JP5025227B2 - Thermoplastic resin composition and molded body - Google Patents
Thermoplastic resin composition and molded body Download PDFInfo
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- JP5025227B2 JP5025227B2 JP2006303740A JP2006303740A JP5025227B2 JP 5025227 B2 JP5025227 B2 JP 5025227B2 JP 2006303740 A JP2006303740 A JP 2006303740A JP 2006303740 A JP2006303740 A JP 2006303740A JP 5025227 B2 JP5025227 B2 JP 5025227B2
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- resin composition
- thermoplastic resin
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- 239000011342 resin composition Substances 0.000 title claims description 59
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 45
- -1 silane compound Chemical class 0.000 claims description 56
- 239000004431 polycarbonate resin Substances 0.000 claims description 43
- 229920005668 polycarbonate resin Polymers 0.000 claims description 43
- 229910000077 silane Inorganic materials 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000003063 flame retardant Substances 0.000 claims description 13
- 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 claims description 12
- 239000000654 additive Substances 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 239000012760 heat stabilizer Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 5
- QKYBEKAEVQPNIN-UHFFFAOYSA-N barium(2+);oxido(oxo)alumane Chemical compound [Ba+2].[O-][Al]=O.[O-][Al]=O QKYBEKAEVQPNIN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims 1
- 239000000049 pigment Substances 0.000 description 43
- 238000000034 method Methods 0.000 description 35
- 125000003118 aryl group Chemical group 0.000 description 23
- 238000002156 mixing Methods 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 16
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000000465 moulding Methods 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- 238000002834 transmittance Methods 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 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
- 230000032683 aging Effects 0.000 description 5
- 229940125782 compound 2 Drugs 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 229920002545 silicone oil Polymers 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
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003017 thermal stabilizer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000006096 absorbing agent Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000004645 aluminates Chemical class 0.000 description 3
- 239000012965 benzophenone Substances 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
- 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
- 238000005286 illumination Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000000463 material 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
- 239000010452 phosphate Substances 0.000 description 3
- 238000012545 processing Methods 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
- 125000001424 substituent group Chemical group 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- MBXOOYPCIDHXGH-UHFFFAOYSA-N 3-butylpentane-2,4-dione Chemical compound CCCCC(C(C)=O)C(C)=O MBXOOYPCIDHXGH-UHFFFAOYSA-N 0.000 description 2
- 235000010893 Bischofia javanica Nutrition 0.000 description 2
- 240000005220 Bischofia javanica Species 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-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
- 239000003153 chemical reaction reagent Substances 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
- 238000002845 discoloration Methods 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
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 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
- 125000005641 methacryl group Chemical group 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
- 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
- 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
- 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
- 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
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- LZFZQYNTEZSWCP-UHFFFAOYSA-N 2,6-dibutyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC(CCCC)=C1O LZFZQYNTEZSWCP-UHFFFAOYSA-N 0.000 description 1
- LLYXTEJGXDIXAB-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(N2N=C3C=CC=CC3=N2)=CC=1C(C)C1=CC=CC=C1 LLYXTEJGXDIXAB-UHFFFAOYSA-N 0.000 description 1
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- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical class C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 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
- 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
- 239000006082 mold release agent 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-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
- 230000035699 permeability Effects 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
- 150000002989 phenols Chemical class 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
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000002994 raw material Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 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
- 238000005507 spraying Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- QJLXRCHPLSKCHD-UHFFFAOYSA-L strontium;chloro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Sr+2].[O-]P([O-])(Cl)=O QJLXRCHPLSKCHD-UHFFFAOYSA-L 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱可塑性樹脂組成物、及びその成形体に関する。さらに詳しくは、機械的強度、耐熱性、耐湿熱性、及び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、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、及びスクリーンなどとして使用できる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 mechanical strength, heat resistance, heat and humidity resistance, and hue at the time of fluorescence, and an electric signboard, a liquid crystal backlight, an illumination display, a traffic sign, comprising the resin composition, The present invention relates to a molded body that can be used as a sign board and a screen.
