CA1253270A - Cationic electrodeposition composition - Google Patents

Abstract

CATIONIC ELECTRODEPOSITION COMPOSITION

Abstract of the Disclosure A cationic electrodeposition composition comprising the reaction product of one or more base alkyds, containing unsaturation of the fatty acid chains to provide oxidative curing and one or more ethylenically unsaturated monomers, and one or more amine functional monomers, which are added to the base alkyd and polymerized. This composition provides a vehicle which is hydrolytically stable. Paints are prepared by the addition of conventional driers, pigments and solvents to the vehicle composition.

Description

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CATIONIC ELECTRODEPOSITION CO~1POSITION

I. DESCRIPTION
Background of the Prior Art Electrocoating compositions are well known and are disclosed in Gilchrist U.S. Patents No. 3,351,675, 3,362,899, 3,575,909 and 3,351,575; in Turpin U.S.
Patents Nos. 4,221,647 and 4,263,194; and in Tsou U.S.
Patents Nos. 4,148,704, 4,155,824 and 4,246,087.
Electrocoating compositions are dispersed in dilute water baths and then electrocoated onto cathodic and anodic substrates immersed in the electrocoating bath. The electrocoated films can be heat-cured with catalysts or cured by ultraviolet energy. Cationic electrodeposition coatings have superior durability as compared to anionic electrodeposition coatings.
In cathodic electrodeposition, the conductive metal substrate is the cathode in the electrical pro-cess, and an anode is placed in the electrodeposition both with the electrodeposition coating being incor-porated in the aqueous electrolyte between the anode and the cathode. After electrodeposition, the coating compositions must be cured. For example, in Tsou U.S.
Patent 4,148,704, the preferred curing is at a temper-ature ranging from about 250F to about 500F (about 120C to about 260C). Air curing by virtue of the high concentration of unsaturated fatty acids is pos-sible, but the corrosion resistance, weather durabil-ity and chalking resistance at low temperature curing are not as satisfactory.
Cathodic electrocoating systems that are based on alkaline cationic resins are solubilized or dis-persed in water with the aid of acid.

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One of the major problems has been obtaining adequate cure at relatively low temperatures of 150 -175C or less. However, the high basicity of the pre-viously known compositions results in poor low tem-perature cure.
Hazan, U.S. Patent 4,337,187 provided a hydro-philic polyamine copolymer backbone that wraps around a hydrophobic polyester or alkyd resin which is co-dispersed with the polyamine copolmer. A substan-tially neutral pH is thereby provided with a lowamount of amine functionality.
Brief Summary of the Invention The present invention provides a novel cationic electrodeposition composition comprising an acrylated alkyd. Upon electrodeposltion of the composition of this invention films are provided having desirable characteristics and at a significantly lower cure tem-perature than conventional electrodeposition systems.
The first of two steps in the composition manu-facture is the preparation of the base alkyd. Thebase alkyd consists generally of fatty acids, polyols, polybasic acids, diacids and monoacids. The base alkyd is designed to have very good hydrolytic stabil-ity, functional groups ta grafting agent) which are capable of co-polymerizing with ethylenic unsaturated monomers and enough unsaturation of the fatty acid chains to ensure satisfactory oxidative cure of the final film.
Once the base alkyd is prepared, ethylenically unsaturated monomers, such as acrylates and vinyls, are reacted with it. Also, for functionality, amine functional monomers, such as dimethylaminoethyl acry-late, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, tertiary-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate and dimethylaminopropyl methacrylamide, are reacted along with the other '7 monomers and the base alkyd. The amine functionality of the acrylic portion of the resultant resin provides water solubility and cationic functionality to the final resin when salted with an appropriate acid such as lactic, acetic, propionic or other similar, weak organic acids. The resultant resin or vehicle is pre-pared so as to have at least about 0.35 equivalents of amine groups per 1,000 grams of acrylated alkyd.
It has been found that the use of grafting lo agents such as conjugated fatty acids, in the alkyd preparation provides reaction sites for the later ad-dition of acrylic monomers.
The grafting agents provide sites for copoly-merization or "grafting" with the vinyl and acrylic monomers. Suitable grafting agents include unsatu-rated monoacids such as fatty acids, crotonic and sorbic acid. Ethylenically unsaturated isocyanates allow the attachment of acrylic functional groups to the alkyd. The use of isocyanates as grafting agents is shown in U.S. Patent 3,455,857 to Holzrichter.
Additionally, ethylenically unsaturated diacids such as maleic ard itaconic acids and anhydrides also provide suitable grafting agents as shown by Konen et al in U.S. Patent 2,877,194. Also, tetrahydrophthalic acid and its anhydrides as described in ~imura, U.S.
Patent 3,634,351 may be utilized as grafting agents which allow the copolymerization of the alkyd to the monomers.
"Tg", which refers to the glass transition state, is normally referred to as a measurement used 5~.'s2~

for acrylic polymers. See Riddle, Monomeric Acr~lic Esters, Reinhold Publishing Corp., reprint of Chapter I -IV, pp. 59-63. It has been found that the acrylated alkyd of the invention is optimized by developing a high Tg for the acrylic portion to pro-vide stability and to enhance deposition. Electro-deposition should preferably be performed at a rela-tively high voltage, such as 125-300 volts, to provide a coating of sufficient thickness to provide good gloss and flow.
It has been found that alkyds with acid values between about 3 and 10 provide acrylated alkyds with good plating voltage, good gloss and good physical resistance properties. The alkyd is also designed to allow a relatively high Tg of the acrylic portion of the final composition.
The alkyd portion of the acrylated alkyd of the invention has good hydrolytic stability since the attached acrylic portion tends to wrap arond the alkyd. The alkyd's ester bonds are protected from breakage by water due to the amine functional acrylic coating. The acrylated alkyd of the invention pro-vides good low temperature, oxidative cure as opposed to the high temperatures required by Hazan.
Conventional free radical catalysts are used for the polymerization and include peroxides, azo catalysts and the like.
The resulting electrodeposition vehicle, i.e., the acrylated alkyd, is prepared for deposition in a known manner. This includes dispersin~ pigments in the resin, neutralizing the resin with an appropriate acid and reducing with water to about 6~ to 20~
solids. Driers, additional solvents, antioxidants and other additives may be included. A part or item to be ~3,~ J~

coated functions as the cathode. An approprlate mate-rial is chosen as the anode and a unidirectional cur-rent is applied resulting in coating. The coating may be air dried hut is preferably force-dried at approxl-mately 200 - 3nnF (93-150C), resulting in a finished film with excellent gloss, good durability, film toughness and film integrity as measured against water, unleaded gas and ethylene glycol immersion. However, the curing may be done at room temperature to 300F
(150C) with good results. Energy requirements for the coating cure and substrate pretreatment are decreased with use of the low temperature cure cationic electro-deposition composition of the invention.
The acrylated alkyds of this invention may be advantageously coated onto surfaces pretreated with either zinc phosphate or iron phosphate pretreatment, although strictly speaking, pretreatment is not re-quired.
Detailed Description of the Invention ALKYD PREPARATION
The alkyd of the invention will include poly-hydric alcohols, polybasic acids, grafting agents, fatty acids and, optionally, a non-fatty monoacid.
Fatty acids, in which at least two percent of the fatty acid is unsaturated are added to a poly-hydric alcohol, a polybasic acid, a grafting agent and, optionally, a non-fatty monoacid in a reaction vessel with an inert atmosphere. Other monoacids can also be included in the alkyd preparation as is gen-erally known in the art. The presently preferrednon-fatty monoacid is ben~oic acid.
Suitable polyhydric alcohols for use in the alkyd preparation include those having at least two carbon atoms per molecule and also having two to six ~2 ~

hydroxyl groups per molecule. Examples include glycerin, pentaerythritol, trimethylolpropane, trimethylpentanediol, cyclohexane dimethylol, trimethylolethane, dipentaerythritol, ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, hydrogenated bisphenol A, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxy propionate, dimethylolpropionic acid, and the like. Presently preferred polyhydric alcohols are pentaerythritol, trimthylolpropane, cyclohexane dimethylol and trimthylolethane.
Presently preferred fatty monobasic acids which have a high linoleic acid content include high purity tall oil fatty acids and soybean fatty acids.
The presently preferred grafting agents include fatty acids such as conjugated tall oil, like the con-jugated fatty acid sold under the trademark PAMOLYN
380 by Hercules, Inc. (PAMOLYN 380 fatty acid has a high concentration of unsaturation at positions 9 and 11 of a C-18 fatty acid. It contains about 70% con-jugated unsaturation of linoleic acid.), linseed fatty acid, dehydrated castor oil fatty acid and tung fatty acids. Also included are monoacids such as crotonic and sorbic acids, ethylenically unsaturated diacids such as maleic, itaconic and tetrahydrophthalic acid and anhydrides and ethlenically unsaturated isocyanates such as isocyanatoethyl methacrylate.
Suitable polybasic acids include saturated and aromatically unsaturated acids and anhydrides with at least two carboxyl groups per molecule. Examples in-clude malonic, glutaric, pimelic, suberic, azelaic, sebacic, succinic, adipic, phthalic, isophthalic, terephthalic, tricarboxylic lower alkyl phthalic and hexahydrophthalic acids, and trimellitic anhydride, 3,3,4,4-benzophenone tetracarboxylic acid dianhydride ~ 3 ~

and dimerized fatty acids. Presently preferred poly-basic acids include adipic, terephthalic, phthalic and isophthalic acids.
The base alkyd includes, by weight, from about 5 up to about 60~ polybasic acid, from about 5 up to about 60% polyhydric alcohol, about 10-9n% monobasic fatty acid and from 0.5 up to about 60% grafting agent and, optionally, from about 0-50~ non~fatty monoacid.
Most preferably, the base alkyd includes by weight, from about 15 to about 30~ polybasic acid, from about 15 to about 30% polyhydric alcohol, from about 40-75% monobasic fatty acid and from about 2 to about 10~ grafting agent.
The mixture is heated to about 460F (about 238C) as water of esterification is removed as is com-monly accepted practice in alkyd manufacture. Once an acid value of approximately 10 is reached, the reac-tion is cooled and the appropriate solvent added for viscosity control.
ACRYLATION OF BASE ALKYD
The base alkyd described hereinabove and an optional solvent, which is preferably of the glycol ether type, are heated to about 200 - 300F (about 93-150C) under an inert atmosphere.
Ethylenically unsaturated monomers are fed into the mixture over a 2-3 hour period. Also, a free radical catalyst is added at the same time to initiate addition polymerization. Examples of suitable ethylenically unsaturated monomers include styrene, methylmethacrylate, butyl methacrylate, butyl acry-late, lauryl methacrylate, and the like. Presently preferred ethylenically unsaturated monomers include styrene, methyl methacrylate and butyl methacrylate.
Dimethylaminoethyl methacrylate and acrylate, tertiary-butylaminoethyl methacrylate and dimethylaminopropyl tp~

methacrylamide are amine functional ethylenically un-saturated monomers which are preferred. Catalysts such as 2,2-azobisisobutyronitrile~ dicumyl peroxide, and the like are preferred.
After all the monomer and catalyst are added, the mixture is held for several hours with one or two additional adds of catalyst. The reaction is held at temperature until the theoretical non-volatile is reached as is common in adclition polymerization.
SPECIFIC EXAMPLES
The components of the base composition are gen-erally present in the following ranges in the pre-ferred amd most preferred embodiments.
TABLE I
Percent by Weight (total 100%) Components Preferred Most Preferred Alkyd 10-90 20-70 Acrylic 10-90 80-30 TABLE II

