JP2014019853A - 樹脂組成物、および、該樹脂組成物を成形してなる成形品 - Google Patents
樹脂組成物、および、該樹脂組成物を成形してなる成形品 Download PDFInfo
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- JP2014019853A JP2014019853A JP2012162853A JP2012162853A JP2014019853A JP 2014019853 A JP2014019853 A JP 2014019853A JP 2012162853 A JP2012162853 A JP 2012162853A JP 2012162853 A JP2012162853 A JP 2012162853A JP 2014019853 A JP2014019853 A JP 2014019853A
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- acid
- resin
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- aliphatic
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- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 36
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Landscapes
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Abstract
【解決手段】脂肪族ポリエステル系樹脂(A)、ポリ乳酸系樹脂(B)およびα−オレフィン−無水マレイン酸共重合体(C)を含有してなり、脂肪族ポリエステル系樹脂(A)の含有割合が80重量%超であり、ポリ乳酸系樹脂(B)の含有割合が20重量%未満であり、α−オレフィン−無水マレイン酸共重合体(C)の含有割合が、脂肪族ポリエステル系樹脂(A)とポリ乳酸系樹脂(B)との合計100重量部に対して、0.01重量部以上0.1重量部未満であることを特徴とする樹脂組成物、および、これを成形してなる成形品とする。
【選択図】なし
Description
[1]
脂肪族ポリエステル系樹脂(A)、ポリ乳酸系樹脂(B)およびα−オレフィン−無水マレイン酸共重合体(C)を含有してなり、脂肪族ポリエステル系樹脂(A)の含有割合が80重量%超であり、ポリ乳酸系樹脂(B)の含有割合が20重量%未満であり、α−オレフィン−無水マレイン酸共重合体(C)の含有割合が、脂肪族ポリエステル系樹脂(A)とポリ乳酸系樹脂(B)の合計100重量部に対して0.01重量部以上0.1重量部未満であることを特徴とする樹脂組成物。
[2]
脂肪族ポリエステル系樹脂(A)が、脂肪族ジオール単位と脂肪族ジカルボン酸単位とを含んでなることを特徴とする[1]に記載の樹脂組成物。
[3]
脂肪族ジオール単位が1,4−ブタンジオールで、脂肪族ジカルボン酸単位がコハク酸であることを特徴とする[2]に記載の樹脂組成物脂。
[4]
脂肪族ジオール単位が1,4−ブタンジオールで、脂肪族ジカルボン酸単位がコハク酸とアジピン酸であることを特徴とする[2]に記載の樹脂組成物脂。
[5]
脂肪族ポリエステル系樹脂(A)のコハク酸単位の含有量が、全脂肪族ジカルボン酸単位中50モル%以上95モル%以下であることを特徴とする[3]又は[4]に記載の樹脂組成物。
[6]
[1]から[5]のいずれかに記載の樹脂組成物を成形して得られる成形品。
[7]
[1]から[5]のいずれかに記載の樹脂組成物を成形して得られるフィルム。
本発明の樹脂組成物は、脂肪族ポリエステル系樹脂(A)、ポリ乳酸系樹脂(B)、α−オレフィン−無水マレイン酸共重合体(C)を含有してなり、脂肪族ポリエステル系樹脂(A)の含有割合が80重量%超であり、ポリ乳酸系樹脂(B)の含有割合が20重量%未満である樹脂組成物である。
脂肪族ポリエステル系樹脂(A)は、脂肪族ジオール単位と脂肪族ジカルボン酸単位とを含んでなる脂肪族ポリエステル系樹脂であることが好ましい。
−O−R1−O− (1)
−OC−R2−CO− (2)
式(1)中、R1は、2価の脂肪族炭化水素基を表す。式(2)中、R2は、2価の脂肪族炭化水素基を表す。
本発明において用いられるポリ乳酸系樹脂(B)は、乳酸モノマーを必須成分として重合したものであればよい。例えば、構造単位がL−乳酸であるポリL−乳酸、構造単位がD−乳酸であるポリD−乳酸、構造単位がL−乳酸およびD−乳酸であるポリDL−乳酸、並びにこれらの混合体を主成分とする重合体であることができる。
本発明において用いられるα−オレフィン−無水マレイン酸共重合体(C)は、下式A、BおよびCで示される繰り返し単位からなり、これらの単位のモル比A:B:Cが10〜50:40〜60:5〜40であって、重量平均分子量が1,000〜50,000である共重合体である。
CH2 =CHCH2 O(R4O)nR5 (3)
(ただし、R4は炭素数が2〜10の直鎖または分岐のアルキル基を示し、R5は炭素数1〜3のアルキル基またはアシル基を示し、nはオキシアルキレン基の平均付加モル数で1〜100である。)
本発明に係る樹脂組成物には、滑剤、フィラー(充填剤)、可塑剤、帯電防止剤、酸化防止剤、光安定剤、紫外線吸収剤、染料、顔料、加水分解防止剤等の各種添加剤や、ポリカプロラクトン、ポリアミド、ポリビニルアルコール、セルロースエステル等の合成樹脂や、澱粉、セルロース、紙、木粉、キチン・キトサン質、椰子殻粉末、クルミ殻粉末等の動物/植物物質微粉末、或いはこれらの混合物が「その他の成分」として含まれていてもよい。これらは、本発明の効果を損なわない範囲で任意に使用できる。これらは1種を単独で用いてもよく、2種以上を混合して使用してもよい。これら添加剤の添加量は、通常、樹脂組成物の物性を損なわないように、混合する化合物の総量が、樹脂組成物の総量に対して、0.01重量%以上40重量%以下であることが好ましい。
例えば、本発明に係る樹脂組成物に滑剤を含ませると、樹脂組成物の成形性を向上させることができる。
本発明に係る樹脂組成物にフィラーを含ませると、樹脂組成物の剛性を向上させることができる。また、樹脂組成物をフィルムとした場合にはフィルム同士のブロッキングを防止することができる。或いは、フィルムを袋に成形した場合に袋の口を開き易くすることもできる。さらに、フィルムや袋を着色し、遮光性や光反射性を向上させることもできる。
なお、樹脂組成物の流れ性が悪い場合は、可塑剤を加えるとよい。特に、樹脂組成物にフィラーを含ませた場合には、樹脂組成物の粘度が上昇して樹脂組成物の流れ性が悪くなる場合があり、樹脂組成物に可塑剤を加えることによって、これを改善することができる。
また、本発明に係る樹脂組成物には、帯電防止剤を含ませることもできる。帯電防止剤としては、本発明の効果を著しく損なわない限り任意のものを用いることができる。具体例としては、界面活性剤型のノニオン系、カチオン系、アニオン系が好ましい。
本発明の樹脂組成物は上記に記載した添加剤の他に、澱粉、耐光剤、紫外線吸収剤、熱安定剤、末端封止剤などを含有させることもできる。
本発明に係る樹脂組成物の製造方法としては、公知の手法を適用することができる。例えば、脂肪族ポリエステル系樹脂(A)、ポリ乳酸系樹脂(B)、および、α−オレフィン−無水マレイン酸共重合体(C)の原料をブレンドしたのち同一の押出機で溶融混合する方法、各々別々の押出機で溶融させた後に混合する方法等が挙げられる。押出機としては、単軸または2軸押出機が利用できる。また、脂肪族ポリエステル系樹脂(A)、ポリ乳酸系樹脂(B)および、α−オレフィン−無水マレイン酸共重合体(C)を混合して加熱溶融させたところに、その他成分を添加して配合することもできる。この際、その他成分を均一に分散させる目的で、ブレンド用オイル等を使用することもできる。
本発明の樹脂組成物から成形品を得る方法は、特に限定されることはなく、通常熱可塑性樹脂に採用されている各種成形方法を適用することができ、射出成形、射出吹込成形、射出圧縮成形、発泡成形などの射出成形法;パイプ・チューブ、異型品、電線被覆、Tダイ法フィルム・シート、インフレーションフィルム、ラミネート加工、モノフィラメントなどの押出成形法;ブロー成形法、真空成形法、カレンダー成形法、圧縮成形法などを挙げることができる。
本発明の樹脂成形品は、外観と透明性に優れ、適度な生分解性を有するという効果をより有効に活用するために、フィルムであることが好ましい。
・MFR値の測定
MFR値は、JIS K7210に基づき、メルトインデクサーを用いて190℃、荷重2.16kgにて測定した。
1H−NMRの測定では、試料約30mgを外径5mmのNMR試料管に量り取り、重クロロホルム0.75mLに加えて溶かした後に、Bruker社製AVANCE400分光計を用い、室温で1H−NMRスペクトルを測定した。化学シフトの基準は、テトラメチルシラン(TMS)を0.00ppmとした。
融点の測定は、パーキンエルマー(株)製示差走査熱量計,製品名:DSC7を用い、10mgのサンプルを流量50mL/分の窒素気流下で加熱溶融させた後、10℃/分の速度で冷却後、引き続き10℃/分の速度で昇温する際の融解ピーク温度を使用した。
製造例1
攪拌装置、窒素導入口、加熱装置、温度計および減圧用排気口を備えた反応容器に、原料としてコハク酸100重量部、1,4−ブタンジオール99.2重量部、リンゴ酸0.24重量部、酸化ゲルマニウムを予め1重量%溶解させた90%DL乳酸水溶液7.0重量部を仕込んだ。容器内容物を攪拌下、窒素ガスを導入し、窒素ガス雰囲気下120℃から反応を開始し、1時間40分かけて200℃まで昇温した。引き続き、1時間25分かけて230℃に昇温すると同時に1mmHg(133Pa)まで減圧し、230℃、1mmHg(133Pa)にて4時間重合を行い、脂肪族ポリエステル系樹脂を得た。以下、この脂肪族ポリエステル系樹脂を「樹脂1」と呼ぶことがある。
製造例1において、コハク酸100重量部、アジピン酸31.0重量部、1,4−ブタンジオール143重量部、リンゴ酸0.345重量部とした以外は製造例1と同様に重合を行い、ポリエステル樹脂を得た。以下、このポリエステル樹脂を「樹脂2」と呼ぶことがある。
製造例1と2で製造した樹脂1、樹脂2と、ポリ乳酸系樹脂(B)に該当する以下に示す「レイシアH−400」、および、α−オレフィン−無水マレイン酸共重合体(C)に該当する以下に示す「ダイヤカルナ 30」を用いて、下記表1に記載の含有比となるように配合し、設定温度200℃で二軸混練機(池貝鉄鋼社製PCM30)にて混練してペレット上の樹脂チップを得た。当該樹脂ペレットを用いて175℃でインフレーション成形し、21μm厚みのフィルムを作成した。
「ダイヤカルナ 30」:三菱化学社製のα−オレフィン−無水マレイン酸共重合体(α−オレフィンの平均炭素数48、重量平均分子量9,000、ケン化価約120mgKOH/g)
フィルムを20cm角に5枚切り出し、拡大鏡を使用して目視にて以下の基準に従って外観の評価を行った。100cm2当りの異物の数が20個未満を合格とした。
○:100cm2当りの異物の数が5個未満であった。
△:100cm2当りの異物の数が5個以上20個未満であった。
×:100cm2当りの異物の数が20個以上であった。
成形して得られたフィルムについて、JIS K7136に準拠して、ヘーズを測定した。当該ヘーズの値が小さいほど透明性が高いことを表す。
成形して得られたフィルムについて、JIS K7127に記載されている「試験片タイプ2」の試験片を打ち抜き刃にて打ち抜き、水分量を20重量%に調整した三菱化学(株)四日市事業所内の土中に該フィルムを埋没させた。生分解試験の温度条件は40℃で、埋設期間は7日、14日、21日、28日で、該フィルムを土中から取り出して外観を観察して、以下の基準に従って生分解性の程度を評価した。△が7日〜28日の間に現れるものを合格とした。
○:フィルムの外観に変化がなかった。
△:フィルムの外観に亀裂や細孔などの変化があった。
×:フィルムが元の形状を留めないほど大きく変化していた。
Claims (7)
- 脂肪族ポリエステル系樹脂(A)、ポリ乳酸系樹脂(B)およびα−オレフィン−無水マレイン酸共重合体(C)を含有してなり、
脂肪族ポリエステル系樹脂(A)の含有割合が80重量%超であり、ポリ乳酸系樹脂(B)の含有割合が20重量%未満であり、
α−オレフィン−無水マレイン酸共重合体(C)の含有割合が、脂肪族ポリエステル系樹脂(A)とポリ乳酸系樹脂(B)との合計100重量部に対して、0.01重量部以上0.1重量部未満であることを特徴とする樹脂組成物。 - 前記脂肪族ポリエステル系樹脂(A)が、脂肪族ジオール単位と脂肪族ジカルボン酸単位とを含んでなることを特徴とする請求項1に記載の樹脂組成物。
- 前記脂肪族ジオール単位が1,4−ブタンジオールで、前記脂肪族ジカルボン酸単位がコハク酸であることを特徴とする請求項2に記載の樹脂組成物。
- 前記脂肪族ジオール単位が1,4−ブタンジオールで、前記脂肪族ジカルボン酸単位がコハク酸とアジピン酸であることを特徴とする請求項2に記載の樹脂組成物。
- 前記脂肪族ポリエステル系樹脂(A)のコハク酸単位の含有量が、全脂肪族ジカルボン酸単位中50モル%以上95モル%以下であることを特徴とする請求項3又は4に記載の樹脂組成物。
- 請求項1から5のいずれかに記載の樹脂組成物を成形して得られる成形品。
- 請求項1から5のいずれかに記載の樹脂組成物を成形して得られるフィルム。
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