JP5872577B2 - Flame retardant masterbatch and method for producing styrenic flame retardant resin composition using the same - Google Patents
Flame retardant masterbatch and method for producing styrenic flame retardant resin composition using the same Download PDFInfo
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- JP5872577B2 JP5872577B2 JP2013539492A JP2013539492A JP5872577B2 JP 5872577 B2 JP5872577 B2 JP 5872577B2 JP 2013539492 A JP2013539492 A JP 2013539492A JP 2013539492 A JP2013539492 A JP 2013539492A JP 5872577 B2 JP5872577 B2 JP 5872577B2
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- flame retardant
- mass
- styrene
- parts
- resin composition
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims description 180
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 178
- 239000004594 Masterbatch (MB) Substances 0.000 title claims description 86
- 239000011342 resin composition Substances 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 194
- 229920005989 resin Polymers 0.000 claims description 59
- 239000011347 resin Substances 0.000 claims description 59
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 27
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 239000000454 talc Substances 0.000 claims description 19
- 229910052623 talc Inorganic materials 0.000 claims description 19
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 9
- 150000003440 styrenes Chemical class 0.000 claims description 8
- 238000011156 evaluation Methods 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 229920001890 Novodur Polymers 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 229920001971 elastomer Polymers 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920002857 polybutadiene Polymers 0.000 description 8
- 239000000428 dust Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 229940057995 liquid paraffin Drugs 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000011115 styrene butadiene Substances 0.000 description 4
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000005063 High cis polybutadiene Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 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
- 239000002216 antistatic agent Substances 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-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
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-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
- 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005064 Low cis polybutadiene Substances 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- FDBMBOYIVUGUSL-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FDBMBOYIVUGUSL-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、スチレン系樹脂に難燃性を付与するために使用される難燃剤マスターバッチ及び、この難燃剤マスターバッチとスチレン系樹脂を使用したスチレン系難燃性樹脂組成物の製造方法及びその成形品の製造方法に関するものである。特に、ＵＬ難燃規格Ｖ−０であるスチレン系難燃性樹脂組成物を得るための難燃剤マスターバッチとそれを使用したスチレン系難燃性樹脂組成物の製造方法である。 The present invention relates to a flame retardant masterbatch used for imparting flame retardancy to a styrene resin, a method for producing a styrene flame retardant resin composition using the flame retardant masterbatch and a styrene resin, and The present invention relates to a method for manufacturing a molded product. In particular, it is a flame retardant masterbatch for obtaining a styrene flame retardant resin composition which is UL flame retardant standard V-0 and a method for producing a styrene flame retardant resin composition using the same.
スチレン系樹脂は、その特性を生かして広範囲な用途に使用されている。中でも高度な難燃性を付与したスチレン系難燃性樹脂は、ワープロ、パーソナルコンピュータ、プリンター、複写機等のＯＡ機器、液晶テレビ、ＶＴＲ、オーディオ等の家電製品等を始めとする多岐の分野で使用されている。 Styrenic resins are used in a wide range of applications by taking advantage of their properties. Above all, styrene-based flame retardant resins with advanced flame retardancy are used in a wide variety of fields, including office automation equipment such as word processors, personal computers, printers, copiers, liquid crystal televisions, VTRs, and audio home appliances. It is used.
昨今、ＯＡ機器や家電製品の分野では、プラスチック部品の大型化に対応するため、大型成形機を使用したホットランナー成形法やガスアシストインジェクション法等が適用される。このため、使用される樹脂には、難燃性以外に優れた成形性が要求される。
このように、多岐の分野に使用されるので、ＵＬ難燃規格の難燃性レベルでも５Ｖ，Ｖ−０、Ｖ−１、Ｖ−２、ＨＢのいずれが要求されるのか、加えて耐熱性、流動性、耐衝撃性等の全て物性が一定の水準以上を満たさなければならないのか、あるいはこれらの特性の中で難燃性に加えて特に耐熱性が必要なのか、さらに耐衝撃性が必要になるのか、など用途によって多様な特性が必要とされる。In recent years, in the field of OA equipment and home appliances, a hot runner molding method using a large molding machine, a gas assist injection method, and the like are applied in order to cope with an increase in the size of plastic parts. For this reason, the resin used is required to have excellent moldability in addition to flame retardancy.
In this way, because it is used in a wide variety of fields, 5V, V-0, V-1, V-2, and HB are required even at the flame retardancy level of UL flame retardance standards, plus heat resistance Whether all the physical properties such as fluidity and impact resistance must meet a certain level or more, in addition to flame retardancy among these properties, especially heat resistance is required, and further impact resistance is required Depending on the application, various characteristics are required.
従来から、スチレン系樹脂に難燃性を付与するために、種々の難燃剤が提案されている。中でも、安価で物性バランスに優れているハロゲン含有有機化合物が難燃剤として多く使用されている。代表的なものとしては、テトラブロモビスフェノールＡ、デカブロモジフェニルエーテル、デカブロモジフェニルエタン、臭素化トリアジン、臭素化エポキシ、又は臭素化エポキシ樹脂のエポキシ基をトリブロモフェノールで封鎖したものが使用される。中でも耐熱性、流動性、及び物性バランスが良好である臭素化トリアジン系の２，４，６−トリス（２，４，６−トリスブロモフェノキシ）−１，３，５−トリアジンの難燃性樹脂への使用が増えている。
これらの難燃剤がスチレン系樹脂に使用されている例は、特許文献１、特許文献２、特許文献３、特許文献４などが挙げられる。Conventionally, various flame retardants have been proposed in order to impart flame retardancy to styrene-based resins. Among them, halogen-containing organic compounds that are inexpensive and excellent in physical property balance are often used as flame retardants. Typical examples include tetrabromobisphenol A, decabromodiphenyl ether, decabromodiphenyl ethane, brominated triazine, brominated epoxy, or a brominated epoxy resin having an epoxy group blocked with tribromophenol. Among them, a brominated triazine-based 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine flame retardant resin having good heat resistance, fluidity, and physical property balance The use for is increasing.
Examples of these flame retardants used in styrene resins include Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.
しかしながら、この２，４，６−トリス（２，４，６−トリスブロモフェノキシ）−１，３，５−トリアジンは顆粒状でスチレン系樹脂ペレットよりも小さい形状で、また大きい比重を有しているので、この難燃剤とスチレン系樹脂ペレットが分級し易く均一に混合し難い問題を有している。このため均一に混合させるためにはすべての押出機本体に別フィードを設置し、均一に溶融混合させる必要があり、簡便な単軸又は二軸押出機では製造し難い問題を有している。 However, this 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine is granular, smaller in shape than styrenic resin pellets, and has a large specific gravity. Therefore, the flame retardant and the styrene resin pellet are easily classified and have a problem that it is difficult to mix them uniformly. For this reason, in order to mix uniformly, it is necessary to install another feed in all the extruder main bodies, and to melt-mix uniformly, and it has the problem that it is difficult to manufacture with a simple single screw or twin screw extruder.
また、スチレン系難燃性樹脂組成物の耐熱性及び剛性を向上させるためにタルクを配合するのが効果的であることが知られている。しかし、タルクは微粉末であり、粉塵の問題を有している。溶融混合させる際に粉塵問題を解決するためにすべての押出機に集塵機を備える必要がある。 Moreover, it is known that it is effective to mix talc in order to improve the heat resistance and rigidity of the styrene-based flame retardant resin composition. However, talc is a fine powder and has the problem of dust. In order to solve the dust problem when melt mixing, it is necessary to provide a dust collector in all the extruders.
本発明の課題は、上記問題を解決し、難燃剤マスターバッチを製造し、その難燃剤マスターバッチを溶融混合することによってスチレン系難燃性樹脂組成物を製造する方法を提供することにある。
すなわち、それぞれ多岐に渡るスチレン系難燃樹脂組成物を別フィード・集塵機付きの二軸押出機を大小多数備えることなく、難燃剤の分散性が良好で、所望の難燃特性を有し、しかも、機械物性など、ポリスチレン系樹脂本来の特性が実質上低下せず、耐熱性、流動性等などのそれぞれの目的にあったスチレン系難燃性樹脂組成物を特に単軸押出機でも提供することにある。The subject of this invention is providing the method of manufacturing a styrene-type flame retardant resin composition by solving the said problem, manufacturing a flame retardant masterbatch, and melt-mixing the flame retardant masterbatch.
In other words, each of a wide variety of styrene-based flame retardant resin compositions is provided with large and small twin-screw extruders with separate feed / dust collectors, good dispersibility of the flame retardant, and the desired flame retardant properties. Providing a styrene-based flame retardant resin composition suitable for each purpose such as heat resistance, fluidity, etc., even with a single-screw extruder, without substantially reducing the original properties of polystyrene-based resins such as mechanical properties. It is in.
