Photocurable polymer composition for 3D printer

Abstract

This invention relates to a photocurable polymer composition for 3D printers, comprising a UV-curable polyurethane oligomer, a photoinitiator, a silane coupling agent, oligomers, and a stabilizer. According to the aforementioned photocurable polymer composition for 3D printers, 3D printed outputs with excellent physical properties such as thermal properties, strength, elastic modulus, and elongation can be manufactured, and 3D printed outputs that can restore their original shape even if deformed through use.

Description

[0001] This application is a divisional application of the application filed on June 14, 2019, with application number 201980029997.4 and invention title "Photocurable Polymer Composition for 3D Printers". Technical Field

[0002] This invention relates to a photocurable polymer composition for 3D printers. More specifically, it is a photocurable polymer suitable for 3D printing. By utilizing it for 3D printing, it is possible to produce 3D printed outputs with excellent physical properties such as thermal properties, strength, elastic modulus and elongation, and shape recovery. Background Technology

[0003] 3D printers operate on the principle of 3D printing, which allows physical objects to be formed in a 3D manner. Research continues on resin compositions used for 3D printing, which are the inks used to enable such printers to form physical objects in 3D.

[0004] The advantages of 3D printing are that even when producing only one product, the production cost is relatively low, and it allows for the creation of products in any shape. In existing model-making technologies, the cost of producing a single product is very high because it involves creating a mold and then using that mold. However, 3D printing technology produces products by layering raw materials without the need for molds, making it ideal for producing a wide variety of products in small quantities.

[0005] Furthermore, 3D printing technology can easily produce products of even the most complex shapes, meaning that the types of products that can be manufactured using 3D printing technology are virtually limitless. Therefore, it is anticipated that 3D printing technology will revolutionize technological paradigms and lead industrial transformation in manufacturing, healthcare, IT, and many other fields.

[0006] Materials used in 3D printers should possess appropriate melting points and flowability to ensure smooth flow at the printer nozzle in FDM applications, and rapid curing speed to prevent deformation of the output after extrusion from the nozzle. Among thermoplastic resins, polylactic acid (PLA) and acrylonitrile butadiene styrene (ABS) are the most widely used filament materials with these properties. Polyetherimide (PEI) and polycarbonate (PC) are used for high heat resistance and high performance. However, there are limitations where the material properties differ significantly from those of materials manufactured from the original injection molding material, and there are no specific methods to further improve strength after output.

[0007] Polylactic acid (PLA), a common material in 3D printers, is an environmentally friendly resin made from corn starch. Even when it is filled with hot food or is bitten or sucked by children, it does not release any harmful substances such as endocrine disruptors or heavy metals, thus possessing stable practical properties.

[0008] Furthermore, while it shares the same characteristics as conventional plastics when used as a biodegradable polymer, it has the advantage of being 100% biodegradable by microorganisms upon disposal. Polylactic acid (PLA) has recently garnered attention regarding plastic waste issues due to its biodegradable properties, which are harmless to humans and the environment.

[0009] However, polylactic acid (PLA), despite its advantages, is limited in applications requiring a soft feel, low impact resistance, and low flexibility due to its high brittleness, poor impact resistance, and low flexibility. This necessitates the continuous development of new materials. Furthermore, the limitations of FDM technology make it difficult to manufacture precision and high-functionality parts. There is a need to invent photopolymer resins with high molecular weight polymer properties that offer high output quality and fast production speeds in industrial professional 3D printers.

[0010] In recent years, 3D printing technology has been applied to various medical fields, offering greater efficiency than existing cutting and processing methods in terms of production time, cost, and process. However, as mentioned above, the limitations of materials such as polylactic acid (PLA) used in 3D printers hinder their application in the medical field due to constraints on the physical properties of the output. Therefore, there is an urgent need to develop materials suitable for photopolymer 3D printers that can be used in a variety of medical applications.

[0011] Existing technical documents Patent documents Patent Document 1 KR 10-1831819 B1 Summary of the Invention The problem the invention aims to solve The purpose of this invention is to provide a photocurable polymer composition for use in 3D printers.

[0012] Another object of the present invention is to provide a photocurable polymer composition for 3D printers that can produce 3D printed outputs with excellent physical properties such as thermal properties, strength, elastic modulus and elongation.

[0013] Another object of the present invention relates to a photocurable polymer composition for a 3D printer capable of producing 3D printed outputs that can restore the shape even if the original shape is deformed by use.

[0014] Methods for solving problems To achieve the aforementioned objective, a photocurable polymer composition for 3D printers according to an embodiment of the present invention may comprise a UV-curable polyurethane oligomer represented by the following chemical formula 1, a photoinitiator, a silane coupling agent, an oligomer, and a stabilizer: [Chemical Formula 1]

[0015] [Chemical Formula 2]

[0016] in, A is a substituent represented by chemical formula 2. * indicates the bonded portion. R1 to R8 may be the same as or different from each other, and each is independently an alkylene group with 1 to 200 carbon atoms (substituted or unsubstituted), an aryl group with 6 to 200 carbon atoms (substituted or unsubstituted), a heteroaryl group with 5 to 200 nuclear atoms (substituted or unsubstituted), or a cycloalkylene group with 3 to 200 carbon atoms (substituted or unsubstituted). The substituted alkylene, substituted arylene, substituted heteroarylene, and substituted cycloalkylene are selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 1 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 5 to 60 carbon atoms, and heteroarylalkyl with 6 to 30 carbon atoms. The substituents are one or more of the following groups: alkoxy groups having 1 to 30 carbon atoms, alkylamino groups having 1 to 30 carbon atoms, aromaticamino groups having 6 to 30 carbon atoms, aralkylamino groups having 6 to 30 carbon atoms, heteroaromaticamino groups having 2 to 24 carbon atoms, alkylsilyl groups having 1 to 30 carbon atoms, arylsilyl groups having 6 to 30 carbon atoms, and aryloxy groups having 6 to 30 carbon atoms, and the substituents are the same as or different from each other when substituted by multiple substituents.

[0017] The weight-average molecular weight of the UV-curable polyurethane oligomer is between 10,000 and 1,000,000.

[0018] The photoinitiator is a compound represented by the following chemical formula 4: [Chemical Formula 4]

[0019] in, X1 is S, O, or N (R) 11 ), R9 to R 11 They may be the same as or different from each other, and each independently consists of hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms. The substituted alkyl and substituted cycloalkyl groups are substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 1 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 5 to 60 carbon atoms, heteroarylalkyl with 6 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, alkylamino with 1 to 30 carbon atoms, arylamino with 6 to 30 carbon atoms, arylalkylamino with 6 to 30 carbon atoms, heteroarylamino with 2 to 24 carbon atoms, alkylsilyl with 1 to 30 carbon atoms, arylsilyl with 6 to 30 carbon atoms, and aryloxy with 6 to 30 carbon atoms, and in the case of substitution by multiple substituents, they may be the same as or different from each other.

[0020] The oligomer can be selected from epoxy acrylate oligomers, H... 12The group consisting of dialkyl-bisglycidyl ethers (polymers of 4,4'-(1-methylethylidene)biscyclohexanol with chloromethyl oxirane), and mixtures thereof.

[0021] The stabilizer may be selected from the group consisting of 2,6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amines, organophosphates, hindered phenols, and mixtures thereof.

[0022] The polymer composition for 3D printers comprises a UV-curable polyurethane oligomer, and relative to 100 parts by weight of the UV-curable polyurethane oligomer, it may contain 1.5 to 15 parts by weight of a photoinitiator; 0.1 to 1.5 parts by weight of a silane coupling agent; 15 to 45 parts by weight of the oligomer; and 0.1 to 2 parts by weight of a stabilizer.

[0023] The present invention will now be described in more detail.

[0024] The 3D printing of this invention refers to the process of manufacturing three-dimensional objects by laminating materials using 3D digital data. In this specification, the 3D printing technologies described are mainly Digital Light Processing (DLP), Stereo Lithography Apparatus (SLA), and the PolyJet method, but it can be understood that other 3D printing technologies are also applicable.

[0025] The photocurable polymer of this invention is a substance that is cured by light irradiation, referring to a polymer that cross-links and polymerizes into a polymer network structure. This specification primarily describes UV light, but it is not limited to UV light and can also be applied to other types of light.

[0026] According to an embodiment of the present invention, a photocurable polymer composition for a 3D printer comprises a UV-curable polyurethane oligomer represented by the following chemical formula 1, a photoinitiator, a silane coupling agent, an oligomer, and a stabilizer: [Chemical Formula 1]

[0027] [Chemical Formula 2]

[0028] in, A is a substituent represented by chemical formula 2. * indicates the combined part. R1 to R8 may be the same as or different from each other, and each is independently an alkylene group with 1 to 200 carbon atoms (substituted or unsubstituted), an aryl group with 6 to 200 carbon atoms (substituted or unsubstituted), a heteroaryl group with 5 to 200 nuclear atoms (substituted or unsubstituted), or a cycloalkylene group with 3 to 200 carbon atoms (substituted or unsubstituted). The substituted alkylene, substituted arylene, substituted heteroarylene, and substituted cycloalkylene are selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 1 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 5 to 60 carbon atoms, and heteroarylalkyl with 6 to 30 carbon atoms. The substituents are one or more from the group consisting of alkoxy groups having 1 to 30 carbon atoms, alkylamino groups having 1 to 30 carbon atoms, arylamino groups having 6 to 30 carbon atoms, arylalkylamino groups having 6 to 30 carbon atoms, heteroarylamino groups having 2 to 24 carbon atoms, alkylsilyl groups having 1 to 30 carbon atoms, arylsilyl groups having 6 to 30 carbon atoms, and aryloxy groups having 6 to 30 carbon atoms, and are the same as or different from each other when substituted by multiple substituents.

[0029] The UV-curable polyurethane oligomer is a polymer with a weight-average molecular weight of 10,000 to 1,000,000.

[0030] More preferably, the UV-curable polyurethane oligomer is a compound represented by the following chemical formula 3: [Chemical Formula 3]

[0031] in, n and m may be the same or different from each other, and each is an independent integer from 1 to 200. A is as defined in chemical formula 1.

[0032] More specifically, it refers to a polymeric compound for UV curing, wherein the photocurable functional groups are substituents represented by the chemical formula 2.

[0033] The substituent represented by the chemical formula 2 contains a double bond structure between carbon atoms, and the carbon-carbon double bond can exhibit photocuring effect.

[0034] In addition, the UV-curable polyurethane oligomer comprises a polyurethane structure as the main chain, on which photocurable functional groups are bonded. The bonding between the polyurethane structure and the photocurable functional groups utilizes chains with flexible functional groups bonded to urethane chains and chains with rigid functional groups bonded to urethane chains.

[0035] When a chain with flexible functional groups is bonded to the urethane, the flexibility of the flexible functional groups can be utilized, while the rigid functional groups can exhibit heat resistance.

[0036] That is, photocurable functional groups are bonded to UV-curable polyurethane oligomers, and flexible and rigid functional groups are used as chains. The carbon skeleton, which is soft at room temperature, can exhibit a flexible effect, while the carbon skeleton, which is hard at room temperature, can exhibit strong heat resistance.

[0037] The UV-curable polyurethane oligomer, by including a rigid carbon skeleton, can produce 3D printed outputs with excellent physical properties such as thermal properties, strength, elastic modulus and elongation.

[0038] In addition, UV-cured polyurethane oligomers, by containing a soft carbon skeleton, can produce 3D printed outputs that can restore their original shape even if they are deformed by use.

[0039] Generally, although compositions used in 3D printers can improve the physical properties of 3D printed outputs by containing only a carbon skeleton with hard properties, they cannot restore the shape when it is deformed by use, resulting in the problem that they cannot be used multiple times.

[0040] Furthermore, when the composition used in a 3D printer contains only a soft carbon skeleton, there is a problem that the thermal properties, strength, elastic modulus, and elongation cannot be shown to the extent that they can be used as output materials due to the low physical properties of the output.

[0041] The composition for 3D printers in this invention contains both a rigid carbon skeleton and a flexible carbon skeleton in a UV-cured polyurethane oligomer. This results in excellent physical properties such as thermal properties, strength, elastic modulus and elongation. Furthermore, it can utilize the flexible properties of the flexible functional groups to restore the shape after deformation during use, thus enabling reuse.

[0042] The photoinitiator is a compound represented by the following chemical formula 4: [Chemical Formula 4]

[0043] in, X1 is S, O, or N (R) 11 ), R9 to R 11They may be the same as or different from each other, and each independently consists of hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms. The substituted alkyl and substituted cycloalkyl groups are substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 1 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 5 to 60 carbon atoms, heteroarylalkyl with 6 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, alkylamino with 1 to 30 carbon atoms, arylamino with 6 to 30 carbon atoms, arylalkylamino with 6 to 30 carbon atoms, heteroarylamino with 2 to 24 carbon atoms, alkylsilyl with 1 to 30 carbon atoms, arylsilyl with 6 to 30 carbon atoms, and aryloxy with 6 to 30 carbon atoms, and in the case of substitution by multiple substituents, they may be the same as or different from each other.

