CN108350297A - 用于3d打印支撑体的墨组合物和使用其的3d打印生产方法 - Google Patents
用于3d打印支撑体的墨组合物和使用其的3d打印生产方法 Download PDFInfo
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- CN108350297A CN108350297A CN201780004085.2A CN201780004085A CN108350297A CN 108350297 A CN108350297 A CN 108350297A CN 201780004085 A CN201780004085 A CN 201780004085A CN 108350297 A CN108350297 A CN 108350297A
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- ink composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Abstract
公开了一种用于3D打印支撑体的墨组合物和使用其的3D打印生产方法，其中所述墨组合物可用于喷墨3D打印机，具有优异的喷射特性，并且在固化之后易溶于水使得支撑体可以被容易地除去。所述用于3D打印支撑体的墨组合物包含：含胺单体；固化剂；和具有含胺聚合物的水溶性聚合物。
Description
技术领域
本申请要求于2016年2月26日提交的韩国专利申请第10-2016-0023280号的优先权的权益，其全部公开内容通过引用并入本文。
本发明涉及用于3D打印支撑体的墨组合物和使用其生产3D打印的方法。更具体地，本发明涉及用于3D打印支撑体的墨组合物和使用其的3D打印生产方法，其中所述墨组合物可用于喷墨3D打印机，具有优异的喷射特性，并且在固化之后易溶于水使得支撑体可以被容易地除去。
背景技术
3D打印机(三维打印机)，一种三维地打印特定物体的打印机类型，是可以如同在纸上打印三维设计一样在三维空间中生产实物的装置。如同通过在将数字化文件传送至喷墨打印机中后将墨喷射至纸的表面上以打印2D图像的原理，除了2D打印机中的前后(x轴)和左右(y轴)移动之外，3D打印机另外地上下(z轴)移动以基于输入的3D图像生产三维物体。当用这样的3D打印机制作雕塑时，桥结构或浮在空中的结构需要支撑材料。这样的支撑材料也起到很好地支撑所述结构的作用，但其也必须稍后被容易地除去。
发明内容
技术问题
如上所述，当使用3D打印机生产桥形状或漂浮形状时，需要支撑材料。对于这样的支撑材料，需要可以用于喷墨3D打印机的用于支撑体的墨。然而，在常规的用于支撑体的墨的情况下，存在需要复杂的除去过程的问题，例如，手动移去支撑体或者使用喷水法逐个除去支撑体等。例如，韩国专利特许公开第2013-0141561号公开了在通过喷墨光成形方法形成光成形制品期间用于支撑形状的支撑材料。然而，在这种情况下，花费大量的时间和精力来除去支撑体，并且不容易彻底除去支撑体。此外，存在支撑体收缩的问题。因此，为了解决这些问题，需要研究这样的墨：其可以光固化，同时在固化之后允许通过简单的方法例如声波处理或浸入水中振荡来除去。
因此，本发明的一个目的是提供用于3D打印支撑体的墨组合物和使用其生产3D打印的方法，所述用于3D打印支撑体的墨组合物可以用于喷墨3D打印机，具有优异的喷射特性，并且在固化之后易溶于水以便于支撑体的除去。
技术方案
为了实现上述目的，本发明提供了用于3D打印支撑体的墨组合物，其包含：含胺单体；固化剂；和含有含胺聚合物的水溶性聚合物。
此外，本发明提供了使用所述用于3D打印支撑体的墨组合物生产3D打印的方法。
发明效果
