RADIATION CURABLE POLYMER COMPOSITION FOR 3D PRINTER

Abstract

The present disclosure relates to a photocurable polymer composition for 3D printing including: a UV-curable polyurethane oligomer; a photoinitiator; an oligomer; and a stabilizer. The photocurable polymer composition for 3D printing can produce a 3D printed product having excellent physical properties such as thermal properties, strength, elastic modulus and tensile elongation. In addition, the photocurable polymer composition can produce a 3D printed product which, even when the original shape thereof is deformed during use, can be restored to the original shape thereof.

Claims

1. A photocurable polymer composition for 3D printing comprising: a UV-curable polyurethane oligomer represented by the following Formula 1; a photoinitiator; a silane coupling agent; an oligomer; and a stabilizer: ##STR00009## wherein A is a substituent represented by Formula 2 above, wherein * represents a moiety that is linked; R.sub.1 to R.sub.8 are the same or different and are each independently a substituted or unsubstituted alkylene group having 1 to 200 carbon atoms, a substituted or unsubstituted arylene group having 6 to 200 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 200 nuclear atoms, or a substituted or unsubstituted cycloalkylene group having 3 to 200 carbon atoms; and the substituted alkylene group, the substituted arylene group, the substituted heteroarylene group and the substituted cycloalkylene group are substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when they are substituted with a plurality of sub stituents, these sub stituents are the same or different.

2. The photocurable polymer composition of claim 1, wherein the UV-curable polyurethane oligomer has a weight-average molecular weight of 10,000 to 1,000,000.

3. The photocurable polymer composition of claim 1, wherein the photoinitiator is a compound represented by the following Formula 4: ##STR00010## wherein X.sub.1 is S, O or N(R.sub.11); R.sub.9 to R.sub.11 are the same or different and are each independently hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; and the substituted alkyl group and the substituted cycloalkyl group are substituted with one or more sub stituents selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when they are substituted with a plurality of sub stituents, these sub stituents are the same or different.

4. The photocurable polymer composition of claim 1, wherein the oligomer is selected from the group consisting of an epoxy acrylate oligomer, H.sub.12 Dian-bis-glycidyl ether (4,4′-(1-methylethylidene)biscyclohexanol polymer with (chloromethyl)oxirane), and a mixture thereof.

5. The photocurable polymer composition of claim 1, wherein the stabilizer is selected from the group consisting of 2,6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, a hindered amine, an organic phosphate, a hindered phenol, and mixtures thereof

6. The photocurable polymer composition of claim 1, wherein the polymer composition comprises the UV-curable polyurethane oligomer and comprises, based on 100 parts by weight of the UV-curable polyurethane oligomer, 1.5 to 15 parts by weight of the photoinitiator, 0.1 to 1.5 parts by weight of the silane coupling agent, 15 to 45 parts by weight of the oligomer, and 0.1 to 2 parts by weight of the stabilizer.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0067] FIG. 1 is a photograph showing a 3D printed product produced using a polymer composition according to an embodiment of the present disclosure.

[0068] FIG. 2 is a graph showing the results of a tensile test for a 3D printed product according to an embodiment of the present disclosure.

[0069] FIG. 3 is a graph showing the results of a flexural test for a 3D printed product according to an embodiment of the present disclosure.

[0070] FIG. 4 is a graph showing the results of a compression test for a 3D printed product according to an embodiment of the present disclosure.

BEST MODE

[0071] The present disclosure is directed to a photocurable polymer composition for 3D printing including: a UV-curable polyurethane oligomer represented by the following Formula 1;

[0072] a photoinitiator; a silane coupling agent; an oligomer; and a stabilizer:

##STR00007##

[0073] wherein

[0074] A is a substituent represented by Formula 2 above,

[0075] wherein * represents a moiety that is linked;

[0076] R.sub.1 to R.sub.8 are the same or different and are each independently a substituted or unsubstituted alkylene group having 1 to 200 carbon atoms, a substituted or unsubstituted arylene group having 6 to 200 carbon atoms, a substituted or unsubstituted heteroarylene group having 5 to 200 nuclear atoms, or a substituted or unsubstituted cycloalkylene group having 3 to 200 carbon atoms; and

[0077] the substituted alkylene group, the substituted arylene group, the substituted heteroarylene group and the substituted cycloalkylene group are substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 nuclear atoms, a heteroarylalkyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms, a heteroarylamino group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, and an aryloxy group having 6 to 30 carbon atoms, and when they are substituted with a plurality of sub stituents, these sub stituents are the same or different.

Mode for Invention

[0078] Hereinafter, embodiments of the present disclosure will be described in detail so that those skilled in the art to which the present disclosure pertains can easily carry out the present disclosure. However, the present disclosure may be embodied in a variety of different forms and is not limited to the embodiments described herein.

PREPARATION EXAMPLE

Preparation of Photocurable Polymer Composition for 3D Printing

[0079] A photocurable polymer composition for 3D printing was prepared by mixing a UV-curable polyurethane oligomer represented by the following Formula 3, a photoinitiator represented by the following Formula 5, 3-methacryloxypropyltrimethoxysilane, an epoxy acrylate oligomer, and 2,6-di-tert-butyl-p-cresol. The oligomer and the like, used in the preparation of the polymer composition, were purchased, and the contents of the components are shown in Table 1 below.

##STR00008##

[0080] wherein

[0081] A is a substituent represented by Formula 2 above, and n and m are the same or different and are each independently an integer ranging from 1 to 200.

TABLE-US-00001 TABLE 1 S10 S20 S30 S40 S50 S60 UV-curable polyurethane 100 100 100 100 100 100 oligomer Photoinitiator 1 1.5 5 10 15 20 Silane coupling agent 0.05 0.1 0.5 1 1.5 2 Oligomer 10 15 25 30 45 50 stabilizer 0.05 0.1 0.5 1 2 3 (unit: parts by weight)

TEST EXAMPLE

Test for Evaluation of Physical Properties

[0082] 1. Test conditions

[0083] 1-1. Tensile test

[0084] Test method: ASTM D638

[0085] Testing instrument: Universal Testing Machine

[0086] Test speed: 50 mm/min

[0087] Distance between grips: 115 mm

[0088] Load cell: 3000 N

[0089] Elasticity range: (0.05 to 0.25)%

[0090] Yield point: 0.2% offset

[0091] Test environment: (23±2)° C. and (50±5)% R.H.

[0092] 1-2. Flexural test

[0093] Test method: ASTM D790

[0094] Testing instrument: Universal Testing Machine

[0095] Test speed: 1.4 mm/min

[0096] Distance between spans: 55 mm

[0097] Load cell: 200 N

[0098] Elasticity range: (0.05 to 0.25)%

[0099] Test environment: (23±2)° C. and (50±5)% R.H.

[0100] 1-3. Izod impact strength

[0101] Test method: ASTM D256

[0102] Notch depth: 2.54 mm (machined by test client)

[0103] Test environment: (23±2)° C. and (50±5)% R.H.

[0104] 1-4. Compression test

[0105] Test method: ASTM D695

[0106] Test speed: 1.3 mm/min

[0107] Load cell: 30,000 N

[0108] Test environment: (23±2)° C. and (50±5)% R.H.

[0109] 1-5. Durometer hardness

[0110] Test method: ASTM D2240

[0111] Test environment: (23±2)° C. and (50±5)% R.H.

[0112] 1-6. Heat deformation temperature

[0113] Test method: ASTM D648

[0114] Test load: 0.45 MPa

[0115] Heating rate: 2° C/min

[0116] 2. Test results

[0117] The above tests were conducted by the Korea Polymer Testing & Research Institute. The specimens provided were the specimens shown in FIG. 1, obtained from the polymer compositions of S10 to S50 in Table 1 above by printing using a 3D printer.

[0118] For comparative testing, specimens were prepared using a product of NextDent B.V., an ABS material and a PC material, respectively, and tested in comparison with S50. The results are shown in Table 2 below.

TABLE-US-00002 TABLE 2 NextDent ABS PC S50 Viscosity (cps, 25° C.) 1,020 — — 492 DOC (mm) IS040949 1.67 — — 1.5 DUROMETER 87 77 83 93 HARDNESS(D) ASTM02240 Flexural Strength ASTM 99 63.7 85.3 137 D790-15 (MPa) Flexural Modulus ASTM 2,400 2,200 2,300 3,250 D790-15 (MPa) Tensile Strength ASTM — 39.2 63 85.1 D638-15 (MPa) Tensile Modulus ASTM 1,780 2,160 2,770 3,800 D638-15 (MPa)

[0119] As shown in Table 2 above, it was confirmed that, in comparison with the commercially available product, S50 showed lower viscosity, indicating easy handling, and exhibited better effects in the tensile test and the flexural test.

[0120] For S10 to S60, compressive strength, tensile strength, yield strength, flexural strength, flexural elasticity, elongation and heat deformation temperature were measured.

TABLE-US-00003 TABLE 3 IZOD Heat Durometer Compressive Tensile Yield Tensile Flexural Flexural impact deformation Specimen hardness strength strength strength Elongation modulus strength modulus strength temperature No. (D-type) (MPa) MPa) (MPa) (%) (MPa) (MPa) (MPa) (KJ/m.sup.2) (° C.) S10 50 44.46 48.28 51.181 3.1 1154 55.54 48.3 1.42 32.1 S20 83 74.55 49.38 49.38 7.56 1621 50.31 1206 2.52 52.5 S30 88 75.65 52.99 33.71 7.24 2042 71.85 1612 4.74 57.6 S40 84 73.45 70.10 45.24 7.62 1545 60.54 2950 5.34 80.5 S50 89 77.75 85.13 33.46 7.14 2151 80.57 3215 5.12 72.1 S60 65 50.45 48.22 4.21 1258 1835 2.23 80.6

[0121] As shown in Table 3 above which show the results of evaluating the physical properties of S10 to S60, it was confirmed that the maximum load, tensile strength, yield strength, gauge length, maximum displacement, elongation and elastic modulus of S10 and S60 were relatively low.

[0122] In addition, it was confirmed that S20 and S30 had a heat deformation temperature of about 52 to 58° C., indicating that when the printed products are deformed during use, they can be restored to the original shape thereof in water at a temperature of about 52 to 58° C. Also, it was confirmed that S20 and S30 exhibited excellent effects in terms of compressive strength, tensile strength, elastic modulus, and the like.

[0123] Furthermore, it was confirmed that S40 and S50 had a higher heat deformation temperature than S20 and S30, but exhibited better effects in terms of the other physical properties.

[0124] The difference in physical properties among S20, S30, S40 and S50 results from a difference in the contents of the components thereamong. Thus, it is possible to select and use a suitable polymer composition depending on the intended use of a printed product to be produced using a 3D printer.

[0125] Although the preferred embodiments of the present disclosure have been described above in detail, the scope of the present disclosure is not limited thereto. Various modifications and improvements, which are made by those skilled in the art without departing from the basic concept of the present disclosure as defined in the appended claims, also fall within the scope of the present disclosure.

INDUSTRIAL APPLICABILITY

[0126] The present disclosure relates to a photocurable polymer composition for 3D printering, and more particularly, to a photocurable polymer composition, which is applicable to 3D printing and can produce a 3D printed product, which has excellent physical properties such as thermal properties, strength, elastic modulus and tensile elongation and can be restored to the original shape thereof, by 3D printing the same.