JPWO2014199915A1 - Polybutylene terephthalate resin composition and injection molded article - Google Patents
Polybutylene terephthalate resin composition and injection molded article Download PDFInfo
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- JPWO2014199915A1 JPWO2014199915A1 JP2015522750A JP2015522750A JPWO2014199915A1 JP WO2014199915 A1 JPWO2014199915 A1 JP WO2014199915A1 JP 2015522750 A JP2015522750 A JP 2015522750A JP 2015522750 A JP2015522750 A JP 2015522750A JP WO2014199915 A1 JPWO2014199915 A1 JP WO2014199915A1
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- mass
- resin composition
- flame retardant
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- polybutylene terephthalate
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- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 108
- 239000011342 resin composition Substances 0.000 title claims abstract description 73
- -1 Polybutylene terephthalate Polymers 0.000 title claims abstract description 64
- 238000002347 injection Methods 0.000 title description 8
- 239000007924 injection Substances 0.000 title description 8
- 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 77
- 239000003063 flame retardant Substances 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- 229910052623 talc Inorganic materials 0.000 claims abstract description 35
- 239000000454 talc Substances 0.000 claims abstract description 34
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- 238000001746 injection moulding Methods 0.000 claims abstract description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- 230000002265 prevention Effects 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000012796 inorganic flame retardant Substances 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- 238000012644 addition polymerization Methods 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229940105990 diglycerin Drugs 0.000 description 6
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 0 *C(*)(*)OC1=C=CC=C=C1 Chemical compound *C(*)(*)OC1=C=CC=C=C1 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000012765 fibrous filler Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- 238000005065 mining Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 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
- 239000004417 polycarbonate Substances 0.000 description 2
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- QJCKBPDVTNESEF-UHFFFAOYSA-N (2,3,4,5,6-pentabromophenyl)methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br QJCKBPDVTNESEF-UHFFFAOYSA-N 0.000 description 1
- 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
- SFUVLEGIZGPPNN-UHFFFAOYSA-N (2-pyridin-2-ylacetyl) 2-pyridin-2-ylacetate Chemical compound C=1C=CC=NC=1CC(=O)OC(=O)CC1=CC=CC=N1 SFUVLEGIZGPPNN-UHFFFAOYSA-N 0.000 description 1
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- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-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
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 1
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- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical group O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-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
- 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 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
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Images
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/308—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- C—CHEMISTRY; METALLURGY
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- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/006—PBT, i.e. polybutylene terephthalate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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Abstract
成形時において薄肉に成形し得るほどに十分な流動性を有し、薄肉に成形した場合でも優れた難燃性を有するポリブチレンテレフタレート樹脂組成物、及び該樹脂組成物を用いてなる射出成形品を提供する。（Ａ）固有粘度０．７０〜１．００g／ｄＬのポリブチレンテレフタレート樹脂１００質量部に対し、（Ｂ）臭素化エポキシ系難燃剤及び／又は臭素化アクリレート系難燃剤を合計で２０〜６５質量部と、（Ｃ）アンチモン系難燃助剤１０〜３０質量部と、（Ｄ）タルク３〜１５質量部と、（Ｅ）水酸基価１００以上の多価水酸基含有化合物１〜１０質量部とを含むポリブチレンテレフタレート樹脂組成物、及び該樹脂組成物を射出成形してなり、少なくとも一部に厚さ０．２〜０．５ｍｍの薄肉部を有する射出成形品である。Polybutylene terephthalate resin composition having sufficient fluidity that can be molded into a thin wall at the time of molding, and excellent flame retardancy even when molded into a thin wall, and an injection-molded product using the resin composition I will provide a. (A) With respect to 100 parts by mass of polybutylene terephthalate resin having an intrinsic viscosity of 0.70 to 1.00 g / dL, a total of 20 to 65 masses of (B) brominated epoxy flame retardant and / or brominated acrylate flame retardant Parts, (C) 10-30 parts by mass of an antimony flame retardant aid, (D) 3-15 parts by mass of talc, and (E) 1-10 parts by mass of a polyhydric hydroxyl group-containing compound having a hydroxyl value of 100 or more. A polybutylene terephthalate resin composition containing the resin composition, and an injection-molded product obtained by injection-molding the resin composition and having a thin portion having a thickness of 0.2 to 0.5 mm at least partially.
Description
本発明はポリブチレンテレフタレート樹脂組成物に関し、より詳細には、薄肉成形品における難燃性や、成形時の流動性に優れたポリブチレンテレフタレート樹脂組成物及び射出成形品に関する。 The present invention relates to a polybutylene terephthalate resin composition, and more particularly to a polybutylene terephthalate resin composition and an injection-molded article excellent in flame retardancy in a thin molded article and fluidity during molding.
ポリブチレンテレフタレート（以下、「ＰＢＴ」とも呼ぶ。）樹脂は、優れた機械的特性、電気的特性等を有するため、特に電気・電子部品分野の種々の成形品の材料として広く用いられている。 Polybutylene terephthalate (hereinafter also referred to as “PBT”) resin is widely used as a material for various molded products, particularly in the field of electrical and electronic parts, because it has excellent mechanical properties, electrical properties, and the like.
このような成形品に用いられる樹脂組成物には、一般的に高い難燃性を有することが求められるため、ＰＢＴ樹脂の難燃性を改善するべく種々の検討がなされてきた（例えば、特許文献１〜３参照）。また近年は、各種部品の小型軽量化の要求から、成形品の肉厚はますます薄くなる傾向にあるため、成形時におけるＰＢＴ樹脂の流動性を向上させる技術も検討されてきている（例えば、特許文献４参照）。さらにこれらの技術を組み合わせて、ＰＢＴ樹脂に難燃性と流動性の双方を付与する検討もなされてきている（例えば、特許文献５〜６参照）。しかし、成形品の肉厚が薄くなるほど難燃性の達成は困難となるため、実際には流動性向上の効果を十分に発揮できるような極めて薄肉の成形品における難燃性を達成できるようなＰＢＴ樹脂組成物は未だ知られていないのが現状である。 Since resin compositions used for such molded articles are generally required to have high flame retardancy, various studies have been made to improve the flame retardancy of PBT resins (for example, patents). References 1-3). In recent years, due to demands for reducing the size and weight of various parts, the thickness of molded products tends to become thinner. Therefore, a technique for improving the fluidity of PBT resin during molding has been studied (for example, (See Patent Document 4). Furthermore, studies have been made to combine these techniques to impart both flame retardancy and fluidity to PBT resins (see, for example, Patent Documents 5 to 6). However, as the thickness of the molded product becomes thinner, it becomes more difficult to achieve flame retardancy, so in practice it is possible to achieve flame retardancy in an extremely thin molded product that can fully demonstrate the effect of improving fluidity. The present situation is that the PBT resin composition is not yet known.
本発明は、成形時において薄肉に成形し得るほどに十分な流動性を有し、薄肉に成形した場合でも優れた難燃性を有するポリブチレンテレフタレート樹脂組成物、及び該樹脂組成物を用いてなる射出成形品を提供することを課題とする。 The present invention uses a polybutylene terephthalate resin composition having sufficient fluidity that can be formed into a thin wall at the time of molding, and excellent flame retardancy even when formed into a thin wall, and the resin composition. It is an object to provide an injection molded product.
前記課題を解決する本発明は以下の通りである。
〔１〕（Ａ）固有粘度０．７０〜１．００g／ｄＬのポリブチレンテレフタレート樹脂１００質量部に対し、（Ｂ）臭素系難燃剤として（Ｂ−１）臭素化エポキシ系難燃剤及び／又は（Ｂ−２）臭素化ポリアクリレート系難燃剤を合計で２０〜６５質量部と、（Ｃ）アンチモン系難燃助剤１０〜３０質量部と、（Ｄ）タルク３〜１５質量部と、（Ｅ）水酸基価１００以上の多価水酸基含有化合物１〜１０質量部とを含むことを特徴とするポリブチレンテレフタレート樹脂組成物。The present invention for solving the above problems is as follows.
[1] (B) Brominated epoxy flame retardant and / or (B-1) brominated flame retardant and 100 mass parts of polybutylene terephthalate resin with an intrinsic viscosity of 0.70 to 1.00 g / dL (B-2) 20 to 65 parts by mass of brominated polyacrylate flame retardant in total, (C) 10 to 30 parts by mass of antimony flame retardant aid, (D) 3 to 15 parts by mass of talc, E) A polybutylene terephthalate resin composition comprising 1 to 10 parts by mass of a polyhydric hydroxyl group-containing compound having a hydroxyl value of 100 or more.
〔２〕さらに、（Ｆ）滴下防止剤を、ポリブチレンテレフタレート樹脂１００質量部に対し０．５〜５質量部含む、前記〔１〕に記載のポリブチレンテレフタレート樹脂組成物。 [2] The polybutylene terephthalate resin composition according to [1], further including (F) 0.5 to 5 parts by mass of an anti-dripping agent with respect to 100 parts by mass of the polybutylene terephthalate resin.
〔３〕さらに、（Ｇ）ガラス繊維を、全体に対し１０〜４０質量％含む、前記〔１〕または〔２〕に記載のポリブチレンテレフタレート樹脂組成物。 [3] The polybutylene terephthalate resin composition according to [1] or [2], further including (G) 10 to 40% by mass of glass fiber.
〔４〕有機成分全体における臭素含有量が１０〜２０質量％である、前記〔１〕から〔３〕のいずれかに記載のポリブチレンテレフタレート樹脂組成物。 [4] The polybutylene terephthalate resin composition according to any one of [1] to [3], wherein the bromine content in the entire organic component is 10 to 20% by mass.
〔５〕前記〔１〕から〔４〕のいずれかに記載のポリブチレンテレフタレート樹脂組成物を射出成形してなり、少なくとも一部に厚さ０．２〜０．５ｍｍの薄肉部を有する射出成形品。 [5] Injection molding formed by injection-molding the polybutylene terephthalate resin composition according to any one of [1] to [4], and having a thin portion having a thickness of 0.2 to 0.5 mm at least partially. Goods.
本発明によれば、成形時において薄肉に成形し得るほどに十分な流動性を有し、薄肉に成形した場合でも優れた難燃性を有するポリブチレンテレフタレート樹脂組成物、及び該樹脂組成物を用いてなる射出成形品を提供することができる。 According to the present invention, there is provided a polybutylene terephthalate resin composition having sufficient fluidity that can be molded into a thin wall at the time of molding, and excellent flame retardancy even when molded into a thin wall, and the resin composition. The injection-molded product used can be provided.
＜ポリブチレンテレフタレート樹脂組成物＞
本発明のポリブチレンテレフタレート樹脂組成物は、（Ａ）固有粘度０．７０〜１．００g／ｄＬのポリブチレンテレフタレート樹脂１００質量部に対し、（Ｂ）臭素系難燃剤として（Ｂ−１）臭素化エポキシ系難燃剤及び／又は（Ｂ−２）臭素化ポリアクリレート系難燃剤を合計で２０〜６５質量部と、（Ｃ）アンチモン系難燃助剤１０〜３０質量部と、（Ｄ）タルク３〜１５質量部と、（Ｅ）水酸基価１００以上の多価水酸基含有化合物１〜１０質量部とを含むことを特徴としている。
本発明のＰＢＴ樹脂は、上記（Ａ）〜（Ｅ）成分を所定量含むことで、ＵＬ９４に準拠した厚さ０．２ｍｍの難燃性をＶ−０とし、所定の射出成形により成形する成形品における厚さ０．５ｍｍの薄肉部の流動長を４０ｍｍ以上とすることができる。つまり、成形時において流動性に優れ、薄肉に成形した場合でも難燃性に優れる。
以下、本発明のＰＢＴ樹脂組成物の各成分について詳述する。<Polybutylene terephthalate resin composition>
The polybutylene terephthalate resin composition of the present invention comprises (B) bromine-based flame retardant (B-1) bromine with respect to 100 parts by weight of (A) polybutylene terephthalate resin having an intrinsic viscosity of 0.70 to 1.00 g / dL. 20 to 65 parts by mass of the totalized epoxy flame retardant and / or (B-2) brominated polyacrylate flame retardant, 10 to 30 parts by mass of (C) antimony flame retardant aid, and (D) talc 3 to 15 parts by mass and (E) 1 to 10 parts by mass of a polyhydric hydroxyl group-containing compound having a hydroxyl value of 100 or more.
The PBT resin of the present invention includes a predetermined amount of the components (A) to (E), so that the flame retardancy with a thickness of 0.2 mm conforming to UL94 is set to V-0, and molding is performed by predetermined injection molding. The flow length of the thin portion having a thickness of 0.5 mm in the product can be 40 mm or more. That is, it is excellent in fluidity at the time of molding and excellent in flame retardancy even when molded into a thin wall.
Hereinafter, each component of the PBT resin composition of this invention is explained in full detail.
［（Ａ）ポリブ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（ＰＢＴ樹脂）は、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１−６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも炭素原子数４のアルキレングリコール（１，４−ブタンジオール）又はそのエステル形成性誘導体（アセチル化物等）を含むグリコール成分とを重縮合して得られる樹脂である。ＰＢＴ樹脂は、ホモポリブチレンテレフタレートに限らず、ブチレンテレフタレート単位を６０モル％以上（特に７５モル％以上９５モル％以下）含有する共重合体であってもよい。[(A) Polybutylene terephthalate resin]
The polybutylene terephthalate resin (PBT resin) is composed of a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C 1-6 alkyl ester, acid halide, etc.), and an alkylene glycol having at least 4 carbon atoms (1 , 4-butanediol) or an ester-forming derivative thereof (acetylated product, etc.) and a resin obtained by polycondensation. The PBT resin is not limited to homopolybutylene terephthalate but may be a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
ＰＢＴ樹脂の末端カルボキシル基量は、本発明の効果を阻害しない限り特に限定されない。ＰＢＴ樹脂の末端カルボキシル基量は、３０ｍｅｑ／ｋｇ以下が好ましく、２５ｍｅｑ／ｋｇ以下がより好ましい。 The amount of the terminal carboxyl group of the PBT resin is not particularly limited as long as the effect of the present invention is not inhibited. The amount of terminal carboxyl groups of the PBT resin is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less.
ＰＢＴ樹脂の固有粘度（ＩＶ）は０．７０〜１．００ｄＬ／ｇであり、好ましくは０．７２〜０．９５ｄＬ／ｇ、さらに好ましくは０．７５〜０．９０ｄＬ／gである。かかる範囲の固有粘度のＰＢＴ樹脂を用いる場合には、得られるＰＢＴ樹脂組成物が特に難燃性と流動性に優れたものとなる。逆に固有粘度０．７０ｄＬ／ｇ未満では優れた難燃性が得られず、１．００ｄＬ／ｇを超えると優れた流動性が得られない。
また、固有粘度が上記範囲のＰＢＴ樹脂は、異なる固有粘度を有するＰＢＴ樹脂をブレンドして、固有粘度を調整することもできる。例えば、固有粘度０．９ｄＬ／ｇのＰＢＴ樹脂と固有粘度０．７ｄＬ／ｇのＰＢＴ樹脂とをブレンドすることにより、固有粘度０．８ｄＬ／ｇのＰＢＴ樹脂を調製することができる。ＰＢＴ樹脂の固有粘度（ＩＶ）は、例えば、ｏ−クロロフェノール中で温度３５℃の条件で測定することができる。The intrinsic viscosity (IV) of the PBT resin is 0.70 to 1.00 dL / g, preferably 0.72 to 0.95 dL / g, and more preferably 0.75 to 0.90 dL / g. When a PBT resin having an intrinsic viscosity in such a range is used, the obtained PBT resin composition is particularly excellent in flame retardancy and fluidity. Conversely, if the intrinsic viscosity is less than 0.70 dL / g, excellent flame retardancy cannot be obtained, and if it exceeds 1.00 dL / g, excellent fluidity cannot be obtained.
The PBT resin having an intrinsic viscosity in the above range can be adjusted by blending PBT resins having different intrinsic viscosities. For example, a PBT resin having an intrinsic viscosity of 0.8 dL / g can be prepared by blending a PBT resin having an intrinsic viscosity of 0.9 dL / g and a PBT resin having an intrinsic viscosity of 0.7 dL / g. The intrinsic viscosity (IV) of the PBT resin can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.
ＰＢＴ樹脂において、テレフタル酸及びそのエステル形成性誘導体以外のジカルボン酸成分（コモノマー成分）としては、例えば、イソフタル酸、フタル酸、２，６−ナフタレンジカルボン酸、４，４’−ジカルボキシジフェニルエーテル等のＣ８−１４の芳香族ジカルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸等のＣ４−１６のアルカンジカルボン酸；シクロヘキサンジカルボン酸等のＣ５−１０のシクロアルカンジカルボン酸；これらのジカルボン酸成分のエステル形成性誘導体（Ｃ１−６のアルキルエステル誘導体や酸ハロゲン化物等）が挙げられる。これらのジカルボン酸成分は、単独で又は２種以上を組み合わせて使用できる。In the PBT resin, as dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl ether, etc. C 8-14 aromatic dicarboxylic acids; C 4-16 alkane dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C 5-10 cycloalkane dicarboxylic acids such as cyclohexane dicarboxylic acid; these dicarboxylic acids Examples thereof include ester-forming derivatives of acid components (C 1-6 alkyl ester derivatives, acid halides, and the like). These dicarboxylic acid components can be used alone or in combination of two or more.
これらのジカルボン酸成分の中では、イソフタル酸等のＣ８−１２の芳香族ジカルボン酸、及び、アジピン酸、アゼライン酸、セバシン酸等のＣ６−１２のアルカンジカルボン酸がより好ましい。Among these dicarboxylic acid components, C 8-12 aromatic dicarboxylic acids such as isophthalic acid, and C 6-12 alkanedicarboxylic acids such as adipic acid, azelaic acid, and sebacic acid are more preferable.
ＰＢＴ樹脂において、１，４−ブタンジオール以外のグリコール成分（コモノマー成分）としては、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３−ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、１，３−オクタンジオール等のＣ２−１０のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等のポリオキシアルキレングリコール；シクロヘキサンジメタノール、水素化ビスフェノールＡ等の脂環式ジオール；ビスフェノールＡ、４，４’−ジヒドロキシビフェニル等の芳香族ジオール；ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等の、ビスフェノールＡのＣ２−４のアルキレンオキサイド付加体；又はこれらのグリコールのエステル形成性誘導体（アセチル化物等）が挙げられる。これらのグリコール成分は、単独で又は２種以上を組み合わせて使用できる。In the PBT resin, as glycol components (comonomer components) other than 1,4-butanediol, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1, C 2-10 alkylene glycol such as 3-octanediol; polyoxyalkylene glycol such as diethylene glycol, triethylene glycol and dipropylene glycol; cycloaliphatic diol such as cyclohexanedimethanol and hydrogenated bisphenol A; bisphenol A, 4, Bisphenols, such as aromatic diols such as 4'-dihydroxybiphenyl; ethylene oxide 2-mole adducts of bisphenol A, propylene oxide 3-mole adducts of bisphenol A, etc. Alkylene oxide adducts of C 2-4 of A; or ester-forming derivatives of these glycols (acetylated, etc.). These glycol components can be used alone or in combination of two or more.
これらのグリコール成分の中では、エチレングリコール、トリメチレングリコール等のＣ２−６のアルキレングリコール、ジエチレングリコール等のポリオキシアルキレングリコール、又は、シクロヘキサンジメタノール等の脂環式ジオール等がより好ましい。Among these glycol components, C 2-6 alkylene glycol such as ethylene glycol and trimethylene glycol, polyoxyalkylene glycol such as diethylene glycol, and alicyclic diol such as cyclohexanedimethanol are more preferable.
ジカルボン酸成分及びグリコール成分の他に使用できるコモノマー成分としては、例えば、４−ヒドロキシ安息香酸、３−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸、４−カルボキシ−４’−ヒドロキシビフェニル等の芳香族ヒドロキシカルボン酸；グリコール酸、ヒドロキシカプロン酸等の脂肪族ヒドロキシカルボン酸；プロピオラクトン、ブチロラクトン、バレロラクトン、カプロラクトン（ε−カプロラクトン等）等のＣ３−１２ラクトン；これらのコモノマー成分のエステル形成性誘導体（Ｃ１−６のアルキルエステル誘導体、酸ハロゲン化物、アセチル化物等）が挙げられる。Examples of comonomer components that can be used in addition to the dicarboxylic acid component and the glycol component include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 4-carboxy-4′-hydroxybiphenyl. Aromatic hydroxycarboxylic acids; Aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; C 3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (ε-caprolactone, etc.); esters of these comonomer components And forming derivatives (C 1-6 alkyl ester derivatives, acid halides, acetylated compounds, etc.).
［（Ｂ）臭素系難燃剤］
本発明のＰＢＴ樹脂組成物は（Ｂ）臭素系難燃剤として（Ｂ−１）臭素化エポキシ系難燃剤及び／又は（Ｂ−２）臭素化ポリアクリレート系難燃剤を含有する。本発明のＰＢＴ樹脂組成物は、特定の（Ｂ）臭素系難燃剤と、後述する（Ｄ）タルクおよび（Ｅ）多価水酸基含有化合物を組み合わせて用いることにより、ＰＢＴ樹脂組成物に高い難燃性を付与しつつ、顕著な流動性の改善効果を示す。（Ｂ）の特定の臭素系難燃剤以外の難燃剤との組み合わせを配合した場合は、十分な難燃性と流動性の改善効果が得られない。[(B) Brominated flame retardant]
The PBT resin composition of the present invention contains (B-1) a brominated epoxy flame retardant and / or (B-2) a brominated polyacrylate flame retardant as (B) a brominated flame retardant. The PBT resin composition of the present invention uses a specific (B) bromine-based flame retardant in combination with (D) talc and (E) a polyhydric hydroxyl group-containing compound, which will be described later. It shows a remarkable fluidity improvement effect while imparting the properties. When a combination with a flame retardant other than the specific brominated flame retardant (B) is blended, sufficient flame retardancy and fluidity improvement effects cannot be obtained.
（Ｂ−１）臭素化エポキシ系難燃剤としては、下記式（１）で表されるポリ（テトラブロム）ビスフェノールＡ型エポキシ化合物が好ましい。
また、（Ｂ−１）臭素化エポキシ系難燃剤として、両方または一方の末端が封止された臭素化エポキシ系難燃剤を使用してもよい。末端を封止した臭素化エポキシ系難燃剤を使用すれば、成形時の樹脂組成物の流動性が高くなるため好ましい。「流動性が高くなる」とは、実施例に記載の方法で測定した厚さ０．５ｍｍでの流動長が、４０ｍｍ以上である。 Moreover, you may use the brominated epoxy flame retardant with which both or one terminal was sealed as (B-1) brominated epoxy flame retardant. It is preferable to use a brominated epoxy flame retardant whose end is sealed because the fluidity of the resin composition at the time of molding becomes high. “High fluidity” means that the flow length at a thickness of 0.5 mm measured by the method described in Examples is 40 mm or more.
末端封止された臭素化エポキシ系難燃剤の中でも、下記式（２）で表されるビスフェノールＡ型エポキシ化合物を用いると、得られる樹脂組成物の機械的特性も優れるため好ましい。なお、末端封止にはブロモフェノールが好ましく使用されるが、ブロモフェノールの中でもトリブロモフェノールが特に好ましく使用される。
（上記式（２）中の、ｘは１以上５以下の整数である。）Among the end-capped brominated epoxy flame retardants, it is preferable to use a bisphenol A type epoxy compound represented by the following formula (2) because the mechanical properties of the resulting resin composition are excellent. Note that bromophenol is preferably used for end-capping, but tribromophenol is particularly preferably used among bromophenols.
(In the above formula (2), x is an integer of 1 or more and 5 or less.)
本発明において（Ｂ）臭素系難燃剤として用いる（Ｂ−１）臭素化エポキシ系難燃剤は、平均重合度ｎが１０〜５０であり、且つ難燃剤として使用できるものであることが好ましい。平均重合度はより好ましくは１１〜４０、さらに好ましくは１１〜２０である。平均重合度が１０以上であれば、臭素化エポキシ系難燃剤のエポキシ当量が大きくなり過ぎないため、ＰＢＴ樹脂との反応による成形加工性の低下を抑制することができ、また、平均重合度が５０以下であれば、ＰＢＴ樹脂組成物の流動性を損なわずに難燃性を付与することができる。 In the present invention, the (B-1) brominated epoxy flame retardant used as (B) a brominated flame retardant preferably has an average polymerization degree n of 10 to 50 and can be used as a flame retardant. The average degree of polymerization is more preferably 11-40, and still more preferably 11-20. If the average degree of polymerization is 10 or more, since the epoxy equivalent of the brominated epoxy flame retardant does not become too large, it is possible to suppress a decrease in molding processability due to the reaction with the PBT resin, and the average degree of polymerization is If it is 50 or less, a flame retardance can be provided, without impairing the fluidity | liquidity of a PBT resin composition.
臭素化エポキシ系難燃剤の製造には公知の製造方法が用いられる。例えばテトラブロムビスフェノールＡとエピクロルヒドリンを反応させて得られるテトラブロムビスフェノールＡジグリシジルエーテルに、更にそのエポキシ基１当量に対して、テトラブロムビスフェノールＡをその水酸基が０〜０．９６当量になるように混合し、塩基性触媒、例えば水酸化ナトリウム、水酸化リチウム、トリブチルアミン等の存在下に１００〜２５０℃で加熱反応させることにより得ることができる。 A well-known manufacturing method is used for manufacture of a brominated epoxy flame retardant. For example, tetrabromobisphenol A diglycidyl ether obtained by reacting tetrabromobisphenol A with epichlorohydrin is further added such that tetrabromobisphenol A has a hydroxyl group of 0 to 0.96 equivalent to 1 equivalent of its epoxy group. It can be obtained by mixing and heating at 100 to 250 ° C. in the presence of a basic catalyst such as sodium hydroxide, lithium hydroxide, tributylamine and the like.
本発明において（Ｂ）臭素系難燃剤として用いる（Ｂ−２）臭素化ポリアクリレート系難燃剤は、ペンタブロモベンジルアクリレート及び／又はペンタブロモベンジルメタクリレートに由来する単位を含む重合体である。臭素化ポリアクリレート系難燃剤の平均重合度は、本発明の効果を阻害しない範囲で制限されず、２０〜１６０であるのが好ましく、５０〜１２０であるのがより好ましい。かかる範囲のものを用いることで、得られるＰＢＴ樹脂組成物が耐熱性と流動性に優れるものとなる。 In the present invention, the (B-2) brominated polyacrylate flame retardant used as the (B) bromine flame retardant is a polymer containing units derived from pentabromobenzyl acrylate and / or pentabromobenzyl methacrylate. The average degree of polymerization of the brominated polyacrylate flame retardant is not limited as long as the effect of the present invention is not impaired, and is preferably 20 to 160, more preferably 50 to 120. By using the thing of this range, the PBT resin composition obtained will be excellent in heat resistance and fluidity | liquidity.
本発明において好適に使用できる（Ｂ−２）臭素化ポリアクリレート系難燃剤の具体例としては、ポリペンタブロムベンジルアクリレート、ポリテトラブロムベンジルアクリレート、ポリトリブロムベンジルアクリレート、ポリペンタブロムベンジルメタクリレート等が挙げられるが、ポリペンタブロムベンジルアクリレートが特に好ましい。 Specific examples of the (B-2) brominated polyacrylate flame retardant that can be suitably used in the present invention include polypentabromobenzyl acrylate, polytetrabromobenzyl acrylate, polytribromobenzyl acrylate, polypentabromobenzyl methacrylate, and the like. Among them, polypentabromobenzyl acrylate is particularly preferable.
本発明における（Ｂ−１）臭素化エポキシ系難燃剤と（Ｂ−２）臭素化ポリアクリレート系難燃剤の含有量は、両者の合計量として、ＰＢＴ樹脂１００質量部に対し、２０〜６５質量部であり、好ましくは３０〜５５質量部である。当該合計含有量が２０質量部未満であるとＰＢＴ樹脂の難燃化効果が十分でなく、また６５質量部を超えると組成物の機械的特性が低下したり、異物が発生し成形品の外観が悪化したりする等の欠点が現れてくる。また、（Ｂ−１）臭素化エポキシ系難燃剤と（Ｂ−２）臭素化ポリアクリレート系難燃剤の含有割合は、特に限定されないが、（Ｂ−１）／（Ｂ−２）＝１００／０〜５０／５０であれば、本発明の難燃性、流動性改良効果が特に発揮されるため好ましい。 In the present invention, the content of (B-1) brominated epoxy flame retardant and (B-2) brominated polyacrylate flame retardant is 20 to 65 mass with respect to 100 mass parts of PBT resin as the total amount of both. Part, preferably 30 to 55 parts by weight. When the total content is less than 20 parts by mass, the flame retarding effect of the PBT resin is not sufficient, and when it exceeds 65 parts by mass, the mechanical properties of the composition are deteriorated or foreign matters are generated and the appearance of the molded product. Defects such as worsening appear. Further, the content ratio of (B-1) brominated epoxy flame retardant and (B-2) brominated polyacrylate flame retardant is not particularly limited, but (B-1) / (B-2) = 100 / If it is 0-50 / 50, since the flame retardance of this invention and a fluid improvement effect are exhibited especially, it is preferable.
