CN110341097B - A thermoplastic polymer based on DLP photocuring 3D printing and its application - Google Patents
A thermoplastic polymer based on DLP photocuring 3D printing and its applicationDownload PDFInfo
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- CN110341097B CN110341097BCN201910717349.XACN201910717349ACN110341097BCN 110341097 BCN110341097 BCN 110341097BCN 201910717349 ACN201910717349 ACN 201910717349ACN 110341097 BCN110341097 BCN 110341097B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/3842—Manufacturing moulds, e.g. shaping the mould surface by machining
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
- B29C33/40—Plastics, e.g. foam or rubber
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
- B29C33/52—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles soluble or fusible
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
- B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- 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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- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及聚合物加工制造领域，尤其涉及一种基于DLP光固化3D打印的热塑性聚合物及应用。The invention relates to the field of polymer processing and manufacturing, in particular to a thermoplastic polymer based on DLP light-curing 3D printing and its application.
背景技术Background technique
3D打印(增材制造)是一种以数字模型文件为基础，通过逐层打印的方式来构造物体的成型技术，已经被广泛用于模具、工业设计的模型制造及一些产品的直接制造。作为一种直接成型技术，不需要使用模具并且其最突出的优势是能够构建一些不规则、复杂的三维结构。3D printing (additive manufacturing) is a molding technology that builds objects by layer-by-layer printing based on digital model files. It has been widely used in molds, industrial design model manufacturing and direct manufacturing of some products. As a direct molding technology, it does not require the use of molds and its most prominent advantage is that it can build some irregular and complex three-dimensional structures.
在构建复杂形状聚合物的打印方法中，数字化光处理DLP(Digital LightProcession)是一种基于数字化投影技术的三维打印工艺，使用一种较高分辨率的数字光处理器来固化液态光聚合物，逐层对液态聚合物进行固化。相比于其他聚合物成型方法包括熔融挤出技术FDM、立体光固化技术SLA的逐点成型，面成型DLP技术具有成型速度快且精度高的优势，但也存在以下缺点：Among the printing methods for constructing complex-shaped polymers, Digital Light Processing (DLP) is a three-dimensional printing process based on digital projection technology, which uses a higher-resolution digital light processor to cure liquid photopolymers. The liquid polymer is cured layer by layer. Compared with other polymer molding methods including melt extrusion technology FDM, stereo light curing technology SLA point-by-point molding, surface molding DLP technology has the advantages of fast molding speed and high precision, but it also has the following disadvantages:
(1)DLP使用的树脂材料往往需要加入预聚物用来降低固化收缩率，但是粘度相对较高，使得打印过程流平困难，极大地降低了打印速度；(1) The resin materials used in DLP often need to add prepolymers to reduce the curing shrinkage rate, but the viscosity is relatively high, which makes it difficult to level the printing process and greatly reduces the printing speed;
(2)另一方面由于多官能度预聚物的引入使得光固化得到的是一种热固性材料，后期难以进行再次加工；(2) On the other hand, due to the introduction of the multifunctional prepolymer, what is obtained by photocuring is a thermosetting material, which is difficult to reprocess later;
(3)另外，由于成型方法依赖于光固化技术，树脂材料必须是能够光引发聚合的材料，对于其他常用材料例如环氧树脂、聚二甲基硅氧烷PDMS等是不能够实现复杂结构的构筑的。(3) In addition, since the molding method relies on photo-curing technology, the resin material must be a material capable of photo-initiated polymerization, and complex structures cannot be realized for other commonly used materials such as epoxy resin, polydimethylsiloxane PDMS, etc. constructed.
因此，如何实现非光固化材料的复杂结构快速成型是一个难点，对于现有的模具制造，周期长且复杂结构脱模困难。光固化热塑性聚合物可为这种矛盾提供一种新的解决手段。Therefore, it is difficult to realize the rapid prototyping of complex structures of non-photocurable materials. For the existing mold manufacturing, the cycle is long and the complex structures are difficult to demould. Photocurable thermoplastic polymers can provide a new solution to this contradiction.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于提供一种基于DLP光固化3D打印的热塑性聚合物，可以采用DLP光固化3D打印的方法快速构建热塑性聚合物，作为水溶性或高温熔化模具，用于多种材料体系的塑形，赋予其更高的附加值。The purpose of the present invention is to provide a thermoplastic polymer based on DLP light-curing 3D printing, which can be quickly constructed by the DLP light-curing 3D printing method, as a water-soluble or high-temperature melting mold, used for plastics of various material systems. shape, giving it a higher added value.
一种基于DLP光固化3D打印的热塑性聚合物，所述热塑性聚合物为光敏树脂前驱液通过DLP光固化3D打印制备，所述光敏树脂前驱液包括单官能团单体、光引发剂、光吸收剂和分子量调节剂，所述单官能团单体为单丙烯酸酯基的丙烯酸酯单体或单丙烯酰胺基的丙烯酰胺单体。A thermoplastic polymer based on DLP photocuring 3D printing, the thermoplastic polymer is a photosensitive resin precursor liquid prepared by DLP photocuring 3D printing, and the photosensitive resin precursor liquid includes a monofunctional monomer, a photoinitiator, and a light absorber and a molecular weight regulator, the monofunctional monomer is a monoacrylate-based acrylate monomer or a monoacrylamide-based acrylamide monomer.
在本发明中，所述光敏树脂前驱液中的单官能团单体含有活性官能团，能在光照射下由光引发剂引发聚合反应；并且只含有一个活性官能团，聚合物形成物理缠结的凝胶网络。优选的，单官能团单体的聚合速度必须很快达到凝胶所需的分子量，并且满足其均聚物的玻璃化转变温度高于室温，用于稳定凝胶网络。In the present invention, the monofunctional monomer in the photosensitive resin precursor liquid contains an active functional group, which can initiate a polymerization reaction by a photoinitiator under light irradiation; and only contains one active functional group, and the polymer forms a physically entangled gel network. Preferably, the polymerization speed of the monofunctional monomer must quickly reach the molecular weight required for the gel, and the glass transition temperature of the homopolymer must be higher than room temperature, so as to stabilize the gel network.
本发明提供的热塑性聚合物采用一类特殊活性单体材料通过光固化DLP技术得到一个分子量可控，结构可控的复杂三维结构热塑性聚合物模型。由于单体的粘度低以及表层氧阻聚特性可以实现快速打印，通过改变链转移剂的含量能够很好地控制材料的分子量，结合单体的热融化或水溶性质实现快速脱模。The thermoplastic polymer provided by the invention adopts a special active monomer material to obtain a complex three-dimensional thermoplastic polymer model with a controllable molecular weight and a controllable structure through the light-curing DLP technology. Due to the low viscosity of the monomer and the oxygen-inhibiting properties of the surface layer, rapid printing can be achieved. By changing the content of the chain transfer agent, the molecular weight of the material can be well controlled, and the thermal melting or water-soluble properties of the monomer can be combined to achieve rapid mold release.
以质量分数计，所述树脂包括0.1-5％的光引发剂、0.01-0.1％的光吸收剂和0.1-2％的分子量调节剂。In terms of mass fraction, the resin includes 0.1-5% of photoinitiator, 0.01-0.1% of light absorber and 0.1-2% of molecular weight regulator.
所述丙烯酸酯单体选自丙烯酸异冰片酯或甲基丙烯酸异冰片酯中的一种或两者的组合；所述丙烯酰胺单体选自丙烯酰吗啉或二甲基丙烯酰胺中的一种或两者的组合。The acrylate monomer is selected from one or a combination of isobornyl acrylate or isobornyl methacrylate; the acrylamide monomer is selected from one of acryloyl morpholine or dimethylacrylamide. species or a combination of both.
优选的，所述单官能团单体为丙烯酰吗啉。丙烯酰吗啉具有良好的水溶性，能够被用于水溶性模具的制备。Preferably, the monofunctional monomer is acryloyl morpholine. Acryloylmorpholine has good water solubility and can be used for the preparation of water-soluble molds.
所述光引发剂选自苯偶姻及衍生物、苯偶酰类、烷基苯酮类、酰基邻氧化物、二苯甲酮类或硫杂蒽酮类中的一种或至少两种的组合。The photoinitiator is selected from one or at least two of benzoin and derivatives, benzil, alkyl phenone, acyl ortho oxide, benzophenone or thioxanthone. combination.
优选的，所述光引发剂选自安息香、安息香双甲醚、二苯基乙酮、二甲氧基苯基苯乙酮、羟烷基苯酮、芳酰基磷氧化物、二苯甲酮、2，4-二羟基二苯甲酮或硫代丙氧基硫杂蒽酮中的一种或至少两种的组合。Preferably, the photoinitiator is selected from benzoin, benzoin dimethyl ether, diphenylethanone, dimethoxyphenylacetophenone, hydroxyalkylphenone, aroyl phosphorus oxide, benzophenone, One or a combination of at least two of 2,4-dihydroxybenzophenone or thiopropoxythioxanthone.
所述分子量调节剂选自脂肪族硫醇、苯乙烯多聚体或戊烯中的一种或至少两种的组合。The molecular weight regulator is selected from one or a combination of at least two of aliphatic thiol, styrene polymer or pentene.
所述分子量调节剂(又称为链转移剂)为具有传递自由基能力的组分。可用于调节聚合物分子量以改善材料的水溶解性能。The molecular weight regulators (also known as chain transfer agents) are components that have the ability to transfer free radicals. It can be used to adjust the molecular weight of polymers to improve the water solubility of the material.
优选的，所述脂肪族硫醇为单官能度硫醇，其结构为：Preferably, the aliphatic thiol is a monofunctional thiol, and its structure is:
R1-SHR1 -SH
其中R1可为脂肪链或芳香环或者其它环状结构，如选自甲基，乙基，丙基及其异构基团，丁基及其异构基团，戊基及其异构基团，己基及其异构基团，庚基及其异构基团，辛基及其异构基团，壬基及其异构基团，癸基及其异构基团，十一碳基及其异构基团，十二碳基及其异构基团，十三碳基及其异构基团，十四碳基及其异构基团，十五碳基及其异构基团，十六碳基及其异构基团；芳基及其同系物基团；糠基，吡啶基，噻吩基，咪唑基，吡咯基等杂环基团中的一种或多种。Wherein R1 can be aliphatic chain or aromatic ring or other cyclic structure, such as selected from methyl, ethyl, propyl and its isomeric groups, butyl and its isomeric groups, pentyl and its isomeric groups group, hexyl and its isomeric groups, heptyl and its isomeric groups, octyl and its isomeric groups, nonyl and its isomeric groups, decyl and its isomeric groups, undecyl and its isomeric group, dodecyl and its isomeric group, tridecyl and its isomeric group, tetradecyl and its isomeric group, pentadecyl and its isomeric group , hexadecyl and its isomeric groups; aryl and its homologue groups; one or more of furfuryl, pyridyl, thienyl, imidazolyl, pyrrolyl and other heterocyclic groups.
优选的，所述树脂还包括光吸收剂，所述光吸收剂选自苏丹Ⅰ、苏丹Ⅱ、苏丹Ⅲ、酞菁绿、酞菁蓝、胭脂红、柠檬黄、钛白粉或炭黑中的一种或至少两种的组合。以质量百分数计，光吸收剂加入量占树脂的0.01％-0.5％。Preferably, the resin further comprises a light absorbing agent, and the light absorbing agent is selected from one of Sudan I, Sudan II, Sudan III, phthalocyanine green, phthalocyanine blue, carmine, tartrazine, titanium dioxide or carbon black one or a combination of at least two. In terms of mass percentage, the added amount of the light absorber accounts for 0.01%-0.5% of the resin.
在本发明中，通过DLP光固化3D打印制备热塑性聚合物的方法为面成型投影仪逐层光照固化成型，配合平台移动完成打印过程。In the present invention, the method for preparing the thermoplastic polymer by DLP light-curing 3D printing is that the surface forming projector is light-cured and formed layer by layer, and the printing process is completed with the movement of the platform.
具体地，所述光敏树脂前驱液通过DLP光固化3D打印制备热塑性聚合物的方法包括以下步骤：Specifically, the method for preparing a thermoplastic polymer by DLP photocuring 3D printing of the photosensitive resin precursor solution includes the following steps:
(1)将光敏树脂前驱液置于承装树脂容器中，根据打印模型的结构设计对应曝光参数，调整平台初始高度开始打印；(1) Place the photosensitive resin precursor liquid in the resin container, and adjust the initial height of the platform to start printing according to the corresponding exposure parameters of the structural design of the printing model;
(2)使用DLP投影仪按预设模型切片对光敏树脂前驱液进行曝光固化，再通过平台连续移动得到三维模型打印件；(2) Use a DLP projector to expose and cure the photosensitive resin precursor liquid according to the preset model slice, and then continuously move the platform to obtain a three-dimensional model print;
(3)将三维模型打印件取下并置于溶剂中洗去残余单体，之后放入紫外固化箱进行后固化，得到热塑性聚合物。(3) The three-dimensional model printed part is removed and placed in a solvent to wash off residual monomers, and then placed in an ultraviolet curing box for post-curing to obtain a thermoplastic polymer.
本发明提供的制备方式是通过数字化投影技术得到一个具有三维复杂结构，分子量可调的热塑性聚合物。本发明方法的关键步骤是使用DLP投影仪对单官能度光敏树脂前驱液进行直接成型。The preparation method provided by the invention is to obtain a thermoplastic polymer with a three-dimensional complex structure and adjustable molecular weight through digital projection technology. The key step of the method of the present invention is to directly shape the monofunctional photosensitive resin precursor liquid by using a DLP projector.
步骤(2)中所述的模型切片处理可利用商业软件完成，切片层厚为10μm-200μm，平台移动的方式可根据模型调节，可分为连续下降，间歇下降，下降抬升三种。投影仪的工作模式为光照+黑屏。平台移动过程中投影仪处于黑屏状态。光照时间根据配方中光引发剂浓度，光吸收剂加入量，链转移剂浓度在0.3-10s之间进行调节。黑屏时间可在0-5s之间调节。The model slicing process described in step (2) can be completed by commercial software, the slice layer thickness is 10 μm-200 μm, and the movement mode of the platform can be adjusted according to the model, which can be divided into three types: continuous descending, intermittent descending, descending and lifting. The working mode of the projector is light + black screen. The projector is in a black screen state while the platform is moving. The illumination time is adjusted between 0.3-10s according to the concentration of photoinitiator in the formula, the amount of light absorber added, and the concentration of chain transfer agent. The black screen time can be adjusted between 0-5s.
本发明中DLP投影仪使用商品化的DLP投影仪。The DLP projector in the present invention uses a commercialized DLP projector.
DLP投影仪光源发出的波段为400-700nm。DLP投影仪也可使用小于400nm的紫外波段的光源置换DLP投影仪中的光源。The wavelength band emitted by the DLP projector light source is 400-700nm. The DLP projector can also replace the light source in the DLP projector with a light source in the ultraviolet band less than 400 nm.
在步骤(3)中，所述溶剂选自乙醇、乙酸乙酯、乙酸丁酯、二氯甲烷、氯仿、苯、甲苯、四氢呋喃或二甲基甲酰胺中的一种或至少两种的组合。紫外固化箱的波长范围为312-700nm。光照时间根据模型结构而定，可在1-1000s之间调节。In step (3), the solvent is selected from one or a combination of at least two of ethanol, ethyl acetate, butyl acetate, dichloromethane, chloroform, benzene, toluene, tetrahydrofuran or dimethylformamide. The wavelength range of the UV curing box is 312-700nm. The lighting time depends on the model structure and can be adjusted between 1-1000s.
本发明还提供一种基于DLP光固化3D打印的热塑性聚合物作为水溶性或高温熔化模具的应用。The invention also provides an application of the thermoplastic polymer based on DLP photocuring 3D printing as a water-soluble or high-temperature melting mold.
优选的，所述水溶性或高温熔化模具用于制备热固性聚合物无，所述热固性聚合物为热固性环氧树脂或聚二甲基硅氧烷。Preferably, the water-soluble or high-temperature melting mold is used for preparing a thermosetting polymer, and the thermosetting polymer is a thermosetting epoxy resin or polydimethylsiloxane.
与现有技术相比，本发明的有益效果体现在：Compared with the prior art, the beneficial effects of the present invention are embodied in:
(1)热塑性聚合物从笔者角度无法从DLP打印方法实现的，本发明通过选择了特殊反应单体实现了热塑性聚合物的打印，由于只有低粘度的反应性单体存在，树脂的流平速度极快，能够帮助实现DLP快速打印而不需要其他辅助设备。(1) Thermoplastic polymers cannot be realized by the DLP printing method from the author's point of view. The present invention realizes the printing of thermoplastic polymers by selecting special reactive monomers. Since only reactive monomers with low viscosity exist, the leveling speed of the resin is reduced. Extremely fast, can help achieve DLP fast printing without the need for other auxiliary equipment.
(2)热塑性聚合物可在高温熔化或者结合并烯酰吗啉的水溶特点，复杂形状可以被赋予其他非光固化打印材料，比如商用热固性环氧树脂，聚二甲基硅氧烷PDMS等。(2) Thermoplastic polymers can be melted at high temperature or combined with the water-soluble characteristics of dimethomorph, and complex shapes can be given to other non-photocurable printing materials, such as commercial thermosetting epoxy resins, polydimethylsiloxane PDMS, etc.
附图说明Description of drawings
图1为本发明采用的数字化投影设备及装置示意图；1 is a schematic diagram of the digital projection equipment and device used in the present invention;
图2为本发明提供的光敏树脂前驱液的光照聚合情况示意图；Fig. 2 is the photopolymerization situation schematic diagram of the photosensitive resin precursor liquid provided by the present invention;
图3为实施例1制备的三维空心结构实物图；Fig. 3 is the physical map of the three-dimensional hollow structure prepared in Example 1;
图4为应用例1中作为水溶性模具的示意图；Fig. 4 is a schematic diagram as a water-soluble mold in Application Example 1;
图5为应用例1中另一作为水溶性模具的示意图。FIG. 5 is a schematic diagram of another water-soluble mold in Application Example 1. FIG.
具体实施方式Detailed ways
以下结合实施例对本发明做进一步说明，但本发明要求保护的范围并不局限于实施例表达的范围。The present invention will be further described below with reference to the examples, but the claimed scope of the present invention is not limited to the scope expressed by the examples.
如图1所示，本发明采用的数字化投影设备及装置制备热塑性固化物，包括：计算机1、DLP投影仪2、打印平台3和树脂槽4；树脂槽内填充有光敏树脂前驱液5。本发明的应用范围不局限于图1中所示的自上而下(top-down)的光固化3D打印方法，也包括其他光固化3D打印方法如自下而上(bottom-up)光固化3D打印方法等使用面投影技术制备光固化聚合物的方法。As shown in FIG. 1 , the digital projection equipment and device used in the present invention to prepare a thermoplastic cured product include: a
DLP投影仪2通过G代码(G code)与计算机1相连，投影的图案由计算机1辅助设计的CAD模型传输至DLP投影仪2；通过DLP投影仪2局部多次投射至光敏树脂前驱液5表面，之后经历一定的黑屏时间，在黑屏时间里平台移动将新鲜树脂补充至已固化的树脂表面形成一层新的液层。待黑屏时间结束投影仪继续投射下一层图案进行固化，逐层堆叠形成三维结构。固化完成后，将固化得到的三维打印件洗去多余单体，拭干后进行后固化处理，至打印件表面不再发粘为止。The
实施例1制备亲水性丙烯酰吗啉树脂Example 1 Preparation of hydrophilic acryloyl morpholine resin
光敏树脂前驱液原料：Photosensitive resin precursor liquid raw materials:
a)丙烯酰吗啉(ACMO)：Lihou(Guangdong)公司；a) Acryloyl morpholine (ACMO): Lihou (Guangdong) company;
b)苏丹Ⅲ：Aladdin公司；b) Sudan III: Aladdin Company;
c)1-癸烷硫醇(decylthiol)：Aladdin公司；c) 1-decylthiol (decylthiol): Aladdin company;
d)苯基双(2,4,6-三甲基苯甲酰基)氧化膦(Irgacure 819)：Sigma-Aldrich公司；d) Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure 819): Sigma-Aldrich;
将单体和其他物质按一定比例(质量分数ACMO:decylthiol:Irgacure 819:SudanⅢ＝100:1:1:0.025)混合均匀，采用图1所示意的数字化投影设备及装置图进行循环投影、曝光和固化：DLP投影仪光源发出的波段为400-700nm，单次投影时间为1.8s，平台下降带动树脂流动形成新的液层，再次曝光下一层图案，通过平台持续向下移动从而得到三维模型打印件。Mix the monomer and other substances in a certain proportion (mass fraction ACMO:decylthiol:Irgacure 819:SudanⅢ=100:1:1:0.025), and use the digital projection equipment and device diagram shown in Figure 1 to perform cyclic projection, exposure and Curing: The wavelength band emitted by the DLP projector light source is 400-700nm, and the single projection time is 1.8s. The platform descends to drive the resin to flow to form a new liquid layer, and the next layer of pattern is exposed again. The platform continues to move downward to obtain a 3D model. print.
图2展示了光敏树脂前驱液的快速流平能力。由于光敏树脂前驱液只有活性单体存在，整体粘度很低，使得光敏树脂前驱液在打印过程中能够很快流平，缩短了黑屏时间。另外由于空气中存在的氧气，使得打印过程中光敏树脂前驱液表层气液两相的氧浓度存在差异。表面氧阻聚的存在进一步加快了新鲜光敏树脂前驱液的渗透，从而可实现快速打印。图2中用单层光敏树脂前驱液的光照聚合情况模拟打印过程中的固化动力学，表层氧阻聚使得固化程度在平行于光源方向由下而上逐渐降低，单体转化率逐渐减小，证明在一定光照条件下固化表层剩余单体较多。Figure 2 demonstrates the fast leveling capability of the photosensitive resin precursor. Since only active monomers exist in the photosensitive resin precursor, the overall viscosity is very low, so that the photosensitive resin precursor can be quickly leveled during the printing process, and the black screen time is shortened. In addition, due to the presence of oxygen in the air, there is a difference in the oxygen concentration of the gas-liquid two phases on the surface of the photosensitive resin precursor during the printing process. The presence of surface oxygen inhibition further accelerates the penetration of fresh photosensitive resin precursor liquid, enabling fast printing. In Figure 2, the photopolymerization of a single-layer photosensitive resin precursor is used to simulate the curing kinetics during the printing process. The surface oxygen inhibition makes the curing degree gradually decrease from bottom to top in the direction parallel to the light source, and the monomer conversion rate gradually decreases. It is proved that there are more residual monomers in the cured surface layer under certain light conditions.
图3展示了基于DLP光固化3D打印的热塑性聚合物的结构，采用实施例1中的光敏树脂前驱液，得到的三维模型打印件为镂空、悬空和空心结构Figure 3 shows the structure of the thermoplastic polymer based on DLP photocuring 3D printing. Using the photosensitive resin precursor in Example 1, the obtained 3D model prints are hollow, suspended and hollow structures.
应用例1Application example 1
图4、5展示了使用实施例1制备的三维模型打印件作为水溶性模具。Figures 4 and 5 show the use of the three-dimensional model print prepared in Example 1 as a water-soluble mold.
图4中展示了作为热固性环氧树脂的复杂结构塑形的水溶性模具。环氧树脂前驱液配方：(摩尔分数环氧E44:二元胺D-230＝1:1)，130℃固化2小时，模具可在50℃水中半小时溶解。Figure 4 shows a water-soluble mold for the shaping of complex structures as thermoset epoxy resins. Epoxy resin precursor solution formula: (molar fraction of epoxy E44: diamine D-230=1:1), cured at 130°C for 2 hours, the mold can be dissolved in water at 50°C for half an hour.
图5为将三维模型打印支架放入PDMS前驱液中，加热固化后通过溶解支架得到三维微流道结构。Figure 5 shows that the three-dimensional model printed scaffold is put into the PDMS precursor solution, and the three-dimensional micro-channel structure is obtained by dissolving the scaffold after heating and curing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9840045B2 (en)* | 2014-12-31 | 2017-12-12 | X Development Llc | Voxel 3D printer |
| CN105818382B (en)* | 2016-04-15 | 2017-12-22 | 浙江大学 | A kind of method based on digital light processing structure three-dimensional structure |
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| CN106696258B (en)* | 2016-11-21 | 2019-09-03 | 浙江大学 | A method for rapid 3D printing |
| CN109280395B (en)* | 2017-07-19 | 2021-09-07 | 北京恒创增材制造技术研究院有限公司 | Product prepared by photocuring rapid molding process and preparation method thereof |
| WO2019124815A1 (en)* | 2017-12-22 | 2019-06-27 | 주식회사 류진랩 | 3d printer and printing system |
| CN108170003B (en)* | 2018-01-05 | 2021-07-13 | 广州谱睿汀新材料科技有限公司 | A kind of elastic photosensitive resin for DLP 3D printing and preparation method thereof |
| CN109940878A (en)* | 2019-04-04 | 2019-06-28 | 南京航空航天大学 | A method for light-driven polymer thin layer self-deformation to generate spatial three-dimensional structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2792647C1 (en)* | 2022-12-08 | 2023-03-22 | Федеральное государственное бюджетное учреждение науки Байкальский институт природопользования Сибирского отделения Российской академии наук (БИП СО РАН) | Photosensitive compositions for the manufacture of heat-resistant mechanically strong objects by dlp 3d printing |
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