Imidazolyl surface treatment additive as well as preparation method and application thereof

Abstract

The invention relates to an imidazolyl surface treatment additive as well as a preparation method and application thereof, and belongs to the technical field of surface treatment. In order to solve the problems of narrow current density range of an acidic copper electroplating bright area and fast consumption of a brightener, the invention provides a preparation method of an imidazolyl surface treatment additive, which comprises the following steps: dissolving sodium hydroxide, imidazole or an imidazole derivative, and pyridine or a pyridine derivative in deionized water, adding epichlorohydrin into the obtained mixed system, and stirring uniformly to obtain the imidazolyl surface treatment additive. And reacting until no epoxy chloropropane suspension is observed to obtain the imidazolyl surface treatment additive. When the prepared imidazolyl electroplating additive is applied to acid sulfate copper plating, the brightness of a copper plating layer in a low-current-density area can be remarkably improved, a plating layer is mirror-surface bright within the wide-current-density range of 0.1-10 A / dm < 2 >, the glossiness is kept to be 480 GU or above, the consumption rate of a sulfur-containing compound main brightener can be remarkably reduced, and the service life of the sulfur-containing compound main brightener is prolonged. Excellent application potential is shown.

Description

Technical Field

[0001] The invention belongs to the technical field of surface treatment, and in particular relates to an imidazole-based surface treatment additive and a preparation method and application thereof. Background Art

[0002] Acid sulfate copper plating is an electroplating process widely used in daily hardware electroplating, printed circuit boards, electroforming and other scenarios. It improves the conductivity of the substrate by forming a coating on the surface of the substrate, improving its appearance, corrosion resistance and cost savings. In the acid sulfate copper plating process, the current density range in the bright area directly affects the performance indicators such as the brightness, uniformity, density and adhesion of the coating. Within the appropriate current density range, acid sulfate copper plating can obtain a bright, smooth and uniform coating. However, for surface treatment technologies such as acid sulfate copper plating, there is a problem that the current density range in the bright area is not wide enough. If the current density exceeds this range, the brightness of the coating will drop significantly, and even other quality problems may occur, such as rough coating, burning, etc.

[0003] At the same time, the quality of the coating, electroplating efficiency and energy consumption are significantly affected by various additives. Acid sulfate copper plating additives are divided into brighteners, inhibitors and levelers. Brighteners can form stable complexes with copper ions, and by controlling the reduction rate and deposition method of copper ions, the coating can obtain higher brightness and more uniform deposits during the formation process. The most common brightener is sodium polydisulfide propane sulfonate (SPS), which can refine the grains and obtain a mirror-bright coating. However, SPS will be embedded in the coating during the electroplating process, and its chemical properties are not stable enough and it is easily oxidized and decomposed. Therefore, there is still a problem of fast consumption of brighteners during the electroplating process. Summary of the invention

[0004] In order to solve the problems of narrow current density range in bright area of ​​acid copper electroplating and fast consumption of brightener, the present invention provides an imidazole-based surface treatment additive and a preparation method and application thereof.

[0005] The technical solution of the present invention:

[0006] The invention discloses a method for preparing an imidazole-based surface treatment additive. The method comprises the following steps: dissolving sodium hydroxide, imidazole or an imidazole derivative, and pyridine or a pyridine derivative in deionized water, adding epichlorohydrin to the obtained mixed system, and reacting until no epichlorohydrin suspension is observed to obtain the imidazole-based surface treatment additive, wherein the ratio of the number of imidazole rings in the imidazole or imidazole derivative to the number of epoxy rings in epichlorohydrin is 0.1-10:0.1-10, and the ratio of the number of imidazole rings in the imidazole or imidazole derivative to the number of pyridine rings in the pyridine or pyridine derivative is 0.1-10:0.1-10.