本発明者らは、上記の課題を解決するために鋭意検討を重ねた結果、下記の特定の組成を有する難燃剤入りマスターバッチと、このマスターバッチを使用するスチレン系難燃性樹脂組成物の製造方法と、を見出すことにより本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a masterbatch containing a flame retardant having the following specific composition and a styrene-based flame-retardant resin composition using the masterbatch The present invention was completed by finding the manufacturing method.
すなわち、本発明は以下の構成を要旨とするものである。
１.（Ａ）スチレン系樹脂７５乃至２５質量部、（Ｂ）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジン１５乃至５０質量部、（Ｃ）三酸化アンチモン２乃至８質量部、及び（Ｄ）タルク５乃至１７質量部を含有し、
かつ、（Ａ）乃至（Ｄ）の合計１００質量部に対し、更に（Ｅ）酸化防止剤０．５乃至２．０質量部を含有することを特徴とする難燃剤マスターバッチ。
２．前記（Ａ）乃至（Ｄ）の合計１００質量部に対し、更に、（Ｆ）カーボンブラック
１．７質量部未満（但し０は含まず。）を含有する前記１に記載の難燃剤マスターバッチ。
３．（Ａ）スチレン系樹脂６５乃至３０質量部、（Ｂ）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジン２５乃至５０質量部、（Ｃ）三酸化アンチモン３乃至８質量部、及び（Ｄ）タルク７乃至１７質量部である前記１又は２に記載の難燃剤マスターバッチ。
４．（Ａ）スチレン系樹脂が、スチレン−ブタジエンブロック共重合体及び／又はランダム共重合体を含有したゴム変性スチレン系樹脂である前記１乃至３のいずれかに記載の難燃剤マスターバッチ。
５．（Ｅ）酸化防止剤が、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートである前記１乃至４のいずれかに記載の難燃剤マスターバッチ。
６．前記１乃至前記５のいずれかに記載の難燃剤マスターバッチ（Ｉ）３０乃至８５質量部と、スチレン系樹脂（ＩＩ）７０乃至１５質量部と、を溶融混合するスチレン系難燃性樹脂組成物の製造方法。
７．前記１乃至前記５のいずれかに記載の難燃剤マスターバッチ（Ｉ）３０乃至６０質量部と、スチレン系樹脂（ＩＩ）７０乃至４０質量部と、を溶融混合するスチレン系難燃性樹脂組成物の製造方法。
That is, the gist of the present invention is as follows.
1. (A) 75 to 25 parts by mass of styrene-based resin, (B) 15 to 50 parts by mass of 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, C) 2 to 8 parts by mass of antimony trioxide, and (D) 5 to 17 parts by mass of talc,
And the flame retardant masterbatch characterized by containing 0.5 to 2.0 mass parts of (E) antioxidant further with respect to a total of 100 mass parts of (A) thru | or (D).
2. (F) Carbon black is further added to 100 parts by mass of the total of (A) to (D).
The flame retardant masterbatch according to 1 above, containing less than 1.7 parts by mass (excluding 0).
3. (A) 65 to 30 parts by mass of styrene-based resin, (B) 25 to 50 parts by mass of 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, (C) The flame retardant masterbatch according to 1 or 2 above, which is 3 to 8 parts by mass of antimony trioxide and (D) 7 to 17 parts by mass of talc.
4). (A) The flame retardant masterbatch according to any one of 1 to 3, wherein the styrene resin is a rubber-modified styrene resin containing a styrene-butadiene block copolymer and / or a random copolymer.
5. (E) The flame retardant master batch according to any one of 1 to 4 above, wherein the antioxidant is octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.
6). The styrene-based flame retardant resin composition comprising 30 to 85 parts by mass of the flame retardant master batch (I) according to any one of 1 to 5 and 70 to 15 parts by mass of the styrene resin (II). Manufacturing method.
7). The styrene flame retardant resin composition comprising 30 to 60 parts by mass of the flame retardant masterbatch (I) according to any one of 1 to 5 and 70 to 40 parts by mass of the styrene resin (II). Manufacturing method.
８．難燃剤マスターバッチ（Ｉ）とスチレン系樹脂（ＩＩ）の合計量１００質量部に、更にポリテトラフルオロエチレン（ＰＴＦＥ）を０．４質量部以下（但し０は含まず。）を添加して溶融混合する前記６又は７に記載のスチレン系難燃性樹脂組成物の製造方法。
９．単軸押出機で溶融混合する前記６乃至８のいずれかに記載のスチレン系難燃性樹脂組成物の製造方法。
１０．二軸押出機で溶融混合する前記６乃至８のいずれかに記載のスチレン系難燃性樹脂組成物の製造方法。
１１．前記スチレン系難燃性樹脂組成物のＵＬ―９４に基づく難燃性の評価がＶ−０である前記６乃至１０のいずれかに記載のスチレン系難燃性樹脂組成物の製造方法。8). To a total amount of 100 parts by mass of the flame retardant masterbatch (I) and the styrene resin (II), 0.4 parts by mass or less (but not including 0) of polytetrafluoroethylene (PTFE) is added and melted. The manufacturing method of the styrene-type flame retardant resin composition of said 6 or 7 to mix.
9. 9. The method for producing a styrene-based flame retardant resin composition as described in any one of 6 to 8 above, which is melt-mixed with a single screw extruder.
10. 9. The method for producing a styrene-based flame retardant resin composition as described in any one of 6 to 8, which is melt-mixed with a twin-screw extruder.
11. 11. The method for producing a styrene flame retardant resin composition according to any one of 6 to 10, wherein the flame retardant evaluation based on UL-94 of the styrene flame retardant resin composition is V-0.
本発明によれば、特定の難燃剤マスターバッチを使用することによって、それぞれ多岐に渡るスチレン系難燃樹脂組成物を別フィード・集塵機付きの二軸押出機を大小多数備えることなく、また単軸押出機でもそれぞれの目的にあったスチレン系難燃性樹脂組成物を提供するものである。
すなわち、得られたスチレン系難燃性樹脂組成物は、難燃性、衝撃強度、耐熱性、流動性等の物性バランスに優れ、溶融混合に単軸押出機を使用して得た組成物でも容易に目的の成形品が得られ、成形品の外観も良好である。According to the present invention, by using a specific flame retardant master batch, each of a wide variety of styrene-based flame retardant resin compositions can be provided with a large number of twin-screw extruders with separate feed / dust collectors, An extruder also provides a styrene-based flame retardant resin composition suitable for each purpose.
That is, the obtained styrene-based flame retardant resin composition is excellent in the balance of physical properties such as flame retardancy, impact strength, heat resistance, and fluidity, and even a composition obtained by using a single screw extruder for melt mixing. The desired molded product can be easily obtained and the appearance of the molded product is also good.
本発明の難燃剤マスターバッチは、（Ａ）スチレン系樹脂、（Ｂ）２，４，６−トリス（２，４，６−トリスブロモフェノキシ）−１，３，５−トリアジン、（Ｃ）三酸化アンチモン、（Ｄ）タルク、及び（Ｅ）酸化防止剤を含有する。 The flame retardant masterbatch of the present invention comprises (A) a styrene resin, (B) 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine, (C) three Contains antimony oxide, (D) talc, and (E) an antioxidant.
本発明の難燃剤マスターバッチに使用する（Ａ）スチレン系樹脂は、ゴム変性スチレン系樹脂を使用するのが好ましい。ゴム変性スチレン系樹脂とは、例えば芳香族ビニル単量体と不活性溶媒の混合液にゴム状重合体を溶解し、攪拌して塊状重合、懸濁重合、溶液重合等を行うことにより得られる、芳香族ビニル重合体のマトリックス中にゴム状重合体が粒子状に分散してなる重合体を言う。マトリックス部分の分子量については特に制限はないが、難燃剤マスターバッチを製造する際又は難燃剤マスターバッチとしての機能を発揮する際に、マトリックス部分の還元粘度（ηｓｐ／Ｃ）が、０．５５乃至０．８５であることが好ましい。ゴム含有量については特に制限はないが、ゴム変性スチレン系樹脂に一般的に使用される５乃至１５質量％が好ましい。また、ゴム状重合体の平均粒子径については特に制限はないが、０．４乃至６．０μｍが好ましい。これらの数値範囲を逸脱することは、難燃剤マスターバッチとしての機能が発揮されにくいので好ましくない。
更には、芳香族ビニル単量体と不活性溶媒の混合液にゴム状重合体を溶解して得られた重合体に、別途得られた芳香族ビニル重合体を混合した混合物であってもよい。The (A) styrene resin used in the flame retardant masterbatch of the present invention is preferably a rubber-modified styrene resin. The rubber-modified styrenic resin is obtained, for example, by dissolving a rubber-like polymer in a mixed liquid of an aromatic vinyl monomer and an inert solvent and stirring to perform bulk polymerization, suspension polymerization, solution polymerization, or the like. A polymer in which a rubbery polymer is dispersed in the form of particles in an aromatic vinyl polymer matrix. The molecular weight of the matrix portion is not particularly limited, but when the flame retardant master batch is produced or when the function as the flame retardant master batch is exhibited, the reduced viscosity (ηsp / C) of the matrix portion is 0.55 to It is preferably 0.85. Although there is no restriction | limiting in particular about rubber content, 5 thru | or 15 mass% generally used for rubber-modified styrene resin is preferable. The average particle diameter of the rubbery polymer is not particularly limited, but is preferably 0.4 to 6.0 μm. Deviating from these numerical ranges is not preferable because the function as a flame retardant masterbatch is difficult to be exhibited.
