MXPA98009873A

MXPA98009873A - Zinc fosfatization with passive position integr

Info

Publication number: MXPA98009873A
Application number: MXPA/A/1998/009873A
Authority: MX
Inventors: Geke Jurgen; Mayer Bernd; Kyhm Peter
Original assignee: Henkel Kgaa 40589 Duesseldorf De
Priority date: 1996-05-28
Filing date: 1998-11-25
Publication date: 1999-10-14

Abstract

A process for the phosphatization of metallic surfaces composed of steel, steel coated with zinc, or steel coated with a zinc alloy, aluminum and / or aluminum-magnesium alloys, characterized in that the phosphatization solution contains: 0.2 to 3 grams per liter of zinc ions, from 3 to 50 grams per liter of phosphate ions, calculated as PO4, from 0.001 to 4 grams per liter of manganese ions, from 0.001 to 0.5 grams per liter of one or more selected polymers among polyethers, polycarboxylates, polymeric phosphonic acids, polymeric phosphinocarboxylic acids and organic nitrogen-containing polymers and one or more accelerators. Preferred polymers are poly (vinylphenol) derivatives containing ami groups

Description

"ZINC FOSFATIZATION WITH INTEGRATED POSTERIOR PASSIVATION" This invention relates to processes for the phosphatization of metal surfaces using aqueous acid phosphate solutions containing zinc ions, manganese ions, phosphate ions and up to 0.5 gram per liter of organic polymers. This invention also relates to the use of these processes as a pretreatment of metal surfaces for a subsequent coating, in particular an electrocoating or a powder coating. The process can be used for the treatment of steel surfaces, zinc coated steel or steel coated with zinc alloy, aluminum, aluminum and magnesium alloys, aluminized steel or steel coated with aluminum alloy, and avoids the passivation rinse required until now. The phosphatization of metals tries to produce on the metal surfaces layers of metal phosphate that adhere firmly, which alone already improve the resistance to corrosion and in combination with paints or other organic coatings, contribute to a considerable increase in the adhesion of the paint and in the resistance to the loss of the paint during a corrosive effort. These phosphatization processes have been known for a long time. The processes of phosphatizing-, of - low zinc content, where the phosphatization solutions have comparatively low zinc ion contents of, for example 0.5 to 2 grams per liter, are particularly suitable for pre-treatment prior to the coating in particular electrocoating. An important factor in these low zinc phosphide baths is the weight ratio of phosphate ions to zinc ions, which is usually greater than 8 and can be up to 30. It has become evident that the layers of phosphate having distinctly improved corrosion protection and paint adhesion properties can be formed by the concomitant use of other polyvalent cations in zinc phosphating baths. By way of example, the processes of low zinc content with the addition of, for example 0.5 to 1.5 grams per liter of manganese ions and, for example, 0.3 to 2.0 grams per liter of nickel ions, find wide application as the so-called trication processes for the treatment of metal surfaces for coatings, for example, for the cathodic electrocoating of the bodywork of the car. Since nickel and cobalt used alternatively are classified as critical from the aspects of both toxicology and water technology - - residual, there is a need for phosphatization processes that have an operating level similar to that of the trication processes but that function with considerably lower concentrations of nickel and / or cobalt in the baths and preferably in these two metals. Patent No. DE-A 20 49 350 discloses a phosphatization solution containing, as essential constituents, from 3 to 20 grams per liter of phosphate ions, from 0.5 to 3 grams per liter of zinc ions, from 0.003 to 0.7 gram. per liter of cobalt ions or from 0.003 to 0.04 gram per liter of copper ions, or preferably from 0.05 to 3 grams per liter of nickel ions, from 1 to 8 grams per liter of magnesium ions, from 0.01 to 0.25 gram per liter of nitrite ions and 0.1 to 3 grams per liter of fluoride ions and / or 2 to 30 grams per liter of chloride ions. Therefore, this process is a zinc-magnesium phosphatization, with the phosphatization solution also containing the ions of one of the cobalt, copper or, preferably, nickel metals. This zinc-magnesium phosphatization has not been successful in obtaining technical acceptance. Patent Number EP-B 18 841 describes an accelerated zinc phosphatization solution by chlorate / nitrate, containing inter alia, from 0.4 to 1 gram per liter of zinc ions, from 5 to 40 grams per liter of - A - phosphate ions as well as optionally, at least 0.2 gram per liter preferably 0.2 to 2 grams per liter, of one or more ions which are selected from nickel, cobalt, calcium and manganese. The optional content of manganese, nickel or cobalt, therefore, at least 0.2 gram per liter. Nickel contents of 0.53 grams per liter and 1.33 grams per liter are given in the examples. Patent Number EP-A 459 541 describes phosphatization solutions which are essentially free of nickel and contain, in addition to zinc and phosphate, 0.2 to 4 grams per liter of manganese and 1 to 30 milligrams per liter of copper. Patent Number DE-A 42 10 513 discloses nickel-free phosphatization solutions containing in addition to zinc and phosphate, from 0.5 to 25 milligrams per liter of copper ions and, as an accelerator, hydroxylamine. These phosphatization solutions optionally contain in addition to 0.15 to 5 grams per liter of manganese. German Patent Application Number 196 06 017.6 discloses a reduced phosphatization solution in heavy metals containing 0.2 to 3 grams per liter of zinc ions, 1 to 150 milligrams per liter of manganese ions and 1 to 30 milligrams per liter. liter of copper ions. This phosphatization solution can optionally contain up to 50 milligrams per liter of nickel ions and up to 100 milligrams per liter of cobalt ions. Lithium ions in amounts between 0.2 and 1.5 grams per liter are another optional constituent. German Patent Application Number DE 195 38 778.3 describes the control of the weight of the layer in phosphate layers by the use of hydroxylamine as an accelerator. The use of hydroxylamine and / or derivatives thereof to influence the configuration of the phosphate crystals is known from a number of published patents. Patent Number EP-A 315 059 mentions, as a specific effect of the use of hydroxylamine in the phosphatization baths, the fact that on steel, the phosphate crystals still form a desired columnar or nodular configuration, if the zinc concentration in The phosphatization bath exceeds the conventional scale for the low zinc content processes. Therefore, it is possible to operate the phosphatization baths at zinc concentrations of up to 2 grams per liter and to use zinc phosphate weight ratios as low as 3.7. More details related to advantageous combinations of cations in these phosphatization baths have not been provided but nickel is used in all cases in the Examples provided in the patent. Nitrates and nitric acid are also used in the Examples, even though the description recommends against the presence of nitrate in larger amounts. The required concentration of the hydroxylamine is provided as 0.5 to 50 grams per liter, preferably 1 to 10 grams per liter. The maximum concentration of hydroxylammonium sulfate in the Examples is 5 grams per liter, from where the calculated hydroxylamine content is 2.08 grams per liter. (Hydroxylammonium sulfate contains 41.5 weight percent hydroxylamine). The phosphatization solution is applied to the steel surfaces by spraying. The document does not mention the problems involved in the processes of immersion leading to phosphate stages having distinctly higher layer weights that are undesirable as a basis for a subsequent coating. Patent Number WO 93/03198 discloses the use of hydroxylamine as an accelerator in tricathion phosphatization baths having zinc contents between 0.5 and 2 grams per liter and contents of nickel and manganese each of 0.2 to 1.5 grams per liter , with defined weight ratios between zinc and the other equivalent cations also having to be maintained. These baths also contain from 1 to 2.5 grams per liter of a "hydroxylamine accelerator", which according to the description means the hydroxylamine salts, preferably hydroxylamine sulfate. If this amount - When expressed is calculated as free hydroxylamine, then hydroxylamine contents of between 0.42 and 1.04 grams per liter are provided. As a general rule, in order to improve the corrosion protection produced by the phosphate layer, a so-called "passivation rinsing", also called subsequent passivation, is carried out in practice. Treatment baths containing chromic acid are still widely used for this purpose. Due to reasons of industrial safety and environmental protection, there is a tendency to replace these chrome-containing passivation baths with chrome-free treatment baths. For this purpose, for example, reactive organic bath solutions containing complex-forming poly (vinylphenols) are known. These compounds are described, for example, in Patent Number DE-C 31 46 265. Particularly effective polymers of this type contain amine substituents and can be obtained by Mannich reaction of poly (vinylphenols) with aldehydes and organic amines. These polymers are described, for example, in the patents Numbers EP-B 91 166, EP-B 319 016 and EP-B 319 017. Polymers of this type are also used for present purposes and therefore these four exposures are incorporated in the present by reference. The passivation rinse solutions also contain polymers having amino groups, the amino group being attached directly to the polymer chain without any intervening aromatic ring. Polymers of this type, which can likewise be used in accordance with the present invention, are described in DE-A 44 09 306. In combination with a passivation rinse, the low zinc phosphatization baths used at present meet the corrosion protection standards established for the manufacture of automobiles. This order of procedure has the disadvantage, however, that the passivation rinse is a separate treatment step that prolongs the production time which increases the space requirement of the pre-treatment line. An object of the present invention is to provide a phosphatization solution that meets corrosion protection standards in the automotive industry and in the case where passivation rinsing can be omitted. Therefore, the space requirement of the pre-treatment line is decreased and the production time can be shortened. The addition of polyacrylic acids to the phosphatization solutions is already known from the literature. An example that can be mentioned is the article by J.I.

Wragg, J.E. Chamberlain, L. Chann, H.W. White, T. Sugama and S. Manalis: "Characterization of Polyuacrilic Acid Modified Zinc Phosphate Crystal Conversion Coatings," Journal of Applied Polymer Science, Volume 50, 917-928 (1993). Here, however, the zinc model phosphatization solutions that were clearly investigated differ from those currently used in practice. They have higher zinc contents; In addition, the manganese widely used and the accelerators usually used today are absent. Therefore, they are not the model for the low zinc phosphatization solutions used in accordance with the present invention. The aforementioned object is filled by a process for the phosphatization of metal surfaces composed of steel, zinc coated steel or steel coated with zinc alloy, and / or aluminum, wherein the metal surfaces, by means of spraying or immersion for a period of between 3 seconds and 8 minutes, they are put in contact with the phosphatization solution containing zinc, characterized in that the phosphatization solution contains: from 0.2 to 3 grams per liter of zinc ions; - from 3 to 50 grams per liter of phosphate ions, calculated as PO4; - from 0.001 to 4 grams per liter of manganese ions; from 0.001 to 0.5 gram per liter of one or more polymers that are selected from polyethers, polycarboxylates, polymeric phosphonic acids, polymeric phosphinocarboxylic acids and organic polymers containing nitrogen; and one or more accelerators that are selected from: 0.3 to 4 grams per liter of chlorate ions; from 0.01 to 0.2 gram per liter of nitrite ions; - from 0.05 to 2 grams per liter of m-nitrobenzene sulfonate ions; from 0.05 to 2 grams per liter of m-nitrobenzaoate ions; - from 0.05 to 2 grams per liter of p-nitrophenol; from 0.005 to 0.15 gram per liter of hydrogen peroxide in free or bound form; - from 0.1 gram to 10 grams per liter of hydroxylamine in free or bound form; - from 0.1 to 10 grams per liter of a reducing sugar. The zinc concentration is preferably between about 0.3 and about 2 grams per liter, particularly between about 0.8 and about 1.6 grams per liter. The zinc contents are greater than approximately 1.6 grams per liter, for example, between 2 and 3 grams per liter, they are of only a slight advantage for the process and on the other hand, they can increase the amount of silt produced in the phosphatization bath . The zinc contents can be established in a functioning phosphatization bath if, during the phosphatization of zinc coated surfaces, an additional amount of zinc enters the phosphatization bath as a result of acid corrosion. Nickel ions and / or cobalt ions within the concentration range of about 1 to about 50 milligrams per liter for nickel of about 5 to about 100 milligrams per liter of cobalt, in combination with as low a content as possible of nitrate, of no more than about 0.5 gram per liter, improve corrosion protection and adhesion to paint compared to that of phosphatization baths that do not contain nickel or cobalt but have a nitrate content of more than 0.5 gram per liter. Therefore, a favorable content is achieved between the operation of the phosphatization baths with a part of residual water terminology requirements in relation to the treatment of the rinse water on the other hand. In the phosphating baths reduced in heavy metals, the manganese content may be within the range of about 0.001 to about 0.2 gram per liter. Otherwise, manganese contents of about 0.5 to about 1.5 grams per liter are usual. From the German Patent Application Number195 00 927.4, it is known that lithium ions where the quantitative scale of about 0.2 to about 1.5 grams per liter improve the corrosion protection capable of being achieved using zinc phosphatization baths. Lithium contents within the quantitative range of 0.2 to about 1.5 grams per liter, particularly from about 0.4 to about 1 gram per liter, also have a favorable effect of corrosion protection achieved in the phosphatization process with integrated subsequent passivation of according to the present invention. In addition to the cations mentioned above, which are incorporated in the phosphate layer or at least have a favorable effect on the crystal growth of the phosphate layer, the phosphatization baths usually contain sodium ions, ions of potassium and / or ammonium ions for the adjustment of the free acid. The concept of free acid is already known to those skilled in the phosphatization art. The method selected herein for determining free acid and total acid is provided in the Examples. Free acid and total acid are important control variables for phosphatization baths, since they have a large influence on the weight of the layer. The values for the free acid between 0 and 1.5 points in the phosphatization of parts and, in the case of continuous phosphatization up to 2.5 points, and the values for the total acid of between approximately 15 and approximately 30 points remain within the scale usual technique and are suitable in accordance with the present invention. In phosphatization baths that are going to be suitable for different substrates it has become conventional to add free fluoride and / or fluoride bound in complex compounds in amounts up to 2.5 grams per liter of total fluoride, up to 1 gram per liter thereof being free fluoride. The presence of these amounts of fluoride is also advantageous in the phosphatization baths according to the present invention. In the absence of fluoride, the aluminum content of the bath should not exceed 3 milligrams per liter. In the presence of fluoride, due to the formation of complexes, higher contents of Al are tolerated, as long as the concentration of Al not formed in complex does not exceed 3 milligrams per liter. The use of fluoride-containing baths is therefore advantageous when the surfaces that are being phosphatized consist of at least partially aluminum or contain aluminum. In these cases, it is beneficial not to use bound fluoride in the complex compounds, without using only free fluoride, preferably in concentrations of 0.5 to 1.0 gram per liter. For the phosphatization of zinc surfaces it is not absolutely necessary that the phosphatization baths contain the so-called accelerators. For the phosphatization of steel surfaces, however, it is necessary that the phosphatization solution contains one or more accelerators. These accelerators are common in the prior art as components of zinc phosphatization baths. They are understood as including substances which, being reduced by themselves, are chemically bound to the hydrogen formed as a result of the attack by the acid on the metal surface. The oxidizing accelerators also have the effect of oxidizing the iron (II) ions liberated by the corrosive attack on steel surfaces to the trivalent state, so that they can precipitate as iron (III) phosphate. The phosphatizing baths according to the present invention may contain as accelerators one or more of the following components: - - from 0 .3 to 4 grams per liter of chlorate ions; from 0.01 to 0.2 gram per liter of nitrite ions; from 0.05 to 2 grams per liter of m-nitrobenzenesulfonate ions; - from 0.05 to 2 grams per liter of m-nitrobenzoate ions; - from 0.05 to 2 grams per liter of p-nitrophenol; from 0.005 to 0.15 gram per liter of hydrogen peroxide in free or bound form; - from 0.1 to 10 grams per liter of hydroxylamine in free or bound form; - from 0.1 to 10 grams per liter of a reducing agent.

