JP2005154762A5 - - Google Patents
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- JP2005154762A5 JP2005154762A5 JP2004321528A JP2004321528A JP2005154762A5 JP 2005154762 A5 JP2005154762 A5 JP 2005154762A5 JP 2004321528 A JP2004321528 A JP 2004321528A JP 2004321528 A JP2004321528 A JP 2004321528A JP 2005154762 A5 JP2005154762 A5 JP 2005154762A5
- Authority
- JP
- Japan
- Prior art keywords
- component
- thermoplastic resin
- group
- weight
- resin composition
- 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.)
- Granted
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- -1 phosphorus compound Chemical class 0.000 claims description 91
- 229920005989 resin Polymers 0.000 claims description 82
- 239000011347 resin Substances 0.000 claims description 82
- 239000003063 flame retardant Substances 0.000 claims description 64
- 229920005992 thermoplastic resin Polymers 0.000 claims description 54
- 239000011342 resin composition Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 46
- 229920001955 polyphenylene ether Polymers 0.000 claims description 33
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 16
- 229920000069 poly(p-phenylene sulfide) Polymers 0.000 claims description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 14
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 230000004580 weight loss Effects 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001225 Polyester resin Polymers 0.000 claims description 4
- 239000004760 aramid Substances 0.000 claims description 4
- 229920003235 aromatic polyamide Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims 1
- 239000004416 thermosoftening plastic Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 40
- 230000000694 effects Effects 0.000 description 20
- 238000002156 mixing Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 125000001424 substituent group Chemical group 0.000 description 11
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- 239000011528 polyamide (building material) Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 229920002302 Nylon 6,6 Polymers 0.000 description 7
- 238000010928 TGA analysis Methods 0.000 description 7
- 125000004432 carbon atoms Chemical group C* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000000779 smoke Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Xylenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-Hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000003014 reinforcing Effects 0.000 description 4
- 239000000565 sealant Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 3
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 125000004437 phosphorous atoms Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-Dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 2
- 229920000122 Acrylonitrile butadiene styrene Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-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
- AYJRCSIUFZENHW-UHFFFAOYSA-L Barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 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
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N Melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N O-Cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920001470 Polyketone Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N Sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N Triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive Effects 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatoms Chemical group 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 230000001771 impaired Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atoms Chemical group 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- ILUAAIDVFMVTAU-OLQVQODUSA-N (1S,2R)-cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)[C@H]1CC=CC[C@H]1C(O)=O ILUAAIDVFMVTAU-OLQVQODUSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-tris(prop-2-enoxy)-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- BIAWAXVRXKIUQB-UHFFFAOYSA-N 2-(2-phenylethenyl)pyridine Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=N1 BIAWAXVRXKIUQB-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-N-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- XHFOXACKHBOLCX-UHFFFAOYSA-N 2-N-[10-[(4,6-diamino-1,3,5-triazin-2-yl)amino]decyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCCCCCCCCCCNC=2N=C(N)N=C(N)N=2)=N1 XHFOXACKHBOLCX-UHFFFAOYSA-N 0.000 description 1
- KYCZUBOPFDXYAU-UHFFFAOYSA-N 2-N-[[(4,6-diamino-1,3,5-triazin-2-yl)amino]methyl]-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NCNC=2N=C(N)N=C(N)N=2)=N1 KYCZUBOPFDXYAU-UHFFFAOYSA-N 0.000 description 1
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N 4,4'-Biphenol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- IXDGHAZCSMVIFX-UHFFFAOYSA-N 6-(dibutylamino)-1H-1,3,5-triazine-2,4-dithione Chemical compound CCCCN(CCCC)C1=NC(=S)NC(=S)N1 IXDGHAZCSMVIFX-UHFFFAOYSA-N 0.000 description 1
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N Acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 229920000180 Alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N Boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- WLPKFQRBARNCNR-UHFFFAOYSA-N C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 Chemical compound C=C.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 WLPKFQRBARNCNR-UHFFFAOYSA-N 0.000 description 1
- 229960005069 Calcium Drugs 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N Calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N Caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 240000002275 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N Cyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N Dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N Hexamethylenediamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
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- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
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- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical group OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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Description
本発明は難燃性熱可塑性樹脂組成物に関する。さらに詳しくは、加工性に優れ、かつ難燃性、耐吸湿性、耐熱性に優れる難燃性熱可塑性樹脂組成物に関する。 The present invention relates to a flame retardant thermoplastic resin composition. More specifically, the present invention relates to a flame retardant thermoplastic resin composition having excellent processability and excellent flame retardancy, moisture absorption resistance, and heat resistance.
従来、易燃性樹脂の難燃化の手法として、含塩素化合物、含臭素化合物、三酸化アンチモンなどを添加する方法や、樹脂中に含塩素化合物、含臭素化合物を含有させる手法が用いられてきたが、これらは環境保護の観点、毒性の面等から好ましくないとの指摘があり、難燃化手法の改善が求められている。含塩素、含臭素系難燃剤を用いない難燃化手法としてリン系難燃剤を用いた難燃化手法が検討されている。 Conventionally, as a technique for making flame-retardant resins flame retardant, a method of adding a chlorine-containing compound, a bromine-containing compound, antimony trioxide, or the like, or a method of containing a chlorine-containing compound or a bromine-containing compound in a resin has been used. However, it has been pointed out that these are not preferable from the viewpoint of environmental protection, toxicity, etc., and improvement of the flame retardant method is demanded. Flame retardant methods using phosphorus-based flame retardants are being studied as flame retardant methods that do not use chlorine-containing or bromine-containing flame retardants.
一例を挙げると、特許文献1には、ポリフェニレンエーテル及びポリスチレンと、ホスファゼン化合物からなる難燃樹脂組成物が開示されていが、これは樹脂組成物の難燃性は優れるものの、加工性や成形品外観などの点において充分満足できるものではなかった。
また、特許文献2では、ポリカーボネート樹脂と無機質充填剤及び、アリールホスフィン又は燐酸エステルからなる樹脂組成物が提案されているが、機械強度の低下を招く等問題があった。
As an example, Patent Document 1 discloses a flame retardant resin composition comprising polyphenylene ether and polystyrene and a phosphazene compound, which is excellent in flame retardancy of the resin composition, but has excellent workability and molded product. It was not satisfactory in terms of appearance and the like.
Further, Patent Document 2 proposes a resin composition comprising a polycarbonate resin, an inorganic filler, and an aryl phosphine or a phosphate ester. However, there are problems such as a decrease in mechanical strength.
また、特許文献3で提案されている、低分子量ポリフェニレンエーテル樹脂及びホスファゼン化合物と併用した難燃剤組成物は、難燃性、機械特性、成型加工性の観点からも有効である。しかし、成型加工性や機械的特性、誘電特性に対する要求、難燃剤添加量の減量化の要求は尽きることはなく、さらなる向上が求められている。 Moreover, the flame retardant composition used in combination with the low molecular weight polyphenylene ether resin and the phosphazene compound proposed in Patent Document 3 is also effective from the viewpoint of flame retardancy, mechanical properties, and moldability. However, the requirements for molding processability, mechanical properties, dielectric properties, and reduction of the amount of flame retardant added are not exhausted, and further improvements are required.
本発明による難燃性熱可塑性樹脂組成物の課題は、塩素、臭素化合物を含まず、樹脂に添加した場合に、難燃性、耐吸湿性、耐熱性、誘電特性、低発煙性、押出作業性に優れる難燃性熱可塑性樹脂組成物を提供するものである。 The problem of the flame retardant thermoplastic resin composition according to the present invention is that it does not contain chlorine or bromine compounds, and when added to the resin, flame retardant, moisture absorption, heat resistance, dielectric properties, low smoke generation, extrusion work A flame retardant thermoplastic resin composition having excellent properties is provided.
本発明者は上記課題を解決するために鋭意検討した結果、熱可塑性樹脂に対して、(A)三価のリン化合物及び、(B)特定のホスファゼン化合物、必要により(C)芳香族含有樹脂を組み合わせてなる難燃剤組成物を用いることにより、樹脂表面への炭化皮膜の形成を促進し、炭化皮膜を形成し難い樹脂に対しても安定した難燃性を得ることができ、且つ優れた耐熱性、耐加水分解性、機械特性、誘電特性、低発煙性、及び成形品外観を有する難燃性熱可塑性樹脂組成物が得られることを見出し、本発明に到達した。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that (A) a trivalent phosphorus compound, (B) a specific phosphazene compound, and (C) an aromatic-containing resin if necessary. Can be used to promote the formation of a carbonized film on the resin surface, provide stable flame retardancy even for resins that are difficult to form a carbonized film, and excellent The present inventors have found that a flame-retardant thermoplastic resin composition having heat resistance, hydrolysis resistance, mechanical properties, dielectric properties, low smoke generation, and appearance of a molded product can be obtained, and the present invention has been achieved.
すなわち、本発明は以下に記載する通りのものである。
1.熱可塑性樹脂に下記(A)成分と下記(B)成分とを含有させてなることを特徴とする難燃性熱可塑性樹脂組成物。
(A)成分:三価のリン化合物
(B)成分:TGAによる不活性ガス雰囲気下、昇温速度10℃/minで常温から600℃まで加熱した時の、50重量%の重量減少時の温度と5重量%の重量減少時の温度の差が40〜100℃であるホスファゼン化合物
That is, the present invention is as described below.
1. A flame retardant thermoplastic resin composition comprising a thermoplastic resin containing the following component (A) and the following component (B).
(A) Component: Trivalent phosphorus compound (B) Component: Temperature at a weight loss of 50% by weight when heated from normal temperature to 600 ° C. at a heating rate of 10 ° C./min in an inert gas atmosphere by TGA And a phosphazene compound having a temperature difference of 40 to 100 ° C. when the weight is reduced by 5% by weight
2.(A)成分と(B)成分の合計100重量部中、(A)成分を0.1〜60重量部、(B)成分を99.9〜40重量部含有することを特徴とする上記1に記載の難燃性熱可塑性樹脂組成物。
3.(B)成分の酸価が1.0以下であり、且つカールフィッシャー法により150℃にて測定した水分量が1000ppm以下である上記1又は2に記載の難燃性熱可塑性樹脂組成物。
4.(B)成分における、TGAによる不活性ガス雰囲気下、昇温速度10℃/minで常温から600℃まで加熱した時の、50重量%の重量減少時の温度が320〜460℃であることを特徴とする上記1〜3のいずれか一項に記載の難燃性熱可塑性樹脂組成物。
5.(A)成分が、TGAによる不活性ガス雰囲気下、昇温速度10℃/minで常温から600℃まで加熱した時の10重量%の重量減少時の温度が120℃〜320℃である上記1〜4のいずれか一項に記載の難燃性熱可塑性樹脂組成物。
2. 1 to 60 parts by weight of component (A) and 99.9 to 40 parts by weight of component (B) in 100 parts by weight of component (A) and component (B). The flame-retardant thermoplastic resin composition as described in 1.
3. The flame retardant thermoplastic resin composition according to 1 or 2 above, wherein the acid value of the component (B) is 1.0 or less and the water content measured at 150 ° C. by the Karl Fischer method is 1000 ppm or less.
