JP3605956B2 - Reinforced polyester resin composition and molded article thereof - Google Patents
Reinforced polyester resin composition and molded article thereof Download PDFInfo
- Publication number
- JP3605956B2 JP3605956B2 JP22159796A JP22159796A JP3605956B2 JP 3605956 B2 JP3605956 B2 JP 3605956B2 JP 22159796 A JP22159796 A JP 22159796A JP 22159796 A JP22159796 A JP 22159796A JP 3605956 B2 JP3605956 B2 JP 3605956B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyester resin
- parts
- resin composition
- copolymer
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 32
- 229920001225 polyester resin Polymers 0.000 title claims description 25
- 239000004645 polyester resin Substances 0.000 title claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 46
- -1 polybutylene terephthalate Polymers 0.000 claims description 46
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 23
- 239000011256 inorganic filler Substances 0.000 claims description 21
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 239000004711 α-olefin Substances 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 14
- 150000001463 antimony compounds Chemical class 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 9
- 150000005526 organic bromine compounds Chemical class 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920001038 ethylene copolymer Polymers 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000003063 flame retardant Substances 0.000 description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 230000001771 impaired effect Effects 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 125000005487 naphthalate group Chemical group 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- FWQNYUYRXNWOOM-UHFFFAOYSA-N 2-nonylpropanedioic acid Chemical compound CCCCCCCCCC(C(O)=O)C(O)=O FWQNYUYRXNWOOM-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 1
- 101000837805 Homo sapiens Testis-expressed protein 44 Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 102100028514 Testis-expressed protein 44 Human genes 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 description 1
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- KIQKNTIOWITBBA-UHFFFAOYSA-K antimony(3+);phosphate Chemical compound [Sb+3].[O-]P([O-])([O-])=O KIQKNTIOWITBBA-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-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
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、良好な機械特性をもち、成形品の異方性が極めて小さく、そりの少ない強化難燃ポリエステル樹脂組成物および成形品に関するものである。
【０００２】
【従来の技術】
ポリブチレンテレフタレート（ＰＢＴ）は、機械的性質、耐熱性および耐薬品性に優れることから最近、電気・電子機器部品、自動車部品および機械・機構部品などの用途に展開されている。さらに、これらの用途に対する要求特性として、例えば、電子コネクターなどの分野においては、さらにコネクターをアセンブリーする際にピンを圧入することが多いため、良好な機械的特性とコネクター結合時に密着性を高めるため異方性が極めて小さく、そりの少ない成形品が要求されていた。また、これらの用途に使用するには、ＵＬ規格に規定される難燃性を満足する材料が要求されていた。
【０００３】
特公昭６２−２９４５０号公報および特公昭６１−５９３４７号公報に示されるポリエステル樹脂にガラス繊維およびガラスパウダーを併用使用する方法、特公昭６２−３８６９号公報に示されるＰＢＴにポリエーテルエステルまたはアクリロニトリル−スチレン共重合体などにガラス繊維と特定粒子径の無機充填剤を用いる方法、特公昭５５−４１６９９号公報や特公昭５５−４１７００号公報に示されるガラスフレークや無機固体とエポキシ化合物を用いる方法、特開昭６３−２９１９４７号公報に示される特定粒子径のフッ素原子含有化合物、ゴムおよび充填剤を防火剤に用いる方法などが開示されている。
【０００４】
しかしながら、これらのポリマや充填剤はある程度の異方性を満足する材料は得られるものの、良好な機械的特性と極めて少ない異方性を兼ね備え、難燃性が付与され、そりが少ない成形品が安定して得られる方法としては十分でなかった。
【０００５】
また、特開昭５９−１８９１７０号公報に示されるＰＢＴにポリカーボネート樹脂、繊維状充填剤および板状充填剤を用いる方法は、衝撃強度と異方性に優れるものの、ＰＢＴ固有の優れた性質である耐薬品性を低下させる問題があった。
【０００６】
【発明が解決しようとする課題】
