EP1396559A1 - Palladium plating solution - Google Patents
Palladium plating solution Download PDFInfo
- Publication number
- EP1396559A1 EP1396559A1 EP01941060A EP01941060A EP1396559A1 EP 1396559 A1 EP1396559 A1 EP 1396559A1 EP 01941060 A EP01941060 A EP 01941060A EP 01941060 A EP01941060 A EP 01941060A EP 1396559 A1 EP1396559 A1 EP 1396559A1
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- EP
- European Patent Office
- Prior art keywords
- palladium
- acid
- plating solution
- ammonium
- palladium plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
Definitions
- the present invention relates to a palladium plating solution, and particularly, to a palladium plating solution suitable to provide a palladium-plated ornamental material in which a nickel allergy problem associated with an ornamental material has been solved.
- Palladium plating solutions have been studied in a wider range from old.
- a deposit resulting from the plating has excellent physical properties, e.g., is excellent in light resistance, corrosion resistance, discoloration resistance, wear resistance and the like. Therefore, palladium plating solutions have been used in applications in a wider field such as an ornamental material, an electric contact of an electronic part, a connector, a circuit board and the like.
- a personal ornament such as a watch case, a watch band, an eyeglass frame, a necklace, an ear-ring and a finger ring to a white plating by a conventional surface-treating technique
- a palladium plating, a palladium-nickel alloy plating, a palladium-cobalt alloy plating, a rhodium plating, a platinum plating, a silver plating and the like are carried out.
- the above plating processes suffer the following disadvantages:
- the rhodium plating is not of practical use, because it is very expensive.
- a plated material is liable to be discolored due to a resulting sulfide.
- a nickel allergy may be produced in some cases and for this reason, the use of the palladium-nickel alloy plating is prohibited in Europe.
- a resulting film has a high stress and for this reason, if a film is formed at a large thickness, the film is liable to be cracked.
- any of sulfite, nitrous acid and sodium and potassium salts thereof is incorporated in a plating solution (see Japanese Patent Publication No.1-47557).
- cerium is incorporated in a plating solution (see Japanese Patent Application Laid-open No.2-43393).
- a palladium plating solution capable of forming a high-purity stable and thick deposit is required as a white metal plating solution capable of preventing the occurrence of the nickel allergy.
- the present inventors has made zealous repeated studies to provide a palladium plating solution which can be practically used even in an industrial scale and which is capable of forming a high-purity palladium deposit, with the above circumstance in view, and as a result, they have found that a palladium plating solution produced by incorporating a soluble palladium salt, pyridine carboxylic acid and/or the soluble trace metal salt thereof, an amide derivative of pyridine carboxylic acid and an anionic surfactant or an ampholytic surfactant exhibits a moderate depositing speed and is excellent in stability, and produces a high-purity palladium deposit film, which has a thickness equal to or larger than 5 ⁇ m, which is excellent in specular gloss and in which cracks are little produced.
- the present invention has been accomplished.
- the present invention provides
- the soluble palladium salt used in the present invention are palladium chloride, dichlorodiamine palladium, dichlorotetraamine palladium and the like. These salts may be used alone or in combination of two or more.
- the concentration of the soluble palladium salt in the palladium plating solution is preferable to be in a range of 1.0 to 40.0 g/l in terms of palladium. If the concentration is equal to or smaller than 1.0 g/l, a film-depositing speed is lower and hence, such concentration is not preferred. If the concentration is equal to or larger than 40.0 g/l, the forming speed cannot be increased and hence, such concentration is not of practical use.
- pyridine carboxylic acid examples include nicotinic acid, picolinic acid, iso- nicotinic acid, 2, 3-quinolinic acid, 2,4-lutidinic acid and 2,6-dipicolinic acid. These pyridine carboxylic acids may be used alone or in combination of two or more.
- the concentration of the pyridine carboxylic acid in the palladium plating solution is in a range of 0.01 to 20.0 g/l, preferably in a range of 1.0 to 10.0 g/l. If the concentration is equal to or smaller than 0.01 g/l, a gloss-enhancing effect is not provided. If the concentration is equal to or larger than 20.0 g/l, the gloss cannot be enhanced and hence, such concentration is not of practical use.
- the soluble metal salt is used in combination with the pyridine carboxylic acid or in place of the pyridine carboxylic acid.
- the soluble metal salt may be, for example, any of soluble iron, thallium, selenium and tellurium salts.
- Particular examples of the soluble metal salt are ferric or ferrous sulfate, ferrous ammonium sulfate, zinc sulfate, thallium sulfate, thallium acetate, selenic acid, selenious acid, sodium selenite, potassium selenite and the like.
- the soluble metal salts may be used alone or in combination of two or more.
- the concentration of the soluble metal salt is in a range of 0.002 to 1.0 g/l, preferably, in a range of 0.005 to 0.7 g/l in terms of metal. If the concentration of the soluble metal salt is equal to or smaller than 0.002 g/l, an effect of reducing the internal stress in the palladium deposit is not provided. On the other hand, if the concentration is equal to or larger than 1. 0 g/l, the internal stress in the palladium deposit cannot be increased, and hence, such concentration is not of practical use.
- amide derivative of the pyridine carboxylic acid examples include nicotinamide, picolinamide, iso-nicotinic acid amide, nicotinic acid amide and the like. These amide derivatives of the pyridine carboxylic acids may be used alone or in combination of two or more.
- concentration of the amide derivative of the pyridine carboxylic acid in the palladium plating solution is in a range of 0.002 to 20.0 g/l, preferably, in a range of 0.005 to 10.0 g/l.
- concentration of the amide derivative is equal to or smaller than 0.002 g/l, a gloss-enhancing effect is not provided, and even if the concentration of the amide derivative exceeds 20.0 g/l, the gloss cannot be enhanced and hence, concentration exceeding 20.0 g/l is not of practical use.
- aldehydebenzoic acid derivative examples are p-phthalaldehyde, o-phthalaldehyde, o-phthalaldehydic acid, p-phthalaldehydic acid, m-phthalaldehyde, iso-phthalaldehydic acid and aldehyde ammonium.
- the aldehydobenzoic acid derivatives may be used alone or in combination of two or more.
- the concentration of the aldehydebenzoic acid derivative in the palladium plating solution is in a range of 0. 002 to 20. 0 g/l, preferably, in a range of 0.005 to 10.0 g/l. If the concentration of the aldehydebenzoic acid derivative is equal to or smaller than 0.002 g/l, a gloss-enhancing effect is not provided. Even if the concentration of the aldehydebenzoic acid derivative exceeds 20.0 g/l, the gloss cannot be enhanced and hence, the concentration exceeding 20.0 g/l is not of practical use.
- the anionic surfactant or the ampholytic surfactant used in the present invention is used to prevent the pitting, and most effective for an ornament material of a complicated shape.
- Particular examples of the anionic surfactant or the ampholytic surfactant are dodecylamine acetate, cetylpyridium bromide, di-2-ethylhexyl sodium sulfosuccinate, sorbitan monopalmitate, polyoxyethylene stearate, sorbitan monostearate, dimethylalkyl betaine and dodecyltrimethyl ammonium chloride, polyoxyethylene sorbitan monopalmitate.
- the anionic surfactants or the ampholytic surfactants may be used alone or in combination of two or more.
- the concentration of the anionic surfactant or the ampholytic surfactant in the palladium plating solution is in a range of 0.001 to 1.2 g/l.
- the concentration of the conductive salt in the plating solution is in a range of 15.0 to 300. 0 g/l. If the concentration of the conductive salt is equal to or smaller than 15.0 g/l, the conductivity of the plating solution is poor. If the concentration of the conductive salt is equal to or larger than 300.0 g/l, the specific gravity of the plating solution is increased, and a tarnishing, a fogging, a scorching or the like is produced and hence, the concentration equal to or larger than 300.0 g/l is not preferred.
- the plating solution according to the present invention can be used in a plating treatment at a temperature in a range of 30 to 55°C. Particularly, when the temperature of the plating solution is in a range of 40 to 55°C, a smooth, glossy good plated film can be formed. As the temperature of the plating solution is higher, the film-depositing speed tends to be higher. Any film-depositing speed can be provided by setting the temperature of the plating solution at an appropriate value in the above-described range. Further, in the plating solution according to the present invention, the film-depositing speed depends on the concentration of palladium in addition to the temperature of the plating solution. Therefore, the film-depositing speed can be also regulated by setting the concentration of palladium at an appropriate value and hence, it is easy to control the thickness of the plated film.
- the plating solution was regulated to pH of 8.5 by ammonia water, and a previously nickel-plated brass plate having a size of 25 x 35mm was immersed in the plating solution at a bath temperature of 50°C and at a current density of 1.0 A/dm 2 for 30 minutes. As a result, a glossy palladium-plated film having an average thickness of 7 ⁇ m was produced. The palladium-plated film was subjected to an ammonia exposure test (for 12 hours at room temperature) and as a result, the generation of cracks was not observed.
- a palladium plating solution having a composition made by removing the ferrous ammonium sulfate and the nicotinamide from the palladium plating solution used in Example 3 and adding 1.0 g/l of EDTA in place of these substances was used to carry out a plating treatment under the same conditions as in Example 3.
- a produced palladium plated film was subj ected to an ammonia exposure test and as a result, cracks were produced in 6 hours at room temperature.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention provides a palladium plating
solution capable of forming a high-purity stable palladium
deposit comprising a plated film having a thickness of 5 µm and
free from cracks.
The palladium plating solution contains 0.1 to 40.0 g/l
of a soluble palladium salt in terms of palladium, 0.01 to 10
g/l of pyridine carboxylic acid and/or 0.002 to 1.0 g/l of at
least one salt selected from the group consisting of soluble
iron, zinc, thallium, selenium and tellurium salts in terms of
metal, 0.005 to 10 g/l of an amine derivative of pyridine
carboxylic acid, and 0.001 to 1.2 g/l of an aldehydebenzoic acid
derivative and 0.001 to 1.2 g/l of an anionic surfactant or an
ampholytic surfactant.
Description
The present invention relates to a palladium plating
solution, and particularly, to a palladium plating solution
suitable to provide a palladium-plated ornamental material in
which a nickel allergy problem associated with an ornamental
material has been solved.
Palladium plating solutions have been studied in a wider
range from old. A deposit resulting from the plating has
excellent physical properties, e.g., is excellent in light
resistance, corrosion resistance, discoloration resistance,
wear resistance and the like. Therefore, palladium plating
solutions have been used in applications in a wider field such
as an ornamental material, an electric contact of an electronic
part, a connector, a circuit board and the like. To subject
a personal ornament such as a watch case, a watch band, an
eyeglass frame, a necklace, an ear-ring and a finger ring to
a white plating by a conventional surface-treating technique,
in general, a palladium plating, a palladium-nickel alloy
plating, a palladium-cobalt alloy plating, a rhodium plating,
a platinum plating, a silver plating and the like are carried
out.
The above plating processes suffer the following
disadvantages: The rhodium plating is not of practical use,
because it is very expensive. In the silver plating, a plated
material is liable to be discolored due to a resulting sulfide.
In the palladium-nickel alloy plating, a nickel allergy may be
produced in some cases and for this reason, the use of the
palladium-nickel alloy plating is prohibited in Europe. In the
palladium plating and the platinum plating, a resulting film
has a high stress and for this reason, if a film is formed at
a large thickness, the film is liable to be cracked.
There are conventionally proposed plating processes
suitable for reducing the internal stress in the palladium
deposit or for improving the gloss of a film in consideration
of the above disadvantages. In one of the proposed plating
processes, any of sulfite, nitrous acid and sodium and potassium
salts thereof is incorporated in a plating solution (see
Japanese Patent Publication No.1-47557). In the other proposed
plating process, cerium is incorporated in a plating solution
(see Japanese Patent Application Laid-open No.2-43393). Even
in such conventional surface-treating technique, however, the
cracking problem due to the internal stress in the thick
palladium deposit or a practical subject for maintaining the
appearance gloss could not be solved sufficiently.
Recently, various ornamental materials made by the
palladium plating are complicated considerably in shapes.
Therefore, it is required that a palladium deposit put into a
processing or working is excellent in extensibility, and that
no crack is produced in a moderately bending treatment.
For ornaments such as a watchcase, a watchband, an
eyeglass frame, a necklace, an ear-ring and a finger ring for
Europe, a palladium plating solution capable of forming a
high-purity stable and thick deposit is required as a white metal
plating solution capable of preventing the occurrence of the
nickel allergy.
Accordingly, it is an object of the present invention to
provide a palladium plating solution from which a palladium
deposit exhibiting high-purity stable physical properties can
be formed.
The present inventors has made zealous repeated studies
to provide a palladium plating solution which can be practically
used even in an industrial scale and which is capable of forming
a high-purity palladium deposit, with the above circumstance
in view, and as a result, they have found that a palladium plating
solution produced by incorporating a soluble palladium salt,
pyridine carboxylic acid and/or the soluble trace metal salt
thereof, an amide derivative of pyridine carboxylic acid and
an anionic surfactant or an ampholytic surfactant exhibits a
moderate depositing speed and is excellent in stability, and
produces a high-purity palladium deposit film, which has a
thickness equal to or larger than 5 µm, which is excellent in
specular gloss and in which cracks are little produced. Thus,
the present invention has been accomplished.
The present invention provides
Examples of the soluble palladium salt used in the present
invention are palladium chloride, dichlorodiamine palladium,
dichlorotetraamine palladium and the like. These salts may
be used alone or in combination of two or more. The concentration
of the soluble palladium salt in the palladium plating solution
is preferable to be in a range of 1.0 to 40.0 g/l in terms of
palladium. If the concentration is equal to or smaller than
1.0 g/l, a film-depositing speed is lower and hence, such
concentration is not preferred. If the concentration is equal
to or larger than 40.0 g/l, the forming speed cannot be increased
and hence, such concentration is not of practical use.
Examples of the pyridine carboxylic acid are nicotinic
acid, picolinic acid, iso- nicotinic acid, 2, 3-quinolinic acid,
2,4-lutidinic acid and 2,6-dipicolinic acid. These pyridine
carboxylic acids may be used alone or in combination of two or
more.
The concentration of the pyridine carboxylic acid in the
palladium plating solution is in a range of 0.01 to 20.0 g/l,
preferably in a range of 1.0 to 10.0 g/l. If the concentration
is equal to or smaller than 0.01 g/l, a gloss-enhancing effect
is not provided. If the concentration is equal to or larger
than 20.0 g/l, the gloss cannot be enhanced and hence, such
concentration is not of practical use.
According to the present invention, to reduce the internal
stress in the palladium deposit, the soluble metal salt is used
in combination with the pyridine carboxylic acid or in place
of the pyridine carboxylic acid. The soluble metal salt may
be, for example, any of soluble iron, thallium, selenium and
tellurium salts. Particular examples of the soluble metal salt
are ferric or ferrous sulfate, ferrous ammonium sulfate, zinc
sulfate, thallium sulfate, thallium acetate, selenic acid,
selenious acid, sodium selenite, potassium selenite and the
like. The soluble metal salts may be used alone or in
combination of two or more.
The concentration of the soluble metal salt is in a range
of 0.002 to 1.0 g/l, preferably, in a range of 0.005 to 0.7 g/l
in terms of metal. If the concentration of the soluble metal
salt is equal to or smaller than 0.002 g/l, an effect of reducing
the internal stress in the palladium deposit is not provided.
On the other hand, if the concentration is equal to or larger
than 1. 0 g/l, the internal stress in the palladium deposit cannot
be increased, and hence, such concentration is not of practical
use.
Examples of the amide derivative of the pyridine
carboxylic acid are nicotinamide, picolinamide, iso-nicotinic
acid amide, nicotinic acid amide and the like. These amide
derivatives of the pyridine carboxylic acids may be used alone
or in combination of two or more. The concentration of the amide
derivative of the pyridine carboxylic acid in the palladium
plating solution is in a range of 0.002 to 20.0 g/l, preferably,
in a range of 0.005 to 10.0 g/l. If the concentration of the
amide derivative is equal to or smaller than 0.002 g/l, a
gloss-enhancing effect is not provided, and even if the
concentration of the amide derivative exceeds 20.0 g/l, the
gloss cannot be enhanced and hence, concentration exceeding
20.0 g/l is not of practical use.
Further, examples of the aldehydebenzoic acid derivative
are p-phthalaldehyde, o-phthalaldehyde, o-phthalaldehydic
acid, p-phthalaldehydic acid, m-phthalaldehyde, iso-phthalaldehydic
acid and aldehyde ammonium. The
aldehydobenzoic acid derivatives may be used alone or in
combination of two or more.
The concentration of the aldehydebenzoic acid derivative
in the palladium plating solution is in a range of 0. 002 to 20. 0
g/l, preferably, in a range of 0.005 to 10.0 g/l. If the
concentration of the aldehydebenzoic acid derivative is equal
to or smaller than 0.002 g/l, a gloss-enhancing effect is not
provided. Even if the concentration of the aldehydebenzoic
acid derivative exceeds 20.0 g/l, the gloss cannot be enhanced
and hence, the concentration exceeding 20.0 g/l is not of
practical use.
Further, the anionic surfactant or the ampholytic
surfactant used in the present invention is used to prevent the
pitting, and most effective for an ornament material of a
complicated shape. Particular examples of the anionic
surfactant or the ampholytic surfactant are dodecylamine
acetate, cetylpyridium bromide, di-2-ethylhexyl sodium
sulfosuccinate, sorbitan monopalmitate, polyoxyethylene
stearate, sorbitan monostearate, dimethylalkyl betaine and
dodecyltrimethyl ammonium chloride, polyoxyethylene sorbitan
monopalmitate. The anionic surfactants or the ampholytic
surfactants may be used alone or in combination of two or more.
The concentration of the anionic surfactant or the
ampholytic surfactant in the palladium plating solution is in
a range of 0.001 to 1.2 g/l.
The concentration of the surfactant equal to or smaller
than 0.001 g/l is not sufficient to prevent the pitting, and
even if the concentration of the surfactant equal to or larger
than 1.2 g/l is used, the prevention of the pitting cannot be
enhanced and hence, the concentration of the surfactant equal
to or larger than 1.2 g/l is not of practical use.
According to the present invention, any of potassium
phosphate, potassium hydrogen phosphate, ammonium hydrogen
phosphate, ammonium chloride, ammonium sulfate, boric acid,
ammonium borate, ammonium nitrate, ammonium sulfamate,
potassium nitrate, potassium sulfate, potassium chloride,
potassium sulfamate and the like may be added to the plating
solution in order to provide a conductivity and a buffering
property to the plating solution. These additives may be used
alone or in combination of two or more.
The concentration of the conductive salt in the plating
solution is in a range of 15.0 to 300. 0 g/l. If the concentration
of the conductive salt is equal to or smaller than 15.0 g/l,
the conductivity of the plating solution is poor. If the
concentration of the conductive salt is equal to or larger than
300.0 g/l, the specific gravity of the plating solution is
increased, and a tarnishing, a fogging, a scorching or the like
is produced and hence, the concentration equal to or larger than
300.0 g/l is not preferred.
The plating solution according to the present invention
is used at pH in a range of 7 to 12, preferably, in a range of
7.5 to 9.5. In this pH range, a good plated film can be formed.
The pH value of the plating solution is adjusted using an acid
such as hydrochloric acid and sulfuric acid, or an alkaline
substance such as sodium hydroxide, potassium hydroxide and
ammonia water.
The plating solution according to the present invention
can be used in a plating treatment at a temperature in a range
of 30 to 55°C. Particularly, when the temperature of the plating
solution is in a range of 40 to 55°C, a smooth, glossy good plated
film can be formed. As the temperature of the plating solution
is higher, the film-depositing speed tends to be higher. Any
film-depositing speed can be provided by setting the
temperature of the plating solution at an appropriate value in
the above-described range. Further, in the plating solution
according to the present invention, the film-depositing speed
depends on the concentration of palladium in addition to the
temperature of the plating solution. Therefore, the film-depositing
speed can be also regulated by setting the
concentration of palladium at an appropriate value and hence,
it is easy to control the thickness of the plated film.
The current density for the plating treatment is in a range
of 0.3 to 1.2 A/dm2.
The present invention will now be described in detail by
way of Examples.
| Composition of Plating Solution | |
| Dichlorodiamine palladium | 10 g/l (in terms of Pd) |
| Tellurous acid | 0.05 g/l (in terms of Te) |
| Ammonium chloride | 80 g/l |
| Ammonium hydrogen phosphate | 20 g/l |
| Nicotinic acid amide | 0.8 g/l |
| Di-2-ethylhexyl sodium sulfosuccinate | 0.01 g/l |
The plating solution was regulated to pH of 8.3 by ammonia
water, and a previously nickel-plated brass plate having a size
of 25 x 35mm was immersed in the plating solution at a bath
temperature of 45°C and at a current density of 1.0 A/dm2 for
30 minutes. As a result, a glossy palladium-plated film having
an average thickness of 7 µm was produced. The palladium-plated
film was subjected to an ammonia exposure test (for 12 hours
at room temperature) and as a result, the generation of cracks
was not observed.
| Composition of Plating Solution | |
| Dichlorodiamine palladium | 10 g/l (in terms of Pd) |
| Ammonium chloride | 90 g/l |
| Boric acid | 10 g/l |
| Nicotinamide | 1.0 g/l |
| 2,6-dipicolinic acid | 0.5 g/l |
| Dodecyl trimethyl ammonium chloride | 0.1 g/l |
The plating solution was regulated to pH of 8.3 by ammonia
water, and a previously nickel-plated brass plate having a size
of 25 x 35mm was immersed in the plating solution at a bath
temperature of 42°C and at a current density of 1.0 A/dm2 for
30 minutes. As a result, a glossy palladium-plated film having
an average thickness of 7 µm was produced. The palladium-plated
film was subjected to an ammonia exposure test (for 12 hours
at room temperature) and as a result, the generation of cracks
was not observed.
| Composition of Plating Solution | |
| Dichlorodiamine palladium | 10 g/l (in terms of Pd) |
| Ferrous ammonium sulfate | 0.1 g/l (in terms of Fe) |
| Ammonium chloride | 90 g/l |
| Boric acid | 10 g/l |
| Nicotinamide | 1.0 g/l |
| 2,6-dipicolinic acid | 0.5g/l |
| Dodecyltrimethyl ammonium chloride | 0.1 g/l |
The plating solution was regulated to pH of 8.3 by ammonia
water, and a previously nickel-plated brass plate having a size
of 25 x 35mm was immersed in the plating solution at a bath
temperature of 42°C and at a current density of 1.0 A/dm2 for
30 minutes. As a result, a glossy palladium-plated film having
an average thickness of 7 µm was produced. The palladium-plated
film was subjected to an ammonia exposure test (for 12 hours
at room temperature) and as a result, the generation of cracks
was not observed.
| Composition of Plating Solution | |
| Dichlorodiamine palladium | 10 g/l (in terms of Pd) |
| Ammonium sulfate | 60 g/l |
| Boric acid | 20 g/l |
| Ammonium hydrogen phosphate | 30 g/l |
| Nicotinic acid | 1.0 g/l |
| Picolinamide | 0.5 g/l |
| Di-2-ethylhexyl sodium sulfosuccinate | 0.1 g/l |
The plating solution was regulated to pH of 8.2 by ammonia
water, and a previously nickel-plated brass plate having a size
of 25 x 35mm was immersed in the plating solution at a bath
temperature of 50°C and at a current density of 1.0 A/dm2 for
30 minutes. As a result, a glossy palladium-plated film having
an average thickness of 7 µm was produced. The palladium-plated
film was subjected to an ammonia exposure test (for 12 hours
at room temperature) and as a result, the generation of cracks
was not observed. The palladium-plated film was also subjected
to an artificial sweat immersion test (for 48 hours in room
temperature) and as a result, the discoloration was not
observed.
| Composition of Plating Solution | |
| Dichlorodiamine palladium | 10 g/l (in terms of Pd) |
| Thallium sulfate | 0.035 g/l (in terms of T1) |
| Ammonium sulfate | 60 g/l |
| Boric acid | 20 g/l |
| Ammonium hydrogen phosphate | 30 g/l |
| Nicotinic acid | 1.0 g/l |
| Picolinamide | 0.5 g/l |
| Di-2-ethylhexyl sodium sulfosuccinate | 0.1 g/l |
The plating solution was regulated to pH of 8.2 by ammonia
water, and a previously nickel-plated brass plate having a size
of 25 x 35mm was immersed in the plating solution at a bath
temperature of 50°C and at a current density of 1.0 A/dm2 for
30 minutes. As a result, a glossy palladium-plated film having
an average thickness of 7 µm was produced. The palladium-plated
film was subjected to an ammonia exposure test (for 12 hours
at room temperature) and as a result, the generation of cracks
was not observed. The palladium-plated film was also subjected
to an artificial sweat immersion test (for 48 hours in room
temperature) and as a result, the discoloration was not
observed.
| Composition of Plating Solution | |
| Dichlorodiamine palladium | 10 g/l (in terms of Pd) |
| Ammonium chloride | 40 g/l |
| Ammonium sulfate | 20 g/l |
| Nicotinic acid | 0.5 g/l |
| Iso-nicotinic acid amide | 0.2 g/l |
| Di-2-ethylhexyl sodium sulfosuccinate | 0.1 g/l |
The plating solution was regulated to pH of 8.5 by ammonia
water, and a previously nickel-plated brass plate having a size
of 25 x 35mm was immersed in the plating solution at a bath
temperature of 50°C and at a current density of 1.0 A/dm2 for
30 minutes. As a result, a glossy palladium-plated film having
an average thickness of 7 µm was produced. The palladium-plated
film was subjected to an ammonia exposure test (for 12 hours
at room temperature) and as a result, the generation of cracks
was not observed.
A palladium plating solution having a composition made
by removing the tellurous acid and nicotinic acid amide from
the palladium plating solution used in Example 1 and adding 1.0
g/l of EDTA in place of these acids was used to carry out a plating
treatment under the same conditions as in Example 1. A produced
palladium plated film was subjected to an ammonia exposure test
and as a result, cracks were produced in 6 hours at room
temperature.
A palladium plating solution having a composition made
by removing the nicotinamide from the palladium plating
solution used in Example 2 was used to carry out a plating
treatment under the same conditions as in Example 2. A produced
palladium plated film was ununiform and had not a gloss.
A palladium plating solution having a composition made
by removing the ferrous ammonium sulfate and the nicotinamide
from the palladium plating solution used in Example 3 and adding
1.0 g/l of EDTA in place of these substances was used to carry
out a plating treatment under the same conditions as in Example
3. A produced palladium plated film was subj ected to an ammonia
exposure test and as a result, cracks were produced in 6 hours
at room temperature.
A palladium plating solution having a composition made
by removing the nicotinic acid from the palladium plating
solution used in Example 6 was used to carry out a plating
treatment under the same conditions as in Example 6. A produced
palladium plated film was ununiform and had not a gloss.
As discussed above, the palladium plating solution
according to the present invention has an extremely good
can-stability and exhibits a good workability and a good working
environment. The depositing speed depends on the concentration
of palladium and the temperature of the plating solution and
hence, it is easy to control the thickness of the plated film.
Even if the film formed by the plating solution according to
the present invention has a thickness of 5 µm or more, it has
a gloss, a lower stress, no crack produced and an excellent
extensibility, and presents a beautiful white specular gloss.
Even in the ammonia exposure test of the plated film for 12 hours
at room temperature, no crack is produced. In the test in which
the plated film is entirely or partially immersed in an
artificial sweat for 48 hours at room temperature, the
discoloration does not occur and thus, an excellent palladium
film can be produced.
Claims (8)
- A palladium plating solution comprising 0.1 to 40.0g/l of a soluble palladium salt in terms of palladium, 0.01 to 10g/l of pyridine carboxylic acid, 0.005 to 10g/l of an amine derivative of pyridine carboxylic acid and 0.001 to 1.2g/l of an anionic or an ampholytic surfactant, characterised by the presence of 0.002 to 1.0g/l of at least one salt selected from soluble iron, zinc, thallium, selenium and tellurim in terms of metal and 0.001 to 1.2g/l of an aldehydebenzoic acid derivative.
- A palladium plating solution according to claim 1, wherein said soluble palladium salt is at least one selected from palladium chloride, dichlorodiamine palladium and dichlorotetraamine palladium.
- A palladium plating solution according to claim 1, wherein said pyridine carboxylic acid is at least one selected from nicotinic acid, picolinic acid, iso-nicotinic acid, 2,3-quinolinic acid, 2,4-lutidinic acid and 2,6-dipicolinic acid.
- A palladium plating solution according to claim 1, wherein each of the soluble, iron, zinc, thallium, selenium and tellurium salts is at least one selected from ferric or ferrous sulfate, ferrous ammonium sulfate, zinc sulfate, thallium sulfate, thallium acetate, selenic acid, selenious acid, sodium selenite and potassium selenite.
- A palladium plating solution according to claim 1, wherein said amine derivative of the pyridine carboxylic acid is at least one selected from nicotinamide, picolinamide, iso-nicotinic acid amide, and nicotinic acid amide.
- A palladium plating solution according to claim 1, wherein said aldehydebenzoic acid derivative is at least one selected from p-phthalaldehyde, o-phthalaldehyde, o-phthalaldehydic acid, p-phthalaldehydic acid, m-phthalaldehyde, iso-phthalaldehydic acid and aldehyde ammonium.
- A palladium plating solution according to claim 1, wherein said anionic surfactant or said ampholytic surfactant is at least one selected from dodecylamine acetate, cetylpyridium bromide, di-2-ethylhexyl sodium sulfosuccinate, sorbitan monopalmitate, polyoxyethylene stearate, sorbitan monostearate, dimethylalkyl betaine and dodecyltrimethyl ammonium chloride and polyoxyethylene sorbitan monopalmitate.
- A palladium plating solution according to any of claims 1 to 7, wherein said palladium plating solution contains a conductive salt which is at least one selected from ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium sulfamate, boric acid, ammonium borate, potassium nitrate, potassium sulfate, potassium chloride and potassium sulfamate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34239299 | 1999-10-27 | ||
| JP2000211927A JP3601005B2 (en) | 1999-10-27 | 2000-06-09 | Palladium plating solution |
| PCT/JP2001/005107 WO2002103084A1 (en) | 1999-10-27 | 2001-06-15 | Palladium plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1396559A1 true EP1396559A1 (en) | 2004-03-10 |
| EP1396559A4 EP1396559A4 (en) | 2006-10-11 |
Family
ID=27278780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01941060A Withdrawn EP1396559A4 (en) | 1999-10-27 | 2001-06-15 | Palladium plating solution |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1396559A4 (en) |
| CN (1) | CN1249270C (en) |
| GB (1) | GB2382353B (en) |
| WO (1) | WO2002103084A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013104877A1 (en) * | 2012-01-12 | 2013-07-18 | Johnson Matthey Public Limited Company | Improvements in coating technology |
| EP3067444A3 (en) * | 2015-03-09 | 2016-12-07 | Ing. W. Garhöfer Gesellschaft mbH | Separation of decorative palladium iron alloy coatings on metallic substances |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102400190A (en) * | 2010-09-17 | 2012-04-04 | 日本电镀工程股份有限公司 | Iridium plating solution and electroplate method thereof |
| ITFI20120098A1 (en) * | 2012-05-22 | 2013-11-23 | Bluclad Srl | GALVANIC BATH WITH BASE OF PALLADIUM AND PHOSPHORUS, ITS USE IN GALVANIC PROCESSES AND ALLOYS OBTAINED BY APPLYING THE GALVANIC PROCESS TO THOSE BATHROOMS. |
| JP6620103B2 (en) * | 2014-09-04 | 2019-12-11 | 日本高純度化学株式会社 | Palladium plating solution and palladium film obtained using the same |
| CN105441998A (en) * | 2015-10-30 | 2016-03-30 | 无锡市嘉邦电力管道厂 | Palladium plating containing sodium nitrite and tetra-n-propylammonium bromide and plating method thereof |
| CN105332021A (en) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | Palladium electroplating solution containing sodium nitrite and tetraphenylarsonium bromide and electroplating method thereof |
| CN105316722A (en) * | 2015-11-20 | 2016-02-10 | 无锡市嘉邦电力管道厂 | Palladium electroplating solution containing tetraphenylarsonium bromide and electroplating method of palladium electroplating solution |
| CN105332023A (en) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | Palladium electroplating solution containing tetra-n-propylammonium bromide and electroplating method thereof |
| CN105332024A (en) * | 2015-11-20 | 2016-02-17 | 无锡市嘉邦电力管道厂 | Palladium electroplating liquid containing isopentyltriphenylphosphonium bromide and electroplating method thereof |
| CN105543913A (en) * | 2016-02-25 | 2016-05-04 | 盈昌集团有限公司 | Palladium-cobalt alloy electroplating liquid and technology of electroplating spectacle frame with same |
| CN106757207A (en) * | 2016-11-29 | 2017-05-31 | 江苏澳光电子有限公司 | A kind of method for pcb board chemical nickel plating palldium alloy |
| CN106757203A (en) * | 2016-11-29 | 2017-05-31 | 江苏澳光电子有限公司 | A kind of molybdenum alloy surface chemical palladium-plating crosses liquid and its application |
| CN106757204A (en) * | 2016-11-29 | 2017-05-31 | 江苏澳光电子有限公司 | It is a kind of to cross liquid and its application in stainless steel surfaces plating palladium |
| CN108004573B (en) * | 2017-12-12 | 2020-10-16 | 安徽启东热能科技有限公司 | Surface treatment process for gas-liquid separation disc body |
| CN119571402B (en) * | 2025-02-05 | 2025-04-04 | 深圳创智芯联科技股份有限公司 | Electroplating thick palladium solution and electroplating method applied to advanced packaging bump process |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3317493A1 (en) * | 1983-05-13 | 1984-11-15 | W.C. Heraeus Gmbh, 6450 Hanau | GALVANIC DEPOSITION OF PALLADIUM COVERS |
| US4911799A (en) * | 1989-08-29 | 1990-03-27 | At&T Bell Laboratories | Electrodeposition of palladium films |
| JPH0711476A (en) * | 1993-06-23 | 1995-01-13 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
| JPH07278870A (en) * | 1994-04-08 | 1995-10-24 | Kojima Kagaku Yakuhin Kk | Palladium plating solution |
| DE19528800C2 (en) * | 1995-08-04 | 1999-05-06 | Ami Doduco Gmbh | Alkaline or neutral bath for the galvanic deposition of palladium or alloys of palladium |
| JP3379412B2 (en) * | 1997-05-30 | 2003-02-24 | 松下電器産業株式会社 | Palladium plating solution, palladium plating film using the same, and lead frame for semiconductor device having the palladium plating film |
| JP4249292B2 (en) * | 1998-07-10 | 2009-04-02 | 株式会社大和化成研究所 | Tin and tin alloy plating bath |
| JP2000303199A (en) * | 1999-02-17 | 2000-10-31 | Nisshin Kasei Kk | Palladium alloy plating solution, palladium-copper alloy plated member and antibacterial member |
| JP3601005B2 (en) * | 1999-10-27 | 2004-12-15 | 小島化学薬品株式会社 | Palladium plating solution |
-
2001
- 2001-06-15 WO PCT/JP2001/005107 patent/WO2002103084A1/en active Search and Examination
- 2001-06-15 GB GB0128788A patent/GB2382353B/en not_active Expired - Fee Related
- 2001-06-15 EP EP01941060A patent/EP1396559A4/en not_active Withdrawn
- 2001-06-15 CN CNB01801111XA patent/CN1249270C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013104877A1 (en) * | 2012-01-12 | 2013-07-18 | Johnson Matthey Public Limited Company | Improvements in coating technology |
| EP3067444A3 (en) * | 2015-03-09 | 2016-12-07 | Ing. W. Garhöfer Gesellschaft mbH | Separation of decorative palladium iron alloy coatings on metallic substances |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002103084A9 (en) | 2003-04-24 |
| GB2382353A (en) | 2003-05-28 |
| CN1249270C (en) | 2006-04-05 |
| GB0128788D0 (en) | 2002-01-23 |
| CN1420947A (en) | 2003-05-28 |
| EP1396559A4 (en) | 2006-10-11 |
| WO2002103084A1 (en) | 2002-12-27 |
| GB2382353B (en) | 2004-10-27 |
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