3D打印光敏树脂材料的研究进展

目前，3D打印已应用于各行业中，打印材料的选择成为制约3D打印技术进一步发展的关键因素。光固化3D打印技术由于打印速度快、成品精度高、对环境无污染等优点被广泛应用，而光敏树脂作为光固化3D打印的主要材料对打印系统的性能起关键作用。本文简单介绍了3D打印光敏树脂的成分，对3D打印光敏树脂的3种类型进行了说明，并对3D打印光敏树脂复合/改性材料的研究进行了阐述。展望指出研究出性能好的3D打印光敏树脂复合/改性材料是3D打印技术不断满足各行各业多元化发展需求的重点课题。     

3D打印用光敏树脂及功能化研究进展

本文介绍了3D打印用光敏树脂的研究现状,综述了三类光敏树脂的原料及引发机理,同时对光敏树脂的功能化研究进行了一定的总结,最后对光敏树脂基3D打印材料的发展趋势及应用前景进行了分析和展望。     

光固化3D打印及光敏树脂改性研究进展

为加深对光固化3D技术及光敏树脂的研究,简述了光固化3D技术的6种主流技术种类及最新的计算轴向光刻(CAL)打印技术,分析了各自的成型原理及优缺点,介绍了光敏树脂固化原理及最新的光敏树脂改性研究,着重分析了在增强增韧、膨胀单体、医用方面和功能化研究进展,同时对光固化3D打印的发展现状进行分析及对前景进行了展望。     

面向光固化3D打印陶瓷构件的光敏树脂体系研究

光敏树脂是光固化3D打印的材料基础,也是光固化3D打印陶瓷的成型媒介。光敏树脂体系影响光固化3D打印陶瓷构件成型过程的收缩率与脱脂过程的应力,本文设计了含环状结构的单官能度树脂、三官能度树脂及引入预聚物及稀释剂的多组分树脂三个树脂体系,测试了三个树脂体系的收缩率,研究表明引入预聚物及稀释剂的树脂体系具有最低的固化收缩率,有效缓解了因固化反应收缩造成的3D打印氧化铝陶瓷素坯开裂的问题。采用热失重分析和热处理实验研究了三个树脂体系的热分解行为,多组分树脂体系具有分阶段热解的特性,采用该树脂体系制备了光敏性氧化铝浆料,优化了光固化打印参数及脱脂气氛,3D打印厚壁实心(12 mm×12 mm×12 mm)样件与大尺寸(?80 mm×50 mm)的氧化铝陶瓷素坯脱脂后均无裂纹等缺陷。     

3D打印用光敏树脂的制备及改性研究进展

介绍了3D打印光敏树脂的研究现状,简述了UV光敏树脂的原料和制备方法:包括自由基引发、阳离子引发和自由基-阳离子混杂引发,总结了光敏树脂的增强增韧改性研究进展,展望了SLA工艺光敏树脂的研究趋势。     

适用于光固化3D打印的光敏树脂的研究进展

以光敏树脂为原料的光固化3D打印技术具有成型精度高、固化速度快、耐候性好等优点,近几年来得到广泛的推广和应用。本文阐述了阳离子型光敏树脂、自由基型光敏树脂、混合型光敏树脂近年来的进展,讨论了阳离子型和自由基型光引发剂对三维打印技术的影响,展望了未来光敏树脂材料发展趋势。     

3D打印高分子材料的研究进展

三维快速成型打印简称为3D打印,属于快速成型制造技术中。本文探究了3D打印所用高分子材料的现状及研究进展,常用的材料有工程塑料、光敏树脂和生物医用材料。随着3D打印技术的发展,针对打印高分子材料的研究成为3D打印技术提升的关键。     

可逆热致变色型光敏树脂的制备与性能研究

为了适应3D打印光固化的要求,从不同的预聚物、稀释剂和光引发剂中选择合适的材料配制光敏树脂,使光敏树脂在3D打印的过程中具有较低的收缩率和黏度、较高的凝胶含量,并通过添加无机热致变色材料使配制的光敏树脂具有可逆热致变色的功能。结果表明,选择双酚F环氧丙烯酸酯为预聚物,二缩三丙二醇二丙烯酸酯(TPGDA)为稀释剂,2,4,6-三甲基苯甲酰基二苯基氧化膦(TPO)为光引发剂,通过研究各组分添加比例对光敏树脂的性能的影响,确定了预聚物、稀释剂和光引发剂的质量分数比为70%∶26%∶4%;热致变色材料的质量分数为5%时在光敏树脂中分散均匀、分布良好。配制所得的光敏树脂黏度为458 m Pa·s,凝胶含量为90.65%,打印制品收缩率为4.34%,在140℃下变色明显且可逆,满足3D打印的要求。     

光固化3D打印用光敏树脂的研究进展

综述了不同类型的光固化三维(3D)打印用光敏树脂的研究进展,包括环氧丙烯酸酯、不饱和聚酯、聚酯丙烯酸酯及聚氨酯丙烯酸酯,对各树脂的合成方法、优缺点进行了比较。根据树脂的光固化速率、黏度、柔韧性、热稳定性、硬度、耐磨性、耐化学药品腐蚀性等对3D打印产品性能的影响,针对不同树脂的缺点总结了提高树脂性能的方法。此外,还指出了光固化3D打印用光敏树脂的发展趋势,为今后探索新型合成方法及树脂性能的改进提供参考。     

一种3D打印光敏树脂的研制及性能

以改性环氧丙烯酸酯为预聚物,采用自由基-阳离子杂化聚合法制备了可在405 nm光照下固化的3D打印光敏树脂。研究了预聚物、稀释剂、光引发剂的含量对光敏树脂力学性能、黏度和体积收缩率的影响。结果表明,当光引发剂添加量为4%时,力学性能最优化;当改性环氧丙烯酸酯含量在48%~58%时,该体系能满足3D打印光固化材料的使用要求;采用本方法制备的光敏树脂具有卓越的热稳定性。     

3D打印材料的研究及发展现状

对3D打印材料进行了分类和论述,将3D打印材料分为有机高分子材料和无机材料两大类,前者包括丙烯腈苯乙烯丁二烯共聚物(ABS)、聚乳酸(PLA)、聚酰胺(PA)、光敏树脂以及水凝胶等;后者包括钛及钛合金、陶瓷和石膏等。分别阐述了其性能和优缺点以及在3D打印领域的应用现状,并对3D打印材料的发展前景进行了展望。     

一种双低聚物3D打印用光敏树脂的制备与性能研究

随着光固化3D打印技术的发展,制备收缩率小、凝胶含量高,性能符合使用要求的光敏树脂极为重要,以纯丙烯酸酯(2官能度,2-AE)、聚氨酯丙烯酸酯(6官能度,6-PUA)为低聚物,二缩三丙二醇二丙烯酸酯(TPGDA)为稀释剂,2,4,6-三甲基苯甲酰基-二苯基氧化膦(TPO)为光敏剂,利用正交试验法配制光敏树脂溶液并通过3D打印完成样品制备。以收缩率、凝胶含量、黏度及硬度为评价指标,通过综合平衡法对测试结果进行分析,研究结果表明,光敏树脂溶液制备的最佳配方为:两种低聚物(纯丙烯酸酯、聚氨酯丙烯酸酯)质量比为2∶1,稀释剂质量分数为57.6%,光敏剂质量分数为3%。样品性能参数为:收缩率4.7%,凝胶含量96.6%(质量分数),黏度105 mPa·s,邵氏硬度80 HD。     

Acrylate-based photosensitive resin for stereolithographic three-dimensional printing

In this article, we report an acrylate-based three-dimensional (3D) printing stereolithography rapid-prototyping photosensitive resin with a low viscosity, small volumetric shrinkage, high photoreactivity, and excellent strength. The resin was a compound prepared with bisphenol A epoxy acrylate (BAEA) as the main matrix, 1,6-hexanediol diacrylate (HDDA) and tri(propylene glycol) diacrylate (TPGDA) as reactive diluents, pentaerythritol triacrylate (PETA) as the crosslinking agent, and 2-hydroxy-2-methyl propiophenone (1173) and diphenyl(2,4,6-trimethyl benzoyl)phosphine oxide (TPO) as photoinitiators. The photocuring kinetics of the resins with different photoinitiator types and loadings were studied via real-time IR spectroscopy, which provided insights into the optimization of photoinitiator composition and printing parameter settings. The results show that the content change of each component affected the viscosity of the photosensitive resin; this was accompanied by fluctuations in the volume shrinkage and mechanical strength of the cured products. Although an increase in the molar ratio of the reactive diluent remarkably reduced the viscosity of the photosensitive resin and thereby boosted photopolymerization, it also caused an increase in the volume shrinkage and a sacrifice of mechanical strength. Finally, as shown by a comparison of the other samples we studied, the resin composed of 30 mmol HDDA, 50 mmol TPGDA, 10 mmol PETA, 10 mmol BAEA, 2.5 mol % TPO, and 2.5 mol % 1173 achieved the best viscosity of 239.53 mPa s at 25 °C, the minimum shrinkage rate of 4.36%, and the maximum tensile strength of 43.19 MPa. The 3D printing curing products had the closest size to the design dimensions of the computer-aided design model; this indicated that the resin seemed to be a most promising candidate for 3D printing applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47487.     

Urethane acrylate-based photosensitive resin for three-dimensional printing of stereolithographic elastomer

Three-dimensional (3D) printing elastomers have received wide attention because of their wide applications in many fields. In this work, we report a urethane acrylate-based photosensitive resin compound for 3D printing whose cured materials are elastic. This resin consists of bifunctional urethane acrylate (Royji 426 as the main matrix, monofunctional urethane acrylate (Royji 425), and isobornyl methacrylate (IBMA) as the diluents, trimethylolpropane triacrylate (TMPTA) as the crosslinker, phenylbis(2,4,6-trimethylbenzoyl)-phosphine oxide (819) and 2-hydroxy-2-methyl propiophenone (1173) as photoinitiators. The results indicate that the mechanical properties of cured materials can be tuned by adjusting the content of different components, but it is also accompanied by the changes in viscosity and volume shrinkage. Real-time Fourier transform infrared spectroscopy was employed to explore the relationship between the photoinitiators and the rate of initiation, and then found the best photoinitiators formulation. The resultant resin exhibits tensile strength of 7.46 MPa, elongation of 180.6%, viscosity of 978.53 mPa·s at 25°C and the volume shrinkage rate of 4.15%. Some complicated structures can be printed with the photosensitive resin such as C₆₀, hollow ball, wrist strap, and porous lattices. These architectures have excellent dimensional accuracy and can undergo any large deformation without damage. This manifested that this resin can provide a solution for existing 3D printing of elastomers.     

胶印PS版用成膜树脂及酯化树脂的发展

胶印PS版由于生产工艺成熟,价格便宜,制版设备简单,是目前印刷领域使用最为广泛的版材。对胶印版材所用的成膜树脂和阳图感光PS版用酯化树脂的相关文献进行了综述。成膜树脂是胶印PS版中非常重要的组成部分。酯化树脂的作用是将感光基团引入感光组成物。成膜树脂重点介绍了酚醛树脂和烯类树脂,酯化树脂则着重于介绍酚醛树脂和酚树脂。     

Yellow resistant photosensitive resin for digital light processing 3D printing

Digital light processing (DLP) has been studied and developed in the field of three-dimensional (3D) printing in recent years due to its fast curing rate and high resolution. To reduce the cost and viscosity of the resin system, the aromatic polyurethane acrylates (PUAs) were used as oligomer. The matrix resin called PUH₂ consists of oligomers (PUA, bisphenol A polyoxyethylene ether dimethyl acrylate) and active diluents (hydroxyethyl acrylate, hydroxyethyl methacrylate). However, the photosensitive resin containing aromatic isocyanate groups was easily yellowed under ultraviolet light. In this article, we developed a resin for DLP 3D printing with yellowing resistance, excellent mechanical properties and high heat resistance. The optimal ratio of 3DP-PUH₂ resin was PUH₂/TPO/RYOJI-292/dye/nanosilica = 100/5/0.4/0.01/0.1, and its viscosity was 500 cp, which is suitable for DLP 3D printing. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48369.     

3D打印用高分子材料及打印成型工艺参数优化研究进展

综述了近年来应用在3D打印成型技术中的高分子材料。其中,通用塑料包括综合性能优异的丙烯腈-丁二烯-苯乙烯三元共聚物、可生物降解的聚乳酸和聚己内酯;典型工程塑料和特种工程塑料主要包括聚碳酸酯和聚醚醚酮;热固性塑料主要有光敏树脂。不同的高分子材料性能不同,所采用的3D打印技术也各不相同,最终制备的3D打印制件应用领域也各不相同。除了对制件母材进行筛选外,3D打印工艺参数也会对制件质量产生显著的影响,而计算机辅助技术在这一方面的应用较为广泛。     

Influence of number average molecular weight on the properties of 3D printed precursor ceramics

A deliberately selected end-capping agent was introduced into the precursor to form a low number average molecular weight precursor and meet the need for liquid crystal display (LCD) 3D printing. The influence of number average molecular weight on the photocuring properties of precursor and the physical properties of pyrolysis samples were studied in detail for the first time. The results proved that a relatively low number average molecular weight precursors had low ceramic yields after pyrolysis. As the number average molecular weight of the precursor decreased, the photocuring ability of the precursor photosensitive resin increased. With the decrease in the number average molecular weight of the precursor in the precursor photosensitive resin, the ceramic yield of 3D printed PDCs decreased from 58.4% to 30.2%, and the linear shrinkage increased from 27.2% to 40.3%. The bending strength of the LCD 3D printed specimen reached 61.5 ± 3.7 MPa. The low cost of precursor synthesis and equipment in this study points the way for the preparation of precursor non-oxide ceramic composites and can be conducive to the development and application of LCD 3D printing precursor ceramics.