A photo-curable ink having an initiation inhibition dual response

Abstract

The application discloses a photocuring ink with initiation inhibition dual response, and relates to the technical field of photocuring materials, and comprises the following components: a photopolymerizable monomer or prepolymer; a photoinitiator which is sensitive to a first waveband of light and generates active free radicals under light; a photo-inhibitor which is sensitive to a second waveband of light and generates active inhibitor substances to quench free radicals under light; wherein the first waveband and the second waveband are orthogonal in the spectrum; and an electron donor adjuvant or an oxygen scavenger for regulating the influence of environmental factors on printing accuracy. The photocuring ink with initiation inhibition dual response realizes digital two-way control of photochemical reaction, builds intelligent photocuring materials with specific triplet photosensitive agents as core switches, and through input of digital light signals with different wavelengths, can trigger two opposite chemical processes of 'polymerization' and 'inhibition', thereby providing an effective material tool for photon-driven precision manufacturing.

Description

Technical Field

[0001] This invention relates to the field of photocurable materials technology, specifically to a photocurable ink with a dual response of initiation and inhibition. Background Technology

[0002] Photopolymer additive manufacturing is one of the core technologies for precision 3D forming. The "over-curing" problem caused by light scattering is the core bottleneck that limits printing accuracy. In order to overcome this limitation in principle, the industry has proposed a new paradigm of simultaneous additive and subtractive manufacturing with orthogonal light fields. Its core principle is to use two beams of orthogonal light to independently control the initiation and inhibition of polymerization reactions, thereby simultaneously achieving additive curing and subtractive inhibition and improving manufacturing accuracy. The core material bottleneck of this technological paradigm lies in the lack of suitable dual-response photocurable inks: conventional photocurable resins can only achieve polymerization initiation at a single wavelength and cannot instantaneously and efficiently quench active free radicals under a second wavelength of light to achieve polymerization inhibition; at the same time, although triplet photosensitizers (such as methylene blue and eosin Y) have the potential to quench free radicals, key issues such as the coupling ratio with traditional ultraviolet-blue light photoinitiators, spectral orthogonality, and process compatibility (viscosity, transmittance, curing rate) have not yet been resolved, making it difficult to form a practical ink system. Summary of the Invention

[0003] To address the shortcomings of existing technologies, this invention provides a photocurable ink with both initiation and inhibition responses, thus solving the problems mentioned in the background section.

[0004] To achieve the above objectives, the present invention provides the following technical solution: a photocurable ink with dual initiation and inhibition responses, comprising the following components: Photopolymerizable monomers or prepolymers; Photoinitiators are sensitive to light in the first wavelength band and generate active free radicals under light irradiation; Photoinhibitors are sensitive to second-wavelength light and produce active inhibitory substances under light irradiation to quench free radicals. Among them, the first band and the second band are orthogonal in the spectrum; It also includes electronic donor additives or oxygen scavengers, used to eliminate interference from external factors on the inhibition reaction and stabilize printing accuracy and process repeatability. External factors include, but are not limited to, dissolved oxygen and ambient temperature.

[0005] Furthermore, the photopolymerizable monomer or prepolymer includes any one of the following: Water-based bio-ink system: The monomer is selected from one of polyethylene glycol diacrylate (PEGDA), gelatin methacryloyl glycol (GelMA), hyaluronic acid methacrylate (HAMA), and sodium alginate methacrylate; the solvent is water or PBS buffer. Resin engineering ink system: The monomer is selected from one of 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), polyurethane acrylate (PUA), and epoxy acrylate; the solvent is an active diluent or solvent-free.

[0006] Furthermore, the photoinhibitor, when excited to a long-lived triplet state under irradiation with the second wavelength light, and possessing a redox potential sufficient to inactivate free radicals, includes any one of the following: Thiazide compounds: one of Methylene Blue, New Methylene Blue, Thionine, or Azure A / B / C; Compounds in the group of tons: Eosin Y, Rose Bengal, Erythrosine B, and one of the fluorescein derivatives; Macrocyclic conjugated compounds: one of tetraphenylporphyrin (TPP), zinc phthalocyanine (ZnPc), or aluminum phthalocyanine (AlPc); Fullerene derivatives: C60, C70 and their water-soluble or fat-soluble modifications.

[0007] Furthermore, the photoinitiator includes any one of the following: Acylphosphine oxide compounds: one of the following: phenyl-2,4,6-trimethylbenzoyl lithium phosphine oxide (LAP), phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure 819), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO); α-Hydroxyketone compounds: one of 1-hydroxycyclohexylphenyl ketone (Irgacure 184) and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure 2959); Benzophenone derivatives or oxime ester derivatives: benzophenone BP or 4-phenylbenzophenone PBZ.

[0008] Furthermore, the spectral matching methods for inks include: Combination A is blue light initiation-red light suppression: the photoinitiator is an acylphosphine oxide compound, with a response of 365-420nm; the photoinhibitor is a thiazide compound, porphyrin compound, or phthalocyanine compound, with a response of 600-700nm; Combination B is blue light initiation-green light suppression: the photoinitiator is an acylphosphine oxide or α-hydroxy ketone compound, with a response of 365-405nm; the photoinhibitor is a tannin compound, with a response of 500-580nm.

[0009] Furthermore, the inhibition mechanism of the photocurable ink is based on photoinduced electron transfer: under the second band of light, the photoinhibitor transitions to the triplet state, acts as an electron acceptor to capture electrons from the free radicals of the growing chain, and generates a semi-reduced photosensitizer, thereby blocking chain growth; Alternatively, the photoinhibitor acts as an energy donor, generating singlet oxygen to achieve inhibition through the oxidation of free radicals.

[0010] Furthermore, the manufacturing method of the photocurable ink is as follows: The additive curing is triggered by the first wavelength of light, while the subtractive curing is triggered by the second wavelength of light. The high-precision forming of the three-dimensional structure is achieved by the dual beams working together for exposure.

[0011] Furthermore, the ink has high transmittance for both the first and second wavelengths of light, with a transmittance of >60%.

[0012] This invention provides a photocurable ink with dual initiation and inhibition responses, which has the following beneficial effects: 1. This photocurable ink with dual triggering and inhibition responses enables digital bidirectional control of photochemical reactions. It constructs an intelligent photocurable material with a specific triplet photosensitizer as the core switch. By inputting digital light signals of different wavelengths, it can trigger two diametrically opposed chemical processes, namely "polymerization" and "inhibition," providing an effective material tool for photon-driven precision manufacturing.

[0013] 2. This photocurable ink, featuring a dual response of initiation and inhibition, utilizes the highly efficient quenching mechanism of triplet single-electron transfer to quench free radicals within microseconds to milliseconds, perfectly matching the exposure timing of high-speed surface projection or scanning printing. Furthermore, the ink framework is widely adaptable to both hydrophilic and hydrophobic monomer systems. By adjusting the concentration ratio of triplet photosensitizer to initiator, it can flexibly match printing systems with different light intensities and exposure strategies, offering a high degree of process tolerance. Attached Figure Description

[0014] Figure 1 This is a schematic diagram illustrating the photochemical principle of initiation-inhibition bidirectional regulation in an embodiment of the present invention; Figure 2 This is a schematic diagram illustrating the verification of the second wavelength's curing suppression effect in an embodiment of the present invention; Figure 3 This is a schematic diagram illustrating the verification of spectral orthogonality in an embodiment of the present invention; Figure 4 This is a schematic diagram of light penetration depth testing in an embodiment of the present invention; Figure 5 This is a schematic diagram illustrating the effect of oxygen content on the inhibition effect in an embodiment of the present invention; Figure 6 This is a schematic diagram illustrating the effect of temperature on the suppression effect in an embodiment of the present invention; Figure 7 This is a schematic diagram illustrating the improved printing accuracy in an embodiment of the present invention. Detailed Implementation

[0015] The embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be construed as limiting the scope of the invention.

