JP6227865B2 - Rubber-modified polystyrene-based resin composition, rubber-modified polystyrene-based flame retardant resin composition, and molded products using these. - Google Patents
Rubber-modified polystyrene-based resin composition, rubber-modified polystyrene-based flame retardant resin composition, and molded products using these. Download PDFInfo
- Publication number
- JP6227865B2 JP6227865B2 JP2012249909A JP2012249909A JP6227865B2 JP 6227865 B2 JP6227865 B2 JP 6227865B2 JP 2012249909 A JP2012249909 A JP 2012249909A JP 2012249909 A JP2012249909 A JP 2012249909A JP 6227865 B2 JP6227865 B2 JP 6227865B2
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- Prior art keywords
- rubber
- modified polystyrene
- resin composition
- flame retardant
- based flame
- Prior art date
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- 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 41
- 239000003063 flame retardant Substances 0.000 title claims description 41
- 239000011342 resin composition Substances 0.000 title claims description 35
- 239000004793 Polystyrene Substances 0.000 title claims description 26
- 229920002223 polystyrene Polymers 0.000 title claims description 26
- 229920005990 polystyrene resin Polymers 0.000 claims description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 8
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000012757 flame retardant agent Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920001971 elastomer Polymers 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000005063 High cis polybutadiene Substances 0.000 description 7
- 230000007774 longterm Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000005064 Low cis polybutadiene Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- -1 2,4,6-tribromophenoxy Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000010452 phosphate 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
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OTFKIJJCSGQDBD-UHFFFAOYSA-N Brc1cc(Br)c(c(Br)c1)-c1nc(nc(n1)-c1c(Br)cc(Br)cc1Br)-c1c(Br)cc(Br)cc1Br Chemical compound Brc1cc(Br)c(c(Br)c1)-c1nc(nc(n1)-c1c(Br)cc(Br)cc1Br)-c1c(Br)cc(Br)cc1Br OTFKIJJCSGQDBD-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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVVFAEKRHJHHOF-UHFFFAOYSA-N (3-hydroxy-2,4-diphenylphenyl) dihydrogen phosphate Chemical compound OC1=C(C=2C=CC=CC=2)C=CC(OP(O)(O)=O)=C1C1=CC=CC=C1 BVVFAEKRHJHHOF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- DEIGXXQKDWULML-UHFFFAOYSA-N 1,2,5,6,9,10-hexabromocyclododecane Chemical compound BrC1CCC(Br)C(Br)CCC(Br)C(Br)CCC1Br DEIGXXQKDWULML-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
- KUJHYJBRSXWIFB-UHFFFAOYSA-N 1,3,5-tribromo-2-[1-(2,4,6-tribromophenoxy)ethoxy]benzene Chemical compound BrC=1C=C(Br)C=C(Br)C=1OC(C)OC1=C(Br)C=C(Br)C=C1Br KUJHYJBRSXWIFB-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
- 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 description 1
- NCVFZIASVZHSOI-UHFFFAOYSA-N 2-chloroethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCl)OC1=CC=CC=C1 NCVFZIASVZHSOI-UHFFFAOYSA-N 0.000 description 1
- QDLYDXLYPXBEKO-UHFFFAOYSA-N 2-ethylhexyl bis(4-methylphenyl) phosphate Chemical compound C=1C=C(C)C=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=C(C)C=C1 QDLYDXLYPXBEKO-UHFFFAOYSA-N 0.000 description 1
- UGIWGFXQNPWKPR-UHFFFAOYSA-M 2-ethylhexyl phenyl phosphate Chemical compound CCCCC(CC)COP([O-])(=O)OC1=CC=CC=C1 UGIWGFXQNPWKPR-UHFFFAOYSA-M 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
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VAAKMKLKGSYLDZ-UHFFFAOYSA-N CC(CCC(C)(C)C)COP(=O)(O)O Chemical compound CC(CCC(C)(C)C)COP(=O)(O)O VAAKMKLKGSYLDZ-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 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
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910000411 antimony tetroxide Inorganic materials 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 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
- OFOXPUGNNSFGPE-UHFFFAOYSA-N bis(2,2-dimethylpropyl) phenyl phosphate Chemical compound CC(C)(C)COP(=O)(OCC(C)(C)C)OC1=CC=CC=C1 OFOXPUGNNSFGPE-UHFFFAOYSA-N 0.000 description 1
