JP5241547B2 - Polylactic acid resin composition and method for producing the same - Google Patents
Polylactic acid resin composition and method for producing the same Download PDFInfo
- Publication number
- JP5241547B2 JP5241547B2 JP2009027211A JP2009027211A JP5241547B2 JP 5241547 B2 JP5241547 B2 JP 5241547B2 JP 2009027211 A JP2009027211 A JP 2009027211A JP 2009027211 A JP2009027211 A JP 2009027211A JP 5241547 B2 JP5241547 B2 JP 5241547B2
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- JP
- Japan
- Prior art keywords
- polylactic acid
- acid resin
- mol
- liquid crystal
- crystal polymer
- 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.)
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 118
- 239000004626 polylactic acid Substances 0.000 title claims description 118
- 239000011342 resin composition Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920005989 resin Polymers 0.000 claims description 71
- 239000011347 resin Substances 0.000 claims description 71
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 70
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 70
- -1 carbodiimide compound Chemical class 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000004898 kneading Methods 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 16
- 229920000728 polyester Polymers 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000004593 Epoxy Substances 0.000 claims description 8
- 238000005191 phase separation Methods 0.000 claims description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 238000010128 melt processing Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 description 28
- 229920000642 polymer Polymers 0.000 description 22
- 239000000178 monomer Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000003484 crystal nucleating agent Substances 0.000 description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 16
- 238000005259 measurement Methods 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 241000790917 Dioxys <bee> Species 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000004310 lactic acid Substances 0.000 description 8
- 235000014655 lactic acid Nutrition 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 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 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000012766 organic filler Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 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 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- 208000010444 Acidosis Diseases 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229930182843 D-Lactic acid Natural products 0.000 description 2
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000007950 acidosis Effects 0.000 description 2
- 208000026545 acidosis disease Diseases 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 229920002988 biodegradable polymer Polymers 0.000 description 2
- 239000004621 biodegradable polymer Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229940022769 d- lactic acid Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000005011 phenolic resin Substances 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
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229960001755 resorcinol Drugs 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
- 239000000377 silicon dioxide Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- HZVFRKSYUGFFEJ-YVECIDJPSA-N (2r,3r,4s,5r)-7-phenylhept-6-ene-1,2,3,4,5,6-hexol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=CC=C1 HZVFRKSYUGFFEJ-YVECIDJPSA-N 0.000 description 1
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-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
- QCHZUINRDLKKJX-UHFFFAOYSA-N 1-n,3-n,5-n-tritert-butylbenzene-1,3,5-tricarboxamide Chemical compound CC(C)(C)NC(=O)C1=CC(C(=O)NC(C)(C)C)=CC(C(=O)NC(C)(C)C)=C1 QCHZUINRDLKKJX-UHFFFAOYSA-N 0.000 description 1
- MXHDSBYJGVZESK-UHFFFAOYSA-N 1-n,4-n-diphenylbenzene-1,4-dicarboxamide Chemical compound C=1C=C(C(=O)NC=2C=CC=CC=2)C=CC=1C(=O)NC1=CC=CC=C1 MXHDSBYJGVZESK-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- MVOSYKNQRRHGKX-UHFFFAOYSA-N 11-Undecanolactone Chemical compound O=C1CCCCCCCCCCO1 MVOSYKNQRRHGKX-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- RDYWHMBYTHVOKZ-UHFFFAOYSA-N 18-hydroxyoctadecanamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCO RDYWHMBYTHVOKZ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XUWOAUCQJYFQLT-UHFFFAOYSA-N 2,2-diphenylpropane-1,1,1-triol Chemical compound C=1C=CC=CC=1C(C(O)(O)O)(C)C1=CC=CC=C1 XUWOAUCQJYFQLT-UHFFFAOYSA-N 0.000 description 1
- BZUILZIKDIMXBK-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)benzoic acid Chemical class OC(=O)C1=CC=CC=C1C(=O)OCC1OC1 BZUILZIKDIMXBK-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- ZDNUPMSZKVCETJ-UHFFFAOYSA-N 2-[4-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=C(C=2OCCN=2)C=C1 ZDNUPMSZKVCETJ-UHFFFAOYSA-N 0.000 description 1
- NYHNVHGFPZAZGA-UHFFFAOYSA-N 2-hydroxyhexanoic acid Chemical compound CCCCC(O)C(O)=O NYHNVHGFPZAZGA-UHFFFAOYSA-N 0.000 description 1
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 description 1
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- 239000005445 natural material Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical class O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001432 poly(L-lactide) Polymers 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 description 1
- 229960003629 potassium salicylate Drugs 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- PYJBVGYZXWPIKK-UHFFFAOYSA-M potassium;tetradecanoate Chemical compound [K+].CCCCCCCCCCCCCC([O-])=O PYJBVGYZXWPIKK-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229960003885 sodium benzoate Drugs 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- XTIVBOWLUYDHKE-UHFFFAOYSA-M sodium;cyclohexanecarboxylate Chemical compound [Na+].[O-]C(=O)C1CCCCC1 XTIVBOWLUYDHKE-UHFFFAOYSA-M 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
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- Biological Depolymerization Polymers (AREA)
Description
本発明は、ポリ乳酸樹脂と液晶ポリマーとを含むポリ乳酸樹脂組成物に関する。具体的には本発明は、ポリ乳酸樹脂中に液晶ポリマーが均一に分散した、耐熱性に優れたポリ乳酸樹脂組成物に関するものである。 The present invention relates to a polylactic acid resin composition containing a polylactic acid resin and a liquid crystal polymer. Specifically, the present invention relates to a polylactic acid resin composition having excellent heat resistance in which a liquid crystal polymer is uniformly dispersed in a polylactic acid resin.
従来のポリマーの殆どは石油資源を原料としているが、石油資源が将来的に枯渇するおそれがあること、また石油資源を大量消費することにより、地質時代より地中に蓄えられていた二酸化炭素が大気中に放出され、さらに地球温暖化が深刻化することが懸念されている。このような地球環境保護の見地から、自然環境下で分解される生分解性ポリマーが注目され、各種環境対応型製品への適用が検討されている。 Most of the conventional polymers are made from petroleum resources. However, there is a risk that the petroleum resources will be depleted in the future, and the large amount of oil resources consumed makes it possible to store carbon dioxide that has been stored underground since the geological era. There are concerns that it will be released into the atmosphere and global warming will become more serious. From such a viewpoint of protecting the global environment, biodegradable polymers that are decomposed in a natural environment are attracting attention, and application to various environmentally-friendly products is being studied.
中でも、最近では温暖化防止の観点から、バイオマスよりなるポリマーが注目されている。バイオマスよりなるポリマーは、もともと植物が光合成により二酸化炭素を同化して作り上げたバイオマスを原料としてなるため、その生産が自然の物質循環サイクルに適合しているだけでなく、使用後に焼却処理をしても大気中の二酸化炭素の濃度を上昇させることにはならない。 Among them, recently, a polymer made of biomass has attracted attention from the viewpoint of preventing global warming. Polymers made of biomass are originally made from biomass assimilated by carbon dioxide by photosynthesis, so that the production is not only compatible with the natural material circulation cycle, but is also incinerated after use. Does not increase the concentration of carbon dioxide in the atmosphere.
このようなバイオマスよりなるポリマーとして、ポリヒドロキシブチレート、ポリブチレンスクシネート、ポリ乳酸などが知られている。これらの中で、ポリ乳酸は、原料である乳酸あるいはラクチドが天然植物から比較的効率よく製造することが可能であるため、単なる生分解性ポリマーとしてだけではなく、その強靭性や高い透明性を生かして汎用性ポリマーとしての幅広い利用が計られている。 As such a polymer comprising biomass, polyhydroxybutyrate, polybutylene succinate, polylactic acid, and the like are known. Among these, polylactic acid can be produced not only as a biodegradable polymer but also in its toughness and high transparency because lactic acid or lactide as raw materials can be produced from natural plants relatively efficiently. It is widely used as a versatile polymer.
しかし、ポリ乳酸の融点はおよそ１７０℃であり、汎用ポリマーとして用いるには、十分であるとは言い難く、機械特性や耐熱性の向上が求められている。 However, the melting point of polylactic acid is about 170 ° C., and it cannot be said that it is sufficient for use as a general-purpose polymer, and improvements in mechanical properties and heat resistance are required.
このため、ポリ乳酸と汎用の樹脂材料をブレンドし、上記欠点を補う検討が行われている。特許文献１では石油資源由来のポリエステルとポリ乳酸とのポリマーアロイについて開示されているが、ポリ乳酸含有量は少量であり環境低負荷性の観点において十分とは言えない。また特許文献２〜４において、ポリ乳酸にポリブチレンテレフタレートやポリアミドなどを分散させ、機械特性、耐熱性を改良した樹脂組成物について開示されているが、機械特性、耐熱性は十分とは言えない。 For this reason, studies have been made to blend the polylactic acid and a general-purpose resin material to make up for the above drawbacks. Patent Document 1 discloses a polymer alloy of polyester and polylactic acid derived from petroleum resources, but the amount of polylactic acid is small and it cannot be said that it is sufficient from the viewpoint of low environmental load. Patent Documents 2 to 4 disclose a resin composition in which polybutylene terephthalate or polyamide is dispersed in polylactic acid to improve mechanical properties and heat resistance, but the mechanical properties and heat resistance are not sufficient. .
