JP5196647B2 - Polylactic acid resin composition and polylactic acid resin molded article - Google Patents
Polylactic acid resin composition and polylactic acid resin molded article Download PDFInfo
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- JP5196647B2 JP5196647B2 JP2008104244A JP2008104244A JP5196647B2 JP 5196647 B2 JP5196647 B2 JP 5196647B2 JP 2008104244 A JP2008104244 A JP 2008104244A JP 2008104244 A JP2008104244 A JP 2008104244A JP 5196647 B2 JP5196647 B2 JP 5196647B2
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims description 112
- 239000004626 polylactic acid Substances 0.000 title claims description 112
- 229920005989 resin Polymers 0.000 title claims description 54
- 239000011347 resin Substances 0.000 title claims description 54
- 239000011342 resin composition Substances 0.000 title claims description 37
- 229940022769 d- lactic acid Drugs 0.000 claims description 30
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 28
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 25
- 229920001432 poly(L-lactide) Polymers 0.000 claims description 24
- 229930182843 D-Lactic acid Natural products 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 18
- -1 nitrogen-containing compound Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000005259 measurement Methods 0.000 claims description 8
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000000646 scanning calorimetry Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 description 27
- 230000008018 melting Effects 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003484 crystal nucleating agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- VJESJEJNMGVQLZ-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)hexadecanamide Chemical compound CCCCCCCCCCCCCCCC(=O)N(CCO)CCO VJESJEJNMGVQLZ-UHFFFAOYSA-N 0.000 description 2
- SKDZEPBJPGSFHS-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)N(CCO)CCO SKDZEPBJPGSFHS-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- MMBILEWCGWTAOV-UHFFFAOYSA-N N-(2-Hydroxypropyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)NCC(C)O MMBILEWCGWTAOV-UHFFFAOYSA-N 0.000 description 1
- PLVXODPVSUQTNW-UHFFFAOYSA-N N-(2-hydroxyethyl)hexadec-2-enamide Chemical compound CCCCCCCCCCCCCC=CC(=O)NCCO PLVXODPVSUQTNW-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000003910 behenoyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000021189 garnishes Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OOCSVLHOTKHEFZ-UHFFFAOYSA-N icosanamide Chemical compound CCCCCCCCCCCCCCCCCCCC(N)=O OOCSVLHOTKHEFZ-UHFFFAOYSA-N 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 125000000400 lauroyl 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])[H] 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001419 myristoyl 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])[H] 0.000 description 1
- UWDGKUMOFQTNHC-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO UWDGKUMOFQTNHC-UHFFFAOYSA-N 0.000 description 1
- JTLQQZSDVWPHLD-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)hexanamide Chemical compound CCCCCC(=O)N(CCO)CCO JTLQQZSDVWPHLD-UHFFFAOYSA-N 0.000 description 1
- SWVSGMCNYLUBIB-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadec-2-enamide Chemical compound CCCCCCCCCCCCCCCC=CC(=O)N(CCO)CCO SWVSGMCNYLUBIB-UHFFFAOYSA-N 0.000 description 1
- XGZOMURMPLSSKQ-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO XGZOMURMPLSSKQ-UHFFFAOYSA-N 0.000 description 1
- KWKIQDVMRFABMA-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)tetracosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO KWKIQDVMRFABMA-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 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 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 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 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Description
本発明はポリ乳酸樹脂組成物及びポリ乳酸樹脂成形体に関する。ポリ乳酸樹脂は、微生物や酵素の働きにより分解する性質、いわゆる生分解性を示し、人体に無害な乳酸や二酸化炭素と水になることから、医療用材料や汎用樹脂の代替物として注目されている。このようなポリ乳酸樹脂は結晶性の樹脂であるが、その結晶化速度は小さく、実際には非晶性の樹脂に近い挙動を示す。したがって、もともとポリ乳酸樹脂はガラス転移温度付近で急激に且つ極度に軟化するため、耐熱性、成形性、離型性等の点で十分な物理特性を得ることが困難であった。本発明は、かかるポリ乳酸樹脂の物理特性を向上するものであって、ポリ乳酸樹脂の結晶化速度を十分に大きくし、且つステレオコンプレックス結晶比率を高くしたポリ乳酸樹脂組成物及びポリ乳酸樹脂成形体に関する。 The present invention relates to a polylactic acid resin composition and a polylactic acid resin molded article. Polylactic acid resin has been attracting attention as an alternative to medical materials and general-purpose resins because it exhibits biodegradability, a property that degrades by the action of microorganisms and enzymes, and is harmless to the human body. Yes. Such a polylactic acid resin is a crystalline resin, but its crystallization rate is small, and actually shows a behavior close to that of an amorphous resin. Therefore, since the polylactic acid resin is softened suddenly and extremely near the glass transition temperature, it has been difficult to obtain sufficient physical properties in terms of heat resistance, moldability, releasability, and the like. The present invention improves the physical properties of such a polylactic acid resin, and is a polylactic acid resin composition and a polylactic acid resin molding in which the crystallization rate of the polylactic acid resin is sufficiently increased and the stereocomplex crystal ratio is increased. About the body.
従来、ポリ乳酸樹脂の結晶化速度を大きくし、且つステレオコンプレックス結晶比率を高くしたポリ乳酸樹脂組成物として、ステレオコンプレックスの形成可能なポリ乳酸樹脂に対し、１）リン酸エステル金属塩を用いた例（例えば、特許文献１参照）、２）芳香族アミド化合物を用いた例（例えば、特許文献２参照）、３）芳香族尿素化合物を用いた例（例えば、特許文献３参照）、４）オキサミド誘導体を用いた例（例えば、特許文献４参照）、５）ホスホノ脂肪酸エステルを用いた例（例えば、特許文献５参照）等の提案がある。 Conventionally, as a polylactic acid resin composition in which the crystallization speed of a polylactic acid resin is increased and the stereocomplex crystal ratio is increased, 1) a phosphate metal salt is used for a polylactic acid resin capable of forming a stereocomplex. Examples (for example, see Patent Document 1), 2) Examples using an aromatic amide compound (for example, see Patent Document 2), 3) Examples using an aromatic urea compound (for example, see Patent Document 3), 4) There are proposals such as an example using an oxamide derivative (for example, see Patent Document 4), 5) an example using a phosphono fatty acid ester (for example, see Patent Document 5), and the like.
