CN116635477A - 形状保持力和界面粘合力优异的3d打印用聚碳酸酯树脂组合物及包含其的3d打印用颗粒和长丝 - Google Patents
形状保持力和界面粘合力优异的3d打印用聚碳酸酯树脂组合物及包含其的3d打印用颗粒和长丝 Download PDFInfo
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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Abstract
本发明涉及一种形状保持力和界面粘合力优异的3D打印用聚碳酸酯树脂组合物以及包含该聚碳酸酯树脂组合物的3D打印用长丝和3D打印用颗粒。更详细地,本发明涉及一种3D打印用聚碳酸酯树脂组合物以及包含该聚碳酸酯树脂组合物的3D打印用颗粒和长丝,其中所述聚碳酸酯树脂组合物包含聚碳酸酯(PC)树脂、聚对苯二甲酸丁二醇酯(PBT)树脂、炭黑母料和碳纤维的特定组合,且保持聚碳酸酯树脂的优异的机械特性,并且如形状保持力和界面粘合力等3D打印用长丝所需的特定物理性能优异地保持平衡。
Description
技术领域
本发明涉及一种形状保持力和界面粘合力优异的3D打印用聚碳酸酯树脂组合物以及包含该聚碳酸酯树脂组合物的3D打印用长丝和3D打印用颗粒,更详细地,涉及一种3D打印用聚碳酸酯树脂组合物以及包含该聚碳酸酯树脂组合物的3D打印用颗粒和长丝,所述3D打印用聚碳酸酯树脂组合物包含聚碳酸酯树脂、聚对苯二甲酸丁二醇酯(PBT)树脂、炭黑母料和碳纤维的特定组合,并且保持聚碳酸酯树脂的优异的机械特性,同时形状保持力和界面粘合力等3D打印用长丝所需的特定物理性能优异地保持平衡。
背景技术
3D打印的输出方式因用途而异,但考虑到设备价格、材料供需、输出难度等,工业和家庭使用最广泛的输出方式是材料挤压法。材料挤压法是一种将以长丝形式提供的材料熔化并堆叠在喷嘴中的方法,这种方法中使用的3D打印长丝用树脂包括聚乳酸(PLA)、丙烯腈-丁二烯-苯乙烯(ABS)、聚碳酸酯(PC)和聚酰亚胺(PI)等。
现有的3D打印机由供应长丝的挤出机(extruder),熔融并喷射长丝的热端喷嘴等组成。通过挤出机供应的长丝(filament)被热端喷嘴的加热器熔化并以珠子(bead)的形式喷出,并通过热端喷嘴在3轴方向上移动的同时堆叠珠子的方法制造三维物品。
为了使三维物品具有适当的质量,重要的是材料具有可以保持恒定的打印质量的特性。特别地,作为决定打印质量的因素,重要的是形状保持力和界面粘合力。形状保持力是指通过喷嘴射出的珠子层层堆叠时,仍然保持射出的圆形(不被压成椭圆形)并堆叠的特性和三维堆叠后的形态保持力的特性。
其中,最常用的3D打印长丝用树脂是聚乳酸树脂。聚乳酸树脂输出时无味,在相对低的温度下也可以输出,因此无需高价的输出装置。但是,由于聚乳酸树脂本身的机械特性差,因此需要如聚乳酸等的可以在相对低的温度下输出的同时可以显示出高强度等优异的机械特性的3D打印长丝用树脂。
聚碳酸酯树脂是具有优异的机械特性、热特性和尺寸稳定性的工程塑料,并用于各种工业领域。然而,将聚碳酸酯树脂用作3D打印长丝用树脂时,发生塌陷现象,并且界面之间的粘合力弱,因此可能会发生刚性的降低。
因此,需要开发一种形状保持力、界面粘合力等3D打印用长丝所需的特定物理性能均优异的3D打印长丝用聚碳酸酯树脂组合物。
发明内容
要解决的技术问题
本发明的目的是提供一种3D打印用聚碳酸酯树脂组合物、包含该聚碳酸酯树脂组合物的3D打印用颗粒和长丝,所述聚碳酸酯树脂组合物保持聚碳酸酯树脂的优异的机械特性,同时形状保持力和界面粘合力等3D打印用长丝所需的特定物理性能优异地保持平衡。
技术方案
为了解决上述技术问题,本发明提供一种3D打印用树脂组合物,其中,以总共100重量份的组合物为基准,所述树脂组合物包含:(1)62-76重量份的聚碳酸酯树脂、(2)1-11重量份的聚对苯二甲酸丁二醇酯树脂、(3)1-9.5重量份的炭黑母料和(4)11-25重量份的碳纤维。
根据本发明的另一个方面,提供一种包含本发明的聚碳酸酯树脂组合物的3D打印用颗粒。
根据本发明的另一个方面,提供一种包含所述本发明的聚碳酸酯树脂组合物的3D打印用长丝。
有益效果
本发明的聚碳酸酯树脂组合物保持聚碳酸酯树脂的独特的优异的机械特性的同时具有优异的界面粘合力。因此,3D打印时输出性优异且形状保持力优异,因此不发生塌陷现象,并且由于界面粘合力优异,防止刚性降低,因此可以适合用作3D打印用颗粒或长丝。
附图说明
图1是例示3D打印用长丝的形状保持力评价基准的图,3D打印时发生塌陷的情况越少,得分越高(最高5分)。
图2是例示3D打印用长丝的界面粘合力评价基准的图,3D打印时界面之前的间隙越少,得分越高(最高5分)。
具体实施方式
以下,对本发明进行详细的说明。
本发明的3D打印用树脂组合物包含(1)聚碳酸酯树脂、(2)聚对苯二甲酸丁二醇酯树脂、(3)炭黑母料和(4)碳纤维。此外,本发明的3D打印用树脂组合物可以任选地进一步包含(5)一种以上的其它添加剂。
(1)聚碳酸酯(PC)树脂
本发明的3D打印用树脂组合物中可包含的聚碳酸酯树脂优选为芳香族聚碳酸酯树脂,但只要可以实现本发明的技术思想,则其种类并不特别受限于此,并且可以使用本领域中通常使用的热塑性芳香族聚碳酸酯树脂。
在本发明的一个具体实施方案中,所述芳香族聚碳酸酯树脂可以由二元酚类、碳酸酯前驱体(precursor)和分子量调节剂等制备,并且可以包含直链状和/或支链状聚碳酸酯均聚物和聚酯共聚物等。
所述二元酚类是组成芳香族聚碳酸酯树脂的单体中的一种,并且可以由以下化学式1表示。
[化学式1]
在所述化学式1中,X表示亚烷基;不具有官能团的直链状、支链状或环状亚烷基;或者具有选自硫醚、醚、亚砜、砜、酮、萘基或异丁基苯基中的一种以上的官能团的直链状、支链状或环状亚烷基,优选地,X是碳原子数为1至10的直链状亚烷基或碳原子数为3至10的支链状亚烷基,或者碳原子数为3至10的环状亚烷基。
R1和R2可以各自独立地表示卤素原子、碳原子数为1至20的直链状烷基、碳原子数为3至20的支链状烷基或碳原子数为3至20的环状烷基,
n和m可以各自独立地表示0至4的整数。
作为所述二元酚类的非限制性的例示,可以选自双(4-羟基苯基)甲烷、双(4-羟基苯基)苯基甲烷、双(4-羟基苯基)萘基甲烷、双(4-羟基苯基)-(4-异丁基苯基)甲烷、1,1-双(4-羟基苯基)乙烷、1-乙基-1,1-双(4-羟基苯基)丙烷、1-苯基-1,1-双(4-羟基苯基)乙烷、1-萘基-1,1-双(4-羟基苯基)乙烷、1,2-双(4-羟基苯基)乙烷、1,10-双(4-羟基苯基)癸烷、2-甲基-1,1-双(4-羟基苯基)丙烷、2,2-双(4-羟基苯基)丙烷、2,2-双(4-羟基苯基)丁烷、2,2-双(4-羟基苯基)戊烷、2,2-双(4-羟基苯基)己烷、2,2-双(4-羟基苯基)壬烷、2,2-双(3-甲基-4-羟基苯基)丙烷、2,2-双(3-氟-4-羟基苯基)丙烷、4-甲基-2,2-双(4-羟基苯基)戊烷、4,4-双(4-羟基苯基)庚烷、二苯基双(4-羟基苯基)甲烷、间苯二酚、对苯二酚、4,4'-二羟基苯基醚(双(4-羟基苯基)醚)、4,4'-二羟基-2,5-二羟基二苯醚、4,4'-二羟基-3,3'-二氯二苯醚、双(3,5-二甲基-4-羟基苯基)醚、双(3,5-二氯-4-羟基苯基)醚、1,4-二羟基-2,5-二氯苯、1,4-二羟基-3-甲基苯、4,4'-二羟基二苯酚(p,p'-二羟基苯基)、3,3'-二氯-4,4'-二羟基苯基、1,1-双(4-羟基苯基)环己烷、1,1-双(3,5-二甲基-4-羟基苯基)环己烷、1,1-双(3,5-二氯-4-羟基苯基)环己烷、1,1-双(3,5-二甲基-4-羟基苯基)环十二烷、1,1-双(4-羟基苯基)环十二烷、1,1-双(4-羟基苯基)丁烷、1,1-双(4-羟基苯基)癸烷、1,4-双(4-羟基苯基)丙烷、1,4-双(4-羟基苯基)丁烷、1,4-双(4-羟基苯基)异丁烷、2,2-双(4-羟基苯基)丁烷、2,2-双(3-氯-4-羟基苯基)丙烷、双(3,5-二甲基-4-羟基苯基)甲烷、双(3,5-二氯-4-羟基苯基)甲烷、2,2-双(3,5-二甲基-4-羟基苯基)丙烷、2,2-双(3,5-二溴-4-羟基苯基)丙烷、2,2-双(3,5-二氯-4-羟基苯基)丙烷、2,4-双(4-羟基苯基)-2-甲基-丁烷、4,4'-硫代联苯酚(双(4-羟基苯基)砜)、双(3,5-二甲基-4-羟基苯基)砜、双(3-氯-4-羟基苯基)砜、双(4-羟基苯基)硫醚、双(4-羟基苯基)亚砜、双(3-甲基-4-羟基苯基)硫醚、双(3,5-二甲基-4-羟基苯基)硫醚、双(3,5-二溴-4-羟基苯基)亚砜、4,4'-二羟基二苯甲酮、3,3',5,5'-四甲基-4,4'-二羟基二苯甲酮、4,4'-二羟基二苯基、甲基氢醌、1,5-二羟基萘及2,6-二羟基萘,但并不必须受限于此。代表性地,可以列举2,2-双(4-羟基苯基)丙烷(双酚A)。除此之外的功能性二元酚类(dihydric phenol)可以参照美国专利US2,999,835号、US3,028,365号、US3,153,008号及US3,334,154号等,所述二元酚类可以单独使用或者两种以上组合使用。
所述碳酸酯前驱体是构成芳香族聚碳酸酯树脂的另一种单体,其非限制性的例示可以列举碳酰氯(光气)、碳酰溴、双卤代甲酸酯、碳酸二苯酯或碳酸二甲酯等。优选地,可以使用碳酰氯(光气)。
作为所述分子量调节剂,可以使用本领域已知的物质,即与用于制备热塑性芳香族聚碳酸酯树脂的单体相似的单官能物质(单官能化合物(monofunctional compound))。作为所述分子量调节剂的非限制性的例示,可以列举基于酚的衍生物(例如,对异丙基苯酚、对叔丁基苯酚(PTBP)、对枯基苯酚、对异辛基苯酚、对异壬基苯酚等)、脂肪醇等。优选地,可以使用对叔丁基苯酚(PTBP)。
本发明的树脂组合物中包含的所述聚碳酸酯树脂的粘均分子量优选可以为15000至50000,更优选可以为16000至30000。
在本发明的3D打印用树脂组合物中,以总共100重量份的组合物为基准,所述聚碳酸酯树脂的含量为62-76重量份。当总共100重量份的组合物中的所述聚碳酸酯树脂的含量小于62重量份时,可能存在3D打印产品的机械强度降低的问题,当所述聚碳酸酯树脂的含量超过76重量份时,可能会发生塌陷现象。
更具体地,以总共100重量份的本发明的3D打印用树脂组合物为基准的树脂组合物中的所述聚碳酸酯树脂的含量可以为62重量份以上、63重量份以上、64重量份以上或65重量份以上,或者可以为76重量份以下、75重量份以下、74重量份以下或72重量份以下。优选地,100重量份的组合物中的所述聚碳酸酯树脂的含量例如可以为62-76重量份,更优选可以为63-75重量份,进一步优选可以为65-72重量份。
(2)聚对苯二甲酸丁二醇酯(PBT)树脂
本发明的3D打印用树脂组合物中包含的聚对苯二甲酸丁二醇酯树脂是以1,4-丁二醇与对苯二甲酸或对苯二甲酸二甲酯为单体通过直接酯化反应或酯交换反应缩聚的聚合物。
本发明的优选的具体例中,所述聚对苯二甲酸丁二醇酯树脂的熔融温度可以为215℃-235℃,更优选可以为220℃-230℃。此外,所述聚对苯二甲酸丁二醇酯树脂的特性粘度(IV)优选为0.45-1.6dl/g,更优选为0.80-1.3dl/g。
在本发明的3D打印用树脂组合物中,以总共100重量份的组合物为基准,所述聚对苯二甲酸丁二醇酯树脂的含量为1-11重量份。当总共100重量份的组合物中的所述聚对苯二甲酸丁二醇酯树脂的含量小于1重量份时,难以改善3D打印产品的塌陷现象,当总共100重量份的组合物中的所述聚对苯二甲酸丁二醇酯树脂的含量超过11重量份时,3D打印产品的机械物理性能降低,并且界面粘合力可能会降低。
更具体地,以总共100重量份的本发明的3D打印用树脂组合物为基准的树脂组合物中的所述聚对苯二甲酸丁二醇酯树脂的含量可以为1重量份以上、2重量份以上、3重量份以上或4重量份以上,并且可以为11重量份以下、10.5重量份以下、10重量份以下、9.5重量份以下、9重量份以下或8重量份以下。优选地,100重量份的组合物中的所述聚对苯二甲酸丁二醇酯树脂的含量例如可以为1-11重量份,更优选可以为2-10重量份,进一步优选可以为3-8重量份。
(C)炭黑母料
所述炭黑母料是指将炭黑分散在热塑性树脂中,优选分散在上述聚碳酸酯树脂中的混合物。通过使用聚碳酸酯树脂中分散炭黑的形式的炭黑母料,炭黑容易被分散,从而可以有效地提高耐光性。
所述炭黑母料中含有的炭黑没有特别限制,例如,可以使用科琴黑、乙炔黑、槽法炭黑或它们的组合。炭黑的粒径优选为10-40nm的范围。所述炭黑的氮吸附比表面积(NSA)没有特别限制,但优选为150-250m2/g,更优选为180-240m2/g。其中,氮吸附比表面积(NSA)是根据JIS K6217-2:2001“第二部分:计算比表面积的的方法-氮吸附法-单点法”测量炭黑表面上的氮吸附量的值。
在本发明的3D打印用树脂组合物中,以总共100重量份的组合物为基准,所述炭黑母料的含量可以为1-9.5重量份。当总共100重量份的组合物中的所述炭黑母料的含量小于1重量份时,由于炭黑的含量过少,难以期待提高界面粘合力的效果,当总共100重量份的组合物中的所述炭黑母料的含量超过9.5重量份时,机械物理性能可能会降低。
更具体地,以总共100重量份的本发明的3D打印用树脂组合物为基准的树脂组合物中的所述炭黑母料的含量可以为1重量份以上、2重量份以上、3重量份以上或4重量份以上,并且可以为9.5重量份以下、9重量份以下、8.5重量份以下、8重量份以下、7重量份以下或6重量份以下。优选地,100重量份的组合物中的所述炭黑母料的含量例如可以为1-9.5重量份,更优选可以为2-8重量份,进一步优选可以为4-6重量份。
(D)碳纤维
所述碳纤维通常可以按照其直径、形态和石墨化程度来分类。这种特性可以由用于合成碳纤维的方法决定。在本发明中,所述碳纤维没有特别限制,但优选可以为沥青或聚丙烯腈(PAN)基纤维,并且可以以单长丝或多长丝的形式存在于组合物中。例如,通过共织、芯/鞘、并排、桔瓣型或基质和原纤维结构等,可以单独使用或与其他类型的纤维组合使用。此外,作为所述碳纤维的增强组合物,可以以例如,粗纱(rovings)、0-90度的织物等机织(woven)纤维增强材料、连续原丝毡、短切(chopped)原丝毡、纸巾、纸和毛毡等非织造纤维增强材料以及预制件(preforms)和编织物(braids)等三维编织增强材料的形式用于所述组合物中。
碳纤维的直径通常为约1-30μm,根据本发明的一个实施方案的纤维的直径可以为2-20μm,优选可以为3-10μm。
在本发明的3D打印用树脂组合物中,以总共100重量份的组合物为基准,所述碳纤维的含量为11-25重量份。当总共100重量份的组合物中的所述碳纤维的含量小于11重量份时,可能不会显示出改善塌陷现象,当所述碳纤维的含量超过25重量份时,可能难以进行挤出加工。
更具体地,以总共100重量份的本发明的3D打印用树脂组合物为基准的树脂组合物中的所述碳纤维的含量可以为11重量份以上、12重量份以上、13重量份以上或15重量份以上,并且可以为25重量份以下、24重量份以下、23重量份以下、22重量份以下、21重量份以下或20重量份以下。优选地,100重量份的组合物中的所述碳纤维的含量例如可以为11-25重量份,更优选可以为13-22重量份,进一步优选可以为15-20重量份。
(E)其它添加剂
除了上述成分(A)、成分(B)、成分(C)和成分(D)之外,本发明的树脂组合物可以进一步包含在注射成型或挤出成型用热塑性树脂组合物中通常添加的一种以上的其它添加剂。本发明的树脂组合物可以进一步包含选自例如无机颗粒、抗氧化剂、滑爽剂、紫外线吸收剂、光稳定剂、抗冲改性剂、消光剂、阻燃剂或它们中的两种或更多种的混合物中的一种或更多种的添加剂。
具体地,所述无机颗粒可以使用选自滑石、晶须、玻璃珠、玻璃薄片、玻璃纤维、碳纤维、粘土、高岭土、云母、碳酸钙和硫酸钡中的至少一种。
具体地,所述抗氧化剂可以使用酚系、亚磷酸酯系、硫酯系或它们中的两种或更多种的混合物等。
具体地,所述滑爽剂可以使用聚乙烯基、乙烯酯基、乙二醇-甘油酯基、褐煤基、乙二醇-甘油褐煤酸酯基或它们中的两种或更多种的混合物等。
所述紫外线吸收剂没有特别限制,并且可以使用市售产品。
具体地,所述光稳定剂可以使用苯并三唑基化合物、羟基苯基三嗪基化合物、嘧啶基化合物、氰基丙烯酸酯基化合物或它们中的两种或更多种的混合物等。
抗冲改性剂可以使用选自丙烯酸酯基共聚物、乙烯-丙烯酸酯基共聚物、含硅共聚物或聚甲基丙烯酸烷基酯基共聚物等中的一种或更多种的核-壳结构的共聚物,但不限于此。所述抗冲改性剂不仅具有抗冲增强的功能,而且改善组合物中的热塑性树脂之间或组合物中的成分之间的相容性,从而可以起到稳定优异且均匀的物理性能的作用。
此外,阻燃剂是降低可燃性的物质,并且可以使用选自磷酸盐基化合物、膦酸盐基化合物、聚硅氧烷、磷腈化合物、次膦酸盐基化合物或三聚氰胺基化合物中的一种或更多种的化合物,但不限于此。消光剂可以是无机化合物或有机化合物,所述无机化合物可以使用二氧化硅、氧化镁、氧化锆、氧化铝、二氧化钛或它们中的两种或更多种的混合物,所述有机化合物是交联的乙烯基共聚物,乙烯基共聚物的单体可以是选自苯乙烯、丙烯腈、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯或(甲基)丙烯酸丁酯等中的一种或更多种的单体。
所述其它添加剂的含量没有特别限制,在不损害本发明的3D打印用树脂组合物的所期望的物理性能的范围内,可以是为了增加进一步的功能而可使用的程度的量。
根据本发明的一个具体实施方案,以本发明的总共100重量份的组合物为基准,其它添加剂的含量可以为0.1-10重量份、优选可以为0.5-10重量份,更优选可以为1-8重量份。当总共100重量份的组合物中的所述其它添加剂的含量小于0.1重量份时,其它添加剂的使用带来的各种功能的改善效果可能甚微,当所述其它添加剂的含量超过10重量份时,树脂组合物的机械物理性能可能会变差。
根据本发明的另一个方面,提供一种包含所述本发明的聚碳酸酯树脂组合物的3D打印用颗粒(pellet)。
根据本发明的另一个方面,提供一种包含所述本发明的聚碳酸酯树脂组合物的3D打印用长丝。
所述3D打印用长丝可以通过将本发明的树脂组合物进行挤出成型来制备。具体地,所述3D打印用长丝可以通过用本发明的树脂组合物制备颗粒并将颗粒进行二次加工(挤出成型等)来制备。
以下,通过实施例及比较例更加详细地说明本发明。但是,本发明的范围并不限于此。
[实施例]
本实施例和比较例中使用的成分具体如下。
(A)聚碳酸酯树脂:粘均分子量为约17000的双酚A型线性聚碳酸酯
(B)聚对苯二甲酸丁二醇酯树脂:特性粘度(Intrinsic Viscisoty,IV)为0.8-1.1dl/g的聚对苯二甲酸丁二醇酯
(C)炭黑母料:Woosung Chemical NB9086
(D)碳纤维:MITSUBISHI PYROFIL TR06UL
(E)其它添加剂:抗冲改性剂、抗氧化剂和滑爽剂
将聚碳酸酯共聚物树脂、聚对苯二甲酸丁二醇酯树脂、炭黑母料按照下表1和表2中示出的实施例和比较例的成分和含量用混合机充分混合并均匀地分散,从而制备热塑性树脂组合物。之后,可以在260℃-280℃和200-250rpm的条件下使用32π双螺杆挤出机(L/D=40,25mm)来对制备的所述热塑性树脂组合物进行挤出,并在侧面加入碳纤维。在相同的温度条件下,使用具有100-200吨的夹紧力的注塑机来制备注塑试片。用于测量机械物理性能的注塑试片的情况下,制备符合各ASTM标准的注塑试片,以适合测量拉伸强度和冲击强度。
<物理性能的评价>
(1)拉伸强度
根据ASTM D638进行评价。
(2)弯曲强度和弯曲模量
根据ASTM D790进行评价。
(3)冲击强度
根据ASTM D256(1/8英寸的厚度,缺口-悬臂梁)进行评价。
(4)热变形温度
根据ASTM D648,以18.6㎏/cm2的载荷进行评价。
(5)形状保持力(塌陷)
在相应的输出温度下,用3D打印机打印出200mm*100mm的四边形试片。当形状保持力不足时,输出物无法保持四边形的形状,因此发生凹痕现象。通过观察输出的产品无法保持原形,并且凹痕的现象最大的位置,并根据程度如以下基准赋予5分至1分。(参考图1)
5分:凹痕小于0.5cm的现象
4分:凹痕为0.5-1.0cm的现象
3分:凹痕为1.0-1.5cm的现象
2分:凹痕为1.5-2.0cm的现象
1分:凹痕超过2.0cm的现象
(6)界面粘合力
在相应的输出温度下,用3D打印机打印出200mm*100mm的四边形试片。之后,用SEM观察四边形试片的5处边缘部分。将树脂之间的界面未完全粘合而可区分的现象表示为界面分离。当未观察到界面分离现象时赋予0分,当观察到界面分离现象时赋予1分。总共观察5处并进行总结,并如以下基准赋予5分至0分。(参考图2)
5分:没有界面分离
4分:在5处中观察到1处界面分离
3分:在5处中观察到2处界面分离
2分:在5处中观察到3处界面分离
1分:在5处中观察到4处界面分离
0分:在5处中观察到5处界面分离
[表1]
[表2]
根据本发明的聚碳酸酯树脂组合物保持了聚碳酸酯树脂独特的优异的机械特性的同时,3D打印时形状保持力优异且不发生塌陷现象,并且界面粘合力优异。从上述表1可知,与比较例中提出的树脂组合物相比,根据本发明的实施例的树脂组合物的界面粘合力上升的同时改善塌陷现象,并且显示出拉伸强度、弯曲强度、冲击强度等机械物理性能中具有优异的平衡的特性。这种聚碳酸酯树脂组合物可以适合用作3D打印用材料。
另一方面,从表2中可知,当比较例1中没有碳母料时,界面粘合力降低,另一方面,可知比较例2的碳母料的含量高,因此可能会发生物理性能的降低。
在比较例3和比较例4中,碳纤维的含量低,因此可知发生塌陷现象。
在比较例5中,可知当没有聚对苯二甲酸丁二醇酯树脂时,固化速度变慢,因此发生塌陷现象,在比较例6中,由于聚对苯二甲酸丁二醇酯树脂的含量高,因此可以确认发生物理性能的降低,并且界面粘合力降低。
Claims (8)
1.一种3D打印用树脂组合物,其中,以总共100重量份的组合物为基准,所述树脂组合物包含:(1)62-76重量份的聚碳酸酯树脂、(2)1-11重量份的聚对苯二甲酸丁二醇酯树脂、(3)1-9.5重量份的炭黑母料和(4)11-25重量份的碳纤维。
2.根据权利要求1所述的3D打印用树脂组合物,其中,所述聚碳酸酯树脂的粘均分子量为15000至50000。
3.根据权利要求1所述的3D打印用树脂组合物,其中,聚对苯二甲酸丁二醇酯树脂的熔融温度为215℃-235℃,特性粘度(IV)为0.45-1.6dl/g。
4.根据权利要求1所述的3D打印用树脂组合物,其中,所述炭黑母料的粒径为10-40nm,氮吸附比表面积(NSA)为150-250m2/g。
5.根据权利要求1所述的3D打印用树脂组合物,其中,所述碳纤维的直径为1-30μm。
6.根据权利要求1所述的3D打印用树脂组合物,其中,所述树脂组合物进一步包含选自无机颗粒、抗氧化剂、滑爽剂、紫外线吸收剂、光稳定剂、抗冲改性剂、消光剂、阻燃剂或它们的混合物中的至少一种添加剂。
7.一种3D打印用颗粒,其包含权利要求1至6中任一项所述的组合物。
8.一种3D打印用长丝,其包含权利要求1至6中任一项所述的组合物。
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