KR102297422B1 - 3D Printing Method using 3D printing slurry - Google Patents

Abstract

According to an embodiment of the present invention, a 3D printing method comprises: a first step of providing a precursor film by applying a first mixture in which a polymer and ceramic powder are mixed; and a second step of providing a printed layer by adding a reaction solution to at least a partial area of the precursor film to cure an area to which the reaction solution is added in the precursor film. On the printed layer provided by performing the first step and the second step, provided is a three-dimensional structure in which a plurality of printed layers are stacked by repeating the first and second step sequentially at least once or more and removing the uncured precursor film. The ceramic powder includes at least one selected from a first metal and an oxide, a hydroxide, a nitride, a halide, and an oxynitride of the first metal. The reaction solution includes a salt of the first metal. Accordingly, the present invention can be applied to various technical fields such as automobiles, ships, trains, aerospace, home appliances, biomedical devices, precision parts, etc.

Description

3D Printing Method using 3D printing slurry

The present invention relates to a method for preparing a slurry for 3D printing prepared by mixing a ceramic, a polymer, and a reaction solution, and a method for performing 3D printing using the slurry for 3D printing prepared by the manufacturing method.

Additive manufacturing (AM), known as 3D printing, is a solid free-form fabrication (SFF) for building or printing physical three-dimensional (3D) articles from computer-aided design (CAD) models of articles. ) to use technology. Additive processes are attractive because they can produce parts with complex geometries without complex tools and with minimal product production time. Lamination processes work with solid, liquid, and powder materials. Therefore, in theory, if the part material can be provided in solid, liquid, or powder form, the part can be produced via additive manufacturing.

Although AM technology has reached the maturity level of metal and polymer materials, the maturity level of ceramic materials is still quite behind. Stereolithography (SLA), selective laser melting or sintering (SLM/SLS), and 3D printing are examples of SFF techniques that can be used to build 3D ceramic parts.

Although SLS/SLM is widely used for metals, its application to ceramics is more complex because of the high thermal gradients created in the process and the lack of ductility of the ceramic material makes it difficult to produce defect-free parts even at high densities.

Ceramic materials have excellent strength, abrasion resistance, corrosion resistance, and heat resistance, but they require a long processing time and high processing cost due to their inherent weakness, which is brittleness. In the ceramic product process, the processing cost in severe cases can account for more than 80% of the total cost required to manufacture ceramic products, making industrial manufacturing of complex-shaped ceramic products practically impossible and acting as a decisive factor limiting the field of application of ceramic materials. come.

In addition, one of the keys to managing the ceramic powder used in the lamination process is to maintain the purity of the powder material used. In the 3D printing process, the incorporation of contaminants may lead to cracks and side effects of the final product, and the failure of the process may result. Purity control is very important because there is a loss of time and money.

Republic of Korea Patent No. 10-2056100

Accordingly, as a result of intensive research efforts on ceramic binders and slurry materials suitable for use in the lamination process, the present inventors have prepared a slurry for 3D printing with improved purity and hardness prepared by adding a reaction solution containing a salt of the same metal as the ceramic. completed.

According to an embodiment of the present invention, a first step of providing a precursor film by applying a first mixture in which a polymer and ceramic powder are mixed; and a second step of providing a printed layer by adding a reaction solution to at least a partial area of the precursor film to cure the area to which the reaction solution is added in the precursor film, wherein the first step and the second step repeating the first step and the second step at least one time or more in sequence on the printed layer provided by performing, and removing the uncured precursor film to provide a three-dimensional structure in which a plurality of layers of the printed layer are laminated, , The ceramic powder includes at least one selected from a first metal, an oxide, a hydroxide, a nitride, a halide, and an oxynitride of the first metal, and the reaction solution includes a salt of the first metal, three-dimensional printing A method is provided.

According to an embodiment of the present invention, the ceramic powder includes an oxide of the first metal, and the reaction solution is a nitrate, carboxylate, sulfate, persulfate, citrate, phosphate, or borate of the first metal. , a three-dimensional printing method is provided, comprising at least one selected from the group consisting of perborates and halides.

According to an embodiment of the present invention, in the second step, curing is induced through a gelation reaction by electrostatic attraction between the salt of the first metal included in the reaction solution and the polymer included in the first mixture, , The first metal included in the reaction solution for inducing curing of the polymer and the first metal in the ceramic powder included in the first mixture are the same type, a three-dimensional printing method is provided.

According to an embodiment of the present invention, the first metal is aluminum (Al), zinc (Zn), cerium (Ce), zirconium (Zr), titanium (Ti), cobalt (Co), iron (Fe), gold (Au), silver (Ag), platinum (Pt), copper (Cu), nickel (Ni), at least one selected from the group consisting of chromium (Cr), a three-dimensional printing method is provided.

According to an embodiment of the present invention, a three-dimensional printing method is provided, wherein the ceramic powder has a particle size of 0.02 to 500 (μm unit base).

According to one embodiment of the present invention, the polymer comprises at least one selected from the group consisting of cellulose, alginic acid, lignin, silk, and collagen, a three-dimensional printing method is provided.

According to an embodiment of the present invention, the polymer includes cellulose, and the cellulose is cellulose cured by infrared irradiation or surface-modified with a carboxyl group, a three-dimensional printing method is provided.

According to an embodiment of the present invention, the cellulose has a viscosity of 100 to 100,000 cps (or) a weight average molecular weight (Mw) of 30,000 to 1,500,000, a three-dimensional printing method is provided.

The present invention facilitates the preparation of a ceramic slurry excellent for lamination process using a polymer binder and a metal salt reaction solution, and the slurry prepared by this manufacturing method can improve the hardness as well as increase the purity compared to the conventional slurry. The present invention can be applied to various technical fields such as automobiles, ships, trains, aerospace, home appliances, biomedical devices, and precision parts.

1 is a flowchart illustrating a three-dimensional printing method.
2 is an image of the curing of the precursor film in the manufacturing method of the present invention.
3 is an image of the product prepared in each step of the manufacturing method of the present invention.
4 to 7 are images showing a first mixture prepared according to an embodiment of the present invention, and a three-dimensional structure printed using the first mixture.

Hereinafter, the present invention will be described in more detail through examples. These Examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by these Examples.

According to an embodiment of the present invention, a three-dimensional structure can be easily and quickly manufactured by applying the first mixture and curing only a desired area with a reaction solution.

1 is a flowchart illustrating a three-dimensional printing method. 2 is a diagram illustrating the curing of the precursor film in the manufacturing method of the present invention.

1 and 2 , the 3D printing method according to an embodiment of the present invention includes a first step of providing a precursor film by applying a first mixture in which a polymer and ceramic powder are mixed; and a second step of providing a printed layer by adding a reaction solution to at least a partial area of the precursor film to cure the area to which the reaction solution is added in the precursor film, wherein the first step and the second step Repeating the first step and the second step at least once in sequence on the printed layer provided by performing, and removing the uncured precursor film to provide a three-dimensional structure in which a plurality of layers of the printed layer are laminated .

In particular, the ceramic powder included in the first mixture used in the 3D printing method includes at least one selected from a first metal, an oxide, a hydroxide, a nitride, a halide, and an oxynitride of the first metal, and the reaction solution includes a salt of the first metal.

According to the present invention, as the mixture of the first metal particles, the first metal ions, and the polymer compound is cured, optionally cured and sintered, a printed layer having high purity and hardness may be provided. In this case, since the metal network formed by oxidation or reduction from the solid metal particles and metal ions is provided as a material of the same element, the purity of the printed layer formed is high. In addition, due to the combination of the oxidized or reduced metal particles provided between the gel-type polymer network and the polymer network, there is relatively little empty space inside the printed layer, and thus the overall hardness of the printed layer may be excellent.

As used herein, the term '3D (three dimension) 　 printing' refers to various manufacturing processes for forming a 3D object through a process of stacking layers of a series of materials. In the 3D printing process, for example, there are various methods such as selective laser sintering molding, extrusion lamination molding, direct metal laser sintering molding, photocuring resin molding, extraction product manufacturing, electron beam sintering, and the like. However, in the case of the present invention, three-dimensional printing may be performed in a manner of manufacturing a three-dimensional structure by applying the first mixture to provide a precursor film, and repeating the process of forming a printed layer by curing some regions of the precursor film. .

First, a precursor film is provided by applying a first mixture in which a polymer and ceramic powder are mixed in the first step. In the first step, a polymer that allows the ceramic powder to be laminated may be mixed. In addition, a step of pulverizing the ceramic raw material may be performed before the first step.

When mixing the polymer and the ceramic powder in the first step, a solvent, deionized water, and a dispersant may be additionally included in addition to the ceramic powder and the polymer.

The ceramic powder includes at least one selected from a first metal, an oxide, a hydroxide, a nitride, a halide, and an oxynitride of the first metal, and specifically alumina (Al ₂ O ₃ ), aluminum nitride (AlN), zirconia ( ZrO ₂ ), silica (SiO ₂ ), zirconium chloride (ZrCl), ceria (CeO ₂ ), aluminum acetate, silicon nitride (Si ₃ N ₄ ), magnesium oxide (MgO), yttria (Y ₂ O ₃ ), etc. There may be, but is not limited thereto.

The particle size of the ceramic powder is in the range of 0.05 to 500 (μm unit base). The particle size is a very important factor in defining the time and temperature required to achieve true density during sintering of the slurry. In the present invention, when the particle size is more than 500 μm, the ceramic powder is inefficiently packed, so that large pores are formed during sintering, thereby reducing strength.

The ceramic powder: polymer mixing ratio (weight ratio) is 99: 1 to 60: 40.

When mixing, the polymer is slowly added and mixed until a target mass fraction is reached, and the mixing time may be approximately 2 to 8 hours, but is not limited thereto.

The 'polymer' of the present invention means an organic binder. The organic binder is an important factor in determining the fluidity and dryness of the slurry. The organic binder is removed in the slurry sintering step so that the 3D printing product using the slurry can obtain desirable mechanical properties. This is because, depending on the percentage of binder present in this post-treatment process (sintering process), it can cause shrinkage of the part.

The polymer of the present invention is to include at least one selected from the group consisting of cellulose, alginic acid, lignin, silk, and collagen.

In the case of alginic acid used in an embodiment of the present invention as the polymer, it may be crosslinked by the addition of polyvalent cations to induce gel formation. Alginic acid has a secondary role in improving the rheological properties of the slurry for the deposition process and preventing cracking during drying by acting as a binder. Also, the addition of alginic acid increases the viscosity of the slurry and causes a higher shear-thinning behavior to have a more uniform flow during slurry deposition. It is also known that different cations have different affinities for alginic acid and different concentrations required to crosslink it. Accordingly, in an embodiment of the present invention, gel formation was induced by adding the same metal salt as the ceramic powder included in the reaction solution in the second step. Similarly, other polymers can be gelled in the same way.

At least one polymer selected from the group consisting of cellulose, alginic acid, lignin, silk, and collagen may be a polymer compound cured by infrared irradiation or surface-modified with a carboxyl group. In addition, the polymer may have a viscosity of 100 to 100,000 cps or a weight average molecular weight (Mw) of 30,000 to 1,500,000.

In some cases, the polymer may be cellulose.

The cellulose of the present invention may be specifically a cellulose surface-modified with a carboxyl group or cured by infrared irradiation. As a result of using the cellulose, it was shown that the purity and hardness were significantly improved as the slurry for 3D printing of the present invention. The cellulose surface-modified with a carboxyl group may be, for example, carboxylmethyl cellulose (CMC). Carboxyl cellulose may be substituted with ions of the first metal included in the second mixture. Specifically, protons of the carboxyl group of cellulose may be substituted with ions of the first metal to exhibit excellent adhesion properties. In addition, the cellulose surface-modified with a carboxyl group may be polymerized with each other in the second step, and may form a gel-type layer.

The cellulose has a weight average molecular weight (Mw) of 30,000 to 1,500,000. If it is less than 30,000, the viscosity may be too low and sedimentation may occur, and if it exceeds 1,500,000, the viscosity is too high and the solubility of cellulose is lowered. When using the cellulose, for example, a photopolymerization method (PP) among 3D printing methods may be introduced. This is a method of manufacturing a three-dimensional shape by selectively irradiating light in the UV or visible ray region to a photocurable material or a composite containing a photocurable material, and it is possible to print by mixing up to 50% of ceramic particles. The content of the ceramic particles may be adjusted according to the particle size, dispersion degree, dispersant, and the like.

After preparing the first mixture, the prepared first mixture is applied to provide a precursor film. There is no limitation on the application method of the first mixture. The thickness of the precursor film is not limited, but may be determined in consideration of the viscosity of the first mixture and the shape of the three-dimensional structure to be manufactured.

Next, a second step of providing a printed layer by adding a reaction solution to at least a partial area of the applied precursor film to harden the area to which the reaction solution is added among the precursor film is performed. Rapid curing may occur in the region where the reaction solution is added in the precursor film applied in the second step.

As used herein, the term 'reactant' means a solution containing a salt of the same metal as the first metal element when the ceramic powder contains a first metal element.

The solvent of the reaction solution may be any one selected from the group consisting of distilled water, ethylene glycol, toluene, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, xylene, and tetrohydrofuran. . However, there is no particular limitation on the solvent of the reaction solution.

The reaction solution is added in an amount of 0.01 to 10 vol% (volume ratio) based on the slurry. If it is less than 0.01, sufficient reaction with the second mixture is not possible, and if it is more than 10, the viscosity of the second mixture may be reduced and restrictions may occur in realization of the shape.

The second mixture produced in the second step may be additionally pulverized and mixed. In this case, the process may use a ball milling process, but is not limited thereto.

The ceramic powder of the present invention includes at least one selected from a first metal, an oxide, a hydroxide, a nitride, a halide, and an oxynitride of the first metal, and the reaction solution includes a salt of the first metal. For example, the salt of the first metal may be at least one selected from nitrate, carboxylate, sulfate, persulfate, citrate, phosphate, borate, perborate, and halide. The salt of the first metal may be provided by dissociation into cations and anions of the first metal in the second mixture.

Specifically, after performing the second step, the salt of the first metal included in the reaction solution and the oxide of the first metal included in the ceramic powder are the same as the first metal after the salt of the first metal is oxidized. It has the technical features of the present invention by being fused with an oxide or reducing a salt of the first metal to form a network with the first metal particles.

The first metal is aluminum (Al), zinc (Zn), cerium (Ce), zirconium (Zr), titanium (Ti), cobalt (Co), iron (Fe), gold (Au), silver (Ag), It may be at least one selected from the group consisting of platinum (Pt), copper (Cu), nickel (Ni), and chromium (Cr). In an embodiment of the present invention, aluminum, zinc, or cerium is used, but the present invention is not limited thereto.

The concentration of the salt of the first metal in the reaction solution may be 0.01 to 1 mol/L. If it is less than 0.01 mol/L, there is a problem in that the polymer is not sufficiently gelled. When it exceeds 1 mol/L, there is a problem that the salt forms a precipitated phase in the reaction solution.

As a result of performing the second step, referring to FIG. 2 , a second mixture (L200) is prepared, and the ceramic powder (a10), the polymer (a20), and M ^{x+, which} is a metal ion in the reaction solution, are present in the solvent (a40). is provided

The mixing of the second step may be performed for approximately 2 to 8 hours and may further include a sieving process.

In the second step, the precursor film is cured by adding the reaction solution. Specifically, the region to which the reaction solution is added in the precursor film is cured.

Referring to Figure 2, the final slurry (L300) is prepared by the addition of the reaction solution, and the polymer and metal ions (M ^x+ ) present in the second mixture (L200) have a gelled form (a30) due to crosslinking, etc. it has been shown In addition, as the solvent (a40) evaporates during the curing step, agglomeration similar to agglomerates may occur.

During the curing process, the polymer is gelled so that the viscosity of the slurry is 100 to 100,000 cps.

The gelled form (a30) in the second step may be a result of polymerization of the polymer compound. For example, alginic acid or cellulose included in the second mixture may be further polymerized by reacting adjacent molecules with each other. A graft polymer may be formed by polymerization. Since the graft polymer includes a main chain and a side chain, it can be provided more densely throughout the printed layer. In addition, metal particles and metal ions are provided between the densely formed polymer compound grafted polymer network and sintered to form a high-density printed layer made of the polymer compound and metal.

According to the prior art, since 3D printing is performed using only metal oxide particles in a solid state, there is a problem in that there are many empty spaces between the particles, and thus the density of the printed layer is relatively low. In addition, in the case of a method of oxidizing or reducing metal ions by providing only metal ions without solid metal oxide particles, there is a problem in that it takes a lot of energy and time to oxidize or reduce all metal ions. According to an embodiment of the present invention, it is possible to provide a high-density printed layer within a short time while reducing energy consumption by using both the solid metal oxide particles and the same metal ions as the metal elements constituting the particles.

As the mixture of the first metal oxide particles, the first metal ions, and the polymer compound is cured in the second step, a printed layer having high purity and hardness may be provided. At this time, as the metal network formed by oxidation or reduction from the solid metal oxide particles and metal ions as described above is provided with the same element material, the purity of the printed layer formed is high. The high purity of the printed layer may mean that the ratio of metal atoms of the same type in the printed layer is high. Accordingly, electrons may move more freely along a network formed by the same type of metal atoms compared to a printed layer in which different metal atoms are mixed. Therefore, the printed layer can exhibit excellent conductivity. In addition, as described above, due to the combination of the oxidized or reduced metal particles provided between the gel-type polymer network and the polymer network, there is relatively little empty space inside the printed layer, and thus the overall hardness of the printed layer can be excellent. .

Next, the first step and the second step may be sequentially repeated at least once on the printed layer provided by performing the first step and the second step. Accordingly, another printed layer may be laminated on the printed layer. After the plurality of printed layers are laminated, the uncured precursor film can be removed.

Accordingly, after the uncured precursor film is removed, a three-dimensional structure formed by stacking a plurality of printed layers may remain.

Another aspect of the present invention is a ceramic; polymer; and a metal ion, wherein the ceramic is at least one selected from oxides, hydroxides, nitrides, halides, and oxynitrides of the first metal, and the polymer is at least selected from the group consisting of cellulose, alginic acid, lignin, silk and collagen. One thing, and the metal ion is to provide a slurry for 3D printing, which is an ion of the same first metal as the ceramic.

The second aspect prepared by the method of the first aspect of the present invention also includes ions of the same first metal as the first metal type constituting the ceramic, providing a slurry with improved hardness and purity, which are important physical properties during the lamination process. It is characterized by being possible.

The first metal of the present invention is aluminum (Al), zinc (Zn), cerium (Ce), zirconium (Zr), titanium (Ti), cobalt (Co), iron (Fe), gold (Au), silver ( Ag), platinum (Pt), copper (Cu), nickel (Ni), may be at least one selected from the group consisting of chromium (Cr).

The ceramic: polymer weight ratio of the present invention is 99: 1 to 60: 40.

The viscosity of the slurry of the present invention is 100 to 100,000 (based on cps units). When the viscosity is more than 100,000, there is a problem in that the flow rate is lowered in the case of the slurry, and when the viscosity is less than 100, there is a problem in that the retention of the shape is deteriorated.

The finally produced slurry of the present invention can be applied to 3D printing in various ways depending on the properties of the constituent ceramic or polymer material and the curing method.

3 is an image of the product prepared in each step of the manufacturing method of the present invention.

Referring to FIG. 3 , a precursor film is formed by first applying the first mixture as in (a). Next, as shown in (b), the area to which the reaction solution is applied is cured by referring to the reaction solution in at least a portion of the precursor film. Next, as in (c), the first mixture is applied again on the printed layer cured by the reaction solution to form a precursor film. Next, another printed layer is provided on the printed layer by adding a reaction solution on the precursor film again as in (d). Finally, as shown in (e), a three-dimensional structure formed by stacking printed layers is provided.

Hereinafter, a three-dimensional printing method according to a specific embodiment of the present invention will be described.

4 to 7 are images showing a first mixture prepared according to an embodiment of the present invention, and a three-dimensional structure printed using the first mixture.

First, referring to FIG. 4 , the first mixtures prepared according to Examples 1 to 3 can be identified.

Example 1. Al ₂ O ₃ Al in the first mixture containing ³⁺ Example of a process in which a second mixture was prepared by mixing a reaction solution containing a metal salt and then cured

(1) preparing a first mixture by mixing ceramic powder and polymer

15 g of alumina powder having a particle size of 0.2 μm was sieved and prepared to have an even particle size. After adding 0.075 g of citric acid to the alumina powder, the mixture was rotated and mixed for 2 hours at a speed of 50 rpm using a ball mill. Then, 5 mL of an aqueous solution-based alginic acid solution (30 g/L) and 5 mL of distilled water were mixed with the mixed powder. A first mixture was prepared by rotationally mixing this for 12 hours at a speed of 50 rpm using a ball mill.

(2) reaction solution preparation step

A reaction solution was prepared by dissolving 2 g of Al(NO ₃ ) ₃ ·9H ₂ O in 20 mL of ethylene glycol. At this time, ^{the concentration of Al 3+} ions in the reaction solution is about 266 mM.

(3) After applying the first mixture to a thickness of 100 ~ 200 ㎛ on the surface of the glass substrate, and then dried with a heat of about 70 degrees. Thereafter, a reaction solution is added to the dried first mixture to selectively induce a curing reaction to prepare a green body.

(4) Repeat the steps (1) to (3) to manufacture a three-dimensional shape.

Example 2. CeO ₂ Ce in the first mixture containing ³⁺ Example of a process in which a second mixture was prepared by mixing a reaction solution containing a metal salt and then cured

(1) preparing a first mixture by mixing ceramic powder and polymer

_{15 g of cerium oxide (CeO 2} ) powder having a particle size of 0.5 μm was sieved and prepared to have an even particle size. After 0.075 g of citric acid was added to the cerium oxide powder, it was rotated and mixed for 2 hours at a speed of 50 rpm using a ball mill. Then, 5 mL of an aqueous solution-based alginic acid solution (30 g/L) and 5 mL of distilled water were mixed with the mixed powder. A first mixture was prepared by rotationally mixing this for 12 hours at a speed of 50 rpm using a ball mill.

(2) reaction solution preparation step

2 g of Ce(NO ₃ ) ₃ ·9H ₂ O was dissolved in 20 mL of ethylene glycol to prepare a reaction solution. At this time, ^{the concentration of Ce 3+} ions in the reaction solution is about 0.307 mM.

(3) After applying the first mixture to a thickness of 100 ~ 200 ㎛ on the surface of the glass substrate, and then dried with a heat of about 70 degrees. Thereafter, a reaction solution is added to the dried first mixture to selectively induce a curing reaction to prepare a green body.

(4) Repeat the steps (1) to (3) to manufacture a three-dimensional shape.

Example 3. Zn in the first mixture containing ZnO ²⁺ Example of a process in which a second mixture was prepared by mixing a reaction solution containing a metal salt and then cured

(1) preparing a first mixture by mixing ceramic powder and polymer

15 g of zinc oxide (ZnO) powder having a particle size of 0.45 μm was sieved and prepared to have an even particle size. After 0.075 g of citric acid was added to the cerium oxide powder, it was rotated and mixed for 2 hours at a speed of 50 rpm using a ball mill. Then, 5 mL of an aqueous solution-based alginic acid solution (30 g/L) and 5 mL of distilled water were mixed with the mixed powder. A first mixture was prepared by rotationally mixing this for 12 hours at a speed of 50 rpm using a ball mill.

(2) reaction solution preparation step

2 g of Zn(NO ₃ ) ₂ .6H ₂ O was dissolved in 20 mL of ethylene glycol to prepare a reaction solution. At this time, ^{the concentration of Zn 3+} ions in the reaction solution becomes about 0.528 mM.

(3) After applying the first mixture to a thickness of 100 ~ 200 ㎛ on the surface of the glass substrate, and then dried with a heat of about 70 degrees. Thereafter, a reaction solution is added to the dried first mixture to selectively induce a curing reaction to prepare a green body.

(4) Repeat the steps (1) to (3) to manufacture a three-dimensional shape.

Although the above has been described with reference to the preferred embodiment of the present invention, those skilled in the art or those having ordinary knowledge in the technical field will not depart from the spirit and technical scope of the present invention described in the claims to be described later. It will be understood that various modifications and variations of the present invention can be made without departing from the scope of the present invention.

Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (8)

A first step of providing a precursor film by applying a first mixture in which a polymer and ceramic powder are mixed; and
a second step of providing a printed layer by adding a reaction solution to at least a partial area of the precursor film to cure the area to which the reaction solution is added in the precursor film,
Repeat the first step and the second step at least once in sequence on the printed layer provided by performing the first step and the second step, and remove the uncured precursor film to print a plurality of layers To provide a three-dimensional structure in which the layers are stacked,
The ceramic powder includes at least one selected from a first metal, an oxide, a hydroxide, a nitride, a halide, and an oxynitride of the first metal,
The reaction solution comprises a salt of the first metal, three-dimensional printing method. According to claim 1,
The ceramic powder comprises an oxide of the first metal,
The reaction solution includes at least one selected from the group consisting of nitrates, carboxylates, sulfates, persulfates, citrates, phosphates, borates, perborates and halides of the first metal, three-dimensional printing Way. According to claim 1,
Inducing curing through a gelation reaction by electrostatic attraction between the salt of the first metal included in the reaction solution and the polymer included in the first mixture in the second step,
The first metal included in the reaction solution for inducing curing of the polymer and the first metal in the ceramic powder included in the first mixture are of the same type. According to claim 1,
The first metal is aluminum (Al), zinc (Zn), cerium (Ce), zirconium (Zr), titanium (Ti), cobalt (Co), iron (Fe), gold (Au), silver (Ag), At least one selected from the group consisting of platinum (Pt), copper (Cu), nickel (Ni), and chromium (Cr), a three-dimensional printing method. According to claim 1,
The particle size of the ceramic powder is 0.02 to 500 (μm unit base) will, a three-dimensional printing method. According to claim 1,
The polymer comprises at least one selected from the group consisting of cellulose, alginic acid, lignin, silk, and collagen, a three-dimensional printing method. 7. The method of claim 6,
At least one polymer selected from the group consisting of cellulose, alginic acid, lignin, silk and collagen is a polymer compound cured by infrared irradiation or surface-modified with a carboxyl group, a three-dimensional printing method. 8. The method of claim 7,
The polymer has a viscosity of 100 to 100,000 cps or a weight average molecular weight (Mw) of 30,000 to 1,500,000, a three-dimensional printing method.

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