CN108368300B - 3d打印的方法 - Google Patents
3d打印的方法 Download PDFInfo
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- CN108368300B CN108368300B CN201680072246.7A CN201680072246A CN108368300B CN 108368300 B CN108368300 B CN 108368300B CN 201680072246 A CN201680072246 A CN 201680072246A CN 108368300 B CN108368300 B CN 108368300B
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Abstract
本申请涉及通过使用熔丝制造打印机来进行的包含热塑性弹性体的聚合物组合物的3D打印的方法。所述聚合物组合物包含0.1‑3重量％的脱模剂和/或外部润滑剂和可选地0.5‑10重量％的消光剂，并且所述热塑性弹性体包含二聚脂肪酸和/或由其衍生的二胺的单体单元。
Description
本申请涉及使用熔丝制造(FFF)打印机进行的聚合物组合物的成型制品的3D打印的方法。
在熔丝制造(FFF)(也被称为熔融沉积模型(FDM))中，聚合物组合物的长丝从这种长丝的卷材供应到挤出喷嘴。在许多FFF机器中，通过例如蜗杆传动齿轮系统或一对异型轮(profiled wheel)，以可控的速度将长丝推入打印头。打印头可以被加热以使长丝熔融，然后熔融长丝通过打印头的挤出喷嘴沉积，通常在基材上沉积第一层，然后在生长的成形物体上沉积。沉积之后，聚合物组合物固化。这种方法和装置的例子例如公开在WO15019212中。
已知方法的问题在于，如果使用热塑性弹性体，则由于来自打印头的熔融聚合物组合物的输出波动，打印过程不流畅。甚至有可能发生全面中断。如果将打印过程的速度提高到经济上可接受的水平，情况尤其如此
本发明的目的是提供一种通过使用熔丝制造打印机来进行包含热塑性弹性体的聚合物组合物的3-D印刷的方法，其没有显示出这个问题。
令人惊奇的是，如果聚合物组合物包含0.1-3.0重量％的脱模剂和/或外部润滑剂和可选地0.5-10重量％的消光剂，并且其中聚合物组合物含有热塑性弹性体，其中热塑性弹性体包含二聚脂肪酸和/或由其衍生的二胺的单体单元，则实现该目的。
与已知方法相比，本发明的方法即使在相当高的速度下也能平稳地运行。在3D打印物体中在后续层之间获得良好的粘附性是至关重要的。尽管使用脱模剂和/或外部润滑剂，但在用本发明方法获得的物体中的粘附性仍处于足够的水平。
优选地，聚合物组合物包含脱模剂和/或外部润滑剂。
脱模剂是促进部件从模具释放的化合物，其优选地通过在部件表面和模腔表面之间产生滑动效果。脱模剂的实例包括基于脂肪酸的化合物，例如硬脂酸金属盐，尤其是硬脂酸钠、硬脂酸锌或硬脂酸钙或者褐煤酸钠、褐煤酸锌或褐煤酸钙。
外部润滑剂是通过在模壁和聚合物熔体之间产生滑动层从而降低挤出模具中的压力的化合物。外部润滑剂的实例包括脂肪酸(例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸、芥酸脂肪酸)，特氟隆，烃蜡(例如PE、PP、石蜡)。优选地，使用酸酯：褐煤蜡、硬脂酸十八醇酯、邻苯二甲酸二硬脂醇酯、金属皂(例如硬脂酸钙、硬脂酸锌)。最优选地，使用酰胺(acid amide)，例如伯酰胺—芥酸酰胺(erucamide)(loxiol)、油酰胺、硬脂酰胺，仲酰胺—乙撑双硬脂酸酰胺(EBS)和乙撑双油酸酰胺(EBO)。使用酰胺不仅在非常高的速度下获得平滑的运行过程，而且在用根据本发明的方法生产的物体中的后续层之间具有非常高的粘附性。
通常化学化合物既适合用作脱模剂又适合用作外部润滑剂。
优选地，根据本发明的聚合物组合物包含至少0.2重量％的脱模剂和/或外部润滑剂，更优选地至少0.3重量％，最优选地至少0.4重量％的脱模剂和/或外部润滑剂。优选地，根据本发明的聚合物组合物包含至多2.5重量％的脱模剂和/或外部润滑剂，更优选地至多2重量％，最优选地至多1重量％的脱模剂和/或外部润滑剂。
聚合物组合物优选地包含消光剂，因为采用消光剂能够获得甚至更高的生产速度，而没有问题。
消光剂包括滑石和二氧化硅颗粒。优选地，颗粒的平均尺寸(d50，基于重量)在1和10微米之间。滑石是一种矿物，其作为消光剂被生产和市售。可在火焰法中生产适合用作消光剂的二氧化硅颗粒，以获得所谓的气相二氧化硅产物。优选地，在沉淀法中获得二氧化硅颗粒，以获得所谓的沉淀二氧化硅。适合用作消光剂的二氧化硅颗粒可商购获得。优选地，根据本发明的聚合物组合物包含至少1重量％、更优选地2重量％、最优选地3重量％的消光剂。优选地，根据本发明的聚合物组合物包含至多8重量％、更优选地至多6重量％的消光剂。
优选地，组合物至少包含脱模剂和/或外部润滑剂。最优选地，组合物包含消光剂和脱模剂和/或外部润滑剂。
根据本发明的方法尤其适合用于邵氏(shore)D硬度<70、优选地<60、更优选地<50、更优选地<40、更优选地<30、更优选地<20的聚合物组合物。根据本发明的方法也适合用于邵氏A硬度小于90或甚至更低的聚合物组合物。这是因为采用具有如此低硬度的热塑性弹性体时，上文提及的问题最为突出，并且希望生产具有如此低硬度的聚合物组合物的成型制品。
共聚酯弹性体和共聚酰胺弹性体是具有弹性性质的热塑性聚合物，其包含聚酯硬链段或聚酰胺硬链段，和衍生另一聚合物的软链段。软链段包含二聚脂肪酸和/或由其衍生的二胺的单体单元。共聚酯弹性体中的聚酯硬链段通常由衍生自至少一种亚烷基二醇和至少一种芳族或脂环族二羧酸的单体单元构成。共聚酰胺弹性体的聚酰胺硬链段通常由来自至少一种芳族和/或脂肪族二胺和至少一种芳族或脂肪族二羧酸和/或脂肪族氨基-羧酸的单体单元构成。
硬链段通常由聚酯或聚酰胺组成，在适用的情况下，所述聚酯或聚酰胺的熔融温度或玻璃化温度远高于室温，并可高达300℃或甚至更高。优选地，所述熔融温度或玻璃化温度为至少150℃、更优选地至少170℃或甚至至少190℃。
优选地，热塑性弹性体是共聚酯弹性体。共聚酯弹性体的示例包括共聚酯酯(copolyesterester)弹性体、共聚碳酸酯酯(copolycarbonateester)弹性体或共聚醚酯(copolyetherester)弹性体；即，带有衍生自二聚脂肪酸和/或由其衍生的二胺的单体单元的软链段的共聚酯嵌段共聚物。共聚酯弹性体可以例如在商品名Arnitel下从荷兰的DSMEngineering Plastics B.V.获得。
硬链段中的芳族二羧酸合适地选自由对苯二甲酸、间苯二甲酸、邻苯二甲酸、2,6-萘二甲酸和4,4-联苯二甲酸及其混合物组成的组。优选地，芳族二羧酸包含对苯二甲酸，更优选地相对于二羧酸的总摩尔量，包含至少50摩尔％、仍然更优选地至少90摩尔％的对苯二甲酸，或甚至完全由对苯二甲酸组成。
硬链段中的亚烷基二醇合适地选自由乙二醇、丙二醇、丁二醇、1,2-己二醇、1,6-环己烷二醇、1,4-丁二醇、苯二甲醇、环己二醇(cyclohexane diol)、环己烷二甲醇及其混合物组成的组。优选地，相对于亚烷基二醇的总摩尔量，亚烷基二醇包含乙二醇和/或1,4-丁二醇，更优选地包含至少50摩尔％、仍然更优选地至少90摩尔％的乙二醇和/或1,4-丁二醇，或甚至完全由乙二醇和/或1,4-丁二醇组成。
硬链段最优选地包含聚对苯二甲酸丁二醇酯链段或者甚至由聚对苯二甲酸丁二醇酯链段组成。
二聚脂肪酸作为软嵌段
使用含有二聚脂肪酸和/或由其衍生的二胺的单体单元的热塑性弹性体，获得非常好的结果。获得各打印层之间非常强的粘附性。本文中理解，包含热塑性弹性体的聚合物组合物也可以使用与其它热塑性弹性体的共混物。
这种二聚脂肪酸可以通过单体不饱和脂肪酸的二聚作用获得，并且由二聚脂肪酸表示。
二聚反应之后，进一步处理(例如通过蒸馏)由此得到的低聚物混合物，以获得具有高含量二聚脂肪酸的混合物。可通过催化加氢使二聚脂肪酸中的双键饱和。本文所使用的术语“二聚脂肪酸”涉及这些二聚脂肪酸的两种类型，饱和的与不饱和的。优选地，二聚脂肪酸是饱和的。
二聚脂肪酸优选地包含32至44个碳原子。最优选地，二聚脂肪酸包含36个碳原子。碳原子的量通常是平均值，因为二聚脂肪酸通常作为混合物市售。
还可以通过利用众所周知的反应中的一种反应，用氨基取代一个或两个酸基来生产二聚脂肪酸的衍生物。
优选地，热塑性弹性体包含20–80重量％的聚对苯二甲酸丁二醇酯硬链段和20至80重量％的二聚脂肪酸和/或由其衍生的二胺的单体单元。更优选地，热塑性弹性体包含40–80重量％的聚对苯二甲酸丁二醇酯硬链段和20至60重量％的二聚脂肪酸和/或由其衍生的二胺的单体单元。高含量的软链段导致较软的材料，对于这较软的材料，在3D打印方面，脱模剂和/或外部润滑剂的存在显示出更多的优点。
本发明还涉及在根据本发明的3D打印方法中使用的长丝。这种长丝可以通过用于该目的的众所周知的挤出工艺来生产。通常长丝是单丝。长丝的直径可以在1mm与3.5mm之间，优选在1.5mm与3mm之间。
本发明还涉及用于将长丝施加到3D打印机并且适于被安装在3D打印机上的系统，该系统包含根据本发明的长丝。这种系统的例子包括卷轴和暗盒(cassette)。
图1示出了可用于根据本发明的方法中的FFF装置的打印头的实例和基材的示意图。
图2示出了印刷板和测试样品。
图3示出了可以在根据本发明的方法中使用的Bowden型FFF装置的传送机构和打印头的实例以及基板的示意图。
图1示出了可以在根据本发明的方法中使用的FFF装置的打印头的示例的示意图。通过一对轮子(2)从卷轴(未示出)将长丝(1)输送到打印头的烘箱(3)中，以使丝线熔融。长丝的熔融材料流过喷嘴(4)。获得这种流动的压力是通过由一对轮子施加在长丝上的力以及在烘箱第一部分中作为活塞的未熔融的长丝获得的。离开喷嘴的挤出物(5)沉积在位于喷嘴下方的基材(6)上，在基材(6)上各自地形成物体。
图2示出了印刷板(3)、第一挤出物(1)、第二挤出物(2)和用于测定断裂伸长率的测试样品(4)。
图3示出了可以在根据本发明的方法中使用的打印加热和传输机构的示例的示意图。在这种所谓的Bowden型挤出机中，通过一对轮子(2)将长丝(1)从卷轴(未示出)输送到打印头的烘箱(3)中，以使长丝熔融。这里，传送轮不是直接连接在打印头的顶部上，而是长丝由柔性管(7)从一对轮引导到打印头中。这种设置需要较长的长丝输送，由于长丝可能卡在管和/或输送机构中，因此无进料的风险较高。
实施例
所用材料：
-Arnitel ECOTM，由荷兰DSM公司交付的一种热塑性共聚酯，其包含聚对苯二甲酸丁二醇酯的硬链段和二聚脂肪酸的软链段，邵氏D硬度为34。
-NinjaflexTM，由美国Fenner Drives Corp.交付的一种热塑性聚氨酯材料。
-Loxiol E spez P，由德国Emery Oleochemicals交付的基于芥酸酰胺(eurecamide)的外部润滑剂。
NipTMCX200gel，由日本Tosch Silica Corp.交付的基于沉淀二氧化硅的消光剂。
对比实验A
将直径1.75mm的Arnitel ECOTM的长丝以各种速度输送穿过由荷兰Maastricht的MaukCC交付的Cartesio 3D打印机的打印头。这种打印机的示意图如图1所示。烘箱温度为240℃，喷嘴直径为0.4mm。如图2所示，离开喷嘴的挤出物在具有平面形式的基材上以直线的模式沉积。基材以与离开喷嘴的挤出物的速度相同的速度在x-y方向上移动到喷嘴下方。
沉积在基材上的挤出物的形状分类如下：
1:光滑的规则形状。
2.不规则表面，但挤出物不中断。
3.不规则表面，挤出物也有中断
对于某些速度，观察到“无进料”，并且不再测试提高的速度，因为没有材料可被进料。
表1中给出各种速度的结果。
实施例I
如对比实验A一样，但是长丝具有包含Arnitel ECOTM、0.5重量％Loxiol E spez P和5重量％NipTMCX200gel的聚合物组合物。结果在表1中给出。
对比实验A2
如对比实验A一样，但是长丝是在230℃的温度下打印的NinjaflexTM。结果在表1中给出。在30mm/s以上的速度时，不再可能进料。
表1
| 速度，mm/s | 实施例I | 对比实验A | 对比实验A2 |
| 10 | 1 | 1 | 1 |
| 20 | 1 | 2 | 2 |
| 30 | 2 | 3 | 无进料 |
| 40 | 2 | 3 |
对比实验B
如对比实验A一样，但是以10mm/s的长丝速度的恒定传输速度。如在对比实验A中一样，在第一步中第一挤出物以直线方式沉积在基材上。使挤出物固化。在第二步中，将第二挤出物沉积在第一挤出物的旁边。以这种方式，第二挤出物粘附到第一挤出物上。重复此过程直至获得长度为120mm的印刷板(参见图2)。通过测定从印刷板上冲出的测试样品的断裂伸长率来测量挤出物之间的粘附性。
ISO 527-2-1BA测试样品的位置如图2所示。拉伸测试在环境温度下以500mm/min的十字头速度进行。
结果在表2中给出。
实施例II
如对比实验B一样，但长丝具有包含Arnitel ECOTM、0.5重量％Loxiol E spez P和5重量％NipTMCX200gel的聚合物组合物。结果在表2中给出。
表2
| 断裂伸长率[％] | |
| 实施例II | 520-620 |
| 对比实验B | 480-600 |
对比实验C
将直径1.75mm的Arnitel ECOTM的长丝以各种速度输送穿过Bowden型打印机的打印头，如图3所示。长丝引导管具有适合长丝直径1.75mm的2mm内径和700mm的长度。烘箱温度为230℃，喷嘴直径为0.35mm。如图2所示，离开喷嘴的挤出物在具有平面形式的基材上以直线的模式沉积。基材以与离开喷嘴的挤出物的速度相同的速度在x-y方向上移动到喷嘴下方。
沉积在基材上的挤出物的形状分类如下：
1:完整打印
2.不完整打印。
对于某些速度，观察到“无进料”，并且不再测试提高的速度，因为没有材料可被进料。同样，在分类为“不完整打印”之后，对于更高的速度，不会进一步进行测试。
表3给出了各种速度的结果。
实施例III
如对比实验C一样，但是长丝具有包含Arnitel ECOTM和0.25重量％Loxiol E spezP的聚合物组合物。结果在表3中给出。
实施例IV
如对比实验C一样，但是长丝具有包含Arnitel ECOTM和0.5重量％Loxiol E spezP的聚合物组合物。结果在表3中给出。
表3
| 速度，mm/s | 实施例III | 实施例IV | 对比实验C |
| 10 | 1 | 1 | 无进料 |
| 20 | 1 | 1 | |
| 30 | 2 | 1 | |
| 40 | 1 | ||
| 50 | 2 |
上述实施例清楚地表明，当存在脱模剂和/或外部润滑剂和/或消光剂时，可印刷性得到改善。速度可以大大提高，同时仍然可以进行打印。对于不含脱模剂和/或外部润滑剂和/或消光剂的聚合物来说，可以达到低得多的速度，或者甚至根本无法进行进料。根据报道，对于根据本发明的方法，长丝间的粘附性是足够的，其在各种速度下表示为“1”或“2”。
Claims (12)
1.通过使用熔丝制造打印机来进行的包含热塑性弹性体的聚合物组合物的3D打印的方法，其特征在于，所述聚合物组合物包含0.1-3重量％的脱模剂和/或外部润滑剂和可选地0.5–10重量％的消光剂，并且所述热塑性弹性体包含二聚脂肪酸和/或由其衍生的二胺的单体单元。
2.根据权利要求1所述的3D打印的方法，其中所述聚合物组合物包含0.4-2重量％的脱模剂和/或外部润滑剂。
3.根据权利要求1或2所述的3D打印的方法，其中所述聚合物组合物包含酰胺。
4.根据权利要求1-2中任意一项所述的3D打印的方法，其中所述聚合物组合物包含芥酸酰胺。
5.根据权利要求1所述的3D打印的方法，其中所述聚合物组合物具有<70的邵氏D硬度。
6.根据权利要求1所述的3D打印的方法，其中所述聚合物组合物具有<60的邵氏D硬度。
7.根据权利要求1所述的3D打印的方法，其中所述聚合物组合物具有<50的邵氏D硬度。
8.根据权利要求1所述的3D打印的方法，其中所述二聚脂肪酸包含32至44个碳原子。
9.根据权利要求8所述的3D打印的方法，其中所述二聚脂肪酸包含36个碳原子。
10.根据权利要求9所述的3D打印的方法，其中所述热塑性弹性体包含40–80重量％的聚对苯二甲酸丁二醇酯硬链段和20至60重量％的二聚脂肪酸和/或由其衍生的二胺的单体单元。
11.一种用于3D打印的长丝，其包含权利要求1-10中任意一项所限定的聚合物组合物。
12.用于将长丝进料到用于3D打印的装置的系统，其包含权利要求11所述的长丝。
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| US5863319A (en) * | 1996-12-10 | 1999-01-26 | Markem Corporation | Thermally stable hot melt ink |
| JP2004156180A (ja) * | 2002-11-07 | 2004-06-03 | Toyobo Co Ltd | 風合いに優れた伸長性不織布及びその製造方法 |
| JP5671765B2 (ja) * | 2009-04-20 | 2015-02-18 | ディーエスエム アイピー アセッツ ビー．ブイ． | 柔軟なポリマー |
| CN102596543B (zh) * | 2009-06-23 | 2014-09-17 | 斯特拉塔西斯公司 | 具有自定义特征的消耗材料 |
| JP2011143615A (ja) * | 2010-01-14 | 2011-07-28 | Asahi Kasei E-Materials Corp | ３次元形状を有する構造体の製造方法及び３次元形状を有する構造体 |
| US8603612B2 (en) * | 2010-04-22 | 2013-12-10 | Xerox Corporation | Curable compositions for three-dimensional printing |
| WO2012080163A2 (en) * | 2010-12-13 | 2012-06-21 | Dsm Ip Assets B.V. | Polymer composition containing a polymer, which polymer contains monomer units of a dimerised fatty acid |
| US20130338278A1 (en) * | 2010-12-16 | 2013-12-19 | Dsm Ip Assets B.V. | Polymer composition containing a polymer, which polymer contains monomer units of a dimerised fatty acid |
