阅读说明：本技术 一种黑化液及其制备方法和使用方法 (Blackening solution and preparation method and use method thereof ) 是由 邵永存 明东远 李晓红 章晓冬 刘江波 童茂军 于 2020-06-30 设计创作，主要内容包括：本发明公开了一种黑化液及其制备方法和使用方法。本发明的黑化液以水为溶剂,包含质量浓度如下的组分：二氧化硒0.1～5g/L、分散剂0.1～5g/L、缓冲剂0.1～10g/L。本发明的黑化液,不仅能够起到很好的黑化效果,明显降低铜的反射率和亮度,目视不明显,达到消影效果,而且铜面黑化均匀、铜网格线路完整、不影响其导电性能,具有良好的黑化效果稳定性。本发明的黑化液的制备方法简单,使用温度贴近常温、操作方便,黑化方法简单、成本低、黑化效果稳定。(The invention discloses a blackening solution and a preparation method and a use method thereof. The blackening solution takes water as a solvent and comprises the following components in mass concentration: selenium dioxide 0.1-5 g/L, dispersant 0.1-5 g/L, buffer 0.1-10 g/L. The blackening solution disclosed by the invention not only can play a good blackening effect, obviously reduce the reflectivity and brightness of copper, achieve the shadow eliminating effect by being unobvious in visual observation, but also has the advantages of uniform blackening of the copper surface, complete copper grid circuit, no influence on the conductivity of the copper grid circuit and good stability of the blackening effect. The blackening solution disclosed by the invention is simple in preparation method, convenient to operate, simple in blackening method, low in cost and stable in blackening effect, and the use temperature is close to normal temperature.)

1. The blackening solution is characterized by taking water as a solvent and comprising the following components in mass concentration:

selenium dioxide 0.1-5 g/L

0.1-5 g/L of dispersant

0.1-10 g/L of buffer.

2. The blackening solution of claim 1, wherein the dispersing agent is any one or a mixture of at least two of fatty alcohol-polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene alkylamide or polyethylene glycol, and is preferably polyethylene glycol.

3. The blackening solution according to claim 1 or 2, wherein the buffer is any one or a mixture of at least two of sulfuric acid, phosphate, hydrochloric acid, citric acid, phosphoric acid, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate or sodium phosphate, preferably phosphoric acid and/or sodium tripolyphosphate.

4. A method for producing the blackening solution according to any one of claims 1 to 3, which comprises the steps of:

1) dissolving selenium dioxide in water;

2) adding a dispersing agent and a buffering agent into the mixed liquid obtained in the step 1), mixing, and adding water to a constant volume to obtain the blackening liquid.

5. The method according to claim 4, wherein the pH of the solution obtained in step 2) is 2 to 3 after the buffer is added.

6. A method for using the blackening solution according to any one of claims 1 to 3, which comprises: and soaking the metal copper product in the blackening solution for blackening, washing with water, and drying to obtain the blackened metal copper product.

7. The use method of claim 6, wherein the metallic copper product is a bright copper film or a copper mesh touch screen.

8. The use method according to claim 6 or 7, wherein the blackening temperature is 20-40 ℃;

preferably, the blackening time is 20-100 s.

9. The use method according to any one of claims 6 to 8, wherein the temperature of the water washing is 20 to 35 ℃;

preferably, the time of the water washing is 30-60 s.

10. The use according to any one of claims 6 to 9, wherein the drying temperature is 50 to 100 ℃;

preferably, the drying time is 5-15 min.

Technical Field

The invention belongs to the technical field of blackening solution, relates to a blackening solution, a preparation method and a use method thereof, and particularly relates to a blackening solution suitable for a bright copper film or copper grid touch screen, and a preparation method and a use method thereof.

Background

Copper is a metal material with good conductivity and low cost, and is the most main conductive substance on devices such as circuit boards, display screens and the like. In some special applications, it is desirable to form an extremely thin copper film on a substrate by sputtering, vapor deposition, or vacuum sputtering. However, these processes generally form copper films having high visibility of metallic luster and high reflectivity, and the copper films are easily perceived by the naked eye when the circuits are formed, thereby affecting the visual effect of the user. Meanwhile, the line width of the copper grid on the touch screen is generally 2-5 μm, generally less than 5 μm, which is not easy to see by naked eyes, but is bright and has strong light reflection, so that the copper needs to be blackened to make the surface of the copper dark, and the reflectivity and brightness of the metal are reduced, so as to achieve the effect of being invisible by naked eyes. Therefore, a blackening process is required to reduce the light reflectivity of the surface.

CN103898498B discloses a blackening solution, which comprises 3-5% of sodium hydroxide, 10-15% of sodium hypophosphite, 10-15% of sodium chloride, 2-4% of benzotriazole and 70-75% of water (by mass). A method for manufacturing a transparent printed circuit board comprises the following steps: providing a copper-clad substrate, wherein the copper-clad substrate comprises a transparent insulating substrate layer and a copper foil layer with one blackened surface, and the first blackened layer is arranged on the surface of the substrate layer; manufacturing the copper foil layer to form a conductive circuit pattern to form a circuit substrate; putting the surface and the side surface of the copper foil layer, which is not blackened, of the conductive circuit pattern into the blackening liquid medicine for blackening so as to form a second black layer on the surface and the side surface of the copper foil layer, which are not blackened, of the conductive circuit pattern; and forming a transparent covering film on the surface of the second blackening layer and the surface of the substrate layer exposed from the conductive circuit pattern to form a transparent printed circuit board. However, the blackening temperature of the blackening solution is 50-80 ℃, and the blackening time is 5-20min, so that the blackening temperature is high, the blackening time is long, and the blackening effect needs to be further improved.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the blackening liquid and the preparation method and the use method thereof.

One of the purposes of the invention is to provide a blackening solution, and in order to achieve the purpose, the invention adopts the following technical scheme:

the blackening solution takes water as a solvent and comprises the following components in mass concentration:

selenium dioxide 0.1-5 g/L

0.1-5 g/L of dispersant

0.1-10 g/L of buffer.

The blackening solution disclosed by the invention is simple in formula, and the prepared blackening solution can play a good blackening role only through selenium dioxide, a dispersing agent, a buffering agent and water, and can generate a dark substance through a chemical reaction with a copper layer, so that the blackening role is played, wherein the dispersing agent uniformly blackens the copper layer, the buffering agent controls the blackening speed, and the blackening solution not only can play a good blackening effect, obviously reduces the reflectivity and brightness of copper, is not obvious in visual observation and achieves a shadow eliminating effect, but also is uniform in copper surface blackening, complete in copper grid line and free from influencing the conductivity of the copper grid line.

Specifically, the blackening solution disclosed by the invention takes water as a solvent, and comprises the following components in mass concentration:

0.1 to 5g/L of selenium dioxide, for example, the mass concentration of selenium dioxide is 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L or 5 g/L.

0.1 to 5g/L of a dispersant, for example, the dispersant has a mass concentration of 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L or 5 g/L.

0.1-10 g/L of buffer, for example, the mass concentration of buffer is 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, 0.5g/L, 0.6g/L, 0.7g/L, 0.8g/L, 0.9g/L, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, 5g/L, 5.5g/L, 6g/L, 6.5g/L, 7g/L, 7.5g/L, 8g/L, 8.5g/L, 9g/L, 9.5g/L or 10 g/L.

Wherein, the addition of the dispersant is beneficial to the blackening solution to uniformly blacken the copper layer. The dispersing agent is any one or a mixture of at least two of fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylates, polyoxyethylene alkylamide or polyethylene glycol, and preferably polyethylene glycol. Typical but non-limiting combinations of the mixture are a mixture of fatty alcohol-polyoxyethylene ether and alkylphenol-polyoxyethylene ether, a mixture of fatty alcohol-polyoxyethylene ether and polyoxyethylene alkylamide, a mixture of fatty alcohol-polyoxyethylene ether and polyethylene glycol, a mixture of alkylphenol-polyoxyethylene ether and polyoxyethylene alkylamide, a mixture of alkylphenol-polyoxyethylene ether and polyethylene glycol, a mixture of polyoxyethylene alkylamide and polyethylene glycol, a mixture of fatty alcohol-polyoxyethylene ether, alkylphenol-polyoxyethylene ether and polyoxyethylene alkylamide, a mixture of fatty alcohol-polyoxyethylene ether, alkylphenol-polyoxyethylene ether and polyethylene glycol, a mixture of alkylphenol-polyoxyethylene ether, polyoxyethylene alkylamide and polyethylene glycol, fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylates, polyoxyethylene alkylamides or polyethylene glycol.

The pH value of the blackening solution is adjusted by adding the buffering agent, the blackening speed can be controlled, and the pH value is 2-3 after the adjustment by the buffering agent. If the pH value is too low and is lower than 2, the blackening degree is too high, and the blackening layer falls off; if the pH value is too high and is higher than 3, the blackening degree is slight and the blackening effect is not obvious. The buffer is any one or a mixture of at least two of sulfuric acid, phosphate, hydrochloric acid, citric acid, phosphoric acid, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate or sodium phosphate, preferably phosphoric acid and/or sodium tripolyphosphate, and preferably, the mass concentration ratio of the phosphoric acid to the sodium tripolyphosphate is 1: 4. Typical but non-limiting combinations of such mixtures are mixtures of two buffers, such as sulfuric acid, a mixture of phosphates, a mixture of hydrochloric acid, citric acid, phosphoric acid, a mixture of sodium tripolyphosphate, sodium pyrophosphate, a mixture of sodium hexametaphosphate or sodium phosphate, and the like; or a mixture of three buffers, such as sulfuric acid, phosphate, hydrochloric acid, citric acid, phosphoric acid, sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium phosphate, and the like; mixtures of four buffers can also be used, such as mixtures of sulfuric acid, phosphate, hydrochloric acid and citric acid, mixtures of hydrochloric acid, citric acid, phosphoric acid and sodium tripolyphosphate, mixtures of sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate or sodium phosphate, mixtures of citric acid, sodium polyphosphate, sodium pyrophosphate and sodium hexametaphosphate, and the like, and mixtures of five, six, seven, eight and nine buffers can also be used, which are not listed.

The second object of the present invention is to provide a method for preparing the blackening solution according to the first object, comprising the steps of:

1) dissolving selenium dioxide in water;

2) adding a dispersing agent and a buffering agent into the mixed liquid obtained in the step 1), mixing, and adding water to a constant volume to obtain the blackening liquid.

In the step 2), the pH value is 2-3 after the buffer is added, for example, the pH value is 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.

Another object of the present invention is to provide a method for using a blackening solution, which comprises: and soaking the metal copper product in the blackening solution for blackening, washing with water, and drying to obtain the blackened metal copper product.

Wherein, the metal copper product is a bright copper film or a copper grid touch screen.

Wherein the blackening temperature is 20-40 ℃; for example, the temperature for blackening is 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃.

Preferably, the blackening time is 20-100 s, for example, the blackening time is 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, and the like.

Wherein the temperature of the water washing is 20-35 ℃; for example, the temperature of the water washing is 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ or 35 ℃.

Preferably, the time of the water washing is 30-60 s, for example, the time of the water washing is 30s, 35s, 40s, 45s, 50s, 55s or 60 s.

Wherein the drying temperature is 50-100 ℃; for example, the drying temperature is 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.

Preferably, the drying time is 5-15 min, for example, the drying time is 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15 min.

Compared with the prior art, the invention has the beneficial effects that:

(1) the blackening solution disclosed by the invention not only can play a good blackening effect, obviously reduce the reflectivity and brightness of copper, and achieve the shadow eliminating effect because the copper is not obvious visually, but also can uniformly blacken the copper surface, complete the copper grid circuit and not influence the conductivity of the copper grid circuit; specifically, the brightness before blackening is 84.7-84.9, and the brightness after blackening is reduced to 37.8-44.3; the reflectivity before blackening is 65.6-65.9%, and the reflectivity after blackening is reduced to 15.9-18.8%; the square resistance before blackening is 0.077-0.078 omega/□, and the square resistance after blackening is 0.088-0.091 omega/□; the blackening effect has good stability, and the blackening effect has no obvious change after being placed for 7 days at the temperature of 85 ℃ and the humidity of 85 percent.

(2) The blackening solution disclosed by the invention is simple in preparation method, convenient to operate (by adopting a soaking mode), simple in blackening method, low in cost and stable in blackening effect, and the use temperature is close to the normal temperature.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.