CN-121990765-A - High-refractive-index photo-curing 3D printing enamel material and preparation method thereof

CN121990765ACN 121990765 ACN121990765 ACN 121990765ACN-121990765-A

Abstract

The application relates to the technical field of photo-curing 3D printing materials, and discloses a high-refractive-index photo-curing 3D printing enamel material and a preparation method thereof. The material takes epoxy acrylate and polyurethane acrylate compound resin as a matrix, rutile type nano titanium dioxide and yttrium stable tetragonal phase nano zirconium oxide composite powder as high refractive index filler, and silane coupling agent, photoinitiator and sintering aid precursor are used as auxiliary materials, wherein the silane coupling agent improves the compatibility of the filler and the matrix, and the sintering aid precursor optimizes the subsequent sintering effect. The preparation method comprises the steps of filler surface modification, resin compounding, multistage gradient dispersion, photocuring 3D printing forming and subsequent programmed sintering treatment. The material can be used for preparing high-precision enamel products in the fields of jewelry, clocks and the like, can better give consideration to photocuring formability, higher refractive index and adaptive sintering performance, is beneficial to improving the comprehensive quality of products, has a standard and controllable preparation method, and can realize the efficient forming of personalized enamel products with complex structures.

Inventors

FENG WENTING
HUANG KEYU
LI ZHENGRU
Qin Zibo
Li Shuoqiu
TIAN YUHAN

Assignees

中国地质大学（武汉）

Dates

Publication Date: 20260508
Application Date: 20260309

Claims (10)

1. The high refractive index photocuring 3D printing enamel material is characterized by comprising, by mass, 30-55 parts of a photosensitive resin matrix, 40-65 parts of a high refractive index inorganic filler, 0.5-3 parts of a surface modifier, 0.1-2 parts of a sintering aid precursor, 1-6 parts of a photoinitiator and 0.5-4 parts of a dispersing and stabilizing aid.
2. The high refractive index photo-curing 3D printing enamel material of claim 1, wherein the high refractive index inorganic filler is composite powder of nano titanium dioxide and nano zirconium oxide, the nano titanium dioxide is rutile type, the average primary particle size is 30-100nm, the nano zirconium oxide is yttrium stable tetragonal phase, the average primary particle size is 50-150nm, the mass ratio of the nano titanium dioxide is 60-90% and the mass ratio of the nano zirconium oxide is 10-40% based on the total mass of the high refractive index inorganic filler.
3. The high refractive index photocurable 3D printing enamel material of claim 1 wherein said surface modifier is gamma-methacryloxypropyl trimethoxysilane.
4. The high-refractive-index photo-curing 3D printing enamel material according to claim 1, wherein the sintering aid precursor is one or more of tetrabutyl titanate, tetrabutyl zirconate, aluminum isopropoxide or cerium acetylacetonate, and the photosensitive resin matrix is a compound of epoxy acrylate and polyurethane acrylate, and the compound ratio of the epoxy acrylate to the polyurethane acrylate is 2:1-1:1.
5. The high-refractive-index photocuring 3D printing enamel material according to claim 1 is characterized in that the photoinitiator is a compound system of 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide and 1-hydroxycyclohexyl phenyl ketone, the mass ratio of the compound system to the compound system is 5:2-4:1, and the dispersing and stabilizing aid comprises a block copolymer type high-molecular hyperdispersant, polyether modified polydimethylsiloxane serving as a leveling agent and polysiloxane serving as a defoaming agent.
6. A method for preparing a high refractive index photo-cured 3D printed enamel material, characterized in that it is used for the high refractive index photo-cured 3D printed enamel material according to any one of claims 1 to 5, comprising the steps of: S1, pre-dispersing a sintering aid precursor, namely dissolving the sintering aid precursor into a small amount of photosensitive resin matrix, and uniformly stirring and mixing under the protection of inert atmosphere to form a sintering aid precursor pre-dispersion liquid; S2, preparing resin premix, namely mixing the residual photosensitive resin matrix with a dispersion stabilizing auxiliary agent, and uniformly stirring to prepare resin premix; S3, preparing high-solid-content composite slurry, namely adding modified composite filler and the sintering aid precursor pre-dispersion liquid obtained in the step S2 in a plurality of times under the stirring condition, adding a photoinitiator after high-shearing fine dispersion treatment, stirring and mixing uniformly in a dark place, and then carrying out vacuum defoaming to finally obtain the high-refractive-index photocuring 3D printing enamel material.
7. The method of preparing a high refractive index photocurable 3D printed enamel material according to claim 6, wherein in step S1, the inert atmosphere is nitrogen or argon, the stirring speed is 200-500rpm, the stirring time is 30-60min, and the temperature is room temperature to 40 ℃.
8. The method for preparing the high refractive index photocuring 3D printing enamel material according to claim 6, wherein in the step S3, the high shearing fine dispersion treatment adopts a multistage gradient grinding process, the high shearing fine dispersion treatment is sequentially carried out for 3-5 times under the dispersion gaps of 45-55 mu m, 20-30 mu m and 10-20 mu m, and the modified composite filler is gradually added into the resin premix for 3-5 times.
9. A method for preparing a high refractive index enamel product, characterized in that it is used for a high refractive index photo-curing 3D printing enamel material according to any one of claims 1 to 5, comprising the steps of: A1, photocuring additive manufacturing and molding, namely photocuring and molding the high-refractive-index photocuring 3D printing enamel material layer by layer to prepare a green blank with a preset three-dimensional structure; a2, cleaning and drying the green blank, namely performing multistage ultrasonic cleaning on the prepared green blank to remove uncured slurry remained on the surface and the inner pores, and performing low-temperature drying treatment after cleaning; and A3, programmed gradient heat treatment, namely placing the dried blank in a programmed temperature-controlled furnace, performing low-temperature pre-carbonization treatment under inert atmosphere, switching to oxidizing atmosphere for thermal degreasing treatment, completely removing organic components in the blank to obtain an inorganic porous blank, heating to perform glazing sintering treatment, densifying inorganic filler particles and forming a continuous vitrified enamel glaze layer, and naturally cooling along with the furnace to obtain the high-refractive-index enamel product.
10. The method according to claim 9, wherein in the step A3, the low-temperature pre-carbonization treatment is performed by heating from room temperature to 250-350 ℃ at a heating rate of 1-2 ℃ per minute under an inert atmosphere of nitrogen or argon and maintaining the temperature for 30-60min, the thermal degreasing treatment is performed by switching to an air oxidizing atmosphere, heating from 250-350 ℃ to 300 ℃ at a heating rate of 0.8-1.2 ℃ per minute and then heating from 300 ℃ to 480-520 ℃ at a heating rate of 0.4-0.6 ℃ per minute and maintaining the temperature for 80-100min, and the enamelling sintering treatment is performed by heating from 710-800 ℃ at a heating rate of 2.5-5.5 ℃ per minute and maintaining the temperature for 10-30min.

Description

High-refractive-index photo-curing 3D printing enamel material and preparation method thereof Technical Field The application relates to the technical field of photocuring 3D printing materials, in particular to a high-refractive-index photocuring 3D printing enamel material and a preparation method thereof, and the obtained material can be used for preparing inorganic nonmetallic enamel products. Background The enamel product has wide application prospect in the fields of jewelry, clocks, artistic decorations, architectural decorations and the like by virtue of excellent chemical stability, decorative performance and durability, and the high refractive index characteristic can further improve the optical performance and the added value of the product. The photocuring 3D printing technology has the technical advantages of high molding precision, good detail reduction degree and capability of realizing complex three-dimensional structure preparation, can break through the limitation of the traditional enamel preparation technology and realize the high-efficiency molding of personalized and high-precision enamel products, so that the development of high-refractive-index enamel materials adapting to the photocuring 3D printing technology becomes a research direction with practical application value in the current industry, and the materials are generally required to have good photocuring molding characteristics, higher refractive index and performance adapting to the subsequent sintering technology at the same time so as to ensure the molding quality and the use reliability of the final enamel products. At present, the existing photocuring 3D printing enamel material often has unreasonable parts in component selection and proportion design, and effective synergistic effect among all components is often difficult to realize. Although part of the materials can meet the basic requirements of light curing molding, the poor compatibility of inorganic fillers and a resin matrix not only causes that the refractive index of the materials is difficult to reach the expected standard, but also can generate defects in the subsequent sintering process, and the other part of the materials is stressed to raise the refractive index, but also can cause that the stability of light curing molding is reduced, the precision requirements of light curing 3D printing are often difficult to adapt, the light curing molding, the high refractive index and the good sintering performance are difficult to be simultaneously considered, the comprehensive quality of enamel products is further influenced, and the high-performance use requirements in practical application are difficult to be fully met. Disclosure of Invention In order to solve the problems that the photo-curing 3D printing enamel material in the prior art is unreasonable in component selection and proportion, effective synergistic effect of all components is difficult to realize, photo-curing formability, high refractive index and good sintering performance are difficult to be effectively considered, and comprehensive quality of enamel products is further affected, the application provides the high refractive index photo-curing 3D printing enamel material and a preparation method thereof. In a first aspect, the application provides a high refractive index photo-curing 3D printing enamel material, which adopts the following technical scheme: The high refractive index photocuring 3D printing enamel material comprises, by mass, 30-55 parts of a photosensitive resin matrix, 40-65 parts of a high refractive index inorganic filler, 0.5-3 parts of a surface modifier, 0.1-2 parts of a sintering aid precursor, 1-6 parts of a photoinitiator and 0.5-4 parts of a dispersing and stabilizing aid. By adopting the technical scheme, the photosensitive resin matrix provides a cross-linking curing skeleton for photopolymerization reaction, the high refractive index inorganic filler endows the material with core optical performance, the surface modifier builds a connecting bridge of an inorganic phase and an organic phase, the sintering aid precursor provides sintering active sites for subsequent heat treatment, the photoinitiator triggers the curing reaction of the system, the dispersion and stabilization aid maintains the stability of the slurry system, and all the components are matched in proportion in a synergistic manner to form a complete material system which can meet the requirements of photocuring 3D printing processing and has subsequent sintering densification potential, so that core composition support is provided for preparing high-performance enamel products. Preferably, the high refractive index inorganic filler is composite powder of nano titanium dioxide and nano zirconium oxide, wherein the nano titanium dioxide is rutile type, the average primary particle size is 30-100nm, the nano zirconium oxide is yttrium stable tetragonal phase, the average primary particle size is 50-150nm,