CA1092267A - Cathodic electrocoating compositions and processes - Google Patents
Cathodic electrocoating compositions and processesInfo
- Publication number
- CA1092267A CA1092267A CA266,855A CA266855A CA1092267A CA 1092267 A CA1092267 A CA 1092267A CA 266855 A CA266855 A CA 266855A CA 1092267 A CA1092267 A CA 1092267A
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- Prior art keywords
- resin
- binder resin
- phenol
- composition
- reaction product
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/901—Electrodepositable compositions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31529—Next to metal
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31688—Next to aldehyde or ketone condensation product
Abstract
ABSTRACT OF THE DISCLOSURE
Heat cured coatings cathodically electrodeposited from an aqueous dispersion of (a) an ionized reaction product of an epoxy resin and a mono-amino alcohol or phenol, said reaction product also having a pendant hydro-carbon group, (b) an acid-functional aminoplast resin, and (c) a water soluble acid solubilizer, where the dispersion is free from water soluble acid which will be retained in the heat cured resinous coating are found to provide exceptional resistance to corrosion of ferrous metal substrates upon exposure to salt spray or detergent solutions.
Heat cured coatings cathodically electrodeposited from an aqueous dispersion of (a) an ionized reaction product of an epoxy resin and a mono-amino alcohol or phenol, said reaction product also having a pendant hydro-carbon group, (b) an acid-functional aminoplast resin, and (c) a water soluble acid solubilizer, where the dispersion is free from water soluble acid which will be retained in the heat cured resinous coating are found to provide exceptional resistance to corrosion of ferrous metal substrates upon exposure to salt spray or detergent solutions.
Description
lOgZZ~7 This invention relates to cathodic electrocoating co~positions and to processes for cathodically electrocoating metal substrates therewith.
In the electrocoating art an organic coating, i.e. a csating co~pris-ing a resinous organic binder and optionally containing other conventional coating components such as pigments, extenders, cross-linking agents, mildew-cides, etc., is formed upon an electrically conductive workpiece by electrode-position from a liquid (usually aqueous) dispersion. Following electrodeposi-tion of the coating material onto the workpiece-electrode, the workpiece is re-moved from contact with the liquid electrocoating dispersion, rinsed to remove adhering portions of that liquid dispersion and, usually, subjected to a curing operation to crosslink the electrodeposited binder resin so as to convert the coating on the workpiece to an insoluble, hard, adherent, protective film.
The liquid dispersion contains an ionized form of the binder resin dispersed in the liquid metium together with the other components of the coat-ing to be deposited and also contains a counter-ion soluble in the liquid dis-persion medium. The ionized resin may be either truly dissolved or merely finoly dispersed as an emulsion or a colloidal dispersion in the liquid dis-persion medium. It is preforred that the counter-ion be truly dissolved in the liquid dispersion medium, as this will lead to the greatest stability of the dispersion of the ionized resin species The electrically conductive work- -piece to be electrocoated is connected through a suitable external circuit in- -cluding a direct current emf source to a counter-electrode and both workpiece and counter-electrodo are brought into contact with a body of the liquid dis-persion. ~hen the emf source in the external circuit is energized so as to chargo the workpiece-electrode (relative tothe counter-electrode) to a polarity opposite to the charge carried by the ionized binder resin in the liquid dis-persion, then that ionized binder resin will electrophoretically migrate toward the workpiece-el trodo and, if the voltage is great enough, will electrodepo-sit theroon by electrical neutralization in the vicinity of the workpiece-dispersion interface. It is found that by suitable selection of materials, , ' " , ' ~ ' ' ''' ' ' lO9ZZf~7 the other optional and un-ionized components of the dispersion can be carried into the coating thus formed on the workpiece electrode, In anodic electrocoating the workpiece-electrode is given a positive electrical charge relative to the counter-electrode and the binder resin contains groups ionizable to form anions. These are most often ca~o-xylic acid groups and they are ionized by adding to the dispersion a base, such as an alkali or an amine, soluble in the dispersion medium. In cathodic electrocoating the resinous binder contains groups capable of ionizing to form cations and the actual degree of ionization of these groups in the dis-persion is enhanced by the incorporation in the dispersion of material ion-izable to form anions soluble in the liquid medium. Ordinarily the ionizable groups on the resinous binder are amine groups and the ionizing material is an acid which forms water soluble anions.
The emf source in the external circuit is used to charge the work-piece electrode as an anode or a cathode relative to the counter-electrode while both are in contact with a body of the liquid dispersion. The ionized resinous binder in the dispersion is electrophoretically attracted toward the workpiece-electrode and deposited thereon by electrical neutralization at the electrode-dispersion interface, while the counter-ions are simultaneously
In the electrocoating art an organic coating, i.e. a csating co~pris-ing a resinous organic binder and optionally containing other conventional coating components such as pigments, extenders, cross-linking agents, mildew-cides, etc., is formed upon an electrically conductive workpiece by electrode-position from a liquid (usually aqueous) dispersion. Following electrodeposi-tion of the coating material onto the workpiece-electrode, the workpiece is re-moved from contact with the liquid electrocoating dispersion, rinsed to remove adhering portions of that liquid dispersion and, usually, subjected to a curing operation to crosslink the electrodeposited binder resin so as to convert the coating on the workpiece to an insoluble, hard, adherent, protective film.
The liquid dispersion contains an ionized form of the binder resin dispersed in the liquid metium together with the other components of the coat-ing to be deposited and also contains a counter-ion soluble in the liquid dis-persion medium. The ionized resin may be either truly dissolved or merely finoly dispersed as an emulsion or a colloidal dispersion in the liquid dis-persion medium. It is preforred that the counter-ion be truly dissolved in the liquid dispersion medium, as this will lead to the greatest stability of the dispersion of the ionized resin species The electrically conductive work- -piece to be electrocoated is connected through a suitable external circuit in- -cluding a direct current emf source to a counter-electrode and both workpiece and counter-electrodo are brought into contact with a body of the liquid dis-persion. ~hen the emf source in the external circuit is energized so as to chargo the workpiece-electrode (relative tothe counter-electrode) to a polarity opposite to the charge carried by the ionized binder resin in the liquid dis-persion, then that ionized binder resin will electrophoretically migrate toward the workpiece-el trodo and, if the voltage is great enough, will electrodepo-sit theroon by electrical neutralization in the vicinity of the workpiece-dispersion interface. It is found that by suitable selection of materials, , ' " , ' ~ ' ' ''' ' ' lO9ZZf~7 the other optional and un-ionized components of the dispersion can be carried into the coating thus formed on the workpiece electrode, In anodic electrocoating the workpiece-electrode is given a positive electrical charge relative to the counter-electrode and the binder resin contains groups ionizable to form anions. These are most often ca~o-xylic acid groups and they are ionized by adding to the dispersion a base, such as an alkali or an amine, soluble in the dispersion medium. In cathodic electrocoating the resinous binder contains groups capable of ionizing to form cations and the actual degree of ionization of these groups in the dis-persion is enhanced by the incorporation in the dispersion of material ion-izable to form anions soluble in the liquid medium. Ordinarily the ionizable groups on the resinous binder are amine groups and the ionizing material is an acid which forms water soluble anions.
The emf source in the external circuit is used to charge the work-piece electrode as an anode or a cathode relative to the counter-electrode while both are in contact with a body of the liquid dispersion. The ionized resinous binder in the dispersion is electrophoretically attracted toward the workpiece-electrode and deposited thereon by electrical neutralization at the electrode-dispersion interface, while the counter-ions are simultaneously
2~ electrophoretically repelled therefrom, although a small proportion of the counter-ion or at least of counter-ion generating species is known to sometimes deposit on the workpiece electrode nonetheless. Other conventional coating components may be present in the liquid dispersion and, if suitably selected, will be co-deposited with the electrically neutralized form of the ionized resin upon the workpiece electrode to form the coating thereon, even though ; in the dispersion these other optional components are not known to bear charges. The mechanisms by which these other components are deposited as part of the coating are not fully understood, but in some cases such co-deposi-tion may arise because the component is soluble the ionized binder resin which is itself present as a finely dispersed secont phase rather than as a -iO~Z267 true solution in the aqueous medium, In other cases the ioniz¢d binder resin may attach by absorption to the other component, thereby conferring electro-phoretic responsiveness upon an otherwise uncharged species.
A wide variety of resin types can be used as the binder component in electrocoating compositions for either anodic or cathodic deposition, so long as they contain a sufficient number of ionizable groups of the appropriate polarity, namely anionic for anodic deposition and cationic for cathodic depo-sition, to impart a useful degree of electrophoretic mobility.
The cure of organic coatings containing resinous binders having ac-tive hydrogens by thermally induced cross-linking reaction with aminoplast resins is well known. The active hydrogens in the binder resin to be cross-linked are typically provided by incorporating hydroxyl, carboxyl, or primary ~mide groups in that resin. In other respects the composition of the binder resin is almost unrestricted, insofar as curability is concerned, so long as a reasonablo intimacy of admixture with the aminoplast resin can be achieved.
Thus curing with amoniplast resins may be used in a wide variety of coating compositions wherein the binder resin may be selected from a wide range of compositions on the basis of availability, cost, application properties, and porformance properties of the final cured coating. Typical resins for use in coating compositions to be cured with aminoplast resins include epoxies, poly-esters, alkyds (espocially maleinized alkyds), acid- or amide-functional acry-lics, and many others. - -Aminoplast resins useful for curing organic coatings by cross-linking the binder rosins of such coatings to form insoluble, high molecular weight matorials having a wido range of proporties, depending on the type of resinous binder, the type of ~minoplast resin, their relativo amounts, the other com-ponents of the coating composition, the conditions under which cure is achievod, otc., are well known in the coatings art. Typical aminoplast resins for such purposes are deri~ed from polyfunctional amines or amides by reac-tion with formaldehydo. A~ong the more important aminoplast resins used , lO9ZZ67 in the organic coatings art are reaction products of for~aldehyde with ureaor with aminotriazines, such as melamine or benzoguanamine, and low molecular weight polymers thereof, and ethers of any of these with lower alkanols, especially methanol where it is desired to enhance water solubility and butanol where it is desired to suppress water solubility.
While the conditions of temperature and time required for cure of any particular coating composition by reaction of an aminoplast resin component with a resin component having active hydrogens will vary somewhat depending upon the particular chemical structures and concentrations involved, it is widely recognized that incorporation of acids in such compositions will tend to reduce the temperature and/or the time required to achieve cure as compared to the same composition in the absence of such acids. In general, the stronger the acid, and the higher its concentration in the coating, the greater will be the reduction in the temperature and/or time required for cure.
Aminoplast resins have been used to cure coatings electrodeposited upon an anode from an aqueous dispersion of the aminoplast resin and an anionic form of a binder resin containing active hydrogens. Dispersion of the anionic resin in the aqueous medium is ordinarily stabilized by the presence of a water soluble cation derived from an added base, such as an amine or alkali. The anions on the resin in the aqueous dispersion are usually deprotonated carbo-xyl groups and it is thought that the carboxylic acid groups are regenerated therefrom by electrical neutralization at the anode during electrodeposition of the coating. These carboxylic acid groups are then perforce available to catalyze the curing reaction between the binder resin and the aminoplast resin co-deposited therewith upon the anode when that coating is subsequently baked.
The cure reaction may, of course, involve reaction of the acid groups them-selves or of other active hydrogen-bearing groups on the binder resin or both with the aminoplast resin.
An i~provement in the anodic electrocoating art, wherein the amino-plast resin also has ionizable carboxylic acid groups, has been described Z2~7 by Coates et al in United States Patent 3,519,627 granted July 7, 1970.
Coates et al therein teach the method of preparation and the usefulness in anodic electrocoating compositions of a certain class of carboxyl-containing ethers of aminotriazine/aldehyde condensates derived from hydroxy alkyl carb-oxylic acids, in particular carboxyl-containing ethers of fully methylolated melamine and benzoguanamine and low polymers thereof. Their utility in ~anodic) electrocoating compositions is ascribed to the fact th~t the carboxyl groups thereon will be ionizable in the aqueous electrocoating dispersion under the same conditions as the carboxyl groups on the binder resin and therefore will co-deposit more effectively with that resin upon an anode in contact with the dispersion. Since there would be numerous carboxylic acid groups on the binder resin electrodeposited on the anode, any enhancem0nt of the acid cata-lysis of the curing reaction between the aminoplast resin ant the binder resin by virtue of the small proportion of additional carboxylic acid groups present on the aminoplast resin would be expected to be hardly noticeable and was not mentioned by Coateset al.
The use of aminoplast curing resin compositions in cathodic electro-coating wherein a coating is electrodeposited upon a cathode in contact with an aqueous dispersion of a cationic form of a binder resin stabilized by the presence of water soluble anion and also containing an aminoplast resin, is also known. Thus, Koral in United States Patent 3,471,388 g~anted October 7, lg69 discloses how to make and to use in both anodic and cathodic electrocoat-ing processes melamine resins comprising a certain class of etherified methy-lolated melamine, The patent contains no suggestion of the existence or utility of acid-functional aminoplast resins, and in particular contains no suggestion of their utility in cathodic electrocoating.
A water soluble alkanolamine-terminated epoxy resin was disclosed by Wong et al in United States Patent 3,336,253. It differs from the binder resins of the ~resent in~ention in being expressly restricted to a single ~r~,~ ~ ,.~/
alkanolamine ~o~* d group and in not being substantially free of epoxide lO9ZZ67 functionality and there is no suggestion of its use in electrocoating.
The compositions of the present invention are cathodic electro-coating compositions comprising in aqueous dispersion:
(a) a cathodically electrodepositable, at least partially cationized binder resin comprising a major proportion of a reaction product of an epoxide-functional resin and a monoamino alcohol or phenol haYing at least one r-eactive hydrogen on the amino nitrogen, said reaction product being sub-stantially devoid of reactive epoxide groups and having an average of at least about two reactive hydroxyl groups and at least about 0,2 directly or indirectly pendant 5 to 20 carbon atom hydrocarbon radical per molecule;
tb) from about 0.05 to about 1 weight parts, per weight part of said binder resin, of an acid-functional aminoplast resin (i) cathodically co-electrodepositable with said binder resin from said aqueous dispersion to form an intermediate product comprising an intimate mixture of the cathod-ically electrodeposited form of said binder resin and said aminoplast resin, (ii) co-reactive in said intermediate product with the cathodically electro-deposited form of said binder resin, upon heating, to transform said inter-metiate product into a cured resinous product, (iii~ having at least about 0.0001 equivalent of titratable acid functionality of PKa not greater than about 5 per gram of said aminoplast resin, and (iv) not soluble independently in the aqueous medium of said dispersion; and tc) from about 20 to about 150 milliequivalents,per 100 grams of (a) and (b), of an anion of a water-soluble acid to enhance and stabilize the cstionization of said binder resin; said aqueous dispersion having a pH of from about 2 to about 7 and being substantially free of any water-soluble acid which will be retained in water-soluble form in said cured resinous product and of anions thereof. Compositions containing partially pre-reacted forms of components (a) and (b) wherein portion of the aminoplast resin is cheDically bonded to the binder resin without exhausting their mutual react-ivity are included among the compositions of the present invention and, where 1~9Z2~;7 a major proportion of the aminoplast resin is thus chemically bonded to thebinder resin, comprise a preferred embodiment.
The processes of the present invention are processes for cathod-ically electrocoating metallic substrates to form a cured resinous coating thereon, comprising - (A) establishing simultaneous contact of said metallic substrate and a counter-electrode with a body of the liquid aqueous dispersion of the above-described cathodic electrocoating composition;
~B) maintaining an electrical potential difference between said metallic substrate and said counter-electrode, while both are in contact with said body of liquid aqueous dispersion, of such polarity that said metallic sub-strate is charged as a cathode relative to said counter-electrode as an anode and of such magnitude that an uncured coating comprising said intermetiate protuct is cathodically electrodeposited upon said metallic substrate;
(C) removing said metallic substrate bearing said uncured coating there-on from contact with said body of liquid aqueous dispersion; and tD) thereafter heating said uncured coating to transform it into a cured resinous coating comprising said cured resinous product, The present invention derives from the discovery that certain highly desirable properties in cathodically electrodeposited coatings can be attained by utilizing a particular class of binder resins capable of being cured by reaction with an aminoplast resin, dispersing the binder resin in the liquid electrocoating bath in cationic form, and providing for catalyzed cure of the coating cathodically electrodeposited therefrom by also dispersing in the - -liquid electrocoating bath an aminoplast resin having acid groups effective for catalyzing the cure reaction chemically bonded thereto, while excluding from the electrocoating bath composition any acids which will deposit as part of the coating on a workpiece-cathode and be retained therein to any signi- -ficant extent in water-soluble form as the coating is beated to effect cure thereof. Since it is not known how to totally prevent the acid used to ionize 10~ 7 the resinous binder from depositing to some extent with the coating on the cathode~and since it appears to be uneconomical to completely w~sh out co-deposited water-soluble acid by rinsing or extraction of the coated workpiece the desired exclusion of such acids from ~he final product coating film can be achieved by restricting the water-soluble acids employed in *he cathodic electrocoating composition to those which will volatilize or decompose upon heating the deposited coating to effect cure or which will react during cure with other components of the coating so as to become water-insoluble even though retained in the film. The presence of the acid groups attached to the aminoplast resin permits the advantages of acid catalysis of the aminoplast curing reaction to be realized, while the exclusion of water-soluble acids which will be retained in water soluble form in the final cured coating sub-stantially reduce~ the water sensitivity of the final cured coating film and the consequent susceptibility of the substrate workpiece to corrosion upon exposure to water- or mois*ure-containing corrosive environments. Carboxyl-containing etherified aminotriazine-formaldehyde condensates, including low polymers thereof, are found to be particularly useful aminoplast resins in this invention. It is especially preferred to partially react the acid-con-taining aminoplast resin with the binder resin before electrodeposition of the coating, thereby improving both the stability of the liquid electrocoating dispersion and the intimacy and uniformity of distribution of the acid-functional aminoplast resin in the deposited coating, so long as this pre-reaction is stopped short of gelation and does not exhaust the mutual react-ivity of the resins. Although the binder resin and the aminoplast resin of the present invention are usually referred to herein as separate and distinct co~ponents of the liquid electrocoating dispersion and of the uncured coating electrodeposited therefrom, it is intended throughout the description of the present invention, except where clearly indicated to the contrary, to include such partially pre-reacted compositions.
The epoxy bindër resins of the present invention are derived from i()~2267 conventional di- or poly-epoxide functional epoxy resins of the bisphenol/
epichlorohydrin type. At least one of the epoxide groups is reacted with a monoamino alcohol or phenol having at least one reactive hydrogen on the amino nitrogen. The epoxy resin is also modified by attaching to at least about 20~ of the molecules thereof a directly or indirectly pendant hydro-carbon radical having from about S to about 20 carbon atoms. These pendant hydrocarbon radicals may be aliphatic, cycloaliphatic, or aromatic, but pref-erably comprise one or more terminal alkyl groups having at least about 5 carbon atoms. These hydrocarbon radicals may be attached to the epoxide resin -by any convenient means, such as esterification of a suitable acid or anhydride by reaction with either-sn epoxide group or a hydroxyl group of the epoxy resin but are preferably attached by ether linkages formed between a suitable alcohol or phenol and an epoxide or hydroxyl group of the epoxy resin. To produce a cured coating with superior resistance to detergent solutions, the ~-required hydrocarbon group must not be susceptible to hydrolysis and should either be attached by an ether linkage or, if by an ester linkage, the acid ~ -reactant should have its carboxyl group on a tertiary carbon atom, for example versatic acid. The resulting binder resin should contain at least about 2 reactive hydroxyl groups per molecule, which will ordinarily and preferably be rosidual hydroxyl groups produced in the condensation of the epichlorohydrin with the bisphenol to form the epoxy resin and not subsequently used up in attaching the required hydrocarbon radicals. For best results it is import-ant that substantially all of the epoxide groups of the epoxy resin be con-sumed by reaction with an alcohol, an amine, a carboxylic acid orothersuit-able reactant so that the binder resin is substantially free of reactive epoxide groups in order that the amine-functional epoxy resin will have the desiret superior stability in storage and use against premature further poly-merization, cross-linking, or gelation. The preferred binder resins are those in which a minor proportion of the epoxide groups are not reacted with the monoamino alcohol or phenol, but are instead consumed by reaction with a _ g _ :
.
lO9ZZ6~
suitable reactant such as an alcohol or alkyl phenol to introduce the required pendant hydrocarbon radical.
A preferred epoxy resin comprises a ma;or proportion by weight of the reaction product of a diepoxide reaction product of bisphenol A and epichlorohydrin having an average molecular weight from 500 to 2500 and from 0.2 to 1 mole of monohydroxyl alcohol or phenol having from 5 to 20, preferably 8 to 10, carbon atoms per mole of said diepoxide. The monoamino alcohol is pre-ferably a dialkanolamine in which each alkanol group contains from 2 to 5 carbon atoms, particularly diethanolamine.
A particularly preferred binder resin is derived from a conventional bisphenol A/epichlorohydrin diepoxide epoxy resin having a molecular weight of about 1050 and available from the Dow Chemical Company under the trademark DER-661. About 75% of the epoxide groups are reacted with diethanolamine and substan-tially all of the remaining epoxide groups are reacted with nonyl-phenol to introduce the required pendant hydrocarbon groups.
The aminoplast resin may comprise any of a broad range of etherified amine-aldehyde or amide-aldehyde condensates containing a plurality of ether groups reactive with groups con-taining active hydrogen such as hydroxyl, carboxyl and amide --groups on the binder resin upon heating. While aminoplast resins derived from urea-formaldehyde condensates will work in the present invention, those derived from aminotriazine-formaldehyde ; condensates such as tetramethylol benzoguanamine and hexamethylol melamine are preferred. The amine-aldehyde condensate should be substantially fully etherified with a mixture of a lower alkanol -~
and a hydroxy acid to form the acid functional aminoplast resin to be used in the invention. This may be accomplished by first substantially fully etherifying with a lower alkanol and then partially transetherifying that reaction product with the hydroxy --. .''.
- ' .' ' ' '.",, ' ., ' . ' : ,", ,, '' ' ' ' : ~: ' , .' .
lV9;~Zti7 acid to produce' an etherified aminoplast resin having an acid number of at least 5.6.
The acid used must have a pKa not greater than about 5 in order to be effective as a catalyst for the cure reaction between the binder resin having active hydrogens and the amino-plast resin. It is found that carboxylic acid groups are gener-ally effective, but aromatic carboxylic groups are preferred.
Other stronger acids such as sulfonic acids may also be used and will produce a greater catalytic effect on the curing reaction.
Since the aminoplast resins are dispersed in an acid medium to form the electrocoating compositions Or the present invention and since it is known that such conditions are con-ducive to reaction and ultimately gelation lO9Z267 of the aminoplast resin, it is desirable to reduce the water solubility of the aminoplast resin so as to decrease its susceptibility to premature reaction and gelation. This can be achieved by etherifying (or transetherifying) the methylol groups with alcohols having a relatively hydrophobic group attached to the alcoholic hydroxyl group. Ordinarily it is found convenient to adjust the hydrophobicity by producing a suitable mixture of methyl and butyl or isobutyl ether groups. In such cases the greatest hydrophobicity, and conse-quently the greatest stability against premature reaction and gelation in the aqueous dispersion, will be achieved with all butyl or isobutyl ether groups.
But since the curing reaction is slower with butyl than with methyl ether groups on the aminoplast resin, it is not always desirable or necessary to shift the butyl/methyl ratio to give maximum hytrophobicity so long as suffic-ient bath stability for the particular composition and process is achieved.
Similar considerations apply where ether groups derived from other alcohols are employed. Of course, the effect on aqueous solubility of the acid-bearing group must also be accommodated in adjusting the set-off between (i) increasing by hydrophobicity and bath stability by incorporating a greater proportion of more hydrophobic ether groups and (ii) increasing the rate of the curing reaction in the deposited film by increasing the proportion of ether groups which decompose to liberate more volatile alcohols. It is found, however, that the acid groups, and particularly aromatic carboxylic acid groups, in- -- -corporated in the aminoplast resin itself do not produce premature reaction and gelation of the aminoplast resin and consequently the reciprocal adjust- ~ -ment of bath stability and cure speed is not adversely affected by the in-corporation of such acid groups except insosr as the aqueous solubility is affected.
Seversl examples of preferred embodiments will be given. Except where clearly indicatet otherwise, parts and percentages are by weight.
Where epoxy or oxirane values or numbers are referred to, they may be deter-minet by the method of Jay, Analytical Chemistry, vol. 36,667-8 (1964).
.
~()9Z267 Example 1 A suitable and preferred binder resin for practice of the present invention can be prepared by charging to a suitable reactor vessel 96.4 parts of diethanol amine and heating to about 130C. Over a period of about two hours, 857.2 parts of a 75% solution in xylene of a low molecular weight epoxide-functional epoxy resin derived from bisphenol-A and epichlorohydrin is added to the reaction vessel while maintaining the temperature at approximat-ely 130C. and retu ming refluxing xylene to the reacting mixture A suitable epoxy resin is the Dow Chemical Company product designated D~EoRo 671 which has a molecular weight of about 1050 and an epoxide equivalent weight of about 525. The above reaction conditions are maintained for about an addition-al hour, at which time 60.6 parts of nonylphenol are added over a period of about 10 minutes and the same reaction conditions are maintained until the epoxide (oxirsne) number is reduced to about 0, a period of about two to three hours. While the temperature is gradually raised from about 130C. to about 160QC. over a period of about one to two hours, about 190 parts of xylene are removed from the reaction mixture by distillation under vacuum. The temperat-ure of the reaction mixture is then lowered to about 125C. and there is ` -added 395.4 parts of an approximately 85% solution in isobutanol of an acid-functional aminoplast resin such as the American Cyanamid product designated CLA-66 which is a substantially fully etherified hexamethylol melamine ether-ified with lower alkanol and hydroxy aromatic carboxylic acid and has an acid number of about 19.6. This reaction mixture is maintained at about 115C.
with return of reflu,xin~ solvent for about one hour, at which time 233.2 parts ~ e~/os~'e of butyl or~ ed-e are added snd the mixture is cooled to room ~emperature.
This resin solution is about 78.5~ non-volatiles, has an acid number (based `
on non-volatiles) of about 4.28 and, after dilution with an equal quantity of C~/OSO~L'C
butyl ~r~o~r~, a viscosity of G on the Gardner-Holt scale, the viscosity solution being slightly cloudy.
. ~ .
~ ~ ~o~S' l~Z267 Exa~le II
A binder resin substantially identical to that of Example 1 can be produced without requiring the removal of solvent by starting with a liquid diepoxide of lower molecular weight, such as the diglycidyl ether of bisphen A, and first producing a higher molecular weight diepoxide therefrom by react-ing 2 moles of the liquid diepoxide with 1 mole of bisphenol A in the presence of a conventional amine or triphenyl phosphine catalyst, all in the absence of solvent.
Specifically, charge to a suitable reaction vessel 2713 parts of Dow Chemical Company liquid diepoxide D~E~Ro 333, having molecular weight-of about 350 and containing catalyst, and 787 parts of bisphenol A. Heat to about 140C. and permit the reaction exotherm to raise the temperature to about 180C. Hold at 180C. for about 2 hours until the viscosity of a ~/~0 s~ve ` sample diluted 1:1 with bu~yl oellosolvc is in the range H-J on the Gardner-Holt scale and the oxirane value is in the range about 3.1 to 3.3, Cool and Ce//r~
dilute with 937 parts butyl ce~H-o~ve. Place 1331 parts of the diepoxide resin solution so produced in a suitable reaction ve~sel, heat to 130 to 140C.,add 157.5 parts of diethanolamine and 99 parts of nonylphenol over about 2 hours, and hold at about 135C. for about 2 hours until the oxirane value is reduced to about 0. Then reduce the temperature to about 115C. and add 644 parts of an 85% solution in isobutanol of the American Cyanamid acid functional ether-ified melamine resin designated CLA-66. Hold at that temperature for about 1 ~e~r~
hour until the viscosity of a sample diluted 1:1 with butyl ~ ~}K ~i~e is about G to H on the Gardner-Holt scale. The acid number of this resin was about 5 and the reaction product about 80.7% non-volatiles. -Example III
In place of the acid functional melamine ether of Examples I and II
Day be substituted an acid functional benzoguanamine ether, whi~h can be made as follows. Place in a suitable reaction vessel 300 parts toluene, 1220 parts paraformaldehyde, 4560 parts n-butanol and 30 parts hexamethylenetetramine (as ,' :
lO9ZZ67 catalyst). Heat to reflux (about 110C.) for 1 to 2 hours until a clear solution is formed. The pH will be about 7 to 7.5. Add 1870 parts benzo-guanamine and hold the temperature at about 105C. until the solution is again clear. The pH will be about 8 to 8.6. Cool to 80C. and add about 8 parts maleic anydride to give a pH of 4.3 to 4.7. Heat to reflux and distill off a water-containing azeotrope over a period of about 6 to lZ hours, removing about 650 parts of water, until the mineral spirits tolerance is at least about 60.
The mineral spirits tolerance is the milliliters of mineral spirits that, mixed with 10 g. of sample, makes the mixture just cloudy enough that an ordin-ary laboratory thermometer becomes not clearly legible when viewed throughthe mixture contained in a 250 ml. beaker. Then distill under vacuum to remove about 2800 to 2900 parts of solvent, the temperature remaining below ` about 105 &. The intermediate product so formed is about 96.4% nonvolatiles, --has a Gardner-Holt viscosity of about Z6 to Z7, and an acid number of about 0.8.
Heat 500 parts of this intermediate product together with 39 parts Ce~/o s~ /~ e salicyclic acid and 76 parts butyl oeL} so}re at about 130C. for about 1 to
A wide variety of resin types can be used as the binder component in electrocoating compositions for either anodic or cathodic deposition, so long as they contain a sufficient number of ionizable groups of the appropriate polarity, namely anionic for anodic deposition and cationic for cathodic depo-sition, to impart a useful degree of electrophoretic mobility.
The cure of organic coatings containing resinous binders having ac-tive hydrogens by thermally induced cross-linking reaction with aminoplast resins is well known. The active hydrogens in the binder resin to be cross-linked are typically provided by incorporating hydroxyl, carboxyl, or primary ~mide groups in that resin. In other respects the composition of the binder resin is almost unrestricted, insofar as curability is concerned, so long as a reasonablo intimacy of admixture with the aminoplast resin can be achieved.
Thus curing with amoniplast resins may be used in a wide variety of coating compositions wherein the binder resin may be selected from a wide range of compositions on the basis of availability, cost, application properties, and porformance properties of the final cured coating. Typical resins for use in coating compositions to be cured with aminoplast resins include epoxies, poly-esters, alkyds (espocially maleinized alkyds), acid- or amide-functional acry-lics, and many others. - -Aminoplast resins useful for curing organic coatings by cross-linking the binder rosins of such coatings to form insoluble, high molecular weight matorials having a wido range of proporties, depending on the type of resinous binder, the type of ~minoplast resin, their relativo amounts, the other com-ponents of the coating composition, the conditions under which cure is achievod, otc., are well known in the coatings art. Typical aminoplast resins for such purposes are deri~ed from polyfunctional amines or amides by reac-tion with formaldehydo. A~ong the more important aminoplast resins used , lO9ZZ67 in the organic coatings art are reaction products of for~aldehyde with ureaor with aminotriazines, such as melamine or benzoguanamine, and low molecular weight polymers thereof, and ethers of any of these with lower alkanols, especially methanol where it is desired to enhance water solubility and butanol where it is desired to suppress water solubility.
