Photocurable resin composition, preparation method and application thereof, photocurable resin material and application thereof

Abstract

The present invention relates to the field of organic light-curing technology, and discloses a kind of light-curing resin composition and its preparation method, light-curing resin material and its application. In parts by weight, the composition includes:3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylformate 10-20 parts, 3,7-bis(3-oxetane)-5-oxonane 1-5 parts, tri(ethylene glycol) divinyl ether 1-3 parts, tripropylene glycol monomethyl ether 1-3 parts, polyester-modified epoxy acrylate 25-45 parts, reactive diluent 20-22 parts, cationic photoinitiator 1-3 parts, free radical photoinitiator 4.5-6 parts, toughener 10-20 parts;The toughener is selected from epoxidation and / or terminal aldehyde epoxidized polyolefin liquid rubber.The light-curing resin material prepared by the composition has low volume shrinkage, high impact strength, tensile strength and gel fraction.

Description

Technical Field

[0001] The present invention relates to the field of organic photocuring technology, and in particular to a photocurable resin composition, a preparation method and application thereof, a photocurable resin material and application thereof. Background Art

[0002] Typically, the polymers generated by curing liquid photosensitive resin materials have a high cross-linking density, resulting in large shrinkage and warping of the molded products, low precision, and poor mechanical properties. In contrast, in a free radical-cationic hybrid photocuring system, free radical polymerization and cationic polymerization occur simultaneously in the reaction system under ultraviolet light. However, the mechanical properties of hybrid cured photocurable resins still need to be improved, and the product shrinkage rate cannot meet demand. Based on the current research status and development prospects of photocurable resins at home and abroad, the development of practical photocurable resins with high tensile strength and impact strength and low shrinkage has become a development trend in domestic photocurable resins.

[0003] In the field of photocuring, liquid rubber is usually used as a modifier to modify prepolymers such as epoxy acrylates or polyurethanes that can participate in photocuring reactions, thereby improving the mechanical properties of photocurable materials.

[0004] CN104449419B discloses a method for toughening photocurable materials using liquid rubber. Specifically, epoxidized hydroxyl-terminated polybutadiene liquid rubber is directly added to a free radical-cationic hybrid photocuring reaction system as a toughening agent. After uniform mixing and curing, the toughened material is achieved. However, the liquid rubber used in this patent is limited in type and range, and has a relatively high viscosity. Summary of the Invention

[0005] The present invention aims to address the problems of existing technologies, such as large shrinkage and warping, low precision, and poor mechanical properties in molded products, by providing a photocurable resin composition, a preparation method and application thereof, a photocurable resin material, and its application. The photocurable resin composition comprises an epoxidized and / or aldehyde-terminated epoxidized polyolefin liquid rubber as a toughening agent, and a cationic photoinitiator and a free radical photoinitiator as initiators. The composition significantly reduces the volume shrinkage of the photocurable resin material produced from the composition, while also improving the impact strength, tensile strength, and gel fraction of the photocurable resin material.

[0006] In order to achieve the above-mentioned object, the first aspect of the present invention provides a photocurable resin composition, characterized in that, in parts by weight, the composition comprises: 10-20 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 1-5 parts of 3,7-bis(3-oxetanyl)-5-oxonane, 1-3 parts of tri(ethylene glycol) divinyl ether, 1-3 parts of tripropylene glycol monomethyl ether, 25-45 parts of polyester-modified epoxy acrylate, 20-22 parts of reactive diluent, 1-3 parts of cationic photoinitiator, 4.5-6 parts of free radical photoinitiator, and 10-20 parts of toughening agent;

[0007] The toughening agent is selected from epoxidized and / or aldehyde-terminated epoxidized polyolefin liquid rubber.

[0008] A second aspect of the present invention provides a method for preparing the above-mentioned photocurable resin composition, characterized in that the method comprises the following steps:

[0009] (1) uniformly mixing 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and polyester-modified epoxy acrylate to obtain a mixed prepolymer;

[0010] (2) Under light-shielding conditions, a cationic photoinitiator, a free radical photoinitiator, 3,7-bis(3-oxetane)-5-oxonane, tri(ethylene glycol) divinyl ether, tripropylene glycol monomethyl ether, a toughening agent, an optional leveling agent, and an optional polymerization inhibitor are fully dissolved in a reactive diluent, and then the mixed prepolymer is added and stirred to obtain a photocurable resin composition.

[0011] A third aspect of the present invention provides a photocurable resin material, characterized in that the photocurable resin material is prepared from the above-mentioned photocurable resin composition.

[0012] A fourth aspect of the present invention provides use of the above-mentioned photocurable resin composition or the above-mentioned photocurable resin material in the field of photocuring rapid prototyping.

[0013] Through the above technical solution, the photocurable resin composition and preparation method thereof provided by the present invention, and the photocurable resin material prepared from the photocurable resin composition achieve the following beneficial effects:

[0014] The photocurable resin composition provided by the present invention uses epoxidized and / or terminal aldehyde epoxidized polyolefin liquid rubber as a toughening agent, and uses a cationic photoinitiator and a free radical photoinitiator as initiators. The volume shrinkage of the photocurable resin material prepared from the composition can be significantly reduced, and the impact strength, tensile strength and gel fraction of the photocurable resin material can be improved.

[0015] Furthermore, in the present invention, the introduction of the rubber phase of the toughening agent further improves the impact strength, tensile strength and gel fraction of the light-curable resin material.

[0016] Furthermore, the preparation process of the photocurable resin composition provided by the present invention is simple, and the performance of the photocurable resin composition is improved and its application field is further broadened. DETAILED DESCRIPTION

[0017] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0018] A first aspect of the present invention provides a photocurable resin composition, characterized in that the composition comprises, in parts by weight: 10-20 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 1-5 parts of 3,7-bis(3-oxetanyl)-5-oxonane, 1-3 parts of tri(ethylene glycol) divinyl ether, 1-3 parts of tripropylene glycol monomethyl ether, 25-45 parts of polyester-modified epoxy acrylate, 20-22 parts of a reactive diluent, 1-3 parts of a cationic photoinitiator, 4.5-6 parts of a free radical photoinitiator, and 10-20 parts of a toughening agent.

[0019] The toughening agent is selected from epoxidized and / or aldehyde-terminated epoxidized polyolefin liquid rubber.

[0020] In the present invention, the epoxidized polyolefin liquid rubber does not contain aldehyde-terminated epoxidized polyolefin liquid rubber.

[0021] In the present invention, the photocurable resin composition provided by the present invention contains a toughening agent epoxidized and / or terminal aldehyde epoxidized polyolefin liquid rubber, and uses a free radical photoinitiator and a cationic photoinitiator together as a photoinitiator. It can combine the advantages of free radical and cationic photocuring systems, so that the volume shrinkage of the photocurable resin material obtained by curing the composition is significantly reduced, thereby ensuring the dimensional stability of the obtained photocurable resin material.

[0022] Furthermore, in the present invention, epoxidized and / or terminal aldehyde epoxidized polyolefin liquid rubber is used as a toughening agent. The introduction of the rubber phase in the toughening agent further increases the gel fraction of the photocurable resin material prepared from the composition, thereby indicating that the prepared photocurable resin material has a high degree of crosslinking and improved mechanical properties.

[0023] Furthermore, when the amount of each component in the photocurable resin composition meets the above range, the mechanical properties of the photocurable resin composition, such as impact strength and tensile strength, can be significantly improved, and the volume shrinkage rate can be reduced.

[0024] According to the present invention, the composition includes, in parts by weight: 15-20 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 2-5 parts of 3,7-bis(3-oxetanyl)-5-oxonane, 1-3 parts of tri(ethylene glycol) divinyl ether, 2-3 parts of tripropylene glycol monomethyl ether, 25-32 parts of polyester-modified epoxy acrylate, 20-22 parts of active diluent, 2-3 parts of cationic photoinitiator, 4.5-6 parts of free radical photoinitiator, and 16-20 parts of toughening agent.

[0025] According to the present invention, the photocurable resin composition further comprises a leveling agent and / or a polymerization inhibitor.

[0026] Furthermore, the photocurable resin composition includes 2-3 parts of a leveling agent and / or 1-1.5 parts of a polymerization inhibitor.

[0027] According to the present invention, the number average molecular weight of the toughening agent is 1,000-30,000.

[0028] In the present invention, the use of epoxidized and / or aldehyde-terminated epoxidized polyolefin liquid rubber having a number average molecular weight that meets the above-mentioned range as a toughening agent for the photocurable resin composition can ensure that the liquid rubber has good dispersion in the resin and can form a good interpenetrating network with the resin matrix, thereby greatly improving the mechanical properties of the photocurable resin composition, such as impact strength and tensile strength.

[0029] Furthermore, the number average molecular weight of the toughening agent is 2000-10000.

[0030] Furthermore, the number average molecular weight of the toughening agent is 3000-8000.

[0031] According to the present invention, the toughening agent is selected from at least one of epoxidized or aldehyde-terminated epoxidized liquid polybutadiene rubber (LBR), epoxidized or aldehyde-terminated epoxidized liquid polyisoprene rubber (LIR), and epoxidized or aldehyde-terminated epoxidized liquid polybutadiene rubber (LIBR).

[0032] According to the present invention, the content of epoxy groups in the epoxidized and / or aldehyde-terminated epoxidized polyolefin liquid rubber is 10-15 wt % based on the total mass of the rubber.

[0033] According to the present invention, the functionality of the polyester-modified epoxy acrylate is 2-4; under the conditions of a solid content of 100 wt% and a temperature of 60° C., the viscosity of the polyester-modified epoxy acrylate is 3000-6500 cps.

[0034] According to the present invention, the reactive diluent is an acrylate reactive diluent.

[0035] In the present invention, in order to adjust the viscosity of the photocurable resin composition, an acrylate reactive diluent is preferably used as the reactive diluent used in the present invention. In particular, the acrylate reactive diluent is selected from at least one of 1,6-hexanediol diacrylate (HDDA), trimethylolpropane trimethacrylate (TMPTMA), tripropylene glycol diacrylate (TPGDA), ethoxylated trimethylolpropane triacrylate (EOTMPTA), pentaerythritol triacrylate (PETA), and carbitol acrylate. The above-mentioned specific type of acrylate reactive diluent contains multiple active functional groups, can directly participate in the photocuring reaction, can significantly improve the curing rate of the photocurable composition, and improve the film-forming performance of the composition.

[0036] Furthermore, the acrylate reactive diluent is 1,6-hexanediol diacrylate (HDDA), trimethylolpropane trimethacrylate (TMPTMA) and ethoxylated trimethylolpropane triacrylate (EOTMPTA).

[0037] In a specific embodiment of the present invention, the mass ratio of the 1,6-hexanediol diacrylate (HDDA), the trimethylolpropane trimethacrylate (TMPTMA) and the ethoxylated trimethylolpropane triacrylate (EOTMPTA) is 5-6:10-12:4-6, thereby further improving the comprehensive performance of the photocurable resin composition.

[0038] According to the present invention, the cationic photoinitiator is selected from sulfonium salt type photoinitiators and / or iodonium salt type photoinitiators.

[0039] In the present invention, the cationic photoinitiator is at least one selected from diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium hexafluoroarsenate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluoroarsenate and triarylsulfonium hexafluorophosphate.

[0040] In the present invention, the cationic photoinitiator is triarylsulfonium hexafluoroantimonate.

[0041] In the present invention, the triarylsulfonium hexafluoroantimonate is preferably dissolved in an organic solvent and introduced as a solution. The organic solvent can be a conventional organic solvent in the art, such as dimethyl carbonate. Specifically, the concentration of the triarylsulfonium hexafluoroantimonate solution is 45-55 wt%.

[0042] According to the present invention, the free radical photoinitiator is selected from at least one of 1-hydroxycyclohexyl benzophenone (184), 2-hydroxy-2-methyl-1-phenylpropanone (1173), (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TPO), a mixture of 2-isopropylthioxanthone (ITX) and ethyl 4-dimethylaminobenzoate (EDAB), and benzophenone (BP).

[0043] Furthermore, the free radical photoinitiator is a mixture of 2-isopropylthioxanthone and ethyl 4-dimethylaminobenzoate (EDAB).

[0044] In the present invention, the aforementioned specific types of cationic photoinitiators and free radical photoinitiators are used as composite photoinitiators for use in photocurable resin compositions. Ionium salts or sulfonium salts, commonly used in cationic systems, can generate active free radicals to initiate free radical photopolymerization under ultraviolet light, and can also generate Bronsted acids or Lewis acids to initiate cationic photopolymerization. However, the absorption wavelength of onium salts is mostly in the short-wavelength region of 250-300 nm, while the wavelength of commonly used UV lamps is mostly above 300 nm. Using cationic photoinitiators such as iodonium salts or sulfonium salts alone is not effective for crosslinking using UV radiation. Free radical photoinitiators, onium salts, have a sensitizing effect on the onium salts and can act synergistically with the cationic initiator onium salts. The composite photoinitiator efficiently absorbs radiation energy, thereby inducing chemical reactions between unsaturated double bonds in the system and enabling the composition to crosslink under irradiation by commonly used UV lamps, thereby improving the efficiency of radiation crosslinking in the photocurable resin.

[0045] According to the present invention, the leveling agent is selected from at least one of an organic silicon surface additive and an acrylate additive.

[0046] According to the present invention, the polymerization inhibitor is selected from 2,6-di-tert-butylphenol and / or p-methylphenol.

[0047] A second aspect of the present invention provides a method for preparing the above-mentioned photocurable resin composition, characterized in that the method comprises the following steps:

[0048] (1) uniformly mixing 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and polyester-modified epoxy acrylate to obtain a mixed prepolymer;

[0049] (2) Under light-shielding conditions, a cationic photoinitiator, a free radical photoinitiator, 3,7-bis(3-oxetane)-5-oxonane, tri(ethylene glycol) divinyl ether, tripropylene glycol monomethyl ether, a toughening agent, an optional leveling agent, and an optional polymerization inhibitor are fully dissolved in a reactive diluent, and then the mixed prepolymer is added and stirred to obtain a photocurable resin composition.

[0050] In the present invention, the preparation method of the photocurable resin composition provided by the present invention has a simple process and ensures that the obtained photocurable resin composition and the photocurable resin material prepared from the photocurable resin composition have improved performance and can be applied to the needs of different fields.

[0051] In the present invention, the preparation method further comprises: weighing raw materials according to a weight ratio at room temperature.

[0052] According to the present invention, in step (2), the stirring conditions include: stirring temperature: 40-60°C, stirring time: 1-2h.

[0053] In the present invention, in order to prevent the light in the environment from adversely affecting the performance of the photocurable resin composition, preferably, the preparation method further comprises: placing the photocurable resin composition in a dark environment for static degassing.

[0054] Preferably, in step (2), the stirring conditions include: stirring temperature of 50-60° C., and stirring time of 1.5-2 h.

[0055] A third aspect of the present invention provides a photocurable resin material, characterized in that the photocurable resin material is prepared from the above-mentioned photocurable resin composition.

[0056] A fourth aspect of the present invention provides use of the above-mentioned photocurable resin composition or the above-mentioned photocurable resin material in the field of photocuring rapid prototyping.

[0057] In one embodiment of the present invention, the photocurable resin material is prepared according to the following steps: taking an appropriate amount of photocurable reaction liquid, dropping it onto a glass sheet, controlling the thickness of the cured layer to 0.2-0.5 mm, placing it in a UV curing machine for photocuring, and preparing the photocurable resin material.

[0058] In the present invention, the conditions for light curing include: a light curing machine power of 1000-1500W, a main emission wavelength of 365nm and 385nm, an irradiation distance of 20-25cm, and a temperature of 20-30°C.

[0059] The present invention will be described in detail below by way of examples.

[0060] Impact strength: tested in accordance with GB / T1043.1-2008 standard.

[0061] Tensile strength and elongation at break: Prepare 5 specimens of size 60×10×4mm according to Type I specimen in GB / T1042-92. 3 The dumbbell-shaped molding block was used to test the tensile strength and elongation at break of the cured material using a universal mechanical testing machine with a loading speed of 5 mm / min.

[0062] Volume shrinkage: The density of the resin system before curing ρ1 and the density after complete curing ρ2 are measured by the pycnometer method at room temperature. The volume shrinkage % = (ρ2-ρ1) / ρ2×100%

[0063] Gel content: The gel content is tested by acetone extraction method. Place the solidified film (mass m0) in a Soxhlet extractor, soak and extract with acetone for 8 hours, dry at 100℃ to constant weight, weigh its mass m1, and calculate η 凝胶 =(m1 / m0)×100%.

[0064] 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, purchased from Adamas;

[0065] 3,7-Bis(3-oxetanyl)-5-oxononane, purchased from Ark Pharm;

[0066] tri(ethylene glycol) divinyl ether (DVE-3), purchased from Sigma-Aldrich;

[0067] Tripropylene glycol monomethyl ether, purchased from Aladdin;

[0068] Polyester-modified epoxy acrylate CM3225, solid content 100 wt%, functionality 2, viscosity 5500 cps at 60°C, Guangzhou Chenglan Materials Technology Co., Ltd.

[0069] The leveling agent is the silicone surface additive BYK-UV3570, BYK Chemical Co., Ltd., Germany;

[0070] Cationic photoinitiator, triarylsulfonium hexafluoroantimonate in dimethyl carbonate solution, mass concentration 50 wt%, purchased from Sigma-Aldrich;

[0071] Epoxidized polybutadiene liquid rubber, number average molecular weight 8000, epoxy group content 12wt%, homemade;

[0072] The aldehyde-terminated epoxidized polybutadiene liquid rubber has a number average molecular weight of 4700 and an epoxy group content of 10 wt%, and is self-made;

[0073] Epoxidized polyisoprene liquid rubber, number average molecular weight 6500, epoxy group content 15wt%, homemade;

[0074] Formaldehyde-terminated epoxidized polyisoprene liquid rubber with a number average molecular weight of 7200 and an epoxy group content of 11 wt% was prepared in-house;

[0075] Epoxidized polybutadiene-pentadiene liquid rubber, number average molecular weight 5400, epoxy group content 14wt%, homemade;

[0076] The aldehyde-terminated epoxidized polybutadiene-pentene liquid rubber has a number average molecular weight of 3000 and an epoxy group content of 10 wt%, and is self-made.

[0077] Other raw materials used in the examples and comparative examples are all commercially available.

[0078] The specific experiments of Examples 1-8 and Comparative Examples 1-5 include the following steps:

[0079] All raw materials were weighed in parts by weight according to the ratio in Table 1, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and CM3225 were added to a container respectively, and magnetically stirred under light-proof conditions until mixed evenly to obtain a mixed prepolymer; then the photoinitiator, 3,7-bis(3-oxetane)-5-oxonane, tri(ethylene glycol) divinyl ether (DVE-3), tripropylene glycol monomethyl ether, leveling agent, inhibitor and toughening agent were fully dissolved in the diluent, and the above-mentioned mixed prepolymer was added, and stirred in the dark for 2 hours at 50°C. After the components were evenly mixed, a light-curing resin composition was obtained, which was placed in a dark environment for degassing.

[0080] Prepare the photocurable resin composition according to the formula shown in Table 1

[0081] Table 1

[0082]

[0083]

[0084] Table 1 (continued)

[0085]

[0086]

[0087] Test Case

[0088] An appropriate amount of the photocurable resin composition of Examples 1-8 and Comparative Examples 1-5 was added dropwise onto a glass sheet to a cured layer thickness of 0.5 mm. The resulting material was then placed in a 1000 W UV curing machine (main emission wavelengths of 365 nm and 385 nm, irradiation distance of 20 cm) and cured at room temperature to obtain a photocurable resin material. The properties of the photocurable resin material were tested, and the results are shown in Table 2.

[0089] Table 2

[0090] <![CDATA[Impact strength / KJ·m 2 > Elongation at break / % Tensile strength / MPa Gel rate / % Volume shrinkage / % Example 1 27.1 26.2 41 92 4.2 Example 2 28.2 27 44 91 4.8 Example 3 25.7 26.9 39 88 4.5 Example 4 36.7 35.2 48 93 3.9 Example 5 40.5 38 51 95 3.8 Example 6 50.9 47.9 59 94 3.5 Example 7 53.2 48.9 54 94 3.2 Example 8 55.1 50.5 61 96 3.1 Comparative Example 1 10.5 6.6 30 80 6.5 Comparative Example 2 19.7 19.0 44 88 4.9 Comparative Example 3 24.4 20.3 30 86 5.0 Comparative Example 4 20.5 11.6 32 40 4.8 Comparative Example 5 33.9 13.5 41 53 4.3

[0091] As can be seen from Table 2, compared with Comparative Examples 1-5, the photocurable compositions described in Examples 1-8 of the present invention, which use epoxidized and / or terminal aldehyde epoxidized polyolefin liquid rubber as a toughening agent and simultaneously add free radical photoinitiators and cationic photoinitiators as photoinitiators, have improved impact strength, tensile strength and gel fraction of the obtained photocurable resins after curing.

[0092] Specifically, compared with Comparative Example 1, in Examples 1, 2, and 3 to which the epoxidized and / or terminal aldehyde epoxidized polyolefin liquid rubber toughener, cationic photoinitiator, and free radical photoinitiator were added at the same time, the impact strength was increased by up to 169%, the tensile strength was increased by up to 47%, the elongation at break was increased by up to 4 times, the gel fraction was increased from 80% to 92%, and the volume shrinkage was reduced from 6.5% to 4.2%. This indicates that the photocurable resin material has a high degree of cross-linking and improved mechanical properties.

[0093] It can be seen from Examples 4-8 that when the amount of each component in the photocurable resin composition meets the more preferred range of the present invention, the composition system has an appropriate viscosity, is easy to operate, and the liquid rubber is well dispersed in the resin and forms an interpenetrating network in the resin matrix, which greatly improves the mechanical properties of the photocurable resin composition, such as impact strength.

[0094] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A photocurable resin composition, characterized in that The composition comprises, in parts by weight: 15-20 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 2-5 parts of 3,7-bis(3-oxetanyl)-5-oxonane, 1-3 parts of tri(ethylene glycol) divinyl ether, 2-3 parts of tripropylene glycol monomethyl ether, 25-32 parts of polyester-modified epoxy acrylate, 20-22 parts of reactive diluent, 2-3 parts of cationic photoinitiator, 4.5-6 parts of free radical photoinitiator, and 16-20 parts of toughening agent. The toughening agent is selected from epoxidized polyolefin liquid rubber and / or terminal aldehyde epoxidized polyolefin liquid rubber; The epoxy group content of the epoxidized or aldehyde-terminated epoxidized polyolefin liquid rubber is 10-15 wt % based on the total mass of the rubber.

2. The photocurable resin composition according to claim 1, wherein The photocurable resin composition further includes a leveling agent and / or a polymerization inhibitor.

3. The photocurable resin composition according to claim 2, wherein The photocurable resin composition further comprises 2-3 parts of a leveling agent and / or 1-1.5 parts of a polymerization inhibitor.

4. The photocurable resin composition according to claim 1 or 2, wherein The number average relative molecular mass of the toughening agent is 1000-30000.

5. The photocurable resin composition according to claim 4, wherein The number average relative molecular mass of the toughening agent is 2000-10000.

6. The photocurable resin composition according to claim 5, wherein The number average relative molecular mass of the toughening agent is 3000-8000.

7. The photocurable resin composition according to claim 1 or 2, wherein The toughening agent is selected from at least one of epoxidized or aldehyde-terminated epoxidized liquid polybutadiene rubber, epoxidized or aldehyde-terminated epoxidized liquid polyisoprene rubber, and epoxidized or aldehyde-terminated epoxidized liquid polybutadiene rubber.

8. The photocurable resin composition according to claim 1 or 2, wherein The functionality of the polyester-modified epoxy acrylate is 2-4; under the conditions of a solid content of 100 wt % and a temperature of 60° C., the viscosity of the polyester-modified epoxy acrylate is 3000-6500 cps.

9. The photocurable resin composition according to claim 1 or 2, wherein The active diluent is an acrylic acid ester active diluent.

10. The photocurable resin composition according to claim 9, wherein The acrylate reactive diluent is selected from at least one of 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, tripropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate and carbitol acrylate.

11. The photocurable resin composition according to claim 10, wherein The acrylic ester active diluents are 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane triacrylate.

12. The photocurable resin composition according to claim 11, wherein The mass ratio of the 1,6-hexanediol diacrylate, the trimethylolpropane trimethacrylate and the ethoxylated trimethylolpropane triacrylate is 5-6:10-12:4-6.

13. The photocurable resin composition according to claim 1 or 2, wherein The cationic photoinitiator is selected from sulfonium salt type photoinitiators and / or iodonium salt type photoinitiators.

14. The photocurable resin composition according to claim 13, wherein The cationic photoinitiator is at least one selected from diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, diaryliodonium hexafluoroarsenate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluoroarsenate and triarylsulfonium hexafluorophosphate.

15. The photocurable resin composition according to claim 14, wherein The cationic photoinitiator is triarylsulfonium hexafluoroantimonate.

16. The photocurable resin composition according to claim 1 or 2, wherein The free radical photoinitiator is selected from at least one of 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-phenylpropanone, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, a mixture of 2-isopropylthioxanthone and ethyl 4-dimethylaminobenzoate, and benzophenone.

17. The photocurable resin composition according to claim 16, wherein The free radical photoinitiator is a mixture of 2-isopropylthioxanthone and ethyl 4-dimethylaminobenzoate.

18. The photocurable resin composition according to claim 2 or 3, wherein The leveling agent is selected from silicone surface additives and / or acrylic additives.

19. The photocurable resin composition according to claim 2 or 3, characterized in that: The polymerization inhibitor is 2,6-di-tert-butylphenol and / or p-methylphenol.

20. A method for preparing the photocurable resin composition according to any one of claims 1 to 19, characterized in that: The method comprises the following steps: (1) uniformly mixing 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate and polyester-modified epoxy acrylate to obtain a mixed prepolymer; (2) Under light-shielding conditions, after fully dissolving the cationic photoinitiator, the free radical photoinitiator, 3,7-bis(3-oxetane)-5-oxonane, tri(ethylene glycol) divinyl ether, tripropylene glycol monomethyl ether, a toughening agent, an optional leveling agent and an optional polymerization inhibitor in a reactive diluent, the mixed prepolymer is added and stirred to obtain a photocurable resin composition.

21. The preparation method according to claim 20, wherein In step (2), the stirring conditions include: stirring temperature of 40-60°C and stirring time of 1-2h.

22. A light-curable resin material, characterized in that: The photocurable resin material is prepared from the photocurable resin composition according to any one of claims 1 to 19.

23. Use of the photocurable resin composition according to any one of claims 1 to 19 or the photocurable resin material according to claim 22 in the field of photocuring rapid prototyping.

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