JP6356700B2 - 連続的液体界相印刷 - Google Patents
連続的液体界相印刷 Download PDFInfo
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- JP6356700B2 JP6356700B2 JP2015557154A JP2015557154A JP6356700B2 JP 6356700 B2 JP6356700 B2 JP 6356700B2 JP 2015557154 A JP2015557154 A JP 2015557154A JP 2015557154 A JP2015557154 A JP 2015557154A JP 6356700 B2 JP6356700 B2 JP 6356700B2
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Description
本出願は、共同所有の、2013年12月23日に出願された米国仮特許出願第61/919,903号(事件整理番号1151−3PR2)、2013年8月14日に出願された米国仮特許出願第61/865,841号(事件整理番号1151−3PR)および2013年2月12日に出願された米国仮特許出願第61/763,746号(事件整理番号1151−2PR)の利益を主張し、これらの開示は、それら全体が参照により本願明細書の一部となすものとする。
本発明を可能にするために、任意の適切な重合性液体を使用することができる。この液体(本明細書において「液体樹脂」、「インク」または単に「樹脂」と称する場合もある)は、モノマー、特に光重合性モノマーおよび/またはフリーラジカル重合性モノマーならびに例えばフリーラジカル開始剤等の適切な開始剤、ならびにこれらの組み合わせを含むことができる。例として、アクリル系樹脂、メタクリル系樹脂、アクリルアミド、スチレン系樹脂、オレフィン、ハロゲン化オレフィン、環状アルケン、無水マレイン酸、アルケン、アルキン、一酸化炭素、官能性オリゴマー、多官能性硬化部位モノマー、官能性PEG等およびこれらの組み合わせが挙げられるがこれらに限定されない。液体樹脂、モノマーおよび開始剤の例として、米国特許第8,232,043号、米国特許第8,119,214号、米国特許第7,935,476号、米国特許第7,767,728号、米国特許第7,649,029号、国際公開第2012129968号、中国特許出願公開第102715751号明細書、特開2012−210408号公報に記載されたものが挙げられるがこれらに限定されない。
上記で述べたいくつかの実施形態では、重合性液体は、フリーラジカル重合性液体(この場合、阻害剤は下記に記載する酸素であることができる)を含むが、その他の実施形態では、重合性液体は、酸触媒のまたはカチオン性の重合性液体を含む。そのような実施形態では、重合性液体は、エポキシド基、ビニルエーテル基等の酸触媒反応に適した基を含有するモノマーを含む。このため、適切なモノマーとして、オレフィン、例えばメトキシエテン、4−メトキシスチレン、スチレン、2−メチルプロパ−1−エン(2-methylprop-1-ene)、1,3−ブタジエン等;複素環式モノマー(ラクトン、ラクタムおよび環式アミンを含む)、例えばオキシラン、チエタン(thietane)、テトラヒドロフラン、オキサゾリン(oxazoline)、1,3,ジオキセパン(1,3, dioxepane)、オキセタン−2−オン(oxetan-2-one)等、およびこれらの組み合わせが挙げられる。酸触媒の重合性液体に含まれる適切な(一般にイオン性のまたは非イオン性の)光酸発生剤(photoacid generator:PAG)の例として、オニウム塩、スルホニウム塩およびヨードニウム塩等、例えばジフェニルヨージドヘキサフルオロホスフェート、ジフェニルヨージドヘキサフルオロアルセネート(diphenyl iodide hexafluoroarsenate)、ジフェニルヨージドヘキサフルオロアンチモネート、ジフェニルp−メトキシフェニルトリフレート、ジフェニルp−トルエニルトリフレート、ジフェニルp−イソブチルフェニルトリフレート、ジフェニルp−tert−ブチルフェニルトリフレート、トリフェニルスルホニウムヘキサフルオロホスフェート(triphenylsulfonium hexafluororphosphate)、トリフェニルスルホニウムヘキサフルオロアルセネート、トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムトリフレート、ジブチルナフチルスルホニウムトリフレート(dibutylnaphthylsulfonium triflate)等、およびこれらの混合物が挙げられるがこれらに限定されない。例えば、米国特許第7,824,839号、米国特許第7,550,246号、米国特許第7,534,844号、米国特許第6,692,891号、米国特許第5,374,500号および米国特許第5,017,461号を参照されたい。また、Photoacid Generator Selection Guide for the electronics industry and energy curable coatings(BASF 2010)も参照されたい。
