JPH10140366A - Medium-temperature manganese phosphate chemical coating solution and chemical conversion treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a chemical film suitable as a high-quality substrate for coating materials, etc., on the surface of a metal by bringing an acidic aq. composition having specified contents of maganeses (II) action and phosphate anion and with the free acidity and total acidity specified into contact with a metallic substrate under specified conditions. SOLUTION: An acidic aq. composition contg. water, 0.30-4.0ppt dissolved manganese (II) cation and the dissolved phosphate anion with the ratio of the dissolved manganese (II) cation concn. to the dissolved phosphate anion concn. controlled to 1.0:5.0 to 1.0:5.0, having -1.5 to 1.5 free acidity and 4-50 total acidity and contg. 0-0.02% each of zinc cation, nickel cation, calcium cation, etc., is prepared. the composition is brought into contact with a metallic substrate at <=75 deg.C for 5.0min without applying a current in the metallic substrate to form a film at about 1.2g/m. Consequently, a chemical film as a high-quality substrate for coating materials and org. fibers is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to compositions and methods for depositing manganese-containing phosphate conversion coatings on metal surfaces, particularly ferrous metals, galvanized steel surfaces, and other predominantly zinc-based surfaces. The present invention particularly relates to a composition for producing a chemical conversion coating suitable as a high-quality base treatment for paints and similar organic coatings at a temperature of 80 ° C. or lower, and a chemical conversion treatment method using the same.

[0002]

BACKGROUND OF THE INVENTION General methods of forming phosphate conversion coatings are well known in the art. For example, M. Hamache
r, "Eco-environmentally safe pretreatment of metal surfaces", Hen
Kel-Referrate 30 (1994), pp.
138-143. This document is hereby incorporated by reference, except for parts contrary to the description in this specification. Briefly, when an active metal such as iron or zinc is brought into contact with an aqueous acidic composition containing a sufficient concentration of phosphate ions, a chemical conversion film containing phosphate ions and metal cations is deposited on the active metal surface. . The metal cation is provided by dissolution of the phosphated active metal, from a metal cation having at least divalent valency present in the aqueous acidic composition, or from both. . In many cases, especially when the phosphating solution contains zinc, nickel or manganese, to increase the speed of the process and improve the uniformity of the film, it is usually included in the film formed. It is common to include in the aqueous acidic composition a component called an "accelerator" that does not come. Representative promoters that are widely used include nitrite and chlorate ions, water-soluble nitroaromatic organic compounds such as p-nitrobenzenesulfonic acid, and hydroxylamine. Hydroxylamine is almost always in the form of a salt or complex, and at concentrations where it is normally used, one of the functions of most other accelerators is Fe,
It differs from most other promoters in that it is not an oxidizer that is strong enough to oxidize (II) ions to Fe (III) ions.

Prior art phosphating solutions containing manganese as substantially the only metal cation having a valence of 2 or more are known and have been used in the past. However, such processing solutions have been used in practice only at relatively high temperatures, almost always above 80 ° C., and often above 88 ° C. Such treatments have a bad reputation due to their tendency to sludge, and this phenomenon occurs in almost all phosphate conversion treatments, and these treatments contain manganese as the main cation having a valence of 2 or more. If it does, it will worsen quantitatively.

Furthermore, such prior art manganese-based chemical conversion coatings are thick, usually giant crystalline conversion coatings,
During cold working of metal objects, it has usually been used only to deposit a conversion coating thereon, which primarily functions as a lubricant carrier. Although this is an important practical application of phosphating, it is even more important to provide a primer treatment for the paint. However, in the past, this object could not be successfully achieved by a phosphating solution in which divalent manganese ions are substantially the only metal cations having two or more valences. A thick phosphate conversion coating that can be easily formed using a manganese phosphate treatment liquid is too thick and / or too brittle as a coating base, and has an adhesive property to a paint to be applied next and similar substances. Not good. This is thought to be because the thick phosphate film easily cracked even with a rather small mechanical impact.
On the other hand, thinner, usually microcrystalline, as well as phosphate conversion coatings that can be easily formed by phosphating solutions containing at least 0.5 g / L of zinc, nickel, cobalt and / or iron in total. It is practically difficult, if not impossible, to control the manganese phosphate treatment solution to form a phosphate conversion coating that is of the type and has good adhesion to the next applied coating. Was. In addition, it is known that the conventional manganese phosphate treatment composition does not form a chemical conversion film of satisfactory quality when only the object to be treated is sprayed, and generally only immersion treatment is performed.

[0005]

SUMMARY OF THE INVENTION An optional and / or combined object of the present invention is to provide (i) phosphoric acid which forms a high quality coating base for paints and similar topcoats containing organic binders. Providing compositions and methods for salt treatment wherein the predominant divalent or higher cation in the composition is manganese ions; (ii) conventional manganese phosphates (Ii) providing a manganese-containing phosphate conversion coating that can be more easily controlled to reduce the amount of manganese deposited per unit area than is normally obtained using a chemical conversion solution;
i) Relatively economical phosphating, producing a good quality coating substrate similar to current conventional phosphating methods using zinc, nickel and / or cobalt containing conversion solutions. Providing a liquid and a chemical conversion method using the same; (iv) providing a chemical conversion coating having excellent coating quality as a coating base by spraying; and (v) environmental pollution by a phosphating solution. Danger,
(V.1) reducing or eliminating the content of "heavy metals" other than zinc, nickel, cobalt, chromium, copper and / or other manganese, and / or (v.2)
By reducing the amount of sludge generated during use of the phosphating composition, and (vi) converting the conversion coating with excellent coating quality as a coating base to 80 ° C.
Provide at the following phosphating temperatures: Other objects will be apparent from the description below.

[0006]

General Principles of Description Except in the claims and examples, or unless otherwise indicated, the quantity or reaction of substances and / or the conditions of use are expressed in this book. All quantities in the specification are to be interpreted as being modified by the word "about" when indicating the broadest scope of the invention. However, implementation within the numerical limits described is preferred.
Also, throughout this specification, unless stated otherwise, percentages, parts and ratios are by weight; a group or class of substances described as suitable or preferred for a given purpose in relation to the invention. Where appropriate, mixtures of two or more of the members of the group or class are likewise suitable or preferred; the description of a component in chemical terms refers to any combination specified in the specification. In terms of the components at the time of the addition, and does not necessarily exclude the chemical interaction between the components of the mixture once mixed; It is intended that there be sufficient counterion to provide overall electrical neutrality for the composition; the implicitly described counterion is, whenever possible, in ionic form. Among the other components explicitly described in the above, should preferably be selected; otherwise, such counterions, except to avoid counterions that behave inconsistently with the purpose of the invention, The terms "molecules" and "moles" and their grammatical variants are to be chosen freely; not only are substances defined by well-defined neutral molecules, but also ionic and elemental , Or other types of chemical entities defined by the number of atoms of each type present therein; the first definition of an acronym or other abbreviation is the same as defined herein It shall apply to all subsequent uses of the abbreviation, and shall apply mutatis mutandis to the normal grammatical variants of the originally defined abbreviation; the term "paint" shall refer to lacquers, Enamel, d , Shellac, and the like, and are intended to include all analogous substances that may be referred to in more specific terms; and the term "polymer" includes "oligomers,""homopolymers,""copolymers" ,
"Terpolymer" and the like are included.

[0007] has a pH of summary least 3.0 of the Invention, water and (A) 2 divalent manganese cations dissolved, and (B) dissolved phosphate anions, and, optionally, one or more of the following components (C) a dissolved acid component that is not part of any of the above components; (D) (1) (i) a carboxyl moiety and a carboxylate moiety; (ii) a hydroxyl moiety that is not part of the carboxyl moiety; (Iii) a group consisting of an organic acid and an anion thereof, which contains at least two moieties selected from the group consisting of a phosphonic acid moiety and a phosphonate moiety per molecule, and (2) is not a part of any of the above-mentioned components. A dissolved component selected from: (E) a dissolved reducing agent and / or a reaction product therefrom that is not part of any of the components described above. (F) a surfactant component that is not a part of any of the above-mentioned components; and (G) a group consisting of a simple anion and a complex anion that contains a fluorine atom and is not a part of any of the above-mentioned components. (H) a dissolved metal cation component having at least two valences, which is not a part of any of the above components, and (J) not a part of any of the above components. Buffer,
And (K) by using a chemical conversion treatment solution that is not part of any of the above components, contains a biocide, preferably consists essentially of the above components, or more preferably consists of the above components. It has been found that one or more of the above objects of the invention can be achieved.

[0008] Various embodiments of the present invention provide a working compo- sition for direct use in metal processing.
make-up conc. to prepare such a treatment solution by dilution with water and then with water.
entrates), suitable replenishers (replenisher co.) to maintain optimal performance of the processing solutions of the present invention.
ncentrates), a method of treating a metal with the treatment liquid of the present invention, and cleaning and surface conditioning of a surface on which a chemical conversion film is formed before being brought into contact with the present chemical treatment liquid (for example, also known as "Jernsted salts"). Activation of steel surface with titanium phosphate sol to be applied), rinsing, and subsequent painting or similar overcoating process for applying an organic binder-containing protective coating on the metal surface treated according to the narrower aspects of the invention. And extended methods that include additional steps that are conventional per se. Articles of manufacture that include surfaces treated by the method of the present invention also fall within the scope of the present invention.

[0009]

DETAILED DESCRIPTION OF THE INVENTION For various reasons, it may be preferable for the compositions of the present invention as defined above to be substantially free of many of the ingredients used in compositions for similar purposes in the prior art. Specifically, where maximum storage stability of the concentrate, avoidance of potentially troublesome anions, economy and / or minimization of potential contamination is desired, each of the following components that should preferably be minimized: Independently, as the preference increases in a given order, the composition comprises the following components at 25, 15, 9, 5, 3, 1.0,.
35, 0.10, 0.08, 0.04, 0.02,.
Preferably it contains no more than 01, 0.001 or 0.0002%: nitrites, halides and perhalates (ie perchlorates, chlorates, iodates, etc.), hydroxylamine and Complexes of its salts and hydroxylamine, chlorides, bromides, iodides,
Organic compounds containing a nitro group, hexavalent chromium, tetravalent manganese, divalent or higher metal cations other than manganese and iron, ferricyanide, ferrocyanide, and pyrazole compounds. While these components may not be harmful in some cases, minimizing them is usually preferred, at least for economic reasons, since they have not been found necessary or advantageous in the present invention. . In addition, independently of it, unlike most other phosphating solutions and methods, the phosphating nights of the present invention are based on another preferred component according to the present invention, which is required together with the other components. (Specified as a preferable component) preferably does not have an oxidizing power greater than the oxidizing power inherently contained in the oxidizing power. This oxidizing power is in equilibrium with atmospheric gases. For this purpose, the oxidizing power of the composition is
Salt bridges known to those skilled in the electrochemical arts
dge), flow junction (flowing juncti)
on), can be measured by the potential of a platinum electrode immersed in the composition as compared to a standard reference electrode that maintains electrical contact with the composition via a semipermeable membrane or the like.

The dissolved manganese cation required for component (A) is obtained from a soluble manganese salt or from a manganese-containing compound which reacts with manganese metal itself or acid water to form a dissolved manganese cation. Can be. Usually preferred sources are manganese carbonate and manganese oxide, mainly for economic reasons.
(When preparing the concentrate composition of the present invention using manganese oxide, the presence of the reducing agent component (E) as defined above is usually preferred because, in the absence of it, the presence of It is believed that the dissolution rate of MnO is very slow because the reducing agent acts catalytically or at least partially catalytically to speed up the dissolution process because MnO.
This is because the amount of reducing agent required to actually accelerate the dissolution rate of O is much less than the stoichiometrically required to react with any manganese present. )

In the chemical conversion treatment solution of the present invention, the concentration of the dissolved manganese cation is preferably at least 0.1, 0. 1 to 0.
2, 0.30, 0.40, 0.50, 0.60, 0.7
0, 0.80, 0.90, 1.00, 1.10, 1.2
0, 1.30, 1.35, 1.40, 1.45 or 1.49 parts / 1000 parts (hereinafter abbreviated as "ppt")
And, independently of it, are preferably 4.0, 3.5, 3,.
0, 2.7, 2.5, 2.3, 2.2, 2.1, or 2.0 ppt or less. At concentrations below the concentrations listed above as preferred minimums, satisfactory films will not be formed within a reasonable amount of time. Concentrations higher than the concentrations listed above for the preferred maximum generally do not improve the quality of the film formed and are uneconomical.

[0012] The dissolved phosphate ions constituting the essential component (B) can also be obtained from various sources known in the art of forming a general phosphate conversion coating. In the chemical conversion treatment solution of the present invention, the substantial total acidity (total acid)
Because of the preferred values described below for d), it is usually preferred that much of the phosphate ion content be provided by the phosphoric acid added to the composition, but all of the stoichiometric equivalents of phosphate ion Phosphoric acid and all of its anionization products in the undissociated solution of is phosphoric acid equivalent to phosphate ion added to the composition in the form of a salt. Together with the ions, secondary phosphate ions or completely neutralized phosphate ions, they should be understood as forming part of component (B), irrespective of the actual degree of ionization present in the composition. It is. When metaphosphoric acid or condensed phosphoric acid or salts thereof are present in the composition, they are also understood to be part of component (B) in stoichiometric equivalent to phosphate ions. However, it is generally preferred that only orthophosphoric acid and its salts be used for component (B).

In the chemical conversion treatment solution of the present invention, the component (B)
Is preferably at least 5, 6, 7, 8, 9, 10, 1 as increasing preference in the order given.
0.5, 11.0, 11.5, 11.8, 12.0, 1
2.2, 12.4 or 12.6 ppt, and preferably independently, 100, 50, 40, 30, 27, 2 as preference increases in the given order.
4, 21, 19.0, 18.0, 17.0, 16.0,
15.0, 14.0, 13.7, 13.3, 13.0 or 12.8 ppt or less. Independently of the above preferred values, the concentration of component (A): component (B) in the chemical conversion treatment solution of the present invention irrespective of whether it is a treatment solution or a construction bath agent.
Are preferably at least 1.0: 50, 1.0: 4 as increasing preference in the order given.
0, 1.0: 35, 1.0: 30, 1.0: 27, 1.
0:24, 1.0: 21, 1.0: 18, 1.0: 1
6, 1.0: 15, 1.0: 14 or 1.0: 13.
7, and independently preferably, in the order given, increasing preference for 1.0: 5.0, 1..
0: 6.0, 1.0: 7.0, 1.0: 8.0, 1.
0: 8.5, 1.0: 9.0, 1.0: 9.5, 1.
0:10, 1.0: 10.5, 1.0: 11.0, 1..
0: 11.5, 1.0: 12.0, 1.0: 12.5,
1.0: 13.0 or 1.0: 13.3 or less.

