JP2003171778A - Method for forming protective film of metal, and protective film of metal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To form a protective film combining uniform, satisfactory appearance and stable corrosion resistance equal to that by treatment with hexavalent chromium on the surfaces of Zn, Ni, Cu, Ag, Fe, Cd, Al, Mg, and their alloys without using harmful hexavalent chromium, nor using fluorine compounds having a strong corrosiveness as essential components. <P>SOLUTION: The method for forming a protective film of a metal has a process where the surface of a metal is coated with a layer chemically converted from an aqueous acid liquid solution, and a process where the aqueous acid liquid composition is dried without rinsing. The aqueous acidic liquid composition contains (A) at least one kind selected from the group consisting of Ti, V, Mn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, and W, and (B) at least one kind selected from the group consisting of organic acid and/or inorganic acid such as the oxyacid of phosphorus, nitric acid, sulfuric acid, hydrochloric acid, and boric acid and/or their salts, and (C) fluorine as an optional component. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention generally relates to zinc, nickel, copper, silver, iron, cadmium, aluminum, magnesium and their alloys, and their plated metal materials. In particular, it relates to a metal material in which the surface of these metals is coated with zinc or a zinc alloy. Furthermore, the present invention relates to an iron-based material whose surface is coated with zinc or a zinc alloy.

[0002]

2. Description of the Related Art Conventionally, zinc plating or zinc alloy plating such as zinc-iron alloy plating and zinc-nickel alloy plating has been widely used as a rust preventive method for iron-based materials, and is widely used for building materials, automobiles, home appliances, etc. It is used in the field. Since zinc plating or zinc-based alloy plating is baser than iron-based materials, it becomes an anode and preferentially corrodes and melts itself to prevent the dissolution of iron-based materials. Because of the suppression, the plated surface will be corroded in a short period of time only by applying zinc plating or zinc alloy plating on the iron-based material. Moreover, the sacrificial anticorrosive effect ends at the same time as the disappearance of zinc. Therefore, in order to suppress the corrosion of the surface of zinc plating or zinc alloy plating, it is common to perform chromate treatment after plating. Chromate treatment is classified into three types: electrolytic chromate treatment, coating-type chromate treatment, and reactive-type chromate treatment. Chromate treatment is not limited to zinc, but can be applied to aluminum, cadmium, magnesium, etc.

Although the corrosion resistance of chromate treatment is very excellent, since many chromate treatments use harmful hexavalent chromium, hexavalent chromium that elutes not only from the treatment liquid but also from the treated product is harmful to the human body and the environment. It has become a big problem in recent years because it has an adverse effect. This is a difficult problem because the chromate film using hexavalent chromium is a film that can exhibit corrosion resistance due to the hexavalent chromium in the film.
As another problem, electrolytic chromate treatment forms a chromate film by electrolysis, so there are always problems with the surroundings, and it is difficult to form a uniform film, and variations in quality (performance) due to current density may occur. is there. Also, chromate mist generated during electrolysis can be a more serious pollution problem than other problems. The coating type chromate treatment is a method in which an acidic aqueous solution containing chromic acid as a main component is coated on a metal surface and then heated and dried without washing with water. Since coating type chromate does not have a step of coating a metal surface with a chemical conversion film like reactive type chromate, it is not suitable for a complicated shape like electrolytic chromate, and the target object is limited to apply a uniform thickness. . However, there is no problem in applying it to steel sheets. On the other hand, reactive chromate has excellent appearance uniformity and applicability to products with complicated shapes, stable corrosion resistance is obtained, and it is often used not only as a coating base but also as a hexavalent chromium. The pollution problem of is left. In order to solve this problem, in recent years, a reactive chromate using trivalent chromium that does not use hexavalent chromium and less harm, and an alternative treatment agent similar to it, and an alternative antirust treatment agent that does not use chromium at all have been developed. Has achieved some results,
The fact is that the practical stable corrosion resistance does not reach that of the reactive chromate using hexavalent chromium. Also, the reaction chromate that does not use hexavalent chromium and less harmful trivalent chromium, an alternative treatment agent similar to it, or an alternative rust preventive agent that does not use chromium at all is used to treat the metal surface with an aqueous acid. Since the time required for the step of coating with the layer formed from the liquid composition is extremely longer than the treatment with the reactive chromate using hexavalent chromium, it may not be possible to introduce it into the field line.

