JP6639894B2 - Polylactic acid resin composition, polylactic acid resin molded article, and method for producing polylactic acid resin molded article - Google Patents
Polylactic acid resin composition, polylactic acid resin molded article, and method for producing polylactic acid resin molded article Download PDFInfo
- Publication number
- JP6639894B2 JP6639894B2 JP2015246299A JP2015246299A JP6639894B2 JP 6639894 B2 JP6639894 B2 JP 6639894B2 JP 2015246299 A JP2015246299 A JP 2015246299A JP 2015246299 A JP2015246299 A JP 2015246299A JP 6639894 B2 JP6639894 B2 JP 6639894B2
- Authority
- JP
- Japan
- Prior art keywords
- polylactic acid
- acid resin
- group
- resin composition
- mass
- 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.)
- Active
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 78
- 239000004626 polylactic acid Substances 0.000 title claims description 78
- 229920005989 resin Polymers 0.000 title claims description 53
- 239000011347 resin Substances 0.000 title claims description 53
- 239000011342 resin composition Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 amide compound Chemical class 0.000 claims description 87
- 239000000126 substance Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000003484 crystal nucleating agent Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 239000002667 nucleating agent Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 150000001340 alkali metals Chemical group 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 5
- 125000005020 hydroxyalkenyl group Chemical group 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 238000000034 method Methods 0.000 description 35
- 238000002425 crystallisation Methods 0.000 description 30
- 230000008025 crystallization Effects 0.000 description 30
- 239000000203 mixture Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000004898 kneading Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229960000448 lactic acid Drugs 0.000 description 4
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 101710148027 Ribulose bisphosphate carboxylase/oxygenase activase 1, chloroplastic Proteins 0.000 description 3
- 101710201629 Ribulose bisphosphate carboxylase/oxygenase activase 2, chloroplastic Proteins 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 229920003232 aliphatic polyester Polymers 0.000 description 3
- 239000002775 capsule Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-N 0.000 description 2
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- RBPNRIYDTUGEEC-UHFFFAOYSA-N S(=O)(=O)(O)C=1C=C(C=C(C(=O)O)C1)C(=O)O.C[Ba]C Chemical compound S(=O)(=O)(O)C=1C=C(C=C(C(=O)O)C1)C(=O)O.C[Ba]C RBPNRIYDTUGEEC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- LJZKUDYOSCNJPU-UHFFFAOYSA-N dotetracontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O LJZKUDYOSCNJPU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 description 2
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LLHSEQCZSNZLRI-UHFFFAOYSA-M sodium;3,5-bis(methoxycarbonyl)benzenesulfonate Chemical compound [Na+].COC(=O)C1=CC(C(=O)OC)=CC(S([O-])(=O)=O)=C1 LLHSEQCZSNZLRI-UHFFFAOYSA-M 0.000 description 2
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- MXJJJAKXVVAHKI-WRBBJXAJSA-N (9z,29z)-octatriaconta-9,29-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O MXJJJAKXVVAHKI-WRBBJXAJSA-N 0.000 description 1
- CPUBMKFFRRFXIP-YPAXQUSRSA-N (9z,33z)-dotetraconta-9,33-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O CPUBMKFFRRFXIP-YPAXQUSRSA-N 0.000 description 1
- KZVIUXKOLXVBPC-UHFFFAOYSA-N 16-methylheptadecanamide Chemical compound CC(C)CCCCCCCCCCCCCCC(N)=O KZVIUXKOLXVBPC-UHFFFAOYSA-N 0.000 description 1
- XHSVWKJCURCWFU-UHFFFAOYSA-N 19-[3-(19-amino-19-oxononadecyl)phenyl]nonadecanamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCC1=CC=CC(CCCCCCCCCCCCCCCCCCC(N)=O)=C1 XHSVWKJCURCWFU-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- RZGKLSBUNPJKTI-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCC(=O)NCC1=CC(=CC=C1)CNC(=O)C(C)CCCCCCCCCCCCCCCC Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCC1=CC(=CC=C1)CNC(=O)C(C)CCCCCCCCCCCCCCCC RZGKLSBUNPJKTI-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QVXFGVVYTKZLJN-KHPPLWFESA-N [(z)-hexadec-7-enyl] acetate Chemical group CCCCCCCC\C=C/CCCCCCOC(C)=O QVXFGVVYTKZLJN-KHPPLWFESA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical group [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 229940022769 d- lactic acid Drugs 0.000 description 1
- GKAWAQNIMXHVNI-UHFFFAOYSA-N decanamide;ethene Chemical compound C=C.CCCCCCCCCC(N)=O.CCCCCCCCCC(N)=O GKAWAQNIMXHVNI-UHFFFAOYSA-N 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VJJBJJBTUXPNEO-UHFFFAOYSA-N docosanamide;ethene Chemical compound C=C.CCCCCCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCCCCCC(N)=O VJJBJJBTUXPNEO-UHFFFAOYSA-N 0.000 description 1
- GFQOFGWPGYRLAO-UHFFFAOYSA-N dodecanamide;ethene Chemical compound C=C.CCCCCCCCCCCC(N)=O.CCCCCCCCCCCC(N)=O GFQOFGWPGYRLAO-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- RKVQXYMNVZNJHZ-UHFFFAOYSA-N hexacosanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCC(N)=O RKVQXYMNVZNJHZ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000004790 ingeo Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- UGKIWQRXZAAROZ-UHFFFAOYSA-N tetracontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O UGKIWQRXZAAROZ-UHFFFAOYSA-N 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- WPJRYESQKIBSTM-UHFFFAOYSA-N triacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WPJRYESQKIBSTM-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Description
本発明は、耐熱性に優れ、結晶化後も透明性を維持できるポリ乳酸樹脂組成物、ポリ乳酸樹脂成形体及びポリ乳酸樹脂成形体の製造方法に関する。 TECHNICAL FIELD The present invention relates to a polylactic acid resin composition, a polylactic acid resin molded product, and a method for producing a polylactic acid resin molded product which have excellent heat resistance and can maintain transparency even after crystallization.
従来、ポリエステル系樹脂と結晶核剤とを含有して成るポリエステル系樹脂組成物として、脂肪族ポリエステルと、脂肪族カルボン酸アミド、脂肪族カルボン酸塩、脂肪族アルコール及び脂肪族カルボン酸エステルから選ばれる少なくとも一種とを含有するもの（例えば、特許文献１及び２参照）、脂肪族ポリエステル樹脂と、特定の芳香族スルホン酸塩と、特定のアミド化合物とを特定割合で含有して成るもの（例えば、特許文献３参照）、脂肪族ポリエステル樹脂と、特定の芳香族スルホン酸塩とを含有して成るもの（例えば、特許文献４参照）等が提案されている。しかし、これら従来のポリエステル系樹脂組成物には、ポリエステル系樹脂としてポリ乳酸樹脂を用いた場合に特に、結晶化が依然として遅く、そのため成形に長時間を要し、したがってそれだけ生産性が悪く、得られる成形品の透明性も悪いという問題がある。 Conventionally, as a polyester-based resin composition containing a polyester-based resin and a crystal nucleating agent, selected from aliphatic polyesters, aliphatic carboxylic acid amides, aliphatic carboxylic acid salts, aliphatic alcohols and aliphatic carboxylic acid esters. (For example, see Patent Literatures 1 and 2), those containing an aliphatic polyester resin, a specific aromatic sulfonate, and a specific amide compound in a specific ratio (for example, And Japanese Patent Application Laid-Open Publication No. H11-163, and a resin containing an aliphatic polyester resin and a specific aromatic sulfonate (for example, see Patent Literature 4). However, in these conventional polyester-based resin compositions, especially when polylactic acid resin is used as the polyester-based resin, the crystallization is still slow, so that a long time is required for molding, and therefore, the productivity is poor and the productivity is low. There is a problem that the transparency of the resulting molded article is also poor.
本発明が解決しようとする課題は、結晶化が速く、したがってそれだけ結晶化時間が短く、結晶化後も透明性を維持できるポリ乳酸樹脂組成物、ポリ乳酸樹脂成形体の製造方法及びポリ乳酸樹脂成形体を提供する処にある。 The problem to be solved by the present invention is to provide a polylactic acid resin composition, a method for producing a polylactic acid resin molded article, and a polylactic acid resin, which can rapidly crystallize, and therefore have a short crystallization time, and can maintain transparency even after crystallization. It is in the process of providing a molded body.
しかして本発明者らは、前記の課題を解決するべく研究した結果、ポリ乳酸樹脂に、結晶核剤として特定の芳香族スルホン酸塩と特定のアミド化合物とを特定割合で含有して成るものを用いたものが正しく好適であることを見出した。 Thus, the present inventors have studied to solve the above-described problems, and as a result, a polylactic acid resin containing a specific aromatic sulfonate and a specific amide compound as a crystal nucleating agent in a specific ratio. Has been found to be correct and suitable.
すなわち本発明は、ポリ乳酸樹脂と結晶核剤とを含有して成るポリ乳酸樹脂組成物であって、該結晶核剤が下記の化１で示される芳香族スルホン酸塩を１〜３０質量％及び下記の化２で示されるアミド化合物を７０〜９９質量％（合計１００質量％）の割合で含有して成ることを特徴とするポリ乳酸樹脂組成物に係る。また本発明はかかるポリ乳酸樹脂組成物から成形されているポリ乳酸樹脂成形体及びかかるポリ乳酸樹脂成形体の製造方法に係る。 That is, the present invention relates to a polylactic acid resin composition comprising a polylactic acid resin and a crystal nucleating agent, wherein the crystal nucleating agent comprises 1 to 30 % by mass of an aromatic sulfonate represented by the following chemical formula 1. And a polylactic acid resin composition comprising an amide compound represented by the following chemical formula 2 at a ratio of 70 to 99% by mass (total 100% by mass). The present invention also relates to a polylactic acid resin molded article molded from such a polylactic acid resin composition and a method for producing such a polylactic acid resin molded article.
化１において、
Ｘ：ベンゼンから３個の水素原子を除いた残基
Ｒ１，Ｒ２：炭素数１〜６の炭化水素基
Ｍ：アルカリ金属原子又はアルカリ土類金属原子
ｎ：１又は２であって、Ｍがアルカリ金属原子の場合はｎ＝１、Ｍがアルカリ土類金属原子の場合はｎ＝２
In Chemical Formula 1,
X: Residues R 1 and R 2 obtained by removing three hydrogen atoms from benzene: a hydrocarbon group having 1 to 6 carbon atoms M: an alkali metal atom or an alkaline earth metal atom n: 1 or 2; Is n = 1 when M is an alkali metal atom, n = 2 when M is an alkaline earth metal atom
化２において、
Ｒ３，Ｒ７ ：炭素数１〜２２の炭化水素基、炭素数１〜２２のヒドロキシアルキル基又は炭素数１〜２２のヒドロキシアルケニル基
Ｒ４ ，Ｒ６ ：水素原子
Ｒ５ ：炭素数１〜６のアルキレン基
In Chemical Formula 2,
R 3 , R 7 : C 1 to C 22 hydrocarbon group, C 1 to C 22 hydroxyalkyl group or C 1 to C 22 hydroxyalkenyl group R 4 , R 6 : Hydrogen atom R 5 : C 1 to C 1 6 alkylene groups
先ず、本発明に係るポリ乳酸樹脂組成物（以下、本発明の組成物という）について説明する。本発明の組成物は、ポリ乳酸樹脂と結晶核剤とを含有して成るポリ乳酸樹脂組成物である。該結晶核剤が前記の化１で示される芳香族スルホン酸塩を１〜４９質量％及び前記の化２で示されるアミド化合物を５１〜９９質量％（合計１００質量％）の割合で含有して成るものが挙げられるが、本発明の組成物は、該結晶核剤が前記の化１で示される芳香族スルホン酸塩を１〜３０質量％及び前記の化２で示されるアミド化合物を７０〜９９質量％（合計１００質量％）の割合で含有して成ることを特徴とするものである。 First, the polylactic acid resin composition according to the present invention (hereinafter, referred to as the composition of the present invention) will be described. The compositions of the present invention, Ru polylactic acid resin composition der comprising a polylactic acid resin and the crystal nucleating agent. The nucleating agent contains 1 to 49% by mass of the aromatic sulfonate represented by Chemical Formula 1 and 51 to 99% by mass (total 100% by mass) of the amide compound represented by Chemical Formula 2. In the composition of the present invention, the nucleating agent comprises 1 to 30 % by mass of the aromatic sulfonate represented by the above formula 1 and 70 % by mass of the amide compound represented by the above formula 2. To 99% by mass (total 100% by mass).
化１で示される芳香族スルホン酸塩において、化１中のＸは、ベンゼンから３個の水素原子を除いた残基である。化１中のＲ１及びＲ２は、メチル基、エチル基、プロピル基、イソプロピル基、イソブチル基、ペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基、アリル基、シクロヘキセニル基等の炭素数１〜６の炭化水素基である。化１中のＭは、リチウム原子、ナトリウム原子、カリウム原子、ルビジウム原子、セシウム原子等のアルカリ金属原子又はベリリウム原子、マグネシウム原子、カルシウム原子、ストロンチウム原子、バリウム原子等のアルカリ土類金属原子であるが、なかでもカリウム原子、バリウム原子、ルビジウム原子、ストロンチウム原子又はカルシウム原子が好ましく、化１中のＭがカリウム原子又はバリウム原子であり、且つＲ１及びＲ２がメチル基がより好ましい。化１中のｎは、１又は２であるが、Ｍがアルカリ金属原子の場合はｎ＝１、Ｍがアルカリ土類金属原子の場合はｎ＝２である。 In the aromatic sulfonate represented by Chemical Formula 1, X in Chemical Formula 1 is a residue obtained by removing three hydrogen atoms from benzene. R 1 and R 2 in Chemical Formula 1 each have 1 to 1 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, an allyl group, and a cyclohexenyl group. 6 hydrocarbon groups. M in Chemical Formula 1 is an alkali metal atom such as a lithium atom, a sodium atom, a potassium atom, a rubidium atom, and a cesium atom, or an alkaline earth metal atom such as a beryllium atom, a magnesium atom, a calcium atom, a strontium atom, and a barium atom. However, among them, a potassium atom, a barium atom, a rubidium atom, a strontium atom or a calcium atom is preferable, M in the chemical formula 1 is a potassium atom or a barium atom, and R 1 and R 2 are more preferably a methyl group. N in Chemical Formula 1 is 1 or 2, and when M is an alkali metal atom, n = 1, and when M is an alkaline earth metal atom, n = 2.
以上説明した化１で示される芳香族スルホン酸塩の具体例としては、１）スルホフタル酸ジアルキルのアルカリ金属塩、２）スルホイソフタル酸ジアルキルのアルカリ金属塩、３）スルホテレフタル酸ジアルキルのアルカリ金属塩、４）スルホフタル酸ジアルキルのアルカリ土類金属塩、５）スルホイソフタル酸ジアルキルのアルカリ土類金属塩、６）スルホテレフタル酸ジアルキルのアルカリ土類金属塩、７）以上の１）〜６）の任意の混合物が挙げられるが、なかでもスルホイソフタル酸ジアルキルのアルカリ金属塩、スルホイソフタル酸ジアルキルのアルカリ土類金属塩が好ましい。 Specific examples of the aromatic sulfonate represented by Chemical formula 1 described above include 1) an alkali metal salt of dialkyl sulfophthalate, 2) an alkali metal salt of dialkyl sulfoisophthalate, and 3) an alkali metal salt of dialkyl sulfoterephthalate. 4) Alkaline earth metal salt of dialkyl sulfophthalate, 5) Alkaline earth metal salt of dialkyl sulfoisophthalate, 6) Alkaline earth metal salt of dialkyl sulfoterephthalate, 7) Any of the above 1) to 6) Of these, an alkali metal salt of dialkyl sulfoisophthalate and an alkaline earth metal salt of dialkyl sulfoisophthalate are preferred.
化１で示される芳香族スルホン酸塩それ自体は、公知の方法で合成できる。これには例えば、特公昭３４−１０４９７号公報、特開２０１０−１５０３６５号公報記載の方法が挙げられる。これらの方法で合成された芳香族スルホン酸塩には、硫酸塩、塩化物塩、酢酸塩、炭酸塩等の金属塩等の副生成物、スルホイソフタル酸ジアルキル及びその金属塩等の原料及び中和に使用した水酸化物等の不純物が含有されている。かかる不純物の含有量に特に制限はないが、５％以下であることが好ましい。 The aromatic sulfonate itself represented by Chemical formula 1 can be synthesized by a known method. For example, the methods described in JP-B-34-10497 and JP-A-2010-150365 can be mentioned. The aromatic sulfonates synthesized by these methods include by-products such as metal salts such as sulfates, chlorides, acetates and carbonates, and raw materials such as dialkyl sulfoisophthalates and metal salts thereof. Contains impurities such as hydroxide used for summation. The content of such impurities is not particularly limited, but is preferably 5% or less.
化２で示されるアミド化合物において、化２中のＲ３及びＲ７は、１）メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘキシル基、ペンチル基、オクチル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基、ドコシル基、ｎ−プロペニル基、イソプロペニル基、ｎ−ブテニル基、イソブテニル基、ｓｅｃ−ブテニル基、ｔｅｒｔ−ブテニル基、ｎ−ペンテニル基、ｎ−ヘキセニル基、ｎ−ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ウンデセニル基、ドデセニル基、トリデセニル基、テトラデセニル基、ペンタデセニル基、ヘキサデセニル基、ヘプタデセニル基、オクタデセニル基、エイコセニル基、ドコセニル基等の炭素数１〜２２の炭化水素基、２）ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシメチル基、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシヘキシル基、ヒドロキシペンチル基、ヒドロキシオクチル基、ヒドロキシデシル基、ヒドロキシドデシル基、ヒドロキシトリデシル基、ヒドロキシテトラデシル基、ヒドロキシヘキサデシル基、ヒドロキシオクタデシル基、ヒドロキシエイコシル基、ヒドロキシドコシル基等の炭素数１〜２２のヒドロキシアルキル基、又は３）ヒドロキシｎ−プロペニル基、ヒドロキシイソプロペニル基、ヒドロキシｎ−ブテニル基、ヒドロキシイソブテニル基、ヒドロキシｓｅｃ−ブテニル基、ヒドロキシｔｅｒｔ−ブテニル基、ヒドロキシｎ−ペンテニル基、ヒドロキシｎ−ヘキセニル基、ヒドロキシｎ−ヘプテニル基、ヒドロキシオクテニル基、ヒドロキシノネニル基、ヒドロキシデセニル基、ヒドロキシウンデセニル基、ヒドロキシドデセニル基、トリデセニル基、ヒドロキシテトラデセニル基、ヒドロキシペンタデセニル基、ヒドロキシヘキサデセニル基、ヒドロキシヘプタデセニル基、ヒドロキシオクタデセニル基、ヒドロキシエイコセニル基、ヒドロキシドコセニル基等の炭素数１〜２２のヒドロキシアルケニル基であるが、なかでも、炭素数１〜１８の炭化水素基、炭素数１〜１８のヒドロキシアルキル基又は炭素数１〜１８のヒドロキシアルケニル基が好ましい。化２中のＲ４及びＲ６は、水素原子である。化２中のＲ５は、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキサレン基等の炭素数１〜６のアルキレン基である。 In the amide compound represented by Chemical formula 2, R 3 and R 7 in Chemical formula 2 are: 1) methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, pentyl group, octyl group, decyl. Group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, n-propenyl group, isopropenyl group, n-butenyl group, isobutenyl group, sec-butenyl group, tert-butenyl group, n-pentenyl group, n-hexenyl group, n-heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, eicosenyl group , A docosenyl group or the like having 1 to 2 carbon atoms 2) hydroxymethyl group, hydroxyethyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyhexyl group, hydroxypentyl group, hydroxyoctyl group, hydroxydecyl group, hydroxydodecyl group A hydroxyalkyl group having 1 to 22 carbon atoms such as a hydroxytridecyl group, a hydroxytetradecyl group, a hydroxyhexadecyl group, a hydroxyoctadecyl group, a hydroxyeicosyl group, a hydroxydocosyl group, or 3) a hydroxy n-propenyl group, Hydroxy isopropenyl group, hydroxy n-butenyl group, hydroxy isobutenyl group, hydroxy sec-butenyl group, hydroxy tert-butenyl group, hydroxy n-pentenyl group, hydroxy n-hexenyl Group, hydroxy n-heptenyl group, hydroxy octenyl group, hydroxy nonenyl group, hydroxy decenyl group, hydroxy undecenyl group, hydroxy dodecenyl group, tridecenyl group, hydroxy tetradecenyl group, hydroxy pentadecyl group A alkenyl group having 1 to 22 carbon atoms such as a senyl group, a hydroxyhexadecenyl group, a hydroxyheptadecenyl group, a hydroxyoctadecenyl group, a hydroxyeicosenyl group, and a hydroxydocosenyl group; Among them, a hydrocarbon group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms or a hydroxyalkenyl group having 1 to 18 carbon atoms is preferable. R 4 and R 6 in Chemical formula 2 are hydrogen atoms. R 5 in Chemical Formula 2 is an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexalene group.
以上説明した化２で示されるアミド化合物の具体例としては、メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスステアリン酸アミド、エチレンビスエルカ酸アミド、エチレンビスベヘニン酸アミド、エチレンビスイソステアリン酸アミド、ブチレンビスステアリン酸アミド、ヘキサメチレンビスラウリン酸アミド、ヘキサメチレンビスオレイン酸アミド、へキサメチレンビスステアリン酸アミド、へキサメチレンビスベヘニン酸アミド、エチレンビス−１２−ヒドロキシステアリン酸アミド、ヘキサメチレンビス−１２−ヒドロキシステアリン酸アミド、エチレンビス−リシノール酸アミド等が挙げられるが、なかでもエチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスステアリン酸アミド、エチレンビス−１２−ヒドロキシステアリン酸アミド、エチレンビス−リシノール酸アミド等が好ましい。これらのアミド化合物は、単独で使用してもよいし、複数を組み合わせて使用してもよい。 Specific examples of the amide compound represented by Chemical formula 2 described above include methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, ethylene bisoleic acid amide, ethylene bis stearic acid amide, ethylene bis erucic acid Amide, ethylene bisbehenic acid amide, ethylene bis isostearic acid amide, butylene bis stearic acid amide, hexamethylene bis lauric acid amide, hexamethylene bis oleic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis stearic acid amide Nitric acid amide, ethylenebis-12-hydroxystearic acid amide, hexamethylenebis-12-hydroxystearic acid amide, ethylenebis-ricinoleic acid amide, etc. Amide, ethylenebis lauric acid amide, ethylenebis oleic acid amide, ethylenebis stearic acid amide, ethylenebis-12-hydroxystearic acid amide, ethylene bis - ricinoleic acid amide, and the like are preferable. These amide compounds may be used alone or in combination of two or more.
結晶核剤は前記したような化１で示される芳香族スルホン酸塩を１〜３０質量％及び化２で示されるアミド化合物を７０〜９９質量％（合計１００質量％）の割合で含有して成るものであるが、なかでも芳香族スルホン酸塩を５〜３０質量％及びアミド化合物を７０〜９５質量％（合計１００質量％）の割合で含有して成るものが好ましい。 The nucleating agent contains 1 to 30 % by mass of the aromatic sulfonate represented by Chemical Formula 1 and 70 to 99% by mass of the amide compound represented by Chemical Formula 2 (total 100% by mass). Among them, preferred are those containing 5 to 30% by mass of an aromatic sulfonic acid salt and 70 to 95% by mass (total 100% by mass) of an amide compound.
本発明の組成物に供する結晶核剤は、その平均粒子径を特に制限されないが、０．０１〜４０μｍの範囲内に調整したものが好ましい。ここで平均粒子径とは、レーザー回折・散乱法により測定して得られえた５０％体積径（メジアン径）を意味する。結晶核剤の平均粒子径が４０μｍより大きいと、結晶化に影響を及ぼすようになり、逆に結晶核剤の平均粒子径が０．０１μｍより小さいと、取り扱い時の粉立ちによって作業環境が悪くなりやすい。 The crystal nucleating agent used in the composition of the present invention is not particularly limited in its average particle diameter, but is preferably adjusted to a range of 0.01 to 40 µm. Here, the average particle diameter means a 50% volume diameter (median diameter) obtained by measurement by a laser diffraction / scattering method. When the average particle diameter of the nucleating agent is larger than 40 μm, the crystallization is affected. On the contrary, when the average particle diameter of the nucleating agent is smaller than 0.01 μm, the working environment is deteriorated due to dusting during handling. Prone.
結晶核剤の平均粒子径を０．０１〜４０μｍに調整する方法としては、特に制限されないが、結晶核剤を、１）ジェットミル、ボールミル、ビーズミル、サイクロンミル等の乾式粉砕機に供してその平均粒子径を調整する方法、２）水、有機溶剤及び水と有機溶剤の混合溶液と共に用い、サンドグラインダー、ボールミル、ビーズミル等の湿式粉砕機に供してその平均粒子径を調整する方法が挙げられる。 The method for adjusting the average particle size of the nucleating agent to 0.01 to 40 μm is not particularly limited, but the nucleating agent is subjected to 1) a dry mill such as a jet mill, a ball mill, a bead mill, a cyclone mill and the like. 2) A method of adjusting the average particle diameter by using together with water, an organic solvent and a mixed solution of water and an organic solvent, and using a water grinder such as a sand grinder, a ball mill, or a bead mill to adjust the average particle diameter. .
本発明の組成物において、組成物中のポリ乳酸樹脂及び結晶核剤の含有割合に特に制限はないが、ポリ乳酸樹脂１００質量部に対し結晶核剤を０．０５〜５質量部の割合で含有して成るものが好ましく、ポリ乳酸樹脂１００質量部に対し結晶核剤を０．１０〜２．５質量部の割合で含有して成るものがより好ましい。 In the composition of the present invention, the content ratio of the polylactic acid resin and the crystal nucleating agent in the composition is not particularly limited, but the nucleating agent is added in a ratio of 0.05 to 5 parts by mass with respect to 100 parts by mass of the polylactic acid resin. It is preferable that the composition contains 0.1 to 2.5 parts by mass of a crystal nucleating agent based on 100 parts by mass of the polylactic acid resin.
本発明の組成物において、ポリ乳酸樹脂の光学純度に特に制限はないが、９５〜１００％のものが好ましく、９６〜１００％のものがより好ましい。光学純度は、「ポリオレフィン等合成樹脂製食品容器包装等に関する自主基準 第３版改訂版 ２００４年６月追補第３部 衛生試験法 Ｐ１２−１３」記載のＤ体含有量の測定方法によって求めることができる。 In the composition of the present invention, the optical purity of the polylactic acid resin is not particularly limited, but is preferably from 95 to 100%, more preferably from 96 to 100%. The optical purity can be determined by the method for measuring the D-form content described in “Voluntary Standards for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins, Third Edition, Revised Edition, June 2004 Supplement, Part 3, Sanitary Testing Methods P12-13”. it can.
本発明の組成物に用いるポリ乳酸樹脂は、公知の方法で合成できる。これには例えば、特開平５−４８２５８号公報、特開平７−３３８６１号公報、特開昭５９−９６１２３号公報、高分子討論会予稿集第４４巻の３１９８−３１９９頁に記載されているような、１）乳酸を直接脱水縮合反応する方法、２）乳酸のラクチドを開環重合する方法等が挙げられる。前記１）の方法では、Ｌ−乳酸、Ｄ−乳酸、ＤＬ−乳酸又はこれらの混合物のいずれの乳酸を用いてもよい。前記２）の方法では、Ｌ−ラクチド、Ｄ−ラクチド、ＤＬ−ラクチド、メソ−ラクチド又はこれら混合物のいずれのラクチドを用いてもよい。原料のラクチドの合成、精製及び重合方法にも、公知の方法を適用できる。これには例えば、米国特許第４０５７５３７号明細書、公開欧州特許出願第２６１５７２号明細書、Ｐｏｌｙｍｅｒ Ｂｕｌｌｅｔｉｎ，１４，４９１−４９５（１９８５）、Ｍａｃｒｏｍｏｌ．Ｃｈｅｍ．，１８７，１６１１−１６２８（１９８６）等に記載されている方法が挙げられる。 The polylactic acid resin used in the composition of the present invention can be synthesized by a known method. Examples of this include those described in JP-A-5-48258, JP-A-7-33861, JP-A-59-96123, and the Preprints of the Society of Polymer Science, Vol. 44, pp. 3198-3199. Examples of the method include 1) a method in which lactic acid is directly dehydrated and condensed, and 2) a method in which lactide of lactic acid is subjected to ring-opening polymerization. In the method 1), any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid or a mixture thereof may be used. In the method 2), any lactide of L-lactide, D-lactide, DL-lactide, meso-lactide or a mixture thereof may be used. Known methods can also be applied to the synthesis, purification and polymerization of lactide as a raw material. This includes, for example, U.S. Pat. No. 4,057,537, Published European Patent Application No. 261572, Polymer Bulletin, 14, 491-495 (1985), Macromol. Chem. , 187, 1611-1628 (1986) and the like.
本発明の組成物に用いるポリ乳酸樹脂の質量平均分子量は特に制限されないが、３００００以上としたものが好ましく、５００００以上としたものがより好ましく、５００００〜４０００００としたものが特に好ましい。得られる成形体の強度や弾性率等の機械特性、更には成形時の流動性をより良く確保するためである。尚、質量平均分子量はゲルパーミエーションクロマトグラフ（ＧＰＣ）法によるポリスチレン換算値である。 The weight average molecular weight of the polylactic acid resin used in the composition of the present invention is not particularly limited, but is preferably 30,000 or more, more preferably 50,000 or more, and particularly preferably 50,000 to 400,000. This is because the mechanical properties such as the strength and elastic modulus of the obtained molded body, and the fluidity at the time of molding are better ensured. The mass average molecular weight is a value in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
本発明の組成物に用いるポリ乳酸樹脂は、これに含まれる残存モノマーを５０００ｐｐｍ以下としたものが好ましく、４０００ｐｐｍ以下としたものがより好ましく、３０００ｐｐｍ以下としたものが特に好ましい。得られる成形体の耐湿熱老化性や耐熱性等をより良く確保するためである。 The polylactic acid resin used in the composition of the present invention preferably has a residual monomer content of 5000 ppm or less, more preferably 4000 ppm or less, and particularly preferably 3000 ppm or less. This is because the obtained molded article is more likely to have wet heat aging resistance, heat resistance, and the like.
本発明の組成物は、得られる成形体の剛性、柔軟性、耐熱性、耐久性等を向上する観点から、その他の樹脂を含有することもできる。かかるその他の樹脂としては、ポリカーボネート、ポリエステル、ポリフェニレンエーテル、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリオキシメチレン、ポリフェニレンスルフィド、ＡＢＳ樹脂、ポリスチレン、ポリメチルメタクリレート、ポリアミド等が挙げられる。これらは単独もしくは２種以上組み合わせて用いることができる。 The composition of the present invention can also contain other resins from the viewpoint of improving the rigidity, flexibility, heat resistance, durability and the like of the obtained molded article. Examples of such other resins include polycarbonate, polyester, polyphenylene ether, polyethylene, polypropylene, polyvinyl chloride, polyoxymethylene, polyphenylene sulfide, ABS resin, polystyrene, polymethyl methacrylate, and polyamide. These can be used alone or in combination of two or more.
本発明の組成物には、合目的的に他の添加剤を含有することもできる。かかる他の添加剤としては、可塑剤、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、顔料、着色剤、各種フィラー、アンチブロッキング剤、帯電防止剤、防曇剤、流滴剤、赤外吸収剤、離型剤、香料、滑剤、難燃剤、発泡剤、充填剤、抗菌・抗カビ剤等が挙げられる。 The composition according to the invention can also optionally contain other additives. Such other additives include a plasticizer, an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, a pigment, a colorant, various fillers, an antiblocking agent, an antistatic agent, an antifogging agent, and a dropping agent. , An infrared absorber, a release agent, a fragrance, a lubricant, a flame retardant, a foaming agent, a filler, an antibacterial / antifungal agent and the like.
本発明の組成物は公知の方法で調製できる。これには例えば、１）粉末又はペレット状のポリ乳酸樹脂、結晶核剤と、要すれば他の添加剤とを、同時にドライブレンドした後、混練する方法、２）粉末又はペレット状のポリ乳酸樹脂と、結晶核剤とを溶融混練した後、更に要すれば他の添加剤をドライブレンドした後、混練する方法、３）粉末又はペレット状のポリ乳酸樹脂を混練溶融した後、サイドフィードにて結晶核剤と、要すれば他の添加剤を添加する方法、４）粉末又はペレット状のポリ乳酸樹脂と、要すれば他の添加剤をドライブレンドし、混練溶融した後、サイドフィードにて結晶核剤を添加する方法、５）粉末又はペレット状のポリ乳酸樹脂と、結晶核剤と、要すれば他の添加剤をドライブレンドした後、混練溶融し、更に要すれば液体の添加物を液体供給装置等により添加する方法、６）粉末又はペレット状のポリ乳酸樹脂と、要すれば他の添加剤をドライブレンドし、混練溶融した後、サイドフィードにて結晶核剤を添加し、要すれば液体の添加物を液体供給装置等により添加する方法等が挙げられる。かかるドライブレンドの装置としては、ミルロール、バンバリーミキサー、スーパーミキサー等が挙げられる。また混練機としては、単軸又は二軸押出機等が挙げられる。混練機の混練温度は、通常１２０〜２８０℃程度とする。ポリ乳酸樹脂の重合段階で、結晶核剤や要すれば他の添加剤を加えることもでき、また結晶核剤や要すれば他の添加剤を高濃度で含有するマスターバッチを作製しておき、これをポリ乳酸樹脂に加えることもできる。 The composition of the present invention can be prepared by a known method. This includes, for example, 1) a method of simultaneously dry-blending a powdery or pelletized polylactic acid resin and a crystal nucleating agent and, if necessary, other additives, followed by kneading, and 2) a powdered or pelletized polylactic acid. After melt-kneading the resin and the crystal nucleating agent, if necessary, dry-blending other additives, and then kneading the mixture. 3) Kneading and melting the powder or pellet-like polylactic acid resin and then feeding the mixture to the side feed. 4) Dry blending of powder or pellet-shaped polylactic acid resin and other additives, if necessary, by kneading and melting, and then into side feed 5) Dry blending of powdered or pelletized polylactic acid resin, crystal nucleating agent, and other additives if necessary, then kneading and melting, and further adding liquid if necessary Object by liquid supply device etc. 6) Dry blending of powdery or pelletized polylactic acid resin with other additives if necessary, kneading and melting, then adding a nucleating agent by side feed, and adding liquid if necessary A method of adding a substance by a liquid supply device or the like. Examples of the dry blending device include a mill roll, a Banbury mixer, a super mixer, and the like. Moreover, as a kneader, a single-screw or twin-screw extruder and the like can be mentioned. The kneading temperature of the kneading machine is usually about 120 to 280 ° C. At the polymerization stage of the polylactic acid resin, a nucleating agent and other additives can be added if necessary, and a master batch containing a high concentration of the nucleating agent and other additives as necessary can be prepared. This can be added to the polylactic acid resin.
次に、本発明に係るポリ乳酸樹脂成形体（以下、本発明の成形体という）について説明する。本発明の成形体は、本発明の組成物から成形されているポリ乳酸樹脂成形体であって、ＪＩＳ Ｋ ７１３６により求められる１００μｍ厚のヘイズ値が２０以下であるポリ乳酸樹脂成形体である。 Next, the polylactic acid resin molded article according to the present invention (hereinafter, referred to as the molded article of the present invention) will be described. The molded article of the present invention is a polylactic acid resin molded article formed from the composition of the present invention, and has a 100 μm-thick haze value determined by JIS K 7136 of 20 or less.
成形方法は特に制限されず、これには例えば、射出成形、押出成形、ブロー成形、インフレーション成形、異形押出成形、射出ブロー成形、真空圧空成形、紡糸等が挙げられる。 The molding method is not particularly limited, and examples thereof include injection molding, extrusion molding, blow molding, inflation molding, profile extrusion molding, injection blow molding, vacuum pressure molding, and spinning.
本発明の成形体は、フィルム、袋、チューブ、シート、カップ、ボトル、トレー、糸等を包含し、その形状、大きさ、厚み、意匠等に関して何ら制限はない。具体的には、本発明の成形体は、包装用袋、食器、フォーク、スプーン、トレイ、ボトル、ラップフィルム、化粧品容器、ゴミ袋、かさ、テント、防水シート、テープ、エアーマット、つり糸、魚網、カプセル、肥料用の容器や包装材及びカプセル、種苗用の容器や包装材及びカプセル、農園芸用フィルム、製品包装用フィルム、オーバーヘッドプロジェクター用フィルム、熱線反射フィルム、液晶ディスプレー用フィルム等に用いることができる。この他、本発明の成形体は、多層構造の積層体の層材とすることもできる。 The molded article of the present invention includes a film, a bag, a tube, a sheet, a cup, a bottle, a tray, a thread, and the like, and there is no limitation on the shape, size, thickness, design, and the like. Specifically, the molded article of the present invention is a packaging bag, tableware, fork, spoon, tray, bottle, wrap film, cosmetic container, garbage bag, cap, tent, waterproof sheet, tape, air mat, hanging thread, Used for fish nets, capsules, containers and packaging materials and capsules for fertilizers, containers and packaging materials and capsules for seedlings, agricultural and horticultural films, films for product packaging, films for overhead projectors, heat ray reflective films, films for liquid crystal displays, etc. be able to. In addition, the molded article of the present invention can be used as a layer material of a multilayer body having a multilayer structure.
最後に、本発明に係るポリ乳酸樹脂成形体の製造方法（以下、本発明の製造方法という）について説明する。本発明の製造方法は、本発明の組成物を熱処理し、成形するポリ乳酸樹脂成形体の製造方法である。熱処理温度に特に制限はないが、５０〜１５０℃で行うことが好ましく、７０〜１４０℃で行うことがより好ましい。 Lastly, a method for producing the polylactic acid resin molded article according to the present invention (hereinafter, referred to as the production method of the present invention) will be described. The production method of the present invention is a method for producing a polylactic acid resin molded article obtained by subjecting the composition of the present invention to heat treatment and molding. Although the heat treatment temperature is not particularly limited, the heat treatment is preferably performed at 50 to 150 ° C, more preferably at 70 to 140 ° C.
本発明の組成物の熱処理方法としては、該組成物の溶融物を金型内に充填し、金型内でそのまま加熱する方法（以下、金型内加熱法という）と、該組成物の非晶性の成形体を熱処理する方法（以下、後加熱法という）を挙げることができる。熱処理方法について特に制限はないが、後加熱法の方が好ましい。 As the heat treatment method of the composition of the present invention, a method in which a melt of the composition is filled in a mold and heated in the mold as it is (hereinafter, referred to as an in-mold heating method), A method of heat-treating a crystalline shaped body (hereinafter referred to as a post-heating method) can be given. The heat treatment method is not particularly limited, but the post-heating method is preferred.
後加熱法による熱処理方法としては、ヒーターの輻射熱で加熱する方法、加温した金属板等に接触させて加熱する方法、送風定温乾燥機を用いて加熱する方法、オーブン（加熱炉）中や温水中に連続的に通過させて加熱する方法、高温空気に接触させて加熱する方法、及びこれらを組み合わせた方法等が挙げられる。本発明の組成物はいずれの熱処理方法にも適応できる。 Examples of the heat treatment method by the post-heating method include a method of heating with radiant heat from a heater, a method of heating by contacting a heated metal plate or the like, a method of heating using a blower constant-temperature dryer, an oven (heating furnace) and hot water. A method of heating by continuously passing through, a method of heating by contacting with high-temperature air, and a method of combining these. The composition of the present invention is adaptable to any heat treatment method.
以上説明した本発明によると、結晶化が速く、したがってそれだけ結晶化時間が短く、結晶化後も透明性を維持できるポリ乳酸樹脂組成物、かかるポリ乳酸樹脂組成物を用いたポリ乳酸樹脂成形体及びかかるポリ乳酸樹脂成形体の製造方法を提供できるという効果がある。 According to the present invention described above, a polylactic acid resin composition that can be rapidly crystallized, and thus has a short crystallization time, and can maintain transparency even after crystallization, and a polylactic acid resin molded article using such a polylactic acid resin composition In addition, there is an effect that a method for producing such a polylactic acid resin molded article can be provided.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, examples and the like will be described in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, parts mean parts by mass, and% means mass%.
・芳香族スルホン酸塩（Ａ−１）の合成と調整
還流管を取り付けた１Ｌのセパラブルフラスコに、イソフタル酸７１．９４ｇ（０．４３モル）と発煙硫酸１９０．４ｇを仕込み、撹拌しながら内温２００〜２５０℃加温してスルホン化物を得た。別に、冷却管を取り付けた１Ｌのセパラブルフラスコにイオン交換水８９．０ｇを加え６０〜９０℃に加温し、前記のスルホン化物を滴下して、滴下後に５０℃以下まで冷却した後、水溶液を除去して５−スルホイソフタル酸を得た。還流管を取り付けた１Ｌのセパラブルフラスコに、得られた５−スルホイソフタル酸とメタノール６２．０ｇを仕込み、撹拌しながらメタノール還流下で反応させた。反応後、内温を５０℃以下まで冷却し、２０％水酸化カリウム水溶液１１２．２ｇを加え、ｐＨを６．５に中和した。冷却管を取り付けた３Ｌのセパラブルフラスコに、得られた中和物を仕込み、イオン交換水１９３０．０ｇを加えた後、撹拌しながら加温してメタノールを留去した。メタノール留去後、内温を３０℃まで徐冷して析出させたところ、５−スルホイソフタル酸ジメチルカリウム塩を含む固形分のスラリーを得た。このスラリーから固形分を濾別し、１００ｇのイオン交換水を加えて水洗処理した。水洗処理した固形分を１０５〜１２０℃の熱風乾燥機で乾燥して白色粉末１２１．６ｇを得た。最後に、得られた白色粉末をジェットミル（セイシン企業社製の商品名シングルトラックジェットミルＳＴＪ−２００型）を用いて粉砕圧力０．７Ｍｐａの条件で粉砕処理して、芳香族スルホン酸塩（Ａ−１）を得た。この芳香族スルホン酸塩（Ａ−１）には、液体クロマトグラフィーを用いて分析した結果、不純物として水酸化カリウムを２８０ｐｐｍ含有していた。
-Synthesis and adjustment of aromatic sulfonate (A-1) In a 1 L separable flask equipped with a reflux tube, 71.94 g (0.43 mol) of isophthalic acid and 190.4 g of fuming sulfuric acid were charged and stirred. The internal temperature was heated to 200 to 250 ° C to obtain a sulfonated product. Separately, 89.0 g of ion-exchanged water was added to a 1 L separable flask equipped with a cooling tube, heated to 60 to 90 ° C., the above-mentioned sulfonated product was dropped, and after dropping, the solution was cooled to 50 ° C. or less, and then an aqueous solution was added. Was removed to obtain 5-sulfoisophthalic acid. The obtained 5-sulfoisophthalic acid and 62.0 g of methanol were charged into a 1 L separable flask equipped with a reflux tube, and reacted under reflux with stirring. After the reaction, the internal temperature was cooled to 50 ° C. or lower, and 112.2 g of a 20% aqueous potassium hydroxide solution was added to neutralize the pH to 6.5. The obtained neutralized product was charged into a 3 L separable flask equipped with a cooling tube, 1930.0 g of ion-exchanged water was added, and the mixture was heated with stirring to distill off methanol. After methanol was distilled off, the internal temperature was gradually cooled to 30 ° C. to cause precipitation, whereby a solid slurry containing dimethyl potassium 5-sulfoisophthalate was obtained. The solid content was separated from this slurry by filtration, and 100 g of ion-exchanged water was added thereto, followed by washing with water. The solid content washed with water was dried with a hot-air dryer at 105 to 120 ° C to obtain 121.6 g of a white powder. Finally, the obtained white powder is pulverized using a jet mill (trade name: Single Track Jet Mill STJ-200, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a pulverization pressure of 0.7 MPa to obtain an aromatic sulfonate ( A-1) was obtained. This aromatic sulfonate (A-1) was analyzed by liquid chromatography and found to contain 280 ppm of potassium hydroxide as an impurity.
・芳香族スルホン酸塩（Ａ−２）の合成と調整
還流管を取り付けた２Ｌのセパラブルフラスコに、５−スルホイソフタル酸ジメチルナトリウム塩１００．０ｇ（０．３４モル）とイオン交換水９００．０ｇを仕込み、撹拌しながら７０〜９０℃に加温し、５−スルホイソフタル酸ジメチルナトリウム塩が溶解したことを確認後、塩化バリウム・２水和物４１．７ｇ（０．１７モル）を加え、３時間撹拌した後、５−スルホイソフタル酸ジメチルバリウム塩を含む固形分のスラリーを得た。内温３０℃以下まで急冷した後、このスラリーから固形分を濾別し、１００ｇのイオン交換水を加えて水洗処理した。水洗処理した固形分を１０５〜１２０℃の熱風乾燥機で４時間乾燥して白色粉末１０１．８ｇを得た。最後に、得られた白色粉末をジェットミル（セイシン企業社製の商品名シングルトラックジェットミルＳＴＪ−２００型）を用いて粉砕圧力０．７Ｍｐａの条件下で粉砕処理して、芳香族スルホン酸塩（Ａ−２）を得た。この芳香族スルホン酸塩（Ａ−２）には、原子吸光分析及び液体クロマトグラフィー分析をした結果、不純物として５−スルホイソフタル酸ジメチルナトリウム塩を０．８％及び塩化ナトリウムを４００ｐｐｍ含有していた。
Synthesis and Preparation of Aromatic Sulfonate (A-2) In a 2 L separable flask equipped with a reflux tube, 100.0 g (0.34 mol) of dimethyl sodium 5-sulfoisophthalate and 900.000 ion-exchanged water were added. After charging 0 g, the mixture was heated to 70 to 90 ° C. with stirring, and after confirming that dimethyl 5-sulfoisophthalate sodium salt was dissolved, 41.7 g (0.17 mol) of barium chloride dihydrate was added. After stirring for 3 hours, a slurry of a solid content containing dimethylbarium 5-sulfoisophthalate was obtained. After quenching to an internal temperature of 30 ° C. or lower, the solid content was separated from the slurry by filtration, and 100 g of ion-exchanged water was added to perform a water washing treatment. The solid content washed with water was dried with a hot air drier at 105 to 120 ° C. for 4 hours to obtain 101.8 g of a white powder. Finally, the obtained white powder was pulverized using a jet mill (trade name: single track jet mill STJ-200, manufactured by Seishin Enterprise Co., Ltd.) under the conditions of a pulverization pressure of 0.7 MPa to obtain an aromatic sulfonate. (A-2) was obtained. As a result of atomic absorption analysis and liquid chromatography analysis, this aromatic sulfonate (A-2) contained 0.8% of dimethyl 5-sulfoisophthalate and 400 ppm of sodium chloride as impurities. .
芳香族スルホン酸塩（Ａ−１）、（Ａ−２）と同様にして、芳香族スルホン酸塩（Ａ−３）〜（Ａ−５）及び（ＲＡ−１）〜（ＲＡ−２）を得た。 The aromatic sulfonates (A-3) to (A-5) and (RA-1) to (RA-2) were converted in the same manner as the aromatic sulfonates (A-1) and (A-2). Obtained.
試験区分１（結晶核剤の調製）
・結晶核剤（Ｃ−１）の調製
予め所定の粒径に調整した表１に示す芳香族スルホン酸塩（Ａ−１）１０部及び表２に示すアミド化合物（Ｂ−１）１０部をブレンダーを用いてドライブレンドし、表３に示す結晶核剤（Ｃ−１）を得た。
Test Category 1 (Preparation of nucleating agent)
Preparation of Crystal Nucleating Agent (C-1) 10 parts of the aromatic sulfonate (A-1) shown in Table 1 and 10 parts of the amide compound (B-1) shown in Table 2, which were adjusted to a predetermined particle size in advance. Dry blending was performed using a blender to obtain a crystal nucleating agent (C-1) shown in Table 3.
・結晶核剤（Ｃ−２）〜（Ｃ−１３）及び（ＲＣ−１）〜（ＲＣ−７）の調製
結晶核剤（Ｃ−１）の調製と同様にして、結晶核剤（Ｃ−２）〜（Ｃ−１３）及び（ＲＣ−１）〜（ＲＣ−７）を調製し、その内容を表１〜３にまとめて示した。
Preparation of crystal nucleating agents (C-2) to (C-13) and (RC-1) to (RC-7) In the same manner as in the preparation of the crystal nucleating agent (C-1), the crystal nucleating agent (C- 2) to (C-13) and (RC-1) to (RC-7) were prepared, and the contents are collectively shown in Tables 1 to 3.
表１において、
Ａ−１：５−スルホイソフタル酸ジメチルカリウム塩（合成品）
Ａ−２：５−スルホイソフタル酸ジメチルバリウム塩（合成品）
Ａ−３：５−スルホイソフタル酸ジメチルカルシウム塩（合成品）
Ａ−４：５−スルホイソフタル酸ジエチルストロンチウム塩（合成品）
Ａ−５：５−スルホイソフタル酸ジイソプロピルルビジウム塩（合成品）
ＲＡ−１：５−スルホイソフタル酸ジオクチルマグネシウム塩（合成品）
ＲＡ−２：５−スルホイソフタル酸ジヘキシルマンガン塩（合成品）
In Table 1,
A-1: 5-Sulfoisophthalic acid dimethyl potassium salt (synthetic product)
A-2: Dimethyl barium 5-sulfoisophthalate (synthetic product)
A-3: 5-Sulfoisophthalic acid dimethyl calcium salt (synthetic product)
A-4: diethylstrontium 5-sulfoisophthalate (synthetic product)
A-5: diisopropyl rubidium 5-sulfoisophthalate (synthetic product)
RA-1: dioctylmagnesium 5-sulfoisophthalate (synthetic product)
RA-2: dihexyl manganese 5-sulfoisophthalate (synthetic product)
表２において、
Ｂ−１：エチレンビスオレイン酸アミド（日本化成社製の商品名スリパックスＯ）
Ｂ−２：エチレンビス−１２−ヒドロキシステアリン酸アミド（日本化成社製の商品名スリパックスＨ）
Ｂ−３：エチレンビスステアリン酸アミド（日本化成社製の商品名スリパックスＥ）
Ｂ−４：ヘキサメチレンビスステアリン酸アミド（日本化成社製の商品名スリパックスＺＨＳ）
ＲＢ−１：ｍ−キシリレンビスステアリン酸アミド（日本化成社製の商品名スリパックスＰＸＳ）
ＲＢ−２：Ｎ，Ｎ’−メチル−ｍ−キシリレンビスステアリン酸アミド（合成品）
In Table 2,
B-1: Ethylene bisoleic acid amide (trade name Slipax O manufactured by Nippon Kasei Co., Ltd.)
B-2: Ethylene bis-12-hydroxystearic acid amide (trade name Slipax H manufactured by Nippon Kasei Co., Ltd.)
B-3: Ethylene bisstearic acid amide (trade name Slipax E manufactured by Nippon Kasei Co., Ltd.)
B-4: Hexamethylene bisstearic acid amide (Slipax ZHS, manufactured by Nippon Kasei Co., Ltd.)
RB-1: m-xylylene bisstearic acid amide (trade name Slipax PXS manufactured by Nippon Kasei Co., Ltd.)
RB-2: N, N'-methyl-m-xylylenebisstearic acid amide (synthetic product)
表３において、
Ａ−１〜Ａ−５及びＲＡ−１〜ＲＡ−２：表１に記載のもの
Ｂ−１〜Ｂ−４及びＲＢ−１〜ＲＢ−２：表２に記載のもの
In Table 3,
A-1 to A-5 and RA-1 to RA-2: those described in Table 1 B-1 to B-4 and RB-1 to RB-2: those described in Table 2
試験区分２（ポリ乳酸樹脂組成物の調製及びポリ乳酸樹脂成形体の製造）
・実施例１
・ポリ乳酸樹脂組成物の調製
ポリ乳酸樹脂（Ｎａｔｕｒｅ Ｗｏｒｋｓ社製の商品名Ｉｎｇｅｏ ２５００ＨＰ）１００部及び結晶核剤（Ｃ−１）１部をブレンダーを用いてドライブレンドして混合材料を得た。この混合材料をホッパーに投入し、２００℃に設定された二軸混練押出機にて溶融混練し、口金よりストランド状に押出し、水で急冷してストランドを得た。このストランドをストランドカッターで切断して、ペレット状のポリ乳酸樹脂組成物を得た。
Test Category 2 (Preparation of polylactic acid resin composition and production of polylactic acid resin molded article)
-Example 1
Preparation of Polylactic Acid Resin Composition 100 parts of a polylactic acid resin (trade name: Ingeo 2500HP, manufactured by Nature Works) and 1 part of a crystal nucleating agent (C-1) were dry-blended using a blender to obtain a mixed material. This mixed material was put into a hopper, melt-kneaded with a twin-screw kneading extruder set at 200 ° C., extruded into a strand shape from a die, and quenched with water to obtain a strand. This strand was cut with a strand cutter to obtain a pellet-shaped polylactic acid resin composition.
次いで、得られたペレット状のポリ乳酸樹脂組成物を、樹脂温度が２００℃に設定されたＴ−ダイ押出成形機にて溶融し、溶融物を温度を３０℃に調整したキャストロール上に押出し、厚み１００μｍのフィルム状のポリ乳酸樹脂成形体を製造した。 Next, the obtained pellet-shaped polylactic acid resin composition was melted by a T-die extruder in which the resin temperature was set to 200 ° C., and the melt was extruded onto a cast roll whose temperature was adjusted to 30 ° C. A 100 μm-thick film-shaped polylactic acid resin molded article was produced.
・実施例２〜１０，１２〜１４、参考例１１，１５及び比較例１〜７
実施例１の場合と同様にして、実施例２〜１０，１２〜１４、参考例１１，１５及び比較例１〜７のポリ乳酸樹脂組成物を調整し、ポリ乳酸樹脂成形体を製造した。これらの内容を表４にまとめて示した。
-Examples 2 to 10, 12 to 14, Reference Examples 11 and 15, and Comparative Examples 1 to 7
In the same manner as in Example 1, the polylactic acid resin compositions of Examples 2 to 10, 12 to 14, Reference Examples 11 and 15, and Comparative Examples 1 to 7 were prepared to produce polylactic acid resin molded articles. These contents are summarized in Table 4.
試験区分３（成形体の評価）
・アニーリング時間
試験区分２で調製した各例のフィルム状のポリ乳酸樹脂成形体について、９０℃又は１３０℃に調整した送風定温乾燥機（ＥＹＥＬＡ社製のＷＦＯ−６００Ｄ）を用い、熱処理時間を１０秒〜３００秒まで５秒刻みで変更する熱処理を行なった後、８０℃のお湯につけ、フィルムが変形しなくなるまでに必要な熱処理時間を求め、次の基準で評価した。結果を表４にまとめて示した。この熱処理時間は短いほど、フィルム状のポリ乳酸樹脂成形体が短時間で結晶化していることを示す。
Test Category 3 (Evaluation of molded body)
Annealing time The heat treatment time of the film-shaped polylactic acid resin molded article of each example prepared in Test Category 2 was adjusted to 10 ° C. by using a blower constant temperature dryer (WFO-600D manufactured by EYELA) adjusted to 90 ° C. or 130 ° C. After performing a heat treatment of changing from 5 seconds to 300 seconds at intervals of 5 seconds, the film was immersed in hot water of 80 ° C., and a heat treatment time required until the film was not deformed was obtained and evaluated according to the following criteria. The results are summarized in Table 4. The shorter the heat treatment time, the faster the film-shaped polylactic acid resin molded product is crystallized.
・アニーリング時間の評価基準
熱処理温度９０℃
ＡＡ：熱処理時間が９０秒未満であった。
Ａ：熱処理時間が９０〜１２０秒であった。
Ｂ：熱処理時間が１２０秒超であった。
熱処理温度１３０℃
ＡＡ：熱処理時間が４５秒未満であった。
Ａ：熱処理時間が４５〜７０秒であった。
Ｂ：熱処理時間が７０秒超であった。
・ Evaluation criteria for annealing time Heat treatment temperature 90 ℃
AA: Heat treatment time was less than 90 seconds.
A: The heat treatment time was 90 to 120 seconds.
B: Heat treatment time was longer than 120 seconds.
Heat treatment temperature 130 ° C
AA: Heat treatment time was less than 45 seconds.
A: The heat treatment time was 45 to 70 seconds.
B: The heat treatment time was longer than 70 seconds.
・結晶化温度（昇温時）
試験区分１で調製した各例のペレット状のポリ乳酸樹脂組成物３ｍｇをアルミニウムセルに充填し、示差走査熱量計（セイコーインスツル社製のＤＳＣ−６２００）を用いて、室温から２００℃まで３０℃／分の昇温速度で昇温し、結晶化ピーク温度を測定し、次の基準で評価した。結果を表４にまとめて示した。かかる結晶化ピーク温度は昇温時の発熱ピークのピークトップ温度を示し、昇温時の結晶化ピーク温度が低い程、昇温時の結晶化が速く、したがってそれだけ昇温時の結晶化時間が短くなることを示す。
・ Crystallization temperature (when heated)
An aluminum cell was filled with 3 mg of the pellet-shaped polylactic acid resin composition of each example prepared in Test Category 1, and the temperature was changed from room temperature to 200 ° C. using a differential scanning calorimeter (DSC-6200 manufactured by Seiko Instruments Inc.). The temperature was raised at a rate of ° C./min, the crystallization peak temperature was measured, and evaluated according to the following criteria. The results are summarized in Table 4. Such a crystallization peak temperature indicates the peak top temperature of the exothermic peak at the time of temperature rise, and the lower the crystallization peak temperature at the time of temperature rise, the faster the crystallization at the time of temperature rise, and accordingly the crystallization time at the time of temperature rise. Indicates shortening.
・昇温時の結晶化温度の評価基準
ＡＡ：結晶化ピーク温度が１００℃未満であった。
Ａ：結晶化ピーク温度が１００〜１１０℃であった。
Ｂ：結晶化ピーク温度が１１０℃超であった。
Evaluation criterion AA for crystallization temperature during temperature rise: The crystallization peak temperature was less than 100 ° C.
A: The crystallization peak temperature was 100 to 110 ° C.
B: The crystallization peak temperature was higher than 110 ° C.
・結晶化温度（降温時）
試験区分１で調製した各例のペレット状のポリ乳酸樹脂組成物３ｍｇをアルミニウムセルに充填し、示差走査熱量計（セイコーインスツル社製のＤＳＣ−６２００）を用いて、３０℃／分で室温から２００℃まで昇温して、５分間保持した後、３５℃／分で２００℃から降温して、結晶化ピーク温度を測定し、次の基準で評価した。結果を表４にまとめて示した。かかる結晶化ピーク温度は降温時の発熱ピークのピークトップ温度を示し、降温時の結晶化ピーク温度が高い程、降温時の結晶化が速く、したがってそれだけ降温時の結晶化時間が短くなることを示す。
・ Crystallization temperature (during cooling)
An aluminum cell was filled with 3 mg of the polylactic acid resin composition in the form of pellets of each example prepared in Test Category 1 and room temperature at 30 ° C./min using a differential scanning calorimeter (DSC-6200 manufactured by Seiko Instruments Inc.). The temperature was raised from 200 ° C. to 200 ° C., and maintained for 5 minutes. Then, the temperature was lowered from 200 ° C. at 35 ° C./min, and the crystallization peak temperature was measured and evaluated according to the following criteria. The results are summarized in Table 4. Such a crystallization peak temperature indicates a peak top temperature of an exothermic peak at the time of temperature decrease.The higher the crystallization peak temperature at the time of temperature decrease, the faster the crystallization at the time of temperature decrease, and accordingly, the shorter the crystallization time at the time of temperature decrease. Show.
・降温時の結晶化温度の評価基準
ＡＡ：結晶化ピーク温度が１００℃超であった。
Ａ：結晶化ピーク温度が９５〜１００℃であった。
Ｂ：結晶化ピーク温度が９５℃未満であった。
Evaluation criterion AA of crystallization temperature at the time of cooling: The crystallization peak temperature was higher than 100 ° C.
A: The crystallization peak temperature was 95 to 100 ° C.
B: The crystallization peak temperature was less than 95 ° C.
・透明性
試験区分１で製造した各例の厚み１００μｍのフィルム状のポリ乳酸樹脂成形体について、ヘーズメーター（日本電色工業製のＮＤＨ５０００）を用いてヘイズ値を測定し、次の基準で評価した。結果を表４にまとめて示した。
Transparency The haze value of a 100 μm-thick film-shaped polylactic acid resin molded article of each example manufactured in Test Category 1 was measured using a haze meter (NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated according to the following criteria. did. The results are summarized in Table 4.
透明性の評価基準
ＡＡ：ヘイズ値が１０未満であった。
Ａ：ヘイズ値が１０〜２０であった。
Ｂ：ヘイズ値が２０超であった。
Evaluation criteria for transparency AA: Haze value was less than 10.
A: The haze value was 10 to 20.
B: The haze value was more than 20.
表１〜３に対応する表４の結果からも明らかなように、本発明のポリ乳酸樹脂組成物を用いると、結晶化が速く、したがってそれだけ結晶化時間が短く、結晶化後も透明性を維持できることが解る。 As is clear from the results of Table 4 corresponding to Tables 1 to 3, when the polylactic acid resin composition of the present invention is used, crystallization is fast, and therefore the crystallization time is short, and the transparency after crystallization is high. You can see that it can be maintained.
Claims (12)
Ｘ：ベンゼンから３個の水素原子を除いた残基
Ｒ１，Ｒ２：炭素数１〜６の炭化水素基
Ｍ：アルカリ金属原子又はアルカリ土類金属原子
ｎ：１又は２であって、Ｍがアルカリ金属原子の場合はｎ＝１、Ｍがアルカリ土類金属原子の場合はｎ＝２）
Ｒ３，Ｒ７：炭素数１〜２２の炭化水素基、炭素数１〜２２のヒドロキシアルキル基又は炭素数１〜２２のヒドロキシアルケニル基
Ｒ４，Ｒ６：水素原子
Ｒ５：炭素数１〜６のアルキレン基） A polylactic acid resin composition comprising a polylactic acid resin and a crystal nucleating agent, wherein the crystal nucleating agent comprises 1 to 30 % by mass of an aromatic sulfonate represented by the following chemical formula 1 and A polylactic acid resin composition comprising the amide compound represented by the formula at a ratio of 70 to 99% by mass (total 100% by mass).
X: Residues R 1 and R 2 obtained by removing three hydrogen atoms from benzene: a hydrocarbon group having 1 to 6 carbon atoms M: an alkali metal atom or an alkaline earth metal atom n: 1 or 2; Is n = 1 when is an alkali metal atom, n = 2 when M is an alkaline earth metal atom)
R 3 , R 7 : C 1 to C 22 hydrocarbon group, C 1 to C 22 hydroxyalkyl group or C 1 to C 22 hydroxyalkenyl group R 4 , R 6 : Hydrogen atom R 5 : C 1 to C 1 6 alkylene groups)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015246299A JP6639894B2 (en) | 2015-12-17 | 2015-12-17 | Polylactic acid resin composition, polylactic acid resin molded article, and method for producing polylactic acid resin molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015246299A JP6639894B2 (en) | 2015-12-17 | 2015-12-17 | Polylactic acid resin composition, polylactic acid resin molded article, and method for producing polylactic acid resin molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017110122A JP2017110122A (en) | 2017-06-22 |
| JP6639894B2 true JP6639894B2 (en) | 2020-02-05 |
Family
ID=59079303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015246299A Active JP6639894B2 (en) | 2015-12-17 | 2015-12-17 | Polylactic acid resin composition, polylactic acid resin molded article, and method for producing polylactic acid resin molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6639894B2 (en) |
-
2015
- 2015-12-17 JP JP2015246299A patent/JP6639894B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2017110122A (en) | 2017-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Simmons et al. | Improvements in the crystallinity and mechanical properties of PLA by nucleation and annealing | |
| JP5654501B2 (en) | Method for producing polylactic acid resin composition | |
| US8835542B2 (en) | Nucleating agent and thermoplastic compositions comprising the same | |
| Srithep et al. | Injection molding and characterization of polylactide stereocomplex | |
| JP2004531613A (en) | New highly versatile nucleating agent for thermoplastics | |
| CN1500117A (en) | Metalsalts of hexahydrophthalic acid as nucleating additives for crystalline thermoplatics | |
| ES2941991T3 (en) | Polylactic acid composite material and application thereof | |
| CN1946807A (en) | Biodegradable resin composition | |
| US6914088B2 (en) | Diacetal composition, polyolefin nucleating agent comprising the diacetal composition, polyolefin resin compositions containing the diacetal composition, method for manufacturing the resin composition, and moldings | |
| WO2008075775A1 (en) | Polylactic acid resin composition and method for producing polylactic acid resin molded body | |
| TWI490257B (en) | Polylactic resin composition | |
| US11859081B2 (en) | Biobased additive for thermoplastic polyesters | |
| JP2010248448A (en) | Aliphatic polyester resin composition and aliphatic polyester resin molded article | |
| KR20180113972A (en) | PBAT resin composition | |
| TW202348722A (en) | Alcohol nucleating agent-containing polyhydroxyalkanoate composition, polyhydroxyalkanoate forming body and preparation method of polyhydroxyalkanoate forming body | |
| US9428607B2 (en) | Polylactic acid-polyalkylene glycol copolymer with fast crystallization rate and composition comprising the same | |
| Balkaev et al. | Novel nucleating agents for polypropylene and modifier of its physical-mechanical properties | |
| TWI492973B (en) | Polyolefin resin composition | |
| JP6639894B2 (en) | Polylactic acid resin composition, polylactic acid resin molded article, and method for producing polylactic acid resin molded article | |
| JP5078174B2 (en) | Crystal nucleating agent for polylactic acid resin, polylactic acid resin composition, method for preparing crystal nucleating agent for polylactic acid resin, and method for preparing polylactic acid resin composition | |
| TWI778225B (en) | Particulate nucleating agent, resin composition, molded article and manufacturing method thereof | |
| JP5196647B2 (en) | Polylactic acid resin composition and polylactic acid resin molded article | |
| TW201504334A (en) | Polyester resin composition containing aminotriazine derivative | |
| Srithep et al. | Characterization of stereocomplex polylactide/nanoclay nanocomposites | |
| TW201838961A (en) | Nucleating agent and resin composition containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD03 | Notification of appointment of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7423 Effective date: 20171226 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20180920 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20190606 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20190625 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20190814 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20191224 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191225 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6639894 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |