Copper brightener at room temperature and its preparation method

Abstract

The application discloses a copper normal-temperature neutral brightener and a preparation method thereof. The brightener is prepared by compounding main materials, including organic amine, organic complexing agent, reducing agent, corrosion inhibitor, surfactant and deionized water, and functional additives, and each component is combined according to a specific proportion. The raw material components of the application can realize efficient bright treatment of copper materials under normal-temperature neutral conditions through mutual synergistic effect, effectively improve the mirror gloss of the surface of the copper part, and significantly reduce the corrosion loss of the brightener to the copper base material. The brightener system has excellent compatibility, a long storage stable period, a simple preparation process, and can be finished product only by mixing and filtering, and is convenient and practical to operate, and is suitable for normal-temperature chemical bright processing scenes of various copper products.

Description

Technical Field

[0001] This invention belongs to the field of cleaning agent technology, and relates to a brightener, specifically a neutral brightener for copper at room temperature. Background Technology

[0002] Copper and copper alloys are widely used in electronics, electrical and communication equipment, precision instruments, and decorative materials due to their excellent electrical and thermal conductivity and good machinability. However, during hot working, machining, and storage, copper surfaces are highly susceptible to oxidation, sulfidation, or corrosion, resulting in dark oxide films, sulfide films, or other stains. These defects severely affect the appearance and subsequent welding, painting, and bonding processes. Therefore, cleaning and polishing copper surfaces to restore their metallic luster is a crucial step in copper processing and applications.

[0003] Currently, the mainstream copper brightening technology in industry mostly uses strong acidic chemical polishing slurries, with inorganic acids such as nitric acid, sulfuric acid, and hydrochloric acid as the main components, supplemented by oxidants or brightening agents. Although this type of strong acid system has the advantages of fast polishing speed and high initial gloss, its application defects are also very prominent: First, the strong acidic environment has a severe corrosive effect on the copper substrate, which can easily cause over-corrosion of the workpiece, resulting in dimensional deviations, whitening of edges and corners, and even perforation of precision copper parts, making it unsuitable for delicate workpieces such as thin-walled copper tubes, micro connectors, and precision terminals; Second, the operation process will release toxic and harmful gases such as nitrogen oxides and acid mists, which seriously endanger the occupational health of operators and corrode equipment in the production workshop; Third, polishing produces a large amount of cleaning wastewater with high acidity and high concentration of heavy metal ions, which has high treatment costs, is difficult to meet emission standards, and has a heavy environmental burden, which is contrary to the current industrial orientation of green manufacturing and clean production.

[0004] To overcome the above-mentioned defects of strong acid systems, the industry has begun to focus on neutral or weakly alkaline brightening treatment technologies in recent years. Existing publicly available neutral copper brightener technologies, such as compounding organic amines, organic acids or their salts with surfactants, attempt to achieve copper surface brightening under mild pH conditions. However, practice shows that existing neutral brightener technologies generally have the following technical limitations: (1) Low polishing efficiency at room temperature and insufficient brightness. Existing formulations have limited ability to remove the oxide film on the copper surface at room temperature of 20-35℃. After polishing, the workpiece surface generally has a hazy layer, poor gloss uniformity, and it is difficult to achieve a mirror-level bright effect. They are mostly suitable for low-end cleaning or matte treatment scenarios; (2) Poor system stability and short service life. During long-term storage or recycling, multi-component organic components are prone to problems such as layering, precipitation, oxidation failure of effective components or microbial growth, resulting in large fluctuations in the brightening effect during batch processing, which makes it difficult to meet the requirements of consistency of reagents for automated continuous production; (3) Reliance on auxiliary strengthening methods, high energy consumption and equipment requirements. Some of the claimed neutral brighteners have insufficient activity at room temperature. In actual applications, they need to be combined with heating (40-60℃), ultrasonic or mechanical stirring and other enhanced conditions to obtain an acceptable brightening effect, which increases the complexity of the process and energy consumption costs.