[0007] Furthermore, the imidazole derivative is a product in which 1 to 4 hydrogen atoms on the imidazole ring are replaced by substituents, and the substituents are hydrocarbon groups, halogens, -NH2, -NHR, -NR2, -PH2, -PHR, -PR2, -OH, -SH, -OR, -SR, -SO2H, -SO3H, -CHO, -COR, -CORNH2, -COOH, -COOR, -C≡N, -N=O, -NO2, -NH-NH2, -CO(NH2), -SiR3, -B(OH)2 or N, S-containing heterocyclic substituents, or substituents obtained by replacing a hydrogen atom or substituent in one of the above groups with one or more of the above groups, and R represents a hydrocarbon group.

[0008] Furthermore, the pyridine derivative is a product obtained by connecting 1 to 5 substituents among all C and N atoms on the pyridine ring, and the substituents are hydrocarbon groups, halogens, -NH2, -NHR, -NR2, -PH2, -PHR, -PR2, -OH, -SH, -OR, -SR, -SO2H, -SO3H, -CHO, -COR, -CORNH2, -COOH, -COOR, -C≡N, -N=O, -NO2, -NH-NH2, -CO(NH2), -SiR3, -B(OH)2 or N, S-containing heterocyclic substituents, or substituents obtained by replacing a hydrogen atom or substituent in one of the above groups with one or more of the above groups, and R represents a hydrocarbon group.

[0009] Furthermore, the concentration of sodium hydroxide in the mixed system is 1 to 100 mol / L.

[0010] An imidazole-based surface treatment additive prepared by the method for preparing the imidazole-based surface treatment additive provided by the invention.

[0011] An application of the imidazole-based surface treatment additive provided by the invention in electroplating or chemical plating.

[0012] Furthermore, the electroplating is acid copper electroplating.

[0013] Furthermore, the acid bright copper plating solution used in the acid copper electroplating comprises the following components:

[0014] 10-1000 mg / L polyether surfactant, 5-50 mg / L sulfur-containing compound main brightener, 5-100 mg / L dye leveler, 1-100 μL / L imidazole-based surface treatment additive of the present invention, 100-300 g / L copper sulfate pentahydrate, 50-200 g / L 98 mass% concentrated sulfuric acid and 10-300 mg / L 37 mass% concentrated hydrochloric acid.

[0015] Furthermore, the polyether surfactant is polyethylene oxide polypropylene oxide monobutyl ether, and the sulfur-containing compound main brightener is sodium polydisulfide dipropylene sulfonate.

[0016] Furthermore, when the acid bright copper plating solution is used for acid copper electroplating, the current density of the bright area is in the range of 0.1 to 10 A / dm 2 .

[0017] Beneficial effects of the present invention:

[0018] The present invention uses epichlorohydrin, imidazole or its derivatives, pyridine or its derivatives as raw materials to prepare imidazole-based electroplating additives. When the imidazole-based electroplating additives are applied to acid sulfate copper plating, only 1 to 100 μL / L of addition is required to significantly improve the brightness of the copper plating layer in the low current density area, achieving 0.1 to 10 A / dm 2 The coating is mirror-bright in a wide current density range, and the glossiness is maintained above 480GU. The imidazole-based electroplating additive of the present invention has a simple preparation process, a small amount of addition, and can significantly reduce the consumption rate of the main brightener containing sulfur compounds, showing excellent application potential.

[0019] The preparation process of conventional surface treatment additives requires complex operations such as dripping and temperature control to obtain a clear target product and avoid side reactions; while the preparation method of the imidazole-based surface treatment additive provided by the present invention avoids complex operations and energy consumption, and only requires the three raw materials to be directly added to the sodium hydroxide solution at room temperature and pressure and mixed and stirred for 1 minute. The preparation process of the present invention is not a simple physical mixing of the raw materials, but a chemical reaction. The water and imidazole or its derivatives in the reaction system can both act as nucleophiles to attack the epoxy structure, so the obtained products are complex and diverse, and unexpected technical effects are achieved. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 1 is an appearance diagram of the Hull cell test pieces in Examples 1-3 and Comparative Example 1, wherein a corresponds to Example 1, b corresponds to Example 2, c corresponds to Example 3, and d corresponds to Comparative Example 1;

[0021] Figure 2 1 is a cyclic voltammogram of the acidic bright copper plating solution of Examples 1-3 and Comparative Example 1, wherein a corresponds to Example 1, b corresponds to Example 2, c corresponds to Example 3, and d corresponds to Comparative Example 1. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is further described below in conjunction with the embodiments, but it is not limited thereto. Any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be included in the protection scope of the present invention. The process equipment or devices not specifically noted in the following embodiments are all conventional equipment or devices in the art. If not specifically specified, the raw materials used in the embodiments of the present invention can be obtained commercially; if not specifically specified, the technical means used in the embodiments of the present invention are all conventional means well known to those skilled in the art.

[0023] The gloss meter used in the examples is NHG60 model, purchased from Shenzhen Sanenshi Technology Co., Ltd.

[0024] The Hull cell used in the examples was purchased from Guangdong Second Light Industry Research Institute.

[0025] The electrochemical workstation used in the examples is CHI670 model, purchased from Shanghai Chenhua Instrument Co., Ltd.

[0026] The raw materials used in the preparation of the imidazole-based additives in the following examples were purchased from Aladdin Reagent Company.

[0027] Example 1

[0028] This embodiment provides an imidazole-based surface treatment additive and a preparation method thereof.

[0029] The steps of the preparation method of the imidazole-based electroplating additive in this embodiment are as follows:

[0030] To 42 g of deionized water, add 6.72 g of sodium hydroxide, 7.00 g of imidazole, and 12.30 g of nicotinic acid (pyridine-3-carboxylic acid), and after dissolving, add 17.55 g of epichlorohydrin, react until no epichlorohydrin suspension is observed, and dilute to 100 mL with deionized water.

[0031] The imidazole-based electroplating additive prepared in this example was used for acid bright copper plating, and an acid bright copper plating solution having the following components was prepared:

[0032] 800 mg / L polyethylene oxide polypropylene oxide monobutyl ether, 20 mg / L sodium polydisulfide dipropylene sulfonate, 10 mg / L blue dye, 1.1 μL / L imidazole surface treatment additive prepared in this embodiment, 200 g / L copper sulfate pentahydrate, 65 g / L 98 mass% concentrated sulfuric acid and 180 mg / L 37 mass% concentrated hydrochloric acid; wherein the average molecular weight of polyethylene oxide polypropylene oxide monobutyl ether is 1340.

[0033] Example 2

[0034] This embodiment provides an imidazole-based surface treatment additive and a preparation method thereof.

[0035] The steps of the preparation method of the imidazole-based electroplating additive in this embodiment are as follows:

[0036] To 42 g of deionized water, 6.72 g of sodium hydroxide, 7.00 g of imidazole, and 12.30 g of nicotinic acid were added, and after dissolution, 17.55 g of epichlorohydrin was added. The reaction was carried out until no epichlorohydrin suspension was observed, and the volume was fixed to 100 mL with deionized water.

[0037] The imidazole-based electroplating additive prepared in this example was used for acid bright copper plating, and an acid bright copper plating solution having the following components was prepared:

[0038] 800 mg / L polyethylene oxide polypropylene oxide monobutyl ether, 15 mg / L sodium polydisulfide dipropylene sulfonate, 10 mg / L blue dye, 1.1 μL / L imidazole-based surface treatment additive prepared in this embodiment, 200 g / L copper sulfate pentahydrate, 65 g / L 98 mass% concentrated sulfuric acid and 180 mg / L 37 mass% concentrated hydrochloric acid; wherein the average molecular weight of polyethylene oxide polypropylene oxide monobutyl ether is 1340.

[0039] Example 3

[0040] This embodiment provides an imidazole-based surface treatment additive and a preparation method thereof.

[0041] The steps of the preparation method of the imidazole-based electroplating additive in this embodiment are as follows:

[0042] To 42 g of deionized water, 6.72 g of sodium hydroxide, 7.00 g of imidazole, and 12.30 g of nicotinic acid were added, and after dissolution, 17.55 g of epichlorohydrin was added. The reaction was carried out until no epichlorohydrin suspension was observed, and the volume was fixed to 100 mL with deionized water.

