BiPbSnNaC alloy powder doped photosensitive resin and preparation method thereof

Abstract

The invention discloses photosensitive resin doped with BiPbSnNaC alloy powder and a preparation method of the photosensitive resin, and belongs to the technical field of organic resin.The Bi, Pb, Sn, Na and C nano-particles are added into a resin matrix, the characteristic that traditional light-cured resin is easy to operate is reserved, the hardness and tensile strength of the photosensitive resin are greatly improved, and the photosensitive resin can be applied to the field of light-emitting devices. The prepared photosensitive resin containing the alloy powder has stable chemical properties, a formed part has better surface precision, and tedious operations such as polishing are not needed.

Description

Technical Field

[0001] The present invention relates to the technical field of organic resins, and particularly relates to a photosensitive resin doped with BiPbSnNaC alloy powder and a preparation method thereof. Background Art

[0002] After traditional photosensitive resin is irradiated by ultraviolet light with a certain wavelength, such as 250nm - 300nm, cross-linking and polymerization reactions occur, and it quickly cures in a short time to play a strengthening role. However, traditional photosensitive resin has the following disadvantages in the use process: (1) Curing shrinkage: The photosensitive resin will undergo volume shrinkage during the curing process, which will cause internal stress in the formed model, easily causing deformation, warping and cracking of the model parts, seriously affecting the accuracy of the parts. (2) Insufficient mechanical properties: The toughness and heat resistance of traditional photosensitive resin are poor, and it is easy to crack, unable to meet the requirements of some high-strength and high-toughness applications. (3) High storage requirements: The photosensitive resin has high requirements for storage conditions, and needs to be stored away from light and in a dry place, and cannot be ventilated or placed directly in the sun. In addition, liquid materials need to be stored in a sealed and classified manner. (4) Health and safety issues: During the printing and manufacturing process, the photosensitive resin will emit irritating gases and has slight toxicity. Due to the problems existing in the above traditional photosensitive resin, it has seriously affected the large-scale industrial application of photosensitive resin. Summary of the Invention

[0003] The present invention provides a photosensitive resin doped with BiPbSnNaC alloy powder and a preparation method thereof, effectively solving the technical problems that traditional photosensitive resin curing shrinkage causes deformation, thus affecting the accuracy of parts, insufficient mechanical properties and unable to meet the application requirements of high strength and high toughness, high storage requirements and safety risks. The present invention dopes Bi, Pb, Sn, Na and C nanoparticles in the resin matrix, not only retaining the easy-to-operate characteristics of traditional photosensitive resin, but also greatly improving the hardness and tensile strength of the photosensitive resin; the photosensitive resin doped with BiPbSnNaC alloy powder prepared by the present invention has stable chemical properties, and the formed parts have better surface accuracy and do not require cumbersome operations such as polishing.

[0004] The first object of the present invention is to provide a preparation method of a photosensitive resin doped with BiPbSnNaC alloy powder, comprising the following steps: Under vacuum conditions, the wire and powder materials are laser scanned and cured in an inert atmosphere to obtain a photosensitive resin doped with BiPbSnNaC alloy powder.

[0005] The wire is composed of a combined preparation of the following components by mass percentage: 40% - 47% acrylate, 20% - 30% alcohol and ethyl cellulose polymer, 12% - 38% photoinitiator and 5% - 15% epoxy resin diluent, totaling 100%.

[0006] The powder material is composed of the following components mixed in mass percentages: 28% - 38% bismuth, 16% - 35% lead, 13% - 18% tin, 10% - 19% sodium, and 13% - 33% carbon, with a total of 100%.

[0007] The mass ratio of the wire material to the powder material is 2.0 - 2.5:1.

[0008] As a preferred embodiment, the wire feeding speed of the wire material is 10 g / min - 30 g / min, and the powder feeding speed of the powder material is 5 g / min - 15 g / min.

[0009] As a preferred embodiment, the parameters of the laser are: laser power is 150 W - 600 W, laser scanning speed is 200 mm / min - 400 mm / min, and spot diameter is 1 mm - 3 mm.

[0010] As a preferred embodiment, the inert gas is helium, and the helium flow rate is 3 L / min - 18 L / min.

[0011] As a preferred embodiment, the parameters of the vacuum are 400 Torr - 600 Torr.

[0012] As a preferred embodiment, the combined preparation of the alcohol and ethyl cellulose polymer is prepared by mixing an alcohol containing 36 - 48 carbon atoms and being liquid at normal temperature and pressure and an ethyl cellulose polymer in a mass ratio of 1 - 1.5:1.7, and the viscosity of the combined preparation of the alcohol and ethyl cellulose polymer is ≥50 mPa·s.

[0013] As a preferred embodiment, the epoxy resin diluent is one or more of acrylic alkyl ester, hydroxy acrylate, hydroxy methacrylate, vinyl acetate, hydroxyethyl acrylate, trimethylolpropane trimethacrylate, methyl benzoylformate, and isobornyl methacrylate.

[0014] As a preferred embodiment, the photoinitiator is TPO photoinitiator, photoinitiator 819, or photoinitiator 1173.

[0015] As a preferred embodiment, the acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate.

[0016] The second object of the present invention is to provide a photosensitive resin doped with BiPbSnNaC alloy powder prepared by the preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder as described above.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: In order to solve the problems in the prior art that after traditional photosensitive resin is irradiated by ultraviolet light of a certain wavelength, cross-linking and polymerization reactions occur, and it cures rapidly in a short time to play a strengthening role, but there is curing shrinkage, resulting in internal stress in the formed model, causing deformation, warping and cracking of the model parts, seriously affecting the accuracy of the parts and the lack of mechanical strength. The present invention proposes adding Bi, Pb, Sn, Na and C nanoparticles into the resin matrix, which solves the technical problems of insufficient mechanical properties and hardness of traditional photocurable resins, specifically manifested as follows: In the photosensitive resin doped with BiPbSnNaC alloy powder of the present invention, a combined preparation of acrylate, alcohol and ethyl cellulose polymer, a photoinitiator and an epoxy resin diluent are mixed to form a resin matrix. An epoxy resin diluent is added to the resin matrix. During subsequent curing and forming, the forming resin can form a macromolecular network structure in a heating environment, enabling the resin small molecules in the resin matrix to further form a resin macromolecule network, improving the degree of internal layer curing of the model, thereby greatly improving the tensile and bending properties, impact resistance and hardness of the forming resin. Adding a combined preparation of alcohol and ethyl cellulose polymer can increase the viscosity of the organic materials in the resin matrix before shaping, facilitating the subsequent curing of the resin. The reaction of synthesizing epoxy resin from acrylate and the combined preparation of alcohol and ethyl cellulose polymer is a step-by-step polymerization reaction, which is carried out in two stages. First, under the action of the photoinitiator, acrylate opens the ring at the primary carbon position and undergoes an addition reaction with the combined preparation of alcohol and ethyl cellulose polymer. Secondly, the epoxy resin diluent acts as a reaction reagent to remove HCl and form a new epoxy group. Adding these nanoparticles of Bi, Pb, Sn, Na and C, and evenly distributing them in the network structure of the resin matrix to form an uneven special network structure. Using bismuth, lead, tin, sodium and carbon powders as raw materials, the formed alloy has a low melting point, which can reach below 100°C. A small amount of oxygen in the air reacts with bismuth to form Bi2O3, and bismuth oxide acts as a catalyst to promote the reaction of other elements in the alloy, thereby reducing the risk of deformation, warping and cracking of the model parts, improving the accuracy of the parts, improving the toughness and heat resistance of the photosensitive resin, and further promoting the large-scale industrial application of the photosensitive resin.

[0018] In the present invention, an auxiliary agent containing alloy powder is added to the photosensitive resin. During the subsequent curing process, the overall rigidity of the resin will be further enhanced, significantly improving the mechanical properties such as the rigidity and impact resistance of the model. In addition, during the curing process of the resin material, a combined preparation containing alcohol and ethyl cellulose polymer is used instead of the traditional organopolysiloxane, which is more environmentally friendly, odorless, and has greater viscosity during the preparation process. The metal network structure formed by the nano-alloy powder and the network structure formed by the organic material of the present invention are melted into a special resin under a laser scanner, having stable chemical properties, not easily oxidizing and deteriorating in oxygen, and having better physical properties. Both the hardness and tensile strength are further improved, enabling it to be applied in more complex environments.

[0019] Compared with traditional photocuring resins, the present invention uses metal powders with controllable melting points and more environmentally friendly organic materials, and the formed resin has better surface accuracy and stable chemical properties. With the combination of organic materials and metal powders, the performance of the resin has changed significantly. The alloy powder photocuring resin has better mechanical properties and also shows excellent performance in terms of tensile and compressive strength. Since metal powders are added during the resin forming process, the formed parts often have better surface accuracy and do not require cumbersome operations such as polishing. Description of the Drawings

[0020] Figure 1 It is a schematic structural diagram of the processing equipment for preparing a photosensitive resin doped with BiPbSnNaC alloy powder by laser scanning curing adopted in the present invention.

[0021] Description of the Reference Numerals in the Drawings: 1. Control system and laser instrument, 2. Cured finished product, 3. Workbench, 4. Resin powder injector, 5. Metal wire injector. Detailed Embodiments

[0022] In order to enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments, but the specific embodiments cited do not limit the present invention. The following test methods and detection methods are all conventional methods unless otherwise specified; the reagents and raw materials are all commercially available unless otherwise specified.

[0023] Traditional photocurable resins are usually obtained by reacting photoinitiators, diluents, resin prepolymers, and additives. However, their mechanical properties, electrical conductivity, thermal conductivity, and chemical corrosion resistance are all insufficient, limiting their application scope. During the curing process of traditional photosensitive resins, volume shrinkage occurs, resulting in internal stress in the formed model, which easily causes deformation, warping, and cracking of model parts, seriously affecting the accuracy of the parts. The toughness and heat resistance of traditional photosensitive resins are poor, and they are prone to brittle fracture, unable to meet the requirements of some high-strength and high-toughness applications. Photosensitive resins have high requirements for storage conditions, need to be stored in the dark and dry, cannot be ventilated or placed directly in the sun. During the printing and manufacturing process, photosensitive resins will emit irritating gases and have slight toxicity. Based on the above technical problems, the present invention provides a photosensitive resin doped with BiPbSnNaC alloy powder and its preparation method.

[0024] The technical solution of the present invention will be described in detail below.

[0025] The present invention first provides a preparation method of a photosensitive resin doped with BiPbSnNaC alloy powder, comprising the following steps: Under vacuum conditions, the wire material and powder material are cured by laser scanning in an inert atmosphere to obtain a photosensitive resin doped with BiPbSnNaC alloy powder.

[0026] The wire material is composed of a combination preparation of the following components by mass percentage: 40% - 47% acrylate, 20% - 30% alcohol and ethyl cellulose polymer, 12% - 38% photoinitiator, and 5% - 15% epoxy resin diluent, totaling 100%.

[0027] The powder material is composed of the following components by mass percentage: 28% - 38% bismuth, 16% - 26% lead, 13% - 18% tin, 7% - 17% sodium, and 13% - 23% carbon, totaling 100%.

[0028] Acrylate is the matrix component of the resin, and its content directly affects the mechanical properties and curing characteristics of the resin. Too low content may lead to insufficient mechanical properties of the resin, while too high content may lead to increased brittleness and decreased flexibility of the resin; adding a combined preparation of alcohol and ethyl cellulose polymer can increase the viscosity of the organic materials in the resin matrix when it is not yet formed, facilitating the subsequent curing of the resin. The reaction of synthesizing epoxy resin from acrylate and the combined preparation of alcohol and ethyl cellulose polymer is a stepwise polymerization reaction, which is carried out in two stages. First, under the action of a photoinitiator, the acrylate opens the ring at the primary carbon position and undergoes an addition reaction with the combined preparation of alcohol and ethyl cellulose polymer. Secondly, the epoxy resin diluent acts as a reaction reagent to remove HCl and form new epoxy groups. Adding nanoparticles composed of Bi, Pb, Sn, Na, and C and evenly distributing them in the network structure of the resin matrix forms an uneven special network structure. Using bismuth, lead, tin, sodium, and carbon powders as raw materials, the formed alloy has a relatively low melting point, which can reach below 100°C. A small amount of oxygen in the air reacts with bismuth to form the oxide Bi2O3, and bismuth oxide acts as a catalyst to promote the reaction of other elements in the alloy, thereby improving the performance of the alloy. Insufficient content of the photoinitiator may lead to incomplete curing of the resin, affecting its final performance; too high content may lead to excessive bubbles generated during the curing process of the resin, affecting its transparency and mechanical properties; the epoxy resin diluent is used to adjust the viscosity of the resin and improve its processability. Too low content may make the resin too viscous and not conducive to processing; too high content may lead to a decline in the mechanical properties of the resin and poor chemical resistance.

[0029] The melting point of the alloy powder is lower than that of its constituent elements. This proportion of alloy powder will melt below 100°C; exceeding or being lower than this proportion, the melting temperature will exceed 100°C.

[0030] The mass ratio of the wire material to the powder material is 2.0 - 2.5:1. If the mass ratio of the wire material is lower than 2.0, too much alloy powder will lead to a decline in the mechanical properties of the finished product because the bonding force of the resin is not sufficient to effectively combine the excessive powder; if the mass ratio of the wire material is higher than 2.5, the insufficient proportion of alloy powder may lead to a decline in the mechanical properties of the composite material, such as the strength, hardness, and toughness may not reach the expected effect.

[0031] As a preferred implementation method, the wire feeding speed of the wire material is 10 g / min - 30 g / min, and the powder feeding speed of the powder material is 5 g / min - 15 g / min. Too fast speed may lead to uneven cladding layer, voids or lack of fusion; too slow speed may lead to excessive melting, affecting the density and uniformity of the cladding layer.

[0032] As a preferred embodiment, the parameters of the laser are as follows: the laser power is 150 W to 600 W. If the power is too low, the formation of the cladding layer or weld seam will be poor, affecting the bonding strength. If the power is too high, it may cause excessive melting, resulting in pores or cracks. The laser scanning speed is 200 mm / min to 400 mm / min. If the speed is too slow, the cladding layer may be too thick, increasing the porosity. If the speed is too fast, the cladding layer may be discontinuous or unfused. The spot diameter is 1 mm to 3 mm. If the spot is too large, the energy will be dispersed, reducing the quality of the cladding layer. If the spot is too small, it may limit the deposition rate of the cladding material, affecting the production efficiency.

[0033] As a preferred embodiment, the inert gas is helium, and the helium flow rate is 3 L / min to 18 L / min. If the flow rate is lower than 3 L / min, the molten pool cannot be effectively protected. If the flow rate is too high, higher than 18 L / min, the molten pool will cool too quickly, affecting the formation and performance of the joint.

[0034] As a preferred embodiment, the parameters of the vacuum are 400 Torr to 600 Torr. An appropriate degree of vacuum helps to remove bubbles during the resin flow process, reducing the porosity, thereby improving the integrity and strength of the product.

[0035] As a preferred embodiment, the combined preparation of the alcohol and ethyl cellulose polymer is prepared by mixing an alcohol containing 36 to 48 carbon atoms and being liquid at normal temperature and pressure and the ethyl cellulose polymer in a mass ratio of 1 to 1.5:1.7, and the viscosity of the combined preparation of the alcohol and ethyl cellulose polymer is ≥50 mPa·s. The above combined preparation has a low viscosity, good fluidity during the molding process, less heat release during curing, a low curing temperature, and a short time from gelation to curing and demolding.

[0036] It should be emphasized that the epoxy resin diluent used in the present invention is one or several of acrylic alkyl esters, acrylic hydroxy esters, methacrylic hydroxy esters, vinyl acetate, hydroxyethyl acrylate, trimethylolpropane trimethacrylate, methyl benzoylformate, and isobornyl methacrylate. The photoinitiator is TPO photoinitiator, photoinitiator 819, or photoinitiator 1173. The acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate.

[0037] The content of the present invention will be specifically described below through the following examples and comparative examples.

[0038] Example 1 A photosensitive resin doped with BiPbSnNaC alloy powder, including a resin matrix and alloy powder.

[0039] The raw materials of the resin matrix by mass percentage are weighed in the following amounts: 40% of acrylate compounds, 30% of a combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1:1.7, 20% of TPO photoinitiator, and 10% of alkyl acrylate and isobornyl methacrylate, totaling 100%.

[0040] The alloy powder consists of the following raw materials by mass percentage: 28% Bi, 26% Pb, 13% Sn, 10% Na, 23% C, totaling 100%.

[0041] The photosensitive resin doped with BiPbSnNaC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0042] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0043] Under a vacuum condition of 400 Torr, in a helium gas atmosphere with a flow rate of 3 L / min, according to a mass ratio of 2.0:1, put the wire and the powder into a wire feeding mechanism and a powder feeding mechanism respectively. The wire is fed at a speed of 10 g / min using Figure 1 the metal wire injector 5 in Figure 1 to feed the wire, and the powder is fed at a speed of 5 g / min using Figure 1 the resin powder injector 4 in

[0044] Example 2 A photosensitive resin doped with BiPbSnNaC alloy powder, including a resin matrix and an alloy powder.

[0045] The resin matrix consists of the following raw materials by mass percentage: 42% of acrylate compounds, 28% of a combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.1:1.7, 16% of TPO photoinitiator, 7% of vinyl acetate, and 7% of isobornyl methacrylate, totaling 100%.

[0046] The alloy powder consists of the following raw materials by mass percentage: 30% Bi, 24% Pb, 14% Sn, 13% Na, 19% C, totaling 100%.

[0047] The photosensitive resin doped with BiPbSnNaC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0048] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0049] Under a vacuum condition of 430 Torr, in a helium atmosphere with a flow rate of 5 L / min, according to a mass ratio of 2.1:1, put the wire material and the powder material into a wire feeding mechanism and a powder feeding mechanism respectively. The wire material is fed at a speed of 14 g / min by using Figure 1 the wire injector 5 for metal wire in Figure 1 the powder injector 4 for resin powder in Figure 1 shown processing equipment, and through the control system and the laser instrument 1, perform laser scanning and curing on the workbench 3 to obtain a cured finished part 2, that is, a photosensitive resin doped with BiPbSnNaC alloy powder.

[0050] Example 3 A photosensitive resin doped with BiPbSnNaC alloy powder, comprising a resin matrix and alloy powder.

[0051] The resin matrix is composed of raw materials in the following mass percentages: 43% acrylate compound, 25% combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.2:1.7, 23% TPO photoinitiator, 4% vinyl acetate, 5% methyl benzoylformate.

[0052] The alloy powder is composed of raw materials in the following mass percentages: 32% Bi, 22% Pb, 15% Sn, 15% Na, 16% C, totaling 100%.

[0053] The above photosensitive resin doped with BiPbSnNaC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire material.

[0054] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0055] Under a vacuum condition of 450 Torr, in a helium atmosphere with a flow rate of 7 L / min, according to a mass ratio of 2.3:1, put the wire material and the powder material into a wire feeding mechanism and a powder feeding mechanism respectively. The wire material is fed at a speed of 17 g / min by using Figure 1 the wire injector 5 for metal wire in Figure 1 the powder injector 4 for resin powder in Figure 1The processing equipment shown performs laser scanning and curing on the workbench 3 through the control system and the laser instrument 1 to obtain a cured finished part 2, that is, a photosensitive resin doped with BiPbSnNaC alloy powder.

[0056] Example 4 A photosensitive resin doped with BiPbSnNaC alloy powder includes a resin matrix and alloy powder.

[0057] The resin matrix is composed of raw materials in the following mass percentages: 43% acrylate compound, 27% combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.3:1.7, 18% TPO photoinitiator, 12% alkyl acrylate, totaling 100%.

[0058] The alloy powder is composed of raw materials in the following mass percentages: 34% Bi, 20% Pb, 16% Sn, 17% Na, 13% C, totaling 100%.

[0059] The above photosensitive resin doped with BiPbSnNaC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire material.

[0060] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder material.

[0061] Under a vacuum condition of 500 Torr, in a helium gas atmosphere with a flow rate of 12 L / min, according to a mass ratio of 2.3:1, put the wire material and the powder material into the wire feeding mechanism and the powder feeding mechanism respectively. The wire material is fed at a speed of 20 g / min using Figure 1 the metal wire injector 5 in Figure 1 to feed the wire, and the powder material is fed at a speed of 11 g / min using Figure 1 the resin powder injector 4 in

[0062] Example 5 A photosensitive resin doped with BiPbSnNaC alloy powder includes a resin matrix and alloy powder.

[0063] The resin matrix is composed of raw materials in the following mass percentages: 47% phenoxyethyl acrylate, 30% combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.4:1.7, 13% TPO photoinitiator, 5% alkyl acrylate, 5% isobornyl methacrylate, totaling 100%.

[0064] The alloy powder is composed of raw materials with the following mass percentages: 36% Bi, 18% Pb, 17% Sn, 11% Na, 18% C, totaling 100%.

[0065] The photosensitive resin doped with BiPbSnNaC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0066] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0067] Under a vacuum condition of 550 Torr, in a helium atmosphere with a flow rate of 15 L / min, according to a mass ratio of 2.4:1, put the wire and the powder into the wire feeding mechanism and the powder feeding mechanism respectively. The wire is fed at a speed of 25 g / min using Figure 1 the wire injector 5 for wire feeding in Figure 1 and the powder is fed at a speed of 13 g / min using Figure 1 the resin powder injector 4 for powder feeding in. With a laser power of 450 W and a laser scanning speed of 340 mm / min, control the spot diameter to be 3 mm. Using the

[0068] Example 6 A photosensitive resin doped with BiPbSnNaC alloy powder, including a resin matrix and an alloy powder.

[0069] The resin matrix is composed of raw materials with the following mass percentages: 45% phenoxyethyl acrylate, 28% combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.5:1.7, 20% TPO photoinitiator, and 7% isobornyl methacrylate, totaling 100%.

[0070] The alloy powder is composed of raw materials with the following mass percentages: 38% Bi, 16% Pb, 18% Sn, 7% Na, 21% C, totaling 100%.

[0071] The photosensitive resin doped with BiPbSnNaC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0072] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0073] Under a vacuum condition of 570 Torr, in a helium atmosphere with a flow rate of 17 L / min, the wire and powder were placed in a wire feeding mechanism and a powder feeding mechanism respectively according to a mass ratio of 2.5:1. The wire was fed at a speed of 27 g / min. Figure 1 The wire is fed by the metal wire ejector 5, and the powder is fed at a speed of 14 g / min. Figure 1 The resin powder injector 4 in the spray gun is used to feed powder. The laser power is 500W, the laser scanning speed is 380mm / min, and the spot diameter is controlled to be 3mm. Figure 1 The processing equipment shown in the figure performs laser scanning and curing on a workbench 3 through a control system and a laser instrument 1 to obtain a cured finished product 2, namely a photosensitive resin doped with BiPbSnNaC alloy powder.

[0074] In order to further illustrate the effect of the present invention, the present invention also sets a comparative example, as follows: Comparative Example 1 Compared with Example 1, the difference is that the Na element is removed and the mass percentage of the C element is increased from 23% to 33%. The alloy powder is composed of the following raw materials in mass percentage: 28% Bi, 26% Pb, 13% Sn, 33% C, totaling 100%.

[0075] A photosensitive resin doped with BiPbSnC alloy powder comprises a resin matrix and alloy powder.

[0076] The raw materials of the resin matrix are weighed in the following proportions by mass: 40% of methyl acrylate compounds, 30% of a combination preparation of alcohol and ethyl cellulose polymer in a mass ratio of 1:1.7, 20% of a TPO photoinitiator, and 10% of alkyl acrylate and isobornyl methacrylate, totaling 100%.

[0077] The alloy powder is composed of the following raw materials in percentage by mass: 28% Bi, 26% Pb, 13% Sn, and 33% C, which totals 100%.

[0078] The photosensitive resin doped with BiPbSnC alloy powder comprises the following steps: The raw materials of the resin matrix are weighed and mixed evenly to obtain a filament.

[0079] The raw materials of the alloy powder are weighed and mixed evenly to obtain a powder material.

[0080] Under 400Torr vacuum conditions, in a helium atmosphere with a flow rate of 3L / min, the wire and powder were placed in a wire feeding mechanism and a powder feeding mechanism respectively according to a mass ratio of 2.0:1. The wire was fed at a speed of 10g / min using Figure 1The wire feeder 5 in it is used to feed the wire, and the powder material is fed at a speed of 5 g / min by Figure 1 The resin powder injector 4 in it is used to feed the powder. At a laser power of 150 W and a laser scanning speed of 200 mm / min, the spot diameter is controlled to be 1 mm. Using Figure 1 The processing equipment shown in it, through the control system and the laser instrument 1, laser scanning and curing are carried out on the workbench 3 to obtain the cured finished part 2, that is, the photosensitive resin doped with BiPbSnC alloy powder.

[0081] Comparative Example 2 Compared with Example 2, the difference is that the Na element is removed, and the mass percentage of the C element is increased from 23% to 33%. The alloy powder is composed of the following raw materials by mass percentage: 30% Bi, 24% Pb, 14% Sn, 32% C, totaling 100%.

[0082] A photosensitive resin doped with BiPbSnC alloy powder, including a resin matrix and alloy powder.

[0083] The resin matrix is composed of the following raw materials by mass percentage: 42% acrylate compound, 28% combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.1:1.7, 16% TPO photoinitiator, 7% vinyl acetate, 7% isobornyl methacrylate, totaling 100%.

[0084] The alloy powder is composed of the following raw materials by mass percentage: 30% Bi, 24% Pb, 14% Sn, 32% C, totaling 100%.

[0085] The above photosensitive resin doped with BiPbSnC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain the wire.

[0086] Weigh the raw materials of the alloy powder, mix them evenly to obtain the powder material.

[0087] Under a vacuum condition of 430 Torr and in a helium atmosphere with a flow rate of 5 L / min, according to a mass ratio of 2.1:1, the wire and the powder material are respectively put into the wire feeding mechanism and the powder feeding mechanism. The wire is fed at a speed of 14 g / min by Figure 1 The wire feeder 5 in it is used to feed the wire, and the powder material is fed at a speed of 7 g / min by Figure 1 The resin powder injector 4 in it is used to feed the powder. At a laser power of 250 W and a laser scanning speed of 240 mm / min, the spot diameter is controlled to be 1 mm. Using Figure 1The processing equipment shown performs laser scanning and curing on the workbench 3 through the control system and the laser instrument 1 to obtain a cured finished part 2, that is, a photosensitive resin doped with BiPbSnC alloy powder.

[0088] Comparative Example 3 Compared with Example 3, the difference is that the Na element is removed, and the mass percentage of the C element is increased from 16% to 31%. The alloy powder is composed of the following raw materials by mass percentage: 32% Bi, 22% Pb, 15% Sn, 31% C, totaling 100%.

[0089] A photosensitive resin doped with BiPbSnC alloy powder, comprising a resin matrix and alloy powder.

[0090] The resin matrix is composed of the following raw materials by mass percentage: 43% acrylate compound, 25% combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.2:1.7, 23% TPO photoinitiator, 4% vinyl acetate, 5% methyl benzoylformate.

[0091] The alloy powder is composed of the following raw materials by mass percentage: 32% Bi, 22% Pb, 15% Sn, 31% C, totaling 100%.

[0092] The above-mentioned photosensitive resin doped with BiPbSnC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0093] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0094] Under a vacuum condition of 450 Torr, in a helium gas atmosphere with a flow rate of 7 L / min, according to a mass ratio of 2.3:1, put the wire and the powder into the wire feeding mechanism and the powder feeding mechanism respectively. The wire is fed at a speed of 17 g / min by using Figure 1 the metal wire injector 5 therein, and the powder is fed at a speed of 9 g / min by using Figure 1 the resin powder injector 4 therein. At a laser power of 300 W and a laser scanning speed of 280 mm / min, control the spot diameter to be 2 mm. Using the Figure 1 processing equipment shown, perform laser scanning and curing on the workbench 3 through the control system and the laser instrument 1 to obtain a cured finished part 2, that is, a photosensitive resin doped with BiPbSnC alloy powder.

[0095] Comparative Example 4 Compared with Example 4, the difference lies in that the mass percentage of Sn element is reduced from 16% to 12%, while the mass percentage of Na element is reduced from 17% to 14%, and the mass percentage of C element is increased from 13% to 20%. The alloy powder is composed of raw materials with the following mass percentages: 34% Bi, 20% Pb, 16% Sn, 17% Na, 13% C, totaling 100%.

[0096] A photosensitive resin doped with BiPbSnNaC alloy powder, comprising a resin matrix and alloy powder.

[0097] The resin matrix is composed of raw materials with the following mass percentages: 43% acrylate compound, 27% combined preparation of alcohol and ethyl cellulose polymer with a mass ratio of 1.3:1.7, 18% TPO photoinitiator, 12% alkyl acrylate, totaling 100%.

[0098] The alloy powder is composed of raw materials with the following mass percentages: 34% Bi, 20% Pb, 16% Sn, 17% Na, 13% C, totaling 100%.

[0099] The above photosensitive resin doped with BiPbSnNaC alloy powder includes the following steps: Weigh the raw materials of the resin matrix, mix them evenly to obtain a wire.

[0100] Weigh the raw materials of the alloy powder, mix them evenly to obtain a powder.

[0101] Under a vacuum condition of 500 Torr and in a helium gas atmosphere with a flow rate of 12 L / min, according to a mass ratio of 2.3:1, put the wire and the powder into a wire feeding mechanism and a powder feeding mechanism respectively. The wire is fed at a speed of 20 g / min using the Figure 1 metal wire injector 5 in it, and the powder is fed at a speed of 11 g / min using the Figure 1 resin powder injector 4 in it. At a laser power of 400 W and a laser scanning speed of 300 mm / min, control the spot diameter to be 2 mm. Using the Figure 1 processing equipment shown, through the control system and the laser instrument 1, perform laser scanning curing on the workbench 3 to obtain a cured finished part 2, that is, a photosensitive resin doped with BiPbSnNaC alloy powder.

[0102] Detect the properties of the photosensitive resins doped with BiPbSnNaC alloy powder provided in the above Examples 1 to 6 and Comparative Example 4 and the photosensitive resins doped with BiPbSnC alloy powder provided in Comparative Examples 1 to 3 respectively. The results are shown in Table 1.

[0103] Table 1 Performance Test Table of Photosensitive Resin in Embodiments and Comparative Examples of the Present Invention

[0104] As can be seen from Table 1, the photosensitive resin doped with BiPbSnNaC alloy powder prepared by the present invention has excellent heat distortion temperature, tensile strength and Barcol hardness. However, the mechanical properties of the photosensitive resins obtained in Comparative Examples 1 to 4 above are not good. The main reasons are as follows: In Comparative Examples 1 to 3, the Na element is missing and the amount of C element is increased. The Na element plays a role in adjusting the properties of the resin. During the resin forming process, Na + combines with the active groups in the resin, affecting the exchange ability and selectivity of the resin. The absence of the Na element may lead to a decrease in the ion exchange ability of the resin, thus affecting its performance in applications such as water treatment. Increasing the amount of C element changes the chemical structure and physical properties of the resin. The increase in C element leads to an increase in the crosslinking density of the resin, thereby increasing the hardness and brittleness of the resin, but reducing its toughness and ductility.

[0105] In Comparative Example 4, the mass percentage of Sn element is reduced from 16% to 12%, at the same time the mass percentage of Na element is reduced from 17% to 14%, and the mass percentage of C element is increased from 13% to 20%. Reducing the mass percentage of Sn element will reduce the stability and mechanical strength of the resin. The reduction of Na element will affect the wettability of the resin and the adhesion to the substrate. Increasing C element increases the hardness of the resin, but reduces its toughness, making the resin more likely to break when subjected to external forces.

[0106] In summary, the present invention dopes alloy powders of Bi, Pb, Sn, Na and C in the resin matrix, uses metal powders with controllable melting points and more environmentally friendly organic materials, and the formed resin has good surface accuracy and stable chemical properties. Under the combination of the organic material and the metal powder, the properties of the resin have changed significantly. The alloy powder photocuring resin has better mechanical properties and also has very good performance in tensile and compressive aspects. Since metal powder is added during the resin forming process, the formed parts often have better surface accuracy and do not require cumbersome operations such as polishing.

[0107] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these changes and variations.

Claims

1. A preparation method of a photosensitive resin doped with BiPbSnNaC alloy powder, characterized in that, It includes the following steps: Under vacuum conditions, the wire material and powder material are laser scanned and cured in an inert atmosphere to obtain a photosensitive resin doped with BiPbSnNaC alloy powder; The wire material is composed of a combined preparation of the following components by mass percentage: 40% - 47% acrylate, 20% - 30% alcohol and ethyl cellulose polymer, 12% - 38% photoinitiator, and 5% - 15% epoxy resin diluent, totaling 100%; The powder material is composed of the following components by mass percentage: 28% - 38% bismuth, 16% - 26% lead, 13% - 18% tin, 7% - 17% sodium, and 13% - 23% carbon, totaling 100%; The mass ratio of the wire material to the powder material is 2.0 - 2.5:

1.

2. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, characterized in that, The wire feeding speed of the wire material is 10 g / min - 30 g / min, and the powder feeding speed of the powder material is 5 g / min - 15 g / min.

3. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, wherein, The parameters of the laser are: laser power is 150 W - 600 W, laser scanning speed is 200 mm / min - 400 mm / min, and spot diameter is 1 mm - 3 mm.

4. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, wherein, The inert gas is helium, and the helium flow rate is 3 L / min - 18 L / min.

5. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, characterized in that, The parameters of the vacuum are 400 Torr - 600 Torr.

6. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, characterized in that, The combined preparation of alcohol and ethyl cellulose polymer is prepared by mixing an alcohol containing 36 - 48 carbon atoms and being liquid at normal temperature and pressure and ethyl cellulose polymer in a mass ratio of 1 - 1.5:1.7, and the viscosity of the combined preparation of alcohol and ethyl cellulose polymer is ≥50 mPa·s.

7. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, characterized in that The epoxy resin diluent is one or several of alkyl acrylate, hydroxy acrylate, hydroxy methacrylate, vinyl acetate, hydroxyethyl acrylate, trimethylolpropane trimethacrylate, methyl benzoylformate, and isobornyl methacrylate.

8. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, characterized in that, The photoinitiator is TPO photoinitiator, photoinitiator 819, or photoinitiator 1173.

9. The preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to claim 1, characterized in that, The acrylate is methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate.

10. A photosensitive resin doped with BiPbSnNaC alloy powder prepared by the preparation method of the photosensitive resin doped with BiPbSnNaC alloy powder according to any one of claims 1 - 9.

Images