Preferably, nitric acid is present in the composition of the present invention, most preferably as the main but not the only component of component (C), although other acids may be present alone or in the composition of the present invention. It can be present with nitric acid. It is recognized that the main purpose of most components (C) is that the total acidity of the compositions of the present invention is greater than that which can be achieved with phosphoric acid alone without exceeding the above preferred maximum for phosphate ions. It is to raise. According to common practice in the art, the total acidity is, for the purposes of this description, a 10 ml exact sample of the composition (a
A "point" defined to be equal to the milliliter ("ml") of 0.1 N NaOH required to titrate 10 ml aliquot sample to pH 8.2 (eg, using a phenolphthalein indicator).
Is measured as

[0015] The total acidity present in the treatment liquid of the present invention is preferably such that the preference increases in the order given.
At least 4, 6, 8, 10, 12.0, 13.0, 1
4.0, 14.5, 15.0, 15.3, 15.5, 1
5.7 or 15.9, and independently of it, preferably 50, 40, 35, 30, 2 as preference increases in the given order, mainly for economic reasons.
5, 20, 18.0, 17.5, 17.0, 16.5 or 16.2 or less.

The "free acidity" of the compositions of the present invention also significantly affects the ability of the processing solution to form high quality phosphate films. The free acidity was determined except that the titration endpoint was pH 3.8 (eg, using a bromophenol blue indicator).
Defined similarly to Total Acidity. If the pH of the composition is at least 3.8 from the beginning, 0.1N instead of NaOH
Titration is performed with a strong acid and is described as the negative free acid or more usually as "consumed acid". The compositions of the present invention preferably have at least -1.5, -1.0, -0.8 in order of increasing preference.
0, -0.70, -0.60, -0.55 or -0.
50, and independently preferably, 1.5, 1.0,
0.80, 0.60, 0.50, 0.40, 0.30,
It preferably has a free acidity of 0.20, 0.15 or 0.10 or less.

Another substance which has been found to be useful as part of component (C) is formic acid, especially formic acid in combination with nitric acid. The concentration of formic acid in the treatment solution of the present invention is preferably at least 0.04, 0.08, 0.15, 0.
20, 0.25, 0.30, 0.35, 0.39 or 0.43 g / L, independently of preference given the order given, mainly for economic reasons, 5, 3.0, 2.0, 1.5, 1.0, 0.90,
0.80, 0.70, 0.65, 0.60, 0.55,
It is 0.50 or 0.45 g / L. Independently of their actual concentrations, when both nitric acid and formic acid are present in the composition according to the invention, the ratio of the concentration of formic acid to the concentration of nitric acid is preferably preferred in the order given. At least 0.002, 0.004, 0.00
6, 0.008, 0.010, 0.015, 0.02
0, 0.023, 0.026, 0.029, 0.032
Or 0.034: 1.0, independently of 0.5, 0.
3, 0.20, 0.10, 0.080, 0.070,
0.060, 0.050, 0.045, 0.041,
0.038 or 0.036: 1.0 or less. The main advantage observed from the presence of formic acid in the composition of the present invention is the more rapid film formation.

When using component (D), one of its important functions is to keep the calcium and magnesium ions, which may be present in the water supply, soluble. Component (D) is not normally required to be present unless the composition of the present invention is to be diluted with hard water. When used, component (D) preferably results from an anion or other molecule containing both at least one carboxyl (carboxylate) moiety and one hydroxyl moiety that is not part of the carboxyl (carboxylate) moiety; citric acid,
Gluconic acid and heptogluonic acid
More preferably, it is obtained from water-soluble salts of C. conic acid) and these acids, most preferably from gluconic acid and its water-soluble salts. Independently of the above, when component (D) is used, the concentration of component (D) in the chemical conversion treatment solution according to the invention is preferably at least 0.4, preferably in the order given, 0.
8, 1.5, 2.0, 2.5, 3.0, 3.5, 4.
0, 4.3, 4.6, 4.8, or 5.0 mmol / liter of the entire composition (hereinafter usually abbreviated as "mM"), and, independently, are used primarily for economic reasons. In this case, the concentration of the component (D) in the treatment liquid of the present invention is preferably 50, 25, 15, 10, 7.0, 5.8, 5 as the preference increases in the order given. .
5 or 5.2 mM or less.

As already mentioned above, the reducing agent component (E)
Is preferably present in the composition of the present invention when producing a concentrated solution by dissolving MnO in phosphoric acid.
When the treatment liquid is prepared directly or when using a Mn (II) ion source that dissolves more easily than MnO,
Component (E) is generally unnecessary. When component (E) is used, it is preferably (i) hydroxylamine,
And salts, complexes, oximes and other reaction products of hydroxylamine, when dissolved in water, establish an equilibrium with free hydroxylamine and when already released are consumed by irreversible reactions Releases more hydroxylamine rapidly, and consequently
One that functions chemically similar to hydroxylamine when dissolved in water (these reaction products); and (i)
i) Ferrous ions are selected from the group consisting of ferrous ions, but ferrous ions which are cheaper and are effective at lower concentrations are more preferred. A water-soluble salt of ferrous ions can be used as a source of ferrous ions. Powdered metallic iron can also be used, but is usually not preferred because it is more difficult to dissolve.

The ratio of the molar concentration of ferrous ion to the molar concentration of MnO used in preparing the composition of the present invention is as follows:
Preferably, at least 0.001: 1.0, 0.003: 1.
0, 0.005: 1.0, 0.006: 1.0, 0.0
070: 1.0, 0.0075: 1.0, 0.008
0: 1.0, 0.0083: 1.0 or 0.008
5: 1.0, and independently of this, preferably 0.50: 1.0, 0.30: 1.0, increasing preference in the order given, mainly for economic reasons.
0.10: 1.0, 0.07: 1.0, 0.05: 1.
0, 0.040: 1.0, 0.030: 1.0, 0.0
25: 1.0, 0.020: 1.0, 0.015: 1.
0, 0.012: 1.0 or 0.0090: 1.0 or less.

If hydroxylamine is used, it is hydroxylamine sulfate, ie, (HONH) S
It is preferably supplied by O (hereinafter abbreviated as “HAS”). Independently, when hydroxylamine is used as component (E), the molar ratio of hydroxylamine: MnO used in preparing the composition of the present invention is preferably in the order given. For preference, at least 0.01:
1.0, 0.03: 1.0, 0.05: 1.0, 0.0
7: 1.0, 0.080: 1.0, 0.090: 1.
0, 0.100: 1.0, 0.105: 1.0, 0.1
10: 1.0, 0.115: 1.0 or 0.119:
1.0, and independently preferably, 1.0: 1.0, 0.8: 1.0, 0.70 as preference increases in the order given, mainly for economic reasons. :
1.0, 0.60: 1.0, 0.50: 1.0, 0.4
0: 1.0, 0.30: 1.0, 0.25: 1.0,
0.20: 1.0, 0.15: 1.0 or 0.13:
1.0 or less.