In the phosphatization of the silica-coated steel, it is necessary that the phosphatization solution contain as little nitrate as possible. Nitrate concentrations of 0.5 gram per liter should not be exceeded, since the highest concentrations of nitrate there is the danger of so-called "white jasper." By this is meant hollows resembling white craters in the phosphate layer. In addition, the adhesion of the paint to the zinc-coated surfaces deteriorates. The use of nitrite as an accelerator leads to technically satisfactory results particularly on steel surfaces. Due to reasons of industrial safety (danger of the evolution of nitrous gases), however, it is advisable not to use nitrite as an accelerator. For the phosphatization of zinc-coated surfaces, this is also convenient in technical fields since nitrate can be formed from nitrite and this, as explained above, can lead to the problem of white jashing and lower adhesion of the paint in the zinc Particularly preferred accelerators are hydrogen peroxide due to reasons of environmental acceptability and hydroxylamine due to technical reasons that involve the possibility of simplified formulations for replacement solutions. The joint use of these two accelerators is not convenient, however, since hydroxylamine is broken down by hydrogen peroxide. If hydrogen peroxide in free or bound form is used as an accelerator, concentrations of 0.005 to 0.02 gram per liter of hydrogen peroxide are particularly preferred. The hydrogen peroxide can be added as is to the phosphatization solution. However, it is also possible to add hydrogen peroxide in bound form as compounds that yield hydrogen peroxide as a result of hydrolysis reactions in the phosphatization bath. Examples of these compounds are per-salts, for example perborates, percarbonates, peroxosulfates or peroxodisulfates. Other suitable sources of hydrogen peroxide are ionic peroxides such as alkali metal peroxides. A preferred thiodality of the present invention involves the use of a combination of chlorate ions and hydrogen peroxide in the phosphatization by an immersion process. In this embodiment, the concentration of the chlorate can be, for example, 2 to 4 grams per liter and the concentration of the hydrogen peroxide can be 10 to 50 parts per million. The use of reducing sugars as the accelerator is known from US Patent Number A 5 378 292. According to the present invention, it can be used in amounts between about 0.01 and about 10 grams per liter, preferably between about 0.5 and about 2.5. grams per liter. Examples of these sugars are galactose, mannose and in particular, glucose (dextrose). Another preferred embodiment of the present invention involves the use of hydroxylamine as an accelerator. The hydroxylamine can be used as a free base, as a hydroxylamine complex as an oxime, which is a condensation product of hydroxylamine and a ketone, or in the form of hydroxylammonium salts. If the free hydroxylamine or a concentrate of the phosphatization bath is added to the phosphatization bath, it will be present greatly in - - the form of hydroxylammonium cations due to the acid nature of these solutions. If used in the form of a hydroxylammonium salt, sulfates and phosphates are particularly suitable in the case of phosphates, and acidic salts are preferred due to the better solubility therein. The hydroxylamine or compounds thereof are added to the phosphatization bath in amounts such that the calculated concentration of the free hydroxylamine is between 0.1 and 10 grams per liter, preferably between 0.3 and 5 grams per liter. Here it is preferred that the phosphatization baths contain hydroxylamine as the only accelerator, possibly together at most 0.5 gram per liter of nitrate. Accordingly, in a preferred embodiment, phosphatization baths are used which do not contain other known accelerators such as nitrite, halogen oxo anions, peroxides or nitrobenzene sulfonate. A positive side effect is that hydroxylamine concentrations greater than about 1.5 grams per liter decrease the risk of rust formation in improperly flooded areas of the structural parts being phosphatized. During the application of the phosphatization process to steel surfaces, the iron passes to the solution in the form of iron (II) ions. If the phosphatization baths present do not contain substances - -that oxidize iron (II), the divalent iron becomes the trivalent state only as a result of atmospheric oxidation, so that it can precipitate as iron (III) phosphate. This is the case, for example, when hydroxylamine is used. Consequently, the iron (II) contents that can accumulate in the phosphatization baths are significantly larger than those in the baths containing oxidizing agents. In this case, iron (II) concentrations of up to 50 parts per million are normal, values up to 500 parts per million are also possible during a short period in the course of production. These iron (II) concentrations are not detrimental to the phosphatization process according to the present invention. When hard water is used, the phosphatization baths can also contain the Mg (II) and Ca (II) hardness cations in a total concentration up to 7 millimoles per liter. The Mg (II) or Ca (II) can also be added to the phosphatization bath in amounts up to 2.5 grams per liter. The weight ratio of phosphate ions to zinc ions in the phosphatization baths can vary within wide limits as long as it is between 3.7 and 30. A weight ratio of between 10 and 20 is particularly preferred. For purposes of manifesting the concentration of - - phosphate, the total phosphorus content of the phosphating bath is considered as being present in the form of phosphate ions PO ^ -. In the calculation of weight ratios, therefore, the fact that, at the pH of the phosphatization baths, which generally fall within the range of three to about 3.6, a very small part of the pH is not taken into account. Phosphate is actually present in the form of negatively charged anions with triplicate. At these pH values, phosphate is more likely to exist primarily as an individual negatively charged dihydrogen phosphate anion together with smaller amounts than the undissociated phosphoric acid or double negatively charged hydrogen phosphate anions. The organic polymers used according to the present invention preferably have molecular weights (which can be determined for example by gel permeation chromatography) and from about 500 to about 50,000, in particular from about 800 to about 20,000. The phosphatization baths preferably contain the organic polymers in a concentration of between about 0.01 and about 0.1 gram per liter. At lower concentrations, the required passivation effect decreases. The highest concentrations do not - - they increase the effect considerably and therefore become increasingly uneconomic. The polymers that can be used in accordance with the present invention can be members of various chemical types. Common to all of them, however, is that they carry oxygen atoms and / or nitrogen atoms either in the polymer chain or in the secondary groups. The simplest polymers of this type are polyalkylene glycols, for example polyethylene glycol or polypropylene glycol which preferably have a molecular weight of 500 to 10,000. Polymeric carboxylic acids such as homo- or co-polymers of acrylic acid, methacrylic acid and maleic acid are also suitable and also are polymeric phosphonic acids or polymeric phosphinocarboxylic acids. One example that can be provided is a polyphosphinocarboxylic acid which can be considered as the copolymer of sodium hypophosphite and acrylic acid and can be obtained commercially as "Belclene® 500" from FMC Corporation of Great Britain. Organic polymers can also be selected from homo- and co-polymeric compounds containing amino groups and containing or consisting of structural units corresponding to the general formula (I): CH. CH, N, 2 C j I O and the hydrolysis products thereof, wherein R1 and R ^ are the same or different and can represent alkyl hydrogen having from 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, iso-propyl, n -butyl, iso-butyl, tertiary butyl, amyl, n-hexyl, iso-hexyl, or Diclohexyl1. A comprehensive view of these polymers can be found in Patent Number DE-A 44 09 306, the disclosure of which is incorporated herein by reference. Specific examples are the hydrolysis products of the homo-, and co-polymers of N-vinyl formamide, N-vinyl-N-methyl-formamide, N-vinylacetamide, N-vinyl acetamide, N-vinyl-N- methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-propionamide and N-vinyl-N-methyl-propionamide, N-vinylformamide being preferred since it is very easily hydrolysable. The appropriate comonomers are acidic 1 This word has not been translated because it has been determined that the original was a mistake and therefore does not have proper translation. - - monoethylenically unsaturated carboxylic acids having from 3 to 8 carbon atoms, as well as the water-soluble salts of these monomers. The organic polymers can also be selected from the poly-4-vinylphenol compounds corresponding to the general formula (II): wherein: n represents a number between 5 and 100, x independently represents hydrogen and / or CRR groups] _OH, where R and R ?. they represent hydrogen, aliphatic and / or aromatic groups having from 1 to 12 carbon atoms. These polymers are described as separate rinse solutions in Patent Number DE-C 31 46 265. In accordance with this specification, poly-4-vinylphenol compounds of the type wherein at least one x represents CH 2 OH, are particularly suitable. A method for the preparation thereof is provided in the aforementioned document. Particularly preferred is the use of organic polymers which are selected from homo- or co-polymeric compounds containing amino groups and which include at least one polymer selected from the group consisting of (a), (b), (c) ) or (d), wherein: (a) comprises a polymeric material having at least one unit corresponding to the formula: wherein: R a R 3 for each of the units are independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 18 carbon atoms; Y to Y4 for each one of the units are independently selected from the group consisting of hydrogen, -CR1 R5OR5, -CH2CI or an alkyl or aryl group having 1 to 18 carbon atoms or Z which is presented below: but at least a fraction of Y f Y21 Y3 or Y4 of the homo- or co-polymeric compound or material must be Z; - - R 5 to R 2 for each of the units is independently selected from the group consisting of hydrogen, an alkyl, aryl, hydroxyalkyl, aminoalkyl, mercaptoalkyl or a phosphoalkyl group; R 2 can also represent -O ^ -1) or -OH; for each of the units it is independently selected from the group consisting of hydrogen, an acyl group, an acetyl group, a benzoyl group; 3-allyloxy-2-hydroxy-propyl; 3-benzyloxy-2-hydroxy-propyl; 3-butoxy-2-hydroxy-propyl; 3-Alkyloxy-2-hydroxypropyl; 2-hydroxy-octyl; 2-hydroxy-alkyl; 2-hydroxy-2-phenylethyl; 2-hydroxy-2-alkyl-phenylethyl; benzyl; methyl; ethyl; propyl; I rent; allyl; alkylbenzyl; haloalkyl; haloalkenyl; 