Copper plating additive composition, copper plating solution and use thereof

Abstract

The present application relates to a copper plating additive composition, a copper plating solution, and a copper brush plating method using the same. The copper plating additive composition includes 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound.

Description

[Technical Field]

[0001] Cross-references to related applications This application claims priority to and the benefit of Chinese patent applications bearing application numbers 2022102992129 and 2022102993386, filed on March 25, 2022, and international applications bearing application numbers PCT / CN2022 / 094709 and PCT / CN2022 / 094681, filed on May 24, 2022, the entire texts of which are incorporated herein by reference.

[0002] This application relates to the technical field of copper plating, and in particular to copper plating additive compositions, copper plating solutions and uses thereof. [Background technology]

[0003] Electric brush plating, also known as metal brush plating, quick plating, or brush plating, is an electrochemical process in which a plating brush immersed in a plating solution serves as the anode, and metal ions are discharged and crystallized on the surface of the cathode (workpiece) to form a metal coating layer.

[0004] Copper brush plating is primarily used in fields with high conductivity requirements, such as electronics, electrical engineering, and aerospace, and is particularly valuable for selective plating and plating layer repair. The rapid relative movement of the cathode and anode during operation allows for high current densities (several to several tens of times higher than those used in plating baths). Furthermore, the high copper ion content in the copper brush plating solution allows for extremely fast plating speeds (five to ten times faster than bath plating). Over the past few decades, scientists around the world have conducted in-depth and long-term research into cyanide-free copper plating processes. Cyanide-free copper plating technology has now been industrialized, achieving significant social and economic benefits. However, cyanide-free copper brush plating still suffers from defects such as uneven plating layers and a dull appearance.

[0005] Furthermore, in the prior art, double-sided copper plating of the surface of a plastic film (e.g., polypropylene (PP) or polyethylene terephthalate (PET)) with a thickness of 3.2 μm to 12 μm typically requires two processes: magnetron sputtering + electroplating, or vapor deposition + electroplating. However, these two processes have the problem of low yield rates in terms of processing quality between processes. The main drawbacks are that the thickness of the copper film formed after magnetron sputtering or vapor deposition is uneven, and burn holes are easily formed during copper electroplating, resulting in frequent failures such as film perforation and film cracking, resulting in an extremely low yield rate.

[0006] Furthermore, the copper film produced by magnetron sputtering or vapor deposition is too thin, resulting in a high sheet resistance, typically around 2000 mΩ. Therefore, increasing the copper layer thickness is necessary to reduce the sheet resistance below 500 mΩ. The traditional solution is to use acid copper electroplating, which can obtain a copper plating layer with dense crystals and achieve the required sheet resistance. However, the biggest drawback is that the cathode roller that contacts the plastic film during acid copper electroplating is plated with copper, and the copper-plated portion of the cathode roller is likely to break through the plastic film layer, resulting in holes in the plated plastic film and resulting in a rejection. Furthermore, the thickness of the plating layer may be poor, the film edge is prone to scorching, and defects such as burn holes, perforations, and film cracks may occur in the film layer, ultimately resulting in low yield rates and efficiency of plated films. On the other hand, significantly reducing sheet resistance using magnetron sputtering or vapor deposition significantly increases the risk of perforations and burn holes in the film. Furthermore, the subsequent acid copper electroplating process cannot use high electroplating currents, significantly reducing the film thickness and preventing the sheet resistance from falling within the required range for the finished product. Conversely, using too high an acid copper electroplating current increases the likelihood and extent of copper plating on the cathode roller, potentially puncturing or burning the plastic film surface. This means that the magnetron sputtering + acid copper electroplating or evaporation + acid copper electroplating processes are complex to operate and difficult to adjust and control, not to mention the difficulty of controlling the yield rate of the finished product in a single process.

[0007] Furthermore, a summary of the phenomena observed in laboratory and factory production shows that metallized plastic film becomes brittle after undergoing the acid copper electroplating process, and acid copper electroplating cannot be repeated multiple times. After one (maximum two) electroplating cycles, the film easily cracks when pulled, resulting in a rejected product. In addition, all of the product film processed in the previous process is discarded, resulting in excessive waste and no economic value.

[0008] To summarize the above, current electric brush plating has defects such as uneven plating layers and insufficient bright appearance of plating layers, and there are many other inconsistent problems in the copper brush plating process for plastic films. Therefore, the industry is urgently in need of a copper plating solution that can rapidly plate and significantly improve the uniformity, brightness and color saturation of the plating layer, as well as a copper brush plating process for plastic films that can improve the thickness and uniformity of the copper layer, prevent punctures of the plastic film, ensure the sheet resistance of the finished film meets the standard, and have good bonding strength between the copper plating layers. Summary of the Invention [Problem to be solved by the invention]

[0009] According to embodiments of the present application, the present application provides a copper plating additive composition, a copper plating solution, and a copper brush plating method. [Means for solving the problem]

[0010] The technical proposal is as follows:

[0011] A copper plating additive composition comprising 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide and an aminopolyol compound.

[0012] In one embodiment, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is (0.6-1.0):(1.2-2.0):(1.8-3.0).

[0013] In one embodiment, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is (0.8-1.0):(1.5-2.0):(2.0-3.0).

[0014] In one embodiment, the aminopolyol compound is 3-amino-1,2-propanediol.

[0015] The present application further provides a copper plating solution comprising the copper plating additive composition.

[0016] In one embodiment, the copper plating solution further comprises water, copper sulfate (CuSO), sulfuric acid, and chloride ions, which can be derived from a chloride-containing compound soluble in water, such as hydrogen chloride.

[0017] In one embodiment, the copper plating solution per liter comprises water, 1,4-cyclohexanedione monoethylene acetal 0.06g to 0.10g, Potassium phthalimide 0.12g~0.20g, Aminopolyol compound 0.18g to 0.30g, Copper sulfate 120g~220g, 50g-70g sulfuric acid, and Contains 60mg to 80mg of chloride ions.

[0018] In one embodiment, the copper plating solution further comprises a brightener, a surfactant, and a leveling agent.

[0019] In one embodiment, the brightener is one or more selected from ethylene thiourea, benzimidazole, and fatty amine ethoxy sulfonate.

[0020] In one embodiment, the surfactant is one or two selected from sodium dodecyl sulfonate and 3,3'-dithiobis(sodium 1-propanesulfonate).

[0021] In one embodiment, the leveling agent is one or more selected from polyethylene glycol, 1,4-butynediol, and polyethyleneimine alkyl salts.

[0022] In one embodiment, the copper plating solution per liter comprises water, 1,4-cyclohexanedione monoethylene acetal 0.06g to 0.10g, Potassium phthalimide 0.12g~0.20g, Aminopolyol compound 0.18g to 0.30g, Copper sulfate 120g~220g, Sulfuric acid 50g-70g, Chloride ions 60mg~80mg, Brightener 0.0002mg~0.0008mg, surfactant 0.05mg to 0.1mg, and Contains 0.05g to 0.1g of leveling agent.

[0023] In one embodiment, the copper plating solution per liter comprises water, 1,4-cyclohexanedione monoethylene acetal 0.06g to 0.10g, Potassium phthalimide 0.12g~0.20g, Aminopolyol compound 0.18g to 0.30g, Copper sulfate 120g~220g, Sulfuric acid 50g-70g, Chloride ions 60mg~80mg, Ethylenethiourea 0.0002mg to 0.0008mg, Sodium dodecyl sulfonate 0.05 mg to 0.1 mg, and Contains 0.05g to 0.1g of polyethylene glycol.

[0024] The present application further provides a method for copper plating a surface of a substrate, comprising the step of contacting the substrate with the copper plating solution to perform a copper plating process.

[0025] In one embodiment, the copper plating method for the surface of the substrate is a copper brush plating method.

[0026] In one embodiment, the copper plating method for the surface of the substrate is performed using one or more parameters selected from the following: plating temperature 35°C to 45°C, plating time 1 minute to 2 minutes, and operating voltage 2V to 7V.

[0027] In some embodiments, the copper plating method for the surface of the substrate is performed under the following parameters: plating temperature 35°C to 45°C, plating time 1 minute to 2 minutes, and operating voltage 2V to 7V.

[0028] The present application further discloses a copper brush plating method for providing a coating layer on a surface of a substrate, the method comprising: performing a copper plating process on a surface of a substrate using a copper brush plating method to form a copper film on the surface of the substrate, wherein the anode during the copper plating process is a brush plating roller; and the copper plating process further comprises contacting the surface of the substrate with a copper plating solution.

[0029] In one embodiment, copper brush plating is performed at one or more parameters selected from the following: plating temperature: 0°C to 45°C; plating time: 1 min to 10 min; operating voltage: 1 V to 7 V; relative movement speed of the plastic film to the brush plating roller: 3 m / min to 10 m / min.

[0030] In some embodiments, copper brush plating is performed under the following parameters: plating temperature 0°C to 45°C, plating time 1 min to 10 min, operating voltage 1 V to 7 V, and relative movement speed of the plastic film to the brush plating roller 3 m / min to 10 m / min.

[0031] In one embodiment, the copper brush plating method further includes a step of performing a first copper plating process on the plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film, thereby forming a substrate.

[0032] In some embodiments, the copper plating solution used in the copper plating process includes water, copper sulfate (CuSO4), sulfuric acid, chloride ions, 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound.

[0033] In some embodiments, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is (0.6-1.0):(1.2-2.0):(1.8-3.0).

[0034] In one embodiment, the copper brush plating method includes the steps of: performing a first copper plating process on a plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film, thereby forming a substrate; performing a second copper plating process on the first copper film using a copper brush plating method to form a third copper film on the first copper film; the anode during the second copper plating process is a brush plating roller; The second copper plating process further comprises contacting the first copper film with a copper plating solution containing the copper plating additive composition.

[0035] In one embodiment, the copper plating solution used in the second copper plating process includes water, copper sulfate (CuSO4), sulfuric acid, chloride ions, 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound.

[0036] In some embodiments, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is (0.6-1.0):(1.2-2.0):(1.8-3.0).

[0037] In one embodiment, the copper brush plating method comprises: performing a first copper plating process on the plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film and a second copper film on the other surface of the plastic film; performing a second copper plating process on the first copper film and the second copper film using a copper brush plating method to form a third copper film on the first copper film and a fourth copper film on the second copper film; the anode during the second copper plating process is a brush plating roller; The second copper plating process further comprises contacting the first copper film and the second copper film with a copper plating solution containing the copper plating additive composition.

[0038] In one embodiment, the copper plating solution for the second copper plating process includes water, copper sulfate (CuSO4), sulfuric acid, chloride ions, 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound.

[0039] In some embodiments, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is (0.6-1.0):(1.2-2.0):(1.8-3.0).

[0040] In one embodiment, the plastic film is made of polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE), polyacrylonitrile (PAN), polyimide (PI), or polydimethylsiloxane (PDMS).

[0041] In one embodiment, the brush plating roller is covered with a sponge-like liquid-absorbing layer.

[0042] In one embodiment, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound used in the copper brush plating method is (0.6-1.0):(1.2-2.0):(1.8-3.0).

[0043] In one embodiment, the aminopolyol compound used in the copper brush plating method is 3-amino-1,2-propanediol.

[0044] In one embodiment, the copper plating solution per liter used in the copper brush plating method comprises water, 1,4-cyclohexanedione monoethylene acetal 0.06g to 0.10g, Potassium phthalimide 0.12g~0.20g, Polyol compound 0.18g to 0.30g, Copper sulfate 120g~220g, 50g-70g sulfuric acid, and Contains 60mg to 80mg of chloride ions.

[0045] In one embodiment, the physical vapor deposition method is magnetron sputtering or evaporation.

[0046] In one embodiment, the sheet resistance of the first copper film and the second copper film is 2200 mΩ or less.

[0047] In one embodiment, the first copper film and the second copper film each independently have a sheet resistance of 100 mΩ to 2200 mΩ.

[0048] In one embodiment, the first copper film and the second copper film each have a thickness independently ranging from 0.1 μm to 0.5 μm.

[0049] In one embodiment, the second copper plating process is performed under one or more parameters selected from the following: a plating temperature of 0°C to 45°C, a plating time of 1 min to 10 min, an operating voltage of 1 V to 7 V, and a relative movement speed of the plastic film with respect to the brush plating roller of 3 m / min to 10 m / min.

[0050] In one embodiment, the second copper plating process is performed under the following parameters: plating temperature 0°C to 45°C, plating time 1 min to 10 min, operating voltage 1 V to 7 V, and relative movement speed of the plastic film with respect to the brush plating roller 3 m / min to 10 m / min.

[0051] In one embodiment, the thickness of the plastic film is 3.2 μm to 12 μm.

[0052] In one embodiment, the copper plating solution used in the copper brush plating method further includes at least one of a brightener, a surfactant, and a leveling agent.

[0053] In one embodiment, the brightener used in the copper brush plating method is one or more selected from ethylene thiourea, benzimidazole, and aliphatic amine ethoxysulfonate.

[0054] In one embodiment, the surfactant used in the copper brush plating method is one or two selected from sodium dodecyl sulfonate and 3,3'-dithiobis(sodium 1-propanesulfonate).

[0055] In one embodiment, the leveling agent used in the copper brush plating method is one or two of polyethyleneimine alkyl salt and polyethylene glycol.

[0056] In one embodiment, the copper plating solution per liter used in the copper brush plating method comprises water, 1,4-cyclohexanedione monoethylene acetal 0.06g to 0.10g, Potassium phthalimide 0.12g~0.20g, Polyol compound 0.18g to 0.30g, Copper sulfate 150g~220g, Sulfuric acid 50g-70g, Chloride ions 60mg~80mg, Brightener 0.0002mg~0.0008mg, surfactant 0.05mg to 0.1mg, and Contains 0.05g to 0.1g of leveling agent. [Brief explanation of the drawings]

[0057] In order to more clearly explain the embodiments of the present invention, reference will now be made to the drawings, which are for illustrative purposes only and are not intended to limit the scope of the present application.

[0058] [Figure 1] 1 is a flowchart of a copper brush plating method for providing a coating layer on a surface of a plastic film in accordance with one or more embodiments of the present application. [Figure 2] 1 is a schematic diagram of a copper brush plating apparatus for use in a copper brush plating method in accordance with one or more embodiments of the present application; [Figure 3] 1A is a diagram of a copper plated layer in Example 1 of the present application, FIG. 1B is a diagram of a copper plated layer in Example 2 of the present application, and FIG. 1C is a diagram of a copper plated layer in Example 3 of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0059] In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be described in detail with reference to the drawings and examples. It should be understood that the specific embodiments described herein are only for illustrating the present disclosure, and are not intended to limit the present disclosure.

[0060] Unless otherwise defined, all technical or scientific terms used herein have the same ordinary meaning as understood by those skilled in the art. As used herein, these terms are intended to describe examples of the present disclosure and are not intended to limit the present application. As used herein, the term "and / or" refers to any and all combinations of one or more of the applicable items.

[0061] As used herein, the use of "including," "having," and "containing" is intended to cover an inclusive inclusion and may include additional components unless express limiting terms such as "only," "consisting of," or the like are used.

[0062] In the description of this application, the orientations or positional relationships indicated by directional terms such as "center," "lateral," "longitudinal," "length," "width," "thickness," "up," "down," "front," "rear," "left," "right," "up," "down," "vertical," "horizontal," "top," "bottom," "inside," "outside," "clockwise," "counterclockwise," etc. are based on the orientations or positional relationships shown in the drawings, and are intended merely to facilitate and simplify the description of this application. They do not indicate or imply that the indicated devices or elements necessarily have a specific orientation or need to be constructed and operated in a specific orientation, and should not be understood as limiting the specific scope of protection of this application.

[0063] When describing positional relationships, unless otherwise specified, when an element, e.g., a layer, film, or substrate, is referred to as being "on" another film layer, it can be directly on top of the other film layer, or there can be intermediate film layers present. Furthermore, when a layer is referred to as being "below" another layer, it can be directly below, or there can be one or more intermediate layers present. Furthermore, when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or there can be one or more intermediate layers present.

[0064] When a range of values ​​is disclosed herein, the range is considered continuous and includes the minimum value, the maximum value, and every value between the minimum and maximum values. Furthermore, when a range refers to an integer, it includes every integer between the minimum and maximum values ​​in the range. It should be noted that when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges contained therein.

[0065] Unless stated to the contrary, singular terms may include plurals and should not be construed as meaning one.

[0066] It should be noted that the drawings are not drawn to a 1:1 scale, and the relative dimensions of each element are illustratively depicted in the drawings to facilitate understanding of the present application, but are not necessarily drawn to a true scale, and the scale in the drawings does not limit the present application.

[0067] The present application provides a copper plating additive composition that can significantly improve the thickness, brightness, and whiteness of the plating layer.

[0068] The technical proposal is as follows:

[0069] The copper plating additive composition includes 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound.

[0070] Here, 1,4-cyclohexanedione monoethylene acetal can significantly improve the brightness of the copper brush plating layer. Potassium phthalimide can effectively increase the dissolution efficiency of 1,4-cyclohexanedione monoethylene acetal, refine the crystal grains, level, and improve the uniformity and thickness of the plating layer. The aminopolyol compound can significantly change the color tone of the copper layer, making it more vivid. Furthermore, this copper plating additive composition has the advantages of being environmentally friendly, non-toxic, and low cost, making it suitable for large-scale industrial production.

[0071] In one embodiment, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is (0.6 to 1.0):(1.2 to 2.0):(1.8 to 3.0), and examples thereof include 0.6:1.2:1.8, 0.6:1.2:1.9, 0.6:1.2:2.0, 0.6:1.2:2.1, 0.6:1.2:2.2, 0.6:1.2:2.3, 0.6:1.2:2.4, 0.6:1.2:2.5, 0.6:1.2:2.6, 0.6:1.2:2.7, 0.6:1.2:2.8, 0.6:1.2:2.9, 0.6:1.2 :3.0, 0.6:1.5:1.8, 0.6:1.5:1.9, 0.6:1.5:2.0, 0.6:1.5:2.1, 0.6:1.5:2.2, 0.6:1.5:2.3, 0.6:1.5:2.4, 0.6:1.5:2.5, 0.6:1.5:2.6, 0.6:1.5:2.7, 0.6:1.5:2.8, 0.6:1.5:2.9, 0.6:1.5:3.0, 0.6:1.8:1.8, 0.6:1.8:1.9, 0.6:1.8:2.0, 0.6:1.8:2.1, 0.6:1.8:2.2, 0.6:1.8:2.3, 0.6:1.8:2.4, 0.6:1 .8:2.5, 0.6:1.8:2.6, 0.6:1.8:2.7, 0.6:1.8:2.8, 0.6:1.8:2.9, 0.6:1.8:3.0, 0.6:2.0:1.8, 0.6:2.0:1.9, 0.6:2.0:2.0, 0.6:2.0:2.1, 0.6:2.0:2. 2, 0.6:2.0:2.3, 0.6:2.0:2.4, 0.6:2.0:2.5, 0.6:2.0:2.6, 0.6:2.0:2.7, 0.6:2.0:2.8, 0.6:2.0:2.9, 0.6:2.0:3.0, 0.8:1.2:1.8, 0.8:1.2:1.9, 0.8 :1.2:2.0, 0.8:1.2:2.1, 0.8:1.2:2.2, 0.8:1.2:2.3, 0.8:1.2:2.4, 0.8:1.2:2.5, 0.8:1.2:2.6, 0.8:1.2:2.7, 0.8:1.2:2.8, 0.8:1.2:2.9, 0.8:1.2: 3.0, 0.8:1.5:1.8, 0.8:1.5:1.9, 0.8:1.5:2.0, 0.8:1.5:2.1, 0.8:1.5:2.2, 0.8:1.5:2.3, 0.8:1.5:2.4, 0.8:1.5:2.5, 0.8:1.5:2.6, 0.8:1.5:2.7, 0.8:1.5:2.8, 0.8:1.5:2.9, 0.8:1.5:3.0, 0.8:1.8:1.8, 0.8:1.8:1.9, 0.8:1.8:2.0, 0.8:1.8:2.1, 0.8:1.8:2.2, 0.8:1.8:2.3, 0.8:1.8:2.4, 0.8:1.8:2.5, 0.8:1.8:2.6, 0.8:1.8:2.7, 0.8:1.8:2.8, 0.8:1.8:2.9, 0.8:1.8:3.0, 0.8:2.0:1.8, 0.8:2 .0:1.9, 0.8:2.0:2.0, 0.8:2.0:2.1, 0.8:2.0:2.2, 0.8:2.0:2.3, 0.8:2.0:2.4, 0.8:2.0:2.5, 0.8:2.0:2.6, 0.8:2.0:2.7, 0.8:2.0:2.8, 0.8:2.0:2.9, 0.8:2.0:3.0, 1.0:1.5:1.8, 1.0:1.5:1.9, 1.0:1.5:2.0, 1.0:1.5:2.1, 1.0:1.5:22, 1.0:1.5:2 .3, 1.0:1.5:2.4, 1.0:1.5:2.5, 1.0:1.5:2.6, 1.0:1.5:2.7, 1.0:1.5:2.8, 1.0:1.5:2.9, 1.0:1.5:3.0, 1.0:1.8:1.8, 1.0:1.8:1.9, 1.0:1.8:2.0, 1.0:1.8:2.1, 1.0:1.8:2.2, 1.0:1.8:2.3, 1.0:1.8:2.4, 1.0:1.8:2.5, 1.0:1.8:2.6, 1.0:1.8:2.7, 1 Including, but not limited to, 1.0:1.8:2.8, 1.0:1.8:2.9, 1.0:1.8:3.0, 1.0:2.0:1.8, 1.0:2.0:1.9, 1.0:2.0:2.0, 1.0:2.0:2.1, 1.0:2.0:2.2, 1.0:2.0:2.3, 1.0:2.0:2.4, 1.0:2.0:2.5, 1.0:2.0:2.6, 1.0:2.0:2.7, 1.0:2.0:2.8, 1.0:2.0:2.9 and 1.0:2.0:3.0.

[0072] In one embodiment, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is (0.8-1.0):(1.5-2.0):(2.0-3.0).

[0073] In one embodiment, the mass ratio of 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and aminopolyol compound is 1.0:2.0:3.0.

[0074] In one embodiment, the aminopolyol compound is 3-amino-1,2-propanediol.

[0075] The present application further provides a copper plating solution comprising the copper plating additive composition.

[0076] In one embodiment, the copper plating solution further comprises water, copper sulfate (CuSO4), sulfuric acid, and chloride ions.

[0077] In one embodiment, the copper plating solution further comprises a brightener, a surfactant, and a leveling agent.

[0078] When the copper plating additive composition is added to a copper plating solution, even a small amount can significantly improve the thickness, brightness, and whiteness of the plating layer, without changing the stability of the original copper plating solution or the performance of the original copper plating layer.

[0079] The present application also provides a copper brush plating method for providing a coating layer on the surface of a plastic film, which has a fast plating speed, can obtain a fine-crystalline, continuous, uniform copper film or layer, does not cause any adverse effects on the copper-plated film or layer, has good bonding strength after plating, and the plated film or layer formed by a single brush plating process has a sheet resistance that meets the requirements of the finished product, and does not puncture the plastic film.

[0080] The present application further provides a method for copper plating a surface of a substrate, comprising contacting the substrate with a copper plating solution to effect copper plating.

[0081] The present application further provides a copper brush plating method for providing a coating layer on a surface of a substrate, the method comprising: performing a copper plating process on a surface of a substrate using a copper brush plating method to form a copper film on the surface of the substrate, wherein the anode during the copper plating process is a brush plating roller; and the copper plating process further comprises contacting the surface of the substrate with a copper plating solution.

[0082] The copper brush plating method may further include performing a first copper plating process on the plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film, thereby forming a substrate.

[0083] In one embodiment, the substrate is made of plastic. Further, the substrate is a plastic film.

[0084] In another embodiment, the substrate includes a first copper film on a surface of a plastic film, where the first copper film is formed by a physical vapor deposition process such as magnetron sputtering or evaporation.

[0085] During the copper plating process, the relative movement speed of the substrate to the brush plating bath is 3m / min to 10m / min.

[0086] In one embodiment, the copper brush plating method of the present invention comprises: performing a first copper plating process on the plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film, thereby forming a substrate; performing a second copper plating process on the first copper film using a copper brush plating method to form a third copper film on the first copper film; the anode during the second copper plating process is a brush plating roller; The second copper plating process further comprises contacting the first copper film on the substrate with a copper plating solution comprising a copper plating additive composition.

[0087] Here, the copper plating additive composition comprises 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide and an aminopolyol compound.

[0088] In one embodiment, the copper brush plating method comprises: performing a first copper plating process on the plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film and a second copper film on the other surface of the plastic film; performing a second copper plating process on the first copper film and the second copper film using a copper brush plating method to form a third copper film on the first copper film and a fourth copper film on the second copper film; the anode during the second copper plating process is a brush plating roller; the second copper plating process further comprises contacting the first copper film and the second copper film with a copper plating solution containing the copper plating additive composition; The copper plating additive composition includes 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound.

[0089] Electric brush plating, also known as metal brush plating, quick plating, or brush plating, is an electrochemical process in which a plating brush immersed in a plating solution serves as the anode, discharging metal ions onto the surface of a negative electrode (workpiece) to crystallize and form a metal coating. This application innovatively replaces the brush plating brush with an anode brush plating roller, significantly improving plating speed, production efficiency, grain refinement, uniformity, and continuity of the plating layer, while also reducing the risk of perforations in plastic films. Furthermore, the use of a copper plating solution containing 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound refines grain size, improves the flatness and uniformity of the copper plating layer, and increases the thickness of the copper plating layer. It also improves the whiteness, brightness, and color of the copper plating layer. Furthermore, the copper brush plating method does not adversely affect the copper plating film or layer produced by conventional physical vapor deposition (PVD). The bonding strength of each film or layer is good after plating, and the plated film or layer formed in a single brush plating process meets the sheet resistance requirements of the finished product. The copper plating solution used in the present invention has the advantages of being environmentally friendly, non-toxic, and low cost, and is suitable for large-scale industrial production.

[0090] In one embodiment, the copper brush plating method includes the following steps S1 and S2, and the flow chart is shown in FIG.

[0091] S1, performing a first copper plating process on a plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film and a second copper film on the other surface of the plastic film;

[0092] In one embodiment, the plastic film is made of polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE), polyacrylonitrile (PAN), polyimide (PI), or polydimethylsiloxane (PDMS).

[0093] In one embodiment, the thickness of the plastic film is 3.2 μm to 12 μm.

[0094] In one embodiment, the physical vapor deposition method is magnetron sputtering or evaporation.

[0095] In one embodiment, the first copper film and the second copper film are both formed by magnetron sputtering.

[0096] In one embodiment, the first copper film and the second copper film are both formed by evaporation.

[0097] In one embodiment, the magnetron sputtering includes the steps of magnetron sputtering nichrome, magnetron sputtering copper.

[0098] In one embodiment, the deposition includes the steps of magnetron sputtering nichrome, magnetron sputtering copper, and evaporating copper.

[0099] In one embodiment, the sheet resistance of the first copper film is 2200 mΩ or less.

[0100] In one embodiment, the sheet resistance of the first copper film is 100mΩ to 2200mΩ, including, but not limited to, 100mΩ, 200mΩ, 300mΩ, 400mΩ, 500mΩ, 600mΩ, 700mΩ, 800mΩ, 900mΩ, 1000mΩ, 1100mΩ, 1200mΩ, 1300mΩ, 1400mΩ, 1500mΩ, 1600mΩ, 1700mΩ, 1800mΩ, 1900mΩ, 2000mΩ, 2100mΩ, or 2200mΩ.

[0101] In one embodiment, the sheet resistance of the first copper film is 1500 mΩ or less.

[0102] In one embodiment, the sheet resistance of the first copper film is less than 500 mΩ.

[0103] In one embodiment, the thickness of the first copper film is between 0.1 μm and 0.5 μm, including but not limited to 0.1 μm, 0.15 μm, 0.2 μm, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, and 0.5 μm.

[0104] In one embodiment, the sheet resistance of the second copper film is 2200 mΩ or less.

[0105] In one embodiment, the sheet resistance of the second copper film is 100mΩ to 2200mΩ, including, but not limited to, 100mΩ, 200mΩ, 300mΩ, 400mΩ, 500mΩ, 600mΩ, 700mΩ, 800mΩ, 900mΩ, 1000mΩ, 1100mΩ, 1200mΩ, 1300mΩ, 1400mΩ, 1500mΩ, 1600mΩ, 1700mΩ, 1800mΩ, 1900mΩ, 2000mΩ, 2100mΩ, or 2200mΩ.

[0106] In one embodiment, the sheet resistance of the second copper film is 1500 mΩ or less.

[0107] In one embodiment, the sheet resistance of the second copper film is less than 500 mΩ.

[0108] In one embodiment, the thickness of the second copper film is between 0.1 μm and 0.5 μm, including but not limited to 0.1 μm, 0.15 μm, 0.2 μm, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, and 0.5 μm.

[0109] S2: A second copper plating process is performed on the first copper film and the second copper film using a copper brush plating method, forming a third copper film on the first copper film and a fourth copper film on the second copper film.

[0110] In this application, the anode during the second copper plating process is a brush plating roller. By changing the brush plating brush to an anode brush plating roller, the plating speed, production efficiency, fineness of crystal grains, uniformity and continuity of the plating layer can be significantly improved, and the risk of perforation of the plastic film can be reduced.

[0111] In one embodiment, the brush plating roller is covered with a sponge-like liquid-absorbing layer, which can eliminate the problem of the brush plating roller being copper-plated and prevent the copper film from being pierced by the copper plating of the brush plating roller.

[0112] In one embodiment, the brush plating equipment of the present application includes an unwinding system, a brush plating system, a rinsing system, a baking system, and a winding system.

[0113] In one embodiment, a schematic diagram of the brush plating equipment of the present application can be seen in Figure 2, and includes an unwinding system 1, a brush plating bath 2, a water-blocking roller 3, a cathode conductive roller 4, an anode brush plating roller 5, a clip oven 6, and a take-up system 7. Multiple water-blocking rollers 3 may be arranged in the equipment. Three to six anode brush plating rollers 5 may be provided in between, and the anode brush plating rollers 5 may be covered with a sponge-like liquid-absorbing layer. The brush plating system and baking system may also include an anti-oxidation system that performs an anti-oxidation treatment on the copper plating layer to improve its anti-oxidation ability and extend its service life.

[0114] In this application, the copper plating solution used in the second copper plating process contains water, copper sulfate, sulfuric acid, chloride ions, 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound. Copper sulfate provides the basis for copper plating, and by forming an adsorption layer with sulfuric acid, it slows the substitution rate, inhibits side reactions, reduces the porosity of the copper layer during the substitution reaction, and improves bonding strength. Chloride ions provide the basis for the formation of a shiny copper plating layer, and also react with monovalent copper ions to form CuCl precipitates, reducing the production of "copper powder" in the plating layer and making the plating layer denser, finer, and less coarse. 1,4-Cyclohexanedione monoethylene acetal can significantly improve the brightness of the copper brush plating layer. Potassium phthalimide can effectively improve the dissolution efficiency of 1,4-cyclohexanedione monoethylene acetal, as well as refine and level the crystal grains, improve the uniformity of the plating layer, and increase the thickness of the plating layer. Aminopolyol compounds can significantly change the color tone of the copper layer, making it more vivid.

[0115] In one embodiment, the second copper plating process is performed under the following parameters: plating temperature 0°C to 45°C, plating time 1 min to 10 min, operating voltage 1 to 7 V, and relative movement speed of the plastic film with respect to the brush plating roller 3 m / min to 10 m / min.

[0116] Plating temperatures include, but are not limited to, 0°C, 2°C, 5°C, 8°C, 10°C, 12°C, 15°C, 18°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, and 45°C. Plating times include, but are not limited to, 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min, 4.5 min, 5 min, 6 min, 6.5 min, 7 min, 7.5 min, 8 min, 8.5 min, 9 min, 9.5 min, and 10 min. The operating voltages include, but are not limited to, 1 V, 2 V, 3 V, 4 V, 5 V, 6 V, and 7 V. The relative movement speeds of the plastic film to the brush plating roller can be understood to be 3 m / min, 3.5 m / min, 4 m / min, 4.5 m / min, 5 m / min, 5.5 m / min, 6 m / min, 6.5 m / min, 7 m / min, 7.5 m / min, 8 m / min, 8.5 m / min, 9 m / min, 9.5 m / min, and 10 m / min.

[0117] The present invention will now be further described with reference to specific examples. [Example]

[0118] (1) In this embodiment, 1,4-Cyclohexanedione monoethylene acetal 10g, 20g potassium phthalimide, and One liter of an aqueous solution of the copper plating additive composition containing 30 g of 3-amino-1,2-propanediol was prepared. (2) In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.10g, Potassium phthalimide 0.20g, 3-amino-1,2-propanediol 0.30g, Copper sulfate 120g, 70g sulfuric acid, Chloride ions 70mg, ethylenethiourea 0.0005mg, Sodium dodecyl sulfonate 0.08 mg, and One liter of the copper plating solution containing 0.07 g of polyethylene glycol was prepared.

[0119] (3) The copper plating solution of this example was prepared by a method including the following steps:

[0120] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 10 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0121] 2) Preparation of potassium phthalimide: 20 g of potassium phthalimide was weighed out on an analytical balance.

[0122] 3) Preparation of 3-amino-1,2-propanediol solution: 30 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0123] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0124] 5) Copper sulfate, sulfuric acid, hydrogen chloride, ethylenethiourea, sodium dodecylsulfonate and polyethylene glycol were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0125] (4) Copper brush plating was carried out to provide a coating layer on the surface of the PP film, and the method included the following steps:

[0126] Copper brush plating was performed on the PP film for 5 minutes under the following conditions: plating temperature of the plating solution was 40°C, relative movement speed of the plastic film to the brush plating roller was 7m / min, and operating voltage of the brush plating was 2V. After that, the plating layer was slowly washed with flowing deionized water and dried. The thickness of the copper plating layer was measured using the Fischei measurement method, and the appearance of the copper plating layer was observed.

[0127] (5) As a comparative example, a PP film was subjected to copper brush plating under the same conditions as (4) using a copper plating solution that did not contain the copper plating additive composition, and the plating layer was washed and dried. The thickness of the copper plating layer was measured using the Fischer method, and the appearance of the copper plating layer was observed.

[0128] (6) Detection results 3, the copper plating layer (a) formed on the workpiece by brush plating with the additive composition was 3.52 μm thick, had a smooth surface, and a glossy copper color, whereas the copper plating layer formed on the workpiece by brush plating without the additive composition was 1.06 μm thick, had a rough surface, and a dull reddish-brown color. [Example]

[0129] (1) In this embodiment, 1,4-cyclohexanedione monoethylene acetal 6g, 12g potassium phthalimide, and One liter of an aqueous solution of the copper plating additive composition containing 18 g of 3-amino-1,2-propanediol was prepared.

[0130] (2) In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.06g, Potassium phthalimide 0.12g, 3-amino-1,2-propanediol 0.18g, Copper sulfate 150g, 60g of sulfuric acid, Chloride ions 70mg, ethylenethiourea 0.0005mg, Sodium dodecyl sulfonate 0.08 mg, and One liter of the copper plating solution containing 0.07 g of polyethylene glycol was prepared.

[0131] (3) The copper plating solution of this example was prepared by a method including the following steps:

[0132] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 6 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0133] 2) Preparation of potassium phthalimide: 12 g of potassium phthalimide was weighed out using an analytical balance.

[0134] 3) Preparation of 3-amino-1,2-propanediol solution: 18 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0135] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0136] 5) Copper sulfate, sulfuric acid, hydrogen chloride, ethylenethiourea, sodium dodecylsulfonate and polyethylene glycol were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0137] (4) Copper brush plating was carried out to provide a coating layer on the surface of the PP film, and the method included the following steps:

[0138] Copper brush plating was performed on the PP film for 5 minutes under the following conditions: plating temperature of the plating solution was 40°C, relative movement speed of the plastic film to the brush plating roller was 7m / min, and operating voltage of the brush plating was 2V. After that, the plating layer was slowly washed with flowing deionized water and dried. The thickness of the copper plating layer was measured using the Fischei measurement method, and the appearance of the copper plating layer was observed.

[0139] (5) As a comparative example, a PP film was subjected to copper brush plating under the same conditions as (4) using a copper plating solution that did not contain the copper plating additive composition, and the plating layer was washed and dried. The thickness of the copper plating layer was measured using the Fischer method, and the appearance of the copper plating layer was observed.

[0140] (6) Detection results 3, the copper plating layer (b) formed on the workpiece by brush plating with the additive composition is 3.14 μm thick, has a smooth surface, and a glossy copper color, while the copper plating layer formed on the workpiece by brush plating without the additive composition is 0.98 μm thick, has a rough surface, and a dull reddish-brown color. [Example]

[0141] (1) In this embodiment, 1,4-cyclohexanedione monoethylene acetal 7g, 14g potassium phthalimide, and One liter of an aqueous solution of the copper plating additive composition containing 21 g of 3-amino-1,2-propanediol was prepared.

[0142] (2) In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.07g, Potassium phthalimide 0.14g, 3-amino-1,2-propanediol 0.21g, Copper sulfate 180g, 50g sulfuric acid, Chloride ions 60mg, ethylenethiourea 0.0002mg, Sodium dodecyl sulfonate 0.05 mg, and One liter of the copper plating solution containing 0.05 g of polyethylene glycol was prepared.

[0143] (3) The copper plating solution of this example was prepared by a method including the following steps:

[0144] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 7 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0145] 2) Preparation of potassium phthalimide: 14 g of potassium phthalimide was weighed out using an analytical balance.

[0146] 3) Preparation of 3-amino-1,2-propanediol solution: 21 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0147] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0148] 5) Copper sulfate, sulfuric acid, hydrogen chloride, ethylenethiourea, sodium dodecylsulfonate and polyethylene glycol were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0149] (4) Copper brush plating was carried out to provide a coating layer on the surface of the PP film, and the method included the following steps:

[0150] Copper brush plating was performed on the PP film for 5 minutes under the following conditions: plating temperature of the plating solution was 40°C, relative movement speed of the plastic film to the brush plating roller was 7m / min, and operating voltage of the brush plating was 2V. After that, the plating layer was slowly washed with flowing deionized water and dried. The thickness of the copper plating layer was measured using the Fischei measurement method, and the appearance of the copper plating layer was observed.

[0151] (5) As a comparative example, a PP film was subjected to copper brush plating under the same conditions as (4) using a copper plating solution that did not contain the copper plating additive composition, and the plating layer was washed and dried. The thickness of the copper plating layer was measured using the Fischer method, and the appearance of the copper plating layer was observed.

[0152] (6) Detection results 3, the copper plating layer (c) formed on the workpiece by brush plating with the additive composition was 3.21 μm thick, had a smooth surface, and a glossy copper color, whereas the copper plating layer formed on the workpiece by brush plating without the additive composition was 1.05 μm thick, had a rough surface, and a dull reddish-brown color. [Example]

[0153] (1) In this embodiment, 1,4-cyclohexanedione monoethylene acetal 8g, 16g potassium phthalimide, and One liter of an aqueous solution of the copper plating additive composition containing 24 g of 3-amino-1,2-propanediol was prepared.

[0154] (2) In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.08g, Potassium phthalimide 0.16g, 3-amino-1,2-propanediol 0.24g, Copper sulfate 200g, 70g sulfuric acid, Chloride ions 80mg, ethylenethiourea 0.0008mg, Sodium dodecyl sulfonate 0.1 mg, and One liter of the copper plating solution containing 0.05 g of polyethylene glycol was prepared.

[0155] (3) The copper plating solution of this example was prepared by a method including the following steps:

[0156] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 8 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0157] 2) Preparation of potassium phthalimide: 16 g of potassium phthalimide was weighed out on an analytical balance.

[0158] 3) Preparation of 3-amino-1,2-propanediol solution: 24 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0159] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0160] 5) Copper sulfate, sulfuric acid, hydrogen chloride, ethylenethiourea, sodium dodecylsulfonate and polyethylene glycol were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0161] (4) Copper brush plating was carried out to provide a coating layer on the surface of the PP film, and the method included the following steps:

[0162] Copper brush plating was performed on the PP film for 5 minutes under the following conditions: plating temperature of the plating solution was 40°C, relative movement speed of the plastic film to the brush plating roller was 7m / min, and operating voltage of the brush plating was 2V. After that, the plating layer was slowly washed with flowing deionized water and dried. The thickness of the copper plating layer was measured using the Fischei measurement method, and the appearance of the copper plating layer was observed.

[0163] (5) As a comparative example, a PP film was subjected to copper brush plating under the same conditions as (4) using a copper plating solution that did not contain the copper plating additive composition, and the plating layer was washed and dried. The thickness of the copper plating layer was measured using the Fischer method, and the appearance of the copper plating layer was observed.

[0164] (6) Detection results In this example, the copper plating layer formed on the workpiece by brush plating with the additive composition was 3.31 μm thick, had a smooth surface, and a glossy copper color, whereas the copper plating layer formed on the workpiece by brush plating without the additive composition was 1.02 μm thick, had a rough surface, and a dull reddish-brown color. [Example]

[0165] (1) In this embodiment, 1,4-cyclohexanedione monoethylene acetal 9g, 18g potassium phthalimide, and One liter of an aqueous solution of the copper plating additive composition containing 27 g of 3-amino-1,2-propanediol was prepared.

[0166] (2) In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.09g, Potassium phthalimide 0.18g, 3-amino-1,2-propanediol 0.27g, Copper sulfate 220g, 70g sulfuric acid, Chloride ions 60mg, ethylenethiourea 0.0008mg, Sodium dodecyl sulfonate 0.1 mg, and One liter of the copper plating solution containing 0.06 g of polyethylene glycol was prepared.

[0167] (3) The copper plating solution of this example was prepared by a method including the following steps:

[0168] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 9 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0169] 2) Preparation of potassium phthalimide: 18 g of potassium phthalimide was weighed out on an analytical balance.

[0170] 3) Preparation of 3-amino-1,2-propanediol solution: 27 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0171] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0172] 5) Copper sulfate, sulfuric acid, hydrogen chloride, ethylenethiourea, sodium dodecylsulfonate and polyethylene glycol were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0173] (4) Copper brush plating was carried out to provide a coating layer on the surface of the PP film, and the method included the following steps:

[0174] Copper brush plating was performed on the PP film for 5 minutes under the following conditions: plating temperature of the plating solution was 40°C, relative movement speed of the plastic film to the brush plating roller was 7m / min, and operating voltage of the brush plating was 2V. After that, the plating layer was slowly washed with flowing deionized water and dried. The thickness of the copper plating layer was measured using the Fischei measurement method, and the appearance of the copper plating layer was observed.

[0175] (5) As a comparative example, a PP film was subjected to copper brush plating under the same conditions as (4) using a copper plating solution that did not contain the copper plating additive composition, and the plating layer was washed and dried. The thickness of the copper plating layer was measured using the Fischer method, and the appearance of the copper plating layer was observed.

[0176] (6) Detection results In this example, the copper plating layer formed on the workpiece by brush plating with the additive composition was 3.36 μm thick, had a smooth surface, and a glossy copper color, whereas the copper plating layer formed on the workpiece by brush plating without the additive composition was 1.34 μm thick, had a rough surface, and a dull reddish-brown color.

[0177] According to the above examples, the present application has the technical effects of improving the bonding strength of the plating layer, refining the crystal grains, and avoiding perforation of the plating layer without adversely affecting the original performance of the high-speed copper brush plating solution, and can obtain a continuous, uniform copper plating layer with fine crystals, which can fully meet the needs of large-scale industrial production. [Example]

[0178] This example provides a copper plating method for a PP film, which includes the following steps:

[0179] (1) A copper plating solution was prepared. In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.1g, Potassium phthalimide 0.2g, 3-amino-1,2-propanediol 0.3g, Copper sulfate 220g, 60g sulfuric acid, and One liter of the copper plating solution containing 70 mg of chloride ions was prepared.

[0180] The copper plating solution of this example was prepared by a method including the following steps.

[0181] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 10 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0182] 2) Preparation of potassium phthalimide: 20 g of potassium phthalimide was weighed out on an analytical balance.

[0183] 3) Preparation of 3-amino-1,2-propanediol solution: 30 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0184] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0185] 5) Copper sulfate, sulfuric acid and hydrogen chloride were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0186] (2) First, magnetron sputtering of nichrome was performed on a PP film, followed by magnetron sputtering of copper (first copper plating process). The resulting copper film was then tested. (1) The sheet resistance of the copper film was tested by sampling at two points on the film. The first test result was 131 mΩ, and the second test result was 207 mΩ. (2) Tape was applied to the copper film and peeled off by hand, resulting in sporadic copper chips peeling off from the tail of the film. (3) Micropores were observed in the copper film by illuminating the back of the film with a mobile phone. (4) The thickness of the copper film measured using the Fischei method was 0.237 μm.

[0187] (3) A second copper plating process was performed on the copper film using a copper brush plating method.

[0188] Using the brush plating equipment shown in Figure 2, a second copper plating process was performed on a copper film under the following parameters: plating temperature 30°C, plating time 1 min, operating voltage 1 V, and relative movement speed of the plastic film relative to the brush plating roller 5 m / min. The resulting copper film was tested. (1) The sheet resistance of the copper film was tested by sampling at two points on the film. The first test result was 3.6 mΩ, and the second test result was 3.26 mΩ. (2) Tape was applied to the copper film and peeled off by hand; no copper was peeled off. Therefore, the copper film passed the adhesion test. (3) The film after copper brush plating was shiny, and no other pores were observed other than those formed during the sheet resistance test. (4) The copper film thickness measured using the Fischei method was 1.995 μm, and the film thickness increased by brush plating was 1.758 μm. [Example]

[0189] This example provides a copper plating method for a PP film, which includes the following steps:

[0190] (1) A copper plating solution was prepared. In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.6g, Potassium phthalimide 0.12g, 3-amino-1,2-propanediol 0.18g, Copper sulfate 220g, 60g sulfuric acid, and One liter of the copper plating solution containing 70 mg of chloride ions was prepared.

[0191] The copper plating solution of this example was prepared by a method including the following steps.

[0192] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 10 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0193] 2) Preparation of potassium phthalimide: 20 g of potassium phthalimide was weighed out on an analytical balance.

[0194] 3) Preparation of 3-amino-1,2-propanediol solution: 30 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0195] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0196] 5) Copper sulfate, sulfuric acid and hydrogen chloride were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0197] (2) First, magnetron sputtering of nichrome was performed on a PP film, followed by magnetron sputtering of copper (first copper plating process), and the resulting copper film was tested. (1) The sheet resistance of the copper film was tested, and the test result was 388 mΩ. (2) Tape was applied to the copper film and peeled off by hand, and the adhesive strength passed the test. (3) By illuminating the back of the film with a mobile phone, the presence of micropores in the copper film was observed. (4) The thickness of the copper film measured using the Fischei method was 0.357 μm.

[0198] (3) A second copper plating process was performed on the copper film using a copper brush plating method.

[0199] Using the brush plating equipment shown in Figure 2, a second copper plating process was performed on the copper film under the following parameters: plating temperature 30°C, plating time 2 min, operating voltage 1 V, and relative movement speed of the plastic film relative to the brush plating roller 5 m / min. The resulting copper film was tested. (1) The copper film's sheet resistance was tested, and the test result was 7.66 mΩ. (2) Tape was applied to the copper film and peeled off by hand, and no copper was peeled off. Therefore, the copper film passed the adhesion test. (3) The film after copper brush plating was shiny, and no other holes were observed other than those formed during the sheet resistance test. (4) The copper film thickness measured using the Fischei method was 0.913 μm, and the film thickness increased by brush plating was 0.556 μm. [Example]

[0200] This example provides a copper plating method for a PP film, which includes the following steps:

[0201] (1) A copper plating solution was prepared. In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.7g, Potassium phthalimide 0.14g, 3-amino-1,2-propanediol 0.21g, Copper sulfate 220g, 60g sulfuric acid, and One liter of the copper plating solution containing 70 mg of chloride ions was prepared.

[0202] The copper plating solution of this example was prepared by a method including the following steps.

[0203] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 10 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0204] 2) Preparation of potassium phthalimide: 20 g of potassium phthalimide was weighed out on an analytical balance.

[0205] 3) Preparation of 3-amino-1,2-propanediol solution: 30 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0206] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0207] 5) Copper sulfate, sulfuric acid and hydrogen chloride were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0208] (2) First, magnetron sputtering of nichrome was performed on a PP film, followed by magnetron sputtering of copper (first copper plating process), and the resulting copper film was tested. (1) The sheet resistance of the copper film was tested, and the test result was 121 mΩ. (2) Tape was applied to the copper film and peeled off by hand, and the adhesion passed. (3) By illuminating the back of the film with a mobile phone, the presence of micropores in the copper film was observed. (4) The thickness of the copper film measured using the Fischei method was 0.371 μm.

[0209] (3) A second copper plating process was performed on the copper film using a copper brush plating method.

[0210] Using the brush plating equipment shown in Figure 2, a second copper plating process was performed on the copper film under the following parameters: plating temperature 30°C, plating time 3 min, operating voltage 1 V, and relative movement speed of the plastic film relative to the brush plating roller 5 m / min. The resulting copper film was tested. (1) The copper film's sheet resistance was tested, and the test result was 5.21 mΩ. (2) Tape was applied to the copper film and peeled off by hand, but no copper peeled off. Therefore, the adhesion test passed. (3) The film surface after copper brush plating was shiny, and no other holes were observed other than those formed during the sheet resistance test. (4) The copper film thickness measured using the Fischei method was 0.875 μm, and the film thickness increased by brush plating was 0.504 μm. [Example]

[0211] This example provides a copper plating method for a PET film, which includes the following steps:

[0212] (1) A copper plating solution was prepared. In this example, water, 1,4-cyclohexanedione monoethylene acetal 0.06g, Potassium phthalimide 0.12g, 3-amino-1,2-propanediol 0.25g, Copper sulfate 200g, 60g of sulfuric acid, Chloride ions 70mg, ethylenethiourea 0.0002mg, Sodium dodecyl sulfonate 0.05 mg, and One liter of the copper plating solution containing 0.05 g of polyethyleneimine alkyl salt was prepared.

[0213] The copper plating solution of this example was prepared by a method including the following steps.

[0214] 1) Preparation of 1,4-cyclohexanedione monoethylene acetal solution: 6 g of 1,4-cyclohexanedione monoethylene acetal was dissolved in 200 ml of deionized water and stirred until clear.

[0215] 2) Preparation of potassium phthalimide: 12 g of potassium phthalimide was weighed out using an analytical balance.

[0216] 3) Preparation of 3-amino-1,2-propanediol solution: 25 g of 3-amino-1,2-propanediol was dissolved in 500 ml of deionized water and stirred until clear.

[0217] 4) Preparation of copper plating additive composition: The potassium phthalimide weighed in step 2) was slowly added to the 1,4-cyclohexanedione monoethylene acetal solution prepared in step 1), and after thorough stirring to dissolve and mix uniformly, the solution was slowly added to the 3-amino-1,2-propanediol solution prepared in step 3), followed by adding deionized water until the total volume reached 1 L, and stirring was continued to mix the components uniformly.

[0218] 5) Copper sulfate, sulfuric acid, hydrogen chloride, ethylenethiourea, sodium dodecylsulfonate and polyethyleneimine alkyl salt were mixed in water, and then 10 ml of the copper plating additive composition prepared in step 4) was added thereto.

[0219] (2) First, magnetron sputtering of nichrome was performed on a PET film, followed by magnetron sputtering of copper (first copper plating process), and the resulting copper film was tested. (1) The sheet resistance of the copper film was tested, and the test result was 400 mΩ. (2) Tape was applied to the copper film and peeled off by hand, and the adhesion passed. (3) Micropores were observed in the copper film by illuminating the back of the film with a mobile phone. (4) The thickness of the copper film measured using the Fischei method was 0.34 μm.

[0220] (3) A second copper plating process was performed on the first copper film and the second copper film using a copper brush plating method.

[0221] Using the brush plating equipment shown in Figure 2, a second copper plating process was performed on the copper film under the following parameters: plating temperature 30°C, plating time 3 min, operating voltage 5 V, and relative movement speed of the plastic film relative to the brush plating roller 7 m / min. The resulting copper film was tested. (1) The copper film's sheet resistance was tested, and the test result was 5.12 mΩ. (2) Tape was applied to the copper film and peeled off by hand, and no copper was peeled off. Therefore, the adhesion test passed. (3) The film surface after brush plating was shiny, and no other holes were observed other than those formed during the sheet resistance test. (4) The copper film thickness measured using the Fischei method was 0.885 μm, and the film thickness increased by brush plating was 0.545 μm.

[0222] The technical features of the above embodiments can be combined in any manner, and for the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, combinations of these technical features should be considered to be within the scope of the present specification unless there is a contradiction.

[0223] The above examples merely illustrate some embodiments of the present application, and although the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention. Those skilled in the art may make various modifications and improvements without departing from the spirit of the present application, and all of these are within the scope of protection of the present application. Therefore, the scope of protection of the present application should be governed by the appended claims.

Claims

1. A copper plating additive composition comprising 1,4-cyclohexanedione monoethylene acetal, potassium phthalimide, and an aminopolyol compound.

2. the mass ratio of 1,4-cyclohexanedione monoethylene acetal to potassium phthalimide to aminopolyol compound is (0.6 to 1.0):(1.2 to 2.0):(1.8 to 3.0); 2. The copper plating additive composition of claim 1.

3. 2. The copper plating additive composition of claim 1, wherein the aminopolyol compound is 3-amino-1,2-propanediol.

4. A copper plating solution comprising the copper plating additive composition according to any one of claims 1 to 3.

5. 5. The copper plating solution according to claim 4, further comprising water, copper sulfate, sulfuric acid, and chloride ions.

6. The copper plating solution per liter contains water, 1,4-cyclohexanedione monoethylene acetal 0.06 g to 0.10 g, Potassium phthalimide 0.12g to 0.20g, 0.18 g to 0.30 g of an aminopolyol compound, Copper sulfate 120g to 220g, 50-70g sulfuric acid, and Contains 60mg to 80mg of chloride ions.

6. The copper plating solution according to claim 5.

7. The copper plating solution further comprises a brightener, a surfactant, and a leveling agent; the brightener is one or more selected from ethylene thiourea, benzimidazole, and aliphatic amine ethoxysulfonate; the surfactant is one or two selected from sodium dodecyl sulfonate and 3,3'-dithiobis(sodium 1-propanesulfonate); 5. The copper plating solution according to claim 4, wherein the leveling agent is one or more selected from the group consisting of polyethylene glycol, 1,4-butynediol, and polyethyleneimine alkyl salts.

8. The copper plating solution per liter contains water, 1,4-cyclohexanedione monoethylene acetal 0.06 g to 0.10 g, Potassium phthalimide 0.12g to 0.20g, 0.18 g to 0.30 g of an aminopolyol compound, Copper sulfate 120g to 220g, Sulfuric acid 50g to 70g, Chloride ions 60mg to 80mg, Brightener 0.0002 mg to 0.0008 mg, 0.05 mg to 0.1 mg of surfactant, and 0.05g to 0.1g of a leveling agent; 7. The copper plating solution according to claim 6.

9. The copper plating solution per liter contains water, 1,4-cyclohexanedione monoethylene acetal 0.06 g to 0.10 g, Potassium phthalimide 0.12g to 0.20g, 0.18 g to 0.30 g of an aminopolyol compound, Copper sulfate 120g to 220g, Sulfuric acid 50g to 70g, Chloride ions 60mg to 80mg, ethylenethiourea 0.0002 mg to 0.0008 mg, Sodium dodecyl sulfonate 0.05 mg to 0.1 mg, and polyethylene glycol 0.05g to 0.1g, 7. The copper plating solution according to claim 6.

10. The copper plating process includes contacting a substrate with the copper plating solution according to claim 4, Plating temperature: 35℃ to 45℃ Plating time: 1 to 2 minutes and an operating voltage of 2V to 7V.

11. performing a copper plating process on the surface of the substrate using a copper brush plating method to form a copper film on the surface of the substrate; the anode during the copper plating process is a brush plating roller; 5. A copper brush plating method for providing a coating layer on a surface of a substrate, wherein the copper plating process further comprises contacting the surface of the substrate with the copper plating solution of claim 4.

12. The method further includes the step of performing a first copper plating process on the plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film, thereby forming a substrate; The thickness of the plastic film is 3.2 μm to 12 μm, the physical vapor deposition method is a magnetron sputtering method or an evaporation method, 12. The copper brush plating method according to claim 11, wherein the brush plating roller is covered with a sponge-like liquid-absorbing layer.

13. performing a first copper plating process on the plastic film using physical vapor deposition to form a first copper film on one surface of the plastic film and a second copper film on the other surface of the plastic film; performing a second copper plating process on the first copper film and the second copper film using a copper brush plating method to form a third copper film on the first copper film and a fourth copper film on the second copper film; the anode during the second copper plating process is a brush plating roller; The second copper plating process further comprises contacting the first copper film and the second copper film with the copper plating solution according to claim 4.

1. A copper brush plating method for providing a coating layer on a surface of a substrate, comprising:

14. The second copper plating process is Plating temperature: 0℃ to 45℃ Plating time: 1 to 10 minutes Operating voltage 1V to 7V, 14. The copper brush plating method according to claim 13, wherein the copper brush plating is performed at one or more parameters selected from the group consisting of: a relative movement speed of the plastic film with respect to the brush plating roller of 3 m / min to 10 m / min;

15. the sheet resistance of each of the first copper film and the second copper film is 2200 mΩ or less, and / or the thickness of each of the first copper film and the second copper film is independently 0.1 μm to 0.5 μm; The thickness of the plastic film is 3.2 μm to 12 μm, the physical vapor deposition method is a magnetron sputtering method or an evaporation method, 14. The copper brush plating method according to claim 13, wherein the brush plating roller is covered with a sponge-like liquid-absorbing layer.

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