RU2125118C1 - Method of producing composition and method of metal treatment with it and its version - Google Patents

Abstract

FIELD: production of compositions for metal treatment. SUBSTANCE: heating of aqueous mixture of such fluorine-containing acid as H₂TiF₆ and such an oxide, hydroxide and/or carbonate as silicon dioxide results in transparent mixture with prolonged stability to settling of any solid phase even in cases when before heating the phase of oxide, hydroxide or carbonate it is presented dispersed solid material in the form of particles large enough to be easily disseminated, and the mixture before heating became turbid. Mixture prepared by heating may be mixed, either with water-soluble and/or dispersed in water polymers which are polyoxyalkyl-substituted polymers and/or copolymers n-vinyl phenol, or with water-soluble hexavalent and/or trivalent chromium with resulting composition which improves metal corrosion resistance after metal treatment with this composition, especially after subsequent painting. EFFECT: higher efficiency. 21 cl, 8 tbl

Description

 The present invention relates to a method for treating metal surfaces with aqueous acidic compositions to increase the corrosion resistance of the treated metal surface either after the treatment is carried out in this way or after its subsequent coating with any conventional organic-based protective layer. The main objective of the present invention is to provide a storage-stable, single-pack processing agent that can be practically free of hexavalent chromium, but capable of practically protecting metals like hexavalent chromium-containing processing agents known in the art, or which can increase the stability of processing solutions containing hexavalent chromium.

 In modern technology there is a very wide variety of materials that are created generally for the same purposes as the present invention, but most of them include hexavalent chromium or other inorganic oxidizing agents that are environmentally undesirable. The following are specific technical solutions that, according to the applicant, are essentially the closest to the present invention.

U.S. Pat. No. 5,089,064, issued February 18, 1992 to Reghi, provides a process for treating aluminum with a composition that includes fluorozirconic acid (H ₂ ZnF ₆ ), a water-soluble or dispersible 3- [N-alkyl ( C ₁ - C ₄ ) -N-2-hydroxyethylaminomethyl] -4-oxystyrene and dispersed silica. Processing with such a tool gives excellent results, but is associated with some inconvenience, since the treatment tool itself is characterized by a slow precipitation of the dispersed silicon dioxide component. In practice, this means that for best results, at least two components, one of which includes silicon dioxide and the other does not contain it, should be stored separately and mixed shortly before use.

 In the description of US patent 4963596, issued October 16, 1990, in the name of Lindert and others, refers to the processing of metals using water-soluble derivatives of polyvinyl phenol, including here, in addition to numerous other options, the combination of these polymeric materials with dispersed silicon dioxide.

 U.S. Patent 4,921,552, issued May 1, 1990 to Sander et al., Refers to treating aluminum with a composition that contains fluorozirconic acid, hydrofluoric acid, and a water-soluble polymer.

 In the description of European patent application 0273698 (published July 6, 1988), aqueous acidic treatment solutions are provided which include trivalent metal compounds, silicon dioxide, and more preferably nickel and / or fluoride ions. Silicon fluoride ions can serve as oppositely charged ions relative to the cations of these trivalent metals, anions.

 In the description of US patent 4341558, issued July 27, 1982 in the name of (Yashiro) and others, it is proposed to treat the metal surfaces of the compositions, which includes a water-soluble salt of zirconium and / or titanium, an ester of phosphoric acid and inositol, and silicon dioxide. This composition may also contain an organic binder such as polyvinyl alcohol.

 In the description of American patent 4277292, issued July 7, 1982 in the name of Tupper, it is proposed to treat aluminum surfaces with an aqueous acidic composition comprising zirconium, fluoride and plant tannin.

 The description of U.S. Patent 3506499, issued April 14, 1970 to Okada et al., Deals with the treatment of aluminum and zinc surfaces with an aqueous solution of chromic acid and colloidal silicon dioxide.

In accordance with the abstract of the work of S.M. Thomsen's "High-Silica Fluosilic Acids Specific Reactions and the Equilibrium with Silica", Jour. Amer. Chem. Soc. 74, 1690 - 93 (1952) refers to the possibility of obtaining highly concentrated silicon dioxide fluorosilicic acids with any desired "excess" content of silicon dioxide, reaching 18% excess in comparison with the composition, which is expressed by the formula H ₂ SiF ₆ , by dissolving hydrated silica in hydrofluoric acid. Silicon fluorosilicates with a high content of silica exhibit characteristic reactions with sodium salts and fluorides. It was found that the equilibrium constant of the hypothetical chemical reaction 4H ⁺ + 5 SiF ₆ ^-2 + SiO ₂ = 3 (SiE ₆ - SiF) ₄ ^-2 + 2H ₂ O
is approximately 100 to 10,000.

