Sulfonate electroplating bath, process for refining metal by electrolytic depositing and process for controlling metal morphology in electrolytic refining

Patent metadata

Field	Value
Publication number	US-2024287696-A1
Application number	US-202218562695-A
Country	US
Kind code	A1
Filing date	May 12, 2022
Priority date	May 20, 2021
Publication date	Aug 29, 2024
Grant date	—

Abstract

The present invention relates to an electroplating bath comprising (A) an alkane sulfonic acid or alkanol sulfonic acid; (B) a soluble metal salt of alkane sulfonic acid or alkanol sulfonic acid; and (C) at least one additive selected from—polyether derivatives of formula (I),—sulfonated or sulfated polyether derivatives of formula (II) or—any combinations thereof, wherein the groups in formulae (I) and (II) are as defined in the description and claims. The present invention also relates to a process for refining metal and a process for controlling morphology of metal deposited on cathode in electrolytic refining of the metal, which comprise using the electroplating bath according to the present invention.

First claim

1 . An electroplating bath, comprising
(A) an alkane sulfonic acid or alkanol sulfonic acid; (B) a soluble metal salt of alkane sulfonic acid or alkanol sulfonic acid; and (C) at least one additive selected from
polyether derivatives of formula (I),

wherein
Ar is phenyl substituted by C 3 -C 12 -alkyl, or
naphthyl which is non-substituted or substituted by C 1 -C 4 -alkyl,

E 1 and E 2 are different from each other and selected from ethyleneoxy and propyleneoxy,
m is 0 or a number in the range of 1 to 40,
n is a number in the range of 1 to 40,
sulfonated or sulfated polyether derivatives of formula (II),

wherein
Ar′ is phenyl substituted by C 3 -C 12 -alkyl and optionally substituted by a group of —SO 3 M, or
naphthyl which is non-substituted or substituted by C 1 -C 4 -alkyl and/or a group of —SO 3 M,
E 1 ′ and E 2 ′ are different alkyleneoxy groups and selected from ethyleneoxy and propyleneoxy,
E 3 is the alkylene moiety of E 2 ,
m′ is 0 or a number in the range of 1 to 40,
is 0 or 1,
the sum of n′+o is a number in the range of 1 to 40, and
M is an alkali metal cation or NH 4 + ,
and
any combinations thereof.

2 . The electroplating bath according to claim 1 , wherein in formula (I), m is 0 or a number in the range of 2 to 35, and in formula (II), m′ is 0 or a number in the range of 2 to 35, o is 0 or 1, and n′+o is a number in the range of 2 to 35.

3 . The electroplating bath according to claim 2 , wherein the at least one additive (C) is selected from
the polyether derivatives of formula (I), wherein
Ar is phenyl substituted by C 3 -C 12 -alkyl, or
naphthyl which is non-substituted or substituted by C 1 -C 4 -alkyl,
E 1 and E 2 are different from each other and selected from ethyleneoxy and propyleneoxy,
m is 0 or a number in the range of 4 to 30,
n is a number in the range of 4 to 30,
sulfonated or sulfated polyether derivatives of formula (II), wherein

Ar′ is phenyl substituted by C 3 -C 12 -alkyl and optionally substituted by a group of —SO 3 M, or
naphthyl which is non-substituted or substituted by C 1 -C 4 -alkyl and/or a group of-SO 3 M,
E 1 ′ and E 2 ′ are different alkyleneoxy groups and selected from ethyleneoxy and propyleneoxy,
E 3 is the alkylene moiety of E 2 ,
m′ is 0 or a number in the range of 4 to 30,
o is 0 or 1,
the sum of n′+o is a number in the range of 4 to 30, and
M is an alkali metal cation or NH 4 + ,
and
any combinations thereof.

4 . The electroplating bath according to claim 1 , wherein the at least one additive (C) is selected from the polyether derivatives of formula (I) wherein m is 0 and n is a number in the range of 4 to 30, the sulfonated or sulfated polyether derivatives of formula (II) wherein m′ is 0, o is 0 or 1 and the sum of n′+o is a number in the range of 4 to 30, or any combinations thereof.

5 . The electroplating bath according to claim 1 , wherein E 2 and E 2 ′ are ethyleneoxy.

6 . The electroplating bath according to claim 3 , wherein the at least one additive (C) is selected from
the polyether derivatives of formula (Ia)

wherein
Ar is 4-(C 3 -C 12 -alkyl)phenyl or non-substituted naphthyl,
n is a number in the range of 4 to 30,
sulfonated or sulfated polyether derivatives of formula (II),

wherein
Ar′ is 4-(C 3 -C 12 -alkyl)phenyl, optionally substituted by a group of —SO 3 M, or
naphthyl which is non-substituted or substituted a group of —SO 3 M,

o is 0 or 1,
the sum of n′+o is a number in the range of 4 to 30, and
M is an alkali metal cation or NH 4 + ,
and
any combinations thereof.

7 . The electroplating bath according to claim 1 , wherein Ar is phenyl substituted by C 4 -C 10 -alkyl, or non-substituted naphthyl.

8 . The electroplating bath according to claim 7 , wherein Ar is non-substituted β-naphthyl.

9 . The electroplating bath according to claim 1 , wherein Ar′ is phenyl substituted by C 4 -C 10 -alkyl and —SO 3 M, or naphthyl which is non-substituted or substituted by —SO 3 M.

10 . The electroplating bath according to claim 9 , wherein Ar′ is 4-(C 4 -C 10 -alkyl)phenyl having a group of —SO 3 M at the 2- or 3-position of the phenyl ring.

11 . The electroplating bath according to claim 1 ,
wherein the at least one additive (C) is selected from
the polyether derivatives of formula (Ia) wherein Ar is non-substituted β-naphthyl, n is a number in the range of 6 to 20,
the sulfonated or sulfated polyether derivatives of formula (Ia) wherein Ar′ is 4-(C 4 -C 10 -alkyl)phenyl having a group of —SO 3 M at the 2- or 3-position of the phenyl ring, o is 0, n′ is a number in the range of 6 to 20, and M is an alkali metal cation or NH 4 + ,
and any combinations thereof.

12 . The electroplating bath according to claim 11 , wherein the at least one additive (C) is selected from
the polyether derivatives of formula (Ia) wherein Ar is non-substituted β-naphthyl, and n is a number in the range of 8 to 15, the sulfonated or sulfated polyether derivatives of formula (Ia) wherein Ar′ is 4-(C 4 -C 10 -alkyl)phenyl having a group of —SO 3 M at the 2- or 3-position of the phenyl ring, o is 0, n′ is a number in the range of 8 to 15, and M is an alkali metal cation or NH 4 + , and any combinations thereof.

13 . The electroplating bath according to claim 12 , wherein the at least one additive (C) is selected from
the polyether derivatives of formula (Ia) wherein Ar is non-substituted β-naphthyl, n is 10, 11, 12 or 13; the sulfonated or sulfated polyether derivatives of formula (IIa) wherein Ar′ is 4-(C 4 -C 10 -alkyl)phenyl having a group of —SO 3 M at the 2- or 3-position of the phenyl ring, o is 0, n′ is 9, 10, 11 or 12, and M is an alkali metal cation or NH 4 + , and any combinations thereof.

14 . The electroplating bath according to claim 1 , wherein M is Na + or K + .

15 . The electroplating bath according to claim 1 , wherein the alkane sulfonic acid (A) is selected from C 1 -C 12 -alkane sulfonic acids.

16 . The electroplating bath according to claim 1 , wherein the alkanol sulfonic acid (A) is selected from C 2 -C 12 -alkanol sulfonic acids.

17 . The electroplating bath according to claim 1 , wherein the soluble metal salt (B) is at least one soluble metal salt of the same alkane sulfonic acid or alkanol sulfonic acid as the component (A).

18 . The electroplating bath according to claim 1 , wherein the metal of the soluble metal salt (B) is selected from lead and tin.

19 . The electroplating bath according to claim 1 , wherein the at least one additive each is comprised in the electroplating bath at a concentration in the range of 0.5 to 5.0 g/L of the bath.

20 . The electroplating bath according to claim 1 , which comprises a combination of at least one polyether derivative and at least one sulfonated or sulfated polyether derivative as the comp

Assignees

• Basf Se

Inventors

• Zhu Si Jun
• Song jin bo
• Xia Jing Cheng
• Chen Yong Ming
• Chang Cong
• Li You Gang
• Xiang Chang Liu
• Yang Sheng Hai

Classifications

• C25D3/36

  characterised by the organic bath constituents used · CPC title

• C25D5/611

  Smooth layers · CPC title

• C25D5/605

  Surface topography of the layers, e.g. rough, dendritic or nodular layers · CPC title

• C25D5/627

  Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance · CPC title

• C25D3/34

  of lead · CPC title