- XIMUORXKUCOUFY-UHFFFAOYSA-N bis(2-ethylhexyl) (4-methylphenyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OC1=CC=C(C)C=C1 XIMUORXKUCOUFY-UHFFFAOYSA-N 0.000 description 1
- ZXZYMQCBRZBVIC-UHFFFAOYSA-N bis(2-ethylhexyl) phenyl phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 ZXZYMQCBRZBVIC-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
- 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
- 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
- 238000010908 decantation Methods 0.000 description 1
- YICSVBJRVMLQNS-UHFFFAOYSA-N dibutyl phenyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OC1=CC=CC=C1 YICSVBJRVMLQNS-UHFFFAOYSA-N 0.000 description 1
- RYSCVIAVOSESIU-UHFFFAOYSA-N didodecyl (4-methylphenyl) phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCC)OC1=CC=C(C)C=C1 RYSCVIAVOSESIU-UHFFFAOYSA-N 0.000 description 1
- OHZIKCOBQFCTDM-UHFFFAOYSA-N didodecyl phenyl phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCC)OC1=CC=CC=C1 OHZIKCOBQFCTDM-UHFFFAOYSA-N 0.000 description 1
- UDTNMDMYVIAQAH-UHFFFAOYSA-N dinaphthalen-2-yl phenyl phosphate Chemical compound C=1C=C2C=CC=CC2=CC=1OP(OC=1C=C2C=CC=CC2=CC=1)(=O)OC1=CC=CC=C1 UDTNMDMYVIAQAH-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000012046 mixed solvent 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
- 238000000465 moulding Methods 0.000 description 1
- FVZFCHKRLYMSEQ-UHFFFAOYSA-N naphthalen-1-yl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C2=CC=CC=C2C=CC=1)(=O)OC1=CC=CC=C1 FVZFCHKRLYMSEQ-UHFFFAOYSA-N 0.000 description 1
- JSJUBNHZCFKUKY-UHFFFAOYSA-N naphthalen-2-yl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C2C=CC=CC2=CC=1)(=O)OC1=CC=CC=C1 JSJUBNHZCFKUKY-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 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
- 239000008188 pellet Substances 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 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
- 239000003381 stabilizer Substances 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、長期耐熱性に優れたゴム変性ポリスチレン系樹脂組成物および成形体に関するものである。 The present invention relates to a rubber-modified polystyrene resin composition and a molded article excellent in long-term heat resistance.
スチレン系樹脂はその特性を生かし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させた難燃樹脂組成物はワープロ、パーソナルコンピュータ、プリンター、複写機等のＯＡ機器、ＴＶ、ＶＴＲ、オーディオ等の家電製品等を初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. Among them, flame retardant resin compositions imparted with a high degree of flame retardancy are used in various fields including office automation equipment such as word processors, personal computers, printers and copiers, and home appliances such as TVs, VTRs and audios. ing.
長期耐熱性に優れたＯＡ機器・家電製品等の分野では、長期間に渡りある程度の熱履歴を受ける用途について、ＡＢＳ樹脂（アクリロニトリル−ブタジエン−スチレン樹脂）やＰＣ／ＡＢＳ樹脂（ポリカーボネート樹脂とＡＢＳ樹脂のポリマーアロイ）が採用されている（特開２０００−２６７１３号公報）。しかし近年は低コスト化の要求から、スチレン系難燃樹脂がこれらの樹脂に代わり採用される様になってきた。それに伴い、ゴム変性ポリスチレン系難燃樹脂組成物においても、フェノール系酸化防止剤を配合し長期間に渡り熱履歴を受ける用途で使用できるよう改良がはかられている（特開２０１２−５７００９号公報）。 In the field of OA equipment and home appliances with excellent long-term heat resistance, ABS resin (acrylonitrile-butadiene-styrene resin) and PC / ABS resin (polycarbonate resin and ABS resin) are used for applications that receive a certain degree of thermal history over a long period of time. (Polymer alloy of No. 2000-26713) is employed. However, in recent years, styrenic flame retardant resins have come to be used instead of these resins due to the demand for cost reduction. Accordingly, the rubber-modified polystyrene-based flame retardant resin composition has been improved so that it can be used in applications where a phenolic antioxidant is blended to receive a heat history over a long period of time (Japanese Patent Laid-Open No. 2012-57009). Publication).
ＯＡ機器や液晶テレビの内部部品や外装材等の用途、特に液晶テレビの外装材では、通常カーボンブラックを用いて黒色に着色するが、デザイン等の理由でベンガラや酸化チタン等を用いて黒色以外の色の需要が高まっている。 Applications such as internal parts and exterior materials for office automation equipment and liquid crystal televisions, especially exterior materials for liquid crystal televisions, are usually colored black using carbon black, but other than black using bengara or titanium oxide for design reasons The demand for colors is increasing.