Percent by Weight of the Alkyd (total 100~) Components PreferredMost Preferred . _ Alkyd Generic:
Polybasic acid 5 to 60 15-30 Polyhydric alcohol 5 to 60 15-30 Fatty acid 10 - 90 40-75 Grafting agent 0.5 to 60 2-10 Non-Fatty monobasic acid 0 - 50 5-35 ~;2~2;~

TABLE III
Percent by Weight of the ethylenicallY
unsaturated monomers (total 100%) Ethylenically unsaturated Monomers-Generic Preferred Most Preferred Acrylic or methacrylic 0 to 95 10-80 Vinyl 0 to 95 10-80 Amine functional 5 - 95 5-45 TABLE IV
lQ Percent by Weight of the Alkyd ~total 100%) Components Preferred Most Preferred Alkyd-Specific Isophthalic acid 5 to 60 15-30 Pentaerythritol 5 to 60 15-30 Unsaturated fatty acid 10 - 90 40-75 Grafting agent 0.5-60 2-10 Benzoic acid 0 - 50 5-35 Percent by l~eight of the ethylenically unsaturated monomers (total 100%) Ethylenically unsaturated Monomers-Specific Methyl Methacrylate0 to 95 10-80 Styrene 0 to 95 10-80 Dimethylaminoethyl5 - 95 5-45 Methacrylate BASE ALKYD PREPARATION
Example I
Into a container equipped with a thermometer, stirrer, and reflux condenser was placed 6080 grams of a high purity vegetable oil fatty acid, such as the 3 . 2 ~ ~

fatty acid sold under the mark SYLFAT V-18~ by Glidden-Durkee, a division of SCM Corporation of Jacksonville, Florida, 6074 grams of benzoic acid, 5155 grams of technical grade pentaerythritol and 3933 geams of isoph~halic acid under a nitrogen environment.
The mixture was heated to about 300F (149C) and 21.0 grams of FASCAT 4201* brand catalyst was added. Heating continued and at 335F ~168C) 100 grams of xylene was added. One houe and 45 minutes later, additional xylene was added to a total of 210 grams.
At 440F (227C), 1400 grams of water has been removed.
At 445F (229C) the reaction mass was clear coming from the container but hazes when xylene was added. The acid value was 56.7 and 1725 grams of water had been removed~
After five hours, the temperature reached 475F (246C) and the acid value droeped to 9.0, the Gardner viscosity when cut to 70~ solids with xylene was X-Y. The removed water weight was about 2000 grams.
4421 grams of SY1FAT V-18 brand high pULity vegetable oil fatty acid with 2333 grams of a conjugated fa~ty acid, sold by Hercules, Inc., of Wilmington, Delaware, under the mark PAMOLYN 380, was added.
At 9 hours, with the temperature up to 440F (227C), 7.0 grams of Y~SCAT 4201 brand catalyst was added. The acid value was 26.8 with a Gardner-Holt viscosity of F in a 70~ solids in xylene.
AT 9 hours 2~ minutes, Z90 grams of xylene was added to a total of 400 grams, since 100 grams were drained off earlier.
A sample taken from the batch at 480F (249C) had an acid value of 22.1 and a viscosity of F in 70~ solids in xylene. Another 300 * Trade Mark 3~

grams of xylene was added, with the head temperature at 180F
(82C), to a total of 700 grams.
A sample taken at 10 hours had an acid value of 17.7 and viscosi~y of G in 70~ solids in xylene. After another 30 minutes, the acid value dropped to 13.5, with the viscosity still at G.
Another 100 grams xylene wece added, and a sample at 11 hours had an acid value of 11.4 and a viscosity of G. The temperature was raised to 485F (252C). The acid value dropped to 9.8.
At twelve hours, the reaction mass was cooled. At 220F
(104C), 3,687 grams of the propyl ether of propylene glycol was added, and the product was filtered.
The alkyd composition had a viscosity at 70~ solids in propyl ether of propylene glycol of M, an acid value of 8.9, non-volatile solids of 83.9 and a color at 70~ solids in propyl ether of propylene glycol of 9 on the Gardner-Holt scale.

Example II

PARTS BY WEIGHT

Portion I
Pamolyn 380* brand fatty acid 254 Emersol 315* brand fatty acid 1137 Benzoic acid 885 Isophthalic acid 746 Pentaerythritol 850 Portion II
Fascat 4201* brand catalyst 3.8 * Trade Mark ;3~
.

Portion III
Xylene 80 Portion IV
Propyl ether of propylene glycol 794 Portion I is charged into a reaction vessel equipped as in Example I and heated to about 250F
(about 121C). Portion II is added and heat is applied and portion III is added as an azeotrope at a rate which water removal permits to about 460F ~238C).
The reaction continues until an acid value of about 5 to 7 and a viscosity of about X to Y on the Gardner scale is obtained with a sample cut to about 70% solids with xylene. The alkyd is cooled, and portion IV is added when the temperature drops below about 300F.

Example III
. _ Parts by ~1eight Portion I
Soybean fatty acid 1268 Pamolyn 380 brand fatty acid210 Trimethylol ethane 856 Isophthalic acid 896 senzoic acid 269 Portion I is charged into a reactor equipped for fusion and heat is applied to a peak of about 480F (249C) as water removal permits. The reaction is run at about 480F (249C) until an acid value of 5 or less is reached.

Example IV

Parts by Weight Portion I
Sylfat V-18 vegetable fatty acid 1230 Isophthalic acid 746 Benzoic acid 700 Pentaerythritol 856 Fascat 4201 brand catalyst 3.6 Portion I is charged into a reactor vessel equipped for fusion and heat is applied to a peak of about 480F (249C) as water removal permits. The reaction is run at about 480F (249C) until an acid value of 5 or less is reached.
ACRYLATION OF BASE ALKYD
Example V
1489 grams of base alkyd prepared from Example I were charged with 281 grams of propyl ether of propylene glycol and heated to 210F (99C), in a nitrogen atmosphere. A total of 250 grams of styrene, 505 grams of methyl methacrylate, 250 grams of butyl methacrylate, 245 grams of dimethylaminoethyl metha-crylate and 35 grams of the polymerization initiator sold under the mark VAZO-64 by E.I. du Pont de Nemours and Company were continuously fed in and mixed over about a t~o hour and forty minute period, while main-taining the temperature at about 210F (99C). Another acceptable addition procedure would be to add one quarter of the monomer each forty minutes. A total of 110 gra~s of diethylene glycol dimethyl ether and an additional 9.5 grams of VAZ0-64 initiator were mixed.

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Sylfat V-18 vegetable fatty acid 1230 Isophthalic acid 746 Benzoic acid 700 Pentaerythritol 856 Fascat 42nl brand catalyst 3.6 Portion I is charged into a reactor vessel equipped for fusion and heat is applied to a peak of about 480F (249C) as water removal permits. The reaction is run at about 480F (249C) until an acid value of 5 or less is reached.
ACR~LATION OF BASE ALKYD
-Example V
1489 grams of base alkyd prepared from Example I were charged with 281 grams of propyl ether of propylene glycol and heated to 210F (99C) in a nitrogen atmosphere. A total of 250 grams of styrene, 505 grams of methyl methacrylate, 250 grams of butyl methacrylate, 245 grams of dimethylaminoethyl metha-crylate and 35 grams of the polymerization initiator sold under the mark VAZO-64 by E.I. du Pont de Nemours and Company were continuously fed in and mixed over about a two hour and forty minute period, while main-taining the temperature at about 210F (99C). An-other acceptable addition procedure would be to add one quarter of the monomer each forty minutes. A
total of 110 grams of diethylene glycol dimethyl ether and an additional 9.5 grams of VAZ0-64 initiator were mixed. One half was added one hour after the monomer catalyst addition and the other half was added an hour later.
After mixing about one more hour at about 200 to 210F (93-99C), the viscosity of a sample diluted to about 70~ solids with propyl ether of propylene glycol was 111 stokes. The non-volatile material level of the acrylated alkyd was 67.7~, compared to a theoretical 7n.0~.