[0043] The imidazole-based electroplating additive prepared in this example was used for acid bright copper plating, and an acid bright copper plating solution having the following components was prepared:

[0044] 800 mg / L polyethylene oxide polypropylene oxide monobutyl ether, 10 mg / L sodium polydisulfide dipropylene sulfonate, 10 mg / L blue dye, 1.1 μL / L imidazole-based surface treatment additive prepared in this embodiment, 200 g / L copper sulfate pentahydrate, 65 g / L 98 mass% concentrated sulfuric acid and 180 mg / L 37 mass% concentrated hydrochloric acid; wherein the average molecular weight of polyethylene oxide polypropylene oxide monobutyl ether is 1340.

[0045] Example 4

[0046] This embodiment provides an imidazole-based surface treatment additive and a preparation method thereof.

[0047] The steps of the preparation method of the imidazole-based electroplating additive in this embodiment are as follows:

[0048] To 42 g of deionized water, 6.72 g of sodium hydroxide, 7.00 g of 4-methylimidazole, and 12.30 g of 5-amino-4-hydroxynicotinic acid were added, and after dissolution, 17.55 g of epichlorohydrin was added, and the mixture was reacted until no epichlorohydrin suspension was observed, and the volume was fixed to 100 mL with deionized water.

[0049] The imidazole-based electroplating additive prepared in this example was used for acid bright copper plating, and an acid bright copper plating solution having the following components was prepared:

[0050] 800 mg / L polyethylene oxide polypropylene oxide monobutyl ether, 10 mg / L sodium polydisulfide dipropylene sulfonate, 10 mg / L blue dye, 1.1 μL / L imidazole-based surface treatment additive prepared in this embodiment, 200 g / L copper sulfate pentahydrate, 65 g / L 98 mass% concentrated sulfuric acid and 180 mg / L 37 mass% concentrated hydrochloric acid; wherein the average molecular weight of polyethylene oxide polypropylene oxide monobutyl ether is 1340.

[0051] Example 5

[0052] This embodiment provides an imidazole-based surface treatment additive and a preparation method thereof.

[0053] The steps of the preparation method of the imidazole-based electroplating additive in this embodiment are as follows:

[0054] To 42 g of deionized water, 6.72 g of sodium hydroxide, 7.00 g of 2-hydroxyethylimidazole, and 12.30 g of 5-hydroxynicotinic acid were added, and after dissolution, 17.55 g of epichlorohydrin was added, and the mixture was reacted until no epichlorohydrin suspension was observed, and the volume was fixed to 100 mL with deionized water.

[0055] The imidazole-based electroplating additive prepared in this example was used for acid bright copper plating, and an acid bright copper plating solution having the following components was prepared:

[0056] 800 mg / L polyethylene oxide polypropylene oxide monobutyl ether, 10 mg / L sodium polydisulfide dipropylene sulfonate, 10 mg / L blue dye, 1.1 μL / L imidazole-based surface treatment additive prepared in this embodiment, 200 g / L copper sulfate pentahydrate, 65 g / L 98 mass% concentrated sulfuric acid and 180 mg / L 37 mass% concentrated hydrochloric acid; wherein the average molecular weight of polyethylene oxide polypropylene oxide monobutyl ether is 1340.

[0057] Example 6

[0058] This embodiment provides an imidazole-based surface treatment additive and a preparation method thereof.

[0059] The steps of the preparation method of the imidazole-based electroplating additive in this embodiment are as follows:

[0060] To 42 g of deionized water, 6.72 g of sodium hydroxide, 7.00 g of 1H-imidazole-5-propanol, and 12.30 g of 1-benzylnicotinic acid were added, and after dissolution, 17.55 g of epichlorohydrin was added, and the mixture was reacted until no epichlorohydrin suspension was observed, and the volume was fixed to 100 mL with deionized water.

[0061] The imidazole-based electroplating additive prepared in this example was used for acid bright copper plating, and an acid bright copper plating solution having the following components was prepared:

[0062] 800 mg / L polyethylene oxide polypropylene oxide monobutyl ether, 10 mg / L sodium polydisulfide dipropylene sulfonate, 10 mg / L blue dye, 1.1 μL / L imidazole-based surface treatment additive prepared in this embodiment, 200 g / L copper sulfate pentahydrate, 65 g / L 98 mass% concentrated sulfuric acid and 180 mg / L 37 mass% concentrated hydrochloric acid; wherein the average molecular weight of polyethylene oxide polypropylene oxide monobutyl ether is 1340.

[0063] Comparative Example 1

[0064] This comparative example provides a method for using a commercial acid bright copper plating additive, wherein the commercial acid bright copper plating additive is 210A, B, and C from a foreign company.

[0065] This comparative example prepares an acid bright copper plating solution having the following components:

[0066] 10mg / L 210 cylinder C, 0.6mL / L 210A, 0.3mL / L 210B, 200g / L copper sulfate pentahydrate, 65g / L 98mass% concentrated sulfuric acid and 180mg / L 37mass% concentrated hydrochloric acid.

[0067] Test Example 1

[0068] 267 mL of the acidic bright copper plating solution prepared in Examples 1 to 3 and Comparative Example 1 were respectively placed in a Hull cell, with a phosphor copper plate as the anode and a 62# brass sheet as the cathode. The current was controlled to be constant at 2A and the electroplating was performed for 10 min. Figure 1 The glossiness of the copper plating layer in different current density areas was measured, and the results are shown in Table 1.

[0069] Table 1

[0070]

[0071] Depend on Figure 1 It can be seen from the test data of the appearance of each group of Hull cell test pieces and the glossiness in different current density areas in Table 1 that Examples 1 to 3 with the imidazole-based electroplating additive prepared by the present invention have a good glossiness at 0.1 A / dm 2The glossiness is above 480GU, which is higher than that of comparative example 1; at 0.2A / dm 2 The glossiness is above 630GU, which is similar to or even higher than that of comparative example 1. 2 The glossiness of the area above 700GU is always maintained above 700GU. It can be seen that the acid copper plating solution containing the imidazole-based additive prepared by the present invention can improve the brightness of the copper plating layer in the low current density area while ensuring the high brightness of the plating layer in the medium and high current density areas.

[0072] Test Example 2

[0073] 100 mL of the acidic bright copper plating solution prepared in Examples 1 to 3 and Comparative Example 1 were placed in beakers, and a cyclic voltammetry test was performed using a rotating disk platinum electrode as a working electrode, a saturated mercury-mercurous sulfate electrode as a reference electrode, and a platinum sheet electrode as a counter electrode. The test parameters are as follows:

[0074] Potential scanning range: -0.6V~0.25V, starting voltage: 0.25V, scanning rate: 0.02V / s, working electrode speed: 1000rpm, scanning segment number: 200.

[0075] Take the 1st, 10th, 20th, 40th, 60th, 80th, and 100th cycles as the experimental results and calculate the copper dissolution peak area. The results are as follows: Figure 2 As shown in Table 2.

[0076] Table 2

[0077]

[0078] Table 2 shows the copper dissolution peak area data of the cyclic voltammetry curves of different turns of each group of electrolyte. It can be seen that the change amplitude of the copper dissolution peak area of ​​Examples 1 to 3 groups with the turn number is always small. The copper dissolution peak area of ​​the 100th turn is only reduced by about 0.88%, 4.6%, and 6.4% respectively compared with the 1st turn, while the copper dissolution peak area of ​​the 10th turn of the comparative example 1 group is reduced by about 34.8% compared with the 1st turn, and then the peak area gradually decreases. Although there is a small rebound after the 80th turn, it is still significantly lower than the peak area of ​​the first turn. The copper dissolution peak area of ​​the 100th turn is reduced by 44.9% compared with the 1st turn, and the decline is still significantly higher than that of Examples 1 to 3. It can be seen that the brightener consumption rate of the acid copper plating solution containing the imidazole-based electrolytic additive prepared by the present invention is significantly reduced.

[0079] The above embodiments only use acid bright copper plating as an example to demonstrate the efficacy of the present invention, and are not intended to limit the present invention. Any application of the present invention to the field of surface treatment, without departing from the principles and spirit of the present invention, and any adjustment or modification, etc., shall fall within the scope of protection of the present invention.

Claims

1. A method for preparing an imidazole-based surface treatment additive, characterized in that: Sodium hydroxide, imidazole or imidazole derivatives, pyridine or pyridine derivatives are dissolved in deionized water, epichlorohydrin is added to the obtained mixed system, and the reaction is carried out until no epichlorohydrin suspension is observed to obtain an imidazole-based surface treatment additive, wherein the ratio of the number of imidazole rings in the imidazole or imidazole derivatives to the number of epoxy rings in epichlorohydrin is 0.1-10:0.1-10, and the ratio of the number of imidazole rings in the imidazole or imidazole derivatives to the number of pyridine rings in the pyridine or pyridine derivatives is 0.1-10:0.1-10.

2. The method for preparing an imidazole-based surface treatment additive according to claim 1, characterized in that: The imidazole derivative is a product in which 1 to 4 hydrogen atoms on the imidazole ring are replaced by substituents, wherein the substituents are hydrocarbon groups, halogens, -NH2, -NHR, -NR2, -PH2, -PHR, -PR2, -OH, -SH, -OR, -SR, -SO2H, -SO3H, -CHO, -COR, -CORNH2, -COOH, -COOR, -C≡N, -N=O, -NO2, -NH-NH2, -CO(NH2), -SiR3, -B(OH)2 or N, S-containing heterocyclic substituents, or substituents obtained by replacing a hydrogen atom or substituent in one of the above groups with one or more of the above groups, and R represents a hydrocarbon group.

3. The method for preparing an imidazole-based surface treatment additive according to claim 1 or 2, characterized in that: The pyridine derivative is a product obtained by connecting 1 to 5 substituents among all C and N atoms on the pyridine ring, and the substituents are hydrocarbon groups, halogens, -NH2, -NHR, -NR2, -PH2, -PHR, -PR2, -OH, -SH, -OR, -SR, -SO2H, -SO3H, -CHO, -COR, -CORNH2, -COOH, -COOR, -C≡N, -N=O, -NO2, -NH-NH2, -CO(NH2), -SiR3, -B(OH)2 or N, S-containing heterocyclic substituents, or substituents obtained by replacing a hydrogen atom or substituent in one of the above groups with one or more of the above groups, and R represents a hydrocarbon group.

4. The method for preparing an imidazole-based surface treatment additive according to claim 3, characterized in that: The concentration of sodium hydroxide in the mixed system is 1-100 mol / L.

5. An imidazole-based surface treatment additive prepared by the method for preparing an imidazole-based surface treatment additive as claimed in any one of claims 1 to 4.

6. Use of the imidazole-based surface treatment additive as claimed in claim 5 in electroplating or chemical plating.

7. The use of the imidazole-based surface treatment additive in electroplating or chemical plating according to claim 6, characterized in that: The electroplating is acid copper electroplating or alkaline cyanide-free zinc plating.

8. The use of the imidazole-based surface treatment additive in electroplating or chemical plating according to claim 7, characterized in that: The acid bright copper plating solution used in the acid copper electroplating comprises the following components: 10-1000 mg / L polyether surfactant, 5-50 mg / L sulfur-containing compound main brightener, 5-100 mg / L dye leveler, 1-100 μL / L imidazole surface treatment additive according to claim 6, 100-300 g / L copper sulfate pentahydrate, 50-200 g / L 98 mass% concentrated sulfuric acid and 10-300 mg / L 37 mass% concentrated hydrochloric acid.

9. The use of the imidazole-based surface treatment additive in electroplating or chemical plating according to claim 8, characterized in that: The polyether surfactant is polyethylene oxide polypropylene oxide monobutyl ether, and the sulfur-containing compound main brightener is sodium polydisulfide dipropane sulfonate.

10. Use of the imidazole-based surface treatment additive in electroplating or chemical plating according to claim 9, characterized in that: When the acid bright copper plating solution is used for acid copper electroplating, the current density range of the bright area is 0.1 to 10 A / dm 2 .

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