U.S. patent number 3,663,402 [Application Number 05/088,533] was granted by the patent office on 1972-05-16 for pretreating electrodepositable compositions.
This patent grant is currently assigned to PPG Industries, Inc.. Invention is credited to Roger M. Christenson, Robert R. Zwack.
United States Patent |
3,663,402 |
Christenson , et
al. |
May 16, 1972 |
PRETREATING ELECTRODEPOSITABLE COMPOSITIONS
Abstract
A method of pretreating electrodepositable compositions prior to
utilization of such compositions, in an electrodeposition process,
which comprises subjecting a synthetic resin ionically solubilized
in an aqueous medium to a selective separation process such as
ultrafiltration which passes an aqueous effluent through a physical
barrier while retaining the solubilized resin component. The method
enables the removal of deleterious impurities and contaminants
which affect coating parameters and thus provides a direct method
of controlling the quality of the deposited film.
Inventors: |
Christenson; Roger M.
(Gibsonia, PA), Zwack; Robert R. (New Kensington, PA) |
Assignee: |
PPG Industries, Inc.
(Pittsburgh, PA)
|
Family
ID: |
22211920 |
Appl.
No.: |
05/088,533 |
Filed: |
November 12, 1970 |
Current U.S.
Class: |
204/482 |
Current CPC
Class: |
C25D
13/24 (20130101); C25D 13/22 (20130101) |
Current International
Class: |
C25D
13/22 (20060101); C25D 13/24 (20060101); B01k
005/02 (); C23b 013/00 () |
Field of
Search: |
;204/181 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Williams; Howard S.
Claims
We claim:
1. In a method of electrodepositing a coating from an
electrodeposition bath to which there is continuously or
intermittently added a replenishment feed composition comprising an
aqueous, ionically solubilized synthetic resin component, the
improvement which comprises subjecting at least a portion of the
feed composition to an ultrafiltration processes wherein an
ultrafiltration membrane passes water and solute of substantially
lower molecular size than said resin component, while retaining
said resin component, adding the ultrafiltered feed composition to
the electrodeposition bath and subsequently electrodepositing a
coating from the bath.
2. A method as in claim 1 wherein the ultrafiltration process is
operated at a pressure gradient between about 10 and about 150 psi
and the ultrafiltration membrane has a flux rate of at least about
4.5 gallons per square foot per day.
3. A method as in claim 1 wherein said vehicle resin component
comprises an ionically solubilized synthetic resin.
4. A method as in claim 3 wherein said synthetic resin is a
polycarboxylic acid resin solubilized with a base.
5. A method as in claim 4 wherein the base is a water-soluble
amine.
6. A method as in claim 4 wherein the base is an alkali metal
hydroxide.
7. A method as in claim 3 wherein said synthetic resin comprises a
polybasic resin solubilized with an acid.
8. A method as in claim 1 wherein the feed composition is diluted
with water before being subjected to the ultrafiltration process.
Description
BACKGROUND OF THE INVENTION
In recent years electrodeposition has become a widely commercially
accepted coating technique. Coatings deposited electrically have
excellent properties for many applications. Electrophoretically
applied coating compositions are particularly useful when the
articles to be coated are of complex and unusual designs since the
structural configuration is ordinarily of little or no significance
when coating by this process. Film compositions applied by
electrodeposition do not run, drip, sag, or wash off during baking.
Virtually any electrically conductive surface may be coated by
electrodeposition. Treated and untreated metals such as iron,
steel, copper, zinc, brass, tin, nickel, chromium and aluminum are
among the most commonly employed substrates. Paper or other
non-conductive materials coated or impregnated with substances to
render them conductive under conditions of the coating may also be
employed as coating substrates.
In the electrodeposition process the articles to be coated are
immersed in an aqueous dispersion of a solubilized, ionized,
film-forming material, such as a synthetic organic vehicle resin.
The article to be coated serves as an electrode through which an
electric current passes to a counter-electrode, causing the
migration and the deposition of the vehicle resin on the charged
article. The articles containing the deposited films are then
withdrawn from the electrodeposition bath, usually rinsed and then
baked in the manner of a conventional finish.
It is known that in the electrodeposition process a delicate ionic
balance must be maintained in order to produce coating compositions
having uniform physical and chemical characteristics. If the ion
balance is not maintained, there may be a deleterious effect on
both operating parameters, as well as film qualities, for example,
a decrease in the efficiency of coating weight per unit of
electricity consumed and a decrease in throwing power are common.
Foreign ion contamination carry-over from the pretreatment section
contained on and in recessed areas and angled flanges of articles
to be coated have been a major source of contamination.
Contaminants such as phosphates, chromates, alkaline metal ions,
acids and the like have been carried over into the
electrodeposition bath, but the particular pretreatment
contaminants will depend somewhat on the type of pretreatment
employed.
Another source of contamination is the atmospheric air over the
electrodeposition bath, for upon exposure to air, CO.sub.2 is
absorbed into the aqueous bath composition. The dissolved CO.sub.2
is ordinarily present in the electrodeposition bath in the form of
carbonates.
Such contamination takes place during the electrodeposition
process, and because of the nature of the process, the contaminants
tend to accumulate and lead to increasing process difficulties. In
copending application Ser. No. 814,789, filed Apr. 9, 1969, now
abandoned, there is described a process in which ultrafiltration is
used to control the electrodeposition bath during the
electrodeposition process.
DESCRIPTION OF THE INVENTION
It has now been discovered that the paint composition used to fill
or feed an electrodeposition bath is itself a source of
contamination and that by subjecting at least a portion of an
electrodeposition bath to a selective separation process, the
contaminant content of such composition is thereby controlled. Upon
addition of such compositions to the electrodeposition bath as
initial fill material or as replenishment for the paint solids
consumed, such treated compositions thereby provide a bath
composition that when deposited produces films having unexpectedly
superior and uniform properties.
Contamination of depositable compositions, prior to utilization,
may be derived from various sources, for example, from the
manufacturing equipment; from the raw materials employed in
formulating the compositions, such as pigments and deionized water;
unreacted acids and monomers; free maleic anhydride, acrylic acid
or oxidized formaldehyde; and from the atmosphere over the
manufacturing container, whereby the composition may absorb carbon
dioxide which exists, for the most part, in the composition in the
form of carbonates; chloride ions which may also be absorbed from
the atmosphere if the composition is exposed to testing equipment
which releases salt spray vapors into the air, or from low purity
deionized water. All have a deleterious effect on bath operating
parameters and physical and chemical characteristics of the
deposited film. For example, rupture voltage decreases, throw power
decreases, conductivity of the bath increases, and the chemical
resistance of the cured film decreases.
In some instances, low molecular weight resin residues, such as
maleinized fatty acid residues, and the like, have also produced
undesirable coating conditions and film properties. Some pigments
have introduced water-soluble chromates and phosphates into the
bath which likewise have deleterious effect because they tend to
accumulate in the bath. Likewise, the solvent and solubilizing
agent concentration can be controlled by subjecting feed
composition to such a selective separation process. Various other
ions, solvents, components, ingredients, and the like may be
removed from the feed compositions or controlled to the extent
necessary to produce the desired product.
In addition to the advantages obtained by the use of the present
process as a precleaning technique, it also provides a method of
concentrating low solids feed compositions, thereby aiding in
control of the electrodeposition bath composition.
When subjecting a feed composition to ultrafiltration, it may be
convenient to dilute the composition with deionized water to aid in
handling and transfer. However, the need for prior dilution is
dependent on the viscosity of the particular composition employed,
the pressure, the type of ultrafilter membrane, and the flux rate
desired. If dilution of the feed composition is employed, it is
usually necessary to obtain an increased volume of ultrafiltrate to
compensate for such dilution addition.
As mentioned above, application Ser. No. 814,789 teaches that
ultrafiltration can be utilized to control an electrodeposition
bath composition during the electrodeposition process. While
exceptional control of a bath composition and removal of
objectional materials accumulated during the process has been
achieved by that process, by utilizing the ultrafiltration process
prior to employment of the compositions in the electrodeposition
process, in accordance with the present invention, the bath thereby
is even more readily controllable, as less contaminants are
introduced into the bath, and an overall process which is easily
practiced yet highly effective is achieved.
The selective filtration process employed in the process of the
instant invention is any process such as ultrafiltration which
separates water from the electrodeposition feed stock through a
physical barrier while retaining the solubilized resin components.
Thus, any means may be utilized which accomplishes this purpose.
Such a filter or barrier will pass not only water, but also solute
of substantially lower molecular weight than the vehicle resin such
as excess amine carbonates, low molecular weight solvent and simple
organic or inorganic anions and cations which may be present in the
feed composition. Examples of means for accomplishing this
separation are reverse osmosis, where water of high purity may be
obtained, and ultrafiltration, as well as other means which
accomplish the intended result. Because ultrafiltration is
particularly useful in controlling or removing contaminants from
feed stock compositions, or other depositable compositions prior to
utilization, ultrafiltration is especially preferred.
The ultrafiltration process separates materials below a given
molecular weight size from the composition. With the proper
selection of membranes, the treatment does not remove any product
or desirable resin from the feed stock composition, but does remove
soluble anionic, cationic and nonionic materials from the paint in
a ratio proportional to their concentration in the water phase of
the feed stock composition.
Ultrafiltration may be defined as a method of concentrating solute
while removing solvent, or selectively removing solvent and low
molecular weight solute from a significantly higher molecular
weight solute. From another aspect, it is a process of separation
whereby a solution containing a solute of molecular dimensions
significantly greater than the solvent is depleted of solute by
being forced under a hydraulic pressure gradient to flow through a
suitable membrane. The first definition is the one which most
fittingly describes the term "ultrafiltration" as applied to an
electrodeposition bath.
Ultrafiltration thus encompasses all membrane-moderated,
pressure-activated separations wherein solvent or solvent and
smaller molecules are separated from modest molecular weight
macromolecules and colloids. The term "ultrafiltration" is
generally broadly limited to describing separations involving
solutes of molecular dimensions below the limit of resolution of
the optical microscope, that is, about 0.5 micron.
The principles of ultrafiltration and filters are discussed in a
chapter entitled "Ultrafiltration" in the Spring, 1968, volume of
Advances in Separations and Purifications, E. S. Perry, Editor,
John Wiley & Sons, New York, as well as in Chemical Engineering
Progress, Volume 64, December 1968, pages 31 through 43.
The basic ultrafiltration process is relatively simple. Solution to
be ultrafiltered is confined under pressure, utilizing, for
example, either a compressed gas or liquid pump in a cell, in
contact with an appropriate filtration membrane supported on a
porous support. Any membrane or filter having chemical integrity to
the system being separated and having the desired separation
characteristic may be employed. Preferably, the contents of the
cell should be subjected to at least moderate agitation to avoid
accumulation of the retained solute on the membrane surface with
the attendant binding of the membrane. Ultrafiltration is
continually produced and collected until the retained solute
concentration in the cell solution reaches the desired level, or
the desired amount of solvent or solvent plus dissolved low
molecular weight solute is removed. A suitable apparatus for
conducting ultrafiltration is described in U.S. Pat. No. 3,494,465,
which is hereby incorporated by reference.
There are two types of ultrafiltration membrane. One is the
microporous ultrafilter, which is a filter in the traditional
sense, that is, a rigid, highly voided structure containing
interconnected random pores of extremely small average size.
Through such a structure, solvent (in the case of
electrodeposition, water) flows essentially viscously under a
hydraulic pressure gradient, the flow rate proportional to the
pressure difference, while dissolved solutes, to the extent that
their hydrated molecule dimensions are smaller than the smallest
pores within the structure, will pass through, little impeded by
the matrix. Larger size molecules, on the other hand, will become
trapped therein or upon the external surface of the membrane and
will thereby be retained. Since the microporous ultrafilters are
inherently susceptible to internal plugging or fouling by solute
molecules whose dimensions lie within the pore size distribution of
the filter, it is preferred to employ for a specific solute a
microporous ultrafilter whose mean pore size is significantly
smaller than the dimensions of the solute particle being
retained.
In contrast, the diffusive ultrafilter is a gel membrane through
which both solvent and solutes are transported by molecular
diffusion under the action of a concentration or activity gradient.
In such a structure, solute and solvent migration occurs via random
thermal movements of molecules within and between the chain
segments comprising the polymer network. Membranes prepared from
highly hydrophilic polymers which swell to eliminate standard water
are the most useful diffusive aqueous ultrafiltration membrane.
Since a diffusive aqueous ultrafilter contains no pores in the
conventional sense and since concentration within the membrane of
any solute retained by the membrane is low and time-independent,
such a filter is not plugged by retained solute, that is, there is
no decline in solvent permeability with time at a constant
pressure. This property is particularly important for a continuous
concentration or separation operation. Both types of filters are
known in the art.
The presently preferred ultrafilter is an anisotropic membrane
structure such as illustrated in FIG. 1. This structure consists of
an extremely thin, about 1/10 to about 10 microns, layer of a
homogeneous polymer 1 supported upon a thicker layer of a
microporous open-celled sponge 2, that is, a layer of about 20
microns to about 1 millimeter, although this dimension is not
critical. If desired, this membrane can be further supported by a
fibrous sheet, for example, paper, to provide greater strength and
durability. These membranes are used with a thin film or skin side
exposed to the high pressure solution. The support provided to the
skin by the spongy substrate is adequate to prevent film
rupture.
Membranes useful in the process are items of commerce and can be
obtained by several methods. One general method is described in
Belgian Pat. No. 721,058. This patent describes a process which, in
summary, comprises (a) forming a casting dope of the polymer in an
organic solvent, (b) forming a film of the casting dope, and (c)
preferentially contacting one side of said film with a diluent
having high compatibility with the casting dope to effect
precipitation of the polymer immediately upon coating the cast film
with the diluent.
The choice of a specific chemical composition for the membrane is
determined to a large extent by its resistance to the chemical
environment. Membranes can be typically prepared from thermoplastic
polymers such as polyvinyl chloride, polyacrylonitrile,
polysulfones, poly(methyl methacrylate), polycarbonates,
poly(n-butyl methacrylate), as well as a large group of copolymers
formed from any of the monomeric units of the above polymers,
including "Polymer 360", a polysulfone copolymer.
Some examples of specific anisotropic membranes operable in the
process of the invention include: Diaflow membrane ultrafilter
PM-30, the membrane chemical composition of which is a polysulfone
copolymer, Polymer 360, and which has the following permeability
characteristics:
---------------------------------------------------------------------------
Solute Retention Characteristics
Solute Molecular Weight Percent Retention
__________________________________________________________________________
Raffinose 594 0 Bacitracin 1,400 20 Cytochrome C 12,400 0 Myoglobin
17,800 65 Pepsin 35,000 85 Ovalbumin 45,000 95 Albumin 67,000 100
Dextran 110 110,000 20
---------------------------------------------------------------------------
Flow Rate--ml./min.
0.25% Pepsin (35,000 mw) Membrane Pressure Distilled In Distilled
Diameter psi Water Water (55 psi)
__________________________________________________________________________
25 mm. 55 8.6 1.1 150 mm. 55 350.0 46.0
__________________________________________________________________________
The membrane is chemically resistant to acids (HCl, H.sub.2
SO.sub.4, H.sub.3 PO.sub.4, all concentrates), alkalis, high
phosphate buffer and solutions of common salts as well as
concentrated urea and quanadine hydrochloride. The membrane is
solvent-resistant to alcohol, acetone and dioxane. The membrane is
not solvent-resistant to dimethylformamide or dimethyl sulfoxide.
This membrane is hereinafter referred to as "Membrane A."
Dorr-Oliver XPA membrane, the membrane chemical composition of
which is Dynel (an acrylonitrile-vinyl chloride copolymer) and
which has the following permeability characteristics:
% Flux Molecular Reten- (gal./sq.ft./day at Solute Weight tion 30
psi, 1.0% solute)
__________________________________________________________________________
Cytochrome C 12,000 50 100 .alpha. Chymotrypsinagen 24,000 90 22
Ovalbumin 45,000 100 45
__________________________________________________________________________
This membrane is hereinafter referred to as "Membrane B."
Dorr-Oliver BPA type membrane, the membrane chemical composition of
which is phenoxy resin (polyhydroxy ether) and which has the
following permeability characteristics:
% Flux Molecular Reten- (gal./sq.ft./day at Solute Weight tion 30
psi, 1.0% solute)
__________________________________________________________________________
Cytochrome C 12,600 50 30
this membrane is hereinafter referred to as "Membrane C."
The microporous ultrafilters are generally isotropic structures,
thus flow and retention properties are independent of flow
direction. It is preferred to use an ultrafilter which is
anisotropic in its microporous membrane structure, FIG. 2. In such
a membrane, the pore size increases rapidly from one face to the
other. When the fine-textured side 4 is used in contact with the
feed solution, this filter is less susceptible to plugging since a
particle which penetrates the topmost layer cannot become trapped
in the membrane because of the larger pore size 5 in the
substrate.
The process of the invention may be operated as either a batch or a
continuous process. In batch selective filtration or batch
ultrafiltration, a finite amount of material is placed in a cell
which is pressurized. A solvent and lower molecular weight solutes
are passed through the membrane. Agitation is provided by a
stirrer, for example, a magnetic stirrer. Obviously, this system is
best used for small batches of material. In a process requiring
continuous separation, a continuous selective filtration process is
preferred. Using this technique, material is continuously
recirculated under pressure against a membrane or series of
membranes through interconnecting flow channels, for example,
spiral flow channels.
Likewise, the ultrafiltration process may be conducted as either a
concentration process or a diafiltration process. Concentration
involves removing solvent and low molecular weight solute from an
increasingly concentrated retentate. Filtration flow rate will
decrease as the viscosity of the concentrate increases.
Diafiltration, on the other hand, is a constant volume process
whereby the starting material is connected to a reservoir of pure
solvent, both of which are placed under pressure simultaneously.
Once filtration begins, the pressure source is shut off in the
filtration cell and, thus, as the filtrate is removed, an equal
volume of new solvent is introduced into the filtration cell to
maintain the pressure balance.
Under ideal conditions, selected low molecular weight solutes would
be filtered as readily as solvent and their concentration in the
filtrate is equal to that in the retentate. Thus, for example, if a
material is concentrated to equal volumes of filtrate and
retentate, the concentration of low molecular weight solute in each
would be the same.
Using diafiltration, retentate solute concentration is not constant
and the mathematical relationship is as follows:
where C.sub.io is the initial solute concentration, C.sub.i is the
final solute concentration of the retentate, V.sub.s is the volume
of solute delivered to the cell (or the volume of the filtrate
collected), and V.sub.o is the initial solution volume (which
remains constant).
Electrodepositable compositions, while referred to as
"solubilized," in fact are considered a complex solution,
dispersion or suspension, or combination of one or more of these
classes in water, which acts as an electrolyte under the influence
of an electric current. While, no doubt in some circumstances the
vehicle resin is in solution, it is clear that in some instances
and perhaps in most the vehicle resin is a dispersion which may be
called a molecular dispersion of molecular size between a colloidal
suspension and a true solution.
The typical industrial electrodepositable composition also contains
pigments, crosslinking resins and other adjuvants which are
frequently combined with the vehicle resin in a chemical and a
physical relationship. For example, the pigments are usually ground
in a resin medium and are thus "wetted" with the vehicle resin. As
can be readily appreciated then, an electrodepositable composition
is complex in terms of the freedom or availability with respect to
removal of a component or in terms of the apparent molecular size
of a given vehicle component.
As applied to the process of this invention, ultrafiltration
comprises subjecting an electrodepositable composition to a
selective separation process before it has been employed in a
coating process. Initially such compositions are usually rich in
contaminants from the air, manufacturing equipment, raw materials
and the like. Thus, in order to preclean such compositions, an
ultrafilter, preferably a diffusive membrane ultrafilter, is
selected to retain the solubilized vehicle resin while passing
water and low molecular weight solute, especially those with a
molecular weight below about 1,000 and preferably below about 500.
As previously indicated, the filters discriminate as to molecular
size rather than actual molecular weight, thus these molecular
weights merely establish an order of magnitude rather than a
distinct molecular weight cut-off. Likewise, as previously
indicated, the retained solutes may, in fact, be colloidal
dispersions or molecular dispersions rather than true solutes.
In practice, a portion of the electrodepositable composition may be
continuously or intermittently removed and passed under pressure
created by a pressurized gas or by means of pressure applied to the
contained fluid in contact with the ultrafilter. Obviously, if
desired, the egress side of the filter may be maintained at a
reduced pressure to create the pressure difference.
The pressures necessary are not severe. The maximum pressure, in
part, depends on the strength of the filter. The minimum pressure
is that pressure required to force water and low molecular weight
solute through the filter at a measurable rate. With the presently
preferred membranes, the operating pressures are between about 10
and 150 psi, preferably between about 25 and 75 psi. Under most
circumstances, the ultrafilter should have an initial flux rate,
measured with the composition to be treated of at least about 3
gal./sq.ft./day (24 hours), the preferred flux rate being at least
about 4.5 gal./sq.ft./day.
As previously indicated, the bath composition should be in motion
at the face of the filter to prevent the retained solute from
impeding the flow through the filter. This may be accomplished by
mechanized stirring or by fluid flow with a force vector parallel
to the filter surface.
The retained solutes comprising the vehicle resin are then employed
to fill or replenish an electrodeposition bath. If desired, the
concentrate may be reconstituted by the addition of water either
before entry to the bath or by adding water directly to the
bath.
A number of electrodepositable resins are known and can be
pretreated in accordance with this invention. Virtually any
water-soluble, water-dispersible or water-emulsifiable vehicle
resin in an aqueous medium can be electrodeposited and, if
film-Forming, provides coatings which may be suitable for certain
purposes. The present invention is applicable to any such
material.
Presently, the most widely used electrodeposition vehicle resins
are ionically solubilized, synthetic resin vehicles. Numerous such
resins are described in U.S. Pat. Nos. 3,230,162; 3,441,489;
3,422,044; 3,403,088; 3,369,983; 3,366,563; 3,516,913 and
3,518,212. They include alkyd resins; modified or unmodified
adducts of drying oil or semi-drying oil fatty acid esters with a
dicarboxylic acid or anhydride, such as maleic anhydride adducts of
linseed oil, soybean oil, or the like, modified in some cases with
monomers such as styrene or a polyol; acrylic polymers, such as
acid-containing interpolymers of acrylic monomers, in many cases
including a hydroxyalkyl ester; mixed partial esters of fatty acids
with resinous polyols, such as polyols derived from epoxy resins or
sytrene-allyl alcohol copolymers; and others, including certain
phenolic resins, hydrocarbon resins, etc. Aminoplast resins,
usually made from condensation of melamine, urea, benzoquanamine or
the like with formaldehyde and etherified with an alcohol such as
methanol, butanol, hexanol or a mixture of alcohols, are also
useful, especially in combination with hydroxyl-containing alkyd or
acrylic resins.
In order to produce an electrodepositable composition from
polycarboxylic acid resins, it is necessary to at least partially
neutralize the acid groups present with a base in order to disperse
the resin in the aqueous electrodeposition bath. Inorganic bases
such as metal hydroxides, especially potassium hydroxide, can be
used, as can ammonia or organic bases such as amines. Water-soluble
amines are often preferred. Commonly used amines include
ethylamine, diethylamine, triethylamine, diethanolamine, and the
like.
Other base-solubilized polyacids which may be employed as
electrodeposition vehicles include those taught in U.S. Pat. No.
3,392,165, wherein the acid groups rather than being solely
polycarboxylic acid groups contain mineral acid groups such as
phosphonic, sulfonic, sulfate and phosphate groups.
The process of the instant invention is equally applicable to
cationic type vehicle resins, that is, vehicle resins which deposit
on the cathode. These include polybases solubilized by means of an
acid, for example, an amine-terminated polyamide or an acrylic
polymer solubilized with acetic acid. Other cationic polymers
include reaction products of polyepoxides with amino-substituted
boron esters and reaction products of polyepoxides with hydroxyl or
carboxyl-containing amines; many such products are described in
copending applications Ser. Nos. 772,366 (now abandoned) and
772,353, (U.S. Pat. No. 3,619,398) both filed Oct. 28, 1968, and
Ser. Nos. 840,847 and 840,848, both filed July 10, 1969 and now
both abandoned.
In addition to the vehicle resin, there may be present in the
electrodepositable compositions any desired pigment or pigment
composition, including practically any of the conventional types of
pigments employed in the art. There is often incorporated into the
pigment composition a dispersing or surface-active agent. Usually
the pigment or surface-active agent, if any, are ground together in
a portion of the vehicle, or alone in an aqueous medium, to make a
paste and this is blended with the vehicle to produce a coating
composition.
In many instances, it is preferred to add to the electrodeposition
bath certain additives to aid dispersibility, viscosity and/or film
quality, such as a nonionic modifier or solvent. There may also be
included additives such as anti-oxidants, wetting agents,
anti-foaming agents, fungicides, bactericides, and the like.
In formulating the coating compositions, ordinary tap water may be
employed, but where such water contains a relatively high level of
metals and cations, deionized water, i.e., water from which free
ions have been removed by the passage through ion-exchange resins,
is preferably employed.
The invention is further described in conjunction with the
following examples, which are to be construed as illustrative
rather than limiting. All parts and percentages in the examples and
throughout the specification are by weight unless otherwise
stated.
EXAMPLE I
The vehicle resin in this example was a maleinized tall oil fatty
acid ester of a styrene-allyl alcohol copolymer (Shell X-450) of
1,150 molecular weight and an average hydroxyl functionality per
mole of 5.2, comprising 38.5 percent of the copolymer, 55.5 percent
tall oil fatty acid, and 6.0 percent maleic anhydride, having an
acid value of 40.6 and a viscosity of 120,000 centipoises at 100
percent solids. It was employed with a black pigment paste made as
follows:
---------------------------------------------------------------------------
Black Paste A
Parts by Weight
__________________________________________________________________________
Anthracite (pigmentary) 62.5 Basic lead silicate 25.0 Manganese
dioxide 6.25 Strontium chromate 6.25
__________________________________________________________________________
The above pigments were ground in a 20 percent maleinized linseed
oil solution, employing 16.5 percent diethylamine as a solubilizing
agent and 1.0 percent cresylic acid as an anti-oxidant.
The electrodepositable composition was made from the following:
Parts by Weight
__________________________________________________________________________
Vehicle resin (above) 1368.0 Sorbitan monolaurate 129.5 (wetting
agent) Hexakis-(methoxymethyl)melamine 64.0 Cellosolve 68.5 Black
Paste A 1025.0 Deionized water 1790.0 Aqueous KOH solution 420.0
(15 percent solids content by weight)
__________________________________________________________________________
This composition had the following characteristics:
Solids Content Pigment-to- (Percent) pH Binder Ratio MEQ*/100 gm.
Solids
__________________________________________________________________________
46.25 8.95 0.23/1.0 69.0 *Milliequivalents of base
Of the above composition, 1,000 parts were reduced with 1,000 parts
of deionized water and the reduced composition was subjected to
ultrafiltration for 13 hours, utilizing "Membrane B," as
hereinabove described, at 50 psi.
During the 13 hours of ultrafiltration, 1,000 parts of
ultrafiltrate were collected; analysis of the ultrafiltrate showed
the following:
Solids content (percent) 1.15 CO.sub.2 (ppm) 236 CrO.sub.4 (ppm) 25
Ethyl Cellosolve (percent) 0.84 Diethylamine (percent) 0.03
Nitrogen (percent) 0.12
Electrodeposition of the thus treated composition is carried out
easily and efficiently, without encountering many of the problems
of unsatisfactory coating parameters and poor film properties often
found with corresponding untreated compositions. For example, it
had higher rupture voltage (420 versus 380), lower conductivity
(1,350 versus 1,700), and after 10 days stirring, the ultrafiltered
paint was still stable, while non-ultrafiltered paint had a rough,
patchy, poor appearance. Succeeding stability tests showed numerous
problems with the non-ultrafiltered paint when compared with the
ultrafiltered system.
EXAMPLE II
A white electrodepositable composition was produced utilizing the
following interpolymer, resin solution and paste:
---------------------------------------------------------------------------
Interpolymer A
Parts by Weight
__________________________________________________________________________
Hydroxyethyl methacrylate 8.7 Styrene 219.0 Methacrylic acid 131.0
Butyl acrylate 517.0 Di-tertiary butyl peroxide 13.2 Cumene
hydroperoxide 8.8 Butyl Cellosolve 306.0
Interpolymer A had the following characteristics:
Solids content (percent by weight) 74.4 Viscosity (centipoises)
90,000 Acid number 66.7 Resin Solution B
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Interpolymer A 100.0 Ethoxymethoxymethyl melamine* 18.5 (XM-1116)
Aqueous KOH solution (45 percent 5.3 solids content by weight)
Deionized water 184.2 *Ratio of ethoxy to methoxy groups about
60/40
Resin solution B was a thin clear fluid at 30 percent solids
content by weight.
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White Paste C
Parts by Weight
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Resin Solution B 208.0 Aqueous KOH solution (45 percent 5.3 solids
content by weight) Titanium dioxide 370.0 Deionized water 100.0
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The above composition was ground in a steel ball mill of the type
utilized widely in the art to produce a Hegman grind gauge reading
of 7.5. The ground White Paste C had the following properties:
Pigment Solids Resin Solids Content (percent) Content (percent) pH
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47.2 11.8 8.9
the electrodepositable composition had the following
composition:
Parts by Weight
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Acrylic Interpolymer A 584 Ethoxymethoxymethyl melamine* 108
Aqueous KOH solution (45 percent 31 solids by weight) Deionized
water 869 White Paste C 508 *Same as in Resin Solution B
the composition had the following characteristics:
Pigment-to-binder ratio 0.4/1.0 pH 8.0 Conductivity, .mu.mhos/cm.,
75.degree. F. 4080 MEQ/100 grams total 16.2 Total solids content
(percent) 41.8 Nitrogen content (percent) 1.16
The above composition was divided into two portions designated
Composition D and Composition E. Composition D was not
ultrafiltered, while Composition E was treated as follows:
To Composition E sufficient deionized water as added to reduce the
solids content to about 20 percent and this composition was then
subjected to ultrafiltration, utilizing Membrane B above, at 50 psi
for 10 hours. The collected ultrafiltrate and resulting concentrate
had the following characteristics:
Ultrafiltrate Concentrate
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pH 7.8 8.0 Conductivity, .mu.mhos/cm., 75.degree. F. 780.0 3890.0
MEQ/100 grams total 0.80 14.2 Total solids content (percent) 0.79
41.7 Nitrogen content (percent) 0.14 1.03 Butyl Cellosolve
(percent) 2.31 --
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To the concentrate (894 parts) there were added 6.6 parts of
ethoxymethoxymethyl melamine in 20.7 parts of butyl Cellosolve and
the mixture was agitated for 2 hours, then mixed with 2,879 parts
of deionized water, the said melamine and Cellosolve were added to
replace equivalent amounts extracted by ultrafiltration. The
treated composition had the following characteristics:
Conductivity, .mu.mhos/cm., 75.degree. F. 1040 MEQ/100 grams solids
34.5 MEQ/100 grams total 3.56 Solids content (percent) 10.30 pH
8.40
composition D was not subjected to ultrafiltration; it was reduced
to coating solids content by the addition of 2,891 parts of
deionized water, and had the following characteristics:
Conductivity 1170 MEQ/100 grams solids 36.2 MEQ/100 grams total 3.6
Solids content (percent) 9.95 pH 8.45
each of Composition D and E were electrodeposited on various
substrates to give a 1 mil thick film using comparable conditions,
and each coating baked at 350.degree. F. for 20 minutes. Generally,
Composition E had improved gloss and smoothness when compared to
Composition D.
The coatings were then evaluated for discoloration, using the
"Yellowness Index." "Yellowness Index" is measured by a
spectrophotometer or with a colorometer, following ASTM Method
D-1925 "Test for Yellowness Index of Plastics," 1968 Book of ASTM
Stendards, Part 27, and ASTM Method E-313-69, "Indexes of Whiteness
and Yellowness of Near-White, Opaque Materials," 1969 Book of ASTM
Standards, Part 21. The readings were as follows:
Yellowness Composition Substrate Index
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D Zinc phosphatized steel 4.31 E Zinc phosphatized steel 1.23 D
Iron phosphatized steel 10.43 E Iron phosphatized steel 6.49 D Zinc
phosphatized steel 2.68 (improved process) E Zinc phosphatized
steel .33 (improved process)
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As can readily be observed, the substrates coated with Composition
E, which was subjected to ultrafiltration, had much better color
retention in each instance than did those coated with Composition
D, which was not subjected to ultrafiltration.
Such control of the color of the deposited coating is of particular
importance in white and pastel electrodepositable compositions,
where discoloration is common and renders the product
unsatisfactory for use.
EXAMPLE III
In this example, there was employed a vehicle resin having the
following composition and characteristics:
Parts by Weight
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2-Ethylhexyl acrylate 30.0 Styrene 15.0 Methyl methacrylate 40.0
Acrylic acid 6.0 Hydroxyethyl methacrylate 9.0 Solids content
(percent by weight in isopropanol) 59.3 Viscosity (centipoises)
3250 Acid number 27.2
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In a manner similar to that in Example II, a white aqueous coating
composition was produced from the above vehicle resin, using a
mixed methyl and butyl ether of methylolated melamine, potassium
hydroxide solubilizing agent, and titanium dioxide pigment. The
coating composition had the following characteristics:
pH 7.9 Conductivity, .mu.mhos/cm., 75.degree. F. 1800 MEQ/100 grams
total 7.56 Solids content (percent 41.30
A portion of this composition ("Composition F") was mixed with
sufficient deionized water to reduce the solids content to about 20
percent and then subjected to ultrafiltration utilizing Membrane B
at 50 psi for 8 hours. The concentrate obtained is mixed as
follows:
Parts by Weight
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Concentrate (at 40.0 percent solids) 944.0 Mixed methyl, butyl
ether of methylolated melamine (90.8 percent solids content) 1.9
Isopropanol 43.4 n-Butanol 10.2 Mix for 2 hours. Deionized water
2800
Composition F then had the following characteristics:
pH 8.01 Conductivity, .mu.mhos/cm., 75.degree. F. 633 MEQ/100 grams
solids 17.2 MEQ/100 total 1.72 Solids content (percent) 10.01
A second portion (920 parts) of the above coating composition
("Composition G") was not subjected to the ultrafiltration process
and was reduced to coating solids content by the addition of 2,880
parts of deionized water.
Composition G then had the following characteristics:
pH 8.03 Conductivity, .mu.mhos/cm., 75.degree. F. 750 MEQ/100 grams
solids 18.9 MEQ/100 grams total 1.82 Solids content (percent)
9.61
Various substrates were coated by electrodeposition using each of
Compositions F and G, using voltages sufficient to obtain a cured
film thickness of 1.0 mil. Due to impurities, Composition G had
high current surges during the initial phases of the coating cycle
and dropped off sharply, when compared to the amperage curve of
Composition F.
The substrates having films deposited from Composition G (not
ultrafiltered) were completely unacceptable, as they were extremely
rough, discolored and had poor chemical and physical properties;
however, the films produced from Composition F (ultrafiltered)
produced smooth, undiscolored films having desirable chemical and
physical properties.
The contrast in the films was reflected in the gloss reading on the
various substrates employed.
Gloss, System Substrate 60.degree. Meter
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Composition G Zinc phosphatized steel 35 Composition F Zinc
phosphatized steel 54 Composition G Iron phosphatized steel 50
Composition F Iron phosphatized steel 70 Composition G Zinc
phosphatized steel 32 (improved process) Composition F Zinc
phosphatized steel 71 (improved process) Composition G Untreated
aluminum 15 Composition F Untreated aluminum 57
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The Yellowness Index reading of the substrates coated with
Compositions F and G showed a correlation similar to that displayed
by the Yellowness Index readings of the substrates coated in
Example II with those from Composition G being substantially
discolored.
In addition to the vehicles described in the examples, the process
described provides similar advantages when used with compositions
made from other vehicles, for example, alkyd resins prepared from
semi-drying or drying oils, esters of epoxides with fatty acids,
including esters of diglycidyl ethers of polyhydric compounds, as
well as other mono-, di- and polyepoxides; mixed esters of a
resinous polyol, such as resinous esters comprising mixed esters of
an unsaturated fatty acid adduct. Cationic resins, i.e., resins
which deposit on the cathode, can also be used in substantially the
same manner using known procedures.
It is also quite feasible to omit the
hexakis-(methoxymethyl)melamine, ethoxymethoxymethyl melamine or
mixed methyl, butyl ether of methylolated melamine, or where such a
material is desired to employ other crosslinking agents such as
N,N'-dimethyl urea, benzyl urea and benzoguanamine or the like may
be used instead.
The aqueous potassium hydroxide solutions employed as a
neutralizing agent in the above examples an readily be substituted
for other metal hydroxides such as lithium or sodium hydroxide, or
with an amine, preferably water-soluble, such as with
isopropanolamine, triethylamine, dimethylethanolamine, or the like.
Acidic solubilizing agents are employed in the case of polybasic
resins.
Also, the pigmentary components may be varied to produce a
particular color or to impart inhibitive properties to the film.
Color such as cadmium yellow, cadmium red, phthalocyanine blue,
chrome yellow, toluidine red, hydrated iron oxide and the like may
be included if desired. Other conventional type pigments employed
in the art may be added, for example, iron oxide, carbon black,
talc, barium sulfate and the like.
Various other components may be utilized to produce a desired
effect. Such components include, for example, wetting agents, flow
agents, fungicides, anti-oxidants, and the like.
In addition, it is also possible to substitute for "Membrane B"
either "Membrane A" or "Membrane C" and similar type membranes with
highly satisfactory results.
As described above, above, the method of the invention is
particularly applicable to the treatment of the feed composition
for an operating electrodeposition bath, where such feed
composition is intermittently or continuously added to the bath.
The feed composition can be the same as or somewhat different from
the composition used to fill the bath, and when treated using a
selective filtration process as described, prior to adding it to
the bath, greatly reduces the control problems normally associated
with operation of electrodeposition processes and maintains the
improved film properties illustrated by the foregoing examples. In
this embodiment of the invention, for example, a feed composition
is produced as in the above examples, ultrafiltered, and added to
the bath, using known procedures, as replenishment for the coating
composition removed by the coating process.
According to the provisions of the patent statutes, there are
described above the invention and what are now considered to be its
best embodiments. However, within the scope of the appended claims,
it is to be understood that the invention can be practiced
otherwise than as specifically described.
* * * * *