[0005] Therefore, developing a brightener that can efficiently achieve a mirror-like finish on copper materials under neutral conditions at room temperature, while also possessing low corrosion, high stability, long-lasting protection, and good substrate compatibility, is of significant technical value and practical importance for meeting the actual production needs of the high-precision copper processing, electronic packaging, and decorative copper material industries. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a room-temperature neutral brightener for copper. This brightener has high cleaning efficiency, significant brightening effect, and no risk of over-corrosion.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: a copper room-temperature neutral brightener, comprising the following components by mass percentage: Organic amines 5-15%; Organic complexing agent 5-10%; Reducing agent 3-6%; Corrosion inhibitor 0.5-2%; Surfactant 10-15%; Thioglycerin 0.1-0.4%; Polyaspartic acid 0.4-0.6%; Hydroxypropyl-β-cyclodextrin 0.1-0.3%; The number-average molecular weight of the polyaspartic acid is 3000~5000 Da; The remainder is deionized water, and the surfactant is a compound of gemini quaternary ammonium salt and isomeric alcohol polyoxyethylene ether in a mass ratio of 1:(0.8-1.2).

[0008] Optimally, the organic amine is a compound of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:(0.8-1.2):(1-3).

[0009] Ideally, the organic complexing agent is a compound of hydroxyethyl ethylenediamine triacetic acid and potassium sodium tartrate in a mass ratio of 1:(1-2).

[0010] Optimally, the reducing agent is a compound of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:(1-2):(0.8-1.2):0.5:(0.4-0.6).

[0011] Furthermore, the aldehyde compound is at least one of glyoxal, vanillin, and furfural.

[0012] Optimally, the sulfite is at least one of sodium sulfite, potassium sulfite, and ammonium sulfite; and the corrosion inhibitor is at least one of 2-methylimidazole and 1-hydroxybenzotriazole.

[0013] Optimally, the gemini quaternary ammonium salt is at least one of dodecyl dimethyl methylene quaternary ammonium salt and dodecylamine polyoxyethylene ether quaternary ammonium salt, and the isomeric alcohol polyoxyethylene ether is branched isomeric tridecyl alcohol polyoxyethylene ether.

[0014] Ideally, its pH value is 6.5~7.5.

[0015] Another objective of this invention is to provide a method for preparing the above-mentioned copper room-temperature neutral brightener, comprising the following steps: mixing and stirring the formulated amounts of organic amine, organic complexing agent, reducing agent, corrosion inhibitor, surfactant, thioglycerol, polyaspartic acid, hydroxypropyl-β-cyclodextrin and deionized water at room temperature until completely dissolved or evenly dispersed; then filtering to remove insoluble matter and trace mechanical impurities; and filling the filtrate to obtain the finished product.

[0016] Ideally, the filtration uses a filter membrane with a pore size of 0.20~1.0 μm.

[0017] Compared with existing technologies, this invention has the following beneficial technical effects: The copper room-temperature neutral brightener of this invention employs multi-component organic amine complex coordination, multi-element reducing agent synergistic reduction, and is combined with compound surfactants and azole corrosion inhibitors. It is also supplemented with thioglycerol, polyaspartic acid, and hydroxypropyl-β-cyclodextrin functional additives for synergistic effect, achieving a uniform and high-brightness finish on copper parts under room-temperature neutral conditions. Specifically, this brightener significantly improves the brightness and micro-leveling of the copper surface, effectively inhibits corrosion and oxidation of the copper substrate, and enhances the stability of the reagent system and the protective performance of the treated workpiece. Compared with existing technologies, this invention effectively avoids the technical defects of conventional brighteners, such as acid corrosion, poor low-temperature activity, uneven gloss, and easy storage failure. It has the outstanding advantages of wide applicability and significantly improved overall performance, and is particularly suitable for neutral room-temperature chemical brightening processing of high-precision copper parts. Detailed Implementation

[0018] This invention relates to a room-temperature neutral brightener for copper, comprising the following components by mass percentage: 5-15% organic amine; 5-10% organic complexing agent; 3-6% reducing agent; 0.5-2% corrosion inhibitor; 10-15% surfactant; 0.1-0.4% thioglycerol; 0.4-0.6% polyaspartic acid; and 0.1-0.3% hydroxypropyl-β-cyclodextrin, wherein the number-average molecular weight of the polyaspartic acid is 3000-5000 Da; the balance is deionized water. The surfactant is a compound of gemini quaternary ammonium salt and isomeric alcohol polyoxyethylene ether in a mass ratio of 1:(0.8-1.2). By employing multi-component organic amine complex coordination, synergistic reduction by multiple reducing agents, and combined with compound surfactants and azole corrosion inhibitors, along with the synergistic effect of thioglycerol, polyaspartic acid, and hydroxypropyl-β-cyclodextrin functional additives, a uniform and high-brightness brightening effect can be achieved on the surface of copper parts under room-temperature neutral conditions. Specifically, this brightener significantly improves the gloss and micro-leveling of copper surfaces, effectively inhibits corrosion and oxidation of the copper substrate, and enhances the stability of the chemical system and the protective performance of the treated workpiece. Compared with existing technologies, this invention effectively avoids the technical defects of conventional brighteners, such as acid corrosion, poor low-temperature activity, uneven gloss, and easy deterioration during storage. It has the outstanding advantages of wide applicability and significantly improved overall performance, and is especially suitable for neutral room-temperature chemical brightening processes for high-precision copper parts.

[0019] The organic amine is a compound of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:(0.8-1.2):(1-3). The organic complexing agent is a compound of hydroxyethylethylenediaminetriacetic acid and sodium potassium tartrate in a mass ratio of 1:(1-2). The reducing agent is a compound of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:(1-2):(0.8-1.2):0.5:(0.4-0.6). The aldehyde compound is at least one of glyoxal, vanillin, and furfural. The sulfite is at least one of sodium sulfite, potassium sulfite, and ammonium sulfite. The corrosion inhibitor is at least one of 2-methylimidazole and 1-hydroxybenzotriazole. The geminal quaternary ammonium salt is at least one of dodecyl dimethylmethylene bisquaternary ammonium salt and dodecylamine polyoxyethylene ether bisquaternary ammonium salt, and the isomeric alcohol polyoxyethylene ether is branched isomeric tridecyl alcohol polyoxyethylene ether. Its pH value is 6.5~7.5.

[0020] The working principle and synergistic mechanism of each component of the copper room temperature neutral brightener of the present invention are as follows: (1) Organic amine complex coordination system: The organic amine is triethylenetetramine, glycine and ethylenediamine are compounded in a mass ratio of 1:(0.8-1.2):(1-3). Triethylenetetramine has a strong multidentate coordination ability and can form a stable soluble complex with copper ions to promote the dissolution and peeling of the surface oxide film; glycine has both coordination and buffering functions, which helps to maintain the pH stability of the system; ethylenediamine, as a small molecule ligand, can penetrate into the microcracks of the oxide film and improve the deep cleaning ability. The three are compounded to form a "strong-medium-weak" multi-level coordination network to achieve mild and controllable peeling of copper surface oxides and avoid over-corrosion. (2) Synergistic solubilization of organic complexing agent: The organic complexing agent is hydroxyethyl ethylenediamine triacetic acid (HEDTA) and potassium sodium tartrate in a mass ratio of 1:(1-2). HEDTA has a strong complexing constant for high-valence copper ions and can effectively capture Cu released during polishing. 2+ To prevent secondary deposition on the surface; potassium sodium tartrate has both complexing and surface conditioning effects, which can improve the wettability and fluidity of the polishing solution. The synergistic use of the two significantly increases the solubility threshold of copper ions during the polishing process and extends the service life of the solution. (3) Selective adsorption of corrosion inhibitor: The corrosion inhibitor is at least one of 2-methylimidazole and 1-hydroxybenzotriazole. The nitrogen atom in the azole compound contains lone pair electrons, which can form coordinate bonds with empty orbitals on the copper surface, and preferentially adsorb on the copper surface to form a dense monomolecular protective film. This film can prevent excessive corrosion by acid oxidation during the polishing process, and can also provide long-term anti-oxidation and anti-sulfurization protection for copper materials after treatment.

[0021] The preparation method of the above-mentioned room-temperature neutral brightener for copper includes the following steps: Mixing and stirring the formulated amounts of organic amine, organic complexing agent, reducing agent, corrosion inhibitor, surfactant, thioglycerol, polyaspartic acid, hydroxypropyl-β-cyclodextrin, and deionized water at room temperature until completely dissolved or evenly dispersed; then filtering to remove insoluble matter and trace mechanical impurities; and finally filling the filtrate to obtain the finished product. The filtration uses a filter membrane with a pore size of 0.20~1.0 μm.

[0022] The present invention will be further described below with reference to embodiments: Examples 1-6 Examples 1-6 provide a copper room temperature neutral brightener and its preparation method, and the dosage of each component is shown in Table 1.

[0023] Table 1. Dosage of each component in Examples 1-6 (unit: kg)

[0024] Note: "-" indicates that it has not been added.

[0025] The specific composition of each compound component in each embodiment is also described in detail (all listed in actual weighing values, which can be directly used for preparation): Example

[0026] Organic amine: composed of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:0.8:1. In 5.0 kg of organic amine, the actual amounts of each component are: triethylenetetramine: 1.79 kg, glycine: 1.43 kg, and ethylenediamine: 1.78 kg.

[0027] Organic complexing agent: composed of hydroxyethyl ethylenediamine triacetic acid (HEDTA) and potassium sodium tartrate in a 1:1 mass ratio. In 5.0 kg of organic complexing agent, the actual amounts of each component are: HEDTA: 2.50 kg, potassium sodium tartrate: 2.50 kg.

[0028] The reducing agent is a compound of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:1:0.8:0.5:0.4. In 3.0 kg of the reducing agent, the actual amounts of each component are: sodium oxalate: 0.81 kg, ascorbic acid: 0.81 kg, hydrazine hydrate: 0.65 kg, aldehyde compound (glyoxal): 0.41 kg, and sulfite (sodium sulfite): 0.32 kg.

[0029] Corrosion inhibitor: 2-methylimidazole, 0.5 kg.

[0030] Surfactant: A compound of gemini quaternary ammonium salt (dodecyl dimethyl methylene bisquaternary ammonium salt) and isomeric alcohol polyoxyethylene ether (branched isomeric tridecyl alcohol polyoxyethylene ether) at a mass ratio of 1:0.8. In 10.0 kg of surfactant, the actual amounts of each component are: gemini quaternary ammonium salt: 5.56 kg, isomeric alcohol polyoxyethylene ether: 4.44 kg.

[0031] Preparation method: Under normal temperature (20–30℃), deionized water, organic amine, organic complexing agent, reducing agent, corrosion inhibitor, and surfactant are added sequentially to a preparation vessel. The mixture is stirred at 300–600 rpm for 15–30 min until completely dissolved or evenly dispersed. The solution is then filtered through a precision microporous membrane with a pore size of 0.22 μm to remove insoluble matter and trace mechanical impurities. The filtrate is then sealed and packaged in a clean environment to obtain the finished product. Example

[0032] Organic amine: composed of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:0.9:1.5. In 7.0 kg of organic amine, the actual amounts of each component are: triethylenetetramine: 2.06 kg, glycine: 1.85 kg, and ethylenediamine: 3.09 kg. Organic complexing agent: composed of HEDTA and sodium potassium tartrate in a mass ratio of 1:1.2. In 7.0 kg of organic complexing agent, the actual amounts of each component are: HEDTA: 3.18 kg, sodium potassium tartrate: 3.82 kg.

[0033] The reducing agent is a compound of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:1.3:0.9:0.5:0.45. In 4.0 kg of the reducing agent, the actual amounts of each component are: sodium oxalate: 0.96 kg, ascorbic acid: 1.25 kg, hydrazine hydrate: 0.87 kg, aldehyde compound (vanillin): 0.48 kg, and sulfite (potassium sulfite): 0.44 kg.

[0034] Corrosion inhibitor: 1-hydroxybenzotriazole, 1.0 kg.

[0035] Surfactant: A compound of gemini quaternary ammonium salt (dodecylamine polyoxyethylene ether bisquaternary ammonium salt) and isomeric alcohol polyoxyethylene ether (branched isomeric tridecyl alcohol polyoxyethylene ether) at a mass ratio of 1:0.9. In 11.0 kg of surfactant, the actual amounts of each component are: gemini quaternary ammonium salt: 5.79 kg, isomeric alcohol polyoxyethylene ether: 5.21 kg.

[0036] Functional additives: Thioglycerin: 0.2 kg, Polyaspartic acid (number average molecular weight 3000 Da): 0.45 kg, Hydroxypropyl-β-cyclodextrin: 0.15 kg.

[0037] Preparation method: Refer to Example 1, add deionized water and each component, stir evenly, filter and fill to obtain the final product. Example

[0038] Organic amine: composed of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:1:2. In 10.0 kg of organic amine, the actual amounts of each component are: triethylenetetramine: 2.50 kg, glycine: 2.50 kg, and ethylenediamine: 5.00 kg.

[0039] Organic complexing agent: composed of HEDTA and sodium potassium tartrate in a mass ratio of 1:1.5. In 8.0 kg of organic complexing agent, the actual amounts of each component are: HEDTA: 3.20 kg, sodium potassium tartrate: 4.80 kg.

[0040] Reducing agent: composed of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:1.5:1:0.5:0.5. In 4.5 kg of reducing agent, the actual amounts of each component are: sodium oxalate: 1.00 kg, ascorbic acid: 1.50 kg, hydrazine hydrate: 1.00 kg, aldehyde compound (furfural): 0.50 kg, and sulfite (ammonium sulfite): 0.50 kg.

[0041] Corrosion inhibitor: 2-methylimidazole, 1.2 kg.

[0042] Surfactant: It is a compound of gemini quaternary ammonium salt (dodecyl dimethyl methylene bisquaternary ammonium salt) and isomeric alcohol polyoxyethylene ether (branched isomeric tridecyl alcohol polyoxyethylene ether) in a mass ratio of 1:1. In 13.0 kg of surfactant, the actual amount of each component is: gemini quaternary ammonium salt: 6.50 kg, isomeric alcohol polyoxyethylene ether: 6.50 kg.

[0043] Functional additives: Thioglycerin: 0.25 kg, Polyaspartic acid (number average molecular weight 3500 Da): 0.50 kg, Hydroxypropyl-β-cyclodextrin: 0.20 kg.

[0044] Preparation method: Refer to Example 1, add deionized water and each component, stir evenly, filter and fill to obtain the final product. Example

[0045] Organic amine: composed of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:1.1:2.5. In 13.0 kg of organic amine, the actual amounts of each component are: triethylenetetramine: 2.83 kg, glycine: 3.11 kg, and ethylenediamine: 7.06 kg.

[0046] Organic complexing agent: composed of HEDTA and sodium potassium tartrate in a mass ratio of 1:1.8. In 9.0 kg of organic complexing agent, the actual amounts of each component are: HEDTA: 3.21 kg, sodium potassium tartrate: 5.79 kg.

[0047] The reducing agent is a compound composed of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:1.8:1.1:0.5:0.55. In 5.5 kg of the reducing agent, the actual amounts of each component are: sodium oxalate: 1.10 kg, ascorbic acid: 1.98 kg, hydrazine hydrate: 1.21 kg, aldehyde compound (glyoxal:vanillin:furfural = 1:1:2): 0.55 kg, and sulfite (sodium sulfite:potassium sulfite:ammonium sulfite = 2:1:2): 0.61 kg.

[0048] Corrosion inhibitor: It is a compound of 2-methylimidazole and 1-hydroxybenzotriazole in a mass ratio of 1:1, with a total amount of 1.8 kg and each of them weighing 0.90 kg.

[0049] Surfactant: A compound of gemini quaternary ammonium salt (dodecyl dimethyl methylene bisquaternary ammonium salt: dodecylamine polyoxyethylene ether bisquaternary ammonium salt = 1:3) and isomeric alcohol polyoxyethylene ether (branched isomeric tridecyl alcohol polyoxyethylene ether) at a mass ratio of 1:1.1. In 14.0 kg of surfactant, the actual amounts of each component are: gemini quaternary ammonium salt mixture: 6.67 kg (of which 1.67 kg isodecyl dimethyl methylene bisquaternary ammonium salt and 5.00 kg isomeric alcohol polyoxyethylene ether): 7.33 kg.

[0050] Functional additives: Thioglycerin: 0.30 kg, Polyaspartic acid (number average molecular weight 4000 Da): 0.55 kg, Hydroxypropyl-β-cyclodextrin: 0.25 kg.

[0051] Preparation method: Refer to Example 1, add deionized water and each component, stir evenly, filter and fill to obtain the final product. Example

[0052] Organic amine: composed of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:1.2:3. In 15.0 kg of organic amine, the actual amounts of each component are: triethylenetetramine: 2.88 kg, glycine: 3.46 kg, and ethylenediamine: 8.66 kg.

[0053] Organic complexing agent: composed of HEDTA and sodium potassium tartrate in a mass ratio of 1:2. In 10.0 kg of organic complexing agent, the actual amounts of each component are: HEDTA: 3.33 kg, sodium potassium tartrate: 6.67 kg.

[0054] The reducing agent is a compound composed of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:2:1.2:0.5:0.6. In 6.0 kg of the reducing agent, the actual amounts of each component are: sodium oxalate: 1.13 kg, ascorbic acid: 2.26 kg, hydrazine hydrate: 1.36 kg, aldehyde compound (glyoxal): 0.57 kg, and sulfite (sodium sulfite): 0.68 kg.

[0055] Corrosion inhibitor: 2-methylimidazole, 2.0 kg.

[0056] Surfactant: A compound of gemini quaternary ammonium salt (dodecyl dimethyl methylene bisquaternary ammonium salt) and isomeric alcohol polyoxyethylene ether (branched isomeric tridecyl alcohol polyoxyethylene ether) at a mass ratio of 1:1.2. In 15.0 kg of surfactant, the actual amounts of each component are: gemini quaternary ammonium salt: 6.82 kg, isomeric alcohol polyoxyethylene ether: 8.18 kg.

[0057] Functional additives: Thioglycerin: 0.40 kg, Polyaspartic acid (number average molecular weight 5000 Da): 0.60 kg, Hydroxypropyl-β-cyclodextrin: 0.30 kg.

[0058] Preparation method: Refer to Example 1, add deionized water and each component, stir evenly, filter and fill to obtain the final product. Example

[0059] Organic amine: composed of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:1:2. In 10.0 kg of organic amine, the actual amounts of each component are: triethylenetetramine: 2.50 kg, glycine: 2.50 kg, and ethylenediamine: 5.00 kg.

[0060] Organic complexing agent: composed of HEDTA and sodium potassium tartrate in a mass ratio of 1:1.5. In 8.5 kg of organic complexing agent, the actual amounts of each component are: HEDTA: 3.40 kg, sodium potassium tartrate: 5.10 kg.

[0061] The reducing agent is a compound of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:1.5:1:0.5:0.5. In 5.0 kg of reducing agent, the actual amounts of each component are: sodium oxalate: 1.11 kg, ascorbic acid: 1.67 kg, hydrazine hydrate: 1.11 kg, aldehyde compound (glyoxal): 0.56 kg, and sulfite (sodium sulfite): 0.56 kg.

[0062] Corrosion inhibitor: 2-methylimidazole, 1.5 kg.

[0063] Surfactant: It is a compound of gemini quaternary ammonium salt (dodecyl dimethyl methylene bisquaternary ammonium salt) and isomeric alcohol polyoxyethylene ether (branched isomeric tridecyl alcohol polyoxyethylene ether) in a mass ratio of 1:1. In 12.5 kg of surfactant, the actual amount of each component is: gemini quaternary ammonium salt: 6.25 kg, isomeric alcohol polyoxyethylene ether: 6.25 kg.

[0064] Functional additives: Thioglycerin: 0.30 kg, Polyaspartic acid (number average molecular weight 4000 Da): 0.50 kg, Hydroxypropyl-β-cyclodextrin: 0.25 kg.

[0065] Preparation method: Refer to Example 1, add deionized water and each component, stir evenly, filter and fill to obtain the final product.

[0066] Comparative Examples 1–4 Comparative Examples 1-4 each provide a copper room-temperature neutral brightener, as detailed below: Comparative Example 1: It is basically the same as Example 5, except that an equal amount of thioglycerol is used instead of hydroxypropyl-β-cyclodextrin (i.e., 0.7 kg of thioglycerol without hydroxypropyl-β-cyclodextrin).

[0067] Comparative Example 2: It is basically the same as Example 5, except that an equal amount of hydroxypropyl-β-cyclodextrin is used instead of thioglycerol (i.e., 0.7 kg of hydroxypropyl-β-cyclodextrin without thioglycerol).

[0068] Comparative Example 3: It is basically the same as Example 5, except that an equal amount of Gemini quaternary ammonium salt is used instead of isomeric alcohol polyoxyethylene ether (i.e., all surfactants are Gemini quaternary ammonium salts).

[0069] Comparative Example 4: It is basically the same as Example 5, except that an equal amount of isomeric alcohol polyoxyethylene ether is used instead of gemini quaternary ammonium salt (i.e., all surfactants are isomeric alcohol polyoxyethylene ether).

[0070] The performance of the copper room-temperature neutral brighteners of Examples 1-6 and Comparative Examples 1-4 was tested. The testing methods all referred to national standards. The specific test items, test methods and national standard references are as follows: (1) pH test: The test was conducted in accordance with GB / T 9724-2007 "General Rules for pH Determination of Chemical Reagents" (using a calibrated pH meter to measure directly at 25±1℃).

[0071] (2) Brightness effect test: The 50mm×50mm×0.5mm T2 copper sheet was completely immersed in the brightener of each sample and soaked at 25℃ and normal humidity for 5 minutes. After being taken out, it was rinsed with room temperature ultrapure water for 30 seconds and dried evenly with room temperature cold air. It was then placed in a desiccator to cool to room temperature for later use. Then, the mirror gloss meter was turned on and preheated for 30 minutes. Zero-point calibration and range calibration were completed using the instrument's matching standard gloss plate to eliminate instrument system errors. The prepared, clean and residue-free, and completely dry copper sample was selected. The gloss was tested at five points in the center area and four corner areas of the sample. Each point was tested three times consecutively. The single test value was recorded. Finally, the arithmetic mean of all test data was taken as the 60° mirror gloss result of the sample, in GU (60° test angle was used uniformly).

[0072] (3) Substrate corrosion rate test: Referring to ASTM G31-21(2025), before the test, the copper sample was dried in an oven at 105℃ for 30 min, then removed and placed in a desiccator to cool to room temperature. The initial mass of the sample was accurately weighed using an electronic analytical balance with an accuracy of 0.0001 g and recorded. The sample was completely immersed in the corresponding brightener solution and soaked at a constant temperature of 25℃ for 5 min. After the treatment, the sample was removed, rinsed with pure water, thoroughly dried with cold air, dried and cooled again, and accurately weighed. The corrosion rate of the copper substrate was calculated based on the mass difference before and after immersion, the sample surface area, and the immersion time. The unit is g / (m²·h). The smaller the value, the lower the corrosion loss of the copper substrate by the agent.

[0073] (4) Storage stability test: The prepared brighteners were placed into sealed, transparent, light-proof storage bottles, with the filling volume uniformly set at 80% of the bottle volume to avoid the influence of thermal expansion and contraction on the stability assessment. All samples were placed in a constant temperature and humidity storage chamber at 25℃ and 55%RH and stored statically. The state of the agents was continuously observed and recorded. The longest storage time during which the agents did not show stratification, turbidity, precipitation, discoloration, off-odor, or activity decay was taken as the storage stability period of the agents, in months. The test results are shown in Table 2.

[0074] Table 2 Performance test data of copper room temperature neutral brightener

[0075] As shown in Table 2, the pH of each brightener system is within the neutral range. The more perfect the formulation components are, the higher the mirror gloss of the copper sheet, the lower the corrosion rate of the substrate, and the better the storage stability of the agent. The performance of the product decreased significantly after replacing or missing key additives, which shows the optimization effect of the synergistic combination of the components.

[0076] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. At the same time, those skilled in the art should understand and implement the above description. Therefore, any equivalent changes or modifications made without departing from the concept disclosed in the present invention should be covered within the scope of protection of the present invention.

Claims

1. A copper room-temperature neutral brightener, characterized in that, Includes the following components by mass percentage: Organic amines 5-15%; Organic complexing agent 5-10%; Reducing agent 3-6%; Corrosion inhibitor 0.5-2%; Surfactant 10-15%; Thioglycerin 0.1-0.4%; Polyaspartic acid 0.4-0.6%; Hydroxypropyl-β-cyclodextrin 0.1-0.3%; The number-average molecular weight of the polyaspartic acid is 3000~5000 Da; The remainder is deionized water, and the surfactant is a compound of gemini quaternary ammonium salt and isomeric alcohol polyoxyethylene ether in a mass ratio of 1:(0.8-1.2). The organic amine is a compound of triethylenetetramine, glycine, and ethylenediamine in a mass ratio of 1:(0.8-1.2):(1-3). The organic complexing agent is a compound of hydroxyethyl ethylenediamine triacetic acid and potassium sodium tartrate in a mass ratio of 1:(1-2); The reducing agent is a compound of sodium oxalate, ascorbic acid, hydrazine hydrate, aldehyde compound, and sulfite in a mass ratio of 1:(1-2):(0.8-1.2):0.5:(0.4-0.6).

2. The copper room-temperature neutral brightener according to claim 1, characterized in that: The aldehyde compound is at least one of glyoxal, vanillin, and furfural, and the sulfite is at least one of sodium sulfite, potassium sulfite, and ammonium sulfite.

3. The copper room-temperature neutral brightener according to claim 1, characterized in that: The corrosion inhibitor is at least one of 2-methylimidazole and 1-hydroxybenzotriazole.

4. The copper room-temperature neutral brightener according to claim 1, characterized in that: The gemini quaternary ammonium salt is at least one of dodecyl dimethyl methylene quaternary ammonium salt and dodecylamine polyoxyethylene ether quaternary ammonium salt, and the isomeric alcohol polyoxyethylene ether is branched isomeric tridecyl alcohol polyoxyethylene ether.

5. The copper room-temperature neutral brightener according to claim 1, characterized in that: Its pH value is 6.5~7.

5.

6. The method for preparing the copper room-temperature neutral brightener according to any one of claims 1-5, characterized in that, The process includes the following steps: mixing the formulated amounts of organic amine, organic complexing agent, reducing agent, corrosion inhibitor, surfactant, thioglycerol, polyaspartic acid, hydroxypropyl-β-cyclodextrin, and deionized water at room temperature until they are completely dissolved or evenly dispersed; then filtering to remove insoluble matter and trace mechanical impurities; and finally filling the filtrate to obtain the finished product.

7. The method for preparing the copper room-temperature neutral brightener according to claim 6, characterized in that: The filtration process uses a filter membrane with a pore size of 0.20~1.0 μm.

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