JP5546115B2 - Flame retardant resin composition - Google Patents
Flame retardant resin composition Download PDFInfo
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- JP5546115B2 JP5546115B2 JP2008250627A JP2008250627A JP5546115B2 JP 5546115 B2 JP5546115 B2 JP 5546115B2 JP 2008250627 A JP2008250627 A JP 2008250627A JP 2008250627 A JP2008250627 A JP 2008250627A JP 5546115 B2 JP5546115 B2 JP 5546115B2
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- 239000003063 flame retardant Substances 0.000 title claims description 24
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 21
- 239000011342 resin composition Substances 0.000 title claims description 19
- 229920005668 polycarbonate resin Polymers 0.000 claims description 32
- 239000004431 polycarbonate resin Substances 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229920001296 polysiloxane Polymers 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 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 10
- 238000011156 evaluation Methods 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 238000013329 compounding Methods 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 125000005027 hydroxyaryl group Chemical group 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 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 3
- 230000007547 defect Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- FDLFMPKQBNPIER-UHFFFAOYSA-N 1-methyl-3-(3-methylphenoxy)benzene Chemical compound CC1=CC=CC(OC=2C=C(C)C=CC=2)=C1 FDLFMPKQBNPIER-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 2
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 2
- QHJPJZROUNGTRJ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)octan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCC)C1=CC=C(O)C=C1 QHJPJZROUNGTRJ-UHFFFAOYSA-N 0.000 description 2
- GRCXOICCGCYITB-UHFFFAOYSA-N 4-[2-[2-[2-(4-hydroxyphenyl)-3-methylphenyl]propan-2-yl]-6-methylphenyl]phenol Chemical compound CC1=CC=CC(C(C)(C)C=2C(=C(C)C=CC=2)C=2C=CC(O)=CC=2)=C1C1=CC=C(O)C=C1 GRCXOICCGCYITB-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000001987 diarylethers Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 2
- HGJYOHAIVZXUML-UHFFFAOYSA-M potassium;3-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=CC=CC=2)=C1 HGJYOHAIVZXUML-UHFFFAOYSA-M 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ZQRQNIXMRZLUOT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluorobutane-1,4-disulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(O)(=O)=O ZQRQNIXMRZLUOT-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- RQTDWDATSAVLOR-UHFFFAOYSA-N 4-[3,5-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC(C=2C=CC(O)=CC=2)=CC(C=2C=CC(O)=CC=2)=C1 RQTDWDATSAVLOR-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LHWZLUXODWUHLZ-UHFFFAOYSA-N 4-methyl-n-(4-methylphenyl)sulfonylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NS(=O)(=O)C1=CC=C(C)C=C1 LHWZLUXODWUHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000004790 diaryl sulfoxides Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- XESFGOBWYAMCMB-UHFFFAOYSA-N potassium;bis(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)azanide Chemical compound [K+].FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XESFGOBWYAMCMB-UHFFFAOYSA-N 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、難燃性樹脂組成物およびそれから成形されてなる成形品に関する。更に詳しくは、耐衝撃性、耐熱性、熱安定性に優れ、塩素または臭素系難燃剤を使用せず難燃性を改善した直鎖状および分岐状ポリカーボネート樹脂からなる樹脂組成物およびその成形品を提供するものである。 The present invention relates to a flame retardant resin composition and a molded article formed therefrom. More specifically, a resin composition comprising a linear and branched polycarbonate resin having excellent impact resistance, heat resistance, and thermal stability and improved flame retardancy without using a chlorine or bromine-based flame retardant, and a molded product thereof Is to provide.
ポリカーボネート樹脂は、耐衝撃性、耐熱性、熱安定性等に優れた熱可塑性樹脂であり、電気、電子、ＩＴＥ、機械、自動車などの分野で広く用いられている。ポリカーボネート樹脂は、自己消火性を備えた難燃性の高いプラスチック材料ではあるが、前述の各分野では、難燃化の要望が強く、さらに安全上の要求を満たすため、アンダーライターズ・ラボラトリーズが定めているＵＬ９４試験（機器の部品用プラスチック材料の燃焼性試験）に準拠した難燃性の評価において、ＵＬ９４Ｖ−０やＶ−１相当の一層高い難燃性が求められている。 Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, thermal stability, and the like, and is widely used in fields such as electricity, electronics, ITE, machinery, and automobiles. Polycarbonate resin is a highly flame-retardant plastic material with self-extinguishing properties. However, in the above-mentioned fields, there is a strong demand for flame retardancy, and underwriters laboratories In the flame retardancy evaluation based on the established UL94 test (flammability test of plastic materials for equipment parts), higher flame retardancy equivalent to UL94V-0 and V-1 is required.
