JP4196862B2 - Flame retardant, flame retardant resin composition - Google Patents
Flame retardant, flame retardant resin composition Download PDFInfo
- Publication number
- JP4196862B2 JP4196862B2 JP2004085480A JP2004085480A JP4196862B2 JP 4196862 B2 JP4196862 B2 JP 4196862B2 JP 2004085480 A JP2004085480 A JP 2004085480A JP 2004085480 A JP2004085480 A JP 2004085480A JP 4196862 B2 JP4196862 B2 JP 4196862B2
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- JP
- Japan
- Prior art keywords
- flame retardant
- resin composition
- weight
- mol
- flame
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003063 flame retardant Substances 0.000 title claims description 251
- 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 232
- 239000011342 resin composition Substances 0.000 title claims description 70
- 239000011347 resin Substances 0.000 claims description 104
- 229920005989 resin Polymers 0.000 claims description 104
- 125000003118 aryl group Chemical group 0.000 claims description 97
- 229920000642 polymer Polymers 0.000 claims description 84
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 53
- 239000004417 polycarbonate Substances 0.000 claims description 44
- 229920000515 polycarbonate Polymers 0.000 claims description 44
- -1 polyethylene terephthalate Polymers 0.000 claims description 40
- 101100323621 Drosophila melanogaster Drip gene Proteins 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 21
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 20
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 20
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 14
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 13
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 12
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 12
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 229920005669 high impact polystyrene Polymers 0.000 claims description 10
- 239000004797 high-impact polystyrene Substances 0.000 claims description 10
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 7
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 7
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 53
- 239000000956 alloy Substances 0.000 description 29
- 229910045601 alloy Inorganic materials 0.000 description 29
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 22
- 239000004810 polytetrafluoroethylene Substances 0.000 description 22
- 239000002243 precursor Substances 0.000 description 22
- 238000002485 combustion reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000004626 polylactic acid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 229920000747 poly(lactic acid) Polymers 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910003475 inorganic filler Inorganic materials 0.000 description 6
- 239000011256 inorganic filler Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical class C1=CN=NN=C1 JYEUMXHLPRZUAT-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
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-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
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- GDYRRZUXJQFSIM-UHFFFAOYSA-N 2,2-dimethylpropyl methyl hydrogen phosphate Chemical compound COP(O)(=O)OCC(C)(C)C GDYRRZUXJQFSIM-UHFFFAOYSA-N 0.000 description 1
- COCTZVNXBOTULM-UHFFFAOYSA-N 2,2-dimethylpropyl phenyl hydrogen phosphate Chemical compound CC(C)(C)COP(O)(=O)OC1=CC=CC=C1 COCTZVNXBOTULM-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NXIFLHKNGSUALF-UHFFFAOYSA-N 2-[(2,3-dibromo-4-methylphenoxy)methyl]oxirane Chemical compound BrC1=C(Br)C(C)=CC=C1OCC1OC1 NXIFLHKNGSUALF-UHFFFAOYSA-N 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- DTXOROCKOGNREW-UHFFFAOYSA-N 3-ethylbenzene-1,2-diol;phosphoric acid Chemical compound OP(O)(O)=O.CCC1=CC=CC(O)=C1O DTXOROCKOGNREW-UHFFFAOYSA-N 0.000 description 1
- DWTILULHYBVBME-UHFFFAOYSA-N 3-phenylbenzene-1,2-diol;phosphorous acid Chemical compound OP(O)O.OC1=CC=CC(C=2C=CC=CC=2)=C1O DWTILULHYBVBME-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- YAAQEISEHDUIFO-UHFFFAOYSA-N C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 Chemical compound C=CC#N.OC(=O)C=CC=CC1=CC=CC=C1 YAAQEISEHDUIFO-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JKABQGPYSRNZDY-UHFFFAOYSA-N ClC1(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl Chemical compound ClC1(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl JKABQGPYSRNZDY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 239000004593 Epoxy Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
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- TZZPHXHCQVXYOM-UHFFFAOYSA-N O(P(OC1=CC=CC=C1)(=O)OP(=O)(O)OCC(CO)(CO)CO)C1=CC=CC=C1 Chemical compound O(P(OC1=CC=CC=C1)(=O)OP(=O)(O)OCC(CO)(CO)CO)C1=CC=CC=C1 TZZPHXHCQVXYOM-UHFFFAOYSA-N 0.000 description 1
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- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
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- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- AVLFIQVWFQCVPP-UHFFFAOYSA-N diethyl [hydroxy-[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]phosphoryl] phosphate Chemical compound O(P(OCC)(=O)OP(=O)(O)OCC(CO)(CO)CO)CC AVLFIQVWFQCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 210000004251 human milk Anatomy 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical class OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical class NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-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
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical class OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000026683 transduction Effects 0.000 description 1
- 238000010361 transduction Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-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
- VRRIVXLVXXAHJA-UHFFFAOYSA-N tris(2,3,4-tribromophenyl) phosphate Chemical compound BrC1=C(Br)C(Br)=CC=C1OP(=O)(OC=1C(=C(Br)C(Br)=CC=1)Br)OC1=CC=C(Br)C(Br)=C1Br VRRIVXLVXXAHJA-UHFFFAOYSA-N 0.000 description 1
- FFULTTXGZNPTQO-UHFFFAOYSA-N tris(2-bromoethyl) phosphate Chemical compound BrCCOP(=O)(OCCBr)OCCBr FFULTTXGZNPTQO-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-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
- 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 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PZRXQXJGIQEYOG-UHFFFAOYSA-N zinc;oxido(oxo)borane Chemical compound [Zn+2].[O-]B=O.[O-]B=O PZRXQXJGIQEYOG-UHFFFAOYSA-N 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
- 229910000568 zirconium hydride Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Fireproofing Substances (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、樹脂組成物に対して難燃性を付与する難燃剤、この難燃剤を含有する難燃性樹脂組成物に関する。 The present invention relates to a flame retardant that imparts flame retardancy to a resin composition, and a flame retardant resin composition containing the flame retardant.
近年、樹脂組成物に対して難燃性を付与する樹脂用難燃剤としては、例えば金属水酸化物系（水酸化マグネシウム、水酸化アルミニウム）難燃剤、珪素系（シリコーン、シリカ）難燃剤、ハロゲン（臭素）系難燃剤、リン系（燐酸エステル、赤燐等）難燃剤、等を挙げることができる。 In recent years, flame retardants for resins that impart flame retardancy to resin compositions include, for example, metal hydroxide (magnesium hydroxide, aluminum hydroxide) flame retardant, silicon (silicone, silica) flame retardant, halogen Examples thereof include (bromine) -based flame retardants and phosphorus-based (phosphate esters, red phosphorus, etc.) flame retardants.
そして、金属水酸化物系難燃剤は、樹脂中に添加量が多くなるため樹脂の機械的特性を損ねるといった不具合や、珪素系難燃剤は、適用可能な樹脂組成物が限られるといった不具合等がある。また、ハロゲン系難燃剤は、動物や母乳から検出されたり、燃焼時に臭素系ダイオキシン等が発生したりする等といった不具合が生じる虞があることから使用量が減少傾向にある。 In addition, the metal hydroxide flame retardant has a problem that the amount of addition in the resin is increased, so that the mechanical properties of the resin are impaired, and the silicon flame retardant has a problem that the applicable resin composition is limited. is there. In addition, halogen flame retardants tend to be used in a reduced amount because there is a risk that they may be detected from animals or breast milk or brominated dioxins may be generated during combustion.
そこで、これらの難燃剤の代替として現在注目されているのがリン系難燃剤である。しかしながら、このリン系難燃剤は、樹脂組成物を射出成形する時にガスを発生させたり、樹脂組成物の耐熱性を低下させたりする等といった問題を有している。 Therefore, phosphorus-based flame retardants are currently attracting attention as an alternative to these flame retardants. However, this phosphorus-based flame retardant has problems such as generating gas when the resin composition is injection-molded and reducing the heat resistance of the resin composition.
また、例えば樹脂組成物としてポリカーボネート樹脂を用いた場合については、金属塩タイプの難燃剤であるポリスチレンスルホン酸塩型の樹脂用難燃剤が提案されている（特許文献１、特許文献２及び特許文献３を参照。）。 For example, when a polycarbonate resin is used as the resin composition, a polystyrene sulfonate type flame retardant for resin, which is a metal salt type flame retardant, has been proposed (Patent Document 1, Patent Document 2 and Patent Document). 3).
しかしながら、これらの提案では、適用可能な樹脂組成物がポリカーボネート樹脂に限定されることや、難燃効果が不十分であることや、樹脂組成物に略均一に分散されない、いわゆる相溶性に乏しい等といった問題があり、さらに難燃効果に優れる樹脂用難燃剤が望まれている。 However, in these proposals, the applicable resin composition is limited to polycarbonate resin, the flame-retardant effect is insufficient, the resin composition is not substantially uniformly dispersed, so-called poor compatibility, etc. In addition, there is a demand for a flame retardant for resin that is further excellent in flame retardant effect.
特に、特許文献３で提案されている樹脂用難燃剤は、水を吸着し易いアミド基やカルボキシル基等を有しており、含有された樹脂組成物を長時間保存すると変色して外観を損なわせたり、樹脂自体が脆くなる、いわゆる機械的強度が低下したりするといった問題が生じる虞がある。 In particular, the flame retardant for resin proposed in Patent Document 3 has an amide group, a carboxyl group or the like that easily adsorbs water, and discolors when the stored resin composition is stored for a long period of time, thereby impairing the appearance. Or the resin itself becomes brittle, so-called mechanical strength may decrease.
本発明は、樹脂組成物に対する相溶性に優れ、含有された樹脂組成物を長期保存しても外観不良や機械的強度の低下が起こることを抑制できる難燃剤、難燃性樹脂組成物を提供するものである。 The present invention provides a flame retardant and a flame retardant resin composition that are excellent in compatibility with a resin composition and can suppress the occurrence of poor appearance and a decrease in mechanical strength even when the contained resin composition is stored for a long period of time. To do.
上述した問題を解決するために、発明者らは、鋭意検討を重ねた結果、所定量の芳香族ポリマーに、所定量のスルホン酸基及び／又はスルホン酸塩基が導入されているものが樹脂用難燃剤として優れていることを見出し、本発明を完成させるに至った。 In order to solve the above-mentioned problems, the inventors have conducted intensive studies. As a result, a resin in which a predetermined amount of a sulfonic acid group and / or a sulfonic acid group is introduced into a predetermined amount of an aromatic polymer is used for a resin. It has been found that it is excellent as a flame retardant, and the present invention has been completed.
すなわち、本発明に係る難燃剤は、樹脂組成物に含有させることで当該樹脂組成物に難燃性を付与し、芳香族骨格を有するモノマー単位を１モル％〜１００モル％の範囲で含有する芳香族ポリマーを有し、この芳香族ポリマーにスルホン酸基及び／又はスルホン酸塩基が０．１モル％〜８．０モル％の範囲で導入されている。 That is, the flame retardant according to the present invention imparts flame retardancy to the resin composition by being contained in the resin composition, and contains a monomer unit having an aromatic skeleton in a range of 1 mol% to 100 mol%. It has aromatic polymer, sulfonic acid groups and / or sulfonate in the aromatic polymer that has been introduced in a range of 0.1 mol% to 8.0 mol%.
また、本発明に係る難燃性樹脂組成物は、樹脂組成物に難燃剤が含有されることで難燃性が付与され、難燃剤が、芳香族骨格を有するモノマー単位を１モル％〜１００モル％の範囲で含有する芳香族ポリマーを有し、この芳香族ポリマーにスルホン酸基及び／又はスルホン酸塩基が０．１モル％〜８．０モル％の範囲で導入されている。 Moreover, the flame retardant resin composition according to the present invention is imparted with flame retardancy by containing a flame retardant in the resin composition, and the flame retardant contains 1 mol% to 100 monomer units having an aromatic skeleton. It has aromatic polymer containing in the range of mole%, sulfonic acid group and / or sulfonate in the aromatic polymer that has been introduced in a range of 0.1 mol% to 8.0 mol%.
本発明によれば、スルホン酸基及び／又はスルホン酸塩基が所定量導入された芳香族ポリマーを難燃剤として用いることで、難燃性を適切に付与することが可能な樹脂組成物の種類を多くでき、樹脂組成物に難燃剤を略均一に分散させることが可能になる。 According to the present invention, by using an aromatic polymer into which a predetermined amount of a sulfonic acid group and / or a sulfonic acid group has been introduced as a flame retardant, the type of resin composition capable of appropriately imparting flame retardancy is provided. The flame retardant can be dispersed substantially uniformly in the resin composition.
また、本発明によれば、水分が３重量％未満のスルホン化剤でスルホン化処理することでスルホン酸基及び／又はスルホン酸塩基が導入された芳香族ポリマーを難燃剤として樹脂組成物に含有させることで、長期保存したときに外観不良や機械的強度の低下が起こることのない優れた難燃性樹脂組成物を得ることができる。 Further, according to the present invention, the resin composition contains, as a flame retardant, an aromatic polymer into which a sulfonic acid group and / or a sulfonic acid group has been introduced by sulfonation with a sulfonating agent having a moisture content of less than 3% by weight. As a result, an excellent flame-retardant resin composition that does not cause poor appearance or lower mechanical strength when stored for a long period of time can be obtained.
以下、本発明を適用した難燃剤、難燃性樹脂組成物について詳細に説明する。 Hereinafter, the flame retardant and the flame retardant resin composition to which the present invention is applied will be described in detail.
本発明を適用した難燃性樹脂組成物は、例えば家電製品や自動車製品、事務機器、文具、雑貨、建材、繊維等に用いられる樹脂材料であり、被難燃樹脂である樹脂組成物に難燃剤が含有されることで難燃性が付与されたものである。 The flame-retardant resin composition to which the present invention is applied is a resin material used for, for example, home appliances, automobile products, office equipment, stationery, miscellaneous goods, building materials, fibers, and the like. Flame retardance is imparted by the inclusion of a flame retardant.
難燃性樹脂組成物に含有される難燃剤は、芳香族骨格を有するモノマー単位を１モル％〜１００モル％の範囲で含有する芳香族ポリマーに、所定量のスルホン酸基及び／又はスルホン酸塩基が導入されたものである。そして、難燃剤に含有される芳香族ポリマーは、芳香族骨格を側鎖に有していても、主鎖に有していてもどちらでも良い。 The flame retardant contained in the flame retardant resin composition includes an aromatic polymer containing a monomer unit having an aromatic skeleton in a range of 1 mol% to 100 mol%, and a predetermined amount of sulfonic acid groups and / or sulfonic acid. A base is introduced. The aromatic polymer contained in the flame retardant may have an aromatic skeleton in the side chain or in the main chain.
具体的に、側鎖に芳香族骨格を有する芳香族ポリマーとしては、例えばポリスチレン（ＰＳ）、ハイインパクトポリスチレン（ＨＩＰＳ：スチレン−ブタジエン共重合体）、アクリロニトリル-スチレン共重合体（ＡＳ）、アクリロニトリル-ブタジエン-スチレン共重合体（ＡＢＳ）、アクリロニトリル-塩素化ポリエチレン-スチレン樹脂（ＡＣＳ）、アクリロニトリル-スチレン-アクリレート共重合体（ＡＳＡ）、アクリロニトリル-エチレンプロピレンゴム-スチレン共重合体（ＡＥＳ）、アクリロニトリル-エチレン-プロピレン-ジエン-スチレン樹脂（ＡＥＰＤＭＳ）等を挙げることができ、これらのうち何れか一種若しくは複数種を混合して用いることができる。 Specifically, examples of the aromatic polymer having an aromatic skeleton in the side chain include polystyrene (PS), high impact polystyrene (HIPS: styrene-butadiene copolymer), acrylonitrile-styrene copolymer (AS), and acrylonitrile. Butadiene-styrene copolymer (ABS), acrylonitrile-chlorinated polyethylene-styrene resin (ACS), acrylonitrile-styrene-acrylate copolymer (ASA), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES), acrylonitrile- An ethylene-propylene-diene-styrene resin (AEPDMS) can be used, and any one or a combination of these can be used.
そして、上述した側鎖に芳香族骨格を有する芳香族ポリマーの重量平均分子量は、１０,０００〜１０,０００,０００の範囲であり、好ましくは５０,０００〜１,０００,０００の範囲であり、さらに好ましくは１０,０００〜５００,０００の範囲である。 The weight average molecular weight of the aromatic polymer having an aromatic skeleton in the side chain described above is in the range of 10,000 to 10,000,000, preferably in the range of 50,000 to 1,000,000. More preferably, it is in the range of 10,000 to 500,000.
側鎖に芳香族骨格を有する芳香族ポリマーにおいては、重量平均分子量が１０,０００〜１０,０００,０００の範囲から外れる場合、被難燃樹脂に略均一に難燃剤を分散させることが困難、すなわち相溶性が低下し、難燃性樹脂組成物に対して適切に難燃性を付与することができなくなる。 In the aromatic polymer having an aromatic skeleton in the side chain, when the weight average molecular weight is out of the range of 10,000 to 10,000,000, it is difficult to disperse the flame retardant substantially uniformly in the flame retardant resin. That is, compatibility falls and it becomes impossible to give a flame retardance appropriately with respect to a flame-retardant resin composition.
また、主鎖に芳香族骨格を有する芳香族ポリマーとしては、例えばポリカーボネート（ＰＣ）、ポリフェニレンオキシド（ＰＰＯ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリスルホン（ＰＳＦ）等を挙げることができ、これらのうち何れか一種若しくは複数種を混合して用いることができる。また、これらの主鎖に芳香族骨格を有する芳香族ポリマーは、他の樹脂等を混合した混合物（アロイ）として用いてよい。具体的に、他の樹脂とのアロイとしては、例えばＡＢＳ/ＰＣアロイ、ＰＳ/ＰＣアロイ、ＡＳ/ＰＣアロイ、ＨＩＰＳ/ＰＣアロイ、ＰＥＴ/ＰＣアロイ、ＰＢＴ/ＰＣアロイ、ＰＶＣ/ＰＣアロイ、ＰＬＡ（ポリ乳酸）/ＰＣアロイ、ＰＰＯ/ＰＣアロイ、ＰＳ/ＰＰＯアロイ、ＨＩＰＳ/ＰＰＯアロイ、ＡＢＳ/ＰＥＴアロイ、ＰＥＴ/ＰＢＴアロイ等の少なくとも１種類以上を挙げることができる。 Examples of the aromatic polymer having an aromatic skeleton in the main chain include polycarbonate (PC), polyphenylene oxide (PPO), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polysulfone (PSF). Any one or a combination of these can be used. Moreover, you may use the aromatic polymer which has aromatic skeleton in these principal chains as a mixture (alloy) which mixed other resin etc. Specific examples of alloys with other resins include ABS / PC alloy, PS / PC alloy, AS / PC alloy, HIPS / PC alloy, PET / PC alloy, PBT / PC alloy, PVC / PC alloy, PLA. (Polylactic acid) / PC alloy, PPO / PC alloy, PS / PPO alloy, HIPS / PPO alloy, ABS / PET alloy, PET / PBT alloy, and the like.
芳香族ポリマーにおいて、芳香族骨格を有するモノマー単位の含有量は、１モル％〜１００モル％の範囲であり、好ましくは３０モル％〜１００モル％の範囲であり、さらに好ましくは４０モル％〜１００モル％である。 In the aromatic polymer, the content of the monomer unit having an aromatic skeleton is in the range of 1 mol% to 100 mol%, preferably in the range of 30 mol% to 100 mol%, more preferably from 40 mol% to 100 mol%.
芳香族骨格を有するモノマー単位が１モル％より少ないと、被難燃樹脂に難燃剤を略均一に分散させることが困難になったり、芳香族ポリマーに対するスルホン酸基及び／又はスルホン酸塩基の導入率が低くなったりすることから、難燃性樹脂組成物に対して適切に難燃性を付与することができなくなる。 When the monomer unit having an aromatic skeleton is less than 1 mol%, it becomes difficult to disperse the flame retardant in the flame retardant resin substantially uniformly, or introduction of sulfonic acid groups and / or sulfonic acid groups into the aromatic polymer. Since a rate becomes low, it becomes impossible to provide a flame retardance appropriately with respect to a flame-retardant resin composition.
芳香族ポリマーを構成する芳香族骨格としては、例えば芳香族炭化水素、芳香族エステル、芳香族エーテル（フェノール類）、芳香族チオエーテル（チオフェノール類）、芳香族アミド、芳香族イミド、芳香族アミドイミド、芳香族エーテルイミド、芳香族サルホン、芳香族エーテルサルホンが代表的で、ベンゼン、ナフタレン、アントラセン、フェナントレン、コロネン等の環状構造を有するものが挙げられる。そして、これら芳香族骨格の中では、ベンゼン環やアルキルベンゼン環構造が最も一般的である。 Examples of the aromatic skeleton constituting the aromatic polymer include aromatic hydrocarbons, aromatic esters, aromatic ethers (phenols), aromatic thioethers (thiophenols), aromatic amides, aromatic imides, and aromatic amide imides. Typical examples include aromatic ether imides, aromatic sulfones, and aromatic ether sulfones, and those having a cyclic structure such as benzene, naphthalene, anthracene, phenanthrene, and coronene. Of these aromatic skeletons, benzene rings and alkylbenzene ring structures are the most common.
芳香族ポリマーに含有される芳香族骨格以外のモノマー単位としては、特に限定はないが、例えばアクリロニトリル、ブタジエン、イソプレン、ペンタジエン、シクロペンタジエン、エチレン、プロピレン、ブテン、イソブチレン、塩化ビニル、α-メチルスチレン、ビニルトルエン、ビニルナフタレン、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、マレイン酸、フマール酸、エチレングリコール等が挙げられ、これらのうちの何れか一種若しくは複数種を用いる。 The monomer unit other than the aromatic skeleton contained in the aromatic polymer is not particularly limited. For example, acrylonitrile, butadiene, isoprene, pentadiene, cyclopentadiene, ethylene, propylene, butene, isobutylene, vinyl chloride, α-methylstyrene. , Vinyl toluene, vinyl naphthalene, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, fumaric acid, ethylene glycol and the like, and any one or more of these are used.
また、芳香族ポリマーには、例えば使用済みとなった回収材や工場内で排出された端材を用いることもできる。すなわち、回収材を原料として使用することで、低コスト化を図ることができる。 In addition, for the aromatic polymer, for example, recovered materials that have been used or scrap materials discharged in the factory can be used. That is, the cost can be reduced by using the recovered material as a raw material.
上述した芳香族ポリマーにスルホン酸基及び／又はスルホン酸塩基を所定量導入することで、被難燃樹脂に含有させた際に高い難燃性を付与できる難燃剤が得られる。そして、芳香族ポリマーにスルホン酸基及び／又はスルホン酸塩基を導入する方法としては、例えば芳香族ポリマーを所定量のスルホン化剤でスルホン化処理する方法がある。 By introducing a predetermined amount of a sulfonic acid group and / or a sulfonic acid group into the aromatic polymer described above, a flame retardant capable of imparting high flame retardancy when contained in a flame retardant resin is obtained. As a method for introducing a sulfonic acid group and / or a sulfonate group into an aromatic polymer, for example, there is a method of sulfonating an aromatic polymer with a predetermined amount of a sulfonating agent.
この場合に芳香族ポリマーをスルホン化処理するのに用いるスルホン化剤としては、例えば含有する水分が３重量％未満のものが望ましい。具体的に、スルホン化剤としては、例えば無水硫酸、発煙硫酸、クロルスルホン酸、ポリアルキルベンゼンスルホン酸類等を挙げることができ、これらのうち何れか一種若しくは複数種を混合して用いる。また、スルホン化剤としては、例えばアルキル燐酸エステルやジオキサン等のルイス塩基との錯体物も用いることができる。 In this case, as a sulfonating agent used for sulfonating the aromatic polymer, for example, a water content of less than 3% by weight is desirable. Specifically, examples of the sulfonating agent include sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, polyalkylbenzenesulfonic acid, and the like, and any one or a combination of these is used. Moreover, as a sulfonating agent, for example, a complex with a Lewis base such as an alkyl phosphate ester or dioxane can be used.
スルホン化剤として９６重量％の濃硫酸等を用いた場合、芳香族ポリマーをスルホン化させて難燃剤を製造する際に、ポリマー中のシアノ基が加水分解されて吸水効果の高いアミド基やカルボキシル基に転換され、これらアミド基やカルボキシル基を含有する難燃剤が生成される。このようなアミド基やカルボキシル基等を多量に含んだ難燃剤を用いると、難燃性樹脂組成物に対して高い難燃性を付与することはできるものの、時間経過とともに外部から水分を吸収して、難燃性樹脂組成物が変色して外観を損なわせたり、樹脂の機械的強度を劣化させたりするといった不具合の原因になる虞がある。具体的に、特開２００１−２９４１号公報等で提案されているスルホン酸塩型の難燃剤はこの類である。 When 96% by weight concentrated sulfuric acid or the like is used as a sulfonating agent, when a flame retardant is produced by sulfonating an aromatic polymer, an amide group or carboxyl having a high water absorption effect due to hydrolysis of the cyano group in the polymer. The flame retardant containing these amide groups and carboxyl groups is produced. If a flame retardant containing a large amount of such amide group or carboxyl group is used, high flame retardancy can be imparted to the flame retardant resin composition, but moisture is absorbed from the outside over time. As a result, the flame retardant resin composition may be discolored to impair the appearance or cause a problem such as deterioration of the mechanical strength of the resin. Specifically, the sulfonate-type flame retardant proposed in Japanese Patent Application Laid-Open No. 2001-2941 and the like is of this kind.
以上のことを考慮すると、芳香族ポリマーにスルホン化処理を施す方法としては、例えば芳香族ポリマーを有機溶剤（塩素系溶剤）に溶解した状態の溶液に、所定のスルホン化剤を所定量添加して反応させる方法がある。この他にも、例えば有機溶媒中に粉末状の芳香族ポリマーを分散させた状態（非溶解状態）の分散溶液に、所定のスルホン化剤を所定量添加して反応させる方法がある。さらには、例えば芳香族ポリマーをスルホン化剤に直接投入して反応させる方法や、粉末状の芳香族ポリマーにスルホン化ガス、具体的には無水硫酸（ＳＯ３）ガスを直接吹きかけて反応させる方法等もある。これらの方法の中でも、有機溶剤を使用しない粉末状の芳香族ポリマーにスルホン化ガスを直接吹き付けて反応させる方法がより好ましい。 Considering the above, as a method for sulfonating an aromatic polymer, for example, a predetermined amount of a predetermined sulfonating agent is added to a solution in which an aromatic polymer is dissolved in an organic solvent (chlorine solvent). There is a way to react. In addition, for example, there is a method in which a predetermined amount of a predetermined sulfonating agent is added to a dispersion solution in a state where a powdered aromatic polymer is dispersed in an organic solvent (non-dissolved state). Furthermore, for example, a method in which an aromatic polymer is directly added to a sulfonating agent to cause a reaction, and a method in which a sulfonated gas, specifically, sulfuric anhydride (SO 3 ) gas is directly blown into a powdered aromatic polymer to cause a reaction. Etc. Among these methods, a method in which a sulfonated gas is directly sprayed and reacted with a powdered aromatic polymer that does not use an organic solvent is more preferable.
そして、芳香族ポリマーには、例えばスルホン酸基（−ＳＯ３Ｈ）の状態、スルホン酸塩基の状態、アンモニアやアミン化合物で中和された状態で導入される。具体的に、スルホン酸塩基としては、例えば、スルホン酸Ｎａ塩基、スルホン酸Ｋ塩基、スルホン酸Ｌｉ塩基、スルホン酸Ｃａ塩基、スルホン酸Ｍｇ塩基、スルホン酸Ａｌ塩基、スルホン酸Ｚｎ塩基、スルホン酸Ｓｂ塩基、スルホン酸Ｓｎ塩基等を上げることができる。 Then, the aromatic polymer, for example, the state of sulfonic acid (-SO 3 H), sulfonate state, is introduced in a state of being neutralized by ammonia or an amine compound. Specifically, examples of the sulfonate group include a sulfonate Na base, a sulfonate K base, a sulfonate Li base, a sulfonate Ca base, a sulfonate Mg base, a sulfonate Al base, a sulfonate Zn base, and a sulfonate Sb. Base, sulfonic acid Sn base, etc. can be raised.
なお、難燃剤においては、芳香族ポリマーに、スルホン酸基よりスルホン酸塩基で導入された方が、難燃性樹脂組成物に対してより高い難燃性を付与することができる。これらの中でも、スルホン酸Ｎａ塩、スルホン酸Ｋ塩、スルホン酸Ｃａ塩等が好適である。 In addition, in a flame retardant, the direction which was introduce | transduced into the aromatic polymer with the sulfonate group rather than the sulfonic acid group can provide a higher flame retardance with respect to a flame retardant resin composition. Among these, sulfonic acid Na salt, sulfonic acid K salt, sulfonic acid Ca salt and the like are preferable.
また、芳香族ポリマーに対するスルホン酸基及び／又はスルホン酸塩基の導入率は、スルホン化剤の添加量や、スルホン化剤を反応させる時間や、反応温度や、ルイス塩基の種類や量等で調整することができる。これらの方法の中でも、スルホン化剤の添加量、スルホン化剤と反応させる時間、反応温度等で調整することがより好ましい。 The introduction rate of sulfonic acid groups and / or sulfonate groups to the aromatic polymer is adjusted by the addition amount of the sulfonating agent, the reaction time of the sulfonating agent, the reaction temperature, the type and amount of Lewis base, etc. can do. Among these methods, it is more preferable to adjust the addition amount of the sulfonating agent, the reaction time with the sulfonating agent, the reaction temperature, and the like.
具体的には、芳香族ポリマーに対するスルホン酸基及び／又はスルホン酸塩基の導入率は０．０１モル％〜１４.９モル％の範囲であり、好ましくは０.０５モル％〜１２モル％の範囲であり、さらに好ましくは１モル％〜１０モル％の範囲である。 Specifically, the introduction ratio of the sulfonic acid group and / or the sulfonic acid group to the aromatic polymer is in the range of 0.01 mol% to 14.9 mol%, preferably 0.05 mol% to 12 mol%. It is a range, More preferably, it is the range of 1 mol%-10 mol%.
芳香族ポリマーに対するスルホン酸基及び／又はスルホン酸塩基の導入率が０．０１モル％より低いと、難燃性樹脂組成物に対して難燃性を付与することが困難になる。一方、芳香族ポリマーに対するスルホン酸基及び／又はスルホン酸塩基の導入率が１４．９モル％より多いと、樹脂組成物との相溶性が低下したり、時間経過と共に難燃性樹脂組成物の機械的強度が劣化したりする虞がある。 When the introduction ratio of the sulfonic acid group and / or sulfonic acid group to the aromatic polymer is lower than 0.01 mol%, it becomes difficult to impart flame retardancy to the flame retardant resin composition. On the other hand, when the introduction ratio of the sulfonic acid group and / or sulfonic acid group to the aromatic polymer is more than 14.9 mol%, the compatibility with the resin composition is reduced, or the flame retardant resin composition is deteriorated over time. There is a risk that the mechanical strength may deteriorate.
芳香族ポリマーに対するスルホン酸基及び／又はスルホン酸塩基の導入率は、例えばスルホン化処理された芳香族ポリマー中に含有される硫黄（Ｓ）成分を燃焼フラスコ法等によって定量分析することで容易に求めることができる。そして、芳香族ポリマーに導入されるスルホン酸基及び／又はスルホン酸塩基の導入率を芳香族ポリマー中に含有される硫黄成分を目安にした場合、芳香族ポリマー中に含有される硫黄成分は、芳香族ポリマーの種類等によっても異なるが、通常、０．００１重量％〜４.１重量％の範囲であり、好ましくは０.００５重量％〜２.５重量％の範囲である。 The introduction rate of sulfonic acid groups and / or sulfonate groups into the aromatic polymer can be easily determined by quantitatively analyzing, for example, the sulfur (S) component contained in the sulfonated aromatic polymer by a combustion flask method or the like. Can be sought. And, when the introduction rate of the sulfonic acid group and / or sulfonic acid group introduced into the aromatic polymer is based on the sulfur component contained in the aromatic polymer, the sulfur component contained in the aromatic polymer is: Although it depends on the type of aromatic polymer, etc., it is usually in the range of 0.001 wt% to 4.1 wt%, preferably 0.005 wt% to 2.5 wt%.
以上で説明した難燃剤が含有されることで難燃性が付与される樹脂組成物、すなわち難燃性樹脂組成物の原料となる被難燃樹脂としては、例えばポリカーボネート（ＰＣ）、アクリロニトリル-ブタジエン-スチレン共重合体（ＡＢＳ）、ポリスチレン（ＰＳ）、アクリロニトリル-スチレン共重合体（ＡＳ）、ポリ塩化ビニル（ＰＶＣ）、ポリフェニレンオキシド（ＰＰＯ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンブチレート（ＰＢＴ）、ポリスルホン（ＰＳＦ）、熱可塑性エラストマー（ＴＰＥ）、ポリブタジエン（ＰＢ）、ポリイソプレン（ＰＩ）、ニトリルゴム（アクリロニトリル-ブタジエンラバー）、ナイロン、ポリ乳酸（ＰＬＡ）等を挙げることができ、これらのうち何れか一種類以上を５重量％以上含有している樹脂組成物を用いる。すなわち、これらの被難燃樹脂は、一種類で用いてもよいし、複数種を混合した混合物（アロイ）として用いてよい。 Examples of the resin composition to which flame retardancy is imparted by containing the flame retardant described above, that is, the flame retardant resin used as a raw material of the flame retardant resin composition include polycarbonate (PC) and acrylonitrile-butadiene. -Styrene copolymer (ABS), polystyrene (PS), acrylonitrile-styrene copolymer (AS), polyvinyl chloride (PVC), polyphenylene oxide (PPO), polyethylene terephthalate (PET), polyethylene butyrate (PBT), Examples include polysulfone (PSF), thermoplastic elastomer (TPE), polybutadiene (PB), polyisoprene (PI), nitrile rubber (acrylonitrile-butadiene rubber), nylon, polylactic acid (PLA), and any of these. Or more than 5% by weight A resin composition is used. That is, these flame retardant resins may be used alone or as a mixture (alloy) in which a plurality of types are mixed.
上述した難燃剤が含有されることで特に効果的に難燃性が付与される被難燃樹脂としては、例えばＰＣ、ＡＢＳ、（ＨＩ）ＰＳ、ＡＳ、ＰＰＯ、ＰＢＴ、ＰＥＴ、ＰＶＣ、ＰＬＡ、ＡＢＳ/ＰＣアロイ、ＰＳ/ＰＣアロイ、ＡＳ/ＰＣアロイ、ＨＩＰＳ/ＰＣアロイ、ＰＥＴ/ＰＣアロイ、ＰＢＴ/ＰＣアロイ、ＰＶＣ/ＰＣアロイ、ＰＬＡ（ポリ乳酸）/ＰＣアロイ、ＰＰＯ/ＰＣアロイ、ＰＳ/ＰＰＯアロイ、ＨＩＰＳ/ＰＰＯアロイ、ＡＢＳ/ＰＥＴアロイ、ＰＥＴ/ＰＢＴアロイ等の少なくとも１種類以上の樹脂を挙げることができる。 Examples of flame retardant resins that are particularly effectively imparted with flame retardancy by containing the above-described flame retardant include PC, ABS, (HI) PS, AS, PPO, PBT, PET, PVC, PLA, ABS / PC alloy, PS / PC alloy, AS / PC alloy, HIPS / PC alloy, PET / PC alloy, PBT / PC alloy, PVC / PC alloy, PLA (polylactic acid) / PC alloy, PPO / PC alloy, PS Examples thereof include at least one resin such as / PPO alloy, HIPS / PPO alloy, ABS / PET alloy, and PET / PBT alloy.
このように、芳香族ポリマーにスルホン酸基及び/又はスルホン酸塩基が０．０１モル％〜１４.９モル％の範囲で導入されたものを難燃剤として用いることで、難燃性を付与できる被難燃性樹脂の種類を多く出来る。 Thus, flame retardancy can be imparted by using, as a flame retardant, an aromatic polymer having a sulfonic acid group and / or a sulfonic acid group introduced in a range of 0.01 mol% to 14.9 mol%. Many types of flame retardant resin can be made.
そして、被難燃樹脂には、上述した難燃剤と同様、例えば使用済みとなった回収材や工場内で排出された端材を用いることもできる。すなわち、回収樹脂を原料として使用することで低コスト化を図ることができる。 As the flame retardant resin, for example, a used recovered material or an end material discharged in a factory can be used as in the above-described flame retardant. That is, the cost can be reduced by using the recovered resin as a raw material.
以上のような構成の難燃性樹脂組成物においては、スルホン酸基及び／又はスルホン酸塩基が０．０１モル％〜１４.９モル％の範囲で導入された芳香族ポリマーを難燃剤として用いることから、被難燃樹脂に対する難燃剤の相溶性が高められ、難燃性を適切に付与することができる。 In the flame retardant resin composition having the above-described configuration, an aromatic polymer into which sulfonic acid groups and / or sulfonic acid groups are introduced in a range of 0.01 mol% to 14.9 mol% is used as a flame retardant. For this reason, the compatibility of the flame retardant with the flame retardant resin is enhanced, and the flame retardancy can be appropriately imparted.
また、この難燃性樹脂組成物においては、含有される難燃剤が、芳香族ポリマーを水分量３重量％未満のスルホン化剤でスルホン化処理されることで得られたものであり、難燃剤中に吸水効果の高いアミド基やカルボキシル基が導入されることが抑えられることから、長期保存中に大気中の水分を吸って変色して外観を損ねたり、機械的強度が低下したりするといった不具合を抑制できる。 In this flame retardant resin composition, the flame retardant contained is obtained by sulfonating an aromatic polymer with a sulfonating agent having a water content of less than 3% by weight. Since the introduction of amide groups and carboxyl groups with high water-absorbing effect is suppressed, it absorbs moisture in the atmosphere during long-term storage and discolors to deteriorate the appearance or reduce mechanical strength. Defects can be suppressed.
さらにまた、難燃性樹脂組成物においては、被難燃樹脂に対して難燃剤の含有量は０.００１重量％〜１０重量％の範囲であり、好ましくは０．００５重量％〜５重量％の範囲であり、さらに好ましくは０.０１重量％〜３重量％の範囲である。 Furthermore, in the flame retardant resin composition, the flame retardant content in the flame retardant resin is in the range of 0.001 wt% to 10 wt%, preferably 0.005 wt% to 5 wt%. More preferably, it is in the range of 0.01% by weight to 3% by weight.
被難燃樹脂に対する難燃剤の含有量が０．００１重量％より少なくなると、難燃性樹脂組成物に対して難燃性を効果的に付与することが困難になる。一方、被難燃樹脂に対する難燃剤の含有量が１０重量％より多くなると、被難燃性樹脂組成物が逆に燃焼し易くなる。 When the content of the flame retardant with respect to the flame retardant resin is less than 0.001% by weight, it becomes difficult to effectively impart flame retardancy to the flame retardant resin composition. On the other hand, when the content of the flame retardant with respect to the flame retardant resin is more than 10% by weight, the flame retardant resin composition is easily burnt.
すなわち、この難燃剤は、被難燃樹脂に少量加えることで難燃性が効果的に付与された難燃性樹脂組成物を得ることができるものである。 That is, this flame retardant can obtain a flame retardant resin composition effectively imparted with flame retardancy by adding a small amount to the flame retardant resin.
以上で説明した難燃性樹脂組成物においては、上述した難燃剤の他に、さらに難燃性を高める目的で、例えば従来公知の難燃剤等を添加させることもできる。 In the flame retardant resin composition described above, for example, a conventionally known flame retardant can be added in addition to the above-mentioned flame retardant for the purpose of further improving the flame retardancy.
従来公知の難燃剤としては、例えば有機リン酸エステル系難燃剤、ハロゲン化リン酸エステル系難燃剤、無機リン系難燃剤、ハロゲン化ビスフェノール系難燃剤、ハロゲン化合物系難燃剤、アンチモン系難燃剤、窒素系難燃剤、ほう素系難燃剤、金属塩系難燃剤、無機系難燃剤、珪素系難燃剤等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Conventionally known flame retardants include, for example, organic phosphate ester flame retardants, halogenated phosphate ester flame retardants, inorganic phosphorus flame retardants, halogenated bisphenol flame retardants, halogen compound flame retardants, antimony flame retardants, Nitrogen-based flame retardants, boron-based flame retardants, metal salt-based flame retardants, inorganic flame retardants, silicon-based flame retardants, etc., can be used, any one or a mixture of these can be used is there.
具体的に、有機リン酸エステル系難燃剤としては、例えばトリフェニルフォスフェート、メチルネオベンジルフォスフェート、ペンタエリスリトールジエチルジフォスフェート、メチルネオペンチルフォスフェート、フェニルネオペンチルフォスフェート、ペンタエリスリトールジフェニルジフォスフェート、ジシクロペンチルハイポジフォスフェート、ジネオペンチルハイポフォスファイト、フェニルピロカテコールフォスファイト、エチルピロカテコールフォスフェート、ジピロカテコールハイポジフォスフェート等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Specifically, examples of the organic phosphate ester flame retardant include triphenyl phosphate, methyl neobenzyl phosphate, pentaerythritol diethyl diphosphate, methyl neopentyl phosphate, phenyl neopentyl phosphate, pentaerythritol diphenyl diphosphate. Fate, dicyclopentyl high positive phosphate, dineopentyl hypophosphite, phenyl pyrocatechol phosphite, ethyl pyrocatechol phosphate, dipyrrocatechol high positive phosphate, etc., any one or a combination of these Can be used.
ハロゲン化リン酸エステル系難燃剤としては、例えばトリス（βークロロエチル）ホスフェート、トリス（ジクロロプロピル）ホスフェート、トリス（βーブロモエチル）ホスフェート、トリス（ジブロモプロピル）ホスフェート、トリス（クロロプロピル）ホスフェート、トリス（ジブロモフェニル）ホスフェート、トリス（トリブロモフェニル）ホスフェート、トリス（トリブロモネオペンチル）ホスフェート、縮合型ポリホスフェート、縮合型ポリホフホネート等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the halogenated phosphate ester flame retardant include tris (β-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (β-bromoethyl) phosphate, tris (dibromopropyl) phosphate, tris (chloropropyl) phosphate, tris (dibromo). Phenyl) phosphate, tris (tribromophenyl) phosphate, tris (tribromoneopentyl) phosphate, condensed polyphosphate, condensed polyphosphonate, etc., and any one or a mixture of these may be used Is possible.
無機リン系難燃剤としては、例えば赤燐、無機系リン酸塩等が挙げられ、これらのうちの一種若しくは両方を混合して用いることが可能である。 Examples of the inorganic phosphorus flame retardant include red phosphorus and inorganic phosphate, and one or both of these can be used in combination.
ハロゲン化ビスフェノール系難燃剤としては、例えばテトラブロモビスフェノールＡ及びこのオリゴマー、ビス（ブロモエチルエーテル）テトラブロモビスフェノールＡ等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the halogenated bisphenol-based flame retardant include tetrabromobisphenol A and its oligomer, bis (bromoethyl ether) tetrabromobisphenol A, and the like, and any one or a combination of these may be used. Is possible.
ハロゲン化合物系難燃剤としては、デカブロモジフェニルエーテル、ヘキサブロモベンゼン、ヘキサブロモシクロドデカン、テトラブロモ無水フタル酸、（テトラブロビスモフェノール）エポキシオリゴマー、ヘキサブロモビフェニルエーテル、トリブロモフェノール、ジブロモクレジルグリシジルエーテル、デカブロモジフェニルオキシド、ハロゲン化ポリカーボネート、ハロゲン化ポリカーボネート共重合体、ハロゲン化ポリスチレン、ハロゲン化ポリオレフィン、塩素化パラフィン、パークロロシクロデカン等を挙げられ、これらのうち何れか一種類若しくは複数種を混合して用いることが可能である。 Halogen compound flame retardants include decabromodiphenyl ether, hexabromobenzene, hexabromocyclododecane, tetrabromophthalic anhydride, (tetrabrobismophenol) epoxy oligomer, hexabromobiphenyl ether, tribromophenol, dibromocresyl glycidyl ether , Decabromodiphenyl oxide, halogenated polycarbonate, halogenated polycarbonate copolymer, halogenated polystyrene, halogenated polyolefin, chlorinated paraffin, perchlorocyclodecane, etc., any one of these or a mixture of two or more Can be used.
アンチモン系難燃剤としては、例えば三酸化アンチモン、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が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the antimony flame retardant include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, and the like, and any one or a mixture of these can be used.
窒素系難燃剤としては、例えばメラミン、アルキル基又は芳香族置換メラミン、メラミンシアヌレート、イソシアヌレート、メラミンフォスフェート、トリアジン、グアニジン化合物、尿素、各種シアヌール酸誘導体、フォスファゼン化合物等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the nitrogen-based flame retardant include melamine, alkyl group or aromatic substituted melamine, melamine cyanurate, isocyanurate, melamine phosphate, triazine, guanidine compound, urea, various cyanuric acid derivatives, phosphazene compound, and the like. Any one or a plurality of them can be used in combination.
ほう素系難燃剤としては、例えばほう素酸亜鉛、メタほう素酸亜鉛、メタほう酸バリウム等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the boron-based flame retardant include zinc borate, zinc metaborate, barium metaborate, and the like, and any one or a combination of these can be used.
金属塩系難燃剤としては、例えばパーフルオロアルカンスルホン酸、アルキルベンゼンスルホン酸、ハロゲン化アルキルベンゼンスルホン酸、アルキルスルホン酸、ナフタレンスルホン酸等のアルカリ金属塩やアルカリ土類金属塩等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the metal salt flame retardant include alkali metal salts and alkaline earth metal salts such as perfluoroalkanesulfonic acid, alkylbenzenesulfonic acid, halogenated alkylbenzenesulfonic acid, alkylsulfonic acid, and naphthalenesulfonic acid. Any one or a plurality of them can be used in combination.
無機系難燃剤としては、例えば水酸化マグネシウム、水酸化アルミニウム、水酸化バリウム、水酸化カルシウム、ドロマイト、ハイドロタルサイト、塩基性炭酸マグネシウム、水素化ジルコニウム、酸化スズの水和物等の無機金属化合物の水和物、酸化アルミニウム、酸化鉄、酸化チタン、酸化マンガン、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化コバルト、酸化ビスマス、酸化クロム、酸化スズ、酸化ニッケル、酸化銅、酸化タングステン等の金属酸化物、アルミニウム、鉄、銅、ニッケル、チタン、マンガン、スズ、亜鉛、モリブデン、コバルト、ビスマス、クロム、タングステン、アンチモン等の金属粉、炭酸亜鉛、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム等の炭酸塩等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of inorganic flame retardants include inorganic metal compounds such as magnesium hydroxide, aluminum hydroxide, barium hydroxide, calcium hydroxide, dolomite, hydrotalcite, basic magnesium carbonate, zirconium hydride, and tin oxide hydrate. Hydrate, aluminum oxide, iron oxide, titanium oxide, manganese oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, chromium oxide, tin oxide, nickel oxide, copper oxide, tungsten oxide, etc. Metal oxides such as aluminum, iron, copper, nickel, titanium, manganese, tin, zinc, molybdenum, cobalt, bismuth, chromium, tungsten, antimony, etc., zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, etc. Such as carbonates, It is possible to use a mixture of one kind or plural kinds of Chi.
そして、無機系難燃剤の中でも、水酸化マグネシウム、水酸化アルミニウム、マグネシウムの含水ケイ酸塩であるタルク、塩基性炭酸マグネシウム、マイカ、ハイドロサルサイト、アルミ等が難燃性や経済性の観点から好適である。なお、使用済みとなった回収材や工場内で排出された端材等を無機系難燃剤として用いることができる。 Among inorganic flame retardants, magnesium hydroxide, aluminum hydroxide, magnesium hydrated talc, basic magnesium carbonate, mica, hydrosalsite, aluminum, etc. are from the viewpoint of flame retardancy and economy. Is preferred. It should be noted that used recovered materials, scrap materials discharged in the factory, and the like can be used as inorganic flame retardants.
珪素系難燃剤としては、例えばポリオルガノシロキサン樹脂（シリコーン、有機シリケート等）、シリカ等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。そして、ポリオルガノシロキサン樹脂としては、例えばポリメチルエチルシロキサン樹脂、ポリジメチルシロキサン樹脂、ポリメチルフェニルシロキサン樹脂、ポリジフェニルシロキサン樹脂、ポリジエチルシロキサン樹脂、ポリエチルフェニルシロキサン樹脂やこれら混合物等を挙げることができる。 Examples of the silicon-based flame retardant include polyorganosiloxane resin (silicone, organic silicate, etc.), silica, and the like, and any one or a combination of these can be used. Examples of the polyorganosiloxane resin include polymethylethylsiloxane resin, polydimethylsiloxane resin, polymethylphenylsiloxane resin, polydiphenylsiloxane resin, polydiethylsiloxane resin, polyethylphenylsiloxane resin, and mixtures thereof. it can.
これらポリオルガノシロキサン樹脂のアルキル基部分には、例えばアルキル基、アルコキシ基、水酸基、アミノ基、カルボキシル基、シラノール基、メルカプト基、エポキシ基、ビニル基、アリールオキシ基、ポリオキシアルキレン基、水素基、ハロゲン等の官能基が含有されていても良く、特にアルキル基、アルコキシ基、水酸基、ビニル基等が含有されることが好ましい。 The alkyl group portion of these polyorganosiloxane resins includes, for example, alkyl groups, alkoxy groups, hydroxyl groups, amino groups, carboxyl groups, silanol groups, mercapto groups, epoxy groups, vinyl groups, aryloxy groups, polyoxyalkylene groups, hydrogen groups. Further, a functional group such as halogen may be contained, and an alkyl group, an alkoxy group, a hydroxyl group, a vinyl group or the like is particularly preferably contained.
そして、ポリオルガノシロキサン樹脂としては、その平均分子量が１００以上、好ましくは５００〜５００００００の範囲であり、その形態については、例えばオイル状、ワニス状、ガム状、粉末状、ペレット状のいずれであっても良い。また、シリカについては、炭化水素系化合物のシランカップリング剤で表面処理されたものが好適である。 The polyorganosiloxane resin has an average molecular weight of 100 or more, preferably in the range of 500 to 5,000,000. The form of the polyorganosiloxane resin is, for example, any of oil, varnish, gum, powder, and pellets. May be. Moreover, about the silica, what was surface-treated with the silane coupling agent of a hydrocarbon type compound is suitable.
以上で説明した従来公知の難燃剤は、その種類や必要とされる難燃性のレベルや被難燃樹脂の種類によって異なるが、その含有量は、通常、被難燃樹脂に対して０.００１重量％〜５０重量％の範囲であり、好ましくは０.０１重量％〜３０重量％の範囲であり、さらに好ましくは０.１重量％〜１０重量％の範囲である。 The conventionally known flame retardant described above varies depending on the type, the required level of flame retardancy, and the type of flame retardant resin, but the content thereof is generally 0. The range is 001 wt% to 50 wt%, preferably 0.01 wt% to 30 wt%, and more preferably 0.1 wt% to 10 wt%.
また、難燃性樹脂組成物においては、上述した難燃剤の他に、機械的強度の向上や、さらなる難燃性の向上を図る目的で、例えば従来公知の無機充填剤等を添加させることもできる。 In addition, in the flame retardant resin composition, in addition to the above-mentioned flame retardant, for example, a conventionally known inorganic filler may be added for the purpose of improving mechanical strength and further improving flame retardancy. it can.
従来公知の無機充填剤としては、例えば結晶性シリカ、溶融シリカ、アルミナ、マグネシア、タルク、マイカ、カオリン、クレー、珪藻土、ケイ酸カルシウム、酸化チタン、ガラス繊維、弗化カルシウム、硫酸カルシウム、硫酸バリウム、燐酸カルシウム、炭素繊維、カーボンナノチューブ、チタン酸カリウム繊維等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。これらの無機充填剤の中でも、タルク、マイカ、カーボン、ガラス、カーボンナノチューブを用いることが好ましい。 Examples of conventionally known inorganic fillers include crystalline silica, fused silica, alumina, magnesia, talc, mica, kaolin, clay, diatomaceous earth, calcium silicate, titanium oxide, glass fiber, calcium fluoride, calcium sulfate, and barium sulfate. , Calcium phosphate, carbon fiber, carbon nanotube, potassium titanate fiber, and the like, and any one or a combination of these may be used. Among these inorganic fillers, talc, mica, carbon, glass, and carbon nanotube are preferably used.
無機充填剤は、難燃性樹脂組成物に対して０．１重量％〜９０重量％の範囲、好ましくは０.５重量％〜５０重量％の範囲、さらに好ましくは１重量％〜３０重量％の範囲で含有されている。 The inorganic filler is in the range of 0.1% to 90% by weight, preferably 0.5% to 50% by weight, more preferably 1% to 30% by weight, based on the flame retardant resin composition. It is contained in the range.
無機充填剤の含有量が０．１重量％より少なくなると、難燃性樹脂組成物の剛性や難燃性の改善効果が低くなる。一方、無機充填剤の含有量が９０重量％より多くなると、難燃性樹脂組成物を射出成形する際に溶融した難燃性樹脂組成物の流動性が低下したり、機械的強度が低下したりするといった不具合が起こる虞がある。 When the content of the inorganic filler is less than 0.1% by weight, the effect of improving the rigidity and flame retardancy of the flame retardant resin composition is lowered. On the other hand, if the content of the inorganic filler is more than 90% by weight, the fluidity of the flame-retardant resin composition melted when the flame-retardant resin composition is injection-molded or the mechanical strength is lowered. There is a risk of malfunctions such as
さらに、難燃性樹脂組成物においては、上述した難燃剤の他に、燃焼時のドリップ現象を抑制する目的で、例えばフルオロオレフィン樹脂等を添加させることもできる。 Furthermore, in the flame retardant resin composition, in addition to the above-mentioned flame retardant, for example, a fluoroolefin resin or the like can be added for the purpose of suppressing a drip phenomenon during combustion.
ドリップ現象を抑制できるフルオロオレフィン樹脂としては、例えばジフルオロエチレン重合体、テトラフルオロエチレン重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、テトラフルオロエチレン-エチレン系モノマーとの共重合体等が挙げられ、これらのうちの何れか一種若しくは複数種を混合して用いることが可能である。 Examples of the fluoroolefin resin capable of suppressing the drip phenomenon include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a copolymer with a tetrafluoroethylene-ethylene monomer. Any one or a combination of these may be used.
これらのフルオロオレフィン樹脂の中でも、特にテトラフルオロエチレン重合体等を用いることが好ましく、その平均分子量は５００００以上であり、好ましくは１０００００〜２０００００００の範囲である。なお、フルオロオレフィン樹脂としては、フィブリル形成能を有するものがより好ましい。 Among these fluoroolefin resins, it is particularly preferable to use a tetrafluoroethylene polymer or the like, and the average molecular weight is 50,000 or more, preferably in the range of 100,000 to 20,000,000. In addition, as fluoroolefin resin, what has fibril formation ability is more preferable.
フルオロオレフィン樹脂は、難燃性樹脂組成物に対して０．００１重量％〜５重量％の範囲、好ましくは０.００５重量％〜２重量％の範囲、さらに好ましくは０.０１重量％〜０.５重量％の範囲で含有されている。 The fluoroolefin resin is in the range of 0.001 wt% to 5 wt%, preferably in the range of 0.005 wt% to 2 wt%, more preferably 0.01 wt% to 0 wt% with respect to the flame retardant resin composition. It is contained in the range of 0.5% by weight.
フルオロオレフィン樹脂の含有量が０．００１重量％より少なくなると、ドリップ現象を抑制させることが困難になる。一方、フルオロオレフィン樹脂の含有量が５重量％より多くなると、ドリップ現象を抑制できる効果が飽和し、コスト高になったり、機械的強度が低下したりするといった不具合が起こる虞がある。 When the content of the fluoroolefin resin is less than 0.001% by weight, it becomes difficult to suppress the drip phenomenon. On the other hand, when the content of the fluoroolefin resin is more than 5% by weight, the effect of suppressing the drip phenomenon is saturated, and there is a possibility that a problem such as an increase in cost and a decrease in mechanical strength may occur.
さらにまた、難燃性樹脂組成物においては、上述した難燃剤の他に、射出成形性、耐衝撃性、外観、耐熱性、耐候性、剛性等の改善を目的で、例えば酸化防止剤（フェノール系、リン系、硫黄系）、帯電防止剤、紫外線吸収剤、光安定化剤、可塑剤、相溶化剤、着色剤（顔料、染料）、抗菌剤、加水分解防止剤、表面処理剤等を添加させることもできる。 Furthermore, in the flame-retardant resin composition, in addition to the above-mentioned flame retardant, for example, an antioxidant (phenol) for the purpose of improving injection moldability, impact resistance, appearance, heat resistance, weather resistance, rigidity, and the like. System, phosphorus system, sulfur system), antistatic agent, UV absorber, light stabilizer, plasticizer, compatibilizer, colorant (pigment, dye), antibacterial agent, hydrolysis inhibitor, surface treatment agent, etc. It can also be added.
そして、以上で説明した難燃性樹脂組成物は、難燃剤、被難燃樹脂、及びその他の添加剤等を、例えばタンブラー、リブレンダー、ミキサー、押出機、コニーダ等といった混練装置にて略均一に分散させた後に、射出成形、射出圧縮成形、押出成形、ブロー成形、真空成形、プレス成形、発泡成形、超臨界成形等といった成形法により所定の形状に成形された状態で得られる。 The flame retardant resin composition described above is substantially uniform in a kneading apparatus such as a tumbler, a reblender, a mixer, an extruder, or a kneader, for example, a flame retardant, a flame retardant resin, and other additives. After being dispersed, the resin is obtained in a state of being molded into a predetermined shape by a molding method such as injection molding, injection compression molding, extrusion molding, blow molding, vacuum molding, press molding, foam molding, supercritical molding or the like.
そして、難燃性樹脂組成物からなる成形品は、例えば家電製品、自動車、情報機器、事務機器、電話機、文房具、家具、繊維等の各種製品の難燃性が付与された筐体や部品材として、種々の分野で用いられる。 And the molded article which consists of a flame-retardant resin composition is the housing | casing and component material which were given the flame retardance of various products, such as household appliances, a motor vehicle, information equipment, office equipment, a telephone, stationery, furniture, textiles, for example As used in various fields.
以下、上述した本発明を実証するための実施例、及び実施例に対して比較するための比較例について説明する。 Hereinafter, the Example for demonstrating this invention mentioned above and the comparative example for comparing with an Example are demonstrated.
先ず、実施例及び比較例に含有される難燃剤として実施サンプル及び比較サンプルを作製した。 First, the implementation sample and the comparison sample were produced as a flame retardant contained in an Example and a comparative example.
〈実施サンプル１〉
実施サンプル１を作製する際は、先ず、芳香族ポリマーとしてスチレンホモポリマー（重量平均分子量：２８万）２．６ｇを、１，２−ジクロロエタン２３．４ｇを注入した丸底フラスコに投入して溶解させ、ポリマー溶液を調製した。次に、９６％硫酸０．２５ｇと無水酢酸０．３ｇとの混合液をポリマー溶液に１０分かけて滴下し、滴下後４時間熟成することで芳香族ポリマーに対してスルホン化処理を行った。次に、沸騰した純水に反応液を注入して溶剤分を取り除き、得られた固体を温純水で３回洗浄した後に、減圧乾燥を行い乾燥した固体を得た。
<Example 1>
When producing the working sample 1, first, 2.6 g of a styrene homopolymer (weight average molecular weight: 280,000) as an aromatic polymer was put into a round bottom flask into which 23.4 g of 1,2-dichloroethane was injected and dissolved. To prepare a polymer solution. Next, a mixture of 0.25 g of 96% sulfuric acid and 0.3 g of acetic anhydride was added dropwise to the polymer solution over 10 minutes, and the aromatic polymer was sulfonated by aging for 4 hours after the addition. . Next, the reaction solution was poured into boiling pure water to remove the solvent, and the obtained solid was washed three times with warm pure water, and then dried under reduced pressure to obtain a dried solid.
このとき、得られた固体について、燃焼フラスコ法による元素分析を行ったところ、得られた難燃剤中に含まれる硫黄成分からスルホン酸基導入率は８モル％であった。 At this time, when the obtained solid was subjected to elemental analysis by a combustion flask method, the sulfonic acid group introduction rate was 8 mol% from the sulfur component contained in the obtained flame retardant.
次に、乾燥した固体を水酸化カリウムで中和した後に、再び乾燥することで、難燃剤を作製した。すなわち、難燃剤としてスルホン酸基が導入された芳香族ポリマーが得られた。 Next, after neutralizing the dried solid with potassium hydroxide, it dried again, and the flame retardant was produced. That is, an aromatic polymer having a sulfonic acid group introduced as a flame retardant was obtained.
〈実施サンプル２〉
実施サンプル２を作製する際は、先ず、芳香族ポリマーとして使用済み扇風機の羽根を粉砕し、８３メッシュパスの粉末状となったアクリロニトリル-スチレン共重合樹脂（アクリロニトリル単位：４４モル％、スチレン単位：５６モル％）３ｇを丸底フラスコに投入し、そのまま攪拌した状態で発煙硫酸４ｇから発生するＳＯ３ガスを室温下で４時間かけて吹き込むことで芳香族ポリマーに対してスルホン化処理を行った。次に、フラスコ中にエアーを送り込むことで丸底フラスコラから残留ＳＯ３ガスを取り除き、固体は３回水洗した後に乾燥した。
<Example 2>
When producing the working sample 2, first, the blades of a used fan as an aromatic polymer were pulverized to form an 83 mesh pass acrylonitrile-styrene copolymer resin (acrylonitrile unit: 44 mol%, styrene unit: 56 mol%) was charged into a round bottom flask, and the aromatic polymer was sulfonated by blowing SO 3 gas generated from 4 g of fuming sulfuric acid over 4 hours at room temperature with stirring. . Next, residual SO 3 gas was removed from the round bottom flask by sending air into the flask, and the solid was washed three times with water and dried.
このとき、得られた固体について、燃焼フラスコ法による元素分析を行ったところ、スルホン酸基導入率は７．２モル％であった。 At this time, when the obtained solid was subjected to elemental analysis by a combustion flask method, the sulfonic acid group introduction rate was 7.2 mol%.
次に、乾燥した固体を水酸化カリウムで中和した後に、再び乾燥することで、淡黄色固体からなる難燃剤を作製した。すなわち、実施サンプル２も、スルホン酸基が導入された芳香族ポリマーである。 Next, the dried solid was neutralized with potassium hydroxide, and then dried again to prepare a flame retardant composed of a pale yellow solid. That is, the working sample 2 is also an aromatic polymer into which a sulfonic acid group has been introduced.
〈実施サンプル３〉
実施サンプル３では、芳香族ポリマーとして使用済み８ｍｍカセットを粉砕し、８３メッシュパスの粉末状となったのアクリロニトリル-ブタジエン-スチレン共重合樹脂（アクリロニトリル単位：３８モル％、スチレン単位：５０モル％、ブタジエン単位：１２モル％、黒色）を用い、スルホン化処理を行った時間を１０分としたこと以外は、上述した実施サンプル２と同様にして難燃剤を得た。すなわち、実施サンプル３も、スルホン酸基が導入された芳香族ポリマーである。そして、得られた難燃剤を上述した実施サンプル１と同様にして、燃焼フラスコ法による元素分析を行ったところ、スルホン酸基導入率は０．１０モル％であった。
<Example 3>
In execution sample 3, acrylonitrile-butadiene-styrene copolymer resin (acrylonitrile unit: 38 mol%, styrene unit: 50 mol%) obtained by grinding an 8 mm cassette used as an aromatic polymer into powder of 83 mesh pass was obtained. A flame retardant was obtained in the same manner as in the above-described sample 2 except that the butadiene unit: 12 mol%, black) was used and the time for sulfonation treatment was 10 minutes. That is, the working sample 3 is also an aromatic polymer into which a sulfonic acid group has been introduced. Then, when the obtained flame retardant was subjected to elemental analysis by the combustion flask method in the same manner as in the above-described Example 1, the sulfonic acid group introduction rate was 0.10 mol%.
〈実施サンプル４〉
実施サンプル４では、芳香族ポリマーとしてポリエチレンテレフタレートを用いたこと以外は、上述した実施サンプル２と同様にして白色固体からなる難燃剤を得た。すなわち、実施サンプル４も、スルホン酸基が導入された芳香族ポリマーである。そして、得られた難燃剤を上述した実施サンプル１と同様にして、燃焼フラスコ法による元素分析を行ったところ、スルホン酸基導入率は０．１２モル％であった。
<Example 4>
In Example Sample 4, a flame retardant composed of a white solid was obtained in the same manner as Example Sample 2 described above except that polyethylene terephthalate was used as the aromatic polymer. That is, the working sample 4 is also an aromatic polymer into which a sulfonic acid group has been introduced. Then, when the obtained flame retardant was subjected to elemental analysis by the combustion flask method in the same manner as in the above-described Example 1, the sulfonic acid group introduction rate was 0.12 mol%.
〈実施サンプル５〉
実施サンプル５では、芳香族ポリマーとして工場で排出された透明光学ディスクを粉砕し、８３メッシュパスの粉末状となったポリカーボネートを用いたこと以外は、上述した実施サンプル２と同様にして白色固体からなる難燃剤を得た。すなわち、実施サンプル５も、スルホン酸基が導入された芳香族ポリマーである。そして、得られた難燃剤を上述した実施サンプル１と同様にして、燃焼フラスコ法による元素分析を行ったところ、スルホン酸基導入率は２モル％であった。
<Example 5>
In the working sample 5, the transparent optical disc discharged at the factory as an aromatic polymer was pulverized, and a white solid was obtained in the same manner as in the working sample 2 described above, except that polycarbonate in powder form of 83 mesh pass was used. Obtained a flame retardant. That is, the working sample 5 is also an aromatic polymer into which a sulfonic acid group has been introduced. Then, when the obtained flame retardant was subjected to elemental analysis by the combustion flask method in the same manner as in the above-described Example 1, the sulfonic acid group introduction rate was 2 mol%.
〈実施サンプル６〉
実施サンプル６では、芳香族ポリマーとしてパウダー状のポリ（２，６−ジメチル−ｐ−フェニレンオキシド）を用いたこと以外は、上述した実施サンプル２と同様にして茶色固体からなる難燃剤を得た。すなわち、実施サンプル６も、スルホン酸基が導入された芳香族ポリマーである。そして、得られた難燃剤を上述した実施サンプル１と同様にして、燃焼フラスコ法による元素分析を行ったところ、スルホン酸基導入率は７.５モル％であった。
<Example 6>
In Working Sample 6, a flame retardant composed of a brown solid was obtained in the same manner as in Working Sample 2 described above, except that powdered poly (2,6-dimethyl-p-phenylene oxide) was used as the aromatic polymer. . That is, the working sample 6 is also an aromatic polymer into which a sulfonic acid group has been introduced. Then, when the obtained flame retardant was subjected to elemental analysis by the combustion flask method in the same manner as in the above-described Example 1, the sulfonic acid group introduction rate was 7.5 mol%.
〈比較サンプル１〉
比較サンプル１を作製する際は、先ず、芳香族ポリマーとして実施サンプル１で使用したスチレンホモポリマー２ｇを、１，２−ジクロロエタン１８ｇを注入した丸底フラスコに投入して溶解させ、ポリマー溶液を調製した。次に、１，２−ジクロロエタン１５ｇと、トリエチルホスフェート０．６ｇと、発煙硫酸２．３ｇとの混合液をポリマー溶液に１．５時間かけて滴下し、滴下後２時間熟成することで芳香族ポリマーに対してスルホン化処理を行った。次に、析出物を取り出し、メタノールに溶解させた後に、ジエチルエーテルにて再沈を行った後に、沈殿物を乾燥して固体を得た。
<Comparative sample 1>
When preparing the comparative sample 1, first, 2 g of the styrene homopolymer used in the implementation sample 1 as an aromatic polymer was introduced into a round bottom flask into which 18 g of 1,2-dichloroethane was injected and dissolved to prepare a polymer solution. did. Next, a mixture of 15 g of 1,2-dichloroethane, 0.6 g of triethyl phosphate, and 2.3 g of fuming sulfuric acid is dropped into the polymer solution over 1.5 hours, and then aged for 2 hours after the dropping. The polymer was sulfonated. Next, the precipitate was taken out, dissolved in methanol, reprecipitated with diethyl ether, and then dried to obtain a solid.
このとき、得られた固体について、上述した実施サンプル１と同様にして、燃焼フラスコ法による元素分析を行ったところ、難燃剤中に含有されるスルホン酸基導入率は６５モル％であった。 At this time, when the obtained solid was subjected to elemental analysis by a combustion flask method in the same manner as in the above-described implementation sample 1, the introduction rate of the sulfonic acid group contained in the flame retardant was 65 mol%.
次に、乾燥した固体を水酸化カリウムで中和した後に、再び乾燥することで、白色固体からなる難燃剤を作製した。すなわち、難燃剤としてスルホン酸基が６５モル％導入された芳香族ポリマーが得られた。 Next, the dried solid was neutralized with potassium hydroxide, and then dried again to prepare a flame retardant composed of a white solid. That is, an aromatic polymer having 65 mol% of sulfonic acid groups introduced as a flame retardant was obtained.
〈比較サンプル２〉
比較サンプル２では、ポリスチレンスルホン酸ナトリウム（重量平均分子量：１.８万）を難燃剤として用いる。そして、この難燃剤を上述した実施サンプル１と同様にして、燃焼フラスコ法による元素分析を行ったところ、スルホン酸基導入率は９９モル％であった。
<Comparative sample 2>
In Comparative Sample 2, sodium polystyrene sulfonate (weight average molecular weight: 18,000) is used as a flame retardant. And when this flame retardant was element-analyzed by the combustion flask method like the implementation sample 1 mentioned above, the sulfonic acid group introduction | transduction rate was 99 mol%.
〈比較サンプル３〉
比較サンプル３では、スルホン化処理に用いるスルホン化剤として９０重量％の濃硫酸を用い、スルホン化処理を８０℃雰囲気下で１時間行ったこと以外は、上述した実施サンプル３と同様にして黒色固体からなる難燃剤を得た。そして、得られた難燃剤を上述した実施サンプル１と同様にして、燃焼フラスコ法による元素分析を行ったところ、スルホン酸基導入率は３６モル％であった。難燃剤としてスルホン酸基が３６モル％導入された芳香族ポリマーが得られた。
<Comparative sample 3>
In Comparative Sample 3, black was used in the same manner as in Example 3 described above, except that 90% by weight concentrated sulfuric acid was used as the sulfonating agent used in the sulfonation treatment, and the sulfonation treatment was performed in an atmosphere at 80 ° C. for 1 hour. A flame retardant consisting of a solid was obtained. Then, when the obtained flame retardant was subjected to elemental analysis by the combustion flask method in the same manner as in the above-described Example 1, the sulfonic acid group introduction rate was 36 mol%. An aromatic polymer into which 36 mol% of sulfonic acid groups were introduced as a flame retardant was obtained.
次に、以上のようにして得られた実施サンプル及び比較サンプル、すなわち難燃剤を所定の被難燃樹脂に含有させて実施例及び比較例を作製した。 Next, the working sample and the comparative sample obtained as described above, that is, a flame retardant was contained in a predetermined flame retardant resin, and examples and comparative examples were produced.
〈実施例１〉
実施例１では、被難燃樹脂としてポリカーボネート樹脂（ビスフェノールＡ型）（以下、ＰＣと記す。）を９９．８重量部と、難燃剤として実施サンプル１を０．１重量部と、ドリップ抑制剤としてポリテトラフルオロエチレン（フィブリル形成性）（以下、ＰＴＦＥと記す。）を０．１重量部とを混合して難燃性樹脂前駆体を調製し、この難燃性樹脂前駆体を押出機に供給して所定の温度で混練し、ペレット化した後、このペレットを射出成形機に投入して所定の温度で射出形成して厚みが１．５ｍｍの難燃性樹脂組成物からなる短冊状の試験片を形成した。
<Example 1>
In Example 1, 99.8 parts by weight of a polycarbonate resin (bisphenol A type) (hereinafter referred to as PC) as a flame retardant resin, 0.1 part by weight of Example Sample 1 as a flame retardant, a drip inhibitor As a mixture, 0.1 part by weight of polytetrafluoroethylene (fibril forming property) (hereinafter referred to as PTFE) is mixed to prepare a flame retardant resin precursor, and this flame retardant resin precursor is used as an extruder. After being fed and kneaded at a predetermined temperature and pelletized, the pellets are put into an injection molding machine and injection-molded at a predetermined temperature to form a strip shape made of a flame retardant resin composition having a thickness of 1.5 mm A test piece was formed.
〈実施例２〉
実施例２では、被難燃樹脂としてＰＣを９９．８５重量部と、難燃剤として実施サンプル２を０．０５重量部と、ドリップ抑制剤としてＰＴＦＥを０．１重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 2>
In Example 2, it was difficult to mix 99.85 parts by weight of PC as a flame retardant resin, 0.05 parts by weight of Example Sample 2 as a flame retardant, and 0.1 parts by weight of PTFE as a drip inhibitor. A strip-shaped test piece was formed in the same manner as in Example 1 described above except that the flammable resin precursor was prepared.
〈実施例３〉
実施例３では、被難燃樹脂としてＰＣを９９．８５重量部と、難燃剤として実施サンプル５を０．０５重量部と、ドリップ抑制剤としてＰＴＦＥを０．１重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 3>
In Example 3, it was difficult to mix 99.85 parts by weight of PC as a flame retardant resin, 0.05 parts by weight of Example Sample 5 as a flame retardant, and 0.1 parts by weight of PTFE as a drip inhibitor. A strip-shaped test piece was formed in the same manner as in Example 1 described above except that the flammable resin precursor was prepared.
〈実施例４〉
実施例４では、被難燃樹脂としてＰＣ８３．８重量部及びアクリロニトリル-ブタジエン-スチレン共重合樹脂（アクリロニトリル／ポリブタジエン／スチレン＝２４／２０／５６：重量比）（以下、ＡＢＳ樹脂と記す。）１５重量部と、難燃剤として実施サンプル３を０．５重量部と、その他の難燃剤である珪素系難燃剤としてポリメチルフェニルシロキサン（以下、ＳＩと記す。）を０．５重量部と、ドリップ抑制剤としてＰＴＦＥを０．２重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 4>
In Example 4, 83.8 parts by weight of PC as a flame retardant resin and acrylonitrile-butadiene-styrene copolymer resin (acrylonitrile / polybutadiene / styrene = 24/20/56: weight ratio) (hereinafter referred to as ABS resin) 15 1 part by weight, 0.5 part by weight of Example 3 as a flame retardant, 0.5 part by weight of polymethylphenylsiloxane (hereinafter referred to as SI) as a silicon flame retardant as another flame retardant, and drip A strip-shaped test piece was formed in the same manner as in Example 1 described above except that PTFE was mixed with 0.2 part by weight as an inhibitor to prepare a flame retardant resin precursor.
〈実施例５〉
実施例５では、被難燃樹脂としてＰＣ８９．５重量部及びゴム変性ポリスチレン（ポリブタジエン／ポリスチレン＝１０／９０：重量比）（以下、ＨＩＰＳ樹脂と記す。）１０重量部と、難燃剤として実施サンプル２を０．１重量部と、その他の難燃剤としてＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．２重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 5>
In Example 5, 89.5 parts by weight of PC as a flame retardant resin and 10 parts by weight of rubber-modified polystyrene (polybutadiene / polystyrene = 10/90: weight ratio) (hereinafter referred to as HIPS resin) and an implementation sample as a flame retardant 2 except 0.1 parts by weight, 0.2 parts by weight of SI as another flame retardant, and 0.2 parts by weight of PTFE as a drip inhibitor were prepared to prepare a flame retardant resin precursor In the same manner as in Example 1 described above, a strip-shaped test piece was formed.
〈実施例６〉
実施例６では、被難燃樹脂としてＰＣ８９．４重量部及びアクリロニトリル-スチレン共重合樹脂（アクリロニトリル／スチレン＝２５／７５：重量比）（以下、ＡＳ樹脂と記す。）１０重量部と、難燃剤として実施サンプル１を０．２重量部と、その他の難燃剤であるＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．２重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 6>
In Example 6, as the flame retardant resin, 89.4 parts by weight of PC and 10 parts by weight of acrylonitrile-styrene copolymer resin (acrylonitrile / styrene = 25/75: weight ratio) (hereinafter referred to as AS resin), flame retardant As a sample, 0.2 parts by weight of sample 1, 0.2 parts by weight of SI as another flame retardant, and 0.2 parts by weight of PTFE as a drip inhibitor were mixed to obtain a flame retardant resin precursor. Except that it was prepared, strip-shaped test pieces were formed in the same manner as in Example 1 described above.
〈実施例７〉
実施例７では、被難燃樹脂としてＰＣ８４重量部及びポリエチレンテレフタレート（以下、ＰＥＴと記す。）１５重量部と、難燃剤として実施サンプル４を０．３重量部と、その他の難燃剤であるＳＩを０．４重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 7>
In Example 7, 84 parts by weight of PC and 15 parts by weight of polyethylene terephthalate (hereinafter referred to as PET) as a flame retardant resin, 0.3 parts by weight of Example Sample 4 as a flame retardant, and SI, which is another flame retardant A strip-shaped test in the same manner as in Example 1 except that 0.4 part by weight and 0.3 part by weight of PTFE as a drip inhibitor were mixed to prepare a flame retardant resin precursor. A piece was formed.
〈実施例８〉
実施例８では、被難燃樹脂としてＰＣ４９重量部及びポリ乳酸（以下、ＰＬＡと記す。）５０重量部と、難燃剤として実施サンプル５を０．２重量部と、その他の難燃剤であるＳＩを０．５重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 8>
In Example 8, 49 parts by weight of PC and 50 parts by weight of polylactic acid (hereinafter referred to as PLA) as a flame retardant resin, 0.2 parts by weight of Example 5 as a flame retardant, and SI, which is another flame retardant A strip-shaped test in the same manner as in Example 1 except that 0.5 part by weight and 0.3 part by weight of PTFE as a drip inhibitor were mixed to prepare a flame retardant resin precursor. A piece was formed.
〈実施例９〉
実施例９では、被難燃樹脂としてＡＢＳ９９重量部と、難燃剤として実施サンプル２を０．５重量部と、その他の難燃剤であるＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 9>
In Example 9, 99 parts by weight of ABS as a flame retardant resin, 0.5 parts by weight of sample 2 as a flame retardant, 0.2 parts by weight of SI as another flame retardant, and PTFE as a drip inhibitor A strip-shaped test piece was formed in the same manner as in Example 1 described above except that 0.3 part by weight was mixed to prepare a flame retardant resin precursor.
〈実施例１０〉
実施例１０では、被難燃樹脂としてＰＥＴ９９重量部と、難燃剤として実施サンプル４を０．５重量部と、その他の難燃剤であるＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 10>
In Example 10, 99 parts by weight of PET as a flame retardant resin, 0.5 parts by weight of Example Sample 4 as a flame retardant, 0.2 parts by weight of SI as another flame retardant, and PTFE as a drip inhibitor A strip-shaped test piece was formed in the same manner as in Example 1 described above except that 0.3 part by weight was mixed to prepare a flame retardant resin precursor.
〈実施例１１〉
実施例１０では、被難燃樹脂としてＰＣ９９．８重量部と、難燃剤として実施サンプル６を０．１重量部と、ドリップ抑制剤としてＰＴＦＥを０．１重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Example 11>
In Example 10, 99.8 parts by weight of PC as a flame retardant resin, 0.1 part by weight of Example Sample 6 as a flame retardant, and 0.1 part by weight of PTFE as a drip inhibitor were mixed to give flame retardancy. A strip-shaped test piece was formed in the same manner as in Example 1 described above except that the resin precursor was prepared.
〈比較例１〉
比較例１では、被難燃樹脂としてＰＣ９９．８重量部と、難燃剤として比較サンプル１を０．１重量部と、ドリップ抑制剤としてＰＴＦＥを０．１重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative example 1>
In Comparative Example 1, 99.8 parts by weight of PC as a flame retardant resin, 0.1 part by weight of Comparative Sample 1 as a flame retardant, and 0.1 part by weight of PTFE as a drip inhibitor are mixed to give flame retardancy. A strip-shaped test piece was formed in the same manner as in Example 1 described above except that the resin precursor was prepared.
〈比較例２〉
比較例２では、被難燃樹脂としてＰＣ９９．８重量部と、難燃剤として比較サンプル２を０．１重量部と、ドリップ抑制剤としてＰＴＦＥを０．１重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative example 2>
In Comparative Example 2, 99.8 parts by weight of PC as a flame retardant resin, 0.1 part by weight of Comparative Sample 2 as a flame retardant, and 0.1 part by weight of PTFE as a drip inhibitor were mixed to give flame retardancy. A strip-shaped test piece was formed in the same manner as in Example 1 described above except that the resin precursor was prepared.
〈比較例３〉
比較例３では、被難燃樹脂としてＰＣ９９．８５重量部と、難燃剤として比較サンプル３を０．０５重量部と、ドリップ抑制剤としてＰＴＦＥを０．１重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative Example 3>
In Comparative Example 3, 99.85 parts by weight of PC as a flame retardant resin, 0.05 parts by weight of Comparative Sample 3 as a flame retardant, and 0.1 parts by weight of PTFE as a drip inhibitor were mixed to give flame retardancy. A strip-shaped test piece was formed in the same manner as in Example 1 described above except that the resin precursor was prepared.
〈比較例４〉
比較例４では、被難燃樹脂としてＰＣ８３．８重量部及びＡＢＳ樹脂１５重量部と、難燃剤として比較サンプル３を０．５重量部と、その他の難燃剤であるＳＩを０．５重量部と、ドリップ抑制剤としてＰＴＦＥを０．２重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative example 4>
In Comparative Example 4, 83.8 parts by weight of PC and 15 parts by weight of ABS resin as flame retardant resin, 0.5 part by weight of Comparative Sample 3 as flame retardant, and 0.5 part by weight of SI as other flame retardants A strip-shaped test piece was formed in the same manner as in Example 1 except that a flame retardant resin precursor was prepared by mixing 0.2 part by weight of PTFE as a drip inhibitor.
〈比較例５〉
比較例５では、被難燃樹脂としてＰＣ８９．５重量部及びＨＩＰＳ樹脂１０重量部と、難燃剤として比較サンプル１を０．１重量部と、その他の難燃剤としてＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．２重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative Example 5>
In Comparative Example 5, 89.5 parts by weight of PC and 10 parts by weight of HIPS resin as a flame retardant resin, 0.1 part by weight of Comparative Sample 1 as a flame retardant, and 0.2 parts by weight of SI as another flame retardant A strip-shaped test piece was formed in the same manner as in Example 1 described above except that a flame retardant resin precursor was prepared by mixing 0.2 part by weight of PTFE as a drip inhibitor.
〈比較例６〉
比較例６では、被難燃樹脂としてＰＣ８９．４重量部及びＡＳ樹脂１０重量部と、難燃剤として比較サンプル２を０．２重量部と、その他の難燃剤であるＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．２重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative Example 6>
In Comparative Example 6, 89.4 parts by weight of PC and 10 parts by weight of AS resin as a flame retardant resin, 0.2 parts by weight of Comparative Sample 2 as a flame retardant, and 0.2 parts by weight of SI as another flame retardant A strip-shaped test piece was formed in the same manner as in Example 1 except that a flame retardant resin precursor was prepared by mixing 0.2 part by weight of PTFE as a drip inhibitor.
〈比較例７〉
比較例７では、被難燃樹脂としてＰＣ８４重量部及びＰＥＴ１５重量部と、難燃剤として比較サンプル３を０．３重量部と、その他の難燃剤であるＳＩを０．４重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative Example 7>
In Comparative Example 7, 84 parts by weight of PC and 15 parts by weight of PET as the flame retardant resin, 0.3 parts by weight of Comparative Sample 3 as the flame retardant, 0.4 parts by weight of SI as the other flame retardant, and drip suppression A strip-shaped test piece was formed in the same manner as in Example 1 described above except that PTFE was mixed with 0.3 part by weight as an agent to prepare a flame retardant resin precursor.
〈比較例８〉
比較例８では、被難燃樹脂としてＰＣ４９重量部及びＰＬＡ５０重量部と、難燃剤として比較サンプル１を０．２重量部と、その他の難燃剤であるＳＩを０．５重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative Example 8>
In Comparative Example 8, 49 parts by weight of PC and 50 parts by weight of PLA as flame retardant resin, 0.2 part by weight of Comparative Sample 1 as a flame retardant, 0.5 part by weight of SI as another flame retardant, and drip suppression A strip-shaped test piece was formed in the same manner as in Example 1 described above except that PTFE was mixed with 0.3 part by weight as an agent to prepare a flame retardant resin precursor.
〈比較例９〉
比較例９では、被難燃樹脂としてＡＢＳ９９重量部と、難燃剤として比較サンプル２を０．５重量部と、その他の難燃剤であるＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative Example 9>
In Comparative Example 9, 99 parts by weight of ABS as a flame retardant resin, 0.5 parts by weight of Comparative Sample 2 as a flame retardant, 0.2 parts by weight of SI as another flame retardant, and PTFE as a drip inhibitor A strip-shaped test piece was formed in the same manner as in Example 1 described above except that 0.3 part by weight was mixed to prepare a flame retardant resin precursor.
〈比較例１０〉
比較例１０では、被難燃樹脂としてＰＥＴ９９重量部と、難燃剤として比較サンプル３を０．５重量部と、その他の難燃剤であるＳＩを０．２重量部と、ドリップ抑制剤としてＰＴＦＥを０．３重量部とを混合して難燃性樹脂前駆体を調製したこと以外は、上述した実施例１と同様にして短冊状の試験片を形成した。
<Comparative Example 10>
In Comparative Example 10, 99 parts by weight of PET as a flame retardant resin, 0.5 part by weight of Comparative Sample 3 as a flame retardant, 0.2 part by weight of SI as another flame retardant, and PTFE as a drip inhibitor A strip-shaped test piece was formed in the same manner as in Example 1 described above except that 0.3 part by weight was mixed to prepare a flame retardant resin precursor.
次に、得られた各実施例及び各比較例について、燃焼性試験と外観検査とを行った。 Next, a flammability test and an appearance inspection were performed for each of the obtained Examples and Comparative Examples.
ここでの燃焼性試験は、ＵＬ９４（アンダーライターズラボラトリー・サブジェクト９４）のＶ−０、Ｖ−１、Ｖ−２規格に従って垂直燃焼試験を行った。具体的には、各実施例及び各比較例の試験片を各５個ずつ用意し、略垂直状に指示した短冊状試験片に対して下側からバーナー炎をあてて１０秒間保ち、その後、バーナー炎を短冊状試験片から離す。炎が消えれば直ちにバーナー炎をさらに１０秒間あてた後、バーナー炎を離す。このとき、１回目と２回目の接炎終了後の有炎燃焼持続時間、２回目の接炎終了後の有炎燃焼持続時間及び無炎燃焼持続時間の合計、５本全ての試験片の有炎燃焼時間の合計、燃焼滴下物の有無で判定する。そして、Ｖ−０規格は、１回目、２回目ともに１０秒以内に、Ｖ−１、Ｖ−２規格は、１回目、２回目ともに３０秒以内に有炎燃焼を終えたときである。また、２回目の有炎燃焼持続時間と無炎燃焼持続時間との合計がＶ−０規格は３０秒以内、Ｖ−１及びＶ−２規格は６０秒以内である。さらに、５本の試験片の有炎燃焼時間の合計がＶ−０規格は５０秒以内、Ｖ−１及びＶ−２規格は２５０秒以内である。さらにまた、燃焼落下物は、Ｖ−２規格のみに許容される。すなわち、ＵＬ燃焼試験法（ＵＬ９４）においては、Ｖ−０、Ｖ−１、Ｖ−２規格の順で難燃性が高くなる。 The flammability test here was a vertical flammability test according to UL94 (underwriters laboratory subject 94) V-0, V-1, V-2 standards. Specifically, five test pieces of each example and each comparative example were prepared, and the burner flame was applied from the lower side to the strip-shaped test piece indicated in a substantially vertical shape for 10 seconds. Separate the burner flame from the strip specimen. Immediately after the flame has disappeared, apply the burner flame for another 10 seconds, and then release the burner flame. At this time, the total of the flammable combustion duration after the first and second flame contact, the flaming combustion duration and the flameless combustion duration after the second flame contact, and the presence of all five test pieces Judgment is based on the total flame burning time and the presence or absence of combustion drops. The V-0 standard is when the flammable combustion is completed within 10 seconds for both the first and second times, and the V-1 and V-2 standards are within 30 seconds for both the first and second times. The total of the second flammable combustion duration and the flameless combustion duration is within 30 seconds for the V-0 standard, and within 60 seconds for the V-1 and V-2 standards. Further, the total flame burning time of the five test pieces is within 50 seconds for the V-0 standard, and within 250 seconds for the V-1 and V-2 standards. Furthermore, combustion fallen objects are allowed only in the V-2 standard. That is, in the UL combustion test method (UL94), flame retardancy increases in the order of the V-0, V-1, and V-2 standards.
また、外観検査は、各実施例及び各比較例の試料片を８０℃雰囲気下、湿度８０％の恒温恒湿槽内に３０日間曝した後に、試験片の外観を目視で確認し、変色が無かった場合は○印で示し、変色が生じた場合は×印で示した。 In addition, in the appearance inspection, the sample pieces of each Example and each Comparative Example were exposed to a constant temperature and humidity chamber of 80% humidity in an 80 ° C. atmosphere for 30 days, and then the appearance of the test piece was visually confirmed, and discoloration was observed. When there was no change, it was indicated by a circle, and when a discoloration occurred, it was indicated by a cross.
以下、表１に、各実施例及び各比較例における燃焼性試験と外観検査について評価した結果を示す。 Table 1 below shows the results of evaluating the flammability test and the appearance inspection in each example and each comparative example.
表１に示す評価結果から、芳香族ポリマーに対するスルホン酸基の導入率が０．１モル％〜８モル％の範囲で難燃剤を含有する実施例１〜実施例３、及び実施例１１は、芳香族ポリマーに対するスルホン酸基の導入率が３６モル％〜９５モル％の範囲で難燃剤を含有する比較例１〜比較例３に比べ、難燃性が高められていることがわかる。 From the evaluation results shown in Table 1, Examples 1 to 3 and Example 11 in which the introduction rate of the sulfonic acid group with respect to the aromatic polymer is within the range of 0.1 mol% to 8 mol%, It can be seen that the flame retardancy is enhanced as compared with Comparative Examples 1 to 3 containing a flame retardant when the introduction rate of the sulfonic acid group to the aromatic polymer is in the range of 36 mol% to 95 mol%.
比較例１〜比較例３では、燃え易いものと燃えにくいものとが発生し、結果として実施例１〜実施例３、及び実施例１１より難燃性の劣ったものしか得られなかった。 In Comparative Example 1 to Comparative Example 3, flammable and non-flammable materials were generated, and as a result, only those having inferior flame retardancy were obtained as compared with Examples 1 to 3 and Example 11.
また、表１に示す評価結果から、難燃剤として比較サンプル３を含有する比較例３、４、７、１０では、高温高湿下に曝すことで難燃性樹脂組成物中に微小な吸湿物の斑点が発生し、外観不良となった。 Further, from the evaluation results shown in Table 1, in Comparative Examples 3, 4, 7, and 10 containing Comparative Sample 3 as a flame retardant, a minute moisture absorbent is contained in the flame retardant resin composition by exposure to high temperature and high humidity. Spots occurred and the appearance was poor.
比較例３、４、７、１０では、スルホン化剤として水分が９０重量％の濃硫酸を用いた比較サンプル３にはスルホン酸基の他に、水分を吸収し易いアミド基やカルボキシル基等が導入されてしまい、このようなアミド基やカルボキシル基等が含有された比較サンプル３を難燃剤として使用したために、水分を吸収し易くなる。 In Comparative Examples 3, 4, 7, and 10, in Comparative Sample 3 using concentrated sulfuric acid having a water content of 90% by weight as a sulfonating agent, in addition to the sulfonic acid group, an amide group or a carboxyl group that easily absorbs water is used. Since the comparative sample 3 containing such an amide group or carboxyl group is used as a flame retardant, it is easy to absorb moisture.
さらに、表１に示す評価結果から、実施例４〜実施例１１は、比較例４〜比較例１０に比べ、難燃性が高められていることがわかる。 Furthermore, from the evaluation results shown in Table 1, it can be seen that the flame retardancy of Examples 4 to 11 is enhanced as compared with Comparative Examples 4 to 10.
実施例４〜実施例１１では、芳香族ポリマーに含有されるスルホン酸基の導入率を低くされた難燃剤を用いることで、難燃剤と被難燃樹脂との相溶性が向上されたことにより、難燃性が適切に付与された難燃性樹脂組成物となる。 In Examples 4 to 11, the compatibility between the flame retardant and the flame retardant resin was improved by using a flame retardant having a reduced introduction rate of sulfonic acid groups contained in the aromatic polymer. The flame retardant resin composition is appropriately provided with flame retardancy.
さらにまた、表１に示す評価結果から、各実施例は、難燃剤を被難燃樹脂に少量加えることで難燃性が効果的に付与されていることがわかる。 Furthermore, from the evaluation results shown in Table 1, it can be seen that in each example, flame retardancy is effectively imparted by adding a small amount of a flame retardant to the flame retardant resin.
以上ことから、難燃性樹脂組成物を作製するに際して、スルホン酸基が０．１モル％〜８モル％の範囲で導入された芳香族ポリマーを難燃剤として用いることは、難燃性が適切に付与され、長期保存されても外観不良が生じることのない優れた難燃性樹脂組成物を得る上で大変重要であることがわかる。
From the above, when preparing a flame retardant resin composition, it is appropriate to use an aromatic polymer having a sulfonic acid group introduced in a range of 0.1 mol% to 8 mol% as a flame retardant. It can be seen that it is very important in obtaining an excellent flame retardant resin composition that does not cause poor appearance even when stored for a long time.
Claims (10)
芳香族骨格を有するモノマー単位を１モル％〜１００モル％の範囲で含有する芳香族ポリマーを有し、この芳香族ポリマーにスルホン酸基及び／又はスルホン酸塩基が０．１モル％〜８．０モル％の範囲で導入されている難燃剤。 In a flame retardant that imparts flame retardancy to the resin composition by containing it in the resin composition,
It has an aromatic polymer containing a monomer unit having an aromatic skeleton in the range of 1 mol% to 100 mol%, and the sulfonic acid group and / or sulfonate group is 0.1 mol% to 8. Flame retardant introduced in the range of 0 mol%.
上記難燃剤は、芳香族骨格を有するモノマー単位を１モル％〜１００モル％の範囲で含有する芳香族ポリマーを有し、この芳香族ポリマーにスルホン酸基及び／又はスルホン酸塩基が０．１モル％〜８．０モル％の範囲で導入されている難燃性樹脂組成物。 In the flame retardant resin composition provided with flame retardancy by containing a flame retardant in the resin composition,
The flame retardant has an aromatic polymer containing a monomer unit having an aromatic skeleton in the range of 1 mol% to 100 mol%, and the sulfonic acid group and / or sulfonate group is 0.1% in the aromatic polymer. A flame retardant resin composition introduced in a range of from mol% to 8.0 mol%.
Priority Applications (19)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004085480A JP4196862B2 (en) | 2004-03-23 | 2004-03-23 | Flame retardant, flame retardant resin composition |
| PCT/JP2005/004830 WO2005090468A1 (en) | 2004-03-23 | 2005-03-17 | Flame retardant, flame-retarded resin compositions, and process for production of the flame retardant |
| KR1020117030483A KR101212869B1 (en) | 2004-03-23 | 2005-03-17 | Flame Retardant, Flame-Retarded Resin Compositions, and Process for Production of the Flame Retardant |
| CN201310656423.4A CN103756275A (en) | 2004-03-23 | 2005-03-17 | Flame retardant, flame-retarded resin compositions, and process for production of the flame retardant |
| EP13003603.1A EP2674458B1 (en) | 2004-03-23 | 2005-03-17 | Flame retarder, flame retardant resin composition and method of producing the flame retarder |
| CA2771888A CA2771888C (en) | 2004-03-23 | 2005-03-17 | Flame retarder, flame retardant resin composition and method of producing the flame retarder |
| EP12000759.6A EP2452977B1 (en) | 2004-03-23 | 2005-03-17 | Flame retarder, flame retardant resin composition and method of producing the flame retarder |
| CN2010102505977A CN101914299A (en) | 2004-03-23 | 2005-03-17 | Flame retardant, flame-retarded resin compositions, and process for production of the flame retardant |
| CA2560245A CA2560245C (en) | 2004-03-23 | 2005-03-17 | Flame retarder, flame retardant resin composition and method of producing the flame retarder |
| AU2005223552A AU2005223552B2 (en) | 2004-03-23 | 2005-03-17 | Flame retardant, flame-retarded resin compositions, and process for production of the flame retardant |
| EP05721017.1A EP1728823B1 (en) | 2004-03-23 | 2005-03-17 | Flame retardant, flame-retarded resin compositions, and process for production of the flame retardant |
| CN2005800165770A CN1957037B (en) | 2004-03-23 | 2005-03-17 | Flame retardant, flame-retardant resin composition and method for producing flame retardant |
| CN2010102505835A CN101906242A (en) | 2004-03-23 | 2005-03-17 | Flame retardant, flame-retarded resin compositions, and process for production of the flame retardant |
| US10/598,899 US8440758B2 (en) | 2004-03-23 | 2005-03-17 | Flame retarder, flame retardant resin composition and method of producing the flame retarder |
| TW094108672A TW200613531A (en) | 2004-03-23 | 2005-03-21 | Flame retardant, flame-retardant resin composition and method for producing flame retardant |
| KR1020067019597A KR101215114B1 (en) | 2004-03-23 | 2006-09-22 | Flame Retardant Flame-Retarded Resin Compositions and Process for Production of the Flame Retardant |
| AU2010214809A AU2010214809A1 (en) | 2004-03-23 | 2010-09-03 | Flame retarder, flame retardant resin composition and method of producing the flame retarder |
| AU2010214811A AU2010214811B2 (en) | 2004-03-23 | 2010-09-03 | Flame retarder, flame-retardant resin composition and method of producing the flame retarder |
| US13/867,601 US10508239B2 (en) | 2004-03-23 | 2013-04-22 | Flame retarder, flame retardant resin composition and method of producing the flame retarder |
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| JP2004085480A JP4196862B2 (en) | 2004-03-23 | 2004-03-23 | Flame retardant, flame retardant resin composition |
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| WO2014033987A1 (en) | 2012-08-31 | 2014-03-06 | ソニー株式会社 | Resin composition and resin-molded article |
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| JP5286634B2 (en) * | 2005-09-02 | 2013-09-11 | ソニー株式会社 | Method for sulfonation of aromatic compound and powder comprising aromatic sulfonic acid compound |
| JP5076675B2 (en) * | 2007-06-26 | 2012-11-21 | ソニー株式会社 | Flame retardant and resin composition |
| JP5029210B2 (en) | 2007-08-20 | 2012-09-19 | ソニー株式会社 | Flame retardant and method for producing the same, and resin composition and method for producing the same |
| JP6855039B2 (en) * | 2016-09-12 | 2021-04-07 | 小西化学工業株式会社 | Method for Producing Sulfonized Polyphenylene Oxide |
| JP7067480B2 (en) * | 2016-10-06 | 2022-05-16 | ソニーグループ株式会社 | Transmissive resin composition and transmissive resin molded product |
| CN116790120A (en) | 2019-05-21 | 2023-09-22 | 旭化成株式会社 | Polyamide composition, method for producing same, and molded article |
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