MXPA01002846A

MXPA01002846A - Autodepositable aqueous compositions including dispersed non-film-forming polymers

Info

Publication number: MXPA01002846A
Application number: MXPA/A/2001/002846A
Authority: MX
Inventors: Rajat K Agarwal
Original assignee: Rajat K Agarwal; Henkel Corporation
Priority date: 1998-09-23
Filing date: 2001-03-19
Publication date: 2001-12-04

Abstract

An autodepositing liquid composition comprises dispersed non-film-forming polymer particles in addition to the dispersed film forming polymer characteristic of all autodepositing liquid compositions. Preferably, the non-film-forming polymer particles are gas-tight microballoons filled with a gas such as air and have an average particle size less than 1&mgr;m. Such particles act in the autodepositing liquid compositions and in the dried coatings formed from them as opaque white pigments, unless the coatings are heated above about 130°C. if so heated, the coatings, unless they contain other heat stable pigments, become irreversibly transparent.

Description

"AUTODEPOSITABLE AQUEOUS COMPOSITIONS INCLUDING SCRAP POLYMERS WITHOUT FILM TRAINERS" FIELD AND BACKGROUND OF THE INVENTION This invention relates to the use of autodepositable aqueous liquid compositions which are both dispersions and solutions in water. By the single contact with these self-depositable liquid compositions, the active metal surfaces can be coated with an adherent polymer film which increases in thickness the longer the contact time, even when the aqueous liquid composition is stable for a considerable period of time against precipitation or spontaneous flocculation of any solid phase, in the absence of contact with the active metal. (For the purposes of this specification, the term "active metal" should 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 that is thermodynamically able to dissolve to produce dissolved cations derived from the metal, with the accompanying evolution of hydrogen gas, when placed in contact with an aqueous solution of a non-oxidizing acid, where the activity of the ions of - - hydrogen is 1.00 equivalent per liter). These liquid compositions are referred to in this specification, and commonly in the art, as "autodeposition" or "self-deposition" compositions, dispersions, emulsions, suspensions, baths, solutions, or a similar term. The autodeposition is often contrasted with electrodeposition, which can produce very similar adhesion films but which requires that the surface to be coated be connected to a direct current source of electricity for the coating to occur. It is generally believed in the art that self-deposition works due to cations dissolving from the metal surface to be coated are, of course, initially limited to the volume of contact liquid in the immediate vicinity of the surface of the metal. metal from which they are dissolving, and these freshly dissolved cations interact with the liquid autodeposition composition in at least one of the following ways: (i) The dissolved cations precipitate the previously dissolved polymers by displacing the previously associated cations or forming residues. cation, in association with which the polymers are soluble, by the newly dissolved 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 dispersion of a polymer with inherently low solubility in water, which however, may remain in a stable suspension for a prolonged period of time in the absence of dissolved polyvalent cations, because the outer surfaces of the dispersed phase units carry a net negative electric charge, derived from anionic components of the dispersed polymer itself, and / or from a dispersing agent used to prepare the self-deposition composition in question. The net negative charge in the units of the dispersed phase in a liquid autodeposition composition is believed to be electrically counterbalanced by a diffuse excess of cations, usually monovalent cations, in the surrounding continuous phase of the dispersion. This excess of cations together with the negative charges in the dispersed phase units is an example of the well-known "double electric layer" or "Helmholz double layer" which is characteristic of most of the interfaces between the liquid phases that contain the particles dissolved solids and solids in contact with these liquid phases. As long as this double layer remains intact, the net negative charge on the outside of each unit of the dispersed phase causes the same to reject other units of the dispersed phase that also carry a net negative charge, and thus prevent the spontaneous coalescence of the dispersed phase units. When the double layer is sufficiently altered (or in the case of a soluble polymer, when the solubility is reduced) by introducing new cations, the polymer portions of numerous dispersed phase units and / or dispersed polymer molecules are added. The polymer molecules added together with a certain amount of liquid in which they were dissolved or dispersed, initially form a wet coating layer with at least sufficient cohesion to resist draining completely under the influence of the gravity of the earth. During further drying, this wet coating layer forms a continuous dry solid film, if the chemical nature of the polymer favors this transition and the temperature during drying is sufficiently well above the glass transition temperature of the related polymer. Polymers having this property of forming a continuous solid film or a body of finely dispersed or finely dispersed particles of the polymer in a liquid dispersion medium or solvent are defined as "film-forming" polymers, and at least one of these polymers is a necessary constituent of each bath of - conventional autodeposition. The continuous solid film formed by the film-forming polymer content of an autodeposition bath can constitute the entire self-deposited solidified and cured coating, and in any case normally constitutes the only continuous solid phase of the self-deposited, solidified and cured coating. It is quite common for a cured autodeposited coating to also include at least one discontinuous phase, more often a pigment such as carbon black. In other kinds of polymers, both coatings and solid objects, it is common to include a discontinuous solid phase usually called "filler or filler" or "reinforcer", that is, dispersed in the continuous polymer phase and acts to alter the properties of the compound formed by the continuous and discontinuous solid phases that those that prevail only in the continuous phase. In many cases, it is possible to both reduce the unit volume cost and increase the mechanical strength by including in a polymer a mineral filler material such as clay, calcium carbonate or the like. Although the inclusion of these materials in a self-deposition coating has been disclosed in the above patents, it is not believed that any use of the solid phases dispersed in the autodeposition baths has achieved beneficially practical success for any purpose except pigmentation. The use of two or more types of the film-forming resins in the autodeposition bath has also been disclosed, but again it is not believed to have achieved beneficially practical success. A principal object of this invention is to provide liquid self-deposition compositions from which it is possible to deposit on coatings of contacting metal surfaces containing dispersed solid phases, which provide for the self-deposited coatings at least some of the advantages achieved practically in other uses. of polymers, by the inclusion of filler materials and / or by the use of composite structures containing more than one type of polymer. Other alternative and / or simultaneous objects will become apparent from the additional description presented below. Except in the claims and working examples, or when expressly stated otherwise, all numerical quantities in this description indicating in quantities of material or reaction conditions, and / or use, shall be understood as being modified by the word "approximately" when describing the broader scope of the invention. Practice within numerical limits manifested, however, is usually preferred. Likewise, through the description, unless stated otherwise, express the opposite: percentage, "parts of", and relationship values are by weight or mass; the term "polymer" includes "oligomer", "copolymer", "terpolymer" and the like; the description of a group or class of materials as appropriate or preferred for a particular object in relation to the invention implies that mixtures of any two or more of the members of the group or class are equally appropriate or preferred; the description of the constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, or of generation in si tu within the composition by the chemical reaction (s) mentioned in the specification between one or more newly added constituents and one or more constituents already present in the composition when the other constituents are added, and does not prevent unspecified chemical interactions between the constituents of a mixture once they have been mixed; the specification of the constituents in ionic form further involves the presence of sufficient counterions to produce electrical neutrality for the composition as a whole or for any substance added to the composition; any of the specified counterions in this way implicitly preferably they are selected from among other constituents explicitly, specified in ionic form, to the greatest possible degree; otherwise, these counterions may be freely selected except to prevent counterions that act detrimentally to an object of the invention; the word "mole" means "gram-mole", and the word itself and all grammatical variations can be used for any chemical species defined by all the types and numbers of atoms present in it, regardless of whether the species is ionic, neutral , unstable, hypothetical, or in fact a stable neutral surface with well-defined molecules; the terms "solution", "soluble", "homogeneous", and the like should be understood as including not only equilibrium solutions or homogeneity but also dispersions that do not show a visually detectable trend towards phase separation over a period of time. observation of at least 100, or preferably at least 1000 hours during which the material is not mechanically altered, and the temperature of the material is maintained within the range of 18 ° C to 25 ° C; and the first definition of an acronym or other abbreviation applies to all subsequent uses of the same acronym or other abbreviation.

BRIEF COMPENDIUM OF THE INVENTION It has been found that at least one of the main objects of the invention can be achieved by including in an autodeposition bath an appropriate amount of the non-film-forming dispersed organic material which is co-deposited with the film-forming resin (s) as well. present in the self-deposition bath towards the wet self-deposited film.

