CN111171488A - Visible light curing photosensitive resin-based silver conductive material for 3D printing and product prepared from visible light curing photosensitive resin-based silver conductive material - Google Patents
Visible light curing photosensitive resin-based silver conductive material for 3D printing and product prepared from visible light curing photosensitive resin-based silver conductive material Download PDFInfo
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Abstract
The invention relates to a visible light curing photosensitive resin-based silver conductive material for 3D printing and a product prepared from the same, and belongs to the field of visible light curing 3D printing conductive materials. The visible light curing photosensitive resin-based silver conductive material initiates reduction of a silver precursor in the material under the induction of visible light, and silver nanoparticles are prepared in situ while a polymer matrix is formed through photocuring, so that the metal nanocomposite material is obtained. The product is prepared by a 3D printing method combining visible light Digital Light Processing (DLP)3D printing and photoinduced silver particle in-situ preparation, and by adopting the visible light cured photosensitive resin-based silver conductive material provided by the invention, the resin material is cured through the visible light layer, and the silver nanoparticles are prepared in situ layer by layer through the visible light induction layer, so that the conductive device with good 3D printing mechanical properties is realized, and the problems of safety and the like of the conventional ultraviolet light cured 3D printed conductive device are solved.
Description
Technical Field
The invention relates to a visible light curing photosensitive resin-based silver conductive material for 3D printing and a product prepared from the same, and belongs to the field of visible light curing 3D printing conductive materials.
Background
The 3D printing technology is an emerging rapid prototyping technology, and has been known as a sign of the third industrial revolution. The 3D printing material will be the dominant market of future 3D printing without any doubt. Market research institutes predict that the global 3D printed material market will reach $ 14 billion by 2021, and 3D printed conductive materials will certainly occupy a very considerable market share as one of the ten largest potential 3D printed materials in the future. At present, conductive materials for 3D printing are mainly based on conductive graphene, metal silver materials and the like. The former is developed by the 3D Lab company of Graphene in the United states, and is expected to be applied to electronic conductive circuits, including interfaces of computers, mainboards, wearable electronic products and the like through an extrusion 3D printing technology. The latter is a silver material based ink that was introduced by Nano Dimension, a producer of israel 3D printers, and is specific to inkjet 3D printers. Recently, the conductive resin product based on in-situ generation of silver particles is prepared by using a photocuring 3D printing mode in the research institution of italy, and the pioneer of photocuring 3D printing conductive materials is opened. However, at present, the curing light source used for photocuring 3D printing is mainly ultraviolet light, and has poor safety performance and high manufacturing cost, so that the application of the curing light source in commercial production is limited. Meanwhile, the mechanical property of the photo-curing material is limited by the characteristic of poor mechanical property of the photosensitive resin material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel visible light curing photosensitive resin-based silver conductive material and a product prepared from the same, wherein the material can be cured by visible light, so that the safety problem caused by adopting ultraviolet light in the prior art is solved; meanwhile, visible light can induce the in-situ generation of silver particles in the resin matrix, the material curing speed is high, the performance is excellent, and the visible light cured photosensitive resin matrix silver conductive material can realize the preparation of 3D printed conductive products under visible light.
Another object of the present invention is to provide an article which is based on visible light curable polymer resin and in which photoinduced in-situ generated metallic silver nanoparticles are embedded, and a method for preparing the same, which can be based on a combination of visible light Digital Light Processing (DLP)3D printing and visible light induced silver particle in-situ preparation. The product prepared by the method has excellent conductivity and mechanical properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
a visible light curing photosensitive resin-based silver conductive material comprises the following components in parts by weight: 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 5-30 parts by weight of silver precursor and 0.01-5 parts by weight of photoinitiator.
According to the invention, the material comprises the following components in parts by weight: 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 8-25 parts by weight of silver precursor and 0.5-3 parts by weight of photoinitiator.
According to the invention, the material comprises the following components in parts by weight: 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 10-20 parts by weight of silver precursor and 1.5-2.5 parts by weight of photoinitiator.
