STORAGE STABLE AUTODEPOSITABLE DISPERSIONS OF EPOXY RESINS AND PROCESSES THEREFOR AND THEREWITH

Abstract: Epoxy resins, particularly those based on bis-phenol-A, can constitute the principal film forming polymer component of a storage stable autodeposition composition when the particle size distribution of all the film forming polymers in the composition satisfies the following criteria: (1) the mean light scattering particle size is at least about 100 but not more than about 300 nm; (2) no more than about 1.0 % of the light scattering particles volume consists of particles with a diameter larger than about 450 nm; (3) no more than about 25 % of the light scattering particles volume consists of particles with a diameter larger than about 250 nm; (4) no more than about 50 % of the light scattering particles volume consists of particles with a diameter larger than about 200 nm; and (5) no more than about 75 % of the light scattering particles volume consists of particles with a diameter larger than about 175 nm. Such dispersion can conveniently be achieved using a two stage process in which a solution of the film forming polymers is emulsified into water to form a preliminary dispersion and this preliminary dispersion is subjected to at least one particle size refinement stage in which the preliminary dispersion is forced through a narrow aperture.

Description: Description STORAGE STABLE AUTODEPOSITABLE DISPERSIONS OF EPOXY RESINS AND PROCESSES THEREFOR AND THEREWITH BACKGROUND OF THE INVENTION Field ofthe Invention This invention relates to the use of aqueous liquid compositions (either disper¬ sions or true solutions) with which active metal surfaces can be coated, by mere contact with the liquid composition, with an adherent polymer film that increases in thickness the longer the time of contact, even though the liquid composition is stable for a long time against spontaneous precipitation or flocculation of any solid phase, in the absence of contact with active metal. (For the purposes of this specification, the term "active met¬ al" is to be understood in its broadest sense as including all metals and alloys more active than hydrogen in the electromotive series, or, in other words, a metal which is thermody¬ namically capable of dissolving to produce dissolved cations derived from the metal, with accompanying evolution of hydrogen gas, when contacted with an aqueous solution ofa non-oxidizing acid in which the activity of hydrogen ions is 1 equivalent per liter.) Such liquid compositions are denoted in this specification, and commonly in the art, as "autodeposition" or "autodepositing" compositions, dispersions, emulsions, suspensions, baths, solutions, or a like term. Autodeposition is often contrasted with electrodeposi- tion, which can produce very similar adherent films but requires that the surface to be coated be connected to a source of direct current electricity for coating to occur. In particular, this invention is concerned with autodeposition of high quality, cor- rosion inhibiting coatings that include epoxy resins and/or products of reaction of mole¬ cules of epoxy resins with one another and/or with other materials. Statement of Related Art It is generally believed in the art that autodeposition works because cations dis¬ solving from the metal surface to be coated, which cations when initially dissolved are, of course, confined to the volume of contacting liquid in the immediate vicinity of the metal surface from which they are dissolving, interact with the liquid autodepositing composition in at least one ofthe following ways: (i) The dissolved cations precipitate previously dissolved polymers by displacing previously associated cations or cation- forming moieties, in association with which the polymers are soluble, by the newly dis- solved cations in association with which the polymers are much less soluble; and/or (ii) the dissolved cations destabilize numerous individual dispersed phase units in a disper¬ sion of a polymer with inherently low water solubility, which nevertheless can remain in stable suspension for a long time in the absence of dissolved polyvalent cations, be- cause the outer surfaces of the dispersed phase units carry a net negative electrical charge, derived from anionic components ofthe dispersed polymer itself and/or from an anionic dispersing agent used to prepare the autodepositing composition in question. The net negative charge on the units ofthe dispersed phase in an autodepositing liquid composition is believed to be electrically counterbalanced by a diffuse excess of cations, usually monovalent cations, in the surrounding continuous phase ofthe disper¬ sion, this excess of cations together with the negative charges on the dispersed phase un¬ its constituting an example of the well known "electrical double layer" or "Helmholz double layer" that is characteristic of most interfaces between liquid phases containing charged solute particles and solids in contact with such liquid phases. As long as this double layer remains intact, the net negative charge on the exterior of each unit of dis¬ persed phase causes it to repel other units ofthe disperse phase that also carry a net nega¬ tive charge, and thereby prevents spontaneous coalescence ofthe dispersed phase units. When the double layer is sufficiently disturbed, or in the case ofa soluble poly¬ mer, when the solubility is reduced, by introduction of new cations, the polymeric parts of numerous dispersed phase units and/or solute polymer molecules can aggregate to form a continuous coating layer, if the chemical nature ofthe polymer favors such a tran¬ sition and the temperature is sufficiently far above the glass transition temperature ofthe polymer concerned. A practically useful autodepositing liquid composition therefore must have a bal- ance between its needs for (i) stability during storage in the absence of particular kinds of metallic cations and (ii) quick transition to local instability, in the presence ofthe con¬ centrations of these particular kinds of metallic cations that are developed in the vicinity of solid metals that are dissolving to produce these particular kinds of metallic cations. In the past practically successful autodepositing liquid compositions have been made from a variety of polymers, but all or almost all of them have been polymers that were initially prepared by polymerization of emulsified vinyl monomers, a process that is usu¬ ally denoted in the art as "emulsion polymerization". However, by no means all poly- mers made by emulsion polymerization have been found useful in autodepositing liquid compositions, and some ofthe best protective coating properties achieved by other meth¬ ods of coating have been achieved with polymers, such as urethane and epoxy resins, that have not been successfully prepared on a practical scale by emulsion polymerization. Practical success in autodepositing polymers of this type has been generally elusive here¬ tofore. DESCRIPTION OF THE INVENTION Objects ofthe Invention A major object of this invention is to provide autodepositing liquid compositions from which it is possible to deposit on contacted metal surfaces epoxy resin based coat¬ ings that will provide at least approximately as much protection against corrosion and against mechanical stresses as do the best quality electrodeposited coatings based on epoxy resins. Another object is to provide an at least reasonably economical method of making such autodepositing liquid compositions on a commercial scale. Still another ob- ject is to utilize the autodepositing liquid compositions provided by the invention for su¬ perior and/or more economical coating processes to produce useful articles. Other ob¬ jects will be apparent from the further description below. General Principles of Description Except in the claims and the specific examples, or where otherwise expressly in- dicated, all numerical quantities in this description indicating amounts of material or con¬ ditions of reaction and/or use are to be understood as modified by the word "about" in describing the broadest scope ofthe invention. Practice within the numerical limits stat¬ ed is generally preferred, however. Also, throughout unless expressly stated to the con¬ trary: percent, amount, "parts of, and ratio values are by weight; the term "polymer" in- eludes "oligomer", "copolymer", "terpolymer", and the like; the first definition or de¬ scription ofthe meaning ofa word, phrase, acronym, abbreviation or the like applies to all subsequent uses ofthe same word, phrase, acronym, abbreviation or the like and ap¬ plies, mutatis mutandis, to normal grammatical variations thereof; the term "mole" and its variations may be applied to ions, moieties, elements, and any other actual or hypo- thetical entity defined by the number and type of atoms present in it, as well as to materi¬ als with well defined neutral molecules; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more ofthe members ofthe group or class are equally suitable or preferred; description of preparation of autodepositing liquid compositions or compon¬ ents thereof by utilizing electrically neutral chemical constituents refers to the constitu¬ ents at the time of first addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture, or physical changes in such properties as dispersed particle sizes and distribution of materi¬ als between dispersed and continuous phases in a dispersion, after mixing has occurred; specification of materials in ionic form implies the presence of sufficient counterions to produce electrical neutrality for the composition as a whole; and any counterions thus im- plicitly specified preferably are selected from among other constituents explicitly speci¬ fied in ionic form, to the extent possible; otherwise such counterions may be freely se¬ lected, except for avoiding counterions that act adversely to the objects ofthe invention. Summary ofthe Invention It has been found that one ofthe most important characteristics determining the suitability of an autodepositing liquid composition containing dispersed epoxy resin is the size distribution ofthe dispersed phase units in the autodepositing liquid composition. The large number ofthe dispersed phase units requires in practice that the size distribu¬ tion be described statistically. The most effective method of measurement and definition of particle distribution for purposes of this description has been found to be one which measures the scattering of laser generated light by particles in Brownian motion in the dispersion and relates the fluctuations in scattered light intensity to the sizes ofthe light scattering units (also optionally called "particles"). This type of analysis is performed by a commercially available apparatus, a NICOMP™ Model 370 Microparticle Analyzer, supplied by Particle Sizing Systems, Inc., Santa Barbara, California USA, which pro- vides a machine-generated histogram plot, and corresponding numerical data, for the vol¬ ume percent ofthe light scattering units in the dispersion falling within various particle size ranges, and also automatically calculates various statistical measures such as the mean diameter, "effective particle size", standard deviation, coefficient of variation, cum¬ ulative volume to various limits, and the like. The machine is capable of analyzing the statistical results either according to an assumption ofa Gaussian distribution or accord¬ ing to another method that allows for bimodal distributions. For the purposes of this specification, however, analysis according to the assumption ofa Gaussian distribution is generally preferred, even when the statistics indicate a low probability that this is the actual distribution ofthe light scattering units. Any errors that this method of analysis may cause have not been found to substantially affect the preferences set forth below. A closely related particle size distribution measurement technique that has also been used measures the scattering of laser generated light by particles in electrophoretic motion rather than more random Brownian motion. The particular commercial apparatus used was a ZETAPLUS™ Zeta Potential Analyzer commercially supplied by Brookhav- en Instruments Corp., Austin, Texas, USA. For preferred particle size distributions, this method of analysis generally appears to give nearly the same results as the most preferred method noted in the immediately preceding paragraph. Other methods may well also be suitable, but the method described in the immediately preceding paragraph is to be under¬ stood as definitive for determining whether particular compositions conform to any de¬ scription below that prescribes limits on particle size distributions. An autodepositing liquid composition according to the present invention compris- es, preferably consists essentially of, or more preferably consists of, water and: (A) a concentration of at least 1.0 %, based on the whole composition, of dispersed or both dispersed and dissolved film forming polymer molecules that include a concentration of at least 0.2 %, based on the whole composition, of dispersed molecules selected from the group consisting of all organic molecules that con- tain at least two 1,2-epoxy moieties per molecule, all of said dispersed or dis¬ solved and dispersed film forming polymer molecules collectively having the fol¬ lowing size distribution characteristics, which are measured as indicated above, in the absence of other light scattering materials such as pigments, in a dis¬ persion, or dispersion and solution, the phrase "dispersion, or dispersion and solu- tion" being hereinafter usually abbreviated as "DDS", ofthe film forming pol¬ ymer molecules in water: (1) the mean light scattering particle size in the DDS is at least 100 but not more than 300 nanometres (hereinafter usually abbreviated "nm"); (2) no more than 1.0 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than 450 nm; (3) no more than 25 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than 250 nm; (4) no more than 50 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than 200 nm; and (5) no more than 75 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than 175 nm; (B) an emulsifying agent component in sufficient quantity to emulsify all dispersed constituent molecules of component (A) so that, in the autodepositing liquid com¬ position, no separation or segregation of bulk phases that is perceptible with nor¬ mal unaided human vision occurs during storage at 25 °C for at least 24 hours after preparation ofthe autodepositing liquid composition, in the absence of con- tact of the autodepositing liquid composition with any metal, particularly any metal that dissolves in the autodepositing composition to produce therein metal cations with a charge of at least two, or other material that reacts with the autode¬ positing liquid composition; and (C) a dissolved accelerator component, selected from the group consisting of acids, oxidizing agents, and complexing agents, sufficient in strength and amount to im¬ part to the total autodepositing liquid composition an oxidation-reduction poten¬ tial that is at least 100 millivolts (hereinafter usually denoted "mV") more oxidiz¬ ing than a standard hydrogen electrode (hereinafter usually abbreviated "SHE"); and, optionally, one or more ofthe following: (D) a component of pigment, filler, or other dispersed solid phase materials other than the materials that constitute any part of any ofthe preceding components; (E) a component of dyes or other dissolved coloring materials other than materials that constitute any part of any ofthe preceding components; (F) a component of solvent in which constituents of component (A) that are insoluble in water were dissolved during some step in the preparation ofthe autodepositing liquid composition, other than materials that constitute any part of any ofthe pre¬ ceding components; (G) a component of coalescing agent, other than materials that form any part of any ofthe preceding components; (H) a plasticizer component, other than materials that constitute part of any of the preceding components; (J) a component of non-polymeric cross-linking agents and monomers that do not constitute part of any other component described above but are chemically react¬ ive with epoxy resin constituents of component (A) at a temperature of 165 °C. In this description and hereinafter: The phrase "film forming polymer molecules" means that the molecules so described, when separated from any water in which they are dis- persed or dissolved and dispersed, by drying or other removal ofthe water at a tempera¬ ture of at least 30 °C from a substantially uniformly thick continuous liquid layer of a DDS ofthe film forming polymer molecules, will spontaneously form a continuous body that is solid at 30 °C; the term "solvent" means a single phase, whether consisting of a single chemical substance or a mixture of chemical substances, that (i) is liquid at 25 °C and (ii) is not constituted exclusively of water and inorganic solutes only; and the term "coalescing agent" means a material that (i) is liquid at 100 °C, (ii) has a boiling point at normal atmospheric pressure that is at least 110 °C or preferably, with increasing pref¬ erence in the order given, at least 120, 130, 140, 150, 160, or 165 °C and independently is not more than 300 °C, or preferably, with increasing preference in the order given, not more than 290, 280, 270, 265, 260, 255, 250, 245 °C, and (iii) promotes the formation of unblistered coatings, as determined by comparison ofthe degree of blistering obtained, under identical processing conditions, by (i) autodeposition from an autodepositing liquid composition containing the material being tested for its coalescing properties, followed by cure ofthe film thus deposited and (ii) an otherwise identical process in which the ma- terial being tested for its coalescing properties is replaced, in the autodepositing liquid composition used in the process, by an equal mass of water. In addition to a complete autodepositing liquid composition as described above, another embodiment ofthe invention is a liquid dispersion in water of epoxy resin and, optionally, other components that is useful as a replenisher composition to replace poly- mer molecules consumed by use of an autodepositing liquid composition according to the invention. Such a liquid replenisher composition according to the invention compris¬ es, preferably consists essentially of, or more preferably consists of, water and: (A 1 ) an amount of dispersed or both dispersed and dissolved film forming polymer molecules that include the same chemical substances in the same relative propor- tions as are consumed during use from component (A) of the autodepositing liquid composition to be replenished, said amount being at least 5 times greater than the amount of the same chemical substances in the autodepositing liquid composition to be replenished; and (B') an emulsifying agent component in sufficient quantity to emulsify all dispersed constituent molecules of component (A 1 ) so that, in the liquid replenisher compo¬ sition, no separation or segregation of bulk phases that is perceptible with normal unaided human vision occurs during storage at 25 °C for at least 5 days after preparation ofthe liquid replenisher composition, in the absence of contact ofthe liquid replenisher composition with any metal, particularly any metal that dis¬ solves in the autodepositing composition to produce therein metal cations with a charge of at least two, or other substance that reacts with the liquid replenisher composition; and, optionally, one or more ofthe following: (C) a dissolved accelerator component, selected from the group consisting of acids, oxidizing agents, and complexing agents; (D') a component of pigment, filler, or other dispersed solid phase materials other than the materials that constitute any part of any ofthe preceding components; (E') a component of dyes or other dissolved coloring materials other than materials that constitute any part of any ofthe preceding components; (F') a component of solvent in which constituents of component (A) that are insoluble in water were dissolved during some step in the preparation ofthe liquid replen¬ isher composition, other than materials that constitute any part of any ofthe pre- ceding components; (G 1 ) a component of coalescing agent, other than materials that form any part of any ofthe preceding components; (H') a plasticizer component, other than materials that constitute any part of any ofthe preceding components; (J') a component of non-polymeric cross-linking agents and monomers that do not constitute part of any other component described above but are chemically react¬ ive with epoxy resin constituents of component (A) at a temperature of 165 °C. A process according to the invention for making a liquid replenisher composition according to the invention as described above comprises steps 1 of: ■ " ^ The word "step" in this specification and in the claims, unless explicitly noted to the contrary, is to be understood as the equivalent ofthe phrase "part ofa process", without any im¬ plication that all the actions recited in the step are necessarily continuous in time. (I) providing a collection of film forming polymer molecules suitable for component (A 1 ) as described above; (II) dissolving the entire collection of film forming polymer molecules provided in step (I) in a solvent component to form a single phase solution from the com- bination of the collection of film forming polymer molecules and the solvent component; (III) emulsifying the single phase solution formed in step (II), along with other materi¬ als as needed, into a volume of water, so as to form a DDS in water of at least those parts of the solution that constitute component (A) as recited above, said DDS comprising, preferably consisting essentially of, or more preferably consist¬ ing of, water, components (A') and (B 1 ) as recited above, and, optionally, one or more of components (C) through (J 1 ) as recited above. A process according to the invention for making an autodepositing liquid compo¬ sition according to the invention as described above comprises steps of: (I 1 ) providing a collection of film forming polymer molecules suitable for component (A) as described above; (II') dissolving the entire collection of film forming polymer molecules provided in step (I') in a solvent component to form a single phase solution from the com¬ bination of the collection of film forming polymer molecules and the solvent component; (III') emulsifying the single phase solution formed in step (IF), along with other mater¬ ials as needed, into a volume of water, so as to form a DDS in water of at least those parts of the solution that constitute component (A) as recited above, said DDS comprising, preferably consisting essentially of, or more preferably consist- ing of, water, components (A) and (B) as recited above, and, optionally, one or more of components (C) through (J) as recited above; and, if component (C) as described above is not present in said DDS, (IV) adding to the DDS formed in step (III') sufficient additional material to provide component (C) and, optionally, any one or more of components (D) through (J) as recited above that is not already present in the DDS formed in step (III'). A process according to the invention for using an autodepositing liquid composi¬ tion according to the invention in its simplest form comprises, preferably consists essenti- ally of, or more preferably consists of, steps of: (I") contacting a solid active metal surface with an autodepositing liquid composition according to the invention for a sufficient time to form over the contacted solid active metal surface a wet continuous coating which contains molecules derived from component (A) ofthe autodepositing liquid composition according to the invention, the wet continuous coating being sufficiently coherent and adherent to the metal surface for at least some part thereof to remain on the metal surface against the force of natural ambient gravity when the metal surface and any non- adherent part ofthe autodepositing liquid composition according to the invention are removed from contact with each other; (II") after step (I"), removing the wet continuous coating formed over the metal sur¬ face from contact with any non-adherent part ofthe autodepositing liquid compo¬ sition according to the invention with which it was contacted in step (I") and, optionally, rinsing the coating with at least one liquid rinse composition that is not an autodepositing liquid composition; and (III") after step (II"), expelling from the wet continuous coating a sufficient amount of water so as to convert the wet continuous coating into a dry continuous coating. Description of Preferred Embodiments For reasons of practicality and economy with commercially available equipment, it is normally preferred to carry out process step (III') or (III") as described above in at least two stages: (.1 ) a primary mixing stage in which there is formed a preliminary DDS which is sufficiently stable that no separation or segregation of bulk phases in the prelim¬ inary DDS that is perceptible with normal unaided human vision would occur during storage at 25 °C for at least 5 hours after preparation ofthe preliminary DDS, in the ab- sence of contact ofthe preliminary DDS with any metal or other material that can react with or dissolve into the preliminary DDS to form solute cations with a charge of at least two therein; and (.2) a particle size refinement stage, in which the preliminary DDS formed in stage (.1), preferably before it shows any visually perceptible evidence of phase segregation, is forced as least once through a narrow aperture of carefully con- trolled size and shape under high pressure, so as to generate a flow velocity high enough to produce cavitation, turbulence, and/or shear forces which divide the product into par¬ ticles that meet the size distribution criteria specified for component (A) or (A') above. Stage (.1) can be conveniently achieved by use of any of a wide variety of labor¬ atory or commercial scale equipment known generally in the art as "high shear" or "high speed" mixers. In this stage emulsifying agent and water are generally added slowly to¬ gether to the solution ofthe film forming polymer molecules, with constant agitation, un- til the mixture, which initially becomes increasingly more viscous as more water is add¬ ed, at least begins to become substantially less viscous with further additions of water, indicating inversion ofthe emulsion from one of water in "oil" to the desired final "oil" in water emulsion, having water and constituents dissolved in water as the continuous phase. If "high shear" mixing equipment is used in this stage, the emulsion produced in this mixing stage will normally have a mean particle diameter no more than 450 nm, while if the more common "high speed" type of mixing equipment is used instead, an emulsion with a mean particle diameter of about 1000 nm is usually produced, in both cases with preferred materials as described further below. Stage (.2) is physically analogous to the homogenization of milk and may be ac- complished with equipment suited to that and similar purposes. Preferred equipment is exemplified by RANNE™ Hyper Homogenizers supplied by the APV Homogenizer Di¬ vision of APV Corp., Wilmington, Massachusetts, USA and MICROFLUIDIZER™ Pro¬ cessors supplied by Microfluidics International Corporation, Newton, Massachusetts, USA. The operations of step (.2) may be repeated as many times as desired, without ap- parent harm to the resulting product, and with substantially to slightly increased particle refinement normally being achieved with each of at least the first few repetitions. If the initial mean particle diameter ofthe preliminary DDS is more than 500 nm, at least one repetition of Stage (.2) is normally preferred, in order to achieve a preferred degree of stability of the finally prepared autodepositing liquid composition, while if the initial mean particle diameter is less than 450 nm, a single mixing in Stage (.2) is often suffi¬ cient. The amount of component (A) in a working autodepositing composition accord¬ ing to the invention preferably is at least, with increasing preference in the order given, 2.0, 2.5, 3.0, 3.5, 4.0, or 4.5 % ofthe total amount ofthe composition and independently preferably is not more than, with increasing preference in the order given, 50, 30, 25, 20, 10, 9.0, 8.5, 8.0, 7.5, 7.0, 6.5, 6.0, or 5.5 % ofthe total amount ofthe composition. Numerous types of epoxy resin are known in the art and may be utilized in this invention. Such resins are often described by the type of central organic moiety or moie¬ ties to which the 1,2-epoxy moieties are attached in a monomer unit having at least two epoxy moieties. Non-exclusive examples of such central moieties are those derived from bis-phenol A and its analogs in which one or two -NH 2 moieties are substituted for an equal number of -OH moieties in bis-phenol A; novolak condensates of formaldehyde with phenol and substituted phenols and their amino analogos, the condensates contain¬ ing at least two aromatic nuclei; triazine; hydantoin; and other organic molecules con¬ taining at least two hydroxyl and/or amino moieties each, in each instance with as many hydrogen atoms deleted from hydroxy and/or amino moieties in the parent molecule as there are epoxy moieties in the molecules of epoxy resin; optionally, the 1,2-epoxide moieties may be separated from the central moieties as defined above by one or more, preferably only one, methylene groups. Oligomers of such monomers, either with them¬ selves or with other organic molecules containing at least two hydroxyl and/or amino moieties each, may also serve as the central organic moiety. Preferably, independently for each criterion stated, the particle size distribution of those parts of component (A) in an autodepositing liquid composition according to the invention or of component (A') in a liquid replenisher composition according to the in¬ vention that are constituted of molecules for which the epoxide equivalent weight 2 is at least 374 conforms to the following criteria, each independently ofthe others, or most preferably to all: The ratio ofthe mean light scattering particle diameter 3 in nm divided by the cube root of the average epoxide equivalent weight for the molecules of component (A) expressed in daltons, this ratio being usually briefly denoted hereinafter as the "diameter ratio", is not more than, with increasing preference in the order given, 2 The epoxide equivalent weight is defined as the molecular weight divided by the num¬ ber of 1,2-epoxy moieties in the molecule. The epoxide equivalent weight of commercial resins is generally specified by the supplier as a range; when such materials are used, the midpoint of the stated range is taken as the epoxide equivalent weight for calculation of diameter ratios. 3 These particle diameter values generally may most conveniently be measured in the ab¬ sence of any substantial amount in component (A) of any epoxy resin for which the epoxide equivalent weight is less than or equal to 200. Such low molecular weight epoxy resins are preferably used only as cross-linking agents in formulations according to this invention, and do not need any particular precautions or special techniques to become properly suspended in the final DDS formed, because such low molecular weight epoxy resins are liquids rather than solids at the normal temperature of addition to a composition according to this invention. 29.2, 28.1, 27.0, 26.0, 25.0, 24.0, 23.5, 23.0, 22.5, 22.0, 21.7, or 21.4 {nm/(dalton % )}; no more than 1.0 % ofthe light scattering particles volume in the distribution consists of particles with a diameter ratio larger than, with increasing preference in the order given, 44.2, 43.1, 42.0, 41.0, 40.0, 39.0, 38.0, 37.0, 36.5, 36.0, 35.5, 35.0, or 34.5 {nm/(dalton 1A )} ; no more than 25 % ofthe light scattering particles volume in the distri¬ bution consists of particles with a diameter ratio larger than, with increasing preference in the order given, 25.1, 24.0, 23.0, 22.5, 22.0, 21.5, 21.0, 20.7, or 20.4 {nm/(dalton % )}; no more than 50 % ofthe light scattering particles volume in the distribution consists of particles with a diameter ratio larger than, with increasing preference in the order given, 20.4, 19.0, 18.5, 18.0, 17.5, 17.0, 16.8, or 16.6 {nm/(dalton % )}; no more than 75 % ofthe light scattering particles volume in the distribution consists of particles with a diameter ratio larger than, with increasing preference in the order given, 17.8, 17.3, 17.0, 16.5, 16.0, 15.5, 15.0, 14.5, 14.0, or 13.6 {nm/(dalton % )}. Preferably, with increasing preference in the order given, at least 10, 20, 30, 40, or 45 % ofthe molecules of component (A) of an autodepositing liquid composition ac¬ cording to the invention are molecules that contain at least two 1 ,2-epoxide moieties and have an epoxide equivalent weight of at least 374, and independently, with increasing preference in the order given, at least 10, 20, 30, 40, 50, 60, 70, 75, 80, 85, or 89 % of the molecules containing at least two 1,2-epoxide moieties in component (A) of an auto- depositing liquid composition according to the invention are selected from the group con¬ sisting of molecules with an epoxide equivalent weight that is at least, with increasing preference in the order given, 446, 574, 731, 873, 1015, 1158, 1299, 1442, 1584, 1726, 1868, or 2010 and independently preferably is, with increasing preference in the order given, not more than 4527, 3816, 3106, 2721, 2437, 2295, or 2152. Independently, it is preferred that an autodepositing liquid composition according to the invention contain a subcomponent (AoJ) selected from the group consisting of molecules having exactly two 1,2-epoxide moietes and an epoxide equivalent weight that is not more than 200 in an amount that is, with increasing preference in the order given, at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 % ofthe amount of molecules having two or more 1 ,2-epoxide moieties and an epoxide equivalent weight of at least 873 and independently, but only if at least 90 % of component (A) is constituted of molecules having at least two 1,2-epoxide moieties, preferably is not more than, with increasing preference in the order given, 25, 24, 23, 22, 21, or 20 % ofthe amount of molecules having two or more 1,2-epoxide moieties and an epoxide equivalent weight of at least 873, because excessive rinse-off of uncured wet autodeposited coatings has sometimes been observed when a higher ratio of epoxides with low epoxide equivalent weights to those with higher molec- ular weights was used and there was little or no other film forming material in component (A) to stabilize the wet autodeposited films. In contrast, when other film forming materi¬ als, such as those contained in most commercially available acrylic polymer latexes, are also included in substantial amounts in component (A), larger ratios of molecules with low epoxide equivalent weights may be included and can even be preferred, if the amount of other film forming polymer is sufficient to prevent excessive rinse-off of the uncured wet autodeposited films. In addition to the diepoxide molecules of subcomponent (AoJ), component (A) and/or component (J) as described above preferably include(s) a subcomponent (CL) of cross-linking agents selected from the group consisting of both ofthe following molecu- lar types: (CL.l) molecules each containing at least two functional groups, such as amine, amide, imine, thiol, hydroxyl, carboxyl, and carboxylic acid anhydride, that are capable of rapid chemical addition reactions with epoxy moietiess when mixed with mol¬ ecules containing such epoxy moieties and heated to a temperature of at least 100 °C; and (CL.2) molecules that are not part of component (CL.l) and that contain at least two blocked isocyanate groups, each such group being blocked with a conventional blocking agent or internally blocked by formation ofa uretdione structure, so that the blocked isocyanate group does not react at any appreciable rate at room tem- perature with hydroxyl groups but does react rapidly with such groups after being unblocked by heating, unblocking occurring at a temperature that is at least 100 °C and preferably is, with increasing preference in the order given, at least 105, 110, 1 15, or 120 °C and independently preferably is, with increasing preference in the order given, not more than 190, 185, 180, 175, 170, or 165 °C. If subcomponent type (CL.1 ) is used, its constituents preferably have terminal hy¬ droxyl, amine, carboxylic acid, or amide groups. If subcomponent type (CL.2) is used, its constituents preferably are chosen from molecules that conform to general formula (II): O H H O H O II I I II I II (ii) , B-C-N-R- (N-C-O-R ' ) m -N-C-B ' wherein each of B and B 1 independently is a monovalent moiety formed by removing the most easily ionized hydrogen atom from an amine, alcohol, amide, or oxime molecule, or B and B 1 are joined to each other to form a uretdione; each of R and R' independently is a divalent hydrocarbon or carbonyl-hydrocarbon moiety derived by removing from any hydrocarbon, or from an oxyhydrocarbon in which all oxygen atoms present are in car¬ bonyl groups, any two hydrogen atoms not attached to the same carbon atom, said dival¬ ent hydrocarbon or carbonyl-hydrocarbon moiety having from 2 to 20 carbon atoms and having no unsaturation except aromatic and carbonyl unsaturation; and m is an integer from 0 - 20, preferably, with increasing preference in the order given, not more than 15, 10, 8, 6, 4, 3, 2, 1, or 0. The blocking groups B and B', which preferably are the same or are joined to form a uretdione, can be derived from any suitable aliphatic, cycloali¬ phatic, aromatic, or alkylaromatic monoalcohol, monoamide, monoamine, or monoox- ime. Ketoximes are especially useful when unblocking at relatively low temperatures such as 120 °C is desired, although their instability in acidic solutions may become a problem if an autodepositing composition according to the invention is to be stored for a considerable time without being used. More sterically hindered and/or more acid stable blocking groups, such as those derived from the lactam of 6-aminohexanoic acid and/or benzotriazole are preferred if unblocking is desired to begin at a substantial rate only at or above 160 °C. In some instances, as described in the examples below, both types of blocking groups are used, in order to effect part ofthe cross-linking during an early part ofthe cure and part ofthe cross-linking during a later part ofthe cure. The preferred cross-linking agents as specified above are believed to be reactive with hydroxyl groups as well as with any intact epoxide groups that may be present in the relatively acidic environment of an autodepositing composition according to this in¬ vention, where most or all of such groups are believed likely to be hydrolyzed to produce hydroxyl groups. Furthermore, even if epoxy groups remain as such, there will normally be at least some hydroxyl groups available for cross-linking reactions such as esterifica¬ tion and etherification. Other constituents of component (A) that do not contain 1 ,2- epoxide moieties may also, and preferably do, have hydroxyl, carboxyl, or similarly re- active groups available for cross-linking reactions. Satisfactory autodeposited coatings for most purposes can be produced when mol¬ ecules containing at least two 1,2-epoxide moieties are substantially the only constituents of component (A) as defined above. However, it is also possible, and can be advantage- ous, especially to achieve economy without unduly sacrificing quality, to utilize blends ofthe epoxy resin with other types of polymers, particularly acrylic polymers containing some acrylic acid monomer residues, which can react with the hydroxyl groups on epoxy resins to form ester groups and thereby