いくつかの実施形態では、適切な樹脂として、ポリ(エチレングリコール)(PEG)およびゼラチンのような光硬化性ヒドロゲルが挙げられる。PEGヒドロゲルは、増殖因子等の様々な生物学的製剤を送達するために使用されているが、連鎖成長重合(chain growth polymerization)により架橋されているPEGヒドロゲルが直面している大きな課題は、不可逆的なタンパク質の損傷(irreversible protein damage)の可能性である。持続的な送達を可能にする光重合の前に、親和性結合(affinity binding)しているペプチド配列をモノマー樹脂溶液へ包含(inclusion)させることにより、光重合したPEGジアクリレートヒドロゲルからの生物学的製剤の最大放出の状態(condition)を増強することができる。ゼラチンは、食品業界、美容業界、製薬業界および写真業界で頻繁に使用されるバイオポリマーである。ゼラチンは、コラーゲンの熱変性または化学的分解および物理的分解により得られる。ゼラチンには、動物、魚およびヒトに見られるものを含む3種が存在する。冷水魚の皮膚由来のゼラチンは、薬学的用途での使用に安全であると考えられている。UV光または可視光を使用して、適切に修飾したゼラチンを架橋させることができる。ゼラチンを架橋させる方法は、ローズベンガル等の染料由来の誘導体を硬化させることを含む。
適切な樹脂として、光硬化性シリコーンが挙げられる。Siliopren(商標)UV Cure Silicone Rubber等のUV硬化シリコーンゴムを、LOCTITE(商標)Cure Silicone接着封止剤(adhesive sealant)として使用することができる。用途として、光学機器、診察用のおよび手術用の器具、外部照明および筐体、電気コネクタ/センサ、光ファイバーならびにガスケットが挙げられる。
生分解性のネジ(screw)およびステント(stent)のような、薬剤を送達するためのまたは一時的な実行用途のための埋め込み型デバイスにとって、生分解性樹脂は特に重要である(米国特許第7,919,162号、米国特許第6,932,930号)。乳酸およびグリコール酸(PLGA)の生分解性コポリマーをジメタクリル酸PEGに溶解させて、使用に適した透明樹脂を得ることができる。ポリカプロラクトンおよびPLGAオリゴマーをアクリル基またはメタクリル基で官能化させて、これらを使用に効果的な樹脂にすることができる。
特に有用な樹脂は、光硬化性ポリウレタンである。(1)脂肪族ジイソシアネートに基づくポリウレタン、即ちポリ(ヘキサメチレンイソフタレートグリコール)および任意選択的に1,4−ブタンジオール、(2)多官能性アクリル酸エステル、(3)光開始剤、および(4)抗酸化剤を含む光重合性ポリウレタン組成物を配合し、その結果、硬質で耐摩耗性のおよび耐汚染性の材料を得ることができる(米国特許第4,337,130号)。光硬化性の熱可塑性ポリウレタンエラストマーは、鎖延長剤(chain extender)として光反応性ジアセチレンジオールを包含する。
いくつかの実施形態では、高性能樹脂を使用する。時として、そのような高性能樹脂は、上記で述べたようにおよび下記で更に論じるように、融解するためにおよび/またはこの高性能樹脂の粘度を低下させるために加熱の使用を必要とする場合がある。そのような樹脂の例として、米国特許第7,507,784号、米国特許第6,939,940号に記載されている、エステル、エステルイミドおよびエステルアミドオリゴマーの液晶ポリマーと称される場合がある、高性能樹脂用の樹脂材料が挙げられるがこれに限定されない。そのような樹脂が高温での熱硬化性樹脂として用いられる場合があることから、本発明では、そのような樹脂は、下記で更に論じるように、照射により架橋を開始するために、適切な光開始剤、例えばベンゾフェノン開始剤、アントラキノン開始剤およびフルオレノン(fluoroenone)開始剤(これらの誘導体を含む)を更に含む。
歯科用途に特に有用な樹脂として、EnvisionTEC’s Clear Guide、EnvisionTEC’s E−Denstone Materialが挙げられる。補聴器産業に特に有用な樹脂として、EnvisionTEC’s e−Shell 300 Seriesの樹脂が挙げられる。特に有用な樹脂として、成型/鋳造用途で加硫ゴムと直接使用するためのEnvisionTEC’s HTM140IV High Temperature Mold Materialが挙げられる。頑丈で硬い部品を製造するのに特に有用な材料として、EnvisionTEC’s RC31樹脂が挙げられる。インベストメント鋳造用途(investment casting application)に特に有用な樹脂として、EnvisionTEC’s Easy Cast EC500が挙げられる。
液体樹脂または重合性材料は、それらに懸濁されているまたは分散されている固体粒子を有していてもよい。製作する最終産物に応じて、任意の適切な固体粒子を使用することができる。この粒子は、金属、有機/ポリマー、無機、またはこれらの組成物もしくは混合物であることができる。この粒子は、非導電性、半導電性または導電性(金属導体および非金属導体またはポリマー導体を含む)であることができ、この粒子は磁性、強磁性、常磁性または非磁性であることができる。この粒子は、球状、楕円状、円柱形等の任意の適切な形状であることができる。この粒子は、下記でも論じるように液体樹脂中に溶解して可溶化され得るが、この粒子は、下記に記載する活性剤または検出可能な化合物を含むことができる。例えば、磁性のまたは常磁性の粒子またはナノ粒子を用いることができる。
本発明で使用する阻害剤または重合阻害剤は、液体または気体の形態であることができる。いくつかの実施形態では、気体の阻害剤が好ましい。具体的な(particular)阻害剤を、重合するモノマーおよび重合反応に応じて決めることができる。フリーラジカル重合モノマーの場合、阻害剤は、好都合なことに酸素であることができ、酸素を、空気、酸素に富む気体(しかしながらいくつかの実施形態では、任意選択的に、可燃性を低減するために追加の不活性ガスを好ましくは含有する)またはいくつかの実施形態では純粋な酸素ガス等の気体の形態で供給することができる。例えば、モノマーが光酸発生開始剤により重合されるという代替の実施形態では、阻害剤は、塩基、例えばアンモニア、微量アミン(例えばメチルアミン、エチルアミン、ジアルキルアミンおよびトリアルキルアミン、例えばジメチルアミン、ジエチルアミン、トリメチルアミン、トリエチルアミン等)または二酸化炭素、およびこれらの混合物または組み合わせであることができる。
いくつかの実施形態では、重合性液体は、この重合性液体中に「粒子」として生細胞を保有することができる。そのような重合性液体は、一般に水性である、酸素化(oxygenate)され得る、および生細胞が不連続相(discrete phase)である「乳濁液(emulsion)」と見なされ得る。適切な生細胞は、植物細胞(例えば単子葉植物、双子葉植物)、動物細胞(例えば哺乳類細胞、鳥類細胞、両生類細胞、爬虫類細胞)、微生物細胞(例えば原核生物、真核生物、原生動物等)等であることができる。生細胞は、任意の種類の組織(例えば血液、軟骨、骨、筋肉、内分泌腺、外分泌腺、上皮、内皮等)由来のもしくはこの組織に対応する分化細胞であることができる、または幹細胞もしくは前駆細胞等の未分化細胞であることができる。そのような実施形態では、重合性液体はヒドロゲルを形成するものであることができ、該重合性液体として、米国特許第7,651,683号、米国特許第7,651,682号、米国特許第7,556,490号、米国特許第6,602,975号、米国特許第5,836,313号等に記載されているものが挙げられるがこれらに限定されない。
本発明の装置の非限定的な実施形態を図2に示す。この装置は、反射鏡13を介して、壁14により画定されているビルドチャンバを照らす電磁放射線12を供給するデジタル光プロセッサ(DLP)等の放射源11と、ビルドチャンバの底部を形成する硬質のビルドプレート15とを含み、ビルドチャンバには液体樹脂16が充填されている。チャンバ15の底部は、下記で更に論じるように、硬質の半透過性部材を含む硬質のビルドプレートで構成されている。構築物(construction)17下の物体の上部は、キャリア18に取り付けられている。キャリアは、リニアステージ(linear stage)19により垂直方向に駆動されるが、下記で論じるように代替の構造を使用することができる。
いくつかの実施形態では、キャリアと3次元物体との間に可溶性の犠牲層(sacrificial layer)またはリリース層(release layer)を設置することができ、その結果、犠牲層をその後可溶化させ、製作の完了時にキャリアから3次元物体を都合良く離すことができる。キャリア上にコーティングされ得るまたはその他の方法で設けられ得る、接着剤等の任意の適切な犠牲層を用いることができ、犠牲リリース層を可溶化するために任意の適切な溶媒(例えば、極性のおよび非極性の有機溶媒、水性溶媒等)を用いることができるが、3次元物体を形成する具体的な材料自体が溶媒により過度に攻撃されないまたは可溶化されないように、犠牲層およびその対応する溶媒を選択しなければならない。噴霧、浸漬コーティング、塗布等の任意の適切な技法により、犠牲層をキャリアに塗布することができる。可溶性の犠牲リリース層に適した材料の例(および対応する溶媒の非限定的な例)として、シアノアクリレート接着剤(アセトン溶媒)、ポリ(ビニルピロリドン)(水および/またはイソプロピルアルコール溶媒)、ラッカー(lacquer)(アセトン溶媒)、ポリビニルアルコール、ポリアクリル酸、ポリ(メタクリル酸)、ポリアクリルアミド、ポリアルキレンオキシド、例えばポリ(エチレンオキシド)、糖類および糖質、例えばスクロースおよびデキストラン(全て水または水性溶媒)等が挙げられるがこれらに限定されない。いくつかの実施形態では、表面エネルギーがより低い溶媒が特に好ましい。
上記で述べたように、本発明は、3次元物体を形成する方法であって、(a)キャリアおよびビルドプレートを準備する工程であり、前記ビルドプレートが半透過性部材を含み、前記半透過性部材がビルド面と前記ビルド面とは別の供給面とを含み、前記ビルド面と前記キャリアとがそれらの間にビルド領域を画定し、前記供給面が重合阻害剤に流体接触する、準備する工程、次いで(同時におよび/または逐次的に)(b)前記ビルド領域に重合性液体を充填する工程であり、前記重合性液体が前記ビルド部分に接触する、充填する工程、(c)前記ビルドプレートを介して前記ビルド領域を照射して、前記ビルド領域中に固体の重合領域を生じさせ、前記固体の重合領域と前記ビルド面との間に、前記重合性液体で構成される液体フィルムのリリース層を形成する工程であり、前記液体フィルムの重合が前記重合阻害剤により阻害される、照射する工程、および(d)前記重合領域に接している前記キャリアを、前記静止しているビルドプレート上の前記ビルド面から離れるように前進させて、前記重合領域と前記上部ゾーンとの間に次のビルド領域を作る工程を含む方法を提供する。一般に、この方法は、(e)互いに接する(adhered)重合領域の堆積の連続または繰り返しにより前記3次元物体が形成されるまで、工程(b)から工程(d)を連続させておよび/または繰り返して、前の重合領域と接する次の重合領域を生じさせることを含む。
