KR102910779B1 - 3D printing zirconia composition, sintered body manufactured thereby and manufacturing method thereof - Google Patents

Abstract

A zirconia 3D printing composition according to one embodiment of the present invention comprises 65 to 90 parts by weight of zirconia powder, 5 to 20 parts by weight of a reactive monomer and a reactive oligomer, 1 to 15 parts by weight of a diluent, and 0.1 to 1 part by weight of a photoinitiator.

Description

Zirconia 3D printing composition, sintered body manufactured thereby, and manufacturing method thereof {3D printing zirconia composition, sintered body manufactured thereby and manufacturing method thereof}

The present invention relates to a zirconia 3D printing composition capable of implementing various colors, a sintered body manufactured thereby, and a method for manufacturing the same.

In general, most ceramic sintered bodies were made by compression molding in a mold and sintering at high temperatures, but this method had limitations in reproducing complex shapes and in terms of economy.

3D printing is a cutting-edge manufacturing technology that decomposes a three-dimensional CAD model into two-dimensional digital cross-sections, then builds up each layer by forming it. It offers the advantage of being able to flexibly manufacture complex, precise structures that are difficult to achieve with conventional casting and machining.

Accordingly, research is being conducted continuously to manufacture ceramic sintered bodies using 3D printing technology.

However, since most of the resins contained a high content of ceramic powder, they showed major problems in high viscosity and dispersion stability.

In addition, up to now, prints and sintered bodies have been obtained using inorganic pigments, etc. to implement various colors, but in this case, there is a problem that the content of the raw material is low and the prints cannot maintain their shape after sintering.

Accordingly, there is a need for a technology for a 3D printing composition capable of producing an output product having an appropriate viscosity and high physical properties even if it contains a high content of ceramic powder, and a method for producing a sintered body using the same.

Meanwhile, the background technology described above cannot necessarily be said to be a publicly known technology disclosed to the general public prior to the filing of the present invention.

Korean Patent Publication No. 10-2146039

One embodiment of the present invention aims to provide a zirconia 3D printing composition capable of stable printing and sintering even with a high content of zirconia powder.

One embodiment of the present invention aims to provide a zirconia 3D printing composition capable of producing a sintered body having various colors and excellent physical properties.

As a technical means for achieving the above-described technical task, the zirconia 3D printing composition of the present invention comprises 65 to 90 parts by weight of zirconia powder, 5 to 20 parts by weight of a reactive monomer and a reactive oligomer, 1 to 15 parts by weight of a diluent, and 0.1 to 1 part by weight of a photoinitiator, per 100 parts by weight of the zirconia 3D printing composition.

For example, the zirconia powder may contain 45 to 90 parts by weight of white zirconia, 5 to 35 parts by weight of yellow zirconia, 1 to 20 parts by weight of pink zirconia, and 0.1 to 3 parts by weight of gray zirconia, per 100 parts by weight of the zirconia powder.

For example, the zirconia 3D printing composition may further include a coloring additive powder contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the zirconia 3D printing composition.

For example, the zirconia 3D printing composition may further include a dispersant contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the zirconia powder and the coloring additive powder.

For example, the coloring additive powder may include a metal oxide or a metal chloride, and the metal oxide may be at least one selected from the group consisting of copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), yttrium (Y), neodymium (Nd), cerium (Ce), erbium (Er), praseodymium (Pr), cobalt (Co), and nickel (Ni), and the metal chloride may be at least one selected from the group consisting of ferric chloride (FeCl ₃ 6H ₂ O), molybdenum chloride (MoCl ₃ ), chromium chloride hexahydrate (CrCl ₃ 6H ₂ O), vanadium chloride (VCl ₃ ), aluminosilicate, copper chromium oxide (Cu/Cr Oxide), iron chromium oxide (Fe/Cr Oxide), iron III oxide (FeO ₃ ), and carbon black. Can be.

For example, the reactive monomer may be characterized by being composed of an acrylate or methacrylate having 1 to 9 functional groups, and being at least one selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, unsaturated amides, aliphatic conjugated dienes, and unsaturated oxetane carboxylate compounds.

For example, the reactive monomer may be characterized as having a molecular weight of 100 to 2,000.

For example, the reactive oligomer may be characterized by being selected from the group consisting of epoxy acrylate, urethane acrylate, polyester acrylate, urethane-modified epoxy acrylate, polyether acrylate, and acrylic acrylate having 1 to 9 functional groups.

For example, the reactive oligomer may be characterized as having a molecular weight of 1,500 to 30,000.

For example, the photoinitiator may be characterized by being at least one selected from the group consisting of Phenyl-bis-(2,4,6trimethylbenzoyl) phosphine oxide (2,4,6-Trimethylbenzoyl)-diphenyl phosphine oxide, Benzophenone, 1-Hydroxy-cyclohexylphenyl-ketone, 2-Hydroxy-2-methyl1-phenyl-1-propanone, 2,2-Dimethoxy-2-phenylacetophenone, and 2-Benzyl-2dimethylamino-1[4-(4-morpholinyl) phenyl]-1-butanone.

For example, the zirconia 3D printing composition may be characterized as having a viscosity of 500 to 200,000 Cp at 25°C.

The method for manufacturing a sintered body using the zirconia 3D printing composition of the present invention includes an output forming step of forming an output by 3D printing using the zirconia 3D printing composition, a degreasing step of degreasing the output, a step of pre-sintering the degreasing output, a coloring step of coloring the pre-sintered sintered body using a metal salt liquid coloring agent, and a final sintering step of finally sintering the colored zirconia pre-sintered body.

For example, the degreasing step may include a first degreasing step of degreasing at 100 to 400°C for 1 to 10 hours, and a second degreasing step of degreasing at 400 to 700°C for 1 to 10 hours, and the step of sintering the degreasing output may include a step of sintering at 700 to 1200°C for 1 to 10 hours.

For example, the output forming step may include a step of forming the output so that the two-point bending strength of the output according to the KS M ISO6872 method is 50 to 500 KPa.

The sintered body of the present invention is manufactured using the above zirconia 3D printing composition.

For example, a sintered body manufactured using the zirconia 3D printing composition may have a three-point flexural strength of 100 to 1,000 MPa according to the KS L ISO 6872 method.

The sintered body manufactured using the above zirconia 3D printing composition may have an L* value of 40 or more, an a* value of -3.04 or more, and a b* value of 40 or less in the CIE colorimetric system (L*a*b*).

According to any one of the above-described problem solving means of the present invention, the zirconia 3D printing composition according to one embodiment of the present invention can provide a sintered body of various colors having excellent strength.

The effects that can be obtained from the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly understood by a person having ordinary skill in the art to which the present invention belongs from the description below.

Figure 1 is a flow chart of a method for manufacturing a sintered body using the zirconia 3D printing composition of the present invention.
Figure 2 is a graph showing the results of evaluating the viscosity of Examples 1 to 6 and Comparative Example 1.
Figure 3 is a graph showing the results of measuring the two-point bending strength of the outputs manufactured by Examples 1 to 6.
Figure 4 is a graph showing the results of measuring the three-point flexural strength of sintered bodies manufactured by Examples 1 to 6.

Below, with reference to the attached drawings, embodiments of the present invention are described in detail so that those skilled in the art can easily implement them. However, the present invention may be implemented in various different forms and is not limited to the embodiments described herein. In the drawings, irrelevant parts have been omitted for clarity of description, and similar reference numerals have been used throughout the specification to indicate similar elements.

Throughout the specification, when a part is said to be "connected" to another part, this includes not only "directly connected" but also "indirectly connected" with other components intervening. Furthermore, when a part is said to "include" a component, this does not exclude other components, but rather includes other components, unless otherwise stated.

A zirconia 3D printing composition according to one embodiment of the present invention comprises zirconia powder, a reactive monomer, a reactive oligomer, a diluent, and a photoinitiator.

Zirconia powder is a main component of a zirconia 3D printing composition according to one embodiment of the present invention and is a material capable of implementing the color of a sintered body.

The zirconia powder can be stabilized by a stabilizer such as yttria (Y ₂ O ₃ ), hafnia (HfO ₂ ), silica (SiO ₂ ), alumina (Al ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ), calcium oxide (CaO), magnesium oxide (MgO), etc. For example, the zirconia powder can be a zirconia powder stabilized by 3 to 8 mol% yttria.

The zirconia powder may be included in an amount of 65 to 90 parts by weight per 100 parts by weight of the zirconia 3D printing composition.

The zirconia powder may include white zirconia powder, yellow zirconia powder, pink zirconia powder and gray zirconia powder.

Specifically, the zirconia powder may include 45 to 90 parts by weight of white zirconia per 100 parts by weight of the zirconia powder, 5 to 35 parts by weight of yellow zirconia per 100 parts by weight of the zirconia powder, 1 to 20 parts by weight of pink zirconia per 100 parts by weight of the zirconia powder, and 0.1 to 3 parts by weight of gray zirconia powder per 100 parts by weight of the zirconia powder.

The reactive monomer is a material that crosslinks the photopolymerization reaction of the oligomer and may be composed of an organic material containing one or more acrylate groups.

The reactive monomer may have a molecular weight of 100 to 2,000 g/mol.

For example, the reactive monomer may be composed of an acrylate or methacrylate having a functional group of 1 to 9. For example, the reactive monomer may include at least one of aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, unsaturated amides, aliphatic conjugated dienes, and unsaturated oxetane carboxylate compounds.

A reactive oligomer is a substance that forms a polymer chain by a photopolymerization reaction, contains at least one organic functional group that causes a photopolymerization reaction, and may have a molecular weight of 1,500 to 30,000 g/mol.

For example, the reactive oligomer may include at least one of an epoxy acrylate having 1 to 9 functional groups, a urethane acrylate, a polyester acrylate, a urethane-modified epoxy acrylate, a polyether acrylate, and an acrylic acrylate.

The reactive oligomer and reactive monomer mixture may be included in an amount of 5 to 20 parts by weight per 100 parts by weight of the zirconia 3D printing composition.

The diluent is an aliphatic compound containing one or more OH groups, and may include, for example, diols such as glycerin, butyl glycol, ethylene glycol, and kaempferol, decahydronaphthalene diol, and the like.

The diluent may be included in an amount of 1 to 15 parts by weight per 100 parts by weight of the zirconia 3D printing composition.

A photoinitiator is a substance that initiates photopolymerization by generating radicals or cations by light, and may include at least one of Phenyl-bis-(2,4,6trimethylbenzoyl) phosphine oxide (2,4,6-Trimethylbenzoyl)-diphenyl phosphine oxide, Benzophenone, 1-Hydroxy-cyclohexylphenyl-ketone, 2-Hydroxy-2-methyl1-phenyl-1-propanone, 2,2-Dimethoxy-2-phenylacetophenone, and 2-Benzyl-2dimethylamino-1[4-(4-morpholinyl) phenyl]-1-butanone.

The photoinitiator may be included in an amount of 0.1 to 1 part by weight per 100 parts by weight of the zirconia 3D printing composition.

Meanwhile, the zirconia 3D printing composition according to one embodiment of the present invention may further include a coloring additive powder.

The color additive powder may contain a metal oxide or metal chloride capable of implementing color.

At this time, the metal oxide may include at least one of copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), yttrium (Y), neodymium (Nd), cerium (Ce), erbium (Er), praseodymium (Pr), cobalt (Co), and nickel (Ni).

The metal chloride may include at least one of ferric chloride (FeCl ₃ 6H ₂ O), molybdenum chloride (MoCl ₃ ), chromium chloride hexahydrate (CrCl ₃ 6H ₂ O), vanadium chloride (VCl ₃ ), aluminosilicate, copper chromium oxide (Cu/Cr Oxide), iron chromium oxide (Fe/Cr Oxide), iron III oxide (FeO ₃ ), and carbon black.

The coloring additive powder may be included in an amount of 0.01 to 1 part by weight per 100 parts by weight of the zirconia 3D printing composition.

Additionally, the zirconia 3D printing composition according to one embodiment of the present invention may further include a dispersant.

A dispersant is a substance that improves the dispersing effect of ceramic particles. BYK series, polyester (amine) series, tween surfactant, sodium lauryl sulfate, sodium dodecyl sulfate, or a mixture thereof can be used, but there are no restrictions on any material that can improve dispersibility.

The dispersant may be included in an amount of 1 to 10 parts by weight per 100 parts by weight of the zirconia powder and the coloring additive powder.

Meanwhile, the zirconia 3D printing composition according to one embodiment of the present invention may have a viscosity suitable for photocurable 3D printing. Specifically, the zirconia 3D printing composition according to one embodiment of the present invention may have a high viscosity of 500 to 200,000 cP by deriving an optimal content ratio for the ratio of zirconia powder, coloring additive powder, dispersant, reactive monomer, reactive oligomer, diluent, and photoinitiator.

A method for manufacturing a sintered body using a zirconia 3D printing composition according to one embodiment of the present invention can be performed using DLP (Digital Light Processing) or SLA (Stereolithography Apparatus). In this specification, among photocuring 3D printing methods, DLP will be described as the standard.

Figure 1 is a flow chart of a method for manufacturing a sintered body using the zirconia 3D printing composition of the present invention.

Referring to FIG. 1, the method for manufacturing a sintered body using the zirconia 3D printing composition of the present invention includes an output forming step (S10) of forming an output by 3D printing using the zirconia 3D printing composition, a degreasing step (S20) of degreasing the output, a pre-sintering step (S30) of pre-sintering the degreasing output, a coloring step (S40) of coloring the pre-sintered pre-sintered body using a metal salt liquid, and a final sintering step (S50) of sintering the colored pre-sintered body.

To manufacture a sintered body using a zirconia 3D printing composition, first, a 3D printing is performed using the zirconia 3D printing composition to form an output (S10).

The output formation (S10) step is performed by photocuring.

Specifically, the output formation step (S10) can form an output by repeating a lamination step of laminating layers with a composition and a photocuring step of photocuring the laminated layers.

The output formation step (S10) can be performed in a bottom-up manner in which light is irradiated from the bottom to the top, or in a top-down manner in which light is irradiated from the top to the bottom.

Bottom-up photocuring involves irradiating light onto photocurable materials through a transparent stage or tank. Therefore, light may be scattered or reflected as it passes through the stage or tank, potentially reducing output precision and efficiency. On the other hand, top-down photocuring directly irradiates light onto photocurable materials, resulting in higher output precision and efficiency than bottom-up photocuring. Therefore, the output formation step (S20) according to one embodiment of the present invention may be more preferably performed using a top-down method.

Additionally, the output formation step (S10) may irradiate light of at least one wavelength among ultraviolet, infrared, or visible light. Specifically, light of a surface unit may be irradiated using a laser or projection method that irradiates point-by-point light of the wavelength range described above.

Meanwhile, the output formation step (S10) can form an output by setting model-related settings such as slicing thickness, supporter settings, and position settings, and shaping-related conditions such as irradiation time, waiting time, and build plate movement distance using software related to the 3D printer.

Meanwhile, the output formed by the above-described method can have a two-point flexural strength of 50 to 500 KPa.

When the output formation is complete, the output is degreased (S20).

The degreasing (S20) step can be performed to remove internal organic matter used to manufacture the composition for 3D printing.

The degreasing (S20) step may be divided into two or more stages to control the discharge of the polymer material as slowly as possible while maintaining low activity.

For example, primary degreasing can be performed at 100 to 400°C for 1 to 10 hours.

Secondary degreasing can be performed at 400 to 700°C for 1 to 10 hours.

Once the degreasing is complete, the degreasing output is sintered (S30).

The sintering step (S30) can be performed to achieve appropriate strength in the output before applying the coloring solution.

The sintering (S30) step can be performed by pressure sintering, which densifies the workpiece by heat treatment at high temperature in air or an inert atmosphere at atmospheric pressure, or pressure sintering, which densifies the workpiece by applying pressure and heat from the outside.

For example, the sintering (S30) step can be performed at 700 to 1200°C for 1 to 10 hours.

If the process is performed at a temperature below 700°C for less than 1 hour, the densification of the material may not occur properly, which may result in a deterioration of the desired properties of the sintered body. Conversely, if the process is performed at a temperature exceeding 1200°C for more than 10 hours, the penetration of the coloring solution may not be easy, making it difficult to achieve the desired color in the coloring (S40) step.

When the sintering is complete, the sintered body is colored (S40) using a coloring solution.

The coloring (S40) step can be performed to implement a more distinct color in the sintered body.

The coloring solution may be composed of a metal salt solution. For example, the coloring solution may be ferric nitrate nonahydrate (FeH ₁₈ N ₃ O ₁₈ ), chromium nitrate nonahydrate (Cr(NO ₃ ) ₃ 9H ₂ O), praseodymium nitrate hexahydrate (Pr(NO ₃ ) ₃ 6H ₂ O), manganese nitrate hexahydrate (Mn(NO ₃ ) ₂ xH ₂ O), erbium nitrate hexahydrate (Er(NO ₃ ) ₃ xH ₂ O), neodymium nitrate hexahydrate (Nd(NO ₃ ) ₃ 6H ₂ O), cobalt nitrate hexahydrate (Co(NO ₃ ) ₂ 6H ₂ O), chromium chloride hexahydrate (CrCl ₃ 6H ₂ O), terbium chloride hexahydrate (TbCl ₃ 6H ₂ O), neodymium chloride hexahydrate (NdCl ₃ ·6H ₂ O), erbium chloride hexahydrate (ErCl ₃ ·6H ₂ O), etc.

Additionally, the coloring solution includes an acid based coloring agent and a water-based coloring agent.

Acidic colorants contain hydrochloric acid, a strong acid, and can impart color through an acid-base reaction. Water-based colorants can impart color by penetrating metal cations into porous zirconia without the need for an acid component.

Meanwhile, the coloring (S40) step can be performed by spraying or spreading a coloring solution on the surface of the sintered body or by immersing the sintered body in a coloring solution.

Once coloring is complete, the colored sintered body undergoes final sintering (S50).

A final sintering (S50) step may be performed to provide a sintered body with improved strength.

Final sintering can be performed at 1,300 to 1,500°C for 2 to 24 hours.

If the process is performed at temperatures below 1300℃ for less than 2 hours, densification between materials may not occur properly, which may deteriorate the physical properties of the sintered body. Conversely, if the process is performed at temperatures exceeding 1500℃ for more than 24 hours, chemical phase transformation of the material may occur.

The final sintering (S50) step can be performed, like the pre-sintering (S30) step, by heat-treating the workpiece at high temperature in air or an inert atmosphere at atmospheric pressure to densify it, or by pressure sintering to densify it by applying pressure and heat from the outside of the workpiece.

The method for manufacturing a sintered body using the composition for 3D printing of zirconia according to the embodiment of the present invention described above manufactures a sintered body using the composition for 3D printing of zirconia, and thus can provide sintered bodies of various colors.

A method for manufacturing a sintered body using a zirconia 3D printing composition according to one embodiment of the present invention includes two or more steps of degreasing and pre-sintering a high-viscosity ceramic 3D printing output, thereby enabling the polymer material to be controlled to be discharged as slowly as possible while maintaining low activity. Accordingly, cracks or delamination on the surface of the sintered body can be prevented during sintering. In other words, a sintered body having excellent strength can be provided.

In addition, the method for manufacturing a sintered body using a composition for zirconia 3D printing according to one embodiment of the present invention includes a step of coloring with a coloring solution, and thus can provide a sintered body having a more distinct color.

Additionally, in the CIE colorimetric system values (L*a*b*), the L* value can be 7 or more, the a* value can be -3.04 or more, and the b* value can be 40 or less.

Hereinafter, the present invention will be described in detail through examples, but the present invention is not limited to these examples.

Example.

Manufacturing Example 1. Manufacturing of a sintered body using a composition for zirconia 3D printing.

Each raw material was added in the content ratio according to [Table 1] and stirred at a speed of 1000 rpm for 5 minutes to prepare a composition for zirconia 3D printing.

division sample Zirconia (wt%) Oligomer (wt%) monomer
(wt%)
Dispersant (wt%) Diluent (wt%) Initiator (wt%) Colorant (wt%) WZ YZ PZ GZ Example 1 YZ 5 75 5 1 1 2 5 5 5 0.1 0.9 Example 2 YZ 10 70 10 Example 3 YZ 20 60 20 Example 4 YZ 25 55 25 Example 5 YZ 30 50 30 Example 6 YZ 35 45 35 Comparative Example 1 YZ 40 40 40 Comparative Example 2 YZ 2 78 2

since, The composition for zirconia 3D printing was printed using a 3D printing device to form a printed product.

The output was heated to 250°C at a rate of 0.5°C/min and then maintained at 370°C for 3 hours to perform the first degreasing, and then heated to 450°C at a rate of 0.5°C/min and then maintained for 3 hours to perform the second degreasing.

After degreasing was completed, sintering was performed at 1,000°C for 2 hours, and coloring was performed with a coloring solution.

After coloring was completed, a sintered body was manufactured by sintering at 1350°C for 2 hours.

Experimental Example 1. Evaluation of Composition Viscosity

In this experiment, the viscosity of the composition was evaluated according to the content of yellow zirconia added to the composition for zirconia 3D printing.

Figure 2 is a graph showing the results of evaluating the viscosity of Examples 1 to 6 and Comparative Example 1.

Referring to FIG. 2, it can be confirmed that examples 1 to 6 have a viscosity of 500 to 200,000 cp.

In contrast, in the case of Comparative Example 1, it can be confirmed that it has a viscosity exceeding 200,000cp.

Specifically, in Comparative Example 1, it was confirmed that as the content of yellow series zirconia exceeded 35 weight ratio with respect to 100 weight ratio of zirconia powder, the influence of metal oxides and metal chlorides in the coloring additive powder increased, resulting in a significant increase in viscosity.

Since Examples 1 to 6 are manufactured with a composition according to one embodiment of the invention, they have an appropriate viscosity of 500 to 200,000 cp, and can prevent the problem of the viscosity of the composition being too high and thus not being able to output the output.

Meanwhile, it can be confirmed that the viscosity of the composition for zirconia 3D printing gradually decreases as the content of yellow zirconia in the zirconia powder decreases.

When the content of yellow zirconia in the zirconia powder is less than 5 weight ratio with respect to 100 weight ratio of the zirconia powder, the coloring power of the sintered body is reduced, making it difficult to feel the color difference from the white zirconia sintered body.

Experimental Example 2. Evaluation of the Flexural Strength of the Printed Product

First, the two-point bending strength of the outputs manufactured by Examples 1 to 6 and Comparative Example 1 was measured according to the KS M ISO6872 method for outputs produced by 3D printing.

The flexural strength value according to the KS M ISO6872 method can be used to determine the degree of curing of the resin, and a higher value means better bonding between layers.

Figure 3 is a graph showing the results of measuring the two-point bending strength of the outputs manufactured by Examples 1 to 6.

Referring to Fig. 3, it can be confirmed that the two-point bending strength of the outputs manufactured by Examples 1 to 6 is 50 to 500 KPa.

In contrast, it can be confirmed that the two-point bending strength of the output manufactured by Comparative Example 1 is less than 50 KPa.

Specifically, in Comparative Example 1, it can be confirmed that the two-point flexural strength is reduced as the content of yellow zirconia exceeds 35 weight ratio with respect to 100 weight ratio of zirconia powder.

Through this, it can be confirmed that Examples 1 to 6 are manufactured with a composition according to one embodiment of the invention and thus have excellent two-point flexural strength of 50 to 500 KPa.

That is, it can be seen that the output of the present invention has excellent strength despite being degreased and sintered, and that post-processing, etc., is easy.

Experimental Example 3. Evaluation of the flexural strength of the sintered body

Meanwhile, the three-point flexural strength of the sintered bodies manufactured by Examples 1 to 6 was measured according to the KS L ISO 6872 method.

Figure 4 is a graph showing the results of measuring the three-point flexural strength of sintered bodies manufactured by Examples 1 to 6.

Referring to Fig. 4, it can be confirmed that the three-point flexural strength of the sintered bodies manufactured by Examples 1 to 6 is 100 to 1,000 MPa.

In contrast, it can be confirmed that the three-point flexural strength of the sintered body manufactured by Comparative Example 1 is less than 100 MPa.

Specifically, in Comparative Example 1, it can be confirmed that the 3-point flexural strength is reduced as the content of yellow zirconia exceeds 35 weight ratio with respect to 100 weight ratio of zirconia powder.

Through this, it can be confirmed that Examples 1 to 6 are manufactured with a composition according to one embodiment of the present invention, and thus have excellent three-point flexural strength of 100 to 1,000 MPa.

That is, in the present invention, although a sintered body was manufactured by applying a 3D printing method, it can be seen that it has similar physical property values to a sintered body manufactured through a traditional ceramic process.

Experimental Example 4. Evaluation of optical properties of sintered bodies

In this experiment, the CIE colorimetric values (L*a*b*) of the sintered body were measured.

At this time, the CIE colorimetric values were measured using a spectrophotometer (CM-5, KONICA MINOLTA, Japan).

Table 2 shows the CIE colorimetric values (L*a*b*) of the sintered body.

division Sample L* a* b* Comparative Example 2 WZ(78wt%)+YZ(2wt%)+
PZ(1wt%)+GZ(1wt%) 70.7 3 13.7 Example 1 WZ(75wt%)+YZ(5wt%)+
PZ(1wt%)+GZ(1wt%) 68.1 7.8 29.9 Example 2 WZ(70wt%)+YZ(10wt%)+PZ(1wt%)+GZ(1wt%) 45.8 7.1 39.5

The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (17)

In zirconia 3D printing compositions
65 to 90 parts by weight of zirconia powder per 100 parts by weight of the above zirconia 3D printing composition;
5 to 20 parts by weight of a reactive monomer and a reactive oligomer per 100 parts by weight of the above zirconia 3D printing composition;
1 to 15 parts by weight of a diluent for 100 parts by weight of the above zirconia 3D printing composition; and
Contains 0.1 to 1 part by weight of a photoinitiator for 100 parts by weight of the above zirconia 3D printing composition,
The above zirconia powder
Based on 100 parts by weight of the above zirconia powder, it contains 45 to 90 parts by weight of white zirconia, 5 to 35 parts by weight of yellow zirconia, 1 to 20 parts by weight of pink zirconia, and 0.1 to 3 parts by weight of gray zirconia.
The above yellow zirconia powder is included in an amount greater than the weight part of the above reactive monomer,
Zirconia 3D printing composition. delete In the first paragraph,
The above zirconia 3D printing composition
Further comprising a coloring additive powder contained in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the above zirconia 3D printing composition.
Zirconia 3D printing composition. In the third paragraph,
The above zirconia 3D printing composition
Further comprising a dispersant contained in an amount of 1 to 10 parts by weight per 100 parts by weight of the zirconia powder and the coloring additive powder.
Zirconia 3D printing composition. In the third paragraph,
The above coloring additive powder
Containing metal oxides or metal chlorides,
The above metal oxide is at least one selected from the group consisting of copper (Cu), iron (Fe), magnesium (Mg), manganese (Mn), yttrium (Y), neodymium (Nd), cerium (Ce), erbium (Er), praseodymium (Pr), cobalt (Co), and nickel (Ni).
The metal chloride is characterized in that it is at least one selected from the group consisting of ferric chloride (FeCl ₃ 6H ₂ O), molybdenum chloride (MoCl ₃ ), chromium chloride hexahydrate (CrCl ₃ 6H ₂ O), vanadium chloride (VCl ₃ ), aluminosilicate, copper chromium oxide (Cu/Cr Oxide), iron chromium oxide (Fe/Cr Oxide), iron III oxide (FeO ₃ ), and carbon black.
Zirconia 3D printing composition. In the first paragraph,
The above reactive monomer is
It is composed of acrylate or methacrylate having 1 to 9 functional groups,
A composition characterized by comprising at least one selected from the group consisting of aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, unsaturated amides, aliphatic conjugated dienes, and unsaturated oxetane carboxylate compounds.
Zirconia 3D printing composition. In the first paragraph,
The above reactive monomer is
Characterized by having a molecular weight of 100 to 2,000,
Zirconia 3D printing composition. In the first paragraph,
The above reactive oligomer is
Characterized in that at least one is selected from the group consisting of epoxy acrylate, urethane acrylate, polyester acrylate, urethane-modified epoxy acrylate, polyether acrylate, and acrylic acrylate having 1 to 9 functional groups.
Zirconia 3D printing composition. In the first paragraph,
The above reactive oligomer is
Characterized in that it has a molecular weight of 1,500 to 30,000,
Zirconia 3D printing composition. In the first paragraph,
The above photoinitiator
Phenyl-bis-(2,4,6trimethylbenzoyl)phosphine oxide
(2,4,6-Trimethylbenzoyl)-diphenyl phosphine oxide
Benzophenone, 1-Hydroxy-cyclohexylphenyl-ketone
2-Hydroxy-2-methyl1-phenyl-1-propanone,
2,2-Dimethoxy-2-phenylacetophenone
2-Benzyl-2dimethylamino-1[4-(4-morpholinyl) phenyl]-1-butanone
Characterized by at least one selected from among
Zirconia 3D printing composition. In the first paragraph,
The above zirconia 3D printing composition
Characterized by having a viscosity of 500 to 200,000 Cp at 25°C,
Zirconia 3D printing composition. An output formation step of forming an output by 3D printing using the zirconia 3D printing composition according to Article 1;
A degreasing step for degreasing the above output;
A step of sintering the above-degreased output;
A coloring step of coloring the above-mentioned sintered body using a metal salt liquid coloring agent; and
Including a final sintering step for finally sintering the colored zirconia sintered body,
A method for manufacturing a sintered body using a zirconia 3D printing composition. In paragraph 12,
The above degreasing step
A first degreasing step of degreasing at 100 to 400°C for 1 to 10 hours; and
Includes a secondary degreasing step of degreasing at 400 to 700°C for 1 to 10 hours,
The step of sintering the above-degreased output is as follows:
Comprising a step of sintering at 700 to 1200°C for 1 to 10 hours,
A method for manufacturing a sintered body using a zirconia 3D printing composition. In paragraph 12,
The above output formation step is,
Including a step of forming the output so that the two-point bending strength of the output according to the KS M ISO6872 method is 50 to 500 KPa.
A method for manufacturing a sintered body using a zirconia 3D printing composition. A sintered body manufactured using the zirconia 3D printing composition according to claim 1. In Article 15,
The sintered body manufactured with the above zirconia 3D printing composition has a three-point flexural strength of 100 to 1,000 MPa according to the KS L ISO 6872 method.
A sintered body manufactured from a zirconia 3D printing composition. In Article 15,
The sintered body manufactured from the above zirconia 3D printing composition
In the CIE colorimetric system (L*a*b*), the L* value is greater than 40, the a* value is greater than -3.04, and the b* value is less than 40.
A sintered body manufactured from a zirconia 3D printing composition.