Process for Cationic Electrodeposition of Amine Acid Salt-Containing Polymers

One thousand and sixteen parts of EPON 1001 which is the polyglycidyl ether of Bisphenol A having an epoxy equivalent weight of 508 and commercially available from Shell Chemical Company were charged into a reactor with 510 parts by weight of polytetramethylene glycol possessing a molecular weight of 1020 and commercially available from Quaker Oats Company as POLYMEG 1020, and 83.8 parts of diethylene glycol diethyl ether. The charge was heated to 60.degree. C. with agitation and 65.9 parts of diethylamine introduced. The batch was then heated to 155.degree.-160.degree. C. and held for approximately 10 hours for chain extension. At this point, the reaction mixture was cooled to 130.degree. C. and thinned with 197.1 parts by weight of ethylene glycol monoethyl ether.

In another reactor a polyurethane crosslinker was prepared by adding 218 parts by weight of 2-ethyl hexanol slowly to 291 parts by weight of an 80/20 isomer mixture of 2,4-/2,6-toluene diisocyanate under agitation and a dry nitrogen blanket, keeping the reaction temperature under 100.degree. F. (38.degree. C.) by external cooling. The charge was held an additional one-half hour at 100.degree. F. (38.degree. C.) and then heated to 140.degree. F. (60.degree. C.) at which point 75 parts by weight of trimethylolpropane were added followed by 0.08 parts of dibutyltin dilaurate catalyst. After an initial exotherm, the batch was held at 250.degree. F. (121.degree. C.) for 11/2 hours until essentially all of the isocyanate moiety was consumed as indicated by infrared scan. The batch was then thinned with 249 parts of ethylene glycol monoethyl ether.

A cationic pigment dispersion was manufactured by first preparing a dispersant by blending 138 parts of alkyl imidazoline (Geigy Amine C), 31 parts of glacial acetic acid, 138 parts of ethylene glycol monobutyl ether, and 383 parts of deionized water. One hundred parts of this dispersant were mixed with 40 parts of acetylenic alcohol commercially available from Air Products and Chemicals Inc. As SURFYNOL 104A, 260 parts of deionized water, 134 parts of 325 mesh anthracite coal, 40 parts of lead silicate, 20 parts of strontium chromate and 6 parts of clay commercially available from National Clay as BENAGEL EW. The resultant slurry was then ground to a Hegman No. 7 fineness reading in a suitable mill.

To prepare the chain extended, electrodepositable thermosetting cationic urethane modified composition, 275 parts of the polytetramethylene glycol chain extended polyether vehicle were blended with 217 parts of a polyurethane crosslinker, and 7.6 parts of dibutyltin dilaurate catalyst, followed by neutralization with 12.9 parts of glacial acetic acid, and reduction with 57 parts of n-butyl alcohol and 458.1 parts of deionized water. To this solubilized vehicle composition was then added 285 parts of the pigment dispersion followed by 1905.4 parts of deionized water to let down the composition to coating solids. This electrodeposition bath showed a pH of 5.6, had a rupture voltage of 320 volts and yielded smooth, hard, flexible films of 0.45 mil thickness when cathodically electrodeposited over zinc phosphated steel panels at 280 volts for 2 minutes and cured for 20 minutes at 400.degree. F. (204.degree. C.).

Into a suitable reactor were charged 970 parts by weight of EPON 1001 having an epoxy equivalent weight of 485 and 265 parts by weight of a polycaprolactone diol sold commercially by Union Carbide Corporation under the trade name of PCP 0200. This particular product was believed to be made by ring opening epsilon-caprolactone with ethylene glycol to produce a polymer product having a molecular weight of approximately 543. This charge was heated to 100.degree. C. under a nitrogen blanket and 0.46 parts of benzyl dimethylamine added. The reaction mixture was heated further to 130.degree. C. where it was held for about 11/2 hours. The batch was then cooled to 110.degree. C. and 110 parts by weight of methyl isobutyl ketone was introduced into the reaction vessel followed by 39.8 parts by weight of a 73 percent non-volatile solution of methyl isobutyl diketimine of diethylene triamine in methyl isobutyl ketone solvent followed by an additional 100 parts by weight of methyl isobutyl ketone. Cooling was continued until the batch reached 70.degree. C. at which point 53.1 parts by weight of diethylamine were introduced and the batch reheated to 120.degree. C. where it was held for 3 hours and then discharged.

To prepare the chain extended electrodepositable thermosetting cationic urethane modified composition, 576 parts of the above-described polycaprolactone diol chain extended polyether was blended with 310 parts by weight of the polyurethane crosslinker of Example I and 13.2 parts of dibutyltin dilaurate catalyst followed by neutralization with 12.3 parts of glacial acetic acid and reduction slowly with 705.5 parts of deionized water. To this solubilized vehicle composition was then added 297 parts of the pigment dispersion of Example I, 39 parts of ethylene glycol monohexyl ether followed by 1886 parts of deionized water to let down the composition to a coating solids of about 10 percent by weight.

This electrodeposition bath showed a pH of 6.1, had a rupture voltage of 390 volts and yielded smooth, hard, flexible films of approximately 0.7 mil film thickness when cathodically electrodeposited over an untreated steel panel at 340 volts for 2 minutes and cured for 20 minutes at 400.degree. F. (204.degree. C.). When scribed and exposed to a salt fog at 100.degree. F. (38.degree. C.) as described in ASTM D-117-73, the panel displayed only 1/32 inch scribe creepage from the scribe mark after 14 days.

Into a suitable reactor were charged 1108 parts by weight of EPON 1001 having an epoxy equivalent of 534 plus 637 parts by weight of a polycaprolactone diol sold commercially by Union Carbide Corporation as PCP 0230. This particular product was believed to be formed by ring opening epsilon-caprolactone with diethylene glycol to produce a polymer having a molecular weight of approximately 1250. This charge was heated to 60.degree. C. at which point 62 parts of diethylamine were added, followed by heating the reaction mixture to 130.degree. C. under a nitrogen blanket and holding at this temperature for 31/2 hours at which point 200 parts of methyl isobutyl ketone were added, the reaction mass heated to 140.degree. C. during which time 20 parts of the volatiles were stripped off. The reaction mixture was cooled to 130.degree. C. and 584.5 parts of methyl isobutyl ketone added. Cooling was continued to 90.degree. C. followed by the addition of 39.8 parts of methyl isobutyl diketimine of diethylene triamine having a solids content of 73 percent in methyl isobutyl ketone. The reaction mass was heated to 130.degree. C. and held for 21/2 hours while stripping off 320.9 parts of volatiles. The mixture was cooled to 100.degree. C. at which point 9 grams of water were added and the mixture held at 100.degree. C. for 10 minutes before discharging.

To prepare the chain-extended electrodepositable thermosetting cationic urethane modified composition, 318 parts of the above-described polycaprolactone diol chain extended polyether were blended with 178 parts of the polyurethane crosslinker of Example I and 7.6 parts of dibutyltin dilaurate catalyst and 5.7 parts of glacial acetic acid. After slow reduction with 206.7 parts of deionized water, 171 parts of the pigment dispersion of Example I were added followed by further reduction with 286.9 parts of deionized water.

This electrodeposition bath showed a pH of 6.1, had a rupture voltage of 370 volts and yielded smooth, hard, flexible films of 0.6 mil when zinc phosphated steel panels were electrodeposited at 300 volts for 2 minutes and cured for 20 minutes at 400.degree. F. (204.degree. C.). When exposed to salt fog at 100.degree. F. (38.degree. C.) according to ASTM D-117-73, the panel displayed only 1/32 of an inch creepage from the scribe mark after 14 days.