重合性液体を液体導管およびリザーバーシステム(reservoir system)からビルドプレートに直接供給することができるが、いくつかの実施形態では、キャリアは該キャリア中に1つまたは複数の供給流路を含む。キャリア供給流路は、重合性液体の供給部、例えばリザーバーおよび関連するポンプと流体連結(fluid communication)されている。異なるキャリア供給流路を同じ供給部と流体連結して互いに同時に作動させることができる、または(例えば、各キャリア供給流路用のポンプおよび/またはバルブを設けることにより)異なるキャリア供給流路を互いに独立して制御することができる。独立して制御可能な供給流路は、同じ重合性液体を含有するリザーバーと流体連結することができる、または異なる重合性流体を含有するリザーバーと流体連結することができる。バルブアセンブリ(valve assembly)の使用により、いくつかの実施形態では、必要に応じて同じ供給流路を介して異なる重合性液体を交互に供給することができる。
本発明の方法および装置は、例えばこの方法の速度および/または信頼性を高めるために、フィードバック制御およびフィードフォワード制御等の、プロセス制御を実施するためのプロセス工程および装置の機能を含むことができる。
本発明の方法およびプロセスにより製造される3次元製品は、最終製品、完成品もしくは実質的な完成品であることができるまたは例えば表面処理、レーザー切断、放電機械加工等の更なる製造工程にかけられる中間製品であることができることが意図されている。中間製品としては、同じ装置中でまたは別の装置中で更なる追加の製造を実行することができる製品が挙げられる。例えば、完成品の一領域を終了させるために、または単に完成品もしくは「ビルド」の特定の領域がその他に比べて脆くないことから、重合ゾーンの勾配を破壊し、次いで元に戻すことにより、進行中の「ビルド」に分断線または切断線を意図的に導入することができる。
[独立した供給面からビルド面への阻害剤の移動]
図5aに示すように、紫外線(UV)硬化性接着剤を一滴、金属プレート上に載置し、TEFLON(登録商標)AFフルオロポリマー(非晶質のガラス状ポリマー)の10mm厚のプレートで覆った。図5bに示すように、Teflon(登録商標) AF側から接着剤にUV放射線を供給した。UV曝露後、これら2枚のプレートを分離した。この2枚のプレートを分離するのに力は必要ないことを見出した。これらの試料の試験において、図5cに示すように、接着剤は金属プレートの隣でのみ硬化し、Teflon(登録商標) AFフルオロポリマープレート上に、および接着剤の硬化部分上にも未硬化の接着剤の薄いフィルムが存在したことを発見した。
[ビルドプレートを介したビルド面への阻害剤の移動]
下記のように、同じ方法で試料1および試料2を調製した。図6aに示すように、UV硬化性接着剤を一滴、金属プレート上に載置し、TEFLON(登録商標)AFフルオロポリマーの10mm厚のプレートで覆った。図6bに示すように、両方の試料を窒素雰囲気(environment:環境)に曝露し、存在する酸素を除去した。次に、両方の試料を標準的な雰囲気環境中に運び、直ちに試料1をUV放射線に曝露し、試料2を、雰囲気環境中に置いてから10分後にUV放射線に曝露した。図6Cおよび図6Eに示すように、両方の試料を同じ量のUV放射線に曝露した。これらの試料の試験では、UV曝露後に、図6Dに示すように、試料1は接着剤が完全に硬化したが、図6Fに示すように、試料2は接着剤が金属プレートの隣でのみ硬化したことを発見した。試料2の場合、Teflon(登録商標) AFフルオロポリマーのプレート上および接着剤の硬化部分上にも未硬化の接着剤の薄いフィルムが存在した。この試験は、雰囲気環境に曝露する10分間の中で、阻害剤である酸素がTeflon(登録商標) AFプレートを介して接着剤に移動したことを示す。
[製作速度の増加:圧力]
酸素透過性がより高く、UVに対して透明な(UV transparent)材料を、本発明の装置において光硬化性樹脂が充填されるチャンバの底部に使用する。構築の間中、物体の上部は、実質的に一定の速度で上昇する支持プレートに接着しており、チャンバの底部の真上では物体の底部が絶えず形成される。物体の底部とチャンバの底部との間のギャップは、樹脂が常に充填される。物体が形成され前進されるので、ギャップ中の樹脂は、チャンバに含まれる供給樹脂と絶えず置き換えられる。
[ロッドおよび繊維の製作]
図9に示すように、本発明の方法を使用して細長いロッドまたは繊維を製造することができ、このロッドまたは繊維は、(例えば)0.01または0.1から10または100ミリメートルの幅または直径を有する。円形断面を示すが、楕円形、多角形(三角形、正方形、五角形、六角形等)、不規則およびこれらの組み合わせ等の任意の適切な断面を用いることができる。ロッドまたは繊維は、任意の適切な直径(例えば、0.1もしくは1ミクロンから10もしくは100ミクロンまたはそれ以上)の複数個(例えば、1個、10個、100個、1,000個、10,000個もしくは100,000個またはそれ以上)の細長い細孔または流路と、上記に記載の任意の適切な断面とを有することができる。任意の適切な技法、例えばブローイング(blowing)、加圧、真空、加熱、乾燥およびこれらの組み合わせにより、細孔または流路中の未重合の液体を(必要に応じて)除去することができる。上記に記載の巻き取りリールを用いることによりロッドまたは繊維の長さを増加させることができ、上記に記載したように加圧下で重合を実行することによりロッドまたは繊維の製作速度を増加させることができる。複数の独立したキャリアまたは巻き取りリールを設けることにより、複数のそのようなロッドまたは繊維を単一のビルドプレートから同時に構築することができる。そのようなロッドまたは繊維を、任意の目的のために、例えばマイクロ流体システムにおける独立した流路として各細孔または流路を用いるために使用することができる。
