルホスファイト、トリ
オクタデシルホスファイト、トリデシルホスファイト、
トリラウリルトリチオホスファイト等のりん系酸化防止
剤I N−n−ブチル−p−アミンフェノール、オクチ
ル化ジフェニルアミン、 N、 N’−ジインプロピル
−p−フェレンジアミン、 N、 N’−ジー5ec−
ブチル−p−7エニレンジアミン、 N、 N’−ビス
(1,4−ジメチルペンチル) −1)−フェニレンシ
アミン、N、N’−ビス(1−エチル−3−メチルペン
チル)−p−フ二二しンジアミン、N−フェニル−N/
−インプロビル−p−フェニレンジアミン、 N、 N
’−ジフェニル−p−ジフェニレンジアミン、N、N’
−シーβ−ナフチル−p−フ二二しンジアミン、フェノ
チアジン、N−フェニル−α−ナフチルアミン等のアミ
ン系酸化防止剤などが用いられ、酸化防止剤の融点が2
00℃以上であるフェノール系酸化防止剤が好ましい。1,&5-tris(&5-di-t-butyl-4-hydroxybenzyl)isocyanurate, I RGANOX
245, IRGANOX259. IRGANOX565
゜IRGANOXIOIO, IRGANOX1035゜El GANOX1076, IRGANOX1081゜I
RGANOX1098. IRGANOX1222゜ELGANOXI 330. IR, GANOXI 425W
Phenolic antioxidants such as L (manufactured by Ciba Geigy, trade name), dilauryl thiodiglovironate, simyristyl thiodipropionate, distearyl thiodiglopionate, lauryl stearyl thiodipropionate, pentaerythritol -tetrakis(3-laurylthiopropionate), 4,4'-thiobis(3-methyl-6-1-butylphenol), 2-2'-thiobis(4-methyl-6-t-butylphenol), bis(
3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, sulfur-based antioxidants such as 2-mercaptobenzimidazole, triphenyl phosphite, triotadecyl phosphite, tridecyl phosphite,
Phosphorous antioxidants such as trilauryltrithiophosphite I N-n-butyl-p-aminephenol, octylated diphenylamine, N,N'-diimpropyl-p-phelenediamine, N,N'-di5ec-
Butyl-p-7enylenediamine, N,N'-bis(1,4-dimethylpentyl)-1)-phenylenecyamine, N,N'-bis(1-ethyl-3-methylpentyl)-p- Phenyl diamine, N-phenyl-N/
-Improvir-p-phenylenediamine, N, N
'-diphenyl-p-diphenylenediamine, N, N'
- Amine-based antioxidants such as β-naphthyl-p-phinidine diamine, phenothiazine, and N-phenyl-α-naphthylamine are used, and the melting point of the antioxidant is 2.
Phenolic antioxidants having a temperature of 00°C or higher are preferred.
特に、4.4’−ジヒドロキシジフェニルスルホン(ビ
スフェノールs>カ好−tしい。酸化防止剤の添加量は
、ポリアミドイミド樹脂に対して1〜40重量%が好ま
しく、5〜20重量%がより好ましい。In particular, it is preferable that 4,4'-dihydroxydiphenylsulfone (bisphenol s > .
酸化防止剤の添加量が1重量−未満であれば加熱時の酸
化防止効果が不十分であり、′!た溶融流動性が低下す
る傾向がある。また40重量%を超えると、加熱時の酸
化、溶融流動性は大幅に改善されるが成形材料としての
耐熱性や機械強度が低下する傾向があるので、酸化防止
能と溶融流動性の付与能とを勘案して、酸化防止剤の添
加量を決めればよい。酸化防止剤の添加は9合成後の樹
脂組成物または脱溶剤を行った粉末樹脂に添加されるが
、特に粉末樹脂に添加することが好ましい。If the amount of antioxidant added is less than 1 weight, the antioxidant effect during heating will be insufficient, and '! There is a tendency for melt fluidity to decrease. If the amount exceeds 40% by weight, oxidation during heating and melt fluidity will be significantly improved, but the heat resistance and mechanical strength as a molding material will tend to decrease, so the ability to provide oxidation prevention ability and melt fluidity will decrease. The amount of antioxidant to be added may be determined by taking these into consideration. The antioxidant is added to the resin composition after 9 synthesis or to the powdered resin from which the solvent has been removed, but it is particularly preferable to add it to the powdered resin.
本発明における一つの好ましい態様は、芳香族ジアミン
として本4′−ジアミノジフエニルメタンまたは芳香族
ジイソシアネートとして4.47−シフエニルメタンジ
イソシアネートを用いて得九ポリアミドイミド樹脂に融
点が200℃以上のフェノール系酸化防止剤として4.
47−ジヒドロキシジフェニルスルホンをポリアミドイ
ミド樹脂に対して1〜40重量%添加したポリアミドイ
ミド樹脂組成物である。One preferred embodiment of the present invention is to use 4'-diaminodiphenylmethane as the aromatic diamine or 4,47-cyphenylmethane diisocyanate as the aromatic diisocyanate to add phenol having a melting point of 200°C or higher to the polyamide-imide resin. 4. As a system antioxidant.
This is a polyamide-imide resin composition in which 1 to 40% by weight of 47-dihydroxydiphenyl sulfone is added to the polyamide-imide resin.
この組成物は汎用な材料を用いて得られるため経済性に
優れる。また4、4′−ジアミノジフェニルメタン、4
4′−ジフェニルメタンジイソシアネートの酸化され易
いメチレン結合の酸化劣化が、4゜4′−ジヒドロキシ
ジフェニルスルホンの添加によって抑制されるので9機
械強度に優れる。さらに融点が高い低分子量の4.4′
−ジヒドロキシジフェニルスルホンの多量添加により溶
融流動性と耐熱性のパラ/スに優れる。This composition has excellent economic efficiency because it can be obtained using general-purpose materials. Also, 4,4'-diaminodiphenylmethane, 4
The addition of 4°4'-dihydroxydiphenylsulfone suppresses oxidative deterioration of the easily oxidized methylene bonds in 4'-diphenylmethane diisocyanate, resulting in excellent mechanical strength. Low molecular weight 4.4' with even higher melting point
- By adding a large amount of dihydroxydiphenyl sulfone, the balance between melt fluidity and heat resistance is excellent.
本発明により得られるポリアミドイミド樹脂組。A polyamide-imide resin set obtained by the present invention.
放物は、所望により異種重合体、添加剤、充填剤。The parabolic material may contain different polymers, additives, and fillers if desired.
補強剤等を配合することもできる。A reinforcing agent or the like may also be added.
本発明により得られるポリアミドイミド樹脂組成物は、
必要に応じて成形後に熱処理(ガラス転移温度より低い
温度で1〜24時間)することにより、物性を著しく向
上させることができる。The polyamide-imide resin composition obtained by the present invention is
If necessary, the physical properties can be significantly improved by heat treatment (at a temperature lower than the glass transition temperature for 1 to 24 hours) after molding.
(発明の効果)
本発明によって、耐熱性、溶融流動性および経済性に優
れたポリアミドイミド樹脂組成物を得ることができる。(Effects of the Invention) According to the present invention, a polyamide-imide resin composition having excellent heat resistance, melt fluidity, and economic efficiency can be obtained.
本発明により得られるポリアミドイミド樹脂組成物は、
熱可塑性成形材料として好適であるが。The polyamide-imide resin composition obtained by the present invention is
It is suitable as a thermoplastic molding material.
例えば、耐熱塗料、耐熱シート、耐熱接触剤、耐熱積層
材料、耐熱摺動材料、耐熱繊維、耐熱フィルム等の耐熱
材料としても有用である。For example, it is useful as a heat-resistant material such as a heat-resistant paint, a heat-resistant sheet, a heat-resistant contact agent, a heat-resistant laminated material, a heat-resistant sliding material, a heat-resistant fiber, and a heat-resistant film.
(実施例) 以下1本発明を実施例により説明する。(Example) The present invention will be explained below with reference to examples.
実施例1
上記成分を、攪拌機、窒素導入管および水分定量器付き
四つロフラスコに入れ、攪拌下に窒素ガスを導入しなが
ら、徐々に205℃まで昇温した。Example 1 The above components were placed in a four-loaf flask equipped with a stirrer, a nitrogen inlet tube, and a moisture meter, and the temperature was gradually raised to 205° C. while introducing nitrogen gas while stirring.
同温度で留出する水を反応系外に速やかに除去し。Water distilled out at the same temperature is quickly removed from the reaction system.
同時に、留出するN−メチルピロリドンを追加補充しな
がら、205〜210℃で反応を進めた。At the same time, the reaction was carried out at 205 to 210°C while additionally replenishing distilled N-methylpyrrolidone.
反応終点を高速流体クロマトグラフで管理し、還元粘度
(ジメチルホルムアミド、0.5g/dl!。The end point of the reaction was controlled by high-performance fluid chromatography, and the reduced viscosity (dimethylformamide, 0.5 g/dl!
30℃、以下同様10.49 (dJ/s)のポリアミ
ドイミド樹脂を得た。A polyamide-imide resin of 10.49 (dJ/s) was obtained at 30°C.
得られたポリアミドイミド樹脂溶液をN−メチルピロリ
ドンで約25重′ft%/Cなるように希釈し。The obtained polyamideimide resin solution was diluted with N-methylpyrrolidone to a concentration of about 25% by weight/C.
この溶液をミキサーで強力に攪拌した水中に投下し、固
形のポリアミドイミド樹脂を回収した。この固形樹脂を
熱水でよく洗浄した後、多量の水で煮沸洗浄した。これ
を濾取した後、160℃の熱風乾燥機で6時間乾燥させ
てポリアミドイミド樹脂粉末を得意。This solution was dropped into water that was vigorously stirred with a mixer, and a solid polyamide-imide resin was recovered. After thoroughly washing this solid resin with hot water, it was boiled and washed with a large amount of water. After filtering this, it is dried in a hot air dryer at 160°C for 6 hours to obtain polyamide-imide resin powder.
得られたポリアミドイミド樹脂粉末に酸化防止剤である
4、4′−ジヒドロキシジフェニルスルホン(ビスフェ
ノールS)を、ポリアミドイミド樹脂粉末に対して5重
量饅添加した。このものをミキサーでさらに混合したの
ち、290〜300℃。4,4'-dihydroxydiphenylsulfone (bisphenol S), which is an antioxidant, was added to the obtained polyamide-imide resin powder in an amount of 5 parts by weight based on the polyamide-imide resin powder. After further mixing this with a mixer, the mixture was heated to 290-300°C.
30rpmのブラベンダーで溶融混線を行い、そノ後、
押出しを行ってペレット状のポリアミドイミド樹脂組成
物を得た。Perform melt crosstalk with a Brabender at 30 rpm, then
Extrusion was performed to obtain a pellet-shaped polyamide-imide resin composition.
実施例2
酸化防止剤であるビスフェノールsをボIJ 7ミドイ
ミド樹脂粉末に対して10重量%添加した以外は実施例
1と全く同様にして、ペレット状のポリアミドイミド樹
脂組成物を得た。Example 2 A pellet-shaped polyamide-imide resin composition was obtained in exactly the same manner as in Example 1, except that 10% by weight of bisphenol s, an antioxidant, was added to the BoIJ 7 mid-imide resin powder.
実施例3
酸、化防止剤であるビスフェノールSt−ポリアミドイ
ミド樹脂粉末に対して20重量%添加した以外は実施例
1と全く同様にしてペレット状のポリアミドイミド樹脂
組成物を得た。Example 3 A pellet-shaped polyamide-imide resin composition was obtained in exactly the same manner as in Example 1, except that 20% by weight of acid and bisphenol St-polyamide-imide resin powder as an antioxidant were added.
比較例1
実施例1で得られたポリアミドイミド樹脂粉末(酸化防
止剤無添加品)を290〜300℃、30rpmのブラ
ベンダーで混練を行った所、混線を始めて約10分位で
樹脂は高温の酸化により硬化した。このものは不溶不融
であった。Comparative Example 1 When the polyamide-imide resin powder obtained in Example 1 (product without antioxidant added) was kneaded in a Brabender at 290 to 300°C and 30 rpm, the resin reached a high temperature about 10 minutes after starting mixing. hardened by oxidation. This material was insoluble and infusible.
比較例2
実施例1で得られたポリアミドイミド樹脂粉末に酸化防
止剤であるビスフェノールSを0.5重量−を添加した
が比較例1と同様の結果となった。Comparative Example 2 Although 0.5 weight of bisphenol S as an antioxidant was added to the polyamide-imide resin powder obtained in Example 1, the same results as in Comparative Example 1 were obtained.
実施例および比較例のポリアミドイミド樹脂組成物の溶
融流れ性、射出成形品のTg及び曲げ強度を次に示す方
法で試験した。また、その評価結果を第1表に示した。The melt flow properties, Tg and bending strength of injection molded products of the polyamide-imide resin compositions of Examples and Comparative Examples were tested by the following methods. The evaluation results are shown in Table 1.
溶融流れ性;
十分に乾燥した試料1.5gを300℃に加熱したシリ
ンダー内に入れて3分間加熱させ念後。Melt flowability: 1.5g of a sufficiently dried sample was placed in a cylinder heated to 300°C and heated for 3 minutes.
300に9・fの荷重でダイス中央ノズル(直径1.0
mm、長さ2画)から押出し、島原製作所社製「高化式
フローテスター、CFT−500Jを用いて測定し7次
。The center nozzle of the die (diameter 1.0
mm, length 2 strokes) and measured using Shimabara Seisakusho's "Koka Type Flow Tester, CFT-500J".
射出成形品のTg及び曲げ強度: 射出成形(バレル温度:290℃〜300℃。Tg and bending strength of injection molded product: Injection molding (barrel temperature: 290℃~300℃.
射出圧カニ1500に9・f/印2金型温度:150℃
)により1010mmX10角の曲げ試験用成形品を作
製し島原&オートグラフ(IM−100型)を用いて室
温(25℃)で曲げ強度を測定した。Injection pressure 1500 to 9 f/mark 2 Mold temperature: 150℃
) was used to prepare a 1010 mm x 10 square molded product for bending test, and its bending strength was measured at room temperature (25° C.) using Shimabara & Autograph (Model IM-100).
また上記成形品のガラス転移温度(Tg)を、パーキ/
エルマ社製熱物理試験機(TMS−1)を用いてエキス
パンショy (Expans ion l法で測定した
。これらの結果を第1表に示す。In addition, the glass transition temperature (Tg) of the above molded product was
It was measured by the Expansion method using a thermophysical tester (TMS-1) manufactured by Elma Corporation.The results are shown in Table 1.
Claims (1)
よび芳香族ジアミン(II)または芳香族ジイソシアネー
ト(III)、必要によりさらにジカルボン酸(IV)およ
び/またはラクタム(V)を極性溶媒中で、反応させて
得られるポリアミドイミド樹脂に酸化防止剤(VI)を添
加してなるポリアミドイミド樹脂組成物。 2、酸化防止剤(VI)が融点200℃以上のフェノール
系酸化防止剤である請求項1記載のポリアミド樹脂組成
物。 3、酸化防止剤(VI)の添加量がポリアミドイミド樹脂
に対して、1〜40重量%である請求項1又は2記載の
ポリアミドイミド樹脂組成物。[Claims] 1. Trimellitic anhydride or its derivative (I) and aromatic diamine (II) or aromatic diisocyanate (III), optionally further containing dicarboxylic acid (IV) and/or lactam (V) A polyamide-imide resin composition obtained by adding an antioxidant (VI) to a polyamide-imide resin obtained by reaction in a polar solvent. 2. The polyamide resin composition according to claim 1, wherein the antioxidant (VI) is a phenolic antioxidant having a melting point of 200°C or higher. 3. The polyamide-imide resin composition according to claim 1 or 2, wherein the amount of the antioxidant (VI) added is 1 to 40% by weight based on the polyamide-imide resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63271440A JPH02117957A (en) | 1988-10-27 | 1988-10-27 | Polyamide-imade resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63271440A JPH02117957A (en) | 1988-10-27 | 1988-10-27 | Polyamide-imade resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02117957A true JPH02117957A (en) | 1990-05-02 |
Family
ID=17500053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63271440A Pending JPH02117957A (en) | 1988-10-27 | 1988-10-27 | Polyamide-imade resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02117957A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0737438A (en) * | 1993-07-22 | 1995-02-07 | Optec Dai Ichi Denko Co Ltd | Insulated electric cable |
JP2006022302A (en) * | 2004-06-11 | 2006-01-26 | New Japan Chem Co Ltd | Solvent-soluble polyimide copolymer and polyimide varnish |
JP2007113011A (en) * | 2004-10-14 | 2007-05-10 | Asahi Kasei Chemicals Corp | Resin composition |
JP2009149757A (en) * | 2007-12-20 | 2009-07-09 | Sumitomo Electric Wintec Inc | Polyamide imide and production method thereof, polyamide imide-based insulating coating, and insulated wire |
US7758951B2 (en) | 2004-03-04 | 2010-07-20 | Hitachi Chemical Company, Ltd. | Prepreg, metal-clad laminate and printed circuit board using same |
US8691898B2 (en) | 2004-10-14 | 2014-04-08 | Asahi Kasei Chemicals Corporation | Resin composition |
US10106702B2 (en) * | 2016-06-06 | 2018-10-23 | Cymer-Dayton, Llc | PAI-based coating compositions |
-
1988
- 1988-10-27 JP JP63271440A patent/JPH02117957A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0737438A (en) * | 1993-07-22 | 1995-02-07 | Optec Dai Ichi Denko Co Ltd | Insulated electric cable |
US7758951B2 (en) | 2004-03-04 | 2010-07-20 | Hitachi Chemical Company, Ltd. | Prepreg, metal-clad laminate and printed circuit board using same |
US7871694B2 (en) | 2004-03-04 | 2011-01-18 | Hitachi Chemical Company, Ltd. | Prepreg, metal-clad laminate and printed circuit board using same |
JP2006022302A (en) * | 2004-06-11 | 2006-01-26 | New Japan Chem Co Ltd | Solvent-soluble polyimide copolymer and polyimide varnish |
JP2007113011A (en) * | 2004-10-14 | 2007-05-10 | Asahi Kasei Chemicals Corp | Resin composition |
US8691898B2 (en) | 2004-10-14 | 2014-04-08 | Asahi Kasei Chemicals Corporation | Resin composition |
JP2009149757A (en) * | 2007-12-20 | 2009-07-09 | Sumitomo Electric Wintec Inc | Polyamide imide and production method thereof, polyamide imide-based insulating coating, and insulated wire |
US10106702B2 (en) * | 2016-06-06 | 2018-10-23 | Cymer-Dayton, Llc | PAI-based coating compositions |
US10421881B2 (en) | 2016-06-06 | 2019-09-24 | Cymer-Dayton, Llc | PAI-based coating composition |
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