JP7314351B2 - 光熱法によるセラミックスまたは金属材料のグリーン体部品の光造形による製造のための硬化性組成物 - Google Patents
光熱法によるセラミックスまたは金属材料のグリーン体部品の光造形による製造のための硬化性組成物 Download PDFInfo
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- JP7314351B2 JP7314351B2 JP2022064361A JP2022064361A JP7314351B2 JP 7314351 B2 JP7314351 B2 JP 7314351B2 JP 2022064361 A JP2022064361 A JP 2022064361A JP 2022064361 A JP2022064361 A JP 2022064361A JP 7314351 B2 JP7314351 B2 JP 7314351B2
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- B22F10/10—Formation of a green body
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Description
コンピュータ支援設計により、製造される部品のコンピュータモデルが構築され、モデルのサイズは、セラミックスまたは金属材料の部品製造時の収縮を見込むように、製造される部品のサイズよりもわずかに大きい、モデル形成ステップ。
部品を製造する以下のステップ:
高剛性支持体上に、少なくとも1種のセラミックスまたは金属材料、光硬化性モノマーおよび/またはオリゴマー、光開始剤、および適切な場合、以下:可塑剤、溶媒、分散剤、または重合阻害剤のうちの少なくとも1つを含む光硬化性組成物の第1の層を形成するステップと、
前記層のモデルに基づく定義されたパターンに従って、(前記層の自由表面のレーザー走査またはダイオード投影システムを使用することによる)照射によって光硬化性組成物の第1の層を硬化させ、第1のステージを形成するステップと、
第1のステージの上に、光硬化性組成物の第2の層を形成するステップと、
光硬化性組成物の第2の層を、前記層に対して定義されたパターンに従って照射することによって硬化させ、第2のステージを形成するステップであって、この照射は、第1の層と同じ方法で行われる、ステップと、
任意選択で、グリーン体部品が得られるまで上記の手順を繰り返するステップ
・光化学的開始:CTC錯体は、UV-可視光を吸収して励起状態を形成する。EDからAEへの電子移動が、分子の切断を引き起こし、主に高反応性ラジカルが放出される。
・熱的開始:高温になると、CTC錯体が切断してフリーラジカルを放出する。この場合、セラミックスまたは金属の粒子は作動波長で吸収し、その後、吸収された光エネルギーは熱に変換され、その後、CTC開始剤によって吸収される。
セラミックス粉末および/または金属粉末から選択される少なくとも1種の粉末と、
少なくとも1種の重合性モノマーおよび/または少なくとも1種の重合性オリゴマーと、
重合性モノマーおよび/または重合性オリゴマーの重合のための少なくとも1種の開始剤とを含む、硬化性組成物において、
開始剤は、
ヨードニウム塩、スルホニウム塩、およびジアゾニウム塩と、
電荷移動錯体を形成するための少なくとも1種のアミンおよび/または少なくとも1種のホスフィンと組み合わせたオニウム塩とから選択され、
開始剤は、UV、可視、またはIR照射源から選択される少なくとも1つの照射源への曝露下で熱重合を開始できることを特徴とする、硬化性組成物に関するものである。
ランタンストロンチウムマンガナイトセラミックスや、イットリア安定化ジルコニアと混合したランタンストロンチウムマンガナイトセラミックス、フェライトなどの、酸化物セラミックス粉末と、
炭化ケイ素、窒化ケイ素、窒化アルミニウムなどの非酸化物セラミックス粉末とから選択され得る。金属粉末は、銀、銅、鉄、タングステン、およびそれらの合金から選択され得る。
25~65体積部の金属および/またはセラミックス粉末と、
20~50体積部のモノマーおよび/またはオリゴマーと、
0.01~5体積部の重合開始剤と、
最大25体積部、特に5~25体積部の可塑剤と、
最大8体積部、特に1~8体積部の分散剤とを含み得る。
Claims (19)