An optional surfactant component (F) is often present in the composition of the present invention to promote complete and uniform wetting of the metal substrate to be phosphated with the chemical conversion solution of the present invention. preferable. A preferred type of surfactant for the chemical conversion solution of the present invention is a surfactant consisting of a partial ester of ether alcohol and phosphoric acid prepared by condensing ethylene oxide and phenol. If used, the amount of surfactant is preferably increased in preference in the order given,
At least 0.01, 0.03, 0.05, 0.07,
0.080, 0.085, 0.090, 0.095 or 0.099 ppt, and independently preferably, preferably 1.0, as a preference increases in the order given, mainly for economic reasons. , 0.8, 0.6, 0.
4, 0.30, 0.25, 0.20, 0.17, 0.1
5, 0.13 or 0.11 ppt or less.

The optional component fluoride (G) is represented by (i)
If the phosphating solution contains a substantial amount of chloride (which may occur with tap water supply), the phosphating of the galvanized surface will result in "white spots" (white spots).
(ii) provide a buffering action to maintain the acidity of the composition in the desired range, and (iii) promote the desired dissolution rate of the phosphatized metal (such as Acceleration is often necessary for the phosphating process to be successful).
It is usually preferred to be present in the composition of the present invention. Steel and aluminum substrates can benefit from this last function, and in the compositions of the present invention, as is known in the art for most other phosphating processes, 100-300 parts / part. 1 million copies (hereinafter usually "pp
m ") is optimal for cold rolled steel substrates with a stoichiometric equivalent concentration of fluorine atoms, and substantially higher fluoride concentrations when aluminum is subjected to a conversion coating process. Is preferred. The amount used in that case preferably amounts to the well-known difficulties that can be caused by the accumulation of aluminum ions in phosphating solutions that do not contain a complexing agent for aluminum ions such as fluoride. Should be large enough to avoid.

The optional divalent metal ion component (H), except for manganese and iron added as part of the reducing agent component (E), is generally not required in the compositions of the present invention;
Thus, for economic reasons at least, it is usually preferred to omit it, but it may be useful in special circumstances. The optional buffer component (J) is often the component (G)
When is omitted, it is preferred that it is present in the composition of the present invention. When used, borates, silicates, acetates and the corresponding acids are suitable components of component (J), although many other materials are well known to those skilled in the art. The biocide, an optional component (K), is usually present in the composition of the present invention when a substantial amount of gluconic acid and / or citric acid and their salts are present in the composition. preferable. The reason is that many microorganisms that are widely present in the normal environment use these organic acids as nutrients,
In the process, it can happen that the composition loses its effectiveness for its intended use and / or renders the composition unpleasant for the personnel handling it, for example by foul odors. Because.

The bath additive of the present invention is a one-pack type concentrated liquid, that is, water and the above-mentioned treatment liquid.
It is an aqueous solution comprising the desired components (A) to (K) in the treatment liquid prepared from the building bath agent. (A)-(K)
Is required together with other components in a treatment solution prepared from a building bath agent. However, in order to adjust the free acidity and the total acidity as described above, components (A) to (B) are added to the treating solution prepared to a volume slightly smaller than the desired final volume. Acids or alkaline substances that are not part of (K) are not contained. Usually, adjustment to make alkaline (alkalinizing adjustment)
ent) is required, in which case it is preferred to use at least one of ammonium hydroxide, potassium hydroxide and sodium hydroxide, mainly for economic reasons. The ratio of the concentration of each component in the bathing agent to the concentration of the same component in the treatment liquid, which is desirably prepared from the bathing agent, is preferable for all components of the bathing agent of the present invention except for water. Is
As preference increases in the order given, at least 5: 1.0, 10: 1.0, 20: 1.0, 30: 1.
It is preferred to be present in the building bath at a concentration of 0, 40: 1.0 or 50: 1.0. .

The concentrate is at least -20 ° C to 50 ° C
And more preferably up to 80 ° C. in a stable temperature range. Stability can be conveniently evaluated by measuring the above-mentioned free acidity and total acidity after diluting a sample to a concentration near a concentration desired for a normal treatment solution. If these values change by no more than 10% of the value before storage after storage, or if the absolute value before storage is less than 2.0 points and only change by 0.2 points or less, the concentrate Can be considered as having storage stability. The concentrates of the present invention may have at least 1, 3, 10,
After storage for 30, 60 or 200 days, it has storage stability in the sense defined above.

The actual conversion coating step in the process of the present invention is preferably carried out in at least 23, 26, 29, 32, 35,
It is carried out at a temperature of 38, 41, 44, 46, 48, 50, 52, 54 or 55 [deg.] C., independently of, preferably, mainly for economic reasons, in particular to minimize the sludge volume. It is performed at a temperature of 75, 72, 70, 68, 66, 64, 62 or 61 ° C. or less, in order of increasing preference.

The contact time in the conversion coating forming step should preferably be sufficient to form a complete coating of microcrystalline phosphate on the surface to be contacted. If the contact between the surface to be chemically converted and the treatment liquid of the present invention is carried out by immersion, the contact time is preferably at least 0.4 as increasing preference in the order given.
0, 0.50, 0.60, 0.70, 0.80, 0.9
0, 1.0, 1.3, 1.5, 1.7 or 2.0 minutes, and when maximum corrosion protection values are required for the steel, more preferably in the order given. Increases by at least 2.2, 2.4, 2.6,
2.8, 3.0, 3.5, 4.0, 4.5 or 5.0
, Independently of each other, preferably for increasing reasons of preference, mainly for economic reasons, in the order given, 15, 10, 8.0, 7.0, 6.5, 6.0,
Unless 5.7, 5.4, 5.2 or 5.0 or less and maximum corrosion protection values are required for the steel from the process, more preferably the preference is given in the given order. 4.5, 4.0, 3.7,
3.5, 3.3, 3.1, 2.9, 2.7, 2.5,
2.3 or 2.1 minutes or less.

Also, if the contact is made by spraying, the contact time is preferably at least 0.40, 0.5, preferably in the order given, increasing in preference.
0, 0.60, 0.70, 0.80, 0.90, 1..
0, 1.3, 1.5, 1.7 or 2.0 minutes independently of each other, preferably for economic reasons,
As the preference increases in the order given, 30, 2
0, 15, 12, 10, 8, 7.0, 6.5, 6.0,
5.5, 5.0, 4.5, 4.0, 3.5, 3.0 or 2.5 minutes or less. When the substrate surface to be applied is mainly zinc-containing, a short contact time is particularly preferable since the film weight does not increase so much after a film completely covering the contact surface is formed. However, even after a film is formed that completely covers the contact surface, the film weight increases with increasing contact time.

The conversion coatings formed by the process of the present invention are preferably at least 0.4, 0.7, 1.0, 1.2,
1.5, 1.7, 1.9, 2.1, 2.3, 2.40,
Having a mass per unit area of 2.50, 2.60, 2.70, 2.80, 2.90, or 2.97 g / application surface m (hereinafter, usually abbreviated as “g / m”); Independently, preferably, the preference increases in the order given, 20, 17, 15, 13, 11, 9.0, 8.
0, 7.0, 6.0, 5.0, 4.5, 4.0, 3.
It has a mass per unit area of no more than 8, 3.6, 3.4, 3.20 or 3.10 g / m.

Prior to applying the conversion coating of the present invention to a metal substrate, the substrate to be subjected to the conversion coating can be completely treated by any of a variety of methods well known to those skilled in the art and suitable for the particular substrate to be coated. It is preferable to wash. When the conversion coating of the present invention is applied to a steel substrate, after cleaning, the substrate is first treated with a conventional manganese hydrogen phosphate and alkali metal pyrophosphate surface conditioner used on steel prior to manganese phosphate treatment according to the prior art. It is preferable to adjust the surface with. When the conversion coating of the present invention is applied to a substrate mainly containing zinc, such as galvanized steel, a Gernsted salt (Jernsteel) is used.
Preferably, a surface conditioning treatment using a titanium phosphate sol, also known as dt salt), is performed between the washing and the phosphate chemical treatment of the present invention. When the chemical conversion coating of the present invention is applied to a substrate having a substantial area of both steel and galvanized steel, the above two types of surface conditioners are required between cleaning and the phosphate conversion treatment of the present invention. Is preferably brought into contact with the mixture of

The embodiments of the present invention described above, including preferred and further preferred embodiments, can be expressed as follows: (1) Applying an external electromotive force on a metal substrate or applying a current in the metal substrate. A method for forming a chemical conversion film on the surface of a metal substrate without the use of water and (A) about 0.3
A concentration expressed in the same units as the concentration of dissolved divalent manganese cation and (B) divalent manganese cation at a concentration of 0 to about 4.0 ppt, wherein the concentration of divalent manganese cation: dissolved phosphate anion Concentration ratio = about 1.0:
An acidic aqueous composition containing a concentration of dissolved phosphate anions of from 50 to about 1.0: 5.0, having a temperature of 75 ° C. or less during contact with the metal substrate, wherein the composition has a temperature of about −1.5. ~ About 1.
It has a free acidity of 5 and a total acidity of about 4 to about 50, and has the following components: zinc cation, nickel cation,
0 to 0.02% for each of calcium, magnesium, cobalt (II) cation, nitrite, all halogen and perhalate, chloride, ferrocyanide and ferricyanide ions. A method comprising contacting an acidic aqueous composition having only a concentration with a metal substrate for a time of not more than 5.0 minutes to form a film having a mass of at least about 1.2 g / m.

(2) The method according to the above (1), wherein the aqueous composition further contains nitric acid, and the concentration of the dissolved phosphate anion is about 40 ppt or less. (3) The aqueous composition further comprises at least 0.15 g /
L contains formic acid, the concentration of dissolved divalent manganese cation is about 0.70 to about 3.0 ppt, and the concentration of dissolved manganese cation: the concentration of dissolved phosphate anion (both concentrations are in the same unit) ) Of about 1.0: 30
The method according to the above (2), wherein the ratio is about 1.0: 8.0. (4) The aqueous composition contains formic acid at a concentration of about 0.25 to about 1.0 g / L, and the ratio of the concentration of formic acid to the concentration of nitric acid (both concentrations are expressed in g / L) is about 0.1. 002: 1.0 to about 0.1.
20: 1.0, the concentration of dissolved divalent manganese cation is about 0.70 to about 2.5 ppt, the concentration of dissolved phosphate anion is about 7 to about 19 ppt, Concentration: The ratio of the concentration of dissolved phosphate anions (both concentrations are expressed in the same units) is about 1.0: 2
The method according to the above (3), which is 4 to about 1.0: 10.0.

(5) The aqueous composition contains formic acid at a concentration of about 0.25 to about 0.70 g / L, and the ratio of the concentration of formic acid to the concentration of nitric acid (both concentrations are expressed in g / L) is About 0.00
8: 1.0 to about 0.10: 1.0, and the concentration of the dissolved divalent manganese cation is about 0.70 to about 2.3 ppt.
And the concentration of the dissolved phosphate anion is about 11.0 to
About 17.0 ppt and the ratio of the concentration of dissolved manganese cation to the concentration of dissolved phosphate anion (both concentrations are expressed in the same units) is about 1.0: 18 to about 1.0: 12.0.
The method according to the above (4), wherein (6) maintaining the aqueous composition at a temperature of about 44 to about 64C for a contact time of about 0.50 to about 5.0 minutes;
The method according to the above (5), wherein a chemical conversion film having a mass per unit area of about 5.0 g / m is formed. (7) The aqueous composition is about 0.35 to about 0.55 g / L.
And the ratio of formic acid concentration: nitric acid concentration (both concentrations are expressed in g / L) was about 0.015: 1.0 to about 0.050: 1.0. The concentration of the divalent manganese cation is about 1.20 to about 2.3 ppt, and the concentration of the dissolved phosphate anion is about 11.0 to about 17.0 ppt.
pt and the total acidity of the aqueous composition is from about 15.0 to about 3
The method according to the above (6), which is 0.

(8) An aqueous concentrated composition useful as a one-part concentrate for building baths which produces a treatment liquid for chemical conversion film formation by dilution, comprising: water; and (A) at least about 1
0.0ppt concentration of dissolved divalent manganese cation, (B) a concentration expressed in the same unit as the concentration of divalent manganese cation, wherein the concentration of divalent manganese cation: the concentration of dissolved phosphate anion Ratio = about 1.0: 50 to about 1.0: 5.0, containing dissolved phosphate anions and (C) nitric acid at a concentration of at least about 3.3%, and comprising the following components: zinc 0 for each of the cation, nickel cation, calcium cation, magnesium cation, cobalt (II) cation, nitrite ion, all halide and perhalate ions, chloride ions, ferrocyanide ions and ferricyanide ions. Aqueous concentrate composition having a concentration of only to 0.2%. (9) The ratio of the concentration of formic acid to the concentration of nitric acid is about 0.002:
The aqueous concentrated composition according to the above (8), further containing formic acid at a concentration of 1.0 to about 0.10: 1.0. (10) The concentration of the dissolved divalent manganese cation is at least about 12.0 ppt, and the ratio of the concentration of the divalent manganese cation to the concentration of the dissolved phosphate anion is about 1.
0:30 to about 1.0: 8.5, the concentration of nitric acid is at least about 5.0%, and the ratio of the concentration of formic acid to the concentration of nitric acid (both concentrations are expressed in the same units) is about 0.5. 008: 1.0-
The aqueous concentrated composition according to the above (9), wherein the composition is about 0.070: 1.0.

(11) The concentration of the dissolved divalent manganese cation is at least about 15.0 ppt, and the ratio of the concentration of the divalent manganese cation to the concentration of the dissolved phosphate anion is from about 1.0: 16 to about 1. 0: 11.0, wherein the concentration of nitric acid is at least about 10.0% and the concentration of formic acid:
The ratio of nitric acid concentration (both concentrations are expressed in the same unit) is about 0.0
20: 1.0 to about 0.060: 1.0.
The aqueous concentrated composition according to 0). (12) Dissolved divalent manganese cation in manganese oxide (I
I) is introduced into the composition by dissolving, and the concentrate composition comprises (1) ferrous ion and its reaction product: the moles of manganese (II) oxide supplied with component (A) A ratio of about 0.006: 1.0 to about 0.040: 1.0
An amount of ferrous ion and its reaction product and (2) hydroxylamine and its salts and complexes which, when dissolved in water, act chemically like hydroxylamine: oxidation provided component (A) Manganese (II)
At least a molar ratio of about 0.07: 1.0 to about 0.25: 1.0 of hydroxylamine and its salts and complexes that, when dissolved in water, act chemically like hydroxylamine. The above (1) further containing one kind
The aqueous concentrated composition according to 1).

