Resin composition, secondary curing preparation method and application thereof

Abstract

The invention provides a resin composition, a secondary curing preparation method and application thereof. The resin composition is prepared from the following components in parts by weight: 12 to 48 parts of modified acrylate prepolymer, 2 to 30 parts of polycyclic carbonate, 3 to 30 parts of monomer and 0.1 to 0.5 part of photoinitiator, and the modified acrylate prepolymer contains a multi-element imine group. According to the invention, the modified acrylate prepolymer containing the multi-element imine group is introduced, and the modified acrylate prepolymer, the multi-element cyclic carbonate, the photocuring monomer and the photoinitiator have a synergistic effect, so that the resin composition capable of being photocured and secondarily cured is obtained. The obtained resin composition has a long storage period of validity, and can form a more stable network structure after 3D printing, curing molding and secondary curing, so that the 3D printing resin has higher strength and elasticity after final curing molding.

Description

Technical Field

[0001] The present invention relates to the field of 3D printing materials, and more particularly to a resin composition, a secondary curing preparation method thereof, and applications thereof. Background Art

[0002] When performing 3D printing using DLP technology (Digital Light Processing), the main components of the consumable photosensitive resin are usually acrylate oligomers, acrylate monomers, and photoinitiators. The polymer molecular backbone obtained after curing such a composition is polyacrylate, and most are chemically crosslinked network structures with a relatively high crosslinking density, which are suitable for manufacturing rigid materials and can achieve relatively high strength and modulus. However, if used to manufacture elastomeric materials, the mechanical properties are usually weak, mainly manifested as poor resilience, low tensile strength, and low elongation at break. Polyurethane elastomeric materials usually have high resilience, high strength, and elongation at break, and are also widely used because their main component is high molecular weight linear polyurethane with a regular structure, and physical crosslinks are formed between urethane structures through hydrogen bond interactions. Therefore, how to introduce a polyurethane structure within the framework of the photocuring 3D printing technology to improve the performance of the cured elastomeric material has become a research hotspot.

[0003] Related technologies disclose a method for preparing three-dimensional objects from materials having multiple hardening mechanisms. The photopolymerizable liquid in this method includes a mixture of a first component and a second curable (or second reactive) component different from the first component. The first component includes a blocked or reactively blocked prepolymer and a reactive diluent (such as a polyisocyanate oligomer, diisocyanate, reactive diluent, and / or chain extender) and a reactive diluent, and the second component includes a chain extender. By performing photocuring on the first component to print a three-dimensional intermediate, and then performing thermal curing to cure the second component to form a three-dimensional object. In this technical solution, since the polyurethane prepolymer used is an isocyanate group, it has a very high activity and can react to form a gel at room temperature. Therefore, it can be foreseen that the service life of such a composition will be very short, and additive manufacturing generally takes more than several hours to complete. During this period, the various properties of the obtained resin material will be significantly invalidated, affecting its use. In addition, isocyanates pose various hazards to the human body and the environment during production and use.

[0004] Based on this, how to provide a resin composition with a relatively long storage shelf life so that it has better mechanical properties, especially higher elasticity, after being 3D printed and cured into a shape is one of the technical problems to be solved in this field. Summary of the Invention

[0005] The main object of the present invention is to provide a resin composition, a method for preparing a three-dimensional object and a product, so as to solve the problems of short storage life of the 3D printing resin composition in the prior art and poor mechanical properties of the resin material obtained after curing and forming.

[0006] To achieve the above object, a first aspect of the present invention provides a resin composition. By weight, the resin composition comprises: 12 to 48 parts of a modified acrylate prepolymer, 2 to 30 parts of a polycyclic carbonate, 3 to 30 parts of a monomer, and 0.1 to 0.5 part of a photoinitiator; the modified acrylate prepolymer contains a polyimine group.

[0007] Further, by weight, the resin composition comprises: 16 to 27 parts of a modified acrylate prepolymer, 2 to 8 parts of a polycyclic carbonate, 4 to 10 parts of a monomer, and 0.2 to 0.3 part of a photoinitiator.

[0008] Further, the polycyclic carbonate includes at least one of a bicyclic carbonate or a tricyclic carbonate; preferably, the polycyclic carbonate is and / or

[0009] Further, the photocurable monomer includes at least one of ethoxyethoxyethyl acrylate, lauryl methacrylate, N-acryloylmorpholine, and isobornyl methacrylate; and / or, the photoinitiator includes at least one of photoinitiator TPO, photoinitiator TMO, photoinitiator 907, photoinitiator 819, and photoinitiator 184.

[0010] Further, the modified acrylate prepolymer includes a compound obtained by reacting a polyamine, a hydroxyl-containing ketone compound, and an acrylate compound.

[0011] Further, the modified acrylate prepolymer includes a compound obtained by reacting polyetheramine D2000, hydroxyacetone, and methyl methacrylate; or, the modified acrylate prepolymer includes a compound obtained by reacting polyetheramine T5000, hydroxyacetone, and methyl methacrylate.

[0012] Further, the modified acrylate prepolymer is prepared by the following steps: Step S1, performing a dehydration bonding reaction on a polyamine and a hydroxyl-containing ketone compound to obtain a hydroxyl-containing polyimine; Step S2, performing a transesterification reaction on the hydroxyl-containing polyimine and an acrylate compound to obtain a modified acrylate prepolymer.

[0013] Further, the weight ratio of the polyamine to the ketone compound containing hydroxyl groups is 1.2:1 to 12:1, preferably 6:1 to 12:1; and / or, the polyamine includes at least one of polyetheramine D2000, polyetheramine T5000, polyetheramine D400, 4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodiphenylmethane, and the ketone compound containing hydroxyl groups is hydroxyacetone and / or 1,3-dihydroxyacetone; and / or, the reaction temperature of the dehydration bonding reaction is 80°C to 120°C, and the dehydration bonding reaction uses an organic acid as a catalyst.

[0014] Further, the weight ratio of the polyimide containing hydroxyl groups to the acrylate compound is 0.05:1 to 0.5:1, preferably 0.2:1 to 0.5:1; and / or, the acrylate compound includes at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, and methyl methacrylate; and / or, the transesterification reaction is carried out at 100°C to 120°C.

[0015] The second aspect of the present invention provides a method for preparing a three-dimensional object, the method comprising: irradiating the resin composition according to any one of the first aspects provided by the present invention with a light source to form an initial three-dimensional object; setting the initial three-dimensional object in a water-containing atmosphere and subjecting it to a reaction at a predetermined temperature range to obtain a final three-dimensional object.

[0016] Further, the relative humidity of the water-containing atmosphere is 60%RH to 100%RH, and the reaction is carried out at 60°C to 130°C; preferably, the relative humidity of the water-containing atmosphere is 80%RH to 100%RH, and the reaction is carried out at 90±5°C.

[0017] Further, the reaction time is 1h to 10h, preferably 8h to 9h.

[0018] Further, the method for preparing the above three-dimensional object further comprises: step (a), providing a light source module capable of emitting light, and at the same time providing a forming module provided with a forming platform and an optically transparent member, the optically transparent member having a construction surface, a construction area is defined between the forming platform and the construction surface, and the forming platform is used to carry the three-dimensional object; step (b), filling the construction area with the above resin composition; step (c), controlling the forming platform to move to a specified position in the construction area; step (d), using the light source module to emit light and making the light irradiate the construction area through the optically transparent member to cure at least a part of the resin composition; step (e), controlling the forming platform to move away from the construction surface; step (f), repeating steps (b) to (e) to form an initial three-dimensional object; step (g), optionally, cleaning the initial three-dimensional object; and step (h), setting the initial three-dimensional object in a water-containing atmosphere and subjecting it to a reaction at a predetermined temperature range to obtain a final three-dimensional object.

[0019] The third aspect of the present invention provides a product prepared by the method for preparing a three-dimensional object according to any one of the second aspects provided by the present invention, and the product includes any one of the following: footwear, sports protectors, toys, and equipment parts.

[0020] By applying the technical solution of the present invention, through the introduction of a modified acrylate prepolymer containing a polyimide group and the synergistic effect with a polycyclic carbonate, a photo-curable monomer, and a photoinitiator, a resin composition that can be photo-cured and secondarily cured is obtained. The obtained resin composition has a long storage shelf life. After 3D printing, curing, and secondary curing, it can form a more stable network structure, so that the 3D printing resin has higher strength and elasticity after final curing. In addition, the resin composition provided by the present invention also has good fluidity and photo-curing performance, is suitable for 3D printing applications with high precision and complex structures, and can significantly improve the printing efficiency and the quality of printed parts. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The specification drawings forming a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation to the present invention. In the drawings:

[0022] Figure 1 It is a schematic structural diagram of a device for forming a three-dimensional object provided by an open embodiment of the present invention.

[0023] Among them, the above-mentioned drawings include the following reference numerals:

[0024] 11, forming platform; 12, optically transparent member; 13, light source module; 14, three-dimensional object; 121, building surface; 122, photo-curable material. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0025] It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0026] As described in the background art, the 3D printing resin composition in the prior art has the problems of short service life and poor elasticity of the three-dimensional object obtained by curing and forming. To solve the above technical problems, the first aspect of the present invention provides a resin composition. By weight, the resin composition includes: 12 to 48 parts of a modified acrylate prepolymer, 2 to 30 parts of a polycyclic carbonate, 3 to 30 parts of a monomer, and 0.1 to 0.5 parts of a photoinitiator; the modified acrylate prepolymer contains a polyimide group.

[0027] The present invention obtains a photocurable and secondary-curable resin composition by introducing a modified acrylate prepolymer containing polyimide groups and making it act synergistically with polycyclic carbonates, photocurable monomers, and photoinitiators. After the obtained resin composition is 3D printed, cured and then secondarily cured, a more stable network structure, namely a polyhydroxy polyurethane structure, can be formed, so that the obtained resin material can exhibit extremely excellent elasticity. In particular, by precisely controlling the proportions of the various components as described above, the polyimide groups can effectively react with polycyclic carbonates to form polyurethane structures under high humidity and high temperature conditions, thereby greatly improving the mechanical properties of the obtained cured resin material, especially the resilience and tensile strength, and is suitable for manufacturing high-performance resin-based elastomers.

[0028] Specifically, the monomer is a photocurable monomer, such as a (meth)acrylate monomer.

[0029] The curing process of the resin composition provided by the present invention is as follows: The (meth)acrylate undergoes photocuring polymerization to achieve printing and forming, and then undergoes secondary curing under high temperature and high humidity. The imine structure reacts with water to generate primary amines, and the generated primary amines react with cyclic carbonates to generate hydroxyl-containing polyurethanes. The specific process is as follows:

[0030]

[0031] Based on this, since traditional photocurable 3D printing materials usually use polyacrylate as the main component, the formed network structure is relatively rigid and lacks good elastic recovery ability. The above-mentioned polyimide structure introduced by the present invention reacts with cyclic carbonates to form polyurethane structures during the secondary curing process. The obtained polyurethane molecules contain alternating flexible segments and hard segments, and can form a microphase-separated structure, where the hard segments (such as urethane segments) provide rigidity, while the flexible segments (such as polyether segments) endow the material with good elasticity. This special structural regularity enables the finally cured resin material to deform under stress without being easily broken, and has high resilience and elongation at break. In addition, the above-mentioned modified acrylate prepolymer provided by the present invention can remain stable under dry conditions, avoiding premature curing of the premixed materials during storage, so the storage time of the composition is relatively long. In the secondary curing stage, that is, under high temperature and high humidity conditions, the imine groups react with water to generate primary amines, and the primary amines then undergo ring-opening condensation with cyclic carbonates to form polyurethane segments. This reaction mechanism not only improves the curing efficiency, but also reduces the internal stress that may be generated in the pre-curing stage, avoiding early deterioration of the material. The generated polyhydroxy polyurethane structure forms hydrogen bonds between molecules, enhancing the physical crosslinking between molecules and improving the cohesion of the material. In addition, the reaction between cyclic carbonates and primary amines can also regulate the curing rate and degree of the resin material, further optimizing its comprehensive performance.

[0032] In summary, by introducing a polyimide structure and precisely controlling the dosage of each component, the present invention realizes a special secondary curing mechanism. The elastomeric material obtained by curing the resin composition not only overcomes the problem of insufficient elasticity of traditional photocurable materials, but also achieves high resilience and high strength required for high-performance elastomers through microphase separation and hydrogen bonding.

[0033] Further, by weight, the resin composition includes: 16 to 27 parts of a modified acrylate prepolymer, 2 to 8 parts of a polycyclic carbonate, 4 to 10 parts of a monomer, and 0.2 to 0.3 parts of a photoinitiator. By narrowing the weight range of each component, the curing characteristics of the obtained secondary curing resin composition can be more precisely controlled, improving its consistency and predictability. Furthermore, it can improve the fluidity and printing accuracy of the material during 3D printing, and at the same time, enable the resin material obtained during secondary curing to form a more uniform and consistent polymer structure, further enhancing its mechanical properties.

[0034] The present invention introduces a polycyclic carbonate as an active ingredient for secondary curing, which can react with primary amines under high-temperature and high-humidity conditions to form a hydroxyl-containing polyurethane structure, thereby enhancing the resilience and tensile strength of the cured resin material. Preferably, the polycyclic carbonate includes at least one of a bicyclic carbonate or a tricyclic carbonate; more preferably, it is (CAS: 25844-34-2) and / or (CAS: 147876-32-2), so as to more effectively react with primary amines during secondary curing to form a more regular polyurethane network, bringing better mechanical properties to the resin material obtained by curing the secondary curing resin composition.

[0035] Further, preferably, the photocurable monomer includes at least one of ethoxyethoxyethyl acrylate (EOEOEA), lauryl methacrylate (LMA), N-acryloylmorpholine (ACMO), and isobornyl methacrylate (IBOMA); and / or, the photoinitiator includes at least one of photoinitiator TPO (2,4,6-trimethylbenzoyl diphenylphosphine oxide), photoinitiator TMO (2,4,6-trimethylbenzoyl-bis(p-tolyl)phosphine oxide), photoinitiator 907 (2-methyl-1-[4-methylthiophenyl]-2-morpholin-1-one), photoinitiator 819 (phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), and photoinitiator 184 (1-hydroxycyclohexyl phenyl ketone). The preferred types of the above photocurable monomers and photoinitiators (especially TPO) promote the primary photocuring efficiency and molding performance of the obtained resin composition during 3D printing. That is, the obtained resin composition can be rapidly cured under UV light irradiation to form a denser initial structure, and then a resin material with a more complete structure and better mechanical properties can be obtained after subsequent secondary curing.

[0036] In several preferred embodiments, in order to optimize the structure of the modified acrylate with a polyimine structure, and thus obtain a resin composition with more excellent properties in all aspects, and make the mechanical properties of the resin material obtained after its secondary curing better, the preferred modified acrylate prepolymer includes a compound obtained by reacting a polyamine, a hydroxyl-containing ketone compound, and an acrylate compound. In particular, the preferred modified acrylate prepolymer is obtained by reacting a polyamine, a hydroxyl-containing ketone compound, and an acrylate compound.

[0037] In a particularly preferred embodiment, by weight, the resin composition comprises: 225 parts of a modified acrylate prepolymer, 25 parts of a polycyclic carbonate 40 parts of the photocurable monomer ethoxyethoxyethyl acrylate and 3 parts of the photoinitiator TPO, and the modified acrylate prepolymer is obtained by reacting polyetheramine D2000, hydroxyacetone, and methyl methacrylate. The proportions of the above components balance the requirements of the two stages of photocuring and thermal curing. Among them, the modified acrylate prepolymer forms a pre-cured structure under UV light irradiation, the polycyclic carbonate opens the ring to form a polyurethane segment in the thermal curing stage, the photocurable monomer EOEOEA provides additional crosslinking points, and the photoinitiator TPO ensures the rapid and complete photocuring. In particular, the polarity and flexible segments of EOEOEA contribute to synergistically modifying the acrylate prepolymer and the polycyclic carbonate, and more significantly improve the resilience of the finally cured resin.

[0038] In another particularly preferred embodiment, by weight, the resin composition comprises: 267 parts of a modified acrylate prepolymer, 20 parts of a polycyclic carbonate 42 parts of the photocurable monomer lauryl methacrylate and 3 parts of the photoinitiator TPO, and the modified acrylate prepolymer is obtained by reacting polyetheramine T5000, hydroxyacetone, and methyl methacrylate. In this embodiment, in addition to the structural improvement brought about by the dosage of each component, as a long-chain photocurable monomer, the introduction of LMA helps to synergistically form more flexible molecular segments, so as to retain a higher elongation at break in the cured resin material. That is, after secondary curing, a resin material with greater elasticity is formed.

[0039] Among them, in particular, the preferred modified acrylate prepolymers include compounds obtained by reacting polyetheramine D2000, hydroxyacetone, and methyl methacrylate, or modified acrylate prepolymers include compounds obtained by reacting polyetheramine T5000, hydroxyacetone, and methyl methacrylate, because the compounds prepared from these raw materials have more suitable chemical activities, so the modified acrylate prepolymers containing them can also provide more excellent mechanical properties for the corresponding resin compositions and resin products.

[0040] Regarding the modified acrylate prepolymer, further preferably, its preparation method includes: Step S1, dehydrating and bonding a polyamine with a hydroxy-containing ketone compound to obtain a hydroxy-containing polyimine; Step S2, transesterifying the hydroxy-containing polyimine with an acrylate compound to obtain a modified acrylate prepolymer. That is, first react the polyamine and the hydroxy-containing ketone compound under specific conditions, and then perform a transesterification reaction with the acrylate compound. This preparation method enables the modified acrylate prepolymer to contain the necessary polyimine groups, while maintaining the photocuring characteristics of the obtained modified acrylate prepolymer, so that the resin composition containing it still retains latent chemical activity after photocuring and can be activated under specific conditions to form a more complex three-dimensional network structure, thereby improving the comprehensive mechanical properties, especially the high elasticity, of the resin material obtained after 3D printing and final curing.

[0041] In step S1, the weight ratio of the polyamine to the ketone compound containing a hydroxyl group is preferably 1.2:1 to 12:1, more preferably 6:1 to 12:1. In the weight range of 1.2:1 to 12:1, the ketone compound containing a hydroxyl group remains in excess during the reaction process, which can ensure the reaction conversion rate of the amino group. However, since the ketone compound containing a hydroxyl group needs to be removed after the reaction is completed, it should not be in excessive amount. Therefore, the more preferred weight ratio range is 6:1 to 12:1. The preferred polyamine includes at least one of polyetheramine D2000, polyetheramine T5000, polyetheramine D400, 4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodiphenylmethane, and the above polyamine is combined with hydroxyacetone and / or 1,3-dihydroxyacetone, so as to promote the efficient generation of polyimine with specific properties, providing necessary active sites for subsequent secondary curing. Under the preferred conditions of the above raw materials, the reaction temperature of the dehydration bonding reaction is further preferably 80°C to 120°C, and the dehydration bonding reaction uses an organic acid as a catalyst. The above preferred reaction temperature conditions help to balance the reaction rate and the yield, while reducing the occurrence of side reactions. And a suitable catalyst can promote the efficient and stable generation of polyimine, providing a higher-quality reactant for the subsequent transesterification reaction, and affecting the comprehensive performance of the final composition. More preferably, the organic acid catalyst used in the dehydration bonding reaction is formic acid, whose acidity is more moderate, and can accelerate the formation of imine groups. At the same time, formic acid is more gentle in controlling the reaction temperature and conditions, and can reduce side reactions or thermal decomposition that may occur at high temperatures, thereby helping to maintain the activity of the reactants and the purity of the key intermediate of polyimine containing a hydroxyl group, and further improving the performance of the finally obtained modified acrylate prepolymer in the resin composition.

[0042] In step S2, the weight ratio of the polyimine containing a hydroxyl group to the acrylate compound is preferably 0.05:1 to 0.5:1, more preferably 0.2:1 to 0.5:1. Such preferred and more preferred dosage ratios can keep the acrylate in an appropriate excess during the reaction process, ensuring the conversion rate of the hydroxyl group, but it needs to be removed after the reaction is completed, so it should not be in excessive amount.

[0043] In several preferred embodiments, the acrylate compound preferably includes at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate. And, based on the above dosage types, the transesterification reaction is preferably carried out at 100°C to 120°C to improve the purity of the modified acrylate product and reduce the generation of by-products. At the same time, this temperature also promotes the gentle progress of the reaction, avoiding possible thermal decomposition, and thus obtaining a more stable modified acrylate prepolymer, making the resin composition in which it is located and the resin material obtained by secondary curing of the resin composition have higher stability.

[0044] Since the above resin composition contains components with special structures, the obtained printing resin material has properties close to those of polyurethane materials, with high elasticity, tensile strength and elongation at break. Compared with directly using polyurethane prepolymer, the resin composition has higher photocuring activity, which is beneficial to the three-dimensional printing process, and the storage stability and printability time are greatly improved.

[0045] The second aspect of the present invention provides a method for preparing a three-dimensional object, comprising: irradiating the resin composition according to any one of the first aspects of the present invention with a light source to form an initial three-dimensional object; setting the initial three-dimensional object in a water-containing atmosphere and subjecting it to a reaction at a predetermined temperature range to obtain a final three-dimensional object.

[0046] Specifically, the water-containing atmosphere can be an atmosphere with humidity or a direct water bath.

[0047] In several typical embodiments, the relative humidity of the water-containing atmosphere is 60% RH to 100% RH, and the reaction is carried out at 60°C to 130°C; that is, the secondary curing is carried out under the conditions of a relative humidity of 60% RH to 100% RH and a temperature of 60°C to 130°C, so as to balance the reaction thermal stability and reaction kinetics during the secondary curing process and more effectively promote the dissociation of imine groups to generate amines and further react with cyclic carbonates to form a polyurethane network.

[0048] In several more typical embodiments, the relative humidity of the water-containing atmosphere is 80% RH to 100% RH, and the reaction is carried out at 90 ± 5°C; that is, the secondary curing is carried out under the conditions of a relative humidity of 80% RH to 100% RH and a temperature of 90 ± 5°C. Such more preferably selected conditions promote the more complete dissociation of imine groups and the more orderly formation of polyurethane segments in a high-humidity environment. At the same time, the temperature of 90 ± 5°C provides sufficient thermal energy to accelerate the reaction, and the curing time of 8h to 9h balances the completeness and efficiency of the reaction. Under these conditions, the resin composition can form a polyurethane elastomer with a more compact structure and more stable performance. In particular, the curing under these humidity and temperature conditions can minimize side reactions and random crosslinking of molecular segments to further improve its high resilience and high strength.

[0049] Furthermore, by preferably setting the reaction time to 1h to 10h, more preferably 8h to 9h, it is convenient to better control the degree of secondary curing, so that the obtained three-dimensional resin product can better balance resilience and mechanical strength.

[0050] When performing three-dimensional object printing, a three-dimensional model of the three-dimensional object to be printed can be first established, and then the three-dimensional digital model of the three-dimensional object is sliced layer by layer. During printing, it can start from the first slice layer, and on the basis of the previously successfully printed slice layer, each slice layer is printed in turn, and finally a complete three-dimensional object is obtained. Figure 1 is a schematic structural diagram of a device for forming a three-dimensional object according to an embodiment of the present disclosure. As Figure 1 shown, the three-dimensional printing device includes: a forming platform 11, an optically transparent member 12 (such as a material tray), and a light source module 13 (such as an optical machine). Among them, the forming platform 11 is configured to carry the three-dimensional object 14, the optically transparent member 12 is configured to hold a photocurable material 122 (such as the resin composition in the present invention), the bottom of the optically transparent member has a building surface 121, and a printing area is defined between the building surface 121 and the forming platform 11; the photocurable material 122 is cured layer by layer under the irradiation of the light source module 13 to form on the forming platform 11 to obtain an initial three-dimensional object 14. The initial three-dimensional object can be cleaned and then placed in a conventional curing box for curing to obtain the final three-dimensional object; or the cleaned initial three-dimensional object is set in a water-containing atmosphere and placed in a predetermined temperature range, and the final three-dimensional object is obtained after the reaction.

[0051] During the preparation process of the above three-dimensional object, that is, the three-dimensional resin product, preferably, the preparation method further includes: step (a), providing a light source module 13 capable of emitting light, and at the same time providing a forming module provided with a forming platform 11 and an optically transparent member 12. The optically transparent member 12 has a building surface 121, and a building area is defined between the forming platform 11 and the building surface 121. The forming platform 11 is used to carry the three-dimensional object 14; step (b), filling the building area with the above resin composition; step (c), controlling the forming platform 11 to move to a specified position in the building area; step (d), using the light source module 13 to emit light and making the light pass through the optically transparent member 12 to irradiate the building area to cure at least a part of the resin composition; step (e), controlling the forming platform 11 to move away from the building surface 121; step (f), repeating steps (b) to (e) to form an initial three-dimensional object; step (g), optionally, cleaning the initial three-dimensional object; and step (h), setting the initial three-dimensional object in a water-containing atmosphere and placing it in a predetermined temperature range for reaction to obtain the final three-dimensional object.

[0052] In the above preparation method, during the printing and exposure using a 3D printing device, the modified acrylic prepolymer in the resin composition cures, while the polycyclic carbonate does not react. After the initial 3D object preparation (the modified acrylic prepolymer cures), a secondary curing treatment of the initial 3D object is required to form the final 3D object. Specifically, the initial 3D object is placed in a humid atmosphere so that the amine of the cured modified acrylic resin reacts with water to generate polyamine. Then, within a predetermined temperature range, the generated polyamine crosslinks and polymerizes with the polycyclic carbonate to generate polyurethane.

[0053] The above secondary curing can be carried out successively in two chambers (humidity chamber and temperature chamber), or simultaneously.

[0054] That is, during the secondary curing, the amine of the cured modified acrylic resin reacts with the polycyclic carbonate and water to generate polyurethane (specifically, water first reacts with the imine structure in the cured modified acrylic resin, and the generated polyamine and cyclic carbonate react to generate polyurethane), thereby obtaining the final resin 3D product.

[0055] The third aspect of the present invention provides a product prepared by using the preparation method of a 3D object according to any one of the second aspects provided by the present invention. The product includes any one of the following: footwear, sports protectors, toys, and equipment parts. The obtained product has good mechanical properties, especially it can exhibit higher elasticity during use.

[0056] The following further describes the present application in detail with specific examples, and these examples should not be construed as limiting the scope claimed by the present application.

[0057] Unless otherwise defined, all the technical terms used hereinafter have the same meaning as commonly understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments, and are not intended to limit the protection scope of the present invention.

[0058] Example 1

[0059] Preparation of a resin composition:

[0060] (1) Preparation of a modified acrylate prepolymer:

[0061] (1-2) Weigh 200 g of polyetheramine D2000 (i.e., polyamine), 30 g of hydroxyacetone (i.e., a ketone compound containing a hydroxyl group, and the weight ratio of polyamine to it is 6.67:1), 230 g of toluene as a solvent, and 1 g of formic acid as a catalyst, and put them into a dehydration rectification reactor. Heat up to 120 °C for a dehydration bonding reaction. After the reaction ends, separate the water generated by the reaction, distill off the solvent and the excess hydroxyacetone to obtain 218 g of an intermediate product, i.e., a polyimine containing a hydroxyl group;

[0062] (1 - 2) Continuously add 654 g of methyl methacrylate (i.e., acrylate compound, and the weight ratio of the polyvalent imine containing hydroxyl groups in the intermediate product to it is 0.3:1) to the above reaction system, and raise the temperature to 110 °C for transesterification reaction. After the reaction is completed, the by - product methanol is separated by distillation, and the excessive methyl methacrylate is removed by distillation to obtain the product, i.e., the modified acrylate prepolymer.

[0063] (2) Prepare the resin composition:

[0064] Mix 225 g of the above product, 25 g of bicyclic carbonate (CAS: 25844 - 34 - 2), 40 g of the photocurable monomer EOEOEA and 3 g of the photoinitiator TPO uniformly to obtain the resin composition.

[0065] Preparation of a three - dimensional object, i.e., a secondary - cured 3D printing resin: Using the printing equipment as Figure 1 shown, perform three - dimensional printing of the obtained resin composition on the three - dimensional printing equipment to make a dumbbell - shaped type 1 test piece and cure it into shape. The specific method is as follows:

[0066] Step a, provide a light source module capable of emitting light, and at the same time provide a forming module provided with a forming platform and an optically transparent member having a construction surface. The optically transparent member has a construction surface, and a construction area is defined between the forming platform and the construction surface. The forming platform is configured to carry a three - dimensional object;

[0067] Among them, the light is ultraviolet light with a wavelength band of 365 - 425 nm; the optically transparent member is a release film;

[0068] Step b, fill the construction area with the obtained resin composition;

[0069] Step c, control the forming platform to move to a specified position in the construction area;

[0070] Step d, use the light emitted by the light source module and make the light irradiate the construction area through the optically transparent member to cure at least a part of the resin composition;

[0071] Step e, control the forming platform to move away from the construction surface;

[0072] Step f, repeat steps (b) to (e) to form an initial three - dimensional object, i.e., an initial dumbbell - shaped type 1 test piece;

[0073] Step g, clean;

[0074] Step h, place the cleaned test piece in a constant - temperature and constant - humidity equipment with a relative humidity of 90% RH, i.e., in a water - containing atmosphere. After reacting at 90 °C for 8 h, obtain a secondary - cured dumbbell - shaped type 1 specimen.

[0075] In the actual preparation process, more specifically, the above-mentioned preparation process can be carried out using the following existing equipment: three-dimensional printing can be carried out using the UltraCraft A series, UltraCraft C series or Reflex series provided by Guangzhou Highsun Information Technology Co., Ltd., and secondary curing can be carried out using, for example, an UltraCraft AirCure curing machine, an UltraCraft Crue curing machine, a water bath, a thermostatic and humidistatic chamber, and an autoclave. However, it should be noted that the equipment series and corresponding models here are only for illustration and do not constitute a limitation to the technical solutions provided by the present invention.

[0076] In addition, for the optically transparent member, it may further include, for example, glass, a release film, coated glass, etc. The release film includes an FEP (fluorinated ethylene propylene copolymer) film, a PTFE (polytetrafluoroethylene) film, an nFEP film (a film made by combining an FEP resin and a PTFE resin copolymer), a PFA (perfluoroethylene copolymerized tetrafluoroethylene) film, a PVDF (polyvinylidene fluoride) film, a PVF (polyvinyl fluoride film) film, an ETFE (ethylene-tetrafluoroethylene copolymer) film, etc.

[0077] Example 2

[0078] Preparation of a resin composition:

[0079] (1) Preparation of a modified acrylate prepolymer:

[0080] (1-2) Weigh 500 g of polyetheramine T5000 (i.e., polyamine), 45 g of hydroxyacetone (i.e., a ketone compound containing a hydroxyl group, and the weight ratio of the polyamine to it is 11.11:1), 545 g of toluene as a solvent, and 2 g of formic acid as a catalyst, and put them into a dehydration rectification reactor, and raise the temperature to 110 °C for dehydration bonding reaction. After the reaction is completed, separate the water generated by the reaction, distill off the solvent and the excess hydroxyacetone to obtain 533 g of an intermediate product, i.e., a polyimine containing a hydroxyl group;

[0081] (1-2) Continuously put 1066 g of methyl methacrylate (i.e., an acrylate compound, and the weight ratio of the polyimine containing a hydroxyl group in the intermediate product to it is 0.5:1) into the above reaction system, and raise the temperature to 120 °C for transesterification reaction. After the reaction is completed, rectify and separate the by-product methanol and distill off the excess methyl methacrylate to obtain the product, i.e., a modified acrylate prepolymer.

[0082] (2) Preparation of the resin composition:

[0083] Put 267 g of the above product and 20 g of a tricyclic carbonate (CAS: 147876-32-2), 42 g of the photocurable monomer LMA and 3 g of the photoinitiator TPO were mixed evenly to obtain the resin composition.

[0084] Preparation of a three-dimensional object: The same as in Example 1.

[0085] Example 3

[0086] Preparation of a resin composition:

[0087] (1) Preparation of a modified acrylate prepolymer:

[0088] (1-2) Weigh 400 g of polyetheramine D400 (i.e., polyamine), 155 g of hydroxyacetone (i.e., a ketone compound containing a hydroxyl group, and the weight ratio of polyamine to it is 2.58:1), 555 g of toluene as a solvent, and 2 g of formic acid as a catalyst, and put them into a dehydration rectification reactor. Heat up to 100 °C for dehydration bonding reaction. After the reaction, separate the water generated by the reaction, distill off the solvent and the excessive hydroxyacetone to obtain 500 g of an intermediate product, i.e., a polyimine containing a hydroxyl group;

[0089] (1-2) Continuously add 2000 g of methyl methacrylate (i.e., an acrylate compound, and the weight ratio of the polyimine containing a hydroxyl group in the intermediate product to it is 0.25:1) to the above reaction system, and heat up to 100 °C for transesterification reaction. After the reaction, rectify and separate the by-product methanol and distill off the excessive methyl methacrylate to obtain the product, i.e., a modified acrylate prepolymer.

[0090] (2) Preparation of the resin composition:

[0091] Mix 162 g of the above product, 69 g of the bicyclic carbonate 88 g of the photocurable monomer ACMO and 3 g of the photoinitiator TPO evenly to obtain the resin composition.

[0092] Preparation of a three-dimensional object:

[0093] The difference between this example and Example 1 is only that the secondary curing step (i.e., step h) is adjusted to:

[0094] Set the cleaned test piece in a constant temperature and humidity equipment with a relative humidity of 100% RH, i.e., in a water-containing atmosphere. React at 120 °C for 2 h to obtain a dumbbell-shaped type 1 specimen after secondary curing.

[0095] Example 4

[0096] Preparation of a resin composition:

[0097] (1) Preparation of a modified acrylate prepolymer:

[0098] (1-2) Weigh 210 g of 4,4'-diaminodicyclohexylmethane (i.e., polyamine), 155 g of hydroxyacetone (i.e., a ketone compound containing a hydroxyl group, and the weight ratio of polyamine to it is 1.35:1), 365 g of toluene as a solvent, and 2 g of formic acid as a catalyst, and put them into a dehydration rectification reactor. Heat up to 120 °C for dehydration bonding reaction. After the reaction is completed, separate the water generated by the reaction, distill off the solvent and the excess hydroxyacetone to obtain 320 g of an intermediate product, namely a polyimine containing a hydroxyl group;

[0099] (1-2) Continuously put 1600 g of methyl methacrylate (i.e., an acrylate compound, and the weight ratio of the polyimine containing a hydroxyl group in the intermediate product to it is 0.2:1) into the above reaction system, and heat up to 120 °C for transesterification reaction. After the reaction is completed, rectify and separate the by-product methanol, and distill off the excess methyl methacrylate to obtain the product, namely a modified acrylate prepolymer.

[0100] (2) Prepare a resin composition:

[0101] Mix 458 g of the above product, 278 g of a bicyclic carbonate 280 g of a photocurable monomer ACMO and 3 g of a photoinitiator TPO evenly to obtain a resin composition.

[0102] The preparation of a three-dimensional object: Keep consistent with Example 3.

[0103] Example 5

[0104] The preparation of a resin composition:

[0105] (1) Prepare a modified acrylate prepolymer:

[0106] (1-2) Weigh 198 g of 4,4'-diaminodiphenylmethane (i.e., polyamine), 155 g of hydroxyacetone (i.e., a ketone compound containing a hydroxyl group, and the weight ratio of polyamine to it is 1.28:1), 353 g of toluene as a solvent, and 2 g of formic acid as a catalyst, and put them into a dehydration rectification reactor. Heat up to 110 °C for dehydration bonding reaction. After the reaction is completed, separate the water generated by the reaction, distill off the solvent and the excess hydroxyacetone to obtain 305 g of an intermediate product, namely a polyimine containing a hydroxyl group;

[0107] (1-2) Continuously put 915 g of methyl methacrylate (i.e., an acrylate compound, and the weight ratio of the polyimine containing a hydroxyl group in the intermediate product to it is 0.3:1) into the above reaction system, and heat up to 110 °C for transesterification reaction. After the reaction is completed, rectify and separate the by-product methanol, and distill off the excess methyl methacrylate to obtain the product, namely a modified acrylate prepolymer.

[0108] (2) Preparation of the resin composition:

[0109] Mix 446 g of the above product, 278 g of a bicyclic carbonate 290 g of a photocurable monomer IBOMA and 3 g of a photoinitiator TPO uniformly to obtain the resin composition.

[0110] Preparation of a three-dimensional object: The same as in Example 3.

[0111] Example 6

[0112] Preparation of a resin composition:

[0113] The difference between this example and Example 1 is only that: the weight ratio of the polyamine to the hydroxy-containing ketone compound in step (1-1) is changed to 1:1, and at the same time, the temperature of the dehydration bonding reaction is changed to 140 °C.

[0114] Preparation of a three-dimensional object: The same as in Example 1.

[0115] Example 7

[0116] Preparation of a resin composition:

[0117] The difference between this example and Example 1 is only that: the weight ratio of the polyamine to the hydroxy-containing ketone compound in step (1-1) is changed to 14:1, and at the same time, the temperature of the dehydration bonding reaction is changed to 60 °C.

[0118] Preparation of a three-dimensional object: The same as in Example 1.

[0119] Example 8

[0120] Preparation of a resin composition:

[0121] The difference between this example and Example 1 is only that: the weight ratio of the hydroxy-containing polyimine to the acrylate compound in step (1-2) is 0.1:1, and at the same time, the temperature of the transesterification reaction is changed to 80 °C.

[0122] Preparation of a three-dimensional object: The same as in Example 1.

[0123] Example 9

[0124] Preparation of a resin composition:

[0125] The difference between this example and Example 1 is only that: the weight ratio of the hydroxy-containing polyimine to the acrylate compound in step (1-2) is 0.6:1, and at the same time, the temperature of the transesterification reaction is changed to 150 °C.

[0126] Preparation of a three-dimensional object: The same as in Example 1.

[0127] Example 10

[0128] Preparation of a resin composition:

[0129] The difference between this example and Example 1 is only that: the bicyclic carbonate used in step (2) is replaced with dicyclohexyl carbonate (CAS No. 4427-97-8).

[0130] Preparation of a three-dimensional object: Consistent with Example 1.

[0131] Example 11

[0132] Preparation of a resin composition: Consistent with Example 1.

[0133] Preparation of a three-dimensional object:

[0134] The difference between this example and Example 1 is only that: the relative humidity during the secondary curing process is changed to 50% RH.

[0135] Comparative Example 1

[0136] Preparation of a resin composition:

[0137] The difference between this comparative example and Example 1 is only that: instead of preparing the modified acrylate prepolymer in step (1), 225 g of methyl methacrylate and 25 g of bicyclic carbonate 40 g of photocurable monomer, and 3 g of photoinitiator TPO are mixed evenly to obtain a resin composition.

[0138] Preparation of a 3D printing resin: Consistent with Example 1.

[0139] Comparative Example 2

[0140] Preparation of a resin composition:

[0141] The difference between this comparative example and Example 1 is only that: instead of preparing the modified acrylate prepolymer in step (1), epoxy acrylate is directly used as the modified acrylate prepolymer.

[0142] Preparation of a 3D printing resin: Consistent with Example 1.

[0143] Comparative Example 3

[0144] Preparation of a resin composition:

[0145] The difference between this comparative example and Example 1 is only that: bicyclic carbonate is not added to the resin composition.

[0146] Preparation of a three-dimensional object: Consistent with Example 1.

[0147] Comparative Example 4

[0148] Preparation of a resin composition:

[0149] The difference between this comparative example and Example 1 is only that: the amount of the modified acrylate prepolymer in step (2) is changed to 100 g, the amount of the bicyclic carbonate is changed to 350 g, the amount of the photocurable monomer IBOMA is changed to 20 g, and the amount of the photoinitiator TPO is changed to 0.5 g.

[0150] Preparation of a three-dimensional object: Consistent with Example 1.

[0151] Comparative Example 5

[0152] Preparation of a resin composition:

[0153] The difference between this comparative example and Example 1 is only that: the amount of the modified acrylate prepolymer in step (2) is changed to 500 g, the amount of the bicyclic carbonate is changed to 10 g, the amount of the photocurable monomer IBOMA is changed to 350 g, and the amount of the photoinitiator TPO is changed to 8 g.

[0154] Preparation of a three-dimensional object: Consistent with Example 1.

[0155] Comparative Example 6

[0156] Preparation of a resin composition:

[0157] The difference between this example and Example 1 is only that: instead of preparing the modified acrylate prepolymer in step (1), polyurethane methacrylate is directly used as the modified acrylate prepolymer.

[0158] Preparation of a three-dimensional object: Consistent with Example 1.

[0159] Performance test method

[0160] Tensile strength and elongation at break test: According to GB / T 528, dumbbell-shaped type 1 specimens obtained from each example and comparative example were tested, and the moving speed of the gripper was 500 mm / min.

[0161] Rebound resilience test: Obtained according to GB / T 1681.

[0162] Test method for the shelf life of the composition: The resin compositions obtained from each example and comparative example were sealed and stored at 25°C, and the total number of days experienced when the viscosity increased by 100% was recorded.

[0163] The above tests were performed on the 3D printed resin test pieces obtained in each embodiment and comparative example, and the results are shown in Table 1.

[0164] Table 1

[0165]

[0166]

[0167] From the above description, it can be seen that, relative to the comparative examples, the above-mentioned embodiments of the present invention achieve the preparation of a resin composition with excellent performance and a long effective period of use, and the polyimide group structure in its components can react with polycyclic carbonate under high humidity and high temperature conditions to generate a polyurethane structure, thereby greatly improving the elasticity and elongation at break of the resin material obtained after 3D printing and secondary curing.

[0168] Specifically, the acrylate of polyimide is synthesized from polyamine, hydroxyl-containing ketone and acrylate. The synthesis process parameters will affect the shelf life of the composition. The composition obtained with the preferred process parameters can have a shelf life of more than 180 days. Selecting a polyamine with a larger molecular weight will result in higher tensile strength and elongation at break of the product. The polycyclic carbonate reacts with amines to form polyurethane during the secondary curing process, which is of great significance for improving mechanical properties. The ratio of the composition and the temperature and humidity parameters of the secondary curing will also affect the mechanical properties.

[0169] Among them, by comparing Examples 1 and 2 with Examples 3 to 5, it can be seen that, when calculated by weight, the resin composition includes: "225 parts of modified acrylic ester prepolymer, 25 parts of polycyclic carbonate 40 parts of photocurable monomer ethoxyethoxyethyl acrylate and 3 parts of photoinitiator TPO, and the modified acrylate prepolymer is obtained by reacting polyetheramine D2000, hydroxyacetone and methyl methacrylate" or "267 parts of modified acrylate prepolymer, 20 parts of polycyclic carbonate 42 parts of photocurable monomer lauryl methacrylate and 3 parts of photoinitiator TPO, and the modified acrylate prepolymer is obtained by reacting polyetheramine T5000, hydroxyacetone and methyl methacrylate", a resin composition with better performance can be obtained. Furthermore, the above-mentioned resin composition, that is, the resin composition provided by Examples 1 and 2, can better balance high rebound value and high mechanical strength when obtaining a resin product after curing and secondary curing.

[0170] Comparing Example 1 with Examples 6 and 7, it can be seen that when preparing the modified acrylate prepolymer, the weight ratio of the polyamine to the hydroxyl-containing ketone compound is preferably 1.2:1 to 12:1, and at the same time, the reaction temperature of the dehydration bonding reaction is preferably 80°C to 120°C, so as to obtain a resin composition that is more storage-resistant and has better comprehensive properties after curing.

[0171] Comparing Example 1 with Examples 8 and 9, it can be seen that during the preparation of the modified acrylate prepolymer, the weight ratio of the hydroxyl-containing polyimine to the acrylate compound is preferably 0.05:1 to 0.5:1, especially 0.2:1 to 0.5:1, which can more effectively ensure the conversion rate of hydroxyl groups; at the same time, the transesterification reaction is preferably carried out at 100°C to 120°C to obtain a modified acrylate prepolymer with a more stable structure, making the resin composition where it is located and the resin product obtained by secondary curing of the resin composition have higher stability.

[0172] Comparing Example 1 with Example 10, it can be seen that compared with other bicyclic carbonates, the bicyclic carbonate preferably selected in the present invention can react more effectively with primary amines during the secondary curing process to form a more regular polyurethane network, bringing better mechanical properties to the resin material cured from the secondary-cured resin composition.

[0173] Comparing Example 1 with Example 11, it can be seen that the relative humidity range of 60% RH to 100% RH can promote the more complete dissociation of imine groups and the more orderly formation of polyurethane segments, that is, it promotes the formation of a polyurethane elastomer with a more compact structure and more stable performance in the resin composition.

[0174] Among them, although the resin composition obtained in Comparative Example 6 contains polyurethane methacrylate, it is actually a polyurethane prepolymer blocked by methacrylate and does not contain isocyanate groups, and its storage time is relatively long. However, after the resin test specimens are prepared, their mechanical properties are poor and it is difficult to be applied in practice.

[0175] It should be noted that the terms "first", "second", etc. in the specification and claims of this application are used to distinguish similar objects and do not necessarily need to describe a specific order or sequence. It should be understood that such terms can be interchanged under appropriate circumstances so that the embodiments of this application described here can be implemented in an order other than those described here, for example.

[0176] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A resin composition, characterized in that, By weight parts, the resin composition comprises: 12 to 48 parts of a modified acrylate prepolymer, 2 to 30 parts of a polycyclic carbonate, 3 to 30 parts of a monomer, and 0.1 to 0.5 part of a photoinitiator; The modified acrylate prepolymer contains a polyimide group.

2. The resin composition according to claim 1, wherein By weight parts, the resin composition comprises: 16 to 27 parts of the modified acrylate prepolymer, 2 to 8 parts of the polycyclic carbonate, 4 to 10 parts of the monomer, and 0.2 to 0.3 part of the photoinitiator.

3. The resin composition according to claim 1 or 2, characterized in that, The polycyclic carbonate includes at least one of a bicyclic carbonate or a tricyclic carbonate; Preferably, the polycyclic carbonate is and / or 4. The resin composition according to any one of claims 1 to 3, wherein The photocurable monomer includes at least one of ethoxyethoxyethyl acrylate, lauryl methacrylate, N-acryloylmorpholine, and isobornyl methacrylate; and / or, The photoinitiator includes at least one of photoinitiator TPO, photoinitiator TMO, photoinitiator 907, photoinitiator 819, and photoinitiator 184.

5. The resin composition according to any one of claims 1 to 4, characterized in that, The modified acrylate prepolymer includes a compound obtained by reacting a polyamine, a hydroxyl-containing ketone compound, and an acrylate compound.

6. The resin composition according to claim 5, wherein The modified acrylate prepolymer includes a compound obtained by reacting polyetheramine D2000, hydroxyacetone, and methyl methacrylate; Or, The modified acrylate prepolymer includes a compound obtained by reacting polyetheramine T5000, hydroxyacetone, and methyl methacrylate.

7. The resin composition according to any one of claims 1 to 6, characterized in that, The modified acrylate prepolymer is prepared by the following steps: Step S1, performing a dehydration bonding reaction on the polyamine and the hydroxyl-containing ketone compound to obtain a hydroxyl-containing polyimide; Step S2, performing a transesterification reaction on the hydroxyl-containing polyimide and the acrylate compound to obtain the modified acrylate prepolymer.

8. The resin composition according to claim 7, wherein In step S1, The weight ratio of the polyamine to the hydroxyl-containing ketone compound is 1.2:1 to 12:1, preferably 6:1 to 12:1; and / or, The polyamine includes at least one of polyetheramine D2000, polyetheramine T5000, polyetheramine D400, 4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodiphenylmethane, and the hydroxyl-containing ketone compound is hydroxyacetone and / or 1,3-dihydroxyacetone; and / or, The reaction temperature of the dehydration bonding reaction is 80°C to 120°C, and the dehydration bonding reaction uses an organic acid as a catalyst.

9. The resin composition according to claim 7 or 8, characterized in that, In step S2, The weight ratio of the hydroxyl-containing polyimide to the acrylate compound is 0.05:1 to 0.5:1, preferably 0.2:1 to 0.5:1; and / or, The acrylate compound includes at least one of methyl acrylate, methyl methacrylate, ethyl acrylate, and methyl methacrylate; and / or, The transesterification reaction is carried out at 100°C to 120°C.

10. A method for preparing a three-dimensional object, characterized in that, Comprises: Irradiate the resin composition according to any one of claims 1 to 9 with a light source to form an initial three-dimensional object; Place the initial three-dimensional object in a water-containing atmosphere and subject it to a reaction at a predetermined temperature range to obtain a final three-dimensional object.

11. The method for preparing a three-dimensional object according to claim 10, characterized in that the relative humidity of the water-containing atmosphere is 60% RH to 100% RH, and the reaction is carried out at 60°C to 130°C; Preferably, the relative humidity of the water-containing atmosphere is 80% RH to 100% RH, and the reaction is carried out at 90 ± 5°C.

12. The method for preparing a three-dimensional object according to claim 10 or 11, characterized in that, The reaction time is 1 h to 10 h, preferably 8 h to 9 h.

13. The method for preparing a three-dimensional object according to any one of claims 10 to 12, characterized in that, The method for preparing the three-dimensional object further includes: Step (a), providing a light source module capable of emitting light, and at the same time providing a forming module provided with a forming platform and an optically transparent member, the optically transparent member having a construction surface, a construction area being defined between the forming platform and the construction surface, and the forming platform being used for carrying a three-dimensional object; Step (b), filling the construction area with the resin composition; Step (c), controlling the forming platform to move to a specified position in the construction area; Step (d), using the light source module to emit light, and making the light irradiate the construction area through the optically transparent member to cure at least a part of the resin composition; Step (e), controlling the forming platform to move away from the construction surface; Step (f), repeating steps (b) to (e) to form the initial three-dimensional object; Step (g), optionally, cleaning the initial three-dimensional object; and Step (h), placing the initial three-dimensional object in the water-containing atmosphere and subjecting it to a reaction at a predetermined temperature range to obtain the final three-dimensional object.

14. A product prepared by the method for preparing a three-dimensional object according to any one of claims 10 to 13, the product including any one of the following: footwear, sports protectors, toys, and equipment parts.

Images