- セラミックスまたは金属材料で作られたグリーン体部品を光造形によって製造するための硬化性組成物であって、前記硬化性組成物は、
セラミックス粉末および/または金属粉末から選択される少なくとも1種の粉末と、
少なくとも1種の重合性モノマーおよび/または少なくとも1種の重合性オリゴマーであって、多官能性(メタ)アクリレートから選択される前記モノマーおよび/または前記オリゴマーと、
前記重合性モノマーおよび/または前記重合性オリゴマーの重合のための少なくとも1種の開始剤とを含む、硬化性組成物において、
前記開始剤は、
ヨードニウム塩、スルホニウム塩、およびジアゾニウム塩と、
電荷移動錯体を形成するための少なくとも1種のアミンおよび/または少なくとも1種のホスフィンと組み合わせたオニウム塩とから選択され、
前記開始剤は、UV、可視、またはIR照射源から選択される少なくとも1つの照射源への曝露下で熱重合を開始できることを特徴とする、硬化性組成物。 - 前記セラミックス粉末は、
酸化物セラミックス粉末と、
非酸化物セラミックス粉末とから選択されることを特徴とする、請求項1に記載の組成物。 - 前記酸化物セラミックス粉末は、ランタンストロンチウムマンガナイトセラミックス、イットリア安定化ジルコニアと混合したランタンストロンチウムマンガナイトセラミックス、又はフェライトであり、
前記非酸化物セラミックス粉末は、炭化ケイ素、窒化ケイ素、又は窒化アルミニウムであることを特徴とする、請求項2に記載の組成物。 - 前記金属粉末は、銀、銅、鉄、タングステン、およびそれらの合金から選択されることを特徴とする、請求項1~3のいずれか一項に記載の組成物。
- 前記多官能性(メタ)アクリレートは、ジエトキシル化ビスフェノールAジメタクリレート、1,6-ヘキサンジオールジアクリレート、3-メチル-1,5-ペンタンジオールジアクリレート、トリメチロールプロパントリアクリレート、およびそれらの混合物から選択されることを特徴とする、請求項1~4のいずれか一項に記載の組成物。
- 少なくとも1種のアミンおよび/または少なくとも1種のホスフィンと組み合わせて使用される前記オニウム塩は、ヨードニウム塩、スルホニウム塩、およびジアゾニウム塩から選択されることを特徴とする、請求項1~5のいずれか一項に記載の組成物。
- 前記ヨードニウム塩は、ジアリールヨードニウムであることを特徴とする、請求項1~6のいずれか一項に記載の組成物。
- 前記ジアリールヨードニウムは、ビス-(4-t-ブチルフェニル)-ヨードニウムヘキサフルオロホスフェートであることを特徴とする、請求項7に記載の組成物。
- 前記スルホニウム塩は、トリアリールスルホニウムであることを特徴とする、請求項1~6のいずれか一項に記載の組成物。
- 前記トリアリールスルホニウムは、プロピレンカーボネートとの混合物中のトリアリールスルホニウムヘキサフルオロアンチモネートであることを特徴とする、請求項9に記載の組成物。
- 前記混合物中のトリアリールスルホニウムヘキサフルオロアンチモネートが50%の割合であることを特徴とする、請求項10に記載の組成物。
- 前記アミンは、第一級、第二級、および第三級の、脂肪族または芳香族アミンから選択されることを特徴とする、請求項1~11のいずれか一項に記載の組成物。
- 前記アミンは、2-[4-(ジメチルアミノ)フェニル]エタノール、2,2’-(4-メチルフェニルイミノ)ジエタノール、エチル4-(ジメチルアミノ)ベンゾエート、およびN-メチルジエタノールアミンから選択されることを特徴とする、請求項12に記載の組成物。
- 前記ホスフィンは、第一級、第二級、および第三級の、脂肪族または芳香族ホスフィンから選択されることを特徴とする、請求項1~13のいずれか一項に記載の組成物。
- 前記ホスフィンは、トリフェニルホスフィン、4-(ジフェニルホスフィノ)スチレン、4-(ジフェニルホスフィノ)安息香酸、2-(ジフェニルホスフィノ)安息香酸2-(ジフェニルホスフィノ)ベンズアルデヒド、(1R、2R)-(+)-1,2-ジアミノシクロヘキサン-N、N’-ビス(2-ジフェニルホスフィノ-1-ナフトイル)または(R、R)-DACH-ナフチル-トロスト配位子、ビス[2-(ジフェニルホスフィノ)フェニル]エーテルから選択されることを特徴とする、請求項14に記載の組成物。
- ポリエチレングリコール、フタル酸ジブチル、およびグリセロールから選択される少なくとも1種の可塑剤をさらに含むことを特徴とする、請求項1~15のいずれか一項に記載の組成物。
