CA1267746A - Treatment of metal with derivative of poly- alkenylphenol - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
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:

where:
R1 through R3 are hydrogen or an alkyl group having from 1 to about 5 carbon atoms;
each Y is hydrogen, Z, CR4R5OR6, Ci2C1, or an alkyl or aryl group having from 1 to 18 carbon atoms;

R4 through R10 are hydrogen or an alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl or phospho-alkyl moiety, said R4 through R10 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 polymer is not soluble or dispersible ;

with the proviso that R1, R2 and R3 cannot simultaneously represent hydrogen when the substituted vinyl group is para to the hydroxyl moiety.

Description

7~--146 IRE~lYENr OF MET~L hITH
DERIVAlIVE-OF PoLY-~LRæ~hLEIENOL

CF ~E ~CN

The present inNentiOn relates to the art of metal surfaoe treatment. More specifically, the present invention relates to treat~ent of metal surfaces with a solution of a - poly-aLkenylphenol derivative or an acid salt of a poly-alke~ylphenol derivative. The treatment imparts improved corrosion resistan oe a~nd paint adhesion characteristics to the metal surfa oe s.
The need for applying protective ooatings to metal surfa oes for improved col~usian resistanoe and paint adhesion characberistics is wel1 kncwn in the metal finishing and other metal arts. Traditionally, metal surfaoe s are treated with chemicals which form a metal phosphate and/or metal oxide oonversion coating on the metal surfa oe to improve the oorrosion resistance and Faint adhesion thereof. Also traditionally, the COnversiQn coated metal surfaces have been rinsed or post-treated with a solutian containin~ a hexavalent chromium compound for even greater oorrosion resistance and Faint adhesion.
Because of the toxic nature of hexavalent chrcmium campounds, expensive treat~ent equipment must be used to remove chronates from plant effluent to prevent the pollution of rivers, , streams, and drinking wat~r sources. ~ence, although the corrosion resistance and paint ad~esion characteristics of oonversion coated me*21 surfaces can be enhanced ~y an af-ter-treat~ent solution o~ntainIng a hcxavalent chrc~ium ccDçx~und, in recent years there have been research and development efforts directed to ~iscovering effective alternatives to the use of such post-treatment solutions.
One alternative is provide~ in applicant's U~S. patent number 4,376,000 of March 8, 1983, entitle~d "Conpositicn for and Method of After-Treatment of Phosphatized Metal Surfaces". The post-treatnent oompound according to this patent is used in post-treatment solutions having an aIkaline pH. It would, however, be desirable to have a post-treatment compound useful in post-treatment solutions over a brc,ad pH range and, in particular, useful in an acidic post-treatment solution.
In aocordance with the present invention a nDvel composition which is an alternative to hexavalent chrcmiuD
oompound oontaining solutions is pr wided for use in post-tr~atnent solutions in a novel process for the post-treat-ment of phosphatized or conversion coated metal surf~rPs.
Also, the present invention provides a solution and me*hod for treating previously untreated metal surfaces i~cluaing aluminum, steel and zinc nEtal surfaces. The solution and mE~x~d of the present invention provide a ccating on the netal surface and are effective to enhance the corr~sion resist~no_ and paint adhesion characteristics of the metal 7~

surface whether previcusly conversion coated or nok. Fur-ther understanding of t~is invention wqll be had from the following disclosure wherein all parts and percentages are by weight unless otherwise indicated.

:~.

~'~ti7'7'~

S~ CF ~HE ~3VE~aN

In accordance wlth the present invention, a metal surface is treated by oontacting the metal surface with a solution compxising an effective amDunt of a soluble or dispersible treatment ccmpound selected from the grcup consisting of a polymer having the fo~low m g general formula, acid salts thereof, and nixtures thereof:

L ~
~ ~ n where:
Rl through R3 æ e hydrogen or an alkyl group having from 1 to about 5 carbon atoms;
each Y is hydrogen, Z, CR4 ~ 0R6, CH2Cl, or an alkyl or æ yl group having from 1 to 18 carbon aboms;

~ / Rg Z is - C - N
R~ \ Rlo R4 through Rlo æ e hydrogen, or an alkyl, aryl, hydroxy-alkyl, anuu~-aLkyl, mercapto-alkyl or phospho-aIkyl moiety, said R4 through Rlo being of c æbon 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.

i7746 The present invention also relates to preferred treatment solutions oc~prising the above treatment ccmpound with Z moieties being present. Preferably, the solution is an aqueous solution and Z mDieties are present in sufficient amLunt that the comp~und is water soluble or water dispersible.
A metal surfa oe contacted with a solution oomprising the aforementioned treatment ccmpcund has enhanced corrosion resistan oe and paint adhesion characteristics.

DEI~ILED DESCRIPqICN OF THE INVENTIoN

Although the solution of the invention can be effectively applied to treated or untreated metal surfaces, generally speaking the best results wilt be obtained if the metal surfa oe has previously been conversion coated. CbnNersion coatin~s æ e well knGwn and have been de Æ ibed, for exa~ple, in Metal ~an~kcok, Volume II, 8th FA;tion, pages 529-547 of the ~merican Society for Metals and in Metal Finishing Guidebook and Directory, pages 590-603 (1972).

In a typical metal treatment operation employing a co~position and pro oe ss of this invention, the metal to be treated is initially cleaned by a chemical or physical process , . . .

1~i77~

and water rinsed to rem3ve grease and dirt from the surface. m e 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 surfa oe in a oonventional D r to form a conversion coating thereon. The conversion coated surfa oe 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 surfa oe s, including metals having surfaces which have been conversion coated with suitable conversion coatings such as iron phosphate, manganese phosphate, zinc phosphate, zinc phosphate mcdified with calcium, nickel, or magnesium ions, mixed metal oxide, and titanium or zirconium organometallic coatings.
Examples of suitable metal surfa oe s include zinc, iron, aluminum and cold-rolled, ground, pickled, and hot-rolled steel and galvanized steel surfa oe s. As used herein, the term "metal surface" includes kokh untreated metal surfaces and conversion coated metal surfa oe s.

~i77~j In accordance with the methcd of the present invention a metal surface is treated by contacting the metal sur~a oe with a solution ccmprising a treat~ent solution of the present invention. The treatment solution cGmprises an ef.ective a unt S of a soluble or dis~ersible treatment ccm¢ound selected frc~ a polymer having the follcwing general formula, acid salts thereof and mixtures thereof:
0}~ -~Y

- F - F--~ R2 n whero:
Rl thrcugn R3 are hydrcgen or an alkvl grcu~ having fl~u 1 to about 5 car on atcms;
each Y is hydrogen, Z, CR4R_OR6, CH2Cl, or an aIkyl or aryl group having from 1 to 18 carcon atcms;

Z is - C - N
R8 Rlo R4 thrcugh Rlo are hydrcgen, or an aL~vl, a~l, hydroxy-aIkyl, amino-alkyl, mercacto-aIkyl or phospho-alkyl moiety, said R~ thrc w h ~ O being of carbon chain lengths UD to a length at ~hich the ccmpound is not soluble or dis~ersible; and n is from 2 up to a number at which the polymer is not soluble or dispersible ;

with the proviso that Rl, R2 and R3 cannot simultaneously represent hydrogen when the substituted vinyl group is para to the hydroxyl moiety.

- 6a -.'' .v`

Preferably the treatment solution has Z moieties present. Also preferably the treatment solution is an aqueous solution and Z moieties æ e present in sufficient amaunt 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 phen~l, monomer l~nits of the above general formula are preferably selecbed from the para and ortho forms.
It will be appreciated that in the polymeric form, the treatment oompound of the present invention can oomprise a plurality of different specific monomer units each of the above general formLla. For example, a poly~eric co~x~md of this inNention can have the following general formula:
OH OH OH OH
Y~ YY~ Y

H (CH--CH2)A--(CH-CH2)B (CH-CH2)C (CH-CH2)D H
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 mDlar percent needed for water solubility or dispersibility depends upon the molecular weight of the polymers as well as the particular R4 through Rlo 7~

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 mancmer.
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 for~Lla 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 moleclllar weight oligomers of 360 ~o 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 hen~o~=~x~ve 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 the æ
derivatives, a typical upper value for "n" is about 850, with values of frcm about 10 to 300 being preferred. Similarly, the carbon chain lengths of the R4 through Rlo substituents will typically be from about l to 18, with carbon chain lengths of fram 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 comFounds 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.
A~vantageously, however, the treatment coaQcunds can also be used in aqueous solution. To provide water solubility or water dispersibility of the comFound, 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, hexa-fluonotitanic acid, hexafluorozirconic acid, and the like; alone or in oombination with each other. The addition of water to the neutralized, overneutralized or partially neutralized treatment ccmpcunds ~2ntioned 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 ., 9 7 L~ ~ j both for the stability of the solution and for best results on the treated metal Æ face.
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, fram about 0.01% to about 5% by weigh~. Practically speaking, a concentration of 0.025~ to 1% is preferred in a working solution. However, under same circumstan oe s, for example, for transporting or storing the solution, a oancentrate of the solution may be preferred. Also, it is o~ntemplated that the treatment solution may camprise a pigment i.e., be a paint oamposition having a film forming component which can be the treatment conçx~md itself, a solvent, and an organic or inorganic pigment.
Of course, the treatment solution of the present inNention can also camprise ingredients in addition to the treatment 03mpound. For example, the treabment solution may optionally camprise, in addition to the treatment compound, fram about 0.001% to about 1.0~ of a metal ion selected fram the group consisting of titanium, ~irconium and hafnium ions and mixtures thereof. It will be appreciated that these ions are of Group rv 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, a oe tate, citrate, and/or chloride salts. Use of such additianal metal ions can impn~ve both the effectiveness or performance of the treatment solution in use and also can reiluce the time of application of treatment solution to the metal ~t.7~

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 ic,n selected fram 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 f m m the gr~up consisting of thiourea, aIkyl or aryl thiourea compo~nds, 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 tan m n, 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 oonventional method. While it is contemplated that the metal surface will preferably be a conversion coated metal sur~ace, the treatment step can 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 70F to 160F. After application of the treatment solution to the metal surfa oe , the surface can optionally be rinsed, although good results can be obtained without rinsing after treatment. For some end uses, for example, in elect~xooat paint application, rinsing may be preferred.

1~i7746 Next, the treated ~etal 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 Æ face 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 elec~xooating. As a result of the treatm~ent step of the present invention, the conversion coated surface has i~pxoved paint adhesion and corrosion resistance characteristics.
Further understanding of the present invention can be had from the following illustrative examples.

EX~D~LE 1 100 Ibs. of 95% ethanol solvent was charged into a lO0 gallon stainless steel reactor con~aining a turbine blade, niLLuyen sparge and condenser. Gentle heating to 50C was started, and 80 Ibs. of poly-4-vinylphenol polymer of a molecular weight of 5000 was slowly added to the solvent with gcod stirring. After all of the polymer was added, the reactor was closed and heated to 80C to aid in dissolving the remaining polymer. The reactor was then ccoled to 40C and 50 lbs. of N-~ethylaminoethanol and lO0 lbs. of deionized water were àdded.
men over one (l) hour 54.1 lbs. of 37~ formaldehyde solution was added while maintaining the temperature at 40C to ~2C. The reactor was then heated for 3 hours at 40C and 315 lbs. of 10%
nitric acid was added and diluted to 10% solids with deionized water to yield a stable solution of a treatment compound of the present invention in water.

100 g. of CELL~CLVE* solvent was charged into a reactor which was a 1000 ml reaction flask equipped with a condenser, nitrogen sparge, overhead mechanical stirrer and thermcmeter.
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 50C. 108 gm of 37% formaldehyde solution was added over 1 hour and heated an additional 3 hours at 50C and then 3 hours at 80C. The reaction was cooled and 65 gm of 75~ phosphoric acid and then 227 gm of deionized water were added. m e product gave a stable solution of a treatment compound of the present invention in water.

E~iD~LE 3 A cold m lled 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 PAROO~ Cleaner 338 by PARKER ~u~FACE T~U~CnY~Nr PRSDUCTS, OCCIDENI~L CHEMICAL OORP.) by a spray application at 150F solution temperature for 60 seconds;

* Trademark .~

i'7~

follcwed by the application of an iron phosphate conversion coating ~sold under the trademark BONDERITE~ 1014 by PA~aCER
SURFALE T~EAIMENT PF~XXX~rS, CCCIDENTAL CHEMICAL OO~P.) for 60 seconds at 110F. After the con~ersion coating treatment, the panels were rinsed with cold tap water for 30 seconds and then treated with a .5% solution of the oompound of Example I for 30 seconds at a 110F solution temperature by a spray application.
The panels were then rinsed and dried in an oven at 350F for 5 minutes.
m e panels were painted with a standard Duracron~ 200 paint (from PPG Industries) and tested by the standard salt spray method. (A$TMo 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.

E~D~LE 4 The procedure of EKample 1 was carried out except that after adding 54.1 lbs. of 37% ~ormaldehyde solution, the reaction was then heated for 3 hours at 80C 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 oompound of the present invention in water.

E~D~LE 5 Cold rolled steel panels were cleaned using a strong alkaline cleaner and the cleaned metal surface was then rinsed 74~

with hot ~ater. An iron phosphate conversion coating IBONDERITE~
1000 made by PARKER SURF~CE 5E~nq~NT PRODUCTS, OCCIDENTAL
CHEMICAL CORP.) was then applied at 160F by spray application and the panels were r m sed with cold water ~efore 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 phosphated metal at 120F. Concentration of the poly-4-vinylphenol derivative and hexafluorotitanic acid content was varied from .05 to .2~ and .06 to .03~ respectively. Some of the post-treated panels were water rinsed others were not rinsed. All panels were then baked in a 350F oven for S minutes. Control panels of PA*~OLENE~ 60 chromium rinse were employed.
The abcve prepared panels were painted with an anodic electrocoat paint system, Powercron~ 300 acrylic electrocoat of PPC Industriesj at lZ0-140 volts for 60-90 seconds at 80F in order to obtain a uniform coatihg appearance and thickness of .95-1.00 mils. Cure of the coating was at 325F peak metal temperature for 20 minutes. The panels ~ere scribed fru~ 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 P~ B117-61 and ccmpared with chromate treated as well as deionized rinsed controls. Results ~quivalent to PAR30LENE~ 60 activated chromium rinse control (made by PAFKER
SURFACE I}Q~:q:~T PRCCUCTS, OCCIDENTAL CHEMICAL CORP.) were obtained with the poly-4-vinylphenol derivative of .1%
concentration with hexafluorotitanic acid at .03% concentration in the treatment bath.

77't~i or complex oxide type. 5a~ples of the substrates prepared as - described abcve were then given a 10 second final rinse wqth one of the follcwinq final rinses:
Final Rinse No. 1. Mbdified chrcmic acid (Parcolenec 62 made by PA~UCER SURFACE I~E~ Yr PRCDUCT5, occmENTAL
CHEMICAL CORP.) Final Rinse No. 2. Deionized water.
FLnal Rinse No. 3. Aquecus solution of 0.25% by weight of an acid salt of a poly-4-vinylphenol derivative, pH 6.0 prepared as in E~ample 4.
Final Rinse No. 4. ~queous solution of 0.25~ by weight of the acid salt of poly-4-vi.~ylphenol derivative as in number 3 above and 0.015% by weight of titaniu~ ions, added as H2TiF6, pH 6.1.
m e panels were then painted with one and two-coat paint systf3ns:
Paint 1 GLIDDEN 71308* POLYLURE 2000 white polyester Paint 2 M & T* black vinyl Paint 3 MIDLAND* white polyester Paint 4 MIDLAND-DE~ZR* 9x165 epoxy primer MIDLI~ND-DE~rER 5x121 crystal white Dexsta~ polyester topcoat The panels were then scribed and subje~ted to standard ASTM
B-117-61 5% sait fog tests, ASTM 2247-64T humidity tests and 180 T-bend adhesion test as described in 2~rM D3794-79. m e results are set forth below:

* Trademark , 16 - : .

~77~i 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 Cbmplex Qxide RLnse 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 1-14S 0-1 FM9 R9 0-1 VF~8 0-375 55%P MD6 0-1 1 O_ls O_lS FM9 R8.5 0-1 VF+8 o_l3s 55~p MD6 0-1

2 70% P 0_1S D9 R5 3-911sF8 2-575 85%P(192Hr.) 7-1214SVF+8 2 70% P N D9 R5 4-811SF6 2_48s 80%P(192Hr.) 40%P

3 1-2 0 15 D9 R5 1-235MD9 1-2 1 36s MD6 0-1 F9 3 1-1 O_ls D9 R6 1-255MDg 1_24s 4-13~D6 2%P 0-12sVF+9

4 2-3 N D8 R5 0_1S MD9 0-125 0-1 MD8 0 lsVF9 4 2_34s 0 ls D9 R5 0-15 MDg 0-1 0-1 ND9 0 14svF+9 VF = very few, F = few, FM = few-~edium, MD = medium-dense, D =
dense, %P = % peel, R = red rust, s = spot, N = nil.
Reported above is the creepback from the scribe, the a~ount 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 fro~ the scribe with the polymer rinse is less than that of the chrcmic 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. ~he adhesion at a 180 T-bend for the polymer-containing rinses was at least equal to that for the chromic acid rinse, and generally better.

77~

Panels were treated as in Example 6, except that the treat~ent time was reduced to 5 seconds. Excellent results as CQn~XL~ed to chramic acid post-treatments were obtained on zinc S 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 .1% con~entration 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 .2% thiourea and .05% tannic acid in the abcve formulation.

E5~D~LE 8 Cleaned aluminum panels were treated with BoNDEFITE~
787 treatment (a chrome-free conversion coating of PARKER SURFA OE
TRS~Y~DENT PR~DUCTS, CCCIDENTAL CHEMICAL CORP.) After rinsing with cold water one set of panels was rinsed with PARCOLENE~ 88 (a ch m me~free rinse from PAE~CER SURFACE TREa~MENT PRODUCIS, CCCIDENI~L 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 remGve excess solution. Ch m me controls were prepared using BONDERITEo 722 treatment and a final PARCOLENE~ 10 rinse (both fram PARKER SURFA OE I$~.~nUENT PRODUCTS, OCCIDENTAL
CHEMICAL CORP.) After the PARfOLENE~ 10 rinse, the panels were also run through squeegee rolls.

~ ~ ~ i 7 7 L~

The treated panels were painted with t~o single coat systems.
1. HANNA* Paint- Hichory Brcwn Polyester XR8298D
2. W PONT* Paint- White acrylic 884-5001 LUCITE 2100 S Series The painted aluminum panels ~æ_e subjected to acetic acid salt spray for 504 hours. Ratings w-ere m2ce after e~ch 16a hours ky tape plllling at the scribed area and obse_ving for loss of paint, 'general blistering and edge creeDage.' Ihe follcwing 10 ratings were obselved after 504 hours:

Poly-4-Vinyl-~787 phenol Derivatives B722 Treatment +P~N 88 as in Ex2mDle 4 +PLN 10 . . _ , .
HANNA Paint E D6, D8 ` E 0-15, D9 ~ 0-15 S 7-10, D6 S o 2s D9 5 0-2

5% P D8 0-15 F9 0_1S F9 DVPONT Paint E D6 E MD9, D9 0_3s 20S 0-2 , 3%P, D6 S 0-1, MD9 S 0-2, l~P, VF99 0-25, 4~P, D6 1%P M9 O-ls, 3%P, VF' E --Edge Rating, S = Scribe Rating The ,salt spray results as measured by cre~page frcm the scribe and bl;stering indicate that aluminum par.els treated with BCND~x1'1~:3 787 treat~ent and Fost-treated with poly-4-vinylphenol derivative of Example 4 is as good as or etter than BCNDE~ITE~
722 treatmen~ plus PARCOLENE~ 10 control systOEn.

* Trademark 7~

B~LE 9 Panels were treated as in Example 5 except each panel was given a 5 second final rinse with one of the solutions below:
PARCC-LENE~ 62 Poly-4- Mcdified Final VinylPhenol Chrcmic Rinse Derivative H Ti F6 Thiourea Tannic Acid Acid No. Wt.~ t.% Wt.~ Wt.~ Wt.% ~
l 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 abcve. The results with Rinse No. 2 were better than or equal to those with Rinse No. l, the chramic acid control, except with the iron phosphate system, where the results were good, but somewhat weaker than with the chrQmic acid control. m e 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 en~xx~nents of the present invention, the ~ sitions and methods described are- intended to illustrate but not limit the present invention, it being understood that the specific emlxXl~nents 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 sccpe of the present invention is to be limited solely by the following claims.

Claims (21)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. The process of treating a metal surface comprising contacting the metal surface with a solution comprising an effective amount of a soluble or dispersible compound selected from the group consisting of a polymer having the following general formula, acid salts thereof and mixtures thereof:

where:
R1 through R3 are hydrogen or an alkyl group having from 1 to about 5 carbon atoms;
each Y is hydrogen, Z, CR4R5OR6, CH2Cl, or an alkyl or aryl group having from 1 to 18 carbon atoms;

R4 through R10 are hydrogen, or an alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl or phospho-alkyl moiety, said R4 through R10 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;

with the proviso that R1, R2 and R3 cannot simultaneously represent hydrogen when the substituted vinyl group is para to the hydroxyl moiety;

and where Z moieties are present in a molar percent of Z per monomer of from about 10% to about 200%.

2. The process of claim 1 wherein said solution is an aqueous solution

3. The process of claim 2 wherein the molar percent of Z per monomer is from about 50% to about 150%.

4. The process of claim 2 wherein the pH is from about 0.5 to about 12.

5. The process of claim 4 wherein the pH is from about 2.0 to about 8Ø

6. The process of claim 1 wherein said compound is present in an amount of from about 0.01% to about 5%.

7. The process of claim 6 wherein said compound is present in an amount of from about 0.025% to about 1%.

8. The process of claim 5 wherein Z is

9. The process of claim 5 wherein Z is

10. The process of claim 1 wherein said compound is the reaction product of a poly-4-vinylphenol, formaldehyde and a secondary amine.

11. A solution for treatment of a metal surface comprising an effective amount of soluble or dispersible compound selected from the group consisting of a polymer having the following general formula, acid salts thereof and mixtures thereof:

where:

R1 through R3 are hydrogen or an alkyl group having from 1 to about 5 carbon atoms;
each Y is hydrogen, Z, CR4R5OR6, CH2Cl, or an alkyl or aryl group having from 1 to 18 carbon atoms;

R4 through R10 are hydrogen, or an alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl or phospho-alkyl moiety, said R4 through R10 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;

with the proviso that R1, R2 and R3 cannot simultaneously represent hydrogen when the substituted vinyl group is para to the hydroxyl moiety;

and where Z moieties are present in a molar percent of Z per monomer of from about 10% to about 200%.

12. The solution of claim 11 wherein said solution comprises, in addition, a pigment.

13. The solution of claim 11 wherein said solution is a paint.

14. The solution of claim 11 wherein said solution is an aqueous solution.

15. The solution of claim 11 wherein the molar percent of Z per monomer is from about 50% to about 150%.

16. The solution of claim 15 wherein the pH is from about 0.5 to about 12.

17. The solution of claim 16 wherein the pH is from about 2.0 to about 8Ø

18. The solution of claim 11 wherein said compound is present in an amount of from about 0.01% to about 5%.

19. The solution of claim 18 wherein said compound is present in an amount of from about 0.025% to about 1%.

20. The solution of claim 11 wherein Z is

21. The solution of claim 11 wherein Z is