MXPA98004916A - Aqueous solutions of phenolym polymers from amino fenoles and polymers of anhydrids or di-epoxy - Google Patents

Abstract

A composition for the treatment of metals with cationic final rinsing, comprising a phenolic polymer soluble or dispersible in water, which is the reaction of: an amino phenol and either an anhydride-containing polymer or a di-epoxide polymer, said polymer includes a group that imparts cationic functionality to the polyme

Description

AQUEOUS SOLUTIONS OF PHENOLIC POLYMERS FROM AMINO FENOLES AND POLYMERS OF ANHYDRIDES OR DI-EPOXIDES BACKGROUND OF THE INVENTION The invention relates to improvements in the chemical pre-treatment of metal surfaces, in particular to improved chrome-free final rinsing compositions. It is well known that the adhesion of paints to metal surfaces and the corrosion resistance of metal can be improved by using a chemical pre-treatment of the surface before painting it. Normally the metal is pretreated with chemicals that favor the formation of a metal phosphate, usually zinc phosphate or iron phosphate, on the surface. Additionally, the pre-treated surface of the metal is rinsed with a chromic acid solution containing hexavalent chromium compounds. The rinses with chromic acid enhance the resistance to corrosion and adhesion to paints. However, due to the toxic nature of the hexavalent chromium compounds, expensive water treatment methods are normally used in order to avoid discharges of water containing chromium to the environment. Therefore, there is a need to replace the rinses with chromic acid in the chemical pre-treatment systems of metal surfaces. Final rinses without chromium, containing at least one metal ion, have been developed. Some examples are described in U.S. Patent Nos. 3,695,942, 3,895,970, 4,457,790 and 5,209,788. However, the majority of nonchronic rinses have not reached a commercially useful final rinsing level. Even though they are useful, chrome-free rinses from prior techniques do not tend to behaviors consistently comparable to chrome-bearing rinses. According to this, rinses without chromium are needed with better efficiency.

SUMMARY OF THE INVENTION According to the present invention, a final chrome-free improved rinse composition 5 is provided for the metal surface treatment comprising an aqueous solution of phenolic polymers that have been prepared from amino phenols and polymers containing anhydride groups or diperoxide groups. More specifically, the chromium-free final rinse composition of the present invention comprises a water-soluble or water-dispersible phenolic polymer which is the reaction product of: (a) an amino phenol having the following general formula \ -5 \ (1) where: X1 to X4 are equal to H, OH, halogen, or an alkyl, aryl, or ether group, or a group that is not reactive with anhydrides or epoxides; R1 is equal to 0 to H or a lower alkyl group having between 1 and 6 carbon atoms; Y, (b) an anhydride-containing polymer having one of the following general formulas: where R2 is equal to H ,, or CH3, Z is a group derived from an ethylenically unsaturated monomer or monomers capable of polymerizing with an unsaturated anhydride , m and n are integers equal to or greater than 1, which sum is sufficient to provide a molecular weight of 600 to 100,000 to the polymer, or (c) a di-epoxide having the following general formula: 0 0 / \ / \ CH, - CH RJ CH - CH, (4i where R3 is an alkyl, aryl or cycloalkyl group, optionally containing functional groups such as ether, hydroxyl groups, or other groups that do not interfere with the reaction The phenolic polymer described above becomes water soluble or water dispersible by copolymerization of a monomer containing a group capable of becoming cationic by neutralization with an acid, or by binding of this group to the polymer, for example by Mannich reaction with subsequent neutralization with an acid.

