KR102412726B1 - Method for producing a mixture for photopolymerization containing mica and a method of preparing a structure including mica using the same - Google Patents

Abstract

It is an object of the present invention to provide a method for preparing a mixture for photopolymerization containing mica, particularly illite, and a method for manufacturing a molded object including mica, particularly illite, using the same. To this end, the present invention comprises the steps of pulverizing the mica raw material; and preparing a mixture for photopolymerization by mixing the powdered mica raw material with a resin for photopolymerization; Introducing a 3D printer to model the sculpture; and sintering the molded object; provides a method for manufacturing a sculpture comprising mica, comprising: a. According to the present invention, mica with excellent adsorption power to heavy metals and flowing gas, high far-infrared emissivity, generating negative ions, and having excellent antibacterial and antiviral properties, especially illite, is used, for example, a method such as three-dimensional lamination modeling. It is possible to prepare a composition for photopolymerization that can be applied to, and by using it, it is possible to prepare a sculpture containing mica having the above characteristics, so that it is possible to provide a sculpture having excellent characteristics of mica according to the needs of various fields. there is an effect

Description

Method for producing a mixture for photopolymerization containing mica, and a method for producing a molded object containing mica using the same

The present invention relates to a method for producing a mixture for photopolymerization containing mica, particularly illite, a method for producing a mixture for photopolymerization containing mica, particularly illite, and a method for manufacturing a sculpture using the same, and a method for manufacturing a sculpture including mica, particularly illite, and It relates to a sculpture including mica, in particular, illite produced by

Mica is a group of minerals belonging to hydrated aluminum phyllosilicate. Biotite (K(Mg,Fe) ₃ (AlSi ₃ O ₁₀ )(OH)), Lepidolite (K(Li,Al) _2-3 (AlSi ₃ O ₁₀ ) )(O,OH,F) ₂ ), Muscovite (KAl ₂ (AlSi ₃ O ₁₀ )(OH) ₂ ),Phlogopite(KMg ₃ (AlSi ₃ O ₁₀ )(OH) ₂ ), Zinnwaldite (K(LiFeAl) ( AlSi ₃ O ₁₀ )(OH,F) ₂ ), Illite Sericite (K _0.8-0.9 (Al,Mg,Fe) ₂ (AlSi) ₄ O ₁₀ (OH) ₂ ), etc. In particular, illite is considered a clay mineral of muscovite, the main mineral phase of industrial mica, and is also treated as sericitic pyrophyllite. Illite, which has a layered structure, has been reported to have excellent adsorption behavior, and it is known that adsorption occurs at two locations: a planar site and a weathered edge site (FES). Among them, the weathered edge portion (FES) is generated when the edge of the illite mineral crystal is weathered, and has the property of adsorbing heavy metals such as cesium well at low concentrations. The amount (frequency and extent) of FES can vary depending on the degree of weathering of illite, and it shows a positive correlation with the adsorption capacity of low concentration cesium (Rajec et al., Clays and Clay Minerals. 1999,47(6), 755- 760).

As described above, Illite has excellent ability to adsorb heavy metals, as well as to adsorb toxic gases, and has excellent far-infrared radiation ability, anion generating ability, antibacterial and antiviral ability, so it is a material that can be applied to various fields of application.

In the case of Korea, Yeongdong-gun, Chungcheongbuk-do is known to have the largest amount of Illite in the country, and Chungcheongbuk-do is already promoting various projects to create high added value by using Illite for industrial purposes together with Yeongdong-gun. Specifically, Yeongdong-gun estimates that the reserves of Illite range from several hundred tons to about 500 million tons.

Until now, Illite has been used in small amounts as a raw material for ceramics, as an additive to livestock feed, as a soil conditioner, and as a household product such as soap.

For example, Korean Patent Application Laid-Open No. 10-2020-0107011 discloses a block for a walkway using Illite, and specifically, the block body 100; Disclosed is a block for walkways using illite, characterized in that it includes; a surface layer 200 containing illite powder to be installed on the block body 100. However, the above technique is a technique of simply forming a surface layer containing illite powder on the block body, and the surface layer is composed of a binder and mixed aggregate containing illite.

In addition, Korean Patent Registration No. 10-1337385 discloses a method for manufacturing an illite board and an illite board according thereto, and specifically, a powder manufacturing step (S10) of preparing illite powder and clay powder, respectively; A mixing step of preparing a powder mixture by mixing the illite powder and the clay powder in a weight ratio of 1:1 (S20); A molding step (S40) of putting the powder mixture into a molding die of a press device and then applying pressure to form a molding; a drying step (S50) of drying the molded product at 150° C. to 250° C. for at least 30 minutes so that the moisture content of the molding is 0 wt % to 2 wt %; Disclosed is a method of manufacturing an illite board comprising a firing step (S60) of heating the dried molding in a kiln at 800°C to 1200°C.

In addition, Korean Patent Laid-Open No. 10-2019-0074871 discloses Illite particles supported with functional substances and a manufacturing method thereof, and Korean Patent Publication No. 10-2013-0024299 discloses a highly moisturizing powder type containing Illite complex functional powder. A color cosmetic composition, Korean Patent Registration No. 10-1962934, discloses an antibacterial functional container containing an illite component.

However, all of the above patents relate to the illite powder itself or take a method of using a small amount of illite mixed with other raw materials such as clay for molding.

On the other hand, 3D printing technology is a technology that creates a three-dimensional shape by stacking a two-dimensionally differentiated structure of a necessary three-dimensional shape layer by layer. In the case of ceramics, it is impossible to control a complex three-dimensional shape due to the fact that it has both hardness but brittleness, and thus there are great limitations in applicable industrial fields. 3D printing can greatly overcome the molding limitations of ceramics, and if technology can be secured to 3D print mica materials including illite, it is expected that it will be possible to create various new industries that maximize the characteristics of mica.

Korean Patent Laid-Open No. 10-2016-0059724 discloses a method for manufacturing a filament composition for a 3D printer including muscovite, sericite and illite, but uses the Fused Deposition Modeling (FDM) method, that is, 5 ~ A composition containing 20% by mass is presented, and when it exceeds 20wt%, the mechanical properties of the filament composition for a 3D printer are lowered, making it difficult to use. On the other hand, the 3D printing technique of the FDM method has a limit in producing industrial parts because the structure precision is determined according to the size of the nozzle, the surface roughness is large, and the structure precision is low. In addition, structures containing 20 wt% or less of inorganic substances are included in the resin, so the functionality of the powder itself can be induced, but if it undergoes degreasing and sintering processes necessary for ceramization, its shape cannot be maintained, so it is difficult to ceramize. .

International Patent Application No. PCT/US2017/066086 proposes a method for improving inter-rod adhesion and fusion of plastic parts by the FDM method to create a three-dimensional shape by stacking filaments melted with heat as in the above patent. In order to reduce the specific heat of the composition, mineral additives are added, and many inorganic substances that can be added are mentioned, and illite is included. However, the technology to be solved does not mention the technology of post-processing the inter-rod bonding and fusion of plastic parts to form a ceramic sintered body, and the low structural precision implementation of the FDM method cannot be overcome.

On the other hand, among various ceramic 3D printing methods, the most excellent structural precision and high-strength physical properties are achieved by uniformly mixing ceramic powder in a photocurable resin that is cured by light to make a material in a slurry state rather than a filament, and this ceramic-light A typical example is a photocurable ceramic 3D printing method that uses a resin slurry to harden a two-dimensional structure by light and build a three-dimensional structure by stacking it layer by layer. However, since the photocurable 3D printing method induces hardening by light, the photocurable potential is different depending on the added ceramic properties, i.e., density, refractive index, light absorptivity and color, etc. It is difficult to induce photocuring due to light absorption, so a ceramic slurry manufacturing technology that improves photocurability is required. In addition, the technology of sintering the 3D printed structure without cracks, distortions or cracks to make the final ceramic should also be developed depending on the material.

Accordingly, the inventors of the present invention prepared a mixture for photopolymerization including illite having various effects, and completed the present invention by researching a mixture for photopolymerization suitable for use in a photopolymerization process using a 3D printer.

Domestic Patent Publication No. 10-2020-0107011 Domestic Registered Patent No. 10-1337385 Republic of Korea Patent Publication No. 10-2019-0074871 Republic of Korea Patent Publication No. 10-2013-0024299 Republic of Korea Patent No. 10-1962934 Republic of Korea Patent Publication No. 10-2016-0059724 International Patent Application PCT/US2017/066086

Rajec et al., Clays and Clay Minerals. 1999,47(6), 755-760

It is an object of the present invention to provide a method for preparing a mixture for photopolymerization containing mica, particularly illite. Another object of the present invention is to provide a mixture for photopolymerization comprising the mica prepared thereby, particularly illite. Another object of the present invention is to provide a method of manufacturing a sculpture using mica, particularly illite, using the same. Another object of the present invention is to provide a sculpture comprising mica, in particular, illite produced thereby.

To this end, the present invention

pulverizing the mica raw material; and

preparing a mixture for photopolymerization by mixing the powdered mica raw material with a resin for photopolymerization;

It provides a method for preparing a mixture for photopolymerization containing mica, and provides a mixture for photopolymerization, which is prepared thereby, and comprises a mica raw material.

Also, the present invention

Forming a sculpture by introducing a mixture for photopolymerization containing mica prepared by the above method into a 3D printer; and

sintering the molded object;

It provides a method for manufacturing a sculpture containing mica, characterized in that it includes, and provides a sculpture containing mica, which is manufactured thereby, and has a far-infrared emissivity of 91% or more compared to a black body.

According to the present invention, using mica having excellent insulating properties, especially illite, which has excellent adsorption power to heavy metals and flowing gas, high far-infrared emissivity, generates negative ions, and has excellent antibacterial and antiviral properties, for example, 3 It is possible to prepare a composition for photopolymerization that can be applied to a method such as dimensional lamination modeling, and by using it, it is possible to prepare a sculpture having a complex three-dimensional shape including mica having the above characteristics, especially illite, According to the needs of the field, there is an effect that can provide a sculpture having excellent properties of mica, particularly illite.

1 is a photograph and graph showing the particle size and distribution of illite used in the present invention after pulverization;
2 is a graph showing the viscosity of the mixture according to the content of illite,
3 is a graph showing the degree of photocuring according to the type of illite,
4 is a graph showing the change in photocurability according to acid treatment,
5 is a photograph of a molded body manufactured by the method of the present invention using yellow illite;
6 is a photograph of a molded body manufactured by the method of the present invention using white illite,
7 is an XRD graph showing the crystal phase change of illite at the heat treatment temperature;
8 is a photograph and graph showing the degree of shrinkage of the sculpture according to the sintering temperature;
9 is a graph showing the change in the density of the sintered compact according to the sintering temperature,
10 is a photograph showing the shape change of the sintered body according to the sintering temperature, a graph showing the mechanical strength,
11 is a table showing the far-infrared emissivity of the shaped body manufactured by the method of the present invention;
12 is a graph showing the antibacterial properties of the molded body manufactured by the method of the present invention;
13 is a photograph showing the shape stability of the molded body manufactured by the method of the present invention;
14 is a photograph and graph showing the particle size and distribution before and after pulverization of muskovite used in the present invention;
15 is a photograph showing the slurry state and applicability before and after pulverization of muscobite used in the present invention;
16 is a graph showing the viscosity change of the mixture according to the dispersant content,
17 is a graph showing the viscosity change according to the muscobite content,
18 is a graph showing the photocurability of a mixture containing muscovite,
19 is a photograph of a molded body manufactured by the method of the present invention using muskovite,
20 is a graph showing the relative density and mechanical strength according to the sintering temperature of the sintered body containing yellow illite,
21 is a graph showing the relative density and mechanical strength according to the sintering temperature of the sintered body containing white illite,
22 is an SEM photograph showing the surface condition according to the sintering temperature when yellow illite is used, and
23 is an SEM photograph showing the surface state according to the sintering temperature when white illite is used.

the present invention

pulverizing the mica raw material; and

preparing a mixture for photopolymerization by mixing the powdered mica raw material with a resin for photopolymerization;

It provides a method for producing a mixture for photopolymerization containing mica comprising a.

Hereinafter, the manufacturing method of the present invention will be described in detail for each step.

The manufacturing method of the present invention includes the step of pulverizing the mica raw material.

The raw material used in the present invention is a raw material containing mica, for example, illite, and has been applied only to applications such as ceramics and tiles, despite beneficial properties such as adsorption properties and antibacterial properties of illite so far. In order to shape a raw material containing such mica, for example, illite in various forms, and apply it to various fields of application, a mixture for photopolymerization including the mica is prepared, and using this, for example, 3D modeling is performed through a 3D printer. In order to apply the mica raw material to such a process, the step of pulverizing the mica raw material must be performed first. In the next step, the powdered mica raw material is mixed with a resin for photopolymerization to prepare a mixture for photopolymerization.

The manufacturing method of the present invention may further include applying a dispersant to the powdered mica raw material. By applying the dispersing agent to the powdered mica raw material, when it is mixed with the resin for photopolymerization afterward, it can be uniformly mixed, and if such an effect can be obtained, it is not necessary to limit the type of the specific dispersant and the content of the specific dispersant. none.

On the other hand, the manufacturing method of the present invention may further include an acid treatment step before mixing the powdered mica raw material with the resin for photopolymerization. Since the photopolymerization mixture maintains the shape of the object by being cured by light in a 3D printer, for example, in the case of the photopolymerization mixture, photocurability characteristics are very important. In the case of mica, for example, illite may contain an iron oxide component, and if the content is large, the photocurability of the photopolymerization mixture may be reduced due to its characteristic red color. Therefore, in the manufacturing method of the present invention, acid treatment is performed on the powdered mica raw material to reduce the iron oxide content in the powdered raw material, and as a result, there is an effect that can prevent deterioration of the photocurability of the photopolymerization mixture. .

In this case, the acid treatment may be performed at 80° C. for 2 hours using, for example, 1M HCl, and the conditions of the acid treatment are in an appropriate range, taking into account the amount of raw material and the content of iron oxide to be reduced. can be adjusted.

The step of pulverizing the raw material for mica in the method for preparing the mixture for photopolymerization containing mica of the present invention may include grinding and sieving the raw material for mica. In order to prepare a mixture for photopolymerization containing mica, the mica raw material must be powdered and mixed with the resin for photopolymerization. In this case, the pulverizing the mica raw material may be performed in various ways, for example, By including the step of pulverizing and sieving it, it is possible to obtain a mica raw material powder having a uniform particle size, but it is not necessarily limited to this method.

The method for preparing a mixture for photopolymerization containing mica of the present invention may further include drying, re-grinding, and sieving after applying a dispersant to the mica raw material. As the dispersant is applied to the powdered raw material, the powders may agglomerate and become wet, so after application of the dispersant, the method further comprises drying the dispersant, re-grinding, and sieving to form a powder having a uniform particle size. can do.

The method for producing a mixture for photopolymerization containing mica according to the present invention comprises the steps of performing the step of pulverizing a raw material for mica by the above method, and then mixing the powdered raw material with a resin for photopolymerization to prepare a mixture for photopolymerization includes Since the mica powder itself cannot form a molded object through photocuring, a step of mixing the mica powder with the resin for photopolymerization is required. At this time, preferably, the powdered mica raw material is mixed with the photopolymerization resin in an amount of 50% by volume based on the total volume of the mixture to prepare a photopolymerization mixture. The photopolymerization mixture is introduced into a molding device such as a 3D printer, for example, and in the case of a molding device such as a 3D printer, the viscosity of the raw material has a very important effect on the printing quality. When introduced into the resin for photopolymerization in excess, since the viscosity of the mixture rapidly increases, there is a problem in that it cannot be used as a mixture for photopolymerization.

According to the manufacturing method of the present invention, a photopolymerization mixture that can be used in a molding apparatus such as a 3D printer is prepared, but a photopolymerization mixture containing mica, for example, illite, having the above-mentioned useful properties can be prepared. This has the advantage that it can be applied to various application fields.

In addition, the present invention provides a mixture for photopolymerization, which is prepared by the method as described above and comprises a mica raw material. Mica, especially illite, is a material that has various advantages such as heavy metal adsorption, far-infrared radiation, anion generation, antibacterial and antiviral, but has never been applied as a material for photopolymerization. By increasing the , there is a problem that is not suitable for use as a material for photopolymerization. Accordingly, the present invention provides a mixture for photopolymerization by pulverizing a mica material and mixing it with a resin for photopolymerization to prepare a mixture for photopolymerization, preferably including up to 50% by volume of the mica raw material relative to the total volume of the mixture. By including the mica raw material, the mixture for photopolymerization according to the present invention not only has the advantages of mica, particularly illite, as mentioned above, but also contains the mica raw material up to 50% by volume relative to the total volume of the mixture, thereby greatly increasing the viscosity of the mixture When applied to a process such as 3D printing, for example, the mixture for photopolymerization according to the present invention has the effect of preventing deterioration of the quality of the object due to viscosity problem.

Also, the present invention

Forming a sculpture by introducing a mixture for photopolymerization containing mica prepared by the above method into a 3D printer; and

sintering the molded object;

It provides a method of manufacturing a sculpture comprising mica, characterized in that it comprises a.

Hereinafter, the manufacturing method of the sculpture of the present invention will be described in detail for each step.

The first step of the method for manufacturing a sculpture of the present invention includes the step of introducing a photopolymerization mixture containing mica prepared by the method of the present invention into a 3D printer to form the object. The step of molding the object of the present invention is characterized in that the photopolymerization mixture containing the mica prepared by the method of the present invention is used as a material, and introducing the material into a 3D printer and molding the material is a general 3D printer. Introduced, for example, it can be carried out by a method such as layered molding. In the photopolymerization mixture containing mica prepared by the method of the present invention, since the mica is uniformly dispersed in the photopolymerization resin, as well as the viscosity of the mixture is appropriately controlled, the quality is lowered in molding the object. There are advantages to avoiding this.

Meanwhile, the mica, particularly illite, of the mixture introduced into the 3D printer in the method of the present invention may be acid-treated mica, particularly illite. Mica, especially illite, contains illite containing iron oxide (Fe ₂ O ₃ ) in a high content, and in this case, the illite takes on a red color, and the photocuring degree is lowered during photocuring in a 3D printer. Problems can arise. Accordingly, the mica contained in the photopolymerization mixture used in the method of the present invention may be acid-treated mica, and by removing iron oxide contained in the mica by such acid treatment, the photocurability of the mixture may be prevented from being lowered. can have an effect.

The mica contained in the mixture used in the production method of the present invention may be illite, particularly white illite. Illite is classified into white illite, yellow illite, etc. according to its color. It may be more advantageous than the case of including.

The method for manufacturing a sculpture of the present invention includes the steps of sintering the molded object in order to complete curing and improve the strength of the object after molding the object through a 3D printer.

At this time, the sintering is preferably performed at a temperature of 1000 °C or lower, and more preferably performed at a temperature of 950 °C or lower. When the sintering is performed at a temperature of more than 1000 ° C., there is a problem in that a change in the crystal phase of mica occurs, and also there is a problem in that the shrinkage of the object is greatly increased. In particular, when sintering is performed at a temperature of 950° C. or lower, it is more preferable in that shrinkage hardly occurs.

On the other hand, when the mica included in the mixture used in the method for manufacturing the object of the present invention is yellow illite, the temperature for sintering the object may be higher than 1000 ° C. When sintering is performed at a temperature exceeding 1000 °C for one object, there is an advantage in that the strength of the sintered body is significantly increased.

The method for manufacturing a sculpture according to the present invention is a 3D printer using a mixture containing mica, particularly illite, having adsorption capacity of heavy metals and flowing gas, radioactivity of far-infrared radiation, ability to generate negative ions, antibacterial and antiviral ability. There is an effect that can prevent the quality of the molded object from being deteriorated while molding the object.

Furthermore, the present invention provides a sculpture comprising mica, which is manufactured by the manufacturing method of the present invention, and has a far-infrared emissivity of 91% or more compared to a black body. In fact, the sculpture containing the mica produced by the method of the present invention has a far-infrared emissivity of 91% or more compared to the black body, and is dispersed in the resin for photopolymerization to form the object through photocuring and sintering. There is an advantage of maintaining similar properties, and therefore, the sculpture produced by the manufacturing method of the present invention has the advantage of the mica raw material as it is, so it has an advantage that can be applied to various fields of application.

In particular, since the sterilization power of the molding containing mica prepared by the method of the present invention is 80%, when the molding containing mica prepared by the method of the present invention is used as a part of a specific product, a separate sterilization treatment is required. The advantage is that you don't have to.

Hereinafter, the present invention will be described in more detail through experimental examples. The following experimental examples are only intended to explain the present invention in more detail, and it is not intended that the scope of the claims claimed by the present invention be limitedly interpreted by the following description.

The illite used below was purchased from Yonggung Illite Co., Ltd., and the components of each (yellow illite and white illite) are shown in the following table.

division SiO ₂ Al ₂ O ₃ Fe ₂ O ₃ TiO ₂ MgO MnO CaO Na ₂ O K ₂ O P ₂ O ₅ L.O.I. yellow 52.01 30.53 2.30 0.46 0.25 0.01 0.01 0.43 7.26 0.02 4.49 White 66.10 23.04 1.31 0.32 0.20 0.00 0.01 0.07 5.90 0.03 3.02

Main component of Illite (wt%)

division Li Cr Co Ni Cu Zn Ga Sr CD Pb yellow 36.0 15.6 0.0 5.2 1.8 29.3 41.5 46.7 0.0 0.0 White 36.8 13.0 0.0 3.9 7.8 25.3 26.8 48.2 0.0 0.0

Trace ingredients of Illite (ppm)

<Experimental Example 1>

Yellow Illite and white Illite purchased from Yonggung Illite Co., Ltd. were respectively pulverized using ball milling, and the particle size distribution was checked with a micro particle size analyzer, and the results are shown in FIG. indicated.

1 , it can be seen that the size distribution of yellow illite and white illite is relatively uniform, and yellow illite is uniformly distributed in smaller sizes.

<Experimental Example 2>

In order to confirm the change in the viscosity of the mixture for photopolymerization according to the content of illite, the following experiment was performed.

White Illite and yellow Illite purchased from Yonggung Illite Co., Ltd. were introduced into the mixture of acrylate-based monomer and photoinitiator, which are resins for photopolymerization, in the same amount as in Table 3 below relative to the total volume of the mixture, and a corotation mixer was used. A mixture for photopolymerization was prepared through a homogenization step. With respect to the prepared mixture for photopolymerization, the viscosity of each mixture was measured using a viscometer, and the results are shown in FIG. 2 . At this time, if necessary, in the case of yellow illite, acid treatment was carried out at 80° C. for 2 hours in 1M HCl (10wt%) to enhance photocurability.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Comparative Example 1 Comparative Example 2 Comparative Example 3 division yellow yellow White White White White White White yellow yellow White content (volume %) 45 50 45 46 47 48 49 50 51 52 51

According to FIG. 2 , in all cases including yellow illite and white illite, when the content of illite exceeds 50% by volume, it can be seen that the viscosity increases sharply, In the case of the photopolymerization mixture of the present invention having a purpose, it can be confirmed that it is important to control the content of illite to 50% by volume or less.

<Experimental Example 3>

In order to confirm the photopolymerization characteristics according to the type of illite, the following experiment was performed.

Using white and red Illite purchased from Yonggung Illite Co., Ltd., a mixture for photopolymerization was prepared through the processes of grinding, classification, and homogeneous mixing with resin for photopolymerization, and this was used as a material film supply type photocurable 3D printer. was applied to photocuring under the condition of a light quantity of 10mW/cm ² , and the thickness of photocuring was confirmed by time, and the results are shown in FIG. 3 .

Referring to FIG. 3 , it can be seen that, in fact, in the case of a mixture containing white illite, photocuring is performed better than a mixture containing yellow illite. Specifically, according to FIG. 3 , in the case of light irradiation for 3 seconds, photocuring already proceeds in the case of a mixture containing white illite, but in the case of a mixture containing yellow illite, it can be confirmed that photocuring does not occur.

<Experimental Example 4>

In order to confirm the effect of acid treatment on the mixture containing yellow illite, the following experiment was performed.

The pulverized and classified illite was soaked in 1M HCl (10wt%) and treated at 80 °C for 2 hours, the powder was recovered through filtration, washed repeatedly with distilled water, and dried.

According to FIG. 4, it can be seen that the mixture containing white illite actually photocures more effectively than the mixture containing yellow illite, and even if yellow illite is used, when it is acid-treated, It can be seen that the photocurability can be improved by lowering the content of the iron oxide component.

<Experimental Examples 5 and 6>

After applying the photo-curable slurry containing 40% by volume of yellow illite to a thickness of 20 micrometers on a transparent film through a doctor blade, apply it evenly and then irradiate the light in a finely divided two-dimensional shape for 10 seconds to complete the three-dimensional shape. The shape of FIGS. 5 and 6 was completed.

According to FIG. 5 , it can be confirmed that objects having various detailed structures can be molded in high quality by using a mixture for photopolymerization including yellow illite. Also, according to FIG. 6 , it can be confirmed that, in the case of using a mixture for photopolymerization including white illite, objects having various and detailed structures can be molded with high quality.

<Experimental Example 7>

In order to confirm the crystal phase change according to the heat treatment of illite, the following experiment was performed.

White illite and yellow illite raw powders were sintered at 900 to 1100 degrees at 10 °C/min, respectively, and then pulverized to analyze the crystal phase according to temperature through X-ray rotation analysis.

According to FIG. 7 , both the white illite and the yellow illite maintain their original crystal structures up to 1000° C., but at 1100° C., it can be confirmed that the crystal phase change occurs through the disappearance of the 28.15° peak. Since the crystalline phase is related to the characteristics of the illite, it can be confirmed that it is preferable to perform the heat treatment at a temperature of 1000 ° C. or less in order to maintain the original characteristics of the illite.

<Experimental Example 8>

After 3D printing was performed using a mixture for photopolymerization containing illite, the following experiment was performed to confirm the volume change of the object according to the sintering temperature.

After degreasing the molded body manufactured by 3D printing at 600 ° C, sintering at 1 ° C/min in the 900 ~ 1100 ° C area, confirming the volume shrinkage of the 3D structure due to sintering, and checking the mechanical properties and the degree of bulking accordingly did

According to FIG. 8 , it can be confirmed that the shrinkage ratio for each axis is significantly increased at a temperature exceeding 1000°C, and in particular, it can be confirmed that the volume shrinkage ratio is greatly increased at a temperature exceeding 950°C. Therefore, it can be seen that it is preferable to perform sintering at a temperature of 1000 °C or less, more preferably 950 °C or less, when standard stability of the object is required.

<Experimental Example 9>

In order to confirm the density change of the molded object according to the sintering temperature, the following experiment was performed.

Densities of the sintered compact containing white illite and the sintered compact containing yellow illite, which were heat treated up to each sintering temperature, were calculated through the Archimedes method.

According to FIG. 9 , it can be seen that even when the sintering temperature exceeds 950° C., the additional density change occurs gently.

When the molded body was held at 100, the shrinkage ratio was measured and investigated. When the X, Y, and Z axes were respectively calculated, it was found that the shrinkage occurred gently up to 1000 ℃ and then rapidly contracted at 1100 ℃. On the other hand, when calculated by volume based on these, it is confirmed that the shrinkage is gradually reduced from 950 °C.

<Experimental Example 10>

In order to confirm the mechanical properties of the sculpture according to the sintering temperature, the following experiment was performed. After sintering the cylindrical 3D-printed structures including white illite and yellow illite at 900 to 1100 °C, mechanical properties were measured under each condition through a compressive strength meter.

According to FIG. 10, when a sculpture is manufactured using a mixture for photopolymerization containing white illite, the compressive strength of the object does not significantly increase even when the sintering temperature is increased, but a mixture for photopolymerization containing yellow illite is used. It can be confirmed that the compressive strength greatly increases while the sintering temperature exceeds 1000 ° C. It can be seen that when compressive strength is required, it is preferable to perform sintering at a high temperature exceeding 1000 °C.

<Experimental Example 11>

The following experiment was performed to confirm the far-infrared emissivity according to whether the molded body manufactured by the method of the present invention was sintered.

The emissivity of the green body and the structure sintered at 1100 ℃ was measured at the Korea Far Infrared Application Evaluation Institute affiliated with the Korea Far Infrared Association. It was tested at 37 ℃ and the measurement results were investigated compared to the black body using FT-IR Spectrometer.

According to FIG. 11, not only the green body before sintering of the molded body manufactured by the method of the present invention, but also the sintered body sintered at 1100 ° C. showed a far-infrared emissivity of 91% or more compared to the emissivity of the black body. It can be seen that the shape shows the far-infrared emissivity similar to that of the Illite raw material.

<Experimental Example 12>

In order to confirm the antibacterial properties of the molded object prepared by the method of the present invention against Staphylococcus aureus, the following experiment was performed.

The evaluation was carried out at the Korea Analytical Testing Institute, inoculated with 50 mL of phosphate buffer for 18 hours, and the concentration of the bacteria was 1.5-3.0 x 105 CFU/mL. Then, 2.0% (=1.0g) of the sample was added and 1 hour. After shaking for a while, the CFU (Colony Forming Unit) of the buffer was measured and the bacterial reduction rate was measured according to the following formula.

Bacterial reduction rate (%) = [(number of cells after culturing of Control)-(number of cells after culturing of sample)] / (number of cells after culturing of Control) X 100

According to FIG. 12, in the case of the green body before sintering, in both cases including yellow illite and white illite, antibacterial properties of 90% or more are shown, and in the case of the sintered body, when yellow illite is included, the antibacterial properties are somewhat lowered. However, in the case of including white illite, it can be confirmed that the molded object manufactured by the method of the present invention effectively maintains the antibacterial properties of the illite raw material by maintaining about 80% or more of the antibacterial properties.

<Experimental Example 13>

The following experiments were performed to confirm the specifications and shape stability of the molded body manufactured by the method of the present invention.

The white illite powder is pulverized, classified, and uniformly mixed with the photopolymerizable resin, and the thickness of the layer is controlled to 20 micrometers through the blade of the material film supply type ceramic 3D printer, and the light irradiation time is 10 seconds/layer. The button shape was molded. At this time, the illite mineral content was 50% by volume. The printed molded body was degreased to remove organic matter (photopolymerizable resin) contained at 600°C, and sintered at 1100°C to secure the final ceramic structure.

According to FIG. 13 , it can be confirmed that the molded body manufactured by the method of the present invention is not distorted or cracked even after sintering, and thus, reliability is ensured in application to various fields of application.

<Experimental Example 14>

With respect to the muscovite itself purchased from INT Korea and the specimen ball milled (2 hours, 450 rpm, planetary mill), the particle size distribution was confirmed with a micro particle size analyzer, The results are shown in FIG. 14 .

According to FIG. 14, it can be seen that the particle size of muskovite before ball milling is large and non-uniform, but in the case of muskovite after ball milling, the particle size is small and the size distribution is relatively uniform.

<Experimental Example 15>

An experiment was performed to prepare a slurry using the muskovite before ball milling and the muscobite after ball milling prepared in Experimental Example 14, and apply it on a film, and the results are shown in FIG. 15 .

According to FIG. 15, when muscovite is used before ball milling, a uniform and stable slurry state cannot be obtained due to a large particle size, and thus it can be seen that the applicability on the film is poor, and ball milling muskovite is used. In this case, it can be seen that the particle size is small, the particle size distribution is improved, and a stable slurry can be obtained, and the applicability on the film is improved.

<Experimental Example 16>

The following experiment was performed to confirm the change in viscosity of the photopolymerization mixture according to the dispersant.

Muscobite purchased from i-T Korea was introduced into the mixture of acrylate-based monomer and photoinitiator, which is a resin for photopolymerization, in an amount of 50% by volume relative to the total volume of the mixture, and 4% by weight, 5% by weight, and 6% by weight. %, 7% by weight, and 8% by weight of each dispersant was mixed, and the homogenization step was performed using a corotation mixer to prepare five photopolymerization mixtures. With respect to the prepared mixture for photopolymerization, the viscosity of each mixture was measured using a viscometer, and the results are shown in FIG. 16 .

According to FIG. 16 , as the amount of the dispersant included increases, the viscosity of the mixture decreases, but it can be seen that when included in 8 wt%, the viscosity slightly increases compared to when included in 7 wt%.

<Experimental Example 17>

In order to confirm the change in the viscosity of the mixture for photopolymerization according to the content of muscobite, the following experiment was performed.

Muscobite purchased from INT Korea was introduced into the mixture of acrylate-based monomer and photoinitiator, which is a resin for photopolymerization, in contents of 40%, 45%, 50%, and 51% by volume relative to the total volume of the mixture, respectively, and 7 wt% % of the dispersant, and a homogenization step using a corotation mixer to prepare a total of four photopolymerization mixtures. For each of the prepared mixtures for photopolymerization, the viscosity of each mixture was measured using a viscometer, and the results are shown in FIG. 17 .

According to FIG. 17, it was confirmed that the viscosity was appropriately adjusted up to a content of 50% by volume, but the viscosity increased rapidly when 51% by volume was included.

<Experimental Example 18>

The following experiment was performed to confirm the photopolymerization characteristics with time of the mixture containing muscobite.

Using ^Muscobite purchased from INT Korea, a mixture for photopolymerization was prepared through the processes of grinding, classification, and homogeneous mixing with resin for photopolymerization. Photocuring was performed under the condition of the amount of light of , and the thickness to be photocured by time was confirmed, and the results are shown in FIG. 18 .

According to FIG. 18, in the case of a mixture containing muscovite, a photocuring of 40 micrometers is made after 2 seconds, and a photocuring layer of 120 micrometers is formed after 4 seconds, and then light irradiation It can be seen that as the time increases, the thickness of the photocurable layer also increases.

<Experimental Example 19>

After applying the light-curable slurry mixed with 40% by volume of muscovite on a transparent film through a doctor blade to a thickness of 0.03 mm and uniformly applied, the light is radiated into a finely divided two-dimensional shape to complete the three-dimensional shape with an intensity of 10 mW/cm ² The shape of FIG. 19 was completed by irradiating for 10 seconds with a furnace.

According to FIG. 19 , it can be confirmed that objects having various detailed structures can be molded with high quality by using the photopolymerization mixture containing muscovite.

<Experimental Example 20>

In order to confirm the change of density and mechanical properties according to the sintering temperature, the following experiment was performed.

The density of the sintered compact containing white illite (47 vol%) and the sintered compact containing yellow illite (46 vol%) that had been heat treated up to the sintering temperature was calculated through the Archimedes method, and the density was measured under each condition through a compressive strength meter. .

The results are shown in FIG. 20 when yellow illite is included, and in FIG. 21 when white illite is included.

According to FIGS. 20 and 21 , it can be confirmed that the relative density increases as the sintering temperature increases, and the mechanical strength also increases with the same tendency.

<Experimental Example 21>

In order to confirm the structural change of illite according to the sintering temperature, the following experiment was performed.

Using yellow illite and white illite powder purchased from Yonggung Illite Co., Ltd., a mixture for photopolymerization was prepared through the processes of grinding, classification, and homogeneous mixing with resin for photopolymerization, which was then applied to a material film supply type photocurable 3D printer. Photocuring was performed under the condition of a light quantity of 10mW/cm ² by application. After degreasing the photocured product at 600 °C, the temperature was raised to 900 °C, 950 °C, 1000 °C, and 1100 °C at a heating rate of 1 °C/min, respectively, and sintered.

22 and 23 show SEM images of the purchased powder, the photocured product (green body), and the result sintered at each temperature.

According to FIGS. 22 and 23, when both yellow illite and white illite are sintered to 1100 °C, it can be confirmed that the density is improved, and accordingly, it can be expected that the compressive strength is increased.

Claims (16)

pulverizing illite or muskovite raw materials; and
mixing the powdered illite or muscobite raw material with the resin for photopolymerization, mixing up to 50% by volume of the total volume of the mixture to prepare a photopolymerization mixture;
A method for producing a mixture for photopolymerization containing illite or muscovite comprising a.
delete The method of claim 1, further comprising the step of applying a dispersant to the powdered mica raw material before mixing the powdered illite or muskovite raw material with the resin for photopolymerization. A method for preparing a mixture for photopolymerization comprising a.
The method of claim 1, further comprising the step of acid-treating the powdered illite or muskovite before mixing the powdered illite or muskovite with the resin for photo-curing. A method for preparing a mixture for photopolymerization containing cobite.
delete delete A mixture for photopolymerization prepared by the method of claim 1 and comprising illite or muscobite raw material, comprising up to 50% by volume relative to the total volume of the mixture.
delete Forming a sculpture by introducing a mixture for photopolymerization containing illite or muskovite prepared by the method of claim 1 into a 3D printer; and
sintering the molded object;
A method of manufacturing a sculpture comprising illite or muscovite, characterized in that it comprises a.
[Claim 10] The method of claim 9, wherein the illite or muskovite of the mixture for photopolymerization containing illite or muskovite is acid-treated illite or muskovite.
[10] The method of claim 9, wherein the illite is white illite.
[10] The method of claim 9, wherein the sintering is performed at a temperature of 1000 °C or less.
[13] The method of claim 12, wherein the sintering is performed at a temperature of 950 °C or less.
[10] The method of claim 9, wherein the illite is yellow illite, and the sintering is performed at a temperature of more than 1000 °C.
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