CN113881279A - 3D printing shape memory epoxy resin ink, preparation method and application thereof, and 3D printing epoxy resin - Google Patents
3D printing shape memory epoxy resin ink, preparation method and application thereof, and 3D printing epoxy resin Download PDFInfo
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- CN113881279A CN113881279A CN202111294560.9A CN202111294560A CN113881279A CN 113881279 A CN113881279 A CN 113881279A CN 202111294560 A CN202111294560 A CN 202111294560A CN 113881279 A CN113881279 A CN 113881279A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
The invention provides 3D printing shape memory epoxy resin ink, a preparation method and application thereof, and 3D printing epoxy resin, and belongs to the technical field of rapid prototyping materials. The 3D printing shape memory epoxy resin ink provided by the invention has excellent photocuring performance and certain universality, and can be suitable for photocuring 3D printers in DLP and SLA forming modes; moreover, the epoxy vinyl resin belongs to unsaturated polyester resin, and can form an insoluble huge high molecular polymer with an infusible space network structure under the action of a photoinitiator, so that the prepared epoxy resin product can keep the excellent mechanical properties, heat resistance, chemical resistance, toughness and the like of the epoxy resin. The 3D printing shape memory epoxy resin ink can be used for quickly preparing complex samples, and the prepared 3D printing epoxy resin has a shape memory function and has wide application prospects in orthodontics, cardiac occluders, various supports and the like.
Description
Technical Field
The invention relates to the technical field of rapid prototyping materials, in particular to 3D printing shape memory epoxy resin ink, a preparation method and application thereof, and 3D printing epoxy resin.
Background
3D printing, also known as additive manufacturing, is a rapid three-dimensional integrated manufacturing technology that has developed in recent years. Compared with the traditional material reduction manufacturing method, the 3D printing is based on a digital model, specific powder, liquid, wire rods and the like are accumulated layer by layer through software and a numerical control system according to modes of extrusion, sintering, melting, photocuring and the like, and then a three-dimensional entity is constructed, so that the method is a manufacturing method which gradually accumulates materials from bottom to top. The 3D printing can be divided into a plurality of processes such as Digital Light Processing (DLP), melt extrusion (FDM), Stereolithography (SLA), Selective Laser Sintering (SLS), direct writing printing (DIW), and the like, according to the difference of the molding modes. SLA and DLP photocuring 3D printing are two kinds of earlier, the technology is more mature relatively in the material increase manufacturing technology, have high printing precision, the quick manufacturing of complex structure and save advantages such as raw materials, have shown huge application prospect in fields such as jewelry, medical education and mould manufacturing.
With the rapid development of advanced manufacturing technology of photo-curing 3D printing, the corresponding printing materials have also gained wide attention, such as acrylic resin, epoxy resin, polyurethane, and other high molecular materials. However, most of the materials can only present the initial structure of printing, and have no intelligent responsiveness under external stimulation. How to combine deformable material and 3D printing technique, further expand its individualized customization in fields such as biological medical treatment, aerospace, be the bottleneck problem of 3D printing research at present.
Shape Memory Polymers (SMP), also known as shape memory polymers, refer to a polymer material that can be restored to an initial shape by external stimuli (such as heat, electricity, light, chemical induction, etc.) after an initial shape of a product is changed and fixed under certain conditions. At present, shape memory polymers have been widely used in the biomedical fields such as sutures, dental braces, aneurysm occluders, etc. And the combination of the shape memory polymer and 3D printing can realize the preparation of relatively complex, personalized and high-precision structural parts similar to cardiac stents or bone stents. In recent years, researchers have developed 3D printing shape memory polyurethanes, polylactic acids, polyimides, and the like, but to date, no substantial progress has been made in the preparation of shape memory epoxy resins with a wide range of application values.
