CN113755059A - Photosensitive resin-based conductive ink and preparation method and application thereof - Google Patents

Photosensitive resin-based conductive ink and preparation method and application thereof Download PDF

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CN113755059A
CN113755059A CN202111050788.3A CN202111050788A CN113755059A CN 113755059 A CN113755059 A CN 113755059A CN 202111050788 A CN202111050788 A CN 202111050788A CN 113755059 A CN113755059 A CN 113755059A
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silver
conductive ink
photosensitive resin
based conductive
ether
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王晓露
朱唐
朱才镇
徐坚
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Shenzhen University
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    • 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
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    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • 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
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/003—Apparatus or processes specially adapted for manufacturing conductors or cables using irradiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

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Abstract

The invention discloses photosensitive resin-based conductive ink and a preparation method and application thereof, wherein the photosensitive resin-based conductive ink comprises the following components in percentage by weight: 5-90% of metal precursor, 1-20% of photosensitive agent, 0.5-10% of surfactant, 5-50% of light-cured resin and 5-30% of solvent. The invention adopts a conductive metal precursor as a conductive metal source, and carries out redox reaction under the action of a photosensitive reagent and a light source to generate metal nano-particles; meanwhile, the size of the metal nano particles is regulated and controlled by the surfactant, the subsequent laser sintering temperature and time are reduced, the high conductivity of the product is ensured, and the particle fusion time and fusion temperature are shortened; in addition, the conductive ink does not contain metal particles, so that the printing equipment cannot be blocked; the technical scheme that this patent provided can be applied to numerous fields such as transistor, ultracapacitor system, flexible display, touch-sensitive screen, intelligent sensor, thing networking through technologies such as printing, 3D print.

Description

Photosensitive resin-based conductive ink and preparation method and application thereof
Technical Field
The invention relates to the technical field of conductive ink materials, in particular to photosensitive resin-based conductive ink and a preparation method and application thereof.
Background
In recent years, flexible electronic devices, such as stretchable solar cells, organic light emitting diodes, and the like, have been rapidly developed, and particularly, the fields of touch and flat panel display are industries with high attention. The flexible electrode material is taken as the basis of flexible electronic equipment, and attracts the attention of extensive researchers. The traditional transparent conductive material Indium Tin Oxide (ITO) has not been able to meet the requirements of flexible electronic devices due to its disadvantages of high rigidity, brittleness, high cost, etc. Therefore, conductive ink materials based on flexible printed electronics have been produced. The traditional flexible printing electronic technology is to prepare a flexible conductive film product in a large area by printing or coating conductive ink on a flexible polyester film substrate. The conductive ink is a key factor restricting the development of the industry at present and becomes a hotspot and a difficulty of research at home and abroad. The conductive ink material has diversity, and mainly comprises particle type conductive metal ink and non-particle type conductive ink. Taking silver conductive ink as an example, the granular silver conductive ink includes silver nanoparticles or silver nanowires as a conductive material, and particularly, silver nanowires attract a great deal of research work by researchers due to high conductivity, good flexibility and high transparency. Common systems include polymer composite films with randomly arranged silver nanowires and materials loaded with ordered silver grids. The former preparation method includes spin coating, spray coating, roll coating, vacuum filtration and the like, but the obtained nano silver wire network structure which does not need to be arranged is not uniform, the contact resistance between the silver wires is high, the silver wires are easy to be intertwined with each other to cause high surface roughness of the material, and the application of the nano silver wire network structure in actual production and life is greatly limited.
In order to further improve the conductivity and ensure the transparency of the secondary material, researchers adopt a Langmuir-Blodgett method or utilize capillary action and the like to assist the directional deposition of the silver wires on the substrate, or utilize a coffee ring effect to obtain a ring structure consisting of the nano silver wires. Through the improvement, the light transmittance of the material can be greatly improved, and the sheet resistance of the material is reduced. However, these methods have various degrees of defects such as the need for a substrate of a specific structure, strict control of solvent evaporation, and the like. The newly reported network structure formed by the silver wires with the nanometer or submicron scale does not depend on a polymer film as a substrate, but independently maintains a two-dimensional network structure, and simultaneously has better transparency and conductivity. However, the adhesion of pure silver material is poor, and further improvement is needed if the system is to be applied to practical application. In addition, other problems are faced in practical application of metallic conductive inks, including silver conductive inks, including: the conductive metal nano particles/nano wires need to be synthesized in advance, and the preparation process is complex; conductive nanoparticles in the ink are easy to generate coagulation, so that the stability of the ink is poor, the ink is difficult to store, printing equipment, pipelines and the like are easy to block in use, the contact resistance of the particle type ink is high, the conductivity is poor, subsequent high-temperature post-treatment is needed, and the application of the particle type ink in a flexible electronic device is limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide photosensitive resin-based conductive ink and a preparation method and application thereof, and aims to solve the problems of poor stability, easy blockage of printing equipment and poor conductivity of the conventional conductive ink.
The technical scheme of the invention is as follows:
a photosensitive resin-based conductive ink comprises the following components in percentage by weight: 5-90% of metal precursor, 1-20% of photosensitive agent, 0.5-10% of surfactant, 5-50% of light-cured resin and 5-30% of solvent.
The photosensitive resin-based conductive ink is characterized in that the metal precursor is one or more of a gold precursor, a silver precursor and a copper precursor.
The photosensitive resin-based conductive ink is characterized in that the gold precursor is one or more of chloroauric acid, sodium chloroaurate and potassium chloroaurate; and/or the silver precursor is one or more of silver nitrate, silver chloride, silver bromide, silver iodide, silver fluoride, silver sulfate, silver phosphate, silver tetrafluoroborate, silver sulfadiazine, silver sulfide, silver p-toluenesulfonate, silver hexafluoroantimonate, silver trifluoromethanesulfonate, silver trifluoroacetate, silver acetate, silver carbonate and silver trifluoromethanesulfonate; and/or the copper precursor is one or more of cupric chloride, cuprous chloride, cupric bromide, cupric sulfate, cupric nitrate, cupric pyrophosphate, cupric citrate, cupric acetate, cupric methanesulfonate, cupric oxalate, cuprous iodide, cuprous thiocyanate, copper trifluoromethanesulfonate, copper acetylacetonate and copper tetrafluoroborate.
The photosensitive resin-based conductive ink is characterized in that the photosensitive reagent is one or more of hematin ether, 5-aminolevulinic acid, m-tetrahydroxyphenyl chlorin, protoporphyrin tin, methylene blue, benzoporphyrin derivatives, hematoporphyrin derivatives, benzoporphyrin derivative monoacids, phthalocyanines, dexsaxaporphyrin, N-asparaginyl chlorin, hypericin, hematoporphyrin monomethyl ether, camphorquinone, ethyl 4-dimethylaminobenzoate, azobisisobutyronitrile, benzoin derivatives, acetophenone derivatives, aromatic ketone compounds, acylphosphine oxides, aromatic diazonium salts, diaryl iodine compounds and triaryl sulfur compounds.
The photosensitive resin-based conductive ink is characterized in that the surfactant is one or more of stearic acid, sodium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene sodium sulfate, sodium cocoyl alcohol sulfate, sodium lauryl alcohol sulfate, monolauryl phosphate, disodium lauryl sulfonate succinate, alkyl glucoside, fatty glyceride, sorbitan fatty acid, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, hexadecyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, cationic guar gum, dodecyl dimethyl amine oxide, alkylolamide, fatty alcohol polyoxyethylene ether, coconut oil fatty acid glycol amide, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.
The photosensitive resin-based conductive ink is characterized in that the light-cured resin is one or more of acrylic acid, polymethacrylic acid, 3-ethoxyacrylic acid, 3-benzoylacrylic acid, 1, 4-benzenediacrylic acid, acrylic ester, dihydroxyethyl acrylate, polyurethane acrylate, ethyl cyanoacrylate, methyl methacrylate, hexyl methacrylate, butyl methacrylate, hydroxypropyl acrylate, adamantyl acrylate, lauryl methacrylate, polyethylene glycol diacrylate, perfluorooctyl acrylate, perfluorodecyl acrylate, ethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, poly (ethylene glycol) methacrylate, polyethylene glycol dimethacrylate and o-phenylphenoxyethyl acrylate.
The photosensitive resin-based conductive ink is characterized in that the solvent is one or more of water, ethanol, ethylene glycol, glycerol, N-butanol, isobutanol, isopropanol, isoamyl alcohol, 1, 3-butanediol, acetone, butanone, cyclohexanone, methyl isobutyl ketone, diisobutyl ketone, ethylene glycol butyl ether, ethylene glycol ethyl ether, dipropylene glycol methyl ether, ethylene glycol phenyl ether, glycidyl ether, ethyl acetate, butyl acetate, isoamyl acetate, N-butyl glycolate, N-hexane, cyclohexane, N-heptane, N-octane, isooctane, toluene, xylene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, sulfuric acid, pentafluorophenol, fluoromethylphenol and trifluoroacetic acid.
A preparation method of photosensitive resin-based conductive ink comprises the following steps:
and under the condition of keeping out of the sun, mixing and uniformly stirring the metal precursor, the photosensitive reagent, the surfactant, the light-cured resin and the solvent to obtain the photosensitive resin-based conductive ink.
The application of the photosensitive resin-based conductive ink is to prepare a conductive device.
The application of the photosensitive resin-based conductive ink comprises the following steps of:
preparing the photosensitive resin-based conductive ink into a conductive pattern by adopting a printing or 3D printing mode;
reducing the metal precursor in the conductive pattern into metal nano particles in situ under the action of a light source, and curing the light-cured resin in the conductive pattern;
fusing the metal nano-particles by means of laser sintering.
Has the advantages that: the invention provides photosensitive resin-based conductive ink without synthesizing conductive metal particles or metal wires in advance, which adopts a conductive metal precursor as a conductive metal source to carry out redox reaction under the action of a photosensitive reagent and a light source to generate metal nanoparticles. Meanwhile, the size of the metal nano particles is regulated and controlled by the surfactant, the subsequent laser sintering temperature and time are reduced, the high conductivity of the product is ensured, and the particle fusion time and fusion temperature are shortened. In addition, the conductive ink can be used for flexible electronic printing of a conductive film and can also be used for photocuring 3D printing of a flexible conductive structure. Since the conductive ink does not contain metal particles, it does not clog a printing apparatus. Meanwhile, the use of adhesives and the like is avoided, so that the conductivity of the printing structure is improved. The technical scheme that this patent provided can be applied to numerous fields such as transistor, ultracapacitor system, flexible display, touch-sensitive screen, intelligent sensor, thing networking through technologies such as printing, 3D print.
Drawings
FIG. 1 is a flow chart of the photosensitive resin-based conductive ink used for preparing a conductive device according to the present invention.
Detailed Description
The invention provides photosensitive resin-based conductive ink and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In some embodiments, there is provided a photosensitive resin-based conductive ink comprising, in weight percent: 5-90% of metal precursor, 1-20% of photosensitive agent, 0.5-10% of surfactant, 5-50% of light-cured resin and 5-30% of solvent.
In the present embodiment, the metal precursor is one or more of a gold precursor, a silver precursor, and a copper precursor, but is not limited thereto. By way of example, the gold precursor is one or more of chloroauric acid, sodium chloroaurate, and potassium chloroaurate, but is not limited thereto; the silver precursor is one or more of silver nitrate, silver chloride, silver bromide, silver iodide, silver fluoride, silver sulfate, silver phosphate, silver tetrafluoroborate, silver sulfadiazine, silver sulfide, silver p-toluenesulfonate, silver hexafluoroantimonate, silver trifluoromethanesulfonate, silver trifluoroacetate, silver acetate, silver carbonate and silver trifluoromethanesulfonate, but is not limited thereto; the copper precursor is one or more of copper chloride, cuprous chloride, cupric bromide, cupric sulfate, cupric nitrate, cupric pyrophosphate, cupric citrate, cupric acetate, cupric methanesulfonate, cupric oxalate, cuprous iodide, cuprous thiocyanate, copper trifluoromethanesulfonate, copper acetylacetonate and copper tetrafluoroborate, but is not limited thereto.
In this embodiment, the photosensitizing agent is one or more of a deuteroporphyrin ether, 5-aminolevulinic acid, m-tetrahydroxyphenyl chlorin, protoporphyrin tin, methylene blue, tolylene blue, a phenylporphyrin derivative, a hematoporphyrin derivative, a benzoporphyrin derivative monoacid, phthalocyanines, dactinoporphyrin, N-asparaginyl chlorin, hypericin, hematoporphyrin monomethyl ether, camphorquinone, ethyl 4-dimethylaminobenzoate, azobisisobutyronitrile, benzoin, a benzoin derivative, an acetophenone derivative, an aromatic ketone compound, an acylphosphine oxide, an aromatic diazonium salt, a diaryl iodide compound, and a triaryl sulfide compound.
In this embodiment, the surfactant is one or more of stearic acid, sodium dodecylbenzene sulfonate, sodium fatty alcohol polyoxyethylene sulfate, sodium cocoyl sulfate, sodium lauryl sulfate, monolauryl phosphate, disodium lauryl sulfosuccinate, alkyl glucoside, fatty glyceride, sorbitan fatty acid, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, cetyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, cationic guar gum, dodecyl dimethyl amine oxide, alkylolamide, fatty alcohol polyoxyethylene ether, coconut oil fatty acid glycol amide, fatty alcohol polyoxyethylene ether, and alkylphenol polyoxyethylene ether, but is not limited thereto.