[例示的装置]
本発明を実行するために使用することができる装置を、紫外線源としてのLOCTITE(商標)UV Curing Wand System、ウィンドウ中で固定され、引張リングにより実質的に強固に張力をかけられている、Biogeneralの0.0025インチ厚のTeflon(登録商標) AF 2400フィルムで構成されているビルドプレート、光学素子:Newport Corporation,Edmund Optics and Thorlabs製、デジタルプロジェクタとしてのTexas InstrumentsのDLP LightCrafter Development Kit、キャリア用のエレベータとして機能する、THK Co.,LTDのボールネジリニアステージ、エレベータおよびキャリアの駆動装置またはモーターとしての、Parallax Incの連続サーボ(continuous servo)、Parallax Inc.のPropellerマイクロ制御装置をベースとするモーション制御装置、Austria Microsystemsの磁気エンコーダ(magnetic encoder)をベースとする位置制御装置、オープンソースのSlic3r 3DスライスソフトウェアであるParallaxにより作られた、SPIN言語で書かれたモーション制御ソフトウェア、およびQtフレームワークおよびVisual C++を使用して書かれたイメージ制御ソフトウェアにより、上記に記載したように組立てた。
[700ミクロンの微小針アレイの製作]
上記の実験例に記載の装置、重合性液体としてのトリメチロールプロパントリアクリレート(trimethylolpropane triacrylate)、および、光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用して、図10に示す微小針のアレイを製造した。キャリアを、秒当たり10ミクロンの連続速度でボールネジにより一方向に前進させ、曝露当たり0.2秒の持続時間で、ビルド方向の高さに沿って2ミクロン毎に曝露を逐次実行した。逐次的な曝露の総数は350回であり、全製作時間は70秒であった。
[2000ミクロンの微小針アレイの製作]
上記実験例6に記載したのと同様の方法で、図11に示す2000ミクロンの微小針アレイを製造し、200秒の全製作時間にわたり逐次曝露は1000回であった。
[リング構造体の製作]
上記の実験例5に記載の装置、重合性液体としてのトリメチロールプロパントリアクリレート、および、光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用してリングを製作した。キャリアを、秒当たり20ミクロンの連続速度でボールネジにより一方向に前進させ、曝露当たり0.5秒の持続時間で、ビルド方向の高さに沿って10ミクロン毎に曝露を逐次実行した。逐次的な曝露の総数は1040回であり、全製作時間は520秒であった。図12は製作中のリングを示し、図13は製作後のリングを示す。製作中に広範囲に張り出す要素のための支持体が存在しないことに留意すべきである。
[チェスの駒の製作]
図14に示すチェスの駒を、上記実験例に記載の装置、重合性液体としてのトリメチロールプロパントリアクリレート、および、光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用して製造した。キャリアを、秒当たり20ミクロンの連続速度でボールネジにより一方向に前進させ、曝露当たり0.5秒の持続時間で、ビルド方向の高さに沿って10ミクロン毎に曝露を逐次実行した。逐次的な曝露の総数は1070回であり、全製作時間は535秒であった。
[リブ付き直方体の製作]
図15に示すリブ付き直方体を、上記実験例に記載の装置、重合性液体としてのトリメチロールプロパントリアクリレート、および、光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用して製造した。キャリアを、秒当たり20ミクロンの連続速度でウォームギアにより一方向に前進させ、曝露当たり0.5秒の持続時間で、ビルド方向の高さに沿って10ミクロン毎に曝露を逐次実行した。逐次的な曝露の総数は800回であり、全製作時間は400秒であった。
[コイル状のまたは螺旋状の構造体の製作]
図16に示すコイルまたは螺旋を、上記実験例に記載の装置、重合性液体としてのトリメチロールプロパントリアクリレート、および、光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用して製造した。キャリアを、秒当たり20ミクロンの連続速度でボールネジにより一方向に前進させ、曝露当たり0.5秒の持続時間で、ビルド方向の高さに沿って10ミクロン毎に曝露を逐次実行した。逐次的な曝露の総数は970回であり、全製作時間は485秒であった。
[硬化深度(curing depth)対曝露時間]
重合性液体としてのトリメチロールプロパントリアクリレート中における様々な濃度の琥珀色のロウソク染料および光開始剤(PI)ならびに光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用して実験を実施した。結果を図17に示す。使用した像は6mmの円であり、硬化した場合に、樹脂槽中でディスク様部品が製造された。このディスクの厚さは、曝露時間ならびに樹脂中における光開始剤および染料の濃度に基づいて変化した。全ての樹脂混合物が急速に硬化し、限界値に達することができた。最適な樹脂は、短期間で硬化するはずであり、限界値は、可能な限り小さいはずである。これらの基準に最も適合するのは、3%の光開始剤および0.05%の染料(細かい点線)と5%の光開始剤および染料なし(実線)との2種の樹脂である。これらの樹脂はまた、コントラストおよび明瞭さを特徴とするという観点で最良の印刷部品も製造する。
[キャリアの可溶性犠牲(またはリリース)層]
これまでの技法の欠陥は、例えばビルドプレートをスライドさせることによりまたは可撓性のビルドプレートを使用することによりビルドプレートからの接着を「破る(break)」必要があるということであり、そのため、製作プロセス中に早々に機能しなくなる可能性があるキャリア上でリリース層または可溶性の接着剤層を用いることは困難であった。本発明により、製作中におけるキャリア上でのリリース層の利用が容易になる。
[リリース層上での直方体の製作]
図21に示す200×200×1000ミリメートルの寸法を有する直方体のアレイを、上記に記載の装置、重合性液体としてのトリメチロールプロパントリアクリレート、光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドおよびリリース層としてのシアノアクリレート接着剤を使用して製造した。キャリアを、秒当たり10ミクロンの連続速度でボールネジにより前進させ、曝露当たり1秒の持続時間で、ビルド方向の高さに沿って10ミクロン毎に曝露を逐次実行した。逐次的な曝露の総数は100回であり、全製作時間は100秒であった。次いで、シアノアクリレートリリース層をアセトンで溶解して、図22に示す自由に浮遊する角柱体(free floating prism)を製造した。
[円筒状のケージ構造体の製作]
図23の円筒状のケージ構造体を、上記実験例に記載の装置、重合性液体としてのトリメチロールプロパントリアクリレートおよび光開始剤としてのジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用して製造した。キャリアを、秒当たり20ミクロンの連続速度でボールネジにより前進させ、曝露当たり0.5秒の持続時間で、ビルド方向の高さに沿って10ミクロン毎に曝露を逐次実行した。逐次的な曝露の総数は1400回であり、全製作時間は700秒であった。片持ち特徴(cantilevered feature)または「張出部」のための取り外し可能な支持構造体は使用しなかった。
[ヒドロゲルからの構造体の製作]
図24および図25はそれぞれ、重合性液体としてPEG(ポリ(エチレングリコール)ジアクリレート、平均Mn 700)を使用し、光開始剤として5%のジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキシドを使用して製作したことを除いて、上記に記載したものと同様の方法で製造したアレイ構造体およびケージ構造体の写真である。その他の処理条件は、既に製作したトリアクリレート部品の場合と同じであった。
[ヒドロゲルをベースとする部品の可撓性]
上記実験例23で製造したおよび図25に示す円筒状のケージ構造体を、2枚のガラスの顕微鏡スライドの間に手動で配置し、円筒状のケージ構造体が変形して実質的に平らになるまで圧力を手動で印加した。次いで、手動の圧力を解除すると、ケージ構造体は以前の実質的な円筒形状に戻った。この物品の可撓性、弾力性および形状記憶特性により、この物品は様々な用途に魅力的であり、該用途として様々な生物医学的応用のためのステントが挙げられるがこれに限定されない。
[治療的使用のための腔内ステントの製作]
ステントは、典型的には、閉塞したまたは部分的に閉塞した動脈およびその他の血管の処置において、経皮経管のバルーン血管形成手術(percutaneous transluminal balloon angioplasty procedure)の補助として使用される。バルーン血管形成手術の一例として、ガイディング(guiding)カテーテルまたはガイディングシース(guiding sheath)を、大腿動脈を通って患者の心臓血管系に経皮的に導入し、ガイディングカテーテルの遠位端(distal end)を病変部(lesion site)の近位(proximal)の箇所に配置するまで脈管構造を通って前進させる。ガイドワイヤと遠位端でバルーンを有する拡張カテーテルとを、ガイドワイヤを拡張カテーテル内にスライドさせて、ガイディングカテーテルを通して導入する。ガイドワイヤを最初にガイドカテーテルから出して患者の脈管構造中に前進させ、血管病変(vascular lesion)と交差するように案内する。続いて、拡張バルーンが血管病変と交差して適切に配置されるまで、拡張カテーテルを、既に前進させたガイドワイヤ上を前進させる。病変と交差する位置ですぐに、比較的高い圧力でX線不透過性液体により拡張バルーンを予め決めたサイズまで膨張させ、病変の動脈硬化プラークを動脈壁の内側に向かって放射状に圧迫し、これにより動脈の管腔を拡張する。次いで、バルーンを小さい断面まで収縮させ、その結果、拡張カテーテルを患者の脈管構造から引き抜くことができ、拡張された動脈を通って血流が再開される。
[治療用微小針アレイの製作]
多くの有望な新規の治療薬は、ペプチド、タンパク質、抗体および核酸等の大きな生体分子である。これらの分子は、導入の従来の経路による送達には過度に大きく、脆弱でありまたは不溶性である可能性がある。皮下注射(血管内、筋肉内等を含む)は、敏感な治療薬の送達を可能にするが、皮下注射は疼痛を誘発し、偶発的な針刺しの機会をもたらし、および、鋭いバイオハザード廃棄物(biohazardous waste)が生じる。さらに、ワクチン送達の場合は、皮下注射の針は、免疫反応を誘発するのに最適な位置に投与量を送達できず、投与量は、皮膚と比べて免疫学的に敏感な細胞の濃度が低いことが知られている領域である筋肉に浸透する。経皮パッチ剤は、(ニコチンおよび乗り物酔い薬のような)選択された時間に放出される薬剤に効果的であるが、表皮(特に角質層)は、皮膚を介したほとんどの薬剤(>500Da)の拡散を制限する。明らかに、治療薬を身体中に効率的に運ぶ能力には重要な課題が依然として存在する。
[垂直解像度の製作速度への依存]
いくつかの実施形態では、部品のビルドプロセス中に、制御装置の画像処理ユニット(IPU)は、部品の断面層の画像を常に更新している。いくつかの実施形態において、画像更新の最大速度fは、ハードウェアに依存して、秒当たり1フレームから秒当たり1000フレームまで様々であることができる。
[製作速度の増加:温度]
圧力による製作速度の増加を、上記で説明している。さらに、上記におよび下記に一般的および具体的の両方で記載している方法および装置は、(加圧の有無に関わらず)重合性液体のビルドゾーンへの充填またはビルドゾーンへの重合性液体の移動を容易にするために、重合性液体または樹脂の粘度を低下させるべくこれらを加熱することにより、製作速度を増加させることができる。上記で述べたものを含む高性能樹脂等のいくつかの樹脂は、室温および室内圧力で固体であることができ、加熱は、この樹脂を液体にする便利な方法であることができる。
[キャリアおよび内部の供給流路を介した樹脂の供給]
実験例3で論じたように、物体の形成速度は、物体の底面の長さ寸法L、樹脂の粘度η、雰囲気圧Pおよび物体とチャンバの底部との間のギャップの高さhに依存している。物体とチャンバの底部との間のギャップを充填するのに必要な時間τは下記の通りである。
[樹脂供給速度の制御:フィードフォワード制御]
部品ビルドプロセス中での樹脂消費速度は、部品の断面積に基づいて変化する。樹脂送達速度を制御するためのプロセスを下記に記載する。ビルド速度がvであり、部品の断面積AがA(t)として時間tと共に変化する場合、樹脂送達速度の全部または一部を、
R(t)=vA(t)
に対応するように調整することができる。
[外部供給導管を介した重合性液体の供給]
キャリア中に形成された1つまたは複数の流路を介して重合性液体が供給されるいくつかの実施形態では、製作する物品の一部または全てが終始固体であることが望ましい場合がある。そのような場合では、重合性液体を供給する1つの流路(または各流路)と流体連通している独立したまたは外部の供給導管を、(製造する物品内に形成される1つまたは複数の内部供給流路とは異なり)製作する物品に隣接して同時に製作することができる。
[複数の供給導管を使った複数の別々の樹脂による製作]
ビルドプラットフォーム(build platform)を介して異なる樹脂を供給することにより複数の樹脂を使用して、および、製作する部品の正確な領域に樹脂を送達するための管または流路を作るために複数の樹脂を使用して、物品を製作することができる。
[方法および装置の制御]
汎用コンピュータと上記に記載の装置との間に適切なインターフェイスハードウェアを有する汎用コンピュータで動作するソフトウェアプログラムにより、上記に記載の方法および装置を制御することができる。多数の代替手段が市販されている。「マイクロ制御装置」がParallax Propellerであり、ステッピングモーターの駆動装置がSparkfun EasyDriverであり、LED駆動回路がLuxeon Single LED Driverであり、シリアルに対するUSBがParallax USB to Serial変換器であり、DLPシステムがTexas Instruments LightCrafterシステムである、構成要素の一組み合わせの非限定的な例を図29〜31に示す。
Claims (20)
- 3次元物体を形成する方法であって、
キャリアと、ビルド面を有する光学的に透明な部材とを準備する工程であり、前記キャリアと前記ビルド面とがそれらの間にビルド領域を画定している、工程と、
前記ビルド領域に重合性液体を充填する工程と、
前記光学的に透明な部材を介して前記ビルド領域を照射する工程であって、この照射により前記重合性液体から固体ポリマーを形成するとともに、前記キャリアを前記ビルド面から離れるように前進させて前記固体ポリマーから前記3次元物体を形成し、さらに
(i)前記ビルド面に接触する重合性液体のデッドゾーンを時間連続的に維持し、かつ
(ii)前記デッドゾーンと前記固体ポリマーとの間であって且つこれらに接触する重合ゾーンの勾配を時間連続的に維持し、前記重合ゾーンの勾配が前記重合性液体を部分的に硬化した形態で含む、工程と