Further, a mixture obtained by dissolving a rubbery polymer in a mixed liquid of an aromatic vinyl monomer and an inert solvent and a separately obtained aromatic vinyl polymer may be mixed. .
上記に挙げた芳香族ビニル単量体としては、主にスチレンであり、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、２，４−ジメチルスチレン、又はこれらの混合物を挙げることができる。特に、スチレンが最も好適である。 The aromatic vinyl monomer mentioned above is mainly styrene, and can include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, or a mixture thereof. . In particular, styrene is most preferred.
また、ゴム状重合体としては、ポリブタジエン、スチレン−ブタジエン共重合体、ポリイソプレン等が挙げられ、中でもポリブタジエン、又はスチレン−ブタジエン共重合体が好ましい。なお、ハイシスポリブタジエンゴムとは、シス−１、４結合を９０モル％以上の比率で含有するポリブタジエンゴムを意味する。また、ローシスポリブタジエンゴムとは、１，４−シス結合含量が好ましくは１０乃至４０質量％であるポリブタジエンゴムを意味する。ゴム状重合体としては、いずれも使用することが出来る。 Examples of the rubber-like polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, and the like. Among them, polybutadiene or styrene-butadiene copolymer is preferable. The high cis polybutadiene rubber means a polybutadiene rubber containing cis-1,4 bonds in a ratio of 90 mol% or more. The low-cis polybutadiene rubber means a polybutadiene rubber having a 1,4-cis bond content of preferably 10 to 40% by mass. Any rubbery polymer can be used.
また、必要に応じて、ゴム変性スチレン系樹脂に、ランダム構造のスチレン−ブタジエン樹脂、ブロック構造のスチレン−ブタジエン樹脂などを混合して使用してもよい。スチレン−ブタジエン樹脂の混合量は、スチレン−ブタジエン樹脂に依存するゴム含有量が、ゴム変性スチレン樹脂における全ゴム含有量中に占める割合として、その２５質量％以下となるように混合することが好ましい。なお、先に記載したように、全ゴム含有量はゴム変性スチレン系樹脂中では、５乃至１５質量％であるのが好ましい。 If necessary, a rubber-modified styrene resin may be used by mixing a styrene-butadiene resin having a random structure, a styrene-butadiene resin having a block structure, or the like. The mixing amount of the styrene-butadiene resin is preferably such that the rubber content depending on the styrene-butadiene resin is 25% by mass or less as a proportion of the total rubber content in the rubber-modified styrene resin. . As described above, the total rubber content in the rubber-modified styrenic resin is preferably 5 to 15% by mass.
本発明で使用する（Ａ）スチレン系樹脂の含有量は、難燃剤マスターバッチにおける前記（Ａ）乃至（Ｄ）の合計１００質量部に対し、２５乃至７５質量部が好ましく、さらに好ましくは３０乃至６５質量部である。含有量が２５質量部未満であると難燃剤が多くなり、スチレン系難燃性樹脂組成物とした場合、シャルピー衝撃強度、及び熱変形温度が劣るようになる。含有量が７５質量部を超えると樹脂成分が多くなり、難燃性能が劣ることになる。その結果、スチレン系難燃性樹脂組成物を得るのに難燃剤マスターバッチの添加量を増やさなければならないので、難燃剤マスターバッチとしての効率が劣ることになる。 The content of the (A) styrenic resin used in the present invention is preferably 25 to 75 parts by mass, more preferably 30 to 30 parts per 100 parts by mass in total of (A) to (D) in the flame retardant masterbatch. 65 parts by mass. When the content is less than 25 parts by mass, the amount of flame retardant increases, and when a styrene-based flame retardant resin composition is used, the Charpy impact strength and the heat distortion temperature become inferior. If the content exceeds 75 parts by mass, the resin component will increase and the flame retardancy will be poor. As a result, the addition amount of the flame retardant masterbatch must be increased to obtain a styrene-based flame retardant resin composition, resulting in poor efficiency as a flame retardant masterbatch.
また、本発明では、（Ｂ）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジンを難燃剤として使用する。
難燃剤マスターバッチにおける前記（Ａ）乃至（Ｄ）の合計１００質量部に対し、該（Ｂ）難燃剤の含有量は、難燃剤マスターバッチとしての機能性、経済性の観点から、１５乃至５０質量部が好ましく、さらに好ましくは２５乃至５０質量部である。含有量が１５質量部未満であれば難燃性能が劣り、難燃剤マスターバッチの添加量を増やさなければスチレン系難燃性樹脂組成物の難燃性が劣ることになり、難燃剤マスターバッチとしての経済効果が低い。含有量が５０質量部を超えると難燃剤が多くなり、スチレン系難燃性樹脂組成物とした場合、シャルピー衝撃強度、及び熱変形温度が劣るようになる。また、樹脂成分が少なくなり、難燃剤マスターバッチとしてスチレン系樹脂と溶融混合してスチレン系難燃性樹脂組成物を製造する際に、難燃剤の分散不良を発生しやすく好ましくない。In the present invention, (B) 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine is used as a flame retardant.
From the viewpoint of functionality and economy as a flame retardant master batch, the content of the flame retardant master batch is 15 to 50 with respect to 100 parts by mass of the total of (A) to (D) in the flame retardant master batch. A mass part is preferable, More preferably, it is 25-50 mass parts. If the content is less than 15 parts by mass, the flame retardancy is inferior, and if the addition amount of the flame retardant masterbatch is not increased, the flame retardancy of the styrene-based flame retardant resin composition will be inferior, and as a flame retardant masterbatch The economic effect is low. When the content exceeds 50 parts by mass, the amount of flame retardant increases, and when a styrene-based flame retardant resin composition is used, the Charpy impact strength and the heat distortion temperature become inferior. Further, when the resin component is reduced and a styrene-based flame retardant resin composition is produced by melt-mixing with a styrene resin as a flame retardant masterbatch, it is not preferable because the flame retardant is poorly dispersed.
さらに、本発明において使用される難燃化助剤である（Ｃ）三酸化アンチモンは、（Ｂ）含臭素系難燃剤の難燃効果をさらに高める働きをする。難燃化助剤は、さらに、三酸化アンチモンともに、例えば、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等の酸化アンチモン、ホウ酸亜鉛、メタホウ酸バリウム、無水ホウ酸亜鉛、無水ホウ酸等のホウ素系化合物、スズ酸亜鉛、ヒドロキシスズ酸亜鉛等のスズ系化合物、酸化モリブデン、モリブデン酸アンモニウム等のモリブデン系化合物、酸化ジルコニウム、水酸化ジルコニウム等のジルコニウム系化合物、硫化亜鉛等の亜鉛系化合物を使用してもよい。
本発明で、難燃剤マスターバッチにおける前記（Ａ）乃至（Ｄ）の合計１００質量部に対し、（Ｃ）三酸化アンチモンの含有量は、２乃至８質量部であり、好ましくは３乃至８質量部である。含有量が２質量部未満であれば、スチレン系難燃性樹脂組成物とした場合、難燃効果を高める効果が小さい。含有量が８質量部を超えると、スチレン系難燃性樹脂組成物とした場合、シャルピー衝撃強度も劣るようになり、燃焼時のグローイング挙動を高めるので好ましくない。Furthermore, (C) antimony trioxide, which is a flame retardant aid used in the present invention, functions to further enhance the flame retardant effect of the (B) bromine-containing flame retardant. The flame retardant aid further includes, for example, antimony trioxide, antimony pentoxide, sodium antimonate, antimony oxide such as antimony tetroxide, zinc borate, barium metaborate, anhydrous zinc borate, and anhydrous boric acid. Boron compounds, zinc compounds such as zinc stannate and zinc hydroxystannate, molybdenum compounds such as molybdenum oxide and ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, and zinc compounds such as zinc sulfide May be used.
In the present invention, the content of (C) antimony trioxide is 2 to 8 parts by mass, preferably 3 to 8 parts by mass with respect to 100 parts by mass in total of (A) to (D) in the flame retardant masterbatch. Part. If content is less than 2 mass parts, when it is set as a styrene-type flame retardant resin composition, the effect which improves a flame-retardant effect is small. When the content exceeds 8 parts by mass, when a styrene-based flame retardant resin composition is used, the Charpy impact strength becomes inferior and the glowing behavior during combustion is increased, which is not preferable.