根据本发明，提供了墨组合物和使用其生产3D打印的方法，所述墨组合物可以用于喷墨3D打印机，具有优异的喷射特性，并且在固化之后易溶于水以便于支撑体的除去。
具体实施方式
在下文中，将详细描述本发明。
根据本发明的用于3D打印支撑体的墨组合物包含含胺单体；固化剂；和含有含胺聚合物的水溶性聚合物。
通过包含如上所述的组分，根据本发明的用于3D打印支撑体的墨组合物可以用于喷墨3D打印机，具有优异的喷射特性，并且在固化之后易溶于水以便于支撑体的除去。
含胺单体没有特别限制，只要其是本领域中使用的即可。优选的是具有1至30个碳原子并且包含至少一个胺基的单体，更优选的是具有2至10个碳原子并且包含至少一个胺基的单体。其实例包括N,N-二甲基丙烯酰胺(DMA)、双丙酮丙烯酰胺(DAA)、N-[3-(二甲基氨基)丙基]甲基丙烯酰胺(DMAPMA)、N-甲基-N-乙烯基乙酰胺(NMNVA)、2-(二甲基氨基)乙基丙烯酸酯(DMAEA)、N-乙烯基吡咯烷酮(VP)、4-丙烯酰吗啉(ACMO)、N-甲基丙烯酰吗啉、N-异丙基丙烯酰胺(NIPA)、2-甲基-2-唑啉、2-乙基-2-唑啉、N-异丙基-2-唑啉、乙烯亚胺、氮丙啶及其混合物。
基于根据本发明的用于3D打印支撑体的墨组合物的总重量，含胺单体可以以10重量％至99.9重量％的量被包含在内。如果含胺单体的含量小于10重量％，则在支撑体除去期间在水中的溶解特性可能不足。如果其超过99.9重量％，则固化特性可能劣化。
固化剂包含在根据本发明的用于3D打印支撑体的墨组合物中并且可以用于通过各种固化方法进行的固化过程。根据固化方法可以使用各种固化剂。可以没有限制地使用常规的固化剂。更具体地，可以使用光引发剂作为固化剂，并且没有特别限制，只要其是本领域中根据待使用的光源使用的即可。优选地，可以使用Irgacure 819(基于双酰基膦的)、Darocur TPO (基于单酰基膦的)、Irgacure 369(基于α-氨基酮的)、Irgacure 184(基于α-羟基酮的)、Irgacure 907(基于α-氨基酮的)、Irgacure 2022(基于双酰基膦/α-羟基酮的)、Irgacure 2100(基于氧化膦的)、Darocur ITX(异丙基噻吨酮)、或者与它们具有类似结构的产品如光引发剂。
基于根据本发明的用于3D打印支撑体的墨组合物的总重量，固化剂可以以0.01重量％至20重量％，优选1重量％至10重量％的量被包含在内。如果固化剂的含量小于0.01重量％，则可能不发生固化。如果固化剂的含量大于20重量％，则固化灵敏度可能过度增加并且头部可能被堵塞。
含有含胺聚合物的水溶性聚合物用于控制墨的粘度并且使得固化产物能够更容易地溶于水。其可以是通过使含胺单体聚合获得的聚合物和其他水溶性聚合物(即，通过使不含胺单体聚合获得的水溶性聚合物)中的任一者或更多者。可以没有限制地使用常规的通过使含胺单体聚合获得的聚合物和常规的水溶性聚合物。然而，通过使含胺单体聚合获得的聚合物和通过使不含胺单体聚合获得的水溶性聚合物不仅可以是由单一类型的单体形成的均聚物，而且可以是由两种或更多种不同的单体形成的共聚物。
由于墨的粘度控制变得容易，所以可以将墨的粘度升高至所需水平(但是，如果墨的粘度较高，则必须加热头部以喷射)。当墨的粘度增加时，可以防止墨在3D雕塑生产中过度扩散，使得其不仅允许以高分辨率制造精确形状，而且还允许提高墨的固化灵敏度。尤其是可以防止墨在雕塑的边缘部分流下并扩散至不期望部分。如果以更高分辨率制造雕塑，则一层的高度变得较高，使得能够增加制造3D雕塑的速度。
在水溶性聚合物中，通过使含胺单体聚合获得的聚合物例示为聚乙烯基吡咯烷酮(PVP)、聚(N,N-二甲基丙烯酰胺)(PDMA)、聚(N-异丙基丙烯酰胺)(PNIPA)、聚(N-丙烯酰吗啉)(PACMO)、聚(N-甲基丙烯酰吗啉)、聚(2-甲基-2-唑啉)、聚(2-乙基-2-唑啉)、聚(N-异丙基-2-唑啉)、聚乙烯亚胺(PEI)、聚(2-异丙烯基-2-唑啉-共聚-甲基丙烯酸甲酯)、聚(乙烯基吡咯烷酮-共聚-乙酸乙烯酯)、聚(N,N-二甲基丙烯酰胺-共聚-2-羟乙基甲基丙烯酸酯)等。
在水溶性聚合物中，除通过使含胺单体聚合获得的聚合物之外的聚合物，即，通过使不含胺单体聚合获得的水溶性聚合物，例示为聚丙烯酸(PAA)、聚(2-羟乙基丙烯酸酯)、聚(2-羟乙基甲基丙烯酸酯)等。
基于根据本发明的用于3D打印支撑体的墨组合物的总重量，水溶性聚合物可以以0.01重量％至30重量％的量被包含在内。如果基于墨组合物的总重量，水溶性聚合物的含量小于0.01重量％，则通过添加来增加溶解度的效果可能变得不显著。如果含量大于30重量％，则墨的粘度变高，使得喷射可能变得不可能。
根据本发明的用于3D打印支撑体的墨组合物还可以包含含有乙烯基和丙烯酸酯基中至少一者的单体(即，V/A单体)。这使得可以控制固化灵敏度和膜的特性，例如固化产物的强度(软度或硬度)。
含有乙烯基和丙烯酸酯基中至少一者的单体没有特别限制，只要其是本领域中使用的即可。优选地，可以使用例如选自以下中的至少一者：乙酸乙烯酯、2-羟乙基(甲基)丙烯酸酯、2-羟甲基(甲基)丙烯酸酯、2-羟丙基(甲基)丙烯酸酯、4-羟丁基(甲基)丙烯酸酯、乙基-2-羟基丙烯酸酯、2-(丙烯酰氧基)乙基氢琥珀酸酯和甲基丙烯酸。
当使用含有乙烯基和丙烯酸酯基中至少一者的单体时，基于根据本发明的用于3D打印支撑体的墨组合物的总重量，含有乙烯基和丙烯酸酯基中至少一者的单体优选以0.01重量％至80重量％的量使用。如果基于墨组合物的总重量，含有乙烯基和丙烯酸酯基中至少一者的单体的含量小于0.01重量％，则难以通过添加单体获得足够的效果。如果单体的含量大于80重量％，则存在固化产物不溶于水的问题。
根据本发明的用于3D打印支撑物的墨组合物还可以包含添加剂，例如表面活性剂、增塑剂、(热)聚合抑制剂、稳定剂、消泡剂、稀释剂和粘度控制剂。从经济角度来看，添加剂可以以能够发挥其作用的最小量被包含在内。优选地，基于墨组合物的总重量，添加剂可以以0.01重量％至5重量％的量被包含在内。
此外，本发明提供了通过上述的用于3D打印支撑体的墨组合物生产的支撑体。支撑体没有特别限制，只要其是在3D打印过程中使用的即可。
此外，本发明提供了用于生产3D打印的方法，特征在于使用所述用于3D打印支撑体的墨组合物。所述方法没有特别限制，只要其与3D打印的过程有关即可。
发明实施方式
在下文中，将描述本发明的优选实施方案以便于理解本发明。对于本领域的技术人员来说显而易见的是，在不偏离本发明的精神或范围的情况下可以对本发明做出各种修改和改变。这些修改和改变旨在落入所附权利要求的范围内。
实施例
墨的制备
如下表1所示地混合含胺单体、固化剂、水溶性聚合物、含有乙烯基和丙烯酸酯基中至少一者的单体(V/A单体)等以制备实施例1至3的墨。此外，用下表1中所示的组成制备比较例1至3的墨。
[表1]
DMA：N,N-二甲基丙烯酰胺
VP：N-乙烯基吡咯烷酮
PVP：聚乙烯基吡咯烷酮
HEMA：2-羟乙基甲基丙烯酸酯
DPHA：二季戊四醇六丙烯酸酯
TPGDA：三丙二醇二丙烯酸酯
PD-6400：丙烯酸树脂(由Almatex，USA制造)
实验例
使用实施例1至3和比较例1至3的墨生产支撑体结构。评估所生产的支撑体结构中的每一者在水中的溶解度和固化度(固化灵敏度)。其结果与每种墨的粘度一起在下表2中示出。
实验例1.在水中的溶解性的评估