Disclosure of Invention
The invention aims to provide 3D printing shape memory epoxy resin ink, a preparation method and application thereof, and 3D printing epoxy resin, wherein the 3D printing shape memory epoxy resin ink has excellent photocuring performance and universality, and the prepared 3D printing epoxy resin has a shape memory function, excellent mechanical performance, heat resistance, chemical resistance and toughness.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides 3D printing shape memory epoxy resin ink which comprises the following components in percentage by mass:
60-70% of epoxy vinyl resin, 10-15% of reactive diluent, 10-15% of functional monomer, 5-10% of cross-linking agent, 1-3% of photoinitiator and 1-3% of additive;
the preparation method of the epoxy vinyl resin comprises the following steps:
bisphenol A diglycidyl ether type epoxy resin, methacrylic acid and a polymerization inhibitor are mixed and modified to obtain the epoxy vinyl resin.
Preferably, the molar ratio of the methacrylic acid to the bisphenol A diglycidyl ether type epoxy resin is 2 (1.0-1.5).
Preferably, the polymerization inhibitor comprises one or more of hydroquinone, p-hydroxyanisole and 2, 6-di-tert-butyl-4-methylphenol; the mass of the polymerization inhibitor is 0.2-0.5% of the total mass of the bisphenol A diglycidyl ether type epoxy resin and the methacrylic acid.
Preferably, the modification temperature is 120 ℃ and the modification time is 4-6 h.
Preferably, the reactive diluent comprises one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, aliphatic urethane acrylate, glycidyl methacrylate, hydroxyethyl methacrylate and cyclic trimethylolpropane formal acrylate.
Preferably, the functional monomer comprises one or more of tripropylene glycol diacrylate, aliphatic urethane acrylate, polyethylene glycol diacrylate and tetrahydrofuran acrylate; the cross-linking agent comprises one or more of propane trimethanol triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate and trimethylolpropane triacrylate.
Preferably, the photoinitiator comprises one or more of Irgacure TPO, Irgacure TPO-L, Irgacure 819, Irgacure 2959 and Irgacure 184; the additive comprises one or more of fluorescent whitening agent, an orizanol dye and vitamin E oil.
The invention provides a preparation method of 3D printing shape memory epoxy resin ink, which comprises the following steps:
mixing epoxy vinyl resin, a reactive diluent, a functional monomer, a cross-linking agent, a photoinitiator and an additive, and removing bubbles to obtain the 3D printing shape memory epoxy resin ink.
The invention provides application of the 3D printing shape memory epoxy resin ink in the technical scheme or the 3D printing shape memory epoxy resin ink prepared by the preparation method in the technical scheme in preparation of 3D printing epoxy resin.
The invention provides 3D printing epoxy resin which is prepared by 3D printing of the 3D printing shape memory epoxy resin ink or the 3D printing shape memory epoxy resin ink prepared by the preparation method in the technical scheme.
In the 3D printing shape memory epoxy resin ink provided by the invention, the epoxy vinyl resin is obtained by using bisphenol A diglycidyl ether type epoxy resin as a substrate and performing double bond end-capping modification by using methacrylic acid, the methacrylic acid has double bonds and can perform photocuring reaction in the printing process, so that the epoxy vinyl resin combines the excellent molding operation performance of the methacrylic acid and the outstanding chemical and physical properties of the epoxy resin, has excellent photocuring performance and certain universality, and can be suitable for photocuring 3D printers in DLP and SLA molding modes; moreover, the epoxy vinyl resin belongs to unsaturated polyester resin, and can form an insoluble and infusible huge high molecular polymer with a spatial network structure under the action of a photoinitiator, so that the prepared 3D printing shape memory epoxy resin can retain the excellent mechanical properties, heat resistance, chemical resistance, toughness and the like of the epoxy resin.
Because the bisphenol A diglycidyl ether type epoxy resin is a typical shape memory polymer and can realize the shape memory function through the stationary phase (fixing and maintaining the shape of a cured sample) and the reversible phase (reversibly softening and hardening under certain conditions), the 3D printing shape memory epoxy resin ink containing the bisphenol A diglycidyl ether type epoxy resin provided by the invention not only can quickly prepare a complex sample, but also has the shape memory function of the prepared 3D printing epoxy resin, and has wide application prospects in orthodontics, heart stoppers, various brackets and the like.
