Search

CN-122011289-A - Light-cured resin composition for 3D printing, 3D printing method and application

CN122011289ACN 122011289 ACN122011289 ACN 122011289ACN-122011289-A

Abstract

The invention provides a photo-curing resin composition for 3D printing, a 3D printing method and application, and belongs to the technical field of 3D printing, wherein the photo-curing resin composition comprises an initial photo-curing resin, a thickening auxiliary agent and permanent magnetic particles, the total mass of the initial photo-curing resin is 100%, the initial photo-curing resin comprises 44-64 wt% of aqueous polyurethane acrylate prepolymer, 35-55 wt% of acrylic monomer and 0.5-1 wt% of photoinitiator, the addition amount of the thickening auxiliary agent is 0.5-4 wt% of the total mass of the initial photo-curing resin, and the addition amount of the permanent magnetic particles is 10-30 wt% based on the total mass of the photo-curing resin composition. The printing piece obtained by the resin composition has the advantages of excellent mechanical property, magnetic response and thermal response, and no biotoxicity.

Inventors

  • JI JIAN
  • WANG SHU
  • XIAO XIAO
  • CHEN MOJUN

Assignees

  • 杭州市滨江区浙医二院经血管植入器械研究院
  • 香港科技大学(广州)

Dates

Publication Date
20260512
Application Date
20260305

Claims (10)

  1. 1. A photocurable resin composition for 3D printing, comprising an initial photocurable resin, a thickening aid and permanent magnetic particles, wherein: The initial photo-curing resin comprises 44-64 wt% of aqueous polyurethane acrylate prepolymer, 35-55 wt% of acrylic monomer and 0.5-1 wt% of photoinitiator based on 100% of the total mass of the initial photo-curing resin; the addition amount of the thickening aid is 0.5-4 wt% of the mass of the initial photo-curing resin; The permanent magnetic particles are added in an amount of 25-40 wt% based on 100% of the total mass of the photo-curable resin composition.
  2. 2. The photocurable resin composition for 3D printing according to claim 1, wherein the aqueous urethane acrylate prepolymer comprises 70-90 wt% aqueous urethane and 10-30 wt% acrylic compound based on 100% total mass of the aqueous urethane acrylate prepolymer.
  3. 3. The photocurable resin composition for 3D printing according to claim 2, wherein the aqueous polyurethane has an average molecular weight of 1000-100000 and a viscosity of 100-10000 mPa s; And/or the acrylic ester compound comprises any one or a combination of at least two of 2-ethylhexyl ester, methyl acrylate, hydroxyethyl methacrylate or butyl acrylate.
  4. 4. The photocurable resin composition for 3D printing according to claim 1, wherein the acryl-based monomer comprises any one or a combination of at least two of acryl morpholine, isobornyl acrylate, tetrahydrofuranyl acrylate, dicyclopentenyl acrylate, or benzyl acrylate.
  5. 5. The photocurable resin composition for 3D printing according to claim 1, wherein the thickening aid comprises any one or a combination of at least two of polyvinylpyrrolidone, sodium polyacrylate, hydroxyethyl cellulose, sodium carboxymethyl cellulose, or polyethylene oxide.
  6. 6. The photocurable resin composition for 3D printing according to claim 1, wherein said permanent magnetic particles comprise any one or a combination of at least two of neodymium iron boron, samarium cobalt, alnico, or iron chromium cobalt; and/or the particle size of the permanent magnetic particles is 5-10 mu m.
  7. 7. The photocurable resin composition for 3D printing according to claim 1, wherein the photoinitiator comprises any one or a combination of at least two of photoinitiator 2959, photoinitiator TPO, photoinitiator 184, photoinitiator 1173, or photoinitiator 819.
  8. 8. A 3D printing method, characterized in that the 3D printing method is performed using the photocurable resin composition for 3D printing according to any one of claims 1 to 7, the method comprising: (a) 3D printing and molding the photo-curing resin composition; (b) And (5) carrying out radiation curing on the molded body to finish 3D printing.
  9. 9. The 3D printing method as defined in claim 8 wherein the radiation curing is radiation curing using ultraviolet rays having a wavelength of 365-405 nm.
  10. 10. Use of the photocurable resin composition for 3D printing according to any one of claims 1-7 in the preparation of medical micro-robots, magnetic implants, magnetic consumer electronics or magnetic industrial components.

Description

Light-cured resin composition for 3D printing, 3D printing method and application Technical Field The invention belongs to the technical field of 3D printing, and particularly relates to a photo-curing resin composition for 3D printing, a 3D printing method and application. Background In recent years, photo-curing 3D printing techniques have shown significant advantages in the manufacture of complex structural members due to their high precision and rapid prototyping capabilities. The photosensitive resin for 3D printing is generally composed of a prepolymer (oligomer), a reactive diluent (monomer), a photoinitiator and various additives, wherein the prepolymer is taken as a main material and is used for determining basic properties of the cured material, such as mechanical strength, hardness, chemical resistance and the like, the monomer is used for adjusting the viscosity of the resin and participating in a photocuring reaction to influence the curing speed, the crosslinking density and the final properties, the photoinitiator absorbs light energy with specific wavelength to generate active groups (free radicals or cations) to initiate polymerization and crosslinking of the monomer and the oligomer, and the additives are used for improving the specific properties of the resin and are not required to be added. However, the existing photosensitive resin material system applied to the technology still has a plurality of limitations, and particularly for high-end applications with intelligent response requirements, the functional singleness of the existing photosensitive resin material system has become a bottleneck in technical development. Currently, the photosensitive resin is generally only suitable for manufacturing fixed teaching molds or supporting pieces without special functions. CN202211582552.9 discloses a 3D printing material with a magnetic complex three-dimensional structure and a method thereof, CN201710442097 discloses a method for preparing a magnetic material product by dual-curing 3D gel printing combining chemical curing and photo-curing, and the above patent application adds magnetic particles into the existing photosensitive resin system to make the photosensitive resin magnetic, so that only simple magnetic driving movement or positioning can be realized, and complex and preset shape memory behaviors can not be realized at the same time. In addition, a series of problems are often caused by simply blending a plurality of functional materials (such as magnetic particles) into photosensitive resin, namely, firstly, the magnetic particles are easy to agglomerate and settle, the uniformity and stability of a 3D printing process are seriously affected, the resolution ratio of a printing finished product is finally lowered, and the mechanical property is finally deteriorated, secondly, the addition of the particles can obviously increase the scattering and absorption of the photosensitive resin to light, seriously reduce the penetration depth and the curing efficiency of a photocuring process, restrict the printing precision and the structural complexity of a forming device, and thirdly, the traditional resin system is difficult to realize the cooperative regulation and control of 'magnetic-thermal' multi-field coupling, so that the printing and forming structure cannot execute continuous and complex tasks of 'magnetic driving movement-thermal triggering deformation' as required, and the application potential of the printing and forming device in the fields of flexible robots, intelligent medical devices and the like is greatly limited. Therefore, it is desirable to provide a photocurable resin for 3D printing that combines thermally triggered deformation with magnetic actuation to meet application requirements. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a photo-curing resin composition for 3D printing, a 3D printing method and application. In order to achieve the aim of the invention, the invention adopts the following technical scheme: in a first aspect, the present invention provides a photocurable resin composition for 3D printing comprising an initial photocurable resin and a thickening aid and permanent magnetic particles, wherein: The initial photo-curing resin comprises 44-64 wt% of aqueous polyurethane acrylate prepolymer, 35-55 wt% of acrylic monomer and 0.5-1 wt% of photoinitiator based on 100% of the total mass of the initial photo-curing resin; the addition amount of the thickening aid is 0.5-4 wt% of the mass of the initial photo-curing resin; The permanent magnetic particles are added in an amount of 25-40 wt% based on 100% of the total mass of the photo-curable resin composition. The photocurable resin composition for 3D printing provided by the invention has the following advantages: i. By selecting the waterborne polyurethane acrylate prepolymer, the principle that the material has different Young modulus at different temper