WO2019242742A1 - 一种低熔点金属的印刷方法 - Google Patents

一种低熔点金属的印刷方法 Download PDF

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Publication number
WO2019242742A1
WO2019242742A1 PCT/CN2019/092310 CN2019092310W WO2019242742A1 WO 2019242742 A1 WO2019242742 A1 WO 2019242742A1 CN 2019092310 W CN2019092310 W CN 2019092310W WO 2019242742 A1 WO2019242742 A1 WO 2019242742A1
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Prior art keywords
substrate
low
melting
point metal
printing
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PCT/CN2019/092310
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English (en)
French (fr)
Inventor
朱唐
梁赟
卢双豪
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北京梦之墨科技有限公司
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Publication of WO2019242742A1 publication Critical patent/WO2019242742A1/zh

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/038—Textiles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1216—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by screen printing or stencil printing
    • H05K3/1225—Screens or stencils; Holders therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1266—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by electrographic or magnetographic printing
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1275—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by other printing techniques, e.g. letterpress printing, intaglio printing, lithographic printing, offset printing

Definitions

  • the invention relates to the field of printing technology, in particular to a printing method for a low melting point metal.
  • low melting point metal As a new functional material with unique physical and chemical properties, low melting point metal has developed rapidly in recent years. How to realize the printing and printing of low melting point metal has gradually become the focus of research. Low-melting-point metals have extremely high surface tension. At present, low-melting-point metals can only perform good printing on a few substrates such as polyvinyl chloride (PVC), which is difficult to print directly, which limits the application of low-melting-point metals.
  • PVC polyvinyl chloride
  • the embodiment of the present invention provides a printing method for a low melting point metal, which can print a low melting point metal on the surface of a substrate to which the low melting point metal is adhered, and expand the application range of the low melting point metal.
  • An embodiment of the present invention provides a method for printing a low-melting-point metal, which adopts the following technical scheme.
  • the method for printing a low-melting-point metal includes: providing a substrate, and the surface of the substrate is adhered with a low-melting-point metal; Performing a treatment to obtain a treated substrate, and the surface of the treated substrate is not adhered to a low melting point metal; an ink that can adhere to the treated substrate and can adhere to the low melting point metal is selected; Printing a target pattern with the ink on the treated substrate surface; curing the ink on the treated substrate surface; step S6, printing the low melting point metal on the treated substrate surface .
  • the substrate is a polyvinyl chloride material, a polyethylene terephthalate substrate, a polybutylene terephthalate substrate, a polypropylene substrate, a polyadipate-pair Butyl phthalate substrate, silicone rubber substrate, natural rubber substrate, isoprene rubber substrate, styrene-butadiene rubber substrate, butadiene rubber substrate, neoprene substrate, ethylene-propylene rubber substrate, butadiene One of a nitrile rubber substrate, a silicone rubber substrate, a polysulfide rubber substrate, a glass substrate, a polyurethane substrate, an acrylic substrate, a stainless steel substrate, a silicon substrate, and a nylon cloth.
  • the treating the substrate to obtain a treated substrate comprises: using a solution consisting of a modifier and a solvent, performing a modification treatment on the surface of the substrate, and subjecting the substrate to the modified treatment The surface of the substrate was dried to obtain the treated substrate.
  • the modifier includes behenane, stearic acid, palmitic acid, arachidic acid, wood wax, palm wax, rice bran wax, jojoba wax, castor wax, bayberry wax, candelilla wax , From beeswax, insect wax, wool wax, whale wax, paraffin wax, microcrystalline paraffin wax, petroleum wax, emulsified wax, montan wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, chlorinated paraffin wax, ethylene-vinyl acetate copolymer wax
  • the solvent includes ether, petroleum ether, n-heptane, n-hexane, cyclohexane, ethyl acetate, methanol, ethanol, acetic acid, chloroform, carbon tetrachloride, benzene Or several of toluene, xylene and xylene.
  • the concentration of the modifier is 1 to 40 mg / mL.
  • the surface of the substrate is modified by one of dipping, spraying, drip coating, and printing, using a solution consisting of a modifier and a solvent; by natural drying, air drying, and heating drying, One is to dry the surface of the substrate after the modification treatment.
  • the ink is one of water-based ink, oil-based self-volatile ink, heat-curable ink, ultraviolet-curable ink, electron beam-curable ink, and laser-curable ink.
  • stencil printing, screen printing, inkjet printing, ultraviolet printing, gravure printing, letterpress printing, lithography, and thermal transfer are performed.
  • a target pattern is printed with the ink.
  • the ink curing method includes at least one of room temperature curing, heat curing, ultraviolet light curing, electron beam irradiation curing, and laser curing.
  • the printing of the low-melting-point metal on the surface of the substrate after the processing includes: printing the low-melting-point metal in a liquid state to the processing.
  • the printing of the low-melting-point metal on the surface of the treated substrate includes: heating the low-melting-point metal in a solid state, so that The low-melting metal is completely melted into a liquid state, and the low-melting metal in a liquid state is printed on the surface of the substrate after the treatment.
  • the printing the liquid low-melting-point metal on the surface of the treated substrate includes: uniformly coating the liquid low-melting-point metal on a roller, and using the roller to preset a first The pressure rolls on the surface of the treated substrate, and a low-melting metal is printed on the surface of the treated substrate; or, the liquid low-melting metal is evenly coated on a water platform, and the treated The substrate is attached to the water platform, and a low-melting-point metal is printed on the surface of the processed substrate under the effect of a second preset pressure, and the processed substrate and the substrate are printed after printing.
  • the low-melting-point metal in a liquid state is loaded into a container, and the treated substrate is immersed in the container for immersion treatment and taken out after a preset immersion time; or, the liquid state
  • the low-melting-point metal is filled into a watering can, and the low-melting-point metal in a liquid state is sprayed onto the surface of the treated substrate by using the watering can under a third preset pressure.
  • the first preset pressure, the second preset pressure, the third preset pressure, or the The preset dipping time is selected.
  • the roller is a heatable roller
  • the water platform is a heatable water platform
  • the container is a heatable container
  • the watering can is a heatable watering can.
  • a method for printing a low-melting-point metal provided by an embodiment of the present invention.
  • the process of printing a low-melting-point metal on the surface of a substrate with a low-melting-point metal using the printing method is as follows: First, the substrate is processed to obtain a treated substrate. Low-melting-point metal is not adhered to the surface of the treated substrate, and then, an ink that can adhere to the treated substrate and adhere to the low-melting metal is selected, and then printed on the surface of the treated substrate with ink The target pattern is followed by curing the ink on the surface of the processed substrate. Finally, a low melting point metal is printed on the surface of the processed substrate. The low melting point metal does not adhere to the surface of the processed substrate but adheres to the ink.
  • the low-melting-point metal After printing the low-melting-point metal on the surface of the processed substrate, only the low-melting-point metal is covered on the ink, and no low-melting-point metal is covered elsewhere on the surface of the processed substrate, so that the pattern of the low-melting-point metal is the same as the preset pattern That is, the printing of the low melting point metal on the surface of the substrate to which the low melting point metal is adhered is realized, and the application range of the low melting point metal is expanded.
  • FIG. 1 is a flowchart of a printing method for a low melting point metal according to an embodiment of the present invention.
  • FIG. 1 is a flowchart of a method for printing a low melting point metal according to an embodiment of the present invention. Printing methods include:
  • Step S1 a substrate is provided, and a low melting point metal is adhered to the surface of the substrate;
  • the melting point of the low-melting-point metal in the embodiment of the present invention is below 300 ° C.
  • the substrate is a polyvinyl chloride material, a polyethylene terephthalate substrate, a polybutylene terephthalate substrate, a polypropylene substrate, and a polyadipate-terephthalic acid.
  • the shape of the substrate can be a film, a sheet, a plate, a spherical surface and other special structures, which are not limited in the embodiments of the present invention. Among them, the specific substrate can be selected according to the actual application.
  • the low-melting-point metal is adhered to the surface of the substrate can be determined by printing through experiments, or can be determined by the following relatively simple methods: placing the substrate on a test stand at an angle of inclination of 20 °, Low-melting-point metal droplets (volume of 80 ⁇ L to 120 ⁇ L, taking 80 ⁇ L as an example) are dropped from a certain height (2 cm to 5 cm, taking 2 cm as an example) to the surface of the substrate. If no low-melting metal remains on the substrate surface, then It means that the low melting point metal is not adhered to the surface of the substrate. If the low melting point metal remains on the surface of the substrate, it means that the low melting point metal is adhered to the surface of the substrate.
  • Step S2 the substrate is processed to obtain a processed substrate, and the surface of the processed substrate does not adhere to a low melting point metal;
  • processing the substrate to obtain a processed substrate includes: using a solution composed of a modifier and a solvent to perform a modification treatment on the surface of the substrate and drying the surface of the substrate after the modification treatment. A treated substrate was obtained.
  • the modifier includes behenicane, stearic acid, palmitic acid, arachidic acid, wood wax, palm wax, rice bran wax, jojoba wax, castor wax, bayberry wax, candelilla wax, self-beeswax , Insect wax, wool wax, whale wax, paraffin wax, microcrystalline paraffin wax, petroleum wax, emulsified wax, montan wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, chlorinated paraffin wax, ethylene-vinyl acetate copolymer wax, ethylene oxide
  • the solvent includes ether, petroleum ether, n-heptane, n-hexane, cyclohexane, ethyl acetate, methanol, ethanol, acetic acid, chloroform, carbon tetrachloride, benzene, toluene, and One or more of xylene.
  • the concentration of the modifier is 1 to 40 mg / mL, where the greater the concentration of the modifier, the less the amount of solution required and the shorter the modification time, those skilled in the art may Need to make a selection.
  • the surface of the substrate is modified by one of dipping, spraying, drip coating, and printing, using a solution consisting of a modifier and a solvent; natural drying, air drying, and heating drying (heating) One of the temperatures (0 to 200 ° C) dries the surface of the substrate after the modification treatment.
  • Step S3 selecting an ink that can adhere to the surface of the substrate after the treatment and can adhere to a low melting point metal
  • the ink is one of water-based ink, oil-based self-volatile ink, heat-curable ink, ultraviolet-curable ink, electron beam-curable ink, and laser-curable ink.
  • whether the ink adheres to the low-melting metal and whether the ink adheres to the treated substrate surface can be determined experimentally by printing, or it can be similar to the method for determining whether the substrate has adhered to the low-melting metal surface described previously. The determination is made, and is not repeated here.
  • Step S4 printing a target pattern with ink on the surface of the processed substrate
  • step S4 printing is performed by using one of stencil printing, screen printing, inkjet printing, ultraviolet printing, gravure printing, letterpress printing, lithography, thermal transfer printing, and electrostatic printing.
  • stencil printing is performed by using one of stencil printing, screen printing, inkjet printing, ultraviolet printing, gravure printing, letterpress printing, lithography, thermal transfer printing, and electrostatic printing.
  • Target pattern is performed by using one of stencil printing, screen printing, inkjet printing, ultraviolet printing, gravure printing, letterpress printing, lithography, thermal transfer printing, and electrostatic printing.
  • Step S5 curing the ink on the surface of the substrate after the treatment
  • the manner of curing the ink can be selected according to the nature of the selected ink and the nature of the substrate after the treatment.
  • the ink curing method includes at least one of room temperature curing, heat curing, ultraviolet light curing, electron beam irradiation curing, and laser curing.
  • Step S6 Printing a low-melting-point metal on the surface of the processed substrate.
  • printing the low-melting-point metal on the surface of the processed substrate in step S6 includes: printing the liquid low-melting-point metal on the surface of the processed substrate;
  • printing the low melting point metal on the surface of the treated substrate includes: heating the solid low melting point metal to completely melt the low melting point metal into a liquid state, and printing the liquid low melting point metal. To the treated substrate surface.
  • the working temperature of the low-melting metal when printing on the surface of the substrate after processing in step S6 may be higher than the melting point of the low-melting metal. Specifically, a reasonable selection can be made in combination with the withstand temperature of the treated substrate and the melting point of the low melting point metal.
  • a liquid low-melting-point metal can be printed on the surface of the treated substrate in various manners, which are described below by way of example:
  • a liquid low-melting-point metal is evenly coated on a roller, and the roller is used to apply a first preset pressure on the surface of the substrate after treatment. Roll and print low melting metal on the surface of the treated substrate.
  • the first preset pressure can be selected according to the material of the processed substrate (including the material of the modifier and the material of the substrate itself) and the target thickness of the low-melting metal to be printed.
  • the first preset pressure does not exceed the pressure limit when the processed substrate is not adhered, the low melting point metal is not printed to a position other than the ink, and the target substrate can be printed with a low thickness on the surface of the processed substrate. Melting point metal.
  • the roller is a heatable roller, which can not only heat the low-melting metal during the process of printing the low-melting metal, prevent the low-melting metal from solidifying or the viscosity is too large to print, but also directly convert the solid
  • the low-melting metal is heated above its melting point to make it liquid and subsequent printing is performed.
  • the liquid low-melting-point metal is evenly coated on the water platform, and the processed substrate is attached to the water platform. Under the action of the second preset pressure, A low melting point metal is printed on the surface of the treated substrate, and the treated substrate is separated from the water platform after printing.
  • the second preset pressure may be selected according to the material of the processed substrate and the target thickness of the low-melting metal to be printed, so that the second preset pressure does not exceed the processed substrate
  • the pressure limit during non-adhesion prevents the low-melting-point metal from printing to a position other than the ink, and enables printing of a low-melting-point metal having a target thickness on the surface of the processed substrate.
  • the water platform is a heatable water platform, which can not only heat the low melting point metal during the process of printing the low melting point metal, prevent the low melting point metal from solidifying or the viscosity is too large to print, but also directly convert the solid The low-melting metal is heated above its melting point to make it liquid and subsequent printing is performed.
  • a liquid low-melting-point metal is charged into a container, and the treated substrate is immersed in the container for immersion treatment and taken out after a preset immersion time (for example, 10 s).
  • the preset immersion time can be selected according to the material of the processed substrate and the target thickness of the low-melting-point metal to be printed, so that the low-melting-point metal will not be printed to a position other than the ink, and can be A low melting point metal having a target thickness is printed on the surface of the treated substrate.
  • the container is a heatable container, which can not only heat the low melting point metal in the process of printing the low melting point metal, prevent the low melting point metal from solidifying or the viscosity is too large to print, but also directly solid the low melting point.
  • the metal is heated above its melting point to make it liquid and subsequent printing is performed.
  • a liquid low-melting-point metal is filled into a watering can, and the liquid low-melting-point metal is sprayed onto the surface of the treated substrate by using a watering can under a third preset pressure.
  • the third preset pressure may be selected according to the material of the processed substrate and the target thickness of the low-melting metal to be printed, so that the third preset pressure does not exceed the processed substrate.
  • the pressure limit during non-adhesion prevents the low-melting-point metal from printing to a position other than the ink, and enables printing of a low-melting-point metal having a target thickness on the surface of the processed substrate.
  • the watering can is a heatable watering can, which can not only heat the low melting point metal in the process of printing the low melting point metal, prevent the low melting point metal from solidifying or the viscosity is too large to print, but also directly change the solid low melting point.
  • the metal is heated above its melting point to make it liquid and subsequent printing is performed.
  • the thickness of the low-melting-point metal printed by using the methods in the first example and the second example is small, and the minimum can reach 1 to 2 ⁇ m.
  • the thickness of the low-melting metal printed by the methods in the third example and the fourth example is relatively large, and is usually 10 ⁇ m or more.
  • the thickness of the low-melting metal obtained by printing can be adjusted by the number of repeated printings.
  • the method for printing a low-melting-point metal in the embodiment of the present invention may further include a step of post-processing the product obtained in step S5 to obtain a desired product.
  • the post-processing may include component mounting, sealing, curing, cutting, One or more of the packaging.
  • the low-melting-point metal in the embodiment of the present invention is a low-melting-point metal element having a melting point of less than 300 ° C, a low-melting point alloy having a melting point of less than 300 ° C, or a blend or blend having a melting point of less than 300 ° C Including at least two of low-melting metal simple substance, low-melting alloy and functional powder, that is, the blend includes low-melting metal simple substance and low-melting alloy, or the blend includes low-melting alloy and functional powder, or The mixture includes a low-melting metal element and a functional powder, or the blend includes a low-melting metal element, a low-melting alloy, and a functional powder.
  • the low-melting metal element may be a mercury element, a gallium element, an indium element, or a tin element.
  • the low melting point alloy may be gallium indium alloy, gallium indium tin alloy, gallium tin alloy, gallium zinc alloy, gallium indium zinc alloy, gallium tin zinc alloy, gallium tin cadmium alloy, gallium zinc cadmium Alloy, bismuth indium alloy, bismuth tin alloy, bismuth indium tin alloy, bismuth indium zinc alloy, bismuth tin zinc alloy, bismuth indium tin zinc alloy, bismuth indium tin lead alloy, bismuth tin cadmium alloy, bismuth lead tin alloy, bismuth tin lead One of cadmium alloy, tin-lead alloy, tin-copper alloy, tin-zinc alloy, tin-zinc-copper alloy, and tin-silver-copper alloy.
  • the functional powder may be nickel simple substance, iron simple substance, titanium simple substance, zinc simple substance, silver simple substance, copper simple substance, iron oxide, copper oxide, zinc oxide, carbon powder, graphene, carbon nanotubes, silicon oxide, nitrogen At least one of boron, bentonite, and kaolin.
  • a method for printing a low-melting-point metal provided by an embodiment of the present invention.
  • the process of printing a low-melting-point metal on the surface of a substrate with a low-melting-point metal using the printing method is as follows: First, the substrate is processed to obtain a treated substrate. Low-melting-point metal is not adhered to the surface of the treated substrate, and then, an ink that can adhere to the treated substrate and adhere to the low-melting metal is selected, and then printed on the surface of the treated substrate with ink The target pattern is followed by curing the ink on the surface of the processed substrate. Finally, a low melting point metal is printed on the surface of the processed substrate. The low melting point metal does not adhere to the surface of the processed substrate but adheres to the ink.
  • the low-melting-point metal is printed on the surface of the treated substrate, only the low-melting-point metal is covered on the ink, and there is no low-melting-point metal covering elsewhere on the surface of the processed substrate, so that the pattern of the low-melting-point metal is the same as the preset pattern. That is, the printing of the low melting point metal on the surface of the substrate to which the low melting point metal is adhered is realized, and the application range of the low melting point metal is expanded.
  • Example 1 A low melting metal RFID tag is printed on the surface of a nylon cloth. The specific process is as follows:
  • Nylon cloth is impregnated with paraffin (modifier) / n-hexane (solvent) at 10 mg / mL in advance for 20 minutes, and dried at room temperature for 10 minutes before use;
  • step (2) using a screen printing method to print an RFID label on the surface of the nylon cloth after the special screen printing ink for nylon is processed in step (1);
  • step (3) The nylon cloth printed with the RFID tag image in step (2) is left at room temperature for 10 seconds, and the ink on it is completely cured;
  • a low melting point metal with a melting point of 58 ° C (Bi31.6% In48.8% Sn19.6%, all of which are weight percentages) is uniformly coated on a water platform heated to 80 ° C in advance, and step (3 The nylon cloth obtained in) is attached to the above-mentioned low-melting-point metal-coated water platform, and the nylon cloth and the low-melting-point metal are closely adhered to each other for 10 seconds with a clean roller at a pressure of 0.7 MPa. ;
  • step (4) The product obtained in step (4) is allowed to stand at room temperature for 1 minute to obtain a low-melting-point metal RFID tag.
  • the thickness of the low-melting-point metal obtained by the printing method is 15 micrometers, and the identification function can be realized after the chip is mounted.
  • Example 2 a low-melting-point metal circuit is printed on the surface of a polybutylene terephthalate (PBT) film.
  • PBT polybutylene terephthalate
  • the PBT membrane was immersed in 10mg / mL beeswax / n-heptane solution for 10min beforehand, and dried at room temperature for 20min before use;
  • step (2) using a screen printing method to print a circuit diagram of the modified vinyl resin ink on the surface of the PBT film treated in step (1);
  • step (3) the PBT film printed with the circuit diagram in step (2) is processed for 10s under the condition of laser irradiation, and the ink on it is completely cured;
  • step (4) The product obtained in step (4) is left to stand at room temperature for 1 minute to obtain a low-melting-point metal circuit.
  • the low-melting-point metal printed by this printing method has a thickness of about 12 microns, a width of 2 mm, and a length of 100 mm.
  • the resistance is about 3.8 ohms.
  • Example 3 a low-melting metal pattern is printed on the surface of a polypropylene (PP) plastic bottle, and the specific process is as follows:
  • PP plastic bottle is sprayed with 15mg / mL polyethylene wax / trichloromethane solution in advance, and treated at 50 ° C for 2 minutes in an oven;
  • step (3) The PP plastic bottle printed with the pattern in step (2) is processed for 10s under the condition of electron beam irradiation, and the ink on it is completely cured;
  • step (4) The product obtained in step (4) is allowed to stand at room temperature for 2 minutes to obtain a low-melting metal pattern.
  • the low-melting-point metal obtained by the printing method has a thickness of about 4 micrometers, is conductive, has good metallic luster, and requires no packaging, and can be directly used for packaging products.
  • Example 4 a low-melting-point metal circuit is printed on the surface of a polyvinyl chloride (PVC) plastic film, and the specific process is as follows:
  • the PVC plastic film is impregnated with 5mg / mL stearic acid / ether solution in advance for 1min, and then blow-dried in cold air for later use;
  • step (2) using a stencil printing method to print a circuit pattern of the polyurea ink on the surface of the PVC plastic film treated in step (1);
  • step (3) The PVC plastic film printed with the circuit pattern in step (2) is processed under an oven at 60 ° C for 1 hour, and the ink on it is completely cured;
  • step (4) The product obtained in step (4) is subjected to sealing treatment, and the low-melting-point metal circuit is obtained after the adhesive is cured and cut.
  • the low-melting-point metal printed by this printing method has a thickness of about 5 microns, a width of 3 mm, and a line with a length of 100 mm having a resistance of about 1.3 ohms.
  • Example 5 a stretchable elastic circuit is printed on the surface of the silicone rubber, and the specific process is as follows:
  • a layer of 10 mg / mL candelilla wax / xylene solution is printed on the surface of the silicone rubber in advance, and dried in an oven at 50 ° C for later use;
  • step (1) using a screen printing method to print a circuit pattern on the surface of the silicone rubber after the urethane acrylate ink is processed in step (1);
  • step (3) irradiate the silicone rubber printed with the circuit pattern in step (2) under ultraviolet light for 30s, and wait for the ink on it to be completely cured;
  • step (4) The product obtained in step (4) is subjected to an elastic glue encapsulation treatment. After the glue is cured and cut, a stretchable elastic circuit is obtained.
  • the low-melting-point metal printed by this printing method has a thickness of about 18 microns, a width of 3 mm, and a length of 100 mm, and the resistance is about 1.1 ohms.
  • the silicone rubber elongation is 30%, the resistance becomes 4.3 ohms.
  • Embodiment 6 a low-melting-point metal circuit is printed on a glass surface, and the specific process is as follows:
  • the glass surface is pre-treated with 20 mg / mL docosane / carbon tetrachloride solution, and dried at room temperature for later use;
  • step (2) using a thermal transfer method to print a circuit pattern on the glass surface treated by the epoxy resin ink in step (1);
  • step (3) the glass with the circuit pattern printed in step (2) is left at room temperature for 2 minutes, and the ink on it is completely dried;
  • step (4) The product obtained in step (4) is left to stand at room temperature for 5 minutes, and the low melting point metal can be completely solidified.
  • the low-melting-point metal printed by this printing method has a thickness of about 7 microns, a width of 1 mm, and a length of 100 mm, and the resistance is about 31 ohms.
  • Example 7 A thin film switch is prepared by printing a low melting point metal circuit on the surface of polyethylene terephthalate (PET). The specific process is as follows:
  • PET is drip-treated with 35mg / mL jojoba wax / n-hexane solution, and dried at room temperature for later use;
  • step (3) The PET film on which the circuit diagram is printed in step (2) is left at room temperature for 1 second, and the ink on it is completely dried;
  • the low melting point metal having a melting point of 58 ° C (Bi31.6% In48.8% Sn19.6%, all of which are weight percentages) is roll-coated in advance on a stainless steel roller heated to 70 ° C, and the uniform coating is used as described above.
  • the metal cloth roll is rolled on the PET surface obtained in step (3) at a pressure of 1.0 MPa, so that the low melting point metal adheres to the ink.
  • step (4) Gluing the product obtained in step (4) to obtain a membrane switch including a low melting point metal circuit.
  • the thickness of the low-melting metal printed by this printing method is only 5 micrometers, and the function of the membrane switch can be achieved by pressing.

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Abstract

提供一种低熔点金属的印刷方法，涉及印刷技术领域。提供的低熔点金属的印刷方法包括：提供一基材，基材表面粘附低熔点金属；对基材进行处理，得到处理后的基材，处理后的基材表面不粘附低熔点金属；选择可粘附处理后的基材，且可粘附低熔点金属的油墨；在处理后的基材表面用油墨印制目标图案；使处理后的基材表面的油墨固化；在处理后的基材表面印刷低熔点金属。提供的技术方案能够在粘附低熔点金属的基材表面上印刷低熔点金属，扩大低熔点金属的应用范围。

Description

一种低熔点金属的印刷方法
本申请要求在2018年06月22日提交中国专利局、申请号为201810651855.9、发明名称为“一种低熔点金属的印刷方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及印刷技术领域，尤其涉及一种低熔点金属的印刷方法。
背景技术
低熔点金属作为一种物理化学性质独特的新兴功能材料，近年来发展迅速，如何实现低熔点金属的打印和印刷逐渐成为研究的重点。低熔点金属的表面张力极大，目前，低熔点金属仅能在聚氯乙烯(PVC)等少数基材上进行较好打印，难以直接印刷，限制了低熔点金属的应用。
发明内容
本发明实施例提供一种低熔点金属的印刷方法，可以在粘附低熔点金属的基材表面上印刷低熔点金属，扩大低熔点金属的应用范围。
本发明实施例提供一种低熔点金属的印刷方法，采用如下技术方案，所述低熔点金属的印刷方法包括：提供一基材，所述基材表面粘附低熔点金属；对所述基材进行处理，得到处理后的基材，所述处理后的基材表面不粘附低熔点金属；选择可粘附所述处理后的基材，且可粘附所述低熔点金属的油墨；在所述处理后的基材表面用所述油墨印制目标图案；使所述处理后的基材表面的所述油墨固化；步骤S6、在所述处理后的基材表面印刷所述低熔点金属。
可选地，所述基材为聚氯乙烯基材、聚对苯二甲酸乙二醇酯基材、聚对苯二甲酸丁二醇酯基材、聚丙烯基材、聚己二酸-对苯二甲酸丁二酯基材、硅橡胶基材、天然橡胶基材、异戊橡胶基材、丁苯橡胶基材、顺丁橡胶基 材、氯丁橡胶基材、乙丙橡胶基材、丁腈橡胶基材、硅橡胶基材、聚硫橡胶基材、玻璃基材、聚氨酯基材、亚克力基材、不锈钢基材、硅基材、尼龙布中的一种。
可选地，所述对所述基材进行处理，得到处理后的基材包括：使用由改性剂和溶剂组成的溶液，对所述基材表面进行改性处理，并使改性处理后的基材表面干燥，得到所述处理后的基材。
可选地，所述改性剂包括二十二烷、硬脂酸、棕榈酸、花生酸、木蜡、棕榈蜡、米糠蜡、荷荷芭蜡、蓖麻蜡、杨梅蜡、小烛树蜡、自蜂蜡、虫白蜡、羊毛蜡、鲸蜡、石蜡、微晶石蜡、石油蜡、乳化蜡、褐煤蜡、费托蜡、聚乙烯蜡、聚丙烯蜡、氯化石蜡、乙烯-乙酸乙烯共聚蜡、氧化乙烯蜡中的一种或几种，所述溶剂包括乙醚、石油醚、正庚烷、正己烷、环己烷、乙酸乙酯、甲醇、乙醇、醋酸、氯仿、四氯化碳、苯、甲苯和二甲苯中的一种或几种。
可选地，所述改性剂的浓度为1～40mg/mL。
可选地，通过浸渍、喷涂、滴涂，印刷中的一种，使用由改性剂和溶剂组成的溶液，对所述基材表面进行改性处理；通过自然干燥、风干、加热干燥中的一种使改性处理后的基材表面干燥。
可选地，所述油墨为水性油墨、油性自挥发油墨、加热固化油墨、紫外固化油墨、电子束固化油墨、激光固化油墨中的一种。
可选地，在所述处理后的基材表面用所述油墨印制目标图案中通过钢网印刷、丝网印刷、喷墨印刷、紫外打印、凹版印刷、凸版印刷、平板印刷、热转印印刷、静电印刷中的一种方式，用所述油墨印制目标图案。
可选地，所述油墨固化的方式包括室温固化、加热固化、紫外光照固化、电子束辐照固化、激光固化中至少一种。
可选地，所述低熔点金属的熔点等于或低于室温时，所述在所述处理后的基材表面印刷所述低熔点金属包括：将液态的所述低熔点金属印刷至所述处理后的基材表面；所述低熔点金属的熔点高于室温时，所述在所述处理后的基材表面印刷所述低熔点金属包括：对固态的所述低熔点金属进行加热，使所述低熔点金属完全熔化呈液态，将液态的所述低熔点金属印刷至所述处理后的基材表面。
进一步地，所述将液态的所述低熔点金属印刷至所述处理后的基材表面包括：在辊筒上均匀涂布液态的所述低熔点金属，用所述辊筒以第一预设压力在所述处理后的基材表面上滚动，在所述处理后的基材表面印刷低熔点金属；或者，在水平台上均匀涂布液态的所述低熔点金属，将所述处理后的基材贴附于所述水平台上，在第二预设压力的作用下，在所述处理后的基材表面印刷低熔点金属，并在印刷之后将所述处理后的基材与所述水平台分离；或者，将液态的所述低熔点金属装入容器内，将所述处理后的基材浸入所述容器中进行浸渍处理经预设浸渍时间后取出；或者，将液态的所述低熔点金属灌装至喷壶中，用所述喷壶在第三预设压力的作用下将液态的所述低熔点金属喷至所述处理后的基材表面。
进一步地，根据所述处理后的基材的材质和需要印刷的低熔点金属的目标厚度，对所述第一预设压力、所述第二预设压力、所述第三预设压力或者所述预设浸渍时间进行选择。
可选地，所述辊筒为可加热的辊筒，所述水平台为可加热的水平台，所述容器为可加热的容器，所述喷壶为可加热的喷壶。
本发明实施例提供的一种低熔点金属的印刷方法，使用该印刷方法在粘附低熔点金属的基材表面印刷低熔点金属的过程如下：首先，对基材进行处理，得到处理后的基材，处理后的基材表面不粘附低熔点金属，然后，选择可粘附处理后的基材，且可粘附低熔点金属的油墨，接着，在处理后的基材表面用油墨印制目标图案，接着，使处理后的基材表面的油墨固化，最后，在处理后的基材表面印刷低熔点金属，由于低熔点金属不粘附处理后的基材表面，但粘附油墨，因此，在处理后的基材表面印刷低熔点金属后，仅油墨上覆盖有低熔点金属，处理后的基材表面其他位置均无低熔点金属覆盖，使得低熔点金属的图形与预设图形相同，即实现了低熔点金属在粘附低熔点金属的基材表面上印刷，扩大了低熔点金属的应用范围。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲， 在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例提供的低熔点金属的印刷方法的流程图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明的是，在不冲突的情况下本发明实施例中的各技术特征均可以相互结合。
针对现有技术中的技术问题，发明人经过研究发现，低熔点金属无法进行印刷的具体原因如下：印刷所采用的大多数基材与低熔点金属之间均不粘附，而即使采用与低熔点金属粘附的基材，基材的各个位置对低熔点金属的粘附性没有选择性，导致在基材上只能整面上印刷低熔点金属，也无法印刷出图案。基于此，本发明实施例提供一种低熔点金属的印刷方法，具体地，如图1所示，图1为本发明实施例提供的低熔点金属的印刷方法的流程图，该低熔点金属的印刷方法包括：
步骤S1、提供一基材，基材表面粘附低熔点金属；
本发明实施例中的低熔点金属的熔点在300℃以下。
可选地，基材为聚氯乙烯基材、聚对苯二甲酸乙二醇酯基材、聚对苯二甲酸丁二醇酯基材、聚丙烯基材、聚己二酸-对苯二甲酸丁二酯基材、硅橡胶基材、天然橡胶基材、异戊橡胶基材、丁苯橡胶基材、顺丁橡胶基材、氯丁橡胶基材、乙丙橡胶基材、丁腈橡胶基材、硅橡胶基材、聚硫橡胶基材、玻璃基材、聚氨酯基材、亚克力基材、不锈钢基材、硅基材、尼龙布中的一种。基材的形状可以为薄膜、片状、板状、球面及其他异型结构，本发明实施例不进行限定。其中，可以根据实际应用确定具体选择哪种基材。
需要说明的是，基材表面是否粘附低熔点金属可以通过实验进行印刷确定，也可以通过以下较为简单的方式确定：将基材倾斜放置于测试台上， 基材的倾斜角度为20°，使低熔点金属液滴(体积为80μL～120μL，以80μL为例)从一定高度(2cm～5cm，以2cm为例)滴落至基材表面上，若基材表面无低熔点金属残留，则表示基材表面不粘附低熔点金属，若基材表面有低熔点金属残留，则表示基材表面粘附低熔点金属。
步骤S2、对基材进行处理，得到处理后的基材，处理后的基材表面不粘附低熔点金属；
步骤S2中，对基材进行处理，得到处理后的基材包括：使用由改性剂和溶剂组成的溶液，对基材表面进行改性处理，并使改性处理后的基材表面干燥，得到处理后的基材。
具体地，改性剂包括二十二烷、硬脂酸、棕榈酸、花生酸、木蜡、棕榈蜡、米糠蜡、荷荷芭蜡、蓖麻蜡、杨梅蜡、小烛树蜡、自蜂蜡、虫白蜡、羊毛蜡、鲸蜡、石蜡、微晶石蜡、石油蜡、乳化蜡、褐煤蜡、费托蜡、聚乙烯蜡、聚丙烯蜡、氯化石蜡、乙烯-乙酸乙烯共聚蜡、氧化乙烯蜡中的一种或几种，所述溶剂包括乙醚、石油醚、正庚烷、正己烷、环己烷、乙酸乙酯、甲醇、乙醇、醋酸、氯仿、四氯化碳、苯、甲苯和二甲苯中的一种或几种。
可选地，改性剂的浓度为1～40mg/mL，其中，改性剂的浓度越大，所需的溶液的量越少，改性处理的时间越短，本领域技术人员可以根据实际需要进行选择。
可选地，通过浸渍、喷涂、滴涂，印刷中的一种，使用由改性剂和溶剂组成的溶液，对所述基材表面进行改性处理；通过自然干燥、风干、加热干燥(加热温度为0～200℃)中的一种使改性处理后的基材表面干燥。
步骤S3、选择可粘附处理后的基材表面，且可粘附低熔点金属的油墨；
其中，可以根据油墨与处理后的基材表面的粘附性，以及与低熔点金属的粘附性等进行选择。可选地，步骤S3中，油墨为水性油墨、油性自挥发油墨、加热固化油墨、紫外固化油墨、电子束固化油墨、激光固化油墨中的一种。
类似地，油墨是否粘附低熔点金属，以及油墨是否粘附处理后的基材表面可以通过实验进行印刷确定，也可以通过与之前所述的确定基材表面 是否粘附低熔点金属类似的方式进行确定，此处不再进行赘述。
步骤S4、在处理后的基材表面用油墨印制目标图案；
其中，可以根据处理后的基材的性质，以及选择的油墨的性质对所需的方式进行选择。可选地，步骤S4中，通过钢网印刷、丝网印刷、喷墨印刷、紫外打印、凹版印刷、凸版印刷、平板印刷、热转印印刷、静电印刷中的一种方式，用油墨印制目标图案。
步骤S5、使处理后的基材表面的油墨固化；
其中，可以根据选择的油墨的性质，以及处理后的基材的性质对油墨固化的方式进行选择。可选地，步骤S5中，油墨固化的方式包括室温固化、加热固化、紫外光照固化、电子束辐照固化、激光固化中至少一种。
步骤S6、在处理后的基材表面印刷低熔点金属。
可选地，低熔点金属的熔点等于或低于室温时，步骤S6中，在处理后的基材表面印刷低熔点金属包括：将液态的低熔点金属印刷至处理后的基材表面；低熔点金属的熔点高于室温时，步骤S6中，在处理后的基材表面印刷低熔点金属包括：对固态的低熔点金属进行加热，使低熔点金属完全熔化呈液态，将液态的低熔点金属印刷至处理后的基材表面。
为了防止印刷过程中低熔点金属温度过低固化或者粘稠度太大无法印刷，步骤S6中在处理后的基材表面印刷低熔点金属时的工作温度可以高于低熔点金属的熔点。具体可以结合处理后的基材的可承受温度，以及低熔点金属的熔点进行合理选择。
本发明实施例中可以通过多种方式，将液态的低熔点金属印刷至处理后的基材表面，以下进行举例描述：
在第一个例子(对应后续实施例2,3,6,7)中，在辊筒上均匀涂布液态的低熔点金属，用辊筒以第一预设压力在处理后的基材表面上滚动，在处理后的基材表面印刷低熔点金属。
在实际使用过程中，可以根据处理后的基材的材质(包括改性剂的材质和基材本身的材质)和需要印刷的低熔点金属的目标厚度，对第一预设压力进行选择，以使得第一预设压力不会超过处理后的基材不粘附时的压力极限，使低熔点金属不会印刷到油墨以外的位置，且能够在处理后的基材表面印刷具有目标厚度的低熔点金属。
可选地，辊筒为可加热的辊筒，不仅可以在印刷低熔点金属的过程中对低熔点金属进行加热，防止低熔点金属凝固或者粘稠度过大无法印刷，还可以直接将固态的低熔点金属加热至其熔点以上，使其成为液态，并进行后续的印刷。
在第二个例子(对应后续实施例1)中，在水平台上均匀涂布液态的低熔点金属，将处理后的基材贴附于水平台上，在第二预设压力的作用下，在处理后的基材表面印刷低熔点金属，并在印刷之后将处理后的基材与水平台分离。
在实际使用过程中，可以根据处理后的基材的材质和需要印刷的低熔点金属的目标厚度，对第二预设压力进行选择，以使得第二预设压力不会超过处理后的基材不粘附时的压力极限，使低熔点金属不会印刷到油墨以外的位置，且能够在处理后的基材表面印刷具有目标厚度的低熔点金属。
可选地，水平台为可加热的水平台，不仅可以在印刷低熔点金属的过程中对低熔点金属进行加热，防止低熔点金属凝固或者粘稠度过大无法印刷，还可以直接将固态的低熔点金属加热至其熔点以上，使其成为液态，并进行后续的印刷。
在第三个例子(对应后续实施例5)中，将液态的低熔点金属装入容器内，将处理后的基材浸入容器中进行浸渍处理经预设浸渍时间(例如10s)后取出。
在实际使用过程中，可以根据处理后的基材的材质和需要印刷的低熔点金属的目标厚度，对预设浸渍时间进行选择，以使得低熔点金属不会印刷到油墨以外的位置，且能够在处理后的基材表面印刷具有目标厚度的低熔点金属。
可选地，容器为可加热的容器，不仅可以在印刷低熔点金属的过程中对低熔点金属进行加热，防止低熔点金属凝固或者粘稠度过大无法印刷，还可以直接将固态的低熔点金属加热至其熔点以上，使其成为液态，并进行后续的印刷。
在第四个例子(对应实施例4)中，将液态的低熔点金属灌装至喷壶中，用喷壶在第三预设压力的作用下将液态的低熔点金属喷至处理后的基材表面。
在实际使用过程中，可以根据处理后的基材的材质和需要印刷的低熔点金属的目标厚度，对第三预设压力进行选择，以使得第三预设压力不会超过处理后的基材不粘附时的压力极限，使低熔点金属不会印刷到油墨以外的位置，且能够在处理后的基材表面印刷具有目标厚度的低熔点金属。
可选地，喷壶为可加热的喷壶，不仅可以在印刷低熔点金属的过程中对低熔点金属进行加热，防止低熔点金属凝固或者粘稠度过大无法印刷，还可以直接将固态的低熔点金属加热至其熔点以上，使其成为液态，并进行后续的印刷。
其中，使用第一个例子和第二个例子中的方式印刷得到的低熔点金属的厚度较小，最小可达1～2μm。使用第三个例子和第四个例子中的方式印刷得到的低熔点金属的厚度较大，通常为10μm以上。在第一个例子至第四个例子中都可以通过重复印刷的次数调节印刷得到的低熔点金属的厚度。
此外，本发明实施例中的低熔点金属的印刷方法还可以包括对步骤S5所得制品进行后处理以得到所需产品的步骤，上述后处理可以包括元器件贴装、封胶、固化、剪裁、包装等中的一个或多个。
可选地，本发明实施例中的低熔点金属为熔点在300℃以下的低熔点金属单质，熔点在300℃以下的低熔点合金，或者，熔点在300℃以下的共混物，共混物包括低熔点金属单质、低熔点合金和功能粉体中的至少两种，即共混物包括低熔点金属单质和低熔点合金，或者，共混物包括低熔点合金和功能粉体，或者，共混物包括低熔点金属单质和功能粉体，或者，共混物包括低熔点金属单质、低熔点合金和功能粉体。
示例性地，低熔点金属单质可以为汞单质、镓单质、铟单质或者锡单质。
示例性地，低熔点合金可以为镓铟合金、镓铟锡合金、镓锡合金、镓锌合金、镓铟锌合金、镓锡锌合金、镓铟锡锌合金、镓锡镉合金、镓锌镉合金、铋铟合金、铋锡合金、铋铟锡合金、铋铟锌合金、铋锡锌合金、铋铟锡锌合金、铋铟锡铅合金、铋锡镉合金、铋铅锡合金、铋锡铅镉合金、锡铅合金、锡铜合金、锡锌合金、锡锌铜合金和锡银铜合金中的一种。
示例性地，功能粉体可以为镍单质、铁单质、钛单质、锌单质、银单 质、铜单质、氧化铁、氧化铜、氧化锌、碳粉、石墨烯、碳纳米管、氧化硅、氮化硼、膨润土、高岭土中的至少一种。
本发明实施例提供的一种低熔点金属的印刷方法，使用该印刷方法在粘附低熔点金属的基材表面印刷低熔点金属的过程如下：首先，对基材进行处理，得到处理后的基材，处理后的基材表面不粘附低熔点金属，然后，选择可粘附处理后的基材，且可粘附低熔点金属的油墨，接着，在处理后的基材表面用油墨印制目标图案，接着，使处理后的基材表面的油墨固化，最后，在处理后的基材表面印刷低熔点金属，由于低熔点金属不粘附处理后的基材表面，但粘附油墨，因此，在处理后的基材表面印刷低熔点金属后，仅油墨上覆盖有低熔点金属，处理后的基材表面其他位置均无低熔点金属覆盖，使得低熔点金属的图形与预设图形相同，即实现了低熔点金属在粘附低熔点金属的基材表面上印刷，扩大了低熔点金属的应用范围。
为了便于本领域技术人员理解和实施本发明实施例中的低熔点金属的印刷方法，下面本发明实施例以几个具体实施例进行举例描述。
实施例1，尼龙布表面印刷低熔点金属RFID标签，具体过程如下：
(1)尼龙布预先经10mg/mL的石蜡(改性剂)/正己烷(溶剂)浸渍处理20min，室温干燥10min后备用；
(2)用丝网印刷法将尼龙专用丝印油墨在经步骤(1)处理后的尼龙布表面印刷出RFID标签图；
(3)将步骤(2)中印刷有RFID标签图的尼龙布在室温下放置10s，待其上的油墨完全固化；
(4)将熔点为58℃的低熔点金属(Bi31.6％In48.8％Sn19.6％，以上均为重量百分比)预先在加热到80℃的水平台上均匀涂布，将步骤(3)中所得的尼龙布贴附于上述涂布了低熔点金属的水平台上，用干净的辊筒以0.7MPa的压力使尼龙布与低熔点金属紧密贴合10s后将尼龙布与水平台分离；
(5)对步骤(4)所得制品在室温下静置1min，即得低熔点金属RFID标签。
该印刷方法印刷所得的低熔点金属的厚度为15微米，贴装芯片后可实现识别功能。
实施例2，聚对苯二甲酸丁二醇酯(PBT)膜表面印刷低熔点金属电路，具体过程如下：
(1)PBT膜预先经10mg/mL蜂蜡/正庚烷溶液浸渍处理10min，室温干燥20min后备用；
(2)用丝网印刷法将改性乙烯基树脂油墨在经步骤(1)处理后的PBT膜表面印刷出电路图；
(3)将步骤(2)中印刷有电路图的PBT膜在激光辐照条件下处理10s，待其上的油墨完全固化；
(4)将熔点为58℃的低熔点金属(Bi31.6％In48.8％Sn19.6％，以上均为重量百分比)预先滚涂在硅胶辊筒上，利用上述均匀涂布低熔点金属的辊筒以0.2MPa的压力在步骤(3)所得的PBT膜表面上滚动，以使低熔点金属粘附在油墨上。
(5)对步骤(4)所得制品在室温下静置1min，即得低熔点金属电路。
该印刷方法印刷所得的低熔点金属的厚度约为12微米，宽2毫米，长100毫米的线条，电阻约为3.8欧姆。
实施例3，聚丙烯(PP)塑料瓶表面印刷低熔点金属图案，具体过程如下：
(1)PP塑料瓶预先经15mg/mL聚乙烯蜡/三氯甲烷溶液喷涂处理，烘箱50℃处理2min后备用；
(2)用凸版印刷法将丙烯酸类油墨在步骤(1)处理后的PP表面印刷出图案；
(3)将步骤(2)中印刷有图案的PP塑料瓶在电子束辐照条件下处理10s，待其上的油墨完全固化；
(4)将包含10％锌粉与熔点为72℃的低熔点合金(Bi34％In66％，以上均为重量百分比)的低熔点金属预先滚涂在加热到90℃的陶瓷辊筒上，利用上述均匀涂布低熔点金属金属的辊筒以0.4MPa的压力在步骤(3)所得的PP塑料瓶表面上滚动，以使低熔点金属粘附在油墨表面。
(5)对步骤(4)所得制品在室温下静置2min，即得低熔点金属图案。
该印刷方法印刷所得的低熔点金属厚度约为4微米，可导电，且具有较好金属光泽，无需封装，可直接用于包装产品。
实施例4，聚氯乙烯(PVC)塑料膜表面印刷低熔点金属电路，具体过程如下：
(1)PVC塑料膜预先经5mg/mL硬脂酸/乙醚溶液浸渍处理1min，冷风吹干后备用；
(2)用钢网印刷法将聚脲油墨在步骤(1)处理后的PVC塑料膜表面印刷出电路图案；
(3)将步骤(2)中印刷有电路图案的PVC塑料膜在60℃烘箱下处理1h，待其上的油墨完全固化；
(4)将熔点为15.5℃(Ga75.5％In24.5％，以上均为重量百分比)的低熔点金属预先灌装在喷壶内，将喷壶喷嘴与步骤(3)中所得的PVC塑料膜保持10cm，以2.0MPa的压力进行喷射，将低熔点金属喷至PVC塑料膜表面；
(5)对步骤(4)所得制品进行封胶处理，胶固化、剪裁后即得低熔点金属电路。
该印刷方法印刷所得的低熔点金属厚度约为5微米，宽3毫米，长100毫米的线条的电阻约为1.3欧姆。
实施例5，硅橡胶表面印刷可拉伸弹性电路，具体过程如下：
(1)硅橡胶表面预先经10mg/mL小烛树蜡/二甲苯溶液印刷一层，50℃烘箱中烘干备用；
(2)用丝网印刷法将聚氨酯丙烯酸酯油墨在步骤(1)处理后的硅橡胶表面印刷出电路图案；
(3)将步骤(2)中印刷有电路图案的硅橡胶在紫外光下照射30s，待其上的油墨完全固化；
(4)将熔点为11℃(Ga67％In20.5％Sn12.5％，以上均为重量百分比)的低熔点金属装入容器内，将步骤(3)中所得的硅橡胶浸入上述装有低熔点金属的容器中，10s后取出；
(5)对步骤(4)所得制品进行弹性胶封装处理，待胶固化、剪裁后即得可拉伸弹性电路。
该印刷方法印刷所得的低熔点金属的厚度约为18微米，宽3毫米，长100毫米的线条，电阻约为1.1欧姆。当硅橡胶伸长率为30％时，电阻变为4.3欧姆。
实施例6，玻璃表面印刷低熔点金属电路，具体过程如下：
(1)玻璃表面预先经20mg/mL二十二烷/四氯化碳溶液滴涂处理，室温干燥备用；
(2)用热转印法将环氧树脂油墨在步骤(1)处理后的玻璃表面印刷出电路图案；
(3)将步骤(2)中印刷有电路图案的玻璃在室温下静置2min，待其上的油墨完全干燥；
(4)将熔点为72℃(Bi34％In66％，以上均为重量百分比)的低熔点金属预先滚涂在加热到100℃的陶瓷辊筒上，利用上述均匀涂布低熔点金属的辊筒以0.7MPa的压力在步骤(3)所得的玻璃表面上滚动，以使低熔点金属粘附在油墨表面。
(5)步骤(4)所得制品室温下静置5min，待低熔点金属完全固化即可。
该印刷方法印刷所得的低熔点金属的厚度约为7微米，宽1毫米，长100毫米的线条，电阻约为31欧姆。
实施例7，聚对苯二甲酸乙二醇酯(PET)表面印刷低熔点金属电路制备薄膜开关，具体过程如下：
(1)PET表面经35mg/mL荷荷芭蜡/正己烷溶液滴涂处理，室温干燥备用；
(2)用静电印刷法将碳素和丙烯酸酯类油墨在步骤(1)处理后的PET表面印刷出电路图；
(3)将步骤(2)中印刷有电路图的PET膜在室温静置1s，待其上的油墨完全干燥；
(4)将熔点为58℃(Bi31.6％In48.8％Sn19.6％，以上均为重量百分比)的低熔点金属预先滚涂在加热到70℃的不锈钢辊筒上，利用上述均匀涂布金属的辊筒以1.0MPa的压力在步骤(3)所得的PET表面上滚动，以使低熔点金属粘附在油墨上。
(5)对步骤(4)所得制品进行胶接，即得包括低熔点金属电路的薄膜开关。
该印刷方法印刷所得的低熔点金属的厚度仅为5微米，可通过按压实现薄膜开关的功能。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (13)

  1. 一种低熔点金属的印刷方法，其特征在于，包括：
    提供一基材，所述基材表面粘附低熔点金属；
    对所述基材进行处理，得到处理后的基材，所述处理后的基材表面不粘附低熔点金属；
    选择可粘附所述处理后的基材表面，且可粘附所述低熔点金属的油墨；
    在所述处理后的基材表面用所述油墨印制目标图案；
    使所述处理后的基材表面的所述油墨固化；
    在所述处理后的基材表面印刷所述低熔点金属。
  2. 根据权利要求1所述的印刷方法，其特征在于，所述基材为聚氯乙烯基材、聚对苯二甲酸乙二醇酯基材、聚对苯二甲酸丁二醇酯基材、聚丙烯基材、聚己二酸-对苯二甲酸丁二酯基材、硅橡胶基材、天然橡胶基材、异戊橡胶基材、丁苯橡胶基材、顺丁橡胶基材、氯丁橡胶基材、乙丙橡胶基材、丁腈橡胶基材、硅橡胶基材、聚硫橡胶基材、玻璃基材、聚氨酯基材、亚克力基材、不锈钢基材、硅基材、尼龙布中的一种。
  3. 根据权利要求1所述的印刷方法，其特征在于，所述对所述基材进行处理，得到处理后的基材包括：使用由改性剂和溶剂组成的溶液，对所述基材表面进行改性处理，并使改性处理后的基材表面干燥，得到所述处理后的基材。
  4. 根据权利要求3所述的印刷方法，其特征在于，所述改性剂包括二十二烷、硬脂酸、棕榈酸、花生酸、木蜡、棕榈蜡、米糠蜡、荷荷芭蜡、蓖麻蜡、杨梅蜡、小烛树蜡、自蜂蜡、虫白蜡、羊毛蜡、鲸蜡、石蜡、微晶石蜡、石油蜡、乳化蜡、褐煤蜡、费托蜡、聚乙烯蜡、聚丙烯蜡、氯化石蜡、乙烯-乙酸乙烯共聚蜡、氧化乙烯蜡中的一种或几种，所述溶剂包括乙醚、石油醚、正庚烷、正己烷、环己烷、乙酸乙酯、甲醇、乙醇、醋酸、氯仿、四氯化碳、苯、甲苯和二甲苯中的一种或几种。
  5. 根据权利要求3所述的印刷方法，其特征在于，所述改性剂的浓度为1～40mg/mL。
  6. 根据权利要求3所述的印刷方法，其特征在于，通过浸渍、喷涂、 滴涂，印刷中的一种，使用由改性剂和溶剂组成的溶液，对所述基材表面进行改性处理；通过自然干燥、风干、加热干燥中的一种使改性处理后的基材表面干燥。
  7. 根据权利要求1所述的印刷方法，其特征在于，所述油墨为水性油墨、油性自挥发油墨、加热固化油墨、紫外固化油墨、电子束固化油墨、激光固化油墨中的一种。
  8. 根据权利要求1所述的印刷方法，其特征在于，在所述处理后的基材表面用所述油墨印制目标图案中，通过钢网印刷、丝网印刷、喷墨印刷、紫外打印、凹版印刷、凸版印刷、平板印刷、热转印印刷、静电印刷中的一种方式，用所述油墨印制目标图案。
  9. 根据权利要求1所述的印刷方法，其特征在于，所述油墨固化的方式包括室温固化、加热固化、紫外光照固化、电子束辐照固化、激光固化中至少一种。
  10. 根据权利要求1所述的印刷方法，其特征在于，
    所述低熔点金属的熔点等于或低于室温时，所述在所述处理后的基材表面印刷所述低熔点金属包括：将液态的所述低熔点金属印刷至所述处理后的基材表面；
    所述低熔点金属的熔点高于室温时，所述在所述处理后的基材表面印刷所述低熔点金属包括：对固态的所述低熔点金属进行加热，使所述低熔点金属完全熔化呈液态，将液态的所述低熔点金属印刷至所述处理后的基材表面。
  11. 根据权利要求10所述的印刷方法，其特征在于，所述将液态的所述低熔点金属印刷至所述处理后的基材表面包括：
    在辊筒上均匀涂布液态的所述低熔点金属，用所述辊筒以第一预设压力在所述处理后的基材表面上滚动，在所述处理后的基材表面印刷低熔点金属；或者，
    在水平台上均匀涂布液态的所述低熔点金属，将所述处理后的基材贴附于所述水平台上，在第二预设压力的作用下，在所述处理后的基材表面印刷低熔点金属，并在印刷之后将所述处理后的基材与所述水平台分离；或者，
    将液态的所述低熔点金属装入容器内，将所述处理后的基材浸入所述容器中进行浸渍处理经预设浸渍时间后取出；或者，
    将液态的所述低熔点金属灌装至喷壶中，用所述喷壶在第三预设压力的作用下将液态的所述低熔点金属喷至所述处理后的基材表面。
  12. 根据权利要求11所述的印刷方法，其特征在于，根据所述处理后的基材的材质和需要印刷的低熔点金属的目标厚度，对所述第一预设压力、所述第二预设压力、所述第三预设压力或者所述预设浸渍时间进行选择。
  13. 根据权利要求11所述的印刷方法，其特征在于，所述辊筒为可加热的辊筒，所述水平台为可加热的水平台，所述容器为可加热的容器，所述喷壶为可加热的喷壶。
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