The epoxy vinyl resin used in the invention takes bisphenol A diglycidyl ether type epoxy resin as a raw material, the raw material is cheap and easy to obtain, the preparation method is simple, the reaction condition is mild, and the industrialization is easy.
Drawings
FIG. 1 is a graph of dynamic thermomechanical analysis of 3D printed shape memory epoxy prepared in application example 1;
fig. 2 is a schematic diagram of the initial-deformation-recovery process of a 3D printed shape memory epoxy resin bearing sample prepared in application example 2 under temperature stimulation.
Detailed Description
The invention provides 3D printing shape memory epoxy resin ink which comprises the following components in percentage by mass:
60-70% of epoxy vinyl resin, 10-15% of reactive diluent, 10-15% of functional monomer, 5-10% of cross-linking agent, 1-3% of photoinitiator and 1-3% of additive;
the preparation method of the epoxy vinyl resin comprises the following steps:
bisphenol A diglycidyl ether type epoxy resin, methacrylic acid and a polymerization inhibitor are mixed and modified to obtain the epoxy vinyl resin.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The 3D printing shape memory epoxy resin ink comprises 60-70% by mass of epoxy vinyl resin, and preferably 65-70% by mass of epoxy vinyl resin. In the present invention, the method for preparing the epoxy vinyl resin comprises the steps of:
bisphenol A diglycidyl ether type epoxy resin, methacrylic acid and a polymerization inhibitor are mixed and modified to obtain the epoxy vinyl resin.
The type of the bisphenol A diglycidyl ether type epoxy resin is not particularly limited, and the bisphenol A diglycidyl ether type epoxy resin can be a commercially available product well known in the art; in the embodiment of the present invention, specifically, epoxy resin E-51.
In the present invention, the molar ratio of the methacrylic acid to the bisphenol a diglycidyl ether type epoxy resin is preferably 2 (1.0 to 1.5), and more preferably 2: 1.1.
In the invention, the polymerization inhibitor preferably comprises one or more of hydroquinone, p-hydroxyanisole and 2, 6-di-tert-butyl-4-methylphenol; when the polymerization inhibitor is two or more than two, the proportion of the polymerization inhibitor is not specially limited, and the polymerization inhibitor can be prepared at any proportion. In the present invention, the mass of the polymerization inhibitor is preferably 0.2 to 0.5%, more preferably 0.3%, of the total mass of the bisphenol a diglycidyl ether type epoxy resin and methacrylic acid.
In the present invention, the process of mixing the bisphenol a diglycidyl ether type epoxy resin, methacrylic acid and polymerization inhibitor preferably comprises adding the bisphenol a diglycidyl ether type epoxy resin to N2Stirring and heating to 80 ℃ in the atmosphere, dropwise adding methacrylic acid and adding a polymerization inhibitor. The stirring rate, the heating rate and the dropping rate are not particularly limited in the present invention, and may be performed according to a procedure well known in the art.
After the methacrylic acid is dripped, continuously heating to the modification temperature; the temperature of the modification is preferably 120 ℃, and the time is preferably 4-6 h.
In the modification process, methacrylic acid modifies bisphenol A diglycidyl ether type epoxy resin to form double bond-terminated epoxy vinyl resin under the action of a polymerization inhibitor.
After finishing the modification, the invention preferably washes the obtained material toluene, and then carries out rotary evaporation to obtain the epoxy vinyl resin. In the present invention, the agent for washing is preferably toluene; the temperature of the rotary evaporation is preferably 60 ℃; the time is preferably 30 min.
The 3D printing shape memory epoxy resin ink comprises 10-15% of reactive diluent, and preferably 12-15% of reactive diluent. In the present invention, the reactive diluent preferably includes one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, aliphatic urethane acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, and cyclic trimethylolpropane formal acrylate, and when the reactive diluent is preferably two or more of the above, the ratio of the different reactive diluents is not particularly limited, and any ratio may be used.
The 3D printing shape memory epoxy resin ink comprises 10-15% of functional monomers by mass percentage, and preferably 10-12%. In the invention, the functional monomer preferably comprises one or more of tripropylene glycol diacrylate, aliphatic urethane acrylate, polyethylene glycol diacrylate and tetrahydrofuran acrylate, and when the functional monomer is preferably two or more of the above, the proportion of different types of functional monomers in the invention is not particularly limited, and any proportion can be adopted.
The 3D printing shape memory epoxy resin ink comprises 5-10% of a cross-linking agent by mass percentage, and preferably 6-8%. In the invention, the cross-linking agent preferably comprises one or more of propane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate and trimethylolpropane triacrylate, and when the cross-linking agent is preferably two or more of the above, the proportion of different cross-linking agents in the invention is not particularly limited, and any proportion can be adopted. The crosslinking agent in the invention has the function of improving the crosslinking degree and the photocuring reaction efficiency.
The 3D printing shape memory epoxy resin ink comprises 1-3% of photoinitiator, and preferably 2-3% of photoinitiator. In the invention, the photoinitiator comprises one or more of Irgacure TPO, Irgacure TPO-L, Irgacure 819, Irgacure 2959 and Irgacure 184; when the photoinitiator is preferably two or more of the above photoinitiators, the ratio of different photoinitiators is not particularly limited, and any ratio may be used.
The 3D printing shape memory epoxy resin ink comprises 1-3% of additive by mass percentage, preferably 1.0-1.5%; the additive comprises one or more of fluorescent whitening agent, an orizanol dye and vitamin E oil; when the addition is preferably two or more of the above, the invention has no special limitation on the proportion of different additives, and any proportion can be used.
The invention provides a preparation method of 3D printing shape memory epoxy resin ink, which comprises the following steps:
mixing epoxy vinyl resin, a reactive diluent, a functional monomer, a cross-linking agent, a photoinitiator and an additive, and removing bubbles to obtain the 3D printing shape memory epoxy resin ink.
The process of mixing the epoxy vinyl resin, the reactive diluent, the functional monomer, the crosslinking agent, the photoinitiator and the additive is not particularly limited and can be carried out according to the process well known in the art; in the embodiment of the invention, the mixing and stirring are specifically carried out for 2-2.5 h. The invention preferably removes bubbles by means of vacuum pumping; the process of the vacuum-pumping is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The invention provides application of the 3D printing shape memory epoxy resin ink in the technical scheme or the 3D printing shape memory epoxy resin ink prepared by the preparation method in the technical scheme in preparation of 3D printing epoxy resin.
The invention provides 3D printing epoxy resin which is prepared by 3D printing of the 3D printing shape memory epoxy resin ink or the 3D printing shape memory epoxy resin ink prepared by the preparation method in the technical scheme.
In the present invention, the method for preparing the 3D printing epoxy resin by using the 3D printing shape memory epoxy resin ink preferably comprises the following steps:
placing the 3D printing shape memory epoxy resin ink into a forming trough, and performing 3D printing to obtain a formed sample;
and (3) carrying out ultrasonic cleaning on the molded sample, and then placing the molded sample in an ultraviolet curing box for post-curing treatment to obtain the 3D printing epoxy resin.
In the invention, the 3D printer used for 3D printing preferably comprises a DLP printer and an SLA printer, and the wavelength range of 3D printing is preferably 350-405 nm. The 3D printing process and the equipment used in the present invention are not particularly limited, and the process may be performed according to the method well known in the art by using the corresponding equipment well known in the art. The 3D printing time is not specially limited, and the time can be adjusted according to the actually required sample.
In the invention, the reagent used for ultrasonic cleaning is preferably industrial ethanol, and the time for ultrasonic cleaning is preferably 10 minutes. The invention removes uncured residual ink by ultrasonic cleaning.
