阅读说明：本技术 用于制造透明矫正装置的3d打印机用光固化型组合物 (Photocurable composition for 3D printer for manufacturing transparent correction device ) 是由 沈云燮 于 2019-07-05 设计创作，主要内容包括：本发明涉及用于制造透明矫正装置的3D打印机用光固化型高分子组合物,提供一种3D打印机用光固化型高分子组合物,其热物理性能、强度、弹性模量和延伸率等物理特性优异,用作患者定制型透明矫正装置时,可降低患者的痛苦,且安装在牙齿结构时能够提高牙齿矫正效果。另外,能够制造出即使原来形状因使用而变形也可以实现形状复原的3D打印透明矫正装置。(The present invention relates to a photocurable polymer composition for 3D printer for manufacturing a transparent orthodontic device, and provides a photocurable polymer composition for 3D printer, which has excellent physical properties such as thermophysical properties, strength, elastic modulus, elongation, etc., can reduce the pain of a patient when used as a patient-customized transparent orthodontic device, and can improve the orthodontic effect when mounted on a dental structure. In addition, a 3D printing transparent correction device that can realize shape recovery even if the original shape is deformed by use can be manufactured.)

1. A photocurable composition for a 3D printer for manufacturing a transparent correction device, wherein,

comprises the following steps:

a UV curable urethane oligomer represented by the following chemical formula 1,

a photo-initiator,

a silane coupling agent,

an oligomer, and

a stabilizer;

[ chemical formula 1]

[ chemical formula 2]

Wherein the content of the first and second substances,

a and A' are substituents represented by the chemical formula 2;

n, m, o, p, q and r are the same or different from each other and each independently is an integer of 1 to 100;

L₁and L₂The same or different from each other, each independently is 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, and a heteroaryl groupA substituted or unsubstituted cycloalkylene group having 3 to 200 carbon atoms;

R₁to R₈The same or different from each other, each is 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 heteroaralkyl 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 arylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having a carbon atom number, 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;

the substituted alkylene, substituted arylene, substituted heteroarylene, substituted cycloalkylene, substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted alkynyl, substituted aralkyl, substituted aryl, substituted heteroaryl, substituted heteroaralkyl, substituted alkoxy, substituted alkylamino, substituted arylamino, substituted aralkylamino, substituted heteroaralmino, substituted alkylsilyl, substituted arylsilyl, and substituted aryloxy are substituted with one or more groups selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxy, alkyl having 1 to 30 carbon atoms, cycloalkyl having 1 to 20 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 24 carbon atoms, aralkyl having 7 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, heteroaryl having 5 to 60 carbon atoms, heteroaralkyl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, substituted alkenyl, substituted alkynyl, substituted aralkyl, substituted aryl, substituted heteroaryl, substituted heteroaralkyl, substituted alkoxy, substituted alkylamino, substituted arylamino, substituted aralkyloxy, substituted alkylsilyl, substituted arylsilyl, and substituted aryloxy, 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 substituted with a plurality of substituents, these substituents are the same as or different from each other.

2. The photocurable composition for a 3D printer used for manufacturing a transparent corrective device according to claim 1,

the transparent correction device using the photo-curable composition for 3D printer has a thickness of 1500-2000N/m²Elastic modulus of 40 to 50N/m²Tensile strength of 45 to 55N/m²The bending strength of (2).

3. The photocurable composition for a 3D printer used for manufacturing a transparent corrective device according to claim 1,

the transparent correction device using the photocurable composition for 3D printer can be restored to the original shape in the range of 40 to 80 ℃.

4. The photocurable composition for a 3D printer used for manufacturing a transparent corrective device according to claim 1,

the weight average molecular weight of the UV curable polyurethane oligomer is 10000 to 1000000.

