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CN-122010462-A - Ceramic-like photo-curing molding 3D printing material and preparation method thereof, ceramic-like 3D printing part with texture appearance and preparation method thereof

CN122010462ACN 122010462 ACN122010462 ACN 122010462ACN-122010462-A

Abstract

The application relates to the technical field of photo-curing materials, in particular to a ceramic-like photo-curing molding 3D printing material and a preparation method thereof, a ceramic-like appearance 3D printing part and a preparation method thereof. The material comprises a double-oligomer skeleton, a quaternary active diluent combination and composite silicon micropowder which is formed by compounding three silicon micropowder with different specific surface areas according to a specific proportion. According to the scheme, on the premise that the filling amount of the inorganic powder is enough to meet the ceramic-like texture appearance, the prepared slurry can still keep moderate viscosity suitable for printing, excellent storage stability and printing stability at a higher solid content, the obtained green body is high in precision and stiffness, the cured product has the ceramic-like texture appearance, and the cured product is high in heat resistance and rigidity, so that the method is suitable for 3D printing manufacturing of high-precision and high-performance ceramic-like products.

Inventors

  • SHEN WEIQIANG
  • YE ZHIKANG

Assignees

  • 汇橙融创(厦门)新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260211

Claims (10)

  1. 1. The ceramic-like photo-curing molding 3D printing material is characterized by comprising the following components in parts by weight: 9-16 parts of skeleton oligomer; 75-95 parts of diluent combination; 2-5 parts of an initiator; 0.1-1 part of dispersing agent; 180-200 parts of composite silicon micropowder; 0.1-0.5 part of anti-settling agent; Wherein the skeleton oligomer comprises polybutadiene dimethacrylate and polyurethane acrylate, and the mass ratio of the polybutadiene dimethacrylate to the polyurethane acrylate is (8-12): 1-4; The composite silicon micro powder comprises first silicon micro powder, second silicon micro powder and third silicon micro powder with different specific surface areas, wherein the mass ratio of the first silicon micro powder to the second silicon micro powder to the third silicon micro powder is (5.5-6.5): (2.0-3.0): 1, the specific surface area of the first silicon micro powder is 1.2-1.8 m2/g, the specific surface area of the second silicon micro powder is 7.0-9.0 m2/g, and the specific surface area of the third silicon micro powder is 16.0-20.0 m2/g.
  2. 2. The ceramic-like photo-curing 3D printing material according to claim 1, wherein the diluent combination comprises acryloylmorpholine, cyclo-trimethylol propane methylacrylate, tricyclodecane dimethanol diacrylate and pentaerythritol triacrylate.
  3. 3. The ceramic-like photo-curing 3D printing material according to claim 2, wherein the mass ratio of the acryloylmorpholine to the cyclotrimethylol propane methylacrylate to the tricyclodecane dimethanol diacrylate to the pentaerythritol triacrylate is (20-25): (15-20): (35-40): (5-10).
  4. 4. The ceramic-like photo-curing molding 3D printing material according to claim 3, which is characterized by comprising the following components in parts by weight: 8-12 parts of polybutadiene dimethacrylate; 1-4 parts of polyurethane acrylic ester; 20-25 parts of acryloylmorpholine; 15-20 parts of cyclotrimethylolpropane methylal acrylate; 35-40 parts of tricyclodecane dimethanol diacrylate; 5-10 parts of pentaerythritol triacrylate; 2-5 parts of an initiator; 0.1-1 part of dispersing agent; 180-200 parts of composite silicon micropowder; 0.1-0.5 part of anti-settling agent.
  5. 5. The ceramic-like photo-cured molded 3D printing material according to claim 1, wherein: The initiator is TPO; The dispersing agent is BYK-358N; The anti-settling agent is BYK420.
  6. 6. A method for preparing the ceramic-like photo-curing molding 3D printing material according to any one of claims 1 to 5, which is characterized by comprising the following steps: The preparation method comprises the steps of weighing all materials except the composite silicon micro powder according to a formula, stirring and uniformly mixing at 52-58 ℃, and then adding the composite silicon micro powder according to parts at intervals for a certain time, stirring and uniformly mixing.
  7. 7. The method for preparing the ceramic-like photo-curing molding 3D printing material according to claim 6, wherein the method comprises the following steps: weighing all materials except the composite silicon micropowder according to a formula, and stirring at 52-58 ℃ for 1.5-2.5 hours to uniformly mix; Adding the composite silicon micropowder for 1-5 times at intervals of 5-15 min, and stirring and mixing for 0.5-1.5 hours to obtain resin; and pouring the stirred resin into a sealed container, and dispersing at a high speed for 2-8 min to obtain the emulsion type ceramic photocuring molding 3D printing material.
  8. 8. The preparation method of the 3D printing part with the ceramic-like texture appearance is characterized by comprising the following steps of: adding the emulsion type ceramic-like photocuring forming 3D printing material into a trough of photocuring forming 3D printing equipment, and carrying out photocuring 3D printing to obtain a green body; After the photo-curing 3D printing is finished, thermally curing the green body at 75-85 ℃ for 20-40 minutes to obtain the photo-curing 3D printing; The emulsion type ceramic-like photo-curing 3D printing material is prepared by the ceramic-like photo-curing 3D printing material according to any one of claims 1-5, or the emulsion type ceramic-like photo-curing 3D printing material is prepared by the preparation method of the ceramic-like photo-curing 3D printing material according to any one of claims 6-7.
  9. 9. The method for preparing a 3D printed article having a ceramic-like texture appearance according to claim 8, wherein the process parameters of the 3D printing are: the exposure time of the base layer 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 1200-480 ms, and the retention time is 0-50ms.
  10. 10. A3D printed article having a ceramic-like appearance, characterized in that it is produced by the method according to any one of claims 8 to 9.

Description

Ceramic-like photo-curing molding 3D printing material and preparation method thereof, ceramic-like 3D printing part with texture appearance and preparation method thereof Technical Field The application relates to the technical field of photo-curing materials, in particular to a ceramic-like photo-curing molding 3D printing material and a preparation method thereof, a ceramic-like appearance 3D printing part and a preparation method thereof. Background Photo-curing 3D printing technology (such as SLA and DLP) is widely applied in the fields of prototype verification, personalized customization and end product manufacturing due to the advantages of high precision, high surface quality and complex structure manufacturing. The traditional light-cured material is mainly a resin system, the traditional molding material used in the three-dimensional light-cured molding technology such as SLA and DLP is photosensitive resin, and the photosensitive resin has the advantages of high curing speed, no need of heating, material saving and the like. However, when the ceramic-like appearance product is prepared, the product prepared from the traditional photosensitive resin has obvious differences in mechanical strength, heat resistance and texture from the traditional ceramic product, and the direct application of the product in the end product requiring high-performance and high-texture ceramic appearance is limited. Some photosensitive resins applied to the preparation of ceramic-like texture appearance have defects of cracks, material sedimentation and the like in printed finished products. In order to impart excellent ceramic-like properties and appearance to the photo-cured articles, a technical route of adding a large amount of inorganic ceramic powder (such as silica micropowder, alumina, etc.) to the photosensitive resin is widely adopted in the industry. The high proportion of inorganic filler can obviously improve the hardness, modulus, heat resistance and wear resistance of the product, and the surface of the product presents the luster and texture similar to ceramics. However, with a significant increase in the inorganic powder content (solids content), a serious series of technical challenges are also created: first, high solids content contradicts low viscosity. To meet the demanding requirements of the photo-curing printing equipment for slurry flowability and paving uniformity, the printing material must maintain a low suitable viscosity. However, the addition of a large amount of inorganic powder can sharply increase the viscosity of the system, so that the fluidity of the slurry is poor, the slurry is difficult to quickly level in the printing process, and even the printing operation cannot be normally performed. Secondly, the sedimentation of the powder and the stability of the system are problems. The inorganic powder and the organic resin have density and compatibility difference, so that sedimentation and delamination are easy to occur under high solid content, and uniformity of the slurry is lost during printing or storage. This not only affects the interlayer bonding and dimensional accuracy of the printed article, but also results in uneven density, severe sedimentation, reduced performance, and even print failure in the final article. Furthermore, there is a balance of cure shrinkage, green strength and final properties. High filled systems still suffer from volume shrinkage during photocuring, and improper shrinkage can lead to green body deformation, cracking or loss of dimensional accuracy. At the same time, the green body needs to be sufficiently "stiff" to support the subsequent release, cleaning and post-treatment processes. In addition, the interfacial bond strength between the resin matrix and the bulk powder directly affects the mechanical properties of the final part. How to design a resin system, while ensuring low shrinkage and high green strength, to achieve firm bonding with powder, thereby obtaining high heat resistance and high strength final performance is a complex systematic problem. Therefore, a photocuring 3D printing material and a photocuring 3D printing method capable of meeting the following requirements are needed in the market, wherein on the premise that the filling amount of inorganic powder is enough to meet the ceramic-like texture appearance, the slurry can still keep excellent long-term storage stability and proper printing viscosity, the size precision of a printed green body is high, the shape retention property is good (high stiffness), and finally a cured product can truly have the ceramic-like appearance texture, high heat resistance and high rigidity, so that the photocuring 3D printing material and the photocuring 3D printing method have important significance for overcoming the technical obstacle that the high-performance ceramic-like appearance product is limited to be manufactured with low cost, high efficiency and high quality through the photocuring