JP5252736B2 - ポリ乳酸系樹脂組成物及びそれよりなる成形体 - Google Patents
ポリ乳酸系樹脂組成物及びそれよりなる成形体 Download PDFInfo
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- JP5252736B2 JP5252736B2 JP2009245602A JP2009245602A JP5252736B2 JP 5252736 B2 JP5252736 B2 JP 5252736B2 JP 2009245602 A JP2009245602 A JP 2009245602A JP 2009245602 A JP2009245602 A JP 2009245602A JP 5252736 B2 JP5252736 B2 JP 5252736B2
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- acid
- polylactic acid
- resin composition
- polylactic
- fatty acid
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- 239000004626 polylactic acid Substances 0.000 title claims description 83
- 239000011342 resin composition Substances 0.000 title claims description 35
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- 239000000194 fatty acid Substances 0.000 claims description 73
- 229930195729 fatty acid Natural products 0.000 claims description 73
- -1 fatty acid ester Chemical class 0.000 claims description 62
- 229920005989 resin Polymers 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 43
- 150000004665 fatty acids Chemical class 0.000 claims description 36
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 30
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- 239000000470 constituent Substances 0.000 claims description 15
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 11
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 28
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- 235000021355 Stearic acid Nutrition 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
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- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- RKHXDCVAPIMDMG-UHFFFAOYSA-N 9-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCC(O)CCCCCCCC(O)=O RKHXDCVAPIMDMG-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
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Description
〔1〕 ポリ乳酸系樹脂及びポリグリセリン脂肪酸エステルを含有してなるポリ乳酸系樹脂組成物であって、該ポリグリセリン脂肪酸エステルの含有量が、ポリ乳酸系樹脂100重量部に対して0.1〜30重量部であり、かつ、ポリグリセリン脂肪酸エステルが、カプリル酸、カプリン酸、及びラウリン酸を構成脂肪酸として含有し、該ラウリン酸の含有量が構成脂肪酸中20mol%以上であり、平均重合度が10のポリグリセリンを含有し、さらに、ポリグリセリン脂肪酸エステルのエステル化率が50〜85%である、ポリ乳酸系樹脂組成物、
〔2〕 前記〔1〕記載のポリ乳酸系樹脂組成物を成形してなる、ポリ乳酸系樹脂成形体、ならびに
〔3〕 前記〔1〕記載のポリ乳酸系樹脂組成物を含む複合体を成形してなる成形体
に関する。
(1)ポリ乳酸、
(2)乳酸−他の脂肪族ヒドロキシカルボン酸コポリマー、
(3)多官能多糖類、及び乳酸単位を含むポリ乳酸系樹脂、
(4)脂肪族多価カルボン酸単位、脂肪族多価アルコール単位、及び乳酸単位を含むポリ乳酸系樹脂、ならびに
(5)これらの混合物
が挙げられる。これらの中でも、得られる成形体の透明性の観点から、ポリ乳酸、及び、乳酸−他の脂肪族ヒドロキシカルボン酸コポリマーが好ましく、ポリ乳酸がより好ましい。
ゲルバーミエーシヨンクロマトグラフィー(GPC)により、ポリスチレンを標準としてShodex GPC SYSTEM−21(示差屈折率検出器)により、カラム温度40℃、クロロホルム溶離液で測定する。
