JP2001509840A - Zinc phosphate treatment with passivation after integration - Google Patents

Abstract

(57) Abstract: A method for phosphating a zinc alloy-coated steel or a metal surface of a zinc-coated steel or steel with aluminum and / or an aluminum-magnesium alloy, wherein the phosphating solution is 0.2%. to 3 g / l of zinc ions, (calculated as PO ₄₎ phosphate ions 3 to 50 g / l, manganese ions, polyether 0.001 to 0.5 g / l of 0.001~4g / l, polycarboxylates A method comprising one or more polymers selected from polymeric phosphonic acids, polymeric phosphinocarboxylic acids and nitrogen-containing organic polymers, and one or more accelerators. Preferred polymers are poly (vinylphenol) derivatives containing amino groups.

Description

DETAILED DESCRIPTION OF THE INVENTION                 Zinc phosphate treatment with passivation after integration   The present invention relates to zinc ions, manganese ions, phosphate ions, and up to 0.5 g / l. Treatment of metal surface using acidic phosphate aqueous solution containing organic polymer On how to do it. The invention relates to subsequent coatings, especially electrodeposition coatings or powder coatings. Also can be used as a method as a pre-treatment of metal surfaces for You. The method of the present invention comprises: steel, galvanized steel or galvanized steel, aluminum, Aluminum-magnesium alloy, aluminized steel or aluminum alloy It can also be used for surface treatment of plated steel, eliminating the previously required passivation cleaning. Can be omitted.   Metal phosphating creates a metal phosphate layer that adheres firmly to the metal surface The layer alone increases the resistance to corrosion And under corrosive stresses by combination with paints or other organic coatings Resistance to the progress of corrosion beneath the paint and improving paint adhesion. It is also required to make contributions. Such phosphating methods have long been known Have been. The low zinc phosphating method is a method in which the phosphate solution has a relatively low content of zinc ON, for example, 0.5 to 2 g / l, and pretreatment before coating, especially before electrodeposition coating. It is particularly suitable for reasons. An important factor in these low zinc phosphating baths Is the weight ratio of phosphate ions to zinc ions, which is generally 8 or less. It may be up to about 30.   Phosphate layers with significantly improved corrosion resistance and paint adhesion are used in zinc phosphate baths. Can be achieved by simultaneously using other polyvalent cations in the It is clear. For example, 0.5 to 1.5 g / l of manganese ions, For example, a low zinc process with 0.3 to 2.0 g / l of nickel ions is applied to paint, For example, the so-called tow for pre-treatment of metal surfaces such as cathodic electrodeposition coating of automobile bodies A wide range of applications has been found in the recation process (trication process), etc. You.   Nickel and its alternative cobalt are toxic and wastewater treatment technologies. It has been classified as less preferred from both perspectives, Phosphating method with performance level equivalent to on-process, but in bath Lower concentrations of nickel and / or cobalt, preferably containing the two metals There is a need for a better way.   For example, according to DE-A 20 49 350, important As components, 3 to 20 g / l phosphate ion, 0.5 to 3 g / l zinc ion, 0 . 003 to 0.7 g / l cobalt ion or 0.003 to 0.04 g / l copper Ions or preferably 0.05 to 3 g / l nickel ions, 1 to 8 g / l Gnesium ion, nitrite (nitrite) ion of 0.01 to 0.25 g / l and And 0.1 to 3 g / l fluoride ion and / or 2 to 30 g / l chloride ion Phosphating solutions containing ON are known. Therefore, this method uses cobalt, Phosphating solution further containing ions of one metal in copper or preferably nickel Is a zinc-magnesium phosphate treatment method. Such zinc-magne Pium phosphate treatment has not been technically acceptable.   European Patent Application Publication (EP-B) 18841 particularly discloses, in particular, 0.4 to 1 g / l. Zinc ions, 5-40 g / l phosphate ions and optionally at least 0 . 2 g / l, preferably 0.2 to 2 g / l of nickel, cobalt, calcium and Containing one or more ions selected from manganese and manganese; Disclosed are zinc phosphate treatment solutions that are promoted by a salt. In some cases The manganese, nickel or cobalt content used is therefore at least 0.2 g / l It is. The nickel content was 0.53 g / l and 1.33 g / l in the examples. Has been described.   EP-A-459 541 contains substantially nickel. First, in addition to zinc and phosphate, 0.2-4 g / l of manganese and 1-30 g / A phosphating solution containing 1 l of copper is disclosed. German Patent Application Publication (DE -A) No. 42 10 513, in addition to zinc and phosphate, 0.5 to 25 mg / L of copper ion and hydroxylamine as a promoter and no nickel New phosphating solutions are disclosed. These phosphating solutions may be May further contain 0.15 to 5 g / l of manganese.   German patent application DE-196 06 017.6 describes a 0.2 to 3 g / l Zinc ion, 1-150 mg / l manganese ion and 1-30 mg / l copper ion A heavy metal reduced phosphating solution containing ON is described. This phosphoric acid The salting solution optionally contains up to 50 mg / l of nickel ions and 100 mg / l. / L of cobalt ions. Lithium in an amount in the range of 0.2 to 1.5 g / l Umium is another optional component that may be used.   German Patent Application DE 195 38 788.3 describes the promotion of hydroxylamine About controlling the layer weight of the phosphate layer by using it as an agent. ing. By using hydroxylamine and / or its derivatives, It is known from many patent documents that it can affect the shape of phosphate crystals. Have been. EP-A-315059 describes a phosphating bath The special effect of using hydroxylamine in If the zinc concentration in the bath exceeds the range customary for low zinc methods, In this case, the phosphate crystals have a desired polygonal columnar or hump-like shape on the surface of the steel. Is described. Thus, at zinc concentrations up to 2 g / l, zinc phosphate It is possible to operate the phosphating bath using a weight ratio of about 3.7 to the phosphating bath. There will be. In this patent, cations are combined in these phosphating baths. The advantages of combining are not described in further detail, but in the examples Nickel is used in all cases. In the examples, nitrate and nitric acid were used. Is used, but it is stated that nitrate is preferably not present in large amounts. ing. The required hydroxylamine concentration is between 0.5 and 50 g / l, preferably 1 -10 g / l. Hydroxyl ammonium sulphate in Examples The maximum concentration of the salt is 5 g / l and the hydroxylamine content calculated therefrom Is 2.08 g / l. (Hydroxylammonium sulfate is 41.5 Contains hydroxylamine by weight. ) Phosphating solution is sprayed Applied to steel surfaces. This document discusses the problems associated with the immersion method. Did not mention. It forms a phosphate layer with a significantly higher layer weight and its The problem is that it is not desirable as a basis for later painting.   