CA1258739A - Polyoxyalkylenepolyamine reaction products and their use in cationic electrodeposition - Google Patents

Abstract

Abstract of the Disclosure Ungelled reaction products of polyoxyalkylenepolyamines with monoapoxides and optionally with a polyfunctional material which contains groups capable of reacting with amino and/or hydroxyl groups are disclosed. The reaction products can be neutralized with acid and dispersed in aqueous medium where they are useful as additives for cationic electrodeposition baths to improve surface appearance of electrodeposited coatings.

Description

:12S~37;;~9 POLYOXYALKYLENEPOLY~INE REACTION PROD~CTS
~'D ~IEIR USE IN CATIONIC ELECTRODEPOSITION

The present inventlon relates to ungelled reaction products prepared from polyoxyalkylenepolyamines and to the use of these reaction products for cationic electrodeposltion.
~ ectrodRposition as a coating application method involves the deposition of a film-forming composition under the influence of applied electrical potential.
Electrodepos.ition has become increasingly important ln the coatings industry because by comparison with non-electrophoretic coating means, electrodeposition oEfers higher paint utilizatiGns, outstanding corrosion protection and low environmental contamination. Initially~ electrodeposi-tion was conducted with the workpiece being coated serving as the anode.
~his was familiarly referred to as anionic electrodeposition. However;
in 1972, cationic electrodeposition was introduced commercially. Since that time, cationic electrodeposition has steadily gained in popularity snd eoday is by far the most prevalent method of electrodeposition.
Throughout ehe world more than 80 percent of all motor vehicles produced are given a primer coatlng by cationic electrodeposition. Other areas of application are primer coatlng or one-coat topcoating of automobile acces-sories, farm machinery, house and electrical appliances, steel furnlture and structural components.
~ serlous problem associated wlth electrodeposition as prac-ticed lndustri~lly is appearance defects in fllms. Such defects lnclude 5~

film rupturing, the formation of pinholes and craters. The sources of film defects unfortunately are many and some of the more important sourc-es are believed to be impur ties or contamlnants ln the electrodeposition bath which may be, for example, oil ~r pretreatment chemicals introduced r.to the bath along wlth the article to be coated. One solution to the problem is to elimina~e the impurities or source or contamination. How-ever, this is not always practical on an industrial scale.
U.S. Patent No. 4,423,166 describes an additive which can be added to a cationic electrodeposition bath to improve surface appearance of thc electrodeposited coatings. The agent is the unaelled reaction produc~ of a polyepoxide and a polyoxyalkylenepolyamine. Unfortunately.
although being effective ln improving surface appearance, the reaction product can cause adheslon problems of the electrodeposited coatlngs to subsequently applied materials such as sealer coats, top coats and adhesives.

In accordance with the present invention, an addltlve for use ln catlonic electrodeposltion to lmprove surface appearance ln electrodeposition coatings ls provided. Besides lmproving surface appear-ance, the additive does not adversely effect the adhesion of subsequently applied macerlaIs such as top coats.
The additive ls the ungelled reaction product of a polyoxy-alliylenepolyamlne with a monoepoxide and optionally a polyfunctional material which contains groups capable of reacting with amino and/or hydroxyl groups.

~X~37;~9 The polyoxyalkylenepolyamines are usually first reacted wlth the monoepoxide and optional]y further reacted with the polyfunctlonal material which contains groups capable of reacting wi~h amines,such as unreacted primary and secondary amln ogroups of the polyoxyalkylene-polyamllle,~and/orcapable of reactlng wich hydroxyl groups,such as those associated with ring opening Os the monoepoxide upon reaction with the polyoxyalkylenepolyamlne. ~lternately, the polyoxyalkylenepolyamine can flrst be reacted ~ith a reactlve polyfunctional material followed by reaction with the monoepoxide, Gr the polyoxyalkylenepolyamine can be reacted simultaneously with the monoepoxide and a reactive polyfunctional material. However, the sequential reaction in which the polyoxyalkylene-polyamine is reacted first with the morloepoxide and then optionally with the polyfunctional material is preferred.
~ he polyoxyalkylenepolyamines useful in the practice of the invention are preferably diamines and examples lnclude those having the following structural formula: -_ _ ; R

H2N - CH - CH20- f 2 - C~2 - CH ~ ~2 R _ n wherein R can be the same or different and is selected from th~ class consisting of hydrogen, lower allcyl radicals having from 1 to 6 carbon atoms and n represents an integer of from about 1 to 50, preferably5 to 35. A number of such polyoxyal~ylenepolyamines are described in more detail in U.S. Patent No. 3,236,395, column 2, llnes 40-72; methods of preparatlon of the polyoxyal~ylenepolyamines are iliustrated in the 587~'3 patent in examples 4, 5, 6 and 8-12 in columns 4 to 9 thereof~

.

Mixed polyoxyalkylenepolyarnines can be used, that is , those in which thè oxyalkylene group can be selected from more than one moiety. Examples would be mixed polyoxyethylene-propylenepolyamines such as those having the following structural formula:

I H L / OCH2 - CH2 /m-OCH2-CH-NH2 wherein n+m is equal to 1 to 50, preferably 5 to 35 ,m is equal to 1 to 49,preferably 5 to 30,and n is equal to 1 to 49 preferably 5 to 30.
3esides the polyoxyalkylenepolyamines mentioned above, derivatives of polyoxyalkylenepolyamines may also be usable~
Examples of suitable derivatives would be aminoalkylene derivatives which are prepared by reacting polyoxyalkylenepolyàmines such as those mentioned above with acr~ylon;tr;le followed by hydrogenation of the reaction product An example of a su;table derivative would be that of the follow;ng structural formula:

H2NCH2 - CH2- CH2- ¦- CH-CH2 - ~ I_cH2 ~ t CH2-~H N (CH2)3'hH2 wherein R and n have the meanings mentioned above.

