TWI630244B - 三維列印用牙科材料及其製備方法與應用 - Google Patents

三維列印用牙科材料及其製備方法與應用 Download PDF

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TWI630244B
TWI630244B TW106118743A TW106118743A TWI630244B TW I630244 B TWI630244 B TW I630244B TW 106118743 A TW106118743 A TW 106118743A TW 106118743 A TW106118743 A TW 106118743A TW I630244 B TWI630244 B TW I630244B
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林元敏
陳翾
李士元
黃品儒
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國立陽明大學
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Abstract

本發明提供一種三維列印用牙科材料，其中包含：雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯以及一二苯基-(2,4,6-三甲基苯甲酰)氧磷(Diphenyl(2,4,6-trimethylbenzoyl)，改良目前的臨時假牙製作過程耗時又費工，且無法大量製造的缺點。

Description

三維列印用牙科材料及其製備方法與應用
本發明係有關一種三維列印之牙科材料，特別是由雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯之組成物與光起始劑的混合形成。
三維列印目前主要的技術可分為(1)光固化成型(stereolithographyappearance，SLA)，是使用光聚合物通過紫外雷射照射來固化。(2)選擇性雷射燒結(selectivelasersintering，SLS)，是用小顆粒的熱塑性材料(包括尼龍等聚合物，青銅合金、鈦合金等金屬，以及陶瓷和玻璃)粉末用高功率雷射來融合。(3)熔融沉積成型(fuseddepositionmodeling，FDM)，是噴出熔融的熱塑性材料或共晶金屬粉末，立即使其凝固。(4)分層實體製造(laminatedobjectmanufacturing，LOM)，是使用膠水把紙張或塑料膜粘在一起，然後用雷射塑形。(5)噴墨列印技術，是將不同種類的細粉末打出來以後，塗上粘接劑，然後列印下一層。噴墨列印技術還可以通過同時列印活體細胞和生物材料來構建一個含有不同組織的三維生物支架，甚至活體器官。
目前口腔種植技術發展，雖然在核心技術上逐漸得到突破和應用，但依然需要有高技術水平、操作經驗豐富的醫師進行數小時的仔細工作，需進行診斷、麻醉、種植體選擇、牙模灌注、臨時冠設計製作、假牙修飾裝配等工作，此為目前口腔種植高價格、高風險的主要原因。三維列印技術在口腔種植領域的應用，就是將口腔掃描、口腔圖像處理和三維列印技術整合起來，採用「圖像數字化採集重構、CAD/CAM專業設計、 標準化三維列印製造、規範化種植治療」等技術系統，最終達到可在術前通過電腦看到術後的效果，只需在手術前，將患者口腔進行斷層掃描，將精確的數據輸入到特定的設計軟體，透過三維設計種植體植入位置，選擇合適種植體類型，然後按照導航模板施術，植入義齒種植體和修復體，並按患者的需求進行大性化修飾。這種方法可克服二維掃描影像重疊容易造成醫生誤判等問題，降低了醫生由於技藝和經驗不足的風險，減少了醫師的工作負荷，提高診療「安全性」，在數字化資源共享下，實現「經濟化」診療。
過往的臨時假牙製作過程耗時又費工，又缺乏可大量製造的方便性。然而，憑藉目前三維列印的製造工法，已經可以將完成品的精準度提升至數個微米的程度，對於牙科這樣的精密加工的領域提供了一股助力。現今可以依靠三維列印的方式在就診時間內便可取得臨時假牙，大大縮短病患等待的時間。目前坊間三維列印材料多為國外設備商所提供，又因取得成本相對昂貴，因此開法一種平價的三維列印用牙科，即為一刻不容緩的發展課題。
有鑑於此，本發明提供牙科常規使用的樹脂為主輔以牙科填料作為三維列印樹脂材料填充材，其成品具有優良的生物相容性且具無毒性不會傷害人體，並可降低牙科材料成本。
本發明旨在提供一種三維列印用牙科材料，其包含：一組合物，係由20%~100%雙酚A乙氧基雙丙烯酸酯樹脂、0%~80%雙甲基丙烯酸氨基甲酸乙酯以及0~20%雙甲基丙烯酸三縮乙二酯所組成；以及一光起始劑，係為該組合物總重量0.1%~5%。
本發明又提供一種前述三維列印用牙科材料的製備方法，其包含以下步驟：(a)將雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯於室溫中攪拌均勻，形成一組合物，其中，雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯的比例為20%~100%：0%~80%：0~20%；以及(b)加入 該組合物總重量0.1%~5%的一光起始劑至該組合物中，混合形成一三維列印用牙科材料。
