Treatment of metal with derivative of poly-alkenylphenol

A metal surface is treated by contacting the surface with a solution comprising an effective amount of a soluble or dispersible treatment compound selected from the group consisting of a polymer having the following general formula, acid salts thereof, and mixtures thereof: ##STR1## where: R.sub.1 through R.sub.3 are hydrogen or an alkyl group having from 1 to about 5 carbon atoms; PA1 each Y is hydrogen, Z, CR.sub.4 R.sub.5 OR.sub.6, CH.sub.2 Cl, or an alkyl or aryl group having from 1 to 18 carbon atoms; Z is ##STR2## R.sub.4 through R.sub.10 are hydrogen, or an alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl or phospho-alkyl moiety, said R.sub.4 through R.sub.10 being of carbon chain lengths up to a length at which the compound is not soluble or dispersible; and PA1 n is from 2 up to a number at which the polymer is not soluble or dispersible. Preferably, the solution is an aqueous solution and "Z" moieties are present in sufficient amount that the compound is water soluble or water dispersible. Metal surfaces contacted with the solution have enhanced corrosion resistance and paint adhesion characteristics.

BACKGROUND OF THE INVENTION 
The present invention relates to the art of metal surface treatment. More 
specifically, the present invention relates to treatment of metal surfaces 
with a solution of a poly-alkenylphenol derivative or an acid salt of a 
polyalkenylphenol derivative. The treatment imparts improved corrosion 
resistance and paint adhesion characteristics to the metal surfaces. 
The need for applying protective coatings to metal surfaces for improved 
corrosion resistance and paint adhesion characteristics is well known in 
the metal finishing and other metal arts. Traditionally, metal surfaces 
are treated with chemicals which form a metal phosphate and/or metal oxide 
conversion coating on the metal surface to improve the corrosion 
resistance and paint adhesion thereof. Also traditionally, the conversion 
coated metal surfaces have been rinsed or post-treated with a solution 
containing a hexavalent chromium compound for even greater corrosion 
resistance and paint adhesion. 
Because of the toxic nature of hexavalent chromium compounds, expensive 
treatment equipment must be used to remove chromates from plant effluent 
to prevent the pollution of rivers, streams, and drinking water sources. 
Hence, although the corrosion resistance and paint adhesion 
characteristics of conversion coated metal surfaces can be enhanced by an 
after-treatment solution containing a hexavalent chromium compound, in 
recent years there have been research and development efforts directed to 
discovering effective alternatives to the use of such post-treatment 
solutions. One alternative is provided in an earlier U.S. patent 
application of Andreas Lindert, Ser. No. 210,910 for "Composition for and 
Method of After-Treatment of Phosphatized Metal Surfaces" filed on Nov. 
28, 1980. The post-treatment compound of my earlier application is used in 
post-treatment solutions having an alkaline pH. It would, however, be 
desirable to have a post-treatment compound useful in post-treatment 
solutions over a broad ph range and, in particular, useful in an acidic 
post-treatment solution. 
In accordance with the present invention a novel composition which is an 
alternative to hexavalent chromium compound containing solutions is 
provided for use in post-treatment solutions in a novel process for the 
post-treatment of phosphatized or conversion coated metal surfaces. Also, 
the present invention provides a solution and method for treating 
previously untreated metal surfaces including aluminum, steel and zinc 
metal surfaces. The solution and method of the present invention provide a 
coating on the metal surface and are effective to enhance the corrosion 
resistance and paint adhesion characteristics of the metal surface whether 
previously conversion coated or not. Further understanding of this 
invention will be had from the following disclosure wherein all parts and 
percentages are by weight unless otherwise indicated. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, a metal surface is treated by 
contacting the metal surface with a solution comprising an effective 
amount of a soluble or dispersible treatment compound selected from the 
group consisting of a polymer having the following general formula, acid 
salts thereof, and mixtures thereof: 
##STR3## 
where: R.sub.1 through R.sub.3 are hydrogen or an alkyl group having from 
1 to about 5 carbon atoms; 
each Y is hydrogen, Z, CR.sub.4 R.sub.5 OR.sub.6, CH.sub.2 Cl, or an alkyl 
or aryl group having from 1 to 18 carbon atoms; 
Z is 
##STR4## 
R.sub.4 through R.sub.10 are hydrogen, or an alkyl, aryl, hydroxy-alkyl, 
amino-alkyl, mercapto-alkyl or phospho-alkyl moiety, said R.sub.4 through 
R.sub.10 being of carbon chain lengths up to a length at which the 
compound is not soluble or dispersible; and 
n is from 2 up to a number at which the polymer is not soluble or 
dispersible. 
The present invention also relates to preferred treatment solutions 
comprising the above treatment compound with Z moieties being present. 
Preferably, the solution is an aqueous solution and Z moieties are present 
in sufficient amount that the compound is water soluble or water 
dispersible. 
A metal surface contacted with a solution comprising the aforementioned 
treatment compound has enhanced corrosion resistance and paint adhesion 
characteristics. 
DETAILED DESCRIPTION OF THE INVENTION 
Although the solution of the invention can be effectively applied to 
treated or untreated metal surfaces, generally speaking the best results 
will be obtained if the metal surface has previously been conversion 
coated. Conversion coatings are well known and have been described, for 
example, in Metal Handbook, Volume II, 8th Edition, pages 529-547 of the 
American Society for Metals and in Metal Finishing Guidebook and 
Directory, pages 590-603 (1972), the contents of both of which are 
specifically incorporated by reference herein. 
In a typical metal treatment operation employing a composition and process 
of this invention, the metal to be treated is initially cleaned by a 
chemical or physical process and water rinsed to remove grease and dirt 
from the surface. The metal surface is then brought into contact with the 
treatment solution of this invention. Alternatively, instead of applying 
the treatment solution following the cleaning process, a conversion 
coating solution is applied to the metal surface in a conventional manner 
to form a conversion coating thereon. The conversion coated surface is 
then water rinsed and the metal surface is immediately brought into 
contact with the treatment solution of the present invention. 
The present invention is useful with a broad range of metal surfaces, 
including metals having surfaces which have been conversion coated with 
suitable conversion coatings such as iron phosphate, manganese phosphate, 
zinc phosphate, zinc phosphate modified with calcium, nickel, or magnesium 
ions, mixed metal oxide, and titanium or zirconium organometallic 
coatings. Examples of suitable metal surfaces include zinc, iron, aluminum 
and cold-rolled, ground, pickled, and hot-rolled steel and galvanized 
steel surfaces. As used herein, the term "metal surface" includes both 
untreated metal surfaces an conversion coated metal surfaces. 
In accordance with the method of the present invention a metal surface is 
treated by contacting the metal surface with a solution comprising a 
treatment solution of the present invention. The treatment solution 
comprises an effective amount of a soluble or dispersible treatment 
compound selected from a polymer having the following general formula, 
acid salts thereof and mixtures thereof: 
##STR5## 
where: R.sub.1 through R.sub.3 are hydrogen or an alkyl group having from 
1to about 5 carbon atoms; 
each Y is hydrogen, Z, CR.sub.4 R.sub.5 OR.sub.6, CH.sub.2 Cl, or an alkyl 
or aryl group having from 1 to 18 carbon atoms; 
Z is 
##STR6## 
R.sub.4 through R.sub.10 are hydrogen, or an alkyl, aryl, hydroxy-alkyl, 
amino-alkyl, mercapto-alkyl or phospho-alkyl moiety, said R.sub.4 through 
R.sub.10 being of carbon chain lengths up to a length at which the 
compound is not soluble or dispersible; and 
n is from 2 up to a number at which the polymer is not soluble or 
dispersible. 
Preferably the treatment solution has Z moieties present. Also preferably 
the treatment solution is an aqueous solution and Z moieites are present 
in sufficient amount that the compound is water soluble or water 
dispersible. 
While the alkyl groups of the polymer backbone or chain in the above 
formula can be located in the ortho, meta, or para positions to the 
hydroxyl group on the aromatic ring of the phenol, monomer units of the 
above general formula are preferably selected from the para and ortho 
forms. 
It will be appreciated that in the polymeric form, the treatment compound 
of the present invention can comprise a plurality of different specific 
monomer units each of the above general formula. For example, a polymeric 
compound of this invention can have the following general formula: 
##STR7## 
where y is defined as above (but is not hydrogen) and wherein A, B, C, and 
D can be from 0 to a number at which the polymer is not soluble or 
dispersible in the solvent under the conditions of use. A+B+C+D must be at 
least 2 and if the water is the solvent then the methylene amine moiety, 
the Z moiety as defined above, must be present in sufficient amount so 
that when neutralized with an acid, the polymer is water soluble or water 
dispersible. The particular amount as a molar percent needed for water 
solubility or dispersibility depends upon the molecular weight of the 
polymers as well as the particular R.sub.4 through R.sub.10 moieties in 
the polymer. Generally speaking, the molar percent of amino group or Z per 
phenolic group may vary from 10% to 200% and is usually 50% to 150%; there 
being one phenolic group per monomer. 
It will, of course, be appreciated that the treatment compound of the 
present invention is based on derivatives of poly-alkenylphenol polymer. 
Examples of poly-alkenylphenols or substituted alkenylphenols useful in 
the present invention include isopropenylphenol, isobutenylphenol, 
dimethylvinylphenol and the like. Suitable derivatives having the above 
general formula can be made, for example, by the Mannich Reaction. For 
example, a poly-4-vinylphenol polymer can be reacted with formaldehyde and 
a secondary amine to yield a product which can be neutralized with an 
organic or inorganic acid to yield a water soluble or dispersible solution 
or emulsion of the treatment compound of this invention. 
The molecular weight of the poly-alkenylphenol used in the preparation of 
derivatives claimed in the present invention can range from the dimer, or 
more usually low molecular weight oligomers of 360 to high molecular 
weight polymers of 30,000 or greater. The upper limit of molecular weight 
being determined by the functional limitation that the derivative 
therefrom be soluble or dispersible. 
The resulting derivatives of the formula set forth hereinabove will 
typically have a molecular weight of up to about 200,000 with molecular 
weights within the range of about 700 to about 70,000 being preferred. In 
the formula given for these derivatives, a typical upper value for "n" is 
about 850, with values of from about 10 to 300 being preferred. Similarly, 
the carbon chain lengths of the R.sub.4 through R.sub.10 substituents will 
typically be from about 1 to 18, with carbon chain lengths of from about 1 
to 12 being preferred. It will, of course, be appreciated, that in each 
instance, a value for "n" and for the carbon lengths, as well as the 
percent of the "Z" moiety, will be selected which will provide the desired 
amount of solubility and/or dispersibility. 
The treatment compounds of this invention are soluble in organic solvents 
and can be used as a treatment solution when dissolved in an organic 
solvent as, for example, ethanol. Advantageously, however, the treatment 
compounds can also be used in aqueous solution. To provide water 
solubility or water dispersibility of the compound, an organic or 
inorganic acid can be used for neutralization of the "Z" moiety thereof. 
Useful acids for this purpose are acetic acid, citric acid, oxalic acid, 
ascorbic acid, phenylphosphonic acid, chloromethylphosphonic acid; mono, 
di and trichloroacetic acid, trifluoroacetic acid, nitric acid, phosphoric 
acid, hydrofluoric acid, sulfuric acid, boric acid, hydrochloric acid, 
hexafluorosilicic acid, hexafluorotitanic acid, hexafluorozirconic acid, 
and the like; alone or in combination with each other. The addition of 
water to the neutralized, overneutralized or partially neutralized 
treatment compounds mentioned above results in a water soluble or 
dispersible solution or emulsion of the polymer useful for metal 
treatment. 
The pH of the aqueous solution can vary from pH 0.5 to 12, but for 
practical purposes is usually kept between 2.0 to 8.0 both for the 
stability of the solution and for best results on the treated metal 
surface. 
It is contemplated that the treatment compound of the present invention 
will generally be used in a working solution at a dilute concentration of, 
for example, from about 0.01% to about 5% by weight. Practically speaking, 
a concentration of 0.025% to 1% is preferred in a working solution. 
However, under some circumstances, for example, for transporting or 
storing the solution, a concentrate of the solution may be preferred. 
Also, it is contemplated that the treatment solution may comprise a 
pigment i.e., be a paint composition having a film forming component which 
can be the treatment compound itself, a solvent, and an organic or 
inorganic pigment. 
Of course, the treatment solution of the present invention can also 
comprise ingredients in addition to the treatment compound. For example, 
the treatment solution may optionally comprise, in addition to the 
treatment compound, from about 0.001% to about 1.0% of a metal ion 
selected from the group consisting of titanium, zirconium and hafnium ions 
and mixtures thereof. It will be appreciated that these ions are of Group 
IV B transition metals of the Periodic Table of the Elements and may be 
provided in aqueous solution by the addition of their water soluble acids 
or salts, for example, hexafluorotitanic acid, hexafluorozirconic acid, 
hexafluorohafnic acid, or the nitrate, sulfate, fluoride, acetate, 
citrate, and/or chloride salts. Use of such additional metal ions can 
improve both the effectiveness or performance of the treatment solution in 
use and also can reduce the time of application of treatment solution to 
the metal surface to as short a time as from about 2 to about 5 seconds, 
as may be required for use on a coil line. 
Still other optional ingredients may be employed in addition to, or instead 
of, the aforementioned metal ions. For example, in addition to the 
treatment compound and a metal ion selected from this group consisting of 
titanium, zirconium, and hafnium ions and mixtures thereof, the treatment 
solution can comprise from about 0.01% to about 4.0% of ingredients 
selected from the group consisting of thiourea, alkyl or aryl thiourea 
compounds, tannic acid, vegetable tannins or gall tannins and mixtures 
thereof. Examples of suitable ingredients include methyl, ethyl or butyl 
thiourea, wattle, mangrove or chestnut tannins, oak gall tannin, and 
valonea acorn cup extract. 
Application of the treatment solution of the present invention in the 
treatment step to a metal surface can be carried out by any conventional 
method. While it is contemplated that the metal surface will preferably be 
a conversion coated metal surface, the treatment step an alternatively be 
carried out on an untreated metal surface to improve the corrosion 
resistance and paint adhesion thereof. For example, the treatment solution 
can be applied by spray coating, roller coating, or dipping. The 
temperature of the solution applied can vary over a wide range, but is 
preferably from 70.degree. F. to 160.degree. F. After application of the 
treatment solution to the metal surface, the surface can optionally be 
rinsed, although good results can be obtained without rinsing after 
treatment. For some end uses, for example, in electrocoat paint 
application, rinsing may be preferred. 
Next, the treated metal surface is dried. Drying can be carried out by, for 
example, circulating air or oven drying. While room temperature drying can 
be employed, it is preferable to use elevated temperatures to decrease the 
amount of drying time required. 
After drying, the treated metal surface is then ready for painting or the 
like. The surface is suitable for standard paint or other coating 
application techniques such as brush painting, spray painting, 
electro-static coating, dipping, roller coating, as well as 
electrocoating. As a result of the treatment step of the present 
invention, the conversion coated surface has improved paint adhesion and 
corrosion resistance characteristics. Further understanding of the present 
invention can be had from the following illustrative examples.

EXAMPLE 1 
100 lbs. of 95% ethanol solvent was charged into a 100 gallon stainless 
steel reactor containing a turbine blade, nitrogen sparge and condenser. 
Gentle heating to 50.degree. C. was started, and 80 lbs. of 
poly-4-vinylphenol polymer of a molecular weight of 5000 was slowly added 
to the solvent with good stirring. After all of the polymer was added, the 
reactor was closed and heated to 80.degree. C. to aid in dissolving the 
remaining polymer. The reactor was then cooled to 40.degree. C. and 50 
lbs. of N-Methylaminoethanol and 100 lbs. of deionized water were added. 
Then over one (1) hour 54.1 lbs. of 37% formaldehyde solution was added 
while maintaining the temperature at 40.degree. C. to .+-.2.degree. C. The 
reactor was then heated for 3 hours at 40.degree. C. and 315 lbs. of 10% 
nitric acid was added and diluted to 10% solids with deionized water to 
yield a solution of a treatment compound of the present invention in 
water. 
EXAMPLE 2 
100 g. of cellosolve solvent was charged into a reactor which was a 1000 ml 
reaction flask equipped with a condenser, nitrogen sparge, overhead 
mechanical stirrer and thermometer. Then 80 gm of poly-4-vinylphenol 
having a molecular weight of 5000 was added and dissolved. 70 gm of 
diethanolamine and 100 gm of deionized water were added and reaction 
heated to 50.degree. C. 108 gm of 37% formaldehyde solution was added over 
1 hour and heated an additional 3 hours at 50.degree. C. and then 3 hours 
at 80.degree. C. The reaction was cooled and 65 gm of 75% phosphoric acid 
and then 227 gm of deionized water was added. The product gave a stable 
solution of a treatment compound of the present invention in water. 
EXAMPLE 3 
A cold rolled steel 24 gauge panel which had been oiled to prevent 
corrosion in shipping was cleaned with mineral oil and then further 
cleaned using an aqueous solution of a strong alkaline cleaner (sold under 
the trademark CO.RTM. Cleaner 338 by KER SURFACE TREATMENT PRODUCTS, 
OCCIDENTAL CHEMICAL CORP.) by a spray application at 150.degree. F. 
solution temperature for 60 seconds; followed by the application of an 
iron phosphate conversion coating (sold under the trademark BONDERITE.RTM. 
1014 by KER SURFACE TREATMENT PRODUCTS, OCCIDENTIAL CHEMICAL CORP.) for 
60 seconds at 110.degree. F. After the conversion coating treatment, the 
panels were rinsed with cold tap water for 30 seconds and then treated 
with a 0.5% solution of the compound of Example I for 30 seconds at a 
110.degree. F. solution temperature by a spray application. The panels 
were then rinsed and dried in an oven at 350.degree. F. for 5 minutes. 
The panels were painted with a standard Duracron.RTM. 200 paint (from PPG 
Industries) and tested by the standard salt spray method. (ASTM.COPYRGT. 
B-117-61.) After 504 hours, the panels treated with Example I as described 
above gave results equivalent to the standard chromium treated control 
panels. 
EXAMPLE 4 
The procedure of Example 1 was carried out except that after adding 54.1 
lbs. of 37% formaldehyde solution, the reaction was then heated for 3 
hours at 80.degree. C. and 326 lbs. of 10% phosphoric acid was added and 
the reactor contents were diluted to 10% solids with deionized water to 
yield a stable solution of a treatment compound of the present invention 
in water. 
EXAMPLE 5 
Cold rolled steel panels were cleaned using a strong alkaline cleaner and 
the cleaned metal surface was then rinsed with hot water. An iron 
phosphate conversion coating (BONDERITE.RTM. 1000 made by KER SURFACE 
TREATMENT PRODUCTS, OCCIDENTAL CHEMICAL CORP.) was then applied at 
160.degree. F. by spray application and the panels were rinsed with cold 
water before application of the post-treatment. Dilute solutions of the 
poly-4-vinylphenol derivatives prepared as in Example 4 were mixed with 
hexafluorotitanic acid and applied to the phosphate metal at 120.degree. 
F. Concentration of the poly-4-vinylphenol derivatives and 
hexafluorotitanic acid content was varied from 0.05 to 0.2% and 0.06 to 
0.03% respectively. Some of the post-treated panels were water rinsed 
others were not rinsed. All panels were then baked in a 350.degree. F. 
oven for 5 minutes. Control panels of COLENE.RTM. 60 chromium rinse 
were employed. 
The above prepared panels were painted with an anodic electrocoat paint 
system, Powercron.RTM. acrylic electrocoat of PPG Industries, at 120-140 
volts for 60-90 seconds at 80.degree. F. in order to obtain a uniform 
coating appearance and thickness of 0.95-1.00 mils. Cure of the coating 
was at 325.degree. F. peak metal temperature for 20 minutes. The panels 
were scribed from corner to corner with an X using a sharp knife and all 
the way to the bare metal. The panels were subjected to standard salt fog 
tests in accordance with ASTM B117-61 and compared with chromate treated 
as well as deionized rinsed controls. Results equivalent to COLENE.RTM. 
60 activated chromium rinse control (made by KER SURFACE TREATMENT 
PRODUCTS, OCCIDENTAL CHEMICAL CORP.) were obtained with the 
poly-4-vinylphenol derivative of 0.1% concentration with hexafluorotitanic 
acid at 0.03% concentration in the treatment bath. or complex oxide type. 
Samples of the substrates prepared as described above were then given a 10 
second final rinse with one of the following final rinses: 
Final Rinse No. 1. Modified chromic acid (Parcolene.RTM. 62 made by KER 
SURFACE TREATMENT PRODUCTS, OCCIDENTAL CHEMICAL CORP.) 
Final Rinse No. 2. Deionized water. 
Final Rinse No. 3. Aqueous solution of 0.25% by weight of an acid salt of a 
poly-4-vinylphenol derivative, pH 6.0 prepared as in Example 4. 
Final Rinse No. 4. Aqueous solution of 0.25% by weight of the acid salt of 
poly-4-vinylphenol derivative as in number 3 above and 0.015% by weight of 
titanium ions, added as H.sub.2 TiF.sub.6, pH 6.1. 
The panels were then painted with one and two-coat paint systems: 
______________________________________ 
Paint 1 Glidden 71308 PolyLure 2000 
white polyester 
Paimt 2 M & T black vinyl 
Paint 3 Midland white polyester 
Paint 4 Midland-Dexter 9 .times. 165 
epoxy primer 
Midland-Dexter 5 .times. 121 
crystal white 
Dexstar .RTM. polyester topcoat 
______________________________________ 
The panels were then scribed and subjected to standard ASTM B-117-61 5% 
salt fog tests, ASTM 2247-64T humidity tests and 180.degree. T-bend 
adhesion test as described in ASTM D3794-79. The results are set forth 
below: T-bend adhesion test as described in ASTM D3794-79. The results are 
set forth below: 
__________________________________________________________________________ 
5% Salt Fog Results 
Final 
Iron Phosphate 
Zinc Phosphate 
Complex Oxide 
Rinse 
Paint 1 
Paint 2 Paint 3 
Paint 4 
Paint 3 Paint 4 
No. 192 Hr. 
192 Hr. 504 Hr. 
1008 Hr. 
504 Hr. 1008 Hr. 
__________________________________________________________________________ 
1 1-1.sup.4s 
0-1.sup.s 
FM9 R9 
0-1 VF + 8 
0-3.sup.7s 
55% P MD6 
0-1 
1 0-1.sup.s 
0-1.sup.s 
FM9 R8.5 
0-1 VF + 8 
0-1.sup.3s 
55% P MD6 
0-1 
2 70% P 
0-1.sup.s 
D9 R5 3-9.sup.11s F8 
2-5.sup.7s 
85% P (192 Hr.) 
7-12.sup.14s VF + 8 
2 70% P 
N D9 R5 4-8.sup.11s F6 
2-4.sup.8s 
80% P (192 Hr.) 
40% P 
3 1-2.sup.3s 
0-1.sup.s 
D9 R5 1-2.sup.3s MD9 
1-2 1-3.sup.6s MD6 
0-1 F9 
3 1-1 0-1.sup.s 
D9 R6 1-2.sup.5s MD9 
1- 2.sup.4s 
4-13MD6 2% P 
0-1.sup.2s VF + 9 
4 2-3 N D8 R5 0-1.sup.s MD9 
0-1.sup.2s 
0-1 MD8 0-1.sup.s VF9 
4 2-3.sup.4s 
0-1.sup.s 
D9 R5 0-1.sup.s MD9 
0-1 0-1 MD9 0-1.sup.4s VF + 9 
__________________________________________________________________________ 
VF = very few, F = few, FM = fewmedium, MD = mediumdense, D = dense, % P 
% peel, R = red rust, s = spot, N = nil. 
Reported above is the creepback from the scribe, the amount of blistering, 
and red rust ratings. The creepback from the scribe produced by the final 
rinses containing the polymer is substantially less than that of the 
deionized water final rinse. With the added titanium, the creepback from 
the scribe with the polymer rinse is less than that of the chromic acid 
rinse in at least four out of the six cases. 
The humidity results for the iron phosphate coated panels rinsed as above 
were essentially equivalent. The adhesion at a 180.degree. T-bend for the 
polymer-containing rinses was at least equal to that for the chromic acid 
rinse, and generally better. 
EXAMPLE 7 
Panels were treated as in Example 6, except that the treatment time was 
reduced to 5 seconds. Excellent results as compared to chromic acid 
post-treatments were obtained on zinc phosphate and complex metal oxide 
conversion coatings but slightly weaker results were obtained on iron 
phosphate when a solution of poly-4-vinylphenol derivative prepared as in 
Example 4 was used at 0.1% concentration along with .02% hexafluorotitanic 
acid at a treatment bath ph of 5.1. Improved corrosion resistance resulted 
by doubling the concentration in the treatment bath of the 
poly-4-vinylphenol derivative and hexafluorotitanic acid, as well as 
incorporation of 0.2% thiourea and 0.05% tannic acid in the above 
formulation. 
EXAMPLE 8 
Cleaned aluminum panels were treated with BONDERITE.RTM. 787 treatment (a 
chrome-free conversion coating of KER SURFACE TREATMENT PRODUCTS, 
OCCIDENTAL CHEMICAL CORP.) After rinsing with cold water one set of panels 
was rinsed with COLENE.RTM. 88 (a chrome-free rinse from KER SURFACE 
TREATMENT PRODUCTS, OCCIDENTAL CHEMICAL CORP.) and the other set was 
rinsed with a post-treatment as prepared in Example 4. 
After rinsing the panels were run through squeegee rolls to remove excess 
solution. Chrome controls were prepared using BONDERITE.RTM. 722 treatment 
and a final COLENE.RTM. 10 rinse (both from KER SURFACE TREATMENT 
PRODUCTS, OCCIDENTAL CHEMICAL CORP.) After the COLENE.RTM. 10 rinse, 
the panels were also run through squeegee rolls. 
The treated panels were painted with two single coat systems. 
1. Hanna Paint--Hickory Brown Polyester XR8298D 
2. DuPont Paint--White acrylic 884-5001 Lucite 2100 Series 
The painted aluminum panels were subjected to acetic acid salt spray for 
504 hours. Ratings were made after each 168 hours by tape pulling at the 
scribed area and observing for loss of paint, general blistering and edge 
creepage. The following ratings were observed after 504 hours: 
______________________________________ 
B787 
Poly-4-Vinyl- 
B787 phenol Derivatives 
B722 
Treatment 
+PLN 88 as in Example 4 
+PLN 10 
______________________________________ 
Hanna Paint 
E D6, D8 E 0-1.sup.s, D9 
E 0-1.sup.s 
S 7-10, D6 S 0-2.sup.s, D9 
S 0-2.sup.s 
5% P D8 0-1.sup.s F9 0-1.sup.s F9 
DuPont Paint 
E D6 E MD9, D9 E 0-2.sup.s 
0-3.sup.s 
S 0-2.sup.s, 
S 0-1.sup.s, MD9 
S 0-2.sup.s, 
3% P, D6 1% P M9 1% P, VF9 
0-2.sup.s, 0-1.sup.s, 
4% P, D6 3% P, VF.sup.+9 
______________________________________ 
E = Edge Rating, S = Scribe Rating 
The salt spray results as measured by creepage from the scribe and 
blistering indicate that aluminum panels treated with BONDERITE.RTM. 787 
treatment and post-treated with poly-4-vinylphenol derivative of Example 4 
is as good as or better than BONDERITE.RTM. 722 treatment plus 
COLENE.RTM. 10 control system. 
EXAMPLE 9 
Panels were treated as in Example 5 except each panel was given a 5 second 
final rinse with one of the solutions below: 
__________________________________________________________________________ 
CO- 
LENE .RTM. 62 
Poly-4- Modified 
Final 
VinylPhenol Chromic 
Rinse 
Derivative 
H.sub.2 Ti F.sub.6 
Thiourea 
Tannic Acid 
Acid 
No. Wt. % Wt. % 
Wt. % 
Wt. % Wt. % pH 
__________________________________________________________________________ 
1 0.4 2.9 
2 0.1 0.02 5.1 
3 0.2 0.04 0.2 0.05 3.6 
__________________________________________________________________________ 
The panels were painted and tested as above. The results with Rinse No. 2 
were better than or equal to those with Rinse No. 1, the chromic acid 
control, except with the iron phosphate system, where the results were 
good, but somewhat weaker than with the chromic acid control. The results 
with Rinse No. 3 were better than or equal to those with Rinse No. 2. 
While the above disclosure sets forth and describes various embodiments of 
the present invention, the compositions and methods described are intended 
to illustrate but not limit the present invention, it being understood 
that the specific embodiments described herein are subject to variation 
and modification by one skilled in the art having benefit of the foregoing 
disclosure. Therefore, it is intended that the scope of the present 
invention is to be limited solely by the following claims.