MXPA00001543A - Hydrophilicizing surfaces, especially aluminum - Google Patents

Abstract

An especially effective hydrophilicizing treatment for solid surfaces, particularly those of conversion coated aluminum, is a liquid mixture of water, organic polymer molecules that include sulfonyl/ate moieties, and preferably also a substance made by mixing with aqueous phosphoric acid at least one metal, metal oxide, or metal hydroxide so as to form a transparent liquid mixture. The treatment liquid preferably has a nearly neutral pH and is applied to a substrate and dried in place by exposure to heat.

Description

HYDROFILIZATION OF SURFACES, ESPECIALLY ALUMINUM BACKGROUND OF THE INVENTION This invention relates to the hydrophilizing treatment for a surface, usually a surface with a base or underlying metal already carrying a protective coating against corrosion. Previously known corrosion protective coatings that do not require the use of chromium during their formation may be combined with the characteristic hydrophilizing treatment according to this invention to form a high quality and durable hydrophilic surface. After the treatment according to this invention, the water will have a tendency to spontaneously disperse on the surface. The invention is particularly and advantageously applicable to aluminum evaporators, heat exchangers and condensers with hydrophilic coatings having good corrosion resistance and little or no tendency to develop undesirable odors during use. Although any of the common structural metals can be used in the construction of practical heat exchange surfaces, aluminum and its alloys are among the most commonly used, due to its high thermal conductivity. On heat exchange surfaces, metals are usually used without any relatively thick protective coating such as paint or lacquer that would generally be used in other types of equipment made of metals and exposed to corrosive environments, to improve the strength of the equipment, but any These relatively thick protective coatings are avoided in heat exchangers because this coating would also reduce the efficiency of heat exchange. During the cooling of the hot air, a common use of these heat exchangers, the moisture contained as vapor in the hot air condenses and initially form drops or pearls of water on the fins of the heat exchanger. If the surface of the fins in the heat exchanger is not sufficiently hydrophilic, these water pearls accumulate on the surface of the fins and tend to form bridges in the small spaces between the fins, thereby preventing the flow of air between the fins. the fins and reducing the efficiency in heat transfer. Condensed water beads also tend to absorb dust and pollutants in the air, such as carbon dioxide, nitrogen oxides and sulfur oxides, which can promote the corrosion of the underlying aluminum, and due to the capillary forces contained in it. Instead of droplets of water that have grown large enough to form bridges between adjacent fins, the normal drainage of fin water that would otherwise entrain these absorbed contaminants is substantially reduced. Therefore, the formation of water beads on the fins of an aluminum heat exchanger not only decreases the heat transfer efficiency but can also physically damage the exchanger. In order to obtain the desired combination of a hydrophilic nature and resistance to corrosion in the metal, particularly aluminum, different coatings and surface treatments have been treated, but satisfactory results have not yet been obtained. A chromate conversion coating without subsequent treatment usually has inadequate corrosion resistance and often develops an unpleasant odor and poor hydrophilicity. The silicate coating on a chromate conversion coating has often been used but does not meet all the requirements for all users. Recently, organic, hydrophilic polymer films have been used, with protection from biocides as subsequent treatments on chromate conversion coatings. Although effective, they have proven to be expensive and difficult to control in some commercial operations.

The main alternative or concurrent objectives of the invention are to achieve (i) a combination of adequate hydrophilicity and corrosion resistance, compared to the prior art, while avoiding the use of contaminating constituents, and highly volatile constituents, particularly organic solvents, with potential toxicity and unpleasant odors for the workers, in the treatment compositions (i) durability of the hydrophilicity under thermal aging and / or practical use, and (iii) avoid the development of unpleasant odors during practical use. Other objectives will be evident from the following description. Except in the specific claims and examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and / or use shall be understood, as modified by the word "approximate" in the description of the broadest scope of the invention. However, practice is generally preferred within established numerical limits. Also, unless otherwise expressly stated: percent "parts of" and proportion values are by weight; the term "polymer" includes "oligomer", "copolymer", "terpolymer", and the like; the first definition or description of the meaning of a word, phrase, acronym, abbreviation or similar applies to all subsequent uses of the same word, phrase, acronym, abbreviation or similar and applies mutatis mutandis to the normal grammatical variations of the same; the description of a group or class of materials as suitable or preferred for a particular purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; chemical descriptions of neutral materials is applied to the materials at the time of addition to any combination specified in the description and / or in situ generation in a combination by chemical reactions described in the specification, and does not necessarily prevent chemical changes for the materials as a result of the reaction not established in the combination; the specification of the materials in ionic form means that the materials are provided to prepare the compositions containing them in the form of soluble substance (s) containing the specified ions and involves the presence of any composition specified to contain sufficient counter ionic materials to produce electrical neutrality for the composition as a whole; any of the thus implicitly specified counterions are preferably selected from among other constituents explicitly specified in ionic form, as far as possible; otherwise, these counterions may be selected freely, except to avoid counterions that adversely affect an objective of the invention.

BRIEF COMPENDI OF THE INVENTION It has been found that a hydrophilicity can be imparted to a wide variety of surfaces, and a desirable combination of hydrophilicity and corrosion resistance can be avoided on a surface with the underlying metal, particularly aluminum and its alloys containing at least 75% by weight of aluminum, contacting the surface, preferably, if the surface has underlying metal, after this metal has already been applied a protective coating against corrosion, with an aqueous liquid composition containing, preferably consists essentially of, or more preferably consists of water, and: (A) a sufficient amount of a polymer component dissolved and / or stably dispersed containing SO3M portions, where M represents hydrogen or a monovalent cation, or a monovalent fraction of a cation with a valence of two or more; and optionally, one or more of the following components: (B) a component of one or more dissolved substances that can be prepared, and preferably actually prepared, by dissolving at least one of the elemental metals metal oxides and metal hydroxides in phosphoric acid aqueous; (C) a component of pH adjusting substances that are not part of any of the components (A) and (B) as already described; and (D) an antimicrobially effective amount of at least one antimicrobial agent that is not part of any of the components (A) to (C) as already described, the amount of the component (A) being sufficient in a process of agreement. with the invention if the specific surface that is being treated has a smaller dispersion contact angle of the pure liquid water on the surface after being treated with a composition according to the invention as compared to that which had the same surface before this treatment; for a comparison according to the invention, the amount of component (A) is sufficient if at least one type of surface can be treated with the composition in a process according to the invention, so that pure, liquid water has a smaller dispersion contact angle on the surface after the treatment than on the surface before the treatment.

One embodiment of the invention is a composition, as already described, suitable for direct use in imparting hydrophilicity to a surface; such a composition can be described hereinafter as a "working composition". Another embodiment of the invention is a concentrated composition, which can be diluted with water to produce a working composition as already specified. A concentrated composition according to this invention preferably contains from 1.5 to 10, more preferably from 2.5 to 5, or even more preferably from 3.6 to 4.4 times the concentrations of each of the components, less water, of a composition of work. Yet another embodiment of the invention is a process for contacting a surface to be hydrophilized with a working composition according to the invention as described above. Other embodiments, such as a manufacturing product containing a hydrophilized surface according to the invention and an expanded process including a simple process according to the invention together with other steps that may be conventional per se, will be evident from the following description.

DETAILED DESCRIPTION OF THE INVENTION The component (A) as already defined, preferably is selected from the group consisting of: (i) vinyl sulfonic acid polymers and (ii) polymeric molecules having the most, or most preferably all , the -SO3M portions directly and chemically bound to an aromatic ring, the latter being more preferred. Any aromatic ring, including those with heteroatoms, is suitable, but for economy and commercial availability, simple phenyl rings are preferred and sulfonated polystyrene is particularly preferred. A sufficient ratio of the SO3M portion to the carbon atoms in the polymers to give the polymer a water solubility of at least, with increasing preference in the given order 0.1, 0.3, 0.5, 0.7, 1.0, 2.0, 3.0 or 4.0% is preferred, and more particularly for polymers containing aromatic rings, the ratio of the -SO3M to the aromatic rings is at least, preferably increasing in the given order 0.25: 1.0, 0.40: 1.0, 0.55: 1.0, 0.65: 1.0 , 0.75: 1.0, 0.85: 1.0, 0.90: 1.0, 0.95: 1.0 or 0.99: 1.0. Regardless of other preferences, the weighted average molecular weight of the polymers in component (A) is preferably at least, with increasing preference in the given order, 1000, 3000, 5000, 7000, 10,000, 20,000, 30,000, 40,000, 50,000 , 60,000, 65,000 or 69,000 and regardless of preference is no greater than, with increasing preference in the given order, 10,000,000 5,000,000, 3,000,000, 1,000,000 800,000, 600,000, 400,000, 300,000, 200,000, 150,000, 120,000, 100,000, 90,000, 85,000, 80,000 , 75,000 or 71,000. Also independently of other preferences, when the component (A) is dissolved in water in the course of the preparation of an aqueous liquid composition according to this invention, it is preferably added in a form for which "M" in the formula general -SO3M represents an alkali metal cation, so that the added polymer is neutral instead of strongly acidic, as it would be if "M" in this general formula represents hydrogen, for reasons of economy "M" in this general formula of higher preference represents sodium. Preferred sources of component (B) as already described, a component, the presence of which is normally highly preferred in an aqueous treatment composition of the invention, can utilize any of the phosphoric acids for its anionic and / or non-ionized parts. and whose phosphorus is in its +5 oxidation state, ie, metaphosphoric acid (HPO3), orthophosphoric acid (H3PO4), pyrophosphoric acid (H4P2O7), or any of the higher condensed phosphoric acids with the general formula H (n + 2) nO (3n + i), where n represents a positive integer with a value of at least 3, or any of the anions obtained from any of these acids. It is generally considered that all these acids are in equilibrium with each other in aqueous solutions, with orthophosphoric acid being the most predominant at low concentrations and temperatures and most condensed acids (including metaphosphoric acid) being important only at high concentrations and temperatures, or when its salts are present in the aqueous solutions together with the acids. At least in part for reasons of economy, orthophosphoric acid is generally preferred for use in this invention. The aqueous solutions of any of the sufficiently water-soluble salts of these phosphoric acid (s) can be used as the component (B) in an aqueous liquid composition according to the invention, but, as already briefly pointed out in the foregoing, it is preferable to use aqueous liquid compositions prepared by dissolving the metal oxide (s) and / or hydroxide (s), hereinafter frequently abbreviated together as "(hydr) oxide (s)", in aqueous solutions of phosphoric acid instead of solutions of the salts themselves. Preferred treatment solutions are described in this form because it is often possible to obtain transparent and otherwise apparently stable solutions by dissolving the metal (hydr) oxide (s) in aqueous solutions of phosphoric acid, although these apparent solutions are " supersaturated "with respect to the salt or salts phosphate and / or phosphate mono- or diacid to which the content of phosphoric acid and metal normally corresponds. Although the invention should not be considered as limited to any theory, it is considered that these "supersaturated" solutions may contain compounds in coordination or other chemical species of unknown structure that are at least part of the reason for their hydrophilizing properties. In addition, it is preferable to dissolve the phosphoric acid (s), followed by the (s) (hydr) metal oxide (s), before the addition of the other ingredients except water, in the preparation of an aqueous liquid composition according to this invention.

An aqueous solution formed in this way can then be added to a solution prepared separately containing some or all of the other ingredients that are to be included in a composition according to the invention, or these ingredients can be added directly to the solution formed by dissolving the (hydr) metal oxide (s) in the aqueous phosphoric acid. Preferably, the metal (s) (hydr) oxide (s) co-dissolved with phosphoric acid in an aqueous liquid composition used according to the invention are metal hydroxides with a valence of at least 2, more preferably exactly 2. The only most preferred metal is magnesium. When the (hydr) oxide (s) of one or more divalent metals are used with orthophosphoric acid as preferred to form the component (B) in situ in the course of the preparation of an aqueous liquid composition according to the invention , the molar ratio of the divalent metal to the phosphorous atoms in the orthophosphoric acid is preferably at least, preferably increasing in the given order, 1.0: 5.0, 1..0: 4.0, 1.0: 3.5, 1.0: 3.0, 1.0: 2.8, 1.0: 2.6, 1.0: 2.4, 1.0: 2.3, 1.0: 2.2, 1.0: 2.1 or 1.0: 2.05, and independently of preference is not greater than 1.0: 0.5, 1.0: 0.8, 1.0: 1.0, 1.0: 1.2, 1.0: 1.4, 1.0: 1.6, 1.0: 1.7, 1.0: 1.8, 1.0: 1.9 or 1.0: 1.95. The center of the most preferred range thus corresponds to the diacid phosphate salt of the metal of the divalent metal. Independently, when mixing the (hydr) metal oxide (s) with aqueous phosphoric acid during the preparation of an aqueous liquid composition according to the invention, the initial concentration of the acid (s) phosphoric acid (s), measured as the sum of the stoichiometric equivalents such as orthophosphoric acid of all the phosphoric acid (s) present (s) in which the phosphorus is in its valence +5 state, preference is at least, with increasing preference in the given order, 0.007, 0.011, 0.020, 0.030, 0.040, 0.050, 0.058, 0.064, 0.068, or 0.072 moles of orthophosphoric acid per kilogram of the total aqueous liquid composition, this unit of concentration , which can be applied to any ingredient of the composition having a defined mole, hereinafter abbreviated as "M / Kg", and independently this concentration value in an aqueous liquid composition according to the invention. n preferably is not more than, with increasing preference in the order given, 1.5, 1.0, 0.8, 0.6, 0.4, 0.200, 0.160, 0.130, 0.100, 0.090, 0.080, or 0.074 M / kg. In the course of preparing an aqueous liquid composition according to the invention, if component (B) is used and prepared in itself as described above, preferably component (A) is added to an aqueous solution containing the component (B) before the addition of the other ingredients of the composition, minus the water. A working composition according to this invention, preferably has a pH value which is at least, with increasing preference in the given order, 3.0, 3.5, 4.0, 4.6, 4.9, 5.2 or 5.4, and independently of preference is not greater than, with increasing preference the given order, 9.0, 8.5, 8.0, 7.5, 7.0, 6.5, 6.2, 6.0, 5.8 or 5.6. If, with the amounts of the components (A) and (B) used in a composition according to the invention, a preferred pH value is not obtained, preferably an alkalizing or acidifying agent, the component (C), should be added to the composition. ) optional. A wide variety of agents suitable for this purpose are known to those skilled in the art. If an alkalinizing agent is necessary, as is normal when components (A) and (B) have their chemical characteristics and more preferred concentrations, preferably the same chemical type (s) of (hydr) are used as alkalizing agents. metal oxide (s) as they were used to form component (B) in si t? during the preparation of the composition. Any amount of (hydr) metal oxide (s) used for this purpose is not considered part of the (hydr) metal oxide that reacts in itself to generate the component (B) as already described, for the purpose of determining compliance with any of the limits of the preferred molar proportions specified in the foregoing for this reaction in itself. It has been observed that the compositions according to the invention, which contain only the components (A) to (C) in addition to water are susceptible to develop mycotic infestations of fungi apparently carried by the ambient air. Therefore, it is usually preferred that at least one fungicide is present in a composition according to the invention as the optional component (D). A particularly suitable fungicide is 2- (4-thiazolyl) benzimidazole, which has the special advantage of being successful in long-term use as a medicine for humans and, thus, is very unlikely to have any unexpected toxicity. A working composition according to the invention, preferably contains, independently for each specified component: component (A) in a concentration that is at least 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 8.5, 9.0, 9.5 or 9.9 parts of component (A) per thousand parts of the total composition by weight, a unit of concentration that can be applied generally to any other specified material as well as to component (A) and henceforth will usually be abbreviated as "ppt", and independently of preference is not greater than, with increasing preference in the given order, 100, 75, 50, 30, 25, 22, 19, 16, 14, 13.0, 12.5, 12.0, 11.5, 11.0, 10.5 or 10.1 ppt; the component (B) in a concentration that is, at least, with increasing preference in the given order, 0.5, 1.0, 1.3, 1.6, 1.9, 2.1, 2.3, 2.5 or 2.7 ppt and independently, preferably is not greater than, with increasing preference in the given order, 25, 15, 10, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.5, 3.3, 3.1 or 2.9 ppt; and component (B) in a concentration that is at least, with increasing preference in the given order, 0.1, 0.3, 0.5, 0.7 or 0.9 ppt and independently, preferably not greater than, with increasing preference in the given order, 5, 3, 2.5, 2.0, 1.8, 1.6, 1.4, 1.2 or 1.0 ppt; all preferred upper limits in the earlier parts of this paragraph are preferred primarily by economics, larger concentrations do not improve the results obtained and are more expensive. The lower limits are preferred to obtain a strongly hydrophilic surface. The amount of the component (C) should preferably be chosen to obtain the preferred pH values for the composition that has already been specified above. For various reasons it is often preferred that the compositions according to the invention, as already defined, should be substantially free of many ingredients used in the compositions for similar purposes in the prior art. Specifically, it may be, with increasing preference in the given order, independently of each component of preference reduced to the minimum indicated in the following, that these compositions, when placed in direct contact with metals in a process according to the invention, contain no more than 1.0, 0.35, 0.10, 0.08, 0.04, 0.02, 0.01 or 0.001% of each of the following constituents, except when such constituents may be part of the necessary or optional components of the compositions as specified above: any metallic element with an atomic number greater than 20, except for titanium, zirconium and hafnium in complex fluoride anions; nitrate and other oxidizing agents (any other being measured as its stoichiometric equivalent oxidant as nitrate); organic liquids with a boiling point below 120 ° C at normal atmospheric pressure; and silica and / or dispersed alumina. After establishing contact between the liquid, aqueous treatment composition and the surface to be hydrophilized, the treated surface is dried, preferably without intermediate rinsing. The surface can be dried simply by exposure to ambient air with a relative humidity of less than 100%, but it is usually preferred to use hot air, which can favor some advantageous chemical reaction in the coating, as well as the definitive acceleration of the drying process. The temperature at which the coating applied according to this invention is preferably dried is at least, preferably increasing in the given order, 100, 125, 135, 138, 142, 145 or 148 ° C and independently of preference is not greater than with increasing preference in the given order, 200, 175, 165, 162, 159, 156, 153 or 150 ° C. The amount of carbon, obtained at least in part from the component (A) in a composition according to the invention and measured in grams of carbon per square meter of treated surface (a unit that can be applied to other materials besides carbon and in the following will usually be abbreviated as "g / m"), which is added to the surface after drying during treatment with a composition according to this invention as described above, a value that can be easily determined from the surface emission analysis, preferably corresponds to at least, with increasing preference in the given order, 0.05, 0.10, 0.14, 0.18, 0.21, 0.24 or 0.26 g / m2 and independently, mainly for reasons of economy, preferably it is not greater than, with increasing preference in the given order, 2.0, 1.5, 1.10, 0.80, 0.50, 0.40, 0.32 or 0.28 g / m. Of course, if the primary treatment applied before the treatment with a composition according to this invention also contains carbon, as in the more preferred primary treatments, the carbon emission from the treated surface must be measured before and after the treatment in accordance with this invention for determining, by difference between the two values, the amount added attributable to the treatment with a composition according to this invention. A hydrophilizing treatment according to this invention can be applied on any type of surface that is not already completely hydrophilic. A hydrophilizing treatment according to this invention is generally advantageous when applied to underlying metals that have already been coated by conversion according to the teachings of any