5. The photocurable composition for a 3D printer used for manufacturing a transparent corrective device according to claim 1,

the photoinitiator is a compound represented by the following chemical formula 3:

[ chemical formula 3]

Wherein, X₁Is S, O or N (R)₁₁)，

R₉To R₁₁The same or different from each other, each independently is hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl group of 1 to 30 carbon atoms, and substituted or unsubstituted cycloalkyl group of 3 to 30 carbon atoms,

the substituted alkyl group and the substituted cycloalkyl group are substituted by a substituent selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxy, alkyl group of 1 to 30 carbon atoms, cycloalkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 30 carbon atoms, alkynyl group of 2 to 24 carbon atoms, aralkyl group of 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 carbon 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, wherein the substituents are the same or different from each other when they are substituted with a plurality of substituents.

6. The photocurable composition for a 3D printer used for manufacturing a transparent corrective device according to claim 1,

the oligomer is selected from epoxy acrylate oligomer, H₁₂Bisphenol a diglycidyl ether (a polymer of 4,4' - (1-methylethylidene) bicyclohexanol and chloromethyloxirane), and mixtures thereof.

7. The photocurable composition for a 3D printer used for manufacturing a transparent corrective device according to claim 1,

the stabilizer is selected from the group consisting of 2, 6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amines, organophosphates, hindered phenols, and mixtures thereof.

8. A transparent orthotic device, wherein,

comprising the photocurable composition for a 3D printer according to any one of claims 1 to 7.

Technical Field

The present invention relates to a photocurable polymer composition for a 3D printer for manufacturing a transparent correction device, and more particularly, to a photocurable composition for a 3D printer, which is a photocurable composition for a 3D printer capable of manufacturing a transparent correction device, and which is composed of a transparent material, is not easily recognized from the outside, and can be restored to an original shape by heating, and thus can be easily restored to an original shape even if it is deformed by use and reused.

Background

In general, teeth and orofacial regions cannot grow neatly at appropriate positions due to dysplasia of teeth and jawbones, bad habits and heredity affecting teeth, and the like, and therefore, uneven dentition, malocclusion, and facial prominence occur. The structure of dentition and oral cavity is an important factor determining impression of a person and a cause of deterioration of food pulverizing function, and thus, interest in orthodontics is increasing.

Orthodontic treatment is a fixed treatment method in which a bracket is attached to a tooth and the tooth is moved by elasticity of an orthodontic wire, a rubber band, or the like, and is most widely used in orthodontic treatment, because the tooth is moved by a certain force. Stents are typically made of metal, but suffer from significant disadvantages during treatment.

To solve this drawback, a transparent correction method is proposed. Transparent orthodontic means a method of making a transparent orthodontic appliance which gradually changes from a tooth state before orthodontic treatment to a tooth state desired orthodontic treatment and correcting dentition by replacement wearing the appliance on teeth.

Specifically, an orthodontic device developed by allied Technology, Inc., in 1997 under the name of "invisalagn System", developed by allied Technology, Inc., of the united states, through the development of a transparent orthodontic device, the technical contents of which are disclosed in U.S. patent nos. 5975893 and 6217325, and the like.

The "invisalagn System" uses a special program to perform three-dimensional scan data on teeth, cuts the teeth one by one on a computer, and creates 20 to 30 pairs of models up to the final position of tooth movement by virtual simulation in each stage, and manufactures a transparent plastic frame for each model and distributes it to a patient, and the frame can move the teeth.

The "invisalagn System" is characterized in that teeth to be straightened are gradually moved to final target points by stepwise fitting a prepared series of orthodontic devices in the form of plastic frames to the teeth, and the plastic frames are made of transparent materials and are not easily recognized from the outside, which may greatly contribute to the daily social life of the orthodontic patient, and the patient can detach the orthodontic devices as needed.

However, even though the transparent orthotic device has the advantages described above over the fixed orthotic device with a brace as described above, it can cause considerable pain to the patient.

Such transparent orthodontic treatment uses a hard sheet (sheet) to induce tooth alignment based on the characteristics of materials for aesthetic reasons, and causes no less pain to a patient due to the characteristics of hard materials making the transparent orthodontic device hard.

In addition, although transparent orthodontic devices have many advantages, a disadvantage over fixed orthodontic devices is that if the devices do not fit well during tooth movement, installation of the devices is difficult and desired tooth movement is difficult. In particular, when the teeth are straightened using the transparent orthodontic device, an unexpected tooth inclination phenomenon occurs.

If the tooth inclination phenomenon continues, the tooth may gradually fall sideways or, in severe cases, collide with the roots of adjacent teeth and cause root absorption, and the first-made transparent appliance is not suitable, with the problems of the necessity of remanufacturing the transparent appliance, the cost and the increase of the orthodontic treatment period.

On the other hand, when rotating teeth using a conventional transparent appliance, or elongating, pressing down, and straightening the tooth axis, the transparent appliance may be used in such a manner that an attachment capable of enhancing each orthodontic effect is attached to the tooth surface.

In this case, the attachment not only looks messy, if two corrective actions are to be applied simultaneously, e.g., rotation and depression, or rotation and elongation, multiple attachments must be attached to one tooth. It is more difficult to wear and remove the transparent appliance in a state where a plurality of attachment devices are mounted on the teeth. Further, the attachment is easily deformed when attached to or detached from the teeth, and the attachment is easily detached.

Since the transparent orthodontic device is not easily recognized from the outside, there are advantages in that it can greatly help the daily social life of the orthodontic patient, and there is an advantage in that the patient can wear or detach the orthodontic device as desired, but as described above, the transparent orthodontic device is hard due to the characteristics of hard materials, pain given to the patient is a big problem, and there are problems in that the device is not well installed and it is difficult to move teeth as desired, and there is a problem in that it is necessary to newly manufacture the transparent orthodontic device when the transparent orthodontic device is not suitable.

There is a need to develop materials for manufacturing transparent orthotic devices that address this problem.

Documents of the prior art

Patent documents:

(patent document 1) KR 10-1822151B 1

Disclosure of Invention

Problems to be solved by the invention

The invention aims to provide a photocurable composition for a 3D printer for manufacturing a transparent correction device.

Another object of the present invention is to provide a photocurable polymer composition for 3D printers, which has excellent physical properties such as thermal physical properties, strength, elastic modulus, and elongation, can reduce pain of patients when used as a transparent orthodontic appliance customized for patients, and can be well attached to a dental structure to improve orthodontic effects.

Another object of the present invention is to provide a photocurable polymer composition for 3D printers, which can be used to manufacture a transparent correction device for 3D printing capable of restoring its original shape even if the original shape is deformed by use.

Means for solving the problems

To achieve the above object, a photocurable composition for a 3D printer for manufacturing a transparent correction device according to an embodiment of the present invention includes a UV curable urethane oligomer represented by the following chemical formula 1:

[ chemical formula 1]

[ chemical formula 2]

Wherein A and A' are substituents represented by the chemical formula 2;

n, m, o, p, q and r are the same or different from each other and each independently is an integer of 1 to 100;

L₁and L₂The same or different from each other, and each independently is 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, and a substituted or unsubstituted cycloalkylene group having 3 to 200 carbon atoms;

R₁to R₈The same or different from each other, each is 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 heteroaryl group having 6 carbon atomsA heteroarylalkyl group of to 30, a substituted or unsubstituted alkoxy group of a carbon number of 1 to 30, a substituted or unsubstituted alkylamino group of a carbon number of 1 to 30, a substituted or unsubstituted arylamino group of a carbon number of 6 to 30, a substituted or unsubstituted aralkylamino group of a carbon number of 6 to 30, a substituted or unsubstituted heteroarylamino group of a carbon number of 2 to 24, a substituted or unsubstituted alkylsilyl group of a carbon number of 1 to 30, a substituted or unsubstituted arylsilyl group of a carbon number of 6 to 30, and a substituted or unsubstituted aryloxy group of a carbon number of 6 to 30;

the substituted alkylene, substituted arylene, substituted heteroarylene, substituted cycloalkylene, substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted alkynyl, substituted aralkyl, substituted aryl, substituted heteroaryl, substituted heteroaralkyl, substituted alkoxy, substituted alkylamino, substituted arylamino, substituted aralkylamino, substituted heteroaralmino, substituted alkylsilyl, substituted arylsilyl, and substituted aryloxy are substituted with one or more groups selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxy, alkyl having 1 to 30 carbon atoms, cycloalkyl having 1 to 20 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 24 carbon atoms, aralkyl having 7 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, heteroaryl having 5 to 60 carbon atoms, heteroaralkyl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, substituted alkenyl, substituted alkynyl, substituted aralkyl, substituted aryl, substituted heteroaryl, substituted heteroaralkyl, substituted alkoxy, substituted alkylamino, substituted arylamino, substituted aralkyloxy, substituted alkylsilyl, substituted arylsilyl, and substituted aryloxy, 1 or more substituents selected from the group consisting of 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, which are the same or different from each other in the case of being substituted with a plurality of substituents.

The transparent correction device using the photo-curable composition for 3D printer has a thickness of 1500-2000N/m²Elastic modulus of 40 to 50N/m²Tensile strength of 45 to 55N/m²The bending strength of (2).

The transparent correction device using the photocurable composition for 3D printer can be restored to the original shape in the range of 40 to 80 ℃.

The weight average molecular weight of the UV curable polyurethane oligomer is 10000 to 1000000.

The photoinitiator is a compound represented by the following chemical formula 3:

[ chemical formula 3]

Wherein, X₁Is S, O or N (R)₁₁)；

R₉To R₁₁The same or different from each other, each independently is 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, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms;

the substituted alkyl group and the substituted cycloalkyl group are substituted by a substituent selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxy, alkyl group of 1 to 30 carbon atoms, cycloalkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 30 carbon atoms, alkynyl group of 2 to 24 carbon atoms, aralkyl group of 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 carbon 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, which are the same as or different from each other in the case of being substituted with a plurality of substituents.

The oligomer can be selected from the group consisting of epoxy acrylate oligomers, H₁₂Bisphenol A diglycidyl ether (4, 4'- (1-Methylethylidene) bicyclohexanol and chloromethyloxirane polymer, 4,4' - (1-Methylethylidene) biscylcohexanol, polymer with (chloromethyloxirane) oxirane), and mixtures thereof.

The stabilizer may be selected from the group consisting of 2, 6-di-t-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amines, organophosphates, hindered phenols, and mixtures thereof.

The transparent correction device of another embodiment of the invention can comprise the photocurable composition for the 3D printer.

The present invention will be described in further detail below.

The 3D printing of the present invention refers to a process of manufacturing a three-dimensional object by laminating materials using 3D digital data. In the present specification, Digital Light Processing (DLP), Stereolithography (SLA), and polymer jet (PolyJet) methods are mainly described as 3D printing techniques, but it is understood that the techniques can be applied to other 3D printing techniques as well.

The photocurable polymer of the present invention is a substance that is cured by irradiation with light, and refers to a polymer that can be crosslinked and polymerized into a polymer network structure. In the present specification, the UV light is mainly described, but the present invention is not limited to the UV light, and other light may be applied.

The photocurable composition for a 3D printer for manufacturing a transparent correction device according to an embodiment of the present invention may include a UV curable urethane oligomer represented by the following chemical formula 1, a photoinitiator, a silane coupling agent, an oligomer, and a stabilizer:

[ chemical formula 1]

[ chemical formula 2]

Wherein A and A' are substituents represented by the chemical formula 2;

n, m, o, p, q and r are the same or different from each other and each independently is an integer of 1 to 100;

L₁and L₂The same or different from each other, and each independently is 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, and a substituted or unsubstituted cycloalkylene group having 3 to 200 carbon atoms;

R₁to R₈The same or different from each other, each independently represents 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 heteroaralkyl 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 arylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted, 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;

the substituted alkylene, substituted arylene, substituted heteroarylene, substituted cycloalkylene, substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted alkynyl, substituted aralkyl, substituted aryl, substituted heteroaryl, substituted heteroaralkyl, substituted alkoxy, substituted alkylamino, substituted arylamino, substituted aralkylamino, substituted heteroaralmino, substituted alkylsilyl, substituted arylsilyl, and substituted aryloxy are substituted with one or more groups selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxy, alkyl having 1 to 30 carbon atoms, cycloalkyl having 1 to 20 carbon atoms, alkenyl having 2 to 30 carbon atoms, alkynyl having 2 to 24 carbon atoms, aralkyl having 7 to 30 carbon atoms, aryl having 6 to 30 carbon atoms, heteroaryl having 5 to 60 carbon atoms, heteroaralkyl having 6 to 30 carbon atoms, heteroaryl having 2 to 30 carbon atoms, substituted alkenyl, substituted alkynyl, substituted aralkyl, substituted aryl, substituted heteroaryl, substituted heteroaralkyl, substituted alkoxy, substituted alkylamino, substituted arylamino, substituted aralkyloxy, substituted alkylsilyl, substituted arylsilyl, and substituted aryloxy, 1 or more substituents selected from the group consisting of 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, which are the same or different from each other in the case of being substituted with a plurality of substituents.

The UV curable urethane oligomer is a polymer having a weight average molecular weight of 10000 to 1000000.

More preferably, the UV curable urethane oligomer is a compound represented by the following chemical formula 4:

[ chemical formula 4]

Wherein A and A' are as defined in chemical formula 1,

n ', m', o ', p', q 'and r', which are the same or different from each other, are each independently an integer of 1 to 100,

R₁₂and R₁₃The alkyl groups are the same or different from each other, and each is independently selected from the group consisting of an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.

More specifically, the present invention is a polymer compound in which a photo-curing functional group, which is a substituent represented by the chemical formula 2, is bonded to a urethane oligomer for UV curing.

The substituent represented by the chemical formula 2 includes a double bond structure between carbon atoms, and light curing can be expressed through the carbon-carbon double bond.

In addition, the UV curable polyurethane oligomer includes a polyurethane structure as a main chain, on which a photo-curable functional group is bonded, and the bonding between the polyurethane structure and the photo-curable functional group may utilize a linker (linker) in which a flexible functional group is bonded on a urethane linker (linker), and a linker (linker) in which a rigid functional group is bonded on a urethane linker (linker).

In the case of a chain in which a flexible functional group is bonded to the urethane linker, the flexible property of the flexible functional group can be used, and a Heat resistance (Heat resistance) can be exhibited by a rigid functional group.

That is, a photo-curable functional group is bonded to a UV-curable urethane oligomer, and a flexible functional group and a rigid functional group are used as a linker (linker), so that a flexible effect can be exhibited by a carbon skeleton having a soft property at normal temperature, and a strong heat resistance can be exhibited by a carbon skeleton having a rigidity at normal temperature.

The UV curable urethane oligomer can produce a 3D printed product (printout) excellent in physical properties such as thermophysical properties, strength, elastic modulus, and elongation by containing a carbon skeleton having rigidity.

In addition, the UV curable urethane oligomer can produce a 3D printed product that can realize shape recovery even if the original shape is deformed by use by including a carbon skeleton having flexibility.

In general, in order to improve physical properties of a 3D printed product, a composition used in a 3D printer may improve physical properties of an output product by including only a carbon skeleton having a rigid property, but when a shape is deformed by use, shape recovery cannot be achieved, and there is a problem that it cannot be used many times.

The composition for a 3D printer according to the present invention, which includes a rigid carbon skeleton and a flexible carbon skeleton in a UV curable urethane oligomer, not only has excellent physical properties such as thermophysical properties, strength, elastic modulus, and elongation, but also can recover its shape when deformed by use by taking advantage of the flexible property of a flexible functional group, thereby enabling reuse.

With the existing transparent orthodontic device, there occurs a problem that it is not suitable for the tooth structure with the lapse of time even though it is originally an orthodontic device suitable for the tooth structure due to fine movement of teeth or deformation caused by use of the orthodontic device.

In this case, there is a problem in that the conventional transparent correction device must be remanufactured, thereby causing a great loss in terms of time and economy. In contrast, with the present invention, even if the shape is deformed by use, it can be restored to its original shape when heated in the range of 40 to 80 ℃.

More specifically, in the case of the present invention, the transparent corrective device, the shape of which is deformed by use, is put into water at 40 to 80 ℃ and it can be restored to its original shape after about 5 to 10 seconds.

The deformed transparent correction device can be restored to the original state by using the warm water provided by the water dispenser which is usually and easily obtained.

In addition, when the composition for a 3D printer includes only a carbon skeleton having a soft property, physical properties of a printed product are low, and there are problems in that thermophysical properties, strength, elastic modulus, and elongation, which can be used as a product, cannot be expressed.

In particular, for use as a transparent orthotic device, only the physical properties of the 3D printed product are high, and the effect as an orthotic device can be exhibited. The conventional transparent orthodontic device has weak orthodontic effect as an orthodontic device because of low physical properties, but the composition for a 3D printer of the present invention has excellent physical properties, has a tensile modulus of 1500 to 2500MPa, a flexural modulus of 1000 to 3500MPa and a tensile strength of 45 to 90MPa, and can exhibit excellent orthodontic effect as an orthodontic device.

The existing transparent orthodontic device is composed of only a transparent material, which is advantageous only in terms of user's beauty, but as described above, the transparent orthodontic device is hard due to the characteristics of its hard material, thus having a problem of causing a great pain to a patient, and a problem of requiring remanufacturing of the transparent orthodontic device when it is difficult to install the device, it is difficult to achieve desired tooth movement, and the transparent orthodontic device is not suitable.

In contrast, when the transparent orthotic device is printed with the photo-curable composition for the 3D printer for manufacturing the transparent orthotic device according to the present invention, since it is formed of a transparent material and, based on its strong material characteristics, the patient suffers less pain than the conventional transparent orthotic device, and the apparatus is easy to install, and can move the teeth according to its excellent physical characteristics, and if the transparent orthotic device is deformed, it can be restored to its original form by heating in the temperature range of 40 to 80 ℃, and thus, there is no need for additional manufacturing.

The photoinitiator is a compound represented by the following chemical formula 3:

[ chemical formula 3]

Wherein, X₁Is S, O or N (R)₁₁)；

R₉To R₁₁The same or different from each other, each independently is hydrogen, deuterium, cyano, nitro, a halogen group, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms;

the substituted alkyl group and the substituted cycloalkyl group are substituted by a substituent selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxy, alkyl group of 1 to 30 carbon atoms, cycloalkyl group of 1 to 20 carbon atoms, alkenyl group of 2 to 30 carbon atoms, alkynyl group of 2 to 24 carbon atoms, aralkyl group of 7 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 5 to 60 carbon 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, wherein the substituents are the same or different from each other when they are substituted with a plurality of substituents.

More preferably, the compound is represented by the following chemical formula 5:

[ chemical formula 5]

The oligomer may be selected from the group consisting of epoxy acrylate oligomers, H₁₂Bisphenol A diglycidyl ether (4, 4'- (1-Methylethylidene) bicyclohexanol and chloromethyloxirane polymer, 4,4' - (1-Methylethylidene) biscylcohexanol, polymer with (chloromethyloxirane) oxirane), and mixtures thereof.

More specifically, as the epoxy acrylate oligomer, 1 or more compounds selected from the group consisting of phenyl epoxy (meth) acrylate oligomer (phenyl epoxy (meth) acrylate), bisphenol a epoxy di (meth) acrylate oligomer (bisphenol a epoxy di (meth) acrylate), aliphatic alkyl epoxy di (meth) acrylate oligomer, and aliphatic alkyl epoxy tri (meth) acrylate oligomer can be used. The oligomer can not only reduce swelling caused by organic solvents, but also improve surface hardness, abrasion resistance, heat resistance, and the like.

The silane coupling agent may be, for example, 3-Methacryloxypropyltrimethoxysilane (3-Methacryloxypropyltrimethoxysilane), but is not limited to the above examples.

The stabilizer is selected from the group consisting of 2, 6-di-t-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amines, organophosphates, hindered phenols, and mixtures thereof, more specifically 2, 6-di-t-butyl-p-cresol.

Conventional additives such as leveling agents, slip agents or stabilizers may also be included in order to improve thermal and oxidative stability, storage stability, surface properties, flow properties, processing properties, etc.

The photo-curable composition for a 3D printer for manufacturing a transparent correction device includes a UV-curable polyurethane oligomer including 1.5 to 15 parts by weight of a photoinitiator, 0.1 to 1.5 parts by weight of a silane coupling agent, 15 to 45 parts by weight of an oligomer, and 0.1 to 2 parts by weight of a stabilizer, with respect to 100 parts by weight of the UV-curable polyurethane oligomer. When the silane coupling agent is used in the above-mentioned range, compatibility with a resin and bonding strength can be improved when the silane coupling agent is used for surface treatment of a pigment, a filler, and the like. When the oligomer exceeds the use range, the surface energy increases to lower the releasability of the mold from the resin, and the surface hardness increases to possibly lower the surface characteristics such as the recovery force after the stamping of the mold. With respect to the stabilizer, environmental curing can be reduced and strength can be improved when used within a range of use.

The manufacture of the transparent corrective device of the present invention comprises the following steps: a 3D input step of receiving 3D information on a tooth structure; a 3D model generation step of setting a range of interest using the 3D information, and generating a plurality of 3D models divided into a plurality of regions with a central axis of the tooth structure as an x-axis; and a 3D output step of outputting the plurality of 3D models in a Digital Light Processing (DLP) mode.

The 3D output unit outputs a plurality of 3D models in a Digital Light Processing (DLP) system. The 3D output unit outputs the respective 3D models simultaneously or not, and thus the entire correction device can be generated in a short time. The 3D output unit may output the transparent correction device with the photocurable composition using the 3D printer according to the setting of the user.

The transparent correcting device is made by using a 3D model and outputting in a DLP mode, and the thickness of a specific part can be adjusted, so that the correcting effect is increased.

The transparent orthotic device may generate a 3D model in such a manner that an attachment is included at a portion corresponding to the inside of the tooth, and the 3D model is output in a Stereolithography Apparatus (SLA) or Digital Light Processing (DLP) method.

More specifically, holes for indirect bonding can be created and also exported for use with wire and indirect bonding parallels.

In addition, the 3D output part may be surface-treated at each interface so as to enhance bonding between a plurality of 3D printouts corresponding to the plurality of 3D models. For example, a UV treatment or a thermal treatment may be performed on the interface of each 3D output, but is not limited thereto. This is to facilitate bonding between adjacent 3D outputs by roughening the interface between the 3D outputs. The divided plural 3D outputs may be bonded by heat treatment or the like after resin is applied to the interface.

Effects of the invention

The invention provides a photo-curable polymer composition for a 3D printer, which has excellent physical properties such as thermal physical properties, strength, elastic modulus, elongation and the like, can reduce the pain of a patient when used as a patient-customized transparent orthodontic device, and can improve the orthodontic effect when being mounted on a tooth structure.

In addition, it is possible to manufacture a 3D printing transparent correction device that can realize shape recovery even if the original shape is deformed by use.

Drawings

Fig. 1 is a picture relating to a 3D printed product using a polymer composition according to an embodiment of the present invention.

FIG. 2 is a 3D model for making a transparent orthotic device according to an embodiment of the present invention.

Fig. 3 is a 3D model of a transparent orthotic device according to an embodiment of the present invention, a 3D model in which a 3D printed structure is formed instead of a steel wire.

Fig. 4 is a 3D model of a transparent orthotic device according to an embodiment of the present invention, which is configured such that a connecting device such as a steel wire can be attached to a portion of the 3D model.

Fig. 5 is a 3D model of a transparent orthotic device according to an embodiment of the present invention, in which a 3D printed structure capable of functioning as a steel wire is partially formed.

Fig. 6 is a 3D model of a transparent orthotic device according to an embodiment of the present invention, the 3D model having a portion of greater thickness.

Fig. 7 is a 3D model of a transparent orthotic device, according to an embodiment of the present invention, in which holes are formed for indirect bonding.

Fig. 8 is a 3D model of a transparent orthotic device according to an embodiment of the present invention, the 3D model having both steel wires and indirect bonds formed.

Detailed Description

The invention relates to a photo-curing composition for a 3D printer for manufacturing a transparent correction device, which comprises a UV-curing polyurethane oligomer, a photoinitiator, a silane coupling agent, an oligomer and a stabilizer.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily carry out the present invention. However, the present invention may be embodied in various forms and is not limited to the embodiments described herein.

[ production example: production of photocurable Polymer composition for 3D Printer

A photocurable polymer composition for a 3D printer was prepared by mixing a UV curable urethane oligomer represented by chemical formula 6 or 7, a photoinitiator represented by chemical formula 5, 3-methacryloxypropyltrimethoxysilane, an epoxy acrylate oligomer, and 2, 6-di-tert-butyl-p-cresol. The oligomer and the like used for producing the polymer composition were purchased and used, and the content of the components is shown in table 1 below.

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 2]

[ chemical formula 5]

Wherein A and A' are substituents represented by the following chemical formula 2,

n ', m', o ', p', q 'and r' are the same or different from each other and are each independently an integer of 1 to 100.

[ Table 1]

(parts by weight)

[ Experimental example: physical Property evaluation test

1. Test conditions

1-1 tensile test

The test method comprises the following steps: ASTM D638

The test instrument: universal Testing Machine (Universal Testing Machine)

Test speed: 50mm/min

Distance between the clamps: 115mm

A load sensor: 3000N

Elastic region: (0.05 to 0.25)%

Yield point: 0.2% offset (offset)

And (3) test environment: (23 + -2) deg.C, and (50 + -5)% R.H.

1-2 bending test

The test method comprises the following steps: ASTM D790

The test instrument: universal Testing Machine (Universal Testing Machine) test speed: 1.4mm/min

Span: 55mm

A load sensor: 200N

Elastic region: (0.05 to 0.25)%

And (3) test environment: (23 + -2) deg.C, and (50 + -5)% R.H.

1-6. heat distortion temperature

The test method comprises the following steps: ASTM D648

Test load: 0.45MPa

Temperature rise rate: 2 ℃/min

2. Test results

The experiment was entrusted with a korean polymer test research institute for experiments, and provided as a test piece by outputting the polymer compositions of S10 to S80 of table 1 as the test piece of fig. 1 using a 3D printer.

Tensile tests and bending tests were performed on S10 to S80, and the results are shown in tables 2 and 3 below. Also, the heat distortion temperature was examined.

[ Table 2]

[ Table 3]

From the tensile test and bending test results of tables 2 and 3, it was confirmed that the photocurable composition of the present invention exhibited excellent tensile strength, bending strength, modulus of elasticity, yield strength, elongation, and deformation rate.

The results of detecting the heat distortion temperatures of S10 to S80 are shown in table 4 below.

[ Table 4]

	S10	S20	S30	S40	S50	S60	S70	S80
									Heat distortion temperature	32.1	52.5	57.6	60.5	62.1	92.6	56.2	57.4

(unit ℃ C.)

From the table 4, it was confirmed that even if deformation occurs in the thermal deformation temperature range, i.e., the temperature of warm water (50 to 70 ℃) of the water dispenser which is easily obtained at ordinary times, it can be confirmed that the shape recovery can be easily achieved.

Although the preferred embodiments of the present invention have been described in detail, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention defined in the claims should also fall within the scope of the present invention.

Industrial applicability

The present invention relates to a photocurable polymer composition for a 3D printer for manufacturing a transparent correction device, and more particularly, to a photocurable composition for a 3D printer capable of manufacturing a transparent correction device, which is a photocurable composition for a 3D printer, is composed of a transparent material, is not easily recognized from the outside, and can be easily restored to an original shape by heating, and thus can be easily restored to the original shape and reused even if it is deformed by use.