Photocurable 3D printing material and method for preparing the same

Abstract

The application provides a photocuring 3D printing material and a preparation method thereof. The material is prepared by using a photocuring oligomer, an active diluent, a photoinitiator and an additive. The photocuring oligomer is capped by a long chain structure, and the prepared photocuring 3D printing material has the characteristics of low viscosity, good flexibility, fast curing speed, high forming precision and good surface curing effect, and is suitable for a photocuring 3D printer.

Description

Technical Field

[0001] This invention belongs to the field of 3D printing technology, and particularly relates to a photopolymerizable 3D printing material and its preparation method. Technical Background

[0002] 3D printing technology is a rapidly developing emerging technology in the manufacturing industry. The manufacturing principle of 3D printing is based on the concept of "additive manufacturing," which is fundamentally different from traditional processing methods that use cutting, grinding, and stamping to form products. Using only three-dimensional design data, 3D printing can quickly and accurately manufacture parts of any complex shape on a single machine. Currently, the mainstream 3D printing technologies include photopolymerization, selective laser sintering (SLS), and fused deposition modeling (FDM), among which photopolymerization 3D printing technology is the most mature and offers the highest printing precision.

[0003] Photopolymer 3D printing utilizes photosensitive resins, whose properties determine the precision, mechanical properties, and thermal properties of the molded parts. Currently, most commercially available photopolymer 3D printing resins developed by domestic and international material companies are high-hardness, high-strength, high-temperature resistant, but with poor toughness. With the rapid development and large-scale application of photopolymer 3D printing technology, material properties will inevitably limit its application scope and development. Therefore, developing flexible photopolymer 3D printing materials is of great significance for expanding the market demand for flexible materials in toy manufacturing, medical fields, and wearable devices.

[0004] Currently, flexible photopolymer 3D printing materials suffer from low strength and poor surface curing effects. These problems are mainly addressed by heating and curing, adding inorganic nanomaterials, and using large amounts of organic solvents for cleaning. However, these methods have drawbacks such as increased costs and inability to balance product flexibility and hardness. Summary of the Invention

[0005] The purpose of this invention is to provide a high-gloss curing 3D printing material and its preparation method. This material has the characteristics of low viscosity, good flexibility, fast curing speed, high molding accuracy, and good surface curing effect.

[0006] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:

[0007] A photopolymerizable 3D printing material, said material being prepared from raw materials comprising the following components:

[0008]

[0009] This invention introduces a long-chain acrylamide end-capping agent, which can directly react with isocyanate as a flexible segment to generate photocurable oligomers, simplifying the synthesis process. Compared with traditional small-molecule end-capping agents, the long-chain end-capping agent has better toughness. The acrylamide end-capping agent contains amino groups, which effectively reduce oxygen inhibition, increase curing speed, improve surface curing effect, and give the product surface good dryness. The photocurable oligomers prepared with the long-chain acrylamide end-capping agent have good compatibility with common photoinitiators and reactive diluents, and can prepare stable photocurable products.

[0010] In this invention, the photocurable oligomer is polyurethane (meth)acrylate; preferably, the photocurable oligomer is prepared by diisocyanate, acrylamide end-capping agent, and optional soft segment compound; preferably, the diisocyanate used in the photocurable oligomer is one or more of toluene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; preferably, the acrylamide end-capping agent used in the photocurable oligomer is one or more of amino polyethylene glycol (meth)acrylamide, hydroxyl polyethylene glycol (meth)acrylamide, and amino polytetrahydrofuran ether glycol (meth)acrylamide; preferably, the number-average molecular weight of the end-capping agent is 200-4000; preferably, the photocurable oligomer uses one or more of polyol polyether polyol, polyester polyol, hydroxyl-terminated polybutadiene, hydroxyl-terminated styrene-butadiene rubber, hydroxyl-terminated butadiene-acrylonitrile rubber, and hydroxyl-terminated polysiloxane as the soft segment; preferably, the number-average molecular weight of the soft segment compound is 1000-6000.

[0011] In this invention, the reactive diluent is an acrylate reactive diluent and / or a vinyl ether reactive diluent; wherein, the acrylate reactive diluent is preferably one or more of the following: tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclotrimethylolpropane methyl acetal acrylate, isobornyl acrylate, and acryloylmorpholine; the vinyl ether reactive diluent is preferably one or more of the following: 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexyldiethanol divinyl ether, and dodecyl vinyl ether.

[0012] In this invention, the photoinitiator is one or more of benzophenone and its derivatives, thioxanthones, anthraquinones, and arylalkyl ketones, preferably one or more of benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexylbenzophenone, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholino-1-propanone, 2-hydroxy-2-methyl-phenylpropanone-1, 2,4,6,-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6,-trimethylbenzoyl)phenylphosphine oxide, and 2,4-diethylthioxanthone.

[0013] In this invention, the additive is one or more of leveling agents, defoamers, and wetting and dispersing agents.

[0014] Another objective of this invention is to provide a method for preparing photopolymerizable 3D printing materials.

[0015] A method for preparing the above-mentioned photopolymerizable 3D printing material, wherein the method is Method I:

[0016] Diisocyanate is added to polyol to react and obtain terminal isocyanate prepolymer; end-capping agent is added to prepolymer to obtain (meth)acrylate oligomer; oligomer is mixed with reactive diluent, photoinitiator and additives to obtain photocurable 3D printing material;

[0017] Alternatively, the method described is method II:

[0018] A capping agent is added to diisocyanate to react and obtain a photocurable oligomer; the oligomer is mixed with an active diluent, a photoinitiator and an additive to obtain a photocurable 3D printing material.

[0019] In this invention, the polyol in method I is one or more of polyether polyol, polyester polyol, hydroxyl-terminated polybutadiene, hydroxyl-terminated styrene-butadiene rubber, hydroxyl-terminated butadiene-acrylonitrile rubber, and hydroxyl-terminated polysiloxane.

[0020] In this invention, the diisocyanate in Method I is one or more of toluene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; preferably, the molar ratio of diisocyanate to polyol in Method I is 2 to 2.1:1.

[0021] In this invention, in Method I, after adding a catalyst, the diisocyanate and polyol react at 60-80°C for 2-4 hours.

[0022] In this invention, the capping agent in Method I is one or more of amino polyethylene glycol (meth)acrylamide, hydroxy polyethylene glycol (meth)acrylamide, and amino polytetrahydrofuran ether glycol (meth)acrylamide; preferably, the molar ratio of the capping agent to the polyol in Method I is 1.95 to 2.05:1.

[0023] In this invention, the capping agent reacts with the polyol in method I for 2 to 4 hours.

[0024] In this invention, in method I, the oligomer is stirred and mixed evenly with the reactive diluent, photoinitiator, and additives.

[0025] In this invention, the diisocyanate in Method II is one or more of toluene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

[0026] In this invention, the capping agent in Method II is one or more of amino polyethylene glycol (meth)acrylamide, hydroxy polyethylene glycol (meth)acrylamide, and amino polytetrahydrofuran ether glycol (meth)acrylamide; preferably, the molar ratio of diisocyanate to capping agent in Method II is 1:2 to 2.1.

[0027] In this invention, in Method II, after the diisocyanate and the capping agent are added to the catalyst, they are reacted at 60-80°C for 2-4 hours.

[0028] In this invention, in method II, the oligomer is stirred and mixed evenly with the reactive diluent, photoinitiator, and additives.

[0029] Another object of the present invention is to provide an application of a photopolymerizable 3D printing material.

[0030] An application of a photocurable 3D printing material, wherein the material is the aforementioned photocurable 3D printing material, or a photocurable 3D printing material prepared by the aforementioned preparation method, and the material is used in the fields of photocurable 3D printing materials, photocurable coatings, and adhesives.

[0031] Compared with the prior art, the positive effects of the present invention are as follows:

[0032] (1) The introduction of long-chain end-capping agents can better balance the flexibility and hardness of the material. When the Shore hardness is 75A, the tear strength can reach 3.2kN / m.

[0033] (2) The end-capping agent is a long-chain acrylate, which combines the functions of end-capping agent and flexible chain segment. It can directly react with isocyanate to synthesize photocurable oligomers, simplifying the synthesis process.

[0034] (3) The end-capping agent contains amino groups, which reduces oxygen inhibition, increases curing speed, improves surface curing effect, and makes the surface of the product have good dryness. Specific Implementation

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] In the following embodiments, the main equipment is as follows:

[0037] Mixing equipment: RW20 digital, IKA

[0038] Mixing equipment: DAC600.2 VAC-LR, SpeedMixer

[0039] 3D Printer: REALMAKER-M, Yiwu Zhuzhen Electronic Technology Co., Ltd.

[0040] Cleaning equipment: FRQ-1006HT, Ultrasonic Cleaner

[0041] Post-curing oven: REALMAKER, Yiwu Zhuzhen Electronic Technology Co., Ltd.

[0042] Multi-purpose tensile testing machine: GT-AI-3000, GOTECH

[0043] Hardness tester: LX-A, Shanghai Liuling Instrument Factory

[0044] Viscometer: HB, BROOKFIELD

[0045] In the following embodiments, the main test characterization methods are as follows:

[0046] Surface curing effect: by touch

[0047] Tensile properties: ISO 37, Type II, 500 mm / min

[0048] Tear resistance: ASTM D624, Die C, 500 mm / min

[0049] In the following embodiments, the main raw materials are sourced from the following sources:

[0050] Hydroxyl-terminated polybutadiene GI-1000: Nippon Soda Co., Ltd., industrial product.

[0051] Polytetrahydrofuran ether diol (Poly THF 2000): BASF, industrial grade.

[0052] Polypropylene glycol DL6000: Lanxing Dongda, industrial product.

[0053] Isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), toluene diisocyanate (TDI80): Wanhua Chemical, industrial products.

[0054] Amino-polyethylene glycol acrylamide (NH2-PEG200-ACA), amino-polytetrahydrofuran ether glycol acrylamide (NH2-PTMEG200-ACA), amino-polytetrahydrofuran ether glycol acrylamide (NH2-PTMEG3000-ACA): Shanghai Tuoyang Biotechnology, industrial products.

[0055] Hydroxy-coated polyethylene glycol acrylamide (HO-PEG200-ACA), hydroxy-coated polyethylene glycol acrylamide (HO-PEG2000-ACA): Xi'an Qiyue Biotechnology, industrial products.

[0056] Polyethylene glycol (400) diacrylate SR344, cyclotrimethylolpropane methyl acetal acrylate SR550, dipropylene glycol diacrylate SR205NS, polyethylene glycol (600) diacrylate (SR610 NS), trimethylolpropane triacrylate (SR350NS), lauryl methacrylate (SR313A), 2(2-ethoxyethoxy)ethyl acrylate (SR256): Sartoma, industrial grade.

[0057] 4-Hydroxybutylvinyl ether, hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA): Aladdin, reagent grade.

[0058] Reactive diluent 6105: Dongguan Sanqi Chemical Co., Ltd., industrial product.

[0059] 2,4,6-Trimethylbenzoyl-diphenylphosphine oxide (photoinitiator TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (photoinitiator 819), benzophenone (photoinitiator BP): Tianjin Jiuri, industrial products.

[0060] TEGO FOAMEX 810: Tego, industrial products.

[0061] BYK3505: BYK, industrial products.

[0062] Acrylic resin BRS-14320: Demas, industrial product.

[0063] Dibutyltin dilaurate: Kaiyin Chemical, industrial products.

[0064] Example 1

[0065] Synthesis of polyurethane acrylate: Take 1 mol of diol compound GI-1000 (number average molecular weight 1000) and add it to 2.05 mol of IPDI. Mix rapidly at 10℃ for 15 minutes. Add 0.03% by mass of dibutyltin dilaurate, and then heat to 75℃ and react for 2.5 hours.

[0066] Add 2.01 mol of NH2-PEG200-ACA (number average molecular weight 200) to the above product, and continue the reaction at 60°C for 4 hours to obtain a photocurable oligomer.

[0067] Take 40g of the above-synthesized resin and mix it with 10g SR344, 10g SR550, 9g reactive diluent 6105, 5g 4-hydroxybutylvinyl ether, 13g SR256, 10g SR205NS, 2g photoinitiator TPO, 0.3g TEGO FOAMEX 810, and 0.7g BYK3505 until homogeneous to obtain photocurable 3D printing material.

[0068] Example 2

[0069] Synthesis of polyurethane acrylate: Take 1 mol of diol compound Poly THF 2000 (number average molecular weight 2000) and add it to 2 mol of HMDI. Mix rapidly at 10℃ for 15 minutes. Add 0.03% by mass of dibutyltin dilaurate, and then heat to 60℃ and react for 4 hours.

[0070] Add 2.03 mol of HO-PEG200-ACA (number average molecular weight 200) to the above product, heat to 75℃ and continue the reaction for 2 hours to obtain the photocurable oligomer.

[0071] Take 30g of the above-synthesized resin and mix it with 40g of SR344, 10g of SR550, 9g of reactive diluent 6105, 9g of SR610NS, 1g of photoinitiator TPO, and 1g of photoinitiator 819 until homogeneous to obtain photocurable 3D printing material.

[0072] Example 3

[0073] Synthesis of polyurethane acrylate: Take 1 mol of diol compound DL6000 (number average molecular weight 6000) and add it to 2 mol of TDI80. Mix rapidly at 10℃ for 15 minutes. Add 0.03% by mass of dibutyltin dilaurate, and then heat to 75℃ and react for 2.5 hours.

[0074] Add 2 mol of NH2-PTMEG200-ACA (number average molecular weight 200) to the above product and continue the reaction for 4 hours to obtain the photocurable oligomer.

[0075] Take 40g of the above-synthesized resin and mix it with 40g of SR344, 10g of SR550, 9g of reactive diluent 6105, 0.7g of photoinitiator TPO, and 0.3g of TEGO FOAMEX 810 until homogeneous to obtain photocurable 3D printing material.

[0076] Example 4

[0077] First, a polyurethane acrylate was synthesized: 1 mol HMDI was taken, and 0.95 mol HO-PEG200-ACA (number average molecular weight 200) and 1 mol HO-PEG2000-ACA (number average molecular weight 2000) were added. The mixture was rapidly mixed at 10℃ for 15 minutes. Then, 0.03% by mass of dibutyltin dilaurate was added, and the temperature was raised to 75℃. The reaction was carried out for 2.5 hours to obtain a photocurable oligomer.

[0078] Take 35g of the above-synthesized resin and mix it with 30g SR344, 5g SR550, 9g reactive diluent 6105, 5g SR350NS, 15g SR313A, 0.7g photoinitiator 819 and 0.3g photoinitiator BP until homogeneous to obtain photocurable 3D printing material.

[0079] Example 5

[0080] First, a polyurethane acrylate was synthesized: 1 mol HMDI was taken, and 1 mol NH2-PEG200-ACA (number average molecular weight 200) and 1 mol NH2-PTMEG3000-ACA (number average molecular weight 3000) were added. The mixture was rapidly mixed at 10℃ for 15 minutes. Then, 0.03% by mass of dibutyltin dilaurate was added, and the temperature was raised to 70℃. The reaction was carried out for 2.5 hours to obtain a photocurable oligomer.

[0081] Take 30g of the above-synthesized resin and mix it with 30g of SR344, 10g of SR550, 29g of reactive diluent 6105, 0.7g of TPO, and 0.3g of TEGO FOAMEX 810 until homogeneous to obtain photocurable 3D printing material.

[0082] Example 6

[0083] Take 20g of the resin synthesized in Example 3, and mix it with 40g of SR344, 10g of SR550, 29g of reactive diluent 6105, 0.7g of photoinitiator 819 and 0.3g of TEGO FOAMEX 810 until homogeneous to obtain photocurable 3D printing material.

[0084] Example 7

[0085] Take 79g of the resin synthesized in Example 3, and mix it with 10g of SR344, 5g of SR550, 4g of reactive diluent 6105 and 2g of photoinitiator 819 until homogeneous to obtain photocurable 3D printing material.

[0086] Comparative Example 1

[0087] Compared to Example 1, the synthesis process of Comparative Example 1 used the conventional small molecule capping agent HEA.

[0088] Synthesis of polyurethane acrylate: Take 1 mol of diol compound GI-1000 (number average molecular weight 1000) and add it to 2.05 mol of IPDI. Mix rapidly at 10℃ for 15 minutes. Add 0.03% by mass of dibutyltin dilaurate, and then heat to 75℃ and react for 2.5 hours.

[0089] 2.01 mol HEA was added to the above product, and the reaction was continued at 60°C for 4 hours to obtain the photocurable oligomer.

[0090] Take 40g of the above-synthesized resin and mix it with 10g SR344, 10g SR550, 9g reactive diluent 6105, 5g 4-hydroxyvinyl ether, 13g SR256, 10g SR205NS, 2g photoinitiator TPO, 0.3g TEGO FOAMEX 810, and 0.7g BYK3505 until homogeneous to obtain photocurable 3D printing material.

[0091] Comparative Example 2

[0092] Compared to Example 2, the synthesis process of Comparative Example 2 used the conventional small molecule capping agent HEMA.

[0093] Synthesis of polyurethane acrylate: Take 1 mol of diol compound Poly THF 2000 (number average molecular weight 2000) and add it to 2 mol of HMDI. Mix rapidly at 10℃ for 15 minutes. Add 0.03% by mass of dibutyltin dilaurate, and then heat to 60℃ and react for 4 hours.

[0094] 2.03 mol HEMA was added to the above product, and the temperature was raised to 75°C and the reaction was continued for 2 hours to obtain the photocurable oligomer.

[0095] Take 30g of the above-synthesized resin and mix it with 40g of SR344, 10g of SR550, 9g of reactive diluent 6105, 9g of SR610NS, 1g of photoinitiator TPO, and 1g of photoinitiator 819 until homogeneous to obtain photocurable 3D printing material.

[0096] Comparative Example 3

[0097] Compared to Example 3, the synthesis process of Comparative Example 3 used the conventional small molecule capping agent HPA.

[0098] Synthesis of polyurethane acrylate: Take 1 mol of diol compound DL6000 (number average molecular weight 6000) and add it to 2 mol of TDI80. Mix rapidly at 10℃ for 15 minutes. Add 0.03% by mass of dibutyltin dilaurate, and then heat to 75℃ and react for 2.5 hours.

[0099] Add 2 mol HPA to the above product and continue the reaction for 4 hours to obtain a photocurable oligomer.

[0100] Take 40g of the above-synthesized resin, and mix it with 40g of SR344, 10g of SR550, 9g of reactive diluent 6105, 0.7g of photoinitiator TPO, and 0.3g of TEGO FOAMEX 810 until homogeneous to obtain photocurable 3D printing material.

[0101] Comparative Example 4

[0102] Compared to Example 6, the resin in Comparative Example 4 was synthesized using the conventional small molecule capping agent HPA.

[0103] Take 20g of the resin synthesized in Comparative Example 3, and mix it with 40g SR344, 10g SR550, 29g reactive diluent 6105, 0.7g photoinitiator TPO, and 0.3g TEGO FOAMEX 810 until homogeneous to obtain photocurable 3D printing material.

[0104] Comparative Example 5

[0105] Compared to Example 7, the resin in Comparative Example 5 was synthesized using the conventional small molecule capping agent HPA.

[0106] Take 79g of the resin synthesized in Comparative Example 3, and mix it with 10g of SR344, 5g of SR550, 4g of reactive diluent 6105 and 2g of photoinitiator TPO until homogeneous to obtain photocurable 3D printing material.

[0107] The 3D printing resins prepared in Examples 1-7 and Comparative Examples 1-5 were used to print test samples using a 3D printer. After printing, the samples were immersed in alcohol, ultrasonically cleaned for 3 minutes, and then irradiated with light from both sides in a light curing chamber for 5 minutes. The viscosity, surface curing effect, folding cracking, hardness, and mechanical properties of the 3D printing resins were tested. The toughness of the resin was characterized by folding cracking and tear strength.

[0108] The performance indicators of the 3D printing resin prepared in the examples and the printed samples are shown in Table 1. As can be seen from Table 1, compared with the comparative examples, under the condition of similar mechanical properties, the 3D printing resin prepared in this invention has excellent surface curing effect and toughness.

[0109] Table 1 Performance indicators of 3D printing resin and printed samples

[0110]

[0111] Compared with Comparative Example 1, Example 2, Example 3, Example 6, and Example 4, and Example 7, under similar conditions of hardness and mechanical properties, the surfaces of Examples 1 and 7 cured dry and did not crack when folded, indicating that Examples 7 have better surface curing effects while maintaining good hardness and toughness. The synthesis process of Examples 4-5 only requires one step, making it simpler and faster than Comparative Examples 1-3.

[0112] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A photopolymerizable 3D printing material, characterized in that, The material is prepared from raw materials containing the following components: The photocurable oligomer is a polyurethane (meth)acrylate, prepared by diisocyanate, acrylamide end-capping agent and optional soft segment compound, wherein the acrylamide end-capping agent is one or more of amino polyethylene glycol (meth)acrylamide, hydroxy polyethylene glycol (meth)acrylamide and amino polytetrahydrofuran ether glycol (meth)acrylamide.

2. The material according to claim 1, characterized in that, The photocurable oligomer uses one or more of toluene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

3. The material according to claim 2, characterized in that, The number-average molecular weight of the capping agent is 200–4000; The photocurable oligomer uses one or more of the following as soft segments: polyol polyether polyol, polyester polyol, hydroxyl-terminated polybutadiene, hydroxyl-terminated styrene-butadiene rubber, hydroxyl-terminated butadiene-acrylonitrile rubber, and hydroxyl-terminated polysiloxane.

4. The material according to claim 3, characterized in that, The number-average molecular weight of soft segment compounds is 1000–6000.

5. The material according to claim 1 or 2, characterized in that, The reactive diluent is an acrylate reactive diluent and / or a vinyl ether reactive diluent.

6. The material according to claim 5, characterized in that, The acrylate reactive diluents are one or more of the following: tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, cyclotrimethylolpropane methyl acetal acrylate, isobornyl acrylate, and acryloylmorpholine; the vinyl ether reactive diluents are one or more of the following: 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, 1,4-cyclohexyldiethanol divinyl ether, and dodecyl vinyl ether.

7. The material according to claim 1, characterized in that, The photoinitiator is one or more of benzophenone and its derivatives, thioxanthones, anthraquinones, and arylalkyl ketones.

8. The material according to claim 7, characterized in that, The photoinitiator is one or more of the following: benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexylbenzophenone, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholino-1-propanone, 2-hydroxy-2-methyl-phenylpropanone-1, 2,4,6,-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6,-trimethylbenzoyl)phenylphosphine oxide, and 2,4-diethylthioxanthrone.

9. The material according to claim 1, characterized in that, The additive is one or more of the following: leveling agent, defoamer, and wetting and dispersing agent.

10. A method for preparing the photopolymerizable 3D printing material according to any one of claims 1-9, characterized in that, The method described is Method I: Diisocyanate is added to polyol to react and obtain terminal isocyanate prepolymer; end-capping agent is added to prepolymer to obtain (meth)acrylate oligomer; oligomer is mixed with reactive diluent, photoinitiator and additives to obtain photocurable 3D printing material; Alternatively, the method described is method II: A capping agent is added to diisocyanate to react and obtain a photocurable oligomer; the oligomer is mixed with an active diluent, a photoinitiator and an additive to obtain a photocurable 3D printing material.

11. The preparation method according to claim 10, characterized in that, In Method I, the polyol is one or more of the following: polyether polyol, polyester polyol, hydroxyl-terminated polybutadiene, hydroxyl-terminated styrene-butadiene rubber, hydroxyl-terminated butadiene-acrylonitrile rubber, and hydroxyl-terminated polysiloxane. And / or, in Method I, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; And / or, in Method I, after adding the catalyst, the diisocyanate and polyol are reacted at 60-80°C for 2-4 hours; And / or, in Method I, the end-capping agent is one or more of amino polyethylene glycol (meth)acrylamide, hydroxy polyethylene glycol (meth)acrylamide, and amino polytetrahydrofuran ether glycol (meth)acrylamide; And / or, in method I, the capping agent reacts with the polyol for 2-4 hours; And / or, in Method I, the oligomer is stirred and mixed evenly with the reactive diluent, photoinitiator, and additives.

12. The preparation method according to claim 11, characterized in that, In Method I, the molar ratio of diisocyanate to polyol is 2–2.1:1; In Method I, the molar ratio of the capping agent to the polyol is 1.95 to 2.05:

1.

13. The preparation method according to claim 10, characterized in that, In Method II, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. And / or, in Method II, the capping agent is one or more of amino polyethylene glycol (meth)acrylamide, hydroxy polyethylene glycol (meth)acrylamide, and amino polytetrahydrofuran ether glycol (meth)acrylamide; And / or, in Method II, after the diisocyanate and the capping agent are added to the catalyst, they are reacted at 60-80°C for 2-4 hours; And / or, in Method II, the oligomer is stirred and mixed evenly with the reactive diluent, photoinitiator, and additives.

14. The preparation method according to claim 13, characterized in that, In Method II, the molar ratio of diisocyanate to capping agent is 1:2 to 2.

1.

15. Use of a photocurable 3D printing material, wherein the material is the photocurable 3D printing material according to any one of claims 1-9, or the photocurable 3D printing material prepared by the preparation method according to any one of claims 10-14, characterized in that, The material is used in the fields of photocurable 3D printing materials, photocurable coatings, and adhesives.

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