Light-cured resin as well as preparation method and application thereof

Abstract

The invention relates to the technical field of resin materials, and discloses a light-cured resin which comprises the following components in percentage by mass: 20-50% of an epoxy resin composition, 10-30% of phosphorus-containing epoxy resin, 5-30% of phosphorus-containing acrylate, 10-40% of a free radical monomer, 1-10% of a photoinitiator and 1-10% of an auxiliary agent, the epoxy resin composition comprises an oxetane compound containing benzyl and derivative groups thereof, and a non-phosphorus-containing epoxy resin. After the oxetane compound containing benzyl and derivative groups thereof, the phosphorus-containing epoxy resin and the phosphorus-containing acrylate are added, the reaction speed of the cationic resin part is increased while the original mechanical property is maintained, so that the initial reaction speed of the light-cured resin is increased, the crosslinking degree is rapidly increased, and the light-cured resin has good light-cured performance. Finally, on the basis of keeping the mechanical property, the flame retardant property and the printing efficiency are effectively balanced, and the photosensitive resin has important practical significance in SLA printing.

Description

Technical Field

[0001] The present invention relates to the technical field of resin materials, and in particular to a photocurable resin and a preparation method and application thereof. Background Art

[0002] Stereolithography (SLA) is an additive manufacturing technology that uses computer-aided design and computer-aided manufacturing software (CAD / CAM) to control ultraviolet (UV) laser irradiation to cure resin and stack them layer by layer to obtain a cured resin product. This method can simply and fully automatically produce complex three-dimensional shapes that have been difficult to produce with various processing methods in the past, and is of great significance in the field of processing technology.

[0003] Photocurable resin refers to liquid monomers or oligomers that can undergo cross-linking reactions under certain specific wavelengths (such as 355nm) when exposed to light. Photocurable resins are converted from free-flowing liquids to non-stick solids after exposure to light. Commonly used photocurable resins include epoxy resins, polyurethane resins, acrylic resins, polyester resins, and various modified resins. The photocurable resins used in existing SLA equipment are mainly free radical-cation hybrid systems, but the components used in existing photocurable resins do not have fire retardant properties and cannot meet the requirements of fire retardant properties in specific use environments. Adding components with fire retardant properties will have an adverse effect on the printing efficiency of 3D printing.

[0004] Therefore, how to provide a photocurable resin that can effectively balance fire resistance and printing efficiency is an urgent problem to be solved by those skilled in the art. Summary of the invention

[0005] In view of this, the present invention provides a photocurable resin to solve the problem that the existing photocurable resin used for 3D printing cannot have both fireproof performance and printing efficiency.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] In one aspect, the present invention provides a photocurable resin, which comprises the following components, measured by mass percentage: 30-60% of epoxy resin composition, 10-30% of phosphorus-containing epoxy resin, 5-30% of phosphorus-containing acrylate, 10-40% of free radical monomer, 1-10% of photoinitiator and 1-10% of auxiliary agent;

[0008] The epoxy resin composition comprises an oxetane compound containing benzyl and its derivative groups and a non-phosphorus-containing epoxy resin.

[0009] Preferably, the mass of the oxetane compound containing benzyl and its derivative groups accounts for 20-60% of the amount of the non-phosphorus-containing epoxy resin added.

[0010] Preferably, the oxetane compound containing benzyl and its derivative groups includes one or more of 3-benzyloxymethyl-3-methyloxetane (BEH), 3-(4-fluorobenzyloxy)methyl-3-methyloxetane (FEH), and 3-(4-methoxybenzyl)methyl-3-methyloxetane (MEH).

[0011] Preferably, the non-phosphorus-containing epoxy resin includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, alicyclic epoxy resin, and hydrogenated bisphenol A epoxy resin.

[0012] Preferably, the phosphorus-containing epoxy resin includes one or both of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-modified epoxy resin and epoxy phosphate.

[0013] Preferably, the phosphorus-containing acrylate has a phosphorus-containing functional group and at least two acrylate functional groups.

[0014] Preferably, the free radical monomer includes one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer, and a multifunctional acrylate monomer.

[0015] Preferably, the photoinitiator includes a free radical initiator and a cationic initiator.

[0016] Preferably, the free radical initiator includes one or more of free radical initiator 184, free radical initiator 1173, free radical initiator 2959, and 2-isopropylthioxanthone (ITX);

[0017] Preferably, the cationic initiator includes one or more of cationic initiator 6976, cationic initiator 6992, and cationic initiator 261.

[0018] Preferably, the auxiliary agent includes one or more of nano silicon dioxide, nano titanium dioxide, a block copolymer with a core-shell structure, polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyether-modified polydimethylsiloxane.

[0019] On the other hand, the present invention also provides a method for preparing the photocurable resin described in any one of the above items, comprising the following steps:

[0020] (1) mixing an epoxy resin composition, a phosphorus-containing epoxy resin, a phosphorus-containing acrylate, a free radical monomer, a photoinitiator and an auxiliary agent to obtain a mixture;

[0021] (2) The mixture is subjected to vacuum degassing to obtain a photocurable resin.

[0022] Preferably, the step (1) is: when the photoinitiator includes a free radical initiator and a cationic initiator, the step (1) is: after mixing the epoxy resin composition, the phosphorus-containing epoxy resin and the cationic initiator, adding the free radical monomer, the phosphorus-containing acrylate and the free radical initiator, adding the auxiliary agent after mixing, and mixing again to obtain the mixture.

[0023] Furthermore, the present invention further provides a use of any of the above-mentioned photocurable resins or the photocurable resins prepared by any of the above-mentioned preparation methods in 3D printing.

[0024] The present invention provides a photocurable resin, which has the following beneficial effects compared with the prior art:

[0025] The present invention adds phosphorus-containing epoxy resin and phosphorus-containing acrylate as reactive flame retardant components, and at the same time greatly improves the curing speed of the cationic resin part in the photocurable material through an oxetane compound containing benzyl and its derivative groups, thereby achieving a balance between the material's mechanical properties, fire resistance and printing efficiency.

[0026] Specifically, the epoxy resin composition of the present invention includes an oxetane compound containing a benzyl group and a derivative group thereof and a non-phosphorus-containing epoxy resin. In the 3D printing process, by adding the oxetane compound containing a benzyl group and a derivative group thereof, the initial conversion rate of the photocurable resin is higher. This is because the free radical initiator can produce proton acid under light conditions, and the benzyl compound participates in the reaction when the epoxy ring is opened. Based on this, while providing hydrogen ions, the terminal of the product molecule generated in the cationic polymerization process can be provided with a hydroxyl group, and the reactant with a hydroxyl group can cause the cationic polymerization to produce a chain transfer, thereby improving the overall speed of cationic curing.

[0027] In addition, the present invention can significantly improve the flame retardant properties by adding phosphorus-containing epoxy resin and acrylate, while controlling the viscosity of the epoxy resin composition in the mixed resin, thereby improving the conversion rate of the photocurable product in the initial curing, and obtaining a photocurable resin that can be normally printed on an SLA device and has certain flame retardant properties. DETAILED DESCRIPTION

[0028] The present invention will be described below by specific examples, and it will be appreciated by those skilled in the art that the following specific examples are only for illustrative purposes, and do not limit the scope of the present invention in any way. In addition, in the following examples, unless otherwise specified, the reagents and equipment used are all commercially available. If in the following examples, specific treatment conditions and treatment methods are not clearly described, then conditions and methods known in the art can be used to process.

[0029] In one aspect of the present invention, the present invention provides a photocurable resin, which comprises the following components, measured by mass percentage: 20-50% of an epoxy resin composition, 10-30% of a phosphorus-containing epoxy resin, 5-30% of a phosphorus-containing acrylate, 10-40% of a free radical monomer, 1-10% of a photoinitiator and 1-10% of an auxiliary agent; the epoxy resin composition comprises an oxetane compound containing a benzyl group and its derivative groups and a non-phosphorus-containing epoxy resin.

[0030] The present invention improves the flame retardant properties by introducing phosphorus-containing functional groups. Both phosphorus-containing epoxy resins and phosphorus-containing acrylates are reactive, which can increase the proportion of flame retardant components in the formula, thereby effectively improving the flame retardant properties. However, the reactivity of the resin with phosphorus-containing functional groups is lower than that of ordinary resins. Based on this, the present invention improves the conversion rate of the initial curing by adding a highly reactive epoxy resin composition.

[0031] The study found that the reactivity of the oxetane compound containing benzyl and its derivative groups is much higher than that of other oxetane compounds. The present invention obtains an epoxy resin composition by mixing a non-phosphorus-containing epoxy resin with an oxetane compound containing benzyl and its derivative groups. The epoxy resin composition can not only reduce the viscosity of the cationic resin part and maintain the viscosity at about 500 cps, but also effectively increase the curing speed of the cationic resin, which is ultimately manifested in the improvement of the initial bending strength of the sample after printing.

[0032] Optionally, the mass of the oxetane compound containing benzyl and its derivative groups accounts for 20-60% of the amount of the non-phosphorus-containing epoxy resin added. If the amount of the oxetane compound containing benzyl and its derivative groups added is not within this range, the curing speed of the cationic will be affected, ultimately affecting the strength of the photocurable resin after the initial curing.

[0033] Among them, the oxetane compound containing benzyl and its derivative groups includes one or more of 3-benzyloxymethyl-3-methyloxetane, 3-(4-fluorobenzyloxy)methyl-3-methyloxetane, and 3-(4-methoxybenzyl)methyl-3-methyloxetane; the non-phosphorus-containing epoxy resin includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, alicyclic epoxy resin, and hydrogenated bisphenol A type epoxy resin.

[0034] Optionally, the phosphorus-containing epoxy resin includes one or both of DOPO-modified epoxy resin and epoxy phosphate, preferably a DOPO-modified epoxy resin, such as DOPO-modified phenolic epoxy resin, 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), etc., which can be purchased from the market.

[0035] Optionally, the phosphorus-containing acrylate has a phosphorus-containing functional group and at least two acrylate functions. For example, the phosphorus-containing acrylate can be prepared by the following method: after mixing cyclic phosphoric anhydride and hydroxyl-containing acrylate monomer in a mass ratio of 3:4, adding a cation exchange resin, and reacting at 120°C for 3-5h to obtain the phosphorus-containing acrylate. In the present invention, the cation exchange resin is used as a catalyst to react cyclic phosphoric anhydride with hydroxyl-containing acrylate monomer to obtain phosphorus-containing acrylate, and the addition of the phosphorus-containing acrylate can effectively improve the flame retardant properties of the product.

[0036] It should be noted that the phosphorus-containing acrylate can also be prepared by other methods or purchased on the market. The phosphorus-containing acrylate only needs to meet the following conditions: it has a phosphorus-containing functional group and at least two acrylate functional groups to ensure that the phosphorus-containing acrylate has high reactivity.

[0037] Optionally, the free radical monomer includes one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer, and a multifunctional acrylate monomer.

[0038] Optionally, the photoinitiator includes a free radical initiator and a cationic initiator, wherein the free radical initiator is used to initiate free radical polymerization of acrylate, including one or more of free radical initiator 184, free radical initiator 1173, free radical initiator 2959, and 2-isopropylthioxanthone; the cationic initiator is used to initiate cationic polymerization of epoxy resin, including one or more of cationic initiator 6976, cationic initiator 6992, and cationic initiator 261. It should be noted that there is no special limitation on the proportion of free radical initiators and cationic initiators, for example, the proportion of free radical initiators is 1-5% of all resins containing acrylate groups, specifically 1%, 2%, 3%, 4%, 5%, etc.; the proportion of cationic initiators is 1-10% of all resins containing epoxy groups, specifically 1%, 2%, 5%, 7%, 10%, etc.

[0039] Preferably, the auxiliary agent includes one or more of nano silicon dioxide, nano titanium dioxide, a block copolymer with a core-shell structure, polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyether-modified polydimethylsiloxane, wherein polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyether-modified polydimethylsiloxane are in liquid form, and nano silicon dioxide, nano titanium dioxide, and a block copolymer with a core-shell structure are in solid form, and the particle size is preferably a powder of about 30 nm.

[0040] It should be noted that the specific selection of the auxiliary agent in the present invention is not particularly limited, and it is a conventional additive in the preparation process of the photocurable resin.

[0041] On the other hand, the present invention also provides a method for preparing the photocurable resin described in any one of the above items, comprising the following steps:

[0042] (1) mixing an epoxy resin composition, a phosphorus-containing epoxy resin, a phosphorus-containing acrylate, a free radical monomer, a photoinitiator and an auxiliary agent to obtain a mixture;

[0043] (2) The mixture is subjected to vacuum degassing to obtain a photocurable resin.

[0044] When the photoinitiator includes a free radical initiator and a cationic initiator, the step (1) is: after mixing the epoxy resin composition, the phosphorus-containing epoxy resin and the cationic initiator, adding the free radical monomer, the phosphorus-containing acrylate and the free radical initiator, adding the auxiliary agent after mixing, and mixing again to obtain a mixture.

[0045] Optionally, the vacuum degree of the vacuum degassing process in step (2) can be -0.99 MPa, and the vacuuming time can be controlled to be 5 minutes. The specific vacuum degree and vacuuming time can be adjusted according to actual conditions and are not particularly limited in the present invention.

[0046] In the preparation process of the photocurable resin of the present invention, the epoxy resin composition, the phosphorus-containing epoxy resin and the cationic initiator are first mixed as a group, and then the free radical monomer, the phosphorus-containing acrylate and the free radical initiator are added and mixed. Through the feeding method and sequence defined in the present invention, the uniformity of material mixing can be improved, thereby improving product performance.

[0047] The technical effects achieved by the present invention are described below in conjunction with specific embodiments.

[0048] Example 1

[0049] The present embodiment provides a photocurable resin, which is composed of the following components: 25% of epoxy resin E-51, 25% of epoxy resin 2021P, 10% of phosphorus-containing epoxy resin (EP), 10% of phosphorus-containing acrylate (OPA), 20% of free radical monomer, 6% of photoinitiator (PI) and 4% of auxiliary agent.

[0050] The phosphorus-containing epoxy resin is a DOPO-type modified phenolic epoxy resin, the free radical monomer is a difunctional acrylate monomer (HDDA), the photoinitiator includes a free radical initiator 184 and a cationic initiator 6992 in a mass ratio of 1:1, and the auxiliary agent is nano-titanium dioxide with a particle size of 30 nm;

[0051] The preparation method of phosphorus-containing acrylate is as follows: cyclic phosphoric anhydride and hydroxyl-containing acrylate monomer are mixed in a mass ratio of 3:4, a cation exchange resin is used as a catalyst, and the mixture is reacted at 120° C. for 4 hours to obtain phosphorus-containing acrylate.

[0052] The preparation method of the photocurable resin is as follows: after mixing epoxy resin E-51, epoxy resin 2021P, phosphorus-containing epoxy resin and cationic initiator at room temperature for 30 minutes, free radical monomer, phosphorus-containing acrylate and free radical initiator are added, after mixing at room temperature for 30 minutes, auxiliary agent is added, mixed again, dispersed for 5 minutes, and a mixture is obtained; the mixture is vacuum defoamed, wherein the vacuum degree is -0.99 MPa, and the vacuuming time is 5 minutes, to obtain a photocurable resin.

[0053] Example 2

[0054] This embodiment is substantially the same as the embodiment 1, the only difference being that the photocurable resin mixture is composed of the following components: 25% of epoxy resin E-51, 20% of epoxy resin 2021P, 15% of BEH, 30% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0055] Example 3

[0056] This embodiment is basically the same as the embodiment 1, the only difference being that the photocurable resin is composed of the following components: 20% of epoxy resin E-51, 20% of epoxy resin 2021P, 15% of BEH, 5% of phosphorus-containing epoxy resin, 30% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0057] Example 4

[0058] This embodiment is basically the same as the embodiment 1, the only difference being that the photocurable resin is composed of the following components: 20% of epoxy resin E-51, 20% of epoxy resin 2021P, 20% of BEH, 10% of phosphorus-containing acrylate, 20% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0059] Example 5

[0060] This embodiment is basically the same as the embodiment 1, the only difference being that the photocurable resin is composed of the following components: 15% of epoxy resin E-51, 15% of epoxy resin 2021P, 15% of BEH, 15% of phosphorus-containing epoxy resin, 10% of phosphorus-containing acrylate, 20% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0061] Example 6

[0062] This embodiment is basically the same as the embodiment 1, the only difference being that the photocurable resin is composed of the following components: 15% of epoxy resin E-51, 10% of epoxy resin 2021P, 15% of BEH, 20% of phosphorus-containing epoxy resin, 15% of phosphorus-containing acrylate, 15% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0063] Example 7

[0064] This embodiment is basically the same as the embodiment 1, the only difference being that the photocurable resin is composed of the following components: 15% of epoxy resin E-51, 10% of epoxy resin 2021P, 5% of BEH, 20% of phosphorus-containing epoxy resin, 20% of phosphorus-containing acrylate, 20% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0065] Example 8

[0066] This embodiment is basically the same as the embodiment 1, the only difference being that the photocurable resin is composed of the following components: 15% of epoxy resin E-51, 20% of epoxy resin 2021P, 15% of BEH, 10% of phosphorus-containing epoxy resin, 5% of phosphorus-containing acrylate, 25% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0067] Example 9

[0068] This embodiment is basically the same as Embodiment 6, the only difference being that the oxetane compound containing benzyl and its derivative groups is replaced by 3-(4-fluorobenzyloxy)methyl-3-methyloxetane.

[0069] Comparative Example 1

[0070] This comparative example is substantially the same as Example 1, except that the photocurable resin is composed of the following components: 35% of epoxy resin E-51, 10% of epoxy resin 2021P, 35% of free radical monomer, 10% of photoinitiator and 10% of auxiliary agent.

[0071] Comparative Example 2

[0072] The difference between this comparative example and Example 1 is that the photocurable resin is composed of the following components: 30% of epoxy resin E-51, 25% of epoxy resin 2021P, 35% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0073] Comparative Example 3

[0074] The difference between this comparative example and Example 1 is that the photocurable resin is composed of the following components: 35% of epoxy resin E-51, 30% of epoxy resin 2021P, 25% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0075] Comparative Example 4

[0076] The difference between this comparative example and Example 1 is that the photocurable resin is composed of the following components: 25% of epoxy resin E-51, 35% of epoxy resin 2021P, 30% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0077] Comparative Example 5

[0078] This comparative example is basically the same as Example 1, except that the photocurable resin is composed of the following components: 15% of epoxy resin E-51, 25% of epoxy resin 2021P, 20% of flame retardant tributyl phosphate, 30% of free radical monomer, 6% of photoinitiator and 4% of auxiliary agent.

[0079] The compositions of the photocurable components of Examples 1-9 and Comparative Examples 1-5 are summarized as shown in Table 1.

[0080] Table 1

[0081]

[0082] Since the purpose of the present invention is to maintain or even improve the curing strength of the material while improving the conversion rate during the initial photocuring, the performance characterization focuses on the initial bending strength at fixed laser power and scanning speed and the final product performance after bending curing.

[0083] In the specific test method, the bending strength is based on the test requirements of ASTM D790, and the SLA equipment is used to print the sample strips of the photocurable resin prepared in different embodiments and comparative examples under different power and scanning speed parameter conditions. After printing, the initial bending strength is tested immediately and other performance indicators are tested after post-curing. The specific results of the initial bending strength are shown in Table 2.

[0084] Table 2

[0085]

[0086] From the test results in Table 2, it can be seen that in the example in which the oxetane compound containing benzyl and its derivative groups was added, the initial bending strength after printing was not much different from that of the comparative example, indicating that the addition of the oxetane compound containing benzyl and its derivative groups balanced the effect of the phosphorus-containing functional group on the curing speed and maintained the conversion rate during the printing process. Among them, the comparative example 5 greatly reduced the strength of the resin after curing because the flame retardant added partially failed to participate in the reaction.

[0087] Except for the initial flexural strength, other final performance indicators after sufficient post-curing are shown in Table 3.

[0088] Table 3

[0089] Number / Performance Bending strength(MPa) Tensile strength(MPa) Flame retardant grade Impact strength (J / m) Example 1 78 42 HB 34 Example 2 74 45 HB 33 Example 3 75 48 V2 36 Example 4 81 44 V2 32 Example 5 75 46 V1 38 Example 6 76 43 V1 35 Example 7 72 40 V1 29 Example 8 75 43 V2 34 Example 9 73 42 V1 32 Comparative Example 1 72 44 HB 31 Comparative Example 2 75 46 HB 34 Comparative Example 3 73 42 HB 33 Comparative Example 4 72 45 HB 36 Comparative Example 5 37 29 V2 27

[0090] It can be concluded from Table 3 that when the resin is fully reacted after post-curing, the mechanical properties of the embodiment and the comparative example do not change significantly, the printing speed is maintained, and the flame retardant properties are increased. Similarly, in comparative example 5, the flame retardant component is added alone, which helps to improve the flame retardant properties, but has a great impact on the overall mechanical properties.

[0091] It should be noted that in Example 7, since the amount of BEH added is small and the phosphorus-containing functional groups are large, both the small amount of BEH and the large amount of phosphorus-containing functional groups will reduce the curing speed and thus reduce the initial flexural strength. Therefore, the initial flexural strength and impact strength of Example 7 are relatively low. The epoxy functional group can continue to undergo dark reaction after the light exposure ends. Based on this, after being placed for a long time, the impact strength of Example 7 can reach a level close to that of Example 1.

[0092] In summary, by adding oxetane compounds containing benzyl and its derivative groups, phosphorus-containing epoxy resins and phosphorus-containing acrylates, the reaction rate of the cationic resin part was improved while maintaining the original mechanical properties, thereby increasing the initial reaction rate of the photocurable resin and rapidly improving the degree of cross-linking. Ultimately, while maintaining the mechanical properties, the flame retardant properties and printing efficiency were effectively balanced, which has important practical significance for photosensitive resins in SLA printing.

[0093] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A photocurable resin, characterized in that: The composition comprises the following components by weight percentage: 30-60% epoxy resin composition, 10-30% phosphorus-containing epoxy resin, 5-30% phosphorus-containing acrylate, 10-40% free radical monomer, 1-10% photoinitiator and 1-10% auxiliary agent; The epoxy resin composition comprises an oxetane compound containing benzyl and its derivative groups and a non-phosphorus-containing epoxy resin.

2. The photocurable resin according to claim 1, characterized in that: The mass of the oxetane compound containing benzyl and its derivative groups accounts for 20-60% of the added amount of the non-phosphorus-containing epoxy resin.

3. The photocurable resin according to claim 2, characterized in that: The oxetane compound containing benzyl and its derivative groups includes one or more of 3-benzyloxymethyl-3-methyloxetane, 3-(4-fluorobenzyloxy)methyl-3-methyloxetane, and 3-(4-methoxybenzyl)methyl-3-methyloxetane; The non-phosphorus-containing epoxy resin includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, alicyclic epoxy resin, and hydrogenated bisphenol A epoxy resin.

4. The photocurable resin according to claim 1, characterized in that: The phosphorus-containing epoxy resin includes one or both of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-modified epoxy resin and epoxy phosphate.

5. The photocurable resin according to claim 1, characterized in that: The phosphorus-containing acrylate has a phosphorus-containing functional group and at least two acrylate functional groups.

6. The photocurable resin according to claim 1, characterized in that: The free radical monomer includes one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer, and a multifunctional acrylate monomer.

7. The photocurable resin according to claim 1, characterized in that: The photoinitiator includes a free radical initiator and a cationic initiator; The free radical initiator includes one or more of free radical initiator 184, free radical initiator 1173, free radical initiator 2959, and 2-isopropylthioxanthone; The cationic initiator includes one or more of cationic initiator 6976, cationic initiator 6992, and cationic initiator 261.

8. A method for preparing the photocurable resin according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) mixing an epoxy resin composition, a phosphorus-containing epoxy resin, a phosphorus-containing acrylate, a free radical monomer, a photoinitiator and an auxiliary agent to obtain a mixture; (2) The mixture is subjected to vacuum degassing to obtain a photocurable resin.

9. The method for preparing a photocurable resin according to claim 8, characterized in that: When the photoinitiator includes a free radical initiator and a cationic initiator, the step (1) is: after mixing the epoxy resin composition, the phosphorus-containing epoxy resin and the cationic initiator, adding the free radical monomer, the phosphorus-containing acrylate and the free radical initiator, adding the auxiliary agent after mixing, and mixing again to obtain the mixture.

10. Use of the photocurable resin according to any one of claims 1 to 7 or the photocurable resin prepared by the preparation method according to any one of claims 8 to 9 in 3D printing.

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