4). (B) In the inert gas atmosphere by TGA, the temperature at the time of weight reduction of 50 weight% when heated from normal temperature to 600 degreeC with the temperature increase rate of 10 degree-C / min is 320-460 degreeC. 4. The flame retardant thermoplastic resin composition according to any one of 1 to 3 above.
5). (1) The above component (A) has a temperature of 120% to 320 ° C. when the weight is reduced by 10% by weight when heated from normal temperature to 600 ° C. at a heating rate of 10 ° C./min in an inert gas atmosphere by TGA. The flame-retardant thermoplastic resin composition as described in any one of -4.
6.(A)成分が、三級ホスフィン類である上記1〜4のいずれか一項に記載の難燃性熱可塑性樹脂組成物。
7.(A)成分が、トリアリールホスフィン類であることを上記1〜4のいずれか一項に記載の難燃性熱可塑性樹脂組成物。
6). (A) The flame-retardant thermoplastic resin composition as described in any one of 1 to 4 above, wherein the component is a tertiary phosphine.
7). (A) The flame-retardant thermoplastic resin composition as described in any one of 1 to 4 above, wherein the component is a triarylphosphine.
8.更に、(C)成分として芳香族樹脂を含有することを特徴とする上記1〜7のいずれか一項に記載の難燃性熱可塑性樹脂組成物。
9.(C)成分が、ポリフェニレンエーテル系樹脂、ポリフェニレンスルフィド系樹脂、フェノール系樹脂、芳香族ポリアミド系樹脂、ポリエステル系樹脂、サーモトロピック液晶から選ばれる少なくとも一種の樹脂であることを特徴とする上記8に記載の難燃性熱可塑性樹脂組成物。
10.(C)成分が、ポリフェニレンエーテル系樹脂であることを特徴とする上記8に記載の難燃性熱可塑性樹脂組成物。
11.(C)成分と(B)成分の比が(C)/(B)=95/5〜5/95であることを特徴とする上記8〜10いずれかに記載の難燃性熱可塑性樹脂組成物。
8 . Furthermore, the flame retardant thermoplastic resin composition as described in any one of 1 to 7 above, which further comprises an aromatic resin as the component (C).
9 . Component (C), a polyphenylene ether resin, polyphenylene sulfide resin, phenol resin, aromatic polyamide resin, a polyester resin, the above 8, wherein the at least one resin selected from the thermotropic liquid crystal The flame-retardant thermoplastic resin composition as described.
10 . 9. The flame retardant thermoplastic resin composition as described in 8 above, wherein the component (C) is a polyphenylene ether resin.
11 . The flame retardant thermoplastic resin composition according to any one of 8 to 10 above, wherein the ratio of the component (C) to the component (B) is (C) / (B) = 95/5 to 5/95. Stuff.
本発明によれば、ハロゲンを含まず、耐熱性、機械特性、加工性、誘電特性及び難燃性のバランスに優れた難燃性熱可塑性樹脂組成物が提供される。 According to the present invention, there is provided a flame retardant thermoplastic resin composition which does not contain halogen and has an excellent balance of heat resistance, mechanical properties, processability, dielectric properties and flame retardancy.
以下に本発明を詳細に説明する。
本発明においては、熱可塑性樹脂に対して、(A)三価のリン化合物及び、(B)特定のホスファゼン化合物で構成された難燃剤組成物を配合することにより大きな効果を発揮し、優れた難燃性及び諸特性を得ることができる。また、(A)三価のリン化合物、(B)特定のホスファゼン化合物及び(C)芳香族樹脂で構成された難燃剤組成物を配合することにより、(C)成分が炭化層の形成をより効率良く行って、優れた難燃性及び諸特性を得ることができる。
The present invention is described in detail below.
In the present invention, the thermoplastic resin exhibits a great effect by blending a flame retardant composition composed of (A) a trivalent phosphorus compound and (B) a specific phosphazene compound . Flame retardancy and various properties can be obtained. In addition, by blending a flame retardant composition composed of (A) a trivalent phosphorus compound, (B) a specific phosphazene compound and (C) an aromatic resin, the component (C) can more effectively form a carbonized layer. It can be carried out efficiently to obtain excellent flame retardancy and various characteristics.
(熱可塑性樹脂)
本発明において使用に供される熱可塑性樹脂は従来公知の熱可塑性樹脂が好適に用いられる。一例を挙げると、ポリフェニレンエーテル系樹脂、ポリフェニレンサルファイド系樹脂、ポリプロピレン系樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、ハイインパクトポリスチレン、エラストマー含有ポリスチレン、シンジオタクテックポリスチレン系樹脂、ABS系樹脂、AS系樹脂、ポリケトン系樹脂、生分解性樹脂、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリトリメチレンテレフタレート等のポリアルキレンテレフタレート系樹脂、ポリアミド系樹脂、サーモトロピック液晶等が挙げられ、特にポリフェニレンエーテル系樹脂、ポリスチレン系樹脂、ABS系樹脂、ポリケトン系樹脂、ポリフェニレンエーテルとポリスチレンのアロイ、ポリフェニレンエーテルとポリアミドのアロイ、ポリフェニレンエーテルとサーモトロピック液晶とのアロイ、ポリフェニレンエーテルとポリフェニレンサルファイドとのアロイが好適に使用される。
これらの樹脂は一種単独で用いても良いし、二種以上の混合物として用いても良い。
(Thermoplastic resin)
A conventionally known thermoplastic resin is preferably used as the thermoplastic resin used in the present invention. For example, polyphenylene ether resin, polyphenylene sulfide resin, polypropylene resin, polyethylene resin, polystyrene resin, high impact polystyrene, elastomer-containing polystyrene, syndiotactic polystyrene resin, ABS resin, AS resin, Examples include polyketone resins, biodegradable resins, polybutylene terephthalate, polyethylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate and other polyalkylene terephthalate resins, polyamide resins, thermotropic liquid crystals, etc., especially polyphenylene ether resins, polystyrene Resin, ABS resin, polyketone resin, polyphenylene ether and polystyrene alloy, polyphenylene ether and poly De alloys, alloy of polyphenylene ether and thermotropic liquid crystal, alloy of polyphenylene ether and polyphenylene sulfide is preferably used.
These resins may be used alone or in a mixture of two or more.
(A)成分:三価のリン化合物
本発明で用いられる三価のリン化合物としては、従来公知のものを好適に用いることができるが、耐熱性及び、難燃性、機械特性のバランスを考慮すると、TGAによる不活性ガス雰囲気下、昇温速度10℃/minで常温から600℃まで加熱した時の10重量%の重量減少時の温度が、150℃〜320℃である三価のリン化合物であることが好ましい。一例を挙げると、トリアリールホスフィン、トリアルキルホスフィン、トリアリールオキシホスフィン、トリアルコキシホスフィン等が挙げられる。より具体的には、その中でも、下記一般式(1)で表されるトリアリールホスフィン類が好適に用いられる。ここで、T1、T2、T3、T4は、独立に水素原子又は炭素数1から12のアルキル基又はアリール基を表し、T5は水素原子又はメチル基を表す。m1、m2、m3、m4は独立に0から5の整数を示し、m5は独立に0から4の整数を表す。また、式中のnは、0〜3の整数を表す。また、アリール基として、ナフチル基も好適に用いることができる。また、リン原子上の三つのアリール基は、すべて同じ基であっても、それぞれ異なる基であっても良い。
Component (A): Trivalent phosphorus compound As the trivalent phosphorus compound used in the present invention, conventionally known compounds can be suitably used, but considering the balance between heat resistance, flame retardancy, and mechanical properties. Then, a trivalent phosphorus compound having a temperature of 10% by weight when heated from room temperature to 600 ° C. in an inert gas atmosphere by TGA at a temperature rising rate of 10 ° C./min is 150 ° C. to 320 ° C. It is preferable that For example, triarylphosphine, trialkylphosphine, triaryloxyphosphine, trialkoxyphosphine and the like can be mentioned. More specifically, among them, triarylphosphines represented by the following general formula (1) are preferably used. Here, T1, T2, T3, and T4 independently represent a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms, and T5 represents a hydrogen atom or a methyl group. m1, m2, m3, and m4 each independently represents an integer of 0 to 5, and m5 independently represents an integer of 0 to 4. Moreover, n in a formula represents the integer of 0-3. Moreover, a naphthyl group can also be used suitably as an aryl group. Further, the three aryl groups on the phosphorus atom may be the same group or different groups.
また、三価のリン化合物は、置換基の種類や構造の違いによっても異なるが、液状、ワックス状、固体状等、さまざまな形態を取ることができ、本発明の効果を損なわないものであれば、どのような形状でも構わない。
これらの三価のリン化合物は一種単独で用いても良いし、二種以上の混合物として用いても良い。
In addition, the trivalent phosphorus compound varies depending on the type and structure of the substituent, but can take various forms such as liquid, wax, solid, etc., and does not impair the effects of the present invention. Any shape can be used.
These trivalent phosphorus compounds may be used alone or as a mixture of two or more.
(B)成分:ホスファゼン化合物
本発明のホスファゼン化合物は、(A)成分と併用して用いた場合の、難燃性、燃焼時の低発煙性、低揮発性等を考慮すると、TGAによる不活性ガス雰囲気下、昇温速度10℃/minで常温から600℃まで加熱した時の、50重量%の重量減少時の温度と5重量%の重量減少時の温度の差が、40〜100℃、好適には40〜90℃、より好ましくは45〜85℃、更に好ましくは45〜75℃、特に好ましくは45〜70℃であるものが好ましい。また、樹脂に対して用いた場合、燃焼時の炭化層形成促進効果による難燃効率を考えると、50重量%の重量減少時の温度が320〜460℃であるものが好ましく、より好ましくは350〜450℃であるものが好ましい。
なお、以下では「〜重量%の重量減少時の温度」を「〜%減量温度」という場合がある。
Component (B): phosphazene compound phosphazene compound of the present invention, (A) when used in combination with components, flame retardant, low smoke emission during combustion, in view of low volatility such as, TGA with an inert In a gas atmosphere, when heated from room temperature to 600 ° C. at a rate of temperature increase of 10 ° C./min, the difference between the temperature when the weight is reduced by 50 wt% and the temperature when the weight is reduced by 5 wt% is 40 to 100 ° C. It is preferably 40 to 90 ° C, more preferably 45 to 85 ° C, still more preferably 45 to 75 ° C, particularly preferably 45 to 70 ° C. Moreover, when it uses with respect to the resin, when the flame retardance efficiency by the carbonization layer formation promotion effect at the time of combustion is considered, what the temperature at the time of 50 weight% weight reduction is 320-460 degreeC is preferable, More preferably, 350 What is -450 degreeC is preferable.
In the following, “a temperature at the time of weight reduction of ˜% by weight” may be referred to as “˜% weight reduction temperature”.