ポリカーボネート樹脂は、耐衝撃性、耐熱性、及び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、発光顔料を混合することが知られている。発光顔料には、紫外線等の外部刺激で刺激されると、その刺激を停止した後もかなりの長時間（数分〜数時間）、残光が肉眼で認められる蓄光（燐光）顔料と、紫外線等で刺激すると発光し、外部刺激を停止すると速やかに発光が減衰する紫外線発光（蛍光）顔料がある。これらの発光顔料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. It is preferably used. Conventionally, mixing a luminescent pigment is known as a method for improving the visibility of a polycarbonate resin. Luminescent pigments, when stimulated by external stimuli such as ultraviolet rays, are phosphorescent (phosphorescent) pigments that are visible to the naked eye for quite a long time (several minutes to several hours) after the stimulus is stopped, and ultraviolet rays. For example, there is an ultraviolet (fluorescent) pigment that emits light when stimulated with a light source and the like, and emits light rapidly when the external stimulus is stopped. When a polycarbonate resin mixed with these luminescent pigments is melt-kneaded, the polycarbonate resin is thermally decomposed, causing discoloration and a decrease in mechanical strength, and only a resin composition with poor practicality can be obtained.
蓄光顔料を混合したポリカーボネート樹脂の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、耐衝撃性の改良は満足できるものではない。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が提案されている（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（特許文献３）、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、シリコーンオイルでコートされた、アルミン酸塩マトリックスを有する発光顔料を含む樹脂組成物（特許文献４）などが提案されている。しかし、いずれの場合もポリカーボネート樹脂の熱分解抑制効果や変色防止効果は満足できるものではなかった。 In order to improve the impact resistance of a polycarbonate resin mixed with a phosphorescent pigment, an aromatic polycarbonate resin composition containing a specific amount of phosphite has been proposed (Patent Document 1). However, the improvement in impact resistance is 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 proposed (Patent Document 2). In addition, as a resin composition that is excellent in thermal stability and hue at the time of processing and that effectively exhibits light emitting performance, a resin composition comprising a polycarbonate resin and an aluminate-based phosphor having a specific particle diameter (Patent Document 3), Resin composition containing a luminescent pigment having an aluminate matrix coated with silicone oil as a resin composition that exhibits melt flow stability and does not cause much graying when blended in an extruder (Patent Document 4) Has been proposed. However, in either case, the effect of suppressing the thermal decomposition and the effect of preventing discoloration of the polycarbonate resin were not satisfactory.
本発明は、前記従来技術の問題点を解決し、機械的強度、耐熱性、耐湿熱性、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成形体を提供することにある。 The present invention solves the above-mentioned problems of the prior art, and provides a thermoplastic resin composition excellent in mechanical strength, heat resistance, heat and humidity resistance, and hue at the time of fluorescence, and a molded article comprising the resin composition. It is in.
上記課題を解決するために、本発明では、ポリカーボネート樹脂（Ａ成分）を１００重量部、紫外線発光顔料（Ｂ成分）を０．１〜５０重量部、及びシラン化合物（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、及び該樹脂組成物からなる成形体を提供する。 In order to solve the above problems, in the present invention, polycarbonate resin (component A) is 100 parts by weight, ultraviolet light emitting pigment (component B) is 0.1 to 50 parts by weight, and silane compound (component C) is B component. A thermoplastic resin composition containing 0.5 to 10% by weight, and a molded body comprising the resin composition are provided.
本発明によれば、機械的強度、耐熱性、耐湿熱性、加工時の熱安定性や色相・蛍光輝度安定性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を提供することができる。 According to the present invention, a thermoplastic resin composition excellent in mechanical strength, heat resistance, heat-and-moisture resistance, heat stability during processing and hue / fluorescence luminance stability, an electric decoration signboard comprising the resin composition, and liquid crystal It is possible to provide a molded article suitable as a backlight, an illumination display, a luminaire cover, a traffic sign, a sign board, a screen, an automobile part such as a reflector or a meter part, or an OA equipment part.
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。
Ａ成分 ポリカーボネート樹脂：
本発明で用いるポリカーボネート樹脂（Ａ成分）につい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、及び芳香族−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.
Component A Polycarbonate resin:
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の例には、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含まれる。中でも、ビスフェノールＡが好ましい。さらに、難燃性が高い組成物を調製する目的で、芳香族ジヒドロキシ化合物として、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 and the like are included. Of these, bisphenol A is preferred. Further, for the purpose of preparing a composition having high flame retardancy, as an aromatic dihydroxy compound, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound, or a phenolic compound having a siloxane structure. OH group-containing polymers or oligomers 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重合体；及び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 a polycarbonate polymer derived from 2,2-bis (4-hydroxyphenyl) propane; and 2,2-bis (4-hydroxyphenyl) propane and Polycarbonate copolymers derived from other 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、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 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 紫外線発光顔料：
本発明で用いる紫外線発光顔料（Ｂ成分）は、紫外線の照射を停止すると速やかに発光が減衰する発光顔料である。該発光顔料の例には、アルミン酸バリウム、硫化酸化イットリウム、酸化ゲルマニウム亜鉛、酸化バリウム、酸化マグネシウム、酸化アルミニウム、塩化リン酸ストロンチウムなどの無機化合物；ローダミンＢ、ローダミン６Ｇ、フルオレセイン、エオシンなどの蛍光染料；及びこれらの蛍光染料を基に合成された蛍光顔料などの有機化合物；が含まれる。中でも、無機化合物の発光顔料は、熱安定性及び耐候性の点で好ましく、希土類元素で付活したアルミン酸バリウム及び硫化酸化イットリウムは、発光輝度に優れるので好ましい。
また、本発明において、Ｂ成分として市販されている紫外線発光顔料を用いてもよい。市販されている紫外線発光顔料の例には、根本特殊化学（株）よりネモトＵＶ蛍光体／Ｄ１１６４、Ｄ１１８０の商品名・グレード名で市販されているもの；及びデイグロ社よりＰｈａｎｔｏｍ Ｐｉｇｍｅｎｔｓ／ＩＰＯ１８、ＩＰＯ１９の商品名・グレード名で市販されているもの；などが含まれる。
B component UV light emitting pigment:
The ultraviolet light-emitting pigment (component B) used in the present invention is a light-emitting pigment whose light emission is rapidly attenuated when ultraviolet light irradiation is stopped. Examples of the luminescent pigment include inorganic compounds such as barium aluminate, yttrium sulfide oxide, zinc zinc oxide, barium oxide, magnesium oxide, aluminum oxide, and strontium chlorophosphate; fluorescence such as rhodamine B, rhodamine 6G, fluorescein, and eosin. Dyes; and organic compounds such as fluorescent pigments synthesized based on these fluorescent dyes. Among these, a luminous pigment of an inorganic compound is preferable from the viewpoint of thermal stability and weather resistance, and barium aluminate and yttrium sulfide oxide activated by a rare earth element are preferable because of excellent emission luminance.
In the present invention, a commercially available ultraviolet light-emitting pigment may be used as the component B. Examples of commercially available ultraviolet light-emitting pigments include those sold under the trade name / grade name of Nemoto UV phosphor / D1164 and D1180 by Nemoto Special Chemical Co., Ltd .; and Phantom Pigments / IPO18 and IPO19 from Deegro. That are commercially available under the trade names and grade names of
紫外線発光顔料（Ｂ成分）は、粉体であることが好ましく、その数平均粒径は、０．１〜１０μｍの範囲が好ましく、特に０．３〜５μｍの範囲が好ましい。平均粒径が０．１μｍ未満では蛍光輝度に劣り、１０μｍを超えると溶融混練時にスクリューやシリンダーの摩耗が発生し易くなり、成形品が黒ずむことがある。紫外線発光顔料（Ｂ成分）は、１種単独で又は２種以上を組み合わせて用いることができる。 The ultraviolet light emitting pigment (component B) is preferably a powder, and the number average particle size thereof is preferably in the range of 0.1 to 10 μm, particularly preferably in the range of 0.3 to 5 μm. When the average particle size is less than 0.1 μm, the fluorescence brightness is inferior, and when it exceeds 10 μm, the wear of the screw or cylinder tends to occur during melt-kneading, and the molded product may become dark. The ultraviolet light emitting pigment (component B) can be used alone or in combination of two or more.
Ｃ成分 シラン化合物：
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。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）
C component Silane 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. Among these, a silane compound represented by the following formula (1) is preferable.
(R 1 O) n Si (R 2 ) (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。 In the formula, R 1 is a C1-4 aliphatic hydrocarbon group, R 2 is a C6-12 aromatic or alicyclic hydrocarbon group, a C1-12 aliphatic hydrocarbon group, C2-16. An ethylenically unsaturated hydrocarbon group or an organic group having a C3-15 epoxy group, preferably a C1-4 aliphatic hydrocarbon group, a C6-12 aromatic hydrocarbon group, a C2-16 It is an organic group which has an ethylenically unsaturated hydrocarbon group or a C3-15 epoxy group, and 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、アクリロキシ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。 Examples of the C6-12 aromatic or alicyclic hydrocarbon group include a phenyl group and a cyclohexyl group. Examples of the C1-12 aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, Examples thereof include an isobutyl group and a decyl group. Examples of the C2-16 ethylenically unsaturated hydrocarbon group include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a methacryloxypropyl group, and an acryloxypropyl group. Examples of the organic group having a C3-15 epoxy group include a 3,4-epoxycyclohexyl group and a 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-glycidoxypropylmethyldiethoxy Examples include silane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and phenyltrimethoxysilane.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、紫外線発光顔料（Ｂ成分）を０．１〜５０重量部、及びシラン化合物（Ｃ成分）をＢ成分の０．５〜１０重量％含有する。Ａ成分１００重量部に対して、Ｂ成分の含有量が０．１重量部未満では発光が弱くなり、一方、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成分の含有量は、Ａ成分１００重量部に対して、０．３〜２０重量部であるのが好ましく、０．５〜１０重量部であるのがより好ましい。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。一方、Ｃ成分の含有量がＢ成分の含有量の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。本発明の熱可塑性樹脂組成物において、Ｃ成分の含有量は、Ｂ成分の含有量の４〜９重量％であるのが好ましい。 The thermoplastic resin composition of the present invention has a polycarbonate resin (component A) of 100 parts by weight, an ultraviolet light emitting pigment (component B) of 0.1 to 50 parts by weight, and a silane compound (component C) of 0. Contains 5 to 10% by weight. When the content of the B component is less than 0.1 parts by weight with respect to 100 parts by weight of the A component, the light emission is weak, while when it exceeds 50 parts by weight, the mechanical strength and thermal stability of the thermoplastic resin composition are lowered. To do. The content of the component B is preferably 0.3 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the component A. 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, Mechanical strength, hue, heat resistance and wet heat resistance are also reduced. On the other hand, if the content of the C component exceeds 10% by weight of the content of the B component, gas is generated during melt-kneading, which is likely to cause mold deposit. In the thermoplastic resin composition of the present invention, the content of the C component is preferably 4 to 9% by weight of the content of the B component.
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、有機スルホン酸金属塩、シリコーン化合物が好適である。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, an organic sulfonic acid metal salt, and a silicone compound are preferable. As the phosphoric ester compound, for example, a compound represented by the following formula (2) is preferable.
式中、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よい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, R 1 , R 2 , R 3 and R 4 each independently represents an optionally substituted aryl group, and X represents a divalent aromatic group which may have another substituent. Indicates. 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、及びこれらの置換体、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、例えば、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, and their substitution products and condensates. 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、難燃性を向上させることができ、且つ耐熱性も良好な樹脂組成物となるので好ましい。 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 since the flame retardancy can be improved and the resin composition has good heat resistance.
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。
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。
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.
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、難燃性を向上させることができ、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 range since the flame retardancy can be improved and the resin composition has good thermal stability.
本発明において使用可能な難燃剤用のシリコーン化合物としては、特開２００６−１６９４５１公報に記載の、直鎖状もしくは分岐状の構造を有するポリオルガノシロキサンが好ましい。ポリオルガノシロキサンが有する有機基は、炭素数が１〜２０のアルキル基及び置換アルキル基のような炭化水素又はビニル及びアルケニル基、シクロアルキル基、ならびにフェニル、ベンジルのような芳香族炭化水素基などの中から選ばれる。
ポリジオルガノシロキサンは、官能基を含有していなくても、官能基を含有していてもよい。官能基を含有しているポリジオルガノシロキサンの場合、官能基はメタクリル基、アルコキシ基又はエポキシ基であることが好ましい。
As the silicone compound for flame retardant that can be used in the present invention, polyorganosiloxane having a linear or branched structure described in JP-A No. 2006-169451 is preferable. The organic group possessed by the polyorganosiloxane includes hydrocarbons such as alkyl groups and substituted alkyl groups having 1 to 20 carbon atoms, vinyl and alkenyl groups, cycloalkyl groups, and aromatic hydrocarbon groups such as phenyl and benzyl. Chosen from.
Even if polydiorganosiloxane does not contain a functional group, it may contain a functional group. In the case of a polydiorganosiloxane containing a functional group, the functional group is preferably a methacryl group, an alkoxy group or an epoxy group.
本発明の熱可塑性樹脂組成物における、難燃剤用シリコーン化合物の含有量は、ポリカーボネート樹脂（Ａ成分）１００重量部に対し、０．５〜１０重量部であるのが好ましい。難燃剤用シリコーン化合物の含有量が前記範囲であると、成形品外観及び弾性率等を損なうことなく、難燃性が良好となるので好ましい。 The content of the flame retardant silicone compound in the thermoplastic resin composition of the present invention is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A). It is preferable for the content of the silicone compound for flame retardant to be in the above-mentioned range since flame retardancy is improved without impairing the appearance of the molded product and the elastic modulus.
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、調色性及び発色性を低下させず、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. It is preferable for the content of the ultraviolet absorber to be in the above-mentioned range since the weather resistance can be improved without deteriorating the toning property and color developability and without causing bleeding out on the surface of the molded product.
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、数平均分子量２００〜１５０００の脂肪族炭化水素化合物、及びポリシロキサン系シリコーンオイル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 preferred release agent is at least one compound selected from an aliphatic carboxylic acid, an aliphatic carboxylic acid ester, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000, and a polysiloxane silicone oil. 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。
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.
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、上記添加剤の他に、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、防菌剤などを添加してもよい。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, an organic or inorganic fine particle light, in addition to the above additives, as long as the purpose of the present invention is not impaired as required. A diffusing agent, an antistatic agent, an antifogging agent, a lubricant / antiblocking agent, a fluidity improving agent, a plasticizer, a dispersing agent, an antibacterial agent and the like may be added. 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）、紫外線発光顔料（Ｂ成分）、シラン化合物（Ｃ成分）及び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成分とを予め混合した後、Ａ成分及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。
Ｂ成分とＣ成分との混合方法の具体例としては、（１）ヘンシェルミキサー、ボールミル、アドマイザーコロイドミル、バンバリーミキサーなどの各種混合機を使用して、紫外線発光顔料（Ｂ成分）を攪拌しつつ、シラン化合物（Ｃ成分）を噴霧、滴下する方法、（２）紫外線発光顔料（Ｂ成分）をシラン化合物（Ｃ成分）によって湿潤させる方法、（３）紫外線発光顔料（Ｂ成分）をシラン化合物（Ｃ成分）に浸漬する方法、などが挙げられる。上記（１）〜（３）の方法によって、Ｂ成分とＣ成分とを混合・接触させる前に、Ｃ成分を水又は溶媒によって希釈することができる。溶媒としては、有機溶媒、水／有機溶媒の混合液などが挙げられる。Ｂ成分とＣ成分とを混合・接触させた後、温度が８０℃以上、より好ましくは１００℃以上、さらに好ましくは１２０℃以上に達するまで、攪拌混合を継続するのが好ましい。攪拌混合時間は、使用する混合機にもよるが、１５分間〜１．５時間の範囲で選ばれるのが好ましい。攪拌混合することによって、Ｂ成分の表面をＣ成分によって被覆し、反応させ、溶媒を飛散（揮発）させることができる。
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 polycarbonate resin (component A), ultraviolet light emitting pigment (component B), silane compound (component C) and additive components blended as necessary is measured, and a tumbler, a Henschel mixer, etc. There is a method of mixing using various mixers. Among them, after mixing the B component and the C component in advance, the method of mixing the A component and the additive component blended as necessary effectively suppresses the surface activity of the B component, and in the thermoplastic resin composition This is a more preferable mixing method from the viewpoint of preventing unnecessary side reactions.
