Resin composition and photocuring three-dimensional printing model

Abstract

The invention discloses a resin composition and a photocuring three-dimensional printing model. A resin composition includes 80 parts by weight of an acrylate mixture, 24 parts by weight of a surfactant, 16 parts by weight of animal hydrolyzed collagen, and 30-32 parts by weight of water. The photocuring three-dimensional printing model prepared from the resin composition has high structural stability and high bionic property.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a composition and a model made of the composition, and particularly relates to a resin composition and a photocured three-dimensional printing model made of the resin composition. BACKGROUND

[0002] Three-dimensional (3D) printing technology is gradually applied in the field of bionics due to its high flexibility and precise and rapid manufacturing capability. However, it is extremely difficult to find a material that is suitable for three-dimensional printing and has ideal bionic properties. For example, the printability requires the material to have appropriate fluidity and curing performance during the printing process, while the bionicity requires the material to meet the standards in mechanical strength, flexibility, and cell adhesion and growth, etc. The above-mentioned requirements often contradict each other and are difficult to satisfy simultaneously. Therefore, how to provide a three-dimensional printing material with printability and bionicity, so as to prepare a three-dimensional printing model with high structural stability and high bionicity, is a subject actively studied by those skilled in the art. SUMMARY

[0003] The present disclosure provides a resin composition and a photocured three-dimensional printing model made of the resin composition. The photocured three-dimensional printing model made of the resin composition of the present disclosure has high structural stability and high bionicity.

[0004] According to some embodiments of the present disclosure, the resin composition comprises 80 parts by weight of an acrylate mixture, 24 parts by weight of a surfactant, 16 parts by weight of animal hydrolyzed collagen, and 30 to 32 parts by weight of water.

[0005] In some embodiments of the present disclosure, the animal hydrolyzed collagen is fish hydrolyzed collagen.

[0006] In some embodiments of the present disclosure, the surfactant is a cationic surfactant.

[0007] In some embodiments of the present disclosure, the cationic surfactant comprises cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, alkyl dimethyl phenyl ammonium chloride, or a combination thereof.

[0008] In some embodiments of the present disclosure, the acrylate mixture comprises 30 to 50 wt% of an acrylate, based on 100 wt% of the total weight of the acrylate mixture.

[0009] In some embodiments of the present disclosure, the viscosity of the acrylate mixture is 75 to 76 mPa·s, measured by Brookfield viscosity measurement method at a temperature of 25°C.

[0010] In some embodiments of the present application, the acrylate-based mixture comprises a polymer copolymerized from phenol methane, epoxy chloropropane and acrylate.

[0011] In some embodiments of the present application, the acrylate-based mixture comprises dipropylene glycol diacrylate.

[0012] In some embodiments of the present application, the acrylate-based mixture comprises glycerol trihydroxypropyl ether triacrylate.

[0013] According to some other embodiments of the present application, the photo-cured three-dimensional printing model is prepared by a photo-cured three-dimensional printing process using the aforementioned resin composition, wherein the acrylate-based mixture is polymerized to form an acrylate-based polymer.

[0014] According to the aforementioned embodiments of the present application, by adjusting the respective proportions of the acrylate-based mixture and the animal hydrolyzed collagen in the resin composition, the resin composition can be stably maintained in a solid state for a long time after curing, and can have structural properties close to those of biological tissues. In this way, the photo-cured three-dimensional printing model made of the resin composition of the present application can have both high structural stability and high bionics. BRIEF DESCRIPTION OF DRAWINGS

[0015] In order to make the above and other objects, features, advantages and embodiments of the present application more comprehensible, the following description of the drawings is provided:

[0016] Figure 1 Flow chart of the preparation method of the resin composition according to some embodiments of the present application;

[0017] Figure 2 Viscosity-shear rate relationship diagram of the acrylate-based mixture according to some embodiments of the present application;

[0018] Figure 3A and Figure 4A Viscosity-shear rate relationship diagrams of the resin compositions of Examples 1-2, respectively;

[0019] Figure 3B and Figure 4B Storage modulus / loss modulus-time relationship diagrams of the resin compositions of Examples 1-2, respectively;

[0020] Figure 5A , Figure 6A , Figure 7A , Figure 8A , Figure 9A , Figure 10A and Figure 11 Viscosity-shear rate relationship diagrams of the resin compositions of Comparative Examples 1-7, respectively;

[0021] Figure 5A ,Figure 6A , Figure 7B , Figure 8B , Figure 9B , Figure 10B Storage modulus / loss modulus versus time graphs for the resin compositions of Comparative Examples 1-6; and

[0022] Figure 12A and Figure 12B The images shown are photographs of a photopolymer 3D printed model before and after drying, according to some embodiments of the present invention. Detailed Implementation

[0023] The following drawings will disclose several embodiments of the present invention. For clarity, many practical details will be described in the following description. However, it should be understood that these practical details should not be used to limit the invention. That is, in some embodiments of the present invention, these practical details are not essential and therefore should not be used to limit the invention. In addition, for the sake of simplicity, some conventional structures and components will be shown in the drawings in a simple schematic manner. Furthermore, for the reader's convenience, the dimensions of the components in the drawings are not drawn to scale.

[0024] This invention provides a resin composition suitable for photopolymerization 3D printing and a photopolymerization 3D printed model prepared from the resin composition. By adjusting the proportions of the acrylate mixture and animal hydrolyzed collagen in the resin composition, the resin composition can stably maintain a solid state for a long time after curing and can possess structural characteristics close to those of biological tissue. Therefore, the photopolymerization 3D printed model made from the resin composition of this invention can combine high structural stability and high biomimicry. Medical researchers can use the photopolymerization 3D printed model of this invention to simulate the structure and feel of biological tissues in vitro, thereby improving the accuracy of medical research such as simulated surgery and organ implantation evaluation.

[0025] In detail, the resin composition of the present invention comprises 80 parts by weight of an acrylate mixture, 24 parts by weight of a surfactant, 16 parts by weight of hydrolyzed animal collagen, and 30 to 32 parts by weight of water. For clarity and ease of explanation, the role and efficacy of each component in the resin composition will be described in some embodiments using the preparation methods of the resin composition.

[0026] Please see Figure 1which is a flow chart of a method for preparing a resin composition according to some embodiments of the present application. The method for preparing a resin composition can comprise steps S10 to S20. In step S10, animal hydrolyzed collagen, a surfactant, and an acrylate mixture are uniformly mixed in water to form a dispersion. In step S20, the respective proportions of the animal hydrolyzed collagen and the acrylate mixture in the dispersion are adjusted to form a resin composition. In the following, each of the above steps will be described in sequence.

[0027] First, in step S10, animal hydrolyzed collagen, a surfactant, and an acrylate mixture are uniformly mixed in water to form a dispersion. In some embodiments, the compatibility of the components can be improved by adjusting the order of addition of the components. For example, the animal hydrolyzed collagen can be added first in water, the surfactant can be added after the animal hydrolyzed collagen is dissolved, and the acrylate mixture can be added after the surfactant is dissolved. In this way, the animal hydrolyzed collagen can be ensured to be coated by the surfactant before contacting the acrylate mixture, thereby improving the compatibility of the components. On the other hand, by controlling the weight ratio of the animal hydrolyzed collagen, the surfactant, and the acrylate mixture to be 2:3:10 as described above, the compatibility of the components can also be improved.