DETAILED DESCRIPTION OF THE INVENTION A liquid self-deposition composition according to the present invention comprises, preferably consists essentially of, or more preferably consists preferably of water and the following components: (A) at least 1.0 percent, based on the entire composition, of a component of dissolved, dispersed or dissolved or dispersed film-forming polymer molecules; (B) a component of the emulsifying agent in an amount sufficient to emulsify any water insoluble part of any other component such that, in the liquid autodeposition composition, no no separation or segregation of the bulk phases occurs which is perceptible with non-assisted human vision during storage at 25 ° C for at least 24 hours after the preparation of the liquid autodeposition composition, in the absence of contact of the liquid composition of self-deposition with any metal that reacts with the liquid self-deposition composition to produce dissolved metal cations thereon with an electric charge of at least two; a dissolved accelerator component that is selected from the group consisting of acids, oxidation agents and complexing agents that do not form part of the components (A) or (B) mentioned immediately above, this accelerator component being sufficient in its tendency of oxidation and its amount to impart to the total autodeposition liquid composition an oxidation reduction potential that is at least 100 millivolts (hereinafter abbreviated generally as "mV") more oxidant than a normal hydrogen electrode; Y ÍD) a component of dispersed non-film-forming organic particles that are not part of of any of the components (A) to (C) mentioned immediately above; and, optionally, one or more of the following components: (E) a pigment component, filler material, or other dispersed solid phase materials other than materials that constitute any part of any of the components (A) to (a) D) mentioned immediately before; (F) a component of dyes or other dissolved coloring materials other than the materials that constitute any part of the components (A) to (E) mentioned immediately above; (G) a component of a coalescing agent, other than the materials that constitute any part of the components (A) to (F) mentioned immediately above; (H) a component of a solvent, other than the materials forming any part of the components (A) to (G) mentioned immediately above, wherein at least one constituent of either or both of the components (A) and (D) which is insoluble in water, dissolved during certain operation in the preparation of the liquid autodeposition composition; and (J) a plasticizer component, other than those materials that constitute part of the components (A) to (H) mentioned immediately above. In this description: The phrase "dispersed or dissolved and dispersed film-forming polymer molecules" means that the molecules described in this manner, when separated from any of the other materials with which they will co-disperse or co-dissolve and co-dispersing and in the form of a layer of at least a thickness of 5 millimeters of a homogeneous liquid mixture in which the polymers constitute at least 5 percent of the mass of the mixture, spontaneously form a continuous body which is solid at 30 ° C during drying or other removal of water, at a temperature of at least 30 ° C, from said layer; the term "solvent component" means a single phase, consisting of a single chemical substance or a mixture of chemical substances, which (i) is liquid at 25 ° C and (ii) is not constituted exclusively of water and inorganic solute materials only; and the term "coalescing agent" means a material that (i) is liquid at 100 ° C, (ii) has a boiling temperature at normal atmospheric pressure that is at least 110 ° C or preferably, preferably increased in the order provided, at least 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C or 165 ° C and independently is not greater than 300 ° C, or preferably, preferably increased in the order, provided, not greater than 290 ° C, 280 ° C, 270 ° C, 265 ° C, 260 ° C, 255 ° C, 250 ° C , 245 ° C, and (iii) activates the formation of dry coatings without coating irregularities (such as craters, blisters, coarse areas, bare areas, or the like) that are easily detectable with normal unassisted human vision, as determined by comparison of the density of the coating irregularities obtained, under identical processing conditions, by (iii) i) self-deposition of a liquid self-deposition composition containing the material being tested for the coalescence properties, followed by curing the film deposited in this way and (iii.ii) an otherwise identical process in the which material that is being tested to determine its coalescence properties is replaced in the liquid self-deposition composition used in the process, by means of an equal mass of water. In addition to a complete autodeposition liquid composition as described above, another embodiment of the invention is a liquid replenishment composition useful for replacing the polymer-forming polymer and other consumed materials by the use of a liquid composition of self-deposition according to the invention, and / or to make a working composition according to the invention by dilution with water and, optionally, the addition of other materials. This liquid replenishment composition according to the invention comprises, preferably consists essentially of, or more preferably consists of, water and: (At) at least 10 percent, based on the entire composition, of polymer molecules forming of film dissolved, dispersed or both dissolved and dispersed; (Bt) a component of the emulsifying agent in an amount sufficient to emulsify any water-insoluble portion of any other component such that, in the liquid refill composition, no separation or segregation of the bulk phases occurs which is perceptible with the normal human vision not aided during storage at 25 ° C for at least 24 hours after the preparation of the liquid refill composition with any metal that reacts with the liquid refill composition, to produce in the same metal cations dissolved with a load of at least two; and (D ') a component of dispersed organic particles not film formers that are not part of either the components (A ') or (B1) mentioned immediately above; and, optionally, one or more of the following components: (C) a dissolved accelerator component that is selected from the group consisting of acids, oxidizing agents, and complexing agents that are not part of any of the components (At), (Bt) or (D ') mentioned immediately above; (Eff) a pigment component, filler material, or other dispersed solid phase materials other than the materials that constitute any part of any of the components (At) to (D ') mentioned immediately above; (F1) a component of dyes or other dissolved coloring materials other than the materials constituting any part of the components (A ') to (E') mentioned immediately above; (G1) a component of a coalescing agent, other than the materials that constitute any part of the components (A ') to (F1) mentioned immediately above; (Ht) a component of the solvent, other than the materials forming any part of the components (A1) to (G ') mentioned in a manner immediately preceding, wherein the constituents of either or both of the components (A ') and (D') which are insoluble in water, were dissolved during some operation in the preparation of the liquid refill composition; and (Jt) a plasticizing component, other than the materials that constitute part of the components (A ') to (H') mentioned immediately above. Generally, each component of a preferred replenishment composition identified by a letter with premium immediately above preferably will have the same chemical composition for each component as for the component with the same letter without a premium in the work composition, as describes in addition to the foregoing, that it will be replenishment with or prepared from the replenishment composition. Therefore, the description below of the preferred constituents for each component and subcomponent thereof in chemical terms will be explicitly provided only for the non-premium components and the subcomponents, but applies equally to the components with premium to the same letter unless otherwise stated. The relationships between the different components, however, may be different between the work restocking compositions, in order to compensate for the faster consumption of some constituents of a work composition than for other constituents of the same composition when the work composition is used. The relationships between the subcomponents of a single principal component may also be different in the replenishment material than in the work composition that is replenished with the same, if the regimes of consumption of the subcomponents of a liquid composition of autodeposition of work are not in proportion with the concentrations of these ingredients in the liquid composition of autodeposition of work. In all cases, the concentrations of all the components except the water that are present in a replenishment composition are usually preferably greater than the concentration for the corresponding component in a liquid autodeposition working composition according to the invention by a factor which is at least, preferably increased in the proportionate order, of 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5.0 independently preferably is not greater than, preferably increased in the proportionate order, of 20, 15, 10, 8 or 6. If the concentration of components other than water in a replenishment composition is too low, the cost to ship it will be more high of what is economically justified, while if the concentration of these components is too high, storage stability will be reduced. A replenishment composition as immediately described above that is to be stored for several weeks or more before its use preferably does not contain an optional component (C) or any of the subcomponents thereof as will be described below, that all these sub-components are detrimental to the storage stability of the replenishment composition. The accelerator components are therefore preferably provided to a liquid working autodeposition composition according to this invention from at least one separate replenishment composition to maintain essentially constant values of the oxidizing power and the fluoride activity during use. of work composition, as is generally known in the art. The components (A), (B) and (C) as described above are conventional for autodeposition baths, and the appropriate and preferred chemical compositions for the same are disclosed in one or more of the following North American Patents and Patent Applications, all exhibitions of which, up to and including - - Not inconsistent with any explicit statement herein, are hereby incorporated by reference: Requests Series Nos. 60 / 087,983, 09 / 029,708, 09 / 000,928, 08 / 958,710, 08 / 745,550, 08 / 740,522 and 08 / 696,958; International Application Number PCT / US 96/12540; and Patent Numbers 5,688,560, 5,667,845, 5,646,211, 5,578,199, 5,545,319, 5,538,644, 5,372,853, 5,510,410, 5,427,863, 5,409,737, 5,393,416, 5,385,798, 5,372,853, 5,342,694, 5,300,323, 5,248,525, 5,164,234, 5,114,751, 5,080,937, 5,061,523, 5,011,715, 4,994,521, 4,800,106, 4,758,621 , 4,661,385, 4,637,839, 4,632,851, 4,564,536, 4,562,098, 4,554,305, 4,414,350, 4,411,950, 4,373,050, 4,366,195, 4,357,372, 4,347,172, 4,318,944, 4,243,704, 4,242,379, 4,229,492, 4,206,169, 4,199, 624, 4,191,676, 4,186,226, 4,186,219 , 4,178,400, 4, 177, 180, 4,160,756, 4,108,817, 4,104,424, 4,030,945, 4,012,351, 3,960,610, 3,955,532, 3,936,546, 3,914,519, 3,839,097, 3,795,546, 3,776,848, 3,791,431, 3, 592, 699 and 3, 585, 084. In a first Especially preferred embodiment of this invention, a polymer molecule of component (A) preferably includes a subcomponent - ^ - (Al) which is selected from the acid polymerization residues 3-The term "subcomponent" when used herein does not necessarily imply that the material designated in this way can not constitute the entire component of what is described as a subcomponent, except when it is additionally qualified, for example, by specifying a smaller portion of 100 percent of the total component that is constituted by the subcomponent. In this specific case, the term "subcomponent" refers to one or more portions of a single polymer molecule having a specific structure identifiable as a "residue" of a specific class of monomer that includes a polymerizable carbon-to-carbon double bond. A chemical compound (monomer) conforming to the general chemical formula: MIM2 IIC = C 1 I M3M4 where each of M ^, M2, M3 and M4 independently represents any monovalent residue, as long as the residues do not impede polymerization addition of the double bond shown in the general formula, when polymerized forms a residue that conforms to the general chemical formula: MXM2 II -C = C- II M3M4 wherein each of M ^ - to M4 has the same meaning as in the general formula for the compound provided above and the open bonds shown on the carbon atoms are attached to other moieties of the polymer molecule, This half it is defined as the "residue" in the polymer molecule of the compound or monomer that conforms to the general chemical formula shown first in this note. acrylic and methacrylic and the salts of both of these acids, in order to activate the crosslinking reactions during the drying and curing of the self-deposited coatings formed eventually. Methacrylic acid is especially preferred for this subcomponent. The average percentage of residues of subcomponent (Al) in the total component (A) of preference is at least, preferably increased in the proportionate order, of 0.50, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 4.9 and preferably independently is not greater than, preferably increased in the order provided, of 15, 10, 9.0, 8.0, 7.0, 6.5, 6.0, 5.5 or 5.1. If the percentage of the subcomponent (Al) is too low, the autodeposited coating formed tends to have a lower thermal resistance than what is desired, whereas if this percentage is too high elevated, the autodeposited coating formed has a tendency to be more susceptible to mechanical shock damage than desired. A polymer molecule of component (A) for this especially preferred first embodiment further includes a subcomponent (A2) which is selected from residues of the polymerization of esters of acrylic and methacrylic acids with alcohols containing at least, preferably increased in the proportioned order, 4, 5, 6, 7 or 8 carbon atoms per molecule and independently preferably contains no more than, preferably increased in the proportionate order of 20, 18, 16, 14, 12 or 10 carbon atoms per molecule. In addition, and independently, the alcohols corresponding to the esters of the subcomponent (A2) are preferably not straight chain alcohols, but instead preferably contain at least one branching outside the longer carbon-carbon chain in a molecule of the alcohol, this branch being independently preferably in the 2-position and preferably at least two-carbon-long. The 2-ethylhexyl acrylate residues are particularly preferred for this subcomponent. Independently of this exact chemical nature, the percentage of the total component (A) that is constituted of the portions of the subcomponent (A2) of - the molecules constituting the component (A), is preferably at least, preferably increased in the order provided of 5, 10, 15, 20, 23, 26, 29 or 32 and preferably independently is not greater than, with increased preference in the proportioned order of 60, 50, 45, 42, 39, 36 or 34. If the percentage of the subcomponent (A2) is too low, the autodeposited coating formed tends to be more susceptible to mechanical shock damage than desirable, whereas if the percentage of sub-component (A2) is too high, the thermal resistance of the autodeposited coating formed tends to be less than desirable. The molecules of component (A) for this first especially preferred embodiment of the invention are furthermore preferred, mainly for reasons of economy, to include a subcomponent (A3) which is selected from addition polymerizable hydrocarbon molecules residues, which of higher Preferably, in order to promote the thermal resistance of the optionally formed self-deposited coating, they are hydrocarbon molecules that include an aromatic core. The only especially preferred hydrocarbon comonomer is styrene. The percentage of the subcomponent (A3) in the component (A) as a preference set is at least, preferably increased in the proportioned order of 10, 15, 20, 23, 26, 29, 32 or 35 and independently preferably is not greater than, preferably increased in the proportioned order of 60, 50, 47, 44, 41 or 38. If the percentage of the subcomponent (A3) is too large, both the resistance Thermal as the susceptibility to damage from mechanical shocks tend to be less than desirable for self-deposited coatings formed from the composition, whereas if the percentage of the subcomponent (A3) is too low, the coatings produced will usually be more expensive than economically justified by any observed performance improvement. The molecules of component (A) for this first especially preferred embodiment of the invention also preferably include a subcomponent (A4) of acrylic monomer residues that are not part of any subcomponent (Al) or (A2) as described immediately below. foregoing. Particularly preferred individual residues are those of acrylonitrile. The percentage of the subcomponent (A4) in component (A) as a preference set at least is, preferably increased in the proportionate order of 5, 10, 13, 15, 17, 19, 21 or 23 and preferably independently is no greater than, preferably increased in the proportioned order of 50, 45, 40, 35, 32, 30, 28 or 26. In a second especially preferred alternative embodiment, the component (A) is selected from the molecules including vinylidene chloride residues to constitute 50 percent to 99 percent of the mass of the molecules and residues of sulfoethyl methacrylate to constitute 0.1 percent to 5 percent of the mass of the molecules, also optionally including the residues of one or more of the other comonomers that are They select from the group consisting of vinyl chloride, acrylonitrile, acrylamides and methacrylamides. The component (B) as described above can be incorporated into the component (A) by copolymerizing with the other monomers described for the component (A), an ionic material significantly soluble in water which is selected from the group of sulphonic acids and their salts having the following general formula: R-Q1-Q2- (S03) -M + wherein the "R" moiety are selected from the group consisting of vinyl and substituted vinyl, for example, alkyl-substituted vinyl; the symbol "Q1" represents a difunctional link group that will activate the double bond in the vinyl group; "Q2" represents one half of - - divalent hydrocarbon that has its valence bonds in different carbon atoms; and the "M +" symbol represents a cation. Sulfoethyl sodium methacrylate of the formula: CH2 = CC-0- (CH2) 2_S03_Na + III H3C 0 is a highly preferred copolymerizable material to be used as component (B) to form the "self-emulsifying" polymers or latexes " self-stabilizing. " More details about the use of this type of emulsifier component is provided in U.S. Patent No. 4,800,106 of January 24, 1989, column 7, line 45 to column 8 line 49. Contrary to the state of the art of autodeposition when resins are used. coating that predominantly contain vinylidene chloride residues, however, if the acrylic coating resins are used in this invention, conventional external emulsifying agents are usually as satisfactory as internal emulsifying agents which are copolymerized as part of the polymer molecules themselves . More particularly, the emulsifying agents and the amounts thereof used by commercial suppliers of acrylic latexes are generally satisfactory and preferably for use in this invention, the preference being mainly due to the cost savings of not having to prepare a special polymer to be used in autodeposition only. These commercially used emulsifying agents are usually privileged but all are believed to be anionic surfactants and most are believed to include arylsulfonic acid groups. The accelerator component (C) as described above can be selected from any material or combination of materials known to the subject in the prior autodeposition technique or otherwise found to provide satisfactory results. The especially preferred component (C) contains the following three subcomponents: (Cl) a concentration of fluoride ions in a working autodeposition bath is at least, preferably increased in the order of 0.4, 0.8, 1.0, 1.2, 1.40, 1.50, 1.55, 1.60, 1.65, 1.70, 1.75 or 1.79 grams of fluoride ions per liter of the total autodeposition bath, a concentration unit that can then be used for any other constituent as well as fluoride ions and hereinafter it is usually abbreviated as "g / 1" and preferably independently is not greater than, preferably increased in the order provided by 5, 4.0, 3.6, 3.3, 3.0, 2. 8, 2.60, 2.50, 2.40, 2.30, 2.25, 2.20, 2.15, 2.10, 2.05, 2.00, 1.95, 1.90 or 1.85 grams per liter of fluoride ions (all the fluorine atom content of any fluorine source in dissolved anions in a self-deposition bath according to the invention should be considered as fluoride ions, for the purpose of testing the conformity to these preferred concentrations of the fluoride ions, regardless of the current degree of ionization, aggregation, formation of complex ions, or similar that could happen); (C2) an amount of the oxidizing agent, preferably selected from the group consisting of hydrogen peroxide and ferric ions, sufficient to provide the working autodeposition liquid composition with an oxidation potential that is measured by the potential of a platinum or other Inert metal electrode in contact with the liquid autodeposition composition, ie, preferably increased in the order provided by at least 150, 175, 200, 225, 250, 275, 300, 325, 340 or 350 V plus oxidant a normal hydrogen electrode and preferably independently is, preferably increased in the order - provided no greater than 550, 525, 500, 475, 450, 425, 410 or 400 mV more oxidant than a normal hydrogen electrode; and (C3) a source of hydrogen cations in an amount sufficient to impart to the autodeposition bath a pH which is at least preferably increased in the order provided of 1.0, 1.4, 1.6, 1.8 or 2.0 and preferably independently is not greater than, preferably increased in the proportionate order of 3.8, 3.6, 3.4, 3.2, 3.0, 2.8 or 2.6. It should be understood that subcomponents (Cl) to (C3) do not all need to be derived from different materials. Hydrofluoric acid, in particular, is preferred as a source for both (Cl) and (C3), and ferric fluoride, which can be made by dissolving iron in hydrofluoric acid, can be supplied both (Cl) and (C2). Especially preferably ferric cations, hydrofluoric acid and hydrogen peroxide are all used to constitute component (C). In a working composition according to the invention, independently for each constituent: the concentration of the ferric cations is preferably at least preferably increased in the proportionate order of 0.5, 0.8, 1.0, 1.20, 1.30, 1.40 or 1.45 grams per liter and preferably independently is not greater than, preferably increased in the order of 2.95, 2.90, 2.85, 2.80, 2.75, 2.70, 2.65, 2.60, 2.55 or 2.50 grams per liter; the concentration of fluorine in anions preferably at least is, preferably increased in the order of 0.5, 0.8, 1.0, 1.2, 1.4, 1.50, 1.55, 1.60, 1.65, 1.70, 1.75 or 1.79 grams per liter and preferably independently is not greater than, preferably increased in the order of 10, 7.0, 5.0, 4.0, 3.0, 2.75, 2.50, 2.40, 2.30, 2.20, 2.15, 2.10, 2.05, 2.00, 1.95, 1.90, 1.85 or 1.81 grams per liter; and the amount of hydrogen peroxide added2 to a freshly prepared working composition is preferably at least, preferably increased in the order given, of 0.050, 0.10, 0.20, 0.30, 0.40, 0.50, 0.54 or 0.57 gram per liter and independently preferably it is no greater than, preferably increased in the order provided of 2.1, 1.8, 1.5, 1.2, 1.00, 0.90, 0.80, 0.70, 0.65 or 0.61 grams per liter.

Due to the numerous chemical reactions, including instantaneous decomposition, where hydrogen peroxide can participate, its concentration as determined analytically will often be considerably less than what corresponds to the amount added.

The component (D) as described above preferably comprises, more preferably consists essentially of, or still especially preferably consists of the particles with an average particle size (ie, larger linear dimension) which is at least, preferably increased in the determined order of 0.05, 0.10, 0.20, 0.25, 0.30, 0.35 or 0.40 micrometers (hereinafter usually abbreviated as "μm") and preferably independently is not greater than, preferably increased in the order provided of 4.0, 3.0, 2.0, 1.0, 0.80, 0.70, 0.65, 0.60 or 0.55 micrometers. Regardless of the actual size, a critical size distribution is preferred. More particularly, independently for each manifested preference: (i) at least, preferably increased in the order provided, 50, 65, 70, 75, 80, 85, 90 or 95 percent in number of the particles have a size that it is at least 62 percent of the average size; (ii) at least, preferably increased in the order provided, 40, 50, 60, 65, 70, 75, 80 or 85 percent in number of the particles have a size that is at least 76 percent of the average size; (iii) at least, preferably increased in the order provided, the 20, 30, 40, 45, 50, 55 or 60 percent in number of the particles have a size which is therefore - minus 86 percent of the average size; (iv) not more than, preferably increased in the proportioned order of 40, 30, 25, 20 or 15 percent in number of the particles have a size that is at least 114 percent of the average size; (v) not more than, preferably increased in the proportionate order of 20, 15, 12, 10, 8, 6 or 4 percent in number of the particles have a size that is at least 124 percent of the average size; and (vi) no more than 1 percent by number of the particles have a size that is at least 170 percent of the average size. The outer surface of the dispersed non-film-forming particles is, by definition of the component (D), an organic substance, preferably a non-film-forming polymer, but inside these particles can be and, at least for reasons of preference is, a gas, more preferably air. Particles of this type, dispersed in liquid water, can be obtained commercially from Rohm and Haas Co. under the ROPAQUE ™ brand, with indications of designation OP-62 LO and OP-96. Particles of polymer walls filled with gas of this type have the interesting property that they act optically as opaque, essentially white pigments. However, it has been found that once the particles are incorporated into the coating Self-deposited, if the coating heats sufficiently, it can become irreversibly transparent. In this way using these materials as the component (D), white and other opaque colors can be obtained for the self-deposited coatings, or the transparent self-deposited coatings can be obtained with sufficient heating. The opaque, light-colored autodeposited coatings have hitherto been practically obtainable even though the possibilities for obtaining these optical properties for self-deposited coatings have been disclosed in several patents. Regardless of its exact chemical and / or structural nature, when at least one initially non-transparent dried and cured self-deposited coating is desirable from a process in accordance with this invention, the component (D) is preferably present in the autodeposition composition used. in a volume, which is measured in milliliters (hereinafter abbreviated usually as "ml"), which has a relationship with respect to the combined mass, which is measured in grams (hereinafter abbreviated usually as "g"), of the total the components (A) and (B) in the same composition as at least is, preferably increased in the proportionate order of, 0.01, 0.03, 0.05, 0.070, 0.080, 0.090 or 0. 100 milliliters per gram. The volume of the component (D) to be used to determine this relationship includes not only the volume of the solid part of the component (D) but also the volume of any gas contained within any gas-tight solid-walled space (s). with particles of the component (D). Further, when the unit volume cost of the component (D) that is incorporated in the dried and cured self-deposited coating formed in a process according to the invention is less than the cost per unit volume of the components incorporated (A) and (B) in the dried and cured self-deposition coating, it is still especially preferred, at least for reasons of economy, that the amount of the component (D) in a self-deposition coating according to the invention have a volume to mass ratio of component (D) with respect to the combined components (A) and (B) which is at least, preferably augmented in the given order of 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60 or 0.64 milliliter per gram, since it has been found that the corrosion resistance of the autodeposited coating produced does not appear to be adversely affected by these ratios of the component (D) with respect to the components is combined (A) and (B).

- Independently, in order to ensure coating integrity, it is preferred that the ratio of the volume of the component (D) to the mass of the combined components (A) and (B) as defined above should not be greater than, increased preference of the proportionate order of, 2.0, 1.7, 1.4, 1.2, 1.0 or 0.8 milliliters per gram. The pigment and / or filler component (E) and the soluble dye component (F) can generally be selected for compositions according to this invention from materials set as satisfactory for similar uses in other liquid film-forming compositions. organic, particularly in previous autodeposition baths. Whether either or both of these optional components are preferably present in a composition according to the invention depends primarily on whether an additionally pigmented and / or otherwise colored coating is desirable. If it is, suitable pigments include, for example, carbon black, phthalocyanine blue, phthalocyanine green, quinacridone red, benzidene yellow and titanium dioxide. Any of the soluble pigments or dyes that tend to react chemically with other constituents of a composition according to the invention or to destabilize any of the dispersed particles present in the composition should normally be avoided. Any pigment and / or soluble dye used should be added to the composition in an amount that imparts the desired color and / or the desired depth or pitch to the composition. It should be understood that the specific amount used will be regulated by the specific coloring materials used and the desired coating color. Generally, the presence of a component of the coalescence agent (G) in a liquid autodeposition composition according to the invention is preferred when the component (A) is selected as described for the first especially preferred embodiment as described above. Preceding, because if this component, self-deposited coatings are usually very susceptible to bladder formation, cracking and / or detachment of the substrate during drying. This component is preferably selected from the group consisting of monoethers and monoesters of glycols, preferably glycols with at least one terminal hydroxy group. Ethylene glycol monoethers can be easily obtained and are effective in reducing the density of coating irregularities, but these ethylene glycol monoethers are restricted during use by anti-contamination laws in many cases. locations and have also been found to have a greater tendency - than the propylene glycol monoethers to destabilize the emulsions formed in products according to the invention. Therefore, propylene glycol monoethers, particularly the n-butyl and phenyl propylene glycol monoethers are preferred among the monoethers. A particularly preferred monoester is 2-methyl monopropionate 2,2,4-trimethyl-1,3-pentanediol; this is the especially preferred of all the materials for component (G). Examples of preferred commercially available coalescing agents are shown in Table 1.

- TABLE 1 Coalescence Agent Weight Tempe-% en Name of Chemical Name Moleratura Solution Factory cular de ebuAcuosa Saturated ll ° C DownolTM PM Propylene glycol monomethyl ether 90.1 120.1 Miscible DowanolTM PtB Propylene glycol mono-t-butyl ether 132.2 151J 14.5 DowanolTM PnB Propylene glycol mono-n-butyl ether 132.1 170.2 6.4 DowanolTM DPnB Dipropylene glycol mono-n-butyl ether 190.3 229 DowanolTM TPM Tripropylene glycol monomethyl ether 206.3 242.4 Miscible DowanolTM PPh Propylene glycol monophenyl ether 152.2 242.7 5.4 TexanolTM 2,2-4-trimethyl-1,3-pentanediol mono-2-ethyl propionate 216.3 244-247 < 0.1 Note to Fit for Table 1 * This material forms an azeotrope with water that boils at 95 ° C.

Regardless of its exact chemical composition, the percentage of the component (G) in a self-deposition liquid composition according to the especially preferred embodiment first described above of the invention is preferably, preferably increased in the order provided by at least 5, 10, 12, 14, 16, 18 or 20 percent of the total solids in the component (A) of the same liquid self-deposition composition as that described above and preferably independently is, preferably increased in the Order provided no greater than 30, 28, 26, 24 or 22 percent on the same basis. In contrast, for the second especially preferred embodiment as described above, component (G) is not necessary and is therefore preferably omitted for reasons of economy. For other types of polymers for component (A), the preference or lack of preference for the coalescence agent (G) can be inferred from the experience with prior art autodeposition compositions containing the same type of polymer for the component (TO) . The optional solvent component (H) may be required during the preparation of the liquid autodeposition compositions, in accordance with this invention, but it is not believed that in most cases contributes any desirable characteristics to the final liquid autodeposition compositions formed, and can still reduce the storage stability of these liquid autodeposition compositions. Therefore, when it is not needed, as it is not needed when any of the two especially preferred types of the component (A) that has already been described above, the solvent component (H) is preferably omitted completely. When the solvent is required during the preparation, such as for example for autodeposition compositions in which a considerable amount of epoxy resin is incorporated, the required solvent can be subsequently removed, when desired or necessary to act in accordance with the Anti-contamination requirements, by means known in the art, such as distillation under reduced pressure of a mixture of the solvent and the desired active ingredient at a temperature at which the active ingredient will remain liquid, before the formation of an oil dispersion -in-water of the desired final components of a liquid autodeposition composition, according to the invention. However, in some cases, the solvents do not unacceptably diminish the technical benefits of the final liquid autodeposition compositions according to the invention, and can be left in place. in the liquid autodeposition compositions according to the invention if they do not violate any legal requirements. Any residual solvent like this will normally be expelled during the curing of the autodeposited coatings. Any material effective as a plasticizer, for example, those known in the art such as di (2-ethylhexyl) phthalate, can be used as the optional component (J). Generally, however, if one of the two especially preferred types of the polymer component (A) is used, this external plasticizer will not be needed. There are no specific difficulties involved in preparing an autodeposition composition according to the invention; the components can simply be mixed together, once both components (A) and (D) have been emulsified separately, suitably, with anionic emulsifiers, to remain suspended in the aqueous solutions. Normally, component (C) is activated only for a short time before beginning to use an autodeposition composition. A process according to the invention for using a liquid autodeposition composition according to the invention in its simplest form comprises, preferably consists essentially of, or more preferably consists of, the operations of: (I) contacting a solid surface, which is capable of reacting with an autodeposition bath in accordance with the invention, to generate cations with a valence of at least two, dissolved in the autodeposition bath, with a self-deposition bath according to the invention as described above for a period of time sufficient to form through the solid surface in contact, a coating wet continuous containing molecules derived from the component (A), and the particles derived from the component (D) of the liquid autodeposition composition, in accordance with the invention, the wet continuous coating being sufficiently coherent and adherent to the solid surface for at least some part of it to remain on the solid surface against the force of the Natural environment gravity when the solid surface and any non-adherent part of the liquid autodeposition composition according to the invention are removed from contact with each other; (II) after the operation (I) as described immediately above, remove the wet continuous coating formed above the solid contact surface with any non-adherent part of the liquid autodeposition composition according to the invention, with which it remained in contact in operation (I) and, optionally, rinse the coating with at least one liquid rinse composition that is not a liquid autodeposition composition; and (III) after operation (II), ejecting from the wet continuous coating a sufficient amount of water and, optionally, other materials to convert it into a solid continuous dry coating in place above the solid surface in contact during the operation (I) All the operations of a conventional autodeposition process after the formation of the wet self-deposited coating containing the characterization component (D) in accordance with this invention, can be carried out in the same manner for a process of according to this invention as for a - Prior art process, except that the susceptibility of developed opacity to a self-deposition coating in accordance with the aforementioned preferred embodiments of this invention to become transparent by heating, should not be lost sight of. As a result of this susceptibility, when a non-transparent coating is desired, it may be necessary to deviate any of the above process operations that used high temperature cure and replace longer cures at lower temperatures. With the especially preferred type of component (D) as indicated above, for example, heating for 15 minutes at 176 ° C made an initially almost opaque coating completely transparent containing 0.10 milliliter of component (D) per gram of the component (A) (dried) and that had been cured initially at 125 ° C for 20 minutes. As with the self-deposition processes of the prior art, for most surfaces of the substrate, the corrosion resistance achieved can be considerably improved by including contact between the wet self-deposited coating and a rinse liquid as part of the operation (II ) as described above. Appropriately, but not - - exhaustively appropriate, rinsing liquids are described in the following North American Patents, each of which, to the extent that it discloses the rinsing of wet self-deposited coatings before drying them and is not contrary to any explicit statement made in the present, it is incorporated herein by reference: Number 5,667,845 of September 16, 1997 granted to Roberto and others; Number 5,342,694 of August 30, 1994, issued to Ahmed and others; Number 5,248,525 of September 28, 1993 granted to Siebert; and Number 4,637,839 of January 20, 1987 granted to Hall. More particularly, for the first especially preferred embodiment of the invention as described above, which uses the acrylic film-forming resin, rinsing liquids containing hexavalent chromium, optionally together with a certain amount of trivalent chromium, are preferred from then, while the second especially preferred embodiment as described above, which utilizes vinylidene chloride polymers predominantly as the component of the film-forming resin, rinsing liquids with ammonium bicarbonate are preferred. The rinse solution can be contacted, in a process according to the invention, - with a non-cured, self-deposited coating by any convenient method of combination of methods, such as spraying, curtain coating, or immersion, with the latter usually preferred. Preferably, the contact time between the rinsing solution and the uncured wet self-deposited coating is, preferably increased in the order provided, not less than 5, 10, 20, 30, 40, 45, 50, 55 or 60 seconds ( then abbreviated frequently as "sec") and independently of preference is, preferably increased in the order provided, not greater than 600, 400, 200, 120, 110, 100, 95 or 90 seconds. The temperature of the rinse solution during contact with a wet uncured autodeposited coating can be at any temperature at which the rinse solution is liquid but is preferably preferably, preferably increased in the order provided, not less than 10, 15. , 18 or 20 ° C and independently preferably, mainly for reasons of economy, which is no greater than, preferably increased in the order provided by 60, 45, 35, 30, 27, 25 or 23 ° C. After the reaction rinsing treatment, the wet self-deposited coating as modified by contact with the reaction rinse is sometimes rinsed again with water, preferably water - - deionized, if any, before drying and, if desired as usually preferred, can be cured by heating to a selected elevated temperature such that the protective properties of the coating develop fully but are not adversely affected. The temperature and time of the treatment will depend on the nature of the specific film-forming resin, that is, the component (A), on the autodeposited coating and the thickness of the coating. With autodeposition baths containing most types of acrylic organic film-forming resins, self-deposited coatings are preferably heated, during or after drying, at a temperature which is, preferably increased in the order provided by at least the 90, 100, 110, 120, 130, 140 or 145 ° C. and independently of preference is, preferably increased in the order provided, not greater than 230, 220, 200, 190, 180, 170, 160 or 165 ° C. When the film-forming resin used consists predominantly of vinylidene chloride residues, the maximum temperature at which the resulting self-deposited coating is heated during its drying and curing preferably is at least, preferably increased in the proportioned order of 30, 50, 70, 80, 85, 90, 95 or 100 ° C and independently preferably is not greater - 4 of, preferably increased in the order of 150, 140, 130, 125, 120, 115, 110 or 105 ° C. Heating times for cure vary preferably from 5 seconds to 30 minutes, depending on the mass of the coated article. Preferably the coating is heated for a period of time until the metal substrate has reached the temperature of the heated environment, typically in a forced air oven. The invention and its benefits can also be seen from the working examples and comparison examples that will be noted below. PREPARATION AND USE OF COMPOSITIONS INCLUDING DISPERSAL ORG NON-FORMER FILM PARTICLES Group 1 With Acrylic Polymer Film Forming Resin In these examples, RHOPLEX ™ WL-91 which is an acrylic latex (hereinafter usually abbreviated as "WL-91") commercially supplied by Rohm & Haas Co. , usually diluted with additional water, and with the surfactant DOWFAX ™ 2A1 (hereinafter usually abbreviated as "2A1") added as a complementary emulsifying agent, was used as a primary precursor dispersion by supplying the entire film-forming polymer component (A ) and at least part of the 9 -. 9 - component of the emulsifying agent (B) of the optional liquid self-deposition composition according to the invention. The WL-91 product is disclosed by its supplier as containing 41 percent to 42 percent solids, of which at least 95 percent are believed to be acrylic polymer solids and any remainder as being the emulsifying agent; the chemical nature and exact amount of the emulsifying agent are not disclosed by the supplier. The ROPAQUE ™ OP-96 pigment dispersion (hereinafter abbreviated usually as "OPO-96") commercially supplied by Rohm and Haas Co. was the source of the component (D); in accordance with its supplier, this material contains 30.5 percent solids in the form of particles that average in size 0.55 micrometer and that normally have at least one interior space filled with air per particle so that the volume percentage of the dispersion Total occupied by its solid content and the gas-tight spaces within the particles of its solids contents is 50 percent, and each gram of the dried dispersion occupies 1.59 milliliters of volume. A basic autodeposition bath is prepared; consisted of, in addition to water: 5.7 percent solids of KWL-91; 1.21 percent of a coalescing agent Texanol ™; 0.04 percent emulsifying agent 2A1; a sufficient amount of dissolved hydrofluoric acid to give the total composition a pH of 2.3; a sufficient amount of ferric fluoride to supply, together with the hydrofluoric acid, 1.8 grams of fluoride ions per liter of the total composition, and sufficient amount of hydrogen peroxide to provide, together with the other components, an oxidation potential for the total solution that was 330 mV more oxidant than a normal hydrogen electrode. Successive additions of the OP-96 product were added to this basic autodeposition bath to produce autodeposition compositions according to the invention, with the volume ratios of component (D) to solid of component (A) shown in Table 2. The normal test boards were provided with a self-deposition coating by immersion for 90 seconds in most of these autodeposition compositions according to the invention, which were maintained at normal room temperature of 22 ° C + 5 ° C, under the conditions of processing also provided in Table 2.

- TABLE 2 Relative Number (s) - Temperature (s) and Time (s) Appearance, Drying Rinse / Healing Tissue- [Reversing ml (D)] / [ (A)] ler ° C 1st Min. 2 ° C 2 ° Min 1 0., 10 Water 125 20 none none Whitish 2 0,, 10 Water 125 20 176 15 Transparent 3 0., 10 1087 RR 125 60 none none Blanquecino l 0., 10 1087 RR 125 30 145 30 Blanquecino 0. .21 1087 RR 125 20 none none Blanquecino 6 0. .21 1087 RR 145 20 none none Blanquecino 0. 21 Water 125 20 none none Whiter than # 0.21 Water 145 20 none none 1 and 2 9,10 0.21 Water 176 20 none none Transparent 11,12 0.31 Water 145 30 none none Opaque, whiter than # 7 and E 13 0.31 1087 RR 145 25 none none Whiter than # 14 0.31 1087 RR 145 45 none none 5 and 6 - ,16 0.43 Water 145 20 none none Opaque white 17 0.43 1087 RR 145 20 none none Whiter than # 18 0.43 1087 RR 145 40 none none 13 and 14 19,20 0.65 Water 145 20 none none Opaque White 21 0.65 1087 RR 145 20 none none Both had the 22 0.65 1087 RR 145 40 none none same appearance 23.24 0.65 Water 175 20 none none Transparent .26 0.65 1087 RR 175 20 none none Brown 7? Breviations for Table 2"Min." means "minute (s);" 1087 RR "means a AUTOPHORETIC® 1087 Reaction Rinse solution, commercially available from Henkel Surface Technologies, Madison Heights, Michigan, used as instructed by the supplier"; "#" means "number". Note to fit for Table 2 * Certain amount of chromium is believed to be retained in and to darken the dried and cured coating when 1087 RR is used.

Group 2 With Poly (Vinylidene Chloride) Film-Forming Resin In these examples, a self-emulsified poly (vinylidene chloride) latex diluted with additional water was used to supply all of the component (A) of the film-forming polymer and all of component (B) of the emulsifying agent, except for any emulsifying agent that is included in OP-96 as described above. Regarding Group 1, a base autodeposition bath was prepared. For this group, the base autodeposition bath consisted of, in addition to water: 5.4 percent of a self-emulsifying film-forming polymer; a sufficient quantity of dissolved hydrofluoric acid to give the total composition a pH of 2.3; a sufficient amount of ferric fluoride to supply, together with the hydrofluoric acid, 1.8 grams of fluoride ions per liter of the total composition, and a sufficient quantity of hydrogen peroxide to provide, together with the other components, an oxidation potential for The total solution was 330 mV more oxidant than a normal hydrogen electrode. Successive additions of the OP-96 product were added to this base autodeposition bath to produce autodeposition compositions according to the invention with the volume ratios of the component (D) to the solids of the component (A) shown in Table 3. The normal test boards were provided with a self-deposition coating by immersion for 90 seconds in the majority of these autodeposition compositions according to the invention, which were maintained at normal room temperature. of 22 ° C + 5 ° C. all these coatings were dried and cured for 20 minutes at 104 ° C. Other processing conditions are provided in Table 3.

TABLE 3 Number (s) Ratio, Appearance Liquid of Iden [ml of (D)] / Pos-Rinse Coating tification [g of (A) and (B)] 27-32 0.12 2150 RR Light Yellow * almost opaque 33.34 0.12 White Water, almost opaque .36 0.37 White Water, opaque 37-40 0.37 2150 RR Yellowish *, opaque - Abbreviations for Table 3"2150 RR" means "a Reaction Rinse solution, AUTOPHORETIC®2 150, commercially available from Henkel Surface Technologies, Madison Heights, Michigan, used in accordance with the supplier's instructions". Note to Fit for Table 3 * It is believed that more iron is retained in and obscures the dried and cured coating when 2150 RR is used.

CORROSION TEST Some of the test boards prepared in Groups 1 and 2 were conventionally assembled and subjected to neutral salt spraying tests according to the American Society for Testing and Normal Material Processing B-117 for 500 hours. The ratio of the volume of component (D) to the mass of component (A) within the scale tested had no significant effect on corrosion resistance. The times and / or the higher drying and curing temperatures improved the corrosion resistance in Group 1, as would be expected for similar self-deposited coatings without the addition of component (D) with this type of film-forming resin. Detailed results are shown in Table 4.

TABLE 4 Number (s) of Width of Shift and Any Identification Other Observations after 500 Hours 4 4 mm 5 16 mm 6 14 mm 13 16 mm 14 18 mm 17 13 mm 18 15 mm 21 15 mm 22 11 mm 25 7 mm; uneven shift 27 2 mm 31 2 mm 32 2 mm 35 2-3 mm 37 2-3 mm; a few spots of field rust

Claims

- - CLAIMS:

1. A liquid autodeposition composition comprising water and the following components: (A) at least 1.0 percent, based on the entire composition, of a component of dissolved, dispersed or dispersed or dispersed film-forming polymer molecules; (B) a component of the emulsifying agent in an amount sufficient to emulsify any water-insoluble part of any other component such that, in the liquid autodeposition composition, no separation or segregation of the bulk phases occurs which is perceptible with human vision Normally not assisted during storage at 25 ° C for at least 24 hours after the preparation of the liquid autodeposition composition, in the absence of contact of the liquid autodeposition composition with any metal that reacts with the liquid autodeposition composition to produce in the same metal cations dissolved with an electric charge of at least two; (C) a dissolved accelerator component that is selected from the group consisting of acids, oxidizing agents and complexing agents that are not part of - of the components (A) or (B) mentioned immediately above, this accelerator component being sufficient in strength and amount to impart to the total autodeposition liquid composition an oxidation reduction potential that is at least 100 millivolts (a then abbreviated usually as "mV") more oxidant than a normal hydrogen electrode; and (D) a component of the dispersed non-film-forming organic particles that do not form part of any of the components (A) to (C) mentioned immediately above.

2. A liquid autodeposition composition according to claim 1, wherein: - the component (A) is selected from molecules containing the following subcomponents between the amounts indicated below: (Al) from about 2.0 to about 7.0 percent of a subcomponent that is selected from the polymerization residues of the acrylic and methacrylic acids and the salts of both of these acids; (A2) of from about 15 to about 50 percent of a selected subcomponent of the polymerization residues of esters of the - - acrylic and methacrylic acids with alcohols containing at least 4 but not more than 20 carbon atoms per molecule. (A3) from about 10 to about 50 percent of a subcomponent that is selected from addition polymerizable hydrocarbon molecules residues; and (A4) from about 10 to about 40 percent of a subcomponent of acrylic monomer residues that do not form part of either the subcomponent (Al) or (A2) as described immediately above; and component (C) contains the following three subcomponents: (Cl) from about 0.8 to about 4.0 grams per liter of fluoride ions; (C2) an amount of the oxidizing agent that provides the liquid autodeposition composition with an oxidation potential that is from about 200 to about 500 mV plus oxidant than a normal hydrogen electrode; and (C3) a source of hydrogen cations in an amount sufficient to impart to the autodeposition bath a pH that is from about 1.0 to about 3.8.

3. A liquid autodeposition composition according to claim 2, wherein: - the component (A) is selected from molecules containing the following subcomponents in the amounts indicated below: (Al) from about 3.5 to about 6.5 percent of a subcomponent that is selected from the polymerization residues of methacrylic acid and its salts; (A2) of from about 26 to about 39 percent of a subcomponent that is selected from residues of the polymerization of esters of acrylic and methacrylic acids with alcohols containing at least 8 but not more than 10 carbon atoms per molecule. (A3) from about 32 to about 44 percent of a subcomponent that is selected from addition polymerizable hydrocarbon molecules residues that contain an aromatic nucleus; and (A4) from about 17 to about 30 percent of a waste subcomponent of the acrylic monomers that are not part of any subcomponent (Al) or (A2) as described immediately above; - component (C) contains the following three subcomponents: (Cl) from about 1.60 to about 2.10 grams per liter of fluoride ions; (C2) an amount of hydrogen peroxide and ferric ions which provides the liquid autodeposition composition with an oxidation potential which is from about 350 to about 400 V more oxidant than a normal hydrogen electrode; and (C3) a source of hydrogen cations in an amount sufficient to impart to the autodeposition bath a pH that is from about 2.0 to about 2.6; and - a component (G) is also contained which is selected from the group consisting of monoethers and monoesters of glycols with at least one terminal hydroxy group, the mass of component (G) being from about 10 to about 30 percent of the mass of the solids in component (A) of the same composition.

4. A liquid autodeposition composition according to claim 1, wherein: - the component (A) incorporates the component (B) and is selected from molecules that include residues of - - vinylidene chloride that make up 50 percent to 99 percent of the mass of the molecules and sulfoethylmethacrylate residues that make up 0.1 percent to 5 percent of the mass of the molecules and, optionally, the residues of one or more of other comonomers that are selected from the group consisting of vinyl chloride, acrylonitrile, acrylamides, and methacrylamides; and component (C) contains the following three subcomponents: (Cl) from about 0.8 to about 4.0 grams per liter of fluoride ions; (C2) an amount of the oxidizing agent that provides the liquid autodeposition composition with an oxidation potential that is approximately 200 to about 500 V more oxidant than a normal hydrogen electrode; and (C3) a source of hydrogen cations in an amount sufficient to impart to the autodeposition bath a pH that is from about 1.0 to about 3.8.

5. A liquid autodeposition composition according to claim 4, wherein component (C) contains the following three subcomponents: (Cl) from about 1.60 to about 2.10 - grams per liter of fluoride ions; (C2) an amount of hydrogen peroxide and ferric ions that provides the liquid autodeposition composition with an oxidation potential that is from about 350 to about 400 mV more oxidant than a normal hydrogen electrode; and (C3) a source of cations in hydrogen in an amount sufficient to impart to the bath at autodeposition at a pH that is from about 2.0 to about 2.6.

6. A liquid autodeposition composition according to claim 5, wherein: the component (D) is selected from particles of non-film-forming polymer walls filled with gas having sizes such that: the average size (is say, the largest linear dimension) of the particles is from about 0.2 to about 1.0 micrometer; at least about 75 percent in number of the particles have a size that is at least 62 percent of the average size; - at least approximately 75 percent in number of the particles have a size that is at least 76 percent of the average size; - at least about 50 percent in number of the particles have a size that is at least 86 percent of the average size; - * - no more than about 25 percent in number of the particles have a size that is at least 114 percent of the average size; - no more than about 10 percent in number of the particles have a size that is at least 124 percent of the average size; - no more than about 1 percent in number of the particles have a size that is at least 170 percent of the average size; the volume, measured in milliliters, of the component (D) in the composition has a relation to the mass, measured in grams, of the total components (A) and (B) in the same composition that is within a scale of approximately 0.30. to approximately 1.7 milliliters per gram. - -

7. A liquid autodeposition composition according to claim 4, wherein: - the component (D) is selected from particles of non-film-forming polymer walls filled with gas having sizes such that: - the average size (is say, the largest linear dimension) of the particles is from about 0.2 to about 1.0 micrometer; - at least about 75 percent in number of the particles have a size that is at least 62 percent of the average size; - at least about 75 percent in number of the particles have a size that is at least 76 percent of the average size; - at least about 50 percent in number of the particles have a size that is at least 86 percent of the average size; - no more than about 25 percent in number of the particles have a size that. it is at least 114 percent of the size average; - no more than about 10 percent in number of the particles have a size that is at least 124 percent of the average size; and - not more than about 1 percent in number of the particles have a size that is at least 170 percent of the average size; and - the volume, measured in milliliters, of the component (D) in the composition, has a relation to the mass, measured in grams, of the total of the components (A) and (B) in the same composition that remains inside a e from about 0.30 to about 1.7 milliliters per gram.

