CN104528801A - Preparation method of nano copper oxide and printing method of metal-matrix printing ink - Google Patents

Abstract

The invention discloses a preparation method of nano copper oxide. The preparation method comprises the following steps: preparing a first dispersion liquid from a copper source; preparing a second dispersion liquid by virtue of strong base; mixing the first dispersion liquid and the second dispersion liquid, refluxing, stirring and reacting at 100-180 DEG C for 10-60min, separating an obtained reaction liquid and reserving a solid so as to obtain the nano copper oxide. The preparation method of the nano copper oxide, by mixing the first dispersion liquid containing the copper source and the second dispersion liquid containing the strong base, and refluxing, stirring and reacting at 100-180 DEG C for 10-60min, can be used for preparing nano copper oxide particles relatively good in dispersibility. Furthermore, the invention also discloses a printing method of metal-matrix printing ink by virtue of the prepared nano copper oxide.

Description

Preparation method of nano-copper oxide and printing method of metal-based ink

technical field

The invention relates to a preparation method of nanometer copper oxide and a printing method of metal-based ink using the prepared nanometer copper oxide.

Background technique

Nano-copper oxide particles, due to their small size effect, macroscopic quantum tunneling effect, surface effect, and volume effect, will show unique properties, and show special performance in light absorption, electrochemistry, catalytic reactions, and energy storage materials. The physical and chemical properties make it more widely used. However, it is difficult to prepare monodisperse small-sized copper oxide, and the method is cumbersome, and organic solvents or high-temperature and high-pressure reaction conditions are often required for micro-preparation.

Among the metal-based inks, the development of nano-silver conductive ink is limited due to its high price and defects such as silver migration. Copper ink has excellent conductivity and lower cost than silver. Nano-copper-based conductive ink replaces traditional chemical etching (or laser etching) or electroplating process, which can not only significantly reduce costs but also print electronics in a green and environmentally friendly way, which is very important for printed circuit boards. (PCB), electronic tags (RFID), touch screens, membrane switches, solar cells, LED/OLED and many other industries and fields have demonstration significance, enabling these industries to realize the transformation from traditional etching and electroplating processes to green environmental protection in terms of electronic circuit technology. The transformation of printed electronics technology has greatly improved the technical level of the industry.

However, small-sized copper is not only difficult to prepare but also easy to oxidize, so it is generally necessary to prepare nano-copper oxide first.

Contents of the invention

Based on this, it is necessary to provide a preparation method of nano-copper oxide and a printing method of metal-based ink using the prepared nano-copper oxide.

A preparation method of nano-copper oxide, comprising the steps of:

Using a copper source to configure the first dispersion;

Using a strong base to prepare the second dispersion; and

The first dispersion liquid and the second dispersion liquid are mixed, refluxed and stirred at 100° C. to 180° C. for 10 min to 60 min, and the obtained reaction liquid remains solid after separation, and the solid is nano-copper oxide.

In one embodiment, the copper source is copper hydroxide, copper chloride, copper sulfate, basic copper carbonate, copper citrate, copper acetate or copper acetylacetonate.

In one embodiment, the concentration of the copper source in the first dispersion liquid is 0.01 mol/L˜1 mol/L.

In one embodiment, the operation of using the copper source to prepare the first dispersion liquid is as follows: adding the copper source into the first solvent, stirring under reflux at 100°C to 180°C for 10min to 60min, to obtain the first dispersion liquid.

In one embodiment, the first solvent is an alcohol-water mixture; the alcohol in the alcohol-water mixture is selected from the group consisting of methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, and At least one of ethylene glycol and glycerol, and the water in the alcohol-water mixture is deionized water.

In one embodiment, the strong base is potassium hydroxide or sodium hydroxide.

In one embodiment, the solvent of the second dispersion is a second solvent, and the second solvent is an alcohol-water mixture;

The alcohol in the alcohol-water mixture is selected from at least one of anhydrous methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, diethylene glycol and glycerol, and the alcohol The water in the water mixture is deionized water.

In one embodiment, the concentration of the strong base in the second dispersion is 0.02mol/L˜2mol/L.

A printing method of metal-based ink, comprising the steps of:

Prepare nano-copper oxide by adopting the above-mentioned preparation method of nano-copper oxide; and

After configuring the obtained nano-copper oxide into ink, it is printed on a printing substrate, and a printed pattern with good conductivity is obtained through low-temperature atmosphere reduction or photoreduction.

In one embodiment, the ink is oily ink or water-based ink, and the ink is printed on the printing substrate by means of inkjet printing, silk screen printing or microgravure.

In one embodiment, in the low-temperature atmosphere reduction operation, the reduction temperature is 150° C. to 300° C., and the reducing atmosphere is at least one of hydrogen, carbon monoxide, hydrogen sulfide and methane.

In one embodiment, in the photoreduction operation, the restoring light beam is ultraviolet light or yellow light, or the restoring light beam is laser light.

The preparation method of this nano-copper oxide mixes the first dispersion liquid containing copper source and the second dispersion liquid containing strong base, and reflux stirring reaction at 100 ° C ~ 180 ° C for 10 min ~ 60 min, which can produce better dispersion. Nano copper oxide particles.

Description of drawings

Fig. 1 is the flowchart of the preparation method of the nano-copper oxide of an embodiment;

Fig. 2 is the flowchart of the printing method of the metal-based ink of an embodiment;

Fig. 3 is the TEM picture of the nano-copper oxide particle that embodiment 1 prepares;

FIG. 4 is the XRD spectrum of the nano-copper oxide particles prepared in Example 2.

Detailed ways

The manufacturing method of the ferrite powder will be further described in detail mainly in conjunction with the accompanying drawings and specific embodiments below.

The preparation method of the nano-copper oxide of one embodiment as shown in Figure 1, comprises the steps:

S10, using a copper source to configure a first dispersion liquid.

The copper source can be copper hydroxide (Cu(OH) ₂ ), copper chloride (CuCl ₂ 2H ₂ O), copper sulfate (CuSO ₄ 5H ₂ O), basic copper carbonate (Cu ₂ (OH) ₂ CO ₃ ), copper citrate (C ₆ H ₆ CuO ₇ ), copper acetate (Cu(CH ₃ COO) ₂ ·H ₂ O) or copper acetylacetonate (Cu(C ₅ H ₇ O ₂ ) ₂ ).

The concentration of the copper source in the first dispersion liquid is 0.01mol/L˜1mol/L.

In S10, the operation of using the copper source to prepare the first dispersion is as follows: adding the copper source to the first solvent, stirring under reflux at 100° C. to 180° C. for 10 min to 60 min, to obtain the first dispersion.

The first solvent is selected as an alcohol-water mixture, and the alcohol in the alcohol-water mixture is selected from methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, diethylene glycol and glycerol. At least one, the water in the alcohol-water mixture is deionized water.

Preferably, the volume ratio of alcohol to water in the alcohol-water mixture is 1:4˜4:1.

The alcohol-water mixture can better disperse the copper source, which is beneficial to the dispersion of the prepared nano-copper oxide.

S20, using a strong base to prepare a second dispersion liquid.

The strong base can be potassium hydroxide or sodium hydroxide.

The concentration of the strong base in the second dispersion liquid is 0.02mol/L˜2mol/L.

In S20, the operation of using the strong base to prepare the second dispersion is as follows: adding the strong base solid into the second solvent, and stirring evenly at room temperature to obtain the second dispersion.

The solvent of the second dispersion liquid is a second solvent, and the second solvent is a mixed liquid of alcohol and water.

The alcohol in the alcohol-water mixture is selected from at least one of anhydrous methanol, ethanol, butanol, cyclohexanol, isopropanol, ethylene glycol, diethylene glycol and glycerol, and the alcohol-water mixture The water is deionized water.

Preferably, the volume ratio of alcohol to water in the alcohol-water mixture is 1:4˜4:1.

In this embodiment, the first solvent is the same as the second solvent.

S30. Mix the first dispersion liquid obtained in S10 and the second dispersion liquid obtained in S20, and reflux and stir the reaction at 100°C to 180°C for 10min to 60min. The obtained reaction liquid remains solid after separation, and the solid is nano-copper oxide .

The preparation method of the nano-copper oxide particles adopts high-temperature reflux combined with an alcohol-water mixed solvent, which can better disperse the copper source, and the prepared nano-copper oxide has high dispersibility.

The preparation method of this kind of nano-copper oxide particles is simple, the prepared nano-copper oxide particles have good dispersion and are easy to separate, the reaction conditions are relatively mild, the reaction time is short, the preparation efficiency is high, and the equipment requirements are low, which meets the requirements of "green chemistry". .

The prepared nano-copper oxide has good dispersibility and is easy to separate, can directly prepare ink, and is convenient to use.

The prepared nano-copper oxide particles avoid the oxidation problem of the nano-copper, and the particle size of the nano-copper oxide particles is small, about 5-50 nm.

The printing method of the metal-based ink of an embodiment as shown in Figure 2, comprises the steps:

S100. Prepare nano-copper oxide by using the above-mentioned method for preparing nano-copper oxide.

S200, after configuring the nano-copper oxide obtained in S100 into ink, printing it on a printing substrate, and obtaining a printed pattern with good conductivity through low-temperature atmosphere reduction or photoreduction.

The mass fraction of nano-copper oxide in the ink is 5% to 80%. The solvent of the ink is selected according to the configuration of commonly used oily and water-based inks. For example, toluene, xylene, ether, etc. are selected for oil-based systems, and water, alcohol, Polyols, low-boiling esters, etc. Commonly used additives are: polyvinyl alcohol, PVDF, cellulose acetate, etc.

In this embodiment, the ink can be configured by nano-copper oxide and solvent according to a mass ratio of 1:0.5-2.

The printing base material can be a common base material, generally PI, PE or PP. The ink can be applied to the substrate by inkjet printing, screen printing or microgravure.

In the low-temperature atmosphere reduction operation, the reduction temperature is 150°C-300°C, and the reducing atmosphere is at least one of hydrogen, carbon monoxide, hydrogen sulfide and methane.

In the photoreduction operation, the restoring light beam is ultraviolet light or yellow light, or the restoring light beam is laser light.

The following are specific examples.

Example 1

Add 0.01 mol of copper acetate into 100 mL of absolute ethanol, reflux and stir at 100° C., and stir evenly to obtain a copper source dispersion.

Add 0.02 mol of potassium hydroxide to 100 mL of deionized water, and stir at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, reflux and stir the reaction at 100° C. for 10 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After preparing the obtained nano-copper oxide into an oil-based ink, inkjet printing is used to print graphics, and the reducing gas hydrogen is used to bake at 150° C. to obtain printed graphics with good conductivity.

FIG. 3 is a TEM picture of the nano-copper oxide particles prepared in Example 1. It can be seen from FIG. 3 that the nano-cuprous oxide prepared in Example 1 has a particle size of about 7nm and good dispersion.

Example 2

Add 0.01 mol of copper chloride into 100 mL of ethylene glycol, reflux and stir at 120° C., and stir evenly to obtain a copper source dispersion.

Add 0.002 mol of sodium hydroxide into 100 mL of absolute ethanol, and stir evenly at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, reflux and stir the reaction at 120° C. for 40 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After preparing the obtained nano-copper oxide into water-based ink, the pattern is printed by screen printing, and the reducing gas carbon monoxide is used to bake at 300° C. to obtain the printed pattern with good conductivity.

FIG. 4 is the XRD spectrum of the nano-copper oxide particles prepared in Example 2. It can be seen from FIG. 3 that the XRD peak of the nano-copper oxide particles prepared in Example 2 conforms to the standard spectrum of copper oxide, and there are no other impurities.

Example 3

Add 0.01 mol of copper hydroxide to 100 mL of diethylene glycol, reflux and stir at 180°C, and stir evenly to obtain a copper source dispersion.

Add 0.2 mol of potassium hydroxide into 100 mL of absolute ethanol, and stir evenly at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid A, reflux and stir the reaction at 180° C. for 10 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After preparing the obtained nano-copper oxide into oil-based ink, the micro-gravure method is used to print the pattern, and the reducing gas hydrogen sulfide is used to bake at 150°C to obtain the printed pattern with good conductivity.

Example 4

Add 0.001 mol of copper sulfate to 100 mL of deionized water, reflux and stir at 180° C., and stir evenly to obtain a copper source dispersion.

Add 0.002 mol of potassium hydroxide to 100 mL of ethylene glycol, and stir at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, and stir and react at high temperature reflux at 180° C. for 60 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After preparing the obtained nano-copper oxide into water-based ink, ink-jet printing is used to print graphics, and the reducing gas methane is used to bake at 300° C. to obtain printed graphics with good conductivity.

Example 5

Add 0.001 mol of basic copper carbonate to 50 mL of absolute ethanol and 50 mL of deionized water, reflux and stir at 120° C., and stir evenly to obtain a copper source dispersion.

Add 0.02 mol of potassium hydroxide to 100 mL of diethylene glycol, and stir at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, reflux and stir the reaction at 120° C. for 10 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After preparing the obtained nano-copper oxide into oily ink, the pattern is printed by silk screen printing, and the photoreduction is carried out by laser to obtain the printed pattern with good conductivity.

Example 6

Add 0.001 mol of copper citrate into 100 mL of absolute ethanol, reflux and stir at 120° C., and stir evenly to obtain a copper source dispersion.

Add 0.2 mol of potassium hydroxide to 50 mL of absolute ethanol and 50 mL of deionized water, and stir evenly at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, reflux and stir the reaction at 120° C. for 60 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After preparing the obtained nano-copper oxide into water-based ink, the micro-gravure method is used to print graphics, and ultraviolet light is used for photoreduction to obtain printed graphics with good conductivity.

Example 7

Add 0.1 mol of copper acetylacetonate into 50 mL of absolute ethanol and 50 mL of deionized water, reflux and stir at 140° C., and stir evenly to obtain a copper source dispersion.

Add 0.002 mol of potassium hydroxide to 100 mL of ethylene glycol, and stir at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, reflux and stir the reaction at 140° C. for 10 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After preparing the obtained nano-copper oxide into oily ink, inkjet printing is used to print graphics, and yellow light is used for photoreduction to obtain printed graphics with good conductivity.

Example 8

Add 0.1 mol of copper acetate into 100 mL of deionized water, reflux and stir at 140°C, and stir evenly to obtain a copper source dispersion.

Add 0.02 mol of potassium hydroxide to 50 mL of ethylene glycol and 50 mL of deionized water, and stir at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, reflux and stir the reaction at 140° C. for 60 minutes to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After the obtained nano-copper oxide is formulated into water-based ink, the pattern is printed by screen printing, and the reducing gas carbon monoxide is used to bake at 150° C. to obtain a printed pattern with good conductivity.

Example 9

Add 0.1 mol of copper acetate to 50 mL of absolute ethanol and 50 mL of deionized water, reflux and stir at 140° C., and stir evenly to obtain a copper source dispersion.

Add 0.2 mol of potassium hydroxide to 50 mL of absolute ethanol and 50 mL of deionized water, and stir evenly at room temperature to obtain a potassium hydroxide dispersion.

Add the KOH dispersion liquid to the copper source dispersion liquid, reflux and stir the reaction for 10 minutes at 160° C. to obtain rapid precipitated nano-copper oxide.

The nano-copper oxide particle solution is separated in a centrifuge and dried to obtain the nano-copper oxide particle for printing electronics.

After the obtained nano-copper oxide is formulated into oily ink, the pattern is printed by micro-gravure, and the reducing gas hydrogen and methane mixed gas is used to bake at 150°C to obtain a printed pattern with good conductivity.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the present invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (12)

1. a preparation method for nano cupric oxide, is characterized in that, comprises the steps:

Copper source is adopted to configure the first dispersion liquid;

Highly basic is adopted to configure the second dispersion liquid; And

By described first dispersion liquid and described second dispersion liquid mixing, reflux stirring reaction 10min ~ 60min at 100 DEG C ~ 180 DEG C, and the reaction solution obtained retains solid after being separated, and described solid is nano cupric oxide.

2. the preparation method of nano cupric oxide as claimed in claim 1, it is characterized in that, described copper source is copper hydroxide, cupric chloride, copper sulfate, ventilation breather, Cuprocitrol, neutralized verdigris or acetylacetone copper.

3. the preparation method of nano cupric oxide as claimed in claim 1 or 2, it is characterized in that, described in described first dispersion liquid, the concentration in copper source is 0.01mol/L ~ 1mol/L.

4. the preparation method of nano cupric oxide as claimed in claim 1, it is characterized in that, described employing copper source configures being operating as of the first dispersion liquid: add in the first solvent by described copper source, and return stirring 10min ~ 60min at 100 DEG C ~ 180 DEG C obtains described first dispersion liquid.

5. the preparation method of nano cupric oxide as claimed in claim 4, it is characterized in that, described first solvent is alcohol-water mixture; Alcohol in described alcohol-water mixture is selected from least one in methyl alcohol, ethanol, butanols, hexalin, Virahol, ethylene glycol, glycol ether and glycerol, and the water in described alcohol-water mixture is deionized water.

6. the preparation method of nano cupric oxide as claimed in claim 1, it is characterized in that, described highly basic is by potassium hydroxide or sodium hydroxide.

7. the preparation method of nano cupric oxide as claimed in claim 1, it is characterized in that, the solvent of described second dispersion liquid is the second solvent, and described second solvent is alcohol-water mixture;

Alcohol in described alcohol-water mixture is selected from least one in anhydrous methanol, ethanol, butanols, hexalin, Virahol, ethylene glycol, glycol ether and glycerol, and the water in described alcohol-water mixture is deionized water.

8. the preparation method of nano cupric oxide as claimed in claim 1, it is characterized in that, described in described second dispersion liquid, strong paper mill wastewater is 0.02mol/L ~ 2mol/L.

9. a printing process for metal matrix ink, is characterized in that, comprises the steps:

The preparation method of the nano cupric oxide according to any one of claim 1 ~ 8 is adopted to prepare nano cupric oxide; And

After the described nano cupric oxide obtained is configured to ink, be printed on printed substrate, the mode through lower-temperature atmosphere reduction or photoreduction obtains obtaining the printing figures with satisfactory electrical conductivity.

10. the printing process of metal matrix ink as claimed in claim 9, it is characterized in that, described ink is oily ink or water-base ink, and described ink is printed on described printed substrate by the mode of spray ink Printing, silk-screen or nick version.

The printing process of 11. metal matrix ink as claimed in claim 9, is characterized in that, in the operation of described lower-temperature atmosphere reduction, reduction temperature is 150 DEG C ~ 300 DEG C, and reducing atmosphere is at least one in hydrogen, carbon monoxide, hydrogen sulfide and methane.

The printing process of 12. metal matrix ink as claimed in claim 9, is characterized in that, in the operation of described photoreduction, going back elementary beam is UV-light or gold-tinted, or to go back elementary beam be laser.