JP5319970B2 - Polylactic acid resin composition - Google Patents
Polylactic acid resin composition Download PDFInfo
- Publication number
- JP5319970B2 JP5319970B2 JP2008164977A JP2008164977A JP5319970B2 JP 5319970 B2 JP5319970 B2 JP 5319970B2 JP 2008164977 A JP2008164977 A JP 2008164977A JP 2008164977 A JP2008164977 A JP 2008164977A JP 5319970 B2 JP5319970 B2 JP 5319970B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- compound
- weight
- polylactic acid
- acid resin
- 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 106
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 106
- 239000011342 resin composition Substances 0.000 title claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 116
- 239000011347 resin Substances 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000004898 kneading Methods 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- -1 phosphorus compound Chemical class 0.000 claims description 62
- 239000011574 phosphorus Substances 0.000 claims description 36
- 229910052698 phosphorus Inorganic materials 0.000 claims description 36
- 229910019142 PO4 Inorganic materials 0.000 claims description 33
- 239000010452 phosphate Substances 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 11
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 11
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 11
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 239000004431 polycarbonate resin Substances 0.000 claims 8
- 229920005668 polycarbonate resin Polymers 0.000 claims 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 4
- 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 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 238000007334 copolymerization reaction Methods 0.000 claims 2
- 229920000578 graft copolymer Polymers 0.000 claims 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims 2
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- CONHAJWVOAJZGC-UHFFFAOYSA-N ethene;oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound C=C.CC(=C)C(=O)OCC1CO1 CONHAJWVOAJZGC-UHFFFAOYSA-N 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 150000003016 phosphoric acids Chemical class 0.000 claims 1
- 229920002725 thermoplastic elastomer Polymers 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 22
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 22
- 239000000203 mixture Substances 0.000 abstract description 10
- 150000003018 phosphorus compounds Chemical class 0.000 abstract description 3
- 239000011369 resultant mixture Substances 0.000 abstract 2
- 239000007858 starting material Substances 0.000 abstract 2
- 235000021317 phosphate Nutrition 0.000 description 31
- 235000014786 phosphorus Nutrition 0.000 description 26
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 16
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000003484 crystal nucleating agent Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000002667 nucleating agent Substances 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000004014 plasticizer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 6
- 229920000388 Polyphosphate Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000001205 polyphosphate Substances 0.000 description 6
- 235000011176 polyphosphates Nutrition 0.000 description 6
- 229930182843 D-Lactic acid Natural products 0.000 description 5
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229940022769 d- lactic acid Drugs 0.000 description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- APOXBWCRUPJDAC-UHFFFAOYSA-N bis(2,6-dimethylphenyl) hydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(=O)OC1=C(C)C=CC=C1C APOXBWCRUPJDAC-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 4
- YMKWWHFRGALXLE-UHFFFAOYSA-N 4-methyl-1-phenyl-2,3-dihydro-1$l^{5}-phosphole 1-oxide Chemical compound C1CC(C)=CP1(=O)C1=CC=CC=C1 YMKWWHFRGALXLE-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920006389 polyphenyl polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 2
- ALDZNWBBPCZXGH-UHFFFAOYSA-N 12-hydroxyoctadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(N)=O ALDZNWBBPCZXGH-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 2
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical class [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical class [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000011575 calcium Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011734 sodium Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- LIPMRGQQBZJCTM-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C LIPMRGQQBZJCTM-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Chemical class 0.000 description 2
- NEXZVOLIDKSFBH-UHFFFAOYSA-N (1,1-diphenyl-2-phosphonooxyethyl) 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(COP(O)(O)=O)(OC(=O)C(=C)C)C1=CC=CC=C1 NEXZVOLIDKSFBH-UHFFFAOYSA-N 0.000 description 1
- MFFNRVNPBJQZFO-UHFFFAOYSA-N (2,6-dimethylphenyl) dihydrogen phosphate Chemical compound CC1=CC=CC(C)=C1OP(O)(O)=O MFFNRVNPBJQZFO-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- DMBUODUULYCPAK-UHFFFAOYSA-N 1,3-bis(docosanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCC DMBUODUULYCPAK-UHFFFAOYSA-N 0.000 description 1
- BOSWPVRACYJBSJ-UHFFFAOYSA-N 1,3-di(p-tolyl)carbodiimide Chemical compound C1=CC(C)=CC=C1N=C=NC1=CC=C(C)C=C1 BOSWPVRACYJBSJ-UHFFFAOYSA-N 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-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
- 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
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- RGMMREBHCYXQMA-UHFFFAOYSA-N 2-hydroxyheptanoic acid Chemical compound CCCCCC(O)C(O)=O RGMMREBHCYXQMA-UHFFFAOYSA-N 0.000 description 1
- YQLRKXVEALTVCZ-UHFFFAOYSA-N 2-isocyanato-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1N=C=O YQLRKXVEALTVCZ-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- OZFLRNPZLCUVFP-UHFFFAOYSA-N 8-methylnonyl dihydrogen phosphate Chemical compound CC(C)CCCCCCCOP(O)(O)=O OZFLRNPZLCUVFP-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CGSLYBDCEGBZCG-UHFFFAOYSA-N Octicizer Chemical compound C=1C=CC=CC=1OP(=O)(OCC(CC)CCCC)OC1=CC=CC=C1 CGSLYBDCEGBZCG-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GTVWRXDRKAHEAD-UHFFFAOYSA-N Tris(2-ethylhexyl) phosphate Chemical compound CCCCC(CC)COP(=O)(OCC(CC)CCCC)OCC(CC)CCCC GTVWRXDRKAHEAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-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
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- HPUPGAFDTWIMBR-UHFFFAOYSA-N [methyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C)OC1=CC=CC=C1 HPUPGAFDTWIMBR-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 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
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 229920006167 biodegradable resin Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000002361 compost Substances 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
- 239000013078 crystal Substances 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- VZEGPPPCKHRYGO-UHFFFAOYSA-N diethoxyphosphorylbenzene Chemical compound CCOP(=O)(OCC)C1=CC=CC=C1 VZEGPPPCKHRYGO-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 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
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- QSACPWSIIRFHHR-UHFFFAOYSA-N dimethylphenyl isocyanide Natural products CC1=CC=CC(C)=C1C#N QSACPWSIIRFHHR-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- TXLQIJBYHKQZME-UHFFFAOYSA-N ethene;octanamide Chemical compound C=C.CCCCCCCC(N)=O.CCCCCCCC(N)=O TXLQIJBYHKQZME-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
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 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
- 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 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 239000000463 material Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- JCNCSCMYYGONLU-UHFFFAOYSA-N n,n'-bis(2-methylphenyl)methanediimine Chemical compound CC1=CC=CC=C1N=C=NC1=CC=CC=C1C JCNCSCMYYGONLU-UHFFFAOYSA-N 0.000 description 1
- IXDCJFUOQJOQCM-UHFFFAOYSA-N n,n'-dioctadecylmethanediimine Chemical compound CCCCCCCCCCCCCCCCCCN=C=NCCCCCCCCCCCCCCCCCC IXDCJFUOQJOQCM-UHFFFAOYSA-N 0.000 description 1
- CMESPBFFDMPSIY-UHFFFAOYSA-N n,n'-diphenylmethanediimine Chemical compound C1=CC=CC=C1N=C=NC1=CC=CC=C1 CMESPBFFDMPSIY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RMNODSGCFHVNDC-UHFFFAOYSA-N phenyl bis(2-propan-2-ylphenyl) phosphate Chemical compound CC(C)C1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1 RMNODSGCFHVNDC-UHFFFAOYSA-N 0.000 description 1
- WQJURGLUMGXTAR-UHFFFAOYSA-N phenylphosphonic acid;zinc Chemical class [Zn].OP(O)(=O)C1=CC=CC=C1 WQJURGLUMGXTAR-UHFFFAOYSA-N 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- QVJYHZQHDMNONA-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1.NC1=NC(N)=NC(N)=N1 QVJYHZQHDMNONA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- QEEHNBQLHFJCOV-UHFFFAOYSA-N tris(2-phenylphenyl) phosphate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(OC=1C(=CC=CC=1)C=1C=CC=CC=1)(=O)OC1=CC=CC=C1C1=CC=CC=C1 QEEHNBQLHFJCOV-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
本発明は、ポリ乳酸樹脂組成物に関する。さらに詳しくは、日用雑貨品、家電部品、自動車部品等として好適に使用し得るポリ乳酸樹脂組成物、該組成物を成形することにより得られるポリ乳酸樹脂成形体及び該成形体の製造方法に関する。 The present invention relates to a polylactic acid resin composition. More specifically, the present invention relates to a polylactic acid resin composition that can be suitably used as daily miscellaneous goods, home appliance parts, automobile parts, etc., a polylactic acid resin molded article obtained by molding the composition, and a method for producing the molded article. .
ポリ乳酸樹脂は、原料となるＬ−乳酸がトウモロコシ、芋等から抽出した糖分を用いて発酵法により生産されるため安価であること、原料が植物由来であるために原料が自然農作物なので総酸化炭素排出量が極めて少ない、また得られた樹脂の性能として剛性が強く透明性が良いという特徴があるので、現在その利用が期待され、フラットヤーン、ネット、育苗用ポット等の農業土木資材分野、窓付き封筒、買い物袋、コンポストバッグ、文具、雑貨等に使用されている。 Polylactic acid resin is inexpensive because L-lactic acid, which is a raw material, is produced by fermentation using sugars extracted from corn, straw, etc., and since the raw material is derived from plants, the raw material is a natural crop, so total oxidation Since carbon emissions are extremely low, and the resulting resin has high rigidity and transparency, it is expected to be used today, such as the field of agricultural civil engineering materials such as flat yarns, nets, seedling pots, Used for envelopes with windows, shopping bags, compost bags, stationery, miscellaneous goods, etc.
しかし、ポリ乳酸樹脂は、高温や高湿度下において加水分解されやすいため、耐久性に劣り、実使用に耐えうる物性を有しておらず、適用できる用途に制限がある。 However, since polylactic acid resin is easily hydrolyzed at high temperatures and high humidity, it is inferior in durability, does not have physical properties that can withstand actual use, and has limited applications.
そこで、耐加水分解性の観点から、カルボジイミド化合物を配合することが知られている。例えば、特許文献１では、カルボジイミド化合物として、モノカルボジイミド化合物とポリカルボジイミド化合物を併用している。また、特許文献２では、耐加水分解性を向上させる観点から、モノカルボジイミド化合物をポリ乳酸樹脂のカルボキシル基と反応させ、ついでポリカルボジイミド化合物を反応させる製造法が開示されている。
しかし、モノカルボジイミド化合物とポリカルボジイミド化合物を反応系に共存させて１段目で反応させる方法では、反応性が劣り、十分な耐加水分解性が得ることができない。また、モノカルボジイミド化合物を反応させてからポリカルボジイミド化合物を反応させる方法では、反応を２段階で行うため生産性に問題がある。またさらに、耐加水分解性に加えて、難燃性も向上した、さらなるポリ乳酸樹脂が要求されている。 However, in the method in which the monocarbodiimide compound and the polycarbodiimide compound are allowed to coexist in the reaction system and reacted in the first stage, the reactivity is inferior and sufficient hydrolysis resistance cannot be obtained. Further, the method of reacting the monocarbodiimide compound and then reacting the polycarbodiimide compound has a problem in productivity because the reaction is performed in two stages. Furthermore, in addition to hydrolysis resistance, further polylactic acid resin having improved flame retardancy is required.
本発明の課題は、耐加水分解性に優れ、かつ、難燃性に優れるポリ乳酸樹脂組成物及び、該組成物を成形することにより得られるポリ乳酸樹脂成形体及び該成形体の製造方法を提供することにある。 An object of the present invention is to provide a polylactic acid resin composition excellent in hydrolysis resistance and excellent in flame retardancy, a polylactic acid resin molded body obtained by molding the composition, and a method for producing the molded body It is to provide.
本発明者らは、上記課題を解決する為に検討を重ねた結果、ポリ乳酸樹脂組成物に、モノカルボジイミド化合物及びポリカルボジイミド化合物に加えて、さらにリン化合物を含有させることにより、１段反応でも耐加水分解性に優れ、かつ難燃性に優れるポリ乳酸樹脂組成物を得られることを見出し、本発明を完成するに至った。 As a result of repeated studies to solve the above-mentioned problems, the present inventors have added a phosphorus compound to the polylactic acid resin composition in addition to the monocarbodiimide compound and the polycarbodiimide compound, thereby allowing a one-step reaction. It has been found that a polylactic acid resin composition having excellent hydrolysis resistance and flame retardancy can be obtained, and the present invention has been completed.
即ち、本発明は、
〔１〕 ポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を含む原料を混合し、溶融混練して得られるポリ乳酸樹脂組成物、
〔２〕 前記〔１〕記載のポリ乳酸樹脂組成物を成形してなるポリ乳酸樹脂成形体、ならびに
〔３〕 ポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を含む原料を混合し、溶融混練する工程を含む、前記〔２〕記載のポリ乳酸樹脂成形体の製造方法
に関する。
That is, the present invention
[1] A polylactic acid resin composition obtained by mixing, melting and kneading raw materials containing a polylactic acid resin, a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound,
[2] A polylactic acid resin molded product obtained by molding the polylactic acid resin composition according to [1], and [3] a raw material containing a polylactic acid resin, a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound are mixed. The method for producing a polylactic acid resin molded article according to the above [2], comprising a step of melt-kneading.
本発明のポリ乳酸樹脂組成物は、耐加水分解性及び難燃性に優れるという優れた効果を奏するものである。また、該組成物は、１段反応により得られることから、生産性にも優れるという効果も奏する。 The polylactic acid resin composition of the present invention has an excellent effect of being excellent in hydrolysis resistance and flame retardancy. Further, since the composition is obtained by a one-step reaction, it also has an effect of being excellent in productivity.
本発明のポリ乳酸樹脂組成物は、ポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及び、リン化合物を含む原料を混合し、溶融混練して得られるものであり、ポリ乳酸樹脂、モノカルボジイミド化合物、及びポリカルボジイミド化合物に加えて、さらにリン化合物を用いることに大きな特徴を有する。本発明においては、モノカルボジイミド化合物及びポリカルボジイミド化合物によりポリ乳酸の末端のカルボキシル基を封鎖して加水分解を抑制する効果が発揮されるが、前記両化合物に加えてリン化合物を含有することにより、その効果をさらに向上することができ、またさらに、耐加水分解性と共に難燃性をも向上できる。その詳細な理由は不明なるも、モノカルボジイミド化合物及びポリカルボジイミド化合物と、リン化合物との相互作用によって、カルボジイミド基とカルボキシル基との反応性が向上し、前記効果が向上するものと考えられる。また、本発明のポリ乳酸樹脂組成物は、原料を混合することにより、モノカルボジイミド化合物及びポリカルボジイミド化合物と、リン化合物との相互作用が得られ、溶融混練によりカルボジイミド基とカルボキシル基との反応性が向上し、前記効果が向上するものと考えられる。 The polylactic acid resin composition of the present invention is obtained by mixing, melting and kneading a raw material containing a polylactic acid resin, a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound. A polylactic acid resin and a monocarbodiimide compound In addition to the polycarbodiimide compound, there is a great feature in using a phosphorus compound. In the present invention, the monocarbodiimide compound and the polycarbodiimide compound exert an effect of blocking hydrolysis by blocking the carboxyl group at the end of polylactic acid, but by containing a phosphorus compound in addition to the both compounds, The effect can be further improved, and further, flame resistance can be improved together with hydrolysis resistance. Although the detailed reason is unknown, it is considered that the reactivity between the carbodiimide group and the carboxyl group is improved by the interaction between the monocarbodiimide compound and the polycarbodiimide compound and the phosphorus compound, and the above effect is improved. In addition, the polylactic acid resin composition of the present invention allows the interaction between the monocarbodiimide compound and the polycarbodiimide compound and the phosphorus compound by mixing the raw materials, and the reactivity between the carbodiimide group and the carboxyl group by melt kneading. It is considered that the above effect is improved.
＜ポリ乳酸樹脂組成物＞
本発明のポリ乳酸樹脂組成物は、ポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及び、リン化合物を含む原料を混合し、溶融混練して得られる。
<Polylactic acid resin composition>
The polylactic acid resin composition of the present invention is obtained by mixing, melting and kneading a raw material containing a polylactic acid resin, a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound.
本発明に用いられるポリ乳酸樹脂としては、ポリ乳酸、又は乳酸とヒドロキシカルボン酸とのコポリマーが挙げられる。ヒドロキシカルボン酸として、グリコール酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシペンタン酸、ヒドロキシカプロン酸、ヒドロキシヘプタン酸等が挙げられ、グリコール酸、ヒドロキシカプロン酸が好ましい。 Examples of the polylactic acid resin used in the present invention include polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid. Examples of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxypentanoic acid, hydroxycaproic acid, hydroxyheptanoic acid and the like, and glycolic acid and hydroxycaproic acid are preferable.
好ましいポリ乳酸の分子構造は、Ｌ−乳酸又はＤ−乳酸いずれかの単位80〜100モル％とそれぞれの対掌体の乳酸単位0〜20モル％からなるものである。また、乳酸とヒドロキシカルボン酸とのコポリマーは、Ｌ−乳酸又はＤ−乳酸いずれかの単位85〜100モル％とヒドロキシカルボン酸単位0〜15モル％からなるものである。 The molecular structure of polylactic acid is preferably composed of 80 to 100 mol% of either L-lactic acid or D-lactic acid and 0 to 20 mol% of each enantiomer. The copolymer of lactic acid and hydroxycarboxylic acid is composed of 85 to 100 mol% of either L-lactic acid or D-lactic acid and 0 to 15 mol% of hydroxycarboxylic acid units.
これらのポリ乳酸樹脂は、Ｌ−乳酸、Ｄ−乳酸及びヒドロキシカルボン酸の中から必要とする構造のものを選んで原料とし、脱水重縮合することにより得ることができる。好ましくは、乳酸の環状二量体であるラクチド、グリコール酸の環状二量体であるグリコリド及びカプロラクトン等から必要とする構造のものを選んで開環重合することにより得ることができる。ラクチドにはＬ−乳酸の環状二量体であるＬ−ラクチド、Ｄ−乳酸の環状二量体であるＤ−ラクチド、Ｄ−乳酸とＬ−乳酸とが環状二量化したメソ−ラクチド及びＤ−ラクチドとＬ−ラクチドとのラセミ混合物であるＤＬ−ラクチドがある。本発明ではいずれのラクチドも用いることができる。但し、主原料は、Ｄ−ラクチド又はＬ−ラクチドが好ましい。 These polylactic acid resins can be obtained by dehydrating polycondensation using L-lactic acid, D-lactic acid and hydroxycarboxylic acid as a raw material by selecting those having the required structure. Preferably, it can be obtained by ring-opening polymerization by selecting a desired structure from lactide, which is a cyclic dimer of lactic acid, glycolide, which is a cyclic dimer of glycolic acid, and caprolactone. Lactide includes L-lactide which is a cyclic dimer of L-lactic acid, D-lactide which is a cyclic dimer of D-lactic acid, meso-lactide obtained by cyclic dimerization of D-lactic acid and L-lactic acid, and D-lactide. There is DL-lactide, which is a racemic mixture of lactide and L-lactide. Any lactide can be used in the present invention. However, the main raw material is preferably D-lactide or L-lactide.
市販されているポリ乳酸樹脂としては、例えば、三井化学社製、商品名レイシアシリーズ；ネイチャーワークス社製、商品名Ｎａｔｕｒｅ ｗｏｒｋｓシリーズ；トヨタ自動車社製、Ｕ’ｚシリーズ等が挙げられる。 Examples of commercially available polylactic acid resins include Mitsui Chemicals, trade name Lacia series; Nature Works, trade name Nature works series; Toyota Motor Corporation, U'z series, and the like.
これらのポリ乳酸樹脂の中でも結晶化速度、物性の観点からＬ−乳酸高純度品である結晶グレードのもの、例えば、三井化学社製、ＬＡＣＥＡ Ｈ−４００、ＬＡＣＥＡ Ｈ−１００、ＬＡＣＥＡ Ｈ−４４０が好ましく、Ｌ−乳酸純度９５％以上のポリ乳酸樹脂、例えば、三井化学社製、ＬＡＣＥＡ Ｈ−４００、ＬＡＣＥＡ Ｈ−１００がさらに好ましい。 Among these polylactic acid resins, L-lactic acid high purity products in terms of crystallization speed and physical properties, for example, LACEA H-400, LACEA H-100, LACEA H-440 manufactured by Mitsui Chemicals, Inc. Preferably, polylactic acid resins having an L-lactic acid purity of 95% or more, such as LACEA H-400 and LACEA H-100 manufactured by Mitsui Chemicals, are more preferable.
本発明に用いられるモノカルボジイミド化合物としては、ジフェニルカルボジイミド、ジ−２，６−ジメチルフェニルカルボジイミド、ジ−２，６−ジエチルフェニルカルボジイミド、ジ−２，６−ジイソプロピルフェニルカルボジイミド、ジ−２，６−ジtert−ブチルフェニルカルボジイミド、ジ−ｏ−トリルカルボジイミド、ジ−ｐ−トリルカルボジイミド、ジ−２，４，６−トリメチルフェニルカルボジイミド、ジ−２，４，６−トリイソプロピルフェニルカルボジイミド、ジ−２，４，６−トリイソブチルフェニルカルボジイミド等の芳香族モノカルボジイミド化合物；ジ−シクロヘキシルカルボジイミド等の脂環族モノカルボジイミド化合物；ジ−イソプロピルカルボジイミド、ジ−オクタデシルカルボジイミド等の脂肪族モノカルボジイミド化合物等が挙げられ、良好な耐加水分解性を得る観点及びポリ乳酸樹脂のカルボキシル基末端濃度を下げる観点から、芳香族モノカルボジイミド化合物が好ましく、ジ−２，６−ジイソプロピルフェニルカルボジイミド、ジ−２，６−ジメチルフェニルカルボジイミドがさらに好ましい。これらのモノカルボジイミド化合物は単独で又は２種以上組み合わせて用いることができる。 Examples of the monocarbodiimide compound used in the present invention include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, di-2,6-diethylphenylcarbodiimide, di-2,6-diisopropylphenylcarbodiimide, di-2,6- Di-tert-butylphenylcarbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-2,4,6-trimethylphenylcarbodiimide, di-2,4,6-triisopropylphenylcarbodiimide, di-2, Aromatic monocarbodiimide compounds such as 4,6-triisobutylphenylcarbodiimide; Alicyclic monocarbodiimide compounds such as di-cyclohexylcarbodiimide; Aliphatic monocarbols such as di-isopropylcarbodiimide and di-octadecylcarbodiimide An aromatic monocarbodiimide compound is preferable from the viewpoint of obtaining good hydrolysis resistance and reducing the carboxyl group terminal concentration of the polylactic acid resin, such as di-2,6-diisopropylphenylcarbodiimide, di- 2,6-dimethylphenylcarbodiimide is more preferred. These monocarbodiimide compounds can be used alone or in combination of two or more.
モノカルボジイミド化合物の配合量は、良好な耐加水分解性を得る観点及びポリ乳酸樹脂のカルボキシル基末端濃度を下げる観点から、ポリ乳酸樹脂100重量部に対して0.1〜10重量部が好ましく、0.1〜5重量部がより好ましい。また透明性の観点から0.1〜3重量部がさらに好ましく、0.1〜1.0重量部がさらに好ましく、0.1〜0.5重量部がさらにより好ましい。なお、本明細書において「配合量」とは、「配合量もしくは含有量」のことを意味する。 The compounding amount of the monocarbodiimide compound is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polylactic acid resin, from the viewpoint of obtaining good hydrolysis resistance and reducing the carboxyl group terminal concentration of the polylactic acid resin. 5 parts by weight is more preferred. Further, from the viewpoint of transparency, 0.1 to 3 parts by weight is more preferable, 0.1 to 1.0 part by weight is further preferable, and 0.1 to 0.5 part by weight is even more preferable. In the present specification, “blending amount” means “blending amount or content”.
本発明に用いられるポリカルボジイミド化合物としては、ポリ(４，４’−ジフェニルメタンカルボジイミド)、ポリ(ｐ−フェニレンカルボジイミド)、ポリ(ｍ−フェニレンカルボジイミド)、ポリ(ジイソプロピルフェニレンカルボジイミド)、ポリ(トリイソプロピルフェニレンカルボジイミド)等の芳香族ポリカルボジイミド化合物；ポリ(４，４’−ジシクロヘキシルメタンカルボジイミド)等の脂環族ポリカルボジイミド化合物；ポリ(ジイソプロピルカルボジイミド)等の脂肪族ポリカルボジイミド化合物が挙げられ、良好な耐加水分解性を得る観点から、芳香族ポリカルボジイミド化合物及び脂環族ポリカルボジイミド化合物が好ましい。これらのポリカルボジイミド化合物は単独で又は２種以上組み合わせて用いることができる。 Examples of the polycarbodiimide compound used in the present invention include poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (diisopropylphenylenecarbodiimide), and poly (triisopropylphenylene). Aromatic polycarbodiimide compounds such as carbodiimide); Alicyclic polycarbodiimide compounds such as poly (4,4′-dicyclohexylmethanecarbodiimide); Aliphatic polycarbodiimide compounds such as poly (diisopropylcarbodiimide); From the viewpoint of obtaining degradability, an aromatic polycarbodiimide compound and an alicyclic polycarbodiimide compound are preferred. These polycarbodiimide compounds can be used alone or in combination of two or more.
ポリカルボジイミド化合物の配合量は、良好な耐加水分解性を得る観点から、ポリ乳酸樹脂100重量部に対して0.1〜10重量部が好ましく、0.1〜5重量部がより好ましい。また、透明性の観点から、0.1〜3重量部がさらに好ましく、0.1〜1.0重量部がさらに好ましく、0.1〜0.5重量部がさらにより好ましい。 The blending amount of the polycarbodiimide compound is preferably 0.1 to 10 parts by weight and more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid resin from the viewpoint of obtaining good hydrolysis resistance. Moreover, from a viewpoint of transparency, 0.1-3 weight part is further more preferable, 0.1-1.0 weight part is further more preferable, 0.1-0.5 weight part is still more preferable.
また、良好な耐加水分解性を得る観点から、ポリカルボジイミド化合物は、モノカルボジイミド化合物とポリカルボジイミド化合物の配合割合〔モノカルボジイミド／ポリカルボジイミド(重量比)〕が、好ましくは1/9〜9/1、より好ましくは3/7〜7/3となるように配合することが好ましく、4/6〜6/4となるように配合することがさらに好ましい。 Further, from the viewpoint of obtaining good hydrolysis resistance, the polycarbodiimide compound is preferably a monocarbodiimide compound and a polycarbodiimide compound in a mixing ratio [monocarbodiimide / polycarbodiimide (weight ratio)] of preferably 1/9 to 9/1. More preferably, it is blended so as to be 3/7 to 7/3, and further preferably blended so as to be 4/6 to 6/4.
なお、モノカルボジイミド化合物及びポリカルボジイミド化合物は、市販のものを用いることができるが、例えば、イソシアネート化合物に、カルボジイミド化触媒(３−メチル−１−フェニル−２−ホスホレン−１−オキシド等)を30〜250℃、好ましくは30〜200℃で1〜10時間反応させることにより調製したものを使用することもできる。 As the monocarbodiimide compound and the polycarbodiimide compound, commercially available compounds can be used. For example, a carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide or the like) is added to an isocyanate compound. What was prepared by making it react at -250 degreeC, Preferably 30-200 degreeC for 1 to 10 hours can also be used.
本発明に用いられるリン化合物としては、モノカルボジイミド化合物、及びポリカルボジイミド化合物との併用により、これらが有するカルボジイミド基とポリ乳酸樹脂のカルボキシル基との反応性を向上させると共にポリ乳酸樹脂組成物の難燃性を向上させる観点から、リン酸エステル、フェニルホスホン酸金属塩、縮合リン酸エステル、リン酸塩及び縮合リン酸塩から選ばれる少なくとも１種が好ましい。 As the phosphorus compound used in the present invention, the combined use of a monocarbodiimide compound and a polycarbodiimide compound improves the reactivity between the carbodiimide group of these compounds and the carboxyl group of the polylactic acid resin, and makes the polylactic acid resin composition difficult. From the viewpoint of improving flammability, at least one selected from phosphoric acid esters, phenylphosphonic acid metal salts, condensed phosphoric acid esters, phosphates and condensed phosphates is preferred.
リン酸エステルとしては、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリ(２−エチルヘキシル)ホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(イソプロピルフェニル)ホスフェート、トリス(フェニルフェニル)ホスフェート、トリナフチルホスフェート、クレジルジフェニルホスフェート、キシレニルジフェニルホスフェート、ジフェニル(２−エチルヘキシル)ホスフェート、ジ(イソプロピルフェニル)フェニルホスフェート、モノイソデシルホスフェート、２−アクリロイルオキシエチルアシッドホスフェート、２−メタクリロイルオキシエチルアシッドホスフェート、ジフェニル−２−アクリロイルオキシエチルホスフェート、ジフェニル−２−メタクリロイルオキシエチルホスフェート、メラミンホスフェート、ジメラミンホスフェート、メラミンピロホスフェート、トリフェニルホスフィンオキサイド、トリクレジルホスフィンオキサイド、メタンホスホン酸ジフェニル、フェニルホスホン酸ジエチル、レジルシノールビス(ジフェニルホスフェート)、ビスフェノールＡビス(ジフェニルホスフェート)、ホスファフェナンスレン等が挙げられ、難燃性の向上の観点から、トリフェニルホスフェート、トリス(イソプロピルフェニル)ホスフェートが好ましい。 Phosphate esters include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (Phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxy Cyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, resilcinol bis (diphenyl) Phosphate), bisphenol A bis (diphenyl phosphate), phosphaphenanthrene, and the like. From the viewpoint of improving flame retardancy, triphenyl phosphate and tris (isopropylphenyl) phosphate are preferred.
フェニルホスホン酸金属塩は、置換基を有しても良いフェニル基とホスホン基(−ＰＯ(ＯＨ)2)を有するフェニルホスホン酸の金属塩であり、フェニル基の置換基としては、炭素数１〜１０のアルキル基、アルコキシ基の炭素数が１〜１０のアルコキシカルボニル基等が挙げられる。フェニルホスホン酸の具体例としては、無置換のフェニルホスホン酸、メチルフェニルホスホン酸、エチルフェニルホスホン酸、プロピルフェニルホスホン酸、ブチルフェニルホスホン酸、ジメトキシカルボニルフェニルホスホン酸、ジエトキシカルボニルフェニルホスホン酸等が挙げられ、無置換のフェニルホスホン酸が好ましい。 The phenylphosphonic acid metal salt is a metal salt of phenylphosphonic acid having a phenyl group which may have a substituent and a phosphonic group (—PO (OH) 2 ), and the substituent of the phenyl group has 1 carbon atom. -10 alkyl groups, alkoxycarbonyl groups having 1 to 10 carbon atoms, and the like. Specific examples of phenylphosphonic acid include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, and diethoxycarbonylphenylphosphonic acid. And unsubstituted phenylphosphonic acid is preferred.
フェニルホスホン酸の金属塩としては、リチウム、ナトリウム、マグネシウム、アルミニウム、カリウム、カルシウム、バリウム、銅、亜鉛、鉄、コバルト、ニッケル等の塩が挙げられ、亜鉛塩が好ましい。 Examples of the metal salt of phenylphosphonic acid include salts of lithium, sodium, magnesium, aluminum, potassium, calcium, barium, copper, zinc, iron, cobalt, nickel, and the like, and zinc salts are preferable.
縮合リン酸エステルとしては、トリアルキルポリホスフェート、レゾルシノールポリフェニルホスフェート、レゾルシノールポリ(ジ−２，６−キシリル)ホスフェート、ビスフェノールＡポリクレジルホスフェート、ハイドロキノンポリ(２，６−キシリル)ホスフェートならびにこれらの縮合物等の縮合リン酸エステルを挙げることができ、難燃性の向上の観点から、レゾルシノールポリ(ジ−２，６−キシリル)ホスフェートが好ましい。市販の縮合リン酸エステルとしては、例えば大八化学工業製ＰＸ−２００(レゾルシノールポリ(ジ−２，６−キシリル)ホスフェート)、ＰＸ−２０１(芳香族縮合リン酸エステル)、ＰＸ−２０２(芳香族縮合リン酸エステル)、ＣＲ−７３３Ｓ(レゾルシノールポリフェニルホスフェート)、ＣＲ−７４１(ビスフェノールＡポリクレジルホスフェート)、ＣＲ７４７(芳香族縮合リン酸エステル)、ＡＤＥＫＡ製アデカスタブＰＦＲ(レゾルシノールポリフェニルホスフェート)、ＦＰ−５００(レゾルシノールポリ(ジ−２，６−キシリル)ホスフェート)、ＦＰ−６００(ビスフェノールＡポリクレジルホスフェート)、ＦＰ−７００(ビスフェノールＡポリクレジルホスフェート)等を挙げることができ、ＰＸ−２００、ＰＸ−２０１、ＰＸ−２０２が好ましい。 Examples of the condensed phosphate ester include trialkyl polyphosphate, resorcinol polyphenyl phosphate, resorcinol poly (di-2,6-xylyl) phosphate, bisphenol A polycresyl phosphate, hydroquinone poly (2,6-xylyl) phosphate, and these A condensed phosphate ester such as a condensate can be mentioned, and resorcinol poly (di-2,6-xylyl) phosphate is preferred from the viewpoint of improving flame retardancy. Examples of commercially available condensed phosphate esters include PX-200 (resorcinol poly (di-2,6-xylyl) phosphate), PX-201 (aromatic condensed phosphate ester), and PX-202 (fragrance) manufactured by Daihachi Chemical Industry. Group condensed phosphate ester), CR-733S (resorcinol polyphenyl phosphate), CR-741 (bisphenol A polycresyl phosphate), CR747 (aromatic condensed phosphate ester), ADEKA ADK STAB PFR (resorcinol polyphenyl phosphate), FP-500 (resorcinol poly (di-2,6-xylyl) phosphate), FP-600 (bisphenol A polycresyl phosphate), FP-700 (bisphenol A polycresyl phosphate), etc. 200, PX-201, and PX-202 are preferred.
リン酸塩、縮合リン酸塩としては、例えば、リン酸及び／又はポリリン酸と、周期律表ＩＡ族〜IVＢ族の金属、アンモニア、脂肪族アミン、芳香族アミンから選ばれる少なくとも一種の金属又は化合物との塩からなるリン酸塩、ポリリン酸塩を挙げることができる。周期律表ＩＡ族〜IVＢ族の金属としてリチウム、ナトリウム、カルシウム、バリウム、鉄(II)、鉄(III)、アルミニウム等が挙げられ、脂肪族アミンとしてメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、エチレンジアミン、ピペラジン等が挙げられ、芳香族アミンとしてはピリジン、トリアジン、メラミン、アンモニウム等が挙げられる。これらの中では、難燃性向上の観点から、リン酸及び／又はポリリン酸と、周期律表ＩＡ族〜IVＢ族の金属及び／又はピペラジンとの塩からなるリン酸塩、ポリリン酸塩、リン酸及び／又はポリリン酸と、周期律表ＩＡ族〜IVＢ族の金属及び／又はピペラジンとの塩からなるリン酸塩、ポリリン酸塩との混合物(リン酸塩複合体)が好ましい。市販のリン酸塩、ポリリン酸塩としては、太平化学産業製タイエンＮ(リン酸アンモニウム)、タイエンＬ(ポリリン酸アンモニウム)、タイエンＥ(リン酸アルミニウム)、タイエンＳ(ポリリン酸アンモニウムアミド)、タイエンＨ(リン酸アルミニウム)、クラリアント製ＣｌａｒｉａｎｔＡＰ４７５(ポリリン酸アンモニウム複合体)、ＣｌａｒｉａｎｔＡＰ７５０(ポリリン酸アンモニウム複合体)、Ｃｌａｒｉａｎｔ１３１２(ポリリン酸アンモニウム複合体)、Ｃｌａｒｉａｎｔ１２５０(リン酸金属塩)、ＡＤＥＫＡ製ＦＰ−２１００(リン酸塩複合体)、ＦＰ−２１００Ｊ(リン酸塩複合体)、ＦＰ−２２００(リン酸塩複合体)、鈴裕化学製ＦＣP７３０(ポリリン酸アンモニウム複合体)、Ｂｕｄｅｎｈｅｉｍｕ製ＢＵＤＩＴ３１６７(ポリリン酸アンモニウム複合体)、日本化学工業製Ｎ−６ＭＥ(ニトロトリス(メチレン)ホスホン酸６メラミン塩)、日産化学工業製ＰＨＯＳＭＥＬ−２００(ポリリン酸メラミン)等が挙げられ、ＡＤＥＫＡ製ＦＰ−２１００、ＦＰ−２１００Ｊ、ＦＰ−２２００、日産化学工業製ＰＨＯＳＭＥＬ−２００が好ましい。 Examples of the phosphate and condensed phosphate include phosphoric acid and / or polyphosphoric acid and at least one metal selected from metals of Groups IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. Mention may be made of phosphates and polyphosphates consisting of salts with compounds. Examples of metals in groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. Examples of aliphatic amines include methylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, Piperazine and the like can be mentioned, and examples of the aromatic amine include pyridine, triazine, melamine and ammonium. Among these, from the viewpoint of improving the flame retardancy, phosphates, polyphosphates, phosphoruss composed of salts of phosphoric acid and / or polyphosphoric acid and metals of group IA to IVB and / or piperazine in the periodic table. A mixture of phosphate and polyphosphate (phosphate complex) composed of a salt of an acid and / or polyphosphoric acid with a metal of Group IA to IVB of the periodic table and / or piperazine is preferable. Examples of commercially available phosphates and polyphosphates include Taiyen N (ammonium phosphate), Taien L (ammonium polyphosphate), Taien E (aluminum phosphate), Taien S (polyammonium amide), Thaien H (aluminum phosphate), Clariant Clariant AP475 (ammonium polyphosphate complex), Clariant AP750 (ammonium polyphosphate complex), Clariant 1312 (ammonium polyphosphate complex), Clariant 1250 (metal phosphate metal salt), FP-2100 (ADEKA) Phosphate complex), FP-2100J (phosphate complex), FP-2200 (phosphate complex), Suzuhiro Chemical FCP730 (ammonium polyphosphate complex), Budenheimu BUDIT 3167 (ammonium polyphosphate) Complex), N-6ME (Nitrotris (methylene) phosphonic acid 6-melamine salt) manufactured by Nippon Kagaku Kogyo, PHOSMEL-200 (melamine polyphosphate) manufactured by Nissan Chemical Industries, etc., and FP-2100 and FP-2100J manufactured by ADEKA FP-2200 and PHOSMEL-200 manufactured by Nissan Chemical Industries are preferred.
これらのリン化合物は単独で又は２種以上組み合わせて用いることができる。 These phosphorus compounds can be used alone or in combination of two or more.
リン化合物の配合量は、良好な耐加水分解性を得る観点から、ポリ乳酸樹脂100重量部に対して5〜40重量部が好ましく、8〜35重量部がより好ましく、10〜35重量部がさらに好ましく、10〜30重量部がさらに好ましい。 The compounding amount of the phosphorus compound is preferably 5 to 40 parts by weight, more preferably 8 to 35 parts by weight, and more preferably 10 to 35 parts by weight with respect to 100 parts by weight of the polylactic acid resin, from the viewpoint of obtaining good hydrolysis resistance. More preferred is 10 to 30 parts by weight.
また、リン化合物の重量と、モノカルボジイミド化合物とポリカルボジイミド化合物の総重量との比〔リン化合物重量／(モノカルボジイミド化合物とポリカルボジイミド化合物の総重量)〕は、良好な耐加水分解性を得る観点から、4/1〜50/1が好ましく、8/1〜40/1がより好ましく、10/1〜30/1がさらに好ましく、15/1〜25/1がさらにより好ましい。 Further, the ratio of the weight of the phosphorus compound to the total weight of the monocarbodiimide compound and the polycarbodiimide compound [phosphorus compound weight / (total weight of the monocarbodiimide compound and polycarbodiimide compound)] is a viewpoint for obtaining good hydrolysis resistance. Therefore, 4/1 to 50/1 is preferable, 8/1 to 40/1 is more preferable, 10/1 to 30/1 is further preferable, and 15/1 to 25/1 is still more preferable.
本発明のポリ乳酸樹脂組成物にはさらに可塑剤、結晶核剤等を配合しても良い。 You may mix | blend a plasticizer, a crystal nucleating agent, etc. with the polylactic acid resin composition of this invention further.
可塑剤としては、特に限定されず、例えば、一般の生分解性樹脂に用いられるグリセリンジアセトモノラウレート、ジグリセリンテトラアセテート、アセチルクエン酸トリブチル等や、分子中に２個以上のエステル基を有するエチレンオキサイド付加物等が挙げられる。これらの中でも、ポリ乳酸樹脂の柔軟性及び透明性の観点から、分子中に２個以上のエステル基を有し、エチレンオキサイドの平均付加モル数が好ましくは２〜９、より好ましくは３〜９の化合物が好ましい。このような化合物としては、コハク酸、アジピン酸、１，３，６−ヘキサントリカルボン酸等の多価カルボン酸とポリエチレングリコールモノアルキルエーテルとのエステル、グリセリン、ポリエチレングリコール等の多価アルコールのアルキルエーテルエステル等が挙げられる。これらの可塑剤は単独又は２種以上組み合わせて用いてもよい。 The plasticizer is not particularly limited, and for example, glycerin diacetomonolaurate, diglycerin tetraacetate, tributyl acetylcitrate, etc. used in general biodegradable resins, and having two or more ester groups in the molecule Examples include ethylene oxide adducts. Among these, from the viewpoint of flexibility and transparency of the polylactic acid resin, the molecule has two or more ester groups, and the average added mole number of ethylene oxide is preferably 2-9, more preferably 3-9. Are preferred. Examples of such compounds include esters of polyvalent carboxylic acids such as succinic acid, adipic acid, 1,3,6-hexanetricarboxylic acid and polyethylene glycol monoalkyl ether, and alkyl ethers of polyhydric alcohols such as glycerin and polyethylene glycol. Examples include esters. These plasticizers may be used alone or in combination of two or more.
可塑剤の配合量は、ポリ乳酸樹脂100重量部に対して、可塑剤の効果を発現し、樹脂の特性を損なわない観点から、5〜70重量部が好ましく、10〜50重量部がより好ましく、10〜30重量部がさらに好ましい。 The blending amount of the plasticizer is preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the polylactic acid resin, from the viewpoint of expressing the effect of the plasticizer and not impairing the properties of the resin. 10 to 30 parts by weight is more preferable.
本発明において結晶核剤としては、有機核剤、無機核剤のいずれも用いることができる。有機核剤としては、ポリ乳酸樹脂の結晶化速度を向上させる観点から、融点が65℃以上のものが好ましく、70〜220℃のものがより好ましい。好ましい有機核剤としては、脂肪族エステル、脂肪族アミド、脂肪酸金属塩等が挙げられ、ポリ乳酸樹脂の結晶化速度を向上させる観点から、１２−ヒドロキシステアリン酸トリグリセライド、ベヘニン酸モノグリセライド、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、１２−ヒドロキシステアリン酸モノエタノールアミド、エチレンビスカプリル酸アミド、エチレンビスカプリン酸アミド等が好ましい。 In the present invention, as the crystal nucleating agent, either an organic nucleating agent or an inorganic nucleating agent can be used. The organic nucleating agent preferably has a melting point of 65 ° C. or higher, more preferably 70 to 220 ° C. from the viewpoint of improving the crystallization speed of the polylactic acid resin. Preferable organic nucleating agents include aliphatic esters, aliphatic amides, fatty acid metal salts and the like. From the viewpoint of improving the crystallization speed of polylactic acid resin, 12-hydroxystearic acid triglyceride, behenic acid monoglyceride, ethylenebis-12 -Hydroxystearic acid amide, hexamethylene bis 12-hydroxystearic acid amide, 12-hydroxystearic acid monoethanolamide, ethylene biscaprylic acid amide, ethylene biscapric acid amide and the like are preferable.
無機核剤としては、特に限定されないが、耐熱性、成形性、結晶化度の向上の観点から、タルク、スメクタイト、ベントナイト、ドロマイト、セリサイト、長石粉、カオリン、マイカ、モンモリロナイト等の珪酸塩が好ましい。 The inorganic nucleating agent is not particularly limited, but silicates such as talc, smectite, bentonite, dolomite, sericite, feldspar powder, kaolin, mica, montmorillonite are used from the viewpoint of improving heat resistance, moldability and crystallinity. preferable.
結晶核剤として有機核剤を用いる場合、有機核剤の配合量はポリ乳酸樹脂100重量部に対して、結晶核剤としての効果発現の観点から、0.1〜5重量部が好ましく、0.3〜5重量部がより好ましい。また、無機核剤を用いる場合、無機核剤の配合量はポリ乳酸樹脂100重量部に対して、結晶核剤としての効果発現の観点から、0.1〜150重量部が好ましく、3〜80重量部がより好ましい。 When an organic nucleating agent is used as the crystal nucleating agent, the blending amount of the organic nucleating agent is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid resin, from the viewpoint of manifesting the effect as a crystal nucleating agent, 0.3 to 5 Part by weight is more preferred. In addition, when an inorganic nucleating agent is used, the blending amount of the inorganic nucleating agent is preferably 0.1 to 150 parts by weight, and 3 to 80 parts by weight with respect to 100 parts by weight of the polylactic acid resin, from the viewpoint of the effect as a crystal nucleating agent. Is more preferable.
本発明のポリ乳酸樹脂組成物には、上記以外の他の成分として、酸化防止剤、滑剤、帯電防止剤、防曇剤、光安定剤、紫外線吸収剤、顔料、無機充填剤、防カビ剤、抗菌剤、発泡剤、難燃剤等を、本発明の目的達成を妨げない範囲で配合することができる。 In the polylactic acid resin composition of the present invention, an antioxidant, a lubricant, an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber, a pigment, an inorganic filler, and an antifungal agent are included as components other than those described above. Antibacterial agents, foaming agents, flame retardants, and the like can be blended within a range that does not hinder the achievement of the object of the present invention.
本発明のポリ乳酸樹脂組成物は、前記ポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を含有するものであれば特に限定なく調製することができる。 The polylactic acid resin composition of the present invention can be prepared without particular limitation as long as it contains the polylactic acid resin, monocarbodiimide compound, polycarbodiimide compound, and phosphorus compound.
＜ポリ乳酸樹脂成形体及びその製造方法＞
本発明のポリ乳酸樹脂成形体は、本発明のポリ乳酸樹脂組成物を成形することにより得られる。具体的には、例えば、押出し機等を用いてポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を混合して溶融させながら、必要により有機結晶核剤や無機充填剤等を配合し、次に得られた溶融物を射出成形機等により金型に充填して成形する。金型温度は、特に限定されないが、作業性を向上させる観点から、110℃以下が好ましく、90℃以下がより好ましく、80℃以下がさらに好ましい。またポリ乳酸樹脂組成物の結晶化速度を向上させる観点から、30℃以上が好ましく、40℃以上がより好ましく、60℃以上がさらに好ましい。かかる観点から、金型温度は30〜110℃が好ましく、40〜90℃がより好ましく、60〜80℃がさら好ましい。
<Polylactic acid resin molded product and method for producing the same>
The polylactic acid resin molded product of the present invention can be obtained by molding the polylactic acid resin composition of the present invention. Specifically, for example, an organic crystal nucleating agent or an inorganic filler is blended as necessary while mixing and melting polylactic acid resin, monocarbodiimide compound, polycarbodiimide compound, and phosphorus compound using an extruder or the like. Then, the obtained melt is filled into a mold by an injection molding machine or the like and molded. The mold temperature is not particularly limited, but is preferably 110 ° C. or less, more preferably 90 ° C. or less, and further preferably 80 ° C. or less from the viewpoint of improving workability. Further, from the viewpoint of improving the crystallization rate of the polylactic acid resin composition, it is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 60 ° C. or higher. From this viewpoint, the mold temperature is preferably 30 to 110 ° C, more preferably 40 to 90 ° C, and further preferably 60 to 80 ° C.
本発明のポリ乳酸樹脂成形体の耐加水分解性は、高温高湿度条件下に保存後の分子量保持率(％)、例えば、80℃／95％RHの条件下に72時間保存後の分子量保持率(％)により表すことができ、分子量保持率(％)が好ましくは80〜100％、より好ましくは90〜100％であることが望ましい。なお、本明細書において、分子量保持率とは、後述の実施例に記載の方法により測定される。 The hydrolysis resistance of the polylactic acid resin molding of the present invention is the molecular weight retention rate (%) after storage under high temperature and high humidity conditions, for example, molecular weight retention after storage for 72 hours under conditions of 80 ° C./95% RH. The molecular weight retention rate (%) is preferably 80 to 100%, more preferably 90 to 100%. In addition, in this specification, molecular weight retention is measured by the method as described in the below-mentioned Example.
本発明のポリ乳酸樹脂成形体の好ましい製造方法は、ポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を含有するポリ乳酸樹脂組成物を溶融混練する工程(以下工程(１)という)と、工程(１)で得られた溶融物を110℃以下の金型内に充填して成形する工程(以下工程(２)という)を含む方法である。 A preferred method for producing the polylactic acid resin molded article of the present invention is a step of melt-kneading a polylactic acid resin composition containing a polylactic acid resin, a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound (hereinafter referred to as step (1)). And a step (hereinafter referred to as step (2)) in which the melt obtained in step (1) is filled in a mold of 110 ° C. or less and molded.
工程(１)における溶融混練温度は、ポリ乳酸樹脂とモノカルボジイミド化合物及びポリカルボジイミド化合物との反応性、及びポリ乳酸樹脂の劣化防止の観点から、180〜230℃が好ましく、190〜220℃がより好ましく、190〜210℃がさらに好ましい。 The melt kneading temperature in the step (1) is preferably 180 to 230 ° C., more preferably 190 to 220 ° C. from the viewpoint of reactivity between the polylactic acid resin, the monocarbodiimide compound and the polycarbodiimide compound, and prevention of deterioration of the polylactic acid resin. Preferably, 190-210 degreeC is more preferable.
本発明においては、工程(１)を経た後、冷却して非晶状態(すなわち高角Ｘ線回折法で測定される結晶化度が１％以下となる条件)とした後、工程(２)を行う方法や、工程(１)を経た後、冷却して直ちに工程(２)を行う方法が好ましく、結晶化速度向上効果発現の観点から、工程(１)を経た後、冷却して直ちに工程(２)を行う方法がより好ましい。 In the present invention, after passing through step (1), it is cooled to an amorphous state (that is, a condition that the degree of crystallinity measured by high-angle X-ray diffraction is 1% or less), and then step (2) is performed. The method of performing and the method of performing step (2) immediately after passing through step (1) are preferred, and from the viewpoint of the effect of improving the crystallization rate, the step of cooling and immediately following step (1) ( The method of performing 2) is more preferable.
工程(２)の具体例としては、例えば、射出成形機等によりポリ乳酸樹脂組成物を110℃以下の金型内に充填し、成形する工程等が挙げられる。工程(２)における金型温度は、結晶化速度向上及び作業性向上の観点から、110℃以下が好ましく、90℃以下がより好ましく、80℃以下がさらに好ましい。また30℃以上が好ましく、40℃以上がより好ましく、60℃以上がさらに好ましい。かかる観点から、金型温度は30〜110℃が好ましく、40〜90℃がより好ましく、60〜80℃がさら好ましい。 Specific examples of the step (2) include, for example, a step of filling a polylactic acid resin composition in a mold of 110 ° C. or lower with an injection molding machine or the like and molding. The mold temperature in the step (2) is preferably 110 ° C. or lower, more preferably 90 ° C. or lower, and further preferably 80 ° C. or lower, from the viewpoint of improving the crystallization speed and improving workability. Moreover, 30 degreeC or more is preferable, 40 degreeC or more is more preferable, and 60 degreeC or more is further more preferable. From this viewpoint, the mold temperature is preferably 30 to 110 ° C, more preferably 40 to 90 ° C, and further preferably 60 to 80 ° C.
工程(２)における金型内での保持時間は5〜600秒が好ましく、ポリ乳酸樹脂組成物が結晶核剤を含有する場合は、相対結晶化度60％以上を達成し、かつ生産性向上の観点から、前記保持時間は5〜60秒が好ましく、8〜50秒がより好ましく、10〜45秒がさらに好ましい。なお、本明細書において、相対結晶化度とは以下の式で表される結晶化度を言う。
相対結晶化度（％）＝｛（（ΔＨｍ−ΔＨｃｃ）／ΔＨｍ×１００）｝
具体的には、相対結晶化度は、ＤＳＣ装置（パーキンエルマー社製ダイアモンドＤＳＣ）を用い、１ｓｔＲＵＮとして、昇温速度20℃／分で20℃から200℃まで昇温し、200℃で5分間保持した後、降温速度-20℃／分で200℃から20℃まで降温し、20℃で１分間保持した後、さらに２ｎｄＲＵＮとして、昇温速度20℃／分で20℃から200℃まで昇温した。１ｓｔＲＵＮに観測されるポリ乳酸樹脂の冷結晶化エンタルピーの絶対値ΔＨｃｃ、２ｎｄＲＵＮに観測される結晶融解エンタルピーΔＨｍを求めることができる。
The holding time in the mold in the step (2) is preferably 5 to 600 seconds. When the polylactic acid resin composition contains a crystal nucleating agent, a relative crystallinity of 60% or more is achieved and productivity is improved. From this viewpoint, the holding time is preferably 5 to 60 seconds, more preferably 8 to 50 seconds, and further preferably 10 to 45 seconds. In the present specification, the relative crystallinity refers to the crystallinity represented by the following formula.
Relative crystallinity (%) = {((ΔHm−ΔHcc) / ΔHm × 100)}
Specifically, the relative crystallinity was increased from 20 ° C. to 200 ° C. at a rate of temperature increase of 20 ° C./min using a DSC apparatus (Diamond DSC manufactured by PerkinElmer Co., Ltd.) at a rate of temperature increase of 20 ° C./min. After holding, the temperature is lowered from 200 ° C to 20 ° C at a temperature drop rate of -20 ° C / minute, held at 20 ° C for 1 minute, and then further increased from 20 ° C to 200 ° C at a temperature increase rate of 20 ° C / minute as 2ndRUN. did. The absolute value ΔHcc of the cold crystallization enthalpy of the polylactic acid resin observed at 1stRUN can be obtained as the crystal melting enthalpy ΔHm observed at 2ndRUN.
本発明のポリ乳酸樹脂成形体は、原料の本発明のポリ乳酸樹脂組成物がポリ乳酸樹脂、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を含有することから、前記原料を溶融混練することにより、モノカルボジイミド化合物及びポリカルボジイミド化合物と、リン化合物との親和性が向上し、耐加水分解性に優れ、かつ難燃性に優れるものである。また、モノカルボジイミド化合物及びポリカルボジイミド化合物と、リン化合物との相互作用の観点から、モノカルボジイミド化合物及びポリカルボジイミド化合物の溶融混練を同時に行うことにより、ポリ乳酸のカルボキシル基の封鎖が効率よく行われるため、本発明のポリ乳酸樹脂成形体の製造方法は、溶融混練工程を１段階で行ってもよく生産性にも優れるものである。 The polylactic acid resin molded article of the present invention is obtained by melting and kneading the raw materials since the raw polylactic acid resin composition of the present invention contains a polylactic acid resin, a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound. The affinity between the monocarbodiimide compound and the polycarbodiimide compound and the phosphorus compound is improved, the hydrolysis resistance is excellent, and the flame retardancy is excellent. In addition, from the viewpoint of the interaction between the monocarbodiimide compound and the polycarbodiimide compound and the phosphorus compound, the carboxyl group of polylactic acid is efficiently blocked by simultaneously performing melt-kneading of the monocarbodiimide compound and the polycarbodiimide compound. In the method for producing a polylactic acid resin molded body of the present invention, the melt-kneading step may be performed in one step, and the productivity is excellent.
合成例１(ジ−２，６−ジメチルフェニルカルボジイミド)
攪拌モーター、窒素ガスバブリング管及び冷却管を付けたフラスコに、２，６−ジメチルフェニルイソシアネート100g、カルボジイミド化触媒(３−メチル−１−フェニル−２−ホスホレン−１−オキシド)1g、及びトリエチレングリコールジメチルエーテル250mLを投入し、100℃で６時間カルボジイミド化反応をおこない、ジ−２，６−ジメチルフェニルカルボジイミドを得た。得られた生成物のＮＣＯ％は０であり、カルボジイミド化が完全に終了していることを確認した。
Synthesis Example 1 (Di-2,6-dimethylphenylcarbodiimide)
In a flask equipped with a stirring motor, a nitrogen gas bubbling tube and a condenser tube, 100 g of 2,6-dimethylphenyl isocyanate, 1 g of carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide), and triethylene 250 mL of glycol dimethyl ether was added, and carbodiimidization reaction was performed at 100 ° C. for 6 hours to obtain di-2,6-dimethylphenylcarbodiimide. NCO% of the obtained product was 0, and it was confirmed that carbodiimidization was completed.
合成例２〔ポリ(４，４’−ジフェニルメタンカルボジイミド)〕
攪拌モーター、窒素ガスバブリング管及び冷却管を付けたフラスコに、４，４’−ジフェニルメタンジイソシアネート100g、カルボジイミド化触媒(３−メチル−１−フェニル−２−ホスホレン−１−オキシド)1g、及びトリエチレングリコールジメチルエーテル250mLを投入し、100℃で３時間カルボジイミド化反応をおこない、ポリ(４，４’−ジフェニルメタンカルボジイミド)を得た。得られた生成物のＮＣＯ％は１８、重合度は５であった。
Synthesis Example 2 [Poly (4,4′-diphenylmethanecarbodiimide)]
In a flask equipped with a stirring motor, a nitrogen gas bubbling tube and a cooling tube, 100 g of 4,4′-diphenylmethane diisocyanate, 1 g of carbodiimidization catalyst (3-methyl-1-phenyl-2-phospholene-1-oxide), and triethylene 250 mL of glycol dimethyl ether was added and carbodiimidization reaction was performed at 100 ° C. for 3 hours to obtain poly (4,4′-diphenylmethanecarbodiimide). The obtained product had an NCO% of 18 and a degree of polymerization of 5.
合成例３(コハク酸とトリエチレングリコールモノメチルエーテルとのジエステル)
攪拌機、温度計、脱水管を備えた3Lフラスコに無水コハク酸500g、トリエチレングリコールモノメチルエーテル2463g、パラトルエンスルホン酸一水和物9.5gを仕込み、空間部に窒素（500mL／分）を吹き込みながら、減圧下4〜10.7kPa、110℃で15時間反応させた。反応液の酸価は1.6（KOHmg/g）であった。反応液に吸着剤キョーワード５００ＳＨ（協和化学工業（株）製）27gを添加して80℃、2.7kPaで45分間攪拌してろ過した後、液温115〜200℃、圧力0.03kPaでトリエチレングリコールモノメチルエーテルを留去し、80℃に冷却後、残液を減圧ろ過して、ろ液として、コハク酸とトリエチレングリコールモノメチルエーテルとのジエステルを得た。得られたジエステルは、酸価0.2（KOHmg/g）、鹸化価276（KOHmg/g）、水酸基価１以下（KOHmg/g）、色相ＡＰＨＡ２００であった。
Synthesis Example 3 (Diester of succinic acid and triethylene glycol monomethyl ether)
A 3L flask equipped with a stirrer, thermometer and dehydration tube was charged with 500g of succinic anhydride, 2463g of triethylene glycol monomethyl ether, and 9.5g of paratoluenesulfonic acid monohydrate, while blowing nitrogen (500mL / min) into the space. The mixture was reacted at 4 to 10.7 kPa and 110 ° C. for 15 hours under reduced pressure. The acid value of the reaction solution was 1.6 (KOHmg / g). Add 27g of adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) to the reaction solution, stir at 80 ° C and 2.7kPa for 45 minutes and filter, then triethylene at a liquid temperature of 115-200 ° C and pressure of 0.03kPa. After distilling off the glycol monomethyl ether and cooling to 80 ° C., the residue was filtered under reduced pressure to obtain a diester of succinic acid and triethylene glycol monomethyl ether as a filtrate. The obtained diester had an acid value of 0.2 (KOHmg / g), a saponification value of 276 (KOHmg / g), a hydroxyl value of 1 or less (KOHmg / g), and a hue of APHA200.
実施例１〜７及び比較例１〜３
表１に示すポリ乳酸樹脂、上記で合成したモノカルボジイミド化合物及びポリカルボジイミド化合物、リン化合物、可塑剤、ならびに結晶核剤を、２軸押出機(池貝鉄工社製、PCM-45)にて190℃で溶融混練し、ストランドカットを行い、実施例１〜７及び比較例１〜３のポリ乳酸樹脂組成物のペレットを得た。得られたペレットは、70℃減圧下で１日乾燥し、水分量を500ppm以下とした。
Examples 1-7 and Comparative Examples 1-3
The polylactic acid resin shown in Table 1, the monocarbodiimide compound and polycarbodiimide compound synthesized above, a phosphorus compound, a plasticizer, and a crystal nucleating agent were 190 ° C. in a twin-screw extruder (Ikegai Iron Works, PCM-45). The mixture was melt-kneaded and the strand was cut to obtain pellets of the polylactic acid resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3. The obtained pellets were dried at 70 ° C. under reduced pressure for 1 day, and the water content was adjusted to 500 ppm or less.
なお、表１における原料は以下の通りである。
〔ポリ乳酸樹脂〕
ＬＡＣＥＡ Ｈ−４００：三井化学社製
〔モノカルボジイミド化合物〕
ジ−２，６−ジイソプロピルフェニルカルボジイミド：ラインケミー社製、スタバクゾール ＬＦ
ジ−２，６−ジメチルフェニルカルボジイミド：上記合成例により調製
〔ポリカルボジイミド化合物〕
ポリ(４，４’−ジシクロヘキシルメタンカルボジイミド)：ラインケミー社製、スタバクゾールＰ
ポリ(４，４’−ジフェニルメタンカルボジイミド)：上記合成例により調製
〔リン化合物〕
ＦＰ−２２００：リン酸塩、アデカ社製
レオフォス６５：リン酸エステル、味の素ファインテクノ社製
ＰＸ−２００：縮合リン酸エステル、大八化学工業社製
ＰＨＯＳＭＥＬ−２００：縮合リン酸塩、日産化学工業社製
〔可塑剤〕
(ＭｅＥＯ３)２ＳＡ：コハク酸とトリエチレングリコールモノメチルエーテルとのジエステル化合物
〔有機結晶核剤〕
ＯＨＣ１８ＥＢ：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、スリパックスH)
ＰＰＡ−Ｚｎ：無置換のフェニルホスホン酸亜鉛塩(日産化学工業社製)
The raw materials in Table 1 are as follows.
[Polylactic acid resin]
LACEA H-400: manufactured by Mitsui Chemicals [monocarbodiimide compound]
Di-2,6-diisopropylphenylcarbodiimide: manufactured by Rhein Chemie, Stavaxol LF
Di-2,6-dimethylphenylcarbodiimide: prepared according to the above synthesis example [polycarbodiimide compound]
Poly (4,4′-dicyclohexylmethanecarbodiimide): manufactured by Rhein Chemie, Stavaxol P
Poly (4,4′-diphenylmethanecarbodiimide): prepared according to the above synthesis example [phosphorus compound]
FP-2200: Phosphate, Adeka Leophos 65: Phosphate ester, Ajinomoto Fine Techno Co., PX-200: Condensed phosphate ester, Daihachi Chemical Industry Co., Ltd. PHOSMEL-200: Condensed phosphate, Nissan Chemical Industries [Plasticizer]
(MeEO 3 ) 2 SA: Diester compound of succinic acid and triethylene glycol monomethyl ether [organic crystal nucleating agent]
OHC18EB: Ethylene bis 12-hydroxystearic acid amide (Nippon Kasei Co., Ltd., SLIPAX H)
PPA-Zn: unsubstituted phenylphosphonic acid zinc salt (manufactured by Nissan Chemical Industries)
次に、実施例１〜７及び比較例１〜３のペレットを、シリンダー温度を200℃とした射出成形機(日本製鋼所製 J75E-D)を用いて射出成形し、金型温度80℃、保持時間600秒（実施例7のみ60秒）でテストピース〔角柱状試験片(125mm×12mm×6mm)〕を成形し、以下の試験例１〜２の方法に従って特性を調べた。結果を表１に示す。 Next, the pellets of Examples 1 to 7 and Comparative Examples 1 to 3 were injection molded using an injection molding machine (Japan Steel Works J75E-D) with a cylinder temperature of 200 ° C., and a mold temperature of 80 ° C. A test piece [a prismatic test piece (125 mm × 12 mm × 6 mm)] was formed at a holding time of 600 seconds (60 seconds only in Example 7), and the characteristics were examined according to the methods of Test Examples 1 and 2 below. The results are shown in Table 1.
〔試験例１〕(難燃性)
角柱状試験片(125mm×12mm×6mm)について、Ｕｎｄｅｒｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ社の安全標準ＵＬ９４ 垂直燃焼試験の手順に基づき、垂直に保持した試料の下端に10秒間ガスバーナーの炎を接炎させ、燃焼が30秒以内に止まったならば、さらに10秒間接炎させ、ｎ＝５にて燃焼試験を実施した。ＵＬ９４垂直燃焼試験(ＵＬ９４Ｖ)の以下に示す判定基準に基づき、Ｖ−０、Ｖ−１、Ｖ−２、又はＮｏｔの判定を行った。
[Test Example 1] (Flame Retardancy)
For a prismatic test piece (125 mm × 12 mm × 6 mm), a gas burner flame was contacted to the lower end of a vertically held sample for 10 seconds based on the safety standard UL94 vertical combustion test procedure of Underwriters Laboratories, and the combustion was 30 If it stopped within seconds, an indirect flame was further applied for 10 seconds, and a combustion test was conducted at n = 5. Based on the criteria shown below in the UL94 vertical combustion test (UL94V), V-0, V-1, V-2, or Not was determined.
(難燃性の判定基準)
以下の基準においては、判定項目の全てについて該当するか否かの判定を行い、全てが該当する場合に、当該基準に相当すると判断する。
＜Ｖ−０＞
いずれの接炎の後も、10秒以上燃焼を続ける試料がない
5個の試料に対する10回の接炎に対する総燃焼時間が50秒を超えない
固定用クランプの位置まで燃焼する試料がない
試料の下方に置かれた脱脂綿を発火させる燃焼する粒子を落下させる試料がない
2回目の接炎の後、30秒以上赤熱を続ける試料がない
＜Ｖ−１＞
いずれの接炎の後も、30秒以上燃焼を続ける試料がない
5個の試料に対する10回の接炎に対する総燃焼時間が250秒を超えない
固定用クランプの位置まで燃焼する試料がない
試料の下方に置かれた脱脂綿を発火させる燃焼する粒子を落下させる試料がない
2回目の接炎の後、60秒以上赤熱を続ける試料がない
＜Ｖ−２＞
いずれの接炎の後も、30秒以上燃焼を続ける試料がない
5個の試料に対する10回の接炎に対する総燃焼時間が250秒を超えない
固定用クランプの位置まで燃焼する試料がない
試料の下方に置かれた脱脂綿を発火させる燃焼する粒子の落下が許容される
2回目の接炎の後、60秒以上赤熱を続ける試料がない
＜Ｎｏｔ＞
いずれの接炎の後も、30秒以上燃焼を続ける
(Flame resistance criteria)
In the following criteria, it is determined whether or not all of the determination items are applicable, and if all are applicable, it is determined that the criteria correspond to the criteria.
<V-0>
No sample continues to burn for more than 10 seconds after any flame contact
A sample that drops burning particles that ignite absorbent cotton placed underneath a sample that does not burn to the position of the clamping clamp where the total burning time for 10 flames of 5 samples does not exceed 50 seconds Absent
After the second flame contact, there is no sample that keeps red heat for 30 seconds or more <V-1>
No sample continues to burn for more than 30 seconds after any flame contact
A sample that drops burning particles that ignite absorbent cotton placed underneath a sample that has no sample to burn to the position of the clamping clamp where the total burning time for 10 flames of 5 samples does not exceed 250 seconds Absent
After the second flame contact, there is no sample that keeps red heat for 60 seconds or more <V-2>
No sample continues to burn for more than 30 seconds after any flame contact
Combustion particles that ignite absorbent cotton placed under the sample without burning sample to the position of the clamping clamp where the total burning time for 10 flames of 5 samples does not exceed 250 seconds are allowed Ru
After the second flame contact, there is no sample that continues red heat for more than 60 seconds <Not>
Continue burning for at least 30 seconds after any flame contact
〔試験例２〕(耐加水分解性)
角柱状試験片(125mm×12mm×6mm)について、80℃／95％RHの恒温湿機(プラチナスシリーズＰＳＬ−２、タバイエスペック社製)内に入れ、７２時間後の重量平均分子量(Ｍｗ)を測定し、次式より分子量保持率(％)を求めた。
分子量保持率(％)＝(７２時間後のＭｗ／初期Ｍｗ)×１００
[Test Example 2] (Hydrolysis resistance)
A prismatic test piece (125 mm x 12 mm x 6 mm) is placed in a constant temperature and humidity machine (Platinus series PSL-2, manufactured by Tabai Espec) at 80 ° C / 95% RH, and the weight average molecular weight (Mw) after 72 hours is calculated. The molecular weight retention rate (%) was determined from the following equation.
Molecular weight retention (%) = (Mw after 72 hours / initial Mw) × 100
なお、重量平均分子量(Ｍｗ)の測定は、ＧＰＣ(ゲルパーミエーションクロマトグラフィー)により、下記条件で行い、サンプル調製はクロロホルム10mLに試料30mgを溶解させて測定した。
カラム：ＧＭＨＨＲ-Ｈ×２
カラム温度：40℃
検出器：ＲＩ又はＵＶ(210nm)
溶離液：クロロホルム
流速：1.0mL／min
注入量：0.1mL
標準：ポリスチレン
The weight average molecular weight (Mw) was measured by GPC (gel permeation chromatography) under the following conditions, and the sample was prepared by dissolving 30 mg of the sample in 10 mL of chloroform.
Column: GMH HR -H × 2
Column temperature: 40 ° C
Detector: RI or UV (210nm)
Eluent: Chloroform flow rate: 1.0 mL / min
Injection volume: 0.1mL
Standard: Polystyrene
表１の結果から、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を含有した本発明のポリ乳酸樹脂組成物(実施例１〜７)は、分子量保持率90％以上の優れた耐加水分解性と、Ｖ−２以上の難燃性を達成することが可能であった。 From the results shown in Table 1, the polylactic acid resin compositions (Examples 1 to 7) of the present invention containing a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound have excellent hydrolysis resistance with a molecular weight retention of 90% or more. It was possible to achieve flame retardancy of V-2 or higher.
一方、モノカルボジイミド化合物とリン化合物、及びポリカルボジイミド化合物とリン化合物のみを含有したポリ乳酸樹脂組成物(比較例１〜２)は分子量保持率90％以上の耐加水分解性を達成することができなかった。また、モノカルボジイミド化合物とポリカルボジイミド化合物のみを含有したポリ乳酸樹脂組成物(比較例３)は、Ｖ−２以上の難燃性を達成することが不可能であった。 On the other hand, polylactic acid resin compositions (Comparative Examples 1 and 2) containing only a monocarbodiimide compound and a phosphorus compound, and a polycarbodiimide compound and a phosphorus compound can achieve hydrolysis resistance with a molecular weight retention of 90% or more. There wasn't. Moreover, the polylactic acid resin composition containing only the monocarbodiimide compound and the polycarbodiimide compound (Comparative Example 3) was unable to achieve flame retardancy of V-2 or higher.
以上の結果から、モノカルボジイミド化合物、ポリカルボジイミド化合物、及びリン化合物を含有した本発明のポリ乳酸樹脂組成物は、分子量保持率90％以上の優れた耐加水分解性を示し、その成形品は優れた難燃性を示すものであることが分かる。 From the above results, the polylactic acid resin composition of the present invention containing a monocarbodiimide compound, a polycarbodiimide compound, and a phosphorus compound exhibits excellent hydrolysis resistance with a molecular weight retention of 90% or more, and the molded product is excellent. It can be seen that it exhibits flame retardancy.
本発明のポリ乳酸樹脂組成物は、日用雑貨品、家電部品、自動車部品等の様々な工業用途に好適に使用することができる。 The polylactic acid resin composition of the present invention can be suitably used for various industrial applications such as household goods, household appliance parts, automobile parts and the like.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008164977A JP5319970B2 (en) | 2008-06-24 | 2008-06-24 | Polylactic acid resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008164977A JP5319970B2 (en) | 2008-06-24 | 2008-06-24 | Polylactic acid resin composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2010006869A JP2010006869A (en) | 2010-01-14 |
| JP2010006869A5 JP2010006869A5 (en) | 2011-05-12 |
| JP5319970B2 true JP5319970B2 (en) | 2013-10-16 |
Family
ID=41587720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008164977A Expired - Fee Related JP5319970B2 (en) | 2008-06-24 | 2008-06-24 | Polylactic acid resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5319970B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5493945B2 (en) * | 2010-02-08 | 2014-05-14 | 富士ゼロックス株式会社 | Polylactic acid-based resin composition, method for producing polylactic acid-based resin composition, and polylactic acid-based resin molded article |
| WO2011122080A1 (en) * | 2010-03-30 | 2011-10-06 | 日本電気株式会社 | Flame-retardant polylactide resin composition, molded object made therefrom, and manufacturing method therefor |
| NL2005163C2 (en) * | 2010-07-28 | 2012-01-31 | Stahl Int Bv | METHOD FOR THE PREPARATION OF MULTIFUNCTIONAL POLYCARBODIIMIDES, WHICH ARE USED AS A NETWORK. |
| WO2012128006A1 (en) * | 2011-03-22 | 2012-09-27 | 日本電気株式会社 | Aliphatic polyester resin composition, method for manufacturing same, and molded article |
| AT511395B1 (en) * | 2011-04-18 | 2013-12-15 | Sunpor Kunststoff Gmbh | FLAME-PROOF EXPANDABLE POLYMERISATE |
| WO2013180120A1 (en) * | 2012-05-30 | 2013-12-05 | 花王株式会社 | Polylactic acid resin composition |
| JP6055319B2 (en) * | 2013-01-21 | 2016-12-27 | 日清紡ケミカル株式会社 | Method for producing polyester resin composition |
| JP6227873B2 (en) * | 2013-01-21 | 2017-11-08 | 日清紡ケミカル株式会社 | Polyester resin composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000170034A (en) * | 1998-09-29 | 2000-06-20 | Toray Monofilament Co Ltd | Polyester monofilament and its use |
| JP2003192925A (en) * | 2001-10-15 | 2003-07-09 | Sony Corp | Biodegradable flame-retardant composite composition and method for producing the same |
| JP2005248032A (en) * | 2004-03-04 | 2005-09-15 | Sakamoto Yakuhin Kogyo Co Ltd | Flame retardant aliphatic polyester resin composition |
| JP4214071B2 (en) * | 2004-03-23 | 2009-01-28 | 東レ株式会社 | Polyester fiber |
| JP4954461B2 (en) * | 2004-10-15 | 2012-06-13 | 三井化学株式会社 | POLYLACTIC ACID RESIN COMPOSITION, FOAM PARTICLE, AND FOAM MOLDED BODY |
| JP2006249152A (en) * | 2005-03-08 | 2006-09-21 | Unitika Ltd | Biodegradable resin composition, molded product and method for producing the same |
| JP4957106B2 (en) * | 2005-07-25 | 2012-06-20 | 東レ株式会社 | Resin composition and molded article comprising the same |
| JP5124951B2 (en) * | 2006-02-03 | 2013-01-23 | 東レ株式会社 | Resin composition and molded article comprising the same |
| JP5259926B2 (en) * | 2006-03-02 | 2013-08-07 | 花王株式会社 | Method for producing polylactic acid resin composition |
| JP2008101083A (en) * | 2006-10-18 | 2008-05-01 | Unitika Ltd | Flame-retardant polylactic acid resin composition and molded article produced by molding the same |
| KR20100059782A (en) * | 2007-09-27 | 2010-06-04 | 유니띠까 가부시키가이샤 | Resin composition and molded body obtained by molding the same |
-
2008
- 2008-06-24 JP JP2008164977A patent/JP5319970B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010006869A (en) | 2010-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5319970B2 (en) | Polylactic acid resin composition | |
| JP5747503B2 (en) | Polylactic acid resin composition and polylactic acid resin molded article | |
| EP2067822B1 (en) | Biodegradable resin composition | |
| KR101150085B1 (en) | biodegradable resin composition | |
| KR101575617B1 (en) | Manufacturing method for polylactic acid resin compositions | |
| JP5009218B2 (en) | Polylactic acid resin composition | |
| JP5503852B2 (en) | Method for producing polylactic acid resin composition | |
| EP2264103B1 (en) | Polylactic acid resin composite | |
| JP5435977B2 (en) | Polylactic acid resin composition | |
| JP5796577B2 (en) | Polylactic acid resin composition and molded body thereof | |
| US9725593B2 (en) | Polylactic acid resin composition | |
| JP5950339B2 (en) | Polylactic acid resin composition | |
| JP2011190380A (en) | Resin composition, molded product, and method for producing the molded product | |
| JP5433197B2 (en) | Resin composition and injection molded body | |
| JP5256068B2 (en) | Polylactic acid resin composition | |
| JPWO2012049896A1 (en) | Polylactic acid resin composition and polylactic acid resin molded article | |
| WO2015079755A1 (en) | Polylactic acid resin composition | |
| JP5836703B2 (en) | Polylactic acid resin composition and molded article | |
| JP2013159672A (en) | Polylactic acid resin composition, and molding | |
| JP2013079356A (en) | Polylactic acid-based resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110323 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110323 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20120523 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120525 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120723 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120815 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120928 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121024 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121211 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130306 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130605 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20130613 |
|
| 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: 20130708 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130712 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5319970 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |