JPH02178339A - Heat resistant polyolefin resin composition and resin molded article - Google Patents
Heat resistant polyolefin resin composition and resin molded articleInfo
- Publication number
- JPH02178339A JPH02178339A JP33503688A JP33503688A JPH02178339A JP H02178339 A JPH02178339 A JP H02178339A JP 33503688 A JP33503688 A JP 33503688A JP 33503688 A JP33503688 A JP 33503688A JP H02178339 A JPH02178339 A JP H02178339A
- Authority
- JP
- Japan
- Prior art keywords
- polyolefin
- ethylene
- polyphenylene sulfide
- propylene
- 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 abstract description 18
- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 15
- 229920005989 resin Polymers 0.000 title description 26
- 239000011347 resin Substances 0.000 title description 26
- 229920000098 polyolefin Polymers 0.000 claims abstract description 27
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 19
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 16
- 239000002344 surface layer Substances 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000001746 injection moulding Methods 0.000 abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 229920001684 low density polyethylene Polymers 0.000 abstract description 4
- 239000004702 low-density polyethylene Substances 0.000 abstract description 4
- 230000003679 aging effect Effects 0.000 abstract 1
- 238000003878 thermal aging Methods 0.000 abstract 1
- -1 Polyethylene Polymers 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- 239000004711 α-olefin Substances 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002366 halogen compounds Chemical class 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 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
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-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
- 239000002253 acid Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 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 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
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000748 compression moulding Methods 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
- 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
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000101 thioether group Chemical group 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
- QRFALSDGOMLVIR-UHFFFAOYSA-N 1,2,3,4-tetrabromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1Br QRFALSDGOMLVIR-UHFFFAOYSA-N 0.000 description 1
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 1
- FHCLGDLYRUPKAM-UHFFFAOYSA-N 1,2,3-tribromopropane Chemical compound BrCC(Br)CBr FHCLGDLYRUPKAM-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
- WXLQTJWFQSFIGM-UHFFFAOYSA-N 2,2-dibromo-1-chloropropane Chemical compound CC(Br)(Br)CCl WXLQTJWFQSFIGM-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
- 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 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
- 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
- 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
- 208000035051 Malignant migrating focal seizures of infancy Diseases 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
- 239000007983 Tris buffer Substances 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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
- 239000004917 carbon fiber 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
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000002178 crystalline material Substances 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
- 230000002542 deteriorative 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
- 150000001993 dienes 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 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
- 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
- 239000003365 glass fiber Substances 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
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection 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
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 208000012054 malignant migrating partial seizures of infancy Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 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
- 238000001000 micrograph Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-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
- 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
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 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
- 239000007921 spray Substances 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
- 229920005992 thermoplastic resin Polymers 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
たポリオレフィ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 [Industrial Field of Application] The present invention relates to a polyolefin resin composition and a resin molded article having excellent heat resistance, particularly heat aging resistance and heat resistance rigidity.
ポリエチレン、ポリプロピレンは耐薬品性、電気特性、
成形性などの優れた特性を有し、代表的な熱可塑性樹脂
として広く利用されている。しがしながら、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、これら樹脂の使用範囲はその融点より低い温
度が限界であった・
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重景％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、ここではポリオレフ
ィ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。Polyethylene and polypropylene have chemical resistance, electrical properties,
It has excellent properties such as moldability and is widely used as a typical thermoplastic resin. However, at temperatures higher than their melting point, they cannot maintain their shape, and the range of use of these resins is limited to temperatures below their melting point.On the other hand, after acid treatment, A resin composition containing 70 to 97% by weight of a washed polyphenylene sulfide resin and 30 to 3% by weight of an olefin copolymer containing α-olefin and glycidyl ester of α,β-unsaturated acid as essential components. has been proposed as a polyphenylene sulfide resin composition with improved impact properties (Japanese Unexamined Patent Publication No. 1983-1999).
No. 153343). However, this document does not disclose anything about improving the heat resistance of polyolefin resins.
