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CN-122011777-A - 3D printing pad based on organic silicon and preparation method thereof

CN122011777ACN 122011777 ACN122011777 ACN 122011777ACN-122011777-A

Abstract

The invention relates to the technical field of organosilicon materials and 3D printing composite, in particular to an organosilicon-based 3D printing pad material and a preparation method thereof. The 3D printing pad based on the organic silicon is obtained by extruding an organic silicon composition through a 3D printer to form a precursor of a hollowed-out pattern, and curing the precursor under a heating condition. The invention obviously improves the maximum unsupported cantilever length in the printing process by designing the system formula. The excellent performance of the silica gel pad is guaranteed, the degree of freedom of structural design is expanded, the steps of supporting materials and post-treatment are reduced, and finally, the solution with high efficiency, low cost and high reliability is realized.

Inventors

  • JIANG SHAN
  • JIA LIYA
  • LI PEI
  • SUN DAGUI
  • CHEN HONG
  • JIANG GUOXIN
  • CHEN CHEN
  • QI PENG

Assignees

  • 埃肯有机硅（上海）有限公司
  • 金茂璞逸品居(上海)科技有限公司

Dates

Publication Date
20260512
Application Date
20260212

Claims (10)

  1. 1. The 3D printing pad based on the organic silicon is characterized in that a precursor of a hollowed-out pattern is formed by extruding an organic silicon composition through a 3D printer, the precursor is cured under a heating condition, and the organic silicon composition comprises the following raw materials in parts by mass: 50-80 parts of vinyl-terminated polydimethylsiloxane, 0.3-10 Parts of hydrogen-containing silicone oil, 20-40 Parts of gas-phase white carbon black, 0.001 To 0.1 part of platinum catalyst, 0-0.1 Part of an inhibitor, and 0.2-5 Parts of thixotropic agent; Wherein the viscosity of the vinyl-terminated polydimethylsiloxane is 1500-300000mpa.s.
  2. 2. The silicone-based 3D printing blanket according to claim 1, wherein the vinyl-terminated polydimethylsiloxane has a vinyl content of 0.1-0.5g/100g, the hydrogen-containing silicone oil has a silicon hydrogen content of 5-20g/100g, and the vinyl-terminated polydimethylsiloxane and the hydrogen-containing silicone oil are used in amounts such that the vinyl-terminated polydimethylsiloxane mass x vinyl content: the hydrogen-containing silicone oil mass x silicon hydrogen content = 1:1-3, preferably 1:1.2-2.6.
  3. 3. The silicone-based 3D printing blanket according to claim 1 or 2, wherein the silicone composition comprises 60-75 parts vinyl-terminated polydimethylsiloxane, the hydrogen-containing silicone oil is 0.3-1 parts side chain hydrogen-containing silicone oil and 5-6.5 parts terminal hydrogen-containing silicone oil, preferably the hydrogen-containing silicone oil is 0.3-0.6 parts side chain hydrogen-containing silicone oil and 5-6.5 parts terminal hydrogen-containing silicone oil, more preferably the hydrogen-containing silicone oil is 0.3-0.5 parts side chain hydrogen-containing silicone oil and 5-6.5 parts terminal hydrogen-containing silicone oil.
  4. 4. A silicone-based 3D printing blanket according to any of claims 1-3, wherein the vinyl-terminated polydimethylsiloxane has a viscosity of 1500-60000mpa.s, the side-chain hydrogen-containing silicone oil has a silicon hydrogen content of 15-20g/100g, and the end-hydrogen-containing silicone oil has a silicon hydrogen content of 3-5.5g/100g.
  5. 5. The silicone-based 3D printing blanket according to any of claims 1 to 4, wherein the fumed silica comprises 20 to 40 wt%, preferably 20 to 30wt%, in the silicone composition formulation, and the fumed silica has a BET specific surface area of 170 to 260 m 2 /g, preferably 200 to 240m 2 /g.
  6. 6. The silicone-based 3D printing blanket according to any of claims 1-5, wherein the platinum catalyst is selected from at least one of platinum catalyst, pt/C catalyst, chloroplatinic acid, cassitter catalyst, speier catalyst, platinum acetylacetonate.
  7. 7. The silicone-based 3D printing blanket according to any of claims 1-6, wherein the inhibitor is selected from at least one of ethynyl cyclohexanol, methylbutynyl alcohol, 3, 5-dimethyl-1-hexynyl-3-ol, 3-methyl-1-dodecyn-3-ol, tetramethyl tetravinyl cyclotetrasiloxane, and/or, The thixotropic agent is at least one selected from phenyl silicone oil and polyether silicone oil.
  8. 8. The silicone-based 3D printing mat of any one of claims 1-7 wherein the maximum unsupported cantilever length of the 3D printing mat is 2D or more and D is the nozzle diameter, preferably the maximum unsupported cantilever length of the 3D printing mat is 2.5D or more, more preferably the maximum unsupported cantilever length of the 3D printing mat is 3D or more.
  9. 9. The method for preparing the silicone-based 3D printing blanket according to any one of claims 1 to 8, comprising the steps of: (S1) uniformly mixing vinyl-terminated polydimethylsiloxane and gas-phase white carbon black in a planetary mixer under vacuum condition, adding hydrogen-containing silicone oil, a platinum catalyst, an inhibitor and a thixotropic agent, uniformly mixing under vacuum condition, and defoaming to obtain a printing material; and (S2) loading the printing material into a 3D printer, performing 3D printing according to a set program, and heating and curing after the printing is finished to prepare the 3D printing pad based on the organic silicon.
  10. 10. The process according to claim 9, wherein in the step (S1), the uniform mixing under vacuum is performed at a rotation speed of 200 to 400rpm under a vacuum of 0.05 to 0.09MPa, and/or, In the step (S2), parameters of 3D printing are set as follows, the diameter of a nozzle is 0.3-3mm, preferably 1-1.5mm, the filling ratio is 20-40%, preferably 25-30%, the extrusion pressure is 0.1-0.8Mpa, preferably 0.3-0.5MPa, the printing speed is 10-70mm/S, preferably 30-50mm/S, and further, in the step (S2), the heating curing condition is 100-150 ℃ and the heat preservation treatment is 0.5-3 hours.

Description

3D printing pad based on organic silicon and preparation method thereof Technical Field The invention relates to the technical field of organosilicon materials and 3D printing composite, in particular to an organosilicon-based 3D printing pad material and a preparation method thereof. Background The 3D printing cushion material has very wide application at present, the 3D printing cushion has the dual characteristics of low density and decorative patterns, and the 3D printing cushion material has customized application in products such as yoga mats, bike seats and the like. The 3D printing pad can accurately regulate and control the density, toughness and hardness of different positions to meet different use requirements. For example, in a bicycle saddle, the ischial locations require more support, while other locations require more flexibility to improve user comfort. At present, the mainstream 3D printing pad products are manufactured by adopting materials such as PVC, TPE, natural rubber and the like through a mould pressing process, but the defects that the performances are uniform, personalized support cannot be provided, part of the materials are not environment-friendly and the like exist. 3D printing techniques offer the possibility for personalized manufacturing. However, applying 3D printing to products with large size and high elasticity requirements such as yoga mats and bike seats faces two major core challenges: 1. Support structure difficulties when printing overhang structures using conventional Fused Deposition (FDM) or light curing (SLA/DLP) techniques, additional support structures must be printed. The support needs to be removed in the later period, so that the process is complex, materials are wasted, scars can be left on the surface of a product, and the touch feeling and the attractiveness of the yoga mat are seriously affected. 2. The material and process suitability is difficult that the common silica gel material does not have rheological property suitable for printing and is easy to collapse and deform after extrusion. Although recently unsupported techniques such as gel suspension printing have emerged, the equipment is complex, costly, and depending on the particular peripheral medium (e.g. hydrogel bath), it is difficult to apply to the production of consumer products on a large scale. CN119529281a discloses a high-strength high-elasticity organic silicon photo-curing 3D printing material, which is obtained by taking multi-arm vinyl silicone oil, polysiloxane polymer containing a silicon hydrogen group, filler and photoinitiator as raw materials to obtain a photosensitive resin material, and performing 3D printing. The vinyl silicone oil used in the patent is multi-arm vinyl silicone oil, has the characteristics of excellent thermal stability, good mechanical property, low dielectric constant, excellent biocompatibility and the like, but has poor flexibility, and is not suitable for being used as a yoga mat. CN104559196A discloses a photocuring 3D printing material, which comprises, by mass, 30-90% of organopolysiloxane containing vinyl groups, 5-30% of organopolysiloxane containing silicon-hydrogen bonds, 0.001-10% of photoinitiator, 0.1-20% of reinforcing filler and 0.5-10% of auxiliary agent. However, compared with the mechanical properties of the addition type silicone rubber, the mechanical properties of the organic silicone material of the patent have larger gap, and the tensile strength and the elongation at break are relatively poor, so that the organic silicone material is not suitable for being used as a yoga mat. The double-nozzle (main body material and supporting material) extrusion 3D printing technology can realize the printing of complex patterns, but has the problems of difficult removal of the supporting material, mixed interface material, impaired appearance and performance, higher equipment cost and the like. In contrast, the single-nozzle 3D printing technology has the advantages of low equipment cost, no need of removing supporting materials, simplified manufacturing process and the like, and is beneficial to improving the manufacturing efficiency and reducing the cost. Meanwhile, the reduction of the supporting structure can improve the surface quality of the product, reduce the defect risk, remarkably expand the freedom degree of structural design and directly print the complicated overhanging, honeycomb or gradual change cavity structure. However, single-jet 3D printing faces the challenges of "small maximum unsupported cantilever length" and difficult to reach the standard for comprehensive mechanical properties, limiting the complexity of printing patterns. Therefore, improving the maximum unsupported cantilever length of the 3D printing material is a key technical approach to achieve high degree of freedom design and reliability. Disclosure of Invention The invention aims at facing the manufacturing requirement of a 3D printing silica gel pad, adopts