Specific examples of the mixing method of the B component and the C component include: (1) While stirring the ultraviolet light emitting pigment (B component) using various mixers such as a Henschel mixer, a ball mill, an admixer colloid mill, and a Banbury mixer. , A method of spraying and dropping a silane compound (component C), (2) a method of wetting an ultraviolet light emitting pigment (component B) with a silane compound (component C), and (3) an ultraviolet light emitting pigment (component B) with a silane compound ( The method of immersing in C component) etc. are mentioned. According to the methods (1) to (3), the C component can be diluted with water or a solvent before the B component and the C component are mixed and contacted. Examples of the solvent include organic solvents, water / organic solvent mixtures, and the like. After mixing and contacting the B component and the C component, stirring and mixing is preferably continued until the temperature reaches 80 ° C. or higher, more preferably 100 ° C. or higher, and even more preferably 120 ° C. or higher. The stirring and mixing time depends on the mixer to be used, but is preferably selected in the range of 15 minutes to 1.5 hours. By stirring and mixing, the surface of the B component can be coated with the C component, reacted, and the solvent can be scattered (volatilized).
上記方法でＢ成分とＣ成分とを予め混合した後、Ａ成分及び所望により添加される添加剤とさらに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。 As a method of premixing the B component and the C component by the above method and then further melt-kneading the A component and optionally added additives, Banbury mixer, roll, Brabender, single screw kneading extruder, twin screw The method of using a kneading extruder, a kneader, etc. is mentioned.
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公知の方法が、制限なく利用できる。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 the molding method, a conventionally known method of molding a molded product from a thermoplastic resin material can be used 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（Ｃ成分）を用いることにより、紫外線発光顔料（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・蛍光輝度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）とほぼ等しいのが好ましく、具体的には、本発明の熱可塑性樹脂組成物のＱ値は、Ｑ0±３０％以内であるのが好ましく、Ｑ0±２０％以内であるのがより好ましい。
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 the silane compound (component C), thermal decomposition during processing of the polycarbonate resin promoted by the presence of the ultraviolet light emitting pigment (component B) is suppressed, and mechanical strength and heat resistance are improved. Reduces changes in hue and fluorescence intensity due to heating. 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 almost the same as the Q value (Q 0 ) of a standard resin composition containing no B component and no C component (the types and blending ratios of the A component and other additives are the same). Specifically, the Q value of the thermoplastic resin composition of the present invention is preferably within Q 0 ± 30%, and more preferably within Q 0 ± 20%.
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.
また、本発明の熱可塑性樹脂組成物は、シラン化合物（Ｃ成分）の添加による透過率の低下がないのが好ましい。本発明の熱可塑性樹脂組成物からなる成形体の全光線透過率は、Ｃ成分を含有しない標準樹脂組成物（Ａ成分、Ｂ成分及びその他の添加剤の種類及び配合割合は同一）からなる成形体の全光線透過率（Ｔ0）とほぼ等しいのが好ましく、具体的には、本発明の熱可塑性樹脂組成物からなる成形体の全光線透過率Ｔは、Ｔ0±１５％以内であるのが好ましく、Ｔ0±１０％以内であるのがより好ましい。
なお、全光線透過率は、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値とする。
Moreover, it is preferable that the thermoplastic resin composition of this invention does not have the fall of the transmittance | permeability by addition of a silane compound (C component). The total light transmittance of the molded article made of the thermoplastic resin composition of the present invention is a molding made of a standard resin composition containing no C component (the types and blending ratios of component A, component B and other additives are the same). It is preferable that the total light transmittance (T 0 ) of the body is substantially equal. Specifically, the total light transmittance T of the molded body made of the thermoplastic resin composition of the present invention is within T 0 ± 15%. And more preferably within T 0 ± 10%.
The total light transmittance is a value measured with a NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd., using a 3 mm-thick flat plate as a test piece in accordance with JIS K-7105.
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、以下の実施例及び比較例において、配合量は重量部を意味する。また、実施例及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） 紫外線発光顔料１：青色発光顔料、根本特殊化学（株）製「商品名：ネモトＵＶ蛍光体／Ｄ１１８０」数平均粒径２．５±１．０μｍ
（Ｂ−２） 紫外線発光顔料２：緑色発光顔料、根本特殊化学（株）製「商品名：ネモトＵＶ蛍光体／Ｄ１１６４」数平均粒径１．１±０．５μｍ
（Ｂ−３） 紫外線発光顔料３：乳酸「和光純薬工業（株）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、上記紫外線発光顔料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、シラン化合物２で予め表面処理された、紫外線発光顔料（Ｂ−３）成分を得た。
（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」
（Ｄ） 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」
（Ｅ） 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」
（Ｆ） 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 structural component of the resin composition used in the Example and the comparative example has the following characteristic.
(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) Ultraviolet luminescent pigment 1: Blue luminescent pigment, “Product name: Nemoto UV phosphor / D1180” manufactured by Nemoto Special Chemical Co., Ltd. Number average particle diameter 2.5 ± 1.0 μm
(B-2) UV light emitting pigment 2: Green light emitting pigment, “Product name: Nemoto UV phosphor / D1164” manufactured by Nemoto Special Chemical Co., Ltd. Number average particle diameter 1.1 ± 0.5 μm
(B-3) Ultraviolet luminescent pigment 3: 6 g of silane compound 2 (C-2) in an aqueous solution in which 0.3% by weight of lactic acid “manufactured by Wako Pure Chemical Industries, Ltd., reagent” 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 pigment 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 an ultraviolet light emitting pigment (B-3) component that had been surface-treated with the silane compound 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”
(D) Silicone oil: methyl hydrogen siloxane, “trade name: SH1107” manufactured by Toray Dow Corning Silicone Co., Ltd.
(E) Thermal stabilizer: Cresyl diphenyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd., “Product name: CDP”
(F) 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１〜３］
芳香族ポリカーボネート樹脂及び各種添加剤を、表１及び表２に示す割合で、タンブラーで２０分間混合した後、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、ストランドとして押出した。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試験片及び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 1-4 and Comparative Examples 1-3]
After mixing the aromatic polycarbonate resin and various additives in the proportions shown in Tables 1 and 2 with a tumbler for 20 minutes, a single-screw extruder with a screw diameter of 40 mm (“SV-40” manufactured by Isuzu Chemical Industries Ltd.) Were kneaded at a cylinder temperature of 280 ° C. and a screw rotation speed of 70 rpm, and extruded as a strand. The extruded strand was cut to produce a pellet.
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. The various 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紫外線発光顔料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試験片及び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及び表２に示す。
[Reference example]
Various ASTM test pieces and a 3 mm-thick flat plate were prepared in the same manner as in the Examples and Comparative Examples except that the ultraviolet light emitting pigment 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 Tables 1 and 2.
［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, HAESTEST, MODEL PC-SIII), the test piece was 100 ° C. in a steam atmosphere at 120 ° C., pressure 1 kg / cm 2 , and humidity 100%. Time treatment was performed, and the presence or absence of deformation of the test piece was observed to provide an index of hydrolysis resistance.
(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及び２は、参考例と同等のＱ値を示し、分子量低下によるＱ値の上昇がないが、一方、同一種の紫外線蛍光顔料２を含有するが、シラ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、Ｑ値が上昇していることが理解できる。その結果、実施例１及び２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及び蛍光時の色相のいずれも優れている。 From the results shown in Table 1, Examples 1 and 2 show a Q value equivalent to that of the Reference Example, and there is no increase in the Q value due to a decrease in molecular weight, but on the other hand, although containing the same type of ultraviolet fluorescent pigment 2, In Comparative Example 1 containing no compound, it can be understood that the Q value is increased due to the decrease in the molecular weight. As a result, Examples 1 and 2 are superior to Comparative Example 1 in all of impact resistance, hue, heat aging characteristics, wet heat resistance, and hue during fluorescence.
表２に示す結果から、実施例３は、参考例と同等のＱ値を示し、分子量低下によるＱ値の上昇がないが、一方、同一種の紫外線蛍光顔料１を含有するが、シラン化合物を含有しない比較例２では、分子量低下によって、Ｑ値が上昇していることが理解できる。その結果、実施例３は、比較例２と比較して、耐衝撃性、色相、耐熱老化特性、耐湿熱特性及び蛍光時の色相のいずれにも優れている。
また、実施例４の熱可塑性樹脂組成物は、シラン化合物２と紫外線発光顔料１とをあらかじめ混合することによって調製された紫外線発光顔料３を含有しているので、透過率がより高くなっていることが理解できる。一方、シラン化合物の代わりにシリコーンオイルを用い、シリコーンオイルで処理された紫外線発光顔料１を含有する比較例３は、Ｑ値の低下はないものの、白色がかっていて、光透過率が低下しているため、高透過率が要求される用途に用いることはできない。
From the results shown in Table 2, Example 3 shows a Q value equivalent to that of the reference example, and there is no increase in the Q value due to a decrease in molecular weight. On the other hand, although it contains the same type of ultraviolet fluorescent pigment 1, In Comparative Example 2 not containing, it can be understood that the Q value is increased due to the decrease in the molecular weight. As a result, Example 3 is superior to Comparative Example 2 in all of impact resistance, hue, heat aging characteristics, moisture and heat resistance, and hue during fluorescence.
Moreover, since the thermoplastic resin composition of Example 4 contains the ultraviolet light-emitting pigment 3 prepared by previously mixing the silane compound 2 and the ultraviolet light-emitting pigment 1, the transmittance is higher. I understand that. On the other hand, the comparative example 3 which uses the silicone oil instead of the silane compound and contains the ultraviolet light-emitting pigment 1 treated with the silicone oil is white, and the light transmittance is reduced although the Q value does not decrease. Therefore, it cannot be used for applications requiring high transmittance.
本発明によれば、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、及びスクリーンなどの成形体の製造に利用可能な熱可塑性樹脂組成物を提供することできる。 ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which can be utilized for manufacture of molded objects, such as an electrical signboard, a liquid crystal backlight, an illumination display, a traffic sign, a sign board, and a screen, can be provided.
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| JP5030550B2 (en) * | 2006-11-22 | 2012-09-19 | 三菱エンジニアリングプラスチックス株式会社 | Thermoplastic resin composition and molded body |
| DE102009043510A1 (en) * | 2009-09-30 | 2011-03-31 | Bayer Materialscience Ag | Polycarbonate compositions with improved melt stability |
| CN103443328B (en) | 2011-03-18 | 2016-02-24 | 三菱化学欧洲有限公司 | The manufacture method of the synthetic resin of thermoplastic resin composition, synthetic resin and band coating |
| CN112322018B (en) * | 2020-11-22 | 2022-08-05 | 上海锦湖日丽塑料有限公司 | Transparent antifogging PC resin and preparation method thereof |
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| JPH086018B2 (en) * | 1987-09-30 | 1996-01-24 | 帝人化成株式会社 | Thermoplastic resin composition |
| JPH05239349A (en) * | 1992-03-02 | 1993-09-17 | Sekiyu Sangyo Kasseika Center | Composite material |
| JPH09241630A (en) * | 1996-03-04 | 1997-09-16 | Kasei Optonix Co Ltd | Surface-treated phosphor and its production |
| JPH09316443A (en) * | 1996-05-27 | 1997-12-09 | Nemoto Tokushu Kagaku Kk | Surface treatment of luminous fluorescent pigment, surface-treated luminous fluorescent pigment and luminous fluorescent coating material using the same |
| JP3046963B1 (en) * | 1999-02-05 | 2000-05-29 | 東北ムネカタ株式会社 | Resin additive |
| US6692659B2 (en) * | 2002-05-31 | 2004-02-17 | General Electric Company | Phosporescent polycarbonate, concentrate and molded articles |
| JP2005082647A (en) * | 2003-09-05 | 2005-03-31 | Teijin Chem Ltd | Polycarbonate resin composition |
| JP4310205B2 (en) * | 2004-02-05 | 2009-08-05 | 帝人化成株式会社 | Flame retardant aromatic polycarbonate resin composition |
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