Ceramic-like photocuring molding 3D printing material and preparation method thereof, and ceramic-like texture appearance 3D printed part and preparation method thereof

Abstract

The invention relates to the technical field of photocuring materials, in particular to a ceramic-like photocuring molding 3D printing material and a preparation method thereof, and a ceramic-like texture appearance 3D printed part and a preparation method thereof. The material comprises a double-oligomer skeleton, a quaternary reactive diluent composition and composite silica powder compounded by three silica powder with different specific surface areas according to a specific proportion, wherein the double-oligomer skeleton and the quaternary reactive diluent composition are in a specific proportion. According to the scheme, on the premise that the sufficient filling amount of the inorganic powder meets the ceramic-like texture appearance, the prepared slurry can still keep the moderate viscosity suitable for printing and excellent storage stability and printing stability when the solid content is high, an obtained green body is high in precision and good in stiffness, and a part obtained after curing has the ceramic-like texture appearance; and the 3D printing material is high in heat resistance and rigidity, and is suitable for 3D printing manufacturing of high-precision and high-performance ceramic workpieces.

Description

Technical Field

[0001] This application relates to the field of photocurable materials technology, and in particular to ceramic-like photocurable 3D printing materials and their preparation methods, as well as 3D printed parts with ceramic-like textures and their preparation methods. Background Technology

[0002] Photopolymer 3D printing technologies (such as SLA and DLP) have been widely used in prototype verification, personalized customization, and end-product manufacturing due to their advantages of high precision, high surface quality, and ability to manufacture complex structures.

[0003] Traditional photocurable materials are primarily resin-based. Stereoscopic printing technologies such as SLA and DLP use photosensitive resins as the traditional molding material. Photosensitive resins offer advantages such as fast curing speed, no need for heating, and material savings. However, when fabricating ceramic-like textured parts, traditional photosensitive resins produce parts with significantly lower mechanical strength, heat resistance, and texture compared to traditional ceramic products, limiting their direct application in end products requiring high-performance, high-quality ceramic appearances. Some photosensitive resins used for fabricating ceramic-like textures also exhibit defects such as cracks and material settling in the printed products.

[0004] To impart ceramic-like properties and appearance to photocured parts, the industry commonly employs a technique of adding a large amount of inorganic ceramic powder (such as silica fume, alumina, etc.) to the photosensitive resin. A high proportion of inorganic fillers can significantly improve the hardness, modulus, heat resistance, and wear resistance of the parts, and give their surface a ceramic-like gloss and texture. However, with the significant increase in the inorganic powder content (solid content), a series of serious technical challenges also arise: First, there's the contradiction between high solids content and low viscosity. To meet the stringent requirements of photopolymer printing equipment for slurry flowability and uniform spreading, the printing material must maintain a suitable low viscosity. However, the addition of a large amount of inorganic powder will drastically increase the system viscosity, leading to poor slurry flowability, difficulty in quickly leveling during the printing process, and even preventing normal printing operations.

[0005] Secondly, there are issues related to powder sedimentation and system stability. Differences in density and compatibility exist between inorganic powders and organic resins, making them highly susceptible to sedimentation and stratification at high solids content. This leads to a loss of uniformity in the slurry during printing or storage. This not only affects the interlayer bonding and dimensional accuracy of the printed parts but also results in uneven density, severe sedimentation, performance degradation, and even printing failure in the final product.

[0006] Furthermore, there is the challenge of balancing curing shrinkage, green strength, and final properties. High-filler systems still experience volume shrinkage during photopolymerization; improper shrinkage can lead to green deformation, cracking, or loss of dimensional accuracy. Simultaneously, the green body needs sufficient rigidity to support subsequent release, cleaning, and post-processing. In addition, the interfacial bonding strength between the resin matrix and the large amount of powder directly affects the mechanical properties of the final part. Designing a resin system that ensures low shrinkage, high green strength, and a strong bond with the powder to achieve high heat resistance and high strength is a complex systemic problem.

[0007] Therefore, there is an urgent need in the market for a photopolymer 3D printing material and method that can simultaneously meet the following requirements: while ensuring sufficient inorganic powder filling to achieve a ceramic-like texture appearance, the slurry can still maintain excellent long-term storage stability and suitable printing viscosity; the printed green body has high dimensional accuracy and good shape retention (high rigidity); and the final cured part can truly possess a ceramic-like appearance, high heat resistance, and high rigidity. This is of great significance for overcoming the technical obstacles that restrict the low-cost, high-efficiency, and high-quality manufacturing of high-performance ceramic-like texture products through photopolymer 3D printing technology. Summary of the Invention

[0008] To address the problems of the prior art mentioned in the background section, this application provides a ceramic-like photopolymerization 3D printing material, the technical solution of which is as follows: This application provides a ceramic-like photopolymerizable 3D printing material, which, by weight, comprises the following components: 9-16 parts of skeletal oligomers; Diluent combination: 75-95 parts; 2-5 parts of initiator; Dispersant 0.1-1 part; 180-200 parts of composite silicon micro powder; 0.1-0.5 parts of anti-settling agent; The skeleton oligomer includes polybutadiene dimethacrylate and polyurethane acrylate; the mass ratio of polybutadiene dimethacrylate to polyurethane acrylate is (8-12):(1-4). The composite silicon micropowder comprises a first silicon micropowder, a second silicon micropowder, and a third silicon micropowder with different specific surface areas; the mass ratio of the first silicon micropowder, the second silicon micropowder, and the third silicon micropowder is (5.5-6.5):(2.0-3.0):1; the specific surface area of ​​the first silicon micropowder is 1.2-1.8 m² / g, the specific surface area of ​​the second silicon micropowder is 7.0-9.0 m² / g, and the specific surface area of ​​the third silicon micropowder is 16.0-20.0 m² / g.

[0009] In some embodiments, the diluent combination includes acrylamide morpholine, cyclotrimethylolpropane methyl acetal acrylate, tricyclodecanediethanol diacrylate, and pentaerythritol triacrylate.

[0010] In some embodiments, the mass ratio of acryloylmorpholine, cyclotrimethylolpropane methyl acetal acrylate, tricyclodecanediethanol diacrylate and pentaerythritol triacrylate is (20-25):(15-20):(35-40):(5-10).

[0011] In some embodiments, it comprises the following components by weight: 8-12 parts of polybutadiene dimethacrylate; 1-4 parts of polyurethane acrylate; 20-25 parts of the acryloylmorpholine; 15-20 parts of cyclotrimethylolpropane methyl acetal acrylate; 35-40 parts of tricyclodecanediethanol diacrylate; 5-10 parts of pentaerythritol triacrylate; 2-5 parts of initiator; Dispersant 0.1-1 part; 180-200 parts of composite silicon micro powder; 0.1-0.5 parts of anti-settling agent.

[0012] In some embodiments, the initiator is TPO.

[0013] In some embodiments, the dispersant is BYK-358N.

[0014] In some embodiments, the anti-settling agent is BYK420.

[0015] This application also provides a method for preparing the ceramic-like photopolymerizable 3D printing material as described above, which includes the following steps: Preparation of emulsion: Weigh all materials except composite silicon micro powder according to the formula, and stir and mix them evenly at 52-58℃; then add composite silicon micro powder in portions at certain intervals and stir and mix evenly.

[0016] In some embodiments, according to the formula, all materials except composite silicon micro powder are weighed and stirred at 52-58°C for 1.5-2.5 hours to mix evenly; then, composite silicon micro powder is added in portions at certain intervals and stirred evenly; then, composite silicon micro powder is added in 1-5 portions at 5-15 minutes intervals and stirred for 0.5-1.5 hours to obtain resin; then, the stirred resin is poured into a sealed container and dispersed at high speed for 2-8 minutes to obtain emulsion-type ceramic photocurable 3D printing material.

[0017] This application also provides a method for preparing a 3D printed part with a ceramic-like texture, which includes the following steps: adding the above-mentioned emulsion-type ceramic photopolymerization 3D printing material into the material tank of a photopolymerization 3D printing equipment, performing photopolymerization 3D printing to obtain a green body; after the photopolymerization 3D printing is completed, the green body is heat-cured at 75-85℃ for 20-40 minutes to obtain the final product. In some embodiments, the 3D printing process parameters are as follows: substrate exposure time 7500-8500ms, illumination time 4200-4800ms, release distance 4-6mm, release speed 0.5-1.5mm / s, lifting distance 4-6mm, lifting speed 3-4mm / s, illumination intensity ratio 30-50%, hovering time 1200-1800ms, and residence time 0-50ms.

[0018] This application also provides a 3D printed part with a ceramic-like texture, which is prepared by the method described above.

[0019] Compared with existing technologies, the solution proposed in this application has the following technical advantages: By combining a synergistic resin design of "dual oligomer framework and quaternary diluent" with a precision filler system of "tertiary specific surface area compounded silica micropowder," the technical barriers of high ceramic content photocurable materials are overcome. While ensuring sufficient inorganic powder filling to achieve a ceramic-like texture, the prepared slurry maintains a suitable viscosity for printing and excellent storage stability even at high solids content. It possesses excellent printability, producing green bodies with high dimensional accuracy and stiffness, directly achieving a ceramic-like texture. After post-curing, the parts exhibit ceramic-like physicochemical properties: combining a ceramic-like appearance, high heat resistance, and high rigidity. This application achieves a balance of high filling, high precision, and high performance without relying on complex additives or expensive equipment, providing a practical solution for low-cost, high-efficiency photocurable 3D printing of complex ceramic-like structures. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be described clearly and completely below. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0021] To verify the effectiveness of the proposed solution, the following embodiments and comparative examples are also provided: The formulations (unit: parts by weight) of the embodiments and comparative examples provided in this application are shown in Table 1 below: Table 1

[0022] Table 2

[0023] In Example 1, 200 parts of the composite silicon micropowder were used. It was composed of three silicon micropowders (ceramic powders) with different surface areas. The specific surface areas of the first silicon micropowder L, the second silicon micropowder M, and the third silicon micropowder H were 1.2-1.8 m² / g, 7.0-9.0 m² / g, and 16.0-20.0 m² / g, respectively. The ratio of L:M:H was 6:2.5:1 (mass ratio), and the total specific surface area of ​​the powder was approximately 4.5 m² / g.

[0024] Table 3

[0025] The molecular weight ranges of the polybutadiene dimethacrylate and polyurethane acrylate are 4800-5500 and 4400-5100, respectively.

[0026] The preparation process of the ceramic-like photopolymer 3D printing material emulsion and the ceramic-like textured 3D printed parts in the above embodiments and comparative examples is as follows: Preparation of emulsion: According to the formula, weigh all materials except composite silicon powder, and stir at 1000 rpm for 2 hours at 55℃ to mix evenly; then add composite silicon powder in 3 batches at 10-minute intervals, and stir for 1 hour to obtain resin; then pour the stirred resin into a sealed container, disperse it with a high-speed disperser (1500 rpm) for 5 minutes to obtain emulsion-type ceramic photocurable 3D printing material.

[0027] Printed parts: Add emulsion-type ceramic photopolymer 3D printing material into the material tank of the photopolymer 3D printing equipment, perform photopolymer 3D printing to obtain a green body; after the photopolymer 3D printing is completed, heat cure the green body at 80℃ for 30 minutes to obtain the final product.

[0028] The 3D printing equipment used was DLP, and the process parameters for 3D printing were as follows: base layer exposure time 8000ms, light exposure time 4500ms, release distance 5mm, release speed 1mm / s, lifting distance 5mm, lifting speed 3.5mm / s, light intensity ratio 40%, hovering time 1500ms, and residence time 0ms.

[0029] The model parameters are: cross shape, model slice layer thickness of 0.05mm, and a total of 3 parallel model parts are made.

[0030] The products obtained in the examples and comparative examples were tested for relevant performance indicators under the same test conditions. The test results are shown in the table below: Table 4

[0031] The illuminance ratio (in %) refers to the proportion of the set working illuminance (in mW / cm²) to the rated illuminance (in mW / cm²) of the equipment. The illuminance of a small desktop DLP photopolymerization 3D printer is usually 1000-2000 mW / cm².

[0032] Table 5

[0033] In the table, "-" indicates that no test was conducted. Stiffness refers to its overall shape being firm, not floppy, and without structural sagging.

[0034] The ceramic-like texture refers to a hard texture with a matte, frosted surface, similar to the appearance of pottery.

[0035] Table 6

[0036] The test methods or standards are as follows: The standard for testing tensile strength is ISO 527; The standard for bending strength testing is ISO 178; The standard for notched impact strength testing of simply supported beams is ISO 179-1; The standard for testing heat distortion temperature under load is ASTM D648@0.455mPa; The aging test was performed using a heating-accelerated aging method.

[0037] The following comparative examples illustrate the changes made to the machining parameters of the parts. Table 7

[0038] Analysis of the performance test data of the above comparative examples and embodiments: 1. Overall advantages of Example 1 Example 1 represents the optimal technical solution of the present invention, which achieves the best balance in material preparation, printing process and final part performance, and its comprehensive advantages are reflected in: Excellent slurry processability: The initial viscosity (2350 cP) is moderate, combining good flowability and anti-settling properties (no hard sedimentation after 5 hours of standing). This ensures stable and uniform slurry spreading even with high solids content (200 parts silica powder), laying the foundation for high-precision printing.

[0039] Excellent printability: The printing process was smooth, and the resulting green body was "tall, precise, and had a ceramic-like appearance." The dimensional accuracy was extremely high (error ≤ 0.01mm for 50mm pieces), indicating good control of material curing shrinkage.

[0040] The final performance is excellent: the sintered part exhibits ceramic-like mechanical and thermal properties. The load heat distortion temperature reaches 151℃, the flexural strength reaches 58 MPa, the flexural modulus reaches 15546 MPa, and it also possesses toughness (notched impact 29 J / m). These figures show significant advantages compared to the comparative model.

[0041] Good system stability: Aging tests showed only slight sedimentation and no pre-curing, indicating that the material has good storage stability.

[0042] In summary, Example 1 successfully integrates high filler content, excellent printability, high dimensional accuracy, and superior ceramic-like mechanical properties, achieving the core objective of this application.

[0043] 2. Analysis of proportional variables and test results Each pair of examples, through the principle of a single variable, reversely verified the necessity of each technical feature of this application.

[0044] (1) Optimization of diluent combination ratio (comparative examples 1-4): These comparative examples demonstrate that specific diluent combinations and ratios are key to achieving performance balance.

[0045] Comparative Example 1 (lower acrylomorpholine content): The reduction in diluent ACMO led to a decrease in the crosslinking density and toughness of the system. The final performance disadvantages were a significant decrease in the load heat distortion temperature (143.3℃), flexural strength (51.2 MPa), and impact toughness (18.9 J / m).

[0046] Comparative Example 2 (lower CTFA): Reduced CTFA diluent affects rheological and curing efficiency. Final performance disadvantages: All mechanical properties (flexural, tensile, impact) deteriorate, and the heat distortion temperature (138.1℃) decreases significantly.

[0047] Comparative Example 3 (lower tricyclodecanediethanol diacrylate): The reduction in the main rigid diluent affects the strength of the skeleton. Ultimately, the performance is inferior: the load heat distortion temperature (126.5℃) and flexural properties are significantly reduced, and the material rigidity (flexural modulus 11575) is severely insufficient.

[0048] Comparative Example 4 (lower pentaerythritol triacrylate): The reduction of the high-functionality diluent pentaerythritol triacrylate affects the crosslinking density. Final performance disadvantage: Although its heat distortion temperature increases slightly, the material toughness (notched impact 15.6 J / m) is significantly sacrificed, indicating that it is crucial for balancing hardness and toughness.

[0049] (2) Optimization of silicon micro powder system (Comparative Example 5-1, Comparative Example 5-2, Comparative Example 6, Comparative Example 7-1, Comparative Example 7-2) These comparative examples demonstrate that the three-stage compound silicon micropowder system and its specific content and ratio are the core technologies.

[0050] Comparative Example 5-1 (insufficient total amount of silica powder): Reduced solid content. Ultimate performance disadvantages: Low slurry viscosity (1587 cP), green body is "soft and easily deformed", and the mechanical properties (such as bending strength 47.5 MPa, heat deformation 78℃) and dimensional accuracy (error 0.5 mm) of the final part are severely degraded, losing its ceramic-like characteristics.

[0051] Comparative Example 5-2 (Excessive Total Silica Powder): Excessive solid content. Final performance disadvantage: Excessively high slurry viscosity (5690 cP), "poor flowability, almost impossible to print normally".

[0052] Comparative Example 6 (Single Specific Surface Area Silica Powder): Silica powder gradation was eliminated. Final performance disadvantages: The slurry "sedimented relatively quickly," resulting in uneven density of the printed green body, leading to a significant and comprehensive deterioration in final performance (flexural strength 23 MPa, heat distortion 54℃), proving that the three-stage compounding is irreplaceable for the close packing of powders and the stability of the slurry.

[0053] Comparative Examples 7-1 and 7-2 (improper three-stage mixing ratio): Changing the L:M:H ratio resulted in an unsuitable total specific surface area. Final performance disadvantages: Comparative Example 7-1 (8:1:1, too low specific surface area): rapid slurry settling, uneven printed layer thickness, and poor mechanical properties. Comparative Example 7-2 (1:1:1, too high specific surface area): uneven slurry dispersion, prone to clumping, unable to print stably, and poor performance. This demonstrates that the specific ratio of 6:2.5:1 is key to achieving the optimal total specific surface area of ​​4.5 m² / g, thereby balancing viscosity, stability, and final performance.

[0054] (3) Key components missing or replaced (Comparative Example 8, Comparative Example 9, Comparative Example 10, Comparative Example 11) These comparative examples demonstrate the indispensability of certain chemical components.

[0055] Comparative Example 8 (without polyurethane acrylate): Only polybutadiene dimethacrylate was used. Final performance disadvantages: insufficient green stiffness; a sharp drop in heat distortion temperature (84°C) and mechanical properties (flexural strength 35 MPa) after curing, demonstrating the synergistic effect of the dual oligomers in providing green strength and final rigidity and toughness.

[0056] Comparative Example 9 (acryloylmorpholine ACMO removed, its parts added evenly to cyclotrimethylolpropane methyl acetal acrylate CTFA / pentaerythritol triacrylate): Disruption of functional balance. Final performance disadvantages: poor slurry stability, rapid settling, and brittle printed green bodies with microcracks, demonstrating that ACMO is crucial for regulating reactivity, reducing shrinkage stress, and improving slurry compatibility.

[0057] Comparative Example 10 (replacing the chemical structure of the key diluent): Disadvantages in final performance: Although the slurry was initially uniform, "phase separation" occurred, resulting in poor surface quality of the green body and a significant decrease in final thermal properties and strength, demonstrating that the chemical structure of a specific diluent makes a unique contribution to compatibility, volume shrinkage, and final performance.

[0058] Comparative Example 11 (without anti-settling agent BYK420): Final performance disadvantage: The slurry "severely settled, with the upper part clear and the lower part hard after 1.5 hours", which completely failed to guarantee the consistency of the printing process, proving that in a high solids content system, anti-settling agent is a necessary auxiliary agent to maintain process stability.

[0059] (4) Optimization of process parameters (Comparative Example 12, Comparative Example 13) These comparative examples demonstrate that the supporting process parameters are part of the technical solution.

[0060] Comparative Example 12 (overexposure): Final performance disadvantage: Printing failed directly ("severe overexposure at the bottom, difficult to remove parts"), proving that the optimized exposure parameters and material formulation in the example are the prerequisites for obtaining accurate curing and good release.

[0061] Comparative Example 13 (Insufficient thermosetting temperature): Disadvantages: Although the green body has a good appearance, the post-curing is insufficient, resulting in the final part performance (heat distortion 93°C, flexural strength 43 MPa) being far below the level of the example. This proves that the 80°C / 30min thermosetting process is essential for sufficient curing and improving the crosslinking network strength to obtain ceramic-like properties.

[0062] 3. Summary The superiority of Example 1 does not stem from a single component, but rather from a synergistic system resulting from the combined effects of the design of component types, proportions, and other factors: The combination of dual oligomers and a specific quaternary diluent creates an organic matrix with moderate reactivity, controllable shrinkage, and the ability to support high filler content. A three-tiered silica powder system (with a specific surface area and a 6:2.5:1 ratio) achieves the densest powder packing, imparting excellent rheological properties, stability, and high ceramic content to the slurry. Specialized additives (dispersants and anti-settling agents) ensure the long-term uniformity and stability of the high-solids-content suspension system. Matched printing and post-processing parameters ensure accurate and reliable conversion from digital models to high-performance ceramic-like parts.

[0063] The results of all comparative examples show that deviations from any element in the above system will cause a chain reaction of significant deterioration in slurry stability, printing process window, green quality, or final part performance.

[0064] In summary, the proposed solution includes at least the following design concepts and technical effects: I. Design Highlights and Concepts The core design concept of this application lies in constructing a multi-component, multi-scale synergistic composite material system and matching it with optimized process parameters to achieve the fabrication of ceramic-like parts with both excellent printability and good final performance on a conventional photopolymerization printing platform. Specific design highlights are as follows: Synergistic design of organic matrix systems: Dual oligomer skeleton: A specific ratio of polybutadiene dimethacrylate and polyurethane acrylate is used to ensure dimensional stability and mechanical property balance from liquid slurry to green body and then to final part.

[0065] A specific combination of diluents with specific functions and structures: A quaternary diluent system composed of acryloylmorpholine (ACMO), cyclotrimethylolpropane methyl acetal acrylate (CTFA), tricyclodecanediethanol diacrylate, and pentaerythritol triacrylate was carefully selected and its ratio optimized. This combination achieves a reasonable distribution of functions (monofunctional, difunctional, and multifunctional), comprehensively controlling the slurry viscosity, curing rate, shrinkage stress, and crosslinking density of the cured network.

[0066] Grading and interface optimization of inorganic fillers: A three-component specific surface area synergistic compounding system is formulated by compounding three types of silica powder with different specific surface areas (low, medium, and high) in a specific mass ratio ((5.5-6.5):(2.0-3.0):1). This design effectively controls the balance of slurry properties such as viscosity and thixotropy, and improves the sedimentation stability problem of high solids content slurries.

[0067] Application of special additives: The use of high-efficiency dispersants (such as BYK-358N) and anti-settling agents (such as BYK420) further enhances the uniform dispersion and long-term suspension stability of powder in the resin matrix, ensuring the uniformity and repeatability of the printing process.

[0068] Optimized photocuring and thermocuring parameters: These provide printing parameters (such as specific exposure times and release speeds) that are highly matched to the material system, as well as the essential post-thermal curing step (80°C / 30 min). This process combination ensures high-precision, high-rigidity molding of the green body and promotes complete curing of the resin matrix, thereby significantly improving the final overall performance of the material.

[0069] II. Beneficial Effects Based on the above design, the solution of this application achieves the following significant and beneficial technical effects: Excellent slurry processability: The prepared printing material maintains moderate viscosity (approximately 2350 cP) and excellent stability (no hard sedimentation after standing for 5 hours) even at a solid content of up to approximately 65 wt%. It has good flowability and thixotropy, making it very suitable for continuous and stable operation of desktop photopolymerization printing equipment.

[0070] Excellent printability: Under optimized parameters, the material cures quickly and has low curing shrinkage, resulting in green body with high dimensional accuracy (error ≤ 0.01mm for 50mm calibration parts), good shape retention (high rigidity), and excellent surface quality, allowing direct acquisition of ceramic-like textured appearance prototypes.

[0071] Excellent final part performance: After post-curing, the parts exhibit ceramic-like physical and chemical properties. High heat resistance: The heat distortion temperature under load reaches above 151℃.

[0072] High rigidity and strength: bending strength can reach 58 MPa, and bending modulus can reach over 15,500 MPa.

[0073] Excellent overall balance and practicality: This solution successfully breaks the contradiction between the poor printability of high-fill slurry and the need for high filler in high-performance ceramic parts. Without over-reliance on expensive raw materials or special equipment, it achieves a balance between printing accuracy, green strength, good ceramic-like texture and appearance, final performance and cost, providing a practical solution for the low-cost and high-efficiency manufacturing of complex structures and personalized ceramic-like products.

[0074] In summary, this application provides a comprehensive ceramic-like photopolymer 3D printing technology solution with excellent overall performance and easy to promote and apply through a whole-chain design of material formulation, structural design and process control.

[0075] It should be noted that: In summary, the specific parameters or some commonly used reagents or raw materials in the above embodiments are specific or preferred embodiments under the concept of this application, and not limitations thereof; those skilled in the art can make adaptive adjustments within the concept and protection scope of this application.

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A ceramic-like photopolymerizable 3D printing material, characterized in that, By weight, it includes the following components: 9-16 parts of skeletal oligomers; Diluent combination: 75-95 parts; 2-5 parts of initiator; Dispersant 0.1-1 part; 180-200 parts of composite silicon micro powder; 0.1-0.5 parts of anti-settling agent; The skeleton oligomer includes polybutadiene dimethacrylate and polyurethane acrylate; the mass ratio of polybutadiene dimethacrylate to polyurethane acrylate is (8-12):(1-4). The composite silicon micropowder comprises a first silicon micropowder, a second silicon micropowder, and a third silicon micropowder with different specific surface areas; the mass ratio of the first silicon micropowder, the second silicon micropowder, and the third silicon micropowder is (5.5-6.5):(2.0-3.0):1; the specific surface area of ​​the first silicon micropowder is 1.2-1.8 m² / g, the specific surface area of ​​the second silicon micropowder is 7.0-9.0 m² / g, and the specific surface area of ​​the third silicon micropowder is 16.0-20.0 m² / g.

2. The ceramic-like photopolymerizable 3D printing material according to claim 1, characterized in that: The diluent combination includes acrylamide, cyclotrimethylolpropane methyl acetal acrylate, tricyclodecanediethanol diacrylate, and pentaerythritol triacrylate.

3. The ceramic-like photopolymerizable 3D printing material according to claim 2, characterized in that: The mass ratio of acryloylmorpholine, cyclotrimethylolpropane methyl acetal acrylate, tricyclodecanediethanol diacrylate and pentaerythritol triacrylate is (20-25):(15-20):(35-40):(5-10).

4. The ceramic-like photopolymerizable 3D printing material according to claim 3, characterized in that: By weight, it includes the following components: 8-12 parts of polybutadiene dimethacrylate; 1-4 parts of polyurethane acrylate; 20-25 parts of the acryloylmorpholine; 15-20 parts of cyclotrimethylolpropane methyl acetal acrylate; 35-40 parts of tricyclodecanediethanol diacrylate; 5-10 parts of pentaerythritol triacrylate; 2-5 parts of initiator; Dispersant 0.1-1 part; 180-200 parts of composite silicon micro powder; 0.1-0.5 parts of anti-settling agent.

5. The ceramic-like photopolymerizable 3D printing material according to claim 1, characterized in that: The initiator is TPO; The dispersant is BYK-358N; The anti-settling agent is BYK420.

6. A method for preparing a ceramic-like photopolymerizable 3D printing material as described in any one of claims 1-5, characterized in that: Includes the following steps: Preparation of emulsion: Weigh all materials except composite silicon micro powder according to the formula, and stir and mix them evenly at 52-58℃; then add composite silicon micro powder in portions at certain intervals and stir and mix evenly.

7. The method for preparing the ceramic-like photopolymerizable 3D printing material according to claim 6, characterized in that: According to the formula, weigh all materials except composite silicon micro powder, and stir at 52-58℃ for 1.5-2.5 hours to mix evenly; Then, the composite silica powder is added in 1 to 5 batches at 5 to 15-minute intervals, and the mixture is stirred for 0.5 to 1.5 hours to obtain the resin. The stirred resin is then poured into a sealed container and dispersed at high speed for 2-8 minutes to obtain an emulsion-type ceramic photocurable 3D printing material.

8. A method for preparing a 3D printed part with a ceramic-like texture, characterized in that: Includes the following steps: Emulsion-type ceramic photopolymerization 3D printing material is added to the material tank of a photopolymerization 3D printing equipment and photopolymerization 3D printing is performed to obtain a green body. After photopolymer 3D printing is completed, the green body is heat-cured at 75-85℃ for 20-40 minutes to obtain the final product. The emulsion-type ceramic photopolymerization 3D printing material is the ceramic photopolymerization 3D printing material as described in any one of claims 1-5; or the emulsion-type ceramic photopolymerization 3D printing material is prepared by the method for preparing the ceramic photopolymerization 3D printing material as described in any one of claims 6-7.

9. The method for preparing a 3D-printed part with a ceramic-like textured appearance according to claim 8, characterized in that, The 3D printing process parameters are as follows: The exposure time for the substrate is 7500–8500 ms, the illumination time is 4200–4800 ms, the release distance is 4–6 mm, the release speed is 0.5–1.5 mm / s, the lifting distance is 4–6 mm, the lifting speed is 3–4 mm / s, the illumination intensity ratio is 30–50%, the hovering time is 1200–1800 ms, and the dwell time is 0–50 ms.

10. A 3D-printed part with a ceramic-like texture, characterized in that: It is prepared by the preparation method described in any one of claims 8-9.

Images