| CN103827191A (zh) * | 2011-09-23 | 2014-05-28 | 帝斯曼知识产权资产管理有限公司 | 含有热塑性聚酯弹性体的聚合物组合物 |
| US20150340122A1 (en) * | 2012-12-18 | 2015-11-26 | Dsm Ip Assets B.V. | The invention relates to an electrical cable comprising a cable cover |
| KR102208200B1 (ko) | 2013-08-09 | 2021-01-27 | 킴벌리-클라크 월드와이드, 인크. | 3차원 인쇄용 중합체 물질 |
| CN103756236B (zh) * | 2014-01-06 | 2017-01-11 | 朱叶周 | 用于制备三维打印快速成型的软性打印材料的热塑性弹性体组合物 |
| WO2015157148A1 (en) * | 2014-04-07 | 2015-10-15 | Sabic Global Technologies B.V. | Powder bed fusing thermoplastic polymers |
| ES2753248T3 (es) * | 2014-07-08 | 2020-04-07 | Emery Oleochemicals Gmbh | Materia prima sinterizable para el uso en dispositivos de impresión 3D |
| CN104448805A (zh) * | 2014-12-18 | 2015-03-25 | 陈梓煜 | 一种用于3d打印的高强尼龙基复合材料及其制备方法 |
| WO2017059025A1 (en) * | 2015-10-01 | 2017-04-06 | Lubrizol Advanced Materials, Inc. | Thermoplastic polyurethane compositions for solid freeform fabrication |
| US10619061B2 (en) * | 2016-03-17 | 2020-04-14 | Ineos Styrolution Group Gmbh | Use of moulding compounds based on blends of san-copolymers and polyamide for 3D printing |
-
2016
- 2016-12-08 US US15/780,365 patent/US20180355196A1/en not_active Abandoned
- 2016-12-08 EP EP16809789.7A patent/EP3387058B1/en active Active
- 2016-12-08 KR KR1020187019544A patent/KR20180094002A/ko not_active Application Discontinuation
- 2016-12-08 WO PCT/EP2016/080346 patent/WO2017097941A1/en active Application Filing
- 2016-12-08 CN CN201680072246.7A patent/CN108368300B/zh active Active
- 2016-12-08 JP JP2018526905A patent/JP2019503889A/ja active Pending
-
2021
- 2021-09-16 JP JP2021151140A patent/JP7172012B2/ja active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2019503889A (ja) | 2019-02-14 |
| JP7172012B2 (ja) | 2022-11-16 |
| EP3387058B1 (en) | 2019-11-13 |
| EP3387058A1 (en) | 2018-10-17 |
| KR20180094002A (ko) | 2018-08-22 |
| US20180355196A1 (en) | 2018-12-13 |
| JP2022000348A (ja) | 2022-01-04 |
| WO2017097941A1 (en) | 2017-06-15 |
| CN108368300A (zh) | 2018-08-03 |
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