JP2012025855A - Processing method of rubber-containing polylactic acid-based thermoplastic resin composition, and regenerated thermoplastic resin composition - Google Patents
Processing method of rubber-containing polylactic acid-based thermoplastic resin composition, and regenerated thermoplastic resin composition Download PDFInfo
- Publication number
- JP2012025855A JP2012025855A JP2010166031A JP2010166031A JP2012025855A JP 2012025855 A JP2012025855 A JP 2012025855A JP 2010166031 A JP2010166031 A JP 2010166031A JP 2010166031 A JP2010166031 A JP 2010166031A JP 2012025855 A JP2012025855 A JP 2012025855A
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- JP
- Japan
- Prior art keywords
- thermoplastic resin
- rubber
- resin composition
- polylactic acid
- lactide
- 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.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 153
- 239000005060 rubber Substances 0.000 title claims abstract description 148
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 142
- 239000011342 resin composition Substances 0.000 title claims abstract description 127
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 99
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 98
- 238000003672 processing method Methods 0.000 title claims description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920001577 copolymer Polymers 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 230000003287 optical effect Effects 0.000 claims description 8
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 4
- 239000000805 composite resin Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000002950 deficient Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 46
- 229920000578 graft copolymer Polymers 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 14
- -1 polyethylene Polymers 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 229920002554 vinyl polymer Polymers 0.000 description 10
- 238000004064 recycling Methods 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
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- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005979 thermal decomposition 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
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010559 graft polymerization reaction Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
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- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 230000006340 racemization Effects 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 3
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- 230000006866 deterioration Effects 0.000 description 2
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- 239000012153 distilled water Substances 0.000 description 2
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
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- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
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- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、ゴム含有ポリ乳酸系熱可塑性樹脂組成物のケミカル・マテリアルリサイクル技術に関するものである。
即ち、本発明はゴム含有ポリ乳酸系熱可塑性樹脂組成物を処理して効率的にラクチドとゴム含有熱可塑性樹脂組成物を分離、回収する方法に関する。本発明はまた、ゴム含有ポリ乳酸系熱可塑性樹脂組成物から回収されたラクチド及びゴム含有熱可塑性樹脂組成物と、このゴム含有熱可塑性樹脂組成物を用いた再生熱可塑性樹脂組成物に関する。
The present invention relates to a chemical / material recycling technique for a rubber-containing polylactic acid-based thermoplastic resin composition.
That is, the present invention relates to a method for efficiently separating and recovering lactide and a rubber-containing thermoplastic resin composition by treating a rubber-containing polylactic acid-based thermoplastic resin composition. The present invention also relates to a lactide recovered from a rubber-containing polylactic acid-based thermoplastic resin composition and a rubber-containing thermoplastic resin composition, and a recycled thermoplastic resin composition using the rubber-containing thermoplastic resin composition.
近年、地球温暖化の要因として、大気中における炭酸ガス濃度の上昇が指摘され、地球規模での炭酸ガス排出規制の必要性が唱えられている。炭酸ガス排出源としては、生物の呼吸、バクテリアによる腐敗・醗酵等も有るが、燃焼による部分が大きく、現状の大気中の炭酸ガス濃度上昇現象は、人間による産業革命以後の石油資源を浪費した経済活動によってもたらされたものと一般的には考えられている。 In recent years, an increase in the concentration of carbon dioxide in the atmosphere has been pointed out as a cause of global warming, and the need for carbon dioxide emission regulations on a global scale has been advocated. Carbon dioxide emission sources include respiration of organisms, rot and fermentation by bacteria, etc., but it is largely due to combustion, and the current phenomenon of rising carbon dioxide concentration in the atmosphere wasted oil resources after the industrial revolution by humans It is generally considered to have been brought about by economic activity.
ところで、最近、カーボンニュートラルとして、炭酸ガスを吸収、固定する植物資源の有効活用が注目されている。即ち、植生によって、炭酸ガスの吸収を図る一方で、将来枯渇が予想される石油資源の代替を図るというものである。 Recently, attention has been focused on effective use of plant resources that absorb and fix carbon dioxide as carbon neutral. In other words, vegetation is intended to absorb carbon dioxide while replacing petroleum resources that are expected to be depleted in the future.
プラスチックにおいても、従来の原油を基礎原料とするものから、バイオマスを利用したプラスチックが開発され、これらは植物由来樹脂としてその活用が推進されている。 As for plastics, biomass-based plastics have been developed from those based on conventional crude oil, and their use is being promoted as plant-derived resins.
一方、昨今の原油価格高騰により、原油から製造するプラスチックやガソリン等の価格上昇が止まらず、社会問題となっている。使用済みの各種プラスチックをケミカル・マテリアルリサイクルすることは、近い将来、危惧される原油枯渇に備えるために必要な技術開発分野であり、企業の社会的責任を果たす観点からもその重要性は高まっている。 On the other hand, with the recent rise in crude oil prices, the rise in prices of plastics and gasoline produced from crude oil has not stopped and has become a social problem. Chemical and material recycling of used plastics is an area of technological development necessary to prepare for the fear of crude oil depletion in the near future, and its importance is increasing from the perspective of fulfilling corporate social responsibility. .
現在、植物由来樹脂としては、ラクチドを開環重合してなるポリ乳酸（ＰＬＡ）が主流であり、他の化石由来樹脂とのアロイ体が工業化されている。 Currently, polylactic acid (PLA) obtained by ring-opening polymerization of lactide is the mainstream as plant-derived resin, and alloys with other fossil-derived resins have been industrialized.
従来、ポリ乳酸の熱分解関連の技術として、例えば、以下のようなものが提案されている。
特許文献１には、廃棄された高分子量ポリ乳酸からラクチドを高純度で回収する方法として、廃棄された高分子量ポリ乳酸を、スズ又はスズ化合物からなる触媒の存在下にラクチドに変換し、回収する技術が開示されている。
特許文献２には、乳酸エステルをモノブチルスズの存在下で、１２０〜２３０℃に加熱することによって、高純度のラクチドを得る技術が開示されている。
特許文献３には、分子量４００〜３０００の乳酸オリゴマーに酸化銅を添加して、１３０℃〜２６０℃に加熱することによって、生成するラクチドのラセミ化を抑制した上でラクチドを得る方法が開示されている。
更に特許文献４には、周期律表ＩＡ，ＩＩＩＡ，ＩＶＡ，ＩＩＢ，及びＶＡ族の触媒を用いた乳酸オリゴマーの解重合反応系内に、水蒸気を吹き込みながら１３０〜２６０℃に加熱することによって、ラセミ化を抑制するラクチドの製造方法が開示されている。
しかしながら、これらの方法であってもラクチドのラセミ化が進み、回収されるラクチドの光学純度が低いという問題がある。
Conventionally, for example, the following has been proposed as a technique related to thermal decomposition of polylactic acid.
In Patent Document 1, as a method for recovering lactide from discarded high molecular weight polylactic acid with high purity, the discarded high molecular weight polylactic acid is converted into lactide in the presence of a catalyst made of tin or a tin compound, and recovered. Techniques to do this are disclosed.
Patent Document 2 discloses a technique for obtaining high-purity lactide by heating a lactic acid ester to 120 to 230 ° C. in the presence of monobutyltin.
Patent Document 3 discloses a method for obtaining lactide while suppressing racemization of the produced lactide by adding copper oxide to a lactic acid oligomer having a molecular weight of 400 to 3000 and heating to 130 ° C. to 260 ° C. ing.
Furthermore, in Patent Document 4, by heating to 130 to 260 ° C. while blowing water vapor into a depolymerization reaction system of a lactic acid oligomer using a catalyst of Periodic Tables IA, IIIA, IVA, IIB, and VA, A method for producing lactide that inhibits racemization is disclosed.
However, even in these methods, there is a problem that racemization of lactide proceeds and the optical purity of the recovered lactide is low.
特許文献５には、ポリ乳酸に、熱分解触媒としてのスズ化合物の他に高沸点のアルコール類を添加して、加アルコール分解の後に解重合させるラクチドの回収方法が開示されている。また、特許文献６には、酸化第一鉄を触媒とする方法、特許文献７には、アルカリ金属の水酸化物やアルコキシド、及びカルボン酸との塩などを触媒とする方法が開示されているが、これらはいずれも乳酸オリゴマーからのラクチド合成の方法である。 Patent Document 5 discloses a method for recovering lactide in which high-boiling alcohols are added to polylactic acid in addition to a tin compound as a thermal decomposition catalyst, and depolymerized after alcoholysis. Patent Document 6 discloses a method using ferrous oxide as a catalyst, and Patent Document 7 discloses a method using an alkali metal hydroxide or alkoxide, a salt with a carboxylic acid, or the like as a catalyst. However, these are all methods for synthesizing lactide from lactic acid oligomers.
特許文献８には、ポリ乳酸を含有するポリマーから高純度のラクチドを回収する方法として、解重合触媒に酸化マグネシウムを用い、反応器としてエクストルーダーを用い、エクストルーダーのベント口からラクチドを回収する方法が開示されている。
この特許文献８では、ポリ乳酸を含有するポリマーとして、ポリ乳酸と直鎖状ポリエチレンとのブレンド物を適用した実施例が記載されているが、ポリ乳酸からのラクチドの分解生成の確認にとどまり、ラクチドとポリエチレンとを分離して、ラクチドだけでなく、ポリエチレンを回収することは行われていない。
即ち、従来の技術はいずれもポリ乳酸からのラクチドの回収を目的としており、従来において、ポリ乳酸含有熱可塑性樹脂組成物からラクチドを回収すると共に、熱可塑性樹脂組成物をもその物性の低下を抑えた上で効率的に分離、回収する技術は提案されていなかった。
In Patent Document 8, as a method for recovering high-purity lactide from a polymer containing polylactic acid, magnesium oxide is used as a depolymerization catalyst, an extruder is used as a reactor, and lactide is recovered from the vent port of the extruder. A method is disclosed.
In this Patent Document 8, an example in which a blend of polylactic acid and linear polyethylene is applied as a polymer containing polylactic acid is described. However, the decomposition of lactide from polylactic acid is only confirmed. Lactide and polyethylene are not separated to recover not only lactide but also polyethylene.
That is, all of the conventional techniques are aimed at recovering lactide from polylactic acid, and conventionally, lactide is recovered from a polylactic acid-containing thermoplastic resin composition, and the physical properties of the thermoplastic resin composition are also reduced. No technology has been proposed for efficient separation and recovery after suppression.
本発明は、上記従来の実状に鑑みてなされたものであって、その目的は、生産工程上発生する不良品や市場から回収されるゴム含有ポリ乳酸系熱可塑性樹脂組成物を処理して、高純度のラクチドとゴム含有熱可塑性樹脂組成物とに効率的に分離、回収する方法を提供することにある。 The present invention has been made in view of the above-described conventional situation, and its purpose is to treat a defective product generated in the production process or a rubber-containing polylactic acid-based thermoplastic resin composition recovered from the market, An object of the present invention is to provide a method for efficiently separating and recovering high-purity lactide and rubber-containing thermoplastic resin composition.
本発明者らは、従来の技術の検証・改良に鋭意努力した結果、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）に特定量のアルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）を添加して押出機で熱処理することにより、高純度のラクチド（Ｄ）とゴム含有熱可塑性樹脂組成物（Ｅ）とを効率的に分離、回収することができることを見出し、本発明に至った。
即ち、本発明は以下を要旨とする。
As a result of diligent efforts to verify and improve the prior art, the present inventors have determined that the rubber-containing polylactic acid-based thermoplastic resin composition (A) has a specific amount of alkaline earth metal oxide (B) and hard (co) It has been found that by adding the polymer (C) and heat-treating with an extruder, the high-purity lactide (D) and the rubber-containing thermoplastic resin composition (E) can be efficiently separated and recovered, The present invention has been reached.
That is, the gist of the present invention is as follows.
［１］ ゴム含有ポリ乳酸系熱可塑性樹脂組成物を処理して、ラクチドとゴム含有熱可塑性樹脂組成物とを分離、回収する方法であって、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）１００重量部と、アルカリ土類金属酸化物（Ｂ）０.００５〜２０重量部と、硬質（共）重合体（Ｃ）５〜２００重量部とを（ただし、（Ｂ）成分と（Ｃ）成分との合計１００重量部中の（Ｂ）成分の割合は０．１〜１０重量部とする）、シリンダー設定温度１８０〜２５０℃の押出機に連続的に投入してラクチド（Ｄ）とゴム含有熱可塑性樹脂組成物（Ｅ）を分離、回収することを特徴とするゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法。 [1] A method of treating a rubber-containing polylactic acid-based thermoplastic resin composition to separate and recover lactide and rubber-containing thermoplastic resin composition, wherein the rubber-containing polylactic acid-based thermoplastic resin composition (A ) 100 parts by weight, alkaline earth metal oxide (B) 0.005 to 20 parts by weight and hard (co) polymer (C) 5 to 200 parts by weight (provided that component (B) and (C The ratio of the component (B) in the total 100 parts by weight of the component) is 0.1 to 10 parts by weight), and continuously charged into an extruder having a cylinder set temperature of 180 to 250 ° C. and lactide (D) A method for treating a rubber-containing polylactic acid-based thermoplastic resin composition, comprising separating and collecting the rubber-containing thermoplastic resin composition (E).
［２］ ［１］において、前記ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）は、樹脂成分としてポリ乳酸とゴム含有熱可塑性樹脂とを含み、ポリ乳酸の含有量が２５〜９５重量％の複合樹脂組成物であるゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法。 [2] In [1], the rubber-containing polylactic acid-based thermoplastic resin composition (A) includes polylactic acid and a rubber-containing thermoplastic resin as resin components, and the content of polylactic acid is 25 to 95% by weight. A method for treating a rubber-containing polylactic acid-based thermoplastic resin composition, which is a composite resin composition.
［３］ ［１］又は［２］において、前記押出機は少なくとも１箇所以上のベント口を有し、該ベント口よりラクチド（Ｄ）を回収し、ダイ部よりゴム含有熱可塑性樹脂組成物（Ｅ）を回収するゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法。 [3] In [1] or [2], the extruder has at least one vent port, and lactide (D) is recovered from the vent port, and a rubber-containing thermoplastic resin composition ( A method for treating a rubber-containing polylactic acid-based thermoplastic resin composition for recovering E).
［４］ ［３］において、前記押出機のベント口より回収されるラクチド（Ｄ）の光学純度が、Ｌ−ラクチド９０％以上であるゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法。 [4] The method for treating a rubber-containing polylactic acid-based thermoplastic resin composition according to [3], wherein the optical purity of the lactide (D) recovered from the vent port of the extruder is 90% or more of L-lactide.
［５］ ［３］又は［４］において、前記押出機のダイ部より回収されるゴム含有熱可塑性樹脂組成物（Ｅ）の樹脂流動性が、ＩＳＯ１１３３に準ずるメルトボリュームフローレート（ＭＶＲ）の測定値で、２２０℃×９８Ｎの条件下、１０〜８０ｃｍ３／１０分であるゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法。 [5] Measurement of melt volume flow rate (MVR) in [3] or [4] in which the resin fluidity of the rubber-containing thermoplastic resin composition (E) recovered from the die part of the extruder conforms to ISO1133. The processing method of the rubber-containing polylactic acid-type thermoplastic resin composition which is 10-80 cm < 3 > / 10 minutes on condition of 220 degreeC x 98N.
［６］ ［１］ないし［５］のいずれかに記載のゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法で回収されたラクチド（Ｄ）。 [6] Lactide (D) recovered by the method for treating a rubber-containing polylactic acid-based thermoplastic resin composition according to any one of [1] to [5].
［７］ ［１］ないし［４］のいずれかに記載のゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法で回収されたゴム含有熱可塑性樹脂組成物（Ｆ）。 [7] A rubber-containing thermoplastic resin composition (F) recovered by the method for treating a rubber-containing polylactic acid-based thermoplastic resin composition according to any one of [1] to [4].
［８］ ［７］に記載のゴム含有熱可塑性樹脂組成物（Ｅ）と他の熱可塑性樹脂（Ｆ）とを混合してなることを特徴とする再生熱可塑性樹脂組成物。 [8] A recycled thermoplastic resin composition comprising the rubber-containing thermoplastic resin composition (E) according to [7] and another thermoplastic resin (F).
本発明によれば、生産工程上発生する不良品や市場から回収されるゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）から高純度のラクチド（Ｄ）とゴム含有熱可塑性樹脂組成物（Ｅ）とを効率的に分離、回収して再利用することができる。従って、地球環境負荷低減、循環型社会構築において、本発明の工業的価値は極めて大きい。 According to the present invention, a high-purity lactide (D) and a rubber-containing thermoplastic resin composition (E) from a defective product generated in the production process or a rubber-containing polylactic acid-based thermoplastic resin composition (A) recovered from the market. ) Can be efficiently separated, recovered and reused. Therefore, the industrial value of the present invention is extremely large in reducing the global environmental load and building a recycling society.
以下に本発明の実施の形態を詳細に説明する。
なお、本発明において、「（共）重合」の文言は「重合」と「共重合」の双方を含む意味で用いる。
Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, the term “(co) polymerization” is used to mean both “polymerization” and “copolymerization”.
［ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）］
まず、本発明における処理対象であるゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）について説明する。
本発明に係るゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）は、樹脂成分としてポリ乳酸とゴム含有熱可塑性樹脂とを含む複合樹脂（アロイ体）組成物である。
[Rubber-containing polylactic acid-based thermoplastic resin composition (A)]
First, the rubber-containing polylactic acid-based thermoplastic resin composition (A) that is a treatment target in the present invention will be described.
The rubber-containing polylactic acid-based thermoplastic resin composition (A) according to the present invention is a composite resin (alloy body) composition containing polylactic acid and a rubber-containing thermoplastic resin as resin components.
＜ポリ乳酸＞
ポリ乳酸には、Ｌ体、Ｄ体、ＤＬ体の３種の光学異性体が存在し、市販されているポリ乳酸としては、Ｌ体の純度が１００％に近いものがあるが、本発明で処理するゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）に含まれるポリ乳酸は、特にその純度を規定するものではなく、また、本発明の効果を損なわない範囲で、他の共重合成分を含んだ共重合体でも構わない。
<Polylactic acid>
Polylactic acid has three optical isomers, L-form, D-form and DL-form, and commercially available polylactic acid has a purity of L-form close to 100%. The polylactic acid contained in the rubber-containing polylactic acid-based thermoplastic resin composition (A) to be treated is not particularly limited in its purity, and other copolymer components are added within a range not impairing the effects of the present invention. It may be a copolymer.
ポリ乳酸に含まれる他の共重合成分としては、エチレングリコール、ブロピレングリコール、ブタンジオール、ヘプタンジオール、ヘキサンジオール、オクタンジオール、ノナンジオ−ル、デカンジオール、１，４−シクロヘキサンジメタノ−ル、ネオペンチルグリコール、グリセリン、ペンタエリスリトール、ビスフェノ−ルＡ、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのグリコール化合物；シュウ酸、コハク酸、アジピン酸、セバシン酸、アゼライン酸、ドデカンジオン酸、マロン酸、グルタル酸、シクロヘキサンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、ナフタレンジカルボン酸、ビス（ｐ−カルボキシフェニル）メタン、アントラセンジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸、５−ナトリウムスルホイソフタル酸、５−テトラブチルホスホニウムイソフタル酸などのジカルボン酸；グリコール酸、ヒドロキシプロピオン酸、ヒドロキシ酪酸、ヒドロキシ吉草酸、ヒドロキシカプロン酸、ヒドロキシ安息香酸などのヒドロキシカルボン酸；カプロラクトン、バレロラクトン、プロピオラクトン、ウンデカラクトン、１，５−オキセパン−２−オンなどのラクトン類などを挙げることができる。このような共重合成分の含有量は、ポリ乳酸中の全単量体成分中通常３０モル％以下の含有量とするのが好ましく、１０モル％以下であることがより好ましい。 Other copolymerization components contained in polylactic acid include ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neo Glycol compounds such as pentyl glycol, glycerin, pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, Glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diph Dicarboxylic acids such as nyl ether dicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid; hydroxycarboxylic acids such as glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid Lactones such as caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one, and the like. The content of such a copolymer component is usually preferably 30 mol% or less, more preferably 10 mol% or less, based on all monomer components in polylactic acid.
ポリ乳酸の分子量や分子量分布については、実質的に成形加工が可能であれば特に制限されるものではないが、重量平均分子量（Ｍｗ）としては、通常１万以上、好ましくは５万以上、さらに１０万以上であることが望ましい。ポリ乳酸の重量平均分子量の上限については特に制限はないが、通常４０万以下である。 The molecular weight and molecular weight distribution of polylactic acid are not particularly limited as long as it can be practically processed, but the weight average molecular weight (Mw) is usually 10,000 or more, preferably 50,000 or more, It is desirable that it is 100,000 or more. Although there is no restriction | limiting in particular about the upper limit of the weight average molecular weight of polylactic acid, Usually, it is 400,000 or less.
なお、分子量の測定はＧＰＣ（溶媒ＴＨＦ：テトラヒドロフラン）にて測定することができるが、ポリ乳酸がペレット状の場合、ＴＨＦに溶解し難い場合があり、その場合は、クロロホルムに溶解させた後、メタノールを用いてポリマー成分を析出させ、そのポリマー成分を乾燥させたものをＴＨＦに溶解させて可溶分の分子量を測定することができる。また、必要に応じて加温するなどして溶解させることもできる。 The molecular weight can be measured by GPC (solvent THF: tetrahydrofuran), but when polylactic acid is in the form of pellets, it may be difficult to dissolve in THF. In that case, after dissolving in chloroform, The polymer component is precipitated using methanol, and the dried polymer component is dissolved in THF, and the molecular weight of the soluble component can be measured. Further, it can be dissolved by heating as necessary.
ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）に含まれるポリ乳酸は、１種のみであっても良く、２種以上が含まれていても良い。
ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）に用いられるポリ乳酸の具体例としては、例えば、市販品のネイチャーワークス社製「インジオ」、中国海生生物材料公司社製「レヴォダ」などが挙げられる。
The polylactic acid contained in the rubber-containing polylactic acid-based thermoplastic resin composition (A) may be only one type or two or more types.
Specific examples of the polylactic acid used in the rubber-containing polylactic acid-based thermoplastic resin composition (A) include, for example, commercially available “Ingeo” manufactured by Nature Works, “Levoda” manufactured by China Marine Biomaterials Corporation, etc. Can be mentioned.
ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）中のポリ乳酸の含有量は、好ましくは、２５〜９５重量％の範囲であるが、より好ましくは３０〜９５重量％、更に好ましくは５０〜９０重量％であることが、カーボンニュートラルの観点や、物性バランスの点で好ましい。この範囲よりも、ポリ乳酸の含有量が少ないとケミカルリサイクルできるＬ−ラクチド（Ｄ）の回収量が極めて少なくなる一方、多いとマテリアルリサイクルされるゴム含有熱可塑性樹脂組成物（Ｅ）中に劣化したポリ乳酸が残存し、再利用する際、材料設計の阻害要因となる。 The content of polylactic acid in the rubber-containing polylactic acid-based thermoplastic resin composition (A) is preferably in the range of 25 to 95% by weight, more preferably 30 to 95% by weight, still more preferably 50 to 50%. 90% by weight is preferable from the viewpoint of carbon neutral and physical property balance. If the content of polylactic acid is less than this range, the recovered amount of L-lactide (D) that can be chemically recycled becomes extremely small, while if it is large, it deteriorates in the rubber-containing thermoplastic resin composition (E) that is material recycled. When the polylactic acid remains and is reused, it becomes an obstacle to material design.
＜ゴム含有熱可塑性樹脂＞
一方、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）に含まれるゴム含有熱可塑性樹脂は、基本的にゴム質重合体に共重合可能なモノマー（以下、「（共）重合性モノマー」と称す。）がグラフト重合したグラフト共重合体（以下、「ゴム含有グラフト共重合体」と称す。）である。
<Rubber-containing thermoplastic resin>
On the other hand, the rubber-containing thermoplastic resin contained in the rubber-containing polylactic acid-based thermoplastic resin composition (A) is basically a monomer copolymerizable with a rubber polymer (hereinafter referred to as “(co) polymerizable monomer”). Is a graft copolymer obtained by graft polymerization (hereinafter referred to as “rubber-containing graft copolymer”).
ゴム含有グラフト共重合体のゴム質重合体としては、例えばポリブタジエン、スチレン／ブタジエン共重合体、アクリル酸エステル／ブタジエン共重合体等のブタジエン系ゴム；スチレン／イソプレン共重合体等の共役ジエン系ゴム；ポリアクリル酸ブチル等のアクリル系ゴム；エチレン／プロピレン共重合体等のオレフィン系ゴム；ポリオルガノシロキサン等のシリコン系ゴムなどが挙げられる。これらゴム質重合体は１種を単独で、又は２種以上を混合して使用することができる。 Examples of the rubbery polymer of the rubber-containing graft copolymer include butadiene rubbers such as polybutadiene, styrene / butadiene copolymer, acrylate ester / butadiene copolymer; and conjugated diene rubbers such as styrene / isoprene copolymer. Acrylic rubbers such as polybutyl acrylate; olefin rubbers such as ethylene / propylene copolymers; and silicon rubbers such as polyorganosiloxane. These rubbery polymers can be used alone or in combination of two or more.
なお、これらゴム質重合体は、モノマーから使用することができ、ゴム質重合体の構造がコア／シェル構造をとっていてもよい。例えば、ポリブタジエンをコアにして、アクリル酸エステルをシェルにしたゴム質重合体とすることもできる。 These rubbery polymers can be used from monomers, and the structure of the rubbery polymer may have a core / shell structure. For example, a rubbery polymer having polybutadiene as the core and acrylic acid ester as the shell can be used.
ゴム質重合体にグラフト重合する（共）重合性モノマーとしては、例えば、芳香族ビニル系単量体、シアン化ビニル系単量体、α，β−不飽和カルボン酸、α，β−不飽和カルボン酸エステル、α，β−不飽和ジカルボン酸無水物類、α，β−不飽和ジカルボン酸のイミド化合物類等が挙げられる。 Examples of the (co) polymerizable monomer that is graft-polymerized to the rubber polymer include, for example, aromatic vinyl monomers, vinyl cyanide monomers, α, β-unsaturated carboxylic acids, α, β-unsaturated monomers. Examples thereof include carboxylic acid esters, α, β-unsaturated dicarboxylic acid anhydrides, and imide compounds of α, β-unsaturated dicarboxylic acid.
これらのうち芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン、ブロムスチレン等が挙げられ、特にスチレン、α−メチルスチレンが好ましい。
また、シアン化ビニル系単量体としては、アクリロニトリル、メタクリルニトリル等が挙げられ、特にアクリロニトリルが好ましい。
α，β−不飽和カルボン酸としては、アクリル酸、メタクリル酸等が挙げられる。
α，β−不飽和カルボン酸エステル類としては、メチル（メタ）アクリレート（「（メタ）アクリレート」は「アクリレート及びメタクリレート」を示す）、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、２−エチル（メタ）アクリレート、２−エチルヘキシルメタクリレート等が挙げられる。
α，β−不飽和ジカルボン酸無水物類としては、無水マレイン酸、無水イタコン酸等が挙げられる。
α，β−不飽和ジカルボン酸のイミド化合物類としては、マレイミド、Ｎ−メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−フェニルマレイミド、Ｎ−ｏ−クロロフェニルマレイミド等が挙げられる。
これらのビニル系単量体は１種を単独で用いても良く、２種以上を混合して用いても良い。
Among these, examples of the aromatic vinyl monomer include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and styrene and α-methylstyrene are particularly preferable.
Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
Examples of the α, β-unsaturated carboxylic acid include acrylic acid and methacrylic acid.
Examples of α, β-unsaturated carboxylic acid esters include methyl (meth) acrylate (“(meth) acrylate” means “acrylate and methacrylate”), ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) ) Acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate and the like.
Examples of the α, β-unsaturated dicarboxylic acid anhydrides include maleic anhydride and itaconic anhydride.
Examples of the imide compounds of α, β-unsaturated dicarboxylic acid include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide.
These vinyl monomers may be used alone or in combination of two or more.
なお、（共）重合性モノマーの使用比率（重量比）としては、特に制限はないが、例えば、芳香族ビニル系単量体／シアン化ビニル系単量体として８０／２０〜６０／４０の範囲で用いることが好ましい。
また、シアン化ビニル系単量体及び芳香族ビニル系単量体以外のその他の（共）重合性モノマーは、全（共）重合性モノマー中３０重量％以下の範囲で使用することが好ましい。
In addition, although there is no restriction | limiting in particular as a use ratio (weight ratio) of a (co) polymerizable monomer, For example, it is 80 / 20-60 / 40 as an aromatic vinyl-type monomer / vinyl cyanide-type monomer. It is preferable to use within a range.
Further, other (co) polymerizable monomers other than the vinyl cyanide monomer and the aromatic vinyl monomer are preferably used in the range of 30% by weight or less in the total (co) polymerizable monomer.
ゴム含有グラフト共重合体中のゴム含有量は好ましくは２０〜８０重量％、より好ましくは３０〜７０重量％、さらに好ましくは４０〜６０重量％の範囲となるように調整する。この範囲よりもゴム含有量が低い場合には、十分な耐衝撃性が得られず、また、この範囲より多くても耐衝撃強度の向上は望めず、分散性不良や、剛性などの機械的特性の低下を招くおそれがある。 The rubber content in the rubber-containing graft copolymer is preferably adjusted to 20 to 80% by weight, more preferably 30 to 70% by weight, and still more preferably 40 to 60% by weight. If the rubber content is lower than this range, sufficient impact resistance cannot be obtained, and if it exceeds this range, no improvement in impact strength can be expected, resulting in poor dispersibility and mechanical properties such as rigidity. There is a risk of deterioration of characteristics.
なお、ゴム含有グラフト共重合体のゴム含有量は、赤外分光測定装置を使用することにより測定することができる。 The rubber content of the rubber-containing graft copolymer can be measured by using an infrared spectrometer.
グラフト重合は、公知の乳化重合、懸濁重合、溶液重合、塊状重合により行うことができ、これらの重合方法を組み合わせた方法でもよいが、不純物中に含まれる金属成分を低減するためには、溶液重合、塊状重合が好ましい。 Graft polymerization can be carried out by known emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and may be a combination of these polymerization methods, but in order to reduce the metal component contained in impurities, Solution polymerization and bulk polymerization are preferred.
ゴム含有グラフト共重合体は、重合方法や成分組成の異なるゴム含有グラフト共重合体の２種以上を混合して用いても良い。 The rubber-containing graft copolymer may be used by mixing two or more kinds of rubber-containing graft copolymers having different polymerization methods and component compositions.
また、本発明におけるゴム含有グラフト共重合体は、前述の（共）重合性モノマーがゴム質重合体にグラフト重合したものであるが、グラフト重合反応系においては、ゴム質重合体にグラフト重合せずに（共）重合性モノマー同士が（共）重合した硬質（共）重合体も生成する。この硬質（共）重合体と同様に耐熱性や流動性、光沢、艶消し、発色性などの特性改良のため他の硬質（共）重合体を配合しても良く、これらを含めて、ゴム含有グラフト共重合体として用いることができる。 The rubber-containing graft copolymer in the present invention is obtained by graft polymerization of the above-mentioned (co) polymerizable monomer onto a rubber polymer. In the graft polymerization reaction system, the rubber-containing graft copolymer is graft polymerized onto the rubber polymer. In addition, a hard (co) polymer in which (co) polymerizable monomers are (co) polymerized with each other is also produced. As with this hard (co) polymer, other hard (co) polymers may be added to improve properties such as heat resistance, fluidity, gloss, matte, and color development. It can be used as a containing graft copolymer.
硬質（共）重合体に用いられる単量体成分としては、先のゴム含有グラフト共重合体で紹介した（共）重合性モノマーを（共）重合したものを用いることができる。具体的には、芳香族ビニル系単量体、シアン化ビニル系単量体、（メタ）アクリル酸エステル、マレイミド化合物が好ましく用いられる。
硬質（共）重合体についても１種を単独で用いても良く、異なる組成、分子量のものを２種以上混合して用いても良い。
As the monomer component used for the hard (co) polymer, a (co) polymerized (co) polymerized monomer introduced in the previous rubber-containing graft copolymer can be used. Specifically, aromatic vinyl monomers, vinyl cyanide monomers, (meth) acrylic acid esters, and maleimide compounds are preferably used.
As for the hard (co) polymer, one kind may be used alone, or two or more kinds having different compositions and molecular weights may be mixed and used.
なお、ゴム含有グラフト共重合体として用いる成分のアセトン可溶分の重量平均分子量は、５０，０００〜６００，０００、特に６０，０００〜３００，０００、とりわけ８０，０００〜２５０，０００の範囲であることが好ましい。
このアセトン可溶分の重量平均分子量が、上記下限よりも低い場合には、本発明のゴム含有ポリ乳酸系熱可塑性樹脂組成物の衝撃強度低下を引き起こし、上記上限を超えるとゴム含有グラフト共重合体の分散性を悪化させる。
The weight-average molecular weight of the acetone-soluble component of the component used as the rubber-containing graft copolymer is in the range of 50,000 to 600,000, particularly 60,000 to 300,000, especially 80,000 to 250,000. Preferably there is.
When the weight-average molecular weight of this acetone-soluble component is lower than the lower limit, the impact strength of the rubber-containing polylactic acid-based thermoplastic resin composition of the present invention is reduced. Impairs dispersibility of coalescence.
本発明に係るゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）において、ゴム含有グラフト共重合体の含有量は、通常６０重量％以下であり、好ましくは５〜６０重量％の範囲であり、さらに好ましくは１０〜４０重量％であることが、本発明の目的を達成する観点及びカーボンニュートラルの観点から好ましい。 In the rubber-containing polylactic acid-based thermoplastic resin composition (A) according to the present invention, the content of the rubber-containing graft copolymer is usually 60% by weight or less, preferably 5 to 60% by weight, More preferably, it is 10 to 40% by weight from the viewpoint of achieving the object of the present invention and from the viewpoint of carbon neutral.
＜その他の成分＞
本発明に係るゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）には、ポリ乳酸、ゴム含有熱可塑性樹脂（ゴム含有グラフト共重合体又はゴム含有グラフト共重合体と硬質（共）重合体）の他、樹脂成分として、ポリカーボネート樹脂、ナイロン樹脂、ポリエステル樹脂などの他の熱可塑性樹脂の１種又は２種以上が含まれていてもよい。
<Other ingredients>
The rubber-containing polylactic acid-based thermoplastic resin composition (A) according to the present invention includes polylactic acid, rubber-containing thermoplastic resin (rubber-containing graft copolymer or rubber-containing graft copolymer and hard (co) polymer). In addition, as a resin component, 1 type, or 2 or more types of other thermoplastic resins, such as polycarbonate resin, nylon resin, and polyester resin, may be contained.
また、本発明に係るゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）には、各種の添加剤を配合することができる。この場合、各種添加剤としては、公知の酸化防止剤、紫外線吸収剤、滑剤、可塑剤、安定剤、離型剤、帯電防止剤、着色剤（顔料、染料など）、炭素繊維やガラス繊維、タルクやウォラストナイト、炭酸カルシウム、シリカなどの充填剤、難燃剤（ハロゲン系難燃剤、リン系難燃剤、アンチモン化合物など）、ドリップ防止剤、抗菌剤、防カビ剤、シリコ−ンオイル、カップリング剤などの１種又は２種以上が挙げられる。 Moreover, various additives can be mix | blended with the rubber-containing polylactic acid-type thermoplastic resin composition (A) based on this invention. In this case, various additives include known antioxidants, ultraviolet absorbers, lubricants, plasticizers, stabilizers, mold release agents, antistatic agents, colorants (pigments, dyes, etc.), carbon fibers and glass fibers, Fillers such as talc, wollastonite, calcium carbonate, silica, flame retardants (halogen flame retardants, phosphorus flame retardants, antimony compounds, etc.), anti-drip agents, antibacterial agents, fungicides, silicone oil, couplings 1 type or 2 types or more, such as an agent, is mentioned.
［アルカリ土類金属酸化物（Ｂ）］
次に、本発明におけるアルカリ土類金属酸化物（Ｂ）について説明する。
[Alkaline earth metal oxide (B)]
Next, the alkaline earth metal oxide (B) in the present invention will be described.
アルカリ土類金属酸化物（Ｂ）としては、酸化カルシウム、酸化マグネシウム、酸化バリウム、酸化ストロンチウム等が挙げられ、コストと供給性、さらに、ラクチド回収率の点から、特に、酸化カルシウム（ＣａＯ）、酸化マグネシウム（ＭｇＯ）の使用が好ましい。
これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。
Examples of the alkaline earth metal oxide (B) include calcium oxide, magnesium oxide, barium oxide, and strontium oxide. From the viewpoint of cost and supplyability, and lactide recovery, calcium oxide (CaO), The use of magnesium oxide (MgO) is preferred.
These may be used alone or in combination of two or more.
［硬質共重合体（Ｃ）］
次に、本発明における硬質共重合体（Ｃ）について説明する。
[Hard copolymer (C)]
Next, the hard copolymer (C) in the present invention will be described.
硬質共重合体（Ｃ）は、芳香族ビニル系単量体、シアン化ビニル系単量体、及び必要に応じて用いられるこれらと共重合可能なその他の単量体から選ばれた１種以上の単量体を（共）重合してなる硬質（共）重合体である。 The hard copolymer (C) is at least one selected from an aromatic vinyl monomer, a vinyl cyanide monomer, and other monomers copolymerizable with these as required. It is a hard (co) polymer obtained by (co) polymerizing these monomers.
これらのうち、芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン、ブロムスチレン等が挙げられ、特にスチレン、α−メチルスチレンが好ましい。また、シアン化ビニル系単量体としては、アクリロニトリル、メタクリルニトリル等が挙げられ、特にアクリロニトリルが好ましい。これらと共重合可能なその他の単量体としてメタクリル酸エステル系単量体、アクリル酸エステル単量体、マレイミド化合物等が挙げられる。メタクリル酸エステル系単量体としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ブチル及びこれらの誘導体等が挙げられる。アクリル酸エステル系単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル及びこれらの誘導体等が挙げられる。マレイミド化合物としては、Ｎ−メチルマレイミド、Ｎ−フェニルマレイミド、シクロヘキシルマレイミド等が挙げられ、Ｎ−フェニルマレイミドが好ましい。上記単量体はそれぞれ、１種又は２種以上を選択して使用することができる。 Among these, examples of the aromatic vinyl monomer include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and styrene and α-methylstyrene are particularly preferable. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable. Other monomers copolymerizable with these include methacrylic acid ester monomers, acrylic acid ester monomers, maleimide compounds and the like. Examples of the methacrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and derivatives thereof. Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and derivatives thereof. Examples of the maleimide compound include N-methylmaleimide, N-phenylmaleimide, cyclohexylmaleimide, and the like, and N-phenylmaleimide is preferable. Each of the above monomers can be used alone or in combination of two or more.
なお、硬質共重合体（Ｃ）を構成する単量体の比率（重量比）としては、芳香族ビニル系単量体／シアン化ビニル系単量体として８０／２０〜６０／４０の範囲で用いることが好ましい。
また、シアン化ビニル系単量体及び芳香族ビニル系単量体以外のその他の共重合可能な単量体は、全単量体成分中３０重量％以下の範囲で使用することが好ましい。
In addition, as a ratio (weight ratio) of the monomer which comprises a hard copolymer (C), it is the range of 80 / 20-60 / 40 as an aromatic vinyl-type monomer / vinyl cyanide-type monomer. It is preferable to use it.
Further, other copolymerizable monomers other than the vinyl cyanide monomer and the aromatic vinyl monomer are preferably used in the range of 30% by weight or less in the total monomer components.
また、硬質共重合体（Ｃ）の分子量は特に制限されるものではないが、ＧＰＣ測定による標準ポリスチレン換算法による重量平均分子量として４万〜２０万程度であることが好ましい。この範囲よりも分子量が大き過ぎると押出機中の樹脂粘度が上がりすぎて、ゴム含有グラフト共重合体の劣化を引き起こす。一方、小さ過ぎるとラクチドの回収量が低下する。 The molecular weight of the hard copolymer (C) is not particularly limited, but is preferably about 40,000 to 200,000 as a weight average molecular weight according to a standard polystyrene conversion method by GPC measurement. If the molecular weight is larger than this range, the resin viscosity in the extruder will increase too much, causing deterioration of the rubber-containing graft copolymer. On the other hand, if it is too small, the amount of lactide recovered decreases.
［処理方法］
本発明においては、押出機のホッパー部から、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）１００重量部と、アルカリ土類金属酸化物（Ｂ）０.００５〜２０重量部と、硬質（共）重合体（Ｃ）５〜２００重量部（ただし、（Ｂ）成分と（Ｃ）成分の合計１００重量部中の（Ｂ）成分の割合は０．１〜１０重量部）とを連続的に投入して、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）中のポリ乳酸の熱分解で生成したラクチド（Ｄ）を回収すると共に、ポリ乳酸が分離されたゴム含有熱可塑性樹脂組成物（Ｅ）を回収する。
[Processing method]
In the present invention, from the hopper part of the extruder, 100 parts by weight of the rubber-containing polylactic acid-based thermoplastic resin composition (A), 0.005 to 20 parts by weight of the alkaline earth metal oxide (B), and hard ( (Co) polymer (C) 5 to 200 parts by weight (however, the ratio of component (B) in the total 100 parts by weight of component (B) and component (C) is 0.1 to 10 parts by weight)) The rubber-containing thermoplastic resin composition in which lactide (D) produced by thermal decomposition of polylactic acid in the rubber-containing polylactic acid-based thermoplastic resin composition (A) is recovered and the polylactic acid is separated. Collect (E).
この処理において、アルカリ土類金属酸化物（Ｂ）は、ポリ乳酸の熱分解の触媒として作用するものであり、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）１００重量部に対するアルカリ土類金属酸化物（Ｂ）の添加量が上記下限未満ではポリ乳酸の熱分解、それによるラクチド（Ｄ）とゴム含有熱可塑性樹脂組成物（Ｅ）の分離、回収を十分に行えず、上記上限を超えると回収されたゴム含有熱可塑性樹脂組成物（Ｅ）の表面状態や機械物性が悪化する傾向にある。アルカリ土類金属酸化物（Ｂ）は、好ましくはゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）１００重量部に対して０．１〜１０重量部の割合で用いられる。 In this treatment, the alkaline earth metal oxide (B) acts as a catalyst for thermal decomposition of polylactic acid, and the alkaline earth metal relative to 100 parts by weight of the rubber-containing polylactic acid-based thermoplastic resin composition (A). If the addition amount of the oxide (B) is less than the above lower limit, the thermal decomposition of polylactic acid, and thereby the lactide (D) and the rubber-containing thermoplastic resin composition (E) cannot be sufficiently separated and recovered, exceeding the above upper limit. The surface state and mechanical properties of the recovered rubber-containing thermoplastic resin composition (E) tend to deteriorate. The alkaline earth metal oxide (B) is preferably used at a ratio of 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber-containing polylactic acid-based thermoplastic resin composition (A).
また、硬質（共）重合体（Ｃ）は、アルカリ土類金属酸化物（Ｂ）の混練作業性の向上、回収されるゴム含有熱可塑性樹脂組成物（Ｅ）の物性向上に有効な成分であり、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）１００重量部に対する硬質（共）重合体（Ｃ）の添加量が上記下限未満では硬質（共）重合体（Ｃ）を用いることによる上記効果を十分に得ることができず、上記上限を超えると回収されたゴム含有熱可塑性樹脂組成物（Ｅ）の物性が損なわれるおそれがある。硬質（共）重合体（Ｃ）は、好ましくはゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）１００重量部に対して５０〜１５０重量部の割合で用いられる。 The hard (co) polymer (C) is an effective component for improving the kneading workability of the alkaline earth metal oxide (B) and improving the physical properties of the recovered rubber-containing thermoplastic resin composition (E). Yes, when the amount of addition of the hard (co) polymer (C) to 100 parts by weight of the rubber-containing polylactic acid-based thermoplastic resin composition (A) is less than the lower limit, the above-described use of the hard (co) polymer (C) An effect cannot fully be acquired and when the said upper limit is exceeded, there exists a possibility that the physical property of the collect | recovered rubber-containing thermoplastic resin composition (E) may be impaired. The hard (co) polymer (C) is preferably used in a proportion of 50 to 150 parts by weight with respect to 100 parts by weight of the rubber-containing polylactic acid-based thermoplastic resin composition (A).
また、アルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）とはその合計１００重量部において、アルカリ土類金属酸化物（Ｂ）の割合が０．１〜１０重量部となるように用いるが、この範囲よりもアルカリ土類金属酸化物（Ｂ）が少ないと、ポリ乳酸の熱分解、それによるラクチド（Ｄ）とゴム含有熱可塑性樹脂組成物（Ｅ）の分離回収を十分に行えず、多いと回収されたゴム含有熱可塑性樹脂組成物（Ｅ）の表面状態や機械物性が悪化する傾向にある。アルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）におけるアルカリ土類金属酸化物（Ｂ）の割合は、特に１〜５重量部であることが好ましい。 The alkaline earth metal oxide (B) and the hard (co) polymer (C) are 100 parts by weight in total, and the ratio of the alkaline earth metal oxide (B) is 0.1 to 10 parts by weight. However, if the alkaline earth metal oxide (B) is less than this range, the polylactic acid is thermally decomposed thereby separating and recovering the lactide (D) and the rubber-containing thermoplastic resin composition (E). If the amount is not sufficient, the surface state and mechanical properties of the recovered rubber-containing thermoplastic resin composition (E) tend to deteriorate. The ratio of the alkaline earth metal oxide (B) in the alkaline earth metal oxide (B) and the hard (co) polymer (C) is particularly preferably 1 to 5 parts by weight.
特に、アルカリ土類金属酸化物（Ｂ）は、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）中のポリ乳酸に対して０．５〜５重量％の割合で用い、硬質（共）重合体（Ｃ）はゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）中のゴム含有グラフト共重合体に対して６０〜１２０重量％の割合で用いることが好ましい。 In particular, the alkaline earth metal oxide (B) is used in a proportion of 0.5 to 5% by weight with respect to the polylactic acid in the rubber-containing polylactic acid-based thermoplastic resin composition (A), and is hard (co) heavy. The blend (C) is preferably used in a proportion of 60 to 120% by weight based on the rubber-containing graft copolymer in the rubber-containing polylactic acid-based thermoplastic resin composition (A).
ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）とアルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）とを押出機に連続的に投入する方法としては、上記（Ａ）〜（Ｃ）成分を一旦、ヘンシェル等で均一に混合して同時に投入しても良く、複数の重量式フィーダーを用いて別々に定量フィードしても良い。あるいは、ハンドリング性のために、例えば、アルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）の全部又は一部を予備混合し、ペレット化したものを所定の添加範囲内となるように供給する方法を採用することも可能である。 As a method for continuously charging the rubber-containing polylactic acid-based thermoplastic resin composition (A), the alkaline earth metal oxide (B), and the hard (co) polymer (C) into the extruder, the above (A ) To (C) may be once mixed uniformly with Henschel and the like, and may be added simultaneously, or may be quantitatively fed separately using a plurality of weight type feeders. Alternatively, for handling properties, for example, all or part of the alkaline earth metal oxide (B) and the hard (co) polymer (C) are premixed, and the pellets are within a predetermined addition range. It is also possible to adopt a method of supplying as described above.
用いる押出機のシリンダー設定温度は１８０〜２５０℃、好ましくは１９０〜２２０℃とする。この温度が１８０℃未満ではラクチド（Ｄ）の回収量が著しく低下し、２５０℃を超えると回収されるゴム含有熱可塑性樹脂組成物（Ｅ）の劣化が激しく再利用に適さなくなる。 The cylinder set temperature of the extruder used is 180 to 250 ° C, preferably 190 to 220 ° C. If this temperature is less than 180 ° C., the recovered amount of lactide (D) is remarkably reduced, and if it exceeds 250 ° C., the recovered rubber-containing thermoplastic resin composition (E) is so deteriorated that it is not suitable for reuse.
本発明においては、好ましくは、１箇所以上、例えば１〜３箇所のベント口を備える押出機を用い、ベント口よりラクチド（Ｄ）を回収し、ダイ部よりゴム含有熱可塑性樹脂組成物（Ｅ）を回収する。これにより効率的にラクチド（Ｄ）とゴム含有熱可塑性樹脂組成物（Ｅ）を分離、回収することができる。１箇所以上のベント口から回収されるラクチド（Ｄ）は、複数の冷却トラップにより捕集される。 In the present invention, preferably, an extruder having one or more, for example, 1 to 3, vent ports is used, lactide (D) is recovered from the vent port, and a rubber-containing thermoplastic resin composition (E ). Thereby, lactide (D) and a rubber containing thermoplastic resin composition (E) can be isolate | separated and collect | recovered efficiently. Lactide (D) recovered from one or more vent openings is collected by a plurality of cooling traps.
用いる押出機のサイズ、スクリュー、シリンダー構成など特に制限は無いが、工業的にはシリンダー径３０ｍｍ以上、例えば４５〜１００ｍｍで、Ｌ／Ｄが２５以上、例えば２８〜３５であることが好ましい。 Although there is no restriction | limiting in particular, such as a size of an extruder to be used, a screw, and a cylinder structure, It is preferable industrially that a cylinder diameter is 30 mm or more, for example, 45-100 mm, and L / D is 25 or more, for example, 28-35.
［回収ラクチド（Ｄ）］
本発明の方法により回収されるラクチド（Ｄ）は、好ましくはＬ−ラクチド９０％以上、より好ましくは９２％以上の光学純度を有するものであり、回収されたラクチド（Ｄ）はポリ乳酸原料として再利用することができる。
[Recovered lactide (D)]
The lactide (D) recovered by the method of the present invention preferably has an optical purity of 90% or more, more preferably 92% or more of L-lactide, and the recovered lactide (D) is used as a polylactic acid raw material. Can be reused.
［回収ゴム含有熱可塑性樹脂組成物（Ｅ）］
本発明の方法で回収されたゴム含有熱可塑性樹脂組成物（Ｅ）は、好ましくは、その樹脂流動性が、ＩＳＯ１１３３に準ずるメルトボリュームフローレート（ＭＶＲ）の測定値で、２２０℃×９８Ｎの条件下、１０〜８０ｃｍ３／１０分、好ましくは２０〜５０ｃｍ３／１０分であるものである。
ゴム含有熱可塑性樹脂組成物（Ｅ）の流動性が上記下限未満では、回収されるゴム含有熱可塑性樹脂組成物（Ｅ）のゴム成分の劣化を生じ、上記上限を超えるとラクチドの回収率が悪化する。
[Recovered rubber-containing thermoplastic resin composition (E)]
The rubber-containing thermoplastic resin composition (E) recovered by the method of the present invention preferably has a resin fluidity of 220 ° C. × 98 N as measured by a melt volume flow rate (MVR) according to ISO 1133. lower, 10~80cm 3/10 min, but preferably from 20 to 50 cm 3/10 min.
When the fluidity of the rubber-containing thermoplastic resin composition (E) is less than the above lower limit, the rubber component of the recovered rubber-containing thermoplastic resin composition (E) is deteriorated, and when the upper limit is exceeded, the lactide recovery rate is increased. Getting worse.
［再生熱可塑性樹脂組成物］
本発明の方法により回収されたゴム含有熱可塑性樹脂組成物（Ｅ）は、これに他の熱可塑性樹脂（Ｆ）又は熱可塑性樹脂（Ｆ）組成物を混合して再生熱可塑性樹脂組成物として各種用途に用いることができる。
[Recycled thermoplastic resin composition]
The rubber-containing thermoplastic resin composition (E) recovered by the method of the present invention is mixed with another thermoplastic resin (F) or a thermoplastic resin (F) composition as a recycled thermoplastic resin composition. It can be used for various purposes.
この再生熱可塑性樹脂組成物の調製のために、回収されたゴム含有熱可塑性樹脂組成物（Ｅ）に混合する他の熱可塑性樹脂（Ｆ）又は熱可塑性樹脂（Ｆ）組成物としては特に制限はないが、本発明に係るゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）に含まれるゴム含有グラフト共重合体（ゴム含有グラフト共重合体と共に硬質（共）重合体を含んでいてもよい）或いはこのようなゴム含有グラフト共重合体にゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）に含まれる他の樹脂成分や各種の添加剤として前述したものを配合してなる熱可塑性樹脂組成物などが挙げられる。
回収されたゴム含有熱可塑性樹脂組成物（Ｅ）に混合する他の熱可塑性樹脂（Ｆ）又は熱可塑性樹脂（Ｆ）組成物には、通常、新品の樹脂又は樹脂組成物が用いられる。
For the preparation of this recycled thermoplastic resin composition, other thermoplastic resins (F) or thermoplastic resin (F) compositions to be mixed with the recovered rubber-containing thermoplastic resin composition (E) are particularly limited. However, the rubber-containing graft copolymer contained in the rubber-containing polylactic acid thermoplastic resin composition (A) according to the present invention may contain a hard (co) polymer together with the rubber-containing graft copolymer. Or a thermoplastic resin composition obtained by blending such a rubber-containing graft copolymer with those described above as other resin components and various additives contained in the rubber-containing polylactic acid-based thermoplastic resin composition (A). Such as things.
For the other thermoplastic resin (F) or thermoplastic resin (F) composition to be mixed with the recovered rubber-containing thermoplastic resin composition (E), a new resin or resin composition is usually used.
回収されたゴム含有熱可塑性樹脂組成物（Ｅ）の混合量としては特に制限はないが、これを混合して得られる再生熱可塑性樹脂組成物中の回収ゴム含有熱可塑性樹脂組成物（Ｅ）の割合として２０重量％以上、例えば３０〜７０重量％程度となるように用いることが好ましい。この回収ゴム含有熱可塑性樹脂組成物（Ｅ）の割合が少な過ぎると回収ゴム含有熱可塑性樹脂組成物（Ｅ）を回収再利用することによる資源再利用の効果が少なく、多過ぎると再生熱可塑性樹脂組成物の機械物性が劣るものとなり、その用途が制限されることになる。 The mixing amount of the recovered rubber-containing thermoplastic resin composition (E) is not particularly limited, but the recovered rubber-containing thermoplastic resin composition (E) in the recycled thermoplastic resin composition obtained by mixing the rubber-containing thermoplastic resin composition (E) The ratio is preferably 20% by weight or more, for example, about 30 to 70% by weight. If the ratio of the recovered rubber-containing thermoplastic resin composition (E) is too small, the recovered rubber-containing thermoplastic resin composition (E) has little effect on resource recycling by recovering and reusing, and if it is too much, the recycled thermoplasticity The mechanical properties of the resin composition will be inferior, and its application will be limited.
以下に、使用材料例、合成例、実施例及び比較例を挙げて、本発明をより具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。なお、以下において、「部」及び「％」は、特に断わらない限り重量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples of materials used, synthesis examples, examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Absent. In the following, “parts” and “%” are based on weight unless otherwise specified.
＜ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）＞
本発明におけるゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）としては、ＵＭＧ ＡＢＳ（株）社製エコペレット（登録商標）Ｌシリーズ「ＬＡ１３Ａ」（ポリ乳酸含有量３０％），「ＬＡ１７Ｂ」（ポリ乳酸含有量６４％），「ＬＡ１８Ｂ」（ポリ乳酸含有量７８％）を、それぞれ射出成形して得られた成形品を粉砕機により破砕して用いた。
<Rubber-containing polylactic acid-based thermoplastic resin composition (A)>
As the rubber-containing polylactic acid-based thermoplastic resin composition (A) in the present invention, Eco pellet (registered trademark) L series “LA13A” (polylactic acid content 30%), “LA17B” (manufactured by UMG ABS Co., Ltd.) Polylactic acid content of 64%) and “LA18B” (polylactic acid content of 78%) were respectively molded and obtained by pulverizing with a pulverizer.
＜硬質共重合体（Ｃ）＞
実施例及び比較例で用いた硬質共重合体（Ｃ）の合成例を下記に示す。
<Hard copolymer (C)>
A synthesis example of the hard copolymer (C) used in Examples and Comparative Examples is shown below.
合成例１：硬質共重合体（Ｃ−１）（ＡＮ／ＳＴ＝２０／８０、Ｍｗ＝５万）の製造法
窒素置換した反応器に蒸留水１２０部、アルキルベンゼンスルホン酸ソーダ０．００２部、ポリビニルアルコール０．５部、アゾイソブチルニトリル０．３部と、ターシャリードデシルメルカプタン（ｔ−ＤＭ）３部、アクリルニトリル２０部及びスチレン８０部からなる単量体混合物を加え、開始温度６０℃として５時間加熱後、１２０℃に昇温して４時間反応後、重合物を取り出した。転化率は９８％で、重量平均分子量は５０，０００であった。
Synthesis Example 1: Production Method of Rigid Copolymer (C-1) (AN / ST = 20/80, Mw = 50,000) 120 parts of distilled water, 0.002 part of sodium alkylbenzene sulfonate in a reactor purged with nitrogen, A monomer mixture consisting of 0.5 parts of polyvinyl alcohol, 0.3 parts of azoisobutyl nitrile, 3 parts of terrestrial decyl mercaptan (t-DM), 20 parts of acrylonitrile and 80 parts of styrene was added, and the starting temperature was 60 ° C. After heating for 5 hours, the temperature was raised to 120 ° C., and after reacting for 4 hours, the polymer was taken out. The conversion was 98% and the weight average molecular weight was 50,000.
合成例２：硬質共重合体（Ｃ−２）（ＡＮ／ＳＴ＝２０／８０、Ｍｗ＝１５万）の製造法
窒素置換した反応器に蒸留水１２０部、アルキルベンゼンスルホン酸ソーダ０．００２部、ポリビニルアルコール０．５部、アゾイソブチルニトリル０．３部と、ターシャリードデシルメルカプタン（ｔ−ＤＭ）０．５部、アクリルニトリル２０部及びスチレン８０部からなる単量体混合物を加え、開始温度６０℃として５時間加熱後、１２０℃に昇温して４時間反応後、重合物を取り出した。転化率は９８％で、重量平均分子量は１５０，０００であった。
Synthesis Example 2: Production Method of Rigid Copolymer (C-2) (AN / ST = 20/80, Mw = 150,000) 120 parts of distilled water, 0.002 part of sodium alkylbenzene sulfonate in a reactor purged with nitrogen, A monomer mixture consisting of 0.5 parts of polyvinyl alcohol, 0.3 parts of azoisobutyl nitrile, 0.5 parts of terrestrial decyl mercaptan (t-DM), 20 parts of acrylonitrile and 80 parts of styrene is added, starting temperature 60 After heating for 5 hours and then raising the temperature to 120 ° C. and reacting for 4 hours, the polymer was taken out. The conversion was 98% and the weight average molecular weight was 150,000.
合成例３：硬質共重合体（Ｃ−３）（ＭＭＡ／ＡＮ／ＳＴ＝５０／１５／３５、Ｍｗ＝１３万）の製造法
窒素置換した反応器に水１２０部、ポリビニルアルコール０．５部、アゾビスイソブチルニトリル０．３部、ターシャリードデシルメルカプタン（ｔ−ＤＭ）０．５部と、メタクリル酸メチル５０部、アクリロニトリル１５部及びスチレン３５部からなる単量体混合物を加え、開始温度６０℃として５時間加熱後、１２０℃に昇温して、４時間反応後、重合物を取り出した。転化率は９６％で、重量平均分子量は１３０，０００であった。
Synthesis Example 3: Production Method of Rigid Copolymer (C-3) (MMA / AN / ST = 50/15/35, Mw = 130,000) 120 parts of water and 0.5 parts of polyvinyl alcohol in a nitrogen-substituted reactor A monomer mixture consisting of 0.3 part of azobisisobutylnitrile, 0.5 part of tertiary decyl mercaptan (t-DM), 50 parts of methyl methacrylate, 15 parts of acrylonitrile and 35 parts of styrene is added, and the starting temperature is 60. After heating for 5 hours at 120C, the temperature was raised to 120C, and after reacting for 4 hours, the polymer was taken out. The conversion was 96% and the weight average molecular weight was 130,000.
[実施例１〜９及び比較例１〜６]
日本製鋼所（株）社製のＴＥＸ４４二軸押出し機（シリンダー径４７ｍｍ、Ｌ／Ｄ＝３１）に、３箇所ベント口を設置し、シリンダーの設定温度を表１，２に示す温度として、重量式定量フィーダーより表１，２に示す割合のゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）、アルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）の混合物（ただし、比較例１ではアルカリ土類金属酸化物（Ｂ）不使用、比較例３では硬質（共）重合体（Ｃ）不使用）を定量フィードしてケミカル・マテリアルリサイクルを実施した。
[Examples 1-9 and Comparative Examples 1-6]
In the TEX44 twin screw extruder (Cylinder diameter 47 mm, L / D = 31) manufactured by Nippon Steel, Ltd., three vent holes were installed, and the set temperatures of the cylinders were set to the temperatures shown in Tables 1 and 2; A rubber-containing polylactic acid-based thermoplastic resin composition (A), a mixture of an alkaline earth metal oxide (B) and a hard (co) polymer (C) in the proportions shown in Tables 1 and 2 from a formula quantitative feeder (however, In Comparative Example 1, an alkaline earth metal oxide (B) was not used, and in Comparative Example 3, a hard (co) polymer (C) was not used.
なお、実施例８では、２台の重量式定量フィーダーを用い、ホッパー上に並列に配置して、一方の重量式定量フィーダーからは、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）を投入し、他方の重量式定量フィーダーからはアルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）の混合物を投入する２系列フィード方式で投入した。
その他の実施例及び比較例では、１台の重量式定量フィーダーにより、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）とアルカリ土類金属酸化物（Ｂ）と硬質（共）重合体（Ｃ）の混合物（ただし、比較例１ではアルカリ土類金属酸化物（Ｂ）不使用、比較例３では硬質（共）重合体（Ｃ）不使用）を押出機のホッパーに一括投入した。
In Example 8, two gravimetric quantitative feeders were used and arranged in parallel on the hopper, and the rubber-containing polylactic acid-based thermoplastic resin composition (A) was charged from one gravimetric quantitative feeder. The other gravimetric quantitative feeder was fed in a two-line feed system in which a mixture of alkaline earth metal oxide (B) and hard (co) polymer (C) was charged.
In other examples and comparative examples, the rubber-containing polylactic acid-based thermoplastic resin composition (A), the alkaline earth metal oxide (B), and the hard (co) polymer (C ) (However, alkaline earth metal oxide (B) is not used in Comparative Example 1, and hard (co) polymer (C) is not used in Comparative Example 3) was charged all at once into the hopper of the extruder.
ラクチド（Ｄ）は押出機のベント口から回収し、ダイ部からゴム含有熱可塑性樹脂組成物（Ｅ）を回収した。ゴム含有熱可塑性樹脂組成物（Ｅ）は、押出機のダイ部からストランド状に取り出した後、ペレタイザーにてカッティングした。 Lactide (D) was recovered from the vent port of the extruder, and the rubber-containing thermoplastic resin composition (E) was recovered from the die part. The rubber-containing thermoplastic resin composition (E) was taken out in a strand form from the die part of the extruder and then cut with a pelletizer.
［評価方法］
回収物について、以下の評価を行って、結果を表１に示した。
[Evaluation methods]
The recovered materials were evaluated as follows, and the results are shown in Table 1.
{ラクチド（Ｄ）の評価}
＜光学純度＞
冷却トラップにより回収されたラクチド（Ｄ）を光学カラム：Ｖａｒｉａｎ社製ｃｙｃｌｏｄｅｘｔｒｉｎｅ−β−２３６Ｍ−１９キャピラリーカラムを装着した島津製作所製ＧＣ−２０１４を用いて分析した。キャリアーガスとしてヘリウムを用い、インジェクタ及びカラム温度はそれぞれ２２０及び１５０℃等温とし、回収ラクチド（Ｄ）約３ｍｇをクロロホルム１ｍＬに溶解した試料を全量注入して回収ラクチド（Ｄ）中のＬ体の割合を測定した。
{Evaluation of lactide (D)}
<Optical purity>
The lactide (D) recovered by the cold trap was analyzed using GC-2014 manufactured by Shimadzu Corporation equipped with an optical column: cyclodextrin-β-236M-19 capillary column manufactured by Varian. Helium was used as the carrier gas, the injector and column temperatures were isothermal at 220 ° C. and 150 ° C., respectively, and a total amount of a sample prepared by dissolving about 3 mg of recovered lactide (D) in 1 mL of chloroform was injected. Was measured.
{ゴム含有熱可塑性樹脂組成物（Ｅ）の評価}
＜表面外観＞
押出機のダイ部から取り出されるストランドの表面状態と色を目視観察し、良否を評価した。
{Evaluation of rubber-containing thermoplastic resin composition (E)}
<Surface appearance>
The surface state and color of the strand taken out from the die part of the extruder were visually observed to evaluate the quality.
＜ＭＶＲ＞
得られたペレットを用いて、ＩＳＯ１１３３に準ずるメルトボリュームフローレート（ＭＶＲ）の測定方法に従って、２２０℃×９８Ｎの条件下での値を求めた。この値が１０〜８０ｃｍ３／１０分の範囲であれば、再資源材料として有効に用いることができる。
<MVR>
Using the obtained pellets, a value under a condition of 220 ° C. × 98 N was determined according to a measurement method of melt volume flow rate (MVR) according to ISO1133. So long as the value is 10~80cm 3/10 min, it can be effectively used as a recycling material.
＜衝撃強度保持率＞
回収したゴム含有熱可塑性樹脂組成物（Ｅ）に混合する他の熱可塑性樹脂（Ｆ）組成物として、ＵＭＧ ＡＢＳ社製 ＵＭＧＡＢＳ（登録商標）「ＥＸ１２０（一般ＡＢＳ）」を用いた。まず、この「ＥＸ１２０」について、ＩＳＯ １７９に準ずる方法で常温のシャルピー衝撃試験を行い、衝撃強度（初期値）を測定した。
次にこの「ＥＸ１２０」に各々の回収ゴム含有熱可塑性樹脂組成物（Ｅ）を混合物中の割合として３０％となるように混合、混練、成形して同様にシャルピー衝撃試験を行い、衝撃強度（再生後）を測定した。
衝撃強度の初期値に対する再生後の衝撃強度の割合（百分率）を算出し、この値（衝撃強度保持率）が９０％以上であればマテリアルリサイクル性が良好であると判断した。
<Shock strength retention>
As another thermoplastic resin (F) composition to be mixed with the recovered rubber-containing thermoplastic resin composition (E), UMGABS (registered trademark) “EX120 (general ABS)” manufactured by UMG ABS was used. First, “EX120” was subjected to a Charpy impact test at room temperature by a method according to ISO 179, and the impact strength (initial value) was measured.
Next, each of the recovered rubber-containing thermoplastic resin compositions (E) was mixed, kneaded and molded in this “EX120” so that the ratio in the mixture was 30%, and the Charpy impact test was conducted in the same manner. After regeneration) was measured.
The ratio (percentage) of the impact strength after reproduction with respect to the initial value of impact strength was calculated, and if this value (impact strength retention) was 90% or more, it was judged that the material recyclability was good.
［評価結果］ [Evaluation results]
［考察］
表１，２から次のことが明らかである。
本発明の請求項の要件を満たす実施例１〜９によれば、ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）を、目的とするラクチド（Ｄ）及びゴム含有熱可塑性樹脂組成物（Ｅ）としてケミカル・マテリアルリサイクルすることができる。
[Discussion]
From Tables 1 and 2, the following is clear.
According to Examples 1 to 9 satisfying the requirements of the claims of the present invention, the rubber-containing polylactic acid-based thermoplastic resin composition (A) is converted into the desired lactide (D) and the rubber-containing thermoplastic resin composition (E ) And chemical materials can be recycled.
これに対して、アルカリ土類金属酸化物（Ｂ）を用いない比較例１の方法では、押出機の運転そのものが不安定となりケミカル・マテリアルリサイクルできない。
アルカリ土類金属酸化物（Ｂ）の使用量が多過ぎる比較例２の方法においては、回収されたゴム含有熱可塑性樹脂組成物（Ｅ）のストランドの外観が悪く、衝撃強度保持率も低くなる。
硬質（共）重合体（Ｃ）を用いない比較例３においては、比較例１と同様に押出機の運転が不安定となり、マテリアルリサイクルできない。
硬質（共）重合体（Ｃ）の使用量が多過ぎる比較例４においては、目的とするラクチドが得られず、回収されたゴム含有熱可塑性樹脂組成物（Ｅ）の樹脂流動性が高すぎ、しかも衝撃強度保持率が目標に達しない。
押出機のシリンダー設定温度が高過ぎる比較例５においては、回収されたゴム含有熱可塑性樹脂組成物（Ｅ）の熱劣化が生じ、その結果、衝撃強度保持率も低下する。一方、押出機のシリンダー温度が低過ぎる比較例６においては、回収されたラクチド（Ｄ）の光学純度が目標に達しない。
On the other hand, in the method of Comparative Example 1 in which no alkaline earth metal oxide (B) is used, the operation of the extruder itself becomes unstable and chemical / material recycling cannot be performed.
In the method of Comparative Example 2 in which the amount of alkaline earth metal oxide (B) used is too large, the appearance of the strands of the recovered rubber-containing thermoplastic resin composition (E) is poor, and the impact strength retention is also low. .
In Comparative Example 3 in which the hard (co) polymer (C) is not used, the operation of the extruder becomes unstable as in Comparative Example 1, and material recycling cannot be performed.
In Comparative Example 4 in which the amount of the hard (co) polymer (C) used is too large, the intended lactide cannot be obtained, and the resin fluidity of the recovered rubber-containing thermoplastic resin composition (E) is too high. Moreover, the impact strength retention rate does not reach the target.
In Comparative Example 5 in which the cylinder set temperature of the extruder is too high, the recovered rubber-containing thermoplastic resin composition (E) is thermally deteriorated, and as a result, the impact strength retention is also reduced. On the other hand, in Comparative Example 6 where the cylinder temperature of the extruder is too low, the optical purity of the recovered lactide (D) does not reach the target.
本発明によれば、市場で各種製品に使用されたゴム含有ポリ乳酸系熱可塑性樹脂組成物や生産工程から排出される不良品のゴム含有ポリ乳酸系熱可塑性樹脂組成物を効率的にラクチドとゴム含有熱可塑性樹脂組成物に分離して回収することができる。その回収品ラクチドは、再びポリ乳酸に合成して再生することができる一方で、ゴム含有熱可塑性樹脂組成物は、ポストコンシューマ品としてマテリアルリサイクルに活用できる。
従って、地球環境負荷低減のため、また循環型社会構築のため、本発明の工業的有用性は極めて高い。
According to the present invention, a rubber-containing polylactic acid-based thermoplastic resin composition used for various products in the market or a defective rubber-containing polylactic acid-based thermoplastic resin composition discharged from a production process is efficiently used as a lactide. It can be separated and recovered into a rubber-containing thermoplastic resin composition. The recovered product lactide can be synthesized again into polylactic acid and recycled, while the rubber-containing thermoplastic resin composition can be utilized for material recycling as a post-consumer product.
Therefore, the industrial utility of the present invention is extremely high for reducing the global environmental load and for building a recycling society.
Claims (8)
ゴム含有ポリ乳酸系熱可塑性樹脂組成物（Ａ）１００重量部と、
アルカリ土類金属酸化物（Ｂ）０.００５〜２０重量部と、
硬質（共）重合体（Ｃ）５〜２００重量部とを（ただし、（Ｂ）成分と（Ｃ）成分との合計１００重量部中の（Ｂ）成分の割合は０．１〜１０重量部とする）、
シリンダー設定温度１８０〜２５０℃の押出機に連続的に投入してラクチド（Ｄ）とゴム含有熱可塑性樹脂組成物（Ｅ）を分離、回収することを特徴とするゴム含有ポリ乳酸系熱可塑性樹脂組成物の処理方法。 A method for separating and recovering lactide and a rubber-containing thermoplastic resin composition by treating a rubber-containing polylactic acid-based thermoplastic resin composition,
100 parts by weight of a rubber-containing polylactic acid-based thermoplastic resin composition (A),
0.005 to 20 parts by weight of an alkaline earth metal oxide (B);
Hard (co) polymer (C) 5 to 200 parts by weight (however, the proportion of component (B) in the total 100 parts by weight of component (B) and component (C) is 0.1 to 10 parts by weight) And)
A rubber-containing polylactic acid-based thermoplastic resin characterized by separating and recovering lactide (D) and rubber-containing thermoplastic resin composition (E) by continuously feeding into an extruder having a cylinder set temperature of 180 to 250 ° C. A method of processing the composition.
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| KR102081304B1 (en) | 2015-12-09 | 2020-02-25 | 토요 세이칸 가부시키가이샤 | How to Recover Lactide |
| KR20180087317A (en) * | 2015-12-09 | 2018-08-01 | 토요 세이칸 가부시키가이샤 | How to retrieve lactide |
| US10336882B2 (en) | 2015-12-09 | 2019-07-02 | Toyo Seikan Co., Ltd. | Method of recovering lactide |
| EP3388478A4 (en) * | 2015-12-09 | 2019-06-12 | Toyo Seikan Co., Ltd. | Method for collecting lactide |
| JP2017128517A (en) * | 2016-01-19 | 2017-07-27 | 東洋製罐株式会社 | Method for recovering lactide |
| JP2017132730A (en) * | 2016-01-29 | 2017-08-03 | 東洋製罐株式会社 | Lactide recovery method |
| US20190016696A1 (en) * | 2016-01-29 | 2019-01-17 | Toyo Seikan Co., Ltd. | Method of recovering lactide |
| CN108602794A (en) * | 2016-01-29 | 2018-09-28 | 东洋制罐株式会社 | The recovery method of lactide |
| US10457661B2 (en) | 2016-01-29 | 2019-10-29 | Toyo Seikan Co., Ltd. | Method of recovering lactide |
| WO2017130551A1 (en) * | 2016-01-29 | 2017-08-03 | 東洋製罐株式会社 | Lactide recovery method |
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