本発明のＰＢＴ樹脂組成物中の有機成分全体における臭素含有量が１０〜２０質量％であることが好ましく、１２〜１８質量％であることがより好ましく、１３〜１７質量％であることが特に好ましい。当該臭素含有量が上記範囲内であると、組成物の機械的特性が低下したり、成形品の外観が悪化したりすることなく、十分な難燃化効果を得ることができる。 The bromine content in the entire organic component in the PBT resin composition of the present invention is preferably 10 to 20% by mass, more preferably 12 to 18% by mass, and particularly preferably 13 to 17% by mass. preferable. When the bromine content is within the above range, a sufficient flame retarding effect can be obtained without deteriorating the mechanical properties of the composition or deteriorating the appearance of the molded product.
［（Ｃ）アンチモン系難燃助剤］
本発明のＰＢＴ樹脂組成物には、難燃助剤として（Ｃ）アンチモン系難燃助剤が含まれる。本発明において用いるアンチモン系難燃助剤は、アンチモンを含有し、良好な難燃効果が得られるものであれば、本発明の効果を阻害しない範囲で特に限定されない。本発明において好適に使用されるアンチモン系難燃助剤の具体例としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、アンチモン酸ナトリウム、ハロゲン化アンチモン等が挙げられる。中でも供給性やコスト面で三酸化アンチモンを用いることが好ましい。[(C) Antimony flame retardant aid]
The PBT resin composition of the present invention contains (C) an antimony flame retardant aid as a flame retardant aid. The antimony flame retardant aid used in the present invention is not particularly limited as long as it contains antimony and a good flame retardant effect can be obtained. Specific examples of the antimony flame retardant aid preferably used in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, antimony halide and the like. Of these, it is preferable to use antimony trioxide in terms of supply and cost.
アンチモン系難燃助剤の形態は特に限定されないが、平均粒子径が０．１〜１０μｍの粒子状であるものが好ましく、平均粒子径が０．３〜５μｍであるものがより好ましく、０．５〜２μｍであるものが特に好ましい。前記平均粒子径が１０μｍより大きいと、得られるＰＢＴ樹脂組成物に機械的な応力が加えられたときに破壊の起点となりやすく脆さを生じる他、難燃性も低下する。また、０．１μｍより小さいと、（Ａ）ＰＢＴ樹脂と（Ｂ）臭素系難燃剤との反応を促し、成形安定性を損なうおそれがある。 The form of the antimony flame retardant aid is not particularly limited, but is preferably in the form of particles having an average particle diameter of 0.1 to 10 μm, more preferably having an average particle diameter of 0.3 to 5 μm, and What is 5-2 micrometers is especially preferable. When the average particle diameter is larger than 10 μm, when mechanical stress is applied to the obtained PBT resin composition, it tends to become a starting point of breakage and causes brittleness, and flame retardancy also decreases. Moreover, when smaller than 0.1 micrometer, there exists a possibility of accelerating | stimulating reaction with (A) PBT resin and (B) bromine-type flame retardant, and impairing molding stability.
前記平均粒子径は、レーザー回折／散乱式粒度分布測定装置ＬＡ−９２０（堀場製作所製）にて、分散媒として蒸留水を用いて測定し、メジアン径として得ることができる。 The average particle diameter can be obtained as a median diameter by measuring with a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.) using distilled water as a dispersion medium.
本発明のＰＢＴ樹脂組成物中の（Ｃ）アンチモン系難燃助剤の含有量は、（Ａ）ＰＢＴ樹脂１００質量部に対し１０〜３０質量部であり、好ましくは１０〜２０質量部である。この含有量が１０質量部より小さい場合には難燃助剤としての効果が十分発揮されず、また３０質量部より大きい場合には機械的特性が低下する等の欠点が現れてくる。また、（Ｂ）臭素系難燃剤の含有量との関係としては、ＰＢＴ樹脂組成物中における、臭素系難燃剤中の臭素原子及びアンチモン系難燃助剤中のアンチモン原子の質量の合計量が、ＰＢＴ樹脂組成物中の有機成分の合計量に対して１０〜２８質量％であってもよく、好ましくは１５〜２６質量％、特に好ましくは１８〜２４質量％であってもよい。また、ＰＢＴ樹脂組成物中における、臭素系難燃剤中の臭素原子の質量と、アンチモン系難燃助剤中のアンチモン原子の質量との比率（臭素原子／アンチモン原子）が、２／１〜４／１であってもよい。アンチモン系難燃助剤が上記を満たすように配合されることで、臭素系難燃剤による難燃性付与効果を効果的に高めることができる。 The content of the (C) antimony flame retardant aid in the PBT resin composition of the present invention is 10 to 30 parts by mass, preferably 10 to 20 parts by mass with respect to 100 parts by mass of the (A) PBT resin. . When the content is less than 10 parts by mass, the effect as a flame retardant aid is not sufficiently exhibited. When the content is more than 30 parts by mass, defects such as deterioration of mechanical properties appear. In addition, the relationship with the content of the brominated flame retardant (B) is that the total amount of bromine atoms in the brominated flame retardant and antimony atoms in the antimony flame retardant auxiliary in the PBT resin composition is The amount of the organic component in the PBT resin composition may be 10 to 28% by mass, preferably 15 to 26% by mass, and particularly preferably 18 to 24% by mass. Moreover, the ratio (bromine atom / antimony atom) between the mass of bromine atoms in the brominated flame retardant and the mass of antimony atoms in the antimony flame retardant auxiliary in the PBT resin composition is 2/1 to 4 / 1 may be sufficient. By blending the antimony flame retardant auxiliary so as to satisfy the above, it is possible to effectively enhance the flame retardancy imparting effect by the bromine flame retardant.
［（Ｄ）タルク］
本発明の樹脂組成物には、無機難燃助剤としてさらに（Ｄ）タルクが含まれる。タルクとは、ケイ酸塩鉱物の一種であり、水酸化マグネシウム及びケイ酸塩等を含む。[(D) Talc]
The resin composition of the present invention further contains (D) talc as an inorganic flame retardant aid. Talc is a kind of silicate mineral and includes magnesium hydroxide and silicate.
従来、タルクは、ＰＢＴ樹脂組成物中に、強化剤、核剤、電気特性向上剤、高熱伝導剤等として添加されてきた。しかし、本発明者らの検討の結果、前述の臭素系難燃剤及びアンチモン系難燃助剤とともにタルクを含むＰＢＴ樹脂組成物においては、タルクは優れた難燃助剤として作用することを見出した。 Conventionally, talc has been added to a PBT resin composition as a reinforcing agent, a nucleating agent, an electrical property improving agent, a high thermal conductive agent, and the like. However, as a result of the study by the present inventors, it has been found that talc acts as an excellent flame retardant aid in the PBT resin composition containing talc together with the brominated flame retardant and antimony flame retardant aid described above. .
従来は、例えば、難燃ポリプロピレン樹脂組成物にタルクを添加すると、該樹脂組成物から得られる成形体の難燃性が低下してしまうことが知られていた（清野充ら、「ＰＰの燃焼特性におよぼす難燃剤及びタルクの分布状態の影響」、成形加工、Ｖｏｌ．２２ Ｎｏ．５ ２０１０等を参照されたい）。このような知見からすれば、ポリプロピレン同様に結晶性樹脂であるポリブチレンテレフタレートと、タルクとが配合された樹脂組成物から得られる成形品の難燃性が高いという本発明の効果は予想外であると言える。 Conventionally, it has been known that, for example, when talc is added to a flame retardant polypropylene resin composition, the flame retardancy of a molded product obtained from the resin composition is reduced (Mitsuaki Seino et al., “Combustion of PP”). Effect of flame retardant and talc distribution on properties ", molding process, Vol.22 No.5 2010 etc.). From such knowledge, the effect of the present invention that the flame retardancy of a molded product obtained from a resin composition in which polybutylene terephthalate, which is a crystalline resin, and talc are blended as in polypropylene is high is unexpected. It can be said that there is.
本発明における（Ｄ）タルクの平均粒子径は、３μｍ以上が好ましく、より好ましくは５μｍ以上であり、特に好ましくは１０μｍ以上である。タルクの平均粒子径が３μｍであると、難燃性が特に有利となるため好ましい。タルクの平均粒子径の上限は特に限定されないが、１００μｍ以下であれば、得られるＰＢＴ樹脂組成物中での分散性が有利となるため好ましい。ここで、タルクの平均粒子径とは、レーザー回折法による測定装置を用い、ＪＩＳ Ｚ８８２５−１に準拠して測定を行い、頻度分布を算術平均した平均粒子径を指す。 In the present invention, the average particle diameter of (D) talc is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. It is preferable that the average particle diameter of talc is 3 μm because flame retardancy is particularly advantageous. The upper limit of the average particle diameter of talc is not particularly limited, but it is preferably 100 μm or less because dispersibility in the obtained PBT resin composition becomes advantageous. Here, the average particle diameter of talc refers to an average particle diameter obtained by performing measurement in accordance with JIS Z8825-1 using a measuring device by a laser diffraction method and arithmetically averaging the frequency distribution.
本発明における（Ｄ）タルクの含有量は、（Ａ）ＰＢＴ樹脂１００質量部に対して３〜１５質量部であり、好ましくは５〜１０質量部、特に好ましくは６〜８質量部である。タルクの含有量がＰＢＴ樹脂１００質量部に対して３〜１５質量部であると、難燃性と機械的特性の両立が可能であるため特に好ましい。逆に、タルクの含有量が３質量部未満であると、得られるＰＢＴ樹脂組成物の難燃性は十分ではない。タルクの含有量が１５質量部を超えると、得られるＰＢＴ樹脂組成物の機械的特性が十分ではない。また、原因は明確ではないが、過剰量のタルクを添加すると、靭性等の機械的特性だけでなく難燃性も低下する場合がある。 Content of (D) talc in this invention is 3-15 mass parts with respect to 100 mass parts of (A) PBT resin, Preferably it is 5-10 mass parts, Most preferably, it is 6-8 mass parts. It is particularly preferable that the content of talc is 3 to 15 parts by mass with respect to 100 parts by mass of the PBT resin because both flame retardancy and mechanical properties can be achieved. On the contrary, if the content of talc is less than 3 parts by mass, the flame retardancy of the resulting PBT resin composition is not sufficient. If the talc content exceeds 15 parts by mass, the mechanical properties of the resulting PBT resin composition are not sufficient. Further, although the cause is not clear, when an excessive amount of talc is added, not only mechanical properties such as toughness but also flame retardancy may be lowered.
本発明のＰＢＴ樹脂組成物中には、（Ｄ）タルクと、（Ｂ）臭素系難燃剤と、（Ｃ）アンチモン系難燃助剤との合計量に対して５．０〜４０．０質量％、好ましくは６．０〜３５．０質量％のタルクが含まれることが好ましい。このような割合でタルクが配合されることにより、得られるＰＢＴ樹脂組成物に優れた流動性と難燃性、さらには優れた機械的物性を付与することができる。 In the PBT resin composition of the present invention, 5.0 to 40.0 mass relative to the total amount of (D) talc, (B) bromine-based flame retardant, and (C) antimony-based flame retardant aid. %, Preferably 6.0 to 35.0% by mass of talc. By blending talc at such a ratio, excellent fluidity and flame retardancy, and further excellent mechanical properties can be imparted to the obtained PBT resin composition.
［（Ｅ）多価水酸基含有化合物］
（Ｅ）多価水酸基含有化合物は、一分子中に水酸基を２個以上有する化合物である。この（Ｅ）多価水酸基含有化合物は、流動性改良剤として働く。通常、（Ａ）ＰＢＴ樹脂に流動性改良剤を添加すると、流動性を向上できても、（Ａ）ＰＢＴ樹脂そのものが有する機械的強度や靱性等の特性の低下を避けることができない。しかし、多価水酸基含有化合物を使用することにより、（Ａ）ＰＢＴ樹脂の特性を高いレベルで保持しつつＰＢＴ樹脂組成物の溶融時の流動性を効率よく向上できる。[(E) Polyhydric hydroxyl group-containing compound]
(E) A polyvalent hydroxyl group-containing compound is a compound having two or more hydroxyl groups in one molecule. This (E) polyhydric hydroxyl group-containing compound works as a fluidity improver. Usually, when a fluidity improver is added to (A) PBT resin, even if fluidity can be improved, deterioration of properties such as mechanical strength and toughness of (A) PBT resin itself cannot be avoided. However, by using the polyvalent hydroxyl group-containing compound, the fluidity at the time of melting of the PBT resin composition can be efficiently improved while maintaining the characteristics of the (A) PBT resin at a high level.
（Ｅ）多価水酸基含有化合物は、従来公知の方法で製造したものを使用してもよいし、市販品を購入して使用してもよい。 (E) As the polyvalent hydroxyl group-containing compound, one produced by a conventionally known method may be used, or a commercially available product may be purchased and used.
（Ｅ）多価水酸基含有化合物は日本油化学会２．３．６．２−１９９６ ヒドロキシル価（ピリジン−無水酢酸法）に準拠して測定した水酸基価が、１００以上であることが好ましく、より好ましくは２００以上である。上記水酸基価が１００以上であれば、上記流動性向上の効果がより高まる傾向にあることに加え、耐加水分解性をも向上させる効果が得られるため好ましい。一方、上記水酸基価が大き過ぎる場合、（Ａ）ポリブチレンテレフタレートとの反応が過剰に進む事で、（Ａ）ポリブチレンテレフタレート樹脂の分子量が低下し、機械特性や耐熱性、耐薬品性といった優れた特性を損なうおそれがある他、成形時のガス発生による成形品の外観不良や金型汚れを生じるおそれがある。好ましい水酸基価は１０００以下であり、６００以下であることがより好ましい。 (E) The polyhydric hydroxyl group-containing compound preferably has a hydroxyl value measured in accordance with 2.3.6.2-1996 hydroxyl value (pyridine-acetic anhydride method) of the Japan Oil Chemical Society, 100 or more. Preferably it is 200 or more. It is preferable that the hydroxyl value is 100 or more because the effect of improving the fluidity tends to be further increased and the effect of improving the hydrolysis resistance is also obtained. On the other hand, if the hydroxyl value is too large, the reaction with (A) polybutylene terephthalate will proceed excessively, and the molecular weight of (A) polybutylene terephthalate resin will decrease, resulting in excellent mechanical properties, heat resistance, and chemical resistance. In addition to impairing the properties of the molded product, it may cause appearance defects and mold contamination due to gas generation during molding. The preferred hydroxyl value is 1000 or less, and more preferably 600 or less.
（Ｅ）多価水酸基含有化合物の含有量は、（Ａ）ＰＢＴ樹脂１００質量部に対して１〜１０質量部であり、好ましくは１．５〜７．５質量部であり、さらに好ましくは２〜５質量部である。当該含有量が１質量部未満であると、流動性向上の効果が十分に得られず、１０質量部を超えると、成形品からの染み出しを生じたり、成形時のガス発生による成形品の外観不良や金型汚れを生じたりするおそれがある。 (E) Content of a polyhydric hydroxyl group containing compound is 1-10 mass parts with respect to 100 mass parts of (A) PBT resin, Preferably it is 1.5-7.5 mass parts, More preferably, it is 2 -5 parts by mass. If the content is less than 1 part by mass, the effect of improving the fluidity cannot be sufficiently obtained, and if it exceeds 10 parts by mass, bleeding from the molded product occurs or the molded product is generated by gas generation during molding. There is a risk of appearance defects and mold contamination.
ＰＢＴ樹脂組成物に溶融時の流動性を付与する観点、又は得られる成形品に（Ａ）ＰＢＴ樹脂の物性をほとんど低下させずに付与する観点から、（Ｅ）多価水酸基含有化合物として、グリセリン脂肪酸エステル又はジグリセリンに酸化アルキレンを付加重合して得られるエーテルを使用することが好ましい。次いで、グリセリン脂肪酸エステル、ジグリセリンに酸化アルキレンを付加重合して得られるエーテルの順で具体例等を示す。 From the viewpoint of imparting fluidity at the time of melting to the PBT resin composition, or from the viewpoint of imparting almost no deterioration in the physical properties of the (A) PBT resin to the obtained molded product, (E) glycerin as a polyhydric hydroxyl group-containing compound It is preferable to use an ether obtained by addition polymerization of an alkylene oxide to a fatty acid ester or diglycerin. Next, specific examples are shown in the order of ether obtained by addition polymerization of alkylene oxide to glycerin fatty acid ester and diglycerin.
先ず、グリセリン脂肪酸エステルは、グリセリン及び／又はその脱水縮合物と脂肪酸とからなるエステルである。グリセリン脂肪酸エステルの中でも、炭素数１２以上の脂肪酸を用いて得られるものが好ましい。炭素数が１２以上の脂肪酸としては、例えば、ラウリン酸、オレイン酸、パルミチン酸、ステアリン酸、１２−ヒドロキシステアリン酸、ベヘニン酸、モンタン酸等が挙げられる。好ましくは炭素数１２以上３２以下の脂肪酸であり、特に好ましくは炭素数１２以上２２以下の脂肪酸である。具体的には、ラウリン酸、ステアリン酸、１２−ヒドロキシステアリン酸又はベヘニン酸が特に好ましい。炭素数１２以上の脂肪酸を用いることで、樹脂の耐熱性を充分に維持することができ、また高温環境下における（Ｅ）多価水酸基含有化合物の染み出しが抑制できる傾向にあるため好ましい。炭素数が３２以下であれば、上記流動性改善の効果が高いため好ましい。 First, glycerol fatty acid ester is ester which consists of glycerol and / or its dehydration condensate, and a fatty acid. Among glycerin fatty acid esters, those obtained using fatty acids having 12 or more carbon atoms are preferred. Examples of the fatty acid having 12 or more carbon atoms include lauric acid, oleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Fatty acids having 12 to 32 carbon atoms are preferred, and fatty acids having 12 to 22 carbon atoms are particularly preferred. Specifically, lauric acid, stearic acid, 12-hydroxystearic acid or behenic acid is particularly preferable. It is preferable to use a fatty acid having 12 or more carbon atoms because the heat resistance of the resin can be sufficiently maintained and the bleeding of the (E) polyvalent hydroxyl group-containing compound in a high temperature environment tends to be suppressed. A carbon number of 32 or less is preferable because the effect of improving the fluidity is high.
好ましいグリセリン脂肪酸エステルを例示すると、グリセリンモノステアレート、グリセリンモノベヘネート、ジグリセリンモノステアレート、トリグリセリンモノステアレート、トリグリセリンステアリン酸部分エステル、テトラグリセリンステアリン酸部分エステル、デカグリセリンラウリン酸部分エステル、グリセリンモノ１２−ヒドロキシステアレート等が挙げられる。 Examples of preferred glycerin fatty acid esters include glycerin monostearate, glycerin monobehenate, diglycerin monostearate, triglycerin monostearate, triglycerin stearic acid partial ester, tetraglycerin stearic acid partial ester, decaglycerin lauric acid partial ester Glycerin mono-12-hydroxystearate and the like.
次いで、ジグリセリンに酸化アルキレンを付加重合して得られるエーテルとしては、例えば、ジグリセリンに酸化プロピレンを付加重合して得られるポリオキシプロピレンジグリセリルエーテルや、ジグリセリンに酸化エチレンを付加重合して得られるポリオキシエチレンジグリセリルエーテルが挙げられる。本発明においては、これらのエーテルの中でも、特に、ポリオキシエチレンジグリセリルエーテルの使用が好ましい。 Next, as an ether obtained by addition polymerization of alkylene oxide to diglycerin, for example, polyoxypropylene diglyceryl ether obtained by addition polymerization of propylene oxide to diglycerin or addition polymerization of ethylene oxide to diglycerin. The polyoxyethylene diglyceryl ether obtained is mentioned. In the present invention, among these ethers, use of polyoxyethylene diglyceryl ether is particularly preferable.
なお、ジグリセリンに酸化アルキレンを付加重合して得られるエーテルなどのアルキレンオキシド単位を含む多価アルコール化合物は、通常液体のため、ハンドリング性の観点、又は高温環境下では成形品の安定性の観点から、固体のグリセリン脂肪酸エステルを使用することがより好ましい。 Since polyhydric alcohol compounds containing alkylene oxide units such as ether obtained by addition polymerization of alkylene oxide to diglycerin are usually liquid, from the viewpoint of handling properties, or from the viewpoint of stability of molded products in a high temperature environment Therefore, it is more preferable to use a solid glycerin fatty acid ester.
［（Ｆ）滴下防止剤］
本発明のＰＢＴ樹脂組成物には、難燃剤と共にフッ素系樹脂等の（Ｆ）滴下防止剤を用いることが好ましい。[(F) Anti-drip agent]
In the PBT resin composition of the present invention, it is preferable to use (F) an anti-drip agent such as a fluorine resin together with a flame retardant.
滴下防止剤は、燃焼時の樹脂の滴下を防止するために使用される。（Ｆ）滴下防止剤の具体例としては、ポリテトラフルオロエチレン、テトラフルオロエチレン／パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン／エチレン共重合体、フッ化ビニリデン、ポリクロロトリフルオロエチレン等のフッ素化ポリオレフィンが挙げられ、中でもポリテトラフルオロエチレン、テトラフルオロエチレン／パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン／エチレン共重合体が好適に使用される。これらの滴下防止剤は１種又は２種以上を混合して使用できる。 The anti-dripping agent is used for preventing dripping of the resin during combustion. (F) Specific examples of the anti-dripping agent include polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, fluorine Fluorinated polyolefins such as vinylidene fluoride and polychlorotrifluoroethylene, among others, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / An ethylene copolymer is preferably used. These anti-drip agents can be used alone or in combination of two or more.
（Ｆ）滴下防止剤の含有量は、（Ａ）ＰＢＴ樹脂１００質量部に対して０．５〜５質量部が好ましく、０．８〜４質量部がより好ましく、１〜３質量部がさらに好ましい。 (F) As for content of a dripping inhibitor, 0.5-5 mass parts is preferable with respect to 100 mass parts of (A) PBT resin, 0.8-4 mass parts is more preferable, and 1-3 mass parts is further. preferable.
［（Ｇ）ガラス繊維］
本発明のＰＢＴ樹脂組成物には、機械的強度の向上のために（Ｇ）ガラス繊維を含有することが好ましい。ガラス繊維の繊維長（溶融混練などにより組成物に調製する前の状態）は１〜１０ｍｍのものが好ましく、ガラス繊維の直径は５〜２０μｍのものが好ましい。
本発明のＰＢＴ樹脂組成物において、（Ｇ）ガラス繊維は、全体に対し、０〜５０質量％、好ましくは１０〜４０質量％、さらに好ましくは１５〜３０質量％含有する。[(G) Glass fiber]
The PBT resin composition of the present invention preferably contains (G) glass fiber in order to improve mechanical strength. The fiber length of the glass fiber (the state before preparation into a composition by melt kneading or the like) is preferably 1 to 10 mm, and the diameter of the glass fiber is preferably 5 to 20 μm.
In the PBT resin composition of the present invention, the (G) glass fiber is contained in an amount of 0 to 50% by mass, preferably 10 to 40% by mass, and more preferably 15 to 30% by mass with respect to the whole.
［他の成分］
本発明のＰＢＴ樹脂組成物には、本発明の効果を損なわない範囲において、上記の成分以外の成分が配合されていてもよい。具体的には、ＰＢＴ樹脂以外の熱可塑性樹脂、ガラス繊維以外の繊維状充填剤（炭素繊維、金属繊維、有機繊維等）、非繊維状充填剤（ガラスフレーク、ガラスビーズ・パウダー等）、酸化防止剤、安定剤、核剤、離型剤、帯電防止剤、着色剤等を挙げることができる。[Other ingredients]
In the PBT resin composition of the present invention, components other than the above components may be blended within a range not impairing the effects of the present invention. Specifically, thermoplastic resins other than PBT resins, fibrous fillers other than glass fibers (carbon fibers, metal fibers, organic fibers, etc.), non-fibrous fillers (glass flakes, glass beads / powder, etc.), oxidation Examples thereof include an inhibitor, a stabilizer, a nucleating agent, a release agent, an antistatic agent, and a coloring agent.
本発明のＰＢＴ樹脂組成物中のその他の成分の含有量は、その合計量が、全体に対して、０〜５０質量％、好ましくは５〜４０質量％、特に好ましくは１０〜３０質量％（例えば２０質量％）とすることができる。 The total content of the other components in the PBT resin composition of the present invention is 0 to 50% by mass, preferably 5 to 40% by mass, particularly preferably 10 to 30% by mass (based on the total). For example, it may be 20% by mass).
［ポリブチレンテレフタレート樹脂組成物の製造方法］
本発明のＰＢＴ樹脂組成物の製造方法は、特に限定されるものではなく、従来公知の樹脂組成物調製法として一般に用いられる設備と方法が使用できる。例えば、各成分を混合した後、１軸又は２軸の押出機又はその他の溶融混練装置により溶融混練し、成形用ペレットとして調製することができる。押出機又はその他の溶融混練装置は複数使用してもよい。また、全ての成分を同時に投入する方法、一部の成分は混練の途中から投入する方法等、何れも使用できる。なお、樹脂成分の一部を細かい粉体としてこれ以外の成分と混合し添加することは、これらの成分の均一配合を行う上で好ましい方法である。[Method for producing polybutylene terephthalate resin composition]
The manufacturing method of the PBT resin composition of this invention is not specifically limited, The installation and method generally used as a conventionally well-known resin composition preparation method can be used. For example, after mixing each component, it can melt-knead with a uniaxial or biaxial extruder or other melt-kneading apparatus to prepare a pellet for molding. A plurality of extruders or other melt kneaders may be used. In addition, any method can be used, such as a method in which all the components are added simultaneously, and a method in which some of the components are added during the kneading. In addition, mixing a part of the resin component as a fine powder with other components and adding it is a preferable method for uniformly blending these components.
＜射出成形品＞
本発明の射出成形品は、既述の本発明のＰＢＴ樹脂組成物を射出成形してなり、少なくとも一部に厚さ０．２〜０．５ｍｍの薄肉部を有する。本発明の射出成形品は、本発明のＰＢＴ樹脂組成物を射出成形してなるものであるため、成形時における流動性に優れ、０．２〜０．５ｍｍの薄肉部を形成でき、かつそのような薄肉部での難燃性に優れる。
本発明の射出成形品を作製する方法としては特に限定はなく、公知の方法を採用することができる。例えば、上記のように本発明のＰＢＴ樹脂組成物を押出機に投入して溶融混練してペレット化し、このペレットを所定の金型を装備した射出成形機に投入し、射出成形することで作製することができる。<Injection molded products>
The injection-molded article of the present invention is formed by injection-molding the above-described PBT resin composition of the present invention, and has a thin portion having a thickness of 0.2 to 0.5 mm at least partially. The injection-molded article of the present invention is formed by injection molding the PBT resin composition of the present invention, so that it has excellent fluidity during molding, can form a thin part of 0.2 to 0.5 mm, and Excellent flame retardance at such thin-walled parts.
There is no limitation in particular as a method of producing the injection molded product of this invention, A well-known method is employable. For example, as described above, the PBT resin composition of the present invention is put into an extruder, melted and kneaded into pellets, and the pellets are put into an injection molding machine equipped with a predetermined mold and produced by injection molding. can do.
