U.S. patent number 3,928,157 [Application Number 05/357,534] was granted by the patent office on 1975-12-23 for cathodic treatment of chromium-plated surfaces.
This patent grant is currently assigned to Shinto Paint Co., Ltd., Uyemura & Co., Ltd.. Invention is credited to Mitsuyasu Kubo, Ryuhei Miyazaki, Yasuo Suematsu, Hironori Uchida, Tsuyoshi Uotani.
United States Patent |
3,928,157 |
Suematsu , et al. |
December 23, 1975 |
Cathodic treatment of chromium-plated surfaces
Abstract
A method for treating a chromium-plated surface is provided
characterized by the fact that a chromium-plated article is dipped
as the cathode in a water-soluble or water-dispersible resin
solution or dispersion prepared by diluting with water a resin salt
of at least one synthetic polyamino resin with a water-soluble
organic acid and/or a water-soluble inorganic acid, and then
passing a direct current in the range of 10 - 300 volts through the
aqueous bath so that there is formed a resin film on the chromium
plated surface the chromium-plated surface is pretreated prior to
the resin coating step by anodization in aqueous chromate solution
or by heat treatment so that the surface electrode potential is
greater than -0.42 volts.
Inventors: |
Suematsu; Yasuo (Itami,
JA), Miyazaki; Ryuhei (Ibaraki, JA), Kubo;
Mitsuyasu (Neyagawa, JA), Uotani; Tsuyoshi
(Hirakata, JA), Uchida; Hironori (Hirakata,
JA) |
Assignee: |
Shinto Paint Co., Ltd.
(Amagasaki, JA)
Uyemura & Co., Ltd. (Osaka, JA)
|
Family
ID: |
27293123 |
Appl.
No.: |
05/357,534 |
Filed: |
May 7, 1973 |
Foreign Application Priority Data
|
|
|
|
|
May 15, 1972 [JA] |
|
|
47-047899 |
May 15, 1972 [JA] |
|
|
47-047900 |
May 15, 1972 [JA] |
|
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47-047901 |
|
Current U.S.
Class: |
205/704; 205/180;
205/917; 525/161; 204/502; 204/501; 205/171; 205/178; 205/209;
525/124; 525/379 |
Current CPC
Class: |
C09D
5/4488 (20130101); Y10S 205/917 (20130101) |
Current International
Class: |
C09D
5/44 (20060101); C25D 013/06 (); C25D 013/20 () |
Field of
Search: |
;204/181 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Weisstuch; Aaron
Attorney, Agent or Firm: Armstrong, Nikaido & Wegner
Claims
What is claimed is:
1. A method for treating a chromium-plated surface characterized by
the fact that a chromium-plated article having an uppermost
chromium-plated layer of a thickness of at least 0.2 micron and
adjacent thereto, an intermediate nickel or nickel-alloy layer, is
dipped as the cathode in a water-soluble or water-dispersible resin
solution or dispersion prepared by diluting with water a resin salt
of at least one synthetic polyamino resin and a water-soluble
organic acid, a water-soluble inorganic acid or a mixture of said
acids and then passing a direct current in the range of 10-300
volts through the aqueous bath so that there is formed a resin film
on the chromium plated surface.
2. A method as claimed in claim 1 wherein after the
electrodeposition the resin-coated article is subjected to an
after-treatment with an aqueous treating agent, said treating agent
being selected from the group consisting of antioxidants,
surface-active agents, organic solvents, acids and bases, and is
thereafter baked or cured.
3. A method as claimed in claim 2 wherein the aqueous treating
agent for the after-treatment contains an anti-oxidant selected
from the group consisting of phenolic-type antioxidants and
phosphite-type antioxidants
at a concentration of 0.01 to 2.0% by weight. 4. A method as
claimed in claim 2 wherein the aqueous treating agent for the
after-treatment contains a surface-active agent selected from the
group consisting of silicone oils and anionic, cationic, nonionic
and amphoteric surface-active agents at a concentration of 0.001 to
2.0 percent by
weight. 5. A method as claimed in claim 2 wherein the aqueous
treating agent for the after-treatment contains an organic solvent
selected from the group consisting of glycol ethers, glycol ether
esters, alcohols, ketones and esters at a concentration of 1 to 90
% by weight, preferably 5
to 70 % by weight. 6. A method as claimed in claim 2 wherein the
aqueous treating agent for the after-treatment contains an acid
selected from the group consisting of phthalic anhydride,
trimellitic anhydride, pyromellitic anhydride and oxalic acid at a
concentration of 0.1 - 5.0 %,
preferably 0.3 - 4.0 % by weight. 7. A method as claimed in claim 2
wherein the aqueous treating agent for the after-treatment contains
a base selected from the group consisting of dicyandiamide and
dibutylamine at a
concentration of 0.1 - 5.0 %, preferably 0.3 - 4.0 % by weight. 8.
A method as claimed in claim 1 wherein the chromium-plated surface
is pretreated before the electrodeposition so that the surface
electrode potential as defined herein before has a value higher
than -0.42 volt by
means of an electrochemical or physical treatment. 9. A method as
claimed in claim 8 wherein the electrochemical treatment is
conducted by the anodic-electrolysis of the chromium-plated surface
in an aqueous solution selected from the group consisting of
chromic acid, chromate or
dichromate. 10. A method as claimed in claim 8 wherein the physical
treatment is conducted by heating the chromium-plated surface such
that the product of the temperature and time of treatment is at
least 3000.degree.C-min. and the upper limit of temperature is
300.degree.C.
A method as claimed in claim 8 wherein the physical treatment is
conducted by exposing the chromium-plated surface to air at the
normal
temperature for at least 24 hours. 12. A method as claimed in cliam
1 wherein the synthetic polyamino resin is a resin containing
primary, secondary, or tertiary amino groups or quaternary ammonium
groups or mixtures of these groups in the molecule, and is selected
from the group consisting of (A) a vinylic or acrylic copolymer
containing amino groups as pendant groups, (B) a resinous polymer
made by introducing amino groups by making a dialkylamine or
dialkanolamine react on an epoxy resin containing two or more epoxy
groups in the molecule, (C) a polyester resin obtained by using an
alkanolamine as one component of a polyol and cocondensing a
polybasic acid with the other polyol, (D) a polyurethane resin
obtained by using an alkanolamine as one component and cocondensing
a polyisocyanate with the other polyol and (E) a terminal amino
group-containing polyamide resin obtained by condensing a
stoichiometrically excess polyamine with a polybasic acid at a
solid part concentration in the electrodepositing bath solution in
a range of 1 to 20
percent by weight. 13. A method as claimed in claim 1 wherein said
water-soluble organic acid and water-soluble inorganic acid are
selected from the group consisting of formic acid, acetic acid,
propionic acid, lactic acid, malonic acid, citric acid,
hydrochloric acid, phosphoric acid, and sulfuric acid and wherein
said water-soluble organic acid, water-soluble inorganic acid or
mixture thereof is employed in an amount of 0.3 to 1.0 equivalent
for 1.0 equivalent of the amino groups in the synthetic polyamino
resin.
Description
This invention relates to the surface treatment of a
chromium-plated surface. More particularly, this invention relates
to a method of treating a chromium-plated surface characterized by
the cathodic-deposition of a resin coating on the chromium-plated
surface (used as the cathode) from an aqueous solution or
dispersion of a resin salt comprising a thermosetting synthetic
polyamino resin and an acid.
The term "chromium-plating" or the like used herein means all kinds
of chromium plating known in the art of metal plating. The
thickness of such chromium-plated layer is at least 0.01 micron,
preferably at least 0.2 micron.
In conventional metal-plating, several metallic layers of copper,
nickel or chromium are plated or electro-coated on a well ground
and conditioned metallic article. The total thickness of such
plated layer is usually about 5 to 50 microns. Particularly, the
chromium plating is superior to any other metal plating in
appearance, metallic-luster and corrosion resistance so that it is
preferable that chromium is electroplated as a final finishing even
on a copper or nickel plated surface to obtain corrosion-resistant
plated articles. However, there is the disadvantage that numerous
pinhole-like pores are present on such metal-plated surfaces so
that it is difficult to prevent corrosion therethrough. In order to
prevent such corrosion, it is necessary to make the thickness of
all the plating layers at least about 50 microns. This would cause
economic disadvantages including the increase in operative
steps.
In order to overcome such disadvantage a coating of an organic
material may be considered. However, with coating processes usually
practiced in the coating industry such as brush coating, dipping or
spraying, it is difficult to form a uniform film which can seal
pores on the chromium-plated surface of an article with complicated
form and which can retain a high grade appearance and an excellent
metallic luster. Further, the adhesion of the organic coating on
the metal surface is low with such conventional coating
methods.
On the other hand, the formation of an organic coating by
electrodeposition has a great advantage in the sealing of pores on
the chromium-plated surface and in the formation of a uniform film
layer. However, the resin to be used for the conventional
electrodeposition coating composition generally has carboxyl groups
and is used in the form of a water-dispersible resin in which the
carboxyl groups are converted into salts with an alkaline
substance. Thus the resin would be present in the form of anions in
the aqueous medium. With the use of such an anionic type resin
solution in the electrodeposition process, the chromium plated
surface to be coated is treated as an anode. Therefore when direct
current is passed the plated metallic chromium will be
electrolytically dissolved out. In this case, if the plated article
is a zinc die-casting or the like, the pores on the plated surface
will become larger and more numerous so that the metallic ions of
the base material and of the plated layers will dissolve out
through such pores and will mix into the organic film. Therefore
the organic coating film will be undesirably discolored and shrunk
and its adhesion to the metal surface will be impaired. Further,
due to the corrosion of the chromium-plating layer, the luster of
the chromium-plated surface will be deteriorated and, in some
cases, the product value will be reduced by the partial exposure of
the base or substrate metal.
The object of the present invention is to overcome all these
drawbacks. Thus this invention relates to the improved surface
treatment of a chromium-plated metal face. More particularly the
present invention relates to a method for the surface treatment of
a chromium-plated surface characterized by the fact that a
chromium-plated article is dipped as a cathode in a water-soluble
or water-dispersible resin solution or dispersion obtained by
diluting with water a resin salt consisting of any one or mixture
of two or more thermosetting synthetic polyamino resins and a
watersoluble organic acid and/or a water-soluble inorganic acid or
an aqueous solution thereof, and then passing a direct current
through the aqueous bath so that there is formed an excellent resin
film on the chromium-plated surface. According to the present
invention the thick film character of the metal plating is enhanced
in appearance without impairing the high grade appearance and
excellent metallic luster of the chromium-plating. The total
thickness of the metal-plating layers may be reduced. Further the
resulting film has corrosion-resistance twice as high as that of a
conventional plating layer of the same thickness, and the adhesion
of the organic film to the chromium-plated surface is far higher
than by any other coating method.
The synthetic polyamino resins to be used in the method of this
invention are resins containing amino groups (such as primary,
secondary or tertiary amino groups or quaternary ammonium groups)
in the molecule, and are vinyl or acrylic copolymers containing
amino groups as pendant groups, resinous polymers made by
introducing amino groups by reacting dialkylamines or
dialkanolamines with epoxy resins containing two or more epoxy
groups in the molecule, polyester resins obtained by using
alkanolamines as one component of polyols and cocondensing
polybasic acids with the other polyols, polyurethane resins
obtained by using alkanolamines as one component and cocondensing
polyisocyanates with the other polyols or polyamide resins having
terminal amino groups obtained by condensing stoichiometrically
excess polyamines with polybasic acids.
In an aqueous solution or dispersion obtained by diluting with
water a resin salt of such resin containing amino groups with a
water-soluble organic acid and/or a water-soluble inorganic acid or
an aqueous solution thereof, the resin acts as polymer cations and
is therefore considered to be a cationic type resin. When a direct
current is passed through the aqueous resin solution or dispersion,
the resin is deposited on the chromium-plated surface used as the
cathode. Therefore, if an insoluble anode such as, for example,
lead, carbon or stainless steel is used the electrolytic
dissolution of metal will be prevented.
If desired, the amino groups contained in such resin can be
alkylated by a known method and can be finally converted to
quaternary ammonium groups. However, in the present invention, it
is not always necessary to convert the amino groups into quaternary
ammonium salts. It is desirable that the resin to be used be
thermosetting or curable. In such a case, self-cross-linkable
functional groups can be introduced in the resin itself. It is also
possible to blend a cross-linking agent with the resin, such as for
example, a lower alcohol (e.g. methanol, butanol, etc.) ether of a
condensate of formaldehyde with phenol, melamine or urea, or an
epoxy compound or a blocked isocyanate. The amount of such
cross-linking agent may be 5 - 30 % by weight based on the total
resin composition.
The acid component to be used for forming a resin salt with the
above mentioned synthetic polyamino resin is selected from
water-soluble organic acids such as formic acid, acetic acid,
propionic acid, lactic acid, malonic acid or citric acid or water
soluble inorganic acids such as hydrochloric acid, phosphoric acid
or sulfuric acid. If desired, a mixture of two or more of them may
be used. The amount of the acid to be used is preferably 0.3 to 1.0
equivalent for 1.0 equivalent of the amino group of the synthetic
polyamino resin. Below 0.3 equivalent, the water-dispersibility of
the resin salt will be so low that the stability of the diluted
resin solution will be low. Above 1.0 equivalent, the redissolution
of the resin composition deposited on the chromium-plated surface
will be considerable and the deposition of bubbles developed in the
electrolysis on the resin coating will be considerable.
The concentration of the resin in the aqueous resin solution or
dispersion prepared by diluting the above mentioned resin salt with
water is preferably 1 to 20 % by weight. Below 1 % by weight, the
deposition of the resin on the cathode will not be easy. Above 20 %
by weight, the resin solution will become sticky.
The temperature of the bath (i.e. the aqueous resin solution or
dispersion) is preferably 10 to 50.degree.C.
In carrying out the cathodic electrodeposition the aqueous resin
solution or dispersion is held in an electrodeposition cell or tank
made of a material not corroded by the resin solution or
dispersion. A carbon rod or lead plate is used as an anode and a
chromium-plated article to be treated is used as a cathode. These
electrodes are dipped into the electrodeposition bath and a
potential difference of 10 to 300 volts is applied between the
electrodes while stirring the bath. The treating time may be
properly varied depending on the particular object but is generally
10 seconds to 5 minutes.
Then the coated cathode is taken out of the tank, washed with water
and is baked and dried to obtain a resin coated chromium-plated
surface high in both appearance and performance.
It has further been found that the surface treatment effect is
further improved if the chromium-plated surface is pretreated prior
to the above mentioned electrodeposition of the resin. Thus, by
this pretreatment the adhesion of the electrodeposited organic
resin layer on the chromium-plated surface is improved and further
the appearance of the resin layer is improved.
This pretreatment is conducted by subjecting the chromium-plated
surface to (1) anodic treatment in an aqueous solution of chromic
acid, (2) heat treatment at a high temperature or (3) exposure to
air for a long period of time, so that the electrode potential
(which is a value measured at 15 seconds after the beginning of the
measurement by using a saturated calomel electrode as a standard in
a buffer solution of 0.1 mol of citric acid, 0.2 mol of sodium
hydrogen phosphate and a pH of 4.7 at a temperature of
25.degree.C., and is referred to merely as a potential hereinafter)
of the chromium-plated surface becomes more noble than -0.42
volt.
As a result of various researches on the treatment of a
chromium-plated surface by anodic electrodeposition processes, we
have found that the adhesion of the cationic type resin film to the
chromium-plated surface is influenced by or depends on the state of
the chromium-plated surface. In other words, the adhesion has a
selectivity for the surface state of the chromium-plating. Such
selectivity is determined by the surface potential of the
chrom-plate. On the other hand, it has been confirmed as a result
of CASS tests (Copper-Accelerated Acetic Acid Test, JIS D-0201) and
sight tests that the adhesion of an organic film to a metal face is
related to the uniformity of the appearance and the degree of the
corrosion resistance of the film.
The state of the chromium-plated surface shall be explained more
concretely with numerical values. It has been found that, when a
chromium-plating has a surface state of a potential higher (more
noble) than -0.42 volt, the adhesion of the film thereto is very
favorable.
We have further found that the potential of a chromium-plated
surface may be made more noble than -0.42 volt if the
chromium-plated surface is subjected to (1) anodic-electrolytic
treatment in 0.1 - 5 % solution of chromic acid, or (2) heating and
drying at a high temperature or (3) air at the normal temperature
for a long time, to modify the surface of the chromiumplated layer.
When the abovementioned electrodeposition of organic resin is
conducted after this pretreatment there is obtained a resinous
coating film having such strong adhesion and high
corrosion-resistance as have never been obtained before.
The pretreatment or surface modification of the chromium-plated
face prior to the electrodeposition of the organic resinous film
thereon will be explained in more detail as follows.
The first method is the anodic-electrolytic treatment of the
chromium surface of a chromium-plated article in an aqueous
solution of chromic acid or dichromate. Usually the electrolysis is
carried out at an anode current density of 0.1 to 5
amperes/dm..sup.2 at the normal temperature for 20 to 180 seconds
in 0.1 - 5 % solution of chromic acid or dichromic acid so that the
potential of the chromium-plated surface becomes nobler than -0.42
volt.
However, the above mentioned particular conditions for the
anodic-electrolysis are not always critical. Thus in case the
treatment is carried out under conditions other than those
mentioned above, the potential of the chromium-plated surface can
be rendered more noble than -0.42 volt.
However, if the electrolysis is conducted for a longer time and/or
the anode current density is made higher, the chromium-plating
itslef will tend to dissolve to expose the base or substrate metal,
so that the chromium-plating will have to be made thicker to
prevent it and therefore such conditions will be not practical. On
the other hand, if the anode current density is made lower, it will
be necessary to conduct the electrolysis for an extremely long
time.
In actual operation it is preferable to conduct this anodic
electrolysis just after the chromium-plating step. After the anodic
electrolysis the pretreated article is subjected to washing with
water, cathodic electrodeposition, washing with water and drying in
the mentioned order.
The second method of the pretreatment is to heat the
chromium-plated surface at a high temperature prior to the
electrodeposition of the resinous coating film. Thus, after the
chromium-plating, the plated article is washed with water and then
heated and dried at a high temperature. The temperature at which
such heating is conducted varies depending upon the time and the
state of the chromium-plating itself to be treated and therefore
the temperature and time can not be definitely specified. However,
it is found that, as a general standard, they may be expressed by
the product (.degree.C.).times.(min.). The minimum standard value
is 3000 (.degree.C.).times.(min.). For example, when the heating is
conducted at 50.degree.C. the minimum time required is 60 minutes
or longer, and when heated and dried at 100.degree.C. the time
required would be at least 30 minutes. In case of 200.degree.C. the
time required is at least 15 minutes. The upper limit of the
temperature is 300.degree.C. This heat treatment can be conducted
in air or in hot water.
Another pretreatment is to expose the chromium-plated surface to
air at the room (or "normal") temperature (e.g. 10.degree. -
35.degree.C.) for a long time. The effect of this treatment is
considered to be that the chromium-plated surface will be oxidized
by oxygen in air so that the potential becomes nobler than in the
case that such exposure is not carried out. Therefore, by this
treatment the potential can be made more noble than -0.42 volt
depending on the degree of the oxidization, that is, the time of
exposure. In this case, the time required to make the potential
nobler than -0.42 volt is at least 24 hours. If the exposure time
is shorter, for example, 18 hours, usually the surface potential of
the chromium-plating will be only -0.46 volt. After this
pretreatment, the chromium-plated article may be subjected to the
electro-deposition mentioned before.
If the chromium-plated surface modified or pretreated as mentioned
above so that the surface potential may be more noble than -0.42
volt is then coated with the above described thermosetting
synthetic polyamino resin film by the cathodic electrodeposition,
the adhesion of the resin film to the chromium surface is improved
and therefore a product having a higher corrosion resistance is
obtained.
The effect of this pretreatment will be demonstrated as follows.
Thus, in order to facilitate the comparison, there were used test
pieces prepared by chromium plating to a thickness of 0.5 micron in
a sargent bath (normal chromium-plating bath) iron pieces (2
dm..sup.2) which have been copper-plated to a thickness of 10
microns and bright-nickel-plated by a thickness of 5 microns. As
for the cation type resin, there was used a resin prepared by
introducing amino groups by making a secondary amine react with an
acrylic copolymer. An aqueous solution of the acetate of the resin
at a pH of 5.0 and a resin concentration of 10 % by weight was used
a cathodic-electrodeposition bath.
The electrodeposition was conducted at a voltage of 70 volts for 1
minute at a temperature of 20.degree.C. After the electrodeposition
the coated film was baked at 200.degree.C. for 30 minutes.
In the above the chromium-plated surface was not pretreated or
modified, and chromium-plating, water-washing (or water-washing and
hot-water-washing), cathodic-electrodeposition, water-washing and
baking were conducted in the mentioned order. The potential of the
chromium-plated surface was -0.49 to -0.54 volt. The
corrosion-resistance of the resulting resin film had a rating
number of 7 in 5 cycles of the CASS Test.
In the case of carrying out the pretreatment i.e.,
anodic-electrolysis, chromium-plating, anodic-electrolysis,
water-washing, cathodic-electrodeposition and baking were conducted
in the mentioned order. The anodic-electrolysis was effected at
25.degree.C., with anode current density of 2 amperes/dm..sup.2 and
for 30 seconds in 1 % aqueous solution of chromic acid. The
potential of the chromium-plated surface became -0.35 volt by this
pretreatment. The adhesion of the resin film was strong and the
corrosion-resistance had a rating number of 10 in 5 and 7 cycles of
the CASS Test.
As another pretreatment the chromium-plated surface was exposed to
the atmosphere (ambient air) for a long time. In this case,
chromium plating, water-washing, exposure to air,
cathodic-electrodeposition, water-washing and baking were conducted
in the mentioned order. When exposed to air for 24 and 48 hours,
the potentials of the chromium plated surface became respectively
-0.39 and -0.34 volt. The appearance of the obtained resin film was
uniform and the corrosion-resistance had rating numbers of 10 in 5
cycles and 9 in 7 cycles of the CASS Test.
Still another pretreatment i.e. heat-treatment at a high
temperature was conducted. In this case, chromium-plating,
water-washing, high temperature heat-treatment,
cathodic-electrodeposition, water-washing and baking were conducted
in the mentioned order. Thus the chromium-plated surface was heated
at 50.degree.C. for 60 minutes, at 100.degree.C. for 30 minutes and
at 200.degree.C. for 15 minutes respectively. By this pretreatment
the potential of the chromium-plated surface became respectively
-0.37, -0.32 and -0.27 volt. The resulting
cathodic-electrodeposited film was uniform and smooth in
appearance, high in the adhesion and had corrosion-resistance of a
rating number of 10 in 5 cycles of the CASS Test.
As apparent from the above mentioned comparative tests, when the
chromiuim-plated surface is pretreated or modified, the potential
of the chromium-plated surface can be made nobler than -0.42 volt
and, when the so pretreated surface is subsequently subjected to
the cathodic-electro-deposition treatment, a film excellent in
appearance and performance is obtained.
As still another aspect of this invention we have also found a
means of further improving the excellent appearance and metallic
luster of a chromium-plating. Thus, according to this invention, it
is preferable to conduct a special after-treatment after an organic
resin film has been formed by the cathodic-electrodeposition.
More particularly, after an organic resin film is formed on the
chromium-plated surface by the before mentioned
cathodic-electrodeposition but before the baking or curing of the
film, there is conducted an after-treatment which comprises
contacting the resin film with an aqueous solution or dispersion
containing one or more of anti-oxidants, surface-active agents,
organic solvents, acids and bases.
In the electrodeposition coating step, in response to the
differences in surface states of the base or substrate of the
article, for example, insufficient defatting, presence of stains,
flaws, differences in rolling and the presence of different kinds
of metals due to welding, etc. the electric characteristics of the
surfaces are different and hence the state of the electrodeposited
film will be much influenced thereby. For example, if the base
metal to be plated is perfectly cleaned and ground and then
chromiumplated the resulting surface state may be not so bad.
However, for example, when a zinc die-casting is plated, the
resulting surface state of the chromium-plating will be poor from
an electrochemical viewpoint. Therefore, in the case of coating by
electro-deposition on a chromium-plated surface, it will be
necessary to take care to prevent the product value from being
reduced by these influences. Further, since the smoothness and
luster in the appearance of a chromium-plated surface are known to
be excellent it is necessary not to impair these favorable effects
by applying an organic film coating thereon.
Further, in the production of the thermosetting synthetic polyamino
resins to be used in the present invention, a basic
nitrogen-containing resin is reacted with an acid to form a salt,
which is dissolved or dispersed in water. When the
nitrogen-containing component is oxidized, it will tend to become
yellowish. When a light colored or colorless transparent coating
film electrodeposited from such aqueous solution or dispersion of
the resin is heat-treated or baked to be cured in the final step,
the surface of the film is likely to be oxidized so that the film
tends to become yellowish. Further, the so called orange peel
phenomenon likely to occur.
We have found that these drawbacks are overcome if the
electrodeposited resin film is treated (before being baked or
cured) with an after-treating agent. By applying this treatment,
not only are the excellent appearance and metallic luster of the
chromium-plating not impaired but also no coated appearance
results, so that the thick film character of the plated layer
increases.
The after-treatment agents that can be used are surface active
agents, antioxidants and organic solvents. They may be used
respectively alone or as mixed. A proper amount of the same is used
as diluted with water.
In carrying out the after-treatment, the electrodeposition resin
coated article is washed with water and then dipped for several
seconds to about 10 minutes in the above described aqueous
after-treating agent. Then the coated film is subjected to setting
or is preheat-treated at about 40.degree. - 90.degree.C. and then
subjected to final baking or curing.
The surface active agent used in this after-treatment is effective
in removing the electrolysis gas deposited on the electrodeposited
film and in improving the smoothness of the coated film surface. By
both of these effects, the nonuniformity of the film is eliminated
and the colored specks produced by the combination of the orange
peel phenomenon and yellowing phenomenon are effectively prevented.
Further there is also an additional effect of improving
wear-resistance such as the surface slip and scratching resistance
of the finished coating film.
The useful surface active agents are silicone surface active
agents, anionic surface active agents, cationic surface active
agents, nonionic surface active agents and amphoteric surface
active agents. The total concentration of such surface active agent
is about 0.001 to 2.0 % by weight.
The antioxidants that may be used as the aftertreating agent are
those having an effect of preventing the cationic type resin from
being discolored by the oxidation. Such antioxidant is easily and
uniformly adsorbed on the surface of the electrodeposited coating
film surface so that the oxidization of the coating film surface by
the heat-treatment at the time of baking or curing is prevented.
Therefore, in a cationic resin coating film of a thickness not more
than about 25 microns, the yellowing phenomenon at the time of
baking or curing of the coated film can be substantially prevented.
Therefore, it is not necessary to add an antioxidant into the resin
composition for the electrodeposition so that the bath control or
handling is easy.
Examples of useful antioxidants are those of phenol derivatives or
phosphites. The concentration thereof in the after-treatment bath
is about 0.01 to 2.0 % by weight.
The organic solvent that can be used as an aftertreating agent
promotes the leveling effect of the coated film by slightly
dissolving the electrodeposited film surface, removing the
electrolysis bubbles on the surface and giving a fluidity so that
the nonuniformity of the film surface is eliminated and the same
effect as of the surface active agent may be obtained even against
color specks. The organic solvent also has a role of helping the
surface active agent and antioxidant to uniformly disperse in the
aftertreating bath.
Therefore, in selecting such an organic solvent, it is necessary to
consider the affinity of the organic solvent with the
electrodeposited coating film. Further, since the after-treating
agent is generally used as diluted with water, it is preferable
that the solvent be compatible with water. Further, the boiling
thereof at the time of the subsequent baking or curing should be
kept minimum. Therefore it is preferable that the organic solvents
are those having a high boiling point, lypophilicity and
hydrophilicity (that is, having a surface active effect). For this
purpose, ethylene glycol monobutyl ether or the like is most
effective.
However, in the case of using a mixture of organic solvents, any
solvent having any role of the above mentioned organic solvents
including hydrophobic organic solvents can be used. For example,
glycol ethers, alcohols, ketones and esters may be used.
The total concentration of such organic solvent in the
after-treating bath is 1 to 90 %, preferably 5 to 70 % by
weight.
When it is desired that the cationic resin coating film be baked or
cured at a lower temperature or its surface hardness be increased,
it is effective to add a curing catalyst or cross-linking agent for
the resin in the aftertreatment bath.
Thus when a lower alcohol ether of a condensate of formaldehyde
with phenol, melamine or urea is blended with the cationic
polyamino resin salt for the electro-deposition coating, an acid
useful for promoting the curing of the condensate may be used as
the after-treating agent. Examples of such acid catalyst are
phthalic anhydride, trimellitic anhydride, pyromellitic anhydride,
oxalic acid, etc. which are well known in the art as catalysts for
promoting the curing of formaldehyde resins. The concentration of
the acid may be about 0.1 - 5.0 % by weight in the after-treating
liquid. By effecting this acid after-treatment the temperature
required for baking or curing the deposited resin film may be
lowered by about 20.degree.C. or more.
Further, when the cationic resin used for the electrodeposition
contains epoxy groups as functional groups, it is preferable to add
to the after-treating liquid a cross-linking or curing agent well
known for curing epoxy resins, e.g. bases such as amines and
amides. More particularly examples thereof are dicyandiamide,
dibutylamine, etc. The concentration of such base in the
after-treating liquid is about 0.1 - 5.0 % by weight. When the
after-treatment with such base is effected, the subsequently baked
or cured resin film is increased in the hardness from 2H (not
after-treated) to 3H, or sometimes even to 4H.
The invention will be further explained by means of the following
Examples wherein all parts and percentages are by weight unless
otherwise specified.
EXAMPLE 1
17.5 parts of styrene, 35 parts of glycidyl methacrylate and 35
parts of 2-ethylhexyl acrylate were polymerized by a
solution-polymerizing process in isopropyl alcohol by using a
polymerization initiator. The obtained copolymer was modified with
12.5 parts of dinormal propylamine and the formed thermosetting
polymer was diluted with water to which malonic acid had been added
to adjust the resin solution concentration to 10 % by weight. At
this time, the pH was 4.0 and a substantially transparent solution
was obtained. Then 3.5 liters of this resin solution were put into
an electrodeposition tank (10 .times. 20 .times. 20 cm.). A carbon
rod of a diameter of 10 mm. was fixed as an anode to one end of the
tank. The bath solution temperature was made 25.degree.C., a
chromium-plated sheet (made by plating an iron sheet with copper 8
microns thick, bright nickel 8 microns thick and chromium 0.3
micron thick, the total thickness of the plated layer being smaller
than in the usual plating) of 1 dm..sup.2 was dipped in the bath as
the cathode. Then a direct current was passed through the bath by
the use of a constant voltage system. After the current was passed
at 50 volts for 1 minute, the coated article (cathode) was taken
out of the bath, water-washed and baked in a hot air drying oven at
170.degree.C. for 30 minutes to obtain a sheet with a uniform resin
coating having a pencil hardness of 2H, a film thickness of 5
microns and excellent appearance. Upon CASS Test (JIS D-0201), the
corrosion-resistance was rating number 10 in 4 cycles and rating
number 9 in 5 cycles. In contrast, when the resin-coating is not
effected the corrosion-resistance is less than rating number 9 in 2
cycles.
EXAMPLE 2
20 parts of dimethylaminoethyl methacrylate, 15 parts of
2-hydroxyethyl methacrylate, 25 parts of methyl methacrylate and 40
parts of 2-ethylhexyl acrylate were polymerized in isopropyl
alcohol by using an azo compound as a polymerization initiator to
obtain a solution of a copolymer (solids content 65 %).
30 % by weight of a 65 % solution of a blocked isocyanate and 70 %
by weight of the above prepared copolymer solution were well mixed
together and the mixture was diluted with water to which formic
acid had been added to adjust the resin solution concentration to
be 15 % by weight. At this time, the pH was 4.3 and the solution
was white-turbid. This resin solution was used as a bath
(25.degree.C.) in the same apparatus as in Example 1. A
chromium-plated sheet (made by plating an iron sheet with a copper
thickness of 8 microns, semi-bright nickel of a thickness of 5.5
microns, bright nickel of a thickness of 2.5 microns and chromium
of a thickness of 0.3 micron) of 1 dm..sup.2 was dipped in the bath
as the cathode. An electric current was passed therethrough by
means of a direct current constant voltage system. After the
current was passed at 70 volts for 1 minute, the resin-coated
article was taken out of the bath, water-washed and then baked in a
hot air drying oven at 160.degree.C. for 30 minutes to obtain a
sheet with a uniform resin coating having a pencil hardness of H, a
film thickness of 7 microns and excellent appearance. The
corrosion-resistance of the resulting sheet was of a rating number
of 9 in 4 cycles but the one not treated by the present method was
of a rating number of 9 in 2 cycles.
EXAMPLE 3
An iron-made bicycle lamp case of 3 dm..sup.2 was plated with a
thickness of 10 microns copper, bright nickel thickness of 6
microns and chromium thickness of 0.4 micron. Immediately
thereafter this article was subjected to anodic-electrolysis with 1
% solution of chromic acid at 25.degree.C. and an anode current
density of 0.5 ampere/dm..sup.2 for 40 seconds and was immediately
water-washed for 2 minutes to prepare an article having a modified
chromium-plated surface.
37 parts of glycidyl methacrylate, 17.5 parts of methyl
methacrylate and 37 parts of butyl acrylate were polymerized in an
ordinary manner in isopropyl alcohol by using an azo compound as a
polymerization initiator. Then 7.5 parts of diethanolamine were
reacted with the above prepared copolymer. 40 parts of ethylene
glycol monobutyl ether and 34 parts of 10 % acetic acid were added
to and well mixed with the resulting resin solution. Deionized
water was added to the resin solution to adjust the resin
concentration to 10 %. At this time, the pH of the solution was
5.0.
The above modified chromium plated article was subjected to the
electrodeposition in 3.5 liters of the above prepared bath at
20.degree.C. at a voltage of 75 volts for 1 minute in the same
apparatus as in Example 1. Then the article was water-washed for 1
minute and was dried and baked at 200.degree.C. for 30 minutes.
The hardness of the resulting film was 2 H, the appearance was
uniform, the adhesion was very high and the corrosion-resistance
was of rating numbers of 10, 10 and 9 respectively in 5, 7 and 9
cycles upon the CASS Test.
EXAMPLE 4
The same article and resin solution as in Example 2 were used and
the modification (or pretreatment) was conducted in the same manner
as in Example 3. Then the electrodeposition was conducted under the
same conditions as in Example 3 except that the temperature was
20.degree.C., voltage was 70 volts and the time was 1 minute. The
same excellent results as in Example 1 were obtained.
EXAMPLE 5
The same chromium-plated sample as in Example 3 was washed with
water for 1 minute and with hot water at 50.degree.C. for 1 minute
after the chromium-plating. Then the sample was left in air for 24
hours at 25.degree.C., was then subjected to the electrodeposition
in the same manner as in Example 3. Then the article was
immediately water-washed for 1 minute and was dried and baked at
200.degree.C. for 40 minutes.
The hardness of the resulting film was higher than 2 H and both
adhesion and appearance were excellent. The corrosion resistance
was of rating numbers 10 in 5 cycles and 9.5 in 7 cycles according
to the CASS Test.
EXAMPLE 6
The same chromium-plated sample as in Example 3 was used.
Immediately after the chromium-plating the sample was washed with
water for 1 minute and with hot water for 1 minute, and then heated
at 100.degree.C. for 30 minutes. Then the pretreated sample was
subjected to the cathodic-electro-deposition in the same bath and
under the same conditions as in Example 3. After the
electrodeposition, the sample was water-washed for 1 minute and was
dried and baked at 200.degree.C. for 30 minutes.
The hardness of the resulting film was 2 H and the adhesion and
appearance of the film was excellent. The corrosion-resistance was
of a rating number of 10 in 5 cycles according to the CASS
Test.
EXAMPLE 7
As an after-treating agent, 2,6-di-t-butyl-4-methyl phenol (a
phenolic antioxidant) was dissolved in ethylene glycol monobutyl
ether, and a water-soluble siliconic surace active agent was added
thereto and uniformly dissolved in the solution. Then the solution
was diluted with water so that the respective concentrations become
0.3 % of the antioxidant, 0.2 % of the surface active agent and 30
% of the organic solvent.
34.5 parts of glycidyl methacrylate, 17.2 parts of styrene and 34.5
parts of 2-ethylhexyl acrylate were polymerized in an ordinary
manner in 35 parts of isopropyl alcohol by using
azobisisobutyronitrile as a polymerization initiator. Then 13.8
parts of diisopropanolamine were added togeher with 18 parts of
ethylene glycol monobutyl ether to react with the obtained
copolymer.
30 parts of ethylene glycol monobutyl ether and 45 parts of 10 %
acetic acid were added to and well mixed with the above prepared
resin solution and deionized water was added thereto to adjust the
resin concentration to be 10 %. The pH at this time was 4.8. In the
apparatus in Example 1, an article to be coated (made by
nickel-chromium-plating a soft steel sheet and left for 24 hours in
air at 20.degree.C.) was used as the cathode and a carbon rod was
used as the anode. A direct current of a voltage of 70 volts was
passed through the cell at 20.degree.C. for 1 minute. A resin film
was electrodeposited on the chromium plated article. The article
was water-washed, was then dipped in the above mentioned
after-treating solution at 20.degree.C. for 30 seconds. The
after-treated article was then predried at50.degree. to
60.degree.C. for 5 minutes and was heat-treated at 200.degree.C.
for 30 minutes to obtain a cured resin coating film (thickness 5
microns). The article perfectly retained the metallic luster of the
chromium-plating, gave no painted sense and the surface pencil
hardness was 3 H.
For comparison the same procedure was repeated except that the
after-treatment was not conducted. The resulting resin film was
lightly yellowish on the surface and was a little lower in surface
smoothness.
EXAMPLE 8
As an after-treating agent, a peroxide decomposing agent and a
phenolic antioxidant were dissolved in diethylene glycol monobutyl
ether. An oil-soluble siliconic surface active agent and a nonionic
surface active agent were added thereto and uniformly dissolved in
the solution. Then the solution was diluted with water so that the
respective concentrations became 0.1 % of the peroxide decomposing
agent, 0.2 % of the antioxidant, 0.01 % of the siliconic surface
active agent, 0.1 % of the nonionic surface acetive agent
(oleylpolyethyleneglycolether) and 25 % of the organic solvent.
A direct current was passed at a voltage of 150 volts through the
same chromium-plated sheet in the same bath as in Example 7 at a
bath temperature of 25.degree.C. for 2 minutes. The resin-coated
sheet was water-washed, was dipped in the above mentioned
after-treating solution at 25.degree.C. for 2 minutes, was then
preheated at 80.degree. to 90.degree.C. for 5 minutes and was then
heat-treated or baked at 200.degree.C. for 30 minutes to obtain a
sheet with a uniform resin film (thickness about 25 microns) which
is excellent in the smoothness, and is substantially colorless and
has a pencil hardness of 2 H.
The same procedure was repeated except that the after-treatment was
not conducted. The resulting resin film was yellowish and had an
orange peel.
EXAMPLE 9
34.5 parts of glycidyl methacrylate, 17.2 parts of styrene and 34.5
parts of 2-ethylhexyl acrylate were polymerized together in an
ordinary manner in 35 parts of isopropyl alcohol in the presence of
an azo compound (polymerization initiator). Then 13.8 parts of
diisopropanolamine were added together with 18 parts of ethylene
glycol monobutyl ether to react with the above obtained
copolymer.
A commercial water-soluble melamine resin (alcohol ether of
melamine-formaldehyde condensate, solids content 70 %) was added to
the above prepared copolymer solution in such an amount that the
solids ratio (copolymer: melamine resin) is 75:25. Then 30 parts of
ethyleneglycol monobutyl ether and 45 parts of 10 % acetic acid
solution were added thereto and the mixture was diluted with
deionized water to prepare a resin solution (pH 4.9) with a resin
solids content of 10 %.
With the use of this resin solution the electro-deposition was
conducted in the same manner as in Example 7. After washing with
water the resin coated sample was dipped for 60 seconds at
20.degree.C. in an after-treating solution which is a 25 % aqueous
solution of ethyleneglycolmonobutylether and then dipped for 15
seconds at 20.degree.C. in a second after-treating solution which
was prepared by dissolving a phenolic antioxidant and a silicone
surfactant into a mixed solvent (ethyleneglycolmonobutyl ether 20
parts, ethyleneglycolmonoethyl ether 40 parts, n-butanol 20 parts
and isopropanol 20 parts), diluting the solution with water and
then adding trimellitic anhydride thereto. The concentrations of
various ingredients in the second after-treating solution were
organic solvents 50 %, antioxidant 0.2 %, surfactant 0.02 %, and
trimellitic anhydride 1.0 %.
After these after-treatments the coated sample was preheated at
70.degree.- 80.degree.C. for about 5 minutes and then baked at
180.degree.C. for 30 minutes to obtain a sheet with a resin coating
film (thickness 7 microns) having a surface pencil hardness of 3 H.
The chromium-plated surface luster was perfectly retained.
For comparison the same procedure was repeated excep that the
after-treatments were not conducted. The resulting resin film had a
surface pencil hardness of H - 2 H.
EXAMPLE 10
The copolymer prepared in Example 9 was modified by
diisopropanolamine in the same manner as in Example 9. The modified
resin was neutralized by 45 parts of 10 % acetic acid solution and
then diluted with deionized water to obtain a resin solution (resin
solids content 10 %, pH 4.8).
With the use of this resin solution the electro-deposition and
subsequent washing were conducted in the same manner as in Example
9. Then the coated sample was after-treated in the same manner as
in Example 9 except that the second after-treating solution
contained 0.5 % of dicyandiamide instead of 1.0 % of trimellitic
anhydride. After this after-treatment, the coated sample was
preheated at 70.degree.- 80.degree.C. for about 5 minutes and then
baked at 200.degree.C. for 30 minutes to obtain a sample with a
resin coating film (thickness 5 microns) having a surface pencil
hardness of 4 H. The luster of the chromium-plated surface was not
impaired by the coating.
For comparison the same procedure was repeated except that the
after-treatment was not conducted. The resulting resin film was
lightly yellowish and had a surface pencil hardness of 2H - 3H.
* * * * *