3D printing ink composition and 3D printing molded article formed by curing same

Abstract

The present disclosure relates to: a 3D printing ink composition comprising alginate, a biocompatible hydrogel, acrylamide-based monomers, a photocrosslinkable polymer, a light absorber, and a solvent; and a 3D printing molded article formed by curing the composition.

Description

3D printing ink composition and 3D printed molded article formed by curing the same

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2024-0141707 filed on October 17, 2024, and includes all contents disclosed in the document of said Korean patent application as part of this specification.

[0002] The present invention relates to a 3D printing ink composition and a 3D printed molded article formed by curing the same.

[0003] A 3D (3-Dimension) printer is equipment that produces an actual three-dimensional shape based on an input 3D drawing, just like printing text or images.

[0004] Recently, 3D printing technology has become a hot topic, and as its application fields expand to automotive, medical, art, and education sectors, it is being widely used to create various models.

[0005] The principles of 3D printers can be broadly divided into subtractive and additive types, and most 3D printers currently in use are additive types that do not involve material loss.

[0006] There are about 20 methods that utilize the additive manufacturing principle, but the most commonly used methods among them are SLA (Stereo Lithography Apparatus), FDM (Fused Deposition Modeling), DIW (Direct Ink Writing), FFF (Fused Filament Fabrication), SLS (Selective Laser Sintering), and DLP (Digital Light Processing).

[0007] SLA is a method of forming by projecting a laser beam into a tank containing liquid photocurable resin, and epoxy-type photopolymers are primarily used as photocurable resins. On the other hand, FDM (or FFF), a method of forming a three-dimensional object by extruding molten material from a printer nozzle that moves along the X, Y, and Z axes, uses thermoplastic plastics as the main material. Meanwhile, SLS implements 3D printing by shooting a laser into a tank containing powdered materials such as metal, plastic, or ceramic powder to selectively sinter them.

[0008] Among the above methods, the FDM method, which uses thermoplastic plastics manufactured in the form of filaments, is the most widely popularized because the price of 3D printers is relatively low and the printing speed is faster than other methods. In the FDM method, rigid materials such as polylactic acid (PLA), ABS (Acrylonitrile Butadiene Styrene), HDPE, and polycarbonate (PC), as well as flexible materials such as thermoplastic elastomers, are generally used because they provide excellent bed adhesion and interlayer adhesion, as well as good shape stability when shaping 3D objects.

[0009] Recently, in addition to the aforementioned FDM method, the Digital Light Processing (DLP) method utilizing a light source is also being widely used. The DLP method allows for the selective formation of molded products by using a Digital Micromirror Device (DMD) chip to express the desired image in great detail within a bath containing photocurable resin. Furthermore, since the molding process is performed by irradiating light from a planar light source, it offers the advantages of fast and uniform processing speeds, as well as the ability to achieve high precision and surface roughness in the molded products.

[0010] The development of so-called '3D bioprinting technology,' which forms artificial tissues or organs using materials such as hydrogels via this DLP method, is also actively underway.

[0011] However, in the case of hydrogels, since the material itself contains a large amount of water, there is a problem that the physical properties of the molded product after printing are weak in supporting external forces, and it is not easy to use various types of materials simultaneously in the processing process. In addition, due to the nature of the DLP method that uses a light source, the physical properties of the molded product may change depending on the control of the light source, such as UV, must also be fully considered.

[0012] Accordingly, there is a need to develop an ink composition that can utilize the above-mentioned DLP light source irradiation-based printing technology while also securing the mechanical properties of the 3D molded product.

[0013] The objective of the present invention is to provide a 3D printing ink composition that can be used for 3D printing, comprising an acrylamide-based monomer and a photocrosslinkable polymer together with alginate and a biocompatible hydrogel, and further comprising a certain amount of a light absorber, so that it is suitable for 3D printing methods that use a light source, such as DLP 3D printing methods, and thereby can secure mechanical properties similar to actual human tissue and enable high-resolution printing when a molded article formed by curing through this is realized as a human tissue-like structure such as an artificial organ.

[0014] One embodiment of the present invention provides a 3D printing ink composition comprising alginate, a biocompatible hydrogel, an acrylamide-based monomer, a photocrosslinkable polymer, a light absorber, and a solvent.

[0015] The above biocompatible hydrogel may include one or more of gelatin, gelatin methacrylate, collagen, fibrinogen, fibrin, hyaluronic acid, methyl cellulose, chitosan, chitin, Extracel™, pectin, polylactic acid (PLA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyphosphate, synthetic peptides, and polyethylene glycol.

[0016] The above acrylamide-based monomers are acrylamide, N-isopropylacrylamide (NIPAM), N-tert-butyl acrylamide, N,N-diethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N,N-ethylmethylacrylamide, N-isopropylmethacrylamide, N-hydroxyethylacrylamide, N-(isobutoxymethyl)acrylamide, and N-tert-butylmethacrylamide. It may include one or more of N,N-diethylmethacrylamide and N-ethylmethacrylamide.

[0017] The above photocrosslinkable polymer may include one or more of polyethylene glycol ethyl methacrylate (PEGMA), polyethylene glycol ethyl acrylate (PEGA), polyethylene glycol ethyl diacrylate (PEGDA), and polyethylene glycol ethyl dimethacrylate (PEGDMA).

[0018] The above light absorbers are tartrazine, Jaune brilliant, sunset yellow FCF, brilliant blue FCF, indigo carmine, fast green FCF anthocyanins, anthocyanidin, erythrosine, Allura red AC, riboflavin, ascorbic acid, quinoline yellow WS, carmoisine, Ponceau 4R, patent blue V, green S, yellow 2G, orange GGN, red 2G, caramel color, and phenol red. It may include one or more of red), methyl orange, 4-nitrophenol, and NADH disodium salt.

[0019] The above composition may include 0.1 to 5 parts by weight of the alginate based on 100 parts by weight of the total composition.

[0020] The biocompatible hydrogel may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the total composition.

[0021] The above composition may include 10 to 50 parts by weight of the acrylamide-based monomer based on 100 parts by weight of the total composition.

[0022] The photocrosslinkable polymer may be included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total composition.

[0023] The light absorber may be included in an amount of 0.005 to 0.5 parts by weight based on 100 parts by weight of the total composition.

[0024] The above composition comprises lithium benzoyl(phenyl)phosphinate (BP), α-hydroxyketone derivatives (irgacure 2959, irgacure 184, irgacure 651, irgacure 369, irgacure 907, etc.), phosphate derivatives (TPO, TPO-Na, LAP, BAPO, BAPO-ONa, BAPO-OLi, etc.), azo-initiator (2,2'-azobis[2-methyl-N-(2-hydroxyethyl) promionamide] (VA-086)), eosin-Y, riboflavin (B2), and camphorquinone. Erythrosine, Rose Bengal, WSPI (1,4-bis(4-N,N-bis(6-N,N,N-trimethylammonium)hexyl)amino)-styryl)-2,5-dimethoxybenzene tetraiodide)), BDEA (2,5-bis-[4-(diethylamino)-benzylidene]-cyclopentanone)), P2CK (3,3'-((((1E,1'E)-(2-oxocyclopentane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))dipropanoate)(P2CK (3,3'-((((1E,1'E)-(2-oxocyclopentane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))dipropanoate)) and G2CK (sodium 2,2'-((((1E,It may further include one or more photoinitiators selected from 1'E)-(5-methyl-2-oxocyclohexane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))diacetate)(G2CK (sodium 2,2'-((((1E,1'E)-(5-methyl-2-oxocyclohexane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))diacetate)).

[0025] The above composition may include 0.1 to 1.5 parts by weight of the photoinitiator based on 100 parts by weight of the total composition.

[0026] Another embodiment of the present invention provides a 3D printed molded article formed by photocuring the 3D printing ink composition.

[0027] The ultimate tensile strength (UTS) of the above 3D printed product may be 100 to 400 kPa.

[0028] The modulus of the above 3D printed molded product may be 40 to 100 kPa.

[0029] The toughness of the above 3D printed molded product is 80 to 700 kJ / m² 3 It could be.

[0030] According to the present invention, an ink composition that can be used for 3D printing comprises an acrylamide monomer and a photocrosslinkable polymer together with alginate and a biocompatible hydrogel, and further comprises a certain amount of a light absorber, so that it is suitable for a 3D printing method that uses a light source, for example, a DLP 3D printing method, and thereby has the advantage of securing mechanical properties similar to actual human tissue and enabling high-resolution printing when a molded article formed by curing through this, particularly when said molded article is realized as a human tissue-like structure such as an artificial organ.

[0031] FIGS. 1a to 1d show images of a 3D printed molded article formed by photocuring a 3D printing ink composition according to one embodiment of the present invention.

[0032] FIGS. 2a to 2e show images of a 3D printed molded article formed by photocuring a 3D printing ink composition according to one comparative example of the present invention.

[0033] FIGS. 3 to 6 are graphs showing the ultimate tensile strength (UTS), modulus, and toughness of a 3D printed molded article formed by photocuring a 3D printing ink composition according to one embodiment and a comparative example of the present invention.

[0034] Embodiments of the present invention will be described in detail below. Prior to this, terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings. Instead, based on the principle that the inventor can appropriately define the concepts of terms to best describe their invention, they should be interpreted in a meaning and concept consistent with the technical spirit of the present invention. Therefore, the configurations described in the embodiments of this specification are merely one preferred embodiment of the present invention and do not represent all aspects of the technical spirit of the present invention. It should be understood that various equivalents and modifications capable of replacing them may exist at the time of filing this application.

[0035] Throughout this specification, when a part is described as 'comprising' a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0036] Furthermore, descriptions that specify components by limiting or adding them may be applied to all inventions unless there are special limitations, and are not limited to specific inventions.

[0037] In addition, throughout the description of the invention and claims of this application, items indicated in the singular include cases where they are plural unless otherwise noted.

[0038] In addition, throughout the description of the invention and the claims of the present invention, "or" includes "and" unless otherwise noted. Therefore, "comprising A or B" means all three of the above cases: including A, including B, or including both A and B.

[0039] In addition, all numerical ranges include the values ​​at both ends and all intermediate values ​​in between, unless explicitly stated to be excluded.

[0040] A 3D printing ink composition according to one embodiment of the present invention will be described below.

[0041] 3D printing ink composition

[0042] The present invention relates to a 3D printing ink composition that can be used for 3D printing, comprising an alginate, a biocompatible hydrogel, a photocrosslinkable polymer, and an acrylamide-based monomer, and further comprising a certain amount of a light absorber, so as to be suitable for a 3D printing method that uses a light source, for example, a DLP 3D printing method, thereby enabling the securing of mechanical properties similar to actual human tissue and high-resolution printing when the molded article formed by curing through this method is realized as a human tissue-like structure such as an artificial organ.

[0043] Hereinafter, each component of the 3D printing ink composition according to one embodiment of the present invention will be described.

[0044] (1) Alginate and biocompatible hydrogel

[0045] The above alginate and biocompatible hydrogel serve to enable the composition according to the present invention to exhibit physical properties similar to human tissue when molded through a 3D printing method.

[0046] In particular, the types of the above-mentioned biocompatible hydrogels include, for example, gelatin methacrylate, collagen, fibrinogen, fibrin, hyaluronic acid, methyl cellulose, chitosan, chitin, Extracel™, pectin, polylactic acid (PLA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyphosphate, synthetic peptides, and polyethylene glycol. The type of material is not limited as long as it exhibits biocompatibility, but preferably, polyvinyl alcohol (PVA), alginate, etc. can be used.

[0047] In one embodiment of the present invention, the content of the alginate may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total composition, for example, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, 0.5 parts by weight or more, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, 1 part by weight or more, 1.1 parts by weight or more, 1.2 parts by weight or more, 1.3 parts by weight or more, 1.4 parts by weight or more, 1.5 parts by weight or more, 1.6 parts by weight or more, 1.7 parts by weight or more, 1.8 parts by weight or more, 1.9 parts by weight or more, 2 parts by weight or more, 2.1 parts by weight or more, 2.2 parts by weight or more, 2.3 parts by weight or more, 2.4 parts by weight or more, or 2.5 parts by weight or more, and 5 parts by weight or less. It may be included in an amount of 4.9 parts by weight or less, 4.8 parts by weight or less, 4.7 parts by weight or less, 4.6 parts by weight or less, 4.5 parts by weight or less, 4.4 parts by weight or less, 4.3 parts by weight or less, 4.2 parts by weight or less, 4.1 parts by weight or less, 4 parts by weight or less, 3.9 parts by weight or less, 3.8 parts by weight or less, 3.7 parts by weight or less, 3.6 parts by weight or less, 3.5 parts by weight or less, 3.4 parts by weight or less, 3.3 parts by weight or less, 3.2 parts by weight or less, 3.1 parts by weight or less, 3 parts by weight or less, 2.9 parts by weight or less, 2.8 parts by weight or less, 2.7 parts by weight or less, or 2.6 parts by weight or less.

[0048] In one embodiment of the present invention, the biocompatible hydrogel may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the total composition, for example, 1 part by weight or more, 1.1 parts by weight or more, 1.2 parts by weight or more, 1.3 parts by weight or more, 1.4 parts by weight or more, 1.5 parts by weight or more, 1.6 parts by weight or more, 1.7 parts by weight or more, 1.8 parts by weight or more, 1.9 parts by weight or more, 2 parts by weight or more, 2.1 parts by weight or more, 2.2 parts by weight or more, 2.3 parts by weight or more, 2.4 parts by weight or more, 2.5 parts by weight or more, 2.6 parts by weight or more, 2.7 parts by weight or more, 2.8 parts by weight or more, 2.9 parts by weight or more, or 3.0 parts by weight or more, and 5 parts by weight or less, 4.9 parts by weight or less, 4.8 parts by weight or less, 4.7 parts by weight or less, 4.6 parts by weight or less, It may be included in an amount of 4.5 parts by weight or less, 4.4 parts by weight or less, 4.3 parts by weight or less, 4.2 parts by weight or less, 4.1 parts by weight or less, 4 parts by weight or less, 3.9 parts by weight or less, 3.8 parts by weight or less, 3.7 parts by weight or less, 3.6 parts by weight or less, 3.5 parts by weight or less, 3.4 parts by weight or less, 3.3 parts by weight or less, 3.2 parts by weight or less, and 3.1 parts by weight or less.

[0049] If the content of each of the alginate and biocompatible hydrogel is below the above range, the molded article formed through the composition may exhibit properties such as reduced Young's modulus and tensile strength compared to actual human tissue, and easily fracture under external force.

[0050] In addition, if the content of the alginate and biocompatible hydrogel exceeds the above range, the viscosity of the composition increases, which may not be suitable for 3D printing and may be difficult to manufacture high-resolution molded articles.

[0051] That is, in the case of a 3D printing ink composition containing alginate and biocompatible hydrogel as major components as in the present invention, it is important to ensure that the physical properties of the molded article produced therefrom, such as Young's modulus and tensile strength, exhibit properties similar to actual human tissue, and to achieve this, the content of each component included in the composition must satisfy an appropriate mixing ratio. In particular, for 3D printing methods such as the DLP method using a light source, controlling the viscosity of the printing ink composition is important to produce high-resolution molded articles, and to control the viscosity of such a composition, it is necessary to satisfy the content of the biocompatible hydrogel in the composition within the range described above.

[0052] (2) Acrylamide monomer

[0053] The 3D printing ink composition according to the present invention further comprises an acrylamide-based monomer together with the alginate and biocompatible hydrogel. The acrylamide-based monomer is a type of hydrogel that changes into polyacrylamid after the composition according to the present invention is cured. The acrylamide-based monomer plays a role in enabling the composition according to the present invention to exhibit physical properties similar to actual human tissue by forming a hydrogel network as it is cured.

[0054] In one embodiment of the present invention, the acrylamide-based monomer is acrylamide, N-isopropylacrylamide (NIPAM), N-tert-butyl acrylamide, N,N-diethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N,N-ethylmethylacrylamide, N-isopropylmethacrylamide, N-hydroxyethylacrylamide, N-(isobutoxymethyl)acrylamide, N-tert-butylmethacrylamide, It may be at least one selected from the group consisting of N,N-diethylmethacrylamide and N-ethylmethacrylamide, for example, acrylamide may be used.

[0055] In one embodiment of the present invention, the acrylamide monomer may be included in an amount of 10 to 50 parts by weight based on 100 parts by weight of the total composition, for example, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, 15 parts by weight or more, 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, 20 parts by weight or more, 21 parts by weight or more, 22 parts by weight or more, 23 parts by weight or more, 24 parts by weight or more, 25 parts by weight or more, 26 parts by weight or more, 27 parts by weight or more, 28 parts by weight or more, 29 parts by weight or more, or 30 parts by weight or more, and 50 parts by weight or less, 49 parts by weight or less, 48 ​​parts by weight or less, 47 parts by weight or less, 46 parts by weight or less, 45 parts by weight or less, 44 parts by weight or less, 43 parts by weight or less, It may be included in an amount of 42 parts by weight or less, 41 parts by weight or less, 40 parts by weight or less, 39 parts by weight or less, 38 parts by weight or less, 37 parts by weight or less, 36 parts by weight or less, 35 parts by weight or less, 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, or 31 parts by weight or less.

[0056] If the content of the acrylamide-based monomer is less than 10 parts by weight based on 100 parts by weight of the total composition, the alginate and biocompatible hydrogel included in the composition may have properties weaker than actual human tissue, so they may easily break when external pressure is applied, or the curing speed may be lowered during the curing process of the composition. If it exceeds 50 parts by weight, the 3D printed product formed through the composition may exhibit properties that are harder than actual human tissue, which may cause a sense of unfamiliarity.

[0057] (3) Photocrosslinkable polymer

[0058] The 3D printing ink composition according to the present invention further comprises a photocrosslinkable polymer together with the alginate, biocompatible hydrogel, and acrylamide-based monomer.

[0059] The above photocrosslinkable polymer is a material that acts as a crosslinker between the networking formed through the alginate, biocompatible hydrogel, and acrylamide-based monomer in the composition, and specifically, by crosslinking the polyacrylamide chains formed by curing the acrylamide-based monomer, it can further improve the mechanical strength and chemical stability of the 3D printed product formed by the composition according to the present invention.

[0060] Therefore, any material capable of crosslinking the networking formed through the alginate, biocompatible hydrogel, and acrylamide-based monomer of the present invention may be used regardless of its type, for example, one or more of polyethylene glycol ethyl methacrylate (PEGMA), polyethylene glycol ethyl acrylate (PEGA), polyethylene glycol ethyl diacrylate (PEGDA), and polyethylene glycol ethyl dimethacrylate (PEGDMA) may be used.

[0061] In one embodiment of the present invention, polyethylene glycol ethyl methacrylate (PEGMA) may be used as the photocrosslinkable polymer, wherein the weight-average molecular weight of the polyethylene glycol ethyl methacrylate may be Mw 300 to 10,000, and preferably Mw 300 to 800.

[0062] The above photocrosslinkable polymer may be included in an amount of 0.1 to 2 parts by weight based on 100 parts by weight of the total composition according to the present invention, for example, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, 0.5 parts by weight or more, 0.6 parts by weight or more, 0.7 parts by weight or more, 0.8 parts by weight or more, 0.9 parts by weight or more, or 1 part by weight or more, and may be included in an amount of 2 parts by weight or less, 1.9 parts by weight or less, 1.8 parts by weight or less, 1.7 parts by weight or less, 1.6 parts by weight or less, 1.5 parts by weight or less, 1.4 parts by weight or less, 1.3 parts by weight or less, 1.2 parts by weight or less, or 1.1 parts by weight or less. If the content of the photocrosslinkable polymer is below the above range, sufficient crosslinking may not be achieved to provide mechanical strength and chemical stability to the 3D printed product formed by the composition according to the present invention, and the product may be weaker than the physical properties of actual human tissue and easily fracture when external pressure is applied; if it exceeds the above range, excessive crosslinking may occur, causing the 3D printed product to exhibit physical properties that are harder than actual human tissue, which may result in a feeling of unnaturalness.

[0063] (4) Light absorber

[0064] The 3D printing ink composition according to the present invention further comprises a light absorber together with the alginate, biocompatible hydrogel, acrylamide-based monomer, and photocrosslinkable polymer.

[0065] The light absorber above serves to increase the output resolution of a 3D printed product using the 3D printing ink composition according to the present invention. When a light source is irradiated onto the 3D printing ink composition according to the present invention, a photoinitiator described below receives light of an appropriate wavelength and initiates a polymer polymerization reaction within the composition. At this time, the light absorber performs the function of controlling the polymer polymerization reaction so that it proceeds only in the area of ​​the desired light source irradiation, thereby enabling the realization of high resolution in the 3D printed product.

[0066] If a 3D printing ink composition used in 3D printing that irradiates a light source such as the DLP method does not include the light absorber mentioned above, the transparency of the composition increases overall, and consequently, as the light source is irradiated throughout the composition, there is a risk that an excessive polymerization reaction may proceed. Therefore, by including the light absorber mentioned above, the 3D printing ink composition of the present invention absorbs the light that is excessively transmitted and its scattered light during the irradiation process, thereby enabling the spot size of the irradiated light source to be maintained appropriately.

[0067] The light absorber can absorb a light source in a wavelength range of, for example, 400 nm to 520 nm or 224 nm to 414 nm.

[0068] In one embodiment of the present invention, the light absorber is tartrazine, Jaune brilliant, sunset yellow FCF, brilliant blue FCF, indigo carmine, fast green FCF anthocyanins, anthocyanidin, erythrosine, Allura Red AC, riboflavin, ascorbic acid, quinoline yellow WS, carmoisine, Ponceau 4R, patent blue V, green S, yellow 2G, orange GGN, red 2G, caramel It may include one or more of color), phenol red, methyl orange, 4-nitrophenol, and NADH disodium salt, and for example, tartrazine and Jaune brilliant may be used as the light absorbers.

[0069] The light absorber may be included in an amount of 0.005 to 0.5 parts by weight based on 100 parts by weight of the total composition included in the composition, for example, 0.005 parts by weight or more, 0.01 parts by weight or more, 0.02 parts by weight or more, 0.03 parts by weight or more, 0.04 parts by weight or more, 0.05 parts by weight or more, 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, 0.1 parts by weight or more, 0.11 parts by weight or more, 0.12 parts by weight or more, 0.13 parts by weight or more, 0.14 parts by weight or more, 0.15 parts by weight or more, 0.16 parts by weight or more, 0.17 parts by weight or more, 0.18 parts by weight or more, 0.19 parts by weight or more, 0.2 parts by weight or more, 0.21 parts by weight or more, 0.22 parts by weight or more, It may be included in an amount of 0.23 parts by weight or more, 0.24 parts by weight or more, or 0.25 parts by weight or more, and 0.5 parts by weight or less, 0.49 parts by weight or less, 0.48 parts by weight or less, 0.47 parts by weight or less, 0.46 parts by weight or less, 0.45 parts by weight or less, 0.44 parts by weight or less, 0.43 parts by weight or less, 0.42 parts by weight or less, 0.41 parts by weight or less, 0.4 parts by weight or less, 0.39 parts by weight or less, 0.38 parts by weight or less, 0.37 parts by weight or less, 0.36 parts by weight or less, 0.35 parts by weight or less, 0.34 parts by weight or less, 0.33 parts by weight or less, 0.32 parts by weight or less, 0.31 parts by weight or less, 0.3 parts by weight or less, 0.29 parts by weight or less, 0.28 parts by weight or less, or 0.27 parts by weight or less. It may be included in an amount of 0.26 parts by weight or less.

[0070] If the content of the light absorber is less than 0.005 parts by weight based on 100 parts by weight of the total composition, the intensity of the light source irradiated onto the composition increases excessively, leading to an excessive polymer polymerization reaction and consequently a decrease in the resolution of the 3D printed product. If it exceeds 0.5 parts by weight, the polymer polymerization reaction is excessively suppressed at the same amount of light and irradiation time, which may result in the 3D printed product not being formed intact.

[0071] (5) solvent

[0072] In one embodiment of the present invention, the solvent in the composition is not limited to any specific type as long as it can effectively dissolve each composition such as alginate, biocompatible hydrogel, acrylamide monomer, photocrosslinkable polymer, and light absorber, but, for example, an aqueous solvent such as water may be used.

[0073] The content of the above solvent may be included in an amount such that each component in the composition can be included within a preferred range according to the purpose of the present invention.

[0074] (6) Other ingredients

[0075] The 3D printing ink composition of the present invention may further include a photoinitiator in addition to the components described above to control physical properties.

[0076] The above photoinitiator is a substance used to initiate a chain reaction for curing the above composition, and specifically refers to a substance that easily generates radicals using a light source such as UV.

[0077] The above photoinitiator may be any substance capable of initiating a curing reaction by a light source, regardless of its type, for example, lithium benzoyl(phenyl)phosphinate (BP), α-hydroxyketone derivatives (irgacure 2959, irgacure 184, irgacure 651, irgacure 369, irgacure 907, etc.), phosphate derivatives (TPO, TPO-Na, LAP, BAPO, BAPO-ONa, BAPO-OLi, etc.), azo-initiator (2,2'-azobis[2-methyl-N-(2-hydroxyethyl) promionamide] (VA-086)), Eosin-Y, Riboflavin (B2), Camphorquinone, Erythrosine, Rose Bengal, WSPI (1,4-bis(4-N,N-bis(6-N,N,N-trimethylammonium)hexyl)amino)-styryl)-2,5-dimethoxybenzene tetraiodide)), BDEA (2,5-bis-[4-(diethylamino)-benzylidene]-cyclopentanone)), P2CK (3,3'-((((1E,1'E)-(2-oxocyclopentane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylaseindiyl))dipropanoate)(P2CK (3,3'-((((1E,1'E)-(2-oxocyclopentane-1,3-diylidene)bis(methanylylidene))bis(4,One or more of 1-phenylene))bis(methylazanediyl))dipropanoate)) and G2CK (sodium 2,2'-((((1E,1'E)-(5-methyl-2-oxocyclohexane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))diacetate)) may be used.

[0078] Specifically, the photoinitiator may use TPO (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) nanoparticles with improved water dispersibility by applying a surfactant so that they can be smoothly dispersed in the solvent included in the 3D printing ink composition according to the present invention.

[0079] In the case of the above photoinitiator, it may be included in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the total composition according to the present invention, for example, 0.1 parts by weight or more, 0.2 parts by weight or more, 0.3 parts by weight or more, 0.4 parts by weight or more, 0.5 parts by weight or more, 0.6 parts by weight or more, 0.7 parts by weight or more, or 0.8 parts by weight or more, and may be included in an amount of 1.5 parts by weight or less, 1.4 parts by weight or less, 1.3 parts by weight or less, 1.2 parts by weight or less, 1.1 parts by weight or less, 1.0 parts by weight or less, or 0.9 parts by weight or less.

[0080] If the content of the above photoinitiator is below the above range, the curing process of the composition according to the present invention may not proceed smoothly or the curing time may be excessively delayed; if it exceeds the above range, a rapid radical reaction may proceed, causing side reactions or unintended effects on other components of the composition according to the present invention, and residual components may remain excessively after curing. Therefore, the composition according to the present invention has the characteristic of enabling high-resolution molded articles to be formed even with a low-intensity light source by appropriately adjusting the content of the above photoinitiator and solvent.

[0081] The composition for 3D printing ink according to the present invention may further include additives such as surfactants, plasticizers, (thermal)polymerization inhibitors, stabilizers, defoaming agents, diluents, and viscosity modifiers. The said additives may be included in a minimum amount for which the said action can occur for economic reasons, and preferably, they may be included in an amount of 0.001 to 0.1 parts by weight based on 100 parts by weight of the total composition.

[0082]

[0083] 3D printed molded product

[0084] Next, a 3D printed molded article according to the present invention will be described.

[0085] The above 3D printed molded article may be a photocurable molded article formed by providing the above-described 3D printing ink composition to a 3D printing machine to form a structure therefrom, and irradiating a light source such as UV onto the formed structure.

[0086] Regarding the 3D printing equipment capable of manufacturing the above-mentioned 3D printed molded article, as long as it can manufacture the 3D printed molded article using the composition according to the present invention, it may not be limited to the detailed configuration thereof, and for example, it may include an output unit for outputting the composition, a pressure control unit for controlling the pressure of the output unit, a temperature control unit for controlling the temperature of the output unit, a sensor unit capable of sensing the conditions to change or select the pressure and temperature conditions according to the type, size, and property conditions of the structure to be output, and a control unit for controlling the pressure control unit and the temperature control unit.

[0087] The 3D printing ink composition according to the present invention includes a light absorber along with alginate, a biocompatible hydrogel, an acrylamide-based monomer, and a photocrosslinkable polymer, so that a pre-curing structure of 3D printing manufactured by methods such as DLP (Digital Light Processing) has excellent rheological properties to the extent that it can maintain a certain shape, and by irradiating it with a UV light source to perform photocuring, it is possible to form a molded article having a high elastic modulus and excellent ultimate tensile strength.

[0088] Accordingly, the ultimate tensile strength of the cured molded article of the 3D printing ink composition according to one embodiment of the present invention may be 100 to 400 kPa, specifically 100 to 365 kPa. The ultimate tensile strength of the 3D printing molded article may be a value measured based on an ASTM D638 specimen. The 3D printing molded article satisfying the aforementioned range of ultimate tensile strength may have excellent mechanical properties.

[0089] In addition, the modulus of the cured molded article of the 3D printing ink composition according to one embodiment of the present invention may be 40 to 100 kPa, and the toughness may be 80 to 700 kJ / m² 3 , or 85 to 650 kJ / m²3 It can satisfy mechanical properties.

[0090] The 3D printed molded article according to the present invention can be manufactured into various shapes or types of molded articles by varying the components of the 3D printing ink composition according to the purpose.

[0091] FIGS. 1a to 1d show 3D printed molded articles manufactured using a 3D printing ink composition according to the present invention. The 3D printed molded article according to the present invention may be manufactured as a multilayer molded article having different physical properties by varying the components of each composition. In addition, the 3D printing ink composition may be more suitablely applied to artificial organs, etc. by utilizing the above characteristics.

[0092] Specific embodiments of the present invention are presented below. However, the embodiments described below are merely for the purpose of specifically illustrating or explaining the present invention and do not limit the present invention. Furthermore, details not described herein can be sufficiently technically inferred by a person skilled in the art, so their description is omitted.

[0093]

[0094] Preparation Example 1: Preparation of a 3D printing ink composition

[0095] (1) 1.28 g of polyvinyl alcohol (PVA) and 0.64 g of alginate (AL) are added to 40 g of deionized water (DIW) as a solvent and stirred to prepare a first mixed solution.

[0096] (2) 12 g of acrylamide (AM), 0.4 g of polyethylene glycol ethyl diacrylate (PEGDA) as a photocrosslinkable polymer (molecular weight Mw=450 g / mol), and 0.008 g of tartrazine (light absorber A) as a light absorber are added to the first mixed solution above, and the mixture is stirred for 1 hour to prepare a second mixed solution.

[0097] (3) 0.16 g of TPO (Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide) nanoparticles are added to the above secondary mixed solution as a photoinitiator, and the mixture is stirred in a dark room for 30 minutes to prepare a 3D printing ink composition.

[0098]

[0099] Preparation Examples 2 to 4: Preparation of 3D printing ink compositions

[0100] A 3D printing ink composition is prepared in the same manner as Preparation Example 1, except that the content of each component included in the composition is as shown in Table 1 below.

[0101]

[0102] Preparation Examples 5 to 7: Preparation of 3D printing ink compositions

[0103] A 3D printing ink composition is prepared in the same manner as Preparation Example 1, except that 0.16 g of Jaune brilliant (light absorber B) is added along with tartrazine as a light absorber, and the content of alginate, biocompatible hydrogel, acrylamide, and photocrosslinkable polymer is as shown in Table 1 below.

[0104]

[0105] Comparative Manufacturing Examples 1 to 10: Preparation of 3D printing ink compositions

[0106] A 3D printing ink composition is prepared in the same manner as Preparation Example 1, except that the content of each component included in the composition is as shown in Table 2 below.

[0107] (Unit: g) Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Preparation Example 7 Solvent 40 40 40 44 38.5 40 Acrylamide 12 12 18 23 18 18 18 PEGDA 0.4 0.4 0.4 0.4 0.4 40.5 4 PVA 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.6 4.6 4.6 4.6 4.6 4.6 4.6 4.9 4.0 9 4.8 1.1 60.1 60.1 60.1 60.0 10.0 10.0 10.0 1 Light absorber B----0.080.080.16

[0108] * Light absorber A: Tartrazine

[0109] * Light absorber B: Jaune brilliant

[0110]

[0111] (Unit: g) Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 Comparative Manufacturing Example 3 Comparative Manufacturing Example 4 Comparative Manufacturing Example 5 Comparative Manufacturing Example 6 Comparative Manufacturing Example 7 Comparative Manufacturing Example 8 Comparative Manufacturing Example 9 Comparative Manufacturing Example 10 Solvent 40 40 40 40 40 40 40 40 Acrylamide 18 18 18 18 18 18 18 18 PEGDA 0.4 0.4 0.5 40.5 40.27 1.5 0.5 40.5 40.5 40.5 40.5 4PVA 1.2 8 1.2 8 1.2 8 1.2 8 1.2 8 1.2 8 1.9 21.2 8 1.2 8 Alginate 0.6 40.9 6 0.8 0.8 0.8 0.8 0.8 0.8 1.2 TPO 0.1 6 0.2 40.0 40.9 6 0.48 0.48 0.48 0.48 0.48 0.48 Light absorber A0.048-0.0010.0010.0010.0010.0010.0010.0010.001 Light absorber B-0.0160.160.160.160.160.160.160.160.16

[0112]

[0113] Example 1: Manufacture of a 3D printed molded article

[0114] The 3D printing ink composition prepared in Manufacturing Example 1 above was loaded into a DLP printer (IM-96, Carima Co.) to manufacture a 3D printed molded product.

[0115] Specifically, after loading the composition prepared in Preparation Example 1 above onto the tray of a DLP printer, with a layer thickness of 0.1 mm and a light intensity of 25 mW / cm² 2 3D printing was performed using a 385 nm LED light source with a burn-in exposure time of 40 seconds and a normal exposure time of 8 to 10 seconds.

[0116] Next, the molded 3D product was cleaned with ethanol for 1 to 5 minutes and dried in a vacuum oven to produce a final 3D printed product.

[0117]

[0118] Examples 2 to 7: Manufacture of 3D printed molded articles

[0119] For each 3D printing ink composition prepared in Preparation Examples 2 to 7, a 3D printed molded article was prepared in the same manner as in Example 1, except that the light intensity, burn-in exposure time, and normal exposure time were as shown in Table 3 below.

[0120] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Light intensity (mW / cm²) 2 )252525252577-In Exposure Time(s)40404040301313 Normal Exposure Time(s)8~108~108~10108~105~75~7

[0121]

[0122] Comparative Examples 1 to 10: Manufacture of 3D printed molded articles

[0123] For each 3D printing ink composition prepared in Comparative Manufacturing Examples 1 to 10, a 3D printed molded article was prepared in the same manner as in Example 1, except that the light intensity, burn-in exposure time, and normal exposure time were as shown in Table 4 below.

[0124] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Light Intensity (mW / cm²) 2 )252577777777 No.-In Exposure Time(s)4010131313131313131313 Normal Exposure Time(s)8~103~566666666

[0125]

[0126] Experimental Example: Evaluation of Physical Properties of 3D Printed Molded Products

[0127] (1) For the 3D printed molded products manufactured in Examples 1 to 7 and Comparative Examples 1 to 10 above, the ultimate tensile strength (UTS), modulus, and toughness were measured in the following manner, and the results are shown in Tables 5 and 6 below.

[0128] 1) Ultimate Tensile Strength (UTS)

[0129] The 3D printed molded products manufactured in the examples and comparative examples were prepared as specimens with dimensions of 50 mm * 10 mm * 3 mm, and measurements were performed. Stress-strain data was measured using a tensile testing machine (Mark-10) while stretching the standardized specimens at a speed of 100 mm / min until the specimens broke. The ultimate tensile strength was measured by extracting the maximum stress value from the measured stress-strain graph.

[0130] 2) Modulus

[0131] The 3D printed molded products manufactured in the examples and comparative examples were prepared as specimens with dimensions of 50 mm * 10 mm * 3 mm, and measurements were performed. Stress-strain data was measured using a tensile testing machine (Mark-10) while stretching the standardized specimens at a speed of 100 mm / min until the specimens broke. The modulus was measured through the slope within the elastic range of the measured stress-strain graph.

[0132] 3) Toughness

[0133] The 3D printed molded products manufactured in the examples and comparative examples were prepared as specimens with dimensions of 50 mm * 10 mm * 3 mm, and measurements were performed. Stress-strain data was measured using a tensile testing machine (Mark-10) while stretching the standardized specimens at a speed of 100 mm / min until the specimens broke. Toughness was measured by calculating the area under the curve in the measured stress-strain graph through integration.

[0134] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 UTS (kPa) 110.4 104.2 236.8 364.0 182.3 177.3 190.5 Modulus (kPa) 4455.2 70.1 63.3 65.7 96.5 81.2 Toughness (kJ / m3) 101.3 89 352.1 623 160.7 165.3 223.7

[0135]

[0136] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 UTS (kPa) Unmeasurable 99.6 Unmeasurable 172.3 130.2 180.0 95.2 190.1 103.1 188.7 Modulus (kPa) Unmeasurable 22.2 Unmeasurable 98.8 54.9 195.2 83.3 79.5 85.2 117.3 Toughness (kJ / m3) Unmeasurable 179 Unmeasurable 149.0 149.7 17832.1 320 581 56.4

[0137]

[0138] (2) Referring to FIG. 3, it can be seen that through Examples 2 to 4, the ultimate tensile strength and toughness increase as the acrylamide-based monomer included in the 3D printing ink composition increases within a certain content range.

[0139] (3) Referring to FIG. 1b and FIG. 2a, it can be seen that in Comparative Example 1 compared to Example 3, when the content of the light absorber exceeds the appropriate range, the 3D printed product is not molded completely. In addition, in Comparative Example 2 compared to Example 3, when tartrazine is not included as a light absorber, it can be seen that the resolution of the 3D printed product is reduced due to overcuring.

[0140] (4) Referring to FIG. 1d and FIG. 2b, it can be seen that when the content of the photoinitiator is included in an amount less than the appropriate range as in Comparative Example 3 compared to Example 7, the 3D printed product is not molded completely, and when the photoinitiator is included in an amount exceeding the appropriate range as in Comparative Example 4, the 3D printing ink composition is overcured.

[0141] (5) Referring to FIG. 4, it can be seen that the modulus increases as the photocrosslinkable polymer included in the 3D printing ink composition increases within a certain content range through Example 7, Comparative Example 5, and Comparative Example 6. However, it can be seen that the ultimate tensile strength and toughness decrease when the photocrosslinkable polymer included in the 3D printing ink composition exceeds a certain content range.

[0142] (6) Referring to FIG. 5, it can be seen that the 3D printing ink composition containing biocompatible hydrogel induces an improvement in ultimate tensile strength and toughness through Example 7, Comparative Example 7 and Comparative Example 8, and that the improvement in toughness becomes more pronounced as the content of biocompatible hydrogel increases within a certain content range.

[0143] (7) Referring to FIG. 6, it can be seen that the 3D printing ink composition containing alginate induces an improvement in ultimate tensile strength and toughness. However, it can be seen that if the alginate included in the 3D printing ink composition exceeds a certain content range, the toughness actually decreases.

[0144]

[0145] 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.

Claims

1. Alginate; Biocompatible hydrogel; Acrylamide monomer; Photocrosslinkable polymer; light absorber; and containing a solvent 3D printing ink composition.

2. In Paragraph 1, The above-mentioned biocompatible hydrogel comprises one or more of gelatin, gelatin methacrylate, collagen, fibrinogen, fibrin, hyaluronic acid, methyl cellulose, chitosan, chitin, Extracel™, pectin, polylactic acid (PLA), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyphosphate, synthetic peptides, and polyethylene glycol. 3D printing ink composition.

3. In Paragraph 1, The above acrylamide-based monomers are acrylamide, N-isopropylacrylamide (NIPAM), N-tert-butyl acrylamide, N,N-diethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N,N-ethylmethylacrylamide, N-isopropylmethacrylamide, N-hydroxyethylacrylamide, N-(isobutoxymethyl)acrylamide, and N-tert-butylmethacrylamide. A compound comprising one or more of N,N-diethylmethacrylamide and N-ethylmethacrylamide, 3D printing ink composition.

4. In Paragraph 1, The above photocrosslinkable polymer comprises one or more of polyethylene glycol ethyl methacrylate (PEGMA), polyethylene glycol ethyl acrylate (PEGA), polyethylene glycol ethyl diacrylate (PEGDA), and polyethylene glycol ethyl dimethacrylate (PEGDMA). 3D printing ink composition.

5. In Paragraph 1, The above light absorbers are tartrazine, Jaune brilliant, sunset yellow FCF, brilliant blue FCF, indigo carmine, fast green FCF anthocyanins, anthocyanidin, erythrosine, Allura red AC, riboflavin, ascorbic acid, quinoline yellow WS, carmoisine, Ponceau 4R, patent blue V, green S, yellow 2G, orange GGN, red 2G, caramel color, and phenol red. A compound comprising one or more of red), methyl orange, 4-nitrophenol, and NADH disodium salt, 3D printing ink composition.

6. In Paragraph 1, The composition comprising 0.1 to 5 parts by weight of the alginate based on 100 parts by weight of the total composition, 3D printing ink composition.

7. In Paragraph 1, The composition comprises 1 to 5 parts by weight of the biocompatible hydrogel based on 100 parts by weight of the total composition. 3D printing ink composition.

8. In Paragraph 1, The composition comprises 10 to 50 parts by weight of the acrylamide-based monomer based on 100 parts by weight of the total composition. 3D printing ink composition.

9. In Paragraph 1, The composition comprises 0.1 to 2 parts by weight of the photocrosslinkable polymer based on 100 parts by weight of the total composition. 3D printing ink composition.

10. In Paragraph 1, The composition comprises 0.005 to 0.5 parts by weight of the light absorber based on 100 parts by weight of the total composition. 3D printing ink composition.

11. In Paragraph 1, The above composition comprises lithium benzoyl(phenyl)phosphinate (BP), α-hydroxyketone derivatives (irgacure 2959, irgacure 184, irgacure 651, irgacure 369, irgacure 907, etc.), phosphate derivatives (TPO, TPO-Na, LAP, BAPO, BAPO-ONa, BAPO-OLi, etc.), azo-initiator (2,2'-azobis[2-methyl-N-(2-hydroxyethyl) promionamide] (VA-086)), eosin-Y, riboflavin (B2), and camphorquinone. Erythrosine, Rose Bengal, WSPI (1,4-bis(4-N,N-bis(6-N,N,N-trimethylammonium)hexyl)amino)-styryl)-2,5-dimethoxybenzene tetraiodide)), BDEA (2,5-bis-[4-(diethylamino)-benzylidene]-cyclopentanone)), P2CK (3,3'-((((1E,1'E)-(2-oxocyclopentane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))dipropanoate)(P2CK (3,3'-((((1E,1'E)-(2-oxocyclopentane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))dipropanoate)) and G2CK (sodium 2,2'-((((1E,Affecting further comprising one or more photoinitiators selected from 1'E)-(5-methyl-2-oxocyclohexane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))diacetate)(G2CK (sodium 2,2'-((((1E,1'E)-(5-methyl-2-oxocyclohexane-1,3-diylidene)bis(methanylylidene))bis(4,1-phenylene))bis(methylazanediyl))diacetate)). 3D printing ink composition.

12. In Paragraph 11, The composition comprises 0.1 to 1.5 parts by weight of the photoinitiator based on 100 parts by weight of the total composition. 3D printing ink composition.

13. A 3D printed molded article formed by photocuring the 3D printing ink composition according to claim 1.

14. In Paragraph 13, The ultimate tensile strength (UTS) of the above 3D printed molded article is 100 to 400 kPa, 3D printed molded product.

15. In Paragraph 13, The modulus of the above 3D printed molded product is 40 to 100 kPa, 3D printed molded product.

16. In Paragraph 13, The toughness of the above 3D printed molded product is 80 to 700 kJ / m² 3 thing that is, 3D printed molded product.

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