以下に、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
［実施例１〜７、比較例１〜２３］
それぞれの実施例・比較例において、（Ａ）ポリブチレンテレフタレート樹脂（ＰＢＴ）、（Ｂ）臭素系難燃剤、（Ｃ）アンチモン系難燃助剤、（Ｄ）タルク、（Ｅ）多価水酸基含有化合物、（Ｆ）滴下防止剤、（Ｇ）ガラス繊維を、各々下記表１〜表３に示す部数を配合し、後述の方法にてＰＢＴ樹脂組成物を調製した。次いで、得られたＰＢＴ樹脂組成物を用い以下の評価を行った。
なお、上記各成分の詳細は以下の通りである。
ＰＢＴ１（ＩＶ＝０．８８）：ウィンテックポリマー（株）製
ＰＢＴ２（ＩＶ＝０．６９）：ウィンテックポリマー（株）製
ＰＢＴ３（ＩＶ＝０．４５）：ウィンテックポリマー（株）製
難燃剤１（臭素化エポキシ系難燃剤（Ｂｒ−ＥＰ））：ブロモケム・ファーイスト（株）製 Ｆ３１００、臭素含有率：約５２質量％
難燃剤２（臭素化ポリアクリレート系難燃剤（Ｂｒ−ＡＣ））：ブロモケム・ファーイスト（株）製 ＦＲ−１０２５、臭素含有率：約７２質量％
難燃剤３（臭素化ポリカーボネート系難燃剤（Ｂｒ−ＰＣ））：帝人化成（株）製 ファイヤーガード７５００
難燃剤４（臭素化フタルイミド系難燃剤（Ｂｒ−イミド））：アルベマール日本（株）製 ＳＡＹＴＥＸ ＢＴ９３Ｗ
難燃剤５（臭素化ポリスチレン系難燃剤（Ｂｒ−ＰＳ））：Ｇｒｅａｔ Ｌａｋｅｓ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ製 ＰＤＢＳ−８０Ｍ
アンチモン系難燃助剤（三酸化アンチモン）：日本精鉱（株）製 ＰＡＴＯＸ−Ｍ、平均粒子径：１．２μｍ
無機難燃助剤１（タルク１）：林化成（株）製 タルカンパウダーＰＫＮＮ（平均粒子径：１３．５μｍ）
無機難燃助剤２（マイカ）：Ｓｕｚｏｒｉｔｅ Ｍｉｎｉｎｇ Ｉｎｃ．製 スゾライトマイカ１５０−Ｓ
無機難燃助剤３（炭酸カルシウム）：東洋ファインケミカル（株）製 ホワイトンＰ−３０
無機難燃助剤４（酸化亜鉛）：三井金属鉱業（株）製 酸化亜鉛１種
無機難燃助剤５（酸化マグネシウム）：協和化学工業（株）製 キョウワマグＭＦ−１５０
無機難燃助剤６（ベーマイト）：Ｎａｂａｌｔｅｃ社製 ＡＣＴＩＬＯＸ Ｂ６０
無機難燃助剤７（タルク２）：松村産業（株）製 クラウンタルクＰＰ（平均粒子径：２．３μｍ）
無機難燃助剤８（タルク３）：林化成（株）製 ミクロンホワイト＃５０００Ａ（平均粒子径：５．０μｍ）
無機難燃助剤９（タルク４）：日本タルク（株）製 タルク３Ａ（平均粒子径：１７．５μｍ）
多価水酸基含有化合物１（グリセリンモノ１２−ヒドロキシステアレート）：理研ビタミン（株）製 リケマールＨＣ−１００（水酸基価４２０）
多価水酸基含有化合物２（グリセリントリステアレート）：理研ビタミン（株）製 ポエムＳ−９５（水酸基価８７）
滴下防止剤（ポリテトラフルオロエチレン）：旭硝子（株）製 フルオンＣＤ−０７６
ガラス繊維：日東紡績（株）製 ＣＳＦ３ＰＥ−９４１（平均繊維径φ１３μｍチョップドストランド）[Examples 1-7, Comparative Examples 1-23]
In each example and comparative example, (A) polybutylene terephthalate resin (PBT), (B) brominated flame retardant, (C) antimony flame retardant auxiliary, (D) talc, (E) polyvalent hydroxyl group-containing The compound, (F) anti-drip agent, and (G) glass fiber were blended in the numbers shown in Tables 1 to 3 below, and PBT resin compositions were prepared by the method described below. Subsequently, the following evaluation was performed using the obtained PBT resin composition.
In addition, the detail of said each component is as follows.
PBT1 (IV = 0.88): Wintech Polymer Co., Ltd. PBT2 (IV = 0.69): Wintech Polymer Co., Ltd. PBT3 (IV = 0.45): Wintech Polymer Co., Ltd. flame retardant 1 (brominated epoxy flame retardant (Br-EP)): F3100 manufactured by Bromochem Farist Co., bromine content: about 52% by mass
Flame retardant 2 (brominated polyacrylate flame retardant (Br-AC)): FR-1025 manufactured by Bromochem Farist Co., bromine content: about 72% by mass
Flame retardant 3 (brominated polycarbonate flame retardant (Br-PC)): Fire guard 7500 manufactured by Teijin Chemicals Ltd.
Flame retardant 4 (brominated phthalimide flame retardant (Br-imide)): SAYTEX BT93W manufactured by Albemarle Japan
Flame retardant 5 (brominated polystyrene flame retardant (Br-PS)): PDBS-80M manufactured by Great Lakes Chemical Corporation
Antimony flame retardant aid (antimony trioxide): NIPPON SEIKO CO., LTD. PATOX-M, average particle size: 1.2 μm
Inorganic flame retardant aid 1 (talc 1): Talcan powder PKNN (average particle size: 13.5 μm) manufactured by Hayashi Kasei Co., Ltd.
Inorganic flame retardant aid 2 (mica): Suzuki Mining Inc. Made Szolite Mica 150-S
Inorganic flame retardant aid 3 (calcium carbonate): Toyo Fine Chemical Co., Ltd. Whiten P-30
Inorganic flame retardant aid 4 (zinc oxide): Class 1 zinc oxide manufactured by Mitsui Mining & Smelting Co., Ltd. Inorganic flame retardant aid 5 (magnesium oxide): Kyowa Chemical Industry Co., Ltd. Kyowa Mag MF-150
Inorganic flame retardant aid 6 (boehmite): ACTILOX B60 manufactured by Nabaltec
Inorganic flame retardant aid 7 (talc 2): Crown talc PP (average particle size: 2.3 μm) manufactured by Matsumura Sangyo Co., Ltd.
Inorganic flame retardant aid 8 (talc 3): Hayashi Kasei Co., Ltd. micron white # 5000A (average particle size: 5.0 μm)
Inorganic flame retardant aid 9 (talc 4): manufactured by Nippon Talc Co., Ltd. Talc 3A (average particle size: 17.5 μm)
Polyhydric hydroxyl group-containing compound 1 (glycerin mono-12-hydroxystearate): Rikenmar HC-100 (hydroxyl value 420) manufactured by Riken Vitamin Co., Ltd.
Polyhydric hydroxyl group-containing compound 2 (glycerin tristearate): Poem S-95 (hydroxyl value 87) manufactured by Riken Vitamin Co., Ltd.
Anti-dripping agent (polytetrafluoroethylene): Asahi Glass Co., Ltd. Fullon CD-076
Glass fiber: Nitto Boseki Co., Ltd. CSF3PE-941 (average fiber diameter φ13 μm chopped strand)
［ポリブチレンテレフタレート樹脂組成物の調製］
上記の材料を以下の表１〜表３に示す割合（単位は質量部）でブレンドし、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製ＴＥＸ３０α）にて２５０℃で溶融混練し、ペレット状のＰＢＴ樹脂組成物を得た。[Preparation of polybutylene terephthalate resin composition]
The above materials are blended in the proportions shown in Tables 1 to 3 below (units are parts by mass), and melt kneaded at 250 ° C. in a twin-screw extruder having a 30 mmφ screw (TEX30α manufactured by Nippon Steel Works). Thus, a PBT resin composition in the form of pellets was obtained.
（１）難燃性
上記のようにして得られた樹脂組成物にて、アンダーライターズ・ラボラトリーズのサブジェクト９４（ＵＬ９４）の方法に準じ、５本の試験片（長さ１２５ｍｍ、幅１３ｍｍ、厚さ０．２ｍｍ）を用いて燃焼性について試験し、ＵＬ９４に記載の評価方法に従って評価した。良好な難燃性を示すＶ−０の判定基準を満たす場合を「ＯＫ」、満たさない場合を「ＮＧ」として評価結果を表１に示す。なお、試験片の成形においては、短辺側から長手方向に射出すると流動性が足りず充填が困難なため、長辺側に幅１２５ｍｍ、厚さ０．２ｍｍのフィルムゲートを設けた金型を用いて射出成形した。成形条件は、シリンダー温度２６０℃、金型温度１００℃、射出速度３５０ｍｍ／ｓ、保圧力５０ＭＰａ、保圧時間１．０秒、冷却時間４．０秒の成形条件で行なった。
一方、上記試験片とは別に、厚さが０．５ｍｍのものと、０．８ｍｍの試験片（長さ及び幅は上記試験片と同じ）を用意し、上記と同様に試験を行なった。
また、厚さが０．２ｍｍの試験片について、ＵＬ９４の燃焼性試験における、２回目の接炎時のドリッピングの有無を観察し、結果を表４に示した。(1) Flame retardancy In the resin composition obtained as described above, five test pieces (length 125 mm, width 13 mm, thickness according to the method of Subject 94 (UL94) of Underwriters Laboratories) Was tested for flammability using the evaluation method described in UL94. Table 1 shows the evaluation results as “OK” when the criterion for V-0 indicating good flame retardancy is satisfied, and “NG” when the criterion is not satisfied. In the molding of the test piece, when injected in the longitudinal direction from the short side, fluidity is insufficient and filling is difficult. Therefore, a mold provided with a film gate having a width of 125 mm and a thickness of 0.2 mm on the long side is used. Used for injection molding. The molding conditions were a cylinder temperature of 260 ° C., a mold temperature of 100 ° C., an injection speed of 350 mm / s, a holding pressure of 50 MPa, a holding pressure time of 1.0 second, and a cooling time of 4.0 seconds.
On the other hand, apart from the above test pieces, those having a thickness of 0.5 mm and 0.8 mm test pieces (the length and width are the same as those of the above test pieces) were prepared, and the test was performed in the same manner as described above.
