JP2021017061A - 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 - Google Patents
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 Download PDFInfo
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Abstract
Description
− コンピュータ支援設計により、製造されるべき部品のコンピュータ・モデルを構築するステップであって、該モデルのサイズは、部品の製造中のセラミック又は金属材料の収縮が予測されるため、製造されるべき部品のサイズよりもわずかに大きい、ステップ
− 以下の通り部品を製造するステップ
− 剛性支持体上に、少なくとも1種のセラミック又は金属材料、光硬化性モノマー及び/又はオリゴマー、光開始剤、及び適切である場合、可塑剤、溶媒、分散剤、又は重合禁止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層を形成するステップ
− 光硬化性組成物の第1層を、該層のモデルに基づいて定められたパターンにしたがって照射することにより(該層の自由表面のレーザ走査によって、又はダイオード投影システムの使用によって)硬化させ、第1段を形成するステップ
− 第1段の上に、光硬化性組成物の第2層を形成するステップ
− 光硬化性組成物の第2層を、該層用に定められたパターンにしたがって照射することによって硬化させ、第2層を形成するステップであって、この照射は、第1層と同じやり方で実行される、ステップ
− 必要に応じて、グリーン体の部品が得られるまで上記のステップを繰り返すステップ
・ペースト・プロセスによる製造では、光硬化性組成物はペーストの形態であり、一方剛性支持体は、構築中の部品の様々な層ばかりでなくペーストを支持する作業トレイであり、それぞれの層は、一般に、作業トレイを下げて、所定の厚さでペーストを広げることによって形成される。ペーストの貯蔵は、タンク内に保管され、各層の所定の量のペーストのタンクが、ピストンを使用して自動的に空にされる。これにより、作業トレイによって前もって下げられている製造中の部品のより上側の層上に広げられるべき、ペーストのビーズが生成される。各層は一般に、作業トレイの作業面上を掃き取る「掻取り具」の刃を使用して掻き取ることで、たとえば直線状に水平方向に前進させることで、広げられる。
・液体プロセスによる製造の場合、光硬化性組成物は低粘度の懸濁液の形態である。
− 液体プロセスによる第1の実施例では、剛性支持体はトレイであり、トレイは、懸濁液の層でトレイを覆うために光硬化性懸濁液の槽の中に下ろされ、該層は次いで、上記で示したように照射されて硬化する。形成中の部品のより上側のレベルが、光硬化性懸濁液の自由表面より下に下ろされて当該の層を形成し、次いで該層が照射を受けるように、トレイを段階的に槽の中に下ろすことにより、続く各層は次いで、この第1層の上に連続的に形成される。
− 液体プロセスによる第2の実施例では、光硬化性懸濁液は、照射を可能にする透明な底部を有するタンク内に収容され、一方製造中の部品は、段階的に上昇するプラットフォームの形態の剛性支持体上に保持される。したがって、基部層を硬化させることから始まり、次いでプラットフォームを1ステップだけ上げて、次いで硬化させる新しい層を懸濁液が形成できるようにする。この工程は、層ごとに連続して繰り返される。
− 液体プロセスによる第3の実施例では、光硬化性懸濁液は、照射のために透明なフィルム上に層状に広げられ、フィルムは、水平に広がるように配置される。部品は、フィルムを通した照射によって硬化する層と接触するために下げられる、剛性のプラットフォーム上に形成される。次いで、新しい光硬化層で被覆されたフィルムの新しいセグメントを広げ、部品の構築が完了するまで工程を繰り返す。
− 少なくとも1種のセラミック又は金属粉末によってそれぞれ形成される、該セラミック又は金属材料、並びに
− 少なくとも1種のモノマー及び/又はオリゴマーと、該1種又は複数種類のモノマー及び/又は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有機要素
を含み、層ごとに定められたパターンにしたがって該重合により連続的に硬化し、第1層は構築プラットフォーム上に形成され、他の各層は先行する層上に形成され、次いで硬化し、
セラミック又は金属材料の、UV、可視、又はIR照射源から選択される少なくとも1つの照射源に対する露光中に、該セラミック又は金属材料によってそれぞれ放出される熱エネルギーの作用下で、熱重合の開始をもたらすことができる、少なくとも1種の熱開始剤が開始剤として使用されることを特徴とする。
− ペルオキシ安息香酸tert−アミル、過酸化ベンゾイル、2,2−ビス(tert−ブチルペルオキシ)ブタン、1,1−ビス(tert−ブチルペルオキシ)シクロヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチルヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチル−3−ヘキシン、ビス(1−(tert−ブチルペルオキシ)−1−メチルエチル)ベンゼン、1,1−ビス(tert−ブチルペルオキシ)−3,3,5−トリメチルシクロヘキサン、過酢酸tert−ブチル、過酸化tert−ブチル、過酸化安息香酸tert−ブチル、炭酸tert−ブチルペルオキシイソプロピル、過酸化シクロヘキサノン、過酸化ジクミル、過酸化ラウロイル、過酸化2,4−ペンタンジオン、過硫酸カリウム、及び過硫酸アンモニウムなどの過酸化物
