JP2017106025A - 農業廃棄物から得られる熱可塑性デンプン組成物 - Google Patents
農業廃棄物から得られる熱可塑性デンプン組成物 Download PDFInfo
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- JP2017106025A JP2017106025A JP2017017340A JP2017017340A JP2017106025A JP 2017106025 A JP2017106025 A JP 2017106025A JP 2017017340 A JP2017017340 A JP 2017017340A JP 2017017340 A JP2017017340 A JP 2017017340A JP 2017106025 A JP2017106025 A JP 2017106025A
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- starch
- glycerol
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- thermoplastic composition
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Abstract
Description
本発明は、熱可塑性デンプン組成物に関する。より具体的には開示された熱可塑性デンプン組成物は、最適化された工程の下、比較的少ないデンプン量を含有する農業廃棄物を利用して製造される。
デンプンは、主として2種の主要な多糖、即ち直鎖状に結合したアミロースおよび分枝状のアミロペクチンで構成された天然ポリマーである。デンプンは、天然の状況では顆粒形態で存在するが、熱可塑性挙動を有する。デンプンは、適切な可塑剤の存在下、90〜180℃の温度でせん断力に供されると、熱可塑性デンプン(TPS)として知られる融解されたプラスチック状態に変換することができる。熱可塑性デンプンでは、多糖と可塑剤の間の弱い水素結合が、本来の多糖間水素結合と置き換わっていて、熱可塑性デンプンを柔軟性および延性にしている。具体的には、可塑剤と多糖の間の新しい結合が、二次結合を大きく低減して、長鎖多糖を保持する。それを考慮すれば、デンプンは再生可能な供給源であり、熱可塑性デンプンは持続性のある生成物である。更にデンプンは、従来の合成プラスチックに比較して2つの重要な欠点、つまり高い水溶性および不十分な機械的強度を有する。TPSの機械的性質を改善して水吸収性を低下させるために、変性がTPSに対して施された。例えば欧州特許出願第0327505号には、TPSと水不溶性合成熱可塑性ポリマーとのポリマーブレンドが記載され、良好な機械的性質および低い水溶性を有する、得られたポリマー組成物が請求されている。Guyらは、カナダ特許出願第2060409号において、少なくとも1つのヒドロキシカルボン酸塩を含有する別のTPS由来熱成形化合物を請求しており、それには得られた化合物が広い温度範囲内で最大の損失正接を有することが請求されている。更にTPS変性は、国際公開第03074604号に見出すことができ、それには形成されたポリマーへの水吸収性を低下させるために可塑剤の代わりに相溶剤を用いて形成されたTPSグラフトポリマーが提供されている。実質的に水を含まない共連続TPSが、米国特許出願第6605657号に記載され、微粒子の充填剤により強化されたTPSが、別の米国特許出願第6231970号に開示されている。
本発明は、農工業廃棄物から得られる熱可塑性デンプン(TPS)組成物を提供することを目的とする。より正確には本発明で用いられる農工業廃棄物は、デンプン量が比較的低く、所望の性質を実現するために特別な加工段階に供されている。
本発明が、その目的を実施して上述の最終目的および利益、ならびにその本質を得るように良好に適合されることを、当業者は容易に理解するであろう。本明細書に記載された実施形態は、本発明の範囲の限定を意図するものではない。
試料1を調製するために、デンプン粕(廃棄物)を、120℃以下で10分間加熱することができる高速ミキサーで過酸化ジクミルの存在下、アルキルアミンおよびエステルのブレンドで前処理または官能化する。この前処理工程の後、二置換されたグリセロールをデンプン粕に添加して5分間混合した後、ステアリン酸カルシウム、ブチル化ヒドロキシトルエン、アセタートコポリマー、およびPPのような他の成分を添加して更に5分間混合した後、反応押出/配合工程を実施するために、混合された組成物を二軸押出機の重量式供給機に排出する。反応押出および配合工程の温度設定は、バレルでは140〜170℃であり、スクリュー速度は、200rpmである。その後、万能引張試験機を用いた機械的試験のために、二軸押出機から得られた樹脂を、80℃で最低でも2時間乾燥させた後、L/Dが25の単軸押出機を用いたシート押出により、厚さ0.5mmおよび幅370mmを有する押出シートを製造する。試験の前に、ダンベル状試験片を20℃/55%RHで48時間コンディショニングする。
(I)穀粒粉 (II)PS (III)無水マレイン酸グラフトPS (IV)アミドおよび脂肪酸誘導体 (V)シラノール (VI)過酸化ジクミル (VII)酸化PEワックス (VIII)ブチル化ヒドロキシトルエン