本発明で好適に用いられるホスファゼン化合物の構造は、例えばJames E. Mark, Harry R. Allcock, Robert West 著、”Inorganic Polymers” Pretice-Hall International, Inc., 1992, p61-p140に記載されている。例えば、下記一般式(2)で示される環状ホスファゼン化合物及び/又は、一般式(3)で示される鎖状ホスファゼン化合物が挙げられ、その中でもこれらの構造を有するホスファゼン化合物を95重量%以上含有するものが好ましい。 The structure of the phosphazene compound preferably used in the present invention is described in, for example, “Inorganic Polymers” Pretice-Hall International, Inc., 1992, p61-p140, by James E. Mark, Harry R. Allcock, Robert West. . Examples thereof include cyclic phosphazene compounds represented by the following general formula (2) and / or chain phosphazene compounds represented by the general formula (3), and among them, the phosphazene compounds having these structures are contained in an amount of 95% by weight or more. Those are preferred.
ここで、式中のnは3〜25の整数、mは3〜10000の整数であり、置換基Xは炭素数が1〜6のアルキル基、炭素数が6〜11のアリール基、フッ素原子、又は下記一般式(4) Here, n in the formula is an integer of 3 to 25, m is an integer of 3 to 10000, the substituent X is an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 11 carbon atoms, a fluorine atom Or the following general formula (4)
で示される置換基を有するアリールオキシ基(式中のY1、Y2、Y3、Y4及びY5は水素原子、フッ素原子、炭素数が1〜5のアルキル基またはアルコキシ基、フェニル基、ヘテロ元素含有基の中からなる群より選ればれた少なくとも一種の置換基を表す)、又はナフチルオキシ基、又は炭素数が1〜6のアルコキシ基やアルコキシ置換アルコキシ基で表される置換基のうち、少なくとも一種の置換基であり、置換基上の水素は一部又は全部がフッ素に置換されていても構わない。また、式中のYは−N=P(O)(X)又は−N=P(X)3を表し、Zは−P(X)4又は−P(O)(X)2を表す。
これらの化合物は、一種単独で用いても、二種以上の混合物として用いても良い。
(Wherein Y 1 , Y 2 , Y 3 , Y 4 and Y 5 are a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, a phenyl group) , Represents at least one substituent selected from the group consisting of heteroelement-containing groups), or a naphthyloxy group, or a substituent represented by an alkoxy group having 1 to 6 carbon atoms or an alkoxy-substituted alkoxy group Among them, it is at least one kind of substituent, and hydrogen on the substituent may be partially or entirely substituted with fluorine. Y in the formula represents -N = P (O) (X) or -N = P (X) 3 , and Z represents -P (X) 4 or -P (O) (X) 2 .
These compounds may be used alone or as a mixture of two or more.
難燃性を決める因子の一つとして、分子中に含有するリン原子の濃度が挙げられる。ホスファゼン化合物において、鎖状構造を有する鎖状ホスファゼンは分子末端に置換基を有することから、環状ホスファゼン化合物よりもリン含有率が低くなり、同量を添加する場合、鎖状ホスファゼン化合物よりも環状ホスファゼン化合物の方がより難燃性付与効果が高いと考えられることから、本発明においては、環状構造を有するホスファゼン化合物の使用が好ましく、環状ホスファゼン化合物を95重量%以上含有するものが好ましい。 One factor that determines flame retardancy is the concentration of phosphorus atoms contained in the molecule. In a phosphazene compound, a chain phosphazene having a chain structure has a substituent at the molecular end, so that the phosphorus content is lower than that of a cyclic phosphazene compound. Since the compound is considered to have a higher flame retardancy-imparting effect, the use of a phosphazene compound having a cyclic structure is preferred in the present invention, and a compound containing 95% by weight or more of a cyclic phosphazene compound is preferred.
ホスファゼン化合物中の置換基Xは特に制限はなく、一例として、メチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、s−ブチル基、tert−ブチル基、n−アミル基、イソアミル基等のアルキル基、フェニル基、2−メチルフェニル基、3−メチルフェニル基、4−メチルフェニル基、2,6−ジメチルフェニル基、3,5−ジメチルフェニル基、2,5−ジメチルフェニル基、2,4−ジメチルフェニル基、3,4−ジメチルフェニル基、4-ターシャリーブチルフェニル基、2-メチル-4-ターシャリーブチルフェニル基等のアリール基、メトキシ基、エトキシ基、n−プロピルオキシ基、イソプロピルオキシ基、n−ブチルオキシ基、tert−ブチルオキシ基、s−ブチルオキシ基、n−アミルオキシ基、イソアミルオキシ基、tert−アミルオキシ基、n−ヘキシルオキシ基等のアルコキシ基、メトキシメトキシ基、メトキシエトキシ基、メトキシエトキシメトキシ基、メトキシエトキシエトキシ基、メトキシプロピルオキシ基等のアルコキシ置換アルコキシ基、フェノキシ基、2−メチルフェノキシ基、3−メチルフェノキシ基、4−メチルフェノキシ基、2,6−ジメチルフェノキシ基、2,5−ジメチルフェノキシ基、2,4−ジメチルフェノキシ基、3,5−ジメチルフェノキシ基、3,4−ジメチルフェノキシ基、2,3,4−トリメチルフェノキシ基、2,3,5−トリメチルフェノキシ基、2,3,6−トリメチルフェノキシ基、2,4,6−トリメチルフェノキシ基、2,4,5−トリメチルフェノキシ基、3,4,5−トリメチルフェノキシ基、2−エチルフェノキシ基、3−エチルフェノキシ基、4−エチルフェノキシ基、2,6−ジエチルフェノキシ基、2,5−ジエチルフェノキシ基、2,4−ジエチルフェノキシ基、3,5−ジエチルフェノキシ基、3,4−ジエチルフェノキシ基、4−n−プロピルフェノキシ基、4−イソプロピルフェノキシ基、4−ターシャリーブチルフェノキシ基、2−メチル−4−ターシャリーブチルフェノキシ基、2−フェニルフェノキシ基、3−フェニルフェノキシ基、4−フェニルフェノキシ基等のアルキル置換フェノキシ基、アリール置換フェノキシ基ナフチル基、ナフチルオキシ基等が挙げられ、これらの基の一部又は全部の水素がフッ素及び/又はヘテロ元素を含有する基に置き換わっていても構わない。ここで、ヘテロ元素を含有する基とは、B、N、O、Si、P、S原子を含有する基であり、一例を挙げると、アミノ基、アミド基、シアノ基、アルデヒド基、グリシジル基、カルボキシル基、水酸基、メルカプト基、シリル基等を含有する基が挙げられる。 The substituent X in the phosphazene compound is not particularly limited, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, tert-butyl group, n-amyl group, Alkyl group such as isoamyl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,5-dimethylphenyl Group, aryl group such as 2,4-dimethylphenyl group, 3,4-dimethylphenyl group, 4-tertiarybutylphenyl group, 2-methyl-4-tertiarybutylphenyl group, methoxy group, ethoxy group, n- Propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, s-butyloxy group, n-amyloxy group, isoamido Alkoxy groups such as ruoxy group, tert-amyloxy group, n-hexyloxy group, alkoxy-substituted alkoxy groups such as methoxymethoxy group, methoxyethoxy group, methoxyethoxymethoxy group, methoxyethoxyethoxy group, methoxypropyloxy group, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,6-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 3,4-dimethylphenoxy group, 2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2, 4,5-trimethylphenoxy group, 3,4,5-trimethyl Enoxy group, 2-ethylphenoxy group, 3-ethylphenoxy group, 4-ethylphenoxy group, 2,6-diethylphenoxy group, 2,5-diethylphenoxy group, 2,4-diethylphenoxy group, 3,5-diethyl Phenoxy group, 3,4-diethylphenoxy group, 4-n-propylphenoxy group, 4-isopropylphenoxy group, 4-tertiarybutylphenoxy group, 2-methyl-4-tertiarybutylphenoxy group, 2-phenylphenoxy group , Alkyl-substituted phenoxy groups such as 3-phenylphenoxy group, 4-phenylphenoxy group, aryl-substituted phenoxy groups, naphthyl groups, naphthyloxy groups, etc., and a part or all of these groups are fluorine and / or hetero It may be replaced with a group containing an element. Here, the group containing a hetero element is a group containing B, N, O, Si, P, and S atoms. For example, an amino group, an amide group, a cyano group, an aldehyde group, and a glycidyl group. , A group containing a carboxyl group, a hydroxyl group, a mercapto group, a silyl group, and the like.
さらに、これらの化合物は国際公開番号WO00/09518号に開示されている技術により、フェニレン基、ビフェニレン基および下記に示す基(5) Further, these compounds are produced by a technique disclosed in International Publication No. WO 00/09518, and a phenylene group, a biphenylene group, and a group (5) shown below.
(式中Xは、―C(CH3)2−、−SO2−、−S−、または−O−を、yは0又は1を表す)からなる群より選ばれた架橋基によって架橋されていても良い。これらの架橋構造を有するホスファゼン化合物は、具体的にはジクロルホスファゼンオリゴマーにフェノールのアルカリ金属塩および芳香族ジヒドロキシ化合物のアルカリ金属塩を反応させることにより製造される。これらのアルカリ金属塩は、ジクロルホスファゼンオリゴマーに対して理論量よりもやや過剰に添加される。
これらのホスファゼン化合物は一種単独で用いても、二種以上の混合物として用いても良い。
(Wherein X is —C (CH 3 ) 2 —, —SO 2 —, —S—, or —O—, y represents 0 or 1), and is crosslinked by a crosslinking group selected from the group consisting of May be. The phosphazene compound having such a crosslinked structure is specifically produced by reacting a dichlorophosphazene oligomer with an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound. These alkali metal salts are added to the dichlorophosphazene oligomer slightly in excess of the theoretical amount.
These phosphazene compounds may be used alone or as a mixture of two or more.
また、ホスファゼン化合物は環状三量体、環状四量体等の環状体や鎖状ホスファゼンといった構造の異なる混合物であるが、難燃樹脂組成物の加工性は環状三量体、四量体含有率が高いほど好ましい傾向にあり、具体的には環状三量体及び/又は四量体化合物を80重量%以上含むホスファゼン化合物が好ましい。さらに好ましくは、三量体を70重量%以上、より好ましくは三量体を80重量%以上含有することが好ましい。 The phosphazene compound is a mixture of different structures such as cyclic trimers and cyclic tetramers, and chain phosphazenes, but the processability of the flame retardant resin composition is cyclic trimer, tetramer content Is higher, and a phosphazene compound containing 80% by weight or more of a cyclic trimer and / or tetramer compound is specifically preferable. More preferably, it is preferable to contain 70% by weight or more of trimer, more preferably 80% by weight or more of trimer.
また、ホスファゼン化合物は、置換基の種類や構造の違いによっても異なるが、液状、ワックス状、固体状等、さまざまな形態を取ることができ、本発明の効果を損なわないものであれば、どのような形状でも構わない。固体状態の場合、嵩密度が0.45g/cm3以上、好ましくは0.45g/cm3以上、0.75g/cm3以下であることが好ましい。
該ホスファゼン化合物中に含有するナトリウム、カリウム等のアルカリ金属成分はそれぞれ200ppm以下、さらに好ましくは50ppm以下であり、より好ましくは、全アルカリ金属成分が50ppm以下である。また、上記一般式(2)中の置換基Xのうち少なくとも一つが水酸基であるホスファゼン化合物、即ちP−OH結合を含有するホスファゼン化合物の含有量が1重量%未満であることが望ましく、且つ、塩素含有量が1000ppm以下、好ましくは500ppm以下、さらに好ましくは300ppm以下であることが望ましい。
The phosphazene compound varies depending on the type and structure of the substituent, but can take various forms such as liquid, waxy, solid, etc., as long as it does not impair the effects of the present invention. Such a shape may be used. If the solid state, the bulk density is 0.45 g / cm 3 or higher, preferably 0.45 g / cm 3 or more and 0.75 g / cm 3 or less.
The alkali metal components such as sodium and potassium contained in the phosphazene compound are each 200 ppm or less, more preferably 50 ppm or less, and more preferably the total alkali metal components are 50 ppm or less. Moreover, it is desirable that the content of the phosphazene compound in which at least one of the substituents X in the general formula (2) is a hydroxyl group, that is, the phosphazene compound containing a P—OH bond is less than 1% by weight, and It is desirable that the chlorine content is 1000 ppm or less, preferably 500 ppm or less, more preferably 300 ppm or less.
置換基Xのうち少なくとも一つが水酸基であるホスファゼン化合物は、下記一般式(6)(式中のa+b=nであり、nは3以上の整数である。また、式中のXは同じであっても異なっても良いアリールオキシ基、及び/又はアルコキシ基を示す)で表されるオキソ体構造をとることもあるが、このようなオキソ体化合物も水酸基含有ホスファゼン化合物と同様に1重量%未満であることが望ましい。上記一般式(3)で表される鎖状構造を有するホスファゼン化合物でも同様である。 A phosphazene compound in which at least one of the substituents X is a hydroxyl group is represented by the following general formula (6) (wherein a + b = n, n is an integer of 3 or more. An oxy-form structure represented by an aryloxy group and / or an alkoxy group, which may be different from each other, may be taken, and such an oxo-form compound is also less than 1% by weight in the same manner as the hydroxyl group-containing phosphazene compound. It is desirable that The same applies to phosphazene compounds having a chain structure represented by the general formula (3).
本発明において好適に使用される(B)成分に含有する水分量は、電気特性、耐加水分解性等を考慮した場合、1000ppm以下、好ましくは800ppm以下、さらに好ましくは650ppm以下、さらには500ppm以下、より好ましくは300ppm以下であり、且つJIS K6751に基づき測定された酸価が1.0以下、好ましくは0.5以下であることが望ましい。 The water content contained in the component (B) suitably used in the present invention is 1000 ppm or less, preferably 800 ppm or less, more preferably 650 ppm or less, further 500 ppm or less, taking into consideration electrical characteristics, hydrolysis resistance, and the like. More preferably, it is 300 ppm or less, and the acid value measured based on JIS K6751 is 1.0 or less, preferably 0.5 or less.
また、本発明で好適に使用される(B)成分は、耐加水分解性、耐吸湿性の観点から、水への溶解度(サンプルを0.1g/mLの濃度で蒸留水に混合し、室温で1時間攪拌後に水中に溶け込んだサンプルの量を指す)が100ppm以下、好ましくは50ppm、より好ましくは、25ppm以下であるものが良い。 In addition, the component (B) preferably used in the present invention has a solubility in water (mixed with distilled water at a concentration of 0.1 g / mL, from the viewpoint of hydrolysis resistance and moisture absorption resistance, The amount of the sample dissolved in water after stirring for 1 hour) is 100 ppm or less, preferably 50 ppm, more preferably 25 ppm or less.
(C)成分:芳香族樹脂
本発明においては、(A)成分、(B)成分の他に、炭化皮膜の形成をより促進する目的で、芳香族樹脂を含有しても良い。
本発明で用いられる芳香族樹脂は、燃焼時に炭化皮膜を形成し易い樹脂であれば特に規定はされず、従来公知の芳香族樹脂を好適に用いることができる。一例を挙げると、ASTM D2863に基づいて測定された酸素指数が24以上であり、且つ、主鎖に芳香族分子を20mol%以上含有している樹脂であることが好ましい。より好ましくは30mol%以上、更に好ましくは40mol%以上、特に好ましくは50mol%以上含有していることが好ましい。具体的には、ポリフェニレンエーテル系樹脂、芳香族ポリアミド系樹脂、芳香族ポリエステル系樹脂、フェノール系樹脂、ポリフェニレンスルフィド系樹脂が挙げられる。その中でも誘電特性、耐熱性、機械物性等も考慮すると、ポリフェニレンエーテル系樹脂、ポリフェニレンスルフィド系樹脂が好ましく、特にポリフェニレンエーテル系樹脂が好適に用いられる。これらの樹脂は一種単独で用いても、二種以上を併用して用いても良い。
ただし、(C)成分として芳香族樹脂を添加する場合、(C)成分は上記熱可塑性樹脂とは異なる樹脂であって、同一の樹脂であることはない。
(C) Component: Aromatic Resin In the present invention, in addition to the (A) component and the (B) component, an aromatic resin may be contained for the purpose of further promoting the formation of the carbonized film.
The aromatic resin used in the present invention is not particularly defined as long as it is a resin that easily forms a carbonized film during combustion, and a conventionally known aromatic resin can be suitably used. For example, a resin having an oxygen index measured based on ASTM D2863 of 24 or more and containing 20 mol% or more of aromatic molecules in the main chain is preferable. More preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more. Specific examples include polyphenylene ether resins, aromatic polyamide resins, aromatic polyester resins, phenol resins, and polyphenylene sulfide resins. Among these, in consideration of dielectric properties, heat resistance, mechanical properties, etc., polyphenylene ether resins and polyphenylene sulfide resins are preferable, and polyphenylene ether resins are particularly preferably used. These resins may be used alone or in combination of two or more.
However, when an aromatic resin is added as the component (C), the component (C) is a resin different from the thermoplastic resin and is not the same resin.
(C−1)ポリフェニレンエーテル系樹脂
本発明で好適に用いることができるポリフェニレンエーテル樹脂は、下記一般式(9)及び/または(10)で表される繰り返し単位を有する単独重合体、あるいは共重合体であることが好ましい。
(C-1) Polyphenylene ether resin The polyphenylene ether resin that can be suitably used in the present invention is a homopolymer or a copolymer having a repeating unit represented by the following general formula (9) and / or (10). It is preferably a coalescence.
(ここで、R1、R2、R3、R4、R5、R6は独立に炭素1〜4のアルキル基、アリール基、水素を表す。但し、R5、R6は同時に水素ではない。) (Here, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen, provided that R 5 and R 6 are simultaneously hydrogen. Absent.)
ポリフェニレンエーテル樹脂の単独重合体の代表例としては、ポリ(2,6−ジメチル−1,4−フェニレン)エーテル、ポリ(2−メチル−6−エチル−14−フェニレン)エーテル、ポリ(2,6−ジエチル−1,4−フェニレン)エーテル、ポリ(2−エチル−6−n−プロピル−1,4−フェニレン)エーテル、ポリ(2,6−ジ−n−プロピル−1,4−フェニレン)エーテル、ポリ(2−メチル−6−n−ブチル−1,4−フェニレン)エーテル、ポリ(2−エチル−6−イソプロピル−1,4−フェニレン)エーテル、ポリ(2−メチル−6−ヒドロキシエチル−1,4−フェニレン)エーテル、等のホモポリマーが挙げられる。 Representative examples of homopolymers of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2,6 -Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether Poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-) And homopolymers such as 1,4-phenylene) ether.
この中で、ポリ(2,6−ジメチル−1,4−フェニレン)エーテルが好ましく、特開昭63−301222号公報等に記載されている、2−(ジアルキルアミノメチル)−6−メチルフェニレンエーテルユニットや2−(N−アルキル−N−フェニルアミノメチル)−6−メチルフェニレンエーテルユニット等を部分構造として含んでいるポリフェニレンエーテルは特に好ましい。 Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether described in JP-A-63-301222 and the like is preferable. A polyphenylene ether containing a unit or a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit as a partial structure is particularly preferred.
ここでポリフェニレンエーテル共重合体とは、フェニレンエーテル構造を主単量体単位とする共重合体である。その例としては、2,6−ジメチルフェノールと2,3,6−トリメチルフェノールとの共重合体、2,6−ジメチルフェノールとo−クレゾールとの共重合体あるいは2,6−ジメチルフェノールと2,3,6−トリメチルフェノール及びo−クレゾールとの共重合体、2,6−ジメチルフェノールと下記一般式(11)で示されるビスフェノールとの共重合体等がある。 Here, the polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2 , 3,6-trimethylphenol and a copolymer of o-cresol, a copolymer of 2,6-dimethylphenol and bisphenol represented by the following general formula (11), and the like.
(ここで、R7、R8、R9、R10は独立に炭素1〜4のアルキル基、アリール基、水素を表す。また、式中Xは、―C(CH3)2−、−SO2−、−S−、または−O−を、yは0又は1を表し、zは0又は1を表す。) (Here, R 7 , R 8 , R 9 , R 10 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen. In the formula, X represents —C (CH 3 ) 2 —, — SO 2- , -S-, or -O-, y represents 0 or 1, and z represents 0 or 1.)
本発明においては、ポリフェニレンエーテル樹脂の一部または全部に、カルボキシル基、エポキシ基、アミノ基、メルカプト基、シリル基、水酸基、無水ジカルボキル基などの反応性官能基を、グラフト反応や、共重合など何らかの方法で導入した変性ポリフェニレンエーテル樹脂も本発明の目的を損なわない範囲で使用できる。これらは1種又は2種以上を組み合わせて用いても良い。 In the present invention, a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group, and an anhydrous dicarboxyl group is grafted or copolymerized on part or all of the polyphenylene ether resin. A modified polyphenylene ether resin introduced by any method can be used as long as the object of the present invention is not impaired. These may be used alone or in combination of two or more.
ポリフェニレンエーテル樹脂の一部又は全部を、不飽和カルボン酸又はその官能的誘導体で変性された変性ポリフェニレンエーテル樹脂は、特開平2−276823号公報、特開昭63−108059号公報、特開昭59−59724号公報等に記載されており、例えばラジカル開始剤の存在下または非存在下において、ポリフェニレンエーテル樹脂に不飽和カルボン酸やその官能的誘導体を溶融混練し、反応させることによって製造される。あるいは、ポリフェニレンエーテルと不飽和カルボン酸やその官能的誘導体とをラジカル開始剤存在下または非存在下で有機溶剤に溶かし、溶液下で反応させることによって製造される。 Modified polyphenylene ether resins obtained by modifying part or all of polyphenylene ether resins with unsaturated carboxylic acids or functional derivatives thereof are disclosed in JP-A-2-276823, JP-A-63-108059, JP-A-59. For example, it is produced by melt-kneading and reacting an unsaturated carboxylic acid or a functional derivative thereof with a polyphenylene ether resin in the presence or absence of a radical initiator. Alternatively, it is produced by dissolving polyphenylene ether and an unsaturated carboxylic acid or a functional derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in a solution.
不飽和カルボン酸又はその官能的誘導体としては、例えばマレイン酸、フマル酸、イタコン酸、ハロゲン化マレイン酸、シス−4−シクロヘキセン−1,2−ジカルボン酸、エンド−シス−ビシクロ(2.2.1)−5−ヘプテン−2,3−ジカルボン酸などや、これらジカルボン酸の酸無水物、エステル、アミド、イミドなど、さらにはアクリル酸、メタクリル酸などや、これらモノカルボン酸のエステル、アミドなどが挙げられる。また、飽和カルボン酸であるが変性ポリフェニレンエーテルを製造する際の反応温度でそれ自身が熱分解し、本発明で用いる官能的誘導体となり得る化合物も用いることができ、具体的にはリンゴ酸、クエン酸などが挙げられる。これらは1種又は2種以上を組み合わせて用いても良い。 Examples of unsaturated carboxylic acids or functional derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and endo-cis-bicyclo (2.2. 1) -5-heptene-2,3-dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., esters of these monocarboxylic acids, amides, etc. Is mentioned. In addition, a compound which is a saturated carboxylic acid but can be thermally decomposed itself at the reaction temperature when producing the modified polyphenylene ether to become a functional derivative used in the present invention can be used. An acid etc. are mentioned. These may be used alone or in combination of two or more.
本発明で用いることのできるポリフェニレンエーテルの分子量は、本発明の効果を損なわない範囲であれば、何等制限されるものではない。具体的には、数平均分子量が500〜30000のものを好適に用いることができる。成型加工性に特に優れた組成物を得る必要がある場合には、ポリフェニレンエーテルの数平均分子量が500以上、5000以下のもの、好ましくは1200以上、4000以下のものを好適に用いることができる。耐熱性が特に優れた組成物を得る必要がある場合には、ポリフェニレンエーテルの数平均分子量が5000を超えるものを用いることが好ましい。ポリフェニレンエーテルは、樹脂組成物とした場合に特に求められている特性に合わせて、適宜適当な分子量のものを用いれば良い。 The molecular weight of the polyphenylene ether that can be used in the present invention is not limited as long as the effects of the present invention are not impaired. Specifically, those having a number average molecular weight of 500 to 30,000 can be suitably used. When it is necessary to obtain a composition particularly excellent in moldability, a polyphenylene ether having a number average molecular weight of 500 or more and 5000 or less, preferably 1200 or more and 4000 or less can be suitably used. When it is necessary to obtain a composition having particularly excellent heat resistance, it is preferable to use a polyphenylene ether having a number average molecular weight exceeding 5000. Polyphenylene ether having an appropriate molecular weight may be used as appropriate in accordance with characteristics particularly required when a resin composition is used.
(C−2)芳香族ポリアミド樹脂
本発明で好適に用いることのできる芳香族含有ポリアミド樹脂は、本発明の効果を発揮するものであれば従来公知のものを広く用いることができ、特に制限されない。一例を挙げると、ε−カプロラクタム、アジピン酸、セバシン酸、ドデカン二酸、イソフタル酸、テレフタル酸、ヘキサメチレンジアミン、テトラメチレンジアミン、2−メチルペンタメチレンジアミン、2,2,4−トリメチルヘキサメチレンジアミン、2,4,4−トリメチルヘキサメチレンジアミン、メタキシリレンジアミン、ビス(3−メチル−4−アミノシクロへキシル)メタン等のポリアミド形成性モノマーを適宜組み合わせて得られるホモポリマー、共重合体及びこれらの混合物を用いることができる。
(C-2) Aromatic polyamide resin The aromatic-containing polyamide resin that can be suitably used in the present invention can be widely used as long as it exhibits the effects of the present invention, and is not particularly limited. . For example, ε-caprolactam, adipic acid, sebacic acid, dodecanedioic acid, isophthalic acid, terephthalic acid, hexamethylenediamine, tetramethylenediamine, 2-methylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine , 2,4,4-trimethylhexamethylenediamine, metaxylylenediamine, homopolymers, copolymers obtained by appropriately combining polyamide-forming monomers such as bis (3-methyl-4-aminocyclohexyl) methane, and copolymers Mixtures of these can be used.
具体的には、ポリアミド6I、ポリアミド6T、ポリアミド9T、ポリアミドMXD6、ポリアミド66/6I、ポリアミド66/6T、ポリアミド6T/6I、ポリアミド66/6I/6、ポリアミド 66/6I/11、ポリアミド66/6I/12、ポリアミド 66/6I/610、ポリアミド 66/6I/612等を挙げることができ、これらは一種単独又は二種以上の混合物として用いることができる。
本発明によるポリアミド樹脂の分子量は、何等規定されるものではないが、JIS K6810規格に示される硫酸相対粘度が1.5〜3.5の範囲にあるものを好適に用いることができる。
Specifically, polyamide 6I, polyamide 6T, polyamide 9T, polyamide MXD6, polyamide 66 / 6I, polyamide 66 / 6T, polyamide 6T / 6I, polyamide 66 / 6I / 6, polyamide 66 / 6I / 11, polyamide 66 / 6I / 12, polyamide 66 / 6I / 610, polyamide 66 / 6I / 612 and the like, and these can be used singly or as a mixture of two or more.
The molecular weight of the polyamide resin according to the present invention is not defined at all, but those having a relative viscosity of sulfuric acid in the range of 1.5 to 3.5 shown in the JIS K6810 standard can be suitably used.
(C−3)サーモトロピック液晶
本発明で好適に用いることのできるサーモトロピック液晶は、本発明の効果を発揮するものであれば従来公知のものを広く用いることができ、特に制限されない。一例を挙げると、p−ヒドロキシ安息香酸及びエチレンテレフタレートを主構成単位とするサーモトロピック液晶ポリエステル、p−ヒドロキシ安息香酸及び2−ヒドロキシ−6−ナフトエ酸を主構成単位とするサーモトロピック液晶ポリエステル、p−ヒドロキシ安息香酸及び4,4’−ヒドロキシビフェニル並びにテレフタル酸を主構成単位とするサーモトロピック液晶ポリエステルなどが挙げられ、特に制限はない。
(C-3) Thermotropic liquid crystal The thermotropic liquid crystal that can be suitably used in the present invention can be widely used as long as it exhibits the effects of the present invention, and is not particularly limited. For example, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and ethylene terephthalate, a thermotropic liquid crystal polyester mainly composed of p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, p Examples thereof include thermotropic liquid crystal polyesters mainly composed of -hydroxybenzoic acid, 4,4'-hydroxybiphenyl, and terephthalic acid, and are not particularly limited.
本発明で好適に用いられるサーモトロピック液晶は、必要に応じて本発明の特徴と効果を損なわない程度の少量の範囲で、他の芳香族ジカルボン酸、芳香族ジオール、芳香族ヒドロキシカルボン酸から生成する構造単位を導入することができる。
本発明のサーモトロピック液晶の溶融時での液晶状態を示し始める温度(以下、液晶開始温度という)は、好ましくは150〜350℃、さらに好ましくは180〜320℃である。液晶開始温度をこの範囲にすることは、得られる樹脂組成物を好ましい色調と耐熱性と成形加工性バランスの良いものとする。
The thermotropic liquid crystal suitably used in the present invention is formed from other aromatic dicarboxylic acids, aromatic diols, and aromatic hydroxycarboxylic acids in a small amount range that does not impair the features and effects of the present invention as necessary. Structural units can be introduced.
The temperature at which the thermotropic liquid crystal of the present invention starts to show a liquid crystal state when melted (hereinafter referred to as a liquid crystal start temperature) is preferably 150 to 350 ° C., more preferably 180 to 320 ° C. Setting the liquid crystal starting temperature within this range makes the obtained resin composition have a good balance of color tone, heat resistance and moldability.
本発明で好適に用いられるサーモトロピック液晶の見かけの溶融粘度(液晶 開始温度+30℃でずり速度100/秒)は本発明の効果が得られる範囲であれば特に規定はないが、特に流動性が必要な場合の溶融粘度は10〜3,000Pa・sであることが好ましく、より好ましくは10〜2,000Pa・s、特に好ましくは10〜1,000Pa・sである。 The apparent melt viscosity (liquid crystal starting temperature + 30 ° C. and shear rate of 100 / second) of the thermotropic liquid crystal suitably used in the present invention is not particularly defined as long as the effect of the present invention is obtained, but the fluidity is particularly limited. The melt viscosity when necessary is preferably 10 to 3,000 Pa · s, more preferably 10 to 2,000 Pa · s, and particularly preferably 10 to 1,000 Pa · s.
(C−4)ポリフェニレンスルフィド系樹脂
本発明で好適に用いることができるポリフェニレンスルフィド系樹脂は、、本発明の効果を発揮するものであれば従来公知のものを広く用いることができ、特に制限されない。一例を挙げると、ポリフェニレンスルフィド、ポリフェニレンスルフィドケトン、ポリビフェニレンスルフィド、ポリフェニレンスルフィドスルホン等が挙げられ、特にポリフェニレンスルフィドを好適に用いることができる。
(C-4) Polyphenylene sulfide-based resin The polyphenylene sulfide-based resin that can be suitably used in the present invention can be widely used as long as it exhibits the effects of the present invention, and is not particularly limited. . For example, polyphenylene sulfide, polyphenylene sulfide ketone, polybiphenylene sulfide, polyphenylene sulfide sulfone and the like can be mentioned, and polyphenylene sulfide can be particularly preferably used.
本発明で好適に用いられるポリフェニレンスルフィドとしては、300℃における溶融粘度(剪断速度1,000/秒)が100〜10,000ポイズであるものの中から任意に選ぶことができ、構造は直鎖状、分岐状いずれでもよく、中でも直鎖状のものを好適に用いることができる。
また、ポリフェニレンスルフィドは、−SX基(Sは硫黄原子、Xはアルカリ金属または水素原子である)量が、15μmol/g以上、好ましくは18〜35μmol/g、特に好ましくは20〜30μmol/gであるものが好ましい。
The polyphenylene sulfide suitably used in the present invention can be arbitrarily selected from those having a melt viscosity at 300 ° C. (shear rate of 1,000 / second) of 100 to 10,000 poise, and the structure is linear. Any of these may be branched, and a straight chain can be preferably used.
The polyphenylene sulfide has a —SX group (S is a sulfur atom, X is an alkali metal or a hydrogen atom) in an amount of 15 μmol / g or more, preferably 18 to 35 μmol / g, particularly preferably 20 to 30 μmol / g. Some are preferred.
本発明において好適に用いられるポリフェニレンスルフィドの製造方法は、通常、ハロゲン置換芳香族化合物、例えばp−ジクロルベンゼンを硫黄と炭酸ソーダの存在下で重合させる方法、極性溶媒中で硫化ナトリウムあるいは硫化水素ナトリウムと水酸化ナトリウムまたは硫化水素と水酸化ナトリウムあるいはナトリウムアミノアルカノエートの存在下で重合させる方法、p−クロルチオフェノールの自己縮合等が挙げられるが、中でもN−メチルピロリドン、ジメチルアセトアミド等のアミド系溶媒やスルホラン等のスルホン系溶媒中で硫化ナトリウムとp−ジクロルベンゼンを反応させる方法が適当である。 The method for producing polyphenylene sulfide preferably used in the present invention is usually a method of polymerizing a halogen-substituted aromatic compound such as p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or hydrogen sulfide in a polar solvent. Examples include polymerization in the presence of sodium and sodium hydroxide or hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate, and self-condensation of p-chlorothiophenol. Among them, amides such as N-methylpyrrolidone and dimethylacetamide A method in which sodium sulfide and p-dichlorobenzene are reacted in a sulfone solvent such as a system solvent or sulfolane is suitable.