本発明の目的は、エチレンまたはプロピレンを主体とす
るポリオレフィン樹脂のｉｔ熱性を改善し。The object of the present invention is to improve the thermal properties of polyolefin resins mainly composed of ethylene or propylene.
ポリオレフィ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ａｈた耐熱老化性および耐熱剛性
を有するポリオレフィン樹脂組成物および樹脂成形物を
提供することである。It is an object of the present invention to provide a polyolefin resin composition and a resin molding that can maintain their shape at a temperature higher than the melting point of the polyolefin resin and have excellent heat aging resistance and heat resistance rigidity.
本発明は、次の耐熱性ポリオレフィ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 polyolefin resin composition and resin molding.
（１，）エチレンまたはプロピレンを主体とするポリオ
レフィン４０〜７８重量％、およびポリフェニレンスル
フィド２２〜６０重量％を含有することを特徴とする耐
熱性ポリオレフィン樹脂組成物。(1.) A heat-resistant polyolefin resin composition containing 40 to 78% by weight of a polyolefin mainly composed of ethylene or propylene, and 22 to 60% by weight of polyphenylene sulfide.
（２）エチレンまたはプロピレンを主体とするポリオレ
フィン４０〜７８重量％、およびポリフェニレンスルフ
ィド２２〜６０重量％を含有し、ポリフェニレンスルフ
ィドが表層部においてｊ−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オレフィン樹脂成形物。(2) It is characterized by containing 40 to 78% by weight of polyolefin mainly composed of ethylene or propylene and 22 to 60% by weight of polyphenylene sulfide, with the polyphenylene sulfide forming a J-shaped continuous phase in the surface layer. A heat-resistant polyolefin resin molded product.
本発明に用いるポリオレフィンはエチレンまたはプロピ
レンを主体とするものであり、具体的にはポリエチレン
および／またはポリプロピレンがあげられる。The polyolefin used in the present invention is mainly composed of ethylene or propylene, and specifically includes polyethylene and/or polypropylene.
本発明に用いるポリエチレンとしては、低密度ポリエチ
レン樹脂、線状低密度ポリエチレン樹脂および高密度ポ
リエチレン樹脂などがあげられる。Examples of the polyethylene used in the present invention include low-density polyethylene resin, linear low-density polyethylene resin, and high-density polyethylene resin.
低密度ポリエチレン樹脂は、エチレンの貼独重合体また
はエチレン・α−オレフィン共重合体であり、１ｏｏｏ
〜２０００気圧、 ２００〜３００℃でラジカル重合し
て合成する高圧法により合成される。 α−オレフィン
としては、炭素数が：３〜２０のもの１例えばプロピレ
ン、ｌ−ブテン等があげられる。 α−オレフィンの含
有量は１５モル％以下、好ましくは１０モル％以下であ
る。The low-density polyethylene resin is a self-adhesive polymer of ethylene or an ethylene/α-olefin copolymer.
It is synthesized by a high-pressure method of radical polymerization at ~2000 atm and 200-300°C. Examples of the α-olefin include those having 3 to 20 carbon atoms, such as propylene and l-butene. The content of α-olefin is 15 mol% or less, preferably 10 mol% or less.
このような低密度ポリエチレン樹脂はＭＦＲｌ、。。Such low density polyethylene resin is MFRl. .
（メルトフローレート： ＡＳＴＭ ０１２３８、（Ｉ
Ｉ）がＱ、５〜５０ｇ／１０分、好ましくは３〜２０ｇ
／１０分、密度が０．９０９〜０．９４０ｇ／ｆｆ１．
好ましくは０．９１５〜０．９３０ｇ／ｃｍのものが好
ましい。(Melt flow rate: ASTM 01238, (I
I) is Q, 5-50g/10 minutes, preferably 3-20g
/10 minutes, density is 0.909-0.940g/ff1.
Preferably, it is 0.915 to 0.930 g/cm.
線状低密度ポリエチレン樹脂は、エチレンと炭素数４〜
２０の α−オレフィンからなるコモノマーの共重合体
であり、３５〜１００気圧で触媒を用いて合成する中圧
法、０〜７気圧で触媒を用いて合成する低圧法などによ
り合成される。コモノマーとしては、例えば１−ブテン
、４−メチル−１−ペンテン、ｌ−ヘキセン、１−オク
テン等があげられる。コモノマーの含有量は通常１〜５
モル％である。このような線状低密度ポリエチレン樹脂
は、ＭＦＲｌ、。、が通常０．１〜５０ｇ／１０分、密
度が通常０．９１〜０．９４ｇ／ａｊである。Linear low-density polyethylene resin has ethylene and carbon atoms of 4 to 4.
It is a copolymer of comonomers consisting of 20 α-olefins, and is synthesized by a medium pressure method using a catalyst at 35 to 100 atmospheres, or a low pressure method using a catalyst at 0 to 7 atmospheres. Examples of the comonomer include 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. The comonomer content is usually 1 to 5
It is mole%. Such linear low density polyethylene resin is MFRl. is usually 0.1 to 50 g/10 min, and the density is usually 0.91 to 0.94 g/aj.
高密度ポリエチレン樹脂は、エチレン単独重合体または
エチレン・α−オレフィン共重合体からなり、チーグラ
ー・ナツタ触媒等による低圧法、フィリップス法等の中
圧法等により合成される。α−オレフィンとしては、炭
素数が３〜１０のもの、例えばプロピレン、ｌ−ブテン
等があげられ、 α−オレフィン含有斌は１５モル％以
下、好ましくは１０モル％以下が好ましい。このような
高密度ポリエチレン樹脂は、ＭＦＲｌ、。、が０．０１
〜５０ｇ／１０分、好ましくはｏ、ｉ〜２０ｇ／ｌＯ分
、密度が０．９４〜０．９７ｇ／ｆｆｌ、好ましくは０
．９５〜０．９６５ｇ／−である。The high-density polyethylene resin is composed of an ethylene homopolymer or an ethylene/α-olefin copolymer, and is synthesized by a low-pressure method using a Ziegler-Natsuta catalyst, a medium-pressure method such as the Phillips method, or the like. Examples of the α-olefin include those having 3 to 10 carbon atoms, such as propylene and l-butene, and the α-olefin content is preferably 15 mol% or less, preferably 10 mol% or less. Such high density polyethylene resin is MFRl. , is 0.01
~50g/10min, preferably o, i~20g/lOmin, density 0.94~0.97g/ffl, preferably 0
．． 95 to 0.965 g/-.
上記のポリエチレンには２場合によって少量、例えば３
０重量％以下の酢酸ビニルを含むエチレン・酢酸ビニル
共重合体などを混合することもでき。The above polyethylene may contain 2 optionally small amounts, e.g.
It is also possible to mix an ethylene/vinyl acetate copolymer containing 0% by weight or less of vinyl acetate.
また９鼠のプロピレン、非共役ジエンを含むエチレン・
プロピレン・非共役ジエン共重合体を混合することもで
きる。In addition, 9% of propylene, ethylene containing non-conjugated dienes, etc.
A propylene/non-conjugated diene copolymer may also be mixed.
本発明に用いるポリプロピレンとしては、ＭＦＲ２３，
、ｃ、（ＡＳＴＭ Ｄ１２３８（Ｌ））がｏ、ｉ〜５０
ｇ／１０分、好ましくは０．５〜２０ｇ／１０分であり
、 プロピレンの噴独重合体、ならびにプロピレンと１
５モル％以下、好ましくは１０モル％以下のエチレン、
１−ブテン、４−メチル−１−ペンテン、トヘキセン、
■−オクテン、１−デセンなど、他のα−オレフィン
との共重合体が用いられる。The polypropylene used in the present invention includes MFR23,
, c, (ASTM D1238(L)) is o, i ~ 50
g/10 minutes, preferably 0.5 to 20 g/10 minutes, and propylene spray polymer as well as propylene and 1 g/10 minutes.