In the present embodiment, the light-curable resin is one or more of acrylic acid, polymethacrylic acid, 3-ethoxyacrylic acid, 3-benzoylacrylic acid, 1, 4-benzenediacrylic acid, acrylate, dihydroxyethyl acrylate, urethane acrylate, ethyl cyanoacrylate, methyl methacrylate, hexyl methacrylate, butyl methacrylate, hydroxypropyl acrylate, adamantyl acrylate, lauryl methacrylate, polyethylene glycol diacrylate, perfluorooctyl acrylate, perfluorodecyl acrylate, ethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, poly (ethylene glycol) methacrylate, polyethylene glycol dimethacrylate, and o-phenylphenoxyethyl acrylate, but is not limited thereto.
In this embodiment, the solvent is one or more of water, ethanol, ethylene glycol, glycerol, N-butanol, isobutanol, isopropanol, isoamyl alcohol, 1, 3-butanediol, acetone, butanone, cyclohexanone, methyl isobutyl ketone, diisobutyl ketone, ethylene glycol butyl ether, ethylene glycol ethyl ether, dipropylene glycol methyl ether, ethylene glycol phenyl ether, glycidyl ether, ethyl acetate, butyl acetate, isoamyl acetate, N-butyl glycolate, N-hexane, cyclohexane, N-heptane, N-octane, isooctane, toluene, xylene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, sulfuric acid, pentafluorophenol, fluoromethylphenol, and trifluoroacetic acid, but is not limited thereto.
In some embodiments, there is also provided a method for preparing a photosensitive resin-based conductive ink, comprising the steps of: and under the condition of keeping out of the sun, mixing and uniformly stirring the metal precursor, the photosensitive reagent, the surfactant, the light-cured resin and the solvent to obtain the photosensitive resin-based conductive ink.
In some embodiments, there is also provided a use of a photosensitive resin-based conductive ink for preparing a conductive device.
In this embodiment, as shown in fig. 1, the step of using the photosensitive resin-based conductive ink to prepare a conductive device includes:
s10, preparing the photosensitive resin-based conductive ink into a conductive pattern by adopting a printing or 3D printing mode;
s20, reducing the metal precursor in the conductive pattern into metal nano particles in situ under the action of a light source, and curing the light-cured resin in the conductive pattern;
and S30, fusing the metal nano particles by means of laser sintering.
In this embodiment, the wavelength of the light source is 400-500nm, and the power is 20-1000mW cm-2(ii) a The laser sintering time is 1min-3 h; in this embodiment, the base material used for the printing or 3D printing may be a planar material, a curved material, a profile structure material, a transparent material, and a frosted material with poor transparency.
In this embodiment, the photosensitive resin-based conductive ink does not need to synthesize conductive metal nanoparticles in advance, but utilizes a photosensitive reagent to induce the redox reaction of a metal precursor under the action of a light source to realize the in-situ generation of the metal nanoparticles, and simultaneously initiates the polymerization of photosensitive resin under the action of the light source to realize the one-time rapid molding of a flexible conductive product; in the embodiment, the surfactant in the photosensitive resin-based conductive ink can effectively regulate and control the size of the generated metal nanoparticles, the quantity and the thickness of the metal nanoparticles can be regulated and controlled through the action time of a light source, and the nanoparticles can be fused through a laser sintering technology, so that a conductive device with excellent conductivity is prepared; in this embodiment, photosensitive resin base conductive ink can be through printing and 3D printing technology rapid prototyping, because printing ink does not contain the metal particle, can not block up printing apparatus to applicable substrate is extensive, can be plane material, curved surface material, special-shaped structure material, transparent material and the poor dull polish material of transparency, has the universality. By way of example, the conductive device may be a transistor, a super capacitor, a flexible display, a touch screen, a smart sensor, or the like.
The photosensitive resin-based conductive ink of the present invention, the preparation method and the application thereof are further explained by the following specific examples:
example 1
1) The photosensitive resin-based silver conductive ink comprises the following raw materials:
silver nitrate: 10 percent of
Camphorquinone: 2 percent of
Ethyl 4-dimethylaminobenzoate: 2 percent of
Acrylate ester: 70 percent of
Monolauryl phosphate: 2 percent of
Ethylene glycol: 14 percent.
2) The application of the photosensitive resin-based silver conductive ink comprises the following steps:
preparing conductive ink, namely uniformly stirring and mixing the raw materials at room temperature by using tinfoil paper to shield light to obtain a uniform mixture;
selecting polyester film as base material, printing preset conductive pattern on the surface of the base material by screen printing method, and then using 445nm wavelength and 250mW cm power-2The pattern is irradiated by the light source for 10min to initiate the reduction of silver nitrate and the polymerization of acrylic ester;
after the nano silver is formed, the nano silver is fused by laser sintering for 5min, and the conductivity of the pattern is further improved.
In this example, silver nitrate was used as the silver precursor, acrylate was the photocurable resin, and camphorquinone and ethyl-4-dimethylaminobenzoate were used as the photosensitizers. Under the action of light source, the photosensitizer can trigger the reduction of silver nitrate to produce nano silver, and at the same time, the photosensitizer can trigger acrylic esterThe polymerization of (2). In addition, the monolauryl phosphate is used as a surfactant, the size of the silver nanoparticles can be regulated and controlled, the size of the generated silver nanoparticles is reduced, and the temperature and time of a subsequent laser sintering process can be reduced, so that the product has good conductivity. The conductive ink prepared in the embodiment is used for screen printing of a silver wire structure on a polyester film, and the conductivity of the silver wire obtained after laser sintering reaches 3.2 x 106S m-1。
Example 2
1) The photosensitive resin-based silver conductive ink comprises the following raw materials:
silver nitrate: 30 percent of
Azobisisobutyronitrile: 5 percent of
Dihydroxyethyl acrylate: 50 percent of
Octadecyl trimethyl ammonium chloride: 3 percent of
Ethylene glycol: 12 percent.
2) The application of the photosensitive resin-based silver conductive ink comprises the following steps:
preparing conductive ink, namely uniformly stirring and mixing the raw materials at room temperature by using tinfoil paper to shield light to obtain a uniform mixture;
selecting a polyimide film as a substrate, printing a preset conductive pattern on the surface of the substrate by a 3D printing method, and simultaneously using a wavelength of 445nm and a power of 250mW cm-2The light source projects upwards from the bottom, firstly penetrates through a substrate material, and then irradiates an ink liquid film on the substrate, so that the reduction of silver nitrate and the polymerization of dihydroxyethyl acrylate are initiated;
after the nano silver is formed, the nano silver is fused by laser sintering for 2min, and the conductivity of the pattern is further improved.
In this example, silver nitrate was used as a silver precursor, dihydroxyethyl acrylate was used as a photocurable resin, and azobisisobutyronitrile was used as a photosensitizer. Under the action of a light source, the photosensitizer can initiate the reduction of silver nitrate to generate nano silver, and simultaneously, the photosensitizer can also initiate the polymerization of dihydroxyethyl acrylate. In addition, the octadecyl trimethyl ammonium chloride is taken as a surfactant, the size of the silver nano-particles can be regulated and controlled,the size of the generated nano silver particles is reduced, and the temperature and time of a subsequent laser sintering process can be reduced, so that the product has good conductivity. The silver wire structure printed by the conductive ink prepared by the embodiment has the thickness of about 100nm after laser sintering, and the conductivity reaches 5.6 x 106S m-1。
Example 3
1) The photosensitive resin-based gold conductive ink comprises the following raw materials:
sodium chloroaurate: 35 percent of
Camphorquinone: 4 percent of
Methyl methacrylate: 40 percent of
Polysorbate 60: 4 percent of
Ethylene glycol ethyl ether: 17 percent.
2) The application of the photosensitive resin-based gold conductive ink comprises the following steps:
preparing conductive ink, namely uniformly stirring and mixing the raw materials at room temperature by using tinfoil paper to shield light to obtain a uniform mixture;
selecting a polypropylene film as a substrate, printing a preset conductive pattern on the surface of the substrate by a 3D printing method, and simultaneously using a wavelength of 445nm and a power of 100mW cm-2The light source projects downwards from the top, and directly irradiates an ink liquid film printed on the surface of the substrate, thereby initiating the reduction of sodium chloroaurate and the polymerization of methyl methacrylate;
after the nano-gold is formed, the nano-gold is fused through laser sintering treatment for 10min, and the conductivity of the pattern is further improved.
In this example, sodium chloroaurate was used as the silver precursor, methyl methacrylate was the photocurable resin, and camphorquinone was the photosensitizer. Under the action of light source, the photosensitizer can initiate the reduction of sodium chloroaurate to produce nano gold, and at the same time, the photosensitizer can also initiate the polymerization of methyl methacrylate. In addition, the polysorbate 60 is used as a surfactant, so that the size of the gold nanoparticles can be regulated, the size of the generated gold nanoparticles is reduced, and the temperature and time of a subsequent laser sintering process can be reduced, so that the product has good conductivity. Preparation Using this exampleThe gold wire structure printed by the conductive ink has the conductive performance reaching 8.7 x 10 after laser sintering6S m-1。
Example 4
1) The photosensitive resin-based copper conductive ink comprises the following raw materials:
copper chloride: 55 percent of
Camphorquinone: 4 percent of
Ethyl 4-dimethylaminobenzoate: 4 percent of
Acrylate ester: 20 percent of
Coconut oil fatty acid glycol amide: 6 percent of
Ethylene glycol: 11 percent.
2) The application of the photosensitive resin-based copper conductive ink comprises the following steps:
preparing conductive ink, namely uniformly stirring and mixing the raw materials at room temperature by using tinfoil paper to shield light to obtain a uniform mixture;
selecting a polyester film as a substrate, printing a preset conductive pattern on the surface of the substrate by a 3D printing method, and simultaneously using a wavelength of 445nm and a power of 250mW cm-2The light source projects downwards from the top, and directly irradiates an ink liquid film printed on the surface of the substrate, thereby initiating the reduction of copper chloride and the polymerization of acrylic ester;
after the nano-copper is formed, the nano-copper is fused through laser sintering treatment for 20min, and the conductivity of the pattern is further improved.
In this example, copper chloride was used as the silver precursor, acrylic ester was the photocurable resin, and camphorquinone and ethyl-4-dimethylaminobenzoate were used as the photosensitizers. Under the action of a light source, the photosensitizer can initiate the reduction of copper chloride to generate nano copper, and meanwhile, the photosensitizer can also initiate the polymerization of acrylic ester. In addition, coconut oil fatty acid glycol amide is used as a surfactant, the size of copper nanoparticles can be regulated, the size of the generated copper nanoparticles is reduced, and the temperature and time of a subsequent laser sintering process can be reduced, so that the product has good conductivity. After the copper wire structure printed by the conductive ink prepared by the embodiment is used, the conductive performance reaches 1.2 x 10 after laser sintering6S m-1。
Example 5
1) The photosensitive resin-based silver conductive ink comprises the following raw materials:
silver chloride: 35 percent of
5-aminolevulinic acid: 5 percent of
Acrylic acid: 30 percent of
Tween 20: 5 percent of
Ethylene glycol: 25 percent.
2) The application of the photosensitive resin-based silver conductive ink comprises the following steps:
preparing conductive ink, namely uniformly stirring and mixing the raw materials at room temperature by using tinfoil paper to shield light to obtain a uniform mixture;
selecting ground glass as a substrate, printing a preset conductive pattern on the surface of the substrate by a screen printing method, and then printing the pattern by using a screen printing method at a wavelength of 445nm and a power of 250mW cm-2The pattern is irradiated by the light source for 30min, and then the reduction of silver chloride and the polymerization of acrylic acid are initiated;
after the nano silver is formed, the nano silver is fused for 15min through laser sintering treatment, so that the conductivity of the pattern is further improved;
in this example, silver chloride was used as a silver precursor, acrylic acid was a photocurable resin, and 5-aminolevulinic acid was a photosensitizer. Under the action of a light source, the photosensitizer can initiate the reduction of silver chloride to generate nano silver, and meanwhile, the photosensitizer can also initiate the polymerization of acrylic acid. In addition, Tween 20 is used as a surfactant, the size of the silver nanoparticles can be regulated, so that the size of the generated silver nanoparticles is reduced, and the temperature and time of a subsequent laser sintering process can be reduced, thereby ensuring that the product has good conductivity. The conductive ink prepared by the embodiment is used for printing the prepared silver wire structure, and the conductive performance reaches 4.4 x 10 after laser sintering6S m-1。
Example 6
1) The photosensitive resin-based silver conductive ink comprises the following raw materials:
silver acetate: 40 percent of
Meta-tetrahydroxyphenyl chlorins: 5 percent of
Butyl methacrylate: 25 percent of
Sodium dodecylbenzenesulfonate: 5 percent of
Butanediol: 25 percent.
2) The application of the photosensitive resin-based silver conductive ink comprises the following steps:
preparing conductive ink, namely uniformly stirring and mixing the raw materials at room temperature by using tinfoil paper to shield light to obtain a uniform mixture;
selecting a polyester pipe as a base material, printing a preset conductive pattern on the surface of a curved surface base material by a 3D printing method, and simultaneously using a wavelength of 445nm and a power of 100mW cm-2The light source projects downwards from the top, and directly irradiates an ink liquid film printed on the surface of the substrate, so that reduction of silver acetate and polymerization of butyl methacrylate are initiated;
after the nano silver is formed, the nano silver is fused through laser sintering treatment for 15min, and the conductivity of the pattern is further improved.
In this example, silver acetate was used as the silver precursor, butyl methacrylate was used as the photocurable resin, and m-tetrahydroxyphenyl chlorin was used as the photosensitizer. Under the action of a light source, the photosensitizer can initiate the reduction of silver acetate to generate nano silver, and simultaneously, the photosensitizer can also initiate the polymerization of butyl methacrylate. In addition, the sodium dodecyl benzene sulfonate is used as a surfactant, the size of the silver nanoparticles can be regulated and controlled, the size of the generated silver nanoparticles is reduced, and the temperature and time of a subsequent laser sintering process can be reduced, so that the product has good conductivity. By using the embodiment, the conductive silver wire structure with the thickness of 80nm can be prepared on the curved surface, and the conductive performance reaches 5.4 x 10 after laser sintering6S m-1。
In summary, the invention provides a novel photosensitive resin-based conductive ink, which contains a metal precursor, a photosensitive agent, a surfactant and a photocurable resin, wherein the size of silver particles is controlled by the surfactant, the absorption of a material system to light is improved by the photosensitive agent, the redox reaction of the metal precursor is induced to realize the in-situ generation of conductive nanoparticles, and the photocuring reaction of the resin is initiated, so that the in-situ self-assembly of the metal nanoparticles is realized, and then the conductive patterns such as conductive metal nanowires and conductive metal grids with good conductivity are formed after laser sintering. The ink does not need to synthesize conductive metal nano particles in advance, and can realize one-step forming of flexible conductive products through printing and 3D printing technologies. The printing ink does not contain conductive metal particles, cannot block printing equipment, avoids the use of binders and the like, and greatly improves the conductivity of a printing structure.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (10)

1. The photosensitive resin-based conductive ink is characterized by comprising the following components in percentage by weight: 5-90% of metal precursor, 1-20% of photosensitive agent, 0.5-10% of surfactant, 5-50% of light-cured resin and 5-30% of solvent.
2. The photosensitive resin-based conductive ink according to claim 1, wherein the metal precursor is one or more of a gold precursor, a silver precursor, and a copper precursor.
3. The photosensitive resin-based conductive ink according to claim 2, wherein the gold precursor is one or more of chloroauric acid, sodium chloroaurate, and potassium chloroaurate; and/or the silver precursor is one or more of silver nitrate, silver chloride, silver bromide, silver iodide, silver fluoride, silver sulfate, silver phosphate, silver tetrafluoroborate, silver sulfadiazine, silver sulfide, silver p-toluenesulfonate, silver hexafluoroantimonate, silver trifluoromethanesulfonate, silver trifluoroacetate, silver acetate, silver carbonate and silver trifluoromethanesulfonate; and/or the copper precursor is one or more of cupric chloride, cuprous chloride, cupric bromide, cupric sulfate, cupric nitrate, cupric pyrophosphate, cupric citrate, cupric acetate, cupric methanesulfonate, cupric oxalate, cuprous iodide, cuprous thiocyanate, copper trifluoromethanesulfonate, copper acetylacetonate and copper tetrafluoroborate.
4. The photosensitive resin-based conductive ink according to claim 1, wherein the photosensitive agent is one or more of a deuteroporphyrin ether, 5-aminolevulinic acid, m-tetrahydroxyphenyl chlorin, tin protoporphyrin, methylene blue, methylene benzyl, a phenylporphyrin derivative, a hematoporphyrin derivative, a benzoporphyrin derivative monoacid, phthalocyanines, texaphyrin, N-asparaginyl chlorin, hypericin, hematoporphyrin monomethyl ether, camphorquinone, ethyl 4-dimethylaminobenzoate, azobisisobutyronitrile, benzoin derivatives, acetophenone derivatives, aromatic ketone compounds, acylphosphine oxides, aromatic diazonium salts, diaryl iodide compounds, and triaryl sulfide compounds.
5. The photosensitive resin-based conductive ink according to claim 1, wherein the surfactant is one or more of stearic acid, sodium dodecylbenzenesulfonate, sodium fatty alcohol polyoxyethylene sulfate, sodium cocoyl sulfate, sodium lauryl sulfate, monolauryl phosphate, disodium lauryl sulfosuccinate, alkyl glucoside, fatty glyceride, sorbitan fatty acid, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, hexadecyl dimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, cationic guar gum, dodecyl dimethyl amine oxide, alkylolamide, fatty alcohol polyoxyethylene ether, coconut oil fatty glycol amide, fatty alcohol polyoxyethylene ether, and alkylphenol polyoxyethylene ether.
6. The photosensitive resin-based conductive ink according to claim 1, the light-cured resin is one or more of acrylic acid, polymethacrylic acid, 3-ethoxyacrylic acid, 3-benzoylacrylic acid, 1, 4-benzenediacrylate, acrylate, dihydroxyethyl acrylate, polyurethane acrylate, ethyl cyanoacrylate, methyl methacrylate, hexyl methacrylate, butyl methacrylate, hydroxypropyl acrylate, adamantyl acrylate, lauryl methacrylate, polyethylene glycol diacrylate, perfluorooctyl acrylate, perfluorodecyl acrylate, ethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methyl ether methacrylate, poly (ethylene glycol) methacrylate, polyethylene glycol dimethacrylate and o-phenylphenoxyethyl acrylate.
7. The photosensitive resin-based conductive ink according to claim 1, wherein the solvent is one or more of water, ethanol, ethylene glycol, glycerol, N-butanol, isobutanol, isopropanol, isoamyl alcohol, 1, 3-butanediol, acetone, butanone, cyclohexanone, methyl isobutyl ketone, diisobutyl ketone, ethylene glycol butyl ether, ethylene glycol ethyl ether, dipropylene glycol methyl ether, ethylene glycol phenyl ether, glycidyl ether, ethyl acetate, butyl acetate, isoamyl acetate, N-butyl glycolate, N-hexane, cyclohexane, N-heptane, N-octane, isooctane, toluene, xylene, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, tetrahydrofuran, N-methylpyrrolidone, sulfuric acid, pentafluorophenol, fluoromethylphenol, and trifluoroacetic acid.
8. A method for preparing the photosensitive resin-based conductive ink as claimed in any one of claims 1 to 7, comprising the steps of:
and under the condition of keeping out of the sun, mixing and uniformly stirring the metal precursor, the photosensitive reagent, the surfactant, the light-cured resin and the solvent to obtain the photosensitive resin-based conductive ink.
9. Use of the photosensitive resin-based conductive ink according to any one of claims 1 to 7 for the preparation of a conductive device.
10. Use of the photosensitive resin-based conductive ink according to claim 9, wherein the use of the photosensitive resin-based conductive ink for the preparation of a conductive device comprises the steps of:
preparing the photosensitive resin-based conductive ink into a conductive pattern by adopting a printing or 3D printing mode;
reducing the metal precursor in the conductive pattern into metal nano particles in situ under the action of a light source, and curing the light-cured resin in the conductive pattern;
fusing the metal nano-particles by means of laser sintering.
CN202111050788.3A 2021-09-08 2021-09-08 Photosensitive resin-based conductive ink and preparation method and application thereof Pending CN113755059A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114262555A (en) * 2022-01-17 2022-04-01 江苏冠军科技集团股份有限公司 Sulfanilamide-silver compound doped graphene zinc powder heavy-duty anticorrosive coating and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090206520A1 (en) * 2008-02-19 2009-08-20 Samsung Electronics Co., Ltd. Photosensitive composition, microfabrication method using the same, and microfabricated structure thereof
CN111117367A (en) * 2018-10-30 2020-05-08 中国科学院化学研究所 Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material
CN111171488A (en) * 2018-10-23 2020-05-19 中国科学院化学研究所 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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090206520A1 (en) * 2008-02-19 2009-08-20 Samsung Electronics Co., Ltd. Photosensitive composition, microfabrication method using the same, and microfabricated structure thereof
CN111171488A (en) * 2018-10-23 2020-05-19 中国科学院化学研究所 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
CN111117367A (en) * 2018-10-30 2020-05-08 中国科学院化学研究所 Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
董国君等: "《表面活性剂化学》", 31 August 2009, 北京理工大学出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114262555A (en) * 2022-01-17 2022-04-01 江苏冠军科技集团股份有限公司 Sulfanilamide-silver compound doped graphene zinc powder heavy-duty anticorrosive coating and preparation method thereof
CN114262555B (en) * 2022-01-17 2022-09-27 江苏冠军科技集团股份有限公司 Sulfanilamide-silver compound doped graphene zinc powder heavy-duty anticorrosive coating and preparation method thereof

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Application publication date: 20211207