技术领域Technical field
本发明涉及3d打印浆料技术领域，特别涉及一种纯铜光固化3D打印的高光敏活性浆料及其制备方法。The invention relates to the technical field of 3D printing slurry, and in particular to a highly photosensitive active slurry for pure copper photo-curing 3D printing and a preparation method thereof.
背景技术Background technique
铜作为一种重要的金属材料，近年来随着电子元器件以及半导体行业的迅速发展而倍受重视。铜具有优异的导电性能、抗氧化性和耐腐蚀性等特点，在制造PCB、微处理器、芯片芯间结构等方面发挥着至关重要的作用。同时，铜也可用于高功率密度射频(RF)模块的制造，可提供低损耗和高效能。但是，对于一些精密加工设计要求较高的零部件，如复杂曲面器件，传统的成型和加工技术难以满足相关技术要求，这些限制了铜材料在各个领域的进一步发展和应用。As an important metal material, copper has attracted much attention in recent years with the rapid development of electronic components and semiconductor industries. Copper has excellent electrical conductivity, oxidation resistance and corrosion resistance, and plays a vital role in manufacturing PCBs, microprocessors, and chip inter-core structures. At the same time, copper can also be used in the manufacture of high-power density radio frequency (RF) modules, which can provide low loss and high performance. However, for some parts with high precision processing design requirements, such as complex curved surface devices, traditional molding and processing technologies are difficult to meet the relevant technical requirements, which limits the further development and application of copper materials in various fields.
近年来光固化3D打印技术在陶瓷市场上应用广泛，目前已有工业化生产氧化铝、氧化锆等零件的成功案例。基于此，通过使用由金属粉末、光引发剂、分散剂和光敏树脂混合而成的浆料，使纯铜高精度复杂结构的生产成为可能。该技术是一种将光线能量聚焦于特定区域，使特定区域的材料快速硬化或凝胶化的制造技术，并可以通过数控程序快速调整参数以打印最佳零件；再通过烧结等加工方式，将生坯烧结为实心铜构件并提高表面质量。与立体光刻(SLA)方案相比，数字光处理(DLP)技术为UV光投影面曝光固化，能够在保证打印精度的同时提高工作效率。因此在大规模和复杂工作任务下表现出色。In recent years, light-curing 3D printing technology has been widely used in the ceramic market, and there are currently successful cases of industrial production of alumina, zirconia and other parts. Based on this, by using a slurry mixed with metal powder, photoinitiator, dispersant and photosensitive resin, it is possible to produce high-precision complex structures of pure copper. This technology is a manufacturing technology that focuses light energy on a specific area to quickly harden or gel the material in the specific area. Parameters can be quickly adjusted through a CNC program to print the best parts; then sintering and other processing methods are used to The green body is sintered into a solid copper component and improves surface quality. Compared with the stereolithography (SLA) solution, digital light processing (DLP) technology uses UV light projection surface exposure and curing, which can improve work efficiency while ensuring printing accuracy. Therefore, it performs well under large-scale and complex work tasks.
然而，纯铜粉末对于市场上大多数工业级DLP打印设备波长范围内(365nm～405nm)的紫外光吸收度高达90％以上，这使得紫外吸光度过高，难以实现光致固化。如专利号为CN201510066529.8所公开的光固化铜电子浆料的制备方法，该光固化铜电子浆料的制备方法所述光固化铜电子浆料以丝网印刷的方式在紫外线中压汞灯照射下进行固化，照射时间高达40～100s。尽管所述铜浆料初步实现了铜的光固化行为，但纯铜粉末对光固化设备的紫外光具有极高的吸收率，这隐匿地降低了光敏浆料的活性。因此使用光固化3D打印方式实现高效率生产纯铜的复杂结构需要提高光敏浆料的活性以提高打印质量。However, the ultraviolet light absorption of pure copper powder in the wavelength range (365nm ~ 405nm) of most industrial-grade DLP printing equipment on the market is as high as more than 90%, which makes the ultraviolet light absorption too high and difficult to achieve photocuring. For example, the patent number is CN201510066529.8, which discloses a method for preparing light-curing copper electronic slurry. In the preparation method of the light-curing copper electronic slurry, the light-curing copper electronic slurry is screen-printed under an ultraviolet medium-pressure mercury lamp. Curing is performed under irradiation, and the irradiation time is as high as 40 to 100 seconds. Although the copper slurry initially realizes the photocuring behavior of copper, the pure copper powder has an extremely high absorption rate of ultraviolet light from the photocuring equipment, which secretly reduces the activity of the photosensitive slurry. Therefore, using light-curing 3D printing to achieve high-efficiency production of complex structures of pure copper requires increasing the activity of the photosensitive slurry to improve printing quality.
发明内容Contents of the invention
有鉴于此，本发明提供了一种纯铜光固化3D打印的高光敏活性浆料及其制备方法，以解决上述技术问题。In view of this, the present invention provides a highly photosensitive active slurry for pure copper photo-curing 3D printing and a preparation method thereof to solve the above technical problems.
一种纯铜光固化3D打印的高光敏活性浆料，其组成包含纯铜粉体，活性稀释剂,光引发剂,以及助剂。所述纯铜粉体的重量百分比含量为87％～92％，所述活性稀释剂的重量百分比含量为5.6％～9.4％，所述助剂的重量百分比含量为2.6％～2.8％，所述光引发剂的重量百分比含量为0.31％～0.54％。所述活性稀释剂为丙烯酸酯类单体，所述光引发剂包括两组其中一组为裂解型自由基光引发剂，选用的是裂解型的α-氨基酮及其衍生物类，另外一组为夺氢型自由基光引发剂，选用的是硫杂蒽酮及其衍生物类。A highly photosensitive active slurry for pure copper photo-curing 3D printing, which consists of pure copper powder, active diluent, photoinitiator, and auxiliaries. The weight percentage content of the pure copper powder is 87% to 92%, the weight percentage content of the reactive diluent is 5.6% to 9.4%, and the weight percentage content of the auxiliary agent is 2.6% to 2.8%. The weight percentage content of the photoinitiator is 0.31% to 0.54%. The reactive diluent is an acrylic ester monomer, and the photoinitiator includes two groups, one of which is a cleavage-type free radical photoinitiator. The cleavage-type α-aminoketone and its derivatives are selected, and the other is a cleavage-type free radical photoinitiator. The group is a hydrogen-abstracting free radical photoinitiator, which uses thioxanthone and its derivatives.
进一步地，所述纯铜粉体为球形或类球形铜粉，所述纯铜粉体的粒径为1-15μm，中位粒径为1.84μm。Further, the pure copper powder is a spherical or spherical copper powder, the particle size of the pure copper powder is 1-15 μm, and the median particle size is 1.84 μm.
进一步地，所述活性稀释剂为丙烯酸酯类单体，具体包括二丙二醇二丙烯酸酯、环状三羟甲基丙烷缩甲醛丙烯酸酯、甲基丙烯酸异冰片酯、三羟甲基丙烷三甲基丙烯酸酯、三丙氧化三羟甲基丙烷三丙烯酸酯中的一种或几种。Further, the reactive diluent is an acrylate monomer, specifically including dipropylene glycol diacrylate, cyclic trimethylolpropane formal acrylate, isobornyl methacrylate, trimethylolpropane trimethyl One or more of acrylate and tripropyoxytrimethylolpropane triacrylate.
进一步地，所述助剂为金属粉体表面改性剂、分散剂、防沉剂中的一种或几种。Further, the auxiliary agent is one or more of a metal powder surface modifier, a dispersant, and an anti-settling agent.
一种纯铜光固化3D打印的高光敏活性浆料的制备方法，其包括以下步骤：A method for preparing highly photosensitive active slurry for pure copper photo-curing 3D printing, which includes the following steps:
步骤S1：按照5.6％～9.4％的质量百分比称取一定量的活性稀释剂，活性稀释剂为丙烯酸酯类单体，按照2.6％～2.8％的质量百分比称取一定量的助剂，按照87％～92％的质量百分比含量称取一定量的铜粉，按照0.31％～0.54％的质量百分比称取一定量的光引发剂，光引发剂一共包括两组，其中一组为裂解型自由基光引发剂，选用的是裂解型的α-氨基酮及其衍生物类，另外一组为夺氢型自由基光引发剂，选用的是硫杂蒽酮及其衍生物类；Step S1: Weigh a certain amount of reactive diluent according to the mass percentage of 5.6% to 9.4%. The reactive diluent is an acrylic ester monomer. Weigh a certain amount of additives according to the mass percentage of 2.6% to 2.8%. According to 87 Weigh a certain amount of copper powder with a mass percentage content of 0.31% to 92%, and weigh a certain amount of photoinitiator with a mass percentage of 0.31% to 0.54%. The photoinitiator includes a total of two groups, one of which is a cleavage type free radical. As photoinitiators, the cleavage-type α-aminoketone and its derivatives are used. The other group is the hydrogen-abstracting free radical photoinitiator, and the thioxanthone and its derivatives are used;
步骤S2：将称取的活性稀释剂、助剂以及光引发剂放入高速分散机中，以1000-2000r/mi n的转速在20-45℃下分散3-10mi n，使其充分混合溶解，从而得到浆料的有机载体；Step S2: Put the weighed reactive diluent, auxiliary and photoinitiator into a high-speed disperser, disperse for 3-10 minutes at 20-45°C at a speed of 1000-2000r/min, and mix and dissolve thoroughly. , thereby obtaining the organic carrier of the slurry;
步骤S3：将有机载体倒入搅拌球磨机中，并以少量多次的方式将称好的铜粉加入，在100-450r/mi n的速度下搅拌1-2h，使其充分混匀；Step S3: Pour the organic carrier into the stirring ball mill, add the weighed copper powder in small amounts and multiple times, and stir for 1-2 hours at a speed of 100-450r/min to mix thoroughly;
步骤S4：将混匀的铜浆料放入真空脱泡机中，在室温条件下进行真空脱泡得到铜浆料成品。Step S4: Put the mixed copper slurry into a vacuum degassing machine, and perform vacuum degassing at room temperature to obtain a finished copper slurry.
进一步地，将采集到的三维陶瓷材料打印构件模型文件如abc,glTF,fbx,obj,dae,stl,3ds,ply等转换为stl文件，导入打印系统中。Further, the collected three-dimensional ceramic material printing component model files such as abc, glTF, fbx, obj, dae, stl, 3ds, ply, etc. are converted into stl files and imported into the printing system.
进一步地，在上述步骤S3中，在装有独立切片及打印一体系统的陶瓷打印机中，系统加载预处理模型的.STL文件，使用切片功能，输出打印模型的二维切片.PNG格式图像。Further, in the above step S3, in the ceramic printer equipped with an independent slicing and printing integrated system, the system loads the .STL file of the preprocessed model, uses the slicing function, and outputs the .PNG format image of the two-dimensional slice of the printed model.
进一步地，在上述步骤S4中，高倍渲染处理为四倍或八倍，定义线型连通区域为四连通或八连通。Further, in the above-mentioned step S4, the high-magnification rendering process is four times or eight times, and the linear connected area is defined as four-connected or eight-connected.
进一步地，在上述步骤S6中，打印机的参数为LED光源波长406nm、打印层厚0.03～0.1mm、光照强度10～200mW/cm2、低曝层数0～9999、低曝时间1～60s、其余层曝光时间1～60s；每层曝光结束后等待时间1～300s。Further, in the above step S6, the parameters of the printer are LED light source wavelength 406nm, printing layer thickness 0.03~0.1mm, light intensity 10~200mW/cm2, number of low exposure layers 0~9999, low exposure time 1~60s, and the rest. The layer exposure time is 1~60s; the waiting time after each layer exposure is 1~300s.
与现有技术相比，本发明提供的纯铜光固化3D打印的高光敏活性浆料通过选取粘度较低的二丙二醇二丙烯酸酯、环状三羟甲基丙烷缩甲醛丙烯酸酯等丙烯酸酯类单体活性稀释剂中的一种或几种，并与助剂复配，获得了低粘度的铜粉浆料。采用α-氨基酮及其衍生物和硫杂蒽酮及其衍生物复配光引发剂体系，有效提升了浆料的光聚合活性。其中所述硫杂蒽酮类光引发剂在360nm～405nm波长左右的紫外光中具有较高的摩尔消光系数，可以与铜粉竞争紫外光以避免铜粉的高吸光系数导致光引发效率降低。同时硫杂蒽酮吸收紫外光后与α-氨基酮类发生能量转移，使α-氨基酮类光引发剂跃迁至激发三线态，间接实现浆料光聚合。对于较短波长的紫外光，两种引发剂复配可以有效拓宽可利用光的波长范围。此外，由于α-氨基酮中叔胺结构的存在，一方面可以与硫杂蒽酮类光引发剂通过复杂的光化学反应形成活性高的氨基烷基自由基，另一方面可以通过氧化还原反应消除氧气对于聚合的不利影响，进一步提升固化效率。在双重作用下，纯铜光敏浆料的光引发效率得到极大地提高，保证铜浆较高固相含量的同时，提高浆料光敏活性，解决铜粉紫外吸光度过高的问题。Compared with the existing technology, the highly photosensitive active slurry for pure copper photo-curing 3D printing provided by the present invention adopts low-viscosity acrylates such as dipropylene glycol diacrylate and cyclic trimethylolpropane formal acrylate. One or more of the monomer reactive diluents are compounded with additives to obtain a low-viscosity copper powder slurry. The photoinitiator system of α-aminoketone and its derivatives and thioxanthone and its derivatives is used to effectively improve the photopolymerization activity of the slurry. The thioxanthone photoinitiator has a high molar extinction coefficient in ultraviolet light with a wavelength of about 360nm to 405nm, and can compete with copper powder for ultraviolet light to avoid the reduction of photoinitiation efficiency caused by the high absorption coefficient of copper powder. At the same time, thioxanthone absorbs ultraviolet light and undergoes energy transfer with α-aminoketones, causing the α-aminoketone photoinitiator to transition to an excited triplet state, indirectly achieving slurry photopolymerization. For shorter wavelength ultraviolet light, the combination of two initiators can effectively broaden the wavelength range of available light. In addition, due to the presence of the tertiary amine structure in α-aminoketone, on the one hand, it can form highly active aminoalkyl radicals through complex photochemical reactions with thioxanthone photoinitiators, and on the other hand, it can be eliminated through redox reactions. The adverse effect of oxygen on polymerization further improves curing efficiency. Under the dual action, the photoinitiation efficiency of the pure copper photosensitive slurry is greatly improved, ensuring a high solid content of the copper slurry while improving the photosensitivity activity of the slurry and solving the problem of excessive UV absorption of copper powder.
附图说明Description of the drawings
图1为本发明提供的一种纯铜光固化3D打印的高光敏活性浆料的制备方法的流程图。Figure 1 is a flow chart of a method for preparing a highly photosensitive active slurry for pure copper photo-curing 3D printing provided by the present invention.
具体实施方式Detailed ways
以下对本发明的具体实施例进行进一步详细说明。应当理解的是，此处对本发明实施例的说明并不用于限定本发明的保护范围。Specific embodiments of the present invention are described in further detail below. It should be understood that the description of the embodiments of the present invention here is not intended to limit the protection scope of the present invention.
一种纯铜光固化3D打印的高光敏活性浆料，其组成包含纯铜粉体，活性稀释剂,光引发剂,以及助剂。所述纯铜粉体的重量百分比含量为87％～92％，所述活性稀释剂的重量百分比含量为5.6％～9.4％，所述助剂的重量百分比含量为2.6％～2.8％，所述光引发剂的重量百分比含量为0.31％～0.54％。A highly photosensitive active slurry for pure copper photo-curing 3D printing, which consists of pure copper powder, active diluent, photoinitiator, and auxiliaries. The weight percentage content of the pure copper powder is 87% to 92%, the weight percentage content of the reactive diluent is 5.6% to 9.4%, and the weight percentage content of the auxiliary agent is 2.6% to 2.8%. The weight percentage content of the photoinitiator is 0.31% to 0.54%.
所述纯铜粉体为球形或类球形铜粉，所述纯铜粉体的粒径为1-15μm，中位粒径为1.84μm。The pure copper powder is a spherical or quasi-spherical copper powder, the particle size of the pure copper powder is 1-15 μm, and the median particle size is 1.84 μm.
所述活性稀释剂为丙烯酸酯类单体，具体包括：二丙二醇二丙烯酸酯、环状三羟甲基丙烷缩甲醛丙烯酸酯、甲基丙烯酸异冰片酯、三羟甲基丙烷三甲基丙烯酸酯、三丙氧化三羟甲基丙烷三丙烯酸酯中的一种或几种。The reactive diluent is an acrylate monomer, specifically including: dipropylene glycol diacrylate, cyclic trimethylolpropane formal acrylate, isobornyl methacrylate, and trimethylolpropane trimethacrylate. , one or more of three propoxytrimethylolpropane triacrylates.
所述光引发剂一共包括两组：其中一组为裂解型自由基光引发剂，选用的是裂解型的α-氨基酮及其衍生物类，含有2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮、2-二甲氨基-2-(4-甲基)苄基-1-[4-(4-吗啉基)苯基]-1-丁酮、2-二甲氨基-2-苄基-1-(4-哌啶苯基)-1-丁酮及2-甲基-1-(4-甲硫基苯基)-2-吗啉-1-丙酮中的一种或几种。另外一组为夺氢型自由基光引发剂，选用的是硫杂蒽酮及其衍生物类，包括2-氯硫杂蒽酮(CTX)、2-异丙基硫杂蒽酮(I TX)和2,4-二乙基硫杂蒽酮(DETX)中的一种或几种。The photoinitiators include two groups in total: one group is a cleavage-type free radical photoinitiator, which is a cleavage-type α-aminoketone and its derivatives, containing 2-phenylbenzyl-2-dimethyl. Amine-1-(4-morpholinobenzylphenyl)butanone, 2-dimethylamino-2-(4-methyl)benzyl-1-[4-(4-morpholinyl)phenyl]-1 -Butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinophenyl)-1-butanone and 2-methyl-1-(4-methylthiophenyl)-2- One or more of morpholine-1-propanone. The other group is a hydrogen-abstracting free radical photoinitiator, which uses thioxanthone and its derivatives, including 2-chlorothioxanthone (CTX), 2-isopropyl thioxanthone (I TX ) and one or more of 2,4-diethylthioxanthone (DETX).
所述助剂为金属粉体表面改性剂、分散剂、防沉剂中的一种或几种The additive is one or more of metal powder surface modifiers, dispersants, and anti-settling agents.
实施例1：Example 1:
以质量百分率为2.5％称取三羟甲基丙烷三甲基丙烯酸酯、以3.3％称取二丙二醇二丙烯酸酯、以2.5％称取甲基丙烯酸异冰片酯、以2.7％称取分散剂，以88.6％称取铜粉，以0.2％称取2-苯基苄-2-二甲基胺-1-(4-吗啉苄苯基)丁酮，以0.2％称取2-氯硫杂蒽酮(CTX)，混合均匀制得光敏铜浆。Weigh trimethylolpropane trimethacrylate with a mass percentage of 2.5%, dipropylene glycol diacrylate with a mass percentage of 3.3%, isobornyl methacrylate with a mass percentage of 2.5%, and dispersant with a mass percentage of 2.7%. Weigh copper powder at 88.6%, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone at 0.2%, and 2-chlorothiapine at 0.2% Anthrone (CTX), mix evenly to prepare photosensitive copper paste.
制得的DLP打印铜浆其粘度为1030mPa·s，在波长为385nm的光源下固化，当曝光功率为230mW/cm2固化成膜的时间为20s，固化层厚为60μm。The viscosity of the prepared DLP printing copper paste is 1030mPa·s, and it is cured under a light source with a wavelength of 385nm. When the exposure power is 230mW/cm2, the curing film formation time is 20s, and the cured layer thickness is 60μm.
实施例2：Example 2:
以质量百分率为1.9％称取三羟甲基丙烷三甲基丙烯酸酯、以2.6％称取环三羟甲基丙烷甲缩醛丙烯酸酯、以1.9％称取三丙氧化三羟甲基丙烷三丙烯酸酯、以2.75％称取分散剂，以90.53％称取铜粉，以0.16％称取2-二甲氨基-2-(4-甲基)苄基-1-[4-(4-吗啉基)苯基]-1-丁酮，以0.16％称取2-异丙基硫杂蒽酮，混合均匀制得光敏铜浆。Weigh trimethylolpropane trimethacrylate at a mass percentage of 1.9%, cyclotrimethylolpropane methyl acrylate at a mass percentage of 2.6%, and tripropoxytrimethylolpropane trimethacrylate at a mass percentage of 1.9%. Acrylate, dispersant was weighed at 2.75%, copper powder was weighed at 90.53%, 2-dimethylamino-2-(4-methyl)benzyl-1-[4-(4-methyl) was weighed at 0.16% Phylyl)phenyl]-1-butanone, weigh 2-isopropylthioxanthone at 0.16%, and mix evenly to prepare a photosensitive copper paste.
制得的DLP打印铜粉浆料其粘度为5890mPa·s，在波长为385nm的光源下固化，当曝光功率为230mW/cm2固化成膜的时间为35s，固化层厚为60μm。The viscosity of the prepared DLP printing copper powder slurry is 5890mPa·s, and it is cured under a light source with a wavelength of 385nm. When the exposure power is 230mW/cm2, the curing film formation time is 35s, and the cured layer thickness is 60μm.
本发明还提供一种纯铜光固化3D打印的高光敏活性浆料的制备方法，包括以下步骤：The invention also provides a method for preparing highly photosensitive active slurry for pure copper photo-curing 3D printing, which includes the following steps:
步骤S1：按照5.6％～9.4％的质量百分比称取一定量的活性稀释剂，活性稀释剂为丙烯酸酯类单体，按照2.6％～2.8％的质量百分比称取一定量的助剂，按照87％～92％的质量百分比含量称取一定量的铜粉，按照0.31％～0.54％的质量百分比称取一定量的光引发剂。光引发剂一共包括两组，其中一组为裂解型自由基光引发剂，选用的是裂解型的α-氨基酮及其衍生物类，另外一组为夺氢型自由基光引发剂，选用的是硫杂蒽酮及其衍生物类。Step S1: Weigh a certain amount of reactive diluent according to the mass percentage of 5.6% to 9.4%. The reactive diluent is an acrylic ester monomer. Weigh a certain amount of additives according to the mass percentage of 2.6% to 2.8%. According to 87 Weigh a certain amount of copper powder according to the mass percentage content of 0.31% to 0.54%. There are two groups of photoinitiators. One group is a cleavage type free radical photoinitiator, which uses the cleavage type α-aminoketone and its derivatives. The other group is a hydrogen abstraction type free radical photoinitiator, which uses are thioxanthone and its derivatives.
步骤S2：将称取的活性稀释剂、助剂以及光引发剂放入高速分散机中，以1000-2000r/mi n的转速在20-45℃下分散3-10mi n，使其充分混合溶解，从而得到浆料的有机载体。Step S2: Put the weighed reactive diluent, auxiliary and photoinitiator into a high-speed disperser, disperse for 3-10 minutes at 20-45°C at a speed of 1000-2000r/min, and mix and dissolve thoroughly. , thereby obtaining the organic carrier of the slurry.
步骤S3：将有机载体倒入搅拌球磨机中，并以少量多次的方式将称好的铜粉加入，在100-450r/mi n的速度下搅拌1-2h，使其充分混匀。Step S3: Pour the organic carrier into the stirring ball mill, add the weighed copper powder in small amounts and multiple times, and stir for 1-2 hours at a speed of 100-450 r/min to mix thoroughly.
步骤S4：将混匀的铜浆料放入真空脱泡机中，在室温条件下进行真空脱泡得到铜浆料成品。Step S4: Put the mixed copper slurry into a vacuum degassing machine, and perform vacuum degassing at room temperature to obtain a finished copper slurry.
在上述步骤S1中，两种光引发剂的比例为1:1，所述光引发剂以及所述助剂的含量各占活性稀释剂的3wt％。In the above step S1, the ratio of the two photoinitiators is 1:1, and the contents of the photoinitiator and the auxiliary agent each account for 3wt% of the reactive diluent.
与现有技术相比，本发明提供的纯铜光固化3D打印的高光敏活性浆料通过选取粘度较低的二丙二醇二丙烯酸酯、环状三羟甲基丙烷缩甲醛丙烯酸酯等丙烯酸酯类单体活性稀释剂中的一种或几种，并与助剂复配，获得了低粘度的铜粉浆料。采用α-氨基酮及其衍生物和硫杂蒽酮及其衍生物复配光引发剂体系，有效提升了浆料的光聚合活性。其中所述硫杂蒽酮类光引发剂在360nm～405nm波长左右的紫外光中具有较高的摩尔消光系数，可以与铜粉竞争紫外光以避免铜粉的高吸光系数导致光引发效率降低。同时硫杂蒽酮吸收紫外光后与α-氨基酮类发生能量转移，使α-氨基酮类光引发剂跃迁至激发三线态，间接实现浆料光聚合。对于较短波长的紫外光，两种引发剂复配可以有效拓宽可利用光的波长范围。此外，由于α-氨基酮中叔胺结构的存在，一方面可以与硫杂蒽酮类光引发剂通过复杂的光化学反应形成活性高的氨基烷基自由基，另一方面可以通过氧化还原反应消除氧气对于聚合的不利影响，进一步提升固化效率。在双重作用下，纯铜光敏浆料的光引发效率得到极大地提高，保证铜浆较高固相含量的同时，提高浆料光敏活性，解决铜粉紫外吸光度过高的问题。Compared with the existing technology, the highly photosensitive active slurry for pure copper photo-curing 3D printing provided by the present invention adopts low-viscosity acrylates such as dipropylene glycol diacrylate and cyclic trimethylolpropane formal acrylate. One or more of the monomer reactive diluents are compounded with additives to obtain a low-viscosity copper powder slurry. The photoinitiator system of α-aminoketone and its derivatives and thioxanthone and its derivatives is used to effectively improve the photopolymerization activity of the slurry. The thioxanthone photoinitiator has a high molar extinction coefficient in ultraviolet light with a wavelength of about 360nm to 405nm, and can compete with copper powder for ultraviolet light to avoid the reduction of photoinitiation efficiency caused by the high absorption coefficient of copper powder. At the same time, thioxanthone absorbs ultraviolet light and undergoes energy transfer with α-aminoketones, causing the α-aminoketone photoinitiator to transition to an excited triplet state, indirectly achieving slurry photopolymerization. For shorter wavelength ultraviolet light, the combination of two initiators can effectively broaden the wavelength range of available light. In addition, due to the presence of the tertiary amine structure in α-aminoketone, on the one hand, it can form highly active aminoalkyl radicals through complex photochemical reactions with thioxanthone photoinitiators, and on the other hand, it can be eliminated through redox reactions. The adverse effect of oxygen on polymerization further improves curing efficiency. Under the dual action, the photoinitiation efficiency of the pure copper photosensitive slurry is greatly improved, ensuring a high solid content of the copper slurry while improving the photosensitivity activity of the slurry and solving the problem of excessive UV absorption of copper powder.
以上仅为本发明的较佳实施例，并不用于局限本发明的保护范围，任何在本发明精神内的修改、等同替换或改进等，都涵盖在本发明的权利要求范围内。The above are only preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions or improvements within the spirit of the present invention are covered by the claims of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310844665.XACN116809921A (en) | 2023-07-11 | 2023-07-11 | A highly photosensitive active slurry for pure copper photo-curing 3D printing and its preparation method |
| Application Number | Priority Date | Filing Date | Title |
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| CN202310844665.XACN116809921A (en) | 2023-07-11 | 2023-07-11 | A highly photosensitive active slurry for pure copper photo-curing 3D printing and its preparation method |
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| CN116809921Atrue CN116809921A (en) | 2023-09-29 |
| Application Number | Title | Priority Date | Filing Date |
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| CN202310844665.XAPendingCN116809921A (en) | 2023-07-11 | 2023-07-11 | A highly photosensitive active slurry for pure copper photo-curing 3D printing and its preparation method |
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| JP2009074152A (en)* | 2007-09-21 | 2009-04-09 | Mitsui Mining & Smelting Co Ltd | Copper powder manufacturing method and copper powder |
| KR20150077649A (en)* | 2013-12-30 | 2015-07-08 | 전자부품연구원 | ceramic slurry composition with low viscosity for 3D printing and manufacturing method of ceramic slurry composition |
| CN113429210A (en)* | 2021-07-16 | 2021-09-24 | 嘉兴饶稷科技有限公司 | Silicon carbide ceramic slurry with high photosensitive activity and preparation method thereof |
| CN114800767A (en)* | 2022-03-18 | 2022-07-29 | 嘉兴饶稷科技有限公司 | Method for preparing transparent ceramic through one-step forming based on photocuring 3D printing technology |
| CN115740486A (en)* | 2022-12-16 | 2023-03-07 | 河源市蓝海米克模具刀具有限公司 | Photocuring printing hard alloy cutter and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009074152A (en)* | 2007-09-21 | 2009-04-09 | Mitsui Mining & Smelting Co Ltd | Copper powder manufacturing method and copper powder |
| KR20150077649A (en)* | 2013-12-30 | 2015-07-08 | 전자부품연구원 | ceramic slurry composition with low viscosity for 3D printing and manufacturing method of ceramic slurry composition |
| CN113429210A (en)* | 2021-07-16 | 2021-09-24 | 嘉兴饶稷科技有限公司 | Silicon carbide ceramic slurry with high photosensitive activity and preparation method thereof |
| CN114800767A (en)* | 2022-03-18 | 2022-07-29 | 嘉兴饶稷科技有限公司 | Method for preparing transparent ceramic through one-step forming based on photocuring 3D printing technology |
| CN115740486A (en)* | 2022-12-16 | 2023-03-07 | 河源市蓝海米克模具刀具有限公司 | Photocuring printing hard alloy cutter and preparation method thereof |
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