cross-link the polymer coating formed by auto¬ deposition. Primarily for reasons of economy and commercial availability, it is generally pre¬ ferred to utilize epoxy resins derived from bis-phenol A in this invention. More particu¬ larly, epoxy moiety containing molecules utilized in this invention preferably conform to general chemical formula (I): O H where A * C H . and n is an integer from 0 to 50. Preferably, independently for each criterion stated, the particle size distribution of those parts of component (A) in an autodepositing liquid composition according to the invention or of component (A') in a liquid replenisher composition according to the invention constituted of molecules for which the value of n in general formula (I) above is at least one conforms to the following criteria: The ratio ofthe mean light scattering particle diameter in nm divided by the cube root ofthe average epoxide equivalent weight 4 for the molecules of component (A) expressed in daltons, this ratio being usually 4 This value, for resins conforming to general formula I, is equal to half of the average molecular weight. The epoxide equivalent weight of commercial resins is generally specified by the supplier as a range; when such materials are used, the midpoint ofthe stated range is taken as the epoxide equivalent weight for calculation of diameter ratios. briefly denoted hereinafter as the "diameter ratio", ofthe part of component (A) or (A) constituted of molecules for which the value of n in general formula (I) above is at least one is not more than, with increasing preference in the order given, 29.2, 28.1, 27.0, 26.0, 25.0, 24.0, 23.5, 23.0, 22.5, 22.0, 21.7, or 21.4 {nm/(dalton % )}; no more than 1.0 % of the light scattering particles volume in the dispersion consists of particles with a diameter ratio larger than, with increasing preference in the order given, 44.2, 43.1, 42.0, 41.0, 40.0, 39.0, 38.0, 37.0, 36.5, 36.0, 35.5, 35.0, or 34.5 {nm (dalton % )}; no more than 25 % ofthe light scattering particles volume in the dispersion consists of particles with a diameter ratio larger than, with increasing preference in the order given, 25.1, 24.0, 23.0, 22.5, 22.0, 21.5, 21.0, 20.7, or 20.4 {nm/(dalton , l ) } ; no more than 50 % of the light scat¬ tering particles volume in the dispersion consists of particles with a diameter ratio larger than 20.4, 19.0, 18.5, 18.0, 17.5, 17.0, 16.8, or 16.6 {nm/(dalton > )}; no more than 75 % ofthe light scattering particles volume in the dispersion consists of particles with a diam¬ eter ratio larger than, with increasing preference in the order given, 17.8, 17.3, 17.0, 16.5, 16.0, 15.5, 15.0, 14.5, 14.0, or 13.6 {nm/(dalton % )}. Preferably, with increasing preference in the order given, at least 10, 20, 30, 40, or 45 % ofthe molecules in component (A) of an autodepositing liquid composition ac¬ cording to the invention conform to formula I when n has a value of at least 1 , and inde¬ pendently, with increasing preference in the order given, at least 10, 20, 30, 40, 50, 60, 70, 75, 80, 85, or 89 % ofthe molecules conforming to formula I in component (A) of an autodepositing liquid composition according to the invention are selected from the group consisting of molecules in which the average value of n in formula (I) is at least, with increasing preference in the order given, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 and independently preferably is, with increasing preference in the order given, not more than 30, 25, 20, 18, 16, 15, or 14. Independently, it is preferred that an autodepositing liquid composition according to the invention contain a subcomponent (AoJ) selected from the group consisting of di¬ glycidyl ether molecules with an epoxide equivalent weight that is not more than 200 in an amount that is, with increasing preference in the order given, at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 % ofthe amount of molecules conforming to formula (I) when n has a value of 5 or greater and independently, but only if at least 90 % of component (A) is constitut¬ ed of molecules conforming to formula (I), preferably is not more than, with increasing preference in the order given, 25, 24, 23, 22, 21 , or 20 % ofthe amount of molecules con¬ forming to formula I when n has a value of 5 or greater, because excessive rinse-off of uncured wet autodeposited coatings has sometimes been observed when a higher ratio of diglycidyl ethers with low epoxide equivalent weights to the molecules conforming to formula (I) when n has a value of 5 or greater was used and there was little or no other film forming material in component (A) to stabilize the wet autodeposited films. In con¬ trast, when other film forming materials, such as those contained in most commercially available acrylic polymer latexes, are also included in substantial amounts in component (A), larger ratios of diglycidyl ethers with low epoxide equivalent weights may be in- eluded and can even be preferred, if the amount of other film forming polymer is suffi¬ cient to prevent excessive rinse-off of the uncured wet autodeposited films. Most preferably, the diglycidyl ether of bisphenol-A, corresponding to general formula (I) when n = 0 and having an epoxide equivalent weight of 182 daltons, is used as subcomponent (AoJ) . Subcomponent (AoJ) when present will form part of compon- ent (A) and/or part or all of component (J) as described above. When subcomponent (CL.2) is present in an autodepositing liquid composition according to the invention in which substantially all ofthe molecules containing at least two 1,2-epoxide moieties conform to general formula (I), the ratio of (i) the number of gram-equivalents ofthe total of epoxy and hydroxyl groups in that part of component (A) that conforms 5 to general formula (I) to (ii) the number of gram-equivalents ofthe total of isocyanate and blocked isocyanate groups in subcomponent (CL.2) preferably is, with increasing preference in the order given, at least 1.0, 2.0, 3.0, 3.5, 3.8, 4.0, or 4.1 and in¬ dependently preferably is, with increasing preference in the order given, not more than 50, 45, 40, 35, 30, 28, 26, 24, 23, 22, 21, or 20. Satisfactory autodeposited coatings for most purposes can be produced when epoxy resins, particularly those constituted of molecules conforming to general formula (I), are substantially the only constituents of component (A) as defined above. However, 5 As with all other materials as already noted generally above, the word "conforms" in this instance is to be interpreted as "conformed at the time of first addition to a mixture as described herein." Therefore, even if the terminal epoxy groups in general formula (I) have hydrolyzed after addition, these groups are still counted for purposes ofthe calculation described in this paragraph as single epoxy groups rather than as the up to two hydroxyl groups that they may have become after addition. it is also possible, and can be advantageous, especially to achieve economy without un¬ duly sacrificing quality, to utilize blends ofthe epoxy resin with other types of polymers, particularly acrylic polymers containing some acrylic acid monomer residues, which can react with the hydroxyl groups on epoxy resins to form ester groups and thereby cross- link the polymer coating formed by autodeposition. Component (B) preferably includes a subcomponent (B.a), which may be the only constituent of component (B), selected from the group consisting of anionic surfactants, and in many circumstances it may advantageously contain other types of emulsifying agents also. Preferred anionic surfactants are ether sulfates that conform to general form- ula (III): M + Ό-SO 2 -O-(CH 2 -CH 2 -O) P -R" (m), where M + represents a monovalent cation or monvalent fraction of cation of higher val¬ ence, preferably sodium or ammonium, more preferably ammomum; p is a positive inte¬ ger that preferably is at least, with increasing preference in the order given, 2, 3, or 4; and R" represents an alkyl or alkylaryl moiety, more preferably an alkyl phenol moiety. In¬ dependently R" preferably has at least, with increasing preference in the order given, 8, 10, 12, 13, 14, or 15 carbon atoms and independently preferably has not more than, with increasing preference in the order given, 30, 28, 26, 24, 22, or 20 carbon atoms. Suitable commercially available anionic emulsifiers include Dowfax™ 2A-1 (sodium salt of alkyl- ated diphenyl oxide disulfonate); Abex™ 26-5; Texapon™ E-12 and K-12; Rhodapex™ CO-128, -433, and -436 and EP-100, -110, -115, -120, and -227; Disponsil™ AES-13, and Aerosol™ OT (sodium dioctylsulfosuccinate). The single most preferred anionic emulsifying agent is Rhodapex™ CO-436, which is reported by its supplier to be an ammonium salt of sulfonated nonylphenol ethoxylate and to contain 58 % of this active ingredient. The preferred amount of active anionic emulsifying agent used is, with in¬ creasing preference in the order given, not less than 0.1, 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.4, or 1.5 %, based on the content in an autodepositing liquid composition according to the invention ofthe sum of molecules conforming to general formula I and any other parts of component (A) that do not include sufficient anionic moieties in the polymer mole- cules themselves to be "self-emulsifying" 6 , and independently preferably is, with increas¬ ing preference in the order given, not more than 5, 4, 3.0, 2.7, 2.4, 2.2, 2.0, 1.9, 1.8, or 1.7 %, on the same basis. Accelerator component (C) is preferably chosen from the group consisting of hy- drofluoric acid and its salts, fluosilicic acid and its salts, fluotitanic acid and its salts, fer¬ ric ions, acetic acid, phosphoric acid, sulfuric acid, nitric acid, hydrogen peroxide, peroxy acids, citric acid and its salts, and tartaric acid and its salts. More preferably, the acceler¬ ator comprises, still more preferably consists essentially of, or most preferably consists ofthe following subcomponents: (C.1 ) a total amount of fluoride ions, which may be simple or complex fluoride ions or both, that provides a concentration thereof in the total autodepositing liquid com¬ position of at least 0.4 g/L and more preferably of, with increasing preference in the order given, at least 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, or 1.9 g/L and independ¬ ently preferably provides to the autodepositing liquid composition a total concen- tration of fluoride ions that is, with increasing preference in the order given, not more than 5, 4.5, 4.0, 3.7, 3.4, 3.1, 2.9, 2.7, 2.5, 2.3, or 2.1 g/L; (C.2) an amount of dissolved trivalent iron atoms that is at least 0.003, or, with increas¬ ing preference in the order given, at least 0.007, 0.010, 0.013, 0.016, 0.019, 0.022, 0.025, or 0.027 and independently preferably is, with increasing prefer- ence in the order given, not more than 0.20, 0.15, 0.11, 0.090, 0.070, 0.055, 0.045, 0.040, 0.035, or 0.030; and (C.3) a source of hydrogen ions in an amount sufficient to impart to the autodeposition composition a pH that is at least 1.6, or preferably is, with increasing preference in the order given, at least 1.7, 1.8, 1.9, 2.0, or 2.1 and independently preferably is, with increasing preference in the order given, not more than 5, 4.5, 3.8, 3.6, 3.4, 3.2, 3.0, 2.8, 2.6, 2.4, or 2.3; and, optionally, 6 As described in detail in U. S. Patent 5,352,726 of Oct. 4, 1994 to Hall at column 6 lines 31 - 44, column 7 line 11 through column 8 line 7, and column 8 line 64 through column 9 line 23, which portions are, to the extent not inconsistent with any explicit statement herein, hereby incoφorated herein by reference, when utilizing addition polymers of vinyl monomers as the principal ingredient ofthe binder for an autodepositing liquid composition, the emulsifying agent is preferably incoφorated into the polymer chain. Any polymers of this type that are present as part of component (A) herein do not need "external" emulsifying agent component (B) as described herein. (C.4) hydrogen peroxide. It should be understood that subcomponents (Cl) through (C.3) need not all be derived from different materials. Hydrofluoric acid, in particular, is preferred as a source for both ( l) and (C.3), and ferric fluoride can supply both (Cl) and (C.2). independently of other preferences, an autodepositing liquid composition accord¬ ing to the invention, when used to coat bare steel, preferably has an oxidation potential, measured by the potential ofa platinum or other inert metal electrode in contact with the autodepositing liquid composition, that is, with increasing preference in the order given, at least 150, 175, 200, 225, 250, 275, 290, or 300 mV more oxidizing than a SHE and in- dependently preferably is, with increasing preference in the order given, not more than 550, 525, 500, 475, 450, 425, 410, or 400 mV more oxidizing than a SHE. Pigment and/or filler component (D) and soluble colorant component (E) may generally be selected for compositions according to this invention from materials estab¬ lished as satisfactory for similar uses in other autodepositing liquid compositions. Solvent component (F) is generally required in the preparation of autodepositing liquid compositions according to this invention, but it is not believed in most cases to contribute any desirable characteristic to the final autodepositing liquid compositions formed, although it may function as a coalescing agent. The preferred solvents, however, are not particularly effective coalescing agents when used alone. The solvent component may be removed, when desired or necessary to comply with anti-pollution requirements, by means known in the art, such as distillation under reduced pressure after formation of an oil-in-water type dispersion ofthe desired final components of an autodepositing li¬ quid composition according to the invention. However, in many cases the solvents do not diminish the technical benefits of the final autodepositing liquid compositions ac- cording to the invention, and may be left in place in the autodepositing liquid composi¬ tions according to the invention if legal requirements are not thereby violated. Any such residual solvent will normally be expelled during cure ofthe autodeposited coatings. The most preferred solvents are mixtures of (i) aromatic hydrocarbons with from 6 to 10 carbon atoms and (ii) ketones with from 3 to 8 carbon atoms. Preferably, with increasing preference in the order given, the percentage of each of components (i) and (ii) in the mixture is at least 10, 20, 25, 30, 35, 40, or 45 %. The single most preferred constituent of type (i) is toluene and the single most preferred constituent of type (ii) is methyl isobutyl ketone. Generally, the presence ofa coalescing agent component (G) in an autodepositing liquid composition according to the invention is preferred. This component is preferably selected from the group consisting of monoethers and monoesters of glycols, preferably glycols with at least one terminal hydroxy group. Monoethers of ethylene glycol are readily available and effective in blistering reduction but are restricted in use by anti-pol¬ lution laws in many locations and also have been found to be more likely than monethers of propylene glycol to destabilize the emulsions formed in products according to the in¬ vention, so that monoethers of propylene glycol, particularly the n-butyl and phenyl monoethers of propylene glycol, are preferred from this class. When glycol monoethers are used, their percentage in an autodepositing liquid composition according to the inven¬ tion preferably is, with increasing preference in the order given, at least 5. 10, 12, 14, 16, 18, or 19 % ofthe total solids in components (A) and (J) (or (A') and (J')) ofthe compo¬ sition and independently preferably is, with increasing preference in the order given, not more than 30, 28, or 26 % on the same basis. Monoesters are slightly less preferred than monoethers where maximum corrosion resistance in the final product is needed, but are generally effective at lower concentrations and may therefore be preferred if economy and/or compliance with stringent solvent emission standards is more important than max¬ imum corrosion resistance. A particularly preferred monoester is 2,2,4-trimethyl-l,3- pentanediol mono 2-methyl propionate. This and other monoesters if used preferably are present in an amount of at least 0.5 % ofthe total autodepositing liquid composition and more preferably, with increasing preference in the order given, are present in amounts of at least 1.0, 1.5, 2.0, 2.5, or 2.9 % but, independently, not more than, with increasing preference in the order given, 10, 8.0, 6.0, 5.0, 4.5, 4.0, 3.5, or 3.1 %. The invention and its benefits may be further appreciated from consideration of the examples and comparisons below. General Procedures Applicable to Many Specific Examples Preparation of Epoxy Resin Dispersions - with Microfluidizer™ Apparatus as the Only Dispersing Apparatus A total of 1 part of epoxy resin(s), cross-linking agent(s), and water-insoluble co¬ alescing agent(s) if the latter were used, and any other substantially water insoluble liquid materials desired in the dispersion was dissolved in a mixture of 1 part each of toluene and methyl isobutyl ketone, with agitation if needed until a homogeneous organic solu¬ tion was achieved. A separate aqueous solution of the emulsifying agent component in 6 parts of deionized (hereinafter usually abbreviated "DI") water was also prepared. (The proportions between or among the epoxy resin(s), cross-linking agent(s), emulsifying agent(s), and other material(s) used in individual instances is shown in tables below.) The organic solution prepared as noted was then introduced into the injection port of a Model 110F MICROFLUIDIZER™ dispersing apparatus, and the aqueous solution prepared as noted above was added to the reservoir ofthe same apparatus. The air pres¬ sure supply to the apparatus was raised to the maximum level, and an empty container of adequate size was placed to receive the dispersion output from the apparatus. The MI¬ CROFLUIDIZER™ apparatus was then operated according to directions supplied with it to produce an output dispersion; if necessary, because ofthe total volume ofthe dis¬ persion to be prepared, additional amounts ofthe aqueous and organic solutions prepared as described next above were added to the apparatus until all of both solutions had passed once through the dispersion mechanism ofthe apparatus. The primary dispersion prepared as described next above was then reintroduced into the reservoir only of the MICROFLUIDIZER™ apparatus and passed through it again, with no new material injected, for further particle size refinement. The initially refined dispersion was normally passed through again, and the entire process repeated, with the output dispersion from each repetition becoming the input dispersion for the next repetition, until all material in the dispersion had passed through the MICROFLU¬ IDIZER™ apparatus four to eight times, to produce a finally refined high volume disper¬ sion. This high volume dispersion was then introduced into a conventional rotary evap- orator apparatus, in which rotation at a rate of 2 - 5 revolutions per minute (hereinafter usually abbreviated "rpm") was begun and the overpressure was initially reduced to about 85 millibars. The vapor evolved from the dispersion in the rotary evaporator appa¬ ratus was condensed and collected in a volume graduated container, and overpressure was gradually reduced, with care to avoid an extent of foaming that would carry non-vap- orized material past the trap for such material in the apparatus, until a volume of liquid that would, if it were pure water, have a mass of 50 % of the original aqueous and organ¬ ic solutions from which the dispersion was made, had collected. (The collected liquid in fact includes much or all of the organic solvents from the organic solution used to make the high volume dispersion, in addition to water.) Evaporation was then discontin¬ ued by admitting atmospheric air to return the overpressure in the apparatus to the pre¬ vailing ambient pressure. The unevaporated dispersion remaining in the rotary evaporat- or apparatus was then retained as concentrated dispersion and was assumed to contain all ofthe originally added materials that are substantially less volatile than water. Any water-soluble coalescents used were post-added with stirring for 2 to 2.5 hours to these concentrated dispersions. Preparation of Autodepositing Liquid Compositions from the Dispersions as Above An amount of concentrated dispersion to provide solids that will constitute 5 % of the final autodepositing liquid composition was dissolved in an amount of DI water that, together with the concentrated dispersion, constituted about 90 % of the desired final volume ofthe autodepositing liquid composition. To this was added, with high me¬ chanical agitation, but avoiding any splashing or foaming, a concentrated solution of fer- ric fluoride, hydrofluoric acid, and hydrogen peroxide in amounts sufficient to provide 1.9 g/L of dissolved fluoride ions and 0.027 of iron(III) atoms after final dilution to the desired volume with more DI water, and to give the final autodepositing liquid com¬ position an oxidation-reduction potential that is 350±50 mV more oxidizing than a SHE. Preparation and Processing of Test Specimens Rectangular test panels of cold rolled steel sheets, with a hole for hanging near the center of one ofthe shorter ends, were the usual substrates coated. Maintenance of Autodepositing Liquid Composition During Use The bath temperature was measured using a dialface thermometer with a sensing element encased in stainless steel. The operating temperature was maintained within the range of 21 to 24 °C The oxidation-reduction potential was constantly monitored with an appropriate instrument and electrodes as known to those skilled in the art. Hydrogen peroxide solu¬ tion in water was added as necessary to maintain the oxidation-reduction potential ofthe autodepositing liquid composition within the range of 350 ± 50 mV. A reading of free fluoride ions activity as measured by a LINEGUARD® 101 Meter and associated free fluoride sensitive electrode (commercially available from Ori¬ on Instruments) was made bi-hourly. Dilute hydrofluoric acid in water was added as nec- essary to maintain the free fluoride activity within a specified operating range of 250 ± 25 microamperes. The total solids content ofthe autodepositing liquid composition was measured at least as often as every 24 hours when the autodepositing liquid composition was used for an extended period of time, and additional amounts of concentrated dispersion of epoxy resin prepared as described above were added as needed to maintain the percent solids within the range of 5.0 ±0.5. Test Methods for Coated Substrates Initial adhesion was measured according to method General Motors 907 IP and o adhesion after water soak (for 2 hours at 38 ° C) was measured according to American So¬ ciety for Testing and Materials (hereinafter usually abbreviated "ASTM") Method Bl 17- 85. Reverse impact was performed according to ASTM Method D 2794-84. Brake fluid resistance was measured by monitoring changes in coating Pencil Hardness, using Gener¬ al Motors DELCO™ Supreme 11 (Department of Transportation Classification 3) brake 5 fluid at room temperature. Thermal stability of the epoxy coatings was measured by heating the panels in a conventional oven for a specified length of time, followed by mea¬ suring reverse impact and brake fluid resistance after specified times. Specific Composition Examples - Group I The basic epoxy resin modifiers tested are described in Table 1 below, and some 0 physical parameters of various coalescing agents used in this group are given in Table 2 below. Table 3 below, in which the abbreviation "N.m." means "Not measured", con¬ tains various coating parameters and corrosion test data for the various coalescing agents with crosslinked Epon™ 1007, a mixture of oligomers ofthe diglycidyl ether of bisphe¬ nol- A with an average epoxide equivalent weight of about 2000 and a corresponding av- 5 erage of about 13 hydroxyl functional groups per chain. Hϋls Vestagon™ B 1530 is an isophorone diisocyanate-based, e-caprolactam blocked isocyanate; it was used as a cross¬ linking agent in each instance shown in Table 3, at a ratio of (1007):(B 1530) = 80:20. The emulsifying agent was 2.7 %, based on epoxy resin solids together with cross-linking agent solids if any, of Rhodapex™ CO-436 (as supplied, with 58 % active emulsifying 30 agent). Cure conditions were 190 °C for 40 minutes, chosen with the expectation that these conditions would achieve the maximum amount of cross-linking practically possib¬ le with the compositions used. TABLE 1 Modifier Trade Chemical Type/Description Supplier Name Epon™ 828 Liquid BPA-Based ER: EEW = 185 - 192 Shell Chem. Co. Epon™ 872 Semi-Solid Chemically-Modified BPA-Based Flexible ER; EEW Shell Chem. Co. = 650 - 750 Epon™ 1020-A-80 -20 % Brominated BPA-Based ER; EEW = 455 - 475 Shell Chem. Co. Epon™ 1031 Solid BPA-Based ER of Functionality = 4; EEW = 200-240 Shell Chem. Co. Kraton™ RP-6565 70 - 95 % Epon™ 828 ER and 5 - 30 % Rubber-Modified ER Shell Chem. Co. XP 71739.00 Phosphate Ester of Epon™ 1004-Type ER Dow Chem. Co. Araldite™ GT-7099 Solid High MW BPA-Based ER Ciba-Geigy PKKM™ 301 Phenoxy Resin; Modified Poly(hydroxyether); MW > - 10,000 Phenoxy Assoc. Heloxy™ 68 DGE of Neopentyl Glycol; EEW = 130 - 140; BP > 148 °C Shell Oil Co. Heloxy™ 107 DGE of Cyclohexane Dimethanol; EEW = 155 - 165; BP > 148 Shell Oil Co. °C Lumiflon™ 400 Crosslinkable Fluoropolymer Resin Zeneca Coφ. Acronyms and Other Abbreviations for Table 1 BPA = Bisphenol-A; ER = epoxy resin; EEW = epoxide equivalent weight; Chem. Co. = Chemical Company; MW = molecular weight; Assoc. = Associates; DGE = diglycidyl ether. TABLE 2 Coalescing Agent Molec¬ Boiling % in Saturated ular Point, Aqueous Trade Name Chemical Name Weight °C Solution Dowanol™ PM Propylene glycol monomethyl ether 90.1 120.1 Miscible Dowanol™ PtB Propylene glycol monomethyl ether 132.2 151 * 14.5 Dowanol™ PnB Propylene glycol monomethyl ether 132.2 170.2 6.4 Dowanol™ DPnB Dipropylene glycol mono-/z-butyl ether 190.3 229 5 Dowanol™ TPM Tripropylene glycol monomethyl ether 206.3 242.4 Miscible Dowanol™ PPh Propylene glycol monophenyl ether 152.2 242.7 5.4 Texanol™ 2,2,4-trimethyl-l ,3-pentanediol mono-2-ethyl 216.3 244 - < 0.1 propionate 247 Footnote for Table 2 ♦ This material forms an azeotrope with water that boils at 95 °C. TABLE 3 Concentration of Coalescing Concentration of Reagent Adhesion Test Value, Pencil Brake Reverse 500 Hours Scribe/Scab Agent, % of Solids in Resin in Post-rinse Initial/After WS Hardness Fluid Impact Salt Spray 20 Cycle and Cross-Linking Agent(s) Resistance Results Test Results None None 0/0 4H 8 Hours 160 5-5 55 % Peel π 0.1% Ammonium citrate 0/0 4H 0.5 Hour 160 6-6 N.m. 15 % of Dowanol™ PM None 0/0 4H 4 Hours 160 9-10 55 % Peel 2 % BONDERITE® 958R N.m. 4H 2 Hours N.m. N.m. N.m. 15 % of Dowanol™ TPM None N.m. N.m. N.m. N.m. N.m. 75 % Peel 3 % of Texanol™ None 0/0 4H 8 Hours 160 N.m. 45 % Peel 0.1% Ammonium citrate 0/0 4H 8 Hours 160 7-7 >21; 20 % -j Peel Bottom 15 % of Dowanol™ PnB None 0/0 4H 8 Hours 160 N.m. 80 % Peel 0.1% Ammonium citrate 0/0 4H ~4 Hours 160 N.m. N.m. 20 % of Dowanol™ PnB None 0/0 4H 8 Hours 160 6-8 5-6; 40 % Peel Bottom 0.1% Ammonium citrate 0/0 4H 8 Hours 160 N.m. 15; 40 % Peel Bottom 25 % of Dowanol™ PnB None 0/0 4H 8 Hours 160 9-9 21; 20 % Peel Bottom 0.1% Ammonium citrate 0/0 4H 8 Hours 160 N.m. 12; 35 % Peel Bottom 15 % of Dowanol™ DPnB None 1/0 4H 8 Hours 160 6-7, 16s 80 % Peel TABLE 4 Concentration of Coalescing Concentration of Reagent Concentration of Flow Brake 500 Hours Salt Spray Scribe/Scab 20 Cycle Agent, as % of Solids in in Post-rinse Modifier, as % of Fluid Results Test Results Resin and Cross-Linking Solids in Resin and Resistance Agent(s) Cross-Linking Agent(s) 15 % of Dowanol™ PnB None None <0.5 Hour 6-7, 21s 95% Peel 0.1 % Ammonium citrate <0.5 Hour 4-5, 1 1s 17; 20 % Peel Bottom None <0.5 Hour 9-10 25; 20 % Peel Edge ro None 1% FC 430 <0.5 Hour N.m. N.m. oo 0.1 % Ammonium citrate <0.5 Hour N.m. 80% Peel None 1% FC 171 N.m. N.m. N.m. 0.1 % Ammonium citrate <0.5 Hour 3-3, 10s; 75% Peel N.m. None 1% SURF 61 N.m. 6-8, 18s 100 % Peel 0.1 % Ammonium citrate 0.5 Hour 5-6, 14s 70 % Peel None 1% SURF 82 0.5 Hour 4-4, 8s 90 % Peel - 0.1 % Ammonium citrate <0.5 Hour 8-12, 24s N.m. 15 % of Dowanol™ DPnB None None 4 Hours 8-9, 14s 95 % Peel 0.1 % Ammonium citrate <0.5 Hour 95% Peel 65 % Peel Table 4 shows the same kind of data as Table 3, except that for Table 4 the base epoxy resin was Epon™ 1004 instead of 1007. Epon™ 1004 is also reported by its sup¬ plier to be a mixture of oligomers ofthe diglycidyl ether of bisphenol- A but has an aver¬ age epoxide equivalent weight of 875 and a corresponding average of about 5 hydroxyl groups per molecule. The ratio of (1004):(B 1530) was 86.3 : 13.7. All other conditions not specifically noted in Table 4 were the same as for Table 3. Various cure conditions, including two-stage cures, were explored with the com¬ bination of Epon™ 1004 epoxy resin and Vestagon™ B 1530 cross-linking agent, in a ratio of 86.3/13.7; the working autodepositing liquid composition also contained 15 % of Dowanol™ PnB coalescent, and a DI water postrinse was used. Cleavage ofthe e- caprolactam blocking group from the crosslinking agent begins at 160 °C when mixtures containing it are heated from a lower temperature. One-stage cure conditions of 170, 180, 185, and 190 °C for 40 minutes were investigated. Also 185 °C cures for 30, 35 and 40 minutes were compared. Two-stage cures involving 10- and 20-minutes of pre- cure at 120, 140, and 150 °C followed by 30 minutes at 185 °C were also investigated. A lower-temperature first-stage cure allows water to leave the coating before deblocking of the isocyanate. (Although lower temperature pre-cures were tried, 120 °C was the minimum temperature at which film formation occurred.) Some results are shown in Table 5 and its notes. In order to establish a baseline on the effect of various epoxy modifiers on coat¬ ings, a wide variety of modifiers as shown in Table 1 were screened, at the same Dowa¬ nol™ PnB coalescing agent levels (15 % for Epon™ 1004 and 20 % for Epon™ 1007). A mixed cross-linking agent, consisting of Vestagon™ B 1530 as before and Bayer Des- modur™ BL 3175 A, which is methyl ethyl ketoxime-blocked hexamethylene diisocyan- ate with a deblocking temperature of 120 °C, in a ratio of 57:43 was used unless other¬ wise indicated. Various reaction rinses and in some cases simply DI water rinses after autodeposited coating formation were used as shown in Table 6. Some test performance data are also shown in Table 6. All examples in this Table also had 0 adhesive loss both initially and after 2 hours of water soaking, initial pencil hardness values of 4 H after curing, and reverse impact test values of 160 before aging with heat as shown in the TABLE 5 Curing Conditions, Temperature in "C/Time of Exposure to Temperature Brake Fluid Resistance Salt Spray, 1000 Hours Scribe/Scab, 20 Cycle 120/10 minutes followed by 185/30 minutes <0.5 Hour 90 % Peel 22 120/20 minutes followed by 185/30 minutes <0.5 Hour 5-8, 15s 28 140/10 minutes followed by 185/30 minutes <0.5 Hour 7-1 1 ; 99 % Peel 27; 90 % Peel 140/20 minutes followed by 185/30 minutes <0.5 Hour 4-7 24 150/10 minutes followed by 185/30 minutes <0.5 Hour 3-6, 10s . 26 150/20 minutes followed by 185/30 minutes <0.5 Hour 4-4, 14s 24 170/40 minutes <0.5 Hour 4-7, 16s 20 o o 180/40 minutes <0.5 Hour 8-12, 20s; 40 % Peel 31 185/30 minutes <0.5 Hour 5-10, 10 % Peel 30 185/35 minutes <0.5 Hour Not measured Not measured 185/40 minutes < 2 Hours 3-9, 10 % Peel 27 190/40 minutes > 4 Hours 5-12, 31s; 45 % Peel 49 Notes for Table 5 All cures shown also produced the following results: Good appearance ofthe coating; 0 loss of adhesion both initially and after 2 hours of water soaking; pencil hardness of 4H; and a reverse impact test value of 160. The autodepositing liquid composition was stable for at least two weeks, during which a total amount of metal surface corresponding to 1 square meter per liter of initial autodepositing liquid composition was coated with the composition. TABLE 6 Table continued on next page ... Modifier and CoCA Reagent in Initial Values After Heat Treating 65 Hours at Results after 500 Results after Concentration Postrinse if Any Brake 177 °C Hours Salt Spray Scribe/Scab 20 Fluid Cycles Resist¬ Reverse Pencil Hardness after 6 ance Impact Hours in Brake Fluid Epon™ 872 (10% O )V B 958 (2 %) 0.5 Hour 60 3H 4-4,6s 14 Epon™ 872 (10%) 0.1%NH 4 HCO, 0.5 Hour 160 4H 4-4 16 B 958 (2 %) 0.5 Hour 60 4H 2-3 13 GT 7099 (10%) 20% None 0.5 Hour 40 5H 3-4,8s 14 GT 7099 (10%) B 958 (2 %) 0.5 Hour 160 Bk Crk 6H 3-3 10 RP 6565 (10%) 20% 0.1%NH 4 HCO 0.5 Hour 160 4H 4-5 16 B 958 (2 %) 0.5 Hour 120 H 4-5 15 ro Heloxy™ 107(5%) 20% 0.1%NH 4 HCO, 2 Hours 160 3H 6-7, 14s 16 B 958 (2 %) 0.5 Hour 160 H 7-7 16 Lumifion™400(10%) 20% 0.1%NH 4 HCO 2 Hour 140 7H 4-4 36 B 958 (2 %) 2 Hour 20 5H 4-5 36; 30 % Peel None 3 20% None ~4 Hours 60 Dark 4H 8-8,24s 14 0.1%NH 4 HCO 3 2 Hours 160 7H 4-4, 10s 18 B 958 (2 %) -0.5 60 2H 4-5 Hour ... Table continued on next page ... Modifier and CoCA Reagent in Initial Values After Heat Treating 65 Hours at Results after 500 Results after Concentration Postrinse if Any Brake 177 °C Hours Salt Spray Scribe/Scab 20 Fluid Cycles Resist¬ Reverse Pencil Hardness after 6 ance Impact Hours in Brake Fluid None 20% B 958 (2 %) <0.5 160 4B 30% Peel 33 Hour Part B: With EPON™ 1004 Epon™ 828 (10%)' 20% None <0.5 120 6H 3-5(l)Blist. 9 Ave. (4& 13) Hour B 958 (2%) <0.5 160 N.m. 1-2(1) 11(1) Hour None <0.5 N.m. N.m. N.m. 14(1) to O Hour Epo n ™872(10%)' None <0.5 N.m. N.m. N.m. 16 Hour 0.1%NH 4 HCO 3 <0.5 160 4H 2-2 15 Hour Epon™ 1031 (10%)' None 2 Hours 80 7H 60 % Peel 12 " 0.1%NH 4 HCO 3 <0.5 160 6H 3-5 N.m. Hour XP 71739 (10%)' None <0.5 N.m. N.m. N.m. 13 Hour " 1 0.1%NH„HCO, 0.5 Hour N.m. N.m. 2-3 N.m. Table continued on next page ... Modifier and CoCA Reagent in Initial Values After Heat Treating 65 Hours at Results after 500 Results after Concentration Postrinse if Any Brake 177 °C Hours Salt Spray Scribe/Scab 20 Fluid Cycles Resist¬ Reverse Pencil Hardness after 6 ance Impact Hours in Brake Fluid XP 71739 (10%) None <0.5 N.m. N.m. N.m. 12 Hour XP 71739 (10%)' None <0.5 N.m. N.m. N.m. 12 Hour XP 71739 (10%) 2 0.1 % NH 4 HCO 3 N.m. 55 5H 2-2 10 Footnotes for Table 6 'For this example, the cure was 20 minutes at 140 °C followed by 40 minutes at 190 °C. 2 The cross-linking agent for this example was B 1530 only. 'For this example, the cure was 20 minutes at 160 °C followed by 40 minutes at 190 °C. Abbreviations and Other Notes for Table 6 CoCA = Concentration of Coalescing Agent; B 958 = BONDERITE * ® 958 Replenisher, commercially available from the Parker Amchem Div. of Henkel Corp., Madison oo Heights, Michigan, USA; this material is an aqueous solution normally intended for preparation of zinc phosphate conversion coating baths and contains zinc, manganese, and - ** --• nickel cations and phosphate and complex fluoride anions along with phosphoric acid; Blist. = Blistering observed. Table. Particle size data in some ofthe dispersions prepared as described in Table 6 are shown in Table 7. TABLE 7 Epoxy Modifier Particle Size in Micrometres Measured in the: Dispersion Dispersion Initial Auto¬ Worked Aut¬ without with depositing odepositing Coalescing DowanoP™ Liquid Com¬ Liquid Com¬ Agent PnB Cis. Ag. position position Epon™ 1007 None 0.21 (0.17) 0.24 (0.21) N.m. 0.93 Epon™ 1007 Epon™ 828 0.18 (0.15) 0.20 (0.16) 0.25 N.m. Epon™ 1007 Epon™ 872 0.25 0.23 N.m. N.m. Epon™ 1007 Heloxy™ 0.13 & 0.26 0.18 N.m. 0.97 Modifier 68 Epon™ 1007 Heloxy™ 0.17 N.m. 0.17 N.m. Modifier 107 Epon™ 1007 raton™ 0.17 0.11 & 0.22 N.m. N.m. Epon™ 1007 1120-A-80 0.16 0.19 0.15 N.m. Epon™ 1007 XP 71739 0.17 0.19 0.24 0.28 Epon™ 1004 None 0.14 0.13 0.12 N.m. Epon™ 1004 Epon™ 828 0.13 0.16 0.15 0.87 Epon™ 1004 Epon™ 872 0.14 N.m. N.m. N.m. Epon™ 1004 XP 71739 0.12 0.13 0.11 N.m. Notes for Table 7 Cis. Ag. = Coalescing Agent; more than one entry in a cell, with either an ampersand or parentheses, indi¬ cates that both values were obtained on different attempts at replication ofthe composition. The values shown are for the most prominent peak in the calculated particle size distribution. Low crosslinker level (4 %) was also screened with the unmodified Epon™ 1007/B 1530/BL 3175 A coating. Using B 958 rinse, the brake fluid resistance was < 0.5 hours, as compared to 2 hours with the higher crosslinker level (18 %) using the same rinse. Composition Group II Based on the results obtained in Group I as described above, a statistical Box- Behnken design was used to optimize coalescing agent (which may alternatively be called "coalescent" for brevity) and concentrations of coalescing agent and modifier, with the following constants: Epoxy Resin: Epon™ 1007F Modifier Resin: Epon 828 Crosslinker: Vestagon™ B 1530 Emulsifying Agent: 2.7 % Rhodapex™ CO 436 Film Build: 20.3 - 25.4 micrometres Post Autodeposition Rinse: 2 % Bonderite® 958 Cure: 20 minutes at 150 °C followed by 40 minutes at 185 °C for Dowanol™ PnB 20 minutes at 125 °C followed by 40 minutes at 185 °C for Dowanol™ PPh. The details ofthe design are shown in Table II-l below, and results, including results from some additional examples not part ofthe Box-Behnken design, are shown in Tables II-2 and II-3 below. Group III - Mixing and Dispersion Variation Examples The variables for this study were resin molecular weight (Epon™ 1007, Epon™ 1004, Epon™ 828), presence or absence of Foamaster™ 111, polymer solution concen¬ tration, and dispersing equipment (Microfluidizer™, Cowles disperser, Kady disperser, IKA in-line disperser and laboratory mixer, and APV homogenizer). The key observab- les were particle size, particle size distribution, and dispersion stability. The microemulsions which are characterized below as "with Cowles blade" were made by a procedure which is typically called inversion emulsion. A polymer solution in organic solvent, the solvent generally being a mixture of equal masses of toluene and methyl isobutyl ketone (hereinafter usually abbreviated "MIBK"), was poured into a con- tainer that also was provided with a Cowles blade. After this blade was brought to a moderately high speed, the desired amounts of surfactant and of DI water were added. The blade was then brought up to its highest speed and allowed to operate for 5 to 20 minutes. Finally, more DI water, about three to six times as much as the first addition of DI water, was added and the blade was then shut off after a few minutes. The result was an emulsion, typically with mean particle size on the order of 700 to 1200 nm. Microemulsions characterized below as made with a MICROFLUIDIZER™ ap¬ paratus were made in the same manner as already described above for making the emul¬ sions for Groups I and II, except that (i) in some instances, as noted in tables below, a preliminary emulsion made with a Cowles blade or a Kady mill was used instead ofthe initial stage of using the injection system ofthe MICROFLUIDIZER™ apparatus as de¬ scribed above and (ii) the particle size was measured after each pass through the MI¬ CROFLUIDIZER™ apparatus instead of using a fixed number of passes as described TABLE II-l Trial # Coalescent Coalescent Con¬ Epoxy/Cross- Modifier Con¬ centration, % Linking Agent centration, % Ratio I ' Dowanol™ PPh 7.5 90:10 15 2 " PnB 10 80:20 10 3 " PPh 0 80:20 15 4 " PnB 10 95:5 10 5 " PnB 20 90:10 20 6 " PnB 20 80:20 15 7 " PPh 7.5 80:20 10 8 " PPh 0 90:10 20 9 " PnB 10 95:5 20 10 " PnB 10 80:20 20 11 " PPh 0 95:5 15 12 " PPh 7.5 95:5 10 13 " PPh 0 90:10 10 14 " PnB 20 80:20 15 15 " PnB 20 90:10 10 16' " PPh 7.5 90:10 15 17 " PPh 15 90:10 10 18 " PPh 15 95:5 15 19 " PPh 15 90:10 20 20 " PPh 7.5 95:5 20 21 " PPh 15 80:20 15 22 " PnB 10 90:10 15 23 " PPh 7.5 