JP2011001486A - Flame-retardant polyphenylene ether-based resin composition and molded article thereof - Google Patents
Flame-retardant polyphenylene ether-based resin composition and molded article thereof Download PDFInfo
- Publication number
- JP2011001486A JP2011001486A JP2009146480A JP2009146480A JP2011001486A JP 2011001486 A JP2011001486 A JP 2011001486A JP 2009146480 A JP2009146480 A JP 2009146480A JP 2009146480 A JP2009146480 A JP 2009146480A JP 2011001486 A JP2011001486 A JP 2011001486A
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- JP
- Japan
- Prior art keywords
- polyphenylene ether
- resin
- resin composition
- flame
- weight
- 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
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 61
- 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 abstract description 59
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 55
- 239000011342 resin composition Substances 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 94
- 229920005989 resin Polymers 0.000 claims abstract description 94
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 33
- 239000010452 phosphate Substances 0.000 claims abstract description 33
- 238000000465 moulding Methods 0.000 claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- -1 phosphate ester compound Chemical class 0.000 claims description 51
- 150000002148 esters Chemical class 0.000 claims description 21
- 239000007789 gas Substances 0.000 abstract description 19
- 229920001577 copolymer Polymers 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000002411 thermogravimetry Methods 0.000 description 12
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920000388 Polyphosphate Polymers 0.000 description 8
- 238000005336 cracking Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000001205 polyphosphate Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000011109 contamination Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229920002545 silicone oil Polymers 0.000 description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 235000011176 polyphosphates Nutrition 0.000 description 4
- 229960001755 resorcinol Drugs 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 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 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 2
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920001890 Novodur Polymers 0.000 description 2
- FRCLQKLLFQYUJJ-UHFFFAOYSA-N P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C Chemical compound P(O)(O)O.P(O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)C)C(C)(C)C FRCLQKLLFQYUJJ-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 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
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- UTGPYHWDXYRYGT-UHFFFAOYSA-N tetratriacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTGPYHWDXYRYGT-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QIKKFTUQKYGBLZ-UHFFFAOYSA-N 1,1,3,3,3-pentafluoropropane-1,2,2-triol Chemical compound OC(F)(F)C(O)(O)C(F)(F)F QIKKFTUQKYGBLZ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- METWAQRCMRWDAW-UHFFFAOYSA-N 2,6-diethylphenol Chemical compound CCC1=CC=CC(CC)=C1O METWAQRCMRWDAW-UHFFFAOYSA-N 0.000 description 1
- NAILKKRDWBJCNH-UHFFFAOYSA-N 2,6-dipropylphenol Chemical compound CCCC1=CC=CC(CCC)=C1O NAILKKRDWBJCNH-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- MQHZSBOMTFGHIH-UHFFFAOYSA-N 2-octyldodecyl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(CCCCCCCC)CCCCCCCCCC MQHZSBOMTFGHIH-UHFFFAOYSA-N 0.000 description 1
- IJAJGQIUSCYZPR-UHFFFAOYSA-N 3,5-diethyl-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound CCC1=C(O2)C(CC)=CC2=C1 IJAJGQIUSCYZPR-UHFFFAOYSA-N 0.000 description 1
- KXRLIZRDCCQKDZ-UHFFFAOYSA-N 3-ethyl-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(CC)=CC2=C1 KXRLIZRDCCQKDZ-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 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
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、難燃性ポリフェニレンエーテル系樹脂組成物及びその成形品に関する。詳しくは、難燃性に優れると共に、成形時のガス発生の問題がなく、金型汚染や成形品の応力腐食割れを防止することができる難燃性ポリフェニレンエーテル系樹脂組成物及びその成形品に関する。 The present invention relates to a flame retardant polyphenylene ether resin composition and a molded article thereof. More specifically, the present invention relates to a flame retardant polyphenylene ether resin composition that is excellent in flame retardancy, has no problem of gas generation during molding, and can prevent mold contamination and stress corrosion cracking of the molded product, and the molded product thereof. .
ポリフェニレンエーテル樹脂は、熱的性質、機械的性質、電気的性質等諸特性に優れたエンジニアリングプラスチックであるが、溶融粘度が高いために成形加工性に劣り、耐衝撃性も劣るという欠点を有している。そこで、ポリフェニレンエーテル樹脂は、通常、その成形加工性や耐衝撃性の改良を目的として、各種の樹脂を配合した樹脂組成物として用いられており、配合樹脂として、スチレン系樹脂を用いたものが提供されている。 Polyphenylene ether resin is an engineering plastic that has excellent properties such as thermal properties, mechanical properties, and electrical properties. However, it has the disadvantages of poor moldability and impact resistance due to its high melt viscosity. ing. Therefore, polyphenylene ether resins are usually used as resin compositions containing various resins for the purpose of improving molding processability and impact resistance, and those using styrenic resins as compounded resins. Is provided.
また、このようなポリフェニレンエーテル樹脂／スチレン系樹脂組成物において、難燃性の改善を目的として、各々の難燃剤を配合したものも提供されている。例えば、特許文献１には、ポリフェニレンエーテル樹脂２０〜９５重量％とスチレン系樹脂５〜８０重量％からなる樹脂成分１００重量部に対し、リン酸エステル系難燃剤を１〜３０重量部配合した樹脂組成物が提案されている。この特許文献１では、難燃剤として、汎用のリン酸エステル系難燃剤、具体的にはフェニル・レゾルシン・ポリホスフェート、クレジル・レゾルシン・ポリホスフェート、フェニル・クレジル・レゾルシン・ポリホスフェート、キシリル・レゾルシン・ポリホスフェート、フェニル−ｐ−ｔｅｒｔ−ブチルフェニル・レゾルシン・ポリホスフェート、フェニル・イソプロピルフェニル・レゾルシン・ポリホスフェート、クレジル・キシレル・レゾルシン・ポリホスフェート、フェニル・イソプロピルフェニル・ジイソプロピルフェニル・レゾルシン・ポリホスフェート、ビスフェノールＡビス（ジフェニルホスフェート）等の縮合リン酸エステル類；リン酸トリフェニル（トリフェニルホスフェート）、リン酸トリクレジル、リン酸ジフェニル２エチルクレジル、リン酸トリ（イソプロピルフェニル）、メチルホスホン酸ジフェニルエステル、フェニルホスホン酸ジエチルエステル、リン酸ジフェニルクレジル、リン酸トリブチル等が用いられている。また、レゾルシノールビス（ジフェニルホスフェート）などが用いられている例もある。
In addition, in such a polyphenylene ether resin / styrene-based resin composition, a composition in which each flame retardant is blended is provided for the purpose of improving the flame retardancy. For example, Patent Document 1 discloses a resin in which 1 to 30 parts by weight of a phosphate ester flame retardant is blended with 100 parts by weight of a resin component composed of 20 to 95% by weight of a polyphenylene ether resin and 5 to 80% by weight of a styrene resin. Compositions have been proposed. In this patent document 1, as a flame retardant, a general-purpose phosphate ester flame retardant, specifically phenyl resorcin polyphosphate, cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, xylyl resorcin Polyphosphate, phenyl-p-tert-butylphenyl-resorcinol-polyphosphate, phenyl-isopropylphenyl-resorcinol-polyphosphate, cresyl-xyler-resorcinol-polyphosphate, phenyl-isopropylphenyl-diisopropylphenyl-resorcinol-polyphosphate, bisphenol A condensed phosphate esters such as bis (diphenyl phosphate); triphenyl phosphate (triphenyl phosphate), tricresyl phosphate,
なお、本発明で難燃剤として用いる特定のリン酸エステル系難燃剤は、特許文献２に記載されている。
In addition, the specific phosphate ester type flame retardant used as a flame retardant in the present invention is described in
しかしながら、このような難燃剤を配合したポリフェニレンエーテル樹脂／スチレン系樹脂組成物に特有の問題として、成形時のガス発生による金型汚染及び成形品の応力腐食割れの問題がある。
即ち、難燃剤を配合した樹脂組成物では、一般に、成形時の加熱で高温にさらされることにより、組成物中の難燃剤が熱分解して分解ガスが発生し、
・発生したガスにより金型が汚染され、この汚染が得られる成形品の品質不良の原因となる。
・発生ガス量が特に多い場合には、金型汚染で成形を継続し得なくなり、連続成形が不可能となる。
・発生ガスが成形品の残留応力の大きい部分、例えば、エッジ部等に付着することで、成形品の割れ等の欠陥の原因となる。
といった問題が生じていた。
However, problems peculiar to the polyphenylene ether resin / styrene-based resin composition containing such a flame retardant include mold contamination due to gas generation during molding and stress corrosion cracking of the molded product.
That is, in a resin composition containing a flame retardant, generally, the flame retardant in the composition is pyrolyzed and decomposed gas is generated by being exposed to a high temperature by heating during molding,
-The mold is contaminated by the generated gas, and this contamination causes the quality defect of the molded product.
・ If the amount of generated gas is particularly large, molding cannot be continued due to mold contamination, and continuous molding becomes impossible.
-The generated gas adheres to a portion having a large residual stress of the molded product, for example, an edge portion, etc., thereby causing defects such as cracking of the molded product.
There was a problem such as.
なお、本発明で用いる特定のリン酸エステル系難燃剤は特許文献２に記載されて公知の難燃剤であり、特許文献２には、このリン酸エステル系難燃剤をポリフェニレンエーテル樹脂に添加し得る旨の記載もある。しかしながら、特許文献２には、ポリフェニレンエーテル樹脂／スチレン系樹脂組成物に特有の上記課題、即ち、成形時のガス発生の問題についての認識は全くなく、また、実際にポリフェニレンエーテル樹脂／スチレン系樹脂組成物に配合した例もなく、そもそも、特許文献２には、このリン酸エステル系難燃剤が樹脂成形時の加熱における耐熱分解性に優れるとの認識もない。
The specific phosphate ester flame retardant used in the present invention is a known flame retardant described in
本発明は上記従来の問題点を解決し、難燃性に優れ、しかも、難燃剤に起因する成形時のガス発生の問題がなく、高品質の成形品を歩留り良く製造することができる難燃性ポリフェニレンエーテル系樹脂組成物と、その成形品を提供することを目的とする。 The present invention solves the above-mentioned conventional problems, is excellent in flame retardancy, has no problem of gas generation during molding due to the flame retardant, and can produce high-quality molded products with good yield An object is to provide a conductive polyphenylene ether-based resin composition and a molded product thereof.
本発明者は、上記課題を解決すべく鋭意検討した結果、特定の難燃剤を用いることにより、成形時のガス発生の問題を解決することができることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventor has found that the problem of gas generation during molding can be solved by using a specific flame retardant, and has completed the present invention.
即ち、本発明（請求項１）の難燃性ポリフェニレンエーテル系樹脂組成物は、ポリフェニレンエーテル樹脂とスチレン系樹脂とを含む樹脂成分１００重量部に対して、下記一般式（１）で表されるリン酸エステル系難燃剤を２〜３０重量部含有してなることを特徴とする。 That is, the flame retardant polyphenylene ether resin composition of the present invention (Claim 1) is represented by the following general formula (1) with respect to 100 parts by weight of a resin component containing a polyphenylene ether resin and a styrene resin. It contains 2 to 30 parts by weight of a phosphate ester flame retardant.
（式中、Ｒ１、Ｒ２は各々独立に水素原子又はメチル基を表し、ｎは１〜５の数を表す。） (Wherein, R 1, R 2 represents a hydrogen atom or a methyl group independently, n represents a number from 1-5.)
請求項２の難燃性ポリフェニレンエーテル系樹脂組成物は、請求項１において、樹脂成分が、ポリフェニレンエーテル樹脂２０〜９５重量％と、スチレン系樹脂５〜８０重量％とを含むことを特徴とする。
The flame-retardant polyphenylene ether resin composition according to
請求項３の難燃性ポリフェニレンエーテル系樹脂組成物は、請求項１又は２において、前記リン酸エステル系難燃剤中の一般式（１）におけるｎが１であるリン酸エステル化合物の割合が９０重量％未満であることを特徴とする。
The flame-retardant polyphenylene ether-based resin composition according to claim 3 is characterized in that, in
請求項４の難燃性ポリフェニレンエーテル系樹脂組成物は、請求項１ないし３のいずれか１項において、前記一般式（１）におけるＲ１及びＲ２が水素原子であることを特徴とする。
The flame-retardant polyphenylene ether-based resin composition according to
本発明（請求項５）の成形品は、請求項１ないし４のいずれか１項に記載の難燃性ポリフェニレンエーテル系樹脂組成物を成形してなることを特徴とする。 The molded product of the present invention (invention 5) is characterized by being formed by molding the flame-retardant polyphenylene ether resin composition according to any one of claims 1 to 4.
本発明で難燃剤として用いる前記一般式（１）で表されるリン酸エステル系難燃剤は、耐熱性（耐熱分解性）に優れ、ポリフェニレンエーテル樹脂／スチレン系樹脂組成物の成形時の加熱温度で殆ど分解することはない。このため、難燃剤として、この特定のリン酸エステル系難燃剤を用いた本発明の難燃性ポリフェニレンエーテル系樹脂組成物によれば、成形時の加熱による分解ガスの発生、それによる金型汚染や、応力腐食による成形品の割れの問題を解決して、高品質の成形品を歩留り良く製造することができる。なお、後述の実施例と比較例との対比からも明らかなように、このリン酸エステル系難燃剤を用いた場合には、成形品の曲げ弾性率等の機械的特性及び耐熱性も改善される。 The phosphate ester flame retardant represented by the general formula (1) used as a flame retardant in the present invention is excellent in heat resistance (heat decomposability) and is a heating temperature at the time of molding a polyphenylene ether resin / styrene resin composition. Almost never decomposes. Therefore, according to the flame retardant polyphenylene ether resin composition of the present invention using this specific phosphate ester flame retardant as a flame retardant, generation of decomposition gas due to heating during molding, resulting in mold contamination In addition, it is possible to solve the problem of cracking of the molded product due to stress corrosion and to manufacture a high-quality molded product with a high yield. As is clear from the comparison between Examples and Comparative Examples described later, when this phosphate ester flame retardant is used, mechanical properties such as bending elastic modulus and heat resistance of the molded product are also improved. The
本発明に係る樹脂成分は、ポリフェニレンエーテル樹脂２０〜９５重量％と、スチレン系樹脂５〜８０重量％とを含むものであることが好ましい（請求項２）。 The resin component according to the present invention preferably contains 20 to 95% by weight of a polyphenylene ether resin and 5 to 80% by weight of a styrene resin (Claim 2).
また、用いるリン酸エステル系難燃剤は、前記一般式（１）におけるｎが１のリン酸エステル化合物の割合が９０重量％未満であることが好ましく（請求項３）、また、Ｒ１及びＲ２が水素原子であることが好ましい（請求項４）。 Moreover, it is preferable that the phosphate ester type flame retardant to be used has a ratio of the phosphate ester compound in which n is 1 in the general formula (1) is less than 90% by weight (Claim 3), and R 1 and R 2 is preferably a hydrogen atom (claim 4).
以下に本発明の実施の形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
［ポリフェニレンエーテル樹脂］
本発明の樹脂組成物に用いられるポリフェニレンエーテル樹脂は、下記一般式（２）で表される構造単位を主鎖に有する重合体であって、単独重合体又は共重合体の何れであっても良い。
[Polyphenylene ether resin]
The polyphenylene ether resin used in the resin composition of the present invention is a polymer having a structural unit represented by the following general formula (2) in the main chain, and may be either a homopolymer or a copolymer. good.
（式中、２つのＲａは、それぞれ独立に、水素原子、ハロゲン原子、第１級若しくは第２級アルキル基、アリール基、アミノアルキル基、ハロアルキル基、炭化水素オキシ基、又はハロ炭化水素オキシ基を表し、２つのＲｂは、それぞれ独立に、水素原子、ハロゲン原子、第１級若しくは第２級アルキル基、アリール基、ハロアルキル基、炭化水素オキシ基、又はハロ炭化水素オキシ基を表す。ただし、２つのＲａがともに水素原子になることはない。） (In the formula, two R a s each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group. Each of the two R b s independently represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group. However, both R a are not hydrogen atoms.)
Ｒａ及びＲｂとしては、水素原子、第１級若しくは第２級アルキル基、アリール基が好ましい。第１級アルキル基の好適な例としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基、ｎ−アミル基、イソアミル基、２−メチルブチル基、２，３−ジメチルブチル基、２−、３−若しくは４−メチルペンチル基又はヘプチル基が挙げられる。第２級アルキル基の好適な例としては、例えば、イソプロピル基、ｓｅｃ−ブチル基又は１−エチルプロピル基が挙げられる。特に、Ｒａは第１級若しくは第２級の炭素数１〜４のアルキル基又はフェニル基であることが好ましい。Ｒｂは水素原子であることが好ましい。 R a and R b are preferably a hydrogen atom, a primary or secondary alkyl group, or an aryl group. Preferable examples of the primary alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, isoamyl group, 2-methylbutyl group, 2,3-dimethylbutyl group, 2 -, 3- or 4-methylpentyl group or heptyl group may be mentioned. Preferable examples of the secondary alkyl group include isopropyl group, sec-butyl group, and 1-ethylpropyl group. In particular, Ra is preferably a primary or secondary alkyl group having 1 to 4 carbon atoms or a phenyl group. R b is preferably a hydrogen atom.
好適なポリフェニレンエーテル樹脂の単独重合体としては、例えば、ポリ（２，６−ジメチル−１，４−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（２，６−ジプロピル−１，４−フェニレンエーテル）、ポリ（２−エチル−６−メチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−プロピル−１，４−フェニレンエーテル）等の２，６−ジアルキルフェニレンエーテルの重合体が挙げられる。共重合体としては、２，６−ジメチルフェノール／２，３，６−トリメチルフェノール共重合体、２，６−ジメチルフェノール／２，３，６−トリエチルフェノール共重合体、２，６−ジエチルフェノール／２，３，６−トリメチルフェノール共重合体、２，６−ジプロピルフェノール／２，３，６−トリメチルフェノール共重合体等の２，６−ジアルキルフェノール／２，３，６−トリアルキルフェノール共重合体、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）にスチレンをグラフト重合させたグラフト共重合体、２，６−ジメチルフェノール／２，３，６−トリメチルフェノール共重合体にスチレンをグラフト重合させたグラフト共重合体等が挙げられる。 Suitable homopolymers of polyphenylene ether resins include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2, 2 such as 6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-methyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), etc. , 6-dialkylphenylene ether polymer. Examples of the copolymer include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymer, and 2,6-diethylphenol. 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymer such as 2,3,6-trimethylphenol copolymer, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymer Polymer, graft copolymer obtained by graft polymerization of styrene to poly (2,6-dimethyl-1,4-phenylene ether), styrene to 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer And a graft copolymer obtained by graft polymerization.
本発明におけるポリフェニレンエーテル樹脂としては、特に、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、２，６−ジメチルフェノール／２，３，６−トリメチルフェノールランダム共重合体が好ましい。また、特開２００５−３４４０６５号公報に記載されているような末端基数と銅含有率を規定したポリフェニレンエーテル樹脂も好適に使用できる。 As the polyphenylene ether resin in the present invention, poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer are particularly preferable. In addition, polyphenylene ether resins that define the number of terminal groups and the copper content as described in JP-A-2005-344065 can also be suitably used.
ポリフェニレンエーテル樹脂の分子量は、クロロホルム中で測定した３０℃の固有粘度が０．２〜０．８ｄｌ／ｇのものが好ましく、０．３〜０．６ｄｌ／ｇのものがより好ましい。極限粘度を０．２ｄｌ／ｇ以上とすることにより、樹脂組成物の機械的強度が向上する傾向にあり、０．８ｄｌ／ｇ以下とすることにより、流動性が向上し、成形加工が容易になる傾向にある。また、固有粘度の異なる２種以上のポリフェニレンエーテル樹脂を併用して、この固有粘度の範囲としてもよい。 The molecular weight of the polyphenylene ether resin is preferably such that the intrinsic viscosity at 30 ° C. measured in chloroform is 0.2 to 0.8 dl / g, more preferably 0.3 to 0.6 dl / g. When the intrinsic viscosity is 0.2 dl / g or more, the mechanical strength of the resin composition tends to be improved, and when it is 0.8 dl / g or less, the fluidity is improved and the molding process is easy. Tend to be. Two or more kinds of polyphenylene ether resins having different intrinsic viscosities may be used in combination to achieve this intrinsic viscosity range.
本発明に使用されるポリフェニレンエーテル樹脂の製造法は、特に限定されるものではなく、公知の方法に従って、例えば、２，６−ジメチルフェノール等のモノマーをアミン銅触媒の存在下、酸化重合することにより製造することができ、その際、反応条件を選択することにより、極限粘度を所望の範囲に制御することができる。極限粘度の制御は、重合温度、重合時間、触媒量等の条件を選択することにより達成できる。 The method for producing the polyphenylene ether resin used in the present invention is not particularly limited. For example, according to a known method, a monomer such as 2,6-dimethylphenol is oxidatively polymerized in the presence of an amine copper catalyst. In this case, the intrinsic viscosity can be controlled within a desired range by selecting reaction conditions. Control of the intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and catalyst amount.
本発明において、ポリフェニレンエーテル樹脂は１種を単独で用いても良く、２種以上を混合して用いても良い。 In this invention, polyphenylene ether resin may be used individually by 1 type, and 2 or more types may be mixed and used for it.
［スチレン系樹脂］
一方、本発明に用いられるスチレン系樹脂としては、スチレン系単量体の重合体、スチレン系単量体と他の共重合可能な単量体との共重合体及びスチレン系グラフト共重合体等が挙げられる。
[Styrene resin]
On the other hand, examples of the styrene resin used in the present invention include a styrene monomer polymer, a copolymer of a styrene monomer and another copolymerizable monomer, and a styrene graft copolymer. Is mentioned.
本発明で使用されるスチレン系樹脂としては、より具体的には、ポリスチレン、スチレン・ブタジエン・スチレン共重合体（ＳＢＳ樹脂）、水添スチレン・ブタジエン・スチレン共重合体（水添ＳＢＳ）、水添スチレン・イソプレン・スチレン共重合体（ＳＥＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）、アクリロニトリル・スチレン共重合体（ＡＳ樹脂）、アクリロニトリル・ブタジエン・スチレン共重合体（ＡＢＳ樹脂）、メチルメタクリレート・ブタジエン・スチレン共重合体（ＭＢＳ樹脂）、メチルメタクリレート・アクリロニトリル・ブタジエン・スチレン共重合体（ＭＡＢＳ樹脂）、アクリロニトリル・アクリルゴム・スチレン共重合体（ＡＡＳ樹脂）、アクリロニトリル・エチレンプロピレン系ゴム・スチレン共重合体（ＡＥＳ樹脂）、スチレン・ＩＰＮ型ゴム共重合体等の樹脂、又は、これらの混合物が挙げられる。さらにシンジオタクティクポリスチレン等のように立体規則性を有するものであってもよい。これらの中でも、ポリスチレン（ＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）が好ましい。 More specifically, examples of the styrene resin used in the present invention include polystyrene, styrene / butadiene / styrene copolymer (SBS resin), hydrogenated styrene / butadiene / styrene copolymer (hydrogenated SBS), and water. Styrene / isoprene / styrene copolymer (SEPS), high impact polystyrene (HIPS), acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / Styrene copolymer (MBS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acrylic rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AE Resin), styrene · IPN type rubber copolymer resin, or mixtures thereof. Further, it may have stereoregularity such as syndiotactic polystyrene. Among these, polystyrene (PS) and impact-resistant polystyrene (HIPS) are preferable.
このようなスチレン系樹脂の製造方法としては、乳化重合法、溶液重合法、懸濁重合法あるいは塊状重合法等の公知の方法が挙げられる。 Examples of the method for producing such a styrene resin include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.
本発明において、スチレン系樹脂は１種を単独で用いても良く、２種以上を混合して用いても良い。 In the present invention, the styrene resin may be used alone or in combination of two or more.
［樹脂成分］
本発明の熱可塑性樹脂組成物中の樹脂成分は、ポリフェニレンエーテル樹脂２０〜９５重量％と、スチレン系樹脂５〜８０重量％からなることが好ましい。ポリフェニレンエーテル樹脂が２０重量％より少ないと、難燃性、荷重撓み温度及び機械的強度が低下する傾向がある。また、ポリフェニレンエーテル樹脂が９５重量％を超えると熱可塑性樹脂組成物の流動性が著しく低下し、成形工程において実用に耐えない場合がある。
[Resin component]
The resin component in the thermoplastic resin composition of the present invention is preferably composed of 20 to 95% by weight of a polyphenylene ether resin and 5 to 80% by weight of a styrene resin. If the polyphenylene ether resin is less than 20% by weight, flame retardancy, load deflection temperature and mechanical strength tend to decrease. On the other hand, when the polyphenylene ether resin exceeds 95% by weight, the fluidity of the thermoplastic resin composition is remarkably lowered and may not be practically used in the molding process.
［リン酸エステル系難燃剤］
本発明で用いるリン酸エステル系難燃剤は、下記一般式（１）で表されるリン酸エステル化合物である。
[Phosphate ester flame retardant]
The phosphate ester flame retardant used in the present invention is a phosphate ester compound represented by the following general formula (1).
（式中、Ｒ１、Ｒ２は各々独立に水素原子又はメチル基、好ましくは水素原子を表し、ｎは１〜５の数を表す。） (In the formula, R 1 and R 2 each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom, and n represents a number of 1 to 5.)
上記一般式（１）で表されるリン酸エステル系難燃剤としては、好ましくは以下の一般式（１Ａ），（１Ｂ）で表されるリン酸エステル化合物が挙げられる。 The phosphate ester flame retardant represented by the general formula (1) is preferably a phosphate ester compound represented by the following general formulas (1A) and (1B).
前記一般式（１）で表されるリン酸エステル化合物の合成方法は特に制限されず、例えば、４，４’−ジヒドロキシビフェニルとフェノールとオキシ塩化リンを塩化マグネシウムなどの触媒の存在下に反応させ脱塩酸するか、トリフェニルホスフェイトと４，４’−ジヒドロキシビフェニルをエステル交換反応することで合成可能である。 The method for synthesizing the phosphate ester compound represented by the general formula (1) is not particularly limited. For example, 4,4′-dihydroxybiphenyl, phenol and phosphorus oxychloride are reacted in the presence of a catalyst such as magnesium chloride. It can be synthesized by dehydrochlorination or by transesterification of triphenyl phosphate with 4,4′-dihydroxybiphenyl.
本発明で用いるリン酸エステル系難燃剤においては、前記一般式（１）におけるｎ＝１であるリン酸エステル化合物が９０重量％未満であることが好ましい。但し、この割合が、８０重量％未満では製造工程において実用的ではないため、８０重量％以上が好ましい。 In the phosphoric acid ester flame retardant used in the present invention, the phosphoric acid ester compound where n = 1 in the general formula (1) is preferably less than 90% by weight. However, if this ratio is less than 80% by weight, it is not practical in the production process, so 80% by weight or more is preferable.
本発明の樹脂組成物中の上記リン酸エステル系難燃剤の配合量は、ポリフェニレンエーテル樹脂及びスチレン系樹脂を含む樹脂成分の合計１００重量部に対して２〜３０重量部、好ましくは３〜２５重量部、特に好ましくは５〜２０重量部である。リン酸エステル系難燃剤の配合割合が２重量部未満では、難燃効果が小さく、３０重量部を超えると耐衝撃性が低下し、発生ガスによる成形品割れの問題が発生するので好ましくない。 The blending amount of the phosphate ester flame retardant in the resin composition of the present invention is 2 to 30 parts by weight, preferably 3 to 25 parts per 100 parts by weight in total of the resin components including polyphenylene ether resin and styrene resin. Part by weight, particularly preferably 5 to 20 parts by weight. When the blending ratio of the phosphate ester flame retardant is less than 2 parts by weight, the flame retarding effect is small, and when it exceeds 30 parts by weight, the impact resistance is lowered, and the problem of cracking of the molded product due to the generated gas occurs.
［その他の成分］
本発明の樹脂組成物は、上記のポリフェニレンエーテル樹脂、スチレン系樹脂、リン酸エステル系難燃剤を必須成分として含有するが、必要に応じその他の添加物を配合しても良い。
[Other ingredients]
The resin composition of the present invention contains the above polyphenylene ether resin, styrene resin, and phosphate ester flame retardant as essential components, but may contain other additives as necessary.
例えば、本発明の樹脂組成物には、組成物の製造及び成形工程における溶融混練時や使用時の熱安定性を向上させる目的で、ヒンダードフェノール系化合物、ホスファイト系化合物、ホスホナイト系化合物、酸化亜鉛から選ばれる少なくとも１種の熱安定剤を配合することが好ましい。 For example, the resin composition of the present invention includes a hindered phenol compound, a phosphite compound, a phosphonite compound, for the purpose of improving the thermal stability during melt kneading and use in the production and molding process of the composition, It is preferable to blend at least one heat stabilizer selected from zinc oxide.
ヒンダードフェノール系化合物の具体例として、ｎ−オクタデシル−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート、１，６−ヘキサンジオール−ビス〔３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕、ペンタエリスリトール−テトラキス〔３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕、２，６−ジ−ｔ−ブチル−４−メチルフェノール、３，９−ビス〔１，１−ジメチル−２−｛β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル〕−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン、トリエチレングリコール−ビス〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート〕、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルホスホネート−ジエチルエステル、１，３，５−トリメチル−２，４，６−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）ベンゼン、２，２−チオ−ジエチレンビス〔３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕、トリス−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−イソシアヌレート、Ｎ，Ｎ’−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナマイド）等が挙げられる。これらの中で、ｎ−オクタデシル−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート、１，６−ヘキサンジオール−ビス〔３−（３’，５’−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕、２，６−ジ−ｔ−ブチル−４−メチルフェノール、３，９−ビス〔１，１−ジメチル−２−｛β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル〕−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカンが好ましい。これらは１種を単独で用いても良く、２種以上を混合して用いても良い。 Specific examples of hindered phenol compounds include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 2 , 6-Di-tert-butyl-4-methylphenol, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} Ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxy) Phenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3 ′, 5′-di-t- Butyl-4′-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], tris- (3,5- And di-t-butyl-4-hydroxybenzyl) -isocyanurate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), and the like. Among these, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3 ′, 5′- t-butyl-4′-hydroxyphenyl) propionate], 2,6-di-t-butyl-4-methylphenol, 3,9-bis [1,1-dimethyl-2- {β- (3-t- Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred. These may be used alone or in combination of two or more.
ホスファイト系化合物の具体例としては、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトール−ジ−ホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−ホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、４，４’−ブチリデン−ビス−（３−メチル−６−ｔ−ブチルフェニル−ジ−トリデシル）ホスファイト、１，１，３−トリス（２−メチル−４−ジトリデシルホスファイト−５−ｔ−ブチル−フェニル）ブタン、トリス（ミックスドモノ及びジ−ノニルフェニル）ホスファイト、トリス（ノニルフェニル）ホスファイト、４，４’−イソプロピリデンビス（フェニル−ジアルキルホスファイト）等が挙げられ、好ましくは、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトール−ジ−ホスファイト等である。これらは１種を単独で用いても良く、２種以上を混合して用いても良い。 Specific examples of the phosphite compound include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2 , 6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene- Bis- (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butyl-phenyl) butane, Tris (mixed mono and di-nonylphenyl) phosphite, Tris (nonylphenyl) phosphite, 4,4'-isopropylidenebis (phenyl) Dialkyl phosphite), etc., preferably tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite. These may be used alone or in combination of two or more.
ホスホナイト系化合物の具体例としては、例えば、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，５−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，３，４−トリメチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，３−ジメチル−５−エチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔ−ブチル−５−エチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，３，４−トリブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４，６−トリ−ｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト等が挙げられ、好ましくは、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイトである。 Specific examples of the phosphonite compound include, for example, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,5-di-t-butylphenyl) -4. , 4′-biphenylenediphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,3-dimethyl-5-ethylphenyl) -4,4′- Biphenylene diphosphonite, tetrakis (2,6-di-t-butyl-5-ethylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3,4-tributylphenyl) -4,4'- Biphenylene diphosphonite, tetrakis (2,4,6-tri-t-butylphenyl) -4,4′-biphenylene diphosphonite , Preferably, tetrakis (2,4-di -t- butyl-phenyl) -4,4'-biphenylene phosphonite.
酸化亜鉛としては、例えば、平均粒子径が０．０２〜１μｍのものが好ましく、平均粒子径が０．０８〜０．８μｍのものがより好ましい。 As zinc oxide, for example, those having an average particle diameter of 0.02 to 1 μm are preferable, and those having an average particle diameter of 0.08 to 0.8 μm are more preferable.
ヒンダードフェノール系化合物、ホスファイト系化合物、ホスホナイト系化合物、酸化亜鉛から選ばれた１種以上の安定剤の配合量は、樹脂成分の合計１００重量部に対し、０．０１〜５重量部、好ましくは０．０３〜３重量部である。安定剤の配合量が０．０１重量部未満では、熱安定性の改善効果が小さく、５重量部を超えると金型汚染が発生したり、機械的強度の低下や経済的なデメリットが大きくなり好ましくない。 The blending amount of one or more stabilizers selected from a hindered phenol compound, a phosphite compound, a phosphonite compound, and zinc oxide is 0.01 to 5 parts by weight with respect to a total of 100 parts by weight of the resin component. Preferably it is 0.03-3 weight part. If the compounding amount of the stabilizer is less than 0.01 parts by weight, the effect of improving the thermal stability is small, and if it exceeds 5 parts by weight, mold contamination occurs, mechanical strength is reduced and economic disadvantages are increased. It is not preferable.
また、本発明においては、成形時の離型性を向上させる目的で、離型剤を配合することが好ましい。離型剤としては、例えば、脂肪族カルボン酸、脂肪族カルボン酸エステル、ポリオレフィン系ワックス、シリコーンオイル等が挙げられる。 Moreover, in this invention, it is preferable to mix | blend a mold release agent in order to improve the mold release property at the time of shaping | molding. Examples of the mold release agent include aliphatic carboxylic acid, aliphatic carboxylic acid ester, polyolefin wax, silicone oil and the like.
脂肪族カルボン酸としては、飽和又は不飽和の脂肪族モノカルボン酸、ジカルボン酸又はトリカルボン酸を挙げることができる。ここで脂肪族カルボン酸は、脂環式カルボン酸も包含する。このうち好ましい脂肪族カルボン酸は、炭素数６〜３６のモノ又はジカルボン酸であり、炭素数６〜３６の脂肪族飽和モノカルボン酸がさらに好ましい。このような脂肪族カルボン酸の具体例としては、パルミチン酸、ステアリン酸、吉草酸、カプロン酸、カプリン酸、ラウリン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、メリシン酸、テトラトリアコンタン酸、モンタン酸、グルタル酸、アジピン酸、アゼライン酸等を挙げることができる。 Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, tetratriacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.
