Photocurable composition for manufacturing patient-customized biliary stent by using 3D printer, and patient-customized biliary stent using same

Abstract

The present invention relates to a photocurable composition for manufacturing a patient-customized biliary stent by using a 3D printer, and a patient-customized biliary stent using same. A conventional photocurable composition for a 3D printer is hard and cannot be used as a biliary stent, but the photocurable composition for a 3D printer, of the present invention, can exhibit physical properties at levels enabling use as a biliary stent, and can be manufactured, using biocompatible material properties, as a stent customized for a patient requiring a biliary stent procedure.

Description

Photocurable composition for manufacturing a patient-specific biliary stent using a 3D printer and a patient-specific biliary stent using the same

[0001] The present invention relates to a photocurable composition for manufacturing a patient-specific biliary stent using a 3D printer and a patient-specific biliary stent using the same.

[0002] Stents, which are widely used in medicine, are utilized in interventional procedures to restore patency to narrowed areas within the body where the lumen through which blood, food, and body fluids travel is narrowed due to atherosclerosis, thrombosis, benign and malignant tumors, post-surgical complications, or pathological causes. This procedure began in the 1980s and continues to be performed as an important procedure to this day.

[0003] These stents are broadly classified into non-vascular and vascular stents, and self-expanding stents are well known, which generally have a metal or polymer mesh structure and possess inherent elasticity, contracting when an external force is applied and returning to their original state when the external force is removed.

[0004] The aforementioned stent procedures are broadly classified into vascular stent implantation and non-vascular stent implantation.

[0005] The former vascular stent insertion procedure is known as a method of expanding narrowed blood vessels by making a hole of about 3mm to 4mm in the thigh, pushing a thin tube called a 'catheter' up the femoral artery to the site of the lesion, and then inserting a stent.

[0006] The latter non-vascular stent insertion procedure is known as a surgical method in which a balloon catheter tube is inserted internally to expand the narrowed area and inflate the balloon in order to secure food intake when the esophagus becomes blocked or progresses due to stenosis caused by cancerous tissue, etc., making oral food intake impossible.

[0007] Stents used in the aforementioned two procedures have been disclosed to date with improved stent functions based on various structures.

[0008] Unless for a special purpose, such stents typically form a hollow cylindrical body of a predetermined length having multiple rhombus-shaped spaces (cells) by crossing superelastic shape memory alloy wires or stainless steel wires at different locations or connecting crooked and ribbed sections in a hook shape.

[0009] Meanwhile, to expand a narrowed lumen caused by stenosis or other lesions, a stent procedure is known in which the stent is fixed in place by being caught on various sphincter tissues within the human organ, and the procedure is performed on the bile duct, etc.

[0010] In other words, as mentioned above, conventional stents have been developed in various structures to improve function, but development into customized stents tailored to the specific type of procedure required by the patient has not progressed. This may be due to material limitations, so it is necessary to devise measures to resolve this issue.

[0011] [Prior Art Literature]

[0012] [Patent Literature]

[0013] KR 10-1691121 B1

[0014] The objective of the present invention is to provide a photocurable composition for manufacturing a patient-specific biliary stent using a 3D printer and a patient-specific biliary stent using the same.

[0015] Another objective of the present invention is to provide a photocurable composition for a 3D printer that, unlike conventional photocurable compositions for 3D printers which are rigid and cannot be used as biliary duct stents, can exhibit physical properties suitable for use as a biliary duct stent and, due to its biocompatible material characteristics, can be manufactured as a customized stent for patients requiring biliary duct stent procedures.

[0016] Another objective of the present invention is to provide a patient-specific biliary stent that can be manufactured into a soft biliary stent using a 3D printer by utilizing a photocurable composition for 3D printers and can suppress the formation of biofilms, thereby eliminating the inconvenience of having to repeat stent procedures due to blockage of the stent.

[0017] To achieve the above-mentioned objective, the present invention may relate to a photocurable composition comprising an oligomer represented by the following chemical formula 1, wherein the oligomer has a number average molecular weight of 4,000 to 5,000 and may be a photocurable composition for manufacturing a patient-specific biliary stent using a 3D printer:

[0018] [Chemical Formula 1]

[0019]

[0020] [Chemical Formula 2]

[0021]

[0022] [Chemical Formula 3]

[0023]

[0024] [Chemical Formula 4]

[0025]

[0026] [Chemical Formula 5]

[0027]

[0028] [Chemical Formula 6]

[0029]

[0030] Here,

[0031] n is an integer from 1 to 100, and

[0032] m is an integer from 1 to 50, and

[0033] A, B, C, and D are identical or different from each other and are repeating units selected independently from the group consisting of compounds represented by chemical formulas 2 to 6, and

[0034] a, b, c, and d are identical or different from each other, and each is independently an integer from 1 to 30, and

[0035] R1 and R2 may be identical or different from each other and may each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

[0036] In addition, the oligomer may have a viscosity of 1,500 cps to 9,000 cps.

[0037] In addition, the oligomer may have a weight average molecular weight of 7,000 to 8,000.

[0038] In addition, the photocurable composition comprises a monomer, and the monomer may be selected from the group consisting of trimethylolpropane formal acrylate (CTFA), 2-hydroxyethyl acrylate (2-HEA), isobornyl acrylate (IBOA), and mixtures thereof.

[0039] Another invention for achieving the above-mentioned purpose may be a patient-specific biliary stent comprising the above-mentioned photocurable composition.

[0040] In addition, the bile duct stent can be printed by a 3D printer using the photocurable composition.

[0041] The present invention relates to a 3D printer photocurable composition that, unlike conventional 3D printer photocurable compositions which are rigid and cannot be used as biliary duct stents, can exhibit physical properties suitable for use as a biliary duct stent and, due to its biocompatible material characteristics, can be manufactured as a customized stent for patients requiring biliary duct stent procedures.

[0042] Figure 1 is the result of measuring the mechanical properties of a specimen using a photocurable composition according to one embodiment of the present invention.

[0043] Figure 2 is a photograph of a biliary stent manufactured using a photocurable composition according to one embodiment of the present invention.

[0044] The present invention relates to a photocurable composition for manufacturing a patient-specific biliary duct stent using a 3D printer, comprising an oligomer represented by the following chemical formula 1, wherein the oligomer has a number average molecular weight of 4,000 to 5,000:

[0045] [Chemical Formula 1]

[0046]

[0047] [Chemical Formula 2]

[0048]

[0049] [Chemical Formula 3]

[0050]

[0051] [Chemical Formula 4]

[0052]

[0053] [Chemical Formula 5]

[0054]

[0055] [Chemical Formula 6]

[0056]

[0057] Here,

[0058] n is an integer from 1 to 100, and

[0059] m is an integer from 1 to 50, and

[0060] A, B, C, and D are identical or different from each other and are repeating units selected independently from the group consisting of compounds represented by chemical formulas 2 to 6, and

[0061] a, b, c, and d are identical or different from each other, and each is independently an integer from 1 to 30, and

[0062] R1 and R2 may be identical or different from each other and may each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

[0063] Hereinafter, embodiments of the present invention are described in detail so that those skilled in the art can easily implement the invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0064] A biliary stent is an interventional procedure of the pancreaticobiliary system in which a stent is inserted to relieve biliary obstruction caused by biliary or pancreatic cancer. Biliary obstruction refers to the narrowing or blockage of the bile duct, which carries bile produced in the liver to the duodenum, by gallstones or tumors.

[0065] The most characteristic symptom of biliary atresia is obstructive jaundice, which is accompanied by upper abdominal pain, fever, and severe itching. If symptoms of biliary atresia appear, biliary drainage, biliary dilation, or biliary stenting must be performed, or surgical intervention must be carried out, to ensure that bile flows properly from the biliary tract to the digestive organs.

[0066] Among these, stent insertion can improve the quality of life by enhancing the effects of anticancer and radiation therapy while reducing the occurrence of complications such as jaundice and sepsis. If biliary obstruction occurs during anticancer treatment, severe jaundice develops, and since anticancer treatment must be stopped in such cases, biliary stenting is effective in improving the patient's symptoms and shortening the treatment period.

[0067] With the introduction of endoscopic retrograde cholangiopancreatography (ERCP) for the diagnosis and treatment of bile duct and pancreatic diseases, palliative treatment of endoscopic bile duct obstruction has become possible. Bile duct stenosis or obstruction can be treated with endoscopic retrograde biliary drainage (ERBD) using ERCP. However, just like stent insertion in other parts of the gastrointestinal tract, this drainage procedure does not restore the normal physiological state prior to the onset of the disease; consequently, various problems inevitably arise with the stent, which serves as an alternative pathway for bile.

[0068] To date, stents introduced for the purpose of bile drainage are broadly classified into two types: those made of plastic and those made of metal.

[0069] When selecting a stent, the operator must consider 1) the stent's bile duct drainage effect and duration of patency, 2) whether the stent is benign or malignant, 3) the location of the stenosis, 4) ease of procedure, 5) the patient's condition and lifespan, and 6) cost-effectiveness.

[0070] However, it can be inserted using an endoscope to drain bile from malignant or benign bile duct stenosis and has the advantages of being relatively inexpensive and easy to remove, but the inner diameter is very small and fixed compared to SEMS, so jaundice and cholangitis may recur as the lumen becomes blocked by bacterial biofilm.

[0071] First, when comparing plastic stents and SEMS, most studies on endoscopic treatment of malignant bile duct stenosis recommend the insertion of SEMS rather than plastic stents, and considering the cost-effectiveness in the domestic context, SEMS is more advantageous for reducing medical costs when the patient's life expectancy is expected to be 3 months or more.

[0072] The selection of an appropriate stent among various SEMS requires an individualized approach that considers the physical characteristics and pros and cons of the product, as well as the characteristics of the patient's bile duct structure and the location or characteristics of the lesion.

[0073] In other words, to be used as a biliary stent, even in the case of SEMS, a stent suitable for each patient must be selected and used. However, in the case of SEMS, using a stent suitable for each patient is limited to adjusting the length or selecting a stent that differs in the degree of shortening after insertion; an individualized approach that considers the structural characteristics of the bile duct and the location or characteristics of the lesion for each patient is virtually impossible.

[0074] In addition, it is known that in the case of benign stenosis, it is appropriate to insert a plastic stent and replace it regularly every three months.

[0075] As mentioned above, in order to use a biliary stent, it is necessary to adjust the shape and length by considering the structure and characteristics of the bile duct and the location and characteristics of the lesion for each patient; however, current metal stents cannot fully adjust the shape in this way.

[0076] Accordingly, the present invention aims to provide a biliary stent printed using a patient-specific 3D printer that can replace existing biliary stents.

[0077] To manufacture such a patient-specific biliary stent, a photocurable composition comprising an oligomer represented by the following chemical formula 1 may be used, wherein the oligomer may be a photocurable composition for manufacturing a patient-specific biliary stent using a 3D printer having a number average molecular weight of 4,000 to 5,000:

[0078] [Chemical Formula 1]

[0079]

[0080] [Chemical Formula 2]

[0081]

[0082] [Chemical Formula 3]

[0083]

[0084] [Chemical Formula 4]

[0085]

[0086] [Chemical Formula 5]

[0087]

[0088] [Chemical Formula 6]

[0089]

[0090] Here,

[0091] n is an integer from 1 to 100, and

[0092] m is an integer from 1 to 50, and

[0093] A, B, C, and D are identical or different from each other and are repeating units selected independently from the group consisting of compounds represented by chemical formulas 2 to 6, and

[0094] a, b, c, and d are identical or different from each other, and each is independently an integer from 1 to 30, and

[0095] R1 and R2 may be identical or different from each other and may each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

[0096] The above-mentioned photocurable oligomer comprises a urethane acrylate structure as a main chain, wherein a photocurable functional group is bonded to the urethane structure, and the compound is characterized by including soft functional groups and hard functional groups.

[0097] Due to the soft functional groups included in the above photocurable composition, the output exhibits flexible properties, and due to the hard functional groups, it can also exhibit heat resistance.

[0098] The above photocurable oligomer may have a number average molecular weight (Mn) of 4,000 to 5,000. Additionally, the above photocurable oligomer may have a weight average molecular weight (Mw) of 7,000 to 8,000. By synthesizing to have a number average molecular weight and a weight average molecular weight within the above ranges, soft properties can be exhibited.

[0099] In addition, to enable the exhibiting of such soft properties, the photocurable oligomer may have a viscosity of 1,500 cps to 9,000 cps. By using an oligomer having viscosity characteristics within the above range and reacting it with the photocurable monomer described below, it is possible to manufacture a stent having soft properties.

[0100] The above A, B, and D may be identical or different from each other and may each be a repeating unit independently selected from a compound represented by chemical formula 2 or 3.

[0101] The above C may be a repeating unit selected from the group consisting of compounds represented by chemical formulas 4 to 6.

[0102] Specifically, the photocurable oligomer represented by Chemical Formula 1 above can be prepared by a method for synthesizing a urethane acrylate series. Basically, the process proceeds as a stepwise polymerization reaction between a diol and a diisocyanate, and an acrylic monomer without reaction sites was used as a suspension to prevent gelation of the material as the molecular weight increases during the polymerization process. As usable acrylic monomers, the monomers used in the synthesis of the oligomer of the present invention may be isobornyl acrylate, cyclic trimethylolpropane formal acrylate, lauryl acrylate, lauryl methacrylate, 3,5,3-trimethelhexyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, etc.

[0103] More specifically, a diol was pre-added to stabilize the monomer base used as a primary monomer, and a diisocyanate was added. As the urethane reaction proceeded, reaction heat was generated, the urethane chain lengthened, and the molecular weight increased.

[0104] As the molecular weight increases, the viscosity of the material may also increase. If the increase in molecular weight proceeds rapidly, the temperature rises sharply, causing the urethane reaction to proceed even faster. Consequently, the oligomer gels before reaching a sufficient molecular weight, making it unusable as a material. Accordingly, to prevent such a reaction, the present invention uses a solvent selected from the group consisting of isobornyl acrylate, cyclic trimethylolpropane formal acrylate, lauryl acrylate, lauryl methacrylate, 3,5,3-trimethylhexyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, and mixtures thereof as the solvent for introducing the diol. The above solvent does not participate in the reaction and is used to control the reaction rate of the material and to prevent a rapid increase in viscosity due to the increase in molecular weight. In addition, the monomers for synthesizing the oligomers of the present invention must not have functional groups capable of reactive urethane reactions, such as hydroxyl groups or urethane groups. Under the above conditions, it is possible to produce oligomers with excellent mass production and process stability according to the present invention.

[0105] In addition, the equivalent ratio of the diol to the diisocyanate was set such that the equivalent weight of the diisocyanate was higher than that of the diol, thereby inducing the oligomer terminals to exist as isocyanate groups. During the reaction process, a reaction catalyst including a Zn-based catalyst may be used. The catalyst may or may not be included. The catalyst is included to accelerate the reaction; although the reaction can proceed even without its essential inclusion, the reaction can be carried out by adding only a very small amount.

[0106] After the temperature increase was stopped following the termination of the urethane reaction, 2-hydroxy acrylate and 2-hydroxy methacrylate were added via a drop method to end-cap the oligomer ends, thereby end-capping the material ends.

[0107] The diol used for the preparation of the above oligomer is as follows:

[0108]

[0109] In addition, the diisocyanate for reacting with the above diol is as follows:

[0110]

[0111]

[0112] In addition, monomers that may be included to terminate the above urethane reaction or increase the molecular weight are as follows:

[0113]

[0114]

[0115]

[0116]

[0117] The compound represented by Chemical Formula 1 prepared by the above manufacturing method may be selected from the group consisting of the following compounds:

[0118]

[0119] Here,

[0120] t is an integer from 1 to 100, and

[0121] s is an integer from 1 to 50.

[0122] Additionally, preferably, the above t and s are the same or different from each other and can each be independently selected as integers with a number average molecular weight of 4,000 to 5,000 of the oligomer.

[0123] The above photocurable composition may comprise 50 to 70 weight percent of the oligomer and the remainder being a reactive monomer. When mixed and used within the above range, not only can it be manufactured as a printed object using a 3D printer, but the manufactured printed object may also exhibit excellent biocompatibility and softness characteristics suitable for use as a stent. The above 3D printer is a DLP type 3D printer.

[0124] The above reactive monomer may be, specifically, an acrylate-based monomer.

[0125] More specifically, the acrylate-based monomer may be selected from the group consisting of trimethylolpropane formal acrylate (CTFA), 2-hydroxyethyl acrylate (2-HEA), isobornyl acrylate (IBOA), and mixtures thereof.

[0126] The above photocurable composition comprises an oligomer and a reactive monomer, and may be included in an amount of 40% to 50% by weight of the oligomer and 50% to 60% by weight of the reactive monomer. When mixed and used within the above range, it may exhibit suitable mechanical properties for use as a biliary stent.

[0127] In addition, the above-mentioned reactive monomer may include one or two types. When two types are included,

[0128] In addition to the oligomers and reactive monomers described above, the above-described photocurable composition may further include a photoinitiator, a stabilizer, and other additives.

[0129] The above photoinitiator may use BP, TPO, DCP, BPO, DPPO, etc., but preferably DPPO (2-hydroxy-2-methylpropiophenone) may be used. However, it is not limited to the above examples, and any photoinitiator capable of producing a photocurable composition may be used without limitation.

[0130] The above stabilizer may be selected from the group consisting of tertiary amines such as diethylethanolamine and trihexylamine, hindered amines, organic phosphates, and hindered phenols, but is not limited to the above examples, and any stabilizer capable of producing a photocurable composition may be used without limitation.

[0131] The above other additives may include conventional additives, such as leveling agents, slip agents, or stabilizers, to improve thermal and oxidation stability, storage stability, surface characteristics, flow characteristics, and process characteristics.

[0132] A patient-specific biliary stent according to another embodiment of the present invention may include the photocurable composition.

[0133] More specifically, the bile duct stent can be printed by a 3D printer using the photocurable composition.

[0134] As described above, conventional biliary stents are manufactured from metal or plastic materials without taking into account the shape, condition, or disease state of the patient's bile duct. Accordingly, the method may involve selecting from standardized shapes and adjusting the length to suit the patient's condition.

[0135] However, the above method has a problem in that it cannot select a shape, etc., optimized for the patient's bile duct condition.

[0136] Accordingly, the present invention makes it possible to provide an optimal biliary stent by utilizing the above-described photocurable composition, taking into account the patient's biliary duct condition and current disease state.

[0137] In other words, the biliary duct stent manufactured using the photocurable composition of the present invention is characterized by the fact that, as a biocompatible material, it is not only suitable for use as a biliary duct stent, but also allows for customized production for the patient by enabling it to be manufactured in an optimal shape that takes into account the patient's condition.

[0138] More specifically, the above patient-specific stent is printed by a 3D printer and then undergoes a post-curing step.

[0139] More specifically, the post-curing step can increase the conversion rate of unreacted monomers within the 3D-printed stent by irradiating the printed stent with UV light under an inert gas atmosphere.

[0140] If the curing process is carried out in an inert gas environment, not only is the curing speed of the stent improved, but its mechanical properties can also be enhanced.

[0141] The above inert gas is selected from the group consisting of nitrogen, argon, helium, krypton, neon, and mixtures thereof, preferably nitrogen, but is not limited to the above examples, and any gas capable of blocking contact with oxygen as an inert gas may be used without limitation.

[0142]

[0143] Preparation Example

[0144] Preparation of a photocurable composition

[0145] Example 1

[0146] Isobornyl acrylate was used as a solvent, polypropylene glycol, cyclohexanedimethanol, and BHT were added and stirred at 10 to 200 rpm at 10 to 50°C, isophorone diisocyanate was added and stirred at the same temperature conditions with the stirring speed varied from 50 to 200 rpm. Subsequently, HEMA was added and stirred at 150 to 500 rpm at 50 to 250°C to prepare an oligomer.

[0147] The intermediate compounds produced by the above reaction are as follows:

[0148]

[0149] The oligomer finally produced by reacting the above intermediate compound is as follows:

[0150]

[0151] The results of the analysis of the oligomers of Examples 1 to 5 above are summarized in Table 1 below:

[0152] Example 1 GPCMn 4179 Mw 6944 PDI 1.68 NMRA (6.44) OB (5.89) OC (5.61) O (39.0) D (4.91) O (87.9) E (6.48) XF (6.49) XG (3.41) O Viscosity (cps) 1,000

[0153] Preparation Example 2

[0154] The oligomer of Example 1 was heated in a 60°C oven for 12 hours and mixed with the monomer. Subsequently, 1% by weight of DPPO was mixed as a photoinitiator relative to the total weight of the mixture of the oligomer and monomer, and the mixture was mixed and degassed using a paste mixer.

[0155] The above monomer used was trimethylolpropane formal acrylate (CTFA) or 2-hydroxyethyl acrylate (2-HEA).

[0156] The weight ratio of the above photocurable composition is as follows:

[0157] Test 1Test 2Test 3Test 4Test 5Synthesis oligomer8075504040CTFA - - 10202-HEA2035505040

[0158] (weight %)

[0159] Experimental Example

[0160] Preparation of specimens

[0161] Using the photocurable compositions of Test 1 to Test 5 above, cubic specimens with width, length, and height of 5 cm, 5 cm, and 1 cm, respectively, were printed using an LCD 3D printer (Photon Mono 2, Anycubic, Shenzhen, China), and then post-cured by irradiating with UV light for 20 minutes under nitrogen conditions to prepare the specimens. The mechanical properties of the specimens were measured under the following conditions.

[0162] - Output Equipment: UNIZ Nbee 100um

[0163] - Inspection Standard: ASTM D638 Type 5 (Thickness: 0.5mm / Speed: 5mm / min)

[0164] The test results are as shown in Figure 1.

[0165] According to Figure 1, the specimens of Test 1 and Test 2 showed high tensile strength values ​​but low ductility values. On the other hand, it was confirmed that the specimens of Test 3 to Test 5 showed lower tensile strength values ​​compared to the specimens of Test 1 and Test 2, but exhibited superior ductility characteristics.

[0166] For use as a bile duct stent, the photocurable compositions of Test 3 to Test 5 are more suitable in that they have low tensile strength, which indicates the degree of stiffness, and excellent ductility.

[0167] The product produced as a bile duct stent using the photocurable composition of Test 5 above is as shown in Fig. 2.

[0168] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims also fall within the scope of the present invention.

[0169]

[0170] This application was filed with the support of the following tasks:

[0171] 1. Project ID: 2410012515

[0172] 2. Project No.: 20023781

[0173] 3. Ministry Name: Ministry of Trade, Industry and Energy

[0174] 4. Project Management Agency: Korea Institute of Industrial Technology Planning and Evaluation

[0175] 5. Research Project Name: Bioindustry Technology Development

[0176] 6. Research Project Title: Development of Symbiotic Biocompatible Medical Device Materials and Commercialization Technology for Patient-Specific Direct-Printed Biliary Stents and Orthodontic Appliances

[0177] 7. Organizing Institution: Yonsei University Industry-Academic Cooperation Foundation

[0178] 8. Research Period: April 1, 2023 – December 31, 2027

[0179] The present invention relates to a photocurable composition for manufacturing a patient-specific biliary stent using a 3D printer and a patient-specific biliary stent using the same.

Claims

1. A photocurable composition comprising an oligomer represented by the following chemical formula 1, and The above oligomer has a number average molecular weight of 4,000 to 5,000. Photocurable composition for manufacturing patient-specific biliary stents using a 3D printer: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] Here, n is an integer from 1 to 100, and m is an integer from 1 to 50, and A, B, C, and D are identical or different from each other and are repeating units selected independently from the group consisting of compounds represented by chemical formulas 2 to 6, and a, b, c, and d are identical or different from each other, and each is independently an integer from 1 to 30, and R1 and R2 may be identical or different from each other and may each be independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 30 carbon atoms.

2. In Paragraph 1, The above oligomer has a viscosity of 1,500 cps to 9,000 cps. Photocurable composition for manufacturing patient-specific biliary stents using a 3D printer.

3. In Paragraph 1, The above oligomer has a weight-average molecular weight of 7,000 to 8,000. Photocurable composition for manufacturing patient-specific biliary stents using a 3D printer.

4. In Paragraph 1, The above photocurable composition includes a monomer, and The above monomer is selected from the group consisting of trimethylolpropane formal acrylate (CTFA), 2-hydroxyethyl acrylate (2-HEA), isobornyl acrylate (IBOA), and mixtures thereof. Photocurable composition for manufacturing patient-specific biliary stents using a 3D printer.

5. A photocurable composition according to paragraphs 1 to 4 Patient-specific biliary stent.

6. In Paragraph 5, The above biliary stent is printed by a 3D printer using the above photocurable composition Patient-specific stent.

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