A multi-resonance skeleton-based photoinitiating system and application thereof

Abstract

The present application relates to a kind of light initiation system based on multiple resonance skeleton and its application.The light initiation system includes triplet-state photocatalyst with multiple resonance skeleton and co-initiator, and the latter produces free radical by electron or energy transfer.The system is compounded with polymerizable monomer to obtain photosensitive resin (photoresist).The photosensitive resin can realize superfast curing under low intensity light irradiation in air atmosphere: single layer exposure only needs 1.5-2 seconds, supports 10 micrometer level high-resolution 3D printing and photoetching processing, and printing speed is as high as 72 cm / h at 400 micrometer layer thickness.The resin also has good biocompatibility, and can manufacture complex three-dimensional structure and micro-nano pattern.The present application provides a kind of new light initiation system for additive manufacturing and photoetching technology, which is efficient, fast and air resistant.

Description

Technical Field

[0001] This invention belongs to the field of photocurable materials and additive manufacturing technology, specifically relating to a photoinitiation system based on a multi-resonance skeleton and its application in 3D printing and photolithography. Background Technology

[0002] 3D printing and photolithography represent important development directions in advanced manufacturing, enabling high-precision customized manufacturing of complex three-dimensional structures at both micro and macro scales. They have broad and far-reaching application value in cutting-edge fields such as high-end equipment, biomedicine, and microelectronics. The performance of these technologies highly depends on the photoinitiation system in the photosensitive resin (photoresist), which is responsible for directly converting light energy into chemical energy, thereby initiating the polymerization reaction. However, traditional photoinitiation systems typically require an inert atmosphere, high light intensity, or long exposure time, making it difficult to achieve rapid and high-precision 3D printing and photolithography in an air environment.

[0003] To overcome the aforementioned shortcomings, a novel photoinitiation system containing a triplet photocatalyst offers a new approach to solving these problems. Triplet excitons possess a long lifetime ranging from microseconds to milliseconds, significantly increasing the concentration of active species, thereby improving polymerization efficiency, shortening reaction time, and effectively suppressing the influence of oxygen. However, the intersystem crossing (ISC) process, where excitons transition from singlet to triplet states in traditional molecules, is inefficient, making it difficult to efficiently generate the desired triplet excitons. Therefore, there is an urgent need in this field to develop new molecular design strategies to construct photocatalysts capable of efficiently generating triplet excitons, and based on this, to develop photosensitive resin (photoresist) systems that can achieve ultrafast photocuring under air atmosphere and low light intensity. Summary of the Invention

[0004] The purpose of this invention is to provide a photoinitiation system composed of a novel triplet photocatalyst based on a multiple resonance strategy and a co-initiator, and to apply it to photosensitive resins (photoresists) to overcome the shortcomings of existing photoinitiation systems that require high light intensity, long exposure time or inert atmosphere protection in an air environment.

[0005] (a) Photoinitiation system To achieve the above objectives, the present invention provides the following technical solution: a novel photoinitiation system, characterized in that it comprises at least one triplet photocatalyst with a multiple resonance framework; at least one co-initiator, wherein the co-initiator is capable of accepting electron transfer or energy transfer of the photocatalyst in the excited state and undergoing chemical bond cleavage to generate free radicals; optionally, it may also comprise other photosensitizers, auxiliaries or stabilizers.

[0006] The co-initiator includes, but is not limited to, one or more of the following compounds: diaryliodonium salts, triarylthionium salts, dialkylphenylthionium salts, etc. N-Alkoxypyridinium salts, oxime esters, sulfonamide compounds, or any combination thereof. Preferably, the co-initiator is a diaryliodomonium salt, such as bis(4-tert-butylphenyl)iodomonium hexafluorophosphate.

[0007] (II) Triplete-state photocatalysts The photocatalyst is characterized by containing electron-donating units (e.g., aromatic amines) and electron-withdrawing units (e.g., boron, carbonyl, phosphine oxide, etc.) in its molecular structure. These units are connected by conjugation, allowing frontier orbitals to alternately distribute on electron-donating and electron-withdrawing atoms, thereby constructing a multiple resonance framework with the following general formula:

[0008] General Formula Type 1: D represents the donor unit (e.g., aromatic amine), A represents the acceptor unit (e.g., carbonyl, thiocarbonyl, sulfoxide, sulfone, arylboron, phosphono, carbium, malononitrile), and X represents the bridging atom (e.g., CR2, SiR2, NR, PR, O, S, Se, Te).

[0009] General Formula Type 2: D represents the donor unit (e.g., aromatic amine), A represents the acceptor unit (e.g., arylboron, phosphonoyl, carbium), and X represents the bridging atom, which can be a heteroatom (e.g., CR2, SiR2, NR, PR, O, S, Se, Te) or an acceptor unit (e.g., carbonyl, thiocarbonyl, sulfoxide, sulfone, arylboron, phosphonoyl, carbium, malononitrile).

[0010] In this invention, each of the R groups is independently selected from hydrogen atoms, C1-C20 alkyl groups, C6-C30 aryl groups, and C3-C30 heteroaryl groups; Ar represents the core aromatic ring, whose conjugation degree can be further increased. Furthermore, any connection between two core structures via single bonds or conjugation, as well as fused ring or spiro ring structures formed by single bond closure, are all within the scope of this invention.

[0011] The following are some representative structures:

[0012]

[0013]

[0014] It should be noted that although the multi-resonance framework compound itself may be known or similar structures have been reported, this invention combines the compound with a specific co-initiator for use in an ultrafast photopolymerization initiation system in photosensitive resins (photoresists). This combination and its application in visible light curing 3D printing and photolithography are not found in the prior art. This application is not a known function of the compound, and the resulting technical effects (such as low light intensity in an air atmosphere, ultra-short exposure time, and high-resolution 3D printing and photolithography) exceed the reasonable expectations of those skilled in the art, exhibiting unexpected technical effects.

[0015] (III) Photosensitive resin (photoresist) composition The present invention also provides a photosensitive resin (photoresist) composition, characterized in that it comprises a photoinitiating system as described above; at least one polymerizable monomer or prepolymer, preferably selected from acrylates, methacrylates, vinyl ethers, epoxy compounds or mixtures thereof; optionally, it may also contain other additives, such as leveling agents, defoamers, dyes, fillers, etc.

[0016] (iv) Application This invention further provides the application of the aforementioned photosensitive resin (photoresist) in 3D printing and photolithography, particularly employing digital light processing (DLP), liquid crystal display (LCD) surface projection, or laser direct-write photolithography technologies to achieve ultrafast, high-resolution three-dimensional structure manufacturing and micro / nano pattern processing under air atmosphere and low-intensity illumination. Specifically, 3D printing utilizes visible light (especially 405nm blue light), while photolithography employs ultraviolet light (such as 365nm), with a single-layer exposure time ≤ 2 seconds and a resolution up to 10 micrometers.

[0017] (v) Beneficial effects Compared with the prior art, the present invention has the following beneficial effects: 1. Ultra-fast curing: Cures under low-intensity visible light (e.g., 4 mW / cm²). 2 Under these conditions, the curing time for a single layer is only 1.5–2 seconds, which is significantly faster than existing visible light initiation systems.

[0018] 2. Open air operation: No inert atmosphere required; triplet excitons are used to efficiently overcome oxygen inhibition.

[0019] 3. High resolution: Enables 3D printing and photolithography with 10-micron precision.

[0020] 4. Wide layer thickness adaptability: Stable 3D printing is possible within the layer thickness range of 10–400 micrometers, with a maximum printing speed of 72 cm / h (excluding platform uptime).

[0021] 5. Low catalyst dosage: The amount of photocatalyst can be as low as 10 ppm–200 ppm, which is economical and facilitates post-treatment.

[0022] 6. Broad Spectrum Applicability: The general formula of this invention covers a variety of multiple resonance derivatives, and the co-initiator can be selected from a variety of onium salts and oxime esters. The reaction can be initiated through two mechanisms: single electron transfer or energy transfer, making it highly versatile.

[0023] 7. Good biocompatibility: Representative compounds show low toxicity to a variety of cells and are suitable for the biomedical field.

[0024] Upon investigation, no existing technology has been found to be exactly the same as the present invention. The present invention is novel, inventive, practical and significantly advanced compared to the prior art. Attached Figure Description

[0025] Figure 1 The preferred chemical structural formula of the photocatalyst QPSO in this invention; Figure 2 Key photophysical properties of QPSO; Figure 3 Electron paramagnetic resonance (EPR) spectra of the QPSO / Iod system before and after illumination; Figure 4 Photopolymerization kinetics curves of the QPSO / Iod system; Figure 5 : A typical formulation diagram of the photosensitive resin of this invention; Figure 6 A "Maya Pyramid" model printed using the photosensitive resin of this invention under different layer thicknesses and exposure times; Figure 7 A comparison of the printing speed and resolution of the photosensitive resin of this invention with data reported in the prior art; Figure 8 Complex three-dimensional models printed using the photosensitive resin of this invention; Figure 9 : A schematic diagram of a typical photoresist formulation for this invention; Figure 10 Micron-scale patterns prepared using the photosensitive resin of this invention via photolithography; Figure 11 Effects of different concentrations of QPSO on the viability of human umbilical vein endothelial cells and human hepatocellular carcinoma cells; Figure 12 : 1H NMR spectrum of QPSO (400 MHz, CDCl3). Detailed Implementation

[0026] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below with reference to specific embodiments. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention. I. Synthesis of Photocatalysts (General Strategy) The core feature of the triplet photocatalyst described in this invention lies in its multiple resonance framework. This multiple resonance framework refers to a type of fused-ring structure in which alternating electron-donating and electron-withdrawing units (such as aromatic amines with boron, carbonyl, sulfone, phosphine oxide, etc.) form spatially separated frontier molecular orbitals, thereby generating short-range charge-transfer excited states. This allows for efficient intersystem crossing, resulting in the generation of triplet excitons with lifetimes ranging from microseconds to milliseconds. Therefore, this type of photocatalyst can be used as a triplet photocatalyst in combination with a co-initiator for photoinduced radical polymerization reactions. The synthesis of this type of compound can employ various methods known in the art, typically but not limited to the following general strategies: Strategy 1 (Aromatic Amine / Carbonyl Type): Starting with aromatic amines or aryl heterocyclic compounds, aryl esters, aryl borate esters, or aryl halides containing leaving groups (such as halogens) in the ortho position are coupled to form aryl-heteroatom-aryl linkages via coupling reactions (such as Ullmann coupling, Buchwald-Hartwig coupling, Suzuki coupling, etc.). Subsequently, fused ring skeletons are formed through intramolecular cyclization (such as Friedel-Crafts acylation, carbon-hydrogen bond activation, nucleophilic aromatic substitution, etc.).

[0027] Strategy 2 (Boron / Nitrogen Doping): First, a coupling reaction is carried out between diarylamines and polyhalogenated aromatic hydrocarbons (such as Ullman coupling and Buchwald-Hartwig coupling). The resulting intermediate is then subjected to a series of boronization and cyclization reactions with boron sources such as boron tribromide or arylboronic acid at high temperature to construct a boron / nitrogen multi-resonance framework.

[0028] Strategy 3 (Other Multiple Resonance Systems): This also includes multiple resonance frameworks containing heteroatoms such as phosphine oxygen and sulfone groups. The synthesis methods can refer to the conventional methods of corresponding heterocyclic chemistry.

[0029] Those skilled in the art can select appropriate starting materials and reaction conditions based on the specific structure of the target molecule, and prepare the above-mentioned photocatalysts by referring to known literature methods.

[0030] As a representative example, when using strategy one above to prepare an aromatic amine / carbonyl type multiple resonance photocatalyst, the compound QPSO (whose core skeleton is a phenselenoquinoline ketone structure, as shown in the image) was prepared by the following method. Figure 1(As shown). It should be understood that this example is merely to illustrate one specific implementation of the photocatalyst of the present invention, and does not limit the present invention to specific structures containing selenium or carbonyl groups.

[0031] The synthesis steps of QPSO: Under nitrogen protection, add 10 to a dry Schlenk tube. H- Phenylselenomethazine (4.92 g, 20 mmol), methyl o-iodobenzoate (5.76 g, 22 mmol), potassium carbonate (4.15 g, 30 mmol), 18 - crown - 6 (1.06 g, 4 mmol), activated copper powder (127 mg, 2 mmol), and cuprous iodide (381 mg, 2 mmol). Add 50 mL of dry 1,2 - Dichlorobenzene was stirred at room temperature for 5 minutes, then heated to 190 °C and reacted for 48 hours. After cooling to room temperature, the mixture was filtered, and the filter cake was washed with dichloromethane. The filtrates were combined and concentrated under reduced pressure to obtain a crude intermediate, which was used directly in the next step.

[0032] The crude intermediate was dissolved in tetrahydrofuran / methanol / water (3:1:1, 50 mL), and lithium hydroxide monohydrate (1.44 g, 60 mmol) was added. The reaction was carried out at 70 °C for 12 hours. After cooling, the organic solvent was removed under reduced pressure. The residue was dissolved in water, and the pH was adjusted to 1-2 with 1M hydrochloric acid. The mixture was extracted three times with ethyl acetate. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated. The resulting solid was dissolved in 50 mL of dry dichloromethane, and 5 drops of DMF were added. Oxaloyl chloride (7.62 g, 60 mmol) was slowly added dropwise under ice bath cooling. After stirring at room temperature for 4 hours, the mixture was cooled again under ice bath cooling. Anhydrous aluminum trichloride (9.08 g, 60 mmol) was added in portions, and the mixture was heated under reflux for 6 hours. After cooling to room temperature, 100 mL of water was slowly added to quench the reaction, and the mixture was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography (petroleum ether and dichloromethane, volume ratio 1:1) to give a yellow solid QPSO (4.04 g, 58%). HRMS (ESI) + ): m / z calculated value C 19 H 12 NOSe [M+H] + 350.0079, measured value 350.0086. 1 HNMR (400 MHz, CDCl3) δ: 7.14-7.23 (m, 3H), 7.30 (t, J = 7.6 Hz, 1H), 7.37 (t, J =8.0 Hz, 1H), 7.52-7.60 (m, 2H), 7.68 (d,J = 6.0 Hz, 1H), 7.72 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 6.8 Hz, 1H), 8.40 (d, J = 6.4 Hz, 1H) ppm.

[0033] Other representative examples: Referring to the above strategy, with 10 H- Oxygen-containing analogs can be prepared from phenothiazine as a raw material, with 10 H- Sulfur-containing analogs can be prepared from phenothiazines. For boron / nitrogen multiple resonance systems, preparation methods from known literature can be used. The above examples are only for illustrating some compounds covered by the general formula of this invention, and not all of them.

[0034] II. Photophysical and photochemical properties of photocatalysts 2.1 Photophysical properties The QPSO prepared in Example 1 was dissolved in toluene to prepare a solution with a concentration of 1×10⁻⁶. -5 The solution of M was measured, and its ultraviolet-visible absorption spectrum was obtained as follows: Figure 2 As shown in figure a, QPSO exhibits a strong absorption peak around 405 nm, with a molar extinction coefficient of approximately 1.15 × 10⁻⁶. 4 M -1 cm -1 This absorption is attributed to its short-range charge transfer (SRCT) characteristics, a typical photophysical feature of the multiple resonance framework. Further, QPSO was dispersed in a polymethyl methacrylate (PMMA) film (1 wt%), and its delayed fluorescence decay curve was measured, with results as follows: Figure 2 As shown in b, QPSO exhibits microsecond-level long-lived delayed fluorescence with a triplet lifetime of τ = 243 μs, confirming its ability to efficiently generate and maintain long-lived triplet excitons. These results demonstrate that QPSO can effectively absorb visible blue light and generate excited states, possessing long-lived triplet excitons, making it suitable for photopolymerization systems excited by 405 nm LED light sources and photolithography systems excited by ultraviolet light.

[0035] 2.2 Photochemical properties use N -Terbutyl- α 3-Phenylonitrile (PBN) was used as a free radical scavenger in electron paramagnetic resonance (EPR) experiments. QPSO and the co-initiator bis(4-phenylnitrile) were used. - tert-butylphenyl)iodonium hexafluorophosphate (Iod) and PBN were mixed in degassed DMSO, and EPR spectra were recorded before and after 405 nm LED illumination. The results are as follows: Figure 3As shown, no obvious signal was observed before illumination; after illumination, a characteristic signal of typical PBN-radical adducts appeared, confirming that the QPSO / Iod system efficiently generates radicals under illumination. This result indicates that the photoinitiation system of this invention efficiently generates initiating radicals through a photoinduced electron transfer mechanism.

[0036] III. Photopolymerization Kinetics Test The photopolymerization process was monitored using attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR). Ethoxylated trimethylolpropane triacrylate (ETPTA, 1.0 g) was used as the monomer, and the photocatalyst QPSO (1.0 × 10⁻⁶ g) was added. -5 mol / g) and co-initiator Iod (2.0 × 10⁻⁶ ... -5 (mol / g), after being thoroughly mixed, was dropped onto the surface of a diamond crystal attached to an ATR. Irradiation was performed in air using a 405 nm LED light source, and the 1636 cm⁻¹ depth was monitored in real time. -1 The peak area change of the acrylate double bond was analyzed, and the double bond conversion rate was calculated. The results are as follows: Figure 4 As shown, the conversion rate reaches 40% after 5 seconds of irradiation, 72% after 10 seconds, and exceeds 99% after 300 seconds. This result demonstrates that the photoinitiation system of this invention possesses ultrafast initiation capability under air atmosphere and low light intensity.

[0037] IV. Preparation of Photosensitive Resin (Photoresist) As a representative approach, the QPSO prepared above is used as a triplet photocatalyst, mixed with the co-initiator Iod in a certain proportion, and dissolved in a polymerizable monomer or crosslinking agent to obtain a novel photosensitive resin (photoresist) containing multiple resonant photocatalysts. A typical formulation is as follows (in molar percentage): QPSO: 0.02%–0.1%, Iod: 0.1%–1.0%, polymerizable monomer or crosslinking agent: balance (e.g., 100 mol%).

[0038] V. 3D Printing Resin formulation: The molar ratio of photocatalyst QPSO, co-initiator Iod, acrylamide monomer (DMA), and trimethylolpropane triacrylate (TMPTA) is 0.02 : 0.30 : 92.28 : 7.72. Figure 5 As shown. Stir and mix thoroughly under light-protected conditions before use.

[0039] Printing equipment: A commercial printer is used, with a light source wavelength of 405 nm and a light intensity of 4.0 mW / cm². 2 The projection resolution is 2560 × 1440 pixels. The entire printing process is carried out in an air atmosphere at room temperature (30–40 ℃).

[0040] Printing parameters: The exposure time for the bottom layer is set to 5–30 seconds depending on the layer thickness, the exposure time for the normal layer is 1.5–2 seconds, and the thickness of a single layer can be adjusted within the range of 10–400 μm.

[0041] Printing Results: Under conditions of 10 μm layer thickness and 1.5 seconds of normal layer exposure, a "Mayan pyramid" model with clear edges and fine texture can be printed, achieving a printing speed of 2.4 cm / h. When the layer thickness is increased to 400 μm and the normal layer exposure is 2 seconds, the printing speed reaches as high as 72 cm / h. The resulting model has a complete structure without delamination or deformation (e.g., Figure 6 (As shown). In contrast, control systems using commercial photoinitiators 2,4-diethylthiazolone (DETX) / Iod, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), or phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO) failed to obtain complete models under the same printing conditions. It is noteworthy that, compared to previously reported literature, the printing speed achieved by this invention has a clear advantage (e.g., Figure 7 (As shown).

[0042] Furthermore, using the aforementioned optimized conditions, various complex multi-scale models were successfully prepared, including an octahedral truss, a small boat, a dental mandible, and a golf ball tower, etc. Figure 8 (As shown). The above results fully demonstrate that the photoinitiation system of the present invention possesses both ultra-fast printing speed and high forming accuracy in air atmosphere and low light intensity.

[0043] VI. Photolithography Applications When used for photolithography, the ratio of monomer to crosslinking agent in the above photosensitive resin needs to be adjusted: the molar ratio of DMA to TMPTA is changed to 0.42:0.58, while the ratio of the photoinitiator system to the polymerization component remains unchanged (e.g., Figure 9 (As shown). Take 100 μL of the adjusted photosensitive resin and spin-coat it onto the surface of a 2×2 cm silicon wafer (spin-coating parameters: rotation speed 1500 rpm, acceleration 500 rpm, time 10 seconds), then bake it on a 90 ℃ hot stage for 5 minutes. Expose it at room temperature using a 365 nm laser direct-write lithography machine (or mask exposure machine) with an exposure dose of 6–40 mJ / cm. 2 After exposure, chloroform is used as the developer. The silicon wafer is immersed in chloroform for about 5 seconds to obtain a photolithographic pattern with micron-level resolution (such as...). Figure 10 As shown, the minimum linewidth can reach 10 μm. Compared with traditional photoresists, the photoresist of this invention has advantages such as high oxygen-resistant polymerization efficiency, low required photoinitiator concentration, and significantly reduced exposure energy.

[0044] VII. Other Applications The photosensitive resin (photoresist) composition described in this invention can also be used in a variety of advanced manufacturing fields. For example: Microfluidic chips: Chips with microchannel structures fabricated using photolithography or 3D printing processes, used for biological detection, chemical analysis, etc.

[0045] Bio-scaffolds: Tissue engineering scaffolds are constructed using high-precision 3D printing, which, combined with their excellent biocompatibility, support cell adhesion and proliferation.

[0046] Flexible electronic devices: Conductive patterns are photolithographically or printed on flexible substrates for use in wearable sensors, flexible circuits, etc.

[0047] Rapid prototyping of complex 3D structures: With ultra-fast curing speed and air resistance, it enables integrated rapid prototyping of large-size, multi-scale complex configurations.

[0048] The above applications are merely examples of some uses of the compositions of the present invention and are not intended to limit their scope of application. Those skilled in the art can apply the photosensitive resins of the present invention to other photocuring-related additive manufacturing or micro / nano fabrication fields according to actual needs.

[0049] 8. Biocompatibility Testing Human umbilical vein endothelial cells (HUVECs) and human hepatocellular carcinoma cells (HepG2) were seeded into 96-well plates and cultured for 24 hours. Different concentrations (0, 6.25, 12.5, 25, 50 μM) of QPSO were then added, and the cells were cultured for another 24 hours. Cell viability was determined using the CCK-8 assay. The results are shown below. Figure 11 As shown, at QPSO concentrations not exceeding 25 μM, the viability of both cell types remained above 80%; when the concentration increased to 50 μM, the viability of HUVEC cells was approximately 67%, and that of HepG2 cells was approximately 78%. These results indicate that QPSO exhibits low cytotoxicity within the tested concentration range and demonstrates good biocompatibility.

[0050] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A photoinitiation system, characterized in that, The method comprises at least one triplet photocatalyst with a multiple resonance framework, and at least one co-initiator; the co-initiator is capable of accepting electron transfer or energy transfer from the photocatalyst in the excited state and undergoing chemical bond cleavage to generate free radicals.

2. The photoinitiation system according to claim 1, characterized in that, The co-initiator includes, but is not limited to, one or more of onium salts, oxime esters, and sulfonamides; preferably, the onium salts include iodonium salts, thiodonium salts, pyridinium salts, ammonium salts, phosphonium salts, etc.

3. The photoinitiation system according to claim 1, characterized in that, The triplet photocatalyst has a multi-resonance framework, which is composed of electron-donating units and electron-withdrawing units, or is composed of heteroatom doping, and its frontier orbitals are arranged in an atomic-level alternation.

4. The photoinitiating system according to any one of claims 1 to 3, characterized in that, The electron-donating unit includes one or more of aromatic amines, carbazole, acridine, phenoxazine, phenothiazine, and phenotelezine; the electron-withdrawing unit includes one or more of boron, carbonyl, phosphoxy, and sulfone; and the heteroatom includes one or more of nitrogen, oxygen, sulfur, selenium, and tellurium.

5. A photosensitive resin composition, characterized in that, It comprises a photoinitiating system according to any one of claims 1 to 3, and at least one polymerizable monomer or prepolymer.

6. The photosensitive resin composition according to claim 5, characterized in that, The polymerizable monomer or prepolymer is selected from one or more monomers containing olefinic unsaturated bonds and epoxy compounds; preferably, the monomers containing olefinic unsaturated bonds include, but are not limited to, one or more of (meth)acrylates, vinyl ethers, vinyl esters, styrene compounds, unsaturated amides, and allyl compounds.

7. The use of the photosensitive resin composition according to claim 5 or 6 in 3D printing or photolithography.

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