KR102136574B1 - Binder composition for a 3D printer comprising benzoxazine derivative, and manufacturing method of binder for 3D printer - Google Patents

Abstract

The present invention relates to a binder composition for a 3D printer comprising a benzoxazine derivative having a small shrinkage and a small thermal distortion and excellent physical strength, further comprising: synthesizing a benzoxazine derivative; And adding and stirring a derivative and an additive to the synthesized benzoxazine; providing a method for manufacturing a binder for an excellent 3D printer that is easy to discharge an adhesive from the printer head and does not precipitate a benzoxazine derivative.

Description

Binder composition for a 3D printer comprising benzoxazine derivative, and manufacturing method of binder for 3D printer}

The present invention relates to a binder composition for a 3D printer and a method for manufacturing the same, and more particularly, to a binder composition for a 3D printer having a small shrinkage rate including benzoxazine derivatives and less thermal deformation and excellent physical strength, and a method for manufacturing the same.

3D printing (printing) technology is defined as a technology for manufacturing a three-dimensional product by processing a metal powder, ceramic, polymer material of a two-dimensional pattern.

Also called additive manufacturing (AM), it is a concept opposite to the manufacturing method of subtractive manufacturing, in which a three-dimensional object is cut or dug through machining. With the high degree of freedom in design, it is possible to manufacture virtual model products without special production tools, thereby reducing development cycles and cost including product modification. The global market for 3D printers is projected to grow by 31% annually and increase to $26 billion by 2021, and is expected to grow significantly in many industries such as medical, bio, aerospace, consumer goods, automotive, and defense industries. .

Such 3D printers are fused deposition modeling (FDM), extrusion based on solids, powder-based selective laser sintering (SLS), powder bed and inkjet head printing (3DP), electron beam melting (EBM), and sight depending on the molding method. It is largely divided into chemical liquid-based stereolithography (SLA), digital light processing (DLP), photopolymer jetting (Polyjet), and laminated object manufacturing (LOM) of laminate method.

Of these, 3DP is a 3D printing method that uses a binder jetting to spray and deposit liquid adhesive on powdery materials such as sand, spread the adhesive on a thin layer of the powdered material, and spray the adhesive on the powdered material using a roller. It is a method of repeatedly stacking the covering process. Among 3D printers, relatively fast molding is possible and color solutions can be sprayed together with adhesives to realize various colors, and there is an advantage in that printing is possible without limitation in size without requiring a support.

Binders are materials that contribute to or connect two particles or materials, and are made of liquid, powder-based, thermoset or thermoplastic resins and the like. It can consist of two components that react when they come into contact with one another, one of which is a liquid and the other can be a dry matter.

In the case of patent document KR 10-1834278, a 3D printer manufactured by ExOne of Germany and its arrangement and production method are described, and furan is included as a binder component of the 3D printer. When using a binder for an existing 3D printer containing furan, phenol, etc., the material does not have ductility and fracture brittleness occurs, volatiles are released during the curing process, and condensation polymerization reaction occurs to generate by-products. do. In addition, after using a strong acid and a strong base as a catalyst, a pre-treatment process in which the curing agent is pre-mixed with the powder material, a method of spraying a binder must be used, and the shortening period of the kneading agent of the curing agent and the powder material is short, about a month. .

KR 10-1834278 KR 10-1788336

In order to solve the above problems, the present invention overcomes the problems of brittleness of existing 3D printer binders, generation of volatiles and by-products during curing, and pre-treatment of powder materials, small shrinkage, low thermal deformation, and physical strength. It is an object to provide a binder composition for a 3D printer comprising an excellent benzoxazine derivative.

In addition, it is an object of the present invention to provide a method for manufacturing a binder for an excellent 3D printer that includes the above features, facilitates ejection of an adhesive from a printer head, and does not precipitate benzoxazine derivatives.

The present invention to solve the above object,

A benzoxazine derivative represented by the following Chemical Formula 1, characterized in that it contains 5-20 wt%, a wetting agent 5-25 wt%, a surface tension modifier 0.1-0.5 wt%, and a solvent 55-89 wt% Provided is a binder composition for a printer:

[Formula 1]

R'and R₂ in Formula 1 are each independently an alkyl group or an aryl group.

The wetting agent includes one selected from glycols or diols, and can adjust the viscosity of the binder.

E In addition, the surface tension modifier includes one selected from surfactants tergitol, polyacrylic acid, methyl cellulose, and ethyl cellulose.

The solvent includes one selected from Diethyleneglycol monomethylether (DGME) and Diethyleneglycol monoethylether (DGEE).

The viscosity range of the binder is 12.5-16.5 cP, and the surface tension range is 33-37 dyne/cm.

The present invention to solve the above other object,

Synthesizing a benzoxazine derivative represented by Formula 1 below; And

It provides a method for manufacturing a binder for a 3D printer, characterized in that it comprises; agitating by adding a derivative and an additive to the synthesized benzoxazine.

[Formula 1]

R'and R₂ in Formula 1 are each independently an alkyl group or an aryl group.

The additive includes a solvent, a wetting agent and a surface tension regulator, and 5-20 wt% of a benzoxazine derivative represented by Formula 1, a wetting agent 5-25 wt%, a surface tension regulator 0.1-0.5 wt%, and a solvent 55-89 wt%.

The present invention includes a benzoxazine derivative, a wetting agent, a surface tension adjusting agent, and a solvent in a binder composition for a 3D printer, so that by-products are not generated in the binder curing process, casting defects during casting are reduced, and small shrinkage and thermal deformation are exhibited. It has an excellent strength effect.

1 is a table showing the sequence of the benzoxazine precursor synthesis process according to Example 1 of the present invention.
2 is a table showing the order of the benzoxazine binder manufacturing method according to the second embodiment of the present invention.
Figure 3 is a view showing the results of the ejection droplet experiment and the droplet printing experiment of the binder prepared according to Example 1 of Table 1 of the present invention.
FIG. 4 is a view showing the results of a discharge droplet experiment and a droplet printing experiment of the binder prepared according to Example 1 of Table B of the present invention.
FIG. 5 is a view showing the results of a test for ejecting droplets and a test for printing droplets of a binder prepared according to C of Example 1 of the present invention.
FIG. 6 is a view showing the results of an experiment of ejection droplets and a droplet printing experiment of a binder prepared according to D of Example 1 of the present invention.
FIG. 7 is a view showing the results of a test for ejecting droplets and a test for printing droplets of a binder prepared according to Table A of the Example 2 of the present invention.
Figure 8 is a view showing the results of the ejection droplet experiment and the droplet printing experiment of the binder prepared according to B of Example 2 of the present invention.
FIG. 9 is a view showing the results of a test for ejection droplets and a test for printing droplets of a binder prepared according to C of Example 2 of the present invention.
10 is a view showing a discharge droplet experiment and a droplet printing experiment of the binder prepared according to D of Table 2 of the embodiment of the present invention.
11 is a view showing the results of the drop droplets of the binder prepared according to Table 3A of Comparative Example of the present invention.
Figure 12 is a view showing the results of the drop droplets of the binder prepared according to B of Comparative Example Table 3 of the present invention.

The present invention relates to a binder composition for a 3D printer and a method for manufacturing the same, and more particularly, to a binder composition for a 3D printer having a small shrinkage rate including benzoxazine derivatives and less thermal deformation and excellent physical strength, and a method for manufacturing the same.

Hereinafter, the present invention will be described in more detail.

According to one aspect of the present invention, the benzoxazine derivative represented by Chemical Formula 1 below is 5-20 wt%, wetting agent 5-25 wt%, surface tension modifier 0.1-0.5 wt%, and solvent 55-89 wt% It provides a binder composition for a 3D printer, comprising:

[Formula 1]

R'and R₂ in Formula 1 are each independently an alkyl group or an aryl group.

The benzoxazine is preferably 6,6'-Propane-2,2-diylbis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazine), 6,6'-Propane-2,2 -diylbis(3-methyl-3,4-dihydro-2H-1,3-benzoxazine).

In order to make the complex description on the specification easy to see, in the following specification, 6,6'-Propane-2,2-diylbis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazine) is Ba, 6 ,6'-Propane-2,2-diylbis(3-methyl-3,4-dihydro-2H-1,3-benzoxazine) is named Bm.

In the present invention, the benzoxazine derivative has little water absorption, is stable at room temperature, has little volume change in the curing process, and does not release toxins. In addition, since a pretreatment process of adding a curing agent to the powder material is not required during curing, a strong acid or a strong base is not used, and all components can be mixed and used for printing in the form of a single solution.

When the Benjok photo is included in a proportion of less than 5 wt%, the strength of the mold to be formed is lowered, so that the mold is not properly formed. Since it is not supported, it preferably contains 5-20 wt%, and more preferably 7-10 wt%.

Binders containing benzoxazine derivatives do not generate by-products during the curing process by ring-opening polymerization, and finally, casting defects are reduced during casting. The ring-opening polymerization reaction is also called a ring-opening polymerization reaction, and is a polymerization reaction in which a ring-shaped compound is opened to become a sun-shaped polymer, and refers to a case where an intramolecular bond is changed to an intermolecular bond to become a polymer.

An alkyl group is an atomic group represented by the general formula of C _n H _2n+1 by removing one hydrogen atom from a chain-like or aliphatic saturated hydrocarbon. Methyl (CH ₃ -), ethyl (C ₂ H ₅ -), propyl (C ₃ H ₇ -), butyl (C ₄ H ₉ -), pentyl (C ₅ H ₁₁ -), hexyl (C ₆ H ₁₃ -) ), heptyl (C ₇ H ₁₅ -), octyl (C ₈ H ₁₇ -), nonyl (C ₉ H ₁₉ -), decyl (C ₁₀ H ₂₁ -), undecyl (C ₁₁ H ₂₃ -), dodecyl (C ₁₂ H ₂₅ -), tridecyl (C ₁₃ H ₂₇ -), tetradecyl (C ₁₄ H ₂₉ -), pentadecyl (C ₁₅ H ₃₁ -), hexadecyl (C ₁₆ H ₃₃ -), heptadecyl (C ₁₇ H ₃₅ -), octadecyl (C ₁₈ H ₃₇ -), nonadecyl (C ₁₉ H ₃₉ -), eicosyl (C ₂₁ H ₄₁ -), and the like.

The aryl group (aryl group) corresponds to an alkyl group in which one hydrogen atom is removed from an aliphatic hydrocarbon, and one hydrogen atom is removed from an aromatic hydrocarbon. There are phenyl group (C ₆ H ₅ -) derived from benzene, anthracene (C ₁₄ H ₉ -) and phenanthryl group (C ₁₄ H ₉ -) derived from anthracene and phenanthrene, which are condensed ring aromatic compounds, and benzene. Biphenyl group (C ₁₂ H ₉ -) derived from biphenyl, a compound in which two nuclei are directly bonded, toluene-derived toryl group (CH ₃ C ₆ H ₄ -), naphthyl derived from naphthalene (C ₁₀ H ₇ -), xylene-derived xylene groups ((CH ₃ ) ₂ C ₆ H ₃ -).

Wetting agent is a substance that absorbs or preserves moisture and is also called a moisturizer. In the present invention, ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, triethylene glycol, dipropylene glycol monoethyl glycol, dipropylene glycol, triethylene glycol , Tetraethylene glycol, tripropylene glycol, isopropylene glycol, isobutylene glycol, glycerol, glycerol carbonate, glycerol monostearate, glycols, and diols.

Viscosity modifier is a component that increases or decreases the viscosity of a contained substance and has a significant effect on the stability, texture and usability of the substance. In the present invention, the wetting agent serves as a viscosity modifier, and is characterized by being soluble in the benzoxazine derivatives and solvents contained in the binder.

At this time, when the wetting agent is included in a proportion of less than 5 wt%, the drying of the liquid in the 3D printer head may occur quickly, and thus ejection of the binder may be inhibited, so that 5-25 wt% is preferably included. It contains 10-22 wt%.

In addition, the surface tension modifier is tergitol, polyacrylic acid, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene Lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy It characterized in that it comprises one selected from surfactants such as poly(ethyleneoxy) ethanol.

Surface tension modifiers are substances or components that control the surface tension defined by the force of the liquid's surface to shrink itself and take as little area as possible. In the present invention, the surface tension adjusting agent is characterized by being soluble with a benzoxazine derivative and a solvent contained in the binder, wherein the surface tension adjusting agent is a liquid in the 3D printer head when it contains less than 0.1 wt% ratio. Since the liquid droplets can form droplets spreading without maintaining the shape when discharging of, it is preferably to contain 0.1-0.5 wt%, and more preferably contains 0.2-0.3 wt%.

In addition, the solvent is characterized in that it comprises one selected from DGME (2-(2-ethoxyethoxy)ethanol, DGEE (2-(2-methoxyethoxy)ethanol), Ethyleneglycol monomethylether (EGME), Ethyleneglycol monoethylether (EGEE).

In the present invention, the solvent is capable of dissolving the benzoxazine derivative, and is capable of discharging from the 3D printer head. At this time, when the solvent is included in an amount exceeding 89 wt%, another composition of the 3D printer binder Since the component cannot be included in the required weight, and finally, the binder cannot be physically and chemically prepared, preferably 55 to 89 wt% is included. More preferably 68-80 wt%.

The viscosity range of the binder prepared by including all of the additives in the present invention is characterized in that 12.5-16.5 cP, and the surface tension range is 33-37 dyne/cm.

When the viscosity range is 12.5 cP or less, ink (binder) may flow out from the printing head, and when it is 16.5 cP or more, ink (binder) may not be discharged from the print head. When the surface tension range is less than 33 dyne/cm, the ink (binder) also flows out of the print head, so printing of a desired shape may be difficult, and when it exceeds 37 dyne/cm, ink (binder) from the print head Is not discharged, and the nozzle may be clogged.

In another aspect, the present invention, the step of synthesizing a benzoxazine derivative represented by Formula 1; And

It provides a method for manufacturing a binder for a 3D printer, characterized in that it comprises; agitating by adding a derivative and an additive to the synthesized benzoxazine.

[Formula 1]

R'and R₂ in Formula 1 are each independently an alkyl group or an aryl group.

The additive includes a solvent, a wetting agent, and a surface tension regulator, and 5-20 wt% of a benzoxazine derivative represented by Formula 1, 5-25 wt%, a wetting agent, 0.1-0.5 wt%, and a solvent 55 -89 wt%.

The present invention will be described in more detail by the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited by the examples. The present invention is made to be complete, and is provided to fully inform the scope of the invention to those of ordinary skill in the art.

<Example>

Example 1. Synthesis of benzoxazine precursor

After adding 60.06 g of 2.0 mol formaldehyde and 400 ml of dioxane to the two flasks, respectively, 1.0 g of 1.0 mol aniline and 100 ml of dioxane in one flask, and 1.0 mol methylamine in the other flask (methylamine) 31.05g and dioxane 100ml was added. To each flask, 114 g of 0.5 mol bisphenol-A (bisphenol-A) and 500 ml of dioxane were added and stirred, and two benzoxazine precursors were synthesized by heating the flask and refluxing for 4 hours.

Thereafter, the solvent was removed in a vacuum, and two benzoxazine precursors in which the solvent was removed were dissolved in 700 ml of dichloromethane (MC), and the MC solution in which the benzoxazine precursor was dissolved was washed with distilled water and 3 N NaOH solution. After the process, the benzoxazine synthesized by drying under vacuum using sodium sulfate was purified.

Example 2 Preparation of benzo photo binder

First, a solvent was added and stirred into the synthesized benzoxazine solid, and then a wetting agent and a surface tension adjusting agent were respectively added and stirred to prepare a binder. Diethyleneglycol monomethylether (DGME), Diethyleneglycol monoethylether (DGEE), Ethyleneglycol monomethylether (EGME), and Ethyleneglycol monoethylether (EGEE) were used as the solvent, and glycerol was used as the wetting agent, and tergitol was used as the surface tension regulator. .

A binder was prepared by mixing each component in various ratios by weight ratio, and the optimum solvent and optimum weight ratios were derived through the results of various examples and comparative examples to be described below.

Example 3. Discharge experiment according to the solvent type of the binder containing B-a

Using a solvent DGME, DGEE, EGME, EGEE to prepare a binder for a 3D printer containing the benzox picture, and performing a discharge experiment to confirm the droplets appearing.

Using the Omnijet100 printer and a drop watcher, the discharged droplets of the prepared binder, the stability of the binder jetting, and whether the nozzles were clogged were checked. It was shown.

Ba

DGME

DGEE

EGME

EGEE

glycerol

tergitol

A

4.70 g
(9.99 wt%)
32.54 g (69.15 wt%) 9.77 g
(20.76 wt%) 0.0471 g
(0.10 wt%)
B

5.45 g
(9.98 wt%)
37.74 g (69.10 wt%) 11.32 g (20.73 wt%) 0.1092 g
(0.20 wt%)
C

5.23 g
(9.98 wt%)
36.21 g (69.08 wt%) 10.87 g (20.74 wt%) 0.1048 g
(0.20 wt%)
D

7.90 g
(9.95 wt%)
54.70 g (68.89 wt%) 16.41 g (20.67 wt%) 0.3970 g
(0.50 wt%)

Example 4. Discharge experiment according to the solvent type of the binder containing B-m

Using a solvent DGME, DGEE, EGME, EGEE to prepare a binder for a 3D printer containing the benzox picture, and performing a discharge experiment to confirm the droplets appearing.

Using the Omnijet100 printer and a drop watcher, the discharged droplets of the prepared binder, the stability of the binder jetting, and whether the nozzles were clogged were checked. It was shown.

Bm

DGME

DGEE

EGME

EGEE

glycerol

tergitol

A
8.03 g
(9.99 wt%) 55.60 g (69.16 wt%) 16.68 g (20.75 wt%) 0.0804 g
(0.10 wt%)
B
3.53 g
(9.98 wt%) 24.44 g (69.08 wt%) 7.34 g
(20.75 wt%) 0.0708 g
(0.20 wt%)
C
5.89 g
(9.84 wt%) 41.4 g
(69.20 wt%) 12.42 g (20.76 wt%) 0.1197 g
(0.20 wt%)
D
0.65 g
(9.99 wt%) 4.5 g
(69.16 wt%) 1.35 g
(20.75 wt%) 0.0065 g
(0.10 wt%)

Comparative Example 1. Discharge experiment according to the weight ratio of the solvent, wetting agent and surface tension adjusting agent of the binder containing B-m

Using a solvent DGME, DGEE, EGME, EGEE to prepare a binder for a 3D printer containing the benzox picture, and performing a discharge experiment to confirm the droplets appearing.

Using the Omnijet100 printer and drop watcher, the discharged droplets of the prepared binder, the stability of the binder jetting, and whether the nozzles were clogged were checked. It was shown.

Bm
DGME DGEE EGME EGEE glycerol tergitol
A
2.45 g
(10.02 wt%) 20.00 g (81.80 wt%) 2.00 g
(8.18 wt%)


B
2.67 g
(10.71 wt%)
20.00 g (80.26 wt%) 2.00 g
(8.03 wt%) 0.2492 g
(1.00 wt%)
C
1.18 g
(5.52 wt%)
20.00 g (93.48 wt%)
0.2139 g
(1.00 wt%)
D
1.20 g
(20.07 wt%) 4.78 g
(79.93 wt%)


E
1.16 g
(19.97 wt%) 4.65 g
(80.03wt%)
F
1.32 g
(20.10 wt%) 5.26 g
(80.11 wt%) 0.0657 g
(1.00 wt%)

<Evaluation and Results>

Results according to Example 1

As a result of benzoxazine precursor synthesis, 6,6'-Propane-2,2-diylbis(3-phenyl-3,4-dihydro-2H-1,3-benzoxazine) and methylamine synthesized using aniline were used. Two benzoxazine photographs synthesized by 6,6'-Propane-2,2-diylbis(3-methyl-3,4-dihydro-2H-1,3-benzoxazine) were prepared.

Scheme 1 below is a benzoxazine synthesis reaction scheme using aniline, and Scheme 2 is a benzoxazine synthesis scheme using methylamine, 6,6'-Propane-2,2-diylbis(3-phenyl-3,4-dihydro-2H -1,3-benzoxazine) and 6,6'-Propane-2,2-diylbis(3-methyl-3,4-dihydro-2H-1,3-benzoxazine) are represented by the following Chemical Formula 2 and Chemical Formula 3, respectively. .

[Scheme 1]

[Scheme 2]

[Formula 2]

[Formula 3]

Results according to Example 3

The results of the ejection experiments according to the solvent type of the binder containing B-a were confirmed in FIGS. 3 to 10. Figures 3-a, 4-a, 5-a and 6-a are discharge evaluation pictures of binders, and Figures 3-b, 4-b, 5-b and 6-b are print evaluation pictures of binders.

Binders prepared using solvents DGME and DGEE formed stable discharge droplets without clogging at the print head nozzles, and formed uniform circular drop droplets with a size of 240-270 μm. On the other hand, the binder produced using the solvent EGME formed stable discharge droplets without clogging at the print head nozzle, but showed poor print quality by forming satellite droplets. The binder produced using EGEE formed stable discharge droplets without clogging at the print head nozzles, but satellite droplets were formed and smearing and agglomeration of falling droplets occurred.

When a satellite droplet is generated when the binder is discharged, a uniform pattern is not formed, and thus, the dimensional precision of the molded object generated through the printing process is lowered, and the uniformity of the overall molded object may be impaired.

Results according to Example 4

The results of the ejection experiments according to the solvent type of the binder containing B-m were confirmed in FIGS. 11 to 18. 7-a, 8-a, 9-a and 10-a are discharge evaluation pictures of the binder, and FIGS. 7-b, 8-b, 9-b and 10-b are printing evaluation pictures of the binder.

Binders prepared using solvents DGME and DGEE formed stable discharge droplets without clogging at the print head nozzles, and formed uniform circular drop droplets with a size of 240-270 μm. On the other hand, the binders produced using the solvents EGME and EGEE formed stable discharge droplets without clogging at the print head nozzles, but showed poor print quality by forming satellite droplets.

Results according to Comparative Example 1

As a result of the discharge test according to the weight ratio of the solvent, wetting agent and surface tension regulator of the binder containing Bm, the same EGEE solvent was used, but the results of A, B, and C differing in the weight ratio of the benzoxazine and the wetting agent and surface tension regulator. By comparison, in the case of C without any wetting agent, discharging of the binder was impossible, and in the case of A and B with wetting agent, smearing of the droplets occurred, but clogging of the print head nozzle did not occur. The drops of A and B were confirmed in FIGS. 11 and 12.

The weight ratio of C is almost the same, but in the case of D using EGME as a solvent, discharge of the binder itself was not possible due to clogging of the printer head nozzle as in C.

Lastly, in the case of E and F, respectively, using DGEE and DGME as solvents, a binder was prepared and tested at a weight ratio almost similar to that, but since no wetting agent was included, clogging of the print head nozzles occurred regardless of the type of solvent. Therefore, the ejection of the binder itself was not possible.

Claims (10)

A benzoxazine derivative represented by the following Chemical Formula 1, characterized in that it contains 5-20 wt%, a wetting agent 5-25 wt%, a surface tension modifier 0.1-0.5 wt%, and a solvent 55-89 wt% Binder composition for printer:
[Formula 1]

In the formula (1), R'and R₂ are each independently an alkyl group or an aryl group. According to claim 1,
The wetting agent is a binder composition for a 3D printer, characterized in that it comprises one selected from glycols or diols. According to claim 1,
The wetting agent is characterized in that it is possible to adjust the viscosity of the binder, a binder composition for a 3D printer. According to claim 1,
The surface tension modifier is a binder composition for a 3D printer, characterized in that it comprises one selected from the surfactants tergitol, polyacrylic acid, methyl cellulose, ethyl cellulose. According to claim 1,
The solvent is characterized in that it comprises one selected from Diethyleneglycol monomethylether (DGME), Diethyleneglycol monoethylether (DGEE), 3D printer binder composition. According to claim 1,
The binder has a viscosity range of 12.5-16.5 cP, characterized in that, 3D printer binder composition. According to claim 1,
The surface tension range of the binder is 33-37 dyne / cm, characterized in that, 3D printer binder composition. Synthesizing a benzoxazine derivative represented by Formula 1 below; And
Characterized in that it comprises a; a step of stirring by adding a derivative and an additive to the synthesized benzoxazine, 3D printer binder manufacturing method:
[Formula 1]

R'and R₂ in Formula 1 are each independently an alkyl group or an aryl group. The method of claim 8,
The additive is characterized in that it comprises a solvent, a wetting agent and a surface tension adjusting agent, 3D printer binder manufacturing method. The method of claim 8,
A benzoxazine derivative represented by Chemical Formula 1, comprising 5-20 wt%, a wetting agent 5-25 wt%, a surface tension modifier 0.1-0.5 wt%, and a solvent 55-89 wt%, 3D Printer binder manufacturing method.

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