脂肪族カルボン酸エステルを構成する脂肪族カルボン酸成分としては、前記脂肪族カルボン酸と同じものが使用できる。一方、脂肪族カルボン酸エステルを構成するアルコール成分としては、飽和又は不飽和の１価アルコール、飽和又は不飽和の多価アルコール等を挙げることができる。これらのアルコールは、フッ素原子、アリール基等の置換基を有していてもよい。これらのアルコールのうち、炭素数３０以下の１価又は多価の飽和アルコールが好ましく、さらに炭素数３０以下の脂肪族飽和１価アルコール又は多価アルコールが好ましい。ここで脂肪族アルコールは、脂環式アルコールも包含する。 As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol.
これらのアルコールの具体例としては、オクタノール、デカノール、ドデカノール、ステアリルアルコール、ベヘニルアルコール、エチレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール、２，２−ジヒドロキシペルフルオロプロパノール、ネオペンチレングリコール、ジトリメチロールプロパン、ジペンタエリスリトール等を挙げることができる。これらの脂肪族カルボン酸エステルは、不純物として脂肪族カルボン酸及び／又はアルコールを含有していてもよく、複数の化合物の混合物であってもよい。 Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds.
脂肪族カルボン酸エステルの具体例としては、蜜ロウ（ミリスチルパルミテートを主成分とする混合物）、ステアリン酸ステアリル、ベヘン酸ベヘニル、ベヘン酸オクチルドデシル、グリセリンモノパルミテート、グリセリンモノステアレート、グリセリンジステアレート、グリセリントリステアレート、ペンタエリスリトールモノパルミテート、ペンタエリスリトールモノステレート、ペンタエリスリトールジステアレート、ペンタエリスリトールトリステアレート、ペンタエリスリトールテトラステアレートを挙げることができる。 Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myristyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin diester Mention may be made of stearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monosterate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate.
ポリオレフィン系ワックスとしては、オレフィンの単独重合体及び共重合体等が挙げられる。オレフィンの単独重合体としては、例えば、ポリエチレンワックス、ポリプロピレンワックス等及びこれらの部分酸化物又はこれらの混合物等が挙げられる。オレフィンの共重合体としては、エチレン、プロピレン、１−ブテン、１−ヘキセン、１−デセン、２−メチルブテン−１、３−メチルブテン−１，３−メチルペンテン−１、４−メチルペンテン−１等のα−オレフィン等の共重合体、これらのオレフィンと共重合可能なモノマー、例えば、不飽和カルボン酸又はその酸無水物（無水マレイン酸、（メタ）アクリル酸等）、（メタ）アクリル酸エステル（（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等の（メタ）アクリル酸の炭素数１〜６のアルキルエステル等）等の重合性モノマーとの共重合体等が挙げられる。また、これらの共重合体には、ランダム共重合体、ブロック共重合体、又はグラフト共重合体が含まれる。オレフィン共重合体は、通常、エチレンと、他のオレフィン及び重合性モノマーから選択された少なくとも１種のモノマーとの共重合体である。これらのポリオレフィンワックスのうち、ポリエチレンワックスが最も好ましい。なお、ポリオレフィンワックスは、線状又は分岐構造であってよい。 Examples of polyolefin waxes include olefin homopolymers and copolymers. Examples of the olefin homopolymer include polyethylene wax, polypropylene wax and the like, partial oxides thereof, and mixtures thereof. Examples of the olefin copolymer include ethylene, propylene, 1-butene, 1-hexene, 1-decene, 2-methylbutene-1, 3-methylbutene-1,3-methylpentene-1, 4-methylpentene-1, and the like. Copolymers such as α-olefins, monomers copolymerizable with these olefins, such as unsaturated carboxylic acids or acid anhydrides thereof (maleic anhydride, (meth) acrylic acid, etc.), (meth) acrylic acid esters And a copolymer with a polymerizable monomer such as (methyl (meth) acrylate, alkyl ester having 1 to 6 carbon atoms of (meth) acrylic acid such as ethyl (meth) acrylate), and the like. Further, these copolymers include random copolymers, block copolymers, or graft copolymers. The olefin copolymer is usually a copolymer of ethylene and at least one monomer selected from other olefins and polymerizable monomers. Of these polyolefin waxes, polyethylene wax is most preferred. The polyolefin wax may have a linear or branched structure.
シリコーンオイルとしては、例えば、ポリジメチルシロキサンからなるもの、ポリジメチルシロキサンのメチル基の一部又は全部がフェニル基、水素原子、炭素数２以上のアルキル基、ハロゲン化フェニル基、フルオロエステル基で置換されたシリコーンオイル、エポキシ基を有するエポキシ変性シリコーンオイル、アミノ基を有するアミノ変性シリコーンオイル、アルコール性水酸基を有するアルコール変性シリコーンオイル、ポリエーテル構造を有するポリエーテル変性シリコーンオイル等が挙げられ、これらは２種類以上併用してもよい。 Examples of silicone oils include those composed of polydimethylsiloxane, and some or all of the methyl groups of polydimethylsiloxane are substituted with phenyl groups, hydrogen atoms, alkyl groups having 2 or more carbon atoms, halogenated phenyl groups, and fluoroester groups. Silicone-modified oil, epoxy-modified silicone oil having an epoxy group, amino-modified silicone oil having an amino group, alcohol-modified silicone oil having an alcoholic hydroxyl group, polyether-modified silicone oil having a polyether structure, and the like. Two or more types may be used in combination.
離型剤の配合量は、ポリフェニレンエーテル樹脂及びスチレン系樹脂を含む樹脂成分の合計１００重量部に対して０．０１〜１０重量部が好ましく、０．１〜６重量部がより好ましく、０．１〜３重量部がさらに好ましい。離型剤の配合量を０．０１重量部以上とすることにより離型効果がより発揮されやすく、１０重量部以下とすることにより、耐熱性や金型汚染、可塑化不良といった問題が発生しにくい傾向にある。 The compounding amount of the release agent is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 6 parts by weight, based on a total of 100 parts by weight of the resin components including the polyphenylene ether resin and the styrene resin. 1 to 3 parts by weight is more preferable. By making the compounding amount of the release agent 0.01 parts by weight or more, the release effect is more easily exhibited, and by making it 10 parts by weight or less, problems such as heat resistance, mold contamination, and poor plasticization occur. It tends to be difficult.
本発明においては、主に、樹脂組成物を補強し剛性、耐熱性、寸法精度等を向上させる目的で無機充填材を配合してもよい。無機充填材の形状等に特に制限はなく、その具体例としては、例えば、ガラス繊維、ガラスフレーク、ガラスビーズ、ミルドファイバー、アルミナ繊維、炭素繊維、酸化チタン、酸化マグネシウム、炭酸カルシウム、硫酸バリウム、窒化硼素、チタン酸カリウィスカー、シリカ、マイカ、タルク、ワラストナイト等が挙げられるが、これらの中でも、ガラス繊維が好ましい例として挙げられる。 In the present invention, an inorganic filler may be blended mainly for the purpose of reinforcing the resin composition and improving rigidity, heat resistance, dimensional accuracy, and the like. The shape of the inorganic filler is not particularly limited, and specific examples thereof include, for example, glass fiber, glass flake, glass bead, milled fiber, alumina fiber, carbon fiber, titanium oxide, magnesium oxide, calcium carbonate, barium sulfate, Examples thereof include boron nitride, potassium titanate whisker, silica, mica, talc, wollastonite and the like. Among these, glass fiber is a preferable example.
本発明で好ましく使用されるガラス繊維は、平均直径が２０μｍ以下のものが好ましく、さらに１〜１５μｍのものが、物性バランス（耐熱剛性、衝撃強度）をより一層高める点、並びに成形反りをより一層低減させる点で好ましい。 The glass fiber preferably used in the present invention preferably has an average diameter of 20 μm or less, and further 1 to 15 μm further enhances the balance of physical properties (heat resistance rigidity, impact strength) and further reduces the molding warp. This is preferable in terms of reduction.
ガラス繊維の長さは特定されるものでなく、長繊維タイプ（ロービング）や短繊維タイプ（チョップドストランド）等から選択して用いることができる。この場合の集束本数は、１００〜５０００本程度であることが好ましい。また、樹脂組成物混練後の樹脂組成物中のガラス繊維の長さが平均０．１ｍｍ以上で得られるならば、いわゆるミルドファイバー、ガラスパウダーと称せられるストランドの粉砕品でもよく、また、連続単繊維系のスライバーのものでもよい。原料ガラスの組成は、無アルカリのものも好ましく、例えば、Ｅガラス、Ｃガラス、Ｓガラス等が挙げられるが、本発明では、Ｅガラスが好ましく用いられる。 The length of the glass fiber is not specified and can be selected from a long fiber type (roving), a short fiber type (chopped strand), or the like. In this case, the number of focusing is preferably about 100 to 5000. If the average length of the glass fiber in the resin composition after kneading the resin composition is 0.1 mm or more, so-called milled fiber or a pulverized product of strands called glass powder may be used. A fiber sliver may also be used. The composition of the raw material glass is preferably non-alkali, and examples thereof include E glass, C glass, and S glass. In the present invention, E glass is preferably used.
無機充填材の配合量は、ポリフェニレンエーテル樹脂及びスチレン系樹脂を含む樹脂成分の合計１００重量部に対して、好ましくは１〜８０重量部、より好ましくは５〜６０重量部である。無機充填材の配合量を１重量部以上とすることにより機械的強度を効果的に改良できる傾向にあり、６０重量部以下とすることにより流動性及び成形品外観をより良好なものとすることができる。 The amount of the inorganic filler is preferably 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the total of the resin components including the polyphenylene ether resin and the styrene resin. There is a tendency that the mechanical strength can be effectively improved by setting the blending amount of the inorganic filler to 1 part by weight or more, and the fluidity and appearance of the molded product should be improved by setting the blending amount to 60 parts by weight or less. Can do.
本発明においては、着色剤を配合してもよい。着色剤としては、熱可塑性樹脂に一般的に用いられる、染料、無機顔料、有機顔料が挙げられる。 In the present invention, a colorant may be blended. Examples of the colorant include dyes, inorganic pigments, and organic pigments generally used for thermoplastic resins.
染料としては、アゾ染料、アントラキノン染料、フタロシアニン染料、インジゴ染料、ジフェニルメタン染料、アクリジン染料、シアニン染料、ニトロ染料、ニグロシン等が挙げられる。無機顔料としては、酸化チタン、べんがら、コバルトブルー等の酸化物顔料、アルミナホワイト等の水酸化物顔料、硫化亜鉛、カドミウムイエロー等の硫化物顔料、ホワイトカーボン、タルク等の珪酸塩顔料、カーボンブラック等が挙げられる。有機顔料としては、ニトロ顔料、アゾ顔料、フタロシアニン顔料、縮合多環顔料等が挙げられる。これらの中でも、成形品表面へブリードアウトしにくい点から、無機顔料が好ましい。また、着色剤は、押出時のハンドリング性改良目的のために、ポリフェニレンエーテル樹脂、ポリスチレン系樹脂や、必要に応じて用いられるその他のポリカーボネート樹脂、アクリル樹脂等の熱可塑性樹脂とマスターバッチ化されたものを用いてもよい。 Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, indigo dyes, diphenylmethane dyes, acridine dyes, cyanine dyes, nitro dyes, and nigrosine. Inorganic pigments include oxide pigments such as titanium oxide, red pepper and cobalt blue, hydroxide pigments such as alumina white, sulfide pigments such as zinc sulfide and cadmium yellow, silicate pigments such as white carbon and talc, and carbon black. Etc. Examples of organic pigments include nitro pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Among these, an inorganic pigment is preferable because it is difficult to bleed out to the surface of the molded product. In addition, the colorant was masterbatched with a thermoplastic resin such as polyphenylene ether resin, polystyrene resin, or other polycarbonate resin or acrylic resin used as necessary for the purpose of improving the handleability during extrusion. A thing may be used.
着色剤の配合量は、ポリフェニレンエーテル樹脂及びスチレン系樹脂を含む樹脂成分の合計１００重量部に対して、好ましくは０．０１〜３０重量部、より好ましくは０．１〜２０重量部である。特に、酸化チタンは樹脂組成物の変色を防止しやすく、淡い色に着色する上で有効である。 The blending amount of the colorant is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of the resin components including the polyphenylene ether resin and the styrene resin. In particular, titanium oxide is easy to prevent discoloration of the resin composition, and is effective in coloring a light color.
上記以外の添加剤成分としては、例えば、ポリテトラフルオロエチレン等の難燃助剤、紫外線吸収剤、光安定剤、発泡剤、滑剤、流動性改良剤、耐衝撃性改良剤、分散剤等が挙げられる。 Examples of additive components other than the above include flame retardant aids such as polytetrafluoroethylene, ultraviolet absorbers, light stabilizers, foaming agents, lubricants, fluidity improvers, impact resistance improvers, and dispersants. Can be mentioned.
また、本発明の樹脂組成物は、本発明の効果を損なわない範囲において、ポリフェニレンエーテル樹脂、スチレン系樹脂以外のその他の樹脂を、樹脂成分の一部として用いてもよい。その他の樹脂としては、例えば、ポリアミド樹脂、ポリエステル樹脂、ポリフェニレンサルファイド樹脂、液晶ポリエステル樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、ポリアクリロニトリル樹脂、アクリル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、エチレン−プロピレン共重合体等のオレフィン系樹脂等の熱可塑性樹脂や、エポキシ樹脂、メラミン樹脂、シリコーン樹脂等の熱硬化性樹脂等が挙げられる。これらの熱可塑性樹脂及び熱硬化性樹脂は、２種以上を組み合わせて使用することもできる。これらその他の樹脂の配合量は、樹脂成分中の５０重量％以下であることが好ましく、４５重量％以下であることがさらに好ましい。 Moreover, the resin composition of this invention may use other resins other than a polyphenylene ether resin and a styrene-type resin as a part of resin component in the range which does not impair the effect of this invention. Other resins include, for example, polyamide resins, polyester resins, polyphenylene sulfide resins, liquid crystal polyester resins, polycarbonate resins, polyacetal resins, polyacrylonitrile resins, acrylic resins, polyethylene resins, polypropylene resins, ethylene-propylene copolymers, and other olefins. And thermoplastic resins such as epoxy resins, and thermosetting resins such as epoxy resins, melamine resins, and silicone resins. These thermoplastic resins and thermosetting resins can be used in combination of two or more. The blending amount of these other resins is preferably 50% by weight or less in the resin component, and more preferably 45% by weight or less.
なお、本発明で用いる前記一般式（１）で表されるリン酸エステル系難燃剤以外の難燃剤を併用することも可能であるが、本発明に係るリン酸エステル系難燃剤以外の難燃剤を併用する場合は、成形時にガスが発生しないように配合量を調整して用いればよい。 In addition, although it is also possible to use together flame retardants other than the phosphate ester flame retardant represented by the general formula (1) used in the present invention, flame retardants other than the phosphate ester flame retardant according to the present invention. When used in combination, the blending amount may be adjusted so that no gas is generated during molding.
［製造方法］
本発明の樹脂組成物の製造は、特定の方法に限定されるものではないが、好ましくは溶融混練によるものであり、熱可塑性樹脂について一般に実用化されている混練方法が適用できる。例えば、ポリフェニレンエーテル樹脂、スチレン系樹脂、リン酸エステル系難燃剤及び必要に応じて用いられるその他の成分等を、ヘンシェルミキサー、リボンブレンダー、Ｖ型ブレンダー等により均一に混合した後、一軸又は多軸混練押出機、ロール、バンバリーミキサー、ラボプラストミル（ブラベンダー）等で混練することができる。各成分は混練機に一括でフィードしても、順次フィードしてもよく、各成分から選ばれた２種以上の成分を予め混合したものを用いてもよい。
[Production method]
Although the production of the resin composition of the present invention is not limited to a specific method, it is preferably by melt kneading, and a kneading method generally put to practical use for thermoplastic resins can be applied. For example, after uniformly mixing polyphenylene ether resin, styrene resin, phosphate ester flame retardant and other components used as necessary with a Henschel mixer, ribbon blender, V-type blender, etc., uniaxial or polyaxial It can be kneaded with a kneading extruder, roll, Banbury mixer, lab plast mill (Brabender) or the like. Each component may be fed all at once to the kneader, or may be fed sequentially, or a mixture of two or more components selected from each component may be used.
混練温度と混練時間は、望まれる樹脂組成物や混練機の種類等の条件により、任意に選ぶことができるが、通常、混練温度は２００〜３５０℃、好ましくは２２０〜３２０℃、混練時間は２０分以下が好ましい。この温度が高過ぎると、ポリフェニレンエーテル樹脂やスチレン系樹脂の熱劣化が問題となり、成形品の物性の低下や外観不良を生じることがある。 The kneading temperature and kneading time can be arbitrarily selected depending on the conditions such as the desired resin composition and the type of kneading machine. Usually, the kneading temperature is 200 to 350 ° C., preferably 220 to 320 ° C., and the kneading time is 20 minutes or less is preferable. When this temperature is too high, thermal deterioration of the polyphenylene ether resin or styrene resin becomes a problem, and the physical properties of the molded product may be deteriorated or the appearance may be deteriorated.
［成形方法］
本発明の樹脂組成物は、熱可塑性樹脂について一般に用いられている成形法、すなわち射出成形、射出圧縮成形、中空成形、押出成形、シート成形、熱成形、回転成形、積層成形、プレス成形等の各種成形法によって成形することができる。特に好ましい成形法は、流動性の観点から射出成形法である。射出成形にあたっては、樹脂温度を、例えば、２７０〜３２０℃にコントロールするのが好ましい。
[Molding method]
The resin composition of the present invention is a molding method generally used for thermoplastic resins, such as injection molding, injection compression molding, hollow molding, extrusion molding, sheet molding, thermoforming, rotational molding, laminate molding, press molding, etc. It can be molded by various molding methods. A particularly preferable molding method is an injection molding method from the viewpoint of fluidity. In the injection molding, the resin temperature is preferably controlled to 270 to 320 ° C., for example.
［成形品］
本発明の樹脂組成物は、１．０ｍｍ以下の薄肉でも高度な難燃性を有し、流動性、耐薬品性にも優れているため、これを成形してなる本発明の成形品は、例えば、電気・電子・ＯＡ機器、その他各種機器の外板やハウジング、構造部品、機構部品等の厳しい難燃性が求められる成形品の材料として有用である。
[Molding]
The resin composition of the present invention has high flame retardancy even at a thin wall thickness of 1.0 mm or less, and is excellent in fluidity and chemical resistance. For example, it is useful as a material for molded products that require severe flame retardancy, such as outer plates, housings, structural parts, and mechanical parts of electric / electronic / OA equipment and other various equipment.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。また、以下の例で使用した材料、得られた樹脂組成物の評価法及び試験片の成形条件は次の通りである。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. In addition, the materials used in the following examples, the evaluation method of the obtained resin composition, and the molding conditions of the test pieces are as follows.
＜材料＞
ポリフェニレンエーテル樹脂：ポリ（２，６−ジメチル−１，４−フェニレン）エーテル（ポリキシレノールシンガポール社製「ＰＸ１００Ｌ」、クロロホルム中で測定した３０℃の固有粘度０．４７ｄｌ／ｇ）
スチレン系樹脂：ハイインパクトポリスチレン（日本ポリスチレン社製「ＨＴ４７８」、分子量（Ｍｗ）２００，０００、ＭＦＲ３．２ｇ／１０分）
ポリカーボネート樹脂：ポリ−４，４−イソプロピリデンジフェニルカーボネート（三菱エンジニアリングプラスチックス（株）製）
ＡＢＳ樹脂：テクノポリマー社製ＡＢＳ樹脂
<Material>
Polyphenylene ether resin: poly (2,6-dimethyl-1,4-phenylene) ether (“PX100L” manufactured by Polyxylenol Singapore, intrinsic viscosity 0.47 dl / g measured at 30 ° C. in chloroform)
Styrenic resin: high impact polystyrene (“HT478” manufactured by Nippon Polystyrene Co., Ltd., molecular weight (Mw) 200,000, MFR 3.2 g / 10 min)
Polycarbonate resin: Poly-4,4-isopropylidene diphenyl carbonate (manufactured by Mitsubishi Engineering Plastics)
ABS resin: ABS resin manufactured by Technopolymer
実施例用難燃剤：ＡＤＥＫＡ社製リン酸エステル系難燃剤
（前記一般式（１）において、ｎ＝１のものが８６重量％、Ｒ１，Ｒ２は水素原子）
比較例用難燃剤：レゾルシノールビス（ジフェニルホスフェート）（大八化学工業社製「ＣＲ−７３３Ｓ」）
Flame retardant for examples: Phosphate ester flame retardant manufactured by ADEKA (in the general formula (1), n = 1 is 86% by weight, R 1 and R 2 are hydrogen atoms)
Flame retardant for comparative example: resorcinol bis (diphenyl phosphate) (“CR-733S” manufactured by Daihachi Chemical Industry Co., Ltd.)
熱安定剤−１：酸化亜鉛（本荘ケミカル社社製「ＺＮＯ」）
熱安定剤−２：ヒンダードフェノール系化合物（チバ・スペシャルティー・ケミカルズ社製「イルガノックス１０７６」）
離型剤−１：ポリエチレンワックス（三洋化成社製「１５１Ｐ」）
離型剤−２：ペンタエリスリトールテトラステアレート（ヘンケル社製）
Thermal stabilizer-1: Zinc oxide ("ZNO" manufactured by Honjo Chemical Co., Ltd.)
Heat stabilizer-2: hindered phenol compound ("Irganox 1076" manufactured by Ciba Specialty Chemicals)
Mold release agent-1: Polyethylene wax (“151P” manufactured by Sanyo Chemical Co., Ltd.)
Release agent-2: Pentaerythritol tetrastearate (Henkel)
＜評価法＞
（１）引張試験
下記記載の方法で得られた樹脂組成物ペレットを、実施例１、２及び比較例１、２は８０℃で４時間、実施例３及び比較例３は１００℃で４時間、参考例１及び２は８０℃で４時間乾燥後、射出成形機（住友重機械工業社製「ＳＧ１２５」）にて、参考例１及び２以外は、シリンダー設定温度２５０〜２８０℃、金型温度９０℃の条件で、参考例１及び２は、シリンダー設定温度２４０℃、金型温度６０℃の条件で射出成形を行い、ＩＳＯ５２７規定タイプの厚み４．０ｍｍの引張試験片を作製した。得られた試験片を用い、ＩＳＯ５２７規格に準じて、引張試験を実施し、降伏点応力を測定した。
<Evaluation method>
(1) Tensile test Resin composition pellets obtained by the method described below were used in Examples 1 and 2 and Comparative Examples 1 and 2 at 80 ° C. for 4 hours, and Example 3 and Comparative Example 3 at 100 ° C. for 4 hours. In Reference Examples 1 and 2, after drying at 80 ° C. for 4 hours, in an injection molding machine (“SG125” manufactured by Sumitomo Heavy Industries, Ltd.), except for Reference Examples 1 and 2, cylinder setting temperature 250 to 280 ° C., mold Under the conditions of a temperature of 90 ° C., in Reference Examples 1 and 2, injection molding was performed under the conditions of a cylinder set temperature of 240 ° C. and a mold temperature of 60 ° C., and a tensile test piece having a thickness of 4.0 mm of an ISO527-regulated type was produced. Using the obtained test piece, a tensile test was performed according to ISO 527 standard, and the yield point stress was measured.
（２）荷重たわみ温度
上記（１）引張試験用の引張試験片を、ＩＳＯ規定の方法で加工し、荷重たわみ温度測定用の試験片を作製した。得られた試験片を用い、ＩＳＯ７５規格に準じて、荷重たわみ温度を測定した。
(2) Deflection temperature under load The tensile test piece for the above (1) tensile test was processed by a method specified by ISO to prepare a test piece for measuring a deflection temperature under load. Using the obtained test piece, the deflection temperature under load was measured according to the ISO75 standard.
（３）曲げ試験
上記（１）引張試験用の引張試験片を、ＩＳＯ規定の方法で加工し、曲げ試験用の試験片を作製した。得られた試験片を用い、ＩＳＯ１７９規格に準じて、曲げ弾性率及び曲げ強度を測定した。
(3) Bending test The tensile test piece for the above (1) tensile test was processed by a method prescribed by ISO to prepare a test piece for a bending test. Using the obtained test piece, the flexural modulus and flexural strength were measured according to the ISO 179 standard.
（４）シャルピー衝撃強度
下記記載の方法で得られた樹脂組成物ペレットを、実施例１、２及び比較例１、２は８０℃で４時間、実施例３及び比較例３は１００℃で４時間、参考例１及び２は８０℃で４時間乾燥後、射出成形機（住友重機械工業社製「ＳＧ１２５」）にて、参考例１及び２以外はシリンダー温度２５０〜２８０℃、金型温度９０℃の条件で、参考例１及び２はシリンダー温度２４０℃、金型温度６０℃の条件で射出成形を行い、厚み４．０ｍｍのＩＳＯ試験片を作成した。得られた試験片にノッチ加工を施し、ＩＳＯ１７９規格に準じてシャルピー衝撃強度を測定した。
(4) Charpy impact strength Resin composition pellets obtained by the method described below were used in Examples 1 and 2 and Comparative Examples 1 and 2 at 80 ° C for 4 hours, and Example 3 and Comparative Example 3 at 100 ° C for 4 hours. Time, Reference Examples 1 and 2 were dried at 80 ° C. for 4 hours, and then injection molding machine (“SG125” manufactured by Sumitomo Heavy Industries, Ltd.), except for Reference Examples 1 and 2, cylinder temperature 250 to 280 ° C., mold temperature Under the conditions of 90 ° C., Reference Examples 1 and 2 were injection-molded under the conditions of a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. to produce an ISO test piece having a thickness of 4.0 mm. The obtained test piece was notched and the Charpy impact strength was measured according to the ISO 179 standard.
（５）難燃性
下記記載の方法で得られた樹脂組成物ペレットを、実施例１、２及び比較例１、２は８０℃で４時間、実施例３及び比較例３は１００℃で４時間、参考例１及び２は８０℃で４時間乾燥後、射出成形機（日本製鋼所社製「Ｊ７５ＥＤ」）にて、参考例１及び２以外はシリンダー温度２５０〜２８０℃、金型温度８０℃の条件で、参考例１及び２はシリンダー温度２４０℃、金型温度６０℃の条件で射出成形を行い、参考例１及び２以外は、５×１／２×厚み１／３２インチの大きさの燃焼試験片を、参考例１及び２は、５×１／２×厚み１／２１インチの大きさの燃焼試験片を作製し、ＵＬ−９４規格に準じて燃焼性の評価を行った。
(5) Flame retardancy The resin composition pellets obtained by the method described below were 4 hours at 80 ° C. for Examples 1 and 2 and Comparative Examples 1 and 2, and 4 at 100 ° C. for Example 3 and Comparative Example 3. Time, Reference Examples 1 and 2 were dried at 80 ° C. for 4 hours, and then injection molding machine (“J75ED” manufactured by Nippon Steel Works), cylinder temperature 250 to 280 ° C., mold temperature 80 except Reference Examples 1 and 2. Reference Example 1 and 2 performed injection molding under the conditions of a cylinder temperature of 240 ° C. and a mold temperature of 60 ° C. under the conditions of 5 ° C., except for Reference Examples 1 and 2, 5 × 1/2 × thickness of 1/32 inch. In the first and second reference samples, a combustion test piece having a size of 5 × ½ × thickness 1/21 inch was prepared, and the combustibility was evaluated according to the UL-94 standard. .
（６）エッジクラック試験
下記記載の方法で得られた樹脂組成物ペレットを、実施例１、２及び比較例１、２は８０℃で４時間、実施例３及び比較例３は１００℃で４時間、参考例１及び２は８０℃で４時間乾燥後、射出成形機（東芝機械社製「ＥＣ１６０ＮＩＩ」）にて、参考例１及び２以外はシリンダー温度２８０℃、金型温度８０℃、射出圧力８０ＭＰａの条件で、参考例１及び２はシリンダー温度２４０℃、金型温度６０℃、射出圧力８０ＭＰａの条件で射出成形を行い、縦５５ｍｍ、横３５ｍｍ、深さ３０ｍｍ、平均肉厚１．５ｍｍの箱形成形品を作製した。得られた成形品を各１０個、８０℃の乾燥機に２時間保存した後成形品を取り出し、成形品外側のエッジ部のクラックの有無を観察した。クラックない成形品１個を０点、クラックのある成形品１個を−１点とし、１０個の合計点数で評価した。成形品のエッジ部は、残留応力が大きく、発生ガスの付着により応力腐食割れが発生しやすい部分である。従って、エッジ部での割れが多いほど、ガスが多く発生していると考えられる。
(6) Edge crack test The resin composition pellets obtained by the method described below were used in Examples 1 and 2 and Comparative Examples 1 and 2 at 80 ° C. for 4 hours, and Example 3 and Comparative Example 3 at 4 ° C. at 4 ° C. Time, Reference Examples 1 and 2 were dried at 80 ° C. for 4 hours, then injection molding machine (“EC160NII” manufactured by Toshiba Machine Co., Ltd.), except for Reference Examples 1 and 2, cylinder temperature 280 ° C., mold temperature 80 ° C., injection Under the conditions of pressure 80 MPa, Reference Examples 1 and 2 perform injection molding under conditions of cylinder temperature 240 ° C.,
（７）熱重量分析(ＴＧＡ）
下記記載の方法で得られた樹脂組成物ペレットについて、５０℃から２８０℃まで２０℃／分の速度で昇温し、２８０℃に６０分保持したときの熱重量分析を行った。
(7) Thermogravimetric analysis (TGA)
The resin composition pellets obtained by the method described below were subjected to thermogravimetric analysis when the temperature was increased from 50 ° C. to 280 ° C. at a rate of 20 ° C./min and held at 280 ° C. for 60 minutes.
［実施例１〜３、比較例１〜３］
表１に示す割合で秤量した原材料をタンブラーミキサーにて均一に混合し、二軸押出機（スクリュウ径３０ｍｍ、Ｌ／Ｄ＝４２）のホッパーに投入し、シリンダー温度２５０〜２８０℃、スクリュー回転数３００ｒｐｍの条件にて、溶融混練させてペレット化した。このペレットを用いてそれぞれ試験片及び成形品を成形して上記（１）〜（６）の評価を行い、その結果を表１に示した。また、上記（７）ＴＧＡの結果は、図１〜６に示した。
[Examples 1-3, Comparative Examples 1-3]
The raw materials weighed in the proportions shown in Table 1 are uniformly mixed with a tumbler mixer, and put into a hopper of a twin screw extruder (screw
［参考例１〜２］
表１に示す割合で秤量した原材料をタンブラーミキサーにて均一に混合し、二軸押出機（スクリュウ径３０ｍｍ、Ｌ／Ｄ＝４２）のホッパーに投入し、シリンダー温度２５０℃、スクリュー回転数３００ｒｐｍの条件にて、溶融混練させてペレット化した。このペレットを用いてそれぞれ試験片及び成形品を成形して上記（２）、（４）〜（６）の評価を行い、その結果を表１に示した。
[Reference Examples 1-2]
The raw materials weighed in the proportions shown in Table 1 are uniformly mixed with a tumbler mixer, and put into a hopper of a twin screw extruder (screw
これらの結果から、本発明の樹脂組成物は、難燃性、耐熱性、機械的特性に優れ、かつ、発生ガスによる応力腐食割れがない、優れた樹脂組成物であることがわかった。しかも、比較例の樹脂組成物に比べ、曲げ弾性率等の機械的特性及び耐熱性も改善されることがわかった。また、本発明の樹脂組成物は、ＴＧＡにおける重量減少が少ないことからも、ガスの発生量が少ないことが確認された（実施例１〜３）。
一方、本発明に係るリン酸エステル系難燃剤を使用しない比較例１〜３の樹脂組成物は、エッジ部での応力腐食割れが多く、耐熱性及び機械的特性も実施例の樹脂組成物に比べ劣るものであった。また、ＴＧＡにおける重量減少が著しいことから、ガスの発生量が多く、加熱により分解しやすいことが確認された。
また、本発明と異なる樹脂成分系では、比較例用難燃剤を用いてもガス発生による応力腐食割れ等の欠陥が問題とはならないことが、参考例１及び２の結果から確認できる。
From these results, it was found that the resin composition of the present invention is an excellent resin composition having excellent flame retardancy, heat resistance and mechanical properties, and having no stress corrosion cracking due to generated gas. And it turned out that mechanical characteristics, such as a bending elastic modulus, and heat resistance are also improved compared with the resin composition of a comparative example. Moreover, since the resin composition of this invention has little weight loss in TGA, it was confirmed that there is little gas generation amount (Examples 1-3).
On the other hand, the resin compositions of Comparative Examples 1 to 3 that do not use the phosphate ester flame retardant according to the present invention have many stress corrosion cracks at the edge, and the heat resistance and mechanical properties are also the same as the resin compositions of the examples. It was inferior compared. Moreover, since the weight loss in TGA was remarkable, it was confirmed that the amount of gas generated was large and it was easily decomposed by heating.
Moreover, in the resin component system different from the present invention, it can be confirmed from the results of Reference Examples 1 and 2 that defects such as stress corrosion cracking due to gas generation are not a problem even when the flame retardant for Comparative Example is used.
Claims (5)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011190371A (en) * | 2010-03-15 | 2011-09-29 | Asahi Kasei Chemicals Corp | Resin composition |
| WO2015025701A1 (en) * | 2013-08-20 | 2015-02-26 | 株式会社Adeka | Flame-retardant synthetic resin composition |
| CN115572473A (en) * | 2021-06-21 | 2023-01-06 | 旭化成株式会社 | Polyphenylene ether resin composition |
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| JP2008202009A (en) * | 2007-02-22 | 2008-09-04 | Adeka Corp | Solid flame-retardant |
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| JPH0827311A (en) * | 1994-07-14 | 1996-01-30 | Asahi Chem Ind Co Ltd | Preparation of flame retardant |
| JP2003226819A (en) * | 2001-11-30 | 2003-08-15 | Polyplastics Co | Flame-retardant resin composition |
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| WO2015025701A1 (en) * | 2013-08-20 | 2015-02-26 | 株式会社Adeka | Flame-retardant synthetic resin composition |
| JPWO2015025701A1 (en) * | 2013-08-20 | 2017-03-02 | 株式会社Adeka | Flame retardant synthetic resin composition |
| CN115572473A (en) * | 2021-06-21 | 2023-01-06 | 旭化成株式会社 | Polyphenylene ether resin composition |
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