[0044] More preferably, it is a compound represented by the following chemical formula 5: [Chemical Formula 5]

[0045] The oligomer may be selected from the group consisting of epoxy acrylate oligomers, H12 dialkyl-bisglycidyl ether (a polymer of 4,4'-(1-methylethylidene)biscyclohexanol with chloromethyl oxirane), and mixtures thereof.

[0046] More specifically, the epoxy acrylate oligomer can be one or more compounds selected from the group consisting of phenyl epoxy (meth) acrylate oligomers, bisphenol A epoxy di(meth) acrylate oligomers, aliphatic alkyl epoxy di(meth) acrylate oligomers, and aliphatic alkyl epoxy tri(meth) acrylate oligomers. These oligomers not only reduce swelling caused by organic solvents but also improve surface hardness, abrasion resistance, and heat resistance.

[0047] The silane coupling agent is more specifically 3-methcryloxypropyltrimethoxysilane, but is not limited to the examples described.

[0048] The stabilizer is selected from the group consisting of 2,6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amines, organophosphates, hindered phenols, and mixtures thereof, more specifically 2,6-di-tert-butyl-p-cresol.

[0049] To improve thermal and oxidative stability, storage stability, surface properties, flow properties, and process properties, conventional additives such as leveling agents, slip agents, or stabilizers may be included.

[0050] The photocurable polymer composition for 3D printers comprises a UV-curable polyurethane oligomer, and relative to 100 parts by weight of the UV-curable polyurethane oligomer, it comprises 1.5 to 15 parts by weight of a photoinitiator, 0.1 to 1.5 parts by weight of a silane coupling agent, 15 to 45 parts by weight of the oligomer, and 0.1 to 2 parts by weight of a stabilizer. When used within the stated scope of use, the silane coupling agent can improve compatibility and adhesive strength with the resin when used for surface treatment of pigments and fillers. When the oligomer is used beyond the stated scope of use, the surface energy increases, reducing the mold release property from the resin, and the surface hardness increases, potentially reducing surface properties such as mold recovery force after stamping. Regarding the stabilizer, when used within the stated scope of use, it can reduce peripheral hardening and improve strength.

[0051] Invention Effects The photocurable polymer composition for 3D printers according to the present invention can produce 3D printed outputs with excellent physical properties such as thermal properties, strength, elastic modulus and elongation.

[0052] In addition, there is a polymer composition for 3D printers that can produce 3D printed outputs that can restore the original shape even if the original shape is deformed by the use of the 3D printed output. Attached Figure Description

[0053] Figure 1 These are photographs of 3D printed outputs of a polymer composition utilizing an embodiment of the present invention.

[0054] Figure 2 This is a table showing the tensile test results of a 3D output object according to an embodiment of the present invention.

[0055] Figure 3 This is a table showing the bending test results of a 3D output object according to an embodiment of the present invention.

[0056] Figure 4 This is a table showing the compression test results of a 3D output from an embodiment of the present invention. Detailed Implementation

[0057] This invention relates to a photocurable polymer composition for 3D printers comprising a UV-curable polyurethane oligomer represented by the following chemical formula 1, a photoinitiator, a silane coupling agent, oligomers, and a stabilizer: [Chemical Formula 1]

[0058] [Chemical Formula 2]

[0059] in, A is a substituent represented by chemical formula 2. * indicates the bonded portion. R1 to R8 may be the same as or different from each other, and each is independently an alkylene group with 1 to 200 carbon atoms (substituted or unsubstituted), an aryl group with 6 to 200 carbon atoms (substituted or unsubstituted), a heteroaryl group with 5 to 200 nuclear atoms (substituted or unsubstituted), or a cycloalkylene group with 3 to 200 carbon atoms (substituted or unsubstituted). The substituted alkylene, substituted arylene, substituted heteroarylene, and substituted cycloalkylene can be selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 1 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 5 to 60 carbon atoms, and heteroarylalkyl with 6 to 30 carbon atoms. The substituents are one or more of the following groups: alkoxy groups having 1 to 30 carbon atoms, alkylamino groups having 1 to 30 carbon atoms, aromaticamino groups having 6 to 30 carbon atoms, aralkylamino groups having 6 to 30 carbon atoms, heteroaromaticamino groups having 2 to 24 carbon atoms, alkylsilyl groups having 1 to 30 carbon atoms, arylsilyl groups having 6 to 30 carbon atoms, and aryloxy groups having 6 to 30 carbon atoms, and the substituents are the same as or different from each other when substituted by multiple substituents.

[0060] Methods of implementing the invention The embodiments of the present invention will now be described in detail to facilitate implementation by those skilled in the art. However, the present invention can be implemented in various different forms and is not limited to the embodiments described herein.

[0061] [Preparation Example: Preparation of a Photocurable Polymer Composition for 3D Printers] A photocurable polymer composition for 3D printers is prepared by mixing a UV-curable polyurethane oligomer represented by Chemical Formula 3, a photoinitiator represented by Chemical Formula 5, 3-methacryloyloxypropyltrimethoxysilane, an epoxy acrylate oligomer, and 2,6-di-tert-butyl-p-cresol. The oligomers and other components used in the preparation of the polymer composition are purchased and their contents are shown in Table 1 below.

[0062] [Chemical Formula 3]

[0063] [Chemical Formula 2]

[0064] [Chemical Formula 5]

[0065] in, A is a substituent represented by chemical formula 2, where n and m are the same or different from each other, and each is an independent integer from 1 to 200.

[0066] [Table 1]

[0067] (Unit weight) [Experimental Example: Physical Property Evaluation Experiment] 1. Test conditions 1-1. Tensile test Test method: ASTM D638 Test instrument: Universal Testing Machine Test speed: 50 mm / min Grip spacing: 115mm Load sensor: 3000N Elastic range: (0.05~0.25)% Yield point: 0.2% offset Test environment: (23±2)℃, (50±5)% RH 1-2. Bending Test Test method: ASTM D790 Test instrument: Universal Testing Machine Test speed: 1.4 mm / min Span: 55mm Load sensor: 200N Elastic range: (0.05~0.25)% Test environment: (23±2)℃, (50±5)% RH 1-3. IZOD impact strength Test method: ASTM D256 Notch depth: 2.54mm (processed by the client) Test environment: (23±2)℃, (50±5)% RH 1-4. Compression test Test method: ASTM D695 Test speed: 1.3 mm / min Load sensor: 30000N Test environment: (23±2)℃, (50±5)% RH 1-5. Hardness tester (Durometer) Test method: ASTM D2240 Test environment: (23±2)℃, (50±5)% RH 1-6. Heat distortion temperature Test method: ASTM D648 Test load: 0.45 MPa Heating rate: 2℃ / min 2. Test Results The experiment was commissioned to the Korea Polymer Testing Institute, and the specimens were output using a 3D printer from the polymer compositions S10 to S50 in Table 1. Figure 1 The test pieces are provided.

[0068] For comparative experiments, specimens were prepared using Next Dent products, ABS materials, and PC materials to confirm the comparative experimental results with S50. The results are shown in Table 2 below.

[0069] [Table 2]

[0070] As shown in Table 2, it was confirmed that, compared with existing products on the market, S50 exhibits lower viscosity and is easier to handle, while showing relatively superior performance in tensile and flexural tests.

[0071] The compressive strength, tensile strength, yield strength, flexural strength, flexural modulus, elongation, and heat distortion temperature of S10 to S60 were measured.

[0072] [Table 3]

[0073] As shown in Table 3, the property evaluation results of S10 to S60 confirm that the maximum load, tensile strength, yield strength, puncture point, maximum displacement, elongation and elastic modulus of the samples of S10 and S60 are relatively low.

[0074] Regarding S20 and S30, it was confirmed that the heat distortion temperature is around 52 to 58°C. When the output material is deformed by use, it can recover its original shape in water at 52 to 58°C, showing excellent performance in terms of compressive strength, tensile strength, and modulus of elasticity.

[0075] Regarding S40 and S50, it was confirmed that they have higher heat distortion temperatures compared to S20 and S30, but exhibit superior performance in other physical properties.

[0076] The differences in physical properties between S20 and S50 are shown by the content of the constituent components, and an appropriate polymer composition can be selected according to the intended use of the output printed by the 3D printer.

[0077] While the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto. Various modifications and improvements made by those skilled in the art that utilize the basic concepts of the present invention as defined in the claims also fall within the scope of the present invention.

[0078] Industrial applicability This invention relates to photocurable polymer compositions for 3D printers, and more specifically, to photocurable polymers suitable for 3D printing, which enable the production of 3D printed outputs with excellent physical properties such as thermal properties, strength, elastic modulus and elongation, and the ability to recover their shape.

Claims

1. A photocurable polymer composition for 3D printers, wherein, Include: UV-curable polyurethane oligomers represented by the following chemical formula 1, Photoinitiator, Silane coupling agents, oligomers, and Stabilizer; [Chemical Formula 1] [Chemical Formula 2] in, A is a substituent represented by chemical formula 2. * indicates the bonded portion. R1 to R8 may be the same as or different from each other, and each is independently an alkylene group with 1 to 200 carbon atoms (substituted or unsubstituted), an aryl group with 6 to 200 carbon atoms (substituted or unsubstituted), a heteroaryl group with 5 to 200 nuclear atoms (substituted or unsubstituted), and a cycloalkylene group with 3 to 200 carbon atoms (substituted or unsubstituted). The substituted alkylene, substituted arylene, substituted heteroarylene, and substituted cycloalkylene are selected from hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 1 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 5 to 60 carbon atoms, and heteroarylalkyl with 6 to 30 carbon atoms. The substituents are one or more from the group consisting of alkoxy groups having 1 to 30 carbon atoms, alkylamino groups having 1 to 30 carbon atoms, arylamino groups having 6 to 30 carbon atoms, arylalkylamino groups having 6 to 30 carbon atoms, heteroarylamino groups having 2 to 24 carbon atoms, alkylsilyl groups having 1 to 30 carbon atoms, arylsilyl groups having 6 to 30 carbon atoms, and aryloxy groups having 6 to 30 carbon atoms, and are the same as or different from each other when substituted by multiple substituents.

2. The photocurable polymer composition for 3D printers according to claim 1, wherein, The weight-average molecular weight of the UV-curable polyurethane oligomer is between 10,000 and 1,000,000.

3. The photocurable polymer composition for 3D printers according to claim 1, wherein, The photoinitiator is a compound represented by the following chemical formula 4: [Chemical Formula 4] in, X1 is S, O, or N (R) 11 ), R9 to R 11 They may be the same as or different from each other, and each independently consists of hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms. The substituted alkyl and substituted cycloalkyl groups are substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, cyano, nitro, halogen, hydroxyl, alkyl with 1 to 30 carbon atoms, cycloalkyl with 1 to 20 carbon atoms, alkenyl with 2 to 30 carbon atoms, alkynyl with 2 to 24 carbon atoms, aralkyl with 7 to 30 carbon atoms, aryl with 6 to 30 carbon atoms, heteroaryl with 5 to 60 carbon atoms, heteroarylalkyl with 6 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms, alkylamino with 1 to 30 carbon atoms, arylamino with 6 to 30 carbon atoms, arylalkylamino with 6 to 30 carbon atoms, heteroarylamino with 2 to 24 carbon atoms, alkylsilyl with 1 to 30 carbon atoms, arylsilyl with 6 to 30 carbon atoms, and aryloxy with 6 to 30 carbon atoms, and in the case of substitution by multiple substituents, they may be the same as or different from each other.

4. The photocurable polymer composition for 3D printers according to claim 1, wherein, The oligomer is selected from epoxy acrylate oligomers, H 12 The group consisting of dialkyl-bisglycidyl ethers and mixtures thereof.

5. The photocurable polymer composition for 3D printers according to claim 1, wherein, The stabilizer is selected from the group consisting of 2,6-di-tert-butyl-p-cresol, diethylethanolamine, trihexylamine, hindered amines, organophosphates, hindered phenols, and mixtures thereof.

6. The photocurable polymer composition for 3D printers according to claim 1, wherein, The photocurable polymer composition for 3D printers comprises UV-curable polyurethane oligomers. Relative to 100 parts by weight of the UV-curable polyurethane oligomer, it comprises 1.5 to 15 parts by weight of photoinitiator, 0.1 to 1.5 parts by weight of silane coupling agent, 15 to 45 parts by weight of oligomer, and 0.1 to 2 parts by weight of stabilizer.

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