[0004]

The object of the present invention is to use harmful hexavalent chromium in forming a protective film on the surfaces of zinc, nickel, copper, silver, iron, cadmium, aluminum, magnesium and their alloys. In other words, a fluorine compound having a strong corrosive property is not included as an essential component, and a film having a uniform and good appearance and stable corrosion resistance comparable to the treatment using hexavalent chromium is formed.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors, they have found that the method using an aqueous acidic liquid composition containing a specific metal as a main component can solve the problems in the prior art. That is, according to the following method (A) or (B), hexavalent chromium is not used, a highly corrosive fluorine compound is not an essential component, and a uniform and good appearance and stability more than the treatment using hexavalent chromium are obtained. It is possible to form a film with excellent corrosion resistance, and it is possible to form a film with stable corrosion resistance comparable to this even if the treatment time is shortened to the level of the current treatment using hexavalent chromium. I found: (A) (A1) Ti, V, Mn, Y, Zr, Nb, Mo, Tc, R
at least one selected from the group consisting of u, Rh, Pd and W and an organic acid and / or an oxygen acid of phosphorus, an inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid, boric acid and / or a salt thereof. And an aqueous acidic liquid composition containing fluorine as an optional component, or
(A2) Trivalent chromium, Ti, V, Mn, Y, Zr, Nb, M
from at least one selected from the group consisting of o, Tc, Ru, Rh, Pd and W, and an organic acid and / or an inorganic acid such as oxyacid of nitric acid, sulfuric acid, hydrochloric acid, boric acid and / or salts thereof. At least one selected from the group consisting of, Li, Na, K, Be, Co, Mg, Ca, A
1, at least one selected from the group consisting of Ni, Si, and further an aqueous acidic liquid composition containing fluorine as an optional component, or (A3) 0.01 to 150 g / L trivalent chromium and / or cobalt At least one selected from the group consisting of organic acids and / or nitric acid and / or salts thereof, and 0.1 to 300 g / L of Ti, V and M
n, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd,
W, Li, Na, K, Be, Mg, Ca, Al, Ni,
At least one selected from the group consisting of Si, and further, a step of coating the metal surface with a chemical conversion film with an aqueous acidic liquid composition containing fluorine as an optional component, without rinsing the aqueous acidic liquid composition after the film formation. (B) (B1) Ti, V, Mn, Y, Zr, Nb, Mo, Tc, R
at least one selected from the group consisting of u, Rh, Pd and W and an organic acid and / or an oxygen acid of phosphorus, an inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid, boric acid and / or a salt thereof. And an aqueous acidic liquid composition containing fluorine as an optional component, or
(B2) Trivalent chromium, Ti, V, Mn, Y, Zr, Nb, M
from at least one selected from the group consisting of o, Tc, Ru, Rh, Pd and W, and an organic acid and / or an inorganic acid such as oxyacid of nitric acid, sulfuric acid, hydrochloric acid, boric acid and / or salts thereof. At least one selected from the group consisting of, Li, Na, K, Be, Co, Mg, Ca, A
1, at least one selected from the group consisting of Ni, Si, and further an aqueous acidic liquid composition containing fluorine as an optional component, or (B3) 0.01 to 150 g / L trivalent chromium and / or cobalt At least one selected from the group consisting of organic acids and / or nitric acid and / or salts thereof, and 0.1 to 300 g / L of Ti, V and M
n, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd,
W, Li, Na, K, Be, Mg, Ca, Al, Ni,
After coating the metal surface with a chemical conversion film by an aqueous acidic liquid composition containing at least one selected from the group consisting of Si and optionally fluorine, the same composition as the aqueous acidic liquid composition and / or another composition And trivalent chromium, T
i, V, Mn, Y, Zr, Nb, Mo, Tc, Ru, R
h, Pd, W, Li, Na, K, Be, Mg, Ca, A
l, Fe, Ni, Co, Si, Sr, In, Ag, Z
n, Cu, Sc, organic acid, inorganic acid, organic acid salt, inorganic acid salt, amino acid, amino acid salt, fluorine, amines, alcohols, water-soluble polymer, surfactant, silane coupling agent, carbon powder, dye , A pigment, an organic colloid, an inorganic colloid, and at least one or more selected from the group consisting of an aqueous liquid composition containing one or more times, after the final immersion, the step of drying without rinsing Method. Further, a protective film with further improved corrosion resistance can be obtained by contacting an aqueous solution containing a silicon compound and / or an aqueous solution containing a resin and / or an inorganic colloid after the film formation, or an aqueous solution having a pH of 7.5 or more. found. Further, it has been found that the film obtained by the present invention is excellent in heat and corrosion resistance, and solves the problem of deterioration of corrosion resistance due to heat treatment, which is a drawback of conventional chromate films.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The details of the present invention are as follows. The aqueous acidic liquid composition of the present invention comprises (1) Ti,
V, Mn, Y, Zr, Nb, Mo, Tc, Ru, Rh,
At least one selected from the group consisting of Pd and W, and at least one selected from the group consisting of organic acids and / or inorganic acids such as oxygen acids of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, boric acid, and / or salts thereof. And a composition containing fluorine as an optional component, (2) trivalent chromium, Ti, V, Mn,
At least one selected from the group consisting of Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd and W and an organic acid and /
Or at least one selected from the group consisting of oxygen acids of phosphorus, inorganic acids such as nitric acid, sulfuric acid, hydrochloric acid, boric acid, and / or salts thereof, and Li, Na, K, Be, Co, M
At least one selected from the group consisting of g, Ca, Al, Ni and Si, and further a composition containing fluorine as an optional component, (3) 0.01 to 150 g / L of trivalent chromium and / or cobalt At least one selected from the group consisting of organic acids and / or nitric acid or salts thereof and 0.1
~ 300 g / L of Ti, V, Mn, Y, Zr, Nb, M
o, Tc, Ru, Rh, Pd, W, Li, Na, K, B
There is a composition containing at least one selected from the group consisting of e, Mg, Ca, Al, Ni and Si, and further fluorine as an optional component.

