Sacrificial photosensitive resin composition capable of realizing single-photon and two-photon polymerization printing

Abstract

The invention provides a sacrifice photosensitive resin composition capable of realizing single-photon and two-photon polymerization printing and application of the sacrifice photosensitive resin composition. The composition comprises 20-60% of a photosensitive resin monomer, 0-25% of an ionic monomer, 0.1-10% of a difunctional photoinitiator and 0-5% of a hydrolyzable additive. The resin can be rapidly cured under excitation of ultraviolet light or two photons, has good water solubility or dissolvability, and facilitates removal of a support or a sacrificial template through dissolution after printing is completed. The preparation method comprises the following steps: mixing the components, uniformly stirring, and filtering to obtain the photosensitive resin with stable performance. The resin is not only suitable for a DLP 3D printing technology of single-photon polymerization, but also compatible with the high-precision printing requirement of two-photon polymerization.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin material and a preparation method thereof, in particular to a sacrificial photosensitive resin applicable to both single - photon and two - photon polymerization, which is applicable to the fields of high - precision 3D printing and micro - nano manufacturing. Background Art

[0002] With the rapid development of 3D printing technology, especially the wide application of single - photon and two - photon polymerization printing technologies, it is of great practical significance to develop a sacrificial photosensitive resin composition applicable to these two printing methods. The single - photon polymerization technology is widely used in the manufacture of complex structures due to its rapid prototyping and high precision. However, traditional photosensitive resins have limitations in printing complex overhanging structures and hollow structures, and it is difficult to meet the requirements of high precision and complex designs. The two - photon polymerization technology, with its high resolution and deep curing ability, provides the possibility for manufacturing micro - nano structures and high - precision devices. However, the development of two - photon printing materials lags behind, especially in the aspect of sacrificial materials.

[0003] Under this background, it is particularly important to develop a sacrificial photosensitive resin composition applicable to single - photon and two - photon polymerization printing. This resin not only needs to have good photosensitivity and mechanical properties to meet the curing and support requirements during printing, but also must have excellent hydrolysis properties so that it can be quickly and completely dissolved after printing to achieve post - processing of complex structures. In addition, this resin composition should also have low shrinkage rate, high transparency and good biocompatibility to meet the requirements of different application scenarios.

[0004] The development of such a sacrificial photosensitive resin composition has far - reaching significance for promoting the application of 3D printing technology in the fields of biomedicine, microfluidic chips, optical devices, etc. For example, in the field of biomedicine, sacrificial photosensitive resins can be used to manufacture complex structures such as tissue engineering scaffolds and drug release devices, providing technical support for personalized medicine. In the manufacture of microfluidic chips, this resin can achieve the construction of high - precision channel networks, improving the performance and function of the chips. In addition, its application in the manufacture of optical devices, such as microlens arrays and photonic integrated circuits, also provides new possibilities for innovation in the optical field.

[0005] In summary, developing a sacrificial photosensitive resin composition applicable to single - photon and two - photon polymerization printing can not only solve the limitations in the prior art, but also provide strong support for the application expansion of 3D printing technology in multiple fields, having important scientific significance and broad application prospects. Summary of the Invention

[0006] In view of the situation and deficiencies of the prior art, the present invention aims to provide a sacrificial photosensitive resin applicable to single-photon and two-photon polymerization printing. This resin has good water solubility or solubility and can be removed by dissolution after printing is completed, thereby enabling the manufacture of complex structures.

[0007] To achieve the above technical objectives, the technical solution adopted by the present invention is as follows: A sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing, the raw materials of which, in terms of mass percentage, include the following components:

[0008]

[0009] The photosensitive resin monomer is an acrylate monomer, which is one or a combination of more than one of α-methyl acrylate, acrylamide, hydroxyethyl acrylate, and acryloyl morpholine.

[0010] The ionic monomer is one or a combination of more than one of acryloyloxyethyl trimethyl ammonium chloride, potassium 3-sulfopropyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid sodium salt.

[0011] The hydrolyzable additive is at least one of polyethylene glycol diacrylate, phosphorylated distarch phosphate, and tannic acid.

[0012] The bifunctional photoinitiator is at least one of oxime ester photoinitiators containing a nitrocarbazole group, benzophenone photoinitiators, and iodonium salt cationic photoinitiators. The oxime ester photoinitiators containing a nitrocarbazole group are at least one of 2-phenyl-4,6-dinitro-1,3,5-triazine-2,4,6-trione oxime ester and 4-nitrocarbazole-9-yl-2-phenyl-2-oxoacetic acid oxime ester; the benzophenone photoinitiators are at least one of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl-ethanone, and 2-hydroxy-2-methyl-1-phenylpropanone; the iodonium salt cationic photoinitiators are at least one of bis(4-methoxyphenyl) iodonium hexafluorophosphate, bis(4-methoxyphenyl) iodonium hexafluoroarsenate, bis(4-methoxyphenyl) iodonium tetrafluoroborate, and bis(4-methoxyphenyl) iodonium trifluoromethanesulfonimide salt.

[0013] The method for preparing the sacrificial photosensitive resin composition is as follows:

[0014] (1) Mix the photosensitive resin monomer, ionic monomer, and hydrolyzable additive, and heat and stir to react to obtain a homogeneous photosensitive resin prepolymer solution A;

[0015] (2) Continue to fully stir solution A with the bifunctional photoinitiator until completely dissolved to obtain the sacrificial 3D printing photosensitive resin composition B.

[0016] In step (1), the molar ratio of the photosensitive resin, ionic monomer and hydrolyzable additive is (1 - 4.5):(1 - 15):(0.1 - 2).

[0017] The heating and stirring in step (1) is carried out at 40 - 60 °C for 0.5 - 2 h.

[0018] The application of the sacrificial photosensitive resin composition in single - photon and two - photon polymerization printing.

[0019] The operation process of single - photon 3D printing is to pour the photosensitive resin composition into the resin tank of the light - curing printing platform, adjust the printing parameters through computer software programs to print the required molded parts. After printing, use a cleaning solution to clean the printed parts and post - process the cured target parts; the operation process of two - photon 3D printing is to load the photosensitive resin composition into the resin tank of the two - photon printer, adjust the printing parameters through computer software programs to print the required molded parts. After printing, use a cleaning solution to clean the printed parts and post - process the cured target parts.

[0020] Beneficial effects

[0021] (1) This resin composition is applicable to both single - photon and two - photon polymerization technologies, broadening the application scope of the material. This resin can be rapidly cured under ultraviolet light or two - photon excitation.

[0022] (2) After printing, the material can be rapidly hydrolyzed at room temperature, facilitating the removal of supports or sacrificial templates by dissolution after printing. The hydrolyzed solution is transparent and has a low viscosity, facilitating post - processing and recycling.

[0023] (3) This composition uses a hydrolyzable additive, reducing the dependence on organic solvents and lowering the usage cost. This resin is not only applicable to the DLP 3D printing technology of single - photon polymerization, but also compatible with the high - precision printing requirements of two - photon polymerization, and can be used to manufacture microfluidic chips, biomedical scaffolds, porous materials, etc. with complex structures. Specific embodiments

[0024] The following further elaborates on the solution of the present invention in combination with specific embodiments:

[0025] A sacrificial photosensitive resin composition, the raw material components of which include, by mass percentage:

[0026]

[0027] The preparation method of the sacrificial photosensitive resin composition is as follows:

[0028] (1) Mix the photosensitive resin monomer, ionic monomer and hydrolyzable additive, where the molar ratio of the photosensitive resin to the ionic monomer is (1 - 4.5):(1 - 15):(0.1 - 2), and stir at 40 - 60 °C for 0.5 - 2 h to obtain a uniform photosensitive resin prepolymer solution A;

[0029] (2) Continue to stir the solution A with the bifunctional photoinitiator until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B.

[0030] Among them, the photosensitive resin monomer described in step (1) is an acrylate monomer, which is one or more combinations of α-methyl acrylate, acrylamide, hydroxyethyl acrylate, and acryloylmorpholine.

[0031] Preferably, the ionic monomer described in step (1) is one or more combinations of acryloyloxyethyl trimethyl ammonium chloride, potassium 3-sulfopropyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid sodium salt.

[0032] Preferably, the hydrolyzable additive described in step (1) is at least one of polyethylene glycol diacrylate, phosphorylated distarch phosphate, and tannic acid.

[0033] Preferably, the bifunctional photoinitiator described in step (2) is at least one of oxime ester photoinitiators containing nitrocarbazole groups, benzophenone photoinitiators, and iodonium salt cationic photoinitiators. The oxime ester photoinitiators containing nitrocarbazole groups are at least one of 2-phenyl-4,6-dinitro-1,3,5-triazine-2,4,6-trione oxime ester and 4-nitrocarbazole-9-yl-2-phenyl-2-oxoacetic acid oxime ester; the benzophenone photoinitiators are at least one of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropanone; the iodonium salt cationic photoinitiators are at least one of bis(4-methoxyphenyl)iodonium hexafluorophosphate, bis(4-methoxyphenyl)iodonium hexafluoroarsenate, bis(4-methoxyphenyl)iodonium tetrafluoroborate, and bis(4-methoxyphenyl)iodonium trifluoromethanesulfonimide salt.

[0034] The prepared photosensitive resin composition can be used for both single - photon and two - photon 3D printing technologies. The operation process of single - photon 3D printing is to pour the photosensitive resin composition into the resin tank of the light - curing printing platform, adjust the printing parameters through computer software programs to print the required molded parts. After printing, use a cleaning solution (isopropyl alcohol or alcohol) to clean the printed parts and post - process to cure the target parts. The operation process of two - photon 3D printing is to load the photosensitive resin composition into the resin tank of the two - photon printer, adjust the printing parameters through computer software programs to print the required molded parts. After printing, use a cleaning solution (isopropyl alcohol or alcohol) to clean the printed parts and post - process to cure the target parts.

[0035] Example 1

[0036] Weigh each component percentage according to the metered percentage:

[0037] (1) Add acrylamide, acryloyloxyethyl trimethyl ammonium chloride, and polyethylene glycol diacrylate to a single - necked flask in a molar ratio of 5:3:1.2. Under the condition of 60 °C, stir for 1 h to obtain a uniform photosensitive resin prepolymer solution A1;

[0038] (2) Continue to stir the solution A1 and 2 - hydroxy - 4 - (2 - hydroxyethoxy) - 2 - methylpropiophenone in a mass ratio of 50:1 until completely dissolved to obtain a sacrificial 3D - printing photosensitive resin composition B1.

[0039] Example 2

[0040] Weigh each component percentage according to the metered percentage:

[0041] (1) Add α - methyl acrylate, acryloyloxyethyl trimethyl ammonium chloride, and polyethylene glycol diacrylate to a single - necked flask in a molar ratio of 2:7:0.3. Under the condition of 60 °C, stir for 1 h to obtain a uniform photosensitive resin prepolymer solution A2;

[0042] (2) Continue to stir the solution A2 and 2 - hydroxy - 4 - (2 - hydroxyethoxy) - 2 - methylpropiophenone in a mass ratio of 50:1 until completely dissolved to obtain a sacrificial 3D - printing photosensitive resin composition B2.

[0043] Example 3

[0044] Weigh each component percentage according to the metered percentage:

[0045] (1) Add acryloylmorpholine, acryloyloxyethyl trimethyl ammonium chloride, and phosphorylated distarch phosphate to a single - necked flask in a molar ratio of 3.5:5:0.5. Under the condition of 60 °C, stir for 1 h to obtain a uniform photosensitive resin prepolymer solution A3;

[0046] (2) Continuously stir solution A3 and 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone in a mass ratio of 50:1 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B3.

[0047] Example 4

[0048] Weigh each component percentage according to the metered percentage:

[0049] (1) Put morpholino acrylate, potassium 3-sulfopropyl methacrylate and tannic acid into a single-necked flask in a molar ratio of 4:5:0.1, and stir at 60 °C for 1 h to obtain a homogeneous photosensitive resin prepolymer solution A4;

[0050] (2) Continuously stir solution A4 and 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone in a mass ratio of 50:1 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B4.

[0051] Example 5

[0052] Weigh each component percentage according to the metered percentage:

[0053] (1) Add 2-hydroxyethyl acrylate, potassium 3-sulfopropyl methacrylate and polyethylene glycol diacrylate into a single-necked flask in a molar ratio of 5:4:1.2, and stir at 60 °C for 1 h to obtain a homogeneous photosensitive resin prepolymer solution A5;

[0054] (2) Continuously stir solution A5 and 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone in a mass ratio of 50:1 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B5.

[0055] Example 6

[0056] Weigh each component percentage according to the metered percentage:

[0057] (1) Add 2-hydroxyethyl acrylate, potassium 3-sulfopropyl methacrylate and tannic acid into a single-necked flask in a molar ratio of 4.5:3.5:0.4, and stir at 60 °C for 1 h to obtain a homogeneous photosensitive resin prepolymer solution A6;

[0058] (2) Continuously stir solution A6 and 2-phenyl-4,6-dinitro-1,3,5-triazine-2,4,6-trione oxime ester in a mass ratio of 50:1 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B6.

[0059] Example 7

[0060] Weigh each component percentage according to the metered percentage:

[0061] (1) acrylamide, sodium 2-acrylamido-2-methylpropane sulfonate and phosphorylated distarch phosphate were added to a single-necked flask at a molar ratio of 4:5.5:0.2, and stirred at 60° C. for 1 h to prepare a uniform photosensitive resin prepolymer solution A7;

[0062] (2) Solution A7 and 4-nitrocarbazole-9-yl-2-phenyl-2-oxoacetic acid oxime ester were stirred at a mass ratio of 100:1.2 until they were completely dissolved, thereby preparing a sacrificial 3D printing photosensitive resin composition B7.

[0063] Example 8

[0064] Weigh the percentage of each component according to the measurement percentage:

[0065] (1) α-methylacrylate, sodium 2-acrylamido-2-methylpropanesulfonate and tannic acid were added into a single-necked flask at a molar ratio of 5:1:0.3, and stirred at 60° C. for 1 h to prepare a uniform photosensitive resin prepolymer solution A8;

[0066] (2) Solution A8 and bis(4-methoxyphenyl)iodonium hexafluorophosphate were further stirred at a mass ratio of 100:1.5 until they were completely dissolved, thereby preparing a sacrificial 3D printing photosensitive resin composition B8.

[0067] Example 9

[0068] Weigh the percentage of each component according to the measurement percentage:

[0069] (1) α-methylacrylate, sodium 2-acrylamido-2-methylpropanesulfonate and phosphorylated distarch phosphate were added into a single-necked flask at a molar ratio of 5:3.5:0.2, and stirred at 60° C. for 1 h to prepare a uniform photosensitive resin prepolymer solution A9;

[0070] (2) Solution A8 and 1-hydroxy-cyclohexyl-phenyl acetone were stirred at a mass ratio of 50:1 until they were completely dissolved, thereby preparing a sacrificial 3D printing photosensitive resin composition B9.

[0071] Example 10

[0072] Weigh the percentage of each component according to the measurement percentage:

[0073] (1) adding acrylamide, sodium 2-acrylamido-2-methylpropanesulfonate and polyethylene glycol diacrylate in a molar ratio of 4:6:1 into a single-necked flask, stirring at 60° C. for 1 h, to prepare a uniform photosensitive resin prepolymer solution A10;

[0074] (2) Continuously and sufficiently stir solution A10 and 2-hydroxy-2-methyl-1-phenylpropanone in a mass ratio of 100:1.3 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B10.

[0075] Example 11

[0076] Weigh the percentage of each component according to the metered percentage:

[0077] (1) Put hydroxyethyl acrylate, acryloyloxyethyl trimethyl ammonium chloride and tannic acid into a flask in a molar ratio of 5:5.5:0.3, and stir at 60 °C for 1 h to obtain a homogeneous photosensitive resin prepolymer solution A11;

[0078] (2) Continuously and sufficiently stir solution A11 and bis(4-methoxyphenyl)iodonium trifluoromethanesulfonimide salt in a ratio of 100:2.5 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B11.

[0079] Example 12

[0080] Weigh the percentage of each component according to the metered percentage:

[0081] (1) Put morpholine acrylate, 2-acrylamido-2-methylpropanesulfonic acid sodium salt and polyethylene glycol diacrylate into a single-necked flask in a molar ratio of 4:3:0.3, and stir at 60 °C for 1 h to obtain a homogeneous photosensitive resin prepolymer solution A12;

[0082] (2) Continuously and sufficiently stir solution A12 and bis(4-methoxyphenyl)iodonium hexafluoromethanesulfonimide salt in a ratio of 50:1.1 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B12.

[0083] Example 13

[0084] Weigh the percentage of each component according to the metered percentage:

[0085] (1) Put α-methyl acrylate, potassium 3-sulfopropyl methacrylate and phosphorylated distarch phosphate into a single-necked flask in a molar ratio of 5:5.5:0.4, and stir at 60 °C for 1 h to obtain a homogeneous photosensitive resin prepolymer solution A13;

[0086] (2) Continuously and sufficiently stir solution A13 and bis(4-methoxyphenyl)iodonium tetrafluoromethanesulfonimide salt in a ratio of 50:1.3 until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B13.

[0087] Example 14

[0088] Weigh the percentage of each component according to the metered percentage:

[0089] (1) acrylamide, sodium 2-acrylamido-2-methylpropanesulfonate and tannic acid were added into a single-necked flask at a molar ratio of 4:6:0.6, and stirred at 60° C. for 1 h to prepare a uniform photosensitive resin prepolymer solution A14;

[0090] (2) Solution A14 and 2-phenyl-4,6-dinitro-1,3,5-triazine-2,4,6-trione oxime ester were stirred at a mass ratio of 50:1 until they were completely dissolved, thereby preparing a sacrificial 3D printing photosensitive resin composition B14.

[0091] Embodiment 15

[0092] Weigh the percentage of each component according to the measurement percentage:

[0093] (1) Add hydroxyethyl acrylate, acryloyloxyethyl trimethyl ammonium chloride and phosphated distarch phosphate in a molar ratio of 4:5.5:0.2 into a single-necked flask, stir for 1 hour at 60° C., and prepare a uniform photosensitive resin prepolymer solution A15;

[0094] (2) Solution A15 and 2-hydroxy-2-methyl-1-phenylpropanone were further stirred at a ratio of 100:3 until they were completely dissolved, thereby preparing a sacrificial 3D printing photosensitive resin composition B15.

[0095] Comparative Example 1

[0096] (1) α-methacrylic acid and polyethylene glycol diacrylate were added into a single-necked flask at a molar ratio of 2:1, and stirred at 60° C. for 1 h to prepare a uniform photosensitive resin prepolymer solution A16;

[0097] (2) Solution A7, acrylamide and 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were mixed in a ratio of 100:1.5 and stirred until they were completely dissolved to prepare a 3D printing photosensitive resin composition B16.

[0098] Comparative Example 2

[0099] α-Methacrylic acid, acrylamide and 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone were stirred in a ratio of 50:0.6 until they were completely dissolved to prepare a 3D printing photosensitive resin composition B17.

[0100] Put the configured photosensitive resin into the Anycubic Photon D2 printer produced by Shenzhen Anycubic Technology Co., Ltd. and the Photonic Professional GT2 printer produced by Nanoscribe GmbH in Germany respectively. Adjust the printing parameters through computer software programs to print the required formed parts. After printing, use a cleaning solution (isopropyl alcohol or alcohol) to clean the printed parts and post-process and cure the target parts.

[0101] For the products obtained in the above embodiments, relevant tests were carried out on the splines of several sacrificial photosensitive resins obtained respectively; the hardness was referred to GB / T 2411-2008; the tensile strength and elongation at break were referred to GB / T1040.1-2006; the flexural strength and flexural modulus were referred to GB / T 9341-2008; the hydrolysis performance test was referred to ISO 175:2010, and the test results are shown in Table 1 below.

[0102]

[0103]

[0104] It can be seen from the above test results of No. 1# to No. 15# that the provided photosensitive resin composition has good hydrolysis performance. When no ionic monomer is added in Comparative Examples 1 and 2, after 24 hours of hydrolysis test at 40 °C, its rectangular samples only swell in water and do not have the ability to hydrolyze. The reason why the mechanical properties of the material in Comparative Example 2 are more excellent is that the addition of a small amount of the hydrolysis aid polyethylene glycol diacrylate with two functional groups enables the resin to form a cross-linked network during printing, which is crucial for the production of high-precision products such as printed sacrificial molds.

[0105] Based on the above results, when the synergistic effect of the photosensitive resin monomer and the ionic monomer enables the material to have good hydrolysis performance, the addition of a hydrolyzable additive with a certain molecular weight can promote the hydrolysis reaction to a certain extent and further enhance its mechanical properties.

[0106] The above are only several embodiments of the present application and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, making some changes or modifications using the technical content disclosed above is equivalent to equivalent implementation cases and all belong to the scope of the technical solution.

Claims

1. A sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing, characterized in that : The raw materials, by mass percentage, include the following components: Photosensitive resin monomer: 20 - 60% Ionic monomer: 10 - 40% Bifunctional photoinitiator: 0.1 - 10% Hydrolyzable additive: 5 - 20%.

2. The sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, wherein : The photosensitive resin monomer is an acrylate monomer, which is one or a combination of more than one of α-methyl acrylate, acrylamide, 2-hydroxyethyl acrylate, and acryloylmorpholine.

3. The sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, wherein : The ionic monomer is one or a combination of more than one of acryloyloxyethyl trimethyl ammonium chloride, potassium 3-sulfopropyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid sodium salt.

4. The sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, wherein : The hydrolyzable additive is at least one of polyethylene glycol diacrylate, phosphorylated distarch phosphate, and tannic acid.

5. The sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, wherein : The bifunctional photoinitiator is at least one of an oxime ester photoinitiator containing a nitrocarbazole group, a benzophenone photoinitiator, and an iodonium salt cationic photoinitiator. The oxime ester photoinitiator containing a nitrocarbazole group is at least one of 2-phenyl-4,6-dinitro-1,3,5-triazine-2,4,6-trione oxime ester and 4-nitrocarbazol-9-yl-2-phenyl-2-oxoacetic acid oxime ester; the benzophenone photoinitiator is at least one of 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 1-hydroxy-cyclohexyl-phenyl-ethanone, and 2-hydroxy-2-methyl-1-phenylpropanone; the iodonium salt cationic photoinitiator is at least one of bis(4-methoxyphenyl) iodonium hexafluorophosphate, bis(4-methoxyphenyl) iodonium hexafluoroarsenate, bis(4-methoxyphenyl) iodonium tetrafluoroborate, and bis(4-methoxyphenyl) iodonium trifluoromethanesulfonimide salt.

6. A method for preparing the sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing according to any one of claims 1 to 5, characterized in that : The steps are as follows: (1) Mix the photosensitive resin monomer, the ionic monomer, and the hydrolyzable additive, and heat and stir to react to obtain a uniform photosensitive resin prepolymer solution A; (2) Continue to stir the solution A and the bifunctional photoinitiator until completely dissolved to obtain a sacrificial 3D printing photosensitive resin composition B.

7. The method according to claim 6, wherein In step (1), the molar ratio of the photosensitive resin, the ionic monomer, and the hydrolyzable additive is (1 - 4.5):(1 - 15):(0.1 - 2).

8. The method according to claim 6, wherein The heating and stirring in step (1) are carried out at 40 - 60 °C for 0.5 - 2 h.

9. Application of the sacrificial photosensitive resin composition capable of single-photon and two-photon polymerization printing according to any one of claims 1 - 5 in single-photon and two-photon polymerization printing.

10. The application according to claim 9, wherein : The operation process of single-photon 3D printing is to pour the photosensitive resin composition into the resin tank of the light-curing printing platform, adjust the printing parameters through computer software programs to print the required shaped parts, and after printing, use a cleaning solution to clean the printed parts and post-process and cure the target parts; the operation process of two-photon 3D printing is to load the photosensitive resin composition into the resin tank of the two-photon printer, adjust the printing parameters through computer software programs to print the required shaped parts, and after printing, use a cleaning solution to clean the printed parts and post-process and cure the target parts.

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