Additive for tin electroplating process by using methanesulfonic acid method
阅读说明：本技术 用于甲基磺酸法电镀锡工艺的添加剂 (Additive for tin electroplating process by using methanesulfonic acid method ) 是由 施闽 于 2019-12-19 设计创作，主要内容包括：本发明公开用于甲基磺酸法电镀锡工艺的添加剂,所述用于甲基磺酸法电镀锡工艺的添加剂为对苯酚磺酸中苯环上的二元取代物,其中两个取代基分别被R<Sub>1</Sub>和R<Sub>2</Sub>,其中R<Sub>1</Sub>为聚氧乙烯醚(EO)或其与聚氧丙烯醚嵌段的共聚物(EO-PO-EO),其中所述聚氧乙烯醚(EO)的结构式和所述聚氧乙烯醚(EO)与聚氧丙烯醚嵌段的共聚物的结构式分别为：<Image he="256" wi="290" file="DDA0002325620740000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>和<Image he="209" wi="700" file="DDA0002325620740000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>所述n＝20～100,m＝20～50,其中R<Sub>1</Sub>的分子量为2000～6000；所述取代基R<Sub>2</Sub>为聚硅氧烷或聚氧丙烯醚,其结构式为：<Image he="274" wi="306" file="DDA0002325620740000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>和<Image he="307" wi="394" file="DDA0002325620740000014.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中K＝1～20,其中J＝1～20。(The invention discloses an additive for a tin electroplating process by a methanesulfonic acid method, which is a binary substituent on a benzene ring in p-phenolsulfonic acid, wherein two substituents are respectively represented by R 1 And R 2 Wherein R is 1 Is polyoxyethylene Ether (EO) or a copolymer (EO-PO-EO) of the polyoxyethylene Ether (EO) and a polyoxypropylene ether block, wherein the structural formula of the polyoxyethylene Ether (EO) and the structural formula of the copolymer of the polyoxyethylene Ether (EO) and the polyoxypropylene ether block are respectively as follows: and n is 20 to 100, m is 20 to 50, wherein R 1 The molecular weight of (A) is 2000-6000; the substituent R 2 Is polysiloxane or polyoxypropylene ether, and has a structural formula as follows: and wherein K is 1-20, and J is 1-20.)
1. The additive for the methanesulfonic acid method tin electroplating process is characterized in that the additive for the methanesulfonic acid method tin electroplating process is a binary substituent on a benzene ring in p-phenolsulfonic acid, wherein two substituents are respectively represented by R1And R2，
Wherein R is1Is polyoxyethylene Ether (EO) or a copolymer (EO-PO-EO) of the polyoxyethylene Ether (EO) and a polyoxypropylene ether block, wherein the structural formula of the polyoxyethylene Ether (EO) and the structural formula of the copolymer of the polyoxyethylene Ether (EO) and the polyoxypropylene ether block are respectively as follows:
n is 20 to 100, m is 20 to 50, wherein R1The molecular weight of (A) is 1000-10000;
the substituent R2Is polysiloxane or polyoxypropylene ether, and has a structural formula as follows:
wherein K is 1-20, and J is 1-20.
2. The additive for tin electroplating process by methane sulfonic acid method according to claim 1, wherein the formula of the additive for tin electroplating process by methane sulfonic acid method is as follows:
3. an additive for use in a process of electroplating tin by the methanesulfonic acid method according to claim 1 or 2, wherein K is 1 to 10.
4. The additive for a methanesulfonic acid tin electroplating process according to claim 3, wherein J-1 to 10.
5. The additive for the methanesulfonic acid tin electroplating process according to claim 1, wherein the molecular weight of R1 is 2000-6000, wherein n: m ranges from 0.5 to 30.
6. The additive for the methanesulfonic acid method tin electroplating process is characterized in that the additive for the methanesulfonic acid method tin electroplating process is a binary substituent on a benzene ring in benzenediol sulfonic acid, wherein two substituents are respectively represented by R3And R4，
Wherein R is3is-OR5Wherein R is5Is polyoxyethylene Ether (EO) or a copolymer (EO-PO-EO) of the polyoxyethylene Ether (EO) and a polyoxypropylene ether block, wherein the structural formula of the polyoxyethylene Ether (EO) and the structural formula of the copolymer of the polyoxyethylene Ether (EO) and the polyoxypropylene ether block are respectively
N is 20 to 100, m is 20 to 50, wherein R5The molecular weight of (A) is 1000-10000;
the substituent R4Is polysiloxane or polyoxypropylene ether, and has a structural formula as follows:
wherein K is 1-20, and J is 1-20.
7. The additive for a tin electroplating process by a methanesulfonic acid method according to claim 5, having a structural formula of:
8. an additive for use in a process of electroplating tin by the methanesulfonic acid method according to claim 5 or 6, wherein K is 1 to 10.
9. The additive for a methanesulfonic acid tin electroplating process according to claim 7, wherein J-1 to 10.
10. The additive for a tin electroplating process by a methyl sulfonic acid method according to claim 6, wherein the molecular weight of R5 is 2000-6000, wherein n: m ranges from 0.5 to 30.
Technical Field
The invention relates to an additive, in particular to an additive for a tin electroplating process by a methanesulfonic acid method.
Background
The tin-electroplated thin steel plate is commonly called tinplate and is a common packaging material. The packaging material is characterized in that both sides of a cold-rolled low-carbon steel sheet or strip are plated with tin. Tin mainly serves to prevent corrosion and rusting. It combines the strength and formability of steel with the corrosion resistance, soldering property and beautiful appearance of tin into one material, and has the characteristics of corrosion resistance, no toxicity, high strength and good ductility.
Disclosure of Invention
An object of the present invention is to provide an additive for a tin electroplating process by a methylsulfonic acid method, wherein the additive for a tin electroplating process by a methylsulfonic acid method can simultaneously function as an antioxidant and a surfactant in tin electroplating by a methylsulfonic acid method.
An object of the present invention is to provide an additive for a tin electroplating process by a methanesulfonic acid method, wherein the additive for a tin electroplating process by a methanesulfonic acid method can be used in a tin electroplating process by a methanesulfonic acid method to reduce process steps so that the tin electroplating process by a methanesulfonic acid method becomes simpler.
An object of the present invention is to provide an additive for a tin electroplating process by a methanesulfonic acid method, wherein the additive for a tin electroplating process by a methanesulfonic acid method is capable of reducing a height of bubbles when used in the tin electroplating process by a methanesulfonic acid method.
In order to achieve at least one of the above objects, the present invention provides an additive for tin electroplating process by methanesulfonic acid method, wherein the additive for tin electroplating process by methanesulfonic acid method is a binary substituent on benzene ring in p-phenolsulfonic acid, and two substituents are respectively represented by R1And R2，
Wherein R is1Is polyoxyethylene Ether (EO) or a copolymer (EO-PO-EO) of the polyoxyethylene Ether (EO) and a polyoxypropylene ether block, wherein the structural formula of the polyoxyethylene Ether (EO) and the structural formula of the copolymer of the polyoxyethylene Ether (EO) and the polyoxypropylene ether block are respectively as follows:
n is 20 to 100, m is 20 to 50, wherein R1The molecular weight of (A) is 1000-10000;
the substituent R2Is polysiloxane or polyoxypropylene ether, and has a structural formula as follows:
wherein K is 1-20, and J is 1-20.
According to an embodiment of the invention, the additive for the tin electroplating process by the methanesulfonic acid method has a structural formula as follows:
in accordance with an embodiment of the present inventionFor example, K is 1 to 10.
According to an embodiment of the present invention, J is 1 to 10.
According to an embodiment of the invention, the molecular weight of R1 is 2000-6000, wherein n: m ranges from 0.5 to 30.
To achieve the above object of the inventionThe invention provides an additive for a tin electroplating process by a methanesulfonic acid method, wherein the additive for the tin electroplating process by the methanesulfonic acid method is a binary substituent on a benzene ring in benzenediol sulfonic acid, and two substituents are respectively substituted by R3And R4，
Wherein R is3is-OR5Wherein R is5Is polyoxyethylene Ether (EO) or a copolymer (EO-PO-EO) of the polyoxyethylene Ether (EO) and a polyoxypropylene ether block, wherein the structural formula of the polyoxyethylene Ether (EO) and the structural formula of the copolymer of the polyoxyethylene Ether (EO) and the polyoxypropylene ether block are respectively
N is 20 to 100, m is 20 to 50, wherein R5The molecular weight of (A) is 1000-10000;
the substituent R4Is polysiloxane or polyoxypropylene ether, and has a structural formula as follows:
wherein K is 1-20, and J is 1-20.
According to an embodiment of the invention, the additive for the tin electroplating process by the methanesulfonic acid method has a structural formula as follows:
according to an embodiment of the invention, the molecular weight of R5 is 2000-6000, wherein n: m ranges from 0.5 to 30.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention, and not to limit the scope of the claims.
In accordance with a preferred embodiment of the present invention, for the methanesulfonic acid processThe additive for tin electroplating process will be described in detail below, and in this embodiment, the additive for tin electroplating process by methane sulfonic acid method is a modified substance of phenolsulfonic acid, specifically a binary substituent on benzene ring in phenolsulfonic acid, wherein two substituents are respectively represented by R1And R2。
In the first embodiment of the present invention, the additive used in the tin electroplating process by the methanesulfonic acid method is a binary substituent on a benzene ring in p-phenolsulfonic acid, which is a modified substance of phenolsulfonic acid. Preferably, the additive used in the tin electroplating process by the methanesulfonic acid method is a para-binary substituent on a benzene ring in p-phenolsulfonic acid, and the structural formula of the additive is as follows:
it is worth mentioning that the substituent R1Is polyoxyethylene Ether (EO) or a copolymer (EO-PO-EO) of the polyoxyethylene ether and polyoxypropylene ether blocks. The substituent R1The substituent R is a hydrophilic group when the modified substance of the p-phenolsulfonic acid is used as an additive of the electrotinning process1Can make the function of grain refinement.
The substituent R1: the structural formula of polyoxyethylene Ether (EO) or polyoxypropylene ether block copolymer (EO-PO-EO) thereof is respectively as follows: specifically, the copolymer (EO-PO-EO) has the structural formula:
wherein n is 20 to 100, m is 20 to 50, and R is1Has a molecular weight of 1000 to 10000, preferably, R1The molecular weight of (A) is 2000-6000. More preferably, n: m is in the range of 0.5 to 30, preferably 1 to 20. R1Too large or too small a molecular weight of (a) may reduce the ability of the p-phenolsulfonic acid modification to refine grains when used as an additive in an electrolytic tinning process.
The substituent R2Is polysiloxane or polyoxypropylene ether, and has a structural formula as follows:
k is 1-20, preferably 1-10. J is 1 to 20, preferably 1 to 10. The substituent R2Is a relatively hydrophobic group, and when the additive for the tin electroplating process by the methanesulfonic acid method is used as the additive for the tin electroplating process, the substituent R2Plays a role in suppressing foaming of the tin plating bath. And the substituent R is different from that of adding a foam inhibitor in the tin plating solution2The anti-foaming agent is directly fixed on the additive through a molecular bond, so that the long-term maintenance of the anti-foaming performance of a tinning plating solution system can be ensured, and the control process of the plating solution is further simplified. The substituent R2The length of the segment(s) determines the bubble suppressing properties, but if the segment(s) is too long, the stability and grain refining properties of the additive in the bath system will be affected.
In another embodiment of the invention, the additive used in the tin electroplating process by the methanesulfonic acid method is a modified product of hydroquinone sulfonic acid, in particular a binary substituent on a benzene ring in the hydroquinone sulfonic acid, wherein two substituents are respectively represented by R3And R4. Preferably, the binary substituent on the benzene ring in the hydroquinone sulfonic acid is a meta-substituent on the benzene ring in the hydroquinone sulfonic acid. The hydroquinone sulfonic acid is modified, so that the modified hydroquinone sulfonic acid can play a role of an antioxidant and a role of grain refinement simultaneously when being used as an additive of an electrotinning process. Specifically, the additive for the tin electroplating process by the methanesulfonic acid method has the structural formula:
it is worth mentioning that the substituent R3is-OR5Wherein R is5Is polyoxyethylene Ether (EO) or a copolymer (EO-PO-EO) of the polyoxyethylene ether and polyoxypropylene ether blocks. The group R5Relatively hydrophilic group, the p-phenolsulfonic acid being used as electrotinningAdditive to the process, said radical R5Can make the function of grain refinement. Specifically, the additive for the tin electroplating process by the methanesulfonic acid method has the structural formula:
the group R5: polyoxyethylene Ether (EO) or polyoxypropylene ether block copolymer thereof (EO-PO-EO).
Specifically, the copolymer (EO-PO-EO) has the structural formula:
wherein n is 20 to 100, m is 20 to 50, and the group R5Has a molecular weight of 1000 to 10000, preferably, R5The molecular weight of (A) is 2000-6000. More preferably, n: m is in the range of 0.5 to 30, preferably 1 to 20.
Preferably, n is 50-80. More preferably, n is 75.
The substituent R4Is polysiloxane or polyoxypropylene ether, and has a structural formula as follows:
k is 1-20, preferably 1-10. J is 1 to 20, preferably 1 to 10. The substituent R4Is a relatively hydrophobic group, and when the p-phenolsulfonic acid is used as an additive in the tin electroplating process, the substituent R4Plays a role in suppressing foaming of the tin plating bath. And the substituent R is different from that of adding a foam inhibitor in the tin plating solution4The anti-foaming agent is directly fixed on the additive through a molecular bond, so that the long-term maintenance of the anti-foaming performance of a tinning plating solution system can be ensured, and the control process of the plating solution is further simplified. The substituent R4The length of the segment(s) determines the foam suppressing properties, but if the segment(s) are too long, this will affect the performance of the additive in the bath systemStability and grain refinement properties.
It can thus be seen that the objects of the invention are sufficiently well-attained. The embodiments for explaining the functional and structural principles of the present invention have been fully illustrated and described, and the present invention is not limited by changes based on the principles of these embodiments. Accordingly, this invention includes all modifications encompassed within the scope and spirit of the following claims.