Cocoa butter-based 3D printing material and preparation method thereof

Abstract

The invention provides a cocoa butter-based 3D printing material. The cocoa butter-based 3D printing material comprises cocoa butter and stearate. The stearate is at least one of calcium stearate, zinc stearate and magnesium stearate. The 3D printing material is good in formability, high in printing precision and excellent in thermal environment stability, and has the capability of loading fat-soluble bioactive components.

Description

Technical Field

[0001] The present invention relates to a cocoa butter-based 3D printing material and a preparation method thereof, belonging to the technical field of 3D printing materials. Background Art

[0002] Cocoa butter, a natural plant fat carefully extracted from cocoa beans, boasts a uniquely rich aroma, a smooth taste, and rich nutritional value. From a chemical perspective, cocoa butter is primarily composed of triglycerides with a specific molecular structure, the most representative of which is 1,3-dipalmitoyl-2-oleoyl-sn-glycerol. This unique chemical structure gives cocoa butter its distinctive physical and chemical properties.

[0003] Cocoa butter is also rich in antioxidants such as polyphenols and tocopherols. These ingredients not only effectively scavenge free radicals in the body but also offer numerous benefits, including improved cardiovascular health, digestive system function, and immune system enhancement. Therefore, it is widely regarded as a high-quality natural food ingredient. Cocoa butter also possesses excellent solvent properties, making it suitable as a solvent medium for loading and delivering fat-soluble active ingredients, thus showing broad application prospects in the pharmaceutical and health product fields.

[0004] In the field of food 3D printing technology, cocoa butter is often used as an auxiliary ingredient, added to chocolate or other primary printing substrates to significantly enhance its fluidity, improve taste, and optimize texture, making the printed food more delicious and appealing. However, when cocoa butter is used as the primary raw material in 3D printing, it exposes a series of significant drawbacks and challenges.

[0005] First, cocoa butter has a relatively low melting point and easily softens and deforms at room temperature. This characteristic results in poor visual stability in the finished printed product, making it difficult to maintain the desired shape over time. Second, cocoa butter's high fat content and low viscosity make it difficult to form a three-dimensional network with sufficient mechanical strength and fine structure during extrusion printing. This not only affects the precision and molding stability of the printed product, but can also cause structural collapse or deformation during printing. These limitations have significantly hindered the widespread application and promotion of cocoa butter as a primary printing material in the 3D printing field. Summary of the Invention The present invention provides a cocoa butter-based 3D printing material and a preparation method thereof, which can effectively solve the above-mentioned problems.

[0006] A cocoa butter-based 3D printing material comprises cocoa butter and stearate. In some embodiments, the stearate is at least one of calcium stearate, zinc stearate, and magnesium stearate.

[0007] In some embodiments, the ratio of cocoa butter, calcium stearate, zinc stearate and magnesium stearate is 8-12 ml: 2-12 g: 2-12 g: 2-12 g.

[0008] A printing method for cocoa butter-based 3D printing materials comprises the steps of melting cocoa butter, adding calcium stearate, zinc stearate, and magnesium stearate, and stirring the mixture to obtain a printing material; and performing 3D printing.

[0009] In some embodiments, the printing parameters of the 3D printing are as follows: nozzle diameter is 0.5-1 mm, extrusion volume is 100-300%, layer height is 0.4-0.6 mm, nozzle temperature is 10-45° C., and nozzle movement speed is 15-40 mm / s.

[0010] A use of the cocoa butter-based 3D printing material in the preparation of an oil-based material loaded with fat-soluble bioactive ingredients.

[0011] In some embodiments, the fat-soluble bioactive component includes at least one of carotenoids, fat-soluble vitamins, sterol compounds, unsaturated fatty acids, and anthracyclines.

[0012] The beneficial effects of the present invention are: The present invention provides a new type of composite 3D printing material, which uses cocoa butter as the main raw material. Specifically, this composite 3D printing material is formulated from cocoa butter and a variety of stearates. This material not only has excellent molding properties, ensuring smooth molding during the 3D printing process, but also has extremely high printing accuracy, which can meet the needs of high-precision printing. In addition, the stability of this material in a thermal environment is better than that of pure cocoa butter, and it can maintain stable physical and chemical properties under certain temperature conditions. More importantly, this composite 3D printing material also has the ability to load fat-soluble bioactive ingredients, which gives it broad application prospects in the biomedical field. Through the application of this material, not only can the practicality and diversity of 3D printing technology be improved, but also new solutions can be provided for the delivery and utilization of fat-soluble bioactive ingredients. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0014] Figure 1 These are the finished printed products of cocoa butter and calcium stearate printing materials in different ratios according to Example 1.

