CN113502520B - Sealing agent suitable for electroplated copper layer and hole sealing method - Google Patents
Sealing agent suitable for electroplated copper layer and hole sealing method Download PDFInfo
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- CN113502520B CN113502520B CN202110743595.XA CN202110743595A CN113502520B CN 113502520 B CN113502520 B CN 113502520B CN 202110743595 A CN202110743595 A CN 202110743595A CN 113502520 B CN113502520 B CN 113502520B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
Abstract
The invention relates to a sealing agent suitable for an electroplated copper layer, which is characterized by comprising the following raw materials in parts by weight: 400-500 parts of deionized water, 1-3 parts of ethanol alcohol, 1-3 parts of polyethylene glycol, 2-4 parts of panthenol, 10-20 parts of polyethyleneimine, 10-15 parts of lauryl methyl polysiloxane copolyol, 1-5 parts of fluorosulfonyl difluoroacetic acid methyl ester and 1-5 parts of nano silicon oxide. The invention also relates to a hole sealing method suitable for the electroplated copper layer, which comprises the following steps: firstly, cleaning the surface of a workpiece electroplated with copper by using water and then drying; step two, mixing the blocking agent of claim 1 with deionization according to the ratio of 1:5-10 to obtain a sealing solution; step three, heating the temperature of the sealing solution to 70-80 ℃ by adopting water bath heating and keeping the temperature; and step four, putting the workpiece into a sealing solution, immersing for 60-90s, taking out, standing for not less than 120s, then washing with water, and then drying.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to a sealing agent suitable for an electroplated copper layer and a hole sealing method.
Background
The electroplated copper layer needs to be subjected to sealing treatment due to the porosity, and a sealing agent is usually directly added into a sealing solution to enhance the sealing effect of the electroplated copper layer. The hole sealing agent is generally composed of some nano-scale particles which can be uniformly filled in the pores of the electroplated copper layer, so that the compactness of the electroplated copper layer becomes better, and the capability of the electroplated copper layer for resisting the corrosion of harmful media is enhanced to a great extent.
However, the technical problems existing in the prior art are as follows: the nano particles are directly added into the sealing solution, so that the nano particles can not be guaranteed to be effectively filled in gaps of the electroplated copper, and the nano particles are added into the sealing solution to cause poor stability of the sealing solution, so that the dispersing capacity and stability of the sealant in the sealing solution are problems to be solved urgently.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a sealing agent and a hole sealing method suitable for an electroplated copper layer.
On one hand, the invention provides a sealing agent suitable for electroplating a copper layer, which comprises the following raw materials in parts by mass: 400-500 parts of deionized water, 1-3 parts of ethanol, 1-3 parts of polyethylene glycol, 2-4 parts of panthenol, 10-20 parts of polyethyleneimine, 10-15 parts of lauryl methyl polysiloxane copolyol, 1-5 parts of fluorosulfonyl difluoroacetic acid methyl ester and 1-5 parts of nano silicon oxide.
On the other hand, the invention also provides a hole sealing method suitable for the electroplated copper layer, which specifically comprises the following steps:
firstly, cleaning the surface of a workpiece electroplated with copper by using water and then drying;
step two, mixing the sealing agent and deionized water according to the proportion of 1:5-10 to obtain a sealing solution;
step three, heating the temperature of the sealing solution to 70-80 ℃ by adopting water bath heating and keeping the temperature;
and step four, putting the workpiece into a sealing solution, immersing for 60-90s, taking out, standing for not less than 120s, then washing with water, and then drying.
Compared with the prior art, the technical scheme provided by the invention has at least the following beneficial effects:
in the sealant provided by the invention, lauryl methyl polysiloxane copolyol and methyl fluorosulfonyl difluoroacetate have a synergistic effect, so that nano silicon oxide can be uniformly dispersed in the sealant and a sealing solution;
the sealant provided by the invention can keep stability in long-term storage through selection and proportioning of components;
in the sealant provided by the invention, lauryl methyl polysiloxane copolyol can promote polyethyleneimine to form a sealing film on the surface of an electroplated copper layer, and lauryl methyl polysiloxane copolyol and fluorosulfonyl difluoroacetic acid methyl ester have a synergistic effect to activate the surface of the electroplated copper layer and improve the bonding strength of the electroplated copper layer and the sealing film;
in the sealant provided by the invention, lauryl methyl polysiloxane copolyol and polyethyleneimine can form a protective layer on the surface of the electroplated copper layer through the synergistic action of chemical adsorption and physical adsorption, and the lauryl methyl polysiloxane copolyol and polyethyleneimine have a plurality of adsorption sites, so that the adsorption effect on the electroplated copper layer is stronger.
Drawings
The figures further illustrate the invention, but the examples in the figures do not constitute any limitation of the invention.
FIG. 1 is a Nyquist plot (corresponding to (a) in the drawing) and a Bode plot (corresponding to (b) in the drawing) of the impedance spectrum of the electroplated copper layer after different capping solution treatments.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The embodiment provides a sealing agent suitable for an electroplated copper layer, which comprises the following raw materials in parts by mass: 480 parts of deionized water, 2 parts of ethanol, 2 parts of polyethylene glycol, 3 parts of panthenol, 14 parts of polyethyleneimine, 12 parts of lauryl methyl polysiloxane copolyol, 4 parts of fluorosulfonyl difluoromethyl acetate and 3 parts of nano-silica.
Example 2
The embodiment provides a hole sealing method suitable for an electroplated copper layer, which specifically comprises the following steps:
step one, cleaning the surface of a workpiece (Q235 steel plate with the thickness of 50mm multiplied by 100mm multiplied by 1 mm) which is electroplated with copper by water, and then drying;
step two, mixing the sealant provided in example 1 with deionized water according to a ratio of 1:10 to obtain a closed solution;
step three, heating the temperature of the sealing solution to 70 ℃ by adopting water bath heating and keeping the temperature;
and step four, putting the workpiece into the sealing solution, immersing for 80s, taking out, standing for 120s, then washing with water, and then drying.
The porosity of the electroplated copper layer after the hole sealing treatment is measured by adopting a porosity detection method (a filter paper attaching method) of the metal plating layer described in QB/T3823-1999, and after the electroplated copper layer on the surface of the workpiece is treated by adopting the hole sealing method provided by the embodiment, no color change point appears on the filter paper after 5min of pasting time.
After the electroplated copper layer on the surface of the workpiece is treated by the hole sealing method provided by the embodiment, the corrosion resistance test method of the metal coating described in GB5938-86 is adopted for testing, and the test result shows that the electroplated copper workpiece treated by the hole sealing method provided by the embodiment can resist 96h neutral salt spray, which is far higher than the industrial requirement.
Comparative example 1
The difference between the sealing agent provided in this embodiment and embodiment 1 is only that the sealing agent provided in this embodiment does not contain nano-silica.
Comparative example 2
Compared with the sealing agent in example 1, the sealing agent provided in this example is different only in that the sealing agent does not contain lauryl methyl polysiloxane copolyol, and the mass part of the fluorosulfonyl difluoroacetic acid methyl ester in the sealing agent provided in this example is increased to 16 parts.
Comparative example 3
The difference between the sealant provided in this example and the sealant provided in example 3 is that the sealant provided in this example does not contain fluorosulfonyl difluoroacetic acid methyl ester, and the mass part of the lauryl methyl polysiloxane copolyol in the sealant provided in this example is increased to 16 parts.
The blocking agents provided in example 1 and comparative examples 1 to 3 were mixed with deionized water in a ratio of 1:10, adopting 4Q 235 steel plates with the same specification, depositing copper layers with the same thickness on the 4Q 235 steel plates by adopting the same copper electroplating process, respectively adopting the four different sealing solutions to carry out sealing treatment on the 4Q 235 steel plates after the copper electroplating (the specific sealing treatment step is the same as the step of the sealing method suitable for the copper electroplating layer provided in the example 2), and respectively marking the Q235 steel plates after the sealing treatment as a (corresponding to the example 1), b (corresponding to the comparative example 1), c (corresponding to the comparative example 2) and d (corresponding to the comparative example 3).
And (3) testing the influence of corrosion resistance of the a, the b, the c and the d to neutral brine by using an alternating current impedance method to obtain an alternating current impedance diagram as shown in figure 1. The EIS experimental data are fitted by using zsimwin software to obtain corresponding total impedance values as shown in table 1, and it can be judged from fig. 1 and table 1 that after the electroplated copper layer is subjected to sealing treatment by using the sealing agent provided in example 1, the diameter corresponding to the capacitive arc resistance is larger, and the corrosion resistance is better. After the electroplated copper layer is subjected to sealing treatment by using the sealing agent provided by the comparative example 3, the diameter of the capacitive arc is small, the formed sealing film layer is poor in compactness, and the nano silicon oxide cannot be well dispersed in the sealing solution, so that the nano silicon oxide cannot be effectively filled in gaps of the electroplated copper layer, and therefore the corrosion resistance is poor. After the copper plating layer is subjected to sealing treatment by using the sealing agent provided in comparative example 2, the diameter of the capacitive arc is smaller, and a contraction phenomenon occurs in a low frequency region of the capacitive arc, the lack of lauryl methyl polysiloxane copolyol results in poor compactness of the formed sealing film layer and poor bonding strength of the sealing film with the copper plating layer, and the nano-silica cannot be well dispersed in the sealing solution to result in inefficient filling in gaps of the copper plating layer, thus being less corrosion resistant. After the sealing treatment of the electroplated copper layer is carried out by using the sealing agent provided by comparative example 1, no nano silicon oxide is filled in the gaps of the electroplated copper layer, so that chloride ions in sodium chloride permeate into the film layer, and the corrosion resistance of the film layer is weakened.
TABLE 1
Adopting a lead acetate drop test to test a, b, c and d, specifically, preparing 5% (mass fraction) of lead acetate solution, respectively dripping a drop of lead acetate liquid on the surfaces of a, b, c and d by using a rubber head dropper, recording the time required for the solution to contact the surfaces of a, b, c and d to generate corrosion (bright spots), wherein the arrangement sequence of the bright spots is as follows: b. c, d, a, b appear the shortest time (about 6 s) and a appear the longest time (about 13.4 s), which is consistent with the electrochemical impedance spectroscopy result.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (2)
1. The sealing agent suitable for the electroplated copper layer is characterized by comprising the following raw materials in parts by mass: 400-500 parts of deionized water, 1-3 parts of ethanol, 1-3 parts of polyethylene glycol, 2-4 parts of panthenol, 10-20 parts of polyethyleneimine, 10-15 parts of lauryl methyl polysiloxane copolyol, 1-5 parts of fluorosulfonyl difluoroacetic acid methyl ester and 1-5 parts of nano silicon oxide.
2. A hole sealing method suitable for an electroplated copper layer is characterized by comprising the following steps:
step one, cleaning the surface of a workpiece electroplated with copper by using water and then drying;
step two, mixing the sealant of claim 1 with deionized water according to a ratio of 1:5-10 to obtain a sealing solution;
step three, heating the temperature of the sealing solution to 70-80 ℃ by adopting water bath heating and keeping the temperature;
and step four, putting the workpiece into a sealing solution, immersing for 60-90s, taking out, standing for not less than 120s, then washing with water, and then drying.
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Citations (7)
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| CN106085088A (en) * | 2016-06-13 | 2016-11-09 | 合肥和安机械制造有限公司 | A kind of copper anticorrosion silane coating and preparation method thereof |
| CN106318200A (en) * | 2016-08-17 | 2017-01-11 | 安徽红桥金属制造有限公司 | Modified waterborne composite sealing agent and preparation method thereof |
| CN107904635A (en) * | 2017-11-07 | 2018-04-13 | 扬州大学 | A kind of electroless nickel layer surface-closed agent prescription and hole-sealing technology |
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| CN110205620A (en) * | 2019-06-27 | 2019-09-06 | 范文莲 | A kind of compound closure agent of high-efficiency environment friendly and preparation method thereof |
| CN111117309A (en) * | 2020-01-07 | 2020-05-08 | 上海益特码科贸有限公司 | Nano sealing agent and preparation method thereof |
| CN112522692A (en) * | 2020-11-29 | 2021-03-19 | 湖南金裕环保科技有限公司 | Water-soluble metal surface sealing protection liquid, preparation method and application |
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2021
- 2021-06-30 CN CN202110743595.XA patent/CN113502520B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106085088A (en) * | 2016-06-13 | 2016-11-09 | 合肥和安机械制造有限公司 | A kind of copper anticorrosion silane coating and preparation method thereof |
| CN106318200A (en) * | 2016-08-17 | 2017-01-11 | 安徽红桥金属制造有限公司 | Modified waterborne composite sealing agent and preparation method thereof |
| CN107904635A (en) * | 2017-11-07 | 2018-04-13 | 扬州大学 | A kind of electroless nickel layer surface-closed agent prescription and hole-sealing technology |
| CN108948899A (en) * | 2018-07-18 | 2018-12-07 | 太仓东旭精密机械有限公司 | One Albatra metal protective layer |
| CN110205620A (en) * | 2019-06-27 | 2019-09-06 | 范文莲 | A kind of compound closure agent of high-efficiency environment friendly and preparation method thereof |
| CN111117309A (en) * | 2020-01-07 | 2020-05-08 | 上海益特码科贸有限公司 | Nano sealing agent and preparation method thereof |
| CN112522692A (en) * | 2020-11-29 | 2021-03-19 | 湖南金裕环保科技有限公司 | Water-soluble metal surface sealing protection liquid, preparation method and application |
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| "SiO2/聚硅氧烷纳米复合防腐涂层的制备与性能";吴春春等;《硅酸盐学报》;20100515;第38卷(第5期);第959-963页 * |
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