 In the description of the broadest aspect of the scope of the present invention, in all cases, with the exception of the claims and working examples, as well as special cases, all quantitative numerical values that indicate the quantities of materials or the conditions of the reactions and / or applications should be understood as modified by the word "about". Moreover, as a rule, values within the given specific limits are practically preferable.

 It has been found that aqueous compositions that include (A) a component of dissolved fluorine acids of one or more metals or metalloid elements selected from a class of elements that encompasses titanium, zirconium, hafnium, boron, silicon, germanium and tin, and (B ) a component of one or more (i) dissolved or dispersed forms of metals and metalloid elements selected from a class of elements that include titanium, zirconium, hafnium, boron, aluminum, silicon, germanium and tin, and (ii) oxides, hydroxides and carbo Nates of such metals and metalloid elements, mixing for periods of time sufficient for the practical course of the reactions, can be converted to an aqueous composition with long-term stability to spontaneous delamination or precipitation even when metal and / or metalloid elements, oxides, the hydroxides and / or carbonates that make up such compositions are in the form of dispersed solid materials that could precipitate in just a few days if they had not ever participated in the reaction.

These compositions, prepared by mixing, then combine either (i) with a water-soluble or dispersible polymer and / or copolymer of one or more X- / NR ¹ -NR ² -aminomethyl) -4-oxystyrenes, in which x = 2, 4, 5 or 6, R ¹ denotes an alkyl group containing from 1 to 4 carbon atoms, preferably a methyl group, and R ² denotes a substituent group that corresponds to the general formula H (CHOH) -, where n is an integer from 3 to 8, more preferably from 4 to 6, or (ii) with a composition containing hexavalent chromium and, optionally, but preferably, three entny chrome. The prepared compositions are suitable for treating metal surfaces with excellent corrosion resistance, in particular after subsequent application of a conventional protective coating containing an organic binder. Such compositions are particularly useful for treating iron and steel, galvanized iron and steel, zinc and those alloys thereof, which include at least 50 at.% Zinc, and, more preferably, aluminum and its alloys, which contain at least 50 at.% aluminum. Such processing may consist either of coating the metal with a liquid film of the composition, followed by drying of the liquid film at the place of application on the metal surface, or simply by bringing the metal into contact with the composition for a period of time sufficient to impart increased surface corrosion resistance, followed by washing before by drying. Such contact can be achieved by spraying, dipping and using similar techniques that are themselves known in the art.

 It should be borne in mind that this description does not exclude the possibility of specifically unspecified chemical interactions between the listed components, but instead illustrates the components of the composition in accordance with the present invention in the form in which they are usually used as ingredients for preparing such a composition.

To the extent that its water solubility is sufficient, the fluorine-containing acid component (hereinafter in some cases referred to as “(A)”), which must be reacted in the process according to one embodiment of the present invention, can be freely selected from the class that covers H ₂ TiF ₆ , H ₂ ZrF ₆ , H ₂ HfF ₆ , H ₂ SiF ₆ , H ₂ GeF ₆ , H ₂ SnF ₆ and HBF ₄ and mixtures thereof, H ₂ TiF ₆ , H ₂ ZrF ₆ , H ₂ HfF ₆ ,
H ₂ SiF ₆ , HBF ₄ and mixtures thereof are preferred: H ₂ TiF ₆ , H ₂ ZrF ₆ , H ₂ SiF ₆ and mixtures thereof are more preferred, and H ₂ TiF ₆ are most preferred. The preferred concentration of the fluorine-containing acid component during the reaction is in the range from 0.01 to 7 mol / L (hereinafter “M”), more preferably from 0.1 to 6 M.

 The component (hereinafter sometimes referred to as "(B)") of metal and / or metalloid elements and / or their oxides, hydroxides and / or carbonates is preferable to choose from the class of oxides, hydroxides and / or carbonates of silicon, zirconium and / or aluminum, more preferably silicon dioxide. When implementing the method in accordance with one embodiment of the present invention, such a component can be used in any form in which it is finely divided so that it can be easily dispersed in water, but with regard to the components of this component having low solubility in water, it is preferable to use such a component in an amorphous form than in crystalline, because for the preparation of a composition, which later turns out to be insensitive to delamination, ristallicheskie materials may require much longer heating periods and / or higher heating temperature. Solutions and / or sols, in particular silicic acid sols, can be used, but it is highly preferred that they are substantially free of alkali metal ions, as described below. However, in general, it is most preferable to use silica dispersions prepared during pyrogenic processes.

