JP5467572B2 - Polycarbonate resin composition and molded article comprising the same - Google Patents
Polycarbonate resin composition and molded article comprising the same Download PDFInfo
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- JP5467572B2 JP5467572B2 JP2009292353A JP2009292353A JP5467572B2 JP 5467572 B2 JP5467572 B2 JP 5467572B2 JP 2009292353 A JP2009292353 A JP 2009292353A JP 2009292353 A JP2009292353 A JP 2009292353A JP 5467572 B2 JP5467572 B2 JP 5467572B2
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- 229920005668 polycarbonate resin Polymers 0.000 title claims description 25
- 239000004431 polycarbonate resin Substances 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 title claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 18
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 238000001579 optical reflectometry Methods 0.000 claims description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 14
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 12
- -1 3-methyl-4hydroxy-5-tert-butylphenyl Chemical group 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 4
- AESQDCMZHBUWPN-UHFFFAOYSA-N 4h-1,3,2-dioxaphosphinine Chemical compound C1OPOC=C1 AESQDCMZHBUWPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 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 7
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- FDLFMPKQBNPIER-UHFFFAOYSA-N 1-methyl-3-(3-methylphenoxy)benzene Chemical compound CC1=CC=CC(OC=2C=C(C)C=CC=2)=C1 FDLFMPKQBNPIER-UHFFFAOYSA-N 0.000 description 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
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- QHJPJZROUNGTRJ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)octan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCC)C1=CC=C(O)C=C1 QHJPJZROUNGTRJ-UHFFFAOYSA-N 0.000 description 1
- GRCXOICCGCYITB-UHFFFAOYSA-N 4-[2-[2-[2-(4-hydroxyphenyl)-3-methylphenyl]propan-2-yl]-6-methylphenyl]phenol Chemical compound CC1=CC=CC(C(C)(C)C=2C(=C(C)C=CC=2)C=2C=CC(O)=CC=2)=C1C1=CC=C(O)C=C1 GRCXOICCGCYITB-UHFFFAOYSA-N 0.000 description 1
- RQTDWDATSAVLOR-UHFFFAOYSA-N 4-[3,5-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC(C=2C=CC(O)=CC=2)=CC(C=2C=CC(O)=CC=2)=C1 RQTDWDATSAVLOR-UHFFFAOYSA-N 0.000 description 1
- XHDKBYRAWKLXGE-UHFFFAOYSA-N 4-[4,6-bis(4-hydroxyphenyl)-4,6-dimethylhept-1-en-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)CC(C)(C=1C=CC(O)=CC=1)CC(=C)C1=CC=C(O)C=C1 XHDKBYRAWKLXGE-UHFFFAOYSA-N 0.000 description 1
- CIEGINNQDIULCT-UHFFFAOYSA-N 4-[4,6-bis(4-hydroxyphenyl)-4,6-dimethylheptan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC(C)(C=1C=CC(O)=CC=1)CC(C)(C)C1=CC=C(O)C=C1 CIEGINNQDIULCT-UHFFFAOYSA-N 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000005275 alloying Methods 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
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000004790 diaryl sulfoxides Chemical class 0.000 description 1
- 150000001987 diarylethers Chemical class 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、高い光反射性を有し、かつ優れた熱安定性を有するポリカーボネート樹脂組成物、および該組成物より成形されてなる成形品に関する。本発明に係わる樹脂組成物は、光反射性および熱安定性に優れ、さらには耐衝撃性、外観にも優れていることから、特に液晶フレームまたはランプホルダー用光反射板に好適に使用できる。 The present invention relates to a polycarbonate resin composition having high light reflectivity and excellent thermal stability, and a molded product formed from the composition. Since the resin composition according to the present invention is excellent in light reflectivity and thermal stability, and further excellent in impact resistance and appearance, it can be suitably used particularly for a light reflector for a liquid crystal frame or a lamp holder.
ポリカーボネート樹脂は、耐衝撃性、耐熱性などに優れた熱可塑性樹脂であり、電気、電子、機械、自動車などの分野に広く用いられている。なかでも液晶表示装置のフレームやランプホルダー等の光反射板の用途においては、耐衝撃性、耐熱性等の面からポリカーボネート樹脂が着目されており、ポリカーボネート樹脂に高い光反射性を付与するために、多量の酸化チタンを配合する方法が提案されている。また、酸化チタンの表面を処理することで所望とする光反射性を得ることが試みられている。（特許文献１〜３を参照） Polycarbonate resin is a thermoplastic resin excellent in impact resistance, heat resistance, and the like, and is widely used in fields such as electricity, electronics, machinery, and automobiles. In particular, in applications of light reflectors such as frames and lamp holders for liquid crystal display devices, polycarbonate resin has attracted attention in terms of impact resistance, heat resistance, etc., in order to impart high light reflectivity to polycarbonate resin. A method of blending a large amount of titanium oxide has been proposed. Further, it has been attempted to obtain a desired light reflectivity by treating the surface of titanium oxide. (See Patent Documents 1 to 3)
液晶フレームやランプホルダーに使用されるポリカーボネート樹脂に対しては、本来有する優れた耐衝撃性や耐熱性といった性能に加えて、高度の難燃性のみならず高度な光反射性が求められていた。多量の酸化チタンを配合した難燃性ポリカーボネート樹脂は、光反射性は向上するものの、多量の酸化チタンを含有するため、射出成形時の熱安定性や成形加工性の低下を招き、さらには成形品の表面外観にシルバーストリーク等が発生するといった問題も有しており、これらの改善も望まれていた。 For polycarbonate resin used in liquid crystal frames and lamp holders, in addition to the inherently superior impact resistance and heat resistance, not only high flame retardancy but also high light reflectivity was required. . Although flame retardant polycarbonate resin containing a large amount of titanium oxide improves light reflectivity, it contains a large amount of titanium oxide, leading to a decrease in thermal stability and molding processability during injection molding. There is also a problem that silver streaks and the like occur on the surface appearance of the product, and these improvements have been desired.
本発明者らは、かかる課題に鑑み鋭意研究を行った結果、酸化チタンを含むポリカーボネート樹脂に環状亜りん酸エステル系酸化防止剤を配合することにより、ポリカーボネート樹脂が有する種々の優れた性能を損なうことなく、優れた光反射性を示し、かつ従来のリン系酸化防止剤を使用した場合と比較して優れた熱安定性を発現することを見出し、本発明を完成するに至った。 As a result of intensive studies in view of such problems, the present inventors impair various excellent performances of the polycarbonate resin by blending a cyclic phosphite-based antioxidant with the polycarbonate resin containing titanium oxide. The present inventors have found that excellent light reflectivity is exhibited and that excellent thermal stability is exhibited as compared with the case where a conventional phosphorus antioxidant is used, and the present invention has been completed.
すなわち、本発明は、ポリカーボネート樹脂（Ａ）１００重量部、酸化チタン（Ｂ）１５〜２５重量部および環状亜リン酸エステル系酸化防止剤（Ｃ）０．００５〜１重量部からなる樹脂組成物であって、前記環状亜りん酸エステル系酸化防止剤（Ｃ）が、２，４，８，１０−テトラ−ｔ−ブチル−６−［３−（３−メチル−４ヒドロキシ−５−ｔ−ブチルフェニル）プロポキシ］ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピンであることを特徴とするポリカーボネート樹脂組成物およびそれからなる成形品を提供するものである。
That is, the present invention provides a resin composition comprising 100 parts by weight of a polycarbonate resin (A), 15 to 25 parts by weight of titanium oxide (B), and 0.005 to 1 part by weight of a cyclic phosphite antioxidant (C) . The cyclic phosphite antioxidant (C) is 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4hydroxy-5-t- It is an object of the present invention to provide a polycarbonate resin composition characterized by being butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine and a molded product comprising the same.
本発明の光反射性に優れたポリカーボネート樹脂組成物は、ポリカーボネート樹脂が有する種々の優れた性能を損なうことなく、高い光反射性および熱安定性を有していることから、液晶フレームまたはランプホルダー用光反射板等の用途に好適であり、実用上の利用価値が極めて高い。 The polycarbonate resin composition having excellent light reflectivity according to the present invention has high light reflectivity and heat stability without impairing various excellent performances of the polycarbonate resin. It is suitable for applications such as a light reflector for use, and has a very high practical utility value.
本発明にて使用されるポリカーボネート樹脂（Ａ）とは、種々のジヒドロキシジアリール化合物とホスゲンとを反応させるホスゲン法、またはジヒドロキシジアリール化合物とジフェニルカーボネートなどの炭酸エステルとを反応させるエステル交換法によって得られる重合体であり、代表的なものとしては、２，２−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）から製造されたポリカーボネート樹脂が挙げられる。 The polycarbonate resin (A) used in the present invention is obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted, or a transesterification method in which a dihydroxydiaryl compound and a carbonate such as diphenyl carbonate are reacted. A typical example of the polymer is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).
上記ジヒドロキシジアリール化合物としては、ビスフェノールＡの他に、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）オクタン、ビス（４−ヒドロキシフェニル）フェニルメタン、２，２−ビス（４−ヒドロキシフェニル−３−メチルフェニル）プロパン、１，１−ビス（４−ヒドロキシ−３−第三ブチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−ブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３、５−ジブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）プロパンのようなビス（ヒドロキシアリール）アルカン類、１，１−ビス（４−ヒドロキシフェニル）シクロペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサンのようなビス（ヒドロキシアリール）シクロアルカン類、４，４′−ジヒドロキシジフェニルエーテル、４，４′−ジヒドロキシ−３，３′−ジメチルジフェニルエーテルのようなジヒドロキシジアリールエーテル類、４，４′−ジヒドロキシジフェニルスルフィドのようなジヒドロキシジアリールスルフィド類、４，４′−ジヒドロキシジフェニルスルホキシド、４，４′−ジヒドロキシ−３，３′−ジメチルジフェニルスルホキシドのようなジヒドロキシジアリールスルホキシド類、４，４′−ジヒドロキシジフェニルスルホン、４，４′−ジヒドロキシ−３，３′−ジメチルジフェニルスルホンのようなジヒドロキシジアリールスルホン類等が挙げられる。 Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like.
これらは、単独または２種類以上混合して使用されるが、ハロゲンで置換されていない方が燃焼時に懸念される当該ハロゲンを含むガスの環境への排出防止の面から好ましい。これらの他に、ピペラジン、ジピペリジルハイドロキノン、レゾルシン、４，４′−ジヒドロキシジフェニル等を混合して使用してもよい。 These are used singly or as a mixture of two or more. However, it is preferable not to be substituted with a halogen from the viewpoint of preventing discharge of a gas containing halogen, which is a concern during combustion, into the environment. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.
さらに、上記のジヒドロキシアリール化合物と以下に示すような３価以上のフェノール化合物を混合使用してもよい。３価以上のフェノールとしてはフロログルシン、４，６−ジメチル−２，４，６−トリ−（４−ヒドロキシフェニル）−ヘプテン、２，４，６−ジメチル−２，４，６−トリ−（４−ヒドロキシフェニル）−ヘプタン、１，３，５−トリ−（４−ヒドロキシフェニル）−ベンゾール、１，１，１−トリ−（４−ヒドロキシフェニル）−エタンおよび２，２−ビス−［４，４−（４，４′−ジヒドロキシジフェニル）−シクロヘキシル］−プロパンなどが挙げられる。 Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.
ポリカーボネート樹脂（Ａ）の粘度平均分子量は通常１００００〜１０００００、好ましくは１２０００〜３５０００、更に好ましくは１５０００〜２８０００である。かかる芳香族ポリカーボネート樹脂を製造するに際し、分子量調節剤、触媒等を必要に応じて使用することができる。上記粘度平均分子量の測定方法は、塩化メチレンを溶媒として０．５重量％の溶液とし、キャノンフェンスケ型粘度管を用い温度２０℃で比粘度（ηsp）を測定し、濃度換算により極限粘度〔η〕を求め下記のＳＣＨＮＥＬＬの式から算出した。
〔η〕＝１．２３×１０−４Ｍ０．８３
The viscosity average molecular weight of the polycarbonate resin (A) is usually 10,000 to 100,000, preferably 12,000 to 35,000, and more preferably 15,000 to 28,000. In producing such an aromatic polycarbonate resin, a molecular weight regulator, a catalyst, and the like can be used as necessary. The viscosity average molecular weight is determined by measuring the specific viscosity (ηsp) at a temperature of 20 ° C. using a Cannon-Fenske type viscosity tube using methylene chloride as a solvent and using a Cannon-Fenske type viscosity tube. η] was obtained and calculated from the following SCHNELL equation.
[Η] = 1.23 × 10 −4 M 0.83
本発明にて使用される酸化チタン（Ｂ）とは、塩素法、硫酸法どちらで製造されたものでもよく、その結晶形態としてはルチル型、アナターゼ型のどちらであっても構わない。また、酸化チタンの粒径としては０．１〜０．５μｍ程度のものが好適である。 The titanium oxide (B) used in the present invention may be one produced by the chlorine method or the sulfuric acid method, and the crystal form may be either rutile type or anatase type. Further, the particle size of titanium oxide is preferably about 0.1 to 0.5 μm.
市販の酸化チタンとしては、ＤｕＰｏｎｔ社製Ｒ９０２，レジノカラー工業社製ＤＣＦ１７００７，Ｋｒｏｎｏｓ社製２２３０、石原産業社製タイペークＰＦ７４０等があげられる。 Examples of commercially available titanium oxide include DuPont R902, Resino Color Industries DCF 17007, Kronos 2230, Ishihara Sangyo Typek PF740, and the like.
酸化チタン（Ｂ）の配合量は、ポリカーボネート樹脂（Ａ）１００重量部あたり５〜２５重量部である。配合量が５重量部未満では光反射性に劣り、また２５重量部を超えると外観や機械強度（衝撃強度）が悪化するので好ましくない。より好適な配合量は９〜２０重量部の範囲である。 The compounding quantity of a titanium oxide (B) is 5-25 weight part per 100 weight part of polycarbonate resin (A). If the blending amount is less than 5 parts by weight, the light reflectivity is inferior, and if it exceeds 25 parts by weight, the appearance and mechanical strength (impact strength) are deteriorated. A more preferable blending amount is in the range of 9 to 20 parts by weight.
本発明にて使用される環状亜リン酸エステル系酸化防止剤（Ｃ）としては、フェノール類又はビスフェノール類と三ハロゲン化リンとアミン化合物とを反応させることにより製造されるものが挙げられる。反応方法としては通常、先ずフェノール類又はビスフェノール類と三ハロゲン化リンとを反応させ中間体を生成し、次いでアミン化合物を反応させるという二段反応法が採用される。反応は通常、有機溶剤中で０〜２００℃の環境下で行われる。環状亜リン酸エステル系酸化防止剤（Ｃ）のうち、特に２，４，８，１０−テトラ−ｔ−ブチル−６−［３−（３−メチル−４ヒドロキシ−５−ｔ−ブチルフェニル）プロポキシ］ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピンが好適であり、市販品として入手可能で住友化学社製スミライザーＧＰが挙げられる。 Examples of the cyclic phosphite antioxidant (C) used in the present invention include those produced by reacting phenols or bisphenols, phosphorus trihalide and amine compounds. As a reaction method, a two-step reaction method is generally employed in which phenols or bisphenols and phosphorus trihalide are first reacted to form an intermediate, and then an amine compound is reacted. The reaction is usually performed in an organic solvent in an environment of 0 to 200 ° C. Among the cyclic phosphite antioxidants (C), 2,4,8,10-tetra-t-butyl-6- [3- (3-methyl-4hydroxy-5-t-butylphenyl) is particularly preferred. Propoxy] dibenzo [d, f] [1,3,2] dioxaphosphine is suitable, and is available as a commercial product, and Sumitomo GP manufactured by Sumitomo Chemical Co., Ltd. may be mentioned.
環状亜リン酸エステル系酸化防止剤（Ｃ）の配合量としては、ポリカーボネート樹脂（Ａ）１００重量部あたり０．００５〜１重量部である。配合量が０．００５重量部未満では熱安定性が劣るので好ましくない。また、１重量部を超えると強度が低下するので好ましくない。この配合量は、好ましくは、０．０１〜０．５重量部、より好ましくは０．０２〜０．１重量部の範囲である。 The amount of the cyclic phosphite antioxidant (C) is 0.005 to 1 part by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.005 parts by weight, the thermal stability is poor, which is not preferable. Moreover, since an intensity | strength will fall when it exceeds 1 weight part, it is unpreferable. This amount is preferably in the range of 0.01 to 0.5 parts by weight, more preferably 0.02 to 0.1 parts by weight.
本発明の各種配合成分（Ａ）、（Ｂ）、（Ｃ）の配合方法は特に制限はなく、任意の混合機、例えばタンブラー、リボンブレンダー、高速ミキサー等によりこれらを混合し、通常の単軸または二軸押出機で容易に溶融混練することができる。また、これらの配合順序についても特に制限はない。 The blending method of the various blending components (A), (B), and (C) of the present invention is not particularly limited, and these are mixed by an optional mixer such as a tumbler, ribbon blender, high-speed mixer, etc. Or it can melt-knead easily with a twin-screw extruder. Moreover, there is no restriction | limiting in particular also about these compounding orders.
更に、本発明の効果を損なわない範囲で、本発明のポリカーボネート樹脂組成物に各種の熱安定剤、酸化防止剤、充填材、離型剤、紫外線吸収剤、帯電防止剤、軟化材、展着剤（エポキシ大豆油、流動パラフィン等）染顔料等の添加剤、他のポリマーを配合しても良い。 Furthermore, various heat stabilizers, antioxidants, fillers, mold release agents, ultraviolet absorbers, antistatic agents, softening materials, spreading materials are added to the polycarbonate resin composition of the present invention within the range not impairing the effects of the present invention. Additives such as dyes and pigments (such as epoxy soybean oil and liquid paraffin) and other polymers may be blended.
充填材としては、例えばガラス繊維、ガラスビーズ、ガラスフレーク、炭素繊維、タルク粉、クレイ粉、マイカ、チタン酸カリウムウィスカー、ワラストナイト粉、シリカ粉、アルミナ粉等が挙げられる。 Examples of the filler include glass fiber, glass bead, glass flake, carbon fiber, talc powder, clay powder, mica, potassium titanate whisker, wollastonite powder, silica powder, and alumina powder.
他のポリマーとしては、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル；ポリスチレン、ハイインパクトポリスチレン、ＡＢＳ樹脂、ＡＥＳ樹脂等のスチレン系ポリマー；ポリプロピレン、さらにポリカーボネートとアロイ化して通常使用されるポリマーが挙げられる。 Examples of other polymers include polyesters such as polyethylene terephthalate and polybutylene terephthalate; styrene polymers such as polystyrene, high impact polystyrene, ABS resin, and AES resin; polypropylene, and polymers that are usually used after alloying with polycarbonate. .
以下、本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。なお、特に断りのない限り、実施例中の「％」、「部」はそれぞれ重量基準に基づく。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. Unless otherwise specified, “%” and “parts” in the examples are based on weight standards.
なお、使用した原材料は以下のものである。
ポリカーボネート樹脂：
ビスフェノールＡとホスゲンから合成されたポリカーボネート樹脂
住友ダウ社製カリバー２００−２０
（粘度平均分子量：１９０００ 以下、ＰＣと略記）
酸化チタン：
Ｋｒｏｎｏｓ社製２２３０
環状亜りん酸エステル系酸化防止剤：
住友化学社製スミライザーＧＰ（以下、ＡＯ１と略記）
リン系酸化防止剤：
チバ・スペシャルティ・ケミカルズ社製イルガフォスＰ１６８（以下、ＡＯ２と略記）
The raw materials used are as follows.
Polycarbonate resin:
Polycarbonate resin synthesized from bisphenol A and phosgene Sumitomo Dow Caliber 200-20
(Viscosity average molecular weight: 19000 or less, abbreviated as PC)
Titanium oxide:
2230 made by Kronos
Cyclic phosphite antioxidants:
Sumitomo Chemical's Sumitizer GP (hereinafter abbreviated as AO1)
Phosphorous antioxidants:
Irgaphos P168 manufactured by Ciba Specialty Chemicals (hereinafter abbreviated as AO2)
本発明における各種評価項目の測定方法等について説明する。
（樹脂組成物ペレットの作成）
以下の表２〜表４に示す配合成分におよび配合比率にて、各種配合成分をタンブラーで混合し、３７ｍｍ径の二軸押出機（神戸製鋼社製ＫＴＸ３７）を用いて、シリンダー温度２８０度にて溶融混練し、各種ペレットを得た。
A method for measuring various evaluation items in the present invention will be described.
(Preparation of resin composition pellets)
In the blending components shown in Tables 2 to 4 below and blending ratios, various blending components are mixed with a tumbler, and the cylinder temperature is set to 280 degrees using a 37 mm diameter twin screw extruder (KTX37 manufactured by Kobe Steel). And kneaded to obtain various pellets.
（光反射性）
得られたペレットを１２５℃で４時間乾燥後、射出成形機（日本製鋼所製Ｊ１００Ｃ−５）を用いて３００℃、射出圧力１６００ｋｇ／ｃｍ２の条件下、光学測定用試験片（幅５０ｍｍ、長さ４０ｍｍ、厚み２ｍｍ）を成形した。前述の試験片を２３℃、湿度５０％の恒温室の中で４８時間放置し、波長４００〜８００ｎｍにおけるＹ値を分光光度計（村上色彩研究所製ＣＭＳ−３５ＳＰ）により測定した。
Ｙ値が９４％以上となるものを合格（○）、９４％未満を不合格（×）とした。
(Light reflectivity)
The obtained pellets were dried at 125 ° C. for 4 hours, and then an optical measurement test piece (width: 50 mm, width: 300 ° C., injection pressure: 1600 kg / cm 2 ) using an injection molding machine (J100C-5 manufactured by Nippon Steel) 40 mm long and 2 mm thick). The aforementioned test piece was left in a thermostatic chamber at 23 ° C. and 50% humidity for 48 hours, and the Y value at a wavelength of 400 to 800 nm was measured with a spectrophotometer (CMS-35SP manufactured by Murakami Color Research Laboratory).
A Y value of 94% or more was judged as acceptable (◯), and a value less than 94% was judged as unacceptable (x).
（耐衝撃性）
得られたペレットを１２５℃で４時間乾燥後、射出成形機（日本製鋼所製Ｊ１００Ｅ−５）を用いて２８０℃、射出圧力１６００ｋｇ／ｃｍ２の条件下、強度測定用試験片（ＩＳＯ規格１７９−２の試験片、厚み４ｍｍ）を成形し、先端角０．２５Ｒのノッチ付き試験片に加工した。前述の試験片をＩＳＯ１７９−１に準拠し２３℃、湿度５０％の恒温室の中で４８時間状態調整後、シャルピー衝撃試験機で衝撃強度を測定した。
シャルピー衝撃強度が１５ＫＪ／ｍ２以上を合格（○）、１５ＫＪ／ｍ２未満を不合格（×）とした。
(Impact resistance)
The obtained pellets were dried at 125 ° C. for 4 hours, and then tested using an injection molding machine (Japan Steel Works J100E-5) under the conditions of 280 ° C. and injection pressure 1600 kg / cm 2 (ISO standard 179). -2 test piece, thickness 4 mm) was molded and processed into a notched test piece with a tip angle of 0.25R. The test piece was conditioned for 48 hours in a constant temperature room at 23 ° C. and 50% humidity in accordance with ISO 179-1, and then the impact strength was measured with a Charpy impact tester.
