AU622149B2

AU622149B2 - Cationic electrodeposition composition

Info

Publication number: AU622149B2
Application number: AU30045/89A
Authority: AU
Inventors: Jeffrey L. Anderson; Robert B. Edenborg; Philip J. Ruhoff
Original assignee: Valspar Corp
Current assignee: Valspar Corp
Priority date: 1983-12-08
Filing date: 1989-02-17
Publication date: 1992-04-02
Anticipated expiration: 2005-03-19
Also published as: CA1253270A; JPH0586824B2; AU4018085A; AU3004589A; JPS61213272A

Description

62 21 4 COMMONWEALTH OF AUSTRAL 6 2 2 m PATENTS ACT 1952-69 COMPLETE SPECIFICATION

'ORIGINAL)

Class Int. Class Application Number: Lodged: a c Ei Complete Specification Lodged: Accepted: Published: Priority: Related Art:

A

Name of Applicant: Address of Applicant: Actual Inventor: Address for Service: THE VALSPAR CORPORATION 1101 Third Street South, United States of America Minneapolos, Minnesota 55415, JEFFREY L. ANDERSON, PHILIP J. RUHOFF and ROBERT B. EDENBORG EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: Cationic Electrodeposition Composition The following statement is a full description of this invention, including the best method of performing it known to :US

LI-~

I

2 CATIONIC ELECTRODEPOSITION COMPOS'ITION I. DESCRIPTION Background of the Prior Art Electrocoating compositions are well known and are disclosed in Gilchrist U.S. Patents No. 3,351,675, 4 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 10 anodic substrates immersed in the electrocoating bath. The electrocoated films can be heat-cured with o* 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 proj cess, and an anode is placed in the electrodeposition both with the electrodeposition coating being incorporated in the aqueous electrolyte between the anode and the cathode. After electrodeposition, the coating compositions must be cured.' For example, in Tsou U.S.

I

S.t. Patent 4,148,704, the preferred curing is at a tempert.t ature ranging from about 250 0 F to about 500°F (about 120 0 C to about 260 0 Air curing by virtue of the high concentration of unsaturated fatty acids is possible, but the corrosion resistance, weather durability and chalking resistance at low temperature curing are not as satisfactory.

Cathodic electrocoating systems that are based on alkaline cationic resins are solubilized or dispersed in water with the aid of acid.

-3- One of the major problems has been obtaining adequate cure at relatively low temperatures of 1500 175 0 C or less. However, the high basicity of the previously known compositions results in poor low temperature cure.

Hazan, U.S. Patent 4,337,187 provided a hydrophilic polyamine copolymer backbone that wraps around a hydrophobic polyester or alkyd resin which is codispersed with the polyamine copolmer. A substantially neutral pH is thereby provided with a low amount of amine functionality.

6 Q eo** e* 6 9 0 S* 0 io 400 *0 I 0 ft 3a The present invention therefore provides an acrylated graft copolymer electrodeposition composition dried at a temperature of 930C to 1400C wherein said composition is the reaction product of a base alkyd and ethylenically unsaturated monomers, the alkyd providing more than 37.5% of the weight of the reaction product, and the ethylenically unsaturated monomers including from 0-40% by weight of monovinyl aromatic hydrocarbon monomers based on the total weight of ethylenically unsaturated monomers and further containing one or more amine functional monomers providing amine functional groups in sufficient quantity, when in amine salt form, to provide to said reaction product water dispersibility and cationic functionality, said 1 0 alkyd being the reaction product of a polyhydric alcohol, a polybasic acid, a fatty acid, and a grafting agent. Preferably the amount of amine functionality is at least 0.35 equivalents per 1000 grams of the graft copolymer. Preferably the alkyd comprises, on a 100% weight percent total weight basis: a. 5 to 60% polybasic acid; 15 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; S, and e. about 0-50% non-fatty acid. Preferably the polybasic acid is isophthalic S' 2 0 or phthalic acid. Preferably the grafting agent is selected from ethylenically unsaturated S• monoacids, ethylenically unsaturated isocyanates, ethylenically unsaturated diacids and c c t their anhydrides and mixtures thereof. It is further preferred that the composition S includes a non-fatty monoacid in the base alkyd. Preferably the ethylenically S, unsaturated monomers are essentially free of hydroxyl functionality. Preferably also S 25 the composition includes pigments, solvents and driers to form a paint composition for electrodeposition.

The invention also provides a process for forming an air-dried water-dispersed cationic electrodeposition comprising: reacting a polyhydric alcohol, polybasic acid, fatty acid and a grafting agent together to form a base alkyd; copolymerizing said base alkyd with ethylenically unsaturated monomers of which 0-40% by weight are monovinyl aromatic hydrocarbon monomers and which includes one or more amine functional monomers sufficient, when in amine salt form, to provide to the reaction product water dispersibility and cationic functionality, the

U./

4 rI 'i 3b quantity of said monomers being chosen so that the base alkyd provides more than 37.5% of the weight of the reaction product; and air-drying the product of at a temperature of 93°C to 1400C.

Preferably the reactants for step include a non-fatty monobasic acid. Preferably the ethylenically unsaturated monomers are essentially free of hydroxyl functionality.

In a preferred embodiment the grafting agent is selected from conjugated fatty acids having at least 2% unsaturation, sorbic, crotonic, maleic, itaconic and tetrahydrophthalic acids and anhydrides and ethylenically unsaturated isocyanates.

t tt ie cii I t t Ci C Ci rCCr ft C t 'C C' C c C S« C 1- ;--CI 3c I.-;rinn o-3:ancerm Preferably the base alkyd includes the addition of non-fatty monobasic acid; the grafting agent is selected from the group consisting ofn conjugated fatty acids having at least 2% unsaturation, sorbic, crotonic, maleic, itaconic, tetrahydrophthalic acids and anhydrides and ethylenically unsaturated isocyanates; the acrylic portion contains amine functionality providing water dispersibility and cationic functionality; the alkyd portion comprises the reaction product of a polyhydric alcohol, a polybasic acid, a fatty acid and a grafting agent; and the amount of amine functionality is at least 0.35 equivalents per 1000 grams of the graft copolymer.

15 The first of two steps in the composition manufacture is the preparation of the base alkyd. The base Salkyd consists generally of fatty acids, polyols, polybasic acids, diacids and monoacids. The base alkyd is designed to have very good hydrolytic stability, functional groups (a S 20 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 Sof 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 Stmonomers, such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, tertiary-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate and dimethylaminopropyl methacrylamide, are reacted along with the other U1 4 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 prepared 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 S,0 agents such as conjugated fatty acids, in the alkyd preparation provides reaction sites for the later addition of acrylic monomers.

The grafting agents provide sites for copolymerization or "grafting" with the vinyl and acrylic monomers. Suitable grafting agents include unsaturated 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 and itaconic acids and anhydrides also provide suitable grafting agents as shown by Konen et al in U.S. Patent 2,877,194. Also, tetrahydrophthalic and its anhydrides as described in Kimura, U.S.

Patent 3,634,351 may be utilized as grafting agents which allow the copolymerization of the alkyd to the monomers.

which refers to the glass transition state, is normally referred to as a measurement used 5 "T 10 t t CCt C I I tt for acrylic polymers. See Riddle, Monomeric Acrylic 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 provide stability and to enhance deposition. Electrodeposition should preferably be performed at a relatively 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 provides 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 dispersing pigments in the resin, neutralizing the resin with an appropriate acid and reducing with water to about 6% to solids. Driers, additional solvents, antioxidants and other additives may be included. A part or item to be r 25 6 Coated functions as the cathode. An appropriate material is chosen as the anode and a unidirectional current is applied resulting in coating. The coating may be air dried but is preferably force-dried at approximately 200 300 0 F (93-150°C), resulting in a finished film with excellent gloss, good durability, film toughness and film integrity as measured against waterunleaded gas and ethylene glycol immersion. However, the curing may be done at room temperature to 300 0

F

S 10 (150°C) with good results. Energy requirements for the *o coating cure and substrate pretreatment are decreased vote with use of the low temperature cure cationic electro- O deposition composition of the invention.

The acrylated alkyds of this invention may be 15 advantageously coated onto surfaces pretreated with either zinc phosphate or iron phosphate pretreatment, although strictly speaking, pretreatment is not ret quired.

Detailed Description of the Invention ALKYD PREPARATION I The alkyd of the invention will include polyhydric alcohols, polybasic acids, grafting agents, fatty acids and, optionally, a non-fatty monoacid.

Fatty acids, in which at least two percent of 25 the fatty acid is unsaturated are added to a polyhydric alcohol, a polybasic-acid, a grafting agent and, optionally, a non-fatty monoacid in a reaction vessel with an inert atmosphere. Other monoacids can Salso be included in the alkyd preparation as is generally known in the art. The presently preferred non-fatty monoacid is benzoic 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 ii: 7 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-3hydroxypropyl-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 oa have a high linoleic acid content include high purity tall oil fatty acids and soybean fatty acids.

