CN104039520B - The manufacture method of the injection-molded article of polylactic acid resin composition - Google Patents
The manufacture method of the injection-molded article of polylactic acid resin composition Download PDFInfo
- Publication number
- CN104039520B CN104039520B CN201280064097.1A CN201280064097A CN104039520B CN 104039520 B CN104039520 B CN 104039520B CN 201280064097 A CN201280064097 A CN 201280064097A CN 104039520 B CN104039520 B CN 104039520B
- Authority
- CN
- China
- Prior art keywords
- group
- ester
- polylactic acid
- production method
- 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.)
- Expired - Fee Related
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 102
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 102
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 98
- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000004014 plasticizer Substances 0.000 claims abstract description 69
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 238000002844 melting Methods 0.000 claims abstract description 41
- 230000008018 melting Effects 0.000 claims abstract description 41
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 26
- 238000001746 injection moulding Methods 0.000 claims abstract description 25
- 230000003746 surface roughness Effects 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 156
- 125000004432 carbon atom Chemical group C* 0.000 claims description 72
- -1 fatty acid ester Chemical class 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 61
- 150000002148 esters Chemical class 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 35
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 34
- 239000000194 fatty acid Substances 0.000 claims description 34
- 229930195729 fatty acid Natural products 0.000 claims description 34
- 125000002947 alkylene group Chemical group 0.000 claims description 30
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- 239000003484 crystal nucleating agent Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- 150000004665 fatty acids Chemical class 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 20
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 239000006082 mold release agent Substances 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 150000005846 sugar alcohols Polymers 0.000 claims description 13
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000001530 fumaric acid Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229960004063 propylene glycol Drugs 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 4
- HCUOEKSZWPGJIM-YBRHCDHNSA-N (e,2e)-2-hydroxyimino-6-methoxy-4-methyl-5-nitrohex-3-enamide Chemical compound COCC([N+]([O-])=O)\C(C)=C\C(=N/O)\C(N)=O HCUOEKSZWPGJIM-YBRHCDHNSA-N 0.000 claims description 4
- 229940035437 1,3-propanediol Drugs 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- 235000013772 propylene glycol Nutrition 0.000 claims description 4
- 150000003628 tricarboxylic acids Chemical class 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 2
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 claims 1
- 150000002688 maleic acid derivatives Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 50
- 239000003054 catalyst Substances 0.000 description 29
- 238000001816 cooling Methods 0.000 description 29
- 238000011109 contamination Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005886 esterification reaction Methods 0.000 description 14
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 12
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 12
- 238000007664 blowing Methods 0.000 description 12
- 230000032050 esterification Effects 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000004904 shortening Methods 0.000 description 11
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002894 organic compounds Chemical class 0.000 description 8
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000001384 succinic acid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- YSARBTHSZMNCIB-UHFFFAOYSA-N hexane-1,3,6-tricarboxylic acid Chemical compound OC(=O)CCCC(C(O)=O)CCC(O)=O YSARBTHSZMNCIB-UHFFFAOYSA-N 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 229920006167 biodegradable resin Polymers 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- YLWQQYRYYZPZLJ-UHFFFAOYSA-N 12-hydroxy-n-[2-(12-hydroxyoctadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCC(O)CCCCCC YLWQQYRYYZPZLJ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- WMNULTDOANGXRT-UHFFFAOYSA-N bis(2-ethylhexyl) butanedioate Chemical compound CCCCC(CC)COC(=O)CCC(=O)OCC(CC)CCCC WMNULTDOANGXRT-UHFFFAOYSA-N 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229930182843 D-Lactic acid Natural products 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
- 239000005977 Ethylene Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229940022769 d- lactic acid Drugs 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 150000005691 triesters Chemical class 0.000 description 3
- ALDZNWBBPCZXGH-UHFFFAOYSA-N 12-hydroxyoctadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(N)=O ALDZNWBBPCZXGH-UHFFFAOYSA-N 0.000 description 2
- 229940114069 12-hydroxystearate Drugs 0.000 description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- FSEJJKIPRNUIFL-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-octadecanoyloxypropyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCCCCCCCCCCCC FSEJJKIPRNUIFL-UHFFFAOYSA-N 0.000 description 2
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008431 aliphatic amides Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical group C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- SAOKZLXYCUGLFA-UHFFFAOYSA-N bis(2-ethylhexyl) adipate Chemical compound CCCCC(CC)COC(=O)CCCCC(=O)OCC(CC)CCCC SAOKZLXYCUGLFA-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229940097275 indigo Drugs 0.000 description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical group C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 229920001432 poly(L-lactide) Polymers 0.000 description 2
- 150000004032 porphyrins Chemical group 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical group C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 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
- 239000010959 steel Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RJRRZABNCURWAM-UHFFFAOYSA-N (2-butylphenyl)phosphonic acid Chemical compound CCCCC1=CC=CC=C1P(O)(O)=O RJRRZABNCURWAM-UHFFFAOYSA-N 0.000 description 1
- YXTSJMYYIRPSDF-UHFFFAOYSA-N (2-methylphenyl)phosphonic acid Chemical compound CC1=CC=CC=C1P(O)(O)=O YXTSJMYYIRPSDF-UHFFFAOYSA-N 0.000 description 1
- GDKNDQBTIVRVAV-UHFFFAOYSA-N (2-propylphenyl)phosphonic acid Chemical compound CCCC1=CC=CC=C1P(O)(O)=O GDKNDQBTIVRVAV-UHFFFAOYSA-N 0.000 description 1
- XVOUMQNXTGKGMA-OWOJBTEDSA-N (E)-glutaconic acid Chemical compound OC(=O)C\C=C\C(O)=O XVOUMQNXTGKGMA-OWOJBTEDSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MORHMXPGPOPWQT-UHFFFAOYSA-N 2-hydroxyethyl octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCO MORHMXPGPOPWQT-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000205754 Colocasia esculenta Species 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FOMSGFMDVIDZMI-QEMDMZNVSA-N OC(C(=O)O)CCCCCCCCCCCCCCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O Chemical compound OC(C(=O)O)CCCCCCCCCCCCCCCC.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O.C([C@H](O)[C@H](O)CO)O FOMSGFMDVIDZMI-QEMDMZNVSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CDSMQIKSBQLILH-UHFFFAOYSA-N [2,3-bis(ethoxycarbonyl)phenyl]phosphonic acid Chemical compound CCOC(=O)C1=CC=CC(P(O)(O)=O)=C1C(=O)OCC CDSMQIKSBQLILH-UHFFFAOYSA-N 0.000 description 1
- VONVWUIMYVDDGL-UHFFFAOYSA-N [2,3-bis(methoxycarbonyl)phenyl]phosphonic acid Chemical compound COC(=O)C1=CC=CC(P(O)(O)=O)=C1C(=O)OC VONVWUIMYVDDGL-UHFFFAOYSA-N 0.000 description 1
- FWCDLNRNBHJDQB-UHFFFAOYSA-N [2-(hydroxymethyl)-3-octadecanoyloxy-2-(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC FWCDLNRNBHJDQB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000011575 calcium Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- MWQBWSPPTQGZII-UHFFFAOYSA-N ethoxy(phenyl)phosphinic acid Chemical compound CCOP(O)(=O)C1=CC=CC=C1 MWQBWSPPTQGZII-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 235000013872 montan acid ester Nutrition 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Chemical class 0.000 description 1
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical class [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Biological Depolymerization Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The present invention relates to the manufacture method of the injection-molded article of polylactic acid resin composition, it is characterized in that, it is that the melting mixing thing of polylactic acid resin composition is filled in injection moulding machine the manufacture method of injection-molded article being shaped in mould, described polylactic acid resin composition contains polylactic resin, there is the plasticizer of polyoxyalkylenes or oxyalkylene group, and the releasing agent that fusing point is 20～75 DEG C, wherein, the at least one of design temperature of the barrel of described injection moulding machine is more than 200 DEG C, the surface temperature of described mould is more than 85 DEG C, the surface roughness of mould is less than 1.0 μm. the molded body obtained by the manufacture method of the present invention is owing to productivity is high and appearance is excellent, thus is applicable to the various industrial uses such as sundry goods product, appliances parts, appliances parts Strapping Material, automobile component.
Description
Technical Field
The present invention relates to a method for producing an injection-molded article of a polylactic acid resin composition. More specifically, the present invention relates to a method for producing an injection-molded article by injection-molding a polylactic acid resin composition which can be suitably used as a household appliance component such as a housing of an information household appliance, and a molded article obtained by the production method.
Background
Polylactic acid resins are expected to be used at present because of the following characteristics: l-lactic acid as a raw material can be produced by fermentation using sugars extracted from corn, taro, etc., and therefore is inexpensive; the raw materials are plant sources, so the emission of carbon dioxide is very little; in addition, it has high rigidity and high transparency as resin properties; and so on.
Patent document 1 describes the following: 0.01 to 3 parts by weight of at least 1 selected from the group consisting of higher fatty acids, higher fatty acid esters, higher fatty acid metal salts and fatty acid amides in total are attached to the surface of the lactic acid resin particles (pellets) per 100 parts by weight of the lactic acid resin, and the resulting material is injection-molded, and is free from variations in metering time and discharge amount and excellent in molding stability such as releasability.
Patent document 2 discloses a method for continuously producing a sheet or the like of a biodegradable resin having excellent flexibility, heat resistance, and temperature sensitivity, in which a resin composition containing a polylactic acid resin, a plasticizer, a crystal nucleus agent, and a lubricant is rolled with a roll and then subjected to a specific heat treatment to obtain a crystallized sheet or film having a relative crystallinity of 30% or more.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-106515
Patent document 2: japanese patent laid-open publication No. 2007-130894
Disclosure of Invention
The present invention relates to the following [1] to [2 ].
[1] A method for producing an injection-molded article of a polylactic acid resin composition, characterized in that a melt-kneaded product of a polylactic acid resin composition containing a polylactic acid resin, a plasticizer having a polyoxyalkylene group or oxyalkylene group, and a mold release agent having a melting point of 20 to 75 ℃ is filled in an injection-molding machine and molded in a mold, wherein the set temperature of at least a part of a cylinder of the injection-molding machine is 200 ℃ or higher, the surface temperature of the mold is 85 ℃ or higher, and the surface roughness of the mold is 1.0 [ mu ] m or lower.
[2] A molded article obtained by the production method according to [1 ].
Detailed Description
In the method of patent document 1, resin particles need to be prepared in advance in order to attach higher fatty acids and the like to the surface, and therefore, not only is the operation complicated, but also it is difficult to achieve uniform attachment, and therefore, it is difficult to obtain an injection molded article having an excellent surface appearance. The method of patent document 2 is a calender molding, and is different from the injection molding method in terms of conditions and apparatus used.
The present invention relates to a method for producing an injection-molded article of a polylactic acid resin composition, which can reduce the time for cooling and holding in a mold, can suppress mold contamination after mold release, and can obtain a molded article having an excellent surface appearance, and a molded article obtained by the production method.
The molded article of the polylactic acid resin composition obtained by the production method of the present invention has excellent mold transferability, and therefore, has an excellent effect of providing a good surface appearance. Further, the molding processability at low temperature is good, and the productivity is also excellent.
The method for producing an injection-molded article of a polylactic acid resin composition of the present invention is a method for producing a polylactic acid resin composition by injection-molding the polylactic acid resin composition in a mold, and is characterized in that the polylactic acid resin composition contains a specific component, the cylinder temperature of an injection molding machine for injection molding is set to 200 ℃ or higher, and a mold having a specific surface temperature and surface roughness is used. When molding is performed under such conditions, the use of a polylactic acid resin composition containing a specific component can improve the releasability of the molded article, and the molded article can be easily released from a mirror mold having a surface roughness of 1.0 μm or less, which is generally difficult to release. This is considered to be because the specific mold release agent is transferred to the surface of the molded article during injection molding, and the molded article is easily released from the mold.
Specifically, first, a step of preparing a melt-kneaded product of the polylactic acid resin composition of the present invention (step 1) is performed, and then, a step of filling the obtained melt-kneaded product in an injection molding machine or an injection mold and molding the melt-kneaded product (step 2) is performed.
< working procedure 1 >
In step 1, a melt-kneaded product of the polylactic acid resin composition of the present invention is prepared.
[ polylactic acid resin composition ]
The polylactic acid resin composition of the present invention contains a plasticizer having a polyoxyalkylene group or an oxyalkylene group and a mold release agent having a melting point of 20 to 75 ℃ in addition to the polylactic acid resin. Since the plasticizer having the above-mentioned skeleton has high affinity with the polylactic acid resin, when a melt-kneaded product of the polylactic acid resin composition containing these components is filled in an injection molding machine at a high temperature set at 200 ℃ or higher, the release agent is likely to be transferred to the surface of the melt along with the softening of the polylactic acid resin. As a result, it is presumed that a molded article having improved releasability from a cylinder and further improved releasability from a mold and excellent surface appearance can be obtained. In the present specification, the plasticizer having a polyoxyalkylene group or an oxyalkylene group means a compound having 1 or 2 or more oxyalkylene groups, and hereinafter, they are collectively referred to simply as "a plasticizer having a polyoxyalkylene group". Therefore, the "plasticizer having a polyoxyalkylene group" refers to both a plasticizer having a polyoxyalkylene group and a plasticizer having an oxyalkylene group, unless otherwise specified.
[ polylactic acid resin ]
As the polylactic acid resin, there can be mentioned a polylactic acid resin synthesized from lactic acid and lactide by a known method, in addition to commercially available polylactic acid resins (for example, trade names: LACEAH-100, H-280, H-400, H-440 and the like manufactured by Mitsui chemical Co., Ltd.; trade names: NatureWorks PLA/NW3001D, NW403 4032D and the like manufactured by NatureWorks Co., Ltd.). From the viewpoint of improving strength and heat resistance, a polylactic acid resin having an optical purity of preferably 90% or more, more preferably 95% or more is preferable, and for example, a polylactic acid resin having a high molecular weight and a high optical purity manufactured by NatureWorks corporation (NW4032D and the like) is preferable. The optical purity is a molar percentage of L-form or D-form in the polylactic acid resin. In the present invention, the optical purity is preferably selected from the viewpoint of improving the surface appearance of the molded article because when poly L-lactic acid, which is a polymer of L-lactic acid, and poly D-lactic acid, which is a polymer of D-lactic acid, are mixed, a stereocomplex crystal is formed and the melting point is higher than that of the poly L-lactic acid crystal alone or that of the poly D-lactic acid crystal alone. The optical purity of polylactic acid can be determined by the method described in WO2011/096299 pamphlet, paragraph 0143.
In the present invention, in addition to the polylactic acid resin, other biodegradable resins may be appropriately contained within a range not to impair the effects of the present invention. Examples of the other biodegradable resins include polyester resins such as polybutylene succinate and polyhydroxyalkanoic acids. The polylactic acid resin may contain a polymer alloy obtained by blending polylactic acid with the above-mentioned other biodegradable resin or non-biodegradable resin such as polypropylene. The term "biodegradability" as used herein refers to a property that can be decomposed into low-molecular compounds by microorganisms in nature, and specifically refers to biodegradability in accordance with the final aerobic biodegradability and decay test under the controlled aerobic composting condition of JISK6953(ISO14855) (な biodegradability and sabelosis bad degrees test of かつ smart in コソポスト condition issued in された good emanation).
From the viewpoint of satisfying both strength and flexibility of the polylactic acid resin composition and improving heat resistance and productivity, the content of the polylactic acid resin in the total resin components contained in the composition is preferably 50% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and substantially more preferably 100% by weight.
[ plasticizer ]
In the present invention, a plasticizer having a polyoxyalkylene group is used. By blending the plasticizer having such a structure, the plasticity of the polylactic acid resin can be improved, crystallization can be promoted, the cooling retention time in the mold can be shortened, and the surface migration property of the release agent can be improved, so that the releasability from the cylinder and the mold can be improved, and the surface appearance of the obtained molded article can have excellent gloss.
The plasticizer having a polyoxyalkylene group is not particularly limited as long as it has such a structure. For example, an ester compound having a polyoxyalkylene group and an ether compound having a polyoxyalkylene group are exemplified, but an ester compound having a polyoxyalkylene group is preferable from the viewpoint of affinity with the polylactic acid resin.
The ester compound having a polyoxyalkylene group is preferably an ester compound in which at least 1 of alcohol components constituting the ester compound is an alcohol having 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms added on an average to 1 hydroxyl group. Among these, an ester compound having 2 or more ester groups in the molecule and at least 1 of the alcohol components constituting the ester compound is an alcohol having 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms added on average to 1 hydroxyl group is more preferable, and a polyol ester or a polycarboxylic acid ether ester having 2 or more ester groups in the molecule and at least 1 of the alcohol components constituting the ester compound is an alcohol having 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms added on average to 1 hydroxyl group is even more preferable. The alkylene oxide having 2 to 3 carbon atoms is preferably ethylene oxide from the viewpoint that the molded article has excellent surface appearance and gloss and mold fouling can be suppressed.
Specifically, preferred are esters formed from an alkylene oxide adduct of a polyhydric alcohol and a monocarboxylic acid, and esters formed from an aliphatic di-or tricarboxylic acid and a polyoxyalkylene glycol monoalkyl ether.
Examples of the polyhydric alcohol in the ester of the alkylene oxide adduct of the polyhydric alcohol and the monocarboxylic acid include ethylene glycol, polyethylene glycol, glycerin, and diglycerin. The monocarboxylic acid preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 2 carbon atoms.
The number of carbon atoms of the monoalkyl ether in the ester of an aliphatic di-or tricarboxylic acid and a polyoxyalkylene glycol monoalkyl ether is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2, and still more preferably 1. The aliphatic dicarboxylic acid is preferably a dicarboxylic acid having 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms. In the above-mentioned carbon number, the carbon number of the aliphatic compound also includes the carbon number of the carboxylic acid. Specific examples thereof include: oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, acid anhydrides thereof, alkyl (1 to 3 carbon atoms) esters thereof, and the like. As the aliphatic tricarboxylic acid, 1,3, 6-hexanetricarboxylic acid is exemplified. The number of carbon atoms does not include the number of carbon atoms of the alkyl ester of the dicarboxylic acid.
Further, from the viewpoint of excellent gloss of the surface appearance of the molded article and suppression of mold staining, specific compounds are preferably an ester formed from an average 3 to 6 mol adduct of acetic acid and ethylene oxide of glycerin, an ester formed from polyethylene glycol having an average mole number of acetic acid and ethylene oxide of 4 to 6, an ester formed from polyethylene glycol monomethyl ether having an average mole number of succinic acid and ethylene oxide of 2 to 3, an ester formed from adipic acid and diethylene glycol monomethyl ether, and an ester formed from 1,3, 6-hexanetricarboxylic acid and diethylene glycol monomethyl ether. From the viewpoints of moldability and impact resistance of the polylactic acid resin composition, and bleed-out resistance, volatility resistance, and pungent odor resistance of the plasticizer, an ester of succinic acid and triethylene glycol monomethyl ether is more preferable.
In addition, from the viewpoint of moldability and migration of the mold release agent, the ester compound having a polyoxyalkylene group is preferably a compound represented by the following formula (I).
R1O-CO-R2-CO-[(OR3)mO-CO-R2-CO-]nOR1(I)
(in the formula, R1Is alkyl of 1-8 carbon atoms, R2Is C2-4 alkylene, R3Is an alkylene group having 2 to 6 carbon atoms, m is a number of 1 to 6, n represents a number of 1 to 12, wherein all R2All R's may be the same or different3May be the same or different)
R in the formula (I)1Represents an alkyl group having 1 to 8 carbon atoms, 2 of which are present in 1 molecule and are present at both ends of the molecule. R1The carbon number is 1 to 8, and the carbon number may be a straight chain or a branched chain. The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 to 2, from the viewpoints of shortening the cooling time, suppressing mold contamination after mold release, and obtaining a molded article having an excellent surface appearance. Specific examples thereof include: among them, methyl group and ethyl group are preferable, and methyl group is more preferable, from the viewpoint of reducing mold contamination after mold release.
Formula (I)R in (1)2The alkylene group having 2 to 4 carbon atoms is represented, and a preferable example thereof is a linear alkylene group. Specific examples thereof include ethylene, 1, 3-propylene and 1, 4-butylene. From the viewpoint of reducing mold contamination after mold release, ethylene, 1, 3-propylene, and 1, 4-butylene are preferable, and ethylene is more preferable. In addition, all R2May be the same or different.
R in the formula (I)3Represents an alkylene group having 2 to 6 carbon atoms, which is present in the repeating unit in the form of an oxyalkylene group. R3The carbon number is 2 to 6, and the carbon number may be a straight chain or a branched chain. The number of carbon atoms of the alkylene group is preferably 2 to 6, more preferably 2 to 3, from the viewpoint of reducing mold contamination after mold release. Specific examples thereof include: ethylene, 1, 2-propylene, 1, 3-propylene, 1, 2-butylene, 1, 3-butylene, 1, 4-butylene, 2-methyl-1, 3-propylene, 1, 2-pentylene, 1, 4-pentylene, 1, 5-pentylene, 2-dimethyl-1, 3-propylene, 1, 2-hexylene, 1, 5-hexylene, 1, 6-hexylene, 2, 5-hexylene, 3-methyl-1, 5-pentylene, of which ethylene, 1, 2-propylene, 1, 3-propylene are preferred. In addition, all R3May be the same or different.
m represents an average number of repetition of oxyalkylene groups, and is a number of 1 to 6, preferably 1 to 4, more preferably 1 to 3, from the viewpoint of moldability.
n represents the average number of repeating units (average polymerization degree) and is a number of 1 to 12. From the viewpoint of improving compatibility with the polylactic acid resin, and improving plasticizing effect and plasticizing efficiency, the amount is preferably 1 to 6, and more preferably 1 to 4. The average polymerization degree can also be determined by analysis such as NMR, and can be calculated by the method described in the examples below.
As specific examples of the compounds represented by the formula (I), R is preferred1All are methyl, R2Is ethylene or 1, 4-butylene, R3A compound which is an ethylene group or a 1, 3-propylene group, m is a number of 1 to 4, and n is a number of 1 to 6,more preferably R1All are methyl, R2Is ethylene or 1, 4-butylene, R3A compound which is an ethylene group or a 1, 3-propylene group, wherein m is a number of 1 to 3 and n is a number of 1 to 5.
The compound represented by the formula (I) is not particularly limited as long as it has the above structure, and is preferably obtained by using the following raw materials (1) to (3). The compounds (1) and (2) obtained by esterification in advance and the compounds (2) and (3) obtained by esterification in advance may be used. (2) Acid anhydride or acid halide may be used.
(1) Monohydric alcohol having alkyl group of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms
(2) Dicarboxylic acid having C2-4 alkylene group
(3) A diol having an alkylene group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms
Specific examples of the above (1) to (3) are preferably:
(1) 1 or more than 2 selected from methanol, ethanol, 1-propanol and 1-butanol,
(2) 1 or 2 or more members selected from succinic acid, adipic acid, glutaric acid, and derivatives thereof (acid anhydride, methyl ester, and ethyl ester, the same applies hereinafter),
(3) 1 or more than 2 selected from diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, tetraethylene glycol and 1, 4-butanediol,
more preferably:
(1) methanol, methanol,
(2) 1 or more than 2 selected from succinic acid and derivatives thereof,
(3) Selected from 1 or more than 2 of diethylene glycol, triethylene glycol and 1, 3-propylene glycol.
The method for obtaining an ester compound using the above (1) to (3) is not particularly limited, and examples thereof include the following methods of schemes 1 and 2. The reaction conditions in each step may be those known to those skilled in the art (for example, Japanese patent laid-open No. 2012-62467).
Scheme 1: a method comprising the steps of (2) synthesizing a dicarboxylic acid ester by performing an esterification reaction between a dicarboxylic acid and (1) a monohydric alcohol (step 1) and (2) performing an esterification reaction between the obtained dicarboxylic acid ester and (3) a dihydric alcohol;
scheme 2: a method comprising a step of reacting (1) a monohydric alcohol, (2) a dicarboxylic acid, and (3) a dihydric alcohol at once.
The compound represented by the formula (I) preferably has an acid value of 1.50mgKOH/g or less, more preferably 1.00mgKOH/g or less, from the viewpoint of shortening the cooling time, suppressing mold contamination after mold release, and obtaining a molded article having an excellent surface appearance, and from the same viewpoint, preferably has a hydroxyl value of 10.0mgKOH/g or less, more preferably 5.0mgKOH/g or less, and still more preferably 4.0mgKOH/g or less. In the present specification, the acid value and the hydroxyl value of the plasticizer can be measured by the methods described in the examples below.
The number average molecular weight of the compound represented by formula (I) is preferably 300 or more, more preferably 400 or more, and preferably 1500 or less, more preferably 1000 or less, from the viewpoints of shortening the cooling time, suppressing mold contamination after mold release, and obtaining a molded article having an excellent surface appearance. Further, the amount is preferably 300 to 1500, and more preferably 400 to 1000. In the present specification, the number average molecular weight of the compound represented by the formula (I) can be measured by the method described in the examples below.
From the viewpoint of shortening the cooling time, suppressing mold contamination after mold release, and obtaining a molded article having an excellent surface appearance, the saponification value of the compound represented by formula (I) is preferably 500mgKOH/g or more, more preferably 550mgKOH/g or more, preferably 800mgKOH/g or less, and more preferably 750mgKOH/g or less. Further, it is preferably 500 to 800mgKOH/g, more preferably 550 to 750 mgKOH/g. In the present specification, the saponification value of the plasticizer can be measured by the method described in the examples below.
The alkyl esterification rate (terminal alkyl esterification rate) of the compound represented by formula (I) with respect to 2 molecular terminals is preferably 95% or more, more preferably 98% or more, from the viewpoints of shortening the cooling time, suppressing mold contamination after mold release, and obtaining a molded article having an excellent surface appearance. In the present specification, the esterification ratio of the terminal alkyl group of the plasticizer can be calculated by the method described in the examples below.
In addition, from the viewpoint of suppressing mold contamination after mold release and obtaining a molded article having excellent surface appearance by improving affinity with the polylactic acid resin and surface migration of the mold release agent, the solubility parameter value (, SP value) of the compound represented by formula (I) obtained by the Fedors method is preferably 10.0 or more, more preferably 10.1 or more, preferably 12.0 or less, more preferably 11.5 or less, and still more preferably 11.0 or less. In addition, the content is preferably 10.0 to 12.0, more preferably 10.1 to 11.5, and still more preferably 10.1 to 11.0.
Fedors formula (SP value) ═ ∑ Deltaei/∑ Deltavi)1/2
[ unit: (cal/cm)3)1/2]
[ wherein,. DELTA.ei: evaporation energy of atoms and atomic groups (cal/mol), Δ vi: molar volume (cm)3/mol)]
In the present invention, the SP value of the compound of formula (I) may be determined based on R1、R2、R3The number of carbon atoms, m, and n.
From the viewpoint of shortening the cooling time, suppressing mold contamination after mold release, and obtaining a molded article having an excellent surface appearance, the content of the plasticizer having a polyoxyalkylene group is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, further preferably 3 parts by weight or more, further preferably 5 parts by weight or more, and further preferably 6 parts by weight or more, relative to 100 parts by weight of the polylactic acid resin, and from the viewpoint of mold contamination, is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, further preferably 20 parts by weight or less, and further preferably 18 parts by weight or less. Further, it is preferably 0.1 to 30 parts by weight, more preferably 1 to 30 parts by weight, further preferably 3 to 25 parts by weight, further preferably 5 to 20 parts by weight, and further preferably 6 to 18 parts by weight. In the present specification, in the case where a plurality of plasticizers having a polyoxyalkylene group are used, the content thereof indicates the total content.
[ Release agent ]
The melting point of the release agent used in the present invention is 20 ℃ or higher, preferably 25 ℃ or higher, and more preferably 28 ℃ or higher from the viewpoint of suppressing bleeding out from the molded article, and is 75 ℃ or lower, preferably 65 ℃ or lower, and more preferably 48 ℃ or lower from the viewpoint of effectively transferring the release agent to the surface of the molded article, suppressing mold contamination after mold release, and obtaining a molded article having an excellent surface appearance. Therefore, from the above viewpoint, the melting point of the release agent is 20 to 75 ℃, preferably 25 to 65 ℃, and more preferably 28 to 48 ℃. In the present specification, the melting point of the release agent can be measured by the method described in the examples described below, and the melting point is also referred to as an ideal melting point.
Specifically, if the affinity with the plasticizer is low, the polylactic acid resin is softened, and the release agent is likely to migrate to the surface of the molten kneaded product, so that the molded product is likely to be released. Therefore, from these viewpoints, the following release agents (1) to (4) are preferable. In addition, a compound having no polyoxyalkylene group is preferable from the viewpoint that the release agent easily migrates to the surface when the affinity with the polylactic acid resin is low.
(1) Aliphatic hydrocarbons
(2) Fatty acids
(3) Fatty acid esters of polyhydric alcohols
(4) Esters or polyesters having perfluoroalkyl groups
As the aliphatic hydrocarbon (1), paraffin is preferable.
The fatty acid (2) is preferably a fatty acid having 12 to 30 carbon atoms, more preferably 14 to 22 carbon atoms. The fatty acid having 12 to 30 carbon atoms is preferably a saturated fatty acid, and more preferably myristic acid, palmitic acid, stearic acid, or behenic acid.
The fatty acid ester of the polyhydric alcohol (3) includes an ester (including a partial ester) of a polyhydric alcohol and a fatty acid having preferably 12 to 30 carbon atoms, more preferably 14 to 22 carbon atoms. The polyol is preferably a polyol having 3 or more hydroxyl groups, preferably one or two or more selected from glycerol, sorbitol and pentaerythritol, and more preferably pentaerythritol. As the fatty acid, the fatty acids described in the above (2) can be preferably mentioned. Specifically, the pentaerythritol fatty acid ester includes pentaerythritol distearate (melting point 50 ℃ C.), pentaerythritol tristearate (melting point 58 ℃ C.), and pentaerythritol tetrastearate (melting point 64 ℃ C.).
Examples of (4) the ester or polyester having a perfluoroalkyl group include: perfluoroalkyl group-containing (meth) acrylate, perfluoroalkyl group-containing maleic acid or fumaric acid ester, and polyester obtained by condensing an acid component containing perfluoroalkyl group-containing acrylic acid, maleic acid or fumaric acid with an alcohol component. The number of carbon atoms of the perfluoroalkyl group is preferably 6 to 18, more preferably 6 to 12.
These release agents may be used alone or in combination of 2 or more. Among them, from the viewpoint of obtaining a molded article excellent in surface appearance by suppressing mold contamination after mold release and suppressing mold release due to the combination with a plasticizer having a polyoxyalkylene group, (3) or (4) is preferable, that is, 1 or 2 or more selected from esters of polyhydric alcohols and fatty acids having 12 to 30 carbon atoms, esters having a perfluoroalkyl group, and polyesters having a perfluoroalkyl group are preferable, 1 or 2 or more selected from pentaerythritol fatty acid esters, esters having a perfluoroalkyl group, and polyesters having a perfluoroalkyl group are more preferable, and esters having a perfluoroalkyl group or polyesters having a perfluoroalkyl group are further preferable.
In the present invention, a combination of a known release agent having a melting point of less than 20 ℃ and a known release agent having a melting point of more than 75 ℃ other than the above release agent having a melting point of 20 to 75 ℃ may be used within a range not to impair the effects of the present invention.
The content of the release agent having the above-described ideal melting point is preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight or more, and further preferably 0.05 parts by weight or more, based on 100 parts by weight of the polylactic acid resin, from the viewpoint of exerting the effect as a release agent, and is preferably 2 parts by weight or less, more preferably 0.9 parts by weight or less, and more preferably 0.4 parts by weight or less, based on excellent mold contamination and surface appearance. Further, it is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 0.9 part by weight, and further preferably 0.05 to 0.4 part by weight.
The ratio of the content of the plasticizer having a polyoxyalkylene group to the content of the mold release agent having a desired melting point (plasticizer/mold release agent) is preferably 100/15 or more, more preferably 100/9 or more, and still more preferably 100/4 or more, from the viewpoint of effectively transferring the mold release agent to the surface of the molded article, and is preferably 100/0.1 or less, more preferably 100/0.3 or less, and still more preferably 100/0.5 or less from the viewpoint of excellent mold contamination and surface appearance. Further, it is preferably 100/0.1 to 100/15, more preferably 100/0.3 to 100/9, and further preferably 100/0.5 to 100/4.
The polylactic acid resin composition of the present invention may further contain an organic crystal nucleating agent in addition to the polylactic acid resin, the plasticizer having a polyoxyalkylene group, and the release agent having a melting point of 20 to 75 ℃. That is, as an embodiment of the polylactic acid resin composition of the present invention, there can be mentioned: an embodiment contains a polylactic acid resin, a plasticizer having a polyoxyalkylene group, a mold release agent having a melting point of 20 to 75 ℃, and an organic crystal nucleating agent.
[ organic nucleating agent ]
As the organic crystal nucleating agent that can be used in the present invention, from the viewpoint of increasing the crystallization rate of the polylactic acid resin and shortening the cooling retention time in the mold for taking out the molded article without deformation, 1 or 2 or more organic crystal nucleating agents selected from the following (a) to (d) are preferable.
(a) 1 or 2 or more organic compounds selected from the group consisting of a compound having an isoindolinone skeleton, a compound having a diketopyrrolopyrrole skeleton, a compound having a benzimidazolone skeleton, a compound having an indigo skeleton, a compound having a phthalocyanine skeleton, and a compound having a porphyrin skeleton [ referred to as an organic crystal nucleating agent (a) ]
(b) 1 or 2 or more organic compounds selected from the group consisting of homodiaminoureas, melamine compounds, uracils and N-substituted ureas [ referred to as organic crystal nucleating agents (b) ]
(c) 1 or 2 or more organic compounds selected from the group consisting of metal salts of dialkyl aromatic sulfonates, metal salts of phosphoric acid esters, metal salts of phenylphosphonic acid, metal salts of abietic acids, aromatic carboxylic acid amides, and abietic acid amides [ referred to as organic nucleating agents (c) ]
(d) 1 or 2 or more organic compounds selected from the group consisting of compounds having a hydroxyl group and an amide group in the molecule and hydroxy fatty acid esters [ referred to as organic nucleating agents (d) ]
Organic crystal nucleating agent (a)
As the organic crystal nucleating agent (a), 1 or 2 or more organic compounds selected from the following group can be exemplified: a compound having an isoindolinone skeleton, a compound having a diketopyrrolopyrrole skeleton, a compound having a benzimidazolone skeleton, a compound having an indigo skeleton, a compound having a phthalocyanine skeleton, and a compound having a porphyrin skeleton.
Organic crystal nucleating agent (b)
As the organic crystal nucleating agent (b), 1 or 2 or more organic compounds selected from the following group can be exemplified: diaminoureas, melamine compounds, uracils, and N-substituted ureas.
Organic crystal nucleating agent (c)
As the organic crystal nucleating agent (c), 1 or 2 or more organic compounds selected from the following group can be exemplified: metal salts of dialkyl aromatic sulfonates, metal salts of phosphoric acid esters, metal salts of phenylphosphonic acid, metal salts of abietic acids, aromatic carboxylic acid amides, and abietic acid amides.
Organic crystal nucleus agent (d)
As the organic crystal nucleating agent (d), 1 or 2 or more organic compounds selected from the following group can be exemplified: a compound having a hydroxyl group and an amide group in the molecule, and a hydroxy fatty acid ester.
Among these organic crystal nucleating agents, the organic crystal nucleating agent (c) and the organic crystal nucleating agent (d) are preferable from the viewpoint of shortening the cooling retention time in the mold.
From the above viewpoint, the organic crystal nucleating agent (c) is more preferably a compound having an optionally substituted phenyl group and a phosphonic acid group (-PO (OH))2) The metal salt of phenylphosphonic acid (b) may include, as a substituent of the phenyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms as an alkoxy group, and the like. Specific examples of phenylphosphonic acid include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, diethoxycarbonylphenylphosphonic acid and the like, with unsubstituted phenylphosphonic acid being preferred.
Examples of the metal salt of phenylphosphonic acid include salts of lithium, sodium, magnesium, aluminum, potassium, calcium, barium, copper, zinc, iron, cobalt, nickel, etc., and a zinc salt is preferable.
The compound having a hydroxyl group and an amide group in the molecule as the organic crystal nucleating agent (d) is preferably an aliphatic amide having a hydroxyl group, more preferably an aliphatic amide having 2 or more hydroxyl groups and 2 or more amide groups in the molecule, from the viewpoint of shortening the cooling retention time in the mold. Specific examples thereof include: and hydroxy fatty acid monoamides such as 12-hydroxystearic acid monoethanolamide, and hydroxy fatty acid bisamides such as methylene bis 12-hydroxystearamide, ethylene bis 12-hydroxystearamide, and hexamethylene bis 12-hydroxystearamide.
The hydroxy fatty acid ester is preferably a hydroxy fatty acid ester having 12 to 22 carbon atoms in a fatty acid, and more preferably a hydroxy fatty acid ester having 2 or more hydroxyl groups and 2 or more ester groups in the molecule. Specific examples thereof include: and hydroxy fatty acid esters such as 12-hydroxystearic acid triglyceride, 12-hydroxystearic acid diglyceride, 12-hydroxystearic acid monoglyceride, pentaerythritol-mono-12-hydroxystearate, pentaerythritol-di-12-hydroxystearate, and pentaerythritol-tri-12-hydroxystearate.
These organic crystal nucleating agents may be used alone or in combination of 2 or more, and among them, from the viewpoint of shortening the cooling retention time in the mold, 1 or more selected from the group consisting of metal salts of hydroxyalkanoic acid bisamides, phenylphosphonic acid, compounds having a phthalocyanine skeleton, and metal salts of aromatic sulfonic acid dialkyl esters is more preferable, and metal salts of ethylenebis 12-hydroxystearamide and phenylphosphonic acid are further preferable.
The content of the organic crystal nucleating agent is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, even more preferably 0.7 to 3 parts by weight, and even more preferably 0.7 to 2 parts by weight, based on 100 parts by weight of the polylactic acid resin, from the viewpoint of shortening the cooling and holding time in the mold for taking out the molded article without deformation. In the present specification, the content of the organic crystal nucleating agent refers to the total content of all the organic crystal nucleating agents contained in the polylactic acid resin composition.
The polylactic acid resin composition of the present invention may contain, as other components than the above, an inorganic crystal nucleating agent, a filler (inorganic filler or organic filler), a hydrolysis inhibitor, a flame retardant, an antioxidant, an ultraviolet absorber, an antistatic agent, an antifogging agent, a light stabilizer, a pigment, an antifungal agent, an antibacterial agent, a foaming agent, and the like, within a range not to impair the effects of the present invention. In addition, other polymer materials and other resin compositions may be added within a range not to impair the effects of the present invention.
The melt-kneaded product of the polylactic acid resin composition of the present invention can be prepared without particular limitation as long as it contains the polylactic acid resin, the plasticizer having a polyoxyalkylene group, and the release agent having a melting point of 20 to 75 ℃. For example, the polylactic acid resin composition can be prepared by melt-kneading raw materials containing the polylactic acid resin, the plasticizer having a polyoxyalkylene group, the release agent having a melting point of 20 to 75 ℃, and various additives used as needed, with a known kneader such as a closed kneader, a uniaxial or biaxial extruder, or an open roll type kneader. The raw materials may be previously mixed uniformly by a henschel mixer, a super mixer, or the like, and then supplied to melt-kneading. In order to promote the plasticity of the polylactic acid resin, the polylactic acid resin composition may be prepared by melt-mixing the polylactic acid resin composition in the presence of a supercritical gas.
The melt kneading temperature is preferably 170 ℃ or higher, preferably 240 ℃ or lower, and more preferably 220 ℃ or lower, from the viewpoint of improving moldability of the polylactic acid resin composition. In addition, the temperature is preferably 170 to 240 ℃, and more preferably 170 to 220 ℃. The melt kneading time is not generally determined depending on the melt kneading temperature and the type of the kneader, but is preferably 30 to 120 seconds.
After melt-kneading, the melt-kneaded product may be dried by a known method.
< step 2 >
In step 2, the molten and kneaded material obtained in step 1 is filled in an injection molding machine, and injected into a mold to be molded.
[ injection Molding machine ]
As the injection molding, a known injection molding machine can be used. For example, an injection molding machine having a cylinder and a screw inserted therein as main components [ J110AD-180H (manufactured by Nippon Steel works Co., Ltd.) ] and the like can be mentioned. In the present invention, from the viewpoint of improving the uniformity of the release agent, a material previously subjected to melt kneading is charged into the injection molding machine.
The set temperature of the cylinder is 200 ℃ or higher, preferably higher than 200 ℃, more preferably 205 ℃ or higher, from the viewpoint of improving the surface migration property of the release agent and improving the releasability of the molded article, and from the viewpoint of obtaining a molded article excellent in design property, and is preferably 230 ℃ or lower, more preferably 220 ℃ or lower, more preferably 214 ℃ or lower, and still more preferably 209 ℃ or lower from the viewpoint of suppressing the deterioration of the polylactic acid resin. When the set temperature of the cylinder is 200 ℃ or higher, the polylactic acid resin is sufficiently softened, the surface migration of the release agent is improved, the transferability of the mirror surface is improved, and the surface appearance is improved. Further, at 230 ℃ or lower, deterioration of the polylactic acid resin does not occur, and deterioration of mechanical properties such as appearance and heat resistance can be avoided. Therefore, the set temperature of the cylinder is preferably 200 to 230 ℃, more preferably higher than 200 ℃ and 230 ℃ or lower, further preferably higher than 200 ℃ and 214 ℃ or lower, further preferably higher than 200 ℃ and 209 ℃ or lower, and further preferably 205 to 209 ℃.
The cartridge is provided with a heater, whereby temperature adjustment can be performed. The number of heaters is not generally determined depending on the type of machine, but is usually 3 to 10 heaters along the longitudinal direction (the direction of travel of the screw). Therefore, in the case of having 2 or more heaters, the set temperature may be adjusted to be within the above range, preferably at least 1, more preferably 1 to (total number of heaters-1), and still more preferably (half of the total number of heaters) (in the case where the number of heaters is an odd number, half of the total number of heaters +1 to (total number of heaters-1). Further, the heater adjusted to the above-mentioned set temperature is preferably present in the vicinity of the molten kneaded material discharge port side (nozzle tip side), and when a plurality of heaters are set to the set temperature, it is more preferable that these heaters are present in order from the molten kneaded material discharge port side (nozzle tip side) toward the reverse direction (reverse direction of the screw).
[ mold ]
The surface roughness of the inside of the mold that can be used in the present invention is 1.0 μm or less, preferably 0.8 μm or less, and more preferably 0.5 μm or less, from the viewpoint of improving the surface appearance of the molded article. In the present invention, since a specific release agent and a plasticizer are used, the mold can be easily removed from the mirror-surface mold as described above. The lower limit is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.3 μm or more. In the present specification, the surface roughness of the mold is an index indicating the surface state of a machined surface when the mold is used to machine a part, and can be measured by the method described in JISB0601, as described in examples below. In addition, it is not necessary that the entire area of the machined surface of the mold satisfies the surface roughness, and at least a design surface of the machined surface, which is required to be a mirror surface, may satisfy the surface roughness. The area of the design surface required to be a mirror surface varies depending on the molded article, but is preferably 1cm2Above, more preferably 10cm2Above, 1 × 10 is preferable5cm2Hereinafter, more preferably 1 × 104cm2The following.
The surface temperature of the mold is preferably 85 ℃ or higher, more preferably 90 ℃ or higher, from the viewpoint of exerting an effect of the mold release agent and improving the mold release property of the molded article and from the viewpoint of improving the transferability of the molded article and obtaining a molded article excellent in design properties. From the viewpoint of promoting crystallization of the polylactic acid resin and improving moldability, it is preferably 120 ℃ or lower, more preferably 110 ℃ or lower, and still more preferably 100 ℃ or lower. Therefore, from the above viewpoint, the surface temperature of the mold is preferably 85 to 120 ℃, more preferably 90 to 110 ℃, and still more preferably 90 to 100 ℃.
From the viewpoint of exerting an effect of the release agent, improving the releasability of the molded body, and improving the transferability of the molded body, the surface temperature of the mold is preferably 10 ℃ or more, more preferably 20 ℃ or more, preferably 65 ℃ or less, more preferably 60 ℃ or less, higher than the melting point of the release agent, preferably 10 to 65 ℃ or more, more preferably 20 to 60 ℃ or more. In the present specification, the surface temperature of the mold is measured by the method described in the examples below, and is expressed as the number average of the measured values at 3 arbitrary points on the surface of the mold.
The holding time in the mold is not generally determined depending on the surface temperature of the mold, but is preferably 5 to 30 seconds, more preferably 5 to 25 seconds, and further preferably 5 to 20 seconds from the viewpoints of improving the surface appearance and suppressing mold contamination.
Thus, the production method of the present invention can reduce the holding time in the mold and suppress mold contamination after mold release, and therefore, a molded article having an excellent surface appearance can be produced with good productivity.
The present invention also provides a molded article obtainable by the production method of the present invention.
The molded article of the present invention is not particularly limited as long as it is obtained by the production method of the present invention, and can be produced by the above-mentioned method. That is, the molded article of the present invention can be obtained as follows: a polylactic acid resin composition containing a polylactic acid resin, a plasticizer having a polyoxyalkylene group, and a release agent having a melting point of 20-75 ℃ is melt-kneaded, and then the kneaded product is injection-molded in a mold having a surface roughness of 85 ℃ or higher by using an injection molding machine heated to a specific temperature. Since the polylactic acid resin composition contains a plasticizer having a high affinity with the polylactic acid resin and a release agent having a melting point of 20 to 75 ℃, the release agent melted by heating at the time of injection molding tends to migrate to the surface of the molten kneaded product, and as a result, transferability of the mold is improved, and a molded article having a glossy surface and excellent heat resistance can be obtained.
The molded article of the present invention has good surface appearance and excellent heat resistance, and therefore can be used at high temperatures, and is applicable to various applications, for example, to housings of information home appliances.
Preferred embodiments of the present invention are described below.
[1] A method for producing an injection-molded article of a polylactic acid resin composition, characterized in that a melt-kneaded product of a polylactic acid resin composition is filled in an injection-molding machine and molded in a mold, wherein the polylactic acid resin composition contains a polylactic acid resin, a plasticizer having a polyoxyalkylene group or oxyalkylene group, and a mold release agent having a melting point of 20 ℃ or higher, preferably 25 ℃ or higher, more preferably 28 ℃ or higher, 75 ℃ or lower, preferably 65 ℃ or lower, more preferably 48 ℃ or lower, and further 20 to 75 ℃, preferably 25 to 65 ℃ or lower, more preferably 28 to 48 ℃, and wherein the set temperature of at least a part of a cylinder of the injection-molding machine is 200 ℃ or higher, the surface temperature of the mold is 85 ℃ or higher, and the surface roughness of the mold is 1.0 [ mu ] m or lower.
[2] The production method according to the above [1], wherein the release agent preferably contains 1 or 2 or more selected from the group consisting of esters of polyhydric alcohols and fatty acids having 12 to 30 carbon atoms, preferably 14 to 22 carbon atoms, esters having perfluoroalkyl groups, and polyesters having perfluoroalkyl groups, and more preferably contains 1 or 2 or more selected from the group consisting of esters of pentaerythritol and fatty acids having 12 to 30 carbon atoms, preferably 14 to 22 carbon atoms, esters having perfluoroalkyl groups, and polyesters having perfluoroalkyl groups.
[3] The production method according to [2], wherein the polyol preferably contains a polyol having 3 or more hydroxyl groups, more preferably contains one or two or more selected from glycerol, sorbitol and pentaerythritol, and still more preferably contains pentaerythritol.
[4] The production method according to the above [2], wherein the ester or polyester having a perfluoroalkyl group comprises: perfluoroalkyl group-containing (meth) acrylate, perfluoroalkyl group-containing maleic acid or fumaric acid ester, or polyester obtained by condensing an acid component containing perfluoroalkyl group-containing acrylic acid, maleic acid or fumaric acid with an alcohol component.
[5] The production method according to any one of the above [1] to [4], wherein the content of the release agent is preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight or more, further preferably 0.05 parts by weight or more, preferably 2 parts by weight or less, more preferably 0.9 parts by weight or less, more preferably 0.4 parts by weight or less, and further preferably 0.01 to 2 parts by weight, more preferably 0.03 to 0.9 parts by weight, further preferably 0.05 to 0.4 parts by weight, based on 100 parts by weight of the polylactic acid resin.
[6] The production method according to any one of the above [1] to [5], wherein a ratio of a content (total content) of the plasticizer having a polyoxyalkylene group or an oxyalkylene group to a content of the release agent (plasticizer/release agent) is preferably 100/15 or more, more preferably 100/9 or more, further preferably 100/4 or more, preferably 100/0.1 or less, more preferably 100/0.3 or less, further preferably 100/0.5 or less, and further preferably 100/0.1 to 100/15, more preferably 100/0.3 to 100/9, further preferably 100/0.5 to 100/4.
[7] The production method according to any one of the above [1] to [6], wherein the plasticizer having a polyoxyalkylene group or an oxyalkylene group contains the following compound: a compound having 2 or more ester groups in a molecule, wherein 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms is added on average to 1 hydroxyl group in at least 1 of alcohol components constituting the ester.
[8] The production method according to any one of the above [1] to [7], wherein the plasticizer having a polyoxyalkylene group or an oxyalkylene group contains 1 or 2 or more species selected from the group consisting of: esters of oxyalkylene adducts of polyhydric alcohols with monocarboxylic acids, and esters of aliphatic di-or tricarboxylic acids with polyoxyalkylene glycol monoalkyl ethers.
[9] The production method according to any one of the above [1] to [6], wherein the plasticizer having a polyoxyalkylene group or oxyalkylene group contains an ester represented by the following formula (I).
R1O-CO-R2-CO-[(OR3)mO-CO-R2-CO-]nOR1(I)
(in the formula, R1Is an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, R2Is an alkylene group having 2 to 4 carbon atoms, preferably 2 carbon atoms, R3Is an alkylene group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms, m is a number of 1 to 6, preferably a number of 1 to 4, more preferably a number of 1 to 3, and n represents a number of 1 to 12, preferably a number of 1 to 6, more preferably a number of 1 to 4. Wherein all R are2All R's may be the same or different3May be the same or different)
[10] The production method according to item [9], wherein the solubility parameter value (SP value) of the ester represented by formula (I) by the Fedors method is 10.0 to 12.0.
[11] The production method according to [9] or [10], wherein the ester represented by the formula (I) is obtained using the following (1) to (3) as a raw material.
(1) A monohydric alcohol having an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms
(2) Dicarboxylic acid having alkylene group having 2 to 4 carbon atoms, preferably 2 carbon atoms
(3) A diol having an alkylene group having 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms
[12] The production method according to [11], wherein (1) the monohydric alcohol having an alkyl group with 1 to 8 carbon atoms contains 1 or 2 or more species selected from methanol, ethanol, 1-propanol and 1-butanol, (2) the dicarboxylic acid having an alkylene group with 2 to 4 carbon atoms contains 1 or 2 or more species selected from succinic acid, adipic acid, glutaric acid and derivatives thereof (anhydride, methyl ester or ethyl ester), (3) the dihydric alcohol having an alkylene group with 2 to 6 carbon atoms contains 1 or 2 or more species selected from diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, tetraethylene glycol and 1, 4-butanediol,
more preferably, (1) the monohydric alcohol having an alkyl group of 1 to 8 carbon atoms contains methanol, (2) the dicarboxylic acid having an alkylene group of 2 to 4 carbon atoms contains 1 or 2 or more members selected from succinic acid and derivatives thereof, and (3) the dihydric alcohol having an alkylene group of 2 to 6 carbon atoms contains 1 or 2 or more members selected from diethylene glycol, triethylene glycol and 1, 3-propanediol.
[13] The production method according to any one of the above [1] to [12], wherein the content (total content) of the plasticizer having a polyoxyalkylene group or an oxyalkylene group is preferably 0.1 part by weight or more, more preferably 1 part by weight or more, further preferably 3 parts by weight or more, further preferably 5 parts by weight or more, further preferably 6 parts by weight or more, preferably 30 parts by weight or less, more preferably 25 parts by weight or less, further preferably 20 parts by weight or less, further preferably 18 parts by weight or less, preferably 0.1 to 30 parts by weight, more preferably 1 to 30 parts by weight, further preferably 3 to 25 parts by weight, further preferably 5 to 20 parts by weight, further preferably 6 to 18 parts by weight, based on 100 parts by weight of the polylactic acid resin.
[14] The production method according to any one of the above [1] to [13], wherein the polylactic acid resin composition further contains an organic crystal nucleating agent.
[15] The production method according to [14], wherein the organic crystal nucleating agent preferably contains 1 or 2 or more selected from the group consisting of a hydroxy fatty acid bisamide, a metal salt of phenylphosphonic acid, a compound having a phthalocyanine skeleton, and a metal salt of aromatic dialkyl sulfonate, and more preferably contains an ethylenebis 12-hydroxystearamide and/or a metal salt of phenylphosphonic acid.
[16] The production method according to [14] or [15], wherein the content of the organic crystal nucleating agent is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, further preferably 0.7 to 3 parts by weight, and further preferably 0.7 to 2 parts by weight, based on 100 parts by weight of the polylactic acid resin.
[17] The production method according to any one of the above [1] to [16], wherein the set temperature of the cylinder is 200 ℃ or more, preferably more than 200 ℃, more preferably 205 ℃ or more, preferably 230 ℃ or less, more preferably 220 ℃ or less, further preferably 214 ℃ or less, further preferably 209 ℃ or less, and further preferably 200 to 230 ℃, more preferably more than 200 ℃ and 230 ℃ or less, further preferably more than 200 ℃ and 214 ℃ or less, further preferably more than 200 ℃ and 209 ℃ or less, further preferably 205 to 209 ℃.
[18] The production method according to any one of the above [1] to [17], wherein the number of heaters in the cylinder is preferably 3 to 10, and when the number of heaters is 2 or more, preferably at least 1, more preferably 1 to (total number of heaters-1), and further preferably (half of the total number of heaters) (wherein when the number of heaters is an odd number, the number is half of the total number of heaters + 1) to (total number of heaters-1) are adjusted to the set temperature of the cylinder.
[19] The production method according to any one of the above [1] to [18], wherein the surface roughness of the mold is preferably 0.8 μm or less, more preferably 0.5 μm or less, preferably 0.1 μm or more, more preferably 0.3 μm or more, and further preferably 0.1 to 1.0 μm, more preferably 0.3 to 0.9 μm.
[20] The production method according to any one of the above [1] to [19], wherein the surface temperature of the mold is preferably 85 ℃ or more, more preferably 90 ℃ or more, preferably 120 ℃ or less, more preferably 110 ℃ or less, further preferably 100 ℃ or less, and further preferably 85 to 120 ℃, more preferably 90 to 110 ℃, further preferably 90 to 100 ℃, further preferably 85 to 120 ℃.
[21] The production method according to any one of the above [1] to [19], wherein the surface temperature of the mold is preferably 10 ℃ or more, more preferably 20 ℃ or more, more preferably 65 ℃ or less, more preferably 60 ℃ or less higher than the melting point of the mold release agent, preferably 10 to 65 ℃ or more, more preferably 20 to 60 ℃ higher than the melting point of the mold release agent.
[22] The production method according to any one of the above [1] to [21], wherein the polylactic acid resin has an optical purity (purity of L-form or D-form) of preferably 90% or more, more preferably 95% or more.
[23] A molded article obtained by the production method according to any one of the above [1] to [22 ].
Examples
The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples, the parts are parts by weight unless otherwise specified. The "normal pressure" is 101.3kPa, and the "normal temperature" is 15 to 25 ℃.
[ acid value, hydroxyl value and saponification value of plasticizer ]
Acid value: analysis was performed according to the test method of JISK0070, except that toluene/ethanol (volume ratio) 2/1 was used as a titration solvent.
Hydroxyl value: analysis was performed according to the test method of JISK0070, except that 1/4 (volume ratio) of acetic anhydride/pyridine was used as an acetylation reagent and the amount of the acetylation reagent added was 3 mL.
Saponification value: the analysis was carried out according to the test method of JIS K0070 except that the temperature of the water bath was set to 95 ℃ and the heating time was set to 1 hour.
[ molecular weight, terminal alkyl esterification ratio, and Ether number of Compound represented by formula (I) ]
Molecular weight: in the present specification, the molecular weight of the compound represented by formula (I) is a number average molecular weight, and is calculated from an acid value, a hydroxyl value, and a saponification value by the following formula.
Average molecular weight
M＝(M1+M2-M3×2)×n+M1-(M3-17.01)×2+(M3-17.01)×p+(M2-17.01)×q+1.01×(2-p-q)
q-hydroxyl value × M ÷ 56110
2-p-q ═ acid number × M ÷ 56110
Average degree of polymerization n ═ saponification value × M ÷ (2 × 56110) -1
Terminal alkyl esterification rate: the ratio of alkyl esterification at the molecular terminal (terminal alkyl esterification ratio) can be determined by the following formula, and when the value of the ratio of alkyl esterification at the molecular terminal is large, it means that the number of free carboxyl groups and hydroxyl groups is small, and the molecular terminal is sufficiently alkyl-esterified.
Terminal alkyl esterification ratio (%) (p/2) × 100
Wherein,
M1: molecular weight of diester of dicarboxylic acid used as raw material and monohydric alcohol used as raw material
M2: molecular weight of diol used as raw Material
M3: molecular weight of monohydric alcohol used as raw material
p: number of terminal alkyl ester groups in one molecule
q: number of terminal hydroxyl groups in one molecule
Ether value: the number of millimoles (mmol) of ether groups in 1g of the compound represented by formula (I), that is, the ether value, was calculated by the following formula.
Ether value (mmol/g) ═ M-1 × n × 1000 ÷ M
Wherein m: average number of repetition of oxyalkylene group (m-1 represents the number of ether groups in one molecule of glycol)
When a plurality of dicarboxylic acids, monohydric alcohols, and dihydric alcohols are used, the molecular weight is a number average molecular weight.
[ molecular weight of plasticizer other than the Compound represented by the formula (I) ]
The molecular weight of the plasticizer other than the compound represented by formula (I) is a weight average molecular weight, and is calculated from the saponification value by the following formula.
Average molecular weight of 56108 × (number of ester groups in 1 molecule)/saponification number
[ melting Point of mold Release agent ]
The melting point of the release agent was determined by a melting point measuring apparatus (model B-545, manufactured by Kashida scientific Co., Ltd.) according to a method based on the light transmittance measuring method of JIS-K0064(1992) (2).
[ surface temperature of mold ]
The surface temperature of the mold was measured at 3 points, i.e., the upper end, the center, and the lower end of the product portion of the mold by a contact thermometer, and the average value thereof was taken as the surface temperature of the mold.
[ surface roughness of mold ]
The surface roughness of the mold was measured at a measuring speed of 0.05mm/s by a stylus surface roughness measuring instrument (SV-C4000CNC, manufactured by Sanfeng Co., Ltd.) based on JISB0601 (2001).
Production example 1 (diester of succinic acid and triethylene glycol monomethyl ether) >, plasticizer
500g of succinic anhydride, 2463g of triethylene glycol monomethyl ether, and 9.5g of p-toluenesulfonic acid monohydrate were charged into a 3L flask equipped with a stirrer, a thermometer, and a dehydration tube, and reacted at 110 ℃ for 15 hours under reduced pressure (4 to 10.7kPa) while blowing nitrogen (500 mL/min) into the void (space). The acid value of the reaction mixture was 1.6 (mgKOH/g). 27g of adsorbent Kyoward500SH (manufactured by Kyowa chemical industries Co., Ltd.) was added to the reaction solution, and after stirring at 80 ℃ and 2.7kPa for 45 minutes, the mixture was filtered, then triethylene glycol monomethyl ether was distilled off at a liquid temperature of 115 to 200 ℃ and a pressure of 0.03kPa, and after cooling to 80 ℃, the residue was filtered under reduced pressure to obtain a filtrate diester of succinic acid and triethylene glycol monomethyl ether. The acid value of the obtained diester was 0.2(mgKOH/g), the saponification value was 276(mgKOH/g), the hydroxyl value was 1 or less (mgKOH/g), and the color tone was APHA 200.
Production example 2 (triester of 1,3, 6-Hexane tricarboxylic acid with triethylene glycol monomethyl Ether) >, plasticizer
Triethylene glycol monomethyl ether, 1,3, 6-hexanetricarboxylic acid and p-toluenesulfonic acid monohydrate as a catalyst were charged into a reaction vessel so that triethylene glycol monomethyl ether/1, 3, 6-hexanetricarboxylic acid/p-toluenesulfonic acid monohydrate (molar ratio) was 4/1/0.02, and dehydration was performed at 120 ℃ under reduced pressure to obtain a triester of 1,3, 6-hexanetricarboxylic acid and triethylene glycol monomethyl ether.
Production example 3 (triester of ethylene oxide adduct of glycerin to 3 moles of ethylene oxide and acetic acid) >, a plasticizer
A process for producing a cosmetic preparation by autoclaving a concentrated glycerin/ethylene oxide ratio of 3 mol/1 mol/mol KOH/0.3 MPa under constant pressure, reacting at 150 ℃ until the pressure becomes constant, and then cooling to 80 ℃ to obtain a product without catalyst neutralization. Kyoward600S (available from Kyowa chemical industries Co., Ltd.) was added to the product in an amount of 8 times the weight of the catalyst as an adsorbent, and the adsorption treatment was carried out at 80 ℃ for 1 hour under a slight nitrogen pressure. Then, the adsorbent was filtered off from the treated liquid using a buchner funnel in which No.2 filter paper was precoated with radius #900, to obtain an ethylene oxide 3 mol adduct of glycerin (hereinafter referred to as POE (3) glycerin). This adduct was put into a four-necked flask, heated to 105 ℃ and stirred at 300r/min, and a predetermined amount of acetic anhydride was added dropwise over about 1 hour so as to react at a ratio of 3.6 moles per 1 mole of POE (3) glycerol. After the dropwise addition, the mixture was aged at 110 ℃ for 2 hours and then at 120 ℃ for 1 hour. After the aging, unreacted acetic anhydride and by-produced acetic acid were distilled off under reduced pressure and then vaporized to obtain POE (3) triacetin.
< production example 4 of plasticizer (production example 1 of Compound represented by formula (I) >)
In a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube and a nitrogen-blowing tube were charged 363g (342 mol) of diethylene glycol and 6.6g (0.034 mol) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst, and methanol was distilled off while stirring at 120 ℃ for 0.5 hour under normal pressure. Then, 1000g (6.84 mol) of dimethyl succinate (Wako pure chemical industries, Ltd.) was added dropwise over 3 hours, and methanol produced in the reaction was distilled off at 120 ℃ under normal pressure. Subsequently, after cooling to 75 ℃ and distilling off methanol by gradually lowering the pressure from normal pressure to 6.7kPa for 1.5 hours, the pressure was returned to normal pressure, and 5.8g (0.030 mol of sodium methoxide) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst was added thereto, and methanol was distilled off by gradually lowering the pressure from normal pressure to 2.9kPa for 2 hours at 100 ℃. Then, the mixture was cooled to 80 ℃ and 18g of Kyoward600S (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The temperature of the filtrate was raised from 70 ℃ to 190 ℃ over 1 hour under a pressure of 0.3kPa to distill off the residual dimethyl succinate, and a yellow liquid at room temperature was obtained. The amount of the catalyst used was 0.94 mol based on 100 mol of the dicarboxylic acid ester.
< production example 5 of plasticizer (production example 2 of Compound represented by formula (I) >)
A four-necked flask (equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube, and a nitrogen-blowing tube) was charged with 581g (5.47 mol) of diethylene glycol and 9.1g (0.047 mol) of a methanol solution containing 28 wt% sodium methoxide as a catalyst, and the mixture was stirred at 120 ℃ for 0.5 hour under normal pressure to distill off methanol. Then, 1200g (8.21 mol) of dimethyl succinate (Wako pure chemical industries, Ltd.) was added dropwise over 2 hours, and methanol produced by the reaction was distilled off at 120 ℃ under normal pressure. Subsequently, after cooling to 75 ℃ and distilling off methanol by gradually lowering the pressure from normal pressure to 6.7kPa for 1.5 hours, the pressure was returned to normal pressure, and 9.8g (0.051 mol of sodium methoxide) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst was added thereto, and methanol was distilled off by gradually lowering the pressure from normal pressure to 2.9kPa for 2 hours at 100 ℃. Then, the mixture was cooled to 80 ℃ and 28g of Kyoward600S (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The temperature of the filtrate was raised from 70 ℃ to 170 ℃ over 2.5 hours under a pressure of 0.3kPa to distill off the residual dimethyl succinate, and a yellow liquid at room temperature was obtained. The amount of the catalyst used was 1.2 mol based on 100 mol of the dicarboxylic acid ester.
< production example 6 of plasticizer (production example 3 of Compound represented by formula (I) >)
In a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube and a nitrogen-blowing tube, 521g (6.84 mol) of 1, 3-propanediol and 5.9g (0.031 mol) of a methanol solution containing 28 wt% sodium methoxide as a catalyst were placed, and methanol was distilled off while stirring at 120 ℃ for 0.5 hour under normal pressure. Then, 1500g (10.26 mol) of dimethyl succinate (Wako pure chemical industries, Ltd.) was added dropwise over 1 hour, and methanol produced by the reaction was distilled off at 120 ℃ under normal pressure. Subsequently, the mixture was cooled to 60 ℃, 5.6g of a 28 wt% sodium methoxide solution in methanol (0.029 mol of sodium methoxide) was added thereto, and the mixture was heated to 120 ℃ over 2 hours, and then the pressure was gradually lowered from normal pressure to 3.7kPa over 1 hour to distill off the methanol. Then, the mixture was cooled to 80 ℃ and 18g of Kyoward600S (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The temperature of the filtrate was raised from 85 ℃ to 194 ℃ over 2.5 hours under a pressure of 0.1kPa to distill off the residual dimethyl succinate, and a yellow liquid at room temperature was obtained. The amount of the catalyst used was 0.58 mol based on 100 mol of the dicarboxylic acid ester.
< production example 7 of plasticizer (production example 4 of Compound represented by formula (I) >)
764g (10.0 mol) of 1, 2-propanediol and 14.0g (0.073 mol) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst were put in a four-necked flask (equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube, and a nitrogen-blowing tube), and methanol was distilled off while stirring at 120 ℃ for 0.5 hour under normal pressure. Then, 2200g (15.05 mol) of dimethyl succinate (Wako pure chemical industries, Ltd.) was added dropwise over 2.5 hours, and methanol produced by the reaction was distilled off at 120 ℃ under normal pressure. Subsequently, after cooling to 75 ℃ and distilling off methanol by gradually lowering the pressure from normal pressure to 6.7kPa over 0.5 hour, the pressure was returned to normal pressure, and 6.4g (0.033 mol) of a methanol solution containing 28 wt% sodium methoxide as a catalyst was added thereto, and methanol was distilled off by gradually lowering the pressure from normal pressure to 5.3kPa over 1 hour at 110 ℃. After cooling to 75 ℃ and returning to normal pressure, 8.4g (0.044 mol) of a 28 wt% sodium methoxide-containing methanol solution was added again as a catalyst, and the pressure was gradually lowered from normal pressure to 1.6kPa at 110 ℃ over 2 hours to distill off methanol. Then, the mixture was cooled to 80 ℃ and 47g of Kyoward600S (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The temperature of the filtrate was raised from 115 ℃ to 200 ℃ over 1 hour under a pressure of 0.4kPa to distill off the residual dimethyl succinate, and a yellow liquid at room temperature was obtained. The amount of the catalyst used was 1.82 mol based on 100 mol of the dicarboxylic acid ester.
< production example 8 of plasticizer (production example 5 of Compound represented by formula (I) >)
Into a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube and a nitrogen-blowing tube were charged 955g (12.6 mol) of 1, 2-propanediol and 15.4g (0.080 mol) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst, and methanol was distilled off while stirring at 120 ℃ for 0.5 hour under normal pressure. Then, 2567g (17.56 mol) of dimethyl succinate (Wako pure chemical industries, Ltd.) was added dropwise over 2 hours, and methanol produced by the reaction was distilled off at 120 ℃ under normal pressure. Subsequently, after cooling to 75 ℃ and distilling off methanol by gradually lowering the pressure from normal pressure to 6.7kPa over 0.5 hour, the pressure was returned to normal pressure, and 8.1g (0.042 mol of sodium methoxide) of a 28 wt% sodium methoxide-containing methanol solution as a catalyst was added thereto, and methanol was distilled off by gradually lowering the pressure from normal pressure to 5.3kPa over 1 hour at 110 ℃. After cooling to 75 ℃ and returning to normal pressure, 10.8g (0.056 mol) of a 28 wt% sodium methoxide-containing methanol solution as a catalyst was added again, and the pressure was gradually lowered from normal pressure to 1.6kPa at 110 ℃ over 4 hours to distill off methanol. Then, the mixture was cooled to 80 ℃ and 47g of Kyoward600S (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The temperature of the filtrate was raised from 102 ℃ to 200 ℃ over 3 hours under a pressure of 0.8kPa to distill off the residual dimethyl succinate, and a yellow liquid at room temperature was obtained. The amount of the catalyst used was 1.71 mol based on 100 mol of the dicarboxylic acid ester.
< production example 9 of plasticizer (production example 6 of Compound represented by formula (I) >)
In a four-necked flask equipped with a stirrer, a thermometer, a distillation tube and a nitrogen gas blowing tube, 369g (3.47 mol) of diethylene glycol and 5.6g (0.029 mol) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst were charged, and methanol was distilled off while stirring at 84 ℃ and under a pressure of 3.6kPa for 0.5 hour. 1600g (6.95 mol) of dibutyl succinate obtained in the same manner as in production example 10 was added dropwise at 79 ℃ under a pressure of 2.7kPa for 2.5 hours, and 1-butanol formed by the reaction was distilled off. Then, the reaction mixture was returned to normal pressure, and 2.1g of a 28 wt% sodium methoxide-containing methanol solution (0.011 mol of sodium methoxide) was added thereto, and the temperature was gradually raised from 85 ℃ and 2.1kPa over 1.5 hours to 146 ℃ and 1.1kPa to distill 1-butanol formed in the reaction. Then, the mixture was cooled to 80 ℃ and 11g of Kyoward600S (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure to obtain a yellow liquid at room temperature. The amount of the catalyst used was 0.58 mol based on 100 mol of the dicarboxylic acid ester.
< production example 10 of plasticizer (production example 7 of Compound represented by formula (I) >)
999g (9.41 mol) of diethylene glycol and 23.6g (0.122 mol) of a methanol solution containing 28 wt% sodium methoxide as a catalyst were put in a four-necked flask (equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube, and a nitrogen-blowing tube), and methanol was distilled off while stirring at normal pressure (101.3kPa) and 120 ℃ for 0.5 hour. Then, 4125g (28.2 mol) of dimethyl succinate (Wako pure chemical industries, Ltd.) was added dropwise over 3 hours, and methanol produced in the reaction was distilled off at 120 ℃ under normal pressure. Subsequently, after cooling to 75 ℃ and distilling off methanol by gradually lowering the pressure from normal pressure to 6.7kPa over 2 hours, the pressure was returned to normal pressure, and 4.4g (0.023 mol) of a methanol solution containing 28 wt% sodium methoxide as a catalyst was added thereto, and methanol was distilled off by gradually lowering the pressure from normal pressure to 2.9kPa over 2 hours at 100 ℃. Then, the mixture was cooled to 80 ℃ and 41g of Kyoward600S (Kyowa chemical Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The temperature of the filtrate was raised from 70 ℃ to 190 ℃ over 4 hours under a pressure of 0.3kPa to distill off the residual dimethyl succinate, and a yellow liquid at room temperature was obtained. The amount of the catalyst used was 0.51 mol based on 100 mol of the dicarboxylic acid ester.
< production example 11 of plasticizer (production example 8 of Compound represented by formula (I) >)
In a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube and a nitrogen blowing tube, 263.5g (2.53 mol) of neopentyl glycol, 1500g (4.05 mol) of bis (2-ethylhexyl) adipate and 5.6g (0.029 mol) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst were charged, and the resulting mixture was reacted at 120 ℃ under a pressure of 3.7kPa for 1.5 hours while distilling off 2-ethylhexanol formed by the reaction. Then, after cooling to 75 ℃, the reaction mixture was returned to normal pressure, and 3.0g (0.016 mol) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst was added thereto, and the temperature was raised from 92 ℃ to 160 ℃ over 1 hour under a pressure of 0.4kPa to distill off 2-ethylhexanol. Then, the mixture was cooled to 80 ℃ and 19g of Kyoward600S (Kyowa chemical Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. 504g of bis (2-ethylhexyl) adipate remaining was distilled off by raising the temperature of the filtrate from 166 ℃ to 214 ℃ over 2 hours under a pressure of 0.3kPa to obtain a yellow liquid at room temperature. The amount of the catalyst used was 1.11 mol based on 100 mol of the dicarboxylic acid ester.
< production example 12 of plasticizer (production example 9 of Compound represented by formula (I) >)
In a four-necked flask equipped with a stirrer, a thermometer, a Dean-Stark apparatus and a nitrogen gas blowing tube, 2515g (19.3 mol) of 2-ethylhexanol (manufactured by Kanto chemical Co., Ltd.), 877g (7.43 mol) of succinic acid (manufactured by Wako pure chemical industries, Ltd.) and 14.1g (0.0742 mol) of p-toluenesulfonic acid monohydrate (manufactured by Wako pure chemical industries, Ltd.) were charged, and reacted from a state of a pressure of 16kPa and 80 ℃ to a state of a pressure of 12kPa and 90 ℃ over 7 hours to distill water. Then, 32g of Kyoward500SH (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The filtrate was charged into a four-necked flask (equipped with a stirrer, a thermometer, a distillation tube and a nitrogen-blowing tube), and after converting the pressure from a state of 0.7kPa and 95 ℃ to a state of 0.5kPa and 185 ℃, the residual 2-ethylhexanol was distilled off, Kyoward500SH16g was added again, and after stirring at a pressure of 4.0kPa and 80 ℃ for 1 hour, filtration was carried out under reduced pressure to obtain bis (2-ethylhexyl) succinate. Then, 467g (1.36 mol) of the bis (2-ethylhexyl) succinate, 250g (2.36 mol) of diethylene glycol, and 2.2g (0.011 mol) of a methanol solution containing 28 wt% of sodium methoxide as a catalyst were charged into a four-necked flask (equipped with a stirrer, a thermometer, a dropping funnel, a distillation tube, and a nitrogen gas blowing tube), and the pressure was gradually decreased from 2.7kPa to 0.9kPa over 45 minutes at 110 ℃ to distill off 2-ethylhexanol produced in the reaction. After cooling to 80 ℃, 1953g (5.70 mol) of bis (2-ethylhexyl) succinate and 5.0g (0.026 mol) of a 28 wt% sodium methoxide solution in methanol were added again, and the pressure was gradually reduced while the temperature was increased over 5.5 hours, thereby changing the temperature from 110 ℃ and 0.8kPa to 158 ℃ and 0.4kPa, and distilling off the 2-ethylhexanol formed by the reaction. Then, the mixture was cooled to 80 ℃ and 10.5g of Kyoward600S (manufactured by Kyowa chemical industries Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ under a pressure of 4.0kPa for 1 hour, followed by filtration under reduced pressure. The filtrate was changed from 178 ℃ and 0.3kPa to 220 ℃ and 0.1kPa by gradually lowering the pressure while increasing the temperature for 4.5 hours, and the residual bis (2-ethylhexyl) succinate was distilled off to obtain a yellow liquid at room temperature. The amount of the catalyst used was 0.53 mol based on 100 mol of the dicarboxylic acid ester.
(calculation example of SP value)
The SP value of the compound represented by the formula (I) was calculated as follows. As a specific example, a calculation example of the compound represented by the formula (I) obtained in production example 7 is shown.
The compound of production example 7 was the following compound.
R1O-CO-R2-CO-[(OR3)mO-CO-R2-CO-]nOR1
(，R1: methyl, R2: ethylene radical, R3: ethylene group, m: 2. n: 1.6)
Namely, the resin composition has 2 methyl groups, 11.6 methylene groups, 5.2 ester groups and 1.6 ether groups.
Thus, when calculated based on the Fedors formula, Δ ei for methyl is 1125(cal/mol), Δ vi is 33.5(cal/mol), Δ ei for methylene is 1180(cal/mol), Δ vi is 16.1(cal/mol), Δ ei for ester group is 4300(cal/mol), Δ vi is 18.0(cal/mol), Δ ei for ether group is 800(cal/mol), Δ vi is 3.8 (cal/mol). The SP value calculated from these values was 10.6.
Fedors formula: (∑ delta ei/∑ delta vi)1/2
[ unit: (cal/cm)3)1/2]
[ wherein,. DELTA.ei: evaporation energy of atoms and atomic groups (cal/mol), Δ vi: molar volume (cm)3/mol)]
The acid value, hydroxyl value and saponification value of the compound represented by the formula (I) were measured, and the number average molecular weight, the terminal alkyl esterification ratio, the average polymerization degree (n) and the ether value were calculated based on the above formula. The SP value was also calculated in the above manner. The results are shown in tables 1 to 2.
[ Table 1]
[ Table 2]
Examples 1 to 29 and comparative examples 1 to 7
The raw materials of the polylactic acid resin compositions shown in tables 3 to 6 were melt-kneaded at 190 ℃ using a homodromous twin-screw extruder (TEM-41 SS manufactured by toshiba corporation) and pelletized (strandcut) to obtain pellets of the polylactic acid resin compositions. The obtained pellets were dried at 110 ℃ for 2 hours to remove moisture so that the moisture content was 500ppm or less.
The obtained pellets were injection-molded using an injection molding machine (J110 AD-180H, manufactured by Japan Steel works, Ltd., cylinder temperature setting of 6 locations). The cylinder temperature was set to the temperatures shown in tables 3 to 6 from the nozzle tip side to the 5 th unit, the remaining 1 unit was set to 170 ℃, and the temperature below the hopper was set to 45 ℃. Molded articles of polylactic acid resin compositions of examples 1 to 29 and comparative examples 1 to 7 were obtained by molding a flat plate (100 mm. times.100 mm. times.2 mm) at a mold temperature shown in tables 3 to 6 by using a mirror mold having a surface roughness shown in tables 3 to 6.
The raw materials in tables 3 to 6 are as follows.
[ polylactic acid resin ]
NW 4032D: NatureWorks4032D manufactured by NatureWorks corporation, L-body purity 98.6%
[ plasticizer ]
(MeEO3)2And SA: diester compound of succinic acid and triethylene glycol monomethyl ether produced in production example 1 of the plasticizer, and average molecular weight 410
DAIFATTY-101: mixed diester of adipic acid and diethylene glycol monomethyl ether/benzyl alcohol 1/1 (Dai-Octao chemical industries, Ltd.), average molecular weight 338
(MeEO3)3TA: triester Compound of 1,3, 6-Hexane tricarboxylic acid and triethylene glycol monomethyl Ether produced in production example 2 of the plasticizer, average molecular weight 656
(AcEO)3Gly: the plasticizer was prepared in example 3, wherein an ethylene oxide adduct comprising 3 moles of ethylene oxide added to glycerin was a triester compound of acetic acid and had an average molecular weight of 350
ATBC: acetyl tributyl citrate (manufactured by Taoka chemical Co., Ltd.), average molecular weight 402
A compound of formula (I): production examples 1 to 9 of Compound represented by formula (I)
[ Release agent ]
DaifreeFB-961: perfluoroalkyl polyester (melting point 30 ℃ C. manufactured by Dajin Co.)
LOXIOLP 728: pentaerythritol distearate (produced by EmeryOleochogicals Japan, melting Point 50 ℃ C.)
LOXIOLVGP 861: pentaerythritol tetrastearate (product of EmeryOleochemicals Japan, melting point 64 ℃ C.)
SlipaxE: ethylene bis stearamide (melting point 144 ℃ C. manufactured by Nippon chemical Co., Ltd.)
Licowax e: montanic acid ester (ethylene glycol octacosanoate) (manufactured by Clariant Japan, melting Point 82 ℃ C.)
[ nucleating agent ]
SlipaxH: ethylene bis 12-hydroxystearamide (manufactured by Nippon Kasei Co., Ltd.)
Ecopromote: unsubstituted zinc phenylphosphonate (manufactured by Nissan chemical industries Co., Ltd.)
Microacept 6: talc (manufactured by Japan Talc Co., Ltd.)
The physical properties of the molded articles obtained were examined by the methods of test examples 1 to 3 below. The results are shown in tables 3 to 6.
< test example 1 > (Cooling time taken to enable extraction without deformation)
The cooling time required for molding without causing a mark or deflection by the plunger (ejjectpin) when a flat plate (100mm × 100mm × 2mm) was molded by a mirror mold at a predetermined barrel temperature and mold temperature was measured. The shorter the cooling time, the more excellent the moldability, and the upper limit was 120 seconds.
< test example 2 > (surface appearance)
The surface appearance of the flat plate produced in test example 1 was visually observed and evaluated according to the following evaluation criteria. The higher the gloss, the better the transferability of the mold and the more excellent the design.
[ evaluation standards ]
A: the mirror surface is transferred and has a gloss as a whole.
B: the mirror surface can be transferred, and about 90% of the whole mirror surface has luster.
C: the mirror surface is transferred, and about 80% of the whole mirror surface has luster.
D: the mirror surface cannot be transferred and the gloss is low.
< test example 3 > (mold contamination)
The surface appearance of the mold after 10 times (10 shots) of the flat plate of test example 1 was produced under each condition was visually observed and evaluated according to the following evaluation criteria. The less mold contamination, the more excellent moldability.
[ evaluation standards ]
A: there is no mold contamination.
B: the mold contamination was substantially insignificant.
C: slightly obvious pollution to the mold
D: the mold is contaminated as a whole.
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
From the results shown in tables 3 to 6, it is understood that the molded articles (examples 1 to 29) obtained by molding the polylactic acid resin composition containing the plasticizer having a polyoxyalkylene group or oxyalkylene group, the mold release agent having a melting point of 20 to 75 ℃ and the crystal nucleus agent under the conditions that the cylinder setting temperature is 200 ℃ or more and the surface temperature of the mold having a specific surface roughness is 85 ℃ or more can be molded without deformation in a short cooling time and are excellent in the surface appearance and mold contamination.
On the other hand, the molded articles of the polylactic acid resin compositions (comparative examples 1 to 2) containing no specific plasticizer could not be molded without deformation. When a composition having the same composition as in example 1 was molded using a mold having a surface roughness of 1.3 μm, a molded article having a poor surface appearance was obtained (comparative example 3). The molded articles of the polylactic acid resin compositions of comparative examples 4 to 5, which did not contain a specific release agent, had a long cooling time and had poor surface appearance and mold fouling. Further, the molded article obtained by molding at a cylinder set temperature of 190 ℃ (comparative example 6) and the molded article obtained by molding at a mold temperature of 80 ℃ (comparative example 7) were poor in surface appearance.
Industrial applicability of the invention
The molded article obtained by the production method of the present invention has high productivity and excellent surface appearance, and therefore, can be suitably used for various industrial applications such as daily miscellaneous goods, home electric appliance parts, binding materials for home electric appliance parts, and automobile parts.
Claims (30)
1. A method for producing an injection-molded article of a polylactic acid resin composition, characterized by comprising charging a melt-kneaded product of a polylactic acid resin composition into an injection-molding machine and molding the mixture in a mold, wherein the polylactic acid resin composition comprises a polylactic acid resin, a plasticizer having a polyoxyalkylene group or an oxyalkylene group, and a mold release agent having a melting point of 20 to 75 ℃,
wherein the set temperature of at least a part of a cylinder of the injection molding machine is 200 ℃ or higher, the surface temperature of the mold is 85 ℃ or higher, the surface roughness of the mold is 1.0 [ mu ] m or less,
the release agent is 1 or more than 2 selected from (1) aliphatic hydrocarbon, (2) fatty acid, (3) fatty acid ester of polyhydric alcohol and (4) ester or polyester with perfluoroalkyl.
2. The production method according to claim 1, wherein the release agent is 1 or 2 or more selected from the group consisting of an ester of a polyhydric alcohol and a fatty acid having 12 to 30 carbon atoms, an ester having a perfluoroalkyl group, and a polyester having a perfluoroalkyl group.
3. The production method according to claim 2, wherein the polyol contains 1 or 2 or more selected from glycerol, sorbitol, and pentaerythritol.
4. The production process according to claim 2, wherein the perfluoroalkyl-containing ester or perfluoroalkyl-containing polyester is at least 1 selected from perfluoroalkyl-containing (meth) acrylates, perfluoroalkyl-containing maleates, perfluoroalkyl-containing fumarates, and perfluoroalkyl-containing polyesters obtained by condensing an acid component containing perfluoroalkyl-containing acrylic acid, perfluoroalkyl-containing maleic acid, or perfluoroalkyl-containing fumaric acid with an alcohol component.
5. The production process according to any one of claims 1 to 4, wherein the content of the release agent is 0.01 to 2 parts by weight based on 100 parts by weight of the polylactic acid resin.
6. The production process according to any one of claims 1 to 4, wherein the melting point of the release agent is 25 to 65 ℃.
7. The production process according to any one of claims 1 to 4, wherein the melting point of the release agent is 28 to 48 ℃.
8. The production method according to any one of claims 1 to 4, wherein the release agent is 1 or 2 or more selected from an ester of a polyhydric alcohol and a fatty acid having 14 to 22 carbon atoms, an ester having a perfluoroalkyl group, and a polyester having a perfluoroalkyl group.
9. The production process according to any one of claims 1 to 4, wherein the content of the release agent is 0.03 to 0.9 parts by weight based on 100 parts by weight of the polylactic acid resin.
10. The production process according to any one of claims 1 to 4, wherein the content of the release agent is 0.05 to 0.4 part by weight based on 100 parts by weight of the polylactic acid resin.
11. The production method according to any one of claims 1 to 4, wherein the ratio of the content of the plasticizer having a polyoxyalkylene group or an oxyalkylene group to the content of the release agent, that is, the plasticizer/release agent is 100/0.1 to 100/15.
12. The production method according to any one of claims 1 to 4, wherein the ratio of the content of the plasticizer having a polyoxyalkylene group or an oxyalkylene group to the content of the release agent, that is, the plasticizer/release agent is 100/0.5 to 100/4.
13. The production method according to any one of claims 1 to 4, wherein the plasticizer having a polyoxyalkylene group or an oxyalkylene group is the following compound: the ester has 2 or more ester groups in the molecule, and 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms is added on average to 1 hydroxyl group in at least 1 alcohol component constituting the ester.
14. The production method according to any one of claims 1 to 4, wherein the plasticizer having a polyoxyalkylene group or an oxyalkylene group is 1 or 2 or more selected from an ester formed from an oxyalkylene adduct of a polyhydric alcohol and a monocarboxylic acid and an ester formed from an aliphatic di-or tricarboxylic acid and a polyoxyalkylene glycol monoalkyl ether.
15. The production method according to any one of claims 1 to 4, wherein the plasticizer having a polyoxyalkylene group or oxyalkylene group is an ester represented by the following formula (I),
R1O-CO-R2-CO-[(OR3)mO-CO-R2-CO-]nOR1(I)
in the formula, R1Is alkyl of 1-8 carbon atoms, R2Is C2-4 alkylene, R3Is an alkylene group having 2 to 6 carbon atoms, m represents a number of 1 to 6, n represents a number of 1 to 12, wherein all R' s2All R's may be the same or different3May be the same or different.
16. The production method according to claim 15, wherein the ester represented by formula (I) has a solubility parameter value (SP value) of 10.0 to 12.0 as measured by the Fedors method.
17. The production process according to claim 15, wherein the ester represented by the formula (I) is obtained by using the following (1) to (3) as a raw material,
(1) a monohydric alcohol having an alkyl group with 1 to 8 carbon atoms,
(2) a dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms,
(3) a glycol having an alkylene group having 2 to 6 carbon atoms.
18. The manufacturing method according to claim 17,
(1) the monohydric alcohol having an alkyl group with 1 to 8 carbon atoms is 1 or more than 2 selected from methanol, ethanol, 1-propanol and 1-butanol,
(2) the dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms is 1 or 2 or more selected from succinic acid, adipic acid, glutaric acid, and derivatives thereof, wherein the derivative is an acid anhydride, a methyl ester or an ethyl ester,
(3) the dihydric alcohol having an alkylene group having 2 to 6 carbon atoms is 1 or more than 2 selected from diethylene glycol, triethylene glycol, 1, 2-propanediol, 1, 3-propanediol, tetraethylene glycol and 1, 4-butanediol.
19. The production method according to any one of claims 1 to 4, wherein the content of the plasticizer having a polyoxyalkylene group or an oxyalkylene group is 0.1 to 30 parts by weight relative to 100 parts by weight of the polylactic acid resin.
20. The production method according to any one of claims 1 to 4, wherein the content of the plasticizer having a polyoxyalkylene group or an oxyalkylene group is 5 to 20 parts by weight relative to 100 parts by weight of the polylactic acid resin.
21. The production method according to any one of claims 1 to 4, wherein the polylactic acid resin composition further contains an organic crystal nucleating agent.
22. The production method according to claim 21, wherein the organic crystal nucleating agent is 1 or 2 or more selected from the group consisting of a hydroxy fatty acid bisamide, a metal salt of phenylphosphonic acid, a compound having a phthalocyanine skeleton, and a metal salt of aromatic dialkyl sulfonate.
23. The method of claim 21, wherein the organic crystal nucleating agent is contained in an amount of 0.5 to 3 parts by weight based on 100 parts by weight of the polylactic acid resin.
24. The production method according to any one of claims 1 to 4, wherein the set temperature of the barrel is higher than 200 ℃ and 230 ℃ or lower.
25. The production method according to any one of claims 1 to 4, wherein the surface roughness of the mold is 0.1 to 1.0 μm.
26. The production method according to any one of claims 1 to 4, wherein the surface temperature of the mold is 85 to 120 ℃.
27. The production method according to any one of claims 1 to 4, wherein the surface temperature of the mold is 10 ℃ or higher than the melting point of the release agent.
28. The production method according to any one of claims 1 to 4, wherein the surface temperature of the mold is 10 to 65 ℃ higher than the melting point of the release agent.
29. The production method according to any one of claims 1 to 4, wherein the polylactic acid resin has an optical purity of 90% or more.
30. A molded article obtained by the production method according to any one of claims 1 to 29.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-283942 | 2011-12-26 | ||
| JP2011283942 | 2011-12-26 | ||
| PCT/JP2012/081303 WO2013099531A1 (en) | 2011-12-26 | 2012-12-04 | Method for producing injection-molded article of polylactic acid resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104039520A CN104039520A (en) | 2014-09-10 |
| CN104039520B true CN104039520B (en) | 2016-06-15 |
Family
ID=48697029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280064097.1A Expired - Fee Related CN104039520B (en) | 2011-12-26 | 2012-12-04 | The manufacture method of the injection-molded article of polylactic acid resin composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6038608B2 (en) |
| CN (1) | CN104039520B (en) |
| WO (1) | WO2013099531A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3912751A4 (en) * | 2019-04-26 | 2022-10-26 | Sekisui Chemical Co., Ltd. | Core resin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111735A (en) * | 2008-11-05 | 2010-05-20 | Teijin Chem Ltd | Polylactic acid composition and molded product thereof |
| CN102089386A (en) * | 2008-08-08 | 2011-06-08 | 花王株式会社 | Biodegradable resin composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08325387A (en) * | 1995-05-30 | 1996-12-10 | Asahi Chem Ind Co Ltd | Polyethylene-based shrink film |
| JP2004331967A (en) * | 2003-04-18 | 2004-11-25 | E I Du Pont De Nemours & Co | Injection-molded article produced from biodegradable aromatic polyester blend composition and method for producing the same |
| JP2004338185A (en) * | 2003-05-14 | 2004-12-02 | Fuji Photo Film Co Ltd | Polylactic acid resin molded product and its manufacturing method |
| JP4766585B2 (en) * | 2003-08-26 | 2011-09-07 | 三菱レイヨン株式会社 | Thermoplastic resin composition, light reflector, and method for producing molded article for light reflector |
| JP4438395B2 (en) * | 2003-12-12 | 2010-03-24 | 東レ株式会社 | Method for molding aliphatic polyester resin composition |
| JP4876507B2 (en) * | 2005-09-28 | 2012-02-15 | 東レ株式会社 | Flexible resin composition and molded article comprising the same |
| JP5150052B2 (en) * | 2006-01-20 | 2013-02-20 | 帝人株式会社 | Method for producing polylactic acid composition |
| JP5082353B2 (en) * | 2006-04-28 | 2012-11-28 | 川崎化成工業株式会社 | Flexibility imparting agent for resin and biodegradable resin composition containing the flexibility imparting agent |
| JP5166706B2 (en) * | 2006-06-26 | 2013-03-21 | リケンテクノス株式会社 | Resin composition and sheet using the same |
| JP5223303B2 (en) * | 2007-11-14 | 2013-06-26 | 東レ株式会社 | Profile extrusion molding |
| JP5542371B2 (en) * | 2009-05-29 | 2014-07-09 | 国立大学法人九州大学 | Interfacial adhesion control using fluorine-containing hyperbranched polymer |
-
2012
- 2012-11-27 JP JP2012258816A patent/JP6038608B2/en not_active Expired - Fee Related
- 2012-12-04 CN CN201280064097.1A patent/CN104039520B/en not_active Expired - Fee Related
- 2012-12-04 WO PCT/JP2012/081303 patent/WO2013099531A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102089386A (en) * | 2008-08-08 | 2011-06-08 | 花王株式会社 | Biodegradable resin composition |
| JP2010111735A (en) * | 2008-11-05 | 2010-05-20 | Teijin Chem Ltd | Polylactic acid composition and molded product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013151650A (en) | 2013-08-08 |
| WO2013099531A1 (en) | 2013-07-04 |
| JP6038608B2 (en) | 2016-12-07 |
| CN104039520A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8722813B2 (en) | Resin composition | |
| KR101346751B1 (en) | Biodegradable resin composition | |
| EP2294140B1 (en) | Fire retardant resin composition | |
| WO2008075775A1 (en) | Polylactic acid resin composition and method for producing polylactic acid resin molded body | |
| KR101889135B1 (en) | Molded product composed of polyester resin composition | |
| JP2008174735A (en) | Polylactic acid resin composition | |
| US10100191B2 (en) | Polylactic acid resin composition | |
| JP2015120807A (en) | Substrate for hot stamp | |
| US9505913B2 (en) | Polylactic acid resin composition | |
| JP4297510B2 (en) | Method for producing polylactic acid resin molded body | |
| CN104039520B (en) | The manufacture method of the injection-molded article of polylactic acid resin composition | |
| JP6202029B2 (en) | Resin composition and resin molded body | |
| JP5950339B2 (en) | Polylactic acid resin composition | |
| JP6381365B2 (en) | Polylactic acid resin composition | |
| JP2013199640A (en) | Crosslinked polylactic acid resin composition | |
| JP6385204B2 (en) | Method for producing injection molded article of polylactic acid resin composition | |
| CN102633645B (en) | Compound, resin composition, and resin molded article | |
| JP2019026728A (en) | Resin composition and resin molding | |
| JP5273847B2 (en) | Polylactic acid resin composition | |
| JP2015127388A (en) | Polylactic acid resin composition | |
| KR101401262B1 (en) | Ether-ester based plasticizers for biodegradable resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160615 Termination date: 20211204 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |