Photocuring 3D printing ink with long afterglow property as well as preparation method and application of photocuring 3D printing ink

Abstract

The invention discloses a photocuring 3D printing ink with a long afterglow property as well as a preparation method and application thereof, and relates to the technical field of organic long afterglow materials. According to the invention, on the basis of the organic long-afterglow material, by adjusting the doping proportion of the organic long-afterglow material and the composition of the photosensitive resin, the regulation and control of the mechanical property are realized, and finally the effect of improving the mechanical property of a structural device by 3.6 times is achieved; the limitation that the mechanical property of a traditional long-afterglow photocuring 3D printing structure always depends on the property of the selected photosensitive resin is broken through. Besides, real-time self-monitoring of the 3D printing process can be achieved by reading the afterglow life and the afterglow duration time of the ink during 3D printing, and the technology has the effect of integrating the printing structure and monitoring. The photocuring 3D printing ink with the long afterglow property developed by the invention has a wide application prospect in the fields of aerospace, automobile manufacturing, biomedical treatment, precise structural part manufacturing and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic long afterglow materials, in particular to a kind of light-cured 3D printing ink with long afterglow properties and its preparation method and application. BACKGROUND

[0002] Organic long afterglow refers to the characteristic that organic luminescent molecules can continue to emit light for a period of time after the excitation light stops. The earliest observation of blue-green organic long afterglow in tetraphenylmethane and tetraphenylsilane crystals was reported by Daniel Clapp in 1939 (J. Am. Chem. Soc. 1939, 61, 523-524.). Subsequently, after years of development, small molecule host-guest doped organic long afterglow systems, polymer-based organic long afterglow systems, supramolecular organic long afterglow systems, and carbon dot organic long afterglow systems have been reported, and a series of long afterglow luminescent materials have been designed based on these systems, enabling their commercial applications in the fields of biomedical, display lighting, wearable devices, sensing and detection, information anti-counterfeiting, etc.

[0003] Self-monitoring materials are a class of intelligent materials that integrate "sensing" and "feedback" functions. Without relying on external complex sensors, they can reflect changes in the physical and chemical properties of the material or structure itself through changes in the color, luminescence, and other visual signals of the material itself. By embedding self-monitoring materials into devices, they can be used for mechanical, micro-crack, fatigue damage, and aging monitoring of devices, as well as monitoring of external environmental humidity, temperature, oxygen concentration, and harmful gases. Such materials have a very promising application prospect in the fields of structural safety, biomedical, food packaging, environmental monitoring, and smart wearables. Organic long afterglow materials are a type of excellent self-monitoring material, and by making them into 3D printing self-monitoring ink, various self-monitoring devices can be personalized manufactured.

[0004] Existing technologies have disclosed light-cured 3D printing ink with long afterglow properties that can achieve self-monitoring in terms of temperature and mechanics, and are applied in temperature self-monitoring systems (Chem. Sci. 2025, 16, 5299-5309) and structural health self-monitoring systems (Nat. Commun. 2024, 15, 1596). However, the self-monitoring function of the light-cured 3D printing ink with long afterglow properties is relatively single and not comprehensive enough, and it is still necessary to expand its self-monitoring field. In addition, there are few reports on long afterglow light-cured 3D printing ink that can improve the mechanical properties of printed structures and monitor the printing state of printed structures in real time, which depends on the inherent properties of the selected photosensitive resin. It is a problem that we have not yet solved to develop a long afterglow light-cured 3D printing ink that can not only improve the mechanical properties of 3D printed structures but also achieve real-time self-monitoring of the 3D printing process. SUMMARY

[0005] In view of the deficiencies in the prior art, the present application mainly solves the technical problem of improving the mechanical properties of the printing structure of the long afterglow photocuring 3D printing ink, and realizing real-time self-monitoring during the 3D printing process, which seriously limits the application of the long afterglow photocuring 3D printing ink in practice. The present application provides a long afterglow photocuring 3D printing ink, a preparation method and an application thereof, which not only breaks through the mechanical property limitation of the traditional photosensitive resin itself, but also realizes real-time self-monitoring of the 3D printing structure during the printing process.

[0006] The first object of the present application is to provide a long afterglow material, and the structural general formula of the long afterglow material comprises one of the following:

[0007]

[0008] In formula (I), formula (II), formula (III), formula (IV), formula (V) and formula (VI), A and B are independently selected from one of halogen atoms, methyl, ethyl, methoxy, bis (4-tert-butylphenyl) amine, diphenylamine and chloro diphenyl phosphine.

[0009] Preferably, the structural formula of the long afterglow material is any one of the following: .

[0010] The second objective of this invention is to provide an application of a long afterglow material in photocurable 3D printing ink.

[0011] The third objective of this invention is to provide a type of photocurable 3D printing ink with long afterglow properties, which includes the aforementioned type of long afterglow material and photosensitive resin matrix. The photosensitive resin matrix includes photosensitive resin monomers, photoinitiators, and crosslinking agents; The photosensitive resin monomer is one or more of the following: acrylate, methacrylate, epoxy acrylate, hydroxyethyl acrylate, tert-butyl acrylate, isobornyl acrylate, aliphatic polyurethane acrylate, polymethyl methacrylate, polyvinyl alcohol resin, and polyethylene glycol diacrylate. The photoinitiator is one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide; The crosslinking agent is polyethylene glycol diacrylate or aliphatic polyurethane diacrylate; Preferably, the photoinitiator accounts for 1 to 2 wt% of the photosensitive resin matrix; and the crosslinking agent accounts for 1 to 40 wt% of the photosensitive resin matrix.

[0012] Preferably, the mass ratio of the long afterglow material to the photosensitive resin matrix is ​​1:10~20000.

[0013] The fourth objective of this invention is to provide a method for preparing a photocurable 3D printing ink with long afterglow properties, comprising the following steps: blending a long afterglow material, a photosensitive resin monomer, a photoinitiator, and a crosslinking agent in a certain proportion to obtain a photocurable 3D printing ink with long afterglow properties.

[0014] The fifth objective of this invention is to provide an application of a photocurable 3D printing ink with long afterglow properties in optical sensing, humidity sensing, temperature sensing, structural health monitoring, mechanical sensing, display lighting, information encryption, biomedicine, self-monitoring sensing, or additive manufacturing.

[0015] The sixth objective of this invention is to provide a structural component obtained by 3D printing using a type of photocurable 3D printing ink with long afterglow properties.

[0016] The seventh objective of this invention is to provide a real-time self-monitoring method for the printing process of 3D printed structural parts. This method uses photocurable 3D printing ink with long afterglow properties to perform real-time self-monitoring of the printing process of 3D printed structural parts through the visualization effect of long afterglow.

[0017] Compared with the prior art, the beneficial effects of the present invention are: This invention provides a type of photocurable 3D printing ink with long-persistence properties, its preparation method, and its applications. Based on a designed and prepared long-persistence luminescent material, this invention incorporates the long-persistence material into a photosensitive resin to prepare a photocurable 3D printing ink with long-persistence properties. Compared with photosensitive resin without long-persistence material, the mechanical properties of the structural device are improved by up to 3.6 times. By adding the long-persistence material, the mechanical properties of the photosensitive resin can be controlled. This breaks the limitation that the mechanical properties of structural devices prepared with traditional 3D printing inks often depend on the mechanical properties of the selected photosensitive resin itself. This innovation lays a solid foundation for in-depth research on the influence of long-persistence materials on the mechanical properties of 3D printed structures.

[0018] The photocurable 3D printing ink with long afterglow properties prepared in this invention provides a visible effect during the 3D printing process. Furthermore, the printing time exhibits a consistent linear relationship with the afterglow lifetime, afterglow duration, and the mechanical properties of the printed structure. These mechanical properties reflect the completion or non-completion of the printing process; that is, the afterglow lifetime and duration of the long afterglow allow for real-time monitoring of the printing process. This invention provides a reasonable method for real-time self-monitoring of the 3D printing process.

[0019] The photocurable 3D printing ink with long afterglow properties prepared in this invention can print complex three-dimensional structural models with excellent mechanical properties through 3D printing technology, and can be applied to real-time self-monitoring of the 3D printing process. This ink has good application prospects in the fields of optical sensing, humidity sensing, temperature sensing, structural health monitoring, mechanical sensing, display lighting, information encryption, biomedicine, self-monitoring sensing and additive manufacturing. Attached Figure Description

[0020] Figure 1This diagram shows the strain-stress curves of the photosensitive resin and four photocurable 3D printing inks with long afterglow properties according to the present invention. The black line represents the strain-stress curve of the photosensitive resin of Example 2, the red line represents the strain-stress curve of photocurable 3D printing ink 1 with long afterglow properties of Example 3, the blue line represents the strain-stress curve of photocurable 3D printing ink 2 with long afterglow properties of Example 4, the green line represents the strain-stress curve of photocurable 3D printing ink 3 with long afterglow properties of Example 5, and the purple line represents the strain-stress curve of photocurable 3D printing ink 4 with long afterglow properties of Example 6.

[0021] Figure 2 These are delayed-motion spectra of four photocurable 3D printing inks with long-persistence properties according to the present invention. The black line represents the delayed-motion spectrum of photocurable 3D printing ink 1 with long-persistence properties in Example 3; the red line represents the delayed-motion spectrum of photocurable 3D printing ink 2 with long-persistence properties in Example 4; the blue line represents the delayed-motion spectrum of photocurable 3D printing ink 3 with long-persistence properties in Example 5; and the green line represents the delayed-motion spectrum of photocurable 3D printing ink 4 with long-persistence properties in Example 6.

[0022] Figure 3 This is a curing depth test of the photocurable 3D printing ink 1 with long afterglow properties in Example 3 of this invention. The black to green curves represent the differences in curing depth at different light intensities.

[0023] Figure 4 In Embodiment 7 of the present invention, after using the photocurable 3D printing ink 1 with long afterglow properties from Embodiment 3 to 3D print a series of complex high-precision hollow structure models and fine solid models, the images show the long afterglow before and after ultraviolet light irradiation.

[0024] Figure 5 In Embodiment 8 of the present invention, 3D printing is performed using the photocurable 3D printing ink 1 with long afterglow properties from Embodiment 3, and the application diagram of the ink in structural mechanical enhancement is shown.

[0025] Figure 6 In Embodiment 9 of the present invention, a curve showing the relationship between 3D printing time and afterglow lifetime was obtained by using photocurable 3D printing ink 3 with long afterglow properties.

[0026] Figure 7 In Embodiment 9 of the present invention, a curve showing the relationship between 3D printing time and afterglow duration was obtained by using photocurable 3D printing ink 3 with long afterglow properties.

[0027] Figure 8This is a graph showing the relationship between 3D printing time and mechanical properties (Young's modulus) measured using photocurable 3D printing ink 3 with long afterglow properties in Embodiment 9 of the present invention.

[0028] Figure 9 This is an application demonstration diagram of real-time self-monitoring of the 3D printing process using photocurable 3D printing ink 3 with long afterglow properties in Embodiment 9 of the present invention.

[0029] Figure 10 This is the NMR spectrum of a long-afterglow material.

[0030] Figure 11 This is the NMR spectrum of a long-afterglow material II.

[0031] Figure 12 This is the NMR spectrum of a long-afterglow material (III).

[0032] Figure 13 This is the NMR spectrum of a long-afterglow material (NMR 4). Detailed Implementation

[0033] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below in conjunction with specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention.

[0034] The purpose of this invention is to provide a type of photocurable 3D printing ink with long afterglow properties, its preparation method, and its applications. This ink comprises a long afterglow material and a photosensitive resin matrix. Based on organic long afterglow materials, this invention achieves control over mechanical properties by adjusting the doping ratio of the organic long afterglow material and the composition of the photosensitive resin, ultimately improving the mechanical properties of the structural device by 3.6 times. This overcomes the limitation that the mechanical properties of traditional long afterglow photocurable 3D printed structures often depend on the properties of the selected photosensitive resin itself. Furthermore, this invention enables real-time self-monitoring of the 3D printing process by reading the afterglow lifetime and afterglow duration of the ink during 3D printing, providing an integrated effect of printing structure and monitoring. The photocurable 3D printing ink with long afterglow properties developed in this invention has broad application prospects in aerospace, automotive manufacturing, biomedicine, and precision structural component manufacturing.

[0035] This invention investigates the influence of organic long-afterglow materials on the luminescence and mechanical properties of photocurable inks through steady-state-transient fluorescence spectroscopy, material mechanics testing, and curing depth testing. It proposes a reasonable design strategy for photocurable 3D printing inks with long-afterglow properties, enabling the control of the mechanical properties of photocurable 3D printing inks with long-afterglow properties and real-time self-monitoring of the 3D printing process.

[0036] This invention utilizes luminescence and mechanical property testing to select photosensitive resin monomers and long-afterglow materials to prepare a real-time self-monitoring ink for the photocurable 3D printing process, exhibiting long-afterglow properties through blending. This ink integrates the functions of printing structure monitoring and control, enabling real-time monitoring of the printed structure's status without the need for external large-scale equipment, offering advantages such as low monitoring cost and ease of use.

[0037] This invention utilizes a designed photopolymer 3D printing ink with long afterglow properties, printed using a P150 printer from Chongqing Mofang Precision Technology Co., Ltd., to create complex three-dimensional hollow structure models and intricate solid structure models. This mechanically tunable long afterglow photopolymer 3D printing ink can be applied to real-time self-monitoring of the 3D printing process, optical sensing, humidity sensing, temperature sensing, structural health monitoring, mechanical sensing, display lighting, information encryption, biomedicine, self-monitoring sensing, and additive manufacturing. To achieve the above objectives, a first aspect of the present invention provides a class of long afterglow materials, wherein the structural formula of the long afterglow material includes one of the following:

[0038]

[0039] In formulas (Ⅰ), (Ⅱ), (Ⅲ), (Ⅳ), (Ⅴ) and (Ⅵ), A and B are independently selected from one of the following: halogen atom, methyl, ethyl, methoxy, bis(4-tert-butylphenyl)amine, diphenylamine and dichlorodiphenylphosphine.

[0040] The structural formula of the long afterglow material is any one of the following: .

[0041] A second aspect of the present invention provides the application of a long afterglow material in photocurable 3D printing ink.

[0042] A third aspect of the present invention provides a type of photocurable 3D printing ink with long afterglow properties, which includes the aforementioned type of long afterglow material and photosensitive resin matrix; The photosensitive resin matrix includes photosensitive resin monomers, photoinitiators, and crosslinking agents; The photosensitive resin monomer includes one or more of the following: acrylate, methacrylate, epoxy acrylate, hydroxyethyl acrylate, tert-butyl acrylate, isobornyl acrylate, aliphatic polyurethane acrylate, polymethyl methacrylate, polyvinyl alcohol resin, and polyethylene glycol diacrylate. The photoinitiator is one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide; The crosslinking agent is polyethylene glycol diacrylate or aliphatic polyurethane diacrylate; The photoinitiator accounts for 1 to 2 wt% of the photosensitive resin matrix; the crosslinking agent accounts for 1 to 40 wt% of the photosensitive resin matrix; and the mass ratio of the long afterglow material to the photosensitive resin matrix is ​​1:10 to 20000.