従って本発明は、良好な機械特性と極めて少ない異方性を兼ね備え、難燃性を付与された強化ポリエステル樹脂組成物であって、そりの少ない成形品を安定して得ることを課題とする。
【０００７】
【課題を解決するための手段】
そこで、本発明者らは、上記課題を解決すべく鋭意検討した結果、本発明に到達した。すなわち、本発明は、「（Ａ）ポリブチレンテレフタレートを必須含有成分とする熱可塑性ポリエステル樹脂１００重量部に対して、（Ｂ）軟化温度が５０℃以下の（ａ）α―オレフィンとエポキシ基含有不飽和単量体とからなるエポキシ基含有共重合体、もしくは（ｂ）エチレンと炭素数３以上のα−オレフィン及び／またはビニル系単量体からなるエチレン共重合体であるポリオレフィン共重合体２〜３０重量部、（Ｃ）有機臭素化合物２〜６０重量部、（Ｄ）アンチモン化合物０．２〜３０重量部、（Ｅ）フッ素系樹脂０〜５重量部、（Ｆ）繊維径２〜５０μｍの繊維状無機充填剤２〜１７０重量部および（Ｇ）板状無機物２〜１７０重量部を含有し、（Ｆ）成分量は（Ｇ）成分の０．２５〜４倍量の範囲であり、（Ｇ）板状無機物の平均粒子径が３００〜３０００μｍであり、流れ方向と流れと直角方向の成形収縮率の差が０．１５〜０．４６である強化ポリエステル樹脂組成物。」および「前記強化ポリエステル樹脂組成物を射出成形してなる成形品」を提供するものである。
【０００８】
【発明の実施の形態】
以下、本発明の実施の形態について説明する。本発明において、「重量」とは「質量」を意味する。
【０００９】
本発明の（Ａ）成分の熱可塑性ポリエステル樹脂は、ポリブチレンテレフタレートまたはその共重合体を必須成分とする。このような重合体は、テレフタル酸あるいはそのエステル形成性誘導体と１，４−ブタンジオールあるいはそのエステル形成性誘導体とを主成分とし重縮合反応によって得られる重合体あるいは共重合体である。これら重合体および共重合体の好ましい例としては、ポリブチレンテレフタレート、ポリブチレン（テレフタレート／イソフタレート）、ポリブチレン（テレフタレート／アジペート）、ポリブチレン（テレフタレート／セバケート）、ポリブチレン（テレフタレート／デカンジカルボキシレート）、ポリブチレン（テレフタレート／ナフタレート）ポリ（ブチレン／エチレン）テレフタレート等が挙げられ、単独で用いても２種以上混合して用いても良い。ポリブチレンテレフタレート構造単位が重合体中に５０重量％以上含有するものが好ましく使用される。なおここで「／」は共重合していることを意味する。
【００１０】
（Ａ）熱可塑性ポリエステル樹脂においてその他の成分が配合できる。上記ポリブチレンテレフタレートまたはその共重合体以外のものであり必須成分ではない。このようなものとしてはジカルボン酸あるいは、そのエステル形成性誘導体とジオールあるいはそのエステル形成性誘導体とを主成分とする重縮合反応により得られる重合体ないしは共重合体である。
【００１１】
上記ジカルボン酸としては、テレフタル酸、イソフタル酸、フタル酸、２，６−ナフタレンジカルボン酸、１，５−ナフタレンジカルボン酸、ビス（ｐ−カルボキシフェニル）メタン、アントラセンジカルボン酸、４，４´−ジフェニルエーテルジカルボン酸、５−ナトリウムスルホイソフタル酸などの芳香族ジカルボン酸、アジピン酸、セバシン酸、アゼライン酸、ドデカンジオン酸などの脂肪族ジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸などの脂環式ジカルボン酸およびこれらのエステル形成性誘導体などが挙げられる。
【００１２】
また、ジオール成分としては、炭素数２〜２０の脂肪族グリコールすなわち、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、デカメチレングリコール、シクロヘキサンジメタノール、シクロヘキサンジオールなど、あるいは分子量４００〜６０００の長鎖グリコール、すなわちポリエチレングリコール、ポリ−１，３−プロピレングリコール、ポリテトラメチレングリコールなどおよびこれらのエステル形成性誘導体などが挙げられる。これらの重合体ないしは共重合体の例としては、ポリブチレン（テレフタレート／イソフタレート）、ポリブチレン（テレフタレート／イソフタレート）、ポリエチレンテレフタレート、ポリエチレン（テレフタレート／イソフタレート）、ポリエチレン（テレフタレート／アジペート）、ビスフェノールＡ（テレフタレート／イソフタレート）、ポリブチレン（テレフタレート／ナフタレ−ト）、ポリエチレンナフタレート、ポリシクロヘキサンジメチレンテレフタレート、ポリシクロヘキサンジメチレン（テレフタレート／イソフタレート）、ポリ（シクロヘキサンジメチレン／エチレン）テレフタレート、ポリ（シクロヘキサンジメチレン／エチレン）（テレフタレート／イソフタレート）などが挙げられる。
【００１３】
また、ポリエーテル成分あるいは脂肪族ポリエステル成分をさらに共重合した共重合体が挙げられる。例えば、ポリブチレンテレフタレート・ポリ（テトラメチレンオキシド）グリコールブロック共重合体、ポリブチレンテレフタレート／イソフタレート・ポリ（テトラメチレンオキシド）グリコールブロック共重合体、ポリブチレンテレフタレート・ポリ（プロピレンオキシド／エチレンオキシド）グリコールブロック共重合体、ポリブチレンテレフタレート／イソフタレート・ポリ（プロピレンオキシド／エチレンオキシド）グリコールブロック共重合体、ポリブチレンテレフタレート・ポリブチレンアジペートブロック共重合体、ポリブチレンテレフタレート・ポリ−ε−カプロラクトンブロック共重合体などが挙げられる。
【００１４】
これらの中で、ポリエチレンテレフタレート、ポリシクロヘキサンジメチレンテレフタレート、ポリ（シクロヘキサンジメチレン／エチレン）テレフタレート、ポリブチレンテレフタレート・ポリ（テトラメチレンオキシド）グリコールのポリエーテルエステル共重合体およびポリブチレンテレフタレート／イソフタレート・ポリ（テトラメチレンオキシド）グリコールのポリエーテルエステル共重合体が好ましく用いられる。また、上記の熱可塑性ポリエステル樹脂のメルトフローレイト（ＭＦＲ）は、示差熱量計で求められる結晶融点プラス２０℃の測定条件において測定されたメルトフローレイト（ＭＦＲ）が１〜１００、とくに２〜８０の範囲にあるものが機械的特性、成形性の点から好適である。ＭＦＲが１未満では成形時の流動性を低下させるため、好ましくない。また、ＭＦＲが８０越えると衝撃強度が低下するため好ましくない。また、（Ａ）熱可塑性ポリエステル樹脂におけるポリブチレンテレフタレートまたはその共重合体の含有量の和は、５０〜１００重量％、さらに５０〜９９重量％、さらに６０〜９９重量％が好ましい。配合量が少ないとポリブチレンテレフタレート固有の耐熱性、耐薬品性を損なう傾向がある。
【００１５】
本発明で用いられる（Ｂ）軟化温度が５０℃以下の（ａ）α―オレフィンとエポキシ基含有不飽和単量体とからなるエポキシ基含有共重合体、もしくは（ｂ）エチレンと炭素数３以上のα−オレフィン及び／またはビニル系単量体からなるエチレン共重合体であるポリオレフィン共重合体とは、ＪＩＳＫ６７３０で測定されるビカット軟化温度が５０℃以下のポリオレフィン系共重合体であり、（ａ）αーオレフィンとエポキシ基含有不飽和単量体とからなるエポキシ基含有共重合体、（ｂ）エチレンと炭素数３以上のαーオレフィンおよび／またはビニル系単量体からなるエチレン共重合体である。これらは高圧ラジカル重合法、溶液重合法、乳化重合法などの公知の方法で製造することができる。上記α−オレフィンとエポキシ基含有不飽和単量体とからなる（ａ）エポキシ基含有共重合体のα−オレフィンとしては、エチレン、プロピレン、ブテン−１などであり、エポキシ基含有不飽和単量体の具体例としては、アクリル酸グリシジル、メタクリル酸グリシジル、エタクリル酸グリシジル、イタコン酸グリシジルなどであり、さらに、ビニルエーテル類、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、メチル、エチル、プロピル、ブチルなどのアクリル酸およびメタクリル酸エステル類などを共重合したグリシジルエ−テル類およびグリシジルエステル類が挙げられる。
【００１６】
エポキシ基含有共重合体の好ましい例としては、エチレン／メタクリル酸グリシジル共重合体、エチレン／酢酸ビニル／メタクリル酸グリシジル共重合体、エチレン／メタクリル酸メチル／メタクリル酸グリシジル共重合体、エチレン／アクリル酸グリシジル共重合体、エチレン／酢酸ビニル／アクリル酸グリシジル共重合体、エチレン／グリシジルエーテル共重合体などが挙げられ、なかでもエチレン／メタクリル酸グリシジル共重合体が最も好ましく、通常エチレン／メタクリル酸グリシジル共重合体中のメタクリル酸グリシジル共重合成分が約２０重量％以上であるとき軟化温度は５０℃以下となる。
【００１７】
上記（ｂ）エチレンと炭素数３以上のα−オレフィンおよび／またはビニル系単量体を共重合してなるエチレン系共重合体における炭素数３以上のα−オレフィンとは、プロピレン、ブテン−１、ペンテン−１、３−メチルペンテン−１、オクタセン−１などが挙げられ、ビニル系モノマーとしては、メチル、エチル、プロピル、ブチルなどのアクリル酸またはメタクリル酸エステルなどが挙げられる。具体例としてはエチレン／プロピレン共重合体、エチレン／ブテン−１共重合体、エチレン／ペンテン−１共重合体、エチレン／プロピレン／ブテン−１共重合体、エチレン／プロピレン／ジシクロペンタジエン共重合体、エチレン／プロピレン／５−エチリデン−２−ノルボーネン共重合体、エチレン／プロピレン／ジシクロペンタジエン共重合体、エチレン／アクリル酸メチル共重合体、エチレン／アクリル酸エチル共重合体などが挙げられ、なかでもエチレン／プロピレン共重合体、エチレン／ブテン−１共重合体、エチレン／メタクリル酸メチル共重合体およびエチレン／アクリル酸エチル共重合体が好ましく使用でき、１種以上併用して用いても良い。さらに、エポキシ化合物、酸無水物、イミドなどをグラフト反応して得た変性共重合体が挙げられる。また、軟化温度は５０℃以下にする具体例として、例えばエチレン／アクリル酸エチル共重合体の場合、アクリル酸エチル共重合成分が約２０重量％以上であるとき軟化温度は５０℃以下となる。
【００１８】
上記の軟化温度が５０℃以下のポリオレフィン共重合体の配合量は、（Ａ）熱可塑性ポリエステル１００重量部に対して、２〜３０重量部、さらに５〜２５重量部が好ましく、２重量部未満では、本発明の効果が少なく好ましくない。また、３０重量部を越すとＰＢＴ固有の耐熱性を損なう傾向がある。
【００１９】
本発明で使用する（Ｃ）有機臭素化合物とは、通常難燃剤として作用するものであり、具体例としては、臭素化ポリカーボネート、臭素化エポキシ樹脂、臭素化フェノキシ樹脂、臭素化ポリフェニレンエーテル樹脂、臭素化ポリスチレン樹脂、臭素化ビスフェノールＡ、臭素化ポリフェニレンフタルイミドなどの１種以上の有機臭素化合物が例示され、熱可塑性ポリエステル１００重量部に対して、２〜６０重量部、さらに３〜５５重量部が好ましく、２重量部未満では難燃性の効果が小さく、６０重量部を越すと本発明の機械特性を損なう傾向がある。プラスチックの燃焼試験であるＵＬ９４規格としてＶ−０、Ｖ−１またはＶ−２が達成されるための量が配合されるのが一般的である。
【００２０】
本発明で使用する（Ｄ）アンチモン化合物とは、（Ｃ）有機臭素化合物と併用することによって、相乗的に難燃性を向上させることができるもので、三酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダおよびリン酸アンチモンなどのアンチモン化合物が例示され、表面処理などが施されているアンチモン化合物も使用できる。また、アンチモン化合物の配合量は、（Ａ）熱可塑性ポリエステル１００重量部に対して、０．２〜３０重量部、さらに０．３〜２５重量部の範囲が好ましく、０．２重量部未満では難燃性の効果がなく、３０重量部を越すと本発明の機械特性を損なうため好ましくない。併用例としては有機臭素化合物中のブロム３原子に対して、アンチモン化合物中のアンチモン１原子の配合に近い混合比の例が挙げられる。
【００２１】
本発明では、必須成分ではないが（Ｅ）フッ素系樹脂が配合できる。（Ｅ）フッ素系樹脂とは、難燃助剤として機能し、（Ｃ）有機臭素化合物および（Ｄ）アンチモン化合物に併用使用することによって、より難燃性を向上させうる性質の難燃助剤である。フッ素系樹脂の具体例としては、ポリフッ化ビニル、ポリフッ化ビニリデンおよびポリテトラフルオロエチレンなどのフッ素置換のポリオレフィンなどであり、表面処理などが施されているフッ素系樹脂も使用できる。その中でも、ポリテトラフルオロエチレンが好ましく用いられ、その量はフッ素系樹脂の５０重量％以上、さらに６０重量％以上が好ましい。上記のポリテトラフルオロエチレンは、乳化重合法あるいは懸濁重合法などで製造され、２次粒子径が１００〜１５００μｍの範囲にあるものが好ましい。フッ素系樹脂の配合量は、０．１〜５重量部が好ましく、さらに０．２〜５重量部が好ましい。多いと成形時の流動性を損なうため好ましくない。
【００２２】
本発明では（Ｄ）繊維径が２〜５０μｍの繊維状無機充填剤が配合される。繊維状無機充填剤としては、一般に樹脂の強化用に用いられるものなら特に限定はないが、ガラス繊維、炭素繊維および金属繊維が例示され、なかでもガラス繊維が好ましく用いられる。繊維状無機充填剤におけるガラス繊維の割合は、５０重量％以上、さらに８０重量％以上、さらに９０重量％以上の範囲が好ましい。上記のガラス繊維としては、例えば長繊維タイプや短繊維タイプのチョップドストランドなどを用いることができる。また、ガラス繊維は熱可塑性樹脂、エポキシ樹脂などの熱硬化性樹脂で被覆または集束されていてもよい。繊維状無機充填剤の大きさは、一般に樹脂の強化用に用いるものなら特に限定はないが、繊維径が２〜５０μｍのものが好ましく使用でき、通常アミノシランやエポキシシランで表面処理したものがより効果を発現する。また、繊維径が２〜５０μｍの繊維状無機充填剤の配合量は、（Ａ）熱可塑性ポリエステル１００重量部に対して、２〜１７０重量部、さらに３〜１４０重量部が好ましい。２重量部未満では、機械特性の改良効果が十分発現しないため好ましくなく、１７０重量部を越すと成形性を損なう傾向がある。
【００２３】
本発明では、（Ｇ）板状無機充填剤が配合される。その平均粒径は３００〜３０００μｍである。ここでいう平均粒径とは、粒度分布で測定される重量平均粒子径を意味する。板状無機充填剤としては、一般に樹脂の強化用に用いるものなら特に限定はないが、ガラスフレーク、雲母、金属箔が好ましく使用され、なかでもガラスフレークが好ましく用いられる。上記のガラスフレークとは、一般に樹脂の強化用に用いるものなら特に限定はなく、熱可塑性樹脂、エポキシ樹脂などの熱硬化性樹脂で被覆または集束されていてもよく、アミノシランやエポキシシランで表面処理したものも好ましく使用される。板状無機充填剤におけるガラスフレークの配合量としては５０重量％以上、さらに８０重量％以上、さらに９０重量％以上の範囲が好ましい。また、板状無機充填剤の配合量は、（Ａ）熱可塑性ポリエステル１００重量部に対して、２〜１７０重量部、さらに３〜１４０重量部が好ましい。２重量部未満では、機械特性の改良効果が十分発現せず、１７０重量部を越すと成形性を損なう傾向がある。
【００２４】
本発明では、前に具体的に例示した無機充填剤の他に、（Ｆ）繊維状無機充填剤、（Ｇ）板状無機充填剤またはその他の充填剤として、セラミックスファイバー、セラミックビーズ、アスベスト、ワラステナイト、タルク、クレー、マイカ、セリサイト、ゼオライト、ベントナイト、ドロマイト、カオリン、微粉ケイ酸、長石粉、チタン酸カリウム、シラスバルーン、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、酸化カルシウム、酸化アルミニウム、酸化チタン、ケイ酸アルミニウム、酸化ケイ素、石膏、ノバキュライト、ドーソナイトおよび白土なども配合できる。
【００２５】
本発明の上記の（Ｆ）繊維径が２〜５０μｍの繊維状無機充填剤と（Ｇ）板状無機充填剤の併用比率は、（Ｆ）成分量に対して、（Ｇ）成分量が０．２５〜４倍量，好ましくは０．３〜３．５倍料の範囲で使用することにより機能はより向上し、０．２５倍量未満の時は、強化ポリエステル組成物の異方性が大きくなる傾向があり、４倍量を越すと機械特性の改良効果が十分発現しないため好ましくない。
【００２６】
本発明に対して、本発明の目的を損なわない範囲で酸化防止剤、紫外線吸収剤、熱安定剤、核剤、滑剤、離形剤、染料および顔料を含む着色剤、核化剤、他の熱可塑性樹脂（例えばポリエチレン、アクリル樹脂、ポリアミド、ポリフェニレンサルファイド樹脂、ポリエーテルエーテルケトン樹脂、液晶ポリエステル樹脂、ポリアセタール、ポリスルホン、ポリフェニレンオキサイドなど）および熱
硬化性樹脂（例えばフェノール樹脂、メラミン樹脂、ポリエステル樹脂、シリコーン樹脂、エポキシ樹脂など）などの少なくとも１種以上をさらに含有することができる。
【００２７】
本発明組成物の製造方法は特に限定されるものではないが、例えばポリブチレンテレフタレート、軟化点が５０℃以下の（ａ）α―オレフィンとエポキシ基含有不飽和単量体とからなるエポキシ基含有共重合体、もしくは（ｂ）エチレンと炭素数３以上のα−オレフィン及び／またはビニル系単量体からなるエチレン共重合体であるポリオレフィン、必要に応じて他の熱可塑性ポリエステル樹脂、有機臭素化化合物、アンチモン化合物、フッ素系樹脂および必要に応じてその他の添加剤を予めブレンドした後、ポリブチレンテレフタレートの融点以上において、ニーディングブロックを１ゾーン以上有する２軸押出機のホッパーに供給し、サイドフィーダから繊維径が２〜５０μｍの繊維状無機充填剤と平均粒径が３００〜３０００μｍ板状無機充填剤を押出機に供給して均一に溶融混練する方法、あるいは全配合組成物を予めブレンドした後、ポリブチレンテレフタレートの融点以上において、スクリュ形状は特に限定されないが例えばダルメージスクリュを挿入した単軸押出機のホッパーに供給して均一に溶融混練する方法などが好ましく用いられる。
【００２８】
得られた強化ポリエステル樹脂組成物は、通常公知の射出成形、押出成形などの任意の方法で成形できる。
【００２９】
本発明の組成物から得られた成形品は、良好な機械特性をもち、特に射出成形で得られた成形品は、異方性が極めて小さく、かつそりの少ない難燃性が付与された成形材料として電気・電子コネクター部品、自動車部品、機械部品などの精密機器部品等種々の用途に使用することができる。
【００３０】
【実施例】
以下、実施例により本発明をさらに詳述する。なお、実施例中の部数は、全て重量基準である。実施例に使用した配合組成物の内容を表１に示す。
【００３１】
【表１】
＜強化難燃ポリエステル樹脂組成物の製造方法＞
日本製鋼所製ＴＥＸ４４・２軸押出機の元込め部とサイドフィーダの間にニーディングブロックを２ゾーン、サイドフィーダと吐出口であるダイスの間にニーディングブロックを１ゾーンを組み込み、加工温度を２６０℃に設定後、元込め部のホッパーに固有粘度０．９２のポリブチレンテレフタレート、表に記載した組成の熱可塑性ポリエステル樹脂、エチレン／アクリル酸エチル共重合体、有機臭素化合物、アンチモン化合物およびフッ素系樹脂を配合したブレンド物を供給し、サイドフィーダからガラス繊維とガラスフレーク供給して溶融混練を行い、ダイスから吐出されたストランドを冷却バスを通し、ストランドカッターでペレット化した。
【００３３】
＜強化難燃ポリエステル樹脂組成物の成形品の評価方法＞
上記の２軸押出機で得られたペレットを用いて、加工温度２５０℃、金型温度８０℃、成形サイクル（射出時間／冷却時間／中間時間）８／１０／５秒で１／８”厚みの引張試験片とアイゾット試験片を射出成形しＡＳＴＭ Ｄ６３８に従い引張試験、ＡＳＴＭ Ｄ２６５に従いアイゾット衝撃試験を行ない、機械特性の評価を行った。
【００３４】
また別の樹脂組成物を用いて、厚さ１ｍｍ、縦８０ｍｍ×横８０ｍｍ角板をフィルムゲート金型で射出成形し、万能投影機により、流れ方向と流れと直角方向の成形収縮率を測定し、流れ方向と流れと直角方向の成形収縮率の差が大きい材料ほど異方性が大きいと判断される。
【００３５】
また、上記の厚さ１ｍｍ、縦８０ｍｍ、横８０ｍｍ角板を幅８０ｍｍ、高さ１．３５ｍｍの空間を持つ長さ５０ｍｍの金属製の治具を通過させ、治具を通過しないものは不良品として取り扱い、上記の角板５０個を通過させ、不良率を算出した。なお、本試験は、そりの評価に有用な試験であり、そりの少ない各板は上記の治具を通過する。
【００３６】
また、ＵＬ９４規格に準じて、難燃性試験を行ない、難燃性ランクの判定を行なった。上記の難燃性ランクの判定基準は、規格外、ＵＬ９４ＨＢ、ＵＬ９４Ｖ−２、ＵＬ９４Ｖ−１、ＵＬ９４Ｖ−０の順に優れており、コネクター部品などの電気部品は、ＵＬ９４のＶ−２〜Ｖ−０の難燃性を持つ材料が要求されている。
【００３７】
実施例１〜１０、比較例１〜１０
上記の強化難燃ポリエステル樹脂組成物の製造方法に従い、表２と表３に示す配合組成の実施例１〜１０、比較例１〜１０の強化難燃ポリエステル樹脂組成物を得た。また、強化難燃ポリエステル樹脂組成物の成形品の評価方法に従い、実施例１〜１０、比較例１〜１０の強化難燃ポリエステル樹脂組成物の成形品の評価を行い、得られた評価結果を配合組成と同じく表２と表３に示す。
【００３８】
【表２】
【表３】
表２と表３の実施例と比較例の結果から、本発明のポリブチレンテレフタレートに軟化温度が５０℃以下の（ａ）α―オレフィンとエポキシ基含有不飽和単量体とからなるエポキシ基含有共重合体、もしくは（ｂ）エチレンと炭素数３以上のα−オレフィン及び／またはビニル系単量体からなるエチレン共重合体であるポリオレフィン、有機臭素化合物、アンチモン化合物、必要に応じてフッ素系樹脂、繊維径２〜５０μｍの繊維状無機充填剤および平均径３００〜３０００μｍの板状無機充填剤からなる強化難燃ポリエステル樹脂組成物は、比較例に比べ良好な機械特性を持ち、異方性がきわめて小さく、難燃性が付与され、そりの少ない射出成形品が安定して得られることが理解できる。
【００４１】
【発明の効果】
本発明の強化難燃ポリエステル樹脂組成物は、良好な機械特性と成形品の異方性が極めて小さく、そりが少なく不良率の少ない難燃性が付与された成形品が得られることから、寸法精度の厳しいコネクターなどの電気・電子部品および精密成形部品の用途に有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a reinforced flame-retardant polyester resin composition having excellent mechanical properties, extremely small anisotropy of a molded article, and low warpage, and a molded article.
[0002]
[Prior art]
BACKGROUND ART Polybutylene terephthalate (PBT) has recently been used in applications such as electric / electronic device parts, automobile parts, and mechanical / mechanical parts because of its excellent mechanical properties, heat resistance and chemical resistance. In addition, as a required characteristic for these applications, for example, in the field of electronic connectors and the like, pins are often pressed in when assembling the connector, so that good mechanical properties and adhesion when the connector is joined are improved. A molded article with extremely small anisotropy and little warpage has been required. In addition, a material satisfying the flame retardancy specified in UL standards has been required for use in these applications.
[0003]
JP-B-62-29450 and JP-B-61-59347, in which glass fiber and glass powder are used in combination with polyester resin, and PBT shown in JP-B-62-3869 with polyetherester or acrylonitrile- A method using a glass fiber and an inorganic filler having a specific particle size in a styrene copolymer or the like, a method using a glass flake or an inorganic solid and an epoxy compound shown in JP-B-55-41699 or JP-B-55-41700, JP-A-63-291947 discloses a method of using a fluorine atom-containing compound having a specific particle size, rubber and a filler as a fire retardant.
[0004]
However, although these polymers and fillers can be obtained as materials satisfying a certain degree of anisotropy, molded articles that have good mechanical properties and extremely low anisotropy, are provided with flame retardancy, and have less warpage are obtained. It was not enough to obtain a stable method.
[0005]
The method of using a polycarbonate resin, a fibrous filler, and a plate-like filler in PBT disclosed in JP-A-59-189170 is excellent in impact strength and anisotropy, but has excellent properties inherent to PBT. There was a problem that chemical resistance was reduced.
[0006]
[Problems to be solved by the invention]
Therefore, an object of the present invention is to provide a reinforced polyester resin composition having good mechanical properties and extremely low anisotropy and imparted with flame retardancy, and to stably obtain a molded article with less warpage.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have made intensive studies to solve the above-described problems, and as a result, have reached the present invention. That is, the present invention provides "(A ) an α-olefin having an softening temperature of 50 ° C. or less and (a) an α-olefin and an epoxy group-containing resin, based on 100 parts by weight of a thermoplastic polyester resin containing (A) polybutylene terephthalate as an essential component. Epoxy group-containing copolymer comprising an unsaturated monomer, or (b) polyolefin copolymer 2 comprising an ethylene copolymer comprising ethylene and an α-olefin having 3 or more carbon atoms and / or a vinyl monomer To 30 parts by weight, (C) 2 to 60 parts by weight of an organic bromine compound, (D) 0.2 to 30 parts by weight of an antimony compound, (E) 0 to 5 parts by weight of a fluororesin, (F) fiber diameter of 2 to 50 μm 2 to 170 parts by weight of the fibrous inorganic filler and (G) 2 to 170 parts by weight of the plate-like inorganic material, and the amount of the component (F) is in a range of 0.25 to 4 times the amount of the component (G). (G) Flat inorganic material Ri particle size 300~3000μm der, the difference in molding shrinkage in the flow direction and flow perpendicular direction Ru der 0.15 to 0.46 reinforced polyester resin composition. "And" the reinforced polyester resin composition Molded articles formed by injection molding ".
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described. In the present invention, “weight” means “mass”.
[0009]
The thermoplastic polyester resin of the component (A) of the present invention contains polybutylene terephthalate or a copolymer thereof as an essential component. Such a polymer is a polymer or copolymer containing terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof as main components and obtained by a polycondensation reaction. Preferred examples of these polymers and copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decane dicarboxylate), and polybutylene. (Terephthalate / naphthalate) poly (butylene / ethylene) terephthalate, etc., which may be used alone or in combination of two or more. Those having a polybutylene terephthalate structural unit content of 50% by weight or more in the polymer are preferably used. Here, "/" means that copolymerization is performed.
[0010]
(A) Other components can be blended in the thermoplastic polyester resin. It is other than the above polybutylene terephthalate or a copolymer thereof, and is not an essential component. Such a polymer is a polymer or copolymer obtained by a polycondensation reaction containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as main components.
[0011]
Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, and 4,4′-diphenyl ether Aromatic dicarboxylic acids such as dicarboxylic acid and 5-sodium sulfoisophthalic acid; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and dodecanedioic acid; 1,3-cyclohexanedicarboxylic acid; and 1,4-cyclohexanedicarboxylic acid And alicyclic dicarboxylic acids and ester-forming derivatives thereof.
[0012]
Examples of the diol component include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, Examples include methylene glycol, cyclohexanedimethanol, cyclohexanediol, and the like, or long-chain glycols having a molecular weight of 400 to 6000, such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and ester-forming derivatives thereof. . Examples of these polymers or copolymers include polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), and bisphenol A ( Terephthalate / isophthalate), polybutylene (terephthalate / naphthalate), polyethylene naphthalate, polycyclohexane dimethylene terephthalate, polycyclohexane dimethylene (terephthalate / isophthalate), poly (cyclohexane dimethylene / ethylene) terephthalate, poly (cyclohexane diol) Methylene / ethylene) (terephthalate / isophthalate) and the like.
[0013]
Further, a copolymer obtained by further copolymerizing a polyether component or an aliphatic polyester component may be used. For example, polybutylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol block Copolymer, polybutylene terephthalate / isophthalate / poly (propylene oxide / ethylene oxide) glycol block copolymer, polybutylene terephthalate / polybutylene adipate block copolymer, polybutylene terephthalate / poly-ε-caprolactone block copolymer, etc. Is mentioned.
[0014]
Among these, polyethylene terephthalate, polycyclohexane dimethylene terephthalate, poly (cyclohexane dimethylene / ethylene) terephthalate, polybutylene terephthalate / poly (tetramethylene oxide) glycol polyetherester copolymer and polybutylene terephthalate / isophthalate / isophthalate A polyether ester copolymer of poly (tetramethylene oxide) glycol is preferably used. Further, the melt flow rate (MFR) of the thermoplastic polyester resin is 1 to 100, particularly 2 to 80, which is the melt flow rate (MFR) measured under the measurement conditions of the crystal melting point plus 20 ° C. determined by a differential calorimeter. Are preferred in terms of mechanical properties and moldability. If the MFR is less than 1, the fluidity at the time of molding is reduced, which is not preferable. On the other hand, if the MFR exceeds 80, the impact strength decreases, which is not preferable. Further, the sum of the contents of polybutylene terephthalate or a copolymer thereof in the thermoplastic polyester resin (A) is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, and further preferably 60 to 99% by weight. If the amount is too small, the heat resistance and chemical resistance inherent in polybutylene terephthalate tend to be impaired.
[0015]
(B) an epoxy group-containing copolymer composed of an α-olefin and an epoxy group-containing unsaturated monomer having a softening temperature of 50 ° C. or lower used in the present invention , or (b) ethylene and a carbon number of 3 or more The polyolefin copolymer which is an ethylene copolymer composed of an α-olefin and / or a vinyl monomer is a polyolefin copolymer having a Vicat softening temperature of 50 ° C. or less as measured by JIS K6730, and (a) ) alpha-olefin and an epoxy group-containing unsaturated monomer comprising a epoxy group-containing copolymer is an ethylene copolymer composed of (b) ethylene and having 3 or more alpha-olefins and carbon / or vinyl monomer . These can be produced by a known method such as a high-pressure radical polymerization method, a solution polymerization method, and an emulsion polymerization method. Examples of the α-olefin of the epoxy group-containing copolymer (a) comprising the α-olefin and the epoxy group-containing unsaturated monomer include ethylene, propylene, butene-1, and the like. Specific examples of the body include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and further, vinyl ethers, vinyl acetate, vinyl esters such as vinyl propionate, methyl, ethyl, propyl, and butyl. Glycidyl ethers and glycidyl esters obtained by copolymerizing acrylic acid and methacrylic acid esters.
[0016]
Preferred examples of the epoxy group-containing copolymer include ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / acrylic acid Glycidyl copolymers, ethylene / vinyl acetate / glycidyl acrylate copolymers, ethylene / glycidyl ether copolymers, etc., among which ethylene / glycidyl methacrylate copolymers are most preferred, and usually ethylene / glycidyl methacrylate copolymers When the amount of the glycidyl methacrylate copolymer component in the polymer is about 20% by weight or more, the softening temperature becomes 50 ° C. or less.
[0017]
The (b) α-olefin having 3 or more carbon atoms in the ethylene copolymer obtained by copolymerizing ethylene with an α-olefin having 3 or more carbon atoms and / or a vinyl monomer includes propylene, butene-1 Pentene-1, 3-methylpentene-1, octacene-1, and the like. Examples of the vinyl monomer include acrylic acid and methacrylic acid esters such as methyl, ethyl, propyl, and butyl. Specific examples include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer , Ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, and the like. However, ethylene / propylene copolymers, ethylene / butene-1 copolymers, ethylene / methyl methacrylate copolymers and ethylene / ethyl acrylate copolymers are preferably used, and one or more of them may be used in combination. Further, a modified copolymer obtained by a graft reaction of an epoxy compound, an acid anhydride, an imide or the like can be used. As a specific example of setting the softening temperature to 50 ° C. or lower, for example, in the case of an ethylene / ethyl acrylate copolymer, the softening temperature is 50 ° C. or lower when the ethyl acrylate copolymer component is about 20% by weight or more.
[0018]
The blending amount of the polyolefin copolymer having a softening temperature of 50 ° C. or less is preferably 2 to 30 parts by weight, more preferably 5 to 25 parts by weight, and preferably less than 2 parts by weight based on 100 parts by weight of the thermoplastic polyester (A). Then, the effect of the present invention is small, which is not preferable. If it exceeds 30 parts by weight, the heat resistance inherent in PBT tends to be impaired.
[0019]
The (C) organic bromine compound used in the present invention generally functions as a flame retardant, and specific examples thereof include brominated polycarbonate, brominated epoxy resin, brominated phenoxy resin, brominated polyphenylene ether resin, and bromine. One or more organic bromine compounds such as brominated polystyrene resin, brominated bisphenol A, and brominated polyphenylene phthalimide are exemplified, and 2 to 60 parts by weight, and more preferably 3 to 55 parts by weight, based on 100 parts by weight of the thermoplastic polyester. If the amount is less than 2 parts by weight, the effect of flame retardancy is small, and if it exceeds 60 parts by weight, the mechanical properties of the present invention tend to be impaired. In general, an amount for achieving V-0, V-1 or V-2 as a UL94 standard, which is a combustion test for plastics, is blended.
[0020]
The (D) antimony compound used in the present invention is a compound that can synergistically improve flame retardancy by being used in combination with the (C) organic bromine compound, and includes antimony trioxide, antimony pentoxide, and antimonic acid. Antimony compounds such as soda and antimony phosphate are exemplified, and antimony compounds having been subjected to a surface treatment or the like can also be used. The compounding amount of the antimony compound is preferably from 0.2 to 30 parts by weight, more preferably from 0.3 to 25 parts by weight, based on 100 parts by weight of the thermoplastic polyester (A). There is no flame-retardant effect, and if it exceeds 30 parts by weight, the mechanical properties of the present invention are impaired, which is not preferable. As an example of the combined use, there is an example in which the mixing ratio is close to that of one atom of antimony in the antimony compound with respect to three atoms of bromo in the organic bromine compound.
[0021]
In the present invention, although not an essential component, (E) a fluorine-based resin can be blended. (E) A fluorine-based resin functions as a flame-retardant aid, and when used together with (C) an organic bromine compound and (D) an antimony compound, a flame-retardant aid having properties capable of further improving flame retardancy. It is. Specific examples of the fluorine-based resin include fluorine-substituted polyolefins such as polyvinyl fluoride, polyvinylidene fluoride, and polytetrafluoroethylene, and a fluorine-based resin subjected to a surface treatment or the like can also be used. Among them, polytetrafluoroethylene is preferably used, and its amount is preferably 50% by weight or more, more preferably 60% by weight or more of the fluorine-based resin. The above polytetrafluoroethylene is produced by an emulsion polymerization method or a suspension polymerization method, and preferably has a secondary particle diameter in a range of 100 to 1500 µm. The amount of the fluorine-based resin is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 5 parts by weight. If it is too large, the fluidity during molding is impaired, which is not preferable.
[0022]
In the present invention, (D) a fibrous inorganic filler having a fiber diameter of 2 to 50 µm is blended. The fibrous inorganic filler is not particularly limited as long as it is generally used for reinforcing a resin, and examples thereof include glass fibers, carbon fibers, and metal fibers, and among them, glass fibers are preferably used. The proportion of glass fibers in the fibrous inorganic filler is preferably in a range of 50% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more. As the glass fiber, for example, a chopped strand of a long fiber type or a short fiber type can be used. Further, the glass fiber may be covered or bundled with a thermosetting resin such as a thermoplastic resin and an epoxy resin. The size of the fibrous inorganic filler is not particularly limited as long as it is generally used for reinforcing a resin, but those having a fiber diameter of 2 to 50 μm can be preferably used, and those having a surface treated with aminosilane or epoxysilane are more preferable. Express the effect. The amount of the fibrous inorganic filler having a fiber diameter of 2 to 50 μm is preferably 2 to 170 parts by weight, more preferably 3 to 140 parts by weight, based on 100 parts by weight of the thermoplastic polyester (A). If the amount is less than 2 parts by weight, the effect of improving mechanical properties is not sufficiently exhibited, so that it is not preferable. If the amount exceeds 170 parts by weight, moldability tends to be impaired.
[0023]
In the present invention, (G) a plate-like inorganic filler is blended. Its average particle size is 300-3000 μm. Here, the average particle diameter means a weight average particle diameter measured by a particle size distribution. The plate-like inorganic filler is not particularly limited as long as it is generally used for reinforcing a resin, but glass flakes, mica, and metal foil are preferably used, and glass flake is particularly preferably used. The above-mentioned glass flakes are not particularly limited as long as they are generally used for strengthening a resin, and may be coated or bundled with a thermosetting resin such as a thermoplastic resin or an epoxy resin, and surface-treated with an aminosilane or an epoxysilane. What has been used is also preferably used. The blending amount of the glass flakes in the plate-like inorganic filler is preferably 50% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more. Further, the compounding amount of the plate-like inorganic filler is preferably from 2 to 170 parts by weight, more preferably from 3 to 140 parts by weight, based on 100 parts by weight of the thermoplastic polyester (A). If it is less than 2 parts by weight, the effect of improving mechanical properties is not sufficiently exhibited, and if it exceeds 170 parts by weight, moldability tends to be impaired.
[0024]
In the present invention, in addition to the inorganic fillers specifically exemplified above, (F) a fibrous inorganic filler, (G) a plate-like inorganic filler or other fillers include ceramic fibers, ceramic beads, asbestos, Wollastenite, talc, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silica, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, oxide Titanium, aluminum silicate, silicon oxide, gypsum, novacurite, dawsonite, clay and the like can also be incorporated.
[0025]
In the present invention, the combination ratio of the (F) fibrous inorganic filler having a fiber diameter of 2 to 50 μm and the (G) plate-like inorganic filler is such that the (G) component amount is 0 with respect to the (F) component amount. When the amount is in the range of 0.25 to 4 times, preferably 0.3 to 3.5 times, the function is further improved, and when the amount is less than 0.25 times, the anisotropy of the reinforced polyester composition is reduced. When the amount exceeds 4 times, the effect of improving the mechanical properties is not sufficiently exhibited, which is not preferable.
[0026]
For the present invention, an antioxidant, an ultraviolet absorber, a heat stabilizer, a nucleating agent, a lubricant, a mold release agent, a coloring agent including a dye and a pigment, a nucleating agent, and the like, as long as the object of the present invention is not impaired. Thermoplastic resins (for example, polyethylene, acrylic resin, polyamide, polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal polyester resin, polyacetal, polysulfone, polyphenylene oxide, etc.) and thermosetting resins (for example, phenol resin, melamine resin, polyester resin, And at least one of them such as silicone resin and epoxy resin).
[0027]
The method for producing the composition of the present invention is not particularly limited. For example, polybutylene terephthalate, (a) having a softening point of 50 ° C. or less, an epoxy group-containing unsaturated monomer comprising an α-olefin and an epoxy group-containing unsaturated monomer. A copolymer, or (b) a polyolefin that is an ethylene copolymer of ethylene and an α-olefin having 3 or more carbon atoms and / or a vinyl monomer , if necessary, another thermoplastic polyester resin, and organic bromination. After pre-blending the compound, antimony compound, fluorine-based resin and other additives as necessary, at a temperature higher than the melting point of polybutylene terephthalate, the mixture is supplied to a hopper of a twin-screw extruder having one or more zones of a kneading block. From the feeder, a fibrous inorganic filler with a fiber diameter of 2 to 50 μm and a plate-like shape with an average particle size of 300 to 3000 μm A method in which a filler is supplied to an extruder and uniformly melt-kneaded, or after all blended compositions have been previously blended, the screw shape is not particularly limited at or above the melting point of polybutylene terephthalate. A method in which the mixture is supplied to a hopper of a screw extruder and uniformly melted and kneaded is preferably used.
[0028]
The obtained reinforced polyester resin composition can be molded by any method such as generally known injection molding, extrusion molding and the like.
[0029]
The molded article obtained from the composition of the present invention has good mechanical properties, and particularly the molded article obtained by injection molding has extremely small anisotropy, and has low warpage and is provided with flame retardancy. As a material, it can be used for various applications such as precision equipment parts such as electric / electronic connector parts, automobile parts, and mechanical parts.
[0030]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. All copies in the examples are on a weight basis. Table 1 shows the content of the composition used in the examples.