さらに、本発明では、（Ｄ）タルクを使用する。（Ｄ）タルクの使用により、スチレン系難燃性樹脂組成物の耐熱性及び剛性を向上させるとともに、難燃剤マスターバッチとして、スチレン系樹脂と溶融混合して樹脂組成物を製造する際に、二軸押出機は無論のこと単軸押出機でも容易に目的のスチレン系難燃物性樹脂組成物を得ることができる。
難燃剤マスターバッチにおける前記（Ａ）乃至（Ｄ）の合計１００質量部に対し、（Ｄ）タルクの含有量は、５乃至１７質量部であり、好ましくは７乃至１７質量部である。含有量が５質量部未満であれば、得られたスチレン系難燃性樹脂組成物の耐熱性及び剛性を低下させるので難燃剤マスターバッチとしての効果が低い。含有量が１７質量部を超えると、スチレン系難燃性樹脂組成物のシャルピー衝撃強度、耐熱性を低下させるので好ましくない。Further, in the present invention, (D) talc is used. (D) The use of talc improves the heat resistance and rigidity of the styrene-based flame retardant resin composition, and as a flame retardant masterbatch, when the resin composition is produced by melting and mixing with a styrene resin, Of course, even a single screw extruder can easily obtain the desired styrene-based flame retardant resin composition.
The content of (D) talc is 5 to 17 parts by mass, preferably 7 to 17 parts by mass with respect to a total of 100 parts by mass of (A) to (D) in the flame retardant masterbatch. If content is less than 5 mass parts, since the heat resistance and rigidity of the obtained styrene-type flame retardant resin composition will be reduced, the effect as a flame retardant masterbatch will be low. When the content exceeds 17 parts by mass, the Charpy impact strength and heat resistance of the styrene-based flame retardant resin composition are lowered, which is not preferable.
更に、本発明では、難燃剤マスターバッチに（Ｅ）酸化防止剤を使用する。
例えばオクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、エチレンビス（オキシエチレン）ビス［３−（５−ｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］等のフェノール系酸化防止剤が使用される。また、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト等のリン系酸化防止剤と併用してもよい。なかでも、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを使用することが好ましい。
難燃剤マスターバッチにおける前記（Ａ）乃至（Ｄ）の合計１００質量部に対し、これらの酸化防止剤の添加量は０．５乃至２．０質量部であり、１．０乃至２．０質量部であることが好ましい。酸化防止剤の添加量が０．５質量部未満であると本発明の難燃剤マスターバッチを使用してスチレン系難燃性樹脂組成物を得た場合、シャルピー衝撃強度が発現し難くなる。また２．０質量部を超えると、耐熱性の低下を招き易くなる。
本発明の難燃性マスターバッチにおいて、前記（Ａ）乃至（Ｄ）の配合割合としては、（Ａ）スチレン系樹脂６５乃至３０質量部、（Ｂ）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジン２５乃至５０質量部、（Ｃ）三酸化アンチモン３乃至８質量部、及び
（Ｄ）タルク７乃至１７質量部であるのが好ましい。Furthermore, in this invention, (E) antioxidant is used for a flame retardant masterbatch.
For example, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate, A phenolic antioxidant such as pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is used. Phosphorus oxidation of 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, etc. You may use together with an inhibitor. Among these, it is preferable to use octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.
The total amount of (A) to (D) in the flame retardant master batch is 100 parts by mass, and the added amount of these antioxidants is 0.5 to 2.0 parts by mass, and 1.0 to 2.0 parts by mass. Part. When the addition amount of the antioxidant is less than 0.5 parts by mass, when the styrene-based flame retardant resin composition is obtained using the flame retardant master batch of the present invention, the Charpy impact strength is hardly exhibited. Moreover, when it exceeds 2.0 mass parts, it will become easy to cause a heat resistant fall.
In the flame retardant masterbatch of the present invention, (A) 65 to 30 parts by mass of styrene resin, (B) 2,4,6-tris (2,4) , 6-tribromophenoxy) -1,3,5-triazine 25 to 50 parts by mass, (C) antimony trioxide 3 to 8 parts by mass, and (D) talc 7 to 17 parts by mass.
また、本発明の難燃剤マスターバッチを得るのに、さらに添加剤として着色剤、熱安定剤、紫外線吸収剤、可塑剤、滑剤及び帯電防止剤等を目的に合わせて混合することができる。 Moreover, in order to obtain the flame retardant masterbatch of the present invention, a colorant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, an antistatic agent, and the like can be further mixed according to the purpose.
例えば、スチレン系難燃性樹脂組成物は、着色成形品として黒色物が多いので、本発明では、顔料として（Ｆ）カーボンブラックを必要に応じて混合して難燃性マスターバッチとすることができる。尚、スチレン系難燃性樹脂組成物中の（Ｆ）カーボンブラックの含有量はＵＬ規格によって０．５質量%未満となる。従って、難燃性マスターバッチに添加出来る（Ｆ）カーボンブラックは、難燃剤マスターバッチにおける前記（Ａ）乃至（Ｄ）の合計１００質量部に対し、１．７質量部未満であるのが好ましく、１．５質量部以下であるのがより好ましい。
For example, since a styrene-based flame retardant resin composition is often a black product as a colored molded product, in the present invention, ( F ) carbon black may be mixed as a pigment as necessary to form a flame retardant masterbatch. it can. The content of ( F ) carbon black in the styrene-based flame retardant resin composition is less than 0.5% by mass according to UL standards. Therefore, ( F ) carbon black that can be added to the flame retardant masterbatch is preferably less than 1.7 parts by mass with respect to a total of 100 parts by mass of (A) to (D) in the flame retardant masterbatch, More preferably, it is 1.5 parts by mass or less.
また、難燃剤マスターバッチを製造する際の製造の容易性、また難燃剤マスターバッチを使用してスチレン系難燃性樹脂組成物を製造する際の製造の容易性、強度アップ等の観点から、滑剤としてポリオレフィン系ワックス、高級脂肪酸アミド、及び高級カルボン酸金属塩等を適宜使用することができる。 In addition, from the viewpoint of ease of production when producing a flame retardant masterbatch, and ease of production when producing a styrene-based flame retardant resin composition using a flame retardant masterbatch, an increase in strength, etc. As the lubricant, polyolefin waxes, higher fatty acid amides, higher carboxylic acid metal salts, and the like can be used as appropriate.
本発明の難燃剤マスターバッチの製造には、バンバリーミキサー、ニーダー、単軸押出機、二軸押出機等の方法を採用することが可能である。しかしながら、難燃剤マスターバッチを得る際には、難燃剤２，４，６−トリス（２，４，６−トリスブロモフェノキシ）−１，３，５−トリアジンを均一混合させるために、押出機本体に他の原料とは別のフィーダーを使用して均一に溶融混合させるのが好ましい。また、タルクを配合する場合はタルクの粉塵対策用に集塵機を備えるのが好ましい。 For the production of the flame retardant masterbatch of the present invention, methods such as a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder can be employed. However, when obtaining the flame retardant master batch, the extruder main body is used to uniformly mix the flame retardant 2,4,6-tris (2,4,6-trisbromophenoxy) -1,3,5-triazine. Further, it is preferable to uniformly melt and mix using a feeder different from other raw materials. Moreover, when mix | blending talc, it is preferable to provide a dust collector for dust countermeasures of talc.
次に、本発明のスチレン系難燃性樹脂組成物の製造方法について述べる。
なお、スチレン系難燃性樹脂組成物を得るのに使用するスチレン系樹脂をスチレン系樹脂（ＩＩ）、また、これまで詳述した難燃剤マスターバッチを難燃剤マスターバッチ（Ｉ）と以下称する。
スチレン系難燃性樹脂組成物を得るのに使用するスチレン系樹脂（ＩＩ）は、難燃剤マスターバッチ（Ｉ）で詳述した（Ａ）スチレン系樹脂と同様のものが使用出来るが、同一組成、同一種類のものである必要はない。勿論同一のものであっても良い。ゴム変性スチレン系樹脂及び／又は芳香族ビニル重合体が好ましく使用される。Next, the manufacturing method of the styrene-type flame retardant resin composition of this invention is described.
The styrene resin used to obtain the styrene flame retardant resin composition is hereinafter referred to as styrene resin (II), and the flame retardant master batch detailed above is referred to as flame retardant master batch (I).
The styrene resin (II) used to obtain the styrene flame retardant resin composition can be the same as (A) the styrene resin detailed in the flame retardant master batch (I), but the same composition. They do not have to be of the same type. Of course, they may be the same. A rubber-modified styrenic resin and / or an aromatic vinyl polymer is preferably used.
難燃剤マスターバッチ（Ｉ）とスチレン系樹脂（ＩＩ）の配合比は、得られるスチレン系難燃性樹脂組成物に要求される難燃性のクラス等により変量することができる。なかでも、難燃剤マスターバッチ（Ｉ）３０乃至８５質量部とスチレン系樹脂（ＩＩ）７０乃至１５質量部の割合で配合することが好ましい。特に、難燃剤マスターバッチ（Ｉ）３０乃至６０質量部とスチレン系樹脂（ＩＩ）７０乃至４０質量部の割合で配合することが好ましい。更に、このスチレン系難燃性樹脂組成物に対して、他の添加剤を配合することができる。
本発明の製造方法で得られるスチレン系難燃性樹脂組成物の難燃性は、米国アンダーライターズ・ラボラトリーズ社のサブジェクト９４号（以下、ＵＬ−９４とも略記する。）の垂直燃焼試験方法に準拠する評価において、V−０であるのが好ましい。The blending ratio of the flame retardant master batch (I) and the styrene resin (II) can be varied depending on the flame retardant class required for the obtained styrene flame retardant resin composition. Especially, it is preferable to mix | blend in the ratio of 30 to 85 mass parts of flame retardant masterbatch (I) and 70 to 15 mass parts of styrene resin (II). In particular, it is preferable to blend in a proportion of 30 to 60 parts by mass of the flame retardant masterbatch (I) and 70 to 40 parts by mass of the styrene resin (II). Furthermore, other additives can be blended with the styrene-based flame retardant resin composition.
The flame retardancy of the styrene-based flame retardant resin composition obtained by the production method of the present invention is determined by the vertical combustion test method of Subject No. 94 (hereinafter also abbreviated as UL-94) of US Underwriters Laboratories. In conforming evaluation, V-0 is preferable.
また、スチレン系難燃性樹脂組成物を得るのに一般的に使用する添加剤として難燃助剤、着色剤、熱安定剤、酸化防止剤、紫外線吸収剤、可塑剤、滑剤及び帯電防止剤等を目的に合わせて、そのままの形態で、或いは難燃剤マスターバッチに事前に添加して供給することもできる。 In addition, flame retardant aids, colorants, heat stabilizers, antioxidants, UV absorbers, plasticizers, lubricants and antistatic agents as additives generally used to obtain styrene-based flame retardant resin compositions In accordance with the purpose, it can be supplied as it is or added to the flame retardant master batch in advance.
特に、スチレン系難燃性樹脂組成物が燃焼した時の溶融滴下防止の目的でポリテトラフルオロエチレン（ＰＴＦＥ）を使用する場合、難燃剤マスターバッチ（Ｉ）とスチレン系樹脂（ＩＩ）の合計量１００質量部に対し、ポリテトラフルオロエチレン（ＰＴＦＥ）を好ましくは０．４質量部以下（但し０は含まず。）、より好ましくは０．１乃至０．３質量部を添加して溶融混合するのが好ましい。この場合、難燃剤マスターバッチ（Ｉ）、スチレン系樹脂（ＩＩ）及びポリテトラフルオロエチレン（ＰＴＦＥ）とを予備混合してから溶融することが好ましい。事前に、難燃剤マスターバッチにポリテトラフルオロエチレン（ＰＴＦＥ）を混合すると、スチレン系難燃性樹脂組成物を得る際に、ポリテトラフルオロエチレン（ＰＴＦＥ）の劣化を促進するので好ましくない。 In particular, when polytetrafluoroethylene (PTFE) is used for the purpose of preventing melt dripping when the styrene flame retardant resin composition burns, the total amount of the flame retardant master batch (I) and the styrene resin (II) Preferably, polytetrafluoroethylene (PTFE) is added in an amount of 0.4 parts by mass or less (excluding 0), more preferably 0.1 to 0.3 parts by mass with respect to 100 parts by mass. Is preferred. In this case, it is preferable that the flame retardant master batch (I), the styrene resin (II) and the polytetrafluoroethylene (PTFE) are premixed and then melted. When polytetrafluoroethylene (PTFE) is mixed in advance with a flame retardant master batch, deterioration of polytetrafluoroethylene (PTFE) is promoted when a styrene-based flame retardant resin composition is obtained.
本発明のスチレン系難燃性樹脂組成物の製造方法で使用する溶融混合の方法としては、バンバリーミキサー、ニーダー、単軸押出機、二軸押出機等の方法を採用することが可能であるが、単軸押出機、又は二軸押出機の溶融押出機を使用することが好ましい。溶融押出におけるシリンダー温度は、一般的なスチレン系難燃性樹脂組成物を押し出す際に使用する温度で行なうことができ、特にこだわるものではないが、２００乃至２５０℃が好ましく、２１０乃至２４０℃がより好ましい。 As a method of melt mixing used in the method for producing a styrene-based flame retardant resin composition of the present invention, a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, or the like can be adopted. It is preferable to use a melt extruder of a single screw extruder or a twin screw extruder. The cylinder temperature in melt extrusion can be performed at a temperature used when extruding a general styrene-based flame retardant resin composition, and is not particularly limited, but is preferably 200 to 250 ° C, and preferably 210 to 240 ° C. More preferred.
本発明の難燃剤マスターバッチ（Ｉ）とスチレン系樹脂（ＩＩ）とを溶融押出機に供給する方法としては、タンブラーやＶブレンダー等の公知の装置を使用して予備混合したものを供給する方法や、押出機の供給口に両材料を別々に定量的に供給する方法を採用することができる。 As a method of supplying the flame retardant master batch (I) and the styrene resin (II) of the present invention to a melt extruder, a method of supplying a premixed mixture using a known apparatus such as a tumbler or V blender. Alternatively, a method of separately and quantitatively supplying both materials to the supply port of the extruder can be employed.
更に、単軸押出機のスクリューは、最も汎用性の高いフルフライトスクリューを使用することができるが、より混練性の高いダルメージタイプ、ピンタイプ、又はマドックタイプのスクリューを使用することもできる。 Further, the most versatile full flight screw can be used as the screw of the single screw extruder, but a dull image type, pin type, or Maddock type screw having higher kneading properties can also be used.
以下に実施例を挙げて具体的に本発明を説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
以下の実施例において、難燃剤マスターバッチを得るのに使用した（Ａ）スチレン系樹脂、及びスチレン系難燃性樹脂組成物を得るのに使用したスチレン系樹脂（ＩＩ）としては、下記の特性を有する、（Ａ−１）、（Ａ−２）及び／又は（Ａ−３）を使用した。
（Ａ−１）：
ゴム状重合体にシス１、４結合を９０モル％以上の比率で含有するハイシスポリブタジエンゴムを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂の組成は、マトリックス部分の還元粘度が０．７５ｄｌ／ｇであり、ゴム状重合体の含有量が９．３質量％であり、ゴム状重合体のゲル含有量が２７．０質量％であり、及びゴム状重合体の体積平均粒子径が２．５３μｍであり、更にゴム変性スチレン系樹脂中の流動パラフィン含有量が１．９質量％である。
（Ａ−２）：
ゴム状重合体にシローシスポリブタジエンゴムを使用したゴム変性スチレン系樹脂である。このゴム変性スチレン系樹脂の組成はマトリックス部分の還元粘度が０．５８ｄｌ／ｇであり、並びにゴム状重合体の含有量が９．９質量％であり、ゴム状重合体のゲル含有量が３０．５質量％であり、及びゴム状重合体の体積平均粒子径が２．５０μｍであり、更にゴム変性スチレン系樹脂中の流動パラフィン含有量が２．０質量％である。
（Ａ−３）：
還元粘度が０．７０ｄｌ／ｇであり、スチレン系樹脂中の流動パラフィン含有量が２．５質量％であるスチレン重合体（ＧＰ）を使用した。
また、ゴム変性スチレン系樹脂に添加したスチレン−ブタジエン共重合体（Ｇ）には、スチレン−ブタジエン−スチレンブロック共重合体（旭化成ケミカルズ社製、商品名タフプレン３１５Ｐ）を使用した。In the following examples, the styrene resin (II) used to obtain the flame retardant master batch and the styrene resin (II) used to obtain the styrene flame retardant resin composition have the following characteristics: (A-1), (A-2) and / or (A-3) were used.
(A-1):
This is a rubber-modified styrene resin using a high-cis polybutadiene rubber containing cis 1,4 bonds in a ratio of 90 mol% or more in the rubber-like polymer. The composition of this rubber-modified styrenic resin is such that the reduced viscosity of the matrix portion is 0.75 dl / g, the content of the rubber-like polymer is 9.3% by mass, and the gel content of the rubber-like polymer is 27%. The rubber-like polymer has a volume average particle size of 2.53 μm, and the liquid paraffin content in the rubber-modified styrenic resin is 1.9% by mass.
(A-2):
It is a rubber-modified styrenic resin using a shirosis polybutadiene rubber as a rubbery polymer. The composition of this rubber-modified styrenic resin has a reduced viscosity of 0.58 dl / g in the matrix portion, a rubber-like polymer content of 9.9% by mass, and a rubber-like polymer gel content of 30. The volume average particle size of the rubber-like polymer is 2.50 μm, and the content of liquid paraffin in the rubber-modified styrenic resin is 2.0% by mass.
(A-3):
A styrene polymer (GP) having a reduced viscosity of 0.70 dl / g and a liquid paraffin content in the styrene resin of 2.5% by mass was used.
Further, as the styrene-butadiene copolymer (G) added to the rubber-modified styrene resin, a styrene-butadiene-styrene block copolymer (manufactured by Asahi Kasei Chemicals Co., Ltd., trade name TUFPRENE 315P) was used.
本発明における、還元粘度、ゲル含有量、ゴム状重合体の含有量及び平均粒子径は以下の方法で測定した。尚、流動パラフィン含有量は仕込み量を示す。 In the present invention, the reduced viscosity, the gel content, the rubbery polymer content and the average particle size were measured by the following methods. The liquid paraffin content indicates the amount charged.
還元粘度（ηｓｐ／Ｃ）：
ゴム変性スチレン系樹脂１ｇにメチルエチルケトン１５ｍｌとアセトン１５ｍｌの混合溶媒を加え、温度２５℃で２時間振とう溶解した。次いで、遠心分離で不溶分を沈降させ、デカンテーションにより上澄み液を取り出し、５００ｍｌのメタノールを加えて樹脂分を析出させ、不溶分を濾過乾燥した。同操作で得られた樹脂分をトルエンに溶解してポリマー濃度が０．４％（質量／体積）の試料溶液を調製した。この試料溶液、及び純トルエンを温度３０℃の恒温でウベローデ型粘度計により溶液流下秒数を測定して、下式にて算出した。
ηｓｐ／Ｃ＝（ｔ１／ｔ０−１）／Ｃ
ｔ０：純トルエン流下秒数
ｔ１：試料溶液流下秒数
Ｃ：ポリマー濃度Reduced viscosity (ηsp / C):
A mixed solvent of 15 ml of methyl ethyl ketone and 15 ml of acetone was added to 1 g of rubber-modified styrenic resin and dissolved by shaking at a temperature of 25 ° C. for 2 hours. Subsequently, the insoluble matter was settled by centrifugation, the supernatant was taken out by decantation, 500 ml of methanol was added to precipitate the resin, and the insoluble matter was filtered and dried. The resin component obtained by the same operation was dissolved in toluene to prepare a sample solution having a polymer concentration of 0.4% (mass / volume). This sample solution and pure toluene were measured at a constant temperature of 30 ° C. using a Ubbelohde viscometer, and the number of seconds during which the solution flowed was measured.
ηsp / C = (t1 / t0-1) / C
t0: Pure toluene flow down seconds
t1: Sample solution flow down seconds
C: Polymer concentration
ゴム状重合体のゲル含有量：
１ｇのゴム変性スチレン系樹脂組成物をメチルエチルケトン１５ｍｌとアセトン１５ｍｌの混合溶媒に加え、温度２５℃で２時間振とう溶解した。次いで、遠心分離して不溶分を沈降させ、デカンテーションにより上澄み液を除去して不溶分を得、温度７０℃で１５時間程度真空乾燥し、２０分間デシケーター中で冷却した後、乾燥した不溶分の質量Ｇ（ｇ）を測定して次の式でより求めた。
ゴム状重合体のゲル含有量（質量％）＝（Ｇ／１）×１００Gel content of rubbery polymer:
1 g of the rubber-modified styrenic resin composition was added to a mixed solvent of 15 ml of methyl ethyl ketone and 15 ml of acetone and dissolved by shaking at a temperature of 25 ° C. for 2 hours. Next, the insoluble matter is settled by centrifugation, the supernatant is removed by decantation to obtain an insoluble matter, vacuum dried at a temperature of 70 ° C. for about 15 hours, cooled in a desiccator for 20 minutes, and then dried insoluble matter. The mass G (g) of was measured and obtained from the following formula.
Gel content (mass%) of rubber-like polymer = (G / 1) × 100
ゴム状重合体の含有量：
ゴム変性スチレン系樹脂をクロロホルムに溶解させ、一定量の一塩化ヨウ素／四塩化炭素溶液を加え暗所に約１時間放置した。次いで、１５質量／体積のヨウ化カリウム溶液と純水５０ｍｌを加え、過剰の一塩化ヨウ素を０．１Ｎチオ硫酸ナトリウム／エタノール水溶液で滴定し、付加した一塩化ヨウ素量から算出した。Rubbery polymer content:
The rubber-modified styrenic resin was dissolved in chloroform, a certain amount of iodine monochloride / carbon tetrachloride solution was added, and the mixture was left in the dark for about 1 hour. Subsequently, 15 mass / volume potassium iodide solution and 50 ml of pure water were added, excess iodine monochloride was titrated with 0.1N sodium thiosulfate / ethanol aqueous solution, and the amount of iodine monochloride added was calculated.
（Ｂ）難燃剤には、（Ｂ−１）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジンである第一工業製薬社製の商品名ピロガードＳＲ２４５を使用した。また、比較用難燃剤として、（Ｂ−２）エチレンビスペンタブロモベンゼンであるアルベマール社製の商品名ＳＡＹＴＥＸ−８０１０（以下、Ｓ８０１０と略記する。）を使用した。 (B) For the flame retardant, (B-1) 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, trade name of Daiichi Kogyo Seiyaku Co., Ltd. Pyroguard SR245 was used. Moreover, the brand name SAYTEX-8010 (henceforth S8010) by the Albemarle company which is (B-2) ethylenebispentabromobenzene was used as a comparative flame retardant.
（Ｃ）難燃助剤には、鈴裕化学社製、商品名ＡＴ−３ＣＮ（三酸化アンチモン）を使用した。 (C) Suzuhiro Chemical Co., Ltd. product name AT-3CN (antimony trioxide) was used for the flame retardant aid.
（Ｄ）タルクには、富士タルク社製の商品名ＫＰタルクを使用した。 (D) The product name KP talc manufactured by Fuji Talc was used as the talc.
（Ｅ）酸化防止剤には、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（ＢＡＳＦジャパン社製、商品名ＩＲＧＡＮＯＸ１０７６）を使用した。 (E) Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (BASF Japan, trade name IRGANOX1076) was used as the antioxidant.
（Ｆ）カーボンブラックには、カーボンブラック含有量が４０質量％である越谷化成社製の商品名ＲＢ９６２Ｐを使用した。 (F) As the carbon black, trade name RB962P manufactured by Koshigaya Kasei Co., Ltd. having a carbon black content of 40% by mass was used.
ポリテトラフルオロエチレン（ＰＴＦＥ）には、三井・デュポンフロロケミカル社製の商品名ＰＴＦＥ３１−ＪＲを使用した。これを（Ｈ）と略記する。 As polytetrafluoroethylene (PTFE), trade name PTFE31-JR manufactured by Mitsui DuPont Fluorochemical Co., Ltd. was used. This is abbreviated as (H).
次に、本発明の難燃剤マスターバッチの混合方法を述べる。（Ａ）スチレン系樹脂、（Ｂ）難燃剤、（Ｃ）難燃助剤、（Ｄ）タルク、（Ｅ）酸化防止剤、（Ｆ）カーボンブラック、及び（Ｇ）スチレン−ブタジエン−スチレン共重合体を表１、表２、表３に示す配合量（質量部）にて、形状別に、ペレット状と粉体状に分けて、それぞれの形状の成分をヘンシェルミキサー（三井三池化工社製、ＦＭ２０Ｂ）にて予備混合した。予備今後物を、二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）にペレット状成分と粉体状成分とを別フィード供給してストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、シリンダー温度２００℃、供給量５０ｋｇ／時間とした。 Next, a method for mixing the flame retardant master batch of the present invention will be described. (A) Styrenic resin, (B) flame retardant, (C) flame retardant aid, (D) talc, (E) antioxidant, (F) carbon black, and (G) styrene-butadiene-styrene copolymer The coalescence is divided into pellets and powders by blending amount (parts by mass) shown in Table 1, Table 2 and Table 3, and the components of each shape are divided into Henschel mixers (FM20B, manufactured by Mitsui Miike Chemical Co., Ltd.). ). The preliminary future product was fed into a twin screw extruder (Toshiki Machine Co., Ltd., TEM26SS) by separately feeding the pellet component and the powder component into strands, cooled with water, then led to a pelletizer and pelletized. At this time, the cylinder temperature was 200 ° C., and the supply amount was 50 kg / hour.
なお、上記予備混合時に、ソジウムアルミノシリケートとＡ型ゼオライトの混合物及びカルシウムステアレートも同時添加した。 During the preliminary mixing, a mixture of sodium aluminosilicate and A-type zeolite and calcium stearate were also added simultaneously.
