JP5252736B2 - Polylactic acid resin composition and molded article comprising the same - Google Patents
Polylactic acid resin composition and molded article comprising the same Download PDFInfo
- Publication number
- JP5252736B2 JP5252736B2 JP2009245602A JP2009245602A JP5252736B2 JP 5252736 B2 JP5252736 B2 JP 5252736B2 JP 2009245602 A JP2009245602 A JP 2009245602A JP 2009245602 A JP2009245602 A JP 2009245602A JP 5252736 B2 JP5252736 B2 JP 5252736B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polylactic acid
- resin composition
- polylactic
- fatty acid
- 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.)
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 83
- 239000004626 polylactic acid Substances 0.000 title claims description 83
- 239000011342 resin composition Substances 0.000 title claims description 35
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 73
- 239000000194 fatty acid Substances 0.000 claims description 73
- 229930195729 fatty acid Natural products 0.000 claims description 73
- -1 fatty acid ester Chemical class 0.000 claims description 62
- 229920005989 resin Polymers 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 43
- 150000004665 fatty acids Chemical class 0.000 claims description 36
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 30
- 238000000465 moulding Methods 0.000 claims description 27
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 22
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 22
- 229920000223 polyglycerol Polymers 0.000 claims description 21
- 239000005639 Lauric acid Substances 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 15
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 11
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 11
- 229960002446 octanoic acid Drugs 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 description 39
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 28
- 125000001931 aliphatic group Chemical group 0.000 description 22
- 238000012360 testing method Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 229960000448 lactic acid Drugs 0.000 description 8
- 150000005846 sugar alcohols Polymers 0.000 description 8
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 235000014655 lactic acid Nutrition 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000004676 glycans Chemical class 0.000 description 6
- 239000004310 lactic acid Substances 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 229920003232 aliphatic polyester Polymers 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920006167 biodegradable resin Polymers 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PAZZVPKITDJCPV-UHFFFAOYSA-N 10-hydroxyoctadecanoic acid Chemical compound CCCCCCCCC(O)CCCCCCCCC(O)=O PAZZVPKITDJCPV-UHFFFAOYSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-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
- RKHXDCVAPIMDMG-UHFFFAOYSA-N 9-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCC(O)CCCCCCCC(O)=O RKHXDCVAPIMDMG-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-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
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
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- 239000004033 plastic Substances 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
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- 238000006068 polycondensation reaction Methods 0.000 description 2
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- 229920000573 polyethylene Polymers 0.000 description 2
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- 239000004800 polyvinyl chloride Substances 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical class [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- XSXIVVZCUAHUJO-AVQMFFATSA-N (11e,14e)-icosa-11,14-dienoic acid Chemical compound CCCCC\C=C\C\C=C\CCCCCCCCCC(O)=O XSXIVVZCUAHUJO-AVQMFFATSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- HVGRZDASOHMCSK-UHFFFAOYSA-N (Z,Z)-13,16-docosadienoic acid Natural products CCCCCC=CCC=CCCCCCCCCCCCC(O)=O HVGRZDASOHMCSK-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
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- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl Salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 description 1
- PHOJOSOUIAQEDH-UHFFFAOYSA-N 5-hydroxypentanoic acid Chemical compound OCCCCC(O)=O PHOJOSOUIAQEDH-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002160 Celluloid Polymers 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- 235000021297 Eicosadienoic acid Nutrition 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
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Description
本発明は、ポリ乳酸系樹脂組成物に関する。さらに詳しくは、透明で、耐衝撃性を有するポリ乳酸系樹脂組成物、該樹脂組成物の成形体、及び該樹脂組成物を含む複合体の成形体に関する。 The present invention relates to a polylactic acid resin composition. More specifically, the present invention relates to a transparent, impact-resistant polylactic acid resin composition, a molded body of the resin composition, and a molded body of a composite including the resin composition.
近年、プラスチック廃棄物の処理がクローズアップされている。包装材料等のプラスチック成形物は、使用後、焼却処理されるか、又は埋め立て処分されるのが一般的である。しかし、プラスチック廃棄物を焼却処理した場合、燃焼熱が高いために焼却炉の耐久性が問題となる。また、ポリ塩化ビニルを含む成形物を燃焼すると、有害ガスが発生して環境汚染の一因となる。一方、埋め立て処分した場合には、プラスチック成形物は分解されずに原形のまま半永久的に残ることから、自然環境への影響が問題となる。 In recent years, the treatment of plastic waste has been highlighted. In general, plastic molded articles such as packaging materials are incinerated after disposal or disposed of in landfills. However, when plastic waste is incinerated, the durability of the incinerator becomes a problem due to high combustion heat. In addition, when a molded product containing polyvinyl chloride is burned, harmful gases are generated and contribute to environmental pollution. On the other hand, in the case of landfill disposal, the plastic molded product remains semipermanent as it is without being decomposed, so that the influence on the natural environment becomes a problem.
このような状況下、自然環境下で微生物によって自然的副産物である炭酸ガス、水等に分解される、種々の生分解性プラスチックが発明されて、実用化レベルに入っている。 Under such circumstances, various biodegradable plastics that can be decomposed by natural microorganisms into carbon dioxide gas, water, etc. in a natural environment have been invented and put into practical use.
例えば、特許文献１には、脂肪族ポリエステルであるポリ乳酸、又は乳酸−その他のヒドロキシカルボン酸共重合体を主成分とする樹脂組成物が開示されており、十分な強度と耐久性を持つことから、分解性カード（シート）の原料として用い得ることが示されている。 For example, Patent Document 1 discloses a resin composition containing polylactic acid, which is an aliphatic polyester, or lactic acid-other hydroxycarboxylic acid copolymer as a main component, and has sufficient strength and durability. Therefore, it is shown that it can be used as a raw material for a degradable card (sheet).
しかし、該樹脂組成物の成形体は、透明性に優れ、弾性率及び剛性は高いものであるが、柔軟性に劣る。例えば、押し出し成形によって得られた成形体は、表面にひび割れや凹凸が認められたり、折り曲げ時には白色化したりするため、ポリエチレン、ポリプロピレン、軟質ポリ塩化ビニル等が汎用されるような柔軟性が要求される用途には適していない。 However, the molded body of the resin composition is excellent in transparency and high in elastic modulus and rigidity, but inferior in flexibility. For example, a molded product obtained by extrusion molding has cracks and irregularities on its surface, or whitens when bent, so that flexibility such as polyethylene, polypropylene, soft polyvinyl chloride, etc. is required. It is not suitable for use.
一般に、樹脂を軟質化する方法としては、可塑剤を添加する方法、コポリマー化する方法、軟質ポリマーをブレンドする方法等が知られている。例えば、特許文献２には、アジピン酸ジイソブチル、セバシン酸ジオクチル等の可塑剤を添加したポリ乳酸系樹脂組成物が開示されている。特許文献３には、ポリエチレンアジペートやポリエステルエーテル等で共重合させたポリ乳酸共重合体と、脂肪族ポリエステルの可塑剤とからなる樹脂組成物が開示されている。また、特許文献４では、ポリカプロラクトン、１,４−ブタンジオールとコハク酸の縮合体（ポリブチレンサクシネート）、ポリグリコリド等の生分解性脂肪族ポリエステルをポリ乳酸に混合した樹脂組成物が開示されている。 In general, as a method for softening a resin, a method of adding a plasticizer, a method of copolymerization, a method of blending soft polymers, and the like are known. For example, Patent Document 2 discloses a polylactic acid resin composition to which a plasticizer such as diisobutyl adipate and dioctyl sebacate is added. Patent Document 3 discloses a resin composition comprising a polylactic acid copolymer copolymerized with polyethylene adipate or polyester ether, and an aliphatic polyester plasticizer. Patent Document 4 discloses a resin composition in which polycaprolactone, a condensate of 1,4-butanediol and succinic acid (polybutylene succinate), a biodegradable aliphatic polyester such as polyglycolide is mixed with polylactic acid. Has been.
可塑剤を添加することで、ポリ乳酸系樹脂組成物の柔軟性を向上させることは可能となる。しかし、その効果は十分ではなく、また、従来の可塑剤は、成形直後又は経時的にブリードが生じて、成形体の柔軟性及び透明性等が変化するという問題がある。 By adding a plasticizer, the flexibility of the polylactic acid resin composition can be improved. However, the effect is not sufficient, and the conventional plasticizer has a problem that bleed occurs immediately after molding or with time, and the flexibility and transparency of the molded body change.
一方、成形体の生分解性を考慮すると、ポリ乳酸とコポリマー化やブレンドする樹脂には生分解性が要求されるため限定されたものとなる。また、生分解性樹脂によってポリ乳酸に柔軟性を付与することが出来たとしても、例えば、引張弾性率が１．０ＧＰａ以下となるためには、生分解性樹脂を多量に（例えば、ポリブチレンサクシネートの場合は、６０重量％以上）添加する必要があり、その結果、ポリ乳酸の特徴である耐熱性、透明性等が損なわれることが判明した。 On the other hand, considering the biodegradability of the molded product, the resin to be copolymerized or blended with polylactic acid is limited because biodegradability is required. In addition, even if flexibility can be imparted to polylactic acid by a biodegradable resin, for example, in order to obtain a tensile elastic modulus of 1.0 GPa or less, a large amount of biodegradable resin (for example, polybutylene is used). In the case of succinate, it is necessary to add 60% by weight or more), and as a result, it has been found that the heat resistance, transparency, etc., which are the characteristics of polylactic acid are impaired.
本発明の課題は、透明性が高く、かつ、耐衝撃性に優れるポリ乳酸系樹脂組成物、該樹脂組成物の成形体、及び該樹脂組成物を含む複合体の成形体を提供することにある。 An object of the present invention is to provide a polylactic acid-based resin composition having high transparency and excellent impact resistance, a molded body of the resin composition, and a molded body of a composite including the resin composition. is there.
本発明者らは、上記の課題を解決するために鋭意検討した結果、ポリ乳酸系樹脂に、カプリル酸、カプリン酸、及びラウリン酸を含み、ラウリン酸含有率が２０ｍｏｌ％以上である構成脂肪酸と、平均重合度が１０であるポリグリセリンとをエステル化率５０〜８０％でエステル化したポリグリセリン脂肪酸エステルを添加することにより、成形体の原料として好適なポリ乳酸系樹脂組成物が得られることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that the polylactic acid-based resin contains caprylic acid, capric acid, and lauric acid, and a constituent fatty acid having a lauric acid content of 20 mol% or more and By adding a polyglycerin fatty acid ester obtained by esterifying polyglycerin having an average degree of polymerization of 10 at an esterification rate of 50 to 80%, a polylactic acid-based resin composition suitable as a raw material for a molded article can be obtained. I found.
即ち、本発明は、
〔１〕 ポリ乳酸系樹脂及びポリグリセリン脂肪酸エステルを含有してなるポリ乳酸系樹脂組成物であって、該ポリグリセリン脂肪酸エステルの含有量が、ポリ乳酸系樹脂１００重量部に対して０．１〜３０重量部であり、かつ、ポリグリセリン脂肪酸エステルが、カプリル酸、カプリン酸、及びラウリン酸を構成脂肪酸として含有し、該ラウリン酸の含有量が構成脂肪酸中２０ｍｏｌ％以上であり、平均重合度が１０のポリグリセリンを含有し、さらに、ポリグリセリン脂肪酸エステルのエステル化率が５０〜８５％である、ポリ乳酸系樹脂組成物、
〔２〕 前記〔１〕記載のポリ乳酸系樹脂組成物を成形してなる、ポリ乳酸系樹脂成形体、ならびに
〔３〕 前記〔１〕記載のポリ乳酸系樹脂組成物を含む複合体を成形してなる成形体
に関する。
That is, the present invention
[1] A polylactic acid resin composition comprising a polylactic acid resin and a polyglycerol fatty acid ester, wherein the content of the polyglycerol fatty acid ester is 0.1 with respect to 100 parts by weight of the polylactic acid resin. -30 parts by weight, and the polyglycerol fatty acid ester contains caprylic acid, capric acid, and lauric acid as constituent fatty acids, and the content of the lauric acid is 20 mol% or more in the constituent fatty acids, and the average degree of polymerization A polylactic acid resin composition, wherein the polyglycerin fatty acid ester has an esterification rate of 50 to 85%,
[2] A polylactic acid resin molded article formed by molding the polylactic acid resin composition according to [1], and [3] a composite containing the polylactic acid resin composition according to [1]. It is related with the molded object formed.
本発明のポリ乳酸系樹脂組成物を成形して得られる成形体は、ポリ乳酸の高い透明性を維持したまま、耐衝撃性に優れるため、成形時に割れや亀裂が発生しないという優れた効果を奏する。 The molded product obtained by molding the polylactic acid-based resin composition of the present invention is excellent in impact resistance while maintaining the high transparency of polylactic acid, and therefore has an excellent effect that cracks and cracks do not occur during molding. Play.
本発明のポリ乳酸系樹脂組成物は、ポリ乳酸系樹脂及びポリグリセリン脂肪酸エステルを含有するものであって、該ポリグリセリン脂肪酸エステルが特定のものであることに１つの特徴を有する。 The polylactic acid-based resin composition of the present invention contains a polylactic acid-based resin and a polyglycerol fatty acid ester, and has one feature that the polyglycerol fatty acid ester is specific.
ポリ乳酸は、結晶性が高く分子構造が剛直であるため、硬く脆く、成型体が破損し易いことから、柔軟性についての改良が求められている。そこで、本発明者らが検討した結果、特定の構成脂肪酸を有するポリグリセリン脂肪酸エステルを含有させることにより、透明性を維持しながら、柔軟性を向上できることを見出した。ポリグリセリン脂肪酸エステルは、同一分子内に親水基と親油基を有する化合物であり、ポリ乳酸にも良好に分散して、ポリ乳酸の透明性を維持することが出来ると考えられる。また、ポリグリセリン脂肪酸エステルは構成成分の一つである脂肪酸の種類によって特性が大きく異なるが、カプリル酸、カプリン酸、及びラウリン酸を含有し、かつ、該ラウリン酸を特定量含有する脂肪酸を構成成分とすることで、ポリ乳酸系樹脂と前記脂肪酸が相互作用して相溶性が高まり、柔軟性が向上すると考えられる。 Since polylactic acid has high crystallinity and a rigid molecular structure, it is hard and brittle, and the molded product is easily damaged. Therefore, improvement in flexibility is required. Thus, as a result of investigations by the present inventors, it has been found that by including a polyglycerol fatty acid ester having a specific constituent fatty acid, flexibility can be improved while maintaining transparency. Polyglycerin fatty acid ester is a compound having a hydrophilic group and a lipophilic group in the same molecule, and can be well dispersed in polylactic acid to maintain the transparency of polylactic acid. Polyglycerin fatty acid esters have different characteristics depending on the type of fatty acid that is one of the constituent components, but they contain caprylic acid, capric acid, and lauric acid, and constitute a fatty acid containing a specific amount of the lauric acid. By using it as a component, it is considered that the polylactic acid-based resin and the fatty acid interact with each other to increase compatibility and improve flexibility.
本発明におけるポリ乳酸系樹脂は、分子中に乳酸単位〔ＣＨ３ＣＨ（ＯＨ）ＣＯＯＨ〕〕を含む脂肪族ポリエステル樹脂であり、分子中に該乳酸単位を少なくとも５０モル％、好ましくは６０モル％以上、より好ましくは７０モル％以上含む脂肪族ポリエステル樹脂である。 The polylactic acid resin in the present invention is an aliphatic polyester resin containing a lactic acid unit [CH 3 CH (OH) COOH]] in the molecule, and the lactic acid unit in the molecule is at least 50 mol%, preferably 60 mol%. More preferably, the aliphatic polyester resin contains 70 mol% or more.
具体的には、
（１）ポリ乳酸、
（２）乳酸−他の脂肪族ヒドロキシカルボン酸コポリマー、
（３）多官能多糖類、及び乳酸単位を含むポリ乳酸系樹脂、
（４）脂肪族多価カルボン酸単位、脂肪族多価アルコール単位、及び乳酸単位を含むポリ乳酸系樹脂、ならびに
（５）これらの混合物
が挙げられる。これらの中でも、得られる成形体の透明性の観点から、ポリ乳酸、及び、乳酸−他の脂肪族ヒドロキシカルボン酸コポリマーが好ましく、ポリ乳酸がより好ましい。
In particular,
(1) polylactic acid,
(2) Lactic acid-other aliphatic hydroxycarboxylic acid copolymer,
(3) a polylactic acid-based resin containing a polyfunctional polysaccharide and a lactic acid unit,
(4) Polylactic acid-based resins containing aliphatic polycarboxylic acid units, aliphatic polyhydric alcohol units, and lactic acid units, and (5) mixtures thereof. Among these, polylactic acid and lactic acid-other aliphatic hydroxycarboxylic acid copolymers are preferable, and polylactic acid is more preferable from the viewpoint of transparency of the obtained molded body.
