JP5030550B2 - Thermoplastic resin composition and molded body - Google Patents
Thermoplastic resin composition and molded body Download PDFInfo
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- JP5030550B2 JP5030550B2 JP2006315123A JP2006315123A JP5030550B2 JP 5030550 B2 JP5030550 B2 JP 5030550B2 JP 2006315123 A JP2006315123 A JP 2006315123A JP 2006315123 A JP2006315123 A JP 2006315123A JP 5030550 B2 JP5030550 B2 JP 5030550B2
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- component
- formula
- resin composition
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- thermoplastic resin
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- 239000011342 resin composition Substances 0.000 title claims description 51
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 40
- -1 silane compound Chemical class 0.000 claims description 56
- 239000004431 polycarbonate resin Substances 0.000 claims description 42
- 229920005668 polycarbonate resin Polymers 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 229910000077 silane Inorganic materials 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 18
- FOUHTHSUSZNYNK-UHFFFAOYSA-M [O-2].[OH-].O.P.[Y+3] Chemical compound [O-2].[OH-].O.P.[Y+3] FOUHTHSUSZNYNK-UHFFFAOYSA-M 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000001931 aliphatic group Chemical group 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003086 colorant Substances 0.000 claims description 10
- 239000003063 flame retardant Substances 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 239000012760 heat stabilizer Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000006082 mold release agent Substances 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 description 32
- 238000012360 testing method Methods 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 13
- 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 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000000049 pigment Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 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 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 229920000515 polycarbonate Polymers 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 229920006361 Polyflon Polymers 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000003017 thermal stabilizer Substances 0.000 description 4
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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
- 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 3
- 239000012965 benzophenone Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- JWCYRADIWYQGTO-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphorous acid Chemical compound P(O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C JWCYRADIWYQGTO-UHFFFAOYSA-N 0.000 description 2
- KBZQKRFMZFQXHE-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphorous acid Chemical compound 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 KBZQKRFMZFQXHE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 2
- 235000010893 Bischofia javanica Nutrition 0.000 description 2
- 240000005220 Bischofia javanica Species 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 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
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052788 barium Chemical group 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal 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
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 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
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 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
- 229930195733 hydrocarbon Natural products 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-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
- 230000003287 optical effect Effects 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229960000969 phenyl salicylate Drugs 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- KMEHEQFDWWYZIO-UHFFFAOYSA-N triacontyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCC KMEHEQFDWWYZIO-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- NZADFKWJIQWGNZ-UHFFFAOYSA-N (2-ethylphenyl) diphenyl phosphate Chemical compound CCC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 NZADFKWJIQWGNZ-UHFFFAOYSA-N 0.000 description 1
- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AWYVETCHVQGXMB-UHFFFAOYSA-N (3-hydroxyphenyl) diphenyl phosphate Chemical compound OC1=CC=CC(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)=C1 AWYVETCHVQGXMB-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- GUYIZQZWDFCUTA-UHFFFAOYSA-N (pentadecachlorophthalocyaninato(2-))-copper Chemical compound [Cu+2].N1=C([N-]2)C3=C(Cl)C(Cl)=C(Cl)C(Cl)=C3C2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC(C2=C(Cl)C(Cl)=C(Cl)C(Cl)=C22)=NC2=NC2=C(C(Cl)=C(C(Cl)=C3)Cl)C3=C1[N-]2 GUYIZQZWDFCUTA-UHFFFAOYSA-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
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-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
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- KCRLWVVFAVLSAP-UHFFFAOYSA-N octyl dihydrogen phosphite Chemical compound CCCCCCCCOP(O)O KCRLWVVFAVLSAP-UHFFFAOYSA-N 0.000 description 1
- AXRSHKZFNKUGQB-UHFFFAOYSA-N octyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC)OC1=CC=CC=C1 AXRSHKZFNKUGQB-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical class C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- WFRUBUQWJYMMRQ-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WFRUBUQWJYMMRQ-UHFFFAOYSA-M 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- OMVLAGBUFPUMGQ-UHFFFAOYSA-M sodium;2,4,5-trichlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC(Cl)=C(Cl)C=C1Cl OMVLAGBUFPUMGQ-UHFFFAOYSA-M 0.000 description 1
- AIXLZRHUNVRXTR-UHFFFAOYSA-M sodium;3,4-dichlorobenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(Cl)C(Cl)=C1 AIXLZRHUNVRXTR-UHFFFAOYSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- FICPQAZLPKLOLH-UHFFFAOYSA-N tricyclohexyl phosphite Chemical compound C1CCCCC1OP(OC1CCCCC1)OC1CCCCC1 FICPQAZLPKLOLH-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QUTZUATVZPXUJR-UHFFFAOYSA-N trinonyl phosphite Chemical compound CCCCCCCCCOP(OCCCCCCCCC)OCCCCCCCCC QUTZUATVZPXUJR-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、熱可塑性樹脂組成物およびその成形体に関する。さらに詳しくは、加工時の熱安定性や成形品の色相・蛍光時の色相に優れた熱可塑性樹脂組成物、及び該樹脂組成物からなる、機械的強度、耐熱性、及び耐湿熱性に優れた、電飾看板、液晶バックライト、照明ディスプレイ、交通標識、サインボード、スクリーン等の成形体に関するものである。 The present invention relates to a thermoplastic resin composition and a molded body thereof. More specifically, a thermoplastic resin composition excellent in thermal stability during processing, hue of molded article, and hue during fluorescence, and composed of the resin composition, excellent in mechanical strength, heat resistance, and moist heat resistance. The present invention relates to molded articles such as electric signboards, liquid crystal backlights, illumination displays, traffic signs, sign boards, screens and the like.
ポリカーボネート樹脂は、耐衝撃性、耐熱性、透明性に優れた熱可塑性樹脂として幅広い用途がある。また、ポリカーボネート樹脂は、無機ガラスに比較して軽量で生産性にも優れているので、さらに視認性を向上させることにより、電飾看板、照明ディスプレイ、交通標識、サインボード、スクリーンなどとしても好適に使用されている。従来から、ポリカーボネート樹脂の視認性を向上させる方法として、発光顔料（蛍光体）を混合することが知られているが、蛍光体を混合したポリカーボネート樹脂を溶融混練するとポリカーボネート樹脂が熱分解し、変色や機械的強度の低下を引き起こし、実用性の乏しい樹脂組成物及び成形体しか得られなかった。 Polycarbonate resins have a wide range of uses as thermoplastic resins having excellent impact resistance, heat resistance, and transparency. Also, polycarbonate resin is lighter and more productive than inorganic glass, so it can be used as an electric signboard, lighting display, traffic sign, signboard, screen, etc. by improving visibility. Is used. Conventionally, as a method for improving the visibility of a polycarbonate resin, it is known to mix a luminescent pigment (phosphor). However, when a polycarbonate resin mixed with a phosphor is melt-kneaded, the polycarbonate resin is thermally decomposed and discolored. In addition, only a resin composition and a molded body having poor practicality were obtained, causing a decrease in mechanical strength.
蓄光顔料を混合したポリカーボネート樹脂の熱分解を抑制し、耐衝撃性を改良するために、特定量の亜燐酸エステルを配合してなる芳香族ポリカーボネート樹脂組成物が提案されている（特許文献１）。しかし、熱分解の抑制効果は不充分で、耐衝撃性の改良も満足できるものではなかった。また、樹脂と混練した後でも黒ずみを生じることなく、優れた長残光性を有する蓄光性蛍光体として、アルカリ土類アルミン酸塩を母体結晶とし、該母体結晶に賦活剤として希土類元素を含有する特定粒子径の蓄光性蛍光体が提案され、及び該蓄光性蛍光体を含有する樹脂組成物も提案されている（特許文献２）。また、加工時の熱安定性や色相に優れ、発光性能を効果的に発揮する樹脂組成物として、ポリカーボネート樹脂と特定粒子径のアルミン酸塩系蛍光体からなる樹脂組成物が提案されている（特許文献３）。しかし、いずれの樹脂組成物も、黒ずみ（色相）の改良効果は限定的であり、実用性の乏しいものであった。また、メルトフロー安定性を示し、押出機での配合時に灰色化をあまり生じない樹脂組成物として、一種以上の熱可塑性樹脂と、式Ｍ−Ａｌ（式中、Ｍはカルシウム、ストロンチウム及びバリウムからなる群から選択される１種以上の金属元素であり、Ａｌはアルミン酸基である）で表されるアルミン酸塩マトリックスを有する発光顔料とを含む熱可塑性樹脂組成物であって、発光顔料がシリコーンオイルでコートされている、熱可塑性樹脂組成物などが提案されている（特許文献４）。しかし、赤色発光性に優れた酸化イットリウム系蛍光体に関する記載はない。 In order to suppress thermal decomposition of the polycarbonate resin mixed with the phosphorescent pigment and improve impact resistance, an aromatic polycarbonate resin composition containing a specific amount of phosphite has been proposed (Patent Document 1). . However, the effect of suppressing thermal decomposition was insufficient, and the improvement in impact resistance was not satisfactory. Moreover, as a phosphorescent phosphor having excellent long persistence without causing darkening even after kneading with a resin, alkaline earth aluminate is used as a base crystal, and the base crystal contains a rare earth element as an activator. A phosphorescent phosphor having a specific particle diameter is proposed, and a resin composition containing the phosphorescent phosphor is also proposed (Patent Document 2). In addition, a resin composition comprising a polycarbonate resin and an aluminate-based phosphor having a specific particle diameter has been proposed as a resin composition that is excellent in thermal stability and hue during processing and that effectively exhibits light-emitting performance ( Patent Document 3). However, any of the resin compositions has a limited effect on improving darkening (hue), and has poor practicality. Further, as a resin composition that exhibits melt flow stability and does not cause much graying when blended in an extruder, one or more thermoplastic resins and a formula M-Al (where M is calcium, strontium, and barium) And a luminescent pigment having an aluminate matrix represented by one or more metal elements selected from the group consisting of Al is an aluminate group, A thermoplastic resin composition coated with silicone oil has been proposed (Patent Document 4). However, there is no description about an yttrium oxide phosphor excellent in red light emission.