DETAILED DESCRIPTION OF THE INVENTION The water-soluble or water-dispersible phenolic polymer of the present invention is obtained by reaction of a suitable amino phenol having the structure (1) indicated above with an anhydride-containing polymer having one of the structures ( 2) or (3) above. Alternatively, the aforementioned amino phenol (1) can be reacted with a di-epoxide having the structure (4) indicated above. Examples of suitable amino phenols include p-aminophenol, o-aminophenol, m-aminophenol, 4-amino-2-chlorophenol, 4-amino-2-fluorophenol, 5-aminoresorcinol, 4-aminoresorcinol, 4-aminocatechol, 2-aminoresorcinol, 3-amino-2-chlorophenol, 2-amino-6-chlorophenol, 4-amino-2-chlorophenol, 2- amino-4-chlorophenol, 3-amino-5-methoxyphenol, 4-amino-3-methoxyphenol, 4-amino-2-methoxyphenol, 3-amino-5-methylphenol, 3-amino-5-methylphenol, 5-amino- 2-methylphenol, 3-N-methylaminophenol, and 4- (ethylamino) phenol.

The anhydride-containing polymers are copolymers of an unsaturated anhydride (for example, maleic anhydride, itaconic anhydride and methylmaleic anhydride) with other ethylenically unsaturated monomers which can be selected from de? Ns (for example ethylene, propylene, isobutylene, 1-hexene), aromatics ethylenically unsaturated (for example styrene, alpha-methyl styrene, para-methyl styrene and vinyl toluene), and / or one or more alkyl esters of acrylic acid or methacrylic acid (for example, methyl methacrylate, isobutyl methacrylate, ethyl methacrylate) , butyl methacrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate). Other suitable copolymerizable ethylenically unsaturated monomers which may be copolymerized with the unsaturated anhydride include nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride and vinyl esters such as vinyl acetate. It should be noted that the monomer units of the polymer-containing anhydride can be repeated in alternating or random sequences. Suitable di-epoxides include polyglycidyl ethers of polyphenols, such as bisphenol A. These are produced by etherification of a polyphenol with epichlorohydrin in the presence of an alkali. The phenolic compound can be 2,2-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) ethane; 1,1-bis (4-hydroxyphenyl) isobutane; 2, 2-bis (4-hydroxy-tert-butylphenyl) propane; bis (2-hydroxynaphthyl) -methane; 1,5-dihydroxynaphthalene; and 1,1-bis (4-hydroxy-3-allylphenyl) ethane. Also suitable are polyglycidyl ethers of polyhydric alcohols derived from polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,2. 6-hexanetriol, glycerin, and 2,2-bis (4-hydroxycyclohexyl) propane. The water-soluble or water-dispersible phenolic polymer of the present invention typically has a weight average molecular weight ranging from about 600 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 2,000 to about 10,000, as it is determined by gel permeation chromatography (GPC) using polystyrene standards. When the water-soluble or water-dispersible phenolic polymer is obtained by reaction of an amino phenol and an anhydride-containing polymer, the ratio of anhydride group to amino group is preferably from about 1: 1 to about 2: 1. Any excess of anhydride groups can be reacted with other amines or alcohols. The final acid number of the polymer should be in the range of from about 0 to about 50, preferably from about 0 to about 20, more preferably from about 0 to about 10. When the phenolic polymer soluble in water or dispersible in water is obtained by Reaction of an amino phenol and a di-epoxide, the ratio of epoxy group to amine hydrogen is preferably from about 2: 1 to 1: 2. Any possible remaining epoxide function can be reacted with primary or secondary amines, or with other chemical species that make the polymer cationic. The resulting phenolic polymer can be imparted the cationic function by Mannich reaction, where the phenolic polymer is reacted with a secondary amine and an aldehyde, preferably formaldehyde, to give a product that can be neutralized with an acid to make the polymer soluble in water or dispersible in water. Alternatively, the cationic function can be imparted to the anhydride based polymer using a co-monomer having a cationic function such as 4-vinyl pyridine (an amine), or methacrylamidopropyl trimethyl ammonium chloride (a quaternary ammonium salt). Cationic polymers can also be obtained by reaction of aziridine with acrylic acid-functional polymers, or by reaction of amines with chlorine-functional monomers.