WO 93/03198 discloses that the zinc content is between 0.5 and 2 g / l, and Nickel and manganese contents are each 0.2-1.5 g / l, zinc and other Trication-phosphate treatment in which the weight ratio between the divalent cation and the divalent cation is strictly maintained. It discloses the use of hydroxylamine as an accelerator in a bath. These baths contain 1 to 2.5 g / l of a "hydroxylamine accelerator". According to the specification, they are hydroxylamines, preferably hydroxylamines. It means a salt of sulphate. The amount described here is free hydroxylamine And the hydroxylamine content is in the range of 0.42 to 1.04 g / l. You.   Generally referred to as so-called “passivation cleaning” or post-passivation. Improving the corrosion resistance by a phosphate layer has been practiced. Chromic acid Treatment baths containing are still widely used for this purpose. Industrial safety and For environmental protection reasons, these chromium-containing passivation baths do not contain chromium It tends to be replaced by a treatment bath. To this end, for example, complexed substituted poly Organic reactive bath solutions containing vinyl phenol are known. Such compounds are For example, it is disclosed in German Patent No. 3146 265. This species is particularly effective Polymers containing amine-substituted, polyvinylphenol and aldehyde Obtained by the Mannich reaction of an organic amine. Such polymers are, for example, For example, European Patent Application Publications (EP-B) 91166, 3119016 and 3 19017. This type of polymer can also be used for the purposes of the present invention. Therefore, by referring to the above-mentioned documents, the disclosure content thereof is described in this specification. Shall be included. The passivating cleaning solution contains a polymer with amino groups The amino group is directly attached to the polymer chain without going through an aromatic ring. Have been. Polymers of this kind can also be used in the invention, for example, It is described in published application 44 09 306.   The low zinc phosphating baths used today in combination with passivating cleaning are: It meets the corrosion resistance standards of the automobile manufacturing industry. The steps of this method, however, Passivation cleaning is a separate process step, which increases production time and However, there is a problem that the demand for the space of the preliminary processing line is increased. ing.   It is an object of the present invention to provide a phosphate which satisfies the corrosion resistance standards in the automotive industry. Providing a processing solution, thereby eliminating the need for passivation cleaning. It is possible. Therefore, the space requirement for the pretreatment line is reduced, Manufacturing time can also be reduced.   The addition of polyacrylic acid to phosphating solutions is already known from various sources. ing. Examples of references described in this regard include J.I.Wragg, J.E. Cham berlain, L .; Chann, H.W. White, T .; Sugama and S.M. "Characteri by Manalis zation of polyacrylic acid modified zinc phosphate crystal conversion co atings ", Journal of Applied Polymer Science, Vol. 50, 917-928 (1993) is there. However, the model of zinc phosphate treatment solution developed is actually It is clearly different from the method used. The method has a higher zinc concentration Manganese, which is more widely used and commonly used today No accelerators are used. Thus, they have been used in accordance with the present invention. It is not a model for low zinc phosphating solutions.   The above purpose is steel, galvanized steel or zinc alloy and / or aluminum etc. A metal surface such as steel plated with zinc is sprayed or dipped into a zinc-containing phosphorus Phosphate by contacting the phosphating solution for 3 seconds to 8 minutes The method   0.2 to 3 g / l zinc ion,   3 to 50 g / l of phosphate ion (PO_FourCalculated as),   0.001 to 4 g / l manganese ion,   0.001-0.5 g / l polyether, polycarboxylate, polymer phos 1 selected from fonic acid, high-molecular phosphinocarboxylic acid and nitrogen-containing organic polymer Species or higher polymers, and   0.3-4 g / l of chloride ion,   0.01 to 0.2 g / l of nitrite ion,   0.05 to 2 g / l of m-nitrobenzene-sulfonate ion,   0.05 to 2 g / l of m-nitrobenzoate ion,   0.05 to 2 g / l p-nitrophenol,   0.005 to 0.15 g / l of hydrogen peroxide in free or bound form,   0.1 to 10 g / l of hydroxylamine in free or bound form,   0.1 to 10 g / l reducing sugar One or more accelerators selected from Is solved by the method characterized by including.   The zinc concentration ranges from about 0.3 to about 2 g / l, especially from about 0.8 to about 1.6 g / l. Preferably, there is. A zinc concentration of 1.6 g / l or more, for example, 2-3 g / l It is not particularly advantageous in the process of the invention, while Can increase the amount of sludge produced. Such zinc content can be found in the galvanized table During the phosphating of the surface in the phosphating bath as a result of being removed by the acid Formed in an operating phosphating bath when additional zinc is added to the Can be done. About 1 to about 50 mg / l nickel and about 5 to about 100 mg / l The nitrate content should be as low as possible within the concentration range of In combination with nickel ions and / or cobalt ions By improving the corrosiveness, it contains neither nickel nor cobalt, 0.5 g / 1 compared with a phosphating bath having a nitrate content of And paint adhesion can be improved. Therefore, on the other hand, the performance of the phosphating bath And, on the other hand, a good balance between wastewater treatment technology requirements for the treatment of wash water. Is done.   In a phosphating bath with a reduced heavy metal content, the manganese content is about 0.000. It may be in the range of 1 to about 0.2 g / l. On the other hand, about 0.5 to about 1.5 g / l The manganese content is a normal value.   From German Patent Application 19500927.4, from about 0.2 to about 1.5 g / l Achieved when using a phosphating zinc treatment bath with a range of amounts of lithium ions. It is known that the corrosion resistance is improved. 0.2 to about 1.5 g / l, especially about Lithium contents in amounts ranging from 0.4 to about lg / l are suitable for the passivation after integration according to the invention. It has a favorable effect on corrosion resistance in the phosphating treatment accompanied by phosphatization. Rin Incorporation into the phosphate layer or at least a favorable effect on the crystal growth of the phosphate layer In addition to the above cations having a phosphating bath, the phosphating bath generally comprises sodium ion Contains potassium, potassium and / or ammonium ions to control free acids I do. The concept of free acids is well known to those skilled in the art of phosphating. You. In the examples, the methods selected herein for measuring free and total acids are used. Is shown. Free and total acids have a significant effect on bed weight and It is an important control variable for the phosphate treatment bath. For phosphating parts Is the free acid value from 0 to 1.5 points, 2.5 poise for continuous phosphating. Values, as well as total acid values in the range of about 15-30 points, are within the ordinary technical scope. The values in the box are suitable for the present invention.   In a phosphating bath suitable for various substrates, the full Oride and / or free fluoride up to 2.5 g / l total fluoride It is customary to add free fluoride up to 1 g / l. I have. The presence of fluoride in such an amount allows the phosphating of the present invention. Benefits are also provided during the bath. If fluoride is not present, bath al The minium content does not exceed 3 mg / l. If fluoride is present, the complex forms The concentration of uncomplexed aluminum is 3 mg Higher aluminum contents are acceptable provided that they do not exceed / l. Obedience The surface to be phosphated is at least partially aluminum or Use fluoride-containing baths if they contain aluminum Is advantageous. In such cases, do not use fluoride that binds to complex compounds Is preferred, but only free fluoride is used at a concentration of 0.5 to 1.0 g / l Is preferred.   For phosphating the zinc surface, the phosphating bath contains a so-called accelerator. It is not always necessary. However, when phosphating the steel surface, Requires that the phosphating solution include one or more accelerators. The accelerator is It is common in the prior art as a component of a zinc phosphate treatment bath. They are gold The genus surface chemically binds to hydrogen produced as a result of being attacked by the acid, It is understood that it contains substances that are themselves reduced. Oxidative accelerator Is a trivalent form of iron (II) ions released by corrosive attack on the steel surface. It has an action of oxidizing to a state, and therefore, precipitation can occur as iron (III) phosphate.   The phosphating bath of the present invention comprises, as an accelerator, the following components:   0.3-4 g / l of chloride ion,   0.01 to 0.2 g / l of nitrite ion,   0.05 to 2 g / l of m-nitrobenzene-sulfonate ion,   0.05 to 2 g / l of m-nitrobenzoate ion,   0.05 to 2 g / l p-nitrophenol,   0.005 to 0.15 g / l of hydrogen peroxide in free or bound form,   0.1 to 10 g / l of hydroxylamine in free or bound form,   0.1 to 10 g / l reducing sugar One or more of the following:   When phosphating galvanized steel, use as little phosphating solution as possible. Contains nitrate. Higher nitrate concentrations are known as pin-holes (p inholing) ", the nitrate concentration should exceed 0.5 g / l Should not be. This results in a white crater-like defect in the phosphate layer. Means that Furthermore, paint adhesion on the galvanized surface may be impaired.   The use of nitrite (nitrite) as an accelerator, especially on steel surfaces Technically satisfactory results. However, industrial safety (acid Use of nitrite as an accelerator. Not recommended. Nitrites can form from nitrites, Can cause pinhole problems as described above or paint Phosphates on the galvanized surface for technical reasons Processing is encouraged to do so.   A particularly preferred accelerator is hydrogen peroxide for environmental compatibility reasons, and Hydroxyl groups for technical reasons related to simplifying the preparation of Min. The combined use of these two accelerators, however, Is not recommended because hydroxylamine is decomposed by hydrogen peroxide. Liberation When hydrogen peroxide in the form or in the form of a bond is used as the promoter, it is 0.005-0. A concentration of 02 g / l hydrogen peroxide is particularly preferred. Hydrogen peroxide is a phosphate-treated solution It can be added to the liquid as it is. However, heating in a phosphating bath water In the form of a compound that forms hydrogen peroxide as a result of the decomposition reaction It is also possible to add hydrogen peroxide. Examples of such compounds include persalts (pe r-salts), for example perborate, percarbonate, peroxosulfate or peroxo Disulfate and the like. Other suitable sources of hydrogen peroxide include ionic peroxides. For example, alkali metal peroxides. In a preferred embodiment of the present invention, phosphate For the treatment, use a combination of hydrogen peroxide and chlorate ions by an immersion method. Also included. In this embodiment, the concentration of the chlorate is, for example, 2-4 g / l. Yes, the concentration of hydrogen peroxide may be from 10 to 50 ppm.   The use of reducing sugars as accelerators is known from US Pat. No. 5,378,292. You. According to the present invention, they are from about 0.01 to about 10 g / l, preferably about 0.5 It can be used in amounts ranging from up to about 2.5 g / l. Examples of such reducing sugars Include galactose, mannose and especially glucose (dextrose) .   In yet another preferred embodiment of the present invention, the promoter is hydroxylamine Is included. Hydroxylamine, as a free base, Oxy is a condensation product of hydroxylamine and ketone Or in the form of a hydroxylammonium salt. Liberation Adding hydroxylamine to the phosphating bath or phosphating concentrate When added in, most of them are hydroxy due to the acid nature of their solutions. It will be present in the form of luammonium cation. Hydroxyl ammonium When used in the form of a salt, sulfates and phosphates are particularly preferred. In the case of phosphates, salts of the acids are preferred since they have better solubility. Hid Roxylamine or its compound has a calculated free hydroxylamine concentration of 0. . Phosphoric acid in an amount such that it ranges from 1 to 10 g / l, preferably 0.3 to 5 g / l Added to salting bath. Phosphating baths provide up to 0.5 g / l of nitrate Accordingly, it is preferable to contain hydroxylamine as a sole accelerator. Obedience Thus, in a preferred embodiment, the phosphating bath contains other known accelerators, such as If nitrite, oxoanion of halogen, peroxide or nitrobenzene Used without any of sulfonates and the like. About 1 effective side effect . Phosphated structures with hydroxylamine concentrations above 5 g / l To reduce the risk of rust formation in poorly immersed areas of material parts it can.   