本発明で検討に使用した難燃マスターバッチの組成物を下記の表１、表２、表３に示す。 The composition of the flame retardant masterbatch used for the study in the present invention is shown in Table 1, Table 2, and Table 3 below.
また、上記で得られた難燃剤マスターバッチ（Ｉ）、スチレン系樹脂（ＩＩ）、及び（Ｈ）ポリテトラフルオロエチレン（ＰＴＦＥ）を表４、表５、表６に示す配合量（質量部）にて、全成分をタンブラーにて予備混合した。予備混合物を、単軸押出機（ＩＫＧ社製 ＰＭＳ４０−２８）及び二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）に供給してストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、二軸押出機はシリンダー温度２３０℃、供給量３０ｋｇ／時間とした。また、単軸押出機はシリンダー温度２３０℃、スクリュー回転数１００ｒｐｍとした。なお、（Ｈ）ポリテトラフルオロエチレン（ＰＴＦＥ）はＰＴＦＥ純量が配合量となるように添加した。 Further, the flame retardant master batch (I), the styrene resin (II), and the (H) polytetrafluoroethylene (PTFE) obtained in the above are shown in Tables 4, 5, and 6 (parts by mass). All components were premixed in a tumbler. The premix was fed to a single screw extruder (PMS PMS40-28 manufactured by IKG) and a twin screw extruder (manufactured by Toshiba Machine Co., TEM26SS) to form a strand, which was cooled with water and led to a pelletizer to be pelletized. At this time, the twin screw extruder was set to a cylinder temperature of 230 ° C. and a supply amount of 30 kg / hour. The single screw extruder was set to a cylinder temperature of 230 ° C. and a screw rotation speed of 100 rpm. Note that (H) polytetrafluoroethylene (PTFE) was added so that the pure amount of PTFE would be the blending amount.
また、（Ａ）スチレン系樹脂、（Ｂ）難燃剤、（Ｃ）難燃助剤、（Ｄ）タルク、（Ｅ）酸化防止剤、（Ｆ）カーボンブラック、（Ｇ）スチレン−ブタジエン−スチレン共重合体、及び（Ｈ）ポリテトラフルオロエチレン（ＰＴＦＥ）を表７に示す配合量（質量部）にて難燃剤マスターバッチ（Ｉ）を使用せずにスチレン系難燃性樹脂組成物を得た。
二軸押出機（東芝機械社製、ＴＥＭ２６ＳＳ）を使用した場合は、形状がペレット状と粉体状の物を分けて、それぞれの形状成分をヘンシェルミキサー（三井三池化工社製、ＦＭ２０Ｂ）にて予備混合し、別フィード供給してストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、シリンダー温度２３０℃、供給量３０ｋｇ／時間とした。
単軸押出機（ＩＫＧ社製 ＰＭＳ４０−２８）を使用した場合は、全成分をタンブラーにて予備混合し、ストランドとし、水冷してからペレタイザーへ導きペレット化した。この際、シリンダー温度２３０℃、スクリュー回転数１００ｒｐｍとした。なお、（Ｈ）ポリテトラフルオロエチレン（ＰＴＦＥ）はＰＴＦＥ純量が配合量となるように添加した。(A) styrene resin, (B) flame retardant, (C) flame retardant aid, (D) talc, (E) antioxidant, (F) carbon black, (G) styrene-butadiene-styrene A styrene-based flame retardant resin composition was obtained without using the flame retardant masterbatch (I) at a blending amount (part by mass) of the polymer and (H) polytetrafluoroethylene (PTFE) shown in Table 7. .
When a twin-screw extruder (Toshiki Machine Co., Ltd., TEM26SS) is used, the shape is divided into pellets and powder, and each shape component is separated by a Henschel mixer (Mitsui Miike Chemical Industries, FM20B). The mixture was preliminarily mixed and fed separately to form a strand, which was cooled with water and then led to a pelletizer to be pelletized. At this time, the cylinder temperature was 230 ° C. and the supply amount was 30 kg / hour.
When a single screw extruder (PMS40-28 manufactured by IKG) was used, all components were premixed with a tumbler to form a strand, cooled with water, and then led to a pelletizer to be pelletized. At this time, the cylinder temperature was 230 ° C. and the screw rotation speed was 100 rpm. Note that (H) polytetrafluoroethylene (PTFE) was added so that the pure amount of PTFE would be the blending amount.
なお、実施例、比較例に示された各種測定は以下の方法により実施した。 Various measurements shown in Examples and Comparative Examples were performed by the following methods.
（１）難燃性の測定
難燃性の測定は、米国アンダーライターズ・ラボラトリーズ社のサブジェクト９４号の垂直燃焼試験方法に準拠し、試験片厚さ１．５ｍｍの燃焼性を評価した。評価結果は下記の様に表記した。
ＮＧ：Ｖ−０でない燃焼性（V−１、V−２、又はHB）を示すもの。(1) Measurement of flame retardance The flame retardancy was measured in accordance with the vertical combustion test method of Subject No. 94 of US Underwriters Laboratories, Inc., and the combustibility with a specimen thickness of 1.5 mm was evaluated. The evaluation results are shown as follows.
NG: What shows non-V-0 flammability (V-1, V-2, or HB).
（２）シャルピー衝撃強度の測定
シャルピー衝撃強度は、ＪＩＳ Ｋ ７１１１−１に基づき測定を行った。
測定装置：シャルピー試験機（東洋精機社製）
ノッチタイプ：タイプＡ
打撃方向：エッジワイズ
測定環境：２３℃(2) Measurement of Charpy impact strength The Charpy impact strength was measured based on JIS K7111-1.
Measuring device: Charpy testing machine (Toyo Seiki Co., Ltd.)
Notch type: Type A
Stroke direction: Edgewise Measurement environment: 23 ° C
（３）荷重たわみ温度（ＨＤＴ）
荷重たわみ温度は、ＪＩＳ Ｋ ７１９１に基づき測定を行った。
測定装置：No．１４８−ＨＤ−ＰＣ−３（安田精機社製）
応力：１．８０ＭＰａ
支点間距離：６４ｍｍ
試験片サイズ：長さ８０ｍｍ 幅１０ｍｍ 高さ４ｍｍ フラットワイズ(3) Deflection temperature under load (HDT)
The deflection temperature under load was measured based on JIS K 7191.
Measuring device: No. 148-HD-PC-3 (manufactured by Yasuda Seiki Co., Ltd.)
Stress: 1.80 MPa
Distance between fulcrums: 64mm
Specimen size: Length 80mm Width 10mm Height 4mm Flatwise
（４）メルトフローレート（ＭＦＲ）
メルトフローレート（ＭＦＲ）は、得られたペレットをＪＩＳ Ｋ ７２１０に基づき測定を行った。
試験温度：２００℃
試験荷重：４９．０３Ｎ(4) Melt flow rate (MFR)
Melt flow rate (MFR) measured the obtained pellet based on JISK7210.
Test temperature: 200 ° C
Test load: 49.03N
（５）外観
射出成形機（日本製鋼所社製、Ｊ１００Ｅ−Ｐ）にて９０ｍｍ角板（厚み２ｍｍ）に成形し、成形品の表面に成形不良（ブツ・フラッシュ等）の有無を観察して外観を評価した。この際、シリンダー温度２３０℃、金型温度３０℃とした。
○：成形品表面の不良（ブツ・フラッシュ）が見られないもの。
×：成形品表面の不良（ブツ・フラッシュ）が見られたもの。(5) Appearance Molded into a 90mm square plate (thickness 2mm) with an injection molding machine (Nippon Steel Works, J100E-P), and observed the presence or absence of molding defects (such as flashing) on the surface of the molded product. Appearance was evaluated. At this time, the cylinder temperature was 230 ° C. and the mold temperature was 30 ° C.
○: No defects on the surface of the molded product (buzz / flash).
X: The surface of the molded product was found to be defective (buzz / flash).
各種試験の試験片の作製条件
シャルピー衝撃強度用試験片、及び荷重たわみ温度試験片として、射出成形機（日本製鋼所社製、Ｊ１００Ｅ−Ｐ）にて、ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）を作製した。成形条件はＪＩＳ Ｋ ６９２６−２に準拠して行った。シャルピー衝撃強度用試験片は、該ダンベル片の中央部より切り出し、切削でノッチ（タイプＡ、ｒ＝０．２５ｍｍ）を入れ、試験に用いた。また、荷重たわみ温度試験片は、該ダンベル片の中央部より切り出し、試験に用いた。Preparation conditions of test pieces for various tests A-type test pieces described in JIS K 7139 as Charpy impact strength test pieces and load deflection temperature test pieces using an injection molding machine (manufactured by Nippon Steel Works, J100E-P) (Dumbell) was produced. Molding conditions were performed according to JIS K 6926-2. The Charpy impact strength test piece was cut out from the center of the dumbbell piece, cut into a notch (type A, r = 0.25 mm), and used for the test. Moreover, the load deflection temperature test piece was cut out from the center part of the dumbbell piece and used for the test.