しかしながら、ベンガラを単独使用した場合は無論のこと、例えばカーボンブラックの他にベンガラを使用してグレーなどに調色した場合、長期間に渡り熱履歴を受けた際、長期耐熱性が悪化する。ゴム変性ポリスチレン系樹脂にフェノール系酸化防止剤を配合しただけでは機械的性質、特にシャルピー強度の保持率および引張歪の保持率が必ずしも満足させるものではない場合が見られ、改良が要求されている。 However, when Bengala is used alone, it goes without saying, for example, when Bengala is used in addition to carbon black and the color is adjusted to gray or the like, the long-term heat resistance deteriorates when it receives a heat history over a long period of time. There are cases where mechanical properties, especially Charpy strength retention and tensile strain retention, are not always satisfied by adding a phenolic antioxidant to a rubber-modified polystyrene resin, and improvements are required. .
本発明は、この様な現状を鑑み、ベンガラを着色剤として使用した場合の上記の問題点を解決し、長期耐熱性に優れたゴム変性ポリスチレン系樹脂組成物を提供することにある。 In view of such a current situation, an object of the present invention is to provide a rubber-modified polystyrene-based resin composition that solves the above-described problems when Bengala is used as a colorant and has excellent long-term heat resistance.
本発明者は、上記課題について鋭意検討した結果、ゴム変性ポリスチレン系樹脂に、着色剤として特定のベンガラを添加する事によって本発明を完成させた。 As a result of intensive studies on the above problems, the present inventor has completed the present invention by adding specific bengara as a colorant to the rubber-modified polystyrene resin.
すなわち、本発明は以下のとおりである。
１．（Ａ）ゴム変性ポリスチレン系樹脂１００質量部に対して、（Ｂ）ベンガラ０．１〜１．０質量部を着色剤として含有し、使用するベンガラ成分の酸化第二鉄の純度が９５％以上であることを特徴とするゴム変性ポリスチレン系樹脂組成物。
２．請求項１に記載のゴム変性ポリスチレン系樹脂組成物に（Ｃ）難燃剤が、含まれるゴム変性ポリスチレン系難燃性樹脂組成物。
３．請求項２に記載のゴム変性ポリスチレン系難燃性樹脂組成物に（Ｄ）難燃助剤が、含まれるゴム変性ポリスチレン系難燃性樹脂組成物。
４．請求項２若しくは３に記載のゴム変性ポリスチレン系難燃性樹脂組成物の（Ｃ）難燃剤が、臭素系難燃剤であるゴム変性ポリスチレン系難燃性樹脂組成物。
５．請求項２から請求項４のいずれか１項に記載のゴム変性ポリスチレン系難燃性樹脂組成物の（Ｃ）難燃剤が、２，４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジンであるゴム変性ポリスチレン系難燃性樹脂組成物。
６．請求項１から請求項５のいずれか１項に記載のゴム変性ポリスチレン系樹脂組成物若しくはゴム変性ポリスチレン系難燃性樹脂組成物から得られる成形体。
That is, the present invention is as follows.
1. (A) 100 parts by mass of rubber-modified polystyrene resin, (B) 0.1 to 1.0 part by mass of Bengala is contained as a colorant, and the purity of ferric oxide of the Bengala component used is 95% or more. A rubber-modified polystyrene resin composition characterized in that
2. A rubber-modified polystyrene-based flame retardant resin composition comprising (C) a flame retardant in the rubber-modified polystyrene-based resin composition according to claim 1.
3. Rubber-modified polystyrene-based flame retardant in the resin composition (D) a flame retardant agent, a rubber-modified polystyrene-based flame retardant resin composition contained in claim 2.
4). A rubber-modified polystyrene-based flame retardant resin composition in which the (C) flame retardant of the rubber-modified polystyrene-based flame retardant resin composition according to claim 2 or 3 is a bromine-based flame retardant.
5. The rubber-modified polystyrene flame-retardant resin composition (C) flame retardant according to any one of claims 2 to 4, wherein 2,4,6-tris (2,4,6-tribromophenoxy) is used. ) A rubber-modified polystyrene-based flame retardant resin composition which is 1,3,5-triazine.
6). A molded product obtained from the rubber-modified polystyrene resin composition or the rubber-modified polystyrene flame-retardant resin composition according to any one of claims 1 to 5.
本発明により、通常、ゴム変性ポリスチレン系樹脂に、ベンガラを用いると長期耐熱性が低下するが、特定のベンガラを使用することによって、この樹脂組成物の長期耐熱性低下を抑えることができる。特に長期間に渡り熱履歴を受けた際のシャルピー強度の保持率などの機械的強度に優れ、耐久性が大幅に向上し、ＯＡ機器や液晶テレビの内部部品や外装材等の、長期間に渡り熱履歴を受ける用途での使用が有利になる。 According to the present invention, the long-term heat resistance of the rubber-modified polystyrene-based resin is usually reduced when long-term heat resistance is used. However, the long-term heat resistance of the resin composition can be suppressed by using a specific bengara. In particular, it has excellent mechanical strength such as the retention rate of Charpy strength when subjected to heat history over a long period of time, greatly improves durability, and is used for a long period of time such as internal parts and exterior materials of OA equipment and LCD TVs. It is advantageous to use in applications that receive a transitional heat history.
本発明の（Ａ）ゴム変性ポリスチレン系樹脂としては、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。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重合体がある。なお、重合体は重合法には限定されるものではない。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) rubber-modified polystyrene resin of the present invention refers to a polymer in which a rubber-like polymer is dispersed in the form of particles in an aromatic vinyl polymer matrix. For example, there is a polymer obtained 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. The polymer is not limited to the polymerization method. 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. .
マトリックス部分の分子量については特に制限ないが、還元粘度(ηsp／Ｃ)で０．５０以上、好ましくは０．５５〜１．００である。１．００を超えると、樹脂組成物とした際の流動性が低く過ぎて成形に支障をきたし、０．５０未満だと実用的に十分な強度が発揮できない等の問題がある。また、（Ａ）ゴム変性ポリスチレン系樹脂としては、ゴム状重合体の含有量は３．５〜１０質量％が適当である。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、一般的には０．４〜６．０μｍが適当である。 Although there is no restriction | limiting in particular about the molecular weight of a matrix part, It is 0.50 or more in reduced viscosity ((eta) sp / C), Preferably it is 0.55-1.00. If it exceeds 1.00, the fluidity at the time of preparing the resin composition is too low, which hinders molding, and if it is less than 0.50, there is a problem that practically sufficient strength cannot be exhibited. As the rubber-modified polystyrene resin (A), the rubbery polymer content is suitably 3.5 to 10% by mass. Although there is no restriction | limiting in particular about the average particle diameter of a rubber-like polymer, Generally 0.4-6.0 micrometers is suitable.
上記の芳香族ビニル単量体としては、主にスチレンである。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−ジメチルスチレン等が挙げられるが、スチレンが最も好適である。また、これらの単量体から２種以上を併用して使用することも出来る。 The aromatic vinyl monomer is mainly styrene. Although o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene and the like can be mentioned, styrene is most preferable. Two or more of these monomers can be used in combination.
上記のゴム状重合体としては、ポリブタジエン、ポリイソプレン、スチレン−ブタジエン共重合体等であり、ポリブタジエンとしてはシス結合の含有量が高いハイシスポリブタジエン、シス結合の含有量が低いローシスポリブタジエン等が挙げられる。用いられるゴム状重合体については特に制限はないが、中でも使用されるゴム状重合体として、シス−１、４結合を９０モル％以上有するハイシスポリブタジエンゴムをゴム状重合体１００質量％中７０質量％以上含有するポリブタジエンが好ましく使用される。具体的には、ハイシスポリブタジエンゴムを単独使用して得られるゴム変性スチレン系樹脂でも、ハイシスポリブタジエンゴムとローシスポリブタジエンゴムを混合使用して得られるゴム変性スチレン系樹脂でも、又はハイシスポリブタジエンゴムを使用して得られたゴム変性スチレン系樹脂とローシスポリブタジエンゴムを使用して得られるゴム変性スチレン系樹脂の混合物においても、これらいずれのゴム変性スチレン系樹脂中に存在するゴム状重合体１００質量％中にシス−１、４結合を９０モル％以上有するハイシスポリブタジエンゴムに依存するゴム状重合体を７０質量％以上含有することが好ましい。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１０〜４０モル％であるポリブタジエンゴムを意味する。 Examples of the rubbery polymer include polybutadiene, polyisoprene, and styrene-butadiene copolymer. Examples of the polybutadiene include high cis polybutadiene having a high cis bond content and low cis polybutadiene having a low cis bond content. Can be mentioned. The rubbery polymer to be used is not particularly limited, but as the rubbery polymer to be used, a high-cis polybutadiene rubber having 90 mol% or more of cis-1,4 bonds is used in 70% by mass of the rubbery polymer. Polybutadiene containing at least mass% is preferably used. Specifically, a rubber-modified styrene resin obtained by using a high-cis polybutadiene rubber alone, a rubber-modified styrene resin obtained by using a mixture of a high-cis polybutadiene rubber and a low-cis polybutadiene rubber, or a high-cis polybutadiene. In a mixture of a rubber-modified styrene resin obtained by using rubber and a rubber-modified styrene resin obtained by using low-cis polybutadiene rubber, a rubbery polymer present in any of these rubber-modified styrene resins. It is preferable to contain 70% by mass or more of a rubbery polymer depending on a high-cis polybutadiene rubber having 90% by mol or more of cis-1,4 bonds in 100% by mass. 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 10 to 40 mol%.
本発明で用いる（Ｂ）ベンガラは、成分の酸化第二鉄の純度が９５％以上であるベンガラを使用する。好ましくは、酸化第二鉄の純度が９７％以上であるベンガラを使用する。但し、樹脂との親和性、分散性を改善するために用いる分散材は含んでもよい。添加量は（Ａ）ゴム変性ポリスチレン系樹脂１００質量部に対して、（Ｂ）ベンガラ０．１〜１．０質量部である。好ましくは０．１〜０．５質量部である。１．０質量部を超えると衝撃強度が損なわれるうえに経済的にも不利である。尚、本発明の組成物で使用する着色剤は、上述のベンガラの他に公知のものを必要に応じて使用しても良い。例えばカーボンブラック等の有機系顔料、酸化チタン等の無機系顔料の他、有機系染料などがある。 As the (B) bengara used in the present invention, a bengara in which the purity of the component ferric oxide is 95% or more is used. Preferably, a bengara whose ferric oxide purity is 97% or more is used. However, a dispersing material used for improving the affinity and dispersibility with the resin may be included. The added amount is 0.1 to 1.0 part by mass of (B) Bengala with respect to 100 parts by mass of (A) rubber-modified polystyrene resin. Preferably it is 0.1-0.5 mass part. If the amount exceeds 1.0 parts by mass, the impact strength is impaired, and it is economically disadvantageous. The colorant used in the composition of the present invention may be a known colorant as required in addition to the above-mentioned bengara. For example, there are organic dyes such as organic pigments such as carbon black, inorganic pigments such as titanium oxide, and the like.
本発明で用いる（Ｃ）難燃剤は、臭素系難燃剤としては、この分野で一般的に使用されるもので、例えばテトラブロモビスフェノールＡ、テトラブロモビスフェノールＡの誘導体、デカブロモジフェニルエーテル、エチレンビステトラブロモフタルイミド、ヘキサブロモシクロドデカン、１,２−ビス（ペンタブロモフェニル）エタン、ビス（２,４,６−トリブロモフェノキシ）エタン、２,４,６−トリス（２,４,６−トリブロモフェニル）−１,３,５−トリアジン等が挙げられる。この中で、２,４,６−トリス（２,４,６−トリブロモフェニル）−１,３,５−トリアジンが好ましく使用される。
リン系難燃剤としては、赤リン、有機リン酸エステル化合物、ホスファゼン化合物、ホスフィン酸塩類、ホスフォン酸塩類、ホスホルアミド化合物等が挙げられ、有機リン酸エステル化合物、ホスファゼン化合物が好ましく、有機リン酸エステル化合物がより好ましい。
有機リン酸エステル化合物としては、例えば、トリフェニルフォスフェート、フェニルビスドデシルホスフェート、フェニルビスネオペンチルホスフェート、フェニル−ビス（３，５，５’−トリメチル−ヘキシルホスフェート）、エチルジフェニルホスフェート、２−エチル−ヘキシルジ（ｐ−トリル）ホスフェート、ビス−（２−エチルヘキシル）ｐ−トリルホスフェート、トリトリルホスフェート、ビス−（２−エチルヘキシル）フェニルホスフェート、トリ−（ノニルフェニル）ホスフェート、ジ（ドデシル）ｐ−トリルホスフェート、トリクレジルホスフェート、ジブチルフェニルホスフェート、２−クロロエチルジフェニルホスフェート、ｐ−トリルビス（２，５，５’−トリメチルヘキシル）ホスフェート、２−エチルヘキシルジフェニルホスフェート、ビスフェノールＡ・ビス（ジフェニルホスフェート）、ジフェニル−（３−ヒドロキシフェニル）ホスフェート、ビスフェノールＡ・ビス（ジクレジルホスフェート）、レゾルシン・ビス（ジフェニルホスフェート）、レゾルシン・ビス（ジキシレニルホスフェート）、２−ナフチルジフェニルフォスフェート、１−ナフチルジフェニルフォスフェート、ジ（２−ナフチル）フェニルホスフェート等が挙げられる。
The flame retardant (C) used in the present invention is one generally used in this field as a brominated flame retardant. For example, tetrabromobisphenol A, tetrabromobisphenol A derivatives, decabromodiphenyl ether, ethylene bistetra Bromophthalimide, hexabromocyclododecane, 1,2-bis (pentabromophenyl) ethane, bis (2,4,6-tribromophenoxy) ethane, 2,4,6-tris (2,4,6-tribromo Phenyl) -1,3,5-triazine and the like. Among these, 2,4,6-tris (2,4,6-tribromophenyl) -1,3,5-triazine is preferably used.
Examples of phosphorus-based flame retardants include red phosphorus, organophosphate compounds, phosphazene compounds, phosphinates, phosphonates, phosphoramide compounds, and the like, and organic phosphate compounds and phosphazene compounds are preferred, and organic phosphate compounds Is more preferable.
Examples of the organic phosphate compound include triphenyl phosphate, phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenyl-bis (3,5,5′-trimethyl-hexyl phosphate), ethyl diphenyl phosphate, 2-ethyl -Hexyl di (p-tolyl) phosphate, bis- (2-ethylhexyl) p-tolyl phosphate, tolyl phosphate, bis- (2-ethylhexyl) phenyl phosphate, tri- (nonylphenyl) phosphate, di (dodecyl) p-tolyl Phosphate, tricresyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis (2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl Phenyl phosphate, bisphenol A bis (diphenyl phosphate), diphenyl- (3-hydroxyphenyl) phosphate, bisphenol A bis (dicresyl phosphate), resorcin bis (diphenyl phosphate), resorcin bis (dixylenyl phosphate), Examples include 2-naphthyl diphenyl phosphate, 1-naphthyl diphenyl phosphate, di (2-naphthyl) phenyl phosphate, and the like.
本発明では（Ｄ）難燃助剤を用いる。難燃助剤としては例えば酸化アンチモンとして三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、アンチモン酸ソーダ等、ホウ素系化合物としてホウ酸亜鉛、メタホウ酸バリウム、無水ホウ酸亜鉛、無水ホウ酸等、スズ系化合物としてスズ酸亜鉛、ヒドロキシスズ酸亜鉛等、モリブデン系化合物として酸化モリブデン、モリブデン酸アンモニウム等、ジルコニウム系化合物として酸化ジルコニウム、水酸化ジルコニウム等、また亜鉛系化合物として硫化亜鉛等が挙げられるが、なかでも三酸化アンチモンを使用することが特に好ましい。 In the present invention, (D) a flame retardant aid is used. Examples of flame retardant aids include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, etc. as antimony oxide, zinc borate, barium metaborate, anhydrous zinc borate, anhydrous boric acid, etc. as boron compounds, tin Zinc stannate, zinc hydroxystannate, etc. as a system compound, molybdenum oxide, ammonium molybdate, etc. as a molybdenum compound, zirconium oxide, zirconium hydroxide, etc. as a zirconium compound, and zinc sulfide as a zinc compound, Among them, it is particularly preferable to use antimony trioxide.
本発明の目的を損なわない範囲で他の添加剤、例えば可塑剤、滑剤、安定剤、酸化防止剤、紫外線吸収剤、充填剤、補強剤等を添加することが出来る。 Other additives such as plasticizers, lubricants, stabilizers, antioxidants, ultraviolet absorbers, fillers, reinforcing agents and the like can be added as long as the object of the present invention is not impaired.
本発明のスチレン系難燃性樹脂組成物の混合方法は、公知の混合技術を適用することが出来る。例えばミキサー型混合機、Ｖ型ブレンダー、及びタンブラー型混合機等の混合装置であらかじめ混合しておいた混合物を、更に溶融混練することで均一な難燃性樹脂組成物とすることが出来る。溶融混練にも特に制限はなく公知の溶融技術を適用出来る。好適な溶融混練装置として、バンバリー型ミキサー、ニーダー、ロール、単軸押出機、特殊単軸押出機、及び二軸押出機等がある。更に押出機等の溶融混練装置の途中から難燃剤等の添加剤を別途に添加する方法がある。 A known mixing technique can be applied to the method for mixing the styrene-based flame retardant resin composition of the present invention. For example, a uniform flame-retardant resin composition can be obtained by further melt-kneading a mixture previously mixed with a mixing apparatus such as a mixer-type mixer, a V-type blender, and a tumbler-type mixer. There is no particular limitation on melt kneading, and a known melting technique can be applied. Suitable melt kneaders include Banbury mixers, kneaders, rolls, single screw extruders, special single screw extruders, and twin screw extruders. Furthermore, there is a method of separately adding an additive such as a flame retardant from the middle of a melt-kneading apparatus such as an extruder.
以下に例を挙げて具体的に本発明を説明するが、本発明はこれらの例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.
実施例及び比較例で使用した（Ａ）ゴム変性ポリスチレン系樹脂には、マトリックス部分のポリスチレンの還元粘度０．６８ｄｌ／ｇ、ゴム状重合体含有量７．１質量％の組成であるものを作成して使用した。 (A) Rubber-modified polystyrene resin used in Examples and Comparative Examples is prepared with a composition having a reduced viscosity of 0.68 dl / g of polystyrene in the matrix portion and a rubbery polymer content of 7.1% by mass. Used.
ゴム変性ポリスチレン樹脂の還元粘度（ηｓｐ／Ｃ）の測定は、上記で得たゴム変性ポリスチレン樹脂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後、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０．４％（質量／体積）の試料溶液を作製した。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
The reduced viscosity (ηsp / C) of the rubber-modified polystyrene resin was measured by adding a mixed solvent of 15 ml of methyl ethyl ketone and 15 ml of acetone to 1 g of the rubber-modified polystyrene resin obtained above, and dissolving by shaking for 2 hours at a temperature of 25 ° C. The insoluble matter was settled by separation, 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
ゴム状重合体含有量の測定は、ゴム変性スチレン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時間放置後、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。 The rubber-like polymer content was measured by dissolving a rubber-modified styrene resin in chloroform, adding a certain amount of iodine monochloride / carbon tetrachloride solution and leaving it in the dark for about 1 hour, and then measuring 15% (mass / volume). Potassium iodide solution and 50 ml of pure water were added, and excess iodine monochloride was titrated with 0.1N sodium thiosulfate / ethanol aqueous solution, and calculated from the amount of iodine monochloride added.
（Ｂ）ベンガラ：（Ｂ−１）ベンガラＡとしてベンガラ成分の酸化第二鉄の純度が９７％であるベンガラを使用、（Ｂ−２）ベンガラＢとしてベンガラ成分の酸化第二鉄の純度が８９％であるベンガラを使用した。 (B) Bengala: (B-1) Bengala having a purity of 97% ferric oxide as the Bengala A is used as the Bengala A, and (B-2) Bengala B having a ferric oxide purity of 89% as the Bengala B % Bengara was used.
使用するベンガラ中の酸化第二鉄の含有量は、試料を灰化後、酸分解処理を行い、パーキンエルマー社製ＩＣＰ発光分析装置（Ｏｐｔｉｍａ４３００ＤＶ）で鉄含有量を測定し、鉄及び酸化第二鉄の原子量比から計算して求めた。 The ferric oxide content in the bengara used is ashed and then acid-decomposed, and the iron content is measured with a Perkin Elmer ICP emission analyzer (Optima 4300 DV). Calculated from the atomic weight ratio of iron.
（Ｃ）難燃剤には、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。 (C) As a flame retardant, a trade name Piroguard SR245 manufactured by Daiichi Kogyo Seiyaku Co., Ltd., which is 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine, was used. .
（Ｄ）難燃助剤：商品名ＡＴ−３ＣＮ（鈴裕化学社製、三酸化アンチモン）を用いた。 (D) Flame retardant aid: Trade name AT-3CN (manufactured by Suzuhiro Chemical Co., Ltd., antimony trioxide) was used.
次に、本発明のゴム変性ポリスチレン系難燃性着色樹脂組成物の混合方法を述べる。（Ａ）ゴム変性ポリスチレン系樹脂、（Ｂ）ベンガラ、（Ｃ）難燃剤、（Ｄ）難燃助剤、を表１、２に示す配合量にて、これら全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、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、シリンダー温度２３０℃、供給量３０ｋｇ／時間とした。 Next, a method for mixing the rubber-modified polystyrene-based flame retardant colored resin composition of the present invention will be described. (A) Rubber-modified polystyrene resin, (B) Bengala, (C) Flame retardant, (D) Flame retardant auxiliary are blended in the amounts shown in Tables 1 and 2 and all these components are mixed into a Henschel mixer (Mitsui Miike Chemical). FM20B) and supplied to a twin-screw extruder (Toshiki Machine Co., Ltd., TEM26SS) to form a strand, which was cooled with water and led to a pelletizer to be pelletized. At this time, the cylinder temperature was 230 ° C. and the supply amount was 30 kg / hour.
なお、予備混合時に、カルシウムステアレート、ミネラルオイル、酸化防止剤、及び有機系着色剤も同時添加した。 At the time of preliminary mixing, calcium stearate, mineral oil, antioxidant, and organic colorant were also added at the same time.
実施例及び比較例に示し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.
得られたペレットを温度７０℃×３時間で加熱乾燥後、射出成形機（日本製鋼所（株）製、Ｊ１００Ｅ−Ｐ）にて、ＪＩＳ Ｋ ７１３９に記載のＡ型試験片（ダンベル）を成形した。この際、シリンダー温度２０５℃、金型温度４５℃とした。得られたダンベル試験片にてシャルピー衝撃強度を測定した。尚、シャルピー試験片は、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。 The obtained pellets were dried by heating at a temperature of 70 ° C. for 3 hours, and then an A-type test piece (dumbbell) described in JIS K 7139 was molded by an injection molding machine (manufactured by Nippon Steel Works, Ltd., J100E-P). did. At this time, the cylinder temperature was 205 ° C. and the mold temperature was 45 ° C. The Charpy impact strength was measured with the obtained dumbbell specimen. In addition, the Charpy test piece was cut out from the center part of the dumbbell piece, and a notch (type A, r = 0.25 mm) was formed by cutting and used for the test.
（加熱試験）
シャルピー片を、ＪＩＳ Ｋ ７２１２のギアーオーブンを用いて７０℃で加熱し、２０００時間後に取り出して物性を測定し、別途測定した加熱前の物性値に対する割合を百分率で求め、保持率とした。保持率７０％以上であれば合格である。なおシャルピー衝撃強度はＪＩＳ Ｋ ７１１１−１に基づき測定を行った。
(Heating test)
The Charpy pieces were heated at 70 ° C. using a gear oven of JIS K 7212, taken out after 2000 hours, measured for physical properties, and determined as a percentage of the separately measured physical property values before heating. If the retention rate is 70% or more, it is acceptable. The Charpy impact strength was measured based on JIS K 7111-1.
実施例１〜４、比較例１〜６の各配合及び結果を表１、２に示す。 Tables 1 and 2 show the respective formulations and results of Examples 1 to 4 and Comparative Examples 1 to 6.
表１の実施例に示したとおり、本願発明の組成及び規定量を満たすことによって長期間に渡り熱履歴を受けた際でもシャルピー強度の保持率が優れていることがわかる。 As shown in the Examples of Table 1, it can be seen that the Charpy strength retention is excellent even when subjected to a heat history over a long period of time by satisfying the composition and specified amount of the present invention.
しかし本発明の規定を満足しない比較例で得られたゴム変性ポリスチレン系樹脂組成物若しくはゴム変性ポリスチレン系難燃性樹脂組成物では、シャルピー強度の保持率が低下していることがわかる。 However, it can be seen that in the rubber-modified polystyrene resin composition or the rubber-modified polystyrene flame-retardant resin composition obtained in the comparative example not satisfying the provisions of the present invention, the Charpy strength retention rate is lowered.
例えば、ベンガラ成分の酸化第二鉄の純度が８９％であるベンガラを使用するとシャルピー強度の保持率が低下している（比較例１、２、５、６）。 For example, when Bengala having a purity of 89% ferric oxide as a Bengala component is used, the Charpy strength retention rate is reduced (Comparative Examples 1, 2, 5, and 6).
ベンガラ成分の酸化第二鉄の純度が９７％であるベンガラを使用しても添加量が１．０質量部以上では、シャルピー強度の保持率が低下している（比較例３、４）。 Even when Bengala having a purity of 97% ferric oxide as a Bengala component is used, the retention rate of Charpy strength is reduced when the addition amount is 1.0 part by mass or more (Comparative Examples 3 and 4).
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