(13) Ferrous ion and its reaction product: ferrous ion and its reaction product: component (A)
Molar ratio of manganese (II) oxide supplied = about 0.0
080: 1.0 to about 0.012: 1.0, the aqueous concentrate composition of (12) above. (14) The dissolved manganese cation is introduced into the acidic aqueous solution for preparing the concentrated liquid composition by dissolving manganese (II) oxide into the composition, and the concentrated liquid composition is obtained by the method (1). Ferrous ion and its reaction products:
The amount of ferrous ion and its reaction product and (2) in which the molar ratio of manganese (II) oxide to which component (A) is supplied is from about 0.006: 1.0 to about 0.040: 1.0. )) Hydroxylamine and its salts and complexes which, when dissolved in water, act chemically like hydroxylamine:
Component (A) is supplied with a molar ratio of manganese (II) oxide of about 0.07: 1.0 to about 0.25: 1.0 of hydroxylamine and hydroxylamine when dissolved in water. The aqueous concentrated composition according to the above (10), further comprising at least one kind of salts and complexes thereof which also act chemically. (15) The ferrous ion and its reaction product are the ferrous ion and its reaction product: the molar ratio of manganese (II) oxide supplied with the component (A) = about 0.0080: 1.
The aqueous concentrate composition of the above (14), which is present at 0 to about 0.012: 1.0.

(16) The dissolved manganese cation is introduced into the concentrated aqueous composition by dissolving manganese (II) oxide in the acidic aqueous solution used in preparing the concentrated liquid composition. (1) Ferrous ion and its reaction product: the molar ratio of manganese (II) oxide to which component (A) is supplied is about 0.006: 1.0 to about 0.04.
Ferrous ion and its reaction products in an amount of 0: 1.0 and (2) hydroxylamine and its salts and complexes which, when dissolved in water, act chemically like hydroxylamine: component (A) Is supplied in a molar ratio of about 0.07: 1.0 to about 0.25:
The aqueous concentrated composition according to the above (9), further comprising an amount of hydroxylamine which is 1.0 and at least one of salts and complexes thereof which act chemically like hydroxylamine when dissolved in water. (17) The ferrous ion and its reaction product are the ferrous ion and its reaction product: the molar ratio of manganese (II) oxide supplied with the component (A) = about 0.0080: 1.
The aqueous concentrate composition of the above (16), which is present at 0 to about 0.012: 1.0.

(18) The dissolved manganese cation is introduced into the concentrated liquid composition by dissolving manganese (II) oxide in the acidic aqueous solution used in preparing the composition, and the concentrated liquid composition is (1) Ferrous ion and its reaction product: the molar ratio of manganese (II) oxide to which component (A) is supplied is about 0.006: 1.0 to about 0.04.
Ferrous ion and its reaction products in an amount of 0: 1.0 and (2) hydroxylamine and its salts and complexes which, when dissolved in water, act chemically like hydroxylamine: component (A) Is supplied in a molar ratio of about 0.07: 1.0 to about 0.25:
The aqueous concentrated composition according to the above (8), further comprising an amount of hydroxylamine which is 1.0 and at least one kind of a salt and a complex thereof which chemically acts like hydroxylamine when dissolved in water. (19) The ferrous ion and its reaction product are ferrous ion and its reaction product: the molar ratio of manganese (II) oxide supplied with the component (A) = about 0.0080: 1.
The aqueous concentrate composition of the above (18), which is present at 0 to about 0.012: 1.0. (20) The component (A) is supplied from manganese (II) oxide, and its dissolution for preparing the aqueous composition according to the above (1) is performed by a precursor in which the manganese (II) physically contacts during dissolution. A method for producing an aqueous composition according to (1) above, which is facilitated by the presence of a dissolved reducing agent in the aqueous body composition.

[0040]

The practice of the present invention is further illustrated by the following non-limiting examples. The advantages of the present invention will become apparent by comparison with the comparative examples given below and by additional comparisons known to those skilled in the art. Examples-Group 1 Substrates used in general processing conditions and their abbreviations used below are listed in Table 1.
It is shown in FIG. The substrate was in the form of a conventional rectangular test panel (test panel).

[0041]

[Table 1] Table 1.1

The adopted processing order is shown in Table 1.2. (FIXODINE), PACO (PARC)
O) or PARCOLENE, all materials identified here by Henkel (Henkel)
kel Corp. ) Parker Amchem section (the
Parker Amchem Division),
Madison Heights,
Michigan and / or Henkel Metal Chemie (He
nkel Metallchemie), Düsseldorf, Germany, with instructions for using them in the process steps described herein. )

[0043]

[Table 2] Table 1.2

Concentrate Example Group 1.1 Concentrates 1.1.1 and 1.1.2 of the present invention were prepared from the constituent materials shown in Table 1.3 below.

[0045]

[Table 3] Table 1.3

Examples and comparison of processing solutions and processing methods
Example Group 2 A treatment liquid 2.1 was prepared by dissolving the components to a total volume of 10 L with the required amount of water in addition to the components listed below: Concentrate (1. 1)
Surfactants composed of 500 g, 10 g of MnCO, 10 g of gluconic acid, a partial ester of phosphoric acid, preferably a partial ester of phosphoric acid with an alcohol having an aromatic moiety, for example Henkel, Emery Group (Hen)
kelCorp. TRYFAC5, commercially available from Cincinnati, Ohio, Emery Group).
555 or 5556 surfactant, RHODAFACBG-510, BG-769, BX-, commercially available from Rhone-Poulenc
660, PE-9, RA-600, RE-610, RE
-960, RM-710, RP-710 or RS-7
10 surfactant, Deforest Enterprises, Ind.
c. ), Commercially available from Boca Raton, Florida
ePhos P-6LF, P6-LF AS or PE
481 surfactants (according to the manufacturer, all the above surfactants are reported to consist essentially of the partial ester of orthophosphoric acid with the alcohol produced by the addition of ethylene oxide with phenol and / or alkylphenol. ) 1.0 g, and a 20% aqueous sodium hydroxide solution to raise the pH of the final treatment to 3.8. The final concentration of manganese (II) cation was 1.
It was 89 ppt and the total acidity was 16.1. Using this treatment solution and its partially modified specifications shown in Table 2.1 below, a rectangular CRS test plate of size 10 × 15 cm was prepared.
It was applied by immersing it in a treatment solution maintained at the temperature shown in Table 2.1 for 3 minutes. The processing steps are the same as in group 1.

