MXPA00003596A

MXPA00003596A - Composition and process for multi-purpose treatment of metal surfaces

Info

Publication number: MXPA00003596A
Application number: MXPA/A/2000/003596A
Authority: MX
Inventors: Bruce H Goodreau; Thomas J Prescott
Original assignee: Bruce H Goodreau; Henkel Corporation; Thomas J Prescott
Priority date: 1997-10-14
Filing date: 2000-04-13
Publication date: 2001-05-17

Abstract

A multipurpose treatment composition for metal surfaces comprises phosphate ions, fluorometallate ions, water soluble polymers containing substituted aminomethylene moieties bonded to benzene rings which also have an oxygen atom bonded to another carbon atom in the same ring, and a distinct kind of film-forming polymer. The compositions are free from chromium and other heavy metals that cause serious pollution problems in some prior art treatment compositions. Coating layers formed in a process according to the invention are effective for at least three different purposes:increasing adhesion of and corrosion protection from subsequently applied paints or other protective coatings with a largely organic matrix;without any subsequently applied protective coating, providing at least temporary protection against staining and development of white rust on zinc or zinc alloy surfaces treated in a process according to the invention, and providing sufficient lubricity to permit roll forming of sheet metals treated in a process according to the invention without the need for additional liquid lubricants such as oil.

Description

COMPOSITION AND PROCESS FOR THE TREATMENT FOR MULTIPLE PURPOSES OF METAL SURFACES BACKGROUND OF THE INVENTION This invention relates to aqueous liquid compositions and processes that employ such liquids for the chemical treatment of metal surfaces to form a coating layer therein. The compositions are free of chromium and other heavy metals that cause severe contamination problems in some prior art treatment compositions. Coating layers formed in a process according to the present invention can be effective for at least three different purposes: increasing the adhesion and protection against corrosion of subsequently applied paints or other protective coatings with a largely organic matrix; without any subsequent applied protective coating, provide at least temporary protection against staining and development of white oxidation on zinc or zinc alloy surfaces treated in a process in accordance with the present invention; and providing sufficient lubrication to allow the formation by lamination of treated metal sheets in a process in accordance with the present invention without the need for additional liquid lubricants such as oil.

Traditionally, most zinciferous and / or aluminiferous surfaces have been passivated by chemical treatment with aqueous liquid compositions containing at least a certain amount of hexavalent chromium. Concerns about environmental pollution led in recent years to the development and dissemination of some chromium-free treatments. However, there is still much to be improved in terms of, among other things, cost, ease of use, and versatility of the coatings formed. Conventional lamination oil lubricants can also pose problems of contamination, cost, and fire hazard. Several alternatives and / or concurrent objects of this invention are: (i) offer a total or substantially chromium free composition and process for passivation that offer adequate resistance against corrosion compared to passivation agents containing high quality chromates employed previously; (ii) offer an economic passivation treatment; (iii) reduce the potential for contamination; (iv) provide a solid coating that provides adequate lubrication for sheet metal rolling without the need for additional organic liquid lubricant; (v) offer improvements in paint adhesion through the same coating as that used for passivation; and (vi) reduce overall operating costs. Except in the claims and in the examples of operation, or when expressly indicated otherwise, all the numerical quantities in this description that refer to quantities of material or conditions of reaction and / or use must be understood modified by the word "approximately "in the description of the broader scope of the invention. However, the practice of the present invention is generally preferred within the numerical limits presented. Also, in this specification, unless expressly stated otherwise: percentage, "parts of", relationship values are established by weight. The description of a group or class of materials as suitable or preferred for a given purpose in relation to the invention implies that mixtures of two or more of the members of the group or class are equally suitable or preferred; the description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not exclude chemical interactions between the constituents of a mixture once mixed; the specification of materials in ionic form implies the presence of a sufficient number of counterions to produce electrical neutrality for the composition globally; the implicitly specified counterions in this way should preferably be selected from among other constituents specified explicitly in ionic form, as far as possible; otherwise, such counterions can be freely selected, except that counterions that act negatively on the objects of the invention should be avoided; the terms "molecule" and "mol" and their grammatical variations can be applied to ionic, elementary entities or to another type of chemical entities defined by the number of atoms of each type present there, as well as to substances with well-defined neutral molecules; the first definition of an acronym or another type of abbreviation applies to all subsequent uses of the same abbreviation and mutatis utandis is applied to normal grammatical variations of the initially defined abbreviation; the term "paint" includes all similar materials that can be designated through more specialized terms such as lacquer, enamel, varnish, finish, and the like; and the term "polymer" includes "oligomer", "homopolymer", "copolymer", "terpolymer", and the like. SUMMARY OF THE INVENTION It has been found that one or more of the objects set forth above for the invention can be achieved by the use of an aqueous liquid composition comprising, preferably consisting essentially, or especially consisting of water and: (A ) a concentration of a component of dissolved anions containing phosphorus; (B) a concentration of a dissolved component selected within the group consisting of simple and complex anions containing fluorine atoms; (C) a concentration of a component of organic molecules dissolved and / or stably dispersed including phenolic ring portions with aminomethyl substituents there as described in greater detail in one or more of the following North American Patents, all of which, except as to the content that may not be consistent with an explicit statement here, they are incorporated by reference: 4,376,000 from March 8, 1983, from Lindert; 4,433,015 of February 21, 1984 of Lindert; 4,457,790 of July 3, 1984 of Lindert; 4,517,028 of May 14, 1984 by Lindert; 5,116,912 of May 26, 1992 by Lindert et al .; 5,068,299 of November 26, 1991, by Lindert et al .; and 4,970,264 of November 13, 1990 by Lindert et al.; and (D) a concentration of a component of dissolved film-forming molecules, stably dispersed, either both dissolved or stably dispersed, said molecules are not part of any of the components mentioned above (A) to (C) ); and, optionally, one or more of the following components: (E) a concentration of a component of a solid material dispersed in a stable manner which in isolation has a coefficient of static friction, measured between two pieces of the solid material itself or between the solid material and cold rolled steel, which is not auro than 0.35, this solid material does not form part of any of the aforementioned components (A) to (D); (F) a surfactant and / or dispersing agent component for one of the components (D) or (E) that is not part of any of the aforementioned components (A) to (E); (G) a preservative component that is not part of any of the aforementioned components (A) to (F); and (H) a dye component that is not part of any of the aforementioned components (A) to (H). The term "stably dispersed" when used to describe an insoluble component in a continuous liquid phase, as in the definitions of the components (C), (D), and (E) above, means that the insoluble component is not concentrated spontaneously in a separate liquid or solid phase perceptible to the naked eye as different from the liquid continuous phase but in contact with said phase within an observation period of the combination of insoluble stable dispersed component and liquid continuous phase for 10 hoursor, preferably, with increasing preference in the indicated order, for 1, 3, 5, 10, 30, 60, 90, 120, 240, or 360 days when stored without mechanical disturbance at a temperature of 20 ° C in a scattered form. Molecules should be understood as "film-forming" for the purposes of this description if, when a homogeneous solution and / or suspension of the molecules in water containing at least 20% of the molecules is dried at a temperature of at least 25 ° C. from a liquid film thickness not greater than 1 millimeter, a continuous and coherent solid film is produced at a temperature of 25 ° C. Various embodiments of the invention include working compositions for direct use in the treatment of metals, replenishment concentrates from which such work compositions can be prepared by dissolving with water and / or by mixing with other concentrate compositions, concentrates fillers suitable for maintaining the optimum performance of the work compositions in accordance with the present invention, processes for treating metals with a work composition according to the invention, and extended processes including additional conventional steps per se, such as work on cold, cleaning, rinsing and subsequent application of paint or some other similar coating process that places a protective coating containing an organic binder on the metal surface treated in accordance with a more limited embodiment of the invention. Fabricated articles that include surfaces treated in accordance with a process of the present invention are also within the scope of the invention. BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING Not applicable DETAILED DESCRIPTION OF THE INVENTION The component (A) is preferably selected from anions containing oxygen where the phosphorus is in its +5 oxidation state. Any phosphorus oxyacid (V) and / or any salt thereof dissolved in an aqueous liquid composition according to the invention is to be understood for the purposes of this description as providing anions to the aqueous liquid composition to the extent of its total equivalent content stoichiometric, based on the phosphorus and oxygen atoms present, of: HP03; acids corresponding to the general formula H (n + 2) PnO (3n + i) / where "n" represents a positive integer; and / or complete and partial salts of all these previously mentioned acids, independently of the magnitude with which the ionization can actually occur in the solution. (It is generally considered in the art that all these acids and / or their anions exist in potential equilibrium between them, the equilibrium having a strong preponderance of entities that contain a single phosphorus atom at low temperatures and low concentrations in water and the entities that they contain several phosphorus atoms and the material conventionally represented by HPO3, considered as a cyclic trimer with the formula H3P3O9, becoming more predominant at high temperatures, high concentrations in water, or highly alkaline conditions in aqueous solutions). At least for reasons of economy, the orthophosphoric acid (ie, H3P04) and its salts are preferred as the source of component (A) in an aqueous liquid composition according to the invention, and the acid is preferably used by taking as the preferred acidic pH value for an aqueous liquid working composition according to the invention. Component (B) is preferably selected from the group consisting of anions with one of the chemical formulas F "1, HF2_1, BF4-1, AIF5" 3, SiF6"2, TiFd" 2, FeF6 ~ 3, ZrF6" 2, HfF6 ~ 2. Within this group, trivalent ions are less preferred than others, complex ions including boron, silicon, titanium, zirconium, or hafnium atoms are preferred over simpler anions containing only fluorine and optionally hydrogen, and titanium containing anions are most preferred.An acid or salt of an acid containing the elements of one of the chemical formulas indicated above preferred anions should be understood for the purposes of this disclosure as providing said anions an aqueous liquid working composition according to the invention in which it dissolves to the total stoichiometric equivalent of the anions in the acid or salt, independently of the magnitude of the actual ionization that may occur in the solution As in the case of the component (A), an acid source for the component (B) is usually preferred taking into account the preferred acid pH of the working compositions according to the invention. Regardless of the source of the anions of the component (B) present in an aqueous liquid composition according to the invention, if these anions contain a metallic element or boron, their concentration preferably is such that their total stoichiometric equivalent concentration of metallic elements and boron in moles per kilogram of the total composition, a unit of concentration usually abbreviated below as "M / kg", has a ratio in relation to the concentration of phosphorus atoms in M / kg which is stoichiometrically equivalent to the concentration of component (A) in the same composition that is at least, preferably increasing in the order indicated, 0.03: 1.0, 0.06: 1.0, 0.09: 1.0, 0.12: 1.0, 0.15: 1.0, 0.18: 1.0, 0.21: 1.0, 0.24 : 1.0, 0.26: 1.0, or 0.28: 1.0 and preferably independently is not more than, with increasing preference in the order indicated, 2.0: 1.0, 1.5: 1.0, 1.0: 1.0, 0.8: 1.0, 0.6: 1.0, 0.50 : 1.0, 0.40: 1.0, 0.35: 1.0, or well 0.30: 1.0. If component (B) does not contain boron or metal atoms, it preferably has a stoichiometrically equivalent concentration at a concentration of fluorine atoms in M / kg having a ratio relative to a concentration of phosphorus atoms in M / kg that is stoichiometrically equivalent to the concentration of component (A) in the same composition as is at least, preferably increasing in the order indicated, 0.3: 1.0, 0.5: 1.0, 0.7: 1.0, 0.9: 1.0, 1.1: 1.0, 1.3: 1.0, 1.5: 1.0, or 1.7: 1.0 and preferably independently is not more than, with increasing preference in the order indicated, 7: 1.0, 5: 1.0, 4.0: 1.0, 3.5: 1.0, 3.2: 1.0, 2.9: 1.0, 2.6: 1.0, 2.4: 1.0, 2.2: 1.0, 2.2: 1.0, 2.0: 1.0, or 1.8: 1.0. Component (C) is preferably selected from the group consisting of materials (a) and (ß), where: (or) consists of polymer molecules each of which has at least one unit corresponding to the general formula (II) presented below: where: each of R2 to R4 is selected, independently from each other and independently from one molecule of the component to another and from one unit to another forming the molecule when there is more than one unit of this type in a single polymeric molecule, within the a group consisting of a hydrogen portion, an alkyl portion with 1 to 5 carbon atoms, and an aryl portion with 6 to 18 carbon atoms; each of Y1 to Y4 is selected, independently of each other, except as indicated below, and independently of one molecule from the component to another and from one unit to another corresponding to this formula when there is more than one unit of this type in the single polymer molecule, of the group consisting of: a hydrogen atom portion; a -CH2C1 portion; an alkyl portion having 1 to 18 carbon atoms; an aryl portion with 6 to 18 carbon atoms; a portion corresponding to the general formula -CR12R13OR14, wherein each of R12 to R14 is selected from the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, an ercaptoalkyl portion, and a phosphoalkyl portion; and a Z portion that corresponds to one of the two general formulas that we present below: R '+ / N or r C- - N R \ R R wherein each of R5 to R8 is independently selected from and independently of one molecule from the component to another and from one unit to another of any polymer molecule according to the formula when there is more than one unit of this type in a molecule single polymer, within the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion and R9 is selected from the group consisting of a portion hydrogen, an alkyl moiety, an aryl moiety, a hydroxy or polyhydroxyalkyl moiety, an amino or polyaminoalkyl moiety, a mercapto or polycarboxy alkyl moiety, a phospho or polyphosphoalkyl moiety, a -O "moiety, and an -OH moiety, at least one moiety Y1 to Y4 in at least one unit of each selected polymer molecule is a Z-portion as defined above, and 1 is selects, independently of one molecule from the component to another and from one unit to another of any polymer molecule that corresponds to this formula when there is more than one unit of this type in a single polymer molecule, within the group consisting of a portion hydrogen, an acyl portion, an acetyl portion, a benzoyl portion; a 3-allyloxy-2-hydroxypropyl portion; a 3-benzyloxy-2-hydroxypropyl portion; a 3-butoxy-2-hydroxypropyl portion; a 3-alkyloxy-2-hydroxypropyl portion; a 2-hydroxyoctyl portion; a 2-hydroxyalkyl portion, a 2-hydroxy-2-phenylethyl moiety; a 2-hydroxy-2-alkylphenylethyl moiety; a benzyl, methyl, ethyl, propyl, unsubstituted alkyl, unsubstituted allyl, or unsubstituted alkylbenzyl moiety; a halo or polyhaloalkyl, or halo or polyhaloalkenyl portion; a portion derived from a condensation polymerization product of ethylene oxide, propylene oxide or a mixture thereof by removal of a hydrogen atom therefrom; and a portion of sodium, potassium, lithium, ammonium or substituted ammonium cation, or substituted phosphonium or phosphonium; and (ß) consists of polymer molecules, none of which includes a unit corresponding to the general formula (II) as indicated above but includes at least one unit corresponding to the general formula (III) presented below : where: each R10 and R11 is selected, independently from each other and independently from one molecule of the component to another and from one unit to another in accordance with this formula when there is more than one unit of this type in a single polymer molecule, within the group consisting of a hydrogen portion, an alkyl portion with 1 to 5 carbon atoms, and an aryl portion with 6 to 18 carbon atoms; each of Y4 to Y6 is selected, independently from each other, except as indicated below, and independently from one molecule of the component to another and from one unit to another of any polymer molecule corresponding to this formula when there is more than one unit of this type in a single polymer molecule within the group consisting of: a hydrogen portion, a -CH2C1 portion; an alkyl portion having 1 to 18 carbon atoms; an aryl portion with 6 to 18 carbon atoms; a portion that complies with the general formula -CR12R13OR14, wherein each of R12 to R14 is selected from the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion; and a Z-portion according to that defined for the material (OI) above, at least one of Y1 to Y4 in at least one unit of each selected polymer molecule is a Z-portion according to that defined above; and W2 is selected, independently of one molecule from the component to another and from one unit to another corresponding to this formula when there is more than one unit of this type in a single polymer molecule, within a group consisting of a portion of hydrogen atom, an acyl portion, an acetyl portion, a benzoyl portion; a 3-allyloxy-2-hydroxypropyl portion; a 3-benzyloxy-2-hydroxypropyl portion; a 3-butoxy-2-hydroxypropyl portion; a 3-alkyloxy-2-hydroxypropyl portion; a 2-hydroxyoctyl portion; a 2-hydroxyalkyl portion; a 2-hydroxy-2-phenylethyl moiety; a 2-hydroxy-2-alkylphenylethyl moiety; a benzyl, methyl, ethyl, propyl, unsubstituted alkyl, unsubstituted allyl or unsubstituted alkylbenzyl moiety; and a halo or polyhaloalkyl, or halo or polyhaloalkenyl portion; a portion derived from a condensation polymerization product of ethylene oxide, propylene oxide or a mixture thereof by removal of a hydrogen atom therefrom; and a portion of sodium, potassium, lithium, ammonium or substituted ammonium cation, or substituted phosphonium or phosphonium; the expression "polymer molecule" in the above definitions of materials (OI) and (ß) includes any electrically neutral molecule with a molecular weight of at least 300 daltons. It will be observed by those skilled in the art that the general formulas (II) and (III) above represent repetitive portions that characterize the compound (s) of component (C) of a composition in accordance with the present invention; non-terminal end portions are illustrated. The end portions of the molecules according to one of the general formulas (II) or (III) can be selected by the expert in the field based on previously presented techniques.

For example, the end groups may result from a specific polymerization process employed or from the intentional addition in order to alter the characteristics of the molecule. Thus, the end groups may be hydrogen, hydroxyl, initiation fragments, chain transfer agents, disproportionation groups, or groups resulting from other methods to terminate a growing polymer chain. For reasons of economy at least, the end groups are preferably hydrogen or hydroxyl. Usually, primarily for reasons of economy, it is preferred to use as materials (a) and / or (ß) predominantly molecules that consist entirely, except in the case of relatively short end groups, of units that comply with one of the general formulas ( II) and (III) in accordance with what is described above. Again for reasons of economy mainly, such materials are generally prepared by the reaction of homopolymers of g-vinylphenol, for the material (), or condensation products of phenol-aldehyde, for the material (b) with formaldehyde and secondary amines to graft Z portions into some of the activated benzene rings in the materials that reacted in this way. However, in some particular cases, it may be useful to employ more chemically complex types of materials (OI) and / or (ß). For example, molecules formed by the reaction of a condensable form of a molecule belonging to the () or (ß) component in accordance with that defined above, except that the molecule reacted, do not initially need to meet the requirement for the component ( a) or (ß) that each molecule contains at least one Z-portion, with at least one other type of molecule selected from the group consisting of phenols, tannins, novolak resins, lignin compounds, aldehydes, ketones, and mixtures thereof, for the purpose of preparing a condensation reaction product which optionally, if required, is further reacted with (1) an aldehyde or ketone and (2) a secondary amine to introduce at least one Z-portion in accordance with the defined above to each molecule, in such a way that the molecule can qualify as material (OÍ) OR (H.H) . Another example of more complex materials that can be used as material (a) is a material in which the polymer chains are at least predominantly copolymers of simple or substituted 4-vinylphenol with another vinyl monomer such as for example acrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl methyl ketone, isopropenyl methyl ketone, acrylic acid, methacrylic acid, acrylamide, methacrylamide, n-amyl methacrylate, styrene, m-bromostyrene, jp-bromostyrene, pyridine, diallyldimethylammonium salts, 1,3-butadiene, n-butyl acrylate, t-butylaminoethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, n-butyl vinyl ether, t-butyl vinyl ether, m-chlorostyrene, o-chlorostyrene, p-chlorostyrene, n-methacrylate decyl, N, N-diallylmelamine, N, N-di-n-butylacrylamide, di-n-butyl itaconate, di-n-butyl maleate, diethylaminoethyl methacrylate, diethylene glycol monovinyl ether, diethyl fumarate, diethyl itaconate, phosphate d e diethyl vinyl, vinyl phosphonic acid, diisobutyl maleate, diisopropyl itaconate, diisopropyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl maleate, di-n-nonyl fumarate, di-n-nonyl maleate, dioctyl fumarate, di-n-octyl itaconate, di-n-propyl itaconate, N-dodecyl vinyl ether, ethyl fumarate acid, ethyl maleate acid, ethyl acrylate, ethyl cinnamate, N-ethyl methacrylamide, ethyl methacrylate, ethyl vinyl ether, 5- ethyl-2-vinylpyridine, 5-ethyl-2-vinylpyridin-1-oxide, glycidyl acrylate, glycidyl methacrylate, n-hexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, isobutyl methacrylate, isobutylvinylether, isoprene, isopropyl methacrylate, isopropylvinylether, itaconic acid, lauryl methacrylate, methacrylamide, methacrylic acid, methacrylonitrile, N-methylolacrylamide , N-methylol-methacrylamide, N-isobutoxymethylacrylamide, N-isobutoxy-methylmethacrylamide, N-alkyloxymethylacrylamide, N-alkyl-oxymethylmethacrylamide, N-vinylcaprolactam, methyl acrylate, N-methylmethacrylamide, α-methylstyrene, m-methylstyrene, o-methylstyrene , p-methylstyrene, 2-methyl-5-vinylpyridine, n-propyl methacrylate, sodium p-styrenesulfonate, stearyl methacrylate, styrene, p-styrenesulfonic acid, p-styrenesulfonamide, vinyl bromide, 9-vinylcarbazole, vinyl, vinylidene chloride, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylpyridine N-oxide, 4-vinylpyrimidine, and N-vinylpyrrolidone. The following preferences, primarily for reasons of economy, improved corrosion resistance and / or improved solubility in water, apply, independently of each preference, to the materials molecules (OI) and (ß): each of R2 to R6, R10, R11, 1, and W2, independently of each other and independently of one unit to another in the same molecule or in a different molecule, is preferably a hydrogen atom moiety; - each of Y1 to Y5 independently from each other and from one unit to another in the same molecule or in a different molecule, is preferably a hydrogen atom portion or a Z portion; averaged over the total content of component (C), each polymer molecule contains a number of units corresponding to one of the general formulas (II) and (III) in accordance with that defined above which is, at least, with increasing preference in the order indicated, 2, 3, 4, 5, 6, 7, or 8 and independently preferably not more than 100, 75, 50, 40, 30, or 20; in the total of the materials (OI) and (ß) in a composition used in step (II) according to the invention, the number of Z portions has a ratio in relation to the number of aromatic nuclei that is at least, with increasing preference in the order indicated, 0.01: 1.0, 0.03: 1.0, 0.05: 1.0, 0.10: 1.0, 0.20: 1.0, 0.40: 1.0, 0.50: 1.0, 0.60: 1.0, 0.70: 1.0, 0.80: 1.0, 0.90: 1.0, or 0.95: 1.0 and independently, preferably, is not more than, with increasing preference in the order indicated, 2.0: 21.0, 1.6: 1.0, 1.50: 1.0, 1.40: 1.0, 1.30: 1.0, 1.20: 1.0, 1.10: 1.0, or 1.00: 1.0; in the total of the materials (OI) and (ß) in a composition used in step (II) according to the invention, the number of "polyhydroxy" Z portions, wherein at least R8 in the general formulas given above for the Z portions have (i) from 3 to 8, or preferably from 4 to 6 carbon atoms and (ii) as many hydroxyl groups, each bonded to a different carbon atom, that one less than the number of carbon atoms in the portion R8, it has a ratio relative to the total number of Z portions in the composition which is at least, preferably increasing in the order indicated, 0.10: 1.0, 0.20: 1.0, 0.30: 1.0, 0.40: 1.0, 0.50: 1.0, 0.60: 1.0, 0.70: 1.0, 0.80: 1.0, 0.90: 1.0, or 0.98: 1.0 (the preparation of such materials is described in the North American Patents cited above); and R7 is an alkyl portion having not more than, preferably increasing in the order indicated, 5, 4, 3, 2 or 1 carbon atom. In addition, and independently of other preferences, at least for reasons of economy, the material of type (OI) is preferred in comparison with the material of type (ß). A poly (5-vinyl-2-hydroxy-N-benzyl) -N-methylglucamine is a specific polymer of the most preferred type which, within the range of acid pH which is preferred to be established, is considered to be present in an aqueous liquid composition according to this invention at least in part as an ammonium salt. Regardless of the exact chemical nature, component (C) is preferably present in an aqueous liquid composition according to the present invention in a concentration having a ratio in relation to the stoichiometrically equivalent concentration with H3PO4 of component (A) in the same aqueous liquid composition which is at least, preferably increasing in the indicated order, 0.02: 1.0, 0.04: 1.0, 0.06: 1.0, 0.08: 1.0, 0.10: 1.0, 0.12: 1.0, 0.14: 1.0, 0.16: 1.0, 0.18: 1.0, or 0.20: 1.0 and preferably, independently, is not more than, with increasing preference in the order indicated, 2.0: 1.0, 1.3: 1.0, 1.0: 1.0, 0.67: 1.0, 0.53: 1.0, 0.40: 1.0, 0.35: 1.0, 0.30: 1.0, 0.26: 1.0, 0.23: 1.0, or 0.21: 1.0. Primarily, for reasons of economy and / or comfort, the component (D) according to the above defined is preferably selected from the large group of commercially available polymer latex dispersions in water and / or solutions in water with phases dispersed that meet the criteria specified above for component (D). For example, synthetic polymers of vinyl esters, styrene and vinylidene and vinylidene chlorides as well as polymers of fully synthetic, natural synthetically modified, and natural polysaccharides are suitable, and polymers of acrylic acid and methacrylic acid of esters, nitriles, and amides thereof two unsaturated acids are preferred. Polymers of the type known in the art as "self-crosslinking" are particularly preferred., which contain comonomers capable of a chemical reaction during or after the drying of latexes in which they are dispersed in order to form chemical bonds between the chains of largely linear polymer structures that were present in the dispersed phase of the latex. In addition, and independently of the other preferences, the constituents of component (D) preferably have a glass transition temperature that is at least, preferably increasing in the order indicated, -10, 0, +5, +10, +15, +20, +25, or + 30 ° C and independently of preference is not more than, preferably with increasing preference in the indicated order, 75, 65, 55, 45, or 40 ° C. Regardless of its exact chemical nature, the component (D) in a dry non-volatile solids base, is preferably present in an aqueous liquid composition according to the present invention in a concentration having a ratio in relation to the concentration stoichiometrically equivalent as H3P04 of component (A) in the same aqueous liquid composition which is at least, preferably increasing in the order indicated, 0.3: 1.0, 0.5: 1.0, 0.7: 1.0, 0.9: 1.0, 1.1: 1.0, 1.3: 1.0, 1.5: 1.0, 1.7: 1.0, 1.9: 1.0, or 2.1: 1.0 and independently of preference is not more than, with increasing preference in the indicated order, 15: 1.0, 10: 1.0, 8.0: 1.0, 7.0: 1.0, 6.0: 1.0, 5.5: 1.0, 5.0: 1.0, 4.5: 1.0, 4.5: 1.0, 4.0: 1.0, 3.7: 1.0, 3.4: 1.0, 3.1: 1.0, 2.9: 1.0, 2.7: 1.0, 2.5: 1.0, or 2.3: 1.0. The optional component (E) is preferably present in a composition according to the present invention more frequently than any of the other optional components. The optional component (E) in preferred amounts reduces the coefficient of friction of a coating formed by the treatment in accordance with this invention. The addition of component (E) also appears to improve corrosion resistance in some but not in all other compositions in accordance with the present invention. Although inorganic materials such as molybdenum disulfide and graphites are suitable for component (E) of an aqueous liquid composition in accordance with this invention, primarily for reasons of economy and dispersion stability, component (E) is preferably selected from among materials organic, particularly solid paraffins, synthetic polyethylene and / or polypropylene polymers (optionally partially or totally halogenated, especially fluorinated), and other natural or synthetic waxes, having a specific gravity no greater than, preferably increasing in the order indicated, 2.2 , 2.0, 1.8, 1.6, 1.4, 1.2, or 1.0 and the required low coefficient of static friction as part of the component (E) With even greater preference, the materials for the component (E) have a coefficient of static friction which is not more than, preferably increasing in the indicated order, 0.30, 0.28, 0.26, 0.24, 0.22, 0.20, 0.18, 0.16,0.14 , or 0.10. Such materials are commercially available in predispersed form, and a material of this type that is stable in an acidic aqueous solution is preferred. In order to achieve said stability, a cationic dispersing agent for the constituent of component (E) is generally preferred; Nonionic dispersing agents are the next most preferred agents, and the anionic dispersing agents are the least preferred because most of the dispersions prepared therewith are unstable in acid compositions according to this invention. Dispersions of high density polyethylene, paraffin wax, or mountain wax are especially preferred, the first two elements being less expensive than the latter and therefore are preferred for this reason. If the minimization of friction is more important than the cost in some particular use however, perfluoroethylene polymers are most preferred. Regardless of its exact chemical nature, if component (E) has the specific gravity of high density polyethylene, the concentration, on a non-volatile solids basis, of component (E) in an aqueous liquid composition according to the invention when the component (E) is preferably used to have a ratio relative to the concentration of component (D) in a dry non-volatile solids base, in the same aqueous liquid composition according to the invention which is at least of increasing preference in the order indicated, 0.005: 1.0, 0.015: 1.0, 0.025: 1.0, 0.035: 1.0, 0.042: 1.0, 0.046: 1.0, 0.050: 1.0, 0.052: 1.0, 0.054: 1.0, 0.056: 1.0, or 0.058 : 1.0 and is independently of preference not greater than, preferably increasing in the order indicated, 0.40: 1.0, 0.25: 1.0, 0.15: 1.0, 0.10: 1.0, 0.075: 1.0, 0.068: 1.0, 0.062: 1.0, or 0.060 : 1.0. If the specific gravity of the component is different from the specific gravity of a high-density polyethylene, the proportions given above must be adjusted in such a way that the same ratio is found between (component constituent volume (E)) and (component weight) (D)) that established for the preferences indicated above in the case of high density polyethylene. Except for the dispersion agent for the component (E) and frequently also for the component (D), the other optional components of an aqueous liquid composition according to this invention are not generally required and therefore are preferably omitted. However, a surfactant may be required to ensure adequate humidification of some metallic substrates and / or to reduce foaming and it may be helpful to provide some cleaning along with the coating; Conservation may be required if the composition is feeding microorganisms in the environment where it is used; and a colorant may be useful for visually estimating the thickness of the applied coating or for providing a decorative effect to the surface. For various reasons, it is sometimes preferred that the compositions according to the invention as defined above are substantially free of many ingredients employed in compositions for similar purposes of the prior art. Specifically, when maximum storage stability of a concentrate is desired, avoiding possible problematic ions and / or minimizing the potential for contamination, it is preferred, preferably increasing in the indicated order, independently of each minimized substance preferably listed below, that these compositions contain no more than 25, 15, 9, 5, 3, 1.0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01, 0.001, or 0.0002, percent of each of the following constituents, except in the extent to which these components can be part of a necessary or optional component of the composition in accordance with the above defined: nitrile; halolates and perfalates (ie, perchlorate, chlorate, iodate, etc.); hydroxylamine and salts and hydroxylamine complexes; chloride; bromide; I last; organic compounds containing nitro groups; hexavalent chromium; ferricyanide; ferrocyanide; pyrazole compounds, and dissolved ions of metals with an atomic number greater than 20. Components such as these may not be harmful in some cases but were not found useful or useful in compositions according to the invention and therefore their minimization is usually preferred to less for reasons of economy. The treatment of a metallic substrate in a process according to this invention preferably comprises the formation of a layer of an aqueous liquid working composition in accordance with the present invention as described above on the surface to be treated, and then the drying in the place, without any rinsing, or any other disturbance, of the layer formed in this way. For this reason, the concentrations of the necessary components (A) to (D) in accordance with that described above in a working composition according to the invention are usually not critical. A thick layer of a working composition at low concentrations will contain the same final constituents according to the invention as a thin layer of a more concentrated working composition. However, it was found that at least a slightly acidic pH is required for a working composition according to the invention, possibly even though the invention is not considered to be limited by this or by any other theory, because a certain degree of Acidity is required to dissolve at least some metal ions from the surface that is being treated for incorporation into the coating. More particularly, the pH value of the working composition according to the invention is preferably at least, preferably increasing in the indicated order, -05, 0.0, 0.5, 1.0, 1.2, 1.4, 1.6, 1.8, or 2.0 and independently of preference is merely that, with increasing preference in the indicated order, 6.0, 5.0, 4.0, 3.8, 3.6, 3.4, 3.2, 3.0, 2.8, 2.4, or 2.2 The liquid layer of a working composition of According to the invention formed in a process according to the invention, it preferably has a thickness such that the average mass increase per unit area of treated metal substrate, measured after drying at the site, is at least, preferably with increasing preference in the order indicated, 0.20, 0.40, 0.60, 0.80, 1.0, 1.5, or 2.0 grams of mass increase per square meter of treated metal substrate surface, this unit is then usually abbreviated as "g / m2" and independently, primarily for reasons of Economy, preferably it is only, with increasing preference in the indicated order, 10, 8, 6, 5.0, 4.0, 3.5, 3.0, 2.5, or 2.2 g / m2. As a general guideline, due to the practical aspects of control of liquid film coating thicknesses, the total content of components (A) to (E) of a working composition according to the invention is at least, with increasing preference in the indicated order, 1, 3, 5, 7, 9 or 11% and independently of preference is not more than, with increasing preference in the indicated order, 50, 45, 40, 35, 30, 25, 20, or fifteen%. The formation of a liquid film on a metallic substrate surface to be treated in a process according to the invention can be achieved by any of numerous methods known to those skilled in the art, such as, for example, transfer roll coating or direct coating , curtain coating, immersion in a volume of a working composition in accordance with the present invention held in a container and then removing said volume, and spraying and then spraying suspension, in all cases with the additional option of removing a Part of the initially adherent liquid cap by using a flow of compressed gas such as air or a brush or other metal device, in order to dry instead a preferred amount of non-volatiles contained in the aqueous liquid working composition. Drying can be achieved by simple exposure to the ambient air for a sufficient time, particularly if the treated surface has been formed at a sufficiently high temperature such that the drying occurs within a few seconds of the contact separation with the aqueous liquid composition. work in accordance with the invention as described above.

Alternatively and usually preferably, one can accelerate the drying by exposing the wet surface after treatment at a higher temperature than the normal room temperature, in an oven or by means of any other device such as infrared radiation heating. , microwave drying, and the like well known per se in a technique. Preferably, the peak temperature of the metal during the drying process does not exceed 150, 125, 100, 90, 80, 76, 70, or 66 ° C. The peak metal temperature can be conveniently controlled by a sensor strip fixed on a part of the substrate during drying. The sensor strip determines an upper limit in terms of the temperature peak by irreversible changes of zones calibrated by temperature of the sensor strip. The peak temperature can also be measured directly during the drying process by other means known to those skilled in the art, for example, an infrared photometer. Preferably, the temperature of the aqueous working composition during the process according to the invention is at least, preferably with increasing preference in the order indicated, 15, 17, 19, 21, 23, or 25 ° C and independently of preference , primarily for reasons of economy, said temperature is not greater than 60, 50, 45, 40, 35, or 30 ° C. The quality of the formed coating layer is not substantially affected as is known by the temperature during the treatment if the temperature is of these preferred limits. The time during which the physical contact is maintained between the metal surface to be treated and an aqueous liquid working composition according to the invention preferably, for reasons of economy of operation, is as short as possible, consistent with the formation of a coating layer as effective as desired. More specifically, the contact time of preference is not greater than, with increasing preference in the given order, 200, 150, 100, 75, 50, 40, 30, 25, 20, 15, 13, 11, 10, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0. 2.0. 1.5, or 1.0 seconds. Prior to the use of the treatment according to this invention for a metal substrate, the substrate is preferably completely cleaned by any of several methods well known in the art suitable for the particular substrate to be treated. As with many other types of metal surface treatment compositions, with those in accordance with the present invention it is economically advantageous to supply their active ingredients to the end users in one or more liquids that contain much higher concentrations of active ingredients than is otherwise known. would normally use in work compositions. In this particular case, it has been found that the more concentrated compensation concentrates that can be prepared do not have consistently the degree of storage stability that is desired if they contain all of the components (A) to (E) of preferred compositions in accordance with invention as described above. However, components (A) to (C) may be present in a primary concentration with good storage stability. Said concentrate preferably contains, independently of each given component: an amount of component (A) that corresponds stoichiometrically to an amount of H3P04 constituting at least, preferably increasing in the indicated order, 20, 24, 28, 31, or 34 % of the total primary concentrate; at least, with increasing preference, in the order indicated, 0.50, 0.60, 0.70, 0.80, 0.90, 0.95, 1.00, or 1.05 moles of one or more metal atoms or boron atoms associated with fluorine atoms in an anion per kilogram of the total primary concentrate; and at least, with increasing preference in the order indicated, 4.0, 4.5, 5.0, 5.5, 6. 0, 6.5, or 7.0% component (C). In addition, the indicated preferences above for the proportions between components (B) and (A) and between component (C) and component (A) in work composition are also applied to these primary concentrates because they contain preferably all components (A) to (C) ) contained in the work compositions in which these primary concentrates are used as ingredients. A working composition for use in accordance with the present invention is preferably prepared from a preferred primary concentrate in accordance with that described above by first diluting a concentrated source, usually a commercially supplied latex, of the predicted amount of component (D) in the working composition with deionized water to about half the final intended volume of the working composition. Then, with stirring, the appropriate amount of preferred primary concentrate is added to introduce the expected amounts of components (A) to (C) into the working composition. Continue mixing until the mixture has a uniform appearance. The amount of component is then added from a concentrated source (E) provided for the final work composition and any additional volume of deionized water that is required to complete the expected mass or work composition volume and the ingredients are mixed together for at least 15 minutes after the last addition, using a mixing method that minimizes the formation of foams. The practice of this invention can be further observed by taking into account the following non-limiting examples and the benefits of the invention can be seen in contrast to the comparison examples presented below and additional comparisons known to those skilled in the art. WORK COMPOSITIONS AND PROCESSES - GROUP 1 These compositions appear in Table 1 below. Each composition was coated or hot-dip galvanized in duplicate on flat test panels at normal room temperature comfortable for humans (ie, 18-23 ° C), employing a drag bar to place an aqueous liquid composition with a substantially uniform thickness which was then dried in place in a convection oven maintained at a temperature of about 120 ° C, but was kept in this oven for a sufficiently short period such that the peak metal temperature did not exceed 66 ° C . After finishing this treatment, the coated panels were subjected to an unprotected salt spray test in accordance with the American Society for Testing and Materials Procedure B117-90. The aggregate masses of coating per unit area and the results of the salt spray test are shown in Table 2, where the results for the panels in duplicate under the same preparation and test conditions appear in side-by-side columns. Table 1 Mass parts of the work composition of: Number Water H3P04 Component (B) of Desioal 75% H2TIF6 composition standard 1.1.0 7.05 0.10 0.10 1.1.1 7.05 0.10 0.10 1.1.2 7.05 0.10 0.10 1.1.3 7.05 0.10 0.10 1.2.0 6.85 0.10 0.30 1.2.1 6.85 0.10 0.30 1.2.2 6.85 0.10 0.30 1.2.3 6.85 0.10 0.30 1.3.0 6.65 0.50 0.10 1.3.1 6.65 0.50 0.10 1.3.2 6.65 0.50 0.10 1.3.3 6.65 0.50 0.10 1.4.0 6.45 0.50 0.30 1.4.1 6.45 0.50 0.30 1.4. 2 6.45 0.50 0.30 1.4.3 6.45 0.50 0.30 1.5.0 6.80 0.10 0.10 1.5.1 6.80 0.10 0.10 1.5.2 6.80 0.10 0.10 1.5.3 6.80 0.10 0.10 1.6.0 6.60 0.10 0.30 1.6.1 6.60 0.10 0.30 1.6.2 6.60 0.10 0.30 1. 6.3 6.60 0.10 0.30 1. 7.0 6.40 0.50 0.10 1. 7.1 6.40 0.50 0.10 1. 7.2 6.40 0.50 0.10 1. 7.3 6.40 0.50 0.10 1. 8.0 6.20 0.50 0.30 1. 8.1 6.20 0.50 0.30 1. 8.2 6.20 0.50 0.30 1. 8.3 6.20 0.50 0.30 1. 1. 23.1 5.50 0.50 0.50 - • ^ > OR •. £. 5.50 0.50 0.50 1. 23.3 5.50 0.50 0.50 1. 24.0 5.00 0.50 1.00 1. 24.1 5.00 0.50 1.00 1. 24.2 5.00 0.50 1.00 1. 24.3 5.00 0.50 1.00 Number Component Component Component (E) Of (C) (D) Composition ChemCor Aqua-ChemCor KSL30N slip 671 392C30 1. 1.0 0.25 2.5 1.1.1 0.25 2.5 0.50 1.1.2 0.25 2.5 0.38 1.1.3 0.25 2.5 0.50 1. 2.0 0.25 2.5 1.2.1 0.25 2.5 0.50 1.2.2 0.25 2.5 0.38 1.2.3 0.25 2.5 0.50 1. 3.0 0.25 2.5 1.3.1 0.25 2.5 0.50 1.3.2 0.25 2.5 0.38 1.3.3 0.25 2.5 0.050 1. 4.0 0.25 2.5 1.4.1 0.25 2.5 0.50 1.4.2 0.25 2.5 0.38 1.4.3 0.25 2.5 0.50 1. 5.0 0.50 2.5 1.5.1 0.50 2.5 0.50 1.5.2 0.50 2.5 0.38 1.5.3 0.50 2.5 0.50 1. 6.0 0.50 2.5 1.6.1 0.50 2.5 0.50 1.6.2 0.50 2.5 0.38 1.6.3 0.50 2.5 0.50 1. 7.0 0.50 2.5 1.7.1 0.50 2.5 0.50 1.7.2 0.50 2.5 0.38 1.7.3 0.50 2.5 0.50 1. 8.0 0.50 2.5 1.8.1 0.50 2.50 0.50 1.8.2 0.50 2.5 0.38 1.8.3 0.50 2.5 0.50. 1. 9.0 1.00 2.5 1.9.1 1.00 2.5 0.50 1.9.2 1.00 2.5 0.38 1.9.3 1.00 2.5 0.50 1. 10.0 1.00 2.5 1.10.1 1.00 2.5 0.50 1.10.2 1.00 2.5 0.38 1.10.3 1.00 2.5 0.50 1. 11.0 1.00 2.5 1.11.1 1.00 2.5 0.50 1.11.2 1.00 2.5 0.38 1.11.3 1.00 2.5 0.50 1. 12.0 1.00 2.5 1.12.1 1.00 2.5 0.50 1.12.2 1.00 2.5 0.38 1.12.3 1.00 2.5 0.50 1. 13.0 0.25 2.5 1.13.1 0.25 2.5 0.50 1.13.2 0.25 2.5 0.38 1.13.3 0.25 2.5 0.50 1. 14.0 0.25 2.5 1.14.1 0.25 2.5 0.50 1.14.2 0.25 2.5 0.38 1.14.3 0.25 2.5 0.50 1. 15.0 0.25 2.5 1.15.1 0.25 2.5 0.50 1.15.2 0.25 2.5 0.38 1.15.3 0.25 2.5 0.50 1. 16.0 0.25 2.5 1.16.1 0.25 2.5 0.50 1.16.2 0.25 2.5 0.38 1.16.3 0.25 2.5 0.50 1. 17.0 0.50 2.5 1.17.1 0.50 2.5 0.50 1.17.2 0.50 2.5 0.38 1.17.3 0.50 2.5 0.50 1. 18.0 0.50 2.5 1.18.1 0.50 2.5 0.50 1.18.2 0.50 2.5 0.38 1.18.3 0.50 2.5 0.50 1.19.0 0.50 2.5 1.19.1 0.50 2.5 0.50 1.19.2 0.50 2.5 0.38 1.19.3 0.50 2.5 0.50 1. 20.0 0.50 2.5 1.20.1 0.50 2.5 0.50 1.20.2 0.50 2.5 0.38 1.20.3 0.50 2.5 0.50 1. 21.0 1.00 2.5 1.21.1 1.00 2.5 0.50 1.21.2 1.00 2.5 0.38 1.; either Rhoplex® HA-16 or HA-12, latexes from Rohm & Haas Co., which, according to its supplier, are dispersions with 41-46% solids of self-crosslinking acrylic acid copolymers. The ChemCor dispersions KSL30N and 392C30 were obtained from ChemCor, Chester, New York and according to their supplier they are dispersions of 29-31% solids in water of ester of montane ester, with a nonionic dispersing agent, and high polyethylene. density, with a cationic dispersing agent, respectively. Aquaslip® 671 is a dispersion that was obtained from Lubrizol (North American distributor for Langer &Co. GMBH, Ritterhude, Germany) and according to its manufacturer presents a dispersion of 40% non-volatiles in water of polyethylene wax in water, with a pH value of 3.5 to 4.5 and a fine particle size. Table 2 Number Aggregate mass Spray test rating of coating after: composition, g / m2 24 Hours 96 Hours tion 1.1.0 2.5 < 1 2 1.1.1 2.7 2 30 1.1.2 2.3 2 10 1.1.3 1.9 5 15 1.2.0 2.2 2 5 1.2.1 2.5 2 20 1.2.2 2.4 1 25 1.2.3 1.9 < 1 10 1.3.0 1.9 3 15 1.3.1 2.4 N 2 1.3.2 2.6 5 50 1.3.3 2.7 10 90 1.4.0 2.1 N < 1 1.4.1 2.1 N N 1.4.2 2.6 N 1 1.4.3 2.3 < 1 5 1.5.0 2.3 1 20 1.5.1 2.5 < 1 15 1.5.2 2.5 1 10 1.5.3 2.1 95 99 1.6.0 1.8 1 15 1.6.1 2.5 N 5 1.6.2 2.4 < 1 10 1.6.3 2.4 75 75 1.7.0 2.4 20 25 1.7.1 2.4 1 5 1. 7.2 2.9 < 1 10 1. 7.3 2.2 95 99 1. 8.0 2.5 N 1 1. 8.1 2.4 N N 1. 8.2 3.1 N N 1. 8.3 2.3 1 5 1. 9.0 2.2 10 50 1. 9.1 2.7 2 15 1. 9.2 2.6 5 15 1. 9.3 2.5 99 99 1., and unless there is a specification to the contrary, it indicates that no red oxidation was observed. "N" indicates that neither white oxidation nor red oxidation was observed. EXAMPLE AND EXAMPLE OF GROUP COMPARISON 2 This group includes comparisons against commercial products of the prior art. The substrates were flat panels of "polished" electro-galvanized steel Pittsburg-Canfield. Prior to treatment with an economical composition with the invention or a comparison composition, the panels were cleaned in accordance with the PARCO® Cleaner 338 process available commercially from the surface technologies division of Henkel Corporation, Madisson Height, Michigan (abbreviated here usually as "HST"), using a 5-point concentration of the cleaner concentrate for 7-10 seconds of spraying on the panels at a temperature of 49 ° C, rinsing, subsequently in hot water, and drying in air. The aqueous liquid compositions tested in accordance with the invention appear in Table 3. The ingredients identified by component letter only have the same meaning as in Table 1. ChemCor 191C30 was commercially obtained from ChemCor and according to its supplier is an emulsion at 29 ° C. -31% in high density linear crystalline polyethylene water stabilized with a cationic dispersion agent. Table 3 Parts per mass in composition of: Number Water H3P04 H2TÍF6 Compo- Compo- Component (E) de Desio- 75% to 60% nently Chemcor ChemCor compo- nized (C) (D) KSL30N 191C30 sicion 2. 0 129 10 6. 0 5. 0 6 0 2. 1 129 10 6. 0 5. 0 6 0 10 2. 2 129 10 6. 0 5. 0 6 0 10 Substrates cleaned in accordance as described above were coated with these compositions and with NOVABRIGHT® C 1005, a commercial product of HST to passivate the galvanized steel surfaces, in the same way as for group 1, then the panels and other obtained of coating processes at commercial plant scale were tested in salt spray in the same manner as for group 1. Aggregate coating masses measured per unit area, metal peak temperatures during drying as part of the treatment in accordance with this invention or with a comparison product, and salt spray test results appear in table 4. Replicated panels were used, and the expected replicas appear one below the other in table 4, with the entries in the two columns plus the left of this table also applies to blank cells between them and the next entry in the same column.

EXAMPLE AND EXAMPLE OF COMPARISON OF GROUP 3 In this group, the friction properties of the coatings formed in accordance with the invention were evaluated. The compositions 2.0 and 2.2 of group 2 were used again, together with the composition 3 according to this invention which had the same materials as the composition 2.2, except that the amount of ChemCor 191C30 used was duplicated while Table 4 added Result of test of peak cation of reverse-spraying of salt after compound metal, ° C, g / m2 of: sition: 24 48 73 96 Hours Hours Hours Hours 2.0 66 2.6 25 25 25 25 2.6 50 60 60 60 1.0 2 2 10 15 1.6 N < 1 2 2 2. 1 66 2.7 10 10 10 10 2.1 1 2 5 10 1.3 1 2 5 10 1.4 N < 1 1 2 2. 2 66 2.5 2 5 5 10 2.3 1 5 5 5 1.4 1 5 15 20 1.0 N 2 5 10 121 2.0 1 5 5 10 2.4 5 5 5 5 1.0 N 5 5 15 1.2 1 2 5 10 NBG 66 2.3 10 95 * 100 * 100 * 1.7 60 100 * 100 * 100 * 1.4 40 99 * 100 * 100 * 1.4 60 90 * 100 * 100 * NBG-c n.k. n.k. 75 99 * 100 * 100 * n.k. 75 95 * 100 * 100 * X-c n.k. 95 100 * 100 * 100 * n. k. 95 100 * 100 * 100 * not treated - - 75- 100 * 100 * 100 * Note and abbreviations for table 4 * at least part of this oxidation was red; on the other hand, all the observed oxidation was white. When observed, red oxidation means corrosion so extensive that the galvanized coating on the substrate is completely penetrated, allowing the oxidation of red iron to replace the zinc corrosion products. "NGB" means "NOVABRIGHT® C1005 product of commercial passivation;" -c "taken from a large-scale commercial line using the treatment mentioned on the left;" X "means a product which is believed to be commercial but processed from a way not known with details; "nk" means "unknown"; "-" indicates "not applicable." That the amounts of the other components remained the same, and the commercial products described in group 2 were also used again. two flat panels of hot dipped galvanized steel were treated with each composition in the same general manner described for group 2. The treated and dried substrates were then tested to determine the average coefficient of friction in a trawl under a pressure of 17 bars This test produces a graph of stretch force against time, which is functionally equivalent to distance, according to the frictional element in The displacement of the traction bench is pulled along the entire length of the stationary test panel. The stretching force typically rises very quickly at the beginning and then remains constant or decreases slightly during the rest of the test. The peak stretch force measured during the initial rapid rise is recorded as the initial force. The total time of the graph is divided into four equal intervals, and the coefficients of friction corresponding to the initial stretching force and the stretching forces measured from the graph at the ends of each of the four intervals appear in the Table 5 below.

Predicted replicas appear one below the other in the Table, with an average for the type of coating after each group of replicas. The results indicate that the compositions in accordance with the present invention are superior in this property to the current standard commercial products, with the composition containing an intermediate amount of wax providing less friction than the composition containing no wax or comparison with the composition that has the highest amount of wax. Table 5 Coefficient of friction ("μ"): Initial type Measured at the end of the number of average coating average: for five measurements 2. 0 0.59 0.44 0.41 0.65 0.28 0.51 0.64 0.53 0.45 0.36 0.35 0.45 0.76 0.59 0.53 0.47 0.42 0.51 2. 0 average 0.66 0.52 0.46 0.50 0.35 0.42 2. 2 0.42 0.42 0.41 0.40 0.37 0.41 0.39 0.40 0.40 0.36 0.35 0.39 0.42 0.45 0.46 0.44 0.42 0.45 0.45 0.47 0.44 0.41 0.39 0.44 2.2 average 0.42 0.43 0.43 0.40 0.38 0.42 3 0.77 0.58 0.46 0.34 0.34 0.46 0. 62 0.59 0.56 0.55 0.42 0.56 0. 65 0.48 0.46 0.45 0.45 0.46 average 0.68 0.54 0.49 0.45 0.40 0.50 NBG 0.38 0.57 0.63 0.57 0.51 0.59 0. 42 0.42 0.42 0.44 0.39 0.43 NBG-c n. k. 0.64 0.63 0.58 n. k 0.62 n.k. 0.59 0.53 0.41 n.k. 0.51 NBG Average 0.40 0.56 0.55 0.50 0.45 0.54 X-c n.k. 0.70 0.76 0.70 n. k. 0.72 n.k. 0.68 0.61 0.58 n. k. 0.62 X-c Average _ 0.69 0.69 0.64 - 0.67

Claims

CLAIMS A process for the formation on a metal surface of a solid adhesive coating that provides the metal surface after coating with at least one of the following changes: (i) protect the treated surface, without any additional coating, against corrosion more effectively that in the absence of any coating; (ii) improving the adhesion of a subsequently applied coating, as compared to the adhesion that could be achieved between the same coating applied subsequently and the uncoated metal surface; and (iii) allowing the treated metal surface to be satisfactorily cold worked without the need for liquid organic lubricant under conditions in which if the metal surface is not coated it can not be satisfactorily cold-worked without the use of an organic liquid lubricant, said process comprises the steps of: (I) coating said metal surface with a layer of an aqueous liquid composition comprising water; and (A) a concentration of a component of dissolved phosphorus-containing anions; (B) a concentration of a dissolved component selected within the group consisting of simple and complex anions containing fluorine atoms; (C) a concentration of a component consisting of materials (á), (ß) or both (á) and (ß) dissolved, dispersed or dissolved and dispersed, where: (á) consists of polymer molecules each of which has at least one unit corresponding to the general formula (II) presented below: where: each of R2 to R4 is selected, independently from each other and independently from one molecule of the component to another and from one unit to another that forms the molecule when there is more than one unit of this type in a single polymer molecule, within the a group consisting of a hydrogen portion, an alkyl portion with 1 to 5 carbon atoms, and an aryl portion with 6 to 18 carbon atoms; each of Y1 to Y4 is selected, independently of each other, except as indicated below, and independently of one molecule from the component to another and from one unit to another corresponding to this formula when there is more than one unit of this type in the single polymer molecule, of the group consisting of: a hydrogen atom portion; a -CH2C1 portion; an alkyl portion having 1 to 18 carbon atoms; an aryl portion with 6 to 18 carbon atoms; a portion corresponding to the general formula -CR12R13OR14, wherein each of R12 to R14 is selected from the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion; and a Z portion that corresponds to one of the two general formulas that we present below: R / N or r N- R \\ R -.v wherein each of R to R is selected, independently from each other and independently of one molecule from the component to another and from one unit to another of any polymer molecule according to the formula when there is more than one unit of this type in a molecule single polymer, within the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion and R9 is selected from the group consisting of a portion hydrogen, an alkyl portion, an aryl portion, a hydroxy or polyhydroxyalkyl portion, an amino or polyaminoalkyl portion, a mercapto or polycaptoalkyl portion, a phospho or polyphosphoalkyl portion, a -0"portion, and an -OH portion, at least one Y1 to Y4 in at least one unit of each selected polymer molecule is a Z-portion as defined above, and 1 is elects, independently of one molecule from the component to another and from one unit to another of any polymer molecule that corresponds to this formula when there is more than one unit of this type in a single polymer molecule, within the group consisting of a portion hydrogen, an acyl portion, an acetyl portion, a benzoyl portion; a 3-allyloxy-2-hydroxypropyl portion; a 3-benzyloxy-2-hydroxypropyl portion; a 3-butoxy-2-hydroxypropyl portion; a 3-alkyloxy-2-hydroxypropyl portion; a 2-hydroxyoctyl portion; a 2-hydroxyalkyl portion, a 2-hydroxy-2-phenylethyl moiety; a 2-hydroxy-2-alkylphenylethyl moiety; a benzyl, methyl, ethyl, propyl, unsubstituted alkyl, unsubstituted allyl, or unsubstituted alkylbenzyl moiety; a halo or polyhaloalkyl, or halo or polyhaloalkenyl portion; a portion derived from a condensation polymerization product of ethylene oxide, propylene oxide or a mixture thereof by removal of a hydrogen atom therefrom; and a portion of sodium, potassium, lithium, ammonium or substituted ammonium cation, or substituted phosphonium or phosphonium; and (ß) consists of polymer molecules, none of which includes a unit corresponding to the general formula (II) as indicated above but includes at least one unit corresponding to the general formula (III) presented below : where: each R10 and R11 is selected, independently from each other and independently from one molecule of the component to another and from one unit to another in accordance with this formula when there is more than one unit of this type in a single polymer molecule, within the a group consisting of a hydrogen portion, an alkyl portion with 1 to 5 carbon atoms, and an aryl portion with 6 to 18 carbon atoms; each of Y4 to Y6 is selected, independently of each other, and independently of one molecule from the component to another and from one unit to another of any polymer molecule corresponding to this formula when there is more than one unit of this type in a molecule of single polymer within the group consisting of: a hydrogen portion, a -CH2C1 portion; an alkyl portion having 1 to 18 carbon atoms; an aryl portion with 6 to 18 carbon atoms; a portion that complies with the general formula -CR12R13OR14, wherein each of R12 to R14 is selected from the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion; and a Z-portion according to that defined for the material (á) above, at least one of Y1 to Y4 in at least one unit of each selected polymer molecule is a Z-portion according to that defined above; and W2 is selected, independently of one molecule from the component to another and from one unit to another corresponding to this formula when there is more than one unit of this type in a single polymer molecule, within a group consisting of a portion of hydrogen atom, an acyl portion, an acetyl portion, a benzoyl portion; a 3-allyloxy-2-hydroxypropyl portion; a 3-benzyloxy-2-hydroxypropyl portion; a 3-butoxy-2-hydroxypropyl portion; a 3-alkyloxy-2-hydroxypropyl portion; a 2-hydroxyoctyl portion; a 2-hydroxyalkyl portion; a 2-hydroxy-2-phenylethyl moiety; a 2-hydroxy-2-alkylphenylethyl moiety; a benzyl, methyl, ethyl, propyl, unsubstituted alkyl, unsubstituted allyl or unsubstituted alkylbenzyl moiety; and a halo or polyhaloalkyl, or halo or polyhaloalkenyl portion; a portion derived from a condensation polymerization product of ethylene oxide, propylene oxide or a mixture thereof by removal of a hydrogen atom therefrom; and a portion of sodium, potassium, lithium, ammonium or substituted ammonium cation, or substituted phosphonium or phosphonium; the expression "polymer molecule" in the above definitions of materials (a) and (ß) includes any electrically neutral molecule with a molecular weight of at least 300 daltons; and (D) a concentration of a component of dissolved film-forming molecules, stably dispersed, or both dissolved and stably dispersed, said molecules are not part of any of the components (A) to (C) mentioned above; and (II) drying the non-volatile contents of the liquid layer, formed in step (I), in such a manner that said solid coating is formed on the metallic surface. an operation according to claim 1, wherein: the solid layer formed in step (II) has a mass unitary area of the coated metal surface that is from about 0.2 to about 10 grams per square meter ("g / m2"); either: the component (B) includes at least one of the elements boron, silicon, titanium, zirconium, and hafnium in anions also containing fluorine atoms, and the concentration, in a unit of moles by volume of aqueous liquid composition, of the total boron, silicon, titanium, zirconium and hafnium elements in the liquid composition from which a layer was formed in step (I) has a ratio in relation to the concentration of phosphorus atoms that is stoichiometrically equivalent to the concentration of component (A) in said aqueous liquid composition, in the same unit as for component (B), which is from about 0.03: 1.0 to about 2.0: 1.0; or component (B) does not include any of the elements boron, silicon, titanium, zirconium and, hafnium, and the concentration in moles of fluorine atoms in the liquid composition from which a layer was formed in step (I) has a ratio relative to the concentration in moles of phosphorus atoms that is stoichiometrically equivalent to the concentration of the component (A) in the same brand of the same liquid composition that is from about 0.3: 1.0 to about 7: 1.0; in said aqueous liquid composition, the concentration of component (C) in a unit mass per volume of aqueous liquid composition, has a ratio relative to the stoichiometrically equivalent concentration as component H3P0 (A), in the same unit as for the component (C), which is from about 0.02: 1.0 to about 2.0: 1.0; in said aqueous liquid composition, the concentration of the component (D), in a unit of mass by volume of the total liquid composition, has a ratio in relation to the concentration of the component (A) in the same unit as for the component (D) ) which is from about 0.3: 1.0 to about 15: 1.0; and the liquid composition also contains a volume of component (E) of stably dispersed solid material which in isolation has a coefficient of static friction, measured between two pieces of solid material per se or between solid material and cold rolled steel, which is not greater than 0.35, this solid material is not part of any of the components (A) to (D), the volume of component (E) in said aqueous liquid composition is such that an equal volume of high density polyethylene has a mass with a ratio relative to the mass of component (D) present in the same liquid composition that is from about 0.005: 1.0 to about 0.40: 1.0. operation according to claim 2, wherein: component (A) was provided to the composition as orthophosphoric acid or at least one salt thereof; component (B) is selected from the group consisting of anions with one of the chemical formulas SiF5"2, TiF6" 2, ZrF6"2, and HfF6" 2; component (C) is selected from molecules of type (á) when: each of R 2 to R 6, R 10, R 11, W 1, and 2, is a hydrogen atom portion; each of Y1 to Y6 is a hydrogen atom portion or a Z portion; on average in the total content of component (C), each polymer molecule contains a number of units corresponding to the general formulas (II) in accordance with what is defined above, which is from about 5, to about 50; on average in the total content of the component (C), the number of portions Z has a ratio in relation to the number of aromatic nuclei that is from approximately 0.20: 1.0 to approximately 2.0: 1.0, - on average in the total content of the component ( C), the number of polyhydroxyl portions Z which are defined as the Z portions in which at least R8 in the general formulas for Z portions has (i) from 4 to 6 carbon atoms and (ii) so many hydroxyl groups, each fixed on a different carbon atom, such as one less than the number of carbon atoms in the R8 portion, has a ratio relative to the total number of Z portions in the composition that is at least about 0.50: 1.0; and - R7 is an alkyl portion with not more than 3 carbon atoms. process according to claim 3, wherein: the solid layer formed in step (II) has a mass per unit area of the coated metal surface that is from about 0.80 to about 4.0 g / m2; component (B) includes at least one of the following elements boron, silicon, titanium, zirconium, and hafnium in anions also containing fluorine atoms, and the concentration in one unit of moles per volume of aqueous liquid composition of the total elements boron, silicon, titanium, zirconium, and hafnium in the liquid composition from which a layer is formed in step (I) has a ratio in relation to the concentration of phosphorus atoms, which is stoichiometrically equivalent to the concentration of component (A), in the same unit as for component (B), is from about 0.12: 1.0 to about 0.40: 1.0; in said aqueous liquid composition, the concentration of component (C) in a unit of mass by volume has a ratio in relation to the stoichiometrically equivalent concentration as component H3P04 (A), in the same unit as for component (C), that is, from about 0.08: 1.0 to about 0.40: 1.0; in said aqueous liquid composition, the concentration of component (D) in a unit of mass by volume of the total liquid composition, has a ratio in relation to the concentration of component (A) in the same unit as for component (D) which is from about 0.9: 1.0 to about 4.0: 1.0; and the liquid composition also contains a volume of component (E) of stably dispersed solid material which in isolation has a coefficient of static friction, measured between two pieces of the solid material itself or between the solid material and cold rolled steel, which is not greater than 0.16, this solid material is not part of any of the components (A) to (D), the volume of component (E) is such that an equal volume of high density polyethylene has a mass with a proportion of relation to the mass of component (D) present in the same liquid composition that is from about 0.025: 1.0 to about 0.10: 1.0. operation according to claim 4, wherein: the solid layer formed in step (II) has a mass per unit area of the coated metal surface that is from about 1.5 to about 2.5 g / m2; in said aqueous liquid composition, the component (B) is hexafluorotitanic acid, and its concentration in a unit of moles of titanium by volume of said liquid composition has a ratio in relation to the concentration of phosphorus atoms that is stoichiometrically equivalent to the concentration of component (A), in the same unit as for component (B), which is from about 0.21: 1.0 to about 0.35: 1.0; component (C) is selected from polymers of 4-vinylphenol to which Z portions have been grafted from the formaldehyde and N-methylglucamine reaction, and the concentration of component (C) in a unit of mass by volume has a ratio relative to the stoichiometrically equivalent concentration as H3PO4 of component (A) in the same unit as for component (C) which is from about 0.14: 1.0 to about 0.35: 1.0; - in said aqueous liquid composition, the concentration of component (D) in a unit of mass by volume of the total liquid composition, has a ratio in relation to the concentration of component (A) in the same unit as for the component (D) ), which is from about 1.5: 1.0 to about 2.9: 1.0; and component (E) is a high density polyethylene and has a mass with a ratio relative to the mass of component (D) present in the same liquid composition that is from about 0.042: 1.0 to about 0.10: 1.0. A process for the formation on a metal surface of a solid adhesive coating that provides the metal surface after coating with at least one of the following changes: (i) protect the treated surface, without any additional coating, against corrosion more effectively that in the absence of any coating; (ii) improving the adhesion of a subsequently applied coating, as compared to the adhesion that could be achieved between the same coating applied subsequently and the uncoated metal surface; and (iii) allowing the treated metal surface to be satisfactorily cold worked without the need for liquid organic lubricant under conditions in which if the metal surface is not coated it can not be satisfactorily cold-worked without the use of an organic liquid lubricant, said The process comprises the steps of: (I) coating said metal surface with a layer of an aqueous liquid composition that has been made by mixing a first mass of water and: (A) a second mass of an anion water soluble source that contain phosphorus; (B) a third mass of a source of water-soluble anions selected from the group consisting of simple and complex anions containing fluorine atoms; (C) a fourth mass of a component consisting of materials (á), (ß) or both (á) and (ß) where: (á) consists of polymer molecules each of which has at least one unit corresponding to the general formula (II) presented below: where: each of R2 to R4 is selected, independently from each other and independently from one molecule of the component to another and from one unit to another that forms the molecule when there is more than one unit of this type in a single polymer molecule, within the a group consisting of a hydrogen portion, an alkyl portion with 1 to 5 carbon atoms, and an aryl portion with 6 to 18 carbon atoms; each of Y1 to Y4 is selected, independently of each other, except as indicated below, and independently of one molecule from the component to another and from one unit to another corresponding to this formula when there is more than one unit of this type in the single polymer molecule, of the group consisting of: a hydrogen atom portion; a -CH2C1 portion; an alkyl portion having 1 to 18 carbon atoms; an aryl portion with 6 to 18 carbon atoms; a portion corresponding to the general formula -CR12R13OR14, wherein each of R12 to R14 is selected from the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion; and a Z portion that corresponds to one of the two general formulas that we present below: wherein each of R5 to R8 is independently selected from and independently of one molecule from the component to another and from one unit to another of any polymer molecule according to the formula when there is more than one unit of this type in a molecule single polymer, within the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion and R9 is selected from the group consisting of a portion hydrogen, an alkyl moiety, an aryl moiety, a hydroxy or polyhydroxyalkyl moiety, an amino or polyaminoalkyl moiety, a mercapto or polycarboxy alkyl moiety, a phospho or polyphosphoalkyl moiety, a -O "moiety, and an -OH moiety, at least one moiety Y1 to Y4 in at least one unit of each selected polymer molecule is a Z-portion as defined above, and W1 s and selects, independently of one molecule from the component to another and from one unit to another of any polymer molecule corresponding to this formula when there is more than one unit of this type in a single polymer molecule, within the group consisting of one hydrogen portion, an acyl portion, an acetyl portion, a benzoyl portion; a 3-allyloxy-2-hydroxypropyl portion; a 3-benzyloxy-2-hydroxypropyl portion; a 3-butoxy-2-hydroxypropyl portion; a 3-alkyloxy-2-hydroxypropyl portion; a 2-hydroxyoctyl portion; a 2-hydroxyalkyl portion, a 2-hydroxy-2-phenylethyl moiety; a 2-hydroxy-2-alkylphenylethyl moiety; a benzyl, methyl, ethyl, propyl, unsubstituted alkyl, unsubstituted allyl, or unsubstituted alkylbenzyl moiety; a halo or polyhaloalkyl, or halo or polyhaloalkenyl portion; a portion derived from a condensation polymerization product of ethylene oxide, propylene oxide or a mixture thereof by removal of a hydrogen atom therefrom; and a portion of sodium, potassium, lithium, ammonium or substituted ammonium cation, or substituted phosphonium or phosphonium; and (ß) consists of polymer molecules, none of which includes a unit corresponding to the general formula (II) as indicated above but includes at least one unit corresponding to the general formula (III) presented below : where: each R10 and R11 is selected, independently from each other and independently from one molecule of the component to another and from one unit to another in accordance with this formula when there is more than one unit of this type in a single polymer molecule, within the group consisting of a hydrogen portion, an alkyl portion with 1 to 5 carbon atoms, and an aryl portion with 6 to 18 carbon atoms; each of Y4 to Y6 is selected, independently of each other, and independently of one molecule from the component to another and from one unit to another of any polymer molecule corresponding to this formula when there is more than one unit of this type in a molecule of single polymer within the group consisting of: a hydrogen portion, a -CH2C1 portion; an alkyl portion having 1 to 18 carbon atoms; an aryl portion with 6 to 18 carbon atoms; a portion that complies with the general formula -CR12R13OR14, wherein each of R12 to R14 is selected from the group consisting of a hydrogen portion, an alkyl portion, an aryl portion, a hydroxyalkyl portion, an aminoalkyl portion, a mercaptoalkyl portion, and a phosphoalkyl portion; and a Z-portion according to that defined for the material (á) above, at least one of Y1 to Y4 in at least one unit of each selected polymer molecule is a Z-portion according to that defined above; and 2 is selected, independently of one molecule from the component to another and from one unit to another corresponding to this formula when there is more than one unit of this type in a single polymer molecule, within a group consisting of a portion of hydrogen atom, an acyl portion, an acetyl portion, a benzoyl portion; a 3-allyloxy-2-hydroxypropyl portion; a 3-benzyloxy-2-hydroxypropyl portion; a 3-butoxy-2-hydroxypropyl portion; a 3-alkyloxy-2-hydroxypropyl portion; a 2-hydroxyoctyl portion; a 2-hydroxyalkyl portion; a 2-hydroxy-2-phenylethyl moiety; a 2-hydroxy-2-alkylphenylethyl moiety; a benzyl, methyl, ethyl, propyl, unsubstituted alkyl, unsubstituted allyl or unsubstituted alkylbenzyl moiety; and a halo or polyhaloalkyl, or halo or polyhaloalkenyl portion; a portion derived from a condensation polymerization product of ethylene oxide, propylene oxide or a mixture thereof by removal of a hydrogen atom therefrom; and a portion of sodium, potassium, lithium, ammonium or substituted ammonium cation, or substituted phosphonium or phosphonium; (D) a fifth mass of a source of dissolved film-forming molecules, stably dispersed or both dissolved and stably dispersed, said molecules do not form part of any of the substances mentioned above (A) a (C); and (II) drying the non-volatile contents of the liquid layer, formed in operation (I), in place on the metal surface, for the purpose of forming said solid coating. process according to claim 6, wherein: - the solid layer formed in step (II) has a mass "per unit area of the coated metal surface that is from about 0.2 to about 10 grams per square meter (" g / m2"), either: - the substance (B) includes at least one of the elements boron, silicon, titanium, zirconium, and hafnium in anions also containing fluorine atoms, and the third mass contains a number of moles of the total boron, silicon, titanium, zirconium, and hafnium elements having a ratio relative to the total number of moles of phosphorus atoms in said liquid composition that is from about 0.03: 1.0 to about 2.0: 1.0, or the substance (B) it does not include any of the elements boron, silicon, titanium, zirconium, and hafnium, and the third mass contains a number of moles of fluorine atoms having a ratio relative to the number of moles of phosphorus atoms corresponding to said second mass that is from about 0.3: 1.0 to about 7: 1.0; the fourth mass has a ratio in relation to the stoichiometrically equivalent mass as H3P04 of the second mass which is from about 0.02: 1.0 to about 2.0: 1.0; the fifth mass has a ratio in relation to the stoichiometrically equivalent mass as H3P04 of the second mass which is from about 0.3: 1.0 to about 15: 1.0; and the liquid composition also contains a volume of a component (E) of stably dispersed solid material which in isolation has a coefficient of static friction, measured between two pieces of the solid material itself or between the solid material and the steel laminated in cold, which is not greater than 0.35, this solid material is not part of any of the components (A) to (D), the volume of component (E) is such that an equal volume of high density polyethylene has a sixth mass with a ratio relative to said fifth mass which is from about 0.005: 1.0 to about 0. 40: 1.0 process according to claim 7, wherein: component (A) was provided to the composition as orthophosphoric acid or at least one salt thereof; component (B) is selected from the group consisting of anions with one of the chemical formulas BF4_1, SiFd "2, TiF6" 2, ZrF6"2, and HfF6" 2; component (C) is selected from molecules of type (á) when: each of R 2 to R 6, R 10, R 11, W 1, and 2, is a hydrogen atom portion; each of Y1 to Y6 is a hydrogen atom portion or a Z portion; - averaged over the total content of component (C), each polymer molecule contains a number of units corresponding to the general formulas (II) in accordance with what is defined above, which is from about 5, to about 50; - averaged over the total content of the component (C), the number of portions Z has a proportion relative to the number of aromatic nuclei that is from about 0.20: 1.0 to about 2.0: 1.0, averaged over the total content of the component (C) , the number of polyhydroxyl portions Z which are defined as the Z portions wherein R8 in the general formulas for Z portions has (i) from 4 to 6 carbon atoms and (ii) so many hydroxyl groups, each fixed on an Different carbon, such as one less than the number of carbon atoms in the R8 portion, has a ratio relative to the total number of Z portions in the composition that is at least about 0.50: 1.0; and R7 is an alkyl portion with not more than 3 carbon atoms. an operation according to claim 8, wherein: the solid layer formed in step (II) has a mass per unit area of the coated metal surface that is from about 0.80 to about 4.0 g / m2; component (B) includes at least one of the following elements boron, silicon, titanium, zirconium, and hafnium in anions also containing fluorine atoms, and the concentration in one unit of moles per volume of aqueous liquid composition of the total elements boron, silicon, titanium, zirconium, and hafnium in the liquid composition from which a layer is formed in step (I) has a ratio relative to the concentration of phosphorus atoms that is stoichiometrically equivalent to the concentration of the component (A), in the same unit as for component (B), is from about 0.12: 1.0 to about 0.40: 1.0; in said aqueous liquid composition, the concentration of component (C) in a unit of mass by volume has a ratio in relation to the stoichiometrically equivalent concentration as component H3P04 (A), in the same unit as for component (C), that is, from about 0.08: 1.0 to about 0.40: 1.0; in said aqueous liquid composition, the concentration of component (D) in a unit of mass by volume of the total liquid composition, has a ratio in relation to the concentration of component (A) in the same unit as for component (D) which is from about 0.9: 1.0 to about 4.0: 1.0; and the liquid composition also contains a volume of component (E) of stably dispersed solid material which in isolation has a coefficient of static friction, measured between two pieces of the solid material itself or between the solid material and cold rolled steel, which is not greater than 0.16, this solid material is not part of any of the components (A) to (D), the volume of component (E) is such that an equal volume of high density polyethylene has a mass with a proportion of relation to the mass of component (D) present in the same liquid composition that is from about 0.025: 1.0 to about 0.10: 1.0. A process according to claim 4, wherein: the solid layer formed in step (II) has a mass per unit area of the coated metal surface that is from about 1.5 to about 2.5 g / m2; component (B) is hexafluorotitanic acid, and said third mass contains a number of moles of titanium having a ratio relative to the number of moles of phosphorus atoms that is stoichiometrically equivalent to the stoichiometric equivalence as H3P04 of said second mass which is from about 0.21: 1.0 to about 0.35: 1.0; component (C) is selected from 4-vinylphenol polymers to which Z portions have been grafted from the reaction of formaldehyde and N-methylglucamine, said fourth mass having a ratio relative to the stoichiometric equivalent as H3P04 of said second mass which is from about 0.14: 1.0 to about 0.35: 1.0; said fourth mass has a ratio relative to said stoichiometric equivalent as H3PO4 of said second mass which is from about 1.5: 1.0 to about 2.9: 1.0; and component (E) is a high density polyethylene and said sixth mass has a ratio relative to said fifth mass which is approximately 0. 042: 1.0 to approximately 0.10: 1.0. 11. A primary concentrate composition that is suitable for mixing with water and, optionally, one or more other materials to produce an aqueous working liquid composition for use in a process according to any of claims 1-10, said composition of primary concentrate comprises water and an amount of component (A) which corresponds stoichiometrically to an amount of H3PO4 constituting at least about 20% of the total primary concentrate; - at least about 0.50 moles of one or more metal atoms or boron atoms associated with fluorine atoms in an anion per kilogram of the total primary concentrate; and at least about 4.0% of component (C). 12. A primary concentrate according to claim 11, wherein: the amount of component (A) corresponds stoichiometrically to an amount of H3P0 constituting at least about 24% of the total primary concentrate; there is at least about 0.60 mol of one or more metal atoms or boron atoms associated with fluorine atoms in an anion per kilogram of the total primary concentrate; and - there is at least about 4.0% of component (C). 13. A primary concentrate according to claim 12, wherein: the amount of component (A) corresponds stoichiometrically to an amount of H3P04 constituting at least about 28% of the total primary concentrate; there is at least about 0.70 mol of one or more metal atoms or boron atoms associated with fluorine atoms in an anion per kilogram of the total primary concentrate; there is at least about 5.0% of the component (C); and component (C) is selected from molecules of type (á) when: each of R 2 to R 6, R 10, R 11, W 1, and W 2, is a hydrogen atom portion; each of Y1 to Y6 is a hydrogen atom portion or a Z portion; averaged over the total content of component (C), each polymer molecule contains a number of units corresponding to general formulas (II) in accordance with what is defined above, which is from about 5, to about 50; averaged over the total content of component (C), the number of portions Z has a ratio to the number of aromatic nuclei that is from about 0.20: 1.0 to about 2.0: 1.0, averaged over the total content of component (C), the number of polyhydroxyl portions Z which are defined as these Z portions wherein at least R8 in the general formulas for Z portions has (i) from 4 to 6 carbon atoms and (ii) so many hydroxyl groups, each bonded to an Different carbon, such as one less than the number of carbon atoms in the R portion, has a ratio relative to the total number of Z portions in the composition that is at least about 0.50: 1.0; and R7 is an alkyl portion having no more than 3 carbon atoms. A primary concentrate according to claim 13, wherein: the amount of component (A) corresponds stoichiometrically to an amount of H3PO4 constituting at least about 31% of the total primary concentrate; there is at least about 0.80 mol of one or more metal atoms or boron atoms associated with fluorine atoms in an anion per kilogram of the total primary concentrate; and there is at least about 5.5% of component (C). A primary concentrate according to claim 14, wherein: - H3PO4 constitutes at least about 34% of the total primary concentrate; there is at least about 0.95 mol of hexafluorotitanic acid per kilogram of the total primary concentrate; and - there is at least about 6.0% polymers of 4-vinylphenol to which Z portions from the reaction of formaldehyde and N-methylglucamine were grafted. 16. A primary concentrate composition that is suitable for mixing with water and, optionally, one or more other materials for producing an aqueous working liquid composition for use in a process according to any of claims 1-10, said primary concentrate composition was made by mixing together a first water body and: a second mass of a water soluble source of component (A) that corresponds stoichiometrically to a mass of H3P04 constituting at least about 20% of the total primary concentrate; a third water-soluble source mass of anions containing a metal atom or a boron atom together with at least four fluorine atoms, said third mass contains at least about 0.50 mol of said metal or boron atoms per kilogram of the total primary concentrate; and a fourth component mass (C) that constitutes at least about 4.0% of the total primary concentrate. 17. A primary concentrate according to claim 16, wherein: said second mass corresponds stoichiometrically to an amount of H3PO4 constituting at least about 24% of the total primary concentrate; said third mass contains at least about 0.60 mol of said metal or boron atoms per kilogram of the total primary concentrate; and said fourth mass constitutes at least about 4.5% of component (C). A primary concentrate according to claim 17, wherein: said second mass corresponds stoichiometrically to an amount of H3PO4 constituting at least about 28% of the total primary concentrate; said third mass contains at least about 0.70 mol of said metal or boron kilogram atoms of the total primary concentrate; - said fourth mass constitutes at least about 5.0% of component (C); and component (C) is selected from molecules of type (á) when: each of R 2 to R 6, R 10, R 11, 1, and 2, is a hydrogen atom portion; each of Y1 to Y6 is a hydrogen atom portion or a Z portion; averaged over the total content of component (C), each polymer molecule contains a number of units corresponding to general formulas (II) in accordance with what is defined above, which is from about 5, to about 50; averaged over the total content of the component (C), the number of portions Z has a proportion with the number of aromatic nuclei that is from about 0.20: 1.0 to about 2.0: 1.0, averaged over the total content of the component (C), the number of polyhydroxyl portions Z which are defined as these Z portions wherein at least R8 in the general formulas for Z portions has (i) of 4 to 6 carbon atoms and (ii) as many hydroxyl groups, each bonded to a different carbon atom, as one less than the number of carbon atoms in the R8 portion, has a ratio relative to the total number of Z portions in the composition that is at least about 0.50: 1.0; and R7 is an alkyl portion with not more than 3 carbon atoms. A primary concentrate according to claim 18, wherein: said second mass corresponds stoichiometrically to an amount of H3PO4 constituting at least about 31% of the total primary concentrate; - said third mass contains at least about 0.80 mol of said metal atoms or boron atoms kilogram of the total primary concentrate; and said fourth mass constitutes at least about 5.0% of the total concentrate. 20. A primary concentrate according to claim 19, wherein: said second mass consists of H3P04 constituting at least about 34% of the total primary concentrate; - said third mass contains at least about 0.95 mol of hexafluorotitanic acid per kilogram of the total primary concentrate; and said fourth mass consists essentially of at least about 6.0% polymers of 4-vinylphenol to which Z portions from the reaction of formaldehyde and N-methylglucamine were grafted. SUMMARY OF THE INVENTION A composition for the multi-purpose treatment of metal surfaces contains phosphate ions, fluorometalate ions, water-soluble polymers containing substituted amino-substituted portions on benzene rings also having one oxygen atom attached on another carbon atom in the same ring, and a characteristic type of film forming polymers. The compositions are free of chromium and other heavy metals that cause severe contamination problems in prior art treatment compositions. The coating layers formed in a process according to the present invention are effective for at least three different purposes: increasing the adhesion and protection against corrosion of subsequently applied paints or other protective coatings with a largely organic matrix; without any subsequent applied protective coating, provide at least temporarily a protection against staining and the development of white oxidation on zinc or zinc alloy surfaces treated in a process according to the invention; and providing sufficient lubricity to allow the formation of sheets of metals treated in a process according to the invention without the need for additional liquid lubricants such as, for example, oil.