実施例1の試料1のカーボンフットプリント(発生地からポリマー工場の門まで)を、PAS 2050に従って計算した[1]。PAS 2050により、わずかな排出量、即ち全排出量の1%未満となる任意の単一供給源を排除することができる。しかしわずかな排出量の合計の割合が、全製品のカーボンフットプリントの5%を超える可能性はない。こうして表面改質剤、触媒、相溶剤および他の添加剤のカーボンフットプリントが、除外された。
Claims (27)
- デンプン含有農業廃棄物から形成される熱可塑性組成物であって、
乾重量で50%未満のデンプン量を含む、45〜70重量%のデンプン含有農業廃棄物と、
25〜50重量%の熱可塑性合成ポリマーと、
0.01〜5重量%の開始剤と、
0.01〜10重量%の可塑剤と、
少なくとも1重量%のカップリング剤との、
加熱配合された混合物を含む、熱可塑性組成物。 - 前記加熱配合された混合物が、充填剤材料、抗酸化剤、および/または着色剤の1つまたはそれ以上をさらに含む、請求項1に記載の熱可塑性組成物。
- 前記乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物が、乾重量で20%未満のアミロース量を含む、請求項1に記載の熱可塑性組成物。
- 前記加熱配合された混合物が、繊維状天然充填剤材料をさらに含む、請求項1に記載の熱可塑性組成物。
- 前記加熱配合された混合物が、粉砕された粉末の天然充填剤材料をさらに含む、請求項1に記載の熱可塑性組成物。
- 前記加熱配合された混合物が、170ミクロン以下の平均粒径を有する天然充填剤材料をさらに含む、請求項1に記載の熱可塑性組成物。
- 0.01〜10重量%の可塑剤をさらに含む、請求項1に記載の熱可塑性組成物。
- 前記可塑剤が、糖アルコール、ポリオール、ソルビトールエトキシラート、グリセロールエトキシラート、ペンタエリトリトールエトキシラート、ソルビトールアセタート、ペンタエリトリトールアセタート、水、尿素、尿素誘導体、糖アルコールの無水物、フタル酸エステル、コハク酸ジメチル、コハク酸ジエチル、コハク酸ジメチルのエステル、コハク酸ジエチルのエステル、一酢酸グリセロール、二酢酸グリセロール、三酢酸グリセロール、グリセロール一酸エステル(glycerol mono acid esters)、クエン酸エステル、アジピン酸エステル、ステアリン酸エステル、オレイン酸エステル、エチレンとアクリル酸とのコポリマー、マレイン酸グラフトポリエチレン、ポリブタジエン−co−アクリル酸、ポリブタジエン−co−マレイン酸、プロピレン−co−アクリル酸、ポリプロピレン−co−マレイン酸、アジピン酸誘導体、安息香酸誘導体、クエン酸誘導体、リン酸誘導体、セバシン酸誘導体、モノグリセリド、ジグリセリド、アセチル化モノグリセリド、アセチル化モノステアリン酸グリセロール、アセチル化グリセロールモノエステル−12−ヒドロキシステアリン酸、グリセロールの酢酸エステル、モノプロピオン酸グリセロール、ジプロピオン酸グリセロール、トリプロピオン酸グリセロール、ブタノアート、ステアラート、アルキルアミド、トリメチロールプロパン、ジメチルスルホキシド、マンニトールモノアセタート、および/またはマンニトールモノエトキシラートの1つまたはそれ以上である、請求項7に記載の熱可塑性組成物。
- 前記熱可塑性合成ポリマーが、ポリビニルアルコールまたは酢酸ポリビニルを含み得るビニルポリマー;ポリビニルカルバゾール;ポリスチレン;ポリ乳酸;ポリ(ヒドロキシブチラート)またはポリヒドロキシルアジパートを含み得るポリエステル;ポリ(アルキレンテレフタラート);ポリアクリロニトリル;ポリ(アルキレンオキシド);ポリイミド;ポリアリールエーテル;ポリカルボナート;ポリプロピレン、ポリエチレンまたはポリイソブチレンを含み得るポリオレフィン;アクリロニトリルブタジエンスチレンコポリマー、スチレンアクリロニトリルコポリマー、スチレンエチレンブタジエンコポリマーまたはスチレンエチレンブチレンスチレンコポリマーを含み得るスチレンコポリマー;エチレン酢酸ビニルコポリマー;エチレンビニルアルコールコポリマー;エチレンアクリル酸コポリマー;エチレンアクリル酸エチルコポリマー、エチレンアクリル酸メチルコポリマー;アクリロニトリル/ブタジエン/スチレンコポリマー;スチレンアクリロニトリルコポリマー;ならびにそれらの組み合わせの1つまたはそれ以上である、請求項1に記載の熱可塑性組成物。
- 前記加熱配合された混合物が、少なくとも25重量%の天然充填剤材料をさらに含む、請求項1に記載の熱可塑性組成物。
- 前記加熱配合された混合物が、木材、ケナフ、ヤシ殻、ココナッツ殻およびモミ殻の少なくとも1つを含む天然充填剤材料をさらに含む、請求項1に記載の熱可塑性組成物。
- 前記加熱配合された混合物が、0.2〜1重量%の抗酸化剤をさらに含む、請求項1に記載の熱可塑性組成物。
- 前記加熱配合された混合物が、3〜10重量%の着色剤をさらに含む、請求項1に記載の熱可塑性組成物。
- 農業廃棄物から熱可塑性組成物を形成する方法であって、
乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物と可塑剤とを混合して第1の混合物を形成するステップと、
合成ポリマーとカップリング剤とを混合して第2の混合物を形成するステップと、
前記第1の混合物と前記第2の混合物とを配合して熱可塑性組成物を形成するステップと、
を含む、方法。 - 前記配合が前記第1の混合物と前記第2の混合物とを混合すること及び共押出することを含む、請求項14に記載の方法。
- 前記配合が前記第1の混合物と前記第2の混合物とを押出機中で混合することおよび前記押出機から前記熱可塑性組成物を押出することを含む、請求項14に記載の方法。
- 前記配合が前記第1の混合物と前記第2の混合物とを二軸押出機中で混合することおよび前記二軸押出機から前記熱可塑性組成物を押出することを含む、請求項14に記載の方法。
- 前記配合が前記第1の混合物と前記第2の混合物とを押出機中で混合し、前記押出機から前記熱可塑性組成物を押出することを含み、前記押出機が30〜60の長さ/直径率を有する、請求項14に記載の方法。
- 前記配合が140℃またはそれ以上の温度で実施される、請求項14に記載の方法。
- 前記第1の混合物の形成が、充填剤材料を、前記乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物および前記可塑剤と混合することを含む、請求項14に記載の方法。
- 前記第1の混合物の形成が、天然充填剤材料を、前記乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物および前記可塑剤と混合することを含む、請求項14に記載の方法。
- 前記第1の混合物の形成が、粉砕された粉末の天然充填剤材料を、前記乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物および前記可塑剤と混合することを含む、請求項14に記載の方法。
- 前記第1の混合物の形成が、繊維状天然充填剤材料を、前記乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物および前記可塑剤と混合することを含む、請求項14に記載の方法。
- 前記第1の混合物の形成が、170ミクロン以下の平均粒径を有する天然充填剤材料を、前記乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物および前記可塑剤と混合することを含む、請求項14に記載の方法。
- 前記合成ポリマーが、ポリビニルアルコールまたは酢酸ポリビニルを含み得るビニルポリマー;ポリビニルカルバゾール;ポリスチレン;ポリ乳酸;ポリ(ヒドロキシブチラート)またはポリヒドロキシルアジパートを含み得るポリエステル;ポリ(アルキレンテレフタラート);ポリアクリロニトリル;ポリ(アルキレンオキシド);ポリイミド;ポリアリールエーテル;ポリカルボナート;ポリプロピレン、ポリエチレンまたはポリイソブチレンを含み得るポリオレフィン;アクリロニトリルブタジエンスチレンコポリマー、スチレンアクリロニトリルコポリマー、スチレンエチレンブタジエンコポリマーまたはスチレンエチレンブチレンスチレンコポリマーを含み得るスチレンコポリマー;エチレン酢酸ビニルコポリマー;エチレンビニルアルコールコポリマー;エチレンアクリル酸コポリマー;エチレンアクリル酸エチルコポリマー、エチレンアクリル酸メチルコポリマー;アクリロニトリル/ブタジエン/スチレンコポリマー;スチレンアクリロニトリルコポリマー;ならびにそれらの組み合わせの1つまたはそれ以上である、請求項14に記載の方法。
- 前記乾重量で50%未満のデンプン量を含むデンプン含有農業廃棄物が乾重量で20%未満のアミロース量を含む、請求項14に記載の方法。
- 前記可塑剤が、糖アルコール、ポリオール、ソルビトールエトキシラート、グリセロールエトキシラート、ペンタエリトリトールエトキシラート、ソルビトールアセタート、ペンタエリトリトールアセタート、水、尿素、尿素誘導体、糖アルコールの無水物、フタル酸エステル、コハク酸ジメチル、コハク酸ジエチル、コハク酸ジメチルのエステル、コハク酸ジエチルのエステル、一酢酸グリセロール、二酢酸グリセロール、三酢酸グリセロール、グリセロール一酸エステル(glycerol mono acid esters)、クエン酸エステル、アジピン酸エステル、ステアリン酸エステル、オレイン酸エステル、エチレンとアクリル酸とのコポリマー、マレイン酸グラフトポリエチレン、ポリブタジエン−co−アクリル酸、ポリブタジエン−co−マレイン酸、プロピレン−co−アクリル酸、ポリプロピレン−co−マレイン酸、アジピン酸誘導体、安息香酸誘導体、クエン酸誘導体、リン酸誘導体、セバシン酸誘導体、モノグリセリド、ジグリセリド、アセチル化モノグリセリド、アセチル化モノステアリン酸グリセロール、アセチル化グリセロールモノエステル−12−ヒドロキシステアリン酸、グリセロールの酢酸エステル、モノプロピオン酸グリセロール、ジプロピオン酸グリセロール、トリプロピオン酸グリセロール、ブタノアート、ステアラート、アルキルアミド、トリメチロールプロパン、ジメチルスルホキシド、マンニトールモノアセタート、および/またはマンニトールモノエトキシラートの1つまたはそれ以上である、請求項14に記載の方法。
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