JP5538188B2 - Flame retardant thermoplastic polyester resin composition - Google Patents
Flame retardant thermoplastic polyester resin composition Download PDFInfo
- Publication number
- JP5538188B2 JP5538188B2 JP2010257098A JP2010257098A JP5538188B2 JP 5538188 B2 JP5538188 B2 JP 5538188B2 JP 2010257098 A JP2010257098 A JP 2010257098A JP 2010257098 A JP2010257098 A JP 2010257098A JP 5538188 B2 JP5538188 B2 JP 5538188B2
- Authority
- JP
- Japan
- Prior art keywords
- mass
- thermoplastic polyester
- polyester resin
- resin composition
- flame
- 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.)
- Active
Links
- 239000003063 flame retardant Substances 0.000 title claims description 71
- 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 title claims description 70
- 229920006230 thermoplastic polyester resin Polymers 0.000 title claims description 55
- 239000000203 mixture Substances 0.000 title claims description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 48
- -1 polybutylene terephthalate Polymers 0.000 claims description 43
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 34
- 229920000578 graft copolymer Polymers 0.000 claims description 29
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 26
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 23
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000012779 reinforcing material Substances 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000000962 organic group Chemical group 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 150000001463 antimony compounds Chemical class 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims 1
- 239000004416 thermosoftening plastic Substances 0.000 claims 1
- 239000011342 resin composition Substances 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 239000012796 inorganic flame retardant Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012778 molding material Substances 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 3
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 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
- QRFTXHFUNIFHST-UHFFFAOYSA-N 4,5,6,7-tetrabromoisoindole-1,3-dione Chemical compound BrC1=C(Br)C(Br)=C2C(=O)NC(=O)C2=C1Br QRFTXHFUNIFHST-UHFFFAOYSA-N 0.000 description 2
- LPUUYZVKCMCHLO-UHFFFAOYSA-N 4,5,6,7-tetrachloroisoindole-1,3-dione Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)NC(=O)C2=C1Cl LPUUYZVKCMCHLO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group 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
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 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
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GRKDVZMVHOLESV-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl prop-2-enoate Chemical compound BrC1=C(Br)C(Br)=C(COC(=O)C=C)C(Br)=C1Br GRKDVZMVHOLESV-UHFFFAOYSA-N 0.000 description 1
- WVJRAJZMOVQFEC-UHFFFAOYSA-N 1,2,3,4-tetrabromo-5,6-dimethylbenzene Chemical group CC1=C(C)C(Br)=C(Br)C(Br)=C1Br WVJRAJZMOVQFEC-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZUHPIMDQNAGSOV-UHFFFAOYSA-N 2-benzyl-2-phenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)(C(O)=O)CC1=CC=CC=C1 ZUHPIMDQNAGSOV-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VSVXWPQYGGGCAC-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[4-[4-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)phenoxy]phenyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O VSVXWPQYGGGCAC-UHFFFAOYSA-N 0.000 description 1
- RHFKNNBDKARGKL-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[4-[[4-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)phenyl]methyl]phenyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1C(C=C1)=CC=C1CC(C=C1)=CC=C1N1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O RHFKNNBDKARGKL-UHFFFAOYSA-N 0.000 description 1
- DWGBBQYNEFJAFH-UHFFFAOYSA-N 4,5,6,7-tetrachloro-2-[4-[4-(4,5,6,7-tetrachloro-1,3-dioxoisoindol-2-yl)phenoxy]phenyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C(=O)N1C(C=C1)=CC=C1OC(C=C1)=CC=C1N1C(=O)C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C2C1=O DWGBBQYNEFJAFH-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- AHNNEQUPFITBDU-UHFFFAOYSA-N [dibromo-(2-bromophenyl)methyl] prop-2-enoate Chemical compound BrC1=CC=CC=C1C(Br)(Br)OC(=O)C=C AHNNEQUPFITBDU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 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 1
- 239000010951 brass Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 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
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UGQZLDXDWSPAOM-UHFFFAOYSA-N pyrrolo[3,4-f]isoindole-1,3,5,7-tetrone Chemical compound C1=C2C(=O)NC(=O)C2=CC2=C1C(=O)NC2=O UGQZLDXDWSPAOM-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- BMENBXQCFCSBAQ-UHFFFAOYSA-N sodium;oxido(dioxo)-$l^{5}-stibane Chemical compound [Na+].[O-][Sb](=O)=O BMENBXQCFCSBAQ-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-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
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、難燃性熱可塑性ポリエステル樹脂組成物に関する。特に、ハロゲン系難燃剤を必須とし、難燃性に加えて、衝撃強度、外観および溶着性に優れた難燃性熱可塑性ポリエステル樹脂組成物に関する。 The present invention relates to a flame retardant thermoplastic polyester resin composition. In particular, the present invention relates to a flame-retardant thermoplastic polyester resin composition that requires a halogen-based flame retardant and is excellent in impact strength, appearance, and weldability in addition to flame retardancy.
熱可塑性ポリエステル樹脂は、その優れた特性から電気及び電子機器部品並びに自動車部品等に広く用いられている。特に、ポリブチレンテレフタレート系樹脂（以下、「ＰＢＴ」と略記することがある。）は、要求特性に応じて様々な処方により高機能化と高性能化を実現してきた。 Thermoplastic polyester resins are widely used in electrical and electronic equipment parts, automobile parts and the like because of their excellent characteristics. In particular, polybutylene terephthalate-based resins (hereinafter sometimes abbreviated as “PBT”) have realized high functionality and high performance by various formulations according to required characteristics.
しかし、近年では部品の軽量小型化の為に、樹脂成形体の薄肉化が進められている。これに伴い、薄肉でも、難燃性に優れ、衝撃強度が高い樹脂成形体を提供できる難燃性熱可塑性ポリエステル樹脂組成物が求められている。さらに、外観に優れることや高い溶着性も重要な課題となっている。 However, in recent years, the thickness of resin molded bodies has been reduced in order to reduce the weight and size of parts. Accordingly, there is a demand for a flame-retardant thermoplastic polyester resin composition that can provide a resin molded article that is excellent in flame retardancy and has high impact strength even if it is thin. Furthermore, excellent appearance and high weldability are also important issues.
ここで、特許文献１には、ハロゲン系難燃剤を必須とする難燃性熱可塑性ポリエステル樹脂組成物が開示されている。しかしながら、特許文献１に記載の組成物では、衝撃強度、外観および溶着性のいずれかが劣ってしまう。
Here,
本発明は上記従来技術の問題点を解決することを目的としたものであって、難燃性に加えて、衝撃強度、外観および溶着性にも優れた難燃性熱可塑性ポリエステル樹脂組成物を提供することを目的とする。 The present invention aims to solve the above-mentioned problems of the prior art, and in addition to flame retardancy, a flame retardant thermoplastic polyester resin composition excellent in impact strength, appearance and weldability is provided. The purpose is to provide.
かかる状況のもと、本発明者が鋭意検討を行った結果、熱可塑性ポリエステル樹脂組成物において、エラストマー成分として、少なくともブタジエンを重合してなるゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させたグラフト重合体を配合し、かつ、ハロゲン系難燃剤を配合することにより、高い難燃性に加えて、優れた衝撃強度、外観および溶着性を達成可能なことを見出し、本発明を完成するに至った。一般的に、エラストマー成分を添加すると、難燃性が低下することが知られているが、本発明では、エラストマー成分として、特定の組成を有するものを採用し、かつ、ハロゲン系難燃剤を添加することにより、高い難燃性を達成したものである。具体的には、以下の手段により、本発明の課題は達成された。
（１）（Ａ）熱可塑性ポリエステル樹脂１００質量部に対し、
（Ｂ）少なくともブタジエンを重合してなるゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させたグラフト重合体を１質量部〜３０質量部、
（Ｃ）ハロゲン系難燃剤を７質量部〜４０質量部、
（Ｄ）無機系難燃助剤を３質量部〜２０質量部および
（Ｅ）無機系強化材を１質量部〜９０質量部
を含み、（Ｂ）グラフト重合体以外のエラストマーの含量が（Ａ）熱可塑性ポリエステル樹脂に対して３質量％以下である難燃性熱可塑性ポリエステル樹脂組成物。
（２）前記（Ｂ）グラフト重合体中のスチレン含有量が、３質量％以上である、（１）に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（３）前記（Ｂ）グラフト重合体が、少なくともスチレンとブタジエンを共重合してなるゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させたグラフト重合体である、（１）または（２）に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（４）熱可塑性ポリエステル樹脂が、ポリブチレンテレフタレート樹脂を含む、（１）〜（３）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（５）熱可塑性ポリエステル樹脂が、ポリブチレンテレフタレート樹脂とポリエチレンテレフタレート樹脂を含む、（１）〜（３）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（６）（Ｃ）ハロゲン系難燃剤が、臭素化エポキシ化合物、下記式（１）で表される化合物および下記式（２）で表される重合体の少なくとも１種を含む、（１）〜（５）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（７）（Ｃ）ハロゲン系難燃剤が臭素系難燃剤である、（１）〜（６）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（８）（Ｄ）無機系難燃助剤が五酸化アンチモンである、（１）〜（７）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（９）ハロゲン系難燃剤以外の難燃剤を実質的に含まない、（１）〜（８）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物。
（１０）（１）〜（９）のいずれか１項に記載の難燃性熱可塑性ポリエステル樹脂組成物を成形してなる成形品。
Under such circumstances, as a result of intensive studies by the present inventors, in the thermoplastic polyester resin composition, at least methyl methacrylate and styrene are graft-polymerized as a rubber polymer obtained by polymerizing at least butadiene as an elastomer component. In addition to high flame retardancy, it was found that by blending the grafted polymer and the halogenated flame retardant, it was possible to achieve excellent impact strength, appearance and weldability, and the present invention was completed. It came to do. In general, it is known that when an elastomer component is added, the flame retardancy is reduced, but in the present invention, an elastomer component having a specific composition is employed and a halogen-based flame retardant is added. By doing so, high flame retardancy is achieved. Specifically, the object of the present invention has been achieved by the following means.
(1) (A) For 100 parts by mass of thermoplastic polyester resin,
(B) 1 to 30 parts by mass of a graft polymer obtained by graft-polymerizing at least methyl methacrylate and styrene to a rubbery polymer obtained by polymerizing at least butadiene;
(C) 7 to 40 parts by mass of a halogen-based flame retardant,
(D) 3 to 20 parts by weight of an inorganic flame retardant aid and (E) 1 to 90 parts by weight of an inorganic reinforcing material, and (B) the content of elastomer other than the graft polymer is (A ) A flame-retardant thermoplastic polyester resin composition that is 3% by mass or less based on the thermoplastic polyester resin.
(2) The flame-retardant thermoplastic polyester resin composition according to (1), wherein the styrene content in the graft polymer (B) is 3% by mass or more.
(3) The graft polymer (B) is a graft polymer obtained by graft-polymerizing at least methyl methacrylate and styrene to a rubbery polymer obtained by copolymerizing at least styrene and butadiene. ) The flame-retardant thermoplastic polyester resin composition.
(4) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (3), wherein the thermoplastic polyester resin contains a polybutylene terephthalate resin.
(5) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (3), wherein the thermoplastic polyester resin comprises a polybutylene terephthalate resin and a polyethylene terephthalate resin.
(6) (C) The halogen-based flame retardant includes at least one of a brominated epoxy compound, a compound represented by the following formula (1), and a polymer represented by the following formula (2), The flame-retardant thermoplastic polyester resin composition according to any one of (5).
(7) The flame retardant thermoplastic polyester resin composition according to any one of (1) to (6), wherein the halogen flame retardant (C) is a bromine flame retardant.
(8) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (7), wherein (D) the inorganic flame-retardant aid is antimony pentoxide.
(9) The flame-retardant thermoplastic polyester resin composition according to any one of (1) to (8), which contains substantially no flame retardant other than a halogen-based flame retardant.
(10) A molded product obtained by molding the flame-retardant thermoplastic polyester resin composition according to any one of (1) to (9).
本発明により、難燃性に加えて、衝撃強度、外観および溶着性に優れた難燃性熱可塑性ポリエステル樹脂組成物を提供可能になった。
本発明の難燃性熱可塑性ポリエステル樹脂組成物を成形して得られる成形品は、自動車分野、特に難燃性が必要な電気自動車用コネクター、電気・電子部品用コネクターとして有用である。
According to the present invention, it is possible to provide a flame retardant thermoplastic polyester resin composition excellent in impact strength, appearance and weldability in addition to flame retardancy.
The molded product obtained by molding the flame-retardant thermoplastic polyester resin composition of the present invention is useful in the automotive field, particularly as a connector for electric vehicles and a connector for electric / electronic parts that require flame retardancy.
以下において、本発明の内容について詳細に説明する。尚、本願明細書において「〜」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。本明細書において、アルキル基等の「基」は、特に述べない限り、置換基を有していてもよいし、有していなくてもよい。さらに、炭素数が限定されている基の場合、該炭素数は、置換基が有する炭素数を含めた数を意味している。 Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has.
本発明の難燃性熱可塑性ポリエステル樹脂組成物は、（Ａ）熱可塑性ポリエステル樹脂１００質量部に対し、（Ｂ）少なくともブタジエンを重合してなるゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させたグラフト重合体を１質量部〜３０質量部、（Ｃ）ハロゲン系難燃剤を７質量部〜４０質量部、（Ｄ）無機系難燃助剤を３質量部〜２０質量部および（Ｅ）無機系強化材を１質量部〜９０質量部を含み、（Ｂ）グラフト重合体以外のエラストマーの含量が（Ａ）熱可塑性ポリエステル樹脂に対して３質量％以下であることを特徴とする。以下、本発明の組成物について詳細に説明する。 The flame-retardant thermoplastic polyester resin composition of the present invention is obtained by grafting (B) at least methyl methacrylate and styrene onto a rubber polymer obtained by polymerizing (B) at least butadiene with respect to (A) 100 parts by mass of the thermoplastic polyester resin. 1 to 30 parts by mass of the polymerized graft polymer, (C) 7 to 40 parts by mass of a halogen-based flame retardant, (D) 3 to 20 parts by mass of an inorganic flame retardant aid and ( E) 1 to 90 parts by mass of the inorganic reinforcing material, and (B) the content of the elastomer other than the graft polymer is 3% by mass or less based on (A) the thermoplastic polyester resin. . Hereinafter, the composition of the present invention will be described in detail.
（Ａ）熱可塑性ポリエステル樹脂
本発明の樹脂組成物（Ａ）の主成分である熱可塑性ポリエステル樹脂とは、ジカルボン酸化合物とジヒドロキシ化合物の重縮合、オキシカルボン酸化合物の重縮合、又はこれらの化合物の混合物の重縮合などによって得られるポリエステルであり、ホモポリエステル、コポリエステルのいずれであってもよい。熱可塑性ポリエステル樹脂を構成するジカルボン酸化合物としては、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェニルエタンジカルボン酸などの芳香族ジカルボン酸、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、アジピン酸、セバシン酸などの脂肪族ジカルボン酸が挙げられる。
(A) Thermoplastic polyester resin The thermoplastic polyester resin which is the main component of the resin composition (A) of the present invention is a polycondensation of a dicarboxylic acid compound and a dihydroxy compound, a polycondensation of an oxycarboxylic acid compound, or these compounds. It is a polyester obtained by polycondensation of the above mixture, and may be either a homopolyester or a copolyester. Examples of the dicarboxylic acid compound constituting the thermoplastic polyester resin include alicyclic acids such as terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyldicarboxylic acid, diphenylether dicarboxylic acid, diphenylethanedicarboxylic acid, and cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids such as dicarboxylic acid, adipic acid and sebacic acid can be mentioned.
これらは周知のように、遊離酸以外にジメチルエステルなどのエステル形成性誘導体として重縮合反応に用いることができる。オキシカルボン酸としてはパラオキシ安息香酸、オキシナフトエ酸、ジフェニレンオキシカルボン酸などが挙げられる。これらは単独で重縮合させることもできるが、ジカルボン酸化合物に少量併用することが多い。 As is well known, these can be used in polycondensation reactions as ester-forming derivatives such as dimethyl esters in addition to free acids. Examples of the oxycarboxylic acid include paraoxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid. These can be polycondensed alone, but are often used in a small amount together with a dicarboxylic acid compound.
ジヒドロキシ化合物としては、エチレングリコール、プロピレングリコール、ブタンジオール、ネオペンチルグリコール、ポリオキシアルキレングリコールなどの脂肪族ジオールが主として用いられるが、ハイドロキノン、レゾルシン、ナフタレンジオール、ジヒドロキシジフェニルエーテル、２，２−ビス（４−ヒドロキシフェニル）プロパンなどの芳香族ジオールやシクロヘキサンジオールなどの脂環式ジオールも用いることができる。 As the dihydroxy compound, aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and polyoxyalkylene glycol are mainly used. Hydroquinone, resorcin, naphthalenediol, dihydroxydiphenyl ether, 2,2-bis (4 Aromatic diols such as -hydroxyphenyl) propane and cycloaliphatic diols such as cyclohexanediol can also be used.
またこのような二官能性化合物以外に、分岐構造を導入するためトリメリット酸、トリメシン酸、ピロメリット酸、ペンタエリスリトール、トリメチロールプロパンなどの三官能以上の多官能化合物や、分子量調節のための脂肪酸などの単官能化合物を少量併用することもできる。 In addition to these bifunctional compounds, trifunctional or higher polyfunctional compounds such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure. A small amount of a monofunctional compound such as a fatty acid can also be used.
本発明では、熱可塑性ポリエステル樹脂としては、通常は主としてジカルボン酸化合物とジヒドロキシ化合物とから成る重縮合物、即ち計算上、ジカルボン酸化合物とジヒドロキシ化合物のエステルである構造単位が、樹脂全体の好ましくは７０質量％以上、より好ましくは９０質量％以上を占めるものを用いる。ジカルボン酸化合物としては芳香族ジカルボン酸が好ましく、ジヒドロキシ化合物としては脂肪族ジオールが好ましい。 In the present invention, the thermoplastic polyester resin is usually a polycondensate composed mainly of a dicarboxylic acid compound and a dihydroxy compound, that is, a structural unit which is an ester of a dicarboxylic acid compound and a dihydroxy compound in calculation, What occupies 70 mass% or more, More preferably, 90 mass% or more is used. The dicarboxylic acid compound is preferably an aromatic dicarboxylic acid, and the dihydroxy compound is preferably an aliphatic diol.
なかでも好ましいのは、酸性分の９５モル％以上がテレフタル酸であり、アルコール成分の９５モル％以上が脂肪族ジオールであるポリアルキレンテレフタレート樹脂である。その代表的なものはポリブチレンテレフタレート樹脂及びポリエチレンテレフタレート樹脂であり、本発明では、少なくとも、ポリブチレンテレフタレート樹脂を含むことが好ましく、ポリブチレンテレフタレート樹脂とポリエチレンテレフタレート樹脂の両方を含むことがより好ましい。ポリブチレンテレフタレート樹脂とポリエチレンテレフタレート樹脂の両方を含むにより、得られる成形品の外観がより良好となる傾向にある。ポリブチレンテレフタレート樹脂とポリエチレンテレフタレート樹脂の配合比（質量比）は、１００：０〜５０：５０であることが好ましい。 Particularly preferred is a polyalkylene terephthalate resin in which 95 mol% or more of the acidic component is terephthalic acid and 95 mol% or more of the alcohol component is an aliphatic diol. Typical examples thereof are polybutylene terephthalate resin and polyethylene terephthalate resin. In the present invention, at least polybutylene terephthalate resin is preferable, and it is more preferable that both polybutylene terephthalate resin and polyethylene terephthalate resin are included. By including both the polybutylene terephthalate resin and the polyethylene terephthalate resin, the appearance of the obtained molded product tends to be better. The blending ratio (mass ratio) of the polybutylene terephthalate resin and the polyethylene terephthalate resin is preferably 100: 0 to 50:50.
熱可塑性ポリエステル樹脂の固有粘度は適宜選択して決定すればよいが、通常０．５〜２ｄｌ／ｇであることが好ましく、中でも樹脂組成物の成形性及び機械的特性の観点から０．６〜１．５ｄｌ／ｇであることが好ましい。固有粘度が０．５ｄｌ／ｇ未満のものを用いると、樹脂組成物から得られる成形品の機械的強度が低くなる傾向にあり、逆に２ｄｌ／ｇより大きいと樹脂組成物の流動性が低下し、成形性が低下する場合がある。 The intrinsic viscosity of the thermoplastic polyester resin may be appropriately selected and determined. However, it is usually preferably 0.5 to 2 dl / g, and in particular, from the viewpoint of moldability and mechanical properties of the resin composition, 0.6 to It is preferably 1.5 dl / g. If a material having an intrinsic viscosity of less than 0.5 dl / g is used, the mechanical strength of the molded product obtained from the resin composition tends to be low, and conversely if it is greater than 2 dl / g, the fluidity of the resin composition decreases. However, moldability may be reduced.
尚、本明細書においてポリエステル樹脂の固有粘度は、テトラクロロエタンとフェノールとの１：１（質量比）の混合溶媒中、３０℃で測定した値である。 In the present specification, the intrinsic viscosity of the polyester resin is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.
（Ｂ）少なくともブタジエンを重合してなるゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させたグラフト重合体
本発明の樹脂組成物は、少なくともブタジエンを重合してなるゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させたグラフト重合体を含む。本発明で用いるグラフト重合体は、通常、コア−シェル構造体と称されるものであるが、コア−シェル構造を有していることを必須とするものではない。
少なくともブタジエンを重合してなるゴム質重合体は、ブタジエンのみからなっていてもよいし、ブタジエンと他の単量体を共重合させたゴム質重合体であってもよい。他の単量体としては、スチレン、α−メチルスチレン、ビニルトルエン等の芳香族アルケニル化合物、アクリロニトリル、メタクリロニトリル等のシアン化ビニル化合物等の各種ビニル系単量体を共重合成分として含んで良い。中でもスチレン、α−メチルスチレンが好ましい。
本発明におけるグラフト重合体は、スチレン含有量が３質量％以上であることが好ましく、また、１０質量％以下であることが好ましい。
本発明におけるゴム質重合体は、その４０質量％以上がブタジエン由来であることが好ましく、より好ましくは、４５質量％以上である。他の単量体成分は、４０質量％以下であることが好ましく、３０〜０．０５質量％であることがより好ましい。他の単量体成分としてスチレン由来の成分を含む場合、その配合量は２５〜０．０５質量％であることが好ましい。スチレンの配合量を、前記範囲とすることにより、難燃性と耐衝撃性が向上する。
本発明で用いるゴム質重合体の体積平均粒子径は特に限定されないが、好ましくは、０．０８〜１．５μｍである。
本発明で用いるグラフト重合体は、上記ゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させて得られるものである。グラフト重合させる単量体は、メチルメタクリレート成分が４０質量％以下、スチレン成分が３０〜０．００５質量％、他の成分が５質量％以下であることが好ましく、メチルメタクリレート成分が３５質量％以下、スチレン成分が２５〜０．００５質量％、他の成分が４質量％以下であることがより好ましい。このような組成比とすることにより、難燃性と耐衝撃性が向上する。
(B) Graft polymer obtained by graft polymerization of at least methyl methacrylate and styrene on a rubber polymer obtained by polymerizing at least butadiene. The resin composition of the present invention comprises at least a rubber polymer obtained by polymerizing butadiene. At least a graft polymer obtained by graft polymerization of methyl methacrylate and styrene is included. The graft polymer used in the present invention is usually referred to as a core-shell structure, but does not necessarily have a core-shell structure.
The rubbery polymer obtained by polymerizing at least butadiene may be composed only of butadiene, or may be a rubbery polymer obtained by copolymerizing butadiene and another monomer. Other monomers include various vinyl monomers such as aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile as copolymerization components. good. Of these, styrene and α-methylstyrene are preferred.
The graft polymer in the present invention preferably has a styrene content of 3% by mass or more, and preferably 10% by mass or less.
The rubber polymer in the present invention is preferably 40% by mass or more derived from butadiene, more preferably 45% by mass or more. The other monomer component is preferably 40% by mass or less, and more preferably 30 to 0.05% by mass. When the styrene-derived component is included as the other monomer component, the blending amount is preferably 25 to 0.05% by mass. By setting the blending amount of styrene within the above range, flame retardancy and impact resistance are improved.
The volume average particle diameter of the rubbery polymer used in the present invention is not particularly limited, but is preferably 0.08 to 1.5 μm.
The graft polymer used in the present invention is obtained by graft-polymerizing at least methyl methacrylate and styrene to the rubber polymer. The monomer to be graft polymerized is preferably 40% by mass or less of methyl methacrylate component, 30 to 0.005% by mass of styrene component, 5% by mass or less of other components, and 35% by mass or less of methyl methacrylate component. More preferably, the styrene component is 25 to 0.005 mass%, and the other components are 4 mass% or less. By setting it as such a composition ratio, a flame retardance and impact resistance improve.
本発明で用いるグラフト重合体の体積平均粒子径は特に限定されないが、好ましくは、０．１〜２．０μｍである。 The volume average particle diameter of the graft polymer used in the present invention is not particularly limited, but is preferably 0.1 to 2.0 μm.
本発明で用いるグラフト重合体は、特開２００５−１１２９０７号公報に記載の方法等公知の方法に従って製造できる。また、市販品を用いることもできる。市販品としては、後述する実施例で採用するもののほか、三菱レイヨン製メタブレンＣ−２１５Ａ、Ｃ―９３０Ａ、Ｃ−２２３Ａが例示される。 The graft polymer used in the present invention can be produced according to a known method such as the method described in JP-A-2005-112907. Commercial products can also be used. Examples of commercially available products include those employed in Examples described later, and Metablene C-215A, C-930A, and C-223A manufactured by Mitsubishi Rayon.
本発明で用いるグラフト重合体の含有量は、（Ａ）熱可塑性ポリエステル樹脂１００質量部に対して、１質量部〜３０質量部であり、１質量部〜２０質量部が好ましく、１質量部〜１５質量部がより好ましい。 Content of the graft polymer used by this invention is 1 mass part-30 mass parts with respect to 100 mass parts of (A) thermoplastic polyester resins, 1 mass part-20 mass parts are preferable, and 1 mass part- 15 parts by mass is more preferable.
そして本発明では、上記グラフト重合体（Ｂ）以外のエラストマー成分を実質的に含んでいないことをも特徴とする。実質的に含まないとは、通常、（Ａ）熱可塑性ポリエステル樹脂成分に対し、３質量％以下である。
グラフト重合体（Ｂ）以外のエラストマー成分含有用が多すぎると、難燃性や外観の低下が生ずる場合があるので、出来る限り含有量を低くすることが好ましい。ここで（Ｂ）以外のエラストマー成分とは、ガラス転移温度（Ｔｇ）が０℃以下の、従来公知の任意のエラストマーを示す。
And this invention is characterized by not containing elastomer components other than the said graft polymer (B) substantially. “Not substantially contained” is usually 3% by mass or less based on the thermoplastic polyester resin component (A).
If the elastomer component other than the graft polymer (B) is contained too much, flame retardancy and appearance may be deteriorated, so it is preferable to make the content as low as possible. Here, the elastomer component other than (B) refers to any conventionally known elastomer having a glass transition temperature (Tg) of 0 ° C. or lower.
（Ｃ）ハロゲン系難燃剤
本発明の樹脂組成物は、ハロゲン系難燃剤を含む。ハロゲン原子としては、好ましくは、フッ素、塩素、臭素が好ましく、臭素がより好ましい。
ハロゲン系難燃剤としては、臭素化エポキシ化合物、ビスイミド構造化合物、またはポリブロム化ベンジル（メタ）アクリレート化合物が好ましい。これらの化合物における臭素原子含有量は任意だが、十分な難燃性を付与する上で、通常、１０質量％以上であり、中でも２０質量％以上、特に３０質量％以上であることが好ましく、その上限は８０質量％、中でも７０質量％以下であることが好ましい。
(C) Halogen flame retardant The resin composition of the present invention contains a halogen flame retardant. The halogen atom is preferably fluorine, chlorine or bromine, more preferably bromine.
As the halogen flame retardant, a brominated epoxy compound, a bisimide structure compound, or a polybrominated benzyl (meth) acrylate compound is preferable. The bromine atom content in these compounds is arbitrary, but is usually 10% by mass or more, preferably 20% by mass or more, particularly preferably 30% by mass or more, in order to impart sufficient flame retardancy. The upper limit is 80% by mass, preferably 70% by mass or less.
臭素化エポキシ化合物
本発明に用いる（Ｃ）ハロゲン系難燃剤としての臭素化エポキシ化合物としては、具体的には例えば、テトラブロモビスフェノールＡエポキシに代表されるビスフェノールＡ型臭素化エポキシ化合物が挙げられる。
Brominated Epoxy Compound Specific examples of the brominated epoxy compound (C) as a halogen-based flame retardant used in the present invention include bisphenol A-type brominated epoxy compounds represented by tetrabromobisphenol A epoxy.
臭素化エポキシ化合物の分子量は任意であり、適宜選択して決定すればよいが、通常、質量平均分子量（Ｍｗ）で１００００〜１０００００であり、中でも分子量が高い方が好ましく、具体的にはＭｗとして１５０００〜８００００、中でも１８０００〜７８０００（Ｍｗ）、更には２００００〜７５０００（Ｍｗ）、特に２２０００〜７００００であることが好ましく、この範囲内に於いても分子量の高いものが好ましい。
本発明で用いる臭素化エポキシ化合物のエポキシ当量が４０００〜４００００ｇ／ｅｑであることが好ましく、中でも４５００〜３５０００ｇ／ｅｑがこのましく、特に１００００〜３００００ｇ／ｅｑであることが好ましい。
The molecular weight of the brominated epoxy compound is arbitrary and may be selected and determined as appropriate. Usually, the mass average molecular weight (Mw) is 10,000 to 100,000, and among them, the higher molecular weight is preferable. It is preferably 15000 to 80000, more preferably 18000 to 78000 (Mw), more preferably 20000 to 75000 (Mw), and particularly preferably 22000 to 70000, and even within this range, those having a high molecular weight are preferable.
The epoxy equivalent of the brominated epoxy compound used in the present invention is preferably 4000 to 40000 g / eq, particularly 4500 to 35000 g / eq, and particularly preferably 10,000 to 30000 g / eq.
また、臭素化エポキシ化合物としてオリゴマーを併用することもできる。この際、例えばＭｗが５０００以下のオリゴマーを０〜５０質量％程度用いることで、難燃性、離型性および流動性を適宜調整することができる。臭素化エポキシ化合物における臭素原子含有量は任意だが、十分な難燃性を付与する上で、通常１０質量％以上であり、中でも２０質量％以上、特に３０質量％以上であることが好ましく、その上限は６０質量％、中でも５５質量％以下であることが好ましい。 Moreover, an oligomer can also be used together as a brominated epoxy compound. In this case, for example, by using about 0 to 50% by mass of an oligomer having Mw of 5000 or less, flame retardancy, mold release property and fluidity can be appropriately adjusted. Although the bromine atom content in the brominated epoxy compound is arbitrary, it is usually 10% by mass or more, preferably 20% by mass or more, particularly preferably 30% by mass or more, in order to impart sufficient flame retardancy. The upper limit is 60% by mass, preferably 55% by mass or less.
ビスイミド構造化合物について
本発明に用いる（Ｃ）ハロゲン系難燃剤としてのビスイミド構造化合物は、以下の一般式（１）で表されるものが好ましい。
About Bisimide Structure Compound The bisimide structure compound as the halogen flame retardant (C) used in the present invention is preferably represented by the following general formula (1).
式（１）中、Ｒ1は２価の有機基を示し、具体的には、メチレン、エチレン、１，４−ブチレン、１，６−ヘキサメチレン、フェニレン、４，４′−メチレンジフェニレン、４，４′−オキシジフェニレン、キシリレン、テトラクロロキシリレン、テトラブロモキシリレン等の、アルキレン基、アリレン基が挙げられる。中でも、エチレン、ブチレン、ヘキサメチレン基等の低級アルキレン基が好ましい。 In the formula (1), R 1 represents a divalent organic group, specifically, methylene, ethylene, 1,4-butylene, 1,6-hexamethylene, phenylene, 4,4′-methylenediphenylene, Examples include alkylene groups and arylene groups such as 4,4'-oxydiphenylene, xylylene, tetrachloroxylylene, and tetrabromoxylylene. Of these, lower alkylene groups such as ethylene, butylene and hexamethylene groups are preferred.
式（１）中、Ｒ2およびＲ3は、２価の有機基であり、少なくとも一方が１つ以上のハロゲン原子を有する二価の有機基である。中でもＲ2及びＲ3の両方が、１つ以上のハロゲン原子を有する二価の有機基であることが好ましい。この二価の有機基としては芳香環を含む構造であることが好ましく、中でも１〜４個のハロゲン原子を有するフェニレン基であることが好ましい。ハロゲン原子としては臭素が好ましく、特にＲ2及びＲ3としては、テトラブロモフェニレン基であることが好ましい。 In formula (1), R 2 and R 3 are divalent organic groups, at least one of which is a divalent organic group having one or more halogen atoms. Among them, it is preferable that both R 2 and R 3 are divalent organic groups having one or more halogen atoms. The divalent organic group preferably has a structure containing an aromatic ring, and particularly preferably a phenylene group having 1 to 4 halogen atoms. The halogen atom is preferably bromine, and particularly R 2 and R 3 are preferably tetrabromophenylene groups.
一般式（１）で示されるビスイミド構造の化合物としては、具体的には、Ｎ，Ｎ′−（ｐ−及びｍ−フェニレン）−ビス〔３・４・５・６−テトラ−クロロフタルイミド〕、Ｎ，Ｎ′−（ｐ−及びｍ−フェニレン）−ビス〔３・４・５・６−テトラ−ブロモフタルイミド〕、Ｎ，Ｎ′−（メチレン−ジ−ｐ−フェニレン）−ビス〔３・４・５・６−テトラクロロフタルイミド〕、Ｎ，Ｎ′−（メチレン−ジ−ｐ−フェニレン）ビス〔３・４・５・６−テトラブロモフタルイミド〕、Ｎ，Ｎ′−（オキシ−ジ−ｐ−フェニレン）−ビス〔３・４・５・６−テトラクロロフタルイミド〕、Ｎ，Ｎ′−（オキシ−ジ−ｐ−フェニレン）−ビス〔３・４・５・６−テトラブロモフタルイミド〕、
Ｎ，Ｎ′−（ｐ−及びｍ−テトラクロロキシリレン）−ビス〔３・４・５・６−テトラクロロフタルイミド〕、Ｎ，Ｎ′−（ｐ−及びｍ−テトラクロロキシリレン）−ビス〔３・４・５・６−テトラブロモフタルイミド〕、Ｎ，Ｎ′−（ｐ−及びｍ−テトラクロロキシリレン）−ビスクロルエンドイミド、Ｎ，Ｎ′−（１・２−エチレン）−ビスクロルエンドイミド、Ｎ，Ｎ′−（１・２−エチレン）−ビス〔３・４・５・６−テトラブロモフタルイミド〕、Ｎ，Ｎ′−ビス（１・２・３・４・５−ペンタブロモベンジル）−ピロメリットイミド、Ｎ，Ｎ′−ビス（２・４・６−トリブロモフェニル）ピロメリットイミド、Ｎ，Ｎ′−（ｐ−及びｍ−フェニレン）−ビスクロルエンドイミド等が挙げられる。尚、これらのうちテトラハロキシリレン基は、１・２・４・５−テトラハロキシリレン及び／又は１・３・４・５−テトラロキシリレン基である。
Specific examples of the compound having a bisimide structure represented by the general formula (1) include N, N ′-(p- and m-phenylene) -bis [3,4,5,6-tetra-chlorophthalimide], N, N '-(p- and m-phenylene) -bis [3,4,5,6-tetra-bromophthalimide], N, N'-(methylene-di-p-phenylene) -bis [3.4 .5,6-tetrachlorophthalimide], N, N '-(methylene-di-p-phenylene) bis [3,4,5,6-tetrabromophthalimide], N, N'-(oxy-di-p -Phenylene) -bis [3,4,5,6-tetrachlorophthalimide], N, N '-(oxy-di-p-phenylene) -bis [3,4,5,6-tetrabromophthalimide],
N, N '-(p- and m-tetrachloroxylylene) -bis [3,4,5,6-tetrachlorophthalimide], N, N'-(p- and m-tetrachloroxylylene) -bis [3,4,5,6-tetrabromophthalimide], N, N '-(p- and m-tetrachloroxylylene) -bischlorendimide, N, N'-(1,2-ethylene) -bis Chlorendoimide, N, N '-(1,2-ethylene) -bis [3,4,5,6-tetrabromophthalimide], N, N'-bis (1,2,3,4,5-penta Bromobenzyl) -pyromellitimide, N, N′-bis (2,4,6-tribromophenyl) pyromellitimide, N, N ′-(p- and m-phenylene) -bischloroendoimide, etc. It is done. Of these, the tetrahaloxylylene group is a 1,2,4,5-tetrahaloxylylene and / or 1,3,4,5-tetraloxylylene group.
これらの中でも、低級アルキレンビステトラブロモフタルイミドが好ましく、特にＮ，Ｎ′エチレンビステトラブロモフタルイミドが好ましい。 Among these, lower alkylene bistetrabromophthalimide is preferable, and N, N′ethylenebistetrabromophthalimide is particularly preferable.
ビスイミド構造化合物における臭素原子含有量は任意だが、十分な難燃性を付与する上で、通常１０質量％以上であり、中でも２０質量％以上、特に５０質量％以上であることが好ましく、その上限は８０質量％、中でも７０質量％以下であることが好ましい。 The bromine atom content in the bisimide structure compound is arbitrary, but is usually 10% by mass or more, preferably 20% by mass or more, and particularly preferably 50% by mass or more, in order to impart sufficient flame retardancy. Is preferably 80% by mass, especially 70% by mass or less.
ポリブロム化ベンジル（メタ）アクリレート化合物について
本発明に用いる（Ｃ）ハロゲン系難燃剤としてのポリブロム化ベンジル（メタ）アクリレート化合物は、以下の一般式（２）で表される化合物が好ましい。
About the polybrominated benzyl (meth) acrylate compound The polybrominated benzyl (meth) acrylate compound as the halogen flame retardant (C) used in the present invention is preferably a compound represented by the following general formula (2).
式（２）中、Ｒ1は水素原子またはメチル基を示し、水素原子が好ましい。Ｒ2は、アルキレン基を示し、炭素数１〜５のアルキレン基が好ましく、中でも炭素数１〜３のアルキレン基が好ましい。ｍは、２以上、中でも４〜５であることが好ましい。式（２）で表される重合体の分子量は１０００００以下が好ましい。１０００００を超えると、樹脂組成物の溶融粘度が高くなり成形性が低下する場合がある。 In the formula (2), R 1 represents a hydrogen atom or a methyl group, and preferably a hydrogen atom. R 2 represents an alkylene group, preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. m is preferably 2 or more, particularly 4 to 5. The molecular weight of the polymer represented by the formula (2) is preferably 100,000 or less. When it exceeds 100,000, the melt viscosity of the resin composition becomes high and moldability may be lowered.
本発明で用いられるポリブロム化ベンジル（メタ）アクリレートとしては、臭素原子を含有するベンジル（メタ）アクリレートを単独で重合、または２種以上を共重合、もしくは他のビニル系モノマーと共重合させることによって得られる重合体であることが好ましい。 As the polybrominated benzyl (meth) acrylate used in the present invention, benzyl (meth) acrylate containing a bromine atom is polymerized alone, or two or more kinds are copolymerized or copolymerized with other vinyl monomers. The resulting polymer is preferred.
該臭素原子を含有するベンジルアクリレートとしては、具体的には例えばペンタブロムベンジルアクリレート、テトラブロムベンジルアクリレート、トリブロムベンジルアクリレートまたはこれらの混合物等が挙げられる。また、臭素原子を含有するベンジルメタクリレートとしては、上記したアクリレートに対応するメタクリレートが挙げられる。 Specific examples of the benzyl acrylate containing a bromine atom include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, and mixtures thereof. Examples of the benzyl methacrylate containing a bromine atom include methacrylates corresponding to the acrylates described above.
臭素原子を含有するベンジル（メタ）アクリレートと共重合させるために使用される他のビニル系モノマーとしては、具体的には例えば、アクリル酸、メチルアクリレート、エチルアクリレート、ブチルアクリレート、ベンジルアクリレートのようなアクリル酸エステル類；メタクリル酸、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、ベンジルメタクリレートのようなメタクリル酸エステル類；スチレン、アクリロニトリル、フマル酸、マレイン酸の様な不飽和カルボン酸またはその無水物；酢酸ビニル、塩化ビニル、などが挙げられる。これらは通常、臭素原子を含有するベンジル（メタ）アクリレートに対して等モル量以下、中でも０．５倍モル量以下が用いることが好ましい。 Specific examples of other vinyl monomers used for copolymerization with benzyl (meth) acrylates containing bromine atoms include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and benzyl acrylate. Acrylic acid esters; methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate; unsaturated carboxylic acids such as styrene, acrylonitrile, fumaric acid, maleic acid, or anhydrides thereof; vinyl acetate , Vinyl chloride, and the like. These are usually preferably used in an equimolar amount or less, particularly 0.5 times the molar amount or less with respect to the benzyl (meth) acrylate containing a bromine atom.
また、ビニル系モノマーとしては、キシレンジアクリレート、キシレンジメタクリレート、テトラブロムキシレンジアクリレート、テトラブロムキシレンジメタクリレート、ブタジエン、イソプレン、ジビニルベンゼンなどを使用することもでき、これらは通常、臭素原子を含有するベンジルアクリレートまたはベンジルメタクリレートに対し、０．５倍モル量以下が使用できる。 In addition, as vinyl monomers, xylene diacrylate, xylene dimethacrylate, tetrabromoxylene diacrylate, tetrabromoxylene dimethacrylate, butadiene, isoprene, divinylbenzene, etc. can be used, and these usually contain bromine atoms. 0.5 mol or less of benzyl acrylate or benzyl methacrylate can be used.
ポリブロム化ベンジル（メタ）アクリレート化合物における臭素原子含有量は任意だが、十分な難燃性を付与する上で、通常３０質量％以上であり、中でも４０質量％以上、特に５０質量％以上であることが好ましく、その上限は８０質量％、中でも７０質量％以下であることが好ましい。 Although the bromine atom content in the polybrominated benzyl (meth) acrylate compound is arbitrary, it is usually 30% by mass or more, particularly 40% by mass or more, and particularly 50% by mass or more in order to impart sufficient flame retardancy. The upper limit is preferably 80% by mass, and more preferably 70% by mass or less.
該ポリブロム化ベンジル（メタ）アクリレートとしては、ポリペンタブロモベンジルアクリレートが、高臭素含有量であることから難燃効果が高い観点で好ましい。 As the polybrominated benzyl (meth) acrylate, polypentabromobenzyl acrylate is preferable from the viewpoint of high flame retardancy because of its high bromine content.
本発明で用いる（Ｃ）ハロゲン系難燃剤は、公知の方法に従って合成してもよいし、市販品を用いることもできる。 The (C) halogen flame retardant used in the present invention may be synthesized according to a known method, or a commercially available product may be used.
ハロゲン系難燃剤の含有量は、（Ａ）熱可塑性ポリエステル樹脂１００質量部に対して、７〜４０質量部であり、１０質量部〜３０質量部が好ましく、１２質量部〜２８質量部がより好ましい。７質量部未満であると難燃性の発現が不十分となり、逆に４０質量部を越えると機械的特性が低下しやすくなる。 Content of a halogenated flame retardant is 7-40 mass parts with respect to 100 mass parts of (A) thermoplastic polyester resin, 10 mass parts-30 mass parts are preferable, and 12 mass parts-28 mass parts are more. preferable. If the amount is less than 7 parts by mass, the expression of flame retardancy becomes insufficient. Conversely, if the amount exceeds 40 parts by mass, the mechanical properties tend to be deteriorated.
本発明に用いる（Ｃ）ハロゲン系難燃剤としては、本発明の難燃性熱可塑性ポリエステル樹脂組成物における諸特性、具体的には難燃性、強度、外観そして溶着性等の諸物性バランスに優れることから、中でも臭素化エポキシ樹脂を用いることが好ましい。 As the halogen-based flame retardant (C) used in the present invention, various properties in the flame-retardant thermoplastic polyester resin composition of the present invention, specifically, balance of various physical properties such as flame retardancy, strength, appearance, and weldability. Among them, it is preferable to use a brominated epoxy resin because it is excellent.
（Ｄ）無機系難燃助剤
本発明の樹脂成物においては、無機系難燃助剤を含む。無機系難燃助剤としては、アンチモン化合物等が挙げられ、アンチモン化合物が好ましい。アンチモン化合物としては酸化アンチモンまたは酸化アンチモンと他の金属の複塩を使用することができる。具体的には例えば、三酸化アンチモン（Ｓｂ2Ｏ3）、四酸化アンチモン（Ｓｂ2Ｏ4）、五酸化アンチモン（Ｓｂ2Ｏ5）、アンチモン酸ナトリウム等のアンチモン酸塩や、これらの複塩が挙げられる。
(D) Inorganic flame retardant aid The resin composition of the present invention includes an inorganic flame retardant aid. Examples of inorganic flame retardant aids include antimony compounds, and antimony compounds are preferred. As the antimony compound, antimony oxide or a double salt of antimony oxide and another metal can be used. Specifically, for example, antimonate such as antimony trioxide (Sb 2 O 3 ), antimony tetraoxide (Sb 2 O 4 ), antimony pentoxide (Sb 2 O 5 ), sodium antimonate, or a double salt thereof. Is mentioned.
中でも五酸化アンチモンまたは五酸化アンチモンと他の金属酸化物との複塩が好ましい。これは五酸化アンチモンが、他のアンチモン化合物に比べてポリエステル樹脂への影響が小さいので、樹脂の分解が他の抑えられる為である。よって樹脂の結晶化温度（Ｔｃ）が維持できるので、射出成形においても離型抵抗力が増加し難く、例えばエジェクターピン痕等の発生を抑制した、表面外観を良好な樹脂成形体が提供できるという効果が得られる。 Of these, antimony pentoxide or a double salt of antimony pentoxide and another metal oxide is preferable. This is because antimony pentoxide has a smaller influence on the polyester resin than other antimony compounds, so that the decomposition of the resin can be suppressed. Therefore, since the crystallization temperature (Tc) of the resin can be maintained, it is difficult to increase the mold release resistance even in the injection molding. An effect is obtained.
また五酸化アンチモン、または五酸化アンチモンと他の金属酸化物との複塩は、ＧＷＩＴ性能が優れている点でも、用いることが好ましい。五酸化アンチモンと他の金属酸化物との複塩としては、具体的には例えば下記一般式（３）又は（４）で示される複塩が好ましい。尚、これらは任意の割合で併用して用いてもよい。 Further, antimony pentoxide or a double salt of antimony pentoxide and another metal oxide is preferably used from the viewpoint of excellent GWIT performance. Specifically, as a double salt of antimony pentoxide and another metal oxide, for example, a double salt represented by the following general formula (3) or (4) is preferable. These may be used in combination at any ratio.
ｎ（Ｘ2Ｏ）・Ｓｂ2Ｏ5・ｍ（Ｈ2Ｏ） （３） n (X 2 O) · Sb 2 O 5 · m (H 2 O) (3)
ｎ（ＹＯ）・Ｓｂ2Ｏ5・ｍ（Ｈ2Ｏ） （４）
（これらの式中、Ｘは１価のアルカリ金属元素、Ｙは２価のアルカリ土類金属元素、ｎは０〜１．５、ｍは０〜４を示す。ｍおよびｎは化学式（３）及び化学式（４）においてそれぞれ独立して決定される）
n (YO) · Sb 2 O 5 · m (H 2 O) (4)
(In these formulas, X represents a monovalent alkali metal element, Y represents a divalent alkaline earth metal element, n represents 0 to 1.5, and m represents 0 to 4. m and n represent the chemical formula (3). And chemical formula (4) are independently determined)
更に好ましくは、下記一般式（５）で示される複塩を使用することができる。
ｎ（Ｎａ2Ｏ）・Ｓｂ2Ｏ5 ・・・・・（５）
（式中、ｎは０．６５〜１．５を示す。）
More preferably, a double salt represented by the following general formula (5) can be used.
n (Na 2 O) · Sb 2 O 5 (5)
(In the formula, n represents 0.65 to 1.5.)
上述の式（３）〜（５）において、Ｘとしてはリチウム、ナトリウム、カリウム、セシウムなどが挙げられ、Ｙとしてはカルシウム、マグネシウム、バリウムなどが挙げられる。ｎは、０より大きく、通常０．３以上、特に０．６５〜１．５が好ましい。ｎが小さすぎると吸着水の脱離速度が小さいために、溶融粘度が変化しやすい傾向にあり、逆にｎが大きすぎると相対的にアンチモンの量が低下することにより難燃助剤としての効果が低減する。 In the above formulas (3) to (5), X includes lithium, sodium, potassium, cesium, and the like, and Y includes calcium, magnesium, barium, and the like. n is larger than 0, usually 0.3 or more, particularly preferably 0.65 to 1.5. If n is too small, the desorption rate of adsorbed water is small, so that the melt viscosity tends to change. Conversely, if n is too large, the amount of antimony will be relatively lowered, and as a flame retardant aid. The effect is reduced.
ｍは０〜４であり、好ましくは０〜２である。ｍが大きすぎるとＰＢＴ系樹脂の加水分解が著しくなるので好ましくない。本発明においては特に、耐加水分解性の点からＮａ2Ｏ・Ｓｂ2Ｏ5（ｎ＝１）で表される、酸化ナトリウムと五酸化アンチモンの１対１の複塩が好ましく、これは具体的には例えば、日産化学社よりＮＡ−１０７０Ｌ等の商品名で市販されているものが挙げられる。 m is 0-4, preferably 0-2. If m is too large, hydrolysis of the PBT resin becomes remarkable, which is not preferable. In the present invention, in particular, a one-to-one double salt of sodium oxide and antimony pentoxide represented by Na 2 O.Sb 2 O 5 (n = 1) is preferable from the viewpoint of hydrolysis resistance. For example, what is marketed by the brand name of NA-1070L etc. from Nissan Chemical Co., Ltd. is mentioned.
無機系難燃助剤の含有量は、（Ａ）熱可塑性ポリエステル樹脂１００質量部に対して、３質量部〜２０質量部であり、５質量部〜１５質量部が好ましく、６質量部〜１４質量部がより好ましい。 Content of an inorganic type flame retardant adjuvant is 3 mass parts-20 mass parts with respect to 100 mass parts of (A) thermoplastic polyester resin, 5 mass parts-15 mass parts are preferable, and 6 mass parts-14 Part by mass is more preferable.
（Ｅ）無機系強化材
また本発明の樹脂組成物には、機械的強度、耐熱性、寸法安定性（耐変形、そり）、電気的性質等の性能に優れた樹脂成形体を得るために、繊維状、粉粒状、板状等の、各種の（Ｅ）無機系強化材を配合する。
(E) Inorganic reinforcing material In addition, in order to obtain a resin molded article excellent in performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warpage), and electrical properties in the resin composition of the present invention. Various kinds of (E) inorganic reinforcing materials such as fiber, powder, and plate are blended.
繊維状無機系強化材としては、例えば、ガラス繊維、カーボン繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化珪素繊維、硼素繊維、チタン酸カリ繊維、更にステンレス、アルミニウム、チタン、銅、真鍮等の金属の繊維状物等が挙げられる。特に代表的な繊維状無機系強化材はガラス繊維、カーボン繊維である。 Examples of the fibrous inorganic reinforcing material include glass fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium , Metal fibrous materials such as copper and brass. Particularly typical fibrous inorganic reinforcing materials are glass fiber and carbon fiber.
粉粒状無機系強化材としては、例えば、カーボンブラック、シリカ、石英粉末、ガラスビーズ、ガラス粉、硅酸カルシウム、硅酸アルミニウム、カオリン、タルク、クレー、硅藻土、ウォラストナイト等の硅酸塩、酸化鉄、酸化チタン、酸化亜鉛、アルミナ等の金属酸化物、炭酸カルシウム、炭酸マグネシウム等の金属の炭酸塩、硫酸カルシウム、硫酸バリウム等の金属の硫酸塩、その他炭化硅素、窒化硅素、窒化硼素、各種金属粉末等が挙げられる。
板状無機系強化材としては、例えば、マイカ、ガラスフレーク、各種の金属箔等が挙げられる。
これらの無機系強化材は単独で、又は２種以上を任意の割合で併用してもよい。
Examples of the granular inorganic reinforcing material include oxalic acid such as carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, talc, clay, diatomaceous earth, and wollastonite. Metal oxides such as salts, iron oxide, titanium oxide, zinc oxide, and alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, and nitride Examples thereof include boron and various metal powders.
Examples of the plate-like inorganic reinforcing material include mica, glass flakes, various metal foils, and the like.
These inorganic reinforcing materials may be used alone or in combination of two or more at any ratio.
これらの無機系強化材の使用にあたっては、必要ならば収束剤や表面処理剤を使用することができる。例えば、エポキシ系化合物、シラン系化合物、チタネート系化合物等の官能性化合物が用いられる。無機系強化材は、予めこれらの化合物によって処理しておいてもよく、または樹脂組成物の製造時に同時に、または個別に添加してもよい。 In using these inorganic reinforcing materials, if necessary, a sizing agent or a surface treatment agent can be used. For example, functional compounds such as epoxy compounds, silane compounds, and titanate compounds are used. The inorganic reinforcing material may be treated with these compounds in advance, or may be added simultaneously or individually during the production of the resin composition.
（Ｅ）無機系強化材の配合量は、成分（Ａ）熱可塑性ポリエステル樹脂１００質量部に対して、１〜９０質量部、好ましくは１０〜８０質量部であり、さらに好ましくは１２〜７７質量部、特に好ましくは１４〜７５質量部である。９０質量部を超えて配合すると、樹脂組成物の靭性を確保することが困難となる。 (E) The compounding quantity of an inorganic type reinforcement is 1-90 mass parts with respect to 100 mass parts of component (A) thermoplastic polyester resins, Preferably it is 10-80 mass parts, More preferably, it is 12-77 mass. Parts, particularly preferably 14 to 75 parts by mass. When it mix | blends exceeding 90 mass parts, it will become difficult to ensure the toughness of a resin composition.
さらに本発明の樹脂組成物には、本発明の目的を損なわない範囲で、熱可塑性樹脂組成物に常用されている種々の添加剤を添加することができる。このような添加剤としては、酸化防止剤、紫外線吸収剤、光安定剤等の安定剤、耐加水分解抑制剤（エポキシ化合物、カルボジイミド化合物など）、帯電防止剤、滑剤、離型剤、染料や顔料等の着色剤、可塑剤、耐候性改良剤などが挙げられる。特に、安定剤及び離型剤の添加は効果的である。これらの添加剤の添加量は、熱可塑性ポリエステル樹脂１００質量部に対し、通常、１０質量部以下であり、好ましくは５質量部以下である。 Furthermore, various additives commonly used in thermoplastic resin compositions can be added to the resin composition of the present invention within a range that does not impair the object of the present invention. Examples of such additives include stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, hydrolysis inhibitors (epoxy compounds, carbodiimide compounds, etc.), antistatic agents, lubricants, mold release agents, dyes, Examples thereof include colorants such as pigments, plasticizers, and weather resistance improvers. In particular, the addition of a stabilizer and a release agent is effective. The addition amount of these additives is usually 10 parts by mass or less, preferably 5 parts by mass or less, with respect to 100 parts by mass of the thermoplastic polyester resin.
中でも本発明においては、耐候性を向上させる目的においては、先述のカーボンブラックを少量含有させることが好ましく、特に（Ｃ）ハロゲン系難燃剤として臭素化エポキシ化合物を用いる場合に効果が顕著となる。耐候性改良剤として用いるカーボンブラックの量は、（Ａ）熱可塑性ポリエステル樹脂１００質量部に対して０．１〜１質量部、中でも０．１〜０．５質量部とすることが好ましい。 Among them, in the present invention, for the purpose of improving the weather resistance, it is preferable to contain a small amount of the above-mentioned carbon black, and the effect is particularly remarkable when a brominated epoxy compound is used as the (C) halogen flame retardant. The amount of carbon black used as a weather resistance improver is preferably 0.1 to 1 part by mass, and more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of (A) the thermoplastic polyester resin.
また、懸濁重合法で得られたポリテトラフルオロエチレンやヒュームドコロイダルシリカなどの滴下防止剤を添加して、燃焼時の滴下防止を行うこともできる。しかしながら、本発明ではこのような滴下防止剤を実質的に含まなくても、高い難燃性を達成できる。実質的に含まないとは、滴下防止剤として機能する添加量で添加されていないことをいい、通常樹脂成分に対し、０．１質量％以下である。 Moreover, dripping prevention at the time of combustion can also be performed by adding a dripping inhibitor such as polytetrafluoroethylene or fumed colloidal silica obtained by suspension polymerization. However, in the present invention, high flame retardancy can be achieved without substantially including such an anti-dripping agent. “Substantially not contained” means that it is not added in an addition amount that functions as an anti-dripping agent, and is usually 0.1% by mass or less based on the resin component.
本発明の樹脂組成物は、ハロゲン系難燃剤以外の難燃剤を実質的に含まないことが好ましい。実質的に含まないとは、難燃剤として機能する添加量で添加されていないことをいい、通常樹脂成分に対し、０．１質量％以下である。ハロゲン系以外の難燃剤としては、リン酸エステル、ポリリン酸塩、赤燐等のリン系難燃剤、水酸化アルミニウム、水酸化マグネシウム等の無機系難燃剤、その他シリコン系難燃剤、トリアジン系難燃剤等が挙げられる。 It is preferable that the resin composition of the present invention does not substantially contain a flame retardant other than the halogen-based flame retardant. “Substantially not contained” means that it is not added in an addition amount that functions as a flame retardant, and is usually 0.1% by mass or less based on the resin component. Non-halogen flame retardants include phosphorus flame retardants such as phosphates, polyphosphates and red phosphorus, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide, other silicon flame retardants, and triazine flame retardants. Etc.
本発明の難燃性熱可塑性ポリエステル樹脂組成物は、更に他の熱可塑性樹脂を補助的に用いてもよく、高温において安定な樹脂であれば使用可能であり、具体的には例えばポリカーボネート、ポリアミド、ポリフェニレンオキサイド、ポリスチレン系樹脂、ポリフェニレンサルファイドエチレン、ポリサルホン、ポリエーテルサルホン、ポリエーテルイミド、ポリエーテルケトン、フッ素樹脂等が挙げられる。 The flame-retardant thermoplastic polyester resin composition of the present invention may further use another thermoplastic resin, and can be used as long as the resin is stable at high temperatures. Specifically, for example, polycarbonate, polyamide , Polyphenylene oxide, polystyrene resin, polyphenylene sulfide ethylene, polysulfone, polyethersulfone, polyetherimide, polyetherketone, fluororesin and the like.
本発明の難燃性熱可塑性ポリエステル樹脂組成物の調製は、樹脂組成物調製の常法に従って行うことができる。通常は各成分及び所望により添加される種々の添加剤を一緒にしてよく混合し、次いで一軸又は二軸押出機で溶融混練する。また各成分を予め混合することなく、ないしはその一部のみを予め混合し、フイーダーを用いて押出機に供給して溶融混練し、本発明の樹脂組成物を調製することもできる。さらには、ポリエステル樹脂の一部に他の成分の一部を配合したものを溶融混練してマスターバッチを調製し、次いでこれに残りのポリエステル樹脂や他の成分を配合して溶融混練してもよい。 The flame-retardant thermoplastic polyester resin composition of the present invention can be prepared according to a conventional method for preparing a resin composition. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Also, the resin composition of the present invention can be prepared by mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Further, a master batch is prepared by melting and kneading a part of a polyester resin and a part of other components, and then the remaining polyester resin and other ingredients are blended and melt kneaded. Good.
本発明の熱可塑性樹脂組成物は、上述した様な溶融状態とした樹脂組成物を、従来公知の任意の製造方法により樹脂成形体とすることが出来る。具体的には例えば、射出成形、押出成形、プレス成形等種々の熱可塑性樹脂成形法により、樹脂成形体に成形することが可能である。中でも、成形サイクルが短く生産性が安定していることから、射出成形法により成形された成形体が、その特徴が顕著となるので好ましい。 In the thermoplastic resin composition of the present invention, the resin composition in a molten state as described above can be formed into a resin molded body by any conventionally known production method. Specifically, for example, it can be molded into a resin molded body by various thermoplastic resin molding methods such as injection molding, extrusion molding, and press molding. Among these, since the molding cycle is short and the productivity is stable, a molded body molded by an injection molding method is preferable because its features become remarkable.
本発明の樹脂成形体は、上述した射出成形によるものの他、樹脂フィルム、樹脂シートの様な樹脂成形体等の様々な形態で、電子材料、構造体材料、自動車材料、建築材料等の各種工業製品、部品部材用途に幅広く用いることが可能である。本発明の樹脂成形体は、現在広く用いられている一般的なプラスチック用成形機での使用が可能であるので、複雑な形状を有する成形体とすることも可能である。 The resin molded body of the present invention can be used in various industries such as electronic materials, structural materials, automobile materials, building materials, etc. in various forms such as resin molded bodies such as resin films and resin sheets, in addition to the above-described injection molding. It can be used widely for products and parts and materials. Since the resin molded body of the present invention can be used in a general plastic molding machine that is widely used at present, it can be formed into a molded body having a complicated shape.
本発明の熱可塑性樹脂組成物は、難燃性に加えて衝撃強度、外観、及び溶着性に優れた特性を有するので、各種工業製品・部品用部材として、好適に用いることが出来る。特に自動車分野における電器・電子部品、具体的には例えばコネクター等の部材部品を構成する樹脂成形体として、好適に用いることが出来る。 Since the thermoplastic resin composition of the present invention has properties excellent in impact strength, appearance, and weldability in addition to flame retardancy, it can be suitably used as a member for various industrial products and parts. In particular, it can be suitably used as a resin molded body constituting electric / electronic parts in the automobile field, specifically, member parts such as connectors.
以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
＜樹脂組成物の評価方法＞
表１に示す質量比で、ガラス繊維以外の成分を一括してスーパーミキサー（新栄機械社製ＳＫ−３５０型）で混合し、混合物をＬ／Ｄ＝４２の２軸押出機（日本製鋼所社製、ＴＥＸ３０ＨＳＳＴ）のホッパーに投入し、ガラス繊維をサイドフィードして、吐出量２０ｋｇ／ｈ、スクリュー回転数２５０ｒｐｍ、バレル温度２６０℃の条件下で押出して、ポリブチレンテレフタレート樹脂組成物のペレットを得た。得られたペレットを上記評価方法に応じた試験片に成形した。
<Evaluation method of resin composition>
At a mass ratio shown in Table 1, components other than glass fiber are mixed together by a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and the mixture is L / D = 42 twin screw extruder (Nippon Steel Works, Ltd.). Made of TEX30HSST), side feed the glass fiber, and extrude under the conditions of discharge rate 20kg / h, screw rotation speed 250rpm, barrel temperature 260 ° C to obtain pellets of polybutylene terephthalate resin composition It was. The obtained pellet was formed into a test piece according to the evaluation method.
得られたポリブチレンテレフタレート樹脂組成物（一次成形材料と二次成形材料は同じ）を用いて、射出成形機（日精株式会社製ＮＥＸ８０−９Ｅ）により、シリンダー温度２６０℃、金型温度８０℃で、図１に示す試験片Ａ（一次成形品）を成形し、熱風オーブン（１２０℃）中で３０分間保持して取り出した後、直ちに二次成形金型内に装着し、上記の得られたポリブチレンテレフタレート樹脂組成物（二次成形材料）を用いて試験片を射出成形し、試験片Ａと二次成形材料からなる試験片とを金型内で溶着させ射出溶着一体成形品Ｂを得た。得られた射出溶着一体成形品について射出溶着強度を測定した。 Using the obtained polybutylene terephthalate resin composition (the primary molding material and the secondary molding material are the same), an injection molding machine (NEX80-9E manufactured by Nissei Co., Ltd.) at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. 1 was molded, held in a hot air oven (120 ° C.) for 30 minutes and then taken out, immediately mounted in a secondary molding die, and the above obtained. A test piece is injection-molded using a polybutylene terephthalate resin composition (secondary molding material), and a test piece A and a test piece made of the secondary molding material are welded in a mold to obtain an injection-welded integrally molded product B. It was. The injection weld strength of the obtained injection welded integral molded product was measured.
難燃性テスト：
ＵＬ−９４の方法に準じ、５本の試験片（厚さ０．７５ｍｍ）を用いて難燃性テストを行い、ＵＬ９４記載の評価方法に従い、Ｖ−０、Ｖ−１、Ｖ−２、ＨＢに分類した（Ｖ−０が最も難燃性が高いことを示す）。合計燃焼時間は、５本の合計燃焼時間（第一接炎時、第二接炎時の燃焼時間を含む）であり、単位は、秒で示した。
Flame retardant test:
According to the method of UL-94, a flame retardancy test is performed using five test pieces (thickness: 0.75 mm), and according to the evaluation method described in UL94, V-0, V-1, V-2, HB (V-0 indicates the highest flame retardancy). The total combustion time is the total combustion time of 5 tubes (including the combustion time at the time of the first flame contact and the second flame contact), and the unit is shown in seconds.
ノッチ付きシャルピー衝撃強度
ポリブチレンテレフタレート樹脂組成物ペレットを用いて、射出成形機（日精樹脂工業株式会社製ＮＥＸ８０−９Ｅ型）にて、ＩＳＯ試験片を成形した。ＩＳＯ１７９−２に準拠してノッチ付シャルピー衝撃強さを測定した。
Charpy impact strength with notch Using a polybutylene terephthalate resin composition pellet, an ISO test piece was molded with an injection molding machine (NEX80-9E type manufactured by Nissei Plastic Industries Co., Ltd.). The notched Charpy impact strength was measured according to ISO 179-2.
成形品表面外観
ポリブチレンテレフタレート樹脂組成物ペレットを用いて、射出成形機（日精樹脂工業株式会社製ＮＥＸ８０−９Ｅ型）にて、樹脂温度２７０℃、金型温度８０℃で、１００ｍｍ径×２ｍｍ厚みの円盤状成形品を成形した。その円盤の表面外観を目視にて観察し、蛍光灯の像がくっきりと写るものを◎、少し揺らいで写るものを○、揺らいで写るものを×として評価した。○以上が実用上問題ないと判断される。
Surface appearance of molded product Using polybutylene terephthalate resin composition pellets, with injection molding machine (NEX80-9E type manufactured by Nissei Plastic Industry Co., Ltd.), resin temperature 270 ° C., mold temperature 80 ° C., 100 mm diameter × 2 mm thickness A disk-shaped molded product was molded. The surface appearance of the disk was visually observed and evaluated as ◎ when the image of the fluorescent light was clearly reflected, ◯ when the image was slightly shaken, and × when the image was shaken. ○ The above are judged to be practically acceptable.
溶着強度の測定：
一体成形品（図１に示す試験片Ｂ）を、曲げ速度２ｍｍ／ｍｉｎ、スパン間距離６４ｍｍの条件で引っ張り、破断時の荷重を測定し、その大きさをｋｇｆで表しこれを溶着強度とした。
Measurement of welding strength:
The integrally molded product (test piece B shown in FIG. 1) was pulled under the conditions of a bending speed of 2 mm / min and a span distance of 64 mm, the load at break was measured, and the size was represented by kgf, which was defined as the welding strength. .
上記表から明らかなとおり、グラフト重合体を用いても、スチレンを含まないグラフト重合体を用いた場合（比較例１〜３）、ハロゲン系難燃剤を含んでいても、実施例１〜３に比べて、難燃性が劣ることが分かった。また、スチレンを含む重合体を用いても、グラフト重合体でない場合（比較例４、５）、ハロゲン系難燃剤を含んでいても、実施例１〜３に比べて、難燃性が劣ることが分かる。また、グラフト重合体を含まない場合（比較例６）や、グラフト重合体を含んでいてもその含量が多い場合（比較例７）では、実施例１、４〜７と比べて、難燃性が劣ることが分かった。 As is clear from the above table, even when a graft polymer is used, when a graft polymer not containing styrene is used (Comparative Examples 1 to 3), even if a halogen-based flame retardant is included, Examples 1 to 3 It was found that the flame retardancy was inferior compared. Moreover, even if it uses the polymer containing styrene and it is not a graft polymer (Comparative Examples 4 and 5), even if it contains a halogenated flame retardant, the flame retardance is inferior compared with Examples 1-3. I understand. Moreover, in the case where the graft polymer is not included (Comparative Example 6) or the case where the graft polymer is included but the content thereof is large (Comparative Example 7), the flame retardancy is higher than those in Examples 1 and 4-7. Was found to be inferior.