of the following United States patents, the descriptions of all of which, except for any part that may be inconsistent with any explicit statement herein, are hereby incorporated by reference: 5,595,611 of January 21, 1997 of Boulos et al.; 5,551,994 of September 3, 1996 of Schriever; 5,534,082 of July 9, 1996 by Dollman et al .; 5,507,084 of April 16, 1996 of Ogino et al .; 5,498,759 of March 12, 1996 from Nakada et al .; 5,498,300 of March 12, 1996 from Aoki et al .; 5,487,949 of January 30, 1996 of Schriever, 5,472,524 of December 5, 1995; 5,472,522 of December 5, 1995 from Kawaguchi et al; 5,452,884 of October 3, 1995; 5,451,271 of September 19, 1995 from Yoshida et al .; 5,449,415 of September 19, 1995 from Dolan; 5,449,414 of September 12, 1995 from Dolan; 5,427,632 of June 27, 1995 from Dolan; 5,415,687 of May 16, 1995 from Schriever; 5,411,606 of May 2, 1995 from Schriever; 5,399,209 of March 21, 1995 of Suda et al .; 5,395,655 of March 7, 1995 de Kazuyuki et al .; 5,391,239 of February 21, 1995 de Boulos; 5,378,392 of January 3, 1995, Miller et al .; 5,366,567 of November 22, 1994 of Ogino et al .; 5,356,490 from October 18, 1994 from Dolan 1 et al .; 5,342,556 of August 30, 1994 from Doian; 5.3i8.640 of June 7, 1994 from lshii et al .; 5,298,092 of March 29, 1994 from Schriever; 5,281,282 of January 25, 1994 from Dolan et al .; 5,268,042 of December 7, 1993 by Carlson; 5,261,973 of November 16, 1993 by Sienkowski et al .; 5,242,714 of September 7, 1993 by Steele et al .; 5,143,562 of September 1, 1992 de Boulos; 5,141,575 of August 25, 1992 from Yoshitake et al .; 5,125,989 of June 30, 1992 from Hall an; 5,091,023 of February 25, 1992 from Saeki et al .; 5,089,064 of February 18, 1992 of Reghi; 5,082,511 of June 21, 1992 de Fariña et al .; 5,073,196 of December 17, 1991; 5,045,130 of September 3, 1991 from Gosset et al .; 5,000,799 of March 19, 1991 from Miyawaki; 4,992,196 of February 13, 1991 by Hallman; 4,985,087 of January 15, 1992 by Mori et al .; 4,966,634 of October 30, 1990 by Saeki et al .; 4,961,794 of October 9, 1990 of Miyamoto et al .; 4,956,027 of September 11, 1990 by Saeki et al .; 4,927,472 of May 22, 1990 from Matsushima et al .; 4,880,476 of November 14, 1989 by Matsuda et al .; 4,874,480 of October 17, 1989 of Sonoda et al .; 4,865,653 of September 12, 1989 by Kra er; 4,849,031 of July 18, 1989 by Hauffe et al .; 4,846,897 of July 11, 1989 by Nakagawa et al .; 4,812,175 of March 14, 1989 by Reghi; 4,801,337 of January 31, 1989 by Higgins; 4,756,805 of July 12, 1988 by Terada et al .; 4,749,418 of June 7, 1988 by Saeki et al .; 4,722,753 of February 2, 1988 de Zurilla et al .; 4,717,431 of January 5, 1988 by Knaster et al .; 4,673,444 of June 16, 1987 by Saito et al .; 4,668,305 of May 26, 1987 by Dollman et al .; 4,650,525 of March 17, 1987 of Yoshida et al .; 4,617,346 of March 3, 1987 from Prescott; 4,644,029 of February 17, 1987 of Cable et al .; 4,643,778 of February 17, 1987 by Donofrio et al .; 4,637,840 of January 20, 1987 by Fuji et al .; 4,637,838 of January 20, 1987 by Rausch et al .; 4,617,068 of October 14, 1986 of King; 4,596,607 of June 24, 1986 by Huff et al .; 4,595,424 of June 17, 1986 of Hacías; 4,565,585 of June 21, 1986 of Matsuda; 4,559,087 of December 17, 1985 de Jórns et al; 4,509,992 of April 9, 1985 by Higgins; 4,498,935 of February 12, 1985 from Kent et al .; 4,496,404 of January 29, 1985 by King; 4,486,241 of December 4, 1984 of Donofrio; 4,475,957 of October 9, 1984 of Sander; 4,433,015 of February 21, 1984 of Lindert; 4,419,199 of December 6, 1983 by Hauffe et al .; 4,419,147 of December 6, 1983 by Murakami et al .; 4,416,705 of November 22, 1983 of Sie und et al .; 4,389,260 of June 21, 1983 by Hauffe et al .; 4,385,096 of May 24, 1983 by Wetzel; 4,281,203 of April 26, 1983 of Reinhold; 4,370,177 of January 25, 1983 by Frelin et al .; 4,341,558 of July 27, 1982 by Yashiro et al .; 4,339,310 of July 13, 1982 by Oda et al .; 4,338,141 of July 6, 1982 by Senzaki et al .; 4,338,140 of July 6, 1982 by Reghi; 4,316,751 of February 23, 1982, Prescott et al .; 4,313,769 of February 2, 1982 by Frelin et al .; 4,311,535 of January 19, 1982 by Yasuhara et al .; 4,306,917 of December 22, 1981 by Oda et al .; 4,295,899 of October 20, 1981 of Oppen; 4,292,096 of September 29, 1981 by Murakami et al .; 4,287,004 from September 1, 1981 by Murakami et al .; 4,278,477 of July 14, 1981 of Reinhold; 4,273,592 of June 16, 1981 of Kelly; 4,264,378 of April 28, 1981 by Oppen et al .; 4,220,486 of September 2, 1980 from Matsushima et al .; 4,191,596 of March 4, 1980 by Dollman et al .; 4,183,772 of June 15, 1980 from Davis; 4,174,980 of November 20, 1979 by Howell, Jr. et al .; 4,169,741 of October 2, 1979 by Lampatzer et al .; 4,163,679 of August 7, 1979 by Nagae et al .; 4,153,479 of May 8, 1979 by Ayano et al .; 4,149,909 of April 17, 1979 from Hamilton; 4,148,670 of April 10, 1979 of Kelly; 4,146,410 of March 27, 1979 of Reinhold; 4,142,917 of March 6, 1979 of Yashiro et al .; 4,136,073 of January 25, 1979 by Mori et al .; 4,131,489 of December 26, Newhard, Jr .; 4,108,690 of August 22, 1978 of Heller; 4,101,339 of July 18, 1978 by Kaneko et al .; 4,063,968 of December 20, 1977 of Matsushima et al .; 4,059,452 of November 22, 1977 from Nishijima et al .; 4,054,466 of October 18, 1977 of King et al .; 4,017,334 of April 12, 1977 of Matsushima et al .; 3,989,550 of November 2, 1976 by Newhard; 3,964,936 of June 22, 1976 from Das; 3,912,458 of October 4, 1975 from Faigen; 3,978,237 of April 22, 1975 of 1975 from Faigen; 3,876,435 of April 8, 1975 from Dollman; 3,860,455 of January 14, 1975 by Hansen et al .; 3,850,700 of November 26, 1975 by Séller; 3,839,099 of October 1, 1974 by Jones; 3,819,424 of June 25, 1974 by Russell et al .; 3,819,422 of June 25, 1974 by Schneider; 3,819,385 of June 25, 1974 by Schumichen et al .; 3,759,549 of March 6, 1974 by Matsushima et al .; 3,758,349 of September 11, 1973 from Engesser; 3,723,334 of March 27, 1973 of Marurer; 3,723,192 of March 27, 1973 from Obi et al .; 3,706,604 of December 19, 1972 from Paxton; 3,697,332 of October 10, 1972 of Kuehner; 3,671,332 of June 20, 1972 from Rausch et al .; 3,660,172 of May 2, 1972 from Otto; 3,645,797 of February 29, 1972 of Lorín; 2,632,447 of January 4, 1972 by Albrecht et al .; 3,625,777 of December 7, 1971 from Okabe et al .; 3,620,777 of November 16, 1971 from Okabe et al .; 3,619,300 of November 9, 1971 from Heller al .; 3,615,912 of October 26, 1971 from Dittel et al; 3,615,890 of October 26, 1971 of Montella; 3,607,453 of September 21, 1971 of Engesser et al; 3,573,997 of April 6, 1971 of Paxton; 3,565,699 of February 23, 1971 of Paxton; 3,547,711 of December 15, 1970 from Ashdown; 3,544,388 of December 1, 1970 from Russell; 3,535,168 of October 20, 1970 from Thompson; 3,533,859 of October 13, 1970 by Engesser et al .; 2,519,494 of July 7, 1970 from Engesser et al .; 3,516,875 of June 23, 1970 from Rausch et al; 3,515,600 of June 2, 1970, Jones et al .; 3,505,129 of April 7, 1970 from Burstein et al .; 3,501,352 from March 17, 1970 from Shan; 3,493,441 of February 3, 1970 from Rausch et al .; 3,493,440 of February 3, 1970 from Ashdown; 3,484,304 of December 16, 1969 from Beach; 3,468,724 of September 23, 1969 of Reinhold; No. 3,467,589 of September 16, 1969 to Rausch et al .; 3,462,319 of August 19, 1969 from Campbell; 3,459,604 of August 5, 1969 by Freeman et al .; 3,454,483 of July 8, 1969 by Freeman; 3,450,578 of June 17, 1969 from Siemund et al .: 3,450,577 of June 18, 1969 from Beach; 3,449,229 and 3,449,222 of June 10, 1969 by Freeman et al .; 3,444,007 of May 13, 1969 by Maurer et al .; 3,425,947 of February 4, 1969 by Rausch et al .; 3,404,046 and 3,404,044 of October 1, 1968 by Russell et al .; 3,404,043 of October 1, 1968 from Dell; 3,397,093 of August 13, 1968 by Oswald et al .; 3,397,092 of August 13, 1968 from Cavanagh; 3,397,091 and 3,397,090 of August 13, 1968 of Russell et al .; 3,385,738 of May 28, 1968 from Russell; 3,380,858 of April 30, 1968 by Champaneria et al .; 3,377,212 of April 9, 1968 by Newhard; 3,348,713 of October 17, 1967 by Lodeseen et al .; 3,338,755 of August 29, 1967, by Jenkins et al .; 3,307,980 of March 7, 1967 by Freeman; 3,297,493 of January 10, 1967 from Blum et al .; 3,294,593 of December 27, 1966 from Wyszomirski et al .; 3,268,367 of August 23, 1966 from Nelson; 3,240,633 of March 18, 1966 from Gowman et al .; 3,222,226 of December 7, 1965, Maurer et al .; 3,218,200 from November 16, 1965 from Henricks; 3,210,219 of October 5, 1965 of Jenkins; 3,202,551 of August 24, 1965 by Gerischer et al .; 3,197,344 of July 27, 1965 from Paxton; 3,185,596 of May 25, 1965 by Schiffman; 3,161,549 of December 15, 1964 from Kallenbach; 3,154,438 of October 27, 1964 by Séller et al .; 3,146,113 of August 25, 1964 of Lantoin; 3,130,086 and 3,130,085 of April 21, 1964 of Otto; 3,101,286 of August 20, 1963 of Reinhold; 3,090,710 of May 21, 1963 from Triggle et al .; 3,046,165 of July 24, 1962 by Halversen et al .; 3,041,215 of June 26, 1962 of Jenkins et al .; 3,007,817 of November 7, 1961 from Cavanagh et al .; 2,988,465 of June 13, 1961 by Newhard et al .; 2,979,430 of April 11, 1961 by Keller et al .; 2,967,791 of January 10, 1961 from Halversen; 2,955,061 of October 4, 1960 by Jenkins et al .; 2,928,763 of March 15, 1960, from Russell et al .; 2,902,390 of September 1, 1959 from Bell; 2,892,884 of June 23, 1959 by Rausch et al .; 2,882,189 of April 14, 1959 of Russell et al; 2,868,682 of January 13, 1959 from Dell; 2,851,385 of September 9, 1958 by Spruance et al .; 2,480,498 of June 24, 1958 from Logue et al .; 2,835,617 of May 20, 1958 of Maurer; 2,832,707 of April 29, 1958 by Rossteutscher; No. 2,825,697 of March 4, 1958, of Carroll et al .; 2,819,193 of January 7, 1958 of Rausch; No. 2,813,814 of November 19, 1957, Goodspeed et al .; 2,813,813 of November 19, 1957 of Ley et al.

No. 2,813,814 of November 19, 1957, from So ers et al. 2,809,138 of October 8, 1957 by Wagner et al. 2,805,969 of September 10, 1957, Goodspeed et al. 2,800,421 of July 23, 1957, Goodspeed et al. 2,798,829 of July 9, 1957 by Newhard et al. 2,796,370 of June 18, 1957 from Ostrander et al. 2,769,737 of November 6, 1956 from Russell; 2,702,768 of February 22, 1955 from Hyams; 2,692,840 of October 26, 1954 from Bell; 2,665,231 of January 5, 1954, Amundsen et al .; 2,609,309 of September 2, 1952 of Gibson; 2,591,479 from April 1, 1952 from Ward; 2,438,887 of March 30, 1948 from Spruance, Jr .; 2,298,280 of October 13, 1942 by Clifford et al .; 2,210,850 of August 6, 1940 of Curtin; 2,121,574 of June 21, 1938 of Ro ing; 2,120,212 of June 7, 1938 of Curtin; 1,911,537 of May 30, 1933 from Tanner; 1,895,968 of January 31, 1933 from Curtin et al .; 1,651,694 of December 6, 1927, from Green et al .; 1,525,904 of February 10, 1925 from Alien; 1,291,352 of January 14, 1919 from Alien; 1,287,605 of December 17, 1918 from Alien; and 1,248,053 of November 27, 1917 from Alien. The hydrophilizing treatment according to the invention is particularly advantageous applied on conversion coatings formed on aluminum by treatment with aqueous, acidic liquid compositions, containing at least one of the chemical species HB4, H2SiF6, H2TiF6, H2? RF6, and the salts of any of these acids. More preferably, the liquid compositions used to form a conversion coating on which a hydrophilizing treatment according to this invention is applied includes at least H2TiFe, H2ZrF6, and salts of both acids, most preferably ZrFg and its salts. Still more preferably, the liquid compositions used to form a conversion coating on which a hydrophilizing treatment in accordance with this invention is applied also includes a poly (vinylphenol) polymer substituted with polyhydroxyalkylaminomethylene, as described in detail in the US Pat. 5,068,299, the entire description of which, except for any part that may be inconsistent with any explicit statement herein, is hereby incorporated by reference. More preferred are the polymers having the composition resulting from the process and the materials described in column 11, lines 47-55 of U.S. Patent 5,068,299. Regardless of other preferences, compositions of this most preferred type to form a conversion coating to be hydrophilized according to this invention preferably contain a total amount of HB4, H2SiF6, H2TiF6, H2ZrFd, this total including the stoichiometric equivalent as the acid corresponding to any of the salts of these acids that may be present and henceforth briefly defined as "total fluoroacid", such that the weight ratio of the total acid fluorine in the composition forming the conversion coating to the content of the poly. { vinyl phenol) substituted with polyhydroxyalkylene methylene as described in detail in U.S. Patent 5,068,299 in the same composition is at least, with increasing preference in the given order 0.02: 1.0, 0.05: 1.0, 0.08: 1.0, 0.11: 1.0, 0.13 : 1.0, 0.15: 1.0, 0.17: 1.0, 0.19: 1.0 or 0.21: 1.0, and independently of preference is no greater than, with increasing preference in the given order 2.0: 1.0, 1.5: 1.0, 1.0: 1.0, 0.80: 1.0 , 0.60: 1.0, 0.50: 1.0, 0.40: 1.0, 0.35: 1.0, 0.30: 1.0, 0.27: 1.0 or 0.24: 1.0. Independently, in a treatment process with such compositions according to the invention, the amount of carbon, coming from the polymer content of the treatment composition, is added to the treated surface as part of its primary coating is at least, preferably increasing in the given order 0.04, 0.08, 0.12, 0.18, 0.24, 0.28, 0.30, 0.34 or 0.36 g / m2, and independently of preference is not greater than, with increasing preference in the given order 4.0, 3.0, 2.0, 1.0, 0.80, 0.60, 0.55, 0.50, 0.45 or 0.40 g / m2. The second most preferred chemical type of conversion coatings to be hydrophilized according to this invention are those described in detail in U.S. Patent Nos. 5,356,490, October 18, 1994, Dolan et al., And 45,427,632, June 27, 1994. 1995 by Dolan, The complete descriptions of both patents, except for any part that may be inconsistent with the statements set forth herein, are hereby incorporated by reference. As is known to those skilled in the art, before forming any type of conversion coating on aluminum, it is usually preferred to clean and deoxidize the surface by one of the means known in the art. The practice and benefits of the invention can be further appreciated by considering the following non-limiting working and comparative examples.