しかし、前記した１）〜５）の提案には、ポリ乳酸樹脂の結晶化速度を十分に大きくし、且つステレオコンプレックス結晶比率を高くするまでには到っていないという問題がある。
本発明が解決しようとする課題は、ステレオコンプレックスの形成可能なポリ乳酸樹脂の結晶化速度を十分に大きくし、且つステレオコンプレックス結晶比率を高くしたポリ乳酸樹脂組成物、該ポリ乳酸樹脂組成物を溶融成形して結晶化させたポリ乳酸樹脂成形体を提供する処にある。 The problems to be solved by the present invention include a polylactic acid resin composition having a sufficiently high crystallization rate of a polylactic acid resin capable of forming a stereocomplex and a high stereocomplex crystal ratio, and the polylactic acid resin composition. The object is to provide a polylactic acid resin molded body crystallized by melt molding.
前記の課題を解決する本発明は、下記のポリ乳酸樹脂１００質量部当たり、下記の化１で示される含窒素化合物を０．０５〜３０質量部の割合で含有することを特徴とするポリ乳酸樹脂組成物に係る。 The present invention for solving the above-mentioned problems comprises a polylactic acid characterized by containing a nitrogen-containing compound represented by the following chemical formula 1 at a ratio of 0.05 to 30 parts by mass per 100 parts by mass of the following polylactic acid resin. It relates to a resin composition.
ポリ乳酸樹脂：ステレオコンプレックス結晶を生成し得るポリ乳酸ブレンド体であって、質量平均分子量１００００〜５０００００のポリＬ−乳酸と質量平均分子量１００００〜５０００００のポリＤ−乳酸とからなり且つ該ポリＬ−乳酸／該ポリＤ−乳酸＝３０／７０〜７０／３０（質量比）の割合で含有するポリ乳酸ブレンド体。 Polylactic acid resin: a polylactic acid blend capable of producing stereocomplex crystals, comprising a poly L-lactic acid having a mass average molecular weight of 10,000 to 500,000 and a poly D-lactic acid having a mass average molecular weight of 10,000 to 500,000. A polylactic acid blend containing lactic acid / the poly-D-lactic acid at a ratio of 30/70 to 70/30 (mass ratio).
化１において、
Ｒ１：炭素数１２〜２２の脂肪族アシル基
Ａ１，Ａ２：２−ヒドロキシエチル基
In chemical formula 1,
R 1 : Aliphatic acyl group having 12 to 22 carbon atoms A 1 , A 2 : 2-hydroxyethyl group
また本発明は、前記した本発明のポリ乳酸樹脂組成物を溶融成形して結晶化させたポリ乳酸樹脂成形体に係る。 The present invention also relates to a polylactic acid resin molded body obtained by melt-molding and crystallizing the above-described polylactic acid resin composition of the present invention.
先ず本発明のポリ乳酸樹脂組成物について説明する。本発明のポリ乳酸樹脂組成物は、ポリ乳酸樹脂と化１で示される含窒素化合物とを含有して成るものである。このポリ乳酸樹脂は、ステレオコンプレックス結晶を生成し得るポリ乳酸ブレンド体である。 First, the polylactic acid resin composition of the present invention will be described. The polylactic acid resin composition of the present invention comprises a polylactic acid resin and a nitrogen-containing compound represented by Chemical Formula 1. This polylactic acid resin is a polylactic acid blend capable of producing stereocomplex crystals.
本発明のポリ乳酸樹脂組成物に用いるポリ乳酸樹脂としてのポリ乳酸ブレンド体は、ポリＬ−乳酸とポリＤ−乳酸とからなるステレオコンプレックス結晶を生成し得るポリ乳酸ブレンド体である。ここでステレオコンプレックス結晶を生成し得るポリ乳酸ブレンド体とは、ポリ乳酸ブレンド体から結晶化したものを広角Ｘ線回折で観測したときにステレオコンプレックス結晶特有のピーク（２θ＝１２°、２１°、２４°）が少しでも観測されるものであって、ホモ結晶特有のピーク（２θ＝１５°、１６°、１８．５°、２２．５°）が同時に観測されるものであってもよいものと定義される。これについての詳細は
Macromolecules １９８７年、２０巻、９０４〜９０６頁に記載されている。
The polylactic acid blend as the polylactic acid resin used in the polylactic acid resin composition of the present invention is a polylactic acid blend capable of producing a stereocomplex crystal composed of poly L-lactic acid and poly D-lactic acid. Here, the polylactic acid blend capable of producing a stereocomplex crystal is a peak (2θ = 12 °, 21 °, peculiar to a stereocomplex crystal when the crystallized from the polylactic acid blend is observed by wide-angle X-ray diffraction. 24 °) may be observed even a little, and peaks unique to homocrystals (2θ = 15 °, 16 °, 18.5 °, 22.5 °) may be observed at the same time. Is defined. More about this
Macromolecules 1987, Vol. 20, pages 904-906.