2-chloropropenyl; sodium; potassium; tetraarylammonium; tetraalkylammonium; tetraalkylphosphonium; tetra-arylphosphonium or a condensation product of ethylene oxide, propylene oxide or a mixture of a copolymer thereof; (b) comprises: a polymeric material having at least one unit corresponding to the formula: wherein: R a R 3 for each of the units are independently selected from the group consisting of hydrogen, an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 18 carbon atoms; And to Y3 for each of the units are independently selected from the group consisting of hydrogen, -CR ?? R5? Rg, -CH2CI or an alkyl or aryl group having from 1 to 18 carbon atoms or Z: but at least a fraction of Y] _, Y2 or Y3 of the final product must be Z; R 4 to R 2 for each of the units are independently selected from the group consisting of hydrogen, an alkyl, aryl, hydroxyalkyl, aminoalkyl, mercaptoalkyl or phosphoalkyl group; R? 2 can also be -o HD or -OH; Wx for each of the units is independently selected from the group consisting of hydrogen, an acyl group, an acetyl group, a benzoyl group; 3-allyloxy-2-hydroxy-propyl; 3-benzyloxy-2-hydroxy-propyl; 3-alkyl-benzyloxy-2-hydroxy-propyl; 3-phenoxy-2-hydroxy-propyl; 3-alkyl-phenoxy-2-hydroxy-propyl; 3-butoxy-2-hydroxy-propyl; 3-alkoxy-2-hydroxy-propyl; 2-hydroxy-octyl; 2-hydroxy-alkyl; 2-hydroxy-2-phenylethyl; 2-hydroxy-2-alkyl-phenylethyl; tencilo; methyl; ethyl; propyl; I rent; allyl; aikil-benzyl; haloalkyl; haloalkenyl; 2-chloro-propenyl or a condensation product of ethylene oxide, propylene oxide or a mixture thereof; (c) comprises: a copolymeric material wherein at least a part of the copolymer has the structure: and at least a fraction of that part is polymerized with one or more monomers which for each unit is independently selected from the group consisting of acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, vinylmethyl ketone, ketone methyl-isopropenyl, acrylic acid, methacrylic acid, acrylamide, methacrylamide, n-amyl methacrylate, styrene, m-bromostyrene, p-bromostyrene, pyridine, diallyl-dimethylammonium salts, 1,3-butadiene, n-butyl acrylate, methacrylate of t-butylaminoethyl, n-butyl methacrylate, t-butyl methacrylate, n-butyl-vinyl ether, - 2 t-butyl-vinyl ether, m-chlorostyrene, o-chlorostyrene, p-chlorostyrene, n-decyl methacrylate, N, N-dialkyl-melamine, N, N-di-n-butylacrylamide, di-n-itaconate butyl, di-n-butyl maleate, diethylaminoethyl methacrylate, diethylene glycol monovinyl ether, diethyl fumarate, diethyl itaconate, diethyl vinyl phosphate, vinyl phosphonic acid, diisobutyl maleate, diisopropyl itaconate, diisopropyl maleate, fumarate of dimethyl, dimethyl itaconate, dimethyl maleate, di-n-nonyl fumarate, di-n-nonyl maleate, dioctyl fumarate, di-n-octyl itaconate, di-n-propyl itaconate, N-ether -dodecylvinyl, ethyl acid fumarate, acidic ethyl maleate, ethyl acrylate, ethyl cinnamate, N-ethyl methacrylamide, ethyl methacrylate, ethylvinyl ether, 5-ethyl-2-vinylpyridine, 5-ethyl-2-vinyl-pyridine -l-oxide, glycidyl acrylate, glycidyl methacrylate, n-hexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydro methacrylate xi-propyl, isobutyl methacrylate, isobutylvinyl ether, isoprene, isopropyl methacrylate, isopropylvinyl ether, itaconic acid, lauryl methacrylate, N-methylolacrylamide, N-methylol-methacrylamide, N-isobutoxy-methylacrylamide, N-isobutoxymethylmethacrylamide , N-alkyloxy-methylacrylamide, N-alkyloxy-methyl-ethacrylamide, N-vinyl-caprolactam, N-methyl-methacrylamide, alpha-methyl-styrene, m-methyl-styrene, o-methyl-styrene, p-methyl-styrene, 2-methyl-5-vinyl-pyridine, n-propyl methacrylate, sodium p-styrene sulfonate, stearyl methacrylate, styrene, p-styrene sulfonic acid, p-styrene sulfonamide, vinyl bromide, carbazole -vinyl, vinyl chloride, vinylidene chloride, 1-vinyl-naphthalene, 2-vinylnaphthalene, 2-vinyl-pyridine, 4-vinyl-pyridine, 2-vinyl-pyridine N-oxide, 4-vinyl-pyrimidine, N -vinyl-pyrrolidone; and W? Yx to Y4 and R to R3 are as described under (a); (d) comprises a condensation polymer of the polymeric materials (a), (b) or (c), a condensable form of (a), (b), (c) or a mixture thereof that is condensed with a second compound which is selected from the group consisting of phenols, tannins, novolac resins, lignin compounds, together with aldehydes, ketones or mixtures thereof, in order to prepare a condensation resin product, forming the condensation resin product by the addition of "Z" to less a part of itself, by further reaction of the resin product with (1) an aldehyde or ketone, (2) a secondary amine, a final adduct that can be reacted with an acid. The methods for preparing these polymers are described in the publications of the already mentioned Patents Nos. EP-B 319 016 and EP-B 319 017. Polymers of this type can be obtained from The Henkel Corporation, Parker Amchen Division, USA, under the factory names Parcolene® 95C, Deoxylyte® 90A, 95A, 95AT, 100NC and TD-1355-CW. In this regard, the particularly preferred polymers are those in which at least a fraction of the Z groups of the organic polymer possesses a polyhydroxy-alkylamine functionality that originates from the condensation of an amine or ammonia with a ketose or aldose having from 3 to 8 carbon atoms. The condensation products, if desired, can be reduced in an amine. Additional examples of these polymers are the condensation products of a polyvinylphenol with formaldehyde or paraformaldehyde and with a secondary organic amine. Here it is preferred to start from polyvinylphenols having a molecular weight of from about 1,000 to about 10,000. Particularly preferred condensation products are those in which the secondary organic amine is selected from methylethanolamine and N-methylglucamine. Within the stated concentration scales, the organic polymers are stable in the phosphatization baths and do not lead to precipitation. They also do not show any detrimental effects on the formation of the layer and therefore do not lead, for example, to the manifestation of passivation, which can inhibit this growth of the phosphate crystals on the metal surface. The organic polymers can also be selected from substituted polyalkylene derivatives containing the structural units: - (CR1-R2) x-CR3-IY wherein R ^, R2, R3 can independently represent hydrogen or a methyl or ethyl group, x represents 1, 2, 3 or 4, and Y represents a substituent that contains minus one nitrogen atom and which is incorporated in the alkylamino group into a saturated or unsaturated mono- or polynuclear heterocyclic compound. Here, those polymers are preferred wherein R 1, R 2, R 3 each represents hydrogen. Preferably, x represents 1. Accordingly, the substituted polyethylenes are particularly preferred. Organic polymers containing one or more of the following structural units are particularly preferred: - - In a further preferred embodiment, the organic polymers are polymeric sugar derivatives that contain an amino group. An example of these are chitosans, which may contain, for example, the following structural group: It is valid for all the organic polymers that contain nitrogen, at the pH of the phosphatization solution, to propose at least some of the nitrogen atoms and therefore carry a positive charge. The phosphatization baths are generally distributed in the form of aqueous concentrates that are adjusted in situ to the concentration to be used by the addition of water. Due to stability reasons, these concentrates can contain an excess of the free phosphonic acid so that during the dilution of the bath concentration, the free acid value is initially too high and the pH was too low. The free acid value is decreased to the scale required by the addition of alkalies such as sodium hydroxide, sodium carbonate or ammonia. It is also known that the content of the free acid may increase over time while the phosphatization bath is in use, as a result of the consumption of the layer-forming cations and possibly as a result of the decomposition reactions of the accelerator. In these cases, it is necessary to re-adjust the value of the free acid to the required scale by adding alkali from time to time. This means that the contents of the alkali metal or the ammonium ions in the phosphatization baths can fluctuate within wide limits and, during the period in which the phosphatization baths are in use, the free acid tends to increase due to the relocation. The weight ratio of the alkali metal ions and / or ammonium ions to, for example, the zinc ions may correspondingly be very low in the case of freshly prepared phosphatizing baths, for example, it may be of < 0.05 and in extreme cases it may still be 0, while it usually rises over time as a result of the bath maintenance procedures, so that the ratio becomes greater than 1 and the values can reach up to 10 and more. As a general rule, low zinc phosphatization baths require additions of alkali metal ions or ammonium ions so that the free acid can be adjusted to within the required scale at the required weight ratio of? 43-: Zn of > 8. Similar observations can be made with respect to the ratios of the alkali metal ions and / or ammonium ions to the other constituents of the bath, for example, to the phosphate ions. In the case of phosphatization baths containing lithium, it is preferred to avoid using the sodium compounds to adjust the free acid, since the beneficial effect of lithium in the protection against correction is suppressed by excessively high sodium concentrations. In this case, the basic lithium compounds are preferably used for the adjustment of the free acid. Alternatively, the potassium compounds may also be appropriate. In principle, the way in which the cations giving rise to or influencing the layer are introduced into the phosphatization baths is not important. Nitrates, however, should be avoided so as not to exceed the preferred upper limit for the nitrate content. Metal ions are preferably used in the form of those - compounds that do not introduce any foreign ions into the phosphatization solution. Due to this reason, it is very advantageous to use the metals in the form of oxides or carbonates thereof. You can also use lithium as sulfated. The phosphatizing baths according to the invention are suitable for phosphatizing composite surfaces of steel, zinc-coated steel, steel coated with zinc alloy, aluminum, aluminized steel or steel coated with aluminum alloy, as well as aluminum-magnesium alloys. . Here, the term "aluminum" includes the common aluminum alloys in technology such as AlMgg .5Si? 4. The aforementioned materials can, as has become increasingly common in the manufacture of automobiles, be placed in juxtaposition. In this regard, the work pieces of the body can also consist of a pre-treated material, as is the case, for example, in the Bonazink® process. Here, the substrate material is first chroma or phosphated and subsequently coated with the organic resin. The phosphatization process according to the present invention then leads to phosphatization on damaged areas of this pretreated layer or untreated reverse sides.

