METHOD FOR FORMING THREE-DIMENSIONAL OBJECT

Abstract

The present invention relates to a method for forming a three-dimensional object; according to the present invention, when the three-dimensional object is manufactured by an inkjet method, a support can be removed without damage to a structure body such that the three-dimensional object can be simply and economically manufactured.

Claims

1. A method for forming a three-dimensional object comprising the steps of: a) forming a three-dimensional object comprising a structure body and a support by laminating a plurality of layers; and b) removing the support by dissolving the support in water, or a mixture solution of water and a polar organic solvent.

2. The method for forming a three-dimensional object according to claim 1, which further comprises a step c) of drying the support-removed three-dimensional object.

3. The method for forming a three-dimensional object according to claim 1, wherein the polar organic solvent is at least one selected from the group consisting of methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, and ethylene glycol monobutyl ether.

4-5. (canceled)

6. The method for forming a three-dimensional object according to claim 1, wherein the support is manufactured through a step of curing an ink composition for a three-dimensional printing support comprising an amine-containing monomer and a curing agent.

7. The method for forming a three-dimensional object according to claim 6, wherein the ink composition for a three-dimensional printing support further comprises a monomer comprising at least one of a vinyl group and an acryl group.

8. The method for forming a three-dimensional object according to claim 7, wherein the ink composition for a three-dimensional printing support further comprises a water-soluble polymer.

9. The method for forming a three-dimensional object according to claim 6 wherein the amine-containing monomer is the compound of the following Chemical Formula 1: ##STR00012## wherein, R.sub.1 is hydrogen or a methyl group, and R.sub.2 and R.sub.3 are each independently hydrogen, a C.sub.1-C.sub.10 alkyl group, a vinyl group, an alkoxyl group, a cyclohexyl group, a phenyl group, a benzyl group, an alkylamine group, an alkyl ester group, or an alkyl ether group.

10-11. (canceled)

12. The method for forming a three-dimensional object according to claim 9, wherein R.sub.2 and R.sub.3 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ##STR00013## wherein 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, 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, C(CH.sub.3).sub.2CH.sub.2CH.sub.3, or CHCH.sub.2.

13. The method for forming a three-dimensional object according to claim 9, wherein the compound of the Chemical Formula 1 is the compound of the following Chemical Formula 1a: ##STR00014## wherein, R.sub.1 is hydrogen or a methyl group, and R.sub.2 and R.sub.3 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, or CHCH.sub.2.

14. The method for forming a three-dimensional object according to claim 6, wherein the amine-containing monomer is the compound of the following Chemical Formula 2: ##STR00015## wherein, R.sub.1 and R.sub.2 are each independently hydrogen, a C.sub.1 to C.sub.10 alkyl group, a vinyl group, an alkoxyl group, a cyclohexyl group, a phenyl group, a benzyl group, an alkylamine group, an alkyl ester group or an alkyl ether group, and R.sub.3 is hydrogen or a methyl group.

15. The method for forming a three-dimensional object according to claim 14, wherein R.sub.1 and R.sub.2 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ##STR00016##

16. The method for forming a three-dimensional object according to claim 6, wherein the amine-containing monomer is the compound of the following Chemical Formula 3: ##STR00017## wherein, R.sub.1 is hydrogen or a methyl group, R.sub.2 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.3 and R.sub.4 are each independently hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, CHCH.sub.2, or CH.sub.2CHCH.sub.2.

17. The method for forming a three-dimensional object according to claim 6, wherein the amine-containing monomer is the compound of the following Chemical Formula 4: ##STR00018## wherein, n is an integer of 1 to 4, A is C, O, N or S, R.sub.1, R.sub.2 and R.sub.3 are each independently hydrogen or a C.sub.1-C.sub.10 alkyl group, and R.sub.4 is CHCH.sub.2, ##STR00019##

18. The method for forming a three-dimensional object according to claim 17, wherein the compound of the Chemical Formula 4 is a compound selected from the following compounds: ##STR00020##

19. The method for forming a three-dimensional object according to claim 6, wherein the amine-containing monomer is the compound of the following Chemical Formula 5, Chemical Formula 6 or Chemical Formula 7: ##STR00021##

20. The method for forming a three-dimensional object according to claim 6, wherein the curing agent is a photo-initiator.

21-23. (canceled)

24. The method for forming a three-dimensional object according to claim 6, which further comprise 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.

25. (canceled)

26. The method for forming a three-dimensional object according to claim 6, wherein the amine-containing monomer is contained in an amount of 10 to 99.9 wt % based on the total weight of the composition, and the curing agent is contained in an amount of 0.01 to 20 wt % based on the total weight of the composition.

27-30. (canceled)

31. The method for forming a three-dimensional object according to claim 1, wherein the support is manufactured through a step of curing a support ink composition comprising a (meth)acrylamide-based monomer, a vinyl-based monomer, a water-soluble polymer, and a curing agent.

32. (canceled)

33. The method for forming a three-dimensional object according to claim 1, wherein the temperature of water or the mixture solution of water and a polar organic solvent when conducting the step b) is 20 C. to 90 C.

34-37. (canceled)

Description

BEST MODE CARRYING OUT THE INVENTION

[0069] A better understanding of the present invention may be obtained via the following examples that are set forth to illustrate, but are not to be construed as limiting the present invention. The scope of the present invention is described in the appended claims, and includes all modifications within ranges and meanings equivalent to the claims. Unless otherwise stated, % and part showing the amounts in the following examples and comparative examples are based on mass

EXAMPLE

Example 1

[0070] a) Step of Forming Three-Dimensional Object Comprising Structure Body and Support by Laminating a Plurality of Layers

[0071] 8 g of Dipentaerythritol hexaacrylate (DPHA), 68.5 g of trimethylolpropane triacrylate (TMPTA), 3.5 g of Irgacure 819, 1 g of isopropyl thioxanthone (ITX), and 0.5 g of monomethyl ether hydroquinone (MEHQ) were mixed to prepare a structure body ink composition.

[0072] Further, 49.2 g of dimethyl acrylamide, 32.8 g of 1-vinyl-2-pyrrolidone (VP), 14 g of polyvinyl pyrrolidone (PVP), and 4 g of Irgacure 819 were mixed to prepare a support ink composition.

[0073] The structure body ink composition and the support ink composition were subjected to three-dimensional printing by an inkjet method (Manufactured by Spectra, Apollo II, head: Dimatix 30 pL 128 nozzle head) to form a three-dimensional object, and curing was performed by using a 395 nm LED (2000 mJ/cm.sup.2).

[0074] b) Step of Removing Support

[0075] The three-dimensional object formed in the step a) is dissolved in water of 50 C. to remove a support.

[0076] c) Step of Drying Support-Removed Three-Dimensional Object

[0077] The support-removed three-dimensional object was dried for 10 min at room temperature by blowing dry air.

Example 2

[0078] The procedure of Example 1 was repeated except for using a mixed solution of water and ethanol (50:50) instead of water in the step b).

Comparative Example 1

[0079] The procedure of Example 1 was repeated except for using ethanol instead of water in the step b).

Comparative Example 2

[0080] The procedure of Example 1 was repeated except for using chlorobenzene instead of water in the step b).

Comparative Example 3

[0081] The procedure of Example 1 was repeated except for using acetonitrile instead of water in the step b).

Comparative Example 4

[0082] The procedure of Example 1 was repeated except for using acetone instead of water in the step b).

Comparative Example 5

[0083] The procedure of Example 1 was repeated except for using ether instead of water in the step b).

Comparative Example 6

[0084] The procedure of Example 1 was repeated except for using toluene instead of water in the step b).

[0085] Whether the support is removed or not and the structure body is damaged or not in Example 1 and 2 and Comparative Example 1 to 6 were checked, and the results are shown in the following Table 1.

TABLE-US-00001 TABLE 1 Whether Whether support is structure body removed is damaged Solvent for or not or not removal (, X) (, X) Note Example 1 Water X Example 2 Water + Ethanol X (50:50) Comparative Ethanol Example 1 Comparative Chlorobenzene Example 2 Comparative Acetonitrile Example 3 Comparative Acetone Example 4 Comparative Ether X X Nonpolar Example 5 solvent Comparative Toluene X Nonpolar Example 6 solvent *Whether support is removed or not: When immersing the three-dimensional object comprising the support in the corresponding solvent, if the support is dissolved in the solvent, marked as , and if it is not dissolved, marked as X. ** Whether structure body is removed or not: If a part of the structure body is dissolved, marked as , if the structure body is damaged, for example, bent or discolored, marked as and if the structure body is not damaged at all, marked as X.

[0086] In the cases of using only water and using the mixture solution of water and an organic solvent as a removal solvent like Examples 1 and 2, the support was removed without damage of the structure body. However, in the case of removing the support with only a polar organic solvent like Comparative Examples 1 to 4, the structure body was partially dissolved or damaged. In the case of using a nonpolar organic solvent like Comparative Examples 5 and 6, the support was not dissolved.