Thereforejin the practice of the ;nvent;on,where the expression " polyox,y..alkylenepolyarnin~s " is used,what ;s:
intended are polyamines containing both oxyalkylene groups and at least two amino groups , prefera-r~

~-' 4 . .
-, . ,' '~ ' :
.
:'' '- , :
,, - :

~;~S~'73~3 bly primary amino groups, per molecule, PreferablyJ the polyo~yalkylene-polyamine contalns oxypropyl groups. The polyamine preferably will have a molecular weight (number average) of about 137 to 3600, more preferably about 400 to 3000, and most preferably 800 to 2500. The polyamines rlill preferably have equivalent ~elghts, i.e., based on amine hydrogen, of about 34 to 900, more prefer2bly about 100 to 750, and most preferably 200 to 625. In deterTnining the equivalent weights, the primary amines ar~ considered to be difunctional. Products with molecular weights much higher chan 3600 and a high alkylene oxide content, that is, greater than C3, are not preferred because of poor solubility characteristics.
The monoepoxides which ~re used in the practice of the inven-tion can be selected from those having the following structural formula:

l \ / 2 0 :;
where Rl and R2 can be the same or different and include hydro-gen, alkyl including cycloalkyl, ,~ preferably containing from l to 1i3 carbon atoms f aryl containing from 6 to 18 carbon atoms, substituted alkyl and substitured aryl mole~ès such as -CH20R3 and .
o Il .' - CH2 - OC - R3 where R3 is slkyl,including cycloalkyl, aryl and substituted alkyl ~ncluding cycloalkYl ~and substituted aryl ;n~which the alkyl contain from 1 ~o~l8 carbon atoms and the aryl contain from 6 to 18 carbon atoms. R and R~ can be unsubstituted or substituted : ~ ~
with substi~uents as long as the substituents do not interfere with the reaction of the epoxy wi~h the polyo~yalkylenepolyamine, ~nd the sub-stituents nre of such a na~ure or employed under conditiolls that they S

' ,,' ,..

l~S~37~.9 will not gel the reactlon mixture. Preferred monoepoxides are 1,2-epoxy-containing materials having the structural formula:

/

wherein Rl is hydrogen or methyl and R~ is hydrogen, alkyl including cycloalkyl, preferably containing rrom 1 to 18 carbon atoms~ aryl contalning from 6 to 18 carbon atoms, substituted alkyl and substituted aryl. moieties such as -CH20R3 and 1l - CH2 - OC - R3 ~here R3 is alkyl including cycloalkyl, aryl and substituteà alkyl including cycloalkyl ,substituted ary.l ;n which the alkyl contain ~ ~.o 18 carbon atoms,and the aryl contain ~rom 6 to 18 carbon atoms. Rl and R2 can be unsubstituted or substituted ~ith substituents as long as the substituents do not interfere ~-irh the reaction of the epoxy with the polyoxyalkylcnepolyam ne, and the sub-stituents are of such a nature or employed under conditions that they will not gel the reaction mixture.
Examples of suitable monoepoxides are alkylene oxidcs contain-ing from 2 to 30 carbon atoms including ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-pentene oxide, 1,2-dodecene oxide, styrene oxide nnd glycidol. Examp].es of other suitable m terials are glycidyl esters of monobasic acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl acetate, glycldyl butyrate, glycidyl palmi~ate, glycidyl laurate and glycidyl esters sold under the trademarlc CARDURA~ E. Other suitable materials are glycidyl ethers of alcohols and phenols such as butyl glycidyl ether, 2-ethylllexyl glyci.dyl ether, phenyl glycidyl ether nnd para-(tertiary-butyl)phenyl glycidyl ether. Other suitabl2 materials ~x5~739 although less preferred are 2,3-butylene oxide, 4-phenoxy-2,3-hutylere oxide. Preferred are h~tyl glycidyl ether and styrene o~ide.
As mentioned above, preferably after reaction of the polyoxy-alkylenepolyamine with the monoepo~lde, the reaction product may optional-ly be further reacted with a polyfunctional material which contains groups reactive with any remaining unreacted amlnO groups and/or reaccive wi~h an~ of the hydro~yl groups which are present or are for~ed from ring of opening/the monoepoxide, i.e., ~ ~ fH CH -0 -NH 0~

Further reaccion with the polyfunctional material chain extends ~he polyoxyall;ylenepolyamine reactlon product ,increasing' its molecular weight and has been found to alleviate some problems such as sticky films, low throwpower and electrode gassing.
Examples of suitable polyfunctional materials are polyacry_lates, polyisocyanat'es,polycarb'oxylic acids'an~ polyepox-ides. ~ ' ` The preferred molecular we~ights of'`said materials are less than 1000,and m~re prefer~bly 'from 100 and 600 -~ amples o~ yolyacrylates are t~ose which contain at leas~ ~wo alpha, beta-ethylenically unsaturated carbonyl groups, i.e., groups of the structure:

- C - C = CH2 per molecule where R is hydrogen,which is preferred~or lower alkyl containing from l to ~ carbon atoms such as methyl.
The unsaturated carbonyl groups are usually attached to a nitro-gen or oxygen atom and are represented by the followlng structural formulas:

~Z587~9 O R O R
ll 14 11 1 4 - O - C - C = CH2 , - N - C - C = CH2 .
wherc r~4is as defined above. The organic radical to which the alphz, beta-elhylenlcally unsaturated carbony~ groups are attached can be select-ed from alkyl, aryl and substituted alkyl and aryl groups provided th~
~ubstituents do not adversely affect reaction wi~h the am~n~ groups The ~rsanic radical preferably has a molecular weight less than abou~ 500.
The preferred reaction scheme ~ith the polyacrylate is ~ia a Michael reac-tion with the amine groups associated with the polyoxyal~ylenepolyamine.
~lternately, reaction may also occur through transamidifica~lon or through transesterification.
The preferred polyacrylates are compounds that can be formed from reacting organic polyols with acrylic or methacrylic acid. Examples of suitable compounds lnclude ethylene glycol dlacrylate, 1,4-butancdlol dimethacrylate, 1,6-hexanediol diacrylate, blsphenol A dlacrylate, di-ethylene glycol diacrylate, and trimethylolpropane triacrylate. Examples of other materials containing the alpha, beta-ethylenically unsaturated carbonyl groups are reuction products of polyisocyanates, preferably diisocyanates such as toluene diisocyanate, with hydroxyl-containiDg acrylic and methacrylic esters such as 2-hydroxyethyl acryla~e or hydroxy-propyl methacrylate; reaction products of polyepoxides preferably diepoxides such as the dlglycidyl ether of bisphenol A wlth acrylic or methacryllc acid; transetheriLicatlol~ reaction products of polyols, preferably dlols such as ethylene glycol, 1,4-butanediol and 1,6-he~ane-diol with N-61koxymethylacrylamides or methacrylamides specifically U-bo~o:cyme th6cl: ial~lid6 .

.

