Photocurable shape-memory polymer composition for direct 3D printing, and orthodontic device manufactured using same

Abstract

The present disclosure relates to a photocurable shape-memory polymer composition for direct 3D printing, and an orthodontic device manufactured using same, and, more specifically, to a photocurable shape-memory polymer composition for direct 3D printing, and an orthodontic device manufactured using same, the composition exhibiting rigidity, stiffness and elasticity that are suitable for orthodontics in a first temperature range and exhibiting original shape restoration characteristics in a second temperature range that differs from the first temperature range.

Description

Photocurable shape-restoring polymer composition for direct 3D printing and orthodontic device manufactured using the same

[0001] The present disclosure relates to a photocurable shape-restoring polymer composition for direct 3D printing and an orthodontic device manufactured using the same, and more particularly, to a photocurable shape-restoring polymer composition for direct 3D printing having rigidity, stiffness, and elasticity suitable for orthodontic treatment in a first temperature range and having circular restoration characteristics in a second temperature range different from the first temperature range, and an orthodontic device manufactured using the same.

[0002]

[0003] Elasticity refers to the property of an object to change shape when force is applied and then return to its original shape when the force is removed. Conventional orthodontic appliances utilize this elasticity to perform their orthodontic function. Specifically, orthodontic appliances are designed with set-up in mind, and based on elasticity, can be smoothly installed on the teeth before orthodontic treatment. After installation, orthodontic appliances can move, rotate, extrude, and / or intrude the teeth to be orthodontized based on elasticity.

[0004] In particular, teeth are fixed within the dental arch by the alveolar bone, periodontal ligament, and gingiva, and the moment the orthodontic force is applied to the teeth by the orthodontic device, a force equal in magnitude and opposite in direction to the orthodontic force is generated by the reaction of the periodontal tissue; this is the resistance force. This resistance force changes throughout the course of orthodontic treatment, and even for the same tooth, it can vary from time to time. Even a tooth with high resistance at the beginning will have its resistance reduced at a certain point and be able to move easily if orthodontic force is continuously applied within the physiological limit from the orthodontic device.

[0005] However, conventional orthodontic appliances, when placed in the oral cavity, can become deformed due to the resistance of the teeth being corrected. This deformation of the appliance makes it impossible to achieve the intended goals of tooth movement, rotation, extrusion, and / or intrusion. Furthermore, to achieve the initial treatment goals, the deformed appliance must be removed and a new one fabricated and placed, creating the inconvenience of this process.

[0006] In addition, general orthodontic devices require a process of taking a mold by directly introducing a specific composition into the oral cavity in order to obtain data on the shape of the oral cavity, which is the object of attachment, in order to achieve the treatment goal, and then custom-manufacturing the device based on this, which is cumbersome because individual orthodontic devices must be manufactured each time based on this process.

[0007] Against this backdrop, there is an urgent need to provide a shape-restoring polymer composition having rigidity, stiffness, and elasticity suitable for orthodontic treatment in a specific temperature range, while having circular restoration properties in a specific temperature range different from the specific temperature range, and an orthodontic device using the same.

[0008] In addition, there is an urgent need to provide a polymer composition having the above characteristics and having photocurability that can be easily and accurately manufactured using a direct 3D printing method, and an orthodontic device using the same.

[0009] Furthermore, there is an urgent need to provide a polymer composition having the above characteristics and maintaining a solid crystalline structure even at high-temperature sterilization temperatures, and an orthodontic device using the same.

[0010] The problem to be solved by the present disclosure is to provide a shape-restoring polymer composition having rigidity, stiffness, and elasticity suitable for orthodontic treatment in a specific temperature range, while having circular restoration characteristics in a specific temperature range different from the specific temperature range, and an orthodontic device using the same.

[0011] Another problem that the present disclosure seeks to solve is to provide a photocurable polymer composition that can be easily and accurately manufactured by direct 3D printing, and an orthodontic device using the same.

[0012] Another problem that the present disclosure seeks to solve is to provide a polymer composition that maintains a solid crystalline structure even at high-temperature sterilization temperatures and an orthodontic device using the same.

[0013] The problems to be solved by the present disclosure are not limited to the problems mentioned above, and problems to be solved by the present disclosure that are not mentioned can be clearly understood by a person having ordinary knowledge in the technical field to which the present disclosure belongs (“ordinary skilled person”) from the description below.

[0014] According to one embodiment of the present invention,

[0015] A photocurable shape-restoring polymer composition comprising a photocurable compound, a photoinitiator, and an antioxidant,

[0016] The photocurable compound comprises at least one selected from aliphatic urethane dimethacrylate, caprolactone urethane triacrylate, bisphenol A ethoxylate dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate,

[0017] The photoinitiator comprises at least one selected from bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, phenylglyoxylic acid methyl ester, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,

[0018] A photocurable shape restoring polymer composition can be provided wherein the antioxidant is 2,6-di-tert-butyl-para-cresol.

[0019] Meanwhile, the photocurable compound may include caprolactone urethane trimethacrylate instead of caprolactone urethane triacrylate.

[0020] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 40 to 70 parts by weight of aliphatic urethane dimethacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0021] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 25 parts by weight of caprolactone urethane triacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0022] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 20 parts by weight of bisphenol A ethoxylate dimethacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0023] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 20 parts by weight of hydroxyethyl methacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0024] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 30 parts by weight of isobornyl methacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0025] For example, the photoinitiator may be a photocurable shape-restoring polymer composition containing 1 to 14 parts by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0026] For example, the photoinitiator may be a photocurable shape-restoring polymer composition containing 0.1 to 15 parts by weight of phenylglyoxylic acid methyl ester based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0027] For example, the photoinitiator may be a photocurable shape-restoring polymer composition containing 5 to 40 parts by weight of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0028] For example, the antioxidant may be a photocurable shape-restoring polymer composition containing 0.3 to 1.5 parts by weight of 2,6-di-tert-butyl-para-cresol based on 100 parts by weight of the total photocurable shape-restoring polymer composition.

[0029] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition having a glass transition temperature of 50 to 110°C after curing.

[0030] Additionally, according to one embodiment of the present disclosure, an orthodontic device manufactured using the photocurable shape-restoring polymer composition can be provided.

[0031] According to the present disclosure, a shape-restoring polymer composition having rigidity, stiffness, and elasticity suitable for orthodontic treatment in a specific temperature range, while having circular restoration properties in a specific temperature range different from the specific temperature range, and an orthodontic device using the same can be provided.

[0032] In addition, according to the present disclosure, a polymer composition having photocurability that can be easily and accurately manufactured by a direct 3D printing method and an orthodontic device using the same can be provided.

[0033] In addition, according to the present disclosure, a polymer composition that maintains a solid crystalline structure even at a high-temperature sterilization temperature and an orthodontic device using the same can be provided.

[0034] The excellent and / or useful effects according to the present disclosure are not limited to the effects of the present disclosure described above, and it should be understood that those skilled in the art will also be able to clearly recognize excellent and / or useful effects of the present disclosure that are not explicitly disclosed in the present disclosure based on the disclosure of the present specification, and that these are intentionally disclosed by the present specification and are clearly included in the scope of the present disclosure.

[0035] Figure 1 is a diagram showing the results of measuring the glass transition temperature of a photocurable shape-restoring composition according to an example of the present disclosure.

[0036] The present invention relates to a photocurable shape-restoring polymer composition comprising a photocurable compound and a photoinitiator,

[0037] The photocurable compound comprises at least one selected from aliphatic urethane dimethacrylate, caprolactone urethane triacrylate, bisphenol A ethoxylate dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate,

[0038] The photoinitiator comprises at least one selected from bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, phenylglyoxylic acid methyl ester, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

[0039] The terms or words used in this specification and claims are not intended to be construed as limited to their commonly used dictionary meanings, and those skilled in the art will clearly understand that the terms or words are used in the sense intended to convey the meaning of the present disclosure within the scope of expressing the concepts that this specification and claims are intended to self-evidently convey.

[0040] In addition, it will be clearly understood by those skilled in the art that the configurations described in the aspects, embodiments, examples, etc. of the present disclosure described in this specification are merely preferred examples presented at the time to enable those skilled in the art to understand and reproduce the present disclosure, and are not intended to limit the present disclosure thereto.

[0041] Furthermore, the descriptions and specific embodiments of each configuration described in this specification can be readily applied to the descriptions and specific embodiments of each other configuration. That is, all possible combinations of the various configurations and specific embodiments disclosed in this specification fall within the scope disclosed in this specification, as will be readily apparent to those skilled in the art.

[0042] The term "and / or" as used herein is a term that includes each and every combination of two or more of the items mentioned. Furthermore, where singular terms are used herein, the plural is also included unless otherwise specified.

[0043] The terms “comprise” and “comprising” used in this specification are terms that allow the presence or addition of items other than the items mentioned, and the terms “consist,” “consist,” “consisting,” and “consisting” used in this specification are terms that do not allow the presence or addition of items other than the items mentioned.

[0044] The term "to" as used herein refers to a numerical range in which the numerical range indicated by using the term "to" includes the values ​​described before and after the term as lower limits and upper limits, respectively. When a plurality of upper and / or lower limits are disclosed for each of an arbitrary numerical range, the numerical range discloses an arbitrary numerical range in which any one of the plurality of lower limits and any one of the plurality of upper limits are each the lower limit and the upper limit, respectively.

[0045] The terms “about” and / or “approximately” as used herein mean a numerical range between 10% of the upper and lower limits based on the values ​​indicated using “about” and / or “approximately” above.

[0046] The terms or words used in this specification and claims should not be construed as limited to their conventional dictionary meanings, but rather should be construed as meanings and concepts consistent with the technical spirit of the present disclosure, based on the principle that the inventor can appropriately define the concept of the term to best describe his or her invention. Therefore, the configurations described in the embodiments described in this specification are merely preferred embodiments of the present disclosure and do not represent all of the technical spirit of the present disclosure. Therefore, it should be understood that various equivalents and modified examples may exist as substitutes for them at the time of this application.

[0047] Meanwhile, each description and embodiment disclosed in this specification may also be applied to each other description and embodiment. That is, all combinations of the various elements disclosed in this specification fall within the scope of this disclosure, and descriptions omitted in one embodiment may be interpreted in the same manner as described in other embodiments. Furthermore, the scope of this disclosure is not limited by the specific descriptions described below.

[0048] According to one embodiment of the present disclosure, a photocurable shape-restoring polymer composition can be provided.

[0049] The above photocurable shape-restoring polymer composition may have rigidity, stiffness, and elasticity suitable for orthodontic treatment in a first temperature range upon curing, and may have shape-restoring properties in a second temperature range different from the first temperature range.

[0050] That is, since the photocurable shape-restoring polymer composition has both an amorphous structure and a crystalline structure, when cured, for example, when formed into an orthodontic device, when the orthodontic device undergoes temporary deformation due to wearing in the oral cavity in a first temperature range, the kinetic energy between molecules in the amorphous region increases in a second temperature range, so that it has elasticity like soft rubber, and when there is no external stress, for example, resistance of the teeth to be orthodonticized, the deformation of the orthodontic device can be restored by utilizing the property of quickly restoring the original shape (Shape Restoration Function), and thereafter, elasticity with stiffness and rigidity, i.e., orthodontic force, can be restored again at a certain temperature, for example, in the first temperature range.

[0051] In general, low-molecular substances begin a phase change from a solid to a liquid state when heated, but in the case of polymer substances, there is a point at which another change occurs before this phase change, and the temperature at this point is called the glass transition temperature. Unlike low-molecular compounds in which molecules form a regular arrangement and pile up to form a solid phase, ordinary polymer compositions have many amorphous regions that are not arranged regularly due to their very large molecular weight and have difficulty forming crystals, so they have a semi-crystalline state in which crystalline and amorphous regions are mixed.

[0052] When heat is applied to a polymer composition, the kinetic energy between molecules in the amorphous region increases, making the micro-Brownian motion more active, and at this time, the hard polymer material changes into a material that has elasticity like soft rubber. In other words, the glass transition temperature (Tg) can be the temperature at which the molecules in the amorphous polymer region become active and start to move, changing into a viscous liquid or rubber-like form, and it can be the temperature at which the amorphous polymer material exhibits glassy state properties such as brittleness, stiffness, and rigidity as the temperature decreases. In addition, polymer materials have their own unique glass transition temperature depending on their characteristics, and accordingly, the glass transition temperature can be used to identify polymer materials.

[0053] Since the glass transition temperature only applies to amorphous polymers, a glass transition temperature may not be defined for pure crystalline polymers, and a pure amorphous polymer material may only have a glass transition temperature (Tm) and not a defined melting temperature. However, many polymer materials have both amorphous and crystalline structures, so most polymer materials can have both a glass transition temperature and a melting temperature. Generally, the glass transition temperature is lower than the melting temperature, and a high glass transition temperature can be interpreted as a polymer that is relatively insoluble.

[0054] That is, the photocurable shape-restoring polymer composition is a composition having both an amorphous structure and a crystalline structure. The composition has rigidity, stiffness, and elasticity suitable for orthodontic treatment in a first temperature range after curing, for example, 15°C to 40°C, and has a glass transition temperature in a second temperature range different from the first temperature range, for example, 50°C to 110°C. In the second temperature range, the molecules of the composition are active and begin to move, so as to quickly restore the shape of the device or product, and when the temperature returns to the first temperature range, the shape and physical properties of the device or product can be restored so that the original shape and rigidity, etc., are substantially equivalent to those at the time of manufacture.

[0055] In addition, the photocurable shape-restoring composition can have high-temperature resistance in which the crystalline structure of the cured composition is still firmly maintained under conditions of 121 to 135°C and 1 atm, which are high-temperature sterilization temperatures (autoclaves) commonly used in dentistry, considering hygiene and disinfection aspects for oral wear when formed into, for example, a dental orthodontic device, and thus, shape memory characteristics can still be maintained even when exposed to high-temperature sterilization conditions.

[0056] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition comprising a photocurable compound, a photoinitiator, and an antioxidant.

[0057] For example, the photocurable compound may include at least one selected from aliphatic urethane dimethacrylate, caprolactone urethane triacrylate, bisphenol A ethoxylate dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate.

[0058] Meanwhile, the photocurable compound may include caprolactone urethane trimethacrylate instead of caprolactone urethane triacrylate.

[0059]

[0060] The photocurable compound may be a photocurable shape-restoring polymer composition comprising 40 to 70 parts by weight of aliphatic urethane dimethacrylate based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the aliphatic urethane dimethacrylate may be comprised in an amount of 50 to 65 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0061] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 25 parts by weight of caprolactone urethane triacrylate based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the caprolactone urethane triacrylate may be contained in an amount of 4 to 25 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0062] Meanwhile, the photocurable compound may contain caprolactone urethane trimethacrylate instead of caprolactone urethane triacrylate in the same component ratio.

[0063] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 20 parts by weight of bisphenol A ethoxylate dimethacrylate based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the bisphenol A ethoxylate dimethacrylate may be contained in an amount of 4 to 22 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0064] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 20 parts by weight of hydroxyethyl methacrylate based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the hydroxyethyl methacrylate may be contained in an amount of 4 to 25 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0065] For example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 30 parts by weight of isobornyl methacrylate based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the isobornyl methacrylate may be contained in an amount of 4 to 35 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0066] For example, the photoinitiator may include at least one selected from bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, phenylglyoxylic acid methyl ester, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

[0067] For example, the photoinitiator may be a photocurable shape-restoring polymer composition containing 1 to 14 parts by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide may be contained in an amount of 1.2 to 15 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0068] For example, the photoinitiator may be a photocurable shape-restoring polymer composition containing 0.1 to 15 parts by weight of phenylglyoxylic acid methyl ester based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the phenylglyoxylic acid methyl ester may be contained in an amount of 0.4 to 14.5 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0069] For example, the photoinitiator may be a photocurable shape-restoring polymer composition containing 5 to 40 parts by weight of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide may be contained in an amount of 5 to 35 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0070] For example, a photocurable shape restoring polymer composition can be provided wherein the antioxidant is 2,6-di-tert-butyl-para-cresol.

[0071] For example, the antioxidant may be a photocurable shape-restoring polymer composition containing 0.3 to 1.5 parts by weight of 2,6-di-tert-butyl-para-cresol based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the 2,6-di-tert-butyl-para-cresol may be contained in an amount of 0.4 to 1.2 parts by weight based on 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0072] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition having a glass transition temperature of 50 to 110°C after curing.

[0073] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition having a characteristic of maintaining crystallinity under conditions of 115 to 140°C and 1 atm after curing.

[0074] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition for direct 3D printing.

[0075] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition for manufacturing an orthodontic device.

[0076] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition for manufacturing a transparent orthodontic device.

[0077] Additionally, according to one embodiment of the present disclosure, an orthodontic device manufactured using the photocurable shape-restoring polymer composition can be provided.

[0078] In general, orthodontic devices used in orthodontic clinical practice adhere to teeth by their elastic properties and internal gaps within a first temperature range (15°C to 40°C) including a usable temperature range of 36.5°C to 37.5°C, which is the range of body temperature, and are deformed (stained) by the resistance of teeth against orthodontic force. At this time, the orthodontic force can be generated and controlled by the elasticity of the orthodontic device, the distance of movement, the angle of rotation, the thickness of the orthodontic device, the distance between the internal gaps, and various accessories.

[0079] An orthodontic appliance manufactured using a photocurable shape-restoring polymer composition according to the present disclosure can quickly restore its original shape and elastic properties to its original shape before deformation, for example, within 5 to 60 seconds, preferably 20 to 30 seconds, at a glass transition temperature, for example, 50 to 110°C. When the appliance is worn again, the orthodontic appliance exerts continuous orthodontic force so that the initially intended tooth movement goal is achieved.

[0080] That is, an orthodontic device manufactured using a photocurable shape-restoring polymer composition according to the present disclosure is manufactured using a polymer composition designed to have a glass transition temperature of, for example, 50 to 110°C and to have stiffness, rigidity, and elasticity properties in a temperature range including room temperature and body temperature. The photocurable shape-restoring polymer composition according to the present disclosure is configured such that the shape restoring force of the orthodontic device is smaller than the resistance force of the teeth at the glass transition temperature, thereby restoring the shape of the orthodontic device in a temperature range with almost no stress, and allowing the orthodontic device to regain its original stiffness, rigidity, and elasticity properties, thereby enabling it to function as an orthodontic device.

[0081] For example, an orthodontic device manufactured using the photocurable shape-restoring polymer composition may be an orthodontic device having a glass transition temperature of 50 to 110°C.

[0082] For example, an orthodontic device manufactured using the photocurable shape-restoring polymer composition may be an orthodontic device having a characteristic of maintaining crystallinity under conditions of 115 to 140°C and 1 atm after curing.

[0083] Hereinafter, the present disclosure will be described in more detail using examples. Process conditions and preparatory steps not specified in the examples below may be process conditions or preparatory steps that are self-evident in the technical field to which the present disclosure pertains. A person skilled in the art will be able to select these conditions and reproduce the problem-solving principles of the present disclosure without difficulty based on the present disclosure.

[0084] In addition, in the manufacturing method according to the present disclosure, unless otherwise specified, each step constituting the manufacturing method is performed at room temperature (15°C to 25°C), and it should be understood that each step is performed by means and tools that can be derived without much difficulty by a person skilled in the art.

[0085]

[0086] Examples 1 to 15: Preparation of photocurable shape-restoring polymer composition according to the present disclosure

[0087] As photocurable compounds, aliphatic urethane dimethacrylate (PP1), caprolactone urethane triacrylate (PP2), bisphenol A ethoxylate dimethacrylate (PP3), hydroxyethyl methacrylate (PP4), isobornyl methacrylate (PP5), as photoinitiators, bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide (ID1), phenylglyoxylic acid methyl ester (ID2), 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide (ID3), and as antioxidants, 2,6-di-tert-butyl-para-cresol were prepared in weights according to the weight parts shown in Tables 1 and 2 below based on 100 g of the total photocurable formation-restoring polymer composition, and then mixed, heated to melt, and then cooled to room temperature to prepare compositions of Examples 1 to 15. Meanwhile, the photocurable compound can also be replaced with caprolactone urethane trimethacrylate instead of caprolactone urethane triacrylate.

[0088]

[0089] Example 12345678910 Photocurable compound PP16060606060606060606060PP22015201520101551510PP30505010515510PP42020100015151550PP5001020205551520 Photoinitiator ID17142214291.51014 ID240.5202144041 ID3433444321.51 Antioxidant 110.51110.5110.5

[0090] Examples Comparative Examples 111213141512345 Photocurable Compound PP 16 0 6 0 6 0 5 0 6 0 20 10 10 5 PP 25 0 5 10 5 6 0 30 6 0 5 10 PP 3 15 10 15 10 15 10 5 10 5 5 PP 4 2 0 0 10 0 0 10 25 10 4 0 40 PP 5 0 30 10 30 20 10 30 10 4 0 40 Photoinitiator ID 11.5 1.5 4 143 127 7 1.5 ID 27 0 4 16 0 0 45 1 ID 30 0 4 4 130 4 22 Antioxidant 111 110.5 0.5 10.2 0.2

[0091] Comparative Examples 1 to 5: Preparation of the compositions of Comparative Examples 1 to 5 Each component was prepared in a weight according to the weight parts described in Table 2 above based on 100 g of the entire photocurable formation-restoration polymer composition, mixed, heated to melt, and then cooled to room temperature to prepare the compositions of Comparative Examples 1 to 5.

[0092] Experimental Example: Measurement of the glass transition temperature of a photocurable shape-restoring polymer composition according to the present disclosure.

[0093] FIG. 1 is a diagram showing the results of measuring the glass transition temperature of a photocurable shape-restoring composition according to an example of the present disclosure. Referring to FIG. 1, it can be confirmed that the glass transition temperature of the composition cured by irradiating the composition of Example 6 with ultraviolet rays is formed in the range of 50 to 110 degrees, and it can be confirmed that the photocurable shape-restoring composition according to the present disclosure has a glass transition temperature in the range of 50 to 110 degrees Celsius, and accordingly, it can be confirmed that it can recover its original shape and elastic properties in a temperature range higher than body temperature.

[0094] Although the preferred embodiments of the present disclosure have been described in detail above, the scope of the present disclosure is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concepts of the present disclosure defined in the following claims also fall within the scope of the present disclosure.

Claims

1. A photocurable shape-restoring polymer composition comprising a photocurable compound and a photoinitiator, The photocurable compound comprises at least one selected from aliphatic urethane dimethacrylate, caprolactone urethane triacrylate, bisphenol A ethoxylate dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate. The photoinitiator comprises at least one selected from bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, phenylglyoxylic acid methyl ester, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. A photocurable shape restoring polymer composition.

2. In paragraph 1, The above photocurable compound contains 40 to 70 parts by weight of aliphatic urethane dimethacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

3. In paragraph 1, The above photocurable compound contains 1 to 25 parts by weight of caprolactone urethane triacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

4. In paragraph 1, The above photocurable compound contains 1 to 20 parts by weight of bisphenol A ethoxylate dimethacrylate based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

5. In paragraph 1, The above photocurable compound contains hydroxyethyl methacrylate in an amount of 1 to 20 parts by weight, based on 100 parts by weight of the total photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

6. In paragraph 1, The above photocurable compound contains 1 to 30 parts by weight of isobornyl methacrylate based on 100 parts by weight of the total photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

7. In paragraph 1, The above photoinitiator comprises 1 to 14 parts by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

8. In paragraph 1, The above photoinitiator contains 0.1 to 15 parts by weight of phenylglyoxylic acid methyl ester based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

9. In any one of paragraphs 1 to 6, The above photoinitiator comprises 5 to 40 parts by weight of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide based on 100 parts by weight of the entire photocurable shape-restoring polymer composition. A photocurable shape restoring polymer composition.

10. In paragraph 1, Based on 100 parts by weight of the entire photocurable shape-restoring polymer composition, Further comprising 0.3 to 1.5 parts by weight of 2,6-di-tert-butyl-para-cresol as an antioxidant. Photocurable shape restoring polymer composition

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