While the conditions of temperature and time required for cure of any particular coating composition by reaction of an aminoplast resin component with a resin component having active hydrogens will vary somewhat depending upon the particular chemical structures and concentrations involved, it is widely recognized that incorporation of acids in such compositions will tend to reduce the temperature and/or the time required to achieve cure as compared to the same composition in the absence of such acids. In general, the stronger the acid, and the higher its concentration in the coating, the greater will be the reduction in the temperature and/or time required for cure.
Aminoplast resins have been used to cure coatings electrodeposited upon an anode from an aqueous dispersion of the aminoplast resin and an anionic form of a binder resin containing active hydrogens. Dispersion of the anionic resin in the aqueous medium is ordinarily stabilized by the presence of a water soluble cation derived from an added base, such as an amine or alkali. The anions on the resin in the aqueous dispersion are usually deprotonated carbo-xyl groups and it is thought that the carboxylic acid groups are regenerated therefrom by electrical neutralization at the anode during electrodeposition of the coating. These carboxylic acid groups are then perforce available to catalyze the curing reaction between the binder resin and the aminoplast resin co-deposited therewith upon the anode when that coating is subsequently baked.
The cure reaction may, of course, involve reaction of the acid groups them-selves or of other active hydrogen-bearing groups on the binder resin or both with the aminoplast resin.
An i~provement in the anodic electrocoating art, wherein the amino-plast resin also has ionizable carboxylic acid groups, has been described Z2~7 by Coates et al in United States Patent 3,519,627 granted July 7, 1970.
Coates et al therein teach the method of preparation and the usefulness in anodic electrocoating compositions of a certain class of carboxyl-containing ethers of aminotriazine/aldehyde condensates derived from hydroxy alkyl carb-oxylic acids, in particular carboxyl-containing ethers of fully methylolated melamine and benzoguanamine and low polymers thereof. Their utility in ~anodic) electrocoating compositions is ascribed to the fact th~t the carboxyl groups thereon will be ionizable in the aqueous electrocoating dispersion under the same conditions as the carboxyl groups on the binder resin and therefore will co-deposit more effectively with that resin upon an anode in contact with the dispersion. Since there would be numerous carboxylic acid groups on the binder resin electrodeposited on the anode, any enhancem0nt of the acid cata-lysis of the curing reaction between the aminoplast resin ant the binder resin by virtue of the small proportion of additional carboxylic acid groups present on the aminoplast resin would be expected to be hardly noticeable and was not mentioned by Coateset al.
The use of aminoplast curing resin compositions in cathodic electro-coating wherein a coating is electrodeposited upon a cathode in contact with an aqueous dispersion of a cationic form of a binder resin stabilized by the presence of water soluble anion and also containing an aminoplast resin, is also known. Thus, Koral in United States Patent 3,471,388 g~anted October 7, lg69 discloses how to make and to use in both anodic and cathodic electrocoat-ing processes melamine resins comprising a certain class of etherified methy-lolated melamine, The patent contains no suggestion of the existence or utility of acid-functional aminoplast resins, and in particular contains no suggestion of their utility in cathodic electrocoating.
A water soluble alkanolamine-terminated epoxy resin was disclosed by Wong et al in United States Patent 3,336,253. It differs from the binder resins of the ~resent in~ention in being expressly restricted to a single ~r~,~ ~ ,.~/
alkanolamine ~o~* d group and in not being substantially free of epoxide lO9ZZ67 functionality and there is no suggestion of its use in electrocoating.
The compositions of the present invention are cathodic electro-coating compositions comprising in aqueous dispersion:
(a) a cathodically electrodepositable, at least partially cationized binder resin comprising a major proportion of a reaction product of an epoxide-functional resin and a monoamino alcohol or phenol haYing at least one r-eactive hydrogen on the amino nitrogen, said reaction product being sub-stantially devoid of reactive epoxide groups and having an average of at least about two reactive hydroxyl groups and at least about 0,2 directly or indirectly pendant 5 to 20 carbon atom hydrocarbon radical per molecule;
tb) from about 0.05 to about 1 weight parts, per weight part of said binder resin, of an acid-functional aminoplast resin (i) cathodically co-electrodepositable with said binder resin from said aqueous dispersion to form an intermediate product comprising an intimate mixture of the cathod-ically electrodeposited form of said binder resin and said aminoplast resin, (ii) co-reactive in said intermediate product with the cathodically electro-deposited form of said binder resin, upon heating, to transform said inter-metiate product into a cured resinous product, (iii~ having at least about 0.0001 equivalent of titratable acid functionality of PKa not greater than about 5 per gram of said aminoplast resin, and (iv) not soluble independently in the aqueous medium of said dispersion; and tc) from about 20 to about 150 milliequivalents,per 100 grams of (a) and (b), of an anion of a water-soluble acid to enhance and stabilize the cstionization of said binder resin; said aqueous dispersion having a pH of from about 2 to about 7 and being substantially free of any water-soluble acid which will be retained in water-soluble form in said cured resinous product and of anions thereof. Compositions containing partially pre-reacted forms of components (a) and (b) wherein portion of the aminoplast resin is cheDically bonded to the binder resin without exhausting their mutual react-ivity are included among the compositions of the present invention and, where 1~9Z2~;7 a major proportion of the aminoplast resin is thus chemically bonded to thebinder resin, comprise a preferred embodiment.
The processes of the present invention are processes for cathod-ically electrocoating metallic substrates to form a cured resinous coating thereon, comprising - (A) establishing simultaneous contact of said metallic substrate and a counter-electrode with a body of the liquid aqueous dispersion of the above-described cathodic electrocoating composition;
~B) maintaining an electrical potential difference between said metallic substrate and said counter-electrode, while both are in contact with said body of liquid aqueous dispersion, of such polarity that said metallic sub-strate is charged as a cathode relative to said counter-electrode as an anode and of such magnitude that an uncured coating comprising said intermetiate protuct is cathodically electrodeposited upon said metallic substrate;
(C) removing said metallic substrate bearing said uncured coating there-on from contact with said body of liquid aqueous dispersion; and tD) thereafter heating said uncured coating to transform it into a cured resinous coating comprising said cured resinous product, The present invention derives from the discovery that certain highly desirable properties in cathodically electrodeposited coatings can be attained by utilizing a particular class of binder resins capable of being cured by reaction with an aminoplast resin, dispersing the binder resin in the liquid electrocoating bath in cationic form, and providing for catalyzed cure of the coating cathodically electrodeposited therefrom by also dispersing in the - -liquid electrocoating bath an aminoplast resin having acid groups effective for catalyzing the cure reaction chemically bonded thereto, while excluding from the electrocoating bath composition any acids which will deposit as part of the coating on a workpiece-cathode and be retained therein to any signi- -ficant extent in water-soluble form as the coating is beated to effect cure thereof. Since it is not known how to totally prevent the acid used to ionize 10~ 7 the resinous binder from depositing to some extent with the coating on the cathode~and since it appears to be uneconomical to completely w~sh out co-deposited water-soluble acid by rinsing or extraction of the coated workpiece the desired exclusion of such acids from ~he final product coating film can be achieved by restricting the water-soluble acids employed in *he cathodic electrocoating composition to those which will volatilize or decompose upon heating the deposited coating to effect cure or which will react during cure with other components of the coating so as to become water-insoluble even though retained in the film. The presence of the acid groups attached to the aminoplast resin permits the advantages of acid catalysis of the aminoplast curing reaction to be realized, while the exclusion of water-soluble acids which will be retained in water soluble form in the final cured coating sub-stantially reduce~ the water sensitivity of the final cured coating film and the consequent susceptibility of the substrate workpiece to corrosion upon exposure to water- or mois*ure-containing corrosive environments. Carboxyl-containing etherified aminotriazine-formaldehyde condensates, including low polymers thereof, are found to be particularly useful aminoplast resins in this invention. It is especially preferred to partially react the acid-con-taining aminoplast resin with the binder resin before electrodeposition of the coating, thereby improving both the stability of the liquid electrocoating dispersion and the intimacy and uniformity of distribution of the acid-functional aminoplast resin in the deposited coating, so long as this pre-reaction is stopped short of gelation and does not exhaust the mutual react-ivity of the resins. Although the binder resin and the aminoplast resin of the present invention are usually referred to herein as separate and distinct co~ponents of the liquid electrocoating dispersion and of the uncured coating electrodeposited therefrom, it is intended throughout the description of the present invention, except where clearly indicated to the contrary, to include such partially pre-reacted compositions.
The epoxy bindër resins of the present invention are derived from i()~2267 conventional di- or poly-epoxide functional epoxy resins of the bisphenol/
epichlorohydrin type. At least one of the epoxide groups is reacted with a monoamino alcohol or phenol having at least one reactive hydrogen on the amino nitrogen. The epoxy resin is also modified by attaching to at least about 20~ of the molecules thereof a directly or indirectly pendant hydro-carbon radical having from about S to about 20 carbon atoms. These pendant hydrocarbon radicals may be aliphatic, cycloaliphatic, or aromatic, but pref-erably comprise one or more terminal alkyl groups having at least about 5 carbon atoms. These hydrocarbon radicals may be attached to the epoxide resin -by any convenient means, such as esterification of a suitable acid or anhydride by reaction with either-sn epoxide group or a hydroxyl group of the epoxy resin but are preferably attached by ether linkages formed between a suitable alcohol or phenol and an epoxide or hydroxyl group of the epoxy resin. To produce a cured coating with superior resistance to detergent solutions, the ~-required hydrocarbon group must not be susceptible to hydrolysis and should either be attached by an ether linkage or, if by an ester linkage, the acid ~ -reactant should have its carboxyl group on a tertiary carbon atom, for example versatic acid. The resulting binder resin should contain at least about 2 reactive hydroxyl groups per molecule, which will ordinarily and preferably be rosidual hydroxyl groups produced in the condensation of the epichlorohydrin with the bisphenol to form the epoxy resin and not subsequently used up in attaching the required hydrocarbon radicals. For best results it is import-ant that substantially all of the epoxide groups of the epoxy resin be con-sumed by reaction with an alcohol, an amine, a carboxylic acid orothersuit-able reactant so that the binder resin is substantially free of reactive epoxide groups in order that the amine-functional epoxy resin will have the desiret superior stability in storage and use against premature further poly-merization, cross-linking, or gelation. The preferred binder resins are those in which a minor proportion of the epoxide groups are not reacted with the monoamino alcohol or phenol, but are instead consumed by reaction with a _ g _ :
.
lO9ZZ6~
suitable reactant such as an alcohol or alkyl phenol to introduce the required pendant hydrocarbon radical.