また、実施例１と実施例１１で作成したＩＳＯ樹脂片（４ｍｍ厚）におけるエジェクターピン痕を観察した。両者は、難燃助剤であるアンチモン化合物のみを変更したものである。観察の結果、難燃助剤として五酸化アンチモンを用いた実施例１の樹脂成形体では、殆どエジェクターピン痕は見受けられなかったが、実施例８では深さ約０．３ｍｍの痕が見られたことから、実施例８の樹脂組成物の方が離型抵抗力が高くなっており、難燃助剤であるアンチモン化合物として、五酸化アンチモンが優れていることが判った。 Moreover, the ejector pin trace in the ISO resin piece (4 mm thickness) created in Example 1 and Example 11 was observed. In both cases, only the antimony compound which is a flame retardant aid is changed. As a result of the observation, almost no ejector pin marks were observed in the resin molded body of Example 1 using antimony pentoxide as a flame retardant aid, but in Example 8, a mark having a depth of about 0.3 mm was observed. From the above, it was found that the resin composition of Example 8 had higher release resistance, and antimony pentoxide was superior as an antimony compound as a flame retardant aid.
また実施例１と実施例１３、１４、そして比較例９〜１１との対比によって、（Ｂ）グラフト重合体以外のエラストマー含有量が多すぎてしまうと、本願発明の効果である難燃性が低下することが分かった。 Moreover, if the elastomer content other than (B) the graft polymer is too much due to the comparison between Example 1 and Examples 13 and 14 and Comparative Examples 9 to 11, the flame retardancy that is the effect of the present invention is obtained. It turns out that it falls.
さらに、実施例１と実施例１０の比較により、樹脂成分としてＰＢＴのみを用いた場合よりも、ＰＢＴとＰＥＴの混合系の方が、燃焼時間と溶着性について、より優れていることが分かった。 Furthermore, a comparison between Example 1 and Example 10 shows that the mixed system of PBT and PET is more excellent in terms of combustion time and weldability than when only PBT is used as the resin component. .
本発明の難燃性熱可塑性ポリエステル樹脂組成物は、電気電子部品、例えばコネクター、ターミナルなどの広範囲の部品への適用が期待できる。そしてさらには、自動車部品や建材部品などにも適用が考えられる。 The flame-retardant thermoplastic polyester resin composition of the present invention can be expected to be applied to a wide range of parts such as electric and electronic parts such as connectors and terminals. Furthermore, it can be applied to automobile parts and building material parts.
１ 試験片Ｂにおける試験片Ａの部分
２ 試験片Ｂにおける二次成形材料からなる成形品部分
３ ２１８ｍｍ
４ １２．８２ｍｍ
５ ２５ｍｍ
６ １２１．５ｍｍ
７ ２８ｍｍ
８ ３．０ｍｍ
９ ３．０ｍｍ
１０ ４５度
1 Part of Test Specimen A in
4 12.82mm
5 25mm
6 121.5mm
7 28mm
8 3.0mm
9 3.0mm
10 45 degrees
Claims (9)
（Ｂ）少なくともブタジエンを重合してなるゴム質重合体に、少なくともメチルメタクリレートとスチレンをグラフト重合させたグラフト重合体を１質量部〜３０質量部、
（Ｃ）ハロゲン系難燃剤を７質量部〜４０質量部、
（Ｄ）アンチモン化合物を３質量部〜２０質量部および
（Ｅ）無機系強化材を１質量部〜９０質量部
を含み、（Ｂ）グラフト重合体以外のエラストマーの含量が（Ａ）熱可塑性ポリエステル樹脂に対して３質量％以下であり、前記（Ｂ）グラフト重合体中のスチレン含有量が、３質量％以上１０質量％以下である、難燃性熱可塑性ポリエステル樹脂組成物。 (A) For 100 parts by mass of the thermoplastic polyester resin,
(B) 1 to 30 parts by mass of a graft polymer obtained by graft-polymerizing at least methyl methacrylate and styrene to a rubbery polymer obtained by polymerizing at least butadiene;
(C) 7 to 40 parts by mass of a halogen-based flame retardant,
(D) 3 parts by mass to 20 parts by mass of an antimony compound and (E) 1 part by mass to 90 parts by mass of an inorganic reinforcing material, and (B) an elastomer content other than the graft polymer is (A) a thermoplastic polyester. der 3 mass% or less with respect to the resin is, the (B) graft styrene content in the polymer is 10 mass% or less than 3 wt%, the flame retardant thermoplastic polyester resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010257098A JP5538188B2 (en) | 2010-11-17 | 2010-11-17 | Flame retardant thermoplastic polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010257098A JP5538188B2 (en) | 2010-11-17 | 2010-11-17 | Flame retardant thermoplastic polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012107126A JP2012107126A (en) | 2012-06-07 |
| JP5538188B2 true JP5538188B2 (en) | 2014-07-02 |
Family
ID=46493093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010257098A Active JP5538188B2 (en) | 2010-11-17 | 2010-11-17 | Flame retardant thermoplastic polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5538188B2 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6039372B2 (en) * | 2012-11-09 | 2016-12-07 | 三菱エンジニアリングプラスチックス株式会社 | Polybutylene terephthalate resin composition |
| JP6278898B2 (en) * | 2012-12-06 | 2018-02-14 | ウィンテックポリマー株式会社 | Resin molded body |
| JP6482755B2 (en) * | 2013-09-10 | 2019-03-13 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| JP6071623B2 (en) * | 2013-02-22 | 2017-02-01 | 三菱エンジニアリングプラスチックス株式会社 | Polybutylene terephthalate-based resin composition molded body |
| JP6298194B1 (en) * | 2017-05-16 | 2018-03-20 | 三菱エンジニアリングプラスチックス株式会社 | Connector port for external connection of electronic equipment |
| JP6231239B1 (en) * | 2016-05-19 | 2017-11-15 | 三菱エンジニアリングプラスチックス株式会社 | Polybutylene terephthalate resin composition and molded article |
| WO2017199989A1 (en) * | 2016-05-19 | 2017-11-23 | 三菱エンジニアリングプラスチックス株式会社 | Polybutylene terephthalate-based resin composition, and molded article |
| JP6483193B2 (en) * | 2017-06-07 | 2019-03-13 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| JP6483228B2 (en) * | 2017-12-13 | 2019-03-13 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| JP6483229B2 (en) * | 2017-12-13 | 2019-03-13 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| JP6483230B2 (en) * | 2017-12-13 | 2019-03-13 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| JP6386652B2 (en) * | 2017-12-13 | 2018-09-05 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| JP6590962B2 (en) * | 2018-01-26 | 2019-10-16 | 三菱エンジニアリングプラスチックス株式会社 | Connector port for external connection of electronic equipment |
| JP6687771B2 (en) * | 2019-02-12 | 2020-04-28 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing thermoplastic resin composition |
| CN113429787A (en) * | 2021-06-18 | 2021-09-24 | 金发科技股份有限公司 | High glow wire PPS composition and preparation method and application thereof |
| US20240010828A1 (en) * | 2022-07-08 | 2024-01-11 | B/E Aerospace, Inc. | Fire resistant polymer matrix composite |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5494553A (en) * | 1978-01-10 | 1979-07-26 | Teijin Ltd | Polyester resin composition |
| JP3235939B2 (en) * | 1994-12-28 | 2001-12-04 | ポリプラスチックス株式会社 | Flame retardant polyester resin composition |
| DE19543186A1 (en) * | 1995-11-20 | 1997-05-22 | Bayer Ag | Flame-retardant themoplastic moldings with improved properties |
| JPH10168291A (en) * | 1996-12-16 | 1998-06-23 | Nippon G Ii Plast Kk | Thermoplastic polyester resin composition |
| JP2005042082A (en) * | 2003-07-04 | 2005-02-17 | Mitsubishi Rayon Co Ltd | Thermoplastic resin composition |
-
2010
- 2010-11-17 JP JP2010257098A patent/JP5538188B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012107126A (en) | 2012-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5538188B2 (en) | Flame retardant thermoplastic polyester resin composition | |
| US9475933B2 (en) | Antimony trioxide free flame retardant thermoplastic composition | |
| WO2011058992A1 (en) | Polybutylene terephthalate resin composition | |
| WO2012147811A1 (en) | Insert molded article | |
| JP2017197676A (en) | Polybutylene terephthalate resin composition | |
| JPH1060242A (en) | Reinforced polyester resin composition and its molded product | |
| WO2013085789A1 (en) | Low antimony or antimony trioxide-free flame retarded thermoplastic composition | |
| JP2003026905A (en) | Resin composition and its molded article | |
| JP6749174B2 (en) | Polyester resin composition for laser direct structuring | |
| EP2289999B1 (en) | Thermoplastic composition | |
| KR100846861B1 (en) | Composition Of Polyester resin | |
| JP2006219626A (en) | Polybutylene terephthalate resin composition and molded article made thereof | |
| JPH08183896A (en) | Flame-retardant polyester resin composition | |
| JP2001011292A (en) | Light colored light-resistant polyester resin composition and luminaire parts molded therefrom | |
| WO1997002302A1 (en) | Graft ethylene-vinyl acetate copolymer and resin composition containing the same | |
| JP6163862B2 (en) | Thermoplastic resin composition and method for producing the same | |
| JP2005240003A (en) | Thermoplastic polyester resin composition and insert-molded article | |
| JP2006206921A (en) | Automobile part comprising polyester resin composition | |
| JPH0959524A (en) | Flame retardant resin composition | |
| JP2007321109A (en) | Polyester resin molded article and polyester resin composition | |
| JPH0551025B2 (en) | ||
| WO2018043334A1 (en) | Epoxy-modified vinyl copolymer, thermoplastic resin composition containing same and molded article of said thermoplastic resin composition | |
| JP2003119362A (en) | Flame retardant reinforced polytrimethylene terephthalate resin composition | |
| JP2020203963A (en) | Method for producing flame-retardant thermoplastic polyester resin composition | |
| JPH0517669A (en) | Flame-retardant polyester resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121214 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130619 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130709 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130904 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140422 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5538188 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140428 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |