Composition for 3D printing

Abstract

The present application relates to a resin composition for 3D printing, a 3D printing method using the same, and a three-dimensional shape comprising the same, and provides a resin composition which is capable of precisely forming a three-dimensional shape and implementing uniform curing properties of a three-dimensional shape.

Claims

1. A composition for 3D printing comprising magnetic particles having at least two magnetic domains, wherein the magnetic domains are irregularly arranged when an external magnetic field is absent and are magnetized by an external magnetic field, and a thermosetting resin, wherein the magnetic particles are vibrated by magnetization reversal, and wherein the magnetic particles satisfy Formula 1 below:
MX.sub.aO.sub.b  [Formula 1] wherein, M is a metal oxide, X includes Fe, Mn, Co, Ni or Zn, and |a×c|=|b×d| is satisfied, where c is the cation charge of X, and d is the anion charge of oxygen, and wherein the magnetic particles have a coercive force in a range of 1 to 200 kOe, and wherein the magnetic particles have an average particle size in a range of 20 to 50 nm.

2. The composition for 3D printing according to claim 1, wherein the magnetic particles have a saturation magnetization value at 25° C. in a range of 20 to 150 emu/g.

3. The composition for 3D printing according to claim 1, wherein the magnetic domains have an average size in a range of 10 to 50 nm.

4. The composition for 3D printing according to claim 1, wherein the magnetic particles are comprised in an amount of 0.01 to 25 parts by weight, relative to 100 parts by weight of the thermosetting resin.

5. The composition for 3D printing according to claim 1, wherein the magnetic particles form magnetic clusters.

6. The composition for 3D printing according to claim 1, wherein the thermosetting resin comprises at least one thermosetting functional group.

7. The composition for 3D printing according to claim 1, further comprising a thermosetting agent.

8. The composition for 3D printing according to claim 7, wherein the filler comprises an organic filler, an inorganic filler, or a mixture thereof.

9. The composition for 3D printing according to claim 1, further comprising a filler.

10. The composition for 3D printing according to claim 1, further comprising a dispersing agent.

11. A 3D printing method comprising a step of applying the composition for 3D printing of claim 1 to form a three-dimensional shape.

12. The 3D printing method according to claim 11, further comprising a step of applying a magnetic field to the applied composition.

13. The 3D printing method according to claim 12, wherein the step of applying a magnetic field applies a magnetic field with a current of 50 A to 500 A for 20 seconds to 60 minutes at a frequency of 100 kHz to 1 GHz.

14. The 3D printing method according to claim 12, wherein the step of applying a magnetic field comprises at least two steps of multi-profile methods.

15. The 3D printing method according to claim 14, wherein the multi-profile method comprises a first step of applying a magnetic field with a current of 10 A to 80 A for 20 seconds to 10 minutes, a second step of applying a magnetic field with a current of 80 A to 130 A for 20 seconds to 10 minutes and a third step of applying a magnetic field with a current of 150 A to 500 A for 5 seconds to 5 minutes, at a frequency of 100 kHz to 1 GHz.

16. A three-dimensional shape comprising a cured product of the composition for 3D printing of claim 1.

Description

BEST MODE

(1) Hereinafter, the present invention will be described in more detail with reference to Example complying with the present invention and Comparative Examples not complying with the present invention, but the scope of the present invention is not limited by the following examples.

Example 1

(2) FeOFe.sub.2O.sub.3 particles (Multi-Magnetic Domains, average particle size about 50 nm: measured by Field Emission Scanning Electron Microscope (using DLS)), which are a soft magnetic material (Soft Type), as magnetic particles, KSR-177 from Kukdo Chemical Co., Ltd. as an epoxy resin and an imidazole curing agent of C11ZA from Shikoku Kasei as a curing agent were mixed at a weight ratio of 5:90:5 (FeOFe.sub.2O.sub.3: KSR-177: C11ZA) to prepare a resin composition.

(3) Immediately after laminating the resin composition on a support through a nozzle in a feeding device, a magnetic field was applied thereto at a current value of 100 A for 10 minutes in an external alternate-current magnetic field generator. The magnetic field was applied by introducing the composition into a sample vial in a solenoid coil (3 turns, OD 50 mm, ID 35 mm) and adjusting the current value and time of the magnetic field generator (Easyheat from Ambrell). The composition was thermally cured with vibrational heat generated through application of the magnetic field to form a pattern or a three-dimensional shape.

Example 2

(4) A resin composition was prepared in the same manner as in Example 1, except that the particle size of the magnetic particles is 100 nm, and allowed to form a three-dimensional shape.

Example 3

(5) A resin composition was prepared in the same manner as in Example 1, except that the contents of the magnetic particles, the resin and the curing agent were included at a weight ratio of 10:90:5, respectively, and allowed to form a three-dimensional shape.

Example 4

(6) A resin composition was prepared in the same manner as in Example 1, except that the particle size of the magnetic particles is 200 nm, and allowed to form a three-dimensional shape.

Example 5

(7) A resin composition was prepared in the same manner as in Example 2, except that MnOFe.sub.2O.sub.3 particles (Multi-Magnetic Domains, average particle size about 100 nm: measured by Field Emission Scanning Electron Microscope (using DLS)) were used as magnetic particles, and allowed to form a three-dimensional shape.

Comparative Example 1

(8) FeOFe.sub.2O.sub.3 particles (Single-Magnetic Domain, average particle size about 100 nm), which are a ferromagnetic material (Hard Type), as magnetic particles, a bisphenol epoxy resin and a curing agent were mixed at a weight ratio of 5:95:5 to prepare a resin composition.

(9) Immediately after laminating the resin composition on a support through a nozzle in a feeding device, a magnetic field was applied thereto at a current value of 100 A for 10 minutes in an external alternate-current magnetic field generator. The magnetic field was applied by introducing the composition into a sample vial in a solenoid coil (3 turns, OD 50 mm, ID 35 mm) and adjusting the current value and time of the magnetic field generator (Easyheat from Ambrell). The composition was thermally cured with vibrational heat generated through application of the magnetic field to form a pattern or a three-dimensional shape.

Comparative Example 2

(10) A resin composition was prepared in the same manner as in Comparative Example 1, except that Fe particles (Single-Magnetic Domain, average particle size about 50 nm), which are a ferromagnetic material (Hard Type), were used as magnetic particles and the contents of the magnetic particles, the resin and the curing agent were included at a weight ratio of 5:90:5, respectively, and allowed to form a three-dimensional shape.

Comparative Example 3

(11) A resin composition was prepared in the same manner as in Comparative Example 1, except that StOFe.sub.2O.sub.3 particles (Single-Magnetic Domain, average particle size about 100 nm), which are a ferromagnetic material (Hard Type), were used as magnetic particles and the contents of the magnetic particles, the resin and the curing agent were included at a weight ratio of 5:90:5, respectively, and allowed to form a three-dimensional shape.

Experimental Example 1—Measurement of Coercive Force and Saturation Magnetization Value (Ms) of Magnetic Particles

(12) The magnetic particles dried at room temperature were placed in a vibrating sample magnetometer (SQUID-Vibrating Sample Magnetometer, measured by Korea Basic Science Institute) and the coercive force and saturation magnetization value Ms were measured using an H-S curve (VSM curve) at an external magnetic field of ±1 Tesla.

Experimental Example 2—Measurement of Temperature of the Composition after Curing

(13) In Examples and Comparative Examples, the temperature inside the three-dimensional shape is confirmed by piercing it with a thermocouple.

Experimental Example 3—Measurement of Cure Degree

(14) (1) Visual Touch

(15) After curing the composition, it was confirmed whether the cured product had flowed when it was turned over after cooling, and then the curing was confirmed by checking the degree of pressing of the cured product with a metal spatula. In the above, it can be confirmed that when there is flowability and the cured product is pressed, the composition has been not cured.

(16) (2) IR Data

(17) Before and after thermosetting of the composition, the cure degree is determined by calculating a conversion ratio (%) using a ratio of an intensity (about 900 cm.sup.−1) of the epoxy group and an intensity (about 1500 cm.sup.−1) of the phenyl group.

(18) (3) DSC Data

(19) The cure degree is determined by measuring a residual heat (J/g) in the endothermic peak section, which is generated when the thermally cured sample after applying the magnetic field is raised to a temperature of 300° C. at a rate of temperature increase of 10° C./min by a cut DSC.

(20) TABLE-US-00001 TABLE 1 Coercive Temperature Measurement of Cure Degree Ms Force after curing Visual (emu/g) (kOe) (° C.) Touch IR DSC Example 1 72 70 170 Cured 42% 12.3 J/g Example 2 74 80 150 Cured 11% 55.1 J/g Example 3 74 80 180 Cured 44%  3.0 J/g Example 4 82 92 145 Cured 25% 84.5 J/g Example 5 80 94 176 Cured 51%  5.8 J/g C. Example 1 218 2000 35 Non-cured Unmeasurable Unmeasurable C. Example 2 154 294 27 Non-cured Unmeasurable Unmeasurable C. Example 3 48 1500 40 Non-cured Unmeasurable Unmeasurable (C. Example: Comparative Example)

(21) In the case of Comparative Examples 1 to 3, heat is generated by eddy current as a technique by electromagnetic induction, and it can be confirmed that heat is generated by hysteresis loss of the magnetic particles. Thus, in Comparative Examples 1 to 3, it is impossible to precisely form a three-dimensional solid shape, and the desired curing properties are not satisfied.