CN107337964B - Colored liquid metal printing ink and preparation method thereof - Google Patents
Colored liquid metal printing ink and preparation method thereof Download PDFInfo
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- CN107337964B CN107337964B CN201710741135.7A CN201710741135A CN107337964B CN 107337964 B CN107337964 B CN 107337964B CN 201710741135 A CN201710741135 A CN 201710741135A CN 107337964 B CN107337964 B CN 107337964B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
Abstract
The invention provides a colored liquid metal printing ink, which comprises, by weight, 40% -70% of liquid metal, 2% -10% of pigment, 10% -30% of wettability improver, 1% -5% of dispersant, 0.5% -3% of coupling agent, 1% -10% of binder, 0.5% -3% of adhesion promoter, 1% -5% of solvent and the balance of other additives; the liquid metal is low-melting-point metal or alloy with the melting point below 300 ℃, or conductive nano fluid formed by mixing metal nano particles and a fluid dispersing agent. The invention provides the concept and the preparation method of the colored liquid metal printing ink for the first time, changes the prior application method of directly adopting pigment powder in liquid metal, adopts color paste rather than pigment to provide color for the liquid metal, further improves the color saturation and the stability of the colored liquid metal composite material, and ensures that the colored liquid metal composite material has good conductivity of the liquid metal and rich colority of the pigment.
Description
Technical Field
The invention belongs to the technical field of printing materials, and particularly relates to printing ink containing liquid metal and a preparation method thereof.
Background
Printing techniques include screen printing, letterpress printing, flexographic printing, gravure printing, and offset printing, among others. Printing with conductive inks is one of the important methods for achieving large area size, fast, low cost, and efficient processing of circuit patterns, and is considered to be a more environmentally friendly, greener, and material-saving process because it does not generate large amounts of waste liquid as in the etching process. The ink can be used for printing, can realize mass production, has low rejection rate and stable product performance, and is a preferred process of various electronic devices. The printing technology can meet the requirement of preparing circuits on traditional rigid materials, can realize printing on flexible base materials, and can prepare wearable flexible intelligent electronic devices. In addition, the printing method easily realizes the preparation processing of high-precision images and the precise control of the thickness of the conductive layer.
Liquid metal in the broadest sense means elemental metal and alloys that are in a liquid state at temperatures below 660 ℃, and more typically liquid metals are those that are in a liquid state at about room temperature, such as gallium or alloys thereof having a melting point below 30 ℃, or low melting point metal alloys that are in a liquid state at slightly higher temperatures, such as 40 ℃ to 200 ℃, such as bismuth indium tin zinc. In recent years, with the progress of a series of important researches, the application value of liquid metal is more and more important. In various applications, liquid metal materials have been introduced into the field of printing of new printed electronics and functional devices in recent years, and become unique and important printable electronic materials, because they can operate in a liquid state, have good fluidity, and have natural conductivity.
However, on one hand, because the existing liquid metal is limited by the physical properties or alloy composition of the liquid metal, the formed liquid metal is mostly silvery white in luster and single in color, so that the printing requirements of industry for high color and aesthetic degree are difficult to meet, the formed circuit can not effectively meet the aesthetic requirements of people, and the partitioning and marking functions of complex circuits by using colors are difficult to realize. The industry gradually proposes the concept of a color liquid metal material, and the chinese patent application publication No. CN105220013A "a color liquid metal and a manufacturing method thereof" discloses a manufacturing method of a color liquid metal, which prepares a color liquid metal material by mixing a liquid metal and a color pigment, however, the application mainly aims at the application scene of a printed circuit, and does not provide a directly usable complete solution for the color liquid metal ink with high viscosity and high adhesion required by printed electronic equipment. The pigments selected in the above patents are not suitable for the processing techniques such as sand milling and ball milling required in the printing ink processing. In addition, the invention provides a method for solving the mixing stability of the liquid metal and the pigment and improving the color saturation, namely, the pigment is firstly processed into color paste and then is mixed with the liquid metal in the presence of a high molecular binder, and the process improvement is beneficial to the wider application of the color liquid metal printing ink in the electronic field.
On the other hand, the high surface tension, low wettability and adhesion of liquid metal make it difficult to adhere to the surface of an object and to achieve precise three-dimensional formation (i.e., precise dimensional control in three dimensions, namely length, width and height). It would be particularly important to be able to obtain a composite material based on liquid metal that has good electrical conductivity, wettability, and adhesion. The present invention is particularly proposed by combining the above analyses.
Disclosure of Invention
Aiming at the problems that the traditional liquid metal is single in color and the preparation method of the traditional color liquid metal material is not suitable for application of printing ink, the invention provides a color liquid metal-based composite printing material.
Another object of the invention is to propose a process for the preparation of said printing ink.
A third object of the invention is to propose the use of said printing ink.
The technical scheme for realizing the above purpose of the invention is as follows:
a colored liquid metal printing ink comprises, by weight, 40% -70% of liquid metal, 2% -10% of pigment, 10% -30% of wettability improver, 1% -5% of dispersant, 0.5% -3% of coupling agent, 1% -10% of binder, 0.5% -3% of adhesion promoter, 1% -5% of solvent and the balance of other additives;
the liquid metal is low-melting-point metal or alloy with the melting point below 300 ℃, or conductive nano fluid formed by mixing metal nano particles and a fluid dispersing agent.
According to the invention, the wettability promoter and the adhesion promoter are reasonably and effectively added into the liquid metal, so that the defects that the liquid metal is poor in wettability and not ideal in adhesion force, cannot be effectively adhered to the surfaces of various objects and is more difficult to accurately form in three dimensions in printed electronic application are overcome, and the efficient wetting and adhesion of the high-wettability colored liquid metal on the surfaces of plastics, rubber, ceramics and paper are realized.
Further, the liquid metal is a simple substance or an alloy formed by a plurality of substances in gallium, indium, tin, zinc, bismuth, lead, cadmium, mercury, sodium, potassium, magnesium, aluminum, iron, cobalt, manganese, titanium and vanadium,
the liquid metal is one of gallium indium alloy, gallium indium tin alloy, gallium zinc alloy, gallium indium zinc alloy, gallium tin zinc alloy, gallium indium tin zinc alloy, gallium tin cadmium alloy, gallium zinc cadmium alloy, bismuth indium alloy, bismuth tin alloy, bismuth indium zinc alloy, bismuth tin zinc alloy, bismuth indium tin zinc alloy, tin lead alloy, tin copper alloy, tin zinc alloy, tin silver copper alloy and bismuth lead tin alloy.
Preferably, the liquid metal is an alloy formed by two or three of gallium, indium, tin, bismuth, aluminum and zinc, and the mass of the liquid metal accounts for 55-70% of that of the color liquid metal printing ink.
The invention preferably uses binary or ternary alloy to realize the improvement of constructability and the reduction of cost, and the binary or ternary alloy is also beneficial to adjusting the melting point.
Wherein, the pigment is an inorganic pigment and/or an organic pigment;
the inorganic pigment is one or more of natural mineral pigments such as cinnabar, laterite, lime yellow, azurite, malachite green, ultramarine, ochre, carbon black and sericite; or one or more of synthetic inorganic pigments such as zirconium oxide, iron oxide black, iron oxide red, iron oxide brown, titanium white, zinc sulfide, cobalt blue, cobalt green, cadmium yellow, cadmium orange and CICP composite inorganic pigment; wherein the CICP composite inorganic pigment is selected from one or more of zinc iron yellow, titanium nickel yellow, titanium chromium brown, titanium manganese yellow, pigment orange 82, pigment brown 24, pigment brown 29, pigment brown 48, pigment blue 28, pigment blue 36, pigment green 50, pigment green 26 and pigment violet 15;
the organic pigment comprises one or more of azo pigments, phthalocyanine pigments, heterocyclic and condensed ring ketone pigments, wherein the azo pigments comprise one or more of benzimidazolone pigment orange 36, pigment brown 25 and pigment red 176, the azo metal lake pigment yellow 183 and the pigment yellow 62, the phthalocyanine pigments comprise one or more of phthalocyanine blue 15:1(α type), phthalocyanine blue 15:3(β type) and phthalocyanine green, and the heterocyclic and condensed ring ketone pigments comprise one or more of pyrrolopyrroledione pigment red 254, quinoxalinedione pigment yellow 213, perylene pigment red 149 and perylene pigment violet 178 and pigment violet 29.
Wherein the wettability improver is selected from one or more of iron powder, copper powder, silver powder, nickel-coated graphite powder, silver-coated copper powder, silver-coated nickel powder, rutile titanium dioxide, zinc oxide, ferroferric oxide, magnesium oxide, monocrystalline silicon powder, aluminum oxide, aluminum silicate, heavy calcium carbonate, barium sulfate, kaolin and mica powder;
the particle size of the wettability improver is 1 nm-100 mu m.
One of the preferable technical schemes of the invention is that the wettability improver is one or two of iron powder, copper powder, silver powder, nickel powder, zinc oxide, ferroferric oxide, magnesium oxide, monocrystalline silicon powder and aluminum oxide, and each wettability modifier accounts for 4-15% of the mass percent of the color liquid metal printing ink. The particle size of the wettability improver is preferably 10nm to 50 μm.
Wherein the dispersant is a block polymer dispersant and/or a comb polymer dispersant;
the dispersant mainly functions to disperse the pigment and the wettability improver. The compatibility of the pigment particles and liquid metal is low, and a polymer dispersant with a block structure is preferably used, wherein the end group is a group with an anchoring function, so that the pigment particles are stably combined, and the middle chain segment provides necessary physical barrier; wettability improvers such as iron powder, nickel powder, and the like are well compatible with liquid metals, but because of their large specific gravity, dispersants that provide greater steric hindrance are needed to ensure that the metal particles do not agglomerate due to impact during high speed dispersion and grinding, and dispersants having a comb-like structure are used. Both types of dispersants are commercially available.
The coupling agent is one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent;
the binder comprises one or more of pure acrylic emulsion, styrene-acrylic emulsion, fluorocarbon emulsion, polyurethane emulsion and organic silicon emulsion;
the adhesion promoter is one or more of graphite, graphene, carbon nano tubes, aerogel powder, hollow microspheres, ceramic microspheres, sepiolite, closed-cell expanded perlite, vermiculite and potassium silicate whiskers;
the solvent is one or more of water, ethyl acetate, butyl acetate, cyclohexane, n-butanol, ethylene glycol and glycerol;
the other auxiliary agents are one or more of thickening agents, defoaming agents and anti-settling agents.
The preparation method of the color liquid metal printing ink is characterized by comprising the following steps of:
step 1: preparing color paste: adding a dispersing agent and a coupling agent into a solvent, dispersing and stirring until the dispersing agent and the coupling agent are uniformly dissolved, adding pigment powder, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding by taking zirconium oxide particles as a grinding medium, and filtering to obtain color paste;
step 2: preparing liquid metal alloy, heating the liquid metal raw material to be above a melting point, and mixing and stirring the liquid metal raw material and the melting point to obtain uniform liquid metal alloy.
And step 3: slowly adding a wettability improver and an adhesion promoter into the liquid metal, and adding the color paste prepared in the step (1) after uniformly mixing; and transferring the mixture into a planetary ball mill with inert gas protection, and grinding for 1-3 h by taking the zirconia particles as grinding media.
And 4, step 4: and fully mixing the ground mixture with a binder, and fully dispersing for 20-40 min at the rotating speed of 1000-2000 r/min to obtain the color liquid metal printing ink.
Further, the step 1 is as follows: adding a dispersing agent and a coupling agent into a solvent, stirring by using a dispersing machine until the dispersing agent and the coupling agent are uniformly dissolved, adding a defoaming agent to remove foams, adding pigment powder into the dispersion, dispersing for 30-60 min at the rotating speed of 500-1000 r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, and grinding for 1-3 h at the speed of 3000-5000 r/min by using zirconium oxide particles as grinding media.
Optionally, step 1 is: adding a dispersing agent and a coupling agent into a solvent, stirring by using a dispersion machine until the dispersing agent and the coupling agent are uniformly dissolved, adding a defoaming agent and a thickening agent (divided into two batches, and adding half of the defoaming agent and the thickening agent) to remove foams, adding pigment powder into the dispersion liquid, fully dispersing for 60min at the rotating speed of 1000r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding for 2h at the condition of 5000r/min by using zirconium oxide particles as grinding media, and adding the rest thickening agent. The remaining antifoam is added in step 3.
The application of the colored liquid metal printing ink is characterized in that the colored liquid metal printing ink is directly printed on plastic, rubber, ceramic, glass, wood, metal foil, cellulose membrane and paper.
The plastic may include polyethylene, polypropylene, polystyrene, polyester, polyacrylate, polycarbonate, polyetheretherketone, polyaryletherketone, ethylene-vinyl acetate copolymer, polyoxymethylene, ABS, polyvinyl chloride, polyvinyl dichloride, polyphenylene oxide, polyimide, phenolic resin, epoxy resin, and the like.
The rubber comprises natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber, nitrile rubber and the like.
The ceramics include oxide ceramics, nitride ceramics, carbide ceramics, sulfide ceramics and the like.
The technical scheme of the invention has the following advantages:
1. the concept and the preparation method of the colored liquid metal printing ink are put forward for the first time, the existing application method of directly adopting pigment powder in liquid metal is changed, color paste rather than pigment is adopted to provide color for the liquid metal, the color saturation and the stability of the colored liquid metal composite material are further improved, and the colored liquid metal composite material has good conductivity of the liquid metal and rich colority of the pigment;
2. the wetting ability of the liquid metal is improved by using the wetting accelerant, so that the liquid metal can be wetted and spread on the surfaces of various plastics, rubbers and glass, and the possibility is provided for printing of liquid metal composite materials;
3. the adhesion stability of the liquid metal is remarkably improved by using the adhesion promoter, so that a film with controllable thickness can be formed on the surface of the base material and stable adhesion can be kept;
4. compared with the traditional liquid metal, the viscosity of the colored liquid metal ink can be adjusted at will, and the colored liquid metal ink can be applied to different fields such as screen printing, gravure printing and even painting on a substrate by directly using a water color pen.
5. The high-adhesion colored liquid metal ink has the characteristics of safety, no toxicity, environmental protection and no pollution, can be used for preparing conducting circuits and devices with controllable sizes, can realize thickness-controllable printing on flexible base materials, and can meet the requirements of new fields such as printed circuits, electronic devices, wearable equipment, membrane switches, electronic skins, RFID antennas, flexible electromagnetic shielding materials, electronic paintings, electronic signatures and the like.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
In the examples, unless otherwise specified, the methods used are conventional in the art.
Experimental examples wettability test
The contact angle data of liquid metal formed by gallium and indium in a mass ratio of 1:2 on different substrates respectively tested by a contact angle measuring instrument are as follows: 156 degrees on polyethylene plastic, 148 degrees on polyvinyl chloride plastic, 149 degrees on polyethylene terephthalate, 148 degrees on nitrile rubber and 155 degrees on glass substrate, and the printing on the substrate by a screen printing method cannot be carried out. The contact angle data for the other alloys on different substrates are shown in table 1.
The contact angle of 60g of gallium-indium alloy with pigment (pigment orange 36, 5g) directly added does not change significantly, and printing by screen printing is impossible.
60g of gallium-indium alloy is added with color paste (prepared by the method of the step 1 in the example 1), and the contact angle measurement result is as follows: the printing can not be carried out by a screen printing method on 145 degrees of polyethylene plastic, 140 degrees of polyvinyl chloride plastic, 140 degrees of polyethylene terephthalate, 142 degrees of nitrile rubber and 145 degrees of glass base material.
60g of gallium-indium alloy is added with a wetting modifier, or 60g of gallium-indium alloy is added with a wetting modifier and color paste, contact angles on polyethylene plastic are 72 degrees and 70 degrees respectively, contact angles on polyvinyl chloride plastic are 63 degrees and 62 degrees respectively, contact angles on polyethylene terephthalate are 63 degrees, contact angles on butadiene-acrylonitrile rubber are 65 degrees and 64 degrees respectively, and contact angles on a glass substrate are 68 degrees respectively.
The mechanism of the above experiment is probably because the selected wetting modifiers such as iron powder and nickel powder are doped into the gallium-indium alloy in an atomic scale under the high-speed dispersing and grinding process, and promote partial oxidation of gallium and indium, so that the gallium atoms, the indium atoms and the acting force between the gallium atoms and the indium atoms are weakened. Thereby reducing the ink tension and improving the wettability of the material. A small amount of dispersant in the color paste can play a certain role in wetting, and for the liquid metal ink, the dispersant also mainly plays a role in wetting a modifier. Other wetting modifiers were also tried by the inventors and are shown in the examples below.
TABLE 1 wettability comparison
Example 1
The formula composition of the high-wettability colored liquid metal printing ink is shown in the following table:
the comb-shaped and the block-shaped in the formula respectively represent a comb-shaped macromolecular dispersant and a block macromolecular dispersant.
The preparation method of the high-wettability colored liquid metal printing ink comprises the following steps of:
step 1: preparing color paste, adding a dispersing agent and a coupling agent into a solvent according to the formula, stirring by using a dispersing machine until the dispersing agent and the coupling agent are uniformly dissolved, adding a defoaming agent and a thickening agent (divided into two batches, half of the dispersing agent is added firstly) to remove foams, adding pigment powder into the dispersion liquid, fully dispersing for 60min at the rotating speed of 1000r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding for 2h at the condition of 5000r/min by taking zirconium oxide particles as a grinding medium, and adding the rest thickening agent to obtain the color paste with the viscosity of 3500cp (measured by a Brookfield viscometer, and the measurement condition is 25 ℃ and 60r/min of a No. 3 rotor).
Step 2: preparing liquid metal alloy, heating the liquid metal raw materials (gallium and indium are respectively heated) to be above the melting point, and mixing and stirring the liquid metal raw materials according to the proportion to obtain the uniform liquid metal alloy.
And step 3: and (2) slowly adding the weighed wettability improver and adhesion promoter into the liquid metal, adding the color paste prepared in the step (1) and the rest defoaming agent after uniformly mixing, transferring the mixture into a planetary ball mill with inert gas protection, and grinding for 3 hours by taking zirconium oxide particles as grinding media.
And 4, step 4: and fully mixing the ground mixture with a binder, and fully dispersing for 40min at the rotating speed of 1500r/min to obtain the color liquid metal printing ink.
Example 2
The formula composition of the high-wettability colored liquid metal printing ink is shown in the following table:
the preparation method of the high-wettability colored liquid metal printing ink comprises the following steps of:
step 1: preparing color paste, adding a dispersing agent and a coupling agent into a solvent according to the formula, stirring by using a dispersing machine until the dispersing agent and the coupling agent are uniformly dissolved, adding half of a defoaming agent and a thickening agent to remove foams, adding pigment powder into the dispersion liquid, fully dispersing for 40min at the rotating speed of 800r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding for 2h at 3000r/min by using zirconium oxide particles as a grinding medium, adding the rest thickening agent, filtering to obtain the color paste with the viscosity of 3900cp, and filtering to obtain the color paste.
Step 2: preparing liquid metal alloy, heating the liquid metal raw materials (tin and bismuth are respectively heated) to the melting point, and mixing and stirring the liquid metal raw materials according to the proportion to obtain the uniform liquid metal alloy.
And step 3: and (2) slowly adding the weighed wettability improver and adhesion promoter into the liquid metal, adding the color paste prepared in the step (1) and the rest defoaming agent after uniformly mixing, transferring the mixture into a planetary ball mill with inert gas protection, and grinding for 2 hours by taking zirconium oxide particles as grinding media.
And 4, step 4: and fully mixing the ground mixture with a binder, and fully dispersing for 30min at the rotating speed of 2000r/min to obtain the color liquid metal printing ink.
Example 3
The formula composition of the high-wettability colored liquid metal printing ink is shown in the following table:
the preparation method of the high-wettability colored liquid metal printing ink comprises the following steps of:
step 1: and (2) preparing color paste, namely adding a dispersing agent and a coupling agent into a solvent according to the formula, stirring by using a dispersing machine until the dispersing agent and the coupling agent are uniformly dissolved, adding a half of defoaming agent and a thickening agent to remove foams, adding pigment powder into the dispersion liquid, fully dispersing for 40min at the rotating speed of 800r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding for 2h at the speed of 3000r/min by taking zirconium oxide particles as a grinding medium, adding the remaining thickening agent, and filtering to obtain the color paste with the viscosity of 4900 cp.
Step 2: preparing liquid metal alloy, heating the liquid metal raw materials (tin and zinc are respectively heated) to the melting point, and mixing and stirring the liquid metal raw materials according to the proportion to obtain the uniform liquid metal alloy.
And step 3: and (2) slowly adding the weighed wettability improver and adhesion promoter into the liquid metal, adding the color paste prepared in the step (1) and the rest defoaming agent after uniformly mixing, transferring the mixture into a planetary ball mill with inert gas protection, and grinding for 2 hours by taking zirconium oxide particles as grinding media.
And 4, step 4: and fully mixing the ground mixture with a binder, and fully dispersing for 40min at the rotating speed of 2000r/min to obtain the color liquid metal printing ink.
Example 4
The formula composition of the high-wettability colored liquid metal printing ink is shown in the following table:
the preparation method of the high-wettability colored liquid metal printing ink comprises the following steps of:
step 1: preparing color paste, adding a dispersing agent and a coupling agent into a solvent according to the formula, stirring by using a dispersing machine until the dispersing agent and the coupling agent are uniformly dissolved, adding a defoaming agent and a thickening agent (divided into two batches, half of the dispersing agent is added firstly) to remove foams, adding pigment powder into the dispersion liquid, fully dispersing for 60min at the rotating speed of 1000r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding for 2h at the condition of 5000r/min by taking zirconium oxide particles as a grinding medium, and adding the rest thickening agent to obtain the color paste with the viscosity of 3500cp (measured by a Brookfield viscometer, and the measurement condition is 25 ℃ and 60r/min of a No. 3 rotor). Step 2: preparing liquid metal alloy, heating the liquid metal raw materials (gallium and indium are respectively heated) to be above the melting point, and mixing and stirring the liquid metal raw materials according to the proportion to obtain the uniform liquid metal alloy.
And step 3: and (2) slowly adding the weighed wettability improver and adhesion promoter into the liquid metal, adding the color paste prepared in the step (1) and the rest defoaming agent after uniformly mixing, transferring the mixture into a planetary ball mill with inert gas protection, and grinding for 3 hours by taking zirconium oxide particles as grinding media.
And 4, step 4: and fully mixing the ground mixture with a binder, and fully dispersing for 40min at the rotating speed of 1500r/min to obtain the color liquid metal printing ink.
Performance testing
In the performance test, the adhesive force is measured according to the standard GB/T13217.7-2009, and the fineness is detected according to the standard 13217.3-2008; the viscosity measurement is according to standard GB/T13217.4-2008.
Comparative example 1 was consistent with example 1 in composition, but did not employ the step of preparing a color paste prior to mixing in step 1.
The composition of the comparative example 2 is consistent with that of the example 2, and the step of firstly preparing color paste and then mixing in the step 1 is not adopted.
Comparative example 3 the composition was identical to example 1 except that no wettability improver was added, and the processing method was identical.
Comparative example 4 the composition was identical to example 1 except that no adhesion promoter was added, and the processing method was identical.
Comparative example 5 the composition was the same as example 1 except that the comb-like polymeric dispersant was not added, and the processing method was the same.
Table 2: results of Performance testing
As can be seen from the comparative data in the table above, the color liquid metal printing ink described in the examples of the present invention has higher storage stability, better fineness and adhesion fastness, and viscosity adjustability, and is suitable for screen printing and gravure printing, compared to the comparative examples.
Although the present invention has been described in the foregoing by way of examples, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (8)
1. A colored liquid metal printing ink is characterized by comprising, by weight, 40% -70% of liquid metal, 2% -10% of pigment, 10% -30% of wettability improver, 1% -5% of dispersant, 0.5% -3% of coupling agent, 1% -10% of binder, 0.5% -3% of adhesion promoter, 1% -5% of solvent and the balance of other additives;
the liquid metal is low-melting-point metal or alloy with the melting point below 300 ℃;
the wettability improver is selected from one or more of iron powder, copper powder, silver powder, nickel-coated graphite powder, silver-coated copper powder, silver-coated nickel powder, rutile titanium dioxide, zinc oxide, ferroferric oxide, magnesium oxide, monocrystalline silicon powder, aluminum oxide, aluminum silicate, heavy calcium carbonate, barium sulfate, kaolin and mica powder; the particle size of the wettability improver is 1 nm-100 mu m;
the dispersant is a block polymer dispersant and/or a comb polymer dispersant;
the coupling agent is one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent;
the binder is one or more of pure acrylic emulsion, styrene-acrylic emulsion, fluorocarbon emulsion, polyurethane emulsion and organic silicon emulsion;
the adhesion promoter is one or more of graphite, graphene, carbon nano tubes, aerogel powder, hollow microspheres, ceramic microspheres, sepiolite, closed-cell expanded perlite, vermiculite and potassium silicate whiskers;
the solvent is one or more of water, ethyl acetate, butyl acetate, cyclohexane, n-butanol, ethylene glycol and glycerol;
the other auxiliary agents are one or more of thickening agent, defoaming agent and anti-settling agent;
the preparation method of the colored liquid metal printing ink comprises the following steps:
step 1: preparing color paste: adding a dispersing agent and a coupling agent into a solvent, stirring by using a dispersing machine until the dispersing agent and the coupling agent are uniformly dissolved, adding a defoaming agent to remove foams, adding pigment powder into the dispersion, dispersing for 30-60 min at the rotating speed of 500-1000 r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding for 1-3 h at 3000-5000 r/min by using zirconium oxide particles as a grinding medium, and filtering to obtain a color paste;
step 2: preparing a liquid metal alloy, heating the liquid metal raw material to be above a melting point, and mixing and stirring the liquid metal raw material and the melting point to obtain a uniform liquid metal alloy;
and step 3: slowly adding a wettability improver and an adhesion promoter into the liquid metal, and adding the color paste prepared in the step (1) after uniformly mixing; transferring the mixture into a planetary ball mill with inert gas protection, and grinding for 1-3 h by taking zirconia particles as grinding media;
and 4, step 4: and fully mixing the ground mixture with a binder, and fully dispersing for 20-40 min at the rotating speed of 1000-2000 r/min to obtain the color liquid metal printing ink.
2. The colored liquid metal printing ink according to claim 1, wherein the liquid metal is a simple substance of one of gallium, indium, tin, mercury or an alloy of a plurality of gallium, indium, tin, zinc, bismuth, lead, cadmium, aluminum.
3. The colored liquid metal printing ink according to claim 2, wherein the liquid metal is one of a gallium-indium alloy, a gallium-indium-tin alloy, a gallium-zinc alloy, a gallium-indium-zinc alloy, a gallium-tin-zinc alloy, a gallium-indium-tin-zinc alloy, a gallium-tin-cadmium alloy, a gallium-zinc-cadmium alloy, a bismuth-indium alloy, a bismuth-tin alloy, a bismuth-indium-zinc alloy, a bismuth-tin-zinc alloy, a bismuth-indium-tin-zinc alloy, a tin-lead alloy, a tin-zinc alloy, and a bismuth-lead-tin alloy.
4. The color liquid metal printing ink according to claim 2, wherein the liquid metal is an alloy formed by two or three of gallium, indium, tin, bismuth, aluminum and zinc, and the mass of the liquid metal accounts for 55-70% of the mass of the color liquid metal printing ink.
5. The colored liquid metal printing ink of claim 1, wherein said pigment is an inorganic pigment and/or an organic pigment;
the inorganic pigment is one or more of natural mineral pigments such as cinnabar, laterite, lime yellow, azurite, malachite green, ultramarine, ochre, carbon black and sericite; or one or more of synthetic inorganic pigments such as zirconium oxide, iron oxide black, iron oxide red, iron oxide brown, titanium white, zinc sulfide, cobalt blue, cobalt green, cadmium yellow, cadmium orange and CICP composite inorganic pigment; wherein the CICP composite inorganic pigment is selected from one or more of zinc iron yellow, titanium nickel yellow, titanium chromium brown, titanium manganese yellow, pigment orange 82, pigment brown 24, pigment brown 29, pigment brown 48, pigment blue 28, pigment blue 36, pigment green 50, pigment green 26 and pigment violet 15;
the organic pigment is one or more of azo pigments, phthalocyanine pigments, heterocyclic and condensed ring ketone pigments, wherein the azo pigments are one or more of benzimidazolone pigment orange 36, pigment brown 25, pigment red 176, azo metal lake pigment yellow 183 and pigment yellow 62, the phthalocyanine pigments are one or more of phthalocyanine blue 15:1(α type), phthalocyanine blue 15:3(β type) and phthalocyanine green, and the heterocyclic and condensed ring ketone pigments are one or more of pyrrolopyrroledione pigment red 254, quinoxalinedione pigment yellow 213, perylene pigment red 149, pigment red 178 and pigment violet 29.
6. The colored liquid metal printing ink according to claim 1, wherein the wettability modifier is one or a mixture of two of iron powder, copper powder, silver powder, nickel powder, zinc oxide, ferroferric oxide, magnesium oxide, monocrystalline silicon powder and aluminum oxide, and each wettability modifier accounts for 4-15% of the colored liquid metal printing ink by mass;
the particle size of the wettability improver is 10 nm-50 mu m.
7. The method of preparing the colored liquid metal printing ink of any one of claims 1 to 6, comprising the steps of:
step 1: preparing color paste: adding a dispersing agent and a coupling agent into a solvent, stirring by using a dispersing machine until the dispersing agent and the coupling agent are uniformly dissolved, adding a defoaming agent to remove foams, adding pigment powder into the dispersion, dispersing for 30-60 min at the rotating speed of 500-1000 r/min, transferring the mixed slurry into a horizontal sand mill after the pigment is uniformly wetted and dispersed, grinding for 1-3 h at 3000-5000 r/min by using zirconium oxide particles as a grinding medium, and filtering to obtain a color paste;
step 2: preparing a liquid metal alloy, heating the liquid metal raw material to be above a melting point, and mixing and stirring the liquid metal raw material and the melting point to obtain a uniform liquid metal alloy;
and step 3: slowly adding a wettability improver and an adhesion promoter into the liquid metal, and adding the color paste prepared in the step (1) after uniformly mixing; transferring the mixture into a planetary ball mill with inert gas protection, and grinding for 1-3 h by taking zirconia particles as grinding media;
and 4, step 4: and fully mixing the ground mixture with a binder, and fully dispersing for 20-40 min at the rotating speed of 1000-2000 r/min to obtain the color liquid metal printing ink.
8. The use of the colored liquid metal printing ink according to any one of claims 1 to 6, wherein the ink is directly printed or written on plastic, rubber, ceramic, glass, wood, metal foil, cellulose film, paper; the printing mode is screen printing or gravure printing.
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| CN111593229B (en) * | 2019-02-20 | 2024-01-23 | 北京梦之墨科技有限公司 | Colored liquid metal and preparation method thereof |
| CN111863308A (en) * | 2019-04-30 | 2020-10-30 | 北京梦之墨科技有限公司 | Colored conductive paste, preparation method thereof and electronic device |
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| CN112538290B (en) * | 2020-10-19 | 2022-02-08 | 浙江大学 | Self-sintering liquid metal ink and preparation method and application thereof |
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| CN105220013B (en) * | 2015-09-17 | 2017-03-29 | 中国科学院理化技术研究所 | A kind of color liquid metal and preparation method thereof |
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