8. A liquid autodeposition composition according to claim 3, wherein: the component (D) is selected from particles of non-film-forming polymer walls filled with gas having sizes such that: the average size (is say, the largest linear dimension) of the particles is from about 0.2 to about 1.0 micrometer; - at least approximately 75 percent in number of the particles have a size that is at least 62 percent of the average size; - at least about 75 percent in number of the particles have a size that is at least 76 percent of the average size; at least about 50 percent in number of the particles have a size that is at least 86 percent of the average size; - no more than about 25 percent in number of the particles have a size that is at least 114 percent of the average size; - no more than about 10 percent in number of the particles have a size that is at least 124 percent of the average size; no more than about 1 percent in number of the particles have a size that is at least 170 percent of the average size; the volume, measured in milliliters, of the component (D) in the composition has a relation to the mass, measured in 'grams, of the total of the components (A) and (B) in the same composition, which is within a e from about 0.30 to about 1.7 milliliters per gram.

9. A liquid autodeposition composition according to claim 2, wherein: the component (D) is selected from non-film-forming polymer wall particles filled with gas having sizes such that: - the average size (ie, the largest linear dimension) of the particles is from about 0.2 to about 1.0 micrometer; - at least about 75 percent in number of the particles have a size that is at least 62 percent of the average size; - at least about 75 percent in number of the particles have a size that is at least 76 percent of the average size; - at least about 50 percent in number of the particles have a size that is at least 86 percent of the average size; -no more than about 25 percent in number of particles have a size that it is at least 114 percent of the average size; - no more than about 10 percent in number of the particles have a size that is at least 124 percent of the average size; and no more than about 1 percent by number of the particles have a size that is at least 170 percent of the "average" size, and the volume, measured in milliliters, of the component (D) in the composition, has a relation to the mass, measured in grams, of the total of components (A) and (B) in the same composition that falls within a range of approximately 0.30 to approximately 1.7 milliliters per gram

10. A liquid self-deposition composition in accordance with claim 1, wherein: the component (D) is selected from non-film-forming polymer wall particles filled with gas, and the volume, measured in milliliters, of the component (D) in the composition, has a ratio to the mass , measured in grams, of the total of components (A) and (B) in the same composition that is at least approximately 0.20 milliliter per gram.

11. A process to form a self-deposited coating, the process comprises the operations of: (I) contacting a solid surface, which is capable of reacting with a liquid autodeposition composition to generate cations with a valence of at least two, dissolved in a liquid autodeposition composition, with a liquid autodeposition composition in accordance with any of claims 1 to 10 for a period of time sufficient to form through the contact solid surface a continuous wet coating containing molecules derived from the component (A), and particles derived from the component (D) of the liquid composition of autodeposition, the wet continuous coating being sufficiently coherent and adherent to the solid surface during at least a certain part of it to remain on the solid surface against the force of gravity natural environment when the solid surface and any non-stick part of the autodeposition liquid composition in accordance with the invention are removed from contact with one another; (II) after operation (I) as described immediately above, remove the wet continuous coating formed above the solid contact surface with any non-adherent part of the liquid autodeposition composition according to the invention, with which was contacted during operation (I) and, optionally, rinsed the coating with at least one liquid rinse composition which is not a liquid autodeposition composition; and (III) after operation (II), ejecting from the wet continuous coating a sufficient amount of water and, optionally, other materials to convert it into a solid continuous dry coating in place above the solid surface with which He was contacted in operation (I).

12. A process according to claim 11 wherein: the liquid autodeposition composition used in step (I) comprises a component (D) that is selects from non-film-forming polymer wall particles filled with gas that act as a white pigment for the liquid autodeposition composition; the volume, measured in milliliters, of the particles of non-film-forming polymer walls filled with gas in the composition has a ratio to the mass, measured in grams, of the total of the components (A) and (B) therein composition that is at least about 0.10 milliliter per gram; and - in step (III), the temperature of the solid coating is controlled so that the self-deposited coating does not become transparent.

13. A liquid replenishment composition comprising water and: (At) at least 10 percent, based on the entire composition, of dissolved, dispersed or dispersed or dispersed film-forming polymer molecules; (B ') a component of the emulsifying agent in an amount sufficient to emulsify any water-insoluble part of any other component so that, in the liquid refill composition, no - no separation or segregation of bulk phases occurs which is perceptible with normal human vision not aided during storage at 25 ° C for at least 24 hours after the preparation of the liquid refill composition, in the absence of contact of the composition of liquid replenishment with any metal that reacts with the liquid replenishment composition to produce dissolved metal cations thereon with a charge of at least two; and (D?) a component of the dispersed non-film-forming organic particles that are not part of any of the components (At) or (Bt) mentioned immediately above.

14. A liquid replenishment composition according to claim 13, wherein the component (At) is selected from the molecules containing the following subcomponents in the amounts indicated below: (A'l) from about 2.0 to about 7.0 by a hundred of a subcomponent that is selected from the polymerization residues of the acrylic and methacrylic acids and the salts of both of these acids; (At2) of approximately 15 to about 50 per - one hundred of a subcomponent that is selected from the ester polymerization residues of the acrylic and methacrylic acids with alcohols containing at least 4 but not more than 20 carbon atoms per molecule. (A '3) from about 10 to about 50 percent of a subcomponent that is selected from addition polymerizable hydrocarbon molecule residues; and (A '4) from about 10 to about 40 percent of a subcomponent of acrylic monomer residues that do not form part of any of the subcomponents (A'l) or (A' 2) as immediately described above. .

15. A liquid replenishment composition according to claim 14, wherein: - the (At) component is selected from molecules that contain the following subcomponents in the amounts indicated below: (A'l) of about 3.5 a about 6.5 percent of a subcomponent that is selected from the polymerization residues of methacrylic acid and its salts; (A'2) from about 26 to about 39 per one hundred of a subcomponent that is selected from the polymerization residues of the esters of the acrylic and methacrylic acids with alcohols containing at least 8 but not more than 10 carbon atoms per molecule. (Ar3) from about 32 to about 44 percent of a subcomponent that is selected from the residues of addition polymerizable hydrocarbon molecules containing an aromatic nucleus; and (A14) from about 17 to about 30 percent of a subcomponent (A '4) of residues of the acrylic monomers that are not part of any subcomponent (A'l) or (A' 2) as described immediately previous; Y - a component (Gt) is also selected which is selected from the group consisting of monoethers and monoesters of glycols with at least one terminal hydroxy group, the mass of the component (G?) being about 10 to about 30 percent of the mass of the solids in the component (A ') of the same composition.

16. A liquid replenishment composition according to claim 13, wherein the - - component (A ') incorporates component (B') and is selected from molecules that include: vinylidene chloride residues that constitute 50 percent to 99 percent of the mass of the molecules; and sulfoethyl methacrylate residues that constitute from 0.1 percent to 5 percent of the mass of the molecules; and, optionally, residues of one or more of the comonomers which are selected from the group consisting of vinylidene chloride, acrylonitrile, acrylamides and methacrylamides.

17. A liquid replenishment composition according to any of claims 13 to 16, wherein: the component (D ') is selected from non-film-forming polymer wall particles filled with gas having sizes such that: the average size (ie, the largest linear dimension ~) of the particles is from about 0.2 to about 1.0 micrometer; - at least about 75 percent in number of the particles have a size that is at least 62 percent of the size - 7 - average; - at least about 75 percent in number of the particles have a size that is at least 76 percent of the average size; - at least about 50 percent in number of the particles have a size that is at least 86 percent of the average size; no more than about 25 percent in number of the particles have a size that is at least 114 percent of the average size; - no more than about 10 percent in number of the particles have a size that is at least 124 percent of the average size; and no more than about 1 percent in number of the particles have a size that is at least 170 percent of the average size; and the volume, measured in milliliters, of the component (Dt) in the composition, has a relation to the mass, measured in grams, of the total of the components (A ') and (B') in the same composition, which remains within from a scale of about 0.30 to about 1.7 milliliters per gram.