ポリカーボネート樹脂に難燃性を付与させる手法として、従来、難燃剤として塩素や臭素系化合物、あるいはリン系化合物を配合する方法が採用されている。しかし、塩素や臭素系難燃剤は、優れた難燃効果を示すものの、射出成形時に成形機スクリューや製品金型を腐食させる等の問題があった。また、リン系難燃剤は縮合リン酸エステル系難燃剤を中心に使用されているが、耐熱性あるいは衝撃強度の極端な低下が発生するという問題があった。これら著しい物性低下や環境面への配慮から、臭素や塩素等のハロゲン系化合物およびリン系化合物を含有しない難燃剤の使用が望まれている。 As a technique for imparting flame retardancy to a polycarbonate resin, conventionally, a method of blending chlorine, a bromine compound, or a phosphorus compound as a flame retardant has been adopted. However, chlorine and bromine-based flame retardants exhibit excellent flame retardant effects, but have problems such as corrosion of molding machine screws and product molds during injection molding. Moreover, although the phosphorus-based flame retardant is mainly used as a condensed phosphate ester-based flame retardant, there is a problem that an extreme decrease in heat resistance or impact strength occurs. In view of these remarkable physical properties and environmental considerations, it is desired to use a flame retardant that does not contain halogen compounds such as bromine and chlorine and phosphorus compounds.
上記難燃剤を使用せず難燃化する方法として、ポリカーボネート樹脂に芳香族スルホン酸金属塩を添加する方法（特許文献１）やパーフルオロアルカンスルホン酸カリウムを添加する方法（特許文献２）および分岐状ポリカーボネート樹脂に有機アルカリ金属塩を添加する方法（特許文献３）などの提案がされてきた。これらの手法を用いることにより、ＵＬ９４試験に準拠した難燃性の評価において、燃焼時間の減少効果および燃焼時における樹脂の滴下（ドリッピング）抑制効果はある程度認められるものの、製品安全上の規格を満たすには十分ではなく、より一層優れた難燃性を有する材料の開発が求められている。 As a method of making flame retardant without using the above flame retardant, a method of adding an aromatic sulfonic acid metal salt to a polycarbonate resin (Patent Document 1), a method of adding potassium perfluoroalkane sulfonate (Patent Document 2), and branching A method of adding an organic alkali metal salt to a glassy polycarbonate resin (Patent Document 3) has been proposed. By using these methods, in the evaluation of flame retardancy based on the UL94 test, the effect of reducing combustion time and the effect of suppressing dripping of resin during combustion are recognized to some extent. There is a need for the development of materials that are not sufficient to satisfy, and that have even better flame retardancy.
一方、分岐状ポリカーボネート樹脂に重量平均分子量が４００〜１５００のポリオルガノシロキサンと有機スルホン酸金属塩をブレンドした樹脂組成物（特許文献４）が開示されている。しかしながら、当該分子量範囲のシロキサンを用いるとシロキサン自体の耐熱性が低下して難燃性の効果が低下し、さらに溶融粘度が低すぎて、成形加工時にポリカーボネート樹脂の成形体表面にシロキサン化合物がブリードアウトして成形体表面の外観を損ねるなど成形性を低下させる場合があるため、難燃性のみならず優れた成形性を有する材料の開発が望まれていた。 On the other hand, a resin composition (Patent Document 4) in which a polyorganosiloxane having a weight average molecular weight of 400 to 1500 and an organic sulfonic acid metal salt is blended with a branched polycarbonate resin is disclosed. However, when a siloxane having the molecular weight range is used, the heat resistance of the siloxane itself is lowered, the flame retardancy effect is lowered, and the melt viscosity is too low. In some cases, the moldability may be deteriorated, for example, by deteriorating the appearance of the surface of the molded body. Therefore, development of a material having not only flame retardancy but also excellent moldability has been desired.
さらに、燃焼時のドリッピングを抑制する方法として、ポリカーボネート樹脂にフッ素化ポリオレフィンを添加した樹脂組成物（特許文献５）が開示されている。このような組成物においては、燃焼時のドリッピングが抑制され難燃性は向上するものの、射出成形時にフッ素化ポリオレフィンが樹脂の流動方向に配向したり、フッ素化ポリオレフィンの凝集物が製品表面の外観不良を引き起こし、製品としての価値が著しく低下するという問題があり、従来からその改善が望まれてきた。 Furthermore, as a method for suppressing dripping during combustion, a resin composition (Patent Document 5) in which a fluorinated polyolefin is added to a polycarbonate resin is disclosed. In such a composition, although dripping during combustion is suppressed and flame retardancy is improved, the fluorinated polyolefin is oriented in the flow direction of the resin during injection molding, or the aggregate of the fluorinated polyolefin is formed on the surface of the product. There has been a problem in that the appearance value is deteriorated and the value as a product is remarkably lowered.
本発明は、上記難燃性、物性低下、外観不良、成形性等の問題を改善し、かつ臭素や塩素等のハロゲン系難燃剤、リン系難燃剤あるいはフッ素化ポリオレフィンを使用することなく、高い難燃性をも具備しうる樹脂組成物およびそれからなる成形品を提供することを目的とする。 The present invention improves the above-mentioned problems such as flame retardancy, deterioration of physical properties, poor appearance, moldability and the like, and is high without using halogen flame retardants such as bromine and chlorine, phosphorus flame retardants or fluorinated polyolefins. It aims at providing the resin composition which can also have a flame retardance, and a molded article consisting thereof.
