Copper surface film treating fluid based on small-molecule corrosion inhibitor and preparation method and application of copper surface film treating fluid

Abstract

The invention belongs to the field of metal surface treatment, and relates to a copper surface film treatment liquid based on a small-molecule corrosion inhibitor and a preparation method and application thereof. The corrosion inhibitor consists of the following components in parts by weight: 4-6 parts of hydrolyzed silane, 0.25-5 parts of a small-molecule corrosion inhibitor and 45-55 parts of an alcohol solvent, wherein the hydrolyzed silane is obtained by hydrolyzing a silane coupling agent; and the small molecule corrosion inhibitor is one or more of CA, HEDP and ATMP. A thicker and more compact silane hybrid membrane is formed by adding the small-molecule corrosion inhibitor, the silane hybrid membrane is tightly combined with copper, the adhesion capacity of the silane hybrid membrane and the surface of the copper is improved, and the silane hybrid membrane shows remarkable corrosion resistance under the condition of low treatment liquid concentration.

Description

Technical Field

[0001] The invention belongs to the field of metal surface treatment, and relates to a copper surface film layer treatment liquid based on a small molecule corrosion inhibitor, and a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Copper and its alloys are widely used in various industrial sectors, such as electronics, pipelines, vehicles and ships. However, performance degradation and material deterioration due to corrosion have greatly affected the practical application of copper and posed risks to the economy, environment and human health.

[0004] Chemical conversion coating technology is widely used in the field of metal corrosion protection due to its advantages such as simple processing and low cost. Chromate passivation film is the most commonly used chemical conversion film, which has high corrosion resistance on copper surfaces. However, due to the serious toxicity and carcinogenicity of chromate compounds, which poses a significant risk to human health and the environment, its use has been gradually restricted or even banned.

[0005] Silane conversion coating has great potential in copper corrosion protection as an effective alternative to harmful chromate treatment due to its relative environmental friendliness, easy preparation, high stability and commercial availability. However, the inventors have found that the poor binding ability of silanol with copper hinders its application on copper surfaces. Summary of the invention

[0006] In view of the problem that the poor binding ability of silanol group with copper affects the application of silane film on copper surface, the purpose of the present invention is to provide a copper surface film treatment liquid based on small molecule corrosion inhibitor and its preparation method and application. The present invention forms a thicker and denser silane hybrid film by adding small molecule corrosion inhibitor, and the silane hybrid film is tightly combined with copper and increases its adhesion ability to the copper surface, showing significant corrosion resistance at a lower treatment liquid concentration.

[0007] In order to achieve the above technical objectives, the present invention provides the following technical solutions:

[0008] In a first aspect, a copper surface film treatment solution based on a small molecule corrosion inhibitor is composed of the following components in parts by weight: 4 to 6 parts of hydrolyzed silane, 0.25 to 5 parts of a small molecule corrosion inhibitor, and 45 to 55 parts of an alcohol solvent;

[0009] The hydrolyzed silane is obtained by hydrolyzing a silane coupling agent; and the small molecule corrosion inhibitor is one or more of citric acid (CA), hydroxyethylidene diphosphonic acid (HEDP), and aminotrimethylene phosphonic acid (ATMP).

[0010] The small molecule corrosion inhibitor added in the present invention contains a plurality of carboxylic acid groups (-COOH) or phosphonic acid groups (-PO(OH)2), which can not only condense with silane, but also form chemical bonds with copper, so that the small molecule corrosion inhibitor can be used as a bridge to further combine the silane conversion film on the copper surface, thereby improving the problem that the silane film and copper are not tightly combined due to the large steric hindrance of silane, thereby causing gaps between the interfaces; and, due to the high activity of -COOH and (-PO(OH)2), the polycondensation of silane can be promoted to make the formed silane conversion film denser and thicker; not only the problem of poor ability of silanol group to combine with copper is improved, but also the anti-corrosion performance of copper is improved.

[0011] CA, HEDP and ATMP can all improve the anti-corrosion performance of copper. However, experiments show that the improvement effects are different. When the small molecule corrosion inhibitor is hydroxyethylidene diphosphonic acid, the improvement effect on the anti-corrosion performance of copper is more significant.

[0012] The hydrolyzed silane is a silane coupling agent, wherein the silane coupling agent can be one or more of γ-aminopropyl triethoxysilane (KH-550), γ-glycidyloxypropyl trimethoxysilane (KH-560) or 3-mercaptopropyl trimethoxysilane (PropS-SH). However, studies have shown that the treatment solution formed by PropS-SH has better copper anticorrosion performance.

[0013] In a second aspect, a method for preparing the above copper surface film treatment solution comprises the following steps:

[0014] Adding a silane coupling agent to an alcohol-water mixed solvent, adjusting the pH value to acidic, and hydrolyzing for 22 to 26 hours to obtain hydrolyzed silane;

[0015] The small molecule corrosion inhibitor is added into an alcohol solvent to dissolve, and then the hydrolyzed silane is added and mixed evenly to obtain the product.

[0016] The present invention first adds the small molecule corrosion inhibitor to dissolve, and then adds the hydrolyzed silane, which is conducive to more uniform mixing of the materials, so that the functions can be better exerted.

[0017] In a third aspect, a use of the above copper surface film treatment liquid in treating the surface of a copper device.

[0018] In a fourth aspect, an anti-corrosion copper device is provided, wherein the copper device is treated with the above copper surface film treatment solution so that a silane conversion film is attached to the copper device.

[0019] The beneficial effects of the present invention are:

[0020] (1) The solute of the copper surface film layer treatment solution provided by the present invention only needs to contain two substances, hydrolyzed silane and small molecule corrosion inhibitor, and the components are simple, the dosage is small, and environmental pollution is reduced.

[0021] (2) The present invention utilizes a small molecule corrosion inhibitor to improve the problem of poor binding ability of silanol and copper. On the one hand, the small molecule corrosion inhibitor acts as a bridge to make the silane film and copper bind more tightly. On the other hand, the small molecule corrosion inhibitor condenses with silane to improve the gap caused by steric hindrance, and the formed conversion film is denser and thicker.

[0022] (3) Treating the copper surface with the copper surface film treatment solution of the present invention can significantly improve the anti-corrosion performance of copper and make it durable.

[0023] (4) The raw materials used in the copper surface film treatment solution provided by the present invention are low in price, easy to operate, and commercially available. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0025] Figure 1 The electrochemical impedance spectra of the copper sheet treated with the copper surface film treatment solution prepared in Examples 1 to 4 and Comparative Example 1 of the present invention;

[0026] Figure 2 The electrochemical impedance spectra of the copper sheet treated with the copper surface film treatment solution prepared in Example 2 and Examples 5-6 of the present invention;

[0027] Figure 3 The present invention uses the copper surface film layer treatment solution prepared in Example 2 and Comparative Example 1 to treat the cross-section of the copper sheet. A is Comparative Example 1, and B is Example 2. DETAILED DESCRIPTION

[0028] It should be noted that the following detailed descriptions are exemplary and are intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which the present invention belongs.

[0029] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0030] In view of the poor binding ability of silanol with copper, which affects the anti-corrosion performance of silane conversion film on the copper surface, the present invention proposes a copper surface film treatment liquid based on small molecule corrosion inhibitor, and a preparation method and application thereof.

[0031] A typical embodiment of the present invention provides a copper surface film treatment solution based on a small molecule corrosion inhibitor, which is composed of the following components in parts by weight: 4 to 6 parts of hydrolyzed silane, 0.25 to 5 parts of a small molecule corrosion inhibitor, and 45 to 55 parts of an alcohol solvent;

[0032] The hydrolyzed silane is obtained by hydrolyzing a silane coupling agent; and the small molecule corrosion inhibitor is one or more of CA, HEDP, and ATMP.

[0033] In some embodiments, the small molecule corrosion inhibitor is HEDP. Studies have shown that using HEDP as a small molecule corrosion inhibitor plays a better role in the present invention and can more significantly improve the anti-corrosion performance of copper.

[0034] In some embodiments, the silane coupling agent is PropS-SH. Studies have shown that PropS-SH contains a thiol group, which is more conducive to the combination of the silane conversion film and copper, thereby further improving the anti-corrosion performance of copper.

[0035] In some embodiments, 4 to 6 parts of hydrolyzed silane, 0.25 to 0.5 parts of small molecule corrosion inhibitor, and 45 to 55 parts of alcohol solvent. The present invention shows that under this ratio, the anti-corrosion performance of copper is better.

[0036] In some embodiments, 4 to 6 parts of hydrolyzed silane, 0.25 to 0.3 parts of small molecule corrosion inhibitor, and 45 to 55 parts of alcohol solvent. The present invention shows that under this ratio, the anti-corrosion performance of copper is better.

[0037] The alcohol solvent of the present invention is a liquid alcohol organic substance (an organic compound containing a hydroxyl group), such as methanol, ethanol, propanol, isopropanol, ethylene glycol, etc. In some embodiments, the alcohol solvent is ethanol. Using ethanol as an organic solvent has lower toxicity and is more conducive to commercialization.

[0038] Another embodiment of the present invention provides a method for preparing the above copper surface film treatment solution, comprising the following steps:

[0039] Adding a silane coupling agent to an alcohol-water mixed solvent, adjusting the pH value to acidic, and hydrolyzing for 22 to 26 hours to obtain hydrolyzed silane;

[0040] The small molecule corrosion inhibitor is added into an alcohol solvent to dissolve, and then the hydrolyzed silane is added and mixed evenly to obtain the product.

[0041] In some embodiments, the pH is adjusted to 3.5-4.5.

[0042] A third embodiment of the present invention provides a use of the above copper surface film treatment solution in treating the surface of a copper device.

[0043] In some embodiments, the processing method includes the following steps:

[0044] Pre-treating the surface of the copper device to remove surface impurities;

[0045] The pre-treated copper material device is placed into the copper surface film layer treatment solution and allowed to stand for treatment to obtain the device.

[0046] Specifically, the pretreatment is: adding the copper material device to an acid solution to remove oxide impurities on the surface. More specifically, the acid solution is one or more of nitric acid, phosphoric acid, sulfuric acid, and hydrochloric acid. More specifically, washing and drying are performed after the pretreatment.

[0047] Specifically, the static treatment time is 50 to 70 minutes.

[0048] Specifically, after the static treatment, washing and drying are performed.

[0049] A fourth embodiment of the present invention provides an anti-corrosion copper device, wherein the copper device is treated with the above-mentioned copper surface film treatment liquid so that a silane conversion film is attached to the copper device.

[0050] In some embodiments, the processing method includes the following steps:

[0051] Pre-treating the surface of the copper device to remove surface impurities;

[0052] The pre-treated copper material device is placed into the copper surface film layer treatment solution and allowed to stand for treatment to obtain the device.

[0053] Specifically, the pretreatment is: adding the copper material device to an acid solution to remove oxide impurities on the surface. More specifically, the acid solution is one or more of nitric acid, phosphoric acid, sulfuric acid, and hydrochloric acid. More specifically, washing and drying are performed after the pretreatment.

[0054] Specifically, the static treatment time is 50 to 70 minutes.

[0055] Specifically, after the static treatment, washing and drying are performed.

[0056] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in combination with specific embodiments and comparative examples.

[0057] Example 1

[0058] A method for preparing a copper surface film treatment solution, comprising the following steps:

[0059] 1. Dissolve 2 mL of PropS-SH in a mixed solvent of 3 mL of water and 45 mL of ethanol, at room temperature, pH 4, and hydrolyze for 24 h to obtain hydrolyzed silane.

[0060] 2. Weigh 0.05 g HEDP and dissolve it in 10 g ethanol.

[0061] 3. Take 1 g of the hydrolyzed silane prepared in step 1 and mix it evenly with the solution obtained in step 2 to prepare a copper surface film treatment solution.

[0062] The copper sheet is treated with the copper surface film treatment solution obtained in this embodiment, and the steps are as follows:

[0063] (1) The copper sheet is placed in a mixed acid solution (nitric acid with a mass concentration of 67%, sulfuric acid with a mass concentration of 97%, phosphoric acid with a mass concentration of 85%, hydrochloric acid with a mass concentration of 37% and water in a volume ratio of 3:2:2:1:2) to remove oxide impurities on the surface, rinse, and dry.

[0064] (2) The copper surface film layer obtained in this embodiment after pretreatment in step (1) is placed in a treatment solution and allowed to stand for 1 hour to obtain a copper sheet with a silane hybrid film bonded to the surface.

[0065] (3) The copper sheet with the silane hybrid film on the surface obtained in step (2) is taken out, rinsed, and placed in an oven for drying for 2 hours to obtain a copper sheet with a silane conversion film attached thereto having corrosion resistance.

[0066] Example 2

[0067] A method for preparing a copper surface film treatment solution, comprising the following steps:

[0068] 1. Dissolve 2 mL of PropS-SH in a mixed solvent of 3 mL of water and 45 mL of ethanol, at room temperature, pH 4, and hydrolyze for 24 h to obtain hydrolyzed silane.

[0069] 2. Weigh 0.10 g of HEDP and dissolve it in 10 g of ethanol.

[0070] 3. Take 1 g of the hydrolyzed silane prepared in step 1 and mix it evenly with the solution obtained in step 2 to prepare a copper surface film treatment solution.

[0071] The copper sheet is treated with the copper surface film treatment solution obtained in this embodiment, and the steps are as follows:

[0072] (1) The copper sheet is placed in a mixed acid solution (nitric acid with a mass concentration of 67%, sulfuric acid with a mass concentration of 97%, phosphoric acid with a mass concentration of 85%, hydrochloric acid with a mass concentration of 37% and water in a volume ratio of 3:2:2:1:2) to remove oxide impurities on the surface, rinse, and dry.

[0073] (2) The copper surface film layer obtained in this embodiment after pretreatment in step (1) is placed in a treatment solution and allowed to stand for 1 hour to obtain a copper sheet with a silane hybrid film bonded to the surface.

[0074] (3) The copper sheet with the silane hybrid film on the surface obtained in step (2) is taken out, rinsed, and placed in an oven for drying for 2 hours to obtain a copper sheet with a silane conversion film attached thereto having corrosion resistance.

[0075] Example 3

[0076] A method for preparing a copper surface film treatment solution, comprising the following steps:

[0077] 1. Dissolve 2 mL of PropS-SH in a mixed solvent of 3 mL of water and 45 mL of ethanol, at room temperature, pH 4, and hydrolyze for 24 h to obtain hydrolyzed silane.

[0078] 2. Weigh 0.20 g of HEDP and dissolve it in 10 g of ethanol.

[0079] 3. Take 1 g of the hydrolyzed silane prepared in step 1 and mix it evenly with the solution obtained in step 2 to prepare a copper surface film treatment solution.

[0080] The copper sheet is treated with the copper surface film treatment solution obtained in this embodiment, and the steps are as follows:

[0081] (1) The copper sheet is placed in a mixed acid solution (nitric acid with a mass concentration of 67%, sulfuric acid with a mass concentration of 97%, phosphoric acid with a mass concentration of 85%, hydrochloric acid with a mass concentration of 37% and water in a volume ratio of 3:2:2:1:2) to remove oxide impurities on the surface, rinse, and dry.

[0082] (2) The copper surface film layer obtained in this embodiment after pretreatment in step (1) is placed in a treatment solution and allowed to stand for 1 hour to obtain a copper sheet with a silane hybrid film bonded to the surface.

[0083] (3) The copper sheet with the silane hybrid film on the surface obtained in step (2) is taken out, rinsed, and placed in an oven for drying for 2 hours to obtain a copper sheet with a silane conversion film attached thereto having corrosion resistance.

[0084] Example 4

[0085] A method for preparing a copper surface film treatment solution, comprising the following steps:

[0086] 1. Dissolve 2 mL of PropS-SH in a mixed solvent of 3 mL of water and 45 mL of ethanol, at room temperature, pH 4, and hydrolyze for 24 h to obtain hydrolyzed silane.

[0087] 2. Weigh 1.00 g of HEDP and dissolve it in 10 g of ethanol.

[0088] 3. Take 1 g of the hydrolyzed silane prepared in step 1 and mix it evenly with the solution obtained in step 2 to prepare a copper surface film treatment solution.

[0089] The copper sheet is treated with the copper surface film treatment solution obtained in this embodiment, and the steps are as follows:

[0090] (1) The copper sheet is placed in a mixed acid solution (nitric acid with a mass concentration of 67%, sulfuric acid with a mass concentration of 97%, phosphoric acid with a mass concentration of 85%, hydrochloric acid with a mass concentration of 37% and water in a volume ratio of 3:2:2:1:2) to remove oxide impurities on the surface, rinse, and dry.

[0091] (2) The copper surface film layer obtained in this embodiment after pretreatment in step (1) is placed in a treatment solution and allowed to stand for 1 hour to obtain a copper sheet with a silane hybrid film bonded to the surface.

[0092] (3) The copper sheet with the silane hybrid film on the surface obtained in step (2) is taken out, rinsed, and placed in an oven for drying for 2 hours to obtain a copper sheet with a silane conversion film attached thereto having corrosion resistance.

[0093] Example 5

[0094] A method for preparing a copper surface film treatment solution, comprising the following steps:

[0095] 1. Dissolve 2 mL of PropS-SH in a mixed solvent of 3 mL of water and 45 mL of ethanol, at room temperature, pH 4, and hydrolyze for 24 h to obtain hydrolyzed silane.

[0096] 2. Weigh 0.1g CA and dissolve it in 10g ethanol.

[0097] 3. Take 1 g of the hydrolyzed silane prepared in step 1 and mix it evenly with the solution obtained in step 2 to prepare a copper surface film treatment solution.

[0098] The copper sheet is treated with the copper surface film treatment solution obtained in this embodiment, and the steps are as follows:

[0099] (1) The copper sheet is placed in a mixed acid solution (nitric acid with a mass concentration of 67%, sulfuric acid with a mass concentration of 97%, phosphoric acid with a mass concentration of 85%, hydrochloric acid with a mass concentration of 37% and water in a volume ratio of 3:2:2:1:2) to remove oxide impurities on the surface, rinse, and dry.

[0100] (2) The copper surface film layer obtained in this embodiment after pretreatment in step (1) is placed in a treatment solution and allowed to stand for 1 hour to obtain a copper sheet with a silane hybrid film bonded to the surface.

[0101] (3) The copper sheet with the silane hybrid film on the surface obtained in step (2) is taken out, rinsed, and placed in an oven for drying for 2 hours to obtain a copper sheet with a silane conversion film attached thereto having corrosion resistance.

[0102] Example 6

[0103] A method for preparing a copper surface film treatment solution, comprising the following steps:

[0104] 1. Dissolve 2 mL of K550 in a mixed solvent of 3 mL of water and 45 mL of ethanol, at room temperature, pH 4, and hydrolyze for 24 h to obtain hydrolyzed silane.

[0105] 2. Weigh 0.1 g of hydroxyethylidene diphosphonic acid and dissolve it in 10 g of ethanol.

[0106] 3. Take 1 g of the hydrolyzed silane prepared in step 1 and mix it evenly with the solution obtained in step 2 to prepare a copper surface film treatment solution.

[0107] The copper sheet is treated with the copper surface film treatment solution obtained in this embodiment, and the steps are as follows:

[0108] (1) The copper sheet is placed in a mixed acid solution (nitric acid with a mass concentration of 67%, sulfuric acid with a mass concentration of 97%, phosphoric acid with a mass concentration of 85%, hydrochloric acid with a mass concentration of 37% and water in a volume ratio of 3:2:2:1:2) to remove oxide impurities on the surface, rinse, and dry.

[0109] (2) The copper surface film layer obtained in this embodiment after pretreatment in step (1) is placed in a treatment solution and allowed to stand for 1 hour to obtain a copper sheet with a silane hybrid film bonded to the surface.

[0110] (3) The copper sheet with the silane hybrid film on the surface obtained in step (2) is taken out, rinsed, and placed in an oven for drying for 2 hours to obtain a copper sheet with a silane conversion film attached thereto having corrosion resistance.

[0111] Comparative Example 1

[0112] A method for preparing a copper surface film treatment solution, comprising the following steps:

[0113] 1. Dissolve 2 mL of PropS-SH in a mixed solvent of 3 mL of water and 45 mL of ethanol, at room temperature, pH 4, and hydrolyze for 24 h to obtain hydrolyzed silane.

[0114] 2. Take 1 g of the hydrolyzed silane prepared in step 1 and mix it evenly with 10 g of ethanol to prepare a copper surface film treatment solution.

[0115] The copper sheet is treated with the copper surface film treatment solution obtained in this embodiment, and the steps are as follows:

[0116] (1) The copper sheet is placed in a mixed acid solution (nitric acid with a mass concentration of 67%, sulfuric acid with a mass concentration of 97%, phosphoric acid with a mass concentration of 85%, hydrochloric acid with a mass concentration of 37% and water in a volume ratio of 3:2:2:1:2) to remove oxide impurities on the surface, rinse, and dry.

[0117] (2) The copper surface film layer obtained in this comparative example after pretreatment in step (1) is placed in a treatment solution and allowed to stand for 1 hour to obtain a copper sheet with a silane hybrid film bonded to the surface.

[0118] (3) The copper sheet with the silane hybrid film on the surface obtained in step (2) is taken out, rinsed, and placed in an oven for drying for 2 hours to obtain a copper sheet with a silane conversion film attached thereto having corrosion resistance.

[0119] Test Method

[0120] The protective performance of the prepared copper sheet with silane conversion film was tested. All electrochemical measurements were performed on an electrochemical workstation (CHI 750). In a three-electrode cell, a platinum sheet was used as the counter electrode, an Ag-AgCl electrode was used as the reference electrode, and the sample was used as the working electrode. The corrosion behavior of the modified copper sheet in 3.5wt.% NaCl solution was studied using electrochemical impedance spectroscopy.

[0121] The electrochemical impedance spectra of the copper sheets treated in Examples 1 to 4 are as follows: Figure 1 As shown in the figure, at the same PropS-SH concentration, as the HEDP concentration increases, the electrochemical impedance spectroscopy radius increases and then decreases, and the corrosion protection effect first increases and then decreases. The best anti-corrosion effect is shown when the HEDP concentration is 1%. It can be seen that the addition of HEDP enhances the corrosion resistance. The electrochemical impedance spectra of the copper sheets treated in Example 2 and Examples 5 to 6 are shown in the figure. Figure 2 As shown in the figure, it can be seen that the combined use of PropS-SH and HEDP has better corrosion resistance than the combined use of PropS-SH and CA and the combined use of KH550 and HEDP. Compared with the -NH2 in KH550, the -SH in PropS-SH has better adsorption ability with copper. After adding HEDP, HEDP acts as a bridge to make the silane film and copper more closely combined, and the small molecule corrosion inhibitor condenses with silane, improving the gap caused by steric hindrance, and the conversion film formed is denser and thicker. The specific results are as follows: Figure 3 shown.

[0122] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A copper surface film treatment solution based on a small molecule corrosion inhibitor, characterized in that: The method is composed of the following components in parts by weight: 4 to 6 parts of hydrolyzed silane, 0.25 to 5 parts of small molecule corrosion inhibitor, and 45 to 55 parts of alcohol solvent; The hydrolyzed silane is obtained by hydrolyzing a silane coupling agent; and the small molecule corrosion inhibitor is one or more of CA, HEDP, and ATMP.

2. The copper surface film treatment solution based on small molecule corrosion inhibitor according to claim 1, characterized in that: The small molecule corrosion inhibitor is hydroxyethylidene diphosphonic acid; Or, the silane coupling agent is KH-550, KH-560 or PropS-SH, preferably PropS-SH.

3. The copper surface film treatment solution based on small molecule corrosion inhibitor according to claim 1, characterized in that: 4-6 parts of hydrolyzed silane, 0.25-0.5 parts of small molecule corrosion inhibitor, 45-55 parts of alcohol solvent; Or, 4 to 6 parts of hydrolyzed silane, 0.25 to 0.3 parts of small molecule corrosion inhibitor, and 45 to 55 parts of alcohol solvent.

4. The copper surface film treatment solution based on small molecule corrosion inhibitor according to claim 1, characterized in that: The alcohol solvent is ethanol.

5. A method for preparing a copper surface film treatment solution according to claim 1, characterized in that: The steps include: Adding a silane coupling agent to an alcohol-water mixed solvent, adjusting the pH value to acidic, and hydrolyzing for 22 to 26 hours to obtain hydrolyzed silane; The small molecule corrosion inhibitor is added into an alcohol solvent to dissolve, and then the hydrolyzed silane is added and mixed evenly to obtain the product.

6. The preparation method according to claim 5, characterized in that: Adjust the pH value to 3.5-4.

5.

7. Use of the copper surface film treatment solution according to any one of claims 1 to 4 in treating the surface of a copper device.

8. The use according to claim 7, characterized in that: The processing method includes the following steps: Pre-treating the surface of the copper device to remove surface impurities; Put the pretreated copper material device into the copper surface film layer treatment solution and let it stand for treatment to obtain; Preferably, the pretreatment is: adding the copper material device into an acid solution to remove oxide impurities on the surface; Preferably, the static treatment time is 50 to 70 minutes.

9. A corrosion-resistant copper device, characterized in that: The copper surface film treatment liquid according to any one of claims 1 to 4 is used to treat a copper device, so that a silane conversion film is attached to the copper device.

10. The anti-corrosion copper material device according to claim 9, characterized in that: The processing method includes the following steps: Pre-treating the surface of the copper device to remove surface impurities; Put the pretreated copper material device into the copper surface film layer treatment solution and let it stand for treatment to obtain; Preferably, the pretreatment is: adding the copper material device into an acid solution to remove oxide impurities on the surface; Preferably, the static treatment time is 50 to 70 minutes.

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