[0043] The fourth aspect of this invention provides a method for preparing a photocurable 3D printing ink with long afterglow properties, comprising the following steps: blending a long afterglow material, a photosensitive resin monomer, a photoinitiator and a crosslinking agent in a certain proportion to obtain a photocurable 3D printing ink with long afterglow properties.

[0044] For example, the prepared long-afterglow material is mixed with photosensitive resin at a mass ratio of 0.05~10wt%, photoinitiator and photosensitive resin at a mass ratio of 1~2wt%, and crosslinking agent and photosensitive resin at a mass ratio of 1~40wt%. After stirring evenly and mixing thoroughly, the photocurable 3D printing ink with long-afterglow properties of the present invention can be obtained.

[0045] The fifth aspect of this invention provides an application of a photocurable 3D printing ink with long afterglow properties in optical sensing, humidity sensing, temperature sensing, structural health monitoring, mechanical sensing, display lighting, information encryption, biomedicine, self-monitoring sensing, or additive manufacturing.

[0046] The sixth aspect of the present invention provides a structural component obtained by 3D printing using a type of photocurable 3D printing ink with long afterglow properties.

[0047] The seventh aspect of the present invention provides a real-time self-monitoring method for the printing process of 3D printed structural parts. The method uses a photocurable 3D printing ink with long afterglow properties to perform real-time self-monitoring of the printing process of 3D printed structural parts through the visualization effect of long afterglow.

[0048] It should be noted that, unless otherwise specified, the experimental methods used in this invention are all conventional methods; and the reagents and materials used, unless otherwise specified, are all commercially available.

[0049] Example 1 Example 1: Design and fabrication of a class of long afterglow materials The design and fabrication of a class of long afterglow materials, with the general molecular structure formula:

[0050]

[0051] In formulas (I), (II), (III), (IV), (V), and (VI), A and B are one of halogen atoms, methyl, ethyl, methoxy, bis(4-tert-butylphenyl)amine, diphenylamine, and dichlorodiphenylphosphine.

[0052] Specifically, the synthesis route for long afterglow material I is as follows:

[0053] Using 2-bromodibenzothiophene (1 g), di(4-tert-butylphenyl)amine (1.07 g), tri-tert-butylphosphine (0.41 g), potassium tert-butoxide (0.43 g), palladium acetate (18 mg), and toluene (40 ml) as reactants, the mixture was heated to 110 °C and stirred for 24 h before the reaction was stopped. The product was purified by silica gel column chromatography to obtain a white powder, which was identified as long afterglow material I. See also... Figure 10 The image shows NMR data for long-afterglow materials.

[0054] Specifically, the synthesis route for long afterglow material II is as follows:

[0055] Using 4-bromodibenzothiophene (1 g), di(4-tert-butylphenyl)amine (1.07 g), tri-tert-butylphosphine (0.41 g), sodium tert-butoxide (0.37 g), tris(dibenzylacetone)dipalladium (0) (18 mg), and toluene (40 ml) as reactants, the mixture was heated to 110 °C and stirred for 24 h before the reaction was stopped. The product was then purified by silica gel column chromatography to obtain a white powder, which is the long afterglow material II. See also... Figure 11 The image shows NMR data for long-afterglow materials.

[0056] Specifically, the synthesis route for long afterglow material III is as follows:

[0057] Using phenothiazine (10 g), 2-bromoiodobenzene (14.34 g), potassium phosphate (29.83 g), cuprous oxide (1.44 g), N,N,N',N'-tetramethylethylenediamine (2.40 g), and o-dichlorobenzene (140 mL) as reactants, the mixture was heated to 180 °C and stirred for 48 h before the reaction was stopped. The compound oBrphpz was purified by silica gel column chromatography. Using compound oBrphpz (2 g), potassium carbonate (2.34 g), tricyclohexylphosphine (0.32 g), and N,N-dimethylformamide (45 mL) as reactants, the mixture was heated to 160 °C and stirred for 48 h before the reaction was stopped. The mixture was then purified by silica gel column chromatography to obtain compound Cphpz, which is the long afterglow material III. See also... Figure 12 The image shows the NMR data for long-afterglow materials.

[0058] Specifically, the synthesis route for long afterglow material IV is as follows:

[0059] Using long afterglow material III (1g), N-bromosuccinimide (0.65g) and oxygen-free dichloromethane solution (50mL) as reactants, the mixture was cooled to 0℃ and stirred for 5h before the reaction was stopped. The compound Cphpz-Br was purified by silica gel column chromatography. Using compound Cphpz-Br (1.56 g) and anhydrous and oxygen-free tetrahydrofuran solution (50 mL) as reactants, the mixture was cooled to -78 °C, and 1.6 M n-butyllithium solution (3.31 mL) was added dropwise. The reaction mixture was stirred at -78 °C for 2 h, followed by the addition of dichlorodiphenylphosphine (1.17 g). The mixture was stirred at -78 °C for 1 h, then the temperature was raised to room temperature, and stirring continued for 12 h. The reaction was quenched by adding water, and the reaction mixture was concentrated by vacuum distillation to obtain the crude product. The crude product was purified by silica gel column chromatography to obtain compound Cphpz-DPP, i.e., long afterglow material IV; see [link to article]. Figure 13 The NMR data for long-afterglow material IV are shown.

[0060] Example 2 A method for preparing a photosensitive resin includes the following steps: weighing 7g of hydroxyethyl acrylate, 3g of acrylic acid, 0.15g of polyethylene glycol diacrylate, and 0.15g of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, mixing them together, and stirring them in a roller mixer for 12 hours until they are evenly mixed to obtain the photosensitive resin.

[0061] The photosensitive resin provided in Example 2 was used to prepare a tensile sample by dropping 160 μL of the resin into a polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing oven for 1 hour, the material's mechanical properties were tested. The measured Young's modulus was 476.1 MPa. Figure 1 As shown by the black curve.

[0062] Example 3 A method for preparing a type of photocurable 3D printing ink with long afterglow properties includes the following steps: weighing the long afterglow material I (0.01g), hydroxyethyl acrylate (7g), acrylic acid (3g), polyethylene glycol diacrylate (0.15g), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (0.15g) designed and prepared in Example 1, mixing them together, and then stirring them in a roller mixer for 12 hours until they are uniformly mixed to obtain photocurable 3D printing ink 1 with long afterglow properties.

[0063] The photocurable 3D printing ink 1 with long afterglow properties provided in Example 3 was prepared by dropping 100 μL of the ink into a polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing chamber for 1 hour, a delayed-wave spectroscopy test was performed. The peak value of the delayed spectrum was measured to be 512 nm. Figure 2 As shown by the black curve.

[0064] A tensile sample was prepared by dripping 160 μL of liquid into a small polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing oven for 1 hour, the material's mechanical properties were tested. The measured Young's modulus was 1710.3 MPa. Figure 1As shown by the red curve.

[0065] In this embodiment, the long-persistence photopolymer 3D printing ink 1 was tested for curing depth to explore the relationship between light source exposure intensity, exposure time, and printing depth during DLP 3D printing. The tests showed that, for a given exposure intensity, a longer exposure time resulted in a deeper curing depth; conversely, for a given exposure time, a higher exposure intensity resulted in a deeper curing depth. During DLP 3D printing, specific printing parameters need to be determined based on the curing depth data and the fineness and complexity of the printed model. The measured curing depth of the long-persistence photopolymer 3D printing ink 1 is as follows: Figure 3 As shown.

[0066] Example 4 A method for preparing a type of photocurable 3D printing ink with long afterglow properties includes the following steps: weighing the long afterglow material II (0.01g), hydroxyethyl acrylate (7g), acrylic acid (3g), polyethylene glycol diacrylate (0.15g), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (0.15g) designed and prepared in Example 1, mixing them together, and then stirring them in a roller mixer for 12 hours until they are uniformly mixed to obtain photocurable 3D printing ink 2 with long afterglow properties.

[0067] The photocurable 3D printing ink 2 with long afterglow properties provided in Example 4 was prepared by dropping 100 μL into a polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing chamber for 1 hour, a delayed-wave spectrum was measured, and the peak value of the delayed spectrum was found to be at 485 nm (with a shoulder peak at 466 nm). Figure 2 As shown by the red curve.

[0068] A tensile sample was prepared by dripping 160 μL of liquid into a small polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing oven for 1 hour, the material's mechanical properties were tested. The measured Young's modulus was 1363.0 MPa. Figure 1 As shown by the blue curve.

[0069] Example 5 A method for preparing a type of photocurable 3D printing ink with long afterglow properties includes the following steps: weighing the long afterglow material IV (0.01g), hydroxyethyl acrylate (7g), acrylic acid (3g), and polyethylene glycol diacrylate (4g) designed and prepared in Example 1, mixing them together, and then stirring them in a roller mixer for 12 hours until they are mixed evenly to obtain photocurable 3D printing ink 3 with long afterglow properties.

[0070] The photocurable 3D printing ink 3 with long afterglow properties provided in Example 4 was used to prepare a thin film sample by dropping 100 μL of the ink into a polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing chamber for 1 hour, a delayed-wave spectroscopy test was performed, and the peak value of the delayed spectrum was found to be at 513 nm. Figure 2 As shown by the blue curve.

[0071] A tensile sample was prepared by dripping 160 μL of liquid into a small polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing oven for 1 hour, the material's mechanical properties were tested. The measured Young's modulus was 1270.3 MPa. Figure 1 As shown by the green curve.

[0072] Example 6 A method for preparing a type of photocurable 3D printing ink with long afterglow properties includes the following steps: weighing the long afterglow material III (0.01g), hydroxyethyl acrylate (7g), acrylic acid (3g), and polyethylene glycol diacrylate (4g) designed and prepared in Example 1, mixing them together, and then stirring them in a roller mixer for 12 hours until they are mixed evenly to obtain photocurable 3D printing ink 4 with long afterglow properties.

[0073] The photocurable 3D printing ink 4 with long afterglow properties provided in Example 4 was prepared by dropping 100 μL into a polytetrafluoroethylene (PTFE) mold using a pipette. After curing in a UV curing chamber for 1 hour, a delayed-wave spectrum was measured, and the peak value of the delayed spectrum was found to be at 480 nm (with a shoulder peak at 460 nm). Figure 2 As shown by the green curve.

[0074] A 160 μL drop was pipetted into a small polytetrafluoroethylene (PTFE) mold to prepare a tensile sample. After curing in a UV curing oven for 1 hour, the material's mechanical properties were tested. The measured Young's modulus was 1269.6 MPa. Figure 1 As shown by the purple curve.

[0075] Example 7 Applications of photopolymer 3D printing inks with long afterglow properties in 3D printing include: The photocurable 3D printing ink 1 with long afterglow properties provided in Example 3 was loaded into a DLP 3D printer. Based on the curing depth data measured in Example 3, the model slice layer thickness was 50 μm, and the exposure intensity was 3.14 ~ 6.4 mW / cm. 3 With an exposure time of 3 seconds, a series of intricate solid objects and complex, high-precision hollow structures were printed. After a 1-hour post-curing period, these structures all exhibited a long afterglow emission property of approximately 4 seconds at room temperature. Photos of the 3D printed models are shown below. Figure 4As shown in the table. The printing parameters for each model, including the number of printing layers, exposure intensity, exposure time, platform descent height, platform descent dwell time, platform ascent height, and platform ascent dwell time, are detailed in Tables 1-4 below.

[0076] Table 1: Printing parameters for long afterglow hollow lattice models

[0077] Table 2: Printing parameters for the hollow model of the long afterglow sieve

[0078] Table 3: Printing Parameters for Long Afterglow Solid Rabbit Model

[0079] Table 4: Printing Parameters for Solid Deer Model with Long Afterglow Sieve

[0080] It should be noted that in Tables 1-4, "Number of Printed Layers" refers to the number of model slice images printed in each stage, with a total of three stages. The specific division depends on the actual model. "Exposure Intensity" refers to the exposure intensity of each printed image. "Exposure Time" refers to the continuous exposure time for each printed image. "Platform Drop / Rise Height": After printing one image, the platform needs to drop 3mm, pause for a period of time to allow ink recirculation, then rise 2.95mm, pause for a period of time, and then begin printing the next image. 3mm - 2.95mm = 50 μm. "Platform Drop / Rise Time": After printing each image, the platform needs to pause for a period of time after dropping or rising to allow sufficient ink recirculation.

[0081] Example 8 Applications of photopolymerizable 3D printing inks with long afterglow properties in structural mechanical enhancement include: The photosensitive resin provided in Example 2 has a Young's modulus of 476.1 MPa, while the photocurable 3D printing ink 1 with long-persistence properties provided in Example 3 has a Young's modulus of 1710.3 MPa, which is 3.6 times that of the photosensitive resin in Example 2 without the addition of long-persistence materials. That is, the addition of long-persistence materials allows for the control of the mechanical properties of photocurable 3D printing inks, breaking through the limitation that the mechanical properties of long-persistence photocurable 3D printed structures often depend on the properties of the selected photosensitive resin itself.

[0082] To more intuitively demonstrate the improvement in mechanical properties after adding long-afterglow materials, the photosensitive resin provided in Example 2 and the photocurable 3D printing ink 1 with long-afterglow properties provided in Example 3 were loaded into a DLP 3D printer, and a table was prepared by 3D printing technology.

[0083] The table made of photosensitive resin provided in Example 2 deformed and collapsed in less than 0.4 seconds under the pressure of a 100g weight; while the table made of photocurable 3D printing ink 1 with long afterglow properties provided in Example 4 remained stable and reliable under the pressure of a 100g weight, and could continuously emit a long afterglow, such as... Figure 5 As shown, the addition of long-afterglow materials can significantly improve the mechanical properties of the ink and optimize the reliability of the structure. This ink has broad application prospects in aerospace, automotive manufacturing, biomedicine, and the manufacturing of precision electronic components.

[0084] Example 9 Applications of a class of photopolymer 3D printing inks with long afterglow properties in real-time self-monitoring of 3D printing include: The photocurable 3D printing ink 3 with long afterglow properties provided in Example 5 was loaded into a DLP 3D printer. After printing for 1, 2, 4, 8, 12, and 18 minutes respectively, the long afterglow lifetime curve, long afterglow duration curve, and mechanical property (expressed as Young's modulus) curves were measured as follows: Figures 5-7 As shown in Table 5 below.

[0085] Table 5: Data on the mechanical properties, long afterglow lifetime, and long afterglow duration of the structure after different printing times.

[0086] Table 5 shows that the printing time of the photocurable 3D printing ink 3 with long afterglow properties has a consistent linear relationship with the afterglow lifetime, afterglow duration, and mechanical properties of the printed structure. The mechanical properties reflect whether the printing of the device is complete. In other words, the printing process of the printed structure can be monitored in real time by observing the lifetime or duration of the long afterglow emission. This invention provides a self-monitoring 3D printing ink and a reasonable self-monitoring method for real-time self-monitoring of the printing process of 3D printed structural parts. This method can be applied to the real-time self-monitoring of the 3D printing process, realizing the integrated function of printing structure and monitoring. It can monitor the status of the printed structure in real time without the need for external large equipment, and has the advantages of low monitoring cost and convenient monitoring.

[0087] To illustrate the relevant performance of the long afterglow curing 3D printing ink provided by this invention, it is described in conjunction with the accompanying drawings.

[0088] Figure 1 This is a strain-stress curve diagram of the photosensitive resin and four photocurable 3D printing inks with long afterglow properties of the present invention. Figure 1It was found that the Young's modulus of the photosensitive resin in Example 2 was 476.1 MPa, the Young's modulus of the photocurable 3D printing ink 1 with long afterglow properties in Example 3 was 1710.3 MPa, the Young's modulus of the photocurable 3D printing ink 2 with long afterglow properties in Example 4 was 1363.0 MPa, the Young's modulus of the photocurable 3D printing ink 3 with long afterglow properties in Example 5 was 1270.3 MPa, and the Young's modulus of the photocurable 3D printing ink 4 with long afterglow properties in Example 6 was 1269.6 MPa. Comparing the mechanical properties of the photocurable 3D printing ink 1 with long afterglow properties in Example 3 with the mechanical properties of the photosensitive resin in Example 2, it can be found that doping with long afterglow materials can improve the mechanical properties of 3D printed structural devices by up to 3.6 times. That is, doping with long afterglow materials can achieve the control of the mechanical properties of 3D printed structural devices, which breaks the limitation that the mechanical properties of structural devices prepared by traditional 3D printing inks often depend on the mechanical properties of the selected photosensitive resin itself. This innovation lays a solid foundation for in-depth research on the impact of long afterglow materials on the mechanical properties of 3D printed structures.

[0089] Figure 2 The images show the delayed-motion spectra of four photocurable 3D printing inks with long afterglow properties according to the present invention. Figure 2 It can be seen that the peak value of the delayed spectrum of photocurable 3D printing ink 1 with long afterglow properties is located at 512 nm, the peak value of the delayed spectrum of photocurable 3D printing ink 2 with long afterglow properties is located at 485 nm (with a shoulder peak of 466 nm), the peak value of the delayed spectrum of photocurable 3D printing ink 3 with long afterglow properties is located at 513 nm, and the peak value of the delayed spectrum of photocurable 3D printing ink 4 with long afterglow properties is located at 480 nm (with a shoulder peak of 460 nm). The difference in the peak values ​​of the delayed spectra of these four photocurable 3D printing inks with long afterglow properties is due to the different types of long afterglow materials and the composition of the photosensitive resin.

[0090] Figure 3 This document describes the curing depth test of the photocurable 3D printing ink 1 with long afterglow properties in Example 3 of this invention. To perform photocurable 3D printing using the photocurable 3D printing ink 1 with long afterglow properties in Example 3, we need to test the curing depth. Experiments show that the curing depth of the photocurable 3D printing ink 1 with long afterglow properties increases with increasing exposure time and exposure intensity, with a critical exposure time of 3 seconds and a minimum curing depth of 20 micrometers. Subsequently, 3D printing can be performed using printing parameters with an exposure time greater than or equal to 3 seconds.

[0091] Figure 4These are images showing the long afterglow effect before and after UV irradiation of a series of fine solid objects and complex, high-precision hollow structures prepared using photocurable 3D printing ink 1 with long afterglow properties in Embodiment 7 of the present invention. Figure 4 As can be seen, using the parameters in Table 1-4 for 3D printing, a series of complex, high-precision hollow structure models and detailed solid models can be printed. The successful printing of these models verifies the applicability of photopolymer 3D printing inks with long afterglow properties in the field of additive manufacturing.

[0092] Figure 5 This illustration demonstrates the application of a type of photocurable 3D printing ink with long-persistence properties prepared according to the present invention in structural mechanical enhancement. The table made of photosensitive resin provided in Example 2 deformed and collapsed in less than 0.4 seconds under the pressure of a 100g weight; while the table made of photocurable 3D printing ink 1 with long-persistence properties provided in Example 4 remained stable and robust under the pressure of a 100g weight, and continuously emitted a long-persistence glow. The addition of long-persistence materials can significantly improve the mechanical properties of the ink and optimize the reliability of the structure. This ink has broad application prospects in aerospace, automotive manufacturing, biomedicine, and the manufacturing of precision electronic components.

[0093] Figure 6 , Figure 7 , Figure 8 In Embodiment 9 of this invention, using photocurable 3D printing ink 3 with long afterglow properties, the following graphs were obtained showing the relationships between printing time and afterglow lifetime, printing time and afterglow duration, and printing time and mechanical properties. These three graphs, combined with Table 5 which shows the mechanical properties, long afterglow lifetime, and long afterglow duration of the structures after printing for different times, demonstrate that the printing time of the photocurable 3D printing ink 3 with long afterglow properties exhibits a consistent linear relationship with the afterglow lifetime, afterglow duration, and mechanical properties of the printed structure. Since mechanical properties reflect the completion or non-completion of the printing process, the printing process of the printed structure can be monitored in real time through the long afterglow lifetime and duration. Figure 9 The image shows an application demonstration of real-time self-monitoring of the 3D printing process using photocurable 3D printing ink 3 with long afterglow properties. This invention provides a reasonable method for real-time self-monitoring of the 3D printing process.