本発明者らは、かかる課題に鑑み鋭意研究を行った結果、直鎖状ポリカーボネート樹脂に分岐状ポリカーボネート樹脂を特定の範囲の配合量で含有させ、さらに特定のシリコーン化合物および有機金属塩を配合することにより、射出成形における不良現象や樹脂の物性低下を抑制し、高い難燃性をも併せ持つ難燃性樹脂組成物が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of such problems, the present inventors have incorporated a branched polycarbonate resin into a linear polycarbonate resin in a specific range of blending amount, and further blended a specific silicone compound and an organic metal salt. As a result, it has been found that a flame retardant resin composition having both high flame retardancy and a flame retardant resin composition that suppresses a defective phenomenon in injection molding and a decrease in physical properties of the resin can be obtained.
すなわち、本発明は、直鎖状ポリカーボネート樹脂（Ａ）２０〜８０重量％および分岐状ポリカーボネート樹脂（Ｂ）８０〜２０重量％からなる樹脂成分１００重量部、主鎖が分岐構造でかつ含有する有機官能基が芳香族基からなるか、または芳香族基と炭化水素基（芳香族基を除く）とからなるシリコーン化合物（C）０．０３〜２重量部および有機金属塩（Ｄ）０．０１〜１重量部からなることを特徴とする難燃性樹脂組成物ならびにそれからなる成形品を提供するものである
That is, the present invention relates to an organic to linear polycarbonate resin (A) 20 to 80 wt% and branched polycarbonate resin (B) 100 parts by weight of the resin component consisting of 80 to 20 wt%, the main chain contains and a branched structure 0.03 to 2 parts by weight of a silicone compound (C) having a functional group comprising an aromatic group or comprising an aromatic group and a hydrocarbon group (excluding an aromatic group) and an organic metal salt (D) 0.01 It provides a flame retardant resin composition characterized by comprising 1 part by weight and a molded product comprising the same.
本発明の難燃性樹脂組成物は、衝撃強度、耐熱性、熱安定性等性能に優れ、高い難燃性を有し、成形性に優れ、かつ外観不良の少ない成形品を得ることができるため、その工業的利用価値は極めて高い。 The flame-retardant resin composition of the present invention is excellent in performance such as impact strength, heat resistance, and thermal stability, has high flame retardancy, excellent moldability, and can provide a molded product with few appearance defects. Therefore, its industrial utility value is extremely high.
本発明にて使用される直鎖状ポリカーボネート樹脂（Ａ）とは、種々のジヒドロキシジアリール化合物とホスゲンとを反応させるホスゲン法、またはジヒドロキシジアリール化合物とジフェニルカーボネートなどの炭酸エステルとを反応させるエステル交換法によって得られる重合体であり、代表的なものとしては、２,２−ビス（４−ヒドロキシフェニル）プロパン（通称ビスフェノールＡ）から製造された直鎖状ポリカーボネート樹脂が挙げられる。 The linear polycarbonate resin (A) used in the present invention is a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example is a linear polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A).
上記ジヒドロキシジアリール化合物としては、ビスフェノールＡの他に、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）オクタン、ビス（４−ヒドロキシフェニル）フェニルメタン、２，２−ビス（４−ヒドロキシフェニル−３−メチルフェニル）プロパン、１，１−ビス（４−ヒドロキシ−３−第三ブチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−ブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）プロパンのようなビス（ヒドロキシアリール）アルカン類、１，１−ビス（４−ヒドロキシフェニル）シクロペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサンのようなビス（ヒドロキシアリール）シクロアルカン類、４，４′−ジヒドロキシジフェニルエーテル、４，４′−ジヒドロキシ−３，３′−ジメチルジフェニルエーテルのようなジヒドロキシジアリールエーテル類、４，４′−ジヒドロキシジフェニルスルフィドのようなジヒドロキシジアリールスルフィド類、４，４′−ジヒドロキシジフェニルスルホキシド、４，４′−ジヒドロキシ−３，３′−ジメチルジフェニルスルホキシドのようなジヒドロキシジアリールスルホキシド類、４，４′−ジヒドロキシジフェニルスルホン、４，４′−ジヒドロキシ−３，３′−ジメチルジフェニルスルホンのようなジヒドロキシジアリールスルホン類等が挙げられる。しかしながら、ハロゲンで置換されていないジヒドロキシジアリール化合物を使用することが環境面から好ましい。 Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like. However, it is preferred from the environmental viewpoint to use a dihydroxydiaryl compound not substituted with halogen.
これらは単独または２種類以上混合して使用されるが、これらの他に、ピペラジン、ジピペリジルハイドロキノン、レゾルシン、４，４′−ジヒドロキシジフェニル等を混合して使用してもよい。 These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.
直鎖状ポリカーボネート樹脂（Ａ）の粘度平均分子量は、特に制限はないが、成形加工性、強度の面より通常１００００〜１０００００、より好ましくは１５０００〜４００００、さらに好ましくは１７０００〜２８０００の範囲である。また、かかるポリカーボネート樹脂を製造するに際し、分子量調整剤、触媒等を必要に応じて使用することができる。 The viscosity average molecular weight of the linear polycarbonate resin (A) is not particularly limited, but is usually in the range of 10,000 to 100,000, more preferably 15,000 to 40,000, and still more preferably 17,000 to 28,000 in terms of moldability and strength. . Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.
本発明にて使用される分岐状ポリカーボネート樹脂（Ｂ）とは、ジヒドロキシジアリール化合物、分岐剤およびホスゲンとを反応させるホスゲン法、またはジヒドロキシジアリール化合物、分岐剤およびジフェニルカーボネートなどの炭酸エステルとを反応させるエステル交換法によって得られる重合体であり、代表的なものとしては、２，２−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）、分岐剤およびホスゲンから製造された分岐状ポリカーボネート樹脂が挙げられる。 The branched polycarbonate resin (B) used in the present invention is a phosgene method in which a dihydroxydiaryl compound, a branching agent and phosgene are reacted, or a dihydroxydiaryl compound, a branching agent and a carbonate such as diphenyl carbonate are reacted. A polymer obtained by a transesterification method, and representative examples thereof include a branched polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), a branching agent and phosgene. .
上記ジヒドロキシジアリール化合物としては、ビスフェノールＡの他に、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）オク
タン、ビス（４−ヒドロキシフェニル）フェニルメタン、２，２−ビス（４−ヒドロキシフェニル−３−メチルフェニル）プロパン、１，１−ビス（４−ヒドロキシ−３−第三ブチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−ブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）プロパンのようなビス（ヒドロ
キシアリール）アルカン類、１，１−ビス（４−ヒドロキシフェニル）シクロペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサンのようなビス（ヒド
ロキシアリール）シクロアルカン類、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシ−３，３’−ジメチルジフェニルエーテルのようなジヒドロキシジアリールエーテル類、４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシ−３，３’−ジメチルジフェニルスルフィドのようなジヒドロキシジアリールスルフィド類、４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジヒドロキシ−
３，３’−ジメチルジフェニルスルホキシドのようなジヒドロキシジアリールスルホキシド類、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシ−３，３’−ジメチルジフェニルスルホンのようなジヒドロキシジアリールスルホン類等が挙げられる。
Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4 ' -Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-
Examples include dihydroxydiaryl sulfoxides such as 3,3′-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, and the like. It is done.
これらは単独または２種類以上混合して使用されるが、これらの他に、ピペラジン、ジピペリジルハイドロキノン、レゾルシン、４，４’−ジヒドロキシジフェニル等を混合
して使用してもよい。
These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.
分岐剤として使用される３価以上のフェノールとしては、フロログルシン、４，６−ジメチル−２，４，６−トリ−（４−ヒドロキシフェニル）−ヘプテン−２、４，６−ジメチル−２，４，６−トリ−（４−ヒドロキシフェニル）−ヘプタン、１，３，５−トリ
−（４−ヒドロキシフェニル）−ベンゾール、１，１，１−トリス−（４−ヒドロキシフェニル）−エタンおよび２，２−ビス−〔４，４−（４，４’−ジヒドロキシジフェニル）−シクロヘキシル〕−プロパンなどが挙げられる。
Examples of the trivalent or higher phenol used as a branching agent include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4. , 6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tris- (4-hydroxyphenyl) -ethane and 2, 2-bis- [4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.
これら分岐剤の含有量には特に制限はないが、成形加工性の面より、分岐状ポリカーボネート樹脂あたり０．０１〜５．０重量％であることが好ましい。 Although there is no restriction | limiting in particular in content of these branching agents, It is preferable that it is 0.01 to 5.0 weight% per branched polycarbonate resin from the surface of a moldability.
分岐状ポリカーボネート樹脂（Ｂ）の分子量には特に制限はないが、成形加工性の面より、メルトフローレイト（ＭＦＲ）（３００℃、１．２Ｋｇ荷重）が１．０〜２０．０ｇ／１０分であることが好ましい。 The molecular weight of the branched polycarbonate resin (B) is not particularly limited, but the melt flow rate (MFR) (300 ° C., 1.2 kg load) is 1.0 to 20.0 g / 10 min from the viewpoint of moldability. It is preferable that
分岐状ポリカーボネート樹脂（Ｂ）は、従来公知の方法により製造することができる。たとえば、特開昭５６−５５３２８、特開昭５８−２３８２５、特開昭５９−４５３１８、特開昭５９−１３３２２３、特開昭５９−１３４７４２、特開昭６２−１００７１、特開昭６２−１５２２３などに記載の方法が挙げられる。 The branched polycarbonate resin (B) can be produced by a conventionally known method. For example, JP-A-56-55328, JP-A-58-23825, JP-A-59-45318, JP-A-59-133223, JP-A-59-134742, JP-A-62-10071, JP-A-62-15223. And the like.
本発明にて使用されるシリコーン化合物（Ｃ）は、主鎖が分岐構造でかつ有機官能基が芳香族基からなるか、または芳香族基と炭化水素基（芳香族基を除く）とからなり、下記一般式（１）にて示される。
一般式（１）
The silicone compound (C) used in the present invention comprises a branched main chain and an organic functional group comprising an aromatic group, or an aromatic group and a hydrocarbon group (excluding an aromatic group). Is represented by the following general formula (1).
General formula (1)
ここで、Ｒ１、Ｒ２およびＲ３は主鎖の有機官能基を、Ｘは末端の官能基を表わす。
すなわち、分岐単位としてＴ単位（ＲＳｉＯ1.５）および／またはＱ単位（ＳｉＯ2.0）を持つことを特徴とする。これらは全体のシロキサン単位（Ｒ３〜０ＳｉＯ２〜０．５）の２０モル％以上含有することが好ましい。（Ｒは有機官能基をあらわす。）また、シリコーン化合物（Ｃ）は、含有される有機官能基のうち芳香族基が２０モル％以上であることが好ましい。
Here, R1, R2, and R3 represent main chain organic functional groups, and X represents a terminal functional group.
That is, it has a T unit (RSiO 1.5 ) and / or a Q unit (SiO 2.0 ) as a branch unit. These preferably contains more than 20 mol% of the total siloxane units (R 3~0 SiO 2~0.5). (R represents an organic functional group.) Further, the silicone compound (C) preferably contains 20 mol% or more of aromatic groups among the organic functional groups contained.
この含有される芳香族基としては、フェニル、ビフェニル、ナフタレンまたはこれらの誘導体であるが、フェニル基が好適に使用できる。 The aromatic group contained is phenyl, biphenyl, naphthalene or a derivative thereof, but a phenyl group can be preferably used.
シリコーン化合物（Ｃ）中の有機官能基で、主鎖や分岐した側鎖に付いたもののうち芳香族基以外の有機基としては、炭素数４以下の炭化水素基が好ましく、メチル基が好適に使用できる。さらに、末端基はメチル基、フェニル基、水酸基の内から選ばれた１種またはこれらの２種から３種までの混合物であることが好ましい。 Of the organic functional groups in the silicone compound (C) attached to the main chain or branched side chain, the organic group other than the aromatic group is preferably a hydrocarbon group having 4 or less carbon atoms, and preferably a methyl group. Can be used. Further, the terminal group is preferably one kind selected from methyl group, phenyl group and hydroxyl group, or a mixture of these two kinds to three kinds.
シリコーン化合物（Ｃ）の平均分子量（重量平均）は、好ましくは３０００〜５０００００であり、更に好ましくは５０００〜２７００００である。３０００未満であるとシリコーン自体の耐熱性が低下して十分な難燃性効果が得られず、さらに溶融粘度が低すぎて成形体表面にシリコーン化合物がブリードアウトして外観を損ねる場合があり、一方、５０００００を超えると溶融粘度が増加してポリカーボネート樹脂中の均一な分散ができず、難燃性および成形性が低下するため好ましくない。さらに好ましくは１００００〜２７００００である。この範囲では溶融粘度が最適となるため、一層良好な難燃性と成形性を達成することができる。 The average molecular weight (weight average) of the silicone compound (C) is preferably 3,000 to 500,000, and more preferably 5,000 to 270000. If it is less than 3000, the heat resistance of the silicone itself is lowered and a sufficient flame retardant effect cannot be obtained. Further, the melt viscosity is too low, and the silicone compound may bleed out on the surface of the molded product, which may impair the appearance. On the other hand, if it exceeds 500,000, the melt viscosity increases and uniform dispersion in the polycarbonate resin cannot be achieved, and the flame retardancy and moldability are lowered, which is not preferable. More preferably, it is 10,000 to 270000. In this range, since the melt viscosity is optimum, better flame retardancy and formability can be achieved.
シリコーン化合物（Ｃ）の配合量は、直鎖状ポリカーボネート樹脂（Ａ）１０〜９０重量％および分岐状ポリカーボネート樹脂（Ｂ）９０〜１０重量％からなる樹脂成分１００重量部あたり、０．０１〜５重量部である。配合量がこの範囲外であると何れも充分な難燃効果が得られないので好ましくない。より好ましくは０．０３〜２重量部の範囲である。 The compounding amount of the silicone compound (C) is 0.01 to 5 per 100 parts by weight of the resin component comprising 10 to 90% by weight of the linear polycarbonate resin (A) and 90 to 10% by weight of the branched polycarbonate resin (B). Parts by weight. If the blending amount is out of this range, any flame retardant effect cannot be obtained. More preferably, it is the range of 0.03 to 2 weight part.
