JP2007002243A - Polylactic acid resin composition and molded article - Google Patents
Polylactic acid resin composition and molded article Download PDFInfo
- Publication number
- JP2007002243A JP2007002243A JP2006146833A JP2006146833A JP2007002243A JP 2007002243 A JP2007002243 A JP 2007002243A JP 2006146833 A JP2006146833 A JP 2006146833A JP 2006146833 A JP2006146833 A JP 2006146833A JP 2007002243 A JP2007002243 A JP 2007002243A
- Authority
- JP
- Japan
- Prior art keywords
- polylactic acid
- film
- plasticizer
- resin composition
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 86
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 86
- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 239000004014 plasticizer Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 27
- -1 phosphate ester Chemical class 0.000 claims description 21
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 15
- 229960000448 lactic acid Drugs 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 6
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000007519 polyprotic acids Polymers 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229920006381 polylactic acid film Polymers 0.000 description 15
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 239000004310 lactic acid Substances 0.000 description 11
- 235000014655 lactic acid Nutrition 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 6
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 229940022769 d- lactic acid Drugs 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 3
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 2
- LVAGMBHLXLZJKZ-UHFFFAOYSA-N 2-o-decyl 1-o-octyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC LVAGMBHLXLZJKZ-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-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
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- YSEKNCXYRGKTBJ-UHFFFAOYSA-N dimethyl 2-hydroxybutanedioate Chemical compound COC(=O)CC(O)C(=O)OC YSEKNCXYRGKTBJ-UHFFFAOYSA-N 0.000 description 2
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001475 halogen functional group Chemical group 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
- 229940049920 malate Drugs 0.000 description 2
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- IOVNHINTOHPELQ-UHFFFAOYSA-N 1-o-butyl 2-o-(8-methylnonyl) benzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C IOVNHINTOHPELQ-UHFFFAOYSA-N 0.000 description 1
- BAZVBVCLLGYUFS-UHFFFAOYSA-N 1-o-butyl 2-o-dodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC BAZVBVCLLGYUFS-UHFFFAOYSA-N 0.000 description 1
- BVGCOMLNDPDLSO-UHFFFAOYSA-N 1-o-decyl 2-o-octan-3-yl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OC(CC)CCCCC BVGCOMLNDPDLSO-UHFFFAOYSA-N 0.000 description 1
- RIXCYAQOGLLEIU-OTDRRXFESA-N 2,3-bis[[(e)-12-acetyloxyoctadec-9-enoyl]oxy]propyl (e)-12-acetyloxyoctadec-9-enoate Chemical compound CCCCCCC(OC(C)=O)C\C=C\CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C\CC(CCCCCC)OC(C)=O)COC(=O)CCCCCCC\C=C\CC(CCCCCC)OC(C)=O RIXCYAQOGLLEIU-OTDRRXFESA-N 0.000 description 1
- IFKLBBIPFXRVBR-UHFFFAOYSA-N 2,3-diacetyloxypropyl decanoate Chemical compound CCCCCCCCCC(=O)OCC(OC(C)=O)COC(C)=O IFKLBBIPFXRVBR-UHFFFAOYSA-N 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- HDIFHQMREAYYJW-FMIVXFBMSA-N 2,3-dihydroxypropyl (e)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C\CCCCCCCC(=O)OCC(O)CO HDIFHQMREAYYJW-FMIVXFBMSA-N 0.000 description 1
- RGUFZILIVUBHAE-UHFFFAOYSA-N 2-(2-decoxy-2-oxoethyl)-2-hydroxybutanedioic acid Chemical compound CCCCCCCCCCOC(=O)CC(O)(C(O)=O)CC(O)=O RGUFZILIVUBHAE-UHFFFAOYSA-N 0.000 description 1
- PHDVPEOLXYBNJY-KTKRTIGZSA-N 2-(2-hydroxyethoxy)ethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOCCO PHDVPEOLXYBNJY-KTKRTIGZSA-N 0.000 description 1
- WGIMXKDCVCTHGW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOCCO WGIMXKDCVCTHGW-UHFFFAOYSA-N 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- RTGQGAXEHFZMBG-UHFFFAOYSA-N 2-(2-nonanoyloxyethoxy)ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCCOCCOC(=O)CCCCCCCC RTGQGAXEHFZMBG-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- ZGHZSTWONPNWHV-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC1CO1 ZGHZSTWONPNWHV-UHFFFAOYSA-N 0.000 description 1
- AHSGHEXYEABOKT-UHFFFAOYSA-N 2-[2-(2-benzoyloxyethoxy)ethoxy]ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOCCOC(=O)C1=CC=CC=C1 AHSGHEXYEABOKT-UHFFFAOYSA-N 0.000 description 1
- UBQXQCCAPASFJR-UHFFFAOYSA-N 2-[2-(2-nonanoyloxyethoxy)ethoxy]ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCCOCCOCCOC(=O)CCCCCCCC UBQXQCCAPASFJR-UHFFFAOYSA-N 0.000 description 1
- JEYLQCXBYFQJRO-UHFFFAOYSA-N 2-[2-[2-(2-ethylbutanoyloxy)ethoxy]ethoxy]ethyl 2-ethylbutanoate Chemical compound CCC(CC)C(=O)OCCOCCOCCOC(=O)C(CC)CC JEYLQCXBYFQJRO-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- UFARNTYYPHYLGN-KHPPLWFESA-N 2-methoxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOC UFARNTYYPHYLGN-KHPPLWFESA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- PZBLUWVMZMXIKZ-UHFFFAOYSA-N 2-o-(2-ethoxy-2-oxoethyl) 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCC PZBLUWVMZMXIKZ-UHFFFAOYSA-N 0.000 description 1
- YJERZJLSXBRUDQ-UHFFFAOYSA-N 2-o-(3,4-dihydroxybutyl) 1-o-methyl benzene-1,2-dicarboxylate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OCCC(O)CO YJERZJLSXBRUDQ-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- NUCFNMOPTGEHQA-UHFFFAOYSA-N 3-bromo-2h-pyrazolo[4,3-c]pyridine Chemical compound C1=NC=C2C(Br)=NNC2=C1 NUCFNMOPTGEHQA-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- LEUWBMAQQQENOO-UHFFFAOYSA-N 4-(4-chlorophenyl)-6-methyl-2-oxo-3,4-dihydro-1h-pyridine-5-carboxylic acid Chemical compound C1C(=O)NC(C)=C(C(O)=O)C1C1=CC=C(Cl)C=C1 LEUWBMAQQQENOO-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- DMIMWGHYIPFAIF-UHFFFAOYSA-N 5-nitro-2-piperidin-1-ylaniline Chemical compound NC1=CC([N+]([O-])=O)=CC=C1N1CCCCC1 DMIMWGHYIPFAIF-UHFFFAOYSA-N 0.000 description 1
- DECACTMEFWAFRE-UHFFFAOYSA-N 6-o-benzyl 1-o-octyl hexanedioate Chemical compound CCCCCCCCOC(=O)CCCCC(=O)OCC1=CC=CC=C1 DECACTMEFWAFRE-UHFFFAOYSA-N 0.000 description 1
- NWSGBTCJMJADLE-UHFFFAOYSA-N 6-o-decyl 1-o-octyl hexanedioate Chemical compound CCCCCCCCCCOC(=O)CCCCC(=O)OCCCCCCCC NWSGBTCJMJADLE-UHFFFAOYSA-N 0.000 description 1
- DLZHIYULEPBYBE-UHFFFAOYSA-N 6-oxo-6-(5-phenylpentoxy)hexanoic acid Chemical compound OC(=O)CCCCC(=O)OCCCCCC1=CC=CC=C1 DLZHIYULEPBYBE-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- GOJCZVPJCKEBQV-UHFFFAOYSA-N Butyl phthalyl butylglycolate Chemical compound CCCCOC(=O)COC(=O)C1=CC=CC=C1C(=O)OCCCC GOJCZVPJCKEBQV-UHFFFAOYSA-N 0.000 description 1
- RXIMDEQGGDXGHI-WLPAHWJHSA-N C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(CCCCCCC\C=C/C[C@H](O)CCCCCC)(=O)O.OCC(O)CO Chemical compound C(C)(=O)O.C(C)(=O)O.C(C)(=O)O.C(CCCCCCC\C=C/C[C@H](O)CCCCCC)(=O)O.OCC(O)CO RXIMDEQGGDXGHI-WLPAHWJHSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
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- WDRCVXGINNJWPH-UHFFFAOYSA-N tris(6-methylheptyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(C(=O)OCCCCCC(C)C)C(C(=O)OCCCCCC(C)C)=C1 WDRCVXGINNJWPH-UHFFFAOYSA-N 0.000 description 1
- FJFYFBRNDHRTHL-UHFFFAOYSA-N tris(8-methylnonyl) benzene-1,2,4-tricarboxylate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC(C)C)C(C(=O)OCCCCCCCC(C)C)=C1 FJFYFBRNDHRTHL-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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Abstract
Description
本発明は、生分解性ポリ乳酸樹脂組成物およびその成形品に関する。 The present invention relates to a biodegradable polylactic acid resin composition and a molded product thereof.
ポリ乳酸は、トウモロコシやサツマイモなどの植物資源を原料として、微生物による乳酸発酵を介して乳酸が作られ、その乳酸またはラクチドを重合することによって得られる。ポリ乳酸は生態環境下において加水分解や酵素分解されることにより、乳酸へと戻り、さらに二酸化炭素と水まで分解される環境循環型の生分解性高分子である。ポリ乳酸は、石油資源の枯渇化からもそれらに変わる代替材料として注目されており、また地球環境の保護と地球資源の有効利用という観点から研究も盛んに行われている。 Polylactic acid is obtained by producing lactic acid through lactic acid fermentation by microorganisms using plant resources such as corn and sweet potato as raw materials, and polymerizing the lactic acid or lactide. Polylactic acid is an environmentally-circulating biodegradable polymer that returns to lactic acid by hydrolysis or enzymatic degradation in an ecological environment, and further decomposes to carbon dioxide and water. Polylactic acid has been attracting attention as an alternative material to replace them even from the depletion of petroleum resources, and research is also actively conducted from the viewpoint of protecting the global environment and effectively using global resources.
ポリ乳酸に関する研究は、１９３２年にCarothersによって乳酸から合成される高分子として開拓されて感心を集めた。当初は低分子量体のみしかえられなかったことから、その機械的特性は乏しく、実用化には遠いものとして考えられていた。１９５４年にDuPont社によって高分子量体の生産が開発された。１９７２年にはEthiconによって高強度を有した生分解性ファイバーとして、生体内において徐々に分解され吸収される生体吸収性縫合糸として、ポリ乳酸とポリグリコール酸の共重合体が報告された。これを境に医用材料として骨固定材や薬剤徐放担体としての応用が検討されている。 The research on polylactic acid was pioneered in 1932 as a polymer synthesized from lactic acid by Carothers. Initially, only low molecular weight substances could be obtained, so their mechanical properties were poor and they were considered far from practical use. In 1954 the production of high molecular weight was developed by DuPont. In 1972, Ethicon reported a copolymer of polylactic acid and polyglycolic acid as a biodegradable fiber having high strength and as a bioabsorbable suture that is gradually decomposed and absorbed in vivo. From this point of view, application as a bone fixing material or a drug sustained-release carrier is being studied as a medical material.
ポリ乳酸は非常に優れた生体適合性と生分解性を有した高分子であるが、その製造にコストがかかり、その適用範囲は非常に制限されたものであった。ここ１０年で生産技術が格段に進歩し、工業的に大量生産が可能となったことから、最近では、ポリ乳酸を安価で入手することができる。 Polylactic acid is a polymer having very excellent biocompatibility and biodegradability, but its production cost is high and its application range is very limited. In recent 10 years, production technology has greatly advanced and industrial mass production has become possible, so recently polylactic acid can be obtained at low cost.
ポリ乳酸は、その透明性、強度等の特性を利用して、包装材やトレー、園芸用資材などの生活用品を含め種々の実用品が開発され市場に投入されている。 Polylactic acid has been developed and put into the market using various properties such as packaging materials, trays, and horticultural materials, utilizing properties such as transparency and strength.
ポリ乳酸は、本質的に、硬くて脆いので、この硬くて脆いポリ乳酸を改質するために、種々研究開発が行われている。 Since polylactic acid is essentially hard and brittle, various research and development have been conducted to modify this hard and brittle polylactic acid.
例えば、特許文献１においては、結晶性のポリ乳酸１００質量部に対し、非結晶性のポリ乳酸を５０質量部以上含ませることにより、耐衝撃性、耐熱性、透明性に優れたシートを提供している。
For example,
またポリ乳酸に可塑剤を添加することにより、ポリ乳酸の物性を改質、改良する技術もしられており、ポリ乳酸用可塑剤は種々検討されている（例えば特許文献２）。 In addition, techniques for modifying and improving the physical properties of polylactic acid by adding a plasticizer to polylactic acid have been developed, and various plasticizers for polylactic acid have been studied (for example, Patent Document 2).
しかし、例えば、結晶性であるポリ乳酸に可塑剤を使用したフィルムの場合、成形初期は良好な透明性、柔軟性が見られるものの、室温付近で結晶化が進行してしまい、時間の経過にともない、その透明性および柔軟性の低下が起こる。また、非結晶性ポリ乳酸に可塑剤を添加した場合、室温以上での物性の温度依存性が強く、耐熱性に問題がある。
本発明は上記事情に鑑みなされたもので、時間が経過しても非常に高い柔軟性と透明性、かつ強度を保持している生分解性ポリ乳酸樹脂組成物および該組成物からなる成形品を提供することを目的とする。 The present invention has been made in view of the above circumstances, and a biodegradable polylactic acid resin composition having very high flexibility, transparency, and strength over time, and a molded article comprising the composition The purpose is to provide.
上記目的は、少なくとも、結晶性ポリ乳酸、非結晶性ポリ乳酸および可塑剤を含有する組成物により達成することができる。 The above object can be achieved by a composition containing at least crystalline polylactic acid, amorphous polylactic acid and a plasticizer.
「結晶性ポリ乳酸」という用語における「結晶性」という用語は、適度な条件下で結晶化後、偏光顕微鏡等で結晶ドメインが観察されるものの意味で使用している。結晶性ポリ乳酸とは、Ｄ体乳酸の重合体（以下、「ポリＤ乳酸」という）またはＬ体乳酸の重合体（以下、「ポリＬ乳酸」という）を包含する意味で使用している。ポリＤ乳酸とポリＬ乳酸の混合物（１００／０〜０／１００：質量比）であってもよい。ポリＤ乳酸あるいはポリＬ乳酸はすでに公知の化合物であり、それ自体は、本質的に硬くて脆い性質を有している。本発明においては、上記「結晶性」という定義に当てはまる限り、ポリＤ乳酸の場合であれば、Ｌ乳酸モノマー単位、または脂肪族ヒドロキシカルボン酸、脂肪族ジオール、脂肪族ジカルボン酸等の乳酸モノマーと共重合可能な他のモノマー単位を含んでいてもよい。ポリＬ乳酸の場合も同様である。本発明においてはそのような共重合体も結晶性ポリ乳酸に含まれる。 The term “crystalline” in the term “crystalline polylactic acid” is used in the sense that a crystalline domain is observed with a polarizing microscope or the like after crystallization under moderate conditions. The crystalline polylactic acid is used in the meaning including a polymer of D-form lactic acid (hereinafter referred to as “poly-D-lactic acid”) or a polymer of L-form lactic acid (hereinafter referred to as “poly-L-lactic acid”). It may be a mixture of poly D lactic acid and poly L lactic acid (100/0 to 0/100: mass ratio). Poly-D lactic acid or poly-L lactic acid is a known compound, and as such, has essentially hard and brittle properties. In the present invention, as long as the definition of “crystallinity” is applied, in the case of poly-D lactic acid, an L-lactic acid monomer unit or a lactic acid monomer such as an aliphatic hydroxycarboxylic acid, an aliphatic diol, or an aliphatic dicarboxylic acid It may contain other monomer units that can be copolymerized. The same applies to poly L lactic acid. In the present invention, such a copolymer is also included in the crystalline polylactic acid.
本発明に使用できる結晶性ポリ乳酸は、適当な溶媒に溶解し、その溶液から溶媒を除去しポリ乳酸のフィルムが形成できる程度の分子量を有していれば特に限定されない。このような結晶性ポリ乳酸として、重量平均分子量（Ｍｗ）５０，０００〜１，０００，０００、好ましくは１００，０００〜５００，０００の範囲で製造あるいは入手可能であり、目的とする用途あるいは成形品により、結晶性ポリ乳酸を適宜選定選択すればない。市販品としてはレイシアＨ−１００（三井化学社製）、トヨタエコプラスチックＵ’ｓ（トヨタ自動車社製）等が入手可能である。
なお、本発明で使用する重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）は、サイズ排除クロマトグラフにより測定された標準ポリスチレン換算値を使用している。以下同様である。
The crystalline polylactic acid that can be used in the present invention is not particularly limited as long as it has a molecular weight that can be dissolved in an appropriate solvent and removed from the solution to form a polylactic acid film. Such crystalline polylactic acid can be produced or available in a weight average molecular weight (Mw) range of 50,000 to 1,000,000, preferably 100,000 to 500,000, and is intended for use or molding. Depending on the product, crystalline polylactic acid has to be selected and selected appropriately. Commercially available products include Lacia H-100 (manufactured by Mitsui Chemicals), Toyota Eco Plastic U's (manufactured by Toyota Motor Corporation), and the like.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) used by this invention are using the standard polystyrene conversion value measured by the size exclusion chromatograph. The same applies hereinafter.
「非結晶性ポリ乳酸」における「非結晶性」という用語は、適度な条件下で結晶化後、偏光顕微鏡等で結晶ドメインが観察されないものの意味で使用している。非結晶性ポリ乳酸とは、Ｄ体乳酸とＬ体乳酸の共重合体（以下、「ポリＤＬ乳酸」という）であるという意味で使用している。Ｄ体とＬ体の比率は上記非結晶性が確保する限りどのような重合比率であってもよく、Ｄ乳酸：Ｌ乳酸の共重合比９０：１０〜１０：９０の範囲から適宜選択選定するようにすればよい。また共重合体の形態は、ブロック共重合体、グラフト共重合体、ランダム共重合体等いずれであってもよい。本発明においては、上記「非結晶性」という定義に当てはまる限り、脂肪族ヒドロキシカルボン酸、脂肪族ジオール、脂肪族ジカルボン酸等の乳酸モノマーと共重合可能な他のモノマー単位を含んでいてもよい。本発明においてはそのような共重合体も非結晶性ポリ乳酸に含まれる。 The term “non-crystalline” in “non-crystalline polylactic acid” is used to mean that the crystal domain is not observed with a polarizing microscope or the like after crystallization under moderate conditions. Amorphous polylactic acid is used to mean a copolymer of D-form lactic acid and L-form lactic acid (hereinafter referred to as “poly-DL lactic acid”). The ratio of the D-form and the L-form may be any polymerization ratio as long as the above-mentioned non-crystalline property is ensured, and is appropriately selected and selected from the range of the copolymerization ratio of D lactic acid: L lactic acid 90:10 to 10:90 What should I do? The form of the copolymer may be any of a block copolymer, a graft copolymer, a random copolymer, and the like. In the present invention, as long as the definition of “non-crystalline” is applied, other monomer units copolymerizable with lactic acid monomers such as aliphatic hydroxycarboxylic acid, aliphatic diol, and aliphatic dicarboxylic acid may be included. . In the present invention, such a copolymer is also included in the amorphous polylactic acid.
本発明に使用できる非結晶性ポリ乳酸は、重量平均分子量（Ｍｗ）５０，０００〜１，０００，０００、好ましくは１００，０００〜５００，０００の範囲で製造あるいは入手可能であり、市販品としてはレイシアＨ−２８０（三井化学社製）等が入手可能である。 The non-crystalline polylactic acid that can be used in the present invention is produced or available in a weight average molecular weight (Mw) range of 50,000 to 1,000,000, preferably 100,000 to 500,000. Laissia H-280 (manufactured by Mitsui Chemicals, Inc.) is available.
非結晶性ポリ乳酸は、結晶性ポリ乳酸と非結晶ポリ乳酸との合計量の５０質量％以下、好ましくは３３質量％以下、より好ましくは３０質量以下、さらに好ましくは少なくとも５質量％以上の量を使用するようにする。このように非結晶性ポリ乳酸を結晶性ポリ乳酸に添加することにより、下記する可塑剤との添加と相俟って、実用可能な強度と耐熱性を保持する程度に結晶化の進行を抑制し、柔軟性、透明性の経時での低下を低減させることができる。非結晶性ポリ乳酸の割合が多すぎても、添加量に見合うさらなる効果の向上が見られず、また強度および熱的耐性の低下、ブロッキングが生じ、少なすぎると本発明の効果を十分に享受できない恐れが生じる。 The amount of the amorphous polylactic acid is 50% by mass or less, preferably 33% by mass or less, more preferably 30% by mass or less, further preferably at least 5% by mass or more of the total amount of the crystalline polylactic acid and the amorphous polylactic acid. To use. By adding non-crystalline polylactic acid to crystalline polylactic acid in this way, the progress of crystallization is suppressed to the extent that it maintains practical strength and heat resistance in combination with the addition of the plasticizer described below. In addition, a decrease in flexibility and transparency over time can be reduced. Even if the proportion of amorphous polylactic acid is too large, no further improvement in the effect commensurate with the amount added will be observed, and the strength and thermal resistance will be reduced and blocking will occur. If it is too small, the effect of the present invention will be fully enjoyed. There is a fear that it cannot be done.
本発明のポリ乳酸樹脂組成物を利用すると、結晶性ポリ乳酸の結晶の大きさ、結晶の分散性、結晶化度を制御することができ、その結果、強度と柔軟性の両立を図れ、かつ透明性を確保することができる。 When the polylactic acid resin composition of the present invention is used, the crystal size, crystal dispersibility, and crystallinity of crystalline polylactic acid can be controlled, and as a result, both strength and flexibility can be achieved, and Transparency can be ensured.
本発明で使用する可塑剤は樹脂に添加して柔軟性を付与する化合物であれば、特に制限はなく用いることができる。本発明の可塑剤としては、例えば、多塩基酸エステル系可塑剤、ポリエステル系可塑剤、多価アルコール系可塑剤、リン酸エステル系可塑剤、エポキシ系可塑剤、脂肪酸系可塑剤、スルホン酸系可塑剤などをあげることができる。好ましい可塑剤は、多価アルコール系可塑剤である。 If the plasticizer used by this invention is a compound which adds to a resin and provides a softness | flexibility, there will be no restriction | limiting in particular and it can use. Examples of the plasticizer of the present invention include polybasic acid ester plasticizers, polyester plasticizers, polyhydric alcohol plasticizers, phosphate ester plasticizers, epoxy plasticizers, fatty acid plasticizers, and sulfonic acids. Examples include plasticizers. A preferred plasticizer is a polyhydric alcohol plasticizer.
多塩基酸エステル系可塑剤の具体例としては、ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジイソブチルフタレート、ジアミルフタレート、ジヘキシルフタレート、ブチルオクチルフタレート、ブチルイソデシルフタレート、ブチルラウリルフタレート、ジ−（２−エチルヘキシル）フタレート、ジ−ｎ−オクチルフタレート、ジ−２−オクチルフタレート、ブチルココナットアルキルフタレート、椰子油の高圧還元による高級アルコールのフタレート、高級アルコールのフタレート、高級アルコールアルキレンオキサイド付加物のフタレート、混合アルコールフタレート、直鎖アルコールフタレート、ジラウリルフタレート、ジヘプチルフタレート、ジイソオクチルフタレート、オクチルデシルフタレート、ｎ−オクチル，ｎ−デシルフタレート、ジイソデシルフタレート、ジトリデシルフタレート、エチルヘキシルデシルフタレート、ジノニルフタレート、ブチルベンジルフタレート、ジシクロヘキシルフタレート、ジアリルフタレート、アルキルアリルフタレート、アルキルアリル変性フタレート、アルキル脂肪酸フタレート、ｎ−アルキル脂肪酸フタレート、ジメトキシエチルフタレート、ジブトキシエチルフタレート、メチルフタリルエチルグリコレート、エチルフタリルエチルグリコレート、ブチルフタリルブチルグリコレート、変性フタレート等のフタル酸エステル；ジ−ｎ−ブチルアジペート、ジイソブチルアジペート、ジ−（２−エチルヘキシル）アジペート、ジイソオクチルアジペート、ジイソデシルアジペート、オクチルデシルアジペート、ジカプリルアジペート、ベンジル−ｎ−ブチルアジペート、ポリプロピレンアジペート、ポリブチレンアジペート、ジブトキシエチルアジペート、ベンジルオクチルアジペート、高級アルコールのアジペート、高級アルコールアルキレンオキサイド付加物のアジペート等のアジピン酸エステル；ジ−２（−エチルヘキシル）アゼレート、ジイソオクチルアゼレート、ジ−２−エチルヘキシル−４−チオアゼレート、ジ−ｎ−ヘキシルアゼレート、ジイソブチルアゼレート等のアゼライン酸エステル。ジメチルセバケート、ジエチルセバケート、ジブチルセバケート、ジ−（２−エチルヘキシル）セバケート、ジイソオクチルセバケート等のセバシン酸エステル；ジ−ｎ−ブチルマレート、ジメチルマレート、ジエチルマレート、ジ−（２−エチルヘキシル）マレート、ジノニルマレート等のマレイン酸エステル；ジブチルフマレート、ジ−（２−エチルヘキシル）フマレート等のフマル酸エステル。トリ−（２−エチルヘキシル）トリメリテート、トリイソデシルトリメリテート、ｎ−オクチル，ｎ−デシルトリメリテート、トリイソオクチルトリメリテート、ジイソオクチルモノイソデシルトリメリテート等のトリメリット酸エステル。トリエチルシトレート、トリ−ｎ−ブチルシトレート、アセチルトリエチルシトレート、アセチルトリ−ｎ−ブチルシトレート、アセチルトリ−ｎ−オクチル，ｎ−デシルシトレート、アセチルトリ−（２−エチルヘキシル）シトレート等のクエン酸エステルなどがあげられる。 Specific examples of the polybasic acid ester plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diamyl phthalate, dihexyl phthalate, butyl octyl phthalate, butyl isodecyl phthalate, butyl lauryl phthalate, di- (2- Ethylhexyl) phthalate, di-n-octyl phthalate, di-2-octyl phthalate, butyl coconut alkyl phthalate, higher alcohol phthalate by high pressure reduction of coconut oil, higher alcohol phthalate, higher alcohol alkylene oxide adduct phthalate, mixed Alcohol phthalate, linear alcohol phthalate, dilauryl phthalate, diheptyl phthalate, diisooctyl phthalate, octyl decyl phthalate, n-oct , N-decyl phthalate, diisodecyl phthalate, ditridecyl phthalate, ethylhexyl decyl phthalate, dinonyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, diallyl phthalate, alkyl allyl phthalate, alkyl allyl phthalate, alkyl fatty acid phthalate, n-alkyl fatty acid phthalate Phthalic acid esters such as dimethoxyethyl phthalate, dibutoxyethyl phthalate, methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, modified phthalate; di-n-butyl adipate, diisobutyl adipate, di -(2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyldecyl adipate Adipic acid esters such as dicapryl adipate, benzyl-n-butyl adipate, polypropylene adipate, polybutylene adipate, dibutoxyethyl adipate, benzyloctyl adipate, adipate of higher alcohol, adipate of higher alcohol alkylene oxide adduct; Azelaic acid esters such as (-ethylhexyl) azelate, diisooctylazelate, di-2-ethylhexyl-4-thioazelate, di-n-hexylazelate, diisobutylazelate. Sebacic acid esters such as dimethyl sebacate, diethyl sebacate, dibutyl sebacate, di- (2-ethylhexyl) sebacate, diisooctyl sebacate; di-n-butyl malate, dimethyl malate, diethyl malate, di- (2 -Maleic acid esters such as ethylhexyl) malate and dinonylmalate; Fumaric acid esters such as dibutyl fumarate and di- (2-ethylhexyl) fumarate. Trimellitic acid esters such as tri- (2-ethylhexyl) trimellitate, triisodecyl trimellitate, n-octyl, n-decyl trimellitate, triisooctyl trimellitate, diisooctyl monoisodecyl trimellitate. Triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri-n-butyl citrate, acetyl tri-n-octyl, n-decyl citrate, acetyl tri- (2-ethylhexyl) citrate, etc. And citric acid esters.