80:20 20 24' " PPh 7.5 90:10 15 Foomote for Table II-l 'This is the center point ofthe Box-Behnken design. TABLE II-2 Ident¬ Ratio Ratio Coa¬ Most Frequent Particle Size, micrometres, Stability of: ifying of of lescent in: Num¬ Epon™ Total and ber 828/ Epoxy/ Percent Disper¬ Disper¬ Initial Worked Dispersion After Add¬ Initial Autodepositing Worked Autodepositing Epon™ Cross- Thereof sion Be¬ sion Autode¬ Autode¬ ing Coalescent Liquid Composition Liquid Composition 1007F Linker if Any fore After positing positing Adding Adding Liquid Liquid at 23 ± at 49 ± l °C at 23 ± 5 °C at 49 ± l at 23 ± 5 at 49 ± l Coales¬ Coales¬ Composi¬ Composi¬ 5 °C °C °C °C cent cent tion tion 1 15:85 90:10 PPh 7.5 - 0.18 0.19 0.22 >1 Mo. >1 Mo. >1 Mo. >1 Mo. >1 Mo. >1 Mo. 2 10:90 80:20 PnB 10 0.19 0.17 0.18 0.20 >l Mo. >1 Mo. >1 Mo. >1 Mo. >1 Mo. >1 Mo. 3 15:85 80:20 None 0.19 - 0.18 0.22 >1 Mo. >l Mo. >1 Mo. >1 Mo. Res. 1 Mo. >1 Mo. 4 10:90 95:5 PnB 10 0.18 0.18 0.18 0.18 >1 Mo. >I Mo. >I Mo. >1 Mo. >1 Mo. >1 Mo. 5 20:80 90:10 PnB 20 0.16 0.18 N.m. 0.17 >I Mo. >1 Mo. Res. 2 Wks. N.m. N.m. >1 Mo. CO CO 6 15:85 80:20 PnB 20 0.17 0.16 0.19 0.25 >1 Mo. >1 Mo. >I Mo. >1 Mo. N.m. >1 Mo. 7 10:90 80:20 PPh 7.5 - 0.17 0.29 >0.5 N.m. N.m. >1 Mo. N.m. >1 Mo. N.m. 8 20:80 90: 10 None 0.18 ~ 0.22 0.21 >1 Mo. >1 Mo. Res. 2 Wks. >I Mo. N.m. >1 Mo. 9 20:80 95:5 PnB 10 0.23 0.16 0.21 0.23 >1 Mo. N.m. >1 Mo. Res. 1 Wk. >1 Mo. Res. 1 Wk. 10 20:80 80:20 PnB 10 0.17 0.18 0.16 0.20 >1 Mo. >1 Mo. >1 Mo. >1 Mo. >1 Mo. Res. 2 Wks. 1 1 15:85 95:5 None 0.16 - 0.26 0.28 N.m. N.m. >1 Mo. >1 Mo. >1 Mo. >l Mo. 12 10:90 95:5 PPh 7.5 - 0.19 0.21 0.26 >1 Mo. >I Mo. >1 Mo. >l Mo. >1 Mo. >I Mo. 13 10:90 90: 10 None 0.18 - 0.20 >0.5 N.m. N.m. >1 Mo. >1 Mo. >1 Mo. Res. I Mo. 14 15:85 80:20 PnB 20 0.17 0.20 0.17 0.18 N.m. N.m. >1 Mo. >1 Mo. >1 Mo. Res. 1 Mo. 15 10:90 90: 10 PnB 20 0.17 0.17 0.18 >0.5 N.m. N.m. >l Mo. | >I Mo. >1 Mo. Res. 2 Wks. Table continued on next page . Ident¬ Ratio Ratio Coa¬ Most Frequent Particle Size, micrometres, Stability of: ifying of of lescent in: Num¬ Epon™ Total and ber 828/ Epoxy/ Percent Disper¬ Disper¬ Initial Worked Dispersion After Add¬ Initial Autodepositing Worked Autodepositing Epon™ Cross- Thereof sion Be¬ sion Autode¬ Autode¬ ing Coalescent Liquid Composition Liquid Composition 1007F Linker if Any fore After positing positing Adding Adding Liquid Liquid at 23 ± at 49 ± l °C at 23 ± S °C at 49 ± I at 23 ± 5 at 49 ± 1 Coales¬ Coales¬ Composi¬ Composi¬ 5 °C °C β C °C cent cent tion tion 16 15:85 90:10 PPh 7.5 ~ N.m. 0.18 0.17 N.m. N.m. >1 Mo. >l Mo. >l Mo. Res. 2 Wks. 17 10:90 90: 10 PPh 15 -- 0.20 0.19 0.20 N.m. >1 Mo. >1 Mo. Res. 1 Mo. >1 Mo. Res. 2 Wks. 18 15:85 95:5 PPh 15 - 0.19 0.20 >0.5 N.m. N.m. >l Mo. N.m. >1 Mo. N.m. 19 20:80 90: 10 PPh 15 - 0.19 0.26 N.m. >1 Mo. >1 Mo. >1 Mo. Res. 1 Mo. N.m. Res. 1 Mo. 20 20:80 95:5 PPh 7.5 - 0.17 0.23 >0.5 N.m. N.m. >1 Mo. >1 Mo. >1 Mo. Res. 1 Mo. 21 15:85 80:20 PPh 15 - 0.17 0.15 N.m. N.m. >l Mo. >1 Mo. Res. 1 Wk. >l Mo. >1 Mo. •-o 22 15:85 90: 10 PnB 10 0.17 0.19 0.20 0.21 >l Mo. N.m. >1 Mo. N.m. >l Mo. N.m. 23 20:80 80:20 PPh 7.5 - 0.15 N.m. 0.15 >1 Mo. >1 Mo. N.m. N.m. >l Mo. >1 Mo. 24 15:85 90: 10 PPh 7.5 - 0.18 0.20 0.18 >1 Mo. N.m. >l Mo. >l Mo. >1 Mo. >l Mo. 25' 10:85:5 80:20 PnB 10 0.16 0.16 >0.5 >0.5 >l Mo. N.m. >l Mo. N.m. >1 Mo. N.m. 26' 10:85:5 80:20 None 0.14 - 0.17 >0.5 >1 Mo. Res. 3 Wks. >l Mo. >1 Mo. >I Mo. >l Mo. 27' 10:85:5 80:20 PPh 5 ~ 0.15 N.m. >0.5 N.m. N.m. N.m. N.m. N.m. N.m. 28 15:85 90:10 None 0.18 ~ 0.15 0.28 >1 Mo. >1 Mo. >l Mo. >l Mo. >l Mo. >l Mo. Foomote for Table II-2 'The third epoxy resin was XP 71739. Other Notes for Table II-2 PnB and PPh are the Dowanol™ solvents identified by the same abbreviations in earlier tables. "Mo." = "Month(s)"; "Wk(s)." = "Week(s)"; "Res." = "Residue was visible after". TABLE II-3 Identifying Ratio of Ratio of Total Coa¬ Pencil Reverse Brake Fluid Num¬ Results after Scribe/Scab, Number Epon™ 828/ Epoxy/ Cross- lescent Hardness Impact Resistance ber of 500 Hours 20 Cycles Epon™ 1007F Linker and Value Panels Salt Spray (Film Percent Pro¬ Testing Thickness, μ) Thereof if cessed (Film Any Thickness, μ) 1 15:85 90:10 PPh 7.5 4H 160 < 0.5 Hour 18 1-1 (23) 12 (28); 19 (17) 2 10:90 80:20 PnB 10 3H 160 > 4 Hours 2 l-2,4s (22) 18 (17) 3 15:85 80:20 None 4H 160 > 4 Hours 6 1-1 (25) 20 (27) 4 10:90 95:5 PnB 10 3H 160 < 0.5 Hour 14 3-4 (24) 14.5 (24) 4 * * O 5 20:80 90:10 PnB 20 4H 160 > 4 Hours 6 0-1 (22) 12 (20) 6 15:85 80:20 PnB 20 4H 160 < 0.5 Hour 24 2-4 (23) 17 (23) 7 10:90 80:20 PPh 7.5 5H 160 N.m. 6 1-3 (25) 20.5 (21) 8 20:80 90:10 None 4H 160 < 0.5 Hour 8 0-1 (24) 16.5 (23) 9 20:80 95:5 PnB 10 5H 160 < 0.5 Hour 12 90%P (19) 85%P (12) 10 20:80 80:20 PnB 10 4H 160 1 Hour 22 1-2 (22) 24.5 (22) 1 1 15:85 95:5 None 4H 160 < 0.5 Hour 4 0-1 (24) 21 (22) 12 10:90 95:5 PPh 7.5 3H 160 < 0.5 Hour 6 4-5,7s (24) 14 (23) 13 10:90 90:10 None 4H 160 < 0.5 Hour 8 1-1 (25) 16 (25) Table continued on next pag . Identifying Ratio of Ratio of Total Coa¬ Pencil Reverse Brake Fluid Num¬ Results after Scribe/Scab, Number Epon™ 828/ Epoxy/ Cross- lescent Hardness Impact Resistance ber of 500 Hours 20 Cycles Epon™ 1007F Linker and Value Panels Salt Spray (Film Percent Pro¬ Testing Thickness, μ) Thereof if cessed (Film Any Thickness, μ) 14 15:85 80:20 PnB 20 4H 160 < 0.5 Hour 0 7-7 (23) 17 (23) 15 10:90 90:10 PnB 20 3H 160 < 0.5 Hour 12 1-9, 5%P 27 (20) (21) 16 15:85 90:10 PPh 7.5 2H 160 < 0.5 Hour 18 1-1 (25) 17 (26) 17 10:90 90:10 PPh 15 4H 160 < 0.5 Hour 8 0-2 (25) 15 (24) 18 15:85 95:5 PPh 15 4H 160 < 0.5 Hour 22 7-8, 8%P 28 (12) (12) 20 20:80 95:5 PPh 7.5 2H 160 < 0.5 Hour 6 0-1 (25) 14.5 (23) 21 15:85 80:20 PPh 15 4H 160 < 0.5 Hour 10 l-2,3s (22) 24.5 (24) 24 15:85 90:10 PPh 7.5 4H 160 0.5 Hour 32 1-3 (N.m.) 30 (NA) 25' 10:85:5 80:20 PnB 10 N.m. N.m. N.m. N.m. N.m. 26 (NA) 27' 10:85:5 80:20 PPh 5 N.m. N.m. N.m. N.m. N.m. 25 (22);(I) 60%P 28 15:85 90:10 None 4H 160 < 0.5 Hour 10 2-3,4s (28) 19 (25) Footnote for Table II-3 'The third epoxy resin was XP 71739. above. Resulting particle size statistics are shown in Table III-l below. Microemulsions characterized below as made with a Kady mill were prepared in a Kady Model L mill. In a typical experiment, 250 parts in total of epoxy resin(s) and any cross-linking agents and/or modifiers used were dissolved in 150 parts of toluene and 150 parts of MIBK. This solution was transferred to a stainless steel mixing vessel equipped with a cooling jacket and the milling means characteristic of the equipment from this manufacturer, which was initially operated at 8,000 rpm. To this solution, a separate solution of 11.4 parts of Rhodapex™ CO-436 emulsifying agent dissolved in 50 parts of DI water was added, and the mixer was then turned up to its full speed of 16,000 φm. It was then allowed to stir for 5 min. Another 100 parts of DI water was then added. At this point the viscosity ofthe emulsion usually became similar to that of whipped cream, indicating that the mixture was at the point of inversion from water-in- oil to oil-in-water. Additional DI water was added slowly until the viscosity dropped to the point that the emulsion readily flowed through the Kady blade. The mill was then allowed to run for one additional hour. Results with the Kady mill varied considerably, depending on which of two stator designs supplied with the machine were used. The "original" stator supplied was report¬ ed by the supplier to be the current standard design. A "new" stator also supplied was reported to be engineered to increase the efficiency of collisions ofthe particles and did in fact produce substantially smaller particle sizes; results are summarized in Table III-2. Two types of preliminary emulsions were subjected to particle refinement in a ho¬ mogenizer: The first sample was an emulsion produced by using a Cowles blade as de¬ scribed above. The second sample was produced by a Kady mill with original stator and had a maximum particle size of 400 nm. These preliminary emulsions were gravity fed into a Rannie™ Model 12.51 H or Model 8.30 homogenizer respectively, each with a single stage homogenizing valve. Samples were taken at several pressures up to 14,500 psi. The maximum temperature of the samples was noted as 63 °C. Results are summar¬ ized in Table III-3. A sample preliminary emulsion prepared with a Cowles blade (identically to the first sample tested in a Rannie™ homogenizer as described above) was run through an IKA DR# 6/6 P in-line milling unit. The generator configuration was designated as super fine, super fine, super fine. Samples were run continuously for 5 minutes and separately Table III-l Epon™ Resin Used Cowles Blade? No. of Passes Particle Diameters in nm Effective Mean 1004 with 1 239.3 232 1004 with 2 215.8 199 1004 with 3 197.2 190 1004 with 4 184.9 157 1004 with 5 182.1 173 1004 with 6 180.8 170 1004 without 1 251.8 239 1004 without 2 174.7 168 1004 without 3 157.3 145 1004 without 4 144.8 132 1004 without 5 143.8 140 1004 without 6 141.2 129 1004 with' 0 384 250 1004 with 1 1 241.9 243 1004 2 without 6 159.9 159 1007 without 1 319 261 1007 without 2 227.9 214 1007 without 3 213.4 200 1007 without 4 212.9 203 1007 without 5 211.5 21 1 1007 without 6 205.0 201 1007 with 1 31 1.8 312 1007 with 2 269.3 225 1007 with 3 247.7 242 1007 with 4 224.9 196 1007 with 5 232.2 219 Footnotes for Table III-l 'This was first dispersed with a Kady mill before being passed through the MICROFLUIDIZER™ appa¬ ratus. 2 Foamaster™ 1 1 1 defoamer in an amount of about 0.5 grams of defoamer per kilogram of total composition was also added to this mixture, along with the other ingredients generally noted above. TABLE III-2 Conditions Particle Size 250 g solids, 200 g of water, original stator 387 nm 400 g solids, 30 g water, original stator 585 nm 250 g solids, 250 g of water, original stator 328 nm 250 g solids, 300 g water, original stator 321 nm 400 g solids, 50 g water, original stator 343 nm 250 g solids, 200 g of water, new stator 212 nm 250 g solids, 200 g of water, new stator 1 316 nm 250 g solids, 200 g of water, original stator 2 200 nm Footnotes for Table III-2 'This emulsion was milled for only 30 minutes after the last addition of water, instead of 60 minutes as for the other emulsions. 2 This emulsion was passed once through the MICROFLUIDIZER™ apparatus after completion ofthe normal Kady milling procedure. for 1 to 3 passes through the milling unit. Other samples were passed through an IKA laboratory disperser/mixer, in the same manner, except for the change of equipment, as described above for the Kady disperser. Results are shown in Table III-4 below. All the procedures, or combinations of procedures, described above within this group which resulted in an average particle size not more than 220 nm were further eval¬ uated for stability in a working autodepositing liquid composition. The epoxy resin dis¬ persions were used either as the sole constituent of component (A) as described above or in a mixture with an equal part by weight, counting only solids in each case, ofa con¬ ventional emulsion polymerized latex dispersion of acrylic polymer, as known generally in the art to have been suitable for autodepositing liquid compositions heretofore. The remaining constituents (B) and (C), along with (G) and/or (J) when used, as described above for Example Group II were then combined to make an autodepositing liquid com¬ position as described for Example Group II. The autodepositing liquid compositions all appeared stable for the first day after being made and were allowed to sit without agita¬ tion for an extended period of time. At selected intervals each sitting autodepositing li¬ quid composition was transferred to another container, and the bottom ofthe container TABLE iπ-3 Pressure, Bars Number of Passes Effective Particle Size For Preliminary Emulsion Made with Cowles Blade — 0 »1000 nm 344 418.7 nm 551 374.7 nm 689 338.8 nm 827 327.8 nm 999 302.9 nm 827 2 217.6 nm 999 2 203.7 nm For Preliminary Emulsion Made with Kady Mill — 0 350.0 nm 1033 1 185.9 nm 1033 2 189.4 nm 1033 3 153.7 nm 1033 4 164.1 nm 1033 5 158.0 nm 1033 6 157.2 nm 1033 7 148.7 nm 1378 7 164.9 nm which had contained the autodepositing liquid composition while it was sitting was checked, visually, for any settling of dispersion. This would represent the first signs of emulsion instability. The results are summarized in Table III-5. TABLE ffl-4 Conditions Effective Particle Size Before any milling 1247 nm Large batch, 1 pass 802 nm Small batch, first pass 675 nm " " , second pass 787 nm " " , third pass 929 nm " " , 5 minutes continuous feed 793 nm Laboratory mill 455 nm TAJ 3LE ffl-5 Component (A) Process Average Stability Stability after Composition Particle Size after 3 Days 11 Days 50/50 Ac/Ep Kady milled only 212 nm Some Significant settling settling 50/50 Ac/Ep Kady mill + 1 Micro- 200 nm Very little Very little fluidizer™ pass settling settling 50/50 Ac Ep Cowles Blade + 2 ho¬ 200 nm Very little Very little mogenizer passes settling settling 100 Ep Kady milled only 212 nm N.m. Significant settling 100 Ep Kady mill + 1 Micro- 200 nm N.m. Very little fluidizer™ pass settling 100 Ep Cowles Blade + 2 ho¬ 200 nm Km. Very little mogenizer passes settling Abbreviations for Table III-5 "50/50 Ac/Ep" means a blend of equal masses of epoxy resin and acrylic latex solids as described in the main text. "100 Ep" means all epoxy resin.

Claims: The invention claimed is: 1. An autodepositing liquid composition comprising water and: (A) a total amount that is at least about 1.0 %, based on the whole composition, of dispersed or both dispersed and dissolved film forming polymer molecules, said amount including at least about 0.2 %, based on the whole composition, of dis¬ persed molecules each containing at least two 1,2-epoxy moieties, the total amount of all of said dispersed or dissolved and dispersed film forming polymer molecules having the following size distribution characteristics in a dispersion, or dispersion and solution, (the phrase "dispersion, or dispersion and solution" being hereinafter usually abbreviated as "DDS") of the film forming polymer molecules in water: ( 1 ) the DDS has a mean light scattering particle size that is at least about 100 but not more than about 300 nm; (2) no more than about 1.0 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than about 450 nm; (3) no more than about 25 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than about 250 nm; (4) no more than about 50 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than about 200 nm; and (5) no more than about 75 % ofthe light scattering particles volume in the DDS consists of particles with a diameter larger than about 175 nm; (B) an emulsifying agent component in sufficient quantity to emulsify any insoluble part of component (A) so that, in the autodepositing liquid composition, no sepa¬ ration or segregation of bulk phases that is perceptible with normal unaided hu- man vision occurs during storage at 25 °C for at least 24 hours after preparation ofthe autodepositing liquid composition, in the absence of contact ofthe autode¬ positing liquid composition with any substance that reacts with the autodeposit¬ ing liquid composition; and (C) a dissolved accelerator component, selected from the group consisting of acids, oxidizing agents, and complexing agents, sufficient in strength and amount to im¬ part to the total autodepositing liquid composition an oxidation-reduction poten¬ tial that is at least 100 mV more oxidizing than a standard hydrogen electrode. 2. An autodepositing liquid composition according to claim 1 , wherein: component (A) is present in an amount that constitutes from about 2.5 to about 10 % of the total com¬ position; an amount of molecules of component (A) that corresponds to at least about 20 % of all molecules of component (A) contains at least two 1,2-epoxide moieties per mol- ecule and has an epoxide equivalent weight of at least about 374; at least about 20 % of the molecules in component (A) that contain at least two 1,2-epoxide moieties and have an epoxide equivalent weight of at least about 374 have an equivalent weight that is at least about 446 but is not more than about 4527; if the composition includes any amount of molecules having at least two 1,2-epoxide moieties and an epoxide equivalent weight of at least 873, the composition also includes an amount of molecules having exactly two 1,2-epoxide moieties and an epoxide equivalent weight not more than about 200 that is at least 4 % of the amount of molecules having at least two 1,2-epoxide moieties and an epoxide equivalent weight of at least 873. 3. A autodepositing liquid composition according to claim 2, also comprising cross- linking agents selected from the group consisting of both of the following molecular types: (CL.1) molecules each containing at least two functional groups, which may be the same or different, selected from the group consisting of amine, amide, imine, thiol, hy¬ droxyl, carboxyl, and carboxylic acid anhydride; and (CL.2) molecules that are not part of component (CL.l) and that contain at least two blocked isocyanate groups, so that the blocked isocyanate groups do not react at any appreciable rate at room temperature with hydroxyl groups but do react rapid¬ ly with hydroxyl groups after being unblocked by heating to a temperature that is at least 100 °C and is not more than 190 °C. 4. An autodepositing liquid composition according to claim 3, wherein: an amount of molecules of component (A) that corresponds to at least about 30 % of all molecules of component (A) contains at least two 1 ,2-epoxide moieties per molecule and has an epoxide equivalent weight of at least about 374; at least about 50 % ofthe molecules in component (A) that contain at least two 1,2-epoxide moieties and have an epoxide equiv- alent weight of at least about 374 have an equivalent weight that is at least about 731 but is not more than about 3106; if the composition includes any amount of molecules having at least two 1,2-epoxide moieties and an epoxide equivalent weight of at least 873, the composition also includes an amount of molecules having exactly two 1,2-epoxide moieties and an epoxide equivalent weight not more than about 200 that is at least 7 % of the amount of molecules having at least two 1,2-epoxide moieties and an epoxide equivalent weight of at least 873; and, for the amount of component (A) constituted of molecules for which the epoxide equivalent weight is at least 374: the ratio ofthe mean light scattering particle diameter in nm divided by the cube root ofthe average epoxide equivalent weight expressed in daltons, this ratio being usually briefly denoted hereinafter as the "diameter ratio", is not more than about 29.2 {nm/(dalton 14 )} ; no more than about 1.0 % ofthe light scattering particles volume consists of particles with a diameter ratio larger than about 44.2; no more than about 25 % ofthe light scattering particles volume consists of particles with a diameter ratio larger than about 25.1 {nm/(dalton % )}; no more than about 50 % of the light scattering particles volume consists of particles with a diameter ratio larger than about 20.4 {nm/(dalton ,4 )} ; and no more than about 75 % ofthe light scattering particles volume consists of particles with a diameter ratio larger than 5 about 17.8 {nm/(dalton ,/4 )}. 5. An autodepositing liquid composition according to claim 4, wherein: component (A) is present in an amount that constitutes from about 3.5 to about 6.5 % of the total composition; an amount of molecules of component (A) that corresponds to at least about 40 % of all molecules of component (A) contains at least two 1,2-epoxide moieties per o molecule and has an epoxide equivalent weight of at least about 374; at least about 80 % ofthe molecules in component (A) that contain at least two 1,2-epoxide moieties and have an epoxide equivalent weight of at least about 374 have an equivalent weight that is at least about 1868 but is not more than about 2295; the composition also includes an amount of molecules having exactly two 1,2-epoxide moieties and an epoxide equivalent 5 weight not more than about 200 that is at least 9 % ofthe amount of molecules having at least two 1,2-epoxide moieties and an epoxide equivalent weight of at least 873; if at least 90 % of component (A) is constituted of molecules having at least two 1,2-epoxide moi¬ eties, the amount of molecules having exactly twol,2-epoxide moieties and an epoxide equivalent weight not more than about 200 is not more than 25 % ofthe amount of mol- 0 ecules having at least two 1,2-epoxide moieties and an epoxide equivalent weight of at least 873; and, for the amount of component (A) constituted of molecules for which the epoxide equivalent weight is at least 374: the overall diameter ratio is not more than about 23.0 {nm/(dalton 4 )}; no more than about 1.0 % ofthe light scattering particles vol¬ ume consists of particles with a diameter ratio larger than about 36.0; no more than about 25 % ofthe light scattering particles volume consists of particles with a diameter ratio larger than about 21.0 {nm/(dalton 1A )}; no more than about 50 % ofthe light scattering particles volume consists of particles with a diameter ratio larger than about 18.0 {nm/(dalton % )}; and no more than about 75 % ofthe light scattering particles volume con¬ sists of particles with a diameter ratio larger than about 15.0 {nm/(dalton 1A )}. 6. An autodepositing liquid composition according to any one of claims 1 through 5, wherein the molecules of component (A) that have at least two 1,2-epoxide moieties conform to general chemical formula (I): O H where C H . and n is an integer from 0 to 50. 7. A process for making an autodepositing liquid composition according to claim 6, said process comprising steps of: (I) providing a collection of film forming polymer molecules suitable to constitute component (A) ofthe autodepositing liquid composition to be made; (II) dissolving the collection of film forming polymer molecules provided in step (I) in a solvent component to form a single phase solution from the combination of the collection of film forming polymer molecules and the solvent component; (III) emulsifying the single phase solution formed in step (II), optionally along with other materials, into a volume of water, so as to form a DDS in water of at least those parts of the single phase solution formed in step (II) that constitute component (A) as recited above to form a DDS comprising at least components (A) and (B) of the autodepositing liquid composition to be made; and, if component (C) ofthe autodepositing liquid composition to be made is not present in said DDS, (TV) adding to the DDS formed in step (in) sufficient additional material to provide said component (C). 8. A process according to claim 7, wherein step (III) includes at least the following two substages: (III.1 ) a primary mixing stage in which there is formed a preliminary DDS which is suf¬ ficiently stable that no separation or segregation of bulk phases in the preliminary DDS that is perceptible with normal unaided human vision would occur during storage at 25 °C for at least 5 hours after preparation ofthe preliminary DDS, in the absence of contact ofthe preliminary DDS with any substance with which it will chemically react; and (III.2) at least one particle size refinement stage, in which the preliminary DDS formed in stage (III.1 ) or an intermediate formed by subjecting the preliminary DDS to at least one prior particle size refinement stage, is forced as least once through a narrow aperture, so as to produce after at least the last particle size refinement stage a final DDS in which particle sizes ofthe total amount of all ofthe dispersed or dissolved and dispersed film forming polymer molecules in component (A) of said autodepositing liquid composition meet the size distribution criteria specified in parts (A)(1) to (A)(5) of claim 6. 9. A process according to claim 8, in which the film forming polymer molecules in the preliminary DDS have an average particle size that is less than about 450 nm. 10. A process according to claim 8, in which the film forming polymer molecules in the preliminary DDS have an average particle size that is more than about 500 nm and step (III.2) is used at least twice. 11. A process for making an autodepositing liquid composition according to any one of claims 1 through 5, said process comprising steps of: (I) providing a collection of film forming polymer molecules suitable to constitute component (A) ofthe autodepositing liquid composition to be made; (II) dissolving the collection of film forming polymer molecules provided in step (I) in a solvent component to form a single phase solution from the combination of the collection of film forming polymer molecules -and the solvent component; (IH) emulsifying the single phase solution formed in step (IT), optionally along with other materials, into a volume of water, so as to form a DDS in water of at least those parts of the single phase solution formed in step (II) that constitute component (A) as recited above to form a DDS comprising at least components (A) and (B) of the autodepositing liquid composition to be made; and, if component (C) ofthe autodepositing liquid composition to be made is not present in said DDS, (TV) adding to the DDS formed in step (HI) sufficient additional material to provide said component (C). 12. A process according to claim 11, wherein step (TH) includes at least the following two substages: (TJI.1) a primary mixing stage in which there is formed a preliminary DDS which is suf- ficiently stable that no separation or segregation of bulk phases in the preliminary DDS that is perceptible with normal unaided human vision would occur during storage at 25 °C for at least 5 hours after preparation ofthe preliminary DDS, in the absence of contact ofthe preliminary DDS with any substance with which it will chemically react; and (IH.2) at least one particle size refinement stage, in which the preliminary DDS formed in stage (III-l) or an intermediate formed by subjecting the preliminary DDS to at least one prior particle size refinement stage, is forced as least once through a narrow aperture, so as to produce after at least the last particle size refinement stage a final DDS in which particle sizes ofthe total amount of all ofthe dispersed or dissolved and dispersed film forming polymer molecules in component (A) of said autodepositing liquid composition meet the size distribution criteria specified in parts (A)(1) to (A)(5) of any one of claims 1 through 5 respectively. 13. A process according to claim 12, in which the film forming polymer molecules in the preliminary DDS have an average particle size that is less than about 450 nm. 14. A process according to claim 12, in which the film forming polymer molecules in the preliminary DDS have an average particle size that is more than about 500 nm and step (iπ.2) is used at least twice.

Inventors: MUELLER BRIAN L, SIEBERT ELIZABETH J, MUELLER, BRIAN, L., SIEBERT, ELIZABETH, J.
Applicants: HENKEL CORP, MUELLER BRIAN L, SIEBERT ELIZABETH J, HENKEL CORPORATION, MUELLER, BRIAN, L., SIEBERT, ELIZABETH, J.
Application year: 1996
Main classification: C08L63
IPC codes: C08G59, C08J3, C08L63, C09D5, C09D163