KR102214666B1 - 3D printing ink composition using a coating of ceramic particles, a method for producing the same, and 3D printing method - Google Patents

Abstract

Provided is a method of manufacturing a three-dimensional printing ink composition, capable of improving durability of a three-dimensional printing product. The method of manufacturing the three-dimensional printing ink composition includes: coating a surface of ceramic particles with a functional material by mixing the ceramic particles and the functional material having a lower refractive index with respect to ultraviolet rays than the ceramic particles; preparing a first base source by mixing the ceramic particles coated with the functional material and a solvent; modifying the surface of the ceramic particles coated with the functional material by mixing the first base source and a surface modifier; preparing a second base source by mixing the first base source having the surface-modified ceramic particles and a photocuring agent; and preparing the ink composition by adding a photoinitiator to the second base source.

Description

A three-dimensional printing ink composition using a coating of ceramic particles, a manufacturing method thereof, and a printing method. {3D printing ink composition using a coating of ceramic particles, a method for producing the same, and 3D printing method}

The present invention relates to a three-dimensional printing ink composition using a coating of ceramic particles, a method of manufacturing the same, and a printing method, and more specifically, to a three-dimensional coating of ceramic particles to produce a three-dimensional printed molded body through the coated ceramic particles. It relates to a printing ink composition and a method of manufacturing the same.

Ceramic materials such as silica, alumina, and zirconia are actively applied in various fields such as aerospace, medical care, eco-friendly, and energy industries due to their excellent physical and chemical properties such as low coefficient of thermal expansion, excellent abrasion resistance, and corrosion resistance.

However, in spite of excellent mechanical, chemical, and thermal properties due to the inherent characteristics of ceramic materials, there are difficulties that are difficult to apply in fields requiring complex shape processing due to high hardness and strong brittleness. In order to overcome the incompetent formation of ceramic materials and improve the processability, the demand for technology is increasing for the implementation of complex shapes by applying 3D printing technology.

3D printing is a process technology that repeatedly stacks two-dimensional sections using digitally designed data and outputs them in a three-dimensional shape. Design design or modification is very free, and the cost and time required for prototyping can be greatly reduced.

Various types of 3D printing facilities are commercially available according to the lamination method, and the development of materials corresponding thereto is actively progressing. Among various 3D printing technologies of various lamination methods, applicable 3D printing methods are somewhat limited because process optimization such as filling rate and surface treatment is required due to the characteristics of ceramic materials in order to manufacture a laminate structure having a desired shape by applying ceramic materials.

Considering the characteristics of these ceramic materials, 3D printing methods such as stereolithography apparatus (SLA), polyjet (Inkjet 3D), digital light processing (DLP), fused deposition modeling (FDM), and binder jetting (BJ) are expected to be applicable. have.

Among the various stacking methods of such 3D printing technology, the DLP type 3D printer stacks photocurable materials using a digital light projector, so that it has high resolution and precision and can secure quality stability of the stacked substrate. In addition, since the light irradiation is performed in a plane unit rather than a line unit, there is an advantage of relatively high manufacturing speed.

However, in the case of DLP 3D printed molded body, after high temperature heat treatment for manufacturing ceramic sintered body (generally more than 1200 degrees), due to the low filling rate of ceramic particles, voids and cracks occur inside and outside the sintering shrinkage process. There is a problem that the strength of the (sintered body) decreases. Accordingly, research and development of a technology capable of improving the strength of the DLP 3D printing molded article is continuously being conducted.

One technical problem to be solved by the present invention is to provide a 3D printing ink composition, a manufacturing method, and a printing method using a coating of ceramic particles having improved durability of a printed molded article.

Another technical problem to be solved by the present invention is to provide a 3D printing ink composition, a manufacturing method thereof, and a printing method using a coating of ceramic particles with a reduced process time.

The technical problem to be solved by the present invention is not limited to the above.

In order to solve the above technical problems, the present invention provides a method of manufacturing a 3D printing ink composition.

According to an embodiment, the manufacturing method of the 3D printing ink composition comprises: coating the functional material on the surface of the ceramic particle by mixing ceramic particles and a functional material having a lower refractive index for ultraviolet rays than the ceramic particles. , Preparing a first base source by mixing the ceramic particles coated with the functional material, and a solvent, and modifying the surface of the ceramic particles coated with the functional material by mixing the first base source and a surface modifier And preparing a second base source by mixing the first base source having the surface-modified ceramic particles with a photocuring agent, and preparing an ink composition by adding a photoinitiator to the second base source. However, the functional material may include those having a concentration of more than 1 wt% and less than 2 wt% of the ceramic particles.

According to an embodiment, the step of coating the functional material on the surface of the ceramic particles comprises mixing a first preliminary source including a first preliminary functional material and a second preliminary source including a second preliminary functional material to obtain a mixing source. Preparing the functional material, wherein the first preliminary functional material and the second functional material are reacted by adding a pH adjusting agent to the mixing source, and mixing the ceramic particles and the functional material It may include.

According to an embodiment, in the preparing of the ink composition, the step of heat-treating the second base source to volatilize the solvent contained in the second base source, and the second base source in which the solvent is volatilized. It may include the step of adding a photoinitiator.

According to an embodiment, the functional material may include any one of MgF ₂ , Al ₂ O ₃ , ThF ₄ , SiO ₂ , and YF ₃ .

In order to solve the above technical problems, the present invention provides a 3D printing ink composition.

According to an embodiment, in an ink composition comprising ceramic particles coated with a functional material, a surface modifier, a photocuring agent, and a photoinitiator, the functional material has a lower refractive index for ultraviolet rays than the ceramic particles, and 1 It may include those having a concentration of greater than wt% and less than 2 wt%.

According to an embodiment, the ceramic particles include zirconia (ZrO ₂ ), the solvent includes methyl alcohol, the surface modifier includes methacryloxypropyl trimethoxy silane (MPTMS), and the photocuring agent is , 1,6-hexanediol diacrylate (HDDA), and the photoinitiator may include phenyl bis(2, 4, 6-trimethylbenzoyl)-phosphineoxide.

In order to solve the above technical problems, the present invention provides a 3D printing method.

According to an embodiment, the 3D printing method includes preparing a 3D printing ink composition according to the above-described embodiment in a container, and irradiating light to the 3D printing ink composition, wherein the Curing a 3D printing ink composition to prepare a 3D printing molded layer, repeating the 3D printing molding layer manufacturing step to prepare a 3D printing molded body in which the 3D printing molding layer is stacked, And sintering the three-dimensional printed compact to produce a three-dimensional printed sintered body.

According to an embodiment, a ratio at which the photocuring agent is cured in the ink composition irradiated with light is 33% or more, and the strength of the 3D printing molded article may be 32 MPa or more.

According to an embodiment, light provided to the 3D printing ink composition in the manufacturing of the 3D printing molding layer may include ultraviolet rays (UV).

According to an embodiment, in the manufacturing of the 3D printing molded body, a preliminary 3D printing molded body in which the 3D printing molding layer is stacked up to a reference layer by repeatedly performing the manufacturing of the 3D printing molding layer up to a reference range Manufacturing, and after manufacturing the preliminary 3D printing molded body, repeating the manufacturing of the 3D printing molding layer to produce the 3D printing molded body in which the 3D printing molding layer is stacked in excess of the reference layer It may include.

According to an embodiment, after the preparation of the preliminary 3D printing molded body, the 3D printing molding layer laminated in excess of the reference layer is manufactured by exposing the 3D printing ink composition for a time of more than 3 seconds and less than 7 seconds. May include what has been done.

According to an embodiment, the three-dimensional printing molding layer included in the preliminary three-dimensional printing molded body may include a product prepared by exposing the three-dimensional printing ink composition for a time period of more than 30 seconds and less than 90 seconds.

A 3D printing method according to an embodiment of the present invention comprises an ink composition comprising ceramic particles coated with a functional material having a concentration of more than 1 wt% and less than 2 wt%, a surface modifier, a photocuring agent, and a photoinitiator relative to the ceramic particles. Preparing, in a method of disposing the ink composition in a container and irradiating light to the ink composition, curing the ink composition on the upper part of the container to prepare a three-dimensional printing molding layer, and the three-dimensional printing molding layer It may include the step of manufacturing a three-dimensional printing molded body in which the three-dimensional printing molding layer is stacked by repeatedly performing the manufacturing step. Accordingly, the durability of the 3D printed molded body can be improved.

1 is a flowchart illustrating a method of manufacturing a 3D printing ink composition according to an embodiment of the present invention.
2 is a flow chart specifically illustrating a ceramic particle coating step in a method of manufacturing a 3D printing ink composition according to an exemplary embodiment of the present invention.
3 is a flowchart illustrating a 3D printing method according to an embodiment of the present invention.
4 to 7 are views showing a 3D printing process according to an embodiment of the present invention.
8 is a photograph of ceramic particles used to manufacture a 3D printing ink composition according to an embodiment of the present invention.
9 is a photograph of a 3D printed molded body according to an embodiment of the present invention.
10 is a graph comparing characteristics of a 3D printing molded article according to the concentration of a functional material included in a 3D printing ink composition according to an exemplary embodiment of the present invention.
11 is a graph comparing characteristics of a 3D printed molded article according to an initial exposure time.
12 is a graph comparing characteristics of a 3D printed molded article according to exposure time.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical idea of the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content may be thorough and complete, and the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In the present specification, when a component is referred to as being on another component, it means that it may be formed directly on the other component or that a third component may be interposed between them. In addition, in the drawings, thicknesses of films and regions are exaggerated for effective description of technical content.

In addition, in various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. Accordingly, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.

Each embodiment described and illustrated herein also includes its complementary embodiment. In addition, in the present specification,'and/or' is used to mean including at least one of the elements listed before and after.

In the specification, expressions in the singular include plural expressions unless the context clearly indicates otherwise. In addition, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, elements, or a combination of the features described in the specification, and one or more other features, numbers, steps, and configurations It is not to be understood as excluding the possibility of the presence or addition of elements or combinations thereof.

Further, in the following description of the present invention, when it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, a detailed description thereof will be omitted.

1 is a flow chart illustrating a method of manufacturing a 3D printing ink composition according to an exemplary embodiment of the present invention, and FIG. 2 is a detailed description of a ceramic particle coating step in a method of manufacturing a 3D printing ink composition according to an exemplary embodiment of the present invention. This is a flowchart to explain.

1 and 2, a method of manufacturing a 3D printing ink composition according to an embodiment of the present invention includes coating a functional material on ceramic particles (S100), manufacturing a first base source (S200), and It may include the step of modifying the surface of the ceramic particles included in the first base source (S300), the second base source manufacturing step (S400), the ink composition manufacturing step (S500). Hereinafter, each step will be described in more detail.

According to an embodiment, the ceramic particle coating step (S100) may include a mixing source manufacturing step (S110), a functional material forming step (S120), and mixing the ceramic particles and a functional material (S130). .

Specifically, the first preliminary source and the second preliminary source may be mixed to prepare the mixed source (S110). According to an embodiment, the first preliminary source may include a first preliminary functional material. For example, the first preliminary functional material may include NaF. The first preliminary source may be prepared by stirring NaF 10g and distilled water 100ml for 1 hour. Alternatively, the second preliminary source may include a second preliminary functional material. For example, the second preliminary functional material may include MgCl ₂ . The second preliminary source may be prepared by stirring MgCl ₂ 10g and distilled water 100ml for 1 hour.

The first preliminary source and the second preliminary source may be mixed in a ratio of 2 mol: 1 mol and then heat treated. Specifically, 2 mol of NaF source and 1 mol of MgCl ₂ source may be mixed and then heat treated to a temperature of 80°C. Accordingly, the mixed sauce can be prepared.

A functional material may be formed by adding a pH adjusting agent to the mixed source (S120). According to an embodiment, when the pH of the mixing source is adjusted, the first preliminary functional material and the second preliminary functional material in the mixing source may react. Accordingly, the functional material may be formed.

More specifically, when the pH is controlled to 11 by adding a pH adjusting agent to the mixed source in which NaF and MgCl ₂ are mixed, NaF and MgCl ₂ may be reacted to form MgF ₂ . In this case, NaOH may be used as the pH adjusting agent. That is, the functional material may be MgF ₂ . Thereafter, the functional material may be cleaned. According to an embodiment, the functional material may be washed three times with distilled water.

The functional material may be mixed with the ceramic particles (S130). Accordingly, the surface of the ceramic particles may be coated with the functional material. For example, the ceramic particles may include zirconia (ZrO ₂ ) having a particle size of 1 μm.

More specifically, MgF ₂ and ZrO ₂ may be mixed through a resonance mixer. For example, the resonance mixer can be operated under the conditions of 60 to 70% power and 3 cycles (5 minutes stop after 10 minutes operation -> 1 cycle). Accordingly, MgF ₂ may be coated on the surface of ZrO ₂ .

The functional material may have a lower refractive index for ultraviolet rays than the ceramic particles (ZrO ₂ refractive index: 2.1 to 2.15, MgF ₂ refractive index: 1.38). For this reason, the ceramic particles coated with the functional material may have a reduced refractive index with respect to ultraviolet rays. In addition, the functional material may have a concentration of more than 1 wt% and less than 2 wt% based on the weight of the ceramic particles. In this case, a reduction ratio of the refractive index to ultraviolet rays of the ceramic particles coated with the functional material may be improved. As a result, the 3D printed molded article manufactured through the 3D ink composition including the ceramic particles coated with the functional material may have improved durability. A more detailed description will be given later.

In describing the functional material coating the ceramic particles, MgF ₂ has been described as an example, but various materials having a lower refractive index to ultraviolet rays than the ceramic particles may be used. For specific examples, Al ₂ O ₃ (refractive index: 1.65), ThF ₄ (refractive index: 1.66), SiO ₂ (refractive index: 1.48), and YF ₃ (refractive index: 1.52) may be used.

The ceramic particles coated with the functional material may be mixed with a solvent. Accordingly, a first base source may be manufactured (S200). For example, the solvent may include methyl alcohol. According to an embodiment, the ceramic particles coated with the functional material and the solvent may be mixed by ball milling for 24 hours.

The first base source may be mixed with a surface modifier. Accordingly, the surface of the ceramic particles coated with the functional material may be modified (S300). For example, the surface modifier may include methacryloxypropyl trimethoxy silane (MPTMS). More specifically, the first base source may be mixed with MPTMS having a concentration of 15 wt% based on the weight of the ceramic particles, and then stirred at a temperature of 50° C. for 24 hours. Accordingly, MPTMS may be adsorbed on the surface of the ceramic particles.

The first base source having the ceramic particles whose surface is modified may be mixed with a photocuring agent. Accordingly, a second base source may be manufactured (S400). For example, the photocuring agent may include 1,6-hexanediol diacrylate (HDDA). More specifically, the first base source having the ceramic particles whose surface has been modified may be mixed with HDDA having a concentration of 40 wt% based on the total weight, and then stirred at room temperature for 3 hours.

The second base source may be mixed with a photoinitiator. Accordingly, an ink composition may be prepared (S500). According to an embodiment, in the step of preparing the ink composition (S500), the second base source is heat-treated to volatilize the solvent contained in the second base source, and the second base source from which the solvent is volatilized. It may include the step of adding a photoinitiator to. For example, the photoinitiator may include phenyl bis(2, 4, 6-trimethylbenzoyl)-phosphineoxide.

More specifically, after heat-treating the second base source for 1 hour at a temperature of 50° C. using an evaporator to volatilize methyl alcohol remaining in the second base source, a concentration of 1.5 wt% based on the weight of the photocuring agent Phenyl bis(2, 4, 6-trimethylbenzoyl)-phosphineoxide having a may be added and stirred at room temperature for 24 hours. Accordingly, the ink composition can be prepared.

In the above, a 3D printing ink composition and a method of manufacturing the same according to an embodiment of the present invention have been described. Hereinafter, a 3D printing method according to an embodiment of the present invention will be described.

3 is a flowchart illustrating a 3D printing method according to an embodiment of the present invention, and FIGS. 4 to 7 are diagrams illustrating a 3D printing process according to an embodiment of the present invention.

3 to 7, a 3D printing method according to an embodiment of the present invention includes preparing a 3D printing ink composition in a container (S10), preparing a 3D printing molding layer (S20), It may include a step (S30) of manufacturing a 3D printed compact, and a step (S40) of manufacturing a 3D printed sintered body. Hereinafter, each step will be described in detail.

A 3D printing ink composition may be prepared in the container 10 (S10). According to an embodiment, the 3D printing ink composition may be a 3D printing ink composition according to an embodiment of the present invention described with reference to FIGS. 1 and 2. Accordingly, a detailed description of the 3D printing ink composition is omitted.

Light is irradiated to the 3D printing ink composition, so that the 3D printing ink composition may be cured. More specifically, when the light is irradiated to the 3D printing ink composition, the 3D printing ink composition on the upper portion of the container 10 may be cured. Accordingly, a 3D printing molding layer 100L may be manufactured (S20). That is, the 3D printing molding layer 100L may be formed by curing at least a portion of the 3D printing ink composition prepared in the container 10.

According to an embodiment, the light may be emitted from the light source 20. For example, the light source may be a digital light processing (DLP) projector. For example, the light may include UV. According to an embodiment, the light may be irradiated while the substrate 30 is in contact with the 3D printing ink composition. Accordingly, the 3D printing molding layer 100L may be formed on the substrate 30. In other words, the 3D printing molding layer 100L may be formed by a digital light processing (DLP) 3D printing method.

The manufacturing step of the 3D printing molding layer 100L may be repeatedly performed. In this case, a plurality of the 3D printing molding layers 100L may be stacked. Accordingly, the 3D printing molded body 100 may be manufactured (S30). That is, the 3D printing molded body 100 may be a stacked one of a plurality of the 3D printing molded layers 100L.

According to an embodiment, the manufacturing step of the 3D printing molding layer 100L may be repeatedly performed up to a reference range. In this case, a preliminary 3D printing molded body 100a in which the 3D printing molded layer 100L is stacked up to a reference layer may be manufactured. For example, the reference range may be 5 times, and the reference layer may be 5 layers. That is, the preliminary 3D printing molded body 100a may be formed by stacking five 3D printing molded layers 100L, as shown in FIG. 6.

After manufacturing the preliminary 3D printing molded body 100a, the manufacturing step of the 3D printing molded layer may be repeatedly performed again. In this case, the 3D printing molding layer 100a may be stacked in excess of the reference layer. Accordingly, the 3D printing molded body 100 may be manufactured. That is, the 3D printing molded body 100 may be a layer in which the 3D printing molded layer 100a exceeds the reference layer.

According to an embodiment, the 3D printing molding layer 100L included in the preliminary 3D printing molded body 100a is stacked in excess of the reference layer after the manufacturing step of the preliminary 3D printing molded body 100a. Compared with the 3D printing molding layer 100L, exposure times of the light provided to the 3D printing ink composition may be different from each other.

More specifically, the 3D printing molding layer 100L included in the preliminary 3D printing molded body 100a may be prepared by exposing the 3D printing ink composition for a time of more than 30 seconds and less than 90 seconds. On the contrary, after the manufacturing step of the preliminary 3D printing molded body 100a, the 3D printing molded layer 100L laminated in excess of the reference layer has a time of the 3D printing ink composition exceeding 3 seconds and less than 7 seconds. It can be prepared by exposure during. In this case, the strength of the 3D printing molded body 100a may be improved. The 3D printing molded body 100 may be sintered. Accordingly, the three-dimensional printing sintered body may be manufactured (S40).

In the case of manufacturing a 3D printing molded article using an existing 3D printing ink composition containing ceramic particles, the 3D printing molded article cannot be smoothly cured due to the high refractive index of the ceramic particles against ultraviolet rays. There has been a problem that the strength and durability of the printed molded article are deteriorated.

However, in the case of the 3D printing ink composition according to the embodiment of the present invention described above, as described above, as the ceramic particles are coated by the functional material, a high refractive index of the ceramic particles may be reduced. Accordingly, the penetration of ultraviolet rays is effectively generated during the manufacturing process of the 3D printed molded body, so that the 3D printed molded body can be smoothly cured. As a result, the strength and durability of the 3D printed molded body can be improved.

In addition, as described above, the concentration of the functional material may be controlled to be greater than 1 wt% and less than 2 wt% based on the weight of the ceramic particles. In this case, the reduction ratio of the refractive index of the ceramic particles through the coating of the functional material may be improved. Accordingly, the ratio at which the photocuring agent is cured in the ink composition may be controlled to be 33% or more, and the strength of the three-dimensional printing molded article may be controlled to be 32 MPa or more. That is, by controlling the concentration of the functional material coated on the ceramic particles to improve the curing ratio of the photocuring agent, the strength and durability of the 3D printed molded article may be improved.

In the above, a 3D printing method according to an embodiment of the present invention has been described. Hereinafter, specific experimental results and characteristic evaluation results of a 3D printing ink composition and a 3D printing method according to an embodiment of the present invention will be described.

Preparation of functional particles according to the embodiment

Each 10g of NaF and MgCl ₂ was added to 100ml of distilled water and stirred for 1 hour. Thereafter, ₂ mol of NaF and 1 mol of MgCl ₂ were mixed and heat-treated to a temperature of 80° C., and the pH was adjusted to 11 using NaOH to precipitate MgF ₂ particles. Thereafter, MgF ₂ particles were washed three times with distilled water to prepare functional particles according to the embodiment.

Preparation of the 3D printing ink composition according to 1 according to the embodiment

After mixing zirconia (ZrO ₂ ) particles having a concentration of 1 μm and a concentration of 60 wt% and methyl alcohol by ball milling, methacryloxypropyl trimethoxy silane (MPTMS) was used to modify the surface of zirconia (ZrO ₂ ). Then, the mixture was stirred at 50° C. for 24 hours to chemically adsorb MPTMS on the zirconia surface. More specifically, MPTMS was used at a concentration of 15 wt% relative to zirconia.

The surface-modified zirconia particles were stirred at room temperature for 3 hours for complexation with 40 wt% concentration of 1,6-hexanediol diacrylate (HDDA), and then heated at 50° C. for 1 hour using an evaporator. Methyl alcohol was volatilized.

Subsequently, phenyl bis(2, 4, 6-trimethylbenzoyl)-phosphineoxide having a concentration of 1.5 wt% compared to HDDA was added and stirred at room temperature for 24 hours to finally prepare a 3D printing ink composition according to Example 1. I did.

Preparation of the 3D printing ink composition according to 2 according to the embodiment

Prepared according to the manufacturing method of the 3D printing ink composition according to the above-described Example 1, but before mixing the zirconia (ZrO ₂ ) particles and methyl alcohol (methyl alcohol), the zirconia (ZrO ₂ ) particles and in the above-described embodiment by mixing in accordance with the functional material (MgF _2), zirconia (ZrO ₂₎ coated with the functional material (MgF ₂₎ on the surface of the particle, the functional material (MgF ₂₎ coating of zirconia (ZrO ₂₎ mixing the particles with methyl alcohol I did. More specifically, the functional material (MgF ₂ ) was used in a concentration of 0.5 wt% based on the weight of zirconia (ZrO ₂ ). In addition, mixing of the zirconia (ZrO ₂ ) particles and the functional material (MgF ₂ ) was performed through a resonance mixer, and the resonance mixer had 60-70% power and 3 cycles (5 minutes stopped after 10 minutes operation -> 1 cycle).

Preparation of 3D printing ink composition according to Example 3

Prepared according to the manufacturing method of the 3D printing ink composition according to the above-described Example 1, but before mixing the zirconia (ZrO ₂ ) particles and methyl alcohol (methyl alcohol), the zirconia (ZrO ₂ ) particles and in the above-described embodiment by mixing in accordance with the functional material (MgF _2), zirconia (ZrO ₂₎ coated with the functional material (MgF ₂₎ on the surface of the particle, the functional material (MgF ₂₎ coating of zirconia (ZrO ₂₎ mixing the particles with methyl alcohol I did. More specifically, the functional material (MgF ₂ ) was used at a concentration of 1.0 wt% based on the weight of zirconia (ZrO ₂ ). In addition, mixing of the zirconia (ZrO ₂ ) particles and the functional material (MgF ₂ ) was performed through a resonance mixer, and the resonance mixer had 60-70% power and 3 cycles (5 minutes stopped after 10 minutes operation -> 1 cycle).

Preparation of 3D printing ink composition according to Example 4

Prepared according to the manufacturing method of the 3D printing ink composition according to the above-described Example 1, but before mixing the zirconia (ZrO ₂ ) particles and methyl alcohol (methyl alcohol), the zirconia (ZrO ₂ ) particles and in the above-described embodiment by mixing in accordance with the functional material (MgF _2), zirconia (ZrO ₂₎ coated with the functional material (MgF ₂₎ on the surface of the particle, the functional material (MgF ₂₎ coating of zirconia (ZrO ₂₎ mixing the particles with methyl alcohol I did. More specifically, the functional material (MgF ₂ ) was used in a concentration of 1.5 wt% based on the weight of zirconia (ZrO ₂ ). In addition, mixing of the zirconia (ZrO ₂ ) particles and the functional material (MgF ₂ ) was performed through a resonance mixer, and the resonance mixer had 60-70% power and 3 cycles (5 minutes stopped after 10 minutes operation -> 1 cycle).

Preparation of 3D printing ink composition according to Example 5

Prepared according to the manufacturing method of the 3D printing ink composition according to the above-described Example 1, but before mixing the zirconia (ZrO ₂ ) particles and methyl alcohol (methyl alcohol), the zirconia (ZrO ₂ ) particles and in the above-described embodiment by mixing in accordance with the functional material (MgF _2), zirconia (ZrO ₂₎ coated with the functional material (MgF ₂₎ on the surface of the particle, the functional material (MgF ₂₎ coating of zirconia (ZrO ₂₎ mixing the particles with methyl alcohol I did. More specifically, the functional material (MgF ₂ ) was used at a concentration of 2.0 wt% based on the weight of zirconia (ZrO ₂ ). In addition, mixing of the zirconia (ZrO ₂ ) particles and the functional material (MgF ₂ ) was performed through a resonance mixer, and the resonance mixer had 60-70% power and 3 cycles (5 minutes stopped after 10 minutes operation -> 1 cycle).

In the manufacturing process of the 3D printing ink composition according to Examples 1 to 5 described above, the concentration of the functional material (MgF ₂ ) coated on the zirconia (ZrO ₂ ) particles is summarized through <Table 1> below.

division MgF ₂ concentration (wt% based on the weight of zirconia) Example 1 0 wt% Example 2 0.5 wt% Example 3 1.0 wt% Example 4 1.5 wt% Example 5 2.0 wt%

Preparation of 3D printing molded body according to Example 1

After preparing the 3D printing ink composition according to Example 1 in a container, UV was irradiated for 30 seconds using a digital light processing (DLP) projector to prepare a 3D printing molded layer. Thereafter, a preliminary three-dimensional printed molded article was manufactured by stacking five layers of three-dimensional printing molded layers.

Subsequently, the three-dimensional printing molded layer was laminated on the preliminary three-dimensional printing molded body, and the three-dimensional printed molded layer laminated on the preliminary three-dimensional printed molded body was produced by irradiation with UV for a period of 3 seconds. As a result, 3D printing was additionally laminated on the preliminary 3D printing molded body, thereby manufacturing a 3D printing molded body according to Example 1.

Manufacturing 3D printing molded body according to Example 2

After preparing the 3D printing ink composition according to Example 2, a 3D printing molded body was manufactured by the method of manufacturing the 3D printing molded body according to Example 1 described above.

Preparation of 3D printing molded body according to Example 3

After preparing the 3D printing ink composition according to Example 3, a 3D printing molded body was manufactured by the method of manufacturing the 3D printing molded body according to Example 1 described above.

Manufacturing of 3D printing molded body according to Example 4

After preparing the 3D printing ink composition according to Example 4, a 3D printing molded body was manufactured by the method of manufacturing the 3D printing molded body according to Example 1 described above.

Manufacturing of 3D printing molded body according to Example 5

After preparing the 3D printing ink composition according to Example 5, a 3D printing molded body was manufactured by the method of manufacturing the 3D printing molded body according to Example 1 described above.

Manufacturing of 3D printing molded body according to Example 6

The three-dimensional printing molded layer included in the preliminary three-dimensional printing molded body was prepared by the manufacturing method of the three-dimensional printing molded body according to the above-described Example 4, UV irradiation to the three-dimensional printing ink composition according to Example 4 for 60 seconds And was manufactured.

Preparation of 3D printing molded body according to Example 7

The three-dimensional printing molded layer included in the preliminary three-dimensional printing molded body was prepared by the method of manufacturing a three-dimensional printing molded body according to Example 4 described above, and UV irradiated for 90 seconds to the three-dimensional printing ink composition according to Example 4. And was manufactured.

Manufacturing of 3D printing molded body according to Example 8

A three-dimensional printing molded layer included in the preliminary three-dimensional printing molded body was prepared by the method of manufacturing a three-dimensional printed molded body according to Example 4 described above, and UV irradiated for 120 seconds to the three-dimensional printing ink composition according to Example 4. And was manufactured.

Manufacturing of 3D printing molded body according to Example 9

A three-dimensional printing molded layer laminated on the preliminary three-dimensional printing molded body was prepared by the method of manufacturing a three-dimensional printing molded body according to the above-described Example 6, and UV irradiated to the three-dimensional printing ink composition according to Example 4 for 1 second. And was manufactured.

Manufacturing of 3D printing molded body according to Example 10

The three-dimensional printing molded layer laminated on the preliminary three-dimensional printing molded body was prepared by the manufacturing method of the three-dimensional printing molded body according to the above-described Example 6, and UV was irradiated to the three-dimensional printing ink composition according to Example 4 for 5 seconds. And was manufactured.

Preparation of 3D printing molded body according to Example 11

A three-dimensional printing molded layer laminated on the preliminary three-dimensional printing molded body was prepared by the method for manufacturing a three-dimensional printed molded body according to Example 6 described above, and UV was irradiated to the three-dimensional printing ink composition according to Example 4 for 7 seconds. And was manufactured.

Manufacture of 3D printing molded body according to Example 12

A three-dimensional printing molded layer laminated on the preliminary three-dimensional printing molded body was prepared by the method for manufacturing a three-dimensional printed molded body according to Example 6 described above, and UV was irradiated to the three-dimensional printing ink composition according to Example 4 for 9 seconds. And was manufactured.

In the manufacturing process of the 3D printing molded body according to Examples 1 to 12 described above, the 3D printing ink composition and UV irradiation time used for manufacturing the 3D printing molded layer are summarized through <Table 2> below. . The initial exposure time means the time of UV provided to the 3D printing ink composition during the manufacturing process of the 3D printing molded layer included in the preliminary 3D printing sintered body. On the other hand, the exposure time refers to the time of UV provided to the 3D printing ink composition in the manufacturing process of the 3D printing molded layer laminated on the preliminary 3D printing molded body after manufacturing the preliminary 3D printing sintered body.

division
(3D printing molded body) 3D printing ink composition used
(MgF ₂ concentration) Initial exposure time Exposure time Example 1 Example 1 (0 wt%) 30s 3s Example 2 Example 2 (0.5 wt%) 30s 3s Example 3 Example 3 (1.0 wt%) 30s 3s Example 4 Example 4 (1.5 wt%) 30s 3s Example 5 Example 5 (2.0 wt%) 30s 3s Example 6 Example 4 (1.5 wt%) 60s 3s Example 7 Example 4 (1.5 wt%) 90s 3s Example 8 Example 4 (1.5 wt%) 120s 3s Example 9 Example 4 (1.5 wt%) 60s 1s Example 10 Example 4 (1.5 wt%) 60s 5s Example 11 Example 4 (1.5 wt%) 60s 7s Example 12 Example 4 (1.5 wt%) 60s 9s

8 is a photograph of ceramic particles used to prepare a 3D printing ink composition according to an embodiment of the present invention.

Referring to FIG. 8, ceramic particles used for preparing the 3D printing ink composition according to Example 2 were photographed by SEM (Scanning Electron Microscopy). As can be seen in FIG. 8, it was confirmed that MgF ₂ was coated on the surface of the incident ZrO ₂ .

9 is a photograph of a 3D printed molded body according to an embodiment of the present invention.

Referring to FIG. 9, a 3D printed molded body according to Examples 1 to 5 of the present invention is photographed and shown. As can be seen from FIG. 9, it was confirmed that the 3D printed molded body was effectively formed in all of Examples 1 to 5 of the present invention.

10 is a graph comparing characteristics of a 3D printing molded article according to a concentration of a functional material included in a 3D printing ink composition according to an exemplary embodiment of the present invention.

Referring to FIG. 10, after preparing a 3D printed molded body according to Examples 1 to 5 of the present invention, the strength (MPa) of each molded body was measured and shown. In addition, in the process of manufacturing the 3D printing molded body according to Examples 1 to 5, the ratio at which the photocuring agent (HDDA) included in the 3D printing ink is cured by ultraviolet rays is also measured and indicated. The ratio at which the photocuring agent (HDDA) is cured by ultraviolet rays is defined as the conversion rate (%).

The results shown in FIG. 10 are summarized through <Table 3> below.

division Conversion rate (%) Molded body strength (MPa) Example 1 21.6 23.1 Example 2 24.9 23.9 Example 3 27.1 25.1 Example 4 30.7 28.8 Example 5 28.0 26.3

As can be seen through Figures 10 and <Table 3>, the three-dimensional according to Examples 2 to 5 prepared through a three-dimensional ink composition containing zirconia (ZrO ₂ ) particles coated with a functional material (MgF ₂ ) Printing molded article, it can be seen that the conversion rate and strength are higher than the three-dimensional printing molded article according to Example 1 manufactured through a three-dimensional ink composition containing zirconia (ZrO ₂ ) particles not coated with a functional material (MgF ₂ ). there was.

In addition, as the concentration of the functional material (MgF ₂ ) increases, the conversion rate and strength of the three-dimensional printing molded body according to Examples 2 to 4 gradually increase, and then the conversion rate and strength decrease from Example 4. I could confirm. As a result, the conversion rate and strength of the three-dimensional printing molded article according to Example 4 prepared through a three-dimensional ink composition containing zirconia (ZrO ₂ ) coated with a functional material (MgF ₂ ) of 1.5 wt% concentration were the highest. I could see that it appeared.

11 is a graph comparing characteristics of a 3D printed molded body according to an initial exposure time.

Referring to FIG. 11, after preparing the 3D printed molded bodies according to Examples 4 and 6 to 8 of the present invention, the strength (MPa) of each molded body was measured and shown. In addition, in the process of manufacturing the 3D printing molded body according to Examples 4 and 6 to 8, the ratio at which the photocuring agent (HDDA) included in the 3D printing ink is cured by ultraviolet rays was also measured and indicated. . The ratio at which the photocuring agent (HDDA) is cured by ultraviolet rays is defined as the conversion rate (%).

The results shown in FIG. 11 are summarized through <Table 4> below.

division Conversion rate (%) Molded body strength (MPa) Example 4 30.7 28.8 Example 6 33.1 32.0 Example 7 31.3 29.4 Example 8 31.1 29.3

As can be seen from Fig. 11 and <Table 4>, the conversion rate (33.1%) of the three-dimensional printed molded body according to Example 6, the progress of comparing Examples 4 and 6 to 8, and the initial exposure time of 60s And the strength (32.0Mpa) was found to be the highest.

12 is a graph comparing characteristics of a 3D printed molded body according to exposure time.

Referring to FIG. 12, after preparing a 3D printed molded body according to Examples 6 and 9 to 12 of the present invention, the strength (MPa) of each formed body was measured and shown. In addition, in the process of manufacturing the 3D printing molded body according to Examples 6 and 9 to 12, the ratio at which the photocuring agent (HDDA) included in the 3D printing ink is cured by ultraviolet rays was also measured and indicated. . The ratio at which the photocuring agent (HDDA) is cured by ultraviolet rays is defined as the conversion rate (%).

The results shown in FIG. 12 are summarized through <Table 5> below.

division Conversion rate (%) Molded body strength (MPa) Example 9 28.7 27.6 Example 6 33.1 32.0 Example 10 33.9 32.4 Example 11 32.6 32.0 Example 12 30.7 29.1

As can be seen from FIG. 12 and <Table 5>, as a result of comparing Example 6 and Example 9 to Example 12, the conversion rate (33.9%) of the 3D printed molded body according to Example 10 in which the exposure time was 5s and It was confirmed that the strength (32.4 MPa) was the highest.

As a result, a 3D printing molded body was prepared using a 3D printing ink composition including ceramic particles coated with a functional material having a concentration of more than 1 wt% and less than 2 wt% based on the weight of the ceramic particles, but the initial exposure time was 30 When the exposure time is controlled to a time of more than 90 seconds and the exposure time is controlled to a time of more than 3 seconds and less than 7 seconds, a three-dimensional printed molded article having a high conversion rate (33% or more) and high strength (32 MPa or more) is effectively It can be seen that it can be manufactured.

In the above, the present invention has been described in detail using preferred embodiments, but the scope of the present invention is not limited to specific embodiments, and should be interpreted by the appended claims. In addition, those who have acquired ordinary knowledge in this technical field should understand that many modifications and variations can be made without departing from the scope of the present invention.

Claims (12)

Coating the functional material on the surface of the ceramic particles by mixing ceramic particles and a functional material having a lower refractive index for ultraviolet rays than the ceramic particles;
Preparing a first base source by mixing the ceramic particles coated with the functional material and a solvent;
Mixing the first base source and a surface modifier to modify the surface of the ceramic particles coated with the functional material;
Preparing a second base source by mixing the first base source having the surface-modified ceramic particles with a photocuring agent; And
Including the step of preparing an ink composition by adding a photoinitiator to the second base source,
The functional material, including those having a concentration of more than 1 wt% and less than 2 wt%,
The ceramic particles include a compound containing metal and oxygen, and the functional material is MgF ₂ , Al ₂ O ₃ , ThF ₄ , SiO ₂ , Preparation of a 3D printing ink composition comprising any one of YF ₃ Way.
The method of claim 1,
Coating the functional material on the surface of the ceramic particle
Preparing a mixed sauce by mixing a first preliminary source comprising a first preliminary functional material and a second preliminary source comprising a second preliminary functional material;
Adding a pH adjusting agent to the mixing source to form the functional material in which the first preliminary functional material and the second preliminary functional material are reacted; And
A method for producing a 3D printing ink composition comprising the step of mixing the ceramic particles and the functional material.
The method of claim 1,
The step of preparing the ink composition,
Heat treating the second base source to volatilize the solvent contained in the second base source; And
A method of manufacturing a 3D printing ink composition comprising the step of adding the photoinitiator to the second base source in which the solvent is volatilized.
The method of claim 1,
The functional material is MgF ₂ , Al ₂ O ₃ , ThF ₄ , SiO ₂ , and YF ₃ Method for producing a 3D printing ink composition comprising any one of.
In the ink composition comprising ceramic particles coated with a functional material, a surface modifier, a photocuring agent, and a photoinitiator,
The functional material includes those having a refractive index lower than that of the ceramic particles with respect to ultraviolet rays and having a concentration of more than 1 wt% and less than 2 wt% of the ceramic particles,
The ceramic particles include a compound containing metal and oxygen, and the functional material is a three-dimensional printing ink composition comprising any one of MgF ₂ , Al ₂ O ₃ , ThF ₄ , SiO ₂ , and YF ₃ .
The method of claim 5,
The ceramic particles include zirconia (ZrO ₂ ), the surface modifier includes methacryloxypropyl trimethoxy silane (MPTMS), the photocuring agent includes 1,6-hexanediol diacrylate (HDDA), and the photoinitiator includes phenyl bis 3D printing ink composition containing (2, 4, 6-trimethylbenzoyl)-phosphineoxide.
Preparing the three-dimensional printing ink composition according to claim 5 in a container;
A method of irradiating light onto the 3D printing ink composition, comprising: curing the 3D printing ink composition on the upper part of the container to prepare a 3D printing molding layer;
Repeating the steps of manufacturing the three-dimensional printing molding layer to manufacture a three-dimensional printed molded body in which the three-dimensional printing molding layer is stacked; And
A three-dimensional printing method comprising the step of sintering the three-dimensional printing compact to produce a three-dimensional printing sintered body.
The method of claim 7,
A 3D printing method comprising: a ratio at which the photocuring agent is cured in the ink composition irradiated with light is 33% or more, and an intensity of the 3D printing molded article is 32 MPa or more.
The method of claim 7,
The light provided to the 3D printing ink composition in the manufacturing of the 3D printing molding layer includes ultraviolet rays (UV).
The method of claim 7,
The manufacturing step of the three-dimensional printing molded body,
Manufacturing a preliminary three-dimensional printed molded article in which the three-dimensional printing molded layer is stacked up to a reference layer by repeatedly performing the manufacturing step of the three-dimensional printing molded layer up to a reference range; And
After manufacturing the preliminary three-dimensional printing molded body, a three-dimensional printing molded body comprising the step of manufacturing the three-dimensional printed molded body in which the three-dimensional printing molded layer is stacked in excess of a reference layer by repeatedly performing the step of manufacturing the three-dimensional printing molding layer How to print.
The method of claim 10,
After the preparation of the preliminary three-dimensional printing molded body, the three-dimensional printing molded layer laminated in excess of the reference layer,
A three-dimensional printing method comprising the three-dimensional printing ink composition prepared by exposure for a time of less than 7 seconds more than 3 seconds.
The method of claim 10,
The three-dimensional printing molding layer included in the preliminary three-dimensional printing molded body,
A three-dimensional printing method comprising the three-dimensional printing ink composition prepared by exposure for a time of more than 30 seconds and less than 90 seconds.

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