用滴管将实施例1至3和比较例1至3中制备的墨中的每一者滴至膜基底上，然后使用高压汞灯以1000mJ/cm2的暴光量进行暴光。随后，重复形成多个层以制备墨的固化产物样品。将样品从基底上取下并浸入水中。然后，将其中浸没了墨的固化产物的瓶在超声仪中声波处理60分钟。通过确定固化支撑体的膜是否溶解在水中来评估溶解性。其结果在下表2中示出。在表2中，符号○表示其中其在水中溶解良好的情况，符号△表示其中其轻微溶解的情况(即，仅部分物质溶解的情况)，符号×表示其中其不溶于水的情况。
实验例2.固化灵敏度的评估
将实施例1至3和比较例1至3中制备的墨中的每一者旋涂至玻璃上，然后使用波长为365nm的LED灯进行曝光，同时控制曝光量分别为125mJ/cm2、250mJ/cm2、500mJ/cm2和1000mJ/cm2。通过视觉观察其是否固化来评估固化灵敏度。墨开始完全固化时的暴露量在表2中示出。
实验例3.图案形成的评估
通过喷射电压为85V且喷射频率为1000Hz的喷墨头(Dimatix 30pL128喷嘴头)喷出(eject)实施例1和比较例1中制备的墨中的每一者，然后使用波长为395nm的LED灯(暴露量：2000mJ/cm2)固化以形成图案。分别在1200dpi和600dpi的分辨率条件下评估图案。其结果在下表2中示出。在表2中，符号○表示其中图案正常形成的情况，符号×表示其中图案没有正常形成的情况。
[表2]
如表2所示，发现由实施例1至3的组成制备的所有墨都具有优异的粘度、在水中的溶解性和固化灵敏度。相反，在由比较例1的组成制备的墨的情况下，在水中的溶解性是优异的，但固化灵敏度和粘度显著低于实施例1至3中制备的墨的固化灵敏度和粘度。此外，在由比较例2和3的组成制备的墨的情况下，固化灵敏度和粘度是优异的，但发现墨的固化支撑体的膜仅部分溶解或根本不溶解，表明在水中的溶解性不好。
此外，在使用墨形成图案时，对于实施例1，在1200dpi的分辨率下很好地形成矩形图案(一层的高度：65μm)，但对于比较例1，墨扩散得太多使得图案在1200dpi的分辨率下塌陷，使得无法形成矩形图案。当将分辨率降低至600dpi时，形成图案。然而，在这种情况下，每单位面积喷出的液滴数量减少，使得一层的高度仅为43μm。即，在其中墨的粘度高的实施例1的情况下，可以在高分辨率下很好地形成图案，并且一层的高度较高，使得可以更快地制造3D雕塑。另一方面，在其中粘度低的比较例1的情况下，墨扩散得太多，并且墨扩散到期望形状的图案之外。如果墨扩散得太多，则其可能与相邻结构的墨混合。因此，可以看出将比较例1的墨用于支撑体是不优选的。
Claims (17)
1.一种用于3D打印支撑体的墨组合物，包含：
含胺单体；
固化剂；和
含有含胺聚合物的水溶性聚合物。
2.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，基于所述用于3D打印支撑体的墨组合物的总重量，所述含胺单体的含量为10重量％至99.9重量％。
3.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，基于所述用于3D打印支撑体的墨组合物的总重量，所述固化剂的含量为0.01重量％至20重量％。
4.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，基于所述用于3D打印支撑体的墨组合物的总重量，所述水溶性聚合物的含量为0.01重量％至30重量％。
5.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述含胺单体为具有1至30个碳原子并且含有至少一个胺基的单体。
6.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述含胺单体选自：N,N-二甲基丙烯酰胺、双丙酮丙烯酰胺、N-[3-(二甲基氨基)丙基]甲基丙烯酰胺、N-甲基-N-乙烯基乙酰胺、2-(二甲基氨基)乙基丙烯酸酯、N-乙烯基吡咯烷酮、4-丙烯酰吗啉、N-甲基丙烯酰吗啉、N-异丙基丙烯酰胺、2-甲基-2-唑啉、2-乙基-2-唑啉、N-异丙基-2-唑啉、乙烯亚胺及其混合物。
7.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述固化剂为光引发剂。
8.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述水溶性聚合物为选自通过使含胺单体聚合获得的聚合物和通过使不含胺单体聚合获得的水溶性聚合物中的至少一者。
9.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述水溶性聚合物是选自均聚物和共聚物的类型。
10.根据权利要求8所述的用于3D打印支撑体的墨组合物，特征在于，所述通过使含胺单体聚合获得的聚合物选自：聚乙烯基吡咯烷酮、聚(N,N-二甲基丙烯酰胺)、聚(N-异丙基丙烯酰胺)、聚(N-丙烯酰吗啉)、聚(N-甲基丙烯酰吗啉)、聚(2-甲基-2-唑啉)、聚(2-乙基-2-唑啉)、聚(N-异丙基-2-唑啉)、聚乙烯亚胺、聚(2-异丙烯基-2-唑啉-共聚-甲基丙烯酸甲酯)、聚(乙烯基吡咯烷酮-共聚-乙酸乙烯酯)和聚(N,N-二甲基丙烯酰胺-共聚-2-羟乙基甲基丙烯酸酯)。
11.根据权利要求8所述的用于3D打印支撑体的墨组合物，特征在于，所述通过使不含胺单体聚合获得的水溶性聚合物选自：聚丙烯酸、聚(2-羟乙基丙烯酸酯)和聚(2-羟乙基甲基丙烯酸酯)。
12.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述用于3D打印支撑体的墨组合物还包含含有乙烯基和丙烯酸酯基中至少一者的单体。
13.根据权利要求12所述的用于3D打印支撑体的墨组合物，特征在于，所述含有乙烯基和丙烯酸酯基中至少一者的单体为选自以下中的至少一者：乙酸乙烯酯、2-羟乙基(甲基)丙烯酸酯、2-羟甲基(甲基)丙烯酸酯、2-羟丙基(甲基)丙烯酸酯、4-羟丁基(甲基)丙烯酸酯、乙基-2-羟基丙烯酸酯、2-(丙烯酰氧基)乙基氢琥珀酸酯和甲基丙烯酸。
14.根据权利要求12所述的用于3D打印支撑体的墨组合物，特征在于，基于所述用于3D打印支撑体的墨组合物的总重量，所述含有乙烯基和丙烯酸酯基中至少一者的单体的含量为0.01重量％至80重量％。
15.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述墨组合物还包含添加剂。
16.根据权利要求1所述的用于3D打印支撑体的墨组合物，特征在于，所述添加剂为选自以下中的至少一者：表面活性剂、增塑剂、(热)聚合抑制剂、稳定剂、消泡剂、稀释剂和粘度控制剂。
17.一种用于生产3D打印的方法，特征在于，使用根据权利要求1至16中任一项所述的用于3D打印支撑体的墨组合物。
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| CN115011172A (zh) * | 2022-06-23 | 2022-09-06 | 北京大华博科智能科技有限公司 | 一种可喷印绝缘结构墨水 |
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| EP3421555A4 (en) | 2019-01-16 |
| WO2017146423A1 (ko) | 2017-08-31 |
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