を含む方法。 - 前記光学的に透明な部材が半透過性部材を含み、前記デッドゾーンを時間連続的に維持することが、前記光学的に透明な部材を介して重合の阻害剤を供給することにより実行され、これにより、前記デッドゾーン中および任意選択的に前記重合ゾーンの勾配の少なくとも一部の中に阻害剤の勾配を生じさせる、請求項1に記載の方法。
- 前記照射する工程が、前記ビルド領域に投影される2次元放射パターンにより実行され、前記パターンが経時的に変化し、前記前進が前記3次元物体を形成するのに十分な時間にわたり連続する、請求項1又は2に記載の方法。
- 前記重合ゾーンの勾配を少なくとも5秒の時間にわたり維持する、請求項1〜3のいずれか1項に記載の方法。
- 前記3次元物体中に切断線を形成するのに十分な時間にわたり前記重合ゾーンの勾配を破壊する工程を更に含む、請求項1〜4のいずれか1項に記載の方法。
- 前記重合性液体を加熱する工程であり、該加熱して前記ビルド領域中における重合性液体の粘度を低下させる、工程を更に含む、請求項1〜5のいずれか1項に記載の方法。
- 前記キャリアが、前記キャリア中に形成された少なくとも1つの流路を有し、前記充填する工程が、前記少なくとも1つの流路を介して前記ビルド領域中に前記重合性液体を通すまたは押し込むことにより実行される、請求項1〜6のいずれか1項に記載の方法。
- 前記キャリアが、前記キャリア上に可溶性の犠牲層を有し、前記3次元物体が、前記可溶性の犠牲層上に形成される、請求項1〜7のいずれか1項に記載の方法。
- 前記ビルド領域の全表面積が、前記ビルド面の全表面積の少なくとも70パーセントを占め、および/または
任意の方向での前記キャリアおよび物体の横方向への移動が、対応する方向における前記ビルド領域の幅の30%以下である、
請求項1〜8のいずれか1項に記載の方法。 - 前記ビルド面が実質的に固定されている、または静止している、請求項1〜9のいずれか1項に記載の方法。
- 重合性液体から3次元物体を形成するための装置であって、
(a)支持体と、
(b)前記支持体に作動可能に関連付けられているキャリアであり、前記キャリア上で前記3次元物体が形成される、キャリアと、
(c)ビルド面を有し、前記ビルド面と前記キャリアとがそれらの間にビルド領域を画定している、光学的に透明な部材と、
(d)前記ビルド面に作動可能に関連付けられている、固化重合用の前記ビルド領域中に液体ポリマーを供給するように構成されている液体ポリマー供給部と、
(e)前記光学的に透明な部材を介して前記ビルド領域を照射し、前記重合性液体から固体ポリマーを形成するように構成されている放射源と、
(f)前記キャリアおよび前記放射源に作動可能に関連付けられている制御装置であって、前記キャリアを前記ビルド面から離れるように前進させて前記固体ポリマーから前記3次元物体を形成するとともに、
(i)前記ビルド面に接触する重合性液体のデッドゾーンを時間連続的に維持し、ならびに
(ii)前記デッドゾーンと前記固体ポリマーとの間のおよびこれらに接触する重合ゾーンの勾配を時間連続的に維持し、前記重合ゾーンの勾配が前記重合性液体を部分的に硬化した形態で含む、制御装置と
を含む装置。 - 前記キャリアが、前記キャリア中に形成された少なくとも1つの流路を有し、前記少なくとも1つの流路を介して前記ビルド領域に前記重合性液体を供給するように構成されており、
任意選択で、前記キャリアが、前記キャリア中に形成された複数の流路を有し、前記複数の流路のうちの異なる1つを介して異なる重合性液体を供給するように構成されている、請求項11に記載の装置。 - 前記物体とは別の少なくとも1本または複数の外部供給導管であって、前記少なくとも1本の供給導管のそれぞれが、前記キャリア中の流路と流体連通しており、前記キャリアから少なくとも1種または複数の異なる重合性液体を前記ビルドゾーンに供給するように構成されている外部供給導管を更に含む、請求項11又は12に記載の装置。
- 前記ビルドプレートが実質的に固定されている、または静止している、請求項11〜13のいずれか1項に記載の装置。
- 前記重合阻害剤の供給源が、前記半透過性部材内の重合阻害剤のリザーバーである、請求項11〜14のいずれか1項に記載の装置。
- 前記半透過性部材が、前記ビルド面とは別の供給面を更に含み、
任意選択で、前記供給面が、前記重合阻害剤の供給源となるように重合阻害剤に流体接触している、請求項11〜15のいずれか1項に記載の装置。 - 前記ビルドプレートおよび/または前記液体ポリマー供給部に作動可能に関連付けられている加熱器を更に含み、前記加熱器が、前記ビルド領域中のまたは前記ビルド領域に供給される重合性液体を加熱するように構成されており、
および/または、前記ビルドプレートに作動可能に関連付けられている、前記ビルド領域中における重合性液体を冷却するように構成されている冷却器を更に含む、請求項11〜16のいずれか1項に記載の方法。 - 前記液体ポリマー供給部に作動可能に関連付けられている圧力源を更に含む、請求項11〜17のいずれか1項に記載の装置。
- 前記キャリアが駆動装置を含み、前記駆動装置および前記制御装置が、前記キャリアを前記ビルド面から一方向に離れるように前進させるように構成されている、請求項11〜18のいずれか1項に記載の装置。
- 前記キャリアが、前記キャリア上に可溶性の犠牲層を有し、前記3次元物体が、前記可溶性の犠牲層上に形成される、請求項11〜19のいずれか1項に記載の装置。
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