JP6042271B2 - Polyester resin composition for reflector and reflector - Google Patents
Polyester resin composition for reflector and reflector Download PDFInfo
- Publication number
- JP6042271B2 JP6042271B2 JP2013113095A JP2013113095A JP6042271B2 JP 6042271 B2 JP6042271 B2 JP 6042271B2 JP 2013113095 A JP2013113095 A JP 2013113095A JP 2013113095 A JP2013113095 A JP 2013113095A JP 6042271 B2 JP6042271 B2 JP 6042271B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- reflector
- resin composition
- mass
- light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001225 polyester resin Polymers 0.000 title claims description 87
- 239000004645 polyester resin Substances 0.000 title claims description 87
- 239000000203 mixture Substances 0.000 title claims description 54
- 239000011256 inorganic filler Substances 0.000 claims description 36
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 36
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 25
- 239000012463 white pigment Substances 0.000 claims description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 239000004611 light stabiliser Substances 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 11
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 5
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- -1 PA9T and PA10T Chemical class 0.000 description 24
- 238000000465 moulding Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 125000002723 alicyclic group Chemical group 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 230000006750 UV protection Effects 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 125000006841 cyclic skeleton Chemical group 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 235000001508 sulfur Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NWHNXXMYEICZAT-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidin-4-ol Chemical compound CN1C(C)(C)CC(O)CC1(C)C NWHNXXMYEICZAT-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- OYNOCRWQLLIRON-UHFFFAOYSA-N 1-n,3-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)benzene-1,3-dicarboxamide Chemical compound C1C(C)(C)NC(C)(C)CC1NC(=O)C1=CC=CC(C(=O)NC2CC(C)(C)NC(C)(C)C2)=C1 OYNOCRWQLLIRON-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- HXJZEGBVQCRLOD-UHFFFAOYSA-N 1-triethoxysilylpropan-2-amine Chemical compound CCO[Si](CC(C)N)(OCC)OCC HXJZEGBVQCRLOD-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ORACIQIJMCYPHQ-MDZDMXLPSA-N 2-[4-[(e)-2-[4-(1,3-benzoxazol-2-yl)phenyl]ethenyl]phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)/C=C/C=3C=CC(=CC=3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ORACIQIJMCYPHQ-MDZDMXLPSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
- ZSPDYGICHBLYSD-UHFFFAOYSA-N 2-methylnaphthalene-1-carboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C)=CC=C21 ZSPDYGICHBLYSD-UHFFFAOYSA-N 0.000 description 1
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 1
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
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- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- AYVGBNGTBQLJBG-UHFFFAOYSA-N [3-(hydroxymethyl)cyclopentyl]methanol Chemical compound OCC1CCC(CO)C1 AYVGBNGTBQLJBG-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- HXXPOZXBLAGNLP-UHFFFAOYSA-N [4-(hydroxymethyl)cycloheptyl]methanol Chemical compound OCC1CCCC(CO)CC1 HXXPOZXBLAGNLP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 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 1
- 238000000071 blow moulding Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920006119 nylon 10T Polymers 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-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
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- CFUDQABJYSJIQY-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CC(C)OCC1CO1 CFUDQABJYSJIQY-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、反射材用ポリエステル樹脂組成物、およびそれを含む反射板に関する。 The present invention relates to a polyester resin composition for a reflector, and a reflector including the same.
発光ダイオード（以下、ＬＥＤと言う）や有機ＥＬなどの光源は、低電力や高寿命といった特長を活かして、照明ならびにディスプレイのバックライトとして幅広く使用されており、今後も大きく拡大する傾向にある。 Light sources such as light emitting diodes (hereinafter referred to as LEDs) and organic ELs are widely used as backlights for lighting and displays, taking advantage of their low power and long life, and will continue to expand greatly in the future.
ＬＥＤの反射板には、機械的強度とともに、プリント配線基板などへの表面実装（リフローはんだ工程等）も行われることから、２５０℃を超える耐熱性、ならびに光を反射する機能上、使用環境下において安定して高い反射率を示すことが求められる。 LED reflectors are not only mechanically strong, but also surface-mounted on printed wiring boards (reflow soldering process, etc.). It is required to stably exhibit a high reflectance.
近年、照明用途向けにおいてもＬＥＤ化が進み、中でも屋外で主に使用される外灯や信号機などでは、今後も一層、ＬＥＤ化が進むと思われる。ＬＥＤ照明は虫を誘導する波長の光（紫外線ほか）をほとんど出射しないため、特定波長の光に反応して集まってくる習性のある虫対策に効果的であり、虫の死骸による器具や周辺の汚れを引き起こさないことから、そのニーズは高まっている。また長寿命であることから、交換し難い場所に設置してある外灯においては特に利便性が高く、交換にかかる費用を抑える点でも有利である。 In recent years, the use of LEDs for lighting applications has progressed, and in particular, outdoor lights and traffic lights that are mainly used outdoors are expected to be used in the future. LED lighting emits almost no light (ultraviolet rays, etc.) of wavelengths that induce insects, so it is effective in combating insects that have the habit of gathering in response to light of specific wavelengths. The need is growing because it does not cause dirt. In addition, since it has a long life, it is particularly convenient for an outdoor light installed in a place where it is difficult to replace, and it is advantageous in that the cost for replacement is reduced.
しかしながら、屋外照明の場合、パソコンやテレビ向けのＬＥＤ材料とは異なり、反射板が太陽光に晒され、変色してしまう。その結果、反射特性が顕著に低下し、明るさを低下させてしまう不具合が問題となっており、耐紫外線（ＵＶ）特性に優れる反射材料へのニーズが高まっている。 However, in the case of outdoor lighting, unlike LED materials for personal computers and televisions, the reflector is exposed to sunlight and changes color. As a result, there is a problem that the reflection characteristics are remarkably lowered and the brightness is lowered, and there is an increasing need for a reflection material having excellent ultraviolet resistance (UV) characteristics.
従来より反射板にはセラミックなどの光や熱に強い材料も多く用いられてきたが、加工と価格面の課題から、一部の製品を除いて、樹脂製反射板が主流となっている。中でも、耐熱性の観点から、半芳香族ポリアミドを用いた反射板が多く使用されているが、近年では加熱の変色性が比較的低い、ＰＡ９ＴやＰＡ１０Ｔといった長鎖ジアミンを原料とした材料が多く採用されている（特許文献１，２、３）。 Conventionally, many materials resistant to light and heat, such as ceramic, have been used for the reflector, but from the viewpoint of processing and price, resin reflectors are the mainstream except for some products. Among them, from the viewpoint of heat resistance, reflectors using semi-aromatic polyamides are often used, but in recent years, there are many materials made from long-chain diamines such as PA9T and PA10T, which have relatively low discoloration during heating. (Patent Documents 1, 2, and 3).
本発明者らの検討によれば、ポリアミドを含む反射材組成物では、耐光安定剤を配合した処方においても、ＵＶ照射条件における長期反射特性の変化が著しく悪いことから、さらなる向上が必要なことがわかった。 According to the study by the present inventors, in the case of a reflector composition containing polyamide, even in a formulation containing a light-resistant stabilizer, the change in long-term reflection characteristics under UV irradiation conditions is extremely bad, so further improvement is necessary. I understood.
従って本発明は、特に耐ＵＶ特性と長期での反射特性に優れるとともに、良好な成形性とＬＥＤの製造工程およびリフローはんだ工程などにおける加熱による反射率の低下も小さい反射板を得ることができる反射材用ポリエステル樹脂組成物を提供することを課題とする。また、前記樹脂組成物を含む反射板を得ることを課題とする。 Therefore, the present invention is particularly excellent in UV resistance and long-term reflection characteristics, and it is possible to obtain a reflector that has good moldability and a small decrease in reflectance due to heating in the LED manufacturing process and reflow soldering process. It is an object to provide a polyester resin composition for a material. Moreover, let it be a subject to obtain the reflecting plate containing the said resin composition.
本発明者らはこのような状況に鑑みて鋭意検討した結果、高い融点もしくはガラス転移温度を有する熱可塑性樹脂、無機充填材、白色顔料、蛍光増白剤および特定の耐光安定剤を含む組成物が、耐ＵＶ特性と反射率の経時安定性を高いレベルで併せ持つことを見出し、本発明を完成した。 As a result of intensive studies in view of such circumstances, the present inventors have found that a composition comprising a thermoplastic resin having a high melting point or glass transition temperature, an inorganic filler, a white pigment, a fluorescent whitening agent, and a specific light-resistant stabilizer. However, the present invention has been completed by finding that it has both UV resistance characteristics and reflectance stability over time at a high level.
本発明の第一は、以下に示す反射材用ポリエステル樹脂組成物に関する。
［１］融点もしくはガラス転移温度が２５０℃以上であるポリエステル樹脂（Ａ）３０〜８０質量％と、無機充填材（Ｂ）１〜５０質量％と、白色顔料（Ｃ）５〜５０質量％と、蛍光増白剤（Ｄ）０．０１〜０．２質量％と、耐光安定剤（Ｅ）０．０１〜０．２質量％と、を含む反射材用ポリエステル樹脂組成物（ただし、ポリエステル樹脂（Ａ），無機充填材（Ｂ），白色顔料（Ｃ），蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）の合計は１００質量％である）。
1st of this invention is related with the polyester resin composition for reflectors shown below.
[1] 30 to 80% by mass of a polyester resin (A) having a melting point or glass transition temperature of 250 ° C. or higher, 1 to 50% by mass of an inorganic filler (B), and 5 to 50% by mass of a white pigment (C) A polyester resin composition for a reflector (however, polyester resin) containing 0.01 to 0.2% by mass of a fluorescent brightening agent (D) and 0.01 to 0.2% by mass of a light stabilizer (E) (A), inorganic filler (B), white pigment (C), fluorescent brightener (D), and light stabilizer (E) are 100% by mass in total).
［２］前記ポリエステル樹脂（Ａ）が、テレフタル酸から誘導されるジカルボン酸成分単位３０〜１００モル％、テレフタル酸以外の芳香族ジカルボン酸成分単位０〜７０モル％からなるジカルボン酸成分単位（ａ−１）並びに、炭素原子数４〜２０の脂環族ジアルコール成分単位（ａ−３）および／または脂肪族ジアルコール成分単位（ａ−４）を含むポリエステル樹脂であることを特徴とする［１］に記載の反射材用ポリエステル樹脂組成物。
［３］前記ポリエステル樹脂（Ａ）に含まれるジアルコール成分単位（ａ−３）が、シクロヘキサン骨格を有することを特徴とする［２］に記載の反射材用ポリエステル樹脂組成物。
［４］前記蛍光増白剤（Ｄ）が、ベンゾキサゾール誘導体であることを特徴とする［１］に記載の反射材用ポリエステル樹脂組成物。
［５］前記耐光安定剤（Ｅ）が、窒素を含むヘテロ環を２個以上有し、分子量が４００ｇ/ｍｏｌ以上の化合物であることを特徴とする［１］に記載の反射材用ポリエステル樹脂組成物。
[2] A dicarboxylic acid component unit (a) in which the polyester resin (A) is composed of 30 to 100 mol% of a dicarboxylic acid component unit derived from terephthalic acid and 0 to 70 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid. -1) and a polyester resin containing an alicyclic dialcohol component unit (a-3) having 4 to 20 carbon atoms and / or an aliphatic dialcohol component unit (a-4) [ 1] The polyester resin composition for reflectors according to [1].
[3] The polyester resin composition for a reflector according to [2], wherein the dialcohol component unit (a-3) contained in the polyester resin (A) has a cyclohexane skeleton.
[4] The polyester resin composition for reflectors according to [1], wherein the optical brightener (D) is a benzoxazole derivative.
[5] The polyester resin for a reflector according to [1], wherein the light-resistant stabilizer (E) is a compound having two or more hetero rings containing nitrogen and having a molecular weight of 400 g / mol or more. Composition.
本発明の第二は、以下に示す反射板に関する。
［６］前記［１］に記載のポリエステル樹脂組成物を含む反射板。
［７］発光ダイオード素子用の反射板であることを特徴とする［６］に記載の反射板。
The second of the present invention relates to the reflector shown below.
[6] A reflector including the polyester resin composition according to [1].
[7] The reflecting plate according to [6], which is a reflecting plate for a light emitting diode element.
本発明の反射材用ポリエステル樹脂組成物は、ポリエステル樹脂、無機充填材、白色顔料および特定の添加剤を含み、反射材料として用いられる。例えば、屋外で使用される反射板に成形するための樹脂組成物として用いられる。さらに詳しくは、本発明の反射材用ポリエステル樹脂組成物は、耐ＵＶ特性と長期での反射特性に優れるとともに、インサート成形に好適である。 The polyester resin composition for a reflective material of the present invention contains a polyester resin, an inorganic filler, a white pigment and a specific additive, and is used as a reflective material. For example, it is used as a resin composition for molding into a reflector used outdoors. More specifically, the polyester resin composition for a reflector of the present invention is excellent in UV resistance and long-term reflection characteristics, and is suitable for insert molding.
１．反射材用ポリエステル樹脂組成物について
本発明の反射材用ポリエステル樹脂組成物は、ポリエステル樹脂（Ａ）、無機充填材（Ｂ）、白色顔料（Ｃ）、蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）を含み、必要に応じて他の添加剤等をさらに含み得る。
1. About the polyester resin composition for reflectors The polyester resin composition for reflectors of the present invention comprises a polyester resin (A), an inorganic filler (B), a white pigment (C), a fluorescent whitening agent (D), and a light-resistant stabilizer. (E), and may further contain other additives as required.
［ポリエステル樹脂（Ａ）]
本発明に好適に使用されるポリエステル樹脂（Ａ）は、少なくとも芳香族ジカルボン酸由来の成分単位と、環状骨格を有するジアルコール由来の成分単位とを含むことが好ましい。
[Polyester resin (A)]
The polyester resin (A) preferably used in the present invention preferably contains at least a component unit derived from an aromatic dicarboxylic acid and a component unit derived from a dialcohol having a cyclic skeleton.
環状骨格を有するジアルコール由来の成分単位の例には、脂環族ジアルコール由来の成分単位や芳香族ジアルコール由来の成分単位が含まれるが、耐熱性や成形性の観点から、脂環族ジアルコール由来の成分単位が好ましい。 Examples of the component unit derived from a dialcohol having a cyclic skeleton include a component unit derived from an alicyclic dialcohol and a component unit derived from an aromatic dialcohol, but from the viewpoint of heat resistance and moldability, an alicyclic group Component units derived from dialcohol are preferred.
そのようなポリエステル樹脂（Ａ）としては、特定のジカルボン酸成分単位と、脂環族ジアルコール成分単位（ａ−３）および／または脂肪族ジアルコール成分単位（ａ−４）とを含むポリエステル樹脂であることが好ましい。 As such a polyester resin (A), a polyester resin containing a specific dicarboxylic acid component unit and an alicyclic dialcohol component unit (a-3) and / or an aliphatic dialcohol component unit (a-4) It is preferable that
ポリエステル樹脂（Ａ）におけるジカルボン酸成分単位（ａ−１）としては、テレフタル酸成分単位を３０〜１００モル％、テレフタル酸以外の芳香族ジカルボン酸成分単位を０〜７０モル％、および／または炭素原子数４〜２０の脂肪族ジカルボン酸成分単位を０〜７０モル％の量で含むことが好ましい。これらのジカルボン酸成分単位の合計量は１００モル％である。 The dicarboxylic acid component unit (a-1) in the polyester resin (A) is 30 to 100 mol% of terephthalic acid component units, 0 to 70 mol% of aromatic dicarboxylic acid component units other than terephthalic acid, and / or carbon. It is preferable to contain an aliphatic dicarboxylic acid component unit having 4 to 20 atoms in an amount of 0 to 70 mol%. The total amount of these dicarboxylic acid component units is 100 mol%.
テレフタル酸以外の芳香族ジカルボン酸成分単位としては、例えばイソフタル酸、２−メチルテレフタル酸、ナフタレンジカルボン酸およびこれらの組み合わせから誘導される成分単位が好ましい。 As the aromatic dicarboxylic acid component unit other than terephthalic acid, for example, component units derived from isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and combinations thereof are preferable.
脂肪族ジカルボン酸成分単位は、その炭素原子数を特に制限するものではないが、炭素原子数は４〜２０、好ましくは６〜１２の脂肪族ジカルボン酸から誘導されうる。脂肪族ジカルボン酸成分単位を誘導するために用いられる脂肪族ジカルボン酸の例としては、アジピン酸、スベリン酸、アゼライン酸、セバシン酸、デカンジカルボン酸、ウンデカンジカルボン酸、ドデカンジカルボン酸などが挙げられ、好ましくはアジピン酸であり得る。 The aliphatic dicarboxylic acid component unit is not particularly limited in the number of carbon atoms, but may be derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Examples of the aliphatic dicarboxylic acid used to derive the aliphatic dicarboxylic acid component unit include adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and the like. Preferably it may be adipic acid.
また、本発明において、ジカルボン酸成分単位は、テレフタル酸成分単位を、好ましくは４０〜１００モル％、より好ましくは４０〜８０モル％；テレフタル酸以外の芳香族ジカルボン酸成分単位を、好ましくは０〜６０モル％、より好ましくは２０〜６０モル％；および／または炭素原子数４〜２０、好ましくは６〜１２の脂肪族ジカルボン酸成分単位を、好ましくは０〜６０モル％、より好ましくは２０〜６０モル％の量で含むことができる。 In the present invention, the dicarboxylic acid component unit is a terephthalic acid component unit, preferably 40 to 100 mol%, more preferably 40 to 80 mol%; an aromatic dicarboxylic acid component unit other than terephthalic acid, preferably 0. -60 mol%, more preferably 20-60 mol%; and / or aliphatic dicarboxylic acid component units having 4-20 carbon atoms, preferably 6-12 carbon atoms, preferably 0-60 mol%, more preferably 20 It can be included in an amount of ˜60 mol%.
本発明においては、ジカルボン酸成分単位として、上記のような構成単位とともに、少量の、例えば、１０モル％以下程度の量の多価カルボン酸成分単位がさらに含まれてもよい。このような多価カルボン酸成分単位として具体的には、トリメリット酸およびピロメリット酸等のような三塩基酸および多塩基酸を挙げることができる。 In the present invention, the dicarboxylic acid component unit may further contain a small amount, for example, an amount of about 10 mol% or less of the polyvalent carboxylic acid component unit together with the above-described structural unit. Specific examples of such polyvalent carboxylic acid component units include tribasic acids and polybasic acids such as trimellitic acid and pyromellitic acid.
また、ポリエステル樹脂（Ａ）は、上記のような成分単位以外に、シクロヘキサンジカルボン酸などの脂環族ジカルボン酸から誘導される成分単位をさらに含むこともできる。 Moreover, the polyester resin (A) can further include a component unit derived from an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid in addition to the above-described component unit.
ポリエステル樹脂（Ａ）における脂環族ジアルコール成分単位（ａ−３）は、炭素数４〜２０の脂環式炭化水素骨格を有するジアルコール由来の成分単位を含むことが好ましい。脂環式炭化水素骨格を有するジアルコールとしては、１,３-シクロペンタンジオール、１,３-シクロペンタンジメタノール、１,４-シクロヘキサンジオール、１,４-シクロヘキサンジメタノール、１,４-シクロヘプタンジオール、１,４-シクロヘプタンジメタノールなどの脂環族ジアルコールを使用することができる。なかでも、耐熱性や吸水性、入手容易性などの観点から、シクロヘキサン骨格を有するジアルコール由来の成分単位が好ましく、シクロヘキサンジメタノール由来の成分単位がさらに好ましい。 The alicyclic dialcohol component unit (a-3) in the polyester resin (A) preferably includes a dialcohol-derived component unit having an alicyclic hydrocarbon skeleton having 4 to 20 carbon atoms. Examples of dialcohol having an alicyclic hydrocarbon skeleton include 1,3-cyclopentanediol, 1,3-cyclopentanedimethanol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and 1,4-cyclohexane. Alicyclic dialcohols such as heptanediol and 1,4-cycloheptanedimethanol can be used. Among these, from the viewpoint of heat resistance, water absorption, availability, etc., a component unit derived from a dialcohol having a cyclohexane skeleton is preferable, and a component unit derived from cyclohexanedimethanol is more preferable.
脂環族ジアルコールの場合、シス、トランス構造などの異性体が存在するが、耐熱性の観点ではトランス構造のほうが好ましい。したがって、シス／トランス比は、好ましくは５０／５０〜０／１００、さらに好ましくは、４０／６０〜０／１００である。 In the case of alicyclic dialcohols, there are isomers such as cis and trans structures, but the trans structure is preferred from the viewpoint of heat resistance. Therefore, the cis / trans ratio is preferably 50/50 to 0/100, more preferably 40/60 to 0/100.
ポリエステル樹脂（Ａ）は、脂環族ジアルコール成分単位（ａ−３）のほかに、樹脂としての溶融流動性を高める目的などで、脂肪族ジアルコール成分単位（ａ−４）をさらに含み得る。脂肪族ジアルコールとしては、具体的には、エチレングリコール、トリメチレングリコール、プロピレングリコール、テトラメチレングリコール、ネオペンチルグリコール、ヘキサメチレングリコール、ドデカメチレングリコールなどを挙げることができる。 In addition to the alicyclic dialcohol component unit (a-3), the polyester resin (A) may further include an aliphatic dialcohol component unit (a-4) for the purpose of improving the melt fluidity as a resin. . Specific examples of the aliphatic dialcohol include ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, and dodecamethylene glycol.
ポリエステル樹脂（Ａ）は、前記脂環族ジアルコール成分単位（ａ−３）のほかに、必要に応じて芳香族ジアルコール成分単位をさらに含み得る。芳香族ジアルコールとしては、ビスフェノール、ハイドロキノン、２,２-ビス（４-β-ヒドロキシエトキシフェニル）プロパン類などの芳香族ジオールなどを挙げることができる。 The polyester resin (A) may further contain an aromatic dialcohol component unit as necessary in addition to the alicyclic dialcohol component unit (a-3). Examples of the aromatic dialcohol include aromatic diols such as bisphenol, hydroquinone, and 2,2-bis (4-β-hydroxyethoxyphenyl) propane.
本発明で用いられるポリエステル樹脂（Ａ）の、示差走査熱量計（ＤＳＣ）で測定した融点（Ｔｍ）、もしくはガラス転移温度（Ｔｇ）は、２５０℃以上である。好ましい下限値は２７０℃、さらに好ましくは２９０℃である。一方、好ましい上限値は３５０℃を例示でき、さらに好ましくは３３５℃である。前記の融点やガラス転移温度が２５０℃以上であると、リフローはんだ時の反射板の変形が抑制される。上限温度は原則的としては制限がないが、融点もしくはガラス転移温度が３５０℃以下であると、溶融成形に際してポリエステル樹脂の分解を抑制できるので好ましい。 The polyester resin (A) used in the present invention has a melting point (Tm) or glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 250 ° C. or higher. A preferred lower limit is 270 ° C, more preferably 290 ° C. On the other hand, a preferable upper limit value may be 350 ° C, and more preferably 335 ° C. When the melting point or glass transition temperature is 250 ° C. or higher, the deformation of the reflector during reflow soldering is suppressed. The upper limit temperature is not limited in principle, but a melting point or glass transition temperature of 350 ° C. or lower is preferable because decomposition of the polyester resin can be suppressed during melt molding.
例えば、ポリエステル樹脂（Ａ）の融点（Ｔｍ）もしくはガラス転移温度（Ｔｇ）は、２７０℃〜３５０℃の範囲内、好ましくは２９０〜３３５℃の範囲内としうる。 For example, the melting point (Tm) or glass transition temperature (Tg) of the polyester resin (A) can be in the range of 270 ° C. to 350 ° C., preferably in the range of 290 to 335 ° C.
ポリエステル樹脂（Ａ）の極限粘度[η]は、０．３〜１．０ｄｌ／ｇであることが好ましい。極限粘度がこのような範囲にある場合、反射材用熱可塑性樹脂組成物の成形時の流動性が優れるものとし得る。ポリエステル樹脂（Ａ）の極限粘度の調整は、ポリエステル樹脂の分子量を調整することなどでなし得る。ポリエステル樹脂の分子量の調整方法は、重縮合反応の進行度合いや単官能のカルボン酸や単官能のアルコールなどを適量加える等の公知の方法を採用することが出来る。 The intrinsic viscosity [η] of the polyester resin (A) is preferably 0.3 to 1.0 dl / g. When the intrinsic viscosity is in such a range, the fluidity at the time of molding of the thermoplastic resin composition for a reflector can be excellent. The intrinsic viscosity of the polyester resin (A) can be adjusted by adjusting the molecular weight of the polyester resin. As a method for adjusting the molecular weight of the polyester resin, a known method such as a degree of progress of the polycondensation reaction or an appropriate amount of a monofunctional carboxylic acid or a monofunctional alcohol can be employed.
ポリエステル樹脂（Ａ）の極限粘度[η]は、ポリエステル樹脂（Ａ）をフェノールとテトラクロロエタンの５０/５０質量％の混合溶媒に溶解し、ウベローデ粘度計を使用し、２５℃±０．０５℃の条件下で試料溶液の流下秒数を測定し、以下の算式で算出される値である。
[η]＝ηＳＰ/[Ｃ（１+０．２０５ηＳＰ）]
[η]：極限粘度（ｄｌ/ｇ）
ηＳＰ：比粘度
Ｃ：試料濃度（ｇ/ｄｌ）
ｔ：試料溶液の流下秒数（秒）
ｔ0：溶媒の流下秒数（秒）
ηＳＰ＝（ｔ−ｔ０）/ｔ０
The intrinsic viscosity [η] of the polyester resin (A) is obtained by dissolving the polyester resin (A) in a 50/50 mass% mixed solvent of phenol and tetrachloroethane and using an Ubbelohde viscometer at 25 ° C. ± 0.05 ° C. It is a value calculated by the following formula by measuring the number of seconds that the sample solution flows under the conditions of
[η] = ηSP / [C (1 + 0.205ηSP)]
[η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
t: Number of seconds that the sample solution flows (seconds)
t0: The number of seconds that the solvent flows (seconds)
ηSP = (t−t0) / t0
［ポリエステル樹脂（Ａ）の調製方法］
ポリエステル樹脂（Ａ）は、例えば反応系内に分子量調整剤等を配合して、少なくともジカルボン酸成分単位（ａ−１）と脂環族ジアルコール成分単位（ａ−３）とを反応させることにより得ることができる。上述のように、反応系内に分子量調整剤を配合することで、ポリエステル樹脂（Ａ）の極限粘度を調整し得る。
[Method for Preparing Polyester Resin (A)]
The polyester resin (A) is prepared by, for example, blending a molecular weight adjusting agent in the reaction system and reacting at least the dicarboxylic acid component unit (a-1) and the alicyclic dialcohol component unit (a-3). Can be obtained. As described above, the intrinsic viscosity of the polyester resin (A) can be adjusted by blending a molecular weight modifier in the reaction system.
分子量調整剤としては、モノカルボン酸およびモノアルコールを使用することができる。上記モノカルボン酸の例としては、炭素原子数２〜３０の脂肪族モノカルボン酸、芳香族モノカルボン酸および脂環族モノカルボン酸を挙げることができる。なお、芳香族モノカルボン酸および脂環族モノカルボン酸は、環状構造部分に置換基を有していてもよい。例えば、脂肪族モノカルボン酸としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、ラウリン酸、トリデシル酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸およびリノ−ル酸を挙げることができる。また、芳香族モノカルボン酸の例としては、安息香酸、トルイル酸、ナフタレンカルボン酸、メチルナフタレンカルボン酸およびフェニル酢酸を挙げることができ、脂環族モノカルボン酸の例としては、シクロヘキサンカルボン酸を挙げることができる。 As the molecular weight modifier, monocarboxylic acid and monoalcohol can be used. Examples of the monocarboxylic acid include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, aromatic monocarboxylic acids, and alicyclic monocarboxylic acids. In addition, the aromatic monocarboxylic acid and the alicyclic monocarboxylic acid may have a substituent in the cyclic structure portion. For example, aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. be able to. Examples of aromatic monocarboxylic acids include benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid. Examples of alicyclic monocarboxylic acids include cyclohexanecarboxylic acid. Can be mentioned.