[0031]
[Table 1]
<Method for producing reinforced flame-retardant polyester resin composition>
Incorporate 2 zones of kneading block between the base part and side feeder of TEX44 twin screw extruder manufactured by Nippon Steel Works and 1 zone of kneading block between side feeder and die which is discharge port. After setting to 260 ° C., a polybutylene terephthalate having an intrinsic viscosity of 0.92 was placed in the hopper in the filling section, a thermoplastic polyester resin having the composition shown in the table, an ethylene / ethyl acrylate copolymer, an organic bromine compound, an antimony compound and fluorine. A blended product containing the base resin was supplied, glass fibers and glass flakes were supplied from a side feeder to perform melt-kneading, and the strand discharged from the die was passed through a cooling bath and pelletized by a strand cutter.
[0033]
<Evaluation method of molded article of reinforced flame-retardant polyester resin composition>
Using the pellets obtained with the above twin screw extruder, a processing temperature of 250 ° C., a mold temperature of 80 ° C., and a molding cycle (injection time / cooling time / intermediate time) of ８ ″ thickness in 8/10/5 seconds The tensile test piece and the Izod test piece were injection molded and subjected to a tensile test according to ASTM D638 and an Izod impact test according to ASTM D265 to evaluate mechanical properties.
[0034]
Using another resin composition, a 1 mm thick, 80 mm long x 80 mm wide square plate was injection molded with a film gate mold, and the molding direction was measured by a universal projector in the flow direction and the direction perpendicular to the flow. A material having a larger difference in molding shrinkage between the flow direction and the direction perpendicular to the flow is judged to have higher anisotropy.
[0035]
In addition, a 1 mm thick, 80 mm long, 80 mm wide square plate is passed through a 50 mm long metal jig having a space of 80 mm wide and 1.35 mm high. And passed through the above-mentioned 50 square plates, and the defect rate was calculated. Note that this test is a useful test for evaluating warpage, and each board with less warp passes through the above jig.
[0036]
In addition, a flame retardancy test was performed according to the UL94 standard, and the flame retardancy rank was determined. The criteria for the above-mentioned flame-retardant rank are as follows: UL94HB, UL94V-2, UL94V-1, UL94V-0. The electrical components such as connector components are UL94 V-2 to V-0. There is a demand for materials having flame retardancy.
[0037]
Examples 1 to 10, Comparative Examples 1 to 10
According to the above-described method for producing a reinforced flame-retardant polyester resin composition, reinforced flame-retardant polyester resin compositions of Examples 1 to 10 and Comparative Examples 1 to 10 having the composition shown in Tables 2 and 3 were obtained. In addition, according to the evaluation method of the molded article of the reinforced flame-retardant polyester resin composition, the molded articles of the reinforced flame-retardant polyester resin compositions of Examples 1 to 10 and Comparative Examples 1 to 10 were evaluated. Tables 2 and 3 show the same as the composition.
[0038]
[Table 2]
[Table 3]
From the results of Examples and Comparative Examples in Tables 2 and 3, the polybutylene terephthalate of the present invention contains (a) an epoxy group containing an α-olefin and an epoxy group-containing unsaturated monomer having a softening temperature of 50 ° C. or less. A polyolefin, an organic bromine compound, an antimony compound, and, if necessary, a fluororesin, which is a copolymer or (b) an ethylene copolymer of ethylene and an α-olefin having 3 or more carbon atoms and / or a vinyl monomer The reinforced flame-retardant polyester resin composition comprising a fibrous inorganic filler having a fiber diameter of 2 to 50 μm and a plate-like inorganic filler having an average diameter of 300 to 3000 μm has better mechanical properties than the comparative example, and has anisotropy. It can be understood that an injection molded product which is extremely small, has flame retardancy, and has little warpage can be stably obtained.
[0041]
【The invention's effect】
The reinforced flame-retardant polyester resin composition of the present invention has good mechanical properties and extremely small anisotropy of the molded product, and a molded product having a small amount of warpage and a small flame-retardant ratio is obtained. Useful for electrical / electronic parts such as connectors with high precision and precision molded parts.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22159796A JP3605956B2 (en) | 1996-08-22 | 1996-08-22 | Reinforced polyester resin composition and molded article thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22159796A JP3605956B2 (en) | 1996-08-22 | 1996-08-22 | Reinforced polyester resin composition and molded article thereof |
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| Publication Number | Publication Date |
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| JPH1060241A JPH1060241A (en) | 1998-03-03 |
| JP3605956B2 true JP3605956B2 (en) | 2004-12-22 |
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| JP22159796A Expired - Lifetime JP3605956B2 (en) | 1996-08-22 | 1996-08-22 | Reinforced polyester resin composition and molded article thereof |
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| JP4266609B2 (en) | 2002-10-08 | 2009-05-20 | 株式会社プライムポリマー | Molding method and resin molded body |
| KR101288561B1 (en) | 2009-12-11 | 2013-07-22 | 제일모직주식회사 | Glass fiber-reinforced polyester resin composition and molded product using the same |
| KR101360892B1 (en) | 2011-06-21 | 2014-02-11 | 제일모직주식회사 | Polyester Resin Composition Having Good Reflectance, Heat Resistance, Yellowing Resistance and Humidity Resistance |
| KR101549492B1 (en) | 2011-12-28 | 2015-09-03 | 제일모직주식회사 | Polyester Resin Composition Having Yellowing Resistance and High Impact Strength |
| KR101484390B1 (en) * | 2012-04-24 | 2015-01-19 | 주식회사 엘지화학 | Thermoplastic polyester elastomer resin composition and molding articles comprising the same |
| US8754171B2 (en) * | 2012-05-10 | 2014-06-17 | E I Du Pont De Nemours And Company | Polyester composition |
| KR20140086738A (en) | 2012-12-28 | 2014-07-08 | 제일모직주식회사 | Resin compositions and articles including the same |
| WO2014104485A1 (en) | 2012-12-28 | 2014-07-03 | 제일모직 주식회사 | Thermoplastic resin composition and moulded article comprising same |
| US10301449B2 (en) | 2013-11-29 | 2019-05-28 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition having excellent light stability at high temperature |
| KR101690829B1 (en) | 2013-12-30 | 2016-12-28 | 롯데첨단소재(주) | Thermoplastic resin composition having excellent Impact resistance and light stability |
| US10636951B2 (en) | 2014-06-27 | 2020-04-28 | Lotte Advanced Materials Co., Ltd. | Thermoplastic resin composition having excellent reflectivity |
| KR101793319B1 (en) | 2014-12-17 | 2017-11-03 | 롯데첨단소재(주) | Polyester resin composition and molded part using the same |
| KR101849830B1 (en) | 2015-06-30 | 2018-04-18 | 롯데첨단소재(주) | Polyester resin composition with excellent impact resistance and light reliability and molded article using the same |
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