[0015] Figure 2 This is a graph showing the fidelity analysis results of the printed products of cocoa butter and calcium stearate at different ratios in Example 1.

[0016] Figure 3 These are the finished printed images of cocoa butter and magnesium stearate printing materials in different ratios according to Example 2.

[0017] Figure 4 This is a graph showing the fidelity analysis results of the printed products of cocoa butter and magnesium stearate at different ratios in Example 2.

[0018] Figure 5 These are the finished printed products of cocoa butter and zinc stearate printing materials in different ratios according to Example 3.

[0019] Figure 6 This is a graph showing the fidelity analysis results of the printed products of cocoa butter and zinc stearate at different ratios in Example 3.

[0020] Figure 7 These are the finished printed products of the cocoa butter mixed formula printing materials at different ratios in Example 4.

[0021] Figure 8 This is a fidelity analysis result diagram of the finished product printed with the cocoa butter mixed formula of Example 4.

[0022] Figure 9 This is a picture of the printed product of the cocoa butter-stearate mixed printing material loaded with β-carotene in Example 5.

[0023] Figure 10 This is a colorimeter result diagram of the cocoa butter-stearate mixed printing material loaded with β-carotene in Example 5.

[0024] Figure 11 This is a printed product image of the cocoa butter-stearate mixed printing material loaded with mitoxantrone in Example 6.

[0025] Figure 12 This is a colorimeter result diagram of the cocoa butter-stearate mixed printing material loaded with mitoxantrone in Example 6.

[0026] Figure 13 This is the heat resistance evaluation result of the 3D printing material of Example 8 (40°C) DETAILED DESCRIPTION In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Therefore, the following detailed description of the embodiments of the present invention provided in the drawings is not intended to limit the scope of the invention for which protection is claimed, but merely represents selected embodiments of the present invention.

[0027] A cocoa butter-based 3D printing material primarily consists of cocoa butter and stearate. Stearate, a widely used additive in various industrial applications, including food and pharmaceuticals, exhibits typical amphiphilic properties and high chemical stability. When combined with cocoa butter to form a composite system, stearate significantly improves the physical and chemical properties of cocoa butter through various mechanisms. Specifically, the hydrophobic long-chain regions of the stearate molecules interact effectively with the triglyceride molecules in cocoa butter. This interaction not only increases the viscosity of the cocoa butter but also promotes the formation of a stable three-dimensional crystalline network. This three-dimensional crystalline network effectively restricts the mobility of the fat molecules, allowing the cocoa butter to gradually transition from a liquid state to a semi-solid or solid state. Furthermore, the metal ions in the stearate can form coordination or ionic bonds with the polar groups of the fatty acids. This bonding not only significantly improves the thermal stability of the cocoa butter but also promotes its crystallization during cooling, further enhancing its solidification. This cocoa butter-based 3D printing material is capable of loading fat-soluble active ingredients.

[0028] In some specific embodiments, the stearate may include at least one of calcium stearate, zinc stearate, and magnesium stearate. These different stearates each have their own unique advantages and application effects in improving the performance of cocoa butter-based 3D printing materials.

[0029] In some embodiments, the ratio of cocoa butter, calcium stearate, zinc stearate, and magnesium stearate is 8-12 ml: 2-12 g: 2-12 g: 2-12 g. This ratio ensures that the ingredients can achieve optimal synergistic effects in the mixture to meet specific application requirements. By strictly controlling the ratio of these ingredients, the performance and stability of the final product can be optimized to a certain extent.

[0030] A printing method for cocoa butter-based 3D printing materials comprises the steps of melting cocoa butter, adding calcium stearate, zinc stearate, and magnesium stearate, and stirring the mixture to obtain a printing material; and performing 3D printing.

[0031] In some specific implementation cases, the printing parameters used in the 3D printing technology involved are set in detail as follows: First, the nozzle diameter is precisely controlled within the range of 0.5-1mm to ensure that the printing material can be extruded at an appropriate flow rate; second, the extrusion rate is set between 100% and 300% to adapt to the fluidity and printing requirements of different materials; third, the layer height of each layer is set between 0.4-0.6mm to ensure the uniformity of the printed layer and the stability of the structure; in addition, the nozzle temperature is controlled between 10-45°C to optimize the fluidity and viscosity of the material; finally, the nozzle movement speed is set between 15-40mm / s to ensure the smoothness of the printing process and the fineness of the print quality. The comprehensive regulation of these parameters is aimed at achieving efficient and high-quality 3D printing results.

[0032] The cocoa butter-based 3D printing material is used to prepare an oil-based material loaded with fat-soluble bioactive ingredients. This material, through its unique structure and properties, can stably bind and release fat-soluble ingredients, thus showing great potential in fields such as biomedicine and nutritional supplements.

[0033] In some embodiments, the fat-soluble bioactive ingredients include at least one of carotenoids, fat-soluble vitamins, sterol compounds, unsaturated fatty acids, and anthracyclines, but are not limited thereto. Carotenoids include β-carotene, α-carotene, γ-carotene, lycopene, and the like. β-carotene, as an important precursor of vitamin A, has multiple physiological functions such as antioxidant and immune enhancement. Fat-soluble vitamins include vitamins A, D, E, and K. Sterol compounds include cholesterol, β-sitosterol, stigmasterol, ergosterol, bile acid, and the like. Unsaturated fatty acids include oleic acid, linoleic acid, arachidonic acid, α-linolenic acid, and the like. Anthracyclines include doxorubicin, daunorubicin, mitoxantrone, and the like. Mitoxantrone is a chemotherapy drug widely used in the treatment of cancer and has significant anti-tumor activity. By loading fat-soluble bioactive ingredients into cocoa butter-based 3D printing materials, not only can their bioavailability be improved, but also precise dosage control and targeted release can be achieved, thereby greatly improving the therapeutic effect and safety.

[0034] Example 1 3D Printability of Cocoa Butter Containing Different Proportions of Calcium Stearate According to the different ratios of cocoa butter and calcium stearate, the following different ratios are set: Ratio 1: Cocoa butter (ml): calcium stearate (g) = 10:0 Ratio 2: Cocoa butter (ml): calcium stearate (g) = 10:2.5 Ratio 3: Cocoa butter (ml): calcium stearate (g) = 10:5 Ratio 4: Cocoa butter (ml): calcium stearate (g) = 10:7.5 Ratio 5: Cocoa butter (ml): calcium stearate (g) = 10:10 Weigh cocoa butter into a beaker and heat in a 50°C water bath to ensure it is completely melted. Add the weighed calcium stearate to the melted cocoa butter and stir for 8-12 minutes to fully incorporate. Place the resulting printing material into a dedicated printing tube and refrigerate until ready to use.

[0035] A cube (length: 20mm, width: 20mm, height: 20mm, filling density: 50%) was used as the printing model. The nozzle diameter, extrusion amount, layer height, nozzle temperature, and nozzle movement speed were set to 1mm, 200%, 0.5mm, 35℃, and 30mm / s, respectively.

[0036] The appearance of each printed product was observed, and its actual dimensions in the three dimensions of length (X-axis), width (Y-axis), and height (Z-axis) were measured. These measurements were compared with the target dimensions set for the original model, and the fidelity of each dimension was calculated: fidelity = 1 - (|measured value - target size| / target size) × 100%. Fidelity reflects the degree of deviation between the actual printed dimensions and the target dimensions. Higher fidelity indicates a closer morphological match between the printed product and the original model, indicating higher printing accuracy. Because 3D printing often uses extrusion stacking and typically involves a transition from a non-Newtonian fluid to a solid, printing speed also affects the quality and accuracy of the printed product.

[0037] Figure 1 The results show that when pure cocoa butter is used for printing, the printed product cannot form internal support and the printability is extremely poor. However, with the gradual addition of calcium stearate, the printing material gradually changes to a semi-fluid state, the support of the printed product becomes better and better, and the appearance contour becomes closer to the cube model, and the printability is significantly improved. From the quantitative fidelity data ( Figure 2 ) showed that, with the exception of the calcium stearate to cocoa butter ratio of 10ml:2.5g, the fidelity of printed products using cocoa butter:calcium stearate ratios of 10ml:5g, 10ml:7.5g, and 10ml:10g was significantly higher than that of the pure cocoa butter group in the X, Y, and Z axes (P < 0.05). The fidelity also showed a gradual upward trend. Overall, the addition of calcium stearate improves the 3D printability of cocoa butter. Example 2 3D Printability of Cocoa Butter Containing Different Proportions of Magnesium Stearate According to the different ratios of cocoa butter and magnesium stearate, the following different ratios are set: Ratio 1: Cocoa butter (ml): magnesium stearate (g) = 10:0 Ratio 2: Cocoa butter (ml): magnesium stearate (g) = 10:2.5 Ratio 3: Cocoa butter (ml): magnesium stearate (g) = 10:5 Ratio 4: Cocoa butter (ml): magnesium stearate (g) = 10:7.5 Ratio 5: Cocoa butter (ml): magnesium stearate (g) = 10:10 Other operations are the same as those in Example 1.

[0038] The appearance of each printed product was observed, and its actual dimensions in the three dimensions of length (X-axis), width (Y-axis), and height (Z-axis) were measured. These measurements were then compared with the target dimensions set for the original model to calculate the fidelity of each dimension. The fidelity calculation formula is: Fidelity = 1 - (|Measured Value - Target Size| / Target Size) × 100%. Fidelity reflects the degree of deviation between the actual print dimensions and the target dimensions. A higher fidelity indicates that the printed product is morphologically closer to the original model, indicating a higher level of printing accuracy.

[0039] In the study of the ratio of magnesium stearate-cocoa butter printing materials (such as Figure 3 (As shown in the figure), we found that when the specific gravity of magnesium stearate was low, the printing performance of cocoa butter was poor; however, as the addition of magnesium stearate increased, the printing support of cocoa butter gradually improved. When the ratio of cocoa butter to magnesium stearate was 10ml:7.5g and 10ml:10g, the material had good printing effects and the printed product had a smooth appearance.

[0040] From the quantitative fidelity data ( Figure 4 ), when the ratio of cocoa butter to magnesium stearate is 10ml:2.5g, the fidelity of the printed product on the X, Y, and Z axes is not much different from that of pure cocoa butter (control); but when the ratio of cocoa butter to magnesium stearate is 10ml:5g, the fidelity of the printed product on the Y and Z axes begins to be significantly higher than that of the control, and the difference is statistically significant (P < 0.05); when the ratio of cocoa butter to magnesium stearate is 10ml:7.5g and 10ml:10g, the fidelity of the printed product on the three axes is significantly higher than that of the control, and the difference is statistically significant (P < 0.05).

[0041] Overall, the addition of magnesium stearate is beneficial to improving the 3D printability of cocoa butter. Example 3 3D Printability of Cocoa Butter Containing Different Proportions of Zinc Stearate According to the different ratios of cocoa butter and zinc stearate, the following different ratios are set: Ratio 1: Cocoa butter (ml): zinc stearate (g) = 10:0 Ratio 2: Cocoa butter (ml): zinc stearate (g) = 10:2.5 Ratio 3: Cocoa butter (ml): zinc stearate (g) = 10:5 Ratio 4: Cocoa butter (ml): zinc stearate (g) = 10:7.5 Ratio 5: Cocoa butter (ml): zinc stearate (g) = 10:10 Other operations are the same as those in Example 1.

[0042] The appearance of each print was observed, and the actual dimensions of the prints in three dimensions—length (X-axis), width (Y-axis), and height (Z-axis)—were measured. These measurements were compared with the target dimensions set for the original model, and the fidelity of each dimension was calculated using the following formula: Fidelity = 1 - (|measured value - target size| / target size) × 100%. Fidelity reflects the degree of deviation between the actual print dimensions and the target dimensions. A higher fidelity indicates a closer conformity of the print to the original model, indicating a higher level of printing accuracy.

[0043] from Figure 5 As can be seen, varying amounts of zinc stearate significantly impact the 3D printing results of cocoa butter. Printing results improve with increasing zinc stearate ratios. When the cocoa butter (ml): zinc stearate (g) ratios are 10:7.5 and 10:10, the printed product exhibits excellent formability and sharp outlines.

[0044] From the quantitative fidelity data ( Figure 6 ) It can be seen that when the cocoa butter: zinc stearate ratio is 10ml:2.5g, the Z-axis fidelity of the printed product is significantly higher than that of the control, and the difference is statistically significant (P < 0.05); when the cocoa butter: zinc stearate ratio is 10ml:5g, the Y- and Z-axis fidelity of the printed product is significantly higher than that of the control, and the difference is statistically significant (P < 0.05); when the cocoa butter: zinc stearate ratio is 10ml:7.5g and 10ml:10g, the fidelity of the printed product on the three axes is significantly higher than that of the control, and the difference is statistically significant (P < 0.05).

[0045] Overall, the addition of zinc stearate helps improve the 3D printability of cocoa butter. Example 4 3D Printability of Cocoa Butter with Different Proportions of Stearate (Mixed) According to the different ratios of cocoa butter and stearate (mixed), set the following different ratios: Ratio 1: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:0:0 Ratio 2: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:3:0:0 Ratio 3: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:3:0 Ratio 4: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:0:3 Ratio 5: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:3:3:3 Other operations are the same as those in Example 1.

[0046] The appearance of each printed product was observed, and its actual dimensions in length (X-axis), width (Y-axis), and height (Z-axis) were measured. These measurements were compared with the target dimensions set for the original model, and the fidelity of each dimension was calculated using the following formula: Fidelity = 1 - (|measured value - target size| / target size) × 100%. Fidelity reflects the degree of deviation between the actual print size and the target size. A higher fidelity indicates that the printed product's morphology is more consistent with the original model, indicating a higher level of printing accuracy.

[0047] like Figure 7 As shown in the figure, when the formula parameters are cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:3:3:3, the printing stability and printing effect are significantly better than the formula of adding calcium stearate, magnesium stearate, and zinc stearate separately, and the printing formability is good. From the quantitative fidelity data ( Figure 8 ) , the fidelity of the finished cubes printed with materials from ratios 2-5 was significantly higher in the X, Y, and Z axes than that of ratio 1 (pure cocoa butter), with statistically significant differences (P < 0.05). Furthermore, the fidelity of the finished products printed with ratio 5 (a mixture of calcium stearate, magnesium stearate, and zinc stearate) was significantly higher in all axes than those printed with ratios 2-4, also with statistically significant differences (P < 0.05). Clearly, the excellent 3D printing properties of ratio 5 are the result of the combined action of the three stearates. Example 5: Loading capacity of printed materials for β-carotene Beta-carotene was added to the cocoa butter-stearate mixture according to the following different ratios.

[0048] Ratio 1: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): β-carotene (mg) = 10:3:3:3:0 Ratio 2: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): β-carotene (mg) = 10:3:3:3:2.5 Ratio 3: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): β-carotene (mg) = 10:3:3:3:5 Ratio 4: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): β-carotene (mg) = 10:3:3:3:7.5 Ratio 5: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): β-carotene (mg) = 10:3:3:3:10 Other operations are the same as those in Example 1.

[0049] like Figure 9 As shown, β-carotene can be evenly incorporated into the cocoa butter-stearate mixed printing material. Furthermore, as the β-carotene content gradually increases, the color of the printed product (orange) gradually darkens. This color change is clearly visible to the naked eye and shows a regular trend of change.

[0050] Subsequently, a colorimeter is used to measure the color of the printed product. During the measurement process, in order to ensure the accuracy and reliability of the data, each sample is measured multiple times, and the obtained LAB values ​​are averaged. Figure 10 As can be clearly seen in the figure, as the β-carotene content increases, the L value gradually decreases, indicating that the color of the printed product becomes darker. The A value gradually increases, indicating that the color shifts toward red on the red-green axis. The B value shows no obvious trend, but the B values ​​of the products printed with ratios 2-5 are all greater than those of ratio 1 (control), and the difference is significant. This LAB value trend is consistent with the color deepening observed by the naked eye, further confirming the β-carotene loading capacity of the cocoa butter-stearate blend printing material. Example 6: Loading capacity of printed materials for mitoxantrone Mitoxantrone was added to the cocoa butter-stearate mixed printing material according to the following different ratios.

[0051] Ratio 1: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): mitoxantrone (mg) = 10:3:3:3:0 Ratio 2: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): mitoxantrone (mg) = 10:3:3:3:2.5 Ratio 3: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): mitoxantrone (mg) = 10:3:3:3:5 Ratio 4: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): mitoxantrone (mg) = 10:3:3:3:7.5 Ratio 5: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g): mitoxantrone (mg) = 10:3:3:3:10 Other operations are the same as in Example 1.

[0052] like Figure 11 As shown, similar to β-carotene, mitoxantrone can be evenly incorporated into the cocoa butter-stearate mixture. As the mitoxantrone content increases, the color of the printed product (blue-green) gradually deepens. Mitoxantrone itself is a dark blue compound, and changes in its concentration in the printing solution directly affect the visual quality of the printed product.

[0053] In order to quantify this color change more accurately, a professional colorimeter is used to measure the printed product multiple times and the obtained LAB values ​​are averaged. Figure 12 As can be seen, as the mitoxantrone content increases, the L value gradually decreases, indicating that the color of the printed product becomes darker; the A value gradually decreases, indicating that the color shifts toward green on the red-green axis; and the B value gradually increases, indicating that the color shifts toward blue on the yellow-blue axis. This LAB value change trend is consistent with the color deepening phenomenon observed by the naked eye, further confirming the mitoxantrone loading capacity of the cocoa butter-stearate mixed printing material.

[0054] Example 7 Evaluation of rheological parameters of 3D printing materials Different printing materials were prepared according to the following ratios, and the preparation method was the same as that in Example 1. Rheological parameters were measured at 38°C.

[0055] Ratio 1: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:0:0 Ratio 2: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:3:0:0 Ratio 3: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:3:0 Ratio 4: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:0:3 Ratio 5: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:3:3:3 Table 1 Storage modulus test results of cocoa butter mixed formula printing materials

[0056] Table 2 Loss modulus test results of cocoa butter mixed formula printing materials

[0057] Table 3 Cocoa butter mixed formula printing material viscosity test results

[0058] The storage modulus G' reflects the material's elasticity, or solid-state properties; while the loss modulus G'' represents the material's viscosity, or liquid-state properties. When G' > G'', the material exhibits primarily elastic properties, with solid-state behavior dominating; conversely, viscosity dominates.

[0059] After performing linear amplitude sweeps on the aforementioned material mixes, the strain value for the modulus test was determined to be 2.5%. The storage modulus and loss modulus results for each mix are shown in Tables 1 and 2, respectively. The loss modulus of mixes 1-5 is higher than the storage modulus, indicating that these mixes exhibit primarily viscous behavior and liquid-like properties. During dynamic deformation, the material's viscous response dominates, with its energy dissipation capacity exceeding its energy storage capacity, placing it in a transition zone from the molten, highly elastic state to the viscous flow state.

[0060] Furthermore, the storage modulus and loss modulus of the material in Mix 5 are both higher than those of Mixes 1-4, and also higher than the linear sum of the values ​​for Mixes 2, 3, and 4. This suggests that calcium stearate, magnesium stearate, and zinc stearate have a synergistic effect on the storage modulus and loss modulus of cocoa butter. Compared to Mixes 1-4, Mix 5 exhibits a high-viscoelastic, liquid-like state, whereas Mixes 1-4 exhibit a low-viscoelastic, liquid-like state.

[0061] Shear viscosity test results (Table 3) show that the viscosity of Formula 5 is significantly higher than the linear sum of the values ​​for Formulas 1-4 and 2-4. This suggests that calcium stearate, magnesium stearate, and zinc stearate synergistically enhance the viscosity properties of cocoa butter. This enhancement is consistent with the superior printability exhibited by Formula 5 compared to Formulas 1-4. At printing temperatures, this formula not only exhibits sufficient fluidity, but its high static viscosity also provides strong structural support for the finished product, ultimately enabling high-precision printing. Example 8: Environmental Heat Resistance Evaluation of 3D Printing Materials To address the problem of poor environmental heat resistance of cocoa butter 3D printed products, the present invention adds stearate to cocoa butter, increases the melting point of the cocoa butter printing material through metal ions, and enhances the stability of the printed products in hot environments.

[0062] Prepare different printing materials according to the following ratios.

[0063] Ratio 1: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:0:0 Ratio 2: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:3:0:0 Ratio 3: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:3:0 Ratio 4: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:0:0:3 Ratio 5: Cocoa butter (ml): calcium stearate (g): magnesium stearate (g): zinc stearate (g) = 10:3:3:3 After solidification at room temperature, it was placed upside down in an oven at 25°C, 30°C, 35°C, and 40°C, and observed at 10 minutes, 15 minutes, and 20 minutes to observe the melting of cocoa butter materials in different proportions, so as to evaluate whether there is any difference in the heat resistance of the materials.

[0064] The results showed that at 25℃ and 30℃, the materials of each ratio did not melt. At 35℃ and 20 minutes, most of the pure cocoa butter had melted, but the cocoa butter material with added stearate did not melt significantly. The results of placing it in an oven at 40℃ are as follows: Figure 13 As shown in the figure, after 15 minutes, the pure cocoa butter was completely melted; after 20 minutes, the cocoa butter with single stearate added (ratio 2-4) began to melt, while the cocoa butter with mixed formula (ratio 5) did not show obvious deformation.

[0065] This shows that after adding mixed stearates, the melting temperature of cocoa butter is significantly increased and its environmental thermal stability is significantly improved. In summary, 3D printing using cocoa butter alone presents numerous technical challenges, primarily due to its inherent physical properties, such as its low melting point, susceptibility to softening and deformation at room temperature, and poor surface stability. These characteristics significantly limit the potential of cocoa butter for additive manufacturing, making it difficult to achieve ideal printing results and product quality in practice.

[0066] To address the above-mentioned issues, the embodiments of the present invention have made systematic and effective improvements in three aspects: printability, environmental heat resistance, and rheological properties. This enables cocoa butter to be directly used as the main raw material for 3D printing, thereby significantly improving its applicability and practicality in the field of additive manufacturing.

[0067] ① Improved printability This invention addresses the problem of cocoa butter collapsing and being difficult to shape during direct 3D printing. By adding stearate, the material is able to restrict the movement of oil molecules and effectively alter its crystal structure. This improvement enables the material to form precise and stable geometric shapes during 3D printing, imparting excellent interlayer bonding and structural strength. This significantly improves the precision and quality of the printed product, resolving the structural instability and blurred details common in traditional cocoa butter printing.

[0068] ② Improved environmental heat resistance The stearate added in this invention not only improves the crystal structure of cocoa butter but also significantly enhances the thermal stability of cocoa butter 3D printed products when the ambient temperature fluctuates. The addition of stearate effectively raises the melting point of the cocoa butter system, overcoming the problem of softening and deformation at room temperature or even higher temperatures, which can lead to loss of structural support. This makes the printed products more adaptable to ambient conditions during storage, transportation, and display, extending their service life.

[0069] ③ Improvement of rheological properties This invention comprehensively optimizes the rheological properties of cocoa butter, resulting in more ideal flow characteristics during the printing process. By improving key parameters such as the material's viscoelasticity and viscosity, the cocoa butter can be extruded more smoothly through the nozzle during printing and rapidly solidify upon cooling, forming a stable structure. This improvement not only improves printing efficiency but also reduces potential blockages and unevenness during printing, ensuring a smooth printing process and consistent quality of the finished product.

[0070] Furthermore, the present invention experimentally demonstrates the ability of cocoa butter composite printing materials to load fat-soluble active ingredients. Therefore, this material can not only be used in conjunction with 3D printing technology to expand its application in areas such as food and cosmetics, but also offers new possibilities in the biomedical field, particularly in personalized nutrition and drug delivery, opening up new application prospects for cocoa butter in high-tech fields.

[0071] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A cocoa butter-based 3D printing material, characterized in that: Contains cocoa butter and stearate.

2. The cocoa butter-based 3D printing material according to claim 1, characterized in that: The stearate is at least one of calcium stearate, zinc stearate and magnesium stearate.

3. The cocoa butter-based 3D printing material according to claim 2, characterized in that: The invention comprises cocoa butter, calcium stearate, zinc stearate and magnesium stearate, wherein the ratio of the cocoa butter, calcium stearate, zinc stearate and magnesium stearate is 8-12 ml: 2-12 g: 2-12 g: 2-12 g.

4. A method for printing a cocoa butter-based 3D printing material according to any one of claims 1 to 3, characterized in that: After cocoa butter is melted, calcium stearate, zinc stearate and magnesium stearate are added and stirred evenly to prepare a printing material; and 3D printing is performed.

5. The printing method according to claim 4, wherein: The printing parameters of the 3D printing are as follows: nozzle diameter of 0.5-1 mm, extrusion volume of 100-300%, layer height of 0.4-0.6 mm, nozzle temperature of 10-45° C., and nozzle movement speed of 15-40 mm / s.

6. Use of the cocoa butter-based 3D printing material according to any one of claims 1 to 3 in the preparation of an oil-based material loaded with fat-soluble bioactive ingredients.

7. The use according to claim 6, characterized in that The fat-soluble bioactive component includes at least one of carotenoids, fat-soluble vitamins, sterol compounds, unsaturated fatty acids, and anthracycline drugs.

Images