JP4846110B2 - Aliphatic polyester film - Google Patents
Aliphatic polyester film Download PDFInfo
- Publication number
- JP4846110B2 JP4846110B2 JP2001051419A JP2001051419A JP4846110B2 JP 4846110 B2 JP4846110 B2 JP 4846110B2 JP 2001051419 A JP2001051419 A JP 2001051419A JP 2001051419 A JP2001051419 A JP 2001051419A JP 4846110 B2 JP4846110 B2 JP 4846110B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- aliphatic polyester
- polyester film
- acid
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920003232 aliphatic polyester Polymers 0.000 title claims description 63
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 33
- 125000001931 aliphatic group Chemical group 0.000 claims description 18
- 235000014655 lactic acid Nutrition 0.000 claims description 17
- 239000004310 lactic acid Substances 0.000 claims description 16
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 12
- 239000004626 polylactic acid Substances 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 7
- 239000012785 packaging film Substances 0.000 claims description 6
- 229920006280 packaging film Polymers 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 239000010408 film Substances 0.000 description 135
- -1 polyethylene Polymers 0.000 description 30
- 238000000034 method Methods 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 24
- 229960000448 lactic acid Drugs 0.000 description 17
- 239000004014 plasticizer Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- 239000008188 pellet Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 235000014113 dietary fatty acids Nutrition 0.000 description 12
- 239000000194 fatty acid Substances 0.000 description 12
- 229930195729 fatty acid Natural products 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 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
- 239000002253 acid Substances 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000004676 glycans Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000002537 cosmetic Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002390 adhesive tape Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 3
- 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
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- NGXUUAFYUCOICP-UHFFFAOYSA-N aminometradine Chemical group CCN1C(=O)C=C(N)N(CC=C)C1=O NGXUUAFYUCOICP-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 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
- 238000001125 extrusion Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-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
- 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
- 229930182843 D-Lactic acid Natural products 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 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
- 239000004698 Polyethylene 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
- 239000003905 agrochemical Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 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
- 230000004888 barrier function Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002361 compost Substances 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000012535 impurity 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
- 238000003475 lamination Methods 0.000 description 2
- 239000000463 material Substances 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
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 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
- 150000003871 sulfonates Chemical class 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
- 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
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-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
- 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
- UOXJNGFFPMOZDM-UHFFFAOYSA-N 2-[di(propan-2-yl)amino]ethylsulfanyl-methylphosphinic acid Chemical compound CC(C)N(C(C)C)CCSP(C)(O)=O UOXJNGFFPMOZDM-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- 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
- SFHYNDMGZXWXBU-LIMNOBDPSA-N 6-amino-2-[[(e)-(3-formylphenyl)methylideneamino]carbamoylamino]-1,3-dioxobenzo[de]isoquinoline-5,8-disulfonic acid Chemical compound O=C1C(C2=3)=CC(S(O)(=O)=O)=CC=3C(N)=C(S(O)(=O)=O)C=C2C(=O)N1NC(=O)N\N=C\C1=CC=CC(C=O)=C1 SFHYNDMGZXWXBU-LIMNOBDPSA-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
- 244000215068 Acacia senegal Species 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
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- 244000000626 Daucus carota Species 0.000 description 1
- 235000002767 Daucus carota Nutrition 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
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- 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
- 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
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
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- 229920001214 Polysorbate 60 Polymers 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 208000010040 Sprains and Strains Diseases 0.000 description 1
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
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- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940116224 behenate Drugs 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
- Bag Frames (AREA)
