Printed circuit board flash corrosion additive resistant to chloride ions and application
An additive system formed by the hydrothermal reaction of UIO-66 and molybdenum disulfide nanosheets solves the problems of reduced etching efficiency and side etching caused by chloride ions in circuit board etching, and achieves stable etching speed and circuit shape.
Patent Information
- Application Number
- CN202511191295.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-25
- Publication Date
- 2025-11-11
AI Technical Summary
Existing circuit board etching systems suffer from reduced etching efficiency and are prone to lateral etching in the presence of chloride ions, affecting the quality of the circuit shape.
UIO-66 was used as a chloride ion scavenger, molybdenum disulfide nanosheets were used as an anti-lateral etching agent, and a stable additive system was formed through hydrothermal reaction. Combined with cocamidopropyl betaine surfactant, the dispersibility and etching speed were improved, and the amount of lateral etching was reduced.
It effectively removes chloride ions, prevents lateral etching, ensures etching speed and line shape quality, and achieves a stable etching process.
Smart Images
Figure CN120924976A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of printed circuit board etching technology, specifically to chloride ion-resistant flash etching additives for printed circuit boards and their applications. Background Technology
[0002] Etching is a crucial process in printed circuit board (PCB) fabrication, but conventional etching techniques struggle to produce fine lines. Currently, the trend is towards using the semi-additive process (SAP) or modified semi-additive process (MSAP) to fabricate lines. This involves layering insulating dielectric films and then chemically plating copper to form a copper conductor layer on the PCB. Because this copper layer is extremely thin, it facilitates the formation of fine lines.
[0003] Existing circuit board etching systems generally employ a hydrogen peroxide-sulfuric acid system, which boasts high etching efficiency. During the etching process, the presence of even small amounts of chloride ions (less than 1 ppm) in the etching bath causes a rapid decrease in micro-etching, impacting normal production. However, these rapid etching stabilizers produce good, rectangular lines with minimal lateral etching and low line loss. Adding a chloride-resistant agent to the rapid etching stabilizer, while stabilizing the etching rate, results in poorer lines, lateral etching, and trapezoidal lines. Therefore, addressing the problems mentioned in the background art, those skilled in the art propose a circuit board flash etching additive that not only rapidly consumes chloride ions but also effectively prevents lateral etching. Summary of the Invention
[0004] The purpose of this invention is to provide a chloride ion-resistant flash etching additive for printed circuit boards to solve the problems mentioned in the background art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: A chloride ion-resistant flash etching additive for printed circuit boards, comprising the following components by weight: Chloride ion remover 0.5-2 parts, anti-lateral corrosion agent 1-3 parts, surfactant 0.1-0.3 parts, and deionized water 42-55 parts; The chloride ion scavenger is a MOF material, specifically UIO-66; The anti-lateral corrosion agent is molybdenum disulfide nanosheets; The surfactant is cocamidopropyl betaine.
[0006] The preparation method of the above-mentioned chloride ion-resistant flash etching additive for printed circuit boards includes the following steps: S1. Disperse the anti-corrosion agent in hydrogen peroxide according to the mass ratio and soak for 0.5-3 hours. Then filter, wash the product with sufficient deionized water and dry it completely at room temperature. S2. Disperse the chloride ion scavenger in a deionized aqueous solution containing 3-aminopropyltriethoxysilane according to the mass ratio and soak for 2-5 hours. Then filter, wash the product with sufficient deionized water and dry it completely at room temperature. S3. Add deionized water to the reactor according to the mass fraction, and add the anti-corrosion agent treated in step S1 and the chloride ion scavenger treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 4-12 hours to obtain the reaction solution. S4. After cooling the reaction solution obtained in step S3 to room temperature, add surfactant according to the mass ratio, stir and mix evenly to obtain a chloride ion resistant printed circuit board flash etching additive.
[0007] Furthermore, in step S1, the mass fraction of hydrogen peroxide is 15-25%, and the mass ratio between the anti-corrosion agent and hydrogen peroxide is 1:20-30.
[0008] Furthermore, in step S2, the mass fraction of 3-aminopropyltriethoxysilane is 0.5-3%, and the mass ratio between the chloride ion scavenger and the deionized aqueous solution containing 3-aminopropyltriethoxysilane is 1:20-30.
[0009] Furthermore, the temperature of the hydrothermal reaction in step S3 is 100-150℃.
[0010] The application of the above-mentioned chloride ion-resistant printed circuit board flash etching additives in the flash etching of printed circuit boards.
[0011] Compared with the prior art, the beneficial effects of the present invention are: 1. In this invention, mof material (UIO-66) is used as a flash corrosion additive. Its huge surface area can adsorb chloride ions in the bath solution, allowing flash corrosion to proceed normally. Molybdenum disulfide nanosheets are used as anti-side corrosion agents, which can be adsorbed on the side of copper to prevent side corrosion. 2. In the preparation of the flash etching additive in this invention, molybdenum disulfide nanosheets and UIO-66 are pretreated respectively, and then combined into a stable system through hydrothermal reaction, which improves dispersibility, increases etching rate, and reduces side etching amount. Attached Figure Description
[0012] Figure 1 This is a process flow diagram for preparing chloride ion-resistant flash etching additives for printed circuit boards according to the present invention. Detailed Implementation
[0013] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0014] Please see Figure 1 The present invention provides: Example 1 A method for preparing a chloride ion-resistant flash etching additive for printed circuit boards includes the following steps: S1. Disperse 1.8 parts of anti-corrosion agent into 20% hydrogen peroxide and soak for 2.2 hours. The amount of hydrogen peroxide used is 44 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S2. Disperse 1.1 parts of chloride ion scavenger into a deionized aqueous solution containing 3-aminopropyltriethoxysilane and soak for 4.2 h. The mass fraction of 3-aminopropyltriethoxysilane is 1.5%, and the amount of deionized aqueous solution of 3-aminopropyltriethoxysilane is 27.5 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S3. Add 44 parts of deionized water to the reactor, and add the anti-corrosion agent treated in step S1 and the chloride ion remover treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 10 hours to obtain the reaction solution. The temperature of the hydrothermal reaction is 120℃. S4. After cooling the reaction solution obtained in step S3 to room temperature, add 0.2 parts of surfactant and stir to mix evenly to obtain a chloride ion resistant flash etching additive for printed circuit boards.
[0015] Example 2 A method for preparing a chloride ion-resistant flash etching additive for printed circuit boards includes the following steps: S1. Disperse 1 part of the anti-corrosion agent into 15% hydrogen peroxide and soak for 0.5 hours. The amount of hydrogen peroxide used is 20 parts. Then filter and wash the product with sufficient deionized water and dry it completely at room temperature. S2. Disperse 0.5 parts of chloride ion scavenger into a deionized aqueous solution containing 3-aminopropyltriethoxysilane and soak for 2 hours. The mass fraction of 3-aminopropyltriethoxysilane is 0.5%, and the amount of deionized aqueous solution of 3-aminopropyltriethoxysilane is 10 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S3. Add 42 parts of deionized water to the reaction vessel, and add the anti-corrosion agent treated in step S1 and the chloride ion remover treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 4 hours to obtain the reaction solution. The temperature of the hydrothermal reaction is 100℃. S4. After cooling the reaction solution obtained in step S3 to room temperature, add 0.1 parts of surfactant and stir to mix evenly to obtain a chloride ion resistant flash etching additive for printed circuit boards.
[0016] Example 3 A method for preparing a chloride ion-resistant flash etching additive for printed circuit boards includes the following steps: S1. Disperse 3 parts of the anti-corrosion agent into 25% hydrogen peroxide and soak for 3 hours. The amount of hydrogen peroxide used is 90 parts. Then filter, wash the product with sufficient deionized water and dry it completely at room temperature. S2. Disperse 2 parts of chloride ion scavenger into a deionized aqueous solution containing 3-aminopropyltriethoxysilane and soak for 5 hours. The mass fraction of 3-aminopropyltriethoxysilane is 3%, and the amount of the deionized aqueous solution of 3-aminopropyltriethoxysilane is 60 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S3. Add 55 parts of deionized water to the reaction vessel, and add the anti-corrosion agent treated in step S1 and the chloride ion remover treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 12 hours to obtain the reaction solution. The temperature of the hydrothermal reaction is 150℃. S4. After cooling the reaction solution obtained in step S3 to room temperature, add 0.3 parts of surfactant and stir to mix evenly to obtain a chloride ion resistant flash etching additive for printed circuit boards.
[0017] Example 4 A method for preparing a chloride ion-resistant flash etching additive for printed circuit boards includes the following steps: S1. Disperse 1.2 parts of anti-corrosion agent into 20% hydrogen peroxide and soak for 2.6 hours. The amount of hydrogen peroxide used is 32 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S2. Disperse 1.6 parts of chloride ion scavenger into a deionized aqueous solution containing 3-aminopropyltriethoxysilane and soak for 3.6 hours. The mass fraction of 3-aminopropyltriethoxysilane is 2%, and the amount of deionized aqueous solution of 3-aminopropyltriethoxysilane is 38 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S3. Add 50 parts of deionized water to the reactor, and add the anti-corrosion agent treated in step S1 and the chloride ion remover treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 8 hours to obtain the reaction solution. The temperature of the hydrothermal reaction is 130℃. S4. After cooling the reaction solution obtained in step S3 to room temperature, add 0.2 parts of surfactant and stir to mix evenly to obtain a chloride ion resistant flash etching additive for printed circuit boards.
[0018] Example 5 A method for preparing a chloride ion-resistant flash etching additive for printed circuit boards includes the following steps: S1. Disperse 1.4 parts of anti-corrosion agent into 20% hydrogen peroxide and soak for 2.2 hours. The amount of hydrogen peroxide used is 30 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S2. Disperse 1.8 parts of chloride ion scavenger into a deionized aqueous solution containing 3-aminopropyltriethoxysilane and soak for 2.8 hours. The mass fraction of 3-aminopropyltriethoxysilane is 2%, and the amount of deionized aqueous solution of 3-aminopropyltriethoxysilane is 40 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S3. Add 48 parts of deionized water to the reactor, and add the anti-corrosion agent treated in step S1 and the chloride ion remover treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 8 hours to obtain the reaction solution. The temperature of the hydrothermal reaction is 150℃. S4. After cooling the reaction solution obtained in step S3 to room temperature, add 0.1 parts of surfactant and stir to mix evenly to obtain a chloride ion resistant flash etching additive for printed circuit boards.
[0019] Example 6 A method for preparing a chloride ion-resistant flash etching additive for printed circuit boards includes the following steps: S1. Disperse 2.6 parts of anti-corrosion agent into 20% hydrogen peroxide and soak for 2.2 hours. The amount of hydrogen peroxide used is 45 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S2. Disperse 1.4 parts of chloride ion scavenger into a deionized aqueous solution containing 3-aminopropyltriethoxysilane and soak for 4.1 h. The mass fraction of 3-aminopropyltriethoxysilane is 3% and the amount of deionized aqueous solution of 3-aminopropyltriethoxysilane is 40 parts. After filtration, the product is washed with sufficient deionized water and dried completely at room temperature. S3. Add 51 parts of deionized water to the reactor, and add the anti-corrosion agent treated in step S1 and the chloride ion remover treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 10 hours to obtain the reaction solution. The temperature of the hydrothermal reaction is 110℃. S4. After cooling the reaction solution obtained in step S3 to room temperature, add 0.2 parts of surfactant and stir to mix evenly to obtain a chloride ion-resistant flash etching additive for printed circuit boards. The chloride ion scavenger used in Examples 1-6 above is a MOF material, specifically UIO-66; the anti-lateral corrosion agent is molybdenum disulfide nanosheets; and the surfactant is cocamidopropyl betaine.
[0020] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the treatment of the anti-corrosion agent with hydrogen peroxide in step S1 was omitted, while the remaining steps are exactly the same as in Example 1.
[0021] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the treatment of chloride ion scavenger with deionized aqueous solution of 3-aminopropyltriethoxysilane in step S2 was omitted; the remaining steps are exactly the same as in Example 1.
[0022] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that the addition of the anti-side corrosion agent was completely eliminated, while the remaining steps were exactly the same as in Example 1.
[0023] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that the addition of chloride ion scavenger was completely eliminated, while the remaining steps are exactly the same as in Example 1.
[0024] Comparative Example 5 The difference between Comparative Example 5 and Example 1 is that the hydrothermal reaction in step S3 is omitted, and the anti-side etching agent treated in step S1, the chloride ion scavenger treated in step S2, the surfactant and deionized water are directly mixed evenly to obtain the flash etching additive for printed circuit boards.
[0025] A flash etching solution was prepared, containing hydrogen peroxide, copper ions, sulfuric acid, and deionized water. The concentrations of hydrogen peroxide, copper ions, and sulfuric acid were 20 g / L and 50 g / L, respectively. A total of 11 groups of flash etching solutions were prepared. Flash etching additives prepared in Examples 1-6 and Comparative Examples 1-4 were added to 10 of these groups of flash etching solutions, with the added flash etching additives accounting for 2% of the total mass of each group of flash etching solutions. No deionized water was added to the 11th group, and the added deionized water accounted for 2% of the total mass of the flash etching solution. The 11th group was designated as the control group.
[0026] Etching tests were conducted on the flash etching solutions containing the flash etching additives prepared in Examples 1-6 and Comparative Examples 1-4, and on the flash etching solution containing deionized water in Group 11. The copper foil on an integrated circuit board with dimensions of 6cm × 6cm × 0.5cm was etched using a static suspension test method, and the etching rate was calculated using the following formula: v = Δm / (S·8.93g / cm³·t) × 10⁻⁶. - 3 ; In the formula above: v is the etching rate, which is the thickness of copper etched by the etchant per unit time, in μm / min; Δm is the etch mass, in mg; and S is the etch area, in mm. 2 t represents the etching time, in minutes. Lateral erosion was observed and recorded using an electron microscope, with units of μm; The experimental results are shown in Table 1 below.
[0027] Table 1: Etching Test Results of Circuit Boards for Each Implementation Method and Control Group As can be seen from Table 1 above, Example 1 and the control group, the addition of chloride ion remover and anti-side etching agent to the flash etching solution of the present invention can ensure the etching rate of the circuit board while reducing the amount of side etching. As can be seen from the data of Example 1 and Comparative Examples 1-2, after the treatment of the anti-side etching agent with hydrogen peroxide and the treatment of the chloride ion remover with the deionized aqueous solution of 3-aminopropyltriethoxysilane are eliminated, the etching rate and the amount of side etching decrease respectively. In addition, the data of Example 1 and Comparative Example 5 show that the anti-side etching agent and chloride ion remover can effectively improve the etching rate and reduce the amount of side etching after hydrothermal reaction.
[0028] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A chloride-resistant flash etching additive for printed circuit boards, characterized in that, By weight, it includes the following components: Chloride ion remover 0.5-2 parts, anti-lateral corrosion agent 1-3 parts, surfactant 0.1-0.3 parts, and deionized water 42-55 parts; The chloride ion scavenger is a MOF material, specifically UIO-66; The anti-lateral corrosion agent is molybdenum disulfide nanosheets; The surfactant is cocamidopropyl betaine.
2. The chloride-resistant flash etching additive for printed circuit boards as described in claim 1, characterized in that, The preparation method of the flash corrosion additive includes the following steps: S1. Disperse the anti-corrosion agent in hydrogen peroxide according to the mass ratio and soak for 0.5-3 hours. Then filter, wash the product with sufficient deionized water and dry it completely at room temperature. S2. Disperse the chloride ion scavenger in a deionized aqueous solution containing 3-aminopropyltriethoxysilane according to the mass ratio and soak for 2-5 hours. Then filter, wash the product with sufficient deionized water and dry it completely at room temperature. S3. Add deionized water to the reactor according to the mass fraction, and add the anti-corrosion agent treated in step S1 and the chloride ion scavenger treated in step S2 to the deionized water respectively. Seal and hydrothermal reaction for 4-12 hours to obtain the reaction solution. S4. After cooling the reaction solution obtained in step S3 to room temperature, add surfactant according to the mass ratio, stir and mix evenly to obtain a chloride ion resistant printed circuit board flash etching additive.
3. The chloride-resistant flash etching additive for printed circuit boards according to claim 2, characterized in that, In step S1, the mass fraction of hydrogen peroxide is 15-25%, and the mass ratio between the anti-corrosion agent and hydrogen peroxide is 1:20-30.
4. The chloride-resistant flash etching additive for printed circuit boards according to claim 2, characterized in that, In step S2, the mass fraction of 3-aminopropyltriethoxysilane is 0.5-3%, and the mass ratio between the chloride ion scavenger and the deionized aqueous solution containing 3-aminopropyltriethoxysilane is 1:20-30.
5. The chloride-resistant flash etching additive for printed circuit boards according to claim 2, characterized in that, The temperature of the hydrothermal reaction in step S3 is 100-150℃.
6. The application of the chloride ion-resistant printed circuit board flash etching additive as described in any one of claims 1-5 in the flash etching of printed circuit boards.