In this detailed description, the equivalent of a metal or metalloid element or its oxide, hydroxide or carbonate is defined as the amount of material containing the total number of atoms of metal and / or metalloid elements of a class that encompasses titanium, zirconium, hafnium, boron, aluminum, silicon, germanium and tin equal to the number of Avogadro (that is, 6.02 • 10 ²³ ). The preferred ratio between the number of moles of the fluoric acid component (A) and the total number of equivalents of component (B) in the aqueous composition heated in accordance with one embodiment of the present invention is in the range from 1: 1 to 50: 1, more preferably from 1, 5: 1.0 to 20: 1, or more preferably 1.5: 1 to 5.0: 1.0. If desired, a component of this component can be treated on its surface with a combination silane agent or the like, which gives oleophilicity to such a surface.

In accordance with one embodiment of the present invention, an aqueous composition comprising, preferably consisting essentially of, or more preferably consisting of water and a fluoric acid component, as well as an ingredient of an oxide (s), hydroxide (hydroxides) and / or carbonate ( carbonates) of a metal (metal) and / or metalloid (metalloid) element (s), as described above, is stirred for a period of time sufficient to prepare a composition that is free from any noticeable stratification during storage for a period of 100 hours or more, preferably 1000 hours. During the mixing process, the preferred temperature is in the range from 25 to 100 ^o C, more preferably in the range from 30 to 80 ^o C, and the period of time during which the composition is maintained at this temperature, is in the range from 3 to 480 minutes, more preferably from 5 to 90 minutes, and even more preferably from 10 to 30 minutes. Usually, for the conversion of compositions in which component (B) is selected only from soluble materials and / or dispersed amorphous substances that are not subjected to any surface treatment to reduce their hydrophilicity, a shorter mixing time and lower temperature within the indicated ranges are better, although in the case of when component (B) includes dispersed solid crystalline materials and / or solids, the surface of which is processed to reduce their hydrophilicity, will likely o, a longer duration and / or higher temperature at the indicated intervals. In especially difficult cases, with the equipment to create pressure above the reaction mixture, the process can be carried out under even higher temperatures than 100 ^o C.

 Regardless of other parameters, in the preferred embodiment, to maintain the above temperature range, the pH of the composition in which components (A) and (B) described above are combined should be maintained in the range from 0 to 4, more preferably in the range from 0.0 to 2 , 0 or even more preferably in the range from 0.0 to 1.0.

In a preferred embodiment, after exposure to the temperature indicated above, the temperature of the composition is brought to a level below 30 ^o C, and then it is mixed with a component (hereinafter sometimes referred to as "(C)"), which includes any (1) water-soluble or water-dispersible polyhydroxylalkylamino derivatives of poly-p-oxystyrene, as mentioned above and as described in more detail in the description of US patent 4963596, which for this reason is fully, if we exclude everything that contradicts any clear statement containing I, in this detailed description, are mentioned here by reference, or (2) solutions of hexavalent chromium and, optionally, but preferably, trivalent chromium, as is itself known in the technique of processing metals, in particular aluminum and its alloys, with the aim of slowing down the process of their corrosion. Acceptable and preferred polymers and methods from the preparation are presented in detail in the description of US patent 4963596. The preferred weight ratio between the contained solid materials of component (C) and the total amount of active ingredients of component (A), which is described above, should be in the range from 0, 1 to 3, more preferably from 0.2 to 2, or even more preferably from 0.20 to 1.6.

 A composition prepared in accordance with the above method constitutes another embodiment of the present invention. Typically, the preferred compositions of the invention as defined above should be substantially free of many of the ingredients used in the compositions for similar purposes in the art. So, specifically, according to the above order of increasing preference, the preferred minimum amount of each of the following components, regardless of the others, such compositions, when they are brought into direct contact with the metal when implementing the method in accordance with the present invention, should contain no more than 1.0, 0 , 35, 0.10, 0.08, 0.04, 0.02, 0.01 or 0.001 wt.% Of each of the following ingredients: hexavalent chromium, ferricyanide, ferrocyanide, anions containing molybdenum or tungsten, nitrates and other oxides Teli (wherein the content of those other compounds is determined according to their oxidizing stoichiometric equivalent as nitrate); phosphorus and sulfur-containing anions that are not oxidizing agents, alkali metal and ammonium cations, as well as organic compounds with two or more hydroxyl groups per molecule and a molecular weight of less than 300. The preference for the minimum amounts of alkali metal and ammonium cations is applicable only to compositions that are used in the implementation of the methods in accordance with the present invention, which include the stage of drying in place of the treated metal surface of its washing after the introduction of the metal surface in contact with a composition which contains components (A), (B), and (C), as defined above; when the composition of the present invention is brought into contact with a metal surface, followed by washing the metal surface with water before drying, all alkali metal and ammonium ions present are usually removed by washing to a degree sufficient to avoid any substantial decrease in the protective ability subsequently applied protective coatings containing an organic binder. In addition, the preference for minimizing the amount of hexavalent chromium present is due to the environmental pollution effect of hexavalent chromium, and in cases where there are no legislative restrictions against environmental pollution and / or there are quite economical means of waste disposal with hexavalent chromium, which do not have harm to the environment, such a preference becomes inapplicable. Indeed, in accordance with one of the special embodiments of the present invention, as mentioned above, hexavalent chromium can be successfully used to further increase the corrosion resistance of the treated metal surfaces.

 However, in accordance with another embodiment of the present invention, there is provided a method for treating a metal with a composition prepared according to the foregoing. According to one embodiment of the present invention, it is preferable to apply an acidic aqueous composition to the metal surface, as mentioned above, followed by drying at the place of application. So, for example, coating a metal with a liquid film can be done by dipping the surface in a container with a liquid composition, spraying it onto the surface of this composition, coating the surface by passing it between the upper and lower rollers, the lower roller of which is immersed in a container with a liquid composition, and the like. way or by a combination of these methods. Excess quantities of the liquid composition, which might otherwise remain on the surface before drying, can be removed before drying by any conventional method, in particular by dripping under its own weight, using a rubber layer, passing between the rollers and the like.

 In the event that the coating is applied to the surface of a flat sheet or a roll and a finely adjustable coating technique is used, in particular a device for coating with a grooved roller, relatively small volumetric amounts of the concentrated composition per unit surface area can be effectively used. On the other hand, in the case where the coating equipment used does not provide simple precise control when coating with a small added volume of liquid, it is equally effective to use a more dilute acidic aqueous composition with a thicker layer of liquid coating that contains approximately the same amounts active components. In any case, the total number of elements selected from the class that covers titanium, zirconium, boron, silicon, germanium, tin contained in the coating material, which is dried at the place of application on the surface to be treated, is in the range from 1 to 300, preferably from 5 to 150, even more preferably 5 to 100, mg / sq. surface finish.

Drying can be carried out by any convenient method, many of which are themselves known in the art; Examples include drying with hot air and infrared. Regardless, it is preferable that the maximum temperature of the metal, which is achieved during the drying process, is in the range from 30 to 200, more preferably from 30 to 150, and even more preferably from 30 to 75 ^o C. It is also preferable to carry out drying regardless a period of time from 0.5 to 300 seconds, more preferably from 2 to 50 seconds, even more preferably from 2 to 10 seconds, after completion of the coating operation.

In accordance with another embodiment of the present invention, the metal to be treated is preferably contacted with a composition prepared as described above at a temperature in the range of 25 to 90 ^° C, more preferably 30 to 85 ^° C, even more preferably 30 to 60 ^° C. for a period of time from 1 to 1800, more preferably from 1 to 300 seconds, even more preferably from 3 to 30 seconds, after which the metal surface thus treated is washed with water in one or more stages, followed by drying. In this embodiment, at least the final washing is preferable to be carried out using deionized, distilled or otherwise purified water. In addition, in such an embodiment, it is preferable that the maximum metal temperature achieved during the drying process is in the range from 30 to 200 ^° C, more preferably from 30 to 150 ^° C, even more preferably from 30 to 75 ^° C, and that independently from which the drying time was in the range from 0.5 to 300 seconds, more preferably from 2 to 50 seconds, even more preferably from 2 to 10 seconds, after completion of the washing operation.

 The implementation of the method in accordance with the present invention, the essential features of which are generally presented above, it is possible and usually preferable to continue applying on a dry metal surface, which is obtained by the above treatment, a desiccant coating or other protective coating, thicker than the coating that is obtained on earlier stages of the method of the present invention, which is set forth above, as is itself known in the art. It has been found that surfaces thus coated exhibit excellent resistance to subsequent corrosion, as illustrated in the examples below. The class of protective coatings of particularly preferred types for use in conjunction with the present invention encompasses paints, enamels, acrylic and polyester varnishes and the like.

 In the implementation of the method of the present invention, which includes other stages after processing and the formation of a layer on the metal surface, as described above, and in accordance with which the process is provided for in an environment in which the discharge of hexavalent chromium into waste is either limited by law or difficult from an economic point of view, it is usually preferable that in none of these other stages was provided contacting surfaces with any composition that includes REFERENCE increasing order of preference more than 1.0 0.35, 0.10, 0.08, 0.04, 0.02, 0.01, 0.003, 0.001 or 0.002 wt.% hexavalent chromium. However, in some special cases, hexavalent chromium can provide the metal surfaces to be treated with significant additional protection against corrosion, which justifies the increasing costs associated with the use of waste-containing waste as specified by law.

 Preferably, the metal surfaces to be treated in accordance with the present invention are first cleaned of all contaminants, in particular organic contaminants and extraneous metal dust and / or inclusions. Such cleaning can be carried out by methods that are known per se to any person skilled in the art and adapted to the particular type of metal material being processed. So, in particular, in the case of galvanized steel surfaces, it is most preferable to clean the material with a conventional hot alkaline cleaning agent, followed by washing with hot water, removing excess moisture and drying. In the case of aluminum, the surface to be treated is most preferably first contacted with a conventional hot alkaline cleaning agent, then rinsed with hot water, and then optionally brought into contact with a neutralizing acid washing agent, followed by contacting with the aqueous acidic composition as described above .

 The feasibility of the practical implementation of the present invention becomes even more clear from a consideration of the following non-limiting explanatory examples, and the advantages of the present invention can be further appreciated by reference to comparative examples.

Examples
Test methods and other general conditions
Test pieces of type 3105 aluminum were cleaned by spraying for 15 seconds at 55 ^° C with an aqueous cleanser that contained 28 g / l of PARCO 305 cleanser (commercially available from Henkel Corp. Parker + Amkem Division, Madison Heights) , Michigan, USA). After cleaning, the panels were washed with hot water, excess moisture was removed from them and dried, followed by roller coating using an acidic aqueous composition, which is described in each specific example and comparative examples below.

For the first group of examples and comparative examples below, in cases that correspond to an alternative on-site drying method, the applied liquid composition of the present invention was thermally dried (instant drying) in an infra-red oven in which the peak temperature of the metal was reached about 49 ^o C. The treated samples were subsequently coated in accordance with the technical recommendations by different suppliers paints which additionally specified audio e.

 T-bend test (T-bend) was carried out in accordance with method D4145-83 of the American society for testing materials (hereinafter "ASTM"); impact tests (impact strength) were carried out in accordance with ASTM method D2794-841E1; salt spray tests were carried out in accordance with ASTM standard method B-117-90; spray tests with acetic acid salts were carried out according to ASTM standard method B-287-74; and moisture tests were performed according to ASTM standard method D2247-8. Immersion tests in boiling water were carried out as follows: 2T-bend and shock reversible deformation were determined on a treated and painted panel. Then, the panel was immersed for 10 minutes in boiling water under normal atmospheric pressure, and the sections of the panel that were most exposed to T-bend and shock reversible deformation were studied in order to determine the percentage of the film of paint from the initial amount that exfoliated. The evaluation results are given as a number, which is a tenth of a percentage of non-peeling paint. Thus, the best possible score is 10, which indicates no peeling: a score of 5 indicates a 50% peeling, etc.

Specific composition
Example 1

5.6 parts by weight amorphous fuming silica
396.2 weight parts deionized water
56.6 weight parts aqueous 60% by weight fluorotitanic acid
325.4 parts by weight deionized water
216.2 weight. including an aqueous solution containing 10 wt.% solids, a water-soluble polymer (Mannich adduct of poly-4-vinylphenol with N-methylglucamine and formaldehyde), obtained in accordance with the instructions given in lines 39-52 of column 11 of the description of US patent 4963596 .

 Example 2

58.8 weight parts aqueous 60% by weight fluorotitanic acid
646.0 weight parts deionized water
5.9 parts by weight amorphous fuming silica
10.5 parts by weight zirconium hydroxides
278.8 weight parts 10% by weight of a solution of a water-soluble polymer used in example 1.

 Example 3

62.9 weight parts aqueous 60% by weight fluorotitanic acid
330.5 weight parts deionized water
6.2 parts by weight amorphous fuming silica
358.9 weight parts deionized water
241.5 parts by weight 10% by weight of a solution of the water-soluble polymer used in example 1.

 Example 4

56.4 parts by weight aqueous 60% by weight fluorotitanic acid
2.1 parts by weight Aerosil R-972 product (surface treated with dispersed silica)
56.4 parts by weight deionized water
667.0 weight parts deionized water
218.1 weight parts 10% by weight of the water-soluble polymer used in example 1.

 Example 5

58.8 weight parts aqueous 60% by weight fluorotitanic acid
3.7 parts by weight amorphous fuming silica
10.3 parts by weight basic zirconium carbonate
647.7 weight parts deionized water
279.5 weight parts 10% by weight of the water-soluble polymer used in example 1.

 Example 6

52.0 parts by weight aqueous 60% by weight fluorotitanic acid
297.2 weight parts deionized water
3.3 parts by weight amorphous fuming silica
9.1 parts by weight basic zirconium carbonate
273.6 weight parts deionized water
364.8 weight parts 10% by weight of the water-soluble polymer used in example 1.

 Example 7

11.0 parts by weight fuming amorphous silica
241.0 parts by weight deionized water
114.2 parts by weight aqueous 60% by weight fluorotitanic acid
633.8 weight. including an aqueous composition prepared from the following components:
5.41 wt.% Chromium trioxide CrO ₃
0.59 wt.% Corn starch
94 wt.% Water
During the experiments of examples 1-6 in this order, the components were loaded into a container equipped with a stirrer (glass containers are sensitive to the chemical effects of the compositions, so they should not be used even in laboratory conditions, it was found that containers of austenitic stainless steels of this type are satisfactory such as steel type 316, and containers made of or fully lined with resistant plastics, in particular polytetrafluoroethylene or chlorotrifluoroethylene polymers). During each experiment, with the exception of the experiment of Example 4, after the addition of the silicon dioxide component and before the subsequent addition of the listed components, the mixture was heated to a temperature of 38-43 ^° C and kept in this temperature range for a period of 20-30 minutes. Then the mixture was cooled to a temperature below 30 ^o C and without further heating the remaining components were mixed, continuing mixing after the introduction of each component until a clear solution was formed.

In the experiment of Example 4, a material with a silane-modified particle surface was used as silicon dioxide, and due to its hydrophobic nature, to achieve transparency, the mixture, which included silicon dioxide in this form, was held for 1.5 hours at a temperature of 70 ^o C. The remaining stages of the process were the same as in the experiment of example 1.

During the experiment of example 7, the first three of the listed components were mixed with each other and kept at a temperature of 40 ± 5 ^o C for 10 min with stirring, and then cooled. In a separate container, chromium trioxide CrO _{3 was} dissolved in water, the weight amount of which was about 15 times its own weight, and corn slurry sludge was added to this solution in water, the weight amount of which was 24 times its own weight. Then this mixture was kept for 90 min with gentle stirring at a temperature of 88 ± 6 ^o C in order to restore part of the hexavalent chromium contained in trivalent chromium. Finally, this mixture was cooled with stirring, and then it was added to a pre-prepared heated mixture of fluorotitanic acid with silica and water. This composition is used in a way that is well known in the art for compositions comprising hexavalent and trivalent chromium and dispersed silicon dioxide, but it is significantly more stable in storage, without phase separation.

Comparative Example 1
18.9 weight. including 60% aqueous by weight of fluorotitanic acid 363.6 parts by weight 10% by weight of a water-soluble polymer used in the experiment of example 1.

 617.5 weight parts deionized water.

Reference Example 2
18.9 weight. including 60% aqueous by weight of fluorotitanic acid 71.8 parts by weight 10% by weight of a water-soluble polymer, which was used in the experiment of example 1.

 909.3 weight parts deionized water.

 During the experiments of comparative examples 1 and 2, the components were added in the indicated order with simultaneous stirring without any heating before use in the treatment of metal surfaces.

 The input mass amounts, specific paints used and the results achieved using some of the compositions that are listed above are presented in the following table. 1-5.

 The storage stability of the compositions prepared in accordance with all of the above examples, with the exception of Example 2, was so good that no phase separation after at least 1,500 hours of storage was observed. As for example 2, after 150 hours, a small amount of an obvious solid phase was precipitated.

To obtain the results that are shown in the following tables, another method of processing metal surfaces in accordance with the present invention using a different aluminum alloy was carried out. So, specifically tested pieces of aluminum of type 5352 or 5182 were cleaned by spraying for 10 seconds at a temperature of 55 ^o C with an aqueous purified product, which included 24 g / l of the cleansing agent PARCO 305 (manufactured by Henkel's Parker + Amkem division industrially Corp., Madison Heights, MI, USA). After cleaning, the panels were washed with hot water, then they were sprayed with appropriate treatment solutions in accordance with the present invention, which were similar to those already described in the examples of the same numbers, except that they were further diluted with water to the concentration indicated in the tables below. for 5 seconds, after which it was washed with water and dried before painting.

The OT Bend column in the tables below shows the results of the test procedure, which was carried out as follows:
1. OT bend test in accordance with ASTM Method D4145-83.

 2. One piece of Scotch # 610 tape is firmly attached to the O-T curved panel section and to an adjacent flat section.

 3. Slowly pull the tape from the bend and adjacent flat section.

 4. Steps 2 and 3 are repeated using a new piece of tape at each turn until additional paint is no longer removed.

5. The data of the maximum distance from the bend of OT to the flat area from which, according to observations, the paint is removed, is estimated according to the following scale:
Loss of paint in mm - Scale score
0 - 5.0
0.8 - 4.5
1.6 - 4.0
2.4 - 3.5
3.2 - 3.0
4.0 - 2.5
4.8 - 2.0
5.6 - 1.5
6.4 - 1.0
7.2 - 0.5
> 7.2 - 0
The 90-minute steam treatment column of the tables below shows the test results, which were carried out as follows.

1. Painted samples are treated with water vapor by holding them in a cooking autoclave or autoclave at a temperature of water vapor of 120 ^o C for 90 minutes

 2. The stained sample is cross-cut - two perpendicular cuts; they use the Gardner tool for cross-cuts with 11 knife blades 1.5 mm apart.

3. subjected notch cross section tightly fixed tape Scotoh ^TM # 610.

 4. Inspect the cross-cut area for evaluating that paint that has not been removed by tape, and assess the condition with a number that corresponds to one tenth of the remaining paint.

 5. Using a microscope with a 10-80-fold magnification, a cross-cut section is visually obtained to determine the degree of swelling, evaluating the size and density of the bubbles.

The column “15-minute boiling with immersion in DOWFAX ^™ 2A1” in the following tables presents the results of the tests carried out after the following processing.

1. Prepare a 1% by volume solution of DOWFAX ^™ 2A1 in deionized water and bring it to a boil.

 2. The painted test panels are immersed in the boiling solution prepared in step 1 and held there for 15 minutes, after which the panels are removed, washed with water and dried.

DOWFAX ^™ 2A1 is commercially available from Dow Chemical, which describes it as 45% active sodium dodecyl diphenyl oxide disulfonate. After this treatment, the cross-cut test was carried out similarly to the above for steps 2-4 after the “90 minute steam treatment”. The test for “reversible shock deformation” was carried out according to ASTM D2794- 84E1 (for impacts of 20 inches, 20 x 25.4 mm x 0.453 kg), after which the procedure was carried out similarly to the above for stages 3-4 after “90-minute water treatment ferry". The bloating test was carried out as follows. Using a conventional knife, a slightly curved “V” tape is engraved from the back of the test panel. Using cutters, approximately 12 mm are cut from the bottom along the letter. The inner side of the letter V is bent away from the side for testing. The sample is placed in a vice and, with the help of ticks, pulled from a curved section with constant slow movement. The part of the panel, which is located between the upper edges in the immediate vicinity of the apex, and the line parallel to the upper edge, but 19 mm away from it, are neglected. On the remainder of the panel, the peeling border is measured in millimeters. The largest of the obtained values is fixed.

 The test results carried out in accordance with these procedures are summarized in the following table. 6-8.

Claims (21)

A method of obtaining a composition for treating metal surfaces, comprising preparing a mixture by mixing the components with water, characterized in that the mixing is carried out in two stages, first a fluorine-containing compound or a mixture of fluorine-containing compounds selected from the group H ₂ TiF ₆ , H ₂ ZrF _{6 is} mixed with water , H ₂ HfF ₆ , H ₂ SiF ₆ , H ₂ GeF ₆ , H ₂ ShF ₆ , HBF ₄ , and a dissolved and / or dispersed component selected from the group Ti, Zr, Hf, Al, Si, Ge, Sn, B as well as oxides, hydroxides, carbonates of these elements and any mixture thereof at temperature and sufficient belts to prevent phase separation during preparation of the mixture and storage stability for at least 100 hours at 20 - 25 ^o C, after which the resulting mixture is mixed with a component selected from the group consisting of water-soluble and water-dispersible polymers and copolymers X- (NR ¹ -NR ² -aminomethyl) -4-oxystyrenes, where X = 2,3,5,6, R ^{1 is an} alkyl group containing from 1 to 4 carbon atoms, R ² is a substituent group with the general formula H _{(CHOH) n, n-3-8} , two or more mixtures thereof, and the dissolved hexavalent chromium at a temperature and time Sufficient to prevent phase separation in the preparation of the mixture and the resulting mixture stability during storage for at least 100 hours at 20 - 25 ^o C. 2. The method according to p. 1, characterized in that a mixture is prepared containing from 0.01 to 7.0 M fluorine-containing compounds or mixtures of fluorine-containing compounds selected from the group H ₂ TiF ₆ , H ₂ ZrF ₆ , H ₂ HfF ₆ , H ₂ SiF ₆ , HBF ₄ , with a molar ratio of the fluorine-containing component in it to a component selected from the group Ti, Zr, Hf, Al, Si, Ge, Sn, B, as well as oxides, hydroxides, carbonates of these elements and any mixture thereof , in the range from 1: 1 to 50: 1, the mixture is kept at 25 - 100 ^o C for 3 - 480 min, the resulting mixture is mixed with a component that includes such a total amount of water-soluble polymers and copolymers dispersed in water, in which the weight ratio between them and the total weight of the fluorine-containing component is in the range from 0.1: 1 to 3: 1. 3. The method according to claim 1, characterized in that a mixture is prepared containing from 0.1 to 6.0, OM of a fluorine-containing compound or a mixture of fluorine-containing compounds selected from the group H ₂ TiF ₆ , H ₂ ZrF ₆ , H ₂ SiF ₆ , with a molar ratio of the fluorine-containing component in it to the total amount of oxides, hydroxides and carbonates of Si, Zr, Al in the range from 1.5: 1.0 milking 20: 1, and a pH value in the range from 0 to 4, the mixture is kept at 30 - 80 ^o C for 5 - 90 min, the resulting mixture was mixed with a component, comprising a total amount of water-soluble and water dipergiruemyh polymers and opolimerov, wherein the weight ratio between them and obshim weight fluoropolymer component is in the range of from 0.2: 1 to 2.0: 1. 4. The method according to claim 3, characterized in that the mixture is first prepared with a molar ratio of components from 1.5: 1 to 5: 1 and a pH in the range from 0 to 2, the mixture is kept at 30 - 80 ^o C for 10 - 30 min, the resulting mixture is mixed with water-soluble and water-dispersible polymers and copolymers and copolymers with a weight ratio of them and the fluorine-containing component in the range 0.2: 1 - 1.6: 1. 5. The method according to claim 1, characterized in that prepare a mixture containing 0.1 to 6.0 MH ₂ TiF ₆ and silicon dioxide with a molar ratio of H ₂ TiF ₆ to the total number of equivalents of silicon dioxide in the range from 1.5: 1.0 to 5: 1 and a pH value of 0 - 1.0, the mixture is kept at 30 - 80 ^o C for 10 - 30 minutes, the resulting mixture is mixed with a component that includes such a total amount of water-soluble and water-dispersible polymers and copolymers of X- {[(N-methylamino) glucamino] methyl} -4-oxystyrenes, where X = 2,3,5,6, in which the weight ratio between them and H ₂ TiF ₆ is in the range e from 0.20: 1 to 1.6: 1. 6. The method of processing metal surfaces, characterized in that the processing is carried out by coating the metal surface with a layer of the composition obtained according to claim 1, a thickness at which the layer contains elements selected from the group Ti, Zr, B, Si, Ge, Sn, common the amount of 1 to 300 mg / m ^{2 of the} metal surface, and drying the layer in place without intermediate washing. 7. The method according to claim 6, characterized in that the metal surface is coated with a layer of the composition with a thickness in which the total number of elements in the layer is from 5 to 100 mg / m ^{2 of the} metal surface, and drying is carried out for 2 to 50 seconds.  8. The method according to claim 6, characterized in that the processing is carried out by the composition obtained according to claim 2.  9. The method according to claim 6, characterized in that the processing is carried out by the composition obtained according to claim 3. 10. The method according to claim 6, characterized in that the treatment is carried out with a layer of the composition obtained according to claim 4, with a layer thickness, the total number of elements in which is from 5 to 150 mg / m ^{2 of the} metal surface. 11. The method according to claim 6, characterized in that the processing is carried out with a layer of the composition obtained according to claim 4, with a layer thickness, the total number of elements in which is from 5 to 100 mg / m ^{2 of the} metal surface, and drying is carried out for 2 - 50 p. 12. The method according to claim 6, characterized in that the metal surface is covered with a layer of a liquid composition obtained according to claim 5, with a layer thickness, the number of elements in which is from 5 to 150 mg / m ^{2 of the} metal surface. 13. The method according to p. 6, characterized in that the processing of the metal surface is carried out by a layer of the composition obtained according to claim 5, with a layer thickness in which the total number of elements is from 5 to 100 mg / m ^{2 of the} metal surface, and drying is carried out in flow 2 - 10 s, with a maximum metal temperature of 30 - 75 ^o C. 14. The method of processing a metal surface, characterized in that the treatment is carried out by bringing the metal surface into contact with the liquid composition obtained according to claim 1, at 25 - 90 ^o C for 1 - 1800 s, removing the surface from the liquid composition, washing with water and drying. 15. The method according to p. 14, characterized in that the contact of the metal surface with the liquid composition is carried out at 30-60 ^o C for 3-30 s, and drying is carried out for 2-50 s.  16. The method according to 14, characterized in that the treatment is carried out by the composition obtained according to claim 2.  17. The method according to 14, characterized in that the treatment is carried out by the composition obtained according to claim 3. 18. The method according to p. 14, characterized in that the contact of the metal surface with the liquid composition obtained according to claim 4, is carried out at 30 - 85 ^o C for 1 to 300 C. 19. The method according to 14, characterized in that the contact of the metal surface with the liquid composition obtained according to claim 4, is carried out at 30 - 60 ^o C for 3 to 30 s, and drying is carried out for 2 to 10 s. 20 . The method according to claim 14, characterized in that the metal surface is contacted with the liquid composition obtained according to claim 5 at 30 - 85 ^° C for 1 to 300 s. 21. The method according to 14, characterized in that the metal surface is contacted with the liquid composition obtained according to claim 5 at 30-60 ^° C for 3-30 seconds, and drying is carried out for 2-10 seconds at maximum metal temperature 30 - 75 ^o C.

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