− tert−ブチルヒドロペルオキシド、クメンヒドロペルオキシド、及び過酢酸などのヒドロペルオキシド
− N−(2−メチルプロピル)−N−(1−ジエチルホスホノ−2,2−ジメチルプロピル)−O−(2−カルボキシプロパ−2−イル)ヒドロキシルアミン(BlocBuilder(登録商標)MA)などのアルコキシアミン、並びに
− 1,1’−アゾビス(シクロヘキサンカルボニトリル)及び2,2’−アゾビスイソブチロニトリル(AIBN)などのアゾ化合物
− 1種又は複数種類のセラミック及び/又は金属粉末
− 1種又は複数種類のモノマー及び/又はオリゴマー、及び
− セラミック又は金属材料の、UV、可視、又はIR照射源から選択された少なくとも1つの照射源に対する露光中に、それぞれ該セラミック又は金属材料によって放出される熱エネルギーの作用下で、熱重合の開始をもたらすことができる、少なくとも1種の熱開始剤
− ペルオキシ安息香酸tert−アミル、過酸化ベンゾイル、2,2−ビス(tert−ブチルペルオキシ)ブタン、1,1−ビス(tert−ブチルペルオキシ)シクロヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチルヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチル−3−ヘキシン、ビス(1−(tert−ブチルペルオキシ)−1−メチルエチル)ベンゼン、1,1−ビス(tert−ブチルペルオキシ)−3,3,5−トリメチルシクロヘキサン、過酢酸tert−ブチル、過酸化tert−ブチル、過酸化安息香酸tert−ブチル、炭酸tert−ブチルペルオキシイソプロピル、過酸化シクロヘキサノン、過酸化ジクミル、過酸化ラウロイル、過酸化2,4−ペンタンジオン、過硫酸カリウム、及び過硫酸アンモニウムなどの過酸化物
− tert−ブチルヒドロペルオキシド、クメンヒドロペルオキシド、及び過酢酸などのヒドロペルオキシド
− N−(2−メチルプロピル)−N−(1−ジエチルホスホノ−2,2−ジメチルプロピル)−O−(2−カルボキシプロパ−2−イル)ヒドロキシルアミン(BlocBuilder(登録商標)MA)などのアルコキシアミン、並びに
− 1,1’−アゾビス(シクロヘキサンカルボニトリル)及び2,2’−アゾビスイソブチロニトリル(AIBN)などのアゾ化合物
から選択でき、具体的には、組成物の全容量に対して0.5から8容量部の割合で存在できる。
懸濁液を調剤し、その組成物を、以下の表に総容量の容量%で示し、やはり表に示した波長、出力、及びビーム径で光造形試験を実行した。こうした実験は、様々なレーザを備えたCERAMAKERタイプの光造形装置を使用して行った。
Claims (14)
- 光造形法を用いてセラミック又は金属材料で作られたグリーン体の部品を製造する方法であって、前記方法によると、硬化性組成物をベースとする層は、
少なくとも1種のセラミック又は金属粉末によってそれぞれ形成される、前記セラミック又は金属材料、並びに
少なくとも1種のモノマー及び/又はオリゴマーと、前記1種又は複数種類のモノマー及び/又は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有機要素
を含み、層ごとに定められたパターンにしたがって前記重合により連続的に硬化し、第1層は構築プラットフォーム上に形成され、他の各層は先行する層上に形成され、次いで硬化する方法において、
前記セラミック又は金属材料の、UV、可視、又はIR照射源から選択される少なくとも1つの照射源に対する露光中に、それぞれ前記セラミック又は金属材料によって放出される熱エネルギーの作用下で、熱重合の開始をもたらすことができる、少なくとも1種の熱開始剤が開始剤として使用されることを特徴とする、方法。 - 前記セラミック粉末は、ランタンストロンチウムマンガナイトセラミック、ランタンストロンチウムマンガナイトセラミックのイットリウム安定化ジルコニアとの混合物、ジルコニア、イットリウム安定化ジルコニア、及びフェライトなどの酸化物系セラミック粉末、並びに炭化ケイ素、窒化ケイ素、及び窒化アルミニウムなどの非酸化物系セラミック粉末から選択され、前記金属粉末は、銀、銅、鉄、タングステン、及びそれらの合金から選択され、具体的には、前記セラミック及び/又は前記金属粉末の、総容量に対して25から65容量部が使用されることを特徴とする、請求項1に記載の方法。
- 前記モノマー及び/又はオリゴマーは、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、及びその混合物などの、多官能性(メタ)アクリレートから選択され、具体的には、総容量に対して20から50容量部の割合で使用されることを特徴とする、請求項1又は2のいずれか一項に記載の方法。
- 前記熱開始剤は、
ペルオキシ安息香酸tert−アミル、過酸化ベンゾイル、2,2−ビス(tert−ブチルペルオキシ)ブタン、1,1−ビス(tert−ブチルペルオキシ)シクロヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチルヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチル−3−ヘキシン、ビス(1−(tert−ブチルペルオキシ)−1−メチルエチル)ベンゼン、1,1−ビス(tert−ブチルペルオキシ)−3,3,5−トリメチルシクロヘキサン、過酢酸tert−ブチル、過酸化tert−ブチル、過酸化安息香酸tert−ブチル、炭酸tert−ブチルペルオキシイソプロピル、過酸化シクロヘキサノン、過酸化ジクミル、過酸化ラウロイル、過酸化2,4−ペンタンジオン、過硫酸カリウム、及び過硫酸アンモニウムなどの過酸化物と、
tert−ブチルヒドロペルオキシド、クメンヒドロペルオキシド、及び過酢酸などのヒドロペルオキシドと、
N−(2−メチルプロピル)−N−(1−ジエチルホスホノ−2,2−ジメチルプロピル)−O−(2−カルボキシプロパ−2−イル)ヒドロキシルアミン(BlocBuilder(登録商標)MA)などのアルコキシアミンと、
1,1’−アゾビス(シクロヘキサンカルボニトリル)及び2,2’−アゾビスイソブチロニトリル(AIBN)などのアゾ化合物と
から選択され、前記熱開始剤は、具体的には、全容量に対して0.5から8容量部の割合で使用されることを特徴とする、請求項1から3までのいずれか一項に記載の方法。 - 具体的には、ポリエチレングリコール、フタル酸ジブチル、及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硬化性組成物が、具体的には、総容量に対して5から25容量部の割合で使用されることを特徴とする、請求項1から4までのいずれか一項に記載の方法。
- 具体的には、リン酸エステルから選択される少なくとも1種の分散剤をさらに含む硬化性組成物が、具体的には、総容量に対して1から8容量部の割合で使用されることを特徴とする、請求項1から5までのいずれか一項に記載の方法。
- 具体的には、4−メトキシフェノール及びフェノチアジンから選択される、少なくとも1種の重合禁止剤をさらに含む硬化性組成物が、具体的には、総容量に対して0.1から3容量部の割合で使用されることを特徴とする、請求項1から6までのいずれか一項に記載の方法。
- 請求項1から7までのいずれか一項に記載の方法を実施するための硬化性組成物であって、前記硬化性組成物は、
1種又は複数種類のセラミック及び/又は金属粉末と、
1種又は複数種類のモノマー及び/又はオリゴマーと、
前記セラミック又は前記金属材料の、UV、可視、又はIR照射源から選択された少なくとも1つの照射源に対する露光中に、それぞれ前記セラミック又は金属材料によって放出される熱エネルギーの作用下で、熱重合の開始をもたらすことができる、少なくとも1種の熱開始剤と
を含むことを特徴とする、組成物。 - 前記セラミック粉末は、ランタンストロンチウムマンガナイトセラミック、ランタンストロンチウムマンガナイトセラミックのイットリウム安定化ジルコニアとの混合物、ジルコニア、イットリウム安定化ジルコニア、及びフェライトなどの酸化物系セラミック粉末、並びに炭化ケイ素、窒化ケイ素、及び窒化アルミニウムなどの非酸化物系セラミック粉末から選択され、前記金属粉末は、銀、銅、鉄、タングステン、及びそれらの合金から選択され、前記セラミック及び/又は金属粉末は、具体的には、前記組成物の総容量に対して25から65容量部の割合で存在することを特徴とする、請求項8に記載の組成物。
- 前記モノマー及び/又はオリゴマーは、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、及びその混合物などの、多官能性(メタ)アクリレートから選択され、具体的には、前記組成物の総容量に対して20から50容量部の割合で存在することを特徴とする、請求項8又は9のいずれか一項に記載の組成物。
- 前記熱開始剤は、
ペルオキシ安息香酸tert−アミル、過酸化ベンゾイル、2,2−ビス(tert−ブチルペルオキシ)ブタン、1,1−ビス(tert−ブチルペルオキシ)シクロヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチルヘキサン、2,5−ビス(tert−ブチルペルオキシ)−2,5−ジメチル−3−ヘキシン、ビス(1−(tert−ブチルペルオキシ)−1−メチルエチル)ベンゼン、1,1−ビス(tert−ブチルペルオキシ)−3,3,5−トリメチルシクロヘキサン、過酢酸tert−ブチル、過酸化tert−ブチル、過酸化安息香酸tert−ブチル、炭酸tert−ブチルペルオキシイソプロピル、過酸化シクロヘキサノン、過酸化ジクミル、過酸化ラウロイル、過酸化2,4−ペンタンジオン、過硫酸カリウム、及び過硫酸アンモニウムなどの過酸化物と、
tert−ブチルヒドロペルオキシド、クメンヒドロペルオキシド、及び過酢酸などのヒドロペルオキシドと、
N−(2−メチルプロピル)−N−(1−ジエチルホスホノ−2,2−ジメチルプロピル)−O−(2−カルボキシプロパ−2−イル)ヒドロキシルアミン(BlocBuilder(登録商標)MA)などのアルコキシアミンと、
1,1’−アゾビス(シクロヘキサンカルボニトリル)及び2,2’−アゾビスイソブチロニトリル(AIBN)などのアゾ化合物と
から選択され、前記熱開始剤は、具体的には、全容量に対して0.5から8容量部の割合で使用されることを特徴とする、請求項8から10までのいずれか一項に記載の組成物。 - 前記組成物は、具体的には、ポリエチレングリコール、フタル酸ジブチル、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、具体的には、前記組成物の総容量に対して5から25容量部の割合でさらに含むことを特徴とする、請求項8から11までのいずれか一項に記載の組成物。
- 前記組成物は、具体的には、リン酸エステルから選択される少なくとも1種の分散剤を、具体的には、前記組成物の総容量に対して1から8容量部の割合でさらに含むことを特徴とする、請求項8から12までのいずれか一項に記載の組成物。
- 前記組成物は、具体的には、4−メトキシフェノール及びフェノチアジンから選択される少なくとも1種の重合禁止剤を、具体的には、前記組成物の総容量に対して0.1から3容量部の割合でさらに含むことを特徴とする、請求項8から13までのいずれか一項に記載の組成物。
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CN103755889A (zh) * | 2014-01-10 | 2014-04-30 | 上海那恒新材料有限公司 | 可发光的高精度三维成型光敏树脂组合物 |
EP3023226B1 (de) | 2014-11-19 | 2017-02-08 | Ivoclar Vivadent AG | Stereolithographievorrichtung mit Heizeinrichtung |
FR3028851B1 (fr) * | 2014-11-24 | 2018-03-16 | S.A.S 3Dceram-Sinto | Procede de fabrication d'une piece ceramique en zircone coloree |
WO2016172788A1 (en) * | 2015-04-30 | 2016-11-03 | Fortier, Raymond | Improved stereolithography system |
CN105198449B (zh) * | 2015-09-16 | 2018-03-09 | 广东工业大学 | 一种光固化成型的高致密陶瓷的制备方法 |
RU2627796C2 (ru) * | 2015-12-10 | 2017-08-11 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Томский государственный университет систем управления и радиоэлектроники" (ТУСУР) | Способ послойного электронно-лучевого спекания изделий из керамического порошка |
FR3070134B1 (fr) * | 2017-08-18 | 2019-08-16 | S.A.S 3Dceram-Sinto | Procede et machine de fabrication d'au moins une piece en au moins un materiau ceramique et/ou metallique par la technique des procedes additifs |
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- 2020-07-21 CN CN202010707624.2A patent/CN112277122A/zh active Pending
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- 2020-07-21 JP JP2020124662A patent/JP7119033B2/ja active Active
- 2020-07-21 UA UAA202004619A patent/UA125270C2/uk unknown
- 2020-07-22 KR KR1020200090933A patent/KR102484206B1/ko active IP Right Grant
- 2020-07-22 US US16/935,277 patent/US20210024422A1/en not_active Abandoned
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JP2022161889A (ja) * | 2021-04-09 | 2022-10-21 | エス.ア.エス. スリーディーセラム - シントー | 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 |
JP7314351B2 (ja) | 2021-04-09 | 2023-07-25 | エス.ア.エス. スリーディーセラム - シントー | 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 |
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US20210024422A1 (en) | 2021-01-28 |
KR102484206B1 (ko) | 2023-01-03 |
FR3099079B1 (fr) | 2021-06-25 |
RU2739093C1 (ru) | 2020-12-21 |
ES2956343T3 (es) | 2023-12-19 |
KR20210011345A (ko) | 2021-02-01 |
EP3769964A1 (fr) | 2021-01-27 |
PT3769964T (pt) | 2023-07-19 |
JP7119033B2 (ja) | 2022-08-16 |
UA125270C2 (uk) | 2022-02-09 |
CN112277122A (zh) | 2021-01-29 |
EP3769964B1 (fr) | 2023-06-21 |
FR3099079A1 (fr) | 2021-01-29 |
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