[0094] In summary, this invention relates to the design and preparation of a class of photocurable 3D printing inks with long afterglow properties and their applications in the fields of 3D printing structural mechanical enhancement, real-time self-monitoring of the 3D printing process, and additive manufacturing.

[0095] This invention designs and prepares organic long-persistent materials and incorporates them into photosensitive resins to create photocurable 3D printing inks with long-persistent properties. By controlling the doping ratio of the long-persistent materials and the composition of the photosensitive resin, the mechanical properties of the ink were successfully controlled from 476.1 MPa to 1710.3 MPa, improving the mechanical properties of the structural devices by 3.6 times. The introduction of long-persistent materials can significantly improve the mechanical properties of the ink and optimize the reliability of the structure, breaking through the limitation that the mechanical properties of long-persistent photocurable 3D printed structures often depend on the properties of the selected photosensitive resin itself. This ink has broad application prospects in aerospace, automotive manufacturing, biomedicine, and precision structural component manufacturing.

[0096] The photopolymerizable 3D printing ink 1 with long afterglow properties developed in Embodiment 3 of this invention was applied to DLP 3D printing and successfully printed a series of complex, high-precision hollow structure models and detailed solid models. This indicates that the ink has good application prospects in fields such as optical sensing, structural health monitoring, mechanical sensing, display lighting, information encryption, biomedicine, and additive manufacturing.

[0097] Furthermore, this invention has successfully applied the photocurable 3D printing ink 3 with long afterglow properties prepared in Example 5 to the field of real-time self-monitoring of the 3D printing process. This technology monitors the printing process of the printed structure in real time by reading the afterglow lifetime and afterglow duration, integrating the functions of printing structure and monitoring. It can monitor the status of the printed structure in real time without the need for external large equipment, reducing monitoring costs. This provides a reasonable method for real-time self-monitoring of the 3D printing process.

[0098] Although embodiments of the present invention have been shown and described above, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A type of long afterglow material, characterized in that, The structural formula of the long afterglow material includes one of the following: In formulas (Ⅰ), (Ⅱ), (Ⅲ), (Ⅳ), (Ⅴ) and (Ⅵ), A and B are independently selected from one of the following: halogen atom, methyl, ethyl, methoxy, bis(4-tert-butylphenyl)amine, diphenylamine and dichlorodiphenylphosphine.

2. The long afterglow material according to claim 1, characterized in that, The structural formula of the long afterglow material is any one of the following: 。 3. The application of a long afterglow material as described in claim 1 or 2 in photocurable 3D printing ink.

4. A type of photocurable 3D printing ink with long afterglow properties, characterized in that, Includes a type of long afterglow material as described in claim 1 or 2 and a photosensitive resin matrix; The photosensitive resin matrix includes photosensitive resin monomers, photoinitiators, and crosslinking agents; The photosensitive resin monomer includes one or more of the following: acrylate, methacrylate, epoxy acrylate, hydroxyethyl acrylate, tert-butyl acrylate, isobornyl acrylate, aliphatic polyurethane acrylate, polymethyl methacrylate, polyvinyl alcohol resin, and polyethylene glycol diacrylate. The photoinitiator is one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide; The crosslinking agent is polyethylene glycol diacrylate or aliphatic polyurethane diacrylate.

5. The photocurable 3D printing ink with long afterglow properties according to claim 4, characterized in that, The photoinitiator accounts for 1 to 2 wt% of the photosensitive resin matrix; the crosslinking agent accounts for 1 to 40 wt% of the photosensitive resin matrix.

6. The photocurable 3D printing ink with long afterglow properties according to claim 4, characterized in that, The mass ratio of the long afterglow material to the photosensitive resin matrix is ​​1:10~20000.

7. A method for preparing a photocurable 3D printing ink with long afterglow properties as described in any one of claims 4 to 6, characterized in that, The process includes the following steps: blending long-afterglow material, photosensitive resin monomer, photoinitiator and crosslinking agent in a certain proportion to obtain photocurable 3D printing ink with long-afterglow properties.

8. The application of a photocurable 3D printing ink with long afterglow properties as described in any one of claims 4 to 6 in optical sensing, humidity sensing, temperature sensing, structural health monitoring, mechanical sensing, display lighting, information encryption, biomedicine, self-monitoring sensing, or additive manufacturing.

9. A structural component, characterized in that, The ink is obtained by 3D printing using a photocurable 3D printing ink with long afterglow properties as described in any one of claims 4 to 6.

10. A method for real-time self-monitoring of the printing process of a 3D printed structural component, characterized in that, Using a photocurable 3D printing ink with long afterglow properties as described in any one of claims 4 to 6, the printing process of 3D printed structural parts can be monitored in real time through the visualization effect of long afterglow.

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