In the invention, the power of the ultraviolet curing box is 30-40W, and the post-curing treatment time is preferably 10-20 minutes. The invention further cures the residual liquid resin on the surface of the 3D printing entity through post-curing treatment, thereby preventing the surface of the surface entity from being sticky.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
390g (1.1mol) of epoxy resin E-51 are weighed and put into a kettle N2Heating to 80 ℃ with stirring, weighing 172g (2.0mol) of methacrylic acid, dropwise adding the methacrylic acid into the flask, simultaneously adding 1.3g of hydroquinone, heating to 120 ℃ after the methacrylic acid is dropwise added, reacting for 6 hours, washing with toluene, and rotationally steaming at 60 ℃ for 30min to obtain the epoxy vinyl resin;
according to the mass percentage, 60% of epoxy vinyl resin, 15% of cyclotrimethylolpropane methylal acrylate, 15% of polyethylene glycol diacrylate, 6% of ethoxylated pentaerythritol tetraacrylate, 3% of Irgacure 819, 0.5% of orlistat dye and 0.5% of fluorescent whitening agent are mixed and stirred for 2.0h, and air bubbles are removed through vacuum pumping, so that the 3D printing shape memory epoxy resin ink is obtained.
Example 2
According to the mass percentage, 70% of the epoxy vinyl resin prepared in example 1, 10% of 1, 6-hexanediol diacrylate, 10% of polyethylene glycol diacrylate, 6% of trimethylolpropane triacrylate, 1.5% of Irgacure 819, 1.5% of Irgacure TPO, 0.5% of vitamin E oil and 0.5% of fluorescent whitening agent are mixed and stirred for 2.5h, and bubbles are removed by vacuumizing, so that the 3D printing shape memory epoxy resin ink is obtained.
Application example 1
Introducing the 3D printing shape memory epoxy resin ink prepared in example 1 into a three-dimensional STL model, and using a photocuring printer (SLA molding, Beijing major industry small square printer), setting the thickness of a printing layer to be 100 μm, the wavelength to be 405nm, and the photocuring printing time to be 7s to obtain a bearing sample; and after printing is finished, taking out the sample, carrying out ultrasonic cleaning for 10 minutes by adopting industrial ethanol, and carrying out post-curing treatment for 10 minutes in an ultraviolet curing box with the power of 36W to obtain the 3D printing bearing.
Application example 2
Introducing the 3D printing shape memory epoxy resin ink prepared in the embodiment 2 into a three-dimensional STL model, and utilizing a photocuring printer (Shenzhen sample Slash 2, DLP molding), wherein the thickness of a printing layer is set to be 100 mu m, the wavelength is 405nm, and the photocuring printing time is 10s, so as to obtain a bearing sample; and after printing is finished, taking out the sample, carrying out ultrasonic cleaning for 10 minutes by adopting industrial ethanol, and carrying out post-curing treatment for 10 minutes in an ultraviolet curing box with the power of 36W to obtain the 3D printing bearing.
Performance testing
1) Fig. 1 is a graph of dynamic thermo-mechanical analysis of a 3D printed shape memory epoxy prepared in application example 1, wherein a is a graph of storage modulus as a function of temperature; b is a graph of loss tangent tan delta as a function of temperature. As can be seen from FIG. 1, the prepared 3D printing shape memory epoxy resin has a storage modulus of 2600MPa and a glass transition temperature of 64 ℃, and is similar to the commercially available E-51 resin (the storage modulus of E-51 resin is 2300MPa and the glass transition temperature is 61 ℃); the 3D printing shape memory epoxy resin has excellent mechanical property and thermal stability.
2) Fig. 2 is a schematic view of an initial-deformation-recovery process of a 3D printed shape memory epoxy bearing sample prepared in application example 2 under temperature stimulation, wherein the left side is an initial state of bearing printing; the middle part is a deformation state after the bearing is extruded and deformed; the right side is the state of the bearing after the initial state is recovered; as shown in fig. 2, when the bearing sample in the initial form is heated to 100 ℃, the bearing sample is extruded to deform and maintain the form, and the temperature is reduced to room temperature, so as to obtain the deformation state of the bearing sample; and then heating the bearing sample after extrusion deformation to 100 ℃ again, and recovering the deformed bearing to the initial state.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The 3D printing shape memory epoxy resin ink comprises the following components in percentage by mass:
60-70% of epoxy vinyl resin, 10-15% of reactive diluent, 10-15% of functional monomer, 5-10% of cross-linking agent, 1-3% of photoinitiator and 1-3% of additive;
the preparation method of the epoxy vinyl resin comprises the following steps:
bisphenol A diglycidyl ether type epoxy resin, methacrylic acid and a polymerization inhibitor are mixed and modified to obtain the epoxy vinyl resin.
2. The 3D printing shape memory epoxy resin ink is characterized in that the molar ratio of methacrylic acid to bisphenol A diglycidyl ether type epoxy resin is 2 (1.0-1.5).
3. The 3D printing shape memory epoxy resin ink as claimed in claim 1, wherein the polymerization inhibitor comprises one or more of hydroquinone, p-hydroxyanisole and 2, 6-di-tert-butyl-4-methylphenol; the mass of the polymerization inhibitor is 0.2-0.5% of the total mass of the bisphenol A diglycidyl ether type epoxy resin and the methacrylic acid.
4. The 3D printing shape memory epoxy resin ink according to claim 1, wherein the temperature of the decoration is 120 ℃ and the time is 4-6 h.
5. The 3D printing shape memory epoxy ink of claim 1, wherein the reactive diluent comprises one or more of 1, 6-hexanediol diacrylate, tripropylene glycol diacrylate, hydroxyethyl methacrylate, aliphatic urethane acrylate, glycidyl methacrylate, hydroxyethyl methacrylate, and cyclic trimethylolpropane formal acrylate.
6. The 3D printing shape memory epoxy ink according to claim 1, wherein the functional monomer comprises one or more of tripropylene glycol diacrylate, aliphatic urethane acrylate, polyethylene glycol diacrylate and tetrahydrofuran acrylate; the cross-linking agent comprises one or more of propane trimethanol triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate and trimethylolpropane triacrylate.
7. The 3D printing shape memory epoxy resin ink according to claim 1, wherein the photoinitiator comprises one or more of Irgacure TPO, Irgacure TPO-L, Irgacure 819, Irgacure 2959, and Irgacure 184; the additive comprises one or more of fluorescent whitening agent, an orizanol dye and vitamin E oil.
8. The preparation method of the 3D printing shape memory epoxy resin ink is characterized by comprising the following steps:
mixing epoxy vinyl resin, a reactive diluent, a functional monomer, a cross-linking agent, a photoinitiator and an additive, and removing bubbles to obtain the 3D printing shape memory epoxy resin ink.
9. Use of the 3D printing shape memory epoxy resin ink according to any one of claims 1 to 7 or the 3D printing shape memory epoxy resin ink prepared by the preparation method according to claim 8 in preparation of 3D printing epoxy resin.
10. 3D printing epoxy resin is characterized in that the 3D printing shape memory epoxy resin ink is prepared by 3D printing according to any one of claims 1 to 7 or the 3D printing shape memory epoxy resin ink prepared by the preparation method according to claim 8.
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| CN115537062A (en) * | 2022-10-27 | 2022-12-30 | 烟台先进材料与绿色制造山东省实验室 | 3D printing ink material, preparation method thereof and bracket-free invisible appliance with shape memory function |
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| CN115537062A (en) * | 2022-10-27 | 2022-12-30 | 烟台先进材料与绿色制造山东省实验室 | 3D printing ink material, preparation method thereof and bracket-free invisible appliance with shape memory function |
| CN115537062B (en) * | 2022-10-27 | 2023-09-22 | 烟台先进材料与绿色制造山东省实验室 | 3D printing ink material, preparation method thereof and bracket-free invisible appliance with shape memory function |
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