A photocurable zirconia ceramic slurry, a photocurable zirconia ceramic material and a method for preparing the same

Abstract

The application belongs to the field of 3D printing, and particularly relates to a photocured zirconia ceramic slurry, a photocured zirconia ceramic material and a preparation method thereof. The photocured zirconia ceramic slurry comprises nano zirconia, a photosensitive resin, a free radical polymerization inhibitor, a photoinitiator and a dispersant; in the photocured zirconia ceramic slurry, the mass ratio of the free radical polymerization inhibitor to the photosensitive resin is (0.25-0.42):100; the photosensitive resin is selected from three kinds of cyclic trihydroxymethyl propane formaldehyde acrylate, lauric acid acrylate, tris(2-hydroxyethyl) isocyanuric acid triacrylate, tricyclodecane dimethylol diacrylate, dipentaerythritol hexaacrylate and tripropylene glycol diacrylate; and the free radical polymerization inhibitor is Sudan red and / or curcumin. The product prepared by 3D printing of the photocured zirconia ceramic slurry has high printing precision, good integrity and excellent formability.

Description

Technical Field

[0001] This invention belongs to the field of 3D printing, specifically relating to a photocurable zirconia ceramic slurry, a photocurable zirconia ceramic material, and a method for preparing the same. Background Technology

[0002] Zirconia ceramics possess excellent structural properties such as high strength, high hardness, high temperature resistance, corrosion resistance, low coefficient of thermal expansion, and a unique phase transformation toughening effect. They also exhibit a wealth of functionalities including dielectric, piezoelectric, semiconductor, and biocompatibility, making them widely used in wear-resistant materials, refractories, machinery, electronics, optics, aerospace, biology, and chemistry. Traditional zirconia ceramic forming methods, such as dry pressing, slip casting, and tape casting, suffer from low precision in irregularly shaped structures. While computer numerical control (CNC) forming can achieve higher levels of precision, the brittleness of zirconia ceramics makes CNC forming prone to defects and limits its ultimate precision. Furthermore, the printing precision of ordinary 3D-printed zirconia ceramics is generally low.

[0003] Therefore, there is an urgent need to develop a photocurable zirconia ceramic slurry that produces products with high precision, good integrity, and good formability during the 3D printing process. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a photocurable zirconia ceramic slurry, a photocurable zirconia ceramic material, and a method for preparing the same. The photocurable zirconia ceramic slurry of this invention can achieve 3D printing with micro-nano level precision, and the printed products have good integrity and formability.

[0005] Specifically, the present invention provides a photocurable zirconia ceramic slurry, which comprises nano-zirconia, photosensitive resin, free radical polymerization inhibitor, photoinitiator, and dispersant; in the photocurable zirconia ceramic slurry, the mass ratio of the free radical polymerization inhibitor to the photosensitive resin is (0.25-0.42):100; the photosensitive resin is selected from three of the following: cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, tri(2-hydroxyethyl) isocyanurate triacrylate, tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate; the free radical polymerization inhibitor is Sudan Red and / or curcumin.

[0006] In one or more embodiments, the mass ratio of the nano-zirconia to the photosensitive resin in the photocurable zirconia ceramic slurry is (3-5.67):1.

[0007] In one or more embodiments, the photoinitiator to the photosensitive resin in the photocurable zirconia ceramic slurry is in a mass ratio of (1-5):100.

[0008] In the photocurable zirconia ceramic slurry, the mass ratio of the dispersant to the photosensitive resin, the photoinitiator, the free radical polymerization inhibitor, and the nano-zirconia is (0.5-4):100.

[0009] In one or more embodiments, the particle size D50 of the nano-zirconia is 200~3000 nm.

[0010] In one or more embodiments, the photoinitiator is selected from one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexylphenyl ketone.

[0011] In one or more embodiments, the dispersant is selected from one or more of BYK-102, BYK-180, BYK-9076, BYK-109, BYK-108, BYK-110, Boltorn H20, Boltorn H2004, PSI-500, PSI-510, PSI520 and PSI-512.

[0012] In one or more embodiments, the photosensitive resin is cyclotrimethylolpropane methyl acetal acrylate, lauryl acrylate, and tri(2-hydroxyethyl) isocyanurate triacrylate, wherein the mass ratio of cyclotrimethylolpropane methyl acetal acrylate, lauryl acrylate, and tri(2-hydroxyethyl) isocyanurate triacrylate is (1-3.5):(0.5-3.6):1.

[0013] In one or more embodiments, the photosensitive resin is cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, and tricyclodecanediethanol diacrylate, wherein the mass ratio of cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, and tricyclodecanediethanol diacrylate is (0.5-3):(0.5-2.5):1.

[0014] In one or more embodiments, the photosensitive resin is tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate, wherein the mass ratio of tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate is (0.3-1.5):(0.2-1.5):1.

[0015] The present invention provides a method for preparing photocurable zirconia ceramic slurry according to any one of the present invention, the method comprising: (a) mixing photosensitive resin, photoinitiator and free radical polymerization inhibitor uniformly; (b) adding nano-zirconia and dispersant to the mixture obtained in step (a), mixing uniformly and then filtering to obtain photocurable zirconia ceramic slurry.

[0016] In one or more embodiments, in step (a), mixing is carried out under vacuum conditions.

[0017] In one or more embodiments, in step (b), mixing is carried out under vacuum conditions.

[0018] This invention provides a method for preparing photocurable zirconia ceramic materials, the method comprising the following steps: (1) Design a printing model of photocurable zirconia ceramic material using 3D modeling software, import the printing model file into the photocurable printer, and perform photocurable printing on any of the photocurable zirconia ceramic slurries described in this invention in the photocurable printer to obtain a printed sample. (2) The printed sample is cleaned and baked to obtain photocurable zirconia ceramic material.

[0019] In one or more embodiments, during step (1), the light intensity during photopolymerization printing is 3000-33000 μW / cm². 2 .

[0020] In one or more embodiments, in step (2), the baking time is 10-40 min.

[0021] In one or more embodiments, in step (2), the baking temperature is 25-60°C.

[0022] This invention provides a photocurable zirconia ceramic material prepared using any of the methods described in this invention.

[0023] Compared with the prior art, the present invention has the following advantages: the photocurable zirconia ceramic slurry of the present invention produces products with high precision, good integrity, and excellent forming effect in 3D printing. Attached Figure Description

[0024] Figure 1 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Example 1 of the present invention.

[0025] Figure 2 This is a magnified microscope image of the photocurable zirconia ceramic material prepared in Example 2 of the present invention.

[0026] Figure 3This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Example 3 of the present invention.

[0027] Figure 4 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Example 4 of the present invention.

[0028] Figure 5 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Comparative Example 1 of the present invention.

[0029] Figure 6 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Comparative Example 2 of the present invention.

[0030] Figure 7 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Comparative Example 3 of the present invention.

[0031] Figure 8 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Comparative Example 4 of this invention.

[0032] Figure 9 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Comparative Example 5 of the present invention.

[0033] Figure 10 This is a magnified microscopic image of the photocurable zirconia ceramic material prepared in Comparative Example 6 of this invention.

[0034] Figure 11 This is a magnified microscopic image of a small-pore sample of the photocurable zirconia ceramic material prepared in Example 2 of the present invention. Detailed Implementation

[0035] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used herein are explained and defined in general terms below. Unless otherwise specified, all technical and scientific terms used herein have the common meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0036] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0037] In this document, the terms “contains,” “includes,” “containing,” and similar terms encompass the meanings of “basically composed of” and “composed of.” For example, when this document discloses “A contains B and C,” “A is basically composed of B and C” and “A is composed of B and C” should be considered as having been disclosed in this document.

[0038] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0039] In this article, the sum of the percentages of each component in the composition is 100%.

[0040] Unless otherwise specified, percentages refer to mass percentages and proportions refer to mass ratios in this article.

[0041] In this document, when describing embodiments or examples, it should be understood that they are not intended to limit the invention to those embodiments or examples. Rather, all alternatives, modifications, and equivalents of the methods and materials described herein are covered within the scope defined herein.

[0042] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0043] The photocurable zirconia ceramic slurry provided by the present invention may include nano-zirconia, photosensitive resin, free radical polymerization inhibitor, photoinitiator and dispersant.

[0044] In this invention, the photosensitive resin can be selected from three of the following: cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, tri(2-hydroxyethyl) isocyanurate triacrylate, tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate. By using these three photosensitive resins, the viscosity of the slurry can be adjusted to a suitable range, resulting in high precision, good integrity, and excellent molding effect in 3D printing of photocured zirconia ceramic slurry. Furthermore, the resulting photocured zirconia ceramic material possesses good toughness and strength, and can to a certain extent prevent cracking during the cleaning process when internal stress is released. The photosensitive resin of this invention is cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, and tricyclodecanediethanol diacrylate. The mass ratio of cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, and tricyclodecanediethanol diacrylate can be (0.5-3):(0.5-2.5):1, for example, 1.3:1.3:1, 1:1.5:1, or 2:2:1. In this invention, using cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, and tricyclodecanediethanol diacrylate as the photosensitive resin and controlling their mass ratio within the above range is beneficial for printing products with high precision, good integrity, and excellent molding effect. The photosensitive resin of this invention is tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate. The mass ratio of tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate can be (0.3-1.5):(0.2-1.5):1, for example, 1:1:1, 0.8:1.2:1, or 0.5:1:1. In this invention, using tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate as the photosensitive resin and controlling their mass ratio within the above range is beneficial for printing products with high precision, good integrity, and excellent molding effect. The photosensitive resin of this invention is cyclotrimethylolpropane methyl acetal acrylate, lauryl acrylate, and tri(2-hydroxyethyl) isocyanurate triacrylate. The mass ratio of cyclotrimethylolpropane methyl acetal acrylate, lauryl acrylate, and tri(2-hydroxyethyl) isocyanurate triacrylate can be (1-3.5):(0.5-3.6):1, for example, 1.2:2:1, 2:2:1, or 3:3:1. In this invention, using cyclotrimethylolpropane methyl acetal acrylate, lauryl acrylate, and tri(2-hydroxyethyl) isocyanurate triacrylate as the photosensitive resin and controlling their mass ratio within the above range is beneficial for printing products with high precision, good integrity, and excellent molding effect.

[0045] In this invention, the free radical polymerization inhibitor can be Sudan Red and / or curcumin. The use of Sudan Red and / or curcumin as a free radical polymerization inhibitor in the slurry has a synergistic effect with the photosensitive resin in the slurry, effectively improving edge curing and thus contributing to obtaining printed products with high precision, good integrity, and excellent molding effect. It also helps to increase the light intensity to the stable range of the printer's light source.

[0046] In the photocurable zirconia ceramic slurry of this invention, the mass ratio of free radical polymerization inhibitor to photosensitive resin can be (0.25-0.42):100, for example, 0.25:100, 0.27:100, 0.30:100, 0.35:100, 0.37:100, 0.40:100, or 0.42:100. Controlling the mass ratio of free radical polymerization inhibitor to photosensitive resin in the photocurable zirconia ceramic slurry within the above range is beneficial for improving edge curing phenomena and ensuring the degree of curing, thereby contributing to obtaining products with high precision, good integrity, and excellent molding effect. It also helps to increase the light intensity to the stable range of the printer light source. In the photocurable zirconia ceramic slurry of this invention, the mass ratio of nano-zirconia to photosensitive resin can be (3-5.67):1, for example, 3.0:1, 3.5:1, 4.0:1, 4.5:1, 5.0:1, or 5.5:1. In this invention, controlling the mass ratio of nano-zirconia to photosensitive resin within the aforementioned range is beneficial for obtaining printed products with high precision, good integrity, and excellent molding effect. It also helps to increase the light intensity to within the stable range of the printer's light source. In the photocurable zirconia ceramic slurry of this invention, the mass ratio of photoinitiator to photosensitive resin can be (1-5):100, for example, 2:100, 2.5:100, 3:100, 3.5:100, 4:100, or 4.5:100. In the photocurable zirconia ceramic slurry of this invention, the mass ratio of dispersant to the sum of photosensitive resin, photoinitiator, free radical polymerization inhibitor, and nano-zirconia can be (0.5-4):100, for example, 0.5:100, 1:100, 1.5:100, 2:100, 2.5:100, 3:100, 3.5:100, or 4:100.

[0047] In this invention, the particle size D50 of nano-zirconia can be 200-3000 nm, for example, 200 nm, 600 nm, 1000 nm, 1400 nm, 1800 nm, 2200 nm, 2600 nm, and 3000 nm. Controlling the particle size D50 of the nano-zirconia powder within the above range in this invention is beneficial for obtaining products with high precision, high integrity, and good formability in 3D printing.

[0048] In this invention, the photoinitiator may be one or more selected from phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexylphenyl ketone. In this invention, the dispersant may be one or more selected from BYK-102, BYK-180, BYK-9076, BYK-109, BYK-108, BYK-110, Boltorn H20, Boltorn H2004, PSI-500, PSI-510, PSI520, and PSI-512.

[0049] The present invention provides a method for preparing the photocurable zirconia ceramic slurry of the present invention, the method comprising: (a) mixing photosensitive resin, photoinitiator and free radical polymerization inhibitor uniformly; (b) adding nano-zirconia and dispersant to the mixture obtained in step (a), mixing uniformly and then filtering to obtain the photocurable zirconia ceramic slurry.

[0050] In step (a), mixing can be carried out under vacuum conditions. In step (b), mixing can be carried out under vacuum conditions.

[0051] This invention provides a method for preparing photocurable zirconia ceramic materials, the method comprising the following steps: (1) Design a printing model of photocurable zirconia ceramic material using 3D modeling software, import the printing model file into the photocurable printer, and perform photocurable printing on any of the photocurable zirconia ceramic slurries described in this invention in the photocurable printer to obtain a printed sample. (2) The printed sample is cleaned and baked to obtain photocurable zirconia ceramic material.

[0052] In step (1), during photopolymerization printing, the light intensity can be 3000-33000 μW / cm². 2 For example, 3000μW / cm 2 4000μW / cm 2 5000μW / cm 2 6000μW / cm 2 7000μW / cm 2 8000μW / cm 2 10000μW / cm 2 15000μW / cm 2 20000μW / cm 2 25000μW / cm 2 30000μW / cm 2In step (2), the baking time can be 10-40 min, for example 10 min, 20 min, 30 min, 40 min. In step (2), the baking temperature can be 25-60℃, for example 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃.

[0053] This invention provides a photocurable zirconia ceramic material prepared using any of the methods described in this invention.

[0054] The present invention will be described below by way of specific embodiments. It should be understood that these embodiments are merely illustrative and are not intended to limit the scope of the invention. The methods, reagents, and materials used in the embodiments are conventional methods, reagents, and materials in the art, unless otherwise stated. The raw material compounds in the embodiments are all commercially available.

[0055] The nano-zirconia used in the embodiments and comparative examples of this invention was purchased from Shanghai Xiangtian Nanomaterials Co., Ltd., and the particle size D50 of the nano-zirconia was 400 nm.

[0056] The cyclotrimethylolpropane methyl acetal acrylate used in the embodiments and comparative examples of this invention was purchased from Chengdu Sicheng New Materials Co., Ltd.

[0057] The lauric acid acrylate used in the embodiments and comparative examples of this invention was purchased from Chengdu Sicheng New Materials Co., Ltd.

[0058] The tri(2-hydroxyethyl) isocyanurate triacrylate used in the embodiments and comparative examples of this invention was purchased from Chengdu Sicheng New Materials Co., Ltd.

[0059] The tricyclodecanediethanol diacrylate used in the embodiments and comparative examples of this invention was purchased from Chengdu Sicheng New Materials Co., Ltd.

[0060] The dipentaerythritol hexaacrylate used in the embodiments and comparative examples of this invention was purchased from Chengdu Sicheng New Materials Co., Ltd.

[0061] The tripropylene glycol diacrylate used in the embodiments and comparative examples of this invention was purchased from Chengdu Sicheng New Materials Co., Ltd.

[0062] The polyurethane acrylate used in the embodiments and comparative examples of this invention was purchased from Chengdu Sicheng New Materials Co., Ltd.

[0063] The BYK-110 used in the embodiments and comparative examples of this invention was purchased from Shanghai Yipu Chemical Co., Ltd., and its brand name is BYK-110.

[0064] The Sudan Red used in the embodiments and comparative examples of this invention was purchased from Wuhan Lanabai Pharmaceutical Chemical Co., Ltd., with the brand name CAS: 85-86-9.

[0065] The 1,1-diphenyl-2-trinitrophenylhydrazine used in the embodiments and comparative examples of this invention was purchased from Fuzhou Feijing Biotechnology Co., Ltd., with the brand name PH1729-C.

[0066] Example 1

[0067] The specific steps for preparing the photocurable zirconia ceramic slurry in this embodiment are as follows: (1) Weigh 30g of photosensitive resin (the photosensitive resin is a mixture of cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate and tri(2-hydroxyethyl) isocyanurate triacrylate, with a mass ratio of cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate and tri(2-hydroxyethyl) isocyanurate triacrylate of 1.33:1.33:1), 1.05g of photoinitiator ethyl 2,4,6-trimethylbenzoylphenylphosphonate and 0.09g of free radical polymerization inhibitor Sudan Red. Add the contents to a plastic container, place the container in a homogenizer, and mix at 1000 rpm under vacuum for 10 minutes. After the first mixing, weigh 150 g of nano-zirconia and 4 g of dispersant BYK-110 and add them to the plastic container. Mix at 2000 rpm under vacuum for 5 minutes to ensure the materials in the plastic container are thoroughly and evenly mixed. After mixing, filter the materials in the plastic container to obtain a photocurable zirconia ceramic slurry. (2) A printing model of photocurable zirconia ceramic material was designed using 3D modeling software. The printing model was a three-dimensional honeycomb structure with dimensions of 10mm×10mm×10mm. The printing model was imported into the photocurable printer, and the photocurable zirconia ceramic slurry in the photocurable printer was directly printed to obtain the printed sample. The printing parameters were: light source of 405nm and light intensity of 22500μW / cm². 2 The single scan time is 1.5s, the number of scans is 1000, and the printing layer thickness is 10μm; (3) Place the printed sample in alcohol and ultrasonically clean it for 2 minutes to rinse off the remaining uncured material. Then, spin dry it in a centrifuge for 10 minutes. Place the spin-dried printed sample in an oven at 50°C for 30 minutes to obtain the photocurable zirconia ceramic material.

[0068] Example 2

[0069] The other conditions in this embodiment are the same as in Embodiment 1, except that the amount of photoinitiator added in this embodiment is 0.45g.

[0070] Example 3

[0071] The other conditions in this embodiment are the same as in Embodiment 1, except that the photosensitive resin in this embodiment is cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate and tricyclodecanediethanol diacrylate, and the mass ratio of cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate and tricyclodecanediethanol diacrylate is 1.33:1.33:1.

[0072] Example 4

[0073] The other conditions in this embodiment are the same as in Embodiment 1, except that the photosensitive resin in this embodiment is tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate and tripropylene glycol diacrylate, and the mass ratio of tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate and tripropylene glycol diacrylate is 1.33:1.33:1.

[0074] Comparative Example 1

[0075] The conditions for this comparative example are the same as those for Example 1, except that no free radical polymerization inhibitor is added and the amount of photosensitive resin added is 30.09g.

[0076] Comparative Example 2

[0077] The conditions for this comparative example are the same as those for Example 1, except that the amount of free radical polymerization inhibitor added is 0.06 g and the amount of photosensitive resin added is 30.03 g.

[0078] Comparative Example 3

[0079] The conditions for this comparative example are the same as those for Example 1, except that the amount of free radical polymerization inhibitor added is 0.14g and the amount of photosensitive resin added is 29.95g.

[0080] Comparative Example 4

[0081] The conditions for this comparative example are the same as those for Example 1, except that the free radical polymerization inhibitor used in this comparative example is 1,1-diphenyl-2-trinitrophenylhydrazine.

[0082] Comparative Example 5

[0083] The conditions for this comparative example are the same as those for Example 1, except that the photosensitive resin used in this comparative example is cyclotrimethylolpropane methyl acetal acrylate and laurate acrylate, and the mass ratio of cyclotrimethylolpropane methyl acetal acrylate to laurate acrylate is 1:1.75.

[0084] Comparative Example 6

[0085] The other conditions of this comparative example are the same as those of Example 1, except that the photosensitive resins used in this comparative example are polyurethane acrylate, laurate acrylate and tri(2-hydroxyethyl) isocyanurate triacrylate, and the mass ratio of polyurethane acrylate, laurate acrylate and tri(2-hydroxyethyl) isocyanurate triacrylate is 1.33:1.33:1.

[0086] Test case

[0087] Viscosity test: At 40℃, the viscosity of the photocurable zirconia ceramic slurries prepared in Examples 1-4 and Comparative Examples 1-6 at different rotation speeds was tested using a digital viscometer. The viscosity of the photocurable zirconia ceramic slurries prepared in Examples 1-4 and Comparative Examples 1-6 at a rotation speed of 60 rpm was compared, and the results are shown in Table 1.

[0088] Curing depth test: at a light source power of 22500μw / cm 2 Under the specified conditions, the photocurable zirconia ceramic slurries prepared in Examples 1-4 and Comparative Examples 1-6 were scanned for 1.5 s using a 405 nm light source to form corresponding cured monolayers. The thickness was measured using a micrometer, and the results are shown in Table 1.

[0089] Printing performance: The photocurable zirconia ceramic materials prepared in Examples 1-4 and Comparative Examples 1-6 are as follows: Figures 1-10 As shown, comparison Figure 1-10 The integrity, surface quality, and printing performance of the photocurable zirconia ceramic material are shown in Table 1.

[0090] Table 1: Viscosity, curing depth, and printing performance of photocurable zirconia ceramic slurries prepared in Examples 1-4 and Comparative Examples 1-6

[0091] In this invention, photocurable zirconia ceramic slurry with excessively low viscosity is prone to sedimentation, which is detrimental to production use. Photocurable zirconia ceramic slurry with excessively high viscosity will affect printing quality and may even lead to printing failure. In this invention, excessive curing depth will weaken the bonding force between layers and easily lead to over-curing and smearing edges. On the other hand, excessively low curing depth will result in limited ultraviolet light penetration depth in actual printing, which will easily lead to delamination.

[0092] Depend on Figure 1-4 It can be seen that the photocurable zirconia ceramic materials printed from the photocurable zirconia ceramic slurry prepared in Examples 1-4 of this invention are complete and have no obvious surface defects, indicating that they have good printing performance. Figure 5-7 It can be seen that the photocurable zirconia ceramic materials printed from the photocurable zirconia ceramic slurry prepared in Comparative Examples 1-3 of this invention are intact, but there is obvious scattering on the surface, indicating poor printing performance. Figure 8As can be seen, the photocurable zirconia ceramic material printed from the photocurable zirconia ceramic slurry prepared in Comparative Example 4 of this invention is intact, but there are obvious scattering and delamination phenomena on the surface, indicating that its printing performance is poor. Figure 9-10 It can be seen that the photocurable zirconia ceramic materials printed from the photocurable zirconia ceramic slurry prepared in Comparative Examples 5-6 of this invention are complete and have good surface precision. However, microscopic observation reveals obvious delamination, indicating poor printing performance. Figure 11 It can be seen that the minimum printable pore size of the photocurable zirconia ceramic material printed in Embodiment 2 of the present invention is 60μm, which indicates that the photocurable zirconia ceramic slurry of the present invention has high printing accuracy in the 3D printing process.

Claims

1. A photocurable zirconia ceramic slurry, characterized in that, The photocurable zirconia ceramic slurry comprises nano-zirconia, photosensitive resin, free radical polymerization inhibitor, photoinitiator, and dispersant; in the photocurable zirconia ceramic slurry, the mass ratio of the free radical polymerization inhibitor to the photosensitive resin is (0.25-0.42):100; the photosensitive resin is selected from three of the following: cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate, tri(2-hydroxyethyl) isocyanurate triacrylate, tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate, and tripropylene glycol diacrylate; the free radical polymerization inhibitor is Sudan Red and / or curcumin.

2. The photocurable zirconia ceramic slurry according to claim 1, characterized in that, The photocurable zirconia ceramic slurry has one or more of the following characteristics: In the photocurable zirconia ceramic slurry, the mass ratio of the nano-zirconia to the photosensitive resin is (3-5.67):1; In the photocurable zirconia ceramic slurry, the mass ratio of the photoinitiator to the photosensitive resin is (1-5):100; In the photocurable zirconia ceramic slurry, the mass ratio of the dispersant to the sum of the photosensitive resin, the photoinitiator, the free radical polymerization inhibitor, and the nano-zirconia is (0.5-4):

100. The particle size D50 of the nano-zirconia is 200-3000 nm.

3. The photocurable zirconia ceramic slurry according to claim 1, characterized in that, The photoinitiator is selected from one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexylphenyl ketone.

4. The photocurable zirconia ceramic slurry according to claim 1, characterized in that, The dispersant is selected from one or more of BYK-102, BYK-180, BYK-9076, BYK-109, BYK-108, BYK-110, Boltorn H20, Boltorn H2004, PSI-500, PSI-510, PSI520 and PSI-512.

5. The photocurable zirconia ceramic slurry according to claim 1, characterized in that, The photocurable zirconia ceramic slurry has one of the following characteristics: The photosensitive resin is cyclotrimethylolpropane methyl acetal acrylate, lauryl acrylate and tri(2-hydroxyethyl) isocyanurate triacrylate, and the mass ratio of cyclotrimethylolpropane methyl acetal acrylate, lauryl acrylate and tri(2-hydroxyethyl) isocyanurate triacrylate is (1-3.5):(0.5-3.6):1; The photosensitive resin is cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate and tricyclodecanediethanol diacrylate, and the mass ratio of cyclotrimethylolpropane methyl acetal acrylate, laurate acrylate and tricyclodecanediethanol diacrylate is (0.5-3):(0.5-2.5):1; The photosensitive resin is tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate and tripropylene glycol diacrylate, and the mass ratio of tricyclodecanediethanol diacrylate, dipentaerythritol hexaacrylate and tripropylene glycol diacrylate is (0.3-1.5):(0.2-1.5):

1.

6. A method for preparing the photocurable zirconia ceramic slurry according to any one of claims 1-5, characterized in that, The method includes: (a) Mix the photosensitive resin, photoinitiator and free radical polymerization inhibitor evenly; (b) Add nano-zirconia and dispersant to the mixture obtained in step (a), mix evenly and then filter to obtain photocurable zirconia ceramic slurry.

7. The method according to claim 6, characterized in that, In step (a), mixing is carried out under vacuum conditions; and / or In step (b), mixing is carried out under vacuum conditions.

8. A method for preparing photocurable zirconia ceramic materials, characterized in that, The method includes the following steps: (1) Design a printing model of photocurable zirconia ceramic material using 3D modeling software, import the printing model file into the photocurable printer, and perform photocurable printing on the photocurable zirconia ceramic slurry of any one of claims 1-5 in the photocurable printer to obtain a printed sample; (2) The printed sample is cleaned and baked to obtain photocurable zirconia ceramic material.

9. The method as described in claim 8, characterized in that, The method has one or more of the following characteristics: In step (1), during photopolymerization printing, the light intensity is 3000-33000 μW / cm². 2 ; In step (2), the baking time is 10-40 minutes; In step (2), the baking temperature is 25-60℃.

10. A photocurable zirconia ceramic material prepared by the method of claim 8 or 9.

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