TEPZZ 

84Z_69A_T
(19)

(11) EP 2 840 169 A1

(12) EUROPEAN PATENT APPLICATION
published in accordance with Art. 153(4) EPC

(43) Date of publication: (51) Int Cl.:

25.02.2015 Bulletin 2015/09 C25D 3/56 (2006.01) C22C 9/06 (2006.01)
C22C 19/03 (2006.01) C25D 3/58 (2006.01)
(21) Application number: 13779037.4
(86) International application number:
(22) Date of filing: 19.04.2013 PCT/JP2013/061667

(87) International publication number:

WO 2013/157639 (24.10.2013 Gazette 2013/43)

(84) Designated Contracting States: (72) Inventors:

AL AT BE BG CH CY CZ DE DK EE ES FI FR GB • INOUE, Manabu
GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Nagareyama-shi
PL PT RO RS SE SI SK SM TR Chiba 270-0121 (JP)
Designated Extension States: • YUASA, Satoshi
BA ME Nagareyama-shi
Chiba 270-0121 (JP)
(30) Priority: 19.04.2012 JP 2012095956 • SAKURAI, Hitoshi
Nagareyama-shi
(71) Applicant: Dipsol Chemicals Co., Ltd. Chiba 270-0121 (JP)
Tokyo 104-0028 (JP)
(74) Representative: Carpmaels & Ransford LLP
One Southampton Row
London WC1B 5HA (GB)

(54) COPPER-NICKEL ALLOY ELECTROPLATING BATH AND PLATING METHOD

(57) The present invention provides a copper-nickel these compounds, (e) a compound that is selected from
alloy electroplating bath which is characterized by con- the group consisting of sulfonic acid compounds, sulfim-
taining (a) a copper salt and a nickel salt, (b) a metal ide compounds, sulfamic acid compounds, sulfone
complexing agent, (c) a plurality of conductivity-imparting amides and salts of these compounds, and (f) a reaction
salts that are different from each other, (d) a compound product of a glycidyl ether and a polyhydric alcohol. This
that is selected from the group consisting of disulfide copper-nickel alloy electroplating bath is also character-
compounds, sulfur-containing amino acids and salts of ized by having a pH of 3-8.
EP 2 840 169 A1

Printed by Jouve, 75001 PARIS (FR)

 EP 2 840 169 A1

Description

Technical Field

5 [0001] The present invention relates to a copper-nickel alloy electroplating bath and a plating method. More specifically,
the present invention relates to a plating bath having excellent bath stability and a plating method which are capable of
obtaining a plated coating having a uniform composition of copper and nickel at any alloy ratio on a workpiece.

Background Art
10
[0002] Generally, copper-nickel alloys exhibit excellent natures of corrosion resistance, ductility, processability, and
high temperature properties by changing the ratio of copper and nickel, and also have characteristic natures such as
electrical resistivity, heat resistivity coefficient, thermal electromotive force, and thermal expansion coefficient. Thus,
studies have been conducted from the past to obtain such properties of copper-nickel alloys by electroplating. Numerous
15 baths have been studied such as a cyan bath, a citric acid bath, an acetic acid bath, a tartaric acid bath, a thiosulfuric
acid bath, an ammonia bath, and a pyrophosphoric acid bath, as the copper-nickel alloy plating bath that has been
conventionally attempted; however, none has been put into practical use. The reasons that no copper-nickel alloy plating
has been practically used include: (i) copper and nickel differ from each other in deposition potential by approximately
0.6 V, so that copper preferentially deposits; (ii) such a plating bath is unstable, so that an insoluble compound such as
20 metal hydroxide is formed; and so forth. Examples of copper-nickel alloy plating baths reported so far include the
followings.

(1) JP-A Sho 49-90234:

25 An electroplating bath containing copper, nickel, and boric acid at a pH of approximately 1, with which a plating
having a copper content of 25% is obtained.

(2) JP-A Sho 54-026962:

30 A bath containing a mixture of copper, nickel, citric acid, and ammonia water, with which a plating having any
alloy composition is obtained.

(3) JP-A Sho 58-133391:

35 A pyrophosphoric acid-based bath containing pyrophosphosphate whose concentration is defined, to which

primary and secondary additives are added to thereby obtain a bright plating.

(4) JP-A Hei 2-285091:

40 A bath containing nickel sulfate, nickel chloride, copper sulfate, sodium citrate, boric acid, and further sodium
borate added thereto, and having a pH of 4 to 7.

(5) JP-A Hei 5-98488:

45 A weak acid bath containing copper, nickel, sodium tetraborate, saccharin, and a carboxylic acid such as malic
acid, gluconic acid, and salicylic acid, with which a plating having a copper content of 20 to 60% and a cupronickel
color is obtained.