[0028] The animal hydrolyzed collagen is formulated to improve the biomimicry of the resin composition, so that the resin composition has structural properties and a hand that are close to biological tissues. For example, the resin composition can have mechanical properties (e.g., Young's modulus) and a hand that are close to human blood vessels. Compared with other types of hydrolyzed collagen such as plant, synthetic hydrolyzed collagen, etc., animal hydrolyzed collagen can achieve better biomimicry; and compared with non-hydrolyzed collagen such as animal, plant non-hydrolyzed collagen, etc., animal hydrolyzed collagen has a smaller molecular weight due to the hydrolysis treatment, and thus has higher solubility. In some embodiments, the animal hydrolyzed collagen can be fish hydrolyzed collagen. Compared with pig, bovine hydrolyzed collagen, fish hydrolyzed collagen has a smaller molecular weight, and thus has higher solubility, can be dissolved in water at room temperature (e.g., 25°C), and does not need to go through an additional heating step to improve its solubility, thereby improving process convenience.

[0029] In addition, the present application controls the weight ratio of the animal hydrolyzed collagen and water in the range of 16:30 to 16:32 (for example, 16:31) to balance the printability, the structural stability after curing and the bionics of the resin composition. Specifically, if the proportion of the animal hydrolyzed collagen in water is too low (for example, the weight ratio of the animal hydrolyzed collagen and water is 15:32), the resin composition cannot be three-dimensionally printed due to the too low viscosity before curing, and cannot have bionics due to the insufficient deformation resistance (too low Young's modulus) after curing; if the proportion of the animal hydrolyzed collagen in water is too high (for example, the weight ratio of the animal hydrolyzed collagen and water is 17:30), the resin composition cannot be three-dimensionally printed due to the too high viscosity before curing, and cannot be stably maintained in the solid state after curing in the form of a gel or a semi-gel.

[0030] The surfactant is formulated to improve the compatibility of the animal hydrolyzed collagen and the acrylate mixture, so that the resin composition has uniform material distribution and stable structure. In some embodiments, the surfactant can be a cationic surfactant, an anionic surfactant, a nonionic surfactant or a combination thereof. In preferred embodiments, the surfactant can be a cationic surfactant. Compared with anionic surfactants or nonionic surfactants, since the cationic surfactant belongs to the water-in-oil (W / O) type of surfactant, it can disperse the water phase animal hydrolyzed collagen in the oil phase acrylate mixture droplets, avoid the animal hydrolyzed collagen from gathering together, thereby forming a stable emulsion system and effectively preventing phase separation. In some embodiments, the cationic surfactant can include cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, alkyl dimethyl phenyl ammonium chloride or a combination thereof. Since each of the above-mentioned cationic surfactants contains a quaternary ammonium salt structure, it can further have good antimicrobial properties and good biocompatibility, thereby improving the accuracy of applying the resin composition to medical research such as simulated surgery, organ implant evaluation, etc. On the other hand, by controlling the weight ratio of the animal hydrolyzed collagen, the surfactant and the acrylate mixture to be 2:3:10 as described above, the compatibility of each component is also improved.

[0031] The acrylate mixture is formulated as the base material of the resin composition, so that the resin composition has photocuring and printability, and has high structural stability after curing. In detail, the acrylate mixture can include a photoinitiator and at least one acrylate monomer, wherein the photoinitiator can initiate polymerization after light exposure, and the acrylate monomers can polymerize with each other with the assistance of the photoinitiator after light exposure. Since the acrylate monomers need to be exposed to light to polymerize with each other to form a polymer with relatively high viscosity, the acrylate mixture can have a suitable viscosity to facilitate three-dimensional printing in the case of no light exposure. Please refer toFigure 2 which is a viscosity-shear rate graph of the acrylate-based mixture according to some embodiments of the present application. As shown, the viscosity of the acrylate-based mixture can be 75 mPa-s to 76 mPa-s. Since the viscosity of the acrylate-based mixture falls within the printable viscosity range (25 mPa-s to 5000 mPa-s) described in the literature 3D printing of ultra-high viscosity resin by a linear scan-based vat photopolymerization system (Nature Communications volume 14, Article number: 4303 (2023)), and the viscosity of the acrylate-based mixture is almost constant and does not change with the change of shear rate, the acrylate-based mixture can be used as a suitable three-dimensional printing base material. It should be understood that the viscosity of the acrylate-based mixture is measured by the Brookfield viscosity measurement method (parallel plate rotor with a diameter of 25 mm) at a temperature of 25°C. Figure 2

[0032] In some embodiments, the photoinitiator in the acrylate-based mixture can be a polymer copolymerized from phenol methane, epichlorohydrin and acrylate, which can generate free radicals after light irradiation, thereby initiating free radical polymerization of acrylate monomers to form a polymer. In some embodiments, the photoinitiator can be a polymer copolymerized from phenol methane, (chloromethyl) oxirane and 2-propenoic acid ester, that is, the photoinitiator can be bisphenol A epoxy diacrylate (CAS NO. 55818-57-0). Bisphenol A epoxy diacrylate can be quickly cured after light irradiation, which helps to quickly form a biomimetic model; and bisphenol A epoxy diacrylate can have good biocompatibility and antimicrobial properties after proper treatment, which can reduce irritation and rejection to biological tissues, helping to improve the accuracy of medical research such as simulation surgery, organ implant evaluation, etc.; and bisphenol A epoxy diacrylate has high mechanical strength and toughness after curing, which is beneficial to simulate the mechanical properties of biological tissues and provides necessary support and elasticity. It is worth noting that bisphenol A epoxy diacrylate has deep curing ability, which has high light absorption efficiency in the visible light range, enabling deep curing reaction, so that not only the inside of the biomimetic model with large thickness can be fully cured to form a uniform structure, but also complex shape design can be achieved. In some embodiments, the content of the polymer copolymerized from phenol methane, epichlorohydrin and acrylate can be 30 wt% to 40 wt% based on 100 wt% of the total weight of the acrylate-based mixture, thereby providing good photocuring property and high structural stability.​

[0033] In some embodiments, the acrylate monomer in the acrylate mixture can include dipropylene glycol diacrylate (CAS NO. 57472-68-1). Compared to other kinds of monomers, the crosslinking density and chemical structure of dipropylene glycol diacrylate can be easily adjusted by adjusting the light exposure time or adjusting the monomer dosage, and such high adjustability helps to meet the needs of different biomimetic applications (for example, the application range can be from soft tissue to hard bone structure). In addition, dipropylene glycol diacrylate has the characteristics of high solubility, low viscosity and low volatility, which helps to improve the dispersion uniformity, viscosity adjustability and stability after curing of the acrylate mixture. In addition, dipropylene glycol diacrylate has a transparent appearance after crosslinking and curing, which is suitable for biomimetic applications that require observation of internal structure or internal function. In some embodiments, the content of dipropylene glycol diacrylate can be 30wt% to 50wt% based on the total weight of the acrylate mixture being 100wt%, so as to achieve an appropriate combination with the photoinitiator and provide a moderate crosslinking density.

[0034] In some embodiments, the acrylate monomer in the acrylate mixture can further include glyceryl trihydroxypropyl ether triacrylate (CAS NO. 52408-84-1). Since glyceryl trihydroxypropyl ether triacrylate has multiple (three) acrylate groups, by further adding glyceryl trihydroxypropyl ether triacrylate, it helps to improve the crosslinking structure density of the polymer, thereby the mechanical strength and elasticity of the polymer, so that the light-cured three-dimensional printing model is suitable for biomimetic applications that require high strength, high thermal stability, high chemical stability, high durability. In addition, since glyceryl trihydroxypropyl ether triacrylate has a low shrinkage rate during crosslinking and curing, it can provide good dimensional stability during printing, which helps to improve the three-dimensional printing precision. In addition, since glyceryl trihydroxypropyl ether triacrylate has a high surface energy after crosslinking and curing, it is beneficial for cell adhesion and growth, so the polymer crosslinked by glyceryl trihydroxypropyl ether triacrylate can well simulate the environment in the body, thereby improving the accuracy of medical research such as simulation surgery and organ implant evaluation. In the embodiments in which the acrylate monomer further includes glyceryl trihydroxypropyl ether triacrylate, the content of dipropylene glycol diacrylate and glyceryl trihydroxypropyl ether triacrylate can each be 15wt% to 25wt% based on the total weight of the acrylate mixture being 100wt%, so as to achieve an appropriate combination of the two. Overall, regardless of the number of acrylate monomers included in the acrylate mixture, the acrylate mixture can include 30wt% to 50wt% of acrylate monomers based on the total weight of the acrylate mixture being 100wt%.

[0035] After the step S10 is completed, a dispersion liquid containing the animal hydrolyzed collagen, the surfactant, the acrylate mixture, and water can be obtained. In some embodiments, the dispersion liquid can be a clear and transparent liquid. In other embodiments, since the acrylate mixture can further include an additive such as a colorant, the dispersion liquid can have a precipitate, in which case, the precipitate in the dispersion liquid can be removed by, for example, decanting the clear liquid and / or filtering the precipitate.

[0036] Subsequently, in the step S20, the respective proportions of the animal hydrolyzed collagen and the acrylate mixture in the dispersion liquid are adjusted to form a resin composition. For example, the respective proportions of the acrylate mixture and the animal hydrolyzed collagen in the dispersion liquid can be controlled by reducing the water in the dispersion liquid or adding additional water to ensure that the resin composition includes 80 parts by weight of the acrylate mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 30 to 32 parts by weight of water. By adjusting the proportion of the acrylate mixture in the resin composition, it can be ensured that the resin composition can stably maintain a solid state for a long time after curing; and by adjusting the proportion of the animal hydrolyzed collagen in the resin composition, it can be ensured that the resin composition has a structure close to that of a biological tissue. In other words, by balancing the respective proportions of the acrylate mixture and the animal hydrolyzed collagen in the resin composition, the photocured three-dimensional printed model made of the resin composition can have both high structural stability and high bionics.

[0037] Subsequently, the photocured three-dimensional printing process can be performed using the resin composition of the present application to form a photocured three-dimensional printed model having both structural stability and bionics. In more detail, the photocured three-dimensional printing process can crosslink and polymerize the acrylate monomers in the resin composition to form an acrylate polymer, thereby providing the photocured three-dimensional printed model with high structural stability, and the appropriate amount of animal hydrolyzed collagen can ensure that the photocured three-dimensional printed model has high bionics while maintaining high structural stability. Overall, the photocured three-dimensional printed model can include about 80 parts by weight of the acrylate polymer, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 30 to 32 parts by weight of water.

[0038] The features and effects of the present application will be described in more detail below with reference to the respective comparative examples and embodiments. It should be understood that the materials used, their amounts and proportions, the processing details, and the processing procedures, etc. can be appropriately changed in accordance with the general knowledge in the art without exceeding the scope of the present application. Therefore, the present application should not be interpreted restrictively by the respective embodiments described below.

[0039] <Description of the respective embodiments and comparative examples>

[0040] Each of the examples and each of the comparative examples is a resin composition prepared by the aforementioned steps S10 to S20. The proportions of the components in each of the examples and each of the comparative examples are described below.

[0041] [Example 1]

[0042] 80 parts by weight of the acrylic ester mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 32 parts by weight of water (the proportion of the animal hydrolyzed collagen in the water is about 50 wt%).

[0043] [Example 2]

[0044] 80 parts by weight of the acrylic ester mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 30.18 parts by weight of water (the proportion of the animal hydrolyzed collagen in the water is about 53 wt%).

[0045] [Comparative Example 1]

[0046] 80 parts by weight of the acrylic ester mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 35.55 parts by weight of water (the proportion of the animal hydrolyzed collagen in the water is about 45 wt%).

[0047] [Comparative Example 2]

[0048] 80 parts by weight of the acrylic ester mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 34.04 parts by weight of water (the proportion of the animal hydrolyzed collagen in the water is about 47 wt%).

[0049] [Comparative Example 3]

[0050] 80 parts by weight of the acrylic ester mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 28.57 parts by weight of water (the proportion of the animal hydrolyzed collagen in the water is about 56 wt%).

[0051] [Comparative Example 4]

[0052] 80 parts by weight of the acrylic ester mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 27.11 parts by weight of water (the proportion of the animal hydrolyzed collagen in the water is about 59 wt%).

[0053] [Comparative Example 5]

[0054] 80 parts by weight of the acrylic ester mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 25.39 parts by weight of water (the proportion of the animal hydrolyzed collagen in the water is about 63 wt%).

[0055] [Comparative Example 6]

[0056] 80 parts by weight of the acrylate-based mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 23.88 parts by weight of water (the proportion of the animal hydrolyzed collagen in water is about 67 wt%).

[0057] [Comparative Example 7]

[0058] 80 parts by weight of the acrylate-based mixture, 24 parts by weight of the surfactant, 16 parts by weight of the animal hydrolyzed collagen, and 22.53 parts by weight of water (the proportion of the animal hydrolyzed collagen in water is about 71 wt%).

[0059] [Experiment Example 1: Viscosity Test of Resin Composition]

[0060] In this experiment example, the viscosity test of the resin composition was carried out by the Brookfield viscosity measurement method (the diameter of the parallel plate rotor is 25 mm) at a temperature of 25°C. The test results of the examples are shown in Table 1 and Table 2, respectively. Figure 3A and Figure 4A , which are the viscosity-shear rate graphs of the resin compositions of Examples 1-2, respectively. As shown in Figure 3A , when the proportion of the animal hydrolyzed collagen in water is about 50 wt%, the viscosity of the resin composition stably falls in the range of 65-75 mPa-s. As shown in Figure 4A , when the proportion of the animal hydrolyzed collagen in water is about 53 wt%, the viscosity of the resin composition stably falls in the range of 87-101 mPa-s. Since both of the above viscosity ranges fall in the printable viscosity range (25-5000 mPa-s) recorded in the document 3D printing of ultra-high viscosity resin by a linear scan-based vat photopolymerization system, and both of the above viscosity ranges are very close to the viscosity of the acrylate-based mixture with excellent printability (as shown in Figure 2 ), it can be seen that the resin compositions of Examples 1-2 have good printability and are suitable for three-dimensional printing.

[0061] In contrast, the test results of the comparative examples are shown in Table 3 and Table 4, respectively. Figure 5A , Figure 6A , Figure 7A , Figure 8A , Figure 9A , Figure 10A and Figure 11 , which are the viscosity-shear rate graphs of the resin compositions of Comparative Examples 1-7, respectively. As shown in Figure 5Aand Figure 6A As shown in FIG. 1, when the proportion of the animal hydrolyzed collagen in water is too low, the viscosity of the resin composition is unstable and is lower than the lower limit value (25 mPa-s) of the printable viscosity range, which is not suitable for three-dimensional printing. As shown in FIG. 2, when the proportion of the animal hydrolyzed collagen in water is too high, the viscosity of the resin composition is unstable and is higher than the upper limit value (5000 mPa-s) of the printable viscosity range, which is not suitable for three-dimensional printing. As shown in FIG. 3, when the proportion of the animal hydrolyzed collagen in water is about 56 wt%, 59 wt%, 63 wt%, and 67 wt%, although the viscosity of the resin composition falls within the printable viscosity range (25-5000 mPa-s), the viscosity is too high and is far from the viscosity of the acrylate-based mixture with excellent printability, and the resin composition cannot be stably maintained in a solid state after three-dimensional printing and curing (which will be described in Experimental Example 2 below). Figure 11 Figure 7A Figure 8A Figure 9A Figure 10A As shown in FIG. 3, when the proportion of the animal hydrolyzed collagen in water is about 56 wt%, 59 wt%, 63 wt%, and 67 wt%, although the viscosity of the resin composition falls within the printable viscosity range (25-5000 mPa-s), the viscosity is too high and is far from the viscosity of the acrylate-based mixture with excellent printability, and the resin composition cannot be stably maintained in a solid state after three-dimensional printing and curing (which will be described in Experimental Example 2 below).

[0062] <Experimental Example 2: Test of structural stability of resin composition after curing>

[0063] In this experimental example, the storage modulus (G') and the loss modulus (G") of the resin compositions of Examples 1-2 and Comparative Examples 1-6 were measured, and the structural stability of the resin compositions after curing was determined by the value of tan delta (i.e., the value of G" / G'). The test method was to take 0.5 grams of the resin composition, irradiate it with ultraviolet light of wavelength 405 nm for 60 seconds, and measure and calculate the G', G", and tan delta of the resin composition using an Anton Paar MCR302, wherein the resin composition was uniformly mixed for 30 seconds (in the dark state) using a parallel plate rotor before irradiation with ultraviolet light. It should be understood that when tan delta > 1, the resin composition is a liquid, when tan delta < 1, the resin composition is a solid, when tan delta = 1, the resin composition is in a gel state (semi-solid state), and tgel represents the time at which the resin composition just enters the solid state after irradiation, that is, the time at which the gel state is reached, that is, the time at which tan delta = 1.

[0064] The test results of the examples can be seen in FIGS. 4-9, which are the storage modulus / loss modulus-time graphs of the resin compositions of Examples 1-2, respectively. As shown in FIG. 4, the resin composition of Example 1 has a storage modulus (G') of 1000 Pa, a loss modulus (G") of 100 Pa, and a tan delta of 0.1, which means that the resin composition is in a solid state after curing. Figure 3B Figure 4B As shown in FIG. 5, the resin composition of Example 2 has a storage modulus (G') of 1000 Pa, a loss modulus (G") of 100 Pa, and a tan delta of 0.1, which means that the resin composition is in a solid state after curing. Figure 3B Figure 4B ​​​​​​As shown, when the proportion of animal hydrolyzed collagen in water is approximately 50 wt% and 53 wt%, the tanδ value of the resin composition after curing is consistently much less than 1, indicating that the resin composition can stably maintain a solid state after curing and has high structural stability. Combining the results of Experiments 1 and 2, it can be seen that the resin compositions of Examples 1 and 2 not only have good printability but also can stably maintain a solid state after curing and molding, exhibiting high structural stability.

[0065] For the comparative examples, please refer to the test results. Figure 5B , Figure 6B , Figure 7B , Figure 8B , Figure 9B and Figure 10B These are storage modulus / loss modulus versus time graphs for the resin compositions of Comparative Examples 1-6. Figure 5B and Figure 6B As shown, when the proportion of animal hydrolyzed collagen in water is approximately 45 wt% and 47 wt%, although the tanδ value of the resin composition after curing is consistently much less than 1, it does not exhibit biomimetic properties (this will be explained in Experimental Example 3 below). Figure 7B , Figure 8B , Figure 9B and Figure 10B As shown, when the proportion of animal hydrolyzed collagen in water is too high, the tanδ value of the resin composition after curing is unstable and / or the tanδ value is relatively close to 1, indicating that the resin composition cannot be stably maintained in a solid state after curing and is prone to exhibiting a gel or semi-gel state.

[0066] <Experimental Example 3: Biomimetic Testing of Resin Components After Curing>

[0067] In this experimental example, the Young's modulus was calculated from the storage modulus (G') of the resin composition, so as to determine whether the resin composition has biomimicry for human arterial blood vessels (Young's modulus of about 1.9 ± 1.4 MPa) and human venous blood vessels (Young's modulus of about 6.9 ± 4.6 MPa). The results showed that the G' values of Examples 1-2 were about 0.020 MPa and 0.027 MPa, respectively, the G' values of Comparative Examples 1-2 were about 0.0018 MPa and 0.0020 MPa, respectively, and the G' values of Comparative Examples 4-6 were about 0.1 MPa, 0.2 MPa, 0.3 MPa, and 0.4 MPa, respectively. Thus, it can be seen that Examples 1-2 have mechanical properties closer to human arterial blood vessels and human venous blood vessels than Comparative Examples 1-2. On the other hand, although Comparative Examples 4-6 have mechanical properties closer to human arterial blood vessels and human venous blood vessels, it can be known from the results of the aforementioned Experimental Example 2 that Comparative Examples 4-6 cannot stably maintain a solid state after curing, and thus even if they have higher biomimicry, they cannot be successfully cured and formed.