[0016] like Figures 1-7 As shown, the present invention provides a technical solution: a photocurable ink with dual initiation and inhibition responses. This ink achieves dual photoresponse of initiation and inhibition with orthogonal spectrum through the combined action of three functional components: a polymerizable matrix, a photoinitiator, and a photoinhibitor. Polymerizable matrix: It constitutes the main body of the ink and the network skeleton after curing. It can be selected from biocompatible hydrogel precursors (such as GelMA) or high-performance engineering resins (such as polyurethane acrylate) according to application requirements. Different matrices can match the performance requirements of different application scenarios such as biomedical and industrial manufacturing. The polymerizable matrix is ​​a photopolymerizable monomer or prepolymer, which serves as both the ink matrix and the cured network framework, and can be divided into two main systems: Water-based bio-ink system: The monomers are selected from polyethylene glycol diacrylate (PEGDA), gelatin methacryloyl (GelMA), hyaluronic acid methacrylate (HAMA), and sodium alginate methacrylate; the solvent is water or PBS buffer. Resin engineering ink system: The monomers are selected from 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), polyurethane acrylate (PUA), and epoxy acrylate; the solvent is a reactive diluent or solvent-free. Photoinitiator: Select a highly efficient free radical photoinitiator that is sensitive to the ultraviolet-blue light band (first wavelength, λ1), such as LAP; it undergoes photolysis under λ1 light irradiation to generate free radicals necessary for initiating chain polymerization; Photoinitiators can be selected from the following categories: Acylphosphine oxides: Lithium phenyl-2,4,6-trimethylbenzoylphosphine oxide (LAP), phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure819), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO); α-Hydroxyketones: 1-Hydroxycyclohexylphenyl ketone (Irgacure184), 2-Hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure2959); Benzophenone or oxime derivatives: Benzophenone (BP), 4-phenylbenzophenone (PBZ); Photoinhibitor: A triplet photosensitizer with strong absorption in the green-red light band (second wavelength, λ2) is selected, preferably methylene blue, eosin Y or thionine; under λ2 light irradiation, it generates a long-lived triplet state through excitation and intersystem crossing; and the long-lived triplet state is the core structural basis for achieving efficient free radical quenching.

[0017] Photoinhibitors can be selected from the following categories: Thiazides: Methylene Blue, Neo-Methylene Blue, Thionium, Azurite A / B / C; Classification of substances: Eosin Y, Rose Red, Erythrosine B, Fluorescein derivatives; Macrocyclic conjugated compounds: tetraphenylporphyrin (TPP), zinc phthalocyanine (ZnPc), aluminum phthalocyanine (AlPc); Fullerene derivatives: C60, C70 and their water-soluble / lipid-soluble modifications.

[0018] Core inhibition mechanism: Triple-state photosensitizers, as excellent electron acceptors, efficiently capture unpaired electrons from free radicals generated by photoinitiators through a single-electron transfer reaction; the free radicals are oxidized and inactivated, and the chain growth reaction is terminated, thereby achieving precise "curing inhibition" in the illuminated area (e.g., Figure 1 , Figure 2 (As shown in the figure). This inhibition process is irreversible, produces no byproducts, and allows for precise control of the solidification zone boundary.

[0019] To ensure the ink system functions effectively in additive and subtractive manufacturing, the following design guidelines must be met: Strict spectral orthogonality: The maximum absorption of the photoinitiator must be concentrated in the λ1 band, while the maximum absorption of the photoinhibitor (triple-state photosensitizer) must be concentrated in the λ2 band. The spectral overlap between the two must be minimal to ensure that the two beams of control light can act independently and without interference on their respective target molecules.

[0020] Spectral orthogonal matching scheme: Combination A (blue light initiation - red light inhibition): The photoinitiator is an acylphosphine oxide, with a response of 365-420nm; the photoinhibitor is a thiazide, porphyrin, or phthalocyanine, with a response of 600-700nm; Combination B (blue light initiation - green light inhibition): The photoinitiator is an acylphosphine oxide or an α-hydroxy ketone, with a response of 365-405 nm; the photoinhibitor is a tannin, with a response of 500-580 nm. Optimized balance between concentration and transmittance: The concentration of triplet photosensitizer needs to be precisely controlled; insufficient concentration results in weak inhibition efficiency; excessive concentration will lead to excessive absorption of λ1 light, weakening initiation efficiency and reducing the overall transmittance of the ink, affecting the manufacturing of thick layers or volumes; this invention establishes the optimal concentration window, enabling the ink to maintain high transmittance (>60%) in the working wavelength range, while high transmittance can ensure the depth of light penetration, meeting the forming requirements of large-size, thick-layer structures; Environmental robustness considerations: The performance of the ink is affected by dissolved oxygen and ambient temperature; oxygen is an effective quencher of triplet states, which may weaken the inhibition effect, so oxygen removal measures need to be taken; temperature interferes with the process by affecting molecular diffusion and reaction rate, so it needs to be used in a stable temperature-controlled environment of 4-50°C. Furthermore, electronic donor additives or oxygen scavengers can be added to the ink to regulate the impact of ambient oxygen content and temperature on printing accuracy; the ink has high transmittance (>60%) for both the first and second wavelengths of light, ensuring light penetration depth and reaction efficiency. Photocurable inks are used for simultaneous additive and subtractive manufacturing in orthogonal light fields: the first wavelength of light triggers additive curing, the second wavelength of light triggers subtractive suppression, and dual-beam collaborative exposure achieves high-precision forming of three-dimensional structures.