- Wrappers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、脂肪族ポリエステルフィルム、及び該フィルムを用いた包装体に関する。詳しくは、自然環境下で分解性を有し、優れた柔軟性と密着性を有する脂肪族ポリエステルフィルム、及び該脂肪族ポリエステルフィルムを用いた包装体に関する。
【０００２】
【従来の技術】
近年、プラスチックの廃棄物問題がクローズアップされている。包装材料のようなプラスチック廃棄物は、使用者が使い終わった後、廃棄され、焼却処理されるか、または埋め立て等により処分されていた。しかし、このようなプラスチック廃棄物を焼却処理した場合、燃焼熱が高く、焼却炉の耐久性の問題や、ポリ塩化ビニルのようなものでは有害なガスを発生し、公害問題を引き起こしていた。さらに、埋め立てた場合には、プラスチック成形物がそのまま分解せずに、原形のままゴミとして半永久的に残り、自然環境への影響が問題となっていた。このような状況の中、自然環境下で微生物により完全に消費され、自然的副産物である炭酸ガスや水に分解する種々の生分解性プラスチックが発明され実用レベルの段階に入っている。
【０００３】
特開平６−３４０７５３号公報には、ポリ乳酸または乳酸とその他のヒドロキシカルボン酸を主成分とする熱可塑性ポリマーからなる組成物が、例えば、分解性のカードとして用い得ること、そして、それは機械的強度が高く、実用に耐えうる耐久性を示すことが開示されている。しかし、該ポリマーは弾性率および剛性が高く、柔軟性に乏しいため、ポリエチレン、ポリプロピレン、ポリ塩化ビニル等の軟質フィルムが使用されている用途には適していなかった。
【０００４】
一般に、樹脂を軟質化する方法として、（１）可塑剤の添加、（２）コポリマー化、（３）軟質ポリマーのブレンド、（４）軟質ポリマーとの積層等の方法が知られている。その中で、（１）については、過去に様々な可塑剤を用いた軟質化の検討がなされている。例えば、特開平４−３３５０６０号公報には、ポリ乳酸に可塑剤を添加した組成物が開示されている。その中で具体的な例として、アジピン酸ジイソブチル、セバシン酸ジオクチル等が可塑剤として挙げられている。しかし、これの化合物を可塑剤として用いたフィルムは、柔軟性はかなり改善されるものの、経時につれて可塑剤が浮き出す等の問題がある。
【０００５】
また、（３）の方法では、本課題の一つである生分解性を考慮すると、ブレンドする樹脂としては、柔軟性を有する生分解性樹脂に限定される。このような樹脂としては、例えば、ポリブチレンサクシネート、ポリエチレンサクシネート、ポリカプロラクトン等が挙げられ、既に特開平８−２４５８６６号公報、および特開平９−１１１１０７号公報に開示されている。しかし、これらの樹脂をブレンドした場合、透明性や耐熱性が低下する等の問題がある。また、（４）の方法では、（３）と同様に生分解性を考慮して、積層する樹脂を選択することにより、柔軟性が付与される。しかし、これらの樹脂と積層した場合、（３）の場合と同様に透明性や耐熱性が低下する等の問題がある。
【０００６】
【発明が解決しようとする課題】
本発明の解決課題は、自然環境下で分解性を有し、優れた柔軟性と密着性を有し、しかも可塑剤がブリードアウトすることがない脂肪族ポリエステルフィルム、及び該フィルムを用いた包装体を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意検討した結果、脂肪族ポリエステルに対し、可塑剤として特定の化合物を用いることにより、可塑剤がブリードアウトすることがなく、優れた透明性、耐熱性、柔軟性及び密着性を有する脂肪族ポリエステルが得られることを見出し、本発明に到った。
【０００８】
即ち、本発明の要旨は、脂肪族ポリエステル１００重量部に対し、一般式（１）〔化２〕
【０００９】
【化２】
（式中、ｎは１〜１０の整数、Ｒ1〜Ｒ4は炭素数１〜１８のアシル基である）で示される化合物（Ａ）、及びグリセリン１〜１０分子の縮合物と炭素数６〜１８のカルボン酸との反応生成物である化合物（Ｂ）から選ばれた少なくとも１種の化合物１０〜６０重量部を含む層を少なくとも一層有する単層または多層の脂肪族ポリエステルフィルムであって、２０℃における貯蔵弾性率（Ｅ’）が１×１０7〜２×１０9Ｐａ、貯蔵弾性率（Ｅ’）に対する損失弾性率（Ｅ’’）の比（Ｅ’’／Ｅ’）である損失正接（ｔａｎδ）が０．１〜１．０の範囲にあることを特徴とする脂肪族ポリエステルフィルムである。
また、本発明の他の発明は、前記脂肪族ポリエステルフィルムを用いて被包装物を包装した包装体である。
【００１１】
本発明に係わる脂肪族ポリエステルフィルムは、優れた耐熱性、柔軟性、透明性及び密着性を有し、しかも可塑剤がブリードアウトしない。更に、脂肪族ポリエステルとして、ポリ乳酸、乳酸と他の脂肪族ヒドロキシカルボン酸との共重合体等を用いた場合には、加水分解性を有するので、使用した後に廃棄しても自然環境下に蓄積することがない。そのため、食品、電子、医療、薬品、化粧品等の各種包装用フィルム、農業用フィルム、土建・建築用フィルム、粘着テープの基材フィルム等の広範囲における資材として好適に使用し得る。特に、食品類の包装材料として好適である。本発明の包装体の被包装物が食品である場合、包装材料と被包装物を分離することなしに、例えば、堆肥化処理等が可能である。
【００１２】
尚、本発明における貯蔵弾性率（Ｅ’）、及び貯蔵弾性率（Ｅ’）に対する損失弾性率（Ｅ’’）の比（Ｅ’’／Ｅ’）である損失正接（ｔａｎδ）は、後述の実施例に記載した方法により測定した値を意味する。
【００１３】
【発明の実施の形態】
以下、本発明について詳細に説明する。先ず、本発明に係わる脂肪族ポリエステルフィルムに用いる脂肪族ポリエステル組成物について説明する。本発明に用いる脂肪族ポリエステル組成物は、脂肪族ポリエステルに、可塑剤として前記化合物（Ａ）及び化合物（Ｂ）から選ばれた少なくとも１種の化合物を添加、混合することにより製造される。
【００１４】
本発明に用いる脂肪族ポリエステルは、分子中に乳酸単位を含む脂肪族ポリエステルである。具体的には、（１）ポリ乳酸、及び乳酸と他の脂肪族ヒドロキシカルボン酸とのコポリマー、（２）多官能多糖類及び乳酸単位を含む脂肪族ポリエステル、（３）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脂肪族ポリエステル、及び（４）これらの混合物である。以下、これらを総称して乳酸系ポリマーという。これらの内、得られるフィルムの透明性、加水分解性等を考慮すると、ポリ乳酸、及び乳酸と他の脂肪族ヒドロキシカルボン酸とのコポリマーが好ましい。
【００１５】
乳酸には、Ｌ−体とＤ−体とが存在するが、本発明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−体との両者を指すこととする。また、ポリマー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。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。乳酸−他の脂肪族ヒドロキシカルボン酸コポリマーの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。
【００１６】
本発明に用いるポリ乳酸の製造方法として、Ｌ−乳酸、Ｄ−乳酸、またはＤＬ−乳酸を直接脱水縮合する方法、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。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い。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の製造方法として、上記各乳酸と上記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。共重合体に含まれる乳酸単位の量は少なくとも４０モル％であることが好ましい。
【００１７】
多官能多糖類及び乳酸単位を含む脂肪族ポリエステルの製造に用いる多官能多糖類としては、例えば、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、ヘミセルロール、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、及びこれらの誘導体が挙げられる。これらの内で特に酢酸セルロース、エチルセルロースが好ましい。
【００１８】
多官能多糖類及び乳酸単位を含む脂肪族ポリエステルの製造方法として、上記多官能多糖類と上記ポリ乳酸、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、上記多官能多糖類と上記各乳酸、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。該脂肪族ポリエステル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。
【００１９】
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脂肪族ポリエステルの製造に用いる脂肪族多価カルボン酸としては、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。
【００２０】
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脂肪族ポリエステルの製造方法として、上記脂肪族多価カルボン酸及び上記脂肪族多価アルコールと、上記ポリ乳酸、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及び上記脂肪族多価アルコールと、上記各乳酸、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。該脂肪族ポリエステル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。
【００２１】
脂肪族ポリエステルの分子量は、フィルムの加工性、得られるフィルムの強度及び分解性に影響を及ぼす。分子量が低いと得られるフィルムの強度が低下し、使用する際に張力で破断することがある。また、分解速度が早くなる。逆に分子量が高いと加工性が低下し、フィルム製膜が困難となる。かかる点を考慮すると、脂肪族ポリエステルの分子量は、約１万〜約１００万程度の範囲が好ましい。さらに好ましい範囲は１０万〜３０万である。
【００２２】
本発明では、脂肪族ポリエステルの可塑剤として、上記一般式（１）で表される化合物（Ａ）、及びグリセリン１〜１０分子の縮合物と炭素数６〜１８のカルボン酸との反応生成物である化合物（Ｂ）から選ばれた少なくとも１種の化合物が用いられる。これらの可塑剤の添加量は、得られる延伸フィルムの結晶化度、柔軟性、耐熱性等に影響を及ぼす。添加量が多すぎると結晶化度及び耐熱性が低下する。少なすぎると十分な柔軟性が得られない。かかる観点から、可塑剤としての上記化合物（Ａ）及び／又は（Ｂ）の添加量は、脂肪族ポリエステル１００重量部に対し１０〜６０重量部であることが好ましい。さらに好ましくは１５〜５０重量部である。
【００２３】
本発明の脂肪族ポリエステル組成物には、主成分である脂肪族ポリエステル、上記化合物（Ａ）、及び上記化合物（Ｂ）の他に、用途に応じて、本発明の目的を損なわない範囲で、シリカ、炭酸カルシウム、チタニア、マイカ、タルク等のアンチブロッキング剤、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、オシキ脂肪酸類、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の滑剤、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、脂肪族アミンおよ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、ポリオキシエチエ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の帯電防止剤、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の防曇剤、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の紫外線吸収剤、パラメトキシフェノール等のフェノール系、トリフェニルホスファイト等のホスファイト系、２−メルカプトベンズイミダゾール等の硫黄系、フェニルナフチルアミン等のアミン系の熱安定剤、酸化防止剤、着色防止剤、硫酸バリウム、酸化チタン、カオリン、カーボンブラック等の充填剤、顔料、デカブロモジフェニルエーテル等のハロゲン系、三酸化アンチモン等のアンチモン系の難燃剤等の他の添加剤を添加してもよい。
