3D printing light-cured resin and method for preparing the same

Abstract

The application discloses a 3D printing light-cured resin and a preparation method thereof, and the preparation method comprises the following steps: weighing acryloyl morpholine, a crosslinking agent and a photoinitiator under constant temperature and humidity conditions with a predetermined temperature and humidity; adding the weighed acryloyl morpholine, the crosslinking agent and the photoinitiator into a container, and stirring the materials in the container under light-proof conditions at a predetermined rotating speed, wherein the container can avoid the materials in the container from absorbing moisture in the air; after stirring for a predetermined time length, adding a polymerization inhibitor into the container, and continuing to stir the materials in the container under light-proof conditions at the predetermined rotating speed for the predetermined time length, so as to obtain the 3D printing light-cured resin. In this way, the resin can provide a basic formula for realizing fast and complete dissolution and high printing precision.

Description

Technical Field

[0001] This application relates to the field of 3D printing polymer materials technology, and in particular to a 3D printing photocurable resin and its preparation method. Background Technology

[0002] Existing photopolymer 3D printing, as a novel rapid prototyping solution, can be used for low-cost, rapid product development, facilitating efficient product iteration. However, current 3D printing photopolymer resins suffer from slow and incomplete dissolution rates, as well as low printing accuracy. Summary of the Invention

[0003] Based on this, this application provides a 3D printing photocurable resin and its preparation method, which provides a basic formulation for achieving rapid and complete dissolution and high printing accuracy.

[0004] In a first aspect, this application provides a 3D printing photocurable resin, the photocurable resin comprising: acryloylmorpholine, a crosslinking agent, a photoinitiator, and a polymerization inhibitor.

[0005] Secondly, this application provides a method for preparing a 3D printing photocurable resin, the method comprising:

[0006] Under constant temperature and humidity conditions, weigh acrylamide, crosslinking agent, and photoinitiator;

[0007] The weighed acrylamide, crosslinking agent, and photoinitiator are added to a container, and the material in the container is stirred at a predetermined speed under light-protected conditions. The container is designed to prevent the material in the container from absorbing moisture from the air.

[0008] After stirring for a predetermined time, the weighed polymerization inhibitor is added to the container, and stirring is continued at the predetermined speed for the predetermined time under light-protected conditions to obtain the 3D printing photocurable resin.

[0009] This application provides a 3D printing photocurable resin and its preparation method. The 3D printing photocurable resin includes acryloylmorpholine, a crosslinking agent, a photoinitiator, and a polymerization inhibitor. Acryloylmorpholine has good water solubility, strong water absorption, and high reactivity, making it a key component for achieving 3D printing and rapid dissolution. The crosslinking agent can solve the problem of self-dissolution and swelling of acryloylmorpholine during printing, and is one of the key components for achieving 3D printing size control (i.e., printing accuracy). The photoinitiator is used to initiate the photocuring reaction and is an essential component of the 3D printing photocurable resin. The polymerization inhibitor can prevent self-reaction of the formulation during storage and extend the shelf life of the formulation. Therefore, this 3D printing photocurable resin can provide a basic formulation for achieving rapid and complete dissolution and high printing accuracy. This basic formulation is relatively simple and easy to prepare. After adjusting the content and further adjusting the formulation based on this 3D printing photocurable resin, the resulting resin can achieve rapid and complete dissolution and high printing accuracy. Attached Figure Description

[0010] Figure 1 This is a schematic flowchart of an embodiment of the method for preparing 3D printing photocurable resin according to this application. Detailed Implementation

[0011] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0012] In this application, the content of the formula is measured in parts by mass. Parts by mass is an intuitive method of mass proportioning used in industry for ease of calculation; the number directly represents the mass of the substances to be proportioned. In practical applications, it is only necessary to add according to the proportion, and the unit can be changed arbitrarily as needed.

[0013] This application provides a 3D printing photocurable resin, which includes: acryloylmorpholine, a crosslinking agent, a photoinitiator, and a polymerization inhibitor.

[0014] Photocurable resin, also known as photosensitive resin, is an oligomer that undergoes rapid physical and chemical changes upon exposure to light, leading to cross-linking and curing. It consists of polymer monomers and prepolymers, with the addition of a photoinitiator (ultraviolet light). Under ultraviolet light of a specific wavelength, it immediately initiates a polymerization reaction, completing the curing process. 3D printing technology, a type of rapid prototyping technology also known as additive manufacturing, is a technique that uses digital model files as a basis and employs powdered metals or plastics and other bondable materials to construct objects layer by layer. 3D printing photocurable resin is the photocurable resin used in 3D printing technology.

[0015] In this embodiment, acrylomorpholine is used as the main component. It possesses excellent water solubility, strong water absorption, and high reactivity, making it a key component for achieving 3D printing and rapid dissolution. The absence of this component will prevent the formulation from achieving its characteristic of dissolution in an aqueous environment. The crosslinking agent is used to address the self-dissolution and swelling of acrylomorpholine during the printing process and is one of the key components for achieving 3D printing dimensional control (i.e., printing accuracy). Without the crosslinking agent, the sample may dissolve during printing, resulting in the inability to obtain the target sample or significant dimensional deviations after printing. Photoinitiators, also known as photosensitizers or photocuring agents, are compounds that absorb energy of a certain wavelength in the ultraviolet or visible light region, generating free radicals, cations, etc., thereby initiating monomer polymerization, cross-linking, and curing. They are essential components of all photocuring 3D printing formulations; without photoinitiators, the formulation cannot be used for photocuring 3D printing. Inhibitors, on the other hand, prevent polymerization from occurring, preventing self-reaction during storage and extending the formulation's shelf life. Without inhibitors, the material will solidify during storage and cannot be stored for long periods.

[0016] Therefore, the 3D printing photocurable resin of this application embodiment can provide a basic formula for achieving rapid and complete dissolution and high printing accuracy. This basic formula is relatively simple and easy to prepare. After optimizing and adjusting the formula based on this 3D printing photocurable resin, a 3D printing photocurable resin with rapid and complete dissolution and high printing accuracy can be obtained.

[0017] In some embodiments, the crosslinking agent includes one or more of ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated bisphenol A decamethacrylate, and ethoxyethoxyethyl acrylate.

[0018] Ethoxylated trimethylolpropane triacrylate (ETPTA) possesses three functional groups: olefin, ester, and ether. It primarily exhibits the properties of acrylates, readily undergoing polymerization and demonstrating good activity in radiation curing reactions, making it a trifunctional monomer. EPTA is an improved version of trimethylolpropane triacrylate (TMPTA). From a polymer perspective, both have similar polymerization activity; however, the elongation of the nonpolar carbon chain results in EPTA having lower viscosity and shrinkage, and stronger flexibility and adhesion than TMPTA. From a synthetic perspective, EPTA is less hydrophilic than TMPTA, requiring less water, resulting in lower energy consumption, less wastewater, and a lower acid value, thus reducing human irritation.

[0019] Ethoxylated pentaerythritol tetraacrylate EQ4PETA is characterized by heat resistance, rapid curing, and low skin irritation.

[0020] Ethylene oxide bisphenol A decamethacrylate has high reactivity, low volatility and good chemical resistance, while having very little skin irritation and is unlikely to cause skin allergies.

[0021] Ethoxyethoxyethyl acrylate has multiple ethoxy structures that are less harmful to the human body, and its soft molecular chain can enhance the flexibility of resin formulations.

[0022] In some embodiments, the photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphine, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthraphenone, and 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone.

[0023] Phenylenol bis(2,4,6-trimethylbenzoyl)phosphine oxide, also known as photoinitiator 819, is a highly efficient photoinitiator with absorption peaks at 370 nm and 405 nm, and a maximum absorption wavelength of up to 450 nm. Its photolysis products contain two trimethylbenzoyl groups and one phenylphosphine acyl radical, both of which are highly active initiating radicals and have higher initiating activity than TPO.

[0024] 2,4,6-Trimethylbenzoylphenylphosphonic acid ethyl ester, also known as photoinitiator TPO-L, is a liquid initiator. It does not have a solubility problem in resin systems, is easier to disperse, is easier to store, and does not have an initiator precipitation problem.

[0025] Diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide, also known as photoinitiator TPO, is a commonly used initiator with the largest application volume and widest range. It has high initiation activity, is inexpensive, and is readily available due to the large number of manufacturers.

[0026] 1-Hydroxycyclohexylphenyl ketone, also known as photoinitiator 184 or UV-184, is a white crystalline powder. It is a highly efficient photoinitiator for ultraviolet curing systems and is mainly used for the UV curing of acrylic varnishes and coatings on paper, wood, metal and plastic surfaces.

[0027] 2-Isopropylthioxanthone, also known as photoinitiator ITX, is a yellow solid with moderate solubility. It is effective at low concentrations and absorbs light at wavelengths of 250–400 nm. It is a highly efficient UV curing initiator; ITX is used as a photoinitiator for UV-curable coatings.

[0028] 2-Methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, also known as photoinitiator 907, is a highly efficient photoinitiator used in UV curing systems to prevent yellowing and extend storage time.

[0029] In some embodiments, the polymerization inhibitor includes one or more of p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, and methylhydroquinone.

[0030] p-Hydroxyanisole (MEHQ) is easy to use, requires no special pretreatment, and can directly participate in the reaction; it also has low toxicity. Methylhydroquinone (THQ) has good solubility, requires only a small amount, and exhibits good thermal stability, having minimal impact on resin curing time and being unaffected by environmental and temperature conditions. 2,6-Di-tert-butyl-p-cresol (BHQ) has a low odor, does not exhibit metallic color reactions, and is therefore not limited by container type; it can be used as a food additive and thus has low toxicity to humans. 2,5-Di-tert-butylhydroquinone (DTBHQ) has the advantages of being non-toxic, odorless, and exhibiting good stability.

[0031] In some embodiments, p-hydroxyanisole is typically used as the polymerization inhibitor because it is inexpensive and readily available.

[0032] It should be noted that in this application, the content of the formula is measured in parts by mass. Parts by mass is an intuitive method of mass proportioning used in industry for ease of calculation; the number directly represents the mass of the substances to be proportioned. In practical applications, it is only necessary to add according to the proportion, and the unit can be changed arbitrarily as needed.

[0033] In some embodiments, the acrylamide is 60-80 parts, for example: 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, etc.

[0034] In some embodiments, the crosslinking agent is 15-40 parts, for example: 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc.

[0035] In some embodiments, the photoinitiator is 1 to 3 parts, for example: 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.

[0036] In some embodiments, the polymerization inhibitor is 0.01 to 0.05 parts, for example: 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, etc.

[0037] In some embodiments, the photocurable resin further includes an ultraviolet (UV) absorber. The UV absorber is used to control light scattering and improve 3D printing accuracy; it is one of the key components for achieving 3D printing size control. A lack of UV absorber leads to severe light scattering during printing, causing the resin around the sample to be cured by scattered light, resulting in significant dimensional deviations in the sample.

[0038] In some embodiments, the ultraviolet absorber is 0.02-0.1 parts, for example: 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, etc.

[0039] In some embodiments, the ultraviolet absorber includes one or more of Sudan I, Sudan II, tartrazine, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone.

[0040] Sudan I and Sudan II are dark in color and have good absorption of ultraviolet light. Tartrazine is a food additive that is inexpensive, readily available, and non-toxic. 2,4-Dihydroxybenzophenone has a wide absorption range, broad applications, and good compatibility with resin materials. 2-Hydroxy-4-n-octyloxybenzophenone (UV531) has a low saturated vapor pressure, is not easily volatilized, and does not easily migrate to the surface of objects, thus preventing blooming.

[0041] In some embodiments, the photocurable resin further includes water-soluble acrylate monomers. Water-soluble acrylate monomers are used to promote the dissolution of the overall cross-linked network, increase the strength of the printed material, and reduce the overall viscosity of the formulation; a lack of water-soluble acrylate monomers will result in the sample not dissolving quickly.

[0042] In some embodiments, the water-soluble acrylate monomer is 5 to 10 parts, for example, 5 parts, 6.5 parts, 8 parts, 10 parts, etc.

[0043] In some embodiments, the water-soluble acrylate monomer includes one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate.

[0044] Hydroxyethyl methacrylate (HEMA) is a medical-grade polymer raw material with low toxicity and good biocompatibility. Hydroxyethyl methacrylate has low viscosity, which is beneficial for resin viscosity control, resulting in high strength after curing. Polyethylene glycol diacrylate (PEG) is a biocompatible and biodegradable environmentally friendly polymer material.

[0045] See Figure 1 , Figure 1 This is a schematic flowchart of an embodiment of the method for preparing 3D printing photocurable resin according to this application. The method includes steps S101, S102 and S103.

[0046] Step S101: Under constant temperature and humidity conditions, weigh acrylamide, crosslinking agent and photoinitiator.

[0047] In some embodiments, the predetermined temperature may be 25°C and the predetermined humidity may be 50%. An electronic balance may be used to weigh the required substances.

[0048] Step S102: Weigh out acrylamide, crosslinking agent and photoinitiator and add them to a container. Stir the material in the container at a predetermined speed under light-protected conditions. The container is designed to prevent the material in the container from absorbing moisture from the air.

[0049] The container must be designed to prevent the material inside from absorbing moisture from the air; for example, a container with a lid that has a hole in the center can be used. In some embodiments, the predetermined rotational speed can be 600 ± 30 r / min.

[0050] Step S103: After stirring for a predetermined time, the weighed polymerization inhibitor is added to the container, and stirring is continued at the predetermined speed for the predetermined time under light-protected conditions to obtain the 3D printing photocurable resin.

[0051] In the preparation of the above-mentioned 3D printing photocurable resin in this application embodiment, acrylamide morpholine, crosslinking agent and photoinitiator are first added to a container and stirred under light-protected conditions. Then, a polymerization inhibitor is added and stirring is continued under light-protected conditions to obtain the 3D printing photocurable resin. The formula is simple and the raw materials are readily available. The preparation method is simple and convenient, can be quickly adjusted according to different needs, and is inexpensive. The reaction conditions are also relatively mild.

[0052] In some embodiments, the predetermined time may be 60 ± 3 minutes. Throughout the entire preparation process described above, care should be taken to minimize the absorption of moisture from the air by the material.

[0053] In some embodiments, the acrylamide is 60-80 parts, for example: 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, etc.

[0054] In some embodiments, the crosslinking agent is 15-40 parts, for example: 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, etc.

[0055] In some embodiments, the photoinitiator is 1 to 3 parts, for example: 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, etc.

[0056] In some embodiments, the polymerization inhibitor is 0.01 to 0.05 parts, for example: 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, etc.

[0057] In some embodiments, the crosslinking agent includes one or more of ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated bisphenol A decamethacrylate, and ethoxyethoxyethyl acrylate.

[0058] In some embodiments, the photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphine, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthraphenone, and 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone.

[0059] In some embodiments, the polymerization inhibitor includes one or more of p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, and methylhydroquinone.

[0060] In some embodiments, p-hydroxyanisole is typically used as the polymerization inhibitor because it is inexpensive and readily available.

[0061] In some embodiments, step S103, after stirring for a predetermined time, may further include adding the weighed polymerization inhibitor and ultraviolet absorber to the container after stirring for a predetermined time.

[0062] In some embodiments, the ultraviolet absorber is 0.02-0.1 parts, for example: 0.02 parts, 0.05 parts, 0.08 parts, 0.1 parts, etc.

[0063] In some embodiments, the ultraviolet absorber includes one or more of Sudan I, Sudan II, tartrazine, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone.

[0064] In some embodiments, step S103, after stirring for a predetermined time, may further include adding the weighed polymerization inhibitor, ultraviolet absorber and water-soluble acrylate monomer to the container after stirring for a predetermined time.

[0065] In some embodiments, the water-soluble acrylate monomer is 5 to 10 parts, for example, 5 parts, 6.5 parts, 8 parts, 10 parts, etc.

[0066] In some embodiments, the water-soluble acrylate monomer includes one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate.

[0067] The following specific embodiments illustrate the 3D printing photocurable resin and its properties according to the present application.

[0068] Printing accuracy was measured by the smallest printable horizontal hole (μm), using a nano Arch S140 3D printer. Solubility was measured by the dissolution time required for a 2mm*2mm*2mm sample to completely dissolve in a 1mol / L NaOH solution.

[0069] Control group:

[0070] The 3D printing photocurable resin includes: 60 parts of acryloylmorpholine, 1 part of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 0.02 parts of p-hydroxyanisole.

[0071] Example A1, corresponding to the control group:

[0072] The 3D printing photocurable resin includes: 60 parts of acryloylmorpholine, 40 parts of bisphenol A decamethacrylate, 1 part of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 0.02 parts of p-hydroxyanisole.

[0073] The experimental data are shown in Table 1:

[0074] Table 1

[0075]

[0076] As shown in Table 1, compared with the control group, the printing accuracy of Example A1 of this application is significantly improved after adding the crosslinking agent bisphenol A decamethacrylate, but the solubility is slightly reduced. In order to achieve precision manufacturing, the solubility can be slightly sacrificed to improve the printing accuracy.

[0077] The first set of embodiments includes embodiments A1 to A5:

[0078] The 3D printing photocurable resin includes: 60-80 parts of acryloylmorpholine, 15-40 parts of crosslinking agent, 1-3 parts of photoinitiator, and 0.01-0.05 parts of p-hydroxyanisole.

[0079] Example A1:

[0080] The 3D printing photocurable resin includes: 60 parts of acryloylmorpholine, 40 parts of bisphenol A decamethacrylate, 1 part of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 0.02 parts of p-hydroxyanisole.

[0081] Example A2:

[0082] The 3D printing photocurable resin includes: 75 parts of acryloylmorpholine, 20 parts of pentaerythritol tetraacrylate ethoxylate, 1.2 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 0.04 parts of p-hydroxyanisole.

[0083] Example A3:

[0084] The 3D printing photocurable resin includes: 65 parts of acrylamide morpholine, 30 parts of ethoxylated trimethylolpropane triacrylate, 1 part of 1-hydroxycyclohexylphenyl ketone, and 0.03 parts of p-hydroxyanisole.

[0085] Example A4:

[0086] The 3D printing photocurable resin includes: 72 parts of acrylamide, 20 parts of ethoxyethoxyethyl acrylate, 2 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and 0.02 parts of p-hydroxyanisole.

[0087] Example A5:

[0088] The 3D printing photocurable resin includes: 80 parts of acrylamide, 15 parts of ethoxyethoxyethyl acrylate, 3 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and 0.01 parts of p-hydroxyanisole.

[0089] The experimental data are shown in Table 2:

[0090] Table 2

[0091]

[0092]

[0093] The second set of embodiments includes embodiments B1 to B5:

[0094] The 3D printing photocurable resin includes: 60-80 parts of acryloylmorpholine, 15-40 parts of crosslinking agent, 1-3 parts of photoinitiator, 0.01-0.05 parts of p-hydroxyanisole, and 0.02-0.1 parts of ultraviolet light absorber.

[0095] Example B1:

[0096] The 3D printing photocurable resin includes: 60 parts of acrylamide, 40 parts of bisphenol A decamethacrylate, 1 part of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 0.02 parts of p-hydroxyanisole, and 0.03 parts of tartrazine.

[0097] Example B2:

[0098] The 3D printing photocurable resin includes: 75 parts acryloylmorpholine, 20 parts pentaerythritol tetraacrylate ethoxylate, 1.2 parts phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.04 parts p-hydroxyanisole, and 0.06 parts Sudan I.

[0099] Example B3:

[0100] The 3D printing photocurable resin includes: 65 parts of acrylamide morpholine, 30 parts of ethoxylated trimethylolpropane triacrylate, 1 part of 1-hydroxycyclohexylphenyl ketone, 0.03 parts of p-hydroxyanisole, and 0.03 parts of tartrazine.

[0101] Example B4:

[0102] The 3D printing photocurable resin includes: 72 parts of acrylamide, 20 parts of ethoxyethoxyethyl acrylate, 2 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.02 parts of p-hydroxyanisole, and 0.05 parts of Sudan II.

[0103] Example B5:

[0104] The 3D printing photocurable resin includes: 80 parts acrylamide, 15 parts ethoxyethoxyethyl acrylate, 3 parts ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.01 parts p-hydroxyanisole, and 0.1 parts Sudan I.

[0105] The experimental data are shown in Table 3:

[0106] Table 3

[0107]

[0108] The third set of embodiments includes embodiments C1 to C5:

[0109] The 3D printing photocurable resin includes: 60-80 parts of acryloylmorpholine, 15-40 parts of crosslinking agent, 1-3 parts of photoinitiator, 0.01-0.05 parts of p-hydroxyanisole, 0.02-0.1 parts of ultraviolet light absorber, and 5-10 parts of water-soluble acrylate monomer.

[0110] Example C1

[0111] The 3D printing photocurable resin includes: 60 parts of acrylamide, 40 parts of bisphenol A decamethacrylate, 1 part of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 0.02 parts of p-hydroxyanisole, 0.03 parts of tartrazine, and 7 parts of hydroxyethyl methacrylate.

[0112] Example C2:

[0113] The 3D printing photocurable resin includes: 75 parts acryloylmorpholine, 20 parts pentaerythritol tetraacrylate ethoxylate, 1.2 parts phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.04 parts p-hydroxyanisole, 0.06 parts Sudan I, and 5 parts polyethylene glycol diacrylate.

[0114] Example C3:

[0115] The 3D printing photocurable resin includes: 65 parts of acrylamide morpholine, 30 parts of ethoxylated trimethylolpropane triacrylate, 1 part of 1-hydroxycyclohexylphenyl ketone, 0.03 parts of p-hydroxyanisole, 0.03 parts of tartrazine, and 7 parts of hydroxyethyl methacrylate.

[0116] Example C4:

[0117] The 3D printing photocurable resin includes: 72 parts acrylamide, 20 parts ethoxyethoxyethyl acrylate, 2 parts ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.02 parts p-hydroxyanisole, 0.05 parts Sudan II, and 6 parts polyethylene glycol diacrylate.

[0118] Example C5:

[0119] The 3D printing photocurable resin includes: 80 parts acrylamide, 15 parts ethoxyethoxyethyl acrylate, 3 parts ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.01 parts p-hydroxyanisole, 0.1 parts Sudan I, and 10 parts hydroxyethyl methacrylate.

[0120] The experimental data are shown in Table 4:

[0121] Table 4

[0122]

[0123]

[0124] Based on the data from Tables 2 to 4 above, we can obtain the following Table 5:

[0125] Table 5

[0126]

[0127] The data above shows that, compared to the control group, the three sets of embodiments in this application exhibit higher printing precision, complete dissolution, and faster dissolution speed. The printing precision of the third set is comparable to that of the second set, but the dissolution speed of the third set is faster than that of the second set. This indicates that water-soluble acrylate monomers facilitate rapid dissolution of the 3D printing photocurable resin. The printing precision of the second and third sets is higher than that of the first set, and their dissolution speeds are also faster than those of the first set. This suggests that the ultraviolet absorber helps improve both printing precision and dissolution speed. The third set was completely dissolved in a 1 mol / L NaOH aqueous solution within 10 hours, demonstrating an extremely high dissolution rate, achieving the requirement of complete dissolution within 24 hours without any residue.

[0128] The 3D printing photocurable resin in this embodiment can be completely dissolved, indicating that the 3D printing photocurable resin has extremely strong water solubility. This 3D printing photocurable resin can be used in the 3D printing industry to achieve harmless treatment of 3D printed samples or for free injection molding.

[0129] The preferred embodiments of this application have been described above with reference to the accompanying drawings, but this does not limit the scope of the claims. Any modifications, equivalent substitutions, and improvements made by those skilled in the art without departing from the scope and spirit of this application shall be within the scope of the claims.

Claims

1. A 3D printing photocurable resin, characterized in that, The photocurable resin includes: acryloylmorpholine, crosslinking agent, photoinitiator, polymerization inhibitor, ultraviolet light absorber, and water-soluble acrylate monomer; By mass fractions, the acrylamide morpholine is 60-80 parts, the crosslinking agent is 15-40 parts, the photoinitiator is 1-3 parts, the polymerization inhibitor is 0.01-0.05 parts, the ultraviolet light absorber is 0.02-0.1 parts, and the water-soluble acrylate monomer is 5-10 parts; The crosslinking agent includes one or more of the following: ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxyethoxyethyl acrylate. The water-soluble acrylate monomers include one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate.

2. The photocurable resin according to claim 1, characterized in that, The photoinitiator includes one or more of the following: phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphine, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthraphenone, and 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone.

3. The photocurable resin according to claim 1, characterized in that, The polymerization inhibitor includes one or more of p-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, and methylhydroquinone.

4. The photocurable resin according to claim 1, characterized in that, The ultraviolet light absorber includes one or more of Sudan I, Sudan II, tartrazine, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone.

5. A method for preparing a 3D printing photocurable resin, characterized in that, The method includes: Under constant temperature and humidity conditions, weigh acrylamide, crosslinking agent, and photoinitiator; The weighed acrylamide, crosslinking agent, and photoinitiator are added to a container, and the material in the container is stirred at a predetermined speed under light-protected conditions. The container is designed to prevent the material in the container from absorbing moisture from the air. After stirring for a predetermined time, the weighed polymerization inhibitor, ultraviolet light absorber and water-soluble acrylate monomer are added to the container, and stirring is continued at the predetermined speed for the predetermined time under light-protected conditions to obtain the 3D printing photocurable resin. Of which, by mass parts, the acrylamide morpholine is 60-80 parts, the crosslinking agent is 15-40 parts, the photoinitiator is 1-3 parts, the polymerization inhibitor is 0.01-0.05 parts, the ultraviolet light absorber is 0.02-0.1 parts, and the water-soluble acrylate monomer is 5-10 parts; The crosslinking agent includes one or more of the following: ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated bisphenol A dimethacrylate, and ethoxyethoxyethyl acrylate. The water-soluble acrylate monomers include one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, and polyethylene glycol diacrylate.

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