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

Abstract

The invention provides a biocompatible photosensitive resin composition capable of realizing single-photon and two-photon polymerization printing and application of the biocompatible photosensitive resin composition in photocuring 3D printing. The composition is prepared from the following components in percentage by weight: 20 to 60 percent of polyurethane acrylate with biocompatibility, 10 to 40 percent of epoxy acrylate, 0 to 25 percent of polyethylene glycol dimethacrylate resin, 0 to 25 percent of reactive diluent, 0.1 to 10 percent of difunctional photoinitiator and 0 to 5 percent of light stabilizer. The prepared photosensitive resin composition can be simultaneously applied to 3D printing technologies of single-photon polymerization and two-photon polymerization, and in single-photon polymerization, the resin shows excellent forming precision and interlayer bonding strength; and in two-photon polymerization, the high absorption efficiency and the low background area polymerization characteristic enable submicron printing precision to be achieved. In addition, the composition also has good mechanical properties and thermal stability, and is suitable for manufacturing of various complex structures.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin material and a preparation method thereof, in particular to a biocompatible 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] Among many 3D printing technologies, the stereolithography 3D printing technology is an additive manufacturing technology that relies on ultraviolet light for rapid curing and has high forming accuracy. Photon polymerization technology is widely used in 3D printing due to its fast printing speed, but its resolution is usually at the level of dozens of micrometers, making it difficult to meet the high-precision requirements. Two-photon polymerization technology can achieve high resolution at the sub-micron level, but has a slow printing speed and high requirements for the two-photon absorption performance of the material. Therefore, it is of great significance to develop a photosensitive resin applicable to both single-photon and two-photon polymerization. Summary of the Invention

[0003] Aiming at the situation and deficiencies of the prior art, the present invention aims to provide a biocompatible photosensitive resin composition that can be printed by single-photon and two-photon polymerization and a preparation method thereof. This material can exhibit good curing performance under both polymerization methods and balance the printing speed and resolution.

[0004] In order to achieve the above technical objectives, the technical solution adopted by the present invention is as follows:

[0005] A biocompatible photosensitive resin composition, the raw material components of which include, by mass percentage:

[0006]

[0007] Preferably, the molecular formula of the biocompatible polyurethane acrylate is shown in Formula (I) or Formula (II):

[0008]

[0009]

[0010] Among them, m = 1, 2, 3 or 4, and the structural formulas of R1 and R2 are any of the following:

[0011] R1:

[0012] R3:

[0013] Preferably, the preparation method of the biocompatible polyurethane acrylate is as follows:

[0014] (1) In a round-bottom flask containing lignin-based polyol, N2 was introduced for protection. With a molar ratio of -NCO: -OH = 2:1, a measured amount of isocyanate and an organotin or organozinc catalyst were slowly added dropwise and mixed. The temperature was set at 60 - 80 °C, and the reaction was carried out for 0.2 - 4 h to obtain Solution A (a prepolymer capped with isocyanate groups).

[0015] (2) Solution A, an acrylate monomer containing -OH, and an organotin catalyst were reacted at a molar ratio of -NCO: -OH = 1:2 at 20 °C - 80 °C for 1 - 4 h to form a lignin-based polyurethane acrylate prepolymer C.

[0016] Among them, the lignin-based polyol described in step (1) is one or more combinations of lignin-based polyether polyol, lignin-based polyester polyol, and lignin-based polycarbonate polyol; the isocyanate described in step (1) is one or more combinations of diphenylmethane diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; the catalyst 1 described in step (1) is one or more combinations of dibutyltin dilaurate, stannous octoate, zinc octoate, and bismuth octoate; the acrylate monomer containing -OH described in step (2) is one or more combinations of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, and pentaerythritol triacrylate (PETA); the organotin catalyst described in step (2) is one or more combinations of stannous octoate, stannous 2-ethylhexanoate, and stannous octoate.

[0017] Preferably, the epoxy acrylate is one or more combinations of bisphenol A epoxy acrylate, polyethylene glycol diglycidyl ether acrylate, and 2,2'-bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]propane diglycidyl ether.

[0018] Preferably, the degree of polymerization of the polyethylene glycol dimethacrylate resin is 1 - 200.

[0019] Preferably, the active diluent is at least one selected from styrene, acrylate diluents, hydroxyacrylate diluents, vinyl ether diluents, and cyclohexane diluents; the acrylate diluents are selected from at least one of methyl methacrylate, 2-methacryloyloxyethyl phosphorylcholine, acrylamide, 1,6-hexanediol diacrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, dipropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol acrylate, and cyclotrimethylolpropane formal acrylate; the hydroxyacrylate diluents are selected from at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxyethyl acrylate; the vinyl ether diluents are selected from at least one of 4-hydroxybutyl vinyl ether and diethylene glycol divinyl ether; the cyclohexane diluents are selected from at least one of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide. The vinyl ether diluents are selected from at least one of 4-hydroxybutyl vinyl ether and diethylene glycol divinyl ether; the cyclohexane diluents are selected from at least one of 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide.

[0020] Preferably, 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, 4-nitrocarbazol-9-yl-2-phenyl-2-oxoacetic acid oxime ester, 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 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.

[0021] Preferably, the light stabilizer is at least one of sodium bicarbonate and pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0022] The preparation method of the described photosensitive resin composition with biocompatibility is to mix an appropriate amount of biocompatible polyurethane acrylate, epoxy acrylate, polyethylene glycol dimethacrylate resin, and reactive diluent in the dark and heat it to 30 - 60°C. After stirring and mixing evenly and cooling, a bifunctional photoinitiator and a light stabilizer are added, and stirred until completely uniform to obtain the photosensitive resin composition with biocompatibility.

[0023] 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 shaped parts. After printing, the printed parts are cleaned with a cleaning solution (isopropyl alcohol or alcohol) and post - processed 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 shaped parts. After printing, the printed parts are cleaned with a cleaning solution (isopropyl alcohol or alcohol) and post - processed to cure the target parts.

[0024] Beneficial effects

[0025] (1) The photosensitive resin of the present invention combines the advantages of single - photon and two - photon polymerization, and can achieve good curing effects in both modes. By adjusting the light source parameters (such as wavelength and power), high - precision and high - efficiency manufacturing can be achieved in different printing modes. In single - photon polymerization, the resin exhibits excellent forming accuracy and interlayer bonding strength; while in two - photon polymerization, its high absorption efficiency and low polymerization characteristics in the background area enable it to achieve sub - micron - level printing accuracy.

[0026] (2) Through the design of the bifunctional photoinitiator, the threshold power of two - photon polymerization is significantly reduced, and the printing efficiency is improved.

[0027] (3) The prepared photosensitive resin retains the biocompatibility and biodegradability of lignin. In addition, this composition also has good mechanical properties and thermal stability, is suitable for the manufacture of various complex structures, and is applicable to the fields of biomedicine and micro - nano manufacturing. Description of the drawings

[0028] Figure 1 It is the photo - curing mechanism diagram of biocompatible polyurethane acrylate. Specific implementation manners

[0029] The following further elaborates on the solution of the present invention in combination with specific implementation manners:

[0030] The raw materials involved in the following examples are as follows:

[0031] Biocompatible polyurethane acrylates, abbreviated as B-1, B-2, and B-3, are prepared as follows:

[0032] Biocompatible polyurethane acrylate B-1

[0033] (1) In a round-bottom flask containing 100 g of lignin-based polyester polyol, under N2 protection and with a molar ratio of -NCO:-OH = 2:1, a measured amount of isophorone diisocyanate and the catalyst bismuth isooctanoate were slowly added dropwise and mixed. The temperature was set at 60 °C and the reaction was carried out for 3 h to obtain solution A1.

[0034] (2) Solution A1 was reacted with 2-hydroxyethyl acrylate and the catalyst stannous octoate at a molar ratio of -NCO:-OH = 1:2 at 20 °C - 80 °C for 4 h to form a lignin-based polyurethane acrylate prepolymer B-1, and its structural formula is:

[0035]

[0036] R1: n = 1, 2, 3.

[0037] Lignin-based polyester polyol: The preparation method refers to the literature "Synthesis and Characterization of Lignin-based Polyester Polyols", Chemistry and Adhesion, Vol. 37, No. 3, 2015;

[0038] Isophorone diisocyanate: Purchased from Covestro AG, product number Desmodur I;

[0039] Bismuth isooctanoate: Purchased from Yantai Sunshine Plastics Co., Ltd., product number LK-2;

[0040] 2-Hydroxyethyl acrylate: Purchased from the official website of Shanghai Macklin Reagents, product number H810915;

[0041] Stannous octoate: Purchased from the official website of Shanghai Macklin Reagents, product number T818482;

[0042] Biocompatible polyurethane acrylate B-2

[0043] (1) In a round-bottom flask containing 100 g of lignin-based polyether polyol, under N2 protection and with a molar ratio of -NCO:-OH = 2:1, a measured amount of diphenylmethane diisocyanate and the catalyst dibutyltin dilaurate were slowly added dropwise and mixed. The temperature was set at 70 °C and the reaction was carried out for 3 h to obtain solution A2.

[0044] (2) React solution A1 with 2-hydroxyethyl methacrylate and stannous octoate catalyst at a molar ratio of -NCO: -OH = 1:2 at 70 °C for 3 h to form lignin-based polyurethane acrylate prepolymer B-2, and its structural formula is:

[0045]

[0046] R1: n = 1, 2, 3

[0047] Lignin-based polyether polyol: The preparation method refers to the literature "The effect of lignin-based polyols on the properties of polyurethane coatings", DOI is 10.1680 / jgrma.23.00040;

[0048] Diphenylmethane diisocyanate: Purchased from Covestro AG, product number is Desmodur H;

[0049] Dibutyltin dilaurate: Purchased from the official website of Shanghai Macklin Biochemical Co., Ltd., product number is D806313;

[0050] 2-Hydroxyethyl methacrylate: Purchased from the official website of Shanghai Macklin Biochemical Co., Ltd., product number is H709021;

[0051] Stannous octoate: Purchased from the official website of Shanghai Macklin Biochemical Co., Ltd., product number is T818482;

[0052] Biocompatible polyurethane acrylate B-3

[0053] (1) In a round-bottom flask containing 100 g of lignin-based polyether polyol, introduce N2 protection, and slowly add a measured amount of lysine diisocyanate and dibutyltin dilaurate catalyst at a molar ratio of -NCO: -OH = 2:1. Set the temperature to 70 °C and react for 3 h to obtain solution A2.

[0054] (2) React solution A1 with pentaerythritol triacrylate and stannous octoate catalyst at a molar ratio of -NCO: -OH = 1:2 at 70 °C for 3 h to form lignin-based polyurethane acrylate prepolymer B-3, and its structural formula is:

[0055]

[0056] R1: n = 1, 2, 3.

[0057] Lignin-based polyether polyol: The preparation method refers to the literature "The effect of lignin-based polyol on the properties of polyurethane coatings", DOI: 10.1680 / jgrma.23.00040;

[0058] Lysine diisocyanate: Purchased from the official website of Shanghai Macklin Reagents, product number L821986;

[0059] Dibutyltin dilaurate: Purchased from the official website of Shanghai Macklin Reagents, product number D806313;

[0060] Pentaerythritol triacrylate: Purchased from the official website of Shanghai Macklin Reagents, product number P830171;

[0061] Stannous octoate: Purchased from the official website of Shanghai Macklin Reagents, product number T818482;

[0062] Epoxy acrylate:

[0063] Bisphenol A epoxy acrylate: Purchased from Sartomer Company, product number CN104 NS, abbreviated as C-1;

[0064] Polyethylene glycol diglycidyl ether acrylate: Purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number P134831, abbreviated as C-2;

[0065] 2,2'-Bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]propane diglycidyl ether: Purchased from Adamas Company, product number A27581, abbreviated as C-3;

[0066] Polyethylene glycol dimethacrylate resin 1: Purchased from Sartomer Company, product number SR210, abbreviated as D-1;

[0067] Polyethylene glycol dimethacrylate resin 2: Purchased from Sartomer Company, product number SR211, abbreviated as D-2;

[0068] Reactive diluent:

[0069] 1,6-Hexanediol diacrylate: Purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number H102721, abbreviated as E-1;

[0070] Hydroxypropyl methacrylate: Purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number H109880, abbreviated as E-2;

[0071] Hydroxyethyl methacrylate: Purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number H103044, abbreviated as E-3;

[0072] Trimethylolpropane triacrylate: purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number T131641, abbreviated as E-4;

[0073] Bifunctional photoinitiator:

[0074] 2-Hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, also known as photoinitiator 2959: purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number H106300, abbreviated as F-1;

[0075] Bis(4-methoxyphenyl)iodonium hexafluorophosphate, also known as photoinitiator PI9388: purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number H106300, abbreviated as F-2;

[0076] 1-Hydroxy-cyclohexyl-phenylethanone: purchased from Aladdin Reagent (Shanghai) Co., Ltd., also known as photoinitiator 184: purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number H106300, abbreviated as F-3;

[0077] Sodium bicarbonate: purchased from Aladdin Reagent (Shanghai) Co., Ltd., product number S112331, abbreviated as G-1;

[0078] Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], also known as antioxidant 1010: purchased from Guangzhou Kayin Chemical Co., Ltd., product number JYANOX-1010, abbreviated as G-2.

[0079] According to the above formulation composition, the following 1# to 18# application formulations are obtained through specific formulations:

[0080]

[0081]

[0082] The preparation steps are as follows: Appropriately mix the biocompatible polyurethane acrylate, epoxy acrylate, polyethylene glycol dimethacrylate resin, and reactive diluent in the dark and heat to 30-60°C. After stirring and mixing evenly and cooling, add the bifunctional photoinitiator and light stabilizer, and stir until completely uniform to obtain the above-mentioned biocompatible photosensitive resin composition (1# to 18#).

[0083] The configured photosensitive resin was separately placed into the Anycubic Photon D2 printer produced by Shenzhen Anycubic Technology Co., Ltd. (Anycubic) and the Photonic Professional GT2 printer produced by Nanoscribe GmbH in Germany. The required formed parts were printed by adjusting the printing parameters through a computer software program. After printing, the printed parts were cleaned with a cleaning solution (isopropyl alcohol or alcohol) and the target parts were post-processed and cured.

[0084] For the products obtained in the above embodiments, relevant tests were carried out on the splines of several photosensitive resins (No. 1# - 18#) with biocompatibility obtained; the hardness referred to GB / T 2411-2008; the tensile strength and elongation at break referred to GB / T 1040.1-2006; the flexural strength and flexural modulus referred to GB / T 9341-2008, and the biocompatibility (MTT in vitro cytotoxicity test) referred to GB / T16886.5-2017. The test results are as follows

[0085] as shown in Table 1.

[0086] Tensile strength / MPa Elongation at break / % Flexural strength / MPa Flexural modulus / MPa Biocompatibility 1# 50.2 5.8 112 2920 84.6％ 2# 56.3 5.6 123 2936 88.2％ 3# 47.8 6.2 109 2795 85.4％ 4# 58.1 5.6 130 3578 92.1％ 5# 54.9 5.9 128 3035 87.3％ 6# 51 4.7 114 3034 83.2％ 7# 55.8 5.3 121 3005 88％ 8# 56 5.7 124 3210 84.2％ 9# 55 4.9 123 3020 74.5％ 10# 56.5 5.3 129 3215 78.9％ 11# 53.5 5.1 123 3006 80.5％ 12# 52.8 5.6 120 2995 75.6％ 13# 54.2 5.8 125 3115 79.5％ 14# 53.6 5.2 124 3102 80.2％ 15# 55.2 5.5 127 3118 81.3％ 16# 52.9 5.7 122 3015 79.9％ 17# 50.4 5.2 117 3036 74.8％ 18# 55.8 5.3 127 3158 84.9％ 19# 53.6 7.1 126 3020 55.9％

[0087] 19 is the control group, without adding biocompatible polyurethane acrylate.

[0088] It can be seen from the above results of No. 1# - 18# that the provided photosensitive resin composition has excellent biocompatibility, and its mechanical properties can be regulated by adjusting the relative content of the two components in the system; compared with Example 19, Example 4 has the best strength, modulus and biocompatibility. This is because the content of biocompatible polyurethane acrylate is relatively high, and there is an interfacial dynamic hydrogen bond effect inside it, which can greatly improve the strength of the material. Moreover, the lignin molecule contains abundant functional groups such as hydroxyl, carbonyl and methoxy groups, and these functional groups endow it with good reactivity and biocompatibility.

[0089] Figure 1 Figure 19 is the photo-curing mechanism diagram of biocompatible polyurethane acrylate. Lignin is the second largest biomass resource after cellulose. It has received wide attention because of its wide source, low cost and excellent ultraviolet shielding function. Introducing lignin-based polyol into polyurethane can not only enhance its strength, but also have biocompatibility. Finally, it is capped with a photosensitive group and can undergo cross-linking and curing under the action of ultraviolet light.

[0090] As described above, these 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 with preferred embodiments as above, 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 disclosed technical content is equivalent to equivalent implementation cases and all belong to the scope of the technical solution.

Claims

1. A biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing, characterized in that : By mass percentage, the raw materials include the following components: The molecular formula of the biocompatible polyurethane acrylate is shown in Formula (I) or Formula (II): Wherein, n = 1, 2, 3; m = 1, 2, 3 or 4, and the structural formula of R1 and R2 is any one of the following: R1: Lignin is lignin; R3:

2. The biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, wherein : The preparation method of the biocompatible polyurethane acrylate is as follows: (1) Prepare a prepolymer capped with isocyanate groups: In a reaction vessel containing lignin-based polyol, under N2 protection, and according to the molar ratio -NCO:-OH = 2:1, slowly dropwise add a measured amount of a mixture of isocyanate and an organotin or organozinc catalyst, set the temperature to 60 - 80 °C, and react for 0.2 - 4 h to obtain Solution A, generating a prepolymer capped with isocyanate groups; (2) Prepare a lignin-based polyurethane acrylate prepolymer: React Solution A with an acrylate monomer containing -OH and an organotin catalyst according to the molar ratio -NCO:-OH = 1:2 at 20 °C - 80 °C for 1 - 4 h to form a biocompatible lignin-based polyurethane acrylate prepolymer.

3. A biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, characterized in that : The lignin-based polyol described in step (1) is one or more combinations of lignin-based polyether polyol and lignin-based polyester polyol; the isocyanate described in step (1) is one or more combinations of diphenylmethane diisocyanate, lysine diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate; the organotin or organozinc catalyst described in step (1) is one or more combinations of dibutyltin dilaurate, stannous octoate, zinc octoate, and bismuth octoate; the acrylate monomer containing -OH described in step (2) is one or more combinations of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, and pentaerythritol triacrylate; the organotin catalyst described in step (2) is one or more combinations of stannous octoate, stannous 2-ethylhexanoate, and stannous octoate.

4. A biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, characterized in that : The epoxy acrylate is one or more combinations of bisphenol A epoxy acrylate, polyethylene glycol diglycidyl ether acrylate, and 2,2'-bis[4-(2-hydroxy-3-acryloyloxypropoxy)phenyl]propane diglycidyl ether.

5. A biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, characterized in that : The degree of polymerization of the polyethylene glycol dimethacrylate resin is 1 - 200.

6. A biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, characterized in that : The active diluent is at least one selected from styrene, acrylate diluents, hydroxyacrylate diluents, vinyl ether diluents, and cyclohexane diluents; the acrylate diluents are at least one selected from methyl methacrylate, 2-methacryloyloxyethyl phosphorylcholine, acrylamide, 1,6-hexanediol diacrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, dipropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol acrylate, and cyclic trimethylolpropane formal acrylate; the hydroxyacrylate diluents are at least one selected from 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxyethyl acrylate; the vinyl ether diluents are at least one selected from 4-hydroxybutyl vinyl ether and diethylene glycol divinyl ether; the cyclohexane diluents are at least one selected from 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide. The vinyl ether diluents are at least one selected from 4-hydroxybutyl vinyl ether and diethylene glycol divinyl ether; the cyclohexane diluents are at least one selected from 4-vinylcyclohexene oxide and 4-vinylcyclohexene oxide.

7. A biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, characterized in that : The bifunctional photoinitiator is at least one selected from 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 selected from 2-phenyl-4,6-dinitro-1,3,5-triazine-2,4,6-trione oxime ester, 4-nitrocarbazol-9-yl-2-phenyl-2-oxoacetic acid oxime ester, 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 photoinitiators are at least one selected from 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 selected from bis(4-methoxyphenyl)iodonium hexafluorophosphate, bis(4-methoxyphenyl)iodonium hexafluoroarsenate, bis(4-methoxyphenyl)iodonium tetrafluoroborate, and bis(4-methoxyphenyl)iodonium trifluoromethanesulfonimide salt.

8. A biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to claim 1, characterized in that : The light stabilizer is at least one selected from sodium bicarbonate and pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

9. A preparation method of a biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing according to any one of claims 1 to 8, characterized in that : An appropriate amount of biocompatible polyurethane acrylate, epoxy acrylate, polyethylene glycol dimethacrylate resin, and active diluent are mixed in the dark and heated to 30 - 60 °C. After stirring and mixing evenly and cooling, a bifunctional photoinitiator and a light stabilizer are added, and stirring is continued until completely uniform to obtain a biocompatible photosensitive resin composition.

10. Use of a biocompatible photosensitive resin composition capable of single-photon and two-photon polymerization printing as described in any one of claims 1 to 9 in photocuring 3D printing, characterized in that : 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 photocuring printing platform, adjust the printing parameters through computer software programs to print the required formed parts, and after printing, use a cleaning solution 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 formed parts, and after printing, use a cleaning solution to clean the printed parts and post-process to cure the target parts.

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