【００２４】
次いで、本発明の脂肪族ポリエステルフィルム、及びその製造方法の一例について説明する。脂肪族ポリエステルに可塑剤を添加、混合する方法としては、脂肪族ポリエステルと可塑剤、場合によっては他の添加剤を高速攪拌機または低速攪拌機など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する方法等を採用することが出来る。本発明に係る樹脂組成物の形状は、通常、ペレット、棒状、粉末等が好ましい。
【００２５】
以上のようにして得られた樹脂組成物を、Ｔダイが装着された押出機を用いる溶融押出法によりフィルム状に成形する。好ましくは、得られたフィルムをロール延伸によって流れ方向（機械方向、以下、ＭＤ方向）に延伸した後、テンター延伸によって横方向（機械方向と直交する方向、以下、ＴＤ方向）に延伸する。延伸の順序は上記の逆でもよい。延伸後、緊張下で熱処理することにより脂肪族ポリエステル延伸フィルムが製造される。一軸延伸する場合は、ＭＤ方向、ＴＤ方向のいずれに延伸してもよい。
【００２６】
上記各種の添加剤を含む脂肪族ポリエステル組成物の溶融押出温度は、好ましくは１００〜２８０℃、より好ましくは１３０〜２５０℃の範囲である。成形温度が低いと成形安定性が得難く、また過負荷に陥り易い。逆に、成形温度が高いと脂肪族ポリエステルが分解することがあり、分子量低下、強度低下、着色等が起こるので好ましくない。
【００２７】
本発明の脂肪族ポリエステルフィルムは、ＭＤ方向及びＴＤ方向の少なくとも一軸方向に、１．５〜５倍延伸することが好ましい。更に好ましくは、ＭＤ方向及びＴＤ方向に２軸延伸された２軸延伸フィルムである。延伸フィルムを製造する場合、延伸倍率が１．５倍未満であると、力学物性や寸法精度の経時安定性をもたらす結晶化が進行し難い。また、５倍を超えると、フィルムの柔軟性がなくなると共に、延伸時にフィルム破れ等が生じ好ましくない。延伸温度は用いる脂肪族ポリエステルのガラス転移温度（Ｔｇ）〜（Ｔｇ＋５０）℃の範囲が好ましい。さらに好ましくは、Ｔｇ〜（Ｔｇ＋３０）℃の範囲である。延伸温度がＴｇ未満では延伸が困難であり、（Ｔｇ＋５０）℃を超えると均一な延伸が困難となり好ましくない。また、耐熱性及び寸法安定性向上のため、延伸後緊張下にて（Ｔｇ＋１０）℃以上、融点未満の温度で熱処理を行う。この際、延伸、熱処理条件を変化させることにより、フィルムの結晶化度を制御することができる。
【００２８】
上記条件で延伸及び熱処理を施すことにより、結晶化度が１０〜６０％である延伸フィルムが得られる。好ましい結晶化度は２０〜５０％である。例えば、乳酸系ポリマー１００重量部に対して、上記化合物（Ａ）のうち、Ｒ１〜Ｒ４が全て炭素数１のアシル基、ｎが１である化合物を２０重量部添加し、Ｔダイを用いて製膜した後、５０℃にて、機械方向に２．５倍、幅方向に２．５倍（以下、２．５×２．５と略記する）に延伸する。その後、緊張下にて１４０℃で熱処理を行うことにより、結晶化度３０％程度の延伸フィルムが得られる。
【００２９】
本発明の脂肪族ポリエステルフィルムは、目的に応じて工程条件を設定することにより、ロール状、テープ状、カットシート状、筒状（シームレス状）に製造することができる。
【００３０】
本発明の脂肪族ポリエステルフィルムは、ショッピングバッグ、ゴミ袋、コンポストバッグ、食品・菓子包装フィルム、食品包装用ラップフィルム、化粧品・香粧品用ラップフィルム、医薬品用ラップフィルム、生薬用ラップフィルム、肩こりや捻挫等に適用される外科用貼付薬用ラップフィルム、農業用・園芸用フィルム、農薬品用ラップフィルム、温室用フィルム、肥料用袋、ビデオやオーディオ等の磁気テープカセット製品包装用フィルム、フロッピーディスク包装用フィルム、製版用フィルム、粘着テープ、防水シート、土嚢用袋、等として、好適に使用することができる。これらの用途の内、好ましくは包装用フィルムとして使用され、包装体が形成される。その場合の被包装物としては、野菜類、果物類、菓子類等の食品、化粧品、医薬品、農薬品、肥料、土壌、家庭ゴミ類、コンポスト、ビデオ、ＣＤ等の電子・電気製品等が挙げられる。本発明のポリエステルフィルムの厚みは用途に応じて適宜替え得るが、通常、５〜１０００μｍの範囲である。
【００３１】
本発明の脂肪族ポリエステルフィルムは、ヒートシール、高周波シールおよび溶断等の方法によって、袋状に加工することができる。例えば、カットシート状に製造されたフィルムを２つ折にし、折り目の側辺の２辺をフィルムのＴｇ（ガラス転移温度）以上の温度のヒートシールバーを用いて、ヒートシールすることにより、袋が得られる。また、ロール状のフィルムを解反しながら、幅方向に２つ折にし、フィルムの融点以上の温度の溶断バーを用いて、長さ方向に一定間隔で溶断することにより、袋が得られる。また、筒状のフィルムを解反しながら、Ｔｇ以上の温度のヒートシールバーを用いて、長さ方向に一定間隔でヒートシールした後、シール部の直近を同間隔でカットすることにより、袋が得られる。
【００３２】
本発明の脂肪族ポリエステル延伸フィルムは、必要に応じてフィルム表面に帯電防止性、防曇性、粘着性、ガスバリヤー性、密着性および易接着性等の機能を有する層をコーティングにより形成することができる。例えば、フィルムの片面あるいは両面に、帯電防止剤を含む水性塗工液を塗布、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。水性塗工液を塗布する方法は、公知の方法が適用できる。すなわち、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が適用できる。
【００３３】
また、アクリル樹脂系粘着剤、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を主成分とし、他のビニル系モノマーを共重合せしめたコポリマーを、有機溶剤中に均一に溶解した溶剤系および水中に粒子状に分散させた水エマルジョン系の塗布液を公知の方法でフィルムに塗布、乾燥させ、粘着性を付与することができる。
【００３４】
本発明の脂肪族ポリエステルフィルムは、必要に応じて、他樹脂およびフィルムをラミネートすることにより、帯電防止性、防曇性、粘着性、ガスバリヤー性、密着性および易接着性等の機能を有する層をコーティングにより形成することができる。その際、押出ラミ、ドライラミ等の公知の方法を用いることができる。
【００３５】
本発明における脂肪族ポリエステルフィルムにおいては、２０℃における貯蔵弾性率（Ｅ’）が１×１０7〜２×１０9Ｐａであり、良好な柔軟性を有する。また、２０℃における損失正接（ｔａｎδ）が０．１〜１．０であり、良好な自己密着性および被包装体等との密着性を有する。また、ヘイズが０．０５〜３％、耐熱温度が１００〜１７０℃、結晶化度が１０〜６０％である。本発明の脂肪族ポリエステルフィルムを少なくとも１軸方向に延伸して得られる脂肪族ポリエステル延伸フィルムの特性についても上記とほぼ同様である。
【００３６】
【実施例】
以下、実施例を示して本発明についてさらに詳細に説明する。尚、〔表１〕〜〔表３〕に記載した記号は下記を意味する。
Ａ１：一般式（１）におけるＲ１〜Ｒ４が全て炭素数１のアシル基、ｎは１。
Ａ２：一般式（１）におけるＲ１〜Ｒ４が全て炭素数８のアシル基、ｎは１。
Ａ３：一般式（１）におけるＲ１〜Ｒ４が全て炭素数１８のアシル基、ｎは２。
Ａ４：一般式（１）におけるＲ１〜Ｒ４が全て炭素数２２のアシル基、ｎは９。
Ｂ１：デカグリセリンプロピオネート。
Ｂ２：テトラグリセリンカプリレート。
Ｂ３：デカグリセリンベヘネート。
【００３７】
また、この実施例に示す結晶化度、貯蔵弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価は、以下に示す方法で行った。
【００３８】
（１）結晶化度（％）
示差走査熱量計〔リガク（株）製、形式：ＴＡＳ１００〕を用い、融解曲線のピーク面積より、融解熱量（ΔＨ）を求め、完全結晶の融解熱量（ΔＨ0）より下記数式（数１）により結晶化度（Ｘc）を算出する。なお、標準物質としてはインジウムを用いる。
ＸC ＝ΔＨ／ΔＨ0・・・（数１）
【００３９】
（２）貯蔵弾性率 Ｅ’（Ｐａ）、ｔａｎδ
動的固体粘弾性測定装置〔レオメトリクス社製、型式：ＲＳＡＩＩ〕を用いて、長さ４０ｍｍ（ＭＤ方向）、幅５ｍｍ（ＴＤ方向）、厚み約１０μｍのフィルムについて、測定温度範囲−１００〜２３０℃、昇温速度５℃／ｍｉｎ．、周波数１Ｈｚの条件下で測定を行ない、２０℃における貯蔵弾性率（Ｅ’）を読み取り、損失弾性率（Ｅ’’）と貯蔵弾性率（Ｅ’）との比（Ｅ’’／Ｅ’）であるｔａｎδを算出する。
【００４０】
（３）ヘイズ（％）
東京電色（株）製、ヘイズ Ｍｅｔｅｒを使用して測定し、ヘイズ値（％）を求める。
【００４１】
（４）耐熱温度（℃）
ＭＤ方向１４ｃｍ、ＴＤ方向３ｃｍのフィルムと同じ幅の板目紙をフィルムと重ねてフィルムの機械方向の両端部２．５ｃｍの部分を粘着テープで板目紙と貼り合わせて固定したものを試料とする。板目紙で補強した試料フィルムのそれぞれの両端２．５cmの部分の上部を全幅にわたって治具に固定し、下端中央部に１０ｇの荷重をかけ、一定温度に調製したエアーオーブン中に迅速に入れ、１時間加熱したときの試料の切断の有無を調べる。試験温度は５℃刻みに上昇させた。１時間経過後、試料が切断しなかった場合は、温度を５℃上げ前記の操作を繰り返す。試料が切断しない最高温度を耐熱温度とする。
【００４２】
調製例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℃、７０００Ｐａにおいて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℃、４０００Ｐａにおいてさらに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℃、４７００Ｐａにおいて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℃、４７００Ｐａにおいて反応を行い、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℃、７０００Ｐａにおいて乾燥した。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℃、７０００Ｐａで乾燥して、平均粒径３０μｍのポリ乳酸粉末６．１ｋｇ（収率８５重量％）を得た。このポリマーのポリスチレン換算重量平均分子量は約１２万であった。
【００４３】
実施例１
調製例１で得られたポリマー１００重量部に対し、化合物Ａ１：３０重量部および化合物Ｂ１：５重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ８０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２．５倍、次いで横方向に３倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は１５％であった。弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価を行った結果を［表１］に示す。
【００４４】
実施例２
調製例１で得られたポリマー１００重量部に対し、化合物Ａ１：２５重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ６０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２倍、次いで横方向に２．５倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は２５％であった。弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価を行った結果を［表１］に示す。
【００４５】
参考例１
調製例１で得られたポリマー１００重量部に対し、化合物Ｂ１：１５重量部および化合物を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ６０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２倍、次いで横方向に３倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は１５％であった。弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価を行った結果を［表１］に示す。
【００４６】
実施例３
調製例１で得られたポリマー１００重量部に対し、化合物Ａ２：５５重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ５０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に１．５倍、次いで横方向に２．５倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は１２％であった。弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価を行った結果を［表１］に示す。
【００４７】
参考例２
調製例１で得られたポリマー１００重量部に対し、化合物Ｂ１：５０重量部および化合物を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ８０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２．５倍、次いで横方向に３倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は１５％であった。弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価を行った結果を［表１］に示す。
【００４８】
実施例４
調製例１で得られたポリマー１００重量部に対し、化合物Ａ３：４０重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ４０μｍの未延伸フィルムを得た。この未延伸フィルムの両面に、調製例１で得られたポリマーからなる厚さ１０μｍのフィルムを張り合せた後、長さ方向に２．５倍、次いで横方向に３倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価を行った結果を［表１］に示す。
【００４９】
実施例５
調製例１で得られたポリマー１００重量部に対し、化合物Ａ３：３０重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ６０μｍの未延伸フィルムを得た。この未延伸フィルムの両面に、ポリブチレンサクシネートからなる厚さ１０μｍのフィルムを張り合せた後、この未延伸フィルムを長さ方向に２．５倍、次いで横方向に３倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。弾性率、ｔａｎδ、ヘイズ、および耐熱温度の評価を行った結果を［表１］に示す。
【００５０】
実施例６
調製例１で得られたポリマー１００重量部に対し、化合物Ａ１：２０重量部を含むペレットを、４０ｍｍのインフレーション成形機（ダイス径４０ｍｍ）にて、１７０℃で成形し、折り径１５０ｍｍ、厚み１２μｍのインフレーションフィルムを得た。得られたフィルムを１４０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却した。このフィルムの結晶化度は１８％であった。評価結果を［表１］に示す。
【００５１】
比較例１
調製例１で得られたポリマー１００重量部に対し、化合物Ａ１：５重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ８０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２．５倍、次いで横方向に３．５倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は３０％であった。評価結果を［表２］に示す。
【００５２】
比較例２
調製例１で得られたポリマー１００重量部に対し、化合物Ｂ１：５重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ８０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２．５倍、次いで横方向に３倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１１μｍの延伸フィルムを得た。得られたフィルムの結晶化度は３５％であった。評価結果を［表２］に示す。
【００５３】
比較例３
調製例１で得られたポリマー１００重量部に対し、化合物Ａ１：７０重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ７０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２倍、次いで横方向に３倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は１５％であった。評価結果を［表２］に示す。
【００５４】
比較例４
調製例１で得られたポリマー１００重量部に対し、化合物Ａ１：５０重量部および化合物Ｂ１：３０重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ５０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に１．５倍、次いで横方向に２．５倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０μｍの延伸フィルムを得た。得られたフィルムの結晶化度は１２％であった。評価結果を［表２］に示す。
【００５５】
比較例５
調製例１で得られたポリマー１００重量部に対し、化合物Ａ４：２０重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ６０μｍの未延伸フィルムを得た。この未延伸フィルムを長さ方向に２倍、次いで横方向に２．５倍延伸し、１３０℃で熱処理を行った後、３０℃の空気を用いてフィルムを冷却し平均厚み１０ｍの延伸フィルムを得た。得られたフィルムの結晶化度は２０％であった。評価結果を［表２］に示す。
【００５６】
比較例６
調製例１で得られたポリマー１００重量部に対し、化合物Ａ１：３０重量部を含むペレットを、１８０℃においてＴダイが装着された押出機を用いて混練、溶融して押出し、厚さ１０μｍの未延伸フィルムを得た。得られたフィルムの結晶化度は４％であった。評価結果を［表２］に示す。
【００５７】
【表１】
【表２】
実施例７
実施例１で得られたフィルムを、長さ１８０ｍｍ、幅５００ｍｍに切り、幅方向に２つ折にした後、折り目の側辺の二辺を１００℃でヒートシールすることにより、開口部の幅約１７５ｍｍ、深さ２５０ｍｍの袋を得た。得られた袋にトマト約５００ｇを充填し、袋の開口部を絞り、結束テープで固定し、包装体を得た。
【００６０】
実施例８
実施例６で得られた折り径１５０ｍｍ、厚み１２μｍのインフレーションフィルムを長さ方向に、２５０ｍｍ間隔で、溶断温度２８０℃にて溶断シールした後、同間隔でカットすることにより、開口部の幅１５０ｍｍ、深さ約２４５ｍｍの袋を得た。得られた袋に人参約５００ｇを充填し、袋の開口部を絞り、結束テープで固定し、包装体を得た。
【００６１】
【発明の効果】
本発明に係わる脂肪族ポリエステルフィルムは、脂肪族ポリエステルが乳酸系ポリマーである場合、乳酸系ポリマーが本来有する自然環境下での分解性を維持し、優れた耐熱性、柔軟性、透明性及び密着性を有し、しかも表面に可塑剤がブリードアウトすることがない。そのため、食品、電子、医療、薬品、化粧品等の各種包装用フィルム、農業用フィルム、土建・建築用フィルム、粘着テープ等の広範囲における資材として好適に使用し得る。使用した後、廃棄されても産業廃棄物、家庭廃棄物として蓄積することがない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aliphatic polyester film and a package using the film. Specifically, the present invention relates to an aliphatic polyester film that has degradability in a natural environment and has excellent flexibility and adhesion, and a package using the aliphatic polyester film.
[0002]
[Prior art]
In recent years, the plastic waste problem has been highlighted. Plastic wastes such as packaging materials are disposed of after being used by the user, disposed of by incineration, or disposed of by landfill. However, when such plastic waste is incinerated, the heat of combustion is high, and the problem of durability of the incinerator, and in the case of things such as polyvinyl chloride, harmful gas is generated, causing pollution problems. Furthermore, when it is landfilled, the plastic molded product is not decomposed as it is, but remains in its original form as rubbish semipermanently, and the influence on the natural environment has become a problem. Under such circumstances, various biodegradable plastics that are completely consumed by microorganisms in a natural environment and decompose into carbon dioxide and water, which are natural by-products, have been invented and are in a practical level.
[0003]
JP-A-6-340753 discloses that a composition comprising polylactic acid or a thermoplastic polymer mainly composed of lactic acid and other hydroxycarboxylic acids can be used, for example, as a degradable card, and it is It is disclosed that it has high strength and exhibits durability that can withstand practical use. However, since the polymer has a high elastic modulus and rigidity and is poor in flexibility, it is not suitable for applications in which soft films such as polyethylene, polypropylene, and polyvinyl chloride are used.
[0004]
In general, as a method for softening a resin, methods such as (1) addition of a plasticizer, (2) copolymerization, (3) blend of soft polymers, and (4) lamination with soft polymers are known. Among them, (1) has been studied for softening using various plasticizers in the past. For example, JP-A-4-335060 discloses a composition obtained by adding a plasticizer to polylactic acid. Specific examples thereof include diisobutyl adipate, dioctyl sebacate and the like as plasticizers. However, a film using such a compound as a plasticizer is considerably improved in flexibility, but has a problem that the plasticizer rises with time.
[0005]
In the method (3), considering biodegradability which is one of the problems, the resin to be blended is limited to a biodegradable resin having flexibility. Examples of such a resin include polybutylene succinate, polyethylene succinate, polycaprolactone and the like, which have already been disclosed in JP-A-8-245866 and JP-A-9-111107. However, when these resins are blended, there are problems such as a decrease in transparency and heat resistance. In the method (4), flexibility is imparted by selecting a resin to be laminated in consideration of biodegradability in the same manner as (3). However, when these resins are laminated, there are problems such as a decrease in transparency and heat resistance as in the case of (3).
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide an aliphatic polyester film that is degradable in a natural environment, has excellent flexibility and adhesion, and does not bleed out from a plasticizer, and packaging using the film To provide a body.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have used a specific compound as a plasticizer for the aliphatic polyester, so that the plasticizer does not bleed out, and has excellent transparency, The inventors have found that an aliphatic polyester having heat resistance, flexibility and adhesion can be obtained, and have reached the present invention.
[0008]
That is, the gist of the present invention is the general formula (1) [Chemical Formula 2] with respect to 100 parts by weight of the aliphatic polyester.
[0009]
[Chemical 2]
(In the formula, n is an integer of 1 to 10, R1~ RFourIs an acyl group having 1 to 18 carbon atoms) and a compound (B) which is a reaction product of a condensate of 1 to 10 molecules of glycerin and a carboxylic acid having 6 to 18 carbon atoms. A monolayer or multilayer aliphatic polyester film having at least one layer containing 10 to 60 parts by weight of at least one selected compound, and having a storage elastic modulus (E ′) at 20 ° C. of 1 × 107~ 2x109Loss tangent (tan δ), which is a ratio (E ″ / E ′) of loss elastic modulus (E ″) to Pa, storage elastic modulus (E ′), is in the range of 0.1 to 1.0. An aliphatic polyester film.
Another aspect of the present invention is a package in which an article to be packaged is packaged using the aliphatic polyester film.
[0011]
The aliphatic polyester film according to the present invention has excellent heat resistance, flexibility, transparency and adhesion, and the plasticizer does not bleed out. Furthermore, when polylactic acid, a copolymer of lactic acid and other aliphatic hydroxycarboxylic acids, etc. are used as the aliphatic polyester, it has hydrolyzability, so even if it is discarded after use, it will remain in the natural environment. There is no accumulation. Therefore, it can be suitably used as a wide range of materials such as various packaging films for food, electronics, medical care, medicine, cosmetics, etc., agricultural films, earthwork / architecture films, and base films for adhesive tapes. In particular, it is suitable as a packaging material for foods. When the packaged article of the packaging body of the present invention is a food, for example, composting can be performed without separating the packaging material and the packaged article.
[0012]
The loss tangent (tan δ), which is the storage elastic modulus (E ′) and the ratio (E ″ / E ′) of the loss elastic modulus (E ″) to the storage elastic modulus (E ′) in the present invention, will be described later. Means a value measured by the method described in the Examples.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. First, the aliphatic polyester composition used for the aliphatic polyester film according to the present invention will be described. The aliphatic polyester composition used in the present invention is produced by adding and mixing at least one compound selected from the compound (A) and the compound (B) as a plasticizer to the aliphatic polyester.
[0014]
The aliphatic polyester used in the present invention is an aliphatic polyester containing a lactic acid unit in the molecule. Specifically, (1) polylactic acid, a copolymer of lactic acid and other aliphatic hydroxycarboxylic acid, (2) an aliphatic polyester containing a polyfunctional polysaccharide and a lactic acid unit, (3) an aliphatic polyvalent carboxylic acid Aliphatic polyesters containing units, aliphatic polyhydric alcohol units, and lactic acid units, and (4) mixtures thereof. Hereinafter, these are collectively referred to as a lactic acid polymer. Among these, considering the transparency and hydrolyzability of the resulting film, polylactic acid and copolymers of lactic acid and other aliphatic hydroxycarboxylic acids are preferred.
[0015]
Lactic acid has an L-form and a D-form. In the present invention, the term lactic acid refers to both the L-form and the D-form unless otherwise specified. The molecular weight of the polymer refers to the weight average molecular weight unless otherwise specified. 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. Examples of hydroxycarboxylic acids of lactic acid-other aliphatic hydroxycarboxylic acid copolymers include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and the like. It is done.
[0016]
Examples of the method for producing polylactic acid used in the present invention include a method of directly dehydrating and condensing 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. It is done. The ring-opening polymerization may be performed in the presence of a compound having a hydroxyl group such as a higher alcohol or a hydroxycarboxylic acid. It may be produced by any method. As a method for producing lactic acid-another aliphatic hydroxycarboxylic acid copolymer, a method of dehydrating polycondensation of each lactic acid and the hydroxycarboxylic acid, a lactide that is a cyclic dimer of each lactic acid, and a cyclic product of the hydroxycarboxylic acid Examples thereof include a ring-opening copolymerization method. It may be produced by any method. The amount of lactic acid units contained in the copolymer is preferably at least 40 mol%.
[0017]
Examples of polyfunctional polysaccharides and polyfunctional polysaccharides used in the production of aliphatic polyesters containing lactic acid units include cellulose, cellulose nitrate, methylcellulose, ethylcellulose, celluloid, viscose rayon, regenerated cellulose, cellophane, cupra, and copper ammonia rayon. , Cuprophan, 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 . Of these, cellulose acetate and ethyl cellulose are particularly preferred.
[0018]
As a method of producing an aliphatic polyester containing a polyfunctional polysaccharide and a lactic acid unit, a method of reacting the polyfunctional polysaccharide with the polylactic acid, lactic acid-other aliphatic hydroxycarboxylic acid copolymer, the polyfunctional polysaccharide and the above The method etc. which react each lactic acid, cyclic ester, etc. are mentioned. It may be produced by any method. The amount of lactic acid units contained in the aliphatic polyester is desirably at least 50 mol%.
[0019]
Examples of the aliphatic polycarboxylic acid used for the production of the aliphatic polyester containing an aliphatic polycarboxylic acid unit, an aliphatic polyhydric alcohol unit and a lactic acid unit include 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 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 can be mentioned.
[0020]
As a method for producing an aliphatic polyester containing an aliphatic polycarboxylic acid unit, an aliphatic polyhydric alcohol unit, and a lactic acid unit, the aliphatic polycarboxylic acid and the aliphatic polyhydric alcohol, and the polylactic acid, lactic acid, etc. And a method of reacting the above aliphatic polycarboxylic acid copolymer and the above aliphatic polycarboxylic acid and the above aliphatic polyhydric alcohol 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 aliphatic polyester is preferably at least 50 mol%.
[0021]
The molecular weight of the aliphatic polyester affects the processability of the film, the strength and degradability of the resulting film. When the molecular weight is low, the strength of the obtained film is lowered, and it may break due to tension when used. In addition, the decomposition speed is increased. On the other hand, if the molecular weight is high, processability is lowered and film formation becomes difficult. Considering this point, the molecular weight of the aliphatic polyester is preferably in the range of about 10,000 to about 1,000,000. A more preferable range is 100,000 to 300,000.
[0022]
In the present invention, as a plasticizer for an aliphatic polyester, the reaction product of the compound (A) represented by the general formula (1) and a condensate of 1 to 10 molecules of glycerin and a carboxylic acid having 6 to 18 carbon atoms. At least one compound selected from the compound (B) is: The added amount of these plasticizers affects the crystallinity, flexibility, heat resistance, and the like of the obtained stretched film. When there is too much addition amount, a crystallinity degree and heat resistance will fall. If the amount is too small, sufficient flexibility cannot be obtained. From this viewpoint, the amount of the compound (A) and / or (B) added as a plasticizer is preferably 10 to 60 parts by weight with respect to 100 parts by weight of the aliphatic polyester. More preferably, it is 15-50 weight part.
[0023]
In the aliphatic polyester composition of the present invention, in addition to the aliphatic polyester as the main component, the compound (A), and the compound (B), depending on the application, the purpose of the present invention is not impaired. Antiblocking agents such as silica, calcium carbonate, titania, mica and talc, 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, lower fatty acids Alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycol esters, aliphatic alcohols, polyhydric alcohols, polyglycols, metal soaps such as calcium stearate, fatty acid salts, higher alcohol sulfates , Liquid fatty oil sulfate salts, aliphatic amines and fats Amide sulfates, aliphatic alcohol phosphate salts, sulfonates of dibasic fatty acid esters, aliphatic amide sulfonates, alkylallyl sulfonates, aliphatic amine salts, quaternary ammonium salts, alkyl pyridium Antistatic agents such as salts, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, imidazoline derivatives, higher alkyl amines, Glycerin fatty acid esters such as glycerol monostearate, sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan monooleate, polyglycerol fatty acid esters, propylene glycol fat Anti-fogging agents such as esters, benzotriazoles such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, benzophenones such as 2-hydroxy-4-methoxybenzophenone, p-tert-butylphenyl salicylate UV absorbers such as salicylic acid derivatives, etc., phenols such as paramethoxyphenol, phosphites such as triphenyl phosphite, sulfurs such as 2-mercaptobenzimidazole, amines such as phenylnaphthylamine, thermal stabilizers, oxidation Add other additives such as inhibitors, anti-coloring agents, fillers such as barium sulfate, titanium oxide, kaolin, carbon black, pigments, halogens such as decabromodiphenyl ether, antimony flame retardants such as antimony trioxide May be.
[0024]
Next, an example of the aliphatic polyester film of the present invention and a method for producing the same will be described. As a method of adding and mixing the plasticizer to the aliphatic polyester, the aliphatic polyester and the plasticizer, and in some cases, other additives are uniformly mixed using a high-speed stirrer or a low-speed stirrer, and then sufficient kneading ability is obtained. For example, a melt kneading method using a uniaxial or multiaxial extruder can be employed. In general, the shape of the resin composition according to the present invention is preferably pellets, rods, powders, and the like.
[0025]
The resin composition obtained as described above is formed into a film by a melt extrusion method using an extruder equipped with a T die. Preferably, the obtained film is stretched in the flow direction (machine direction, hereinafter referred to as MD direction) by roll stretching, and then stretched in the transverse direction (direction perpendicular to the machine direction, hereinafter referred to as TD direction) by tenter stretching. The order of stretching may be the reverse of the above. After stretching, a stretched aliphatic polyester film is produced by heat treatment under tension. In the case of uniaxial stretching, the stretching may be performed in either the MD direction or the TD direction.
[0026]
The melt extrusion temperature of the aliphatic polyester composition containing the various additives is preferably in the range of 100 to 280 ° C, more preferably 130 to 250 ° C. If the molding temperature is low, molding stability is difficult to obtain, and overload tends to occur. On the other hand, if the molding temperature is high, the aliphatic polyester may be decomposed, which is not preferable because molecular weight reduction, strength reduction, coloring and the like occur.
[0027]
The aliphatic polyester film of the present invention is preferably stretched 1.5 to 5 times in at least a uniaxial direction in the MD direction and the TD direction. More preferably, it is a biaxially stretched film biaxially stretched in the MD direction and the TD direction. In the case of producing a stretched film, if the stretch ratio is less than 1.5 times, it is difficult for crystallization to bring about aging stability of mechanical properties and dimensional accuracy. On the other hand, if it exceeds 5 times, the flexibility of the film is lost, and film breakage or the like occurs during stretching, which is not preferable. The stretching temperature is preferably in the range of the glass transition temperature (Tg) to (Tg + 50) ° C. of the aliphatic polyester used. More preferably, it is the range of Tg- (Tg + 30) degreeC. If the stretching temperature is less than Tg, stretching is difficult, and if it exceeds (Tg + 50) ° C., uniform stretching becomes difficult, which is not preferable. In order to improve heat resistance and dimensional stability, heat treatment is performed at a temperature of (Tg + 10) ° C. or higher and lower than the melting point under tension after stretching. At this time, the crystallinity of the film can be controlled by changing the stretching and heat treatment conditions.
[0028]
By performing stretching and heat treatment under the above conditions, a stretched film having a crystallinity of 10 to 60% is obtained. A preferable crystallinity is 20 to 50%. For example, R in the compound (A) with respect to 100 parts by weight of the lactic acid polymer.1~ R420 parts by weight of a compound having all of an acyl group having 1 carbon atom and n of 1 and forming a film using a T-die, then, at 50 ° C., 2.5 times in the machine direction and 2. in the width direction. Stretch 5 times (hereinafter abbreviated as 2.5 × 2.5). Then, a stretched film having a crystallinity of about 30% is obtained by performing heat treatment at 140 ° C. under tension.
[0029]
The aliphatic polyester film of the present invention can be produced in a roll shape, a tape shape, a cut sheet shape, or a tubular shape (seamless shape) by setting process conditions according to the purpose.
[0030]
Aliphatic polyester film of the present invention is a shopping bag, garbage bag, compost bag, food / confectionery packaging film, food packaging wrap film, cosmetic / cosmetic wrap film, pharmaceutical wrap film, herbal medicine wrap film, stiff shoulder Wrapping film for surgical patches applied to sprains, agricultural / horticultural film, wrapping film for agricultural chemicals, greenhouse film, fertilizer bag, film for packaging magnetic tape cassette products such as video and audio, floppy disk packaging Film, plate-making film, adhesive tape, waterproof sheet, sandbag bag, and the like. Of these uses, it is preferably used as a packaging film to form a package. Examples of packages include foods such as vegetables, fruits, and confectionery, cosmetics, pharmaceuticals, agricultural chemicals, fertilizers, soil, household garbage, compost, video, and electronic products such as videos and CDs. It is done. The thickness of the polyester film of the present invention can be appropriately changed according to the use, but is usually in the range of 5 to 1000 μm.
[0031]
The aliphatic polyester film of the present invention can be processed into a bag shape by a method such as heat sealing, high frequency sealing and fusing. For example, by folding the film manufactured in a cut sheet shape in two and heat-sealing the two sides of the fold using a heat seal bar having a temperature equal to or higher than the Tg (glass transition temperature) of the film, can get. Moreover, a bag is obtained by breaking the roll-shaped film into two in the width direction and fusing at a constant interval in the length direction using a fusing bar having a temperature equal to or higher than the melting point of the film. In addition, after unsealing the cylindrical film, using a heat seal bar with a temperature of Tg or higher, heat-sealing at regular intervals in the length direction, and then cutting the immediate vicinity of the seal portion at the same interval, can get.
[0032]
In the stretched aliphatic polyester film of the present invention, a layer having functions such as antistatic property, antifogging property, tackiness, gas barrier property, adhesion and easy adhesion is formed on the film surface by coating as necessary. Can do. For example, the antistatic layer can be formed by applying and drying an aqueous coating solution containing an antistatic agent on one or both sides of the film. A known method can be applied as a method of applying the aqueous coating solution. That is, 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 can be applied.
[0033]
In addition, a solvent system in which an acrylic resin-based pressure-sensitive adhesive such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. as a main component and a copolymer obtained by copolymerizing other vinyl monomers is uniformly dissolved in an organic solvent and A water-emulsion coating solution dispersed in the form of particles in water can be applied to a film by a known method and dried to impart tackiness.
[0034]
The aliphatic polyester film of the present invention has functions such as antistatic properties, antifogging properties, tackiness, gas barrier properties, adhesion and easy adhesion by laminating other resins and films as necessary. The layer can be formed by coating. At that time, a known method such as extrusion lamination or dry lamination can be used.
[0035]
In the aliphatic polyester film of the present invention, the storage elastic modulus (E ′) at 20 ° C. is 1 × 10.7~ 2x109Pa and has good flexibility. Further, the loss tangent (tan δ) at 20 ° C. is 0.1 to 1.0, and it has good self-adhesion and adhesion to a packaged body and the like. The haze is 0.05 to 3%, the heat resistant temperature is 100 to 170 ° C., and the crystallinity is 10 to 60%. The characteristics of the stretched aliphatic polyester film obtained by stretching the aliphatic polyester film of the present invention in at least one axial direction are substantially the same as described above.
[0036]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the symbol described in [Table 1]-[Table 3] means the following.
A1: R in the general formula (1)1~ R4Are all acyl groups having 1 carbon atom, and n is 1.
A2: R in the general formula (1)1~ R4Are all acyl groups having 8 carbon atoms, and n is 1.
A3: R in the general formula (1)1~ R4Are all acyl groups having 18 carbon atoms, and n is 2.
A4: R in the general formula (1)1~ R4Are all 22 acyl groups and n is 9.
B1: Decaglycerin propionate.
B2: Tetraglycerin caprylate.
B3: Decaglycerin behenate.
[0037]
In addition, the crystallinity, storage elastic modulus, tan δ, haze, and heat resistant temperature shown in this example were evaluated by the following methods.
[0038]
(1) Crystallinity (%)
Using a differential scanning calorimeter [manufactured by Rigaku Corporation, type: TAS100], the heat of fusion (ΔH) is obtained from the peak area of the melting curve, and the heat of fusion of the complete crystal (ΔH)0), The crystallinity (Xc) is calculated by the following mathematical formula (Equation 1). Note that indium is used as the standard substance.
XC= ΔH / ΔH0... (Equation 1)
[0039]
(2) Storage elastic modulus E ′ (Pa), tan δ
Using a dynamic solid viscoelasticity measuring apparatus (Rheometrics, model: RSAII), a measurement temperature range of −100 to 230 for a film having a length of 40 mm (MD direction), a width of 5 mm (TD direction), and a thickness of about 10 μm. ° C, heating rate 5 ° C / min. , Measured at a frequency of 1 Hz, read storage elastic modulus (E ′) at 20 ° C., and ratio of loss elastic modulus (E ″) to storage elastic modulus (E ′) (E ″ / E ′) ) Which is) is calculated.
[0040]
(3) Haze (%)
The haze value (%) is determined by using a haze meter manufactured by Tokyo Denshoku Co., Ltd.
[0041]
(4) Heat-resistant temperature (℃)
A sample of a sheet of paper having the same width as the film of 14 cm in the MD direction and 3 cm in the TD direction is overlapped with the film, and the portions of 2.5 cm at both ends in the machine direction of the film are bonded to the board with an adhesive tape and fixed. To do. Fix the upper part of each 2.5cm part of the sample film reinforced with board paper to the jig across the entire width, apply a load of 10g to the center of the lower end, and quickly put it in an air oven adjusted to a constant temperature The sample is examined for the presence or absence of cutting when heated for 1 hour. The test temperature was increased in increments of 5 ° C. If the sample does not cut after 1 hour, the temperature is raised by 5 ° C. and the above operation is repeated. The maximum temperature at which the sample does not cut is the heat resistant temperature.
[0042]
Preparation Example 1
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. and 7000 Pa for 3 hours, 6.2 g of tin powder was added, and the mixture was further oligomerized by stirring at 150 ° C. and 4000 Pa for 2 hours. To this oligomer, 28.8 g of tin powder and 21.1 kg of diphenyl ether were added, azeotropic dehydration reaction was performed at 150 ° C. and 4700 Pa, and the distilled water and the solvent were separated by a water separator, and the aqueous layer was sequentially extracted to obtain only the solvent. Was returned to the 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. The reaction was carried out at 150 ° C. and 4700 Pa 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. and 7000 Pa. This powder was added with 12 kg of 0.5N hydrochloric acid and 12 kg of ethanol, stirred for 1 hour at 35 ° C., filtered, dried at 60 ° C. and 7000 Pa, and 6.1 kg of polylactic acid powder having an average particle size of 30 μm (yield: 85 wt. %). The polystyrene equivalent weight average molecular weight of this polymer was about 120,000.
[0043]
Example 1
To 100 parts by weight of the polymer obtained in Preparation Example 1, pellets containing 1 part by weight of Compound A and 1: 5 parts by weight of Compound B were kneaded and melted at 180 ° C. using an extruder equipped with a T die. And an unstretched film having a thickness of 80 μm was obtained. This unstretched film is stretched 2.5 times in the length direction and then 3 times in the transverse direction, heat-treated at 130 ° C., and then cooled with air at 30 ° C. to obtain a stretched film having an average thickness of 10 μm. Obtained. The crystallinity of the obtained film was 15%. The results of evaluation of elastic modulus, tan δ, haze, and heat resistant temperature are shown in [Table 1].
[0044]
Example 2
Pellets containing 25 parts by weight of Compound A1: 25 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded using an extruder equipped with a T die at 180 ° C., and the thickness was 60 μm. An unstretched film was obtained. This unstretched film was stretched twice in the length direction and then 2.5 times in the transverse direction, and after heat treatment at 130 ° C., the film was cooled with air at 30 ° C. to obtain a stretched film having an average thickness of 10 μm. Obtained. The crystallinity of the obtained film was 25%. The results of evaluation of elastic modulus, tan δ, haze, and heat resistant temperature are shown in [Table 1].
[0045]
referenceExample1
With respect to 100 parts by weight of the polymer obtained in Preparation Example 1, 15 parts by weight of compound B and pellets containing the compound were kneaded, melted and extruded using an extruder equipped with a T die at 180 ° C. A 60 μm unstretched film was obtained. This unstretched film was stretched twice in the length direction and then three times in the transverse direction, and after heat treatment at 130 ° C., the film was cooled using air at 30 ° C. to obtain a stretched film having an average thickness of 10 μm. . The crystallinity of the obtained film was 15%. The results of evaluation of elastic modulus, tan δ, haze, and heat resistant temperature are shown in [Table 1].
[0046]
Example3
Pellets containing 55 parts by weight of compound A2 with respect to 100 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded at 180 ° C. using an extruder equipped with a T die, and the thickness was 50 μm. An unstretched film was obtained. This unstretched film is stretched 1.5 times in the length direction and then 2.5 times in the transverse direction, heat-treated at 130 ° C., and then cooled with air at 30 ° C. to draw an average thickness of 10 μm. A film was obtained. The crystallinity of the obtained film was 12%. The results of evaluation of elastic modulus, tan δ, haze, and heat resistant temperature are shown in [Table 1].
[0047]
referenceExample2
With respect to 100 parts by weight of the polymer obtained in Preparation Example 1, 50 parts by weight of compound B and pellets containing the compound were kneaded, melted and extruded using an extruder equipped with a T die at 180 ° C. An unstretched film of 80 μm was obtained. This unstretched film is stretched 2.5 times in the length direction and then 3 times in the transverse direction, heat-treated at 130 ° C., and then cooled with air at 30 ° C. to obtain a stretched film having an average thickness of 10 μm. Obtained. The crystallinity of the obtained film was 15%. The results of evaluation of elastic modulus, tan δ, haze, and heat resistant temperature are shown in [Table 1].
[0048]
Example4
Pellets containing 40 parts by weight of Compound A3: 100 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded at 180 ° C. using an extruder equipped with a T die, and the thickness was 40 μm. An unstretched film was obtained. After pasting the 10 μm-thick film made of the polymer obtained in Preparation Example 1 on both sides of this unstretched film, the film was stretched 2.5 times in the length direction and then 3 times in the transverse direction at 130 ° C. After the heat treatment, the film was cooled using air at 30 ° C. to obtain a stretched film having an average thickness of 10 μm. The results of evaluation of elastic modulus, tan δ, haze, and heat resistant temperature are shown in [Table 1].
[0049]
Example5
Pellets containing 30 parts by weight of compound A3 with respect to 100 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded at 180 ° C. using an extruder equipped with a T die, and the thickness was 60 μm. An unstretched film was obtained. After pasting a 10 μm-thick polybutylene succinate film on both sides of this unstretched film, the unstretched film was stretched 2.5 times in the length direction and then 3 times in the transverse direction, Then, the film was cooled using air at 30 ° C. to obtain a stretched film having an average thickness of 10 μm. The results of evaluation of elastic modulus, tan δ, haze, and heat resistant temperature are shown in [Table 1].
[0050]
Example6
A pellet containing Compound A1: 20 parts by weight with respect to 100 parts by weight of the polymer obtained in Preparation Example 1 was molded at 170 ° C. with a 40 mm inflation molding machine (die diameter: 40 mm), a fold diameter of 150 mm, and a thickness of 12 μm. Inflation film was obtained. After heat-treating the obtained film at 140 ° C., the film was cooled using 30 ° C. air. The crystallinity of this film was 18%. The evaluation results are shown in [Table 1].
[0051]
Comparative Example 1
Pellets containing 5 parts by weight of compound A1: 100 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded at 180 ° C. using an extruder equipped with a T die, and the thickness was 80 μm. An unstretched film was obtained. This unstretched film is stretched 2.5 times in the length direction and then 3.5 times in the transverse direction, heat-treated at 130 ° C., and then cooled with air at 30 ° C. to draw an average thickness of 10 μm. A film was obtained. The crystallinity of the obtained film was 30%. The evaluation results are shown in [Table 2].
[0052]
Comparative Example 2
Pellets containing 5 parts by weight of compound B with respect to 100 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded using an extruder equipped with a T die at 180 ° C., and the thickness was 80 μm. An unstretched film was obtained. This unstretched film was stretched 2.5 times in the length direction and then 3 times in the transverse direction, and after heat treatment at 130 ° C., the film was cooled using air at 30 ° C. to obtain a stretched film having an average thickness of 11 μm. Obtained. The crystallinity of the obtained film was 35%. The evaluation results are shown in [Table 2].
[0053]
Comparative Example 3
Pellets containing Compound A1: 70 parts by weight with respect to 100 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded at 180 ° C. using an extruder equipped with a T die, and the thickness was 70 μm. An unstretched film was obtained. This unstretched film was stretched twice in the length direction and then three times in the transverse direction, and after heat treatment at 130 ° C., the film was cooled using air at 30 ° C. to obtain a stretched film having an average thickness of 10 μm. . The crystallinity of the obtained film was 15%. The evaluation results are shown in [Table 2].
[0054]
Comparative Example 4
Pellets containing 1:50 parts by weight of compound A and 1:30 parts by weight of compound B were kneaded and melted at 180 ° C. using an extruder equipped with a T die with respect to 100 parts by weight of the polymer obtained in Preparation Example 1. And an unstretched film having a thickness of 50 μm was obtained. This unstretched film is stretched 1.5 times in the length direction and then 2.5 times in the transverse direction, heat-treated at 130 ° C., and then cooled with air at 30 ° C. to draw an average thickness of 10 μm. A film was obtained. The crystallinity of the obtained film was 12%. The evaluation results are shown in [Table 2].
[0055]
Comparative Example 5
Pellets containing 20 parts by weight of compound A4 with respect to 100 parts by weight of the polymer obtained in Preparation Example 1 were kneaded, melted and extruded using an extruder equipped with a T die at 180 ° C., and the thickness was 60 μm. An unstretched film was obtained. This unstretched film was stretched twice in the length direction and then 2.5 times in the transverse direction, and after heat treatment at 130 ° C., the film was cooled using air at 30 ° C. to obtain a stretched film having an average thickness of 10 m. Obtained. The crystallinity of the obtained film was 20%. The evaluation results are shown in [Table 2].
[0056]
Comparative Example 6
With respect to 100 parts by weight of the polymer obtained in Preparation Example 1, pellets containing 1 part by weight of Compound A were kneaded, melted and extruded at 180 ° C. using an extruder equipped with a T die, and the thickness was 10 μm. An unstretched film was obtained. The crystallinity of the obtained film was 4%. The evaluation results are shown in [Table 2].
[0057]
[Table 1]
[Table 2]
Example7
The film obtained in Example 1 was cut into a length of 180 mm and a width of 500 mm, folded in two in the width direction, and then heat-sealed at 100 ° C. on the two sides of the fold, thereby reducing the width of the opening. A bag of 175 mm and a depth of 250 mm was obtained. The obtained bag was filled with about 500 g of tomato, the opening of the bag was squeezed and fixed with a binding tape to obtain a package.
[0060]
Example8
Example6The blown film having a folding diameter of 150 mm and a thickness of 12 μm obtained in the above is melt-sealed at 250 mm intervals at a fusing temperature of 280 ° C. in the length direction, and then cut at the same intervals, whereby the opening width is 150 mm and depth A bag of about 245 mm was obtained. The obtained bag was filled with about 500 g of carrot, the opening of the bag was squeezed and fixed with a binding tape to obtain a package.
[0061]
【The invention's effect】
When the aliphatic polyester is a lactic acid polymer, the aliphatic polyester film according to the present invention maintains the degradability in the natural environment inherent to the lactic acid polymer, and has excellent heat resistance, flexibility, transparency, and adhesion. And the plasticizer does not bleed out on the surface. Therefore, it can be suitably used as a wide range of materials such as various packaging films for food, electronics, medicine, medicine, cosmetics, etc., agricultural films, earthwork / architecture films, and adhesive tapes. Even if it is discarded after use, it does not accumulate as industrial waste or household waste.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001051419A JP4846110B2 (en) | 2001-02-27 | 2001-02-27 | Aliphatic polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001051419A JP4846110B2 (en) | 2001-02-27 | 2001-02-27 | Aliphatic polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002249603A JP2002249603A (en) | 2002-09-06 |
| JP4846110B2 true JP4846110B2 (en) | 2011-12-28 |
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| JP2001051419A Expired - Fee Related JP4846110B2 (en) | 2001-02-27 | 2001-02-27 | Aliphatic polyester film |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4628649B2 (en) * | 2003-02-10 | 2011-02-09 | 理研ビタミン株式会社 | Antistatic method of biodegradable polyester resin composition and film, sheet and molded article |
| JP2005002269A (en) * | 2003-06-13 | 2005-01-06 | Three M Innovative Properties Co | Pressure-sensitive adhesive tape |
| DE602005021860D1 (en) * | 2004-02-26 | 2010-07-29 | Mitsubishi Plastics Inc | BIODEGRADABLE WRAPPING FOIL |
| KR100793447B1 (en) | 2005-05-16 | 2008-01-14 | 에스케이씨 주식회사 | Biodegradable Aliphatic Polyester Film |
| JP4678651B2 (en) * | 2006-03-30 | 2011-04-27 | 三菱樹脂株式会社 | Multilayer film |
| JP2006219684A (en) * | 2006-05-29 | 2006-08-24 | Mitsubishi Plastics Ind Ltd | Biodegradable soft film |
| JP5078399B2 (en) * | 2007-03-16 | 2012-11-21 | 三菱樹脂株式会社 | Multi-layered lactic acid soft film |
| JP5092521B2 (en) * | 2007-04-19 | 2012-12-05 | 大日本印刷株式会社 | Multilayer laminated film |
| JP4880579B2 (en) * | 2007-12-27 | 2012-02-22 | 三菱樹脂株式会社 | Packaging film |
| GB2494177A (en) * | 2011-09-02 | 2013-03-06 | Univ Loughborough | Determining interlaminar shear mechanical properties of composite laminates |
| JP2013159747A (en) * | 2012-02-08 | 2013-08-19 | Toray Ind Inc | Polylactic acid-based film |
| JP7396011B2 (en) * | 2019-12-12 | 2023-12-12 | 株式会社レゾナック | Screening method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE69918233T2 (en) * | 1998-03-05 | 2005-02-24 | Mitsui Chemicals, Inc. | POLYMIC ACID COMPOSITION AND FILM MANUFACTURED THEREOF |
| JP3383256B2 (en) * | 1999-02-18 | 2003-03-04 | 三井化学株式会社 | Aliphatic polyester composition and stretched film obtained from the composition |
| JP2001049098A (en) * | 1999-08-10 | 2001-02-20 | Mitsui Chemicals Inc | Lactic acid resin composition and molding form |
| JP3410075B2 (en) * | 2000-11-17 | 2003-05-26 | ユニチカ株式会社 | Crystalline polylactic acid resin composition, film and sheet using the same |
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