A preferred epoxy resin comprises a ma;or proportion by weight of the reaction product of a diepoxide reaction product of bisphenol A and epichlorohydrin having an average molecular weight from 500 to 2500 and from 0.2 to 1 mole of monohydroxyl alcohol or phenol having from 5 to 20, preferably 8 to 10, carbon atoms per mole of said diepoxide. The monoamino alcohol is pre-ferably a dialkanolamine in which each alkanol group contains from 2 to 5 carbon atoms, particularly diethanolamine.
A particularly preferred binder resin is derived from a conventional bisphenol A/epichlorohydrin diepoxide epoxy resin having a molecular weight of about 1050 and available from the Dow Chemical Company under the trademark DER-661. About 75% of the epoxide groups are reacted with diethanolamine and substan-tially all of the remaining epoxide groups are reacted with nonyl-phenol to introduce the required pendant hydrocarbon groups.
The aminoplast resin may comprise any of a broad range of etherified amine-aldehyde or amide-aldehyde condensates containing a plurality of ether groups reactive with groups con-taining active hydrogen such as hydroxyl, carboxyl and amide --groups on the binder resin upon heating. While aminoplast resins derived from urea-formaldehyde condensates will work in the present invention, those derived from aminotriazine-formaldehyde ; condensates such as tetramethylol benzoguanamine and hexamethylol melamine are preferred. The amine-aldehyde condensate should be substantially fully etherified with a mixture of a lower alkanol -~
and a hydroxy acid to form the acid functional aminoplast resin to be used in the invention. This may be accomplished by first substantially fully etherifying with a lower alkanol and then partially transetherifying that reaction product with the hydroxy --. .''.
- ' .' ' ' '.",, ' ., ' . ' : ,", ,, '' ' ' ' : ~: ' , .' .
lV9;~Zti7 acid to produce' an etherified aminoplast resin having an acid number of at least 5.6.
The acid used must have a pKa not greater than about 5 in order to be effective as a catalyst for the cure reaction between the binder resin having active hydrogens and the amino-plast resin. It is found that carboxylic acid groups are gener-ally effective, but aromatic carboxylic groups are preferred.
Other stronger acids such as sulfonic acids may also be used and will produce a greater catalytic effect on the curing reaction.
Since the aminoplast resins are dispersed in an acid medium to form the electrocoating compositions Or the present invention and since it is known that such conditions are con-ducive to reaction and ultimately gelation lO9Z267 of the aminoplast resin, it is desirable to reduce the water solubility of the aminoplast resin so as to decrease its susceptibility to premature reaction and gelation. This can be achieved by etherifying (or transetherifying) the methylol groups with alcohols having a relatively hydrophobic group attached to the alcoholic hydroxyl group. Ordinarily it is found convenient to adjust the hydrophobicity by producing a suitable mixture of methyl and butyl or isobutyl ether groups. In such cases the greatest hydrophobicity, and conse-quently the greatest stability against premature reaction and gelation in the aqueous dispersion, will be achieved with all butyl or isobutyl ether groups.
But since the curing reaction is slower with butyl than with methyl ether groups on the aminoplast resin, it is not always desirable or necessary to shift the butyl/methyl ratio to give maximum hytrophobicity so long as suffic-ient bath stability for the particular composition and process is achieved.
Similar considerations apply where ether groups derived from other alcohols are employed. Of course, the effect on aqueous solubility of the acid-bearing group must also be accommodated in adjusting the set-off between (i) increasing by hydrophobicity and bath stability by incorporating a greater proportion of more hydrophobic ether groups and (ii) increasing the rate of the curing reaction in the deposited film by increasing the proportion of ether groups which decompose to liberate more volatile alcohols. It is found, however, that the acid groups, and particularly aromatic carboxylic acid groups, in- -- -corporated in the aminoplast resin itself do not produce premature reaction and gelation of the aminoplast resin and consequently the reciprocal adjust- ~ -ment of bath stability and cure speed is not adversely affected by the in-corporation of such acid groups except insosr as the aqueous solubility is affected.
Seversl examples of preferred embodiments will be given. Except where clearly indicatet otherwise, parts and percentages are by weight.
Where epoxy or oxirane values or numbers are referred to, they may be deter-minet by the method of Jay, Analytical Chemistry, vol. 36,667-8 (1964).
.
~()9Z267 Example 1 A suitable and preferred binder resin for practice of the present invention can be prepared by charging to a suitable reactor vessel 96.4 parts of diethanol amine and heating to about 130C. Over a period of about two hours, 857.2 parts of a 75% solution in xylene of a low molecular weight epoxide-functional epoxy resin derived from bisphenol-A and epichlorohydrin is added to the reaction vessel while maintaining the temperature at approximat-ely 130C. and retu ming refluxing xylene to the reacting mixture A suitable epoxy resin is the Dow Chemical Company product designated D~EoRo 671 which has a molecular weight of about 1050 and an epoxide equivalent weight of about 525. The above reaction conditions are maintained for about an addition-al hour, at which time 60.6 parts of nonylphenol are added over a period of about 10 minutes and the same reaction conditions are maintained until the epoxide (oxirsne) number is reduced to about 0, a period of about two to three hours. While the temperature is gradually raised from about 130C. to about 160QC. over a period of about one to two hours, about 190 parts of xylene are removed from the reaction mixture by distillation under vacuum. The temperat-ure of the reaction mixture is then lowered to about 125C. and there is ` -added 395.4 parts of an approximately 85% solution in isobutanol of an acid-functional aminoplast resin such as the American Cyanamid product designated CLA-66 which is a substantially fully etherified hexamethylol melamine ether-ified with lower alkanol and hydroxy aromatic carboxylic acid and has an acid number of about 19.6. This reaction mixture is maintained at about 115C.
with return of reflu,xin~ solvent for about one hour, at which time 233.2 parts ~ e~/os~'e of butyl or~ ed-e are added snd the mixture is cooled to room ~emperature.
This resin solution is about 78.5~ non-volatiles, has an acid number (based `
on non-volatiles) of about 4.28 and, after dilution with an equal quantity of C~/OSO~L'C
butyl ~r~o~r~, a viscosity of G on the Gardner-Holt scale, the viscosity solution being slightly cloudy.
. ~ .
~ ~ ~o~S' l~Z267 Exa~le II
A binder resin substantially identical to that of Example 1 can be produced without requiring the removal of solvent by starting with a liquid diepoxide of lower molecular weight, such as the diglycidyl ether of bisphen A, and first producing a higher molecular weight diepoxide therefrom by react-ing 2 moles of the liquid diepoxide with 1 mole of bisphenol A in the presence of a conventional amine or triphenyl phosphine catalyst, all in the absence of solvent.
Specifically, charge to a suitable reaction vessel 2713 parts of Dow Chemical Company liquid diepoxide D~E~Ro 333, having molecular weight-of about 350 and containing catalyst, and 787 parts of bisphenol A. Heat to about 140C. and permit the reaction exotherm to raise the temperature to about 180C. Hold at 180C. for about 2 hours until the viscosity of a ~/~0 s~ve ` sample diluted 1:1 with bu~yl oellosolvc is in the range H-J on the Gardner-Holt scale and the oxirane value is in the range about 3.1 to 3.3, Cool and Ce//r~
dilute with 937 parts butyl ce~H-o~ve. Place 1331 parts of the diepoxide resin solution so produced in a suitable reaction ve~sel, heat to 130 to 140C.,add 157.5 parts of diethanolamine and 99 parts of nonylphenol over about 2 hours, and hold at about 135C. for about 2 hours until the oxirane value is reduced to about 0. Then reduce the temperature to about 115C. and add 644 parts of an 85% solution in isobutanol of the American Cyanamid acid functional ether-ified melamine resin designated CLA-66. Hold at that temperature for about 1 ~e~r~
hour until the viscosity of a sample diluted 1:1 with butyl ~ ~}K ~i~e is about G to H on the Gardner-Holt scale. The acid number of this resin was about 5 and the reaction product about 80.7% non-volatiles. -Example III
In place of the acid functional melamine ether of Examples I and II
Day be substituted an acid functional benzoguanamine ether, whi~h can be made as follows. Place in a suitable reaction vessel 300 parts toluene, 1220 parts paraformaldehyde, 4560 parts n-butanol and 30 parts hexamethylenetetramine (as ,' :
lO9ZZ67 catalyst). Heat to reflux (about 110C.) for 1 to 2 hours until a clear solution is formed. The pH will be about 7 to 7.5. Add 1870 parts benzo-guanamine and hold the temperature at about 105C. until the solution is again clear. The pH will be about 8 to 8.6. Cool to 80C. and add about 8 parts maleic anydride to give a pH of 4.3 to 4.7. Heat to reflux and distill off a water-containing azeotrope over a period of about 6 to lZ hours, removing about 650 parts of water, until the mineral spirits tolerance is at least about 60.
The mineral spirits tolerance is the milliliters of mineral spirits that, mixed with 10 g. of sample, makes the mixture just cloudy enough that an ordin-ary laboratory thermometer becomes not clearly legible when viewed throughthe mixture contained in a 250 ml. beaker. Then distill under vacuum to remove about 2800 to 2900 parts of solvent, the temperature remaining below ` about 105 &. The intermediate product so formed is about 96.4% nonvolatiles, --has a Gardner-Holt viscosity of about Z6 to Z7, and an acid number of about 0.8.
Heat 500 parts of this intermediate product together with 39 parts Ce~/o s~ /~ e salicyclic acid and 76 parts butyl oeL} so}re at about 130C. for about 1 to
3 hours until the viscosity is about Z7 to Z8 to form the desired butylated, acid-functional benzoguanamine resin. This product will be about 76.4 non-volatiles and will have an acid number of about 14, based on nonvolatiles.
This and similar acid functional benzoguanamine ethers may be sub-stituted for melamine derivatives as the aminoplast resin in any of the electrocoating compositions or processes and will have superior resistance to premature reac~ion and/or gelation in the acidic a~ueous composition. However, ~`
because the cost is higher than melamine derivatives, the melamine derivatives will usually be selected for large volume uses.
ExaDple IV
The amino epoxy binder resin may be incorporated in the aqueous electrocoating for~ulation without pre-reaction with the aminoplast resin and it is usually preferred that the pigment be ground with a portion of the binder - 14 _ , resin in aqueous dispersion in the absence of any aminoplast resin before mixing with further dispersed binder resin and aminoplast resin to form the aqueous electrocoating composition. Suitable procedures for making such binder resins comprise adapting the procedures of Examples I and II to omit the intro-duction of aminoplast resin.
