JP2021503394A - 3d印刷のための改善されたフィラメント - Google Patents
3d印刷のための改善されたフィラメント Download PDFInfo
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- JP2021503394A JP2021503394A JP2020527011A JP2020527011A JP2021503394A JP 2021503394 A JP2021503394 A JP 2021503394A JP 2020527011 A JP2020527011 A JP 2020527011A JP 2020527011 A JP2020527011 A JP 2020527011A JP 2021503394 A JP2021503394 A JP 2021503394A
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- 238000010146 3D printing Methods 0.000 title claims abstract description 23
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- 239000000835 fiber Substances 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000001913 cellulose Substances 0.000 claims abstract description 25
- 229920002678 cellulose Polymers 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 19
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- 229920000573 polyethylene Polymers 0.000 claims abstract description 17
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- 239000000203 mixture Substances 0.000 claims abstract description 16
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- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 11
- 229920002959 polymer blend Polymers 0.000 claims abstract description 7
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims abstract description 6
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- VBUBYMVULIMEHR-UHFFFAOYSA-N propa-1,2-diene;prop-1-yne Chemical compound CC#C.C=C=C VBUBYMVULIMEHR-UHFFFAOYSA-N 0.000 description 13
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
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Abstract
Description
本出願は、2017年11月16日に出願された米国仮特許出願第62/587,233号への優先権を主張し、その全内容は参照により本明細書に組み込まれる。
一部の実施形態では、複合材は、「高速マスターバッチ製造プロセス」を使用して調製され得る。例えば、ポリマーマトリクスおよび複数の繊維は、オーブン中で、例えば、90℃を超える温度で少なくとも1時間(例えば、105℃で2時間)、乾燥することができる。例えば、ポリマーマトリクスは、(i)ポリプロピレン(PP)およびポリエチレン(PE)[例えば、高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)]を含むポリマーブレンド、(ii)改質(例えば、耐衝撃性改良)ポリプロピレンコポリマー、ならびに/または(iii)ポリプロピレンランダムコポリマーからなる群より選択される1種または複数のメンバーを含む組成物を有し得る。例えば、ポリマーマトリクスは、非限定例として、70/30、75/25、80/20、85/15または90/10のPP/PEの組成物を有し得る。一部の実施形態では、複数の繊維は、複数の天然セルロースナノファイバー(例えば、セルロースナノフィブリル)であり得るまたはこれを含み得る。例えば、繊維は、約1000nm未満(例えば、900nm、800nm、700nm、600nm、500nm、400nm、300nm、200nmまたは100nm未満)の平均直径を有し得る。
一部の実施形態では、複合材のフィラメントは、さらなる改質なしに印刷され得る。一部の実施形態では、印刷の間に、プレートが比較的高温で維持されて、複合材の結晶化および収縮が減少し得る。
実施形態の一例では、iPPホモポリマー(H19G−01)を、Ineos Olefins & Polymers USA(League City、TX)から得た。iPPホモポリマー(H19G−01)は、0.91g/cm3の密度、160℃の融点、19g/10分(230℃/2.16kg)のメルトフローインデックス、37.2MPaの引張強さ(降伏)、1.78GPaの曲げ率および2.8kJ/m2のノッチ付きアイゾッド衝撃強さを有する。約1.0重量%の無水マレイン酸含有量を有するMAPPペレット(Polybond 3200)をChemtura Corporation(Lawrenceville、GA)から得た。MAPPペレット(Polybond 3200)は、0.91g/cm3の密度および115g/10分(190℃/2.16kg)のMFIを有する。セルロースナノフィブリル(CNF)(約3重量%)の懸濁物を、メイン大学のProcess Development Centerから得た。CNF粉末を、パイロットスケールの噴霧乾燥機(GEA−Niro、Germany)を使用して1.2重量%CNF懸濁物を噴霧乾燥することによって得た。乾燥は、250℃の入口温度、30,000rpmのディスク回転速度および0.4L/分のポンプ供給速度で実施した。
非等温結晶化研究を、TA Instruments Q 2000 Calorimeter(New Castle、Delaware、USA)を使用して実施した。各試料約1mg〜2mgを、対応するペレットから切断し、Tzeroアルミニウム製鍋に密封した。試料を、まず50℃/分の加熱速度で190℃に加熱し、190℃で5分間維持して熱履歴を最小にした。次いで、試料を、4つの冷却速度(5、10、15および20℃/分)で50℃に冷却した。冷却速度を、装置の冷却能および試験の温度に基づいて選択した。示差走査熱量測定(DSC)のために、最速の冷却速度である20℃/分を使用して50℃の温度にした。20℃/分を超える冷却速度は、これらの研究の例において使用した装置では維持できなかった。次いで、試料を、10℃/分の速度で50℃から190℃に再加熱して、溶融情報を得た。すべての測定は、50mL/分の流量の窒素雰囲気下で実施した。
に基づいて計算した。異なる冷却速度について異なる試料を使用した。
から計算することができる結晶化温度の関数である。Xtの値はまた、T対t間の関係による結晶化時間に関連し得る:
t=(T0−T)/λ
[式中、λは冷却速度である]。
Jeziorny法
等温および非等温結晶化プロセスの両方は、Avramiのモデルによって記載され得る。相対結晶化度(Xt)および結晶化経過時間(t)間の関係は以下の通りである:
1−Xt=exp(−Ktn)
ln[−ln(1−Xt)]=nln t+ln K
ln KJ=(ln K)/λ
Ozawa法は、非等温結晶化プロセスを、結晶化期間にわたる無限小時間に生じる多くの等温結晶化プロセスの和としてモデリングする。この数学的モデルもまた、Avramiの等式:
1−Xt=exp[−K(T)/λm]
[式中、K(T)は、結晶化定数であり、結晶化温度に依存し、mは、Ozawaベキ指数である]
に基づく。上の等式から、両対数形態も得ることができる:
ln[−ln(1−Xt)]=ln K(T)−mln(λ)
Liuらは、AvramiおよびOzawa法を組み合わせることによって非等温結晶化動力学を正確に記載する方法を提案した[30]。等式は、以下である:
ln λ=lnF(T)−αlnt、
F(T)=[K(T)/K]1/m、
α=n/m
[式中、F(T)は、ある特定の結晶化度を有するポリマーについての単位結晶化時間の間に必要とされる冷却速度である]。より小さい値のF(T)は、より速い結晶化速度に対応し得る。KはAvrami定数であり、nはAvramiベキ指数であり、K(T)はOzawa定数であり、mはOzawaベキ指数であり、λは冷却速度である。図3は、ln λ対ln tのプロットを示している。αおよびln F(T)の値は、これらの曲線の傾きおよび切片から得た。
ポリマー結晶化の間の有効活性化エネルギー(ΔE)は、高分子セグメントを結晶の表面に輸送するために必要なエネルギーの尺度を提供する。Kissingerの等式を使用して、結晶化ピーク温度(Tp)および冷却速度(λ)からΔEを計算した。Kissinger法の等式は以下である:
iPP/CNF複合材の例の結晶モルホロジーを評価するために、ME520 Series偏光顕微鏡(PLM)(AmScope、USA)を利用した。Sorvall MT2−B Ultramicrotomeを使用して、3μm厚の切片を、射出成形試験片の断面から得た。各切片をガラススライドとカバーガラスの間に置き、次いで、200℃のホットプレート(Thermo Scientific)に2分間移した後、室温に冷却した。
熱膨張測定を、ASTM D 696−16に従って、流れ方向に沿って射出成形試験片に対して行った。iPPは、0℃に近いガラス転移温度を有することから、熱膨張測定を、−30℃〜30℃の温度範囲で別々に実施した。iPPのTgよりも上での熱膨張は、Tg未満での熱膨張よりも大きかった。この研究について、Tgよりも上での熱膨張が、より目的のものであると考えた。熱膨張係数を計算するために使用した等式は以下であった:
α=ΔL/L0ΔT
[式中、ΔLは、温度変化によって引き起こされた、試験片の長さの変化であり、L0は室温での試験片の長さであり、ΔTは温度(30℃)の変化であった]。条件に関して、3回の反復を測定した。
(項目1)
ポリマーマトリクスを含む複合材(例えば、付加製造、例えば、溶融層モデリングのための、例えば、複合熱可塑性材料)。
(項目2)
前記ポリマーマトリクスが、(i)ポリプロピレン(PP)およびポリエチレン(PE)[例えば、高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)]を含むポリマーブレンド、(ii)改質(例えば、耐衝撃性改良)ポリプロピレンコポリマーならびに/または(iii)ポリプロピレンランダムコポリマーからなる群より選択される1種または複数のメンバーを含む組成物を有する、項目1に記載の複合材。
(項目3)
前記ポリマーマトリクスのメルトフローインデックス(MFI)が、約5〜30g/10分の範囲である、先行する項目のいずれか1項に記載の複合材。
(項目4)
複数の繊維(例えば、天然セルロースナノファイバー)をさらに含む、先行する項目のいずれか1項に記載の複合材。
(項目5)
前記複数の繊維が、複数の天然セルロースナノファイバー(例えば、セルロースナノフィブリル)(例えば、ナノファイバーの平均直径が約1000nm未満である天然セルロースナノファイバー)を含む、項目4に記載の複合材。
(項目6)
前記複数の繊維の重量パーセントが、3%〜30%(前記複合材の総重量に対して)の範囲である、項目4または5に記載の複合材。
(項目7)
先行する項目のいずれか1項に記載の複合材を含むペレット。
(項目8)
先行する項目のいずれか1項に記載の複合材を含むフィラメント。
(項目9)
項目7に記載のフィラメントを用いて3D印刷することを含む、3D印刷の方法。
(項目10)
基材(例えば、印刷が実施されるプレート)の温度が、少なくとも35℃(例えば、比較的高温で維持して、複合材の結晶化および収縮を減少させる)である、項目9に記載の方法。
(項目11)
項目9または10に記載の方法による3D印刷のためのシステム。
(項目12)
項目8に記載のフィラメントを調製するためのシステム。
Claims (12)
- ポリマーマトリクスを含む複合材(例えば、付加製造、例えば、溶融層モデリングのための、例えば、複合熱可塑性材料)。
- 前記ポリマーマトリクスが、(i)ポリプロピレン(PP)およびポリエチレン(PE)[例えば、高密度ポリエチレン(HDPE)、低密度ポリエチレン(LDPE)、直鎖状低密度ポリエチレン(LLDPE)]を含むポリマーブレンド、(ii)改質(例えば、耐衝撃性改良)ポリプロピレンコポリマーならびに/または(iii)ポリプロピレンランダムコポリマーからなる群より選択される1種または複数のメンバーを含む組成物を有する、請求項1に記載の複合材。
- 前記ポリマーマトリクスのメルトフローインデックス(MFI)が、約5〜30g/10分の範囲である、先行する請求項のいずれか1項に記載の複合材。
- 複数の繊維(例えば、天然セルロースナノファイバー)をさらに含む、先行する請求項のいずれか1項に記載の複合材。
- 前記複数の繊維が、複数の天然セルロースナノファイバー(例えば、セルロースナノフィブリル)(例えば、ナノファイバーの平均直径が約1000nm未満である天然セルロースナノファイバー)を含む、請求項4に記載の複合材。
- 前記複数の繊維の重量パーセントが、3%〜30%(前記複合材の総重量に対して)の範囲である、請求項4または5に記載の複合材。
- 先行する請求項のいずれか1項に記載の複合材を含むペレット。
- 先行する請求項のいずれか1項に記載の複合材を含むフィラメント。
- 請求項7に記載のフィラメントを用いて3D印刷することを含む、3D印刷の方法。
- 基材(例えば、印刷が実施されるプレート)の温度が、少なくとも35℃(例えば、比較的高温で維持して、複合材の結晶化および収縮を減少させる)である、請求項9に記載の方法。
- 請求項9または10に記載の方法による3D印刷のためのシステム。
- 請求項8に記載のフィラメントを調製するためのシステム。
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JP2017065111A (ja) * | 2015-09-30 | 2017-04-06 | 三菱樹脂株式会社 | 付加製造技術用熱可塑性樹脂フィラメント |
JP2017128073A (ja) * | 2016-01-22 | 2017-07-27 | 国立大学法人岐阜大学 | 立体構造物の製造方法 |
JP2017170881A (ja) * | 2016-03-18 | 2017-09-28 | スターライト工業株式会社 | 3dプリンタ用造形材料、その製造方法、および三次元造形物 |
CN106243508A (zh) * | 2016-08-29 | 2016-12-21 | 山东三岭汽车内饰有限公司 | 一种轻量化环保新型汽车内饰材料 |
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WO2023013514A1 (ja) * | 2021-08-06 | 2023-02-09 | 国立大学法人静岡大学 | セルロース含有樹脂組成物、3dプリンタ用フィラメント、及びセルロース含有樹脂組成物の製造方法 |
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EP3710237A1 (en) | 2020-09-23 |
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