本発明にて使用される有機金属塩（Ｄ）としては、芳香族スルホン酸の金属塩、パーフルオロアルカンスルホン酸の金属塩、パーフルオロアルカンスルホン酸イミドの金属塩等があげられる。金属の種類としては、アルカリ金属、アルカリ土類金属等が挙げられる。好適には、４−メチル−Ｎ−（４−メチルフェニル）スルフォニル−ベンゼンスルフォンアミドのカリウム塩、ジフェニルスルホン−３−スルホン酸カリウム、ジフェニルスルホン−３−３´−ジスルホン酸カリウム、パラトルエンスルホン酸ナトリウム、パーフルオロブタンスルホン酸カリウム塩、パーフルオロブタンジスルホン酸ナトリウム、パーフルオロプロパンジスルホンイミドカリウム塩、ビス（ノナフルオロブタンスルホニル）イミドカリウム等が使用できる。 Examples of the organic metal salt (D) used in the present invention include aromatic sulfonic acid metal salts, perfluoroalkanesulfonic acid metal salts, and perfluoroalkanesulfonic acid imide metal salts. Examples of the metal include alkali metals and alkaline earth metals. Preferably, potassium salt of 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, paratoluenesulfonic acid Sodium, potassium perfluorobutanesulfonate, sodium perfluorobutanedisulfonate, potassium perfluoropropanedisulfonimide, potassium bis (nonafluorobutanesulfonyl) imide, etc. can be used.
有機金属塩（Ｄ）の配合量は、直鎖状ポリカーボネート樹脂（Ａ）１０〜９０重量％および分岐状ポリカーボネート樹脂（Ｂ）９０〜１０重量％からなる樹脂成分１００重量部に対して、０．０１〜１重量部である。０．０１重量部未満では難燃性が低下するので好ましくない。また、１重量部を超えると、熱安定性に劣り、射出成形時にシルバーストリークといった外観不良が発生するので好ましくない。好ましくは０．０２〜０．５重量部、より好ましくは０．０４〜０．２重量部である。 The compounding amount of the organic metal salt (D) is 0.1% with respect to 100 parts by weight of the resin component consisting of 10 to 90% by weight of the linear polycarbonate resin (A) and 90 to 10% by weight of the branched polycarbonate resin (B). 01 to 1 part by weight. If it is less than 0.01 part by weight, the flame retardancy is lowered, which is not preferable. On the other hand, when the amount exceeds 1 part by weight, the thermal stability is inferior, and appearance defects such as silver streak occur at the time of injection molding. Preferably it is 0.02-0.5 weight part, More preferably, it is 0.04-0.2 weight part.
本発明の各種配合成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）の配合方法および溶融混練方法には特に制限はなく、任意の混合機、例えばタンブラー、リボンブレンダー、高速ミキサー等によりこれらを混合し、通常の一軸または二軸押出機等で溶融混練することができる。また、これら配合成分の配合順序や一括混合、分割混合を採用することについても特に制限はない。 There are no particular limitations on the blending method and melt kneading method of the various blending components (A), (B), (C), and (D) of the present invention. These can be mixed and melt-kneaded with a normal single-screw or twin-screw extruder. Moreover, there is no restriction | limiting in particular also about the mixing | blending order of these compounding components, collective mixing, and division | segmentation mixing.
また、混合時、必要に応じて他の公知の添加剤、例えば離型剤、紫外線吸収剤、充填剤、帯電防止剤、酸化防止剤、リン系熱安定剤、染顔料、展着剤（エポキシ化大豆油、流動パラフィン等）等を配合することができる。 In addition, other known additives such as mold release agents, ultraviolet absorbers, fillers, antistatic agents, antioxidants, phosphorous heat stabilizers, dyes and pigments, spreading agents (epoxies) may be used as necessary. Modified soybean oil, liquid paraffin, and the like).
以下に、本発明を実施例により具体的に説明するが、本発明はこれら実施例により何ら制限されるものではない。なお、部や％は特に断りのない限り重量基準に基づく。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Parts and% are based on weight unless otherwise specified.
使用した配合成分の詳細は、以下のとおりである。
直鎖状ポリカーボネート樹脂：
住友ダウ社製 カリバー２００−２０（粘度平均分子量：１９０００）
（以下、ＰＣ−１と略記）
分岐状ポリカーボネート樹脂：
ダウ・ケミカル社製 カリバー６００−３（粘度平均分子量：２４０００）
（以下、ＰＣ−２と略記）
The details of the used blending components are as follows.
Linear polycarbonate resin:
Caliber 200-20 (viscosity average molecular weight: 19000) manufactured by Sumitomo Dow
(Hereinafter abbreviated as PC-1)
Branched polycarbonate resin:
Caliber 600-3 (viscosity average molecular weight: 24000) manufactured by Dow Chemical
(Hereafter abbreviated as PC-2)
シリコーン化合物：（以下「シリコーン」と略記）
シリコーンは、一般的な製造方法に従って製造した。すなわち、適量のジオルガノジクロロシラン、モノオルガノトリクロロシランおよびテトラクロロシラン、あるいはそれらの部分加水分解縮合物を有機溶剤中に溶解し、水を添加して加水分解して、部分的に縮合したシリコーン化合物を形成し、さらにトリオルガノクロロシランを添加して反応させることによって重合を終了させ、その後、溶媒を蒸留等で分離した。上記方法で合成したシリコーンの構造特性は、以下のとおり：
・主鎖構造のＤ／Ｔ／Ｑ単位の比率：４０／６０／０（モル比）
・全有機官能基中のフェニル基の比率(＊)：６０モル％
・末端基：メチル基のみ
・重量平均分子量(＊＊)：１５０００
＊：フェニル基は、Ｔ単位を含むシリコーン中ではＴ単位にまず含まれ、残った場合がＤ単位に含まれる。Ｄ単位にフェニル基が付く場合、１個付くものが優先し、さらにフェニル基が残余する場合に２個付く。末端基を除き、有機官能基は、フェニル基以外は全てメチル基である。
＊＊：重量平均分子量は、有効数字２桁。
Silicone compound: (hereinafter abbreviated as “silicone”)
Silicone was produced according to a general production method. That is, a silicone compound partially condensed by dissolving an appropriate amount of diorganodichlorosilane, monoorganotrichlorosilane and tetrachlorosilane, or a partially hydrolyzed condensate thereof in an organic solvent, adding water and hydrolyzing. Then, triorganochlorosilane was added and reacted to terminate the polymerization, and then the solvent was separated by distillation or the like. The structural properties of the silicone synthesized by the above method are as follows:
・ D / T / Q unit ratio of main chain structure: 40/60/0 (molar ratio)
-Ratio of phenyl group in all organic functional groups (*): 60 mol%
-Terminal group: methyl group only-Weight average molecular weight (**): 15000
*: The phenyl group is first contained in the T unit in the silicone containing the T unit, and the remaining D group is contained in the D unit. When the phenyl group is attached to the D unit, the one attached is preferential, and when the phenyl group remains, two are attached. Except for the terminal group, the organic functional group is a methyl group except for the phenyl group.
**: Weight average molecular weight is two significant digits.
有機金属塩：
パーフルオロブタンスルホン酸カリウム（以下Ｄ−１と略記）
ジフェニルスルホン−３−スルホン酸カリウム（以下Ｄ−２と略記）
パラトルエンスルホン酸ナトリウム（以下Ｄ−３と略記）
Organometallic salt:
Perfluorobutane sulfonate potassium (hereinafter abbreviated as D-1)
Potassium diphenylsulfone-3-sulfonate (hereinafter abbreviated as D-2)
Sodium paratoluenesulfonate (hereinafter abbreviated as D-3)
（成形品の外観評価）
表２〜表４に示す配合成分および配合比率に基づき得られた各種樹脂組成物のペレットを１２５℃で４時間乾燥した後に、射出成形機（日本製鋼所製Ｊ−１００ＳＡＩＩ）を用いて設定温度３２０℃にて外観評価用試験片（１５０ｘ９０ｘ３．０ｍｍ）を作成した。成形品外観を目視にて観察し、以下の基準に基づき外観の判定を行い、○を合格とした。結果を表２〜表４に示す。
外観良好（○）：成形品にシルバーストリークや焼けが発生せず、一様な外観が得られ
る。
外観不良（×）：成形品にシルバーストリークや焼けが発生し、製品全体が黄変する。
(Appearance evaluation of molded products)
The pellets of various resin compositions obtained based on the blending components and blending ratios shown in Tables 2 to 4 were dried at 125 ° C. for 4 hours, and then set using an injection molding machine (Japan Steel Works J-100SAII). A test piece for appearance evaluation (150 × 90 × 3.0 mm) was prepared at 320 ° C. The appearance of the molded product was visually observed, and the appearance was determined based on the following criteria. The results are shown in Tables 2-4.
Appearance is good (○): Silver streaks and burns do not occur in the molded product, and a uniform appearance is obtained.
The
Appearance defect (×): Silver streaks and burns occur in the molded product, and the entire product turns yellow.
（成形性の評価）
得られた各種樹脂組成物のペレットを１２５℃で４時間乾燥した後に、射出成形機（日本製鋼所製Ｊ−１００ＳＡＩＩ）を用いて設定温度２８０℃、射出圧力１６００ｋｇ／ｃｍ２にて難燃性評価用試験片（１２５ｘ１３ｘ１．６ｍｍ）を作成した。得られた試験片を目視にて観察し、以下の基準の基づき成形性の判定を行い、○および△を合格とした。結果を表２〜表４に示す。
良好（○） ：製品末端まで完全に樹脂が充填される。
やや悪い（△）：製品末端にヒケが見られる。
悪い（×） ：製品末端まで樹脂が充填されない。
(Evaluation of formability)
After the pellets of the various resin compositions obtained were dried at 125 ° C. for 4 hours, flame retardancy was performed at a set temperature of 280 ° C. and an injection pressure of 1600 kg / cm 2 using an injection molding machine (J-100SAII manufactured by Nippon Steel). A test piece for evaluation (125 × 13 × 1.6 mm) was prepared. The obtained test piece was visually observed, the moldability was determined based on the following criteria, and ○ and Δ were set as acceptable. The results are shown in Tables 2-4.
Good (O): The resin is completely filled to the end of the product.
Slightly bad (△): sink marks are observed at the end of the product.
Poor (x): Resin is not filled to the end of the product.
（難燃性評価）
得られた各種樹脂組成物のペレットを１２５℃で４時間乾燥した後に、射出成形機（日本製鋼所製Ｊ−１００ＳＡＩＩ）を用いて設定温度２８０℃にて難燃性評価用試験片（１２５ｘ１３ｘ１．６ｍｍおよび１２５ｘ１３ｘ１．２ｍｍ）を作成した。得られた試験片を用いて温度２３℃、湿度５０％の恒温室の中で７２時間放置し、アンダーライターズ・ラボラトリーズが定めているＵＬ９４試験（機器の部品用プラスチック材料の燃焼性試験）に準拠した難燃性の評価を行い、Ｖ−０またはＶ−１を合格とした。結果を表２〜表４に示す。なお、ＵＬ９４の難燃性クラスは表１のとおり。
(Flame retardance evaluation)
After the pellets of the various resin compositions obtained were dried at 125 ° C. for 4 hours, a test piece for flame retardancy evaluation (125 × 13 × 1...) At a set temperature of 280 ° C. using an injection molding machine (J-100SAII manufactured by Nippon Steel) 6 mm and 125 × 13 × 1.2 mm). The obtained specimen is left in a constant temperature room at 23 ° C. and 50% humidity for 72 hours, and is subjected to UL94 test (flammability test of plastic materials for equipment parts) defined by Underwriters Laboratories. The compliant flame retardancy was evaluated, and V-0 or V-1 was determined to be acceptable. The results are shown in Tables 2-4. The flame resistance class of UL94 is as shown in Table 1.
残炎時間とは、着火源を遠ざけた後の試験片が、有炎燃焼を続ける時間の長さであり、ドリップによる綿の着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火されるかどうかによって決定される。 The after flame time is the length of time that the test piece after the ignition source is moved away from the flame, and the ignition of the cotton by the drip is for the sign about 300 mm below the lower end of the test piece. Of cotton is ignited by a drip from the specimen.
樹脂組成物が本発明の構成要件を満足する場合（参考例７および８を除く、実施例１〜１３）にあっては、全ての評価項目にわたり良好な結果を示した。
In the case where the resin composition satisfies the constituent requirements of the present invention ( Examples 1 to 13 except Reference Examples 7 and 8 ), good results were exhibited over all the evaluation items.
一方、樹脂組成物が本発明の構成要件を満足しない場合においては、いずれの場合も何らかの欠点を有していた。
比較例１は、分岐状ポリカーボネート樹脂の配合比率が本発明の定める範囲よりも少ない場合であり、難燃性に劣っていた。
比較例２は、分岐状ポリカーボネート樹脂の配合比率が本発明の定める範囲よりも多い場合であり、成形品外観および成形性に劣っていた。
比較例３は、シリコーン化合物の配合量が本発明の範囲よりも少ない場合であり、難燃性に劣っていた。
比較例４は、シリコーン化合物の配合量が本発明の範囲よりも多い場合であり、難燃性および成形品外観に劣っていた。
比較例５は、有機金属塩の配合比率が本発明の定める範囲よりも少ない場合であり、難燃性に劣っていた。
比較例６は、有機金属塩の配合比率が本発明の定める範囲よりも多い場合であり、成形品外観に劣っていた。
On the other hand, in the case where the resin composition does not satisfy the constituent requirements of the present invention, each case had some drawbacks.
Comparative Example 1 was a case where the blending ratio of the branched polycarbonate resin was less than the range defined by the present invention, and was inferior in flame retardancy.
Comparative Example 2 was a case where the blending ratio of the branched polycarbonate resin was larger than the range defined by the present invention, and the molded product appearance and moldability were inferior.
Comparative Example 3 was a case where the compounding amount of the silicone compound was less than the range of the present invention and was inferior in flame retardancy.
The comparative example 4 is a case where the compounding quantity of a silicone compound is more than the range of this invention, and was inferior to a flame retardance and a molded article external appearance.
Comparative Example 5 was a case where the compounding ratio of the organic metal salt was less than the range defined by the present invention, and was inferior in flame retardancy.
The comparative example 6 is a case where the compounding ratio of the organic metal salt is larger than the range defined by the present invention, and the appearance of the molded product was inferior.
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