Radiation curable resin composition, preparation method and application thereof, and product thereof

Abstract

The invention discloses a radiation curable resin composition and a preparation method, application and a product thereof, the resin composition is composed of, by mass, 40%-45% of oligomer, 53%-58% of reactive diluent and 2%-5% of photoinitiator, the oligomer comprises polyether urethane acrylate, aliphatic urethane acrylate, or a composition of the polyether urethane acrylate and the aliphatic urethane acrylate; the active diluent is prepared from a composition of acryloyl morpholine and 3, 3, 5-trimethyl cyclohexyl acrylate, or a composition of acryloyl morpholine, 3, 3, 5-trimethyl cyclohexyl acrylate and 2-hydroxyethyl acrylate, and the active diluent is prepared from a composition of acryloyl morpholine, 3, 3, 5-trimethyl cyclohexyl acrylate and 2-hydroxyethyl acrylate; the resin composition provided by the invention can be used for realizing a high-performance material which is suitable for being printed by light-cured 3D printing equipment adopting a surface exposure process, such as DLP or LCD, and has high elongation at break, high tearing strength and high precision.

Description

Technical Field

[0001] This application relates to the field of 3D printing technology, and particularly to a radiation-curable resin composition for 3D printing, a preparation method and application thereof, and articles thereof. Background Art

[0002] A radiation-curable resin composition (also known as a photosensitive resin composition) refers to a material composition used for photocuring rapid prototyping, which is mainly composed of an oligomer, a diluent, a photoinitiator, and an auxiliary agent. The liquid photosensitive resin composition will rapidly cause a polymerization reaction under the irradiation of ultraviolet light with a certain wavelength to complete the solid-state transformation; when the liquid photosensitive resin composition is applied in the field of 3D printing, for example, through a photocuring 3D printing device such as SLA, DLP, or LCD, a three-dimensional model divided into multiple cross-sectional layers is read, and then an entity is constructed by layer-by-layer printing. The photocuring 3D printing device has high forming accuracy and is widely used in customized products, medical jigs, prostheses, etc.

[0003] Among the materials of all current material compositions for photocuring rapid prototyping, there are materials with high elongation at break and materials with high tear resistance, but there is no material composition for photocuring rapid prototyping that can have both the characteristics of high elongation at break and high tear resistance. In addition, since such materials are all very soft materials, the accuracy of the 3D objects printed in actual printing is often very low, especially the accuracy of the 3D objects printed by photocuring 3D printing devices such as DLP or LCD that use surface exposure technology. Summary of the Invention

[0004] In view of the above-mentioned disadvantages of the related art, the purpose of this application is to provide a radiation-curable resin composition, a preparation method and application thereof, and articles thereof, aiming to achieve a high-performance material with high elongation at break, high tear resistance, and high precision that is applicable to photocuring 3D printing devices such as DLP or LCD that use surface exposure technology.

[0005] To achieve the above purpose and other related purposes, the first aspect of this application provides a radiation-curable resin composition, which is composed of: an oligomer with a mass fraction of 40%-45%, an active diluent with a mass fraction of 53%-58%, and a photoinitiator with a mass fraction of 2%-5%. Among them, the oligomer includes polyether polyurethane acrylate, aliphatic polyurethane acrylate, or a combination of polyether polyurethane acrylate and aliphatic polyurethane acrylate; the active diluent includes a combination of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate, or a combination of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate.

[0006] In an embodiment of the first aspect, the mass fraction of the polyether polyurethane acrylate is 20%-45%.

[0007] In an embodiment of the first aspect, the polyether polyurethane acrylate is selected from: BOMAR BR116, BOMAR BR204, BOMAR BR343, or BOMAR BR345.

[0008] In an embodiment of the first aspect, the mass fraction of the aliphatic polyurethane acrylate is 20%-40%.

[0009] In an embodiment of the first aspect, the aliphatic polyurethane acrylate is selected from: QR8121, QR8205, QR8206, SD8976 or CN8881NS.

[0010] In an embodiment of the first aspect, the mass fraction of the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate is 55%.

[0011] In an embodiment of the first aspect, in the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate with a mass fraction of 55%, the mass fraction of acryloylmorpholine is 5%-10%, and the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 45%-50%.

[0012] In an embodiment of the first aspect, the mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate is 53% or 58%.

[0013] In an embodiment of the first aspect, in the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate with a mass fraction of 53%, the mass fraction of acryloylmorpholine is 5%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

[0014] In an embodiment of the first aspect, in the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate with a mass fraction of 58%, the mass fraction of acryloylmorpholine is 10%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

[0015] In an embodiment of the first aspect, the photoinitiator includes (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO), or a composition of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone.

[0016] In an embodiment of the first aspect, the mass fraction of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) is 2%-3%.

[0017] In an embodiment of the first aspect, in the composition of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone, the mass fraction of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) is 3%, and the mass fraction of 1-hydroxycyclohexyl phenyl ketone is 2%.

[0018] The second aspect of the present application further provides a preparation method of a resin composition. The preparation method includes the following steps: putting an initiator with a mass fraction of 2%-5% and an active diluent with a mass fraction of 53%-58% into a stirring kettle for mixing, stirring at a speed of 600 r / min at room temperature for 30 min until dissolved; then adding an oligomer with a mass fraction of 40%-45% into the stirring kettle for mixing, and stirring at a speed of 600 r / min at room temperature for 30 min until dispersed to obtain the resin composition; wherein, the oligomer includes polyether polyurethane acrylate, aliphatic polyurethane acrylate, or a composition of polyether polyurethane acrylate and aliphatic polyurethane acrylate; the active diluent includes a composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate, or a composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl-2-hydroxyethyl acrylate.

[0019] The third aspect of the present application further provides the application of the radiation-curable resin composition as described in the first aspect above in 3D printing.

[0020] The fourth aspect of the present application further provides a resin material or resin product cured from the radiation-curable resin composition as described in the first aspect above. Brief Description of the Drawings

[0021] The specific features involved in the present application are shown in the appended claims. The features and advantages of the invention involved in the present application can be better understood by referring to the exemplary embodiments and drawings described in detail below. A brief description of the drawings is as follows:

[0022] Figure 1 It shows a flowchart of the preparation method of the radiation-curable resin composition of the present application in an embodiment. Detailed Description of the Embodiments

[0023] The following specific embodiments illustrate the implementation manners of the present application. Those skilled in the art can easily understand other advantages and effects of the present application from the content disclosed in this specification.

[0024] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts shall fall within the protection scope of the present application.

[0025] In the present application, the term "comprising" generally means including the expressly specified features, but not excluding other elements.

[0026] In the present application, the term "about" generally means varying within a range of 0.5% - 10% above or below the specified value. For example, it can vary within a range of 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10% above or below the specified value.

[0027] In the present application, the term "disperse" refers to the process of uniformly mixing, such as oligomers, reactive diluents, or photoinitiators, through, for example, stirring motion or centrifugal motion to evenly distribute various mixtures. In specific embodiments, the filler mixture can be incorporated into the resin through different mixing and dispersing systems, such as dissolvers, planetary mixers, paddle mixers, rotor-stator dispersers, or mixers operating on the principle of dual asymmetric centrifuges (DAC). On a laboratory scale, the DAC mixer can quickly and simply disperse particles and simultaneously degas even in highly viscous matrices.

[0028] In the present application, "min" is the abbreviation of "minute" and is used to represent minutes. For example, a stirring speed of 600 r / min hereinafter means that the number of revolutions per minute, such as the number of revolutions of the paddle of a paddle mixer or the rotor of a rotor-stator disperser, is 600. Another example is that a duration of 30 min represents a time length of 30 minutes. Similarly, "4 h" represents 4 hours.

[0029] In the present application, "oligomer" generally refers to a polymer composed of a relatively small number of repeating units. Generally speaking, it can be a polymer composed of ≤50, ≤40, ≤30, ≤20, or 5 - 10, 10 - 15, 15 - 20, 10 - 20 repeating units. Oligomers can usually undergo polymerization reactions with the same or other types of molecules to form polymers with higher molecular weights.

[0030] In the present application, the oligomer, also known as prepolymer, is a photosensitive resin with a relatively low molecular weight and has groups that can undergo photocuring reactions, such as various unsaturated double bonds or epoxy groups. Among the components of the radiation-curable resin composition in the present application, the oligomer is the main body of the resin composition, and its properties basically determine the main properties of the cured material. Therefore, the selection of the oligomer is undoubtedly the most important part of the design of photocuring products.

[0031] The radiation-curable resin composition contains an oligomer. In some embodiments, the oligomer includes polyether polyurethane acrylate, or aliphatic polyurethane acrylate, or a composition of polyether polyurethane acrylate and aliphatic polyurethane acrylate with a mass fraction of 40%-45%. For 3D printing materials, polyether polyurethane acrylate or aliphatic polyurethane acrylate has good flexibility, yellowing resistance, and low viscosity, but relatively low mechanical strength and hardness. For example: BOMAR (Bomar Corporation, USA) BR116, BOMAR BR204, BOMAR BR343, BOMAR BR345, as well as QR8121, QR8205, QR8206, SD8976, and CN8881NS developed or provided by other companies.

[0032] The mass fraction of the polyether polyurethane acrylate is 20%-45%. In some embodiments, the mass fraction of the oligomer, such as polyether polyurethane acrylate, used is 20%-45%. For example, the selected mass fraction can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, or 45%. The oligomer, such as polyether polyurethane acrylate, used is selected from one of BOMAR BR116, BOMAR BR204, BOMAR BR343, or BOMAR BR345 of Bomar Corporation, USA. For example, the mass fraction of the polyether polyurethane acrylate selected from BOMAR BR345 is 45%.

[0033] Taking the polyether polyurethane acrylate selected from BOMAR BR116 as an example, its reactive group is MA (MA = methacrylate), the functionality before curing is 3, and it has good flexibility after curing. This resin material has characteristics such as enhanced softness, base color, low shrinkage rate, good oil and chemical resistance, enhanced adhesion and flexibility, and good hydrolysis resistance stability.

[0034] Taking polyether polyurethane acrylate selected from BOMAR BR204 as an example, its reactive group is MA, the functionality before curing is 2, and it has good flexibility after curing. This resin material has characteristics such as high bonding strength, high elongation at break, low chromaticity, low viscosity, and good hydrolysis resistance stability.

[0035] Taking polyether polyurethane acrylate selected from BOMAR BR345 as an example, its reactive group is A (A = acrylate), the functionality before curing is 2, and it has good flexibility after curing. This resin material has characteristics such as good color stability, low hygroscopicity, low glass transition temperature Tg, low surface hardness, and impact resistance.

[0036] Taking polyether polyurethane acrylate selected from BOMAR BR343 as an example, its functionality is 2. This resin material has moderate elongation and low modulus, and at the same time has good color stability, does not yellow, has high clarity, and is easy to clean with solvents.

[0037] In some other embodiments, the mass fraction of the oligomer such as aliphatic polyurethane acrylate used is 20% - 40%. For example, the selected mass fraction can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%. In some embodiments, in the examples where the oligomer such as aliphatic polyurethane acrylate used is selected from QR8121, QR8205, QR8206, SD8976 or CN8881NS, for example, in one embodiment, the mass fraction of the aliphatic polyurethane acrylate selected from QR8121 is 20%; in another embodiment, the mass fraction of the aliphatic polyurethane acrylate selected from SD8976 is 40%; in yet another embodiment, the mass fraction of the aliphatic polyurethane acrylate selected from CN8881NS is 40%.

[0038] Taking the aliphatic polyurethane acrylate selected from QR8121 as an example, the QR8121 material is an aliphatic polyurethane acrylate resin material developed by Jiaxing Sudi Molecular Materials Co., Ltd., its functionality is 2, and the density is 1.02 g / cm 3 , and the refractive index at room temperature of 25 °C is 1.47. The QR8121 resin material has characteristics such as excellent flexibility, high strength, high elongation at break, and high resilience.

[0039] Taking the aliphatic polyurethane acrylate selected from QR8205 as an example, the QR8205 material is an aliphatic polyurethane acrylate resin material developed by Jiaxing Sudi Molecular Materials Co., Ltd., its functionality is 2, and the density is 1.00 g / cm3 , the refractive index at room temperature of 25°C is 1.47, and the QR8121 resin material has characteristics such as good adhesion, high strength, and high elongation at break.

[0040] Taking the aliphatic polyurethane acrylate selected from QR8206 as an example, the QR8206 material is an aliphatic polyurethane acrylate resin material developed by Jiaxing Sudi Molecular Materials Co., Ltd., with a functionality of 2 and a density of 1.00 g / cm 3 , the refractive index at room temperature of 25°C is 1.47, and the QR8121 resin material has characteristics such as good adhesion, high elongation at break, and high resilience.

[0041] Taking the aliphatic polyurethane acrylate selected from SD8976 as an example, the SD8976 resin material is a 2-functional aliphatic polyurethane acrylate developed by Guangzhou Songda New Materials Technology Co., Ltd., with a functionality of 2, and has characteristics such as a very fast curing speed, good adhesion, and toughness.

[0042] Taking the aliphatic polyurethane acrylate selected from CN8881NS as an example, the CN8881NS resin material is an aliphatic polyurethane acrylate resin material with a functionality of 2 from Sartomer (Guangzhou) Chemical Co., Ltd. (abbreviated as SARTOMER), which can provide an excellent balance between high elongation at break and tensile strength, and CN8881NS also shows excellent wear resistance, weather resistance, and adhesion to plastics and polycarbonates.

[0043] In an embodiment of the present application, it is also possible to use the oligomer of the composition of the polyether polyurethane acrylate and the aliphatic polyurethane acrylate. When using the composition of the polyether polyurethane acrylate and the aliphatic polyurethane acrylate, a ratio of 1:1 of the two can be used for combination. For example, the total mass fraction of the polyether polyurethane acrylate and the aliphatic polyurethane acrylate selected from the combination of BOMAR BR345 and QR8121 is 40%. Among them, in the combination ratio of BOMAR BR345 and QR8121, 20% by mass of BOMAR BR345 and 20% by mass of QR8121 are respectively used.

[0044] The radiation-curable resin composition contains an active diluent, also known as a monomer or functional monomer, which is a small molecule containing polymerizable functional groups. The active diluent is used to dissolve and dilute the oligomer to adjust the system viscosity, and also participates in the photocuring reaction, thereby affecting various properties of the photocured product. Therefore, selecting a suitable active diluent is an important part of the formulation design of photocured products. In the examples, the active diluents are classified into monofunctional active diluents, difunctional active diluents, and polyfunctional active diluents according to the number of reactive groups contained in each molecule. The more functional groups it has, the higher the reaction activity, the higher the crosslinking density, the poorer the flexibility, the greater the shrinkage, the better the mechanical properties, the higher the hardness, and the higher the heat resistance; otherwise, it is the opposite.

[0045] In some embodiments, the active diluent includes: two or three of morpholino acrylate, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate. For example, in one embodiment, the active diluent includes a composition of morpholino acrylate and 3,3,5-trimethylcyclohexyl acrylate; in another embodiment, the active diluent includes a composition of morpholino acrylate, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate.

[0046] The morpholino acrylate (ACMO) is a heat-resistant functional monomer with excellent performance, which has the characteristics of low viscosity and rapid curing. The ACMO material has good dilutability and solubility, and has good compatibility with oligomers. The nitrogen free radical in the ACMO molecule can inhibit the polymerization reaction caused by oxygen, and ACMO has good retention and elongation stability.

[0047] As a diluent, 3,3,5-trimethylcyclohexyl acrylate (TMCHA) can achieve low viscosity, low curing shrinkage rate, good heat resistance, and has a high Tg in the acrylic monomer. Compared with other aliphatic cyclic monomers, it has less odor, high Tg, and low viscosity UV diluent.

[0048] The 2-hydroxyethyl acrylate (HEA) is used as an active diluent and crosslinking agent in the radiation curing system. HEA can increase the overall transparency and flexibility, and can also be used as a light stabilizer for photosensitive polymers.

[0049] In some embodiments, the mass fraction of the active diluent used is 53%-58%; for example, it can be 53%, 54%, 55%, 56%, 57%, or 58%.

[0050] In one embodiment, the mass fraction of the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate is 55%. In the embodiment of the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate with a mass fraction of 55%, the mass fraction of acryloylmorpholine is 5% - 10%, and the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 45% - 50%. For example, when the mass fraction of acryloylmorpholine is 5%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 50%; for another example, when the mass fraction of acryloylmorpholine is 10%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 45%.

[0051] The mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate is 53% or 58%.

[0052] For example, the mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate is 53%. In this embodiment, the mass fraction of acryloylmorpholine is 5%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

[0053] For example, the mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate is 58%. In this embodiment, the mass fraction of acryloylmorpholine is 10%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

[0054] In the present application, the radiation-curable resin composition contains a photoinitiator with a mass fraction of 2% - 5%. The photoinitiator is the main component and also the key part of the photocured product, and it plays a decisive role in the photocuring rate of the photocured product. A photoinitiator is a substance that can absorb radiant energy, undergo a chemical change upon excitation, and generate active intermediates with the ability to initiate polymerization. It absorbs ultraviolet light irradiation to excite free radicals or cations, thereby initiating a polymerization reaction.

[0055] In a photocurable product, the content of the photoinitiator is much lower than that of the oligomer and the reactive diluent, generally 1% - 5%. However, in the resin composition of the present application, a photoinitiator with a mass fraction of 2% - 5% is selected. Different photoinitiators have their own unique absorption wavelength ranges. In the present application, the corresponding photoinitiator is selected as (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO), or a composition of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone (184). The selection of the photoinitiator mainly considers the reaction rate and its corresponding absorption wavelength. Different photoinitiators have their own unique absorption wavelength ranges. For the ultraviolet light wavelength generated by the corresponding equipment in one application implementation of the present application, it is approximately 405 nm.

[0056] In one embodiment, the photoinitiator contained in the radiation-curable resin composition may only select (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO). In this embodiment, the mass fraction of the (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) can be 2%.

[0057] In another embodiment, the photoinitiator contained in the radiation-curable resin composition selects a composition of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone (184). Among them, the mass fraction of the (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) is 3%, and the mass fraction of the 1-hydroxycyclohexyl phenyl ketone (184) is 2%.

[0058] The present application also provides a preparation method of a radiation-curable resin composition for 3D printing. The key lies in providing a combination of an oligomer and a reactive diluent to make the resin composition have a high elongation at break and a high tear strength and be able to meet most of the mechanical property requirements of 3D printing materials. Please refer to Figure 1 , which shows a flowchart of the preparation method of the radiation-curable resin composition of the present application in one embodiment. As shown in the figure, the preparation method includes the following steps:

[0059] First, step S1 is executed. A photoinitiator with a mass fraction of 2% - 5% and a reactive diluent with a mass fraction of 53% - 58% are put into a stirring kettle for mixing, and stirred at a speed of 600 r / min for 30 min at room temperature until dissolved. Among them, the reactive diluent includes a composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate, or a composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate.

[0060] In one embodiment, the photoinitiator contained in the radiation-curable resin composition may only select (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO). In this embodiment, the mass fraction of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) may be 2%.

[0061] In another embodiment, the photoinitiator contained in the radiation-curable resin composition selects a composition of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone (184). Among them, the mass fraction of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) is 3%, and the mass fraction of 1-hydroxycyclohexyl phenyl ketone (184) is 2%.

[0062] In some embodiments, the reactive diluent includes: two or three of morpholine acrylate, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate mixed. For example, in one embodiment, the reactive diluent includes a composition of morpholine acrylate and 3,3,5-trimethylcyclohexyl acrylate; in another embodiment, the reactive diluent includes a composition of morpholine acrylate, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate.

[0063] The morpholine acrylate (ACMO) is a heat-resistant functional monomer with excellent performance, which has the characteristics of low viscosity and rapid curing. The ACMO material has good dilutability and solubility, has good compatibility with oligomers, the nitrogen free radicals in the ACMO molecule can inhibit the polymerization reaction caused by oxygen, and ACMO has good retention and elongation stability.

[0064] The 3,3,5-trimethylcyclohexyl acrylate (TMCHA) is used as a diluent. TMCHA can achieve low viscosity, low curing shrinkage rate, good heat resistance, and has a high Tg in the acrylic monomer. Compared with other aliphatic cyclic monomers, it has less odor, high Tg, and low viscosity UV diluent.

[0065] The 2-hydroxyethyl acrylate (HEA) is used as a reactive diluent and crosslinking agent in the radiation curing system. HEA can increase the overall transparency and flexibility, and can also be used as a light stabilizer for photosensitive polymers.

[0066] In some embodiments, the mass fraction of the reactive diluent used is 53% - 58%; for example, it can be 53%, 54%, 55%, 56%, 57%, or 58%.

[0067] In one embodiment, the mass fraction of the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate is 55%. In the embodiment of the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate with a mass fraction of 55%, the mass fraction of acryloylmorpholine is 5% - 10%, and the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 45% - 50%. For example, when the mass fraction of acryloylmorpholine is 5%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 50%; for another example, when the mass fraction of acryloylmorpholine is 10%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 45%.

[0068] The mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate is 53% or 58%.

[0069] For example, the mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate is 53%. In this embodiment, the mass fraction of acryloylmorpholine is 5%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

[0070] For example, the mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate and 2-hydroxyethyl acrylate is 58%. In this embodiment, the mass fraction of acryloylmorpholine is 10%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

[0071] Then step S2 is executed, and an oligomer with a mass fraction of 40% - 45% is added to the stirring kettle for mixing, and stirred at a rotation speed of 600 r / min at room temperature for 30 min until dispersed to obtain the resin composition; the oligomer includes polyether polyurethane acrylate, aliphatic polyurethane acrylate, or a composition of polyether polyurethane acrylate and aliphatic polyurethane acrylate.

[0072] In some embodiments, the oligomer comprises 40%-45% by mass of polyether polyurethane acrylate, or aliphatic polyurethane acrylate, or a composition of polyether polyurethane acrylate and aliphatic polyurethane acrylate. For 3D printing materials, polyether polyurethane acrylate or aliphatic polyurethane acrylate has good flexibility and yellowing resistance and relatively low viscosity, mechanical strength, and hardness. For example: BOMAR (Bomar Inc., USA) BR116, BOMAR BR204, BOMAR BR343, BOMAR BR345, as well as QR8121, QR8205, QR8206, SD8976, and CN8881NS developed or provided by other companies.

[0073] The mass fraction of the polyether polyurethane acrylate is 20%-45%. In some embodiments, the mass fraction of the oligomer such as polyether polyurethane acrylate used is 20%-45%. For example, the selected mass fraction can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, or 45%. The oligomer such as polyether polyurethane acrylate used is selected from one of BOMAR BR116, BOMAR BR204, BOMAR BR343, or BOMAR BR345 of Bomar Inc., USA. For example, the mass fraction of the polyether polyurethane acrylate selected from BOMAR BR345 is 45%.

[0074] Taking the polyether polyurethane acrylate selected from BOMAR BR116 as an example, its reactive group is MA (MA = methacrylate (Methacrylic Acid) ester), the functionality before curing is 3, and it has good flexibility after curing. This resin material has characteristics such as enhanced softness, base color, low shrinkage rate, good oil and chemical resistance, enhanced adhesion and flexibility, and good hydrolysis resistance stability.

[0075] Taking the polyether polyurethane acrylate selected from BOMAR BR204 as an example, its reactive group is MA, the functionality before curing is 2, and it has good flexibility after curing. This resin material has characteristics such as high adhesion strength, high elongation at break, low chromaticity, low viscosity, and good hydrolysis resistance stability.

[0076] Taking polyether polyurethane acrylate selected from BOMAR BR345 as an example, its reactive group is A (A = acrylate), the functionality before curing is 2, and it has good flexibility after curing. This resin material has the characteristics of good color stability, low hygroscopicity, low glass transition temperature Tg, low surface hardness, and impact resistance.

[0077] Taking polyether polyurethane acrylate selected from BOMAR BR343 as an example, its functionality is 2. This resin material has moderate elongation and low modulus, and at the same time has good color stability, no yellowing, high clarity, and easy cleaning with solvents and other characteristics.

[0078] In some other embodiments, the mass fraction of the oligomer such as aliphatic polyurethane acrylate used is 20% - 40%. For example, the selected mass fraction can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%. In some embodiments, in the examples where the oligomer such as aliphatic polyurethane acrylate used is selected from QR8121, QR8205, QR8206, SD8976 or CN8881NS, for example, in one embodiment, the mass fraction of the aliphatic polyurethane acrylate selected from QR8121 is 20%; in another embodiment, the mass fraction of the aliphatic polyurethane acrylate selected from SD8976 is 40%; in yet another embodiment, the mass fraction of the aliphatic polyurethane acrylate selected from CN8881NS is 40%.

[0079] Taking the aliphatic polyurethane acrylate selected from QR8121 as an example, the QR8121 material is an aliphatic polyurethane acrylate resin material developed by Jiaxing Sudi Molecular Materials Co., Ltd., its functionality is 2, and the density is 1.02 g / cm 3 , and the refractive index at room temperature of 25 °C is 1.47. The QR8121 resin material has the characteristics of good flexibility, high strength, high elongation at break, and high resilience and other characteristics.

[0080] Taking the aliphatic polyurethane acrylate selected from QR8205 as an example, the QR8205 material is an aliphatic polyurethane acrylate resin material developed by Jiaxing Sudi Molecular Materials Co., Ltd., its functionality is 2, and the density is 1.00 g / cm 3 , and the refractive index at room temperature of 25 °C is 1.47. The QR8121 resin material has the characteristics of good adhesion, high strength, high elongation at break and other characteristics.

[0081] Taking aliphatic polyurethane acrylate selected from QR8206 as an example, the QR8206 material is an aliphatic polyurethane acrylate resin material developed by Jiaxing Sudy Molecular Materials Co., Ltd., with a functionality of 2 and a density of 1.00 g / cm 3 , and the refractive index at 25°C room temperature is 1.47. The QR8121 resin material has characteristics such as good adhesion, high elongation at break, and high resilience.

[0082] Taking aliphatic polyurethane acrylate selected from SD8976 as an example, the SD8976 resin material is a 2-functional aliphatic polyurethane acrylate developed by Guangzhou Songda New Materials Technology Co., Ltd., with a functionality of 2, and has characteristics such as a very fast curing speed, good adhesion, and toughness.

[0083] Taking aliphatic polyurethane acrylate selected from CN8881NS as an example, the CN8881NS resin material is an aliphatic polyurethane acrylate resin material with a functionality of 2 from Sartomer (Guangzhou) Chemical Co., Ltd. (abbreviated as SARTOMER). It can provide an excellent balance between high elongation at break and tensile strength. CN8881NS also shows excellent wear resistance, weather resistance, and adhesion to plastics and polycarbonates.

[0084] In an embodiment of the present application, oligomers of the composition of the polyether polyurethane acrylate and the aliphatic polyurethane acrylate can also be used. When using the composition of the polyether polyurethane acrylate and the aliphatic polyurethane acrylate, a ratio of 1:1 of the two can be used for combination. For example, the total mass fraction of the polyether polyurethane acrylate and the aliphatic polyurethane acrylate selected from the combination of BOMAR BR345 and QR8121 is 40%. Among them, in the combination ratio of BOMAR BR345 and QR8121, 20% by mass of BOMAR BR345 and 20% by mass of QR8121 are respectively used.

[0085] In another embodiment provided by the present application, the resin material or resin product cured from the radiation-curable resin composition can be used as a liquid resin material suitable for light-curing 3D printing, such as using a light-curing 3D printing device that adopts a surface exposure process such as DLP or LCD to print 3D objects.

[0086] In still another embodiment provided by the present application, the products made by 3D printing the radiation-curable resin composition, for example, are suitable for preparing devices with soft properties (such as flexible ducts), external prostheses, in-vivo implants, rubber gaskets, seat cushions, ductile sleeves, or rubber sleeves, etc., which are made by light-curing 3D printing.

[0087] Example 1:

[0088] Example 1 is provided below. This example provides a radiation-curable resin composition for 3D printing, which is composed of the following components in parts by mass fraction:

[0089] The oligomer is selected as polyether polyurethane acrylate (for example, BOMAR BR345) 45 parts; the reactive diluent is selected as morpholine acrylate 5 parts, 3,3,5-trimethylcyclohexyl acrylate 20 parts, and 2-hydroxyethyl acrylate 28 parts; the photoinitiator is selected as (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) 2 parts.

[0090] The specific implementation method of Example 1 is as follows: Mix the photoinitiator (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) in the composition of morpholine acrylate, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate, which are used as reactive diluents, and disperse at a rotation speed of 600 r / min for 30 min until completely dissolved; then add the oligomer of polyether polyurethane acrylate (BOMAR BR345) to the uniformly mixed liquid and continue to disperse at a rotation speed of 600 r / min for 30 min until completely and uniformly dispersed, thus obtaining the radiation-curable resin composition for 3D printing required in Example 1.

[0091] Using a 3D printer of the Raise3D Edge E2 model, adopting the curing technology of an LCD (its LCD screen is a 9.25-inch 6K black and white screen) radiation light source, pour the radiation-curable resin composition prepared by the above preparation method into the resin tank of the 3D printing device. Under normal room temperature (for example, at a room temperature condition of 25 ± 5 °C) and normal humidity conditions (for example, 50 ± 20%), at a wavelength of 405 nm, a layer thickness of 0.05 mm, and a light intensity of 4 mW / cm 2 and a forming speed setting parameter of 75 mm / h, perform 3D printing. Subsequently, place the sample of the 3D component completed by 3D printing at 25 - 30 °C and under a secondary curing light source (for example, placed in a curing box, and the light source of this curing box is 60 mW / cm 2 , ultraviolet light with a wavelength of 405 nm) for 10 - 60 min of secondary ultraviolet curing, and place it at normal room temperature (for example, at a room temperature condition of 25 ± 5 °C) and normal humidity conditions (for example, 50 ± 20%) for 24 h to obtain a 3D-printed sample. Test the viscosity (mpa.S), elongation at break (%), tear strength (N / m), and Shore hardness (A) of this sample. The test results are shown in Table 1. Then, clean it with alcohol, perform reverse scanning on the completed sample using a 3D scanner to obtain its accuracy, and store it at room temperature for 3 days to verify its storage capacity. The test results are shown in Table 2.

[0092] Example 2:

[0093] Example 2 is provided below. This example provides a radiation-curable resin composition for 3D printing, which is composed of the following components in parts by mass fraction:

[0094] The oligomer is 40 parts of aliphatic polyurethane acrylate (CN8881NS); the reactive diluent is 10 parts of acryloylmorpholine, 20 parts of 3,3,5-trimethylcyclohexyl acrylate, and 28 parts of 2-hydroxyethyl acrylate; the photoinitiator is 2 parts of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO).

[0095] The specific implementation method of Example 2 is as follows: Mix the photoinitiator (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) in the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate, which is the reactive diluent, and disperse it at a rotation speed of 600 r / min for 30 min until it is completely dissolved; then add the oligomer of aliphatic polyurethane acrylate (CN8881NS) to the uniformly mixed liquid and continue to disperse it at a rotation speed of 600 r / min for 30 min until it is completely and uniformly dispersed to obtain the radiation-curable resin composition for 3D printing required in Example 2.

[0096] Using the same 3D printer as in Example 1, print the sample of Example 2 under the same parameter configuration and conditions, test the viscosity (mpa.S), elongation at break (%), tear strength (N / m), and Shore hardness (A) of the sample. The test results are shown in Table 1. Then, clean it with alcohol, perform reverse scanning to obtain its accuracy, and store it at room temperature for 3 days to verify its storage capacity. The test results are shown in Table 2.

[0097] Example 3:

[0098] Example 3 is provided below. This example provides a radiation-curable resin composition for 3D printing, which is composed of the following components in parts by mass fraction:

[0099] The oligomer is 40 parts of aliphatic polyurethane acrylate (SD8976); the reactive diluent is 10 parts of acryloylmorpholine, 20 parts of 3,3,5-trimethylcyclohexyl acrylate, and 28 parts of 2-hydroxyethyl acrylate; the photoinitiator is 2 parts of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO).

[0100] The specific implementation method of Example 3 is as follows: The photoinitiator (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) is mixed in a composition of morpholine acrylate, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate, which are active diluents, and dispersed at a rotation speed of 600 r / min for 30 min until completely dissolved; then the oligomer of aliphatic polyurethane acrylate (SD8976) is added to the uniformly mixed liquid and continuously dispersed at a rotation speed of 600 r / min for 30 min until completely and uniformly dispersed, thus obtaining the radiation-curable resin composition for 3D printing required by Example 3.

[0101] Using the same 3D printer as in Example 1, a sample of Example 3 was printed under the same parameter configuration and conditions. The viscosity (mpa.S), elongation at break (%), tear strength (N / m), and Shore hardness (A) of the sample were tested. The test results are shown in Table 1. Then, it was cleaned with alcohol and reverse scanned to obtain its accuracy, and its storage capacity was verified by storing it at room temperature for 3 days. The test results are shown in Table 2.

[0102] Example 4:

[0103] The following provides Example 4. This example provides a radiation-curable resin composition for 3D printing, which is composed of the following components in parts by mass fraction:

[0104] The oligomer is selected as a composition of polyether polyurethane acrylate and aliphatic polyurethane acrylate, totaling 40 parts (including 20 parts of BOMAR BR345 and 20 parts of QR8121); the active diluent is selected as 5 parts of morpholine acrylate and 50 parts of 3,3,5-trimethylcyclohexyl acrylate; the photoinitiator is selected as 3 parts of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 2 parts of 1-hydroxycyclohexyl phenyl ketone (184).

[0105] The specific implementation method of Example 4 is as follows: The photoinitiators (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone (184) are mixed in a composition of morpholine acrylate and 3,3,5-trimethylcyclohexyl acrylate, which are active diluents, and dispersed at a rotation speed of 600 r / min for 30 min until completely dissolved; then the oligomers of polyether polyurethane acrylate and aliphatic polyurethane acrylate (BOMAR BR345 and QR8121) are added to the uniformly mixed liquid and continuously dispersed at a rotation speed of 600 r / min for 30 min until completely and uniformly dispersed, thus obtaining the radiation-curable resin composition for 3D printing required by Example 4.

[0106] The sample of Example 4 was printed using the same 3D printer as in Example 1 under the same parameter configuration and conditions. The viscosity (mpa.S), elongation at break (%), tear strength (N / m), and Shore hardness (A) of the sample were tested. The test results are shown in Table 1. Then, it was cleaned with alcohol, reverse scanned to obtain its accuracy, and stored at room temperature for 3 days to verify its storage capacity. The test results are shown in Table 2.

[0107] Example 5 is provided below. This example provides a radiation-curable resin composition for 3D printing, which is composed of the following components in parts by mass fraction:

[0108] The oligomer is a composition of polyether polyurethane acrylate and aliphatic polyurethane acrylate, totaling 40 parts (including 20 parts of BOMAR BR345 and 20 parts of QR8121); the reactive diluent is 10 parts of acryloylmorpholine and 45 parts of 3,3,5-trimethylcyclohexyl acrylate; the photoinitiator is 3 parts of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 2 parts of 1-hydroxycyclohexyl phenyl ketone (184).

[0109] The specific implementation method of Example 5 is as follows: Mix the photoinitiators of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone (184) in the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate, which is the reactive diluent, and disperse it at a speed of 600 r / min for 30 min until completely dissolved; then add the oligomers of polyether polyurethane acrylate and aliphatic polyurethane acrylate (BOMAR BR345 and QR8121) to the uniformly mixed liquid and continue to disperse it at a speed of 600 r / min for 30 min until completely and uniformly dispersed to obtain the radiation-curable resin composition for 3D printing required in Example 5.

[0110] The sample of Example 5 was printed using the same 3D printer as in Example 1 under the same parameter configuration and conditions. The viscosity (mpa.S), elongation at break (%), tear strength (N / m), and Shore hardness (A) of the sample were tested. The test results are shown in Table 1. Then, it was cleaned with alcohol, reverse scanned to obtain its accuracy, and stored at room temperature for 3 days to verify its storage capacity. The test results are shown in Table 2.

[0111] The following provides a comparative example. This comparative example provides a radiation-curable resin composition for 3D printing, which is composed of the following components in parts by mass fraction:

[0112] 50 parts of polyether polyurethane acrylate (BOMAR BR345) were selected as the oligomer; 25 parts of 2-hydroxyethyl acrylate, 5 parts of acryloylmorpholine, 13 parts of isobornyl acrylate (IBOA), and 5 parts of tetrahydrofurfuryl acrylate were selected as the reactive diluents; 2 parts of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) were selected as the photoinitiator.

[0113] The specific implementation method of the comparative example was as follows: The photoinitiator (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) was mixed in the composition of 2-hydroxyethyl acrylate, acryloylmorpholine, isobornyl acrylate, and tetrahydrofurfuryl acrylate, which was used as the reactive diluent, and dispersed at a speed of 600 r / min for 30 min until completely dissolved; then the oligomer of polyether polyurethane acrylate (BOMAR BR345) was added to the uniformly mixed liquid and continuously dispersed at a speed of 600 r / min for 30 min until completely and uniformly dispersed, thus obtaining the radiation-curable resin composition for 3D printing required by this comparative example.

[0114] Using the same 3D printer as in Example 1, samples of the comparative example were printed under the same parameter configuration and conditions, and the viscosity (mpa.S), elongation at break (%), tear strength (N / m), and Shore hardness (A) of the samples were tested. The test results are shown in Table 1. Then, the samples were cleaned with alcohol and reverse scanned to obtain their accuracy, and their storage capacity was verified by storing them at room temperature for 3 days. The test results are shown in Table 2.

[0115] The resins provided in the above Examples 1-5 and the comparative example were printed according to the method provided in the above application example, and samples for testing of Examples 1 to 5 and the comparative example were obtained respectively. At the same time, the following methods and test standards were referred to for performance testing:

[0116] 1. The viscosity of the resin was tested according to GB / T 2794-2013 "Determination of Viscosity of Adhesives - Single Cylinder Rotational Viscometer Method", and the viscosity unit was mpa.s.

[0117] 2. The tensile properties were tested according to ASTM-D412 "Test Method for Tensile Properties of Vulcanized Rubber and Thermoplastic Elastomers", the unit of elongation at break was %, and the unit of tensile strength was MPa.

[0118] 3. The tear resistance was tested according to ASTM-D624 "Tear Strength of Rubber and Thermoplastic Elastomers", and the unit of tear strength was N / m.

[0119] 4. The hardness was tested according to ASTM-D2240-2015 "Standard Test Method for Rubber Hardness by Durometer", and the unit was determined according to the durometer selected for the test.

[0120] The test results are shown in Table 1:

[0121] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example Viscosity (mpa.S) 305 429 342 367 409 589 Elongation at break (%) 147 131 172 256 298 143 Tear strength (N / m) 11 32 30 32 39 7.5 Shore hardness (A) 51 72 79 62 78 52

[0122] The resins provided in the above-mentioned examples and comparative examples were printed according to the method provided in the above-mentioned application examples to obtain test specimens of Examples 1 to 5 and the comparative example respectively. At the same time, tests were also carried out on the performance of the specimens of the photocuring 3D printing, such as whether they are suitable for alcohol cleaning, whether the surface is sticky, and whether the specimens of the 3D printing can be stored for a long time at room temperature. Among them, for the accuracy test of the specimens of the photocuring 3D printing, a three-dimensional scanner that meets the requirements of GB / T 39111 was used to perform reverse scanning on the completed model to obtain its three-dimensional scanning data. A third-party three-dimensional comparison software (such as Geomagic2013) was used to compare the three-dimensional scanning data with the original model, and the coincidence rate between the three-dimensional scanning data and the original model data was calculated, that is, the scanning accuracy (%), and the test results are shown in Table 2.

[0123] The test results are shown in Table 2:

[0124] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example Alcohol cleaning Sticky surface Sticky surface Sticky surface OK OK Sticky surface Storage capacity OK OK OK OK OK OK Scanning accuracy 82％ 85％ 82％ 91％ 91％ 78％

[0125] From the comparison of the above Examples 1-5 and the comparative example, it can be seen from the test data given by the comparative example that when 50% of polyether polyurethane acrylate is used in the resin composition, and 48% of the composition contains active diluents such as 2-hydroxyethyl acrylate, acryloylmorpholine, isobornyl acrylate, and tetrahydrofuran acrylate, and 2% of photoinitiator is used, the prepared resin composition is found to have a relatively high viscosity, and the elongation at break of the sample of the comparative example, especially its tear strength, is significantly lower than the data of the above Examples 1-5, and the accuracy of the specimens obtained from the resin composition prepared in this comparative example is also significantly lower than that of the above Examples 1-5; while the test specimens prepared from the radiation-curable resin composition of the present application have good performance in terms of viscosity, elongation at break, tear strength, Shore hardness and printing accuracy. In particular, the optimal combination is Example 5, which can reach a viscosity of 409 mPa·s; an elongation at break of 298%; a tear strength of 39 N / m; a Shore hardness of 78A; a printing accuracy of over 90%, and it is easy to be cleaned with alcohol and has high storage stability. From the above results, it can be concluded that the radiation-curable resin composition provided by the present application can be used as a photocuring material for photocuring 3D printing equipment such as DLP or LCD using surface exposure technology. The 3D components printed therefrom have the advantages of high elongation at break, high tear strength and low viscosity, and can meet most of the mechanical property requirements of 3D printing materials.

[0126] The radiation-curable resin composition provided by the present application can be used in photocuring forming technology. The radiation-curable resin composition can generally undergo a polymerization reaction and cure to form a formed body under conditions capable of triggering a free radical initiator. The curing forming technology can include but is not limited to radiation curing forming technology, etc., and more specifically can include but is not limited to DLP photocuring forming technology, LCD photocuring forming technology, etc. In an embodiment provided by the present application, the application of the radiation-curable resin composition in 3D printing. In this embodiment, the usage method of the radiation-curable resin composition includes the following steps:

[0127] Step 1: Introduce the radiation-curable resin composition prepared by the above preparation method into the resin tank of the 3D printing device. Under normal room temperature (for example, at a room temperature condition of 25 ± 5 °C) and normal humidity conditions (for example, 50 ± 20%), let the 3D printing device perform a 3D printing operation to cure and form, so as to obtain a 3D component / model; the light source used in this process is ultraviolet light with a wavelength of 405 nm and an intensity of 4 mW / cm 2 .

[0128] Step 2: Subsequently, place the 3D component / model completed by 3D printing under a secondary curing light source (for example, placed in a curing box) at 25 - 30 °C for 10 - 60 min of secondary ultraviolet light curing, and place it at normal room temperature (for example, at a room temperature condition of 25 ± 5 °C) and normal humidity conditions (for example, 50 ± 20%) for 24 h to obtain a photocured model. The light source for this process is ultraviolet light with a wavelength of 405 nm and an intensity of 60 mW / cm 2 .

[0129] The 3D component / model printed by the above 3D printing method has the advantages of high elongation at break, high tear resistance, and low viscosity, and can meet most of the mechanical property requirements of 3D printing materials.

[0130] The above embodiments only illustratively explain the principles and effects of the present application, rather than limiting the present application. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present application. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the relevant technical field without departing from the spirit and technical idea disclosed by the present application should still be covered by the claims of the present application.

Claims

1. A radiation-curable resin composition, characterized in that, The resin composition consists of: an oligomer with a mass fraction of 40%-45%, a reactive diluent with a mass fraction of 53%-58%, and a photoinitiator with a mass fraction of 2%-5%. Among them, the oligomer includes polyether polyurethane acrylate, aliphatic polyurethane acrylate, or a composition of the polyether polyurethane acrylate and the aliphatic polyurethane acrylate; the reactive diluent includes a composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate, or a composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate.

2. The radiation-curable resin composition according to claim 1, wherein The mass fraction of the polyether polyurethane acrylate is 20%-45%.

3. The radiation-curable resin composition according to claim 1, wherein The polyether polyurethane acrylate is selected from: BOMAR BR116, BOMAR BR204, BOMAR BR343, or BOMAR BR345.

4. The radiation-curable resin composition according to claim 1, wherein The mass fraction of the aliphatic polyurethane acrylate is 20%-40%.

5. The radiation-curable resin composition according to claim 1, characterized in that, The aliphatic polyurethane acrylate is selected from: QR8121, QR8205, QR8206, SD8976, or CN8881NS.

6. The radiation-curable resin composition according to claim 1, wherein The mass fraction of the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate is 55%.

7. The radiation-curable resin composition according to claim 6, characterized in that, In the composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate with a mass fraction of 55%, the mass fraction of acryloylmorpholine is 5%-10%, and the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 45%-50%.

8. The radiation-curable resin composition according to claim 1, wherein, The mass fraction of the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate is 53% or 58%.

9. The radiation-curable resin composition according to claim 8, wherein, In the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate with a mass fraction of 53%, the mass fraction of acryloylmorpholine is 5%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

10. The radiation-curable resin composition according to claim 8, wherein, In the composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate with a mass fraction of 58%, the mass fraction of acryloylmorpholine is 10%, the mass fraction of 3,3,5-trimethylcyclohexyl acrylate is 20%, and the mass fraction of 2-hydroxyethyl acrylate is 28%.

11. The radiation-curable resin composition according to claim 1, characterized in that, The photoinitiator includes (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO), or a composition of the (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone.

12. The radiation-curable resin composition according to claim 11, wherein The mass fraction of the (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) is 2%-3%.

13. The radiation-curable resin composition according to claim 11, wherein, In the composition of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) and 1-hydroxycyclohexyl phenyl ketone, the mass fraction of (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) is 3%, and the mass fraction of 1-hydroxycyclohexyl phenyl ketone is 2%.

14. A method for preparing a resin composition, characterized in that, The preparation method includes the following steps: Put an initiator with a mass fraction of 2%-5% and an active diluent with a mass fraction of 53%-58% into a stirring kettle for mixing, and stir at a speed of 600 r / min for 30 min at room temperature until dissolved; Then add an oligomer with a mass fraction of 40%-45% to the stirring kettle for mixing, and stir at a speed of 600 r / min for 30 min at room temperature until dispersed to obtain the resin composition; Among them, the oligomer includes polyether polyurethane acrylate, aliphatic polyurethane acrylate, or a composition of polyether polyurethane acrylate and aliphatic polyurethane acrylate; the active diluent includes a composition of acryloylmorpholine and 3,3,5-trimethylcyclohexyl acrylate, or a composition of acryloylmorpholine, 3,3,5-trimethylcyclohexyl acrylate, and 2-hydroxyethyl acrylate.

15. Application of the radiation-curable resin composition according to any one of claims 1-13 in 3D printing.

16. A resin material or resin product cured from the radiation-curable resin composition according to any one of claims 1-13.

17. An article made by 3D printing using the radiation-curable resin composition according to any one of claims 1-13.

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