このような分子量調整剤は、上述のジカルボン酸成分単位（ａ−１）と脂環族ジアルコール成分単位（ａ−３）との反応の際に、反応系におけるジカルボン酸成分単位の合計量１モルに対して、通常は、０〜０．０７モル、好ましくは０〜０．０５モルの量で使用される。 Such a molecular weight modifier is used in the reaction of the dicarboxylic acid component unit (a-1) and the alicyclic dialcohol component unit (a-3) described above with a total amount 1 of dicarboxylic acid component units in the reaction system. Usually, it is used in an amount of 0 to 0.07 mol, preferably 0 to 0.05 mol, relative to mol.
また、本発明においては、必要に応じて、物性の異なるポリエステル樹脂（Ａ）を複数併用してもよい。また、本発明の目的の範囲内であれば、他の熱可塑性樹脂を併用してもよい。 In the present invention, if necessary, a plurality of polyester resins (A) having different physical properties may be used in combination. Further, other thermoplastic resins may be used in combination as long as they are within the object of the present invention.
［無機充填材（Ｂ）］
本発明の反射材用ポリエステル樹脂組成物に含まれる無機充填材（Ｂ）として、公知の無機充填材を制限無く用いることができる。具体的には、繊維状、粉状、粒状、板状、針状、クロス状、マット状等の高いアスペクト比を有する形状の種々の無機補強材を使用することが好ましい。具体的には、ガラス繊維、カルボニル構造を有する無機化合物（例えば、炭酸カルシウムなどの炭酸塩のウィスカーなど）、ハイドロタルサイト、チタン酸カリウム等のチタン酸塩、ワラストナイト、ゾノトライトなどを挙げることができる。
[Inorganic filler (B)]
As the inorganic filler (B) contained in the polyester resin composition for a reflector of the present invention, a known inorganic filler can be used without limitation. Specifically, it is preferable to use various inorganic reinforcing materials having a shape having a high aspect ratio, such as a fibrous shape, a powdery shape, a granular shape, a plate shape, a needle shape, a cloth shape, and a mat shape. Specific examples include glass fibers, inorganic compounds having a carbonyl structure (for example, whiskers of carbonates such as calcium carbonate), hydrotalcite, titanates such as potassium titanate, wollastonite, and zonotolite. Can do.
その中でも、ガラス繊維（ＢＧ）や、カルボニル構造を有する無機化合物（ＢＷ）であることが好ましい。これらの無機充填材は、シリコーン化合物等の公知の化合物で処理されていてもより。特にシリコーン化合物で処理されたガラス繊維は好ましい態様の一つである。 Among these, it is preferable that they are glass fiber (BG) and the inorganic compound (BW) which has a carbonyl structure. Even if these inorganic fillers are treated with known compounds such as silicone compounds. In particular, glass fiber treated with a silicone compound is one of preferred embodiments.
上記のような無機充填材の平均長さは１０μｍ〜１０ｍｍ、好ましくは１０μｍ〜５ｍｍの範囲にあり、アスペクト比（Ｌ平均繊維長/Ｄ平均繊維径）は１〜５００、好ましくは１０〜３５０の範囲にある。このような範囲にある無機充填材を使用すると、強度の向上や線膨張係数の低下などの面で好ましい。また、無機充填材の平均長さは１０〜１００μｍ、好ましくは１０〜５０μｍの範囲にあり、アスペクト比（Ｌ（繊維の平均長）／Ｄ（繊維の平均外径））は１〜１００、好ましくは５〜７０の範囲にあってもよい。 The average length of the inorganic filler as described above is in the range of 10 μm to 10 mm, preferably 10 μm to 5 mm, and the aspect ratio (L average fiber length / D average fiber diameter) is 1 to 500, preferably 10 to 350. Is in range. Use of an inorganic filler in such a range is preferable in terms of improvement in strength and reduction in linear expansion coefficient. The average length of the inorganic filler is 10 to 100 μm, preferably 10 to 50 μm, and the aspect ratio (L (average fiber length) / D (average fiber outer diameter)) is 1 to 100, preferably May be in the range of 5-70.
無機充填材（Ｂ）は、異なる長さや異なるアスペクト比を有する二種以上の無機充填材を組み合わせて用いてもよい。 The inorganic filler (B) may be used in combination of two or more inorganic fillers having different lengths and different aspect ratios.
長さやアスペクト比が大きな無機充填材（Ｂ１）として、具体的には、前述のガラス繊維、ワラストナイト（珪酸カルシウム）等の珪酸塩、チタン酸カリウムウィスカーなどのチタン酸塩等を挙げることができる。これらの中でもガラス繊維が好ましい。 Specific examples of the inorganic filler (B1) having a large length and aspect ratio include the aforementioned glass fibers, silicates such as wollastonite (calcium silicate), and titanates such as potassium titanate whiskers. it can. Among these, glass fiber is preferable.
このような長さやアスペクト比の大きな無機充填材（Ｂ１）の好ましい長さの下限値は１５μｍ、好ましくは３０μｍ、より好ましくは５０μｍである。一方、好ましい上限値は１０ｍｍ、より好ましくは８ｍｍ、さらに好ましくは６ｍｍ、特に好ましくは５ｍｍである。特にガラス繊維の場合、好ましい下限値は５００μｍ、より好ましくは７００μｍ、さらに好ましくは１ｍｍである。 The lower limit of the preferable length of the inorganic filler (B1) having such a large length and aspect ratio is 15 μm, preferably 30 μm, more preferably 50 μm. On the other hand, a preferable upper limit is 10 mm, more preferably 8 mm, still more preferably 6 mm, and particularly preferably 5 mm. Particularly in the case of glass fiber, the preferred lower limit is 500 μm, more preferably 700 μm, and even more preferably 1 mm.
また、無機充填材（Ｂ１）のアスペクト比の好ましい下限値は２０、より好ましくは５０、さらに好ましくは９０である。一方、好ましい上限値は５００、より好ましくは４００、さらに好ましくは３５０である。 Moreover, the preferable lower limit of the aspect ratio of the inorganic filler (B1) is 20, more preferably 50, and still more preferably 90. On the other hand, the preferred upper limit is 500, more preferably 400, and even more preferably 350.
長さやアスペクト比が、無機充填材（Ｂ１）よりも相対的に小さい無機充填材（Ｂ２）の例としては、カルボニル基を有する無機充填材（ＢＷ）が好ましい例としてあげられ、具体的には炭酸カルシウムなどの炭酸塩のウィスカーを挙げることが出来る。 As an example of the inorganic filler (B2) whose length and aspect ratio are relatively smaller than those of the inorganic filler (B1), a preferred example is an inorganic filler (BW) having a carbonyl group. Mention may be made of carbonate whiskers such as calcium carbonate.
前記カルボニル基を有する無機充填材（ＢＷ）のアスペクト比は、好ましくは１〜３００、より好ましくは５〜２００、更に好ましくは１０〜１５０である。 The aspect ratio of the inorganic filler (BW) having a carbonyl group is preferably 1 to 300, more preferably 5 to 200, and still more preferably 10 to 150.
これらの無機充填材を組み合わせるとベースポリマーへの無機充填材の分散性が改良され、またベースポリマーと無機充填材との親和性が向上することにより、耐熱性、機械強度などを向上させるだけでなく、後述する白色顔料（Ｃ）の分散性を向上させることがあると考えられる。 When these inorganic fillers are combined, the dispersibility of the inorganic filler in the base polymer is improved, and the affinity between the base polymer and the inorganic filler is improved, so that only heat resistance, mechanical strength, etc. are improved. However, it is considered that the dispersibility of the white pigment (C) described later may be improved.
［白色顔料（Ｃ）］
本発明の反射材用ポリエステル樹脂組成物に含まれる白色顔料（Ｃ）としては、ポリエステル樹脂（Ａ）などと併用して該樹脂を白色化することで、光反射機能を向上できるものであればよい。具体的には、酸化チタン、酸化亜鉛、硫化亜鉛、鉛白、硫酸亜鉛、硫酸バリウム、炭酸カルシウム、酸化アルミナなどが挙げられる。これらの白色顔料は、単独で用いてもよく、二種以上組み合わせて用いてもよい。また、これらの白色顔料は、シランカップリング剤あるいはチタンカップリング剤などで処理して使用することもできる。例えば、白色顔料は、ビニルトリエトキシシラン、２-アミノプロピルトリエトキシシラン、２-グリシドキシプロピルトリエトキシシランなどのシラン系化合物で表面処理されていてもよい。
[White pigment (C)]
As the white pigment (C) contained in the polyester resin composition for a reflector of the present invention, any white pigment can be used in combination with the polyester resin (A) to improve the light reflection function. Good. Specific examples include titanium oxide, zinc oxide, zinc sulfide, white lead, zinc sulfate, barium sulfate, calcium carbonate, and alumina oxide. These white pigments may be used alone or in combination of two or more. These white pigments can also be used after being treated with a silane coupling agent or a titanium coupling agent. For example, the white pigment may be surface-treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, or 2-glycidoxypropyltriethoxysilane.
白色顔料としては、特に酸化チタンが好ましい。酸化チタンを使用することにより反射率、隠蔽性といった光学特性が向上する。酸化チタンは、ルチル型が好ましい。酸化チタンの粒子径は、０．１〜０．５μｍ、好ましくは０．１５〜０．３μｍである。 As the white pigment, titanium oxide is particularly preferable. By using titanium oxide, optical characteristics such as reflectivity and concealability are improved. The titanium oxide is preferably a rutile type. The particle diameter of titanium oxide is 0.1 to 0.5 μm, preferably 0.15 to 0.3 μm.
これらの白色顔料は、反射率を均一化させるためなどの理由で、アスペクト比の小さい、すなわち球状に近いものが好ましい。 These white pigments preferably have a small aspect ratio, that is, a spherical shape, for the purpose of making the reflectance uniform.
［蛍光増白剤（Ｄ）］
本発明の反射材用ポリエステル樹脂組成物に含まれる蛍光増白剤（Ｄ）とは、紫外線を吸収し、青色の可視光線に変えて放出する剤である。蛍光増白剤は、スチルベン骨格やスチリル骨格を有することが多いが；本発明における蛍光増白剤（Ｄ）は、好ましくは、ベンズオキサゾール誘導体に由来する。より具体的な例には、４,４'-ビス(２-ベンズオキサゾリル)スチルベンや、その誘導体が含まれる。蛍光増白剤は、クラリアントジャパン（株）からＨｏｓｔａｌｕｘ ＫＳとして商業的に入手することもでき、Eastman Chemicals社からEASTOBRITE（登録商標）添加剤として商業的に入手することもできる。
[Fluorescent brightener (D)]
The fluorescent whitening agent (D) contained in the polyester resin composition for a reflector according to the present invention is an agent that absorbs ultraviolet rays and converts them into blue visible light. The optical brightener often has a stilbene skeleton or a styryl skeleton; however, the optical brightener (D) in the present invention is preferably derived from a benzoxazole derivative. More specific examples include 4,4′-bis (2-benzoxazolyl) stilbene and derivatives thereof. The optical brightener can also be obtained commercially as Hostalux KS from Clariant Japan Co., Ltd. or commercially available as an EASTOBRITE® additive from Eastman Chemicals.
［耐光安定剤（Ｅ）］
本発明の反射材用ポリエステル樹脂組成物に含まれる耐光安定剤（Ｅ）は、主に紫外線等の光による樹脂の劣化を防止し、光に対する安定性を向上させる作用を有するものである。耐光安定剤としては、紫外線そのものを吸収する紫外線吸収剤や、ラジカル捕捉作用のある光安定剤等を挙げることができる。
[Light Stabilizer (E)]
The light-resistant stabilizer (E) contained in the polyester resin composition for a reflector according to the present invention has an effect of preventing deterioration of the resin due to light such as ultraviolet rays and improving the stability to light. Examples of the light-resistant stabilizer include an ultraviolet absorber that absorbs ultraviolet rays and a light stabilizer that has a radical scavenging action.
耐光安定剤（Ｅ）は、ベンゾトリアゾール類、トリアジン類、ベンゾフェノン類、ベンゾエート類、ヒンダードアミン類、オギザニリド類等でありうるが；好ましくはヒンダードアミン系化合物からなる耐光安定剤である。 The light-resistant stabilizer (E) can be benzotriazoles, triazines, benzophenones, benzoates, hindered amines, oxanilides, etc .; preferably, it is a light-resistant stabilizer comprising a hindered amine compound.
ヒンダードアミン系化合物を窒素雰囲気下で温度２５℃から３４０℃まで２０℃／分で昇温した後に、温度３４０℃で１０分間保持したときの、ヒンダードアミン系化合物の質量減少率が０〜５０質量％、好ましくは０〜４０質量％，さらに０〜３０質量％であることが好ましい。 After the hindered amine compound was heated at a temperature of 20 ° C./min from a temperature of 25 ° C. to 340 ° C. under a nitrogen atmosphere, the hindered amine compound had a mass reduction rate of 0 to 50% by mass when held at 340 ° C. for 10 minutes, Preferably it is 0-40 mass%, Furthermore, it is preferable that it is 0-30 mass%.
ヒンダートアミン系化合物の具体例には、Ｎ，Ｎ’−ビス−２，２，６，６−テトラメチル−４−ピペリジル−１，３−ベンゼンジカルボキシアミド、１，２，３，４-ブタンテトラカルボン酸と１，２，２，６，６-ペンタメチル-４-ピペリジノールおよび３，９-ビス（２-ヒドロキシ-１，１-ジメチルエチル）-２，４，８，１０-テトラオキサスピロ［５.５］ウンデカンとの混合エステル化物、Ｎ,Ｎ',Ｎ”,Ｎ'''-テトラキス-（４,６-ビス-（ブチル-（Ｎ-メチル-２,２,６,６-テトラメチルピペリジン-４-イル）アミノ）-トリアジン-２-イル）-４,７-ジアザデカン-１,１０-ジアミン、ポリ[{６-（１,１,３，３-テトラメチルブチル）アミノ-１,３,５-トリアジン-２,４-ジイル}{（２,２,６,６-テトラメチル-４-ピペリジル）イミノ}ヘキサメチレン｛（２,２,６,６-テトラメチル-４-ピペリジル）イミノ｝]などが含まれる。 Specific examples of hindered amine compounds include N, N′-bis-2,2,6,6-tetramethyl-4-piperidyl-1,3-benzenedicarboxamide, 1,2,3,4- Butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] Mixed esterified product with undecane, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-) Tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [{6- (1,1,3,3-tetramethylbutyl) amino- 1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2 , 6,6-tetramethyl-4-piperidyl) imino}] and the like.
［その他の添加剤］
本発明の反射材用ポリエステル樹脂組成物は、発明の効果を損なわない範囲で、用途に応じて、任意の添加剤を含んでいてもよい。任意の添加剤の例には、酸化防止剤（フェノール類、アミン類、イオウ類、リン類等）、耐熱安定剤（ラクトン化合物、ビタミンＥ類、ハイドロキノン類、ハロゲン化銅、ヨウ素化合物等）、他の重合体（ポリオレフィン類、エチレン・プロピレン共重合体、エチレン・１−ブテン共重合体等のオレフィン共重合体、プロピレン・１−ブテン共重合体等のオレフィン共重合体、ポリスチレン、ポリアミド、ポリカーボネート、ポリアセタール、ポリスルフォン、ポリフェニレンオキシド、フッ素樹脂、シリコーン樹脂、ＬＣＰ等）、難燃剤（臭素系、塩素系、リン系、アンチモン系、無機系等）、可塑剤、増粘剤、帯電防止剤、離型剤、顔料、結晶核剤などの、種々公知の添加剤が含まれる。
[Other additives]
The polyester resin composition for a reflector of the present invention may contain any additive depending on the application within a range not impairing the effects of the invention. Examples of optional additives include antioxidants (phenols, amines, sulfurs, phosphorus, etc.), heat stabilizers (lactone compounds, vitamin Es, hydroquinones, copper halides, iodine compounds, etc.), Other polymers (olefins such as polyolefins, ethylene / propylene copolymer, ethylene / 1-butene copolymer, olefin copolymers such as propylene / 1-butene copolymer, polystyrene, polyamide, polycarbonate , Polyacetal, polysulfone, polyphenylene oxide, fluorine resin, silicone resin, LCP, etc.), flame retardant (bromine, chlorine, phosphorus, antimony, inorganic, etc.), plasticizer, thickener, antistatic agent, Various known additives such as release agents, pigments, crystal nucleating agents and the like are included.
これら添加剤は、その成分の種類によって異なるが、ポリエステル樹脂（Ａ）と無機充填材（Ｂ）と白色顔料（Ｃ）と蛍光増白剤（Ｄ）と耐光安定剤（Ｅ）との合計１００質量％に対して、０〜１０質量％が好ましく、より好ましくは０〜５質量％、さらに好ましくは０〜３質量％の割合で用いられ得る。 These additives vary depending on the types of the components, but a total of 100 of the polyester resin (A), the inorganic filler (B), the white pigment (C), the fluorescent brightener (D), and the light stabilizer (E). 0-10 mass% is preferable with respect to the mass%, More preferably, it is 0-5 mass%, More preferably, it may be used in the ratio of 0-3 mass%.
本発明の樹脂組成物を他の成分と組み合わせて使用する場合、前記添加剤の選択が重要になる場合がある。例えば、組合せ使用する他の成分に触媒などが含まれる場合、前記添加剤に触媒毒になる成分や元素が含まれている物は避けることが好ましいのは自明である。前記のような避けた方が好ましい添加剤としては、例えば、リンや硫黄などを含む成分を挙げることができる。 When the resin composition of the present invention is used in combination with other components, the selection of the additive may be important. For example, when a catalyst or the like is included in other components used in combination, it is obvious that it is preferable to avoid a component or element that contains a catalyst poison in the additive. Additives that are preferably avoided as described above include, for example, components containing phosphorus, sulfur and the like.
［反射材用ポリエステル樹脂組成物の組成］
本発明の反射材用ポリエステル樹脂組成物は、ポリエステル樹脂（Ａ）、無機充填材（Ｂ）、白色顔料（Ｃ）、蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）の総量に対して、ポリエステル樹脂（Ａ）を３０〜８０質量％で含むことが好ましく、３０〜７０質量％、より好ましくは４０〜６０質量％の割合で含み得る。ポリエステル樹脂（Ａ）の含有率が前記の範囲にあると、成形性を損なうことなく、はんだリフロー工程に耐え得る耐熱性に優れた反射材用ポリエステル樹脂組成物を得ることができる。
[Composition of polyester resin composition for reflector]
The polyester resin composition for a reflector of the present invention is based on the total amount of the polyester resin (A), inorganic filler (B), white pigment (C), fluorescent brightener (D), and light stabilizer (E). The polyester resin (A) is preferably contained at 30 to 80% by mass, more preferably 30 to 70% by mass, and more preferably 40 to 60% by mass. When the content of the polyester resin (A) is in the above range, a polyester resin composition for a reflector having excellent heat resistance that can withstand the solder reflow process can be obtained without impairing moldability.
本発明の反射材用ポリエステル樹脂組成物は、ポリエステル樹脂（Ａ）、無機充填材（Ｂ）、白色顔料（Ｃ）、蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）の総量に対して、無機充填材（Ｂ）を１〜５０質量％、さらには１０〜５０質量％、１５〜３５質量％の割合で含むことが好ましい。無機充填材（Ｂ）の量が前記下限値以上であると、射出成形時やはんだリフロー工程で成形物が変形することが無く、また、反射率の経時安定性に優れる傾向がある。また前記上限値以下であると、成形性および外観が良好な成形品を得ることができる。 The polyester resin composition for a reflector of the present invention is based on the total amount of the polyester resin (A), inorganic filler (B), white pigment (C), fluorescent brightener (D), and light stabilizer (E). The inorganic filler (B) is preferably contained in an amount of 1 to 50 mass%, more preferably 10 to 50 mass%, and 15 to 35 mass%. When the amount of the inorganic filler (B) is equal to or more than the lower limit value, the molded product is not deformed during the injection molding or the solder reflow process, and the reflectance stability with time tends to be excellent. Moreover, the molded product with favorable moldability and external appearance can be obtained as it is below the said upper limit.
本発明の反射材用ポリエステル樹脂組成物は、ポリエステル樹脂（Ａ）、無機充填材（Ｂ）、白色顔料（Ｃ）、蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）の総量に対して、白色顔料（Ｃ）を５〜５０質量％の割合で含むことが好ましく、より好ましくは１０〜５０質量％、さらに好ましくは１０〜４０質量％の割合で含み得る。白色顔料（Ｃ）の量が５質量％以上であると、反射率等の十分な光の反射特性を得ることができる。また５０質量％以下であれば、成形性を損なうことがなく好ましい。 The polyester resin composition for a reflector of the present invention is based on the total amount of the polyester resin (A), inorganic filler (B), white pigment (C), fluorescent brightener (D), and light stabilizer (E). The white pigment (C) is preferably contained in a proportion of 5 to 50% by mass, more preferably 10 to 50% by mass, and still more preferably 10 to 40% by mass. When the amount of the white pigment (C) is 5% by mass or more, sufficient light reflection characteristics such as reflectance can be obtained. Moreover, if it is 50 mass% or less, a moldability is not impaired and it is preferable.
本発明の反射材用ポリエステル樹脂組成物は、ポリエステル樹脂（Ａ）、無機充填材（Ｂ）、白色顔料（Ｃ）、蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）の総量に対して、蛍光増白剤（Ｄ）を０．０１〜０．２質量％の割合で含むことが好ましく、より好ましくは、０．０１〜０．１質量％である。 The polyester resin composition for a reflector of the present invention is based on the total amount of the polyester resin (A), inorganic filler (B), white pigment (C), fluorescent brightener (D), and light stabilizer (E). The brightening agent (D) is preferably contained in a proportion of 0.01 to 0.2% by mass, more preferably 0.01 to 0.1% by mass.
本発明の反射材用ポリエステル樹脂組成物は、ポリエステル樹脂（Ａ）、無機充填材（Ｂ）、白色顔料（Ｃ）、蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）の総量に対して、耐光安定剤（Ｅ）を０．０１〜０．２質量％の割合で含むことが好ましく、より好ましくは、０．０１〜０．１５質量％である。 The polyester resin composition for a reflector of the present invention is based on the total amount of the polyester resin (A), inorganic filler (B), white pigment (C), fluorescent brightener (D), and light stabilizer (E). The light stabilizer (E) is preferably contained in an amount of 0.01 to 0.2% by mass, more preferably 0.01 to 0.15% by mass.
本発明の反射材用ポリエステル樹脂組成物において、蛍光増白剤（Ｄ）と耐光安定剤（Ｅ）との質量比率は、２／１０〜５／１０であることが好ましい。蛍光増白剤（Ｄ）と耐光安定剤（Ｅ）とを、上記比率で組み合わせることで、反射材用ポリエステル樹脂組成物の耐紫外線性安定性がより向上する。 In the polyester resin composition for a reflector of the present invention, the mass ratio of the fluorescent brightener (D) and the light stabilizer (E) is preferably 2/10 to 5/10. By combining the fluorescent whitening agent (D) and the light-resistant stabilizer (E) in the above ratio, the ultraviolet resistance stability of the polyester resin composition for a reflector is further improved.
［反射材用ポリエステル樹脂組成物の用途］
本発明の反射材用ポリエステル樹脂組成物は、成形物の機械強度が高く、耐熱性に優れ、流動性、成形性に優れ、反射率が高く、経時的な反射率低下が少ない（特に、紫外線に曝されたときの劣化が少なく、反射率が低下しにくい）ことから、種々の反射板に好適である。特に限定されないが、半導体レーザーや発光ダイオード等の光源からの光線を反射する反射板に好適である。
[Use of polyester resin composition for reflective material]
The polyester resin composition for a reflector of the present invention has a molded article having high mechanical strength, excellent heat resistance, excellent fluidity and moldability, high reflectivity, and little decrease in reflectivity over time (especially ultraviolet light). Therefore, it is suitable for various reflectors. Although not particularly limited, it is suitable for a reflector that reflects light from a light source such as a semiconductor laser or a light emitting diode.
［反射材用ポリエステル樹脂組成物の調製］
本発明の反射材用熱可塑性樹脂組成物は、上記の各成分を、公知の方法、例えばヘンシェルミキサー、Ｖブレンダー、リボンブレンダー、タンブラーブレンダーなどで混合する方法、あるいは混合後さらに一軸押出機、多軸押出機、ニーダー、バンバリーミキサーなどで溶融混練後、造粒あるいは粉砕する方法により製造することができる。
[Preparation of polyester resin composition for reflector]
The thermoplastic resin composition for a reflective material of the present invention is prepared by mixing the above-described components by a known method such as a Henschel mixer, a V blender, a ribbon blender, a tumbler blender or the like, or after mixing, a single screw extruder, It can be produced by a method of granulation or pulverization after melt-kneading with a shaft extruder, kneader, Banbury mixer or the like.
２．反射板
本発明の反射板は、上述の反射材用ポリエステル樹脂組成物を任意の形状に成形したものでありうる。
2. Reflector The reflector of the present invention may be formed by molding the above-described polyester resin composition for a reflector into an arbitrary shape.
反射板とは、少なくとも光を放射する方向の面が開放された、または開放されていないケーシングやハウジング一般を包括している。より具体的には、箱状または函状の形状を有するもの、漏斗状の形状を有するもの、お椀状の形状を有するもの、パラボラ状の形状を有するもの、円柱状の形状を有するもの、円錐状の形状を有するもの、ハニカム状の形状を有するもの等、光を反射する面（平面、球面、曲面等の面）を有する三次元形状の成形体一般をも包含する。 The reflection plate includes a general casing or housing in which at least a surface in the direction of emitting light is open or not open. More specifically, one having a box shape or box shape, one having a funnel shape, one having a bowl shape, one having a parabolic shape, one having a columnar shape, a cone In general, a three-dimensional shaped product having a light reflecting surface (a surface such as a flat surface, a spherical surface, or a curved surface), such as a material having a shape like a honeycomb or a material having a honeycomb shape, is also included.
特に、本発明の反射材用ポリエステル樹脂組成物の成形物である反射板は、薄肉形状であっても十分な強度を有しつつ、反射率の保持性に優れる。つまり、紫外線などの太陽光に長時間曝されても、反射率を低下させない。 In particular, the reflection plate, which is a molded product of the polyester resin composition for a reflector according to the present invention, is excellent in reflectivity retention while having sufficient strength even if it is thin. That is, the reflectance is not lowered even when exposed to sunlight such as ultraviolet rays for a long time.
本発明の反射板の用途として、特に好ましくは発光ダイオード素子用の反射板が挙げられる。本発明の発光ダイオード（ＬＥＤ）素子用反射板は、上述の反射材用熱可塑性樹脂組成物を、射出成形、特にフープ成形等の金属のインサート成形、溶融成形、押出し成形、インフレーション成形、ブロー成形等の加熱成形により、所望の形状に賦形することで得られる。そして、該反射板に、ＬＥＤ素子とその他の部品を組み込み、封止用樹脂により封止、接合、接着等して、発光ダイオード素子を得ることができる。 The use of the reflector of the present invention is particularly preferably a reflector for a light-emitting diode element. The light-emitting diode (LED) element reflector of the present invention is obtained by injection-molding the above-mentioned thermoplastic resin composition for reflectors, particularly metal insert molding such as hoop molding, melt molding, extrusion molding, inflation molding, and blow molding. It can be obtained by shaping into a desired shape by thermoforming. Then, the LED element and other components are incorporated into the reflector, and the light emitting diode element can be obtained by sealing, bonding, bonding, etc. with a sealing resin.
また、本発明のポリエステル樹脂組成物および反射板はＬＥＤ用途のみならず、その他の光線を反射する用途にも適応することができる。具体的な例としては、各種電気電子部品、室内照明、天井照明、屋外照明、自動車照明、表示機器、ヘッドライト等の発光装置用の反射板として使用できる。 Moreover, the polyester resin composition and reflector of the present invention can be applied not only to LED applications but also to other applications that reflect light rays. As a specific example, it can be used as a reflector for light emitting devices such as various electric and electronic components, indoor lighting, ceiling lighting, outdoor lighting, automobile lighting, display equipment, and headlights.
ポリエステル樹脂（Ａ）の製造
ジメチルテレフタレートｌ０６．２部と、１,４-シクロヘキサンジメタノール（シス／トランス比：３０／７０）９４．６部との混合物に、テトラブチルチタネート０．００３７部を加え、１５０℃から３００℃まで３時間３０分かけて昇温して、エステル交換反応をさせた。エステル交換反応終了時に、１,４-シクロヘキサンジメタノールに溶解した酢酸マグネシウム・四水塩０．０６６部を加えて、引き続きテトラブチルチタネート０．１０２７部を導入して重縮合反応を行った。
Preparation of polyester resin (A) To a mixture of 106.2 parts of dimethyl terephthalate and 94.6 parts of 1,4-cyclohexanedimethanol (cis / trans ratio: 30/70), 0.0037 parts of tetrabutyl titanate was added. The temperature was raised from 150 ° C. to 300 ° C. over 3 hours and 30 minutes to carry out a transesterification reaction. At the end of the transesterification reaction, 0.066 part of magnesium acetate tetrahydrate dissolved in 1,4-cyclohexanedimethanol was added, and then 0.1027 part of tetrabutyl titanate was introduced to carry out a polycondensation reaction.
重縮合反応は常圧から１Ｔｏｒｒまで８５分かけて徐々に減圧し、同時に所定の重合温度３００℃まで昇温させた。温度と圧力を保持して、所定の撹拌トルクに到達した時点で反応を終了した。生成した重合体を取り出した。 In the polycondensation reaction, the pressure was gradually reduced from normal pressure to 1 Torr over 85 minutes, and at the same time, the temperature was raised to a predetermined polymerization temperature of 300 ° C. The reaction was terminated when the temperature and pressure were maintained and a predetermined stirring torque was reached. The produced polymer was taken out.
さらに、得られた重合体を２６０℃、１Torr以下で３時間固相重合を行なった。得られた重合体（ポリエステル樹脂（Ａ））の[η]は０．６ｄｌ/ｇ、融点は２９０℃であった。 Further, the obtained polymer was subjected to solid phase polymerization at 260 ° C. and 1 Torr or less for 3 hours. [Η] of the obtained polymer (polyester resin (A)) was 0.6 dl / g, and the melting point was 290 ° C.
ポリアミド樹脂の製造（参考例）
テレフタル酸３２８２７ｇ（１９７．６モル）と、１,９-ノナンジアミン２５３２６ｇ（１６０モル）と、２-メチル-１,８-オクタンジアミン６３３１．６ｇ（４０モル）と、安息香酸５８６．２ｇ（４．８モル）と、次亜リン酸ナトリウム一水和物６５ｇ（原料に対して０．１重量％）と、蒸留水４０リットルとを、オートクレーブに入れ、窒素置換した。１００℃で３０分間攪拌し、２時間かけて内部温度を２１０℃に昇温した。この時、オートクレーブ内の圧力は２２ｋｇ／ｃｍ２まで昇圧した。そのまま１時間反応を続けた後に、２３０℃に昇温し、その後２時間、２３０℃に温度を保ち、水蒸気を徐々に抜いて圧力を２２ｋｇ／ｃｍ２に保ちながら反応させた。次に、３０分かけて圧力を１０ｋｇ／ｃｍ２まで下げ、更に１時間反応させて、極限粘度［η］が０．２５ｄｌ／ｇのプレポリマーを得た。
Manufacture of polyamide resin (reference example)
32827 g (197.6 mol) of terephthalic acid, 25326 g (160 mol) of 1,9-nonanediamine, 6331.6 g (40 mol) of 2-methyl-1,8-octanediamine, and 586.2 g of benzoic acid (4. 8 mol), 65 g of sodium hypophosphite monohydrate (0.1% by weight based on the raw material) and 40 liters of distilled water were placed in an autoclave and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At this time, the pressure in the autoclave was increased to 22 kg / cm 2 . The reaction was continued for 1 hour as it was, and then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 22 kg / cm 2 . Next, the pressure was reduced to 10 kg / cm 2 over 30 minutes and the reaction was further continued for 1 hour to obtain a prepolymer having an intrinsic viscosity [η] of 0.25 dl / g.
プレポリマーを、１００℃、減圧下で１２時間乾燥させた。乾燥物を、粒径２ｍｍ以下の大きさまで粉砕した。粉砕物を２３０℃、０．１ｍｍＨｇ下にて、１０時間固相重合し、融点が３０１℃、極限粘度［η］が１．２ｄｌ／ｇのナイロン９Ｔを得た（以下このポリアミド樹脂を（Ｐ）という）。 The prepolymer was dried at 100 ° C. under reduced pressure for 12 hours. The dried product was pulverized to a particle size of 2 mm or less. The pulverized product was subjected to solid phase polymerization at 230 ° C. and 0.1 mmHg for 10 hours to obtain nylon 9T having a melting point of 301 ° C. and an intrinsic viscosity [η] of 1.2 dl / g (hereinafter, this polyamide resin is referred to as (P )).
無機充填材（Ｂ）：ガラス繊維：長さ３ｍｍ、異形アスペクト比３００（セントラル硝子（株）製ＥＣＳ０３−６１５、シラン化合物処理品） Inorganic filler (B): Glass fiber: length 3 mm, irregular aspect ratio 300 (Central Glass Co., Ltd. ECS03-615, silane compound treated product)
白色顔料（Ｃ）：酸化チタン（粉末状、平均粒径０．２１μm） White pigment (C): Titanium oxide (powder, average particle size 0.21 μm)
蛍光増白剤（Ｄ）：Ｈｏｓｔａｌｕｘ ＫＳ（クラリアントジャパン（株）） Optical brightener (D): Hostalux KS (Clariant Japan Co., Ltd.)
耐光安定剤（Ｅ１）：ナイロスタブ Ｓ−ＥＥＤ（クラリアントジャパン（株））
耐光安定剤（Ｅ２）：アデカスタブＬＡ−６３Ｐ（アデカ（株））
Light-resistant stabilizer (E1): Nylostab S-EED (Clariant Japan Co., Ltd.)
Light-resistant stabilizer (E2): ADK STAB LA-63P (ADEKA Corporation)
酸化防止剤（Ｆ）：イルガノックス１０１０（ＢＡＳＦ） Antioxidant (F): Irganox 1010 (BASF)
離型剤（Ｇ）：公知の固体状チタン触媒成分で得られたエチレン重合体系ワックスとスチレンとの混合物を公知のラジカル発生剤の存在下に反応させて、以下の低分子量熱可塑性樹脂（Ｇ）を得た。
デカリン中１３５℃で測定した粘度：０．１０ｄｌ／ｇ
１４０℃での溶融粘度：１,１００ｍＰｓ・ｓ
スチレン単位含有率：６０質量％
Release agent (G): A mixture of an ethylene polymer wax obtained with a known solid titanium catalyst component and styrene is reacted in the presence of a known radical generator to produce the following low molecular weight thermoplastic resin (G )
Viscosity measured at 135 ° C. in decalin: 0.10 dl / g
Melt viscosity at 140 ° C: 1,100 mPs · s
Styrene unit content: 60% by mass
［実施例１］
前記ポリエステル樹脂（Ａ）、無機充填材（Ｂ）、白色顔料（Ｃ）、蛍光増白剤（Ｄ）、耐光安定剤（Ｅ１とＥ２）、およびその他の共有配合剤（酸化防止剤(Ｆ)と離型剤(Ｇ)）を、表１に示す割合でタンブラーブレンダーを用いて混合した。混合物を、二軸押出機（（株）日本製鋼所製ＴＥＸ３０α）にて、シリンダー温度３００℃で原料を溶融混錬後、ストランド状に押出した。押出し物を水槽で冷却後、ペレタイザーでストランドを引き取り、カットすることでペレット状組成物を得た。（すなわち良好なコンパウンド性を示した。）
[Example 1]
The polyester resin (A), inorganic filler (B), white pigment (C), optical brightener (D), light stabilizer (E1 and E2), and other shared compounding agents (antioxidant (F) And the release agent (G)) were mixed at a ratio shown in Table 1 using a tumbler blender. The mixture was extruded into a strand after melt-kneading the raw material at a cylinder temperature of 300 ° C. with a twin-screw extruder (TEX30α manufactured by Nippon Steel). The extrudate was cooled in a water tank, and then a strand was drawn with a pelletizer and cut to obtain a pellet-shaped composition. (In other words, it showed good compounding properties.)
［実施例２］、［比較例１〜７］
各成分の組成を表１に示す組成とした以外は、実施例１と同様にして、ペレット状組成物を調製した。
[Example 2], [Comparative Examples 1 to 7]
A pellet-shaped composition was prepared in the same manner as in Example 1 except that the composition of each component was changed to the composition shown in Table 1.
各実施例および比較例で得られたペレット状組成物について、以下の物性を評価した。それらの結果を表１に示した。 The following physical properties were evaluated for the pellet-like compositions obtained in each Example and Comparative Example. The results are shown in Table 1.