5 mol% or less, preferably 10 mol% or less of ethylene,
1-butene, 4-methyl-1-pentene, tohexene,
(2) Copolymers with other α-olefins such as -octene and 1-decene are used.
本発明で用いるポリオレフィンとしては、上記のポリエ
チレンおよびポリプロピレンをそれぞれ単独でまたは混
合して用いることができ、さらに他の樹脂またはゴム成
分を配合することもできる。As the polyolefin used in the present invention, the above-mentioned polyethylene and polypropylene can be used alone or in combination, and other resins or rubber components can also be blended.
本発明では上記のようなポリオレフィンは不飽和カルボ
ン酸またはその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, the polyolefin as described above may be partially or completely modified with an unsaturated carboxylic acid or a derivative thereof.
ここで用いられる変性ポリオレフィンとしては、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ｏ、ｏｉ〜１０重量％、
好ましくは０．１〜５重量％の範囲でグラフト変性され
たポリオレフィンであり、通常デカリン溶媒１３５℃に
おける極限粘度が０．４〜１５ｄＱ／ｇ、好ましくは０
．６〜１０ｄＱ／ｇの範囲、融点（ＡＳＴＭ ０３４１
８）が１３０℃以上の結晶性のものが使用できる。上記
範囲の特性値を有する変性ポリオレフィンは、ポリフェ
ニレンスルフィドとの相溶性、耐熱性、機械的強度、耐
水性に優れているので好ましい。The modified polyolefin used here is partially or entirely a graft monomer selected from unsaturated carboxylic acids or derivatives thereof, o, oi to 10% by weight,
It is preferably a polyolefin graft-modified in a range of 0.1 to 5% by weight, and usually has an intrinsic viscosity of 0.4 to 15 dQ/g at 135°C in a decalin solvent, preferably 0.
．． Range of 6-10 dQ/g, melting point (ASTM 0341
8) A crystalline material with a temperature of 130° C. or higher can be used. A modified polyolefin having characteristic values within the above range is preferable because it has excellent compatibility with polyphenylene sulfide, heat resistance, mechanical strength, and water resistance.
本発明において前記ポリオレフィ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。In the present invention, the unsaturated carboxylic acid or its derivative to be grafted to the polyolefin is as follows.
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，
２，１１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、特にマレイン酸、ナ
ジック酸またはこれらの酸無水物が好適である。Acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo[2,
Unsaturated carboxylic acids such as 2,11hept-5-ene-2,3-dicarboxylic acid (registered trademark) or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc. , maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like. 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オレフィンにグラフト共
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。Various conventionally known methods can be employed to produce a modified product by graft copolymerizing a graft monomer selected from these unsaturated carboxylic acids or derivatives thereof onto the polyolefin.
例えば、重合体を溶融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、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。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。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。 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。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（ｔｅｒ
ｔ−ブチルペルオキシ）ヘキシン−３、２，５−ジメチ
ル−２，５−ジ（ｔａｒｔ−ブチルペルオキシ）ヘキサ
ン。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. 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. The grafting reaction is usually carried out at a temperature of 60 to 350°C. 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. As radical initiators, organic peroxides, organic bersesters,
Other examples include azo compounds. Among these radical initiators, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert)
t-butylperoxy)hexane-3,2,5-dimethyl-2,5-di(tart-butylperoxy)hexane.
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
。Dialkyl peroxides such as 1,4-bis(tart-butylperoxyisopropyl)benzene are preferred.
本発明の樹脂組成物を構成する変性ポリオレフィンは、
不飽和カルボン酸またはその誘導体のグラフト社が前記
範囲内にある限り、全部が不飽和カルボン酸等でグラフ
ト変性されたポリオレフィンまたは未変性のポリオレフ
ィンとの混合物、すなわち一部が変性された変性ポリオ
レフィンであってもよい。なお、未変性のポリオレフィ
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２
５重量％までのグラフト量の変性ポリオレフィンを混合
してもよい。The modified polyolefin constituting the resin composition of the present invention is
As long as the amount of grafting of unsaturated carboxylic acids or derivatives thereof is within the above range, polyolefins that are entirely graft-modified with unsaturated carboxylic acids or the like or mixtures with unmodified polyolefins, i.e., modified polyolefins that are partially modified, are used. There may be. In addition, when mixing with unmodified polyolefin, as long as the amount of grafted unsaturated carboxylic acid etc. in the mixture falls within the above range, the concentration is slightly higher, usually 2.
A grafted amount of up to 5% by weight of modified polyolefins may be mixed.
本発明に用いるポリフェニレンスルフィドは、成分とす
るものであり、少量の他の共重合可能なこれらのポリフ
ェニレンスルフィドは、３００℃、すり速度す＝ ２０
０ｓｅｃ−’の条件下での溶融粘度が好ましくは５０〜
５ｏｏｏｏボイズ、 特に１００〜１００００ボイズの
範囲にあるのが好ましい。The polyphenylene sulfide used in the present invention is a component, and a small amount of other copolymerizable polyphenylene sulfide is used at a temperature of 300°C and a sliding speed of 20.
The melt viscosity under the condition of 0 sec-' is preferably 50~
It is preferably in the range of 5oooo voids, particularly 100 to 10,000 voids.
本発明の樹脂組成物は、上記のエチレンまたはプロピレ
ンを主体とするポリオレフィン４０〜７８″Ａｉ麓％、
好ましくは６０〜７８重電％、およびポリフェニレンス
ルフィド２２〜６０重量％、好ましくは２２〜４０重量
％を必須成分とする組成物である。The resin composition of the present invention comprises the above-mentioned polyolefin mainly composed of ethylene or propylene, with 40 to 78"Ai foot%,
The composition preferably contains 60 to 78% by weight of heavy electric current and 22 to 60% by weight, preferably 22 to 40% by weight of polyphenylene sulfide as essential components.
上記の樹脂組成物においては、エチレンまたはプロピレ
ンを主体とするポリオレフィ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を
配合しても、ポリオレフィ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、ポリオレフィンの融点より
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, polyolefin mainly composed of ethylene or propylene occupies the main part of the resin composition, so even if a small amount of polyphenylene sulfide is blended with it, the shape will not be retained beyond the melting point of the polyolefin. Although this cannot be considered in common sense, the above composition improves heat resistance, allows it to maintain its shape even at temperatures higher than the melting point of polyolefin, and improves heat aging resistance.
Heat resistance and rigidity are also improved.
本発明の樹脂組成物には一ヒ記成分のほかに強化繊維を
配合してもよい、配合可能な強化繊維としては、ガラス
繊維、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。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−アミノエナル
）−γ−アミノプロピルトリメトキシシラン、γグリシ
ドキシプロピルトリメトキシシラン等で処理しておいて
もよい。The resin composition of the present invention may contain reinforcing fibers in addition to the above-mentioned components. Examples of reinforcing fibers that can be blended include glass fibers, carbon fibers, boron fibers, potassium titanate fibers,
Examples include fibrous substances made of inorganic substances such as wollastonite and asbestos fibers, and organic substances such as aramid fibers known under trademarks such as Kevlar. Additionally, the surface of the fibers may be coated with silane compounds such as vinyltriethoxysilane,
It may be treated with γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-(β-aminoenal)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or the like.
また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２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 also 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, 2 rust inhibitors, etc. may be added within a range that does not impair the purpose of the present invention.
例えば難燃剤としては、トリクレジルホスフェ−ｈ、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）ホスフェート、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、＃ｉ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（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特に
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、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 phosphoric acid esters such as tricresyl phosphate, cresyl diphenyl phosphate, diphenyloctyl phosphate, and tributyl phosphate; tris(β-chloroethyl) phosphate, tris(
Halogen-containing phosphate esters such as dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, and tris(bromochloropropyl) phosphate;
Chlorinated paraffin, chlorinated polyethylene, brominated polyphenyl, chlorinated polyphenyl, dechlorane, dechlorane plus, tetrabromoethane, tetrabromobutane, 1
．． 2-dibromo-3-chloropropane, 1,2,3
- tribromopropane, hexabromocyclododecane,
Tetrabromobenzene, #i hydrogenated diphenyl, decabromodiphenyl oxide, N,N'-ethylenebis(tetrabromophthalimide), tribromopolystyrene,
Halogen compounds such as polydibromobenzene oxide and bistribromophenoxyethane; Antimony compounds such as antimony dioxide, potassium antimony tartrate, and triphenylstibine; Boron compounds such as borax, zinc borate, and barium metaborate; Magnesium hydroxide, hydroxide There are metal hydroxides such as aluminum, calcium hydroxide, barium hydroxide, etc. Among these, halogen compounds, especially dechlorane, decabromidiphenyl oxide, N, N'
- A combination of a halogen compound such as ethylene bis(tetrabromophthalimide) or brominated epoxy with antimony dioxide, or magnesium hydroxide is preferable because flame retardancy can be imparted without deteriorating heat resistance or mechanical strength.
本発明の樹脂組成物を得る方法としては、ＭｉＪ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 each component listed in MiJ within the above range.
混合方法としては種々公知の方法１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、混合後さらに一軸押
出機、二軸押出機、ニーダ−等により溶融混練後、造粒
あるいは粉砕する方法などがあげられる。As a mixing method, there are various known methods 1. For example, mixing using a Henschel mixer, ■-blender, ribbon blender, tumbler blender, etc. After mixing, melt kneading using a single screw extruder, twin screw extruder, kneader, etc., and then manufacturing. Examples include methods such as granulation or pulverization.
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が成形
物の表層部において層状の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 forms a continuous layer in the surface layer of the molded product. Since the 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２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ｍ鏡写真（１００倍）であり、
表層部にボリフエニレンスルフイドの層状の連続相が形
成されていることがわかる。FIG. 1 is a microscopic photograph (100x) of a cross section showing the dispersion state of the polymer constituting the composition in the surface layer of the resin molded article of Example 2, which will be described later, manufactured by injection molding.
It can be seen that a layered continuous phase of polyphenylene sulfide is formed in the surface layer.
本発明によれば、エチレンまたはプロピレンを主体とす
るポリオレフィンにポリフェニレンスルフィドを配合し
たので、ポリオレフィ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オレフィン樹脂組成物が得られる
。According to the present invention, since polyphenylene sulfide is blended with polyolefin mainly composed of ethylene or propylene, it is possible to maintain the shape at a temperature higher than the melting point of the polyolefin resin, and has excellent heat aging resistance and heat resistance rigidity. A polyolefin resin composition is obtained.
また本発明のポリオレフィン樹脂成形物は、表層部にお
いてポリフェニレンスルフィドが層状の連続相を形成し
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。Further, in the polyolefin resin molded product of the present invention, since polyphenylene sulfide forms a layered continuous phase in the surface layer portion, heat aging resistance and heat resistance rigidity are further improved.
以下、本発明の実施例について説明する。 Examples of the present invention will be described below.
実施例１
ポリエチレン（ＭＦＲｌ、。６６ ｇ／ｌｏ分、密度：
０，９５７ｇ／−１以下ＰＥＩと記す）、ポリフェニ
レンスルフィトＴ−１（）−−プレン社製、商品名、２
９０℃、９＝１０００ｓｅｃ−１における溶融粘度：
２５００ボイズ、以下Ｔ−１と記す）および無水マレイ
ン酸グラフト変性ポリエチレン（グラフト割合＝２．０
重社％、ＭＦＲ工、。、：５ｇ／１０分、密度： ０．
９６に／ｄ、極限粘度〔η〕：２ｄＱ／ｇ、融点：Ｉ３
５℃、以下ＭＰＥＩと記す）を重量比で７０：３０：１
の割合でブレンドし樹脂混合物を得た後、２９０°Ｃで
射出成形して厚さ０．５ｍ＋ｎのキャップ状の薄肉の樹
脂成形品を得た。Example 1 Polyethylene (MFRl, .66 g/lo min, density:
0,957g/-1 (hereinafter referred to as PEI), polyphenylene sulfite T-1 ()--manufactured by Prene Co., Ltd., trade name, 2
Melt viscosity at 90°C, 9=1000 sec-1:
2500 voids, hereinafter referred to as T-1) and maleic anhydride graft modified polyethylene (graft ratio = 2.0
Jusha%, MFR Engineering,. , :5g/10min, density: 0.
96/d, intrinsic viscosity [η]: 2dQ/g, melting point: I3
5°C, hereinafter referred to as MPEI) in a weight ratio of 70:30:1
A resin mixture was obtained by blending at a ratio of 1, and then injection molded at 290°C to obtain a cap-shaped thin resin molded product with a thickness of 0.5 m+n.
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.
実施例２
実施例１で使用したポリエチレンの代わりにポリプロピ
レン（ＭＦＲｚ３゜−ｅ ： １３ｇ／１０分、密度：
０．９１ｇ／ｄ、以下ＰＰＩと記す）、無水マレイン
酸グラフト変性ポリエチレンの代わりに無水マレイン酸
クラフト変性ポリプロピレン（グラフト割合：３．０重
量％、極限粘度〔η） ： ０，４ｄ１２／ｇ、融点：
１６５℃、以下ＭＰＰＩと記す）を使用した以外は実施
例１と同様に行った。結果を表１に示す。Example 2 Polypropylene (MFRz3°-e: 13 g/10 min, density:
0.91 g/d, hereinafter referred to as PPI), maleic anhydride graft modified polypropylene instead of maleic anhydride graft modified polyethylene (graft ratio: 3.0% by weight, intrinsic viscosity [η): 0.4d12/g, melting point :
The same procedure as in Example 1 was conducted except that 165° C. (hereinafter referred to as MPPI) was used. The results are shown in Table 1.
比較例１
実施例１で使用した樹脂混合物の代わりにＰＥＩを単独
に使用した以外は実施例１と同様に行った。Comparative Example 1 A comparative example was carried out in the same manner as in Example 1 except that PEI was used alone instead of the resin mixture used in Example 1.
結果を表１に示す。The results are shown in Table 1.
比較例２
実施例２で使用した樹脂混合物の代わりにＰＰＩを屯独
に使用した以外は実施例２と同様に行った。Comparative Example 2 The same procedure as in Example 2 was carried out except that PPI was used instead of the resin mixture used in Example 2.
結果を表１に示す。The results are shown in Table 1.
実施例３．４
実施例１．２で用いたＰＥＩまたはＰＰ１とＴ−１とを
重量比で７８ ： ２２の割合でブレンドし、２９０℃
で射出成形または圧縮成形により１２５ｏｕ＋＋ Ｘ
２５ｍｍ Ｘ ２＋ａ鵬の樹脂成形品を得た。Example 3.4 PEI or PP1 used in Example 1.2 and T-1 were blended at a weight ratio of 78:22 and heated at 290°C.
125ou++ by injection molding or compression molding
A resin molded product measuring 25 mm x 2+a was obtained.
得られた成形品の一端を保持して水平に保ち、オーブン
中で所定の温度で６０分間保持して、熱たわみ試験を行
った。６０分後の先端の垂下がり距離（ｍＩｌ）を測定
した結果を表２に示す。A heat deflection test was conducted by holding one end of the obtained molded product to keep it horizontal and holding it in an oven at a predetermined temperature for 60 minutes. Table 2 shows the results of measuring the hanging distance (mIl) of the tip after 60 minutes.
表 ２ （
単位：ＩＩＩＩｌ）次に耐熱老化性を調べるため上記樹
脂成形品をオーブン中１６０℃に保つ前と後の引張強度
（ｋｇ／ａＪ）をａｔ１１定した。結果を表３に示す。Table 2 (
Unit: III) Next, in order to examine heat aging resistance, the tensile strength (kg/aJ) of the resin molded article was determined before and after keeping it in an oven at 160°C. The results are shown in Table 3.
表 ３ （単位：ｋｇ／ｃｎ
）Table 3 (Unit: kg/cn
)
第１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。FIG. 1 is a micrograph showing the particle structure of the resin molded product of the present invention.
Claims (2)
フィン４０〜７８重量％、およびポリフェニレンスルフ
ィド２２〜６０重量％を含有することを特徴とする耐熱
性ポリオレフィン樹脂組成物。(1) A heat-resistant polyolefin resin composition containing 40 to 78% by weight of a polyolefin mainly composed of ethylene or propylene, and 22 to 60% by weight of polyphenylene sulfide.
フィン４０〜７８重量％、およびポリフェニレンスルフ
ィド２２〜６０重量％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オレフィン樹脂成形物。(2) A heat-resistant product containing 40 to 78% by weight of polyolefin mainly composed of ethylene or propylene and 22 to 60% by weight of polyphenylene sulfide, with the polyphenylene sulfide forming a layered continuous phase in the surface layer. molded polyolefin resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33503688A JPH02178339A (en) | 1988-12-29 | 1988-12-29 | Heat resistant polyolefin resin composition and resin molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33503688A JPH02178339A (en) | 1988-12-29 | 1988-12-29 | Heat resistant polyolefin resin composition and resin molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02178339A true JPH02178339A (en) | 1990-07-11 |
Family
ID=18284024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33503688A Pending JPH02178339A (en) | 1988-12-29 | 1988-12-29 | Heat resistant polyolefin resin composition and resin molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02178339A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0499468A2 (en) * | 1991-02-13 | 1992-08-19 | Tosoh Corporation | Process for preparing a polyphenylene sulfide resin composition |
| WO1997035923A1 (en) * | 1996-03-26 | 1997-10-02 | Kureha Kagaku Kogyo K.K. | Resin composition |
| WO2001027204A1 (en) * | 1999-10-12 | 2001-04-19 | Toray Industries, Inc. | Resin structure and use thereof |
| JP2009149792A (en) * | 2007-12-21 | 2009-07-09 | National Institute Of Advanced Industrial & Technology | Polypropylene resin composition and method for producing the same |
-
1988
- 1988-12-29 JP JP33503688A patent/JPH02178339A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0499468A2 (en) * | 1991-02-13 | 1992-08-19 | Tosoh Corporation | Process for preparing a polyphenylene sulfide resin composition |
| WO1997035923A1 (en) * | 1996-03-26 | 1997-10-02 | Kureha Kagaku Kogyo K.K. | Resin composition |
| WO2001027204A1 (en) * | 1999-10-12 | 2001-04-19 | Toray Industries, Inc. | Resin structure and use thereof |
| EP1270671A1 (en) * | 1999-10-12 | 2003-01-02 | Toray Industries, Inc. | Resin structure and use thereof |
| EP1270671A4 (en) * | 1999-10-12 | 2004-06-16 | Toray Industries | Resin structure and use thereof |
| US6830792B1 (en) | 1999-10-12 | 2004-12-14 | Toray Industries, Inc. | Resin structure and use thereof |
| US6900272B2 (en) | 1999-10-12 | 2005-05-31 | Toray Industries, Inc. | Resin structure |
| US7115312B2 (en) | 1999-10-12 | 2006-10-03 | Toray Industries, Inc. | Resin structure and use thereof |
| JP2009149792A (en) * | 2007-12-21 | 2009-07-09 | National Institute Of Advanced Industrial & Technology | Polypropylene resin composition and method for producing the same |
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