Highly-filled photosensitive ink as well as preparation method and application thereof

Abstract

The invention discloses high-filling photosensitive ink as well as a preparation method and application thereof, and belongs to the technical field of preparation of high-temperature-resistant composite materials. The highly-filled photosensitive ink comprises matrix resin, a high-temperature-resistant filler, a photoinitiator, a solvent and an auxiliary agent. The method can be used in a collaborative printing technology of a photocuring technology and an ink direct-writing technology, and high-performance high-temperature-resistant complex-structure workpieces can be produced through direct-writing deposition, UV curing and comprehensive post-curing treatment. Wherein the high-filling photosensitive ink is large in filling amount and low in cost, the temperature resistance of a workpiece can be improved, the expansion coefficient can be reduced, the high-filling advantage of direct writing and the high-precision advantage of photocuring are both achieved through the collaborative technology, and therefore it is guaranteed that the workpiece is stably formed. The prepared high-temperature-resistant composite material can be used for aerospace, electronic packaging and other complex structure scenes needing high temperature resistance and high strength.

Description

Technical Field

[0001] This application belongs to the field of high-temperature resistant composite material preparation technology, specifically involving a high-filling photosensitive ink, its preparation method and application. Background Technology

[0002] In industrial production and high-end manufacturing, materials that can maintain stable performance under high-temperature environments are frequently used. For example, in the aerospace field, lightweight, high-strength aircraft structural components must withstand extreme temperatures for extended periods while maintaining structural integrity; in mold manufacturing, high-temperature resistant irregular-shaped molds must withstand continuous high temperatures during the molding process without performance degradation; in electronics manufacturing, electronic component packaging materials must protect circuit boards from external environmental corrosion such as high temperatures and humidity, ensuring stable component operation; furthermore, medical devices, special packaging, and other fields also have specific requirements for the high-temperature resistance and comprehensive performance of materials. High-temperature resistant photosensitive resins, due to their combination of the convenience of photocuring and performance stability under high-temperature environments, have become key candidate materials in these fields, and their application demand continues to grow with technological advancements and industrial upgrading.

[0003] Currently, high-temperature resistant photosensitive resins typically employ epoxy and acrylic resin systems, with inorganic fillers added to enhance the temperature resistance and mechanical properties of the photocurable resin. However, the introduction of inorganic fillers significantly degrades the printability of the photocurable resin. Therefore, a technology that balances both high-temperature resistance and printability is urgently needed. Summary of the Invention

[0004] The purpose of this application is to provide a high-filling photosensitive ink, its preparation method and application, which can solve the problem of deterioration in printing performance after the addition of inorganic fillers, and ensure the molding accuracy, high temperature resistance and structural integrity of composite materials.

[0005] To achieve the above objectives, this application provides a high-filling photosensitive ink, which, based on 100 parts, comprises the following components by weight: 10 to 30 parts of matrix resin, 70 to 90 parts of high-temperature resistant filler, 1 to 5 parts of photoinitiator, and the balance being solvent and additives.

[0006] Furthermore, the matrix resin includes at least one of acrylate, epoxy resin, methacrylate, and siloxane resin; the high-temperature resistant filler includes at least one of alumina, silica, boron nitride, zirconium oxide, and high-temperature ceramic microspheres, with a filler particle size of 5 nm to 100 µm; the photoinitiator includes at least one of benzoin dimethyl ether, benzophenone, peroxides (including but not limited to benzoyl peroxide, methyl ethyl ketone peroxide, etc.), acylphosphine oxide, thioxanone, and their derivatives.

[0007] Furthermore, the additives include dispersants and other additives. The dispersants include at least one of polymeric dispersants, nonionic surfactants, ionic surfactants, and special dispersants (e.g., carboxylates, sulfonates, polyacrylates, and polyurethane dispersants). The other additives include at least one of leveling agents, defoamers, thickeners, and antioxidants.

[0008] Furthermore, the solvent includes at least one of N-methylpyrrolidone, γ-butyrolactone, ethyl acetate, and dimethylacetamide.