Further, with respect to the test piece having a thickness of 0.2 mm, the presence or absence of dripping at the second flame contact in the flammability test of UL94 was observed, and the results are shown in Table 4.
（２）流動性
上記のようにして得られた樹脂組成物を、射出成形機にてシリンダー温度２５０℃、金型温度６５℃、射出圧力１２５ＭＰａ、射出速度７０ｍｍ／ｓ、射出時間５．０秒、冷却時間５．０秒の成形条件で、図１に示すように、幅５．０ｍｍ、厚さ０．２ｍｍの棒状の試験片を成形し、図１においてハッチングで示す部位の長さＤを測定した。測定結果を表１に示す。(2) Flowability The resin composition obtained as described above was subjected to a cylinder temperature of 250 ° C., a mold temperature of 65 ° C., an injection pressure of 125 MPa, an injection speed of 70 mm / s, and an injection time of 5.0 seconds using an injection molding machine. As shown in FIG. 1, a rod-shaped test piece having a width of 5.0 mm and a thickness of 0.2 mm was molded under the molding conditions of a cooling time of 5.0 seconds, and the length D of the portion indicated by hatching in FIG. It was measured. The measurement results are shown in Table 1.
なお、表２と表３において難燃性の結果が「−」である比較例２、４、８、１３、１５、１７は、難燃性試験において試験片を成形しようとしたが、流動性の不足により成形できず難燃性試験を実行できなかった。
また、比較例４については、実施例の成形条件では流動性不足により燃焼性試験片を成形することができなかったが、シリンダー温度を２８０℃に上げることで、かろうじて成形することができた。そして、その試験片を用いて、難燃性試験を行なったところ、成形時の熱でＰＢＴ樹脂が分解していたため、燃焼時に著しい滴下が見られ「ＮＧ」となった。In Tables 2 and 3, Comparative Examples 2, 4, 8, 13, 15, and 17 in which the result of flame retardancy is “−” tried to mold a test piece in the flame retardancy test, but the fluidity Due to the shortage of the material, molding could not be performed and the flame retardancy test could not be performed.
In Comparative Example 4, the combustibility test piece could not be formed due to insufficient fluidity under the molding conditions of the example, but it was barely possible to mold by raising the cylinder temperature to 280 ° C. And when the flame retardance test was done using the test piece, since the PBT resin was decomposed | disassembled with the heat | fever at the time of shaping | molding, remarkable dripping was seen at the time of combustion and it became "NG".
表１より、本発明を適用した実施例１〜７はいずれも、難燃性と流動性に優れたＰＢＴ樹脂組成物が得られたことが分かる。これに対して、比較例１〜２３においては、難燃性と流動性を同時に満足させることができなかった。
また、以下の通り、各実施例・比較例から以下のことが分かる。すなわち、
（１）ＰＢＴの固有粘度のみが実施例１と異なる比較例３では難燃性の評価に劣っていたことから、ＰＢＴを低粘度とすると難燃性が悪化する。
（２）実施例１と比較例５とでは、流動性においてほぼ同じ評価結果となっているが、比較例５においては（Ｅ）多価水酸基含有化合物を添加せずに流動性を向上させており、難燃性が劣る結果となったが、実施例１は当該（Ｅ）成分を用いて流動性を向上させており、難燃性をも確保できた。
また、比較例７は、（Ｂ）成分を多量に含有させているため、異物の発生による成形品の外観不良を生じた。From Table 1, it can be seen that in Examples 1 to 7 to which the present invention was applied, a PBT resin composition excellent in flame retardancy and fluidity was obtained. On the other hand, in Comparative Examples 1 to 23, flame retardancy and fluidity could not be satisfied at the same time.
Further, as described below, the following can be understood from each of the examples and comparative examples. That is,
(1) Since only the intrinsic viscosity of PBT was inferior to the evaluation of flame retardancy in Comparative Example 3, which was different from Example 1, the flame retardancy deteriorated when the PBT had a low viscosity.
(2) In Example 1 and Comparative Example 5, the fluidity is almost the same evaluation result, but in Comparative Example 5, the fluidity is improved without adding (E) a polyvalent hydroxyl group-containing compound. However, although the flame retardancy was inferior, Example 1 improved the fluidity using the component (E), and was able to ensure the flame retardancy.
Moreover, since the comparative example 7 contained a large amount of the component (B), the appearance of the molded product was poor due to the generation of foreign matter.
表４より、平均粒子径が３μｍ以上のタルクを用いた実施例１および９〜１０では、ドリッピングが発生せず、特に難燃性に優れたＰＢＴ樹脂組成物が得られたことが分かる。
From Table 4, it can be seen that in Examples 1 and 9 to 10 using talc having an average particle diameter of 3 μm or more, dripping did not occur and a PBT resin composition excellent in flame retardancy was obtained.
Claims (5)
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| 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 |
| CN112236478B (en) * | 2018-06-05 | 2023-03-14 | 宝理塑料株式会社 | Flame-retardant polybutylene terephthalate resin composition |
| CN112771115B (en) * | 2018-09-28 | 2023-03-24 | 宝理塑料株式会社 | Flame-retardant polybutylene terephthalate resin composition |
| US20220195112A1 (en) * | 2019-03-26 | 2022-06-23 | Toyobo Co., Ltd. | Polybutylene terephthalate resin composition |
| WO2020203436A1 (en) * | 2019-04-01 | 2020-10-08 | ポリプラスチックス株式会社 | Method for improving alkaline solution resistance of thermoplastic resins |
| JP7454343B2 (en) * | 2019-07-31 | 2024-03-22 | ポリプラスチックス株式会社 | Flame retardant polybutylene terephthalate resin composition |
| WO2021065094A1 (en) * | 2019-09-30 | 2021-04-08 | ポリプラスチックス株式会社 | Polybutylene terephthalate resin composition |
| WO2022044947A1 (en) * | 2020-08-25 | 2022-03-03 | ポリプラスチックス株式会社 | Flame-retardant resin composition and molded article thereof |
| JP6993545B1 (en) * | 2020-08-25 | 2022-01-13 | ポリプラスチックス株式会社 | Flame-retardant resin composition and its molded products |
| CN112679916B (en) * | 2020-12-09 | 2022-04-19 | 金发科技股份有限公司 | PBT composition and preparation method and application thereof |
| CN114539732B (en) * | 2022-02-21 | 2023-08-11 | 江苏金发科技新材料有限公司 | Polybutylene terephthalate composition and application thereof |
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| JP2915168B2 (en) * | 1991-05-29 | 1999-07-05 | ポリプラスチックス株式会社 | Flame retardant polybutylene terephthalate resin composition |
| JPH0641371A (en) * | 1992-07-23 | 1994-02-15 | Mitsubishi Cable Ind Ltd | Flame retardant composition |
| JP3316164B2 (en) * | 1996-06-28 | 2002-08-19 | ポリプラスチックス株式会社 | Thermoplastic resin composition |
| JP3598034B2 (en) * | 1999-12-24 | 2004-12-08 | 帝人株式会社 | Flame-retardant polyester resin composition and molded article thereof |
| JP2002128998A (en) * | 2000-10-30 | 2002-05-09 | Teijin Ltd | Flame-retardant polyester resin composition |
| JP2004263174A (en) * | 2003-02-12 | 2004-09-24 | Mitsubishi Engineering Plastics Corp | Thermoplastic polyester-based flame-retardant resin composition and molded product of the same |
| KR101126980B1 (en) * | 2003-07-10 | 2012-03-23 | 사빅 이노베이티브 플라스틱스 아이피 비.브이. | Fire-retarded polycarbonate resin composition |
| CN1980996B (en) * | 2004-06-29 | 2010-11-03 | 三菱工程塑料株式会社 | Flame-retardant polybutylene terephthalate composition and molded product |
| CN101218305B (en) * | 2005-07-08 | 2011-03-23 | 宝理塑料株式会社 | Flame retardant resin composition |
| JP2007161946A (en) * | 2005-12-16 | 2007-06-28 | Wintech Polymer Ltd | Insulating material part |
| JP2008115209A (en) * | 2006-10-31 | 2008-05-22 | Toray Ind Inc | Thermoplastic resin composition |
| JP5131088B2 (en) * | 2007-08-31 | 2013-01-30 | 東レ株式会社 | Flame retardant thermoplastic polyester resin composition |
| CN101802090B (en) * | 2007-10-17 | 2012-07-04 | 胜技高分子株式会社 | Polybutylene terephthalate resin composition and thin molded article |
| JP5236394B2 (en) * | 2007-11-12 | 2013-07-17 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition and thin-walled molded article |
| JP5368727B2 (en) * | 2008-05-07 | 2013-12-18 | 出光興産株式会社 | Thermoplastic resin composition and molded body |
| CN102186910B (en) * | 2008-10-20 | 2014-07-02 | 沙伯基础创新塑料知识产权有限公司 | Flow-enhanced thermoplastic compositions and methods for enhancing the flow of thermoplastic compositions |
| JP5683793B2 (en) * | 2009-06-03 | 2015-03-11 | ウィンテックポリマー株式会社 | Molded parts for electric car parts |
| JP5677926B2 (en) * | 2011-11-14 | 2015-02-25 | 三菱エンジニアリングプラスチックス株式会社 | POLYESTER RESIN COMPOSITION FOR LASER MARKING AND MOLDED ARTICLE |
| CN102617995A (en) * | 2012-03-12 | 2012-08-01 | 苏州萃智新技术开发有限公司 | Nano-bentonite composite reinforced flame retardant PBT (polybutylene terephthalate) engineering plastic |
| JP6177252B2 (en) * | 2012-10-29 | 2017-08-09 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition |
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| CN105377983B (en) | 2017-12-12 |
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