As a specific example, in a suitable reaction vessel heat 536 parts of diethanolamine to about 130C. and, while maintaining the temperature at -about 130 to 140C., add 4764 parts of Dow Chemical Company diepoxide resin solution (75% in xylene) D.E.R. 671X75 over a period of about 3 hours. Hold the reaction mixture in that temperature range for an additional hour and then add 337 parts of nonylphenol over about one-half hour. Maintain the temperat-ure for about 2 more hours until the oxirane value is about 0. Distill off about 900 parts of solvent as the temperature is gradually increased to about 150C. and then a vacuum is gradually applied. Pinally add 1111.5 parts butyl )~ ~ ~,~/~s;o~e co~losolvc and cool to room temperature. This resin solution is about 78.7%
nonvolatiles and has a vis¢osity of about J.
Example V
The required pendant hydrocarbon group can be incorporated by reacting a suitable hydrocarbon monoepoxide with a hydroxyl group on the epoxy resin. In the present example it is thought that this reaction involves a primary hydroxyl on the diethanol amine group rather than a secondary hydroxyl on the epoxy chain.
Heat 210 parts diethanola~ine in a suitable reaction vessel to --about 130C. and, while maintaining that temperature, add 1400 parts D.E.R.
671X75 diepoxide resin solution ~75% in xylene) over a period of about 3 hours. Hold at thattemperature for about 2 hours, then add 140 parts alpha-Olefin Epoxide 14-16, a Union Carbide Corporation product having the structure ~0~
CnH2n~l-CH _ CH2 , n = 14 to 16 and continue maintaining the temperature at about 130C. for about 2 to 3 . .
.
lO9ZZ67 hours until the oxirane value i~ reduced to about 0. Distill off under vacuum substantially all the xylene, add 355 parts butyl Cell~olve, and cool. This binder resin solution is about 79.8% nonvolatiles, ha~ an acid number of about 0, and a viscosity of about 1 to J upon 1:1 dilution ~ith butyl Cellosol~e.
Example VI
The required pendant hydrocarbon group may be attached to the binder resin by an ester linkage if the hydrocarbon group pendant from the carboxyl carbon is a tertiary hydrocarbon so that the ester group is resis-tant to hydrolysis. Versatic acid is a suitable commerically available acid and its glycldyl ester is available from Shell Chemical Company as a product deslgnated as Cardura E.
As a specific example, heat ~20 parts diethanolamine in a suitable reaction vessel to about 130C, add 2800 parts D.E.R. 671X75 Dow Chemical Company diepoxide resin solution over about 2 hours and maintain the tempera-ture for about another 1 to 2 hours until the oxirane value is about 0. Then add about ~5 parts Cardura E and hold at about 130C. for about 2 to 3 hours until the oxirane value is again reduced to about 0. Distill under vacuu~ to remo~e about 600 parts xylene, add 691 parts butyl Cellosolve and cool.
Thls binder resin solution is about 79.9% nonvolatiles, has an acid number of about 0 and a viscosity (diluted 1:1 with butyl Gellosolve) of about G to H.
ExamDle VII
By a procedure similar to that of Example 1 a binder resin part-ially reacted with an acid functional etherified melamine resin of lower acid number can be produced. A particularly suitable amino resin for use where an aminoplsst resln of lower acid number is desired is a butylated hexamethoxy melamine partially etherified with an aromatic carboxylic acid. The American Cyanamld Compsny product aeslgnated CLA-115 is such an aminoplast resin (85%
ln isobutanol) havin~ an acid number o~ about 13,7.
:
,, , ' lO~Z267 Heat 157.5 parts diethanol~mine in a suitable rea~tiGn vessel tc about 130C., add 1400 parts D.E.R. 671X75 diepoxide resin solution ~75% in xylene) over a period of about 2 hours and hold at that temperature for about one additional hour. Then add 99 parts nonylphenol and maintain the temperature for about 2-3 hours until the oxirane value is about 0. M still off about 320 parts solvent under vacuum while raising the te~perature grad-ually to about 150C. Reduce the temperature to about 115C, add 668 parts CLA-115, and maintain this temperature for about 1 hour. Add 358.6 parts butyl Cellosolve and cool to room temperature. ~his binder resin/aminoplast resin solution is about 78.5% nonvolatiles, hQs an acid number of about 2.9 (based on nonvolatiles) and a viscosity (diluted 1:1 with butyl Cellosolve) of about H.
While the electrocoating compositions of the present invention can be used without pigment so as to form clear coatings, ordinarily these comp-ositions will include conventional pigmentation. Because of the superior corrosion resistance and in particular resistance to detergent solutions, the use of these compositions will be further illustrated in formulation~
containing conventional pigmentation for gray appliance primer coatings.
Exam~le VIII
445 parts of the aminoplast-free binder resin solution of Ex y le N , 36 parts hexyl Cellosolve, 36 parts lactic acid, and 1083 parts deionized water sre mixed together to form a pigment grind vehicle. 482 parts of this grind vehicle, 54 parts butyl Cellosolve, 79 parts deionized water, 104 parts fine particle kaolin clay, 271 parts rutile titania, 5 parts furnace black, and 5 parts non-ionic 6urfactant defoamer are mixed together in conventional pigment paste grinding apparatus and 2.5 parts lactic acid are then added thereto and the resultlng mixture ground to a Hegeman fineness of about 6-1/2 to 7 to rOrm a pigment grind pQste. In a separate container are mixed to-gether 229 parts Or the partially pre-reacted binder resin-aminoplast resin solution of Exa~ple 1, lô parts hexyl Cellosolve, 18 parts lactic acid, and .
'.: ~ ' ' Z2~;7 235 parts deionized water To this mixture add 124 parts of the pigment grind paste and 1520 parts of deionized water to form an electrocoating dispersion composition having about 12% nonvolatiles and a pH of about 4.2 to
This and similar acid functional benzoguanamine ethers may be sub-stituted for melamine derivatives as the aminoplast resin in any of the electrocoating compositions or processes and will have superior resistance to premature reac~ion and/or gelation in the acidic a~ueous composition. However, ~`
because the cost is higher than melamine derivatives, the melamine derivatives will usually be selected for large volume uses.
ExaDple IV
The amino epoxy binder resin may be incorporated in the aqueous electrocoating for~ulation without pre-reaction with the aminoplast resin and it is usually preferred that the pigment be ground with a portion of the binder - 14 _ , resin in aqueous dispersion in the absence of any aminoplast resin before mixing with further dispersed binder resin and aminoplast resin to form the aqueous electrocoating composition. Suitable procedures for making such binder resins comprise adapting the procedures of Examples I and II to omit the intro-duction of aminoplast resin.
As a specific example, in a suitable reaction vessel heat 536 parts of diethanolamine to about 130C. and, while maintaining the temperature at -about 130 to 140C., add 4764 parts of Dow Chemical Company diepoxide resin solution (75% in xylene) D.E.R. 671X75 over a period of about 3 hours. Hold the reaction mixture in that temperature range for an additional hour and then add 337 parts of nonylphenol over about one-half hour. Maintain the temperat-ure for about 2 more hours until the oxirane value is about 0. Distill off about 900 parts of solvent as the temperature is gradually increased to about 150C. and then a vacuum is gradually applied. Pinally add 1111.5 parts butyl )~ ~ ~,~/~s;o~e co~losolvc and cool to room temperature. This resin solution is about 78.7%
nonvolatiles and has a vis¢osity of about J.
Example V
The required pendant hydrocarbon group can be incorporated by reacting a suitable hydrocarbon monoepoxide with a hydroxyl group on the epoxy resin. In the present example it is thought that this reaction involves a primary hydroxyl on the diethanol amine group rather than a secondary hydroxyl on the epoxy chain.
Heat 210 parts diethanola~ine in a suitable reaction vessel to --about 130C. and, while maintaining that temperature, add 1400 parts D.E.R.
671X75 diepoxide resin solution ~75% in xylene) over a period of about 3 hours. Hold at thattemperature for about 2 hours, then add 140 parts alpha-Olefin Epoxide 14-16, a Union Carbide Corporation product having the structure ~0~
CnH2n~l-CH _ CH2 , n = 14 to 16 and continue maintaining the temperature at about 130C. for about 2 to 3 . .
.
lO9ZZ67 hours until the oxirane value i~ reduced to about 0. Distill off under vacuum substantially all the xylene, add 355 parts butyl Cell~olve, and cool. This binder resin solution is about 79.8% nonvolatiles, ha~ an acid number of about 0, and a viscosity of about 1 to J upon 1:1 dilution ~ith butyl Cellosol~e.
Example VI
The required pendant hydrocarbon group may be attached to the binder resin by an ester linkage if the hydrocarbon group pendant from the carboxyl carbon is a tertiary hydrocarbon so that the ester group is resis-tant to hydrolysis. Versatic acid is a suitable commerically available acid and its glycldyl ester is available from Shell Chemical Company as a product deslgnated as Cardura E.
As a specific example, heat ~20 parts diethanolamine in a suitable reaction vessel to about 130C, add 2800 parts D.E.R. 671X75 Dow Chemical Company diepoxide resin solution over about 2 hours and maintain the tempera-ture for about another 1 to 2 hours until the oxirane value is about 0. Then add about ~5 parts Cardura E and hold at about 130C. for about 2 to 3 hours until the oxirane value is again reduced to about 0. Distill under vacuu~ to remo~e about 600 parts xylene, add 691 parts butyl Cellosolve and cool.
Thls binder resin solution is about 79.9% nonvolatiles, has an acid number of about 0 and a viscosity (diluted 1:1 with butyl Gellosolve) of about G to H.
ExamDle VII
By a procedure similar to that of Example 1 a binder resin part-ially reacted with an acid functional etherified melamine resin of lower acid number can be produced. A particularly suitable amino resin for use where an aminoplsst resln of lower acid number is desired is a butylated hexamethoxy melamine partially etherified with an aromatic carboxylic acid. The American Cyanamld Compsny product aeslgnated CLA-115 is such an aminoplast resin (85%
ln isobutanol) havin~ an acid number o~ about 13,7.
:
,, , ' lO~Z267 Heat 157.5 parts diethanol~mine in a suitable rea~tiGn vessel tc about 130C., add 1400 parts D.E.R. 671X75 diepoxide resin solution ~75% in xylene) over a period of about 2 hours and hold at that temperature for about one additional hour. Then add 99 parts nonylphenol and maintain the temperature for about 2-3 hours until the oxirane value is about 0. M still off about 320 parts solvent under vacuum while raising the te~perature grad-ually to about 150C. Reduce the temperature to about 115C, add 668 parts CLA-115, and maintain this temperature for about 1 hour. Add 358.6 parts butyl Cellosolve and cool to room temperature. ~his binder resin/aminoplast resin solution is about 78.5% nonvolatiles, hQs an acid number of about 2.9 (based on nonvolatiles) and a viscosity (diluted 1:1 with butyl Cellosolve) of about H.
While the electrocoating compositions of the present invention can be used without pigment so as to form clear coatings, ordinarily these comp-ositions will include conventional pigmentation. Because of the superior corrosion resistance and in particular resistance to detergent solutions, the use of these compositions will be further illustrated in formulation~
containing conventional pigmentation for gray appliance primer coatings.
Exam~le VIII
445 parts of the aminoplast-free binder resin solution of Ex y le N , 36 parts hexyl Cellosolve, 36 parts lactic acid, and 1083 parts deionized water sre mixed together to form a pigment grind vehicle. 482 parts of this grind vehicle, 54 parts butyl Cellosolve, 79 parts deionized water, 104 parts fine particle kaolin clay, 271 parts rutile titania, 5 parts furnace black, and 5 parts non-ionic 6urfactant defoamer are mixed together in conventional pigment paste grinding apparatus and 2.5 parts lactic acid are then added thereto and the resultlng mixture ground to a Hegeman fineness of about 6-1/2 to 7 to rOrm a pigment grind pQste. In a separate container are mixed to-gether 229 parts Or the partially pre-reacted binder resin-aminoplast resin solution of Exa~ple 1, lô parts hexyl Cellosolve, 18 parts lactic acid, and .
'.: ~ ' ' Z2~;7 235 parts deionized water To this mixture add 124 parts of the pigment grind paste and 1520 parts of deionized water to form an electrocoating dispersion composition having about 12% nonvolatiles and a pH of about 4.2 to
4.4.
Example IX
Coatings can be deposited from the aqueous electrocoating composit-ion of Example VIII in conventional electrocoating apparatus by connecting the workpiece substrate to be coated as the cathode electrode and maintaining a voltage of about lS0 volts between the workpiece cathode and the counter-electrode with the liquid electrocoating dispersion maintained at a tempera-ture of about 70P. Under these conditions a final coating thickness of about 1/2 mil is deposited in about 90 seconds. The coatings so deposited can be baked at about 375F. for about 20 minutes to give hard, tough, ad-herent cured coatings. On either galvanized steel or cold rolled steel sub-strates these cured coatings provide exceptional resistance to corrosion of the substrate when exposed to either salt spray or detergent solutions.
In continuous operation, the electrodepositable components of the electrocoating dispersion must be periodically or continuously replaced. It is prefersble that this be done with a high solids, low acid replacement feed composition in order to minimize the build-up of solubilizing acid and of water in the bath and the consequent requirement that such excess acid and/or water be removed by ultrafiltration, reverse osmosis or similar well-known techniques.
Example X
A suitable replacement feed composition for use in conjunction with the bath composition of Example VIII can be made by mixing together 205 parts of the bind~r r~s n/aminoplast resin solution of Example 1, 16 parts of hexyl o ~ e~ , 5 parts lactic acid, 8 parts denatured alcohol, and 31 parts deionized water and mixing that solution with 104 parts of the pigment grind paste of Example VIII. This replacement composition is about 61% non-~olatiles and should be added to the 12% bath composition of Example VIII
either intermittently or continuously so as to approximately replace the components depleted from the bath during its use in an electrocoating process.
.
- ; .. .. .. ...
Example IX
Coatings can be deposited from the aqueous electrocoating composit-ion of Example VIII in conventional electrocoating apparatus by connecting the workpiece substrate to be coated as the cathode electrode and maintaining a voltage of about lS0 volts between the workpiece cathode and the counter-electrode with the liquid electrocoating dispersion maintained at a tempera-ture of about 70P. Under these conditions a final coating thickness of about 1/2 mil is deposited in about 90 seconds. The coatings so deposited can be baked at about 375F. for about 20 minutes to give hard, tough, ad-herent cured coatings. On either galvanized steel or cold rolled steel sub-strates these cured coatings provide exceptional resistance to corrosion of the substrate when exposed to either salt spray or detergent solutions.
In continuous operation, the electrodepositable components of the electrocoating dispersion must be periodically or continuously replaced. It is prefersble that this be done with a high solids, low acid replacement feed composition in order to minimize the build-up of solubilizing acid and of water in the bath and the consequent requirement that such excess acid and/or water be removed by ultrafiltration, reverse osmosis or similar well-known techniques.
Example X
A suitable replacement feed composition for use in conjunction with the bath composition of Example VIII can be made by mixing together 205 parts of the bind~r r~s n/aminoplast resin solution of Example 1, 16 parts of hexyl o ~ e~ , 5 parts lactic acid, 8 parts denatured alcohol, and 31 parts deionized water and mixing that solution with 104 parts of the pigment grind paste of Example VIII. This replacement composition is about 61% non-~olatiles and should be added to the 12% bath composition of Example VIII
either intermittently or continuously so as to approximately replace the components depleted from the bath during its use in an electrocoating process.
.
- ; .. .. .. ...
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cathodic electrocoating composition comprising, in aqueous disper-sion:
(a) a cathodically electrodepositable, at least partically cationized binder resin comprising a major proportion by weight of a reaction product of an epoxide-functional resin and a monoamino alcohol or phenol having at least one reactive hydrogen on the amino nitrogen, said reaction product being sub-stantially devoid of reactive epoxide groups and having an average of at least about two reactive hydroxyl groups and an average of at least about 0.2 directly or indirectly pendant 5 to 20 carbon atom hydrocarbon radical per molecule;
(b) from about 0.05 to about 1 weight parts, per weight part of said binder resin, of an acid-functional aminoplast resin (i) cathodically co-electrodepositable with said binder resin from said aqueous dispersion to form an intermediate product comprising an intimate mixture of the cathodic-ally electrodeposited forms of said binder resin and said aminoplast resin, (ii) co-reactive in said intermediate product with the cathodically electro-deposited form of said binder resin, upon heating, to transform said inter-mediate product into a cured resinous product, (iii) having at least about 0.0001 equivalent of titratable acid functionality of PKa not greater than about 5 per gram of said aminoplast resin, and (iv) not soluble in the aqueous medium of said dispersion; and (c) from about 20 to about 150 milliequivalents, per 100 grams of (a) and (b), of an anion of a water-soluble acid to induce and stabilize the cationization of said binder resin; said aqueous dispersion having a pH of from about 2 to about 7 and being substantially free of any water-soluble acid which will be retained in water-soluble form in said cured resinous product and of anions thereof.
2. The composition of Claim 1 wherein said hydrocarbon radical is attached to said reaction product by an ether linkage or by an ester linkage, provided that the hydrocarbon radical is a tertiary radical on the carboxyl carbon atom of said ester linkage.
3. The composition of Claim 1 wherein said monoamino alcohol or phenol is a dialkanol amine in which each alkanol group has from 2 to 5 carbon atoms.
4, The composition of Claim 1 wherein said epoxy resin comprises a major proportion by weight of the reaction product of a diepoxide reaction product of bisphenol A and epichlorohydrin having an average molecular weight from about 500 to about 2500 and from about 0.2 to about 1 mole of a mono-hydroxyl alcohol or phenol having from 5 to 20 carbon atoms per mole of said diepoxide.
5. The composition of Claim 4 wherein said monoamino alcohol or phenol is a dialkanol amine in which each alkanol group has from 2 to 5 carbon atoms.
6. The composition of Claim 5 wherein said monohydroxyl alcohol or phenol is an alkylphenol in which the alkyl group has from 8 to 10 carbon atoms and wherein said monoamino alcohol or phenol is diethanol amine.
7. The composition of Claim 1 wherein said anion of a water-soluble acid is the anion of lactic acid.
8. A process for cathodically electrocoating a metallic substrate to form a cured resinous coating thereon, said process comprising (A) establishing simultaneous contact of said metallic substrate and a counter-electrode with a body of liquid aqueous dispersion having dispersed therein (a) a cathodically electrodepositable, at least partically cationized binder resin comprising a major proportion by weight of a reaction product of an epoxide-functional resin and a monoamino alcohol or phenol having at least one reactive hydrogen on the amino nitrogen, said reaction product being substantially devoid of reactive epoxide groups and having an average THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cathodic electrocoating composition comprising, in aqueous disper-sion:
(a) a cathodically electrodepositable, at least partically cationized binder resin comprising a major proportion by weight of a reaction product of an epoxide-functional resin and a monoamino alcohol or phenol having at least one reactive hydrogen on the amino nitrogen, said reaction product being sub-stantially devoid of reactive epoxide groups and having an average of at least about two reactive hydroxyl groups and an average of at least about 0.2 directly or indirectly pendant 5 to 20 carbon atom hydrocarbon radical per molecule;
(b) from about 0.05 to about 1 weight parts, per weight part of said binder resin, of an acid-functional aminoplast resin (i) cathodically co-electrodepositable with said binder resin from said aqueous dispersion to form an intermediate product comprising an intimate mixture of the cathodic-ally electrodeposited forms of said binder resin and said aminoplast resin, (ii) co-reactive in said intermediate product with the cathodically electro-deposited form of said binder resin, upon heating, to transform said inter-mediate product into a cured resinous product, (iii) having at least about 0.0001 equivalent of titratable acid functionality of PKa not greater than about 5 per gram of said aminoplast resin, and (iv) not soluble in the aqueous medium of said dispersion; and (c) from about 20 to about 150 milliequivalents, per 100 grams of (a) and (b), of an anion of a water-soluble acid to induce and stabilize the cationization of said binder resin; said aqueous dispersion having a pH of from about 2 to about 7 and being substantially free of any water-soluble acid which will be retained in water-soluble form in said cured resinous product and of anions thereof.
(a) a cathodically electrodepositable, at least partically cationized binder resin comprising a major proportion by weight of a reaction product of an epoxide-functional resin and a monoamino alcohol or phenol having at least one reactive hydrogen on the amino nitrogen, said reaction product being sub-stantially devoid of reactive epoxide groups and having an average of at least about two reactive hydroxyl groups and an average of at least about 0.2 directly or indirectly pendant 5 to 20 carbon atom hydrocarbon radical per molecule;
(b) from about 0.05 to about 1 weight parts, per weight part of said binder resin, of an acid-functional aminoplast resin (i) cathodically co-electrodepositable with said binder resin from said aqueous dispersion to form an intermediate product comprising an intimate mixture of the cathodic-ally electrodeposited forms of said binder resin and said aminoplast resin, (ii) co-reactive in said intermediate product with the cathodically electro-deposited form of said binder resin, upon heating, to transform said inter-mediate product into a cured resinous product, (iii) having at least about 0.0001 equivalent of titratable acid functionality of PKa not greater than about 5 per gram of said aminoplast resin, and (iv) not soluble in the aqueous medium of said dispersion; and (c) from about 20 to about 150 milliequivalents, per 100 grams of (a) and (b), of an anion of a water-soluble acid to induce and stabilize the cationization of said binder resin; said aqueous dispersion having a pH of from about 2 to about 7 and being substantially free of any water-soluble acid which will be retained in water-soluble form in said cured resinous product and of anions thereof.
