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

Abstract

This disclosure relates to a photocurable shape-restoring polymer composition for direct 3D printing and an orthodontic device manufactured therefrom, and more specifically, to a photocurable shape-restoring polymer composition for direct 3D printing having rigidity, straightness, and elasticity suitable for orthodontic use in a first temperature range and having shape-restoring properties in a second temperature range different from the first temperature range, and an orthodontic device manufactured therefrom.

Description

Technical Field

[0001] This disclosure relates to a photocurable shape-restoring polymer composition for direct 3D printing and an orthodontic device manufactured therefrom, and more specifically, to a photocurable shape-restoring polymer composition for direct 3D printing having rigidity, straightness, and elasticity suitable for orthodontic use in a first temperature range and having shape-restoring properties in a second temperature range different from the first temperature range, and an orthodontic device manufactured therefrom. Background Technology

[0002] Elasticity refers to the property of an object to change shape when a force is applied and to return to its original state when the force is removed. Orthodontic appliances typically utilize this elasticity to perform their orthodontic function. That is, orthodontic appliances are designed with setup in mind, allowing for smooth installation in the anterior dentition based on elasticity, and enabling the teeth to move, rotate, protrude, and / or be indented after installation.

[0003] In particular, teeth are fixed within the dental arch by alveolar bone, periodontal ligament, and gingiva. When orthodontic appliances apply corrective force to the teeth, the periodontal tissues generate a force of the same magnitude but opposite direction to the corrective force – this is resistance. This resistance changes during orthodontic treatment, even for the same tooth, depending on the stage. Even teeth with high resistance at the beginning will experience reduced resistance at a certain point when corrective force is continuously applied within physiological limits, making them easier to move.

[0004] However, when a typical orthodontic appliance is installed in the mouth, its shape may deform due to the resistance of the teeth being treated. Because of this deformation, it is impossible to achieve the intended goals of moving, rotating, protruding, and / or indenting the teeth by simply installing the appliance. In order to achieve the initial treatment goals, there is a cumbersome process of removing the deformed appliance and making and installing a new one.

[0005] In addition, in order to achieve treatment goals, conventional orthodontic appliances require the direct introduction of a specific composition into the oral cavity and the taking of an impression in the process of custom manufacturing based on the oral cavity morphology data of the patient to achieve the treatment goals. Each time, an individual orthodontic appliance needs to be made, which is cumbersome.

[0006] In this context, there is an urgent need to provide shape-restoring polymer compositions and orthodontic devices that possess rigidity, stiffness, and elasticity suitable for orthodontic treatment within a specific temperature range, while exhibiting original shape restoration properties within a specific temperature range different from the stated specific temperature range.

[0007] Furthermore, there is an urgent need to provide photocurable polymer compositions that, while possessing the characteristics described above, can be easily and accurately manufactured by direct 3D printing, and orthodontic devices using the same.

[0008] Furthermore, there is an urgent need to provide polymeric compositions that, while possessing the characteristics described above, maintain a robust crystalline structure even at high-temperature sterilization temperatures, and orthodontic devices using the same. Summary of the Invention

[0009] Technical issues The problem to be solved by this disclosure is to provide a shape-restoring polymer composition that has rigidity, stiffness and elasticity suitable for orthodontic treatment within a specific temperature range, and shape-restoring properties within a specific temperature range different from the stated specific temperature range, and an orthodontic device using the same.

[0010] Another issue to be addressed by this disclosure is to provide a photocurable polymer composition that can be easily and accurately manufactured by direct 3D printing, and a dental orthodontic device using the same.

[0011] Another problem to be solved by this disclosure is to provide a polymer composition that maintains a robust crystalline structure even at high-temperature sterilization temperatures, and a dental orthodontic device using the same.

[0012] The problems to be solved by this disclosure are not limited to those mentioned above. Any problems to be solved by this disclosure not mentioned may be clearly understood by those skilled in the art ("those skilled in the art") from the following description.

[0013] Technical solution According to one embodiment of the invention, a photocurable shape-restoring polymer composition comprising a photocurable compound, a photoinitiator, and an antioxidant is provided. The photocurable compound comprises one or more selected from the group consisting of aliphatic carbamate dimethacrylate, caprolactone carbamate triacrylate, bisphenol A ethoxylated dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate. The photoinitiator comprises one or more selected from the group consisting of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methyl phenylglyoxylate, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. The antioxidant, 2,6-di-tert-butyl-p-cresol, is a photocurable shape-restoring polymer composition that can be provided.

[0014] On the other hand, the photocurable compound may contain caprolactone carbamate trimethacrylate instead of caprolactone carbamate triacrylate.

[0015] As an example, the photocurable compound may be a photocurable shape-restoring polymer composition comprising 40 to 70 parts by weight of aliphatic urethane dimethacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0016] As an example, the photocurable compound may be a photocurable shape-restoring polymer composition comprising 1 to 25 parts by weight of caprolactone carbamate triacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0017] As an example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 20 parts by weight of bisphenol A ethoxylated dimethacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0018] As an example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 20 parts by weight of hydroxyethyl methacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0019] As an example, the photocurable compound may be a photocurable shape-restoring polymer composition containing 1 to 30 parts by weight of isoborneol methacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0020] As an example, the photoinitiator may be a photocurable shape recovery polymer composition comprising 1 to 14 parts by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide relative to 100 parts by weight of the entire photocurable shape recovery polymer composition.

[0021] As an example, the photoinitiator may be a photocurable shape-restoring polymer composition containing 0.1 to 15 parts by weight of methyl phenylglyoxylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0022] As an example, the photoinitiator may be a photocurable shape recovery polymer composition comprising 5 to 40 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide relative to 100 parts by weight of the entire photocurable shape recovery polymer composition.

[0023] As an example, the antioxidant may be a photocurable shape recovery polymer composition containing 0.3 to 1.5 parts by weight of 2,6-di-tert-butyl-p-cresol, relative to 100 parts by weight of the entire photocurable shape recovery polymer composition.

[0024] As an example, the photocurable shape recovery polymer composition may be a photocurable shape recovery polymer composition that has a glass transition temperature at 50 to 110°C after curing.

[0025] Furthermore, according to one embodiment of this disclosure, a dental orthodontic device manufactured using the aforementioned light-curable shape-restoring polymer composition can be provided.

[0026] Invention Effects According to this disclosure, a shape-restoring polymer composition and a dental orthodontic device using the same can be provided, which have rigidity, stiffness and elasticity suitable for orthodontic treatment within a specific temperature range, and have original shape restoration properties within a specific temperature range different from the stated specific temperature range.

[0027] Furthermore, according to this disclosure, a photocurable polymer composition that can be easily and accurately manufactured by direct 3D printing and a dental orthodontic device using the same can be provided.

[0028] Furthermore, according to this disclosure, a polymer composition that maintains a robust crystalline structure even at high-temperature sterilization temperatures and a dental orthodontic device using the same can be provided.

[0029] The superior and / or useful effects of this disclosure are not limited to those described above. Those skilled in the art, based on the disclosure in this specification, can also readily recognize the superior and / or useful effects of this disclosure that are not explicitly disclosed in this specification. This should be understood as content that this specification intends to disclose and is obviously included within the scope of this disclosure. Attached Figure Description

[0030] Figure 1 A graph showing the test results of the glass transition temperature (Tg) of a photocurable shape recovery composition according to an embodiment of the present disclosure.

[0031] Best practice This invention relates to a photocurable shape-restoring polymer composition comprising a photocurable compound and a photoinitiator. The photocurable compound comprises one or more selected from the group consisting of aliphatic carbamate dimethacrylate, caprolactone carbamate triacrylate, bisphenol A ethoxylated dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate. The photoinitiator comprises one or more selected from the group consisting of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methyl phenylglyoxylate, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Detailed Implementation

[0032] The terms or words used in this specification and claims are not intended to be limited to their general dictionary meanings. Those skilled in the art will clearly understand that the terms or words are within the scope of the concepts obviously intended to be conveyed in this specification and claims, and are used within the scope of meaning intended to convey the content of this disclosure.

[0033] Furthermore, the aspects, implementation methods, embodiments, etc., of this disclosure described in this specification are presented as preferred examples at the time only to enable those skilled in the art to understand and reproduce this disclosure, and are not intended to limit this disclosure.

[0034] Furthermore, the descriptions and specific embodiments of various configurations in this specification are also readily applicable to the descriptions and specific embodiments of other configurations. That is, those skilled in the art will clearly understand that all possible combinations of the various configurations and specific embodiments disclosed in this specification fall within the scope of this specification.

[0035] The term "and / or" as used in this specification is a term that includes each item mentioned and all combinations of two or more items. Furthermore, when a singular term is used in this specification, it is disclosed in a manner that includes the plural form, unless otherwise stated.

[0036] The terms “comprise” and “comprising” used in this specification are terms that allow the presence or addition of items other than those mentioned. The terms “consist”, “consisting”, and “consisting” used in this specification are terms that do not allow the presence or addition of items other than those mentioned.

[0037] As used in this specification, the term "to" refers to the range of values ​​encompassed by the values ​​preceding and following the term, respectively, as the lower and upper limits. Where the upper and / or lower limits of any numerical range are disclosed in multiple forms, the numerical range discloses any numerical range using any one of the multiple lower limits and any one of the multiple upper limits as the lower and upper limits, respectively.

[0038] As used in this specification, the terms “about” and / or “approximately” refer to a numerical range between the upper and lower limits of 10%, based on the values ​​represented by the “about” and / or “approximately”.

[0039] The terms or words used in this specification and claims should not be limited to their usual dictionary meanings, but should be interpreted as meanings and concepts consistent with the technical spirit of this disclosure, based on the principle that the inventors may appropriately define the terms and concepts to best illustrate their own invention. Therefore, the embodiments described in this specification are merely preferred embodiments of this disclosure and do not represent the entirety of the technical spirit of this disclosure. It should be understood that various equivalents and modifications may exist at the time of this application.

[0040] On the other hand, the descriptions and embodiments disclosed in this specification are also applicable to various other descriptions and embodiments. That is, all combinations of the various elements disclosed in this specification fall within the scope of this disclosure, and any omissions in one embodiment may be interpreted in accordance with the manner described in other embodiments. Furthermore, the scope of this disclosure should not be considered limited by the following specific description.

[0041] According to one embodiment of the present disclosure, a photocurable shape-restoring polymer composition can be provided.

[0042] The photocurable shape-restoring polymer composition, when cured, exhibits rigidity, straightness, and elasticity suitable for orthodontic treatment within a first temperature range, and possesses original shape restoration properties within a second temperature range different from the first temperature range.

[0043] That is, the photocurable shape-restoring polymer composition simultaneously possesses an amorphous and a crystalline structure. During curing, for example, when formed into an orthodontic appliance, when the orthodontic appliance undergoes temporary deformation due to wearing in the oral cavity within a first temperature range, the intermolecular motion energy in the amorphous region increases within a second temperature range, making it elastic like soft rubber. Furthermore, utilizing its property of rapidly restoring its original shape without external stress, such as the resistance of the teeth being orthodontized, the deformation of the orthodontic appliance can be restored. Subsequently, it can regain its elasticity with stiffness and rigidity, i.e., the orthodontic force, at a certain temperature, such as within the first temperature range.

[0044] Typically, low-molecular-weight substances undergo a phase transition from a solid to a liquid phase upon heating. In contrast, high-molecular-weight substances exhibit another change before undergoing this phase transition, and the temperature at this point is considered the glass transition temperature. Unlike low-molecular-weight compounds where molecules are regularly arranged and stacked to form a solid phase, typical high-molecular-weight compositions have very large molecular weights, resulting in irregular arrangements and numerous amorphous regions that are difficult to crystallize. Therefore, they exhibit semi-crystalline properties, a mixture of crystalline and amorphous regions.

[0045] When a polymer composition is heated, the intermolecular energy in these amorphous regions increases, and the micro-Brownian motion becomes more active. At this point, the rigid polymer transforms into a soft, rubber-like elastic substance. That is, the glass transition temperature (Tg) can be the temperature at which the molecules in the amorphous polymer regions become active and begin to move, thus transforming into a viscous liquid or rubbery state. Alternatively, it can be the temperature at which the amorphous polymer exhibits glassy properties such as brittleness, stiffness, and rigidity as the temperature decreases. Furthermore, polymers possess inherent glass transition temperatures based on their properties; therefore, the glass transition temperature can be used to identify polymers.

[0046] Since the glass transition temperature (TVT) applies only to amorphous polymers, it may not be defined for purely crystalline polymers. Similarly, for purely amorphous polymers, the melting temperature (Tm) is not defined; only the TVT can be defined. However, many polymers possess both amorphous and crystalline structures, meaning most polymers may have both a TVT and a melting temperature. Generally, the TVT is lower than the melting temperature; a high TVT can be interpreted as a polymer that is relatively difficult to melt.

[0047] That is, the photocurable shape-restoring polymer composition is a composition that simultaneously possesses an amorphous structure and a crystalline structure. After curing, the composition exhibits rigidity, straightness, and elasticity suitable for orthodontic treatment within a first temperature range, for example, 15°C to 40°C, and has a glass transition temperature within a second temperature range different from the first temperature range, for example, 50°C to 110°C. Within the second temperature range, the molecules of the composition are active and begin to move, thereby rapidly restoring the shape of the device or even the product. Furthermore, when the first temperature range is reached again, the shape and physical properties are restored, making the device or even the product substantially equivalent to its original shape and rigidity at the time of manufacture.

[0048] Furthermore, when the light-curable shape-restoring composition is cured, for example in the case of forming a dental orthodontic appliance, considering hygiene and disinfection for intraoral use, the crystalline structure of the cured composition can still be firmly maintained under the high-temperature sterilization conditions commonly used in dentistry (autoclave), namely 121 to 135°C and 1 atmosphere, thus exhibiting high-temperature resistance. Therefore, even when exposed to high-temperature sterilization conditions, the shape memory properties can still be maintained.

[0049] For example, the photocurable shape recovery polymer composition may be a photocurable shape recovery polymer composition comprising a photocurable compound, a photoinitiator, and an antioxidant.

[0050] For example, the photocurable compound may contain one or more selected from the group consisting of aliphatic carbamate dimethacrylate, caprolactone carbamate triacrylate, bisphenol A ethoxylated dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate.

[0051] On the other hand, the photocurable compound may contain caprolactone carbamate trimethacrylate instead of caprolactone carbamate triacrylate.

[0052] For example, the photocurable compound may be a photocurable shape-restoring polymer composition comprising 40 to 70 parts by weight of aliphatic urethane dimethacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the aliphatic urethane dimethacrylate may comprise 50 to 65 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0053] For example, the photocurable compound may be a photocurable shape-restoring polymer composition comprising 1 to 25 parts by weight of caprolactone carbamate triacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the caprolactone carbamate triacrylate may comprise 4 to 25 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0054] On the other hand, the photocurable compound may contain caprolactone carbamate trimethacrylate in the same proportions as caprolactone carbamate triacrylate.

[0055] For example, the photocurable compound may be a photocurable shape-restoring polymer composition comprising 1 to 20 parts by weight of bisphenol A ethoxylated dimethacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the bisphenol A ethoxylated dimethacrylate may comprise 4 to 22 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0056] For example, the photocurable compound may be a photocurable shape-restoring polymer composition comprising 1 to 20 parts by weight of hydroxyethyl methacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the hydroxyethyl methacrylate may comprise 4 to 25 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0057] For example, the photocurable compound may be a photocurable shape-restoring polymer composition comprising 1 to 30 parts by weight of isoborneol methacrylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the isoborneol methacrylate may comprise 4 to 35 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0058] For example, the photoinitiator may comprise one or more of the group consisting of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methyl phenylglyoxylate, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0059] For example, the photoinitiator may be a photocurable shape-restoring polymer composition comprising 1 to 14 parts by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide may comprise 1.2 to 15 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0060] For example, the photoinitiator may be a photocurable shape-restoring polymer composition comprising 0.1 to 15 parts by weight of methyl phenylglyoxylate relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the methyl phenylglyoxylate may comprise 0.4 to 14.5 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0061] For example, the photoinitiator may be a photocurable shape-restoring polymer composition comprising 5 to 40 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition. Preferably, the 2,4,6-trimethylbenzoyl-diphenylphosphine oxide may comprise 5 to 35 parts by weight relative to 100 parts by weight of the entire photocurable shape-restoring polymer composition.

[0062] For example, a photocurable shape-restoring polymer composition in which the antioxidant is 2,6-di-tert-butyl-p-cresol can be provided.

[0063] For example, the antioxidant may be a photocurable shape recovery polymer composition comprising 0.3 to 1.5 parts by weight of 2,6-di-tert-butyl-p-cresol relative to 100 parts by weight of the entire photocurable shape recovery polymer composition. Preferably, the 2,6-di-tert-butyl-p-cresol may comprise 0.4 to 1.2 parts by weight relative to 100 parts by weight of the entire photocurable shape recovery polymer composition.

[0064] For example, the photocurable shape recovery polymer composition may be a photocurable shape recovery polymer composition that has a glass transition temperature at 50 to 110°C after curing.

[0065] For example, the photocurable shape recovery polymer composition may be a photocurable shape recovery polymer composition that retains crystallinity after curing at 115 to 140°C and 1 atmosphere.

[0066] For example, the photocurable shape recovery polymer composition may be a photocurable shape recovery polymer composition for direct 3D printing.

[0067] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition used in the manufacture of orthodontic devices.

[0068] For example, the photocurable shape-restoring polymer composition may be a photocurable shape-restoring polymer composition used in the manufacture of transparent orthodontic devices.

[0069] Furthermore, according to one embodiment of this disclosure, a dental orthodontic device manufactured using the aforementioned light-curable shape-restoring polymer composition can be provided.

[0070] Typically, orthodontic appliances used in clinical orthodontic practice conform to the teeth within a usable temperature range, specifically the first temperature range (15°C to 40°C) encompassing the body temperature range of 36.5°C to 37.5°C. They adhere to the teeth based on their elasticity and internal surface gaps, and deform (stain) due to resistance to the orthodontic force. The orthodontic force can then be generated and adjusted by the appliance's elasticity, movement distance, rotation angle, thickness, internal surface gap spacing, and various auxiliary devices.

[0071] Orthodontic appliances manufactured using the photocurable shape-restoring polymer composition according to this disclosure can rapidly recover their original shape and elastic properties before deformation, for example, after 5 to 60 seconds, preferably 20 to 30 seconds, at a glass transition temperature, such as 50 to 110°C. Subsequently, upon re-wearing, the orthodontic appliance will exert a continuous corrective force to achieve the initially intended tooth movement target.

[0072] That is, orthodontic appliances manufactured using the photocurable shape-restoring polymer composition according to this disclosure are, for example, manufactured using a polymer composition designed to have a glass transition temperature of 50 to 110°C and to possess stiffness, rigidity, and elasticity within a temperature range including room temperature and body temperature. The photocurable shape-restoring polymer composition according to this disclosure is configured such that the shape-restoring force of the orthodontic appliance at the glass transition temperature is less than the resistance force of the teeth, thereby restoring the shape of the orthodontic appliance within a temperature range with almost no stress, and restoring the orthodontic appliance to its original rigidity, rigidity, and elasticity, thus enabling it to function as an orthodontic appliance.

[0073] For example, orthodontic appliances manufactured using the aforementioned light-curable shape-restoring polymer composition may be orthodontic appliances having a glass transition temperature at 50 to 110°C.

[0074] For example, a dental orthodontic device manufactured using the aforementioned light-curable shape-restoring polymer composition may be a dental orthodontic device that retains its crystallinity after curing at 115 to 140°C and 1 atmosphere.

[0075] The present disclosure will be further described in detail below using examples. Process conditions and preparation steps not explicitly described in the following examples may be obvious process conditions or preparation steps in the technical field to which this disclosure pertains. Those skilled in the art can select them without difficulty based on this disclosure and reproduce the problem-solving principles of this disclosure.

[0076] Furthermore, in the manufacturing method according to this disclosure, unless otherwise expressly stated, the steps constituting the manufacturing method are performed at room temperature (15°C to 25°C), and it should be understood that the steps are performed by means and tools that can be derived without difficulty by those skilled in the art.

[0077] Examples 1 to 15: Preparation of photocurable shape-restoring polymer compositions according to the present disclosure Aliphatic carbamate dimethacrylate (PP1), caprolactone carbamate triacrylate (PP2), bisphenol A ethoxylated dimethacrylate (PP3), hydroxyethyl methacrylate (PP4), and isobornyl methacrylate (PP5) were used as photocurable compounds. Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (ID1), methyl phenylglyoxylate (ID2), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (ID3) were used as photoinitiators. 2,6-di-tert-butyl-p-cresol was used as an antioxidant. The mixtures were prepared according to the weights corresponding to the parts listed in Tables 1 and 2 below, based on 100g of the entire photocurable shape-recovery polymer composition. The mixtures were then heated to melt and cooled to room temperature to prepare the compositions of Examples 1 to 15. Alternatively, caprolactone carbamate trimethacrylate can be used instead of caprolactone carbamate triacrylate as the photocurable compound.

[0078] [Table 1] [Table 2] Comparative Examples 1-5: Each component was weighed according to the proportions shown in Table 2, based on 100g of the photocurable shape recovery polymer composition. After mixing, the components were heated to melt and then cooled to room temperature to obtain the compositions corresponding to Comparative Examples 1-5.

[0079] Experimental Example: Determination of the glass transition temperature of photocurable shape-restoring polymer compositions Figure 1 The results of measuring the glass transition temperature (Tg) of a photocurable shape recovery composition according to an embodiment of this disclosure are shown. See also Figure 1 The glass transition temperature of the composition obtained in Example 6 was measured after curing by ultraviolet light. The results showed that the cured composition formed a glass transition region in the range of 50°C to 110°C. Therefore, it can be confirmed that the photocurable shape-restoring composition according to this disclosure has a glass transition temperature of 50°C to 110°C and is able to restore its original shape and elastic properties within a temperature range higher than human body temperature.

[0080] The preferred embodiments of this disclosure have been described in detail above, but the scope of this disclosure is not limited thereto. Various modifications and improvements made by those skilled in the art based on the basic concepts defined in the following claims also fall within the scope of protection of this disclosure.

Claims

1. A photocurable shape-restoring polymer composition, characterized in that, It includes photocurable compounds and photoinitiators. The photocurable compound comprises one or more selected from the group consisting of aliphatic carbamate dimethacrylate, caprolactone carbamate triacrylate, bisphenol A ethoxylated dimethacrylate, hydroxyethyl methacrylate, and isobornyl methacrylate; the photoinitiator comprises one or more selected from the group consisting of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, methyl phenylglyoxylate, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

2. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the entire photocurable shape-recovery polymer composition, the photocurable compound comprises 40 to 70 parts by weight of aliphatic urethane dimethacrylate.

3. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the entire photocurable shape-recovery polymer composition, the photocurable compound contains 1 to 25 parts by weight of caprolactone carbamate triacrylate.

4. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the photocurable shape-recovery polymer composition, the photocurable compound comprises 1 to 20 parts by weight of bisphenol A ethoxylated dimethacrylate.

5. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the photocurable shape-recovery polymer composition, the photocurable compound contains 1 to 20 parts by weight of hydroxyethyl methacrylate.

6. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the entire photocurable shape-recovery polymer composition, the photocurable compound contains 1 to 30 parts by weight of isobornyl methacrylate.

7. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the entire photocurable shape-recovery polymer composition, the photoinitiator comprises 1 to 14 parts by weight of bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

8. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the entire photocurable shape-recovery polymer composition, the photoinitiator comprises 0.1 to 15 parts by weight of methyl phenylglyoxylate.

9. The photocurable shape-restoring polymer composition according to any one of claims 1 to 6, characterized in that, Based on 100 parts by weight of the entire photocurable shape-recovery polymer composition, the photoinitiator comprises 5 to 40 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

10. The photocurable shape-restoring polymer composition according to claim 1, characterized in that, Based on 100 parts by weight of the entire photocurable shape-recovery polymer composition, it also contains 0.3 to 1.5 parts by weight of 2,6-di-tert-butyl-p-cresol as an antioxidant.

Images