ポリグリセリン脂肪酸エステルのエステル化率は、(構成脂肪酸のmol数/ポリグリセリンのmol数)×100(%)の式に基づいて計算される。
ポリグリセリンの重合度は、以下の式に基づいて、水酸基価より決定される。
GOHV=56110(n+2)/(74n+18)
GOHV:ポリグリセリンの水酸基価
n :ポリグリセリンの重合度
Dien−Starkトラップを設置した100リットル反応容器に、90モル%L−乳酸(不純物の含有量0.5モル%)10kgを150℃/50mmHgで3時間攪拌しながら水を留出させた後、錫末6.2gを加え、150℃/30mmHgでさらに2時間攪拌してオリゴマー化した。このオリゴマーに錫末28.8gとジフェニルエーテル21.1kgを加え、150℃/35mmHg共沸脱水反応を行い留出した水と溶媒を水分分離機で分離して、水層を逐次抜き出し、溶媒のみを反応器に戻した。2時間後(この時点で不純物の含有量は0.05モル%であった)、反応器に戻す有機溶媒を4.6kgのモレキュラーシーブ3Aを充填したカラムに通してから反応器に戻すようにして、150℃/35mmHgで反応を行い、ポリスチレン換算重量平均分子量12万のポリ乳酸溶液を得た。この溶液に脱水したジフェニルエーテル44kgを加え希釈した後、40℃まで冷却して、析出した結晶をろ過し、10kgのn−ヘキサンで3回洗浄して60℃/50mmHgで乾燥した。この粉末を0.5N−塩酸12kgとエタノール12kgを加え、35℃で1時間攪拌した後ろ過し、60℃/50mmHgで乾燥して、平均粒径50μmのポリ乳酸A粉末を6.1kg(収率85%)得た。このポリマーのポリスチレン換算重量平均分子量(Mw)は15万、D−体含有量は1.2%であった。
ポリグリセリン(平均重合度:10、デカグリセリン)と、表1に記載の構成脂肪酸を混合したものとを、不活性ガス中、リン酸、p−トルエンスルホン酸、又は苛性ソーダの存在下で、120〜260℃で加熱し生成水を系外に除去することによって、ポリグリセリン脂肪酸エステルを得た。
表2又は3に示す種類と量のポリ乳酸系樹脂、及び表2又は3に示す種類と量のポリグリセリン脂肪酸エステルをヘンシェルミキサーで混合した後、二軸押出し機「TEM−35B」(東芝機械社製)を用いて、140〜210℃にて溶融混練し、ペレット化した。得られたペレットを、Tダイが装着されたφ40mmの押出機(Placo社製)を用いて、180〜200℃で加熱溶融押出し、厚さ250μmの成形体(シート)を得た。
〔ポリ乳酸系樹脂〕
LACEA H−400:三井化学販売、ポリ乳酸(Mw=20万、D−体含有量1.8%)
LACEA H−440:三井化学販売、ポリ乳酸(Mw=20万、D−体含有量4.4%)
JIS K−7136に準じ、東京電色社製、Haze Meterを用いて、厚さ250μmのシートの濁度(%)を求める。
JIS K6732に準じて、厚さ250μmのシートを、東洋精機社製引張試験機を用いて、測定温度23℃、チャック間70mm、試験片幅10mm、試験速度200mm/minの条件で測定し、強度を求めて、引張物性を評価する。測定値が大きいほど引張物性(強度)が強いことを示す。なお、表中のMD/TDは、シートに対し引張試験の方向を意味するもので、シートを製造する際のシート流れに平行な方向をMD、垂直な方向をTDとしている。
厚さ250μmのシートを、高速衝撃試験機を用い、測定温度23℃、ストライカ径1/2inch、試験速度3m/minの条件で測定し、衝撃吸収エネルギー(ハイレートインパクト、mJ)を求めて、耐衝撃性を評価する。ハイレートインパクト(mJ)が大きいほど耐衝撃性が強いことを示し、100mJ以上のハイレートインパクトで良好な耐衝撃性を有すると判断することができる。
JIS P 8115に規定される方法に準じて測定する。試験片形状が長さ約90mm×幅15mm、厚さ250μmのシートを、MIT型耐折試験機を用い試験荷重1kg、折り曲げ角度を270度(左右135度)、折り曲げ速度を175回/分の条件下で測定し、シートが破断するまでの折り曲げ回数を求める。折り曲げ回数が多いほど、耐折強度が強いことを示す。なお、表中のMD/TDは、シートに対し耐折試験の方向を意味するもので、シートを製造する際のシート流れに平行な方向をMD、垂直な方向をTDとしている。
厚さ250μmのポリ乳酸系樹脂組成物のシートを圧空真空成形機を用いて、金型形状上部口径が100mm、底部口径が80mm、高さ25mm、絞り比0.25のトレーを成形した後、耳の部位を打抜き刃にて打ち抜く。打ち抜いた時のシート及び成形品の状況により、以下の基準に従って、二次加工性を評価する。
○:シート、成形品に割れは生じる事なく、良好に打抜きができる
×:打抜き時にシートあるいは成形品に割れや亀裂、白化が生じる
Claims (4)
- ポリ乳酸系樹脂及びポリグリセリン脂肪酸エステルを含有してなるポリ乳酸系樹脂組成物であって、該ポリグリセリン脂肪酸エステルの含有量が、ポリ乳酸系樹脂100重量部に対して0.1〜30重量部であり、かつ、ポリグリセリン脂肪酸エステルが、カプリル酸、カプリン酸、及びラウリン酸を構成脂肪酸として含有し、該ラウリン酸の含有量が構成脂肪酸中20mol%以上であり、平均重合度が10のポリグリセリンを含有し、さらに、ポリグリセリン脂肪酸エステルのエステル化率が50〜85%である、ポリ乳酸系樹脂組成物。
- 請求項1記載のポリ乳酸系樹脂組成物を成形してなる、ポリ乳酸系樹脂成形体。
- JIS規格 K7136に準拠した曇り度(Haze)が5%未満である、請求項2記載のポリ乳酸系樹脂成形体。
- 請求項1記載のポリ乳酸系樹脂組成物を含む複合体を成形してなる成形体。
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