乳酸には、Ｌ−体とＤ−体の光学異性体が存在する。本発明に用いるポリ乳酸としては、構成単位がＬ−乳酸のみからなるポリ（Ｌ−乳酸）、Ｄ−乳酸のみからなるポリ（Ｄ−乳酸）、及びＬ−乳酸単位とＤ−乳酸単位とが種々の割合で存在するポリ（ＤＬ−乳酸）等が挙げられる。なお、本明細書において、単に乳酸という場合は、特にことわりがない限り、Ｌ−体とＤ−体の両者を意味する。 Lactic acid has optical isomers of L-form and D-form. The polylactic acid used in the present invention includes poly (L-lactic acid) whose structural unit is composed only of L-lactic acid, poly (D-lactic acid) composed of only D-lactic acid, and L-lactic acid units and D-lactic acid units. Examples thereof include poly (DL-lactic acid) present in various proportions. In the present specification, the term “lactic acid” means both L-form and D-form unless otherwise specified.
ポリ乳酸の製造方法として、Ｌ−乳酸、Ｄ−乳酸、又はＤＬ−乳酸を直接脱水重縮合する方法、これら各乳酸の環状２量体であるラクチドを開環重合する方法等が挙げられる。また、何れの重合方法においても、重合の途中段階で鎖延長剤を添加して分子量を上げても良い。また開環重合は、高級アルコール、ヒドロキシカルボン酸等の水酸基を有する化合物の存在下で行ってもよく、何れの方法によって製造されたものでもよい Examples of the method for producing polylactic acid include a method of directly dehydrating polycondensation of L-lactic acid, D-lactic acid or DL-lactic acid, a method of ring-opening polymerization of lactide which is a cyclic dimer of these lactic acids, and the like. In any polymerization method, a molecular weight may be increased by adding a chain extender in the middle of the polymerization. The ring-opening polymerization may be performed in the presence of a compound having a hydroxyl group such as a higher alcohol or hydroxycarboxylic acid, or may be produced by any method.
乳酸−他の脂肪族ヒドロキシカルボン酸コポリマーの脂肪族ヒドロキシカルボン酸としては、グリコール酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、４−ヒドロキシ吉草酸、５−ヒドロキシ吉草酸、６−ヒドロキシカプロン酸等が挙げられる。 Examples of the aliphatic hydroxycarboxylic acid of the lactic acid-other aliphatic hydroxycarboxylic acid copolymer include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and the like. Is mentioned.
乳酸−他の脂肪族ヒドロキシカルボン酸コポリマーの製造方法として、上記各乳酸と上記脂肪族ヒドロキシカルボン酸を脱水重縮合する方法、上記各乳酸の環状２量体であるラクチドと上記脂肪族ヒドロキシカルボン酸の環状体を開環共重合する方法等が挙げられる。何れの方法によって製造されたものでもよい。乳酸−他の脂肪族ヒドロキシカルボン酸コポリマーに含まれる乳酸単位の量は少なくとも５０モル％であることが好ましい。 As a method for producing lactic acid-other aliphatic hydroxycarboxylic acid copolymer, dehydration polycondensation of each lactic acid and aliphatic hydroxycarboxylic acid, lactide which is a cyclic dimer of each lactic acid, and aliphatic hydroxycarboxylic acid And a ring-opening copolymerization method. It may be produced by any method. The amount of lactic acid units contained in the lactic acid-other aliphatic hydroxycarboxylic acid copolymer is preferably at least 50 mol%.
多官能多糖類、及び乳酸単位を含むポリ乳酸系樹脂における多官能多糖類としては、例えば、セルロース、酢酸セルロース、硝酸セルロース、メチルセルロース、エチルセルロース、セルロイド、ビスコースレーヨン、再生セルロース、セロハン、キュプラ、銅アンモニアレーヨン、キュプロファン、ベンベルグ、ヘミセルロース、デンプン、アクロペクチン、デキストリン、デキストラン、グリコーゲン、ペクチン、キチン、キトサン、アラビアガム、グァーガム、ローカストビーンガム、アカシアガム等、及びこれらの混合物、ならびに、これらの誘導体が挙げられる。これらの内、酢酸セルロース、及びエチルセルロースが好ましい。 Examples of polyfunctional polysaccharides and polyfunctional polysaccharides in polylactic acid resins containing lactic acid units include cellulose, cellulose acetate, cellulose nitrate, methylcellulose, ethylcellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, copper Ammonia rayon, cuprophane, bemberg, hemicellulose, starch, acropectin, dextrin, dextran, glycogen, pectin, chitin, chitosan, gum arabic, guar gum, locust bean gum, acacia gum, and mixtures thereof, and derivatives thereof Is mentioned. Of these, cellulose acetate and ethyl cellulose are preferred.
多官能多糖類、及び乳酸単位を含むポリ乳酸系樹脂の製造方法として、上記多官能多糖類と、上記ポリ乳酸又は乳酸−他の脂肪族ヒドロキシカルボン酸コポリマー等を反応させる方法、上記多官能多糖類と、上記各乳酸及び環状エステル類等を反応させる方法等が挙げられる。何れの方法によって製造されたものでもよい。前記ポリ乳酸系樹脂に含まれる乳酸単位の量は少なくとも５０モル％であることが望ましい。 As a method for producing a polyfunctional polysaccharide and a polylactic acid resin containing a lactic acid unit, a method of reacting the polyfunctional polysaccharide with the polylactic acid or a lactic acid-other aliphatic hydroxycarboxylic acid copolymer, the polyfunctional polysaccharide Examples include a method of reacting a saccharide with each of the above lactic acid and cyclic esters. It may be produced by any method. The amount of lactic acid units contained in the polylactic acid resin is preferably at least 50 mol%.
脂肪族多価カルボン酸単位、脂肪族多価アルコール単位、及び乳酸単位を含むポリ乳酸系樹脂における脂肪族多価カルボン酸単位としては、例えば、シュウ酸、コハク酸、マロン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、ウンデカン二酸、ドデカン二酸等、及びこれらの無水物が挙げられる。これらは、酸無水物との混合物であってもよい。また、脂肪族多価アルコール単位としては、例えば、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−ブタンジオール、１，４−ブタンジオール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、ネオペンチルグリコール、テトラメチレングリコール、１，４−シクロヘキサンジメタノール等が挙げられる。 Examples of the aliphatic polycarboxylic acid unit in the polylactic acid resin containing an aliphatic polycarboxylic acid unit, an aliphatic polyhydric alcohol unit, and a lactic acid unit include, for example, oxalic acid, succinic acid, malonic acid, glutaric acid, adipine Examples include acids, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, and the like, and anhydrides thereof. These may be a mixture with an acid anhydride. Examples of the aliphatic polyhydric alcohol unit include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 3-methyl-1,5. -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol and the like.
脂肪族多価カルボン酸単位、脂肪族多価アルコール単位、及び乳酸単位を含むポリ乳酸系樹脂の製造方法として、上記脂肪族多価カルボン酸単位及び上記脂肪族多価アルコール単位と、上記ポリ乳酸又は乳酸−他の脂肪族ヒドロキシカルボン酸コポリマー等を反応する方法、上記脂肪族多価カルボン酸単位及び上記脂肪族多価アルコール単位と、上記各乳酸及び環状エステル類等を反応する方法等が挙げられる。何れの方法によって製造されたものでもよい。前記ポリ乳酸系樹脂に含まれる乳酸単位の量は少なくとも５０モル％であることが好ましい。 As a method for producing a polylactic acid resin containing an aliphatic polycarboxylic acid unit, an aliphatic polyhydric alcohol unit, and a lactic acid unit, the aliphatic polycarboxylic acid unit, the aliphatic polyhydric alcohol unit, and the polylactic acid are used. Or a method of reacting lactic acid-other aliphatic hydroxycarboxylic acid copolymer, etc., a method of reacting the above aliphatic polycarboxylic acid unit and the above aliphatic polyhydric alcohol unit with each of the above lactic acid and cyclic esters, etc. It is done. It may be produced by any method. The amount of lactic acid units contained in the polylactic acid resin is preferably at least 50 mol%.
ポリ乳酸系樹脂の分子量は、組成物の熱成形時の加工性や、得られるシート等の成形体の機械的物性及び分解性等に影響を及ぼす。分子量が低いと、得られる成形体の強度が低下して使用する際に破断したり、分解速度が早くなったりする。逆に分子量が高いと、加工性が低下して各種成形が困難となる。かかる点を考慮すると、ポリ乳酸系樹脂の分子量は、１万〜１００万程度の範囲が好ましく、１０万〜５０万がより好ましく、１０万〜３０万がさらに好ましい。なお、本明細書における樹脂の分子量は、特にことわりがない限り、重量平均分子量を指すこととする。 The molecular weight of the polylactic acid-based resin affects the processability during thermoforming of the composition, the mechanical properties and the decomposability of the molded article such as a sheet to be obtained. When the molecular weight is low, the strength of the resulting molded product is reduced, and the resulting molded product may be broken or used at a high rate of decomposition. On the other hand, if the molecular weight is high, processability is reduced and various moldings are difficult. Considering this point, the molecular weight of the polylactic acid resin is preferably in the range of about 10,000 to 1,000,000, more preferably 100,000 to 500,000, and further preferably 100,000 to 300,000. In addition, unless otherwise indicated, the molecular weight of the resin in this specification refers to the weight average molecular weight.
本発明の組成物には、前記ポリ乳酸系樹脂以外に、他の生分解性樹脂が本発明の効果を損なわない範囲で適宜含有されていてもよい。他の生分解性樹脂としては、ポリエチレンサクシネート、ポリブチレンサクシネート、ポリブチレンサクシネートアジペート、ポリエチレンテレフタレートアジペート、ポリブチレンテレフタレートアジペート等が挙げられる。前記ポリ乳酸系樹脂の含有量は、特に限定されないが、組成物を構成する樹脂の総重量中、７０重量％以上が好ましく、８０重量％以上がより好ましく、９０重量％以上がさらに好ましく、実質的に１００重量％であることがさらに好ましい。 In addition to the polylactic acid resin, other biodegradable resins may be appropriately contained in the composition of the present invention as long as the effects of the present invention are not impaired. Other biodegradable resins include polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polyethylene terephthalate adipate, polybutylene terephthalate adipate, and the like. The content of the polylactic acid resin is not particularly limited, but is preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, based on the total weight of the resin constituting the composition. More preferably, it is 100% by weight.
ポリ乳酸系樹脂の含有量は、本発明の組成物中、７０重量％以上が好ましく、８０重量％以上がより好ましく、９０重量％以上がさらに好ましく、９５重量％以上がさらに好ましい。 In the composition of the present invention, the content of the polylactic acid resin is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and further preferably 95% by weight or more.
ポリグリセリン脂肪酸エステルは、グリセリンの重合物であるポリグリセリンに脂肪酸がエステル化されたものである。本発明におけるポリグリセリン脂肪酸エステルは、前記脂肪酸（構成脂肪酸）として、カプリル酸、カプリン酸、及びラウリン酸を含有し、かつ、該ラウリン酸を構成脂肪酸中、２０ｍｏｌ％以上含有するものである。 The polyglycerol fatty acid ester is obtained by esterifying a fatty acid with polyglycerol which is a polymer of glycerol. The polyglycerol fatty acid ester in the present invention contains caprylic acid, capric acid, and lauric acid as the fatty acid (constituent fatty acid), and contains 20 mol% or more of the lauric acid in the constituent fatty acid.
カプリル酸は炭素数８の、カプリン酸は炭素数１０の、ラウリン酸は炭素数１２の飽和の直鎖脂肪酸である。これらの直鎖脂肪酸がポリグリセリンに結合すると、得られるエステル体は、親水性と疎水性のバランスが良好なため、凝集することなくポリ乳酸系樹脂中に良分散することができる。また、前記脂肪酸のなかでも、ラウリン酸が構成脂肪酸中に２０ｍｏｌ％以上、好ましくは２０〜８５ｍｏｌ％、より好ましくは２０〜７５ｍｏｌ％、さらに好ましくは２０〜６０ｍｏｌ％、さらに好ましくは２０〜５０ｍｏｌ％、さらに好ましくは２０〜３０ｍｏｌ％含有されることで、得られたポリグリセリン脂肪酸エステルとポリ乳酸系樹脂との相互作用が高まって相溶性が向上し、得られる成形体が柔軟性を有するものとなる。 Caprylic acid is a saturated linear fatty acid having 8 carbon atoms, capric acid is having 10 carbon atoms, and lauric acid is having 12 carbon atoms. When these linear fatty acids are bonded to polyglycerin, the resulting ester has a good balance between hydrophilicity and hydrophobicity, and therefore can be well dispersed in the polylactic acid resin without agglomeration. Among the fatty acids, lauric acid is 20 mol% or more in the constituent fatty acids, preferably 20 to 85 mol%, more preferably 20 to 75 mol%, still more preferably 20 to 60 mol%, still more preferably 20 to 50 mol%, More preferably, by containing 20 to 30 mol%, the interaction between the obtained polyglycerin fatty acid ester and the polylactic acid-based resin is enhanced, the compatibility is improved, and the resulting molded product has flexibility. .
カプリル酸及びカプリン酸の構成脂肪酸における総含有量は、ラウリン酸の含有量が前記範囲内であれば特に限定はないが、１５〜８０ｍｏｌ％が好ましく、２５〜８０ｍｏｌ％がより好ましく、４０〜８０ｍｏｌ％がさらに好ましく、５０〜８０ｍｏｌ％がさらに好ましい。 The total content of the constituent fatty acids of caprylic acid and capric acid is not particularly limited as long as the content of lauric acid is within the above range, but is preferably 15 to 80 mol%, more preferably 25 to 80 mol%, and more preferably 40 to 80 mol. % Is more preferable, and 50 to 80 mol% is more preferable.
カプリル酸とカプリン酸の含有量比〔カプリル酸／カプリン酸（モル比）〕は、３／１〜１／３が好ましく、２／１〜１／２がより好ましい。 The content ratio [caprylic acid / capric acid (molar ratio)] of caprylic acid and capric acid is preferably 3/1 to 1/3, and more preferably 2/1 to 1/2.
また、構成脂肪酸としては、前記カプリル酸、カプリン酸、及びラウリン酸以外に、本発明の効果を損なわない範囲で、他の脂肪酸を含有してもよい。他の脂肪酸としては、炭素数６〜２２の、飽和あるいは不飽和、直鎖あるいは分岐の脂肪酸、即ち、カプロン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキン酸、ノナデカン酸、べヘン酸、パルミトレイン酸、オレイン酸、ガドレイ酸、エルカ酸、リノール酸、エイコサジエン酸、ドコサジエン酸、リノレン酸、アラキドン酸、イソステアリン酸、リシノレイン酸、１２−ヒドロキシステアリン酸、９−ヒドロキシステアリン酸、１０−ヒドロキシステアリン酸、水素添加ヒマシ油脂肪酸（１２−ヒドロキシステアリン酸の他に少量のステアリン酸及びパルミチン酸を含有する脂肪酸）等が挙げられる。カプリル酸、カプリン酸、及びラウリン酸の総含有量は、構成脂肪酸中、９５ｍｏｌ％以上が好ましく、９９ｍｏｌ％以上がより好ましく、実質的に１００ｍｏｌ％がさらに好ましい。 In addition to the caprylic acid, capric acid, and lauric acid, the constituent fatty acid may contain other fatty acids as long as the effects of the present invention are not impaired. Other fatty acids include C6-C22 saturated or unsaturated, linear or branched fatty acids, that is, caproic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, nonadecanoic acid, behenic acid, palmitolein Acid, oleic acid, gadleyic acid, erucic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, arachidonic acid, isostearic acid, ricinoleic acid, 12-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, And hydrogenated castor oil fatty acid (fatty acid containing a small amount of stearic acid and palmitic acid in addition to 12-hydroxystearic acid). The total content of caprylic acid, capric acid, and lauric acid is preferably 95 mol% or more, more preferably 99 mol% or more, and still more preferably 100 mol% in the constituent fatty acids.
エステル化率は、ポリグリセリンと脂肪酸の仕込み比率、反応温度、反応時間、触媒の種類及び添加量等を変化させることにより調整することができるが、シート物性の観点から、５０〜８５％であり、５５〜８５％が好ましく、６０〜８５％がより好ましく、７０〜８５％がさらに好ましい。本明細書において、エステル化率は、後述の実施例に記載の方法により算出される。 The esterification rate can be adjusted by changing the charging ratio of polyglycerin and fatty acid, reaction temperature, reaction time, type of catalyst and addition amount, etc., but from the viewpoint of sheet physical properties, it is 50 to 85%. 55 to 85% is preferable, 60 to 85% is more preferable, and 70 to 85% is more preferable. In the present specification, the esterification rate is calculated by the method described in Examples described later.
また、ポリグリセリン脂肪酸エステルのもう一つの構成成分であるポリグリセリンとしては、平均重合度が１０であるポリグリセリンが挙げられる。本明細書において、重合度は、後述の実施例に記載の方法により算出される。 Moreover, as polyglycerin which is another structural component of polyglyceryl fatty acid ester, the polyglycerin whose average degree of polymerization is 10 is mentioned. In the present specification, the degree of polymerization is calculated by the method described in Examples described later.
ポリグリセリンと脂肪酸とのエステル化は、特に限定されないが、例えば、ポリグリセリンと脂肪酸を、酸触媒（リン酸、ｐ−トルエンスルホン酸等）もしくはアルカリ触媒（苛性ソーダ等）存在下、又は無触媒で水を除去しながら、好ましくは１００〜３００℃、より好ましくは１２０〜２６０℃の範囲で加熱することにより行うことができる。また、反応は不活性ガスの存在下で行なってもよい。このようにして得られたエステルは目的に応じて精製しても良い。精製には減圧下での蒸留、分子蒸留、水蒸気蒸留といった蒸留技術の他、有機溶剤による抽出、分画や合成吸着剤、ゲル濾過剤を充填したカラムによるクロマト分離も利用できる。 Esterification of polyglycerol and fatty acid is not particularly limited. For example, polyglycerol and fatty acid can be used in the presence of an acid catalyst (phosphoric acid, p-toluenesulfonic acid, etc.) or an alkali catalyst (caustic soda, etc.) or without catalyst. While removing water, the heating can be carried out preferably at 100 to 300 ° C, more preferably 120 to 260 ° C. The reaction may be performed in the presence of an inert gas. The ester thus obtained may be purified according to the purpose. For purification, in addition to distillation techniques such as distillation under reduced pressure, molecular distillation, and steam distillation, extraction with an organic solvent, fractionation, a synthetic adsorbent, and chromatographic separation with a column packed with a gel filtration agent can be used.
ポリグリセリン脂肪酸エステルの含有量は、ポリ乳酸系樹脂１００重量部に対して、０．１〜３０重量部であり、０．５〜５重量部が好ましく、１．０〜３重量部がより好ましい。 The content of the polyglycerin fatty acid ester is 0.1 to 30 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably 1.0 to 3 parts by weight with respect to 100 parts by weight of the polylactic acid resin. .
本発明のポリ乳酸系樹脂組成物は、前記ポリ乳酸系樹脂、及びポリグリセリン脂肪酸エステル以外に、用途に応じて、本発明の目的を損なわない範囲で、アンチブロッキング剤、滑剤、帯電防止剤、防曇剤、紫外線吸収剤、熱安定剤、酸化防止剤、着色防止剤、充填剤、顔料、難燃剤等の他の添加剤を含有してもよい。 In addition to the polylactic acid resin and polyglycerin fatty acid ester, the polylactic acid resin composition of the present invention is an antiblocking agent, a lubricant, an antistatic agent, as long as the object of the present invention is not impaired, depending on the use. You may contain other additives, such as an antifogging agent, a ultraviolet absorber, a heat stabilizer, antioxidant, a coloring inhibitor, a filler, a pigment, and a flame retardant.
アンチブロッキング剤としては、シリカ、炭酸カルシウム、チタニア、マイカ、タルク等が挙げられる。 Examples of the antiblocking agent include silica, calcium carbonate, titania, mica, talc and the like.
滑剤としては、流動パラフィン、ポリエチレンワックス等の炭化水素類、ステアリン酸等の脂肪酸類、オキシ脂肪酸類、脂肪酸アミド類、アルキレンビス脂肪酸アミド類、脂肪酸低級アルコールエステル類、脂肪酸多価アルコールエステル類、脂肪酸ポリグリコールエステル類、脂肪族アルコール類、多価アルコール類、ポリグリコール類、ステアリン酸カルシウム等の金属石鹸類等が挙げられる。 Lubricants include hydrocarbons such as liquid paraffin and polyethylene wax, fatty acids such as stearic acid, oxy fatty acids, fatty acid amides, alkylene bis fatty acid amides, fatty acid lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acids Examples include polyglycol esters, aliphatic alcohols, polyhydric alcohols, polyglycols, and metal soaps such as calcium stearate.
帯電防止剤としては、脂肪酸塩類、高級アルコール硫酸エステル類、液体脂肪油硫酸エステル塩類、脂肪族アミン及び脂肪族アマイド硫酸塩類、脂肪族アルコ−ルリン酸エステル塩類、二塩基性脂肪酸エステルのスルホン酸塩類、脂肪族アミドスルホン酸塩類、アルキルアリルスルホン酸塩類、脂肪族アミン塩類、第４級アンモニウム塩類、アルキルピリジウム塩類、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェノールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、ポリオキシエチレンソルビタンアルキルエステル類、イミダゾリン誘導体、高級アルキルアミン類等が挙げられる。 Antistatic agents include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfate esters, aliphatic amine and aliphatic amide sulfate salts, aliphatic alcohol phosphate esters, dibasic fatty acid ester sulfonates , Aliphatic amide sulfonates, alkyl allyl sulfonates, aliphatic amine salts, quaternary ammonium salts, alkyl pyridium salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters Sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, imidazoline derivatives, higher alkyl amines, and the like.
防曇剤としては、グリセリンモノステアレート等のグリセリン脂肪酸エステル、ソルビタンモノラウレート、ソルビタンモノオレート等のソルビタン脂肪酸エステル、ポリグリセリン脂肪酸エステル、プロピレングリコール脂肪酸エステル等が挙げられる Examples of the antifogging agent include glycerin fatty acid esters such as glycerin monostearate, sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monooleate, polyglycerin fatty acid ester, propylene glycol fatty acid ester and the like.
紫外線吸収剤としては、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール等のベンゾトリアゾール類や、２−ヒドロキシ−４−メトキシベンゾフェノン等のベンゾフェノン類、サリチル酸ｐ−ｔｅｒｔ−ブチルフェニル等のサリチル酸誘導体等が挙げられる。 Examples of ultraviolet absorbers include benzotriazoles such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, benzophenones such as 2-hydroxy-4-methoxybenzophenone, and p-tert-butylphenyl salicylate. And salicylic acid derivatives.
熱安定剤、酸化防止剤、及び着色防止剤としては、パラメトキシフェノール等のフェノール系化合物、トリフェニルホスファイト等のホスファイト系化合物、２−メルカプトベンズイミダゾール等の硫黄系化合物、フェニルナフチルアミン等のアミン系化合物等が挙げられる。 Examples of heat stabilizers, antioxidants, and anti-coloring agents include phenol compounds such as paramethoxyphenol, phosphite compounds such as triphenyl phosphite, sulfur compounds such as 2-mercaptobenzimidazole, and phenyl naphthylamine. Examples include amine compounds.
充填剤としては、硫酸バリウム、酸化チタン、カオリン、カーボンブラック等が挙げられる。 Examples of the filler include barium sulfate, titanium oxide, kaolin, and carbon black.
難燃剤としては、デカブロモジフェニルエーテル等のハロゲン系化合物、三酸化アンチモン等のアンチモン系化合物等が挙げられる。 Examples of the flame retardant include halogen compounds such as decabromodiphenyl ether and antimony compounds such as antimony trioxide.
本発明のポリ乳酸系樹脂組成物は、前記ポリ乳酸系樹脂、及びポリグリセリン脂肪酸エステルを含有するものであれば特に限定なく調製することができる。例えば、ポリ乳酸系樹脂、及びポリグリセリン脂肪酸エステル、必要により他の添加剤を、高速攪拌機又は低速攪拌機等を用いて均一に混合した後、十分な混練能力を有する一軸あるいは多軸の押出機を用いて溶融混練して、調製することが出来る。 The polylactic acid resin composition of the present invention can be prepared without particular limitation as long as it contains the polylactic acid resin and the polyglycerin fatty acid ester. For example, a polylactic acid resin, polyglycerin fatty acid ester, and optionally other additives are mixed uniformly using a high-speed stirrer or a low-speed stirrer, etc., and then a single-screw or multi-screw extruder having sufficient kneading ability is used. It can be prepared by melt kneading.
本発明のポリ乳酸系樹脂組成物の形状は、ペレット、棒状、粉末等が好ましい。 The shape of the polylactic acid resin composition of the present invention is preferably pellets, rods, powders and the like.
また、本発明は、本発明のポリ乳酸系樹脂組成物を成形することにより得られるポリ乳酸系樹脂成形体を提供する。 Moreover, this invention provides the polylactic acid-type resin molded object obtained by shape | molding the polylactic acid-type resin composition of this invention.
本発明のポリ乳酸系樹脂組成物を成形する方法としては、特に限定はなく、例えば、押出機等を用いてポリ乳酸系樹脂、及びポリグリセリン脂肪酸エステル、必要により他の添加剤を溶融混練し、得られた溶融混練物を公知の成形機等により金型に充填して成形する方法が挙げられる。成形機としては、射出成形、フィルムやシートの押出し成形、繊維、（モノあるいはマルチ）フィラメント、ヤーンの射出あるいは押出しブロー成形、インフレーション成形等の成形機を用いることができる。 The method for molding the polylactic acid-based resin composition of the present invention is not particularly limited. For example, a polylactic acid-based resin and a polyglycerin fatty acid ester, and if necessary, other additives are melt-kneaded using an extruder or the like. And a method of filling the obtained melt-kneaded product into a mold with a known molding machine or the like and molding it. As the molding machine, a molding machine such as injection molding, film or sheet extrusion molding, fiber, (mono or multi) filament, yarn injection or extrusion blow molding, inflation molding or the like can be used.
また、Ｔダイが装着された押出機を用いることにより、ポリ乳酸系樹脂、及びポリグリセリン脂肪酸エステル、必要により他の添加剤を溶融混練したものを、そのまま押出してシート状に成形することができる。 Also, by using an extruder equipped with a T-die, a polylactic acid resin, polyglycerin fatty acid ester, and if necessary other melt-kneaded ones can be extruded as they are to form a sheet. .
成形温度は、好ましくは１００〜２８０℃、より好ましくは１３０〜２５０℃、さらに好ましくは１６０〜２３０℃の範囲である。成形温度が低いと成形安定性が得難く、また成形操作の過負荷に陥り易い。逆に、成形温度が高いとポリ乳酸系樹脂が分解することがあり、分子量低下、強度低下、着色等が起こる場合があるので好ましくない。 The molding temperature is preferably in the range of 100 to 280 ° C, more preferably 130 to 250 ° C, and still more preferably 160 to 230 ° C. If the molding temperature is low, molding stability is difficult to obtain, and overloading of the molding operation tends to occur. On the other hand, when the molding temperature is high, the polylactic acid resin may be decomposed, and molecular weight reduction, strength reduction, coloring, and the like may occur.
なお、溶融混練したものをそのまま成形した場合、通常、非晶状態の成形体が得られるが、該成形体を冷却することによって結晶化を促進させて、結晶化させた成形体も得ることができる。 When the melt-kneaded product is molded as it is, an amorphous molded product is usually obtained, but by cooling the molded product, crystallization can be promoted to obtain a crystallized molded product. it can.
また、シート状の成形体には、必要に応じて、シート表面に帯電防止性、防曇性、粘着性、ガスバリヤー性、密着性、易接着性等の機能を有する層を形成することができる。これらの層を形成する方法としては、塗布法、ラミネート法等が挙げられる。 Further, in the sheet-like molded body, a layer having functions such as antistatic properties, antifogging properties, tackiness, gas barrier properties, adhesion, and easy adhesion may be formed on the sheet surface as necessary. it can. Examples of a method for forming these layers include a coating method and a laminating method.
塗布法としては、スプレーコート方式、エアーナイフ方式、リバースコート方式、キスコート方式、グラビアコート方式、マイヤーバー方式、ロールブラッシュ方式等の公知の方法が挙げられ、例えば、シートの片面あるいは両面に帯電防止剤等を含む塗工液を、前記方法に従って、塗布、乾燥することによって帯電防止層を形成することができる。ラミネート法としては、押出ラミネート法、ドライラミネート法等の公知の方法を用いることができ、前記機能を有するフィルムを積層することができる。 Examples of the coating method include known methods such as a spray coating method, an air knife method, a reverse coating method, a kiss coating method, a gravure coating method, a Meyer bar method, a roll brush method, and the like, for example, antistatic on one or both sides of a sheet. An antistatic layer can be formed by applying and drying a coating liquid containing an agent and the like according to the above-described method. As a laminating method, known methods such as an extrusion laminating method and a dry laminating method can be used, and films having the above functions can be laminated.
粘着層を形成する方法としては、例えば、エチルアクリレート、ブチルアクリレート、２−エチルヘキシルアクリレート等のアクリル酸アルキルエステルに対し、他のビニルモノマー類を共重合して得られたコポリマー等のアクリル系樹脂を含む塗布液を、シートに塗布、乾燥する方法が挙げられる。塗布液は、上記コポリマーの有機溶剤溶液でも良いし、水エマルジョンでも良い。 As a method of forming the adhesive layer, for example, an acrylic resin such as a copolymer obtained by copolymerizing other vinyl monomers with an acrylic acid alkyl ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or the like. The method of apply | coating and drying the coating liquid containing to a sheet | seat is mentioned. The coating solution may be an organic solvent solution of the above copolymer or a water emulsion.
かくして得られる、本発明の成形体は、ポリグリセリン脂肪酸エステルが良好に分散しているため透明性に優れ、ＪＩＳ規格 Ｋ７１３６に準拠した曇り度（Ｈａｚｅ）が好ましくは５％未満である。 The molded article of the present invention thus obtained is excellent in transparency because the polyglycerin fatty acid ester is well dispersed, and the haze according to JIS standard K7136 is preferably less than 5%.
本発明の別態様として、本発明のポリ乳酸系樹脂組成物を含む複合体を成形した成形体が挙げられる。 As another embodiment of the present invention, a molded body obtained by molding a composite containing the polylactic acid resin composition of the present invention can be mentioned.
複合体とは、２種以上の材料を組み合わせて作った成形品、又は材料（加工用材料）をいう。例えば、本発明のポリ乳酸系樹脂組成物と補強材等とを組み合わせた材料（加工用材料）や、それらの多層押出成形品などが挙げられ、複数のフィルムの積層体などの形状をとる。 A composite refers to a molded product or material (processing material) made by combining two or more materials. For example, the material (processing material) which combined the polylactic acid-type resin composition of this invention, the reinforcing material, etc., those multilayer extrusion molding products, etc. are mentioned, It takes the shape of the laminated body of a some film.
またさらに、本発明は、本発明の成形体の二次成形品である熱成形品を提供する。熱成形品とは、例えば、本発明のポリ乳酸系樹脂組成物を用いて得られた非晶性のシートや、場合によっては適度に結晶化したシートを、真空成形、真空圧空成形、熱板圧空成形、プレス成形等の公知の成形方法によって、成形時に特定の温度に設定した金型に接触させながら成形（賦形）と、場合によっては結晶化とを、同時にして得られる成形品である。 Furthermore, the present invention provides a thermoformed product that is a secondary molded product of the molded article of the present invention. The thermoformed product is, for example, an amorphous sheet obtained by using the polylactic acid-based resin composition of the present invention, or a sheet that is appropriately crystallized in some cases, by vacuum forming, vacuum pressure forming, hot plate It is a molded product that can be obtained at the same time by molding (shaping) and, in some cases, crystallization, in contact with a mold set at a specific temperature during molding by a known molding method such as pressure forming or press molding. is there.
例えば、真空成形機を用いた成形方法の場合、予めシートを加熱した後、場合によっては特定の温度範囲に設定した金型に接触させ、真空、あるいは圧空により、さらにはプラグでアシストする事により賦形される。例えば、ポリ乳酸系樹脂がポリ乳酸の場合には、シートを、好ましくは６０〜１３０℃、より好ましくは７０〜１２０℃、さらに好ましくは８０〜１１０℃、さらに好ましくは８５〜１０５℃に予め加熱した後、金型に接触させながら成形することができる。前記温度範囲で成形することにより、成形品の形状が良く、且つ透明性の高い熱成形品が得られる。 For example, in the case of a forming method using a vacuum forming machine, after heating a sheet in advance, it may be brought into contact with a mold set to a specific temperature range in some cases, by assisting with a vacuum or compressed air, and further with a plug. Shaped. For example, when the polylactic acid-based resin is polylactic acid, the sheet is preferably preheated to 60 to 130 ° C, more preferably 70 to 120 ° C, still more preferably 80 to 110 ° C, and further preferably 85 to 105 ° C. Then, it can be molded while being in contact with the mold. By molding in the temperature range, a thermoformed product having a good shape and high transparency can be obtained.
プラグアシストを併用して成形する場合は、プラグの形状や温度は、シートの厚みや目的の成形品の形状等によって、適宜選択する事ができる。 In the case of molding using plug assist together, the shape and temperature of the plug can be appropriately selected depending on the thickness of the sheet, the shape of the target molded product, and the like.
以下、本発明を実施例及び比較例に基づいて説明するが、本発明はこれらの実施例等によりなんら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited at all by these Examples.
〔樹脂の重量平均分子量（Ｍｗ）〕
ゲルバーミエーシヨンクロマトグラフィー（ＧＰＣ）により、ポリスチレンを標準としてＳｈｏｄｅｘ ＧＰＣ ＳＹＳＴＥＭ−２１（示差屈折率検出器）により、カラム温度４０℃、クロロホルム溶離液で測定する。
[Weight average molecular weight of resin (Mw)]
It is measured by gel vermeation chromatography (GPC) with Shodex GPC SYSTEM-21 (differential refractive index detector) using polystyrene as a standard with a column temperature of 40 ° C. and a chloroform eluent.
〔ポリグリセリン脂肪酸エステルのエステル化率〕
ポリグリセリン脂肪酸エステルのエステル化率は、(構成脂肪酸のｍｏｌ数／ポリグリセリンのｍｏｌ数)×１００（％）の式に基づいて計算される。
[Esterification rate of polyglycerol fatty acid ester]
The esterification rate of the polyglycerol fatty acid ester is calculated based on the formula of (number of moles of constituent fatty acid / number of moles of polyglycerol) × 100 (%).
〔ポリグリセリンの平均重合度〕
ポリグリセリンの重合度は、以下の式に基づいて、水酸基価より決定される。
ＧＯＨＶ＝５６１１０（ｎ＋２）／（７４ｎ＋１８）
ＧＯＨＶ：ポリグリセリンの水酸基価
ｎ ：ポリグリセリンの重合度
[Average degree of polymerization of polyglycerol]
The degree of polymerization of polyglycerol is determined from the hydroxyl value based on the following formula.
GOHV = 56110 (n + 2) / (74n + 18)
GOHV: hydroxyl value of polyglycerin
n: Degree of polymerization of polyglycerol
ポリ乳酸系樹脂の製造例１
Ｄｉｅｎ−Ｓｔａｒｋトラップを設置した１００リットル反応容器に、９０モル％Ｌ−乳酸（不純物の含有量０．５モル％）１０ｋｇを１５０℃／５０ｍｍＨｇで３時間攪拌しながら水を留出させた後、錫末６．２ｇを加え、１５０℃／３０ｍｍＨｇでさらに２時間攪拌してオリゴマー化した。このオリゴマーに錫末２８．８ｇとジフェニルエーテル２１．１ｋｇを加え、１５０℃／３５ｍｍＨｇ共沸脱水反応を行い留出した水と溶媒を水分分離機で分離して、水層を逐次抜き出し、溶媒のみを反応器に戻した。２時間後（この時点で不純物の含有量は０．０５モル％であった）、反応器に戻す有機溶媒を４．６ｋｇのモレキュラーシーブ３Ａを充填したカラムに通してから反応器に戻すようにして、１５０℃／３５ｍｍＨｇで反応を行い、ポリスチレン換算重量平均分子量１２万のポリ乳酸溶液を得た。この溶液に脱水したジフェニルエーテル４４ｋｇを加え希釈した後、４０℃まで冷却して、析出した結晶をろ過し、１０ｋｇのｎ−ヘキサンで３回洗浄して６０℃／５０ｍｍＨｇで乾燥した。この粉末を０．５Ｎ−塩酸１２ｋｇとエタノール１２ｋｇを加え、３５℃で１時間攪拌した後ろ過し、６０℃／５０ｍｍＨｇで乾燥して、平均粒径５０μｍのポリ乳酸Ａ粉末を６．１ｋｇ（収率８５％）得た。このポリマーのポリスチレン換算重量平均分子量（Ｍｗ）は１５万、Ｄ−体含有量は１．２％であった。
Production example 1 of polylactic acid resin
After distilling water into a 100 liter reaction vessel equipped with a Dien-Stark trap while stirring 10 kg of 90 mol% L-lactic acid (impurity content 0.5 mol%) at 150 ° C./50 mmHg for 3 hours, 6.2 g of tin powder was added, and the mixture was further oligomerized by stirring at 150 ° C./30 mmHg for 2 hours. To this oligomer, 28.8 g of tin powder and 21.1 kg of diphenyl ether were added, 150 ° C / 35 mmHg azeotropic dehydration reaction was performed, the distilled water and the solvent were separated with a water separator, the aqueous layer was sequentially extracted, and only the solvent was removed. Returned to reactor. After 2 hours (at this point, the impurity content was 0.05 mol%), the organic solvent to be returned to the reactor was passed through a column packed with 4.6 kg of molecular sieve 3A and then returned to the reactor. Then, the reaction was performed at 150 ° C./35 mmHg to obtain a polylactic acid solution having a polystyrene-equivalent weight average molecular weight of 120,000. The solution was diluted with 44 kg of dehydrated diphenyl ether, cooled to 40 ° C., and the precipitated crystals were filtered, washed 3 times with 10 kg of n-hexane, and dried at 60 ° C./50 mmHg. To this powder, 12 kg of 0.5N hydrochloric acid and 12 kg of ethanol were added, stirred for 1 hour at 35 ° C., filtered, dried at 60 ° C./50 mmHg, and 6.1 kg of polylactic acid A powder having an average particle size of 50 μm (concentration). 85%). This polymer had a weight average molecular weight (Mw) in terms of polystyrene of 150,000 and a D-form content of 1.2%.
ポリグリセリン脂肪酸エステルの製造例１
ポリグリセリン（平均重合度：１０、デカグリセリン）と、表１に記載の構成脂肪酸を混合したものとを、不活性ガス中、リン酸、ｐ−トルエンスルホン酸、又は苛性ソーダの存在下で、１２０〜２６０℃で加熱し生成水を系外に除去することによって、ポリグリセリン脂肪酸エステルを得た。
Production example 1 of polyglycerol fatty acid ester
Polyglycerin (average polymerization degree: 10, decaglycerin) and a mixture of the constituent fatty acids listed in Table 1 in an inert gas in the presence of phosphoric acid, p-toluenesulfonic acid, or caustic soda, 120 A polyglycerol fatty acid ester was obtained by heating at ˜260 ° C. and removing generated water out of the system.
実施例１〜６及び比較例１〜８
表２又は３に示す種類と量のポリ乳酸系樹脂、及び表２又は３に示す種類と量のポリグリセリン脂肪酸エステルをヘンシェルミキサーで混合した後、二軸押出し機「ＴＥＭ−３５Ｂ」（東芝機械社製）を用いて、１４０〜２１０℃にて溶融混練し、ペレット化した。得られたペレットを、Ｔダイが装着されたφ４０ｍｍの押出機（Ｐｌａｃｏ社製）を用いて、１８０〜２００℃で加熱溶融押出し、厚さ２５０μｍの成形体（シート）を得た。
Examples 1-6 and Comparative Examples 1-8
After mixing the type and amount of polylactic acid resin shown in Table 2 or 3 and the type and amount of polyglycerol fatty acid ester shown in Table 2 or 3 with a Henschel mixer, a twin screw extruder “TEM-35B” (Toshiba Machine) The product was melt kneaded at 140 to 210 ° C. and pelletized. The obtained pellets were melt-extruded by heating at 180 to 200 ° C. using a φ40 mm extruder (Placo) equipped with a T die to obtain a molded body (sheet) having a thickness of 250 μm.
なお、表２又は３に記載の原料は以下の通りである。
〔ポリ乳酸系樹脂〕
ＬＡＣＥＡ Ｈ−４００：三井化学販売、ポリ乳酸（Ｍｗ＝２０万、Ｄ−体含有量１．８％）
ＬＡＣＥＡ Ｈ−４４０：三井化学販売、ポリ乳酸（Ｍｗ＝２０万、Ｄ−体含有量４．４％）
In addition, the raw material of Table 2 or 3 is as follows.
[Polylactic acid resin]
LACEA H-400: Mitsui Chemicals, polylactic acid (Mw = 200,000, D-form content 1.8%)
LACEA H-440: Mitsui Chemicals, polylactic acid (Mw = 200,000, D-form content 4.4%)
実施例１〜６及び比較例１〜８の成形体の物性を、以下の試験例１〜５の方法に従って調べた。結果を表２及び３に示す。 The physical properties of the molded bodies of Examples 1 to 6 and Comparative Examples 1 to 8 were examined according to the methods of Test Examples 1 to 5 below. The results are shown in Tables 2 and 3.
＜試験例１＞〔透明性（ヘイズ）〕
ＪＩＳ Ｋ−７１３６に準じ、東京電色社製、Ｈａｚｅ Ｍｅｔｅｒを用いて、厚さ２５０μｍのシートの濁度（％）を求める。
<Test Example 1> [Transparency (Haze)]
In accordance with JIS K-7136, the turbidity (%) of a sheet having a thickness of 250 μm is determined using Haze Meter manufactured by Tokyo Denshoku Co., Ltd.
＜試験例２＞〔引張物性（強度）〕
ＪＩＳ Ｋ６７３２に準じて、厚さ２５０μｍのシートを、東洋精機社製引張試験機を用いて、測定温度２３℃、チャック間７０ｍｍ、試験片幅１０ｍｍ、試験速度２００ｍｍ／ｍｉｎの条件で測定し、強度を求めて、引張物性を評価する。測定値が大きいほど引張物性（強度）が強いことを示す。なお、表中のＭＤ／ＴＤは、シートに対し引張試験の方向を意味するもので、シートを製造する際のシート流れに平行な方向をＭＤ、垂直な方向をＴＤとしている。
<Test Example 2> [Tensile property (strength)]
According to JIS K6732, a sheet having a thickness of 250 μm was measured using a tensile tester manufactured by Toyo Seiki Co., Ltd. under conditions of a measurement temperature of 23 ° C., a chuck interval of 70 mm, a test piece width of 10 mm, and a test speed of 200 mm / min. To evaluate tensile properties. It shows that tensile property (strength) is so strong that a measured value is large. MD / TD in the table means the direction of the tensile test with respect to the sheet, and MD is the direction parallel to the sheet flow when the sheet is manufactured, and TD is the direction perpendicular to the sheet flow.
＜試験例３＞〔耐衝撃性（ハイレートインパクト）〕
厚さ２５０μｍのシートを、高速衝撃試験機を用い、測定温度２３℃、ストライカ径１／２ｉｎｃｈ、試験速度３ｍ／ｍｉｎの条件で測定し、衝撃吸収エネルギー（ハイレートインパクト、ｍＪ）を求めて、耐衝撃性を評価する。ハイレートインパクト（ｍＪ）が大きいほど耐衝撃性が強いことを示し、１００ｍＪ以上のハイレートインパクトで良好な耐衝撃性を有すると判断することができる。
<Test Example 3> [Shock resistance (high rate impact)]
A sheet having a thickness of 250 μm was measured using a high-speed impact tester under the conditions of a measurement temperature of 23 ° C., a striker diameter of 1/2 inch, and a test speed of 3 m / min to determine impact absorption energy (high rate impact, mJ). Evaluate impact properties. The higher the high rate impact (mJ), the stronger the impact resistance, and it can be determined that the high rate impact of 100 mJ or more has good impact resistance.
＜試験例４＞〔耐折強度〕
ＪＩＳ Ｐ ８１１５に規定される方法に準じて測定する。試験片形状が長さ約９０ｍｍ×幅１５ｍｍ、厚さ２５０μｍのシートを、ＭＩＴ型耐折試験機を用い試験荷重１ｋｇ、折り曲げ角度を２７０度（左右１３５度）、折り曲げ速度を１７５回／分の条件下で測定し、シートが破断するまでの折り曲げ回数を求める。折り曲げ回数が多いほど、耐折強度が強いことを示す。なお、表中のＭＤ／ＴＤは、シートに対し耐折試験の方向を意味するもので、シートを製造する際のシート流れに平行な方向をＭＤ、垂直な方向をＴＤとしている。
<Test Example 4> [Folding strength]
Measured according to the method specified in JIS P 8115. A test piece having a length of about 90 mm × width of 15 mm and a thickness of 250 μm was tested using a MIT type folding tester with a test load of 1 kg, a bending angle of 270 degrees (135 degrees on the left and right), and a bending speed of 175 times / minute. Measure under the conditions to determine the number of folding times until the sheet breaks. It shows that folding strength is so strong that there are many times of bending. In the table, MD / TD means the direction of the folding test for the sheet, and MD is the direction parallel to the sheet flow when manufacturing the sheet, and TD is the direction perpendicular to the sheet flow.
＜試験例５＞〔二次加工性（打抜き性）〕
厚さ２５０μｍのポリ乳酸系樹脂組成物のシートを圧空真空成形機を用いて、金型形状上部口径が１００ｍｍ、底部口径が８０ｍｍ、高さ２５ｍｍ、絞り比０．２５のトレーを成形した後、耳の部位を打抜き刃にて打ち抜く。打ち抜いた時のシート及び成形品の状況により、以下の基準に従って、二次加工性を評価する。
<Test Example 5> [Secondary workability (punchability)]
After forming a sheet of a polylactic acid resin composition having a thickness of 250 μm using a compressed air vacuum molding machine, a tray having a mold shape upper diameter of 100 mm, a bottom diameter of 80 mm, a height of 25 mm, and a drawing ratio of 0.25 is formed. Punch the ear part with a punching blade. The secondary workability is evaluated according to the following criteria according to the state of the sheet and the molded product when punched.
〔二次加工性の評価基準〕
○：シート、成形品に割れは生じる事なく、良好に打抜きができる
×：打抜き時にシートあるいは成形品に割れや亀裂、白化が生じる
[Evaluation criteria for secondary workability]
○: The sheet or molded product can be punched well without cracking ×: The sheet or molded product is cracked, cracked, or whitened during punching
結果、実施例の組成物は、比較例に比べて、ヘイズが低く、かつ、引張強度にも優れながらも耐衝撃性が強く、良好な柔軟性を有するものであることが分かる。 As a result, it can be seen that the compositions of the examples have low haze and excellent tensile strength while having excellent haze and good flexibility as compared with the comparative examples.
本発明のポリ乳酸系樹脂組成物は、例えば、農業用資材、食品包装資材、その他の包装資材等に好適に用いられる。 The polylactic acid resin composition of the present invention is suitably used for, for example, agricultural materials, food packaging materials, other packaging materials, and the like.
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| US9062177B2 (en) * | 2011-08-18 | 2015-06-23 | Taiyo Kagaku Co., Ltd. | Agent for imparting impact resistance to polylactic acid resin |
| JP5907698B2 (en) * | 2011-11-10 | 2016-04-26 | 三菱樹脂株式会社 | Aliphatic polyester resin sheet and plastic case for packaging container using the same |
| JP6055646B2 (en) * | 2012-02-10 | 2016-12-27 | 三菱樹脂株式会社 | Aliphatic polyester resin laminate sheet and plastic case for packaging container using the same |
| JP6306917B2 (en) * | 2014-03-25 | 2018-04-04 | 大東化成工業株式会社 | Method for producing spherical biodegradable polymer powder |
| CN113337090B (en) * | 2021-05-28 | 2023-04-18 | 湖南航天磁电有限责任公司 | Heat-resistant modified polylactic acid material and preparation method and application thereof |
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