Biocompatible polymer composition having 4d characteristics and capable of photocurable 3D printing, and use thereof

Abstract

The present invention relates to a biocompatible polymer composition for application to photocurable 3D printing, and more specifically, to a polymer composition suitable for 3D printing that can impart 4D properties, wherein, after deformation at a specific temperature, the deformed shape is maintained upon cooling, and the original shape is restored when reheated to the specific temperature.

Description

Biocompatible polymer composition capable of photocuring 3D printing with 4D properties and use thereof

[0001] This application claims priority to Republic of Korea Patent Application No. 10-2024-0074295, filed June 7, 2024, the entire disclosure of which is incorporated herein by reference.

[0002] The present invention relates to a biocompatible polymer composition for application to a photocuring 3D printing method and its use, and more particularly, to a polymer composition suitable for 3D printing that can be provided with 4D characteristics, such as being able to deform a shape at a specific temperature, maintain the deformed shape when the temperature is lowered, and return to a circular shape when a specific temperature is applied again.

[0003] 3D printing, a key driver of the Fourth Industrial Revolution, is seeing increasing demand due to its ability to create diverse and complex shapes. Consequently, research is underway on various processes and materials to incorporate plastics and metals into 3D printing. Meanwhile, the recent growth of the bio-health market has led to a rapid increase in the need for personalized medical devices and healthcare equipment. These devices, tailored to the bio-health sector, must be biocompatible and minimize deformation due to patient movement.

[0004] However, the 3D printing technology currently being applied in the bio-health field is mainly for dental orthodontic devices, splints, etc., and its application field is very narrow (Korean Patent Publication No. 10-2024-0055911, Korean Patent Publication No. 10-2021-0079928). Moreover, the materials being applied are also limited to polyurethane-based materials (Korean Patent Publication No. 10-2444341). Dental orthodontic devices are items that are replaced after a short period of use, and splints have a relatively flexible period of use, but both items have little or no contact with body tissues, and materials such as silicone used for body insertion are not suitable for application to the 3D printing process due to their low viscosity and hardening method. Therefore, there is a need to develop 3D printing materials that have a large area of ​​contact with body tissues or have new biocompatibility for body insertion.

[0005] Accordingly, in order to overcome these limitations, the present invention has made efforts to develop a new polymer composition applicable to a light-sensitive 3D printing process that has shape memory properties in addition to biocompatibility.

[0006] [Prior Art Literature]

[0007] [Patent Document]

[0008] (Patent Document 1) Republic of Korea Publication No. 10-2024-0055911

[0009] (Patent Document 2) Republic of Korea Publication No. 10-2021-0079928

[0010] (Patent Document 3) Republic of Korea Publication No. 10-2444341

[0011] The purpose of the present invention is to provide a biocompatible polymer composition for application to a photocuring 3D printing method and a method for producing the same, a photocuring 3D printing output using the polymer composition, and a 3D printing method.

[0012] To achieve the above object, the present invention provides a photocurable 3D printing composition comprising a copolymer comprising a lactone monomer and glycidyl methacrylate, a photoinitiator, and a reactive diluent.

[0013] In the present invention, the copolymer may be at least one selected from the group consisting of the following chemical formulas (1) to (4):

[0014] Chemical formula (1)

[0015]

[0016] In the above chemical formula (1),

[0017] R1, R2 and R3 are each independently hydrogen (H) or an alkyl group having 1 to 6 carbon atoms,

[0018] m and n are integers from 1 to 20, independently of each other,

[0019] A, B1 and B2 are independently oxygen (O) or sulfur (S),

[0020] x and y represent the mole % of repeating units,

[0021] x+y is 100, and x is between 70 and 99;

[0022] Chemical formula (2)

[0023]

[0024] In the above chemical formula (2),

[0025] x is an integer from 1 to 20,

[0026] m and n represent the mole % of repeating units,

[0027] m+n is 100, and m is between 70 and 99;

[0028] Chemical formula (3)

[0029]

[0030] In the above chemical formula (3),

[0031] x and y are integers from 1 to 20, independently of each other,

[0032] m and n represent the mole % of repeating units,

[0033] m+n is 100, m is 70 to 99,

[0034] Chemical formula (4)

[0035]

[0036] In the above chemical formula (4),

[0037] x and y are integers from 1 to 20, independently of each other,

[0038] m and n represent the mole % of repeating units,

[0039] m+n is 100, and m is between 70 and 99.

[0040] In the present invention, the reactive diluent may be at least one selected from the group consisting of isobornyl acrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, N-methylpyrrolidone, N-vinylpyrrolidone, ethyl acetate, benzyl alcohol, chloroform, and tetrahydrofuran.

[0041] In the present invention, the reactive diluent may be included in an amount of 50 to 100 parts by weight based on 100 parts by weight of the copolymer.

[0042] In the present invention, the composition may additionally include a reactive oligomer.

[0043] In the present invention, the reactive oligomer may be at least one selected from the group consisting of diurethane dimethacrylate, epoxy oligomer, epoxidized soybean oil, acrylated epoxidized soybean oil, epoxy methacrylate, amine modified acrylate, polyester acrylate, and liquid silicone rubber.

[0044] In the present invention, the reactive oligomer may be included in an amount of 0 to 150 parts by weight based on 100 parts by weight of the copolymer.

[0045] In the present invention, the photoinitiator may be at least one selected from the group consisting of Irgacure, Darocure, LAP (Lithium phenyl-2,4,6-trimethylbenzoylphosphinate), TPO (Diphenyl(2,4,6-Trimethylbenzoyl)Phosphine), and TPO-L (Ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate).

[0046] In the present invention, the photoinitiator may be included in an amount of 0.5 to 3.0 parts by weight based on 100 parts by weight of the copolymer.

[0047] The present invention also provides a photocurable 3D printing output product in which the composition is 3D printed.

[0048] In the present invention, the composition can exhibit 4D characteristics through a photocrosslinking reaction by light energy irradiation.

[0049] In the present invention, the output may have a shape restoring ability of 60% or more at a temperature of 30 to 50°C.

[0050] In the present invention, the output material may be a medical material or an industrial material.

[0051] The present invention also provides a method for manufacturing the photocurable 3D printing composition:

[0052] (a) mixing a copolymer comprising a lactone monomer and glycidyl methacrylate with a reactive diluent; and

[0053] (b) A step of mixing a photoinitiator into the mixture of step (a).

[0054] In the present manufacturing method, the step (a) may be to additionally mix a reactive oligomer.

[0055] In the present manufacturing method, the copolymer may be at least one selected from the group consisting of chemical formulas (1) to (4).

[0056] Chemical formula (1)

[0057]

[0058] In the above chemical formula (1),

[0059] R1, R2 and R3 are each independently hydrogen (H) or an alkyl group having 1 to 6 carbon atoms,

[0060] m and n are integers from 1 to 20, independently of each other,

[0061] A, B1 and B2 are independently oxygen (O) or sulfur (S),

[0062] x and y represent the mole % of repeating units,

[0063] x+y is 100, and x is between 70 and 99;

[0064] Chemical formula (2)

[0065]

[0066] In the above chemical formula (2),

[0067] x is an integer from 1 to 20,

[0068] m and n represent the mole % of repeating units,

[0069] m+n is 100, and m is between 70 and 99;

[0070] Chemical formula (3)

[0071]

[0072] In the above chemical formula (3),

[0073] x and y are integers from 1 to 20, independently of each other,

[0074] m and n represent the mole % of repeating units,

[0075] m+n is 100, m is 70 to 99,

[0076] Chemical formula (4)

[0077]

[0078] In the above chemical formula (4),

[0079] x and y are integers from 1 to 20, independently of each other,

[0080] m and n represent the mole % of repeating units,

[0081] m+n is 100, and m is between 70 and 99.

[0082] In the present manufacturing method, the reactive diluent may be at least one selected from the group consisting of isobornyl acrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, N-methylpyrrolidone, N-vinylpyrrolidone, ethyl acetate, benzyl alcohol, chloroform, and tetrahydrofuran.

[0083] In the present manufacturing method, the reactive oligomer may be at least one selected from the group consisting of diurethane dimethacrylate, epoxy oligomer, epoxidized soybean oil, acrylated epoxidized soybean oil, epoxy methacrylate, amine modified acrylate, polyester acrylate, and liquid silicone rubber.

[0084] In the present manufacturing method, the photoinitiator may be at least one selected from the group consisting of Irgacure, Darocure, LAP (Lithium phenyl-2,4,6-trimethylbenzoylphosphinate), TPO (Diphenyl(2,4,6-Trimethylbenzoyl)Phosphine), and TPO-L (Ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate).

[0085] In the present manufacturing method, the reactive diluent may be mixed in an amount of 50 to 100 parts by weight relative to 100 parts by weight of the copolymer.

[0086] In the present manufacturing method, the reactive oligomer may be mixed in an amount of 0 to 150 parts by weight based on 100 parts by weight of the copolymer.

[0087] In the present manufacturing method, the photoinitiator may be mixed in an amount of 0.5 to 3.0 parts by weight relative to 100 parts by weight of the copolymer.

[0088] The present invention also provides a photocurable 3D printing method comprising the following steps:

[0089] (a) a step of manufacturing the photocurable 3D printing composition; and

[0090] (b) A step of 3D printing by irradiating light energy to the photocurable 3D printing composition.

[0091] In the present invention, the step (b) may be irradiating light energy having a wavelength of 365 nm to 405 nm.

[0092] The present invention also provides the above-described photocurable 3D printing composition for use in the manufacture of medical or industrial structures, or a photocurable 3D printing output manufactured by 3D printing the same.

[0093] The present invention also provides a use of the above-described photocurable 3D printing composition for use in the manufacture of medical or industrial structures or a photocurable 3D printing output manufactured by 3D printing the same.

[0094] When the polymer composition according to the present invention is applied to 3D printing, it has the advantage of being biocompatible and having shape memory properties added by irradiating light energy, making it possible to easily manufacture various medical products or industrial products that have a large contact area with the body or that must be inserted into the body through 3D printing.

[0095] Figures 1a to 1c show the results of photocuring printing output using polymer compositions according to examples and comparative examples of the present invention.

[0096] Figure 2 shows an output using a polymer composition according to one embodiment of the present invention (Example 3).

[0097] Figure 3 shows the results of confirming the 4D characteristics of an output using a polymer composition according to one embodiment (Example 3) of the present invention.

[0098] Figure 4 confirms the crosslinking form of an output product using a polymer composition according to one embodiment of the present invention (Example 3).

[0099] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In general, the nomenclature used herein and the experimental methods described below are well known and commonly used in the art.

[0100] In the present invention, it should be understood that terms such as “include” or “have” are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof.

[0101] In the present invention, 4D printing is an extension of 3D printing, and refers to a technology for creating objects that can self-deform over time. Specifically, in the present invention, it refers to a technology for creating objects whose 3D printed output changes shape in response to temperature.

[0102] Composition

[0103] In the present invention, it was confirmed that when a photoinitiator, a reactive diluent, and optionally a reactive oligomer are mixed in a specific ratio with a copolymer including a lactone monomer and glycidyl methacrylate, 3D printing is possible in which excellent biocompatibility and 4D characteristics can be imparted by crosslinking through light energy irradiation.

[0104] Accordingly, the present invention relates, in one aspect, to a polymer composition comprising a copolymer comprising a lactone monomer and glycidyl methacrylate, a photoinitiator and a reactive diluent.

[0105] In the present invention, the polymer composition may be characterized as being a composition for photocuring 3D printing.

[0106] The above copolymer may be at least one compound selected from the group consisting of the following chemical formulas (1) to (4).

[0107] Chemical formula (1)

[0108]

[0109] In the above chemical formula (1),

[0110] R1, R2 and R3 are each independently hydrogen (H) or an alkyl group having 1 to 6 carbon atoms,

[0111] m and n are integers from 1 to 20, independently of each other,

[0112] A, B1 and B2 are independently oxygen (O) or sulfur (S),

[0113] x and y represent the mole % of repeating units,

[0114] x+y is 100, and x is between 70 and 99.

[0115] The above chemical formula (1) can be represented by the following chemical formula (1'):

[0116] Chemical formula (1')

[0117]

[0118] In the above chemical formula (1')

[0119] m and n are integers from 1 to 20, independently of each other,

[0120] x and y represent the mole % of repeating units,

[0121] x+y is 100, and x is between 80 and 99.

[0122] In the above chemical formula (1) or (1'), x and y represent the mol% of repeating units, x+y is 100, and x can be 80 to 99, 80 to 95, 88 to 99, or 88 to 94.

[0123] In the present invention, the 2-arm copolymer of chemical formula (1) is described in detail in Korean Patent No. 10-2355542, which is incorporated herein by reference in its entirety.

[0124] Chemical formula (2)

[0125]

[0126] In the above chemical formula (2),

[0127] x is an integer from 1 to 20,

[0128] m and n represent the mole % of repeating units,

[0129] m+n is 100, and m is between 70 and 99.

[0130] In the above chemical formula (2), m can be 80 to 96.

[0131] In the present invention, the 4-arm copolymer of chemical formula (2) is described in detail in Korean Patent Publication No. 10-2021-0158356, which is incorporated herein by reference in its entirety.

[0132] Chemical formula (3)

[0133]

[0134] In the above chemical formula (3),

[0135] x and y are integers from 1 to 20, independently of each other,

[0136] m and n represent the mole % of repeating units,

[0137] m+n is 100, and m is between 70 and 99.

[0138] In the present invention, the 6-arm copolymer of chemical formula (3) is described in detail in Korean Patent No. 10-2516991, which is incorporated herein by reference in its entirety.

[0139] Chemical formula (4)

[0140]

[0141] In the above chemical formula (4),

[0142] x and y are integers from 1 to 20, independently of each other,

[0143] m and n represent the mole % of repeating units,

[0144] m+n is 100, and m is between 70 and 99.

[0145] In the present invention, the 8-arm copolymer of chemical formula (4) is described in detail in Korean Patent No. 10-2610524, which is incorporated herein by reference in its entirety.

[0146] In the present invention, the reactive diluent may be at least one selected from the group consisting of isobornyl acrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, N-methylpyrrolidone, N-vinylpyrrolidone, ethyl acetate, benzyl alcohol, chloroform, and tetrahydrofuran, but is not limited thereto.

[0147] In one embodiment, the reactive diluent may be isobornyl acrylate.

[0148] In the present invention, the reactive diluent may be included in an amount of 50 to 100 parts by weight relative to 100 parts by weight of the copolymer. In this case, if the reactive diluent is included in an amount of less than 50% by weight relative to the weight of the copolymer, it is difficult to output a normal structure by 3D printing, and if the reactive diluent is included in an amount of more than 100% by weight relative to the weight of the copolymer, there is a problem in that the concentration of the final composition becomes diluted and it has a property that is easily broken by 3D printing.

[0149] In the present invention, the composition may additionally include a reactive oligomer.

[0150] In the present invention, the reactive oligomer may be at least one selected from the group consisting of diurethane dimethacrylate, epoxy oligomer, epoxidized soybean oil, acrylated epoxidized soybean oil, epoxy methacrylate, amine modified acrylate, polyester acrylate, and liquid silicone rubber, but is not limited thereto.

[0151] In the present invention, the reactive oligomer may be included in an amount of 0 to 150 parts by weight relative to 100 parts by weight of the copolymer. In this case, if the reactive oligomer is included in an amount exceeding 150% by weight relative to the weight of the copolymer, the melting temperature becomes significantly higher than the body temperature range, which is problematic in that it is not suitable for developing materials that have a wide body application area or are inserted into the body.

[0152] In the present invention, the photoinitiator may be at least one selected from the group consisting of Irgacure, Darocure, LAP (Lithium phenyl-2,4,6-trimethylbenzoylphosphinate), TPO (Diphenyl(2,4,6-Trimethylbenzoyl)Phosphine), and TPO-L (Ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate), but is not limited thereto.

[0153] In the present invention, the photoinitiator may be included in an amount of 0.5 to 3.0 parts by weight based on 100 parts by weight of the copolymer, and when the weight ratio is as described above, photocrosslinking (i.e., photocuring) can effectively occur upon irradiation with light energy in a 3D printing process.

[0154] use

[0155] From another aspect, the present invention relates to a photocurable 3D printing output product in which the composition is 3D printed.

[0156] In the present invention, the composition can exhibit 4D characteristics through a photocrosslinking reaction by light energy irradiation.

[0157] In the present invention, the output may have a shape restoring ability of 60% or more at a temperature of 30 to 50°C.

[0158] For example, the output may have a shape resilience of at least 50%, preferably, but not limited to, at a temperature of 30 to 50°C, or at any range of temperatures within 30 to 50°C, such as at a temperature of 40 to 45°C, or at any temperature within 35 to 50°C, such as at about 35°C, about 36°C, about 37°C, about 38°C, about 39°C, about 40°C, about 41°C, about 42°C, about 43°C, about 44°C, about 45°C, about 46°C, about 47°C, about 48°C, about 49°C, about 50°C.

[0159] In one embodiment, the output may have a shape restorability of 80% or more at a temperature of 40 to 45°C.

[0160] In the present invention, the output material may be a medical material or an industrial material.

[0161] The above medical material may be a material suitable for manufacturing a medical product having a large surface area in contact with the body of a human or mammal or a medical product (e.g., a medical device or medical apparatus) inserted into the body of a human or mammal.

[0162] In the present invention, the medical device may include, but is not limited to, a vascular stent, a non-vascular stent, a cardiac stent, a dental medical device, an artificial joint, an artificial organ, a membrane-type medical device, a tubular medical device, an implant medical device having a three-dimensional structure, etc., and it will be apparent to a person skilled in the art that the medical device can be applied to all medical devices capable of three-dimensional printing that require shape memory characteristics.

[0163] The above industrial materials may be, but are not limited to, materials suitable for manufacturing industrial products that have a high surface area in contact with the body of a human or mammal.

[0164] In the present invention, the industrial products may include, but are not limited to, health products, automobile interior and exterior materials, interior products, customized accessories, shoe insoles, figures, etc., and it will be apparent to those skilled in the art that the industrial products may be applied to all industrial products capable of 3D printing that require shape memory characteristics.

[0165] From this perspective, the present invention provides the above-described photocurable 3D printing composition for use in the manufacture of medical or industrial structures, or a photocurable 3D printing output manufactured by 3D printing the same.

[0166] The present invention also provides a use of the photocurable 3D printing composition or the photocurable 3D printing output for use in the manufacture of medical or industrial structures.

[0167] Furthermore, a medical or industrial structure manufactured using the photocurable 3D printing composition according to the present invention or a photocurable 3D printing output manufactured by 3D printing the same is provided.

[0168] In the present invention, the medical structure may refer to the aforementioned medical product, and the industrial structure may refer to the aforementioned industrial product.

[0169] Manufacturing method

[0170] In another aspect, the present invention provides a method for manufacturing a photocurable 3D printing composition, comprising the following steps:

[0171] (a) mixing a copolymer comprising a lactone monomer and glycidyl methacrylate with a reactive diluent; and

[0172] (b) A step of mixing a photoinitiator into the mixture of step (a).

[0173] In the present invention, the step (a) may further include mixing a reactive oligomer.

[0174] In the present invention, the copolymer may be at least one selected from the group consisting of chemical formulas (1) to (4).

[0175] In one embodiment, the reactive diluent may be isobornyl acrylate, but in addition, triethylene glycol dimethacrylate (Sigma-aldrich), hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, Sigma-aldrich), methylpyrrolidone (N-methylpyrrolidone, Sigma-aldrich), vinylpyrrolidone (N-vinylpyrrolidone, Sigma-aldrich), ethyl acetate (Daejung chemical), benzyl alcohol (Daejung chemical), chloroform (Daejung chemical), or tetrahydrofuran (Sigma-aldrich) may also be used.

[0176] In the present invention, the step (a) may be characterized by mixing 50 to 100 parts by weight of the reactive diluent relative to 100 parts by weight of the copolymer.

[0177] In one embodiment, the reactive oligomer may be diurethane dimethacrylate, but in addition, epoxy oligomer (Epoxy oligomer, Sigma-aldrich), epoxidized soybean oil (Epoxidized soybean oil, Sigma-aldrich), acrylated epoxidized soybean oil (Acrylated epoxidized soybean oil, Sigma-aldrich), epoxy methacrylate (Arkema), amine modified acrylate (Arkema), polyester acrylate (Arkema), or ultraviolet-curable liquid silicone rubber (Liquid silicone rubber, Elkem) may be used.

[0178] In the present invention, the step (a) may be characterized by mixing the reactive oligomer in an amount of 0 to 150 parts by weight relative to 100 parts by weight of the copolymer.

[0179] In the present invention, the step (b) may be characterized in that the photoinitiator is mixed in an amount of 0.5 to 3.0 parts by weight relative to 100 parts by weight of the copolymer.

[0180] In another aspect, the present invention relates to a photocurable 3D printing method comprising the following steps:

[0181] (a) a step of manufacturing the photocurable 3D printing composition; and

[0182] (b) A step of 3D printing by irradiating light energy to the photocurable 3D printing composition.

[0183] In the present invention, the step (b) may be characterized by irradiating light energy having a wavelength of 365 nm to 405 nm.

[0184] In the present invention, the 3D printing step may be performed using an SLA (StereoLithography Apparatus) printer, a PolyJet printer, a DLP (Digital Light Processing) printer, or an MJF (Multi Jet Fusion) printer, but is not limited thereto. A specific 3D printing method can be easily implemented by a person skilled in the art according to the instructions of each printer manufacturer.

[0185] The composition according to the present invention facilitates the implementation of customized and complex shapes required in various medical and industrial fields, and its shape can be controlled under specific conditions, making it applicable to a wide range of applications. In particular, the composition according to the present invention can induce customized shapes by considering the characteristics of each industrial product and patient, and it has the advantage of ensuring stability and ease of use by utilizing excellent biocompatibility and 4D characteristics.

[0186] From this perspective, the photocuring 3D printing method can be applied to a method for manufacturing a medical or industrial structure using the photocuring 3D printing composition according to the present invention.

[0187] In the present invention, the medical structure may refer to the aforementioned medical product, and the industrial structure may refer to the aforementioned industrial product.

[0188] Hereinafter, the composition and effects of the present invention will be described in more detail through examples and experimental examples. These examples and experimental examples are intended solely to illustrate the present invention, and the scope of the present invention is not limited by these examples and experimental examples.

[0189] [Example]

[0190] Composition (phr) PCL-PGMAUDMAIBOAIrgacure 819 Example 1 100-1001 Example 2 100-801 Example 3 100-501 Example 4 10030501 Example 5 10050501 Example 6 100100501 Example 7 100150501

[0191] [Comparative example]

[0192] Composition (phr) PCL-PGMAUDMAIBOAIrgacure 819 Comparative Example 1100-451 Comparative Example 2100200501

[0193] A resin-based polymer composition was prepared by mixing a caprolactone glycidyl methacrylate copolymer having a six-arm structure (6 arm 94PCL-06PGMA, INNOSELF 1-6, TMDLAB co., Ltd), a reactive oligomer, diurethane dimethacrylate (UDMA, Sigma-Aldrich), a reactive diluent, isobornyl acrylate (IBOA, TCI chemical), and a photoinitiator, Irgacure 819 (Sigma Aldrich), in the ratios shown in Table 1 or Table 2. In Table 1 and Table 2, phr is the ratio of the added weight to the polymer weight (here, PCL-PGMA).

[0194] [Experimental Example 1]

[0195] 3D printing output performance comparison

[0196] 3D printing using a photocuring method was performed using the polymer compositions of the examples and comparative examples. 3D printing was performed using Anycubic's Photonmono X, and the wavelength of the lamp used was 405 nm.

[0197] As a result of the 3D printing experiment, in the case of the examples, it was confirmed that structures in the designed form could be printed in all tested compositions. However, in Comparative Example 1, normal structure printing was not achieved, and it was confirmed that normal structure printing was possible only when the reactive diluent was included in an amount of at least 50 wt% relative to the copolymer (Figs. 1 and 2).

[0198] [Experimental Example 2]

[0199] Thermal characteristics

[0200] In order to confirm the thermal properties of the sample printed through Experimental Example 1, the melting temperature was measured within the temperature range of -70 to 200℃ using Differential Scanning Calorimetry (DSC).

[0201] As a result, as shown in Table 3, in the case of the examples, the melting temperature was observed in the range of 35 - 42℃, but in the case of Comparative Example 1, it was difficult to determine the melting temperature because the structure was not printed, and in the case of Comparative Example 2, the melting temperature was confirmed to be 52℃, which is significantly higher than the body temperature range. From the above results, it was confirmed that for 3D printing of medical materials for application in the body, the reactive oligomer should be combined so as not to exceed 200 wt% of the copolymer.

[0202] Melting temperature (℃) Example 1 35.4 Example 2 35.5 Example 3 36.7 Example 4 39.9 Example 5 40.3 Example 6 41.4 Example 7 42.6 Comparative Example 252.3

[0203] [Experimental Example 3]

[0204] 4D characteristics

[0205] In order to confirm the 4D characteristics of the examples and comparative examples, each sample 3D printed in Experimental Example 1 was stretched to 100%, the stretched sample was exposed to a temperature of 40 - 45°C, and then the shape recovery ability (%) was confirmed according to Equation (1).

[0206] ------------ Equation (1)

[0207] As a result, it exhibited shape recovery ability as in Fig. 3, and in particular, as in Table 4, in the case of the example, it exhibited shape recovery ability of 80% or more at all tensile ratios tested. On the other hand, in the case of comparative example 2, the recovery ability at 40-45℃ was at the level of 50%, showing 4D characteristics that were significantly lower than in the example.

[0208] ClassificationInitial length (mm)Deformation length (mm)Recovery length (mm)Shape recovery ability (%)Example 1102010.892Example 2102010.793Example 3102010.496Example 4102011.288Example 5102011.585Example 6102011.684Example 7102011.882Comparative example 2102014.654

[0209] [Experimental Example 4]

[0210] Cross-linking properties

[0211] In order to confirm the crosslinking characteristics of the sample of Example 3 printed through Experimental Example 1, the manufactured sample was placed in chloroform to check the degree of solubility.

[0212] As a result, it was confirmed that a network was formed by a cross-linking reaction, as shown in Fig. 4, and that it existed in a solid form without being dissolved in chloroform solvent.

[0213] While specific aspects of the present invention have been described in detail above, it will be apparent to those skilled in the art that these specific descriptions merely represent preferred embodiments and are not intended to limit the scope of the present invention. Therefore, the substantial scope of the present invention is defined by the appended claims and their equivalents.

[0214] The national research and development projects that supported this invention are as follows.

[0215] [Project ID] 1711200487

[0216] [Assignment Number] 00302125 (RS-2023-00302125)

[0217] [Ministry Name] Ministry of Science and ICT

[0218] [Name of Project Management (Specialist) Institution] National Research Foundation of Korea

[0219] [Research Project Name] STEAM Research (Future Convergence Technology Development Project)

[0220] [Research Project Title] Development of Source Technology for Energy-Responsive Self-Structured Medical Materials Applicable to Biosystems

[0221] [Name of the project performing organization] TMD Lab Co., Ltd.

[0222] Research Period: September 1, 2023 - December 31, 2027

Claims

A photocurable 3D printing composition comprising a copolymer comprising a lactone monomer and glycidyl methacrylate, a photoinitiator, and a reactive diluent. In the first paragraph, the photocurable 3D printing composition is at least one selected from the group consisting of the following chemical formulas (1) to (4): Chemical formula (1) In the above chemical formula (1), R1, R2 and R3 are each independently hydrogen (H) or an alkyl group having 1 to 6 carbon atoms, m and n are integers from 1 to 20, independently of each other, A, B1 and B2 are independently oxygen (O) or sulfur (S), x and y represent the mole % of repeating units, x+y is 100, and x is between 70 and 99; Chemical formula (2) In the above chemical formula (2), x is an integer from 1 to 20, m and n represent the mole % of repeating units, m+n is 100, and m is between 70 and 99; Chemical formula (3) In the above chemical formula (3), x and y are integers from 1 to 20, independently of each other, m and n represent the mole % of repeating units, m+n is 100, m is 70 to 99, Chemical formula (4) In the above chemical formula (4), x and y are integers from 1 to 20, independently of each other, m and n represent the mole % of repeating units, m+n is 100, and m is between 70 and 99. A photocurable 3D printing composition in claim 1, wherein the reactive diluent is at least one selected from the group consisting of isobornyl acrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, N-methylpyrrolidone, N-vinylpyrrolidone, ethyl acetate, benzyl alcohol, chloroform, and tetrahydrofuran. A photocurable 3D printing composition in claim 1, wherein the reactive diluent is contained in an amount of 50 to 100 parts by weight relative to 100 parts by weight of the copolymer. A photocurable 3D printing composition according to claim 1, wherein the composition further comprises a reactive oligomer. In claim 5, the reactive oligomer is a photocurable 3D printing composition, wherein at least one selected from the group consisting of diurethane dimethacrylate, epoxy oligomer, epoxidized soybean oil, acrylated epoxidized soybean oil, epoxy methacrylate, amine modified acrylate, polyester acrylate, and liquid silicone rubber. A photocurable 3D printing composition in claim 5, wherein the reactive oligomer is contained in an amount of 0 to 150 parts by weight relative to 100 parts by weight of the copolymer. A photocurable 3D printing composition in claim 1, wherein the photoinitiator is at least one selected from the group consisting of Irgacure, Darocure, LAP (Lithium phenyl-2,4,6-trimethylbenzoylphosphinate), TPO (Diphenyl(2,4,6-Trimethylbenzoyl)Phosphine), and TPO-L (Ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate). A photocurable 3D printing composition in claim 1, wherein the photoinitiator is included in an amount of 0.5 to 3.0 parts by weight relative to 100 parts by weight of the copolymer. A photocurable 3D printing output product comprising a composition according to any one of claims 1 to 9, 3D printed. In claim 10, the composition is a photocurable 3D printing output that exhibits 4D characteristics through a photocrosslinking reaction by light energy irradiation. In claim 11, the output is a photocurable 3D printing output having a shape restorability of 60% or more at a temperature of 30 to 50°C. In claim 10, the output is a photocurable 3D printing output that is a medical material or an industrial material. A method for manufacturing a photocurable 3D printing composition of claim 1, comprising the following steps: (a) mixing a copolymer comprising a lactone monomer and glycidyl methacrylate with a reactive diluent; and (b) A step of mixing a photoinitiator into the mixture of step (a). A method for manufacturing a photocurable 3D printing composition, wherein step (a) further comprises mixing a reactive oligomer in the 14th paragraph. In claim 14, the copolymer is at least one selected from the group consisting of chemical formulas (1) to (4), a method for producing a photocurable 3D printing composition: Chemical formula (1) In the above chemical formula (1), R1, R2 and R3 are each independently hydrogen (H) or an alkyl group having 1 to 6 carbon atoms, m and n are integers from 1 to 20, independently of each other, A, B1 and B2 are independently oxygen (O) or sulfur (S), x and y represent the mole % of repeating units, x+y is 100, and x is between 70 and 99; Chemical formula (2) In the above chemical formula (2), x is an integer from 1 to 20, m and n represent the mole % of repeating units, m+n is 100, and m is between 70 and 99; Chemical formula (3) In the above chemical formula (3), x and y are integers from 1 to 20, independently of each other, m and n represent the mole % of repeating units, m+n is 100, m is 70 to 99, Chemical formula (4) In the above chemical formula (4), x and y are integers from 1 to 20, independently of each other, m and n represent the mole % of repeating units, m+n is 100, and m is between 70 and 99. A method for manufacturing a photocurable 3D printing composition in claim 14, wherein the reactive diluent is at least one selected from the group consisting of isobornyl acrylate, triethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, N-methylpyrrolidone, N-vinylpyrrolidone, ethyl acetate, benzyl alcohol, chloroform, and tetrahydrofuran. A method for producing a photocurable 3D printing composition according to claim 15, wherein the reactive oligomer is at least one selected from the group consisting of diurethane dimethacrylate, epoxy oligomer, epoxidized soybean oil, acrylated epoxidized soybean oil, epoxy methacrylate, amine modified acrylate, polyester acrylate, and liquid silicone rubber. A method for producing a photocurable 3D printing composition in claim 14, wherein the photoinitiator is at least one selected from the group consisting of Irgacure, Darocure, LAP (Lithium phenyl-2,4,6-trimethylbenzoylphosphinate), TPO (Diphenyl(2,4,6-Trimethylbenzoyl)Phosphine), and TPO-L (Ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate). A method for producing a photocurable 3D printing composition, wherein the reactive diluent is mixed in an amount of 50 to 100 parts by weight relative to 100 parts by weight of the copolymer in claim 14. A method for producing a photocurable 3D printing composition, wherein the reactive oligomer is mixed in an amount of 0 to 150 parts by weight relative to 100 parts by weight of the copolymer in the 15th paragraph. A method for producing a photocurable 3D printing composition, wherein the photoinitiator is mixed in an amount of 0.5 to 3.0 parts by weight relative to 100 parts by weight of the copolymer in the 14th paragraph. A photocurable 3D printing method comprising the following steps: (a) a step of preparing a photocurable 3D printing composition according to any one of claims 14 to 22; and (b) A step of 3D printing by irradiating light energy to the photocurable 3D printing composition. A photocuring 3D printing method in claim 23, wherein step (b) is irradiating light energy having a wavelength of 365 nm to 405 nm. In claim 23, the photocuring 3D printing method is applied to a method for manufacturing medical or industrial structures. A photocurable 3D printing composition according to any one of claims 1 to 9 or a photocurable 3D printing output according to claim 10, for use in the manufacture of medical or industrial structures. A photocurable 3D printing composition according to any one of claims 1 to 9 or a photocurable 3D printing output according to claim 10, for use in the manufacture of medical or industrial structures. A medical or industrial structure manufactured by the photocuring 3D printing method of Article 23.

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