前記のポリ乳酸ブレンド体に用いるポリＬ−乳酸とポリＤ−乳酸において、ポリＬ−乳酸及びポリＤ−乳酸の質量平均分子量は、１００００〜５０００００とするが、５００００〜４５００００とするのが好ましく、１０００００〜４０００００とするのが特に好ましい。ポリＬ−乳酸及びポリＤ−乳酸の質量平均分子量が１００００未満であると、得られる成形体の強度や弾性率等の機械物性が低下する傾向を示し、またポリＬ−乳酸及びポリＤ−乳酸の質量平均分子量が５０００００を超えると、その成形加工性が低下する傾向を示す。ポリＬ−乳酸とポリＤ−乳酸との割合は、ポリＬ−乳酸／ポリＤ−乳酸＝３０／７０〜７０／３０（質量比）とするが、３５／６５〜６５／３５（質量比）とするのが好ましく、４５／５５〜５５／４５（質量比）とするのが特に好ましい。ポリＬ−乳酸とポリＤ−乳酸との含有割合の差が大きいほど、得られる成形体におけるステレオコンプレックス結晶の含有割合が減少し、得られる成形体の機械物性が低下する傾向を示す。ポリＬ−乳酸及びポリＤ−乳酸の光学純度は、これもまた特に制限されないが、それぞれ８５モル％以上であることが好ましく、９０モル％以上であることがより好ましく、９５モル％以上であることが更に好ましく、９８モル％以上であることが特に好ましい。ポリＬ−乳酸及びポリＤ−乳酸の光学純度が８５モル％未満であると、立体規則性の低下により結晶化が阻害される傾向を示す。 In the poly L-lactic acid and poly D-lactic acid used in the polylactic acid blend, the mass average molecular weight of the poly L-lactic acid and the poly D-lactic acid is 10,000 to 500,000, preferably 50,000 to 450,000. It is especially preferable to set it as 100,000 to 400,000. When the mass average molecular weight of the poly L-lactic acid and the poly D-lactic acid is less than 10,000, the mechanical properties such as strength and elastic modulus of the resulting molded product tend to be lowered, and the poly L-lactic acid and the poly D-lactic acid When the mass average molecular weight of exceeds 500,000, the moldability tends to decrease. The ratio of poly L-lactic acid to poly D-lactic acid is poly L-lactic acid / poly D-lactic acid = 30/70 to 70/30 (mass ratio), but 35/65 to 65/35 (mass ratio). It is preferable to set it as 45 / 55-55 / 45 (mass ratio). As the difference in the content ratio between poly L-lactic acid and poly D-lactic acid is larger, the content ratio of the stereocomplex crystals in the obtained molded body is decreased, and the mechanical properties of the obtained molded body tend to be lowered. The optical purity of poly L-lactic acid and poly D-lactic acid is also not particularly limited, but is preferably 85 mol% or more, more preferably 90 mol% or more, and more preferably 95 mol% or more. Is more preferable, and it is especially preferable that it is 98 mol% or more. When the optical purity of poly L-lactic acid and poly D-lactic acid is less than 85 mol%, crystallization tends to be inhibited due to a decrease in stereoregularity.
以上説明したポリ乳酸ブレンド体の製造方法は特に制限されない。これには例えば、１）ポリＬ−乳酸とポリＤ−乳酸とをクロロホルム等の溶媒を用いて混合した後に溶媒を除去する方法、２）ポリＬ−乳酸とポリＤ−乳酸とを１６０〜２６０℃程度の温度に加熱して溶融混合する方法等が挙げられる。ポリ乳酸ブレンド体を製造するための原料として用いるポリＬ−乳酸及びポリＤ−乳酸の製造方法も特に制限されない。これには例えば、Ｌ−乳酸又はＤ−乳酸の直接重縮合法、乳酸の環状２量体であるＬ−ラクチド又はＤ−ラクチドの開環重合法が挙げられる。 The method for producing the polylactic acid blend described above is not particularly limited. This includes, for example, 1) a method in which poly L-lactic acid and poly D-lactic acid are mixed using a solvent such as chloroform and then the solvent is removed, and 2) poly L-lactic acid and poly D-lactic acid are 160 to 260. Examples thereof include a method of heating and mixing at a temperature of about 0 ° C. The method for producing poly L-lactic acid and poly D-lactic acid used as a raw material for producing a polylactic acid blend is not particularly limited. Examples thereof include a direct polycondensation method of L-lactic acid or D-lactic acid, and a ring-opening polymerization method of L-lactide or D-lactide which is a cyclic dimer of lactic acid.
本発明のポリ乳酸樹脂組成物に用いる化１で示される含窒素化合物において、化１中のＲ１としては、ドデカノイル基、テトラデカノイル基、ヘキサデカノイル基、オクタデカノイル基、エイコセノイル基、ドコサノイル基等の炭素数１２〜２２の脂肪族アシル基が挙げられるが、なかでも炭素数１２〜１８の脂肪族アシル基が好ましい。 In the nitrogen-containing compound represented by Chemical Formula 1 used in the polylactic acid resin composition of the present invention, R 1 in Chemical Formula 1 includes dodecanoyl group, tetradecanoyl group, hexadecanoyl group, octadecanoyl group, eicosenoyl group, Examples thereof include an aliphatic acyl group having 12 to 22 carbon atoms such as a docosanoyl group, among which an aliphatic acyl group having 12 to 18 carbon atoms is preferable.
また化１中のＡ１及びＡ２は、共に２−ヒドロキシエチル基である。 A 1 and A 2 in Chemical Formula 1 are both 2-hydroxyethyl groups.
化１で示される含窒素化合物の具体例としては、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）ドデカンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）テトラデカンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）ヘキサデカンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）オクタデカンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）エイコサンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）ドコサンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）ヘキサデセンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）オクタデセンアミド等のアシル基の炭素数１２〜２２のＮ，Ｎ−ビス（２−ヒドロキシエチル）アルカン（又はアルケン）アミドが挙げられる。なかでも、化１で示される窒素化合物としては、炭素数１２〜１８のＮ，Ｎ−ビス（２−ヒドロキシエチル）アルカン（又はアルケン）アミドが好ましく、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）ドデカンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）テトラデカンアミド、Ｎ，Ｎ−ビス（２−ヒドロキシエチル）ヘキサデカンアミドか特に好ましい。 Specific examples of the nitrogen-containing compound represented by Chemical Formula 1 include N, N-bis (2-hydroxyethyl) dodecanamide, N, N-bis (2-hydroxyethyl) tetradecanamide, N, N-bis (2- Hydroxyethyl) hexadecanamide, N, N-bis (2-hydroxyethyl) octadecanamide, N, N-bis (2-hydroxyethyl) eicosanamide, N, N-bis (2-hydroxyethyl) docosanamide, N, N, N-bis (2-hydroxyethyl) alkanes having 12 to 22 carbon atoms of acyl groups such as N-bis (2-hydroxyethyl) hexadecenamide and N, N-bis (2-hydroxyethyl) octadecenamide ( Or alkene) amide. Among these, as the nitrogen compound represented by Chemical Formula 1, N, N-bis (2-hydroxyethyl) alkane (or alkene) amide having 12 to 18 carbon atoms is preferable, and N, N-bis (2-hydroxyethyl) is preferable. Particularly preferred are dodecanamide, N, N-bis (2-hydroxyethyl) tetradecanamide, and N, N-bis (2-hydroxyethyl) hexadecanamide.
本発明のポリ乳酸樹脂組成物は、以上説明したポリ乳酸樹脂１００質量部当たり、化１で示される含窒素化合物を０．０５〜３０質量部の割合で含有するものとするが、０．１〜２５質量部の割合で含有するものとするのが好ましく、０．３〜５質量部の割合で含有するものとするのがより好ましい。ポリ乳酸樹脂１００質量部当たり、化１で示される含窒素化合物が０．０５質量部未満では、得られるポリ乳酸樹脂成形体におけるステレオコンプレックス結晶の含有割合が減少し、結晶化速度の向上の程度が減少する傾向を示す。逆に、ポリ乳酸樹脂１００質量部当たり、化１で示される含窒素化合物の含有割合が３０質量部を超えると、化１で示される含窒素化合物による可塑剤的作用が強く発現するようになって、得られるポリ乳酸樹脂成形体の剛性が低下する傾向を示し、化１で示される含窒素化合物がブリードアウトしてポリ乳酸樹脂成形体の外観が低下する傾向を示す。 The polylactic acid resin composition of the present invention contains 0.05 to 30 parts by mass of the nitrogen-containing compound represented by Chemical formula 1 per 100 parts by mass of the polylactic acid resin described above. It is preferable to contain in the ratio of -25 mass parts, and it is more preferable to contain in the ratio of 0.3-5 mass parts. When the nitrogen-containing compound represented by Chemical Formula 1 is less than 0.05 parts by mass per 100 parts by mass of the polylactic acid resin, the content ratio of the stereocomplex crystals in the obtained polylactic acid resin molded product is reduced, and the degree of improvement of the crystallization speed Shows a tendency to decrease. On the contrary, when the content ratio of the nitrogen-containing compound represented by Chemical Formula 1 exceeds 30 parts by mass per 100 parts by mass of the polylactic acid resin, the plasticizer action by the nitrogen-containing compound represented by Chemical Formula 1 is strongly expressed. Thus, the rigidity of the resulting polylactic acid resin molded product tends to decrease, and the nitrogen-containing compound represented by Chemical Formula 1 bleeds out, and the appearance of the polylactic acid resin molded product tends to decrease.
本発明のポリ乳酸樹脂組成物は、その特性を損なわない限りにおいて、タルク、層状粘土鉱物等の充填剤、可塑剤、顔料、安定剤、帯電防止剤、紫外線吸収剤、酸化防止剤、難燃剤、離型剤、滑剤、染料、抗菌剤、末端封止剤等の添加剤を含有することもできる。このような添加剤の含有割合は、ポリ乳酸樹脂１００質量部当たり、２０質量％以下とするのが好ましい。 As long as the properties of the polylactic acid resin composition of the present invention are not impaired, fillers such as talc and layered clay minerals, plasticizers, pigments, stabilizers, antistatic agents, ultraviolet absorbers, antioxidants, flame retardants Further, additives such as mold release agents, lubricants, dyes, antibacterial agents, and end-capping agents can be contained. The content of such additives is preferably 20% by mass or less per 100 parts by mass of the polylactic acid resin.
次に本発明のポリ乳酸樹脂成形体について説明する。本発明のポリ乳酸樹脂成形体は、以上説明したような本発明のポリ乳酸樹脂組成物を溶融成形して結晶化させたものである。本発明のポリ乳酸樹脂組成物を溶融成形する際の溶融温度は特に制限されないが、１６０〜２６０℃とするのが好ましい。この溶融温度が１６０℃未満であると、ポリ乳酸樹脂組成物の溶融が不十分となり、その成分が均一に分散しにくくなる傾向がある。逆に、この溶融温度が２６０℃を超えると、ポリ乳酸樹脂の分子量が低下して得られるポリ乳酸樹脂成形体の物性が損なわれる傾向がある。 Next, the polylactic acid resin molded product of the present invention will be described. The polylactic acid resin molded body of the present invention is obtained by melt-molding and crystallizing the polylactic acid resin composition of the present invention as described above. Although the melting temperature at the time of melt-molding the polylactic acid resin composition of the present invention is not particularly limited, it is preferably 160 to 260 ° C. When the melting temperature is less than 160 ° C., the polylactic acid resin composition is not sufficiently melted, and the components tend not to be uniformly dispersed. On the other hand, when the melting temperature exceeds 260 ° C., the physical properties of the polylactic acid resin molded product obtained by reducing the molecular weight of the polylactic acid resin tend to be impaired.
本発明のポリ乳酸樹脂組成物を溶融成形する際の溶融温度の保持時間は特に制限されないが、０．１〜３０分とするのが好ましい。溶融温度の保持時間が０．１分未満であると、得られるポリ乳酸樹脂成形体におけるポリ乳酸樹脂の結晶化が不十分となる傾向があり、逆に溶融温度の保持時間が３０分を超えると、ポリ乳酸樹脂の分子量が低下して、得られるポリ乳酸樹脂成形体の物性が損なわれる傾向がある。 The holding time of the melting temperature when melt-molding the polylactic acid resin composition of the present invention is not particularly limited, but is preferably 0.1 to 30 minutes. If the melting temperature holding time is less than 0.1 minutes, the resulting polylactic acid resin molded product tends to have insufficient crystallization of the polylactic acid resin, and conversely, the melting temperature holding time exceeds 30 minutes. And the molecular weight of polylactic acid resin falls, and there exists a tendency for the physical property of the obtained polylactic acid resin molding to be impaired.
本発明のポリ乳酸樹脂組成物を溶融成形して結晶化させる方法は特に制限されないが、溶融状態から３０〜１６０℃の温度まで冷却し、１０秒間〜３０分間、その温度で保持する方法が好ましい。保持時間が１０秒間未満であると、得られるポリ乳酸樹脂成形体におけるポリ乳酸樹脂の結晶化が不十分となる傾向があり、逆に保持時間が３０分間を超えると、ポリ乳酸樹脂成形体を得るのに長時間が必要となり、実用上好ましくない傾向がある。 The method for melt-molding and crystallizing the polylactic acid resin composition of the present invention is not particularly limited, but a method of cooling from a molten state to a temperature of 30 to 160 ° C. and holding at that temperature for 10 seconds to 30 minutes is preferable. . If the holding time is less than 10 seconds, crystallization of the polylactic acid resin in the resulting polylactic acid resin molded product tends to be insufficient. Conversely, if the holding time exceeds 30 minutes, the polylactic acid resin molded product It takes a long time to obtain, and this tends to be unpractical in practice.
以上説明した本発明のポリ乳酸樹脂成形体のなかでも、ポリ乳酸樹脂組成物として前記のポリ乳酸ブレンド体と化１で示される含窒素化合物とを含有するものを用いたポリ乳酸樹脂成形体であって、その示差走査熱量測定（以下、ＤＳＣ測定という）による溶融状態からの降温測定（降温速度：２０℃／分）により求めた結晶化ピーク温度が１１５℃以上であり且つ結晶化ピークの発熱量が２０Ｊ／ｇ以上であるものが好ましく、結晶化ピークの発熱量が３０Ｊ／ｇ以上であるものがより好ましい。なかでも、ＤＳＣ測定により求めたホモ結晶融解ピークの融解吸熱量（ΔＨｍ，ｈｏｍｏ）とステレオコンプレックス結晶融解ピークの融解吸熱量（ΔＨｍ，ｓｔｅｒｅｏ）とから求めたステレオコンプレックス結晶比率｛ステレオ結晶比率：（ΔＨｍ，ｓｔｅｒｅｏ／（ΔＨｍ，ｈｏｍｏ＋ΔＨｍ，ｓｔｅｒｅｏ）×１００（％）｝が９０％以上のものが好ましく、９５％以上のものがより好ましい。冷却過程でのかかる降温測定における結晶化温度（ピークトップ温度）が高温側で観測されるほど、結晶化速度が大きいことになり、また冷却過程でのかかる降温測定における結晶化に基づく発熱量（ピーク発熱量）が大きいほど、結晶化度向上効果が高いことになる。更にポリ乳酸樹脂成形体における結晶部分のうちでステレオコンプレックス結晶の割合が高いほど、ポリ乳酸樹脂成形体の耐熱性が向上する傾向にある。 Among the polylactic acid resin moldings of the present invention described above, a polylactic acid resin molding using a polylactic acid resin composition containing the above-mentioned polylactic acid blend and the nitrogen-containing compound represented by Chemical Formula 1 is used. The crystallization peak temperature obtained by the temperature drop measurement (temperature drop rate: 20 ° C./min) from the molten state by differential scanning calorimetry (hereinafter referred to as DSC measurement) is 115 ° C. or higher, and the crystallization peak exotherm. Those having an amount of 20 J / g or more are preferred, and those having a calorific value of crystallization peak of 30 J / g or more are more preferred. Among them, the stereocomplex crystal ratio obtained from the melting endotherm (ΔHm, homo) of the homocrystal melting peak determined by DSC measurement and the melting endotherm (ΔHm, stereo) of the stereocomplex crystal melting peak {stereocrystal ratio: ( ΔHm, stereo / (ΔHm, homo + ΔHm, stereo) × 100 (%)} is preferably 90% or more, and more preferably 95% or more, and the crystallization temperature (peak top temperature) in the temperature drop measurement during the cooling process. ) Is observed on the higher temperature side, the crystallization rate increases, and the higher the calorific value (peak calorific value) based on crystallization in the temperature drop measurement during the cooling process, the higher the crystallinity improvement effect. Furthermore, stereocomplex among the crystal parts in the polylactic acid resin molded product. As the ratio of crystals is high, the heat resistance of the polylactic acid resin molded article tend to be improved.
本発明のポリ乳酸樹脂成形体を製造するための成形方法は特に制限されず、その成形方法としては、射出成形、押出成形、ブロー成形、インフレーション成形、異形押出成形、射出ブロー成形、真空圧空成形、紡糸等が挙げられる。本発明のポリ乳酸樹脂組成物によると、十分に大きい結晶化速度が達成されるため、これを例えば射出成形に供した場合であっても、十分に結晶性を有し且つステレオコンプレックス結晶比率の高いポリ乳酸樹脂成形体を得ることができる。本発明のポリ乳酸樹脂成形体は、ステレオコンプレックス結晶比率が高く、耐熱性に優れるため、バンパー、ラジエーターグリル、サイドモール、ガーニッシュ、ホイールカバー、エアロパーツ、インストルメントパネル、ドアトリム、シートファブリック、ドアハンドル、フロアマット等の自動車部品、家電製品のハウジング、製品包装用フィルム、防水シート、各種容器、ボトル等として有用である。また、本発明のポリ乳酸樹脂成形体をシートとする場合には、紙又は他のポリマーシートと積層し、多層構造の積層体とすることもできる。 The molding method for producing the polylactic acid resin molded product of the present invention is not particularly limited, and the molding method includes injection molding, extrusion molding, blow molding, inflation molding, profile extrusion molding, injection blow molding, and vacuum / pressure molding. , Spinning and the like. According to the polylactic acid resin composition of the present invention, a sufficiently high crystallization rate is achieved. Therefore, even when this is subjected to, for example, injection molding, it has sufficient crystallinity and has a stereocomplex crystal ratio. A high polylactic acid resin molding can be obtained. Since the polylactic acid resin molded article of the present invention has a high stereo complex crystal ratio and excellent heat resistance, it is a bumper, radiator grill, side molding, garnish, wheel cover, aero parts, instrument panel, door trim, seat fabric, door handle. It is useful as automobile parts such as floor mats, housings for home appliances, film for product packaging, waterproof sheets, various containers, bottles and the like. Moreover, when using the polylactic acid resin molding of this invention as a sheet | seat, it can also laminate | stack with paper or another polymer sheet, and can also be set as the laminated body of a multilayer structure.
以上説明した本発明のポリ乳酸樹脂組成物によると、ポリ乳酸樹脂の結晶化速度を十分に大きくし、且つステレオコンプレックス結晶比率を高くすることができるという効果がある。 According to the polylactic acid resin composition of the present invention described above, there are effects that the crystallization rate of the polylactic acid resin can be sufficiently increased and the stereocomplex crystal ratio can be increased.