(6) JP-A Hei 6-173075:

50
A weak acid bath containing copper, nickel, an aminocarboxylic acid, and sodium heptonate, with which a plating
having a copper content of 18 to 64% and a cupronickel color is obtained.

Summary of Invention
55
[0003] The target alloy coatings are obtained using the above-described copper-nickel alloy plating baths. Neverthe-
less, there are some problems to be solved in order to stably obtain coatings having a uniform composition at an industrial
level.

2
 EP 2 840 169 A1

(1) JP-A Sho 49-90234:

The bath is a low pH bath (pH: approximately 1) containing no complexing agent, and the composition is obtained
by adding a small amount of copper to a large amount of nickel. The preferential deposition of copper cannot
5 be suppressed. Accordingly, there is a problem that the composition of a coating is strongly influenced by current
density.

(2) JP-A Sho 54-026962:

10 Since the bath contains ammonia, the pH greatly varies. The bath is such that if the pH is low (in an acidic
range), copper is likely to deposit, and if the pH is high (in an alkaline range), nickel is likely to deposit. The bath
has a problem that as the bath pH varies, the composition of a plated coating varies. Moreover, there is another
problem that since the effect of suppressing preferential copper deposition is weak, the composition of a plated
coating is poor in uniformity due to the influence of cathode current density.
15
(3) JP-A Sho 58-133391:

The pyrophosphoric acid bath requires pyrophosphosphate in a molar amount twice or more than the metal
concentration in the bath. The metal nickel concentration in the bath is restricted to 30 g/L or less. Accordingly,
20 there are problems that the deposition efficiency is low and that the range where the brightness is obtained is
narrow.

(4) JP-A Hei 2-285091:

25 Since the nickel concentration and the copper concentration in the bath are high, the action of suppressing
preferential copper deposition is weak. There is a problem that if the cathode current density is in a low range,
copper preferentially deposits. In addition, since the nickel concentration and the sodium citrate concentration
in the bath are high, this brings about a problem that insoluble nickel citrate precipitates over time.

30 (5) JP-A Hei 5-98488:

The stability over time of the bath is improved by incorporating a carboxylic acid such as malic acid, gluconic
acid, and salicylic acid, and the appearance of the plating is improved by adding saccharin. Nevertheless, the
bath has problems that the effect of suppressing preferential copper deposition is insufficient and that stirring
35 or the like causes preferential copper deposition.

(6) JP-A Hei 6-173075:

The weak acid bath contains copper, nickel, an aminocarboxylic acid, and sodium heptonate, with which a
40 plating having a copper content of 18 to 64% and a cupronickel color is obtained. Nonetheless, there is a problem
that as the copper and nickel concentrations in the bath vary, the composition of a plated coating also greatly
varies. This makes it hard to obtain a coating having a stable composition. Further, there are problems that
stirring lowers the action of suppressing preferential copper deposition and that the composition of the deposited
coating is strongly influenced by cathode current density.
45
[0004] An object of the present invention is to provide a copper-nickel alloy plating bath and a plating method which
solve the above-described problems of the conventional plating baths, and which are capable of stably obtaining a plating
having any desired composition without precipitation and the like, the composition of the plated coating being less likely
to be influenced by cathode current density.
50 [0005] The present invention provides a copper-nickel alloy electroplating bath comprising: (a) a copper salt and a
nickel salt; (b) a metal complexing agent; (c) a plurality of conductivity-providing salts different from each other; (d) a
compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and salts thereof;
(e) a compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid
compounds, sulfonamides, and salts thereof; and (f) a reaction product between a glycidyl ether and a polyvalent alcohol,
55 wherein the bath has a pH of 3 to 8.
[0006] Moreover, the present invention provides a method for electroplating a substrate with a copper-nickel alloy, the
substrate being selected from the group consisting of metal substrates made of copper, iron, nickel, silver, gold, and
alloys thereof, and glass, ceramic, and plastic substrates whose surfaces are modified with any of the metals and alloys,

3
 EP 2 840 169 A1

the method comprising electroplating by using the copper-nickel alloy electroplating bath according to any one of claims
1 to 7.
[0007] The present invention makes it possible to provide a copper-nickel alloy plating bath and a plating method
which are capable of stably obtaining a plating having any composition without precipitation and the like, the composition
5 of the plated coating being less likely to be influenced by cathode current density.

Description of Embodiments

[0008] A copper-nickel alloy electroplating bath of the present invention contains (a) a copper salt and a nickel salt,
10 (b) a metal complexing agent, (c) multiple conductivity-providing salts different from each other, (d) a compound selected
from the group consisting of disulfide compounds, sulfur-containing amino acids, and salts thereof, (e) a compound
selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sul-
fonamides, and salts thereof, and (f) a reaction product between a glycidyl ether and a polyvalent alcohol.

15 (a) Copper Salt and Nickel Salt

[0009] The copper salt includes copper sulfate, copper(II) halides, copper sulfamate, copper methanesulfonate, cop-
per(II) acetate, basic copper carbonate, and the like, but is not limited thereto. These copper salts may be used alone,
or may be used as a mixture of two or more thereof. The nickel salt includes nickel sulfate, nickel halides, basic nickel
20 carbonate, nickel sulfamate, nickel acetate, nickel methanesulfonate, and the like, but is not limited thereto. These nickel
salts may be used alone, or may be used as a mixture of two or more thereof. The concentration of the copper salt and
the nickel salt in the plating bath has to be selected in various manners in accordance with the composition of a plated
coating to be obtained, but is 0.5 to 40 g/L, preferably 2 to 30 g/L for copper ion, and 0.25 to 80 g/L, preferably 0.5 to
50 g/L for nickel ion.
25
(b) Metal Complexing Agent

[0010] The metal complexing agent stabilizes the metals copper and nickel. The metal complexing agent includes
monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, oxycarboxylic acids, keto-carboxylic acids, amino acids,
30 aminocarboxylic acids, salts thereof, and the like, but is not limited thereto. Specifically, the metal complexing agent
includes malonic acid, maleic acid, succinic acid, tricarballylic acid, citric acid, tartaric acid, malic acid, gluconic acid, 2-
sulfoethylimino-N,N-diacetic acid, iminodiacetic acid, nitrilotriacetic acid, EDTA, triethylenediaminetetraacetic acid, hy-
droxyethyliminodiacetic acid, glutamic acid, aspartic acid, β-alanine-N,N-diacetic acid, and the like. Among these, pref-
erable are malonic acid, citric acid, malic acid, gluconic acid, EDTA, nitrilotriacetic acid, and glutamic acid. Moreover,
35 salts of these carboxylic acids include magnesium salts, sodium salts, potassium salts, ammonium salts, and the like,
but are not limited thereto. These metal complexing agents may be used alone, or may be used as a mixture of two or
more thereof. The concentration of the metal complexing agent in the plating bath is preferably 0.6 to 2 times, more
preferably 0.7 to 1.5 times, the metal ion concentration (molar concentration) in the bath.

40 (c) Conductivity-Providing Salts

[0011] The conductivity-providing salts provide the copper-nickel alloy electroplating bath with electrical conductivity.
In the present invention, the conductivity-providing salts used have to be multiple conductivity-providing salts and different
from each other. The conductivity-providing salts preferably include an inorganic halide salt and a salt selected from the
45 group consisting of inorganic sulfates and lower alkanesulfonates.
[0012] The inorganic halide salt includes chloride salts, bromide salts, iodide salts of each of magnesium, sodium,
potassium, and ammonium, and the like, but is not limited thereto. These inorganic halide salts may be used alone, or
may be used as a mixture of two or more thereof. The concentration of the inorganic halide salt in the plating bath is
preferably 0.1 to 2.0 mol/L, more preferably 0.2 to 1.0 mol/L.
50 [0013] The inorganic sulfates include magnesium sulfate, sodium sulfate, potassium sulfate, ammonium sulfate, and
the like, but are not limited thereto. These inorganic sulfates may be used alone, or may be used as a mixture of two or
more thereof.
[0014] The lower alkanesulfonates include magnesium salts, sodium salts, potassium salts, ammonium salts, and the
like, and more specifically includes magnesium, sodium, potassium, and ammonium salts of methanesulfonic acid or 2-
55 hydroxypropanesulfonic acid, and the like, but are not limited thereto. These sulfonates may be used alone, or may be
used as a mixture of two or more thereof.
[0015] The concentration of the sulfate and/or the sulfonate in the plating bath is preferably 0.25 to 1.5 mol/L, more
preferably 0.5 to 1.25 mol/L.

4
 EP 2 840 169 A1

(d) Compound Selected from Group Consisting of Disulfide Compounds, Sulfur-Containing Amino Acids, and Salts
Thereof

[0016] The compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and
5 salts thereof includes, but is not limited to, disulfide compounds represented by a general formula (I), and the like:

A-R1-S-S-R2-A (I)

where R1 and R2 each represent a hydrocarbon group, and A represents a SO3Na group, a SO3 H group, an OH group,
10 a NH2 group, or a NO2 group.
[0017] The hydrocarbon group is preferably an alkylene group, more preferably an alkylene group having 1 to 6 carbon
atoms. Specific examples of the disulfide compounds include bis-sodium sulfoethyl disulfide, bis-sodium sulfopropyl
disulfide, bis-sodium sulfopentyl disulfide, bis-sodium sulfohexyl disulfide, bis-sulfoethyl disulfide, bis-sulfopropyl di-
sulfide, bis-sulfopentyl disulfide, bis-aminoethyl disulfide, bis-aminopropyl disulfide, bis-aminobutyl disulfide, bis-ami-
15 nopentyl disulfide, bis-hydroxyethyl disulfide, bis-hydroxypropyl disulfide, bis-hydroxybutyl disulfide, bis-hydroxypentyl
disulfide, bis-nitroethyl disulfide, bis-nitropropyl disulfide, bis-nitrobutyl disulfide, sodium sulfoethyl propyl disulfide, sul-
fobutyl propyl disulfide, and the like, but are not limited thereto. Among these disulfide compounds, bis-sodium sulfopropyl
disulfide, bis-sodium sulfobutyl disulfide, bis-aminopropyl disulfide are preferable.
[0018] The sulfur-containing amino acids include, but are not limited to, sulfur-containing amino acids represented by
20 a general formula (II), and the like:

R-S-(CH2)nCHNHCOOH (II)

where R represents a hydrocarbon group, -H, or -(CH2)nCHNHCOOH, and each n is independently 1 to 50.
25 [0019] The hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms.
Specific examples of the sulfur-containing amino acids include methionine, cystine, cysteine, ethionine, cystine disul-
foxide, cystathionine, and the like, but are not limited thereto. In addition, the salts thereof include sulfates, halide salts,
methanesulfonates, sulfamates, acetates, and the like, but are not limited thereto.
[0020] These disulfide compounds, sulfur-containing amino acids, and salts thereof may be used alone, or may be
30 used as a mixture of two or more thereof. The concentration of the compound selected from the group consisting of
disulfide compounds, sulfur-containing amino acids, and salts thereof in the plating bath is preferably 0.02 to 10 g/L,
more preferably 0.1 to 5 g/L. (e) Compound Selected from Group Consisting of Sulfonic Acid Compounds, Sulfimide
Compounds, Sulfamic Acid Compounds, Sulfonamides, and Salts Thereof
[0021] The compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic
35 acid compounds, sulfonamides, and salts thereof makes the copper-nickel alloy-electroplated coating dense.
[0022] The sulfonic acid compounds and salts thereof include aromatic sulfonic acids, alkene sulfonic acids, alkyne
sulfonic acids, salts thereof, and the like, but are not limited thereto. Specifically, the sulfonic acid compounds and salts
thereof include sodium 1,5-naphthalenedisulfonate, sodium 1,3,6-naphthalenetrisulfonate, sodium 2-propene-1-sul-
fonate, and the like, but are not limited thereto.
40 [0023] The sulfimide compounds and salts thereof include benzoic sulfimide (saccharin), salts thereof, and the like,
but are not limited thereto. Specifically, the sulfimide compounds and salts thereof include sodium saccharin, and the
like, but are not limited thereto.
[0024] The sulfamic acid compounds and salts thereof include acesulfame potassium, sodium N-cyclohexylsulfamate,
and the like, but are not limited thereto.
45 [0025] The sulfonamides and salts thereof include para-toluenesulfonamides, and the like, but are not limited thereto.
[0026] These sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sulfonamides, and salts
thereof may be used alone, or may be used as a mixture of two or more thereof. The concentration of the compound
selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic acid compounds, sul-
fonamides, and salts thereof in the plating bath is preferably 0.2 to 5 g/L, more preferably 0.4 to 4 g/L.
50
(f) Reaction Product between Glycidyl Ether and Polyvalent Alcohol

[0027] The reaction product between a glycidyl ether and a polyvalent alcohol makes the copper-nickel alloy-electro-
plated coating dense.
55 [0028] In the reaction product between a glycidyl ether and a polyvalent alcohol, the glycidyl ether serving as the
reaction raw material includes glycidyl ethers containing two or more epoxy groups in the molecules, glycidyl ethers
containing one or more hydroxyl groups and one or more epoxy groups in the molecules, and the like, but is not limited
thereto. Specifically, the glycidyl ether includes glycidol, glycerol polyglycidyl ether, ethylene glycol diglycidyl ether,

5
 EP 2 840 169 A1

polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, and the like.
[0029] The polyvalent alcohol includes ethylene glycol, propylene glycol, glycerin, polyglycerin, and the like, but is not
limited thereto.
[0030] The reaction product between the glycidyl ether and the polyvalent alcohol is preferably a water soluble polymer
5 obtained by a condensation reaction between an epoxy group of the glycidyl ether and a hydroxyl group of the polyvalent
alcohol.
[0031] The reaction products between these glycidyl ethers and the polyvalent alcohol may be used alone, or may be
used as a mixture of two or more thereof. The concentration of the reaction product between the glycidyl ether and the
polyvalent alcohol in the plating bath is preferably 0.05 to 5 g/L, more preferably 0.1 to 2 g/L.
10 [0032] The copper-nickel alloy electroplating bath of the present invention has to be adjusted to have a pH of 3 to 8,
preferably pH of 4 to 7. The pH of the plating bath can be adjusted with sulfuric acid, hydrochloric acid, hydrobromic
acid, methanesulfonic acid, sodium hydroxide, potassium hydroxide, ammonia water, ethylenediamine, diethylenetri-
amine, triethylenetetramine, or the like.
[0033] Next, a plating method using the plating bath of the present invention will be described. A workpiece which can
15 be electroplated by using the plating bath of the present invention, includes copper, iron, nickel, silver, alloys thereof,
and the like. In addition, a glass substrate, a ceramic substrate, and a plastic substrate whose surfaces are modified
with any of the metals and alloys, and the like are also effective.
[0034] When electroplating is conducted, it is possible to use, as an anode, an insoluble anode such as carbon,
platinum, or platinum-plated titanium can be used. Alternatively, a copper-nickel alloy anode, an anode using copper
20 and nickel in combination, and the like can also be used. Nevertheless, in this case, it is necessary to carefully control
the metal concentration in the bath by examining the cathode deposition efficiency and the anode dissolution efficiency.
[0035] The bath temperature is generally 15 to 60°C, preferably 20 to 50°C. The cathode current density is generally
0.01 to 5 A/dm 2, preferably 0. 05 to 4.0 A/dm2. The plating time depends on a demanded thickness of a plating, but is
generally 1 to 180 minutes, preferably 15 to 120 minutes.
25 The liquid in the bath may be stirred by air, liquid flow, or mechanically with a cathode rocker or the like. The thickness
can be set in a wide range, but is generally 0.5 to 50 mm, preferably 3 to 20 mm. While plating is being conducted, the
pH of the plating bath has to be maintained at 3 to 8 using the aforementioned pH adjuster.
[0036] The use of the plating bath of the present invention enables the metal coating to be deposited to have a
copper/nickel composition ratio of 5/95 to 95/5.
30 [0037] When plating is conducted, the workpiece is subjected to a pre-treatment according to a conventional method
and then the plating step.
In the pre-treatment step, at least one operation is performed: soak cleaning, electrolytic washing of a cathode or an
anode, washing with an acid, and activation. Water washing is performed between every successive two operations.
After the plating, it is only necessary that the resulting coating should be washed with water or hot water, followed by
35 drying. Moreover, after the copper-nickel alloy plating is conducted, an anti-oxidation treatment, tin plating, tin alloy
plating, or the like may also be carried out. The plating bath of the present invention can be used over a long time period
without replacing the liquid, by maintaining each bath component at a constant level by using an appropriate replenishing
agent.
[0038] Next, the present invention will be described based on Examples. However, the present invention is not limited
40 to these. The composition of the plating bath and the plating conditions may be arbitrarily altered according to such gists
that it is possible to obtain a plated coating having a uniform composition of copper and nickel at any alloy ratio on the
above-described target workpiece, and that a copper-nickel alloy plating having excellent bath stability is obtained.

[Examples]
45
(Examples 1 to 7 and Comparative Examples 1 to 7)

[0039] For the evaluation of plating in Examples, the test piece used was an iron plate (SPCC) of 0.53653100 mm
whose one surface was sealed with a Teflon (registered trademark) tape. The iron plate as the test piece was degreased
50 with 5 w/v % Dasshi-39 [manufactured by DIPSOL CHEMICALS Co., Ltd.] and then washed with an acid of 10.5 w/w
% hydrochloric acid, followed by electrolytic washing with 5 w/w % NC-20 [manufactured by DIPSOL CHEMICALS Co.,
Ltd.] and 7 w/v % sodium hydroxide solution. After the electrolytic washing, the iron plate was activated with 3.5%
hydrochloric acid. Water washing was sufficiently performed between every successive two operations.
[0040] Next, each plating liquid shown in Table-1 was introduced into a plating tank made of an acrylic resin. A platinum
55 plate was used as an anode, and the iron plate activated above as the test piece was connected to a cathode. The
plating was conducted under conditions in Table-2. The thickness and the alloy composition of the obtained plating were
determined with an X-ray fluorescence spectrometer. Table-3 shows the result.
[0041] In Comparative Examples also, plating was conducted in the same manner as in Examples under conditions

6
 EP 2 840 169 A1

shown in Table-5 using plating liquids having compositions shown in Table-4. The thickness and the alloy composition
of the obtained plating were determined with an X-ray fluorescence spectrometer. Table-6 shows the result.

Table-1 Compositions of plating baths of Examples

5
Example
concentrations of components
1 2 3 4 5 6 7
(a) Cu2+ (g/L) 3 25 9 7.5 7.5 7.5 5

10 (a) Ni2+ (g/L) 50 40 20 15 7.5 7.5 1

metal concentration (mol/L) (Cu2+ + Ni2+) 0.9 1.1 0.5 0.37 0.25 0.25 0.1
(b) malonic acid (mol/L) - - 0.6 0.55 - - 0.07
(b) diammonium citrate (mol/L) 0.8 - - - 0.2 - -
15
(b) nitrilotriacetic acid (mol/L) - 1.1 - - - 0.2 -
metal complexing agent/metal molar concentration ratio
0.9 1.0 1.2 1.5 0.8 0.8 0.7
(fold)
(c) sodium chloride (mol/L) - 0.75 - 0.5 - 0.6 0.5
20
(c) potassium bromide (mol/L) 1 - 0.2 - 0.25 - -
(c) magnesium sulfate (mol/L) - 0.5 - 1 - 0.9 0.8
(c) ammonium methanesulfonate (mol/L) 1 - 1.25 - 0.75 - -
25 (d) bis-sodium sulfopropyl disulfide (g/L) - 2 - 1 - 2.5 0.1
(d) cysteine methanesulfonate (g/L) 5 - 0.5 - 0.2 - -
(e) sodium 1,5-naphthalenedisulfonate (g/L) - 0.5 4 - 0.4 - 0.6
(e) sodium saccharin (g/L) 2 0.5 - 1 - 1.5 -
30
(f) reaction product of ethylene glycol diglycidyl ether with
- 1 - 0.25 - 1 0.25
propylene glycol (g/L)
(f) reaction product of glycerol polyglycidyl ether with
2 - 1.5 - 0.1 - -
polyglycerin (g/L)
35
pH 4 5 5 5 8 7 6

[0042] Copper salt species: copper (II) methanesulfonate (Examples 1 and 5), copper(II) sulfate (Examples 2 and 4),
copper(II) sulfamate (Example 3), copper(II) acetate (Example 6), copper(II) chloride
40

(Example 7)

[0043] Nickel salt species: nickel methanesulfonate (Examples 1 and 5), nickel sulfate (Examples 2 and 4), nickel
sulfamate (Example 3), nickel acetate (Example 6), nickel chloride (Example 7) pH adjuster: methanesulfonic acid
45
(Example 1), sodium hydroxide (Examples 2, 4, 6, and 7), potassium hydroxide (Example 3), ammonia water (Example 5)

Table-2 Plating conditions of Examples

Example
50 Items 1 2 3 4 5 6 7
plating time (min.) cathode current density (A/dm2)
0.5 120
2 30
55
5 10
bath temperature (°C) 50 50 50 25 25 25 50

7
 EP 2 840 169 A1

(continued)

Example
Items 1 2 3 4 5 6 7
5
stirring with stirring & without stirring

Table-3 Results obtained in Examples

10
Items cathode Example
current
density 1 2 3 4 5 6 7
(A/dm2)
15 0.5 13 13 12 12 12 12 12
thickness (mm)
2 12 12 11 11 11 11 10
with stirring
5 9 9 8.5 8.5 8.5 8.5 8
coating 0.5 9 25 44 62 79 79 88
20 composition
2 10 22 42 60 80 80 91
(Cu %) without
stirring 5 11 20 40 60 81 81 92

coating 0.5 9 25 45 61 79 80 88
25 composition
2 10 22 42 61 80 80 91
(Cu %) with
stirring 5 8 20 40 58 82 81 92
appearance silver silver silver silver cupronickel cupronickel pale
0.5
with stirring white white white white color color cupronickel
30
color semi-
glossy glossy glossy glossy semi-glossy semi-glossy
glossy
pale
silver silver silver silver cupronickel cupronickel
cupronickel
2 white white white white color semi- color semi-
35 color semi-
glossy glossy glossy glossy glossy glossy
glossy
pale
silver silver silver silver cupronickel cupronickel
cupronickel
5 white white white white color semi- color semi-
color semi-
40 glossy glossy glossy glossy glossy glossy
glossy
stability of plating bath
formation of turbidity
precipitates after allowed to none none none none none none none
45 stand for 7 days at room
temperature

Table-4 Compositions of plating baths of Comparative Examples

50
concentrations of components Comparative Example
1 2 3 4 5 6 7
(a) Cu2+ (g/L) 3 25 9 7.5 7.5 7.5 5
55 (a) Ni2+ (g/L) 50 40 20 15 7.5 7.5 1
metal concentration (mol/L) (Cu2+ + Ni2+) 0.9 1.1 0.5 0.37 0.25 0.25 0.1

8
 EP 2 840 169 A1

(continued)

concentrations of components Comparative Example

1 2 3 4 5 6 7
5
(b) malonic acid (mol/L) - - 0.6 0.55 - - 0.07
(b) diammonium citrate (mol/L) 0.8 - - - 0.2 - -
(b) nitrilotriacetic acid (mol/L) - 1.1 - - - 0.2 -
10 metal complexing agent/metal molar concentration ratio
0.9 1.0 1.2 1.5 0.8 0.8 0.7
(fold)
(c) sodium chloride (mol/L) - 0.75 - 0.5 - - 0.5
(c) potassium bromide (mol/L) 1 - 0.2 - 0.25 - -
15
(c) magnesium sulfate (mol/L) - 0.5 - 1 - 0.9 -
(c) ammonium methanesulfonate (mol/L) 1 - 1.25 - 0.75 - -
(d) bis-sodium sulfopropyl disulfide (g/L) - 2 - 1 - 2.5 0.1

20 (d) cysteine methanesulfonate (g/L) - - - - - - -

(e) sodium 1,5-naphthalenedisulfonate (g/L) - 0.5 4 - 0.4 - 0.6
(e) sodium saccharin (g/L) - 0.5 - - - 1.5 -
(f) reaction product of ethylene glycol diglycidyl ether with
25
- - - 0.25 - 1 0.25
propylene glycol (g/L)
(f) reaction product of glycerol polyglycidyl ether with
- - 1.5 - - - -
polyglycerin (g/L)
pH 4 5 5 5 8 7 6
30

Copper salt species: copper(II) methanesulfonate (Comparative Examples 1 and 5), copper(II) sulfate (Comparative
Examples 2 and 4), copper(II) sulfamate (Comparative Example 3), copper(II) acetate (Comparative Example 6), cop-
per(II) chloride (Comparative Example 7)
Nickel salt species: nickel methanesulfonate (Comparative Examples 1 and 5), nickel sulfate (Comparative Examples
35
2 and 4), nickel sulfamate (Comparative Example 3), nickel acetate (Comparative Example 6), nickel chloride (Compar-
ative Example 7)
pH adjuster: methanesulfonic acid (Comparative Example 1), sodium hydroxide (Comparative Examples 2, 4, 6, and 7),
potassium hydroxide (Comparative Example 3), ammonia water (Comparative Example 5)

40
Table-5 Plating conditions of Comparative Examples
Comparative Example
Items 1 2 3 4 5 6 7
plating time (min.) cathode current density (A/dm2)
45
0.5 120
2 30
5 10
50
bath temperature (°C) 50 50 50 25 25 25 50
stirring with stirring & without stirring

55

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 5

55
50
45
40
35
30
25
20
15
10
Table-6 Results obtained in Comparative Examples
Items cathode current Comparative Example
density (A/dm 2) 1 2 3 4 5 6 7
0.5 13 13 12 12 12 12 12
thickness (mm) with stirring 2 12 12 11 11 11 11 10
5 9 9 8.5 8.5 8.5 8.5 8
0.5 100 95 55 75 88 69 83
coating composition (Cu %)
2 0 22 41 60 83 77 91
without stirring
5 0 18 38 55 79 81 95
0.5 100 100 80 90 93 65 80
coating composition (Cu %)
2 0 22 42 63 83 74 89
with stirring
5 0 18 40 56 79 81 95
appearance with stirring copper red copper red copper red
cupronickel copper red copper red cupronickel
0.5 crude crude crude
color not glossy crude deposit crude deposit color not glossy
deposit deposit deposit

10
cupronickel
silver white silver white silver white silver white cupronickel copper red not
2 color semi-
glossy glossy glossy glossy color not glossy glossy
EP 2 840 169 A1

glossy
silver white silver white silver white silver white cupronickel cupronickel copper red not
5
glossy glossy glossy glossy color not glossy color not glossy glossy
stability of plating bath formation of turbidity
precipitates after allowed to stand for 7 days at none none none none none none none
room temperature
 EP 2 840 169 A1

Claims

1. A copper-nickel alloy electroplating bath comprising:

5 (a) a copper salt and a nickel salt;

(b) a metal complexing agent;
(c) a plurality of conductivity-providing salts different from each other;
(d) a compound selected from the group consisting of disulfide compounds, sulfur-containing amino acids, and
salts thereof;
10 (e) a compound selected from the group consisting of sulfonic acid compounds, sulfimide compounds, sulfamic
acid compounds, sulfonamides, and salts thereof; and
(f) a reaction product between a glycidyl ether and a polyvalent alcohol, wherein

the bath has a pH of 3 to 8.

15
2. The copper-nickel alloy electroplating bath according to claim 1, wherein the conductivity-providing salts (c) include
an inorganic halide salt and a salt selected from the group consisting of inorganic sulfates and lower alkanesulfonates.

3. The copper-nickel alloy electroplating bath according to claim 2, wherein the inorganic halide salt is selected from
20 the group consisting of chloride salts, bromide salts, and iodide salts of each of magnesium, sodium, potassium,
and ammonium.

4. The copper-nickel alloy electroplating bath according to claim 2 or 3, wherein the inorganic sulfates are selected
from the group consisting of magnesium sulfate, sodium sulfate, potassium sulfate, and ammonium sulfate.
25
5. The copper-nickel alloy electroplating bath according to any one of claims 2 to 4, wherein the lower alkanesulfonates
are selected from the group consisting of magnesium salts, sodium salts, potassium salts, and ammonium salts.

6. The copper-nickel alloy electroplating bath according to any one of claims 1 to 5, wherein the compound (d) includes
30 a disulfide compound represented by general formula (I):

A-R1-S-S-R2-A (I)

wherein R1 and R2 each represent a hydrocarbon group, and A represents a SO3Na group, a SO3H group, an OH
35 group, a NH2 group, or a NO2 group.

7. The copper-nickel alloy electroplating bath according to any one of claims 1 to 6, wherein the compound (d) includes
a sulfur-containing amino acid represented by general formula (II) or a salt thereof:

40 R-S-(CH2)nCHNHCOOH (II)

wherein R represents a hydrocarbon group, -H, or -(CH2)nCHNHCOOH, and each n is independently 1 to 50.

8. The copper-nickel alloy electroplating bath according to any one of claims 1 to 7, wherein the compound (e) includes
45 a sulfonic acid compound selected from the group consisting of aromatic sulfonic acids, alkene sulfonic acids, and
alkyne sulfonic acids, or a salt thereof.

9. The copper-nickel alloy electroplating bath according to any one of claims 1 to 8, wherein the compound (e) includes
benzoic sulfimide (saccharin) or a salt thereof.
50
10. The copper-nickel alloy electroplating bath according to any one of claims 1 to 9, wherein the reaction product (f)
between a glycidyl ether and a polyvalent alcohol is a water soluble polymer obtained by a condensation reaction
between an epoxy group of the glycidyl ether and a hydroxyl group of the polyvalent alcohol.

55 11. The copper-nickel alloy electroplating bath according to any one of claims 1 to 10, wherein the metal complexing
agent (b) is selected from the group consisting of monocarboxylic acids, dicarboxylic acids, polycarboxylic acids,
oxycarboxylic acids, keto-carboxylic acids, amino acids, aminocarboxylic acids, and salts thereof.

11
 EP 2 840 169 A1

12. The copper-nickel alloy electroplating bath according to any one of claims 1 to 11, wherein a metal coating to be
deposited has a copper/nickel composition ratio of 5/95 to 95/5.

13. A method for electroplating a substrate with a copper-nickel alloy, the substrate being selected from the group
5 consisting of metal substrates made of copper, iron, nickel, silver, gold, and alloys thereof, and a glass substrate,
a ceramic substrate, and a plastic substrate whose surfaces are modified with any of the metals and alloys,
the method comprising
electroplating by using the copper-nickel alloy electroplating bath according to any one of claims 1 to 12.

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 EP 2 840 169 A1

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 EP 2 840 169 A1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• JP SHO4990234 A [0002] [0003] • JP HEI2285091 A [0002] [0003]

• JP SHO54026962 A [0002] [0003] • JP HEI598488 A [0002] [0003]
• JP SHO58133391 A [0002] [0003] • JP HEI6173075 A [0002] [0003]

14