Photocurable composition for 3D printer for producing patient-customized cast

Abstract

The present disclosure relates to a photocurable composition for 3D printing for producing a patient-specific splint or cast. The photocurable composition easily produces a splint or cast conforming to the patient's body shape using 3D printing and makes it possible to adjust the immobilizing force of the splint or cast. In addition, the present disclosure provides a patient-specific splint or cast using a photocurable composition for 3D printing, which may produce a splint or cast, which may provide a necessary degree of compression by adjusting the immobilizing force thereof and is attachable and detectable as needed.

Claims

1. A photocurable composition for 3D printing for producing a patient-specific splint or cast using 3D printing, the composition comprising: a UV-curable polyurethane oligomer represented by the following Formula 1; a photoinitiator; a silane coupling agent; an oligomer; and a stabilizer, wherein the patient-specific splint or cast has a tensile strength of 50 to 60 N/m.sup.2 and a flexural strength of 60 to 75 N/m.sup.2: ##STR00010## wherein A and A′ are each a substituent represented by Formula 2 above; n, m, o, p, q and r are the same or different and are each independently an integer ranging from 1 to 100; L.sub.1 and L.sub.2 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; R.sub.1 to R.sub.8 are the same or different and are each independently selected from the group consisting of 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, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms; and the substituted alkylene group, the substituted arylene group, the substituted heteroarylene group, the substituted cycloalkylene group, the substituted alkyl group, the substituted cycloalkyl group, the substituted alkenyl group, the substituted alkynyl group, the substituted aralkyl group, the substituted aryl group, the substituted heteroaryl group, the substituted heteroarylalkyl group, the substituted alkoxy group, the substituted alkylamino group, the substituted arylamino group, the substituted aralkylamino group, the substituted heteroarylamino group, the substituted alkylsilyl group, the substituted arylsilyl group and the substituted aryloxy 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 alkyl amino 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 substituents, these substituents are the same or different.

2. The photocurable 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 composition of claim 1, wherein the photoinitiator is a compound represented by the following Formula 3: ##STR00011## 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 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 substituents, these substituents are the same or different.

4. The photocurable 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 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 composition of claim 1, wherein an implant is additionally formed in the patient-specific splint or cast in order to prevent the splint or cast from loosening due to changes in the state of the patient's affected area and maintain the ability of the splint or cast to support the patient's affected area.

7. A patient-specific splint or cast produced using 3D printing, the splint or cast comprising the photocurable composition for 3D printing according to claim 1.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a view illustrating a patient-specific splint or cast formed by a digital printing apparatus for printing a splint or cast using 3D information according to an embodiment of the present disclosure.

(2) FIG. 2 is a view illustrating that a first model is formed by division of a 3D model according to an embodiment of the present disclosure.

(3) FIG. 3 is a view illustrating that a second model is formed by division of a 3D model according to an embodiment of the present disclosure.

(4) FIG. 4 is a view illustrating an implant model that is added into a 3D model according to an embodiment of the present disclosure.

(5) FIG. 5 is a view illustrating a model in which holes are formed at both sides of the boundary in a 3D model according to an embodiment of the present disclosure.

(6) FIG. 6 is a view illustrating a model in which holes are formed at both sides of the boundary in a 3D model according to an embodiment of the present disclosure.

BEST MODE

(7) The present disclosure is directed to a photocurable composition for producing a patient-specific splint or cast using 3D printing, the photocurable composition including: a UV-curable polyurethane oligomer represented by the following Formula 1; a photoinitiator; a silane coupling agent; an oligomer; and a stabilizer, wherein the patient-specific splint or cast has a tensile strength of 50 to 60 N/m.sup.2 and a flexural strength of 60 to 75 N/m.sup.2:

(8) ##STR00008##

(9) wherein

(10) A and A′ are each a substituent represented by Formula 2 above;

(11) n, m, o, p, q and r are the same or different and are each independently an integer ranging from 1 to 100;

(12) L.sub.1 and L.sub.2 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;

(13) R.sub.1 to R.sub.8 are the same or different and are each independently selected from the group consisting of 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, a substituted or unsubstituted cycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 24 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms;

(14) the substituted alkylene group, the substituted arylene group, the substituted heteroarylene group, the substituted cycloalkylene group, the substituted alkyl group, the substituted cycloalkyl group, the substituted alkenyl group, the substituted alkynyl group, the substituted aralkyl group, the substituted aryl group, the substituted heteroaryl group, the substituted heteroarylalkyl group, the substituted alkoxy group, the substituted alkylamino group, the substituted arylamino group, the substituted aralkylamino group, the substituted heteroarylamino group, the substituted alkylsilyl group, the substituted arylsilyl group and the substituted aryloxy 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 alkyl amino 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 substituents, these substituents are the same or different.

MODE FOR INVENTION

(15) 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

(16) Photocurable polymer compositions for 3D printing were prepared by mixing a UV-curable polyurethane oligomer represented by the following Formula 7 or 8, a photoinitiator represented by the following Formula 5, 3-methacryloxypropyltrimethoxysilane, an epoxy acrylate oligomer represented by the following Formula 6, and 2,6-di-tert-butyl-p-cresol. The oligomer and the like, used in the preparation of the polymer compositions, were purchased, and the contents of the components are shown in Table 1 below.

(17) ##STR00009##

(18) wherein

(19) A and A′ are each a substituent represented by Formula 2 above, and

(20) n′, m′, o′, p′, q′ and r′ are the same or different and are each independently an integer ranging from 1 to 100.

(21) TABLE-US-00001 TABLE 1 G10 G20 G30 G40 G50 G60 G70 G80 Formula 7 100 100 100 100 100 100 — — Formula 8 — — — — — — 100 100 Photoinitiator 1 1.5 5 10 15 20 10 15 Silane 0.05 0.1 0.5 1 1.5 2 1 1.5 coupling agent Oligomer 10 50 60 70 80 90 70 80 Stabilizer 0.05 0.1 0.5 1 2 3 1 2 (unit: parts by weight)

Test Example: Test for Evaluation of Physical Properties

(22) 1. Test conditions

(23) 1-1. Tensile test

(24) Test method: ASTM D638

(25) Testing instrument: Universal Testing Machine

(26) Test speed: 50 mm/min

(27) Distance between grips: 115 mm

(28) Load cell: 3000 N

(29) Elasticity range: (0.05 to 0.25)%

(30) Yield point: 0.2% offset

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

(32) 1-2. Flexural test

(33) Test method: ASTM D790

(34) Testing instrument: Universal Testing Machine

(35) Test speed: 1.4 mm/min

(36) Distance between spans: 55 mm

(37) Load cell: 200 N

(38) Elasticity range: (0.05 to 0.25)%

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

(40) 2. Test results

(41) The above tests were conducted by the Korea Polymer Testing & Research Institute. The specimens provided were obtained from the polymer compositions of S10 to S80 in Table 1 above by printing using a 3D printer.

(42) The results of the tensile test are shown in Table 2 below.

(43) TABLE-US-00002 TABLE 2 S10 S20 S30 S40 S50 S60 S70 S80 Maximum 1659.23 1752.34 1955.11 2224.92 2234.82 1827.21 2251.64 2244.52 load (N) Tensile 46.21 50.12 51.14 55.38 56.24 47.58 57.25 58.62 strength (N/m.sup.2) Yield 46.55 50.10 50.59 54.28 55.89 48.21 56.54 58.42 strength (N/m.sup.2) Elongation 35.98 38.10 38.89 39.85 40.23 37.12 40.69 42.34 (%) Elastic 1498.23 1645.54 1688.54 1721.32 1722.25 1521.54 1744.35 1746.24 modulus (N/m.sup.2)

(44) The results of the flexural test are shown in Table 3 below.

(45) TABLE-US-00003 TABLE 3 S10 S20 S30 S40 S50 S60 S70 S80 Maximum 94.1 95.4 96.1 96.3 97.1 95.2 98.4 98.6 load (N) Flexural 48.4 60.1 64.2 69.3 70.2 58.1 72.8 74.2 strength (N/m.sup.2) Strain (%) 10.12 12.98 12.95 13.04 13.25 11.75 14.11 14.52 Elastic 1109.14 1204.72 1214.46 1215.72 1227.43 1201.58 1241.14 1282.43 modulus (N/m.sup.2)

(46) From the tensile test and flexural test results in Tables 2 and 3 above, it was confirmed that the photocurable compositions of the present disclosure exhibited excellent tensile strength, flexural strength, elastic modulus, yield strength, elongation and strain.

(47) 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

(48) The present disclosure relates to a photocurable composition for 3D printing for producing a patient-specific splint or cast, and more particularly, to a photocurable composition for 3D printing which can produce a splint or cast conforming to a patient's affected area through 3D information on the patient's affected area, in which the splint or cast can provide excellent immobilization by being produced using the photocurable composition for 3D printing.