Thermosetting fluorescent photosensitive resin for DLP-3D printing and preparation method and application thereof

Abstract

The invention discloses thermosetting fluorescent photosensitive resin for DLP-3D printing as well as a preparation method and application of the thermosetting fluorescent photosensitive resin. The preparation method provided by the invention comprises the following steps: taking epoxy resin as a prepolymer, combining with AIE fluorescent dye molecules with groups such as-COOH,-OH,-SH or-NH2 through condensation reaction, and then copolymerizing with acrylic acid and methacrylic acid monomers; and then adding a diluent and a photoinitiator to prepare the novel thermosetting photosensitive resin with fluorescence after curing. The photosensitive resin is small in smell, high in curing rate and high in precision of printed parts; and a workpiece cured under the ultraviolet of 405nm can emit strong blue fluorescence under the excitation of an ultraviolet lamp of 365nm.

Description

Technical Field

[0001] The present invention belongs to the technical field of DLP-3D printing materials, and in particular relates to a thermosetting fluorescent photosensitive resin for DLP-3D printing and a preparation method and application thereof. Background Art

[0002] After decades of in-depth research and development, 3D printing technology has produced many different types. The most commonly used ones are the following: Selective Laser Sintering (SLS), Selective Laser Melting (SLM), Fused Deposition Modeling (FDM), Stereo Lithography Apparatus (SLA and Digital Light Procession, DLP), and Poly Jet. Among them, DLP stereolithography is the most widely studied, mature and widely used rapid prototyping method in the world. DLP printing uses photosensitive resin as the material. The photosensitive resin is prepared by oligomers, diluents, photoinitiators and various additives according to a certain experimental ratio. The purpose of curing and molding is achieved by using photosensitive resin to polymerize under the illumination of a specific wavelength. The curing process is to complete the curing of one surface and then the projector solidifies the liquid photosensitive resin layer by layer to finally create a three-dimensional entity.

[0003] In recent years, due to the popularity of DLP-3D printing technology and photosensitive resins, people are no longer satisfied with just designing and printing various three-dimensional models. A variety of printing materials have recently appeared, such as 4D printing materials, which can change shape under the stimulation of light and heat. Human demand for multifunctional printing materials is increasing day by day.

[0004] Chinese patent applications with publication numbers CN115057708B, CN113045708B, CN112812623B, CN111171251B and CN111205467B all disclose 3D printing materials with fluorescent effects. However, the above-mentioned disclosed technologies are all based on traditional fluorescent dyes, which have the disadvantages of being easily quenched and bleached, hindering their practical application.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] In view of the shortcomings of existing commercial photosensitive resins, the purpose of the present invention is to provide a method for preparing a thermosetting fluorescent photosensitive resin for DLP-3D printing. The thermosetting fluorescent photosensitive resin prepared by the method not only has a small irritating odor, a fast curing speed, and high printing accuracy; but also the printed model can emit strong blue fluorescence under 365nm ultraviolet excitation, and this fluorescence is not easily quenched or bleached.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] The preparation method of the thermosetting fluorescent photosensitive resin for DLP-3D printing provided by the present invention is to use epoxy resin as a prepolymer, graft AIE fluorescent dye molecules through a condensation reaction, and then copolymerize with acrylic monomers; then add a diluent and a photoinitiator to obtain the thermosetting fluorescent photosensitive resin for DLP-3D printing.

[0009] The specific preparation method comprises the following steps:

[0010] (1) mixing the AIE fluorescent dye molecule and the epoxy resin prepolymer and subjecting them to a reflux reaction to obtain a reaction system 1;

[0011] (2) dissolving triphenylphosphine in an acrylic monomer and adding the mixture into the reaction system 1 to continue the reflux reaction;

[0012] (3) The product obtained in step (2) is placed at room temperature, and a photoinitiator and a diluent are added thereto, and reacted at room temperature to obtain the thermosetting fluorescent photosensitive resin for DLP-3D printing.

[0013] In step (1) of the above method, the AIE fluorescent dye molecule has at least one active group that can undergo a ring-opening reaction with an epoxy group, including but not limited to: a carboxyl group, a hydroxyl group, a thiol group or an amino group;

[0014] Furthermore, the AIE fluorescent dye molecule may be a tetraphenylethylene (TPE) fluorescent molecule; according to an embodiment of the present invention, the AIE fluorescent dye molecule is TPE-COOH (McLean, CAS No.: 197153-87-0).

[0015] In step (1) of the above method, the epoxy resin prepolymer includes but is not limited to common reagents such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin or novolac epoxy resin.

[0016] According to an embodiment of the present invention, the epoxy resin prepolymer is bisphenol A epoxy resin (McLean, CAS No.: 30583-72-3).

[0017] In step (1) of the above method, the AIE fluorescent dye molecule is monocarboxyl TPE-COOH, and the mass ratio of the monocarboxyl TPE-COOH to the epoxy resin prepolymer is (0.01-0.05) g:(80-100) g;

[0018] According to an embodiment of the present invention, the feed mass ratio of TPE-COOH to bisphenol A epoxy resin may be 0.01:80, 0.03:80, 0.05:80 or 0.01:100.

[0019] In step (1) of the above method, the reaction conditions of the reflux reaction are: stirring under reflux at 80-85° C. for 1-2 h, specifically, stirring under reflux at 80° C. for 1 h. The stirring rate may be 250 r / min.

[0020] In step (2) of the above method, the acrylic monomer includes but is not limited to: acrylic acid and methacrylic acid monomers. According to an embodiment of the present invention, the acrylic monomer is methacrylic acid.

[0021] In step (2) of the above method, the feed ratio of triphenylphosphine to methacrylic acid is (0.72-1.44) g:(40-60) g.

[0022] According to an embodiment of the present invention, the feed ratio of triphenylphosphine to methacrylic acid is 0.72g:40g, 0.72g:50g or 0.72g:60g.

[0023] According to an embodiment of the present invention, triphenylphosphine is dissolved in methacrylic acid and then dripped into the reaction system 1 within 1 to 1.5 hours.

[0024] In step (2) of the above method, the reaction conditions of the reflux reaction are: stirring under reflux at 100-110° C. for 4-5 hours, specifically stirring under reflux at 100° C. for 4 hours. The stirring rate is 350 r / min.

[0025] In step (3) of the above method, the photoinitiator is a long-wave photoinitiator, including but not limited to: 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone (910), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylphosphonic acid ethyl ester (TPO-L), 2-isopropylthioxanthenone (2,4 isomer mixture) (ITX) and other common long-wave photoinitiators.

[0026] In step (3) of the above method, the diluent includes but is not limited to: isopropyl alcohol acrylate, ethoxyethoxyethyl ethyl acrylate, and neopentyl glycol diacrylate.

[0027] According to an embodiment of the present invention, the photoinitiator is 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone (910), and the diluent is ethoxyethoxyethyl ethyl acrylate.

[0028] The feed ratio of the photoinitiator 910 and the diluent ethoxyethoxyethyl ethyl acrylate is (4-8) g: (40-60) g;

[0029] In step (3) of the above method, the reaction is stirred at room temperature for 1 to 2 hours, specifically for 1 hour. The stirring rate is 80 r / min.

[0030] In the method of the present invention, the ratio of the raw material TPE-COOH, epoxy resin prepolymer (such as bisphenol A epoxy resin), triphenylphosphine, methacrylic acid, photoinitiator (such as photoinitiator 910), and diluent ethoxyethoxyethyl acrylate is (0.01-0.05) g: (80-100) g: (0.72-0.144) g: (40-60) g: (4-8) g: (40-60) g.

[0031] Preferably, in step (1), the amount of TPE-COOH is 0.01 g, the amount of bisphenol A epoxy resin is 80 g, and the stirring rate is 250 r / min.

[0032] Preferably, in step (2), the amount of triphenylphosphine used is 0.72 g, the amount of methacrylic acid used is 40 g, and the reflux stirring condition is 100° C., 350 r / min, and stirring for 4 h.

[0033] Preferably, in step (3), the amount of the photoinitiator 910 is 4 g, the amount of the diluent ethoxyethoxyethyl acrylate is 40 g, and the stirring condition is continuous stirring at 80 r / min for 1 hour at room temperature.

[0034] The present invention aims to provide a method for preparing 3D printed AIE fluorescent resin. Different types of epoxy resins, AIE dye molecules, monomer types, diluent types, and photoinitiator types all fall within the protection scope of this patent.

[0035] The thermosetting fluorescent photosensitive resin for DLP-3D printing prepared by the above method also belongs to the protection scope of the present invention.

[0036] The present invention also provides an application of the above-mentioned thermosetting fluorescent photosensitive resin for DLP-3D printing.

[0037] The application is the use of thermosetting fluorescent photosensitive resin for DLP-3D printing in the preparation of at least one of the following products.

[0038] The present invention also provides a DLP-3D printed resin product.

[0039] The above-mentioned DLP-3D printed resin product is prepared according to a method comprising the following steps: using the above-mentioned thermosetting fluorescent photosensitive resin to perform 3D printing through a DLP-3D printing method to obtain.

[0040] The present invention is designed to utilize the property of aggregation-induced emission (AIE) molecules to emit fluorescence when their motion is restricted, combined with photosensitive resin, to invent a new type of DLP-3D thermosetting photosensitive resin that has no fluorescence in a liquid state and emits fluorescence after curing. The photosensitive resin not only has a small irritating odor, fast curing speed, and high printing accuracy, but also the cured model emits strong fluorescence under 365nm ultraviolet excitation, and this fluorescence is not easily quenched or bleached. It is even possible to design a three-primary color AIE molecule combined with a photosensitive resin, and then a colorful printing model can be printed by adjusting the mixing ratio of the photosensitive resin, making the printing process more interesting.

[0041] After adopting the above technical scheme, the present invention provides a method for preparing a thermosetting fluorescent photosensitive resin for DLP-3D printing. In step (1), the carboxyl group of TPE-COOH is first used to react with bisphenol A epoxy resin to undergo a ring-opening polymerization reaction. The synthesis process is simple, the raw materials AIE fluorescent molecules and bisphenol A epoxy resin are widely available, the production cost is low, the operation is simple, and it is easy to expand production. When the AIE molecule TPE-COOH is in a monodisperse state, it exhibits a phenomenon of weak fluorescence emission or even no light emission. However, in an aggregated state or when the movement of the benzene ring on the molecule is restricted, the fluorescence intensity of the molecule will be greatly enhanced. This phenomenon is completely opposite to the quenching (ACQ) effect of traditional dyes. Based on the characteristic that TPE-COOH molecules emit fluorescence when their movement is restricted, we designed to cross-link the molecule with bisphenol A epoxy resin by condensation. In step (2), triphenylphosphine is used as a catalyst and dissolved in methacrylic acid and then polymerized with bisphenol A epoxy resin. Triphenylphosphine is a very common reagent, which is easy to obtain, low in cost and easy to expand production. In addition, methacrylic acid can alleviate the yellowing of the finished product to a certain extent compared with acrylic acid. In step (3), 910 is used as a photoinitiator and ethoxyethoxyethyl ethyl acrylate is used as a diluent. Compared with other photoinitiators, its absorption wavelength is relatively broad, which can alleviate the yellowing of the finished product to a certain extent.

[0042] Therefore, the new DLP-3D thermosetting photosensitive resin prepared by this method not only has low irritating odor, fast curing speed and high printing accuracy, but also the cured model emits strong fluorescence under 365nm ultraviolet excitation. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 The raw material prepared in Example 8 is used for the fluorescence emitted by the DLP-3D printing model example under 365nm excitation. DETAILED DESCRIPTION

[0044] The present invention is further described in detail below in conjunction with specific embodiments, and the examples provided are only for illustrating the present invention, rather than for limiting the scope of the present invention. The examples provided below can be used as a guide for further improvements by those of ordinary skill in the art, and do not constitute a limitation of the present invention in any way.

[0045] The experimental methods in the following examples, unless otherwise specified, are all conventional methods, and are performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials, reagents, etc. used in the following examples, unless otherwise specified, can all be obtained from commercial channels.

[0046] In the following examples, bisphenol A epoxy resin (McLean, CAS No.: 30583-72-3), TPE-COOH (McLean, CAS No.: 197153-87-0), diluent ethoxyethoxyethyl acrylate (McLean, CAS No.: 7328-17-8), and photoinitiator 910 (McLean, CAS No.: 119313-12-1) were selected as research objects, and the preparation method of the thermosetting fluorescent photosensitive resin for DLP-3D printing was specifically introduced.

[0047] In the following embodiments, the "good, medium, and poor" standards for the degree of formation are based on 3D printing of a 5×5 array of "1μm×1μm×1μm" cubes. A good degree is when the formation rate of all printed cubes is 100%; a medium degree is when the formation rate is above 60%; and a poor degree is when the formation rate is below 60%.

[0048] Embodiment 1

[0049] (1) 0.01 g of monocarboxylic TPE-COOH (4-(1,2,2-triphenylvinyl)benzoic acid) was added to 80 g of bisphenol A epoxy resin and transferred to a 250 g flask. The mixture was refluxed at 80° C. with stirring (250 r / min) for 1 h.

[0050] (2) Dissolve 0.72 g of triphenylphosphine in 40 g of methacrylic acid, add the solution dropwise into the flask over 1 h and continue to stir at 350 r / min and 100 °C for 4 h.

[0051] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature to obtain a thermosetting fluorescent photosensitive resin.

[0052] The thermosetting fluorescent photosensitive resin obtained above was subjected to DLP-3D printing (model: Longer Orange 10) to obtain a finished printed model.

[0053] The tensile stress of the fluorescent photosensitive resin tested above is 25MPa, and the 3D printing molding degree is good.

[0054] Embodiment 2

[0055] (1) 0.03 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0056] (2) Dissolve 0.72 g of triphenylphosphine in 40 g of methacrylic acid, add the solution dropwise into the flask over 1 h and continue to stir at 350 r / min and 100 °C for 4 h.

[0057] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0058] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0059] The tensile stress of the fluorescent photosensitive resin tested above is 30MPa, and the 3D printing molding degree is good.

[0060] Embodiment 3

[0061] (1) 0.05 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0062] (2) Dissolve 0.72 g of triphenylphosphine in 40 g of methacrylic acid, add the solution dropwise into the flask over 1 h and continue to stir at 350 r / min and 100 °C for 4 h.

[0063] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0064] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0065] The tensile stress of the fluorescent photosensitive resin tested above is 42MPa, and the 3D printing molding degree is good.

[0066] Embodiment 4

[0067] (1) 0.01 g of monocarboxyl TPE-COOH was added to 100 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80°C and stirred at 250 r / min for 1 h.

[0068] (2) Dissolve 0.72 g of triphenylphosphine in 40 g of methacrylic acid, add the solution dropwise into the flask over 1 h and continue to stir at 350 r / min and 100 °C for 4 h.

[0069] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0070] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0071] The tensile stress of the fluorescent photosensitive resin tested above is 26MPa, and the 3D printing molding degree is medium.

[0072] Embodiment 5

[0073] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0074] (2) Dissolve 0.72 g of triphenylphosphine in 50 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 100 °C, 350 r / min, and reflux for 4 h.

[0075] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0076] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0077] The tensile stress of the fluorescent photosensitive resin tested above is 25MPa, and the 3D printing molding degree is good.

[0078] Embodiment 6

[0079] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol F epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0080] (2) Dissolve 0.72 g of triphenylphosphine in 60 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 350 r / min and reflux at 100 °C for 4 h.

[0081] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0082] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0083] The tensile stress of the fluorescent photosensitive resin tested above is 23MPa, and the 3D printing molding degree is medium.

[0084] Embodiment 7

[0085] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0086] (2) Dissolve 0.72 g of triphenylphosphine in 60 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 350 r / min and reflux at 100 °C for 4 h.

[0087] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0088] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0089] The tensile stress of the fluorescent photosensitive resin tested above is 25MPa, and the 3D printing molding degree is good.

[0090] Embodiment 8

[0091] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol F epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0092] (2) Dissolve 0.72 g of triphenylphosphine in 60 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 350 r / min and reflux at 100 °C for 4 h.

[0093] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0094] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0095] The tensile stress of the fluorescent photosensitive resin tested above is 26MPa, and the 3D printing molding degree is good.

[0096] The raw material prepared in Example 8 was used for DLP-3D printing, and the model emitted strong fluorescence under 365nm excitation. Figure 1 shown.

[0097] Embodiment 9

[0098] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0099] (2) Dissolve 0.72 g of triphenylphosphine in 60 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 350 r / min and reflux at 100 °C for 4 h.

[0100] (3) The product obtained in step (2) was then placed at room temperature, 6 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0101] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0102] The tensile stress of the fluorescent photosensitive resin tested above is 25MPa, and the 3D printing molding degree is good.

[0103] Embodiment 10

[0104] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0105] (2) Dissolve 0.72 g of triphenylphosphine in 60 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 350 r / min and reflux at 100 °C for 4 h.

[0106] (3) The product obtained in step (2) was then placed at room temperature, 8 g of photoinitiator 910 and 40 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0107] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0108] The tensile stress of the fluorescent photosensitive resin tested above is 24MPa, and the 3D printing molding degree is good.

[0109] Embodiment 11

[0110] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0111] (2) Dissolve 0.72 g of triphenylphosphine in 60 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 350 r / min and reflux at 100 °C for 4 h.

[0112] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 50 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0113] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0114] The tensile stress of the fluorescent photosensitive resin tested above is 20MPa, and the 3D printing molding degree is medium.

[0115] Embodiment 12

[0116] (1) 0.01 g of monocarboxyl TPE-COOH was added to 80 g of bisphenol A epoxy resin and transferred to a 250 mL flask. The reaction was refluxed at 80 °C and stirred at 250 r / min for 1 h.

[0117] (2) Dissolve 0.72 g of triphenylphosphine in 60 g of methacrylic acid, add the solution dropwise into the flask within 1 h, and continue to stir at 350 r / min and reflux at 100 °C for 4 h.

[0118] (3) The product obtained in step (2) was then placed at room temperature, 4 g of photoinitiator 910 and 60 g of diluent ethoxyethoxyethyl acrylate were added to the flask, and stirred at 80 r / min for 1 h at room temperature.

[0119] The thermosetting fluorescent photosensitive resin obtained above is subjected to DLP-3D printing to obtain a finished printed model.

[0120] The tensile stress of the fluorescent photosensitive resin tested above is 18MPa, and the 3D printing molding degree is medium.

[0121] Table 1

[0122] The present invention has been described in detail above. It will be apparent to those skilled in the art that the present invention may be implemented in a wide range under equivalent parameters, concentrations and conditions without departing from the spirit and scope of the present invention and without the need for unnecessary experimentation. Although the present invention provides specific embodiments, it should be understood that further improvements may be made to the present invention. In short, according to the principles of the present invention, this application intends to include any changes, uses or improvements to the present invention, including changes made by conventional techniques known in the art that depart from the scope disclosed in this application. Applications of some of the basic features may be made within the scope of the following appended claims.

Claims

1. A method for preparing a thermosetting fluorescent photosensitive resin for DLP-3D printing, which is to use epoxy resin as a prepolymer, graft AIE fluorescent dye molecules through a condensation reaction, and then copolymerize with acrylic monomers; then add a diluent and a photoinitiator to obtain the thermosetting fluorescent photosensitive resin for DLP-3D printing.

2. The preparation method according to claim 1, characterized in that: The method comprises the following steps: (1) mixing the AIE fluorescent dye molecule and the epoxy resin prepolymer and subjecting them to a reflux reaction to obtain a reaction system 1; (2) dissolving triphenylphosphine in an acrylic monomer and adding the mixture into the reaction system 1 to continue the reflux reaction; (3) The product obtained in step (2) is placed at room temperature, and a photoinitiator and a diluent are added thereto, and reacted at room temperature to obtain the thermosetting fluorescent photosensitive resin for DLP-3D printing.

3. The preparation method according to claim 1 or 2, characterized in that: The AIE fluorescent dye molecule has at least one active group that can undergo a ring-opening reaction with an epoxy group, including but not limited to: a carboxyl group, a hydroxyl group, a thiol group or an amino group; The AIE fluorescent dye molecule is a tetraphenylethylene (TPE) fluorescent molecule; And / or, the epoxy resin prepolymer includes but is not limited to: bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin or novolac epoxy resin; And / or, the acrylic monomers include but are not limited to: acrylic and methacrylic monomers.

4. The preparation method according to claim 2, characterized in that: In the step (1), the AIE fluorescent dye molecule is monocarboxyl TPE-COOH, and the mass ratio of the monocarboxyl TPE-COOH to the epoxy resin prepolymer is (0.01-0.05) g:(80-100) g; And / or, in the step (2), the acrylic monomer is methacrylic acid, and the feed ratio of triphenylphosphine to methacrylic acid is (0.72-1.44) g:(40-60) g.

5. The preparation method according to any one of claims 2 to 4, characterized in that: In the step (1), the reaction conditions of the reflux reaction are: stirring under reflux at 80-85° C. for 1-2 h; And / or, in step (2), the reaction conditions of the reflux reaction are: stirring under reflux at 100-110° C. for 4-5 hours; And / or, in step (3), the reaction is stirred continuously at room temperature for 1 to 2 hours.

6. The preparation method according to any one of claims 1 to 5, characterized in that: In the step (3), the photoinitiator is a long-wavelength photoinitiator, including but not limited to: 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone (910), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylphosphonic acid ethyl ester (TPO-L), 2-isopropylthioxanthenone (2,4 isomer mixture) (ITX); And / or, in the step (3), the diluent includes but is not limited to: isopropyl alcohol acrylate, ethoxyethoxyethyl ethyl acrylate, neopentyl glycol diacrylate.

7. The preparation method according to any one of claims 1 to 6, characterized in that: In the step (3), the photoinitiator is 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone (910), the diluent is ethoxyethoxyethyl ethyl acrylate, and the feed ratio of the photoinitiator 910 to the ethoxyethoxyethyl ethyl acrylate is (4-8) g:(40-60) g.

8. The thermosetting fluorescent photosensitive resin for DLP-3D printing according to any one of claims 1 to 7.

9. Use of the thermosetting fluorescent photosensitive resin for DLP-3D printing according to claim 8 in the preparation of at least one of the following products.

10. A DLP-3D printed resin product, characterized in that: The DLP-3D printed resin product is prepared according to a method comprising the following steps: using the thermosetting fluorescent photosensitive resin for DLP-3D printing described in any one of claims 1 to 7 to perform 3D printing by a DLP-3D printing method.

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