A Charpy impact strength of 15 KJ / m 2 or more was determined to be acceptable (◯), and less than 15 KJ / m 2 was determined to be unacceptable (x).
（熱安定性）
得られたペレットを１２５℃で４時間乾燥後、射出成形機（日本製鋼所製Ｊ１００Ｃ−５）を用いて３００℃、射出圧力１６００ｋｇ／ｃｍ２の条件下、７０×４０×３ｍｍの平板を成形した。その後、設定温度３００℃のシリンダー内で１０分滞留させた後、さらに成形した。滞留前の成形品と滞留後の成形品のイ エローネスインデックス（ＹＩ）をＡＳＴＭ Ｄ−１９２５に準拠して測定した。滞 留前のＹＩと滞留後のＹＩとの差をΔＹＩとし、２以下を合格とした。また、滞留後の成形品外観を下記の通り評価し、○を合格とした。
○：シルバーストリーク無し
×：シルバーストリーク発生
(Thermal stability)
The obtained pellets were dried at 125 ° C. for 4 hours, and then a 70 × 40 × 3 mm flat plate was formed using an injection molding machine (J100C-5 manufactured by Nippon Steel) under the conditions of 300 ° C. and injection pressure 1600 kg / cm 2. did. Then, after making it retain for 10 minutes in the cylinder of preset temperature 300 degreeC, it shape | molded further. The yellowness index (YI) of the molded product before residence and the molded product after residence was measured in accordance with ASTM D-1925. The difference between YI before retention and YI after residence was ΔYI, and 2 or less was accepted. In addition, the appearance of the molded product after staying was evaluated as follows, and ○ was set as acceptable.
○: No silver streak ×: Silver streak occurred
表１に示すとおり、本発明の構成を満足する場合（実施例１〜３）には、全ての評価項目において十分な性能を有していた。 As shown in Table 1, when the configuration of the present invention was satisfied (Examples 1 to 3), all the evaluation items had sufficient performance.
一方、表２に示すとおり、本発明の構成を満足しない場合には、いずれの場合も何らかの欠点を有していた。
比較例１は、酸化チタンの配合量が規定量よりも少ない場合で、光反射性に劣っていた。
比較例２は、酸化チタンの配合量が規定量よりも多い場合で、耐衝撃性に劣っていた。
比較例３は、本発明の環状亜リン酸エステル系酸化防止剤が規定量よりも少ない場合で、熱安定性に劣っていた。
比較例４は、本発明の環状亜リン酸エステル系酸化防止剤が規定量よりも多い場合で、耐衝撃性が劣っていた。
比較例５は、本発明の環状亜リン酸エステル系酸化防止剤以外の酸化防止剤（ＡＯ２）を使用した場合で、熱安定性が劣っていた。
On the other hand, as shown in Table 2, when the configuration of the present invention was not satisfied, each case had some drawbacks.
Comparative Example 1 was inferior in light reflectivity when the blending amount of titanium oxide was less than the specified amount.
In Comparative Example 2, the compounding amount of titanium oxide was larger than the specified amount, and the impact resistance was inferior.
In Comparative Example 3, the cyclic phosphite antioxidant of the present invention was less than the specified amount, and the thermal stability was poor.
In Comparative Example 4, the cyclic phosphite antioxidant of the present invention was more than the specified amount, and the impact resistance was inferior.
Comparative Example 5 was a case where an antioxidant (AO2) other than the cyclic phosphite antioxidant of the present invention was used, and the thermal stability was poor.
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