本発明は、前記従来技術の問題点をすべて解決し、加工時の熱安定性や成形品の色相・蛍光時の色相に優れ、機械的強度、耐熱性、及び耐湿熱性に優れた成形体を製造するのに有用な熱可塑性樹脂組成物を提供すること、ならびに機械的強度、耐熱性、及び耐湿熱性（湿熱による色相の変化がない又は少ない）に優れた成形体を提供することを課題とする。 The present invention solves all the above-mentioned problems of the prior art, and provides a molded article excellent in thermal stability during processing, hue of molded article and hue during fluorescence, and excellent in mechanical strength, heat resistance, and moisture and heat resistance. It is an object of the present invention to provide a thermoplastic resin composition useful for production, and to provide a molded article excellent in mechanical strength, heat resistance, and wet heat resistance (with little or no change in hue due to wet heat). To do.
上記課題を解決するために、本発明は、ポリカーボネート樹脂（Ａ成分）を１００重量部、酸化イットリウム系蛍光体（Ｂ成分）を０．１〜５０重量部、及びシラン化合物及び／又はシリコーン化合物（Ｃ成分）をＢ成分の０．５〜１０重量％含有する熱可塑性樹脂組成物、及び該熱可塑性樹脂組成物からなる成形体を提供する。 In order to solve the above problems, the present invention provides 100 parts by weight of polycarbonate resin (component A), 0.1 to 50 parts by weight of yttrium oxide phosphor (component B), and a silane compound and / or silicone compound ( A thermoplastic resin composition containing 0.5 to 10% by weight of component B) and a molded article comprising the thermoplastic resin composition are provided.
本発明によれば、加工時の熱安定性や成形品の色相・蛍光時の色相に優れた熱可塑性樹脂組成物を提供することができる。該樹脂組成物からなる成形体は、機械的強度、耐熱性、耐湿熱性（湿熱による色相の変化が少ない又はない）に優れ、電飾看板、液晶バックライト、照明ディスプレイ、照明器具カバー、交通標識、サインボード、スクリーン、反射板やメーター部品等の自動車部品、ＯＡ機器部品などとして好適な成形体となる。 ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition excellent in the heat stability at the time of a process, the hue of the molded article, and the hue at the time of fluorescence can be provided. The molded body made of the resin composition is excellent in mechanical strength, heat resistance, and heat and humidity resistance (changes in hue due to wet heat are little or not), electric signboard, liquid crystal backlight, lighting display, lighting equipment cover, traffic sign It becomes a molded article suitable for automobile parts such as sign boards, screens, reflectors and meter parts, and OA equipment parts.
以下、本発明を詳細に説明する。なお、本明細書において「〜」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
［ポリカーボネート樹脂組成物］
本発明のポリカーボネート樹脂組成物は、以下のＡ〜Ｃ成分を所定の割合で含有することを特徴とする。
ポリカーボネート樹脂（Ａ成分）：
本発明で用いるポリカーボネート樹脂（Ａ成分）としては特に制限されず、芳香族ポリカーボネート、脂肪族ポリカーボネート、芳香族−脂肪族ポリカーボネートのいずれも用いることができる。中でも芳香族ポリカーボネートが好ましく、さらに、芳香族ジヒドロキシ化合物をホスゲン又は炭酸のジエステルと反応させることによって得られる熱可塑性芳香族ポリカーボネート重合体又は共重合体がより好ましい。
Hereinafter, the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
[Polycarbonate resin composition]
The polycarbonate resin composition of the present invention is characterized by containing the following components A to C in a predetermined ratio.
Polycarbonate resin (component A):
The polycarbonate resin (component A) used in the present invention is not particularly limited, and any of an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-aliphatic polycarbonate can be used. Among them, an aromatic polycarbonate is preferable, and a thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic dihydroxy compound with phosgene or a carbonic acid diester is more preferable.
該芳香族ジヒドロキシ化合物としては、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）、テトラメチルビスフェノールＡ、ビス（４−ヒドロキシフェニル）−Ｐ−ジイソプロピルベンゼン、ハイドロキノン、レゾルシノール、４，４−ジヒドロキシジフェニルなどが挙げられ、好ましくはビスフェノールＡが挙げられる。さらに、難燃性が高い組成物を調製する目的で、上記の芳香族ジヒドロキシ化合物にスルホン酸テトラアルキルホスホニウムが１個以上結合した化合物、又はシロキサン構造を有する両末端フェノール性ＯＨ基含有のポリマーもしくはオリゴマー等を、使用することができる。 Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4, 4-dihydroxydiphenyl etc. are mentioned, Preferably bisphenol A is mentioned. Further, for the purpose of preparing a composition having a high flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a polymer containing both terminal phenolic OH groups having a siloxane structure or Oligomers and the like can be used.
本発明で用いるポリカーボネート樹脂（Ａ成分）の好ましい例には、２，２−ビス（４−ヒドロキシフェニル）プロパンから誘導されるポリカーボネート樹脂；２，２−ビス（４−ヒドロキシフェニル）プロパンと他の芳香族ジヒドロキシ化合物とから誘導されるポリカーボネート共重合体；が含まれる。本発明では、Ａ成分として、２種以上のポリカーボネート樹脂を併用してもよい。 Preferred examples of the polycarbonate resin (component A) used in the present invention include polycarbonate resins derived from 2,2-bis (4-hydroxyphenyl) propane; 2,2-bis (4-hydroxyphenyl) propane and other Polycarbonate copolymers derived from aromatic dihydroxy compounds. In the present invention, two or more polycarbonate resins may be used in combination as the component A.
ポリカーボネート樹脂（Ａ成分）の分子量は、溶媒としてメチレンクロライドを用い、温度２５℃で測定された溶液粘度より換算した粘度平均分子量で、１４，０００〜３０，０００であるのが好ましく、１５，０００〜２８，０００であるのがより好ましく、１６，０００〜２６，０００であるのがさらに好ましい。粘度平均分子量が前記範囲であると、機械的強度がより良好となり、且つ成形性もより良好となるので好ましい。 The molecular weight of the polycarbonate resin (component A) is preferably 14,000 to 30,000 in terms of viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, and 15,000. It is more preferably ˜28,000, and further preferably 16,000 to 26,000. It is preferable for the viscosity average molecular weight to be in the above range since the mechanical strength becomes better and the moldability becomes better.
前記ポリカーボネート樹脂の製造方法については、特に限定されるものではなく、本発明には、ホスゲン法（界面重合法）、及び溶融法（エステル交換法）等の、いずれの方法で製造したポリカーボネート樹脂も使用することができる。また、本発明には、一般的な溶融法の製造工程を経た後に、末端基のＯＨ基量を調整する工程を経て製造されたポリカーボネート樹脂を使用してもよい。 The method for producing the polycarbonate resin is not particularly limited, and the present invention also includes a polycarbonate resin produced by any method such as a phosgene method (interfacial polymerization method) and a melting method (transesterification method). Can be used. Moreover, you may use the polycarbonate resin manufactured through the process of adjusting the amount of OH groups of a terminal group, after passing through the manufacturing process of a general melting method in this invention.
さらに、本発明で用いるポリカーボネート樹脂（Ａ成分）は、バージン原料としてのポリカーボネート樹脂のみならず、使用済みの製品から再生されたポリカーボネート樹脂、いわゆるマテリアルリサイクルされたポリカーボネート樹脂、であってもよい。使用済みの製品としては、光学ディスクなどの光記録媒体、導光板、自動車窓ガラスや自動車ヘッドランプレンズ、風防などの車両透明部材、水ボトルなどの容器、メガネレンズ、防音壁やガラス窓、波板などの建築部材などが好ましく挙げられる。また、再生ポリカーボネート樹脂の形態についても特に制限されず、製品の不適合品、スプルー、又はランナーなどの粉砕品、及びそれらを溶融して得たペレットなどいずれも使用可能である。 Further, the polycarbonate resin (component A) used in the present invention may be not only a polycarbonate resin as a virgin raw material but also a polycarbonate resin regenerated from a used product, a so-called material recycled polycarbonate resin. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. Further, the form of the recycled polycarbonate resin is not particularly limited, and any non-conforming product, pulverized product such as sprue or runner, and pellets obtained by melting them can be used.
Ｂ成分 酸化イットリウム系蛍光体：
本発明の樹脂組成物は、赤色発色性に優れた酸化イットリウム系蛍光体（Ｂ成分）を含有する。酸化イットリウム系蛍光体の例には、Ｙ2Ｏ3：Ｅｕ、Ｙ2Ｏ2Ｓ：Ｅｕ、（Ｙ、Ｇｄ）ＢＯ3：Ｅｕ、ＹＢＯ3：Ｅｕ、（Ｙ、Ｌａ）2Ｏ3：Ｅｕ、及びＹＶＯ4：Ｅｕなどが含まれる。これらの酸化イットリウム系蛍光体（Ｂ成分）として、市販品を用いてもよく、例えば、根本特殊化学（株）よりネモトＵＶ蛍光体／Ｄ１１２０の商品名・グレード名で市販されているもの、デイグロ社よりＰｈａｎｔｏｍＰｉｇｍｅｎｔｓ／ＩＰＯ１３の商品名・グレード名で市販されているものを使用できる。
B component Yttrium oxide phosphor:
The resin composition of the present invention contains an yttrium oxide phosphor (component B) excellent in red color development. Examples of the yttrium oxide phosphor include Y 2 O 3 : Eu, Y 2 O 2 S: Eu, (Y, Gd) BO 3 : Eu, YBO 3 : Eu, (Y, La) 2 O 3 : Eu. , And YVO 4 : Eu. As these yttrium oxide phosphors (component B), commercially available products may be used. For example, those commercially available under the trade name / grade name of Nemoto UV phosphor / D1120 from Nemoto Special Chemical Co., Ltd. Commercially available products under the trade name / grade name of Phantom Pigments / IPO13 can be used.
本発明で用いる酸化イットリウム系蛍光体（Ｂ成分）の平均粒径は、０．１〜１０μｍが好ましく、０．３〜５μｍがより好ましい。なお、酸化イットリウム系蛍光体の粒径は、ストークス径の粒度分布測定法により測定することができる。Ｂ成分として、酸化イットリウム系蛍光体の１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The average particle diameter of the yttrium oxide phosphor (component B) used in the present invention is preferably from 0.1 to 10 μm, more preferably from 0.3 to 5 μm. The particle size of the yttrium oxide phosphor can be measured by a Stokes diameter particle size distribution measurement method. As the component B, one type of yttrium oxide phosphor may be used alone, or two or more types may be used in combination.
Ｃ成分 シラン化合物及び／又はシリコーン化合物：
本発明に用いるシラン化合物（Ｃ）としては、アルコキシ基を有するシラン化合物；ビニル基、アクリル基、メタクリル基、エポキシ基、アミノ基等の反応性の官能基を有するシラン化合物；フェニル基の様な通常反応性のない基を有するシラン化合物；等が挙げられる。また、アルコキシシランと称される無機物質の表面改質や樹脂の改質剤等に用いられているシラン化合物；及びビニルシラン、アクリルシラン、エポキシシラン等の充填剤等のカップリング剤として使用されるシラン化合物；等も好ましい。
Component C Silane compound and / or silicone compound:
As the silane compound (C) used in the present invention, a silane compound having an alkoxy group; a silane compound having a reactive functional group such as a vinyl group, an acrylic group, a methacryl group, an epoxy group, or an amino group; Examples thereof include silane compounds having a group that is usually not reactive. Also used as a coupling agent for fillers such as vinyl silane, acrylic silane, and epoxy silane; and silane compounds used for surface modification of inorganic substances called alkoxysilanes and resin modifiers; Silane compounds; etc. are also preferred.
中でも、下記式（１）で表されるシラン化合物が好ましい。
（Ｒ1Ｏ）nＳｉ（Ｒ2）(4-n) （１）
式中、Ｒ1は、Ｃ1〜4の脂肪族炭化水素基であり、Ｒ2は、Ｃ6〜12の芳香族もしくは脂環式炭化水素基、Ｃ1〜12の脂肪族炭化水素基、Ｃ2〜16のエチレン性不飽和炭化水素基、又はＣ3〜15のエポキシ基を有する有機基であり、好ましくは、Ｃ1〜4の脂肪族炭化水素基、Ｃ6〜12の芳香族炭化水素基、Ｃ2〜16のエチレン性不飽和炭化水素基又はＣ3〜15のエポキシ基を有する有機基であり、ｎは１〜３である。
Among these, a silane compound represented by the following formula (1) is preferable.
(R 1 O) n Si (R 2 ) (4-n) (1)
In the formula, R 1 is an aliphatic hydrocarbon group of C 1 ~ 4, R 2 is C 6 aromatic or alicyclic hydrocarbon group having 1-12, aliphatic hydrocarbon group of C 1 ~ 12, ethylenically unsaturated hydrocarbon group of C 2 ~ 16, or an organic group having an epoxy group of C 3 ~ 15, preferably an aliphatic hydrocarbon group of C 1 ~ 4, aromatic C 6 ~ 12 carbon hydrogen group, an organic group having an ethylenically unsaturated hydrocarbon group or a C 3 ~ 15 epoxy groups of the C 2 ~ 16, n is 1-3.
Ｃ6〜12の芳香族若しくは脂環式炭化水素基としては、フェニル基、シクロヘキシル基などが挙げられ、Ｃ1〜12の脂肪族炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、デシル基などが挙げられ、Ｃ2〜16のエチレン性不飽和炭化水素基としては、ビニル基、アリル基、イソプロペニル基、ブテニル基、メタクリロキシプロピル基、アクリロシキプロピル基などが挙げられ、Ｃ3〜15のエポキシ基を有する有機基としては、３，４−エポキシシクロヘキシル基、グリシドキシプロピル基などが挙げられる。 The aromatic or cycloaliphatic hydrocarbon radical of C 6 ~ 12, a phenyl group, and cyclohexyl group. Examples of the aliphatic hydrocarbon group of C 1 ~ 12, a methyl group, an ethyl group, a propyl group, butyl group, isobutyl group, decyl group, and examples of the ethylenically unsaturated hydrocarbon group of C 2 ~ 16, vinyl group, allyl group, isopropenyl group, butenyl group, methacryloxypropyl group, acryloxypropyl Shiki propyl and the like, Examples of the organic group having an epoxy group of C 3 ~ 15, 3,4-epoxycyclohexyl group, and the like glycidoxypropyl group.
本発明で用いるシラン化合物（Ｃ）の具体例としては、メチルトリメトキシシラン、オクチルトリメトキシシラン、デシルトリメトキシシラン、ジメチルジメトキシシラン、メチルトリエトキシシラン、トリメチルメトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、β−（３，４エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、フェニルトリメトキシシランなどが挙げられる。Ｃ成分として、シラン化合物の一種を単独で、又は二種以上を混合して用いることができる。 Specific examples of the silane compound (C) used in the present invention include methyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, isobutyltrimethoxysilane, vinyltri Methoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, phenyltrimethoxysilane, and the like. As the component C, one kind of silane compound can be used alone, or two or more kinds can be mixed and used.
本発明に用いるシリコーン化合物（Ｃ）としては、ポリオルガノハイドロジェンシロキサン類、及びオルガノポリシロキサン類のいずれであってもよい。また、その分子量についても特に制限されず、オリゴマー及びポリマーのいずれの群に属するものであってもよい。より具体的には、特公昭６３−２６１４０号公報に記載されている式（イ）〜式（ハ）で表されるポリオルガノハイドロジェンシロキサン類、及び特公昭６３−３１５１３号公報に記載されている式（ｂ）で表される炭化水素オキシシロキサン類などが好ましい。Ｃ成分として用いるシリコーン化合物は、ポリオルガノハイドロジェンシロキサン類から選択されるのが好ましい。例えば、下記式（Ｉ）を繰り返し単位とするポリシロキサン、ならびに式（II）及び（III）で表される化合物を用いるのが好ましい。
式（Ｉ）
（Ｒ）a（Ｈ）bＳｉＯ((4-a-b)/2)
上記（Ｉ）式中、ＲはＣ1〜10の直鎖状又は分岐状のアルキル基であり、ａ及びｂは４以下の整数である。
The silicone compound (C) used in the present invention may be any of polyorganohydrogensiloxanes and organopolysiloxanes. The molecular weight is not particularly limited, and may belong to any group of oligomers and polymers. More specifically, the polyorganohydrogensiloxanes represented by the formulas (A) to (C) described in JP-B-63-26140 and JP-B-63-31513 are described. Hydrocarbon oxysiloxanes represented by the formula (b) are preferred. The silicone compound used as component C is preferably selected from polyorganohydrogensiloxanes. For example, it is preferable to use polysiloxane having the following formula (I) as a repeating unit and compounds represented by formulas (II) and (III).
Formula (I)
(R) a (H) b SiO ((4-ab) / 2)
In the above formula (I), R is a linear or branched alkyl group of C 1 ~ 10, a and b is an integer of 4 or less.
式（ＩＩ）
上記式（II）中、Ａ及びＢは各々以下の群から選ばれる基であり、ｎは１〜５００の整数である。 In said formula (II), A and B are groups respectively selected from the following groups, and n is an integer of 1-500.
式（III）
上記式（III）中、Ａ及びＢは前記式（II）中におけるそれぞれと同義であり、ｍは１〜５０の整数である。 In said formula (III), A and B are synonymous with each in said Formula (II), and m is an integer of 1-50.
前記シリコーン化合物として市販品を用いてもよく、例えば、ＳＨ１１０７(東レ・ダウコーニング・シリコーン（株）製品等の商品名で市販されているシリコーンオイルを用いてもよい。
なお、本発明では、Ｃ成分として、シリコーン化合物の一種を単独で、又は二種以上を混合して用いることができる。
A commercially available product may be used as the silicone compound. For example, a silicone oil marketed under the trade name of SH1107 (Toray Dow Corning Silicone Co., Ltd.) may be used.
In the present invention, as the component C, one kind of silicone compound can be used alone, or two or more kinds can be mixed and used.
本発明の熱可塑性樹脂組成物は、ポリカーボネート樹脂（Ａ成分）を１００重量部、酸化イットリウム系蛍光体（Ｂ成分）を０．１〜５０重量部、及びシラン化合物及び／又はシリコーン化合物（Ｃ成分）をＢ成分の０．５〜１０重量％含有する。Ｂ成分の含有量が０．１重量部未満では、発光が弱くなり、５０重量部を越えると熱可塑性樹脂組成物の機械的強度や熱安定性が低下する。Ｂ成分の好ましい混合量は０．３〜２０重量部であり、より好ましい混合量は０．５〜１０重量部である。また、本発明の熱可塑性樹脂組成物において、Ｃ成分の含有量がＢ成分の含有量の０．５重量％未満であると、熱可塑性樹脂組成物の熱安定性が低下し、さらに、機械的強度、色相、耐熱性及び耐湿熱性も低下する。Ｃ成分の混合量が１０重量％を越えると溶融混練時にガスが発生し、モールドデボジットの原因となりやすい。Ｃ成分の好ましい含有量は、Ｂ成分の１〜９重量％である。 The thermoplastic resin composition of the present invention comprises 100 parts by weight of polycarbonate resin (component A), 0.1 to 50 parts by weight of yttrium oxide phosphor (component B), and a silane compound and / or silicone compound (component C). ) In an amount of 0.5 to 10% by weight of component B. When the content of the B component is less than 0.1 parts by weight, the light emission becomes weak, and when it exceeds 50 parts by weight, the mechanical strength and thermal stability of the thermoplastic resin composition are lowered. A preferable mixing amount of the component B is 0.3 to 20 parts by weight, and a more preferable mixing amount is 0.5 to 10 parts by weight. Further, in the thermoplastic resin composition of the present invention, when the content of the C component is less than 0.5% by weight of the content of the B component, the thermal stability of the thermoplastic resin composition decreases, and further, the machine The strength, hue, heat resistance, and heat and humidity resistance are also reduced. If the mixing amount of component C exceeds 10% by weight, gas is generated during melt-kneading, which tends to cause mold deposit. The preferred content of component C is 1 to 9% by weight of component B.
