Method for additive manufacturing of bio-based solid state lighting element
By modifying saturated fatty acid-based photosensitive resins, the problem of low reactivity was solved, enabling rapid photocuring and expanding its applications in additive manufacturing and solid-state lighting, especially in innovative applications in 3D printing and solid-state lighting devices.
Patent Information
- Application Number
- CN202511650535.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-12
- Publication Date
- 2026-03-03
AI Technical Summary
In existing technologies, saturated fatty acids lack photosensitive groups and have low reactivity, making it difficult to achieve rapid photocuring and limiting their application in additive manufacturing and solid-state lighting.
By employing a specific modification method, saturated fatty acids and modifiers are mixed under certain conditions, and catalysts and additives are added to prepare a saturated fatty acid-based photosensitive resin with rapid photocuring capability. This resin is then cured layer by layer by a 3D printer using ultraviolet light to form a bio-based solid-state lighting element.
The prepared photosensitive resin has the characteristics of rapid photocuring, which is suitable for photocuring additive manufacturing, expands the application of bio-based materials in the field of solid-state lighting, and achieves high-precision lighting effects.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of solid-state lighting technology, specifically relating to a saturated fatty acid-based photosensitive resin and a method for additively manufacturing solid-state lighting elements using the same. Background Technology
[0002] Faced with the increasingly severe challenges of global resource scarcity and environmental problems, traditional petroleum-based materials are facing widespread scrutiny due to their non-renewability, difficulty in degradation, and significant environmental damage. Promoting the development of green and sustainable materials has become a key research direction in materials science. Against this backdrop, bio-based resins, as polymers derived from renewable resources, are gradually becoming an important alternative to petroleum-based resins due to their renewability, biodegradability, and lower environmental impact, playing a vital role in achieving green manufacturing and sustainable development.
[0003] Photosensitive resins, as a class of polymeric materials that can rapidly cure under ultraviolet light, offer significant advantages over traditional thermosetting resins, including faster curing speeds and lower energy consumption. This not only greatly improves production efficiency but also effectively reduces energy consumption. Furthermore, their precise curing control makes them outstanding in precision machining and the manufacture of complex structures, while their solvent-free nature further reduces environmental pollution. These advantages make photosensitive resins a promising candidate for applications in additive manufacturing, coating technology, and precision machining, and they contribute to the green transformation of the materials industry. Therefore, developing photosensitive resins using bio-based raw materials can reduce dependence on petroleum resources and the consumption of non-renewable resources, while also contributing to the achievement of global carbon emission reduction targets, making it a key pathway to promoting green manufacturing.
[0004] Currently, research has explored the use of bio-based raw materials in the development of photosensitive resins. Unsaturated fatty acids, due to their presence of reactive groups such as carbon-carbon double bonds, are easily introduced with photosensitive functional groups through reactions like epoxidation and acrylate modification, making them a primary raw material for bio-based photosensitive resins. However, unsaturated fatty acids are limited in source and expensive, and their unsaturated structure leads to poor oxidative stability, restricting their application. In contrast, saturated fatty acids are more widely available, inexpensive, and possess excellent chemical stability and antioxidant properties, making them a highly promising bio-based raw material. However, the application of saturated fatty acids in photosensitive resins still faces significant technical bottlenecks. This is primarily because saturated fatty acid molecules lack photosensitive groups such as carbon-carbon double bonds and epoxy groups, resulting in low reactivity. Conventional modification methods (such as the epoxy-acrylic acid method) are insufficient for photochemical modification, hindering effective photocuring. Furthermore, the photocuring rate and degree of curing after modification with saturated fatty acids often fail to meet the requirements of high-precision additive manufacturing, further limiting their application in advanced manufacturing technologies such as 3D printing.
[0005] Therefore, developing a saturated fatty acid-based photosensitive resin that can effectively overcome the low reactivity of saturated fatty acids, achieve rapid photocuring, and is suitable for additive manufacturing is of great significance for expanding the application of bio-based materials in green manufacturing, especially in high-end fields such as solid-state lighting. Summary of the Invention
[0006] The purpose of this invention is to address the shortcomings of existing technologies by providing a saturated fatty acid-based photosensitive resin and a method for additive manufacturing solid-state lighting elements using the same. This invention solves the problem that saturated fatty acids lack photosensitive groups and cannot be photocured. The obtained saturated fatty acid-based photosensitive resin has a faster curing speed and can be applied to photocuring additive manufacturing. At the same time, the prepared solid-state lighting elements can be used in the field of solid-state lighting.
[0007] To achieve the above objectives, the present invention adopts the following technical solution: A method for additive manufacturing of bio-based solid-state lighting elements, wherein the bio-based solid-state lighting elements are prepared by photopolymerization 3D printing using saturated fatty acid-based photosensitive resin.
[0008] Further, by weight, the saturated fatty acid-based photosensitive resin comprises: 55-68 parts of saturated fatty acid, 32-45 parts of modifier, 2 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2 parts of triethylamine, and 0-5 parts of microcrystalline cellulose.
[0009] Furthermore, the saturated fatty acid is any one of caprylic acid, capric acid, lauric acid, myristic acid, and palmitic acid.
[0010] Furthermore, the modifier is any one of hydroxyethyl methacrylate, glycidyl methacrylate, and butyl methacrylate.
[0011] Furthermore, the saturated fatty acid-based photosensitive resin is prepared by uniformly mixing saturated fatty acids and modifiers at 90°C, heating to 100°C, adding triethylamine and stirring for 3 hours, then restoring to room temperature, adding 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and microcrystalline cellulose, and mechanically stirring for 30 minutes.
[0012] Furthermore, the photopolymerization 3D printing specifically involves pouring the saturated fatty acid-based photosensitive resin into the material tank of an ultraviolet-treated 3D printer, and curing it layer by layer under ultraviolet light irradiation at a wavelength of 405 nm according to a preset three-dimensional model, at a printing speed of 20 mm / h.
[0013] The method of using the bio-based solid-state lighting element prepared by the above method is to couple one end of the bio-based solid-state lighting element to an optical fiber and connect the other end to a laser emitter to form a lighting device; after being powered on, the highly directional point light source can be transformed into a uniform surface light source through the bio-based solid-state lighting element.
[0014] The beneficial effects of this invention are as follows: (1) This invention utilizes renewable saturated fatty acids to prepare photosensitive resins, and effectively solves the problems of low reactivity and inability to be photocured by saturated fatty acids through simple esterification or transesterification reactions; the prepared photosensitive resins have the characteristics of rapid photocuring and are comparable to commercial photosensitive resins.
[0015] (2) The purpose of this invention is to overcome the shortcomings of the prior art and provide a saturated fatty acid-based photosensitive resin and its application method in additive manufacturing of solid-state lighting elements. Compared with the unsaturated fatty acids commonly used in the past, saturated fatty acids are difficult to achieve effective photocuring due to the lack of photosensitive groups, low reactivity, and high difficulty in modification. This invention successfully solves the above-mentioned technical problems through a specific modification method, enabling the saturated fatty acid-based resin to have the ability to be rapidly photocured, making it suitable for photocuring additive manufacturing processes. In addition, the prepared solid-state lighting elements can be effectively applied in the field of solid-state lighting, expanding the innovative application of bio-based materials in 3D printing. Attached Figure Description
[0016] Figure 1 The image shows the photocuring rheology of the saturated fatty acid-based photosensitive resin prepared in Example 11, where G-C8, G-C10, G-C12, G-C14, and G-C16 represent photosensitive resins prepared from octanoic acid, capric acid, lauric acid, myristic acid, and palmitic acid, respectively.
[0017] Figure 2 The image shows the illuminance results of the solid-state lighting element prepared in Example 12. In this image, pG-C10 and pG-C16 represent photocured decanoic acid and palmitic acid-based photosensitive resins, respectively, and pG-C16-3% represents palmitic acid-based photosensitive resin with 3% added microcrystalline cellulose. Detailed Implementation
[0018] A method for additive manufacturing of bio-based solid-state lighting elements involves pouring saturated fatty acid-based photosensitive resin into the material tank of an ultraviolet-treated 3D printer, and then curing it layer by layer under ultraviolet light irradiation at a wavelength of 405 nm according to a preset three-dimensional model, thereby obtaining the bio-based solid-state lighting element.
[0019] The preparation method of the saturated fatty acid-based photosensitive resin is as follows: 55-68 parts by weight of saturated fatty acid and 32-45 parts by weight of modifier are uniformly mixed at 90°C, the temperature is raised to 100°C, then 2 parts by weight of triethylamine are added and stirred for 3 hours, then the mixture is restored to room temperature, and then 2 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 0-5 parts by weight of microcrystalline cellulose are added and mechanically stirred for 30 minutes to obtain the resin.
[0020] The saturated fatty acid is any one of caprylic acid, capric acid, lauric acid, myristic acid, and palmitic acid. The modifier is any one of hydroxyethyl methacrylate, glycidyl methacrylate, and butyl methacrylate.
[0021] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.
[0022] Raw materials: Caprylic acid, capric acid, lauric acid, myristic acid and palmitic acid were purified by hydrolysis of vegetable oil; hydroxyethyl methacrylate, glycidyl methacrylate, butyl methacrylate, triethylamine, microcrystalline cellulose (100~200 mesh) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide were purchased from Shanghai Maclean Biochemical Technology Co., Ltd.
[0023] 1. Static mechanical property testing: The tensile strength and modulus tests of the saturated fatty acid-based photosensitive resin were performed on an Instron 3365 microcomputer-controlled electronic universal testing machine in the United States, with a loading rate of 10 mm / min. The tensile strength samples were dumbbell-shaped (specifications: length 50 mm, standard width 15 mm, narrow section width 4 mm, thickness 3 mm).
[0024] 2. Photocuring rheological test: Rheological tests of the photocured saturated fatty acid-based photosensitive resins were conducted using a TA Instruments DHR-3 rheometer. Tests were performed between parallel plates consisting of a 20 mm diameter upper heating plate fixture and a 20 mm diameter quartz base plate. All tests were conducted with a 25 mm gap. μ The ultraviolet light for testing was turned on 20 seconds after the start of the test, and the wavelength of the ultraviolet light was 405 nm.
[0025] 3. Illuminance test: Illuminance testing of additively manufactured solid-state lighting components was performed using a Far East SPIC-300AW illuminance meter, with one point measured at every 10-degree angle.
[0026] Example 1 65 g of palmitic acid and 35 g of glycidyl methacrylate were mixed and stirred evenly at 90°C, then heated to 100°C and 2 g of triethylamine were added. After mixing and stirring for 3 hours, the mixture was allowed to return to room temperature. Then, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 5 g of microcrystalline cellulose were added and stirred evenly for 30 min to obtain saturated fatty acid-based photosensitive resin.
[0027] The obtained saturated fatty acid-based photosensitive resin was poured into a photopolymerization 3D printer and printed at a single-layer printing speed of 20 mm / h under ultraviolet light with a wavelength of 405 nm to obtain a bio-based solid-state lighting element.
[0028] Example 2 In Example 1, 65 g of palmitic acid and 35 g of glycidyl methacrylate were replaced with 68 parts of palmitic acid and 32 parts of hydroxyethyl methacrylate, and the other steps were the same as in Example 1.
[0029] Example 3 In Example 1, 65 g of palmitic acid and 35 g of glycidyl methacrylate were replaced with 64 parts of palmitic acid and 36 parts of butyl methacrylate, and the other steps were the same as in Example 1.
[0030] Example 4 Replace 5 g of microcrystalline cellulose in Example 1 with 0 g of microcrystalline cellulose, and follow the same steps as in Example 1.
[0031] Example 5 Replace 5 g of microcrystalline cellulose in Example 1 with 3 g of microcrystalline cellulose, and follow the same steps as in Example 1.
[0032] Example 6 60 g of lauric acid and 40 g of glycidyl methacrylate were mixed and stirred evenly at 90°C, then heated to 100°C and 2 g of triethylamine were added. After mixing and stirring for 3 hours, the mixture was allowed to return to room temperature. Then 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide was added and stirred evenly for 30 min to obtain saturated fatty acid-based photosensitive resin.
[0033] The obtained saturated fatty acid-based photosensitive resin was poured into a photopolymerization 3D printer and printed at a single-layer printing speed of 20 mm / h under ultraviolet light with a wavelength of 405 nm to obtain a bio-based solid-state lighting element.
[0034] Example 7 In Example 6, 60 g of lauric acid and 40 g of glycidyl methacrylate were replaced with 63 g of myristic acid and 37 g of glycidyl methacrylate, and the other steps were the same as in Example 1.
[0035] Example 8 In Example 6, 60 g of lauric acid and 40 g of glycidyl methacrylate were replaced with 58 g of decanoic acid and 42 g of glycidyl methacrylate, and the other steps were the same as in Example 1.
[0036] Example 9 In Example 6, 60 g of lauric acid and 40 g of glycidyl methacrylate were replaced with 55 g of caprylic acid and 45 g of glycidyl methacrylate, and the other steps were the same as in Example 1.
[0037] Example 10 60 g of palmitic acid and 40 g of glycidyl methacrylate were mixed and stirred evenly at 90°C, then heated to 100°C and 2 g of triethylamine were added. After mixing and stirring for 3 hours, the mixture was allowed to return to room temperature. Then, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 5 g of microcrystalline cellulose were added and stirred evenly for 30 min to obtain saturated fatty acid-based photosensitive resin.
