Two-component reactive 3D printing wax material and preparation method and use method thereof

Abstract

The present invention provides a two-component reactive 3D printing wax material and a preparation method and a use method thereof, and specifically relates to the technical field of 3D printing materials. The two-component reactive 3D printing wax material comprises component A and component B; component A comprises refined paraffin wax, aromatic dihydroxy compound monomer, catalyst and antioxidant; component B comprises refined paraffin wax, carbonyl compound monomer and antioxidant. The present invention reduces the melt viscosity of the printing wax material by separating the aromatic dihydroxy compound monomer and the carbonyl compound monomer through two components, effectively solves the fluidity problem of traditional polymer polycarbonate in MJP jet printing, and makes the printing process smoother. The generated polycarbonate is combined with other components in the wax material, which not only improves the overall mechanical properties of the printing mold, but also significantly improves the dimensional accuracy of the mold, meeting the strict requirements of high-precision investment casting.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing materials, and in particular to a two-component reactive 3D printing wax material and a preparation method and a use method thereof. Background Art

[0002] 3D printing technology, as a rapidly developing rapid free-form prototyping technology, has demonstrated its importance in many fields. Multi-nozzle jetting technology (MJP), as a branch of 3D printing technology, is particularly suitable for printing models based on wax materials. These models play an important role in investment casting because they can replace traditional mold opening methods, thereby saving costs and shortening production cycles. At present, MJP technology has been widely used in medical devices, jewelry, handicrafts, model making, industrial casting and precision casting.

[0003] However, MJP technology faces some challenges in practical applications. The wax materials currently used perform poorly in terms of thermal deformation and mechanical properties, which results in large deviations in the shape and position tolerances of the printed molds and cannot meet the needs of high-precision investment casting. In order to improve the mechanical properties of 3D printed wax materials, some fillers, such as cross-linked polystyrene, are usually added. Although these fillers can significantly improve the mechanical properties of the material, they themselves have high melt viscosity and viscoelasticity, which makes them difficult to print directly through 3D printing technologies such as MJP.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] One of the purposes of the present invention is to provide a two-component reactive 3D printing wax material, aiming to solve at least one of the above-mentioned technical problems of the prior art.

[0006] A second object of the present invention is to provide a method for preparing a two-component reactive 3D printing wax material.

[0007] A third object of the present invention is to provide a method for using a two-component reactive 3D printing wax material.

[0008] In order to solve the above technical problems, the present invention particularly adopts the following technical solutions:

[0009] A first aspect of the present invention provides a two-component reactive 3D printing wax material including component A and component B;

[0010] Wherein, the component A comprises refined paraffin, aromatic dihydroxy compound monomer, catalyst and antioxidant;

[0011] The component B comprises refined paraffin, a carbonyl compound monomer and an antioxidant.

[0012] Furthermore, the component A or the component B independently further comprises at least one of a mechanical modifier, liquid paraffin, a tackifying resin, a nucleating agent and a color powder.

[0013] Furthermore, in parts by weight, the component A comprises 50-70 parts of refined paraffin wax, 10-25 parts of aromatic dihydroxy compound monomer, 0.01-0.5 parts of catalyst and 0.01-0.5 parts of antioxidant;

[0014] The component B comprises 50-70 parts of refined paraffin wax, 10-25 parts of carbonyl compound monomer and 0.01-0.5 parts of antioxidant.

[0015] Furthermore, in parts by weight, the component A further comprises at least one of 2 to 10 parts of a mechanical modifier, 1 to 5 parts of liquid paraffin, 1 to 5 parts of a tackifying resin, 1 to 3 parts of a nucleating agent, and 0.1 to 0.3 parts of a color powder.

[0016] In terms of weight, the component B further comprises at least one of 2 to 10 parts of a mechanical modifier, 3 to 10 parts of liquid paraffin, 1 to 5 parts of a tackifying resin, 1 to 3 parts of a nucleating agent, and 0.1 to 0.3 parts of a color powder.

[0017] Furthermore, the refined paraffin wax includes at least one of unsaturated hydrocarbon wax, natural plant wax and synthetic wax.

[0018] The aromatic dihydroxy compound monomer includes at least one of bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol Z and tetramethyl bisphenol F.

[0019] The catalyst includes at least one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide and tetrabutyl titanate.

[0020] The antioxidant includes a thiol antioxidant.

[0021] The carbonyl compound monomer includes at least one of diphenyl carbonate, bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate and bis(4-nitrophenyl) carbonate.

[0022] Furthermore, the mechanical modifier includes at least one of palm wax, candelilla wax, butadiene styrene copolymer and POE.

[0023] The tackifying resin includes at least one of terpene resin, rosin, rosin derivatives, petroleum resin and modified petroleum resin.

[0024] The nucleating agent includes at least one of microcrystalline wax, ethylene-vinyl acetate copolymer, polyethylene wax, stearic acid and palmitic acid. The toner includes at least one of inorganic toner, organic toner, composite pigment, fluorescent pigment and pearlescent pigment. The second aspect of the present invention provides a method for preparing the two-component reactive 3D printing wax material, comprising the following steps:

[0025] a. Mix the raw materials in the component A at 150-180° C. to obtain a molten liquid of the component A, and filter and cool to obtain the component A;

[0026] b. Mix the raw materials in the component B at 110-130° C. to obtain a molten liquid of the component B, and filter and cool to obtain the component B.

[0027] The third aspect of the present invention provides a method for using the two-component reactive 3D printing wax material. In a multi-nozzle jet printing process, a nozzle with multiple nozzles is used to print component A and component B respectively. Under heating conditions, component A and component B are fused and reacted to form the layer structure. Finally, the printing platform is moved up and the printing steps are repeated to obtain a model.

[0028] Furthermore, the separate printing is to use two nozzles to first print component A and then print component B at the same position.

[0029] or,

[0030] The separate printing is to use two nozzles to first print component A in a certain layer to form a continuous component A layer, and then print component B on the component A layer to form a component B layer.

[0031] Furthermore, the separate printing is to print component A and component B on the same layer in a dot matrix interlaced manner using different channels of a single nozzle.

[0032] Compared with the prior art, the present invention has at least the following beneficial effects:

[0033] The two-component reactive 3D printing wax material provided by the present invention reduces the melt viscosity of the printing wax material by separating the aromatic dihydroxy compound monomer and the carbonyl compound monomer through the two components, effectively solves the fluidity problem of the traditional polymer polycarbonate in MJP jet printing, and makes the printing process smoother. During the 3D printing process, the two monomers react rapidly under the action of the catalyst to generate polycarbonate with high mechanical strength, high toughness and high resistance to thermal deformation. This polycarbonate combined with other components in the wax material not only improves the overall mechanical properties of the printing mold, but also significantly improves the dimensional accuracy of the mold, meeting the strict requirements of high-precision investment casting.

[0034] The preparation method provided by the present invention ensures the uniformity of the chemical and physical properties of the melt of component A and component B by mixing the raw materials within a specific temperature range, which helps to achieve better reactivity and stability during the printing process. The filtering and cooling steps further ensure the purity and curing quality of the components, avoiding the potential impact of impurities on the printing quality and the performance of the final product. The preparation method has a simple process and a large batch processing capacity, and is suitable for large-scale industrial production.

[0035] The use method provided by the present invention ensures that component A and component B are evenly distributed on the printing platform, and achieves close bonding between layers. It not only improves printing efficiency, but also ensures the mechanical properties and dimensional stability of the printed part through immediate chemical reaction, so that the final 3D printed model has higher precision and durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0037] Figure 1 Component A in Example 1 is printed in the form of a dot matrix;

[0038] Figure 2 Component B in Example 1 is printed in the form of a dot matrix at the same position of component A. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. The components of the embodiments of the present invention described and shown herein can be arranged and designed in various different configurations.

[0040] A first aspect of the present invention provides a two-component reactive 3D printing wax material including component A and component B;

[0041] Wherein, the component A comprises refined paraffin, aromatic dihydroxy compound monomer, catalyst and antioxidant;

[0042] The component B comprises refined paraffin wax, carbonyl compound monomer and antioxidant. The component A and the component B are isolated from each other and do not contact each other before printing.

[0043] The two-component reactive 3D printing wax material provided by the present invention reduces the melt viscosity of the printing wax material by separating the aromatic dihydroxy compound monomer and the carbonyl compound monomer through the two components, effectively solves the fluidity problem of the traditional polymer polycarbonate in MJP jet printing, and makes the printing process smoother. During the 3D printing process, the two monomers react rapidly under the action of the catalyst to generate polycarbonate with high mechanical strength, high toughness and high resistance to thermal deformation. This polycarbonate combined with other components in the wax material not only improves the overall mechanical properties of the printing mold, but also significantly improves the dimensional accuracy of the mold, meeting the strict requirements of high-precision investment casting.

[0044] The present invention adopts a method of printing two components in sequence to effectively achieve the fusion of ink droplets, thereby promoting the occurrence of polymerization reaction. This method involves two different components, which are ejected from the nozzle in sequence during the printing process and quickly fuse after contact. This fusion not only occurs on the surface of the ink droplets, but also because the ink droplets are small in volume (usually between 1-6 picoliters), they have a large specific surface area, which helps to accelerate the mixing and reaction between the components.

[0045] In addition, paraffin wax, as part of the wax material, cools relatively slowly, a property that provides more time for the ink droplets to fuse. This adequate fusion is critical because it allows the monomers to combine more effectively during the polymerization process, ultimately forming a polycarbonate filler. This filler not only enhances the mechanical properties of the wax material, but also forms a composite structure that is particularly useful in multi-nozzle jet printing (MJP) technology because it can improve the accuracy and stability of printed parts.

[0046] Through this two-component printing and fusion technology, the distribution and polymerization reaction of ink droplets can be precisely controlled to produce 3D printed products with specific properties. The application of this method opens up new possibilities for high-precision and functional 3D printing.

[0047] In one embodiment of the present invention, the reaction occurring during the process is as follows:

[0048]

[0049] Polycarbonate is a high-performance thermoplastic, usually produced by melt transesterification of low-viscosity monomers. In the 3D printing process, this reaction can be carried out inside the printing device, avoiding the direct addition of high molecular weight polycarbonate, which would result in excessive viscosity and viscoelasticity of the material system, making it difficult to process wax materials through 3D printing technology.

[0050] Since the monomers have good melt fluidity, they are well compatible with the wax material while maintaining high thermal stability. This property is crucial for the 3D printing process because it ensures the fluidity and reactivity of the material during the printing process. In addition, the melt fluidity and thermal stability of the monomers enable them to undergo a smooth melt transesterification reaction during the printing process after being mixed with the wax material, without affecting the printing quality due to temperature changes or improper reaction conditions.

[0051] The matching of this reaction process with the melt printing process ensures that the monomers can react quickly to form polycarbonate during the printing process, while maintaining the accuracy and strength of the printed parts. In this way, 3D printing technology can produce composite materials that have both the characteristics of wax materials and the excellent properties of polycarbonate, broadening the possibilities of 3D printing in different application fields, such as precision manufacturing, medical devices and the production of high-end consumer products.

[0052] Furthermore, the component A or the component B independently further comprises at least one of a mechanical modifier, liquid paraffin, a tackifying resin, a nucleating agent and a color powder.

[0053] Furthermore, in parts by weight, the component A comprises 50-70 parts of refined paraffin wax, 10-25 parts of aromatic dihydroxy compound monomer, 0.01-0.5 parts of catalyst and 0.01-0.5 parts of antioxidant;

[0054] The component B comprises 50-70 parts of refined paraffin wax, 10-25 parts of carbonyl compound monomer and 0.01-0.5 parts of antioxidant.

[0055] Typically but not limiting, the composition of component A can be calculated in parts by weight as follows: refined paraffin can be 50 parts, 55 parts, 60 parts, 65 parts, 67 parts, 68 parts, 69 parts or 70 parts, or any value within the range of 50-70 parts; the aromatic dihydroxy compound monomer can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts or 25 parts, or any value within the range of 10-25 parts. ; The catalyst can be 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.4 part, 0.45 part or 0.5 part, or any value within the range of 0.01~0.5 part; the antioxidant can also be 0.01 part, 0.02 part, 0.03 part, 0.04 part, 0.05 part, 0.4 part, 0.45 part or 0.5 part, or any value within the range of 0.01~0.5 part.

[0056] Similarly, the composition of component B can also be calculated in parts by weight as follows: refined paraffin can also be 50 parts, 55 parts, 60 parts, 65 parts, 67 parts, 68 parts, 69 parts or 70 parts, or any value within the range of 50-70 parts; the carbonyl compound monomer can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts or 25 parts, or any value within the range of 10-25 parts; the number of parts of the antioxidant can also be 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.4 parts, 0.45 parts or 0.5 parts, or any value within the range of 0.01-0.5 parts.

[0057] Furthermore, in parts by weight, the component A further comprises at least one of 2 to 10 parts of a mechanical modifier, 3 to 10 parts of liquid paraffin, 1 to 5 parts of a tackifying resin, 1 to 3 parts of a nucleating agent, and 0.1 to 0.3 parts of a color powder.

[0058] Furthermore, in parts by weight, the component B further comprises at least one of 2 to 10 parts of a mechanical modifier, 3 to 10 parts of liquid paraffin, 1 to 5 parts of a tackifying resin, 1 to 3 parts of a nucleating agent, and 0.1 to 0.3 parts of a color powder.

[0059] Typically but not limiting, component A may also include at least one of a mechanical modifier, liquid paraffin, a tackifying resin, a nucleating agent and a toner. Specifically, the mechanical modifier may be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or any value within the range of 2 to 10 parts; the liquid paraffin may be 1 part, 2 parts, 3 parts, 4 parts or 5 parts, or any value within the range of 1 to 5 parts; the tackifying resin may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any value within the range of 1 to 5 parts; the nucleating agent may be 1 part, 2 parts, 3 parts, or any value within the range of 1 to 3 parts; the toner may be 0.1 part, 0.2 part, 0.25 part, 0.3 part, or any value within the range of 0.1 to 0.3 parts.

[0060] Component B may also include at least one of a mechanical modifier, liquid paraffin, a tackifying resin, a nucleating agent and a toner. Specifically, the mechanical modifier may be 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or any value within the range of 2 to 10 parts; the liquid paraffin may be 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts, or any value within the range of 3 to 10 parts; the tackifying resin may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any value within the range of 1 to 5 parts; the nucleating agent may be 1 part, 2 parts, 3 parts, or any value within the range of 1 to 3 parts; the toner may be 0.1 part, 0.2 part, 0.25 part, 0.3 part, or any value within the range of 0.1 to 0.3 parts.

[0061] Furthermore, the refined paraffin wax includes at least one of unsaturated hydrocarbon wax, natural plant wax, synthetic wax and low molecular weight polyethylene wax.

[0062] The aromatic dihydroxy compound monomer includes at least one of bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol Z and tetramethyl bisphenol F.

[0063] The catalyst includes at least one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide and tetrabutyl titanate.

[0064] The antioxidant includes a thiol antioxidant.

[0065] The carbonyl compound monomer includes at least one of diphenyl carbonate, bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate and bis(4-nitrophenyl) carbonate.

[0066] Furthermore, the mechanical modifier includes at least one of palm wax, candelilla wax, butadiene styrene copolymer and POE.

[0067] The tackifying resin includes at least one of terpene resin, rosin, rosin derivatives, petroleum resin and modified petroleum resin.

[0068] The nucleating agent includes at least one of microcrystalline wax, ethylene-vinyl acetate copolymer, polyethylene wax, stearic acid and palmitic acid.

[0069] The toner includes at least one of inorganic toner, organic toner, composite pigment, fluorescent pigment and pearlescent pigment.

[0070] The second aspect of the present invention provides a method for preparing the two-component reactive 3D printing wax material, comprising the following steps:

[0071] a. Mix the raw materials in the component A at 150-180° C. to obtain a molten liquid of the component A, and filter and cool to obtain the component A;

[0072] b. Mix the raw materials in the component B at 110-130° C. to obtain a molten liquid of the component B, and filter and cool to obtain the component B.

[0073] The preparation method provided by the present invention ensures the uniformity of the chemical and physical properties of the melt of component A and component B by mixing the raw materials within a specific temperature range, which helps to achieve better reactivity and stability during the printing process. The filtering and cooling steps further ensure the purity and curing quality of the components, avoiding the potential impact of impurities on the printing quality and the performance of the final product. The preparation method has a simple process and a large batch processing capacity, and is suitable for large-scale industrial production.

[0074] The third aspect of the present invention provides a method for using the two-component reactive 3D printing wax material. In a multi-nozzle jet printing process, a nozzle with multiple nozzles is used to print component A and component B respectively. Under heating conditions, component A and component B are fused and reacted to form the layer structure. Finally, the printing platform is moved up and the printing steps are repeated to obtain a model.

[0075] The use method provided by the present invention ensures that component A and component B are evenly distributed on the printing platform, and achieves close bonding between layers. It not only improves printing efficiency, but also ensures the mechanical properties and dimensional stability of the printed part through immediate chemical reaction, so that the final 3D printed model has higher precision and durability.

[0076] It should be noted that equal volumes of component A and component B are mixed, and the corresponding ratios of reactive monomers in component A and component B are adjusted to ensure that the chemical equivalent ratio of the two components during the reaction during the printing process is appropriate, thereby helping to achieve optimal chemical reaction conditions and performance of the final product.

[0077] Furthermore, the separate printing is to use two nozzles to first print component A and then print component B at the same position.

[0078] or,

[0079] The separate printing is to use two nozzles to first print component A in a certain layer to form a continuous component A layer, and then print component B on the component A layer to form a component B layer.

[0080] Furthermore, the separate printing is to print component A and component B on the same layer in a dot matrix interlaced manner using different channels of a single nozzle.

[0081] In the following, some embodiments of the present invention are described in detail in conjunction with the embodiments. In the absence of conflict, the following embodiments and the features in the embodiments can be combined with each other. The raw materials used in the present invention can be obtained by commercial purchase unless otherwise specified.

[0082] The thiol antioxidant used in the following examples and comparative examples is tetrabutylthiuram disulfide, light yellow powder, Hubei Xinghengye Technology Co., Ltd.

[0083] Example 1

[0084] This embodiment provides a two-component reactive 3D printing wax material, and the preparation method is as follows:

[0085] Component A: Take 600g of 90# refined paraffin, 217.5g of bisphenol A monomer, 2.5g of tetrabutylammonium hydroxide, 50g of 95# microcrystalline wax, 50g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 160°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0086] Component B: Take 602.5g of 90# refined paraffin, 217.5g of diphenyl carbonate, 30g of 95# microcrystalline wax, 70g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 120°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0087] Printing method: In the 3D printing process, the model file is first imported into the slicing software of the MJP printer, which is responsible for breaking the model into a series of printable slice files. Next, use the nozzle 1 and nozzle 2 of the MJP printer to print component A and component B respectively.

[0088] like Figure 1 As shown, the nozzle 1 accurately prints component A in the form of a small droplet array on the base plate or the previously printed structure. Figure 2 As shown, nozzle 2 prints small droplets of component B of equal volume at the same position to ensure that the two components can be accurately aligned and fused. In order to achieve more uniform fusion, nozzle 1 will adjust the injection position so that the new component A droplets are interspersed in the previously printed droplet array. Subsequently, nozzle 2 sprays component B at the same position again to ensure that the two components are fully in contact and mixed.

[0089] Under the action of the catalyst, the top layer is infrared heated to 140°C to promote the rapid polymerization of component A and component B to form a composite structure of polycarbonate polymer and wax material. After the polymerization is completed, the infrared heating is turned off to allow the layer to cool and solidify, completing the printing of the layer.

[0090] The printing platform then moves up one layer, repeating the printing and polymerization process to build the model layer by layer. This continuous layer-by-layer printing technology allows complex three-dimensional structures to be accurately manufactured until the entire model is printed.

[0091] Example 2

[0092] This embodiment provides a two-component reactive 3D printing wax material. The difference from Embodiment 1 is that the formula of the two-component reactive 3D printing wax material is the same, and the printing method is as follows:

[0093] In the preparation process of 3D printing model, the model file is first imported into the slicer software of MJP printer, which converts the model into a series of printable slice paths. The printing process involves nozzle 1 and nozzle 2, which are responsible for printing component A and component B respectively.

[0094] Nozzle 1 prints component A on the substrate or the previously printed structure in the form of continuous adjacent contact droplets along a single straight path. Then, nozzle 2 prints component B in the same way on the same straight path, ensuring that it closely overlaps with the droplets of component A to form a continuous straight line. By alternately printing components A and B, a continuous plane is gradually constructed.

[0095] While printing each layer, the catalyst and the top infrared heating system work together to maintain the temperature at 140°C, promoting the chemical reaction and polymerization of components A and B to form a composite structure of polycarbonate polymer and wax material. After the polymerization is completed, the infrared heating is turned off to allow the layer to cool and solidify, completing the printing of the layer.

[0096] The printing platform then moves up to the height of the next layer, and the above printing, polymerization and cooling processes are repeated to build the model layer by layer. This layer-by-layer printing method ensures that each layer can be accurately combined with the next layer until the entire model is printed.

[0097] Example 3

[0098] This embodiment provides a two-component reactive 3D printing wax material. The difference from Embodiment 1 is that the formula of the two-component reactive 3D printing wax material is the same, and the printing method is as follows:

[0099] In the process of preparing the 3D printed model, the model file is first imported into the slicing software of the MJP printer, which is responsible for converting the model into a series of printable slice paths. The printing process involves two nozzles, nozzle 1 is responsible for printing component A, and nozzle 2 is responsible for printing component B.

[0100] When printing starts, nozzle 1 first prints a continuous layer of component A on the base plate to form the initial printing layer. Then, nozzle 2 prints a continuous layer of component B at the same position to ensure that it quickly merges with component A, which has not yet completely cooled. This instant fusion process, with the help of the catalyst and the top infrared heating system raising the temperature to 140°C, promotes the chemical reaction and polymerization of the two components to form a composite structure of polycarbonate polymer and wax material.

[0101] After polymerization is completed, the infrared heating system is turned off to allow the layer to cool and solidify, completing the printing of the current layer. Subsequently, the printing platform moves upward to the height of the new layer, and the above printing, fusion, polymerization and cooling processes are repeated to build the model layer by layer. This continuous stacking printing technology ensures that each layer can be accurately combined with the next layer until the entire model is printed.

[0102] Example 4

[0103] This embodiment provides a two-component reactive 3D printing wax material, and the preparation method is as follows:

[0104] Component A: Take 300g of 95# refined paraffin, 250g of ceresin, 50g of beeswax, 217.5g of bisphenol A monomer, 2.5g of tetrabutylammonium hydroxide, 50g of 85# microcrystalline wax, 50g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 160°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0105] Component B: Take 302.5g of 95# refined paraffin, 250g of ceresin, 50g of beeswax, 217.5g of diphenyl carbonate, 30g of 85# microcrystalline wax, 70g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 130 degrees, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it through a candle filter with a filtration diameter of 3μm, then cool and seal it for storage.

[0106] Printing method: same as in Example 1.

[0107] Example 5

[0108] This embodiment provides a two-component reactive 3D printing wax material, and the preparation method is as follows:

[0109] Component A: Take 600g of 90# refined paraffin, 180g of bisphenol A monomer, 37.5g of bisphenol S monomer, 2.5g of tetramethyl phosphine acetate, 50g of 95# microcrystalline wax, 50g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 160°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0110] Component B: Take 602.5g of 90# refined paraffin, 217.5g of diphenyl carbonate, 30g of 95# microcrystalline wax, 70g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 120°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0111] Printing method: same as in Example 1.

[0112] Example 6

[0113] This embodiment provides a two-component reactive 3D printing wax material, and the preparation method is as follows:

[0114] Component A: Take 700g of 90# refined paraffin, 117.5g of bisphenol A monomer, 2.5g of tetrabutylammonium hydroxide, 50g of 95# microcrystalline wax, 50g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 160°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0115] Component B: Take 702.5g of 90# refined paraffin, 117.5g of diphenyl carbonate, 30g of 95# microcrystalline wax, 70g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 120°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0116] Printing method: same as in Example 1.

[0117] Comparative Example 1

[0118] The comparative example provides a single-component 3D printing wax material. 820 g of 90# refined paraffin wax, 50 g of 95# microcrystalline wax, 50 g of white wax oil, and 5 g of thiol antioxidant are added into a beaker, heated to 160°C, and mechanically stirred evenly. Then, 50 g of hydrogenated rosin resin, 20 g of PE wax, and 5 g of 112 color powder are added, and stirring is continued to be evenly performed to obtain a uniformly dispersed molten liquid. After filtering with a candle filter, the filtration diameter is 3 μm and then the molten liquid is added into a container, and then cooled, sealed, and stored for later use.

[0119] Printing method: Import the 3D printing model file into the MJP printer slicing software to generate a slicing file, use a single nozzle to spray wax droplets to form a continuous liquid surface, allow the wax material to cool naturally, and print layer by layer.

[0120] Comparative Example 2

[0121] The present comparative example provides a single-component 3D printing wax material. 820 g of 85# refined paraffin wax, 50 g of 90# microcrystalline wax, 20 g of ethylene-vinyl acetate copolymer, 30 g of white wax oil, and 5 g of thiol antioxidant are added into a beaker, heated to 160°C, and mechanically stirred evenly. Then, 40 g of hydrogenated rosin resin, 10 g of C5 tackifying resin, 20 g of PE wax, and 5 g of 112 color powder are added, and stirring is continued to be evenly performed to obtain a uniformly dispersed molten liquid. The molten liquid is filtered through a candle filter and added into a container with a filtration diameter of 3 μm, and then cooled, sealed, and stored for later use.

[0122] Printing method: Import the 3D printing model file into the MJP printer slicing software to generate a slicing file, use a single nozzle to spray wax droplets to form a continuous liquid surface, allow the wax material to cool naturally, and print layer by layer.

[0123] Comparative Example 3

[0124] This comparative example provides a single-component 3D printing wax material, which includes 590 g of 90# refined paraffin wax, 230 g of polycarbonate powder particles, 50 g of 95# microcrystalline wax, 50 g of white wax oil, 5 g of thiol antioxidant, 50 g of hydrogenated rosin resin, 20 g of PE wax, and 5 g of 112 color powder. The materials are added into a beaker, heated to 300 degrees, and mechanically stirred to obtain a uniformly dispersed molten liquid with poor fluidity, which cannot be directly printed.

[0125] Comparative Example 4

[0126] This comparative example provides a two-component reactive 3D printing wax material, and the preparation method is as follows:

[0127] Component A: Take 730g of 90# refined paraffin, 117.5g of bisphenol A diglycidyl ether, 70g of 95# microcrystalline wax, and 5g of thiol antioxidant, add into a beaker, heat to 120℃, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0128] Component B: Take 780g of 90# refined paraffin, 40g of diethylenetriamine, 30g of 95# microcrystalline wax, 70g of white wax oil, and 5g of thiol antioxidant, add into a beaker, heat to 120°C, stir mechanically evenly, then add 50g of hydrogenated rosin resin, 20g of PE wax, and 5g of 112 color powder, continue to stir evenly to obtain a uniformly dispersed molten liquid, filter it with a candle filter, and add it into a container with a filtration diameter of 3μm, then cool and seal it for storage.

[0129] Printing method: same as in Example 1.

[0130] Test Example 1

[0131] In the examples and comparative examples, the viscosity of component A and component B is measured respectively, and then the viscosity of component A and component B after reaction is measured. The viscosity of single-component 3D printing wax material is represented by the viscosity of component A.

[0132] The viscosity test instrument is Anton Paar MCR92 rotational viscosity tester. The measurement system uses a flat rotor and the shear rate is 2000s. -1 , the test spacing is 0.1mm.

[0133] The obtained data are shown in Table 1 below.

[0134] Table 1

[0135]

[0136] Test Example 2

[0137] The models printed in the embodiments and comparative examples were subjected to thermogravimetric TGA test.

[0138] The thermogravimetric TGA test instrument is a Mettler TGA2 (SF) thermogravimetric analyzer, with a heating rate of 10°C / min, a maximum temperature of 600°C, and a test sample mass of 20 mg. T0 is the temperature corresponding to the initial sample mass loss of 1%, 350°C is the minimum temperature to ensure that more than 99% of the wax material components are volatilized, and T1 is the temperature when the mass reduction rate of the sample increases to 0.05% / min after the wax material components are volatilized. This temperature is considered to be the starting temperature when the remaining polycarbonate begins to accelerate decomposition. The data obtained are shown in Table 2 below.

[0139] Table 2

[0140]

[0141] The results in Table 2 verify the generation of polycarbonate in the wax material printed by component A and component B. Comparing Example 1 and Comparative Example 1, the sample of Example 1 has an obvious accelerated decomposition stage after T1, while Comparative Example 1 does not decompose at a higher rate after T1, corresponding to the generation of polycarbonate by the two-component printing method of Example 1; Examples 2-6 show the effects of different printing methods, types and contents of reactive monomers on the content of generated polycarbonate. Comparative Example 2 shows the effect of not adding polycarbonate fillers to the wax material on the thermal stability of the sample; Comparative Example 3 shows the effect of directly adding polycarbonate powder particles to the printed wax material on the thermal stability of the final sample performance; Comparative Example 4 shows the effect of adding non-polycarbonate monomers (epoxy resin monomers) to component A and component B on the thermal stability of the components.

[0142] Test Example 3

[0143] Mechanical tests were performed on the models printed in the embodiments and comparative examples, including tests on tensile strength, tensile modulus and deformation size.

[0144] The size of the tensile test strip is 80*10*4mm, the testing instrument is Instron universal testing machine 34TM-10, the tensile rate is 10mm / min; the deformation dimension measuring instrument is an electronic oven and a vernier caliper. The obtained data are shown in Table 3 below.

[0145] Table 3

[0146]

[0147] Table 3 shows the comparison of mechanical properties and thermal deformation resistance of the printed samples of various embodiments and comparative examples. The results of Example 1 show the highest performance improvement, and Examples 2-6 respectively show the effects of different printing methods, types and contents of reactive monomers on the performance improvement to varying degrees. Comparative Example 2 shows the effect of wax material without adding polycarbonate fillers on the mechanical and thermal deformation resistance of the sample; Comparative Example 3 shows the effect of directly adding polycarbonate powder particles to the printed wax material on the thermal stability of the mechanical and thermal deformation resistance of the final sample; Comparative Example 4 shows the effect of adding non-polycarbonate monomers (epoxy resin monomers) to component A and component B on the mechanical and thermal deformation resistance of the components.

[0148] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A two-component reactive 3D printing wax material, characterized in that: Comprising component A and component B; In terms of weight, the component A comprises 50-70 parts of refined paraffin wax, 10-25 parts of aromatic dihydroxy compound monomer, 0.01-0.5 parts of catalyst and 0.01-0.5 parts of antioxidant; The component B comprises 50-70 parts of refined paraffin wax, 10-25 parts of carbonyl compound monomer and 0.01-0.5 parts of antioxidant; The aromatic dihydroxy compound monomer includes at least one of bisphenol A, bisphenol S, bisphenol F, bisphenol AF, bisphenol Z and tetramethyl bisphenol F; The carbonyl compound monomer includes at least one of diphenyl carbonate, bis(4-methylphenyl) carbonate, bis(4-chlorophenyl) carbonate and bis(4-nitrophenyl) carbonate.

2. The two-component reactive 3D printing wax material according to claim 1, characterized in that: The component A or the component B independently further comprises at least one of a mechanical modifier, liquid paraffin, a tackifying resin, a nucleating agent and a toner; The mechanical modifier includes at least one of palm wax, candelilla wax, butadiene styrene copolymer and POE.

3. The two-component reactive 3D printing wax material according to claim 1, characterized in that: In terms of weight, the component A further comprises at least one of 2 to 10 parts of a mechanical modifier, 1 to 5 parts of liquid paraffin, 1 to 5 parts of a tackifying resin, 1 to 3 parts of a nucleating agent, and 0.1 to 0.3 parts of a color powder; The component B further comprises at least one of 2 to 10 parts of a mechanical modifier, 3 to 10 parts of liquid paraffin, 1 to 5 parts of a tackifying resin, 1 to 3 parts of a nucleating agent and 0.1 to 0.3 parts of a color powder.

4. The two-component reactive 3D printing wax material according to any one of claims 1 to 3, characterized in that: The refined paraffin wax includes at least one of unsaturated hydrocarbon wax, natural plant wax and synthetic wax; The catalyst comprises at least one of tetramethylammonium hydroxide, tetrabutylammonium hydroxide and tetrabutyl titanate; The antioxidant includes a thiol antioxidant.

5. The two-component reactive 3D printing wax material according to claim 2 or 3, characterized in that: The tackifying resin includes at least one of terpene resin, rosin, rosin derivatives, petroleum resin and modified petroleum resin; The nucleating agent comprises at least one of microcrystalline wax, ethylene-vinyl acetate copolymer, polyethylene wax, stearic acid and palmitic acid; The toner includes at least one of inorganic toner, organic toner, composite pigment, fluorescent pigment and pearlescent pigment.

6. A method for preparing a two-component reactive 3D printing wax material according to any one of claims 1 to 5, characterized in that: The following steps are involved: a. Mix the raw materials in the component A at 150-180° C. to obtain a molten liquid of the component A, and filter and cool to obtain the component A; b. Mix the raw materials in the component B at 110-130° C. to obtain a molten liquid of the component B, and filter and cool to obtain the component B.

7. A method for using the two-component reactive 3D printing wax material according to any one of claims 1 to 5, characterized in that: In the multi-nozzle jet printing process, a nozzle with multiple nozzles is used to print component A and component B separately. Under heating conditions, component A and component B are fused and reacted to form the layer structure. Finally, the printing platform is moved up to repeat the printing steps to obtain the model.

8. The method of use according to claim 7, characterized in that: The separate printing is to use two nozzles to first print component A and then print component B at the same position; or, The separate printing is to use two nozzles to first print component A in a certain layer to form a continuous component A layer, and then print component B on the component A layer to form a component B layer.

9. The method of use according to claim 7, characterized in that: The separate printing is to use different channels of a single nozzle to print component A and component B on the same layer in a dot matrix interlaced manner.

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