[0068] <Experimental Example 4: Flexibility and storage of the photocured three-dimensional printing model>

[0069] Please refer to Figure 12A and Figure 12B , which are photographs of the photocured three-dimensional printing model according to some embodiments of the present application before and after drying, respectively. Specifically, Figure 12A and Figure 12B , the photocured three-dimensional printing model was prepared by three-dimensional printing using the resin composition of Example 1. As shown in Figure 12A , the photocured three-dimensional printing model has good flexibility and can be bent according to the needs, which helps to achieve the effect of biomimicry. As shown in Figure 12B , after the photocured three-dimensional printing model was left to dry at room temperature (25°C) for 72 hours, the hardness of the photocured three-dimensional printing model was improved, and although it could not be bent, it was convenient for storage. However, after the dried photocured three-dimensional printing model shown in Figure 12B was soaked in water, the photocured three-dimensional printing model could return to Figure 12A . In this way, the storage convenience and reusability of the photocured three-dimensional printing model can be greatly improved.

[0070] From the results of the experiments of Examples 1 to 3, it can be seen that, by adjusting the proportion of the animal hydrolyzed collagen in the resin composition, the content of the animal hydrolyzed collagen and the acrylate mixture is balanced, so that the resin composition can be stably maintained in a solid state for a long time after curing, and the resin composition can have a structure close to that of a biological tissue (for example, a human blood vessel) after curing. In this way, the photocured three-dimensional printing model made of the resin composition of the present application can have high structural stability and high bionics. In addition, from the results of Example 4, it can be seen that the photocured three-dimensional printing model of the present application can also have storage convenience and reusability.

[0071] Although the present application has been disclosed with the above-mentioned embodiments, it is not intended to limit the present application, and any person skilled in the art can make various modifications and improvements without departing from the spirit and scope of the present application, and the scope of protection of the present application shall be subject to the scope defined by the appended claims.

[0072] Symbol explanation:

[0073] S10-S20: steps

Claims

1. A resin composition, characterized in that, include: 80 parts by weight of an acrylate-based mixture; 24 parts by weight of surfactant; 16 parts by weight of hydrolyzed animal collagen; as well as 30 to 32 parts by weight of water.

2. The resin composition of claim 1, wherein the animal hydrolyzed collagen is fish hydrolyzed collagen.

3. The resin composition according to claim 1, wherein the surfactant is a cationic surfactant.

4. The resin composition of claim 3, wherein the cationic surfactant comprises hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, alkyldimethylphenylammonium chloride, or a combination thereof.

5. The resin composition of claim 1, wherein the acrylate mixture comprises 30 wt% to 50 wt% of acrylates, based on a total weight of 100 wt% of the acrylate mixture.

6. The resin composition of claim 1, wherein the viscosity of the acrylate mixture is 75 mPa·s to 76 mPa·s, as measured by the Brookfield viscosity measurement method at a temperature of 25°C.

7. The resin composition of claim 1, wherein the acrylate mixture comprises a polymer copolymerized from phenolic methane, epichlorohydrin and acrylate.

8. The resin composition of claim 1, wherein the acrylate mixture comprises dipropylene glycol diacrylate.

9. The resin composition of claim 1, wherein the acrylate mixture comprises glycerol trihydroxypropyl ether triacrylate.

10. A photopolymerizable 3D printed model, characterized in that, It is prepared by photopolymerization 3D printing process using the resin composition as described in claim 1, wherein the acrylate mixture is polymerized to form an acrylate polymer.

Images