[0038] The obtained saturated fatty acid-based photosensitive resin was poured into a photopolymerization 3D printer and printed at a single-layer printing speed of 20 mm / h under ultraviolet light with a wavelength of 405 nm to obtain a bio-based solid-state lighting element.
[0039] Table 1
[0040] Table 1 shows the mechanical properties of the prepared saturated fatty acid-based photocurable resin. As shown in Table 1, the optimal tensile strength of the prepared saturated fatty acid-based photocurable resin is 6.0 MPa, and the tensile modulus is 301 MPa.
[0041] Example 11 65 g of different saturated fatty acids and 35 g of glycidyl methacrylate were mixed and stirred evenly at 90°C. The mixture was then heated to 100°C and 2 g of triethylamine was added. After mixing and stirring for 3.5 hours, the mixture was allowed to return to room temperature. Then, 2 g of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 5 g of microcrystalline cellulose were added and stirred evenly for 30 minutes to obtain saturated fatty acid-based photosensitive resin.
[0042] Figure 1The figure shows the photocuring rheological profiles of saturated fatty acid-based photosensitive resins prepared using different saturated fatty acids. As can be seen from the figure, the storage modulus and loss modulus of all saturated fatty acid-based photosensitive resins intersect within 10 s after the 405 nm UV lamp is turned on. This corresponds to the photocuring gel point of the photosensitive resin, indicating that all prepared saturated fatty acid-based photosensitive resins can gel within 10 s, demonstrating their excellent photocuring ability and rapid curing after UV excitation.
[0043] Example 12 65 g of decanoic acid or palmitic acid and 35 g of glycidyl methacrylate were mixed and stirred evenly at 90°C. The mixture was then heated to 100°C and 2 g of triethylamine was added. After mixing and stirring for 3 hours, the mixture was allowed to return to room temperature. Then, 2 g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and a certain amount of microcrystalline cellulose were added and stirred evenly for 30 minutes to obtain saturated fatty acid-based photosensitive resin.
[0044] The obtained saturated fatty acid-based photosensitive resin was poured into a photopolymerization 3D printer and printed at a single-layer printing speed of 20 mm / h under ultraviolet light with a wavelength of 405 nm to obtain a bio-based solid-state lighting element.
[0045] Figure 2 The figure shows the illuminance results of the obtained solid-state lighting element. As can be seen from the figure, when light passes through pG-C10 resin, almost no scattering occurs; for pG-C16 resin, due to the presence of internal microcrystalline domains, light scattering occurs in a small range; and the addition of microcrystalline cellulose makes the internal crystal region of pG-C16-3% more uniform, and the scattered light is more uniform.
[0046] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.
Claims
1. A method for additive manufacturing of bio-based solid-state lighting elements, characterized in that: The bio-based solid-state lighting element is fabricated using saturated fatty acid-based photosensitive resin via photopolymerization 3D printing. The saturated fatty acid-based photosensitive resin, by weight, comprises: 55-68 parts of saturated fatty acid, 32-45 parts of modifier, 2 parts of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2 parts of triethylamine, and 0-5 parts of microcrystalline cellulose.
2. The method for additive manufacturing of bio-based solid-state lighting elements according to claim 1, characterized in that: The saturated fatty acid is any one of caprylic acid, capric acid, lauric acid, myristic acid, and palmitic acid.
3. The method for additive manufacturing of bio-based solid-state lighting elements according to claim 1, characterized in that: The modifier is any one of hydroxyethyl methacrylate, glycidyl methacrylate, and butyl methacrylate.
4. The method for additive manufacturing of bio-based solid-state lighting elements according to claim 1, characterized in that: The saturated fatty acid-based photosensitive resin is prepared by uniformly mixing saturated fatty acids and modifiers at 90°C, heating to 100°C, adding triethylamine and stirring for 3 hours, then restoring to room temperature, adding 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and microcrystalline cellulose, and mechanically stirring for 30 minutes.
5. The method for additive manufacturing of bio-based solid-state lighting elements according to claim 1, characterized in that: Specifically, the photopolymerization 3D printing involves curing saturated fatty acid-based photosensitive resin layer by layer at a printing speed of 20 mm / h under ultraviolet light irradiation with a wavelength of 405 nm.
6. A method for illumination using a bio-based solid-state lighting element prepared by the method of claim 1, characterized in that: The bio-based solid-state lighting element is coupled at one end to an optical fiber and at the other end to a laser emitter, thereby forming a lighting device.