さらに特許文献５において、ポリ乳酸と結晶性の芳香族ポリエステルをブレンドして、芳香族ポリエステルが連続相、ポリ乳酸が分散相となる相構造の熱可塑性樹脂組成物が開示されている。しかし、この様な特殊な相構造を形成させるためには、ポリ乳酸と芳香族ポリエステルとのブレンドにおいて、両者の粘度比を特定の範囲に調整する必要があったり、溶融混練を行う際に特殊な構成のスクリューが必要になるなど、製造工程が煩雑となり、またポリ乳酸の含有量や耐熱性においても十分満足できるものではない。したがって、これらの点において更なる改良が求められている。 Further, Patent Document 5 discloses a thermoplastic resin composition having a phase structure in which polylactic acid and a crystalline aromatic polyester are blended so that the aromatic polyester is a continuous phase and the polylactic acid is a dispersed phase. However, in order to form such a special phase structure, in the blend of polylactic acid and aromatic polyester, it is necessary to adjust the viscosity ratio of the two to a specific range, or when performing melt-kneading. The manufacturing process becomes complicated, for example, a screw having a different configuration is required, and the polylactic acid content and heat resistance are not sufficiently satisfactory. Accordingly, further improvements are required in these respects.
本発明の目的は、ポリ乳酸樹脂の欠点であった耐熱性が大幅に向上され、かつ簡易なプロセスで製造し得るポリ乳酸樹脂組成物を提供することにある。 An object of the present invention is to provide a polylactic acid resin composition that is greatly improved in heat resistance, which has been a drawback of the polylactic acid resin, and can be manufactured by a simple process.
本発明者らは、ポリ乳酸樹脂の性能向上について鋭意検討した結果、ポリ乳酸樹脂に、所定量の液晶ポリマーおよび相溶化剤を配合して得られるポリ乳酸樹脂組成物は、特殊な相構造を形成することなく耐熱性が著しく向上することを見出し、本発明を完成するに至った。 As a result of intensive studies on improving the performance of the polylactic acid resin, the present inventors have found that a polylactic acid resin composition obtained by blending a predetermined amount of a liquid crystal polymer and a compatibilizer into a polylactic acid resin has a special phase structure. The inventors have found that the heat resistance is remarkably improved without being formed, and have completed the present invention.
すなわち本発明は、ポリ乳酸樹脂、ポリ乳酸樹脂１００重量部に対して５〜１００重量部の液晶ポリマー、および、ポリ乳酸樹脂１００重量部に対して０．５〜１０重量部の相溶化剤を含む、ポリ乳酸樹脂組成物を提供する。 That is, the present invention includes a polylactic acid resin, 5 to 100 parts by weight of a liquid crystal polymer with respect to 100 parts by weight of the polylactic acid resin, and 0.5 to 10 parts by weight of a compatibilizer with respect to 100 parts by weight of the polylactic acid resin. A polylactic acid resin composition is provided.
また、本発明は、ポリ乳酸樹脂、ポリ乳酸樹脂１００重量部に対して５〜１００重量部の液晶ポリマー、およびポリ乳酸樹脂１００重量部に対して０．５〜１０重量部の相溶化剤を配合し、１７０〜２５０℃の温度下で溶融混練することを含む、ポリ乳酸樹脂が連続相、液晶ポリマーが分散相となる相構造を形成するポリ乳酸樹脂組成物を製造する方法を提供する。 The present invention also provides a polylactic acid resin, 5 to 100 parts by weight of a liquid crystal polymer with respect to 100 parts by weight of the polylactic acid resin, and 0.5 to 10 parts by weight of a compatibilizer with respect to 100 parts by weight of the polylactic acid resin. There is provided a method for producing a polylactic acid resin composition comprising a blending and melt-kneading at a temperature of 170 to 250 ° C. to form a phase structure in which a polylactic acid resin is a continuous phase and a liquid crystal polymer is a dispersed phase.
本発明によるポリ乳酸樹脂と液晶ポリマーとを含有するポリ乳酸樹脂組成物は、ポリ乳酸樹脂の欠点であった耐熱性が大幅に向上しており、かつ、簡単なプロセスで製造することができる。また、本発明によるポリ乳酸樹脂組成物は、均一な相構造を示すため、強度などの物性においても均一性を示す。 The polylactic acid resin composition containing the polylactic acid resin and the liquid crystal polymer according to the present invention has greatly improved heat resistance, which has been a drawback of the polylactic acid resin, and can be produced by a simple process. In addition, since the polylactic acid resin composition according to the present invention exhibits a uniform phase structure, it also exhibits uniformity in physical properties such as strength.
本発明において、ポリ乳酸樹脂とは、Ｌ−乳酸および／またはＤ−乳酸を主たる構成成分とし、乳酸以外の他の共重合成分を含んでいてもよいポリマーをいう。乳酸以外の他の共重合成分の含有量は、ポリ乳酸樹脂を構成する単量体、すなわち、Ｌ−乳酸および／またはＤ−乳酸と、他の共重合成分の合計量に対して、３０モル％以下であり、１０モル％以下であることが好ましい。 In the present invention, the polylactic acid resin refers to a polymer which contains L-lactic acid and / or D-lactic acid as a main constituent component and may contain a copolymer component other than lactic acid. The content of other copolymerization components other than lactic acid is 30 mol based on the total amount of monomers constituting the polylactic acid resin, that is, L-lactic acid and / or D-lactic acid, and other copolymerization components. % Or less, and preferably 10 mol% or less.
乳酸以外の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、ノナンジオール、デカンジオール、１，４−シクロヘキサンジメタノール、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、ビスフェノールＡ、ポリエチレングリコール、ポリプロピレングリコールおよび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、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、およびカプロラクトン、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を挙げることができる。 As copolymerization components other than lactic acid, ethylene glycol, propylene glycol, butanediol, heptanediol, hexanediol, octanediol, nonanediol, decanediol, 1,4-cyclohexanedimethanol, neopentylglycol, glycerin, Glycol compounds such as pentaerythritol, bisphenol A, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, oxalic 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′-diphenyl ether Dicarboxylic acids such as carboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium isophthalic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid and the like, and Examples include lactones such as caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.
本発明において用いる、ポリ乳酸樹脂は、相溶性の点から、乳酸成分の光学純度が高いものが好ましい。すなわち、ポリ乳酸樹脂に含まれる総乳酸成分の内、Ｌ体が８０％以上含まれるかあるいはＤ体が８０％以上含まれるものが好ましく、Ｌ体が９０％以上含まれるかあるいはＤ体が９０％以上含まれるものがさらに好ましく、Ｌ体が９５％以上含まれるかあるいはＤ体が９５％以上含まれるものが特に好ましい。なお、本発明においてはＬ体またはＤ体を主成分とする光学純度の高いポリ乳酸を単独で使用してもよいし、それらの混合物を使用してもよい。 The polylactic acid resin used in the present invention preferably has a high optical purity of the lactic acid component from the viewpoint of compatibility. That is, among the total lactic acid components contained in the polylactic acid resin, those containing 80% or more of the L isomer or 80% or more of the D isomer are preferred, and those containing 90% or more of the L isomer or 90% of the D isomer. %, More preferably 95% or more of L-form or 95% or more of D-form. In the present invention, polylactic acid having a high optical purity mainly composed of L-form or D-form may be used alone or a mixture thereof may be used.
ポリ乳酸樹脂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、重量平均分子量としては、通常１０，０００以上、好ましくは４０，０００以上、より好ましくは８０，０００以上であるものが望ましい。ここでいう重量平均分子量とは、ゲルパーミエーションクロマトグラフィーで測定したポリメチルメタクリレート（ＰＭＭＡ）換算の分子量をいう。 The molecular weight and molecular weight distribution of the polylactic acid resin are not particularly limited as long as it can be substantially molded, but the weight average molecular weight is usually 10,000 or more, preferably 40,000 or more. Preferably it is 80,000 or more. The weight average molecular weight here refers to the molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography.
ポリ乳酸樹脂の融点については、特に制限されるものではないが、１２０〜２４０℃であるものが好ましく、１６０〜２３０℃であるものがより好ましい。 The melting point of the polylactic acid resin is not particularly limited, but is preferably 120 to 240 ° C, more preferably 160 to 230 ° C.
ポリ乳酸樹脂の製造方法としては、公知の重合方法を用いることができ、例えば、乳酸からの直接重合法、およびラクチドを介する開環重合法などを挙げることができる。 As a method for producing the polylactic acid resin, a known polymerization method can be used, and examples thereof include a direct polymerization method from lactic acid and a ring-opening polymerization method via lactide.
本発明において、ポリ乳酸樹脂に配合される液晶ポリマーは、異方性溶融相を形成するポリエステルまたはポリエステルアミドであり、当業者にサーモトロピック液晶ポリエステルまたはサーモトロピック液晶ポリエステルアミドと呼ばれるものであれば特に制限されない。 In the present invention, the liquid crystal polymer blended in the polylactic acid resin is a polyester or polyester amide that forms an anisotropic melt phase, and is particularly suitable if it is called a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyester amide by those skilled in the art. Not limited.
異方性溶融相の性質は直交偏向子を利用した通常の偏向検査法、すなわちホットステージにのせた試料を窒素雰囲気下で観察することにより確認できる。 The property of the anisotropic molten phase can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere.
本発明に用いる液晶ポリマーを構成する主たる繰返し単位は、芳香族オキシカルボニル繰返し単位、芳香族ジカルボニル繰返し単位、芳香族ジオキシ繰返し単位、芳香族アミノオキシ繰返し単位、芳香族ジアミノ繰返し単位、芳香族アミノカルボニル繰返し単位、芳香族オキシジカルボニル繰返し単位、および脂肪族ジオキシ繰返し単位から選択される１種以上とする。 The main repeating units constituting the liquid crystal polymer used in the present invention are aromatic oxycarbonyl repeating units, aromatic dicarbonyl repeating units, aromatic dioxy repeating units, aromatic aminooxy repeating units, aromatic diamino repeating units, aromatic amino One or more selected from a carbonyl repeating unit, an aromatic oxydicarbonyl repeating unit, and an aliphatic dioxy repeating unit.
また、本発明に用いる液晶ポリマーは本発明の目的を損なわない範囲で、上記の主たる繰り返し単位以外の繰り返し単位を構成成分として含んでいてもよく、例えば、チオエステル結合を含むものであってもよい。このような結合を与える単量体としては、メルカプト芳香族カルボン酸、および芳香族ジチオールおよびヒドロキシ芳香族チオールなどが挙げられる。これらの主たる繰り返し単位以外の繰り返し単位を与える単量体の使用量は、芳香族オキシカルボニル繰返し単位、芳香族ジカルボニル繰返し単位、芳香族ジオキシ繰返し単位、芳香族アミノオキシ繰返し単位、芳香族ジアミノ繰返し単位、芳香族アミノカルボニル繰り返し単位、芳香族オキシジカルボニル繰返し単位、および脂肪族ジオキシ繰返し単位を与える主たる単量体の合計量に対して１０モル％以下とする。 Further, the liquid crystal polymer used in the present invention may contain a repeating unit other than the main repeating unit as a constituent component within a range not impairing the object of the present invention, and may contain, for example, a thioester bond. . Examples of the monomer that gives such a bond include mercapto aromatic carboxylic acid, aromatic dithiol, and hydroxy aromatic thiol. The amount of the monomer that gives a repeating unit other than these main repeating units is aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic aminooxy repeating unit, aromatic diamino repeating unit. It is made into 10 mol% or less with respect to the total amount of the main monomer which gives a unit, an aromatic aminocarbonyl repeating unit, an aromatic oxydicarbonyl repeating unit, and an aliphatic dioxy repeating unit.
これらの各繰返し単位から構成される液晶ポリマーは構成成分およびポリマー中の組成比、シークエンス分布によっては、異方性溶融相を形成するものとしないものが存在するが、本発明に使用される液晶ポリマーは異方性溶融相を形成するものに限られる。 The liquid crystal polymer composed of each of these repeating units may or may not form an anisotropic molten phase depending on the constituent components, the composition ratio in the polymer, and the sequence distribution, but the liquid crystal used in the present invention. Polymers are limited to those that form an anisotropic melt phase.
芳香族オキシカルボニル繰返し単位を与える単量体の具体例としては、例えば、４−ヒドロキシ安息香酸、メタヒドロキシ安息香酸、オルトヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸、５−ヒドロキシ−２−ナフトエ酸、３−ヒドロキシ−２−ナフトエ酸、４’−ヒドロキシフェニル−４−安息香酸、３’−ヒドロキシフェニル−４−安息香酸、４’−ヒドロキシフェニル−３−安息香酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。これらの中では、パラヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸が得られる液晶ポリマーの特性や結晶融解温度を調整しやすいという点から好ましい。 Specific examples of the monomer that gives an aromatic oxycarbonyl repeating unit include, for example, 4-hydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2- Naphthoic acid, 3-hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid, their alkyl, alkoxy Alternatively, halogen-substituted products, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides can be used. Among these, parahydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable from the viewpoint of easy adjustment of the characteristics and crystal melting temperature of the liquid crystal polymer from which they are obtained.
芳香族ジカルボニル繰返し単位を与える単量体の具体例としては、例えば、テレフタル酸、イソフタル酸、２,６−ナフタレンジカルボン酸、１,６−ナフタレンジカルボン酸、２,７−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸、４,４’−ジカルボキシビフェニル等の芳香族ジカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。これらの中では、テレフタル酸、２,６−ナフタレンジカルボン酸が得られる液晶ポリマーの機械物性、耐熱性、結晶融解温度、成形性を適度なレベルに調整しやすいことから好ましい。 Specific examples of the monomer giving the aromatic dicarbonyl repeating unit include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1 , 4-naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-dicarboxybiphenyl, alkyl, alkoxy or halogen-substituted products thereof, ester derivatives thereof, and ester-forming derivatives such as acid halides. . Among these, terephthalic acid, 2,6-naphthalenedicarboxylic acid is preferable because it easily adjusts the mechanical properties, heat resistance, crystal melting temperature, and moldability of the liquid crystal polymer to an appropriate level.
芳香族ジオキシ繰返し単位を与える単量体の具体例としては、例えば、ハイドロキノン、レゾルシン、２,６−ジヒドロキシナフタレン、２,７−ジヒドロキシナフタレン、１,６−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、４,４’−ジヒドロキシビフェニル、３,３’−ジヒドロキシビフェニル、３,４’−ジヒドロキシビフェニル、４,４’−ジヒドロキシビフェニルエ−テル等の芳香族ジオール、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのエステル形成性誘導体が挙げられる。これらの中では、ハイドロキノンおよび４,４’−ジヒドロキシビフェニルが重合時の反応性や得られる液晶ポリマーの特性などの点から好ましい。 Specific examples of the monomer that gives an aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, Aromatic diols such as 4,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl ether, alkyl, alkoxy or halogen substituents thereof, And ester-forming derivatives such as acylated products thereof. Among these, hydroquinone and 4,4'-dihydroxybiphenyl are preferable from the viewpoint of reactivity during polymerization and characteristics of the obtained liquid crystal polymer.
芳香族アミノオキシ繰返し単位を与える単量体の具体例としては、例えば、ｐ−アミノフェノール、ｍ−アミノフェノール、４−アミノ−１−ナフトール、５−アミノ−１−ナフトール、８−アミノ−２−ナフトール、４−アミノ−４’−ヒドロキシビフェニル等の芳香族ヒドロキシアミン、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのエステルまたはアミド形成性誘導体が挙げられる。 Specific examples of the monomer that gives an aromatic aminooxy repeating unit include, for example, p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, and 8-amino-2. -Aromatic amines such as naphthol and 4-amino-4'-hydroxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and ester or amide-forming derivatives thereof such as acylated products thereof.
芳香族ジアミノ繰返し単位を与える単量体の具体例としては、例えば、ｐ−フェニレンジアミン、ｍ−フェニレンジアミン、１，５−ジアミノナフタレン、１，８−ジアミノナフタレン等の芳香族ジアミン、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのアミド形成性誘導体が挙げられる。 Specific examples of the monomer that gives an aromatic diamino repeating unit include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, and alkyls thereof. , Alkoxy- or halogen-substituted products, and amide-forming derivatives thereof such as acylated products thereof.
芳香族アミノカルボニル繰返し単位を与える単量体の具体例としては、例えば、ｐ−アミノ安息香酸、ｍ−アミノ安息香酸、６−アミノ−２−ナフトエ酸等の芳香族アミノカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステルまたはアミド形成性誘導体が挙げられる。 Specific examples of the monomer that gives an aromatic aminocarbonyl repeating unit include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, 6-amino-2-naphthoic acid, and alkyls thereof. , Alkoxy- or halogen-substituted products, and ester or amide-forming derivatives thereof such as acylated products, ester derivatives, and acid halides.
芳香族オキシジカルボニル繰返し単位を与える単量体の具体例としては、例えば、３−ヒドロキシ−２，７−ナフタレンジカルボン酸、４−ヒドロキシイソフタル酸、および５−ヒドロキシイソフタル酸等のヒドロキシ芳香族ジカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Specific examples of monomers that give aromatic oxydicarbonyl repeating units include hydroxy aromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid. Examples include acids, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof.
脂肪族ジオキシ繰返し単位を与える単量体の具体例としては、例えば、エチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオールなどの脂肪族ジオール、ならびにそれらのアシル化物が挙げられる。また、ポリエチレンテレフタレートや、ポリブチレンテレフタレートなどの脂肪族ジオキシ繰返し単位を含有するポリエステルを、前記の芳香族オキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、芳香族ヒドロキシアミン、芳香族ジアミン、芳香族アミノカルボン酸、芳香族オキシジカルボン酸およびそれらのアシル化物、エステル誘導体、酸ハロゲン化物などと反応させることによっても、脂肪族ジオキシ繰返し単位を含む液晶ポリマーを得ることができる。 Specific examples of the monomer that gives an aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. Polyesters containing aliphatic dioxy repeating units, such as polyethylene terephthalate and polybutylene terephthalate, are converted into the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxyamines, aromatic diamines, aromatics. A liquid crystal polymer containing an aliphatic dioxy repeating unit can also be obtained by reacting with an aminocarboxylic acid, an aromatic oxydicarboxylic acid and an acylated product, an ester derivative, an acid halide or the like thereof.
以上、本発明において用いる液晶ポリマーに含まれる繰返し単位とそれを与える単量体について説明したが、本発明において用いる液晶ポリマーとしては、示差走査熱量計により測定される結晶融解温度が１７０〜２５０℃、好ましくは１８０〜２３０℃であるものが好適である。結晶融解温度が１７０〜２５０℃の範囲にある液晶ポリマーを用いれば、ポリ乳酸の分解を抑制しつつ液晶ポリマーをブレンドでき、ポリ乳酸連続相中に液晶ポリマーが均一に分散したポリ乳酸樹脂組成物が得られる。 As described above, the repeating unit contained in the liquid crystal polymer used in the present invention and the monomer that gives it have been described. The liquid crystal polymer used in the present invention has a crystal melting temperature of 170 to 250 ° C. measured by a differential scanning calorimeter. Preferably, a temperature of 180 to 230 ° C. is suitable. If a liquid crystal polymer having a crystal melting temperature in the range of 170 to 250 ° C. is used, the liquid crystal polymer can be blended while suppressing the decomposition of polylactic acid, and the liquid crystal polymer is uniformly dispersed in the polylactic acid continuous phase. Is obtained.
液晶ポリマーの結晶融解温度が１７０℃を下回る場合、溶融混練時に攪拌モーターへの負荷が大きくなり混練機を破損してしまうおそれがあり、たとえ混練が可能であったとしてもポリ乳酸連続相中での液晶ポリマー相の分散が不均一となる傾向がある。また、２５０℃を上回る場合、ポリ乳酸の分解が顕著となり、十分な性能が得られなくなる傾向がある。 If the crystal melting temperature of the liquid crystal polymer is lower than 170 ° C., the load on the stirring motor may increase during melt kneading, and the kneader may be damaged. Even if kneading is possible, The liquid crystal polymer phase tends to be non-uniformly dispersed. Moreover, when it exceeds 250 degreeC, decomposition | disassembly of polylactic acid becomes remarkable and there exists a tendency for sufficient performance not to be obtained.
１７０〜２５０℃の結晶融解温度の範囲を満たす液晶ポリマーとして、本質的に、以下の式［Ｉ］〜［ＩＶ］で示される繰返し単位により構成される液晶ポリエステルが特に好適に使用される。
本明細書および特許請求の範囲において、「本質的に、以下の式［Ｉ］〜［ＩＶ］で示される繰返し単位により構成され」とは、液晶ポリマーがその構成成分として式［Ｉ］〜［ＩＶ］で示される繰返し単位の他に、液晶ポリマーの結晶融解温度が１７０〜２５０℃の範囲となる限り他の繰り返し単位を含有していてもよいことを意味する。
なお、本明細書および特許請求の範囲において、ｐ＋ｑ＋ｒ＋ｓ＝１００モル％である。
さらに、本明細書および特許請求の範囲において、「２価の芳香族基」とは、エステル結合またはアミド結合を形成することができる置換基を２つ有する芳香族基を意味する。
０．４≦ｐ／ｑ≦２．０
２モル％≦ｒ≦１５モル％、および
２モル％≦ｓ≦１５モル％］。
As a liquid crystal polymer satisfying the crystal melting temperature range of 170 to 250 ° C., a liquid crystal polyester composed essentially of repeating units represented by the following formulas [I] to [IV] is particularly preferably used.
In the present specification and claims, “essentially constituted by the repeating units represented by the following formulas [I] to [IV]” means that the liquid crystal polymer is represented by the formula [I] to [[ In addition to the repeating unit represented by IV], it means that other repeating units may be contained as long as the crystal melting temperature of the liquid crystal polymer is in the range of 170 to 250 ° C.
In the present specification and claims, p + q + r + s = 100 mol%.
Furthermore, in the present specification and claims, the “divalent aromatic group” means an aromatic group having two substituents capable of forming an ester bond or an amide bond.
0.4 ≦ p / q ≦ 2.0
2 mol% ≦ r ≦ 15 mol%, and 2 mol% ≦ s ≦ 15 mol%].
ｐ、ｑ、ｒ、ｓの好ましい範囲としては以下の式を満たすものである。
３５モル％≦ｐ≦４８モル％、
３５モル％≦ｑ≦４８モル％、
２モル％≦ｒ≦１５モル％、および
２モル％≦ｓ≦１５モル％。
A preferable range of p, q, r, and s satisfies the following formula.
35 mol% ≦ p ≦ 48 mol%,
35 mol% ≦ q ≦ 48 mol%,
2 mol% ≦ r ≦ 15 mol%, and 2 mol% ≦ s ≦ 15 mol%.
また、式［ＩＩＩ］および式［ＩＶ］において、Ａｒ１およびＡｒ2の好ましいものは、
Ａｒ１が、
Ａｒ2が、
であるものである。
In the formulas [III] and [IV], Ar 1 and Ar 2 are preferably
Ar 1 is
Ar 2 is
It is what is.
本発明における液晶ポリマーは、成形時の流動性を改良するなどの目的で、２種以上の液晶ポリマーをブレンドしたものを用いてもよい。 As the liquid crystal polymer in the present invention, a blend of two or more liquid crystal polymers may be used for the purpose of improving fluidity during molding.
以下、本発明において用いる液晶ポリマーの製造方法について説明する。 Hereinafter, a method for producing a liquid crystal polymer used in the present invention will be described.
本発明において用いる液晶ポリマーの製造方法に特に制限はなく、前記の単量体の組み合わせからなるエステル結合またはアミド結合を形成させる公知の重縮合方法、例えば溶融アシドリシス法、スラリー重合法などを用いることができる。 The production method of the liquid crystal polymer used in the present invention is not particularly limited, and a known polycondensation method for forming an ester bond or an amide bond composed of a combination of the above monomers, for example, a melt acidosis method, a slurry polymerization method, or the like is used. Can do.
溶融アシドリシス法とは、最初に単量体を加熱して反応物質の溶融液を形成し、反応を継続することにより溶融ポリマーを得る方法であり、本発明で用いる液晶ポリマーの製造方法として好ましい方法である。なお、縮合の最終段階で副生する揮発物（例えば、酢酸、水等）の除去を容易にするために真空を適用してもよい。 The melt acidosis method is a method in which a monomer is first heated to form a molten liquid of a reactant, and the reaction is continued to obtain a molten polymer, which is a preferred method for producing the liquid crystal polymer used in the present invention. It is. Note that a vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of the condensation.
スラリー重合法とは、熱交換流体の存在下で反応させる方法であって、固体生成物は熱交換媒質中に懸濁した状態で得られる。 The slurry polymerization method is a method of reacting in the presence of a heat exchange fluid, and the solid product is obtained in a state suspended in a heat exchange medium.
溶融アシドリシス法およびスラリー重合法の何れの場合においても、液晶ポリマーを製造する際に使用する重合性単量体成分は、ヒドロキシル基および／またはアミノ基をアシル化した変性形態、すなわち低級アシル化物として反応に供することもできる。低級アシル基は炭素原子数２〜５のものが好ましく、炭素原子数２または３のものがより好ましい。特に好ましくは前記単量体のアセチル化物を反応に用いる方法が挙げられる。 In both cases of the melt acidification method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystal polymer is a modified form in which hydroxyl groups and / or amino groups are acylated, that is, as a lower acylated product. It can also be used for the reaction. The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method using an acetylated product of the monomer in the reaction.
単量体のアシル化物は、別途アシル化して予め合成したものを用いてもよいし、液晶ポリマーの製造時に単量体に無水酢酸等のアシル化剤を加えて反応系内で生成せしめることもできる。 The acylated product of the monomer may be prepared by separately acylating and synthesized in advance, or it may be generated in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during the production of the liquid crystal polymer. it can.
溶融アシドリシス法またはスラリー重合法の何れの場合においても反応時、必要に応じて触媒を用いてもよい。 In any case of the melt acidification method or the slurry polymerization method, a catalyst may be used as needed during the reaction.
触媒の具体例としては、ジアルキルスズオキシド（たとえばジブチルスズオキシド）、ジアリールスズオキシドなどの有機スズ化合物；三酸化アンチモン；二酸化チタン；アルコキシチタンシリケート、チタンアルコキシドなどの有機チタン化合物；カルボン酸のアルカリまたはアルカリ土類金属塩（たとえば酢酸カリウム）；無機酸塩類（たとえば硫酸カリウム）；ルイス酸（例えば三フッ化硼素）；ハロゲン化水素（例えば塩化水素）などの気体状酸触媒などが挙げられる。 Specific examples of the catalyst include organotin compounds such as dialkyltin oxide (for example, dibutyltin oxide) and diaryltin oxide; antimony trioxide; titanium dioxide; organotitanium compounds such as alkoxytitanium silicate and titanium alkoxide; alkali or alkali of carboxylic acid Examples include earth metal salts (for example, potassium acetate); inorganic acid salts (for example, potassium sulfate); Lewis acid (for example, boron trifluoride); gaseous acid catalysts such as hydrogen halide (for example, hydrogen chloride).
触媒の使用割合は、通常モノマー重量に対して１０〜１０００ｐｐｍ、好ましくは２０〜２００ｐｐｍである。 The ratio of the catalyst used is usually 10 to 1000 ppm, preferably 20 to 200 ppm, based on the monomer weight.
このような重縮合反応によって得られた液晶ポリマーは、それぞれ溶融状態で重合反応槽より抜き出された後に、ペレット状、フレーク状、または粉末状に加工される。 The liquid crystal polymers obtained by such a polycondensation reaction are each extracted from the polymerization reaction tank in a molten state, and then processed into pellets, flakes, or powders.
本発明のポリ乳酸樹脂組成物における、ポリ乳酸樹脂と液晶ポリマーの配合比は、ポリ乳酸樹脂１００重量部に対し、液晶ポリマー５〜１００重量部、好ましくは、１０〜９０重量部であり、より好ましくは１５〜８５重量部である。 The blending ratio of the polylactic acid resin and the liquid crystal polymer in the polylactic acid resin composition of the present invention is 5 to 100 parts by weight, preferably 10 to 90 parts by weight, based on 100 parts by weight of the polylactic acid resin. Preferably it is 15-85 weight part.
なお、ポリ乳酸樹脂および液晶ポリマーは、それらの性質を損なわない範囲で、それぞれポリ乳酸樹脂および液晶ポリマー以外のポリマーや、粒子、難燃剤、帯電防止剤等の添加物を添加したものを配合に供してもよい。これらの添加物のポリ乳酸樹脂および液晶ポリマーに対する配合量は、ポリ乳酸樹脂および液晶ポリマー１００重量部に対して、それぞれ０．１〜２０重量部までとする。 In addition, polylactic acid resin and liquid crystal polymer are blended with polymers other than polylactic acid resin and liquid crystal polymer, and those with additives such as particles, flame retardant, antistatic agent, etc., as long as their properties are not impaired. May be provided. The blending amount of these additives with respect to the polylactic acid resin and the liquid crystal polymer is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polylactic acid resin and the liquid crystal polymer.
ポリ乳酸樹脂１００重量部に対する液晶ポリマーの配合量が５重量部を下回ると、得られるポリ乳酸樹脂組成物の耐熱性向上効果が十分に望めない。液晶ポリマーの配合量が１００重量部を上回ると、バイオマスの利用量が低下し、大気中の二酸化炭素濃度上昇抑制に貢献するポリマーを提供するという本発明の趣旨から逸脱することとなる。 When the blending amount of the liquid crystal polymer with respect to 100 parts by weight of the polylactic acid resin is less than 5 parts by weight, the effect of improving the heat resistance of the obtained polylactic acid resin composition cannot be sufficiently expected. When the blending amount of the liquid crystal polymer exceeds 100 parts by weight, the amount of biomass used decreases, which departs from the gist of the present invention to provide a polymer that contributes to the suppression of the increase in carbon dioxide concentration in the atmosphere.
本発明において、ポリ乳酸樹脂と液晶ポリマーの相溶性を向上させる目的で、ポリ乳酸樹脂１００重量部に対して、０．５〜１０重量部、好ましくは１〜５重量部の相溶化剤が配合される。 In the present invention, for the purpose of improving the compatibility between the polylactic acid resin and the liquid crystal polymer, 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight of a compatibilizer is blended with respect to 100 parts by weight of the polylactic acid resin. Is done.
相溶化剤の配合量が０．５重量部より少ないと、十分な相溶性向上効果が得られず、１０重量部を上回ると、得られるポリ乳酸樹脂組成物の溶融粘度が著しく増加し流動性が低下する傾向がある。 If the blending amount of the compatibilizer is less than 0.5 parts by weight, a sufficient compatibility improving effect cannot be obtained, and if it exceeds 10 parts by weight, the melt viscosity of the resulting polylactic acid resin composition is remarkably increased and the fluidity is increased. Tends to decrease.
なお、本明細書および特許請求の範囲において、相溶化剤とは、ブレンドポリマーを構成する各ポリマーの相の界面に局在し、それらの相間の界面張力を低下させる機能を有するものをいう。 In the present specification and claims, the compatibilizing agent means one having a function of localizing at the interface between phases of each polymer constituting the blend polymer and reducing the interfacial tension between these phases.
相溶化剤の好ましい例としては、カルボキシル基反応性化合物、カルボキシル基、エポキシ基もしくは酸無水物基などを有するポリマーなどを挙げることができる。 Preferable examples of the compatibilizing agent include a carboxyl group-reactive compound, a polymer having a carboxyl group, an epoxy group or an acid anhydride group.
本発明において、相溶化剤として使用されるカルボキシル基反応性化合物としては、ポリ乳酸樹脂のカルボキシル末端基と反応性のある化合物であれば特に限定されるものではないが、ポリ乳酸樹脂の熱分解や加水分解などで生成する酸性低分子化合物のカルボキシル基とも反応性を有するものであればより好ましく、熱分解により生成する酸性低分子化合物のヒドロキシル基末端基とも反応性を有する化合物であることがより好ましい。 In the present invention, the carboxyl group-reactive compound used as the compatibilizer is not particularly limited as long as it is a compound reactive with the carboxyl end group of the polylactic acid resin, but the thermal decomposition of the polylactic acid resin is not limited. It is more preferable if it is reactive with the carboxyl group of the acidic low molecular compound produced by hydrolysis or the like, and it is also a compound reactive with the hydroxyl group end group of the acidic low molecular compound produced by thermal decomposition. More preferred.
このようなカルボキシル基反応性化合物としては、ビスフェノールＡ、レゾルシノール、ハイドロキノン、ピロカテコール、ビスフェノールＦ、サリゲニン、１，３，５−トリヒドロキシベンゼン、ビスフェノールＳ、トリヒドロキシ−ジフェニルジメチルメタン、４，４’−ジヒドロキシビフェニル、１，５−ジヒドロキシナフタレン、カシューフェノール、２，２，５，５−テトラキス（４−ヒドロキシフェニル）ヘキサン等のビスフェノール−グリシジルエーテル系エポキシ化合物、フタル酸グリシジルエステル等のグリシジルエステル系エポキシ化合物、Ｎ−グリシジルアニリン等のグリシジルアミン系エポキシ化合物、グリシジルイミド化合物、脂環式エポキシ化合物、２つ以上のエポキシ基を含有する多官能エポキシ化合物、２，２’−ｍ−フェニレンビス（２−オキサゾリン）、２，２’−ｐ−フェニレンビス（２−オキサゾリン）などのオキサゾリン化合物、オキサジン化合物、Ｎ，Ｎ’−ジ−２，６−ジイソプロピルフェニルカルボジイミド、２，６，２’，６’−テトライソプロピルジフェニルカルボジイミド、ポリカルボジイミドなどのカルボジイミド化合物、エポキシ基、アミノ基、イソシアネート基、水酸基、メルカプト基、ウレイド基の中から選ばれた少なくとも１種の官能基を有するアルコキシシランなどの有機シラン化合物などから選ばれる少なくとも一種の化合物を使用することが好ましく、なかでも多官能エポキシ化合物、エポキシ基、イソシアネート基を有する有機シラン化合物、カルボジイミド化合物が好ましく、特に好ましくは多官能エポキシ化合物、カルボジイミド化合物である。上記カルボキシル基反応性化合物は、一種または二種以上の化合物を任意に選択して使用することができる。 Examples of such carboxyl group-reactive compounds include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4 ′. -Bisphenol-glycidyl ether type epoxy compounds such as dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, glycidyl ester type epoxy such as glycidyl phthalate Compounds, glycidylamine epoxy compounds such as N-glycidylaniline, glycidylimide compounds, alicyclic epoxy compounds, polyfunctional epoxy compounds containing two or more epoxy groups, 2 Oxazoline compounds such as 2′-m-phenylenebis (2-oxazoline) and 2,2′-p-phenylenebis (2-oxazoline), oxazine compounds, N, N′-di-2,6-diisopropylphenylcarbodiimide, At least one functional group selected from carbodiimide compounds such as 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide, polycarbodiimide, epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group, and ureido group It is preferable to use at least one kind of compound selected from organic silane compounds such as alkoxysilanes having a polyvalent epoxy compound, an epoxy group, an organic silane compound having an isocyanate group, and a carbodiimide compound. Multifunctional Epoxy compounds, carbodiimide compounds. As the carboxyl group-reactive compound, one or more compounds can be arbitrarily selected and used.
また、予めこれらの相溶化剤として使用されるカルボキシル基反応性化合物に、乳酸および／または液晶ポリマーを構成するカルボキシル基を有する化合物を反応させた形態で配合に供してもよい。 Moreover, you may use for a mixing | blending in the form with which the carboxyl group-reactive compound used as these compatibilizing agents was made to react with the compound which has a carboxyl group which comprises lactic acid and / or a liquid crystal polymer.
本発明において相溶化剤として使用される、カルボキシル基、エポキシ基もしくは酸無水物基などを有するポリマーとしては、エチレン／（メタ）アクリル酸グリシジル共重合体、エチレン／（メタ）アクリル酸エチル−ｇ−無水マレイン酸共重合体、（「ｇ」はグラフトを表わす、以下同じ）、エチレン／（メタ）アクリル酸グリシジル−ｇ−（メタ）アクリル酸メチル共重合体、エチレン／（メタ）アクリル酸エチル／無水マレイン酸共重合体−ｇ−（メタ）アクリル酸メチル共重合体、二重結合を有する高分子の二重結合部をエポキシ化したエポキシ基含有高分子化合物、ノボラック型フェノール樹脂にエピクロルヒドリンを反応させたノボラック型エポキシ樹脂などを挙げることができる。 Examples of the polymer having a carboxyl group, an epoxy group or an acid anhydride group used as a compatibilizing agent in the present invention include ethylene / (meth) acrylate glycidyl copolymer, ethylene / ethyl (meth) acrylate-g. -Maleic anhydride copolymer ("g" represents graft, the same applies hereinafter), ethylene / glycidyl (meth) acrylate-g-methyl (meth) acrylate copolymer, ethylene / ethyl (meth) acrylate / Maleic anhydride copolymer-g- (meth) acrylic acid methyl copolymer, an epoxy group-containing polymer compound obtained by epoxidizing a double bond part of a polymer having a double bond, epichlorohydrin to a novolac type phenol resin A reacted novolac type epoxy resin can be used.
本発明のポリ乳酸樹脂組成物は、上記で説明した、ポリ乳酸樹脂１００重量部に対し、液晶ポリマー５〜１００重量部、および相溶化剤０．５〜１０重量部を配合し、１７０〜２５０℃の温度下で溶融混練することにより製造される。溶融混練温度が１７０℃を下回ると、混練時に攪拌モーターへの負荷が大きくなり混練機を破損してしまうおそれがあり、また、たとえ混練が可能であったとしても液晶ポリマー相の分散が不均一となる傾向がある。一方、溶融混練温度が２５０℃を超えると、ポリ乳酸の分解が顕著となり、十分な性能が得られなくなる傾向がある。 The polylactic acid resin composition of the present invention contains 5 to 100 parts by weight of a liquid crystal polymer and 0.5 to 10 parts by weight of a compatibilizing agent with respect to 100 parts by weight of the polylactic acid resin described above. It is manufactured by melt-kneading at a temperature of ° C. If the melt kneading temperature is lower than 170 ° C., the load on the stirring motor may increase during kneading and the kneader may be damaged, and even if kneading is possible, the dispersion of the liquid crystal polymer phase is not uniform. Tend to be. On the other hand, when the melt kneading temperature exceeds 250 ° C., the decomposition of polylactic acid becomes remarkable, and there is a tendency that sufficient performance cannot be obtained.
本発明のポリ乳酸樹脂組成物の製造に際しては、バンバリーミキサー、ニーダー、一軸もしくは二軸押出し機などの混練機が使用される。例えば、二軸押出し機を用いた場合などは、非エネルギー（吐出量あたりの押出機仕事量（ｋＷ・ｈ／ｋｇ））０．１〜０．２５で、ベントポートを真空にしながら行うのがよいが、これに限らず、不活性ガス雰囲気下で行ってもよい。 In the production of the polylactic acid resin composition of the present invention, a kneader such as a Banbury mixer, a kneader, a uniaxial or biaxial extruder is used. For example, when a twin-screw extruder is used, it is performed with a non-energy (extruder work amount per discharge amount (kW · h / kg)) of 0.1 to 0.25 while the vent port is evacuated. However, the present invention is not limited to this, and it may be performed in an inert gas atmosphere.
このようにして製造された本発明のポリ乳酸樹脂組成物は、電子顕微鏡で観察される樹脂相分離構造において、ポリ乳酸樹脂が連続相、液晶ポリマーが分散相となる相構造を形成する。しかも、ポリ乳酸樹脂中に液晶ポリマーが均一に分散しているため、耐熱性に優れるものである。 The polylactic acid resin composition of the present invention thus produced forms a phase structure in which the polylactic acid resin is a continuous phase and the liquid crystal polymer is a dispersed phase in a resin phase separation structure observed with an electron microscope. Moreover, since the liquid crystal polymer is uniformly dispersed in the polylactic acid resin, it has excellent heat resistance.
本発明のポリ乳酸樹脂組成物には、必要により、無機充填材および／または有機充填材を配合してもよい。 If necessary, the polylactic acid resin composition of the present invention may contain an inorganic filler and / or an organic filler.
本発明のポリ乳酸樹脂組成物に配合してもよい、無機充填材および／または有機充填材としては、たとえばガラス繊維、シリカアルミナ繊維、アルミナ繊維、炭素繊維、チタン酸カリウム繊維、ホウ酸アルミニウム繊維、アラミド繊維、タルク、マイカ、グラファイト、ウォラストナイト、ドロマイト、クレイ、ガラスフレーク、ガラスビーズ、ガラスバルーン、炭酸カルシウム、硫酸バリウム、および酸化チタンからなる群から選択される１種以上が挙げられる。これらの中では、ガラス繊維が物性とコストのバランスが優れている点で好ましい。 Examples of the inorganic filler and / or organic filler that may be blended in the polylactic acid resin composition of the present invention include glass fiber, silica alumina fiber, alumina fiber, carbon fiber, potassium titanate fiber, and aluminum borate fiber. And at least one selected from the group consisting of aramid fiber, talc, mica, graphite, wollastonite, dolomite, clay, glass flake, glass beads, glass balloon, calcium carbonate, barium sulfate, and titanium oxide. In these, glass fiber is preferable at the point which the balance of a physical property and cost is excellent.
無機充填材および／または有機充填材の配合量は、ポリ乳酸樹脂および液晶ポリマーの合計量１００重量部に対して、０．１〜２００重量部、好ましくは１〜１００重量であるのがよい。 The blending amount of the inorganic filler and / or the organic filler is 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the polylactic acid resin and the liquid crystal polymer.
本発明のポリ乳酸樹脂組成物には、ポリ乳酸樹脂および液晶ポリマー以外に、本発明の目的を損なわない範囲で、さらに他の樹脂成分を配合してもよい。他の樹脂成分としては、たとえばポリアミド、ポリエステル、ポリアセタール、ポリフェニレンエーテル、およびその変性物、ならびにポリスルホン、ポリエーテルスルホン、ポリエーテルイミド、ポリアミドイミドなどの熱可塑性樹脂や、フェノール樹脂、エポキシ樹脂、ポリイミド樹脂などの熱硬化性樹脂が挙げられる。 In addition to the polylactic acid resin and the liquid crystal polymer, the polylactic acid resin composition of the present invention may further contain other resin components as long as the object of the present invention is not impaired. Examples of other resin components include polyamide, polyester, polyacetal, polyphenylene ether, and modified products thereof, and thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, phenol resin, epoxy resin, and polyimide resin. And other thermosetting resins.
他の樹脂成分は、単独で、あるいは２種以上を組み合わせて配合することができる。他の樹脂成分の配合量は、ポリ乳酸樹脂および液晶ポリマーの合計量１００重量部に対して０．１〜１００重量部、好ましくは０．１〜８０重量部となる範囲で配合するのが良い。 Other resin components can be blended alone or in combination of two or more. The compounding amount of the other resin component is 0.1 to 100 parts by weight, preferably 0.1 to 80 parts by weight, based on 100 parts by weight of the total amount of the polylactic acid resin and the liquid crystal polymer. .
また本発明のポリ乳酸樹脂組成物には、ポリ乳酸樹脂の結晶核の形成を促進する結晶核剤を添加することができる。 In addition, a crystal nucleating agent that promotes the formation of crystal nuclei of the polylactic acid resin can be added to the polylactic acid resin composition of the present invention.
本発明で使用される結晶核剤としては、一般にポリマーの結晶核剤として用いられるものを特に制限なく用いることができ、無機系結晶核剤および有機系結晶核剤のいずれも使用することができる。無機系結晶核剤の具体例としては、タルク、カオリナイト、モンモリロナイト、合成マイカ、クレー、ゼオライト、シリカ、グラファイト、カーボンブラック、酸化亜鉛、酸化マグネシウム、酸化チタン、硫化カルシウム、窒化ホウ素、炭酸カルシウム、硫酸バリウム、酸化アルミニウム、酸化ネオジウムおよびフェニルホスホネートの金属塩などを挙げることができる。これらの無機系結晶核剤は、組成物中での分散性を高めるために、有機物で修飾されていることが好ましい。無機系結晶核剤の平均粒径は１０μｍ以下が好ましく、５μｍ以下がさらに好ましく、３μｍ以下が特に好ましい。有機系結晶核剤の具体例としては、安息香酸ナトリウム、安息香酸カリウム、安息香酸リチウム、安息香酸カルシウム、安息香酸マグネシウム、安息香酸バリウム、テレフタル酸リチウム、テレフタル酸ナトリウム、テレフタル酸カリウム、シュウ酸カルシウム、ラウリン酸ナトリウム、ラウリン酸カリウム、ミリスチン酸ナトリウム、ミリスチン酸カリウム、ミリスチン酸カルシウム、オクタコサン酸ナトリウム、オクタコサン酸カルシウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸リチウム、ステアリン酸カルシウム、ステアリン酸マグネシウム、ステアリン酸バリウム、モンタン酸ナトリウム、モンタン酸カルシウム、トルイル酸ナトリウム、サリチル酸ナトリウム、サリチル酸カリウム、サリチル酸亜鉛、アルミニウムジベンゾエート、カリウムジベンゾエート、リチウムジベンゾエート、ナトリウムβ−ナフタレート、ナトリウムシクロヘキサンカルボキシレートなどの有機カルボン酸金属塩、ｐ−トルエンスルホン酸ナトリウム、スルホイソフタル酸ナトリウムなどの有機スルホン酸塩、ラウリン酸アミド、ステアリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスステアリン酸アミド、パルチミン酸アミド、ヒドロキシステアリン酸アミド、エルカ酸アミド、トリメシン酸トリス（ｔ−ブチルアミド）、テレフタル酸ジアニリドなどの有機カルボン酸アミド、低密度ポリエチレン、高密度ポリエチレン、ポリプロピレン、ポリイソプロピレン、ポリブテン、ポリ−４−メチルペンテン、ポリ−３−メチルブテン−１、ポリビニルシクロアルカン、ポリビニルトリアルキルシラン、高融点ポリ乳酸などのポリマー、エチレン−アクリル酸またはメタクリル酸コポリマーのナトリウム塩、スチレン−無水マレイン酸コポリマーのナトリウム塩などのカルボキシル基を有する重合体のナトリウム塩またはカリウム塩（いわゆるアイオノマー）、ベンジリデンソルビトールおよびその誘導体、ナトリウム−２，２’−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）フォスフェートなどのリン化合物金属塩、および２，２−メチルビス（４，６−ジ−ｔ−ブチルフェニル）ナトリウムなどを挙げることができる。 As the crystal nucleating agent used in the present invention, those generally used as a polymer crystal nucleating agent can be used without particular limitation, and both inorganic crystal nucleating agents and organic crystal nucleating agents can be used. . Specific examples of inorganic crystal nucleating agents include talc, kaolinite, montmorillonite, synthetic mica, clay, zeolite, silica, graphite, carbon black, zinc oxide, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, Examples thereof include metal salts of barium sulfate, aluminum oxide, neodymium oxide and phenylphosphonate. These inorganic crystal nucleating agents are preferably modified with an organic substance in order to enhance dispersibility in the composition. The average particle size of the inorganic crystal nucleating agent is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 3 μm or less. Specific examples of organic crystal nucleating agents include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate , Sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, stearic acid Barium, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum Organic carboxylic acid metal salts such as minium dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalate, sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate, lauric acid amide , Stearic acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, palmitic acid amide, hydroxy stearic acid amide, erucic acid amide, trimesic acid tris (t-butylamide), organic carboxylic acid amides such as terephthalic acid dianilide, low Density polyethylene, high density polyethylene, polypropylene, polyisopropylene, polybutene, poly-4-methylpentene, poly-3-methylbutene-1, polyvinyl Sodium or potassium salt of a polymer having a carboxyl group such as a polymer such as loalkane, polyvinyltrialkylsilane, high melting point polylactic acid, sodium salt of ethylene-acrylic acid or methacrylic acid copolymer, sodium salt of styrene-maleic anhydride copolymer (So-called ionomers), benzylidene sorbitol and derivatives thereof, phosphorus compound metal salts such as sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, and 2,2-methylbis (4,6 -Di-t-butylphenyl) sodium and the like.
本発明で使用する結晶核剤としては、上記に例示したもののなかでも、特にタルク、有機カルボン酸金属塩および有機カルボン酸アミドから選択された少なくとも１種が好ましい。好ましいタルクとしては、平均粒径０．５〜７μｍであり、かつ燃焼時の損失分を除いた成分中のＳｉＯ２とＭｇＯの割合が９３重量％以上であるタルクを挙げることができる。結晶核剤は、１種または２種以上を併用してもよい。 As the crystal nucleating agent used in the present invention, among those exemplified above, at least one selected from talc, organic carboxylic acid metal salts and organic carboxylic acid amides is particularly preferable. Preferable talc includes talc having an average particle size of 0.5 to 7 μm and a ratio of SiO 2 and MgO in the component excluding a loss during combustion of 93% by weight or more. The crystal nucleating agent may be used alone or in combination of two or more.
結晶核剤の配合量は、ポリ乳酸樹脂および液晶ポリマーの合計量１００重量部に対して、０．０１〜３０重量部が好ましく、０．０５〜２０重量部がより好ましく、０．１〜１５重量部が特に好ましい。 The compounding amount of the crystal nucleating agent is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 20 parts by weight, with respect to 100 parts by weight of the total amount of the polylactic acid resin and the liquid crystal polymer. Part by weight is particularly preferred.
また、本発明のポリ乳酸樹脂組成物には、結晶化を促進するために、固相状態で加熱処理を施してもよい。加熱処理は減圧下または不活性ガス雰囲気下で、８０〜２１０℃の温度下で３〜６０分行うのがよい。 In addition, the polylactic acid resin composition of the present invention may be subjected to a heat treatment in a solid phase state in order to promote crystallization. The heat treatment is preferably performed under reduced pressure or in an inert gas atmosphere at a temperature of 80 to 210 ° C. for 3 to 60 minutes.
以上説明した、無機充填材および／または有機充填材、他の樹脂成分および結晶核剤は、ポリ乳酸樹脂、液晶ポリマーおよび相溶化剤と共に、バンバリーミキサー、ニーダー、一軸もしくは二軸押出し機などを用いて溶融混練することによって、ポリ乳酸樹脂組成物に配合してもよいし、ポリ乳酸樹脂、液晶ポリマーおよび相溶化剤を配合して得られたポリ乳酸樹脂組成物を成形加工する際に配合してもよい。 As described above, the inorganic filler and / or organic filler, other resin components and crystal nucleating agent, together with polylactic acid resin, liquid crystal polymer and compatibilizer, use Banbury mixer, kneader, single screw or twin screw extruder, etc. It may be blended into the polylactic acid resin composition by melt kneading, or blended when molding the polylactic acid resin composition obtained by blending the polylactic acid resin, liquid crystal polymer and compatibilizer. May be.
本発明のポリ乳酸樹脂組成物は、射出成形機、押出機などを用いる公知の成形方法によって溶融加工され、成形品、フィルムおよび繊維などの製品とされる。本発明のポリ乳酸樹脂組成物は、耐熱性が優れることから、機械部品、電気・電子部品、建築・土木部材、家庭・事務用品、家具用部品および日用品など各種用途に利用することができる。 The polylactic acid resin composition of the present invention is melt-processed by a known molding method using an injection molding machine, an extruder, or the like to obtain products such as molded products, films and fibers. Since the polylactic acid resin composition of the present invention has excellent heat resistance, it can be used in various applications such as mechanical parts, electrical / electronic parts, construction / civil engineering members, household / office supplies, furniture parts, and daily necessities.
以下、実施例により本発明を詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example.
実施例および比較例において、ポリ乳酸樹脂、液晶ポリマー、相溶化剤および結晶核剤は、以下のものを使用した。
ポリ乳酸樹脂：三井化学株式会社製ポリＬ−乳酸、レイシアＨ−４００（数平均分子量１０４，０００、重量平均分子量２１１,０００、結晶融解温度１６６℃）。
液晶ポリマーＡ：上野製薬株式会社製芳香族液晶ポリエステル（パラヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／ハイドロキノン／テレフタル酸共重合体、結晶融解温度２２０℃）。
液晶ポリマーＢ：上野製薬株式会社製芳香族液晶ポリエステル（パラヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸共重合体、結晶融解温度２８０℃）。
相溶化剤：日清紡績株式会社製ポリカルボジイミド、カルボジライトＨＭＶ−８ＣＡ。
結晶核剤：新日本理化株式会社製１,３,５−ベンゼントリカルボキサミド、エヌジェスター ＴＦ−１。
In Examples and Comparative Examples, polylactic acid resin, liquid crystal polymer, compatibilizing agent and crystal nucleating agent were used as follows.
Polylactic acid resin: Poly L-lactic acid manufactured by Mitsui Chemicals, Inc., Lacia H-400 (number average molecular weight 104,000, weight average molecular weight 211,000, crystal melting temperature 166 ° C.).
Liquid crystal polymer A: Aromatic liquid crystal polyester (parahydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / hydroquinone / terephthalic acid copolymer, crystal melting temperature 220 ° C.) manufactured by Ueno Pharmaceutical Co., Ltd.
Liquid crystal polymer B: Aromatic liquid crystal polyester (parahydroxybenzoic acid / 6-hydroxy-2-naphthoic acid copolymer, crystal melting temperature 280 ° C.) manufactured by Ueno Pharmaceutical Co., Ltd.
Compatibilizing agent: Nisshinbo Co., Ltd. polycarbodiimide, carbodilite HMV-8CA.
Crystal nucleating agent: 1,3,5-benzenetricarboxamide, NJester TF-1 manufactured by Shin Nippon Rika Co., Ltd.
（樹脂相分離構造の観察）
溶融混練により得られたポリ乳酸樹脂組成物サンプルを液体窒素で冷却し、破断した後で白金蒸着したサンプルを日立製作所社製電子顕微鏡ＨｉｔａｃｈｉＳ−３００Ｎを用いて倍率１０００倍で観察した。
(Observation of resin phase separation structure)
The polylactic acid resin composition sample obtained by melt-kneading was cooled with liquid nitrogen, and the sample on which platinum was vapor-deposited after rupture was observed at a magnification of 1000 times using Hitachi Electron Microscope Hitachi S-300N.
（結晶融解温度の測定）
サンプル３ｍｇを専用アルミニウムパンに入れ、島津製作所社製の示差走査熱量計ＳＨＩＭＡＤＺＵ ＤＳＣ−５０を用いて、窒素ガス雰囲気下、昇温速度１０℃／分で測定を行った。１５０℃以上に観察される吸熱ピークのピークトップ温度を結晶融解温度とした。
(Measurement of crystal melting temperature)
3 mg of a sample was put in a dedicated aluminum pan, and measurement was performed using a differential scanning calorimeter SHIMADZU DSC-50 manufactured by Shimadzu Corporation at a heating rate of 10 ° C./min in a nitrogen gas atmosphere. The peak top temperature of the endothermic peak observed at 150 ° C. or higher was defined as the crystal melting temperature.
（耐熱性の測定）
溶融混練により得られたポリ乳酸樹脂組成物サンプルを、１００℃で６時間減圧乾燥し、２３０℃でプレスした後に急冷し、厚み０．２ｍｍのフィルムを作成した。このようにして作成したポリ乳酸樹脂組成物フィルムを５ｍｍの幅に切り出し測定サンプルとした。株式会社ユービーエム社製動的粘弾性測定装置ＵＢＭ Ｒｈｅｏｇｅｌ−Ｅ４０００を用いて、このサンプルの引っ張り動的貯蔵弾性率を昇温速度３℃／分の下で測定し評価した。測定に際し、周波数３２Ｈｚ、チャック間距離１５ｍｍとした。
(Measurement of heat resistance)
A polylactic acid resin composition sample obtained by melt kneading was dried under reduced pressure at 100 ° C. for 6 hours, pressed at 230 ° C., and then rapidly cooled to prepare a film having a thickness of 0.2 mm. The polylactic acid resin composition film thus prepared was cut into a width of 5 mm and used as a measurement sample. Using a dynamic viscoelasticity measuring device UBM Rheogel-E4000 manufactured by UBM Co., Ltd., the tensile dynamic storage elastic modulus of this sample was measured and evaluated at a heating rate of 3 ° C./min. In the measurement, the frequency was 32 Hz and the distance between chucks was 15 mm.
（固相加熱処理）
動的粘弾性測定用に作成したポリ乳酸樹脂組成物フィルムを加熱圧縮機で１ＭＰａ加圧下、１００℃で１時間加熱処理を行った。
(Solid phase heat treatment)
The polylactic acid resin composition film prepared for dynamic viscoelasticity measurement was subjected to heat treatment at 100 ° C. for 1 hour under 1 MPa pressure with a heating compressor.
（実施例１）
ポリ乳酸樹脂２４．０ｇ、液晶ポリマーＡ６．００ｇ、相溶化剤０．２４ｇを混合し、８０℃で１０時間減圧乾燥した。この乾燥混合物を株式会社オオバ機械社製一軸混練押出し機を使用し、シリンダー温度２３０℃で、直径０．５ｍｍのノズルを使用しスクリュー回転速度２０ｒｐｍで混練しながら押し出し、ポリ乳酸樹脂組成物サンプルを作成した。このポリ乳酸樹脂組成物サンプルの相分離構造の観察を行ったところ、ポリ乳酸樹脂が連続相、液晶ポリマーＡが分散相である相分離構造が確認された。実施例１のサンプルの電子顕微鏡による観察写真を図１に示す。また、動的粘弾性測定により耐熱性を評価した。結果を図３および表１に示す。
Example 1
24.0 g of polylactic acid resin, 6.00 g of liquid crystal polymer A and 0.24 g of compatibilizer were mixed and dried under reduced pressure at 80 ° C. for 10 hours. This dry mixture was extruded using a uniaxial kneading extruder manufactured by Ooba Machinery Co., Ltd. at a cylinder temperature of 230 ° C. using a nozzle with a diameter of 0.5 mm at a screw rotation speed of 20 rpm, and a polylactic acid resin composition sample was obtained. Created. When the phase separation structure of this polylactic acid resin composition sample was observed, a phase separation structure in which the polylactic acid resin was a continuous phase and the liquid crystal polymer A was a dispersed phase was confirmed. An observation photograph of the sample of Example 1 with an electron microscope is shown in FIG. Moreover, heat resistance was evaluated by dynamic viscoelasticity measurement. The results are shown in FIG.
ポリ乳酸樹脂単独の場合、その貯蔵弾性率が１６０℃付近から１７０℃付近で急激に低下し、１８０℃ではほとんど底値（Ｅ’＝約３.００Ｅ＋０１Ｐａ）であるのに対して、ポリ乳酸樹脂、液晶ポリマーＡおよび相溶化剤を配合した本実施例では１６０℃付近から１７０℃付近での動的貯蔵弾性率の低下割合が著しく抑制され、耐熱性が改善されたものであった。 In the case of the polylactic acid resin alone, its storage elastic modulus sharply decreases from around 160 ° C. to around 170 ° C., and is almost the bottom value (E ′ = about 3.00E + 01 Pa) at 180 ° C., whereas the polylactic acid resin, In this example in which the liquid crystal polymer A and the compatibilizing agent were blended, the rate of decrease in the dynamic storage modulus from around 160 ° C. to around 170 ° C. was remarkably suppressed, and the heat resistance was improved.
（実施例２〜６）
相溶化剤の添加量、混練温度、結晶核剤の添加量を表１のとおりとした以外は実施例１と同様にしてポリ乳酸樹脂組成物サンプルを作成し、相分離構造の観察、耐熱性の評価を行った。結果を表１に示す。また、実施例２について、動的粘弾性の測定結果を図４に示す。
(Examples 2 to 6)
A polylactic acid resin composition sample was prepared in the same manner as in Example 1 except that the addition amount of the compatibilizing agent, the kneading temperature, and the addition amount of the crystal nucleating agent were as shown in Table 1. Observation of the phase separation structure, heat resistance Was evaluated. The results are shown in Table 1. Moreover, about Example 2, the measurement result of dynamic viscoelasticity is shown in FIG.
（実施例７）
実施例２で得られたサンプルを固相加熱処理し、耐熱性の評価を行った。結果を図５および表１に示す。ポリ乳酸樹脂単独の場合はその貯蔵弾性率が１６０℃付近から１７０℃付近で急激に低下し１８０℃ではほとんど底値であるのに対して、ポリ乳酸樹脂、液晶ポリマーＡおよび相溶化剤を配合し、更に固相加熱処理を施した本実施例では１６０℃付近から１７０℃付近での動的貯蔵弾性率の低下割合が著しく抑制され、さらに２４０℃付近においてもその値が保持され、耐熱性が大幅に改善されたものであった。
(Example 7)
The sample obtained in Example 2 was subjected to solid phase heat treatment, and the heat resistance was evaluated. The results are shown in FIG. In the case of polylactic acid resin alone, its storage elastic modulus suddenly decreases from around 160 ° C. to around 170 ° C. and is almost bottom at 180 ° C., whereas polylactic acid resin, liquid crystal polymer A and compatibilizing agent are blended. Further, in the present example, which was further subjected to solid phase heat treatment, the rate of decrease in the dynamic storage modulus from around 160 ° C. to around 170 ° C. was remarkably suppressed, and the value was maintained even around 240 ° C. It was a great improvement.
（比較例１〜３）
相溶化剤を使用しない（比較例１）、混練温度を２６０℃とした（比較例２）、液晶ポリマーとして結晶融解温度２８０℃の液晶ポリマーＢを用いた（比較例３）以外は実施例１と同様にしてポリ乳酸樹脂組成物サンプルを作成した。比較例１のサンプルの電子顕微鏡による観察写真を図２に、動的粘弾性の測定結果を図６に示す。
(Comparative Examples 1-3)
Example 1 except that no compatibilizer was used (Comparative Example 1), the kneading temperature was 260 ° C. (Comparative Example 2), and liquid crystal polymer B having a crystal melting temperature of 280 ° C. was used as the liquid crystal polymer (Comparative Example 3). In the same manner, a polylactic acid resin composition sample was prepared. FIG. 2 shows a photograph of the sample of Comparative Example 1 observed with an electron microscope, and FIG. 6 shows the measurement result of dynamic viscoelasticity.
比較例１では、相分離構造の観察においてポリ乳酸樹脂が連続相、液晶ポリマーＡが分散相である相分離構造が確認されたが、相溶化剤を添加した場合に比べて分散相の径が大きく、分散状態も不均一であった。また連続相と分散相の界面が明瞭であった。動的貯蔵弾性率の測定においては１０５℃付近から貯蔵弾性率が急激に低下し、１２０℃付近で既に底値となり、耐熱性が非常に低いものであった。 In Comparative Example 1, the phase separation structure in which the polylactic acid resin was the continuous phase and the liquid crystal polymer A was the dispersed phase was observed in the observation of the phase separation structure, but the diameter of the dispersed phase was larger than that in the case where the compatibilizing agent was added. It was large and the dispersion state was uneven. The interface between the continuous phase and the dispersed phase was clear. In the measurement of the dynamic storage elastic modulus, the storage elastic modulus suddenly decreased from around 105 ° C., already reached the bottom around 120 ° C., and the heat resistance was very low.
比較例２においては、溶融混練中に分解ガスが発生し、安定したポリ乳酸樹脂組成物を得ることができなかった。 In Comparative Example 2, decomposition gas was generated during melt kneading, and a stable polylactic acid resin composition could not be obtained.
比較例３においては、混練開始時にスクリューの攪拌トルクが上限値を示し、最後まで混練することができなかった。 In Comparative Example 3, the stirring torque of the screw showed an upper limit value at the start of kneading, and kneading could not be performed to the end.
Claims (7)
液晶ポリマーの示差走査熱量計により測定される結晶融解温度が１７０〜２５０℃であり、
液晶ポリマーが本質的に、以下の式［Ｉ］〜［ＩＶ］で示される繰返し単位により構成される、ポリ乳酸樹脂組成物：
０．４≦ｐ／ｑ≦２．０
２モル％≦ｒ≦１５モル％、および
２モル％≦ｓ≦１５モル％］。 Polylactic acid resin, 5 to 100 parts by weight of liquid crystal polymer with respect to 100 parts by weight of polylactic acid resin, and 0.5 to 10 parts by weight of compatibilizer with respect to 100 parts by weight of polylactic acid resin,
The crystal melting temperature measured by a differential scanning calorimeter of the liquid crystal polymer is 170 to 250 ° C.,
A polylactic acid resin composition in which the liquid crystal polymer is essentially composed of repeating units represented by the following formulas [I] to [IV]:
0.4 ≦ p / q ≦ 2.0
2 mol% ≦ r ≦ 15 mol%, and
2 mol% ≦ s ≦ 15 mol%] .
３５モル％≦ｐ≦４８モル％、
３５モル％≦ｑ≦４８モル％、
２モル％≦ｒ≦１５モル％、および
２モル％≦ｓ≦１５モル％。 Formula [I] ~ composition ratio of the repeating unit represented by the [IV] is one that satisfies the following formula, according to claim 1, wherein the polylactic acid resin composition:
35 mol% ≦ p ≦ 48 mol%,
35 mol% ≦ q ≦ 48 mol%,
2 mol% ≦ r ≦ 15 mol%, and 2 mol% ≦ s ≦ 15 mol%.
Ａｒ2が、
Ar 2 is
ここで、
液晶ポリマーの示差走査熱量計により測定される結晶融解温度は１７０〜２５０℃であり、
液晶ポリマーは本質的に、以下の式［Ｉ］〜［ＩＶ］で示される繰返し単位により構成される：
０．４≦ｐ／ｑ≦２．０
２モル％≦ｒ≦１５モル％、および
２モル％≦ｓ≦１５モル％］。 A polylactic acid resin, 5 to 100 parts by weight of a liquid crystal polymer with respect to 100 parts by weight of the polylactic acid resin, and 0.5 to 10 parts by weight of a compatibilizer with respect to 100 parts by weight of the polylactic acid resin are blended. A method for producing a polylactic acid resin composition comprising a phase structure in which a polylactic acid resin is a continuous phase and a liquid crystal polymer is a dispersed phase, including melt kneading at a temperature of ° C.
here,
The crystal melting temperature measured by a differential scanning calorimeter of the liquid crystal polymer is 170-250 ° C.,
The liquid crystal polymer is essentially composed of repeating units represented by the following formulas [I] to [IV]:
0.4 ≦ p / q ≦ 2.0
2 mol% ≦ r ≦ 15 mol%, and
2 mol% ≦ s ≦ 15 mol%].
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