ポリフェニレンスルフィドの製造方法は、公知の方法で得られるものであれば特に限定されるものではなく、例えば、米国特許第2513188号明細書、特公昭44−27671号公報、特公昭45−3368号公報、特公昭52−12240号公報、特開昭61−225217号および米国特許第3274165号明細書、さらに特公昭46−27255号公報、ベルギー特許第29437号明細書、特開平5−222196号公報、等に記載された方法やこれら特許等に例示された先行技術の方法で得ることが出来る。 The method for producing polyphenylene sulfide is not particularly limited as long as it can be obtained by a known method. For example, US Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671, Japanese Patent Publication No. 45-3368 JP-B-52-12240, JP-A-61-225217 and U.S. Pat. No. 3,274,165, JP-B-46-27255, Belgian Patent No. 29437, JP-A-5-222196, And the prior art methods exemplified in these patents.
(C−5)フェノール系樹脂
本発明において好適に用いられるフェノール系樹脂としては、従来公知のものを好適に用いることができる。一例を挙げると、フェノールとアルデヒドを塩基性触媒で付加、縮合して得られるレゾール型フェノール樹脂、フェノールとアルデヒドを酸触媒で付加、縮合して得られるノボラック型フェノール樹脂等がある。中でもノボラック型フェノール樹脂が好適に用いられる。これらのフェノール樹脂は一種単独でも二種以上を併用して用いても良い。
また、本発明で用いられるフェノール樹脂の数平均分子量は、特に制限はされないが、300〜50000のものが好適に用いられ、分子量の異なるフェノール樹脂を併用しても良い。
(C-5) Phenolic Resin As a phenolic resin suitably used in the present invention, a conventionally known resin can be suitably used. As an example, there are a resol type phenol resin obtained by adding and condensing phenol and aldehyde with a basic catalyst, and a novolak type phenol resin obtained by adding and condensing phenol and aldehyde with an acid catalyst. Among these, novolac type phenol resins are preferably used. These phenol resins may be used alone or in combination of two or more.
The number average molecular weight of the phenol resin used in the present invention is not particularly limited, but those having a molecular weight of 300 to 50,000 are preferably used, and phenol resins having different molecular weights may be used in combination.
(配合割合)
本発明における熱可塑性樹脂組成物において、難燃剤組成物を構成する成分の配合割合は、本願の効果が得られる範囲であれば特に規定はされないが、本願の効果を効率良く得ようとした場合、(A)成分と(B)成分の配合割合は、(A)成分と(B)成分の合計100重量部中、(A)成分を0.1〜60重量部、(B)成分を99.9〜40重量部、好ましくは(A)成分を0.1〜50重量部、(B)成分を99.9〜50重量部であることが好ましい。更には、(A)成分を0.1〜37重量部、(B)成分を99.9〜63重量部であることが好ましい。
(Mixing ratio)
In the thermoplastic resin composition of the present invention, the blending ratio of the components constituting the flame retardant composition is not particularly specified as long as the effect of the present application is obtained, but when the effect of the present application is efficiently obtained. The blending ratio of the (A) component and the (B) component is 0.1 to 60 parts by weight for the (A) component and 99 for the (B) component in a total of 100 parts by weight of the (A) and (B) components. 0.9 to 40 parts by weight, preferably 0.1 to 50 parts by weight of component (A) and 99.9 to 50 parts by weight of component (B). Furthermore, it is preferable that (A) component is 0.1-37 weight part and (B) component is 99.9-63 weight part.
また、(C)成分の芳香族樹脂を配合する場合の配合割合は、(C)成分と(B)成分の比が(C)/(B)=95/5〜5/95、より好ましくは、(C)/(B)=90/10〜10/95であることが好ましい。
本発明の熱可塑性樹脂と難燃剤組成物との配合割合は、本発明の効果を得ることのできる割合であればよく特に規定はされないが、熱可塑性樹脂成分100重量部に対し、難燃剤組成物を1〜1000重量部であることが好ましい。より好ましくは、熱可塑性樹脂100重量部に対し、難燃剤組成物は5〜500重量部である。
The blending ratio when blending the aromatic resin of the component (C) is such that the ratio of the component (C) to the component (B) is (C) / (B) = 95/5 to 5/95, more preferably (C) / (B) = 90/10 to 10/95 is preferable.
The blending ratio of the thermoplastic resin of the present invention and the flame retardant composition is not particularly limited as long as it is a ratio capable of obtaining the effects of the present invention. However, the composition of the flame retardant is 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin component. It is preferable that a thing is 1-1000 weight part. More preferably, the flame retardant composition is 5 to 500 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
(難燃剤組成物の形状)
本発明の難燃性熱可塑性樹脂組成物において用いる難燃剤組成物の形状は、本発明の効果が達成できるものであれば特に規定するものではない。例えば、粉体、錠剤型、ペレット、塊状、ワックス、液体、オイル等の状態で供給される。また、必要であれば、難燃剤組成物を気化させて用いることもできる。また、本発明において用いる難燃剤組成物においては、各成分は完全に相溶させても良いし、単純に混合させて用いても良い。また、相溶させたものと単純混合のものとの混合物でも良い。
(Shape of flame retardant composition)
The shape of the flame retardant composition used in the flame retardant thermoplastic resin composition of the present invention is not particularly defined as long as the effects of the present invention can be achieved. For example, it is supplied in the state of powder, tablet form, pellet, lump, wax, liquid, oil or the like. Further, if necessary, the flame retardant composition can be vaporized and used. Moreover, in the flame retardant composition used in the present invention, each component may be completely compatible or simply mixed. Moreover, the mixture of what was made compatible and a simple mixture may be sufficient.
(他の樹脂との組合せ)
本発明の難燃性熱可塑性樹脂組成物は、必要により従来公知の硬化性樹脂と組み合わせて使用することができる。一例を挙げると、不飽和ポリエステル樹脂、ビニルエステル樹脂、ジアリルフタレート樹脂、エポキシ樹脂、シアネート樹脂、キシレン樹脂、トリアジン樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ウレタン樹脂、オキセタン樹脂、ケトン樹脂、アルキド樹脂、フラン樹脂、スチリルピリジン樹脂、シリコン樹脂、合成ゴムが挙げられる。
これらの樹脂は、一種単独でも、二種以上の樹脂を組み合わせて用いても良い。
(Combination with other resins)
The flame-retardant thermoplastic resin composition of the present invention can be used in combination with a conventionally known curable resin, if necessary. For example, unsaturated polyester resin, vinyl ester resin, diallyl phthalate resin, epoxy resin, cyanate resin, xylene resin, triazine resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, urethane resin, oxetane resin, ketone resin Alkyd resin, furan resin, styrylpyridine resin, silicone resin, and synthetic rubber.
These resins may be used alone or in combination of two or more resins.
(添加剤)
本発明による難燃性熱可塑性樹脂組成物においては、本発明の効果が達成できる範囲で、従来公知のノンハロゲン、ノンアンチモンの難燃剤を併用することができる。例示すると、トリアリールホスフィン、トリアルキルホスフィン、ビス(ジアリールホスフィノ)ベンゼン、トリス(ジアリールホスフィノ)ベンゼン等の三級ホスフィン類の酸化物や硫化物、ホスフィン酸やホスホン酸等の金属塩、アミド、アンモニウム塩、メラミンとの誘導体、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウム、アルミン酸カルシウム等の金属水酸化物、メラミン、メラム、メレム、メロン、メチレンジメラミン、エチレンジメラミン、デカメチレンジメラミン、1,3−シクロヘキシルジメラミン、4,4’−ジエチレンジメラミン、ジエチレントリメラミン、ベンゾグアナミン、ジベンゾグアナミン、サクシノグアナミン、メチルグアナミン、アセトグアナミン、メラミン樹脂等や、上記化合物のシアヌル酸塩、硫酸塩、リン酸塩、硼酸塩、2−ジブチルアミノ−4,6−ジメルカプト−S−トリアジン、2−N−フェニルアミノ−4,6−ジメルカプト−S−トリアジン、2,4,6−トリメルカプト−S−トリアジン、トリアリルシアヌレート、トリメタアリルイソシアヌレート等のトリアジン系化合物、バナジウム、二オブ、タンタル、鉄、ルテニウム、ニッケル、パラジウム、白金、銅、銀、金等の酸化物や硫化物、硼酸、硼酸亜鉛化合物等の硼素含有化合物、ポリオルガノシロキサン、シルセスキオキサン、シリコン樹脂等の珪素含有化合物、シリカ、カオリンクレー、タルク、ウォラストナイト等の無機珪素化合物を添加して更なる難燃性の向上も可能である。
(Additive)
In the flame-retardant thermoplastic resin composition according to the present invention, conventionally known non-halogen and non-antimony flame retardants can be used in combination as long as the effects of the present invention can be achieved. Examples include oxides and sulfides of tertiary phosphines such as triarylphosphine, trialkylphosphine, bis (diarylphosphino) benzene, tris (diarylphosphino) benzene, metal salts such as phosphinic acid and phosphonic acid, amides , Ammonium salts, derivatives with melamine, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, calcium aluminate and other metal hydroxides, melamine, melam, melem, melon, methylene dimelamine, ethylene dimelamine, decamethylene di Melamine, 1,3-cyclohexyl dimelamine, 4,4′-diethylene dimelamine, diethylenetrimelamine, benzoguanamine, dibenzoguanamine, succinoguanamine, methylguanamine, acetoguanamine, melamine resin, and the like Lurate, sulfate, phosphate, borate, 2-dibutylamino-4,6-dimercapto-S-triazine, 2-N-phenylamino-4,6-dimercapto-S-triazine, 2,4, Oxidation of triazine compounds such as 6-trimercapto-S-triazine, triallyl cyanurate, trimethallyl isocyanurate, vanadium, niobium, tantalum, iron, ruthenium, nickel, palladium, platinum, copper, silver, gold, etc. Boron-containing compounds such as oxides, sulfides, boric acid, zinc borate compounds, polyorganosiloxanes, silsesquioxanes, silicon-containing compounds such as silicon resins, inorganic silicon compounds such as silica, kaolin clay, talc and wollastonite Thus, further improvement in flame retardancy is possible.
また、本発明の難燃性熱可塑性樹脂組成物には、機械物性を向上させる目的で、従来公知の充填材を配合することができる。例えば、シリカ、カオリンクレー、タルク、ウォラストナイト、酸化チタン、ガラスビーズ、ガラスフレーク、ガラス繊維、炭酸カルシウム、炭酸バリウム、硫酸カルシウム、硫酸バリウム、珪酸カルシウム、チタン酸カリウム、硼酸アルミニウム、硼酸マグネシウムや、ケナフ繊維、炭素繊維、シリカ繊維、アルミナ繊維、石英繊維等の繊維状補強剤や、非繊維状補強剤が挙げられる。これらは、有機物や無機物等で被覆されていても良い。 Moreover, a conventionally well-known filler can be mix | blended with the flame-retardant thermoplastic resin composition of this invention for the purpose of improving a mechanical physical property. For example, silica, kaolin clay, talc, wollastonite, titanium oxide, glass beads, glass flake, glass fiber, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, calcium silicate, potassium titanate, aluminum borate, magnesium borate, And fibrous reinforcing agents such as kenaf fiber, carbon fiber, silica fiber, alumina fiber, and quartz fiber, and non-fibrous reinforcing agent. These may be coated with organic materials and inorganic materials, and the like.
本発明の難燃性熱可塑性樹脂組成物を使用する場合、剛性や寸法安定性等の他の特性を付与するため、本発明の効果を損なわない範囲で他の添加剤、例えば可塑剤、酸化防止剤、及び紫外線吸収剤、光安定剤などの安定剤、硬化剤、硬化促進剤、帯電防止剤、導電性付与剤、応力緩和剤、離型剤、結晶化促進剤、加水分解抑制剤、潤滑剤、衝撃付与剤、摺動性改良剤、相溶化剤、核剤、強化剤、補強剤、流動調整剤、染料、増感材、着色用顔料、ゴム質重合体、導電性高分子等を予め添加することができる。 When using the flame-retardant thermoplastic resin composition of the present invention, other additives such as plasticizer, oxidation, etc. are added within the range not impairing the effects of the present invention in order to impart other characteristics such as rigidity and dimensional stability. Stabilizers, and stabilizers such as ultraviolet absorbers and light stabilizers, curing agents, curing accelerators, antistatic agents, conductivity imparting agents, stress relaxation agents, mold release agents, crystallization accelerators, hydrolysis inhibitors, Lubricants, impact imparting agents, slidability improvers, compatibilizers, nucleating agents, reinforcing agents, reinforcing agents, flow regulators, dyes, sensitizers, coloring pigments, rubbery polymers, conductive polymers, etc. Can be added in advance.
(配合順序)
本発明の難燃性熱可塑性樹脂組成物における各成分の配合方法は、本発明の効果が達成できる方法であれば特に規定するものでない。熱可塑性樹脂、(A)成分及び(B)成分を予め混合して用いても良いし、(A)成分と(B)成分を混合した後、熱可塑性樹脂に配合しても良い。また、熱可塑性樹脂と(A)成分を混合した後、(B)成分を配合しても良いし、熱可塑性樹脂と(B)成分を混合した後、(A)成分を配合しても良い。(C)成分を添加する場合も、同様に本発明の効果が達成できる方法で混合すればよく、特に規定するものではない。
(Mixing order)
The blending method of each component in the flame retardant thermoplastic resin composition of the present invention is not particularly defined as long as the effect of the present invention can be achieved. The thermoplastic resin, the component (A) and the component (B) may be mixed and used in advance, or after mixing the component (A) and the component (B), they may be blended in the thermoplastic resin. Moreover, after mixing a thermoplastic resin and (A) component, (B) component may be mix | blended, and after mixing a thermoplastic resin and (B) component, you may mix | blend (A) component. . Even when the component (C) is added, it may be mixed by a method capable of achieving the effect of the present invention, and is not particularly defined.
(配合方法)
本発明の難燃性熱可塑性樹脂組成物における各成分の配合方法は、本発明の効果が達成できる方法であれば特に規定するものではない。例えば、押出機、加熱ロール、ニーダー、バンバリーミキサー等の混練機を用いて混練製造することができる。その中でも押出機による溶融混練が、生産性の面で好ましい。溶融混練温度は、ベース樹脂の好ましい加工温度に従えばよく、目安としては140〜360℃の範囲、好ましくは180〜320℃の範囲である。
(Mixing method)
The blending method of each component in the flame retardant thermoplastic resin composition of the present invention is not particularly defined as long as the effect of the present invention can be achieved. For example, kneading can be performed using a kneader such as an extruder, a heating roll, a kneader, or a Banbury mixer. Among them, melt kneading with an extruder is preferable in terms of productivity. The melt-kneading temperature may be in accordance with the preferred processing temperature of the base resin, and as a guide, it is in the range of 140 to 360 ° C, preferably in the range of 180 to 320 ° C.
また本発明の難燃性熱可塑性樹脂組成物の成形体は、射出成形、シート成形、ブロー成形、インジェクションブロー成形、インフレーション成形、プレス成形、押出成形、発泡成形、フィルム成形等、公知の方法で成形することが可能であり、圧空成形、真空成形等の二次加工成形法も用いることができる。 The molded body of the flame retardant thermoplastic resin composition of the present invention can be obtained by known methods such as injection molding, sheet molding, blow molding, injection blow molding, inflation molding, press molding, extrusion molding, foam molding, film molding, and the like. It is possible to mold, and secondary processing molding methods such as pressure forming and vacuum forming can also be used.
(難燃性熱可塑性樹脂組成物の用途)
本発明の難燃性熱可塑性樹脂組成物は、コイルボビン、フライバックトランス、コネクター、偏光ヨーク等の電気・電子機器部品、プリント配線板、プリント基板、封止剤、電気絶縁材料、電気被覆剤、積層板、高速演算用ワニス、先端複合材料、電線、アンテナ剤、ケーブル、高性能成型材料等の電気・電子材料用途、塗料、接着剤、コーティング材、食器、ボタン、繊維・紙処理剤、化粧板、UV硬化型インキ、シーラント、合成皮革、断熱緩衝材料、塗膜防水材、防食ライニング、鋳型用バインダー、ラッカー、ペイント、インキの改質材、樹脂変性材、航空機内装剤、複合材料用マトリックス、家庭用品、OA機器、AV機器、電池電装用、照明機器、自動車部品用途、ハウジング用途、ETC、ITC、携帯電話等に最適に使用される。
(Use of flame retardant thermoplastic resin composition)
The flame-retardant thermoplastic resin composition of the present invention includes coil bobbins, flyback transformers, connectors, electrical and electronic equipment parts such as polarizing yokes, printed wiring boards, printed boards, sealants, electrical insulating materials, electrical coatings, Laminates, varnishes for high-speed computing, advanced composite materials, electric wires, antenna agents, cables, high-performance molding materials and other electrical and electronic materials, paints, adhesives, coating materials, tableware, buttons, textile and paper treatment agents, makeup Board, UV curable ink, sealant, synthetic leather, heat insulation buffer material, waterproof coating material, anticorrosion lining, mold binder, lacquer, paint, ink modifier, resin modifier, aircraft interior agent, matrix for composite materials Ideal for household appliances, OA equipment, AV equipment, battery electrical equipment, lighting equipment, automotive parts use, housing use, ETC, ITC, mobile phones, etc. That.
以下、実施例によって本発明を具体的に説明するが、本発明は以下の例に限定されるものではない。また、本発明の組成物の調整方法は、各種材料を均一に混合することができる手法であれば特に限定されるものではない。
まず、実施例及び比較例で得られたサンプルの評価方法について述べる。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following examples. Moreover, the adjustment method of the composition of this invention will not be specifically limited if it is a method which can mix various materials uniformly.
First, a method for evaluating samples obtained in Examples and Comparative Examples will be described.
(1) 難燃性
UL−94垂直燃焼試験に基づき、約1.6mm厚みの射出成形試験片を用いて測定し、10回接炎時の平均燃焼時間と燃焼時の滴下物による脱脂綿着火の有無を評価した。
(1) Flame retardance Based on the UL-94 vertical combustion test, measured using an injection molded test piece with a thickness of about 1.6 mm. The presence or absence was evaluated.
(2) 燃焼時の発煙性
UL−94垂直燃焼試験は、UL燃焼テストチャンバー(HVUL−C;(株)東洋精機製作所製)を用いて行い、燃焼試験時に発生する煙がチャンバーからほとんど漏れでなかった場合は○、少し漏れ出た場合は△、多量に漏れ出た場合は×として、目視により評価を行った。
(2) Smoke emission during combustion The UL-94 vertical combustion test is performed using a UL combustion test chamber (HVUL-C; manufactured by Toyo Seiki Seisakusho Co., Ltd.), and smoke generated during the combustion test is almost leaked from the chamber. When there was no leakage, the evaluation was made visually as ◯, when it leaked a little, Δ when it leaked a lot, and evaluated as visual.
(3) TGA(Thermogravimetric Analysis;熱重量分析)
サンプル約10mgを、パーキンエルマー社製Thermal Analysis System 7 Seriesを用いて、窒素気流30ml/min中、10℃/minの速度で600℃まで昇温したときの重量が、5%減量した時の温度及び、50%減量した時の温度を測定し、その差を測定した。
(3) TGA (Thermogravimetric Analysis)
The temperature when about 10 mg of a sample was heated to 600 ° C. at a rate of 10 ° C./min in a nitrogen stream 30 ml / min using Thermal Analysis System 7 Series manufactured by PerkinElmer, Inc., and the weight was reduced by 5%. And the temperature when it reduced 50% was measured, and the difference was measured.
(4) 水分量測定
設定温度150℃で、カールフィッシャー法により測定した。
(5) 耐熱性(DTUL)
ASTM−D−648に基づき、厚さ6.4mmの試験片を用いて、18.6kg荷重にて測定した。
(6) 誘電特性
厚さ約2.5mmの成型片を用いて、比誘電率を周波数1GHzにて容量法で測定した。
(4) Moisture content measurement The moisture content was measured by the Karl Fischer method at a set temperature of 150 ° C.
(5) Heat resistance (DTUL)
Based on ASTM-D-648, the measurement was performed at a load of 18.6 kg using a test piece having a thickness of 6.4 mm.
(6) Dielectric properties Using a molded piece having a thickness of about 2.5 mm, the relative dielectric constant was measured by a capacitance method at a frequency of 1 GHz.
(7) 離型性
下記設定温度にて、射出成形により、ASTM−D−638ダンベル型試験片を成形し、成形した際に、試験片およびランナーの金型からの型離れのし易さの程度を目視判定した。離型が良いものは○、離型が良くないものは×で表した。
実施例1〜3、比較例1 バレル温度220℃ 金型温度 60℃
実施例4〜6、比較例2〜5 バレル温度280℃ 金型温度 80℃
(7) Mold releasability ASTM-D-638 dumbbell mold test piece is molded by injection molding at the following set temperature, and when the mold is molded, it is easy to release the mold from the test piece and runner mold. The degree was visually determined. Those with good mold release are indicated by ○, and those with poor release are indicated by x.
Examples 1-3, Comparative Example 1 Barrel temperature 220 ° C. Mold temperature 60 ° C.
Examples 4-6, Comparative Examples 2-5 Barrel temperature 280 ° C Mold temperature 80 ° C
(8) 押出作業性
加熱シリンダーの最高温度を下記の温度で設定し、スクリュー直径25mmの二軸押出機で、スクリュー回転数300rpmで溶融混合した。
実施例1〜3、比較例1 − 220℃
実施例4〜6、比較例2〜7、参考例1、2 − 300℃
10分間溶融混錬を行ったときに、ストランドが途中で二度以上切れたものは×、一度切れたものを△、一度も切れなかったものを○として目視により判定を行った。
実施例及び比較例で用いた各成分は以下のものである。
(8) Extrusion workability The maximum temperature of the heating cylinder was set at the following temperature, and the mixture was melt-mixed at a screw rotation speed of 300 rpm with a twin screw extruder having a screw diameter of 25 mm.
Examples 1 to 3, Comparative Example 1-220 ° C
Examples 4 to 6 , Comparative Examples 2 to 7 , Reference Examples 1, 2 to 300 ° C
When melt-kneading was performed for 10 minutes, the strands were judged by visual inspection as “x” when the strand was cut twice or more, Δ when the strand was cut once, and ○ when it was never cut.
Each component used in Examples and Comparative Examples is as follows.
(A)三価のリン化合物
(P−1)
トリフェニルホスフィン(和光純薬工業(株)社製)。
(P−2)
トリス(m−メチルフェニル)ホスフィン(和光純薬工業(株)社製)。
(P−3)
1−ブロモ−2−メチルベンゼン(TolBr)と金属マグネシウムから調製した2−メチルフェニルマグネシウムブロマイド(TolMgBr)と三塩化リンとの反応により得たトリス(o−メチルフェニル)ホスフィン。
(A) Trivalent phosphorus compound (P-1)
Triphenylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.).
(P-2)
Tris (m-methylphenyl) phosphine (manufactured by Wako Pure Chemical Industries, Ltd.).
(P-3)
Tris (o-methylphenyl) phosphine obtained by reaction of 2-methylphenylmagnesium bromide (TolMgBr) prepared from 1-bromo-2-methylbenzene (TolBr) and metallic magnesium with phosphorus trichloride.
(B)五価のリン化合物
(B−1)
(FR−1)
下記一般式(12)においてn=3が93.6wt%、n=4が4.0wt%、n≧5が2.4wt%であるフェノキシホスファゼン。5%減量温度;336℃、50%減量温度;398℃、500℃残渣量;4.7重量%、酸価;0.17、含有水分量;182ppm。
(B) Pentavalent phosphorus compound (B-1)
(FR-1)
Phenoxyphosphazene in which n = 3 is 93.6 wt%, n = 4 is 4.0 wt%, and n ≧ 5 is 2.4 wt% in the following general formula (12). 5% weight loss temperature: 336 ° C., 50% weight loss temperature: 398 ° C., 500 ° C. Residue amount: 4.7 wt%, acid value: 0.17, water content: 182 ppm.
(FR−2)
下記一般式(12)において、n=3が85.3wt%、n=4が9.3wt%、n≧5が5.4wt%であるフェノキシホスファゼン。5%減量温度;318℃、50%減量温度;421℃、500℃残渣量;14.2重量%、酸価1.04、含有水分量;1100ppm。
(FR-2)
In the following general formula (12), phenoxyphosphazene in which n = 3 is 85.3 wt%, n = 4 is 9.3 wt%, and n ≧ 5 is 5.4 wt%. 318 ° C., 50% weight loss temperature; 421 ° C., 500 ° C. Residue amount; 14.2 wt%, acid value 1.04, moisture content contained: 1100 ppm.
(FR−3)
レゾルシンと2,6−キシレノールを原料として合成される縮合リン酸エステルで、PX−200(大八化学工業(株)社製)。酸価0.11、5%減量温度:319℃、50%減量温度;388℃、500℃残渣量;0.9重量%、含有水分量;235ppm。
(FR-3)
PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), a condensed phosphate ester synthesized from resorcin and 2,6-xylenol. Acid value 0.11, 5% weight loss temperature: 319 ° C., 50% weight loss temperature; 388 ° C., 500 ° C. Residue amount; 0.9 wt%, moisture content: 235 ppm.
(FR−4)
ビスフェノールAとフェノールを原料として合成される縮合リン酸エステルで、下記化学式(13)において、n=1である化合物を85.3重量%、n=2である化合物を12.6重量%含有する縮合リン酸エステル。酸価0.18、5%減量温度;359℃、50%減量温度;433℃、500℃残渣量;2.1重量%、含有水分量;324ppm。
(FR-4)
Condensed phosphate ester synthesized using bisphenol A and phenol as raw materials, and containing 85.3% by weight of a compound where n = 1 and 12.6% by weight of a compound where n = 2 in the following chemical formula (13) Condensed phosphate ester. Acid value 0.18, 5% weight loss temperature; 359 ° C., 50% weight loss temperature; 433 ° C., 500 ° C. Residue amount; 2.1 wt%, moisture content: 324 ppm.
(樹脂他)
(1) ポリフェニレンエーテル系樹脂(PPE)
30℃のクロロホルム溶液で測定したηsp/cが0.54のポリ−2,6−ジメチル−1,4−フェニレンエーテル。
(2)ゴム補強ポリスチレン(HIPS)
ゴム含量9%、30℃、トルエン溶液で測定したマトリックスポリスチレンのηsp/cが0.64、体積平均ゴム粒子径が1.5μmのゴム補強ポリスチレン。
(3)ポリスチレン(GPPS)
トルエン溶液で測定したηsp/cが、0.8のポリスチレン
(4)ポリカーボネート樹脂(PC)
パンライトL−1250Y(帝人化成(株)製);非難燃透明グレード。
(Resin etc.)
(1) Polyphenylene ether resin (PPE)
Poly-2,6-dimethyl-1,4-phenylene ether having a ηsp / c of 0.54 measured with a 30 ° C. chloroform solution.
(2) Rubber reinforced polystyrene (HIPS)
A rubber-reinforced polystyrene having a rubber content of 9%, 30 ° C., ηsp / c of the matrix polystyrene measured with a toluene solution is 0.64, and the volume average rubber particle diameter is 1.5 μm.
(3) Polystyrene (GPPS)
Polystyrene (4) polycarbonate resin (PC) having a ηsp / c of 0.8 measured with a toluene solution
Panlite L-1250Y (manufactured by Teijin Chemicals Ltd.); non-flame retardant transparent grade.
[実施例1〜8、比較例1〜8、参考例1、2]
各成分を表1〜4に示す割合で混合し、加熱シリンダーの最高温度を200〜330℃に設定したスクリュー直径25mmの二軸押出機に供給して、スクリュー回転数300rpmで溶融混合し、ストランドを冷却裁断して樹脂組成物ペレットを得た。
次に、得られた樹脂組成物ペレットを、射出成形により200〜330℃にて物性試験片を成形し、上記試験法により物性試験を行い、表1〜4の結果を得た。
[Example 1-8, Comparative Examples 1-8, Reference Examples 1 and 2
Each component is mixed in the ratio shown in Tables 1 to 4, and supplied to a twin screw extruder having a screw diameter of 25 mm with the maximum temperature of the heating cylinder set to 200 to 330 ° C., and melt mixed at a screw rotation speed of 300 rpm. Was cut by cooling to obtain a resin composition pellet.
Next, the obtained resin composition pellets were molded into physical property test pieces at 200 to 330 ° C. by injection molding, and subjected to physical property tests by the above test methods, and the results shown in Tables 1 to 4 were obtained.
本発明による、熱可塑性樹脂及び、(A)三価のリン化合物、(B)特定のホスファゼン化合物、必要により(C)芳香族樹脂からなる難燃性熱可塑性樹脂組成物は、難燃性、低発煙性、耐熱性、耐吸湿性、誘電特性等に優れており、コイルボビン、フライバックトランス、コネクター、偏光ヨーク等の電気・電子機器部品、プリント配線板、プリント基板、封止剤、電気絶縁材料、電気被覆剤、積層板、高速演算用ワニス、先端複合材料、電線、アンテナ剤、ケーブル、高性能成型材料等の電気・電子材料用途、塗料、接着剤、コーティング材、食器、ボタン、繊維・紙処理剤、化粧板、UV硬化型インキ、シーラント、合成皮革、断熱緩衝材料、塗膜防水材、防食ライニング、鋳型用バインダー、ラッカー、ペイント、インキの改質材、樹脂変性材、航空機内装剤、複合材料用マトリックス、家庭用品、OA機器、AV機器、電池電装用、照明機器、自動車部品用途、ハウジング用途、ETC、ITC、携帯電話等に最適に使用される。 According to the present invention, a flame retardant thermoplastic resin composition comprising a thermoplastic resin and (A) a trivalent phosphorus compound, (B) a specific phosphazene compound, and optionally (C) an aromatic resin, Excellent in low smoke generation, heat resistance, moisture absorption, dielectric properties, etc. Electrical and electronic equipment parts such as coil bobbins, flyback transformers, connectors, polarizing yokes, printed wiring boards, printed boards, sealants, electrical insulation Materials, electrical coatings, laminates, varnishes for high-speed computation, advanced composite materials, electric wires, antenna agents, cables, high-performance molding materials and other electrical and electronic materials, paints, adhesives, coating materials, tableware, buttons, textiles・ Paper treatment agent, decorative board, UV curable ink, sealant, synthetic leather, heat insulating cushioning material, waterproof coating material, anticorrosion lining, mold binder, lacquer, paint, ink modifier, Fat-modified material, aircraft interiors agents, matrix composite material, household goods, OA equipment, AV equipment, battery electrical, lighting equipment, automobile parts application, housing applications, ETC, ITC, is optimally used in cellular phones.
Claims (11)
(A)成分:三価のリン化合物
(B)成分:TGAによる不活性ガス雰囲気下、昇温速度10℃/minで常温から600℃まで加熱した時の、50重量%の重量減少時の温度と5重量%の重量減少時の温度の差が40〜100℃であるホスファゼン化合物 A flame retardant thermoplastic resin composition comprising a thermoplastic resin containing the following component (A) and the following component (B).
(A) Component: Trivalent phosphorus compound (B) Component: Temperature at a weight loss of 50% by weight when heated from normal temperature to 600 ° C. at a heating rate of 10 ° C./min in an inert gas atmosphere by TGA And a phosphazene compound having a temperature difference of 40 to 100 ° C. when the weight is reduced by 5% by weight
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JP2004321528A JP3973106B2 (en) | 2003-11-07 | 2004-11-05 | Flame retardant thermoplastic resin composition |
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JP2003377980 | 2003-11-07 | ||
JP2004321528A JP3973106B2 (en) | 2003-11-07 | 2004-11-05 | Flame retardant thermoplastic resin composition |
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JP2005154762A JP2005154762A (en) | 2005-06-16 |
JP2005154762A5 true JP2005154762A5 (en) | 2007-06-07 |
JP3973106B2 JP3973106B2 (en) | 2007-09-12 |
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JP3932198B2 (en) * | 2003-11-07 | 2007-06-20 | 旭化成ケミカルズ株式会社 | Flame retardant composition |
JP6231452B2 (en) * | 2014-08-06 | 2017-11-15 | 旭化成株式会社 | Flame retardant resin composition and method for producing the same |
JP6927438B2 (en) * | 2019-03-27 | 2021-09-01 | 大日本印刷株式会社 | Transparent resin film, decorative material, and manufacturing method of decorative material |
US11993063B2 (en) | 2019-04-18 | 2024-05-28 | Dai Nippon Printing Co., Ltd. | Transparent resin film, transparent resin film production method, and decorative material |
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