[0047]

[Table 4] Table 2.1

Note 1 in Table 2.1 Between the test plates 2.2 and 2.3, 20 additional test plates were treated with the treatment liquid to ripen the treatment liquid (the coating weight was not measured. ). This slightly reduced the total acidity to 16.0. Good appearance phosphate coatings were obtained for all these 20 additional test plates. 2. Between the test plates 2.4 and 2.5, sufficient HAS was added to the treatment liquid in which the test plate was immersed, so that the HAS concentration in the treatment liquid was 0.25%. 3. Between the test plates 2.6 and 2.7, additional HAS was added to the treatment liquid in which the test plate was immersed, so that the total HAS concentration in the treatment liquid was 0.6%. 4 Between the test plates 2.6 and 2.7, additional HAS was added to the treatment liquid in which the test plate was immersed, so that the total HAS concentration in the treatment liquid was 2.0%. Formed very thin (spar
se) The phosphate film does not contain a substantial content of manganese and is understood to be only iron phosphate.

Example 3 of Treatment Solution and Treatment Method The pH was adjusted to 3.0 without using gluconic acid and manganese carbonate.
The treatment liquid was manufactured in the same manner as in Group 2 except that the acidity was adjusted to 75 and the total acidity was 16.4. 3.07 g of a CRS test plate applied by immersion at 54.4 ° C. for 3 minutes
/ M phosphate coating. Example 4 and Comparative Example of Treatment Solution and Treatment Method Group 4 The above concentrated solution 1.1 was diluted to a manganese (II) concentration of 2.5 to 2.8 ppt, and the total acidity was 2 with sodium hydroxide.
Adjusted to 9.3 and free acidity 1.4. 6 test plates
The coating was applied by dipping at 5.6 ° C., and the results shown in Table 4.1 were obtained.

[0050]

[Table 5] Table 4.1

While the coating obtained for test plate 4.1 did not completely cover the surface, for all other test plates in Table 4.1, the coating obtained completely coated the surface. I was Examples and Comparative Examples Concentrate, treatment liquid, and treatment method
Example Group 5 The concentrates prepared for this group are shown in Table 5.1 below.

[0052]

[Table 6]

HNO and HPO in Table 5.1 were added in the form of aqueous solutions of the density or concentration indicated in the table heading. Baume 42 ° nitric acid contains about 69% pure HNO. The remainder for all concentrations, not specified in the table, was water.

The concentrated liquid shown in Table 5.1 was the composition No. 5.
All were stable except those of 9 and 5.11. When the concentrates 5.1 to 5.9 were diluted with water to prepare a treatment liquid containing 100 g of the concentrate per 1 L of the treatment liquid, the treatment liquid was as shown in Table 5.2 (the treatment liquid number is shown in Table 5. (Corresponding to the composition number in Example No. 1).

[0055]

[Table 7]

Footnotes, abbreviations and their descriptions for Table 5.2
Other notes The last number shown in these columns is not necessarily significant (s
ignitant). "Beginning" means the point of preparation before use, while "End" means after all of the following processing steps have been completed without any intermediate replenishment.
As shown in the other tables below, when the same composition was used more than once, the first and last values were averaged for all use conditions. The variation when averaging in this way did not exceed each other in the last number shown in the table. Prior to use on the coated test panels shown in the table below, each treatment solution was aged by dipping several cold rolled steel sheets into it, sufficient to reach 0.5 cm per liter of treatment solution. (Was aged). These "aged" plates were left in place for 5 minutes.

The treatment solutions 5.1 to 5.8 and 5.10 shown in Table 5.2 correspond to the corresponding concentrated solutions 5.1 shown in Table 5.1.
~ 5.8. First, the corresponding concentrate, 90%
Formic acid and gaffac (GAFAC) in the form of an aqueous solution
Add RP-710 (surfactant) to water and concentrate about 12
Make a preliminary solution containing 0 g / L. The pre-solution is then brought to final volume with more water and 50% aqueous sodium hydroxide in an amount containing sodium required to produce the sodium concentration shown in Table 5.2. As a result, the final free acidity is a value in the range of 0.20 to 0.33, the final concentration of the concentrate is 100 g / L, the final concentration of formic acid is 0.044%, and the concentration of Gaffa RP-710 The final concentration will be 0.02%. Formic acid and Gaffa P at the same concentrations specified above for the other treatments shown in Table 5.2.
The processing solution 5.9 shown in Table 5.2, containing R-710, was prepared directly from the base components. Treatment liquid 5.1-5.
Concentrations of nitrate and phosphate ions shown in Table 5.2 for Sample No. 8 were determined by a three-factor steric assignment experimental design (three-f
actor face centered cubic
Construct three variable values for two of the three factors in experimental design. Treatment 5.9 was initially planned to have the highest nitric acid and phosphoric acid concentrations, respectively, to complete this experimental design, but this may not be possible due to the instability of the treatment. found. Thus, treatment liquid 5.9 was prepared at slightly lower values shown for these components in Table 5.2.
These concentrations were found to be stable. The third factor in this experimental design was the immersion time shown in Table 5.4 and below. The processing solutions shown in Table 5.2 were used in the expansion process according to the invention, having the characteristics shown in Table 5.3 below.

[0058]

[Table 8]

Footnotes in Table 5.3 * This process was applied only to cold rolled steel.

Substrates treated in this group were cold rolled steel, double-sided and single-sided galvanized steel (double-sided and single-sided EG steel), and nickel-flashed steel (nicke).
1-flashed steel). Before the test, the substrate used for the corrosion test was Durakuron (DURA).
CRON) 200 (relatively poor against corrosion (poo)
r) paints which only provide protection and are therefore suitable for distinguishing the degree of protection afforded by the phosphate coating) and of the phosphating according to the invention and the highly protective organic base overcoat of said phosphate coating. Obtained by combination,
To determine the highest level of protection, a highly protective coating system of the type currently commonly used in new vehicles manufactured in the United States was applied without chemical post-treatment of the formed conversion coating. (It is believed that better post-treatment corrosion protection is achieved). Table 5.4 below shows the immersion time, the amount of coating per unit area, and the results of various corrosion tests on substrates treated by immersion in one of the treatment solutions described in detail in Table 5.2. Table 5.4
The amount of coating shown in the figure is the stripping of a sample with a phosphate coating formed but no coating applied, except for a single-sided galvanized substrate.
And in the case of a single-sided electrogalvanized substrate, A
soma Instruments, Inc. (121
2-H Technology Blvd. ASOMA ™ model 86 supplied by Austin, Texas, and used as directed by the manufacturer.
The calculation was based on the measurement of the phosphorus content in the film performed using a 20X-ray fluorescence measurement apparatus. Processing solution 5.1 in Table 5.2
0 was contacted by spraying instead of dipping. 60 ° C
Spraying for 2 minutes produced a film with good visual appearance.

[0061]

[Table 9]

[0062]

[Table 10]

[0063]

[Table 11]

The abbreviations for Table 5.4 and other notes "SEM" are used for scanning electron microscopy.
electron microscope), and "S
"S" stands for "salt spray" (American Society)
for Testing and Material
s) Means method ASTM-B-7, and the values given in the table indicate the maximum width of the corroded area of the test plate from the first scribing, therefore lower values are preferred.
The scab test is a general motors method 9
Performed according to 540P-B, the values shown in the table indicate the maximum width of the total creep, so lower values are preferred. "N.
m. "Not measured
Indicates that Visual and SEM appearance evaluation is 1 (best)
５5 (worst). For visual evaluation, 1 corresponds to a uniform film appearance showing tightly packed microcrystals, and 5 indicates a stained surface with a perceivable void area without magnification. The SEM evaluation was mainly based on the size of the crystal. A rating of 1 corresponds to a fine, well defined crystal,
A rating of 5 corresponds to a large, mottled crystal. The "R" in the appearance rating column indicates the presence of slight rust at the edge of the painted sample, which is likely due to finger contact during the painting process.

[0065]

According to the invention, alternatively and / or simultaneously, (i) a composition for phosphating to form a high quality coating base for paints and similar topcoats containing organic binders. (Ii) providing a composition and a treatment method, wherein the main one of the divalent or higher cations in the composition is a manganese ion, and (ii) a conventional manganese phosphate chemical conversion treatment solution. Providing a manganese-containing phosphate conversion coating that can be more easily controlled to reduce the amount of manganese deposited per unit area than normally obtained with (iii) a zinc, nickel and / or cobalt-containing chemical conversion treatment A relatively economical phosphating solution and treatment that produces a good quality coating substrate similar to current conventional phosphating methods using liquor (V) providing a chemical conversion coating having excellent coating quality as a coating base by spraying, and (v) reducing the risk of environmental pollution by a phosphating solution. Sludge produced by reducing or eliminating the content of "heavy metals" other than zinc, nickel, cobalt, chromium, copper and / or other manganese and / or (v.2) during use of the phosphating solution By reducing the amount of (C), it is possible to provide (vi) a conversion coating having excellent coating quality as a coating base at a phosphating temperature of 75 ° C. or less.

 ────────────────────────────────────────────────── ─── Continued on front page (72) Inventor Michael Petchell 48307, Michigan, USA, Rochester Hills, Stoneberry Drive 2604

Claims (10)

[Claims] 1. A method for forming a chemical conversion film on a surface of a metal substrate without applying an external electromotive force or applying a current to the metal substrate, comprising the steps of: A concentration expressed in the same unit as the concentration of the dissolved divalent manganese cation and (B) the divalent manganese cation at a concentration of ~ 4.0 ppt, wherein the concentration of the divalent manganese cation: the concentration of the dissolved phosphate anion An acidic aqueous composition containing dissolved phosphate anions in a concentration of from 1.0: 50 to 1.0: 5.0, having a temperature of 75 ° C. or less during contact with the metal substrate. , −
It has a free acidity of 1.5-1.5, has a total acidity of 4-50, and has the following components: zinc cation, nickel cation, calcium cation, magnesium cation,
An acid having a concentration of only 0 to 0.02% for each of the cobalt (II) cation, nitrite ion, all halogen and perhalate ions, chloride ions, ferrocyanide ions and ferricyanide ions Contacting the aqueous composition with the metal substrate for a time of not more than 5.0 minutes to form a coating having a mass of at least about 1.2 g / m. 2. The method of claim 1 wherein said aqueous composition further comprises nitric acid and the concentration of dissolved phosphate anions is less than about 40 ppt. 3. The aqueous composition further comprising at least 0.1
It contains formic acid at a concentration of 5 g / L, the concentration of the dissolved divalent manganese cation is 0.70 to 3.0 ppt, and the concentration of the dissolved manganese cation: the concentration of the dissolved phosphate anion (both concentrations are in the same unit). ) Is 1.0: 30.
The method according to claim 2, wherein the ratio is 1.0 to 8.0. 4. The composition according to claim 1, wherein the aqueous composition is 0.25 to 1.0 g / L.
And the ratio of the concentration of formic acid to the concentration of nitric acid (both concentrations are expressed in g / L) is 0.002: 1.0 to 0.2.
0: 1.0, the concentration of dissolved divalent manganese cation is 0.70-2.5 ppt, the concentration of dissolved phosphate anion is 7-19 ppt, and the concentration of dissolved manganese cation: dissolved The ratio of the phosphate anion concentrations (both concentrations are expressed in the same unit) is 1.0: 24 to 1.0:
4. The method of claim 3, wherein the value is 10.0. 5. The aqueous composition is maintained at a temperature of 44-64 ° C. for a contact time of 0.50-5.0 minutes, wherein the temperature is 1.9-5.
The method according to claim 4, wherein a chemical conversion film having a mass per unit area of 0 g / m is formed. 6. An aqueous composition comprising 0.35 to 0.55 g /
L containing formic acid, wherein the ratio of formic acid concentration: nitric acid concentration (both concentrations are expressed in g / L) is 0.015: 1.0-0.
050: 1.0, the concentration of the dissolved divalent manganese cation is 1.20 to 2.3 ppt, the concentration of the dissolved phosphate anion is 11.0 to 17.0 ppt,
The total acidity of the aqueous composition is from 15.0 to 30.
The described method. 7. An aqueous concentrated composition useful as a one-part concentrate for a bath for forming a chemical conversion film-forming treatment liquid by dilution thereof, comprising: water; and (A) a concentration of at least 10.0 ppt.
A concentration expressed in the same unit as the concentration of the dissolved divalent manganese cation and (B) the divalent manganese cation, and the ratio of the concentration of the divalent manganese cation to the concentration of the dissolved phosphate anion = 1.0: 50. Dissolved phosphate anion at a concentration of １．０1.0: 5.0 and (C) at least 3.3%
And the following components: zinc cation, nickel cation, calcium cation, magnesium cation, cobalt (II) cation, nitrite ion, all halide and perhalate ions, chloride ion, An aqueous concentrate composition having a concentration of only 0 to 0.2% for each of the Russian and ferricyanide ions. 8. The ratio of the concentration of formic acid to the concentration of nitric acid is 0.00.
The aqueous concentrated composition according to claim 7, further comprising formic acid at a concentration of 2: 1.0 to 0.10: 1.0. 9. A method for preparing manganese oxide (I) by dissolving a dissolved manganese cation in an acidic aqueous solution for preparing the concentrated liquid composition.
I) is introduced into the composition by dissolving, and the concentrate composition comprises (1) ferrous ion and its reaction product: the moles of manganese (II) oxide supplied with component (A) An amount of ferrous ion and its reaction product in a ratio of 0.006: 1.0 to 0.040: 1.0, and (2)
The molar ratio of hydroxylamine and its salts and complexes which, when dissolved in water, acts chemically like hydroxylamine: manganese (II) oxide supplied with component (A) is 0.07: 1.0-0 An aqueous concentrated composition according to claim 8, further comprising hydroxylamine in an amount of .25: 1.0 and at least one of its salts and complexes which, when dissolved in water, act chemically like hydroxylamine. . 10. A method for preparing manganese oxide (I) by dissolving a dissolved manganese cation in an acidic aqueous solution for preparing the concentrated liquid composition.
I) is introduced into the composition by dissolving, and the concentrate composition comprises (1) ferrous ion and its reaction product: the moles of manganese (II) oxide supplied with component (A) An amount of ferrous ion and its reaction product in a ratio of 0.006: 1.0 to 0.040: 1.0, and (2)
The molar ratio of hydroxylamine and its salts and complexes which, when dissolved in water, acts chemically like hydroxylamine: manganese (II) oxide supplied with component (A) is 0.07: 1.0-0 The aqueous concentrated composition according to claim 7, further comprising hydroxylamine in an amount of .25: 1.0 and at least one of its salts and complexes which, when dissolved in water, act chemically like hydroxylamine. .