According to the invention, the polymerizable monomer is one or more of acrylate compounds, vinyl ether compounds and epoxy compounds. More preferably, the vinyl-based compound is, for example, vinylpyrrolidone or the like; examples of the acrylate compound include methacrylate, trimethylolpropane triacrylate, and dihydroxyethyl acrylate.
According to the invention, the polymerizable oligomer is one or more of unsaturated polyester, epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy resin and organic silicon oligomer. More preferably, the oligomer is one or more of an unsaturated polyester, an epoxy acrylate, an epoxy resin, or a urethane acrylate; further preferably, the unsaturated polyester is, for example, glycidyl methacrylate, the epoxy acrylate is, for example, bisphenol a type epoxy acrylate, the epoxy resin is, for example, phenol type epoxy resin, and the urethane acrylate is, for example, aliphatic urethane acrylate.
According to the invention, the silver precursor is silver nitrate, silver oxide, silver chloride, silver hexafluorophosphate, silver hexafluoroantimonate, and one or more mixtures of aliphatic carboxylic acid silver, aromatic carboxylic acid silver or alicyclic carboxylic acid silver which has 1-3 carboxyl groups, 0-2 hydroxyl groups and 1-17 carbon atoms, such as silver butyrate, silver caprylate and silver stearate.
According to the invention, the photoinitiator is one or more of compounds which are active under the irradiation of visible light with the wavelength of 415-780 nm, such as: quinone compounds, cyclopentadienyl titanium compounds, iodonium salt compounds and sulfonium salt compounds. Preferably, the quinone compound is, for example, camphorquinone or the like. Preferably, the titanocene compound is, for example, fluorinated diphenyltitanocene and the like. Preferably, the iodonium salt compound is, for example, an alkyl iodonium salt or the like. Preferably, the sulfonium salt compound is, for example, an alkyl sulfonium salt.
According to the invention, the material also comprises the following components in parts by weight: 0-5 parts of photoinitiator assistant and 0-20 parts of other functional assistants.
According to the invention, the material also comprises the following components in parts by weight: 1-4 parts of photoinitiator assistant and 0-15 parts of other functional assistants.
According to the invention, the material also comprises the following components in parts by weight: 1.5-3 parts of photoinitiator assistant and 0-10 parts of other functional assistants.
According to the invention, the photoinitiator auxiliary agent is one of a secondary amine compound, a tertiary amine compound, a secondary alcohol compound and a tertiary alcohol compound. Preferably, the secondary amine compound is, for example, triethylamine. Preferably, the tertiary amine compound is, for example, ethyl 4-dimethylaminobenzoate. Preferably, the secondary alcohol compound is, for example, one of sec-butyl alcohol, sec-amyl alcohol and 2-hexanol. Preferably, the tertiary alcohol compound is, for example, one of tert-butanol and 2-methyl-2-butanol.
According to the invention, the other functional auxiliary agents comprise one or more of pigments (such as cadmium yellow, cadmium red, cadmium green, iron blue and the like), stabilizers (such as surfactants, poly-N-vinyl pyrrolidone and the like), and polymerization inhibitors (such as hydroxyanisole, hydroquinone and the like). Further preferably, the stabilizer is, for example, poly-N-vinylpyrrolidone; the polymerization inhibitor is, for example, hydroquinone.
According to the invention, the material is obtained by mixing the above components.
According to the invention, the viscosity of the material is 3-800 cps at normal temperature. Preferably 40 to 700cps at normal temperature.
According to the invention, the material can be rapidly cured under the irradiation of visible light with the wavelength of 415-780 nm, and the material can be rapidly cured under the irradiation of the following light sources: thermoluminescent light sources, gas discharge light sources or solid illumination light sources. Preferably, the thermoluminescent light source is, for example, an incandescent lamp, a halogen lamp, or the like. Preferably, the gas discharge light source is, for example, a fluorescent lamp, a metal halide, or the like. Preferably, the solid-state illumination light source is, for example, an LD laser, an LED laser, or the like. Preferably, the light source has an emission wavelength of 420 to 500nm, more preferably 430 to 480nm, and even more preferably 440 to 475 nm. The light source is further preferably a 445nm or 470nm blue solid illumination light source (e.g., LD laser, LED laser, etc.).
According to the invention, the material preferably has a setting time under irradiation with visible light of less than 5 seconds, more preferably less than 2 seconds.
The invention also provides the following technical scheme:
the visible light curing photosensitive resin-based silver conductive material is used for 3D printing.
The invention further provides the following technical scheme:
the product is prepared by taking the visible light curing photosensitive resin-based silver conductive material as a raw material and performing visible light curing.
Preferably, the ink is prepared by visible light curing 3D printing.
Preferably, the article is an electrically conductive article.
The invention further provides the following technical scheme:
a method of making the above article, the method comprising the steps of:
1) mixing the components to prepare the visible light curing photosensitive resin-based silver conductive material;
2) curing the visible light curing photosensitive resin-based silver conductive material obtained in the step 1) layer by utilizing a projection pattern formed on a workbench by a light source to form a three-dimensional polymer matrix material, and simultaneously initiating in-situ generation of silver nanoparticles to prepare a three-dimensional metal nano composite material;
3) sintering the three-dimensional metal nano composite material obtained in the step 2) in an air atmosphere at 100-300 ℃, and fusing silver nano particles to obtain the product.
According to the invention, the process for preparing said article is based on a combination of visible light Digital Light Processing (DLP)3D printing technology and photoinduced in-situ reduction of silver precursors.
According to the invention, in step 1), the mixing is carried out at ambient temperature.
According to the invention, the visible light curing photosensitive resin-based silver conductive material in the step 1) is preferably preserved in a shading way; for example, tinfoil paper is selected for shading storage.
According to the invention, in the step 3), the sintering temperature is preferably 120-200 ℃.
According to the invention, the method comprises the following steps:
(1) stirring and uniformly mixing 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 5-30 parts by weight of silver precursor, 0.01-5 parts by weight of photoinitiator, 0-5 parts by weight of photoinitiator aid and 0-20 parts by weight of other functional aids at normal temperature to obtain a uniform mixture;
(2) placing the mixture obtained in the step (1) in a material tank of a device based on a visible light Digital Light Processing (DLP)3D printing technology, projecting the mixture onto the interface between the bottom of the material tank and the mixture on a lifting table through a light source, solidifying the mixture layer by layer, reducing the silver precursor in the mixture layer by layer to prepare silver nanoparticles, and finally printing a three-dimensional metal nano composite part;
(3) sintering the three-dimensional metal nano composite part obtained in the step (2) in an air atmosphere at the temperature of 100-300 ℃, and fusing the silver nano particles.
The invention has the beneficial effects that:
1. the invention creatively provides a visible light curing photosensitive resin-based silver conductive material which can be subjected to 3D printing through 415-780 nm visible light for the first time. By adding the photoinitiator and the silver precursor, the material can be rapidly cured under visible light, and is completely suitable for the requirements of 3D printing.
2. The visible light curing photosensitive resin-based silver conductive material provided by the invention initiates the reduction of the silver precursor in the material under the induction of visible light, and silver nanoparticles are prepared in situ while a polymer matrix is formed by photocuring, so that the metal nano composite material is obtained.
3. The invention provides a method for preparing a product by taking a visible light curing photosensitive resin-based silver conductive material as a raw material, which is a 3D printing method based on the combination of visible light Digital Light Processing (DLP)3D printing and photoinduced silver particle in-situ preparation.
Drawings
Fig. 1 is a schematic view of a photocuring 3D printing apparatus according to the present invention;
FIG. 2 is a photograph of a 3D printing device before and after sintering in example 1 of the present invention;
FIG. 3 is a surface SEM photograph of a conductive device in example 1 of the present invention;
fig. 4 is an application example of a 3D printing device in the present invention;
FIG. 5 shows the results of mechanical testing of a printing device in example 2 of the present invention;
FIG. 6 shows the results of mechanical testing of the printed device of comparative example 1 according to the present invention.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Operating device
Fig. 1 is a schematic view of a photocuring 3D printing apparatus according to the present invention; referring to fig. 1, the 3D printing apparatus used in the present invention includes a lifting table, a trough, and a visible light source, wherein the lifting table is disposed above the trough; the bottom of the trough is provided with a transparent substrate which is made of any material not absorbing visible light; the visible light source is placed under the trough, in particular under the transparent substrate.
In the operation process, the material is placed in a material groove; the visible light source downwards projects a preset pattern to the interface of the trough bottom transparent substrate and the mixture, the material at the trough bottom transparent substrate is quickly photocured to form a polymer material after being irradiated by the visible light, meanwhile, silver nanoparticles are reduced in situ from a silver precursor and embedded into the polymer material to obtain a single-layer metal nanocomposite, the formed single-layer metal nanocomposite is separated from the trough bottom by stripping and is adhered to the lifting platform, and the material in the trough covers the transparent substrate at the trough bottom again. And continuously projecting a series of patterns, repeating the steps, controlling the lifting platform to lift, and solidifying layer by layer to obtain the 3D printed unsintered product embedded with the silver nanoparticles.
Wherein, the standard sample bar has the size of 28 multiplied by 6 multiplied by 1mm dumbbell type.
Example 1 visible light curing 3D printing conductive device
1) 100 parts by weight of dihydroxyethyl acrylate monomer, 20 parts by weight of silver nitrate precursor, 2 parts by weight of photoinitiator camphorquinone, 2 parts by weight of photoinitiator aid ethyl 4-dimethylaminobenzoate, 10 parts by weight of stabilizer poly N-vinyl pyrrolidone (PVP) are uniformly stirred and stirred at room temperature by tinfoil paper in a shading mode to obtain a uniform mixture, and the uniform mixture is placed in a material tank.
2) The unsintered article is prepared using the apparatus and method of operation described above.
3) Sintering the unsintered product of step 2) at 150 ℃ for 2 hours in an air atmosphere to obtain the conductive 3D printing device.
FIG. 2 is a photograph of a 3D printing device before and after sintering in example 1 of the present invention; as can be seen from fig. 2, the unsintered 3D printed device is dark brown and shows the color of metallic silver after sintering.
FIG. 3 is a surface SEM photograph of a conductive device in example 1 of the present invention; the surface of the sintered device was observed by a Scanning Electron Microscope (SEM) to find that the silver nanoparticles were closely arranged and fused with each other. The conductivity of the material is tested by a four-probe method, and the average sheet resistance of the surface of the device is about 3.0 omega sq-1. The obtained conductive device and the LED lamp beads are communicated in a conductive loop, and the lamp beads are lightened when the device is electrified, so that the good conductive performance of the device is further verified.
Example 23D mechanical Properties Studies of printed conductive articles
2-1 acrylate monomer-containing 3D printing conductive material
1) 100 parts by weight of dihydroxyethyl acrylate monomer, 10 parts by weight of silver nitrate precursor, 2 parts by weight of photoinitiator camphorquinone and 2 parts by weight of photoinitiator aid ethyl 4-dimethylaminobenzoate, wherein the tin foil paper is shaded and stirred uniformly at room temperature to obtain a uniform mixture, and the uniform mixture is placed in a material tank.
2) Standard sample bars are prepared by adopting the equipment and the operation method.
2-2 3D printing conductive material containing oligomer EBECRYL270 polyurethane acrylate
1) 50 parts by weight of dihydroxyethyl acrylate monomer, 50 parts by weight of urethane acrylate (EBECRYL270, purchased from Qinggang chemical Co., Ltd., Shanghai), 10 parts by weight of silver nitrate precursor, 2 parts by weight of photoinitiator camphorquinone and 2 parts by weight of photoinitiator aid ethyl 4-dimethylaminobenzoate, the tinfoil paper is uniformly stirred and mixed under the condition of shading to obtain a uniform mixture, and the uniform mixture is placed in a material tank.
2) Standard sample bars are prepared by adopting the equipment and the operation method.
2-3-oligomer EBECRYL8402 polyurethane acrylate-containing 3D printing conductive material
1) 50 parts by weight of dihydroxyethyl acrylate monomer, 50 parts by weight of urethane acrylate (EBECRYL8402), 10 parts by weight of silver nitrate precursor, 2 parts by weight of photoinitiator camphorquinone and 2 parts by weight of photoinitiator auxiliary agent 4-ethyl dimethylaminobenzoate, wherein the tin foil paper is shielded from light, stirred and mixed uniformly at room temperature to obtain a uniform mixture, and the uniform mixture is placed in a material tank.
2) Standard sample bars are prepared by adopting the equipment and the operation method.
2-4 Poly N-vinyl pyrrolidone-containing 3D printing photo-curing resin material (silver-free)
1) Uniformly stirring and mixing 100 parts by weight of dihydroxyethyl acrylate monomer, 2 parts by weight of photoinitiator camphorquinone, 2 parts by weight of photoinitiator auxiliary agent 4-ethyl dimethylaminobenzoate and 10 parts by weight of stabilizer PVP (polyvinyl pyrrolidone) at room temperature in a shading mode for tinfoil paper to obtain a uniform mixture, and placing the uniform mixture in a material tank.
2) Standard sample bars are prepared by adopting the equipment and the operation method.
2-53D printing light-cured resin material (without silver)
1) 100 parts by weight of dihydroxyethyl acrylate monomer, 2 parts by weight of photoinitiator camphorquinone and 2 parts by weight of photoinitiator aid ethyl 4-dimethylaminobenzoate are uniformly mixed by shading and stirring tin foil paper at room temperature to obtain a uniform mixture, and the uniform mixture is placed in a material tank.
2) Standard sample bars are prepared by adopting the equipment and the operation method.
2-6 acrylate monomer-containing and PVP 3D printing conductive material
1) 100 parts by weight of dihydroxyethyl acrylate monomer, 2 parts by weight of photoinitiator camphorquinone, 2 parts by weight of photoinitiator auxiliary agent 4-ethyl dimethylaminobenzoate, 10 parts by weight of stabilizer PVP and 10 parts by weight of silver nitrate precursor are uniformly mixed by shading and stirring tin foil paper at room temperature to obtain a uniform mixture, and the uniform mixture is placed in a material tank.
2) Standard sample bars are prepared by adopting the equipment and the operation method.
The wide applicability of the material system and method of the present invention is demonstrated by the series of 3D printed splines with different components obtained as described in example 2. Mechanical property research is carried out on the sample strips (as shown in figure 5), and the result shows that compared with a light-cured resin material system, the addition of the conductive factor silver material realizes 3D printing of a resin-based conductive device, but the mechanical property of the material is poor. Firstly, the addition of different urethane acrylate oligomers can increase the breaking stress value of the material, increase the hardness of the material, and however, deteriorate the flexibility of the material. And the stabilizer poly-N-vinyl pyrrolidone (PVP) is added into an acrylate polymer system, so that the fracture stress and strain of the acrylate polymer system can be obviously improved, the reduction of mechanical properties caused by the addition of silver materials is compensated, and as shown in figure 5, the materials can keep better mechanical properties. The results further confirm the superiority and wide applicability of the photosensitive resin-based silver conductive material provided by the invention.
Comparative example 1 conductive material for 3D printing of acrylate monomer and silver nanoparticle mixture
1) Dispersing 10 parts by weight of silver nanoparticles (AgNPs) in 100 parts by weight of dihydroxyethyl acrylate monomer by ultrasonic at room temperature, uniformly stirring and mixing with 2 parts by weight of photoinitiator camphorquinone and 2 parts by weight of photoinitiator auxiliary agent 4-ethyl dimethylaminobenzoate at room temperature in a shading mode to obtain a uniform mixture, and placing the uniform mixture in a material tank.
2) And (3) preparing the polymer-based standard sample strip mixed with the silver nanoparticles by adopting the equipment and visible light DLP 3D printing.
It was found through mechanical property tests that, as shown in fig. 6, the sample strip prepared by using the material system mixed with silver nanoparticles in advance has a smaller stress and strain than the sample strip prepared by adding silver nitrate precursor and preparing silver nanoparticles through in-situ reduction according to the example 2-1 of the present invention. The reason is that when the silver nanoparticles are dispersed in the acrylate monomer, although the dispersion is assisted by ultrasound, the nanoparticles are easy to agglomerate, so that the silver nanoparticles cannot be well dispersed in a polymer network in the 3D printing process, local defects of printed products are caused, and the mechanical properties of the materials are influenced. In contrast, according to the silver nanoparticle in-situ preparation provided by the invention, the used printing material is that a silver precursor is dissolved in the photocuring resin, and the silver precursor in the material exposure area is synchronously reduced into silver nanoparticles and embedded into the polymer matrix in the 3D printing process, so that the mechanical property is prevented from being influenced by the agglomeration of the silver particles.
3) The above-mentioned sample bar was sintered in an air atmosphere at 150 ℃ for 2 hours.
The mean sheet resistance of the resulting sample surface was about 2.8. omega. sq.sq.-1The conductivity of the prepared product is basically the same as that of the product prepared by the material system. The silver content of the two material systems is basically the same, and the conductivity of the prepared product is derived from the silver nanoparticles and a conductive path formed after the silver nanoparticles are fused. However, the material system has obvious defects, and the viscosity of the material is increased sharply due to the addition of a large amount of silver nanoparticles, so that the material can be used for printing only simple splines shown in the comparative example, and printing of a complex three-dimensional structure cannot be carried out.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The visible light curing photosensitive resin-based silver conductive material is characterized by comprising the following components in parts by weight: 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 5-30 parts by weight of silver precursor and 0.01-5 parts by weight of photoinitiator.
2. The visible light-curable photosensitive resin-based silver conductive material according to claim 1, wherein the material comprises the following components in parts by weight: 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 8-25 parts by weight of silver precursor and 0.5-3 parts by weight of photoinitiator.
Preferably, the material comprises the following components in parts by weight: 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 10-20 parts by weight of silver precursor and 1.5-2.5 parts by weight of photoinitiator.
3. The visible light-curable photosensitive resin-based silver conductive material according to claim 1 or 2, wherein the polymerizable monomer is one or more of an acrylate compound, a vinyl ether compound, and an epoxy compound. More preferably, the vinyl-based compound is, for example, vinylpyrrolidone or the like; examples of the acrylate compound include methacrylate, trimethylolpropane triacrylate, and dihydroxyethyl acrylate.
Preferably, the polymerizable oligomer is one or more of unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, epoxy resin, silicone oligomer. More preferably, the oligomer is one or more of an unsaturated polyester, an epoxy acrylate, an epoxy resin, or a urethane acrylate; further preferably, the unsaturated polyester is, for example, glycidyl methacrylate, the epoxy acrylate is, for example, bisphenol a type epoxy acrylate, the epoxy resin is, for example, phenol type epoxy resin, and the urethane acrylate is, for example, aliphatic urethane acrylate.
Preferably, the silver precursor is silver nitrate, silver oxide, silver chloride, silver hexafluorophosphate, silver hexafluoroantimonate, and one or more of aliphatic carboxylic acid silver, aromatic carboxylic acid silver, and alicyclic carboxylic acid silver, which have 1 to 3 carboxyl groups, 0 to 2 hydroxyl groups, and 1 to 17 carbon atoms, such as silver butyrate, silver caprylate, and silver stearate.
Preferably, the photoinitiator is one or more of compounds having activity under the irradiation of visible light with the wavelength of 415-780 nm, such as: quinone compounds, cyclopentadienyl titanium compounds, iodonium salt compounds and sulfonium salt compounds. Preferably, the quinone compound is, for example, camphorquinone or the like. Preferably, the titanocene compound is, for example, fluorinated diphenyltitanocene and the like. Preferably, the iodonium salt compound is, for example, an alkyl iodonium salt or the like. Preferably, the sulfonium salt compound is, for example, an alkyl sulfonium salt.
4. The visible light-curing photosensitive resin-based silver conductive material according to any one of claims 1 to 3, further comprising the following components in parts by weight: 0-5 parts of photoinitiator assistant and 0-20 parts of other functional assistants.
Preferably, the material further comprises the following components in parts by weight: 1-4 parts of photoinitiator assistant and 0-15 parts of other functional assistants.
Preferably, the material further comprises the following components in parts by weight: 1.5-3 parts of photoinitiator assistant and 0-10 parts of other functional assistants.
5. The visible light-curing photosensitive resin-based silver conductive material according to any one of claims 1 to 4, wherein the photoinitiator auxiliary is one of a secondary amine compound, a tertiary amine compound, a secondary alcohol compound, and a tertiary alcohol compound. Preferably, the secondary amine compound is, for example, triethylamine. Preferably, the tertiary amine compound is, for example, ethyl 4-dimethylaminobenzoate. Preferably, the secondary alcohol compound is, for example, one of sec-butyl alcohol, sec-amyl alcohol and 2-hexanol. Preferably, the tertiary alcohol compound is, for example, one of tert-butanol and 2-methyl-2-butanol.
Preferably, the other functional auxiliary agents comprise one or more of pigments (such as cadmium yellow, cadmium red, cadmium green, iron blue and the like), stabilizers (such as surfactants, poly-N-vinyl pyrrolidone and the like), polymerization inhibitors (such as hydroxyanisole, hydroquinone and the like). Further preferably, the stabilizer is, for example, poly-N-vinylpyrrolidone; the polymerization inhibitor is, for example, hydroquinone.
6. The visible light-curable photosensitive resin-based silver conductive material according to any one of claims 1 to 5, wherein the material has a viscosity of 3 to 800cps at normal temperature. Preferably 40 to 700cps at normal temperature.
Preferably, the material can be cured under the irradiation of visible light with the wavelength of 415-780 nm.
Preferably, the material achieves rapid curing upon irradiation with a light source that: thermoluminescent light sources, gas discharge light sources or solid illumination light sources.
Preferably, the thermoluminescent light source is an incandescent lamp, a halogen lamp.
Preferably, the gas discharge light source is a fluorescent lamp, a metal halide.
Preferably, the solid-state illumination light source is an LD laser, an LED laser, or the like.
Preferably, the light source has an emission wavelength of 420 to 500nm, more preferably 430 to 480nm, and even more preferably 440 to 475 nm. The light source is further preferably a 445nm or 470nm blue solid illumination light source (e.g., LD laser, LED laser, etc.).
Preferably, the material sets under visible light irradiation for less than 5 seconds, preferably less than 2 seconds.
7. Use of the visible light-curable photosensitive resin-based silver conductive material according to any one of claims 1 to 6 for 3D printing.
8. An article prepared by visible light curing the visible light curing photosensitive resin-based silver conductive material according to any one of claims 1 to 6.
Preferably, the ink is prepared by visible light curing 3D printing.
Preferably, the article is an electrically conductive article.
9. A method of making the article of claim 8, the method comprising the steps of:
1) mixing the raw material components to prepare the visible light curing photosensitive resin-based silver conductive material;
2) curing the visible light curing photosensitive resin-based silver conductive material obtained in the step 1) layer by utilizing a projection pattern formed on a workbench by a light source to form a three-dimensional polymer matrix material, and simultaneously initiating in-situ generation of silver nanoparticles to prepare a three-dimensional metal nano composite material;
3) sintering the three-dimensional metal nano composite material obtained in the step 2) in an air atmosphere at 100-300 ℃, and fusing silver nano particles to obtain the product.
10. The method of making according to claim 9, wherein the method of making the article is a method based on a combination of visible light Digital Light Processing (DLP)3D printing technology and photoinduced in-situ reduction of silver precursors.
Preferably, in the step 3), the sintering temperature is preferably 120-200 ℃.
Preferably, the method comprises the steps of:
(1) stirring and uniformly mixing 100 parts by weight of polymerizable monomer and/or polymerizable oligomer, 5-30 parts by weight of silver precursor, 0.01-5 parts by weight of photoinitiator, 0-5 parts by weight of photoinitiator aid and 0-20 parts by weight of other functional aids at normal temperature to obtain a uniform mixture;
(2) placing the mixture obtained in the step (1) in a material tank of a device based on a visible light Digital Light Processing (DLP)3D printing technology, projecting the mixture onto the interface between the bottom of the material tank and the mixture on a lifting table through a light source, solidifying the mixture layer by layer, reducing the silver precursor in the mixture layer by layer to prepare silver nanoparticles, and finally printing a three-dimensional metal nano composite part;
(3) sintering the three-dimensional metal nano composite part obtained in the step (2) in an air atmosphere at the temperature of 100-300 ℃, and fusing the silver nano particles.
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