Alternative methods of imparting cationic functionality to phenolic polymers prepared from di-epoxides may include the reaction of some of the epoxy groups with sulfides such as bis-hydroxyethyl sulfide to form ternary sulfonium salts, or by reaction of groups epoxy with amines or with hydroxyl-containing amines to form polymers with amine radicals which can be made soluble in water or dispersible in water by neutralization with acid. Suitable acids include hydrochloric acid, acetic acid, nitric acid, sulfamic acid and methane sulfonic acid. Co-solvents may be present to contribute to the solubility or dispersibility of the phenolic polymer in water. These solvents are usually compounds that contain both polar and non-polar character. Examples of suitable co-solvents include n-methyl pyrrolidone, dimethyl formamide, diethylene glycol dimethyl ether, l-methoxy-2-propanol, and n-butanol. The concentration of the soluble or water dispersible phenolic polymer in the aqueous composition of the present invention could be between about 0.01 and about 10 weight percent, preferably between about 0.05 and about 1 weight percent. The pH of the aqueous composition may vary between about 1 and about 8, preferably between about 2 and about 6. In the practice of the invention, the final rinse-free aqueous composition is applied to a substrate that has been previously treated by coating of conversion with, for example, a phosphate conversion coating. The aqueous rinse composition can be applied by spraying or immersion techniques. The rinsing time should be prolonged enough to ensure wetting of the surface with the aqueous rinse composition. Typically, the rinsing time is from about 5 seconds to about 10 minutes and, preferably, from about 15 seconds to about 1 minute at a temperature range of about 15 ° C to about 100 ° C and, preferably 20 ° C to about 60 ° C. After the final rinsing, the metal is usually dried either by air drying under ambient conditions or by forced drying. In some cases a rinsing with water is used after the final rinsing. A protective or decorative coating is usually applied to the substrate after it has been pre-treated as indicated above. It has been found that metal substrates that have been pretreated by phosphate conversion coating followed by a final rinse with the preferred non-chromic rinsing compositions of the present invention exhibit a corrosion and adhesion resistance that is at least equivalent to that of results from the use of final rinses containing chromium. This and other aspects of the invention are further illustrated with the following non-limiting examples.

EXAMPLES The following examples show the non-chromic rinsing of this invention, the methods of preparation and use thereof, and the comparison of the claimed rinses with the prior art compositions. The panels treated in the examples that follow had all been pre-treated according to the following sequence of processes unless otherwise indicated in the example. 1. Cleaning with solution of CHEMKLEEN 166 and CHEMKLEEN 171A which are alkaline cleaning agents manufactured by PPG Chemfil, Troy, Michigan, by spraying for 2 minutes at 49 -. 49-52 ° C. The cleaning solution consisted of a mixture of 15 parts by weight of CHEMKLEEN 166 with 1 part by weight of CHEMKLEEN 171A, with 59 milliliters of the resulting mixture added to 3.8 liters of water. 2. Rinse the panels with hot water by immersion for 15 seconds in water at 46 ° C to 49 ° C. 3. Application of nucleating agent "Rinse Conditioner" manufactured by PPG Chemfil, by spraying for 60 seconds at 38 ° C to 41 ° C. 4. Application of CHEMFOS 710, zinc phosphate conversion coating, of PPG Chemfil, by spraying for 2 minutes at 52 ° C - 54 ° C. 5. Rinse by immersion in deionized water for 15 seconds at room temperature. 6. Final rinsing treatment by immersion for 60 seconds at room temperature. The concentration of the aqueous rinse compositions was adjusted to 1000 ppm based on solids of the final rinse composition. 7. Rinsing with deionized water by spraying for 60 seconds at room temperature. All panels were then coated with ENVIROPRIME ™ III electrocoating primer, marketed by PPG Industries, Inc., Cleveland, Ohio, and cured for 30 minutes at 171 ° C with a resulting dry film thickness of 0.02-0, 03 mm. The test panels were then coated with a white acrylic enamel top coat "DHT-5920" marketed by PPG Industries, Inc. and cured for 30 minutes at 121 ° C, with a dry film thickness of 0.04. - 0.05 millimeters The test panels were then subjected to 50 cycles of chopping test as described below.

TESTING CYCLE TESTING The test panels were first screened by fastening a test panel on an Erichsen 508 Gravelometer and subjecting the test panel to shocks with steel shot 1/16 S-780 at nozzle pressure to the panel of 26, psi (1.8 bar). The test panels were then subjected to the following cycle: First the panels were hung vertically and immersed in a 5% salt solution (sodium chloride) at room temperature for 15 minutes. Second, the panels of the salt solution were removed and allowed to recover for 75 minutes. Third, the test panels were placed in a humidity chamber maintained at a relative humidity of 85% and 60 ° C for 22.5 hours. The total time for one cycle was 24 hours and it was repeated 50 times (50 cycles). Each panel was placed in water, then taken out of the water, dried by rubbing and immediately tested with masking tape covering the target area with 3M Scott Brand 898 tape and then quickly removing the tape from the test panel with a quick pull. The percentage of paint loss was then calculated by comparing the area of paint stripped from a target area of a square of 100 cm (4 inches) with the total target area.

EXAMPLE A A preparation of an anhydride-containing polymer was made from the following mixture of ingredients. Ingredients Weight in grams Load 1 Methyl isobutyl ketone 450 Load 2 Methyl isobutyl ketone 475 Styrene 550 Maleic anhydride 450 Load 3 Methyl isobutyl ketone 120 tert-Dodecyl mercaptan 20 LUPERSOLR 5751 50 Load 4 Methyl isobutyl ketone 30 LUPERSOL 575 5 Load 5 Methyl-pyrrolidinone 1075 1 t-amyl peroctoate from Elf Atochem.

Charge 1 was heated at 100 ° C under nitrogen in a stirred reaction vessel. Charge 2 and Charge 3 were added by separate streams to the reaction vessel simultaneously and followed substantially continuously over a period of 3 hours while maintaining the reaction mixture at 100 ° C. Charge 4 was then added to the reaction mixture over a period of 1 hour and then the reaction mixture was maintained at 100 ° C for 1 hour. The reaction mixture was then cooled to 70 ° C and then the Charge was added . The resulting mixture was reheated to 100 ° C and the distillate was removed in vacuo. The resulting anhydride-containing polymer had a total solids content of 61.4 percent determined at 110 ° C for 1 hour, and a weight average molecular weight of 6045 determined by gel permeation chromatography (GPC) using polystyrene patterns.

EXAMPLE B The anhydride-containing polymer of Example A was reacted with 4-amino phenol to form the phenolic polymer as follows. Ingredients Weight in grams Load 1 Copolymer of Example A 944.6 m-Pyrrolidinone 572.9 Load 2 4-aminophenol 224.5 Charge 1 was heated under nitrogen in a reaction vessel with stirring at 70 ° C. Charge 2 was then added and the reaction mixture was heated to 150 ° C and maintained for sufficient time for the reaction to be completed while the distillate was continuously removed. The reaction was considered complete when the acid MEQ was equal to 0.125. The resulting polymer had a total solids weight content of 47.6 percent determined at 110 ° C for 2 hours.

EXAMPLE C Cationic functionality was imparted to the phenolic polymer of Example B by use of the Mannich reaction and the resulting product made soluble by neutralization with acid as follows: Ingredients Weight in grams Load 1 Phenolic polymer of Example B 422.8 C ^ rga 2 Deionized water 9.0 Methyl ethanol amine 43.5 Load 3 Formaldehyde 37% 40.5 Load 4 Hydrochloric acid 37% 49.3 Deionized water 100.0 Load 5 Deionized water 154.6 Charge 1 was heated under nitrogen in a suitable reaction vessel with stirring at 30 ° C. Then the Charge 2 and the reaction mixture was heated to 50 ° C. Charge 3 was then added continuously over a period of 1 hour. The resulting reaction mixture was kept for 3 hours at 50 ° C, then heated to 80 ° C and maintained at that temperature for 3 hours. The reaction mixture was then cooled to 50 ° C and then Charge 4 was added and mixed well before adding Charge 5. The reaction mixture was cooled to room temperature, and the resulting polymer had a total weight content of solids of 40.6 percent, determined at 110 ° C for 2 hours, and an acid index of 39.25.

EXAMPLE D Example D shows the preparation of a phenolic polymer by reaction of "SMA-1000A" a maleic anhydride styrene copolymer manufactured by Elf Atochem, with 4-amino phenol, on which the cationic functionality was imparted by use of the reaction of Mannich, and then made soluble in water by neutralization with hydrochloric acid.

Ingredients Weight in grams Load 1 SMA-1000A 233.8 m-Pyrrolidinone 545.5 Load 2 4-Aminophenol 112.3 Load 3 Deionized water 36.0 Methyl ethanol amine 75.0 Load 4 Formaldehyde 37% 81.1 Load 5 37% hydrochloric acid 98.6 Deionized water 200.0 Charge 6 Deionized water 243.0 Charge 1 was heated under nitrogen in a suitable reaction vessel with stirring at 70 ° C. Charge 2 was then added and the reaction mixture was heated to 150 ° C and kept long enough for the reaction to be completed while the distillate was continuously removed. The reaction mixture was considered complete when the acid number was equal to 19.4.

The reaction mixture was then cooled to 50 ° C and then Charge 3. The Charge was then added continuously. 4 over a period of 1 hour. The resulting mixture was kept for 3 hours at 50 ° C, then heated to 80 ° C and maintained at that temperature for 3 hours. The reaction mixture was then cooled to 50 ° C and then Charge 5 was added and mixed well before Charge 6 was added. The reaction mixture was cooled to room temperature, and the resulting polymer had a total solids content of 36.3 percent determined at 110 ° C for 2 hours, and an acid index of 34.

EXAMPLE E A phenolic polymer was prepared from the reaction of styrene-maleic anhydride copolymer SMA 1000A with 4-aminophenol as follows. Ingredients Weight in grams Load 1 m-Pyrrolidinone 1038.0 Load 2 SMA-1000A 467.5 Load 3 4-Aminophenol 224.3 Charge 1 was heated under nitrogen in a reaction vessel at 100 ° C with stirring. Charge 2 was then added and then the reaction mixture was cooled to 70 ° C. Charge 3 was then added and the reaction mixture was heated to 150 ° C and kept long enough for the reaction to be completed while the distillate was continuously removed. The reaction was considered complete when the MEQ of the acid was equal to 0.197. The resulting polymer had a total solids weight content of 47.5 percent determined at 110 ° C for 2 hours.

EXAMPLE F The cationic functionality was imparted to the phenolic polymer of Example E using the Mannich reaction and the resulting product made soluble in water by neutralization with hydrofluoric acid as follows.

Ingredients Weight in grams Load 1 Phenolic polymer of Example E 839.8 Load 2 Deionized water 36.0 Methyl ethanol amine 86.3 Load 3 Formaldehyde 37% 81.1 Charge 1 was heated under nitrogen in a suitable reaction vessel with stirring at 50 ° C, then Charge 2. Charge 3 was added continuously over a period of 1 hour. The resulting reaction mixture was kept for 3 hours at 50 ° C, then heated to 80 ° C and maintained at that temperature for 3 hours. The reaction mixture was then cooled to room temperature. To neutralize the resulting phenolic polymer, 146 grams of 10% hydrofluoric acid was added to 759.2 grams of the phenolic polymer, mixed well and 239.5 grams of deionized water was added to the mixture. The resulting polymer had a total weight of solids content of 31.2 percent determined at 110 ° C for 2 hours.

Example 1 Cold-rolled and electro-galvanized steel test panels were pre-treated and coated in the manner described above using final rinsings prepared in Examples C, D and F, then subjected to 50 cycles of the Shock Cycle Test as It has been detailed before. These panels were compared with panels prepared and tested in a similar manner, but using as final rinse either deionized water or CHEMFOS 20, a final rinse composition containing chromium marketed by PPG Chemfil, Troy, MI. The results are as follows.

Percentage of paint loss Final rinsing Cold rolled steel Electroplated Example C 1.0 0.6 Example D 2.1 1.2 Example F 3.9 0.9 CHEMFOS 20 3.6 1.3 Deionized water 7.6 1.8 EXAMPLE G A polymer containing anhydride was prepared from the following mixture. Ingredients Weight in grams Caraa 1 m-Pyrrolidinone 700 Load 2 Methyl methacrylate 1140 Styrene 460 Maleic anhydride 400 tert-Dodecyl mercaptan 40 Load 3 m-Pyrrolidinone 218 LUPERSOL 575 102 Load 3A m-Pyrrolidinone 43.6 LUPERSOL 575 20.4 Charge 1 was heated under nitrogen in a suitable reaction vessel with stirring at 120 ° C. Charge 2 and Charge 3 in separate streams were added simultaneously to the reaction vessel and continued substantially continuously over a period of 2 hours while maintaining the reaction mixture at 120 ° C. Charge 3A was then added over a period of 20 minutes and then the reaction mixture was maintained at 120 ° C for 1 hour. The reaction mixture was then cooled to room temperature and the resulting polymer containing anhydride had a total solids content by weight of 75.3 percent determined at 110 ° C for 2 hours and a weight average molecular weight of 3852 determined by gel penetration chromatography (GPC) using polystyrene standards.

EXAMPLE H The polymer containing anhydride of Example G was reacted with 4-aminophenol to form a phenolic polymer as follows. Ingredients Weight in grams Load 1 Copolymer of Example G 2250.0 m-Pyrrolidinone 599.5 4-Aminophenol 336.8 Load 2 Butyl CELLOSOLVE1 637.3 1 Monobutyl ether of ethylene glycol, from Union Carbide Charge 1 was heated under nitrogen in a reaction vessel at 150 ° C with stirring and was maintained long enough for the reaction to complete while the distillate was continuously removed. The reaction was considered complete when the acid number was equal to 10.1. Charge 2 was added and the reaction mixture was cooled to room temperature. The resulting polymer had a total solids content of 55.1 percent, determined at 110 ° C for 2 hours.

EXAMPLE I Cationic functionality was imparted to the phenolic polymer of Example H by use of the Mannich reaction and the resulting product was made soluble in water by neutralization with an acid as follows: Ingredients Weight in grams Load 1 Phenolic polymer of Example H 309.4 Butyl CELLOSOLVE 77.4 Charge 2 Deionized water 43.5 Methyl ethanol amine 25.5 Charge 3 Formaldehyde 37% 20.2 Charge 4 37% hydrochloric acid 24.6 Deionized water 55.4 Charge 5 Deionized water 100.0 Charge 1 was heated under nitrogen in a suitable reaction vessel at 50 ° C with stirring, and then Charge 2. Charge 3 was added continuously over a period of 1 hour. The resulting reaction mixture was kept for 3 hours at 50 ° C, then heated to 80 ° C and maintained at that temperature for 3 hours. The reaction mixture was then cooled to 50 ° C and then Charge 4 was added and mixed well before Charge 5 was added. The reaction mixture was cooled to room temperature and the resulting polymer had a total solids content by weight of 33.1 percent determined at 110 ° C for 2 hours, and an acid index of 28.6.

EXAMPLE J A phenolic polymer was prepared from the reaction of styrene-maleic anhydride copolymer SMA 1000A with 4-aminophenol as follows. Ingredients Weight in grams Load 1 m-Pyrrolidinone 1085.8 SMA-1000A 489.0 Load 2 4-Aminophenol 234.9 Charge 1 was heated under nitrogen in a reaction vessel with stirring at 70 ° C. Charge 2 was then added and the reaction mixture was heated to 150 ° C and kept long enough to complete the reaction while the distillate was continuously removed. The reaction was considered complete when the acid number was equal to 7.8. The resulting polymer had a total solids content of 49.4 percent determined at 110 ° C for 2 hours.

EXAMPLE K Cationic functionality was imparted to the phenolic polymer of Example J by use of the Mannich reaction and the resulting product was made soluble in water by neutralization with nitric acid as follows: Ingredients Weight in grams Load 1 Phenolic polymer of Example J 432.9 Load 2 Deionized water 18.0 Methyl ethanol amine 37.5 Load 3 Formaldehyde 40.6 Load 4 Nitric acid 70% 45.0 Deionized water 100.0 Load 5 Deionised water 183.7 Charge 1 was heated under nitrogen in a suitable reaction vessel with stirring at 50 ° C, then Charge 2 was added. Charge 3 was then added continuously over a period of 1 hour. The resulting reaction mixture was kept for 3 hours at 50 ° C, then heated to 80 ° C and maintained at this temperature for 3 hours. The reaction mixture was then cooled to 50 ° C. Charge 4 was added to the reaction mixture to neutralize the resulting phenolic polymer, mixed well and then Charge 5. The resulting polymer had a total solids content of 35.6 percent determined at 110 ° C for 2 hours. hours.

EXAMPLE 2 Cold-rolled steel test panels were pretreated and coated as described in detail before using the final rinsings prepared in Examples D, I and K, then subjected to 50 cycles of the above-described chopping cycle test. . These panels were compared with panels prepared in a similar way and tested, but using deionized water or CMEMFOS 20 as final rinse. CHEMFOS 20 is a final rinse containing chromium marketed by PPG Chemfil, Troy. MY. The results are the following: Percentage of paint loss Final rinse Cold rolled steel Example D 14 Example I 20 Example K 20 CHEMFOS 20 22 Deionized water 51 EXAMPLE L Example L shows the preparation of a phenolic polymer by reaction of EPON 828, a di-epoxide manufactured by Shell Chemical, with 4-amino phenol, on which cationic functionality was imparted using the Mannich reaction and which became soluble in water by neutralization with acetic acid.

Ingredients Weight in grams Load 1 4-Aminophenol 164.0 OD ANOL PM1 109.3 Load 2 EPON 828 423.0 DOWANOL PM 282.0 Load 3 Deionized water 54.0 Methyl ethanol amine 112.5 Load 4 Formaldehyde 37% 121 , 5 Loading 5 Acetic acid 90.0 Loading 6 Deionized water 505.0 1 Monomethyl propylene glycol, from Dow Chemical Charge 1 under nitrogen in a suitable reaction vessel with stirring to dissolve it was heated to the reflux temperature and then cooled to 100 ° C. Charge 2 was then added over a period of 1 hour and then the reaction mixture was heated to 120 ° C and maintained for a sufficient time for the reaction to be completed. The reaction was considered complete when the epoxy equivalent was 55.555. The reaction mixture was then cooled to 100 ° C and then Charge 3. The reaction mixture was cooled to 50 ° C and then Charge 4 was added continuously over a period of 1 hour. The resulting mixture was kept for 3 hours at 50 ° C, then heated to 80 ° C and maintained at that temperature for 3 hours. Charge 5 was then added and the reaction mixture was thoroughly mixed before Charge 6 was added. The reaction mixture was cooled to room temperature and the resulting polymer had a total solids content of 44., 3 percent determined at 110 ° C for 2 hours, and an acid number of 58.7. The invention has been described in connection with specific embodiments in order to describe the best mode of carrying out the invention. It is to be understood, however, that other variations and modifications known to those skilled in the art can be made without departing from the scope of the invention as defined by the following claims.

Claims (14)

CLAIMS 1. An aqueous composition comprising between about 0.01 percent and about 10 percent by weight of water-soluble or water-dispersible phenolic polymer comprising the reaction product of: (a) an amino phenol having the following formula: where: X1 to X4 are H, OH, halogen, or an alkyl, aryl, or ether group, or a group that is not reactive with anhydrides or epoxides; R1 is H or a lower alkyl group having between 1 and 6 carbon atoms; Y. (b) an anhydride-containing polymer having one of the following general formulas: wherein: R 2 is H, or CH 3, Z is a group derived from an ethylenically unsaturated monomer or monomers capable of polymerizing with an unsaturated anhydride, m and n are integers equal to or greater than 1, the sum of which is sufficient to provide a molecular weight of 600 to 100,000 to the polymer, or, (c) a di-epoxide having the following general formula:
1. O O / \ / \ CH, CH RJ CH CH, wherein: R3 is an alkyl, aryl or cycloalkyl group, optionally containing functional groups such as ether, hydroxyl groups, or other groups that do not interfere with the reaction; said water-soluble or water-dispersible polymer being a group that imparts cationic functionality to the polymer.
2. 2. The composition according to claim 1 wherein the phenolic polymer has the following formula: A-NR1 0 where: > R1 is the same as H or a lower alkyl group having between 1 and 6 carbon atoms; R4 and R5 are identical to ethyl, methyl, hydroxyalkyl group, or where R4 and R5 taken together are cycloalkyl group, which may contain one or more N or 0 atoms; and '^. A is equal to the polymer derived from the anhydride-containing polymer or the di-epoxide.
3. 3. The composition according to claim 1 wherein the phenolic polymer has the following formula: A ^ N-A2 wherein: R4 and R5 are the same as ethyl group, methyl, hydroxyalkyl, or where R4 and R5 taken together are cycloalkyl group, which may contain one or more N or 0 atoms; and A1 and A2 are equal to polymer segments derived from the anhydride-containing polymer or the di-epoxide.
4. 4. The aqueous composition according to claim 1 wherein the water-soluble or water-dispersible phenolic polymer is present in an amount of about 0.01 percent to about 1 percent by weight. -,
5. 5. The composition according to claim 1 wherein the pH of the composition is from about 1 to about 8.
6. 6. The composition according to claim 1 wherein the pH of the composition is about 2 to about 6.
7. 7. The composition according to claim 1 wherein the phenolic polymer soluble in water or dispersible in water has a weight average molecular weight between about 600 and 100,000.
8. 8. The composition according to claim 7 wherein the phenolic polymer soluble in water or dispersible in water has a weight average molecular weight between about 1000 and 50,000.
9. 9. The composition according to claim 8 wherein the water-soluble or water-dispersible phenolic polymer has a weight average molecular weight between about 2000 and 10,000.
10. 10. The composition according to claim 1 wherein the aminophenol (a) is reacted with an anhydride (b), wherein the ratio of anhydride group to amine group in the reaction is from about 1: 1 to 3: 1.
11. 11. The composition according to claim 1 wherein the ratio of anhydride group to amine group in the water-soluble or water-dispersible phenolic polymer is from about 1: 1 to 2: 1.
12. 12. The composition according to claim 1 wherein R3 is an alkyl, aryl or cycloalkyl group.
13. 13. The composition according to claim 16 wherein R3 contains ether or hydroxyl functional groups.
14. 14. The composition according to claim 1 wherein the amino phenol (a) is reacted with a di-epoxide (c), wherein the ratio of epoxy groups to amine hydrogen in the reaction is from about 1: 2 to 3: 1.