- - The present process is suitable for application by immersion, spraying or spraying / immersion. It can be used particularly in the manufacture of automobiles, where the treatment times of between 1 and 8 minutes, particularly from 2 to 5 minutes, are conventional. However, its use in the continuous phosphatization of steel works, where the treatment times are between 3 and 12 seconds, is possible as well. When using continuous phosphatization processes, it is convenient to adjust the bath concentrations in each case within the upper half of the preferred scale according to the present invention. For example, the zinc content may be 1.5 to 2.5 grams per liter and the content of the free acid may be 1.5 to 2.5 points. Especially zinc-coated steel and electrolytically galvanized steel in particular are suitable as substrates for continuous phosphatization. It is also conventional in other known phosphatization baths, suitable bath temperatures, regardless of the field of application, which are between 30 ° C. and 70 ° C, with the temperature scale between 45 ° C and 60 ° C being preferred. The phosphatization process according to the present invention is intended in particular for the treatment of metal surfaces previously - mentioned before coating, for example, before a cathode electrocoating, as is conventional in the manufacture of automobiles. It is also suitable as a pre-treatment before a powder coating, such as is used, for example, for household appliances. The phosphatization process must be seen as an individual step in the conventional industrial pre-treatment chain. In this chain, the steps involving cleaning and defatting, intermediate rinsing and activation precede the phosphatization process with activation being carried out generally by means of activation agents containing titanium phosphate.

Examples The phosphatization processes according to the present invention the comparison processes were tested on sheets of ST 1405 steel, which were used in the manufacture of automobiles. The immersion process carried out was the following conventional procedure in the manufacture of the body of the car: 1. Cleaning by means of an alkaline cleaner (Ridoline® 1501, Henkel KGaA), formulation of 2 percent in water of the key , at 55 ° C, for 4 minutes. 2. Rinse with tap water, at room temperature, - - 1 minute . Activation by means of an activation agent containing titanium phosphate (Fixodine® 950, Henkel KGaA), 0.1 percent formulation in non-ionized water, at room temperature, 1 minute. Phosphatization using phosphatization baths of the following composition: 1.0 gram per liter of Zn2 + 1.0 gram per liter of Mn2 + 0.1 gram per liter of Fe ^ + 14 grams per liter of PO43- 0.95 gram per liter of SiFg2- 0.2 gram of F ~ 1.7 grams of (NH3OH) 2S04 Polymers as in the Table In addition to the cations listed above, the nitrate-free phosphatization baths contained, if necessary, sodium ions to adjust the free acid. The number of free acid points was 0. 9 and that of the total acid was 23; the pH was 3.35. The number of free acid points means the required consumption in milliliters of a 0.1 N sodium hydroxide solution to titrate 10 milliliters of the bath solution until - a pH of 3.6 is achieved. Similarly, the number of total acid points indicates the consumption in milliliters to achieve a pH of 8.2. 5. Rinse with demineralized water 6. Blow dry using compressed air. The mass per unit area ("weight of the layer") was determined by dissolving in 5 percent of a chromic acid solution in accordance with DIN 50942. It is shown in the Table. The sheets of the phosphatized specimen were coated with cathodic dip paint from BASF (FT 85-7042). The anticorrosive action was tested in an alternative weather test by VDA 621-415 through 9 cycles. The result is included in the Table as the loss of a painting during scratching (half-space width).

- Table: Phosphatization baths and phosphatization results No. Polymer Weight Loss of paint (concentration) layer (width of medium (g / cm ^) space) Comp. 1 Polyethylene 3.7 1.9 Ex. 1 Polyethylene glycol Molecular weight of 1000, 10 parts per million 3.2 1.7 Ex. 2 Co or Example 1, 50 parts per million 3.9 1.5 Ex. 3 TD-1355-C 3000 *) 3.5 1.5 Ex. 4 As in Example 3, 50 parts per million 3. 8 1. 3 E j. 5 TD-1355-CW 8600 **) 3. 7 1. 4 Ex. 6 As in Example 5, 50 parts per million 3.2 1.1 *) The Mannich reaction product of polyvinylphenol (molecular weight of 3000, determined by gel permeation chromatography) with paraformaldehyde and glucamine (Parker Amchen, USA). **) as above, molecular weight of polyvinylphenol: 8600.

Claims

- CLAIMS:

1. A process of phosphatization of metal surfaces composed of steel, zinc-coated steel or steel coated with zinc alloy, aluminum and / or aluminum-magnesium alloys, where the metal surfaces, by means of spraying or dipping during a period of between 3 seconds and 8 minutes, they are put in contact with a phosphatization solution containing zinc, characterized in that the phosphatization solution contains: from 0.2 to 3 grams per liter of zinc ions-from 3 to 50 grams per liter of phosphate ions, which is calculated as PO4; from 0.001 to 4 grams per liter of manganese ions; from 0.001 to 0.5 gram per liter of one or more polymers which are selected from polyethers, polycarboxylates, polymeric phosphonic acids, polymeric phosphinocarboxylic acids and organic nitrogen-containing polymers; and one or more accelerators that are selected from: 0.3 to 4 grams per liter of chlorate ions; from 0.01 to 0.2 gram per liter of nitrite ions; - - from 0.05 to 2 grams per liter of m-nitrobenzenesulfonate ions; from 0.05 to 2 grams per liter of m-nitrobenzaoate ions; from 0.05 to 2 grams per liter of p-nitrophenol; from 0.005 to 0.15 gram per liter of hydrogen peroxide in free or bound form; from 0.1 gram to 10 grams per liter of hydroxylamine in free or bound form; 0.1 to 10 grams per liter of a reducing sugar.

2. A process according to claim 1, wherein the phosphatization solution contains, in admeasure, from 1 to 50 milligrams per liter of nickel ions and / or from 5 to 100 milligrams per liter of cobalt ions.

3. A process according to either or both of claims 1 and 2, wherein the phosphatizing solution further contains 0.2 to 1.5 grams per liter of lithium ions.

4. A process according to one or more of claims 1 to 3, wherein the phosphatization solution contains, in addition, fluoride in amounts of up to 2.5 grams per liter of total fluoride, up to 1 gram per liter, being free fluoride, in each case that is calculated as F-.

5. A process according to one or more of claims 1 to 4, wherein the phosphatizing solution contains an accelerator of 5 to 150 milligrams per liter of hydrogen peroxide in free or bound form.

6. A process according to one or more of claims 1 to 4, wherein the phosphatizing solution contains as the accelerator 0.1 to 10 grams per liter of hydroxylamine in free or bound form.

7. A process according to one or more of claims 1 to 6, wherein the phosphatization solution contains no more than 0.5 gram per liter of nitrate.

8. A process according to one or more of claims 1 to 7, wherein the phosphatization solution contains the organic polymers in a concentration of between 0.01 and 0.1 gram per liter.

9. A process according to one or more of claims 1 to 8, wherein the organic polymers are polyalkylene glycols having a molecular weight of 500 to 10,000.

10. A process according to one or more of claims 1 to 8, wherein the organic polymers are selected from homo- or copolymer compounds containing amino groups and containing o- they consist of structural units corresponding to the general formula (I): cw. CH- N R 2 / and the hydrolysis products thereof, wherein R1 and R2 are the same or different and may represent hydrogen or alkyl having 1 to 6 carbon atoms.

11. A process according to one or more of claims 1- to 8, wherein the organic polymers are selected from the poly-4-vinylphenol compounds corresponding to the general formula (II): wherein: n represents a number between 5 and 100, x independently represents hydrogen and / or CRR? OH groups, wherein R and R represent hydrogen, aliphatic and / or aromatic groups having from 1 to 12 carbon atoms.

12. A process according to one or more of the claims ß, wherein the organic polymers are selected from the homo- or copolymer compounds containing amino groups that includes at least one polymer selected from the group consisting of of (a), (b), (c) or (d), wherein: (a) comprises a polymeric material having at least one unit corresponding to the formula: wherein: Rx to R3 for each of the units are independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 5 carbon atoms or an aryl group having from 6 to 18 carbon atoms; Y to Y4 for each of the units are independently selected from the group consisting of hydrogen, -CRXXR5OR5, -CH2CI or an alkyl or aryl group having 1 to 18 carbon atoms or Z which is presented below: but at least a fraction of Y ?? Y2, Y3 or Y4 of the homo- or co-polymeric compound or material must be Z; R 5 to R 2 for each of the units are independently selected from the group consisting of hydrogen, an alkyl, aryl, hydroxyalkyl, aminoalkyl, mercaptoalkyl or phosphoalkyl group; R? 2 can also represent -? (~ L) or -OH; x for each of the units is independently selected from the group consisting of hydrogen, an acyl group, an acetyl group, a benzoyl group; 3-allyloxy-2-hydroxy-propyl; 3-benzyloxy-2-hydroxy-propyl; 3-butoxy-2-hydroxy-propyl; 3-Alkyloxy-2-hydroxypropyl; 2-hydroxy-octyl; 2-hydroxy-alkyl; 2-hydroxy-2-phenylethyl; 2-hydroxy-2-alkyl-phenylethyl; benzyl; methyl; ethyl; propyl; I rent; allyl; alkylbenzyl; haloalkyl; haloalkenyl; 2-chloropropenyl; sodium; potassium; tetraarylammonium; tetraalkylammonium; tetraalkylphosphonium; tetra-arylphosphonium or a condensation product of ethylene oxide, propylene oxide or a mixture or copolymer thereof; (b) comprises a polymeric material having at least one unit corresponding to the formula: wherein: Rx to R2 for each of the units are independently selected from the group consisting of hydrogen, an alkyl group having from 1 to 5 carbon atoms or an aryl group having from 6 to 18 carbon atoms; Yx to Y3 for each non-unit are independently selected from the group consisting of hydrogen, -CRXXR5OR5, -CH2CI or an alkyl or aryl group having 1 to 18 carbon atoms or Z which is presented below: but at least a fraction of Yx, Y2 or Y3 of the final product must be Z; R 4 to R 2 of each of the units are independently selected from the group consisting of hydrogen, an alkyl, aryl, hydroxy-alkyl, amino-alkyl, mercapto-alkyl or a phospho-alkyl group; R 2 can also represent -o '"" 1' or -OH; 2 for each of the units is independently selected from the group consisting of hydrogen, an acyl group, an acetyl group, a benzoyl group; 3-allyloxy-2-hydroxy-propyl; 3-benzyloxy-2-hydroxy-propyl; 3-alkyl-benzyloxy-2-hydroxy-propyl; 3-phenoxy-2-hydroxypropyl; 3-alkyl-phenoxy-2-hydroxy-propyl; 3-butoxy-2-hydroxy-propyl; 3-Alkyloxy-2-hydroxypropyl; 2-hydroxy-octyl; 2-hydroxy-alkyl; 2-hydroxy-2-phenylethyl; 2-hydroxy-2-alkyl-phenylethyl; benzyl; methyl; ethyl; propyl; I rent; allyl; alkyl benzyl; haloalkyl; haloalkenyl; 2-chloro-propenyl or a condensation product of ethylene oxide, propylene oxide or a mixture thereof; (c) comprises a copolymeric material wherein at least a part of the copolymer has the structure: and at least a fraction of that part is polymerized with one or more monomers which for each unit are independently selected from the group consisting of acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, vinylmethyl ketone, ketone isopropenyl ethyl, acrylic acid, methacrylic acid, acrylamide, methacrylamide, n-amyl methacrylate, styrene, m-bromostyrene, p-bromostyrene, pyridine, diallyl-dimethylammonium salts, 1,3-butadiene, n-butylacrylate, methacrylate -butylaminoethyl, n-butyl methacrylate, tertiary butyl methacrylate, n-butyl-vinyl ether, t-butyl-vinyl ether, m-chlorostyrene, o-chlorostyrene, p-chlorostyrene, n-decyl methacrylate, N, N-dialkyl-melamine, N, N-di-n-butylacrylamide, di-n-butyl itaconate, di-n-butyl maleate, diethylamino-ethyl methacrylate, diethylene glycol monovinyl ether, diethyl fumarate, diethyl itaconate, diethyl vinyl phosphate, vinyl phosphonic acid, maleate diisobutyl, diisopropyl itaconate, diisopropyl maleate, dimethyl fumarate, dimethyl itaconate, dimethyl maleate, di-n-nonyl fumarate, di-n-nonyl maleate, dioctyl fumarate, di-n-octyl itaconate, di-n-propyl itaconate, N-dodecyl vinyl ether, ethyl acid fumarate, ethyl acid maleate, ethyl acrylate, ethyl cinnamate, N-ethyl methacrylamide, ethyl methacrylate, ethylvinyl ether, 5-ethyl- 2-vinylpyridine, 5-ethyl-2-vinyl-pyridine-1-oxide, glycidyl acrylate, glycidyl methacrylate, n-hexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxy-propyl methacrylate, methacrylate isobutyl, isobutylvinyl ether, isoprene, isopropyl methacrylate, isopropylvinyl ether, itaconic acid co, lauryl methacrylate, N-methylolacrylamide, N-methylol-methacrylamide, N-isobutoxy-methylacrylamide, N-isobutoxy-methyl methacrylamide, N-alkyloxy-methylacrylamide, N-alkyloxymethylmethacrylamide, N-vinyl-caprolactam, N-methyl- methacrylamide, alpha-methyl-styrene, m-methyl-styrene, o-methyl-styrene, p-methyl-styrene, 2-methyl-5-vinyl-pyridine, n-propyl methacrylate, sodium p-styrene sulfonate, stearyl methacrylate, styrene, p-styrenesulfonic acid, p-styrenesulfonamide, vinyl bromide, 9-vinyl carbazole, vinyl chloride, vinylidene chloride, 1-vinyl-naphthalene, 2-vinylnaphthalene, 2-vinyl-pyridine, 4 -vinyl-pyridine, 2-vinyl-pyridine N-oxide, 4-vinyl-pyrimidine, N-vinyl-pyrrolidone; Y ? Yx to Y4 and Rx to R3 are as described under (a); (d) comprises a condensation polymer made of polymeric materials (a), (b) or (c), a condensable form of (a), (b), (c) or a mixture thereof which is condensed with a second compound that is selected from - - group consisting of phenols, tannins, novolac resins, lignin compounds, together with aldehydes, ketones or mixtures thereof, in order to prepare a condensation resin product, forming the condensation resin product by the addition of " Z "to at least a part of itself, by additional reaction of the resin product with (1) an aldehyde or ketone, (2) a secondary amine, a final adduct that can be reacted with an acid.

13. A process according to claim 12 wherein at least a fraction of the Z groups of the organic polymer possesses a polyhydroxy-alkylamine functionality that originates from the condensation of an amine or ammonia with a ketose or aldose having from 3 to 8 carbon atoms.

14. A process according to claim 12, wherein the organic polymer is a condensation product of a polyvinylphenol, having a molecular weight of from about 1,000 to about 10,000, with formaldehyde or paraformaldehyde and with a secondary organic amine.

15. A process according to claim 14, wherein the secondary organic amine is selected from methylethanolamine and N-methylglucamine. - -

16. A process according to one or more of claims 1 to 8, wherein the organic polymers are selected from substituted polyalkylene derivatives: - (CR1-R2) x-CR3- wherein R ^, R2, R3 can independently represent hydrogen or a methyl or ethyl group, x represents 1, 2, 3 or 4, and Y represents a substituent containing at least one nitrogen atom and is incorporated into a group of alkylamino or a saturated or unsaturated mono- or polynuclear heterocyclic compound.

17. A process according to claim 16 wherein R - * -, R2, R3 each represents hydrogen and x represents 1.

18. A process according to claim 16 or 17, wherein the organic polymers contain one or more of the following structural units: -

19. A process according to one or more of claims 1 to 8 wherein the organic polymers are polymeric sugar derivatives containing amino groups.

20. A process according to claim 19 wherein the polymeric sugar derivatives contain the following structural groups: