JP2004269703A - Polytrimethylene terephthalate resin composition - Google Patents
Polytrimethylene terephthalate resin composition Download PDFInfo
- Publication number
- JP2004269703A JP2004269703A JP2003062864A JP2003062864A JP2004269703A JP 2004269703 A JP2004269703 A JP 2004269703A JP 2003062864 A JP2003062864 A JP 2003062864A JP 2003062864 A JP2003062864 A JP 2003062864A JP 2004269703 A JP2004269703 A JP 2004269703A
- Authority
- JP
- Japan
- Prior art keywords
- polytrimethylene terephthalate
- terephthalate resin
- resin composition
- brominated
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Polytrimethylene terephthalate Polymers 0.000 title claims abstract description 86
- 229920002215 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 50
- 239000011342 resin composition Substances 0.000 title claims abstract description 38
- 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 claims abstract description 34
- 239000003063 flame retardant Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 11
- 239000011256 inorganic filler Substances 0.000 claims description 29
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001463 antimony compounds Chemical class 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 239000000835 fiber Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
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- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-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
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920006361 Polyflon Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 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
- 239000006096 absorbing agent Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000010425 asbestos Substances 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 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
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003484 crystal nucleating agent Substances 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012760 heat stabilizer 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
- 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 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-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
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
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- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-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
- WYBOEVJIVYIEJL-UHFFFAOYSA-N 3,3',5-tribromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 WYBOEVJIVYIEJL-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
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- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical class C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 229910052918 calcium silicate Inorganic materials 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
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- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
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- 235000011187 glycerol Nutrition 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は薄肉難燃性に優れるポリトリメチレンテレフタレート樹脂組成物に関する。詳しくは、機械的特性が良好で、成形品外観と薄肉難燃性、特に燃焼時の滴下防止性に優れたポリトリメチレンテレフタレート樹脂組成物に関する。
【０００２】
【従来の技術】
ポリエチレンテレフタレートやポリブチレンテレフタレートに代表される熱可塑性ポリエステルは、機械特性、耐薬品性および電気的特性に優れるため、自動車部品、電気・電子部品などの広い分野でその使用が期待されている。そしてそれらの市場の多様化に伴い、高度な性能、用途に応じた特殊性能、高度な品質が求められている。電気・電子部品用途においては、アンダーライターズ・ラボラトリーのＵＬ−９４規格に基づく難燃性レベルの要求がなされている。
【０００３】
この要求に対し、ポリプロピレンテレフタレートまたはポリブチレンテフタレートとデカブロモジフェニルエーテル、三酸化アンチモンおよびアスベストからなる樹脂組成物が提案されている。（例えば、特許文献１参照。）
また、ポリエチレンテレフタレート、ポリトリメチレンテレフタレート、ポリテトラメチレンテレフタレートなどポリエステル樹脂とブタジエンポリマーとビニルモノマーのグラフトコポリマー、デカブロモジフェニルエーテル、臭素化ポリカーボネートオリゴマー、臭素化エポキシ化合物などのハロゲン難燃剤、酸化アンチモン、ガラス繊維からなる樹脂組成物が提案されている。（例えば、特許文献２参照。）
しかしアスベスト、またはグラフトコポリマーを用いたこれらの組成物では、薄肉での滴下防止効果が十分でなく、また成形品の外観も悪化する。
【０００４】
また、滴下防止効果を損なうことなく、成形表面不良を防止し優れた外観特性を得るために、熱可塑性ポリエステル樹脂とハロゲン含有難燃剤、無機系難燃助剤、フッ素樹脂組成物にオレフィン系重合体、ヒンダードフェノール系重合体を配合したポリエステル樹脂組成物（例えば、特許文献３参照。）、２種の異なる溶融粘度を持つ熱可塑性ポリエステルと臭素化芳香族化合物、アンチモン化合物、特定のポリテトラフルオロエチレン、無機充填材を配合した組成物（例えば、特許文献４参照。）、熱可塑性ポリエステルと臭素化芳香族化合物、アンチモン化合物、特定のポリテトラフルオロエチレン、オレフィン系ポリマー、無機充填材を配合した組成物（例えば、特許文献５参照。）などが提案されている。しかしいずれの場合も、滴下防止効果を保持したまま、優れた成形品外観を達成することは難しい。
【０００５】
【特許文献１】
特開昭５０−４９３６１号公報
【特許文献２】
米国特許第４１３１５９４号明細書
【特許文献３】
特開平１１−３５８０９号公報
【特許文献４】
特開平１１−１８１２５６号公報
【特許文献５】
特開平１１−１９９７６４号公報
【０００６】
【発明が解決しようとする課題】
本発明の課題は、機械的特性、耐候性、耐熱老化性および耐加水分解性に加え、成形品外観が良好で、薄肉難燃性、特に燃焼時の滴下防止性に優れたポリテトラメチレンテレフタレート樹脂組成物を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者等は、特定の熱可塑性ポリエステル、すなわち無機充填材で強化した時にも良好な成形品外観を保ち優れた機械的特性を持つ（Ａ）ポリトリメチレンテレフタレート樹脂と（Ｂ）臭素系難燃剤、（Ｃ）難燃助剤および（Ｄ）フッ素系樹脂からなる樹脂組成物により、上記課題を解決できることを見出し、本発明に至った。
【０００８】
すなわち本発明は、
１．（Ａ）ポリトリメチレンテレフタレート樹脂、（Ｂ）臭素系難燃剤、（Ｃ）難燃助剤および（Ｄ）フッ素系樹脂からなることを特徴とするポリトリメチレンテレフタレート樹脂組成物、
２．（Ａ）ポリトリメチレンテレフタレート樹脂１００重量部に対し、（Ｂ）臭素系難燃剤１〜１００重量部、（Ｃ）難燃助剤１〜６０重量部および（Ｄ）フッ素系樹脂０．１〜５重量部からなることを特徴とする上記１に記載のポリトリメチレンテレフタレート樹脂組成物、
３．該ポリトリメチレンテレフタレート樹脂組成物が更に（Ｅ）無機充填材５〜３００重量部を含む上記１または２に記載のポリトリメチレンテレフタレート樹脂組成物、
【０００９】
４．（Ｂ）臭素系難燃剤が、臭素化芳香族ビスイミド化合物、臭素化エポキシ化合物、臭素化ベンジルアクリレート化合物および臭素化ポリカーボネートから選ばれた難燃剤であることを特徴とする上記１〜３のいずれかに記載のポリトリメチレンテレフタレート樹脂組成物、
５．（Ｃ）難燃助剤が、アンチモン化合物であることを特徴とする上記１〜４のいずれかに記載のポリトリメチレンテレフタレート樹脂組成物、
【００１０】
６．（Ｄ）フッ素系樹脂が、ポリテトラフルオロエチレンであることを特徴とする上記１〜５のいずれかに記載のポリトリメチレンテレフタレート樹脂組成物、
７．（Ｅ）無機充填材が、ガラス繊維であることを特徴とする上記３〜６のいずれかに記載のポリトリメチレンテレフタレート樹脂組成物、
８．上記１〜７のいずれかに記載のポリトリメチレンテレフタレート樹脂組成物からなる成形品、
９．成形品が、射出成形品である上記８に記載の成形品、である。
【００１１】
【発明の実施の形態】
以下、本発明のポリトリメチレンテレフタレート樹脂組成物に関して詳細に説明する。
本発明のポリトリメチレンテレフタレート（以下、ＰＴＴと略称することがある。）とは、酸成分としてテレフタル酸を用い、グリコール成分としてトリメチレングリコールを用いたポリエステルポリマーを示している。
ここで、トリメチレングリコールとしては、１，３−プロパンジオール、１，２−プロパンジオール、１，１−プロパンジオール、２，２−プロパンジオール、又はこれらの混合物の中から選ばれるが、結晶化速度の観点から１，３−プロパンジオールが特に好ましい。
【００１２】
なお、本発明の目的を損なわない範囲で、酸成分として、テレフタル酸以外の芳香族ジカルボン酸、例えばフタル酸、イソフタル酸、２，６−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、ジフェノキシエタンジカルボン酸、ジフェニルメタンジカルボン酸、ジフェニルケトンジカルボン酸、ジフェニルスルフォンジカルボン酸等；コハク酸、アジピン酸、セバシン酸等の脂肪族ジカルボン酸；シクロヘキサンジカルボン酸等の脂環族ジカルボン酸；ε−オキシカプロン酸、ヒドロキシ安息香酸、ヒドロキシエトキシ安息香酸等のオキシジカルボン酸を、また、グリコール成分として、エチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール、キシリレングリコール、ジエチレングリコール、ポリオキシアルキレングリコール、ハイドロキノン等を用いて共重合したものも、本発明におけるＰＴＴに含まれる。
【００１３】
共重合する場合、共重合成分の量は、本発明の目的を損なわない範囲であれば特に制限はないが、通常、全酸成分の２０モル％以下、あるいは全グリコール成分の２０モル％以下とすることが好ましい。
また、上述のポリエステル成分に分岐成分、例えばトリカルバリル酸、トリメシン酸、トリメリット酸等の三官能又は四官能のエステル形成能を持つ酸、又はグリセリン、トリメチロールプロパン、ペンタエリトリット等の三官能又は四官能のエステル形成能を持つアルコールを共重合してもよく、その場合、これらの分岐成分の量は全酸成分または全グリコール成分の１．０モル％以下、好ましくは０．５モル％以下、さらに好ましくは０．３モル％以下である。更に、ＰＴＴはこれらの共重合成分を２種類以上組み合わせて使用しても構わない。
【００１４】
本発明に用いられるＰＴＴの製造方法は、特に限定されるものではなく、例えば、特開昭５１−１４０９９２号公報、特開平５−２６２８６２号公報、特開平８−３１１１７７号公報等に記載されている方法に従って得ることができる。
例えば、テレフタル酸又はそのエステル形成性誘導体（例えばジメチルエステル、モノメチルエステル等の低級アルキルエステル）とトリメチレングリコール又はそのエステル形成性誘導体とを、触媒の存在下、好適な温度・時間で加熱反応させ、更に得られたテレフタル酸のグリコールエステルを触媒の存在下、好適な温度・時間で所望の重合度まで重縮合反応させる方法が挙げられる。
【００１５】
重合方法についても、特に限定されず、溶融重合、界面重合、溶液重合、塊状重合、固相重合及びこれらを組み合わせた方法を利用することができる。
本発明で用いられるＰＴＴには、必要に応じて、各種の添化剤、例えば、熱安定剤、消泡剤、整色剤、酸化防止剤、紫外線吸収剤、赤外線吸収剤、結晶核剤、蛍光増白剤、艶消し剤等を共重合又は混合してもよい。
本発明のＰＴＴの極限粘度［η］については特に制限はないが、機械特性、疲労特性の面から０．５０以上であることが好ましく、０．６０以上がより好ましく、０．７０以上が最も好ましい。
【００１６】
極限粘度［η］については、オストワルド粘度計を用い、３５℃において、樹脂をｏ−クロロフェノール中に溶質（ＰＴＴ成分）濃度が１．００ｇ／ｄｌになるように溶解させ、不溶分（無機質充填材等）が沈殿した後、その上澄み液を用いて比粘度ηｓｐを測定し、下記式により求めることができる。
［η］＝０．７１３×（ηｓｐ／Ｃ）＋０．１０８６
Ｃ＝１．００ｇ／ｄｌ
【００１７】
次に、本発明の（Ｂ）臭素系難燃剤としては、一般に熱可塑性樹脂に用いられる臭素系難燃剤を用いることができ、例えば、臭素化芳香族ビスイミド化合物、臭素化エポキシ化合物、ビスフェノールＡの低分子量臭素化化合物、臭素化ベンジルアクリレート化合物、臭素化ポリカーボネート、臭素化ポリスチレン、臭素化ポリフェニレンエーテル等が挙げられる。特に、臭素化芳香族ビスイミド化合物、臭素化エポキシ化合物、臭素化ベンジルアクリレート化合物、臭素化ポリカーボネートが好ましい。
ここで臭素化芳香族ビスイミド化合物とは、下記一般式（１）で示されるものであり、式中Ｒ１は２価の有機基を表し、一般的にはアルキレン基、アリーレン基であり、特に好ましいのは低級アルキレン基である。またＸは少なくとも１つ以上が臭素である。
【００１８】
【化１】
更には、低級アルキレンビステトラブロモフタルイミド、特にＮ，Ｎ’−エチレンビステトラブロモフタルイミドがより好ましい。
臭素化エポキシ化合物とは、一般式（２）
【００２０】
【化２】
で表されるビスフェノールＡ型エポキシ化合物であり、式中のＸは少なくとも１つ以上が臭素である。ｎは２以上の数であり、好ましい平均重合度ｎは２〜８０、より好ましくは１０〜５０である。
【００２２】
臭素化エポキシ化合物は公知の方法、例えば臭素化ビスフェノールＡとエピクロルヒドリン、あるいは臭素化ビスフェノールジグリシジルエーテルと臭素化ビスフェノールとを重合条件を調整することにより縮合させて得ることができる。
臭素化ベンジルアクリレート化合物とは、下記一般式（３）で表される構造を有する化合物であり、式中のＸは少なくとも１つ以上が臭素であり、ｍは２〜６の数である。臭素化ベンジルアクリレート化合物は平均分子量５０万以下が好ましく、更に好ましくは１万から２０万である。
【００２３】
【化３】
臭素化ポリカーボネートは、一般式（４）で表されるカーボネート単位を有する化合物であり、式中のＸは少なくとも１つ以上が臭素である。ｒは２以上の数であり、好ましい平均重合度ｎは２〜５０、より好ましくは３〜２０である。臭素化ビスフェノール類、特にトリブロモビスフェノールＡから得られるポリカーボネートが好ましい。また末端封止剤としては、アルキルフェノール、ハロゲン化フェノールを用いることが好ましく、ｔ−ブチルフェノール、トリブロモフェノールが特に好ましい。
【００２５】
【化４】
本発明の臭素系難燃剤の配合量は、ＰＴＴ１００重量部に対して、難燃性の改良効果の点から１重量部以上であり、成形加工性や機械特性の点から１００重量部以下であることが好ましく、３〜９０重量部がより好ましく、５〜８０重量部が最も好ましい。
【００２７】
本発明の（Ｃ）難燃助剤としては、三酸化二アンチモン、四酸化二アンチモン、五酸化二アンチモン、アンチモン酸ナトリウム、酒石酸アンチモンなどのアンチモン化合物や、ホウ酸亜鉛、メタホウ酸バリウム、水和アルミナ、酸化ジルコニウム、ポリリン酸アンモニウム、酸化スズ、酸化鉄などを挙げられるが、この中でも、難燃化効果の観点から、アンチモン化合物が好ましく、三酸化二アンチモンが最も好ましい。
また、難燃助剤（Ｃ）の配合量は、ＰＴＴ１００重量部に対して、難燃性の改良効果の点から１重量部以上であり、成形加工性や機械特性の点から６０重量部以下であることが好ましく、３〜４０重量部がより好ましい。
【００２８】
本発明の（Ｄ）フッ素系樹脂としてはポリテトラフルオロエチレン、ヘキサフロロプロピレン、フッ化ビニリデンなどを用いることができる。更にポリテトラフルオロエチレンがこのましく、フィブリル形成能を有するポリテトラフルオロエチレンが最も好ましい。フィブリル形成能を有するポリテトラフルオロエチレンは樹脂中に容易に分散し、かつ重合体同士が結合して繊維状材料を形成し、ＡＳＴＭ規格ではタイプ３に分類される。フィブリル形成能を有するポリテトラフルオロエチレンとしては、例えばダイキン化学工業（株）のポリフロンＦＡ−５００またはＦ−２０１Ｌ、旭硝子（株）のフルオンＣＤ−１２３、三井・デュポンフロロケミカル（株）のテフロン（登録商標）６Ｊなどが好適に用いられる。また、ポリテトラフルオロエチレンのハンドリング性などを改良するために表面処理を施したもの、樹脂でコーティング処理を施したものなども使用することができる。
【００２９】
本発明の（Ｅ）無機充填材としては、目的に応じて、繊維状無機充填材、粉粒状無機充填材及び板状無機充填剤からなる群から選ばれる少なくとも一種以上の無機充填材を用いることができる。
繊維状無機充填材としては、ガラス繊維、炭素繊維、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、窒化硅素繊維、硼素繊維、チタン酸カリウムウィスカー、ウォラストナイト、さらにステンレス、アルミニウム、チタン、銅、真鍮等の金属の繊維状物等の繊維状無機充填材が挙げられる。なお、無機充填材と併用してポリアミド、フッ素樹脂、アクリル樹脂等の高融点有機質繊維状物質も使用することができる。
【００３０】
ここで、繊維状無機充填材の平均繊維長（以下、「Ｌ」ともいう）、平均繊維径（以下、「Ｄ」ともいう）、及びアスペクト比（以下、「Ｌ／Ｄ」ともいう）については、特に限定されないが、平均繊維長は機械的特性及び疲労特性の点から５０μｍ以上であることが好ましく、平均繊維径は５μｍ以上であることが好ましく、アスペクト比は１０以上であることが好ましい。
また、炭素繊維については、平均繊維長（Ｌ）が１００〜７５０μｍ、平均繊維径（Ｄ）が３〜３０μｍ、アスペクト比（Ｌ／Ｄ）が１０〜１００であるものが好ましく用いられる。さらに、ウォラストナイトは、平均繊維長が１０〜５００μｍ、平均繊維径が、３〜３０μｍ、アスペクト比（Ｌ／Ｄ）が３〜１００のものが好ましく用いられる。
【００３１】
粉粒状無機充填材としてはカーボンブラック、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、クレー、硅藻土などの硅酸塩、酸化鉄、酸化チタン、酸化亜鉛、アルミナなどの金属の酸化物、炭酸カルシウム、炭酸マグネシウムなどの金属の炭酸塩、硫酸カルシウム、硫酸バリウムなどの金属の硫酸塩、その他、炭化硅素、窒化硅素、窒化硼素、各種金属粉末が挙げられる。なお、タルク、マイカ、カオリン、炭酸カルシウム、チタン酸カリウムについては平均粒径が０．１〜１００μｍのものが最も好ましく用いられる。
【００３２】
板状無機充填材としてはタルク、マイカ、ガラスフレーク、各種の金属箔等が挙げられる。
本発明の無機充填材としては、機械的特性及び疲労特性の面からガラス繊維が最も好ましく用いられる。ガラス繊維は通常、ポリエステル樹脂に配合されるものであればよく、その種類等について特に制限はない。
また、無機充填材は一種のみ用いても、二種以上を併用してもよい。ガラス繊維とガラス繊維以外の無機充填材との併用、特にガラス繊維と粒状及び／又は板状無機充填剤との併用が、機械的強度と寸法精度、電気的性質等を兼備する上で好ましい。
【００３３】
本発明の（Ｅ）無機充填材の配合量は、ＰＴＴ１００重量部に対して５〜３００重量部が好ましく、５〜２００重量部がより好ましい。これらの無機充填材は、特に表面処理を施したものが好ましく用いられる。表面処理としては公知のカップリング剤やフィルム形成剤を用いて行う。好ましく用いられるカップリング剤としては、シラン系カップリング剤、チタン系カップリング剤があげられる。またフィルム形成剤としては、エポキシ系ポリマー、ウレタン系ポリマー、アクリル酸系ポリマー、及びこれらの混合物が好ましく用いられる。
【００３４】
本発明の難燃性ポリトリメチレンテレフタレート樹脂組成物には、上記のポリトリメリレンテレフタレート樹脂、臭素化エポキシ化合物、難燃助剤、無機充填材に加え、各種用途及び目的に応じて、その他の成分を適宜添加することができる。
本発明の樹脂組成物に結晶核剤をさらに配合すると、より機械的強度の高い組成物が得られる。結晶核剤としては、有機物及び無機物のいずれも使用することができる。
【００３５】
また、本発明の樹脂組成物に、成形性改良剤をさらに配合すると、より成形加工特性及び成形品外観に優れた難燃性樹脂組成物が得られる。成形性改良剤としては、リン酸エステル類、亜リン酸エステル類、高級脂肪酸類、高級脂肪酸金属塩類、高級アルコールと高級脂肪酸とのエステル類及び多価アルコールと高級脂肪酸とのエステル類等の高級脂肪酸エステル類、高級脂肪酸アミド化合物類、ポリアルキレングリコールあるいはその末端変性物類、低分子量ポリエチレンあるいは酸化低分子量ポリエチレン類、置換ベンジリデンソルビトール類、ポリシロキサン類、カプロラクトン類が挙げられるが、特に好ましいのは、高級脂肪酸類、高級脂肪酸金属塩類、高級脂肪酸エステル類である。
【００３６】
また、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、通常使用される紫外線吸収剤、耐熱安定剤、酸化防止剤、可塑剤、着色剤、衝撃強度改良剤、他の難燃剤等の添加剤を配合することもできる。
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、熱可塑性樹脂を配合してもよい。熱可塑性樹脂としては、ポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスチレン系樹脂（ゴム強化ポリスチレン、アクリロニトリル−ブタジエン−スチレン樹脂等）等が挙げられる。
【００３７】
本発明の難燃性ポリトリメチレンテレフタレート樹脂組成物の製造方法は特に限定されないが、ポリトリメチレンテレフタレート樹脂、難燃剤、難燃助剤、無機充填材、及び必要に応じて添加剤等の混合物を単軸又は多軸の押出機、ニーダー、ミキシングロール、バンバリーミキサー等の公知の溶融混練機を用いて、２００〜４００℃の温度で溶融混練する方法を挙げることができる。特に、押出機を用いて溶融混練することが簡便で望ましい。
【００３８】
本発明の難燃性ポリトリメチレンテレフタレート樹脂組成物は、従来の樹脂組成物に比較し、機械的特性、耐候性、耐熱老化性、耐加水分解性に加え、成形性、成形品外観が良好で、薄肉難燃性、特に燃焼時の滴下防止性に優れるため、射出成形、押出成形、圧縮成形、ブロー成形等の公知の成形方法、特に射出成形によって、例えば、コネクター、コイルボビン、ブレーカー、ホルダー、プラグ、スイッチ等の電気電子部品、自動車部品、機械機構部品用等の各種成形品に成形される。
【００３９】
【実施例】
以下実施例で本発明をさらに詳細に説明するが、本発明はこれら実施例に限定するものではない。なお、実施例および比較例に記載した諸特性は以下の方法により評価した。
（試料の成形方法）
試料は、射出成形機を用いて成形した。装置は日精樹脂（株）製ＰＳ４０Ｅ、金型温度８０℃、シリンダー温度は２６０℃に設定し成形品を得た。
【００４０】
（評価方法）
（１）難燃性
米国ＵＮＤＥＲ ＷＲＩＴＥＲＳ ＬＡＢＯＲＡＴＯＲＩＥＳで定められたＵＬ−９４Ｖの規格に従って、厚みが１／３２インチの試験片で実施した。
（２）曲げ弾性率（ＧＰａ）
ＡＳＴＭ Ｄ７９０に準じて行った。
（３）曲げ強度（ＭＰａ）
ＡＳＴＭ Ｄ７９０に準じて行った。
（４）成形体外観
堀場製ハンディー光沢計ＩＧ３２０を用い、ＪＩＳ−Ｋ７１５０に準じてＧｓ６０℃を測定した。数値が７０以上の場合には○、７０未満の場合には×とした。
【００４１】
実施例及び比較例で用いた材料を以下に記す。
（Ａ）樹脂
ＰＴＴ：ポリトリメチレンテレフタレート樹脂［η］＝１．０１
ＰＢＴ：ポリブチレンテレフタレート樹脂、ポリプラスチックス（株）製：ジュラネックス２００２
ＰＥＴ：ポリエチレンテレフタレート樹脂、ユニチカ（株）製：ＮＥＨ−２０５
【００４２】
（Ｂ）臭素系難燃剤
（ｂ−１）坂本薬品工業（株）製：ＳＲ−Ｔ５０００（平均分子量１００００、臭素含有量５２％）
（ｂ−２）アルベマール社製エチレンビステトラブロモフタルイミド：ＳＡＹＴＥＸ ＢＴ−９３（平均分子量９５１、臭素含有料６７．２％）
（ｂ−３）グレートレイクス社製テトラブロモビスフェノールＡポリカーボネートオリゴマー：ＢＣ−５８（分子量３５００、臭素含有量５８．７％）
【００４３】
（Ｃ）難燃助剤
三酸化二アンチモン：日本精鉱社精 パトックスＭ
（Ｄ）ポリテトラフルオロエチレン
（ｄ−１）ダイキン工業社製：ポリフロンＦＡ−５００
（ｄ−２）ＧＥスペシャリティケミカルス社製：ＢＬＥＮＤＥＸ Ｂ４４９
（Ｅ）無機充填材
ガラス繊維：日本電気硝子（株）製０３Ｔ−１８７／ＰＬ
【００４４】
【実施例１〜３、比較例１〜４】
（Ａ）ポリトリメチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂、（Ｂ）臭素系難燃剤、（Ｃ）難燃助剤、（Ｄ）フッ素系樹脂及び（Ｅ）無機充填材を表１に示す配合割合で、ブレンダーを用いて予備混合後、二軸押出機（東芝機械製ＴＥＭ３５）を用いてシリンダー設定温度２６０℃、スクリュウ回転数２００ｒｐｍの条件下で、溶融混練し、ストランド状に取り出し冷却後カッターで造粒しペレットを得た。ペレットを前記した測定法によって諸特性を調べた。その結果を表１に示す。
なお、ポリエチレンテレフタレート樹脂を用いた比較例３においては射出成形の段階で離型不良等の成形性に問題を生じ，物性の評価をするにいたらなかった。
【００４５】
【表１】
【発明の効果】
本発明のポリトリメチレンテレフタレート樹脂組成物は，機械的特性、耐薬品性、耐候性、耐熱老化性、耐加水分解性に加え、成形品外観が良好で薄肉難燃性、特に燃焼時の滴下防止性に優れる。したがって、コネクター、コイルボビン、ブレーカー、ホルダー、プラグ、スイッチ等の電気電子部品、自動車部品、機械機構部品用等に好適に用いることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polytrimethylene terephthalate resin composition having excellent thin flame retardancy. More specifically, the present invention relates to a polytrimethylene terephthalate resin composition having good mechanical properties and excellent in appearance of a molded article and flame retardancy with a thin wall, particularly, excellent drip prevention during burning.
[0002]
[Prior art]
Thermoplastic polyesters represented by polyethylene terephthalate and polybutylene terephthalate have excellent mechanical properties, chemical resistance and electrical properties, and are therefore expected to be used in a wide range of fields such as automobile parts and electric / electronic parts. With the diversification of these markets, high performance, special performance according to the application, and high quality are required. In electrical and electronic parts applications, there is a demand for a flame retardancy level based on the UL-94 standard of Underwriters Laboratory.
[0003]
To meet this requirement, a resin composition comprising polypropylene terephthalate or polybutylene terephthalate, decabromodiphenyl ether, antimony trioxide and asbestos has been proposed. (For example, refer to Patent Document 1.)
In addition, halogen flame retardants such as polyethylene terephthalate, polytrimethylene terephthalate, graft copolymers of butadiene polymers and vinyl monomers such as polyester resins such as polytrimethylene terephthalate, polytetramethylene terephthalate, decabromodiphenyl ether, brominated polycarbonate oligomers, brominated epoxy compounds, antimony oxide, and glass Resin compositions comprising fibers have been proposed. (For example, see Patent Document 2.)
However, these compositions using asbestos or a graft copolymer do not have a sufficient effect of preventing dripping at a thin wall and deteriorate the appearance of a molded article.
[0004]
In addition, in order to prevent molding surface defects and obtain excellent appearance characteristics without impairing the effect of preventing dripping, the thermoplastic polyester resin and the halogen-containing flame retardant, inorganic flame retardant auxiliary, and fluorine resin Polyester resin composition blended with a coalesced or hindered phenolic polymer (see, for example, Patent Document 3), two kinds of thermoplastic polyesters having different melt viscosities, a brominated aromatic compound, an antimony compound, and a specific polytetrafluoroethylene. A composition containing fluoroethylene and an inorganic filler (for example, see Patent Document 4), a thermoplastic polyester and a brominated aromatic compound, an antimony compound, a specific polytetrafluoroethylene, an olefin-based polymer, and an inorganic filler. A composition (for example, see Patent Document 5) has been proposed. However, in any case, it is difficult to achieve an excellent appearance of a molded product while maintaining the effect of preventing dripping.
[0005]
[Patent Document 1]
JP-A-50-49361 [Patent Document 2]
US Patent No. 4,131,594 [Patent Document 3]
JP-A-11-35809 [Patent Document 4]
JP-A-11-181256 [Patent Document 5]
JP-A-11-199764
[Problems to be solved by the invention]
An object of the present invention is to provide a polytetramethylene terephthalate having excellent mechanical properties, weather resistance, heat aging resistance and hydrolysis resistance, a good appearance of a molded product, thin-walled flame retardancy, and particularly excellent dripping prevention during combustion. It is to provide a resin composition.
[0007]
[Means for Solving the Problems]
The present inventors have developed a (A) polytrimethylene terephthalate resin and (B) a bromine-based resin having a good appearance of a molded article and excellent mechanical properties even when reinforced with a specific thermoplastic polyester, that is, an inorganic filler. The present inventors have found that the above-mentioned problems can be solved by a resin composition comprising a flame retardant, (C) a flame retardant auxiliary, and (D) a fluororesin, and have accomplished the present invention.
[0008]
That is, the present invention
1. A polytrimethylene terephthalate resin composition comprising (A) a polytrimethylene terephthalate resin, (B) a bromine-based flame retardant, (C) a flame-retardant auxiliary, and (D) a fluorine-based resin;
2. (A) 1 to 100 parts by weight of a brominated flame retardant, (C) 1 to 60 parts by weight of a flame retardant auxiliary, and (D) 0.1 to 100 parts by weight of polytrimethylene terephthalate resin. The polytrimethylene terephthalate resin composition according to the above 1, wherein the composition comprises 5 parts by weight;
3. 3. The polytrimethylene terephthalate resin composition according to the above 1 or 2, wherein the polytrimethylene terephthalate resin composition further comprises (E) 5 to 300 parts by weight of an inorganic filler.
[0009]
4. (B) the flame retardant selected from the group consisting of a brominated aromatic bisimide compound, a brominated epoxy compound, a brominated benzyl acrylate compound and a brominated polycarbonate; Polytrimethylene terephthalate resin composition according to,
5. (C) The polytrimethylene terephthalate resin composition according to any one of (1) to (4) above, wherein the flame retardant aid is an antimony compound.
[0010]
6. (D) The polytrimethylene terephthalate resin composition according to any one of (1) to (5) above, wherein the fluorine-based resin is polytetrafluoroethylene.
7. (E) The polytrimethylene terephthalate resin composition according to any of 3 to 6, wherein the inorganic filler is glass fiber.
8. A molded article comprising the polytrimethylene terephthalate resin composition according to any one of the above 1 to 7,
9. 9. The molded article according to the above item 8, wherein the molded article is an injection molded article.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the polytrimethylene terephthalate resin composition of the present invention will be described in detail.
The polytrimethylene terephthalate (hereinafter sometimes abbreviated as PTT) of the present invention indicates a polyester polymer using terephthalic acid as an acid component and trimethylene glycol as a glycol component.
Here, the trimethylene glycol is selected from among 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, or a mixture thereof. From the viewpoint of speed, 1,3-propanediol is particularly preferred.
[0012]
As long as the object of the present invention is not impaired, aromatic dicarboxylic acids other than terephthalic acid, for example, phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxy acid, as the acid component. Ethanedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylketonedicarboxylic acid, diphenylsulfonedicarboxylic acid, etc .; aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; ε-oxycaproic acid Oxydicarboxylic acids such as hydroxybenzoic acid and hydroxyethoxybenzoic acid; and glycol components such as ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and octane glycol. Glycol, neopentyl glycol, cyclohexanedimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycols, also those copolymerized with hydroquinone, included in the PTT in the present invention.
[0013]
In the case of copolymerization, the amount of the copolymer component is not particularly limited as long as the object of the present invention is not impaired, but is usually 20 mol% or less of the total acid component or 20 mol% or less of the total glycol component. Is preferred.
Further, a branched component, for example, an acid having a trifunctional or tetrafunctional ester forming ability such as tricarballylic acid, trimesic acid, trimellitic acid, or a trifunctional acid such as glycerin, trimethylolpropane, or pentaerythritol is added to the above-mentioned polyester component. Alternatively, an alcohol having a tetrafunctional ester-forming ability may be copolymerized, in which case the amount of these branched components is 1.0 mol% or less, preferably 0.5 mol%, of the total acid components or the total glycol components. Or less, more preferably 0.3 mol% or less. Further, PTT may be used in combination of two or more of these copolymer components.
[0014]
The method for producing PTT used in the present invention is not particularly limited, and is described, for example, in JP-A-51-140992, JP-A-5-262882, JP-A-8-31177, and the like. Can be obtained according to the method.
For example, terephthalic acid or an ester-forming derivative thereof (eg, a lower alkyl ester such as dimethyl ester or monomethyl ester) and trimethylene glycol or an ester-forming derivative thereof are heated and reacted at a suitable temperature and time in the presence of a catalyst. And a method of subjecting the resulting glycol ester of terephthalic acid to a polycondensation reaction at a suitable temperature and time to a desired degree of polymerization in the presence of a catalyst.
[0015]
The polymerization method is also not particularly limited, and melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, solid phase polymerization, and a method combining these can be used.
In the PTT used in the present invention, if necessary, various additives such as a heat stabilizer, an antifoaming agent, a tinting agent, an antioxidant, an ultraviolet absorber, an infrared absorber, a crystal nucleating agent, Fluorescent whitening agents, matting agents and the like may be copolymerized or mixed.
The intrinsic viscosity [η] of the PTT of the present invention is not particularly limited, but is preferably 0.50 or more, more preferably 0.60 or more, most preferably 0.70 or more from the viewpoint of mechanical properties and fatigue properties. preferable.
[0016]
The intrinsic viscosity [η] was determined by using an Ostwald viscometer at 35 ° C. to dissolve the resin in o-chlorophenol so that the concentration of the solute (PTT component) became 1.00 g / dl. After the material is precipitated, the specific viscosity η sp is measured using the supernatant, and can be determined by the following equation.
[Η] = 0.713 × (η sp /C)+0.1086
C = 1.00 g / dl
[0017]
Next, as the brominated flame retardant (B) of the present invention, brominated flame retardants generally used for thermoplastic resins can be used. For example, brominated aromatic bisimide compounds, brominated epoxy compounds, bisphenol A Examples include low molecular weight brominated compounds, brominated benzyl acrylate compounds, brominated polycarbonates, brominated polystyrenes, brominated polyphenylene ethers, and the like. In particular, a brominated aromatic bisimide compound, a brominated epoxy compound, a brominated benzyl acrylate compound, and a brominated polycarbonate are preferred.
Here, the brominated aromatic bisimide compound is represented by the following general formula (1), wherein R1 represents a divalent organic group, and is generally an alkylene group or an arylene group, and is particularly preferable. Is a lower alkylene group. X is at least one of bromine.
[0018]
Embedded image
Further, lower alkylenebistetrabromophthalimide, particularly N, N'-ethylenebistetrabromophthalimide, is more preferred.
The brominated epoxy compound is represented by the general formula (2)
[0020]
Embedded image
Wherein at least one X in the formula is bromine. n is a number of 2 or more, and the preferable average degree of polymerization n is 2 to 80, more preferably 10 to 50.
[0022]
The brominated epoxy compound can be obtained by a known method, for example, by condensing brominated bisphenol A and epichlorohydrin, or brominated bisphenol diglycidyl ether and brominated bisphenol by adjusting the polymerization conditions.
The brominated benzyl acrylate compound is a compound having a structure represented by the following general formula (3), wherein X is at least one or more bromine, and m is a number of 2 to 6. The average molecular weight of the brominated benzyl acrylate compound is preferably 500,000 or less, more preferably 10,000 to 200,000.
[0023]
Embedded image
Brominated polycarbonate is a compound having a carbonate unit represented by the general formula (4), wherein at least one of X in the formula is bromine. r is a number of 2 or more, and a preferable average degree of polymerization n is 2 to 50, and more preferably 3 to 20. Preference is given to polycarbonates obtained from brominated bisphenols, in particular tribromobisphenol A. As the terminal blocking agent, an alkylphenol or a halogenated phenol is preferably used, and t-butylphenol and tribromophenol are particularly preferable.
[0025]
Embedded image
The amount of the brominated flame retardant of the present invention is at least 1 part by weight based on 100 parts by weight of PTT from the viewpoint of the effect of improving the flame retardancy and at most 100 parts by weight from the viewpoint of moldability and mechanical properties. It is preferably 3 to 90 parts by weight, and most preferably 5 to 80 parts by weight.
[0027]
Examples of (C) the flame retardant aid of the present invention include antimony compounds such as diantimony trioxide, diantimony tetroxide, diantimony pentoxide, sodium antimonate and antimony tartrate; zinc borate; barium metaborate; Alumina, zirconium oxide, ammonium polyphosphate, tin oxide, iron oxide and the like can be mentioned. Among them, antimony compounds are preferable, and diantimony trioxide is most preferable from the viewpoint of the flame retardant effect.
The amount of the flame retardant aid (C) is at least 1 part by weight based on 100 parts by weight of PTT from the viewpoint of the effect of improving the flame retardancy, and at most 60 parts by weight from the viewpoint of moldability and mechanical properties. And more preferably 3 to 40 parts by weight.
[0028]
As the fluorine resin (D) of the present invention, polytetrafluoroethylene, hexafluoropropylene, vinylidene fluoride and the like can be used. Further, polytetrafluoroethylene is preferred, and polytetrafluoroethylene having fibril-forming ability is most preferred. Polytetrafluoroethylene having a fibril-forming ability is easily dispersed in a resin, and a polymer is combined with each other to form a fibrous material. The polytetrafluoroethylene is classified into Type 3 according to the ASTM standard. Examples of the polytetrafluoroethylene having a fibril-forming ability include polyflon FA-500 or F-201L of Daikin Chemical Industries, Ltd., Fluon CD-123 of Asahi Glass Co., Ltd., and Teflon (Mitsui-DuPont Fluorochemical Co., Ltd.) (Registered trademark) 6J or the like is preferably used. In addition, polytetrafluoroethylene that has been subjected to a surface treatment in order to improve the handling properties and the like and that that has been subjected to a coating treatment with a resin can be used.
[0029]
As the inorganic filler (E) of the present invention, at least one inorganic filler selected from the group consisting of a fibrous inorganic filler, a granular inorganic filler, and a plate-like inorganic filler is used according to the purpose. Can be.
Examples of the fibrous inorganic filler include glass fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, wollastonite, stainless steel, aluminum, Examples include fibrous inorganic fillers such as fibrous materials of metals such as titanium, copper, and brass. In addition, a high melting point organic fibrous substance such as polyamide, fluororesin, and acrylic resin can be used in combination with the inorganic filler.
[0030]
Here, the average fiber length (hereinafter also referred to as “L”), average fiber diameter (hereinafter also referred to as “D”), and aspect ratio (hereinafter also referred to as “L / D”) of the fibrous inorganic filler are described. Is not particularly limited, but the average fiber length is preferably 50 μm or more from the viewpoint of mechanical properties and fatigue properties, the average fiber diameter is preferably 5 μm or more, and the aspect ratio is preferably 10 or more. .
As the carbon fibers, those having an average fiber length (L) of 100 to 750 μm, an average fiber diameter (D) of 3 to 30 μm, and an aspect ratio (L / D) of 10 to 100 are preferably used. Further, wollastonite having an average fiber length of 10 to 500 μm, an average fiber diameter of 3 to 30 μm, and an aspect ratio (L / D) of 3 to 100 is preferably used.
[0031]
Powdered inorganic fillers include carbon black, silica, quartz powder, glass beads, glass powder, silicates such as calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, iron oxide, titanium oxide, and zinc oxide. , Oxides of metals such as alumina, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, and others, silicon carbide, silicon nitride, boron nitride, and various metal powders. . Incidentally, talc, mica, kaolin, calcium carbonate and potassium titanate having an average particle diameter of 0.1 to 100 μm are most preferably used.
[0032]
Examples of the plate-like inorganic filler include talc, mica, glass flake, various metal foils, and the like.
As the inorganic filler of the present invention, glass fibers are most preferably used in terms of mechanical properties and fatigue properties. Generally, the glass fiber may be any one as long as it is blended with the polyester resin, and there is no particular limitation on the type and the like.
Further, only one inorganic filler may be used, or two or more inorganic fillers may be used in combination. The combined use of glass fiber and an inorganic filler other than glass fiber, particularly the combined use of glass fiber and a granular and / or plate-like inorganic filler, is preferable in terms of having both mechanical strength, dimensional accuracy, electrical properties, and the like.
[0033]
The amount of the inorganic filler (E) of the present invention is preferably 5 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on 100 parts by weight of PTT. As these inorganic fillers, particularly those subjected to surface treatment are preferably used. The surface treatment is performed using a known coupling agent or film forming agent. Examples of the coupling agent preferably used include a silane coupling agent and a titanium coupling agent. As the film forming agent, an epoxy polymer, a urethane polymer, an acrylic acid polymer, and a mixture thereof are preferably used.
[0034]
The flame-retardant polytrimethylene terephthalate resin composition of the present invention includes, in addition to the above-mentioned polytrimethylene terephthalate resin, a brominated epoxy compound, a flame-retardant aid, and an inorganic filler, various other applications and purposes. Components can be added as appropriate.
When a nucleating agent is further added to the resin composition of the present invention, a composition having higher mechanical strength can be obtained. As the crystal nucleating agent, any of an organic substance and an inorganic substance can be used.
[0035]
Further, when a moldability improver is further added to the resin composition of the present invention, a flame-retardant resin composition having more excellent molding processing characteristics and appearance of a molded product can be obtained. Examples of the moldability improver include higher esters such as phosphate esters, phosphite esters, higher fatty acids, higher fatty acid metal salts, esters of higher alcohols and higher fatty acids, and esters of polyhydric alcohols and higher fatty acids. Fatty acid esters, higher fatty acid amide compounds, polyalkylene glycols or terminal modified products thereof, low molecular weight polyethylene or oxidized low molecular weight polyethylenes, substituted benzylidene sorbitols, polysiloxanes, caprolactones, but particularly preferred are , Higher fatty acids, metal salts of higher fatty acids, and higher fatty acid esters.
[0036]
Further, the resin composition of the present invention, within a range that does not impair the purpose of the present invention, commonly used ultraviolet absorbers, heat stabilizers, antioxidants, plasticizers, coloring agents, impact strength improvers, other Additives such as flame retardants can also be included.
Further, a thermoplastic resin may be added to the resin composition of the present invention as long as the object of the present invention is not impaired. Examples of the thermoplastic resin include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and polystyrene resins (rubber reinforced polystyrene, acrylonitrile-butadiene-styrene resin, and the like).
[0037]
The method for producing the flame-retardant polytrimethylene terephthalate resin composition of the present invention is not particularly limited, but a mixture of a polytrimethylene terephthalate resin, a flame retardant, a flame retardant auxiliary, an inorganic filler, and an additive if necessary. Using a known melt kneader such as a single-screw or multi-screw extruder, a kneader, a mixing roll, a Banbury mixer or the like at a temperature of 200 to 400 ° C. Particularly, it is convenient and desirable to perform melt kneading using an extruder.
[0038]
The flame-retardant polytrimethylene terephthalate resin composition of the present invention has better moldability and appearance of a molded product in addition to mechanical properties, weather resistance, heat aging resistance and hydrolysis resistance as compared with conventional resin compositions. In order to achieve excellent thin-walled flame retardancy, particularly excellent dripping prevention during combustion, injection molding, extrusion molding, compression molding, known molding methods such as blow molding, particularly injection molding, for example, connectors, coil bobbins, breakers, holders It is molded into various molded products such as electric and electronic parts such as plugs and switches, automobile parts and mechanical mechanism parts.
[0039]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Various properties described in Examples and Comparative Examples were evaluated by the following methods.
(Method of forming samples)
The sample was molded using an injection molding machine. The apparatus was PS40E manufactured by Nissei Plastics Co., Ltd., the mold temperature was set at 80 ° C., and the cylinder temperature was set at 260 ° C. to obtain a molded product.
[0040]
(Evaluation method)
(1) Flame retardancy In accordance with the UL-94V standard set by UNDER WRITERS LABORATORIES in the United States, a test piece having a thickness of 1/32 inch was used.
(2) Flexural modulus (GPa)
Performed according to ASTM D790.
(3) Flexural strength (MPa)
Performed according to ASTM D790.
(4) Appearance of molded article Gs60 ° C. was measured using HORIBA Handy Gloss Meter IG320 according to JIS-K7150. When the numerical value was 70 or more, it was evaluated as ○, and when it was less than 70, it was evaluated as ×.
[0041]
The materials used in the examples and comparative examples are described below.
(A) Resin PTT: polytrimethylene terephthalate resin [η] = 1.01
PBT: polybutylene terephthalate resin, manufactured by Polyplastics Co., Ltd .: Duranex 2002
PET: polyethylene terephthalate resin, manufactured by Unitika Ltd .: NEH-205
[0042]
(B) Brominated flame retardant (b-1) manufactured by Sakamoto Pharmaceutical Co., Ltd .: SR-T5000 (average molecular weight 10,000, bromine content 52%)
(B-2) Albemarle ethylene bistetrabromophthalimide: SAYTEX BT-93 (average molecular weight 951, bromine-containing material 67.2%)
(B-3) Tetrabromobisphenol A polycarbonate oligomer manufactured by Great Lakes Co .: BC-58 (molecular weight 3500, bromine content 58.7%)
[0043]
(C) Flame retardant diantimony trioxide: Nippon Seikosha Patox M
(D) Polytetrafluoroethylene (d-1) manufactured by Daikin Industries: Polyflon FA-500
(D-2) GE Specialty Chemicals: BLENDEX B449
(E) Inorganic filler glass fiber: 03T-187 / PL manufactured by NEC Corporation
[0044]
Examples 1-3, Comparative Examples 1-4
Table 1 shows (A) polytrimethylene terephthalate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, (B) brominated flame retardant, (C) flame retardant auxiliary, (D) fluororesin, and (E) inorganic filler. After pre-mixing using a blender at the mixing ratio shown in the table, melt-kneading is performed using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 200 rpm, and the mixture is taken out into a strand. After cooling, it was granulated with a cutter to obtain pellets. The pellets were examined for various properties by the above-described measurement methods. Table 1 shows the results.
In Comparative Example 3 using a polyethylene terephthalate resin, there was a problem in moldability such as mold release failure at the stage of injection molding, and it was not possible to evaluate physical properties.
[0045]
[Table 1]
【The invention's effect】
The polytrimethylene terephthalate resin composition of the present invention has good mechanical appearance, chemical resistance, weather resistance, heat aging resistance, and hydrolysis resistance, as well as good molded product appearance and thin-walled flame retardancy. Excellent prevention. Therefore, it can be suitably used for electrical and electronic parts such as connectors, coil bobbins, breakers, holders, plugs, switches, automobile parts, mechanical mechanism parts, and the like.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003062864A JP2004269703A (en) | 2003-03-10 | 2003-03-10 | Polytrimethylene terephthalate resin composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003062864A JP2004269703A (en) | 2003-03-10 | 2003-03-10 | Polytrimethylene terephthalate resin composition |
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| JP2004269703A true JP2004269703A (en) | 2004-09-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007007663A1 (en) * | 2005-07-08 | 2007-01-18 | Polyplastics Co., Ltd. | Flame retardant resin composition |
| WO2009020943A1 (en) * | 2007-08-06 | 2009-02-12 | E.I. Du Pont De Nemours And Company | Flame retardant polytrimethylene terephthalate composition |
| JP2012224719A (en) * | 2011-04-18 | 2012-11-15 | Kaneka Corp | Highly thermoconductive thermoplastic resin composition |
-
2003
- 2003-03-10 JP JP2003062864A patent/JP2004269703A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007007663A1 (en) * | 2005-07-08 | 2007-01-18 | Polyplastics Co., Ltd. | Flame retardant resin composition |
| JPWO2007007663A1 (en) * | 2005-07-08 | 2009-01-29 | ポリプラスチックス株式会社 | Flame retardant resin composition |
| CN101218305B (en) * | 2005-07-08 | 2011-03-23 | 宝理塑料株式会社 | Flame retardant resin composition |
| JP5186210B2 (en) * | 2005-07-08 | 2013-04-17 | ポリプラスチックス株式会社 | Flame retardant resin composition |
| WO2009020943A1 (en) * | 2007-08-06 | 2009-02-12 | E.I. Du Pont De Nemours And Company | Flame retardant polytrimethylene terephthalate composition |
| JP2012224719A (en) * | 2011-04-18 | 2012-11-15 | Kaneka Corp | Highly thermoconductive thermoplastic resin composition |
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