JP2012167219A - Plasticizer for polylactic acid resin, polylactic acid resin composition, and polylactic acid resin molding - Google Patents
Plasticizer for polylactic acid resin, polylactic acid resin composition, and polylactic acid resin molding Download PDFInfo
- Publication number
- JP2012167219A JP2012167219A JP2011030438A JP2011030438A JP2012167219A JP 2012167219 A JP2012167219 A JP 2012167219A JP 2011030438 A JP2011030438 A JP 2011030438A JP 2011030438 A JP2011030438 A JP 2011030438A JP 2012167219 A JP2012167219 A JP 2012167219A
- Authority
- JP
- Japan
- Prior art keywords
- polylactic acid
- acid resin
- resin composition
- plasticizer
- composition according
- 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
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 120
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 120
- 229920005989 resin Polymers 0.000 title claims abstract description 92
- 239000011347 resin Substances 0.000 title claims abstract description 92
- 239000004014 plasticizer Substances 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 39
- 238000000465 moulding Methods 0.000 title claims abstract description 12
- 239000004359 castor oil Substances 0.000 claims abstract description 25
- 235000019438 castor oil Nutrition 0.000 claims abstract description 25
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 25
- -1 oxyalkylene glycol Chemical compound 0.000 claims description 38
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 21
- 230000003287 optical effect Effects 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 11
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 229940022769 d- lactic acid Drugs 0.000 claims description 10
- 239000011256 inorganic filler Substances 0.000 claims description 9
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 9
- 239000002667 nucleating agent Substances 0.000 claims description 8
- 229910052623 talc Inorganic materials 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 239000000454 talc Substances 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 229930182843 D-Lactic acid Natural products 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical group OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000007974 melamines Chemical class 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 150000003672 ureas Chemical class 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 30
- 125000002947 alkylene group Chemical group 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229920001432 poly(L-lactide) Polymers 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229960000448 lactic acid Drugs 0.000 description 6
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920001434 poly(D-lactide) Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- 239000003484 crystal nucleating agent Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000003074 decanoyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C(*)=O 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
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- 125000000268 heptanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000016 octadecenoyl group Chemical group O=C([*])C([H])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 125000001312 palmitoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 238000007493 shaping process Methods 0.000 description 2
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
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- 235000004443 Ricinus communis Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
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- BEWFIPLBFJGWSR-UHFFFAOYSA-N butyl 12-acetyloxyoctadec-9-enoate Chemical compound CCCCCCC(OC(C)=O)CC=CCCCCCCCC(=O)OCCCC BEWFIPLBFJGWSR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010449 novaculite Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明はポリ乳酸樹脂用可塑剤、ポリ乳酸樹脂組成物及びポリ乳酸樹脂成形体に関する。近年、自然環境保護の見地から、自然環境のなかで分解する生分解性樹脂が注目され、なかでも農産物を原料とする製造技術が確立している上、溶融成形性や耐熱性に優れるため、ポリ乳酸樹脂が最も注目されている。しかし、ポリ乳酸樹脂は、もともと脆く、硬く、可撓性に欠ける特性のため、その利用は硬質成形品の分野に限られ、射出成形体等で成形される軟質又は半硬質の分野にまでは広がっていないのが現状である。またポリ乳酸樹脂は結晶化速度が遅く、その成形品は通常非晶状態となり、しかもガラス転移温度（Ｔｇ）が６０℃と低く、その成形品は耐熱性に劣るというのが現状である。本発明は、ポリ乳酸樹脂の利用を、軟質又は半硬質の分野にまで問題なく広げることができるポリ乳酸樹脂用可塑剤、かかる可塑剤を含有するポリ乳酸樹脂組成物及びかかる組成物を成形して得られるポリ乳酸樹脂成形体に関する。 The present invention relates to a plasticizer for polylactic acid resin, a polylactic acid resin composition, and a polylactic acid resin molded article. In recent years, biodegradable resins that decompose in the natural environment have attracted attention from the standpoint of protecting the natural environment, and in particular, manufacturing technology using agricultural products as raw materials has been established, and because it has excellent melt moldability and heat resistance, Polylactic acid resin has received the most attention. However, polylactic acid resin is inherently brittle, hard, and lacks flexibility, so its use is limited to the field of hard molded products, and even to the soft or semi-rigid field molded by injection molded articles. The current situation is not widespread. In addition, the polylactic acid resin has a low crystallization rate, the molded product is usually in an amorphous state, and the glass transition temperature (Tg) is as low as 60 ° C., and the molded product is inferior in heat resistance. The present invention relates to a plasticizer for a polylactic acid resin that can broaden the use of a polylactic acid resin to the soft or semi-rigid field, a polylactic acid resin composition containing such a plasticizer, and such a composition. It is related with the polylactic acid resin molding obtained by this.
従来、ポリ乳酸樹脂を含有する組成物から得られる成形品の柔軟性を向上させるため、可塑剤を用いる方法が知られており（例えば特許文献１及び２参照）、またポリ乳酸樹脂を含有する組成物から得られる成形品の耐熱性を向上させるため、結晶核剤を用いて結晶化させる方法が知られている（例えば特許文献３及び４参照）。しかし、これらの従来法では、ポリ乳酸樹脂を含有する組成物の成形性、かかる組成物から得られる成形品の耐熱性や耐衝撃性等が依然として不充分という問題があり、更なる改善が求められている。 Conventionally, in order to improve the flexibility of a molded product obtained from a composition containing a polylactic acid resin, a method using a plasticizer is known (see, for example, Patent Documents 1 and 2), and also contains a polylactic acid resin. In order to improve the heat resistance of a molded product obtained from the composition, a method of crystallization using a crystal nucleating agent is known (for example, see Patent Documents 3 and 4). However, in these conventional methods, there is a problem that the moldability of a composition containing a polylactic acid resin and the heat resistance and impact resistance of a molded product obtained from such a composition are still insufficient, and further improvement is required. It has been.
本発明が解決しようとする課題は、低い金型温度でも優れた成形性のポリ乳酸樹脂組成物を調製することができ、またかかる組成物から優れた耐熱性、耐衝撃性及び耐ブリード性のポリ乳酸樹脂成形体を得ることができるポリ乳酸樹脂用可塑剤、かかる可塑剤を含有するポリ乳酸樹脂組成物及びかかる組成物を成形して得られるポリ乳酸樹脂成形体を提供することにある。 The problem to be solved by the present invention is that a polylactic acid resin composition having excellent moldability even at a low mold temperature can be prepared, and excellent heat resistance, impact resistance and bleed resistance can be prepared from such a composition. It is providing the plasticizer for polylactic acid resin which can obtain a polylactic acid resin molding, the polylactic acid resin composition containing this plasticizer, and the polylactic acid resin molding obtained by shape | molding this composition.
しかして本発明者らは、前記の課題を解決するべく研究した結果、ポリ乳酸樹脂用の可塑剤として特定の硬化ヒマシ油誘導体を用いることが、正しく好適であることを見出した。 As a result of studying the above problems, the present inventors have found that the use of a specific hardened castor oil derivative as a plasticizer for a polylactic acid resin is correctly suitable.
すなわち本発明は、下記の化１で示される硬化ヒマシ油誘導体から成ることを特徴とするポリ乳酸樹脂用可塑剤に係る。また本発明は、かかる可塑剤を含有するポリ乳酸樹脂組成物及びかかる組成物を成形して得られるポリ乳酸樹脂成形体に係る。
That is, the present invention relates to a plasticizer for polylactic acid resin comprising a hardened castor oil derivative represented by the following chemical formula 1. The present invention also relates to a polylactic acid resin composition containing such a plasticizer and a polylactic acid resin molded article obtained by molding such a composition.
化１において、
Ｒ１，Ｒ２，Ｒ３：水素原子、炭素数１〜２０の脂肪族アシル基又は分子中に炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜２００の（ポリ）オキシアルキレングリコールから一方の水酸基を除いた残基（但し、Ｒ１〜Ｒ３のうちで少なくとも一つは炭素数２〜２２の脂肪族アシル基）
Ｒ４，Ｒ５，Ｒ６：分子中に炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜２００の（ポリ）オキシアルキレングリコールからすべての水酸基を除いた残基
ｐ，ｑ，ｒ：０又は１の整数（但し、ｐ〜ｒのうちで少なくとも一つは１）
In chemical formula 1,
R 1 , R 2 , R 3 : hydrogen atom, aliphatic acyl group having 1 to 20 carbon atoms or carbon number 2 having a (poly) oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in the molecule Residue obtained by removing one hydroxyl group from ˜200 (poly) oxyalkylene glycol (wherein at least one of R 1 to R 3 is an aliphatic acyl group having 2 to 22 carbon atoms)
R 4 , R 5 , R 6 : all hydroxyl groups from a (poly) oxyalkylene glycol having 2 to 200 carbon atoms and having a (poly) oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in the molecule Excluded residues p, q, r: an integer of 0 or 1 (provided that at least one of p to r is 1)
先ず、本発明に係るポリ乳酸樹脂用可塑剤（以下、単に本発明の可塑剤という）について説明する。本発明の可塑剤は、前記したように化１で示される硬化ヒマシ油誘導体から成るものである。化１で示される硬化ヒマシ油誘導体には、１）硬化ヒマシ油のアルキレンオキサイド付加物、２）硬化ヒマシ油のアルキレンオキサイド付加物のモノエステル、３）硬化ヒマシ油のアルキレンオキサイド付加物のジエステル、４）硬化ヒマシ油のアルキレンオキサイド付加物のトリエステル等が挙げられるが、なかでも硬化ヒマシ油のアルキレンオキサイド付加物のモノエステル、硬化ヒマシ油のアルキレンオキサイド付加物のジエステル、硬化ヒマシ油のアルキレンオキサイド付加物のトリエステルが好ましい。これらは、１種を用いても、又は２種以上を用いてもよい。 First, the plasticizer for polylactic acid resin according to the present invention (hereinafter simply referred to as the plasticizer of the present invention) will be described. The plasticizer of the present invention comprises a hardened castor oil derivative represented by Chemical Formula 1 as described above. The hardened castor oil derivative represented by Chemical Formula 1 includes 1) an alkylene oxide adduct of hardened castor oil, 2) a monoester of an alkylene oxide adduct of hardened castor oil, 3) a diester of an alkylene oxide adduct of hardened castor oil, 4) Triesters of alkylene oxide adducts of hardened castor oil, among others, monoesters of alkylene oxide adducts of hardened castor oil, diesters of alkylene oxide adducts of hardened castor oil, alkylene oxides of hardened castor oil Adduct triesters are preferred. These may use 1 type or may use 2 or more types.
化１中のＲ１、Ｒ２及びＲ３は、１）水素原子、２）アセチル基、プロパノイル基、ブタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ヘキサデカノイル基、オクタデカノイル基、ヘキサデセノイル基、オクタデセノイル基、エイコセノイル基等の炭素数２〜２２の脂肪族アシル基、又は３）分子中にオキシエチレン単位、オキシプロピレン単位、オキシブチレン単位等の炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜２００の（ポリ）オキシアルキレングリコールから一方の水酸基を除いた残基である。但し、Ｒ１〜Ｒ３のうちで少なくとも一つは、炭素数２〜２２の脂肪族アシル基である。なかでもＲ１〜Ｒ３としては、水素原子又はアセチル基、プロパノイル基、ブタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ヘキサデカノイル基、オクタデカノイル基、ヘキサデセノイル基、オクタデセノイル基、エイコセノイル基等の炭素数２〜２２の脂肪族アシル基が好ましい。 R 1 , R 2 and R 3 in Chemical Formula 1 are 1) hydrogen atom, 2) acetyl group, propanoyl group, butanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, hexadecanoyl group, C2-C22 aliphatic acyl group such as octadecanoyl group, hexadecenoyl group, octadecenoyl group, eicosenoyl group, or 3) C2-C4 such as oxyethylene unit, oxypropylene unit, oxybutylene unit in the molecule This is a residue obtained by removing one hydroxyl group from a (poly) oxyalkylene glycol having 2 to 200 carbon atoms and having a (poly) oxyalkylene group composed of oxyalkylene units. However, at least one of R 1 to R 3 is an aliphatic acyl group having 2 to 22 carbon atoms. Among them, as R 1 to R 3 , a hydrogen atom or acetyl group, propanoyl group, butanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, hexadecanoyl group, octadecanoyl group, hexadecenoyl group, C2-C22 aliphatic acyl groups such as octadecenoyl group and eicosenoyl group are preferred.
また化１中のＲ４、Ｒ５及びＲ６は、分子中にオキシエチレン単位、オキシプロピレン単位、オキシブチレン単位等の炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜２００の（ポリ）オキシアルキレングリコールからすべての水酸基を除いた残基であり、ｐ、ｑ及びｒは０又は１の整数である。但し、ｐ〜ｒのうちで少なくとも一つは１である。なかでもＲ４〜Ｒ６としては、分子中にオキシエチレン単位及び／又はオキシプロピレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜２００の（ポリ）オキシアルキレングリコールからすべての水酸基を除いた残基が好ましく、分子中にオキシエチレン単位及び／又はオキシプロピレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜１００の（ポリ）オキシアルキレングリコールからすべての水酸基を除いた残基がより好ましい。 In addition, R 4 , R 5 and R 6 in Chemical Formula 1 are (poly) oxyalkylene groups composed of oxyalkylene units having 2 to 4 carbon atoms such as oxyethylene units, oxypropylene units and oxybutylene units in the molecule. And a residue obtained by removing all hydroxyl groups from a (poly) oxyalkylene glycol having 2 to 200 carbon atoms and p, q and r are integers of 0 or 1. However, at least one of p to r is 1. Among them, R 4 to R 6 include all hydroxyl groups from (poly) oxyalkylene glycol having 2 to 200 carbon atoms having a (poly) oxyalkylene group composed of oxyethylene units and / or oxypropylene units in the molecule. Residues are preferably removed, and all hydroxyl groups are removed from a (poly) oxyalkylene glycol having 2 to 100 carbon atoms having a (poly) oxyalkylene group composed of oxyethylene units and / or oxypropylene units in the molecule. More preferred are residues.
次に、本発明に係るポリ乳酸樹脂組成物（以下、単に本発明の組成物という）及びポリ乳酸樹脂成形体（以下、単に本発明の成形体という）について説明する。本発明の組成物は、ポリ乳酸樹脂と前記した本発明の可塑剤とを含有して成るものであるが、更に有機核剤及び／又は無機充填剤を含有して成るものが好ましい。 Next, a polylactic acid resin composition according to the present invention (hereinafter simply referred to as the composition of the present invention) and a polylactic acid resin molded body (hereinafter simply referred to as the molded body of the present invention) will be described. The composition of the present invention comprises a polylactic acid resin and the above-described plasticizer of the present invention, but preferably further comprises an organic nucleating agent and / or an inorganic filler.
本発明の組成物に供する本発明の可塑剤、有機核剤及び無機充填剤の含有量について特に制限はないが、ポリ乳酸樹脂１００質量部当たり本発明の可塑剤を１〜３０質量部の割合で含有するものが好ましく、ポリ乳酸樹脂１００質量部当たり本発明の可塑剤を１〜３０質量部及び有機核剤を０．０１〜１０質量部の割合で含有して成るものがより好ましく、ポリ乳酸樹脂１００質量部当たり本発明の可塑剤を１〜３０質量部、有機核剤を０．０１〜１０質量部及び無機充填剤を１〜３０質量部の割合で含有して成るものが特に好ましい。 Although there is no restriction | limiting in particular about content of the plasticizer of this invention used for the composition of this invention, an organic nucleus agent, and an inorganic filler, The ratio of 1-30 mass parts of plasticizers of this invention per 100 mass parts of polylactic acid resin In which the plasticizer of the present invention is contained in an amount of 1 to 30 parts by mass and the organic nucleating agent in an amount of 0.01 to 10 parts by mass. Particularly preferred are those containing 1 to 30 parts by weight of the plasticizer of the present invention, 0.01 to 10 parts by weight of an organic nucleating agent and 1 to 30 parts by weight of an inorganic filler per 100 parts by weight of lactic acid resin. .
本発明の組成物に供する有機核剤の種類について特に制限はなく、これにはアミド化合物、脂肪酸エステル化合物、アミド化合物の金属塩、ヒドラジド化合物、有機カルボン酸金属塩、有機スルホン酸金属塩、フェニルホスホン酸金属塩、リン酸エステル金属塩、メラミン化合物、ウラシル類、尿素類等が挙げられるが、なかでもフェニルホスホン酸金属塩、芳香族カルボン酸アミドの金属塩、芳香族スルホン酸ジアルキルエステル金属塩、リン酸エステル金属塩、ロジン酸類の金属塩、ロジン酸アミド、カルボヒドラジド類、Ｎ−置換尿素類、メラミン化合物の塩及びウラシル類から選ばれる１種又は２種以上が好ましく、フェニルホスホン酸金属塩、芳香族スルホン酸ジアルキルエステル金属塩がより好ましい。 There are no particular restrictions on the type of organic nucleating agent used in the composition of the present invention, and this includes amide compounds, fatty acid ester compounds, metal salts of amide compounds, hydrazide compounds, organic carboxylic acid metal salts, organic sulfonic acid metal salts, phenyl Examples include phosphonic acid metal salts, phosphoric acid ester metal salts, melamine compounds, uracils, ureas, among others, phenylphosphonic acid metal salts, metal salts of aromatic carboxylic acid amides, aromatic sulfonic acid dialkyl ester metal salts 1 or more selected from phosphoric acid ester metal salts, metal salts of rosin acids, rosin acid amides, carbohydrazides, N-substituted ureas, salts of melamine compounds and uracils, and phenylphosphonic acid metal Salts and aromatic sulfonic acid dialkyl ester metal salts are more preferred.
また本発明の組成物に供する無機充填剤の種類について特に制限はなく、これには通常熱可塑性樹脂の強化に用いられる繊維状、板状、粉末状のものを用いることができる。具体的には、ガラス繊維、アスベスト繊維、炭素繊維、チタン酸カリウムウイスカー、ホウ酸アルミニウムウイスカー、マグネシウム系ウイスカー、珪素系ウイスカー、ワラステナイト、セピオライト、アスベスト、スラグ繊維、ゾノライト、エレスタダイト、石膏繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化硼素繊維及び硼素繊維等の繊維状無機充填剤、ガラスフレーク、非膨潤性雲母、膨潤性雲母、グラファイト、金属箔、セラミックビーズ、タルク、クレー、マイカ、セリサイト、ゼオライト、ベントナイト、有機変性ベントナイト、モンモリロナイト、有機変性モンモリロナイト、ドロマイト、スメクタイト、カオリン、微粉ケイ酸、長石粉、チタン酸カリウム、シラスバーン、炭酸カルシウム、水酸化マグネシウム、水酸化アルミニウム、炭酸マグネシウム、硫酸バリウム、酸化カルシウム、酸化アルミニウム、シリカ、酸化マグネシウム、酸化チタン、ケイ酸アルミニウム、酸化ケイ素、石膏、ノバキュライト、ドーソナイト及び白土等の板状や粒状の無機充填剤が挙げられるが、なかでも炭素繊維、ガラス繊維、ワラステナイト、タルク、マイカ及びカオリンから選ばれる１種又は２種以上が好ましく、タルク、マイカがより好ましい。 Moreover, there is no restriction | limiting in particular about the kind of inorganic filler provided to the composition of this invention, The thing of the fibrous form, plate shape, and powder form which are normally used for reinforcement | strengthening of a thermoplastic resin can be used for this. Specifically, glass fiber, asbestos fiber, carbon fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, zonolite, elestadite, gypsum fiber, silica Fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron nitride fiber and boron fiber and other inorganic fillers, glass flakes, non-swellable mica, swellable mica, graphite, metal foil, ceramic beads, talc, Clay, mica, sericite, zeolite, bentonite, organic modified bentonite, montmorillonite, organic modified montmorillonite, dolomite, smectite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu barn, calcium carbonate Plate-like and granular inorganic materials such as magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, silica, magnesium oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and clay Examples of the filler include one or more selected from carbon fiber, glass fiber, wollastonite, talc, mica, and kaolin, and talc and mica are more preferable.
本発明の組成物に供するポリ乳酸樹脂の光学純度について特に制限はないが、なかでもＬ−乳酸又はＤ−乳酸の光学純度が８０〜１００％の範囲にあるものが好ましく、９６〜１００％の範囲にあるものがより好ましい。本発明の組成物に供するポリ乳酸樹脂としては、前記した光学純度の双方の混合物からなるステレオコンプレックスポリ乳酸を用いることもできる。この場合、その混合比は、Ｌ−乳酸単位が豊富なポリ乳酸（ＰＬＬＡ）とＤ−乳酸単位が豊富なポリ乳酸（ＰＤＬＡ）が、（ＰＬＬＡ）／（ＰＤＬＡ）＝１０／９０〜９０／１０（重量比）の範囲にあるものを用いることができる。ステレオコンプレックスポリ乳酸を構成する各ポリ乳酸（ＰＬＬＡ及びＰＤＬＡ）に使用することができる乳酸以外の共重合成分としては、分子中に２個以上の官能基を有するジカルボン酸、多価アルコール、ヒドロキシカルボン酸、ラクトン等が挙げられ、また分子中に２個以上の未反応のカルボキシル基及び／又はヒドロキシル基を有するポリエステル、ポリエーテル、ポリカーボネート等が挙げられる。 Although there is no restriction | limiting in particular about the optical purity of the polylactic acid resin used for the composition of this invention, The thing in which the optical purity of L-lactic acid or D-lactic acid exists in the range of 80-100% is preferable, and it is 96-100% Those within the range are more preferred. As the polylactic acid resin to be used in the composition of the present invention, stereocomplex polylactic acid composed of a mixture of both of the optical purity described above can also be used. In this case, the mixing ratio of polylactic acid (PLLA) rich in L-lactic acid units and polylactic acid (PDLA) rich in D-lactic acid units is (PLLA) / (PDLA) = 10/90 to 90/10. What is in the range of (weight ratio) can be used. Examples of copolymer components other than lactic acid that can be used for each polylactic acid (PLLA and PDLA) constituting stereocomplex polylactic acid include dicarboxylic acids, polyhydric alcohols, and hydroxycarboxylic acids having two or more functional groups in the molecule. Examples include acids, lactones, and the like, and polyesters, polyethers, polycarbonates, and the like having two or more unreacted carboxyl groups and / or hydroxyl groups in the molecule.
ポリ乳酸樹脂の光学純度は、「ポリオレフィン等合成樹脂製食品容器包装等に関する自主基準 第３版改訂版 ２００４年６月追補 第３部 衛生試験法 Ｐ１２−１３」に記載のＤ体含有量の測定方法によって求めることができる。具体的には、ポリ乳酸樹脂の光学純度の測定方法は以下の通りである。 The optical purity of the polylactic acid resin is determined by measuring the D-form content as described in “Voluntary Standard for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins, Third Edition, Revised June 2004, Part 3 Sanitation Test Method P12-13” It can be determined by the method. Specifically, the method for measuring the optical purity of the polylactic acid resin is as follows.
すなわち、精製したポリ乳酸樹脂に水酸化ナトリウム／メタノールを加え、６５℃に設定した水浴振とう器にセットして、樹脂分が均一溶液になるまで加水分解を行い、さらに加水分解が完了したアルカリ溶液に希塩酸を加えて中和し、その分解溶液を純水にて定溶した後、一定容量をメスフラスコに分液して高速液体クロマトグラフィー（ＨＰＬＣ）移動相溶液により希釈し、ｐＨが３〜７の範囲になるように調整してメスフラスコを定量し、メンブレンフィルター（０．４５μｍ）によりろ過する。ＨＰＬＣにてこの調整溶液のＤ−乳酸、Ｌ−乳酸を定量することによってポリ乳酸樹脂の光学純度を求めることができる。 That is, sodium hydroxide / methanol was added to the purified polylactic acid resin, set in a water bath shaker set at 65 ° C., and hydrolyzed until the resin content became a homogeneous solution. The solution is neutralized by adding dilute hydrochloric acid, and the decomposition solution is dissolved in pure water, and then a predetermined volume is separated into a volumetric flask and diluted with a high performance liquid chromatography (HPLC) mobile phase solution, and the pH is 3 The volumetric flask is quantified by adjusting to a range of ˜7, and filtered through a membrane filter (0.45 μm). The optical purity of the polylactic acid resin can be determined by quantifying D-lactic acid and L-lactic acid in this adjusted solution by HPLC.
尚、ＨＰＬＣの測定は以下の条件で行うことができる。
カラム：光学分割カラム（例えば、住化分析センター社製の商品名スミキラルＯＡ６１００（４６ｍｍφ×１５０ｍｍ、５μｍ））
プレカラム：光学分割カラム（例えば、住化分析センター社製の商品名スミキラルＱＡ６１００（４ｍｍφ×１０ｍｍ、５μｍ））
カラム温度：２５℃
移動相：２．５％メタノール含有１．５ｍＭ硫酸銅水溶液
移動相流量：１．０ｍｌ／分
検出器：紫外線検出器（ＵＶ２５４μｍ）
注入量：２０μｌ
In addition, the measurement of HPLC can be performed on condition of the following.
Column: optical resolution column (for example, Sumika Chiral OA6100 (46 mmφ × 150 mm, 5 μm) manufactured by Sumika Chemical Analysis Co., Ltd.)
Precolumn: optical resolution column (for example, Sumika Chiral QA6100 (4 mmφ × 10 mm, 5 μm) manufactured by Sumika Chemical Analysis Co., Ltd.)
Column temperature: 25 ° C
Mobile phase: 1.5 mM copper sulfate aqueous solution containing 2.5% methanol Mobile phase flow rate: 1.0 ml / min Detector: UV detector (UV254 μm)
Injection volume: 20 μl
本発明の組成物に供するポリ乳酸樹脂それ自体は、公知の方法で合成できる。これには例えば、特開平５−４８２５８号公報、特開平７−３３８６１号公報、特開昭５９−９６１２３号公報、高分子討論会予稿集第４４巻の３１９８−３１９９頁に記載されているような、１）乳酸を直接脱水縮合反応する方法、２）乳酸のラクチドを開環重合する方法等が挙げられる。前記１）の方法では、Ｌ−乳酸、Ｄ−乳酸、ＤＬ−乳酸又はこれらの混合物のいずれの乳酸を用いてもよい。前記２）の方法では、Ｌ−ラクチド、Ｄ−ラクチド、ＤＬ−ラクチド、メソ−ラクチド又はこれら混合物のいずれのラクチドを用いてもよい。原料のラクチドの合成、精製及び重合方法にも、公知の方法を適用できる。これには例えば、米国特許４０５７５３７号明細書、欧州特許出願公開第２６１５７２号明細書、Ｐｏｌｙｍｅｒ Ｂｕｌｌｅｔｉｎ，１４，４９１−４９５（１９８５）、Ｍａｃｒｏｍｏｌ．Ｃｈｅｍ．，１８７，１６１１−１６２８（１９８６）等に記載されている方法が挙げられる。 The polylactic acid resin itself used for the composition of the present invention can be synthesized by a known method. This is described in, for example, JP-A-5-48258, JP-A-7-33861, JP-A-59-96123, and Polymer Sciences Conference Proceedings Vol. 44, pages 3198-3199. 1) a method of directly dehydrating condensation reaction of lactic acid, and 2) a method of ring-opening polymerization of lactide of lactic acid. In the method 1), any lactic acid of L-lactic acid, D-lactic acid, DL-lactic acid, or a mixture thereof may be used. In the method 2), any one of L-lactide, D-lactide, DL-lactide, meso-lactide, or a mixture thereof may be used. Known methods can also be applied to the synthesis, purification, and polymerization methods of the starting lactide. For example, US Pat. No. 4,057,537, European Patent Application No. 261572, Polymer Bulletin, 14, 491-495 (1985), Macromol. Chem. 187, 1611-1628 (1986) and the like.
本発明の組成物に供するポリ乳酸樹脂の質量平均分子量（ゲルパーミエーショクロマトグラフ分析によるポリスチレン換算値、以下同じ）に特に制限はないが、５００００〜４０００００としたものが好ましく、１０００００〜２０００００としたものがより好ましく、１１００００〜２０００００としたものが特に好ましい。ポリ乳酸樹脂の質量平均分子量が５００００未満では得られる成形体の強度や弾性率等の機械特性が不充分となり易く、質量平均分子量が高くなるほどこのような機械的特性が向上する傾向を示す。またポリ乳酸樹脂の質量平均分子量が４０００００以下であると、成形に都合の良い流動性を示す。 Although there is no restriction | limiting in particular in the mass mean molecular weight (The polystyrene conversion value by a gel permeation chromatograph analysis, and the following is the same) of the polylactic acid resin used for the composition of this invention, What was set to 50000-400000 is preferable, It was set to 100000-200000 More preferred are those with 110,000-200000. When the mass average molecular weight of the polylactic acid resin is less than 50000, the mechanical properties such as strength and elastic modulus of the obtained molded product tend to be insufficient, and such mechanical properties tend to improve as the mass average molecular weight increases. Moreover, the fluidity | liquidity convenient for shaping | molding is shown as the mass average molecular weight of a polylactic acid resin is 400,000 or less.
本発明の組成物に供するポリ乳酸樹脂は、これに含まれる残存モノマーを５０００ｍｇ／Ｌ以下としたものが好ましく、２０００ｍｇ／Ｌ以下としたものがより好ましく、５００ｍｇ／Ｌ以下としたものが特に好ましい。ポリ乳酸樹脂中の残存モノマー量が５０００ｍｇ／Ｌを超えると、残存モノマーが加水分解の触媒として作用するため、カルボジイミド系化合物、オキサゾリン系化合物、イソシアネート系化合物等の既知の加水分解抑制剤を添加してもその効果が充分に発揮されず、耐湿熱老化性及び耐熱性が不充分となり易い。ポリ乳酸中の残存モノマーは低くなるほど耐湿熱老化性及び耐熱性が向上する傾向を示す。 The polylactic acid resin used in the composition of the present invention preferably has a residual monomer contained therein of 5000 mg / L or less, more preferably 2000 mg / L or less, and particularly preferably 500 mg / L or less. . If the residual monomer amount in the polylactic acid resin exceeds 5000 mg / L, the residual monomer acts as a hydrolysis catalyst. Therefore, a known hydrolysis inhibitor such as a carbodiimide compound, an oxazoline compound, or an isocyanate compound is added. However, the effect is not sufficiently exhibited, and the moisture and heat aging resistance and heat resistance are likely to be insufficient. The lower the residual monomer in the polylactic acid, the higher the moist heat aging resistance and the heat resistance.
本発明の組成物は、剛性、柔軟性、耐熱性、耐久性等の物性向上の観点から、その他の樹脂を含有することもできる。かかるその他の樹脂の具体例としては、合成樹脂としてはポリカーボネート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステル、ポリフェニレンエーテル、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリオキシメチレン、ポリフェニレンスルフィド、ＡＢＳ樹脂、ＡＳ樹脂、ＨＩＰＳ等のポリスチレン系樹脂、ポリメチルメタクリレート等のアクリル系樹脂、ポリアミド等を挙げることができる。これらは単独でもしくは２種以上を組み合わせて用いることができる。なかでもポリ乳酸樹脂との相溶性の観点から、分子中にエステル結合、カーボネート結合等のカルボニル基を含む結合を有する樹脂が好ましく、ＡＢＳ樹脂、ポリブチレンテレフタレート、ポリカーボネートがより好ましい。 The composition of the present invention can also contain other resins from the viewpoint of improving physical properties such as rigidity, flexibility, heat resistance, and durability. Specific examples of such other resins include synthetic resins such as polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like, polyphenylene ether, polyethylene, polypropylene, polyvinyl chloride, polyoxymethylene, polyphenylene sulfide, and ABS resin. , AS resins, polystyrene resins such as HIPS, acrylic resins such as polymethyl methacrylate, polyamides, and the like. These can be used alone or in combination of two or more. Among these, from the viewpoint of compatibility with the polylactic acid resin, a resin having a bond containing a carbonyl group such as an ester bond or a carbonate bond in the molecule is preferable, and an ABS resin, polybutylene terephthalate, or polycarbonate is more preferable.
本発明の組成物は、合目的的に他の添加剤を含有することもできる。かかる他の添加剤としては、酸化防止剤、熱安定剤、光安定剤、紫外線吸収剤、顔料、着色剤、各種フィラー、帯電防止剤、離型剤、香料、滑剤、難燃剤、発泡剤、充填剤、抗菌・抗カビ剤等が挙げられる。 The composition of the present invention may contain other additives as appropriate. Such other additives include antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, pigments, colorants, various fillers, antistatic agents, mold release agents, fragrances, lubricants, flame retardants, foaming agents, Examples include fillers, antibacterial / antifungal agents, and the like.
以上説明した本発明の組成物は、公知の方法で調製できる。これには例えば、１）粉末又はペレット状のポリ乳酸樹脂と、有機結晶核剤と、要すれば他の添加剤とを、同時にドライブレンドし、溶融混練した後、液体注入型の液体供給装置等にて本発明の可塑剤を添加して更に溶融混練する方法、２）粉末又はペレット状のポリ乳酸樹脂を溶融混練しつつ、サイドフィードにて有機結晶核剤と、要すれば他の添加剤を添加し、更に本発明の可塑剤を液体注入型の液体供給装置等にて添加する方法等が挙げられる。前記のドライブレンドの装置としては、ミルロール、バンバリーミキサー、スーパーミキサー等が挙げられる。また溶融混練機としては、単軸又は二軸の押出機等が挙げられる。溶融混練機の混練温度は、通常１２０〜２４０℃程度とする。ポリ乳酸樹脂の重合段階で、結晶核剤や要すれば他の添加剤を加えることもでき、また結晶核剤や要すれば他の添加剤を高濃度で含有するマスターバッチを作製しておき、これをポリ乳酸樹脂に加えることもできる。 The composition of the present invention described above can be prepared by a known method. For this, for example, 1) a powder or pellet-like polylactic acid resin, an organic crystal nucleating agent, and if necessary, other additives are simultaneously dry blended, melt-kneaded, and then a liquid injection type liquid supply device 2) A method of adding the plasticizer of the present invention and further melt-kneading, 2) While melt-kneading the powder or pellet-like polylactic acid resin, side feed and other additions if necessary And a method of adding a plasticizer of the present invention with a liquid injection type liquid supply device or the like. Examples of the dry blending apparatus include a mill roll, a Banbury mixer, and a super mixer. Examples of the melt kneader include a single screw or twin screw extruder. The kneading temperature of the melt kneader is usually about 120 to 240 ° C. In the polymerization stage of polylactic acid resin, a crystal nucleating agent and other additives can be added if necessary, and a master batch containing a high concentration of the crystal nucleating agent and other additives if necessary is prepared. This can also be added to the polylactic acid resin.
本発明に係るポリ乳酸樹脂成形体（以下、単に本発明の成形体という）は、前記した本発明の組成物を成形して得られるものである。成形方法に特に制限はないが、射出成形機等により本発明の組成物を１４０℃以下の金型に充填して成形する方法が挙げられる。金型温度は、３０℃〜１２０℃とするのが好ましく、７０℃〜１１０℃とするのがより好ましい。 The polylactic acid resin molded product according to the present invention (hereinafter simply referred to as the molded product of the present invention) is obtained by molding the above-described composition of the present invention. Although there is no restriction | limiting in particular in a shaping | molding method, The method of filling the composition of this invention in a 140 degrees C or less metal mold | die with an injection molding machine etc. is mentioned. The mold temperature is preferably 30 ° C to 120 ° C, and more preferably 70 ° C to 110 ° C.
本発明の可塑剤を用いると、低い金型温度でも優れた成形性を示すポリ乳酸樹脂組成物を調製でき、またかかる組成物から優れた耐熱性、耐衝撃性及び耐ブリード性を有するポリ乳酸樹脂成形体を得ることができる。 When the plasticizer of the present invention is used, a polylactic acid resin composition exhibiting excellent moldability even at a low mold temperature can be prepared, and polylactic acid having excellent heat resistance, impact resistance and bleed resistance can be prepared from such a composition. A resin molded body can be obtained.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（ポリ乳酸樹脂用可塑剤の合成）
・実施例１（ポリ乳酸樹脂用可塑剤（Ａ１）の合成）
エチレンオキサイド用の計量槽の付いた１０Ｌの攪拌回転式オートクレーブ中に、硬化ヒマシ油を３０００ｇ及び水酸化カリウムを７．２ｇ仕込み、窒素置換を行った後、１２０℃に昇温し、３０．０ｋＰａで１時間脱水を行った。次に、１５０℃に昇温し、エチレンオキサイドを３．０ｋｇ／ｃｍ２の圧力で２９５９ｇオートクレーブ中に導入し、圧力が低下して一定になるまで反応させた。反応終了後、温度を低下させて合成したサンプルを抜き出した。抜き出したサンプルを１０Ｌフラスコに移し、リン酸を加えて中和した後、脱水を行い、析出した塩を濾過して５９５０ｇの硬化ヒマシ油のエチレンオキサイド付加物を得た。
Test category 1 (Synthesis of plasticizer for polylactic acid resin)
Example 1 (Synthesis of plasticizer for polylactic acid resin (A1))
In a 10-liter stirring rotary autoclave equipped with a measuring tank for ethylene oxide, 3000 g of hardened castor oil and 7.2 g of potassium hydroxide were charged, and after nitrogen substitution, the temperature was raised to 120 ° C. and 30.0 kPa For 1 hour. Next, the temperature was raised to 150 ° C., ethylene oxide was introduced into the 2959 g autoclave at a pressure of 3.0 kg / cm 2 , and reacted until the pressure decreased and became constant. After completion of the reaction, the synthesized sample was extracted at a reduced temperature. The extracted sample was transferred to a 10 L flask, neutralized by adding phosphoric acid, dehydrated, and the deposited salt was filtered to obtain an ethylene oxide adduct of 5950 g of hardened castor oil.
前記の硬化ヒマシ油のエチレンオキサイド付加物２３１３ｇ、オレイン酸７０２ｇ、メタンスルホン酸２５ｇ及びジ亜リン酸７．５ｇを１Ｌのフラスコに仕込み、撹拌装置を用いて攪拌しながら反応温度１２０℃で１時間反応させ、更に１４５℃の減圧下で１時間熟成した。反応終了後、メタンスルホン酸及びオレイン酸を水酸化ナトリウム水溶液で中和し、生成した塩を水洗により除去した後、水分を減圧留去して、化１で示される硬化ヒマシ油誘導体（硬化ヒマシ油のエチレンオキサイド付加物のオレイン酸ジエステル）を得た。この硬化ヒマシ油誘導体をポリ乳酸樹脂用可塑剤（Ａ１）とした。 2313 g of the above-mentioned hydrogenated castor oil ethylene oxide adduct, 702 g of oleic acid, 25 g of methanesulfonic acid and 7.5 g of diphosphorous acid were charged into a 1 L flask and stirred at a reaction temperature of 120 ° C. for 1 hour using a stirrer. The reaction was allowed to proceed, followed by aging under reduced pressure at 145 ° C for 1 hour. After completion of the reaction, methanesulfonic acid and oleic acid were neutralized with an aqueous sodium hydroxide solution, and the salt formed was removed by washing with water, and then the water was distilled off under reduced pressure to give a hardened castor oil derivative (hardened castor) represented by Chemical Formula 1. An oleic acid diester of an ethylene oxide adduct of oil) was obtained. This hardened castor oil derivative was used as a plasticizer for polylactic acid resin (A1).
・実施例２〜４（ポリ乳酸樹脂用可塑剤（Ａ２〜Ａ４）の合成）
実施例１のポリ乳酸樹脂用可塑剤（Ａ１）の合成と同様にして、実施例２〜４のポリ乳酸樹脂用可塑剤（Ａ２〜Ａ４）を合成した。合成したポリ乳酸樹脂用可塑剤（Ａ１〜Ａ４）の内容を表１にまとめて示した。
Examples 2 to 4 (Synthesis of plasticizers for polylactic acid resin (A2 to A4))
In the same manner as in the synthesis of the plasticizer for polylactic acid resin (A1) of Example 1, the plasticizers for polylactic acid resin (A2 to A4) of Examples 2 to 4 were synthesized. The contents of the synthesized plasticizers for polylactic acid resin (A1 to A4) are summarized in Table 1.
表１において、
Ｒ１〜Ｒ６：化１中の記号に相当（尚、Ａ１〜Ａ４のｐ、ｑ及びｒは１）
＊１：炭素数１４のポリオキシエチレングリコールから一方の水酸基を除いた残基
＊２：炭素数３３のポリオキシプロピレングリコールから一方の水酸基を除いた残基
＊３：炭素数６のポリオキシエチレングリコールから一方の水酸基を除いた残基
＊４：炭素数４８のポリオキシエチレングリコールから一方の水酸基を除いた残基
Ａ１：硬化ヒマシ油のエチレンオキサイド付加物のオレイン酸ジエステル
Ａ２：硬化ヒマシ油のプロピレンオキサイド付加物のラウリン酸トリエステル
Ａ３：硬化ヒマシ油のエチレンオキサイド付加物
Ａ４：硬化ヒマシ油のエチレンオキサイド付加物
In Table 1,
R 1 to R 6 : Corresponds to the symbols in Chemical Formula 1 (wherein p, q and r of A1 to A4 are 1)
* 1: Residue obtained by removing one hydroxyl group from polyoxyethylene glycol having 14 carbon atoms * 2: Residue obtained by removing one hydroxyl group from polyoxypropylene glycol having 33 carbon atoms * 3: Polyoxyethylene having 6 carbon atoms Residue obtained by removing one hydroxyl group from glycol * 4: Residue obtained by removing one hydroxyl group from polyoxyethylene glycol having 48 carbon atoms A1: Oleic acid diester of ethylene oxide adduct of hydrogenated castor oil A2: of hydrogenated castor oil Lauric acid triester of propylene oxide adduct A3: Ethylene oxide adduct of hydrogenated castor oil A4: Ethylene oxide adduct of hydrogenated castor oil
試験区分２（ポリ乳酸樹脂の合成）
・ポリ−Ｌ−乳酸樹脂（Ｌ１）の合成
Ｌ−ラクチド（武蔵野化学研究所社製）１００部に、ステアリルアルコールを０．１部及びオクチル酸スズを０．００５部加え、窒素雰囲気下、攪拌翼のついた反応機中にて、１９０℃で２時間反応させた後、減圧して残存するラクチドを除去し、チップ化して、ポリ−Ｌ−乳酸樹脂（Ｌ１）を得た。得られたポリ−Ｌ−乳酸樹脂（Ｌ１）の質量平均分子量は１３万、光学純度は９８．６％、ガラス転移点（Ｔｇ）は６０℃、融点は１６８℃であった。
Test Category 2 (Synthesis of polylactic acid resin)
Synthesis of poly-L-lactic acid resin (L1) To 100 parts of L-lactide (manufactured by Musashino Chemical Laboratory Co., Ltd.), 0.1 part of stearyl alcohol and 0.005 part of tin octylate were added and stirred in a nitrogen atmosphere. After reacting at 190 ° C. for 2 hours in a reactor equipped with a blade, the remaining lactide was removed by reducing the pressure and chipped to obtain a poly-L-lactic acid resin (L1). The obtained poly-L-lactic acid resin (L1) had a mass average molecular weight of 130,000, an optical purity of 98.6%, a glass transition point (Tg) of 60 ° C., and a melting point of 168 ° C.
・ポリ−Ｄ−乳酸樹脂（Ｌ２）の合成
Ｄ−ラクチド（武蔵野化学研究所社製）１００部に、ステアリルアルコールを０．１部及びオクチル酸スズを０．００５部加え、窒素雰囲気下、攪拌翼のついた反応機中にて、１９０℃で２時間反応させた後、減圧して残存するラクチドを除去し、チップ化して、ポリ−Ｄ−乳酸樹脂（Ｌ２）を得た。得られたポリ−Ｄ−乳酸樹脂（Ｌ２）の質量平均分子量は１５万、光学純度は９８．５％、ガラス転移点（Ｔｇ）は６０℃、融点は１６７℃であった。
Synthesis of poly-D-lactic acid resin (L2) To 100 parts of D-lactide (manufactured by Musashino Chemical Laboratory Co., Ltd.), 0.1 part of stearyl alcohol and 0.005 part of tin octylate are added and stirred in a nitrogen atmosphere. After reacting at 190 ° C. for 2 hours in a reactor equipped with a blade, the remaining lactide was removed by reducing the pressure and chipped to obtain a poly-D-lactic acid resin (L2). The obtained poly-D-lactic acid resin (L2) had a mass average molecular weight of 150,000, an optical purity of 98.5%, a glass transition point (Tg) of 60 ° C., and a melting point of 167 ° C.
・ポリ−Ｌ−乳酸樹脂（Ｌ３）の合成
Ｌ−ラクチド（武蔵野化学研究所社製）１００部に、ステアリルアルコールを０．１部及びオクチル酸スズを０．００５部加え、窒素雰囲気下、攪拌翼のついた反応機中にて、１９０℃で２時間反応させた後、減圧して残存するラクチドを除去し、チップ化して、ポリ−Ｌ−乳酸樹脂（Ｌ３）を得た。得られたポリ−Ｌ−乳酸樹脂（Ｌ３）の質量平均分子量は１８万、光学純度は９５．５％、ガラス転移点（Ｔｇ）は６０℃、融点は１４８℃であった。
Synthesis of poly-L-lactic acid resin (L3) To 100 parts of L-lactide (manufactured by Musashino Chemical Laboratory Co., Ltd.), 0.1 part of stearyl alcohol and 0.005 part of tin octylate were added and stirred in a nitrogen atmosphere. After reacting at 190 ° C. for 2 hours in a reactor equipped with a blade, the pressure was reduced to remove the remaining lactide and chipped to obtain a poly-L-lactic acid resin (L3). The obtained poly-L-lactic acid resin (L3) had a mass average molecular weight of 180,000, an optical purity of 95.5%, a glass transition point (Tg) of 60 ° C., and a melting point of 148 ° C.
・ステレオコンプレックスポリ乳酸樹脂（Ｌ４）の合成
前記のポリ−Ｌ−乳酸樹脂（Ｌ１）５０部、前記のポリ−Ｄ−乳酸樹脂（Ｌ２）５０部及び二オクタデカン酸カルシウム０．５部を攪拌装置のついた反応容器中で、窒素雰囲気下、２５０℃で溶融混練し、ステレオコンプレックスポリ乳酸樹脂（Ｌ４）を得た。得られたステレオコンプレックスポリ乳酸樹脂（Ｌ４）の質量平均分子量は１６万、融点は２１７℃であった。
Synthesis of stereocomplex polylactic acid resin (L4) 50 parts of the poly-L-lactic acid resin (L1), 50 parts of the poly-D-lactic acid resin (L2) and 0.5 part of calcium dioctadecanoate were stirred. Were melt-kneaded in a nitrogen atmosphere at 250 ° C. in a nitrogen atmosphere to obtain a stereocomplex polylactic acid resin (L4). The obtained stereocomplex polylactic acid resin (L4) had a mass average molecular weight of 160,000 and a melting point of 217 ° C.
試験区分３（ポリ乳酸樹脂組成物の調製）
実施例５（ポリ乳酸樹脂組成物（Ｎ−１）の調製）
前記のポリ―Ｌ―乳酸樹脂（Ｌ１）１００部、有機核剤として５−スルホイソフタル酸ジメチルカリウム塩０．９部及び無機充填剤としてタルク（日本タルク社製の商品名ＭｉｃｒｏＡｃｅＰ−６）１０部をドライブレンドし、混合材料を得た。この混合材料をホッパーに投入して、２００℃に設定された二軸混練押出機にて溶融混練し、更にポリ乳酸樹脂用可塑剤（Ａ１）１０部を液体注入型の液体供給装置から添加して溶融混練した後、口金よりストランド状に押出し、水で急冷してストランドを得た。このストランドをストランドカッターで切断して、ペレット状のポリ乳酸樹脂組成物（Ｎ−１）を得た。
Test Category 3 (Preparation of polylactic acid resin composition)
Example 5 (Preparation of polylactic acid resin composition (N-1))
100 parts of the above-mentioned poly-L-lactic acid resin (L1), 0.9 part of dimethyl potassium salt of 5-sulfoisophthalic acid as an organic nucleating agent, and 10 parts of talc (trade name MicroAceP-6 manufactured by Nippon Talc Co., Ltd.) as an inorganic filler Were dry blended to obtain a mixed material. This mixed material is put into a hopper, melt-kneaded in a twin-screw kneading extruder set at 200 ° C., and 10 parts of a plasticizer for polylactic acid resin (A1) is added from a liquid injection type liquid supply device. After melt-kneading, it was extruded into a strand shape from a die and quenched with water to obtain a strand. This strand was cut with a strand cutter to obtain a pellet-shaped polylactic acid resin composition (N-1).
実施例６〜１６及び比較例１〜７（ポリ乳酸樹脂組成物（Ｎ−２〜Ｎ−１２、ｍ−１〜ｍ−７）の調製）
実施例５のポリ乳酸樹脂組成物（Ｎ−１）の調製と同様にして、実施例６〜１６のポリ乳酸樹脂組成物（Ｎ−２）〜（Ｎ−１２）及び比較例１〜７のポリ乳酸樹脂組成物（ｍ−１）〜（ｍ−７）を調製した。調製したポリ乳酸樹脂組成物（Ｎ−１〜Ｎ−１２、ｍ−１〜ｍ−７）の内容を表２にまとめて示した。
Examples 6 to 16 and Comparative Examples 1 to 7 (Preparation of polylactic acid resin composition (N-2 to N-12, m-1 to m-7))
In the same manner as in the preparation of the polylactic acid resin composition (N-1) of Example 5, the polylactic acid resin compositions (N-2) to (N-12) of Examples 6 to 16 and Comparative Examples 1 to 7 were used. Polylactic acid resin compositions (m-1) to (m-7) were prepared. The contents of the prepared polylactic acid resin compositions (N-1 to N-12, m-1 to m-7) are shown together in Table 2.
表２において、
使用量：質量部
Ｌ１：ポリ−Ｌ−乳酸樹脂（光学純度９８．６％、重量平均分子量１３万）
Ｌ２：ポリ−Ｄ−乳酸樹脂（光学純度９８．５％、重量平均分子量１５万）
Ｌ３：ポリ−Ｌ−乳酸樹脂（光学純度９５．５％、重量平均分子量１８万）
Ｌ４：ステレオコンプレックスポリ乳酸樹脂（ＰＬＬＡ光学純度９８．６％、ＰＤＬＡ光学純度９８．５％、ＰＬＬＡ／ＰＤＬＡ＝５０／５０、重量平均分子量１６万）
Ａ１〜Ａ４：表１に記載のもの
ａ１：ヒマシ硬化油（伊藤製油社製の商品名ヒマシ硬化油）
ａ２：ヒマシ油のエチレンオキサイド１０モル付加物（伊藤製油社製の商品名ＳＵＲＦＲＩＣ ＣＯ−１０）
ａ３：ジグリセリンテトラアセテート（理研ビタミン社製の商品名リケマールＰＬ−７１０）
ａ４：グリセリンジアセトモノカプレート（理研ビタミン社製の商品名リケマールＰＬ−０１９）
ａ５：ブチルアセチルリシノレート（伊藤製油社製の商品名リックサイザーＣ４０１）
Ｂ１：フェニルホスホン酸亜鉛（日産化学社製の商品名エコプロモート）
Ｂ２：５−スルホイソフタル酸ジメチルカリウム塩
Ｂ３：オクタンジカルボン酸ジベンゾイルヒドラジド（アデカ社製の商品名Ｔ−１２８７Ｎ）
Ｃ１：タルク（日本タルク社製の商品名ＭｉｃｒｏＡｃｅＰ−６）
Ｃ２：マイカ（ヤマグチマイカ社製の商品名ＣＳ−３２５ＤＣ）
In Table 2,
Amount used: parts by mass L1: poly-L-lactic acid resin (optical purity 98.6%, weight average molecular weight 130,000)
L2: Poly-D-lactic acid resin (optical purity 98.5%, weight average molecular weight 150,000)
L3: Poly-L-lactic acid resin (optical purity 95.5%, weight average molecular weight 180,000)
L4: Stereocomplex polylactic acid resin (PLLA optical purity 98.6%, PDLA optical purity 98.5%, PLLA / PDLA = 50/50, weight average molecular weight 160,000)
A1 to A4: those described in Table 1 a1: castor oil (trade name castor oil manufactured by Ito Oil Co., Ltd.)
a2: Castor oil ethylene oxide 10 mol adduct (trade name SURFRIC CO-10, manufactured by Ito Oil Co., Ltd.)
a3: Diglycerin tetraacetate (trade name Riquemar PL-710, manufactured by Riken Vitamin Co., Ltd.)
a4: Glycerin diacetomonocaprate (trade name Riquemar PL-019 manufactured by Riken Vitamin Co., Ltd.)
a5: Butylacetylricinoleate (trade name Rick Sizer C401, manufactured by Ito Oil Co., Ltd.)
B1: Zinc phenylphosphonate (trade name Eco Promote manufactured by Nissan Chemical Co., Ltd.)
B2: Dimethyl potassium salt of 5-sulfoisophthalic acid B3: Octanedicarboxylic acid dibenzoyl hydrazide (trade name T-1287N manufactured by Adeka)
C1: Talc (trade name MicroAceP-6 manufactured by Nihon Talc)
C2: Mica (trade name CS-325DC manufactured by Yamaguchi Mica)
試験区分４（ポリ乳酸樹脂組成物の評価）
・成形性の評価
試験区分３で調製した各例のポリ乳酸樹脂組成物を１００℃で２時間除湿乾燥し、絶乾状態にした後、シリンダー温度を２００℃に設定した射出成形機（ＦＡＮＵＣ社製の商品名ＲＯＢＯＳＨＯＴ Ｓ−２０００ｉ５０Ｂ）を用いて、表３に示す金型温度で射出成形し、テストピース（１２７ｍｍ×１２．７ｍｍ×３ｍｍ）の離形に必要な金型保持時間を下記の基準で評価し、結果を表３に示した。
Test Category 4 (Evaluation of polylactic acid resin composition)
・ Evaluation of moldability The polylactic acid resin composition of each example prepared in Test Category 3 was dehumidified and dried at 100 ° C. for 2 hours and completely dried, and then an injection molding machine (FANUC Co., Ltd.) set the cylinder temperature to 200 ° C. Using the product name ROBOSHOT S-2000i50B) manufactured by injection molding at the mold temperature shown in Table 3, the mold holding time required for releasing the test piece (127 mm x 12.7 mm x 3 mm) is as follows: The results are shown in Table 3.
金型温度１１０℃の場合の成形性の評価基準
３：テストピースに変形が無く、取り出しが容易と判断される時間が２０秒未満であった。
２：テストピースに変形が無く、取り出しが容易と判断される時間が２０秒以上４０秒未満であった。
１：テストピースに変形が無く、取り出しが容易と判断される時間が４０秒以上６０秒未満であった。
０：テストピースに変形が無く、取り出しが容易と判断される時間が６０秒以上であった。
Evaluation criteria for moldability at a mold temperature of 110 ° C. 3: The test piece was not deformed and the time taken to be easily removed was less than 20 seconds.
2: The test piece was not deformed and the time taken to be easily removed was 20 seconds or more and less than 40 seconds.
1: The test piece was not deformed and the time taken to be easily taken out was 40 seconds or more and less than 60 seconds.
0: The test piece was not deformed and the time taken to be easily removed was 60 seconds or longer.
金型温度８０℃の場合の成形性の評価基準
３：テストピースに変形が無く、取り出しが容易と判断される時間が４０秒未満であった。
２：テストピースに変形が無く、取り出しが容易と判断される時間が４０秒以上６０秒未満であった。
１：テストピースに変形が無く、取り出しが容易と判断される時間が６０秒以上１２０秒未満であった。
０：テストピースに変形が無く、取り出しが容易と判断される時間が１２０秒以上であった。
Evaluation criteria for moldability at a mold temperature of 80 ° C. 3: The test piece was not deformed and the time taken to be easily taken out was less than 40 seconds.
2: The test piece was not deformed and the time taken to be easily taken out was 40 seconds or more and less than 60 seconds.
1: The test piece was not deformed and the time taken to be easily removed was 60 seconds or more and less than 120 seconds.
0: The test piece was not deformed and the time taken for easy removal was 120 seconds or more.
・耐熱性の評価
試験区分３で調製した各例のポリ乳酸樹脂組成物を１００℃で２時間除湿乾燥し、絶乾状態にした後、ラボプラストミルにて２４０℃で５分間混練したときの発煙を、下記の基準で目視にて評価し、結果を表３に示した。
２：発煙なし。
１：発煙が認められる。
・ Evaluation of heat resistance When the polylactic acid resin composition of each example prepared in Test Category 3 was dehumidified and dried at 100 ° C. for 2 hours, completely dried, and then kneaded at 240 ° C. for 5 minutes in a lab plast mill. Smoke was visually evaluated according to the following criteria, and the results are shown in Table 3.
2: No smoke.
1: Smoke is recognized.
・耐衝撃性の評価
試験区分３で調製した各例のポリ乳酸樹脂組成物を１００℃で２時間除湿乾燥し、絶乾状態にした後、シリンダー温度を２００℃に設定した射出成形機（ＦＡＮＵＣ社製の商品名ＲＯＢＯＳＨＯＴ Ｓ−２０００ｉ５０Ｂ）を用いて、１１０℃の金型温度で射出成形してテストピース（１２７ｍｍ×１２．７ｍｍ×３ｍｍ）を得た。このテストピースを用いて、ＪＩＳ−Ｋ７１１０に基づき、ノッチなし試験片を作製し、アイゾット（Ｉｚｏｄ）衝撃強度を測定して、下記の基準で評価し、結果を表３に示した。
３：アイゾット衝撃強度が２０ＫＪ／ｍ２以上であり、耐衝撃性は非常に良好であった。
２：アイゾット衝撃強度が１５ＫＪ／ｍ２以上２０ＫＪ／ｍ２未満であり、耐衝撃性は良好であった。
１：アイゾット衝撃強度が１２ＫＪ／ｍ２以上１５ＫＪ／ｍ２未満であり、耐衝撃性は概ね良好であった。
０：アイゾット衝撃強度が１２ＫＪ／ｍ２未満であり、耐衝撃性は悪かった。
・ Evaluation of impact resistance The polylactic acid resin composition of each example prepared in Test Category 3 was dehumidified and dried at 100 ° C. for 2 hours and completely dried, and then an injection molding machine (FANUC) in which the cylinder temperature was set to 200 ° C. A test piece (127 mm × 12.7 mm × 3 mm) was obtained by injection molding at a mold temperature of 110 ° C. using a trade name ROBOSHOT S-2000i50B) manufactured by the company. Using this test piece, a test piece without a notch was prepared based on JIS-K7110, the Izod impact strength was measured and evaluated according to the following criteria, and the results are shown in Table 3.
3: The Izod impact strength was 20 KJ / m 2 or more, and the impact resistance was very good.
2: Izod impact strength was 15 KJ / m 2 or more and less than 20 KJ / m 2 , and the impact resistance was good.
1: The Izod impact strength was 12 KJ / m 2 or more and less than 15 KJ / m 2 , and the impact resistance was generally good.
0: Izod impact strength was less than 12 KJ / m 2 and impact resistance was poor.
・耐ブリード性の評価
試験区分３で調整した各例のポリ乳酸樹脂組成物１ｋｇを、金属製の容器（１００ｃｍ×３０ｃｍ×５ｃｍ）に入れ、８０℃で２４時間熱風乾燥して、可塑剤のブリード性について下記の基準で評価し、結果を表３に示した。
３：ポリ乳酸樹脂組成物のペレット及び金属製の容器の双方に可塑剤由来の濡れがなく、耐ブリード性は非常に良好であった。
２：金属製の容器に可塑剤由来の濡れが認められたが、ポリ乳酸樹脂組成物のペレットに可塑剤由来の濡れは無く、耐ブリード性は良好であった。
１：ポリ乳酸樹脂組成物のペレット及び金属製の容器の双方に可塑剤由来の濡れが認められたが、ペレット同士が可塑剤の濡れにより結着して塊状になっていることはないため、耐ブリード性は概ね良好であった。
０：ポリ乳酸樹脂組成物のペレット及び金属製の容器の双方に可塑剤由来の濡れが認められ、ペレット同士が可塑剤由来の濡れにより結着して塊状になっていたため、耐ブリード性は悪かった。
・ Evaluation of bleed resistance 1 kg of the polylactic acid resin composition of each example prepared in Test Category 3 was placed in a metal container (100 cm × 30 cm × 5 cm) and dried with hot air at 80 ° C. for 24 hours to obtain a plasticizer. Bleedability was evaluated according to the following criteria, and the results are shown in Table 3.
3: Both the pellets of the polylactic acid resin composition and the metal container were free from plasticizer, and the bleed resistance was very good.
2: Wetting due to the plasticizer was observed in the metal container, but the pellet of the polylactic acid resin composition had no wetting due to the plasticizer, and the bleed resistance was good.
1: Although wetting from the plasticizer was observed in both the pellets of the polylactic acid resin composition and the metal container, the pellets are not bound together by the wetting of the plasticizer and are not agglomerated, Bleed resistance was generally good.
0: Wetting due to the plasticizer was observed in both the pellets of the polylactic acid resin composition and the metal container, and the pellets were bound together by wetting due to the plasticizer to form a lump, so the bleed resistance was poor. It was.
表３の結果からも明らかなように、本発明の可塑剤を用いると、低い金型温度でも優れた成形性を示すポリ乳酸樹脂組成物を調製することができ、またかかる組成物から優れた耐熱性、耐衝撃性及び耐ブリード性のポリ乳酸樹脂成形体を得ることができる。 As is clear from the results of Table 3, when the plasticizer of the present invention is used, a polylactic acid resin composition exhibiting excellent moldability even at a low mold temperature can be prepared, and the composition is excellent from this composition. A heat-resistant, impact-resistant and bleed-resistant polylactic acid resin molded body can be obtained.
Claims (12)
Ｒ１，Ｒ２，Ｒ３：水素原子、炭素数２〜２２の脂肪族アシル基又は分子中に炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜２００の（ポリ）オキシアルキレングリコールから一方の水酸基を除いた残基（但し、Ｒ１〜Ｒ３のうちで少なくとも一つは炭素数２〜２２の脂肪族アシル基）
Ｒ４，Ｒ５，Ｒ６：分子中に炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基を有する炭素数２〜２００の（ポリ）オキシアルキレングリコールからすべての水酸基を除いた残基
ｐ，ｑ，ｒ：０又は１の整数（但し、ｐ〜ｒのうちで少なくとも一つは１）｝ A plasticizer for polylactic acid resin, comprising a hardened castor oil derivative represented by the following chemical formula 1:
R 1 , R 2 , R 3 : a hydrogen atom, an aliphatic acyl group having 2 to 22 carbon atoms, or a carbon number 2 having a (poly) oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in the molecule Residue obtained by removing one hydroxyl group from ˜200 (poly) oxyalkylene glycol (wherein at least one of R 1 to R 3 is an aliphatic acyl group having 2 to 22 carbon atoms)
R 4 , R 5 , R 6 : all hydroxyl groups from a (poly) oxyalkylene glycol having 2 to 200 carbon atoms and having a (poly) oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in the molecule Excluded residues p, q, r: an integer of 0 or 1 (provided that at least one of p to r is 1)}
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