Abstract:
An effective autodeposition bath with low volatile organic compound emissions can be compounded with polymer solids made by polymerizing a mixture of monomers consisting of certain acrylates and other monomers. E.g., a suitable mixture is, in percents by weight, 44% butyl acrylate, 36% acrylonitrile, 10% styrene, 7% methacrylic acid, 2% of the methyl ether of methacrylamide, and 1.5% of hydroxyethyl acrylate.

Description:
FIELD OF THE INVENTION 
     This invention relates to the use of liquid, usually aqueous, solutions or dispersions in which active metal surfaces of inserted objects are coated with an adherent polymer film that increases in thickness the longer the metal object remains in the bath, even though the liquid is stable for a long time against spontaneous precipitation or flocculation of any solid polymer, in the absence of contact with active metal. Such compositions are commonly denoted in the art, and in this specification, as &#34;autodeposition&#34; compositions, dispersions, emulsions, suspensions, baths, solutions, or a like term. Autodeposition is often contrasted with electrodeposition, which can produce very similar adherent films but requires that metal or other objects to be coated be connected to a source of direct current electricity for coating to occur. 
     DESCRIPTION OF RELATED ART 
     U.S. Pat. No. 3,592,699 of July 13, 1971, to Steinbrecher et al. is one of the early basic patents on autodeposition. It teaches autodeposition baths generally containing an appropriate polymer latex, an appropriate amount of a soluble oxidizing agent such as hydrogen peroxide or dichromate ion, fluoride ions, and sufficient acid to keep the pH within the range of about 2.5-3.5. The entire specification of this patent, to the extent not inconsistent with any explicit statement in this specification, is hereby incorporated herein by reference. 
     U.S. Pat. No. 4,030,945 of June 21, 1977, to Hall et al. teaches that the corrosion resistance of ferriferous surfaces coated by autodeposition can be substantially improved by treatment of the uncured autodeposited film with a variety of chromium containing materials. The entire specification of this patent, to the extent not inconsistent with any explicit statement herein, is hereby incorporated herein by reference. 
     U.S. Pat. No. 4,191,676 of Mar. 4, 1980, to Hall teaches that it is advantageous in autodeposition compositions and processes to keep the amount of surfactant in the aqueous phase of the composition below the critical micelle concentration. As a preferred method of achieving this goal, this patent teaches a method of polymerization called &#34;seed polymerization&#34;, which avoids the formation of any substantial amount of a separate phase of monomer(s) during the polymerization process. The portion of the specification of U.S. Pat. No. 4,191,676 between column 4 line 53 and column 6 line 9, inclusive, is hereby incorporated herein by reference. 
     U.S. Pat. No. 4,313,861 of Feb. 2, 1982, to Bassett et al. teaches the use of acrylic latexes in autodeposition compositions and processes. The latexes used are emulsion copolymers of acrylic acid or a substituted acrylic acid and another polymerizable monoethylenically unsaturated monomer, which may be styrene and/or acrylonitrile; the copolymers may also include up to 20% by weight of other comonomers containing a functional hydroxyl group, which may be hydroxyethyl acrylate, and the copolymers may also include up to 1.5% by weight of a polyunsaturated cross linker such as ethylene glycol di(meth)acrylate, and up to 0.3 weight % of a chain transfer agent such as a mercaptan. 
     U.S. Pat. No. 4,874,673 of Oct. 17, 1989, to Donovan et al. teaches that cracking of autodeposited films composed primarily of resin with a glass transition temperature of not less than 55° C. may be avoided by including in the autodeposition composition a fugitive plasticizer (alternatively called a coalescent), with the most preferred such plasticizer being 2,2,4-trimethylpentane diol-1,3 monoisobutyrate. The preferred resin for an autodeposition composition according to this invention is one prepared by copolymerizing methacrylic acid, ethyl hexyl acrylate, acrylonitrile, and styrene. The amount of fugitive plasticizer is normally from 8 to 30 percent by weight % of the latex resin solids used, with an amount from 10 to 25 weight % of the amount of latex resin solids more preferred. Commercial embodiments of the invention disclosed in this patent generally contain fugitive plasticizer to the extent of at least 15 weight % of the resin solids present. 
     The complete specification of the above summarized U.S. Pat. No. 4,874,673, to the extent not inconsistent with any explicit statement herein, is also incorporated herein by reference. 
     The coatings produced by commercial embodiments of the invention described in U.S. Pat. No. 4,874,673 are of high quality, but the high content of fugitive plasticizer in such embodiments produces emissions of volatile organic compounds (&#34;VOC&#34;) that are sometimes too high to be allowed in smog-prone urban areas under current environmental laws. It is an object of the present invention to provide autodeposition compositions and processes that produce coatings of at least as high quality as those now produced by commercialized autodeposition compositions and processes, but with substantially lower VOC emissions. 
     DESCRIPTION OF THE INVENTION 
     Except in the operating examples, or where otherwise explicitly indicated, in the broadest scope of the invention described here, all numerical quantities in this description indicating amounts of material or reaction conditions are to be understood as modified by the word &#34;about&#34;. Operation within the exact numerical ranges specified is generally preferred. 
     It has now been found that autodeposition compositions based on acrylic type polymer resins within a relatively narrow composition range specified further below allow the achievement of high quality coatings with little or even no coalescent needed. 
     Specifically, the dispersed solids in an autodeposition bath according to the present invention consist essentially of a copolymer of the following mixture of monomers: 
     (A) from 40-50 percent by weight (&#34;w/o&#34;), preferably from 43-45 w/o, of monomers selected from the group having the general formula I: ##STR1##  where R 1  is a saturated, branched or unbranched, alkyl group having from 3 to 8 carbon atoms and is preferably n-butyl and R 2  is hydrogen or methyl; 
     (B) from 30-40 w/o, preferably from 35-37 w/o, of acrylonitrile; 
     (C) from 0-20 w/o, preferably from 5-20 w/o, more preferably from 8-12 w/o, of monomers selected from the group consisting of styrene, α-methyl styrene, and methyl methacrylate, with styrene preferred; 
     (D) from 5-10 w/o, preferably from 6-8 w/o, of monomers selected from the group consisting of acrylic acid and methacrylic acid, with the latter preferred; 
     (E) from 0-5 w/o, preferably from 1-5 w/o, more preferably from 1.5-2.5 w/o, of the methyl ether of methyl acrylamidoglycolate, having chemical formula II ##STR2## (F) from 0-5 w/o, preferably from 1-5 w/o, more preferably from 1-2 w/o, of monomers selected from the group having the general chemical formula III ##STR3##  where R 2  has the same meaning as in part (A) and R 3  is a saturated, branched or unbranched, divalent hydrocarbon moiety having from 2 to 4, preferably 2, carbon atoms and having the two open valences on distinct carbon atoms. 
     In order to possess reasonable stability to aging, the latex to be used in the invention and containing dispersed solids of the copolymer composed of the residues after polymerization of monomers as specified above preferably also contains an emulsifying agent in an amount of from 0.3 to 1.0 w/o, preferably from 0.5-0.7 w/o, of the total weight in the latex of the monomers as set forth above. Any suitable emulsifying agent known in the art may be used, with anionic emulsifiers preferred. For example, suitable commercially available emulsifiers include Dowfax™ 2A-1 (sodium salt of alkylated diphenyl oxide disulfonate), Abex™ 26-5 Texapon™ E-12 and K-12, Alipal™ CO-433 (sodium salt of sulfated alkyl phenol ethoxylate with an average of 4 ethylene oxide molecules per phenyl ring), CO-436 (ammonium salt, otherwise the same as CO-433), EP-110, and EP-120, Disponsil™ AES-13, and Aerosol™ OT (sodium dioctylsulfosuccinate). The most preferred emulsifier is Dowfax™ 2A-1. Preferably, the latex is made by &#34;seed polymerization&#34; as described in U.S. Pat. No. 4,191,676 already noted above. 
     The polymer in the latex used in an autodeposition bath according to this invention preferably has a glass transition temperature (&#34;T g  &#34;) in the range from 55°-70° C., preferably in the range from 58°-66° C. The average particle size of the polymer particles in the latex preferably is within the range from 0.07 to 0.14 microns (&#34;μ&#34;), more preferably from 0.09 to 0.11μ, still more preferably from 0.096 to 0.104μ. The standard deviation of the particle size from the average or mean value is preferably not greater than 0.03μ, and more preferably is not greater than 0.02μ. The glass transition temperature of the polymer and the mean particle size and standard deviation therefrom may be measured by methods well known in the art. 
     The process of polymerization, including the initiation of polymerization, of the monomers already described above to produce a latex for use according to the invention may be accomplished by any appropriate method known in the art. Thus, for example, in a polymerization to be carried out at 80° C., ammonium persulfate in an amount of from 0.3 to 0.7 w/o of the total monomer weight may be successfully used to initiate polymerization. It has been found preferable, however, to utilize an initiator that combines a free radical generator such as persulfate with reducing agents such as sodium bisulfite and ferrous iron ions. The most preferred initiator contains ammonium persulfate, sodium bisulfite, and ferrous iron ions. When the latter component is supplied by ferrous sulfate heptahydrate as preferred, the amounts of each component are preferably from 0.2-0.4, more preferably from 0.27-0.33, w/o of ammonium persulfate; from 0.05-0.3, more preferably from 0.08-0.2, still more preferably from 0.13-0.17, w/o of sodium bisulfite; and from 0.0002-0.0015, more preferably from 0.00029-0.0007, still more preferably from  0.00050-0.00058, w/o of ferrous sulfate heptahydrate, with all these percentages by weight being based on the total weight of monomers to be polymerized. 
     In order to further reduce the VOC emissions from compositions according to this invention, the residual monomers are preferable stripped from the latex after normal polymerization is complete. Without such stripping, levels of both butyl acrylate and acrylonitrile monomers are likely to be more than 2,000 parts per million by weight (&#34;ppm&#34;) each. Reduction in these levels may be accomplished by conventional means such as exposure to vacuum, for example by exposure of the latex in a rotary evaporator for 2 hours at a temperature of 45°-47° C. at a pressure of 80-100 millibars. Such treatment was successful in reducing residual acrylonitrile from more than 1,000 ppm to less than 25 ppm and also substantially reduced residual butyl acrylate. About 13 w/o of the total aqueous phase distilled during this stripping process. Alternatively, stripping at 85° C. at atmospheric pressure may be used. 
     Another and often more convenient method that can give adequate stripping effect is to add more initiator after the polymerization at elevated temperature(s) is completed. For example, 0.1 w/o of ammonium persulfate may be added after the initially formed latex has cooled, and this will reduce the residual acrylonitrile and butyl acrylate by factors of about 2 to 4, i.e., down to less than 1,000 ppm for butyl acrylate and less than 400 ppm for acrylonitrile. This &#34;chaser&#34; method may advantageously be combined with stripping by distillation of volatiles if desired. The most preferred &#34;chaser&#34; consists of 0.1 w/o t-butyl hydroperoxide and 0.1 erythorbic acid, with the percentages being based on the total weight of monomers originally used to make the polymer in the latex treated. 
     Contrary to the prior art, many polymers as described above can be used within the scope of this invention to prepare satisfactory crack-free coatings, even when the T g  of the polymer is above 55° C., even though no coalescent or plasticizer is used in the autodeposition composition along with the polymer. In some cases, however, the quality of the coating formed by autodeposition may be further increased by addition of a coalescent along with a latex containing copolymer resin solids as described above. In such cases, the same coalescents as are described as &#34;fugitive plasticizers&#34; in U.S. Pat. No. 4,874,673 are preferred for use with this invention, including the highest preference for 2,2,4-trimethylpentane diol-1,3 monoisobutyrate as the coalescent. According to this invention, however, the amount of coalescent used is, with increasing preference, no greater than 8, 5, 4, or 1.5 w/o of the total weight of polymer solids in the autodeposition bath. 
     Except for the particular copolymer resin solids, coalescent content, and other conditions noted explicitly above, autodeposition compositions and processes according to this invention may be and preferably are essentially the same as in the prior art. Thus, a complete autodeposition bath contains, in addition to the dispersed resin solids and optional coalescent, an acidic component, preferably hydrofluoric acid, in sufficient amount to produce a pH of less than 7, preferably a pH in the range from 1.6 to 3.8. The autodeposition composition also contains an oxidizer component, preferably hydrogen peroxide, preferably in sufficient amount to maintain the oxidizing power of the solution, as measured by the potential of a platinum electrode immersed in the solution, at a potential at least 325 millivolts (&#34;mv&#34;) more oxidizing than a silver-saturated silver chloride reference electrode. When a bath is fresh, especially when it contains relatively little dissolved iron, considerably higher oxidizing potentials are generally preferred, sufficient that at least 0.2 grams of iron per square meter of ferriferous surface immersed in the bath will dissolve within the first minute of immersion. After iron accumulates in the bath, or when iron is added deliberately from the beginning of the process as taught in U.S. Pat. No. 4,411,937, the entire specification of which (except for any part that may be inconsistent with any explicit statement herein) is hereby incorporated herein by reference, the oxidizing potential is preferably kept somewhat lower than this, for example in the range from 350 to 375 mv more oxidizing than a standard silver-saturated silver chloride reference electrode. 
     Precleaning processes before use of an autodeposition bath according to this invention, the time and temperature of autodeposition treatment, and post-treatment(s) after formation of the wet autodeposited coating are all preferably the same in a process according to this invention as are preferred in the prior art, with the possible exception that the &#34;dwell time&#34; between removal of a coated part from the autodeposition bath and its first rinsing in a process according to this invention preferably is passed in an atmosphere with a relative humidity of at least 50%, or more preferably of at least 60%. Consistently with the prior art, the use of a chromium containing rinse of the wet autodeposited coatings as taught in U.S. Pat. No. 4,030,945 is highly preferred as part of, or in connection with, an autodeposition process according to this invention. 
     The practice of this invention may be further appreciated from the following non-limiting examples and comparison examples. 
     GENERAL PROCEDURES 
     Latex Synthesis 
     I. Thermal Initiator 
     The total intended final water content of the latex, except for a possible small fraction of the total reserved to dissolve part of the initiator, a specified fraction (5% unless otherwise indicated) of the mixture of monomers to be polymerized to form the latex, and a specified fraction (20% unless otherwise indicated) of the initiator to be used were introduced into a stirred vessel and brought to a temperature of 80° C. with constant stirring. The amount of emulsifier, and the distribution of this amount between the initial charge to the reaction vessel and the materials added later, are specified in the tables below. 
     After the temperature had reached 80°, the remainder of the monomer mix and initiator, together with any specified amount of emulsifier, were fed into the reaction vessel at a constant rate over 150 minutes (&#34;min&#34;). After completion of these additions, the latex was heated to 85° C. for 60 min, then cooled and filtered through cheesecloth. Some latexes where specifically indicated were &#34;chased&#34; after synthesis with a mixture of t-butyl hydroperoxide and erythorbic acid. 
     II. Mixed Thermal and Redox Initiation 
     This was performed in the same manner as for the purely thermal initiation described in part I, except that 
     (1) the temperature of synthesis was 60° C., 
     (2) the initiator comprised three components, and 10% of the persulfate, 10% of the bisulfite, and all of the ferrous sulfate heptahydrate were introduced in the initial charge, along with 5% of the monomer mix, and 
     (3) monomer mix, bisulfite, and persulfate, the latter two in aqueous solution, were fed separately during the remainder of the syntheses. 
     Latex and Polymer Analysis 
     (1) T g  was determined on a sample of polymer prepared by drying a sample of the latex at 140° for 30 min, using a Perkin Elmer Model DSC-4 differential scanning calorimeter at a scan rate of 40° C. per min. The value given is for the midpoint of the transition. 
     (2) Percent solids was determined on an accurately weighed 1-2 gram sample of the latex after drying in a forced air oven at 140° C. for 30 min. 
     (3) Percent conversion is defined as 100 times the ratio of the weight of dry polymer produced to the weight of monomers introduced. 
     (4) Latex surface tension (&#34;γ&#34;) was measured by the du Nouy method with a Fisher Tensiomat™. Values reported are uncorrected. 
     (5) Polymer particle size average and standard deviation in the latex were measured with a Nicomp™ Model 370 Submicron Particle Sizer. 
     (6) Latex viscosity values were measured with a Brookfield rotametric viscosimeter at 60 revolutions per minute with spindle #1. 
     (7) Percent wet gum is 100 times the ratio of the amount of material recovered by filtration through multiple layers of cheesecloth to the total weight of the batch of latex tested. 
     Autodeposition Formulation and Process Conditions 
     The normal formulation of an autodeposition composition was: 
     
         ______________________________________Latex               145 parts by weightAqueous solution containing:(0.75  --M HF)(0.54  --M FeF.sub.3)                53 parts by weight(0.06  --M H.sub.2 O.sub.2)Aquablack ™ 255 dispersion                4 parts by weightof carbon black pigmentDeionized water     798 parts by weightCoalescent          Variable as indicated______________________________________ 
    
     The autodeposition coating, for a time sufficient to produce a film 17.7±0.8μ thick, was normally followed by 60 seconds (&#34;sec&#34;) dwell time after removal from the bath, then 60 sec tap water rinse (at a water temperature of about 20° C.), then 60 sec treatment with a hexavlaent chromium containing rinse as described in U.S. Pat. No. 4,030,945, then 20 min in an oven at 160° C. for final cure. Coatings were applied to conventionally cleaned cold rolled steel panels, and these were performance tested in a conventional manner for wet adhesion and then after final curing for salt spray resistance, edge crack resistance, reverse impact at 0.45 and/or 1.8 kilogram-meters (=40 and 160 inch-pounds, respectively), pencil hardness of the film, and brake fluid resistance. 
     The following trademarks and acronyms and/or other abbreviations are used in the following tables and discussion: BOTM=based on total monomers; BA=butyl acrylate; AN=acrylonitrile; AM=acrylamide; S=styrene; AMS=α-methyl styrene; AA=acrylic acid; MAA=methacrylic acid; MAGME™=methylacrylamidoglycolate, methyl ether; HEA=hydroxyethyl acrylate; APS=ammonium persulfate; SMB=sodium (meta)bisulfite; t-BHP=tertiary butyl hydroperoxide; Texanol™=2,2,4-trimethylpentane diol-1,3 monoisobutyrate. 
     Table 1 shows that the amount of the preferred cross-linking combination monomers MAGME and HEA can be varied within a factor of three with relatively little effect on the quality of coating obtained when no coalescent is used. All these compositions are acceptable for some conditions. Table 2 shows that the T g  value is quite sensitive to the BA/AN ratio. Latex JG 1257-04, with the highest ratio shown, is less preferred because of its reduced brake fluid resistance. However, all these formulation can provide acceptable autodeposition coatings for some conditions of use. 
     Tables 3-6 show the effects of varying levels of four different emulsifiers, with the monomer composition constant. Aerosol™ OT (Table 3) and Alipal™ CO-433 (Table 4) showed little if any plasticizing effect from higher levels of emulsifier, while Alipal™ CO-433 (Table 5) showed a modest plasticizing effect and Dowfax™ 2A-1 (Table 6) showed a definite plasticizing effect. At the highest levels shown in the Tables, all these emulsifiers appeared to reduce wet adhesion and salt spray resistance. The results shown in these Tables are without any coalescent; when 8 parts by weight per hundred parts of polymer resin solids (&#34;PHR&#34;) of Texanol™ was added to these formulations, all edge cracking was substantially eliminated and all compositions passed the wet adhesion test. 
     Table 7 illustrates the effect of substituting the preferred HEA with HEMA. Brake fluid resistance and salt spray field results were less favorable than in Table 1. 
     Table 8 illustrates the effect of substituting AA for the preferred MAA. Coating properties were comparable to those obtained with 5-7% MAA, yielding a T g  of about 62° C. However, wet gum levels were undesirably higher and the wet adhesion test results were not as good as with MAA; the latter property could be overcome by addition of 8 PHR of Texanol™. 
     
