3D printing photo-curable resin and preparation method therefor

Abstract

Disclosed in the present application are a 3D printing photo-curable resin and a preparation therefor. The preparation method comprises: under the constant-temperature and constant-humidity conditions of a preset temperature and a preset humidity, weighing 50-80 parts of an acrylate oligomer, 10-40 parts of a reactive diluent, 0.05-0.1 parts of an ultraviolet light absorber, and 0.01-0.05 parts of p-hydroxyanisole, adding the weighed substances into a container, and stirring the materials in the container at a first preset rotation speed; and after stirring for a first preset time, adding the weighed 5-10 parts of a cross-linking agent and 1-3 parts of a photoinitiator into the container while stirring, and stirring same for a second preset time at a second preset rotation speed under dark conditions, so as to obtain the 3D printing photo-curable resin. In this way, the resin has an extremely high strength and toughness, without a filler being added, and can avoid the problems of unstable material performance and poor printing precision.

Description

3D printing light-curing resin and preparation method thereof

[0001] This application claims priority to Chinese patent application number 202410117786.9, filed with the State Intellectual Property Office of China on January 26, 2024, entitled “3D printing photocurable resin and preparation method thereof,” portions of which are incorporated herein by reference. Technical Field

[0002] The present application relates to the technical field of 3D printing polymer materials, and in particular to a 3D printing photocurable resin and a preparation method thereof. Background Art

[0003] There has always been a huge market demand for 3D printing engineering materials. Due to mechanical stress, impact and other environmental factors in engineering applications, the materials have certain requirements on mechanical properties, such as tensile strength and elongation at break. At present, domestic and foreign light-curing 3D printing manufacturers all have their own models of high-strength and high-toughness resins, but these materials still have many problems: (1) The tensile strength of the materials is generally lower than 70MPa, which is difficult to meet some high-strength requirements; (2) The elongation at break of the materials is generally less than 10%; (3) The performance of the materials is unstable due to the uneven dispersion of the fillers; (4) The materials with fillers are prone to poor molding accuracy due to the scattering of light by the filler particles.

[0004] Application Contents

[0005] Based on this, the present application provides a 3D printing photocurable resin and a preparation method thereof. The resin has extremely high strength and toughness, is very suitable for precision parts that require high strength and high toughness, and does not require the addition of fillers, which can avoid the problems of unstable material properties and poor printing accuracy.

[0006] In a first aspect, the present application provides a 3D printing photocurable resin, which includes, by mass: 50-80 parts of an acrylate oligomer, 10-40 parts of a reactive diluent, 5-10 parts of a cross-linker, 1-3 parts of a photoinitiator, 0.05-0.1 parts of an ultraviolet light absorber, and 0.01-0.05 parts of p-hydroxyanisole.

[0007] In a second aspect, the present application provides a method for preparing a 3D printing light-curable resin, the method comprising:

[0008] Under constant temperature and humidity conditions of a predetermined temperature and predetermined humidity, weighing 50-80 parts of an acrylate oligomer, 10-40 parts of a reactive diluent, 0.05-0.1 parts of an ultraviolet light absorber, and 0.01-0.05 parts of p-hydroxyanisole, and adding the weighed acrylate oligomer, reactive diluent, ultraviolet light absorber, and p-hydroxyanisole to a container, and stirring the materials in the container at a first predetermined speed;

[0009] After stirring for a first predetermined time, 5 to 10 parts of a cross-linking agent and 1 to 3 parts of a photoinitiator are added to the container while stirring, and stirred at a second predetermined speed for a second predetermined time under light-proof conditions to obtain the 3D printing light-curing resin.

[0010] The present application provides a 3D printing light-curing resin and a preparation method thereof. The 3D printing light-curing resin includes: 50-80 parts of an acrylate oligomer, 10-40 parts of a reactive diluent, 5-10 parts of a cross-linking agent, 1-3 parts of a photoinitiator, 0.05-0.1 parts of an ultraviolet light absorber, and 0.01-0.05 parts of p-hydroxyanisole. The acrylate oligomer provides a basic skeleton for the resin, ensuring that the resin has a certain strength and toughness. The reactive diluent is used to reduce the viscosity of the resin, ensure printing accuracy, reduce the self-leveling time of the resin, and increase printing efficiency. , adjust the polymer molecular chain structure to make the resin have high toughness; the cross-linking agent is used to increase the cross-linking density of the resin and improve the strength and toughness of the resin; the photoinitiator is used to initiate the polymerization reaction of the resin, so that the resin is polymerized from liquid small molecules to solid macromolecules; the ultraviolet light absorber is used to control the printing accuracy of the resin; p-Hydroxyanisole as an inhibitor can prevent the formula from self-reaction during storage and extend the shelf life of the formula; therefore, the resin has extremely high strength and toughness, which is very suitable for precision parts that require high strength and high toughness, and no filler is added, which can avoid the problems of unstable material properties and poor printing accuracy. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] FIG1 is a schematic flow chart of an embodiment of a method for preparing a 3D printing light-curing resin according to the present invention. DETAILED DESCRIPTION

[0012] The following will be combined with the accompanying drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0013] In this application, the content of the formula is measured in parts by mass. Parts by mass is an intuitive mass ratio method used in industry for calculation convenience. The number directly represents the mass of the required proportion. In actual application, only the proportion needs to be added, and the unit can be changed as needed.

[0014] An embodiment of the present application provides a 3D printing photocurable resin, which includes, by weight, 50-80 parts of an acrylate oligomer, 10-40 parts of a reactive diluent, 5-10 parts of a crosslinker, 1-3 parts of a photoinitiator, 0.05-0.1 parts of an ultraviolet light absorber, and 0.01-0.05 parts of p-hydroxyanisole.

[0015] Photocurable resin, also known as photosensitive resin, is an oligomer that undergoes rapid physical and chemical changes upon exposure to light, resulting in crosslinking and solidification. It is composed of monomers and prepolymers, with the addition of a photo (UV) initiator. Exposure to UV light of a certain wavelength immediately triggers polymerization and completes curing. 3D printing, a form of rapid prototyping technology, also known as additive manufacturing, is a technique that uses digital model files as a foundation and uses adhesive materials such as powdered metal, plastic, or photosensitive resin to construct objects layer by layer. 3D printing photocurable resin is a type of photocurable resin used in 3D printing.

[0016] Acrylate oligomers are polymers formed by polymerization of acrylate monomers. They have multiple acrylate groups that can undergo cross-linking reactions under appropriate conditions. Acrylate oligomers provide a basic skeleton for the resin, ensuring that the resin has a certain strength and toughness. For example, the mass fractions of acrylate oligomers are 50 parts, 60 parts, 70 parts, 80 parts, etc.

[0017] Reactive diluent, also known as monomer or functional monomer, is an organic small molecule containing a polymerizable functional group. It is an important component in the various components of photocuring. It not only dissolves and dilutes oligomers, but also participates in the photocuring process, affecting the photocuring speed of the photocurable product and the various properties of the cured film. It is used to reduce the viscosity of the resin, ensure printing accuracy, reduce the self-leveling time of the resin, increase printing efficiency, and adjust the polymer molecular chain structure to make the resin have high toughness. For example: the mass fraction of the active diluent is 10 parts, 20 parts, 30 parts, 40 parts, etc.

[0018] The cross-linking agent is used to increase the cross-linking density of the resin and improve the strength and toughness of the resin; for example, the mass fraction of the cross-linking agent is 5 parts, 7 parts, 8 parts, 10 parts, etc.

[0019] The photoinitiator is used to initiate the polymerization reaction of the resin, so that the resin is polymerized from liquid small molecules to solid macromolecules; for example: the mass fraction of the photoinitiator is 1 part, 2 parts, 2.5 parts, 3 parts, etc.

[0020] The ultraviolet light absorber is used to control the printing accuracy of the resin; for example, the mass fraction of the ultraviolet light absorber is 0.05 parts, 0.07 parts, 0.08 parts, 0.1 parts, and the like.

[0021] As an inhibitor, p-hydroxyanisole can prevent the self-reaction of the formula during storage and extend the shelf life of the formula; for example: the mass fractions of p-hydroxyanisole are 0.01 parts, 0.02 parts, 0.035 parts, 0.05 parts, etc.

[0022] Therefore, the 3D printing photocurable resin of the embodiment of the present application has extremely high strength and toughness, and is very suitable for precision parts that require high strength and high toughness. No fillers are added, which can avoid the problems of unstable material properties and poor printing accuracy.

[0023] In some embodiments, the acrylate oligomer includes one or more of urethane dimethacrylate (UDMA), bisphenol A diglycidyl methacrylate (Bis-GMA), 2,2-bis[4-(2-ethoxy-3-methacryloyloxypropoxy)phenyl]propane (Bis-EMA), and triethylene glycol dimethacrylate (TEGDMA).

[0024] Urethane dimethacrylate (UDMA) exhibits excellent biocompatibility, film-forming properties, and rapid reaction. Bisphenol A diglycidyl methacrylate (Bis-GMA) exhibits excellent biocompatibility and mechanical properties. Its polymerization reaction rate is moderate, neither too fast nor too slow, resulting in a polymer with excellent properties. Triethylene glycol dimethacrylate (TEGDMA), a low-viscosity aliphatic dimethacrylate monomer, is an ideal comonomer for improving hardness and mechanical properties. TEGDMA is low-viscosity, easy to handle, non-toxic, and non-allergenic.

[0025] The four acrylate oligomers selected in the examples of the present application all have high strength, good biocompatibility, moderate reactivity, and high hardness after curing.

[0026] In some embodiments, the reactive diluent includes one or more of polyethylene glycol diacrylate (PEGDA), hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), isobornyl methacrylate (IBOMA), isobornyl acrylate (IBOA), 1,6-hexanediol diacrylate (HDDA), and 4-acryloylmorpholine (ACMO).

[0027] Polyethylene glycol diacrylate (PEGDA), a derivative of polyethylene glycol, is an environmentally friendly, biocompatible, and biodegradable polymer material. It can initiate polymerization reactions using a certain amount of initiator under heating, light, and radiation. Hydroxyethyl acrylate (HEA) has low viscosity, which is beneficial for controlling the viscosity of the resin and provides high strength after curing. Hydroxyethyl methacrylate (HEMA), a medical polymer raw material, has low toxicity and good biocompatibility. Its molecules contain vinyl functional groups, which easily generate active free radicals under the initiation of light or heat, leading to polymerization. It is a monomer that is relatively prone to polymerization reactions. 4-Acryloylmorpholine (ACMO) has good water solubility and strong water absorption.

[0028] The active diluent selected in the embodiment of the present application has low viscosity, medium reactivity, low toxicity, good chemical corrosion resistance after curing, and can form a relatively good copolymer system with the selected acrylate oligomer.

[0029] In some embodiments, the crosslinking agent includes one or more of ethoxylated bisphenol A dimethacrylate ((EO)BPADMA), ethoxylated bisphenol A diacrylate ((EO)BPADA), tripropylene glycol diacrylate (TPGDA), and ethoxylated pentaerythritol tetraacrylate (PPTTA).

[0030] Ethoxylated bisphenol A dimethacrylate (EO) BPADMA offers good solubility and a fast cure rate. Tripropylene glycol diacrylate TPGDA is a bifunctional crosslinker with low viscosity, low irritation, good compatibility, high activity, and a fast light cure rate. Ethoxylated pentaerythritol tetraacrylate PPTTA offers excellent flexibility, low viscosity, and high reactivity.

[0031] The cross-linking agents selected in the embodiments of the present application all have multiple reactive functional groups, high reactivity, high hardness after curing, high cross-linking density, and are compatible with the selected acrylate oligomers.

[0032] In some embodiments, the photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthone, and 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone.

[0033] Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, also known as photoinitiator 819 in Chinese, is a highly efficient photoinitiator with absorption peaks at 370nm and 405nm, and a maximum absorption wavelength of 450nm. The photolysis product contains two trimethylbenzoyl and one phenylphosphonyl free radicals, both of which are highly active free radicals, and have higher initiation activity than TPO.

[0034] 2,4,6-Trimethylbenzoylphenylphosphonic acid ethyl ester, also known as photoinitiator TPO-L in Chinese, is a liquid initiator. It has no solubility problems in the resin system, is easier to disperse, is conducive to storage, and does not have the problem of initiator precipitation.

[0035] Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, also known as photoinitiator TPO in Chinese, is a commonly used initiator. It is currently the largest and most widely used initiator. It has high initiation activity, is inexpensive, has many manufacturers, and is very easy to obtain.

[0036] 1-Hydroxycyclohexylphenyl ketone, also known as photoinitiator 184 or UV-184 in Chinese, is a white crystalline powder. It is a highly efficient photoinitiator for UV-curing systems and is mainly used for UV curing of acrylic varnish coatings on paper, wood, metal and plastic surfaces.

[0037] 2-Isopropylthioxanthone, also known as photoinitiator ITX in Chinese, is a yellow solid with average solubility. It is effective at low concentrations and has an absorption wavelength of 250-400 nm. It is a highly effective UV-curing initiator; photoinitiator ITX is used as a photoinitiator for UV-curable coatings.

[0038] 2-Methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, also known as photoinitiator 907 in Chinese, is a highly efficient photoinitiator used in UV curing systems, which can prevent yellowing for a long time and extend storage.

[0039] The photoinitiators selected in the embodiments of the present application all have the property of initiating free radical polymerization in the ultraviolet light band.

[0040] In some embodiments, the ultraviolet light absorber includes one or more of Sudan I, Sudan II, tartrazine, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone.

[0041] Sudan I and Sudan II are dark in color and have excellent UV absorption. Tartrazine can be used as a food additive, is inexpensive, readily available, and non-toxic. 2,4-Dihydroxybenzophenone has a wide absorption range, a wide range of uses, and good compatibility with resin materials. 2-Hydroxy-4-n-octyloxybenzophenone (UV531) has a low saturated vapor pressure, is not easily volatile, and is unlikely to migrate to surfaces and cause blooming.

[0042] The absorbents selected in the embodiments of the present application all have the property of high absorption of ultraviolet light, which can effectively reduce the over-curing effect of the material caused by scattered light.

[0043] In some embodiments, the acrylate oligomer has a glass transition temperature greater than or equal to 50°C and less than or equal to 160°C.

[0044] The glass transition temperature (Tg) refers to the temperature corresponding to the transition from the glassy state to the elastic state; the glass transition is an inherent property of amorphous polymer materials and is a macroscopic manifestation of the transformation of the polymer's motion form. It directly affects the performance and process performance of the material. Therefore, it has long been the main content of polymer physics research; Tg is the lowest temperature at which molecular chain segments can move, and its level is directly related to the flexibility of the molecular chain. The greater the flexibility of the molecular chain, the lower the Tg; the greater the rigidity of the molecular chain, the higher the Tg.

[0045] If the glass transition temperature of the acrylate oligomer is greater than 160°C, the resin may be too brittle. If the glass transition temperature of the acrylate oligomer is less than 50°C, the resin may be too soft.

[0046] Referring to FIG. 1 , FIG. 1 is a flow chart of an embodiment of a method for preparing a 3D printing light-curable resin according to the present application, the method comprising: step S101 and step S102 .

[0047] Step S101: Under constant temperature and humidity conditions of a predetermined temperature and a predetermined humidity, 50 to 80 parts of an acrylate oligomer, 10 to 40 parts of a reactive diluent, 0.05 to 0.1 parts of an ultraviolet light absorber, and 0.01 to 0.05 parts of p-hydroxyanisole are weighed in parts by mass, and the weighed acrylate oligomer, reactive diluent, ultraviolet light absorber, and p-hydroxyanisole are added to a container, and the materials in the container are stirred at a first predetermined speed.

[0048] Acrylate oligomer: 50-80 parts by weight, for example, 50, 60, 70, and 80 parts by weight of acrylate oligomer. Reactive diluent: 10-40 parts by weight, for example, 10, 20, 30, and 40 parts by weight of reactive diluent. UV absorber: 0.05-0.1 parts by weight, for example, 0.05, 0.07, 0.08, and 0.1 parts by weight of UV absorber. p-Hydroxyanisole: 0.01-0.05 parts by weight, for example, 0.01, 0.02, 0.035, and 0.05 parts by weight of p-Hydroxyanisole.

[0049] In some embodiments, the predetermined temperature is 25±5° C., and the predetermined humidity is 50±10%. An electronic balance can be used to weigh the required substances.

[0050] Step S102: After stirring for a first predetermined time, 5 to 10 parts of a cross-linking agent and 1 to 3 parts of a photoinitiator are added to the container while stirring, and the mixture is stirred at a second predetermined speed for a second predetermined time under light-shielding conditions to obtain the 3D printing light-curable resin.

[0051] The cross-linking agent is 5 parts to 10 parts, for example, the mass parts of the cross-linking agent are 5 parts, 7 parts, 8 parts, 10 parts, etc. The photoinitiator is 1 part to 3 parts, for example, the mass parts of the photoinitiator are 1 part, 2 parts, 2.5 parts, 3 parts, etc.

[0052] In some embodiments, the first predetermined rotational speed is 400±20 rpm, the first predetermined time is 3±0.3 h, the second predetermined rotational speed is 220±11 rpm, and the second predetermined time is 10±1 h.

[0053] In the embodiment of the present application, in preparing the above-mentioned 3D printing light-curing resin, an acrylate oligomer, a reactive diluent, an ultraviolet light absorber, and p-hydroxyanisole are first added to a container and stirred, and then a cross-linking agent and a photoinitiator are added and stirred under light-proof conditions to obtain the 3D printing light-curing resin. The formula is simple, the raw materials are easily available; the preparation method is simple and convenient, the cost is low, and the reaction conditions are relatively mild.

[0054] In some embodiments, the acrylate oligomer includes one or more of urethane dimethacrylate, bisphenol A diglycidyl methacrylate, 2,2-bis[4-(2-ethoxy-3-methacryloyloxypropoxy)phenyl]propane, and triethylene glycol dimethacrylate.

[0055] In some embodiments, the reactive diluent includes one or more of polyethylene glycol diacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, isobornyl methacrylate, isobornyl acrylate, 1,6-hexanediol diacrylate (HDDA), and 4-acryloylmorpholine.

[0056] In some embodiments, the crosslinking agent includes one or more of ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol A diacrylate, tripropylene glycol diacrylate, and ethoxylated pentaerythritol tetraacrylate.

[0057] In some embodiments, the photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthone, and 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone.

[0058] In some embodiments, the ultraviolet light absorber includes one or more of Sudan I, Sudan II, tartrazine, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-n-octyloxybenzophenone.

[0059] In some embodiments, the glass transition temperature of the acrylate oligomer is greater than or equal to 50°C and less than or equal to 160°C.

[0060] The following describes the 3D printing photocurable resin and its properties according to the embodiment of the present application through specific examples.

[0061] The tensile properties were tested using an ADMET micro-tensile testing machine, following the ASTM D1708 standard, and the printing accuracy was tested using a BMF NanoArch S140.

[0062] The first group includes Example A and Comparative Examples A1 to A3.

[0063] Example A:

[0064] The 3D printing light-curing resin includes: 60 parts of dimethacrylate urethane, 33 parts of polyethylene glycol diacrylate, 5 parts of ethoxylated bisphenol A dimethacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of Sudan I, and 0.03 parts of p-hydroxyanisole.

[0065] Comparative Example A1 (without crosslinking agent):

[0066] The 3D printing light-curing resin includes: 65 parts of dimethacrylate urethane, 33 parts of polyethylene glycol diacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of Sudan I, and 0.03 parts of p-hydroxyanisole.

[0067] Comparative Example A2 (no active diluent):

[0068] The 3D printing light-curing resin includes: 83 parts of dimethacrylate urethane, 15 parts of ethoxylated bisphenol A dimethacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of Sudan I, and 0.03 parts of p-hydroxyanisole.

[0069] Comparative Example A3: (without acrylate oligomer)

[0070] The 3D printing light-curing resin includes: 50 parts of polyethylene glycol diacrylate, 48 parts of ethoxylated bisphenol A dimethacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of Sudan I, and 0.03 parts of p-hydroxyanisole.

[0071] The experimental data are shown in Table 1:

[0072] Table 1

[0073] The test results in Table 1 show that the lack of a reactive diluent (Comparative Example A2) or a crosslinker (Comparative Example A1) results in a brittle material, preventing the production of a high-toughness material. The lack of an acrylate oligomer (Comparative Example A3) results in an extremely soft material, resulting in a lack of strength. Therefore, the resin formulation of this example (Example A) can produce a 3D printing material that combines high strength and toughness, while also offering the advantage of high printing precision.

[0074] The second group includes Example B and Comparative Example B1 to Comparative Example B3.

[0075] Example B:

[0076] The 3D printing light-curing resin includes: 75 parts of bisphenol A diglycidyl methacrylate, 18 parts of hydroxyethyl methacrylate, 5 parts of ethoxylated pentaerythritol tetraacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.08 parts of tartrazine, and 0.03 parts of p-hydroxyanisole.

[0077] Comparative Example B1 (no crosslinking agent):

[0078] The 3D printing light-curing resin includes: 80 parts of bisphenol A diglycidyl methacrylate, 18 parts of hydroxyethyl methacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.08 parts of tartrazine, and 0.03 parts of p-hydroxyanisole.

[0079] Comparative Example B2 (no active diluent):

[0080] The 3D printing light-curing resin includes: 83 parts of bisphenol A dimethacrylate glycidyl ester, 15 parts of ethoxylated pentaerythritol tetraacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.08 parts of tartrazine, and 0.03 parts of p-hydroxyanisole.

[0081] Comparative Example B3: (without acrylate oligomer)

[0082] The 3D printing light-curing resin includes: 50 parts of hydroxyethyl methacrylate, 48 parts of ethoxylated pentaerythritol tetraacrylate, 1.89 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.08 parts of tartrazine, and 0.03 parts of p-hydroxyanisole.

[0083] The experimental data are shown in Table 2:

[0084] Table 2

[0085] The test results in Table 2 show that the lack of a reactive diluent (Comparative Example B2) or a crosslinker (Comparative Example B1) results in a brittle material, preventing the production of a high-toughness material. The lack of an acrylate oligomer (Comparative Example B3) results in an extremely soft material, resulting in a lack of strength. Therefore, the resin formulation of this example (Example B) can produce a 3D printing material that combines high strength and toughness, while also offering the advantage of high printing precision.

[0086] The third group includes Examples C1 to C7.

[0087] The 3D printing light-curing resin includes: 50-80 parts of acrylate oligomer, 10-40 parts of reactive diluent, 5-10 parts of cross-linking agent, 1-3 parts of photoinitiator, 0.05-0.1 parts of ultraviolet light absorber, and 0.01-0.05 parts of p-hydroxyanisole.

[0088] Example C1:

[0089] 50 parts of dimethacrylate urethane, 40 parts of polyethylene glycol diacrylate, 8 parts of ethoxylated bisphenol A dimethacrylate, 1.94 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of Sudan I, and 0.01 parts of p-hydroxyanisole.

[0090] Example C2:

[0091] 55 parts of bisphenol A dimethacrylate glycidyl ester, 38 parts of hydroxyethyl acrylate, 5 parts of ethoxylated bisphenol A diacrylate, 1.93 parts of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 0.06 parts of Sudan II, and 0.01 parts of p-hydroxyanisole.

[0092] Example C3:

[0093] 60 parts of 2,2-bis[4-(2-ethoxy-3-methacryloyloxypropoxy)phenyl]propane, 29 parts of hydroxyethyl methacrylate, 8 parts of tripropylene glycol diacrylate, 2.92 parts of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of tartrazine, and 0.03 parts of p-hydroxyanisole.

[0094] Example C4:

[0095] 65 parts of triethylene glycol dimethacrylate, 25 parts of isobornyl methacrylate, 7 parts of ethoxylated pentaerythritol tetraacrylate, 2.94 parts of 1-hydroxycyclohexyl phenyl ketone, 0.03 parts of 2,4-dihydroxybenzophenone, and 0.03 parts of p-hydroxyanisole.

[0096] Example C5:

[0097] 70 parts of dimethacrylate urethane, 16.92 parts of isobornyl acrylate, 10 parts of ethoxylated pentaerythritol tetraacrylate, 3 parts of 2-isopropylthioxanthone, 0.03 parts of 2-hydroxy-4-n-octyloxybenzophenone, and 0.05 parts of p-hydroxyanisole.

[0098] Example C6:

[0099] 75 parts of dimethacrylate urethane, 14 parts of 1,6-hexanediol diacrylate, 7.9 parts of ethoxylated bisphenol A dimethacrylate, 3 parts of 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 0.05 parts of Sudan I, and 0.05 parts of p-hydroxyanisole.

[0100] Example C7:

[0101] 80 parts of bisphenol A dimethacrylate glycidyl ester, 10 parts of 4-acryloylmorpholine, 8.88 parts of ethoxylated bisphenol A dimethacrylate, 1 part of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.1 parts of tartrazine, and 0.02 parts of p-hydroxyanisole.

[0102] The experimental data are shown in Table 3:

[0103] Table 3

[0104] As can be seen from Table 3, the resin material of the embodiment of the present application has extremely high printing accuracy, and at the same time has the characteristics of high strength and high toughness, and has a wide range of applications.

[0105] In addition, the components used in this resin are all liquid components, which avoids the sedimentation and scattering problems caused by the addition of fillers; these raw materials are widely available, low-cost, and have no irritating odor, and the resin preparation process is simple and rapid, making it very suitable for large-scale industrial applications.

[0106] The preferred embodiments of the present application are described above with reference to the accompanying drawings, but are not intended to limit the scope of the present application. Any modifications, equivalent substitutions, and improvements made by those skilled in the art without departing from the scope and essence of the present application shall fall within the scope of the present application.

Claims

1. A 3D printing photocurable resin, wherein, By mass fraction, the photocurable resin comprises: 50 parts - 80 parts of acrylate oligomer, 10 parts - 40 parts of reactive diluent, 5 parts - 10 parts of crosslinking agent, 1 part - 3 parts of photoinitiator, 0.05 parts - 0.1 parts of ultraviolet light absorber, and 0.01 parts - 0.05 parts of p-methoxyphenol.

2. The photocurable resin according to claim 1, wherein the acrylate oligomer comprises one or more of dimethylacryloyl carbamate, bisphenol A diglycidyl dimethacrylate, 2,2-bis[4-(2-ethoxy-3-methacryloyloxypropoxy)phenyl]propane, and triethylene glycol dimethacrylate.

3. The photocurable resin according to claim 1, wherein, The reactive diluent comprises one or more of polyethylene glycol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, isobornyl methacrylate, isobornyl acrylate, 1,6-hexanediol diacrylate (HDDA), and 4-acryloylmorpholine.

4. The photocurable resin according to claim 1, wherein, The crosslinking agent comprises one or more of ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol A diacrylate, dipropylene glycol diacrylate, and ethoxylated pentaerythritol tetraacrylate.

5. The photocurable resin according to claim 1, wherein, The photoinitiator comprises one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthioxanthone, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholin-1-one.

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

7. The photocurable resin according to claim 1, wherein, The glass transition temperature of the acrylate oligomer is greater than or equal to 50 °C and less than or equal to 160 °C.

8. A preparation method of 3D printing photocurable resin, wherein, The method comprises: Under the constant temperature and humidity conditions of a predetermined temperature and a predetermined humidity, by mass fraction, weigh 50 parts - 80 parts of acrylate oligomer, 10 parts - 40 parts of reactive diluent, 0.05 parts - 0.1 parts of ultraviolet light absorber, and 0.01 parts - 0.05 parts of p-methoxyphenol, and add the weighed acrylate oligomer, reactive diluent, ultraviolet light absorber, and p-methoxyphenol into a container, and stir the materials in the container at a first predetermined rotation speed; After stirring for a first predetermined time period, then add the weighed 5 parts - 10 parts of crosslinking agent and 1 part - 3 parts of photoinitiator into the container under stirring, and stir for a second predetermined time period at a second predetermined rotation speed under light-shielded conditions to obtain the 3D printing photocurable resin.

9. The method according to claim 8, wherein The predetermined temperature is 25 ± 5 °C, and the predetermined humidity is 50 ± 10%.

10. The method according to claim 8, wherein, The first predetermined rotation speed is 400 ± 20 rpm, the first predetermined time period is 3 ± 0.3 h, the second predetermined rotation speed is 220 ± 11 rpm, and the second predetermined time period is 10 ± 1 h.

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