JP2019521883A - 積層造形により3次元物体を形成するための方法および組成物 - Google Patents
積層造形により3次元物体を形成するための方法および組成物 Download PDFInfo
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- JP2019521883A JP2019521883A JP2018566481A JP2018566481A JP2019521883A JP 2019521883 A JP2019521883 A JP 2019521883A JP 2018566481 A JP2018566481 A JP 2018566481A JP 2018566481 A JP2018566481 A JP 2018566481A JP 2019521883 A JP2019521883 A JP 2019521883A
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本出願は、2017年7月22日に出願された欧州特許出願第16180915.7号、2016年10月28日に出願された同第16196328.5号、および2017年4月21日に出願された同第17167544.0号(これらはそれぞれ、参照によってその全体が本明細書に援用される)からの優先権を主張する国際特許出願である。
本発明は、積層造形による3次元物体の形成方法と、積層造形により3次元物体を形成するために有用であり得る組成物および材料のキットと、積層造形により形成された3次元物体とに関する。
3次元印刷としても知られている積層造形は、最終の3次元物体が製造されるまで一度に一部分ずつ物体を築き上げることにより3次元物体を形成するための技術である。積層技術は、最終の3次元物体を製造するためにより大量の材料から材料の一部分が除去されるミリングなどの減法技術と対比させることができる。
本発明の実施形態において、3次元物体の形成方法は、
a.微粒子組成物の層を形成するステップであって、微粒子組成物が、
i.第1の樹脂(第1の樹脂は第1の樹脂重合性基を含み、第1の樹脂重合性基は、電子吸引性基に直接結合した炭素−炭素二重結合を含む)を含む樹脂成分、
ii.樹脂成分中に分散または溶解された熱ラジカル開始剤、および
iii.樹脂成分中に分散または溶解された遅延剤
を含む複数の第1の粒子を含む、ステップと、
b.3次元物体の少なくとも一部分の形状に対応するコンピュータデータに従って、微粒子組成物の層の上に液体組成物を選択的に付着させるステップであって、液体組成物が、
i.第1の液体重合性成分(第1の液体重合性成分は第1の液体重合性基を含み、第1の液体重合性基は、第1の樹脂重合性基と(共)重合することができる炭素−炭素二重結合を含む)
を含む、ステップと、
c.任意選択的に、液体組成物が選択的に付着された微粒子組成物の層の複数の位置に電磁放射線を照射するステップと、
d.液体組成物が選択的に付着された微粒子組成物の層の複数の位置において熱ラジカル開始剤を活性化するステップと、
e.ステップa〜dを複数回繰り返して、3次元物体を形成するステップと
を含む。
一般に、3次元物体の層は、微粒子組成物の層を形成するステップと、3次元物体の少なくとも一部分の形状に対応するコンピュータデータに従って、微粒子組成物の層の上に液体組成物を選択的に付着させるステップとを含むプロセスによって形成され得る。本プロセスを付加的な回数繰り返して、更なる層を形成することができ、最終的に、所望の3次元物体が築き上げられる。任意選択的に、各層の硬化を助けるために電磁放射線を照射することができる。温度または光による処理などの後処理ステップも存在し得る。
a.微粒子組成物の層を形成するステップであって、微粒子組成物が、
i.第1の樹脂(第1の樹脂は第1の樹脂重合性基を含み、第1の樹脂重合性基は、電子吸引性基に直接結合した炭素−炭素二重結合を含む)を含む樹脂成分、
ii.樹脂成分中に分散または溶解された熱ラジカル開始剤、および
iii.樹脂成分中に分散または溶解された遅延剤
を含む複数の第1の粒子を含む、ステップと
b.3次元物体の少なくとも一部分の形状に対応するコンピュータデータに従って、微粒子組成物の層の上に液体組成物を選択的に付着させるステップであって、液体組成物が、
i.第1の液体重合性成分(第1の液体重合性成分は第1の液体重合性基を含み、第1の液体重合性基は、第1の樹脂重合性基と(共)重合することができる炭素−炭素二重結合を含む)
を含む、ステップと、
c.任意選択的に、液体組成物が選択的に付着された微粒子組成物の層の複数の位置に電磁放射線を照射するステップと、
d.液体組成物が選択的に付着された微粒子組成物の層の複数の位置において熱ラジカル開始剤を活性化するステップと、
e.ステップa〜dを複数回繰り返して、3次元物体を形成するステップと
を含む。
微粒子組成物は、1つまたは複数の異なる種類の粒子、例えば、異なる化学組成を有する粒子を含み得る。複数の粒子は、樹脂成分と、樹脂成分中に分散または溶解された熱ラジカル開始剤と、樹脂成分中に分散または溶解された遅延剤とを含む第1の粒子である。このような第1の粒子は、通常、微粒子組成物の40〜100wt%、例えば、微粒子組成物の50wt%〜99wt%の量で存在する。
第1の粒子は樹脂成分を含む。樹脂成分は、第1の樹脂、第2の樹脂などの複数の樹脂を含み得る。樹脂成分は少なくとも第1の樹脂を含み、第1の樹脂は、第1の樹脂重合性基を含む。第1の樹脂重合性基は、電子吸引性基に直接結合した炭素−炭素二重結合を含む。第1の樹脂のみが以下において言及されるが、第1の樹脂の説明は、任意選択的な第2の樹脂または更なる樹脂の可能性のある態様についても説明することが意図される。
熱ラジカル開始剤は、熱ラジカル開始剤が活性化温度よりも高いかそれに等しい温度にさらされたときに、2時間以内に第1の樹脂の重合を開始させるのに十分なラジカルを生成する成分であり、活性化温度は30℃よりも高い。従って、活性化温度は、熱ラジカル開始剤が、2時間以内に第1の樹脂の重合を開始させるのに十分なラジカルを生成する最低温度である。実施形態において、熱ラジカル開始剤の活性化温度は、40℃、50℃、60℃、70℃、80℃、90℃、100℃、120℃、または150℃よりも高い。実施形態において、熱ラジカル開始剤の活性化温度は、300℃、250℃、200℃、180℃、160℃、140℃、120℃、100℃、80℃、60℃、または50℃よりも低い。ラジカルは、例えば、熱ラジカル開始剤の分解によって生成され得る。
から計算することができ、式中、t1/2は半減期(秒)であり、kdは熱ラジカル開始剤解離の速度定数(s−1)であり、以下の式(2):
により決定され、式中、Aはアレニウスの頻度因子(s−1)であり、Eaは開始剤解離の活性化エネルギー(J/モル)であり、Rは8.3142J/モル・Kであり、Tは温度(K)である。
遅延剤は、樹脂成分中に分散または溶解される。実施形態において、液体組成物は更に遅延剤を含む。実施形態において、遅延剤は、熱ラジカル開始剤により生成されるラジカルに応答して、第1の粒子重合性基の重合の開始を阻害する。遅延剤は、単に樹脂と混合することによって樹脂中に分散または溶解され得る。例えば、遅延剤が樹脂成分中に分散または溶解されるように、樹脂、熱ラジカル開始剤、および遅延剤を含む組成物を混合した後に、組成物から粒子を形成することによって、遅延剤は樹脂中に分散または溶解され得る。樹脂成分粒子を遅延剤粒子と単にブレンドすることは、遅延剤を樹脂成分中に溶解または分散させることではない。遅延剤を樹脂成分中に溶解または分散させるために、溶媒処理、押出、または混練が必要とされ得る。
液体組成物は、噴霧、ジェッティング(例えば、圧電による)、サーマルもしくはバブルインクジェット、またはマスクもしくはステンシル上での付着などの任意の適切なプロセスを用いて、選択的に付着され得る。液体組成物は、少なくとも、第1の液体重合性基を含む第1の液体重合性成分を含む。
液体重合性成分は、樹脂成分中の第1の重合性基と(共)重合することができる。実施形態において、液体重合性成分は、樹脂の第1の重合性基と(共)重合可能な反応性部分として不飽和を含む。液体重合性成分は、第1の液体重合性成分、第2の液体重合性成分などの1つまたは複数の液体重合性成分を含み得る。以下の開示が「液体重合性成分」または「液体重合性基」について言及する場合、第1、第2、および/または第3などの液体重合性成分または液体重合性基も開示される。液体重合性成分は、モノマー、オリゴマー、および/またはポリマーである成分、ならびに一官能性または多官能性であり得る成分を含み得る。
実施形態において、促進剤は液体組成物中に存在する。促進剤が熱ラジカル開始剤と接触されると、熱ラジカル開始剤は、促進剤が存在しない場合に熱ラジカル開始剤が分解可能である温度よりも低い温度で分解可能である。実施形態において、促進剤は微粒子組成物中に付加的に存在し、熱ラジカル開始剤は液体組成物中に付加的に存在する。実施形態において、液体組成物を微粒子組成物上に付着させた後、促進剤は熱ラジカル開始剤と接触され、それにより、促進剤が存在しない場合に熱ラジカル開始剤が十分なラジカルを生成することができる温度よりも低い温度において、熱ラジカル開始剤に十分なラジカルを生成させる。実施形態において、促進剤が存在しない場合に熱ラジカル開始剤が十分なラジカルを生成することができる温度は微粒子組成物の温度よりも高いが、促進剤の存在下で熱ラジカル開始剤がラジカルを生成することができる温度は、微粒子組成物の温度よりも低い。
実施形態において、液体組成物は更に液体ラジカル開始剤を含む。液体ラジカル開始剤という用語は、液体組成物中のラジカル開始剤を指すために使用される。液体ラジカル開始剤は、それ自体が液体である必要はない。しかしながら、実施形態において、液体ラジカル開始剤は30℃で液体である。液体ラジカル開始剤は、第1の樹脂および/または液体重合性成分の重合をもたらすラジカルを生成することができる。実施形態において、液体ラジカル開始剤は、上記のような熱ラジカル開始剤である。
実施形態において、液体組成物は更に可塑剤を含む。実施形態において、可塑剤は液体である。実施形態において、可塑剤はポリアルキレンエーテルである。実施形態において、可塑剤は、デカノール、グリセロール、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、プロピレングリコール、または脂肪酸である。実施形態において、可塑剤は、フタル酸ジオクチルなどのジアルキルフタラートである。実施形態において、可塑剤は、トリメリット酸トリメチル、トリメリット酸トリ−(2−エチルヘキシル)、トリメリット酸トリ−(n−オクチル,n−デシル)、トリメリット酸トリ−(ヘプチル,ノニル)、トリメリット酸n−オクチル、アジピン酸ビス(2−エチルヘキシル)、アジピン酸ジメチル、アジピン酸モノメチル、アジピン酸ジオクチル、セバシン酸ジブチル、マレイン酸ジブチル、またはマレイン酸ジイソブチルである。実施形態において、可塑剤の量は、全液体組成物の25、20、15、または10wt%未満である。実施形態において、可塑剤の量は、全液体組成物の1、5、10、または20wt%よりも多い。
実施形態において、液体組成物または微粒子組成物は更に吸収剤を含む。吸収剤は、電磁放射線を吸収することができる。実施形態において、吸収剤は、赤外光、近赤外光、および可視光のうちの1つまたは複数を吸収する。吸収剤を包含させ、液体組成物が選択的に付着された微粒子組成物の層の複数の位置に電磁放射線を照射する任意選択のステップを実行することにより、吸収剤が存在する微粒子組成物の層においてより高い温度を得ることができる。吸収剤により吸収される波長は、電磁放射線の波長と重複しなければならない。
他に言及されない限り、本特許出願において報告または特許請求される任意の測定値は以下のように得られる。
実施例で使用される種々の成分のいくつかは、以下の表0.1および0.2に記載される。WPUは、不飽和当たりの重量(weight per unsaturation)である。WPUは、製造された材料の重量を、添加した不飽和のモル数で割ることによって計算される。
SOEAは以下のように形成される。最初に、ポリエステルポリオールを形成する:20モルのテレフタル酸、20モルのネオペンチルグリコールおよび1モルのトリメチロールプロパンを、酸価が10未満になるまで180〜240℃において0.1%のBuSnCl(OH)2を用いてエステル化する。次に、得られたポリエステルポリオールを以下のようにアクリレート化する。ステップ1のポリエステルポリオールを120℃に冷却し、105モル%のアクリル酸(OH量に対して)、15wt%のトルエン、1wt%のp−トルエンスルホン酸(PTSA)、および0.2wt%のジブチルヒドロキノン(全てポリエステルポリオール+アクリル酸の量に基づく)と混合する。反応混合物を通して空気をパージし、トルエンが沸騰するまで温度を上昇させる。次に、Dean−Stark装置を備えたフラスコ内で、混合物を8時間還流させる(120〜140℃)。必要に応じて、圧力を低下させて、トルエンの還流を保持する。8時間後にサンプルを取り、電位差により滴定して、遊離PTSAに属する酸価(AV1)およびカルボン酸の酸価(AV2)を決定する。105モル%(PTSAのAV1に対して)の3−エチル−3−ヒドロキシメチルオキセタンを添加して、PTSAを中和する。15分後にサンプルを取り、AV1=0であるかどうかを検査し、続いて、160℃および50mmHgにおける蒸留により溶媒および残留アクリル酸を除去する。最終値は、AV1=0およびAV2=8.9である。樹脂のTg(DSC)は45℃である。
PU−maを含有しない微粒子組成物については、樹脂成分は、そして熱ラジカル開始剤および/または遅延剤が樹脂成分中に分散または溶解されている場合には樹脂成分および/または遅延剤は、ブレンダー内で混合され、続いて、押出機の最大値の70〜90%のトルクに達するようにスクリュー速度を調節して70℃のPRISM TSE16 PCツインスクリューにおいて押出される。押出物を室温まで冷却させ、破壊してチップにする。0.5mmの環状のふるいを備えたRetsch ZM100において18000rpmでチップを粉砕し、そしてふるいにかける。粒径が90μm未満のふるい画分を捕集する。
液体組成物の成分を室温で十分に混合する。
0.8mm厚のクロム酸アルミニウム(chromate aluminum)Q−パネル(タイプALQ−46)上に微粒子組成物を適用する。樹脂成分としてPU−maを含有するものを除く全ての微粒子組成物を処理済Q−パネル上に適用する。PU−maは、未処理のQ−パネル上に形成される。処理済Q−パネルは、Loctiteからの1−STEP Frekote(登録商標)離型剤でQ−パネルを処理し、次にHeraeus Instruments UT6120オーブンにおいて130℃で15分間乾燥させることによって形成される。この手順を更に2回、各Q−パネルにつき全部で3回繰り返して、処理済Q−パネルを形成する。
形成されたフィルムを周囲条件で数日間貯蔵した後、数滴のアセトンをフィルムに付着させ、約10秒後にアセトンを布で除去する。次に、層を目視検査で評価する。「+」は、層がASTにより損なわれないことを示す。「+/−」は、最上層が損なわれるか、または部分的に拭き取られることを示す。「−」は、層が完全にまたはほぼ完全に拭き取られることを示す。
幅約2mmのサンプルを硬化フィルムから打ち抜く。厚さは、較正されたHeidenhain厚さ計で測定される。動的機械分析は、ASTM D5026に従い、RSA−III試験システムを用いて、1Hzの周波数において5℃/分の加熱速度で−100℃〜200℃の範囲の温度にわたって実行される。測定の間に、貯蔵弾性率(E’)、損失弾性率(E”)およびタンジェントデルタ(tanδ)が温度の関数として決定される。「n.t.」は試験されないことを意味する。
複数の粒子を含む種々の微粒子組成物を形成する。粒子は、非晶質不飽和ポリエステル(UPE1010)およびビニルエーテル(P1900)を含む樹脂成分を含む。反応性不飽和のビニルエーテル基に対するモル比は、おおよそ1:0.5である。微粒子組成物は、樹脂成分中に分散または溶解された熱ラジカル開始剤(T.R.I.)として3.6wt%のmBPOを含む。いくつかの実験では、遅延剤として250ppmのヒドロキノンを樹脂成分中に溶解させる。全ての成分を押出により混合する。
種々の微粒子組成物を形成する。粒子は、非晶質不飽和ポリエステル(UPE1010)およびビニルエーテル(P1900)を含む樹脂成分を含む。反応性不飽和のビニルエーテル基に対するモル比は、おおよそ1:0.5である。熱ラジカル開始剤(T.R.I.)としての3.6wt%のmBPOは、樹脂成分中に分散または溶解されている(「D」)か、存在しない(「−」)か、あるいは別の微粒子としてブレンドされている(「B」)。遅延剤としての250ppmのヒドロキノンは、樹脂成分中に溶解されている(「D」)か、あるいは存在しない(「−」)。
種々の微粒子組成物を形成する。熱ラジカル開始剤(T.R.I.)としての3.6wt%のmBPOは、樹脂成分中に溶解される(「D」)か、あるいは別の微粒子としてブレンドされている(「B」)。遅延剤としての250ppmのヒドロキノンは、押出により樹脂成分中に溶解されている(「D」)か、あるいは存在しない(「−」)。規定される樹脂成分は、微粒子組成物の残りを構成する。樹脂成分が不飽和ポリエステルおよびビニルエーテルの両方を含む場合、反応性不飽和のビニルエーテル基に対するモル比は、おおよそ規定される通りである。
種々の微粒子組成物を形成する。熱ラジカル開始剤(T.R.I.)としての3.6wt%のmBPOおよび遅延剤としての250ppmのヒドロキノンを押出により樹脂成分中に分散または溶解させる。規定される樹脂成分は、微粒子組成物の残りを構成する。樹脂成分が不飽和ポリエステルおよびビニルエーテルの両方を含む場合、反応性不飽和のビニルエーテル基に対するモル比は、おおよそ規定される通りである。
種々の微粒子組成物を形成する。実施例5.5の場合(TRIとしての2wt%のtBu−ペルオキシベンゾアートおよび遅延剤としての130ppmの2,6−ジ−tert−ブチル−4−メチルフェノールを樹脂成分中に溶解させる)を除いて、熱ラジカル開始剤(T.R.I.)としての3.6wt%のmBPOおよび遅延剤としての250ppmのヒドロキノンを押出により樹脂成分中に溶解させる。規定される樹脂成分は、微粒子組成物の残りを構成する。樹脂成分が不飽和ポリエステルおよびビニルエーテルの両方を含む場合、反応性不飽和のビニルエーテル基に対するモル比は、おおよそ規定される通りである。
1)a.微粒子組成物の層を形成するステップであって、微粒子組成物が、
i.第1の樹脂(第1の樹脂は第1の樹脂重合性基を含み、第1の樹脂重合性基は、電子吸引性基に直接結合した炭素−炭素二重結合を含む)を含む樹脂成分、
ii.樹脂成分中に分散または溶解された熱ラジカル開始剤、および
iii.樹脂成分中に分散または溶解された遅延剤
を含む複数の第1の粒子を含む、ステップと、
b.3次元物体の少なくとも一部分の形状に対応するコンピュータデータに従って、微粒子組成物の層の上に液体組成物を選択的に付着させるステップであって、液体組成物が、
i.第1の液体重合性成分(第1の液体重合性成分は第1の液体重合性基を含み、第1の液体重合性基は、第1の樹脂重合性基と(共)重合することができる炭素−炭素二重結合を含む)
を含む、ステップと、
c.任意選択的に、液体組成物が選択的に付着された微粒子組成物の層の複数の位置に電磁放射線を照射するステップと、
d.液体組成物が選択的に付着された微粒子組成物の層の複数の位置において熱ラジカル開始剤を活性化するステップと、
e.ステップa〜dを複数回繰り返して、3次元物体を形成するステップと
を含む、3次元物体の形成方法。
ii.樹脂成分中に分散または溶解された熱ラジカル開始剤、および
iii.樹脂成分中に分散または溶解された遅延剤
を含む複数の第1の粒子を含む微粒子組成物と、
b.i.第1の液体重合性成分(第1の液体重合性成分は第1の液体重合性基を含み、第1の液体重合性基は、第1の樹脂重合性基と(共)重合することができる炭素−炭素二重結合を含む)
を含む液体組成物と
を含む、積層造形プロセスにより物体を形成するための材料のキット。
b.モールドを用いて3次元物体を形成するステップと
を含む、3次元物体の形成方法。
b.モールドを用いて3次元物体を形成するステップと
を含む、3次元物体の形成方法。
Claims (17)
- a.微粒子組成物の層を形成するステップであって、前記微粒子組成物が、
i.第1の樹脂(前記第1の樹脂は第1の樹脂重合性基を含み、前記第1の樹脂重合性基は、電子吸引性基に直接結合した炭素−炭素二重結合を含む)を含む樹脂成分、
ii.前記樹脂成分中に分散または溶解された熱ラジカル開始剤、および
iii.前記樹脂成分中に分散または溶解された遅延剤
を含む複数の第1の粒子を含む、ステップと、
b.3次元物体の少なくとも一部分の形状に対応するコンピュータデータに従って、前記微粒子組成物の層の上に液体組成物を選択的に付着させるステップであって、前記液体組成物が、
i.第1の液体重合性成分(前記第1の液体重合性成分は第1の液体重合性基を含み、前記第1の液体重合性基は、前記第1の樹脂重合性基と(共)重合することができる炭素−炭素二重結合を含む)
を含む、ステップと、
c.任意選択的に、前記液体組成物が選択的に付着された前記微粒子組成物の層の複数の位置に電磁放射線を照射するステップと、
d.前記液体組成物が選択的に付着された前記微粒子組成物の層の複数の位置において前記熱ラジカル開始剤を活性化するステップと、
e.ステップa〜dを複数回繰り返して、3次元物体を形成するステップと
を含む、3次元物体の形成方法。 - 前記液体組成物が、前記熱ラジカル開始剤の促進剤を更に含む、請求項1に記載の方法。
- 前記熱ラジカル開始剤が前記促進剤と接触していないときに前記熱ラジカル開始剤が6分以下の半減期を有する温度と、前記熱ラジカル開始剤が前記促進剤と接触しているときに前記熱ラジカル開始剤が6分以下の半減期を有する温度との間の差が30℃〜100℃である、請求項2に記載の方法。
- 前記第1の樹脂重合性基が、メタクリレート、フマラート、マレアート、またはイタコナートを含む、請求項1〜3のいずれか一項に記載の方法。
- 前記樹脂成分の各分子中の重合性基の平均数で割った前記樹脂成分のMnが450〜1200g/molである、請求項1〜4のいずれか一項に記載の方法。
- 前記第1の樹脂が非晶質であり、20〜60℃のガラス転移温度(Tg)を有する、請求項1〜5のいずれか一項に記載の方法。
- 前記第1の樹脂が結晶性であり、−70〜100℃のガラス転移温度(Tg)を有する、請求項1〜5のいずれか一項に記載の方法。
- 前記第1の樹脂が不飽和ポリエステルを含み、前記第1の液体重合性基がビニルエーテルである、請求項1〜7のいずれか一項に記載の方法。
- 前記液体組成物が、第2の液体重合性基を含む第2の液体重合性成分を更に含み、前記第2の液体重合性基がフマラートを含む、請求項1〜8のいずれか一項に記載の方法。
- 前記熱ラジカル開始剤が過酸化物を含み、前記促進剤がアミンを含む、請求項2〜9のいずれか一項に記載の方法。
- 前記液体組成物が、3次元物体の一部分を表す複数のボクセルに従って前記微粒子組成物の層の上に選択的に分配され、ボクセル当たりのビニルエーテル基のフマラートおよびマレアート基に対するモル比が1.5:1〜1:1.5である、請求項1〜10のいずれか一項に記載の方法。
- 前記液体組成物が吸収剤を更に含み、前記液体組成物が選択的に付着された前記微粒子組成物の層の複数の位置に電磁放射線を任意選択的に照射する前記ステップが実行される、請求項1〜11のいずれか一項に記載の方法。
- 前記微粒子組成物に阻害剤を選択的に付着させるステップを更に含む、請求項1〜12のいずれか一項に記載の方法。
- 積層造形プロセスにより物体を形成するための材料のキットであって、
a.i.第1の樹脂(前記第1の樹脂は第1の樹脂重合性基を含み、前記第1の樹脂重合性基は、電子吸引性基に直接結合した炭素−炭素二重結合を含む)を含む樹脂成分、
ii.前記樹脂成分中に分散または溶解された熱ラジカル開始剤、および
iii.前記樹脂成分中に分散または溶解された遅延剤
を含む複数の第1の粒子を含む微粒子組成物と、
b.i.第1の液体重合性成分(前記第1の液体重合性成分は第1の液体重合性基を含み、前記第1の液体重合性基は、前記第1の樹脂重合性基と(共)重合することができる炭素−炭素二重結合を含む)
を含む液体組成物と
を含む、キット。 - 前記第1の樹脂がテレケリック型であり、少なくとも2つの第1の樹脂重合性基を末端基として含み、そして前記第1の樹脂重合性基が(メタ)アクリレート基を含む、前述の例示的実施形態のいずれか一項に記載の方法またはキット。
- 前記熱ラジカル開始剤の活性化よりも前または活性化と同時に、前記液体組成物が選択的に付着された前記微粒子組成物の層の複数の位置において前記第1の樹脂を融解させることを更に含み、前記微粒子組成物が乾燥温度を有し、前記乾燥温度が前記微粒子組成物の層の表面における温度であり、前記第1の樹脂が結晶性または半結晶性であり、そして前記第1の樹脂が、前記微粒子組成物が前記液体組成物と接触しているときには前記乾燥温度よりも低いかそれに等しい温度で融解するが、前記微粒子組成物が前記液体組成物と接触していないときには前記乾燥温度で融解しない、前述の例示的実施形態のいずれか一項に記載の方法。
- 請求項1〜16のいずれか一項に記載の方法または材料のキットから形成された3次元物体。
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