本發明再提供一種以前述三維列印用牙科材料的假牙製作方法，其包含以下步驟：(a)將一三維列印用牙科材料倒入一容槽中；(b)取得一假牙之連續切面圖，其中，該些由切面圖相距一間距；(c)由該假牙頂部開始選擇其一切面圖，透過一光源聚合照射該容槽底部形成一片狀模型；以及(d)待固定後，向上挪移該片狀模型該間距，重覆步驟(c)至該假牙底部，形成一假牙模型。
由此，本發明所提供之三維列印用牙科材料以樹脂為主，輔以無機物填料作為填充材，其成品具有優良的生物相容性，又因該三維列印用牙科材料呈乳膠狀，得由注入或容槽承載為現有三維列印機材所使用。
為了使任何熟習相關技藝者瞭解本發明之技術內容並據以實施，且根據本說明書所揭露之內容、申請專利範圍及圖式，任何熟習相關技藝者可輕易地理解本發明相關之目的及優點，因此將在實施方式中詳細敘述本發明之詳細特徵以及優點。
步驟101至103‧‧‧為本發明三維列印用牙科材料的製備方法流程
步驟201至204‧‧‧為本發明三維列印用牙科材料的假牙製作方法流程
第一圖係為本發明三維列印用牙科材料的製備方法流程圖；第二圖係為本發明三維列印用牙科材料的假牙製作方法流程圖；
為讓鈞院貴審查委員及習於此技術人士，對本發明之功效完全瞭解，就本發明較佳之實施例說明如下，本發明旨在提供一種三維列印用牙科材料，其包含：一組合物，係由20%~100%雙酚A乙氧基雙丙烯酸酯樹脂(Ethoxylated bisphenol A diacrylate，BisEMA)(化學式I)，較佳地，該雙酚A乙氧基雙丙烯酸酯樹脂具有2個n,m=2、4或10的乙氧基鏈、 0%~80%雙甲基丙烯酸氨基甲酸乙酯(Diurethane dimethacrylate，UDMA)(化學式I)以及 0~20%雙甲基丙烯酸三縮乙二酯(Triethylene glycol dimethacrylate，TEGDMA)(化學式III)所組成；以及 一光起始劑，係為該組合物總重量0.1%~5%，較佳地，該光起始劑為二苯基-(2,4,6-三甲基苯甲酰)氧磷(Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide，TPO)。
在一實施例中，前述三維列印用牙科材料包含一阻光劑，係由該組合物總重量0.1%~5%的二氧化矽或矽烷化二氧化矽、該組合物總重量0.01%~1.0%的二氧化鈦所組成。
再一實施例中，前述三維列印用牙科材料包含一調色劑，係由該組合物總重量0.01~0.05%的水合氧化鐵(III)或該組合物總重量0.001%~0.05%的三氧化二鐵所組成，較佳地，該氧化鐵可為四氧化三鐵、無水氧化鐵、無水氧化鐵(III)、水合氧化鐵、一氧化鐵、鐵氧化鐵、或鐵(II、III)氧化物。
本發明又提供一種前述三維列印用牙科材料的製備方法，請參考第二圖所示，其包含以下步驟：(a)將雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯於室溫中攪拌均勻，形成一組合物，其中，雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯的比例為20%~100%：0%~80%：0~20%，步驟101；以及(b)加入該組合物總重量0.1%~5%的一光起始劑至該組合物中，混合形成一三維列印用牙科材料，步驟102。
在一實施例中，前述三維列印用牙科材料的製備方法包含步驟(c)加入一阻光劑或一調色劑至該組合物中，改變該三維列印用牙科材料的顏色，步驟103，其中，該阻光劑由該組合物總重量0.1%~5%的二氧化矽或矽烷化二氧化矽、該組合物總重量0.01%~1.0%的二氧化鈦所組成，且該調色劑係由該組合物總重量0.01~0.05%的水合氧化鐵(III)或該組合物總重量0.001%~0.05%的三氧化二鐵所組成。
本發明再提供一種以前述三維列印用牙科材料的假牙製作方法，請參考第三圖所示，其包含以下步驟：(a)將一三維列印用牙科材料倒入一容槽中，步驟201；(b)取得一假牙之連續切面圖，其中，該些由切面圖相距一間距，步驟202；(c)由該假牙頂部開始選擇其一切面圖，透過一光源聚合照射該容槽底部形成一片狀模型，步驟203，較佳地，係透過波長範圍為385至500nm的光源聚合照射該容槽底部0~8秒，較佳地為3~5秒之間；以及(d)待固定後，向上挪移該片狀模型該間距，重覆步驟(c)至該假牙底部，形成一假牙模型，步驟204，並進行清洗與後固化處理。
在一實施例中，本發明進一步測試該三維列印用牙科材料特性，係揭示(1)表面微硬度：本發明牙科材料其表面微硬度利用維克氏硬度試驗儀(Vickers hardness test，HMV-2，Shimadzu，京都，日本)，當壓痕器荷重0.1公斤，加壓於試片25秒，量測結果微硬度為15.9HV；以及，(2)抗彎曲測試：本材料抗壓能力係利用萬能材料試驗機(AGS-500G，Shimadzu，京都，日本)進行三點彎曲測試，試驗機上配備有100kg荷重元。兩支撐架之間的距離為25mm，荷重元其下降的速度為每分鐘2mm，量測結果抗彎曲能力為97.4MPa。
惟上述各實施例係用以說明本發明之特點，其目的在使熟習前述技術者能瞭解本發明之內容並據以實施，而非限定本發明之專利範圍，故凡其他未脫離本發明所揭示之精神而完成之等效修飾或修改，仍應包含在以下所述之申請專利範圍中。

Claims (9)

  1. 一種三維列印用牙科材料，其包含：一組合物，係由20%~100%雙酚A乙氧基雙丙烯酸酯樹脂、0%~80%雙甲基丙烯酸氨基甲酸乙酯以及0~20%雙甲基丙烯酸三縮乙二酯所組成；一光起始劑，係為該組合物總重量0.1%~5%；以及一調色劑，係由該組合物總重量0.01~0.05%的水合氧化鐵(III)或該組合物總重量0.001%~0.05%的三氧化二鐵所組成。
  2. 如申請專利範圍第1項所述之三維列印用牙科材料，其中，該雙酚A乙氧基雙丙烯酸酯樹脂化學式所敘如下，具有2個n,m=1、2、4或10的乙氧基鏈。
  3. 如申請專利範圍第1項所述之三維列印用牙科材料，其中，該光起始劑為二苯基-(2,4,6-三甲基苯甲酰)氧磷。
  4. 如申請專利範圍第1項所述之三維列印用牙科材料，其進一步包含：一阻光劑，係由該組合物總重量0.1%~5%的二氧化矽或矽烷化二氧化矽、該組合物總重量0.01%~1.0%的二氧化鈦所組成。
  5. 如申請專利範圍第1項所述之三維列印用牙科材料，其中，該氧化鐵可為四氧化三鐵、無水氧化鐵、無水氧化鐵(III)、水合氧化鐵、一氧化鐵、鐵氧化鐵、或鐵(II、III)氧化物。
  6. 一種如申請求範圍第1項所敘之三維列印用牙科材料的製備方法，其包含以下步驟：(a)將雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯於室溫中攪拌均勻，形成一組合物，其中，雙酚A乙氧基雙丙烯酸酯樹脂、雙甲基丙烯酸氨基甲酸乙酯、雙甲基丙烯酸三縮乙二酯的比例為20%~100%：0%~80%：0~20%；(b)加入該組合物總重量0.1%~5%的一光起始劑至該組合物中；以及(c)加入一調色劑至該組合物中，該調色劑係由該組合物總重量0.01~0.05%的水合氧化鐵(III)或該組合物總重量0.001%~0.05%的三氧化二鐵所組成，混合形成一三維列印用牙科材料。
  7. 如申請專利範圍第6項所述之製備方法，其進一步包含以下步驟：(d)加入一阻光劑至該組合物中，改變該三維列印用牙科材料的顏色，其中，該阻光劑由該組合物總重量0.1%~5%的二氧化矽或矽烷化二氧化矽、該組合物總重量0.01%~1.0%的二氧化鈦所組成。
  8. 一種以申請求範圍第1項所敘之三維列印用牙科材料的假牙製作方法，其包含以下步驟：(a)將一三維列印用牙科材料倒入一容槽中；(b)取得一假牙之連續切面圖，其中，該些由切面圖相距一間距；(c)由該假牙頂部開始選擇其一切面圖，透過一光源聚合照射該容槽底部形成一片狀模型；以及(d)待固定後，向上挪移該片狀模型該間距，重覆步驟(c)至該假牙底部，形成一假牙模型。
  9. 如申請專利範圍第8項所述之假牙製作方法，其中，步驟(c)係透過波長範圍為385至500nm的光源聚合照射該容槽底部0~8秒。
TW106118743A 2017-03-07 2017-06-06 三維列印用牙科材料及其製備方法與應用 TWI630244B (zh)

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