An alkaline super-roughening solution, a method for preparing the same, and a super-roughening method

Abstract

This invention discloses an alkaline ultra-roughening solution and its preparation and ultra-roughening methods, relating to the field of printed circuit board manufacturing technology. The alkaline ultra-roughening solution comprises the following components by mass concentration: ammonium sulfate 5-40 g / L, potassium chloride 2-10 g / L, ammonia water 5-20 g / L, a roughening and leveling agent 2-10 g / L, antioxidant 0.05-0.5 g / L, stabilizer 0.3-1.5 g / L, dispersant 0.1-1.0 g / L, accelerator 0.2-2.0 g / L, copper surface corrosion inhibitor 0.1-1.0 g / L, with the balance being deionized water. The alkaline ultra-roughening solution of this invention can significantly increase the specific surface area of ​​copper foil, forming a uniform micro-rough structure, improving the adhesion of dry film, wet film, and solder resist to the copper surface. It is particularly suitable for the fine circuit fabrication of HDI boards and processes such as chemical immersion tin and immersion nickel-gold, effectively preventing solder resist peeling and improving the yield of the ultra-roughening process.

Description

Technical Field

[0001] This invention relates to the field of printed circuit board manufacturing technology, and in particular to an alkaline ultra-roughening solution and its preparation and ultra-roughening methods. Background Technology

[0002] In recent years, as electronic devices have become lighter, thinner, shorter, and smaller, the same requirements for thinner and lighter PCBs have been placed on them. Circuit board designs are becoming increasingly dense, with smaller line widths and spacings. Besides high electroplating uniformity, another key aspect of fabricating fine circuits is optical imaging. Regardless of whether it's a positive or negative film process, the smaller the line width and spacing, the smaller the contact area between the dry film (resist or resist layer) and the copper surface. This presents a severe challenge to the adhesion of the dry film, easily leading to problems such as plating bleed and short circuits in positive films, and open circuits and gaps in negative films.

[0003] A common method to improve dry film adhesion is copper surface pretreatment, which increases the roughness and surface area of ​​the copper surface, thereby increasing the contact area between the copper and the dry film. Currently, commonly used dry film pretreatment methods include brushing, sandblasting, sodium persulfate micro-etching, sulfuric acid-hydrogen peroxide micro-etching, volcanic ash, and ultra-roughening. Among these, the ultra-roughening process, often used for solder mask pretreatment, is increasingly being adopted by manufacturers due to its excellent roughening effect, low cost, and minimal maintenance. The most significant difference between solder mask pretreatment and dry film pretreatment is that after PCB solder mask printing, the pads are exposed after exposure and development, and subsequent processes are generally surface treatment. However, after dry film pretreatment, the negative board undergoes exposure, development, etching, and film removal, and its copper surface needs to be inspected by AOI scanning, requiring higher standards for copper surface color and cleanliness; otherwise, false spots may be difficult to detect. The positive board undergoes exposure, development, pattern electroplating, and then film removal and etching, requiring a high degree of cleanliness in the film removal process. If dry film residue remains on the copper surface, it will lead to residual copper, causing short circuits. Therefore, introducing an ultra-roughening process into the dry film pretreatment and green oil pretreatment can solve the above problems. Of course, this places higher demands on the precision and stability of the ultra-roughening solution.

[0004] The sulfuric acid-hydrogen peroxide-based ultra-roughening solution described in Chinese invention patent CN114686885A only improved copper surface oxidation and AOI inspection yield, but it lacked a specific solution for the problem of oil shedding from immersion tin boards. Furthermore, hydrochloric acid washing after ultra-roughening also posed some quality risks and increased production process and environmental wastewater treatment costs. The research and application of alkaline ultra-roughening solutions can not only improve production efficiency, reduce production costs, and enhance quality yield, but also reduce environmental pollution. Therefore, developing more efficient alkaline ultra-roughening solutions to replace traditional ultra-roughening solutions has become a future development trend. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an alkaline ultra-roughening solution, its preparation method, and the ultra-roughening method. This solution can enhance the adhesion between the dry film, solder resist ink, and copper layer, solve the problem of ink detachment from the tinplate, improve copper surface oxidation, increase the yield of the AOI process, and eliminate the need for hydrochloric acid washing after ultra-roughening. This can improve production efficiency and reduce costs, while maintaining stable quality.

[0006] Specifically, the following technical solutions are included:

[0007] In a first aspect, an alkaline ultra-roughening solution is provided, comprising the following components by mass concentration: ammonium sulfate 5-40 g / L, potassium chloride 2-10 g / L, ammonia water 5-20 g / L, roughening and leveling agent 2-10 g / L, antioxidant 0.05-0.5 g / L, stabilizer 0.3-1.5 g / L, dispersant 0.1-1.0 g / L, accelerator 0.2-2.0 g / L, copper surface corrosion inhibitor 0.1-1.0 g / L, with the balance being deionized water.

[0008] The roughening and leveling agent is selected from at least one of 2-mercaptothiazoline, fluoropolyether modified polysiloxane, ammonium molybdate, and 2-mercaptobenzimidazole;

[0009] The antioxidant is selected from at least one of sodium sulfite, sodium thiosulfate, and cysteine;

[0010] The stabilizer is selected from at least one of polyacrylamide, betaine, and sodium fatty alcohol polyoxyethylene ether sulfate;

[0011] The dispersant is selected from at least one of sodium polyacrylate, fatty acid polyoxyethylene ether, alkylphenol polyoxyethylene ether, and dodecyl dimethyl betaine;

[0012] The accelerator is selected from at least one of 2-mercapto-1-methylimidazolium, thiazolidin-2-thione, and 4,6-dimethyl-2-mercaptopyrimidine;

[0013] The copper surface corrosion inhibitor is selected from at least one of sodium silicate, hexamethyleneamine, dodecylamine, and sodium polyphosphate.

[0014] Furthermore, the mass ratio of the roughening and leveling agent to the dispersant is 1:(0.02-0.4).

[0015] Preferably, the mass concentration of the roughening and leveling agent is 4-6 g / L.

[0016] Preferably, the antioxidant has a mass concentration of 0.2-0.3 g / L.

[0017] Preferably, the mass concentration of the stabilizer is 0.8-1.0 g / L.

[0018] Preferably, the mass concentration of the dispersant is 0.4-0.6 g / L.

[0019] Preferably, the mass concentration of the accelerator is 0.8-1.2 g / L.

[0020] Preferably, the mass concentration of the copper surface corrosion inhibitor is 0.4-0.6 g / L.

[0021] Furthermore, the alkaline ultra-roughening solution comprises the following components by mass concentration: ammonium sulfate 18-24 g / L, potassium chloride 4-6 g / L, ammonia 10-12 g / L, roughening and leveling agent 4-6 g / L, antioxidant 0.2-0.3 g / L, stabilizer 0.8-1.0 g / L, dispersant 0.4-0.6 g / L, accelerator 0.8-1.2 g / L, copper surface corrosion inhibitor 0.4-0.6 g / L, with the balance being deionized water.

[0022] Furthermore, the alkaline ultra-roughening solution is composed of the following components by mass concentration: ammonium sulfate 20 g / L, potassium chloride 5 g / L, ammonia water 11 g / L, roughening and leveling agent 5 g / L, antioxidant 0.25 g / L, stabilizer 0.9 g / L, dispersant 0.5 g / L, accelerator 1.0 g / L, copper surface corrosion inhibitor 0.5 g / L, with the balance being deionized water.

[0023] In a second aspect, a method for preparing the alkaline ultra-roughening solution as described in the first aspect is provided, comprising the following steps: adding ammonium sulfate, potassium chloride, ammonia, a roughening and leveling agent, an antioxidant, a stabilizer, a dispersant, an accelerator, and a copper surface corrosion inhibitor to deionized water and mixing them evenly to obtain the alkaline ultra-roughening solution.

[0024] Preferably, the mixing time is 20-40 minutes.

[0025] Thirdly, a method for roughening the copper surface of a circuit board using an alkaline roughening solution as described in the first aspect is provided, comprising the following steps: using the alkaline roughening solution described in the first aspect to perform micro-etching on the copper surface of the circuit board by horizontal spraying.

[0026] Furthermore, the spray pressure of the horizontal spray method is 1.5-2.5 kg / cm². 2 The micro-etching time on the board surface is 40-80 seconds.

[0027] Furthermore, the temperature for the micro-etching of the plate surface is 25-35℃. Preferably, the temperature for the micro-etching of the plate surface is 28-32℃.

[0028] Preferably, the alkaline ultra-roughening solution used in the ultra-roughening method has a concentration of 100 wt%.

[0029] In some specific embodiments, the method for roughening the alkaline ultra-roughening solution includes the following steps: feeding the board - brushing - washing with water - ultra-roughening - washing with water - drying - collecting the board - dry film or solder resist ink.

[0030] The alkaline ultra-coarsening solution, its preparation method, and the ultra-coarsening method provided by this invention have the following advantages:

[0031] (1) The copper surface roughness after alkaline ultra-roughening solution treatment is consistent (Ra value reaches 0.35-0.45μm), the micro-etching amount is stable and controllable, it does not damage fine lines, and the board surface is not easily oxidized after treatment, and can be stored for a long time without affecting the quality.

[0032] (2) The absence of hydrochloric acid washing process improves production efficiency and reduces production costs. Using alkaline substances instead of formic acid or sulfuric acid hydrogen peroxide series of ultra-coarsening solutions can effectively improve the environmental pollution problem.

[0033] (3) Through the interaction of effective components in the alkaline ultra-roughening solution, the specific surface area of ​​copper foil is significantly increased, forming a uniform micro-rough structure, thereby improving the adhesion between dry film, wet film and solder resist green oil to copper surface. It is especially suitable for fine circuit fabrication of HDI board and chemical immersion tin, immersion nickel gold and other processes, effectively preventing solder resist from falling off. Attached Figure Description

[0034] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the following description of the embodiments will be briefly introduced. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0035] Figure 1 This is an example of the oil shedding condition of the tinplate after testing on the alkaline ultra-roughening solution production line in Example 1 of the present invention.

[0036] Figure 2 This is an example of the oil shedding condition of the tinplate after testing on the alkaline ultra-roughening solution production line in Example 2 of the present invention.

[0037] Figure 3 This is an example of the oil shedding condition of the tinplate after testing on the alkaline ultra-roughening solution production line in Example 3 of the present invention.

[0038] Figure 4 This is a comparison of the oil shedding of the tinplate after testing the alkaline ultra-roughening solution production line of Comparative Example 1 of this invention.

[0039] Figure 5 This is a comparison of the oil shedding of the tinplate after testing the alkaline ultra-roughening solution production line of Comparative Example 2 of this invention.

[0040] Figure 6This is a comparison of the oil shedding of the tinplate after testing on the production line of the alkaline ultra-roughening solution in Comparative Example 3 of this invention.

[0041] Figure 7 This is a comparison of the oil shedding of the tinplate after testing the alkaline ultra-coarsening solution production line of Comparative Example 4 of this invention. Detailed Implementation

[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. 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.

[0043] It should be understood that, when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0044] To better understand the technical content of the present invention, the technical solution of the present invention will be further introduced and explained below with reference to specific embodiments.

[0045] Unless otherwise stated, "g / L" in this invention refers to mass concentration.

[0046] In this invention, micro-etching refers to ultra-coarsening.

[0047] The ultra-roughening method of alkaline ultra-roughening solution includes the following process: S1 loading onto the plate; S2 washing with water; S3 grinding; S4 washing with water; S5 ultra-roughening (alkaline); S6 washing with water; S7 drying; S8 collecting the plate.

[0048] The S5 etching step is as follows: First, the alkaline ultra-roughening solution from the example or comparative example is used to prepare the chemical bath on a horizontal ultra-roughening line, and the temperature is raised to 25-35℃. Then, the circuit board is ground, and the surface of the circuit board is micro-etched using a horizontal line spraying method at an ultra-roughening trolley speed of 3-6 m / min. The spraying pressure for the horizontal line spraying method is 1.5-2.5 kg / cm². 2 The roughening time is 40-80 seconds. Finally, the roughened circuit board undergoes washing in step S6, drying in step S7, and board collection in step S8.

[0049] The alkaline ultra-coarsening solution used in the initial tank preparation process is at a concentration of 100 wt%.

[0050] Verification test of the effect of alkaline ultra-coarsening solution (production line test):

[0051] Circuit boards treated with alkaline ultra-roughening solutions from both the examples and comparative examples were subjected to dry film etching, nickel-gold plating, and tin plating tests. Normal micro-etching tests were conducted on the ultra-roughening production line, with 5 PCBs produced for each method. The dry film boards were scanned using AOI to observe the micro-etching effect. The nickel-gold and tin plating boards underwent an oil-shedding test using adhesive tape. The following parameters were measured: micro-etching amount (µm), AOI yield (%), residual copper (%), open circuit percentage (%), short circuit percentage (%), notch percentage (%), and oil shedding on the nickel-gold and tin plating boards. The reasonable ranges for residual copper percentage, open circuit percentage, short circuit percentage, and notch percentage were all 0-0.1%. The reasonable condition for nickel-gold plating was no oil shedding, and the reasonable condition for tin plating was no oil shedding.

[0052] The AOI yield calculation method for circuit boards is as follows: Product yield = (Number of qualified product units / Total number of production units) × 100%.

[0053] Example 1

[0054] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 6 g / L ammonium sulfate, 4 g / L potassium chloride, 5 g / L ammonia, 2 g / L 2-mercaptothiazoline, 0.1 g / L sodium sulfite, 0.3 g / L polyacrylamide, 0.1 g / L sodium polyacrylate, 0.2 g / L 2-mercapto-1-methylimidazolium, 0.2 g / L sodium silicate, with the balance being deionized water.

[0055] The preparation method of the alkaline ultra-roughening solution includes the following steps: adding ammonium sulfate, potassium chloride, ammonia, roughening and leveling agent, antioxidant, stabilizer, dispersant, accelerator, and copper surface corrosion inhibitor to deionized water and mixing and stirring for 40 minutes to obtain the alkaline ultra-roughening solution of Example 1.

[0056] The method for ultra-roughening the alkaline ultra-roughening solution includes the following steps:

[0057] S1 Loading; S2 Washing; S3 Grinding; S4 Washing; S5 Roughening (Alkaline); S6 Washing; S7 Drying; S8 Retrieving.

[0058] The S5 ultra-roughening step is as follows: First, the alkaline ultra-roughening solution from Example 1 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 28°C. Then, the circuit board is ground, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 4 m / min. The spraying pressure for the horizontal spray method is 2.0 kg / cm². 2 The micro-etching time is 60 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation is 100 wt%.

[0059] The preparation methods of the alkaline ultra-coarsened solutions in Examples 2-9 are the same as those in Example 1.

[0060] Example 2

[0061] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 5 g / L ammonium sulfate, 4 g / L potassium chloride, 11 g / L ammonia, 5 g / L fluoropolyether modified polysiloxane, 0.2 g / L sodium thiosulfate, 0.9 g / L betaine, 0.4 g / L fatty acid polyoxyethylene ether, 0.9 g / L thiazolidin-2-thione, 1.0 g / L hexamethyleneamine, with the balance being deionized water.

[0062] The difference between the alkaline ultra-roughening solution method in Example 2 and that in Example 1 is that the ultra-roughening step S5 in Example 2 is as follows: First, the alkaline ultra-roughening solution from Example 2 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 28°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 5 m / min. The spraying pressure for the horizontal spray method is 2.2 kg / cm². 2 The micro-etching time was 48 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation was 100 wt%.

[0063] Example 3

[0064] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 30 g / L ammonium sulfate, 10 g / L potassium chloride, 15 g / L ammonia, 5 g / L ammonium molybdate, 0.3 g / L cysteine, 1.0 g / L sodium fatty alcohol polyoxyethylene ether sulfate, 0.6 g / L alkylphenol polyoxyethylene ether, 2.0 g / L 4,6-dimethyl-2-mercaptopyrimidine, 0.6 g / L hexamethyleneamine, with the balance being deionized water.

[0065] The difference between the alkaline ultra-roughening solution method in Example 3 and that in Example 1 is that the ultra-roughening step S5 in Example 3 is as follows: First, the alkaline ultra-roughening solution of Example 3 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 29°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 6 m / min. The spraying pressure for the horizontal spray method is 2.1 kg / cm². 2 The micro-etching time is 40 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation is 100 wt%.

[0066] Example 4

[0067] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 40 g / L ammonium sulfate, 3 g / L potassium chloride, 20 g / L ammonia, 4 g / L fluoropolyether modified polysiloxane, 0.3 g / L cysteine, 1.0 g / L fatty alcohol polyoxyethylene ether sodium sulfate, 1.0 g / L alkylphenol polyoxyethylene ether, 1.6 g / L 4,6-dimethyl-2-mercaptopyrimidine, 0.8 g / L sodium polyphosphate, with the balance being deionized water.

[0068] The difference between the alkaline ultra-roughening solution method in Example 4 and that in Example 1 is that the ultra-roughening step S5 in Example 4 is as follows: First, the alkaline ultra-roughening solution of Example 4 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 28°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 6 m / min. The spraying pressure for the horizontal spray method is 2.4 kg / cm². 2 The micro-etching time is 40 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation is 100 wt%.

[0069] Example 5

[0070] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 25 g / L ammonium sulfate, 8 g / L potassium chloride, 15 g / L ammonia, 5 g / L 2-mercaptobenzimidazole, 0.5 g / L cysteine, 1.5 g / L betaine, 0.1 g / L alkylphenol polyoxyethylene ether, 1.5 g / L 4,6-dimethyl-2-mercaptopyrimidine, 0.6 g / L sodium polyphosphate, with the balance being deionized water.

[0071] The difference between the alkaline ultra-roughening solution method in Example 5 and that in Example 1 is that the ultra-roughening step S5 in Example 5 is as follows: First, the alkaline ultra-roughening solution of Example 5 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 30°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 4.5 m / min. The spraying pressure for the horizontal spray method is 2.5 kg / cm². 2 The micro-etching time was 54 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation was 100 wt%.

[0072] Example 6

[0073] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 35 g / L ammonium sulfate, 6 g / L potassium chloride, 16 g / L ammonia, 2.0 g / L 2-mercaptobenzimidazole, 0.2 g / L cysteine, 1.2 g / L betaine, 0.8 g / L dodecyl dimethyl betaine, 0.9 g / L thiazolidin-2-thione, 0.9 g / L dodecylamine, with the balance being deionized water.

[0074] The difference between the alkaline ultra-roughening solution method in Example 6 and that in Example 1 is that the ultra-roughening step S5 in Example 6 is as follows: First, the alkaline ultra-roughening solution of Example 6 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 30°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 5 m / min. The spraying pressure for the horizontal spray method is 2.0 kg / cm². 2 The micro-etching time was 48 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation was 100 wt%.

[0075] Example 7

[0076] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 15 g / L ammonium sulfate, 7 g / L potassium chloride, 14 g / L ammonia, 10 g / L ammonium molybdate, 0.05 g / L sodium sulfite, 1.0 g / L betaine, 0.9 g / L alkylphenol polyoxyethylene ether, 1.4 g / L thiazolidin-2-thione, 0.1 g / L sodium silicate, with the balance being deionized water.

[0077] The difference between the alkaline ultra-roughening solution method in Example 7 and that in Example 1 is that the ultra-roughening step S5 in Example 7 is as follows: First, the alkaline ultra-roughening solution of Example 7 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 32°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 5.5 m / min. The spraying pressure for the horizontal spray method is 2.2 kg / cm². 2 The micro-etching time was 44 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation was 100 wt%.

[0078] Example 8

[0079] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 35 g / L ammonium sulfate, 4 g / L potassium chloride, 12 g / L ammonia, 8 g / L 2-mercaptothiazoline, 0.4 g / L sodium thiosulfate, 1.3 g / L polyacrylamide, 0.4 g / L dodecyl dimethyl betaine, 1.5 g / L 2-mercapto-1-methylimidazole, 0.8 g / L hexamethyleneamine, with the balance being deionized water.

[0080] The difference between the alkaline ultra-roughening solution method in Example 8 and that in Example 1 is that the ultra-roughening step S5 in Example 8 is as follows: First, the alkaline ultra-roughening solution of Example 8 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 29°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 4.5 m / min. The spraying pressure for the horizontal spray method is 2.2 kg / cm². 2 The micro-etching time was 54 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation was 100 wt%.

[0081] Example 9

[0082] An alkaline ultra-coarsening solution comprises the following components by mass concentration: 25 g / L ammonium sulfate, 2 g / L potassium chloride, 20 g / L ammonia, 6 g / L 2-mercaptobenzimidazole, 0.5 g / L sodium sulfite, 1.1 g / L betaine, 0.7 g / L sodium polyacrylate, 1.9 g / L thiazolidin-2-thione, 0.3 g / L sodium silicate, with the balance being deionized water.

[0083] The difference between the alkaline ultra-roughening solution method in Example 9 and that in Example 1 is that the ultra-roughening step S5 in Example 9 is as follows: First, the alkaline ultra-roughening solution of Example 9 is used to prepare the chemical bath along the horizontal micro-etching line, and the temperature is raised to 31°C. Then, the circuit board is subjected to grinding treatment, and the board surface is micro-etched using a horizontal spray method at a micro-etching speed of 3.5 m / min. The spraying pressure for the horizontal spray method is 2.3 kg / cm². 2 The micro-etching time was 68 seconds. The amount of the alkaline ultra-roughening solution used in the initial tank preparation was 100 wt%.

[0084] To better illustrate the technical effects of the present invention, comparative examples 1-9 were provided based on Example 1. The differences between comparative examples 1-9 and Example 1 are shown in Table 1 below:

[0085] Table 1. Differences between Comparative Examples 1-9 and Example 1

[0086]

[0087] The only difference between Comparative Examples 1-9 and Example 1 is the composition of the alkaline ultra-coarsening solution; all other conditions are the same.

[0088] To further illustrate the technical effects of the present invention, the following experiments were conducted for verification.

[0089] I. Component Verification Test of Alkaline Ultra-coarsening Solution

[0090] 1) The alkaline ultra-roughening solutions of Examples 1-9 were treated with an ultra-roughening method on the production line, with 5 pnls produced for each example. The board layout was 80 units / pnl. Then, quality tests were performed on the AOI, nickel plating, and tin plating processes of the circuit boards. The test results are shown in Table 2.

[0091] Table 2 Test results of alkaline ultra-coarsening solutions in Examples 1-9

[0092]

[0093] 2) The alkaline ultra-roughening solutions of Comparative Examples 1-9 were treated with an ultra-roughening method on the production line, with 5 pnls produced for each comparative example. The board layout was 80 units / pnl. Then, quality tests were conducted on the AOI, nickel plating, and tin plating processes of the circuit boards. The test results are shown in Table 3.

[0094] Table 3 Test results of alkaline ultra-coarsened solutions of Comparative Examples 1-9

[0095]

[0096] Example 1: The tinplate exhibiting no ink loss after testing on the alkaline ultra-roughening solution production line. Figure 1 As shown; Example 2: Ink shedding on the tinplate after testing on the alkaline ultra-roughening solution production line (no ink shedding) is as follows. Figure 2 As shown; Example 3: The tinplate's ink shedding condition after testing on the alkaline ultra-roughening solution production line (no ink shedding) is as follows. Figure 3 As shown; the oil shedding of the tinplate after testing with the alkaline ultra-roughening solution in Comparative Example 1 (see the marked positions in the figure). Figure 4 As shown; the oil shedding of the tinplate after testing with the alkaline ultra-roughening solution in Comparative Example 2 (see the marked positions in the figure). Figure 5 As shown; the oil shedding of the tinplate after testing with the alkaline ultra-roughening solution in Comparative Example 3 (see marked locations in the figure). Figure 6 As shown; the oil shedding of the tinplate after testing with the alkaline ultra-roughening solution in Comparative Example 4 (see marked locations in the figure). Figure 7 As shown.

[0097] Depend on Figure 1-7 As shown in Tables 2 and 3, the lack of one or more components in the alkaline ultra-roughening solution has a significant impact on the micro-etching amount and quality. Therefore, this invention improves the AOI inspection yield of circuit boards by utilizing the interaction between ammonium sulfate, potassium chloride, ammonia, roughening and leveling agent, antioxidant, stabilizer, dispersant, accelerator, and copper surface corrosion inhibitor in the alkaline ultra-roughening solution, eliminating ink fading defects in electroless gold and electroless tin boards, and reducing quality problems such as open circuits, short circuits, and gaps in circuit boards.

[0098] II. Effect of different mass concentrations of ammonium sulfate

[0099] The difference between Comparative Examples 10 and 11 and Example 1 is the mass concentration of ammonium sulfate; all other conditions are the same. The alkaline ultra-roughening solutions of Examples 1 and 9-11 were treated with an ultra-roughening method on the production line. Each example produced 5 pnls, with a board layout of 80 units / pnl. Quality tests were then conducted on the AOI, nickel-gold plating, and tin plating processes of the circuit boards. The test results are shown in Table 4.

[0100] Table 4 Test results of Example 1 and Comparative Examples 9-11

[0101]

[0102] As shown in Table 4, the production line test results were unsatisfactory when ammonium sulfate was not added to the alkaline ultra-coarsening solution (Comparative Example 9). The production line test results were also unsatisfactory when the ammonium sulfate concentration was below 5 g / L (Comparative Example 10) or above 40 g / L (Comparative Example 11). Therefore, the preferred ammonium sulfate content in the alkaline ultra-coarsening solution is 5-40 g / L.

[0103] III. Effect of Different Mass Concentrations of Dispersant

[0104] The difference between Comparative Examples 7, 12, and 13 and Example 1 is the mass concentration of the dispersant; all other conditions are the same. The alkaline over-roughening solutions from Examples 1, 7, 12, and 13 were treated with an over-roughening method on the production line. Each example produced 5 pnls, with a board layout of 80 units / pnl. Quality tests were then conducted on the AOI, nickel-gold plating, and tin plating processes of the circuit boards. The test results are shown in Table 5.

[0105] Table 5 Test results of Example 1, Comparative Example 7, Comparative Example 12, and Comparative Example 13

[0106]

[0107] As shown in Table 5, the production line test results were unsatisfactory when no dispersant was added to the alkaline ultra-roughening solution (Comparative Example 7). The production line test results were also unsatisfactory when the dispersant concentration was below 0.1 g / L (Comparative Example 12) or above 1 g / L (Comparative Example 13). Therefore, the preferred dispersant concentration in the alkaline ultra-roughening solution is 0.1-1.0 g / L.

[0108] IV. Effects of Different Mass Concentrations of Antioxidants

[0109] The difference between Comparative Examples 5, 14, and 15 and Example 1 is the mass concentration of the antioxidant; all other conditions are the same. The alkaline ultra-roughening solutions from Examples 1, 5, 14, and 15 were treated with an ultra-roughening method on the production line. Each example produced 5 pnls, with a board layout of 80 units / pnl. Quality tests were then conducted on the AOI, nickel-gold plating, and tin plating processes of the circuit boards. The test results are shown in Table 6.

[0110] Table 6 Test results of Example 1, Comparative Example 5, Comparative Example 14, and Comparative Example 15

[0111]

[0112] As shown in Table 6, the production line test results were unsatisfactory when no antioxidant was added to the alkaline ultra-harshening solution (Comparative Example 5). The production line test results were also unsatisfactory when the antioxidant concentration was below 0.05 g / L (Comparative Example 14) or above 0.5 g / L (Comparative Example 15). Therefore, the preferred antioxidant concentration in the alkaline ultra-harshening solution is 0.05-0.5 g / L.

[0113] V. Effects of Different Mass Concentrations of Accelerator

[0114] The difference between Comparative Examples 6, 16, and 17 and Example 1 is the mass concentration of the accelerator; all other conditions are the same. The alkaline over-roughening solutions from Examples 1, 6, 16, and 17 were treated with an over-roughening method on the production line. Each example produced 5 pnls, with a board layout of 80 units / pnl. Quality tests were then conducted on the AOI, nickel-gold plating, and tin plating processes of the circuit boards. The test results are shown in Table 7.

[0115] Table 7 Test results of Example 1, Comparative Example 6, Comparative Example 16, and Comparative Example 17

[0116]

[0117] As shown in Table 7, the production line test results were unsatisfactory when no accelerator was added to the alkaline ultra-roughening solution (Comparative Example 6). The production line test results were also unsatisfactory when the accelerator concentration was below 0.2 g / L (Comparative Example 16) or above 2.0 g / L (Comparative Example 17). Therefore, the preferred accelerator concentration in the alkaline ultra-roughening solution is 0.2-2.0 g / L.

[0118] VI. Effects of Different Mass Concentrations of Stabilizer

[0119] The difference between Comparative Examples 4, 18, and 19 and Example 1 is the mass concentration of the stabilizer; all other conditions are the same. The alkaline ultra-roughening solutions from Examples 1, 4, 18, and 19 were treated with an ultra-roughening method on the production line. Each example produced 5 pnls, with a board layout of 80 units / pnl. Quality tests were then conducted on the AOI, nickel-gold plating, and tin plating processes of the circuit boards. The test results are shown in Table 8.

[0120] Table 8 Test results of Example 1, Comparative Example 4, Comparative Example 18, and Comparative Example 19

[0121]

[0122] As shown in Table 8, the production line test results were unsatisfactory when no stabilizer was added to the alkaline ultra-roughening solution (Comparative Example 4). Similarly, the production line test results were unsatisfactory when the accelerator concentration was below 0.3 g / L (Comparative Example 18) or above 1.5 g / L (Comparative Example 29). Therefore, the preferred stabilizer concentration in the alkaline ultra-roughening solution is 0.3-1.5 g / L.

[0123] VII. The Influence of Different Mass Concentrations of Copper Surface Corrosion Inhibitors

[0124] The difference between Comparative Examples 3, 20, and 21 and Example 1 is the mass concentration of the copper surface corrosion inhibitor; all other conditions are the same. The alkaline ultra-roughening solutions of Examples 1, 3, 20, and 21 were treated with an ultra-roughening method on the production line. Each example produced 5 pnls, with a board layout of 80 units / pnl. Quality tests were then conducted on the AOI, nickel plating, and immersion tin processes of the circuit boards. The test results are shown in Table 9.

[0125] Table 9 Test results of Example 1, Comparative Example 3, Comparative Example 20, and Comparative Example 21

[0126]

[0127] As shown in Table 9, the production line test results were unsatisfactory when no copper surface corrosion inhibitor was added to the alkaline ultra-roughening solution (Comparative Example 3). The production line test results were also unsatisfactory when the mass concentration of the copper surface corrosion inhibitor was below 0.1 g / L (Comparative Example 20) or above 1.0 g / L (Comparative Example 21). Therefore, the preferred mass concentration of the copper surface corrosion inhibitor in the alkaline ultra-roughening solution is 0.1-1.0 g / L.

[0128] 8. Effect of different mass ratios of roughening and leveling agents and dispersants

[0129] The difference between Comparative Examples 22 and 23 and Example 1 is the mass ratio of the roughening and leveling agent and the dispersant; all other conditions are the same. The alkaline ultra-roughening solutions of Examples 1, 22, and 23 were treated with an ultra-roughening method on the production line. Each example produced 5 pnls, with a board layout of 80 units / pnl. Quality tests were then conducted on the AOI, nickel plating, and tin plating processes of the circuit boards. The test results are shown in Table 10.

[0130] Table 10 Test results of Example 1, Comparative Example 22, and Comparative Example 23

[0131]

[0132] As shown in Table 10, the test results are unsatisfactory when the proportion of dispersant in the mass ratio of roughening and leveling agent to dispersant in the alkaline ultra-roughening solution is small (Comparative Example 22) or large (Comparative Example 23). Therefore, the preferred mass ratio of roughening and leveling agent to dispersant in the alkaline ultra-roughening solution is 1:(0.02-0.4).

[0133] IX. The effect of hydrochloric acid washing on quality after ultra-roughening with alkaline ultra-roughening solution

[0134] After preparation using the alkaline ultra-roughening solution method in Example 1, the solution was normally treated with an ultra-roughening method on the production line. After ultra-roughening, it was washed with hydrochloric acid and not washed with hydrochloric acid, producing a total of 5 pnls. The board layout was 80 units / pnl. The subsequent processes were carried out normally. Then, the quality of the AOI, nickel plating, and tin plating processes of the circuit boards was tested. The test results are shown in Table 11.

[0135] Table 11 Test Results

[0136]

[0137] In summary, the alkaline ultra-roughening solution, its preparation method, and the ultra-roughening method provided by this invention can enhance the adhesion between the dry film and the solder resist ink and the copper layer, improve the problem of solder tin board oil shedding, completely improve copper surface oxidation, improve the yield of AOI process, eliminate the need for hydrochloric acid washing after ultra-roughening, improve production efficiency and reduce costs, and ensure stable quality.

[0138] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in the present invention, and these modifications or substitutions should all be covered within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. An alkaline ultra-coarsening solution, characterized in that, It consists of the following components in mass concentration: ammonium sulfate 5-40 g / L, potassium chloride 2-10 g / L, ammonia water 5-20 g / L, roughening and leveling agent 2-10 g / L, antioxidant 0.05-0.5 g / L, stabilizer 0.3-1.5 g / L, dispersant 0.1-1.0 g / L, accelerator 0.2-2.0 g / L, copper surface corrosion inhibitor 0.1-1.0 g / L, with the balance being deionized water; The roughening and leveling agent is selected from at least one of 2-mercaptothiazoline, fluoropolyether modified polysiloxane, ammonium molybdate, and 2-mercaptobenzimidazole; The antioxidant is selected from at least one of sodium sulfite, sodium thiosulfate, and cysteine; The stabilizer is selected from at least one of polyacrylamide, betaine, and sodium fatty alcohol polyoxyethylene ether sulfate; The dispersant is selected from at least one of sodium polyacrylate, fatty acid polyoxyethylene ether, alkylphenol polyoxyethylene ether, and dodecyl dimethyl betaine; The accelerator is selected from at least one of 2-mercapto-1-methylimidazolium, thiazolidin-2-thione, and 4,6-dimethyl-2-mercaptopyrimidine; The copper surface corrosion inhibitor is selected from at least one of sodium silicate, hexamethyleneamine, dodecylamine, and sodium polyphosphate; The mass ratio of the roughening and leveling agent to the dispersant is 1:(0.02-0.4).

2. The alkaline ultra-coarsening solution as described in claim 1, characterized in that, The mass concentration of the dispersant is 0.4-0.6 g / L.

3. The alkaline ultra-coarsening solution as described in claim 1, characterized in that, The mass concentration of the stabilizer is 0.8-1.0 g / L.

4. The alkaline ultra-coarsening solution as described in claim 1, characterized in that, It consists of the following components in mass concentration: ammonium sulfate 18-24 g / L, potassium chloride 4-6 g / L, ammonia water 10-12 g / L, roughening and leveling agent 4-6 g / L, antioxidant 0.2-0.3 g / L, stabilizer 0.8-1.0 g / L, dispersant 0.4-0.6 g / L, accelerator 0.8-1.2 g / L, copper surface corrosion inhibitor 0.4-0.6 g / L, with the balance being deionized water.

5. The alkaline ultra-coarsening solution as described in claim 1, characterized in that, It consists of the following components in mass concentration: ammonium sulfate 20 g / L, potassium chloride 5 g / L, ammonia 11 g / L, roughening and leveling agent 5 g / L, antioxidant 0.25 g / L, stabilizer 0.9 g / L, dispersant 0.5 g / L, accelerator 1.0 g / L, copper surface corrosion inhibitor 0.5 g / L, with the balance being deionized water.

6. The method for preparing the alkaline ultra-coarsening solution according to any one of claims 1-5, characterized in that, Includes the following steps: Ammonium sulfate, potassium chloride, ammonia, roughening and leveling agent, antioxidant, stabilizer, dispersant, accelerator, and copper surface corrosion inhibitor are added to deionized water and mixed evenly to obtain the alkaline ultra-roughening solution.

7. A method for overcoarsening, characterized in that, The process includes the following steps: using the alkaline ultra-roughening solution described in any one of claims 1-5, the copper surface of the circuit board is micro-etched by horizontal spraying.

8. The over-coarsening method as described in claim 7, characterized in that, The spray pressure of the horizontal line spray mode is 1.5-2.5 kg / cm 2 The plate surface etching time is 40-80 s.

9. The over-coarsening method as described in claim 7, characterized in that, The temperature for the micro-etching of the plate surface is 25-35℃.

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