[0021] Example 1: Verification of Spectral Orthogonality and Preparation of Basic Ink Spectroscopic characterization: 0.03% (w / v) LAP aqueous solution and 0.001% (w / v) methylene blue aqueous solution were prepared, and UV-Vis absorption spectroscopy was performed; Figure 1 As shown, LAP has a strong absorption peak at ~375 nm, and its absorption in the >500 nm region is negligible; methylene blue has a characteristic absorption peak at ~665 nm, and its absorption in the <450 nm region is weak; the spectra of the two are well separated at 405 nm (commonly used for initiation light) and 635 nm (commonly used for suppression light), satisfying the orthogonality requirement. Figure 3 This result directly verifies that the spectra of the initiator and the inhibitor do not overlap, which meets the core requirement of two-way light control. Basic ink preparation: (1) Monomer: 15% (w / v) polyethylene glycol diacrylate (PEGDA 700); (2) Photoinitiator: 0.05% (w / v) LAP; (3) Light inhibitor: 0.002% (w / v) methylene blue; (4) Solvent: Deionized water; Stir under light-protected conditions until all components are completely dissolved to form a homogeneous, clear, light-curable ink; Verification of the effect of inhibiting curing: such as Figure 2As shown, the prepared photocurable ink was placed in an irradiation field of a 405nm surface light source (initiating light), while a 635nm point light source (suppression light) was used to irradiate a local area of ​​the ink. The experimental results showed that in the area irradiated by the overlapping beams, the ink remained liquid and did not solidify. In contrast, the background area irradiated only by the 405nm initiating light was completely cross-linked and solidified. This phenomenon directly confirms the effective suppression of the polymerization reaction initiated by the 635nm light field on the 405nm initiating light. This proves that the ink of the present invention can achieve precise local curing suppression and control the curing boundary.

[0022] Example 2: Optimization of light transmittance and determination of key concentration window Transmittance test: With the LAP concentration fixed at 0.05%, a series of inks were prepared by systematically changing the methylene blue concentration (0.0001%, 0.0005%, 0.001%, 0.002%, 0.005%); the penetration depth was tested using 405nm and 635nm lasers respectively; the results are as follows. Figure 3 As shown; Results Analysis and Window Determination: When the methylene blue concentration is ≤0.002%, the ink transmittance for 405nm light remains >85%, with minimal impact on initiation efficiency; the transmittance for 635nm light decreases systematically with increasing concentration; at a concentration of 0.002%, the transmittance for 635nm light is approximately 65%, ensuring sufficient photons are absorbed to generate an effective concentration of triplet states for the suppression light, while avoiding severe attenuation of the initiation light; this concentration region is determined to be the optimal process window that balances initiation efficiency and suppression effect. Figure 4 This concentration window provides a clear quantitative standard for the actual printing of the formula.

[0023] Example 3: Study on the Influence of Environmental Factors (Oxygen Content, Temperature) Dissolved oxygen effect experiment: Two samples of ink prepared according to Example 1 were taken. One sample was tested in air, and the other sample was bubbled with nitrogen for 10 minutes to remove dissolved oxygen. The evolution of storage modulus (G') was monitored using an optorheometer under the condition of simultaneous irradiation with 405nm (5 mW / cm²) and 635nm (10 mW / cm²) light. Results: The gelation time of the deoxygenated sample was significantly longer than that of the non-deoxygenated sample, confirming that dissolved oxygen quenches some triplet methylene blue, thereby weakening the inhibition effect; for printing tasks requiring extremely high precision, it is recommended to perform the printing in an inert atmosphere or a low-oxygen environment. Figure 5 This provides direct experimental evidence for environmental control in high-precision printing. Temperature effect experiment: The ink was subjected to the same photorheological test under constant temperature conditions of 20°C, 25°C and 30°C respectively; the results showed that the increase in temperature slightly accelerated gelation, because the increased molecular thermal motion promoted electron transfer and free radical diffusion; this indicates that maintaining a stable printing environment temperature is beneficial to process repeatability; by clearly defining the temperature control range, the consistency of printing dimensional accuracy can be guaranteed.

[0024] Example 4: Verification of broad compatibility with different monomer systems Hydrogel system adaptation: The monomers were replaced with a composite system of 10% (w / v) GelMA and 5% (w / v) PEGDA, while keeping the concentrations of LAP and methylene blue unchanged; the resulting ink remained clear and uniform, and exhibited dual photoresponse characteristics similar to those in Example 1. Adaptation to lipid-soluble resin systems: A lipid-soluble system was constructed; 1,4-butanediol diacrylate was used as the monomer and solvent to dissolve a lipid-soluble LAP analog (such as TPO) as the initiator, and a lipid-soluble eosin Y ester was selected as the inhibitor; 455nm blue light was used as the initiation light and 532nm green light was used as the inhibition light; the double bond conversion rate was monitored by real-time infrared spectroscopy, successfully verifying that a clear "blue light initiation, green light inhibition" effect also exists in this system, proving the universality of the ink design principle of this invention. Figure 6 This demonstrates that the technical solution of the present invention can cover both aqueous and lipid-soluble systems, and its application scenarios are not limited by solvent type.

[0025] Example 5: Verification of the Precision Improvement Effect in Additive and Subtractive Manufacturing Verification was performed using a printing system equipped with a dual-wavelength DLP optical engine at 405nm and 635nm. Printing test: Design and print a hollow pentagram model; Control group: The "initiation-inhibition" dual-response ink formulated according to Example 1 was used; during printing, only 405nm light projection line patterns (orthographic projection) were used for printing; Experimental group: Using the "initiation-inhibition" dual-response ink formulated according to Example 1; during printing, the 405nm light projects the line pattern (positive projection), and the 635nm light synchronously projects the background areas on both sides of the lines (negative projection). Effect comparison: such as Figure 7 As shown, the star-shaped structure printed in the control group had blurred edges and the internal channels were almost closed due to over-curing; while the structure printed in the experimental group had sharp edges, clear star-shaped corners, and transparent internal channels, perfectly reproducing the fine features of the design model and significantly improving printing accuracy and fidelity; this intuitively verifies that the ink of this invention can completely solve the over-curing problem in orthogonal light field manufacturing and achieve high-precision three-dimensional forming.

[0026] In summary, this photocurable ink with dual triggering and inhibition responses enables digital bidirectional control of photochemical reactions, constructing an intelligent photocurable material with a specific triplet photosensitizer as the core switch. By inputting digital light signals of different wavelengths, it can trigger two diametrically opposed chemical processes, "polymerization" and "inhibition," respectively, providing an effective material tool for photon-driven precision manufacturing. Moreover, through rigorous spectral orthogonal design and concentration optimization, the ink ensures high transmittance in the working wavelength range, meeting the complex manufacturing needs of thick-layer forming and bulk curing.

[0027] Utilizing the highly efficient quenching mechanism of triplet single-electron transfer, free radical quenching is completed within microseconds to milliseconds, perfectly matching the exposure timing of high-speed surface projection or scanning printing. Furthermore, the ink frame is widely adaptable to both hydrophilic and hydrophobic monomer systems. By adjusting the concentration ratio of triplet photosensitizer and initiator, it can flexibly match printing systems with different light intensities and exposure strategies, offering a wide process tolerance. Moreover, by adding electron donor auxiliaries and oxygen scavengers, environmental interference is effectively reduced, improving the stability and applicability of the ink in actual printing scenarios.

[0028] The embodiments of the present invention are given for illustrative and descriptive purposes only, and are not intended to be exhaustive or to limit the invention to the forms disclosed. Many modifications and variations will be apparent to those skilled in the art. The embodiments were chosen and described in order to better illustrate the principles and practical application of the invention, and to enable those skilled in the art to understand the invention and to design various embodiments with various modifications suitable for a particular purpose.

Claims

1. A photocurable ink with dual initiation and inhibition responses, characterized in that: It contains the following components: Photopolymerizable monomers or prepolymers; Photoinitiators are sensitive to light in the first wavelength band and generate active free radicals under light irradiation; Photoinhibitors are sensitive to second-wavelength light and produce active inhibitory substances under light irradiation to quench free radicals. Among them, the first band and the second band are orthogonal in the spectrum; It also includes electronic donor additives or oxygen scavengers, used to eliminate interference from external factors on the inhibition reaction and stabilize printing accuracy and process repeatability. External factors include, but are not limited to, dissolved oxygen and ambient temperature.

2. The photocurable ink with dual initiation and inhibition responses according to claim 1, characterized in that: The photopolymerizable monomer or prepolymer includes any one of the following: Water-based bio-ink system: The monomer is selected from one of polyethylene glycol diacrylate (PEGDA), gelatin methacryloyl glycol (GelMA), hyaluronic acid methacrylate (HAMA), and sodium alginate methacrylate; the solvent is water or PBS buffer. Resin engineering ink system: The monomer is selected from one of 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), polyurethane acrylate (PUA), and epoxy acrylate; the solvent is an active diluent or solvent-free.

3. The photocurable ink with dual initiation and inhibition responses according to claim 1, characterized in that: The photoinhibitor, which is excited to a long-lived triplet state under irradiation with the second wavelength light and has a redox potential sufficient to inactivate free radicals, includes any one of the following: Thiazide compounds: one of Methylene Blue, New Methylene Blue, Thionine, or Azure A / B / C; Compounds in the group of tons: Eosin Y, Rose Bengal, Erythrosine B, and one of the fluorescein derivatives; Macrocyclic conjugated compounds: one of tetraphenylporphyrin (TPP), zinc phthalocyanine (ZnPc), or aluminum phthalocyanine (AlPc); Fullerene derivatives: C60, C70 and their water-soluble or fat-soluble modifications.

4. The photocurable ink with dual triggering and inhibiting responses according to claim 1, characterized in that: The photoinitiator includes any one of the following: Acylphosphine oxide compounds: one of the following: phenyl-2,4,6-trimethylbenzoyl lithium phosphine oxide (LAP), phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (Irgacure 819), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO); α-Hydroxyketone compounds: one of 1-hydroxycyclohexylphenyl ketone (Irgacure 184) and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure 2959); Benzophenone derivatives or oxime ester derivatives: benzophenone BP or 4-phenylbenzophenone PBZ.

5. The photocurable ink with dual initiation and inhibition responses according to claim 1, characterized in that: The spectral matching methods for inks include: Combination A is blue light initiation-red light suppression: the photoinitiator is an acylphosphine oxide compound, with a response of 365-420nm; the photoinhibitor is a thiazide compound, porphyrin compound, or phthalocyanine compound, with a response of 600-700nm; Combination B is blue light initiation-green light suppression: the photoinitiator is an acylphosphine oxide or α-hydroxy ketone compound, with a response of 365-405nm; the photoinhibitor is a tannin compound, with a response of 500-580nm.

6. The photocurable ink with dual triggering and inhibiting responses according to claim 1, characterized in that: The inhibition mechanism of photocurable ink is based on photoinduced electron transfer: under the second band of light, the photoinhibitor transitions to the triplet state, acts as an electron acceptor to capture electrons from the free radicals of the growing chain, and generates a semi-reduced photosensitizer, thereby blocking chain growth; Alternatively, the photoinhibitor acts as an energy donor, generating singlet oxygen to achieve inhibition through the oxidation of free radicals.

7. The photocurable ink with dual initiation and inhibition responses according to claim 1, characterized in that: The manufacturing method of UV-curable ink is as follows: The additive curing is triggered by the first wavelength of light, while the subtractive curing is triggered by the second wavelength of light. The high-precision forming of the three-dimensional structure is achieved by the dual beams working together for exposure.

8. The photocurable ink with dual initiation and inhibition responses according to claim 1, characterized in that: The ink has high transmittance for both the first and second wavelengths of light, with a transmittance of >60%.

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