燃焼性の評価用試験片は、射出成形機（日本製鋼所社製、Ｊ１００Ｅ−Ｐ）にて、１２７×１２.７×１．５ｍｍの燃焼用試験片を成形した。この際、シリンダー温度１９０℃、金型温度３０℃とした。 The test piece for evaluation of combustibility was formed as a 127 × 12.7 × 1.5 mm combustion test piece with an injection molding machine (manufactured by Nippon Steel Works, J100E-P). At this time, the cylinder temperature was 190 ° C. and the mold temperature was 30 ° C.
難燃マスターバッチを使用したスチレン系難燃性樹脂組成物の溶融混合方法及びそれらの物性値を以下の表４、表５、表６に示す。 The following Table 4, Table 5, and Table 6 show the melt mixing method of the styrene-based flame retardant resin composition using the flame retardant masterbatch and the physical property values thereof.
難燃性マスターバッチを使用しないで単軸押出機で押出したスチレン系難燃性樹脂組成物の評価結果を表７に示す。 Table 7 shows the evaluation results of the styrene-based flame-retardant resin composition extruded with a single screw extruder without using the flame-retardant masterbatch.
上記の実施例にみられるように、本発明の難燃剤マスターバッチを使用し、本発明の製造方法で得られたスチレン系難燃性樹脂組成物は、難燃性、衝撃強度、耐熱性、流動性のバランスが良く、更に外観も良好であることがわかる。
しかし、本発明の要件を満足しない比較例で得られたスチレン系難燃性樹脂組成物は、難燃性、衝撃強度、耐熱性、流動性の何れかに優れることはあっても、その全てに優れていることはないことがわかる。As seen in the above examples, using the flame retardant master batch of the present invention, the styrene-based flame retardant resin composition obtained by the production method of the present invention is flame retardant, impact strength, heat resistance, It can be seen that the fluidity balance is good and the appearance is also good.
However, the styrene-based flame retardant resin composition obtained in the comparative example that does not satisfy the requirements of the present invention is excellent in any of flame retardancy, impact strength, heat resistance, and fluidity, but all of them. It is clear that there is nothing better than
例えば、難燃剤マスターバッチの（Ａ）スチレン系樹脂が規定量より多いと難燃性が劣り（比較例１）、少ないとシャルピー衝撃強度及び耐熱性が低い（比較例２）。また、難燃剤マスターバッチの（Ｂ）難燃剤が規定量より多いとシャルピー及び耐熱性が低く（比較例３）、少ないと難燃性に劣りＵＬ９４燃焼試験でのＶ−０レベルが確保できなくなり（比較例４）、難燃剤種をＳ８０１０にするとシャルピー、流動性が低い（比較例１６）。また、難燃剤マスターバッチの（Ｃ）難燃助剤が規定量より多いとＵＬ９４燃焼試験でグローイング時間が延びてＶ−０レベルが確保できなくなり、シャルピーも低く（比較例５）、少ないと難燃性に劣りＵＬ９４燃焼試験でのＶ−０レベルが確保できなくなる（比較例６）。 For example, if the amount of (A) styrene resin in the flame retardant master batch is larger than the specified amount, the flame retardancy is inferior (Comparative Example 1), and if it is small, the Charpy impact strength and heat resistance are low (Comparative Example 2). In addition, when the flame retardant masterbatch (B) flame retardant is more than the specified amount, Charpy and heat resistance are low (Comparative Example 3), and when it is small, flame retardancy is inferior and the V-0 level in the UL94 combustion test cannot be secured. (Comparative Example 4) When the flame retardant species is S8010, Charpy and fluidity are low (Comparative Example 16). In addition, if the flame retardant master batch (C) flame retardant aid is more than the specified amount, the glowing time is extended in the UL94 combustion test, the V-0 level cannot be secured, and the Charpy is low (Comparative Example 5). It is inferior in flammability and cannot secure the V-0 level in the UL94 combustion test (Comparative Example 6).
また、難燃剤マスターバッチの（Ｄ）タルクが規定量より多いと難燃性に劣りＵＬ９４燃焼試験でのＶ−０レベルが確保できなくなり、シャルピーも低く（比較例７）、少ないと耐熱性が低い（比較例８）。また、難燃剤マスターバッチの（Ｅ）酸化防止剤を添加しないとシャルピーが低い（比較例９乃至１１）。また、難燃剤マスターバッチが規定量のものを使用しても、難燃剤マスターバッチ配合量が規定量より少ないと難燃性に劣りＵＬ９４燃焼試験でのＶ−０レベルが確保できなくなり（比較例１２）、多いと耐熱性が低い（比較例１３）。また、難燃剤マスターバッチが規定量のものを使用しても、（Ｈ）ＰＴＦＥが規定量より多いとＵＬ９４燃焼試験でグローイング時間が延びてＶ−０レベルが確保できなくなる（比較例１４）。また、難燃剤マスターバッチを使用し、溶融混合は単軸押出機・二軸押出機どちらも同じ物性になり容易に単軸押出機でスチレン系難燃性樹脂組成物を得ることができる（実施例１０、１１、比較例１４、１５）。 In addition, if the flame retardant master batch (D) talc is more than the specified amount, the flame retardancy is inferior and the V-0 level in the UL94 combustion test cannot be secured, the Charpy is low (Comparative Example 7), and if it is low, the heat resistance is low. Low (Comparative Example 8). Moreover, Charpy is low unless the (E) antioxidant of a flame retardant masterbatch is added (Comparative Examples 9 to 11). Moreover, even if a flame retardant masterbatch having a specified amount is used, if the amount of the flame retardant masterbatch is less than the specified amount, the flame retardancy is inferior and the V-0 level in the UL94 combustion test cannot be secured (Comparative Example). 12) If too much, the heat resistance is low (Comparative Example 13). Further, even when a flame retardant master batch having a specified amount is used, if the amount of (H) PTFE is larger than the specified amount, the glowing time is extended in the UL94 combustion test and the V-0 level cannot be secured (Comparative Example 14). Also, using a flame retardant masterbatch, melt mixing has the same physical properties for both single-screw and twin-screw extruders, and a styrene-based flame-retardant resin composition can be easily obtained with a single-screw extruder. Examples 10, 11 and Comparative Examples 14, 15).
また、難燃剤マスターバッチ（Ｉ）を使用せずにスチレン系難燃性樹脂組成物を単軸押出機で溶融混合するとシャルピー、耐熱性、外観が劣る（比較例１７乃至１９）。難燃剤マスターバッチを使用して得たスチレン系難燃性樹脂組成物は表４、表５の実施例に示したとおり難燃性、衝撃強度、耐熱性、流動性のバランスが良く、更に外観も良好である。 Further, when the styrene flame retardant resin composition is melt-mixed with a single screw extruder without using the flame retardant master batch (I), the Charpy, heat resistance and appearance are inferior (Comparative Examples 17 to 19). Styrenic flame retardant resin compositions obtained using the flame retardant masterbatch have a good balance of flame retardancy, impact strength, heat resistance, and fluidity as shown in the examples of Tables 4 and 5, and further the appearance. Is also good.
本発明の難燃剤マスターバッチは、スチレン系難燃性樹脂組成物の製造に利用できる。 The flame retardant masterbatch of the present invention can be used for the production of a styrene-based flame retardant resin composition.
Claims (11)
（Ｂ）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジン１５乃至５０質量部、
（Ｃ）三酸化アンチモン２乃至８質量部、及び
（Ｄ）タルク５乃至１７質量部を含有し、
かつ、（Ａ）乃至（Ｄ）の合計１００質量部に対し、更に
（Ｅ）酸化防止剤０．５乃至２．０質量部を含有することを特徴とする難燃剤マスターバッチ。(A) 75 to 25 parts by mass of a styrene resin,
(B) 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine 15 to 50 parts by mass,
(C) 2 to 8 parts by mass of antimony trioxide, and (D) 5 to 17 parts by mass of talc,
And the flame retardant masterbatch characterized by further containing (E) antioxidant 0.5 thru | or 2.0 mass part with respect to a total of 100 mass parts of (A) thru | or (D).
（Ｂ）２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジン２５乃至５０質量部、
（Ｃ）三酸化アンチモン３乃至８質量部、及び
（Ｄ）タルク７乃至１７質量部である請求項１又は２に記載の難燃剤マスターバッチ。(A) 65 to 30 parts by mass of a styrene resin,
(B) 25 to 50 parts by mass of 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine,
The flame retardant masterbatch according to claim 1 or 2, wherein (C) 3 to 8 parts by mass of antimony trioxide and (D) 7 to 17 parts by mass of talc.
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