Roughening liquid for metal surface treatment and application

Abstract

The invention provides a roughening solution for metal surface treatment and application thereof.The roughening solution comprises, by concentration, 200-250 ml / L of a sulfuric acid solution, 200-250 ml / L of hydrogen peroxide, 0.4-0.5 g / L of a stabilizer, 10-20 ml / L of a dispersing agent and 0.1-0.2 g / L. The stabilizer is formed by compounding potassium polyaspartate, an organic amine compound and cucurbit [7] uril. The molecular weight of the potassium polyaspartate is 1000 to 2000; the stabilizer obtained by compounding cucurbit [7] uril, an organic amine compound and potassium polyaspartate destroys hydroxides of heavy metal ions in a complexing manner, effectively inhibits decomposition of hydrogen peroxide, is applied to copper surface treatment, and can significantly improve the Rz value of a copper plate to 15-30 [mu] m.

Description

Technical Field

[0001] The invention relates to the technical field of metal surface treatment, and in particular to a roughening liquid for metal surface treatment and application thereof. Background Art

[0002] Copper plates are widely used in the electronics, communications, and automotive industries, especially in applications that require heat dissipation. However, after the browning treatment of ordinary copper plates, their Rz value is usually only 1-3μm, which results in weak bonding strength between the browned copper plates and thermally conductive epoxy resins, affecting product reliability and service life. In order to improve the bonding strength, it is necessary to increase the Rz value of the copper plate as much as possible.

[0003] There are many types of commercial micro-etching and roughening solutions on the market, most of which are organic acid / Cu 2+ System or sulfuric acid hydrogen peroxide system. CN111349937A discloses a micro-etching solution for the surface of copper or copper alloy and a treatment method thereof, wherein the micro-etching solution is composed of the following components in percentage by mass: 0.1% to 1% hydrogen peroxide, 0.1% to 10% sulfuric acid, 0.01% to 10% hydrogen peroxide stabilizer, 0.01% to 1% protective agent, 0.001% to 0.02% halogen ion, and the balance is deionized water. However, this sulfuric acid hydrogen peroxide roughening system is susceptible to chloride ion contamination, and it is difficult to maintain a stable etching rate and roughening effect within a wider range of chloride ion concentrations. Hydrogen peroxide is prone to premature catalytic decomposition in the presence of heavy metal ions, resulting in decreased stability, so additives such as stabilizers and dispersants have to be added, which not only affects the effect of the final metal surface treatment, but also increases the industrial processing cost.

[0004] In view of this, the existing technology related to the roughening liquid for metal surface treatment still needs to be further improved. Summary of the invention

[0005] The invention provides a roughening liquid for metal surface treatment and its application, which solves the technical problem that hydrogen peroxide in the existing roughening liquid decomposes when encountering heavy metal ions, resulting in decreased stability and affecting the roughening effect of the metal surface.

[0006] In order to solve the above problems, the present invention proposes the following technical solutions:

[0007] On the one hand, the present invention provides a roughening liquid for metal surface treatment, which includes the following components, measured by component concentration: 200-250 ml / L sulfuric acid solution, 200-250 ml / L hydrogen peroxide, 0.4-0.5 g / L stabilizer, 10-20 ml / L dispersant, and 0.1-0.2 g / L organic additive.

[0008] The stabilizer is a compound of potassium polyaspartate, an organic amine compound and a seven-membered cucurbitacin, and the molecular weight of the potassium polyaspartate is 1000-2000.

[0009] On the basis of this technical solution, it is further preferred that the organic additive is one of sodium polydisulfide propane sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium phenyl polydisulfide propane sulfonate or sodium N,N-dimethyl-disulfide carbonyl propane sulfonate.

[0010] On the basis of this technical solution, further preferably, the organic amine compound is one of ethanolamine, diethanolamine, triethanolamine, ethylenediamine or di-n-butylamine.

[0011] On the basis of this technical solution, further preferably, the preparation method of the stabilizer comprises the following steps:

[0012] The seven-membered cucurbitacin and the organic amine compound are dissolved in water to obtain the seven-membered cucurbitacin aqueous solution and the organic amine aqueous solution respectively. The organic amine aqueous solution is added dropwise into the seven-membered cucurbitacin aqueous solution at 25° C. After the reaction is completed by nuclear magnetic resonance monitoring, the solvent is removed, the mixture is purified, potassium polyaspartate is added, and the mixture is reacted at 30-45° C. for 2-4 hours to obtain the stabilizer.

[0013] On the basis of this technical solution, it is further preferred that the mass ratio of the potassium polyaspartate, the organic amine compound and the seven-membered cucurbitacin is (2.5-5):(1.4-2):1.

[0014] Based on this technical solution, further preferably, the dispersant is sodium citrate or polyvinyl pyrrolidone.

[0015] Based on this technical solution, it is further preferred that the mass concentration of the sulfuric acid solution is 50-65%, and the mass concentration of the hydrogen peroxide is 45-50%.

[0016] On the other hand, the present invention also provides the use of the roughening liquid for metal surface treatment described in any one of the first aspects in roughening the surface of a copper plate.

[0017] Based on this technical solution, it is further preferred that the following steps are included:

[0018] The copper plate is cleaned and degreased, and the copper plate is laser embossed using a laser device;

[0019] Take out the copper plate, use the roughening liquid to roughen it, solidify it, and wash it with the liquid; then perform the secondary roughening;

[0020] Complete secondary liquid washing, drying and post-processing.

[0021] On the basis of this technical solution, it is further preferred that the laser is 1045-1064 nm, the power is 50-60 W, and the drying temperature is 90-98°C.

[0022] Compared with the prior art, the technical effects achieved by the present invention include:

[0023] The invention provides a roughening liquid for metal surface treatment, which adopts a stabilizer obtained by compounding a seven-membered cucurbit ring, an organic amine compound and potassium polyaspartate. The seven-membered cucurbit ring has a suitable cavity and good water solubility, and shows good chemical stability and inclusion capacity in an acidic environment, can effectively stabilize hydrogen peroxide, reduce free radical generation, and promote micro-etching rate; potassium polyaspartate contains peptide bonds and carboxyl groups, has strong adsorption and chelation effects, and can better prevent metal corrosion; further, the seven-membered cucurbit ring and the organic amine compound can form a complex, and together with potassium polyaspartate, destroy the hydroxide of heavy metal ions in a complexed form, and effectively inhibit the decomposition of hydrogen peroxide.

[0024] The organic additives of the present invention, sodium polydisulfide propane sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium phenyl polydisulfide propane sulfonate or sodium N,N-dimethyl-disulfide carbonyl propane sulfonate, can enable the roughening liquid to maintain a stable micro-etching rate and a roughening effect within a wider chloride ion window, and are applied to copper surface treatment to significantly improve the Rz value of the copper plate to 15 to 30 μm, and significantly enhance the bonding strength between the copper plate and the thermally conductive epoxy resin. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The roughening liquid obtained in Example 1 is used for roughening patterns of metal surface treatment;

[0026] Figure 2 The roughening liquid obtained in Example 2 is used for the roughening pattern of metal surface treatment;

[0027] Figure 3 The roughening liquid obtained in Example 3 is used for the roughening pattern of metal surface treatment;

[0028] Figure 4 The roughening liquid obtained in Example 1 is used for roughening patterns of metal surface treatment;

[0029] Figure 5 The roughening liquid obtained in Example 1 is used for roughening patterns of metal surface treatment;

[0030] Figure 6 This is a side view of the roughening pattern of the roughening liquid obtained in Example 1 used for metal surface treatment. DETAILED DESCRIPTION

[0031] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments. Obviously, the embodiments to be described below are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field based on the technology to which the claims of the present invention belong without creative work are within the scope of protection of the present invention.

[0032] It should be understood that the terms used in this description of the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the embodiments of the present invention. As used in the description of the embodiments of the present invention and the appended claims, unless the context clearly indicates otherwise, the singular forms of "a", "an" and "the" are intended to include plural forms.

[0033] The present invention provides a roughening liquid for metal surface treatment and its application, comprising the following components: 200-250 ml / L sulfuric acid solution, 200-250 ml / L hydrogen peroxide, 0.4-0.5 g / L stabilizer, 10-20 ml / L dispersant, and 0.1-0.2 g / L organic additive; wherein the stabilizer is a compound of potassium polyaspartate, an organic amine compound and a seven-membered cucurbit ring, and the molecular weight of the potassium polyaspartate is 1000-2000. The use of special roughening liquid and process parameters can significantly improve the Rz value of the copper plate to 15-30 μm, the surface roughness of the copper plate after roughening is uniform, and the bonding strength with the thermal conductive epoxy resin is significantly improved.

[0034] Example 1

[0035] A roughening liquid for metal surface treatment comprises the following components, measured by component concentration: 250 ml / L sulfuric acid solution, 250 ml / L hydrogen peroxide, 0.5 g / L stabilizer, 20 ml / L dispersant, and 0.2 g / L organic additive.

[0036] The stabilizer is a compound of potassium polyaspartate, an organic amine compound and a seven-membered cucurbitacin, and the molecular weight of the potassium polyaspartate is 1000.

[0037] In this embodiment, specifically, the organic additive is sodium poly(dipropane disulfide sulfonate).

[0038] In this embodiment, specifically, the organic amine compound is triethanolamine.

[0039] In this embodiment, specifically, the preparation method of the stabilizer comprises the following steps:

[0040] The seven-membered cucurbitacin and triethanolamine are dissolved in water to obtain the seven-membered cucurbitacin aqueous solution and the triethanolamine aqueous solution respectively. The triethanolamine aqueous solution is added dropwise into the seven-membered cucurbitacin aqueous solution at 25° C. After the reaction is completed by nuclear magnetic resonance monitoring, the solvent is removed, the reaction is purified, potassium polyaspartate is added, and the reaction is carried out at 45° C. for 2 hours to obtain the stabilizer.

[0041] In this embodiment, specifically, the mass ratio of potassium polyaspartate, triethanolamine and seven-membered cucurbitacin is 2.5:1.4:1.

[0042] In this embodiment, specifically, the dispersant is sodium citrate.

[0043] In this embodiment, specifically, the mass concentration of the sulfuric acid solution is 50%, and the mass concentration of the hydrogen peroxide solution is 45%.

[0044] Example 2

[0045] A roughening solution for metal surface treatment comprises the following components, measured by component concentration: 200 ml / L sulfuric acid solution, 200 ml / L hydrogen peroxide, 0.4 g / L stabilizer, 10 ml / L dispersant, and 0.1 g / L organic additive.

[0046] The stabilizer is a compound of potassium polyaspartate, an organic amine compound and a seven-membered cucurbitacin, and the molecular weight of the potassium polyaspartate is 2000.

[0047] In this embodiment, specifically, the organic additive is sodium phenyl polydisulfide propane sulfonate.

[0048] In this embodiment, specifically, the organic amine compound is ethylenediamine.

[0049] In this embodiment, specifically, the preparation method of the stabilizer comprises the following steps:

[0050] The seven-membered cucurbitacin and ethylenediamine were dissolved in water to obtain the seven-membered cucurbitacin aqueous solution and the ethylenediamine aqueous solution respectively. The ethylenediamine aqueous solution was added dropwise into the seven-membered cucurbitacin aqueous solution at 25° C. After the reaction was completed by nuclear magnetic resonance monitoring, the solvent was removed, the mixture was purified, potassium polyaspartate was added, and the mixture was reacted at 30° C. for 4 hours to obtain the stabilizer.

[0051] In this embodiment, specifically, the mass ratio of potassium polyaspartate, ethylenediamine and seven-membered cucurbitacin is 5:2:1.

[0052] In this embodiment, specifically, the dispersant is sodium citrate.

[0053] In this embodiment, specifically, the mass concentration of the sulfuric acid solution is 65%, and the mass concentration of the hydrogen peroxide solution is 50%.

[0054] Example 3

[0055] A roughening solution for metal surface treatment comprises the following components, measured by component concentration: 225 ml / L sulfuric acid solution, 225 ml / L hydrogen peroxide, 0.45 g / L stabilizer, 15 ml / L dispersant, and 0.14 g / L organic additive.

[0056] The stabilizer is a compound of potassium polyaspartate, an organic amine compound and a seven-membered cucurbitacin, and the molecular weight of the potassium polyaspartate is 1500.

[0057] In this embodiment, specifically, the organic additive is a kind of sodium N,N-dimethyl-dithiocarbonylpropane sulfonate.

[0058] In this embodiment, specifically, the organic amine compound is ethanolamine.

[0059] In this embodiment, specifically, the preparation method of the stabilizer comprises the following steps:

[0060] The seven-membered cucurbitacin and the organic amine compound are dissolved in water to obtain the seven-membered cucurbitacin aqueous solution and the ethanolamine aqueous solution respectively. The ethanolamine aqueous solution is added dropwise into the seven-membered cucurbitacin aqueous solution at 25° C. After the reaction is completed by nuclear magnetic resonance monitoring, the solvent is removed, the reaction is purified, potassium polyaspartate is added, and the reaction is carried out at 35° C. for 3 hours to obtain the stabilizer.

[0061] In this embodiment, specifically, the mass ratio of potassium polyaspartate, ethanolamine and seven-membered cucurbitacin is 3:1.65:1.

[0062] In this embodiment, specifically, the dispersant is polyvinyl pyrrolidone PVP40.

[0063] In this embodiment, specifically, the mass concentration of the sulfuric acid solution is 55%, and the mass concentration of the hydrogen peroxide solution is 49%.

[0064] Comparative Example 1

[0065] A roughening liquid for metal surface treatment, which differs from Example 1 in that the stabilizer is not added.

[0066] Comparative Example 2

[0067] A roughening liquid for metal surface treatment, which differs from Example 2 in that the stabilizer is potassium polyaspartate.

[0068] Comparative Example 3

[0069] A roughening liquid for metal surface treatment, which is different from Example 3 in that the stabilizer is a seven-membered cucurbitacin and ethanolamine.

[0070] Comparative Example 4

[0071] A roughening liquid for metal surface treatment, which differs from Example 1 in that no organic additive is added.

[0072] Comparative Example 5

[0073] A roughening liquid for metal surface treatment, the preparation method of which refers to the method with publication number CN111349937A.

[0074] Application Example 1

[0075] The application of the roughening liquid for metal surface treatment obtained in Example 1 to roughening the surface of a copper plate comprises the following steps:

[0076] The copper plate is cleaned and degreased, and the copper plate is laser embossed using a laser device;

[0077] Specifically, a copper plate with epoxy resin as the base is selected, the surface thickness of the copper plate is 10 μm, the thickness of the base material is 1 mm, the laser is 1064 nm, and the power is 60 W.

[0078] Take out the copper plate, use the roughening liquid to roughen it, solidify it, and wash it with the liquid; then perform the secondary roughening;

[0079] Complete secondary liquid washing, hot air drying at 98°C, and post-processing.

[0080] Results: Figure 1 visible, Figure 1 The roughening liquid obtained in Example 1 is used for the roughening pattern of metal surface treatment. The width between the cells is 40 to 100 μm, indicating that the roughening effect is good, and there is no micro-etching uneven color difference and darkening. In addition, Figure 2-5 The roughening liquid obtained in Example 2, Example 3 and Example 1 is used for the roughening pattern of metal surface treatment, and the width between the cells is 40 to 100 μm. It can be seen that the roughening liquid of the present application is applied to the surface treatment of the copper plate and can be processed into various patterns; Figure 6 This is a side view of the processing effect of Application Example 1. The roughening depth is 5-30μm. It can be seen that the roughening effect is good. Through the process treatment of this application example, the Rz value of the copper plate can reach 20-30μm, and the bonding strength with the thermal conductive epoxy resin is significantly improved.

[0081] Performance Testing

[0082] The roughening solutions obtained in the examples and comparative examples were applied to the surface treatment of the copper plates, and the treatment effects were tested.

[0083] Micro-etching amount detection: A 100mm×100mm double-sided copper-clad laminate is passed through a horizontal spray device according to the process of the embodiment, and the weight change of the copper product before and after is measured, and the thickness of the copper layer etched away is calculated as the micro-etching amount.

[0084] Appearance inspection: Observe the treated copper surface under a 20x magnifying glass. If the appearance is uniform in color, without white spots or bright spots, it is qualified; otherwise, it is unqualified.

[0085] Table 1

[0086] Performance Testing

[0087] project Appearance inspection Micro-etching amount detection / μm Example 1 qualified 1.44 Example 2 qualified 1.36 Example 3 qualified 1.31 Comparative Example 1 Failure 0.72 Comparative Example 2 Failure 0.81 Comparative Example 3 Failure 0.84 Comparative Example 4 Failure 0.86 Comparative Example 5 qualified 1.17

[0088] As can be seen from Table 1, the appearance and micro-etching amount of Examples 1-3 are better than those of Comparative Examples 1-5. It can be seen that the micro-etching effect of the copper plate can be significantly improved through special roughening liquid and process parameters, and the appearance of the treated copper plate is qualified.

[0089] In summary, the roughening liquid for metal surface treatment and its application proposed in the present invention can effectively stabilize hydrogen peroxide, reduce the generation of free radicals, and promote the micro-etching rate; combined with the laser embossing method and applied to copper surface treatment, it can significantly improve the Rz value of the copper plate to 15 to 30 μm.

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A roughening liquid for metal surface treatment, characterized in that: According to the concentration of the components, it includes the following components: sulfuric acid solution 200-250ml / L, hydrogen peroxide 200-250ml / L, stabilizer 0.4-0.5g / L, dispersant 10-20ml / L, organic additive 0.1-0.2g / L, The stabilizer is a compound of potassium polyaspartate, an organic amine compound and a seven-membered cucurbitacin, and the molecular weight of the potassium polyaspartate is 1000-2000.

2. The roughening liquid for metal surface treatment according to claim 1, characterized in that: The organic additive is one of sodium polydisulfide propane sulfonate, sodium 3-mercapto-1-propane sulfonate, sodium phenyl polydisulfide propane sulfonate or sodium N,N-dimethyl-disulfide carbonyl propane sulfonate.

3. The roughening liquid for metal surface treatment according to claim 1, characterized in that: The organic amine compound is one of ethanolamine, diethanolamine, triethanolamine, ethylenediamine or di-n-butylamine.

4. The roughening liquid for metal surface treatment according to claim 1, characterized in that: The preparation method of the stabilizer comprises the following steps: The seven-membered cucurbitacin and the organic amine compound are dissolved in water to obtain the seven-membered cucurbitacin aqueous solution and the organic amine aqueous solution respectively. The organic amine aqueous solution is added dropwise into the seven-membered cucurbitacin aqueous solution at 25° C. After the reaction is completed by nuclear magnetic resonance monitoring, the solvent is removed, the mixture is purified, potassium polyaspartate is added, and the mixture is reacted at 30-45° C. for 2-4 hours to obtain the stabilizer.

5. The roughening liquid for metal surface treatment according to claim 4, characterized in that: The mass ratio of the potassium polyaspartate, the organic amine compound and the seven-membered cucurbitacin is (2.5-5):(1.4-2):

1.

6. The roughening liquid for metal surface treatment according to claim 1, characterized in that: The dispersant is sodium citrate or polyvinyl pyrrolidone.

7. The roughening liquid for metal surface treatment according to claim 1, characterized in that: The mass concentration of the sulfuric acid solution is 50-65%, and the mass concentration of the hydrogen peroxide is 45-50%.

8. Use of the roughening liquid for metal surface treatment as claimed in any one of claims 1 to 7 in roughening the surface of a copper plate.

9. The use of the roughening liquid for metal surface treatment as claimed in claim 8 in roughening the surface of a copper plate, characterized in that: The following steps are involved: The copper plate is cleaned and degreased, and the copper plate is laser embossed using a laser device; Take out the copper plate, use the roughening liquid to roughen it, solidify it, and wash it with the liquid; then perform the secondary roughening; Complete secondary liquid washing, drying and post-processing.

10. The use of the roughening liquid for metal surface treatment according to claim 9 in roughening the surface of a copper plate, characterized in that: The laser has a wavelength of 1045-1064 nm, a power of 50-60 W, and a drying temperature of 90-98° C.

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