3D printing light-cured polyurethane resin as well as preparation method and application thereof

Abstract

The invention relates to the field of polyurethane resin, and particularly discloses 3D printing light-cured polyurethane resin as well as a preparation method and application thereof. The 3D printing light-cured polyurethane resin is prepared from the following raw materials in parts by weight: 60-80 parts of a polyurethane acrylate prepolymer, 15-25 parts of a diluting monomer, 8-12 parts of a dispersing filler, 6-8 parts of a photoinitiator and 3-5 parts of a stabilizer, the polyurethane acrylate prepolymer is prepared from aliphatic diisocyanate, trimethylolpropane diallyl ether, dipentaerythritol hexaacrylate, o-phenyl phenoxyethyl acrylate and a catalyst, and the polyurethane acrylate prepolymer is prepared from the aliphatic diisocyanate, the trimethylolpropane diallyl ether, the dipentaerythritol hexaacrylate, the o-phenyl phenoxyethyl acrylate and the catalyst; the polyurethane resin prepared by the invention has relatively good flexibility and elasticity, low shrinkage rate and low possibility of deformation, and can be applied to products with complex structures and high dimensional requirements, such as soles and underwear mold cups prepared by 3D printing.

Description

Technical Field

[0001] The present application relates to the field of polyurethane resins, and more specifically, to a 3D printing light-curing polyurethane resin and a preparation method and application thereof. Background Art

[0002] 3D printing, also known as additive manufacturing, is a technology that constructs three-dimensional objects based on digital model files through layer-by-layer printing. It has the advantages of rapid prototyping, variable prototyping structures, high precision, and material saving. Therefore, it has been widely used in tissue engineering, soft robotics, aerospace, transportation, daily consumer goods and other fields.

[0003] As a commonly used material in 3D printing, photocurable materials have excellent elasticity and formability. Photocurable materials are generally composed of difunctional (multifunctional) photosensitive monomers, diluent monomers, photoinitiators and a small amount of additives, and are quickly cured under ultraviolet light. During the curing process, the active functional groups of difunctional (multifunctional) photosensitive monomers and diluent monomers are quickly cross-linked, giving the photocurable materials excellent flexibility and mechanical strength. However, the active functional groups are prone to shrinkage during the rapid curing process, which causes the size of the prepared photocurable materials to change and easily deform, reducing the applicability of photocurable materials in 3D printing with complex structures and high size requirements. Summary of the invention

[0004] In order to solve the problem that photocurable materials used in 3D printing with complex structures cannot have a good balance of flexibility, elasticity and dimensional stability, the present application provides a 3D printing photocurable polyurethane resin and a preparation method and application thereof.

[0005] In the first aspect, the present application provides a 3D printing light-curable polyurethane resin, which adopts the following technical solution: A 3D printing light-curing polyurethane resin is prepared from the following raw materials in parts by weight: Polyurethane acrylate prepolymer 60-80 parts Dilute monomer 15-25 parts Dispersed filler 8-12 parts Photoinitiator 6-8 parts 3-5 parts of stabilizer; The polyurethane acrylate prepolymer is prepared from aliphatic diisocyanate, trimethylolpropane diallyl ether, dipentaerythritol hexaacrylate, o-phenylphenoxyethyl acrylate and a catalyst.

[0006] By adopting the above technical scheme, the present application uses a polyurethane acrylate prepolymer to be compounded with a diluent monomer, a dispersed filler, a photoinitiator and a stabilizer. The polyurethane acrylate prepolymer is prepared from aliphatic diisocyanate, trimethylolpropane diallyl ether, dipentaerythritol hexaacrylate, o-phenylphenoxyethyl acrylate and a catalyst. The polyurethane acrylate prepolymer prepared in this way has a densely interwoven network molecular structure. While improving the flexibility and elasticity of the prepared polyurethane resin, it can reduce the shrinkage rate of the polyurethane resin during curing, improve the dimensional stability of the prepared polyurethane resin, and is not easy to deform; under the action of the photoinitiator, the polyurethane acrylate prepolymer and the diluent monomer are further cross-linked, the dispersed filler plays a role in reinforcing the performance of the polyurethane material, and the stabilizer can produce a good synergistic effect with the polyurethane acrylate prepolymer, further improve the flexibility and elasticity of the prepared polyurethane resin, and reduce the curing shrinkage rate. The polyurethane acrylate prepolymer can be applied to 3D printing to prepare products with complex structures and high size requirements such as soles and underwear mold cups.

[0007] Preferably, the polyurethane acrylate prepolymer is prepared from the following raw materials in weight percentage: Aliphatic diisocyanate 30-40 parts Trimethylolpropane diallyl ether 16-22 parts Dipentaerythritol hexaacrylate 15-20 parts 8-12 parts of o-phenylphenoxyethyl acrylate The first catalyst 0.05-0.2 parts 0.1-0.3 parts of the second catalyst; The first catalyst is an organic tin catalyst, and the second catalyst is dibenzoyl peroxide.

[0008] Preferably, the polyurethane acrylate prepolymer is prepared by the following steps: S1, reacting aliphatic diisocyanate, trimethylolpropane diallyl ether and a first catalyst at a temperature of 75-90° C. for 1-2 hours to obtain a vinyl terminated polyurethane prepolymer; S2. Add dipentaerythritol hexaacrylate, o-phenylphenoxyethyl acrylate and a second catalyst to a vinyl-terminated polyurethane prepolymer, and react at a temperature of 60-80° C. for 2-3 hours to obtain a polyurethane acrylate prepolymer.

[0009] By adopting the above technical scheme, under the action of a catalyst, aliphatic diisocyanate provides isocyanate groups and trimethylolpropane diallyl ether provides hydroxyl groups, and the two react under optimal temperature and time conditions to obtain a vinyl-terminated polyurethane prepolymer with a branched cross-linked structure; then dipentaerythritol hexaacrylate and o-phenylphenoxyethyl acrylate are added, and the reaction continues under the action of the catalyst under optimal temperature and time conditions to obtain a polyurethane acrylate prepolymer with a branched network interwoven molecular structure, and dipentaerythritol hexaacrylate and o-phenylphenoxyethyl acrylate play a good synergistic effect, which gives the polyurethane acrylate prepolymer excellent elasticity, and the phenyl group of o-phenylphenoxyethyl acrylate gives the network interwoven polyurethane acrylate prepolymer excellent molecular segment stability, which improves the flexibility and elasticity of the polyurethane acrylate prepolymer, and makes the polyurethane acrylate prepolymer difficult to shrink when reacting with a diluent monomer during the preparation of the polyurethane resin, and has good dimensional stability.

[0010] Preferably, the aliphatic diisocyanate is isophorone diisocyanate and / or hexamethylene diisocyanate.

[0011] By adopting the above technical solution, the above aliphatic diisocyanate has excellent flexibility, wear resistance and aging resistance, provides isocyanate groups for the polyurethane acrylate prepolymer, and can improve the stability and comprehensive performance of the prepared polyurethane resin.

[0012] Preferably, the diluent monomer consists of methyl methacrylate, lauryl acrylate and glycidyl methacrylate in a weight ratio of 1:(1-2):(2-3).

[0013] By adopting the above technical scheme, a dilution monomer is composed of methyl methacrylate, lauryl acrylate and glycidyl methacrylate in a relatively optimal weight ratio, which has a good synergistic effect with the polyurethane acrylate prepolymer, can improve the processing fluidity and curing stability of the polyurethane resin, and thus enhance the flexibility, elasticity and application dimensional stability of the obtained polyurethane resin.

[0014] Preferably, the dispersed filler is silanized white carbon black.

[0015] By adopting the above technical solution, the silanized white carbon black has a higher specific surface area and surface activity, and can be evenly dispersed in the polyurethane resin, further improving the strength and application dimensional stability of the prepared polyurethane resin.

[0016] Preferably, the stabilizer is composed of polybutadiene polyurethane acrylate and vinyl tri(2-methoxyethoxy)silane in a weight ratio of 1:(0.2-0.5).

[0017] By adopting the above technical scheme, the stabilizer compound composed of polybutadiene polyurethane acrylate and vinyl tri(2-methoxyethoxy) silane has a good synergistic effect with the polyurethane acrylate prepolymer of the present application, which can further improve the crosslinking density of the polyurethane resin, while improving the flexibility and elasticity of the polyurethane resin, further reducing the shrinkage rate during the curing process, and improving the dimensional stability of the application.

[0018] Preferably, the photoinitiator consists of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 1-hydroxycyclohexylphenyl ketone in a weight ratio of (1-2):1.

[0019] By adopting the above technical scheme, a photoinitiator composed of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 1-hydroxycyclohexylphenyl ketone in an optimal weight ratio can efficiently initiate the cross-linking reaction of polyurethane acrylate prepolymer and diluted monomer under ultraviolet light, thereby improving the photocuring speed and efficiency, reducing the shrinkage rate during the curing process, improving dimensional stability, and reducing deformation.

[0020] In a second aspect, the present application provides a method for preparing a 3D printing light-curable polyurethane resin, using the following technical solution: A method for preparing a 3D printing light-curing polyurethane resin comprises the following preparation steps: adding a polyurethane acrylate prepolymer, a diluent monomer, a dispersing filler, a stabilizer and a photoinitiator into a reaction device, stirring them evenly and performing vacuum degassing to prepare the 3D printing light-curing polyurethane resin.

[0021] By adopting the above technical scheme, the preparation method of the present application is simple and easy to operate, and the various components are mixed evenly before degassing, which effectively reduces the bubbles in the polyurethane resin and improves the stability in use.

[0022] In a third aspect, the present application provides an application of a 3D printing light-curing polyurethane resin, using the following technical solution: An application of 3D printing light-curing polyurethane resin is applied to shoe soles and underwear mold cups. The shoe soles and underwear mold cups are both composed of several material layers, each material layer is provided with several hollow areas, and the hollow areas of several material layers are staggered.

[0023] By adopting the above technical scheme, the 3D printed light-cured polyurethane resin has excellent flexibility, cushioning and elasticity when applied to the soles and underwear cups, and at the same time has good dimensional stability and is not easy to deform; by arranging multiple material layers and arranging hollow areas in each material layer, the hollow areas of the multiple material layers are staggered, so that the prepared soles and underwear cups have good support, elasticity and cushioning, and at the same time have good softness and breathability, thereby improving the comfort and durability of use.

[0024] In summary, this application has the following beneficial effects: 1. The 3D printing photocurable polyurethane resin of the present application is prepared from a polyurethane acrylate prepolymer, a diluent monomer, a dispersed filler, a photoinitiator and a stabilizer. The polyurethane acrylate prepolymer is prepared from an aliphatic diisocyanate, trimethylolpropane diallyl ether, dipentaerythritol hexaacrylate, o-phenylphenoxyethyl acrylate and a catalyst. The prepared polyurethane resin has good flexibility and elasticity, low shrinkage and dimensional stability, and is not easy to deform. It can be used in 3D printing to prepare products with complex structures such as soles and underwear mold cups.

[0025] 2. A compound of polybutadiene polyurethane acrylate and vinyl tri(2-methoxyethoxy) silane in a preferred weight ratio as a stabilizer has a good synergistic effect with the polyurethane acrylate prepolymer of the present application, which can further increase the crosslinking density of the polyurethane resin, while improving the flexibility and elasticity of the polyurethane resin, further reducing the shrinkage rate during the curing process, and improving the dimensional stability of the application.

[0026] 3. When the 3D printed photocurable polyurethane resin of the present application is applied to shoe soles and underwear mold cups, multiple material layers are arranged and hollow areas are arranged on the surface of each material layer. The hollow areas of the multiple material layers are arranged in an alternating manner, so that the prepared shoe soles and underwear mold cups have good support, elasticity and cushioning properties, while having good softness and breathability, thereby improving the comfort and durability of use. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a physical picture of a shoe sole made using the 3D printed light-cured polyurethane resin of the present application; Figure 2 This is a physical picture of an underwear mold cup made using the 3D printing light-cured polyurethane resin of the present application. DETAILED DESCRIPTION

[0028] The following is combined with Figure 1-2 The present application is further described in detail with reference to the accompanying drawings and embodiments.

[0029] The following are the sources and specifications of some raw materials of this application. The raw materials used in the preparation examples and embodiments of this application can be obtained from the market, including but not limited to the raw materials of the following models and manufacturers. Raw materials with equivalent performance can be used: 1. White carbon black: Shanghai Zhuzi New Materials, K5 silane-modified white carbon black, specific surface area 135m 2 / g, oil absorption value 2.2ml / g, pH = 6.8; 2. Polybutadiene polyurethane acrylate: American Dymax, BR-640D; Preparation Example of Polyurethane Acrylate Prepolymer Preparation Example 1 Preparation Example 1 discloses a polyurethane acrylate prepolymer, which is prepared by the following steps: S1, 3 kg of isophorone diisocyanate as aliphatic diisocyanate, 1.6 kg of trimethylolpropane diallyl ether and 0.005 kg of stannous octoate as a first catalyst, reacting at a temperature of 75 ° C for 2 hours to obtain a vinyl terminated polyurethane prepolymer; S2. Add 1.5 kg of dipentaerythritol hexaacrylate, 0.8 kg of o-phenylphenoxyethyl acrylate and 0.01 kg of dibenzoyl peroxide as a second catalyst to the vinyl-terminated polyurethane prepolymer, and react at 60° C. for 3 hours to obtain a polyurethane acrylate prepolymer.

[0030] Preparation Example 2-3 The difference between Preparation Example 2-3 and Preparation Example 1 is that the amount of raw materials used and the preparation conditions are different, see Table 1 below for details.

[0031] Table 1 Parameters of Preparation Examples 1-3 Preparation Comparative Example 1 The difference between Preparation Comparative Example 1 and Preparation Example 1 is that an equal amount of o-phenylphenoxyethyl acrylate is replaced by isooctyl acrylate, and the rest is the same as Preparation Example 1.

[0032] Preparation Comparative Example 2 The difference between Preparation Comparative Example 2 and Preparation Example 1 is that an equal amount of trimethylolpropane diallyl ether is replaced by hydroxypropyl methacrylate, and the rest is the same as Preparation Example 1.

[0033] Preparation Comparative Example 3 The difference between Preparation Comparative Example 3 and Preparation Example 1 is that an equal amount of dipentaerythritol hexaacrylate is replaced by trimethylolpropane triacrylate, and the rest is the same as Preparation Example 1.

[0034] Preparation Comparative Example 4 The difference between Preparation Comparative Example 4 and Preparation Example 1 is that an equal amount of o-phenylphenoxyethyl acrylate is replaced by dipentaerythritol hexaacrylate, and the rest is the same as Preparation Example 1. Example

[0035] Example 1 Example 1 discloses a 3D printing light-curable polyurethane resin, which is prepared by the following steps: The polyurethane acrylate prepolymer, diluent monomer, dispersed filler, stabilizer and photoinitiator are added into the reaction equipment, stirred evenly and then vacuum degassed to obtain 3D printing light-curing polyurethane resin.

[0036] Example 2-3 The difference between Example 2-3 and Example 1 is that the amount of raw materials used and the preparation conditions are different, and the source of the polyurethane acrylate prepolymer is different, see Table 2 below for details.

[0037] Table 2 Parameters of Examples 1-3 Example 4 The difference between Example 4 and Example 1 is that the type of stabilizer is different. The stabilizer of Example 4 is composed of polybutadiene polyurethane acrylate and vinyl tri(2-methoxyethoxy)silane in a weight ratio of 1:0.2, and the rest is the same as Example 1.

[0038] Example 5 The difference between Example 5 and Example 1 is that the stabilizer consists of polybutadiene polyurethane acrylate and vinyl tri(2-methoxyethoxy)silane in a weight ratio of 1:0.5, and the rest is the same as Example 1.

[0039] Comparative Example Comparative Examples 1-5 The difference between Comparative Examples 1-5 and Example 1 is that the sources of the polyurethane acrylate prepolymer are different, see Table 3 below for details.

[0040] Table 3 Sources of polyurethane acrylate prepolymers of Comparative Examples 1-5 Comparative Example Source table of polyurethane acrylate prepolymers Comparative Example 1 Preparation Comparative Example 1 Comparative Example 2 Preparation Comparative Example 2 Comparative Example 3 Preparation Comparative Example 3 Comparative Example 4 Preparation Comparative Example 4 Comparative Example 5 Commercially available The commercially available polyurethane acrylate prepolymer is EBECRYL4491 from Allnex.

[0041] Application Examples Application Example 1 Application Example 1 discloses a shoe sole, such as Figure 1 As shown, the thickness of the heel of the sole is 23.5 mm, the thickness of the forefoot of the sole is 11.5 mm, the sole is composed of five layers of material, the edge thickness of the material layer is 3 mm, and each material layer is provided with a number of hollow areas. Preferably, the hollow areas are triangular in shape, and the density of the hollow areas is 10 / cm 2 The hollow area is formed by interweaving several connecting parts with a width of 2mm, and the hollow areas of several layers of material are staggered; there are several supporting parts between adjacent material layers, and a supporting skeleton composed of several supporting triangles is formed between the several supporting parts and the adjacent material layers. The width of the supporting part is 2mm, and the distribution density of the supporting triangle is 8 / cm 2.

[0042] The printing process of the sole is as follows: Based on the CAD model of the sole, the model is discretized into layer data through layering software and input into a light-curing 3D printer. The light-curing polyurethane resin prepared in Example 1 is used to print at a printing speed of 80 mm / s using a light-curing 3D printer. While printing, 355 nm ultraviolet light is used for photocuring. The light-curing 3D printer moves vertically to print the material layers in sequence to obtain a sole.

[0043] Application Example 2 The difference between Application Example 2 and Application Example 1 is that the photocurable polyurethane resin prepared in Example 4 is used for printing, and the rest is the same as Application Example 1.

[0044] Application Example 3 The difference between Application Example 3 and Application Example 1 is that the photocurable polyurethane resin prepared in Comparative Example 4 is used for printing, and the rest is the same as Application Example 1.

[0045] Application Example 4 The difference between Application Example 4 and Application Example 1 is that the photocurable polyurethane resin prepared in Comparative Example 5 is used for printing, and the rest is the same as Application Example 1.

[0046] Application Example 5 Application Example 5 discloses an underwear mold cup, such as Figure 2 As shown, the edge thickness of the bra cup is 2 mm, the center thickness of the bra cup is 5 mm, and the bra cup is composed of two material layers. Each material layer is interwoven with several connecting parts to form several regular hexagonal hollow areas, and the distribution density of the hollow areas is 5 / cm 2 The width of the connecting part is 1mm, and several hollow areas of the two material layers are staggered; the two material layers are connected by a supporting part, and the two ends of the supporting part are respectively connected to the connecting part of the two material layers, and the width of the supporting part is 1mm.

[0047] The printing process of underwear cup is as follows: Based on the CAD model of the underwear cup mold, the model is discretized into layer data through layering software and input into a light-curing 3D printer. The light-curing polyurethane resin prepared in Example 1 is used to print at a printing speed of 80 mm / s using a light-curing 3D printer. While printing, 355 nm ultraviolet light is used for photocuring. The light-curing 3D printer moves vertically to print the material layers in sequence to obtain an underwear cup mold.

[0048] Application Example 6 The difference between Application Example 6 and Application Example 5 is that the photocurable polyurethane resin prepared in Example 4 is used for printing, and the rest is the same as Application Example 5.

[0049] Application Example 7 The difference between Application Example 7 and Application Example 5 is that the photocurable polyurethane resin prepared in Comparative Example 4 is used for printing, and the rest is the same as Application Example 5.

[0050] Application Example 8 The difference between Application Example 8 and Application Example 5 is that the photocurable polyurethane resin prepared in Comparative Example 5 is used for printing, and the rest is the same as Application Example 5.

[0051] Performance testing 1. The performance of the photocurable polyurethane resins prepared in Examples 1-5 and Comparative Examples 1-5 was tested as follows: 1. Elongation at break test: Referring to the test method in GB / T 528-2009, the light-curable polyurethane resin is cured to form a test sample, and cut into a dumbbell-shaped specimen of type 1, and the elongation at break of the sample is tested (unit: %), and the test results are tested and recorded; 2. Rebound resilience test: Referring to the test method in GB / T 1681-2009, the light-curable polyurethane resin is cured to form a test sample, the rebound rate (unit: %) of the test sample is detected, and the test results are tested and recorded; 3. Shrinkage test: The photocurable polyurethane resin was filled into a mold with a length * width * height of 5cm * 2cm * 0.2cm, and photocured to obtain a test sample. The change rate of the area of ​​the test sample after curing and the area before curing was tested, which was recorded as the shrinkage rate (unit: %). The test results were tested and recorded. The following are the performance test data of the photocurable polyurethane resins obtained in Examples 1-5 and Comparative Examples 1-5, see Table 4 below for details.

[0052] Table 4 Performance data of Examples 1-5 and Comparative Examples 1-5 Combining Examples 1-3 and Comparative Examples 1-5 and Table 4, it can be concluded that the photocurable polyurethane resin prepared using the polyurethane acrylate prepolymer of the present application has good flexibility and elasticity, a small shrinkage rate after curing, and good dimensional stability; further combining Example 1 and Examples 4-5 and Table 4, it can be concluded that using the polybutadiene polyurethane acrylate and vinyl tri(2-methoxyethoxy)silane of the present application as stabilizers can further improve the performance of the prepared photocurable polyurethane resin. Compared with Example 1, Examples 4-5 have an elongation at break increased by 18%, a rebound rate increased by 1.5%, and a shrinkage rate reduced by 0.4%.

[0053] 2. The performance tests of the soles prepared according to the following corresponding examples 1-4 are carried out: 1. According to the mechanical impact test standard operating procedure 190701, the peak acceleration (unit: g) and rebound rate (%) of the heel of the sole are tested. The peak acceleration represents the cushioning and shock absorption performance. The peak acceleration is less than 9.5, which is professional; 9.5<peak acceleration<11 is good, 11<peak acceleration<12 is ordinary, and the peak acceleration is greater than 12 is poor. Test and record the test results; 2. Referring to the test method in SATRATM92, the sole is subjected to a bending resistance test. Under the temperature condition of 23°C, the sole is bent at 90°, the bending rate is controlled to be 100 times / min, and the cycle test is performed 100,000 times. Observe whether the sole is broken, and test and record the test results; The following is the performance test data table of the soles of Application Examples 1-4, see Table 5.

[0054] Table 5 Performance data of the soles of application examples 1-4 Combining Application Examples 1-4 and Table 5, it can be concluded that the light-cured polyurethane resin prepared using the polyurethane acrylate prepolymer of the present application is applied to 3D printed soles, and the prepared soles have good cushioning and shock absorption effects, with a peak acceleration of 8.89g and a rebound rate of 67.3%, and will not break after the folding test; Application Examples 3 and 4, compared with Application Example 1, changed the source of the polyurethane acrylate prepolymer, and the cushioning and resilience of the prepared soles were reduced, and they broke during the bending test.

[0055] 3. The following is a performance test of the underwear cup corresponding to Examples 4-8: Washing deformation test: refer to the test method in GB / T 8629-2017, select type A washing machine, standard detergent 1, and conduct cleaning test on the underwear cup. After 50 cycles of washing, dry it, and test the dimensional change rate (unit: %) of the width between the upper and lower edges of the underwear before and after washing along the longitudinal direction of the BP of the underwear. Test and record the test results; The following is the performance test data table of the soles of Application Examples 1-4, see Table 6.

[0056] Table 6 Performance data of the soles of application examples 1-4 Combining Application Examples 5-8 and Table 5, it can be concluded that the photocurable polyurethane resin prepared using the polyurethane acrylate prepolymer of the present application is used in 3D printed underwear mold cups. The prepared mold cups have good water washing dimensional stability and a dimensional change rate of 0.5%. Compared with Application Examples 7 and 8, the dimensional stability is significantly improved.

[0057] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A 3D printing light-curing polyurethane resin, characterized in that: Made from the following raw materials in parts by weight: Polyurethane acrylate prepolymer 60-80 parts Dilute monomer 15-25 parts Dispersed filler 8-12 parts Photoinitiator 6-8 parts 3-5 parts of stabilizer; The polyurethane acrylate prepolymer is prepared from aliphatic diisocyanate, trimethylolpropane diallyl ether, dipentaerythritol hexaacrylate, o-phenylphenoxyethyl acrylate and a catalyst.

2. A 3D printing light-curing polyurethane resin according to claim 1, characterized in that: The polyurethane acrylate prepolymer is prepared from the following raw materials in weight percentage: Aliphatic diisocyanate 30-40 parts Trimethylolpropane diallyl ether 16-22 parts Dipentaerythritol hexaacrylate 15-20 parts 8-12 parts of o-phenylphenoxyethyl acrylate The first catalyst 0.05-0.2 parts 0.1-0.3 parts of the second catalyst; The first catalyst is an organic tin catalyst, and the second catalyst is dibenzoyl peroxide.

3. A 3D printing light-curing polyurethane resin according to claim 1, characterized in that: The aliphatic diisocyanate is isophorone diisocyanate and / or hexamethylene diisocyanate.

4. A 3D printing light-curing polyurethane resin according to claim 2 or 3, characterized in that: Described polyurethane acrylate prepolymer is prepared by following steps: S1, reacting aliphatic diisocyanate, trimethylolpropane diallyl ether and a first catalyst at a temperature of 75-90° C. for 1-2 hours to obtain a vinyl terminated polyurethane prepolymer; S2. Add dipentaerythritol hexaacrylate, o-phenylphenoxyethyl acrylate and a second catalyst to a vinyl-terminated polyurethane prepolymer, and react at a temperature of 60-80° C. for 2-3 hours to obtain a polyurethane acrylate prepolymer.

5. The 3D printing light-curing polyurethane resin according to claim 1, characterized in that: The diluent monomer is composed of methyl methacrylate, lauryl acrylate and glycidyl methacrylate in a weight ratio of 1:(1-2):(2-3).

6. A 3D printing light-curing polyurethane resin according to claim 1, characterized in that: The dispersed filler is silanized white carbon black.

7. The 3D printing light-curing polyurethane resin according to claim 1, characterized in that: The stabilizer is composed of polybutadiene polyurethane acrylate and vinyl tri(2-methoxyethoxy)silane in a weight ratio of 1:(0.2-0.5).

8. The 3D printing light-curing polyurethane resin according to claim 1, characterized in that: The photoinitiator consists of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 1-hydroxycyclohexylphenyl ketone in a weight ratio of (1-2):

1.

9. A method for preparing a 3D printing light-curable polyurethane resin according to any one of claims 1 to 8, characterized in that: The following steps are involved: The polyurethane acrylate prepolymer, diluent monomer, dispersed filler, stabilizer and photoinitiator are added into the reaction equipment, stirred evenly and then vacuum degassed to obtain 3D printing light-curing polyurethane resin.

10. An application of a 3D printing light-curable polyurethane resin as claimed in any one of claims 1 to 8, characterized in that: The invention is applied to shoe soles and underwear mold cups. The shoe soles and underwear mold cups are both composed of several material layers. Each material layer is provided with several hollow areas. The hollow areas of the several material layers are arranged in a staggered manner.

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