[0009] This application also provides a method for preparing a highly filled photosensitive ink, comprising the following steps: The matrix resin is mixed with the photoinitiator to form a first mixed solution; The high-temperature resistant filler, solvent, and additives are mixed to form a second mixed solution; The first mixed solution is added to the second mixed solution in batches, and the mixture is stirred to obtain a slurry; The slurry was subjected to vacuum degassing to obtain the highly filled photosensitive ink; The slurry is subjected to a shear rate of 1 second at room temperature. -1 ~100s -1 At that time, the viscosity was 10 mPa•s to 100 mPa•s.

[0010] Furthermore, the stirring speed is 200 rpm to 500 rpm, and the stirring time is 2 h to 5 h.

[0011] This application also provides an application of highly filled photosensitive ink in the preparation of high-temperature resistant composite materials. This can expand the application fields of high-temperature resistant high-performance composite materials, for example, in aerospace, automotive manufacturing, and electronic packaging, especially for materials requiring high temperature resistance, high strength, and complex geometries.

[0012] Furthermore, the preparation of the high-temperature resistant composite material includes the following steps: The high-filling photosensitive ink is extruded and printed using ink direct writing technology, and then cured by UV light source to obtain the first layer of material; layers are stacked one by one until the printing of the entire three-dimensional structure is completed to obtain a preform; the preform is then fully cured in a UV oven to obtain the final product.

[0013] This application introduces a photopolymerization precision direct-write co-fabrication technology, which enables low-cost fabrication of high-temperature resistant, high-performance precision parts. By using highly filled composite materials and a multi-stage curing mechanism, the temperature resistance and overall performance of the printed parts are effectively improved, and the coefficient of thermal expansion is effectively controlled. Furthermore, this photopolymerization precision direct-write co-fabrication technology can produce high-performance parts with excellent surface quality. Through photopolymerization micro-nano scale precision control and precise ink flow control, the surface smoothness of the printed parts can be improved.

[0014] Furthermore, the extrusion parameters include: needle diameter of 0.1mm~1.0mm, extrusion pressure of 0.25MPa~1.0MPa, printing speed of 5mm / s~20mm / s, and exposure time of 5s~50s.

[0015] Furthermore, it also includes improving the high-temperature resistance and mechanical properties of the high-temperature resistant composite material through heat treatment, wherein the heat treatment temperature is 80℃~150℃ and the time is 2h~8h.

[0016] Furthermore, the temperature for the full curing treatment is 10℃~40℃, and the time is 1h~5h.

[0017] In summary, this application has the following advantages: 1. To address the contradiction between high filling and flowability in traditional inorganic filler modification, this application combines high-temperature resistant inorganic fillers with photosensitive resin to prepare a composite ink that combines high filling characteristics with good ink direct-write printing properties. This retains the enhancing effect of inorganic fillers on the high-temperature resistance and mechanical strength of the material, while avoiding the extrusion difficulties caused by the flowability decay of traditional high-filler systems, thus laying a material foundation for low-cost preparation.

[0018] 2. This application relies on the deposition characteristics of ink direct writing technology to achieve uniform deposition of highly filled materials. Compared with traditional filling methods, it can enable inorganic fillers to form a micro-uniformly distributed structure in the resin matrix, reduce the performance shortcomings caused by filler agglomeration, and thus improve the overall mechanical properties and thermal stability of the composite material. At the same time, combined with the precision molding advantages of photocuring technology, it provides structural guarantee for the high-precision construction of subsequent three-dimensional structures. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the printing method involved in the embodiments of this application. Detailed Implementation

[0020] The principles and features of this application are described below with reference to embodiments. The examples are for illustrative purposes only and are not intended to limit the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0021] Photosensitive resins, as important photocurable rapid prototyping materials, are widely used in 3D printing, precision manufacturing, and other fields due to their high molding precision and fast molding speed. However, conventional photosensitive resins have poor heat resistance, and their mechanical properties and chemical stability decrease sharply at high temperatures, which greatly limits their application in fields requiring high-temperature operating conditions. Research on high-temperature resistant photosensitive resins mainly focuses on two aspects: First, through molecular structure design, developing intrinsically high-temperature resistant resin systems, such as polyimide resins and cyanate ester resins. Although these resins can fundamentally endow materials with excellent heat resistance, their synthesis processes are complex and technically challenging, resulting in extremely high production costs and hindering large-scale commercialization. Second, to reduce costs, lower-cost epoxy resins or acrylic resins are used as the base system, and inorganic fillers are added to improve their temperature resistance and mechanical properties. However, this method has obvious inherent defects. For example, the introduction of a large amount of inorganic filler will significantly reduce the fluidity of the resin, resulting in poor leveling and uneven curing during the 3D printing process. This leads to serious problems such as warping, delamination, debonding, and even falling off of the printed parts, which seriously affects the stability of the printing process and the molding quality and precision of the final product.