ポリエステル系可塑剤の具体例としては、アジピン酸、セバチン酸、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸、ジフェニルジカルボン酸などの酸成分と、プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、１，６−ヘキサンジオール、エチレングリコール、ジエチレングリコールなどのジオール成分からなるポリエステルや、ポリカプロラクトンなどのヒドロキシカルボン酸からなるポリエステルなどを挙げることができる。これらのポリエステルは単官能カルボン酸もしくは単官能アルコールで末端封鎖されていてもよく、またエポキシ化合物などで末端封鎖されていてもよい。 Specific examples of the polyester plasticizer include acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, propylene glycol, 1,3-butanediol, 1,4-butane. Examples thereof include polyesters composed of diol components such as diol, 1,6-hexanediol, ethylene glycol and diethylene glycol, and polyesters composed of hydroxycarboxylic acid such as polycaprolactone. These polyesters may be end-capped with a monofunctional carboxylic acid or monofunctional alcohol, or may be end-capped with an epoxy compound or the like.
多価アルコール系可塑剤の具体例としては、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−プロパンジオール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオール、ペンタンジオール、ヘキサンジオール、デカンジオール、ネオペンチルグリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリ（エチレンオキサイド・プロピレンオキサイド）ブロックおよび／又はランダム共重合体、ポリテトラメチレングリコール、ビスフェノール、グリセリン、ジグリセリン、ポリグリセリン、エリスリトール、キシリトール、マンニトール、ソルビトール、トリメチレンプロパノール、ペンタエリスリトール、ジペンタエリスリトール等の多価アルコールやこれらの重合体、また、エチレンオキシド付加重合体、プロピレンオキシド付加重合体などのアルキレンオキシド付加重合体などをあげる事ができる。さらにこれらの多価アルコールの誘導体も好適に用いることが出来、例えば、トリエチレングリコールジ−（２−エチルブチレート）、トリエチレングリコールジ−（２−エチルヘキソエート）、トリエチレングリコールジベンゾエート、ポリエチレングリコールジ−（２−エチルヘキソエート）、ジブチルメチレンビス−チオグリコレート、グリセリンモノアセテート、グリセリンジアセテート、グリセリントリアセテート、グリセリントリブチレート、グリセリントリプロピオネート、グリセリンジアセトモノカプレート、グリセリンモノアセトモノラウレート、グリセリンジアセトモノオレート、グリセリンモノリシノレートトリアセテート、グリセリンモノアセトモノモンタネート、ポリオキシエチレングリセリントリアセテート、ジグリセリンテトラアセテート、ポリグリセリンモノラウレートアセテートなどを挙げることができる。 Specific examples of the polyhydric alcohol plasticizer include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, pentanediol, hexanediol, decanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, bisphenol, glycerin , Diglycerin, polyglycerin, erythritol, xylitol, mannitol, sorbitol, trimethylene propanol, pentaerythritol, dipentaene Polyhydric alcohols and these polymers such Suritoru, also ethylene oxide addition polymers, such as alkylene oxide addition polymer of propylene oxide addition polymer can be cited. Furthermore, derivatives of these polyhydric alcohols can also be suitably used. For example, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), triethylene glycol dibenzoate , Polyethylene glycol di- (2-ethylhexoate), dibutylmethylenebis-thioglycolate, glycerol monoacetate, glycerol diacetate, glycerol triacetate, glycerol tributyrate, glycerol tripropionate, glycerol diacetate monocaprate, glycerol Monoacetomonolaurate, glycerol diacetomonooleate, glycerol monoricinoleate triacetate, glycerol monoacetomonomontanate, polyoxyethylene glycerol triacetate, Glycerol tetraacetate, etc. polyglycerol monolaurate acetate can be mentioned.
リン酸エステル系可塑剤の具体例としては、リン酸トリエチル、リン酸トリブチル、リン酸トリ−２−エチルヘキシル、リン酸トリオクチル、リン酸トリフェニル、リン酸ジフェニル−２−エチルヘキシル、リン酸トリキシリルおよびリン酸トリクレシルなどを挙げることができる。 Specific examples of the phosphoric ester plasticizer include triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, triphenyl phosphate, diphenyl-2-ethylhexyl phosphate, trixylyl phosphate and phosphorus. Examples include tricresyl acid.
エポキシ系可塑剤の具体例としては、ブチルエポキシステアレート、エポキシモノエステル、オクチルエポキシステアレート、エポキシ化ブチルオレート、ジ−（２−エチルヘキシル）４，５−エポキシシクロヘキサン−１，２−カーボキシレート、エポキシ化半乾性油、エポキシ化トリグリセライド、エポキシブチルステアレート、エポキシオクチルステアレート、エポキシデシルステアレート、エポキシ化大豆油、エポキシ化亜麻仁油、メチルエポキシヒドロステアレート、グリセリルトリ−（エポキシアセトキシステアレート）、イソオクチルエポキシステアレート、主にビスフェノールＡとエピクロロヒドリンを原料とするような、いわゆるエポキシ樹脂等が挙げられる。 Specific examples of the epoxy plasticizer include butyl epoxy stearate, epoxy monoester, octyl epoxy stearate, epoxidized butyl oleate, di- (2-ethylhexyl) 4,5-epoxycyclohexane-1,2-carboxylate Epoxidized semi-drying oil, epoxidized triglyceride, epoxy butyl stearate, epoxy octyl stearate, epoxy decyl stearate, epoxidized soybean oil, epoxidized linseed oil, methyl epoxy hydrostearate, glyceryl tri- (epoxy acetoxy systemate ), Isooctyl epoxy stearate, and so-called epoxy resins mainly using bisphenol A and epichlorohydrin as raw materials.
脂肪酸系可塑剤の具体例としては、メチルオレート、ブチルオレート、メトキシエチルオレート、テトラヒドロフルフリルオレート、グリセリルモノオレート、ジエチレングリコールモノオレート、メチルアセチルリシノレート、ブチルアセチルリシノレート、グリセリルモノリシノレート、ジエチレングリコールモノリシノレート、グリセリルトリ−（アセチルリシノレート）、アルキルアセチルリシノレート、ｎ−ブチルステアレート、グリセリルモノステアレート、ジエチレングリコールジステアレート、安定化ペンタクロロメチルステアレート、塩素化メチルステアレート、塩素化アルキルステアレート、ジエチレングリコールモノラウレート、ジエチレングリコールジペラルゴネート、トリエチレングリコールジペラルゴネート、ブチルセロソルブペラルゴネート、クロルヒドリンメチルエーテル構造を含む直鎖脂肪酸エステル等が挙げられる。 Specific examples of the fatty acid plasticizer include methyl oleate, butyl oleate, methoxyethyl oleate, tetrahydrofurfuryl oleate, glyceryl monooleate, diethylene glycol monooleate, methyl acetyl ricinolate, butyl acetyl ricinolate, glyceryl mono ricinoleate, diethylene glycol mono acrylate. Sinolate, glyceryl tri- (acetylricinoleate), alkylacetylricinoleate, n-butyl stearate, glyceryl monostearate, diethylene glycol distearate, stabilized pentachloromethyl stearate, chlorinated methyl stearate, chlorinated alkyl Stearate, diethylene glycol monolaurate, diethylene glycol dipelargonate, triethylene glycol dipelargonate, Chill cellosolve pelargonate, etc. straight chain fatty ester containing a chlorohydrin methyl ether structure.
スルホン酸系可塑剤の具体例としては、ベンゼンスルホンブチルアミド、ｏ−トルエンスルホンアミド、ｐ−トルエンスルホンアミド、Ｎ−エチル−ｐ−トルエンスルホンアミド、ｏ−トルエンエチルスルホンアミド、ｐ−トルエンエチルスルホンアミド、Ｎ−シクロヘキシル−ｐ−トルエンスルホンアミド、フェノール及びクレゾールのアルキルスルホン酸エステル、スルホンアミド−ホルムアミド等が挙げられる。 Specific examples of the sulfonic acid plasticizer include benzenesulfone butyramide, o-toluenesulfonamide, p-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, o-tolueneethylsulfonamide, p-tolueneethylsulfone. Examples include amide, N-cyclohexyl-p-toluenesulfonamide, alkylsulfonic acid ester of phenol and cresol, sulfonamide-formamide, and the like.
可塑剤は、組成物全量（固形分）の３０質量％以下、好ましくは２５質量％以下であり、少なくとも５質量％含有させるようにする。その含有量が、多すぎると可塑剤のブリーディング、強度及びフィルム成形能、透明性の低下などの問題があり、少なすぎると十分な柔軟性が得られないといった問題がある。 The plasticizer is 30% by mass or less, preferably 25% by mass or less, and at least 5% by mass with respect to the total amount (solid content) of the composition. When the content is too large, there are problems such as bleeding of plasticizer, strength and film forming ability, and a decrease in transparency, and when the content is too small, there is a problem that sufficient flexibility cannot be obtained.
本発明のポリ乳酸樹脂組成物には、本発明の目的効果を損なわない限り、その他の添加剤、例えば紫外線等の光吸収剤、熱安定剤、染顔料、無機充填剤、結晶核剤、加水分解抑制剤、帯電防止剤、アンチブロッキング剤、防曇剤等、その他ポリ乳酸に相溶性があり所望の特性を有する物質を適宜選択して添加してもよい。 The polylactic acid resin composition of the present invention has other additives such as light absorbers such as ultraviolet rays, heat stabilizers, dyes and pigments, inorganic fillers, crystal nucleating agents, Other substances having compatibility with polylactic acid and having desired characteristics, such as a decomposition inhibitor, an antistatic agent, an antiblocking agent, and an antifogging agent, may be appropriately selected and added.
本発明のポリ乳酸樹脂組成物は、種々の形態、例えばフィルム、板状体、糸状体、ペレット、ボール（フレイク）にすることができ、最終成形体として、ラップ等の包装体、トレー、ボトル等の日用品等もちろん、現在使用されている非生分解性合成樹脂の代替樹脂成形品として種々適用することができる。成形方法は従来公知のいずれの成形方法、例えば加熱溶融法、溶媒法、スピンキャスト法、ディップコート等を採用することができる。それらの成形品は、柔軟で透明であり、かつ実用的強度、耐熱性を有し、しかもそれらの特性を長期間保持できる。 The polylactic acid resin composition of the present invention can be made into various forms such as films, plates, filaments, pellets and balls (flake), and the final molded body is a package such as a wrap, a tray, or a bottle. Of course, it can be variously applied as a substitute resin molded product of the non-biodegradable synthetic resin currently used. As the molding method, any conventionally known molding method such as a heat melting method, a solvent method, a spin casting method, dip coating, or the like can be adopted. These molded articles are flexible and transparent, have practical strength and heat resistance, and can retain their properties for a long period of time.
本発明のポリ乳酸樹脂組成物を、例えばフィルムに成形した場合、そのフィルムの有する諸特性を以下に示す。なお、下記には、フィルムの物性値を例示しているが、フィルム以外の成形品も、それらの諸物性が反映されて、時間が経過しても非常に高い柔軟性と透明性、かつ強度を保持していることは言うまでもない。 When the polylactic acid resin composition of the present invention is formed into, for example, a film, various properties of the film are shown below. In addition, although the physical property value of a film is illustrated below, as for molded articles other than a film, those physical properties are reflected and very high flexibility and transparency and strength are obtained even if time passes. Needless to say, it holds.
諸物性測定の対象の「フィルム」は、結晶性ポリ乳酸、非結晶性ポリ乳酸および可塑剤を含有し、非結晶性ポリ乳酸が、結晶性ポリ乳酸と非結晶性ポリ乳酸との合計量の３０質量％以下の割合で含まれるポリ乳酸樹脂組成物を、１００ｍｇ、溶媒（クロロホルム）１０ｍｌに室温で溶解させ、シャーレにキャスト後、室温で４８時間乾燥させ、直径３００ｍｍ ｘ （厚さ）４０μｍに成形することにより形成した。 The “film” to be measured for various physical properties contains crystalline polylactic acid, noncrystalline polylactic acid and a plasticizer, and the noncrystalline polylactic acid is the total amount of crystalline polylactic acid and noncrystalline polylactic acid. A polylactic acid resin composition contained in a proportion of 30% by mass or less is dissolved in 100 mg, 10 ml of a solvent (chloroform) at room temperature, cast into a petri dish, dried at room temperature for 48 hours, and adjusted to a diameter of 300 mm x (thickness) 40 μm. It was formed by molding.
結晶粒子（結晶化度、結晶子径、球晶）
（１）結晶化度（％）：２３％以下、３％以上、好ましくは７％以上、
大気環境下６０℃、１時間処理後の結晶化度：４２％以下、２２％以上、好ましくは４０％以上
結晶化度(crystalinity)（％）とは、試料全体に対する結晶質の割合を意味し、Ｘ線回折装置により測定した回折パターンから非晶質に起因するブロードなハロー及び結晶質に起因するシャープなピーク面積を算出し、結晶質と非晶質のピーク面積の和に対する結晶質の割合を示したものである。
Crystal particles (crystallinity, crystallite diameter, spherulites)
(1) Crystallinity (%): 23% or less, 3% or more, preferably 7% or more,
Crystallinity after treatment at 60 ° C. for 1 hour under atmospheric environment: 42% or less, 22% or more, preferably 40% or more The crystallinity (%) means the ratio of the crystalline to the whole sample. From the diffraction pattern measured by the X-ray diffractometer, the broad halo caused by the amorphous and the sharp peak area caused by the crystalline are calculated, and the ratio of the crystalline to the sum of the crystalline and amorphous peak areas Is shown.
結晶化度は、本発明に於いて引っ張り強度と柔軟性に大きく影響し、その値が大きくなる程、引っ張り強度が増加するのに対し、柔軟性が低下する。一方、その値が小さすぎる場合には、実用に十分な強度、耐熱性が得られなくなる。 The crystallinity greatly affects the tensile strength and flexibility in the present invention. As the value increases, the tensile strength increases, but the flexibility decreases. On the other hand, if the value is too small, strength and heat resistance sufficient for practical use cannot be obtained.
（２）結晶子径
結晶子径（Å）：１１０〜１４０
大気環境下６０℃、１時間処理後の結晶化度：１６０〜１９０
結晶子(crystallite)とは、単結晶とみなせる最大の集まりを意味し、結晶子径(crystallite size)（Å）は、X線回折により得られた回折ピークから半価幅をScherrerの式（Ｄ＝Ｋ・λ/βcosθ Ｄ：結晶子の大きさ λ：測定Ｘ線波長 β：半価幅 θ：回折線のブラッグ角 Ｋ：Scherrer定数）に代入することにより算出したものである。結晶子径は、本発明に於いて光透過性に影響し、その値が増加すると、透明性の低下を招く）。
(2) Crystallite diameter Crystallite diameter (Å): 110-140
Crystallinity after treatment for 1 hour at 60 ° C. in atmospheric environment: 160 to 190
The crystallite means the largest group that can be regarded as a single crystal, and the crystallite size (Å) indicates the half-value width from the diffraction peak obtained by X-ray diffraction. = K · λ / β cos θ D: crystallite size λ: measurement X-ray wavelength β: half-value width θ: Bragg angle of diffraction line K: Scherrer constant) In the present invention, the crystallite diameter affects the light transmittance, and when the value increases, the transparency decreases.
（３）球晶
最大球晶径：４〜１０μｍ
球晶(spherulite)とは、単結晶の球状集合体で、最大球晶径(spherulite size)は、偏光顕微鏡観察により得られた画像をWinROOFで解析することにより測定し算出したものである。最大球晶径は、本発明に於いて透明性に大きく影響し、その値が大きくなる程、透明性は低下する。
(3) Spherulite Maximum spherulite diameter: 4 to 10 μm
The spherulite is a single crystal spherical aggregate, and the maximum spherulite size is measured and calculated by analyzing an image obtained by observation with a polarizing microscope using WinROOF. The maximum spherulite diameter greatly affects the transparency in the present invention, and the greater the value, the lower the transparency.
球晶径分布
直径１μｍ以下の球晶の個数割合が４０％以上
球晶径分布は、偏光顕微鏡観察により得られた画像をWinroofで解析することにより測定し算出したものである。球晶径分布は、本発明に於いて透明性に大きく影響し、より小さい球晶の分布割合が多くなればなるほど、透明性は増す。
Spherulite size distribution The ratio of the number of spherulites having a diameter of 1 μm or less is 40% or more. The spherulite size distribution is measured and calculated by analyzing an image obtained by observation with a polarizing microscope using Winroof. The spherulite diameter distribution greatly affects the transparency in the present invention, and the transparency increases as the distribution ratio of smaller spherulites increases.
