Ink composition for 3D printing support and 3D printing manufacturing method using the same

Abstract

The present invention relates to an ink composition for a 3D printing support, comprising an amine-containing monomer and a curing agent. According to the present invention, an ink composition for a 3D printing support, which retains an excellent jetting property, is well dissolved in water after being photo-cured to be easily removed, and has less curing contraction and excellent storage stability, can be provided.

Claims

1. An ink composition for a 3D printing support, the ink composition comprising an amine-containing monomer, a photoinitiator, a water soluble polymer, a vinyl ether compound, and a monomer containing at least one of a vinyl group and an acrylate group, wherein the amine-containing monomer is the compound of the following Formula 1: ##STR00012## wherein R.sub.1 is hydrogen or methyl, and R.sub.2 and R.sub.3 are each independently hydrogen, C.sub.1 to C.sub.10 alkyl, vinyl, alkoxyl, cyclohexyl, phenyl, benzyl, alkylamine, alkyl ester, alkyl ether, ##STR00013## wherein the water soluble polymer is at least one of the compounds of the following Formula 8a to Formula 8d: ##STR00014## wherein n is 50 to 25,000, and the water soluble polymer is included in an amount of 0.1 to 30 wt % based on the total weight of the ink composition, and wherein the vinyl ether compound is selected from 4-hydroxybutyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, diethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, triethylene glycol divinyl ether or 1,4-butanediol divinyl ether, wherein the ink composition when cured is dissolvable in water.

2. The ink composition for a 3D printing support according to claim 1, wherein the C.sub.1 to C.sub.10 alkyl is methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, or ##STR00015## the alkylamine is ##STR00016## and the alkyl ether is R.sub.1OR.sub.2, wherein R.sub.1 is CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2C(CH.sub.3).sub.2 or C(CH.sub.3).sub.2CH.sub.2CH.sub.2, R.sub.2 and R.sub.3 are each independently hydrogen, CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CH(CH.sub.3).sub.2, CH.sub.2C(CH.sub.3).sub.3, CH(CH.sub.3).sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, C(CH.sub.3).sub.2CH.sub.2CH.sub.3 or CHCH.sub.2, R.sub.1 is CH.sub.2, CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH(CH.sub.2)CH.sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.2, CH.sub.2C(CH.sub.3).sub.2 or C(CH.sub.3).sub.2CH.sub.2CH.sub.2, and R.sub.2 is hydrogen, CH.sub.3, CH.sub.2CH.sub.3, CH.sub.2CH.sub.2CH.sub.3, CH.sub.2CH(CH.sub.3).sub.2, CH.sub.2C(CH.sub.3).sub.3, CH(CH.sub.3).sub.2, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, or C(CH.sub.3).sub.2CH.sub.2CH.sub.3.

3. The ink composition for a 3D printing support according to claim 1, wherein the compound of Formula 1 is the compound of the following Formula 1a: ##STR00017## wherein R.sub.1 is hydrogen or methyl, and R.sub.2 and R.sub.3 are each independently methyl, ethyl, propyl, isopropyl, n-butyl, or tert-butyl.

4. The ink composition for a 3D printing support according to claim 1, wherein the monomer containing at least one of a vinyl group and an acrylate group is at least one selected from the group consisting of vinyl acetate, 2-hydroxyethyl(meth)acrylate, 2-hydroxymethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, ethyl-2-hydroxyacrylate, 2-(acryloyloxy)ethyl hydrogen succinate and methacylic acid.

5. The ink composition for a 3D printing support according to claim 1, which further comprises an additive, which is at least one selected from the group consisting of a surfactant, a plasticizer, a polymerization inhibitor, an antifoaming agent, a diluent, a thermal stabilizer and a viscosity controlling agent.

6. A manufacturing method for 3D printing which uses the ink composition for a 3D printing support of claim 1.

Description

BEST MODE CARRYING OUT THE INVENTION

(1) The present invention will be explained in detail with reference to the following examples, including test examples. However, these examples are provided for illustrative purposes only and are not intended to limit the scope of the invention.

EXAMPLE

(2) 1. Preparation of Ink Composition

(3) As shown in the following Table 1, a monomer containing at least one of an amine-containing monomer, a vinyl group and an acrylate group (V/A monomer), a curing agent, a water soluble polymer, a vinyl ether compound and the like were mixed to prepare ink compositions of Examples 1 to 26.

(4) TABLE-US-00001 TABLE 1 Water Vinyl Amine-containing Curing V/A soluble ether monomer agent monomer polymer compound Example 1 DMA I 819 (96.6 wt %) (3.4 wt %) Example 2 DMA + DAA TPO (64.4 + 32.2 wt %) (3.4 wt %) Example 3 DMA + DMAPMA I 819 (64.4 + 32.2 wt %) (3.4 wt %) Example 4 DMA + NMNVA I 819 (64.4 + 32.2 wt %) (3.4 wt %) Example 5 DMA + DMAEA I 819 (64.4 + 32.2 wt %) (3.4 wt %) Example 6 DMA + VP I 819 (48.3 + 48.3 wt %) (3.4 wt %) Example 7 ACMO + VP I 819 (48.3 + 48.3 wt %) (3.4 wt %) Example 8 NIPA + VP I 819 (48.3 + 48.3 wt %) (3.4 wt %) Example 9 DMA + VP I 819 VA (38.25 + 38.25 wt %) (3.5 wt %) (20 wt %) Example 10 DMA + VP I 819 HEA (43.25 + 43.25 wt %) (3.5 wt %) (10 wt %) Example 11 DMA I 819 HEA (86.5 wt %) (3.5 wt %) (10 wt %) Example 12 DMA + VP I 819 HBA (45 + 36.5 wt %) (3.5 wt %) (15 wt %) Example 13 DMA I 819 HEMA (46.5 wt %) (3.5 wt %) (50 wt %) Example 14 DMA + VP I 819 MA (59.0 + 29.5 wt %) (3.5 wt %) (8 wt %) Example 15 DMA I 819 HEMA PVP (43.0 wt %) (3.5 wt %) (41.5 wt %) (0.5 wt %) Example 16 DMA + VP I 819 PAA (48.0 + 48.0 wt %) (3.5 wt %) (0.5 wt %) Example 17 HDMA + VP I 819 PEI (43.75 + 43.75 wt %) (3.5 wt %) (9 wt %) Example 18 DMA + VP I 819 HEMA PEI (45.75 + 35.75 wt %) (3.5 wt %) (10 wt %) (5 wt %) Example 19 DMA + VP I 819 HEMA PAA (60.25 + 25.75 wt %) (3.5 wt %) (10 wt %) (0.5 wt %) Example 20 DMA + DAAM + VP I 819 PVP HBVE (31.0 + 10.0 + 21.0 wt %) (4.0 wt %) (14 wt %) (20 wt %) Example 21 DMA + VP I 819 HBVE (46 + 32.5 wt %) (3.5 wt %) (18 wt %) Example 22 DMA + VP I 819 HEMA HBVE (46 + 12.5 wt %) (3.5 wt %) (20 wt %) (18 wt %) Example 23 DMA + VP I 819 PVP IBVE (38 + 38 wt %) (3.5 wt %) (0.5 wt %) (20 wt %) Example 24 DMA + VP I 819 IBVE (46 + 32.5 wt %) (3.5 wt %) (18 wt %) Example 25 DMA + VP I 819 HEMA IBVE (46 + 12.5 wt %) (3.5 wt %) (20 wt %) (18 wt %) Example 26 DMA + VP I 819 HEMA PVP HBVE (41 + 21 wt %) (3.5 wt %) (4 wt %) (10 wt %) (20 wt %) DMA: N,N-dimethylacrylamide DAA: Diacetone acrylamide DMAPMA: N-[3-(dimethylamino)propyl]methacrylamide NMNVA: N-methyl-N-vinylacetamide *DMAEA: 2-(dimethylamino)ethyl acrylate VP: N-vinyl pyrrolidone ACMO: 4-acryloylmorpholine NIPA: N-isopropylacrylamide VA: Vinyl acetate HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate HBA: 4-hydroxybutylacrylate MA: Methacrylic acid PVP: Polyvinylpyrrolidone PEI: Polyethyleneimine PAA: Polyacrylic acid HBVE: 4-hydroxybutylvinyl ether IBVE: Isobutylvinyl ether

(5) Further, ink compositions of Comparative Examples 1 to 7 were prepared as follows.

(6) TABLE-US-00002 TABLE 2 A B C D Comparative BA I 819 DPGDA Example 1 (48.25 wt %) (3.5 wt %) (48.25 wt %) Comparative TMPTA I 819 DPGDA Example 2 (48.25 wt %) (3.5 wt %) (48.25 wt %) Comparative EA I 819 GDGDA Example 3 (76.5 wt %) (3.5 wt %) (20 wt %) Comparative TMPTA I 819 HEMA Example 4 (48.25 wt %) (3.5 wt %) (48.25 wt %) Comparative DPGDA I 819 HEA Example 5 (48.25 wt %) (3.5 wt %) (48.25 wt %) Comparative I 819 HEMA PVP Example 6 (3.5 wt %) (88.5 wt %) (8.0 wt %) Comparative IBOA I 819 GDGDA Example 7 (86.5 wt %) (3.5 wt %) (10 wt %) BA: Butyl acrylate DPGDA: Dipropylene Glycol Diacrylate TMPTA: Trimethylolpropane triacrylate EA: Ethyl acrylate IBOA: Isobornyl acrylate GDGDA: Glycerol 1,3-diglycerolate diacrylate

Test Example

(7) Supports were prepared using the ink compositions prepared in Examples 1 to 25 and Comparative Examples 1 to 7. Specifically, 4 to 5 drops of the ink composition was dropped on a substrate and then exposed to a high pressure mercury lamp at 1000 mJ/cm.sup.2 to prepare a support. Then, hardness, solubility in water and improvement of curing contraction were evaluated as follows.

Test Example 1. Evaluation of Hardness

(8) The ink composition was spin coated on a glass and exposed to a LED lamp of wavelength of 365 nm. Whether the composition was cured or not was observed with eyes while controlling exposure amount to 120 to 1000 mJ/cm.sup.2 and then curing sensitivity was decided. If the composition was cured successfully, it was decided as o, and if the composition was cured unsuccessfully, it was decided as x. The results are shown in Table 3.

Test Example 2. Evaluation of Solubility in Water

(9) The ink composition was dropped on a film substrate using a spuit, and then exposed to a high pressure mercury lamp at 1000 mJ/cm.sup.2. Multiple layers were repeatedly formed to make a support ink cured product sample, and the sample was peeled off from the substrate and immersed in water. A bottle where the ink cured product was immersed was put in a sonicator and sonicated for 60 mins. Then, whether the cured product sample was dissolved or not was confirmed to evaluate solubility.

(10) If the sample was dissolved well in water, it was decided as o, if the sample was dissolved little, it was decided as , and if the sample was not dissolved in water, it was decided as x. The results are shown in Table 3.

Test Example 3. Evaluation of Curing Contraction Improvement

(11) The ink composition was dropped on a film substrate using a spuit, and then exposed to light for curing. Then whether the film was bent or not was observed. If the film was bent sharply, it was decided that curing contraction was happened, and if original shape of the film was kept, it was decide that there was no curing contraction.

(12) If there was no curing contraction, it was decided as o, if there was small curing contraction, it was decided as , if there was large curing contraction, it was decided as x, and if the was sample was not dissolved in water, it was decided asbecause improvement of curing contraction was not measured. The results are shown in Table 3.

(13) TABLE-US-00003 TABLE 3 Improvement of Hardness Solubility in water curing contraction Example 1 x Example 2 x Example 3 Example 4 Example 5 x Example 6 x Example 7 x Example 8 x Example 9 x Example 10 x Example 11 x Example 12 x Example 13 x Example 14 x Example 15 x Example 16 x Example 17 Example 18 Example 19 x Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Comparative x Example 1 Comparative x Example 2 Comparative x Example 3 Comparative x Example 4 Comparative x Example 5 Comparative x Example 6 Comparative x Example 7

(14) As shown in Table 2 of Test Example, the ink compositions of Example 1 to Example 26 had excellent hardness and solubility in water. In particular it can be found that the compositions of Example 17, Example 18, and Example 20 to Example 26 are excellent in terms of curing contraction. Herein, the term soluble means all states that, when the cured product is immersed in water and then shaken or sonicated, lumps of the cured product are dissolved in water, the cured product is dispersed in water, or the cured product is floated in water in the shape of fine powder. Thus, the ink compositions of Example 1 to Example 26 were evaluated that it is very sufficient for the ink composition for a support used in a 3D printing process.

(15) In comparison, the compositions of Comparative Example 1 to Comparative Example 7 not containing the amine-containing monomer was hardly removed later when it was used as a support ink because the cured product was not dissolved in water. Thus, the ink compositions of Comparative Example 1 to Comparative Example 7 was evaluated that it is insufficient for the ink composition for a support used in a 3D printing process.