One half was added one hour after the mono~er catalyst addition and the other half was added an houe later.
After mixing about one more hour at about 200 to 210F (93-99C), the viscosity of a sample diluted to about 70% solids with propyl ether oE propylene glycol was 111 stokes. I'he non-volatile material 1QVe1 ~f the acr~ 'ed al.~yd was 67.7~, compared to a theoretical 70.0~.
Example VI

Parts by ~eight Portion I
Propyl ether of propylene glycol 604 Portion II
Methyl Methacrylate 555 Styrene 200 Dimethylaminoethyl Methacrylate 245 Vazo 67*brand polymerization initiator 32.2 Alkyd prepared by Example II1875 Portion III
Propyl ether of propylene glycol 40 Portion IV
DiCup R brand catalyst 30 Propyl ether of propylene glycol 100 Portion I is charged into a reactor and heated to about ~00F (93C) under an inert atmosphere. Por-tion II is added (with 10% initially) incrementally over the next two hours and 55 minutes at 200F (93C~.
Portion III is then used to flush any pumping lines and the batch is held for one hour at 200F (93C).
* Trade.Mark 7~

One-half of Portion IV is added and the temperature is raised to about 280F (138C) over 30 minutes. The batch is held one hour and the remainder of Portion IV
is added, and held at two hours before cooling.

Example VII
_ Parts by Weight Portion I
Alkyd prepared by Example III 600 Ethylene glycol monobutylether 212 Portion II
Methyl Methacrylate 284 t-Butylaminoethyl Methacrylate 116 Dicumyl peroxide 12 Portion III
Ethylene glycol monobutylether 40 Dicumyl peroxide 4 Portion I is charged into a reactor and heated to about 290F (143C). Portion II is then blended into a uniform mixture and one-quarter of the mix is added to the reactor and held at about 290F (143C) for 30 minutes. The mix of Portion II is added by quarters as above at 290F (143C). One hour after the last aliquot of Portion II has been added, one-half of a mixture of Portion III is added and held for one hour. The remainder of Portion III is then added and held for 2 hours. The acrylated alkyd composition is then cooled and filtered.

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Example VIII
_ Parts by Weight Portion I
Alkyd prepared by Example :[V 515 Dibutyltin dilaurate 0.5 Portion II
Isocyanatoethylmethacrylate 12.5 Diethylene glycol dimethyl ether15.2 Portion III
Ethylene glycol monobutyl ether220 Portion IV
Methyl methacrylate 200 Styrene 100 Butyl methacrylate 90 Dimethylaminoethyl methacrylate 98 Vazo 64 brand polymerization initiator 14 Portion V
Vazo 64 brand polymerization initiator 4 Ethylene glycol monobutyl ether 50 Portion I is charged in a reactor and heated to about 75C. A mixture of Portion II is added over 30 minutes and then held for 30 minutes at 75C. Portion III is added and the temperature is raised to about 93C. The mixture of Portion IV is then added to the reactor, 10% intially being added. After 15 minutes, the rest of Portion IV is added to the reactor over 150 minutes in about 10% aliquots. After 60 minutes ~r~ s~

from the last aliquot, one-half of Portion V is added. The remainder of Portion V is added after another 60 minutes and the batch is held for about 120 minutes at 93C. The resultant acrylated alkyd com-position had 74.5% non-volatile materials. ~ sample adjusted to 70% solids with the addition of ethylene glycol monobutyl ether had a viscosity of 25C stokes.

Example IX

Parts by Weight Portion I
-Alkyd prepared by Example IV 3181 Sorbic Acid 34 Xylene 120 Portion II
Propyl ether of propylene glycol2064 Portion III
Methyl Methacrylate 1189.6 Styrene 428.7 Dimethylaminoethyl methacrylate525.1 Dicumyl peroxide 64.3 Portion IV
Propyl ether of propylene glycol171.5 Dicumyl peroxide 17.1 Portion I is charged into a reactor and heated to about 400F (204C) in an inert atmosphere. The batch is held at about 400-420F (204-216C) using a xylene reflux to remove water until the acid value ~ ~.532~

drops to the value the base alkyd had initially. The batch is allowed to cool to about 280F (138C). Por-tion II is then added and the temperature is raised to 290F (143C). Initially, 10% of a mixture of Portion III is added to the reactor and held 15 minutes. The remainder of Portion III is added in roughly equal increments over 120 minutes~ After the monomers have all been added for 60 minutes, one-half of Portion IV
is added. The remainder Portion IV is added after one hour and the batch is held for about 120 minutes. The acrylated alkyd is then cooled and filtered. The com-position had a 68~ non-volatile material content and a viscosity of 100 stokes when adjusted to 65~ solids with propyl ether of propylene glycol.
PAINT PREPARATION
Paints for cationic electrodeposition are pre-pared in a conventional manner by adding pigments, solvents and/or driers to the electrodeposition vehicle of this invention, as desired. The paint is then electroplated from a tank with the acrylated alkyd and an organic acid such as propionic acid. A
one mil (0.0254 mm) coating is developed when electro-plated at 125 volts at ambient temperature for about two minutes. Examples of paint compositions using the base compositions of the invention are described below Example X

-Parts by Weight .
Portion I - Electrodeposition Vehicle Acrylated alkyd from Example VII179.4 Phthalo Green 4.52 Yellow iron oxide 16.62 ~i~S ~ 3 ~ ~) Ciba 2 &LTE* 1.41 Ethylene glycol monohexyl ether 17.0 Ethylene glycol monobutyl ether 2.1 Portion II ~ Piqments, solvents. etc.
Lactic acid (B0%) 8.9 12~ Cobalt naphthenate drier 1.0 Methyl ethyl ketoxime 1.0 Portion III
Deionized water 1468.05 Portion I is charged into a conventional sand mill and is milled to about a 7 g . The components of Portion II
are added to the resultant paste in order and mixed. Portion III
is then added. The eaint has a solids content of about 10%, a pH
of 4.9 and conductivity of 900 umhos. A Bonderite 1000* brand panel from Hooker Chemical Corp. of Detroit, Michigan plated for two minutes at 15b vol~s gava a 1.0 mil (0.0254 mm) film. After force drying for 45 minutes at 200F (93C), a gloss reading of gO/75 at 60~20 meters on a Hunter D48D~ gloss meter was obtained.

ExamPle XI

Parts by Weight -Portion I - Electrodeposition Vehicle Acrylated alkyd from Example VIII112.3 Ethylene glycol monobutyl ether 1.9 Ethylene glycol monohexyl ether 10.0 Titanium oxide (rutile~ 16.7 ~ Trade Mark ~ ;3~2~d~

Portion II - Pigments, solvents, etc.
Lactic acid (80%) 5.3 12% Cobalt naphthenate drier 0.5 Methylethyl ketoxime 1.0 Portion III
-Deionized water 854 Portion I is sandmilled at high speed to a value of about a 7-1/2 + Hegman mixed into the dispersion and water from Portion III
is added resulting in a paint with 10~ solids, pH 4.7 and a conductivity of 720 umhos. Plating at 150-200 volts produced a 1 mil (0.0254 mm) film. After force drying for 30 minutes at 250F (121C), a hard, smoo~h coating is produced. Reflection is greater than 80%
on the 60 Hunter D48D gloss meter.

Example XII
.
Parts by Weight Portion I
Alkyd from Example II 8.85

2-ethyl hexyl alcohol 3.20 Titanium dioxide (rutile) 28.35 Portion II
Acrylated alkyd from Example VIl9S.9 2-ethyl hexyl alcohol 10.9 Propionic acid 5.6 Manganese drier 5% 2.5 ~ ~53~

Activ B bcand deiec pro~oter ~COQ
Vanderbilt Chemical Co. 0.37 Ortho-t-butyl phenol 0.57 Deinoized watec 1443.76 This paint is mixed and milled as above. The paint had a conductivity of 800 umhos and a pH of 4.5 at 10~ solids Plating a~ 140 volts of direct cucrent pcoduced a one mil ~0.0254 mm~ film. The coated Bondecite 1000 bcand panel fcom Hookec Chemical Cocp.
of Detcoit, Hichigan ~as then cuced at 200F (93C) foc 45 minutes. The finished coat had a gloss of 94 on the 60~ Huntec D48D gloss metec.
rn considering the invention, it should be ceQembeced that the pcesent disclosuce including the -~ preferced embodiments is illustcative only, and that the scope of the invention should be determined by the appended claims.

Trade Mark

Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An acrylated alkyd graft copolymer electrodeposition composition in which the acrylic portion contains amine functionality providing water dispersibility and cationic functionality.

2. The composition of Claim 1 wherein said alkyd portion comprises the reaction product of a polyhydric alcohol, a polybasic acid, a fatty acid and a grafting agent.

3. The composition of Claim 1 wherein the amount of amine functionality is at least 0.35 equivalents per 1000 grams of the graft copolymer.

4. A cationic electrodeposition coating vehicle comprising the reaction product of:
a) a base alkyd, including a grafting agent; and b) ethylenically unsaturated monomers, at least one of which includes an amine functional monomer, said amine functional groups in a quantity to provide a water dispersible and cationically electrodepositable composition.

5. The electrodeposition vehicle of Claim 4 wherein said alkyd comprises, on a 100 weight percent total weight basis:
a) 5 to 60% polybasic acid;
b) 5 to 60% polyhydric alcohol;
c) 0.5 to 60% grafting agent;
d) about 10-90% fatty acid, said fatty acid having at least 2% unsaturation; and e) about 0 - 50% non-fatty monobasic acid.

6. The electrodeposition vehicle of Claim 5 wherein said polybasic acid is isophtalic or phthalic acid.

7. The electrodeposition vehicle of Claim 5 wherein said grafting agent is selected from the group consisting of ethylenically unsaturated monoacids ethylenically unsaturated isocyanates, ethylenically unsaturated diacids and their anhydrides and mixtures thereof.

8. A cationic electrodeposition coating composition comprising:
a reaction product of a base alkyd and ethylenically unsaturated monomers at least some of which are amine functional monomers, said base alkyd comprising the reaction product of a polyhydric alcohol, a polybasic acid, a fatty acid, and a grafting agent; and said product including amine functional groups in a quantity to provide a water dispersible and cationically depositable composition.

9. The electrodeposition composition of Claim 8 including a non-fatty monoacid in the base alkyd.

10. The electrodeposition composition of Claim 8 including pigments, solvents and driers to form a paint composition for electrodeposition.

11. The process for forming a water dispersible cationic electrodeposition vehicle comprising:
a) reacting a polyhydric alcohol, polybasic acid, fatty acid and a grafting agent together to form a base alkyd, and b) copolymerizing said base alkyd with ethylenically unsaturated monomers at least one of which is an amine functional monomer.

12. The process of claim 11 wherein said base alkyd includes the addition of non-fatty monobasic acid.

13. The process of claim 11 wherein said grafting agent is selected from the group consisting of conjugated fatty acids having at least 2% unsaturation, sorbic, crotonic, maleic, itaconic, tetrahydrophthalic acids and anhydrides and ethylenically unsaturated isocyanates.