15 The presently preferred grafting agents include fatty acids such as conjugated tall oil, like the conjugated 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% conjugated unsaturation of linoleic acid.), linseed fatty a 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 isocyanate's such as isocyanatoethyl methacrylate.

Suitable polybasic acids include saturated and aromatically unsaturated acids and anhydrides with at least two carboxyl groups per molecule. Examples include malonic, glutaric, pimelic, suberic, azelaic, sebacic, succinic, adipic, phthalic, isophthalic, terephthalic, cricarboxylic lower alkyl phthalic and hexahydrophthalic acids, and trimellitic anhydride, 3,3,4,4-benzophenone tetracarboxylic acid dianhydride 8 As r I

E

rt c t te t tt Cr r Sc~ and dimerized fatty acids. Presently preferred polybasic 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 10-90% 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 460 0 F (about 238 0 C) as water of esterification is removed as is commonly accepted practice in alkyd manufacture. Once an acid value of approximately 10 is reached, the reaction is cooled and the appropriate solvent added for viscosity control.

20 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 200 300°F (about 93-150 0 C) under an inert atmosphere.

25 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 acrylate, lauryl methacrylate, and the like. Presently preferred ethylenically unsaturated monomers include styrene, methyl methacrylate and butyl methacrylate.

Dimethylaminoethyl methacrylate and acrylate, tertiarybutylaminoethyl methacrylate and dimethylaminopropyl r 9 methacrylamide are amine functional ethylenically unsaturated 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 addition polymerization.

SPECIFIC EXAMPLES The components of the base composition are generally present in the following ranges in the preferred amd most preferred embodiments.

TABLE I Percent by Weight (total 100%) a. a S4

S

a .4 *i a t ComDonents Preferred Most Preferred Alkyd Acrylic 10-90 10-90 20-70 80-30 TABLE II Percent by Weight of the Alkyd (total 100%) A, Components Alkvd'Generic: Polybasic acid Polyhydric alcohol Fatty acid Grafting agent Non-Fatty monobasic acid Preferred Most Preferred 5 to 60 5 to 60 10 90 0.5 to 60 0 50 15-30 15-30 40-75 2-10 5-35 :i .I :i 10 TABLE III Percent by Weight of the ethylenically unsaturated monomers (total 100%) Ethylenically unsaturated Monomers-Generic Acrylic or methacrylic Vinyl Amine functional Preferred 0 to 95 0 to 95 5 95 Most Preferred 10-80 10-80 5-45 a be) S aI S "baa S* r

LIE

TABLE IV Percent by Weight of the Alkyd (total 100%) Components Alkyd-Specific Isophthalic acid Pentaerythritol Unsaturated fatty acid Grafting agent Benzoic acid Preferred 5 to 60 5 to 60 10 90 0.5-60 0 50 Most Preferred 15-30 15-30 40-75 2-10 5-35 Percent by Weight of the ethylenically unsaturated monomers (total 100%) Ethylenically unsaturated Monomers-Specific Methyl Methacrylate Styrene Dimethylaminoethyl Methacrylate 0 to 95 0 to 95 5 !5 10-80 10-80 5-45 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 1- 1 I I -11fatty 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 grams of isophthalic acid under a nitrogen environment. The mixture was heated to about 300 0 F (149 0 C) and 21.0 grams of FASCAT 4201 brand catadyst was added. Heating continued and at 335 0 F (168 0 C) 100 grams of xylene was added. One hour and 45 minutes later, additional xylene was added to a total of 210 grams.

At 440 0 F (227 0 1400 grams of water had been removed. At 445 0 F (229 0 C) the reaction mass was clear coming from the container but hazes when xylene was 6010 added. The acid value was 56.7 and 1725 grams of 9 4. 15 water had been removed.

After five hours, the temperature reached 475 0

F

(246 0 C) and the acid value dropped to 9.0, the Gardner viscosity when cut to 70% solids with xylene was X-Y.

4 The removed water weight was about 2000 grams.

64 20 4421 grams of SYLFAT V-18 brand high purity a vegetable oil fatty acid with 2333 grams of a conjugated fatty acid, sold by Hercules, Inc., of Wilmington, Delaware, under the mark PAMOLYN 380, was Sadded.

At 9 hours, with the temperature up to 440 0

F

(227 0 7.0 grams of FASCAT 4201 brand catalyst was added. The acid value was 26.8 with a Gardner-Holt Sgviscosity of F in a 70% solids in xylene.

At 9 hours 25 minutes, 290 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 480 0 F (249 0 C) had an acid value of 22.1 and a viscosity of F in 70% solids in xylene. Another 300 ea d e i auews 67an 72 raso 10 15wtrhdbenrmvd 12 grams of xylene was added, with the head temperature at 180 0 F (82 0 to a total of 700 grams.

A sample taken at 10 hours had an acid value of 17.7 and viscosity 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 lu0 grams xylene were added, and a sample at 11 hours had an acid value of 11.4 and a viscosity of G. The temperature was raised to 485 0

F

(252 0 The acid value dropped to 9.8.

t At twelve hours, the reaction mass was cooled.

i 'At 220°F (104 0 3,687 grams of the propyl ether of *propylene glycol was added, and the product was I filtered.

15 The alkyd composition had a viscosity at 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 t t glycol of 9 on the Gardner-Holt scale.

cV 1 t 20 Example II S Parts by Weight Portion I v 25 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

A§

u 1 1 r c: t 11 13 Portion III Xylene 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 250°F (about 121°C). Portion II is added and heat is applied and portion III is added as an azeotrope at a rate S* which water removal permits to about 460°F (238°C).

The reaction continues until an acid value of about to 7 and a viscosity of about X to Y on the Gardner scale is obtained with a sample cut to about 70% solids S. with xylene. The alkyd is cooled, and portion IV is S" added when the temperature drops below about 300 0

F.

Example III a t Parts by Weight Portion I S, Soybean fatty acid 1268 Pamolyn 380 brand fatty acid 210 Trimethylol ethane 856 Isophthalic acid 896 Benzoic acid 269 Portion I is charged into a reactor equipped for fusion and heat is applied to a peak of about 480"F (249 0 C) as water removal permits. The reaction is run at about 480 0 F (249 0 C) until an acid value of or less is reached.

i i .t 14 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 C f S 10 Portion I is charged into a reactor vessel equipped for fusion and heat is applied to a peak of about 480°F (249°C) as water removal permits. The e reaction is run at about"480 0 F (249 0 C) until an acid value of 5 or less is reached.

ACRYLATION OF BASE ALKYD Example V a 1489 grams of base alkyd prepared from Example "I I were charged with 281 grams of propyl ether of propylene glycol and heated to 210 0 F (99 0 in a 1 20 nitrogen atmosphere. A total of 250 grams of styrene, 505 grams of methyl methacrylate, 250 grams of butyl methacrylate, 245 grams of dimethylaminoethyl metha- Scrylate and 35 grams of the polymerization initiator sold under the mark VAZQ-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- 7' taining the temperature at about 210 0 F (99 0 A-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 VAZO-64 initiator were mixed.

15 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 480 0 F (2490C) as water removal permits. The reaction is run at about 480°F (249 0 C) until an acid value of 5 or less is reached.

SACRYLATION OF BASE ALKYD Example V S,,o .1489 grams of base alkyd prepared from Example I were charged with 281 grams of propyl ether of propylene glycol and heated to 210 0 F (99 0 C) in a S* nitrogen atmosphere. A total of 250 grams of styrene, 505 grams of methyl methacrylate, 250 grams of butyl methacrylate, 245 grams of dimethylaminoethyl methacrylate and 35 grams of the polymerization initiator sold under the mark VAZO-64 by E.I. du Pont de Nemours 4 and Company were continuously fed in and mixed over about a two hour and forty minute period, while maintaining the temperature at about 210°F Ano 2 other acceptable addition procedure would be to add 25 one quarter of the monomer each forty minutes. A Stotal of 110 grams of diethylene glycol dimethyl ether and an additional 9.5 grams of VAZO-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 2000 i to 210°F (93 0 -990C), 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 Stheoretical 70.0%.

j 16 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 2000 to 210°F (93-990C), 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 70.0%.

Example VI Parts by Weight 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 o, Alkyd prepared by Example II 1875 Portion III Propyl ether of propylene glycol S Portion IV DiCup R brand catalyst Propyl ether of propylene glycol 100 Portion I is charged into a reactor and heated to about 200 0 F (93 0 C) under an inert atmosphere. Portion II is added (with 10% initially) incrementally over the next two hours and 55 minutes at 200 0 F (93 0

C).

Portion III is then used to flush any pumping lines and the batch is held for one hour at 200 0 F (93 0

C).

rpiehro rpln lcl4 2 :i 17 One-half of Portion IV is added and the temperature is raised to about 280 0 F (1380C) 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 10 Portion I Alkyd prepared by Example III 600 Ethylene glycol monobutylether 212 9 S Portion II 15 Methyl Methacrylate 284 t-Butylaminoethyl Methacrylate 116 Dicumyl peroxide 12 4 a* Portion III Ethylene glycol monobutylether SDicumyl peroxide 4 Portion I is charged into a reactor and heated to about 290°F (143 0 Portion I is then blended 25 into a uniform mixture and one-quarter of the mix is added to the reactor and held at about 290 0 F (143 0

C)

for 30 minutes. The mix of Portion II is added by quarters as above at 290 0 F (143 0 'One hour after the last aliquot of Portion II has been added, onehalf 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.

i-A j I 18 Example VIII Parts by Weight Portion I Alkyd prepared by Example IV 515 Dibutyltin dilaurate Portion II S Isocyanatoethylmethacrylate 12.5 I Diethylene glycol dimethyl ether 15.2 Portion III 10 Ethylene glycol monobutyl ether 220 Portion IV Methyl methacrylate 200 S. Styrene 100 S" Butyl methacrylate 1 5 Dimethylaminoethyl methacrylate 98 Vazo 64 brand polymerization initiator 14 i Portion V Vazo 64 brand polymerization initiator 4 *I Ethylene glycol monobutyl ether Portion I is charged in a reactor and heated to about 75 0 C. A mixture of Portion II is added over minutes and then held for 30 minutes at 75 0 C. Portion III is added and the temperature is raised to about 93 0 C. 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 a 19 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 93 0 C. The resultant acrylated alkyd com- S position had 74.5% non-volatile materials. A sample adjusted to 70% solids with the addition of ethylene glycol monobutyl ether had a viscosity of 250 stokes.

Example IX Parts by Weight 10 Portion I Alkyd prepared by Example .IV 3181 0 Sorbic Acid 34 Xylene 120 'Portion II 15 Propyl ether of propylene glycol 2064 S* Portion III Methyl Methacrylate 1189.6 i Styrene 428.7 Dimethylaminoethyl methacrylate 525.1 20 Dicumyl peroxide 64.3 Portion IV Propyl ether of propylene glycol 171.5 Dicumyl peroxide 17.1 Portion I is charged into a reactor and heated to about 400 0 F (204 0 C) in an inert atmosphere. The batch is held at about 400-420 0 F (204-216 0 C) using a xylene reflux to remove water until the acid value 1: i L 20 drops to the value the base alkyd had initially. The batch is allowed to cool to about 280 0 F (138 0 Portion II is then added and the temperature is raised to 290°F (143 0 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 10 hour and the batch is held for about 120 minutes. The acrylated alkyd is then cooled and filtered. The como' 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.

15 PAINT PREPARATION Paints for cationic electrodeposition are prepared in a conventional manner by adding pigments, solvents and/or driers to the electrodeposition SC 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 electroplated at 125 volts at ambient temperature for about two minutes. Examples of paint compositions using the 25 base compositions of the invention are described below.

Example X Parts by Weight Portion I Electrodeposition Vehicle Acrylated alkyd from Example VII 179.4 Phthalo Green 4.52 Yellow iron oxide 16.62 1 .1 I 1 21 Ciba 2 GLTE 1.41 Ethylene glycol monohexylether 17.0 Ethylene glycol monobutylether 2.1 Portion II Pigments, solvents, etc.

Lactic acid 8.9 12% Cobalt naphthenate drier Methyl ethyl ketoxime Portion III Deionized water 1468.05 10 Portion I is charged into a conventional sand mill and is milled to about a 7 egman The components of Portion II are added to the resultant paste in order and mixed. Portion III is then added. The paint has a solids content of about 10%, a pH of 4.9 15 and conductivity of 900 umhos. A Bonderite 1000 brand panel from Hooker Chemical Corp. of Detroit, Michigan plated for two minutes at 150 volts gave a 1.0 mil 4' C (0.0254 mm) film. After force drying for 45 minutes at 200 0 F (93 0 a gloss reading of 90/75 at 60 0 /20 0 meters on a Hunter D48D gloss meter was obi tained.

Example XI Parts by Weight Portion I Electrodeposition Vehicle Acrylated alkyd from Example VIII 112.2 Ethylene glycol monobutyl ether 1.9 Ethylene glycol monohexyl ether 10..0 Titanium oxide (rutile) 16.7

I

1 22 Portion II Pigments, solvents, etc.

Lactic acid (80%) 12% Cobalt naphthenate drier Methylethyl ketoxime Portion III Deionized water 5.3 854 4 944 4e4 10 9 4 #944 4P *15 99 4,b 4* 4 9 t Portion I is sandmilled at high speed to a value of about a 7-1/2 Portion II is 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 250°F (121 0 a hard, smooth coating is produced. Reflection is greater than on the 600 Hunter D48D gloss meter.

Example XII Parts by Weight t t '20 Portion I Alkyd from Example II 2-ethyl hexyl alcohol Titarium dioxide (rutile) Portion II Acrylated alkyd from Example VI 2-ethyl hexyl alcohol Propionic acid Manganese drier 5% 8.85 3.20 28.35 195.9 10.9 5.6 I r 23 Activ 8 brand drier promoter from Vanderbilt Chemical Co. 0.37 Ortho-t-butyl phenol 0.57 Deinoized water 1443.76 This paint is mixed and milled as above. The paint had a conductivity of 800 umhos and a pH of at 10% solids. Plating at 140 volts of direct current produced a one mil (0.0254 mm) film. The coated Bonderite 1000 brand panel from Hooker Chemical Corp.

"0 lof Detroit, Michigan was then cured at 200°F (93 0

C)

for 45 minutes. The finished coat had a gloss of 94 on the 600 Hunter D48D gloss meter.

t *In considering the invention, it should be Sremembered that the present disclosure including the preferred embodiments is illustrative only, and that t, the scope of the invention should be determined by the t rr appended claims.

t r

I..

Claims

1. An acrylated graft copolymer electrodeposition composition dried at a temperature of 93°C to 140°C wherein said composition is the reaction product of a base alkyd and ethylenically unsaturated monomers, the alkyd providing more than 37.5% of the weight of the reaction product, and the ethylenically unsaturated monomers including from 0-40% by weight of monovinyl aromatic hydrocarbon monomers based on the total weight of ethylenically unsaturated monomers and further containing one or more amine functional monomers providing amine functional groups in sufficient quantity, when in amine salt form, to provide to said reaction product water dispersibility and cationic functionality, said alkyd being the reaction product of a polyhydric alcohol, a polybasic acid, a fatty acid, and a grafting agent. o 2. The composition of claim 1 wherein the amount of amine functionality is at least 0.35 equivalent per 1000 grams of the graft copolymer. I o* 3. The composition of claim 1 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 acid.

4. The composition of claim 3 wherein said polybasic acid is isophthalic or phthalic acid. The composition of claim 3 wherein said grafting agent is selected from ethylenically unsaturated monoacids, ethylenically unsaturated isocyanates, ethylenically unsaturated diacide and their anhydrides and mixtures thereof.

6. The composition of claim 1 including a non-fatty monoacid in the base alkyd. 2 7. The composition of claim 1 in which the ethylenically unsaturated monomers are ,LIA, essentially free of hydroxyl functionality. il

7- 1 4 1 .4. *tee.' 44 4 0 I *It 'i

8. The composition of any of claims 1-7 including pigments, solvents and driers to form a paint composition for electrodeposition.

9. The process for forming an air-dried water-dispersed cationic electrodeposition comprising: reacting a polyhydric alcohol, polybasic acid, fatty acid and a grafting agent together to form a base alkyd; copolymerizing said base alkyd with ethylenically unsaturated monomers of which 0-40% by weight are monovinyl aromatic hydrocarbon monomers and which includes one or more amine functional monomers sufficient, when in amine salt form, to provide to the reaction product water dispersibility and cationic functionality, the quantity of said monomers being chosen so that the base alkyd provides more than 37.5% of the weight of the reaction product; and air-drying the product of at a temperature of 93°C to 1400C. The process of claim 9 including, in the reactants for step a non-fatty monobasic acid.

11. The process of claim 9 in which the ethylenically unsaturated monomers are essentially free of hydroxyl functionality.

12. The process of any one of claims 9-11 wherein the grafting agent is selected from conjugated fatty acids having at least 2% unsaturation, sorbic, crotonic, maleic, itaconic and tetrahydrophthalic acids and anhydrides and ethylenically unsaturated isocyanates. DATED this 23rd day of January, 1992. THE VALSPAR CORPORATION WATERMARK PATENT TRADEMARK ATTORNEYS THE ATRIUM 290 BURWOOD ROAD HAWTHORN VICTORIA 3122 AUSTRAUA IAS:JZ (DOC 007) AU3004589.WPC