2. The composition of Claim 1 wherein said hydrocarbon radical is attached to said reaction product by an ether linkage or by an ester linkage, provided that the hydrocarbon radical is a tertiary radical on the carboxyl carbon atom of said ester linkage.
3. The composition of Claim 1 wherein said monoamino alcohol or phenol is a dialkanol amine in which each alkanol group has from 2 to 5 carbon atoms.
4. The composition of Claim 1 wherein said epoxy resin comprises a major proportion by weight of the reaction product of a diepoxide reaction product of bisphenol A and epichlorohydrin having an average molecular weight from about 500 to about 2500 and from about 0.2 to about 1 mole of a mono-hydroxyl alcohol or phenol having from 5 to 20 carbon atoms per mole of said diepoxide.
5. The composition of Claim 4 wherein said monoamino alcohol or phenol is a dialkanol amine in which each alkanol group has from 2 to 5 carbon atoms.
6. The composition of Claim 5 wherein said monohydroxyl alcohol or phenol is an alkylphenol in which the alkyl group has from 8 to 10 carbon atoms and wherein said monoamino alcohol or phenol is diethanol amine.
7. The composition of Claim 1 wherein said anion of a water-soluble acid is the anion of lactic acid.
8. A process for cathodically electrocoating a metallic substrate to form a cured resinous coating thereon, said process comprising (A) establishing simultaneous contact of said metallic substrate and a counter-electrode with a body of liquid aqueous dispersion having dispersed therein (a) a cathotically electrodepositable, at least partically cationized binder resin comprising a major proportion by weight of a reaction product of an epoxide-functional resin and a monoamino alcohol or phenol having at least one reactive hydrogen on the amino nitrogen, said reaction product being substantially devoid of reactive epoxide groups and having an average
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US642,694 | 1975-12-22 | ||
| US05/642,694 US4066525A (en) | 1975-12-22 | 1975-12-22 | Cathodic electrocoating process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1092267A true CA1092267A (en) | 1980-12-23 |
Family
ID=24577632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA266,855A Expired CA1092267A (en) | 1975-12-22 | 1976-11-30 | Cathodic electrocoating compositions and processes |
Country Status (11)
| Country | Link |
|---|---|
| US (2) | US4066525A (en) |
| JP (1) | JPS5278932A (en) |
| BE (1) | BE849457A (en) |
| BR (1) | BR7608438A (en) |
| CA (1) | CA1092267A (en) |
| DE (1) | DE2658016A1 (en) |
| ES (1) | ES454407A1 (en) |
| FR (1) | FR2336459A1 (en) |
| GB (1) | GB1521200A (en) |
| IT (1) | IT1069840B (en) |
| NL (1) | NL7614171A (en) |
Families Citing this family (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE31616E (en) * | 1977-12-12 | 1984-06-26 | Wyandotte Paint Products | Cathodic electrodeposition coating compositions containing diels-alder adducts |
| USRE31803E (en) * | 1977-12-12 | 1985-01-15 | Wyandotte Paint Products Company | Method for cathodic electrodeposition of coating compositions containing diels-alder adducts |
| US4159233A (en) * | 1978-02-03 | 1979-06-26 | Scm Corporation | Cathodic electrocoating process for forming resinous coating using an aqueous dispersion of polyamino polyhydroxy polyether resinous adduct and acid-functional aminoplast |
| US4167499A (en) * | 1978-05-09 | 1979-09-11 | E. I. Du Pont De Nemours And Company | Graft copolymer useful in electrodeposition |
| US4374965A (en) * | 1978-08-31 | 1983-02-22 | Ford Motor Company | Alkaline resistant organic coatings for corrosion susceptible substrates II |
| US4374213A (en) * | 1978-08-31 | 1983-02-15 | Ford Motor Company | Alkaline resistant organic coatings for corrosion susceptible substrates III |
| US4339368A (en) * | 1978-11-22 | 1982-07-13 | Wyandotte Paint Products Company | Cationic coating compositions containing nitrogen heterocyclic materials |
| US4231907A (en) * | 1978-12-22 | 1980-11-04 | Grow Group Inc. | Cathodic electrodeposition compositions employing fatty acid derivatives |
| US4246089A (en) * | 1979-11-30 | 1981-01-20 | E. I. Du Pont De Nemours And Company | Graft copolymer useful in electrodeposition |
| US4383073A (en) * | 1981-08-20 | 1983-05-10 | The Dow Chemical Company | Cationic resin curable with acid catalyzed cross-linkers |
| EP0127915B1 (en) * | 1983-06-03 | 1988-12-07 | Shell Internationale Researchmaatschappij B.V. | Novel polyglycidyl ethers, their preparation and their use as thermosetting coating compositions |
| GB8315230D0 (en) * | 1983-06-03 | 1983-07-06 | Shell Int Research | Polyglycidyl ethers |
| DE3329693A1 (en) * | 1983-08-17 | 1985-03-07 | Basf Farben + Fasern Ag, 2000 Hamburg | METHOD FOR THE PRODUCTION OF SELF-CROSSLINKING RESINS AND THEIR USE |
| US4686248A (en) * | 1984-02-28 | 1987-08-11 | Shell Oil Company | Preparation of binders for coatings, thermosetting coating compositions and their use |
| US4639493A (en) * | 1984-12-10 | 1987-01-27 | Ford Motor Company | Conjugated diene functional modified aminoepoxy resins |
| US4617348A (en) * | 1984-12-10 | 1986-10-14 | Ford Motor Company | Crosslinkable composition comprising modified aminoepoxy resins-II |
| US4657979A (en) * | 1984-12-10 | 1987-04-14 | E. I. Du Pont De Nemours And Company | Blocked dieneophile functional modified aminoepoxy resins |
| US4720523A (en) * | 1984-12-10 | 1988-01-19 | E. I. Du Pont De Nemours And Company | Blocked dieneophile functional modified aminoepoxy resins |
| US4715898A (en) * | 1986-06-30 | 1987-12-29 | Ppg Industries, Inc. | Sulfonium resins useful as pigment grinding vehicles in cationic electrodeposition |
| GB8616162D0 (en) * | 1986-07-02 | 1986-08-06 | Shell Int Research | Cationic coating compositions |
| US4812215A (en) * | 1986-12-29 | 1989-03-14 | Ppg Industries, Inc. | Low temperature curable aqueous electrodepositable coating compositions |
| JPH0751693B2 (en) * | 1987-11-06 | 1995-06-05 | 関西ペイント株式会社 | Coating resin composition |
| US5076900A (en) * | 1989-08-28 | 1991-12-31 | E. I. Du Pont De Nemours And Company | Aminoplast containing cathodic electrodeposition baths |
| US4980429A (en) * | 1990-01-26 | 1990-12-25 | E. I. Du Pont De Nemours And Company | Low cure aminoplast cathodic electrodeposition baths |
| US5116914A (en) * | 1990-12-18 | 1992-05-26 | E. I. Du Pont De Nemours And Company | Cathodic electrodeposition coatings containing alkyl metal acetonate catalyst |
| US6099808A (en) * | 1993-10-05 | 2000-08-08 | Texas Instruments Incorporated | Particulate removal from point of use exhaust scrubbers |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3965058A (en) * | 1965-04-01 | 1976-06-22 | Ppg Industries, Inc. | Coreaction products |
| GB1145831A (en) * | 1965-05-20 | 1969-03-19 | British Industrial Plastics | Improvements in aminoplastic resins |
| GB1102384A (en) * | 1965-10-11 | 1968-02-07 | Coates Brothers & Co | Melamine-formaldehyde resins for electrodeposition |
| US3471388A (en) * | 1966-02-07 | 1969-10-07 | American Cyanamid Co | Electrodeposition of aqueous coatings containing etherified methylolated melamine |
| US3519627A (en) * | 1968-04-09 | 1970-07-07 | Ashland Oil Inc | Carboxyl-containing ethers of amino-triazine/aldehyde condensates |
| US3676312A (en) * | 1970-03-13 | 1972-07-11 | Desoto Inc | Aminoplast resins particularly adapted for electrocoating and process for producing the same |
| US3891527A (en) * | 1971-07-14 | 1975-06-24 | Desoto Inc | Water-dispersible cationic polyurethane resins |
| GB1423973A (en) * | 1973-03-28 | 1976-02-04 | M & T Chemicals Inc | Aqueous coating compositions |
-
1975
- 1975-12-22 US US05/642,694 patent/US4066525A/en not_active Expired - Lifetime
-
1976
- 1976-11-30 CA CA266,855A patent/CA1092267A/en not_active Expired
- 1976-12-03 GB GB5058476A patent/GB1521200A/en not_active Expired
- 1976-12-16 BE BE1007829A patent/BE849457A/en unknown
- 1976-12-16 BR BR7608438A patent/BR7608438A/en unknown
- 1976-12-17 DE DE19762658016 patent/DE2658016A1/en not_active Withdrawn
- 1976-12-17 IT IT5266776A patent/IT1069840B/en active
- 1976-12-18 ES ES454407A patent/ES454407A1/en not_active Expired
- 1976-12-20 NL NL7614171A patent/NL7614171A/en not_active Application Discontinuation
- 1976-12-20 FR FR7638383A patent/FR2336459A1/en active Granted
- 1976-12-20 JP JP15213076A patent/JPS5278932A/en active Pending
-
1977
- 1977-07-05 US US05/813,082 patent/US4119599A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| BR7608438A (en) | 1977-12-13 |
| US4066525A (en) | 1978-01-03 |
| US4119599A (en) | 1978-10-10 |
| BE849457A (en) | 1977-06-16 |
| FR2336459A1 (en) | 1977-07-22 |
| GB1521200A (en) | 1978-08-16 |
| IT1069840B (en) | 1985-03-25 |
| NL7614171A (en) | 1977-06-24 |
| DE2658016A1 (en) | 1977-06-30 |
| ES454407A1 (en) | 1977-12-01 |
| JPS5278932A (en) | 1977-07-02 |
| FR2336459B1 (en) | 1981-02-13 |
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