When the phosphating method is applied to the steel surface, iron is in the form of iron (II) ions in the solution. Melts in a state. The phosphating bath of the present invention contains a substance that oxidizes divalent iron ions. Otherwise, divalent iron is converted to a trivalent state as a result of air oxidation, and It can precipitate as iron (III) acid. It uses, for example, hydroxylamine That is the case. Thus, iron (II) ions which can be formed in the phosphating bath The content is significantly higher than in the case of baths containing oxidizing agents. in this case, Iron (II) concentrations up to 50 ppm are normal and values up to 500 ppm In a short time. The concentration of these iron (II) ions depends on the phosphorus content of the present invention. Not so harmful for the salting method. If hard water is used, phosphate treatment The bath contains the hardness-forming cations Mg (II) and Ca (II) in a total concentration of up to 7 mm / l I can do it. Mg (II) or Ca (II) is present in the phosphating bath in amounts up to 2.5 g / l. Can be added.   The weight ratio of phosphate ions to zinc in the phosphating bath is 3.7-3. It can vary over a wide range provided that it is within the range of 0. 10 A weight ratio in the range of to 20 is particularly preferred. When discussing phosphate levels, The total phosphorus content of the phosphate bath is considered to be in the form of phosphate ions. You. Therefore, in calculating the weight ratio, generally, the pH of the phosphating bath is about 3 to When it is in the range of about 3.6, it is actually in the form of a trivalent negatively charged anion. The fact that there is a very small amount of phosphate ion (phosphate ion) , Is not really considered. At these pH values, the phosphoric acid is not dissociated With a small amount of phosphate and a divalent negatively charged monohydrogenphosphate anion, It is considered that a charged dihydrogen phosphate anion is mainly present.   The organic polymer used in the present invention has a content of about 500 to about 50,000, especially about 800 Molecular weight in the range of from about 20,000 to about 20,000 (e.g., gel permeation chromatograph (Which can be measured by GPC).   The phosphating bath contains the organic polymer at a concentration ranging from about 0.01 to about 0.1 g / l. It is preferred to contain. At lower concentrations, the required passivation effect Lost. At higher concentrations, the effect is not substantially increased and therefore It is not economically favorable.   Polymers that can be used in the present invention belong to various chemical groups. May be. Common to them is that oxygen and / or nitrogen atoms can be replaced by polymer chains or It means that it has any of the side chains. The simplest type of polymer is poly Alkylene glycols such as polyethylene glycol or polypropylene glycol Preferably, the coal has a molecular weight of 500 to 10,000. No. Polymeric carboxylic acids such as acrylic acid, methacrylic acid and maleic acid Or a copolymer or the like is also preferable, and a polymeric phosphonic acid or a polymeric phosphinocarbo Acids are also suitable. As an example, polyphosphinocarboxylic acid is an acrylic acid. Sodium hypophosphate phosphite copolymer can also be referred to as FMC Co. Marketed as “Belclene® 500” by Poration (UK) You.   The organic polymer contains an amino group and has the following general formula (I): [Wherein, R¹And R^TwoMay be the same or different and represent a hydrogen or carbon atom Alkyl groups of formulas 1 to 6, for example, a methyl group, an ethyl group, an n-propyl group, Propyl group, n-butyl group, isobutyl group, t-butyl group, amyl group, n-hexyl Or an isohexyl group or a dicyclohexyl group. ] A homopolymer compound comprising the structural unit represented by Can be selected from copolymer compounds.   An extensive list of such polymers is given in DE-A-440 930. No. 6 and incorporated herein by reference. . Specific examples include N-vinyl-formamide, N-vinyl-N-methyl-form Amide, N-vinyl-acetamide, N-vinyl-N-methyl-acetamide, N-vinyl-N-ethyl-acetamide, N-vinyl-propionamide and N − There is vinyl-N-methyl-propionamide and N-vinyl-formamide is non- It is preferable because it always has easy hydrolyzability. Preferred comonomers have carbon atoms 3-8 monoethylenically unsaturated carboxylic acids and water-soluble salts of these monomers It is.   The organic polymer also has the general formula (II): [Wherein, n is a numerical value from 5 to 100, and x is each independently hydrogen and / or CRR₁OH groups (where R and R₁Are hydrogen and a fatty acid having 1 to 12 carbon atoms, respectively. An aliphatic and / or aromatic group. ). ] May be selected from the poly-4-vinylphenol compounds represented by   These polymers are divided into German patents (DE-C) 3146265. After washing solution. According to this specification, at least one x Is CH_TwoPoly-4-vinylphenol compounds of the type which are OH are particularly preferred. It is. The production method is described in the above-mentioned literature.   More preferred organic polymers to use contain amino groups and are shown below. At least one selected from the group consisting of general formulas (a), (b), (c) and (d) One selected from a homopolymer compound or a copolymer compound containing one kind of polymer. Machine polymer,   (A) has the general formula: [Wherein, R₁~ R_ThreeIs hydrogen, carbon atom number independently for each structural unit Selected from the group consisting of an alkyl group having 1 to 5 or an aryl group having 6 to 18 carbon atoms. Y₁~ Y_FourIs, independently for each structural unit, hydrogen, -CR₁₁ R_FiveOR₆, -CH_TwoCl or an alkyl group having 1 to 18 carbon atoms or aryl Or a group of formula Z: Is a group selected from the groups represented by Is a substance, Y₁, Y_Two, Y_ThreeOr Y_FourAt least one is a group represented by the formula Z Must be; R for each unit_Five~ R₁₂Are each independently hydrogen, Alkyl group, aryl group, hydroxyalkyl group, aminoalkyl group, mercapto An alkyl group or a phosphonoalkyl group;₁₂Is -O^(-1)Or with OH May be; W for each unit₁Is independently hydrogen, an acyl group, Cetyl group, benzoyl group, 3-allyloxy-2-hydroxy-propyl group; Nzoyloxy-2-hydroxy-propyl group: 3-butoxy-2-hydroxy-pro Pill group; 3-alkyloxy-2-hydroxy-propyl group; 2-hydroxy-octyl 2-hydroxy-alkyl group; 2-hydroxy-2-phenylethyl group; Droxy-2-alkyl-phenylethyl group; benzyl group; methyl group; ethyl group; Propyl group; alkyl group; allyl group; alkyl-benzyl group; haloalkyl group; Haloalkenyl group; 2-chloropropenyl group; sodium; potassium; tetra-a Reel ammonium; tetra-alkyl ammonium; tetra-alkyl phosphoni ; Tetra-arylphosphonium or ethylene oxide, propyleneoxy Or a condensation product of a mixture thereof or a copolymer thereof. ] A polymer substance having at least one unit represented by: (B) has the general formula: [In the formula, R for each unit₁And R_TwoAre independently hydrogen and carbon atoms Selected from the group consisting of an alkyl group having 1 to 5 or an aryl group having 6 to 18 carbon atoms. Group Y₁~ Y_ThreeIs each independently hydrogen, -CR_FourR_FiveOR₆, -CH_TwoCl or carbon An alkyl or aryl group having 1 to 18 atoms or a formula Z: Is a group selected from the groups represented by₁, Y_TwoOr Y_Three Must be a group of formula Z; R for each unit_Four ~ R₁₂Is independently hydrogen, an alkyl group, an aryl group, Kill group, aminoalkyl group, mercaptoalkyl group or phosphonoalkyl group And R₁₂Is -O^(-1)Or OH; for each unit, W_TwoIs Each independently represents hydrogen, an acyl group, an acetyl group, a benzoyl group, Xy-2-hydroxy-propyl group; 3-benzoyloxy-2-hydroxy-propyl Group; 3-alkyl-benzoyloxy-2-hydroxy-propyl group; 3-phenoxy C-2-hydroxy-propyl group; 3-alkyl-phenoxy-2-hydroxy-pro Pill group; 3-butoxy-2-hydroxy-propyl; 3-alkyloxy-2-hydro 2-hydroxy-octyl group; 2-hydroxy-alkyl group; 2- Hydroxy-2-phenylethyl group; 2-hydroxy-2-alkyl-phenylethyl Group; benzyl group; methyl group; ethyl group; propyl group; alkyl group; Lequil- Benzyl group; haloalkyl group; haloalkenyl group; 2-chloropropenyl group; Is a condensation product of ethylene oxide, propylene oxide or a mixture thereof It is. ] A polymer substance having at least one unit represented by:   (C) is at least partially represented by the formula: [Where W₁, Y₁~ Y_Four, And R₁~ R_ThreeIs as described above for the polymer (a) Same as the ones. ] And at least a part of this portion is made of acrylonitrile , Methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl alcohol Acetate, vinyl methyl ketone, isopropenyl methyl ketone, acrylic acid, Tacrylic acid, acrylamide, methacrylamide, n-amyl methacrylate, Styrene, m-bromostyrene, p-bromostyrene, pyridine, diallyl-di Methyl ammonium salt, 1,3-butadiene, n-butyl acrylate, t-butyl Tylaminoethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate Acrylate, n-butyl vinyl ether, t-butyl vinyl ether, m-chloro Rostyrene, o-chlorostyrene, p-chlorostyrene, n-decyl methacrylate N, N-diallyl-melamine, N, N-di-n-butylacrylamide, -N-butyl itaconate, di-n-butyl maleate, diethylamino-ethyl Methacrylate, diethylene glycol monovinyl ether, diethyl fumare , Diethyl itaconate, diethyl-vinyl phosphate, vinyl-phospho Acid, diisobutyl maleate, diisopropyl itaconate, diisopropyl Maleate, dimethyl fumarate, dimethyl itaconate, dimethyl maleate , Di-n-nonyl fumarate, di-n-nonyl maleate, dioctyl fumarate , Di-n-octyl itaconate, di-n-propyl itaconate, N-dodecy Vinyl ether, acid ethyl fumarate, acid ethyl fumarate, ethyl acetate Acrylate, ethyl cinnamate, N-ethyl-methacrylamide, ethyl meth Acrylate, ethyl vinyl ether, 5-ethyl-2-vinyl-pyridine, 5- Ethyl-2-vinyl-pyridine-1 oxide, glycidyl acrylate, glycidyl Zyl methacrylate, n-hexyl methacrylate, 2-hydroxy-ethyl Tacrylate, 2-hydroxy-propyl methacrylate, isobutyl methacrylate Acrylate, isobutyl vinyl ether, isoprene, isopropyl methacrylate , Isopropyl vinyl ether, itaconic acid, lauryl methacrylate, N-meth Tyrol acrylamide, N-methylol-methacrylamide, N-isobutoki C-ethylacrylamide, N-isobutoxy-methyl-methacrylamide, N -Alkyloxy-methyl acrylamide, N-alkyloxy-methyl methacrylate Rilamide, N-vinyl-caprolactam, N-methyl-methacrylamide, α -Methylstyrene, m-methyl-styrene, o-methyl-styrene, p-methyl -Styrene, 2-methyl-5-vinylpyridine, 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-na Phthalene, 2-vinyl-naphthalene, 2-vinyl-pyridine, 4-vinyl-pyri Gin, 2-vinyl-pyridine N-oxide, 4-vinyl-pyrimidine, N-vinyl One or more monomer units independently selected from the group consisting of le-pyrrolidone A copolymer material that has been polymerized with   (D) is (a), (b), (c) or a condensable form of a mixture thereof, Selected from the group consisting of phenols, tannins, novolak resins, and lignin compounds And another compound is condensed with an aldehyde, a ketone or a mixture thereof. To form a condensation resin product, at least one of which By adding a group represented by the above formula Z to the (1) aldehyde or Ketones, (2) further reacting with secondary amines to form final addition products which can react with acids The condensation polymer formed from the polymer substance (a), (b) or (c) Organic polymers, such as those comprising a polymeric material.   A method for preparing such a polymer is described in the aforementioned European Patent Application Publication (EP-B) 31. No. 9016 and No. 319017. This type of polymer is Henkel Corporation, Parker Amchen Di Vision (Parker Amchen Division), United States (USA)) ) (Registered trademark) 95C, Deoxylyte (registered trademark) 90A, 95A , 95AT, 100NC and TD-1355-CW. Wear.   In this context, particularly preferred polymers are the organic polymer groups of the formula Z At least a part of which has 3 to 8 carbon atoms of ketose or aldose, and an amine or Is a polyhydroxy-alkylamine functionality obtained by condensation with ammonia It has.   Further examples of such polymers are polyvinylphenol and formaldehyde. And a condensation product of para- or paraformaldehyde with a secondary organic amine. In this case, the polyvinyl phenol starts with a molecular weight of about 1000. Thus, those having a molecular weight of about 10,000 are preferred. Particularly preferred condensation products In the composition, the secondary organic amine is methylethanolamine and N-methylglucamine. It is a condensation product selected from the following:   Within the above concentration range, the organic polymer is stable in the phosphating bath, No precipitate is formed. These do not adversely affect the formation of the layer and are therefore It does not lead to a passivation phenomenon on the metal surface, which can suppress the growth of the acid salt crystals.   The organic polymer has the formula: Can also be selected from substituted polyalkylene derivatives containing the structural unit represented by .   Where R¹, R^Two, R^ThreeAre preferably hydrogen. x is 1 Ah Preferably. Accordingly, substituted polyethylene is a particularly preferred polymer. The following formula: Organic polymers having one or more structural units represented by are particularly preferred. .   In a further preferred embodiment, the organic polymer is a high molecular sugar derivative containing an amino group. You. An example of such a polymeric sugar derivative is chitosan, for example, of the formula:May have a structural group represented by   For all organic polymers containing nitrogen atoms, the relationship between the pH of the phosphating solution and By the way, at least some of the nitrogen atoms are protonated, thus carrying a positive charge That is true.   Phosphating baths are generally handled in the form of an aqueous concentrate, which is in situ (in si tu), adjusted to the concentration used by adding water. In terms of stability, These concentrates may contain excess phosphoric acid, thus diluting the bath concentration In some cases, the concentration of free acid is initially quite high and the pH value is rather low. You. The value of the free acid may be an alkali, such as sodium hydroxide, sodium carbonate or It can be reduced to the required range by adding ammonia You. The free acid content is a consequence of, and possibly promoting, the layer-forming cations. Over time while the phosphating bath is in use as a result of the decomposition reaction of the promoter May increase. In such cases, the occasional addition of alkali can lead to free acid Need to be readjusted to the required range. This means that the phosphating bath Alkali metal or ammonium ion content varies widely And the use of dealkalisation during the use of the phosphating bath. Therefore, the free acid tends to increase. Therefore, alkali metal The weight ratio of ions and / or ammonium ions to, for example, zinc ions is: It can be very low for freshly prepared phosphating baths, for example 0.05 May be 0, and may be 0 in some cases. As a result, it rises over time, resulting in a value of 1 or more and 10 or less. Sometimes it reaches the top. In general, low zinc phosphating baths require more than 8 PO of value_Four ^3-: It is possible to adjust the free acid within a necessary range in the Zn weight ratio. It is necessary to add alkali metal ions or ammonium ions to You. Other components of the bath, such as alkali metal ions and / or ammonium ions, such as For example, the same observation result can be obtained for the ratio to the phosphate ion.   Corrosion due to very high sodium concentration in lithium-containing phosphating baths Sodium has a negative effect on the regulation of free acids, as the beneficial effect of lithium on protection is reduced. It is preferred to avoid using a compound. In such cases, the free acid It is preferable to use a basic lithium compound for the adjustment of the concentration. Alternatively, Kariu System compounds can also be used.   In principle, cations that form or affect the layer are reduced. The form introduced into the phosphate treatment bath is not critical. However, The nitrate content should not exceed the preferred upper limit. Should be avoided. Metal ions introduce other ions into the phosphating solution It is preferred to use them in the form of a compound that does not. For this reason, metal ion It is most advantageous to use the compound in its oxide or carbonate form. Lithium It can also be used in the form of sulfate.   The phosphating bath of the present invention can be used for steel, galvanized steel or galvanized steel, Luminium, aluminum-plated steel or aluminum alloy-plated steel, and It is suitable for phosphate treatment of a surface made of an aluminum-magnesium alloy or the like. The term "aluminum" as used herein is technically normal. Aluminum alloy, for example, AlMg_0.5Si_1.4including. The above materials are automatic car It is becoming more common in the manufacturing industry in recent years, it can.   In this connection, parts of the vehicle body are also, for example, Bonazink (registered trademark) ) Form using materials that have already been pretreated, such as is done in the process. It can also be done. Here, the substrate material is first chromated or phosphated. Treatment (phosphate treatment) and then coating with an organic resin. Of the present invention The phosphating method involves remedying the damaged area of the pretreatment layer or the untreated opposite side. The phosphate treatment is performed.   The method of the invention is suitable for application by dipping, spraying or spraying / dipping. This one The method can be used especially in the automobile manufacturing industry, in which case the processing time is 1 to 8 Minutes, especially 2 to 5 minutes, are conventional. However, continuous phosphating in steel mills , A processing time of 3 to 12 seconds can be used. Continuous phosphoric acid If a salt treatment is performed, the bath concentration is in each case in the preferred range of the invention. It is desirable to adjust to the upper half range of the box. For example, when the zinc concentration is 1.5 to 2. 5 g / l and a free acid content of 1.5 to 2.5 points. In particular Substrates for continuous phosphating are, in particular, galvanized and electrolytic galvanized steel. Is preferred.   Suitable bath temperatures, as is customary in other known phosphating baths, depend on the application. Regardless of the field, it is in the range of 30 to 70 ° C, and the temperature range of 45 to 60 ° C is preferable. Good.   The phosphating method of the present invention is particularly useful for coating, for example, cathodic electrodeposition coating, for example, Before painting, as is usually done in the automotive industry, The purpose of the present invention is to carry out the treatment of a smooth metal surface. The method of the present invention also includes For example, it is also suitable for pretreatment before powder coating used for household appliances and the like. . The phosphating method is a series of pretreatments that are usually performed in industry, It can be seen as a process. In such a series of operations, cleaning and The steps related to the cleaning and activation of fats, intermediates, and The activation is generally performed using an activator containing titanium phosphate. It is done.Example The phosphating method of the present invention and the method as a comparative example are used for manufacturing automobiles. A thin steel plate ST1405 was tested. Common in the manufacture of car bodies The immersion process was performed according to the following procedure.   1. Alkaline cleaner (Ridoline® 1501, Henke) (Henkel KGaA product), 2% batch in tap water, 55 ° C, 4 Minutes.   2. Washing with tap water, room temperature, 1 minute.   3. An activator containing titanium phosphate (Fixodine (registered trademark) 950) , Henkel product), 0.1% batch in deionized water, room temperature, 1 minute while.   4. The following ingredients:     1.0 g / l Zn²⁺,     1.0 g / l Mn²⁺,     0.1 g / l Fe²⁺,     14g / l PO_Four ^3-,     0.95 g / l SiF₆ ^2-,     0.2 g / l F^-,as well as     1.7 g / l of (NH_ThreeOH)_TwoSO_Four,   And polymers as shown in the table Using a phosphating bath containing In addition to the above cations, nitrate-free phosphating baths can be used if necessary. Contained sodium ions to control the free acid content. Free acid poi The number of points was 0.9, the number of points for all acids was 23 and the pH value was 3.35. Was. The number of free acid points is required to titrate 10 ml of the bath solution to a pH of 3.6. It is understood to be the consumption of 0.1 N sodium hydroxide in ml. same Thus, the total acid points indicate the amount consumed in ml until reaching a pH value of 8.2. .   5. Washing with deionized water.   6. Spray drying with compressed air.   The weight per area ("layer weight") is determined according to DIN 50942. It was determined by dissolving in a 5% chromic acid solution. This is shown in the table You.   The phosphate-treated test piece was coated with a cathodic immersion paint (FT8, available from BASF). 5-7042). Corrosion resistance tests were performed by Fau d Zel Klima Test (VDA-Wechselklimatest, Alternating Weather Test) 621-415 For 9 cycles. The result is calculated in steps (Lacku nterwanderung).Table: Phosphating bath and phosphating results (*) Polyvinylphenol (molecular weight 3000, gel permeation Matrix (GPC)) and paraformaldehyde and glucamine (Pa rker Amchen, USA). (**) Same as above Mannich reaction product, except that the molecular weight of polyvinylphenol Is 8600.

Claims (1)

[Claims]   1. Steel, galvanized or galvanized steel, aluminum and / or A metal surface made of an aluminum-magnesium alloy is treated with a phosphate treatment containing zinc. Phosphate by contacting by dipping or spraying in a liquid for a time ranging from 3 seconds to 8 minutes A method of processing,   The phosphating solution is   0.2 to 3 g / l zinc ion,   3 to 50 g / l of phosphate ion (PO_FourCalculated as),   0.001 to 4 g / l manganese ion, and   0.001-0.5 g / l polyether, polycarboxylate, polymer phos 1 selected from fonic acid, high-molecular phosphinocarboxylic acid and nitrogen-containing organic polymer Species or higher polymers, and   0.3-4 g / l of chloride ion,   0.01 to 0.2 g / l of nitrite ion,   0.05 to 2 g / l of m-nitrobenzene-sulfonate ion,   0.05 to 2 g / l of m-nitrobenzoate ion,   0.05 to 2 g / l p-nitrophenol,   0.005 to 0.15 g / l of hydrogen peroxide in free or bound form,   0.1 to 10 g / l of hydroxylamine in free or bound form, and   0.1 to 10 g / l reducing sugar One or more accelerators selected from A method comprising:   2. The phosphating solution is 1-50 mg / l nickel ions and / or 2. The composition according to claim 1, further comprising 100 mg / l of cobalt ions. the method of.   3. The phosphating solution may further comprise 0.2-1.5 g / l of lithium ions. The method according to claim 1 or 2, wherein:   4. The phosphating solution converts the fluoride, in each case F^-Calculated as Up to 2.5 g / l total fluoride, including up to 1 g / l free fluoride Contract The method according to any one of claims 1 to 3.   5. The phosphating solution contains 5-150 mg / l of hydrogen peroxide as an accelerator. A method according to any of claims 1 to 4, comprising in free or bound form.   6. The phosphating solution contains 0.1 to 10 g / l of hydroxyl as an accelerator. A method according to any of claims 1 to 4, comprising the amine in free or bound form. .   7. A phosphating solution comprising at least 0.5 g / l of nitrate. 7. The method according to any one of claims 1 to 6.   8. The phosphating solution is an organic polymer at a concentration ranging from 0.01 to 0.1 g / l. The method according to any one of claims 1 to 7, comprising:   9. The organic polymer is a polyalkylene having a molecular weight of 500 to 10,000. The method according to any one of claims 1 to 8, which is a recall.   10. The organic polymer contains an amino group and has the following general formula (I): [Wherein, R¹And R^TwoMay be the same or different and represent a hydrogen or carbon atom It is an alkyl group of the formulas 1 to 6. ] A homopolymer compound comprising the structural unit represented by The method according to any one of claims 1 to 8, wherein is selected from copolymer compounds.   11. The organic polymer has the general formula (II): [Wherein, n is a numerical value from 5 to 100, and x is each independently hydrogen and / or CRR₁OH groups (where R and R_FourAre hydrogen and a fatty acid having 1 to 12 carbon atoms, respectively. An aliphatic and / or aromatic group. ). ] 9. The method according to claim 1, which is selected from poly-4-vinylphenol compounds represented by The method according to any of the above.   12. The organic polymer contains an amino group and has the following general formulas (a), (b), Homopolymer containing at least one polymer selected from the group consisting of (c) and (d) A polymer selected from a polymer compound or a copolymer compound,   (A) has the general formula: [Wherein, R₁~ R_ThreeIs hydrogen, carbon atom number independently for each structural unit Selected from the group consisting of an alkyl group having 1 to 5 or an aryl group having 6 to 18 carbon atoms. Y₁~ Y_FourIs, independently for each structural unit, hydrogen, -CR₁₁ R_FiveOR₆, -CH_TwoCl or an alkyl group having 1 to 18 carbon atoms or aryl Or a group of formula Z: Is a group selected from the groups represented by Is a substance, Y₁, Y_Two, Y_ThreeOr Y_FourAt least one is a group represented by the formula Z Must be; R for each unit_Five~ R₁₂Are each independently hydrogen, Alkyl group, aryl group, hydroxyalkyl group, aminoalkyl group, mercapto An alkyl group or a phosphonoalkyl group;₁₂Is -O^(-1)Or with OH May be; W for each unit₁Is independently hydrogen, an acyl group, Cetyl group, benzoyl group, 3-allyloxy-2-hydroxy-propyl group; Nzo Yloxy-2-hydroxy-propyl group; 3-butoxy-2-hydroxy-propyl Group; 3-alkyloxy-2-hydroxy-propyl group; 2-hydroxy-octyl group 2-hydroxy-alkyl group; 2-hydroxy-2-phenylethyl group; 2-hydro Xy-2-alkyl-phenylethyl group; benzyl group; methyl group; ethyl group; Pill group; alkyl group; allyl group; alkyl-benzyl group; haloalkyl group; Alkenyl group; 2-chloropropenyl group; sodium; potassium; tetra-aryl Ruammonium; tetra-alkylammonium; tetra-alkylphosphonium A tetra-arylphosphonium or ethylene oxide or propylene oxide Or a condensation product of these mixtures or a copolymer thereof. ] A polymer substance having at least one unit represented by:   (B) has the general formula: [In the formula, R for each unit₁And R_TwoAre independently hydrogen and carbon atoms Selected from the group consisting of an alkyl group having 1 to 5 or an aryl group having 6 to 18 carbon atoms. Group Y₁~ Y_ThreeIs independently hydrogen, -CR_FourR_FiveOR₆, -CH_TwoCl or carbon source An alkyl or aryl group having 1 to 18 children or a formula Z:Is a group selected from the groups represented by₁, Y_TwoOr Y_Three Must be a group of formula Z; R for each unit_Four ~ R₁₂Is independently hydrogen, an alkyl group, an aryl group, Kill group, aminoalkyl group, mercaptoalkyl group or phosphonoalkyl group And R₁₂Is -O^(-1)Or OH; for each unit, W_TwoIs Each independently represents hydrogen, an acyl group, an acetyl group, a benzoyl group, or a 3-allyloxy group; C-2-hydroxypropyl group; 3-benzoyloxy-2-hydroxy-propyl Group; 3-alkyl-benzoyloxy-2-hydroxy-propyl group; 3-phenoxy -2-hydroxy-propyl group; 3-alkyl-phenoxy-2-hydroxy-propyl Group; 3-butoxy-2-hydroxy-propyl; 3-alkyloxy-2-hydroxy- Propyl group; 2-hydroxy-octyl group; 2-hydroxy-alkyl group; 2-hydr Roxy-2-phenylethyl group; 2-hydroxy-2-alkyl-phenylethyl group; Benzyl group; methyl group: ethyl group; propyl group; alkyl group; allyl group; Haloalkyl group; haloalkenyl group; 2-chloropropenyl group; Or condensation formation of ethylene oxide, propylene oxide or a mixture thereof Things. ] A polymer substance having at least one unit represented by:   (C) is at least partially represented by the formula: [Where W₁, Y₁~ Y_Four, And R₁~ R_ThreeIs as described above for the polymer (a) Same as the ones. ] And at least a part of this portion is made of acrylonitrile , Methacrylonitrile, methyl acrylate, methyl methacrylate, vinyl alcohol Acetate, vinyl methyl ketone, isopropenyl methyl ketone, acrylic acid, Tacrylic acid, acrylamide, methacrylamide, n-amyl methacrylate, S Tylene, m-bromostyrene, p-bromostyrene, pyridine, diallyl-dimethyl Tyl ammonium salt, 1,3-butadiene, n-butyl acrylate, t-butyl L-aminoethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate Relate, n-butyl vinyl ether, t-butyl vinyl ether, m-chloro Styrene, o-chlorostyrene, p-chlorostyrene, n-decyl methacrylate G, N, N-diallyl-melamine, N, N-di-n-butylacrylamide, di- n-butyl itaconate, di-n-butyl maleate, diethylamino-ethyl Methacrylate, diethylene glycol monovinyl ether, diethyl fumaray G, diethyl itaconate, diethyl-vinyl phosphate, vinyl-phosphone Acid, diisobutyl maleate, diisopropyl itaconate diisopropyl maleate Ethate, dimethyl fumarate, dimethyl itaconate, dimethyl maleate, di -N-nonyl fumarate, di-n-nonyl fumarate, dioctyl fumarate, Di-n-octyl itaconate, di-n-propyl itaconate, N-dodecyl Vinyl ether, acid ethyl fumarate, acid ethyl fumarate, ethyl acetate Relate, ethyl cinnamate, N-ethyl-methacrylamide, ethyl methacrylate Acrylate, ethyl vinyl ether, 5-ethyl-2-vinyl-pyridine, 5-ethyl 2-vinyl-pyridine-1 oxide, glycidyl acrylate, glycidyl Methacrylate, n-hexyl methacrylate, 2-hydroxy-ethyl methacrylate Acrylate, 2-hydroxy-propyl methacrylate, isobutyl methacrylate G, isobutyl vinyl ether, isoprene, isopropyl methacrylate, Sopropyl vinyl ether, itaconic acid, lauryl methacrylate, N-methylo Acrylamide, N-methylol-methacrylamide, N-isobutoxy- Ethyl acrylamide, N-isobutoxy-methyl-methacrylamide, N-A Alkyloxy-methyl acrylamide, N-alkyloxy-methyl methacryl Amide, N-vinyl-caprolactam, N-methyl-methacrylamide, α-meth Butylstyrene, m-methyl-styrene, o-methyl-styrene, p-methyl-s Tylene, 2-methyl-5-vinylpyridine, n-propyl methacrylate, nato Lithium p-styrenesulfonate, stearyl methacrylate, styrene, p- Styrenesulfonic acid, p-styrenesulfonamide, vinyl bromide, 9-bi Nyl-carbazole, vinyl chloride, vinylidene chloride, 1-vinyl-naph Taren, 2-vinyl-naphthalene, 2-vinyl-pyridine, 4-vinyl-pyridi 2-vinyl-pyridine N-oxide, 4-vinyl-pyrimidine, N-vinyl One or more monomer units independently selected from the group consisting of pyrrolidone Is a copolymer material polymerized with   (D) is (a), (b), (c) or a condensable form of a mixture thereof, Selected from the group consisting of phenols, tannins, novolak resins, and lignin compounds And another compound is condensed with an aldehyde, a ketone or a mixture thereof. To form a condensation resin product, at least one of which By adding a group represented by the above formula Z to the (1) aldehyde or Ketones, (2) further reacting with secondary amines to form final addition products which can react with acids The condensation polymer formed from the polymer substance (a), (b) or (c) Have A method according to any of claims 1 to 8.   13. At least a part of the group represented by the formula Z in the organic polymer has 3 to 3 carbon atoms. 8 by condensation of ketose or aldose with amine or ammonia 13. The method of claim 12, having a polyhydroxy-alkylamine functionality.   14． The organic polymer has a molecular weight of about 1,000 to about 10,000. Phenol, formaldehyde or paraformaldehyde, and secondary The method according to claim 12, which is a condensation product with an amine.   15. The secondary organic amine is methylethanolamine and N-methylglucamine; 15. The method according to claim 14, wherein the method is selected from the group consisting of:   16. Organic polymer, formula: [Wherein, R¹, R^Two, R^ThreeIs independently a hydrogen or a methyl group or An ethyl group, x is a numerical value of 1, 2, 3, or 4, Y has at least one nitrogen atom, and the nitrogen atom is an alkylamino group or Is contained in a saturated or unsaturated mononuclear or polynuclear heterocyclic compound. ] 2. The method according to claim 1, which is selected from substituted polyalkylene derivatives containing a structural unit represented by The method according to any one of claims 1 to 8.   17． R¹, R^Two, R^ThreeIs hydrogen, and x is 1. The method described.   18. The organic polymer has the formula: 18. The method according to claim 16, which has one or more structural units represented by Method.   19. The organic polymer is a high molecular sugar derivative containing an amino group. 9. The method according to any one of items 8.   20. The high molecular sugar derivative has the formula:20. The method according to claim 19, which has a structural group represented by: