Three-dimensional ferromagnetic super-hydrophobic material, preparation method and use thereof

Abstract

The application provides a kind of three-dimensional ferromagnetic super-hydrophobic material, which is sequentially covered with copper layer and nickel layer on three-dimensional structure material;The copper layer is prepared by mixing film forming agent, laser sensitizing agent and solvent, brushing on the surface of the material, drying, then using laser to irradiate the surface to form an activated pattern, and then using chemical plating to selectively metallize the activated area;The nickel layer is prepared by electroplating nickel on the copper layer under a specific current density, and then exposing it to air for more than 7 days to obtain a magnetic super-hydrophobic nickel layer.The application also provides a preparation method and application of the three-dimensional ferromagnetic super-hydrophobic material.The three-dimensional ferromagnetic super-hydrophobic material provided by the application not only ensures the high conductivity and ferromagnetism of the nickel layer, but also makes the nickel layer have excellent patterning precision and super-hydrophobicity.The above advantages make the nickel layer play an important role in high-precision electronic equipment, magnetic actuators, corrosion prevention, self-cleaning and other fields, and have a wide application prospect in weather-resistant electronics.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of three-dimensional ferromagnetic super-hydrophobic material and its preparation method and use. BACKGROUND

[0002] Nickel is a kind of ferromagnetic metal material, with good chemical stability, is widely used in electronic devices, corrosion-resistant coating, magnetic actuator and other fields. Traditional manufacturing method can be printed on circuit board, etching, inkjet printing and other processes in two-dimensional plane to make patterned circuit. However, two-dimensional manufacturing method cannot be applied to the line conduction of three-dimensional structure, which seriously limits the application range of electronic products. The rise of 3D printing technology makes the manufacture of three-dimensional patterned circuit possible, and people can directly manufacture electrically functional wires and patterns on three-dimensional surfaces with freely customizable shapes, and directly install components on three-dimensional surfaces to realize the manufacture of three-dimensional electronic products. Especially in communication antennas, electromagnetic shielding, flexible robots and other aspects, it is difficult to achieve by traditional two-dimensional manufacturing method.

[0003] In particular, for magnetic drive robots, there is a strong demand for three-dimensional customization of magnetic parts. Magnetic drive robots are a kind of high-tech products that use magnetic field to control the movement and deformation of robots. They have wide application prospects in medical, biological engineering, micro-nano technology and other fields. Magnetic drive robots are usually composed of magnetic materials and soft materials, and can realize movement and deformation through the control of external magnetic field. For example, by locally heating the magnetic soft material to above Curie temperature by laser, the magnetic particles of the material become paramagnetic, and then a magnetic field is applied during the cooling process to reorient the magnetic domains of the magnetic particles, thereby realizing the programming and control of the soft robot.

[0004] Currently, the directly manufactured nickel layer metal is still susceptible to environmental influences and thus electrochemical corrosion due to its high surface energy and certain hydrophilicity. Utilizing biomimetic structures to obtain super-hydrophobic properties for the metal layer solves the problem of electrochemical corrosion caused by the intrinsic hydrophilicity of the metal, thereby further improving the weather resistance of the metal layer.

[0005] Chinese patent application CN116277953A discloses a method for selectively metallizing a nickel layer by hybrid additive manufacturing technology. However, the metal layer prepared by this method does not have super-hydrophobicity, and the patent document does not mention whether it can guarantee the ferromagnetism of nickel. Moreover, this method uses a complex multi-material 3D printer, which not only increases the equipment cost, but also limits the types of 3D printing to only the method provided in the document. SUMMARY

[0006] The present application provides a kind of three-dimensional ferromagnetic super-hydrophobic material, which is suitable for communication antennas, electromagnetic shielding, flexible robots, especially for magnetic drive robot field.

[0007] The application provides a three-dimensional ferromagnetic super-hydrophobic material, which comprises a copper layer and a nickel layer successively coated on a three-dimensional material.

[0008] The copper layer is prepared by mixing a film forming agent, a laser sensitizing agent and a solvent, brushing the mixture on the surface of a resin material, drying, performing surface radiation by laser to form an activated pattern, and then performing selective metallization on the activated area by chemical plating.

[0009] The nickel layer is prepared by electroplating nickel on the copper layer under a specific current density, and then exposing the nickel layer to air for more than 7 days to obtain a magnetic super-hydrophobic nickel layer.

[0010] The laser sensitizing agent and the film forming agent are used in a percentage of 5%-70% and 30%-95% respectively.

[0011] The laser sensitizing agent and the film forming agent are used in a percentage of 5%-70% and 30%-95% respectively.

[0012] The film forming agent is one or more than two of polyvinyl alcohol, polyvinylpyrrolidone, acrylic acid copolymer, gelatin, agar, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, povidone, alcohol-soluble polyamide, acrylic ester homopolymer, acrylic ester copolymer, SEBS, SEPS, SBS, SIS, polyurethane, K resin, polycarbonate, styrene-maleic anhydride copolymer, polystyrene; preferably, the film forming agent is one of polyvinyl alcohol, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, alcohol-soluble polyamide, acrylic ester homopolymer, acrylic ester copolymer, SEBS, polycarbonate, styrene-maleic anhydride copolymer.

[0013] The solvent is one or more than two of water, acetonitrile, methanol, ethanol, propanol, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, chloroform, bromoethane, benzene, chloropropane, toluene, carbon tetrachloride, carbon disulfide, cyclohexane, hexane, heptane.

[0014] The laser sensitizer is one or two or more of a salt of copper, an oxide of copper, a hydroxide of copper, an organic complex of copper, a salt of bismuth, an oxide of bismuth, a hydroxide of bismuth, an organic complex of bismuth, a salt of chromium, a hydroxide of chromium, an organic complex of chromium, a salt of tin, an oxide of tin, a hydroxide of tin, an organic complex of tin, a doped oxide of tin, a salt of antimony, an oxide of antimony, a hydroxide of antimony, an organic complex of antimony, a salt of molybdenum, an oxide of molybdenum, a hydroxide of molybdenum, a sulfide of molybdenum, a hydroxide of molybdenum, a molybdenum-containing acid, a salt of indium, an oxide of indium, a hydroxide of indium, an organic complex of indium, an oxide of zinc, a sulfide of zinc, a hydroxide of zinc, a salt of zinc, an oxide of tungsten, a sulfide of tungsten, a tungsten-containing acid, a salt of tungsten, an oxide of lanthanum, an oxide of niobium, an oxide of neodymium, an oxide of nickel, a salt of nickel, an oxide of tellurium, an oxide of zirconium, an oxide of silver, or a salt of silver.

[0015] The material of the three-dimensional structure is prepared by a 3D printing method, and the 3D printing method comprises any one of stereolithography (SLA), digital light processing (DLP), selective laser sintering (SLS), fused deposition modeling (FDM), multi-beam selective laser sintering (MJF), binder jetting (BJ) and direct energy deposition (DED).

[0016] The wavelength of the laser is 300-1200 nm, the laser power is 1-20 W, the laser scanning speed is 1000-2000 mm / s, and the laser frequency is 30-60 kHz.

[0017] The plating solution formula for the electroplated nickel comprises 6.2 g of boric acid, 23.8 g of nickel chloride hexahydrate and 26.3 g of nickel sulfate per liter of aqueous solution, the plating part is used as a cathode, and a platinum sheet is used as an anode; the current density for electroplating is 100-500 mA / cm 2 , and the electroplating time is 5-20 minutes. 2 , and the electroplating time is 5-10 minutes.

[0018] The placement time is 7-30 days.

[0019] The water contact angle of the super-hydrophobic nickel layer is greater than 150°, and the rolling angle is less than 5°.

[0020] The application provides a preparation method of the three-dimensional ferromagnetic super-hydrophobic material.

[0021] Step S1: according to the requirement, the three-dimensional structure of the three-dimensional electronic device is designed, and the designed three-dimensional structure is printed by using the 3D printing technology;

[0022] Step S2: the film forming agent is mixed with the solvent, then the laser sensitizing agent is added to obtain the laser sensitizing agent suspension or solution, then the suspension or solution is brushed on the surface of the three-dimensional printing part, and then the solvent is removed by drying;

[0023] Step S3: the surface of the three-dimensional part obtained in step S2 is irradiated by laser, and an activation pattern is formed in the irradiation area, the activation area is selectively metalized by chemical plating, and a copper layer is obtained on the surface of the three-dimensional part;

[0024] Step S4: the copper layer obtained in step S3 is electroplated with nickel under a certain current density for a certain time, then the nickel layer is exposed to air for a period of time, and a three-dimensional ferromagnetic super-hydrophobic nickel layer is obtained.

[0025] The application provides the use of the three-dimensional ferromagnetic super-hydrophobic material in preparing communication antennas, electromagnetic shields and flexible robots.

[0026] The three-dimensional ferromagnetic super-hydrophobic material is used for preparing a magnetically driven robot.

[0027] When the inventors of the application improve the weather resistance of the copper layer prepared by selective metallization by electroplating nickel, it is found that after electroplating the copper layer with a certain current density for a certain time, the nickel layer obtained can inherit the biomimetic microstructure on the surface of the copper layer, and by exposing to air for a period of time, it can spontaneously reach a super-hydrophobic state, and has excellent ferromagnetism. This makes it possible to manufacture three-dimensional electronic products with excellent weather resistance, for example, for three-dimensional antennas or electromagnetic shielding structures exposed to the outside world, the method of the application can directly manufacture three-dimensional patterned circuits with super-hydrophobicity, which realizes the functionality and ensures the corrosion resistance. Especially for magnetically driven robots, the application solves the problem of three-dimensional patterning of the magnetic part, while ensuring its weather resistance.

[0028] The existing nickel layer selective metallization method is achieved by depositing the base part and the metallized part of the component respectively through multi-material three-dimensional printing, which makes the production of patterned metal layer have to rely on the special three-dimensional printer and the corresponding printing ink developed separately, greatly increasing the manufacturing cost and production limitation. Compared with the existing method, the present application directly prepares a ferromagnetic nickel layer with superhydrophobicity by laser selective metallization and electroplating, which has the advantages of good weather resistance, high production efficiency, convenient process, wide applicability and high precision of the patterned metal layer obtained by laser selective metallization. In addition, there is also a method of making the nickel layer superhydrophobic by depositing a low surface energy substance, but the nickel layer prepared by this method can directly obtain superhydrophobicity by exposure to air, which can significantly reduce the cost and pollution waste in the production process, and is suitable for large-scale production.

[0029] The three-dimensional ferromagnetic superhydrophobic material of the present application not only ensures the high conductivity and ferromagnetic property of the nickel layer, but also makes the nickel layer have excellent patterned precision and superhydrophobicity. The above advantages make this nickel layer play an important role in high-precision electronic equipment, magnetic actuators, corrosion prevention, self-cleaning and other fields, and has a wide application prospect in weather-resistant electronics.

[0030] Obviously, according to the above content of the present application, according to the ordinary technical knowledge and conventional means in the art, other various forms of modification, replacement or change can be made without departing from the above basic technical idea of the present application.

[0031] The above content of the present application will be further explained in detail through the specific embodiments below. However, this should not be understood as limiting the scope of the above subject matter of the present application to the following examples. Any technology realized based on the above content of the present application belongs to the scope of the present application. DETAILED DESCRIPTION

[0032] The raw materials and equipment used in the specific embodiments of the present application are known products, which can be obtained by purchasing commercially available products.

[0033] (1) The equipment information used in the present application is as follows:

[0034] Stereolithography printer, model Form 3, produced by Formlabs Co., Ltd.;

[0035] Digital light processing printer, model DLP-D150, produced by Chuangxi Sanzhong Co., Ltd.;

[0036] Selective laser sintering printer, model Fuse 1, produced by Formlabs Co., Ltd.;

[0037] Fused deposition modeling printer, model F3300, produced by Stratasys Co., Ltd.

[0038] Laser marking machine, model MUV-E-R, pulsed laser marking machine, maximum power of laser 5W, laser wavelength 355nm;

[0039] Laser marking machine, model DZ-Q, pulsed laser marking machine, maximum power of laser 8W, laser wavelength 395nm;

[0040] Laser marking machine, model MF-E-A, fiber pulsed laser marking machine, maximum power of laser 20W, laser wavelength 1064nm;

[0041] Laser marking machine, model YK-F20G, semiconductor continuous laser marking machine, maximum power of laser 10W, laser wavelength 533nm.

[0042] Laser marking machine, model BOT808-1000DT, fiber pulsed laser marking machine, maximum power of laser 7W, laser wavelength 808nm.

[0043] (2) The resin used for three-dimensional printing according to the present application is as follows:

[0044] The stereolithography printing resin Somos GP, Somos Taurus is purchased from Stratasys Co., Ltd., Godart8001 is purchased from Zhongshan Dajian Technology Co., Ltd., Elastic 50A Resin, White Resin V5 is purchased from Formlabs Co., Ltd. The digital light processing printing resin AmeraLabs AMD-3, AmeraLabs TGM-7 is purchased from AmeraLabs Co., Ltd. The selective laser sintering printing resin Polypropylene Powder, TPU 90A Powder is purchased from Formlabs Co., Ltd. The fused deposition modeling printing resin ABS-M30, ABS-ESD7 is purchased from Stratasys Co., Ltd.

[0045] (3) Coating adhesion test:

[0046] According to ASTM D3359, a square grid with a size of 1mm x 1mm is drawn on the coating area using a grid. Then, Scotch 3M 600-1PK test tape is pasted to the grid area, and the tape is quickly torn off. The adhesion strength is judged according to the area of the metal layer falling off. In the ASTM D3359 grading standard, the higher the grade, the higher the adhesion between the polymer substrate and the coating. Among them:

[0047] 0B The peeling area of the grid is greater than 65%;

[0048] 1B grid with a flaking area of 35-65%;

[0049] 2B grid with a flaking area of 15-35%;

[0050] 3B grid with a flaking area of 5-15%;

[0051] 4B grid with a flaking area of 5%;

[0052] 5B without any grid flaking.

[0053] (4) Water contact angle test:

[0054] The water contact angle of the surface of the nickel layer is measured by a contact angle meter. When the contact angle is greater than 150° and the rolling angle is less than 10°, the metal layer exhibits super-hydrophobicity; when the contact angle is greater than 90° and less than 150° or the contact angle is greater than 150° and the rolling angle is greater than 10°, the metal layer exhibits hydrophobicity; when the contact angle is less than 90°, the metal layer exhibits hydrophilic property.

[0055] (5) Ferromagnetic test:

[0056] The ferromagnetic property of the metal nickel layer is measured by a vibrating sample magnetometer. If the volume magnetization χ of the nickel layer is greater than 10, the ferromagnetic property is good.

[0057] Example 1

[0058] First, the designed three-dimensional structure is printed using a stereolithography printer Form 3, and the printing resin is Somos GP. The laser sensitizer copper hydroxide (10 wt.%) is mixed with the film forming agent water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%) to obtain a laser sensitizer solution, which is brushed onto the surface of the printed three-dimensional component and dried to remove the solvent. The three-dimensional component surface brushed with the laser sensitizer is irradiated with a pulsed laser (1064 nm) for laser activation, with a laser power of 20 W, a scanning speed of 2000 mm / s, a laser frequency of 30 kHz, and deionized water to clean the excess laser sensitizer. According to the known laser activation selective metalization electroless plating method and process in the art, the three-dimensional component after laser activation is electroless plated with copper. The electroless copper plating uses a reducing system with formaldehyde as the reducing agent and copper sulfate as the copper salt. The resin composition is placed in a 45°C electroless copper plating solution for 40 minutes, with uninterrupted air stirring to ensure the uniformity of the copper layer. Finally, according to the known electroplating nickel process in the art, 100 mA / cm 2The current density for electroplating nickel on the conductive copper pattern was 100 mA / cm2, and the electroplating time was 5 minutes to obtain the patterned ferromagnetic nickel layer. The plating solution used for electroplating nickel was an aqueous solution of boric acid (6.2 g / L), nickel chloride hexahydrate (23.8 g / L), and nickel sulfate (26.3 g / L). The plating part was used as the cathode, and a platinum sheet was used as the anode. This electroplating solution was a phosphorus-free formula, and the produced nickel layer had good ferromagnetic properties. After the metal nickel layer was exposed to air for 7 days, the surface metal nickel layer was tested for water contact angle.

[0059] The test results are shown in Table 1.

[0060] Example 2

[0061] A three-dimensional component, a laser sensitizer solution, and an activated component were prepared according to the method of Example 1, with the difference that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: copper hydroxide (5 wt.%), water (44 wt.%), polyvinyl alcohol (7 wt.%), ethanol (44 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The current density for electroplating nickel was 100 mA / cm2, and the electroplating time was 5 minutes. After electroplating nickel, the nickel layer was exposed to air for 7 days. 2

[0062] The test method was the same as that of Example 1, and the test results are shown in Table 1.

[0063] Example 3

[0064] A three-dimensional component, a laser sensitizer solution, and an activated component were prepared according to the method of Example 1, with the difference that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: copper hydroxide (15 wt.%), water (40 wt.%), polyvinyl alcohol (5 wt.%), ethanol (40 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The current density for electroplating nickel was 100 mA / cm2, and the electroplating time was 5 minutes. After electroplating nickel, the nickel layer was exposed to air for 7 days. 2

[0065] The test method was the same as that of Example 1, and the test results are shown in Table 1.

[0066] Example 4

[0067] ​​A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (20 wt.%), water (38 wt.%), polyvinyl alcohol (4 wt.%), and ethanol (38 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0068] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0069] Example 5

[0070] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (25 wt.%), water (35 wt.%), polyvinyl alcohol (5 wt.%), and ethanol (35 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0071] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0072] Example 6

[0073] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (30 wt.%), water (33 wt.%), polyvinyl alcohol (4 wt.%), and ethanol (33 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0074] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0075] Example 7

[0076] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 14 days.

[0077] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0078] Example 8

[0079] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 21 days.

[0080] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0081] Example 9

[0082] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 15 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0083] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0084] Example 10

[0085] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 10 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0086] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0087] Example 11

[0088] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 200 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0089] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0090] Example 12

[0091] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 300 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0092] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0093] Example 13

[0094] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 400 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0095] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0096] Example 14

[0097] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 10 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0098] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0099] Example 15

[0100] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 15 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0101] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0102] Example 16

[0103] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 20 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0104] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0105] Example 17

[0106] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 40 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0107] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0108] Example 18

[0109] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 50 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0110] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0111] Example 19

[0112] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 60 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0113] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0114] Example 20

[0115] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 355 nm, the laser power was 5 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0116] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0117] Example 21

[0118] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 395 nm, the laser power was 8 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0119] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0120] Example 22

[0121] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 533 nm, the laser power was 10 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0122] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0123] Example 23

[0124] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 808 nm, the laser power was 7 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0125] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0126] Example 24

[0127] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos Taurus, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0128] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0129] Example 25

[0130] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that a stereolithography printer Form 3 was used as the three-dimensional printing method, Godart 8001 was used as the resin, and a laser sensitizer solution was used, which was composed of copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0131] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0132] Example 26

[0133] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that a stereolithography printer Form 3 was used as the three-dimensional printing method, Elastic 50A Resin was used as the resin, and a laser sensitizer solution was used, which was composed of copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0134] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0135] Example 27

[0136] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that a stereolithography printer Form 3 was used as the three-dimensional printing method, White Resin V5 was used as the resin, and a laser sensitizer solution was used, which was composed of copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0137] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0138] Example 28

[0139] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in the same manner as in Example 1, except that a digital light processing printer DLP-D150 was used as the three-dimensional printer, AmeraLabs AMD-3 was used as the resin, and a laser sensitizer solution containing copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%) was used. The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for plating nickel was 100 mA / cm2, and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days. 2 The test method was the same as in Example 1, and the test results are shown in Table 1.

[0140] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0141] Example 29

[0142] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in the same manner as in Example 1, except that a digital light processing printer DLP-D150 was used as the three-dimensional printer, AmeraLabs TGM-7 was used as the resin, and a laser sensitizer solution containing copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%) was used. The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for plating nickel was 100 mA / cm2, and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days. 2 The test method was the same as in Example 1, and the test results are shown in Table 1.

[0143] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0144] Example 30

[0145] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in the same manner as in Example 1, except that a selective laser sintering printer Fuse 1 was used as the three-dimensional printer, Polypropylene Powder was used as the resin, and a laser sensitizer solution containing copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%) was used. The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for plating nickel was 100 mA / cm2, and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days. 2 The test method was the same as in Example 1, and the test results are shown in Table 1.

[0146] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0147] Example 31

[0148] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, except that the three-dimensional printing method used a selective laser sintering printer Fuse 1, the resin used TPU 90A Powder, the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), ethanol (42 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating nickel current density was 100 mA / cm 2 , and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days.

[0149] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0150] Example 32

[0151] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, except that the three-dimensional printing method used a fused deposition modeling printer F3300, the resin used ABS-M30, the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), ethanol (42 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating nickel current density was 100 mA / cm 2 , and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days.

[0152] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0153] Example 33

[0154] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, except that the three-dimensional printing method used a fused deposition modeling printer F3300, the resin used ABS-ESD7, the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), ethanol (42 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating nickel current density was 100 mA / cm 2 , and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days.

[0155] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0156] Example 34

[0157] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in the same manner as in Example 1, except that a stereolithography printer Form 3 was used as the three-dimensional printer, Somos GP was used as the resin, and a laser sensitizer solution was prepared by dissolving zinc oxide (10 wt.%) in water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for plating nickel was 100 mA / cm2, and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days. 2 The test method was the same as in Example 1, and the test results are shown in Table 1.

[0158] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0159] Example 35

[0160] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in the same manner as in Example 1, except that a stereolithography printer Form 3 was used as the three-dimensional printer, Somos GP was used as the resin, and a laser sensitizer solution was prepared by dissolving zinc oxide (10 wt.%) in water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for plating nickel was 100 mA / cm2, and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days. 2 The test method was the same as in Example 1, and the test results are shown in Table 1.

[0161] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0162] Example 36

[0163] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in the same manner as in Example 1, except that a stereolithography printer Form 3 was used as the three-dimensional printer, Somos GP was used as the resin, and a laser sensitizer solution was prepared by dissolving zinc oxide (10 wt.%) in water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for plating nickel was 100 mA / cm2, and the plating time was 5 minutes. After plating nickel, the nickel layer was exposed to air for 7 days. 2 The test method was the same as in Example 1, and the test results are shown in Table 1.

[0164] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0165] Example 37

[0166] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: copper acetate (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0167] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0168] Example 38

[0169] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: copper acetate (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0170] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0171] Example 39

[0172] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: copper acetate (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0173] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0174] Example 40

[0175] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), chloroform (84 wt.%), and polycarbonate (6 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0176] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0177] Example 41

[0178] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), cyclohexane (84 wt.%), and SEBS (6 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0179] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0180] Example 42

[0181] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), acetone (84 wt.%), and an acrylate copolymer (6 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0182] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0183] Example 43

[0184] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), acetone (84 wt.%), and acrylate homopolymer (6 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0185] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0186] Example 44

[0187] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), ethanol (42 wt.%), propanol (42 wt.%), and alcohol-soluble polyamide (6 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0188] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0189] Example 45

[0190] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (84 wt.%), and styrene-maleic anhydride copolymer (6 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0191] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0192] Example 46

[0193] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), hydroxypropyl cellulose (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0194] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0195] Example 47

[0196] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), hydroxypropyl methyl cellulose (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0197] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0198] Comparative Example 1

[0199] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used water (47 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (47 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0200] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0201] Comparative Example 2

[0202] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (2 wt.%), water (46 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (46 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0203] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0204] Comparative Example 3

[0205] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 500 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0206] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0207] Comparative Example 4

[0208] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 700 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0209] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0210] Comparative Example 5

[0211] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), ethanol (42 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for nickel plating was 900 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0212] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0213] Comparative Example 6

[0214] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: basic copper phosphate (2 wt.%), water (46 wt.%), polyvinyl alcohol (6 wt.%), ethanol (46 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0215] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0216] Comparative Example 7

[0217] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used: zinc hydroxide (2 wt.%), water (46 wt.%), polyvinyl alcohol (6 wt.%), ethanol (46 wt.%), the laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0218] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0219] Comparative Example 8

[0220] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 10 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0221] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0222] Comparative Example 9

[0223] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 5 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0224] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0225] Comparative Example 10

[0226] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 1 day.

[0227] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0228] Comparative Example 11

[0229] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 5 days.

[0230] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0231] Comparative Example 12

[0232] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 355 nm, the laser power was 1 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0233] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0234] Comparative Example 13

[0235] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 395 nm, the laser power was 1 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0236] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0237] Comparative Example 14

[0238] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 30 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0239] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0240] Comparative Example 15

[0241] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 40 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0242] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0243] Comparative Example 16

[0244] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 90 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0245] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0246] Comparative Example 17

[0247] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinyl alcohol (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 100 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0248] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0249] Comparative Example 18

[0250] The nickel plating was performed directly on the surface of a commercially available conductive copper foil. The plating current density was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0251] The other test methods were the same as in Example 1, and the test results are shown in Table 1.

[0252] Comparative Example 19

[0253] The nickel plating was performed directly on the surface of a commercially available conductive copper foil. The plating current density was 300 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0254] The other test methods were the same as in Example 1, and the test results are shown in Table 1.

[0255] Comparative Example 20

[0256] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), polyvinylpyrrolidone (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0257] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0258] Comparative Example 21

[0259] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), gelatin (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0260] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0261] Comparative Example 22

[0262] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (42 wt.%), agar (6 wt.%), and ethanol (42 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0263] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0264] Comparative Example 23

[0265] A three-dimensional member, a laser sensitizer solution, and an activated member were prepared in accordance with the method of Example 1, with the exception that the three-dimensional printing method used a stereolithography printer Form 3, the resin used Somos GP, and the laser sensitizer solution used copper hydroxide (10 wt.%), water (45 wt.%), and ethanol (45 wt.%). The laser wavelength was 1064 nm, the laser power was 20 W, and the laser frequency was 30 kHz. The plating current density for the nickel plating was 100 mA / cm 2 , and the plating time was 5 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0266] The test method was the same as in Example 1, and the test results are shown in Table 1.

[0267] Comparative Example 24

[0268] A three-dimensional member, a laser sensitizer solution and an activated member were prepared according to the method of Example 1, except that the plating method was electroless plating and the plating solution composition was an aqueous solution of NiSO4-6H2O (25 g / L), Na3C6H5O7-2H2O (30 g / L), CH3COONa (20 g / L), Na2H2PO2-H2O (30 g / L), and the electroless plating time was 40 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0269] The test method was the same as in Example 1 and the test results are shown in Table 1.

[0270] Comparative Example 25

[0271] A three-dimensional member, a laser sensitizer solution and an activated member were prepared according to the method of Example 1, except that the plating method was electroless plating and the plating solution composition was an aqueous solution of NiSO4-6H2O (25 g / L), Na3C6H5O7-2H2O (30 g / L), CH3COONa (20 g / L), Na2H2PO2-H2O (30 g / L), and the electroless plating time was 70 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0272] The test method was the same as in Example 1 and the test results are shown in Table 1.

[0273] Comparative Example 26

[0274] A three-dimensional member, a laser sensitizer solution and an activated member were prepared according to the method of Example 1, except that the plating method was electroless plating and the plating solution composition was an aqueous solution of NiSO4-6H2O (25 g / L), Na3C6H5O7-2H2O (30 g / L), CH3COONa (20 g / L), Na2H2PO2-H2O (30 g / L), and the electroless plating time was 40 minutes. After the nickel plating, the nickel layer was exposed to air for 14 days.

[0275] The test method was the same as in Example 1 and the test results are shown in Table 1.

[0276] Comparative Example 27

[0277] A three-dimensional member, a laser sensitizer solution and an activated member were prepared according to the method of Example 1, except that the plating method was electroless plating and the plating solution composition was an aqueous solution of NiSO4 (30 g / L), NaH2PO2 (20 g / L), C6H 17 N3O7 (50 g / L), and the electroless plating time was 40 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0278] The test method was the same as in Example 1 and the test results are shown in Table 1.

[0279] Comparative Example 28

[0280] The three-dimensional member, the laser sensitizing agent solution and the activated member were prepared according to the method of Example 1, with the difference that the plating method was electroless plating, and the plating solution was an aqueous solution of NiCl2(30 g / L), NaH2PO2(10 g / L) and NH4Cl(50 g / L), and the electroless plating time was 40 minutes. After the nickel plating, the nickel layer was exposed to air for 7 days.

[0281] The test method was the same as that of Example 1, and the test results are shown in Table 1.

[0282] When the polymer surface cannot be selectively metalized by laser activation or has no test value, the performance test cannot be carried out, and thus "no performance" is indicated.

[0283] Table 1 shows the summary of the raw material parameters. "None" indicates that the corresponding substance or method is not used.

[0284] Table 1, test results of performance tests of Examples 1-38 and Comparative Examples 1-13

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296] As can be seen from the test results in Table 1, Examples 1-47 successfully prepared a patterned super-hydrophobic nickel layer on the surface of a three-dimensional resin by using laser selective metalization combined with electroplating nickel, by using different three-dimensional printing methods, different three-dimensional resins, different laser sensitizing agents and contents, different film formers, different laser wavelengths, different laser powers, different laser frequencies, different electroplating current densities, different electroplating times, and different air exposure times.

[0297] From the test results of Table 1, it can be seen that the comparative example 1 does not add a laser sensitizer, and cannot be plated; the comparative examples 2, 6-7 have a laser sensitizer content less than 4 wt.%, and cannot be plated or partially plated with low plating layer adhesion and no practical value; the comparative examples 3-5 have a plating nickel current greater than 500 mA / cm 2 , although normal plating can be achieved, super-hydrophobicity cannot be achieved, and the plating layer adhesion decreases; the comparative examples 8-9, 12-13 have a laser power less than 50% of the maximum power of the laser, and the nickel layer cannot be normally plated; the comparative examples 10, 11 have an air exposure time less than 6 days, and the nickel layer cannot achieve super-hydrophobicity; the comparative examples 14-15 have an electroplating nickel time greater than 20 minutes, although normal plating can be achieved, the nickel layer cannot achieve super-hydrophobicity; the comparative examples 16-17 have a laser frequency greater than 60 kHz, and cannot be plated; the comparative examples 18-19 directly electroplate nickel on the surface of a commercial conductive copper foil, and the nickel layer cannot achieve super-hydrophobicity; the comparative examples 20-23 do not use polyvinyl alcohol, ethylene-vinyl acetate copolymer, hydroxypropyl cellulose, hydroxypropyl methyl cellulose as a film former or do not use a film former, and cannot be plated. The comparative examples 24-28 use chemical plating for plating nickel, and the nickel layer cannot achieve super-hydrophobicity, and since the plating solution composition contains phosphorus elements, the plating layer has no magnetism.

[0298] The experimental results of the examples and comparative examples show that when the laser sensitizer addition amount is 5-20 wt.%, the metal layer can be normally plated and the use amount of the sensitizer can be best balanced. When the film former composition is selected from one of polyvinyl alcohol, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, alcohol-soluble polyamide, acrylic ester homopolymer, acrylic ester copolymer, SEBS, polycarbonate, and styrene-maleic anhydride copolymer, successful plating can be achieved. When the laser power is 100% of the maximum power of the laser and the laser frequency is 30 kHz, the laser activation effect is best. When the plating nickel current density is 100 mA / cm 2 , and the electroplating time is controlled to be 5-10 minutes, the super-hydrophobic effect of the nickel layer is best. After the plating layer is exposed to air for seven days, excellent super-hydrophobic performance can be achieved.

[0299] In summary, the three-dimensional ferromagnetic super-hydrophobic material provided by the present application has no special requirements for three-dimensional printing methods, can spontaneously achieve super-hydrophobicity without manual modification, the pattern can be freely customized, and the ferromagnetism of the nickel layer is ensured, which has important significance in the corrosion resistance, self-cleaning, anti-fouling, ice resistance, and other weather resistance of the conductive metal layer. The method uses laser for selective metallization and does not rely on manual deposition of low surface energy substances, has the advantages of high precision, low cost, and high universality, and has a wide application prospect in the three-dimensional electronic technology industry.

Claims

1. A three-dimensional ferromagnetic superhydrophobic material, characterized in that: It is sequentially covered with copper layer, nickel layer on the three-dimensional structure material; The copper layer is prepared by mixing film forming agent, laser sensitizing agent and solvent, brushing on the surface of resin material, drying, then using laser to radiate the surface to form activated pattern, and then using chemical plating to selectively metalize the activated area; The nickel layer is prepared by electroplating nickel on the copper layer under specific current density, then exposing in air for more than 7 days to obtain magnetic super-hydrophobic nickel layer; The percentage of the use amount of the laser sensitizing agent and the film forming agent is: The percentage of the use amount of the laser sensitizing agent and the film forming agent is: The film forming agent is one of polyvinyl alcohol, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, alcohol-soluble polyamide, acrylic ester homopolymer, acrylic ester copolymer, SEBS, SEPS, SBS, SIS, polycarbonate and styrene-maleic anhydride copolymer; The solvent is one or more of water, acetonitrile, methanol, ethanol, propanol, acetone, dioxane, tetrahydrofuran, methyl ethyl ketone, n-butanol, chloroform, bromoethane, benzene, chloropropane, toluene, carbon tetrachloride, carbon disulfide, cyclohexane and hexane; The laser sensitizing agent is one or more of copper salt, copper oxide, copper hydroxide, copper organic complex, bismuth salt, bismuth oxide, bismuth hydroxide, bismuth organic complex, chromium salt, chromium hydroxide, chromium organic complex, tin salt, tin oxide, tin hydroxide, tin organic complex, tin doped oxide, antimony salt, antimony oxide, antimony hydroxide, antimony organic complex, molybdenum salt, molybdenum oxide, molybdenum sulfide, molybdenum hydroxide, molybdenum-containing acid, indium salt, indium oxide, indium hydroxide, indium organic complex, zinc oxide, zinc sulfide, zinc hydroxide, zinc salt, tungsten oxide, tungsten sulfide, tungsten-containing acid, tungsten salt, lanthanum oxide, niobium oxide, neodymium oxide, nickel oxide, nickel salt, tellurium oxide, zirconium oxide, silver oxide and silver salt; The three-dimensional structure material is prepared by 3D printing method; The wavelength of the laser is 300-1200 nm, the laser power is 1-20 W, the laser scanning speed is 1000-2000 mm / s and the laser frequency is 30-60 kHz; The current density used in the electroplating is 100-500 mA / cm 2 , and the electroplating time is 5-20 minutes. The placing time is 7-30 days.

2. The three-dimensional ferromagnetic superhydrophobic material of claim 1, wherein: The percentage of the use amount of the laser sensitizing agent and the film forming agent is: The percentage of the use amount of the laser sensitizing agent and the film forming agent is:

3. The three-dimensional ferromagnetic superhydrophobic material of claim 1, wherein: The 3D printing method includes any one of stereolithography (SLA), digital light processing (DLP), selective laser sintering (SLS), fused deposition modeling (FDM), multi-beam selective laser sintering (MJF), binder jetting (BJ) and direct energy deposition (DED).

4. The three-dimensional ferromagnetic super-hydrophobic material according to claim 1, wherein: The wavelength of the laser is 1064 nm, the laser power is 20 W and the laser frequency is 30 kHz.

5. The three-dimensional ferromagnetic super-hydrophobic material according to claim 1, wherein: The plating solution formula of the electroplated nickel comprises 6.2 g of boric acid, 23.8 g of nickel chloride hexahydrate and 26.3 g of nickel sulfate per liter of water solution, the plating part is used as cathode, and the platinum sheet is used as anode.

6. The three-dimensional ferromagnetic superhydrophobic material of claim 1, wherein: The current density used in the electroplating is 100 mA / cm 2 and the electroplating time is 5-10 minutes.

7. The three-dimensional ferromagnetic superhydrophobic material according to any one of claims 1-6, wherein: The water contact angle of the super-hydrophobic nickel layer is greater than 150°, and the rolling angle is less than 5°.

8. A method for preparing the three-dimensional ferromagnetic superhydrophobic material according to any one of claims 1-7, characterized in that: It comprises the following steps: Step S1: designing a three-dimensional structure of a three-dimensional electronic device according to requirements, and printing the designed three-dimensional structure by using a 3D printing technology; Step S2: mixing a film-forming agent with a solvent, adding a laser sensitizing agent to obtain a laser sensitizing agent suspension or solution, brushing the suspension or solution on the surface of the three-dimensional printed part, and then drying to remove the solvent; Step S3: irradiating the surface of the three-dimensional part obtained in step S2 by using a laser, forming an activated pattern in the irradiated area, selectively metallizing the activated area by using electroless plating, and obtaining a copper layer on the surface of the three-dimensional part; Step S4: electroplating nickel on the copper layer obtained in step S3 under a specific current density for a certain time, and then exposing the nickel layer to air for a period of time to obtain a three-dimensional ferromagnetic super-hydrophobic nickel layer.

9. Use of the three-dimensional ferromagnetic super-hydrophobic material according to any one of claims 1-7 in the preparation of communication antennas, electromagnetic shielding and flexible robots.

10. Use according to claim 9, characterized in that: The three-dimensional ferromagnetic super-hydrophobic material is used for preparing a magnetically driven robot.

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