EXAMPLE AND COMPARATIVE EXAMPLE GROUP 1 The treated surfaces were in sample sheets (panels) of one of the type 3003 aluminum-coated or alloy panels of the type used for automobile air-conditioning heat exchangers. The sequence of the processing for all the examples included the following steps in succession in the order shown below: 1. Cleaning by immersing the substrate surfaces for two minutes (henceforth usually abbreviated as "min") in a solution 1.5% of RIDOLINE® 53 Concetrate, commercially available from Henkel Surface technologies Div. Of Henkel Corp., Madison Heights, this provider being henceforth commonly abbreviated, as "HST", this solution being maintained during use at 60 ° C; 2. Rinse with cold running water for 40 minutes (henceforth commonly abbreviated as "sec"). 3. Treatment of the primary protective coating - see details for specific cases below. 4. Rinse with cold running water for 40 seconds.

. Hydrophilizing treatment - see details of the composition for specific cases below. The sample was immersed in the liquid composition at normal ambient atmospheric pressure and room temperature (ie, 18-23 ° C), and after a few seconds, it was removed from the immersion with a coating of the liquid adhering to its surface. In many cases no deliberate effort was made to thin this coating, while in other cases stirring, air blowing or the like was used to thin the coating to a desired degree, without complete drying. 6. Heat the substrates with the liquid coating from the end of step 5 still in the passage thereof, at 149 ° C for 20 minutes. In this group, the primary protective coating treatment was provided by one of the two methods as follows (the Roman numerals shown on the left are used for identification in the following table (s)): I. Contact with an aqueous liquid composition consisting of the following ingredients in addition to water: (i) 2.0 ppt of a poly (4-vinylphenol) substituted with polyhydroxyalkylaminsmethylene of the chemical type produced as described in column 11, lines 47-56 of US Patent 5, 068, 299, (ii) 10.0 ppt of boric acid (ie, H3BO3) and (iii) 0.43 ppt of fluorochirconic acid (ie, H2ZrF6). This composition had a pH of 3.7 and was maintained at 43 ° C while the aluminum panels were submerged therein for 90 minutes. II. The same as in I, except that 0.24 ppt of fluorotitanic acid (ie, H ^ TiFg) was replaced by all the fluorocirconic acid used in alternative I. 2 This cleaner is not recommended for cleaning before the primary protective coatings chromator, because it does not attack the cleaned surfaces with this enough to remove all the oxides from the surfaces, and usually resulting in thin and non-uniform chrome coatings. However, it is completely satisfactory as a cleaner for primary protective coatings actually used in this group of examples.

The hydrofilizing treatment compositions used were as follows (with the upper case letters shown on the left used for identification in the following table (s)): A 0.5% water solution of a chemical corresponding to the salt sodium of a 4-vinyl benzene sulfonic acid polymer (actually prepared by polystyrene sulfonation), with a weight average molecular weight (such as the sodium salt) of about 70,000. B) A water solution of 0.5% of the sodium salt of a vinyl sulfonic acid polymer, with a weighted average molecular weight (such as the sodium salt) reported by the representative of its supplier (Aldrich Chemical Co.). as approximately 4,000 to 6,000. The details of the carbon added in the masses and some test results in the finished panels are given in Table 1 below. 4 replicates were used for each identification number shown in Table 1, and the results of each replicate were averaged to obtain the values reported in the table. The soak test in water for which the results are shown consisted in submerging the coated substrates to be tested in a constant volume of deionized water through which the fresh deionized water kept flowing constantly at a sufficient rate to replace all the constant volume of deionized water in which the tested substrates were submerged every 12 minutes.

EXAMPLE AND COMPARATIVE EXAMPLE GROUP 2 In this group, the treated surfaces were those in the sample sheets (panels) of one of the aluminum alloys type 3003, 5052 or 6061 or on sample pieces of coil structures or commercial evaporator fin and stacked plate of the type used for the heat exchangers of the air conditioning of the automobiles.

Table 1 / Abbreviations for Table 1? HR "means" relative humidity ".

(These structures have a spacing between the plates, through the channels in which the refrigerant heat transfer fluid flows when an air conditioner incorporating such a structure, of approximately 1 cm, and a spacing between the fins is in use, around which the air flows when an air conditioner is in use incorporating such a structure, approximately 1 ml.) The processing sequence for all the examples included the following steps in succession in the order shown below: 1. Alkaline attack / cleaning by immersing the samples in a 5% by volume solution of the concentrated cleaning formulation PARCO® Cleaner 305, available commercially from HST, in water at 60 ° C for 2.0 minutes. 2. Rinse twice with cold running water for 20 seconds each time. 3. Deoxidize by immersion in a 12% by volume solution of a 70% solution of HNO3 in water during 2. 5 minutes at 21 ° C. 4. Rinse twice with cold running water for 20 seconds each time. 5. Treatment of the primary protective coating - see details for specific cases below. 6. Rinse twice with cold running water for 40 seconds. 7. Hydrophilizing treatment - see details of the composition for specific cases below. The sample was immersed in the liquid composition at normal ambient atmospheric pressure and room temperature (i.e., 18-23 ° C), and after at least a few seconds, removed from the immersion with a coating of the liquid adhering to its surface.

In many cases no deliberate effort was made to thin this coating, while in other cases stirring, air blowing or the like was used to thin the coating to a desired degree, without drying it completely. 8. Heat the substrates with the liquid coating from the end of step 7 still in place therein, at 149 ° C for 20 minutes. The primary protective coating treatment for Group 2 was provided by Method I as used in Group 1 or by one of the methods as follows (Roman numerals shown on the left are used for identification in the following table (s)) ): III. Chromium conversion coating by immersion in a 4% by weight solution in water of the conversion coating concentrate ALODINE® 713 Chromium (HST) at 38 ° C for 180 seconds to produce an additive-type mass of approximately 1050 mg / m . IV. The same as in Method I for Group I, except that no boric acid was used in the liquid treatment composition. V. A solution was prepared and used as described in the examples of U.S. Patent 5,356,490 of October 18, 1994, from Dolan et al., But with the following amounts of materials: 27.9 ppt of 60% fluorotitanic acid; 1.4 ppt of silica; 4.9 ppt of basic zirconium carbonate; 68 ppt of the 10% solution of the polymer prepared according to the instructions in column 11, lines 39-52 of U.S. Patent 4,963,596; and the difference water. A solution containing 94 ppt of magnesium acetate tetrahydrate and 149 ppt of a solution of cobalt nitrate in water containing 13% cobalt, with the difference of water, was used to treat the aluminum substrates by immersion for 4 minutes at 54 minutes. ° C. The following hydrophilizing treatment compositions were used (uppercase letters being used for identification in the following table): Four (4) liters of an aqueous solution containing 1. 0% of the sodium salt of the polymers of 4-vinyl benzene sulfonic acid and 0.10% of 2- (4-thiazolyl) benzimidazole (fungicide) was mixed with 300 grams of a separate aqueous solution, formerly formed by the addition of water 121 ppt of 75% H3PO4 in water and then 26.3 ppt of 95% Mg (OH) 2 for a total of 1000 parts of solution. The pH of the resulting mixture was then adjusted to 5.2 by the addition of approximately 1.5 grams of 95% MG (HO) 2 to the mixture. D. PALENE® 4546 hydrophilizing treatment concentrate prepared as mentioned by the manufacturer, Nihon Parkerizing Co., Ltd. This treatment composition does not contain polymers with sulfonic acid or its salt portions in the polymer and therefore does not agree with this invention. E. An aqueous solution formed by the addition to water of 121 ppt of 75% H3PO4 in water and 26.3 ppt of 95% Mg (0H) 2 for a total of 1000 parts of solution - is not in accordance with this invention. F. The same as in C, except that additions of the solution containing a reaction product of phosphoric acid and magnesium hydroxide and additional magnesium hydroxide were omitted. G. A 15 ppt water solution of ammonium decavanadate - not according to the invention. H. A solution in water of: 39 ppt of lithium hydroxide monohydrate; 57 ppt glacial acetic acid; 12 ppt sodium ammonium decavanadate; 0.02 ppt of CHEMEEN ™ C12G surfactant, and the water difference. Table 2 below gives additional details and the hydrophilicity test (water contact angle) as results for the examples on the sample sheets. The soak test in water for which the results are reported was performed in the same way as for Group 1. Table 3 below gives results of the corrosion test on five types of samples after exposure to air for 1008 hours at Relative humidity of 100% and a temperature of 38 ° C. The scale of classifications for the two columns on the right of Table 3 was as follows: 1 = undetectable discoloration, 2 = some slight discoloration; 3 = light discoloration and some white corrosion products on the surface; 4 = evident discoloration and some white corrosion products on the surface. Some of the samples were also evaluated for odor production by a trained panel and operated according to the methods of the American Society for Testing and Materials Standard Test Procedures 758, 434, and 594. These classifications indicate that the products prepared in accordance with the preferred embodiments of the invention they did not present a tendency and may have had less tendency, in comparison with the hydrophilizing products currently in commerce with better resistance to developing unpleasant odors, to develop odors that can be objected by most of the classifiers.

Table 2 Abbreviations for Table 2"n.s" means "not significant, because there is <0.015 p g / m carbon even before soaking".

Table 3 Abbreviations for table 3"% W" means "percent of the surface that had white corrosion products in it when it was observed"; "1 (SwS)" means "a small white spot was observed on the surface, but otherwise there was no discoloration of the surface"; ? n.p 'means? Or tested. "

Claims (20)

1. A process for increasing the hydrophilicity of a solid surface over which pure liquid water has, under normal atmospheric pressure and temperature within the range of 18-23 ° C, an initial contact angle that is at least 5 °, the process consists of in the steps of: (I) forming on the solid surface a coating of a liquid hydrophilizing composition containing water and a concentration of a component (A) selected from the group consisting of, dissolved, stably dispersed or dissolved and dispersed from stably, organic polymeric molecules containing -S03M moieties wherein M represents hydrogen, a monovalent cation or a monovalent moiety of a cation with a valence of 2 or greater; and (II) drying the coating of the liquid composition formed in step (I) to form a modified solid surface in which at least part of the polymers containing the -SO3M portions that were in the coating of the liquid hydrophilizing composition formed in step (i) remain attached, pure liquid water under normal atmospheric pressure and temperature having an initial contact angle on the modified solid surface that is smaller than its contact angle on the solid surface coated in step (I) .

2. The process according to claim 1, wherein the concentration of the component (A) in the liquid hydrophilizing composition is in a range from about 1.0 to about 100 ppt and the liquid hydrophilizing composition further comprises a concentration that is from about 0.5. at about 25 ppt of a component (B) of one or more of the dissolved substances, selected from the group consisting of substances that have been prepared by dissolving at least one of the divalent elemental metals, divalent metal oxides and divalent metal hydroxides in the acid aqueous phosphoric

3. The process according to claim 2, wherein the liquid hydrophilizing composition has a pH value from about 4.0 to about 8.0. The process according to claim 2, wherein the solid surface coated in step (I) has been formed by treating an aluminum substrate with an aqueous, acidic liquid composition comprising at least one of the chemical species selected from the group consisting of HB4, H2SiFg, H2TiF6, H2ZrF6 and the salts of any of these acids. 5. The process according to claim 4, wherein: the component (A) is selected from the group consisting of sulfonated polystyrene molecules in which there is a proportion of the -SO3M-portions to the aromatic rings which is at least 0.85. : 1.0; the concentration of component (A) in the liquid hydrophilizing composition is from about 8.0 to about 13.0 ppt; the concentration of component (B) in the liquid hydrophilizing composition is from about 2.1 to about

4.

5 ppt; The pH value is the liquid hydrophilizing composition is from about 4.6 to about 6.2; component (B) is selected from materials prepared by mixing (i) a number of kilograms of an aqueous solution of phosphoric acid having a stoichiometrically corresponding concentration at a concentration from about 0.058 to about 0.100 M / kg of orthophosphoric acid, with ( ii) an amount of magnesium hydroxide, magnesium oxide or magnesium hydroxide and magnesium oxide containing a number of moles of magnesium having a relation to the mathematical product of the number of kilograms of and the concentration in M / kq of the solution aqueous phosphoric acid that is from

1. 0: 2.2 to approximately 1.0: 1.8; step (II) of the process occurs at a temperature in a range from about 135 to about 175 ° C; and - desdp r.frr.Pi dp 0.14 to r.prr.Pi of 0.50 g / m2 of SP carbon added to the solid surface treated in step (I) after completing step (II).

6. A process for increasing the hydrophilicity of a solid surface in which the pure liquid water has, under normal atmospheric pressure and a temperature within the range of 18-23 ° C, an initial contact angle that is at least 5 degrees, the process comprises the steps of: (I) forming on the solid surface a coating of a liquid hydrophilizing composition that has been prepared by mixing water and an amount of one component (A) selected from the group consisting of, dissolved, stably dispersed or dissolved and stably dispersed, organic polymeric molecules containing portions of -SO3M where M represents hydrogen, a monovalent cation or a monovalent fraction of the cation with a valency of 2 or more; Y (II) drying the coating of the liquid composition formed in step (I) to form a modified solid surface on which at least part of the polymers containing the -SO3M portions that were in the coating of the liquid hydrophilizing composition formed in the step (I) remain united, pure liquid water under normal atmospheric pressure and temperature having an initial contact angle on the modified solid surface less than its contact angle on the solid surface coated in step (I).

The process according to claim 6, wherein the liquid hydrophilizing composition is prepared by mixing with water: an amount of the component (A) which corresponds to a concentration from about 1.0 to about 100 ppt of the component (A) in the liquid hydrophilizing composition; and an amount of a component (B) of one or more dissolved substances selected from the group consisting of substances that have been prepared by dissolving at least one of the elemental divalent metals, divalent metal oxides and divalent metal hydroxides in aqueous phosphoric acid, the amount of component (B) corresponding to a concentration that is from about 0.5 to about 25 ppt of component (B) in the liquid hydrophilizing composition.

The process according to claim 7, wherein the liquid hydrophilizing composition has a pH value from about 4.0 to about 8.0.

The process according to claim 8, wherein the solid surface coated in step (I) has been formed by treating an aluminum substrate with an aqueous, acidic liquid composition containing at least one of the selected chemical species of the product. group consisting of HB4, H2SiF6, H2 iF6, H2ZrFβ and the salts of any of these acids.

The process according to claim 9, wherein: the component (A) is selected from the group consisting of sulfonated polystyrene molecules in which there is a proportion of the -S03M-portions to the aromatic rings which is at least 0.85. : 1.0; the amount of the component (A) mixed with water to form the liquid hydrophilizing composition corresponds to a concentration of the component (A) in the liquid hydrophilizing composition that is from about 8.0 to about 13.0 ppt; - the amount of component (B) mixed with water to form the liquid hydrophilizing composition corresponds to a concentration of component (B) in the liquid hydrophilizing composition that is from about 2.1 to about 4.5 ppt; the pH value of the liquid hydrophilizing composition is from about 4.6 to about 6.2; - the component (B) is selected from materials prepared by mixing (i) a number of kilograms of an aqueous solution of phosphoric acid having a stoichiometrically corresponding concentration at a concentration from about 0.058 to about 0.100 M / kg of orthophosphoric acid, with (ii) an amount of magnesium hydroxide, magnesium oxide or magnesium hydroxide and magnesium oxide containing a number of moles of magnesium having a relation to the mathematical product of the number of kilograms of v and the concentration in M / kq of the Aqueous solution of phosphoric acid which is from 1.0: 2.2 to about 1.0: 1.8; step (II) of the process occurs at a temperature in a range from about 135 to about 175 ° C; and s / x c * added on the solid surface treated in step (I) after completing step (II).

11. A liquid composition of material suitable for treating a solid surface to increase the hydrophilicity thereof, the composition contains water and: (A) from about 1.0 to about 100 ppt of a component (A) selected from the group consisting of, dissolved, stably dispersed or dissolved and stably dispersed, organic polymer molecules containing -SO3M moieties where M represents hydrogen, a monovalent cation or a monovalent moiety of the cation with a valence of 2 or greater; and (B) from 0.5 to about 25 ppt of a component (B) of one or more of dissolved substances selected from the group consisting of: substances that have been prepared by dissolving in aqueous phosphoric acid at least one material selected from the group consisting of in metals, metal oxides and metal hydroxides.

The composition according to claim 11, wherein the pH value is from about 4.0 to about 8.0.

13. The composition according to claim 12, further contains a fungicide. The composition according to claim 13, wherein: - the component (A) is selected from the group consisting of: (I) polymers of vinyl sulfonic acid and (ii) polymer molecules having the greater part, or more preferably all ratios -SO3M chemically bound to an aromatic ring; the concentration of component (A) in the liquid composition is from about 4.0 to about 30 ppt; - the concentration of component (B) in the liquid composition is from about 1.3 to about 10 ppt; the pH value is the liquid composition is from about 4.0 to about 7.0; component (B) is selected from materials prepared by dissolving at least one material selected from the group consisting of oxides and hydroxides of metals in which the metal has a valence of at least 2. The composition according to claim 14, wherein: component (A) is selected from the group consisting of sulfonated polystyrene molecules in which there is a ratio of the -SO3M ratios to the aromatic rings which is at least 0.85: 1.0; - the concentration of the component (A) in the liquid composition is from about 8.0 to about 13.0 ppt; - the concentration of component (B) in the liquid composition is from about 2.1 to about 4.5 ppt; the pH value of the liquid composition is from about 4.6 to about 6.2; component (B) is selected from materials prepared by mixing (i) a number of kiloquars of an aqueous solution of phosphoric acid having a stoichiometrically corresponding concentration at a concentration from about 0.058 to about 0.100 M / kq of orthophosphoric acid, with ( ii) an amount of magnesium hydroxide, magnesium oxide or magnesium hydroxide and magnesium oxide containing a number of moles of magnesium with a ratio to a mathematical product of the number of kilograms of and the concentration in M / kg of the solution aqueous phosphoric acid that is from 1.0: 2.2 to about 1.0: 1.8; there is a concentration from about 0.5 to about 1.6 ppt of 2- (4-thiazolyl) benzimidazole present as a fungicide. 16. A liquid composition of material suitable for the treatment of a solid surface to increase the hydrophilicity thereof, the composition having been prepared by mixing water and: (A) an amount of the component (A) selected from the group consisting of, dissolved stably dispersed or stably dispersed and dispersed, organic polymer molecules containing -SO3M moieties where M represents hydrogen, a monovalent cation or a monovalent moiety of a cation with a valence of 2 or greater; the amount of component (A) corresponding to the concentration of, from about 1.0 to about 100 ppt of component (A) in the liquid composition; and (B) an amount of a component (B) of one or more water-soluble substances selected from the group consisting of substances that have been prepared by dissolving in phosphoric acid and at least one material selected from the group consisting of metals, oxides metallic and metal hydroxides, the amount of the component (B) corresponding to a concentration from about 0.5 to about 25 ppt of the component (B) in the aqueous liquid composition. The composition according to claim 16, wherein the liquid composition has a pH value from about 4.0 to about 8.0. 18. The composition according to claim 17, wherein a fungicide has been mixed. The composition according to claim 18, wherein: - the component (A) is selected from the group consisting of: (I) polymers of vinyl sulfonic acid and (ii) polymeric molecules having the greater part, or most preferably all the -SO3M portions directly chemically bound to an aromatic ring; the amount of component (A) corresponds to a concentration of component (A) in the liquid composition that is from about 4.0 to about 30 ppt; - the amount of component (B) corresponds to a concentration of component (B) in the liquid composition that is from about 1.3 to about 10 ppt; the pH value of the liquid composition is from about 4.0 to about 7.0; component (B) is selected from materials prepared by dissolving at least one material selected from the group consisting of oxides and hydroxides of metals in which the metal has a valence of at least 2. The composition according to claim 19, wherein: component (A) is selected from the group consisting of sulfonated polystyrene molecules in which there is a ratio of the -SO3M ratios to the aromatic rings which is at least 0.85: 1.0; - the concentration of component (A) corresponds to a concentration of component (A) in the liquid composition from about 8.0 to about 13.0 ppt; - the amount of component (B) corresponds to a concentration of component (B) in the liquid composition that is from about 2.1 to about 4.5 ppt; the pH value of the liquid composition is from about 4.6 to about 6.2; component (B) is selected from materials prepared by mixing (i) a number of kilograms of an aqueous solution of phosphoric acid having a stoichiometrically corresponding concentration at a concentration from about 0.058 to about 0.100 M / kg of orthophosphoric acid, with ( ii) an amount of magnesium hydroxide, magnesium oxide or magnesium hydroxide and magnesium oxide containing a number of moles of magnesium having a relation to the mathematical product of the number of kilograms of the concentration in M / ks of the solution aqueous phosphoric acid which is from 1.0: 2.2 to about 1.0: 1.8; an amount of fungicide 2- (4-thiazolyl) benzimidazole corresponding to a concentration from about 0.5 to about 1.6 ppt of this fungicide has been mixed in the liquid composition.