                       TABLE 1______________________________________EFFECT OF TOTAL AMOUNT OF MAGME ™ + HEAPolymer Composition: (43 + x)BA/(45 + y)AN/7MAA/(3 - x)MAGME/(2 - y)HEALatex No.      NS1245-17 NS1245-21 NS1245-25______________________________________Latex Properties.sup.aMAGME/HEA      3/2       2/1.3     1/0.7x              0         1         2y              0         0.7       1.3% Wet Gum      0.23      0.10      0.05% Solids       41.9      41.9      41.9% Conv.        97.9      97.9      97.9Nicomp Mean d(μ)          0.136     0.129     0.124Brookfield Visc., 60 RPM          19.1      19.5      22.9(cps)γ (dynes/cm) (Uncorr.)          53.4      56.9      55.4Tg by DSC (°C.)          73.6      70.9      67.2AC Test Results.sup.bRinse-Off      v. sl.    None      NoneWet Adhesion3&#39;             P         F (spot).sup.c                              PScribe         P         P         PEdge Cracking  sl.-mod.  sl.-mod.  mod.-sev.Pencil Hardness          4H        4H        4HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.       4H        4H        3H 1 hr.         3H        3H        4H 2 hr.         3H        3H        3H 4 hr.         3H        4H        3H16 hr.         2H        F         3HSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         7         7+        7+Field          9+        9         10______________________________________ .sup.a Emulsifier: 0.30% Dowfax 2A1 (BOTM); all included in seed charge. .sup.b No coalescent employed in the formulation. .sup.c Failed similarly on retest. 
    
     
                                           TABLE 2__________________________________________________________________________EFFECT OF BA/AN RATIO IN MONOMERSPol. Comp.: (89.7-x)BA/xAN/7MAA/2MAGME/1.3HEALatex No.    NS1245-21              NS1245-27                    JG1257-01                          JG1257-04__________________________________________________________________________Latex Properties.sup.a% AN, x      45.7  43.7  41.7  39.7% Wet Gum    0.10  0.09  0.19  0.15% Solids     41.9  41.8  41.7  41.8% Conv.      97.9  97.7  97.4  97.7Nicomp Mean d(μ)        0.129 0.117 0.115 0.129Brookfield Visc., 60 RPM        19.5  20.8  14.1  23.0(cps)γ (dynes/cm) (Uncorr.)        56.9  54.1  55.1  55.6pH           4.30  4.20  3.80  4.15Tg by DSC (°C.)        70.9  69.5  67.0  63.1AC Test Results.sup.bRinse-Off    None  None  v.sl. NoneWet Adhesion3&#39;           F (spot)              P     P     PScribe       P     P     P     PEdge Cracking        sl.-mod.              sl.-mod.                    sl.-mod.                          sl.-mod.Pencil Hardness        4H    3H    4H    3HReverse Impact @        10/10 10/10 10/10 10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.     4H    3H    4H    3H 1 hr.       3H    3H    3H    3H 2 hr.       3H    3H    3H    2H  4 hr.      4H    3H    3H    HB16 hr.       F     3B    3B    3B++Salt Spray Resistance(0.7 mil; 504 hr.)Scribe       7+    7+    7     7Field        9     9+    9+    9__________________________________________________________________________ .sup.a Emulsifier: 0.30% Dowfax 2A1 (BOTM); all included in seed charge. .sup.b No coalescent employed in formulation. 
    
     
                       TABLE 3______________________________________EFFECT OF AEROSOL ™ OT EMULSIFIER LEVELPolymer Composition48BA/41.7AN/7MAA/2MAGME/1.3HEALatex No.      JG1257-31 JG1257-16 JG1257-13______________________________________Latex Properties.sup.a% Aerosol OT   0.15      0.30      0.60% Wet Gum      0.15      0.05      0.05% Solids       41.9      41.9      42.0% Conv.        98.1      97.9      97.9Nicomp Mean d(μ)          0.133     0.089     0.089Brookfield Visc., 60 RPM          21.5      44.2      76.0(cps)γ (dynes/cm) (Uncorr.)          45.1      42.3      38.9pH             4.45      4.50      4.40Tg by DSC (°C.)          68.9      66.4      66.4AC Test Results.sup.bRinse-Off      None      None      NoneWet Adhesion3&#39;             P         F (spot).sup.c                              F (spot).sup.cScribe         P         P         PEdge Cracking  tr.-mod.  tr.-sl.   tr.-sl.Pencil Hardness          3H        3H        3HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.       3H        3H        3H 1 hr.         3H        3H        3H 2 hr.         2H        3H        3H 4 hr.         3H        3H        3H16 hr.         3B        B         BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         7+         9        8-Field          8+        10        9+______________________________________ .sup.a All emulsifier (Aerosol OT) included in seed charge. .sup.b No coalescent employed in the formulation. .sup.c Failed on retest. 
    
     
                       TABLE 4______________________________________EFFECT OF ALIPAI ™ CO-433 EMULSIFIER LEVELPolymer Composition48BA/41.7AN/7MAA/2MAGME/1.3HEALatex No.      JG1257-19 JG1257-22 JG1264.15______________________________________Latex Properties% Alipal CO-433          0.30.sup.a                    0.60.sup.a                              1.0.sup.b% Wet Gum      0.10      0.06      0.10% Solids       42.0      42.1      42.2% Conv.        98.1      98.1      97.9Nicomp Mean d(μ)          0.092     0.073     0.077Brookfield Visc., 60 RPM          41.8      44.6      55.7(cps)γ (dynes/cm) (Uncorr.)          55.2      51.3      49.5pH             4.25      4.25      4.25Tg by DSC (°C.)          60.1      65.8      63.6AC Test Results.sup.cRinse-Off      None      None      NoneWet Adhesion3&#39;             P.sup.d   P         PScribe         P         P         PEdge Cracking  tr.-sl.   v.sl.-sl. sl.-sev.Pencil Hardness          3H        3H        3HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.       3H        3H        3H 1 hr.         3H        3H        2H 2 hr.         2H        3H        3H 4 hr.         H         3H        2B16 hr.         B         B         3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         7+        7         3Field          9         9+        8______________________________________ .sup.a All emulsifier included in seed charge. .sup.b Half emulsifier in seed charge; other half added during feed. .sup.c No coalescent employed in formulation. .sup.d Initially showed spot failure. Passed on retest. 
    
     
                       TABLE 5______________________________________EFFECT OF ALIPAL ™ CO-436 EMULSIFIER LEVELPolymer Composition48BA/41.7AN/7MAA/2MAGME/1.3HEALatex No.      JG1257-25 JG1257-28 JG1264-12______________________________________Latex Properties% Alipal CO-436          0.30.sup.a                    0.60.sup.a                              1.0.sup.b% Wet Gum      0.22      0.06      0.14% Solids       41.8      42.1      42.3% Conv.        97.7      98.1      98.1Nicomp Mean d(μ)          0.098     0.089     0.072Brookfield Visc., 60 RPM          38.0      53.9      77.4(cps)γ (dynes/cm) (Uncorr.)          53.9      52.3      51.0pH             4.25      4.20      4.25Tg by DSC (°C.)          67.7      63.4      63.3AC Test Results.sup.cRinse-Off      None      None      NoneWet Adhesion3&#39;             F (spot).sup.d                    P         PScribe         P         P         PEdge Cracking  tr.-v.sl. tr.-sl.   sl.-mod.Pencil Hardness          3H        3H        2HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.       2H        3H        2H 1 hr.         3H        3H        2H 2 hr.         3H        3H        B  4 hr.        2H        2H        2B16 hr.         2B        2B        3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         7+        7+        2Field          10        10        9______________________________________ .sup.a All emulsifier included in seed charge. .sup.b Half emulsifier in seed charge; other half added during feed. .sup.c No coalescent employed in formulation. .sup.d Failed similarly on retest. 
    
     
                       TABLE 6______________________________________EFFECT OF DOWFAX ™ 2A-1 EMULSIFIER LEVELPolymer Composition48BA/41.7AN/7MAA/2MAGME/1.3HEALatex No.      JG1264-03 JG1264-06 JG1264-09______________________________________Latex Properties% Dowfax 2A-1  0.30.sup.a                    0.60.sup.a                              1.0.sup.b% Wet Gum      0.09      0.06      0.04% Solids       41.8      42.2      42.0% Conv.        97.7      98.4      97.5Nicomp Mean d(μ)          0.112     0.087     0.096Brookfield Visc., 60 RPM          26.0      35.8      29.3(cps)γ (dynes/cm) (Uncorr.)          55.2      54.9      49.5pH             4.95      4.20      4.35Tg by DSC (°C.)          68.9      65.3      63.6AC Test Results.sup.cRinse-Off      None      None      NoneWet Adhesion3&#39;             P         P         PScribe         P         P         PEdge Cracking  v.sl.-mod.                    v.sl.-mod.                              sl.-mod.Pencil Hardness          3H        3H        3HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.       2H        3H        3H 1 hr.         H         3H        2H 2 hr.         HB        H         HB 4 hr.         3B        H         2B16 hr.         3B        2B        3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         6         7         5Field          7         7         7+______________________________________ .sup.a All emulsifier included in seed charge. .sup.b Half emulsifier in seed charge; other half added during feed. .sup.c No coalescent employed in formulation. 
    
     
                       TABLE 7______________________________________EFFECT OF SUBSTITUTING HEMA FORHEA IN MONOMER MIXPol. Comp.: 48BA/(45-x-y)AN/7MAA/xMAGME/yHEMALatex No.      JG1257-86 JG1257-80 JG1257-83______________________________________     Latex Properties.sup.a     % MAGME, x          3         2         1     % HEMA, y          2.25      1.5       0.75     % Wet Gum          0.14      0.06      0.05     % Solids          41.9      41.5      41.5     % Conv.          97.9      97.0      97.0     Nicomp Mean d(μ)          0.108     0.104     0.112     Brookfield Visc., 60 RPM          24.9      22.4      25.1     (cps)     γ (dynes/cm) (Uncorr.)          56.6      56.0      56.9     pH   3.90      4.55      4.70     Tg by DSC (°C.)          69.4      66.1      71.0     AC Test Results.sup.b     Rinse-Off          None      None      None     Wet Adhesion     3&#39;   P         P         P     Scribe          P         P         P     Edge Cracking          v.sl.-mod.                    sl.-mod.  v.sl.-mod.     Pencil Hardness          2H        2H        3H     Reverse Impact @          10/10     10/10     10/10     160 in-lbs.     Brake Fluid Resistance     (Pencil Hardness after     soak for)      1/2 hr.          2H        H         2H      1 hr.          H         HB        2H      2 hr.          B         HB        2H      4 hr.          3B        3B        3B     16 hr.          3B        3B        3B     Salt Spray Resistance     (0.7 mil; 504 hr.)     Scribe          7         7+        7+     Field          7         8+        7+______________________________________ .sup.a Emulsifier: 0.3% Dowfax 2A.1 (BOTM); all included in seed charge. .sup.b No coalescent employed in formulation. 
    
     
                       TABLE 8______________________________________EFFECT OF REPLACING MAA WITH AAAT CONSTANT T.sub.gPol. Comp.: (51-1/2x)BA/(45.7-1/2x)AN/xAA/2MAGME/1.3HEALatex No.      JG1257-34 JG1257-37 JG1257-40______________________________________Latex Properties.sup.a% AA, x        2         4         6% Wet Gum      0.26      0.33      0.70% Solids       41.9      41.8      41.8% Conv.        97.9      97.7      97.7Nicomp Mean d(μ)          0.131     0.111     0.112Brookfield Visc., 60 RPM          15.8      17.2      17.6(cps)γ (dynes/cm) (Uncorr.)          55.5      55.2      53.2pH             4.25      3.90      3.75Tg by DSC (°C.)          62.0      61.8      63.4AC Test Results.sup.bRinse-Off      None      v.sl.     NoneWet Adhesion3&#39;             F (spot)  F (spot)  F (spot)Scribe         P         P         PEdge Cracking  sl.-mod.  v.sl.-mod.                              sl.-sev.Pencil Hardness          2H        2H        2HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.       2H        2H        2H 1 hr.         2H        2H        2H 2 hr.         2H        2H        2H 4 hr.         H         2H        2H16 hr.         B         B         BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         7+        7+        7-Field          9         10        9______________________________________ .sup.a Emulsifier: 0.3% Dowfax 2A1 (BOTM); all included in seed charge. .sup.b No coalescent employed in formulation. 
    
     Some results with redox initiated polymerization are shown in Tables 9 and 10. All except NS1245-29 had relatively less brake fluid resistance than most thermally initiated polymers as shown in the preceding tables. The edge cracking shown in the Tables could be eliminated by adding 8 PHR of Texanol™. 
     Table 11 shows some properties of latexes made with thermally initiated polymerization, incorporating some additional emulsifier types not included in Tables 3-6. All these latexes produced autodeposited coatings adequate for use under many conditions, even without any coalescent, as shown in Table 12. The excellent reverse impact test results are particularly notable. The edge cracking shown in Table 12 can be essentially eliminated by addition of 8 PHR of Texanol™. 
     Table 13 shows the effect of various levels of addition of coalescent to formulation NS1217-86, which is described in more detail in Tables 11 and 12. Even though this latex has a T g  well above 55° C., the edge cracking that otherwise occurs with it can be entirely eliminated by addition of as little as 2 PHR of coalescent, when the air drying time is only 60 seconds. 
     Table 14 illustrates the effect of varying the ratio between HEA and MAGME. When the ratio is sufficiently high, as shown for latex JG1264-44 in the rightmost column of the Table, edge cracking can be completely eliminated, without any significantly adverse effect on deposited film properties compared with latex JG1264-50, where these two components are in equimolar ratio. Although applicant does not wish to be bound by any particular theory, it is believed that the hydroxy functionality of HEA operates to retain water somewhat more tenaciously during the dwell period between coating and rinsing and perhaps also during later drying, thus contributing to more even and less defect-prone film formation. 
     
                                           TABLE 9__________________________________________________________________________PROPERTIES OF LATEXES WITH REDOX INITIATED POLYMERIZATIONPolymer Composition: 48BA/41.7AN/7MAA/2MAGME/1.3HEA                                    Brookfield                                           γ  % Emulsifier  %     %   %   Nicomp                                    Visc. @                                           (dynes/cm)                                                    Tg byLatex No.  Seed   Feed   Wet Gum                      Solids                          Conv.                              Mean d(μ)                                    60 RPM (cps)                                           (Uncorr.)                                                 pH DSC__________________________________________________________________________                                                    (°C.)NS1245-29.sup.b,c  0.3% Dowfax           --   0.55  42.1                          98.1                              0.117 15.5   57.8  3.10                                                    64.6  2A-1NS1245-45.sup.d  0.3% Dowfax           --   0.20  41.7                          97.4                              0.106 19.4   60.7  3.45                                                    65.0  2A-1NS1245-34.sup.d  0.5% Dowfax         0.5% Dowfax                nil   41.7                          97.4                              0.083 22.2   50.4  3.40                                                    64.7  2A-1   2A-1NS1245-43.sup.d  0.3% Alipal           --   0.20  40.9                          98.3                              0.097 15.0   56.7  3.45                                                    65.0  CO-436NS1245-37.sup.c  0.5% Alipal         0.5% Alipal                nil   41.5                          96.1                              0.075 37.9   49.9  3.55                                                    67.0  CO-436 CO-436__________________________________________________________________________ .sup.a Redox Initiator: 0.3% APS/0.3% SMB/Trace Fe++, unless indicated otherwise. Polymerization Temperature: 60° C. .sup.b No Fe++ in redox system. .sup.c No chaser added. .sup.d tBHP/isoascorbic acid chaser employed. 
    
     
                                           TABLE 10__________________________________________________________________________PROPERTIES OF AUTODEPOSITED COATINGS WITH LATEXES SHOWN IN TABLE 9Polymer Composition: 48BA/41.7AN/7MAA/2MAGME/1.3HEA     Wet             Reverse                           Brake Fluid Resistance                                          Salt Spray (504 hr/Rinse     Adhesion           Edge Pencil                     Impact @                           Pencil Hardness after Soak                                          Resistance 0.7 mil)Latex No. Off 3&#39;       Scribe           Cracking                Hardness                     160 in-lbs                           1/2 hr                              1 hr                                 2 hr                                    4 hr                                       16 hr                                          Scribe                                               Field__________________________________________________________________________NS1245-29 None     P P   sl. sev.                4H   10/10 3H 3H 3H 3H 2B 8-   10NS1245-45 None     P P   tr.-sl.                2H   10/10 2H F  F  2B 2B 7-   7+NS1245-34 None     P P   sl.-sev.                2H   10/10 2H 2H H  B  3B 7-   7+NS1245-43 None     P P   tr.-sl.                2H   10/10 2H 2H H  2B 2B 7+   10NS1245-37 Slight     P P   mod. 2H   10/10 2H 2H F  B  2B 2    8__________________________________________________________________________ .sup.a No coalescent in formulation. 
    
     
                                           TABLE 11__________________________________________________________________________EFFECT OF EMULSIFIER TYPE ON LATEX PROPERTIES FOR A CONSTANT MONOMERCOMPOSITIONComposition 50BA/45AN/5MAA                                 Brookfield                                        γ             %.sup.b                   %   %   Nicomp                                 Visc. @                                        (dynes/cm)                                              Tg byLatex No. % Emulsifier.sup.a             Wet Gum                   Solids                       Conv.                           Mean d(μ)                                 60 RPM (cps)                                        (Uncorr.)                                              DSC (°C.)__________________________________________________________________________NS1217-59.sup.c 0.47% Dowfax 2A-1             0.08  41.6                       97.9                           0.118 16.6   55.8  49.5NS1217-68 0.47% Abex 26-5             0.13  41.9                       97.7                           0.092 52.5   62.2  61.4NS1217-70 0.47% Texapon K-12             nil   41.9                       97.7                           0.073 85.5   59.8  62.1NS1245-02 0.20% Texapon K-12             0.08  41.9                       98.1                           0.112 30.0   61.1  57.3NS1217-84 0.47% Alipal CO-436             0.03  42.1                       98.1                           0.087 46.1   54.4  59.6NS1217-92 0.30% Alipal CO-436             0.08  42.0                       98.1                           0.081 46.0   57.5  62.0NS1217-99 0.20% Alipal CO-436             0.15  42.0                       98.4                           0.111 35.6   59.2  65.9NS1217-86 0.47% Alipal CO-433             0.03  41.9                       97.7                           0.084 52.0   56.6  64.7NS1217-88 0.47% Alipal EP-110             0.03  42.1                       98.1                           0.097 72.5   58.7  57.9NS1217-95 0.47% Alipal EP-120             0.45  42.1                       98.1                           0.107 48.2   65.9  64.3NS1217-90 0.47% Disponil AES-13             0.04  41.9                       97.7                           0.106 26.4   56.5  59.4NS1217-97 0.30% Aerosol OT             0.03  41.9                       97.9                           0.098 47.9   44.1  63.7__________________________________________________________________________ .sup.a All included in seed charge. .sup.b Based on total batch weight. .sup.c Polymer Composition: 55BA/40AN/5MAA, for this latex only. 
    
     
                                           TABLE 12__________________________________________________________________________PROPERTIES OF AUTODEPOSITED COATING FROM LATEXES SHOWN IN TABLE 11for the Polymer Composition 50BA/45AN/5MAA       Wet                Reverse                                Brake Fluid Resistance                                                Salt Spray (504 hr/   Rinse       Adhesion               Edge  Pencil                          Impact @                                Pencil Hardness after Soak                                                Resistance 0.7 mil)Latex No.   Off 3&#39;  Scribe               Cracking                     Hardness                          160 in-lbs                                1/2 hr                                   1 hr                                      2 hr                                          4 hr                                             16 hr                                                Scribe                                                     Field__________________________________________________________________________NS1217-59.sup.b   None       P   P   sl. trace                     H    10/10 F  F  B   3B 3B 6     8NS1217-68   None       F(spot)           P   --    2H   10/10 2H 2H 2H  F  HB 7    10NS1217-70   None       F(spot)           P   None  2H   10/10 2H 2H 2H  F  HB 6    10NS1245-02   None       F(spot)           P   sl.-mod.                     3H   10/10 3H 3H 3H  3H 2B 6    10NS1217-84   None       F(spot)           P   sl.   3H   10/10 3H 3H 3H  F  2B 7     9NS1217-92   None       F(spot)           P   v. sl.                     3H   10/10 3H 3H H   H  B  8    10NS1217-99   None       F(spot)           P   sl.-mod.                     3H   10/10 3H 2H 2H  H  HB 7      9+NS1217-86   None       F(spot)           P   sl.-mod.                     3H   10/10 3H 3H H   B  2B 7      8+NS1217-88   None       F(spot)           P   sl.   2H   10/10 2H 2H 2H  2H B  7     9NS1217-95   None       F(spot)           P   sl.   3H   10/10 3H 2H 2H  H  2B 8    10NS1217-90   None       F(spot)           P   trace 2H   10/10 2H F  HB  HB 2B  6+    9+NS1217-97   None       F(spot)           P   sl.-mod.                     3H   10/10 3H 3H 2H  3H 2B 6     9__________________________________________________________________________ .sup.a No coalescent employed in the formulation. .sup.b Polymer composition: 55BA/40AN/5MAA, for this latex only. 
    
     
                                           TABLE 13__________________________________________________________________________EFFECT OF COALESCENT LEVEL AND CYCLE AIR DRYING TIME ON EDGE CRACKINGAutophoretic Cycle.sup.a                               Cure    Dry FilmTexanolCoating Time       Air Dry            Tap Water Rinse.sup.b                     Air Dry                          1077 RR                               Time                                   Temp                                       Thickness                                             EdgeLevel(sec.) (sec.)            (sec.)   (sec.)                          (sec.)                               (min.)                                   (°C.)                                       (mil) Cracking__________________________________________________________________________0    45      60  60        60  60   20  160 0.73  trace2    41      60  60        60  60   20  160 0.68  none4    43      60  60        60  60   20  160 0.68  none0    45     180  60       180  60   20  160 0.79  very slight2    41     180  60       180  60   20  160 0.68  very slight4    43     180  60       180  60   20  160 0.70  very slight0    45     300  60       300  60   20  160 0.78  moderate2    41     300  60       300  60   20  160 0.72  moderate4    43     300  60       300  60   20  160 0.73  moderate__________________________________________________________________________ .sup.a AC701 type formulation with indicated Texanol level. Room Conditions: 71° F./35% R.H. .sup.b Water Temp.  58° F. 
    
     
                                           TABLE 14__________________________________________________________________________EFFECT OF HEA/MAGME RATIO        Latex No.        JG1264-50   JG1264-47    JG1264-44        Polymer Comp.        48BA/41.7AN/7MAA/                    46.6BA/41.7AN/7MAA/                                 46BA/41AN/7MAA/        2MAGME/1.3HEA                    2MAGME/2.7HEA                                 2MAGME/4HE__________________________________________________________________________Latex Properties.sup.a% Wet Gum     0.10        0.15         0.15% Solids     42.1        42.0         41.7% Conv.      98.1        97.9         97.2Nicomp Mean d(μ)          0.073       0.078        0.084Brookfield Visc., 60 RPM        61.3        54.5         50.6(cps)γ(dynes/cm)(Uncorr.)        52.1        50.8         50.2pH            4.35        4.45         4.40Tg by DSC (°C.)        62.5        65.4         66.7AC Test Results.sup.bRinse-Off    None        None         NoneWet Adhesion3&#39;           F(spot)     F(spot)      PScribe       P           P            PEdge Cracking        None-v. sl. none-tr.     nonePencil Hardness        4H          2H(4H).sup.c 4HReverse Impact @        10/10       10/10        10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.     4H          2H(4H).sup.c 4H 1 hr.       4H          2H(2H).sup.c 4H 2 hr.       3H          H(H).sup.c   3H 4 hr.       HB          H(H).sup.c   HB16 hr.       2B          B(B).sup.c   BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe       4           6              5+Field          8+          8+         8__________________________________________________________________________ .sup.a Emulsifier: 0.6% Alipal CO436 (BOTM); all included in seed charge. .sup.b No coalescent employed in the formulation. .sup.c Results on retest. 
    
     Table 15 shows the effect of some variations of amount of chromium content in the preferred post-treatment composition for coatings deposited in accordance with this invention and in the temperature of final film cure. Generally, 6% post-treatment solution resulted in better salt spray resistance, with little if any corresponding disadvantage, while the two cure temperatures tried produced about the same results. 
     Table 16 shows that the hydroxyethyl acrylate component can be replaced by acrylamide, with little change in properties of either latex or coated film. On the other hand, other data not shown in detail were collected concerning the possible replacement of butyl acrylate by 2-ethylhexyl acrylate. This substitution produced excessive amounts of wet gum at the latex stage and poor wet adhesion after coating and thus is definitely not preferred. 
     Tables 17-19 illustrate two other possible variations within the scope of the invention the use of blends and heteroblock polymerization. Table 17 shows the properties of two latexes deliberately synthesized to give one with very high and one with very low T g . Properties of coatings made with blends of these two latexes are shown in Table 18. An attempt was made to determine the glass transition temperature of each of the blends used in Table 18, but the DSC curves failed to exhibit any sharp transition. Increasing amounts of the lower T g  component were positively correlated with reduced brake fluid resistance and film hardness, but all the blends had excellent resistance to edge cracking as shown in the Table. 
     Table 19 illustrates the results of successive polymerizations of monomer mixes that give the high or low T g  component when used alone, compared with each other and one of the blends from Table 17-18. The results with successive polymerization are much the same as with blends. 
     
                       TABLE 15______________________________________EFFECT OF CURE TEMPERATURE AND CHROMIUMCONCENTRATION IN THEPOST-TREATMENT SOLUTION______________________________________JG1264-44: 46BA/41AN/7MAA/2MAGME/4HEACure Temp. (°C.)           160.sup.b                   160      180   180DY-41 Conc. (%)  4       6        4     6Pencil Hardness 3H      3H       3H    4HReverse Impact @           10/10   10/10    10/10 10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.        2H      3H       4H    4H 1 hr.          4H      4H       3H    4H 2 hr.          2H      2H       3H    4H 4 hr.          H       H        3H    3H16 hr.          F       H        H     2HSalt Spray Resistance(0.7 mil; 504 hr.)Scribe           4+.sup.c                    6+.sup.c                             4     6Field            8+      10       9     9+JG1264-47: 46.6BA/41.7AN/7MAA/2MAGME/2.7HEACure Temp. (°C.)           160.sup.b                   160      180   180DY-41 Conc. (%)  4       6        4     6Pencil Hardness 4H      4H       3H    4HReverse Impact @           10/10   10/10    10/10 10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.        4H      4H       3H    3H  1 hr.         4H      4H       4H    5H 2 hr.          4H      4H       4H    4H 4 hr.          3H      2H       2H    3H16 hr.          H       H        H     HSalt Spray Resistance(0.7 mil; 504 hr.)Scribe           3+      6+       4     6+Field            8       10       9+    10-JG1264-50: 48BA/41.7AN/7MAA/2MAGME/1.3HEACure Temp. (°C.)           160.sup.b                   160      180   180DY-41 Conc. (%)  4       6        4     6Pencil Hardness 3H      3H       4H    4HReverse Impact @           10/10   10/10    10/10 10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.        3H      4H       4H    4H 1 hr.          4H      4H       3H    3H 2 hr.          4H      4H       2H    3H 4 hr.          H       2H       2H    2H16 hr.          B       H        HB    HSalt Spray Resistance(0.7 mil; 504 hr.)Scribe           5+.sup.c                    7.sup.c  4+    6+Field            9       10-      8     9______________________________________ .sup.a Standard coating conditions at immersion time which gave 0.7 mil dry film. Cure Time = 20 min. .sup.b Same conditions as those used for data in Table 7. .sup.c Films appeared to be hydroplasticized. 
    
     
                       TABLE 16______________________________________EFFECT OF REPLACING HYDROXYETHYL ACRYLATEWITH ACRYLAMIDEPolymer Composition: 48BA/(43-x)AN/7MAA/2MAGME/xAMLatex No.      JG1264-72 JG1264-75 JG1264-78______________________________________Latex Properties.sup.a% AM, x         0.8       1.6       2.4% Wet Gum       0.07      0.10      0.10% Solids       41.9      41.0      41.8% Conv.        97.7      95.6      97.4Nicomp Mean d(μ)            0.075     0.076     0.080Brookfield Visc., 60 RPM          81.0      77.8      94.3(cps)γ(dynes/cm)(Uncorr.)          53.0      51.7      50.1pH              4.35      4.45      4.55Tg by DSC (°C.)          62.5      66.5      61.5AC Test Results.sup.bRinse-Off      None      None      NoneWet Adhesion3&#39;             F(spot)   F(spot)   F(spot)Scribe         P         P         PEdge Cracking  none-v. sl.                    none-v. sl.                              none-v. sl.Pencil Hardness          3H        2H        3HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for) 1/2 hr.       3H        2H        3H 1 hr.         2H        2H        3H 2 hr.         2H        2H        2H 4 hr.         HB        H         H16 hr.         B         HB        HBSalt Spray Resistance(0.7 mil; 504 hr.)Scribe            7-       6+      6Field            8+        7+      6______________________________________ .sup.a Emulsifier: 0.6% Alipal CO436 (BOTM; all in seed charge. .sup.b No coalescent employed in the formulation. 
    
     
                       TABLE 17______________________________________PROPERTIES OF LATEXES PREPAREDFOR STUDY OF BLENDSPolymer Comp: xBA/yAN/7 MAA/2 MAGME/1.3 HEAEmuls.: 0.6% Alipal CO-436Init.: 0.38% APSLatex No.           JG1264-97 JG1274-04______________________________________% BA/% AN, x/y      40/49.7   60/29.7% Wet Gum           1.1       0.08% Solids            42.1      42.0% Conv.             98.1      97.9Nicomp Mean d (μ)               0.081     0.076Brookfield Visc., 60 RPM (cps)               36.9      63.2γ (dynes/cm) (Uncorr.)               49.0      57.2pH                  4.50      4.00Tg by DSC (°C.)               76.0      47.2______________________________________ 
    
     
                       TABLE 18______________________________________PROPERTIES OF COATINGS FROM BLENDED LATEXESBlend No.      JG1274-11 JG1274-10 JG1274-12______________________________________Wt. % JG1264-97.sup.b          75        50        25Wt. % JG1274-04.sup.b          25        50        75Rinse-Off      None      None      NoneWet Adhesion3&#39;             F (spot)  P         PScribe         P         P         PEdge Cracking  None      None      NonePencil Hardness          3H        2H        HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        3H         H        HB1 hr.          2H         F        2B2 hr.          2H         B        3B4 hr.           F        3B         3B+16 hr.         HB        2B        3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         5         6         5Field          8         8         8______________________________________ .sup.a No coalescent employed in the formulation. 
    
     
                                           TABLE 19__________________________________________________________________________COMPARISON OF TWO-STAGE POLYMERIZED LATEXES WITH COR-RESPONDING SINGLE-STAGE POLYMERIZED LATEX AND A BLENDPolymer Comp.: xBA/yAN/3.5 MAA/1 MAGME/0.65 HEA//x&#39;BA/y&#39;AN/3.5 MAA/1 MAGME/0.65 HEALatex No.      JG1274-07                JG1274-13                      JG1274-16                            JG1274-10__________________________________________________________________________Latex Properties.sup.a% BA/% ANStg. I x/y     20/24.9                30/14.8                      50/39.7.sup.c                            50/50Stg. II x&#39;/y&#39;  30/14.8                20/24.9                      50/39.7.sup.c                            Blend% Wet Gum      0.11  0.12  0.08  --% Solids       41.9  41.9  42.0  42.1% Conv.        97.7  97.7  97.9  --Nicomp Mean d (μ)          0.085 0.088 0.081 --Brookfield Visc., 60 RPM (cps)          36.8  33.6  57.0  --γ (dynes/cm) (Uncorr.)          53.0  51.8  53.5  --pH             4.40  4.55  4.45  --Tg by DSC (°C.)          v. broad                v. broad                      62.5  v. broadAC Test Results.sup.bRinse-Off      None  None  None  NoneWet Adhesion3&#39;             P     P     F (spot)                            PScribe         P     P     P     PEdge Cracking  None  None  None  NonePencil Hardness          2H    2H    2H    2HReverse Impact @          10/10 10/10 10/10 10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.         H     H    2H     H1 hr.          HB    HB    2H     F2 hr.           B     B    HB     B4 hr.          3B    2B     B    3B16 hr.         3B    2B     B    3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe          5+    3+   5     6Field          8     0      9+   8__________________________________________________________________________ .sup.a Emulsifier: 0.6% Alipal CO436 (BOTM); all in seed charge. .sup.b No coalescent employed in formulation. .sup.c Homogeneous composition: 50 BA/39.7 AN/7 MAA/2 MAGME/1.3 HEA 
    
     Table 20 illustrates the effect of partial substitution of acrylonitrile by methacrylic acid. There is less edge cracking at the highest level of methacrylic acid shown, but better salt spray resistance at the middle level. 
     Tables 21 and 22 illustrate the effect of including styrene in the monomer mix, with and without the cross-linking monomers HEA and MAGME respectively. Salt spray resistance is considerably improved by the inclusion of styrene in either case, but only with the cross-linking monomers included is the brake fluid resistance adequate for most purposes, and the edge cracking (without any coalescent added) is reduced. Edge cracking can be eliminated completely by adding 8 PHR of Texanol™ before autodepositing the coatings. 
     Tables 23-25 illustrate both the effect of &#34;chasing&#34; as described above to reduce the residual monomer content in latexes within the composition range of this invention and the importance of adequate humidity during the dwell stage in a complete autodeposition process according to this invention. The very poor salt spray resistance results shown in Table 24 were due to the low humidity during dwell when these samples were coated, as is shown by the comparisons in Table 25. 
     Tables 26 and 27 illustrate combined chasing and vacuum stripping, or in one case post heating of the latex without vacuum stripping, and also illustrate the effect of lowering the amount of emulsifier at two different initiator levels. The combination of higher initiator and higher emulsifier results in lower residual monomer content under the same physical conditions, but the higher initiator level slightly reduces salt spray resistance. The slight edge cracking shown can be eliminated by use of 7 PHR of Texanol™. 
     
                       TABLE 20______________________________________EFFECT OF SUBSTITUTING METHACRYLIC ACID FORACRYLONITRILEPolymer Composition: 48 BA/(48.7-x)AN/xMAA/2 MAGME/1.3 HEALatex No.      JG1274-29 JG1274-37 JG1274-41______________________________________Latex Properties.sup.a% MAA, x       7         10        13% Wet Gum      0.13      0.11      0.09% Solids       42.3      41.9      41.9% Conv.        98.8      97.9      97.9Nicomp Mean d (μ)          0.107     0.101     0.101Brookfield Visc., 60 RPM          34.6      27.6      32.8(cps)γ (dynes/cm) (Uncorr.)          58.1      56.5      56.2pH             4.65      4.55      4.50Tg by DSC (°C.)          63.9      67.4      69.8AC Test Results.sup.bRinse-Off      None      None      NoneWet Adhesion3&#39;             P         P         PScribe         P         P         PEdge Cracking  None-tr.  None-tr.  nonePencil Hardness          3H        2H        3HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        2H        2H        2H1 hr.          2H        2H        2H2 hr.          HB        2B        3B4 hr.          3B        3B         3B+16 hr.          B        2B        3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         6+        7-        6Field          7+        9         7+______________________________________ .sup.a Emulsifier: 0.3% Dowfax 2A1; all in seed charge. .sup.b No coalescent employed in the formulation. 
    
     
                       TABLE 21______________________________________EFFECT OF INCLUDING STYRENE WITHOUTCROSS-LINKING MONOMERSLatex No.      NS1280-06    NS1280-08______________________________________Latex Properties.sup.aPolymer Comp.  47.5 BA/35.5 45.5 BA/27.5          AN/10 S/7 MAA                       AN/20 S/7 MAA% Wet Gum      &lt;0.02        &lt;0.05% Solids       41.8         41.8% Conv.        97.7         98.7Nicomp Mean d (μ)          0.094        0.091Brookfield Visc., 60 RPM          40.0         45.1(cps)γ (dynes/cm) (Uncorr.)          62.8         64.9pH             4.80         4.65Tg by DSC (°C.)          64.0         58.7AC Test Results.sup.bRinse-Off      None         NoneWet Adhesion3&#39;             P            PScribe         P            PEdge Cracking  v. sl.-mod.  v. sl.-mod.Pencil Hardness          2H           HReverse Impact @          10/10        10/10160 ins-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.         H            H1 hr.           B           3B2 hr.          3B            3B+4 hr.          3B            3B+16 hr.         2B            3B+Salt Spray Resistance(0.7 mil; 504 hr.)Scribe         8             7Field          9            10______________________________________ .sup.a Emulsifier: 0.3% Dowfax 2A1; all in seed charge. .sup.b No coalescent employed in the formulation. 
    
     
                       TABLE 22______________________________________EFFECT OF INCLUDING STYRENE WITH CROSS-LINKING MONOMERSLatex No.      NS1280-02    NS1280-04______________________________________Latex Properties.sup.aPolymer Comp.  46 BA/33.7 AN/                       44 BA/25.7 AN/          10 S/7 MAA/  20 S/7 MAA          2 MAGME/     2 MAGME/          1.3 HEA      1.3 HEA% Wet Gum      0.05         0.05% Solids       41.6         41.9% Conv.        97.2         97.9Nicomp Mean d (μ)          0.099        0.102Brookfield Visc., 60 RPM          33.0         36.1(cps)γ (dynes/cm) (Uncorr.)          62.1         61.9pH             4.35         4.15Tg by DSC (°C.)          58.0         64.1AC Test Results.sup.bRinse-Off      None         NoneWet Adhesion3&#39;             P            PScribe         P            PEdge Cracking  tr.-v. sl.   v. sl.-mod.Pencil hardness          2H           2HReverse Impact @          10/10        10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        2H           2H1 hr.          2H            H2 hr.          HB            B4 hr.          3B            3B+16 hr.         3B           3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         8-           9Field          9+           9______________________________________ .sup.a Emulsifier: 0.3% Dowfax 2A1; all in seed charge. .sup.b No coalescent employed in the formulation. 
    
     
                       TABLE 23______________________________________USE OF CHASERS WITH BOTH THERMAL AND REDOXINITIATIONLatex No.      NS1280-35.sup.b                    NS1280-38.sup.c______________________________________Latex Properties.sup.aInitiator      0.4% APS  0.3% APS/0.15% SMB/                    0.00054% FeSO.sub.4.7H.sub.2 OChaser         0.2% APS  0.15% APS/0.075%                    SMB% Wet Gum      &lt;0.05     &lt;0.05% Solids       42.0      42.0% Conv.        98.6      98.6Nicomp Mean d (μ)          0.110     0.082Brookfield Visc., 60 RPM          16.0      19.4(cps)γ (dynes/cm) (Uncorr.)          49.8      52.2pH             3.65      2.95Tg by DSC (°C.)          68.9      67.1Residual Monomer (ppm)AN             1090       830BA             1140      1270AC Test Results.sup.dRinse-Off      None      NoneWet Adhesion3&#39;             P         PScribe         P         PEdge Cracking  mod.-sev. sl.-mod.Pencil Hardness          3H        3HReverse Impact @          10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        3H        3H1 hr.          2H        3H2 hr.           H         B4 hr.          2B        3B16 hr.          3B+      3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         6+          7+Field          9+        10______________________________________ .sup.a Emulsifier: 1.0% Dowfax 2A1 (0.3% in seed/0.7% in feed) .sup.b 80° C. Thermal, batch seed/gradual feed process. Chaser added over 1 hr. period while temp. was increased to 85° C. Held a 85° C. for an additional 1.5 hr. .sup.c 60° C. Redox, batch seed/gradual feed process. Chaser added at 60° C. over 1 hr. period. After chaser added, heated to 65° C. and held for 1.5 hr. .sup.d No coalescent employed in formulation. Laboratory conditions when panels coated were 72° F., 52-66% R.H. 
    
     
                       TABLE 24______________________________________USE OF CHASERS WITH LOW HUMIDITY DURINGDWELL TIME AFTER COATINGPolymer Composition46 BA/31 AN/10 S/7 MAA/2 MAGME/4 HEALatex No.      NS1280-54 NS1280-57 NS1280-64.sup.c______________________________________Latex Properties.sup.aEmulsifier (% BOTM).sup.b          1.0%      1.0%      1.0%          Dowfax    Alipal    Dowfax          2A-1      CO 436    2A-1% Wet Gum      0.05      0.10      0.10% Solids       42.1      42.0      42.8% Conv.        98.8      98.6      99.1Nicomp Mean d (μ)          0.112     0.115     0.117Brookfield Visc., 60 RPM          15.2      15.4      16.0(cps)γ (dynes/cm) (Uncorr.)          49.0      47.7      48.3pH             3.65      3.60      3.65Tg by DSC (°C.)          62.1      57.4      59.8Residual Monomer (ppm)AN             730       390       160BA             990       660       600AC Test Results.sup.cRinse-Off      None      None      NoneWet Adhesion3&#39;             P         P         PScribe         P         P         PEdge Cracking  sl.-mod.  mod.      sl.-sev.Pencil Hardness          2H        2H        2HReverse Impact @          10/10     10/10     10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        2H        2H        3H1 hr.           F        2H        2H2 hr.           3B+       3B+       3B+4 hr.           3B+        3B++     3B+16 hr.          3B+        3B++      3B++Salt Spray Resistance(0.7 mil; 504 hr.)Scribe         0         0         0Field          --        --        --______________________________________ .sup.a All prepared by 80° C. thermal, batch seed/gradual feed (2. hr.) process with 0.4% APS as initiator. Chaser (0.2% APS) was added over a 1 hr. period at 80° C. Batch was held at 85° C. for an additional 2 hr. .sup.b 0.5% in seed, 0.5% in feed. .sup.c A portion of aqueous phase (≈2.5%) was removed by atmospheric stripping during the 85° C. hold period. .sup.d No coalescent employed in formulation. Laboratory conditions when panels were coated were 71-74° F., 25-33% R.H. 
    
     
                                           TABLE 25__________________________________________________________________________COMPARISON OF HIGH AND LOW HUMIDITY DURING DWELL TIME AFTER COATING                 Brake Fluid Resistance                                  Salt Spray Resistance           Edge  (Pencil Hardness after soak for)                                  (0.7 mil; 504 hr.)   Cure Time/min.           Cracking                 1/2 hr.                    1 hr.                       2 hr.                          4 hr.                              16 hr.                                  Scribe                                        Field__________________________________________________________________________NS1280-54Original Result   20      sl.-mod.                 2H  F 3B+                          3B+ 3B+ 0     --Retest  20      sl.   3H 3H  B 3B  3B  5     6+Retest  40      sl.   3H 2H  B 3B  3B   4+   8NS1280-57Original Result   20      mod.  2H 2H 3B+                          3B++                              3B++                                  0     --Retest  20      sl.   3H 2H 3B 3B  3B   6-   7+Retest  40      sl.   3H 2H  B 3B  3B   6-   8+NS1280-64Original Result   20      mod.-sev.                 3H 2H 3B+                          3B+ 3B++                                  0     --Retest  20      sl.   3H  H 3B 3B+ 3B+  6-   6+Retest  40      sl.   2H  H 2B 3B  3B+ 4     7__________________________________________________________________________ .sup.a Dwell carried out in a covered sink with running hot water (60-80% R.H.). .sup.b Cure Temp. = 160° C. 
    
     
                                           TABLE 26__________________________________________________________________________EFFECT OF REDUCED EMULSIFIER AT LOW INITIATORLEVELPolymer Comp.: 42/BA/35 AN/10 S/7 MAA/2 MAGME/4 HEALatex No.      NS1280-73                 NS1280-83                        NS1280-77                               NS1280-80__________________________________________________________________________Latex Properties.sup.aEmulsifier (% BOTM)          0.6% Alipal                 0.3% Alipal                        0.6% Dowfax                               0.3% Dowfax          CO-436.sup.b                 CO-436.sup.c                        2A-1.sup.b                               2A-1.sup.c% Wet Gum      &lt;0.05  0.40   0.10   0.15% Solids       42.3   42.8   42.7   42.4% Conv.        98.6   98.4   98.2   98.9Nicomp Mean d (μ)          0.096  0.105  0.105  0.107Brookfield Visc., 60 RPM (cps)          22.0   25.0   24.3   28.0γ (dynes/cm) (Uncorr.)          52.3   56.8   53.9   59.2pH             4.40   4.30   4.35   4.40Tg by DSC (°C.)          65.2   68.4   68.8   63.7Residual Monomer (ppm)AN             222    291    320    196BA             610    839    900    807AC Test Results.sup.dRinse-Off      None   None   None   NoneWet Adhesion3&#39;             F (spot)                 F (spot)                        P      PScribe         P      P      P      PEdge Cracking  v. sl.-mod.                 tr.-sl.                        mod.   mod.Pencil Hardness          3H     3H     3H     3HReverse Impact @          10/10  10/10  10/10  10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        2H     3H     3H     3H1 hr.          2H     3H     2H     3H2 hr.          2H     2H     2H     3H4 hr.           B     2B     3B     3B16 hr.         3B     3B     3B     3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe          5+     7-     6     5+Field          9      10     10     8+__________________________________________________________________________ .sup.a All prepared by 80° C. thermal, batch seed/gradual feed (2. hr.) process with 0.3% APS as initiator. Chaser (0.1% APS) was added over a 1 hr. period at 80° C. The batch was heated to 85° C. and held at 85° C. for 2 hr. while a portion of the aqueous phase (≈4-6%) was removed by stripping at atmospheric pressure. .sup.b 0.5% in seed; 0.5% in feed. .sup.c All in seed. .sup.d No coalescent employed in formulation. Dwell carried out in a covered sink with running hot water (60-90% R.H.). 
    
     
                                           TABLE 27__________________________________________________________________________EFFECT OF REDUCED EMULSIFIER AT HIGH INITIATORLEVELPolymer Comp.: 42 BA/35 AN/10 S/7 MAA/2 MAGME/4 HEALatex No.      NS1280-95                 NS1280-92                        NS1280-98                               NS1280-86__________________________________________________________________________Latex Properties.sup.aEmulsifier (% BOTM)          0.6% Alipal                 0.3% Alipal                        0.6% Dowfax                               0.3% Dowfax          CO-436.sup.b                 CO-436.sup.c                        2A-1.sup.b                               2A-1.sup.c% Wet Gum      0.05   0.5    0.05   2+% Solids       43.4   43.4   43.7   41.6% Conv.        99.1   99.1   98.9   97.9Nicomp Mean d (μ)          0.108  0.140  0.135  0.111Brookfield Visc., 60 RPM (cps)          15.3   16.0   16.4   14.7γ (dynes/cm) (Uncorr.)          48.9   54.1   52.8   60.7pH             3.85   3.95   3.90   4.00Tg by DSC (°C.)          67.1   65.0   66.7   66.0Residual Monomer (ppm)AN             100    130    120    568BA             420    490    530    824AC Test Results.sup.dRinse-Off      None   None   None   NoneWet Adhesion3&#39;             P      P      P      PScribe         P      P      P      PEdge Cracking  sl.-mod.                 mod.   mod.   mod.Pencil Hardness          2H     2H     2H     2HReverse Impact @          10/10  10/10  10/10  10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        2H     2H     3H     2H1 hr.          2H     2H     3H     2H2 hr.           H     2H     2H     2H4 hr.           3B+   3B      B      H16 hr.          3B+   3B     3B     3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         4      2       4-    4+Field           6+    5      8      7+__________________________________________________________________________ .sup.a All prepared by 80° C. thermal, batch seed/gradual feed (2. hr.) process with 0.4% APS as initiator. Chaser (0.2% APS) was added over a 1 hr. period at 80° C. Except for NS128086, the batch was heated to 85° C. for 2 hr. while a portion of the aqueous phase (≈5-6%) was removed by stripping at atm. pressure. For NS128086, the batch temp. was maintained at 80° C. for 4 hr. without stripping. .sup.b 0.4% in seed; 0.2% in feed. .sup.c All in seed. .sup.d No coalescent employed in formulation. Dwell carried out in a covered sink with running hot water (60-90% R.H.). 
    
     Use of the most preferred chaser combination, t-butyl hydroperoxide+erythorbic acid+Fe +2  ions, is illustrated in Table 28. As may be seen from the Table, excellent reduction of both residual acrylonitrile and butyl acrylate was achieved. 
     Table 29 shows that dwell times varying over a factor of four (at &gt;50% relative humidity) had relatively little effect on the results. 
     Tables 30-32 compare the coating results from several coatings according to this invention with those from a commercial, polyacrylic latex-containing autodeposition bath (Autophoretic™ Coating 701, available from Parker+Amchem Div., Henkel Corp., Madison Heights, Mich.) in three well known measures of corrosion and/or shock damage resistance: the gravelometer/scab corrosion test, the gravelometer/salt spray test, and the scab corrosion test. In some cases, there are also comparison results against a conventional commercial cathodically electrodeposited paint (Uniprime™ from PPG Corporation, Pittsburgh, Pa.). Most or all of the coatings according to this invention were better than those from the commercial product(s) in the first of these tests and about equal to the commercial product(s) in the other two tests. 
     
                                           TABLE 28__________________________________________________________________________EFFECT OF MOST PREFERRED CHASER COMPOSITIONPolymer Comp.: (A.) 42 BA/35 AN/10 S/7 MAA/2 MAGME/4 HEA(B.) 44 BA/35.7 AN/10 S/7 MAA/2 MAGME/1.3 HEALatex No.      NS1292-09                 NS1292-17                        NS1292-13                               POL1285-77__________________________________________________________________________Latex Properties.sup.aPolymer Comp.  A.sup.b                 A.sup.c                        B.sup.b                               B.sup.cEmulsifier (% Dowfax 2A-1)          0.6    0.3    0.6    0.3Initiator (% APS)          0.4    0.3    0.4    0.3% Wet Gum      0.10   0.5+   &lt;0.05  0.1+% Solids       41.8   41.6   42.0   41.8% Conv.        98.6   98.1   99.1   98.6Nicomp Mean d (μ)          0.104  0.103  0.093  0.108Brookfield Visc., 60 RPM (cps)          19.4   22.9   21.0   25.4γ (dynes/cm) (Uncorr.)          53.7   57.5   54.7   61.8pH             3.65   4.05   3.65   4.00Tg by DSC (°C.)          64.9   67.1   66.3   66.0Residual Monomer (ppm)AN             &lt;25    &lt;25    &lt;25    &lt;25BA             &lt;25    &lt;25    &lt;25    &lt;25AC Test Results.sup.dRinse-Off      None   None   None   NoneWet Adhesion3&#39;             P      P      P      PScribe         P      P      P      PEdge Cracking  sl.    sl.-mod.                        sl.-mod.                               sl.-mod.Pencil Hardness          2H     2H     2H     HReverse Impact @          10/10  10/10  10/10  10/10160 in-lbs.Brake Fluid Resistance(Pencil Hardness aftersoak for)1/2 hr.        2H     2H     2H     2H1 hr.          2H     2H     2H     2H2 hr.           H      H      H     2H4 hr.          2B     3B     3B     2B16 hr.         3B     3B     3B     3BSalt Spray Resistance(0.7 mil; 504 hr.)Scribe         6+     7      6+     7Field          8+      9+    8+      9+__________________________________________________________________________ .sup.a All prepared by 80° C. thermal, batch seed/gradual feed (2. hr.) process. After addition batch was heated at 85° C. for 1 hr., then cooled to 65° C. At 65° C. a trace of FeSO.sub.4.7H.sub.2 O (0.00054%) was added as a 0.1% aq. soln. While temperature was maintained at 65° C., aq. solutions of .sub.- tBHP and Erythorbic acid were added during a 1 hr. period. .sup.b Emulsifier: 0.4% in seed; 0.2% in feed. Chaser levels: 0.22% .sub. tBHP/0.22% Erythorbic Acid. .sup.c Emulsifier: All in seed. Chaser levels: 0.15% .sub.- tBHP/0.15% Erythorbic Acid. .sup.d No coalescent employed in formulation. Dwell carried out in a covered sink with running hot water (60-90% R.H.). 
    
     
                                           TABLE 29__________________________________________________________________________EFFECT OF DWELL TIME VARIATION AFTER AUTODEPOSITION COATING       Film       Brake Fluid Resistance                                  Salt Spray ResistanceDwell       Thickness             Pencil                  (Pencil Hardness after soak for)                                  (504 hr.; 0.7 mil)Latex No..sup.c Time (sec.)       (mil) Hardness                  1/2 hr.                     1 hr.                        2 hr.                           4 hr.                              16 hr.                                  Scribe                                        Field__________________________________________________________________________JG1264-38.sup.d 15    0.70  4H   4H 4H 4H 2H H   7     9+ 30    0.72  4H   4H 4H 2H HB B    6+   9 45    0.73  4H   4H 4H 4H 2H HB  7     9+ 60    0.70  3H   3H 3H 2H  H HB  7     8+JG1264-69.sup.e 15    0.73  4H   3H 4H 3H 2H F    7+   9+ 30    0.70  4H   3H 4H 3H  H HB  6     8+ 45    0.73  4H   4H 4H 4H 2H HB  8     10 60    0.69  4H   3H 3H 3H 2H HB   7-   8+JG1274-29.sup.f 15    0.72  4H   4H 3H 3H 2H B   7     8+ 30    0.73  4H   4H 3H 3H 2H B    7-   8+ 45    0.72  5H   4H 3H 3H 2H HB  7     9 60    0.71  4H   3H 2H 2H HB B   7     9__________________________________________________________________________ .sup.a Coating cyle: Bath immersion to give 0.7 mil dry film; dwell; 60 sec. tap H.sub.2 O rinse; 60 sec. RR 1077 Reaction Rinse; Cure 20 min. @ 160° C. .sup.b No coalescent employed in formulation. .sup.c Polymer Comp.: 48 BA/41.7 AN/7 MAA/2 MAGME/1.3 HEA. All prepared b 80° C. thermally initiated process. .sup.d Emulsifier: 0.6% Texapon K12 .sup.e Emulsifier: 0.6% Alipal CO436 .sup.f Emulsifier: 0.3% Dowfax 2A1 
    
     
                                           TABLE 30__________________________________________________________________________RESULTS OF GRAVELOMETER/SCAB CORROSION TESTING             Film  Grav./ Cure        Thickness                   ScabCoating.sup.a Time (min)/Temp (°C.)             (mil) Cycles                       GM9508P Rating__________________________________________________________________________NS1280-02 20/160      0.73  8   GM6, SAE 3B, ASTM 4BNS1280-02 20/180      0.74  8   GM6, SAE 3B, ASTM 4BNS1280-02 20/160      1.04  8   GM7, SAE 3A, ASTM 4ANS1280-02 20/180      1.01  8   GM5, SAE 2B, ASTM 3BNS1280-04 20/160      0.76  8   GM3, SAE 2C, ASTM 3CNS1280-04 20/160      1.12  8   GM3, SAE 2C, ASTM 3CJG1264-44 20/160      0.73  8   GM3, SAE 2C, ASTM 3CJG1264-44 20/180      0.74  8   GM2, SAE 3D, ASTM 4DJG1264-44 20/160      1.04  8   GM3, SAE 2C, ASTM 3CJG1264-44 20/180      1.07  8   GM4, SAE 3C, ASTM 4CJG1264-50 20/160      0.70  8   GM5, SAE 2B, ASTM 3BJG1264-50 20/160      1.08  8   GM5, SAE 2B, ASTM 3BAC-701.sup.b 20/160      0.73  8   GM1, SAE 1D, ASTM 2DAC-701.sup.b 20/160      1.08  8   GM1, SAE 1D, ASTM 2DCED.sup.c --          1.0   10  GM6, SAE 3B, ASTM 4B__________________________________________________________________________ .sup.a Latex number given for experimentals; all formulated without any coalescent. .sup.b Contains 18 phr Texanol. .sup.c PPG Uniprime applied by cationic electrodeposition. 
    
     
                       TABLE 31______________________________________RESULTS OF GRAVELOMETER/SALT SPRAYCORROSION TESTING              Film   Cure       Thick-   Time (min)/              nessCoating.sup.a   Temp (°C.)              (mil)   GM9508P Rating.sup.b______________________________________NS1280-02   20/160     0.72    GM5, SAE 2B, ASTM 3BNS1280-02   20/180     0.70    GM3, SAE 2C, ASTM 3CNS1280-02   20/160     1.06    GM6, SAE 3B, ASTM 4BNS1280-02   20/180     1.02    GM4, SAE 3C, ASTM 4CNS1280-04   20/160     0.74    GM4, SAE 3C, ASTM 4CNS1280-04   10/160     1.07    GM5, SAE 2B, ASTM 3BJG1264-44   20/160     0.74    GM4, SAE 3C, ASTM 4CJG1264-44   20/180     0.75    GM1, SAE 1D, ASTM 2DJG1264-44   20/160     1.09    GM6, SAE 3B, ASTM 4BJG1264-44   20/180     1.09    GM3, SAE 2C, ASTM 3CJG1264-50   20/160     0.72    GM5, SAE 2B, ASTM 3BJG1264-50   20/160     1.05    GM6, SAE 3B, ASTM 4BAC-701.sup.c   20/160     0.76    GM4, SAE 3C, ASTM 4CAC-701.sup.c   20/160     1.05    GM4, SAE 3C, ASTM 4C______________________________________ .sup.a Latex number given for experimentals; all formulated without any coalescent. .sup.b After 336 hr. neutral salt spray. .sup.c Contains 18 phr Texanol. 
    
     
                       TABLE 32______________________________________RESULTS OF SCAB CORROSION TESTING          Film.sup.bCure           Thick-  15 Cycle Results.sup.b   Time (min)/              ness    Scribe Width                               FieldCoating.sup.a   Temp (°C.)              (mil)   Failure (in.)                               Failure (%)______________________________________NS1280-02   20/160     0.71    0.16     5NS1280-02   20/180     0.72    0.25     5NS1280-02   20/160     1.05    0.19     2NS1280-02   20/180     1.02    0.11     1NS1280-04   20/160     0.76    0.22     0NS1280-04   20/160     1.04    0.22     0JG1264-44   20/160     0.73    1.13     3JG1264-44   20/180     0.77    0.81     18JG1264-44   20/160     0.98    0.50     20JG1264-44   20/180     1.06    0.81     3JG1264-50   20/160     0.75    0.19     1JG1264-50   20/160     1.07    0.22     4AC-701.sup.c   20/160     0.73    0.22     2AC-701.sup.c   20/160     1.06    0.38     6CED.sup.d   --         1.0     0.13     0CED.sup.d   --         1.0     0.09     0______________________________________ .sup.a Latex number given for experimentals; all formulated without any coalescent. .sup.b Average of two panels for each condition. .sup.c Contains 18 phr Texanol. .sup.d PPG Uniprime applied by cationic electrodeposition.