引張強度、引張率
引張強度：９０Ｍｐａ以上
切断時の伸張率：１９０％以上
Tensile strength, tensile rate Tensile strength: 90 Mpa or more Elongation rate at cutting: 190% or more
透明性（ＨＡＺＥ値（単位厚さ（μｍ）当たり））
ＨＡＺＥ値：０．４５以下
大気環境下６０℃、１時間処理後のＨＡＺＥ値：０．４５以下
Transparency (HAZE value (per unit thickness (μm))
HAZE value: 0.45 or less HAZE value after treatment at 60 ° C. for 1 hour in an atmospheric environment: 0.45 or less
ＨＡＺＥとは、試験片を通過する透過光のうち、前方散乱によって、入射光から２．５°以上それた透過光の百分率を意味し、透明性を評価する目安となる値である。その値が大きいほどフィルムは不透明であり、反対にその値が小さいほどフィルムは透明である。 HAZE means the percentage of the transmitted light that passes through the test piece that deviates by 2.5 ° or more from the incident light due to forward scattering, and is a value that serves as a standard for evaluating transparency. The larger the value, the more opaque the film, and the smaller the value, the clearer the film.
［発明の効果］
柔軟で透明であり、かつ実用的強度、耐熱性を有し、しかもそれらの特性を長期間保持できる生分解性ポリ乳酸樹脂組成物および該組成物からなる成形品を提供した。
[The invention's effect]
The present invention provides a biodegradable polylactic acid resin composition that is flexible and transparent, has practical strength and heat resistance, and can retain these properties for a long period of time, and a molded article made of the composition.
［ポリ乳酸フィルムの作製］
本実施例では、結晶性ポリ乳酸として、
ポリＬ乳酸（ＰＬＬＡ）、
重量平均分子量（Ｍｗ）：１５００００、
数平均分子量（Ｍｎ）：７４０００、
Ｍｗ／Ｍｎ＝２．１、
融点（ｍｐ）：１６４℃、
［α］Ｄ ２５＝−１５０°、
溶融粘度（ＭＦＲ）：７．７（１９０℃、２．１６ｋｇ）のものを用いた。
[Production of polylactic acid film]
In this example, as crystalline polylactic acid,
Poly-L-lactic acid (PLLA),
Weight average molecular weight (Mw): 150,000,
Number average molecular weight (Mn): 74000,
Mw / Mn = 2.1,
Melting point (mp): 164 ° C.
[Α] D 25 = −150 °,
A melt viscosity (MFR): 7.7 (190 ° C., 2.16 kg) was used.
また、非結晶性ポリ乳酸として、
ポリＤＬ乳酸（ＰＤＬＬＡ）、
重量平均分子量（Ｍｗ）：２２００００、
数平均分子量（Ｍｎ）：１１００００、
Ｍｗ／Ｍｎ＝２．０、
融点（ｍｐ）：なし
［α］Ｄ ２５＝−１１８°、
溶融粘度（ＭＦＲ）：２．５（１９０℃、２．１６ｋｇ）を用いた。
As non-crystalline polylactic acid,
Poly DL lactic acid (PDLLA),
Weight average molecular weight (Mw): 220,000,
Number average molecular weight (Mn): 110000,
Mw / Mn = 2.0,
Melting point (mp): None [α] D 25 = −118 °,
Melt viscosity (MFR): 2.5 (190 ° C., 2.16 kg) was used.
可塑剤としてジグリセロールテトラアセテート（ＤＧＴＡ）（リケマールＰＬ−７１０；理研ビタミン社製）、Ｃ８，Ｃ１０アセチル化モノグリセリド（８，１０ＡＭＧ）（リケマールＰＬ−０１９；理研ビタミン社製の２種類、多価アルコール系化合物を用いた。 Diglycerol tetraacetate (DGTA) (Riquemar PL-710; manufactured by Riken Vitamin Co., Ltd.), C8, C10 acetylated monoglyceride (8,10AMG) (Riquemar PL-019; Riken Vitamin Co., Ltd., two types of polyhydric alcohols as plasticizers Series compounds were used.
ＰＬＬＡ、ＰＤＬＬＡ、可塑剤（ＤＧＴＡ）をそれぞれクロロホルムに１ｇ／ｄｌの濃度で溶解させた。その溶液を使用し、ＰＬＬＡとＰＤＬＬＡの合計量に対してＰＤＬＬＡが質量含有率で５、１５、２５、３０％含まれるポリ乳酸フィルムを作製した。 PLLA, PDLLA, and plasticizer (DGTA) were each dissolved in chloroform at a concentration of 1 g / dl. Using this solution, polylactic acid films containing PDLLA in a mass content of 5, 15, 25, and 30% with respect to the total amount of PLLA and PDLLA were prepared.
すべてのサンプルに対し可塑剤は、フィルム全量（固形分）の１５質量％とした。 The plasticizer was 15% by mass of the total amount (solid content) of the film for all samples.
フィルムは、ＰＬＬＡ、ＰＤＬＬＡおよび可塑剤を所定の割合で混合した溶液（１０ｍｌ）をシャーレにキャスト後、室温で４８時間乾燥させて得た。 The film was obtained by casting a solution (10 ml) in which PLLA, PDLLA and a plasticizer were mixed at a predetermined ratio into a petri dish and then drying at room temperature for 48 hours.
［結晶性］
得られたフィルムの結晶状態を、偏光顕微鏡（OLYMPUS BX51：OLYMPUS社製）を用いて観察した。
[crystalline]
The crystal state of the obtained film was observed using a polarizing microscope (OLYMPUS BX51: manufactured by OLYMPUS).
非結晶性ポリ乳酸を添加していない可塑剤（ＤＧＴＡ）添加ポリ乳酸フィルムは、室温に置いて約１週間経過した後に、フィルム全体に渡って結晶が確認されたが、非結晶性ポリ乳酸を添加したフィルムにおいてはほとんど結晶の形成が観察されなかった。 The plasticizer (DGTA) -added polylactic acid film to which amorphous polylactic acid has not been added was confirmed to have crystallized over the entire film after about one week at room temperature. Little crystal formation was observed in the added film.
得られたフィルムを大気環境下６０℃で１時間処理し、上記と同様に結晶状態を観察した。非結晶性ポリ乳酸を添加したフィルムは、このような熱処理をした後においても、結晶の形成が観察されなかった。 The obtained film was treated at 60 ° C. for 1 hour in an atmospheric environment, and the crystal state was observed in the same manner as described above. In the film to which amorphous polylactic acid was added, no crystal formation was observed even after such heat treatment.
［結晶粒子］
図５に、上記で得られたフィルムの偏光顕微鏡（OLYMPUS BX51：OLYMPUS社製）を示した。例えば、Ｌ：ＤＬ（１００：０）の写真中、白点がポリ乳酸の球晶である。
ＰＤＬＬＡの割合が多くなるほど、ポリ乳酸の球晶の大きさが小さくなっているのがわかる。
下記表１に、結晶化度（％）、結晶子径（Å）、最大球晶径をまとめた。表２にフィルムを大気環境下６０℃で１時間処理した後の結晶化度（％）、結晶子径（Å）をまとめた。表３に、球晶径分布を示した。
[Crystal particles]
FIG. 5 shows a polarizing microscope (OLYMPUS BX51: manufactured by OLYMPUS) of the film obtained above. For example, in a photograph of L: DL (100: 0), the white point is a polylactic acid spherulite.
It can be seen that the larger the proportion of PDLLA, the smaller the size of polylactic acid spherulites.
Table 1 below summarizes the degree of crystallinity (%), the crystallite diameter (Å), and the maximum spherulite diameter. Table 2 summarizes the crystallinity (%) and crystallite diameter (Å) after the film was treated at 60 ° C. for 1 hour in an atmospheric environment. Table 3 shows the spherulite diameter distribution.
結晶化度(crystalinity)（％）は、X線回折装置（Rint 2000：Rigaku社製）により測定した値を示している。回折パターンから非晶質に起因するブロードなハロー及び結晶質に起因するシャープなピーク面積を算出し、結晶質と非晶質のピーク面積の和に対する結晶質の割合を示したものである。
X線回折測定は５゜＜２θ＜３５゜の範囲で行い１６.７゜、１９゜の位置に現れるピークを結晶質由来のピークとして測定を行った。
The crystallinity (%) indicates a value measured by an X-ray diffractometer (Rint 2000: manufactured by Rigaku). From the diffraction pattern, a broad halo attributed to amorphous and a sharp peak area attributed to crystalline are calculated, and the ratio of crystalline to the sum of crystalline and amorphous peak areas is shown.
X-ray diffraction measurement was performed in the range of 5 ° <2θ <35 °, and the peak appearing at 16.7 ° and 19 ° was measured as the peak derived from the crystalline substance.
表１，２におけるフィルムの結晶化度をグラフで表したものが図６である。図６からＰＤＬＬＡの添加量が増加するに従い、結晶化度が低下していることが明瞭にわかる。 FIG. 6 is a graph showing the crystallinity of the films in Tables 1 and 2. FIG. 6 clearly shows that the degree of crystallinity decreases as the amount of PDLLA added increases.
結晶子径(crystallite size)（Å）は、Ｘ線回折装置（Rint 2000：Rigaku社製）により得られた、回折ピークから半価幅をScherrerの式（Ｄ＝Ｋ・λ／βcosθ Ｄ：結晶子の大きさ λ：測定Ｘ線波長（CuKα＝1.54Å） β：半価幅 θ：回折線のブラッグ角 Ｋ：Scherrer定数(0.94)）に代入することにより算出したものである。 The crystallite size (Å) is obtained from an X-ray diffractometer (Rint 2000: manufactured by Rigaku). The half width from the diffraction peak is Scherrer's formula (D = K · λ / βcosθ D: crystal Child size λ: Measurement X-ray wavelength (CuKα = 1.54Å) β: Half width θ: Bragg angle of diffraction line K: Scherrer constant (0.94))
結晶子径は、本発明に於いて光透過性に影響し、その値が可塑剤やＰＤＬＬＡの添加によって増加していないことから、透明性の低下を抑えていることが分かる。 In the present invention, the crystallite diameter affects the light transmittance, and since the value does not increase by the addition of a plasticizer or PDLLA, it can be seen that the decrease in transparency is suppressed.
最大球晶径(spherulite size)は、偏光顕微鏡観察（OLYMPUS BX51：OLYMPUS社製）により得られた画像をWinROOFで解析することにより測定し算出したものである。 The maximum spherulite size is measured and calculated by analyzing an image obtained by observation with a polarizing microscope (OLYMPUS BX51: manufactured by OLYMPUS) using WinROOF.
表１における最大球晶径をグラフで表したものが図７である。図７からＰＤＬＬＡの添加量を増加させる程、最大球晶径が減少するということが明瞭にわかる。 FIG. 7 is a graph showing the maximum spherulite diameter in Table 1. FIG. 7 clearly shows that the maximum spherulite diameter decreases as the addition amount of PDLLA is increased.
球晶径分布は、偏光顕微鏡観察（OLYMPUS BX51：OLYMPUS社製）により得られた画像をWinROOFで解析することにより測定し算出したものである。ＰＤＬＬＡの添加量が増加するに従い、１μｍ以下の球晶の割合が増加していることが分かる。 The spherulite diameter distribution is measured and calculated by analyzing an image obtained by observation with a polarizing microscope (OLYMPUS BX51: manufactured by OLYMPUS) using WinROOF. It can be seen that the proportion of spherulites of 1 μm or less increases as the amount of PDLLA added increases.
表３における球晶径分布をグラフで表したものが図８である。図８からＰＤＬＬＡの添加量が増加するに従い、球晶のサイズが減少していることが明瞭にわかる。 FIG. 8 is a graph showing the spherulite diameter distribution in Table 3. FIG. 8 clearly shows that the size of the spherulites decreases as the amount of PDLLA added increases.
［引張強度、伸張率］
フィルムの引張強度、切断時の伸長率を、引張試験機（KYOWA）を用いて室温（２０±２℃）にて行った。サンプルは、横幅３０ｍｍ、縦７ｍｍの中１２ｍｍを４ｍｍ幅とした厚さ５０μｍのダンベル状（図１参照）にカットしたものを使用した。結果を図２に示す。
図２から、本発明のポリ乳酸フィルムは、適度な引張強度を保持したままで伸張率が増加していることがわかる。
[Tensile strength, elongation rate]
The tensile strength of the film and the elongation at break were measured at room temperature (20 ± 2 ° C.) using a tensile tester (KYOWA). The sample used was cut into a dumbbell shape (see FIG. 1) having a thickness of 30 μm and a width of 7 mm and 12 mm out of 7 mm having a width of 4 mm and a thickness of 50 μm. The results are shown in FIG.
From FIG. 2, it can be seen that the polylactic acid film of the present invention has an increased stretch rate while maintaining an appropriate tensile strength.
フィルムを大気環境下６０℃で１時間処理し、上記と同様に引張強度、切断時の伸長率を測定した。結果を図３に示す。
結晶性ポリ乳酸を添加していないフィルムにおいては、熱処理により完全に結晶化が進行し、非常に硬くて脆いフィルムに変化した。非結晶性ポリ乳酸を添加したフィルムにおいては、６０℃で１時間処理したにもかかわらず、高い切断伸張率を保持した。
The film was treated at 60 ° C. for 1 hour in an atmospheric environment, and the tensile strength and elongation at break were measured in the same manner as described above. The results are shown in FIG.
In the film to which crystalline polylactic acid was not added, crystallization progressed completely by heat treatment, and the film was changed to a very hard and brittle film. The film to which the amorphous polylactic acid was added maintained a high elongation at break despite being treated at 60 ° C. for 1 hour.
［透明性］
ＰＬＬＡ、ＰＤＬＬＡ、可塑剤（８，１０ＡＭＧ）をそれぞれクロロホルムに１ｇ／ｄｌの濃度で溶解させた。その溶液を使用し、ＰＬＬＡとＰＤＬＬＡの合計量に対してＰＤＬＬＡが質量含有率で５、１５、２５％含まれるポリ乳酸フィルムを作製した。可塑剤はフィルム全量（固形分）の質量１５％含有させた。
[transparency]
PLLA, PDLLA, and plasticizer (8,10AMG) were each dissolved in chloroform at a concentration of 1 g / dl. Using the solution, a polylactic acid film containing PDLLA in a mass content of 5, 15, 25% with respect to the total amount of PLLA and PDLLA was produced. The plasticizer was contained in a mass of 15% of the total amount of the film (solid content).
上記で得られたフィルムおよび大気環境下６０℃で１時間処理したフィルムの透明性を、ＪＩＳＫ７１３６に従って測定した。その際使用した測定機器は、ＮＤＨ２０００（日本電色工業社製）である。結果を下記表４に示す。単位厚さ当たりのＨＡＺＥ値（熱処理前後）のグラフを図４に示す。 Transparency of the film obtained above and a film treated for 1 hour at 60 ° C. in an atmospheric environment was measured according to JISK7136. The measuring instrument used at that time is NDH2000 (Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 4 below. A graph of the HAZE value (before and after heat treatment) per unit thickness is shown in FIG.
図４に示されているように、本発明のポリ乳酸フィルムは、単位厚さ（１μｍ−１）当たり０．４以下であり、また熱処理による透明性の変化も少なく、熱処理後であっても、０．４５以下であり）、透明性に優れている。 As shown in FIG. 4, the polylactic acid film of the present invention is 0.4 or less per unit thickness (1 μm −1 ), and there is little change in transparency due to heat treatment, even after heat treatment. 0.45 or less) and is excellent in transparency.
［耐熱性］
フィルム作製
ＰＬＬＡとＰＤＬＬＡの合計量に対して、ＰＤＬＬＡが５％、２５％、３０％含まれるようにＰＬＬＡ、ＰＤＬＬＡ、可塑剤（８，１０ＡＭＧ）、アンチブロッキング剤（エルカ酸アミド）をストレンドダイを備えた２軸押出機にて２００℃で混練しコールドカットしてペレットを作製した。作製したペレットは８０℃で５時間乾燥した。作製したペレットを用い、Ｔダイを備えた単軸押出機にて、加工温度２００℃にて３０μｍ厚のフィルムを成型した。得られたフィルムは幅２ｃｍ、縦１０ｃｍにカットした後、６０℃、１時間熱処理を行った。また、比較サンプルとしてＰＬＬＡ、可塑剤、アンチブロッキング剤よりなるフィルムおよび、ＰＤＬＬＡ、可塑剤、アンチブロッキング剤よりなるフィルムを作製した。
[Heat-resistant]
Film production PLLA, PDLLA, plasticizer (8, 10AMG) and anti-blocking agent (erucic amide) are used to make PDLLA 5%, 25% and 30% of the total amount of PLLA and PDLLA. The mixture was kneaded at 200 ° C. with a twin-screw extruder equipped with a cold cut to produce pellets. The produced pellet was dried at 80 ° C. for 5 hours. Using the prepared pellets, a 30 μm-thick film was molded at a processing temperature of 200 ° C. using a single screw extruder equipped with a T die. The obtained film was cut into a width of 2 cm and a length of 10 cm, and then heat-treated at 60 ° C. for 1 hour. Moreover, the film which consists of PLLA, a plasticizer, and an antiblocking agent and the film which consists of PDLLA, a plasticizer, and an antiblocking agent were produced as a comparative sample.
すべてのサンプルに対し可塑剤は、フィルム全量（固形分）の１５質量％、アンチブロッキング剤は１．０質量％とした。作製したフィルムは２０℃湿度５０％の条件で保管した。 For all samples, the plasticizer was 15% by mass of the total amount of film (solid content), and the antiblocking agent was 1.0% by mass. The produced film was stored under the conditions of 20 ° C. and 50% humidity.
測定温度に調整したオーブン中に、フィルム下部に１０ｇの荷重をかかるようにして吊り下げ、１時間後フィルムが切断しているかを観察した。フィルムが切断していない場合は、測定温度を５℃上げて、新しいフィルムにて再度テストを行った。フィルムが切断した温度を耐熱温度とした。結果を図９に示した。本発明のフィルムは高い耐熱温度（１２０℃以上）を有していることがわかる。 The film was suspended in an oven adjusted to the measurement temperature so that a load of 10 g was applied to the lower part of the film, and it was observed whether the film was cut after 1 hour. When the film was not cut, the measurement temperature was raised by 5 ° C. and the test was performed again with a new film. The temperature at which the film was cut was defined as the heat resistant temperature. The results are shown in FIG. It turns out that the film of this invention has high heat-resistant temperature (120 degreeC or more).
［経時物性変化］
フィルム作成１日後および４ヶ月後のフィルムの引張強度、引張弾性率、切断時の伸張率を引張り試験機にて室温にて測定した。また透明性（単位当たり）を測定した。結果を表５に示した。
[Changes in physical properties over time]
The tensile strength, tensile elastic modulus, and elongation at break of the film after 1 day and 4 months after film formation were measured at room temperature using a tensile tester. Transparency (per unit) was also measured. The results are shown in Table 5.
引張強度：成型直後（１日後）の引張強度を４ヶ月後においても９０％以上維持（室温）。
切断時の伸張率：成型直後（１日後）の切断時の伸張率を４ヶ月後においても９０％以上維持（室温）。
本発明のフィルムは成型直後の物性を４ヶ月後においても維持していた。
Tensile strength: Maintains 90% or more of tensile strength immediately after molding (after 1 day) even after 4 months (room temperature).
Elongation rate at the time of cutting: 90% or more of the elongation rate at the time of cutting immediately after molding (after 1 day) is maintained even after 4 months (room temperature).
The film of the present invention maintained the physical properties immediately after molding even after 4 months.
なお、引張弾性率は、フィルムの柔軟性の目安であり、その値が大きいほどフィルムは硬くなり、逆に、その値が小さいほどフィルムは柔軟である。 The tensile modulus is a measure of the flexibility of the film. The larger the value, the harder the film, and the smaller the value, the more flexible the film.
Claims (9)
It consists essentially of crystalline polylactic acid, amorphous polylactic acid and a plasticizer, and the amorphous polylactic acid is 5 to 33% by mass or less of the total amount of crystalline polylactic acid and amorphous polylactic acid, plasticizer Is a polylactic acid resin composition containing 30% by mass or less of the total amount of the composition, and when the composition is formed into a film, the number ratio of spherulites having a diameter of 1 μm or less in the spherulite diameter distribution is 40. %, And the maximum spherulite size is 15 μm or less, and the HAZE value per unit thickness after the film is treated at 60 ° C. for 1 hour has a value of 0.45 or less. Resin composition.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031069A (en) * | 2006-07-27 | 2008-02-14 | Osaka Univ | Benzyl diglycerol acetate and polyester resin composition containing the compound |
| JP2009155378A (en) * | 2007-12-25 | 2009-07-16 | Unitika Ltd | Biodegradable polyester resin composition, and cellular material and molding obtained therefrom |
| JP2009155489A (en) * | 2007-12-27 | 2009-07-16 | Toray Ind Inc | Molding and manufacturing method therefor |
| JP2013018995A (en) * | 2012-10-22 | 2013-01-31 | Toray Ind Inc | Molded article and manufacturing method therefor |
| JP2014055222A (en) * | 2012-09-12 | 2014-03-27 | Arakawa Chem Ind Co Ltd | Polymerized rosin-based polyester, plasticizer for lactic acid-based resin, lactic acid-based resin composition and molded product |
| JP2015030814A (en) * | 2013-08-05 | 2015-02-16 | 株式会社リコー | Polylactic acid, and production method thereof |
| JP6821863B1 (en) * | 2019-08-30 | 2021-01-27 | 三栄源エフ・エフ・アイ株式会社 | A solid composition containing an amorphous poorly water-soluble material, and a method for producing the same. |
| JP2021507034A (en) * | 2018-06-15 | 2021-02-22 | 金発科技股▲フン▼有限公司Ｋｉｎｇｆａ Ｓｃｉ． ＆ Ｔｅｃｈ． Ｃｏ．， Ｌｔｄ． | Polylactic acid 3D printing material and its preparation method |
| WO2021040027A1 (en) * | 2019-08-30 | 2021-03-04 | 三栄源エフ・エフ・アイ株式会社 | Solid composition containing amorphous, poorly water-soluble material, and method for producing same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002002771A (en) * | 2000-06-23 | 2002-01-09 | Unitika Ltd | Polylactic-acid-based packing band |
| JP2003073532A (en) * | 2001-06-19 | 2003-03-12 | Riken Vitamin Co Ltd | Aliphatic polyester composition and flexible molded product |
| WO2004000939A1 (en) * | 2002-06-20 | 2003-12-31 | Toray Industries, Inc. | Polylactic acid base polymer composition, molding thereof and film |
| JP2004149636A (en) * | 2002-10-29 | 2004-05-27 | Asahi Kasei Life & Living Corp | Polylactic acid resin composition and molded article |
| JP2004204128A (en) * | 2002-12-26 | 2004-07-22 | Mitsubishi Plastics Ind Ltd | Polylactic acid polymer composition for thermoforming, polylactic acid polymer sheet, and thermoformed product using the sheet |
| JP2004314460A (en) * | 2003-04-17 | 2004-11-11 | Unitika Ltd | Biodegradable composite |
| JP2005036172A (en) * | 2003-07-18 | 2005-02-10 | Hiroshima Kasei Ltd | Composition for biodegradable soft transparent film and biodegradable soft transparent film produced therefrom |
-
2006
- 2006-05-26 JP JP2006146833A patent/JP4928157B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002002771A (en) * | 2000-06-23 | 2002-01-09 | Unitika Ltd | Polylactic-acid-based packing band |
| JP2003073532A (en) * | 2001-06-19 | 2003-03-12 | Riken Vitamin Co Ltd | Aliphatic polyester composition and flexible molded product |
| WO2004000939A1 (en) * | 2002-06-20 | 2003-12-31 | Toray Industries, Inc. | Polylactic acid base polymer composition, molding thereof and film |
| JP2004149636A (en) * | 2002-10-29 | 2004-05-27 | Asahi Kasei Life & Living Corp | Polylactic acid resin composition and molded article |
| JP2004204128A (en) * | 2002-12-26 | 2004-07-22 | Mitsubishi Plastics Ind Ltd | Polylactic acid polymer composition for thermoforming, polylactic acid polymer sheet, and thermoformed product using the sheet |
| JP2004314460A (en) * | 2003-04-17 | 2004-11-11 | Unitika Ltd | Biodegradable composite |
| JP2005036172A (en) * | 2003-07-18 | 2005-02-10 | Hiroshima Kasei Ltd | Composition for biodegradable soft transparent film and biodegradable soft transparent film produced therefrom |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031069A (en) * | 2006-07-27 | 2008-02-14 | Osaka Univ | Benzyl diglycerol acetate and polyester resin composition containing the compound |
| JP4676932B2 (en) * | 2006-07-27 | 2011-04-27 | 国立大学法人大阪大学 | Benzyldiglycerin acetate and polyester resin composition containing the compound |
| JP2009155378A (en) * | 2007-12-25 | 2009-07-16 | Unitika Ltd | Biodegradable polyester resin composition, and cellular material and molding obtained therefrom |
| JP2009155489A (en) * | 2007-12-27 | 2009-07-16 | Toray Ind Inc | Molding and manufacturing method therefor |
| JP2014055222A (en) * | 2012-09-12 | 2014-03-27 | Arakawa Chem Ind Co Ltd | Polymerized rosin-based polyester, plasticizer for lactic acid-based resin, lactic acid-based resin composition and molded product |
| JP2013018995A (en) * | 2012-10-22 | 2013-01-31 | Toray Ind Inc | Molded article and manufacturing method therefor |
| JP2015030814A (en) * | 2013-08-05 | 2015-02-16 | 株式会社リコー | Polylactic acid, and production method thereof |
| JP2021507034A (en) * | 2018-06-15 | 2021-02-22 | 金発科技股▲フン▼有限公司Ｋｉｎｇｆａ Ｓｃｉ． ＆ Ｔｅｃｈ． Ｃｏ．， Ｌｔｄ． | Polylactic acid 3D printing material and its preparation method |
| JP7129480B2 (en) | 2018-06-15 | 2022-09-01 | 金発科技股▲ふん▼有限公司 | Polylactic acid 3D printing material and its preparation method |
| JP6821863B1 (en) * | 2019-08-30 | 2021-01-27 | 三栄源エフ・エフ・アイ株式会社 | A solid composition containing an amorphous poorly water-soluble material, and a method for producing the same. |
| WO2021040027A1 (en) * | 2019-08-30 | 2021-03-04 | 三栄源エフ・エフ・アイ株式会社 | Solid composition containing amorphous, poorly water-soluble material, and method for producing same |
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