NZ208077A - Anticorrosive treatment of metal surfaces using polyalkenylphenol derivatives - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £08077 No.: Date: r»Mi r Priority Date(o). . A.. • • Complete Specification Class: fcD,6S;. A0c|06t.0». v Publication Date: P.O. Journal, No: luVA-^1 2 080 77 NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION "TREATMENT OF METAL WITH DERIVATIVE OF POLY-AIKENYLPHENOL" K/We, PARKER CHEMICAL COMPANY, a Delaware corporation, of 32100 Stephenson Highwayi Madison Heights, Michigan 48071, U.S.A., hereby declare the invention lor which I / we pray that a patent may be granted to Xtte/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page la) Cacfl No■ ■ P-lljl05 I 2 08 0 TREATMENT OF METAL WITH DERIVATIVE OF FOLY-AEJCENYLPHENQL O background of the invention The present invention relates to the art of metal surface treatment. Mare specifically, the present invention relates to treatment of metal surfaces with a solution of a 10 poly-alkenylphenol derivative or an acid salt of a poly- alkenylpbenol derivative. The treatment imparts inproved corrosion resistance and paint adhesion characteristics to the metal surfaces.

Hie need for applying protective coatings to metal 15 surfaces for inproved 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 codde —conversion coating on the metal surface to iraprove the corrosion 20 resistance and paint adhesion thereof. Also traditionally, the conversion coated metal surfaces have been rinsed or post-treated with a solution containing a haxavalent chrcndun compound for ^ even greater corrosion resistance and paint adhesion.

Because of the toxic nature of haxavalent chromium 25 oaqpounds, expensive treatment equipment rtust be used to remove chromates from plant effluent to prevent the pollution of rivers, — i — 208077 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 ccropound, 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 N.Z. patent application of Andreas Lindert, Serial Number 198671 for "Composition for and Method of After-Treatment of phosphatized Metal Surfaces"; filed on October 16, 1981. The post-treatment ccnqpound of iry earlier application is used in post-treatment solutions having an alkaline pH. It would, hcwever, 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 poet-treatment solution.

In accordance with the present invention a novel composition which is an alternative to hexavalent chrcniun ccnpound containing solutions is provided for use in post-treatment solution 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 aluninun, 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. 2 2 Oo 0 7 SttfCffg OF THE INVENTION In accordance with the present invention, a metal surface is treated by contacting the metal surface with a solution oooprising an effective amount of a soluble or dispersible treatment oanpound selected from the group consisting of a polymer having the following general fornula, acid salts thereof, and mixtures thereof: where: R^ through R^ are hydrogen or an alkyl group having from 1 to about 5 carbon atoms; each Y is hydrogen, Z, CR^ORg, CHgCl# or an alkyl or aryl group having from 1 to 18 carbon atoms; r4 through are hydrogen, or an alkyl, aryl, hydraxy-aUsyl, amino-aUcyl, mercapto-alkyl or phospho-alkyl moiety, said through R^0 being of carbon chain lengths up to a length at which the oGOpound is not soluble or dispersiJble; and n is from 2 vp to a ranter at which the polymer is not soluble or dispersible.

OH Rj Bj n *8 "lO 2 08 0 The present invention also relates to preferred treatment solutions conprising the above treatment conpound with Z moieties being present. Preferably, the solution is an aqueous solution and Z moieties are present in sufficient amount that the oaqxxmd is water soluble or water dispersible.

A metal surfaoe contacted with a solution oonprising the aforementioned treatment ocnpound has enhanced corrosion resistance and paint adhesion characteristics. nTPATT.FP OE3CK1MION OP THE INVEKTICN Although the solution of the invention can be effectively applied to treated or untreated metal surfaces, generally speaking the bast results will be obtained if the metal surface has previously been conversion coated. Conversion costings are well kncwn and have been described, for exanple, in Metal Handbook, \fel\xoe 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 ccnpoaiticn and process of this invention, the metal to be treated is initially cleaned by a chemical or physical process 2 08077 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 foon 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 magnesiun ions, mixed metal codde, and titanium or zirooniun organometallic coatings. Exanples 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 and conversion coated metal surfaces. 2 080 7 7 In accordance with the method of the present invention a metal surface is treated by contacting the metal surface with a solution ccnprising a treatment solution of the present invention. The treatment solution ocnprises an effective amount of a soluble or dispersible treatment caqpcund selected from a polymer having the following general formula, acid salts thereof and mixtures thereof: where: R^ through R3 are hydrogen or an alkyl group having frcm 1 to about 5 carbon atoms; each Y is hydrogen, Z, CR^CRg, CHjCl, or an alkyl or aryl group having from 1 to 18 carbon atoms; R4 through Rjq are hydrogen, or an alkyl, aryl, hydroocyalkyl, andno-alkyl, mercapto-alJcyl or phospho-alkyl moiety, said through being of carbon chain lengths up to a length at which the uiujuuimI is not soluble or dispersible; and n is from 2 up to a number at which the polymer is not soluble or dispersible.

GH Rj &2 n Z is 2 030 7 7 Preferably the treatment solution has Z moieties present. Also preferably the treatment solution is an aqueous solution and Z moieties are present in sufficient amount that the canpound is water soluble or water dispersible.

While the alkyl groups of the polymer backbone or chain in the above fnrmiiln can be located in the artho, rata, or para positions to the hydrtayl group on the arena tic ring of the phenol, monomer units of the above general formula are preferably selected from the para and artho forms.

It will be appreciated that in the polymeric form, the treatment ouiiminrt of the present invention can cowpriae a plurality of different specific monomer units each of the above general formula. For exanple, a polymeric ccnpound of this invention can have the following general fbxnula: where Y is defined as above (but is not hydrogen) and wherein A, B, C, and D can be fran 0 to a iraber 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 diapersibility depends upon the molecular weight of the polymers as well as the particular R^ through R^q 2 08077 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 ccnpound of the present invention is based on derivatives of poly-allcenylphenol polymer. Examples of poly-alkenylphenols or substituted alkenylphenols useful in the present invention include isopropenylphenol, isobutenylphenol, dimethylvinylpheaol and the like. Suitable derivatives having the above general formula can be mader for example, by the Mannich Reaction. Far exanple, 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 amils-tra of the treatment ocnpound of this invention.

The nr>1era,ilar weight of the poly-alkenylphenol used in the preparation of derivatives claimed in the present invention can range from the diner, or mare 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 functioned, 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 8 ° 08 0 7 7 values of fran about 10 to 300 being preferred. Similarly, the carbon chain lengths of the R4 through R^0 substituents will typically be from about 1 to 18, with carbon chain lengths of fran 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 diapersibility.

The treatment oonpounds of this invention are soluble in organic solvents and can be used as a treatment solution when dissolved in an organic solvent as, for exanple, ethanol. Advantageously, however, the treatment compounds can also be used in aqueous solution, lb provide water solubility or water dispersibility of the confound, 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, phenylphosphanic acid, chloronethylphosphonic acid; mono, di and trichloroacetic acid, trlfluoroacetic acid, nitric acid, phosphoric add, hydrofluoric acid, sulfuric acid, boric acid, hydrochloric acid, hexafluorosilicic acid, hexa-fluocotitanic 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 ocmpcmnris mentioned above results in a water soluble or dispersible solution or enulsion 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 2 080 77 both for the stability of the solution and for best results on the treated metal surface.

It is contemplated that the treatment conpound of the present invention will generally be used in a working solution at a dilute concentration of, for exanple, 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 sane circumstances, for exanple, for transporting or storing the solution, a concentrate of the solution may be preferred. Also, it is contenplated that the treatment solution may ocnprise a pigment i.e., be a paint composition having a film forming oonponent which can be the treatment oonpound itself, a solvent, and an organic or inorganic pigment.