~;~587~9 The polyisocyanates which are usable in the practice of the invention are organlc polyisocyanates which are capable of reacting with both the aminJOand hydroxyl groups. Specific examples include aliphatlc compounds such as trlmethylene, tetramethylcne, hexamethylene dlisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, 2,2,l~-trimethyl-hexane-l~6-dlisocyanate; cycloalkylene compounds such as 1,4-cyclohexanc diisocyanate; .~roma~ic compounds such as p-phenylene dilsocyzna~e;
aliphatlc-aromatlc compounds such as ~,4'-diphenylene methane diisocyana~e, 2,4- or 2~6-eolucne diisocyanate lncluding isomer~c mixtures thereof. Higher polyisocyznates can be employed such as tri-isocyanates, although thelr use is not preferred. An example would include triphenylmethane-4,4',4"-tliisocyanate. Also, NCO-prepolymers which are obtained from reacting the organic polyisocyanates described above with a polymeric polyol such that there ls:an excess of isocyanate to hydroxyl groups~ Examples of sultab~le polymeric polyol~ lnclude -polyether polyols and polyester polyols includinc polycaprolactone polyols.
The polycarboxylic acids which are usable in the practice of the invention are those which are capable of reacting with the hydroxyl groups or with primary or secondary amin_ogroups and include not only the acids themselves but their reactive functional equivalents such as anhy-drides and lower alkyl, l.e., Cl-C4 alcohol esters thereof. Examples of suitable materials include phthalic acid, isophthallc acid, tere-phthalic acid, tetrahydrophthallc acid, hexahvdrophthallc acid, ad~pic acid, azelaic acld, sebacic acld and the llke.
The polyepoxides whlch are usable in the practicc of the lnven-tion are those whlch are capable of reacting with the remainlng amino ~1 2~739 grollps of theqpolyoxyalky]enepolyamille, Alternately, the polyoxyal~.ylene-polyamine ~ay be modified such that it conta~ns carboxylic acld functionallty whlch is roactive wlt.h the polyepoxlde. An e~:a~ple of tl- s is shown belo~. Examples of suitable polyepoxides are those which con-ealn two or more and preferably only two epoxy groups per molecule. The polyepoxides may be any Gf the well~kr.own types of polyglycidyl ethers of polyphenol, for example, bisphenols such as bisphenol ~. "lso, poly-glycidyl ethers of polyhydric alcohols such as eth~-lene glycol, propylene glycol and diethylene glycol may be used. ~so, polyglycldyl esters of polycarbo~ylic aclds such as those~mentloned above may be used.
The reactlon conditions for preparing the Feactlon products of the inventlon are not difficult nor extreme. For example, the mono-epoxlde can be added to the polyoxyalkylenepolyamine under a nitroger.
atmosphere and at G temperature sufficien. to induce reaction,~ror e~ample, fron about 50 to 200C. ~he progress of thé reaction can be monltored spectral].y by the disappearance of epoxide functior.ality or by tltracion and the reactlon will usually take at least one hour, typicalIy from about l ~o lO0 hours.
The polyfunFtlonal materiel can be added to the re~ction mi.~-ture at a temperature below that of reaction and the temperature aradual-ly raise~ to lnduce reaction~. The progress of the subsequent chain exten-.
slon reacclon can be monitored by lncreOses in viscosity or bP monitoredby the disappeaLance of funccionality which can be determined spectrallv such as NC0 or epoxlde. The time and temperature of the subsequent rsac-tion uill vary dependin~ on the react2nts selected, their amounts and the presence or absence of catalyst.

1~5873'3 With regard to the amounts of polyoxyalkylenepolyamine, molto-epoxide and polyfunctional material which are reacted with one another, the amounts will vary ~uite wiclely. For each equivalent of polyoxyalkyl-enepolyamine, there should be at least 0.01 equivalent of monoepoxide.
An equlvalent excess of mono~poxide does not appear ~o be disadvantageous Although amounts greater than 1.7 equivalent per equivalent of polyamine do not appear to offer any advantage. The preferred equ valent range is 0.05 to 1.5, more preferably 0.1 to 1.3 equivalen~s of monoepoxide per equivalent of amine.The term equivalent indicates the number of reacting groups in the molecule, The amount of polyflmccional material is preferably one equiva-lent or lcss per equivalent of amine and/or hydroxyl, more preferably 0.7 equivalents or less.
The reaction products of the pr~sent invention can be modified by reaction with other materials, for example, pa~rtially capped polyiso-cyanates. These ~taterials will participate in curing of ~he electro- "'`t l, .
deposited coating-and can assist in the dispersion of the reaction prod-uct, for example, using a neutral-zable amine such as dimethylethanol-amine as the capping agent. Besides partially capped polyisocy~r.ate, the reaction products of the present inventlon can be present with ful]y capped polyisocyanates.
The reactions described above can be conducted nezt or in the presence of solvcnt. The solvent is one which is non-reactive with the various f~mctlonalities such as epoxlde groups, amin~ groups, hydroxyl groups, isocyanate groups, carboxylic acid groups and unsaturated groups under the reaction conditions employed. Suitable solvents include hydro-carbons, ethers, and esters. Tbe amount of solvent used will vary between about 0 to 90 a~d preferably about 5 to 50 percen~ by weight based on total weigllt of the reaction mixture.

1~

., ' - ' ' ' ' .

`. ~L2~87~9 The reactlon products o the present lllventlon are ungelled whlch means they are substantially free of crosslinking and have a measurable intrinsic viscosity when dissolved in a suitable solvent. The intrinsic viscositv of the reaction product is an indication oI its molecular weight. A gelled reaction product, on thè ocher hand, since it is of essentially infinitely high molecular weight, will have an lntrin-sic viscosity too high to ~easure.
Some specific examples of reactlon products in accordance ~ith the present invention include:

1 mole (4 equivalents`i,e. 4 H to be substituted )of polyoxypropylene-diamine,tmolecular weight(MW) about 2000)

2 moles (2 equivalents) of the monoepoxlde butyl glycidyl ether or styrene oxide and mole (1 equivalent) of the diacrylate 1,6-hexanedio] diacrylate 1 mol~ (4 equivalents) of polyoxypropylenediamlne (MW about 2000) 4-5 moles (4-5 equivalents) of butyl glycidyl ether or styrene oxide 1 mole (4 equivalents) of polyoxypropyIenedianine (MW about 2000) 4 moles (4-5 equivalents) of butyl glycidyl ether or styrene oxlde 0.1 to 1 mole (0.2 to 2 equivalents) oE isophorone dlisocyanate Increasing the amounts of the isocyanate will increase the molecular ~eight of the reaction producc and may increase throwpowcr of the electrodeposi~ion bath to which the reaction product is added.
Besides chain extending through the reaction sequence as described above, other reaction sequences can be used ir. che chain exten-sion reaction. For example, an ungelled reactlon product from the follow-ing reactants can be prepared:

~s87~g l mole (4 equivalents) of polyoxyalkylenedlamine (MW - 2000) 4 moles (4 equivalents) of a monoepoxide 2 moles (2 aslhydride equivalent) Gf an acid anhydride 1 snole (2 equlvalents) of a diepoxide.
In the example above, the reaction of the polyoxyalkylen~poly-amine with the monoepoxlde will form a reaction product containing on average 4 hydroxyl groups per molecule. This reaction product can then be reacted with the anhydride to form a reaction product having on averagé two hydroxyl groups and two carboxylic acid groups per molecule.
This reaction product can then be chain extended with the diepoxide ~hrough the reactlon of the carboxylic acid and ~he epoxide groups.
Also, a reaction product from the following reactants can be prepared:
l mole (4 equivalents) of a polyoxyalkylenediamin~MW ~ 2000) 4 moles (4 equivalents) of a monoepoxide 2 moles of a half-capped diisocyanate 1 mole (2 equivalents) of a diol In thls example, the polyoxyalkylenepolyamine reacts with the snonoepoxide to form a tetraol. This reaction product is then reacted with th~ partially capped diisocyanate to form a reaction product contain-ing on an average two hydroxyl groups and two capped isocyanate groups per molecule. This reactiosl product in turn can ehasl be chaizl extended --wlth a diol by heatlng the two at a temperature suffic ent to uncap the capped diisocyanate groups and permitring chain extenslon through reac-tion with the diol.
For use ln cationlc electrodepositlon, the reaction products are at-least partially neutralized wlth acid to form amine salts or are quaternlzed with excess monoepoxide and acld to form quaternary ammonlum salts.

`

,' .' `' ; ' - ' ~'' .' l~S~q;3~

Suitable aclds lnclude organic acids such as for~ic acid, lactic acid and acetic acid, and inorganic acids such as phosphorlc acid. The extent of neutrali~ation depends upon the particular rcaction product and usually only sufflcient acid ls added to solubilize or dis-pcrse the reactlon product.
The reaction products may be dispersible by the~selves, or may have to be combined wlth a surfactant for dispersion. A conventional way of dispersing the reaction products is to cGmbine them with a portion of the pigment grinding vehicle or with the electrocoating resin and dispers-ing the mlxture in aqueous medium.
The reaction products of thc present invention are particularly useful in combination wlth high throwpGwer cationlc electrodepositable resins (main film-forming resin) which are used ln the elec~roccating of rticles with complex shapes such as au~omohiles. ~
Throwpower, as used in the conte~t of this invention, is the ubility of the cationic resin to coa~ completely the recessed areas and shielded portions of the cathode. Several methods have been proposed for ~easuring throwpower lncluding the Ford cell test~and the Gneral Motors cell test. See, for example, ~rewer et al, JO~RNAL OF PAINT TEC}lNOLOGY, 41, No. 535, pages 461-471 (1969); and Gilchrist et al, AllERICAN CHEl~ICAL
SOCIETY, DIV. OF ORGANIC COATINGS AND PLASTICS C~EMISTRY, PREPRINT BOOK
31, No. l, pages 346-356, Los Ange1es ~leetlng, March-April 1971. Throw-power is reported in inches, the higher the value, the greater the throw-power. In this inventlon, where throwpower is mentioned, General l~lotors or G~l throwpower is intended.
Accordlngly, the re~ction products of the present invention which typically have Gll throwpower o~ 6 inches (15.2 c~) or less are .

~L~5~373~:3 useful in comb~nation with high throwpower cationlc electrodeposltable resins having GM throwpower of 10 inches (25.4 cm), preferably 12 inches (30.5 cm) or more.
Examples of high thro~ower catior.lc electrodeposl~able resins include amine salt group-containing reslns which are the acid-solubill~ed reaction products of polyepoxides and primary or secondary amines such as described in U.S. Patent No. 4,031,050 to Jerabek. Usually, these amine salt group-cont~ining resins are used irl combinatlon with a blocl~ed isocyanate curing agent. The isocyanate call be fully blocked as descrlbed ln the aforementloned U.S. Patent No. 4,031,050, or the lsocyanate can be partially blocked and reacted wich a resin. Such resinous systems are described ln U.S. Patent No. 3,947,35~ to Jerabek et al. Also, such one-component compositions are described in U.S. Patent No. 4,134,ô66 and DE-~S No.~ 2,752,255. Besides high throwpower cationic electrodeposltabile resins, the cationic adducts of the inven~ion can also be used wlth low throwpower resins such as cationic acrylic resins. Exam-: ; ples of these resins are described in U.S. Patents Nos. 3,455,806 and

3,928,157.
Besides amine salt group-containing resins, quaternary an~onium salc group-containing resins can also be employed. Examples of these resins are those ~ihich are formed from reaccing an organic polyepoxlde with a terciary amine acid salt. Such resins are described in U.S.
Patents Nos. 3J-962,165; 3,975,~346 and 4,001,156 to Bosso and Wismer.
Examples of other cationic resins are cernary sulfonium salt group-containlng resins such as those described in U.S. Patent No. 3,793,273 to VeBona. Also, cationic electrodeposltable resins which cure via a transesterification mechanism such as described ln European Patent Appli-cucion 12463 can also he employed.

, ~25~73'3 The amoun~ of the reactlon product of the in~entlon present in the coating composition is usunlly within the range of about 0.1 to 50, preferably 0.5 to ~0, more preferably from about 1 to lO percent by weight, based on total weight of resin solids. The principal film-forming cationic electrodepositable resin is present in amounts of S0 to 99, preferably 75 to 95 percent by weight based on weight of resin solids.
In addition to the principal film-forming cationlc resin and the reaction products of the present invention, other organic materials which contribute to resin solids content may be present in the aqueous dispersion, Such materials include plasticizers such as polycaprolac-tones, plgment grinding vehicles, high boiling esters such as esters of phthalic acid with monohydric aliphatic alcohols having 4-lO carbon atoms such as n-butanol and octanol. Also, aliphatic snd aromatic polyether polyols such as ethylene and/or propylene oxide reaction products of phenols such as cresol and nonyl phenol and bisphenol A can be present.
Also, surfactants, wetting agents and defoa~crs can be present. Examples includa allcyl i~idazolines, acetylenic alcohols and sll~cones. When used, these materials are present in amoun~s up to 25 percent by weigh~
based on weight of resin solids.
The resin solids conten~ of the aqueous dispersion is zt least 0.5 nnd usually from about 1 to 50 percent by weight based on total weight of the aqueous dispersion.
Besides water, the aqueous disperslon may contain a coalescing solvent. Useful coalescing so]vents include hydrocarbons, alcohols, estars, ethers and ketones. The preferred coalesclug solvents include alcohols, polyols and ketones. Specific coalescing solven~s lnclude .

` lX58739 isopropanol, butanol, ~-ethylhexanol, isophorone, 4-methoxy,4-methyl-2-pentanone, e~hylene and propylene glycol, and the monoethyl, monobutyl and monohexyl ethers of ethylene glycol. The amount of coalescing solvent is not unduly critical and is generally between about 0.01 and 40 percent, preferably about 0.05 to about 25 percent by weight based on total weight of the aqueous medium.
In some instances, a pigment composltion is lncludcd in the dispersion. The pigr~ent composition ~ay be of rhe conventional types, comprising, for example, iron oxides~ lead oxides, strontium chromate, carbon black, clay, titanium dloxide, talc, barium sulfate, as well as color plgments such as cadmlum yellow, cadmium red, chromium yellow and the like. The pigment content of the dispersion ls usuall~ expressed as the pigment-to-resln ratio. In the pracrice of the present invention, the pigmerlt-to-resin ratio is usuallv within the range of 0.02 to l:l.
llhen the aqueous dispersions as described above are used in ;:
electrodeposition, the aqueous dispersion is placed in contact with an eleccrically conductive anode and an electrlcaliy conductive cathode wi`th ch~ surface to be coated being the cathode, Following contact with the aqueo~ls dlspersion, an adherent fllm of the coating composition is depos-ited on the cathode and a sufficient voltage ls impressed between the electrodes. The conditions under which the electrodeposition is carried out are, in general, similar to those used in electrodepositon of other Cypes of coatings. The applied voltage may be varied and can be, for e~ample, as low as one volt to as high as several thousand volts, but typically between 50 and 500 volts. The current density is usually between 0.5 ampere and 15 amperos per square foot (10.~-lfil.5 amp~res per square meter) and tends to decrease during electrodepositiorl indicating the for~atlon of an lnsulnting fllm.

].7 .

.
.` ' . ' ~ ' ' ''` '' ' .

lX5~7~3 The coating compositions of the present lnvention can be applied to a variety of electroconductivc substrates especially metal such as steel, aluminum, copper, magnesiuTn and the like, but also includ-ing metallized plastlc and conductivc carbon-coated rnaterials.
After the coating has been applied by electrocoatlng, it is cured, usually by baking at eleva~ed temperature such as 90-260C. for ~bouc 1-30 minutes.
Illustrating the invention are tllc following examples which, however, are not to be considered as l.imi~ing the invention to their details, All parts and percentages in the examples as well as throughout the specificaticn are by weight unless otherwise indicated~

.
Example A
A conventional catlonlc resin was prepared from the following mixture of ingredients:
''`

`- ' ' ~2~

ngredients Parts by Wei~ht Solids EPON 829 702.2 702.2 PCP-02002 263.4 263.4 Xylene 61.6 Bisphenol A 197.8 197.
~en~yldimethylamine 3.~
Capped isocyanate erosslinker 891 629.1 Di~etimine derived from diethylenetriamine and methyl isobutyl ~eto~e (73% solids in methyl isobutyl ketone)75.8 54.7 ~-methyl~h2nolamine 59.1 59.1 Phenoxypropanol 126.9 Acetic acid 29.5 Cationic surfac~ant4 29.3 Deionized water 2553.1 lEpoxy resin made from reacting epichlorohydrin and bisphenoi A
having an epo~y equivalent of 188 co~mercially available from Shell ~hemical Company.
Pclycaprolactone diol available from Uoion Carbide Corp.
3Polyurethane crosslin~.er formed from half-capping toluene ùii~ocyanate (80/20 2,4-/2,6-isomer mixture) with 2-ethylhe~anol and reactin~ this pro~uc~ with trimethylolpropane in a 3:1 ~olar ratio. The croxslinker ls present as a solution in 2-ethoxyetharol.
4Câtlonic surfactant prepared by blending 120 parts or an alkyl imidazoline commercially avail~hle from Gelgy Industr-i21 Chemicals as CEICY .~IINE C, 120 parts by weight of an acetylenic alcohol commercialIy uvailable from Air Products and Chemicals as SUR~YNOL 104, 120 parts of ~-buto~vethanol and 221 parts by weight of deionized water and 19 parts of glaclal acetic acid.
The EPON 829, PCP-0200 and xylene were charged ~o 2 reaction vessel and heated under a nitrogen at~osphere to 210C. The reaction was held at reflux for about 12 hour to remove wa~er. T~le reaction mixture * trade mark '. . , .. : ,, .. , . . . :
:, ,, -' ' ' " ' ' . .

l;~S~37~9 was cooled to 150~C. and tlle bisphenol A and 1.6 parts of the benzyldl-methylamine (catalyst) added. The reaction mixture was heated to 150-1~0C, and held at this tempcrature for nbout 1~ hours and then cooled to 130C. The remaining portlon nf the benzyldimethylamine catalyst was added and the reaction mixture held at 130C. for 2!~ hours until a reduced Gardner-lloldt viscosity (50 percent resin sollds solution in 2-ethoxyethanol) of ~ was obtalned.
The polyurethane crosslink2r, the d~ketimine aerivacive and the ~-methylethanolamine were then added and the temperature of the reaction ~ixture brought to 1]0C. and held at this temperature for 1 hour.
The phenoxypropânol was added and the reaction mixture was dlspersed in water by adding ~he reaction mixture to a mixture of the acetic acid, deionized water and the cationic surfuctan~.

Example B
A polyoxyalkylenepolyamine-monoepoxide-polyacrylate was pre-pared from ehe following mixture of ingredlents:
_gredients Parts by Welght Solids Equivalents JEFFAMI~E D-20001 4056 4056 8 Butyl glycldyl cther520 520 4 Hexanedlol dlacrylate 226 226 2 Lactlc acid (88%) 204 Deionlzed water 107 Butyl glycidyl ether640 640 4.9 The JEFF~IINE D-2000 ls a polyoxypropylenedlamine havil~g a ~lolecular welgllt of 2000 avallable from Jefferson Chemical Company.

* trade ~na~k . ~ 20 ~
' :
~, ' ' .

~25~37;~

The JEFFA~IIN~ D-2000 and the first portion of butyl glycldyl ether were charged to a reactlon vessel under a nitrogen atmosphere and heated at 130C. until a stalled viscosity (Q-R) and an epo~y cquivalent of greater than lOtOOO was obtalned.
The temperature was adjusted to 120C. followed by the addition of ~he hexanediol diacrylate. The reaction mixturc was held at 130C.
for about 7 hours until a Gardner-Holdt viscosity of V was obtained.
The tempera~ure was decreased to 80C. and the l~ctic acid und water were then added. After 5 minutes the remalning portion of the butyl glycidyl ether t~as added~and the reactlon mixture held at 80C. for ahout 8 hours untll an acid value below 6 was obtained.

. .
Example C

A polyoxypropylenediamlne having a molecular weight of 2000 was reacted with butyl glycldyl ether as follows:

Ingredients Parts by Weight Sollds Equivalents JEFFI~lINE D-2000 2000 2000 4 ~utyl glycidyl ether 546 546 4.2 Uethyl isobutyl ketone 25 The JEFF~WI~IE D-2000 and the butyl glycidyl ether we~e charged to ~ reaction vessel under a nitrogen ~tmosphere and heated to 180C.

The reaction mix~ure ~as held at thls temperature until 95 percent of the epo~y groups wcre consumed, i.e., an epo~y equlvalent of greater than , 10,000. The reaction mixture was then cooIed to 120C., the methyl :
isobutyl ketone added, and the reaction mixture vacuum stripped.
- ~ ~
~. :

2~1 - .
. .

.

' :1~58~3 . Example D
Isophorone diisocyanate half-capped with dimethylethanolamine was prepared from the followlng reaction mixture:
Ingredients Parts by Weight Solids Equivalents Isophorone di`lsocyanate 221 221 2 Dimethylethanolamine 89 89 llechyl isobuty] ketone 17 The isophorone diisocyanate and methyl isobutyi kecone were charged to a reaction vessel under a nitrogen atmosphere and heated to 40C. The dimethylethanolamlne was added slowly (2-3 hours) so as the temperature not to exceed 50C. The reaction mixture was then held for one hour at 50C. until an NCO equivalent of 320-340 was obtained.

Example E
A half-capped isocyanate was prepared from condensing toluene diisocyanate (100 percent 2,4 isomer) with 2-ethylhexanol according to a ``
process similar to Example D.
Ingredients Parts by ~leight Solids Equivalents Toluene diisocyanate174 174 2 2-F,thylhexanol 133 133 1.02 Methyl isobutyl ketone 16 - .
- ' .

' .- 22 ~2S~3'739 Example F
The polyoxypropylenedlamin~-butyl glycldyl ether reactlon prod-uct of Example C (average hydroxyl f~nctlonality = 4) was reacted wlth the partially capped polylsocyanates of Examples D and E from the follow-ing ingredients:
Ingredients Parts b~ Wei~ht Solids Equivalents Reaction procluc~ of Example C 1273 1273 2 rartially capped isocyanate of Example E 323 307 Parcially capped isocyanate of Example D 343 325 1.05 2-Butoxyethanol 97 Lactic acid (88% pure in water) 86 Cationic surf~ctant of Example A 63 Deionized water 3108 The reaction product of Example C and the partially capped isocyanate of Example E were charged to a reaction vessel under a nitro-gen blanket and heated to 100C. After 30 minutes at this tempera~ure, el~e reaction mixture was checked by infra-red and no NC0 groups were detected. The partialiy capped isocyanate of Example D was added and the temperature maintained at lC0C. for 2 hours followed by the addition of ehe 2-butoxyethanol. The reaceion mixtur~ was dispersed in water by adding the resin to a mlxture of lactic acid, deionized water and the cationic surfactant. This dispersion was then diluted to 36 percent with deionized water. ~ -- ' :
-:' .
- . ~, ' 1~5~3~7~

Exa.mple C
A polyoxypropy].enediamine havin~ a mo].ecular weight of 2000 WâS
reacted with ethyl hexyl glycidyl ether as follows:
Ingredlents Parts by Weight Solids Ea,uivalents JEFF~INE D-2000 2000 20C0 Ethyl hexyl glycidyl ether 775 775 4.1 IIQthyl lsobutyl ketone 250 The JEFF~ lE D-2000 and ethyl hexyl glycidyl ether were charged to a reaction vessel under a nitrogen atmosphere and heated to 180C. The reaction mixture was held at this temperature until 96 per-cent ot ehe epoxy groups were consumed, l.e., epoxy equivalent of greater than lO,000. The reaction mixture was then cooled to 120C. and the methyl isobutyl ketone added. The reaction mixture was then vacuum stripped.

Example Ei The polyoxypropylenediamine-b~tyl glycidyl ether reaction prod-uct o Example C was reacted with isophorone diisocyanate and the partial-ly capped polyisocyanates of Examples D and E as follows:
Ingredients Parts by Weight Solids Equivalents Example C - 7638 7638 12 .
Isophorone diisocyanate 442 442 4 Example D 1308 1240 4 Example E 1292 1228 4 ' ~4 , - ~2S87.'~'3 The reactlon prodnct of Exampl~ C was reacted under nitrogen wlth lsophorone diisocyanate at 110-120C. untll all the NCO groups were consumed as indicated by infra-red analysis. Then, the partia~ly capped lsocyanate of Exampie E was added slowly at 100C. I~hen all isocyanatc ~roups were consumed, the reac~ion was continued with Example n according to the same process.

Example I
An aqueous dispersion of polyepoxide polyoxyalkylenepolyamine resln was prepared as generally described in Example I of U.S. Patent

4,43?,850 from the following mixture of ingredients:
Ingredients Parts by Weight JEFF~`IINE D-20n0 1415.9 EPON l0011 489.1 2-Butoxyethanol 179.8 Polyurethar.e crosslinker~ 1814.3 Polyglycidyl ether of bisphenol;l~ having an epoxide equivalent of 523 available from Shell Che~ical Company.
Poly~lrethane crosslinker formed from half-capping toluene dii`socyanate (80/20 2,4-/2,6-isomer mixture) with 2-butoxyethanol and r~accing thls product wi~h trimethylolpropane in a 3:1 molar ratio. The crosslinker is a 70 percent solution in 2-ethoxyethanol.
The JEFF~IINE D-2000 was charged to a reaction vessel under a nitrogen atmosphere and beated to 90C., followed by the addl~ion of a solution of the EPON 1001 in the 2-butoxyethanol. The reaction mixture was heated to 110C., held for ewo hours, followed by the addition of the polyurethane crosslin~er. The reaction mlxture was dispersed by combin-ing 370n parts by weight of the reaction mixture with 50.3 parts oi lactic acid, 75.3 parts of the catlonic 5urfactant of Example A and 4679.1 parts by weight of deionized water to form the disperslon.

' , 125~ 3 Plgment Paste Quaternizing Agent - Ingredlents Parts by Weight Solids 2-Ethylhexanol half-capped toluene diisocyanate iu methyl isobutyl ketone 320 304 `
Dimethylethanolamine 87.2 87.2 Aqueous lactic acid solution 117.6- 88.2 2-Butoxyethanol 39.2 The 2-ethylhexanol half-capped toluene diisocyanate was added to the dimethylethanolamine in a suitable reaction vessel at room tempera-ture. The mixture exothermed and was stirred for one hour at 80C. Lac-tic acid was then chargad followed by the addition of 2-butoxyethanol.
The reaction mixture was stirred for about one hour at 65C. to form the desired quaternizing agent.

~.
; Plgment Grtndlng Vehicle Example J
.
A pigmen~ grinding vehicle uas prepared from the following charge: - ~

, .
:

' : :

..

, '. . ~.

" 125~37~'~

Ingredlents Parts by Weight Sollds EPON 829 722.10 693.20 Bisphenol ~ 278.40 278.40 2-Ethylhexanol monouretllane of 2,4-toluene diisocyanatc in methyl isobutyl ketone 406.40 386.10 Quaternizing ~gent as descrlbed above 553 470 Deionized water 71.2 ~-Butoxyethanol 1490 The EPON 829 and bisphenol A were charged under a nitrogen atmosphere to a suitable reaction vessel and heated to 150-160C. to lnitiate an exotherm. The reaction mix~ure uas permitted to exother~ for o~e hour at 150-160C. The reection mi~ture was then cooled to 120C.
and the 2-ethylhexanol half-capped toluene diisocyanate added. The tem-perature of the reaction mixture was held at 110-120C. for one hour folloued by the adclition of the 2-butoxyetllanol. The reaction mixture was then cooled to 85-90C., homogenized anci then charged with water followed by the addition of ~he quaternizing agent. The temperature of the reaction mix~ure was held at 8Q-85C. until an acid value of about 1 was obtained.

Example A dibutyltinoxide catalyst paste was prepared as follows:
Ingredients Parts by ~eight Pigment Grlnding Vehlcle of Example J 28.3 Dibutyltinoxicle 25.0 Deionized water 46.7 , . .

' 12S~ 9 The above ingredients were ground in a mill to a Hegman No.7 grind.
EXAMPLE L
A pigment paste was prepared from the following mixture of ingredients:

Ingredients Parts by weight Titanium d;ox;de 44.42 Lead s;licate 2.9 Carbon black 0-37 P;gment Gr;nding Vehicle of example J 18.5 Deionized water 27.51 Catalyst Paste as descr;bed above 6.3 The above ;ngred;ents were ground ;n a mill to a Hegman No.7 grind~ -Cationic Electrodepositable Coatlng Compositions The following examples are of cationic electrodepositable coat;ng compositions containing the novel additives of the ;nvent;on to enhance surface appearance w;thout adversely affecting adhesivness. The~compositions were cathodically electrodeposited over zinc phospha~te pretreated steel panels, -the electrodeposited coatings cured at elevated temperature, and the cured coating evaluated for surface appearance.The cured electrodeposited coatings were -then coated with various `
alkyd and polyester coating compos;t;ons,and the top coat .
cured and evaluated for adhesion ~o the electrodeposition primer.The dry film thlckness~of the top coat was about `35-40 microns. For comparative purposes,compositions with an additive of the prior art ~8 ~LX587~

(U.S. Pat~nc 4,432,850), and for the purposes of control, compositions with no additive were also evalu~ted. The results of ~he testlng are sum~arized-in Table I below.

Example 1 As a control, a catiollic electrodeposition bath with r!o addi-tive was prepared by blending the following mixture of ingredients:
Ingredients - Parts by ~eight Cationic Electrodepos~tion P.esln of Example A 1316 Pigment Paste of Example L 210 Deionized water 1474 The bath had a pH of 6.6 and a resistivity at 20C. of 660 ohm cm . Zlnc phosphate pretreated steel panels were cathodically electro-coated in the elec~rodeposition bath at 240 volts for 2 mlnutes at a bath temperature of 27C. The wet films were cured zt 170C. for 30 minutcs.
: . `

Example 2 As a comparative example, a catlonlc elecerodeposi~ion bath wlth the additive oE U.S.~Patent;4,432,850 was prepared by blen~ing the ~ollowing mixture of ingredients:

In~redients ~ ~ Parts by ~elght Catlonic Electrodepo~ltlon Resin~
of Example A ~ 1270 , Reactlon Product of Exa~ple 1 46 Plgmenc Paste oP Example L ~ 210::
Deionized water 1440 .
: ~

:
~ ~ 29 ~-- - . .
.. . . . .
.. . .
.
' . , ' ' . ,' ~5~7;~3 The bath had a pH of 6.6 and a reslstivity at 20C. of 680 ohm cm . Phosphated pretreated steel panels were cathodically electro-coated and cured 2S described for Example 1.

Example 3 A resin mixture was prepared by blending the following lngredl-~nts:
In~redients Parts by l~'elght Grinding ~ehicle of E~ample J 27 Reaction Product of Example C 16 Deionlzed water 37 Cationic Resln of Example A 1233 The grinding vehicle and reac~ion product of Example C were miY.ed together for Z0 minutes at room temperaturc, then the deionized water was added slo~ly under gocd agitatlon. The- solu~lon was agitated for 30 mlnutes and theD incorporated into the cationlc resin of Example A.
A cationic electrodeposition bath coataining the adduct of EY~ample C was then prepared by blending the following lngredients:
.
Ingredients Parts by l~eight Resin miYtUre as described abo-~c ~ ~ 1313 Pigment Paste of Example L ~ 210 ` Deionized water ~ 1477 The bath had a pH~of 6.7 and a re:slseivity at 20C. of 800 ohm .
cm l. Zinc phosphate pretreated steel panel~ were cathodically electro-coated as described for Example~

: ,~

: ~

- ~ ' ' . ' ' ;' ~ " ' ~ ' .
'~ ' ' , . .
- ~, , ,. :,, ` ~2587;:~

- Example 4 A resitl mlxture ~as prepared by blending the following ingredi-ents:
Ingredients Parts by ~eight Grinding Vehicle of Example J 27 Reaction Product of Example G 16 Deionized water 37 Cationic Resin of Example A 1233 The components were mixed as described for Example 3.
A catior.ic electrodeposition bath was prep~red by blending 1313parts by weight of the resin mixture, 210 parts by weight of the plgment paste of Example L and 1477 parts by welght of deionized water. The bath had a pH of 6.6 and a resistivity at 20~C. of 680 ohm cm 1, Zlnc phosphate pretreated steel panels were cathodically electrodeposited as described in Example 1. ~ , Example 5 A resin mixture ~las prepared by blending the following l~gredi-ents:
Ingredients Parts by Weight Grinding Vehicle of Example J 27 Reaction Product of Example B 16 Deioniæed water 37 Cationic Resin of F.xample A 1233 A cationic electrodeposition bath was prepared by blendin~ 1313parts by weight of the resin mixture, 210 parts by weight of ~he p~gment paste of Example L and l477 parts by weight of deionized water. The bath ~2587;~9 had a pll of 6.45 and s re~istivity at 20C. of 680 ohm cm l, Zinc phos-phat-~ pretreated steel panels were cathodically electrodeposited as described in Example l.

~ .
Example 6 A resin mi~ture was prepared by blending the following ingredi-~nts:
Ingredients Parts by ~lelght Grinding ~ehicle of E~ample J 27 Reaction Product of Example H 13 Deionized water 35 Cationic Resin of Example A1233 A cationic electrodeposition bath was-prepared by blending 1313 part~ by weight of the resin mixture, 210 parts by weigh~ of the pigment paste of Example L and 1477 parts by weight of deioni~.ed water. The bath ~-had a p~{ of 6.70 and a resistivity at 20C. of 740 ohm cm . Zinc phosphate pretreated steel panels were cathodically electrodeposited as described in Example l.

Example 7 A cationic electrodeposltion bath was prepared by blending the following lngredien~s:
., Ingredients Parts by Weight Cationic Rlectrodeposition Resin of Example A 1270 Reaction Product of Example F 46 , Pigment Paste of Example L210 Deionized water 1474 - , .

25873~
.

The bath had a pl~ of 6. 6 and a reslstivlt~ at 20C. of 70G oh~

Cm . ~ , . , . . ~

'` : ' . ~.
` : ' ' ' " `
.

- lX~;87;~'3 ~

r- ~ 1. ~ O O O O O O O O
.

,~o ~n ~ U~
o~ .
P. E U) ~ I o o o o o o o o-o O rl C C
o o C~
. ~q o~ o o o o o o o o o C~0 .
o C~
~ t~
Cl ~rl 0~ :
P. ~ ~~
~o . ~ II o o oooooo C ~r( , C

3 o C~ oo ' 6 ~ ,1 :

`

o ,_ e II o o o o o o o o V ~ ~

:
. ~ , :
zo O

~r( 6 / u~ ~ ,1 o u~
¢ X/. ~ ~ ,~ . o . ~ c JJ
E~ ~ v ~1 ~ :O t~) ~ JJ O 4 o ~ o 4 ~ ~e e ~ o O a4)~E~ U E~
$, ~rl C ~ O h ~u t~ o t~ o ~ o o P~ ~ ) ~ ~ ~ Y ~ O~ ~ ~ , 3 '~

. ` . ' ' ` . .
.

.

12587~.9 Surface appcarance was evaluated vlsually. Ratings of 0 to 5 are assigned ~ith 0 belng very good with very few craters (small rough depressiolls in the surface of the coatlng) and 5 be~ng very poor with many cracers.
Crosshatch adheslon determined by scrlblng a crosshatch pattern on the topcoat, taping the crosshatch area and pulling the tape away at a 180 angle. Coatings with good adhesion will not be removed by the tapes whereas coatings with poor adhesion will be pulled off. Ratings of 0 to

5 are assigned with 0 being very good, l.e., r.o topcoat removal, and 5 being very poor with complete topcoat removal.
Topcoat is a conventional alkyd topcoat available form DuPont Cie, ln Europe as Nero Black.
4Crosshatch adhesion determlned as described above bu~ after first treating the topcoated pane] in a condenslng humidity chamber at 60C.
(QCT chamber) for 16 hours.
5Topcoat 2 is a conventional alkyd topcoat avallable from Corona Cie. in Europ~ as Leaf Green.
Topcoat 3 is a conventional alkyd topcoat available from Corona Cie. in Europe as Belg~ ~tlas.
lTopcoat 4 is a convantional polyester topcoat available from Levis Cie. in Europe as Rosso Levis.

Claims (20)

CLAIMS:

1.An ungelled polyoxyalkylenepolyamine reaction product which is suitable for use in cationic electrodeposition which is characterized as the reaction product of a polyoxyalkylenepolyamine with a monoepoxide.

2. An ungelled polyoxyalkylenepolyamine reaction product which is suitable for use in cationic electrodeposition which is characterized as the reaction product of a polyoxyalkylenepolyamine with a monoepoxide and a polyfunctional material which contains groups capable of reacting with amino and/or hydroxyl groups.

3.The reaction product of claim 2 in which the polyoxyalkylenepolyamine is first reacted with the monoepoxide and then reacted with the polyfunctional material.

4.The product of claim 1, 2or 3 in which the polyoxyalkylenepolyamine contains oxypropylene moieties.

5 The product of claim 1 or 2 in which the polyoxyalkylenepolyamine is a diamine.

6. The product of claim 1 or 2 in which the polyoxyalkylenepolyamine has a molecular weight of 137-3600.

7.The product of claim 1 in which the monoepoxide is selected from those having the following structural formula:

where R1 is hydrogen and methyl and R2 is hydrogen, alkyl including cycloalkyl,aryl and substituted alkyl and aryl groups.

8. The product of claim 2 in which the monoepoxide is selected from those having the following structural formula:

where R1 is hydrogen and methyl and R2 is hydrogen, alkyl including cycloalkyl, aryl and substituted alkyl and aryl groups.

9. The product of claim 7 or 8 in which the monoepoxide is selected from the class consisting of butyl glycidyl ether 2-ethylhexylglycidylether and styrene oxide.

10.The product of claim 2 or 3 in which the polyfunctional material is selected from the class consisting of polyacrylates, polyisocyanates, polycarboxylic acids and polyepoxides.

11.The product of claim 2 or 3 in which the polyoxyalkylenepolyamine:monoepoxide:polyfunctional materials are present in the following equivalent ratio: 1:0.01-1.7:0-1Ø

12.The product of claim 2 in which the polyoxyalkylenepolyamine is first reacted with the monoepoxide such that the amine/epoxide equivalent ratio is greater than 1 and the reaction product is further reacted with a polyacrylate.

13. The product of claim 2 in which the polyoxyalkylenepolyamine is first reacted with the monoepoxide and the reaction product is further reacted with a polyisocyanate.

14 . The product of claim 1 or 2 which is at least partially neutralized with acid.

15.The product of claim 1 which contains blocked polyisocyanate functionality.

16.The product of claim 2 which contains blocked polyisocyanate functionality.

17.The product of claim 15 or 16 in which the reaction product contains blocked isocyanate groups.

18.An aqueous resinous dispersion which contains a cationic electrodepositable resin and from 0.1 to 50 percent by weight of the product of claim 13;the percentage by weight being based on weight of resin solids.

19. The aqueous dispersion of claim 18 which contains a blocked polyixocyanate curing agent.

20. A method of electrocoating an electrically conductive surface serving as a cathode in an electrical circuit comprising said cathode and an anode immersed in an aqueous resinous dispersion, comprising passing electric current between the anode and the cathode to cause a coating composition to deposit on the cathode,wherein the aqueous resinous dispersion is that of claim 18 or 19.