（薄肉曲げ試験）
下記射出成形機を用い、下記成形条件で調製した長さ６４ｍｍ、幅６ｍｍ、厚さ０．８ｍｍの試験片を、温度２３℃、窒素雰囲気下で２４時間放置した。次いで、温度２３℃、相対湿度５０％の雰囲気下で、曲げ試験機（ＮＴＥＳＣＯ社製ＡＢ５）で、スパン２６ｍｍ、曲げ速度５ｍｍ／分で曲げ試験を行い、試験片の強度、弾性率、およびたわみ量を測定した。
成形機：（株）ソディック プラステック、ツパールＴＲ４０Ｓ３Ａ
成形機シリンダー温度：融点（Ｔｍ）＋１０℃、金型温度：１５０℃
(Thin wall bending test)
Using the following injection molding machine, a test piece having a length of 64 mm, a width of 6 mm, and a thickness of 0.8 mm prepared under the following molding conditions was allowed to stand at a temperature of 23 ° C. in a nitrogen atmosphere for 24 hours. Next, a bending test was performed at a span of 26 mm and a bending speed of 5 mm / min with a bending tester (AB5 manufactured by NTSCO) in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%. The strength, elastic modulus, and deflection of the test piece were The amount was measured.
Molding machine: Sodick Plustech Co., Ltd. Tupar TR40S3A
Molding machine cylinder temperature: melting point (Tm) + 10 ° C., mold temperature: 150 ° C.
（初期反射率）
下記成形機を用い、下記成形条件で射出成形して調製した長さ３０ｍｍ、幅３０ｍｍ、厚さ０．５ｍｍの試験片を得た。得られた試験片の反射率を、ミノルタ（株）ＣＭ３５００ｄを用いて、波長領域３６０nmから７４０nmの範囲で求めた。４５０nmの反射率を代表値として初期反射率を評価した。
成形機：住友重機械工業（株）社製、ＳＥ５０ＤＵ
シリンダー温度：融点（Ｔｍ）＋１０℃、金型温度：１５０℃
(Initial reflectance)
Using the following molding machine, a test piece having a length of 30 mm, a width of 30 mm, and a thickness of 0.5 mm prepared by injection molding under the following molding conditions was obtained. The reflectance of the obtained test piece was determined in the wavelength range of 360 nm to 740 nm using Minolta CM3500d. The initial reflectance was evaluated using the reflectance at 450 nm as a representative value.
Molding machine: SE50DU, manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder temperature: melting point (Tm) + 10 ° C., mold temperature: 150 ° C.
（加熱後反射率）
初期反射率の測定に用いたサンプルを、１５０℃のオーブンに５０４時間放置した。このサンプルを初期反射率と同様の方法で反射率を測定し、加熱後反射率とした。
(Reflectance after heating)
The sample used for the measurement of the initial reflectance was left in an oven at 150 ° C. for 504 hours. The reflectance of this sample was measured by the same method as the initial reflectance, and was defined as the reflectance after heating.
（流動性）
幅１０ｍｍ、厚み０．５ｍｍのバーフロー金型を使用して以下の条件で射出し、金型内の樹脂の流動長（ｍｍ）を測定した。
射出成形機：（株）ソディック プラステック、ツパールＴＲ４０Ｓ３Ａ
射出設定圧力：２０００ｋｇ／ｃｍ２、シリンダー設定温度：融点（Ｔｍ）＋１０℃
金型温度：３０℃
(Liquidity)
A bar flow mold having a width of 10 mm and a thickness of 0.5 mm was used for injection under the following conditions, and the flow length (mm) of the resin in the mold was measured.
Injection molding machine: Sodick Plustec, Tupar TR40S3A
Injection set pressure: 2000 kg / cm 2 , cylinder set temperature: melting point (Tm) + 10 ° C.
Mold temperature: 30 ℃
（耐ＵＶ特性）
初期反射率の測定に用いたサンプルに、メタルハライドランプ（大日本プラスチック（株）製、アイ・スーパーＵＶテスター（４０ｍＷ／ｃｍ２，４８ｈ））にて８５℃、５０ｍＷ／ｃｍ２で、３００時間の光を照射した。光照射前後における反射板の、波長４５０ｎｍの光の反射率を測定した（反射率測定器：ミノルタ（株）ＣＭ３５００ｄ）。
(UV resistance)
The sample used for the measurement of the initial reflectance was a metal halide lamp (Dainippon Plastic Co., Ltd., Eye Super UV Tester (40 mW / cm 2 , 48 h)) at 85 ° C. and 50 mW / cm 2 for 300 hours. Irradiated with light. The reflectance of light having a wavelength of 450 nm on the reflector before and after the light irradiation was measured (reflectance measuring instrument: Minolta Co., Ltd. CM3500d).
光照射前の反射率に対する照射後の値の比率を、以下の式に基づき算出した。
反射率保持率（％）＝［Ｒ２／Ｒ１］×１００
Ｒ１：メタルハライドランプによる光照射前の、波長４５０ｎｍの光の反射率
Ｒ２：メタルハライドランプによる光照射後の、波長４５０ｎｍの光の反射率
The ratio of the value after irradiation to the reflectance before light irradiation was calculated based on the following formula.
Reflectance holding ratio (%) = [R2 / R1] × 100
R1: Reflectance of light having a wavelength of 450 nm before light irradiation by a metal halide lamp R2: Reflectance of light having a wavelength of 450 nm after light irradiation by a metal halide lamp
実施例１および２の反射板は、加熱により反射率の低下（加熱後反射特性）も、紫外線の照射による反射率の低下（耐ＵＶ特性）も小さいことがわかる。一方で、比較例１〜７の反射板は、いずれも、紫外線の照射による反射率の低下が大きいことがわかる。 It can be seen that the reflectors of Examples 1 and 2 have a small decrease in reflectance (reflecting characteristics after heating) due to heating and a small decrease in reflectance (ultraviolet resistance) due to ultraviolet irradiation. On the other hand, it can be seen that all of the reflection plates of Comparative Examples 1 to 7 have a large decrease in reflectance due to irradiation with ultraviolet rays.
本発明の反射材用ポリエステル樹脂組成物は、反射材料として用いられる。例えば、屋外での使用される反射板に成形するための樹脂組成物として用いられる。さらに詳しくは、本発明の反射材用ポリエステル樹脂組成物は、耐ＵＶ特性と長期での反射特性に優れるとともに、インサート成形に好適である。
The polyester resin composition for a reflective material of the present invention is used as a reflective material. For example, it is used as a resin composition for molding into a reflector used outdoors. More specifically, the polyester resin composition for a reflector of the present invention is excellent in UV resistance and long-term reflection characteristics, and is suitable for insert molding.
Claims (6)
無機充填材（Ｂ）１〜５０質量％と、
白色顔料（Ｃ）５〜５０質量％と、
蛍光増白剤（Ｄ）０．０１〜０．２質量％と、
耐光安定剤（Ｅ）０．０１〜０．２質量％と、
を含み、
前記耐光安定剤（Ｅ）が、窒素を含むヘテロ環を２個以上有し、分子量が４００ｇ/ｍｏｌ以上の化合物である、
反射材用ポリエステル樹脂組成物（ただし、ポリエステル樹脂（Ａ），無機充填材（Ｂ），白色顔料（Ｃ），蛍光増白剤（Ｄ）および耐光安定剤（Ｅ）の合計は１００質量％である）。 30-80% by mass of a polyester resin (A) having a melting point or glass transition temperature of 250 ° C. or higher,
1-50% by mass of inorganic filler (B),
White pigment (C) 5-50 mass%,
Optical brightener (D) 0.01-0.2 mass%,
Light-resistant stabilizer (E) 0.01-0.2 mass%,
Only including,
The light-resistant stabilizer (E) is a compound having two or more hetero rings containing nitrogen and having a molecular weight of 400 g / mol or more.
Reflector polyester resin composition (however, the total of polyester resin (A), inorganic filler (B), white pigment (C), fluorescent brightener (D) and light stabilizer (E) is 100% by mass) is there).
テレフタル酸から誘導されるジカルボン酸成分単位３０〜１００モル％、テレフタル酸以外の芳香族ジカルボン酸成分単位０〜７０モル％からなるジカルボン酸成分単位（ａ−１）並びに、
炭素原子数４〜２０の脂環族ジアルコール成分単位（ａ−３）および／または脂肪族ジアルコール成分単位（ａ−４）
を含むポリエステル樹脂である、請求項１に記載の反射材用ポリエステル樹脂組成物。 The polyester resin (A) is
Dicarboxylic acid component units derived from terephthalic acid 30-100 mol%, dicarboxylic acid component units (a-1) consisting of aromatic dicarboxylic acid component units other than terephthalic acid 0-70 mol%, and
C4-C20 alicyclic dialcohol component unit (a-3) and / or aliphatic dialcohol component unit (a-4)
The polyester resin composition for reflectors according to claim 1, which is a polyester resin containing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013113095A JP6042271B2 (en) | 2013-05-29 | 2013-05-29 | Polyester resin composition for reflector and reflector |
Applications Claiming Priority (1)
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| JP2017071728A (en) * | 2015-10-09 | 2017-04-13 | 三井化学株式会社 | Polyester resin composition, method for manufacturing reflector and method for manufacturing light-emitting diode (led) element |
| CN110036500B (en) | 2016-12-26 | 2022-03-11 | 株式会社Lg化学 | Cylindrical battery cell with heat shrinkable tube containing ultraviolet stabilizer |
| JP7450400B2 (en) * | 2019-03-14 | 2024-03-15 | ダイセルミライズ株式会社 | Light-resistant thermoplastic resin composition |
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| US20100072416A1 (en) * | 2006-10-31 | 2010-03-25 | Techno Polymer Co. Ltd | Heat-dissipating resin composition, substrate for led mounting, reflector, and substrate for led mounting having reflector portion |
| JP5115083B2 (en) * | 2007-08-08 | 2013-01-09 | 東レ株式会社 | White polyester film for LCD reflector |
| US9062198B2 (en) * | 2011-04-14 | 2015-06-23 | Ticona Llc | Reflectors for light-emitting diode assemblies containing a white pigment |
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