- リン酸エステルから選択される少なくとも1種の分散剤も含むことを特徴とする、請求項1~16のいずれか一項に記載の組成物。
- 総体積に対して、
25~65体積部の前記金属および/またはセラミックス粉末と、
20~50体積部の前記モノマーおよび/またはオリゴマーと、
0.01~5体積部の重合開始剤と、
最大25体積部の前記可塑剤と、
最大8体積部の前記分散剤と
を含むことを特徴とする、請求項1~17のいずれか一項に記載の組成物。 - 光造形により、セラミックスまたは金属でできたグリーン体部品を製造する方法であって、前記方法によると、重合によって硬化可能であり、セラミックスまたは金属のグリーン体部品を製造することがそれぞれ望まれるかどうかに応じて、セラミックスまたは金属の粉末を含む組成物に基づく層が、各層に定義されたパターンに従って前記重合によって連続的に硬化され、第1の層は作業トレイ上に形成され、他の各層は前の層上に形成された後に硬化される、前記方法において、
請求項1~18のいずれか一項に記載の硬化性組成物が使用され、熱重合が、UV、可視、またはIR照射源の中から選択される少なくとも1つの照射源への曝露の作用下で各層に実施される、方法。
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JP2001181221A (ja) | 1999-12-21 | 2001-07-03 | Ciba Specialty Chem Holding Inc | 潜伏性酸供与体としてのヨードニウム塩 |
JP2007506836A (ja) | 2003-09-26 | 2007-03-22 | スリーエム イノベイティブ プロパティズ カンパニー | トリアリールスルホニウムおよびアリールスルフィン酸イオンを有する光開始剤 |
JP2009191367A (ja) | 2003-12-18 | 2009-08-27 | Showa Denko Kk | アルミニウム合金成形品の製造方法 |
JP2021017061A (ja) | 2019-07-22 | 2021-02-15 | エス.ア.エス. スリーディーセラム − シントー | 光造形法によるセラミック又は金属材料のグリーン体の部品(green piece)の、光熱ルート(photo−thermal route)を用いた製造方法 |
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FR3028851B1 (fr) * | 2014-11-24 | 2018-03-16 | S.A.S 3Dceram-Sinto | Procede de fabrication d'une piece ceramique en zircone coloree |
FR3059997B1 (fr) * | 2016-12-08 | 2019-07-05 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Composition de ceramique pour stereolithographie notamment sla |
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JP2001181221A (ja) | 1999-12-21 | 2001-07-03 | Ciba Specialty Chem Holding Inc | 潜伏性酸供与体としてのヨードニウム塩 |
JP2007506836A (ja) | 2003-09-26 | 2007-03-22 | スリーエム イノベイティブ プロパティズ カンパニー | トリアリールスルホニウムおよびアリールスルフィン酸イオンを有する光開始剤 |
JP2009191367A (ja) | 2003-12-18 | 2009-08-27 | Showa Denko Kk | アルミニウム合金成形品の製造方法 |
JP2021017061A (ja) | 2019-07-22 | 2021-02-15 | エス.ア.エス. スリーディーセラム − シントー | 光造形法によるセラミック又は金属材料のグリーン体の部品(green piece)の、光熱ルート(photo−thermal route)を用いた製造方法 |
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