[0022] Based on this, this application develops a novel high-temperature resistant photosensitive resin and a compatible printing technology that combines high heat resistance, excellent mechanical properties, and good printability without sacrificing printing process performance. The printing technologies of this application include photopolymerization printing technology and ink-to-ink printing technology. The principle of photopolymerization printing technology is to build a three-dimensional structure layer by layer by curing photosensitive materials using a light source (such as ultraviolet light). After each layer of ink is deposited, or after all layers are deposited, the material is irradiated with ultraviolet light of a specific wavelength or other light source, triggering the photosensitizer to cause a cross-linking reaction in the polymers or resins in the ink, thereby rapidly curing. The cured material may require further heat treatment or other treatments to enhance its mechanical properties or improve its temperature resistance. It features high precision and rapid manufacturing; therefore, inks suitable for this technology typically have low filler content to ensure fluidity. The principle of ink-to-ink printing technology is to use extrusion printing to directly deposit ink onto the substrate through a nozzle to form a three-dimensional structure. During this process, the viscosity, surface tension, and rheology of the ink need to be precisely controlled to ensure print quality. The advantages of this technology are its wide range of material selection and low cost, making it suitable for printing high-filling ink materials. This application combines these two technologies and configures a suitable high-filling photosensitive ink, which has the following advantages: (1) Precise and controllable: Ink direct writing technology can achieve high-filling material deposition, making the material more uniform in microstructure, thereby improving the overall performance of composite materials. Photocuring technology can quickly cure the material after deposition, further ensuring the stability and accuracy of the structure. (2) Wide range of material adaptability: By adjusting the ink formula, it can adapt to different substrates and functional requirements. (3) Low cost and high efficiency: The combination of the two technologies can realize the manufacturing of complex geometries. Since the price of high-filling filler raw materials is about 10% of that of high-performance resins and has the characteristics of low thermal expansion coefficient, it can reduce costs and reduce the shrinkage rate of parts, which has unique advantages for the manufacturing of large-size high-temperature resistant composite materials.

[0023] Specifically, in its first aspect, this application provides a highly filled photosensitive ink, comprising, by weight, the following components per 100 parts: 10-30 parts matrix resin, 70-90 parts high-temperature resistant filler, 1-5 parts photoinitiator, with the balance being solvent and additives. This application allows for flexible adjustment of the ink formulation to precisely match the specific performance requirements of various application fields. For example, for the high-temperature resistance requirements in the aerospace field, the filler ratio can be optimized to enhance the thermal stability of the material; for the electrical requirements in the electronic component packaging field, conductive / insulating functional fillers can be introduced to achieve electrical performance; for the mechanical strength requirements in the mold manufacturing field, the matrix-filler interface bonding can be adjusted to improve structural strength.

[0024] The matrix resin in this application can be any type or model of monomer / oligomer used to prepare the photosensitive resin, or an oligomer raw material prepared according to existing technology. The high-temperature resistant filler in this application can be any material used as a functional filler, such as carbon-based fillers or conductive fillers. The photoinitiator in this application can be any material capable of initiating a polymerization reaction under light irradiation. The dispersant or other additives in this application are mainly used to improve filler distribution and printing performance; therefore, they can be selected according to actual needs, such as leveling agents, defoamers, thickeners, antioxidants, flame retardants, and anti-aging agents. However, the selection of raw materials in this application should be based on the principle that it should not negatively affect the effectiveness of this application.

[0025] In a specific embodiment, the matrix resin includes at least one of acrylate, epoxy resin, methacrylate and siloxane resin; the high-temperature resistant filler includes at least one of alumina, silica, boron nitride, zirconium oxide and high-temperature ceramic microspheres; and the photoinitiator includes at least one of benzoin dimethyl ether, benzophenone, peroxides, acylphosphine oxides, thioxanone and their derivatives.

[0026] In a specific embodiment, the additives include dispersants and other additives. The dispersants include at least one of polymeric dispersants, nonionic surfactants, ionic surfactants, and special dispersants. The other additives include at least one of leveling agents, defoamers, thickeners, and antioxidants.

[0027] In a specific embodiment, the solvent includes at least one of N-methylpyrrolidone, γ-butyrolactone, ethyl acetate, and dimethylacetamide.

[0028] Secondly, this application provides a method for preparing a highly filled photosensitive ink, including: S101. The matrix resin and photoinitiator are mixed to form a first mixed solution, so that the photoinitiator is fully dispersed in the matrix resin.

[0029] S102. After mixing the high-temperature resistant filler, solvent and additives, a second mixed solution is formed, so that the high-temperature resistant filler and dispersant work synergistically and are fully dispersed in the solvent.

[0030] S103. The first mixed solution is added to the second mixed solution in batches and stirred to obtain a slurry.

[0031] In a specific embodiment, the stirring speed is 200 rpm to 500 rpm, and the stirring time is 2 h to 5 h.

[0032] S104. The slurry is subjected to vacuum degassing to obtain the highly filled photosensitive ink. The slurry is subjected to a shear rate of 1 s at room temperature. -1~100s -1 At that time, the viscosity was 10 mPa•s to 100 mPa•s. The viscosity of this application is based on the standard set to meet the printability performance of ink direct writing printing, but it is not the only standard for measuring whether an ink material is printable.

[0033] Thirdly, this application provides a method for preparing high-temperature resistant composite materials using a high-filling photosensitive ink and photopolymerization precision direct writing co-manufacturing technology. This method combines the high precision of photopolymerization technology with the high filling capacity and material compatibility of ink direct writing technology, achieving low-cost preparation of high-temperature resistant, high-performance composite materials. This can also be referred to as photopolymerization precision direct writing co-manufacturing technology. Specifically, the method retains the inherent high-precision molding characteristics of photopolymerization technology, effectively avoiding molding defects such as uneven curing and part detachment / debonding caused by inorganic fillers, thus ensuring the molding accuracy and structural integrity of the composite material. The method also integrates the high filling capacity and wide material compatibility of ink direct writing technology. High filling capacity improves temperature resistance and mechanical strength, while avoiding the flowability degradation problem caused by filler introduction in traditional printing technologies. Furthermore, it achieves a low-cost preparation path without relying on high-cost polyimide and cyanate ester resin systems.

[0034] Specifically, a method for preparing high-temperature resistant composite materials includes the following steps: S201. The high-filler photosensitive ink is extruded and printed, and then cured using a UV light source to obtain the first layer of material. The extrusion deposition of the high-filler photosensitive ink utilizes the controllable deposition capability of the equipment to initially construct the three-dimensional structural outline of the composite material, ensuring the microscopic uniformity of the high-filler material. Immediately after material extrusion deposition, photocuring technology is used to solidify and sculpt the initially formed structure. The rapid curing characteristics of photocuring quickly fix the material morphology, preventing structural deformation after deposition. Simultaneously, the high precision of photocuring refines the details of the three-dimensional structure, ensuring the precision molding accuracy of the part and solving the problem of decreased molding accuracy caused by high filler in traditional printing.

[0035] In a specific embodiment, the extrusion parameters include: needle diameter of 0.1mm to 1.0mm, extrusion pressure of 0.25MPa to 1.0MPa, printing speed of 5mm / s to 20mm / s, and exposure time of 5s to 50s.

[0036] S202. Stack the layers one by one until the printing of the entire three-dimensional structure is completed to obtain the preform; S203. The preform is fully cured in a UV oven to obtain the final product. Further UV post-treatment of the precision-formed part can enhance the curing effect, improve the cross-linking degree and performance stability of the material, ultimately yielding a high-temperature resistant, high-performance, and precisely molded composite material part.

[0037] In a specific embodiment, the temperature of the full curing treatment is 10℃~40℃, and the time is 1h~5h.

[0038] In a specific embodiment, the high-temperature resistant composite material is further improved by heat treatment, wherein the heat treatment temperature is 80℃~150℃ and the time is 2h~8h.

[0039] This application provides a high-filling photosensitive ink, its preparation method, and its application, which have at least the following advantages: Firstly, this application develops a photosensitive resin formulation containing a high proportion of high-temperature resistant fillers (such as ceramic particles and carbon fibers). Through the controllability of direct-write deposition and the instant shaping capability of photocuring, it can accommodate a high proportion of fillers to enhance material properties while avoiding printing failures caused by filler agglomeration or decreased flowability. This significantly improves the thermal stability and mechanical strength of printed parts, meeting the high-temperature requirements of aerospace, mold manufacturing, and other fields. Furthermore, it eliminates the need for expensive resins such as polyimide and cyanate esters, achieving high performance using ordinary photosensitive resin as the matrix, thus offering a low-cost advantage. The introduction of a high proportion of inorganic fillers reduces the overall coefficient of thermal expansion of the material, meeting the core requirement of dimensional stability in electronic component packaging.

[0040] Secondly, based on the structural support provided by the high-filling ink itself, this application first achieves rapid shaping after deposition through instant UV curing, avoiding precision deviations caused by deformation of uncured materials; then, combined with subsequent heat treatment or UV post-curing processes, it promotes the full cross-linking reaction within the material. This further enhances the long-term temperature resistance, chemical stability, and mechanical strength of the composite material, ensuring its performance stability under long-term high-temperature conditions.

[0041] In summary, the method of this application, through the synergy of ink direct writing technology and photopolymerization technology, not only solves the problems of uniform deposition of high-filling materials and low-cost material application, ensuring the performance and cost advantages of the materials; but also solves the problems of precision forming and structural stability, ensuring the accuracy and morphological stability of the parts, ultimately obtaining low-cost, high-performance complex parts.

[0042] The technical solutions described above in this application will be explained in detail below with reference to specific embodiments.

[0043] Example 1 This embodiment provides a method for preparing low-cost acrylate / alumina high-temperature resistant composite materials using photopolymerization printing technology and ink direct writing technology, including the following steps: (1) Preparation of highly filled photosensitive ink Weigh out the components, including 25 parts acrylate resin, 55 parts alumina powder, 4 parts 2,2-dimethoxy-2-phenylacetophenone (DMPA, photoinitiator), 2 parts dispersant sodium polyacrylate, 4 parts other additives (including 2 parts sodium polyacrylate, 1 part antioxidant BHT and 1 part leveling agent Tego Glide 420), and 10 parts N-methylpyrrolidone (NMP, solvent), for a total of 100 parts.

[0044] Ink preparation includes: 1.1) Under normal temperature conditions, acrylate resin and DMPA are mixed and stirred until completely dissolved to form the first mixed solution; 1.2) After mixing alumina powder with N-methylpyrrolidone, sodium polyacrylate, antioxidant, and leveling agent, mechanical stirring is performed. If necessary, ultrasonic treatment (ultrasonic power of 1000W, time of 30min) is used to fully mix the mixture to form a second mixed solution. 1.3) Gradually add the first mixed solution to the second mixed solution and stir at 500 rpm for 3 hours using a high-speed mixer until the filler reaches the ideal dispersion state in the resin to obtain the ink slurry; 1.4) The shear rate of the thoroughly mixed ink slurry at room temperature is 1 s. -1 ~100s -1 At that time, the viscosity was ≤1000mPa•s.

[0045] 1.5) Vacuum degassing of the ink slurry removes air bubbles to obtain highly filled photosensitive ink, thus avoiding defects during the printing process.

[0046] (2) High-temperature resistant composite materials were prepared by using high-filling photosensitive ink. 2.1) The prepared high-filling photosensitive ink is loaded into a photocurable printing consumable cartridge; 2.2) Start the printing program. The computer controls the nozzle to move along the set path and extrude ink. The extrusion parameters are: needle diameter 0.3mm, pressure 0.5MPa, and printing speed 10mm / s. 2.3) During extrusion, such as Figure 1 As shown, a UV light source is precisely irradiated onto the newly deposited ink, causing it to quickly solidify and form based on the ink's original support force. This allows for precise modification and shaping of the printed high-temperature resistant, high-performance, complex structural parts. The exposure time is 30 seconds. 2.4) Stack the layers one by one until the entire three-dimensional structure is printed to obtain the preform; 2.5) After printing, remove any uncured excess resin from the preform and clean it with ethanol; 2.6) The preform is placed in a UV oven and cured at 30°C for 2 hours to further improve the crosslinking density and performance of the material, resulting in a high-temperature resistant and low-cost acrylic / alumina complex structure part.

[0047] Example 2 This embodiment provides a method for preparing low-cost epoxy resin / silica high-temperature resistant composite materials using photopolymerization printing technology and ink direct writing technology, including the following steps: (1) Preparation of highly filled photosensitive ink Weigh out the components, including 20 parts epoxy resin, 66 parts silica powder, 4 parts benzophenone, 1 part sodium polyacrylate and 10 parts toluene, for a total of 100 parts.

[0048] Ink preparation includes: 1.1) Under normal temperature conditions, epoxy resin and benzophenone are mixed and stirred until completely dissolved to form the first mixed solution; 1.2) Mix silica powder, toluene, and sodium polyacrylate and then mechanically stir. If necessary, use ultrasonic treatment (ultrasonic power of 1000W for 30min) to fully mix and form a second mixed solution. 1.3) Gradually add the first mixed solution to the second mixed solution and stir at 500 rpm for 3 hours using a high-speed mixer until the filler reaches the ideal dispersion state in the resin to obtain the ink slurry; 1.4) The shear rate of the thoroughly mixed ink slurry at room temperature is 1 s. -1 ~100s -1 At that time, the viscosity was 85 mPa•s.

[0049] 1.5) Vacuum degassing of the ink slurry removes air bubbles to obtain highly filled photosensitive ink, thus avoiding defects during the printing process.

[0050] (2) High-temperature resistant composite materials were prepared by using high-filling photosensitive ink. 2.1) The prepared high-filling photosensitive ink is loaded into a photocurable printing consumable cartridge; 2.2) Start the printing program. The computer controls the nozzle to move along the set path and extrude ink. The extrusion parameters are: needle diameter 0.4 mm, pressure 0.6 MPa, and printing speed 10 mm / s. 2.3) During extrusion, a UV light source is precisely irradiated onto the newly deposited ink, allowing it to quickly solidify and form based on the ink's original support force. This enables precise modification and shaping of the printed high-temperature resistant, high-performance, complex structural parts. The exposure time is 30 seconds. 2.4) Stack the layers one by one until the entire three-dimensional structure is printed to obtain the preform; 2.5) After printing, remove any uncured excess resin from the preform and clean it with ethanol; 2.6) The preform is placed in a UV oven and cured at 30°C for 2 hours to further improve the crosslinking density and performance of the material, resulting in a high-temperature resistant and low-cost acrylic / alumina complex structure part.

[0051] Experimental Example The performance and cost of the complex structural parts prepared in Examples 1 and 2, as well as commercially available polyimide and other high-temperature photosensitive resin parts, were compared.

[0052] Test method: (1) The heat distortion temperature is determined by the test method of the temperature of the plastic sample when it is bent to a certain extent under a certain load, and GB / T 1634.1-2004 (Determination of the load distortion temperature of plastics - Part 1: General test method). (2) The coefficient of thermal expansion was tested by the linear expansion method, and the method of GB / T 1036-2008 (Determination of linear thermal expansion coefficient of plastics) was used.

[0053] The test results are shown in Table 1.