他の添加剤：
本発明の熱可塑性樹脂組成物は、本発明の効果を損なわない範囲で、種々の添加剤から選ばれる一種又は二種以上を含有していてもよい。添加剤としては、難燃剤、滴下防止剤、熱安定剤、酸化防止剤、紫外線吸収剤、離型剤及び着色剤からなる群から選ばれる添加剤が好ましい。
Other additives:
The thermoplastic resin composition of the present invention may contain one or more selected from various additives within a range not impairing the effects of the present invention. As the additive, an additive selected from the group consisting of a flame retardant, an anti-dripping agent, a heat stabilizer, an antioxidant, an ultraviolet absorber, a release agent, and a colorant is preferable.
難燃剤：
本発明の熱可塑性樹脂組成物には、難燃性を付与するために難燃剤を添加するのが好ましい。難燃剤としては、組成物の難燃性を向上させるものであれば特に限定されないが、リン酸エステル化合物及び有機スルホン酸金属塩が好適である。前記リン酸エステル化合物としては、例えば、下記式（２）で表される化合物が好ましい。
Flame retardants:
It is preferable to add a flame retardant to the thermoplastic resin composition of the present invention in order to impart flame retardancy. The flame retardant is not particularly limited as long as it improves the flame retardancy of the composition, but a phosphoric acid ester compound and an organic sulfonic acid metal salt are preferable. As the phosphoric ester compound, for example, a compound represented by the following formula (2) is preferable.
前記式（２）中、Ｒ1、Ｒ2、Ｒ3及びＲ4は互いに独立して、置換されていてもよいアリール基を示し、Ｘは他に置換基を有していても良い２価の芳香族基を示す。ｎは０〜５の数を示す。
上記式（２）においてＲ1〜Ｒ4で示されるアリール基としては、フェニル基、ナフチル基等が挙げられる。またＸで示される２価の芳香族基としては、フェニレン基、ナフチレン基や、例えばビスフェノールから誘導される基等が挙げられる。これらの置換基としては、アルキル基、アルコキシ基、ヒドロキシ基等が挙げられる。ｎが０の場合はリン酸エステルであり、ｎが０より大きい場合は縮合リン酸エステル（混合物を含む）である。
In the formula (2), R 1 , R 2 , R 3 and R 4 each independently represent an optionally substituted aryl group, and X represents a divalent optionally further substituted group. An aromatic group of n shows the number of 0-5.
In the above formula (2), examples of the aryl group represented by R 1 to R 4 include a phenyl group and a naphthyl group. Examples of the divalent aromatic group represented by X include a phenylene group, a naphthylene group, and a group derived from, for example, bisphenol. Examples of these substituents include an alkyl group, an alkoxy group, and a hydroxy group. When n is 0, it is a phosphate ester, and when n is greater than 0, it is a condensed phosphate ester (including a mixture).
具体的には、ビスフェノールＡビスホスフェート、ヒドロキノンビスホスフェート、レゾルシンビスホスフェート、レゾルシノール−ジフェニルホスフェート、あるいはこれらの置換体、縮合体などを例示できる。かかる成分として好適に用いることができる市販の縮合リン酸エステル化合物としては、たとえば、大八化学工業（株）より、「ＣＲ７３３Ｓ」（レゾルシノールビス（ジフェニルホスフェート））、「ＣＲ７４１」（ビスフェノールＡビス（ジフェニルホスフェート））、旭電化工業（株）より「ＦＰ５００」（レゾルシノールビス（ジキシレニルホスフェート））といった商品名で販売されており、容易に入手可能である。 Specific examples include bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, and substituted and condensates thereof. Examples of commercially available condensed phosphate compounds that can be suitably used as such components include, for example, “CR733S” (resorcinol bis (diphenyl phosphate)), “CR741” (bisphenol A bis ( Diphenyl phosphate)) and Asahi Denka Kogyo Co., Ltd. under the trade name “FP500” (resorcinol bis (dixylenyl phosphate)) and are readily available.
本発明の熱可塑性樹脂組成物における難燃剤用のリン酸エステル化合物の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対し１〜５０重量部であるのが好ましく、３〜４０重量部であるのがより好ましく、５〜３０重量部であるのがさらに好ましい。難燃剤用リン酸エステル化合物の含有量が前記範囲であると、難燃性があり、且つ耐熱性も良好な樹脂組成物となるので好ましい。
本発明において使用可能な難燃剤用の有機スルホン酸金属塩としては、好ましくは脂肪族スルホン酸金属塩及び芳香族スルホン酸金属塩等が挙げられる。有機スルホン酸金属塩を構成する金属としては、好ましくは、アルカリ金属、アルカリ土類金属などが挙げられ、アルカリ金属及びアルカリ土類金属としては、ナトリウム、リチウム、カリウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム及びバリウム等が挙げられる。有機スルホン酸金属塩は、２種以上の塩を混合して使用することもできる。
The content of the phosphoric acid ester compound for the flame retardant in the thermoplastic resin composition of the present invention is preferably 1 to 50 parts by weight, and 3 to 40 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A). More preferably, it is 5 to 30 parts by weight. It is preferable for the content of the phosphoric acid ester compound for the flame retardant to be in the above range because the resin composition has flame retardancy and good heat resistance.
Preferred examples of the organic sulfonic acid metal salt for flame retardant that can be used in the present invention include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. The metal constituting the organic sulfonic acid metal salt is preferably an alkali metal, an alkaline earth metal, etc., and the alkali metal and the alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium. , Calcium, strontium and barium. The organic sulfonic acid metal salt can also be used by mixing two or more kinds of salts.
該脂肪族スルホン酸塩としては、好ましくは、フルオロアルカン−スルホン酸金属塩、より好ましくは、パーフルオロアルカン−スルホン酸金属塩が挙げられる。フルオロアルカン−スルホン酸金属塩としては、好ましくは、フルオロアルカン−スルホン酸のアルカリ金属塩、フルオロアルカン−スルホン酸のアルカリ土類金属塩などが挙げられ、より好ましくは、炭素数４〜８のフルオロアルカンスルホン酸のアルカリ金属塩、アルカリ土類金属塩などが挙げられる。該フルオロアルカン−スルホン酸金属塩の具体例としては、パーフルオロブタン−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、パーフルオロメチルブタン−スルホン酸ナトリウム、パーフルオロメチルブタン−スルホン酸カリウム、パーフルオロオクタン−スルホン酸ナトリウム、パーフルオロオクタン−スルホン酸カリウムなどが挙げられる。 The aliphatic sulfonate preferably includes a fluoroalkane-sulfonic acid metal salt, and more preferably a perfluoroalkane-sulfonic acid metal salt. Preferred examples of the fluoroalkane-sulfonic acid metal salt include an alkali metal salt of fluoroalkane-sulfonic acid, an alkaline earth metal salt of fluoroalkane-sulfonic acid, and more preferably, a fluoroalkane having 4 to 8 carbon atoms. Examples include alkali metal salts and alkaline earth metal salts of alkanesulfonic acid. Specific examples of the fluoroalkane-sulfonic acid metal salt include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluoro Examples include octane-sodium sulfonate and potassium perfluorooctane-sulfonate.
また、芳香族スルホン酸金属塩としては、好ましくは、芳香族スルホン酸アルカリ金属塩、芳香族スルホン酸アルカリ土類金属塩、芳香族スルホンスルホン酸アルカリ金属塩、芳香族スルホンスルホン酸アルカリ土類金属塩などが挙げられ、芳香族スルホンスルホン酸アルカリ金属塩、芳香族スルホンスルホン酸アルカリ土類金属塩は重合体であってもよい。該芳香族スルホン酸金属塩の具体例としては、３，４−ジクロロベンゼンスルホン酸ナトリウム塩、２，４，５−トリクロロベンゼンスルホン酸ナトリウム塩、ベンゼンスルホン酸ナトリウム塩、ジフェニルスルホン−３−スルホン酸のナトリウム塩、ジフェニルスルホン−３−スルホン酸のカリウム塩、４，４'−ジブロモジフェニル−スルホン−３−スルホン酸のナトリウム塩、４，４'−ジブロモジフェニル−スルホン−３−スルホン酸のカリウム塩、４−クロロ−４'−ニトロジフェニルスルホン−３−スルホン酸のカルシウム塩、ジフェニルスルホン−３，３'−ジスルホン酸のジナトリウム塩、ジフェニルスルホン−３，３'−ジスルホン酸のジカリウム塩などが挙げられる。 The aromatic sulfonic acid metal salt is preferably an aromatic sulfonic acid alkali metal salt, an aromatic sulfonic acid alkaline earth metal salt, an aromatic sulfone sulfonic acid alkali metal salt, or an aromatic sulfone sulfonic acid alkaline earth metal. Salts, and the like, and the aromatic sulfonesulfonic acid alkali metal salt and the aromatic sulfonesulfonic acid alkaline earth metal salt may be a polymer. Specific examples of the aromatic sulfonic acid metal salt include 3,4-dichlorobenzenesulfonic acid sodium salt, 2,4,5-trichlorobenzenesulfonic acid sodium salt, benzenesulfonic acid sodium salt, diphenylsulfone-3-sulfonic acid. Sodium salt, potassium salt of diphenylsulfone-3-sulfonic acid, sodium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid, potassium salt of 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid calcium salt, diphenylsulfone-3,3′-disulfonic acid disodium salt, diphenylsulfone-3,3′-disulfonic acid dipotassium salt, and the like. Can be mentioned.
本発明の熱可塑性樹脂組成物における、難燃剤用の有機スルホン酸金属塩の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対し、０．０１〜５重量部であるのが好ましく、０．０２〜３重量部であるのがより好ましく、０．０３〜２重量部であるのがさらに好ましい。難燃剤用有機スルホン酸金属塩の含有量が前記範囲であると、難燃性があり、且つ熱安定性が良好な樹脂組成物となるので好ましい。 The content of the organic sulfonic acid metal salt for flame retardant in the thermoplastic resin composition of the present invention is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A). The amount is more preferably 0.02 to 3 parts by weight, and still more preferably 0.03 to 2 parts by weight. It is preferable for the content of the organic sulfonic acid metal salt for flame retardant to be in the above-mentioned range since the resin composition has flame retardancy and good thermal stability.
滴下防止剤：
また、本発明の熱可塑性樹脂組成物には、燃焼時の滴下防止を目的として、滴下防止剤を添加してもよい。滴下防止剤の好ましい例として、フッ素樹脂が挙げられる。より具体的には、ジフルオロエチレン重合体、テトラフルオロエチレン重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、テトラフルオロエチレンとフッ素を含まないエチレン系モノマーとの共重合体等のフルオロエチレン構造を含む重合体及び共重合体である。中でも、ポリテトラフルオロエチレン（ＰＴＦＥ）が好ましい。その平均分子量は、５００，０００以上であるのが好ましく、５００，０００〜１０，０００，０００であるのがより好ましい。
Anti-dripping agent:
Moreover, you may add a dripping inhibitor to the thermoplastic resin composition of this invention for the purpose of dripping prevention at the time of combustion. A preferable example of the anti-dripping agent is a fluororesin. More specifically, a fluoroethylene structure such as a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, or a copolymer of tetrafluoroethylene and an ethylene monomer not containing fluorine is used. Including polymers and copolymers. Among these, polytetrafluoroethylene (PTFE) is preferable. The average molecular weight is preferably 500,000 or more, more preferably 500,000 to 10,000,000.
なお、ポリテトラフルオロエチレンのうち、フィブリル形成能を有するものを用いると、さらに高い溶融滴下防止性を付与することができる。フィブリル形成能を有するポリテトラフルオロエチレン（ＰＴＦＥ）には特に制限はないが、例えば、ＡＳＴＭ規格において、タイプ３に分類されるものが挙げられる。その具体例としては、テフロン（登録商標）６−Ｊ（三井・デュポンフロロケミカル（株）製）、ポリフロンＤ−１、ポリフロンＦ−１０３、ポリフロンＦ２０１（ダイキン工業（株）製）、ＣＤ０７６（旭アイシーアイフロロポリマーズ（株）製）等が挙げられる。また、上記タイプ３に分類されるもの以外では、例えばアルゴフロンＦ５（モンテフルオス（株）製）、ポリフロンＭＰＡ、ポリフロンＦＡ−１００（ダイキン工業（株）製）等が挙げられる。これらのポリテトラフルオロエチレン（ＰＴＦＥ）は、単独で用いてもよいし、２種以上を組み合わせてもよい。上記のようなフィブリル形成能を有するポリテトラフルオロエチレン（ＰＴＦＥ）は、例えばテトラフルオロエチレンを水性溶媒中で、ナトリウム、カリウム、アンモニウムパーオキシジスルフィドの存在下で、１〜１００ｐｓｉの圧力下、温度０〜２００℃、好ましくは２０〜１００℃で重合させることによって得られる。 In addition, when polytetrafluoroethylene having a fibril forming ability is used, it is possible to impart higher melt dripping prevention property. Although there is no restriction | limiting in particular in the polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTM standard is mentioned. Specific examples thereof include Teflon (registered trademark) 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries, Ltd.), CD076 (Asahi) Ic eye fluoropolymers Co., Ltd.). Other than those classified as type 3, for example, Argoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned. These polytetrafluoroethylene (PTFE) may be used independently and may combine 2 or more types. Polytetrafluoroethylene (PTFE) having the fibril-forming ability as described above is prepared by, for example, using tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, at a pressure of 1 to 100 psi, at a temperature of 0. It is obtained by polymerizing at ˜200 ° C., preferably 20˜100 ° C.
本発明の熱可塑性樹脂組成物における、滴下防止剤の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対し、０．０５〜２重量部であるのが好ましく、０．１〜１重量部であるのがより好ましい。滴下防止剤の含有量が前記範囲であると、成形品の外観を損なうことなく、滴下防止性が良好となるので好ましい。 The content of the anti-dripping agent in the thermoplastic resin composition of the present invention is preferably 0.05 to 2 parts by weight, and 0.1 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin (component A). It is more preferable that It is preferable for the content of the anti-dripping agent to be in the above-mentioned range since the anti-dripping property becomes good without impairing the appearance of the molded product.
熱安定剤：
本発明の熱可塑性樹脂組成物には、熱安定性を向上させるために熱安定剤を添加するのが好ましい。好ましい熱安定剤としては、亜リン酸エステル、リン酸エステル等のリン系熱安定剤が好ましい。上記の亜リン酸エステルとしては、例えば、トリ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、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリノニルホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジステアリルペンタエリスリトールジホスファイト、トリシクロヘキシルホスファイト、モノブチルジフエニルホスファイト、モノオクチルジフエニルホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールホスファイト、ビス（２．６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールホスファイト、２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト等の亜リン酸のトリエステル、ジエステル、モノエステル等が挙げられる。
Thermal stabilizer:
In order to improve thermal stability, it is preferable to add a thermal stabilizer to the thermoplastic resin composition of the present invention. As a preferable heat stabilizer, phosphorus-based heat stabilizers such as phosphites and phosphates are preferable. Examples of the phosphite include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonyl phosphite, tridecyl phosphite, and trioctyl. Phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tricyclohexyl phosphite, monobutyl diphenyl phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di -Tert-butylphenyl) pentaerythritol phosphite, bis (2.6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t rt- butylphenyl) triesters of phosphorous acid such as octyl phosphite, diesters, monoesters, and the like.
上記のリン酸エステルとしては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリス（ノニルフェニル）ホスフェート、２−エチルフェニルジフェニルホスフェート、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４−ジフエニレンホスフォナイト等が挙げられる。 Examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, tetrakis (2,4- And di-tert-butylphenyl) -4,4-diphenylene phosphonite.
上記のリン系熱安定剤の中では、ジステアリルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールホスファイト、ビス（２．６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールホスファイト、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイトが好ましく、中でもビス（２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールホスファイトやトリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイトが特に好ましい。なお、熱安定剤は、単独で使用してもよく、二種以上を組み合わせて使用してもよい。 Among the above phosphorus-based heat stabilizers, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2.6-di-tert-butyl-4) -Methylphenyl) pentaerythritol phosphite and tris (2,4-di-tert-butylphenyl) phosphite are preferred. Among them, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite and Tris (2,4-di-t-butylphenyl) phosphite is particularly preferred. In addition, a heat stabilizer may be used independently and may be used in combination of 2 or more type.
本発明の熱可塑性樹脂組成物における熱安定剤の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対し、通常０．００５〜０．２重量部程度であるのが好ましく、０．０１〜０．１重量部であるのがより好ましい。熱安定剤の含有量が前記範囲であると、加水分解等を発生させることなく、熱安定性を改善できるので好ましい。 The content of the heat stabilizer in the thermoplastic resin composition of the present invention is usually preferably about 0.005 to 0.2 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A). More preferably, it is 0.1 parts by weight. It is preferable for the content of the thermal stabilizer to be in the above-mentioned range since the thermal stability can be improved without causing hydrolysis or the like.
酸化防止剤：
また、本発明の熱可塑性樹脂組成物には、酸化防止剤を添加するが好ましい。酸化防止剤としては、フェノール系酸化防止剤が好ましく、より具体的には、２，６−ジ−オブチル−４−メチルフェノール、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、テトラキス［メチレン−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］メタン、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、４，４'−ブチリデンビス−（３−メチル−６−ｔ−ブチルフェノール）、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−ヒドロキシ−５−メチルフェニル）プロピオネート］、及び３，９−ビス｛２−［３−（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］−１，１−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン等が挙げられる。中でも、テトラキス［メチレン−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］メタンが好ましい。これらの酸化防止剤は一種を単独で用いてもよいし、二種以上を併用してもよい。
Antioxidant:
Moreover, it is preferable to add an antioxidant to the thermoplastic resin composition of the present invention. As the antioxidant, a phenolic antioxidant is preferable, and more specifically, 2,6-di-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-). Butyl-4'-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-t-butyl-4- Hydroxybenzyl) isocyanurate, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-hydroxy-5-methylphenyl) propionate], And 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl Ethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. Among them, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferable. These antioxidants may be used individually by 1 type, and may use 2 or more types together.
本発明の熱可塑性樹脂組成物における酸化防止剤の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対し、２００〜５０００ｐｐｍ程度であるのが好ましい。前記範囲であると、本発明の効果を阻害せずに、酸化防止性を改善できるので好ましい。 The content of the antioxidant in the thermoplastic resin composition of the present invention is preferably about 200 to 5000 ppm with respect to 100 parts by weight of the polycarbonate resin (component A). The above range is preferable because the antioxidant property can be improved without inhibiting the effects of the present invention.
紫外線吸収剤：
本発明の熱可塑性樹脂組成物には、紫外線吸収剤を添加するのが好ましい。成形品は、太陽光や蛍光灯のような光線下に長期間曝されると、紫外線によって黄色味を帯びる傾向があるが、紫外線を添加することで、成形品が黄色味を帯びるのを、防止又は遅延させることができる。紫外線吸収剤としては、ベンゾフェノン系、ベンゾトリアゾール系、サリチル酸フェニル系、ヒンダードアミン系などが挙げられる。
UV absorber:
It is preferable to add an ultraviolet absorber to the thermoplastic resin composition of the present invention. Molded products have a tendency to become yellowish due to ultraviolet rays when exposed to light such as sunlight or fluorescent lamps for a long time, but by adding ultraviolet rays, the molded product becomes yellowish. Can be prevented or delayed. Examples of the ultraviolet absorber include benzophenone, benzotriazole, phenyl salicylate, and hindered amine.
ベンゾフェノン系紫外線吸収剤の具体例としては、２，４−ジヒドロキシ−ベンゾフェノン、２−ヒドロキシ−４−メトキシ−ベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシ−ベンゾフェノン、２−ヒドロキシ−４−ドデシロキシ−ベンゾフェノン、２−ヒドロキシ−４−オクタデシロキシ−ベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシ−ベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシ−ベンゾフェノン、２，２’，４，４’−テトラヒドロキシ−ベンゾフェノン等が挙げられる。 Specific examples of benzophenone ultraviolet absorbers include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone. 2-hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4 And '-tetrahydroxy-benzophenone.
ベンゾトリアゾール系紫外線吸収剤の具体例としては、２−（２Ｈ−ベンゾトリアゾール−２−イル）−ｐ−クレゾール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４，６−ビス（１−メチル−１−フェニルメチル）フェノール、２−［５−クロロ（２Ｈ）−ベンゾトリアゾール−２−イル］−４−メチル−６−（ｔｅｒｔ−ブチル）フェノール、２，４−ジ−ｔｅｒｔ−ブチル−６−（５−クロロベンゾトリアゾール−２−イル）フェノール、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４−（１，１，３，３−テトラブチル）フェノール、２，２'−メチレンビス［６−（２Ｈ−ベンゾトリアゾール−２−イル）−４−（１，１，３，３−テトラブチル）フェノール］等が挙げられる。 Specific examples of the benzotriazole ultraviolet absorber include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1- Methyl-1-phenylmethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2,4-di-tert-butyl- 6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol, 2,2′-methylenebis [ 6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetrabutyl) phenol] and the like.
サリチル酸フェニル系紫外線吸収剤の具体例としては、フェニルサルチレート、２，４−ジターシャリーブチルフェニル−３，５−ジターシャリーブチル−４一ヒドロキシベンゾエート等が挙げられる。ヒンダードアミン系紫外線吸収剤の具体例としては、ビス（２，２，６，６−テトラメチルピペリジン−４−イル）セバケート等が挙げられる。 Specific examples of the phenyl salicylate UV absorber include phenyl saltylate, 2,4-ditertiary butylphenyl-3,5-ditertiary butyl-4 monohydroxybenzoate, and the like. Specific examples of the hindered amine ultraviolet absorber include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
本発明の熱可塑性樹脂組成物における紫外線吸収剤の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対して、０．０１〜２重量部であるのが好ましく、０．０５〜１．５重量部であるのがより好ましく、０．１〜１重量部であるのがさらに好ましい。紫外線吸収剤の含有量が前記範囲であると、調色性及び酸化イットリウム系蛍光体の励起光吸収による発色性の低下が生じず、且つ成形品表面にブリードアウト等を発生させずに、耐候性を改善できるので好ましい。 The content of the ultraviolet absorber in the thermoplastic resin composition of the present invention is preferably 0.01 to 2 parts by weight, and 0.05 to 1.5 parts per 100 parts by weight of the polycarbonate resin (component A). More preferably, it is 0.1 part by weight. When the content of the ultraviolet absorber is within the above range, the color resistance and the color development due to absorption of the excitation light of the yttrium oxide phosphor do not deteriorate, and the weather resistance does not occur on the surface of the molded product. It is preferable because the property can be improved.
離型剤：
本発明の熱可塑性樹脂組成物は、離型剤を含有するのが好ましい。好ましい離型剤は、脂肪族カルボン酸、脂肪族カルボン酸エステル、及び数平均分子量２００〜１５０００の脂肪族炭化水素化合物から選ばれる少なくとも１種の化合物である。中でも、脂肪族カルボン酸、及び脂肪族カルボン酸エステルから選ばれる少なくとも１種の化合物が好ましく用いられる。
Release agent:
The thermoplastic resin composition of the present invention preferably contains a release agent. A preferable mold release agent is at least one compound selected from an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, and an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000. Among these, at least one compound selected from aliphatic carboxylic acids and aliphatic carboxylic acid esters is preferably used.
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。本明細書では、脂肪族カルボン酸の用語は、脂環式カルボン酸も包含する意味で用いる。脂肪族カルボン酸の中でも、炭素数６〜３６のモノ又はジカルボン酸が好ましく、炭素数６〜３６の脂肪族飽和モノカルボン酸がより好ましい。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. In the present specification, the term “aliphatic carboxylic acid” is used to include alicyclic carboxylic acids. Among the aliphatic carboxylic acids, mono- or dicarboxylic acids having 6 to 36 carbon atoms are preferable, 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, mellic acid, and tetrariacontanoic 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。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。脂肪族カルボン酸エステルの具体例としては、蜜ロウ（ミリシ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アレート、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。離型剤は一種を単独で使用してもよいし、二種以上を併用してもよい。 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. 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. Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin Examples thereof include distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate. A mold release agent may be used individually by 1 type, and may use 2 or more types together.
本発明の熱可塑性樹脂組成物における離型剤の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対し、０．０１〜１重量部であるのが好ましい。離型剤の含有量が前記範囲であると、耐加水分解性の低下がなく、離型効果が得られるので好ましい。 The content of the release agent in the thermoplastic resin composition of the present invention is preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polycarbonate resin (component A). It is preferable for the content of the release agent to be in the above-mentioned range since there is no decrease in hydrolysis resistance and a release effect can be obtained.
着色剤：
本発明の熱可塑性樹脂組成物には、より視認性を高めるために着色剤を添加することが好ましい。使用可能な着色剤としては、無機顔料、有機顔料、有機染料等が挙げられる。無機顔料としては、例えばカーボンブラック、カドミウムレッド、カドミウムイエロー等の硫化物系顔料、群青等の珪酸塩系顔料、酸化チタン、亜鉛華、弁柄、酸化クロム、鉄黒、チタンイエロー、亜鉛−鉄系ブラウン、チタンコバルト系グリーン、コバルトグリーン、コバルトブルー、銅−クロム系ブラック、銅−鉄系ブラック等の酸化物系顔料、黄鉛、モリブデートオレンジ等のクロム酸系顔料、紺青等のフェロシアン系顔料等があげられる。有機顔料及び有機染料としては、銅フタロシアニンブルー、銅フタロシアニングリーン等のフタロシアニン系染顔料、ニッケルアゾイエロー等のアゾ系、チオインジゴ系、ペリノン系、ペリレン系、キナクリドン系、ジオキサジン系、イソインドリノン系、キノフタロン系等の縮合多環染顔料、アンスラキノン系、複素環系、メチル系の染顔料等が挙げられる。例えば、本発明のＡ成分、Ｂ成分、Ｃ成分と黄色の着色剤を同時に混合した組成物により、紫外線照射時の発光色を橙色に見せたり、本発明のＡ成分、Ｂ成分、Ｃ成分と青色の着色剤を同時に混合した組成物により、紫外線照射時の発光色を紫色に見せたりすることができる。
Colorant:
It is preferable to add a colorant to the thermoplastic resin composition of the present invention in order to enhance visibility. Examples of the colorant that can be used include inorganic pigments, organic pigments, and organic dyes. Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow, silicate pigments such as ultramarine blue, titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, and zinc-iron. -Based brown, titanium-cobalt green, cobalt-green, cobalt-blue, oxide-based pigments such as copper-chromium black, copper-iron-based black, chromic pigments such as yellow lead, molybdate orange, ferrocyans such as bitumen And pigments. As organic pigments and organic dyes, phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green, azo series such as nickel azo yellow, thioindigo series, perinone series, perylene series, quinacridone series, dioxazine series, isoindolinone series, Examples thereof include condensed polycyclic dyes such as quinophthalone, anthraquinone, heterocyclic, and methyl dyes. For example, by using a composition in which the A component, B component, and C component of the present invention are mixed at the same time with a yellow colorant, the luminescent color upon irradiation with ultraviolet light is made orange, or the A component, B component, and C component of the present invention With the composition in which the blue colorant is mixed at the same time, the emission color upon irradiation with ultraviolet rays can be made purple.
本発明の熱可塑性樹脂組成物における着色剤の含有量の好ましい範囲は、着色目的と着色剤の種類によって異なる。例えば、反射板用に酸化チタンを使用する場合は、ポリカーボネート樹脂１００重量部に対して、着色剤の含有量は１〜３０重量部であるのが好ましい。一般的な用途における着色剤の配合量は、３重量部以下であるのが好ましく、１重量部以下であるのが好ましく、０．３重量部以下であるのがさらに好ましい。該着色剤は一種を単独で用いてもよいし、二種以上を併用してもよい。 The preferable range of the content of the colorant in the thermoplastic resin composition of the present invention varies depending on the purpose of coloring and the type of the colorant. For example, when titanium oxide is used for the reflector, the colorant content is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polycarbonate resin. The blending amount of the colorant in a general application is preferably 3 parts by weight or less, preferably 1 part by weight or less, and more preferably 0.3 parts by weight or less. The colorant may be used alone or in combination of two or more.
本発明の熱可塑性樹脂組成物には、必要に応じて本発明の目的を損なわない範囲で、上記成分のほかに、ポリカーボネート樹脂以外の熱可塑性樹脂、無機フィラー、有機又は無機の微粒子状光拡散剤、帯電防止剤、防曇剤、滑剤・アンチブロッキング剤、流動性改良剤、可塑剤、分散剤、防菌剤などを配合できる。これらは、一種類でも二種類以上を併用してもよい。 The thermoplastic resin composition of the present invention includes a thermoplastic resin other than the polycarbonate resin, an inorganic filler, organic or inorganic fine particle light diffusion, in addition to the above components, as long as the purpose of the present invention is not impaired as necessary. Agents, antistatic agents, antifogging agents, lubricants / antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents and the like can be blended. These may be used alone or in combination of two or more.
本発明の熱可塑性樹脂組成物は、従来から知られている方法で混合し、溶融混練することにより製造できる。具体的な混合方法としては、ポリカーボネート樹脂（Ａ成分）、酸化イットリウム系蛍光体（Ｂ成分）と、シラン化合物及び／又はシリコーン化合物（Ｃ成分）、必要に応じて配合される添加成分を所定量秤量し、タンブラーやヘンシェルミキサーなどの各種混合機を用いて混合する方法がある。中でも、Ｂ成分とＣ成分を予め混合後、Ａ成分および必要に応じて配合される添加成分を混合する方法が、Ｂ成分の表面活性を効果的に抑制し、熱可塑性樹脂組成物中で不必要な副反応を生じさせないという観点から、より好ましい混合方法である。上記方法で各成分を予め混合した後、溶融混練する方法としてはバンバリーミキサー、ロール、ブラベンダー、単軸混練押出機、二軸混練押出機、ニーダーなどを使用する方法が挙げられる。 The thermoplastic resin composition of the present invention can be produced by mixing and melt-kneading by a conventionally known method. As a specific mixing method, a predetermined amount of a polycarbonate resin (component A), an yttrium oxide phosphor (component B), a silane compound and / or a silicone compound (component C), and an additive component blended as necessary There is a method of weighing and mixing using various mixers such as a tumbler and a Henschel mixer. Among them, the method of mixing the B component and the C component in advance and then mixing the A component and the additive component blended as necessary effectively suppresses the surface activity of the B component, and is not effective in the thermoplastic resin composition. This is a more preferable mixing method from the viewpoint of not causing a necessary side reaction. Examples of a method for melt-kneading after mixing each component in advance by the above method include a method using a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader and the like.
本発明の熱可塑性樹脂組成物は、各種製品（成形品）の製造（成形）用樹脂材料として使用される。成形方法は、熱可塑性樹脂材料から成形品を成形する従来から知られている方法が、制限なく適用できる。具体的には、一般的な射出成形法、超高速射出成形法、射出圧縮成形法、二色成形法、ガスアシストなどの中空成形法、断熱金型を用いた成形法、急速加熱金型を用いた成形法、発泡成形（超臨界流体も含む）、インサート成形、インモールドコーティング（ＩＭＣ）成形法、押出成形法、シート成形法、熱成形法、回転成形法、積層成形法、プレス成形法などが挙げられる。 The thermoplastic resin composition of the present invention is used as a resin material for production (molding) of various products (molded products). As a molding method, a conventionally known method of molding a molded product from a thermoplastic resin material can be applied without limitation. Specifically, general injection molding methods, ultra-high speed injection molding methods, injection compression molding methods, two-color molding methods, hollow molding methods such as gas assist, molding methods using heat insulating molds, rapid heating molds Molding method used, foam molding (including supercritical fluid), insert molding, in-mold coating (IMC) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method Etc.
本発明では、シラン化合物及び／又はシリコーン化合物（Ｃ成分）を用いることにより、酸化イットリウム系蛍光体（Ｂ成分）の存在によって促進されるポリカーボネート樹脂の加工時の熱分解を抑制し、機械的強度及び耐熱性を改善するとともに、加熱による色相・赤色蛍光色相の変化を軽減している。ポリカーボネートの熱分解の程度は、流動性（Ｑ値 単位：×１０-2ｃｃ／ｓ）によって知ることができる。本発明の熱可塑性樹脂組成物のＱ値は、Ｂ成分及びＣ成分を含有しない標準樹脂組成物（Ａ成分及びその他の添加剤の種類及び配合割合は同一）のＱ値（Ｑ0）に対して、Ｑ0＋１００％以内であるのが好ましく、Ｑ0＋７０％以内であるのがより好ましく、ほぼ等しいのがさらに好ましい。
なお、Ｑ値は、高化式フローテスター（島津製作所製）を使用して、温度２８０℃、荷重１６０ｋｇｆ／ｃｍ2の条件下で、乾燥したペレット状の樹脂組成物について、単位時間あたりの流出量として測定される値とする。この際使用するオリフィスは、直径１ｍｍ×長さ１０ｍｍとする。
In the present invention, by using a silane compound and / or a silicone compound (component C), thermal decomposition during processing of the polycarbonate resin promoted by the presence of the yttrium oxide phosphor (component B) is suppressed, and mechanical strength is increased. In addition to improving heat resistance, changes in hue and red fluorescent hue due to heating are reduced. The degree of thermal decomposition of polycarbonate can be known from the fluidity (Q value unit: × 10 −2 cc / s). The Q value of the thermoplastic resin composition of the present invention is relative to the Q value (Q 0 ) of a standard resin composition that does not contain the B component and the C component (the types and blending ratios of the A component and other additives are the same). Thus, it is preferably within Q 0 + 100%, more preferably within Q 0 + 70%, and even more preferably substantially equal.
In addition, Q value is the outflow per unit time about the pellet-shaped resin composition dried using the Koka type flow tester (manufactured by Shimadzu Corporation) under the conditions of a temperature of 280 ° C. and a load of 160 kgf / cm 2. The value measured as a quantity. The orifice used at this time is 1 mm in diameter × 10 mm in length.
以下に本発明を実施例によって詳しく説明するが、本発明はこれらの範囲内に限定されるものではない。なお、以下の実施例および比較例において、配合量は重量部を意味する。また、実施例および比較例において使用した樹脂組成物の構成成分は、次の特性を有する。
（Ａ）芳香族ポリカーボネート樹脂：三菱エンジニアリングプラスチックス（株）製品「商品名：ユーピロン（登録商標）Ｓ−３０００Ｆ」（以下、「Ｓ−３０００」と略記する）、粘度平均分子量 ２２，０００
（Ｂ−１）酸化イットリウム系蛍光体１：赤色発光顔料、根本特殊化学（株）製「商品名：ネモトＵＶ蛍光体／Ｄ１１２０」
（Ｂ−２）酸化イットリウム系蛍光体２：乳酸「湘南和光純薬社製、試薬」０．３重量％を、イオン交換水２０ｇに溶解した水溶液に、シラン化合物２（Ｃ−２）を６ｇ添加・撹拌して、水分散液を得た。つぎに、１Ｌのビーカーに、上記紫外線発光材料１（Ｂ−１）成分１００ｇを仕込み、マグネットスターラーで攪拌しながら、シラン化合物２の水分散液を添加した。ついで、１００℃のホットプレート上で攪拌・混合を続け、水溶液を蒸発させることにより、予め表面処理された酸化イットリウム系蛍光体２（Ｂ−２）を得た。
（Ｃ−１）シラン化合物１：メチルトリメトキシシラン、純正化学（株）製試薬
（Ｃ−２）シラン化合物２：デシルトリメトキシシラン、信越化学工業（株）製「商品名：ＫＢＭ３１０３」
（Ｃ−３）シリコーンオイル：メチル水素シロキサン、東レ・ダウコーニング・シリコーン（株）製「商品名：ＳＨ１１０７」
（Ｄ）熱安定剤：クレジルジフェニルホスフェート、大八化学工業（株）製、「商品名：ＣＤＰ」
（Ｅ）離型剤：ペンタエリスリトールテトラステアレート、日本油脂（株）製「商品名：ユニスターＨ４７６」
EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these ranges. In the following examples and comparative examples, the blending amount means parts by weight. Moreover, the component of the resin composition used in the Example and the comparative example has the following characteristics.
(A) Aromatic polycarbonate resin: Mitsubishi Engineering Plastics Co., Ltd. product “trade name: Iupilon (registered trademark) S-3000F” (hereinafter abbreviated as “S-3000”), viscosity average molecular weight 22,000
(B-1) Yttrium oxide phosphor 1: red luminescent pigment, manufactured by Nemoto Special Chemical Co., Ltd. “trade name: Nemoto UV phosphor / D1120”
(B-2) Yttrium oxide phosphor 2: 6 g of silane compound 2 (C-2) was added to an aqueous solution in which 0.3% by weight of lactic acid “manufactured by Shonan Wako Pure Chemical Industries, Ltd.” was dissolved in 20 g of ion-exchanged water. Addition and stirring were performed to obtain an aqueous dispersion. Next, 100 g of the ultraviolet light emitting material 1 (B-1) component was charged into a 1 L beaker, and an aqueous dispersion of the silane compound 2 was added while stirring with a magnetic stirrer. Subsequently, stirring and mixing were continued on a hot plate at 100 ° C. to evaporate the aqueous solution, thereby obtaining a surface-treated yttrium oxide phosphor 2 (B-2) in advance.
(C-1) Silane compound 1: Methyltrimethoxysilane, a reagent manufactured by Junsei Chemical Co., Ltd. (C-2) Silane compound 2: Decyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd. “trade name: KBM3103”
(C-3) Silicone oil: methyl hydrogen siloxane, manufactured by Toray Dow Corning Silicone Co., Ltd. “Product Name: SH1107”
(D) Thermal stabilizer: Cresyl diphenyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd., “Product name: CDP”
(E) Release agent: Pentaerythritol tetrastearate, manufactured by Nippon Oil & Fats Co., Ltd. “Product Name: Unistar H476”
［実施例１〜４及び比較例１］
芳香族ポリカーボネート樹脂及び各種添加剤を表１に示す割合で配合し、タンブラーで２０分間混合後、スクリュー径４０ｍｍのベント付き単軸押出機（いすず化工機社製「ＳＶ−４０」）により、シリンダー温度２８０℃、スクリュー回転数７０ｒｐｍで混練し、押出されたストランドを切断してペレットを作製した。
得られたペレットを１２０℃、５時間乾燥後、射出成形機（名機製作所製「Ｍ１５０ＡＩＩ−ＳＪ」）にて、シリンダー温度２９０℃、金型温度８０℃、成形サイクル５０秒の条件で射出成形を行い、各種ＡＳＴＭ試験片および３ｍｍ厚の平板を作製した。このような方法で作製した成形品を、下記評価用の試験片として用い評価を行った。
[Examples 1 to 4 and Comparative Example 1]
Aromatic polycarbonate resin and various additives are blended in the proportions shown in Table 1, mixed with a tumbler for 20 minutes, and then cylindered with a single screw extruder with a screw diameter of 40 mm (“SV-40” manufactured by Isuzu Chemical Industries). The mixture was kneaded at a temperature of 280 ° C. and a screw rotation speed of 70 rpm, and the extruded strand was cut to produce pellets.
The obtained pellets are dried at 120 ° C. for 5 hours, and then injection molded on an injection molding machine (“M150AII-SJ” manufactured by Meiki Seisakusho) under the conditions of a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., and a molding cycle of 50 seconds. A variety of ASTM test pieces and a 3 mm thick flat plate were produced. The molded product produced by such a method was evaluated using the following test piece for evaluation.
[参考例]
芳香族ポリカーボネート樹脂に酸化イットリウム系蛍光体を添加しなかった他は、実施例及び比較例と同様な方法により、各種ＡＳＴＭ試験片および３ｍｍ厚の平板を作製した。後述の流動性（Ｑ値）、耐衝撃性、耐熱老化試験、耐湿熱試験の指標とする。特に、参考例に対するＱ値の上昇は、ポリカーボネート樹脂の分子量低下を意味する。
評価結果を表１に示す。
[Reference example]
Various ASTM test pieces and 3 mm-thick flat plates were prepared by the same method as in the Examples and Comparative Examples, except that the yttrium oxide phosphor was not added to the aromatic polycarbonate resin. It is used as an index for fluidity (Q value), impact resistance, heat aging test, and moist heat test described later. In particular, an increase in the Q value relative to the reference example means a decrease in the molecular weight of the polycarbonate resin.
The evaluation results are shown in Table 1.
［評価方法］
（１）流動性（Ｑ値）（単位：×１０-2ｃｃ／ｓ）：高化式フローテスター（島津製作所製）を使用して、温度２８０℃、荷重１６０ｋｇｆ／ｃｍ2の条件下で、乾燥したペレット状の樹脂組成物について、単位時間あたりの流出量Ｑ値を測定した。この際使用したオリフィスは、直径１ｍｍ×長さ１０ｍｍのものである。
（２）耐衝撃性（アイゾット衝撃強度）（単位：Ｊ／ｍ）：ＡＳＴＭ Ｄ２５６に準拠して、厚さ３．２ｍｍのノッチ付き試験片について、２３℃の温度でアイゾット衝撃強度（単位：Ｊ／ｍ）を測定した。数値が大きいほど、耐衝撃性が優れていることを意味する。
（３）全光線透過率： ＪＩＳ Ｋ−７１０５に準じ、３ｍｍ厚の平板を試験片とし、日本電色工業（株）製、ＮＤＨ−２０００型ヘイズメーターで測定した。
（４）Ｌ値、ＹＩ値： ＪＩＳ Ｋ−７１０５に準じ、３ｍｍ厚の平板を試験片とし、日本電色工業（株）製のＳＥ２０００型分光式色彩計で、反射法により測定した。
（５）耐熱老化試験： 試験片を１３０℃、空気雰囲気中で５００時間熱貯蔵し、この熱貯蔵前後のＹＩ値の変化をΔＹＩとして算出し、耐熱性の指標とした。
（６）耐湿熱性試験： プレッシャークッカー試験機（（株）平山製作所製、ＨＡＳＴＥＳＴ、ＭＯＤＥＬ ＰＣ−ＳIII）にて、試験片を１２０℃、圧力１ｋｇ／ｃｍ2、湿度１００％の水蒸気雰囲気中で１００時間処理し、試験片の変形の有無を観察して耐加水分解性の指標とした。
（７）ＵＶ照射時の色相（蛍光発光性): 全光線透過率の測定に用いた試験片と同じく３ｍｍ厚の試験片を作製し、松下電工（株）製蛍光灯マグネットライトに松下電工（株）製のブラックライト・ブルー（ＦＬ４ＢＬ−Ｂ：波長３５２ｎｍ）を装着した装置を用いてＵＶ照射を行い、蛍光発光の色相を、以下の４段階で目視により評価した。また、（５）の耐熱老化試験後の試験片にも同様の試験を行い、評価を行った。
○：蛍光発光の色調が明るく綺麗である。
△：蛍光発光の色調が少し暗く黄色味あり。
×：蛍光発光の色調が暗く黄色味が目立つ。
−：蛍光発光せず。
[Evaluation methods]
(1) Fluidity (Q value) (unit: × 10 −2 cc / s): Using a Koka type flow tester (manufactured by Shimadzu Corporation) under the conditions of a temperature of 280 ° C. and a load of 160 kgf / cm 2 , About the dried pellet-shaped resin composition, the outflow amount Q value per unit time was measured. The orifice used here has a diameter of 1 mm and a length of 10 mm.
(2) Impact resistance (Izod impact strength) (unit: J / m): According to ASTM D256, Izod impact strength (unit: J / M) was measured. The larger the value, the better the impact resistance.
(3) Total light transmittance: Measured with a NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K-7105, using a 3 mm-thick flat plate as a test piece.
(4) L value, YI value: According to JIS K-7105, a 3 mm-thick flat plate was used as a test piece, and this was measured by a reflection method using a SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd.
(5) Heat aging test: The test piece was heat-stored in an air atmosphere at 130 ° C. for 500 hours, and the change in the YI value before and after the heat storage was calculated as ΔYI, which was used as an index of heat resistance.
(6) Moisture and heat resistance test: Using a pressure cooker tester (manufactured by Hirayama Seisakusho Co., Ltd., HAESTEST, MODEL PC-SIII), the test piece was 120 ° C., pressure 1 kg / cm 2 and humidity 100% in a steam atmosphere for 100 hours. It was processed and the presence or absence of the deformation | transformation of the test piece was observed, and it was set as the hydrolysis resistance parameter | index.
(7) Hue during UV irradiation (fluorescence emission): A test piece having a thickness of 3 mm was prepared in the same manner as the test piece used for measuring the total light transmittance, and Matsushita Electric Works ( UV irradiation was performed using a device equipped with Black Light Blue (FL4BL-B: wavelength 352 nm) manufactured by Co., Ltd., and the hue of fluorescence was visually evaluated in the following four stages. Moreover, the same test was performed and evaluated on the test piece after the heat aging test of (5).
○: The color of fluorescent light emission is bright and beautiful.
Δ: Fluorescent color tone is slightly dark and yellowish.
X: The color tone of fluorescence emission is dark and yellowish is conspicuous.
-: No fluorescence emission.
表１に示す結果から、実施例１〜４は、参考例と同等の流動性を示し、分子量低下による流動性の上昇がないが、一方、Ｃ成分であるシラン化合物及びシリコーン化合物を含有しない比較例１では、分子量低下によって、流動性が上昇していることが理解できる。また、実施例１〜４は、比較例に比べて、アイゾット衝撃値や全光線透過率に優れ、成形品の色相も比較例に比べてＬ値（明るさ）が高く、ＹＩ値（黄味）が低く、外観が優れている。また、実施例１〜４は、耐熱老化性試験の影響も、比較例に比べて少なくて、耐熱老化性に優れている。更に、実施例１〜４は、耐湿熱性にも優れている。また、蛍光発光性も実施例１〜４のものは良好である。
即ち、実施例１〜４は、比較例１と比較して、耐衝撃性、色相、耐熱老化特性及び耐湿熱特性のいずれにも優れている。
From the results shown in Table 1, Examples 1 to 4 show fluidity equivalent to that of the Reference Example, and there is no increase in fluidity due to a decrease in molecular weight, but on the other hand, a comparison that does not contain the C component silane compound and silicone compound. In Example 1, it can be understood that the fluidity is increased by decreasing the molecular weight. Moreover, Examples 1-4 are excellent in an Izod impact value and a total light transmittance compared with a comparative example, and the hue of a molded article is high L value (brightness) compared with a comparative example, and YI value (yellowishness). ) Is low and the appearance is excellent. Moreover, Examples 1-4 have few influences of a heat aging resistance test compared with a comparative example, and are excellent in heat aging resistance. Furthermore, Examples 1-4 are excellent also in heat-and-moisture resistance. Moreover, the thing of Examples 1-4 is also favorable for fluorescence luminescent property.
That is, Examples 1-4 are excellent in all of impact resistance, hue, heat aging characteristics, and heat-and-moisture resistance characteristics as compared with Comparative Example 1.
本発明によれば、機械的強度、耐久性、耐湿性、ならびに非蛍光時及び蛍光時の色相に優れた、電飾看板、液晶バックライト、照明ディスプレイ、サインボード、スクリーン等の成形体を提供することができる。 According to the present invention, a molded body such as an electric signboard, a liquid crystal backlight, an illumination display, a signboard, and a screen, which is excellent in mechanical strength, durability, moisture resistance, and non-fluorescent and fluorescent hues is provided. can do.
Claims (5)
式（１）
（Ｒ 1 Ｏ） n Ｓｉ（Ｒ 2 ） (4-n) （１）
（式中、Ｒ 1 は、Ｃ 1 〜 4 の脂肪族炭化水素基であり、Ｒ 2 は、Ｃ 6 〜 12 の芳香族もしくは脂環式炭化水素基、Ｃ 1 〜 12 の脂肪族炭化水素基、Ｃ 2 〜 16 のエチレン性不飽和炭化水素基、又はＣ 3 〜 15 のエポキシ基を有する有機基であり、ｎは１〜３である。）
式（Ｉ）
（Ｒ） a （Ｈ） b ＳｉＯ ((4-a-b)/2)
（上記（Ｉ）式中、ＲはＣ 1 〜 10 の直鎖状又は分岐状のアルキル基であり、ａ及びｂは４以下の整数である。）
式（II）
Formula (1)
(R 1 O) n Si (R 2 ) (4-n) (1)
(In the formula, R 1 is an aliphatic hydrocarbon group of C 1 ~ 4, R 2 is C 6 aromatic or alicyclic hydrocarbon group having 1-12, aliphatic hydrocarbon group of C 1 ~ 12 , an organic group having a C 2 ~ 16 ethylenically unsaturated hydrocarbon group, or a C 3 ~ 15 epoxy group, n is 1-3.)
Formula (I)
(R) a (H) b SiO ((4-ab) / 2)
(In the above formula (I), R is a linear or branched alkyl group of C 1 ~ 10, a and b is an integer of 4 or less.)
Formula (II)
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| KR20140095110A (en) | 2012-06-06 | 2014-07-31 | 미쓰비시 엔지니어링-플라스틱스 코포레이션 | Resin composition for laser direct structuring, resin-molded article, and method for manufacturing molded article with plated layer |
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