Of course, the treatment solution of the present invention can also concise ingredients in addition to the treatment oonpound. For example, the treatment solution may optionally comprise, in addition to the treatment conpound, fran about 0.001% to about 1.0% of a metal ion selected fran 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 exanple, hexafluarotitanic acid, hexafluorozizconic acid, hexafluarohafnic acid, or the nitrate, sulfate, fluoride, acetate, citrate, and/or chloride salts. Ute of such additional metal ions can inprove 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 2 08077 surface to as short a time as froa about 2 to about 5 seocnds r as nay be required for use on a coil line.

Still other optional ingredients may be enployed in addition to, or instead of, the aforementioned metal ions. For exanple, in addition to the treatment conpound and a metal ion selected fran this group consisting of titanium, ziroonium, and hafnium ions and mixtures thereof, the treatment solution can oarprise from about 0.01% to about 4.0% of ingredients selected fran the group consisting of thiourea, alkyl or aryl thiourea oonpounds, tannic acid, vegetable tannins or gall tannins and mixtures thereof. Exanples of suitable ingredients include methyl, ethyl or butyl thiourea, wattle, mangrove or chestnut tannins, oak gall tannin, and valcnea 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 contenplated that the metal surface will preferably be a conversion coated metal surface, the treatment step can alternatively be carried out on an untreated metal surface to inprove the corrosion resistance and paint adhesion thereof. For exanple, the treatment solution can be applied by spray coating, roller coating, or dipping. The tenperature of the solution applied can vary over a wide range, but is preferably from 70°F to 160°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. Far some end uses, for exanple, in electroooat paint application, rinsing may be preferred. 11 ^ • 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# JP 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 15 examples. The inclusion of the Group IV B metal in these examples is optioned for the purposes of the present invention.

ZVVU/7 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^c was started# and 80 lbs. of poly-4-vinylphenol polymer of a 25 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^C to aid in dissolving the remaining polymer* The reactor was thai cooled to 40^C and 50 lbe. 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 tenperature at 40 to +2®C. The 2 0807 reactor was then heated for 3 hours at 40°C 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 coopound of the present invention in water.

EXAMPIE 2 100 9. of celloaolve solvent was charged into a reactor which was a 1000 nil reaction flask equipped with a condenser, nitrogen sparge, overhead mechanical stirrer and thermometer. Then 80 gm of poly-4-virylphenol having a molecular weight of 5000 was added and dissolved. 70 gm of dlethanolamine and 100 9m of deionized water were added and reaction heated to 50°C. 108 gm of 37% formaldehyde solution was added over 1 hour and heated an additional 3 hours at 50°C and then 3 hours at 80°C. The reaction was cooled and 65 gn of 75% phosphoric acid and thai 227 gm of deionized water ware added. The product gave a stable solution of a treatment conpound of the present invention in water. aawiE 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 BAROOe 338 by PARKER SURFACE TREATMENT PRODUCTS, OOCIDQJTftL CHEMICAL CORP.) by a spray application at 150°F solution tenperature for 60 seconds; 13 2 080 followed by the application of an iron phosphate conversion coating (sold under the trademark BCNDERITE® 1014 by PARKER SURFACE TREATMENT PRODUCES, OCCIDENTAL CHEMICAL CORP.) for 60 seconds at 110°F. After the conversion coating treatment, the panels were rinsed with cold tap water for 30 seconds and then treated with a .5% solution of the conpound of Exanple I for 30 seconds at a 110°F solution tenperature by a spray application. The panels were then rinsed and dried in an oven at 350°F for 5 minutes.

The panels were painted with a standard Duracrona 200 paint (from PPG Industries) and tested by the standard salt spray method. (ASTMe B-117-61.) After 504 hours, the panels treated with Exanple I as described above gave results equivalent to the standard chrcndun treated control panels.

BaMPI£ 4 The procedure of Etanple 1 was carried out except that after adding 54.1 lbs. of 37% formaldehyde solution, the reaction was than heated for 3 hours at 80°C and 326 lbs. of 10% phosphoric acid was added and the reactor contents were diluted to 10% solids with deionlged water to yield a stable solution of a UeaLiueiiL conpound of the present invention in water. example; 5 Gold rolled steel panels were cleaned using a strong alkaline cleaner and the cleaned metal surface was then rinsed 14 2 03 0 with hot water. An iron phosphate conversion coating (BGNDERHE& 1000 made by PAFKER SUFFICE TREATMENT PRODUCTS, OCCIDENTAL CHEMICAL CORP.) was then applied at 160°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 Exanple 4 were mixed with hexafluorotitanic acid and applied to the phosphated metal at 120°F. Concentration of the poly-4-vinylphenol derivative and hexafluorotitanic acid content was varied fran .05 to .2% and .06 to .03% respectively. Seme of the post-treated panels were water rinsed others were not rinsed. All panels were thai baked in a 350°F oven for 5 minutes. Control panels of PARODUHEe 60 chromium rinse were ecployed.

The above prepared panels were painted with an anodic electrocoat paint system, Powercron® 300 acrylic electrocoat of PPG Industries, at 120-140 -volts for 60-90 seconds at 80°F in order to obtain a uniform coating appearance and thickness of .95-1.00 mils. Cure of the coating was at 325°F peak metal tsnperature for 20 minutes. The panels were scribed from comer 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 AS3M B! 17-61 and compared with chromate treated as well as deionized rinsed controls. Results equivalent to PAROQLQIEe 60 activated clitonitm rinse control (made by PARKER SURFACE TSEASMBfT PRODUCTS, OCCIDENTAL CHEMICAL CORP.) were obtained with the poly-4-vinylphenol derivative of . 1% concentration with hexafluocotitanic acid at .03% concentration in the treatment bath. example 6 208077 J Cold-rolled steel (GRS) panels were cleaned and treated to yield an iron phosphate conversion coating on the panel. Tenper-rolled galvanized steel panels (TOG) were cleaned and treated to yield conversion coatings of either the zinc phosphate or canplex 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 Mb. 1. Modified chronic acid (Parcolene© 62 made by PARKER SURFACE TREATMENT PRODUCTS, OCCIDENTAL CHEMICAL CORP.) Deionized water.

Aqueous solution of 0.25% by weight of an acid salt of a poly-4-vinylphenol derivative# pB 6.0 prepared as in Example 4. Aqueous solution of 0.25% by weight of an acid salt of a poly-4-vinyl phenol derivative# as in number 3 above and 0.015% by weight of titanium ions# added as B^TiFg# pH 6.1.

The panels were then painted with one and two-coat paint systems: Glidden 71308 Final Rinse MO. 2. Final Rinse MO. 3.

Final Rinse Mb* 4.

Paint 1 Paint 2 Paint 3 Paint 4 M & T Midland Midland-Dexter 9x165 PolyLure 2000 white polyester black vinyl white polyester epoxy primer Midland-Dexter 5x121 crystal white Dexstar ® polyester topcoat The panels were then scribed and subjected to standard ASTM B-117-61 5% salt fog tests# ASTM 2247-64T tumidity tests and 180° 2 0J 0 7 7 T-bend adhesion test as described in ASTM D3794-79. The results are set forth below: % Salt Fog Results Final Rinse No.

Iron Phosphate Paint 1 Paint 2 192 Hr. 192 Hr.

Zinc Phosphate Paint 3 Paint 4 504 Hr. 1008 Hr.

Canplex Oxide Paint 3 Paint 4 504 Hr. 1008 Hr. 1 l-l4s 0-13 FM9 R9 0-1 VF+8 0-37s 55«P £06 0-1 1 0-18 0-lS EM9 R8.5 0-1 VF+8 0-l3s 55%P M)6 0-1 2 70% P 0-1® D9 R5 3-9U®F8 2-57" 85%P(192Hr.) 7-1214®VF+8 2 70% P N D9 RS 4-8U®F6 2-48s 80%P (192Hr.) 40%P 3 S CM A 0-lS D9 RS 1-23SM)9 1-2 1-36® MX 0-1 F9 3 1-1 0-lS D9 R6 1-25sM>9 1-24s 4-13M36 2%P 0-l2SVF+9 4 2-3 N D8 RS 0-lS *D9 0-128 0-1 MD8 0-lSVF9 4 2-348 0-1® D9 R5 0-1® M>9 0-1 0-1 M39 0-14sVF+9 VF « very few, . F ■ few, EM * few^-mediucr I, M) « medium-dense, D m dense, %P - % peel, R ■ red rust, s « spot, N - nil.

Reported above is the creepback fran the scribe, the amount of blistering, and red rust ratings. Ihe creepback from the scribe produced by the final rinses containing the polymer is substantially less than that of the deionized water fined, rinse. NELth the added titanium, the creepback fran the scribe with the polymer rinse is less than that of the chronic acid rinse in at least four cut of the six cases.

The humidity results for the iron phosphate coated panels rinsed as above were essentially equivalent. Ihe adhesion at a 180° T-bend £otr the polymer-containing rinses was at least equal to that for the chronic acid rinse, and generally better. 17 2 03077 EXAMPLE 7 Panels were treated as in Exanple 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 conpLex metal oxide conversion coatings but slightly weaker results were obtained on iron phosphate when a solution of poly-4-vinylphenol derivative prepared as in Exanple 4 was used at .1% concentration along with .02% hexafluorotitanic acid at a UealiumiL 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 above foxnulation.

EXMCIS 8 Cleaned alunixnan panels were treated with BCNDER1TB* 787 treatment (a chrane-free conversion coating of PARKER SURFACE EBHDBIT PRODUCTS, OCCIDENTAL CHEMICAL C30HP.) After rinsing with cold water one set of panels was rinsed with PAROQEJiHEe 88 (a chrane-free rinse fran PARKER SURFACE TTCEAJMENT PRODUCTS, OOCIEGNXnL CHEMICAL CORP.) and the other set was rinsed with a post-treatment as prepared in Exanple 4 .

After rinsing the panels were run through squeegee rolls to remove excess solution. Chrane controls were prepared using BGNDERTIE® 722 treatment and a final PAFOOUNEe 10 rinse (both fran PARKER SURFACE TREATMENT PRODUCTS, OCCIDENTAL CHEMICAL CORP.) After the PAROQUBlEe 10 rinse, the panels were also run through squeegee rolls. 18 2 08 0 7 7 The treated panels were painted with two single coat 1. Hanna Paint - Hickory Brown Polyester XR8298D 2. DuFont Paint - White acrylic 884-5001 Lucite 2100 Series The painted aluminum panels were subjected to acetic acid salt spray for 504 hours. Eatings were made after each 168 hours fcy 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 Foly-4-Vinyl-B787 phenol Derivatives B722 +PIU 88 as in Bcanple 4 +PIN 10 Banna Paint E D6, D8 E 0-ls, D9 E 0-1* S 7-10, D6 S Or2s, D9 S 0-2® % P D8 0-1® F9 0-1® F9 DuFcnt Faint E D6 E M59, D9 E 0-2® 0-3® S 0-2®, 3%P, D6 S 0-1®, MD9 S 0-2®, 1%P, VF9Q 0-2 , 4%P, D6 1%P M9 0-1®, 3%P, VF+y E "Edge Rating, S ■ Scribe Rating The salt spray results as measured by croppage frcm the scribe and blistering indicate that alundrun panels treated with BOBERTIE® 787 treatment and post-treated with poly-4-vinylphenol derivative of Bcaqple 4 is as good as or better than BQNDE8ITE* 722 treatment plus PARGOUNEe 10 control system. 19 Z 08077/ EXAMPLE 9 Panels were treated as in Exanple 5 except each panel was given a 5 second final rinse with one of the solutions below: PARQO-1BHB9 62 Foly-4- Modified Final VinylPhenol Chronic Rinse Derivative H_Ti Ffi Thiourea Tannic Add Acid NO. Wt.% Wt.% Wt.% Wt.% gH 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 ware painted and tested as above. The results with Rinse No. 2 were better than or equal to those with Rinse No. 1, the chronic acid control, except with the iron phosphate system, where the results were good, but sanewhat weaker than with the chronic acid control. The results with Rinse Mo. 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 oppositions and methods described are intended to illustrate but not limit the present invention, it being understood that the specific enbodiments described herein are subject to variation and iwflrtififlatinn 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.

SUOUYY

Claims (24)

WHAT WE CLAIM IS:

1. The process of treating a metal surface couprising contacting the metal surface with a solution conprising ah effective amount of a soluble or dispersible conpound selected from the group consisting of a polymer having the following general formula, acid salts thereof and mixtures thereof: .fs J 5 10 15 20 25 where: *2 J" Rl through R3 are hydrogen or an alkyl group having from 1 to 5 carbon atoms; each 7 is hydrogen, Z, CR4R5OP6, CH2CI, or an alkyl or aryl group having from 1 to 18 carbon atoms; * Z is V •c N I \ ®8 *10 R4 through Rio are hydrogen, or an alkyl, aryl, hydroxy^alkyl, amino-alkyl, mercapto-alkyl or phospho-alkyl, moiety, said B4 through Rio being of carbon chain lengths up to a length at which the conpound is not soluble or dispersible; and n is from 2 up to a number at which the polymer is not soluble or dispersible. o' '/'V ■f-S JULI987S 208077 but excluding confounds and salts thereof having the following general formula; wherein n is from 5 to 100; each X is H or CRRjOHj and of R and Rl is hydrogen or an aliphatic or aronatic organic moiety having from 1 to 12 carbon atcns._ ■ ■■■ 208077

2. The process of claim 1 wherein said solution is an aqueous solution and Z moieties are present in a molar percent of Z per

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

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

5. The process of claim 4 wherein the pH is from 2.0 to 8.0.

6. The process of claim 1 wherein said compound is present in an amount of fran 0.01% to 5% by weight.

7. The process of claim 6 wherein said conpound is present in an amount of from 0.0 25% to 1% by weight.

8. The process of claim 5 wherein Z is moncmer of fran 10% to 200%

- CH - N 2 -23- 208077

10. Hie process of claim 1 wherein said conpound 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 caqoound selected from the group consisting of a polymer having the following general formula, acid salts thereof and mixtures thereof: from 1 to 5 carbon atoms; each Y is hydrogen# Z, CR4R5OR5, CH2CI, or an alkyl or aryl group having from 1 to 18 carbon atoms; R4 through R^j are hydrogen, or an alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl or phospho-alkyl moiety, said S4 through R^o being of carbon chain lengths up to a length at which the conpound is not soluble or 203077 n is from 2 up to a nunber at which the polymer is not soluble or dispersible; and when one or more Y is Z, Z moieties are present in a molar ratio expressed as percent of Z per mononer of from 10% to 200% f but excluding ccnpounds and salts thereof having the following general formula: wherein n is fran 5 to 100; each x is H or CRRjOH; and each of' R and R i is hydrogen or an aliphatic or aronatic organic moiety having fran 1 to 12 carbon atoms.

12. Hie solution of Claim 11 wherein said solution comprises, in addition, a pigment.

13. Hie 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 mononer is from 50% to 150%.

16. The solution of Claim 15 wherein the pH is from 0.5 to 12. H(-CH - CHa -) nH •• 'i " -25- 208077

17. The solution of Claim 16 wherein the pH is from 2.0 to 8.0.

18. The solution of Claim 11 wherein said conpound is present in an amount of from 0.01% to 5% by weight.

19. The solution of Claim 18 wherein said conpound is present in an amount of from 0.025% to 1% by weight.

20. The solution of Claim 11 wherein Z is ^^CHa-CH,OH -CHa- N

21. The solution of Claim 11 wherein Z is CHa-CHaOH -CHa- N CHaCHaOH

22. The solution of Claim 11 wherein said compound is the reaction product of a poly-4-vinylphenol, formaldehyde and a secondary amine.

23. A process of treating a metal surface as claimed in any one of Claims 1-10 substantially as herein described with reference to the Exanples.

24. A solution for treatment of a metal surface as claimed in any one of Claims 11 -22 substantially as herein described with reference to the Examples. DA7ED wS <2*4^DAY AJ. PARK & SON per /] vLluau f . -26 - AGENTS FOR THE