[0054] Table 1. Test results of heat distortion temperature and coefficient of thermal expansion

[0055] As shown in Table 1, the parts prepared by the method of this application not only have a cost of approximately 5% to 10% of commercially available high-temperature resistant polyimide photosensitive resin parts, but also exhibit a significant advantage in heat distortion temperature compared to commercially available products. Furthermore, because this application introduces photopolymerization precision direct writing technology and uses high-filler ink for molding, the high-temperature resistant filler possesses advantages and characteristics of high temperature resistance and low coefficient of thermal expansion. The parts prepared in the embodiments of this application all have a higher coefficient of thermal expansion than commercially available products, which is of great significance in the field of preparing high-temperature resistant, low-expansion-coefficient precision parts, and can significantly improve the problems of large shrinkage and difficult dimensional control of traditional photosensitive resins.

[0056] In summary, this application, by introducing photopolymerization precision direct writing collaborative preparation technology, breaks through the functional limitations of single technology, deeply integrates the high-precision molding characteristics of photopolymerization technology with the high filling capacity and wide material compatibility of ink direct writing technology, fundamentally solving the problem that existing high-temperature resistant composite materials are difficult to balance in terms of cost, performance and moldability.

[0057] While specific embodiments of this application have been described in detail, this should not be construed as limiting the scope of protection of this application. Various modifications and variations that can be made by those skilled in the art without inventive effort within the scope described in the claims still fall within the scope of protection of this application.

Claims

1. A high-filling photosensitive ink, characterized in that, Based on 100 parts, it includes the following components by weight: 10 to 30 parts of matrix resin, 70 to 90 parts of high-temperature resistant filler, 1 to 5 parts of photoinitiator, and the balance being solvent and additives.

2. The high-filling photosensitive ink according to claim 1, characterized in that, The matrix resin includes at least one of acrylate, epoxy resin, methacrylate, and silicone resin; The high-temperature resistant filler includes at least one of alumina, silicon dioxide, boron nitride, zirconium oxide, and high-temperature ceramic microspheres; The photoinitiator includes at least one of benzoin dimethyl ether, benzophenone, peroxides, acylphosphine oxides, thioxanone and their derivatives.

3. The high-filling photosensitive ink according to claim 1, characterized in that, The additives include dispersants and other additives. The dispersants include at least one of polymeric dispersants, nonionic surfactants, ionic surfactants, and special dispersants. The other additives include at least one of leveling agents, defoamers, thickeners, and antioxidants.

4. The high-filling photosensitive ink according to claim 1, characterized in that, The solvent includes at least one of N-methylpyrrolidone, γ-butyrolactone, ethyl acetate, and dimethylacetamide.

5. A method for preparing a high-filling photosensitive ink according to any one of claims 1-4, characterized in that, Includes the following steps: The matrix resin is mixed with the photoinitiator to form a first mixed solution; The high-temperature resistant filler, solvent, and additives are mixed to form a second mixed solution; The first mixed solution is added to the second mixed solution in batches, and the mixture is stirred to obtain a slurry; The slurry was subjected to vacuum degassing to obtain the highly filled photosensitive ink; The slurry is subjected to a shear rate of 1 second at room temperature. -1 ~100s -1 At that time, the viscosity was 10 mPa•s to 100 mPa•s.

6. The method for preparing the high-filling photosensitive ink according to claim 5, characterized in that, The stirring speed is 200 rpm to 500 rpm, and the stirring time is 2 h to 5 h.

7. The application of a high-filling photosensitive ink according to any one of claims 1-4 in the preparation of high-temperature resistant composite materials.

8. The application according to claim 7, characterized in that, The preparation of the high-temperature resistant composite material includes the following steps: The highly filled photosensitive ink is extruded and printed, and then cured by UV light source to obtain the first layer material; Layer by layer, until the entire three-dimensional structure is printed, resulting in a preform; The preform is obtained by fully curing it in a UV oven.

9. The application according to claim 8, characterized in that, The parameters for the extrusion printing include: needle diameter of 0.1mm to 1.0mm, extrusion pressure of 0.25MPa to 1.0MPa, printing speed of 5mm / s to 20mm / s, and exposure time of 5s to 50s.

10. The application according to claim 8, characterized in that, It also includes improving the high-temperature resistance and mechanical properties of the high-temperature resistant composite material through heat treatment, wherein the heat treatment temperature is 80℃~150℃ and the time is 2h~8h.

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