Environment-friendly titanium alloy etching solution and preparation method and etching method thereof

Abstract

The invention discloses an environment-friendly titanium alloy etching solution as well as a preparation method and an etching method thereof, and relates to the technical field of printed circuit board production. The environment-friendly titanium alloy etching solution comprises the following components in percentage by mass: 10-30% of ammonium fluoride, 5-15% of an oxidant, 0.1-1% of a wetting agent, 0.3-1.5% of a stabilizer, 2-10% of an accelerator and 0.5-3% of a lateral erosion inhibitor. The stabilizer is selected from at least one of Tween 20, Tween 40 and Tween 85; and the accelerator is selected from at least one of sodium methylene dinaphthalene sulfonate, sodium dibutyl naphthalene sulfonate and dodecyl benzoate. The environment-friendly titanium alloy etching solution disclosed by the invention can selectively and quickly etch titanium alloy without corroding a copper surface and other metals, so that etching factors are effectively increased, and the problem of lateral erosion of a fine circuit is solved. Meanwhile, ammonium fluoride is used as a main agent of the etching liquid instead of hydrofluoric acid, so that the environmental pollution can be effectively reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of printed circuit board production, and particularly relates to an environmentally friendly titanium alloy etching solution, a preparation method thereof, and an etching method. Background Art

[0002] With the development of the global economy, especially the rapid development in high-tech fields such as aerospace, military, medical, and electronics, the demand for titanium alloy materials in these fields has been continuously increasing. Due to its high strength, low density, excellent corrosion resistance, and biocompatibility, titanium alloy has become an indispensable material in these fields. As a key technology in the processing of titanium alloy, the importance of titanium alloy etching solution is self-evident. However, the development of the industry has been significantly affected by global environmental protection regulations. With the enhancement of environmental awareness, governments around the world have successively introduced a series of environmental protection regulations, putting forward higher requirements for industrial emissions. In recent years, due to the expansion of the titanium alloy etching solution market and the surge in demand for high-performance electronic products, higher requirements have been put forward for the accuracy, stability, and environmental protection of the etching solution.

[0003] The development of titanium alloy etching solution is also promoted by technological innovation. With the continuous breakthroughs in cutting-edge technologies such as nanotechnology and green chemistry, the production process has been significantly improved. The research and application of new environmentally friendly titanium alloy etching solutions not only improve the etching efficiency, reduce the production cost, but also reduce environmental pollution. Technological innovation has brought new development opportunities for titanium alloy etching solutions, and at the same time put forward higher requirements for enterprises. In order to improve the etching effect and production efficiency of titanium alloy etching solutions, new technical means and methods will continue to emerge. Developing more efficient additives to improve the etching speed and selectivity of the etching solution, and researching more environmentally friendly and safe new etching solutions to replace traditional etching solutions have become the future development trend. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides an environmentally friendly titanium alloy etching solution, a preparation method thereof, and an etching method. This environmentally friendly titanium alloy etching solution can selectively and rapidly etch titanium alloy, does not etch the copper surface and other metals, effectively improves the etching factor, and improves the side etching problem of fine lines. At the same time, since ammonium fluoride is used instead of hydrofluoric acid as the main agent of the etching solution, environmental pollution can be effectively reduced.

[0005] Specifically, it includes the following technical solutions: In the first aspect, an environmentally friendly titanium alloy etching solution is provided, including the following components in mass percentage: Ammonium fluoride 10 - 30%, oxidant 5 - 15%, wetting agent 0.1 - 1%, stabilizer 0.3 - 1.5%, accelerator 2 - 10%, side etching inhibitor 0.5 - 3%; The oxidant is selected from at least one of nitric acid, sulfuric acid, and hydrogen peroxide; The wetting agent described above is selected from at least one of dioctyl sulfosuccinate, fatty alcohol polyoxyethylene ether, and sodium lauryl ether sulfate; The stabilizer described above is selected from at least one of Tween 20, Tween 40, and Tween 85: The accelerator described above is selected from at least one of sodium methylene bisnaphthalene sulfonate, sodium dibutylnaphthalene sulfonate, and dodecyl benzoate; The side-etch inhibitor described above is selected from at least one of benzotriazole, methylbenzotriazole, sodium mercaptobenzothiazole, and benzyltriethylammonium chloride.

[0006] Preferably, the oxidizing agent described above is selected from at least one of nitric acid (mass concentration 69%), sulfuric acid (mass concentration 98%), and hydrogen peroxide (mass concentration 50%).

[0007] Furthermore, the mass ratio of the accelerator to the stabilizer is 1:(0.05 - 0.3).

[0008] Furthermore, the mass percentage of the accelerator in the environmentally friendly titanium alloy etching solution is 5 - 7%.

[0009] Furthermore, the mass percentage of the stabilizer in the environmentally friendly titanium alloy etching solution is 0.6 - 1.0%.

[0010] Furthermore, the mass percentage of ammonium fluoride in the environmentally friendly titanium alloy etching solution is 18 - 22%.

[0011] Furthermore, the environmentally friendly titanium alloy etching solution consists of the following components by mass percentage: ammonium fluoride 18 - 22%, oxidizing agent 8 - 12%, wetting agent 0.4 - 0.6%, stabilizer 0.8 - 1.2%, accelerator 5 - 7%, side-etch inhibitor 1.5 - 2%, and the balance is water.

[0012] In a second aspect, there is provided a method for preparing the environmentally friendly titanium alloy etching solution as described in the first aspect, including the following steps: adding ammonium fluoride, oxidizing agent, wetting agent, stabilizer, accelerator, and side-etch inhibitor to water and mixing evenly to obtain the environmentally friendly titanium alloy etching solution.

[0013] In a third aspect, there is provided an etching method for the environmentally friendly titanium alloy etching solution as described in the first aspect, including the following steps: using the environmentally friendly titanium alloy etching solution as described in the first aspect, etching the circuit board by horizontal spraying at a temperature of 40 - 60°C for an etching time of 0.5 - 1.5 min.

[0014] Furthermore, the spraying pressure of the horizontal spraying is 1.5 - 2.5 kg / cm 2 , and the etching speed is 4 - 8 m / min.

[0015] Further, the temperature is 45 - 55°C and the etching rate is 5 - 7 m / min.

[0016] Preferably, the initial charge amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is at a concentration of 100 wt%.

[0017] Preferably, both the line width and line pitch of the circuit board are 30 μm.

[0018] The beneficial effects of the present invention are as follows: (1) The environmentally friendly titanium alloy etching solution uses low-toxic or non-toxic chemical components, reducing environmental pollution. And it can provide a more stable etching effect, reducing fluctuations during the etching process, thereby improving processing efficiency and precision. By optimizing the formula of the etching solution and the etching method, material consumption and energy consumption during the etching process can be reduced, thus lowering the overall processing cost; (2) Through the interaction of the active components in the environmentally friendly titanium alloy etching solution, an oxide film will be formed on other metals except titanium alloy during the etching process. This oxide film can effectively prevent other metals from being corroded, while the etching solution can selectively etch only titanium metal without damaging other metals; (3) The side-etching additive generates an insoluble passivation film on metals other than titanium metal during the etching reaction. The pressure of the etching copper wire nozzle can break through this passivation film from the front, but for both sides of the circuit, due to insufficient pressure, the passivation film can be maintained, thus achieving the purpose of reducing side etching. Description of the Drawings

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for description in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0020] Figure 1 It is a schematic diagram of the etching factor calculation method; Figure 2 It is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Embodiment 1 of the present invention; Figure 3 It is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Embodiment 2 of the present invention; Figure 4 It is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Embodiment 3 of the present invention; Figure 5 It is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Embodiment 4 of the present invention; Figure 6 It is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Comparative Example 1 of the present invention; Figure 7 This is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Comparative Example 2 of the present invention; Figure 8 This is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Comparative Example 3 of the present invention; Figure 9 This is the effect diagram of the production line test of the environmentally friendly titanium alloy etching solution in Comparative Example 4 of the present invention. Detailed implementation manners

[0021] Next, the technical solutions in the embodiments of the present invention will be described clearly and completely. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0022] It should be understood that when used in this specification and the appended claims, the terms "comprises" and "comprising" indicate the presence of the described features, wholes, steps, operations, elements, and / or components, but do not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components, and / or their combinations.

[0023] It should also be understood that the terms used in this specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. As used in this specification of the present invention and the appended claims, unless the context clearly indicates otherwise, the singular forms "a", "an", and "the" are intended to include the plural forms.

[0024] It should be further understood that the term " / and" used in this specification of the present invention and the appended claims refers to any combination and all possible combinations of one or more of the associated listed items, and includes these combinations.

[0025] To more fully understand the technical content of the present invention, the technical solutions of the present invention will be further introduced and described below in conjunction with specific embodiments.

[0026] Unless otherwise specified, "%" in the present invention is the mass percentage.

[0027] The etching method of the environmentally friendly titanium alloy etching solution includes the following steps: S1 Loading the board; S2 Swelling; S3 Stripping the film; S4 Washing with water; S5 Etching; S6 Washing with water; S7 Drying; S8 Unloading the board.

[0028] Among them, the S5 etching step is as follows: First, use an environmentally friendly titanium alloy etching solution to open the etching machine's chemical solution tank and heat it up to 40 - 60°C. Then, perform a film stripping treatment on the circuit board and etch it at an etching speed of 4 - 8 m / min in the form of horizontal line spraying, with a spraying pressure of 1.5 - 2.5 kg / cm 2 , and the etching time is 0.5 - 1.5 min.

[0029] Preferably, the spraying pressure is 1.8 - 2.2 kg / cm 2 , the temperature is 45 - 55°C, and the etching speed is 5 - 7 m / min.

[0030] Preferably, the opening amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is 100 wt% concentration.

[0031] Preferably, both the line width and line pitch of the circuit board are 30 μm.

[0032] Effect verification test of environmentally friendly titanium alloy etching solution (production line test): After the environmentally friendly titanium alloy etching solutions of the examples and comparative examples are processed by the etching method of the environmentally friendly titanium alloy etching solution, normal etching tests are carried out on the etching production line, and 5 pnl are produced for each. The circuit boards are sliced, and the etching effect of the lines is observed with a microscope. The etching rate (μm / min), open circuit ratio, short circuit ratio, notch ratio, etching amount (μm), and etching factor are tested. Among them, the reasonable range of the etching rate is 3 - 5, the reasonable range of the open circuit ratio is 0 - 0.5%, the reasonable range of the short circuit ratio is 0 - 0.3%, the reasonable range of the notch ratio is 0 - 0.2%, the reasonable range of the side etching amount is 0 - 5, and the reasonable range of the etching factor is 5 - 12. The etching factor of 5 - 10 levels is considered qualified, and the etching factor of 1 - 4 levels is considered unqualified.

[0033] Among them, the slicing production process of the circuit board line type effect diagram is as follows: sampling → resin infusion → grinding and slicing → microscopic observation → photographing → saving pictures.

[0034] The schematic diagram of the etching factor calculation method is as Figure 1 shown, where E = V / X, E is the etching factor, V is the etching depth, and X is the side etching depth (measured from the width of the groove at the resist edge to the thinnest copper waist).

[0035] Example 1 An environmentally friendly titanium alloy etching solution is composed of the following components by mass percentage: Ammonium fluoride 18%, oxidant 8% (nitric acid with a mass concentration of 69%), wetting agent 0.4% (dioctyl sulfosuccinate), stabilizer 0.8% (Tween 20), accelerator 5% (sodium methylene dinaphthalene sulfonate), side etching inhibitor 1.5% (benzotriazole), and the balance is deionized water.

[0036] The preparation method of the environmentally friendly titanium alloy etching solution includes the following steps: adding ammonium fluoride, an oxidizing agent, a wetting agent, a stabilizer, an accelerator, and a side-etching inhibitor into water and mixing evenly to obtain the environmentally friendly titanium alloy etching solution.

[0037] The etching method of the environmentally friendly titanium alloy etching solution includes the following steps: S1 Loading the board; S2 Swelling; S3 Stripping the film; S4 Washing with water; S5 Etching; S6 Washing with water; S7 Drying; S8 Unloading the board.

[0038] Among them, the S5 etching step is as follows: First, use the environmentally friendly titanium alloy etching solution to carry out chemical solution tank filling in the etching machine and heat up to 48 °C. Then, perform film stripping treatment on the circuit board and etch it at an etching speed of 6 m / min in the way of horizontal line spraying, and the spraying pressure is 1.5 kg / cm 2 , the etching time is 1.0 min, and the line width and line pitch of the circuit board are both 30 μm. The tank filling amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is 100 wt% concentration.

[0039] The preparation method of the environmentally friendly titanium alloy etching solution in Examples 2 - 9 is the same as that in Example 1.

[0040] Example 2 An environmentally friendly titanium alloy etching solution is composed of the following components in mass percentage: Ammonium fluoride 19%, oxidizing agent 8% (sulfuric acid with a mass concentration of 98%), wetting agent 0.5% (fatty alcohol polyoxyethylene ether), stabilizer 0.8% (Tween 40), accelerator 6% (sodium dibutylnaphthalenesulfonate), side-etching inhibitor 1.5% (benzotriazole), and the balance is deionized water.

[0041] The difference between the etching method of the environmentally friendly titanium alloy etching solution in Example 2 and that in Example 1 is that the S5 etching step in Example 2 is as follows: First, use the environmentally friendly titanium alloy etching solution to carry out chemical solution tank filling in the etching machine and heat up to 52 °C. Then, perform film stripping treatment on the circuit board and etch it at an etching speed of 6 m / min in the way of horizontal line spraying, and the spraying pressure is 1.8 kg / cm 2 , the etching time is 1.0 min, and the line width and line pitch of the circuit board are both 30 μm. The tank filling amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is 100 wt% concentration.

[0042] Example 3 An environmentally friendly titanium alloy etching solution is composed of the following components in mass percentage: Ammonium fluoride 21%, oxidizer 10% (hydrogen peroxide with a mass concentration of 50%), wetting agent 0.5% (fatty alcohol polyoxyethylene ether), stabilizer 1.0% (Tween 40), accelerator 6% (sodium dibutylnaphthalenesulfonate), side-etch inhibitor 1.5% (benzotriazole), and the balance is deionized water.

[0043] The difference in the etching method of the environmentally friendly titanium alloy etching solution in Example 3 from that in Example 1 is that the S5 etching step in Example 3 is as follows: First, use the environmentally friendly titanium alloy etching solution to open the tank of the etching machine and heat it up to 55 °C. Then, perform a film stripping treatment on the circuit board, and etch it at an etching speed of 6 m / min in the form of horizontal line spraying, with a spraying pressure of 1.8 kg / cm 2 , the etching time is 1.0 min, and the line width and line pitch of the circuit board are both 30 μm. The opening amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is 100 wt% concentration.

[0044] Example 4 An environmentally friendly titanium alloy etching solution is composed of the following components in mass percentage: Ammonium fluoride 18%, oxidizer 11% (sulfuric acid with a mass concentration of 98%), wetting agent 0.5% (fatty alcohol polyoxyethylene ether), stabilizer 0.8% (Tween 85), accelerator 6% (dodecyl benzoate), side-etch inhibitor 1.7% (methylbenzotriazole), and the balance is deionized water.

[0045] The difference in the etching method of the environmentally friendly titanium alloy etching solution in Example 4 from that in Example 1 is that the S5 etching step in Example 4 is as follows: First, use the environmentally friendly titanium alloy etching solution to open the tank of the etching machine and heat it up to 51 °C. Then, perform a film stripping treatment on the circuit board, and etch it at an etching speed of 6 m / min in the form of horizontal line spraying, with a spraying pressure of 2.0 kg / cm 2 , the etching time is 1.0 min, and the line width and line pitch of the circuit board are both 30 μm. The opening amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is 100 wt% concentration.

[0046] Example 5 An environmentally friendly titanium alloy etching solution is composed of the following components in mass percentage: Ammonium fluoride 22%, oxidizer 11% (nitric acid with a mass concentration of 69%), wetting agent 0.6% (sodium fatty alcohol polyoxyethylene ether sulfate), stabilizer 0.8% (Tween 20), accelerator 5% (sodium dibutylnaphthalenesulfonate), side-etch inhibitor 2% (sodium mercaptobenzothiazole), and the balance is deionized water.

[0047] The difference between the etching method of the environmentally friendly titanium alloy etching solution in Example 5 and that in Example 1 is that the S5 etching step in Example 5 is as follows: First, use the environmentally friendly titanium alloy etching solution to open the chemical solution in the etching machine and heat it up to 55 °C. Then, perform a film stripping treatment on the circuit board and etch it at an etching speed of 6 m / min in the form of horizontal line spraying, with a spraying pressure of 2.4 kg / cm 2 , the etching time is 1.0 min, and the line width and line pitch of the circuit board are both 30 μm. The opening amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is 100 wt% concentration.

[0048] Example 6 An environmentally friendly titanium alloy etching solution is composed of the following components by mass percentage: Ammonium fluoride 20%, oxidant 10% (nitric acid with a mass concentration of 69%), wetting agent 0.6% (sodium dodecyl polyoxyethylene sulfate), stabilizer 1.2% (Tween 40), accelerator 7% (dodecyl benzoate), side-etching inhibitor 1.9% (sodium mercaptobenzothiazole), and the balance is deionized water.

[0049] The difference between the etching method of the environmentally friendly titanium alloy etching solution in Example 6 and that in Example 1 is that the S5 etching step in Example 6 is as follows: First, use the environmentally friendly titanium alloy etching solution to open the chemical solution in the etching machine and heat it up to 52 °C. Then, perform a film stripping treatment on the circuit board and etch it at an etching speed of 6 m / min in the form of horizontal line spraying, with a spraying pressure of 2.5 kg / cm 2 , the etching time is 1 min, and the line width and line pitch of the circuit board are both 30 μm. The opening amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is 100 wt% concentration.

[0050] Example 7 An environmentally friendly titanium alloy etching solution is composed of the following components by mass percentage: Ammonium fluoride 19%, oxidant 9% (hydrogen peroxide with a mass concentration of 50%), wetting agent 0.4% (dioctyl sulfosuccinate), stabilizer 0.8% (Tween 85), accelerator 6% (sodium methylene bisnaphthalene sulfonate), side-etching inhibitor 1.8% (benzotriazole), and the balance is deionized water.

[0051] The difference between the etching method of the environmentally friendly titanium alloy etching solution in Example 7 and that in Example 1 is that the S5 etching step in Example 7 is as follows: First, use the environmentally friendly titanium alloy etching solution to open the chemical solution in the etching machine and heat it up to 54 °C. Then, perform a film stripping treatment on the circuit board and etch it at an etching speed of 6 m / min in the form of horizontal line spraying, with a spraying pressure of 2.2 kg / cm 2, the etching time is 1.0 min, and both the line width and line pitch of the circuit board are 30 μm. The initial charge amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is at a concentration of 100 wt%.

[0052] Example 8 An environmentally friendly titanium alloy etching solution is composed of the following components by mass percentage: Ammonium fluoride 22%, oxidizing agent 10% (nitric acid with a mass concentration of 69%), wetting agent 0.6% (dioctyl sulfosuccinate), stabilizer 1.1% (Tween 40), accelerator 6% (dodecyl benzoate), side-etching inhibitor 1.9% (benzyltriethylammonium chloride), and the balance is deionized water.

[0053] The difference in the etching method of the environmentally friendly titanium alloy etching solution in Example 8 from that in Example 1 lies in that the S5 etching step in Example 8 is as follows: First, use the environmentally friendly titanium alloy etching solution to perform chemical solution initial charge in the etching machine and heat up to 50 °C. Then, perform the film stripping treatment on the circuit board, and perform etching at an etching speed of 6 m / min in the form of horizontal line spraying, and the spraying pressure is 2.3 kg / cm 2 , the etching time is 1.0 min, and both the line width and line pitch of the circuit board are 30 μm. The initial charge amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is at a concentration of 100 wt%.

[0054] Example 9 An environmentally friendly titanium alloy etching solution is composed of the following components by mass percentage: Ammonium fluoride 22%, oxidizing agent 10% (sulfuric acid with a mass concentration of 98%), wetting agent 0.5% (aliphatic alcohol polyoxyethylene ether), stabilizer 1.2% (Tween 20), accelerator 6% (dodecyl benzoate), side-etching inhibitor 2% (benzyltriethylammonium chloride), and the balance is deionized water.

[0055] The difference in the etching method of the environmentally friendly titanium alloy etching solution in Example 9 from that in Example 1 lies in that the S5 etching step in Example 9 is as follows: First, use the environmentally friendly titanium alloy etching solution to perform chemical solution initial charge in the etching machine and heat up to 55 °C. Then, perform the film stripping treatment on the circuit board, and perform etching at an etching speed of 6 m / min in the form of horizontal line spraying, and the spraying pressure is 2.3 kg / cm 2 , the etching time is 1.0 min, and both the line width and line pitch of the circuit board are 30 μm. The initial charge amount of the environmentally friendly titanium alloy etching solution in the etching of the circuit board is at a concentration of 100 wt%.

[0056] To better illustrate the technical effects of the present invention, Comparative Examples 1-9 are set on the basis of Example 1, and the differences between Comparative Examples 1-9 and Example 1 are shown in Table 1 below: Table 1 Differences between Comparative Examples 1-9 and Example 1

[0057] The differences between Comparative Examples 1-9 and Example 1 are only in the components of the environmentally friendly titanium alloy etching solution, and the other conditions are the same.

[0058] To further illustrate the technical effects of the present invention, the following tests are carried out for verification.

[0059] I. Verification Test on the Composition Effect of Environmentally Friendly Titanium Alloy Etching Solution 1) The environmentally friendly titanium alloy etching solutions of Examples 1-9 are subjected to production line tests, and the test results are shown in Table 2: Table 2 Production Line Test Results of Environmentally Friendly Titanium Alloy Etching Solutions of Examples 1-9

[0060] 2) The environmentally friendly titanium alloy etching solutions of Comparative Examples 1-9 are subjected to production line tests, and the test results are shown in Table 3: Table 3 Production Line Test Results of Environmentally Friendly Titanium Alloy Etching Solutions of Comparative Examples 1-9

[0061] Among them, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Example 1 of the present invention are as Figure 2 shown, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Example 2 of the present invention are as Figure 3 shown, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Example 3 of the present invention are as Figure 4 shown, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Example 4 of the present invention are as Figure 5 shown, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Comparative Example 1 of the present invention are as Figure 6 shown, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Comparative Example 2 of the present invention are as Figure 7 shown, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Comparative Example 3 of the present invention are as Figure 8 shown, the effect diagrams of the production line tests of the environmentally friendly titanium alloy etching solution of Comparative Example 4 of the present invention are as Figure 9 shown.

[0062] From Figures 2 - 9 and the test results in Tables 2-3, it can be seen that when one or more components are missing in the environmentally friendly titanium alloy etching solution, it has a very great impact on the etching rate and quality. Thus, it can be seen that the present invention improves the etching rate of high-precision titanium alloy circuit boards and reduces quality problems such as open circuits, short circuits, and notches in circuit boards through the interaction between ammonium fluoride, oxidant, wetting agent, stabilizer, accelerator, and side-etch inhibitor in the environmentally friendly titanium alloy etching solution.

[0063] II. Influence of Different Mass Percentages of Ammonium Fluoride Examples 9 - 11 are different from Example 1 in the mass percentage of ammonium fluoride, and the other conditions are the same. The production line tests were carried out on the environmentally friendly titanium alloy etching solutions of Example 1 and Comparative Examples 9 - 11, and the test results are shown in Table 4: Table 4 Production Line Test Results of the Environmentally Friendly Titanium Alloy Etching Solutions of Example 1 and Comparative Examples 9 - 11

[0064] It can be seen from the test results in Table 4 that when ammonium fluoride is not added to the environmentally friendly titanium alloy etching solution (Comparative Example 9), the production line test results are not ideal. When the mass percentage of ammonium fluoride is less than 10% (Comparative Example 10) or higher than 30% (Comparative Example 11), the production line test results are not ideal. Therefore, the mass percentage (mass concentration) of ammonium fluoride in the environmentally friendly titanium alloy etching solution is preferably 10 - 30%.

[0065] III. Influence of Different Mass Percentages of Oxidizing Agent Comparative Example 7, Comparative Examples 12 - 13 are different from Example 1 in the mass percentage of the oxidizing agent, and the other conditions are the same. The production line tests were carried out on the environmentally friendly titanium alloy etching solutions of Example 1, Comparative Example 7 and Comparative Examples 12 - 13, and the test results are shown in Table 5: Table 5 Production Line Test Results of Example 1, Comparative Example 7 and Comparative Examples 12 - 13

[0066] It can be seen from the test results in Table 5 that when the oxidizing agent is not added to the environmentally friendly titanium alloy etching solution (Comparative Example 7), the production line test results are not ideal. When the mass percentage of the oxidizing agent is less than 5% (Comparative Example 12) or higher than 15% (Comparative Example 13), the production line test results are not ideal. Therefore, the mass percentage of the oxidizing agent in the environmentally friendly titanium alloy etching solution is preferably 5 - 15%.

[0067] IV. Influence of Different Mass Percentages of Wetting Agent Comparative Example 5, Comparative Examples 14 - 15 are different from Example 1 in the mass percentage of the wetting agent, and the other conditions are the same. The production line tests were carried out on the environmentally friendly titanium alloy etching solutions of Example 1, Comparative Example 5 and Comparative Examples 14 - 15, and the test results are shown in Table 6: Table 6 Production Line Test Results of Example 1, Comparative Example 5 and Comparative Examples 14 - 15

[0068] As can be seen from the test results in Table 6, when the wetting agent is not added to the environmentally friendly titanium alloy etching solution (Comparative Example 5), the production line test results are not ideal. When the mass percentage of the wetting agent is less than 0.1% (Comparative Example 14) or higher than 1% (Comparative Example 15), the production line test results are not ideal. Therefore, the mass percentage of the wetting agent in the environmentally friendly titanium alloy etching solution is preferably 0.1 - 1.0%.

[0069] V. Influence based on different mass percentages of stabilizer In Comparative Example 4, Comparative Examples 16 - 17, the difference from Example 1 is the mass percentage of the stabilizer, and the remaining conditions are the same. The environmentally friendly titanium alloy etching solutions of Example 1, Comparative Example 4, and Comparative Examples 16 - 17 were tested on the production line, and the test results are shown in Table 7: Table 7 Production line test results of Example 1, Comparative Example 4, and Comparative Examples 16 - 17

[0070] As can be seen from the test results in Table 7, when the stabilizer is not added to the environmentally friendly titanium alloy etching solution (Comparative Example 4), the production line test results are not ideal. When the mass percentage of the stabilizer is less than 0.3% (Comparative Example 16) or higher than 1.5% (Comparative Example 17), the production line test results are not ideal. Therefore, the mass percentage of the stabilizer in the environmentally friendly titanium alloy etching solution is preferably 0.3 - 1.5%.

[0071] VI. Influence based on different mass percentages of accelerator In Comparative Example 6, Comparative Examples 18 - 19, the difference from Example 1 is the mass percentage of the accelerator, and the remaining conditions are the same. The environmentally friendly titanium alloy etching solutions of Example 1, Comparative Example 6, and Comparative Examples 18 - 19 were tested on the production line, and the test results are shown in Table 8: Table 8 Production line test results of Example 1, Comparative Example 6, and Comparative Examples 18 - 19

[0072] As can be seen from the test results in Table 8, when the accelerator is not added to the environmentally friendly titanium alloy etching solution (Comparative Example 6), the production line test results are not ideal. When the mass percentage of the accelerator is less than 2% (Comparative Example 18) or higher than 10% (Comparative Example 19), the production line test results are not ideal. Therefore, the mass percentage of the accelerator in the environmentally friendly titanium alloy etching solution is preferably 2 - 10%.

[0073] VII. Influence based on different mass percentages of side - etching inhibitor In Comparative Example 8, Comparative Examples 20 - 21, the difference from Example 1 is the mass percentage of the side - etching inhibitor, and the remaining conditions are the same. The environmentally friendly titanium alloy etching solutions of Example 1, Comparative Example 8, and Comparative Examples 20 - 21 were tested on the production line, and the test results are shown in Table 9: Table 9 Production line test results of Example 1, Comparative Example 8 and Comparative Examples 20-21

[0074] As can be seen from the test results in Table 9, when no side-etch inhibitor is added to the environmentally friendly titanium alloy etching solution (Comparative Example 8), the production line test results are not ideal. When the mass percentage of the side-etch inhibitor is lower than 0.5% (Comparative Example 20) or higher than 3% (Comparative Example 21), the production line test results are not ideal. Therefore, the mass percentage of the side-etch inhibitor in the environmentally friendly titanium alloy etching solution is preferably 0.5 - 3%.

[0075] VIII. Influence based on different mass ratios of accelerator and stabilizer Comparative Examples 22 - 23 are different from Example 1 in the mass ratio of the accelerator and the stabilizer, and the other conditions are the same. The environmentally friendly titanium alloy etching solutions of Example 1 and Comparative Examples 22 - 23 were subjected to production line tests, and the test results are shown in Table 10: Table 10 Production line test results of the environmentally friendly titanium alloy etching solutions of Example 1 and Comparative Examples 22 - 23

[0076] As can be seen from the test results in Table 10, when the proportion of the stabilizer in the mass ratio of the accelerator to the stabilizer in the environmentally friendly titanium alloy etching solution is relatively small (Comparative Example 22) or when the proportion of the stabilizer in the mass ratio of the accelerator to the stabilizer is relatively large (Comparative Example 23), the production line test results are not ideal. Therefore, the mass ratio of the accelerator to the stabilizer in the new environmentally friendly titanium alloy etching solution is preferably 1:(0.05 - 0.3).

[0077] In summary, the environmentally friendly titanium alloy etching solution provided by the present invention can selectively etch titanium alloy rapidly, does not etch the copper surface and other metals, effectively improves the etching factor and improves the side-etch problem of fine lines, and has an obvious effect on improving the yield of production boards. Using ammonium fluoride instead of hydrofluoric acid as the main agent of the etching solution can effectively reduce environmental pollution.

[0078] The above is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention can easily think of various equivalent modifications or substitutions, and these modifications or substitutions should all be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. An environmentally friendly titanium alloy etching solution, characterized in that: Includes the following mass percentage components: Ammonium fluoride 10-30%, oxidant 5-15%, wetting agent 0.1-1%, stabilizer 0.3-1.5%, accelerator 2-10%, side corrosion inhibitor 0.5-3%; The oxidant is selected from at least one of nitric acid, sulfuric acid and hydrogen peroxide; The wetting agent is selected from at least one of dioctyl sodium sulfosuccinate, fatty alcohol polyoxyethylene ether, and fatty alcohol polyoxyethylene ether sodium sulfate; The stabilizer is selected from at least one of Tween 20, Tween 40 and Tween 85: The accelerator is selected from at least one of sodium methylene dinaphthalene sulfonate, sodium dibutylnaphthalene sulfonate, and dodecanol benzoate; The lateral corrosion inhibitor is selected from at least one of benzotriazole, tolutriazole, sodium mercaptobenzothiazole and benzyltriethylammonium chloride.

2. The environmentally friendly titanium alloy etching solution according to claim 1, characterized in that: The mass ratio of the accelerator to the stabilizer is 1:(0.05-0.3).

3. The environmentally friendly titanium alloy etching solution according to claim 1, characterized in that: The mass percentage of the accelerator in the environmentally friendly titanium alloy etching solution is 5-7%.

4. The environmentally friendly titanium alloy etching solution according to claim 1, characterized in that: The mass percentage of the stabilizer in the environmentally friendly titanium alloy etching solution is 0.6-1.0%.

5. The environmentally friendly titanium alloy etching solution according to claim 1, characterized in that: The mass percentage of the ammonium fluoride in the environmentally friendly titanium alloy etching solution is 18-22%.

6. The environmentally friendly titanium alloy etching solution according to claim 1, characterized in that: The invention is composed of the following components in percentage by weight: 18-22% of ammonium fluoride, 8-12% of oxidant, 0.4-0.6% of wetting agent, 0.8-1.2% of stabilizer, 5-7% of accelerator, 1.5-2% of side corrosion inhibitor, and the balance of water.

7. The method for preparing the environmentally friendly titanium alloy etching solution according to any one of claims 1 to 6, characterized in that: The following steps are involved: Ammonium fluoride, an oxidant, a wetting agent, a stabilizer, an accelerator, and a side corrosion inhibitor are added into water and mixed evenly to obtain an environmentally friendly titanium alloy etching solution.

8. The etching method of the environmentally friendly titanium alloy etching solution according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: using the environmentally friendly titanium alloy etching liquid described in any one of claims 1 to 6 to etch the circuit board in a horizontal line spraying manner at a temperature of 40-60° C. and an etching time of 0.5-1.5 min.

9. The etching method of the environmentally friendly titanium alloy etching solution according to claim 8, characterized in that: The spray pressure of the horizontal spray is 1.5-2.5kg / cm 2 , the etching speed is 4-8m / min.

10. The etching method of environmentally friendly titanium alloy etching solution according to claim 9, characterized in that: The temperature is 45-55° C., and the etching speed is 5-7 m / min.

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