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（ポリ乳酸樹脂組成物の調製）
・実施例１｛ポリ乳酸樹脂組成物（Ｐ−１）の調製｝
Ｄ−ラクチド１００ｇ、ドデシルアルコール０．１ｇ、オクチル酸スズ１００mgを反応容器に入れ、反応容器内を１×１０−２mmＨｇまで減圧した。続いて、内容物を十分に攪拌しながら除々に温度を上昇させ、１６０℃で１時間保持した。得られた反応生成物をクロロホルムに溶解し、メタノール中に滴下してポリＤ−乳酸を単離精製した。得られたポリＤ−乳酸は、質量平均分子量１２００００、光学純度９９％であった。次に、ポリＬ−乳酸（トヨタ自動車製、エコプラスチックＵ’ｚＳ−１７、質量平均分子量１４００００、光学純度９９％）５０部、前記のポリＤ−乳酸５０部及びＮ，Ｎ−ビス（２−ヒドロキシエチル）ドデカンアミド１部を、ブレンダーを用いてドライブレンドし、ポリ乳酸樹脂組成物（Ｐ−１）を調製した。
Test category 1 (Preparation of polylactic acid resin composition)
Example 1 {Preparation of polylactic acid resin composition (P-1)}
100 g of D-lactide, 0.1 g of dodecyl alcohol, and 100 mg of tin octylate were placed in a reaction vessel, and the pressure in the reaction vessel was reduced to 1 × 10 −2 mmHg. Subsequently, the temperature was gradually increased while the contents were sufficiently stirred, and maintained at 160 ° C. for 1 hour. The obtained reaction product was dissolved in chloroform and dropped into methanol to isolate and purify poly-D-lactic acid. The obtained poly-D-lactic acid had a mass average molecular weight of 120,000 and an optical purity of 99%. Next, 50 parts of poly L-lactic acid (manufactured by Toyota Motor Corporation, Ecoplastic U'zS-17, mass average molecular weight 140000, optical purity 99%), 50 parts of the above poly D-lactic acid and N, N-bis (2- 1 part of hydroxyethyl) dodecanamide was dry blended using a blender to prepare a polylactic acid resin composition (P-1).
・実施例又は参考例２〜１５及び比較例１〜８｛ポリ乳酸樹脂組成物（Ｐ−２）〜（Ｐ−１５）及び（Ｒ−１）〜（Ｒ−８）の調製｝
ポリ乳酸樹脂組成物（Ｐ−１）の調製と同様にして、ポリ乳酸樹脂組成物（Ｐ−２）〜（Ｐ−１５）及び（Ｒ−１）〜（Ｒ−８）を調製した。これらの内容をポリ乳酸樹脂組成物（Ｐ−１）も含めて表１にまとめて示した。
Examples or Reference Examples 2 to 15 and Comparative Examples 1 to 8 {Preparation of polylactic acid resin compositions (P-2) to (P-15) and (R-1) to (R-8)}
Polylactic acid resin compositions (P-2) to (P-15) and (R-1) to (R-8) were prepared in the same manner as the preparation of the polylactic acid resin composition (P-1). These contents are collectively shown in Table 1 including the polylactic acid resin composition (P-1).
・参考例１６（ポリ乳酸樹脂組成物Ｐ−１７の調製）
Ｌ−ラクチド１００ｇ、１，１２−ドデカンジオール３ｇ、オクチル酸スズ１００mgを反応容器に入れ、反応容器内を１×１０−２mmＨｇまで減圧した。続いて、内容物を十分に攪拌しながら徐々に温度を上昇させ、１５０℃で３時間保持した。得られた反応生成物をクロロホルムに溶解し、メタノール中に滴下して質量平均分子量が約２３０００のポリＬ−乳酸を得た。次に、Ｄ−ラクチド４０ｇ、前記のポリＬ−乳酸８０ｇを、窒素雰囲気下に、２００℃で均一に溶解した。続いて室温まで放冷後、オクチル酸スズ４０mgを加え、１５０℃で３時間反応させた。得られた反応生成物をヘキサフルオロイソプロパノールに溶解し、メタノール中に滴下して質量平均分子量が５４０００のポリ乳酸ステレオブロック共重合体（Ｂ−１）（ポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸）を得た。次に、Ｌ−ラクチド２０ｇ、前記のポリ乳酸ステレオブロック共重合体（Ｂ−１）８０ｇを、窒素雰囲気下に、２２０℃で均一に溶解した。続いてオクチル酸スズ２０mgを反応容器に入れ、１５０℃で３時間反応させた。得られた反応生成物をヘキサフルオロイソプロパノールに溶解し、メタノール中に滴下して質量平均分子量が約８１０００のポリ乳酸ステレオブロック共重合体（Ｂ−２）（ポリＬ−乳酸−ポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸−ポリＬ−乳酸）を得た。次に、Ｄ−ラクチド１０ｇ、得られたポリ乳酸ステレオブロック共重合体（Ｂ−２）８０ｇを、窒素雰囲気下に、２４０℃で均一に溶解した。続いて室温まで放冷後、オクチル酸スズ１０ｍｇを加え、１５０℃で３時間反応させた。得られた反応生成物をヘキサフルオロイソプロパノールに溶解し、メタノール中に滴下して質量平均分子量が約１１５０００のポリ乳酸ステレオブロック共重合体（Ｂ−３）（ポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸）を得た。次に、ポリ乳酸ステレオブロック共重合体（Ｂ−３）１００部及びＮ，Ｎ−ビス（２−ヒドロキシエチル）ドデカンアミド１部を、ブレンダーを用いてドライブレンドし、ポリ乳酸樹脂組成物（Ｐ−１６）を調製した。内容を表１に示した。
Reference Example 16 (Preparation of polylactic acid resin composition P-17)
L-lactide 100 g, 1,12-dodecanediol 3 g, and tin octylate 100 mg were placed in a reaction vessel, and the pressure in the reaction vessel was reduced to 1 × 10 −2 mmHg. Subsequently, the temperature was gradually increased while the contents were sufficiently stirred, and maintained at 150 ° C. for 3 hours. The obtained reaction product was dissolved in chloroform and dropped into methanol to obtain poly L-lactic acid having a mass average molecular weight of about 23,000. Next, 40 g of D-lactide and 80 g of the above poly L-lactic acid were uniformly dissolved at 200 ° C. in a nitrogen atmosphere. Subsequently, after allowing to cool to room temperature, 40 mg of tin octylate was added and reacted at 150 ° C. for 3 hours. The obtained reaction product was dissolved in hexafluoroisopropanol and dropped into methanol to give a polylactic acid stereoblock copolymer (B-1) having a mass average molecular weight of 54,000 (poly D-lactic acid-poly L-lactic acid-poly). D-lactic acid) was obtained. Next, 20 g of L-lactide and 80 g of the polylactic acid stereoblock copolymer (B-1) were uniformly dissolved at 220 ° C. in a nitrogen atmosphere. Subsequently, 20 mg of tin octylate was placed in a reaction vessel and reacted at 150 ° C. for 3 hours. The obtained reaction product was dissolved in hexafluoroisopropanol and dropped into methanol to give a polylactic acid stereoblock copolymer (B-2) having a mass average molecular weight of about 81,000 (poly L-lactic acid-poly D-lactic acid- Poly L-lactic acid-poly D-lactic acid-poly L-lactic acid) was obtained. Next, 10 g of D-lactide and 80 g of the obtained polylactic acid stereoblock copolymer (B-2) were uniformly dissolved at 240 ° C. in a nitrogen atmosphere. Subsequently, after cooling to room temperature, 10 mg of tin octylate was added, and the mixture was reacted at 150 ° C. for 3 hours. The obtained reaction product was dissolved in hexafluoroisopropanol and dropped into methanol to give a polylactic acid stereoblock copolymer (B-3) having a mass average molecular weight of about 115,000 (poly D-lactic acid-poly L-lactic acid- Poly D-lactic acid-poly L-lactic acid-poly D-lactic acid-poly L-lactic acid-poly D-lactic acid) was obtained. Next, 100 parts of a polylactic acid stereoblock copolymer (B-3) and 1 part of N, N-bis (2-hydroxyethyl) dodecanamide were dry blended using a blender to produce a polylactic acid resin composition (P -16) was prepared. The contents are shown in Table 1.
表１において、
Ｌ−１：ポリＬ−乳酸、質量平均分子量１４００００、光学純度９９％
Ｌ−２：ポリＬ−乳酸、質量平均分子量２４００００、光学純度９９％
Ｌ−３：ポリＬ−乳酸、質量平均分子量３００００、光学純度９９％
Ｌ−４：ポリＤ−乳酸、質量平均分子量４００００、光学純度９９％
Ｌ−５：ポリＤ−乳酸、重量平均分子量１２００００、光学純度９９％
Ｌ−６：ポリＤ−乳酸、重量平均分子量１８００００、光学純度９９％
Ｌ−７：ポリＤ−乳酸、重量平均分子量３３００００、光学純度９９％
Ｌ−８：質量平均分子量１１５０００、その構成がポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸−ポリＬ−乳酸−ポリＤ−乳酸からなるポリ乳酸ステレオブロック共重合体（Ｂ−３）
Ｍ−１〜Ｍ−８：表２に記載した化１で示される含窒素化合物
ｍ−１：Ｎ，Ｎ−ビス（２−ヒドロキシエチル）ヘキサンアミド
ｍ−２：Ｎ，Ｎ−ビス（２−ヒドロキシエチル）テトラコサンアミド
ｍ−３：Ｎ−（２−メチル−２−ヒドロキシエチル）ドデカンアミド
ｍ−４：ドデカンアミド
ｍ−５：アミド系結晶核剤（日本化成製の商品名スリパックスＨ、エチレンビス−１２−ヒドロキシステアリン酸アミド）
ｍ−６：イソフタル酸ジメチル
ｍ−７：スルホン酸系結晶核剤（５−スルホイソフタル酸ジメチル＝バリウム）
ｍ−８：芳香族尿素系結晶核剤（日本化成製の商品名ハクリーンＳＸ、キシリレンビスステアリル尿素）
In Table 1,
L-1: Poly L-lactic acid, mass average molecular weight 140000, optical purity 99%
L-2: Poly L-lactic acid, mass average molecular weight 240000, optical purity 99%
L-3: Poly L-lactic acid, mass average molecular weight 30000, optical purity 99%
L-4: Poly-D-lactic acid, mass average molecular weight 40000, optical purity 99%
L-5: Poly-D-lactic acid, weight average molecular weight 120,000, optical purity 99%
L-6: Poly-D-lactic acid, weight average molecular weight 180000, optical purity 99%
L-7: Poly-D-lactic acid, weight average molecular weight 330000, optical purity 99%
L-8: Polylactic acid having a mass average molecular weight of 115000 and comprising poly D-lactic acid-poly L-lactic acid-poly D-lactic acid-poly L-lactic acid-poly D-lactic acid-poly L-lactic acid-poly D-lactic acid. Stereoblock copolymer (B-3)
M-1 to M-8: Nitrogen-containing compound represented by Chemical Formula 1 described in Table 2 m-1: N, N-bis (2-hydroxyethyl) hexanamide m-2: N, N-bis (2- Hydroxyethyl) Tetracosanamide m-3: N- (2-methyl-2-hydroxyethyl) dodecanamide m-4: Dodecanamide m-5: Amide crystal nucleating agent (trade name Sripax H, manufactured by Nippon Kasei) Bis-12-hydroxystearic acid amide)
m-6: dimethyl isophthalate m-7: sulfonic acid crystal nucleating agent (dimethyl 5-sulfoisophthalate = barium)
m-8: Aromatic urea-based crystal nucleating agent (trade name Haclean SX, xylylene bisstearyl urea manufactured by Nippon Kasei)
試験区分２（ポリ乳酸樹脂成形体のプレス成形及びその評価）
試験区分１で調製したポリ乳酸樹脂組成物（Ｐ−１）〜（Ｐ−１６）、（Ｒ−１）〜（Ｒ−８）をラボプラストミルに投入し、２１０℃にて１分間溶融混練した後、プレス成形してポリ乳酸樹脂成形体を得た。得られたポリ乳酸樹成形体を１００℃で２４時間除湿乾燥し、絶乾状態にした後、試料を採取して、下記の示差走査熱量計に供し、下記の条件下で、結晶化ピーク温度、結晶化ピークの発熱量、ホモ結晶融解ピーク温度、ホモ結晶融解ピークの融解吸熱量、ステレオコンプレックス結晶融解ピーク温度、ステレオコンプレックス結晶融解ピークの融解吸熱量を求めた。結果を表３にまとめて示した。
・示差走査熱量計の条件
示差走査熱量計（パーキンエルマー社製の商品名Ｄｉａｍｏｎｄ ＤＳＣ）を用いて、試料１０mgをアルミニウムセルに充填し、１００℃／分で室温から２７０℃まで昇温し、１分間保持して溶融させた後、２０℃／ｍｉｎの冷却速度で０℃まで冷却し、その際のポリ乳酸の結晶化ピーク温度（Ｔｃ，ｃｏｏｌ）及び結晶化ピークの発熱量（ΔＨｃ，ｃｏｏｌ）を求めた（降温測定）。
Test category 2 (Press molding of polylactic acid resin molding and its evaluation)
The polylactic acid resin compositions (P-1) to (P-16) and (R-1) to (R-8) prepared in Test Category 1 were put into a lab plast mill and melt kneaded at 210 ° C. for 1 minute. After that, press molding was performed to obtain a polylactic acid resin molded body. The obtained polylactic acid tree molded body was dehumidified and dried at 100 ° C. for 24 hours and completely dried, and then a sample was taken and subjected to the following differential scanning calorimeter, and the crystallization peak temperature was measured under the following conditions: The calorific value of the crystallization peak, the homocrystal melting peak temperature, the melting endotherm of the homocrystal melting peak, the stereocomplex crystal melting peak temperature, and the melting endotherm of the stereocomplex crystal melting peak were determined. The results are summarized in Table 3.
-Conditions of differential scanning calorimeter Using a differential scanning calorimeter (trade name Diamond DSC, manufactured by Perkin Elmer), 10 mg of a sample was filled in an aluminum cell, and the temperature was raised from room temperature to 270 ° C at 100 ° C / min. After being held for a minute and melted, it is cooled to 0 ° C. at a cooling rate of 20 ° C./min. The crystallization peak temperature (Tc, cool) and the calorific value of the crystallization peak (ΔHc, cool) at that time Was obtained (temperature decrease measurement).
次いで、前記のように冷却したものをそのまま１分間保持した後、１００℃／ｍｉｎの昇温速度で２７０℃まで再昇温し、その際の結晶化ピーク温度（Ｔｃ，ｈｏｔ）、結晶化ピークの発熱量（ΔＨｃ，ｈｏｔ）、ピークトップが１６０℃〜１８０℃に現れるホモ結晶融解ピーク温度（Ｔｍ，ｈｏｍｏ）、ホモ結晶融解ピークの融解吸熱量（ΔＨｍ，ｈｏｍｏ）、ピークトップが１９０℃〜２４０℃に現れるステレオコンプレックス結晶融解ピーク温度（Ｔｍ，ｓｔｅｒｅｏ）、ステレオコンプレックス結晶融解ピークの融解吸熱量（ΔＨｍ，ｓｔｅｒｅｏ）を求めた（再昇温測定）。また、ステレオコンプレックス結晶比率を、ホモ結晶融解ピークの融解吸熱量（ΔＨｍ，ｈｏｍｏ）とステレオコンプレックス結晶融解ピークの融解吸熱量（ΔＨｍ，ｓｔｅｒｅｏ）とから、下記の数１より算出した。なお、結晶化ピーク温度及び融解ピーク温度は共にピークトップの温度である。
Subsequently, the cooled product is held for 1 minute as it is, and then heated again to 270 ° C. at a rate of 100 ° C./min. The crystallization peak temperature (Tc, hot), crystallization peak at that time Exothermic amount (ΔHc, hot), homocrystal melting peak temperature (Tm, homo) where the peak top appears at 160 ° C. to 180 ° C., melting endotherm (ΔHm, homo) of the homocrystal melting peak, and peak top of 190 ° C. to The stereocomplex crystal melting peak temperature (Tm, stereo) appearing at 240 ° C. and the melting endotherm (ΔHm, stereo) of the stereocomplex crystal melting peak were determined (re-temperature rise measurement). Further, the stereocomplex crystal ratio was calculated from the following formula 1 from the melting endotherm (ΔHm, homo) of the homocrystal melting peak and the melting endotherm (ΔHm, stereo) of the stereocomplex crystal melting peak. The crystallization peak temperature and the melting peak temperature are both peak top temperatures.
表３において、
Ｔ−Ｃ−Ｃ：Ｔｃ，ｃｏｏｌ
Ｔ−Ｃ−Ｈ：Ｔｃ，ｈｏｔ
Ｔ−Ｍ−Ｈ：Ｔｍ，ｈｏｍｏ
Ｔ−Ｍ−Ｓ：Ｔｍ，ｓｔｅｒｅｏ
ΔＨ−Ｃ−Ｃ：ΔＨｃ，ｃｏｏｌ
ΔＨ−Ｃ−Ｈ：ΔＨｃ，ｈｏｔ
ΔＨ−Ｍ−Ｈ：ΔＨｍ，ｈｏｍｏ
ΔＨ−Ｍ−Ｓ：ΔＨｍ，ｓｔｅｒｅｏ
In Table 3,
TC-C: Tc, cool
T-C-H: Tc, hot
T-M-H: Tm, homo
TMS: Tm, stereo
ΔH-C-C: ΔHc, cool
ΔH-C-H: ΔHc, hot
ΔH-M-H: ΔHm, homo
ΔH-MS: ΔHm, stereo
Claims (6)
ポリ乳酸樹脂：ステレオコンプレックス結晶を生成し得るポリ乳酸ブレンド体であって、質量平均分子量１００００〜５０００００のポリＬ−乳酸と質量平均分子量１００００〜５０００００のポリＤ−乳酸とからなり且つ該ポリＬ−乳酸／該ポリＤ−乳酸＝３０／７０〜７０／３０（質量比）の割合で含有するポリ乳酸ブレンド体。
Ｒ１：炭素数１２〜２２の脂肪族アシル基
Ａ１，Ａ２ ：２−ヒドロキシエチル基 A polylactic acid resin composition comprising 0.05 to 30 parts by mass of a nitrogen-containing compound represented by the following chemical formula 1 per 100 parts by mass of the following polylactic acid resin.
Polylactic acid resin: a polylactic acid blend capable of producing stereocomplex crystals, comprising a poly L-lactic acid having a mass average molecular weight of 10,000 to 500,000 and a poly D-lactic acid having a mass average molecular weight of 10,000 to 500,000. A polylactic acid blend containing lactic acid / the poly-D-lactic acid at a ratio of 30/70 to 70/30 (mass ratio).
R 1 : Aliphatic acyl group having 12 to 22 carbon atoms A 1 , A 2 : 2 -hydroxyethyl group
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