Into a suitable reactor were charged 975.6 parts by weight of EPON 1004 which is a polyglycidyl ether of Bisphenol A and epichlorohydrin having an epoxy equivalent of 975.6 and commercially available from Shell Chemical Company, plus 489.6 parts of polycaprolactone diol sold commercially by Union Carbide Corporation as PCP 0240 plus 257.6 parts by weight of methyl isobutyl ketone. The PCP 0240 is believed to be prepared by ring opening epsilon-caprolactone with diethylene glycol to produce a polymer having a molecular weight of approximately 2000. The mixture was heated to 135.degree. C. and held for 38 minutes while stripping off the dissolved water. The reaction mixture was then cooled to 55.degree. C. at which point 21.6 parts of diethylamine were added followed by reheating to 130.degree.-134.degree. C. and holding for 3 hours. The reaction product was then allowed to cool overnight.

The following morning there was added 79.6 parts of methyl isobutyl diketimine of diethylene triamine as a 70 percent solids solution in methyl isobutyl ketone. The mixture was heated to 135.degree. C. and held for 9 hours at which point 379.6 parts of methyl isobutyl ketone were added followed by 7 parts of deionized water and holding the reaction mass at 125.degree. C. for 21/2 hours. To prepare the chain-extended electrodepositable thermosetting cationic urethane modified composition, 383 parts of the above polycaprolactone diol extended polyether were blended with 178 parts of the polyurethane crosslinker of Example I, 7.6 parts of dibutyltin dilaurate catalyst, and 7.2 parts by weight of glacial acetic acid. After slow reduction with 184.2 parts of deionized water, 171 parts of the pigment dispersion of Example I was added followed by further reduction with 2869 parts of deionized water.

This electrodeposition bath showed a pH of 6.0, a rupture voltage of 380 volts and yielded smooth, hard, flexible films of 0.7 mil when untreated steel panels were electrodeposited at 330 volts for 2 minutes at 88.degree. F. (31.degree. C.) and cured for 20 minutes at 400.degree. F. (204.degree. C.).

The 2-ethyl hexanol monourethane of 2,4-toluene diisocyanate was prepared by adding 1953 parts of 2-ethyl hexanol to 2610 parts of 2,4-toluene diisocyanate and 200 parts of methyl butyl ketone over a 5-hour period with agitation and external cooling to maintain the batch reaction temperature below 20.degree. C. The batch was then thinned with 100 parts of methyl butyl ketone and stored under dry nitrogen.

In another reactor, 576 parts of EPON 828, 118 parts of 1,6-hexanediol and 50 parts of toluene were charged. EPON 828 is the polyglycidyl ether of Bisphenol A having an epoxy equivalent of about 192 and is commercially available from Shell Chemical Company. The mixture was heated to its reflux temperature of 165.degree. C. and held for one hour. After cooling to 100.degree. C., 15 parts of a catalyst solution of 23.8 percent aluminum isopropoxide in benzene were added and the reaction mixture was reheated to 180.degree. C. and held for 135 minutes.

Six hundred fifty-three parts of the above hexanediol chain-extended diglycidyl ether were charged into a new reactor along with 174.5 parts of methyl butyl ketone, and the mixture heated to 100.degree. C. Four hundred thirty-eight parts of the previously prepared monourethane plus 22 drops of dibutyltin dilaurate were added to the reaction mixture, and the mixture heated to 120.degree. C. and held for 50 minutes, at which point all isocyanate was essentially consumed as indicated by an infrared scan. The reaction mixture was then cooled to 110.degree. C. at which time 77.5 parts of diethylamine and 27 parts of the methyl isobutyl ketone diketimine of diethylene triamine were added. The reaction mixture was then heated to 120.degree. C. and held for 65 minutes.

Twelve hundred parts of the above resin were dispersed by pouring hot from the reactor into an agitated solution of 87 parts of 88 percent lactic acid and 1588 parts deionized water.

A cationic pigment dispersant was prepared by heating a mixture of 744.2 parts of stearyl glycidyl ether (Proctor and Gamble's EPOXIDE 45) and 156.6 parts of ethylene glycol monobutyl ether to about 70.degree. C. and then adding 150.2 parts of n-methyl ethanolamine over a 25-minute period with external cooling to keep the bath temperature below 85.degree. C. Ten more parts of ethylene glycol monobutyl ether were then added and the reaction mixture was heated to 140.degree. C. and held for 30 minutes. One hundred eighty-eight parts of this dispersant were then solubilized by blending with 132 parts of ethylene glycol monobutyl ether, 40 parts of 88 percent lactic acid and 440 parts deionized water.

To prepare a pigment paste, 90 parts of a catonic pigment dispersant prepared as described above were blended with 4 parts of acetylenic alcohol defoamer (SURFYNOL 104A), 306 parts of deionized water, 46.4 parts of phthalocyanine blue pigment, 108.6 parts brown iron oxide pigment, 30 parts of lead silicate and 15 parts of strontium chromate and the resultant slurry was ground in a suitable mill.

To prepare the chain-extended, electrodepositable thermosetting cationic urethane modified composition, 952 parts of the dispersed 1,6-hexanediol chain extended polyether vehicle were further reduced with 7.4 parts dibutyltin dilaurate, 228 parts of pigment paste and 2613 parts of deionized water. This electrodeposition bath had a rupture voltage of 380 volts and yielded smooth, hard, flexible films of 0.5 mil thickness when cathodically electrodeposited over zinc phosphated steel at 300 volts for 2 minutes and cured for 20 minutes at 400.degree. F. (204.degree. C.).

Into a suitable reactor were charged 1108 parts by weight of EPON 1001 having an epoxy equivalent weight of 554, plus 122 parts of methyl isobutyl ketone. The reaction mixture was heated to 190.degree. C. and 73.3 parts of volatiles were removed by distillation. After cooling to 110.degree. C., there was added 369.3 parts of the 2-ethyl hexanol monourethane of 2,4-toluene diisocyanate prepared as described in Example V above. The reaction mixture was heated to 120.degree. C. and held for one hour at which time there was added 265 parts of polycaprolactone diol commercially available from Union Carbide Corporation as PCP 0200 and 0.92 parts benzyl dimethylamine catalyst. The reaction mixture was then heated to 130.degree. C. and held for 4 hours at which time there were added 525.4 parts of methyl isobutyl ketone. The reaction mixture was cooled to 70.degree. C. and 39.8 parts of a 73 percent by weight solution in methyl isobutyl ketone of a methyl isobutyl ketone diketimine of diethylene triamine were added, followed by 62 parts of diethylamine.

The reaction mixture was then heated to 115.degree. C. and held for 4 hours at which point 11.8 parts of diamyl amine were added and the reaction mixture held for another 2 hours.

To prepare the chain-extended electrodepositable thermosetting cationic urethane modified composition, 518 parts of the above polycaprolactone diol extended polyurethane resin were blended with 7.6 parts of dibutyltin dilaurate and 9.3 parts of glacial acetic acid, followed by careful reduction with 225.1 parts of deionized water. To this solubilized vehicle composition was then added 171 parts of the pigment dispersion of Example I, 19 parts of ethylene glycol monohexyl ether and 2869 parts of deionized water. This electrodeposition bath had a rupture voltage of 300 volts, pH of 5.8 and yielded smooth, hard, flexible films when cathodically electrodeposited over zinc phosphated steel at 270 volts for 2 minutes and cured for 20 minutes at 400.degree. F. (204.degree. C.). When scribed and exposed to a salt fog at 100.degree. F. (38.degree. C.) as described in ASTM D-117-73, the panel displayed less than 1/32 inch scribe creepage from the scribe mark after 14 days.