JPH0267348A - Heat-resistant poly(4-methyl-1-pentene) resin composition and molded item thereof - Google Patents
Heat-resistant poly(4-methyl-1-pentene) resin composition and molded item thereofInfo
- Publication number
- JPH0267348A JPH0267348A JP21974988A JP21974988A JPH0267348A JP H0267348 A JPH0267348 A JP H0267348A JP 21974988 A JP21974988 A JP 21974988A JP 21974988 A JP21974988 A JP 21974988A JP H0267348 A JPH0267348 A JP H0267348A
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- pentene
- weight
- poly
- heat
- 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
- -1 poly(4-methyl-1-pentene) Polymers 0.000 title abstract description 10
- 229920000306 polymethylpentene Polymers 0.000 title abstract 2
- 239000011116 polymethylpentene Substances 0.000 title abstract 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 22
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 22
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 13
- 239000002344 surface layer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 239000003365 glass fiber Substances 0.000 abstract description 6
- 239000000155 melt Substances 0.000 abstract description 5
- 239000004711 α-olefin Substances 0.000 abstract description 4
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 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
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-N 0.000 description 1
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- AONKGGMHQHWMSM-UHFFFAOYSA-N 1,1,1-tribromopropane Chemical compound CCC(Br)(Br)Br AONKGGMHQHWMSM-UHFFFAOYSA-N 0.000 description 1
- QRFALSDGOMLVIR-UHFFFAOYSA-N 1,2,3,4-tetrabromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1Br QRFALSDGOMLVIR-UHFFFAOYSA-N 0.000 description 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-UHFFFAOYSA-N 0.000 description 1
- WBEJYOJJBDISQU-UHFFFAOYSA-N 1,2-Dibromo-3-chloropropane Chemical compound ClCC(Br)CBr WBEJYOJJBDISQU-UHFFFAOYSA-N 0.000 description 1
- 229940100682 1,2-dibromo-3-chloropropane Drugs 0.000 description 1
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XDRAKJQFCQVBMP-UHFFFAOYSA-N 2-but-2-enyl-3-methylbutanedioic acid Chemical compound CC=CCC(C(O)=O)C(C)C(O)=O XDRAKJQFCQVBMP-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- IPFYOMWSZXUSIQ-UHFFFAOYSA-N NCCCO[Si](OC)(OC)CCCN.NCCC[Si](OC)(OC)OC Chemical compound NCCCO[Si](OC)(OC)CCCN.NCCC[Si](OC)(OC)OC IPFYOMWSZXUSIQ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- UGQQAJOWXNCOPY-UHFFFAOYSA-N dechlorane plus Chemical compound C12CCC3C(C4(Cl)Cl)(Cl)C(Cl)=C(Cl)C4(Cl)C3CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl UGQQAJOWXNCOPY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 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
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-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
- 239000002667 nucleating agent Substances 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- LKOCAGKMEUHYBV-UHFFFAOYSA-N tris(3-bromo-3-chloropropyl) phosphate Chemical compound ClC(Br)CCOP(=O)(OCCC(Cl)Br)OCCC(Cl)Br LKOCAGKMEUHYBV-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は耐熱性、特に耐熱老化性および耐熱剛性に優れ
たポリ４−メチル−１−ペンテン樹脂組成物および樹脂
成形物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a poly-4-methyl-1-pentene resin composition and a resin molded article having excellent heat resistance, particularly heat aging resistance and heat-resistant rigidity.
ポリ４−メチル−１−ペンテン樹脂は透明性および機械
的特性に優れた樹脂として広く利用されている。このポ
リ４−メチル−１−ペンテン樹脂は融点が２３５℃と、
他のポリオレフィンに比べて高いことから、耐熱性に優
れた樹脂として、成形品に使用されている。しかしなが
ら、融点より高い温度では、当然のことながらその形状
を保持することはできず、成形品の使用範囲はその融点
より低い温度が限界であった。Poly-4-methyl-1-pentene resin is widely used as a resin with excellent transparency and mechanical properties. This poly-4-methyl-1-pentene resin has a melting point of 235°C.
Because it is more expensive than other polyolefins, it is used in molded products as a resin with excellent heat resistance. However, at temperatures higher than the melting point, it is naturally impossible to maintain the shape, and the range of use of molded products is limited to temperatures lower than the melting point.
一方酸処理を施されたのち洗浄されたポリフェニレンス
ルフィド樹脂７０〜９７重量％と、α−オレフィンおよ
びα、β−不飽和酸のグリシジルエステルを必須成分と
するオレフィン系共重合体３０〜３重量％を含有する樹
脂組成物が、衝撃特性の改良されたポリフェニレンスル
フィド樹脂組成物として提案されている（特開昭６２−
１５３３４３号）。しかしながら、ここではポリ４−メ
チル−１−ペンテン樹脂の耐熱性を改善する点について
は全く開示されていない。On the other hand, 70 to 97% by weight of a polyphenylene sulfide resin that has been acid-treated and washed, and 30 to 3% by weight of an olefin copolymer containing α-olefin and glycidyl ester of α,β-unsaturated acid as essential components. A resin composition containing polyphenylene sulfide has been proposed as a polyphenylene sulfide resin composition with improved impact properties.
No. 153343). However, this publication does not disclose anything about improving the heat resistance of poly-4-methyl-1-pentene resin.
本発明の目的は、ポリ４−メチル−１−ペンテン樹脂の
耐熱性を改善し、ポリ４−メチル−１−ペンテン樹脂の
融点より高い温度で形状を保持することが可能で、かつ
優れた耐熱老化性および耐熱剛性を有するポリ４−メチ
ル−１−ペンテン樹脂組成物および樹脂成形物を提供す
ることである。The purpose of the present invention is to improve the heat resistance of poly-4-methyl-1-pentene resin, to be able to maintain its shape at a temperature higher than the melting point of poly-4-methyl-1-pentene resin, and to have excellent heat resistance. It is an object of the present invention to provide a poly4-methyl-1-pentene resin composition and a resin molded product having aging resistance and heat-resistant rigidity.
本発明は、次の耐熱性ポリ４−メチル−１−ペンテン樹
脂組成物および樹脂成形物である。The present invention is the following heat-resistant poly-4-methyl-1-pentene resin composition and resin molding.
（１）ポリ４−メチル−１−ペンテン８０〜９０重量％
およびポリフェニレンスルフィド１０〜２０重量％を含
有する樹脂分１００重量部に対して、強化繊維１０〜６
０重量部を含有することを特徴とする耐熱性ポリ４−メ
チル−１−ペンテン樹脂組成物。(1) Poly 4-methyl-1-pentene 80-90% by weight
and 10 to 6 parts by weight of reinforcing fibers per 100 parts by weight of the resin containing 10 to 20% by weight of polyphenylene sulfide.
A heat-resistant poly-4-methyl-1-pentene resin composition, characterized in that it contains 0 parts by weight.
（２）ポリ４−メチル−１−ペンテン８０〜９０重量％
およびポリフェニレンスルフィド１０〜２０重量％を含
有する樹脂分１００重量部に対して、強化繊維１０〜６
０重量部を含有し、ポリフェニレンスルフィドが表層部
において層状の連続相を形成していることを特徴とする
耐熱性ポリ４−メチル−１−ペンテン樹脂成形物。(2) Poly 4-methyl-1-pentene 80-90% by weight
and 10 to 6 parts by weight of reinforcing fibers per 100 parts by weight of the resin containing 10 to 20% by weight of polyphenylene sulfide.
1. A heat-resistant poly-4-methyl-1-pentene resin molded article containing 0 parts by weight of polyphenylene sulfide and forming a layered continuous phase in the surface layer.
本発明において用いるポリ４−メチル−１−ペンテンは
、４−メチル−１−ペンテンの単独重合体、もしくは４
−メチル−１−ペンテンと他のα−オレフィン、例えば
エチレン、プロピレン、１−ブテン、■−ヘキセン、１
−オクテン、１−デセン、１−テトラデセン、１−オク
タデセン等の炭素数２ないし２０のα−オレフィンとの
共重合体で、通常４−メチル−１−ペンテンを８５モル
％以上、好ましくは９１モル％以上含む４−メチル−１
−ペンテンを主体とした重合体である。The poly-4-methyl-1-pentene used in the present invention is a homopolymer of 4-methyl-1-pentene or a 4-methyl-1-pentene homopolymer.
-Methyl-1-pentene and other α-olefins, such as ethylene, propylene, 1-butene, -hexene, 1
- A copolymer with an α-olefin having 2 to 20 carbon atoms such as octene, 1-decene, 1-tetradecene, and 1-octadecene, usually containing 4-methyl-1-pentene in an amount of 85 mol% or more, preferably 91 mol%. 4-methyl-1 containing % or more
- It is a polymer mainly composed of pentene.
ポリ４−メチル−１−ペンテンのメルトフローレート（
荷重：５ｋｇ、温度＝２６０℃）は好ましくは５ないし
５００ｇ／１０■ｉｎ、特に好ましくは２５ないし１５
０ｇ／１０ｗ１ｎの範囲のものである。メルトフローレ
ートが５ ｇ／１０＋＋＋ｉｎ未満のものは溶融粘度が
高くて成形性に劣り、メルトフローレートが５００ｇ／
１０ｍ１ｎを越えるものは溶融粘度が低くて成形性に
劣り、また機械的強度も低い。Melt flow rate of poly-4-methyl-1-pentene (
load: 5 kg, temperature = 260° C.) is preferably 5 to 500 g/10 in, particularly preferably 25 to 15
It is in the range of 0g/10w1n. If the melt flow rate is less than 5 g/10+++in, the melt viscosity is high and the moldability is poor;
Those exceeding 10 m1n have low melt viscosity and poor moldability, and also have low mechanical strength.
本発明ではこのようなポリ４−メチル−１−ペンテンは
不飽和カルボン酸または誘導体により一部または全部を
変性したものを使用することができる。In the present invention, such poly-4-methyl-1-pentene may be partially or completely modified with an unsaturated carboxylic acid or a derivative.
ここで用いられる変性ポリ４−メチル−１−ペンテンは
一部もしくは全部が不飽和カルボン酸またはその誘導体
から選ばれるグラフトモノマーで０．０１ないし１０重
量％、好ましくは０．１ないし５重量％の範囲でグラフ
ト変性されたポリ４−メチル−１−ペンテンであり、通
常デカリン溶媒１３５℃における極限粘度が０．５ない
し１５ｄｆｉ／ｇ、好ましくは０．６ないし１０ｄｆ１
／ｇの範囲の好ましくは融点（ＡＳＴＭ ０３４１ｇ）
が２００℃以上の結晶性の重合体である。不飽和カルボ
ン酸またはその誘導体のグラフト量が０．０１重量％未
満のものは前記ポリフェニレンスルフィドとの相溶性に
劣り、耐熱性、機械的強度が劣った組成物となるおそれ
がある。一方、グラフト量が１０重量％を越えるものは
樹脂組成物の耐水性が劣る傾向にある。The modified poly-4-methyl-1-pentene used herein is partially or entirely a graft monomer selected from unsaturated carboxylic acids or derivatives thereof, with an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight. It is poly 4-methyl-1-pentene graft-modified in a range of 0.5 to 15 dfi/g, preferably 0.6 to 10 dfi/g at 135°C in a decalin solvent.
preferably in the range of /g (ASTM 0341g)
is a crystalline polymer with a temperature of 200°C or higher. If the grafting amount of the unsaturated carboxylic acid or its derivative is less than 0.01% by weight, the compatibility with the polyphenylene sulfide may be poor, resulting in a composition with poor heat resistance and mechanical strength. On the other hand, if the amount of grafting exceeds 10% by weight, the water resistance of the resin composition tends to be poor.
本発明において前記ポリ４−メチル−１−ペンテンにグ
ラフトする不飽和カルボン酸またはその誘導体としては
、アクリル酸、マレイン酸、フマール酸、テトラヒドロ
フタル酸、イタコン酸、シトラコン酸、クロトン酸、イ
ソクロトン酸、ナジック酸（エンドシス−ビシクロ［２
，２，１］ヘプト−５−エン−２，３−ジカルボン酸の
登録商標）などの不飽和カルボン酸またはその誘導体、
例えば酸ハライド、アミド、イミド、無水物、エステル
などが挙げられ、具体的には、塩化マレニル、マレイミ
ド、無水マレイン酸、無水シトラコン酸、マレイン酸モ
ノメチル、マレイン酸ジメチル、グリシジルマレエート
などが例示される。これらの中では、不飽和ジカルボン
酸またはその酸無水物が好適であり、とくにマレイン酸
、ナジック酸またはこれらの酸無水物が好適である。In the present invention, unsaturated carboxylic acids or derivatives thereof to be grafted to the poly-4-methyl-1-pentene include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Nadic acid (endocys-bicyclo[2
,2,1]hept-5-ene-2,3-dicarboxylic acid) or its derivatives;
Examples include acid halides, amides, imides, anhydrides, esters, etc. Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc. Ru. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.
これらの不飽和カルボン酸またはその誘導体から選ばれ
るグラフトモノマーを前記ポリ４−メチル−１−ペンテ
ンにグラフト共重合して変性物を製造するには、従来公
知の種々の方法を採用することができる。たとえば、重
合体を溶融させグラフトモツマーを添加してグラフト共
重合させる方法、あるいは溶媒に溶解させグラフトモノ
マーを添加してグラフト共重合させる方法などがある。Various conventionally known methods can be employed to graft copolymerize a graft monomer selected from these unsaturated carboxylic acids or derivatives thereof to the poly-4-methyl-1-pentene to produce a modified product. . For example, there is a method in which a polymer is melted and a graft monomer is added to carry out graft copolymerization, or a method in which a polymer is dissolved in a solvent and a graft monomer is added to carry out graft copolymerization.
いずれの場合にも、前記グラフトモノマーを効率よくグ
ラフト共重合させるためには、ラジカル開始剤の存在下
に反応を実施することが好ましい、グラフト反応は通常
６０ないし３５０℃の温度で行われる。In any case, in order to efficiently graft copolymerize the graft monomer, it is preferable to carry out the reaction in the presence of a radical initiator, and the graft reaction is usually carried out at a temperature of 60 to 350°C.
ラジカル開始剤の使用割合は重合体１００重量部に対し
て通常０．００１ないし１重量部の範囲である。The proportion of the radical initiator used is usually in the range of 0.001 to 1 part by weight per 100 parts by weight of the polymer.
ラジカル開始剤としては有機ペルオキシド、有機ベルエ
ステル、その他アゾ化合物が挙げられる。Examples of the radical initiator include organic peroxides, organic bersesters, and other azo compounds.
これらラジカル開始剤の中でもジクミルペルオキシド、
ジーｔｅｒｔ−ブチルペルオキシド、２，５−ジメチル
−２，５−ジ（ｔａｒｔ−ブチルペルオキシ）ヘキシン
−３，２，５−ジメチル−２，５−（ｔａｒｔ−ブチル
ペルオキシ）ヘキサン、１，４−ビス（ｔａｒｔ−ブチ
ルペルオキシイソプロビル）ベンゼンなどのジアルキル
ペルオキシドが好ましい。Among these radical initiators, dicumyl peroxide,
Di-tert-butylperoxide, 2,5-dimethyl-2,5-di(tart-butylperoxy)hexyne-3,2,5-dimethyl-2,5-(tart-butylperoxy)hexane, 1,4-bis Dialkyl peroxides such as (tart-butylperoxyisopropyl)benzene are preferred.
本発明の樹脂組成物を構成する変性ポリ４−メチル−１
−ペンテンは、不飽和カルボン酸またはその誘導体のグ
ラフト量が前記範囲内にある限り、全部が不飽和カルボ
ン酸等でグラフト変性されたポリ４−メチル−１−ペン
テンまたは未変性のポリ４−メチル−１−ペンテンとの
混合物、すなわち一部が変性された変性ポリ４−メチル
−１−ペンテンであってもよい、なお、未変性のポリ４
−メチル−１−ペンテンと混合する場合は、混合物で不
飽和カルボン酸等のグラフト量が前記範囲内に入る限り
、やや高濃度、通常２５重量％までのグラフト量の変性
ポリ４−メチル−１−ペンテンを用いてもよい。Modified poly-4-methyl-1 constituting the resin composition of the present invention
- Pentene may be poly-4-methyl-1-pentene completely graft-modified with unsaturated carboxylic acid or unmodified poly-4-methyl, as long as the grafting amount of unsaturated carboxylic acid or its derivative is within the above range. -1-Pentene, i.e. partially modified poly-4-methyl-1-pentene, or unmodified poly-4-methyl-1-pentene
- When mixed with methyl-1-pentene, as long as the amount of grafting of unsaturated carboxylic acid, etc. in the mixture falls within the above range, modified poly-4-methyl-1 may be used at a slightly higher concentration, usually up to 25% by weight of grafting. - Pentene may also be used.
次に本発明に用いるポリフェニレンスルフィドは、構造
式へ匝温ｓ−５で示される繰り返し単位を主成分とする
ものであり、少量の他の共重合可司シ０合Ｓ＋、ポジｓ
ｏ、合Ｓ＋、
これらのポリフェニレンスルフィドは、３００℃、すり
速度； ＝ ２００ｓｅｃ−”の条件下での溶融粘度が
好ましくは５０ないし５ｏｏｏｏポイズ、特に１００な
いし５０００ポイズの範囲にあるのが好ましい。Next, the polyphenylene sulfide used in the present invention is mainly composed of a repeating unit represented by a structural formula with a temperature of s-5, and a small amount of other copolymerized resins, s+, s+, and s-5.
These polyphenylene sulfides preferably have a melt viscosity of 50 to 5000 poise, particularly 100 to 5000 poise, at 300° C. and a sliding speed of 200 sec.
本発明に用いる強化繊維としては、ガラス繊維。The reinforcing fiber used in the present invention is glass fiber.
炭素繊維、ボロン繊維、チタン酸カリウム繊維、ウオラ
ストナイト、アスベスト繊維等の無機物あるいはケブラ
ー等の商標で知られるアラミド繊維等の有機物からなる
繊維状物質などがあげられる。Examples include fibrous materials made of inorganic materials such as carbon fibers, boron fibers, potassium titanate fibers, wollastonite, and asbestos fibers, and organic materials such as aramid fibers known under trademarks such as Kevlar.
また繊維の表面をシラン系化合物、例えばビニルトリエ
トキシシラン、γ−アミノプロピルトリエトキシシラン
、γ−アミノプロピルトリメトキシシラン、Ｎ−（β−
アミノエチル）−γ−アミノプロピルトリメトキシシラ
ン、γ−グリシドキシプロビルトリメトキシシラン等で
処理しておいてもよい。The surface of the fibers may also be coated with silane compounds such as vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-
It may be treated with γ-aminopropyltrimethoxysilane (aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or the like.
本発明の樹脂組成物は、上記ポリ４−メチル−１−ペン
テン８０〜９０重量％、好ましくは８０〜８７重量％、
およびポリフェニレンスルフィド１０〜２０重量％、好
ましくは１３〜２０重量％を含有する樹脂分１００重量
部に対して、強化繊維１０〜６０重量部を含有する組成
物である。The resin composition of the present invention comprises 80 to 90% by weight of the above poly-4-methyl-1-pentene, preferably 80 to 87% by weight,
The composition contains 10 to 60 parts by weight of reinforcing fibers per 100 parts by weight of a resin containing 10 to 20% by weight, preferably 13 to 20% by weight of polyphenylene sulfide.
上記の樹脂組成物においては、ポリ４−メチル−１−ペ
ンテンは樹脂組成物の主要部を占めるため、これに少量
のポリフェニレンスルフィドおよび強化繊維を配合して
も、ポリ４−メチル−１−ペンテンの融点を超えて形状
を保持することは常識的に考えられないが、上記組成と
することにより耐熱性は改善され、ポリ４−メチル−１
−ペンテンの融点より高い温度でも形状を保持すること
ができ、耐熱老化性、耐熱剛性等も向上する。In the above resin composition, since poly-4-methyl-1-pentene occupies the main part of the resin composition, even if a small amount of polyphenylene sulfide and reinforcing fibers are added, poly-4-methyl-1-pentene Although it is common sense that poly-4-methyl-1 cannot maintain its shape beyond its melting point, the heat resistance is improved by using the above composition.
- It can maintain its shape even at temperatures higher than the melting point of pentene, and its heat aging resistance and heat resistance rigidity are also improved.
本発明の樹脂組成物には、耐熱安定剤、耐候安定剤、難
燃剤、核剤、顔料、染料、滑剤、発錆防止剤等の通常ポ
リオレフィンに添加混合して用いることのできる各種配
合剤を本発明の目的を損なわない範囲で添加してもよい
。The resin composition of the present invention contains various compounding agents that can be added and mixed with ordinary polyolefins, such as heat stabilizers, weather stabilizers, flame retardants, nucleating agents, pigments, dyes, lubricants, and rust inhibitors. It may be added within a range that does not impair the purpose of the present invention.
たとえば難燃剤としては、トリクレジルホスフェート、
クレジルジフェニルホスフェート、ジフェニルオクチル
ホスフェート、トリブチルホスフェート等の燐酸エステ
ル、トリス（β−クロルエチル）ホスフェート、トリス
（ジクロルプロピル）ホスフエート、トリス（２，３−
ジブロムプロピル）ホスフェート、トリス（ブロムクロ
ルプロピル）ホスフェート等の含ハロゲン燐酸エステル
、塩素化パラフィン、塩素化ポリエチレン、臭素化ポリ
フェニル、塩素化ポリフェニル、デクロラン、デクロラ
ンプラス、テトラブロムエタン、テトラブロムブタン、
１，２−ジブロム−３−クロルプロパン、１，２．３−
トリブロムプロパン、ヘキサブロムシクロドデカン、テ
トラブロムベンゼン、塩素化ジフェニル、デカブロムジ
フェニルオキシド、Ｎ、Ｎ’−エチレンビスーテトラブ
ロムフタルイミド、トリブロモポリスチレン、ポリジブ
ロモベンゼンオキシド、ビストリブロモフェノキシエタ
ン等のハロゲン化合物、二酸化アンチモン、酒石酸アン
チモンカリウム、トリフェニルスチビン等のアンチモン
系化合物、硼砂、硼酸亜鉛、メタ硼酸バリウム等の硼素
系化合物、水酸化マグネシウム、水酸化アルミニウム、
水酸化カルシウム、水酸化バリウム等の金属水酸化物な
どがあり、これらの中ではハロゲン化合物とくにデクロ
ラン、デカブロムジフェニルオキシド、Ｎ、Ｎ’−エチ
レンビス−テトラブロムフタルイミド、臭素化エポキシ
等のハロゲン化合物と二酸化アンチモンとの併用あるい
は水酸化マグネシウムが耐熱性１機械的強度の低下を招
くことなく難燃性を付与できるので好ましい。For example, flame retardants include tricresyl phosphate,
Phosphate esters such as cresyl diphenyl phosphate, diphenyloctyl phosphate, tributyl phosphate, tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (2,3-
Halogen-containing phosphate esters such as dibromopropyl) phosphate, tris(bromochloropropyl)phosphate, chlorinated paraffin, chlorinated polyethylene, brominated polyphenyl, chlorinated polyphenyl, dechlorane, dechlorane plus, tetrabromoethane, tetrabrome butane,
1,2-dibromo-3-chloropropane, 1,2.3-
Halogen compounds such as tribromopropane, hexabromocyclododecane, tetrabromobenzene, chlorinated diphenyl, decabromo diphenyl oxide, N,N'-ethylenebis-tetrabromophthalimide, tribromopolystyrene, polydibromobenzene oxide, bistribromophenoxyethane, etc. , antimony compounds such as antimony dioxide, potassium antimony tartrate, triphenylstibine, boron compounds such as borax, zinc borate, barium metaborate, magnesium hydroxide, aluminum hydroxide,
There are metal hydroxides such as calcium hydroxide and barium hydroxide, and among these, halogen compounds such as dechlorane, decabromidiphenyl oxide, N,N'-ethylenebis-tetrabromphthalimide, and brominated epoxy A combination of antimony dioxide and antimony dioxide or magnesium hydroxide is preferable because flame retardancy can be imparted without causing a decrease in heat resistance 1 and mechanical strength.
本発明の樹脂組成物を得る方法としては、前記各成分を
前記範囲で混合することにより得られる。The resin composition of the present invention can be obtained by mixing the above-mentioned components within the above-mentioned ranges.
混合方法としては種々公知の方法例えばヘンシェルミキ
サー、■−ブレンダー、リボンブレンダータンブラーブ
レンダー等で混合する方法、混合後頁に一軸押出機、二
軸押出機、ニーダ−等により溶融混線後、造粒あるいは
粉砕する方法があげられる。There are various known methods for mixing, such as Henschel mixer, ■-blender, ribbon blender, tumbler blender, etc. After mixing, melt mixing using a single screw extruder, twin screw extruder, kneader, etc., followed by granulation or One method is to crush it.
本発明の樹脂組成物は射出成形、圧縮成形、押出成形等
の一般の成形方法により樹脂成形物とされるが、このう
ち射出成形を行うと、ポリフェニレンスルフィドおよび
強化繊維が成形物の表層部において層状の複合連続相を
形成するため、成形物の耐熱性が大幅に向上し、特に耐
熱老化性および耐熱剛性が優れた成形物が得られる。The resin composition of the present invention is made into a resin molded product by general molding methods such as injection molding, compression molding, and extrusion molding. When injection molding is performed, polyphenylene sulfide and reinforcing fibers are formed in the surface layer of the molded product. Since a layered composite continuous phase is formed, the heat resistance of the molded product is greatly improved, and a molded product with particularly excellent heat aging resistance and heat-resistant rigidity can be obtained.
第１図は射出成形により製造された後述の実施例１の樹
脂成形物の表層部における組成物を構成するポリマーの
分散状態を示す断面の顕微鏡写真（４５０倍）、第２図
は同じく中央部の分散状態を示す断面の顕微鏡写真（４
５０倍）であり、表層部にポリフェニレンスルフィドお
よび強化繊維の層状の複合連続相が形成されていること
がわかる。Figure 1 is a micrograph (450x) of a cross section showing the dispersion state of the polymer constituting the composition in the surface layer of the resin molded product of Example 1, which will be described later, manufactured by injection molding, and Figure 2 is the same at the center. A micrograph of a cross section showing the dispersion state of
50 times), and it can be seen that a layered composite continuous phase of polyphenylene sulfide and reinforcing fibers is formed in the surface layer.
本発明によれば、ポリ４−メチル−１−ペンテンにポリ
フェニレンスルフィドおよび強化繊維を配合したので、
ポリ ４−メチル−１−ペンテン樹脂の融点より高い温
度で形状を保持することが可能で、かつ優れた耐熱老化
性および耐熱剛性を有するポリ４−メチル−１−ペンテ
ン樹脂組成物が得られる。According to the present invention, since polyphenylene sulfide and reinforcing fiber are blended with poly4-methyl-1-pentene,
A poly-4-methyl-1-pentene resin composition is obtained that can maintain its shape at a temperature higher than the melting point of the poly-4-methyl-1-pentene resin and has excellent heat aging resistance and heat-resistant rigidity.
また本発明のポリ４−メチル−１−ペンテン樹脂成形物
は、表層部においてポリフェニレンスルフィドおよび強
化繊維が層状の複合連続相を形成しているので、耐熱老
化性および耐熱剛性はさらに向上する。Furthermore, since the polyphenylene sulfide and reinforcing fibers form a layered composite continuous phase in the surface layer of the poly4-methyl-1-pentene resin molded product of the present invention, heat aging resistance and heat resistance rigidity are further improved.
次に実施例を挙げて本発明をさらに具体的に説明するが
５本発明はこれら実施例に限定されるものではない。Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.
１ ポリオレフィンの
４−メチル−１−ペンテン単独重合体（［η］ １．７
ｄＲ／ｇ、Ｍｗ／Ｍｎ ７．５、融点２４１’Ｃ１結晶
化度４２％、ＤＳＣパラメータ３．０）を用い、トルエ
ン溶媒中、１４５℃でジクミルペルオキシド触媒により
無水マレイン酸のグラフト反応を行った。得られた反応
物に大過剰のアセトンを加えることにより、ポリマーを
沈澱させ、濾取し、沈澱物をアセトンで繰返し洗浄する
ことにより、無水マレイン酸グラフト変性ポリ４−メチ
ル−１−ペンテンＡ（以下変性ＴＰＸ（Ａ）と呼ぶ）を
得た。1 Polyolefin 4-methyl-1-pentene homopolymer ([η] 1.7
dR/g, Mw/Mn 7.5, melting point 241'C1 crystallinity 42%, DSC parameters 3.0), the grafting reaction of maleic anhydride was carried out with dicumyl peroxide catalyst at 145 °C in toluene solvent. Ta. By adding a large excess of acetone to the obtained reaction product, the polymer was precipitated, collected by filtration, and the precipitate was repeatedly washed with acetone to obtain maleic anhydride graft-modified poly-4-methyl-1-pentene A ( (hereinafter referred to as modified TPX (A)) was obtained.
この変性ポリマーの無水マレイン酸単位のグラフト割合
は、４．０重量％であり、［η］ ０．９５ｄＱ／ｇ、
融点２１０℃、結晶化度１８％、ＭＩ＃／Ｍｎ ４．５
、ＤＳＣパラメータ２．８であった。The grafting ratio of maleic anhydride units in this modified polymer was 4.0% by weight, [η] 0.95dQ/g,
Melting point 210°C, crystallinity 18%, MI#/Mn 4.5
, DSC parameter was 2.8.
参考例２ 性ポリオレフィンの製造
４−メチル−１−ペンテン単独重合体（［η］ ３．８
ｄＱ／ｇ、Ｍｗ／Ｍｎ ７．３、融点２４０℃、結晶化
度４１％、ＤＳＣパラメータ３．２）に対し、無水マレ
イン酸および２，５−ジメチル−２，５−ジ（ｔｅｒｔ
−ブチルペルオキシ）ヘキシン−３を添加し、この混合
物をＮ３雰囲気下２６０℃に設定した一軸押出機に供給
し、溶融混練することにより、無水マレイン酸グラフト
変性ポリ４−メチル−１−ペンテンＢ（以下変性ＴＰＸ
（Ｂ ）と呼ぶ）を得た。Reference Example 2 Production of polyolefin 4-methyl-1-pentene homopolymer ([η] 3.8
dQ/g, Mw/Mn 7.3, melting point 240°C, crystallinity 41%, DSC parameters 3.2), maleic anhydride and 2,5-dimethyl-2,5-di(tert
-butylperoxy)hexyne-3 was added, and the mixture was supplied to a single-screw extruder set at 260°C under an N3 atmosphere and melt-kneaded to produce maleic anhydride graft-modified poly4-methyl-1-pentene B ( Modified TPX below
(B)) was obtained.
この変性ポリマーの無水マレイン酸単位のグラフト割合
は、１．４重量％であり、［η］ ０．１５ｄＱ／ｇ、
融点２１２℃、結晶化度２４％、Ｍｙ／Ｍｎ ５．２、
ＤＳＣパラメータ４．３であった。The grafting ratio of maleic anhydride units in this modified polymer was 1.4% by weight, [η] 0.15dQ/g,
Melting point 212°C, crystallinity 24%, My/Mn 5.2,
The DSC parameter was 4.3.
去ｍ本、ｉｕ側
ポリフェニレンスルフィド（ｐｐｓ、トーブレン社製Ｔ
−４）と、参考例で得たＴＰＸ （Ａ）および未変性ポ
リ４−メチル−１−ペンテン（三井石油化学工業株式会
社製、ＴＰＸ （登録商標） ＲＴ１８）、さらにガラ
ス繊維（ＧＦ）とを表１に示す割合で混合した後、二軸
押出機を用いて成形温度２９０℃で溶融混練し１次いで
射出成形機（東芝機械社製ｌ５５０）によって２９０℃
で射出成形して厚さ０．５ｍｍのキャップ状の薄肉の樹
脂成形品を得た。Iu side polyphenylene sulfide (pps, T made by Torblen)
-4), TPX (A) obtained in Reference Example, unmodified poly-4-methyl-1-pentene (manufactured by Mitsui Petrochemical Industries, Ltd., TPX (registered trademark) RT18), and glass fiber (GF). After mixing in the proportions shown in Table 1, the mixture was melt-kneaded using a twin-screw extruder at a molding temperature of 290°C, and then heated to 290°C using an injection molding machine (L550 manufactured by Toshiba Machinery Co., Ltd.).
A cap-shaped thin resin molded product with a thickness of 0.5 mm was obtained by injection molding.
上記の樹脂成形品をオーブンに入れ、所定の温度を５分
間維持し、形状保持性テストを行った。The above resin molded product was placed in an oven, a predetermined temperature was maintained for 5 minutes, and a shape retention test was conducted.
結果を表１に示す。The results are shown in Table 1.
夫鞭災Ａ
実施例１におけるＴＰＸとＴＰＸ （Ａ）の代わりに、
参考例２で得たＴＰＸ （Ｂ）を使用した以外は、実施
例１と同様に行った。In place of TPX and TPX (A) in Example 1,
The same procedure as in Example 1 was performed except that TPX (B) obtained in Reference Example 2 was used.
結果を表１に示す。The results are shown in Table 1.
匝敗斑よ
実施例１において、ＧＦを除きＴ−４を１５重量％に減
量し、しかもＴＰＸを８４重量％に増量した以外は、実
施例１と同様に行った。The same procedure as in Example 1 was repeated except that GF was removed, T-4 was reduced to 15% by weight, and TPX was increased to 84% by weight.
結果を表１に示す。The results are shown in Table 1.
崖笠桝主
実施例１において、Ｔ−４を除きＴＰＸを９９重量％に
増量した以外は、実施例１と同様に行った。Example 1 was carried out in the same manner as in Example 1, except that T-4 was removed and TPX was increased to 99% by weight.
結果を表１に示す。The results are shown in Table 1.
共１Ｌ匠３
実施例１において、ＧＦを用いず、しかもＰＰＳを４０
重量％に増量し、ＴＰＸを５９重量％に減量した以外は
、実施例１と同様に行った。Both 1L Takumi 3 In Example 1, GF was not used and PPS was 40
The same procedure as in Example 1 was conducted except that the amount of TPX was increased to 59% by weight and the amount of TPX was decreased to 59% by weight.
結果を表１に示す。The results are shown in Table 1.
表 １ 注）０：外観の変化が全く認められない。Table 1 Note) 0: No change in appearance observed at all.
Δ：形状の変形は認められないが表面の肌が荒れている
。Δ: No shape deformation is observed, but the surface texture is rough.
Ｘ：形状が大きく崩れている。X: The shape is greatly distorted.
４、4,
第１図および第２図は本発明の樹脂成形物の粒子構造を
示す顕微鏡写真である。FIGS. 1 and 2 are micrographs showing the particle structure of the resin molded product of the present invention.
Claims (2)
およびポリフェニレンスルフィド１０〜２０重量％を含
有する樹脂分１００重量部に対して、強化繊維１０〜６
０重量部を含有することを特徴とする耐熱性ポリ４−メ
チル−１−ペンテン樹脂組成物。(1) Poly 4-methyl-1-pentene 80-90% by weight
and 10 to 6 parts by weight of reinforcing fibers per 100 parts by weight of the resin containing 10 to 20% by weight of polyphenylene sulfide.
A heat-resistant poly-4-methyl-1-pentene resin composition, characterized in that it contains 0 parts by weight.
およびポリフェニレンスルフィド１０〜２０重量％を含
有する樹脂分１００重量部に対して、強化繊維１０〜６
０重量部を含有し、ポリフェニレンスルフィドが表層部
において層状の連続相を形成していることを特徴とする
耐熱性ポリ４−メチル−１−ペンテン樹脂成形物。(2) Poly 4-methyl-1-pentene 80-90% by weight
and 10 to 6 parts by weight of reinforcing fibers per 100 parts by weight of the resin containing 10 to 20% by weight of polyphenylene sulfide.
1. A heat-resistant poly-4-methyl-1-pentene resin molded article containing 0 parts by weight of polyphenylene sulfide and forming a layered continuous phase in the surface layer.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21974988A JPH0267348A (en) | 1988-09-02 | 1988-09-02 | Heat-resistant poly(4-methyl-1-pentene) resin composition and molded item thereof |
| MYPI89001179A MY104182A (en) | 1988-09-02 | 1989-08-28 | Heat resistant poly-4-methyl-1-pentene resin composition and shaped article thereof. |
| EP19890308776 EP0360439A3 (en) | 1988-09-02 | 1989-08-30 | Heat resistant poly-4-methyl-1-pentene resin compostition and shaped article thereof |
| CN89107757A CN1042945C (en) | 1988-09-02 | 1989-09-02 | Heat resistant poly-4-methyl 1-pentene composition and shaped article thereof |
| KR1019890012691A KR910008890B1 (en) | 1988-09-02 | 1989-09-02 | Heat-resistant poly-4-methyl-1-pentene resin composition and the molded article therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21974988A JPH0267348A (en) | 1988-09-02 | 1988-09-02 | Heat-resistant poly(4-methyl-1-pentene) resin composition and molded item thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0267348A true JPH0267348A (en) | 1990-03-07 |
Family
ID=16740391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21974988A Pending JPH0267348A (en) | 1988-09-02 | 1988-09-02 | Heat-resistant poly(4-methyl-1-pentene) resin composition and molded item thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0267348A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160118159A1 (en) * | 2014-01-22 | 2016-04-28 | Sumitomo Electric Industries, Ltd. | Insulated electrical wire and coaxial cable |
-
1988
- 1988-09-02 JP JP21974988A patent/JPH0267348A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160118159A1 (en) * | 2014-01-22 | 2016-04-28 | Sumitomo Electric Industries, Ltd. | Insulated electrical wire and coaxial cable |
| US9799422B2 (en) * | 2014-01-22 | 2017-10-24 | Sumitomo Electric Industries, Ltd. | Insulated electrical wire and coaxial cable |
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