WO2005123831A1 - ポリ乳酸含有樹脂組成物及びそれより得られる成形体 - Google Patents
ポリ乳酸含有樹脂組成物及びそれより得られる成形体 Download PDFInfo
- Publication number
- WO2005123831A1 WO2005123831A1 PCT/JP2005/010947 JP2005010947W WO2005123831A1 WO 2005123831 A1 WO2005123831 A1 WO 2005123831A1 JP 2005010947 W JP2005010947 W JP 2005010947W WO 2005123831 A1 WO2005123831 A1 WO 2005123831A1
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- WIPO (PCT)
- Prior art keywords
- polylactic acid
- resin composition
- mass
- pmma
- containing resin
- Prior art date
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 95
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 95
- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 36
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003607 modifier Substances 0.000 claims abstract 3
- 239000000463 material Substances 0.000 claims description 36
- 239000004609 Impact Modifier Substances 0.000 claims description 16
- 239000010410 layer Substances 0.000 claims description 12
- 239000012792 core layer Substances 0.000 claims description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 description 27
- -1 phospho-dimethyl sulfoisophthalic acid Chemical compound 0.000 description 19
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- 229920001971 elastomer Polymers 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920006167 biodegradable resin Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 230000006872 improvement Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
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- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920000800 acrylic rubber Polymers 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
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- 229920002223 polystyrene Polymers 0.000 description 5
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 4
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- 239000004743 Polypropylene Substances 0.000 description 4
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- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 150000002892 organic cations Chemical class 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
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- 230000003287 optical effect Effects 0.000 description 3
- 229910052615 phyllosilicate Inorganic materials 0.000 description 3
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- 229920000570 polyether Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
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- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- FAEIVMXWKPDFTP-UHFFFAOYSA-N 2-[dodecyl(methyl)amino]ethane-1,1-diol Chemical compound CCCCCCCCCCCCN(C)CC(O)O FAEIVMXWKPDFTP-UHFFFAOYSA-N 0.000 description 2
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 2
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
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- 238000004040 coloring Methods 0.000 description 2
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- 238000000354 decomposition reaction Methods 0.000 description 2
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 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
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
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- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
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- NMUWSGQKPAEPBA-UHFFFAOYSA-N 1,2-dibutylbenzene Chemical group CCCCC1=CC=CC=C1CCCC NMUWSGQKPAEPBA-UHFFFAOYSA-N 0.000 description 1
- PAALZGOZEUHCET-UHFFFAOYSA-N 1,4-dioxecane-5,10-dione Chemical compound O=C1CCCCC(=O)OCCO1 PAALZGOZEUHCET-UHFFFAOYSA-N 0.000 description 1
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- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
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- IRKZUKXVNJNVOO-UHFFFAOYSA-N [F].O[Si](O)(O)O.O[Si](O)(O)O.O[Si](O)(O)O.O[Si](O)(O)O Chemical compound [F].O[Si](O)(O)O.O[Si](O)(O)O.O[Si](O)(O)O.O[Si](O)(O)O IRKZUKXVNJNVOO-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 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
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000013361 beverage Nutrition 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
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate 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
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 229940022769 d- lactic acid Drugs 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- VFFDVELHRCMPLY-UHFFFAOYSA-N dimethyldodecyl amine Natural products CC(C)CCCCCCCCCCCN VFFDVELHRCMPLY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-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
- 238000009826 distribution Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 235000013410 fast food Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000003898 horticulture Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- SZEGKVHRCLBFKJ-UHFFFAOYSA-N n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNC SZEGKVHRCLBFKJ-UHFFFAOYSA-N 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-N n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-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
- 229930014626 natural product Natural products 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 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
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical group C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- FAUOSXUSCVJWAY-UHFFFAOYSA-N tetrakis(hydroxymethyl)phosphanium Chemical compound OC[P+](CO)(CO)CO FAUOSXUSCVJWAY-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WSNJABVSHLCCOX-UHFFFAOYSA-J trilithium;trimagnesium;trisodium;dioxido(oxo)silane;tetrafluoride Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WSNJABVSHLCCOX-UHFFFAOYSA-J 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
Definitions
- the present invention relates to a polylactic acid-containing resin composition and a molded product obtained therefrom.
- polylactic acid has excellent transparency, has a high melting point (Tm) as compared with other aliphatic polyesters, and has such characteristics.
- Tm melting point
- polylactic acid has a low glass transition temperature (Tg), and thus tends to have insufficient heat resistance in a temperature range above Tg, and is used as a molded article having a low impact strength due to being hard and brittle. Have limited uses.
- a transparent resin such as an acrylic resin having a higher Tg and a higher compatibility than polylactic acid must be used. It can be blended. Based on this idea, a technique of blending polylactic acid with polymethyl methacrylate (hereinafter abbreviated as "PMMA") or a copolymer of acrylic resin has been developed and disclosed in the following documents. . [0005] [1] Polymer, 39 (26), 6891 (1998)
- Document [6] proposes a method of adding an impact resistance improving material in order to improve the impact strength of polylactic acid.
- an impact resistance improving material was added.
- a crystallization nucleating agent or the like is added, although the heat resistance is improved, polylactic acid crystallizes and becomes cloudy, resulting in poor transparency.
- polylactic acid is subject to hydrolysis, and there is a need for improvement in this regard as soon as it is achieved.
- a resin composition in which such an impact modifier is applied to a combined system of polylactic acid and PMMA, and which has all of transparency, heat resistance, impact resistance, and durability, Not yet known.
- the present invention solves the above-mentioned problems, and is not only excellent in heat resistance, transparency, and moldability, but also has a polylactic acid-containing resin composition improved in impact resistance and durability.
- the object is to obtain a product and a molded product obtained therefrom.
- a polylactic acid-containing resin composition comprising polylactic acid, PMMA, and an impact resistance improving material, having excellent heat resistance, moldability, and durability, having high transparency, and also having impact resistance.
- the purpose is to obtain the obtained molded body.
- the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a specific impact resistance improving material is mixed with a resin composition comprising polylactic acid and PMMA.
- the fat composition was found to be excellent in heat resistance and transparency, and also had high impact resistance, and reached the present invention.
- the gist of the present invention is as follows.
- a resin composition containing polylactic acid comprising 100 to 100 parts by mass of a resin containing 20 to 98% by mass of polymethyl methacrylate and 80 to 2% by mass of polylactic acid, and an impact resistance improving material 1 to: Including LOO parts by mass.
- the polylactic acid-containing resin composition according to (1) which is a polymer containing an acrylic monomer as a structural unit.
- RIa is the refractive index of the impact modifier
- Rib is the refractive index of the resin consisting of polymethyl methacrylate and polylactic acid
- the refractive index of the impact modifier RIa satisfies the following formula (i).
- the polylactic acid-containing resin composition according to any one of (1) to (5). [0015] Rib— 0.005 ku RIa ku RIb + O. 005 ⁇ ⁇ ⁇ (i)
- 0.05 to 30 parts by mass of a swellable layered silicate is further added to 100 parts by mass of the resin composition, and the polystyrene of any one of (1) to (6) is characterized in that Lactic acid-containing resin composition.
- a polylactic acid-containing resin composition having transparency, heat resistance, moldability, durability, and impact resistance can be obtained by an industrially simple method.
- various molded articles can be obtained by using this resin by various molding methods such as extrusion molding, injection molding, and blow molding.
- the polylactic acid used in the present invention is a polymer containing L-lactic acid and Z or D-lactic acid as a main component, but other resins may be added as necessary within a range not to impair the effect of the present invention. You may copolymerize! /.
- Examples of other copolymer component units include polycarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, and ratatone. Specifically, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, fumaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2, 6 Polycarboxylic acids such as naphthalene dicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutyl phospho-dimethyl sulfoisophthalic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol Aromatic polyhydric alcohols obtained by the addition reaction of
- diethylene Dali Konore triethylene glycol, polyethylene glycol, polypropylene glycol, polyhydric alcohols such as port polytetramethylene glycol, glycolic acid, 3-hydroxybutyric acid , 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, hydroxycarboxylic acids such as hydroxybenzoic acid, glycolide, ⁇ -force prolatataton glycolide, ⁇ -one force ratatone, j8-propiolatatatone, ⁇ butyrolataton, 13
- ratatones such as ⁇ -butyrolataton, pivalolataton, and ⁇ -valerolataton can be used.
- the optical purity of the lactic acid component in the polylactic acid is not particularly limited, but the lactic acid component obtained from a raw material derived from a natural product is mainly in the L-form. U, which preferably contains more than 80 mol%.
- a known polymerization method can be used. Specifically, a direct polymerization method from lactic acid, a ring-opening polymerization method via lactide, and the like can be employed. Solid phase polymerization may be used in combination.
- the molecular weight and molecular weight distribution of polylactic acid are not particularly limited as long as the resin can be processed, but preferably have a weight average molecular weight of 50,000 or more, more preferably 100,000 or more.
- the upper limit for good molding is a weight average molecular weight of about 500,000.
- ⁇ used in the present invention is not particularly limited, but preferably contains 80% by mass or more of methyl methacrylate units. ⁇ may contain 20% by mass or less of a monomer unit other than methyl methacrylate.
- the butyl monomer include alkyl (meth) acrylate and styrene other than methyl methacrylate.
- the molecular weight of 2 is preferably 20,000 to 300,000, more preferably 50,000 to 250,000 in terms of weight average molecular weight. If the weight average molecular weight exceeds 300,000, compatibility with polylactic acid may be difficult to obtain, and if the weight average molecular weight is less than 20,000, properties such as heat resistance and transparency possessed by ⁇ may be manifested. .
- polylactic acid and ⁇ are completely compatible with each other in an industrially useful melt-kneading method, and are excellent in heat resistance, transparency, and processability. A fat composition can be obtained.
- the impact modifier used in the present invention is not particularly limited, but examples thereof include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-non-conjugated gen, and ethylene butyl acetate.
- the impact resistance improving material one obtained by crosslinking a crosslinkable component such as dibutylbenzene unit, allyl acrylate unit or butylene glycol acrylate, or a material having a vial group, etc.
- a crosslinkable component such as dibutylbenzene unit, allyl acrylate unit or butylene glycol acrylate, or a material having a vial group, etc.
- those having various other structures such as a cis structure and a trans structure can also be used.
- a polymer containing an acrylic monomer as a constituent unit is preferred, and a polymer containing a (meth) acrylic acid alkyl ester unit is more preferred! / ⁇ .
- Preferred examples of the unit include a methyl acrylate unit, an ethyl acrylate unit, a butyl acrylate unit, a methyl methacrylate unit, an ethyl methacrylate unit, and a butyl methacrylate unit. These have excellent compatibility between polylactic acid and PMMA, which not only improve impact resistance as an elastomer, but also improve the heat resistance and transparency of the resin.
- These impact modifiers are composed of a core layer and one or more shell layers that cover the core layer, and a so-called core in which adjacent layers are composed of different polymers.
- 'It is preferably a shell-type multilayer polymer.
- the multi-layer structure polymer contains, as a core layer, an elastomer component such as SBR rubber, butadiene, acrylonitrile-styrene copolymer, and a polymer having (meth) acrylate units (eg, acrylic rubber), and a shell layer. , Polystyrene, and a polymer having a (meth) acrylate unit.
- the shell layer plays a role of maintaining the shape of the core layer, which is an elastomer component. It is evenly and finely dispersed in fat and can exhibit excellent impact resistance. Further, it is possible to absorb the impact at the boundary between the core layer and the shell layer and at the boundary between the shell layer and the matrix, so that further improvement in impact resistance can be expected.
- polylactic acid and PMMA are effective.
- a polymer containing methyl methacrylate units is contained in the shell layer, and acrylic acid is used in view of the effect of improving impact resistance and adjusting the refractive index.
- the core layer contains a polymer having an alkyl ester unit.
- Acrylic rubber is preferred as the polymer having an alkyl acrylate suitable for the core layer.
- Acrylic rubber is a general term for synthetic rubbers containing alkyl acrylate as a main component.
- Typical examples include a copolymer (ACM) of alkyl acrylate and 2-chloroethylbutyl ether, and acrylic rubber.
- Copolymers (ANMs) of acid alkyl esters with Atari-tolyl can be exemplified.
- the mass ratio of the core Z shell is not particularly limited, but is preferably in the range of 10Z90 to 90ZlO.
- the size of the impact modifier is not particularly limited, but the average particle size is preferably in the range of 0.01 to 1 ⁇ m, and the average particle size is preferably in the range of 0.02 to 0.5 m. Is more preferable. If the average particle size is less than 0.01 m, it may be difficult to develop impact resistance. If the average particle size is more than Lm, fluidity and moldability may be impaired.
- the refractive index of the impact resistance improving material be in the range of 1.402 to 1.542.
- the refractive index includes the refractive index of polylactic acid of 1.454 and the refractive index of PMMA of 1.490, with the upper limit and lower limit of the value of 0.070, centered on the average value of 1.472. It is. More preferably, it is in the range of 1.430 to 1.510, and still more preferably 1.450 to 1.490. If the refractive index of the impact modifier is less than 1.402 or greater than 1.542, the difference in refractive index between the resin and the impact modifier will increase, and the resin will be scattered by light based on it. Transparency of the composition is likely to decrease.
- the refractive index of the impact resistance improving material is defined as RIa
- the refractive indices of PMMA and the polylactic acid resin are defined as Rib.
- the refractive index RIa of the improving material satisfies the following expression (i).
- the refractive index of the impact resistance improving material close to that of the PMMAZ polylactic acid resin composition, it is possible to suppress a decrease in transparency due to light scattering.
- the ratio of PMMA to polylactic acid in the resin composition of the present invention is determined by PMMAZ polylactic acid.
- PMMAZ polylactic acid 25-95% by mass Z75-5% by mass
- PMMAZ polylactic acid 30-95% by mass Z70- More preferably, it is set to 5% by mass.
- the content of polylactic acid exceeds 80% by mass, the rise in Tg from polylactic acid alone becomes smaller.
- the content of PMMA exceeds 98% by mass, it is difficult to say that the composition is environmentally friendly by using polylactic acid.
- the blending amount of the impact resistance improving material must be 1 to 100 parts by mass, preferably 3 to 50 parts by mass, based on 100 parts by mass of the total amount of PMMA and polylactic acid.
- the amount of the impact resistance improving material is less than 1 part by mass, the improvement in impact strength is low.
- the method for producing the resin composition of the present invention is not particularly limited, and for example, a melt-kneading method that is industrially simplest can be employed.
- the resin composition can be obtained by melt-kneading polylactic acid, PMMA and an impact resistance improving material by a melt-kneading method.
- a general extruder can be used for melt-kneading, and it is preferable to use a twin-screw extruder for improving the kneading state.
- a dry blend of all the raw materials may be supplied to one hopper in advance, or each resin may be supplied to three hoppers. It is also possible to supply while metering with a screw below the hopper.
- the kneading method of each component is not particularly limited, and polylactic acid, PMMA and the impact resistance improving material may be kneaded at the same time, or polylactic acid and PMMA may be kneaded first, and then the impact resistance improving material may be kneaded. You can knead them together! The order of kneading hardly affects the performance of the resin composition of the present invention such as transparency.
- the resin composition of the present invention may contain other resin components as long as the effects of the present invention are not impaired.
- biodegradable resins polydalicholic acid, poly (3-hydroxybutyric acid), poly (3-hydroxyvaleric acid), poly (3-hydroxycaproic acid), polyethylene succinate, polybutylene succinate, and polybutylene succinate (Butylene adipate Z butylene terephthalate) copolymer, poly (ethylene adipate Z ethylene terephthalate) copolymer, copolymers thereof, and mixtures thereof.
- Synthetic resins other than biodegradable resins include polyethylene glycol or derivatives thereof as thermoplastic resins.
- Polytetra Fluorocarbon resin such as fluoroethylene, cellulose resin such as polystyrene, polypropylene, cellulose acetate butyrate, other acrylic resin, acrylonitrile-butadiene-styrene or acrylo-tolyl-styrene, polycarbonate, polyvinyl acetate, Thermoplastic resins or grafts such as ethylene butyl acetate, polybutyl alcohol, polyoxymethylene, polyformaldehyde, polyacetal, and polyethylene terephthalate, polyethers.
- thermosetting resins include polyurethane, silicone, fluorosilicone, phenol resin, melamine resin, melamine 'formaldehyde, urea formaldehyde, and copolymers thereof. Coalescence, and mixtures thereof.
- the resin composition of the present invention includes a pigment, a heat stabilizer, an antioxidant, a weathering agent, a flame retardant, a plasticizer, a lubricant, a release agent, and a charge as long as the effects of the present invention are not impaired. Inhibitors, fillers, lubricants and the like may be added.
- As the heat stabilizer or the anti-oxidizing agent for example, hindered phenols, phosphorus-containing compounds, hindered amines, zeo compounds, copper compounds, alkali metal halides or mixtures thereof can be used.
- These additives such as a heat stabilizer, an antioxidant, and a weathering agent are generally added during melt-kneading or polymerization.
- Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Black, zinc oxide, antimony trioxide, zeolite, hydrated talcite, metal fibers, metal whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, glass fibers, carbon fibers, and the like.
- the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, bran, and kenaf, and modified products thereof.
- a swellable layer Preferably, a silicate is added.
- a silicate By adding a swellable layered silicate, it is possible to impart heat-resistant deformation properties and Z or gas nolia properties.
- the addition amount is not particularly limited, but is suitably 0.05 to 30 parts by mass per 100 parts by mass of the resin composition.
- one or both components may contain a swellable layered silicate.Also, when the polylactic acid and PMMA component are mixed, the swellable layered silicate may be added. Silicates can be added simultaneously.
- the swellable phyllosilicate dispersed in the resin has an interlayer distance of 2 nm (20 A) or more and a particle size of 1 to about LOOO nm.
- the swellable layered silicate include smectite, vermiculite, and swellable fluoromica.
- smectites include montmorillonite, paiderite, hectorite, saponite and the like.
- Examples of the swellable fluorine mica include Na-type fluorine tetrasilicate mica, Na- type teolite, and Li-type teolite.
- These swellable phyllosilicates can be previously subjected to an organic cation treatment, if necessary, in order to improve the dispersibility in the resin component.
- organic cation include primary to tertiary amine tertiary amines, quaternary ammonium, and organic phosphonium.
- the primary amine include octylamine, dodecylamine, and octadecylamine.
- Examples of the secondary amine include octylamine, methyloctadecylamine, dioctadecylamine, and the like.
- Tertiary amines include trioctylamine, dimethyldodecylamine, didodecylmonomethylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, and dimethylamine.
- Examples include stearylamine, dilaurylmonomethylamine, tributylamine, trioctylamine, N, N-dimethylaniline and the like.
- the organic phosphonium include tetraethylphosphonium, tetrabutylphosphonium, tetrakis (hydroxymethyl) phosphonium, 2-hydroxyshethyltriphenylphosphonium and the like.
- the resin composition of the present invention for the purpose of improving the durability, it is preferable to block the terminal of polylactic acid with a hydrolysis inhibitor.
- the hydrolysis inhibitor include carbodiimide, oxazoline, and epoxy conjugate.
- the amount added is not particularly limited, but is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin composition.
- the method of adding the hydrolysis preventing material include a method of dry blending the hydrolysis preventing material with another raw material before supplying the material to the extruder, a method of supplying the hydrolysis preventing material from a supply port in the middle of the extruder, and the like. Is mentioned.
- the resin composition of the present invention can be formed into various molded articles by a known molding method such as injection molding, blow molding, or extrusion molding.
- the injection molding method a gas injection molding method, an injection press molding method, or the like can be employed in addition to a general injection molding method.
- the cylinder temperature during injection molding must be higher than the melting point (Tm) of polylactic acid or higher than the flow start temperature, preferably in the range of 150 to 230 ° C, and more preferably in the range of 180 to 210 ° C. It is. If the molding temperature is too low, molding may become unstable due to short-circuiting in the molding or overload. Conversely, if the molding temperature is too high, problems such as decomposition of the polylactic acid, reduction in the strength of the obtained molded body, and occurrence of coloring during molding are likely to occur.
- the mold temperature must be equal to or lower than the Tg of the resin composition, and preferably (Tg-10 ° C) or lower.
- blow molding method examples include a direct blow method in which molding is directly performed from raw material chips, an injection blow molding method in which a preform (bottom parison) is molded by injection molding, and then blow molding is performed.
- a blow molding method and the like can be given.
- Injection blow molding methods include the hot parison method, in which blow molding is performed continuously after molding of the preformed body, and the cold parison method, in which the preformed body is cooled, taken out, and heated again to perform blow molding. Method can also be adopted.
- the extrusion temperature must be higher than the melting point (Tm) of the raw material polylactic acid or higher than the flow start temperature, and is preferably in the range of 150 to 230 ° C, more preferably 180 to 210 ° C. If the molding temperature is too low, the molding becomes unstable or easily overloaded. Conversely, if the molding temperature is too high, the polylactic acid component is decomposed, and the strength of the obtained extruded product is reduced, Problems such as coloring of the formed article are likely to occur. Sheets and pipes can be produced by extrusion.
- the form of the molded article produced by the above molding method is not particularly limited!
- dishes such as plates, bowls, bowls, bowls, chopsticks, spoons, forks, knives, etc .
- containers for fluids such as plates, bowls, bowls, bowls, chopsticks, spoons, forks, knives, etc .
- containers for fluids such as plates, bowls, bowls, bowls, chopsticks, spoons, forks, knives, etc .
- containers for fluids such as rulers, writing utensils, clear cases, CD cases
- Daily necessities such as trash cans, washbasins, toothbrushes, combs, hangers, etc .
- Agriculture such as flowerpots, seedling pots
- gardening materials various toys such as plastic models
- Automotive resin parts such as instrument panels and door trims.
- the form of the fluid container is not particularly limited, but is preferably formed to a depth of 20 mm or more to accommodate the fluid.
- the thickness of the fluid container is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.1 to 5 mm, from the viewpoint of a strong point force.
- Specific examples of containers for fluids include drink cups and bottles for beverages such as dairy products, soft drinks, and liquors; temporary storage containers for seasonings such as soy sauce, sauces, mayonnaise, ketchup, and edible oils; Containers for rinsing and the like; containers for cosmetics; containers for agricultural chemicals and the like.
- Specific uses of the sheet or pipe obtained by the extrusion molding method include a raw sheet for deep drawing, a raw sheet for batch foaming, cards such as credit cards, underlays, clear files, straws, and the like. And hard pipes for agriculture and horticulture. Sheets are made by deep drawing such as Sarakoko, vacuum forming, compressed air forming, and vacuum press forming to produce food containers, agricultural / horticultural containers, blister pack containers, press-through pack containers, etc. can do.
- the deep drawing temperature and the heat treatment temperature are preferably (Tg + 20 ° C.) to (Tg + 100 ° C.).
- the deep drawing temperature is lower than (Tg + 20 ° C), deep drawing becomes difficult, and if the deep drawing temperature exceeds (Tg + 100 ° C), polylactic acid is decomposed, causing uneven thickness and orientation. In some cases, impact resistance may be reduced due to collapse.
- the form of the container such as a food container, an agricultural / horticultural container, a blister pack container, and a press-through pack container is not particularly limited, but a depth of 2 mm or more is required to accommodate food, articles, medicines, and the like. It is preferable that the sheet is deep drawn.
- the thickness of the container is not particularly limited. From the viewpoint of power and strength, it is preferable that the thickness be 50 m or more. Is more preferable. Examples of food containers include fresh food trays, instant food containers, fast food containers, lunch boxes, and the like. Examples of containers for agricultural and horticultural use include pots for raising seedlings. Examples of blister pack containers include food containers, packaging containers for various product groups such as office supplies, toys, and dry batteries.
- the resin composition of the present invention can also form capilla fibers.
- This resin composition can be processed into various fibers as multifilaments, monofilaments, and the like.
- the production method is not particularly limited, but a method of drawing after melt-spinning is preferred.
- the melt spinning temperature is preferably from 160 ° C to 260 ° C. If the temperature is lower than 160 ° C, melt extrusion tends to be difficult. If the temperature exceeds 250 ° C, the decomposition of polylactic acid becomes remarkable, and it tends to be difficult to obtain high-strength fibers.
- the melt-spun fiber yarn is preferably drawn at a temperature of Tg or more so as to have a desired fiber diameter.
- the resin composition of the present invention is amorphous, it is difficult to obtain a remarkable improvement in physical properties by stretching as in the case of crystalline resin.However, since the orientation of molecular chains is slightly caused by stretching, the resin composition was stretched. Physical properties such as strength are improved.
- the stretching magnification is preferably about 1 to 20 times.
- the fiber obtained by the above method is used as a fiber for clothing, a fiber for industrial materials, and the like.
- a multifilament it can be used for various clothing fibers, industrial fibers such as ropes and various nets, and advertising fibers such as flags and notice nets.
- advertising fibers such as flags and notice nets.
- the transparency is high, a unique atmosphere comes out for the purpose of advertisement and is characteristic.
- a monofilament it can be applied to various nets, guts, fishing lines, polishing applications, and the like.
- the present invention can be applied to a composite obtained by combining a resin with a resin.
- the resin composition of the present invention has the characteristic of having a birefringence power, and specifically has a birefringence of 0.005 or less. Therefore, it can be favorably used for optical applications such as DVD substrates and CD substrates. This birefringence can be measured by the method described below.
- the temperature was raised from 25 ° C. to 200 ° C. at + 20 ° C./min using a DSC device (Pyrisl DSC manufactured by PerkinElmer). Thereafter, the temperature was kept at 200 ° C for 10 minutes, and the temperature was lowered from 200 ° C to 0 ° C at ⁇ 20 ° C for Z minutes. Thereafter, the temperature was kept at 0 ° C for 5 minutes, the temperature was raised from 0 ° C to 200 ° C by + 20 ° CZ (2nd scan), and the 2nd ⁇ scan was measured.
- MFR Melt viscosity
- the refractive indices were measured in three directions, where the flow direction of the resin in Example 1 was the X direction, the direction perpendicular to the X direction was the Y direction, and the direction perpendicular to the XY plane was the Z direction.
- the refractive index in the X direction was adopted as the refractive index of the sample.
- the refractive index RIa of the impact resistance improving material and the refractive index Rib of the resin composed of polymethyl methacrylate and polylactic acid were obtained.
- the total light transmittance was measured by a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd.) using a test piece having a thickness of 2 mm according to JIS K7105 (light transmittance measurement method A). This total light transmittance value is 85 If it is at least%, it can be favorably used for various applications requiring transparency.
- Specimens of 65 mm x 12 mm x 3 mm were prepared according to ASTM-256, and the Izod impact strength was measured with a notch.
- Thickness unevenness due to "sink" which was a defect at the time of molding was measured.
- the moldability was evaluated as excellent ( ⁇ ), and when the thickness unevenness of the molded piece was 0.0 Olmm or more and less than 0.05 mm. It was evaluated as ⁇ as good, and the case where the thickness unevenness of the molded piece was 0.05 mm or more and less than 0.10 mm was evaluated as slightly inferior, and the case where the thickness unevenness of the molded piece was 0.10 mm or more was poor.
- X As X.
- the thickness of a molded piece having a length of 125 mm, a width of 12 mm and a thickness of 3 mm was measured using a micrometer manufactured by Mitutoyo Co., Ltd. at three locations in the length direction (gate side). , Middle, tip side). Then, the difference between the maximum value and the minimum value was defined as thickness unevenness.
- a 125mmX12mmX3mm specimen was stored for 500 hours under constant temperature and humidity conditions of 60 ° C and 95% RH, and before and after that, the bending strength was increased by applying a load at a deformation speed of ImmZ according to JIS K-7203. A measurement was made. As a result, if the initial bending strength after storage for 500 hours was 90% or more, the durability was evaluated as ⁇ . If the strength was 80% or more and less than 90%, the durability was good. Was evaluated as ⁇ , and when it was 50% or more and less than 80%, it was evaluated as ⁇ as slightly inferior.
- PLA—A weight-average molecular weight 190,000, L-form 99 mol%, D-form 1 mol%, melting point 168 ° C, MFR3gZlO, Min.
- PLA-B Weight average molecular weight 80,000, L-form 99 mol%, D-form 1 mol%, melting point 168 ° C, MFR20gZlO content, Cargill Dow's “Nature Works”.
- PLA-C weight-average molecular weight 110,000, L-form 92 mol%, D-form 8 mol%, softening point 120 ° C, MFR8gZlO content, “Nature Works” manufactured by Cargill Dow.
- PMMA—A weight average molecular weight 100,000, Tgl 15 ° C, Mitsubishi Rayon “Ataripet VH” 0
- PMMA-C The amount of normal dodecyl mercaptan used in the production of PMMA-B was 0.5 parts by mass. Other than that, the same operation was performed to obtain PMMA-C. Its weight average molecular weight was 250,000 and Tg was 115 ° C.
- MB—1 Metablen W—450A (trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
- SF-1 Staphyloid IM-601 (trade name, manufactured by Ganz Kasei Co., Ltd.)
- Table 1 shows the composition, refractive index, and the like of the above-mentioned impact resistance improving material. Properties of impact resistant material Composition
- Mc-l Organically treated swellable phyllosilicate (trade name: S-BEN W, organic cation: dimethyldioctadecylammonium, manufactured by Hoziyun Co., Ltd.)
- Mc— 2 Swellable layered silicate treated with organic treatment (Made by Coop Chemical Co., Ltd., trade name: MEE, organic cation: dihydroxyethylmethyldodecylammonium)
- MF-1 Carposimide compound (Polylactic acid end blocking material, manufactured by Matsumoto Yushi Co., Ltd., trade name: EN-160)
- a twin-screw kneading extruder manufactured by Ikegai Co., Ltd., product number PCM-30, die diameter 4mm x 3 holes, cylinder temperature 210 ° C, die outlet temperature 200 ° C), 60 parts by mass of PLA-A, 40 parts by mass PMMA-A and 10 parts by mass of MP-1 were dry-blended and supplied from a hopper, extruded, processed into a pellet, and dried to obtain a resin composition.
- the obtained resin composition pellets were subjected to injection molding machine IS-80G manufactured by Toshiba Machine Co., Ltd., using a cylinder temperature of 200 ° C, an injection pressure of 60%, a mold temperature of 25 ° C, an injection time of 10 seconds, Injection molding was performed with a cooling time of 20 seconds, and various evaluations were performed.
- a resin composition comprising 60 parts by mass of PLA-A and 40 parts by mass of PMMA-A was extruded and molded in the same manner as described above, and the refractive index was measured. Met.
- Table 2 summarizes the results of Examples 1 to 20 and Comparative Examples 1 to 3.
- the refractive index of the impact resistance improving material was in the range of ⁇ 0.070 centered at 1.472, and therefore the transparency was particularly good.
- the refractive index (RIa) of the impact modifier was within the range of ⁇ 0.005 of the refractive index (Rlb) of polylactic acid ZPMMA resin, and The transparency was better.
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US11/629,264 US20090018237A1 (en) | 2004-06-16 | 2005-06-15 | Polylactic acid-containing resin composition and product molded therefrom |
EP05750878A EP1785453B1 (en) | 2004-06-16 | 2005-06-15 | Polylactic acid-containing resin composition and molded body obtained from same |
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JP2007186562A (ja) * | 2006-01-12 | 2007-07-26 | Three M Innovative Properties Co | ポリ乳酸含有樹脂組成物、ポリ乳酸含有樹脂フィルム及び樹脂繊維 |
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JP2008133445A (ja) * | 2006-10-31 | 2008-06-12 | Toray Ind Inc | 樹脂組成物およびそれからなる成形品 |
WO2008036335A3 (en) * | 2006-09-19 | 2008-08-14 | Du Pont | Toughened poly(hydroxyalkanoic acid) compositions |
JP2008221504A (ja) * | 2007-03-09 | 2008-09-25 | Toray Ind Inc | 積層シートおよびそれからなる成形体 |
JP2009007528A (ja) * | 2007-06-29 | 2009-01-15 | Nippon A & L Kk | 熱可塑性樹脂組成物 |
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Also Published As
Publication number | Publication date |
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JPWO2005123831A1 (ja) | 2008-04-10 |
US20090018237A1 (en) | 2009-01-15 |
EP1785453A4 (en) | 2007-12-19 |
JP5305590B2 (ja) | 2013-10-02 |
EP1785453B1 (en) | 2012-04-18 |
EP1785453A1 (en) | 2007-05-16 |
JP2013100553A (ja) | 2013-05-23 |
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