The exact behavior of each component in the composition (1) is unknown, but Ti, V, Mn, Y, Zr, Nb,
Mo, Tc, Ru, Rh, Pd, and W are presumed to form the skeleton of the film by depositing as a hydroxide or salt, or by being deposited on the metal surface by substitution, and oxygen of organic acid and / or phosphorus. Inorganic acids such as acids, nitric acid, sulfuric acid, hydrochloric acid, boric acid and / or their salts ensure the stability of metal components in a liquid and zinc, nickel, copper, silver, iron, cadmium, aluminum, magnesium and the like. It is presumed that the alloy surface of No. 3 is moderately etched and contributes to the smooth film formation. Ti, V, Mn, Y, Zr, Nb, Mo, Tc, R
u, Rh, Pd and W are supplied as salts or metal oxide salts such as titanium sulfate, ammonium titanate, sodium vanadate, manganese chloride and ammonium molybdate, but the supply source is not limited. It is presumed that some of these are ionized in the liquid and maintain an appropriate equilibrium state. The total amount of these is preferably 0.01 to 150 g / L and preferably 0.5 to 80 g / L. If it is less than this, it is difficult to form a good film, and a film does not form,
The film may be thin and the required performance may not be obtained. On the other hand, if the amount is larger than the above range, the appearance and gloss of the film are deteriorated and the corrosion resistance is deteriorated. If added, the economic loss due to pumping out will be large and it is not appropriate.

As organic acids and / or inorganic acids such as oxygen acids of phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, boric acid and / or salts thereof, any chemicals can be used, and the chemicals used are not limited. . The total amount of these is 0.01 to 300 g / L
Therefore, 1 to 100 g / L is preferable. If it is less than this range, not only good film formation is not carried out, but also the stability of the liquid is deteriorated due to precipitation formation and movement of equilibrium. If the amount is larger than the above range, a poor appearance of the treatment occurs due to over-etching of the metal surface, and good corrosion resistance cannot be obtained. The pH is 0.1 to 6.5, preferably 1.0 to 4.0. If it is lower than this, uniform film formation becomes difficult, and if it is higher, the corrosion resistance tends to be slightly lowered. As the chemicals used to adjust the pH, acids such as nitric acid and sulfuric acid may be added when the pH is high, and ammonia such as aqueous ammonia and sodium hydroxide may be added when the pH is low. is not.

Although the exact behavior of each component in the composition of (2) is unknown, trivalent chromium, Ti, V, Mn, Y, Z
It is presumed that r, Nb, Mo, Tc, Ru, Rh, Pd, and W are deposited as hydroxides or salts, or are deposited on the metal surface by substitution to form the skeleton of the film. Alternatively, phosphorus acid oxygen acid, inorganic acid such as nitric acid, sulfuric acid, hydrochloric acid, boric acid, and / or salts thereof ensure the stability of the metal component in the liquid and zinc, nickel, copper, silver, iron, cadmium, aluminum. It is presumed that it contributes to the smooth film formation by appropriately etching the surfaces of magnesium, magnesium and their alloys. In addition, Li, Na, K, Be, Co, M
It is speculated that g, Ca, Al, Ni, and Si contribute to the improvement of corrosion resistance by controlling the film formation and changing the film structure so that the corrosion current is easily dispersed. Trivalent chromium,
Ti, V, Mn, Y, Zr, Nb, Mo, Tc, Ru,
Rh, Pd, W are salts or metal oxide salts such as chromium chloride, chromium sulfate, titanium sulfate, ammonium titanate,
It is supplied by sodium vanadate, manganese chloride, ammonium molybdate, etc., but the supply source is not limited. It is presumed that some of these are ionized in the liquid and maintain an appropriate equilibrium state. The total amount of these is 0.
01 to 150 g / L and 0.5 to 80 g / L are preferable.
If the amount is less than this, it is difficult to form a good film, the film is not formed, or the film is thin and the required performance is not obtained. On the other hand, if the amount is larger than the above range, the appearance and gloss of the film are deteriorated and the corrosion resistance is deteriorated. If added, the economic loss due to pumping out will be large and it is not appropriate.

As the organic acid and / or inorganic acid such as oxygen acid of phosphorus, nitric acid, sulfuric acid, hydrochloric acid, boric acid and / or salts thereof, any chemical can be used, and the chemicals used are not limited. . The total amount of these is 0.01 to 300 g / L
Therefore, 1 to 100 g / L is preferable. If it is less than this range, not only good film formation is not carried out, but also the stability of the liquid is deteriorated due to precipitation formation and movement of equilibrium. If the amount is larger than the above range, a poor appearance of the treatment occurs due to over-etching of the metal surface, and good corrosion resistance cannot be obtained. The pH is 0.1 to 6.5, preferably 1.0 to 4.0. If it is lower than this, uniform film formation becomes difficult, and if it is higher, the corrosion resistance tends to be slightly lowered. As the chemicals used to adjust the pH, acids such as nitric acid and sulfuric acid may be added when the pH is high, and ammonia such as aqueous ammonia and sodium hydroxide may be added when the pH is low. is not.

Li, Na, K, Be, Co, Mg, C
The a, Al, Ni, and Si are supplied as salts, hydroxides, oxides, etc., such as sodium chloride, potassium hydroxide, cobalt sulfate, sodium silicate, etc., but the supply source is not limited. The total amount of these is 0.1 to 300 g / L and 1
~ 200 g / L is preferred. If it is less than this range, it becomes difficult to obtain the effect of improving the corrosion resistance. If added, the economic loss due to pumping out will be large and it is not appropriate.

Although the exact behavior of each component in the composition of (3) is unknown, trivalent chromium and cobalt are deposited as hydroxides or salts, or are deposited on the metal surface due to substitution, etc. It is presumed to form the skeleton, and organic acids, nitric acid, and their salts ensure the stability of metal components in liquids and protect zinc, nickel, copper, silver, iron, cadmium, aluminum, magnesium, and their alloy surfaces. It is presumed that it contributes to smooth film formation by etching moderately. In addition, Li, Na, K, Be, Co, Mg, Ca,
It is presumed that Al, Ni, and Si contribute to the improvement of corrosion resistance by controlling the film formation and changing the film structure so that the corrosion current is easily dispersed. Trivalent chromium and cobalt are supplied as salts such as chromium chloride, chromium sulfate, chromium nitrate, cobalt chloride, cobalt sulfate and cobalt nitrate, but the supply source is not limited. It is presumed that some of these are ionized in the liquid and maintain an appropriate equilibrium state. The total amount of these is preferably 0.01 to 150 g / L and preferably 0.5 to 80 g / L. If it is less than this, it is difficult to form a good film, and a film does not form,
The film may be thin and the required performance may not be obtained. On the other hand, if the amount is larger than the above range, the appearance and gloss of the film are deteriorated and the corrosion resistance is deteriorated. If added, the economic loss due to pumping out will be large and it is not appropriate.

As the organic acid and / or nitric acid and / or salts thereof, any chemical other than nitric acid can be used, and the chemicals used are not limited. These are 0.0 in total
It is necessary to contain 1 to 300 g / L, preferably 1 to 100 g / L. If it is less than this range, not only good film formation is not carried out, but also the stability of the liquid is deteriorated due to precipitation formation and movement of equilibrium. If the amount is larger than the above range, a poor appearance of the treatment occurs due to over-etching of the metal surface, and good corrosion resistance cannot be obtained. The pH is preferably 0.1 to 6.5, more preferably 1.0 to 4.0. If it is lower than this, uniform film formation becomes difficult, and if it is higher, the corrosion resistance tends to be slightly lowered. High pH for chemicals used to adjust pH
In such a case, an acid such as nitric acid or sulfuric acid may be added, and in the case of a low pH, an aqueous ammonia, an alkali such as sodium hydroxide may be added, and the chemicals to be added are not limited.

Li, Na, K, Be, Co, Mg, C
The a, Al, Ni, and Si are supplied as salts, hydroxides, oxides, etc., such as sodium chloride, potassium hydroxide, cobalt sulfate, sodium silicate, etc., but the supply source is not limited. The total amount of these is 0.1 to 300 g / L, preferably 1 to 200 g / L. If it is less than this range, it becomes difficult to obtain the effect of improving the corrosion resistance. If added, the economic loss due to pumping out will be large and it is not appropriate.

The treatment time for film formation can be applied within a very wide range. For example, a long-time treatment of about 250 seconds or a treatment time of a general reaction type chromate using hexavalent chromium, which is 10 to 30 seconds or less, can be applied.

It has been found that a film having a beautiful glossy appearance and excellent corrosion resistance can be formed without using hexavalent chromium by drying without a rinsing step after the film formation treatment. The drying method may be a conventional drying method such as warm air drying or centrifugal drying, but the method is not limited. By drying without performing the rinsing step, the corrosion resistance is significantly improved as compared with the case where the rinsing step is performed. It is speculated that this is due to the fact that the active ingredient is not eluted by rinsing and the amount of the active ingredient attached is increased.

Further, after coating the surface of the metal with a layer formed from each of the above-mentioned aqueous acidic liquid compositions, one or a plurality of times is applied to an aqueous liquid composition having the same composition and / or different composition from each of the above-mentioned aqueous acidic liquid compositions. It has been found that a film having a beautiful glossy appearance and excellent corrosion resistance can be formed without using hexavalent chromium even in the step of dipping once and, after the final dipping, drying without rinsing. The aqueous liquid composition is trivalent chromium, T
i, V, Mn, Y, Zr, Nb, Mo, Tc, Ru, R
h, Pd, W, Li, Na, K, Be, Mg, Ca, A
l, Fe, Ni, Co, Si, Sr, In, Ag, Z
n, Cu, Sc, organic acid, inorganic acid, organic acid salt, inorganic acid salt, amino acid, amino acid salt, fluorine, amines, alcohols, water-soluble polymer, surfactant, silane coupling agent, carbon powder, dye , A pigment, an organic colloid, and an inorganic colloid.

The behavior of each component of the aqueous liquid composition is unknown, but trivalent chromium, Ti, V, Mn, Y, Zr and N are used.
b, Mo, Tc, Ru, Rh, Pd, W, Li, Na,
K, Be, Mg, Ca, Al, Fe, Ni, Co, S
i, Sr, In, Ag, Zn, Cu, Sc, organic acid, inorganic acid, organic acid salt, inorganic acid salt, amino acid, amino acid salt, fluorine, amines, alcohols, water-soluble polymer, surfactant, silane It is presumed that the coupling agent, carbon powder, dye, pigment, organic colloid, and inorganic colloid contribute to the reinforcement of active ingredients and the improvement of covering property by forming a layer by adhesion or chemical conversion on the surface of the chemical conversion film.

Trivalent chromium, Ti, V, Mn, Y, Zr,
Nb, Mo, Tc, Ru, Rh, Pd, W, Li, N
a, K, Be, Mg, Ca, Al, Fe, Ni, Co,
Si, Sr, In, Ag, Zn, Cu, Sc, organic acid,
Inorganic acid, organic acid salt, inorganic acid salt, amino acid, amino acid salt,
Fluorine, amines, alcohols, water-soluble polymers, surfactants, silane coupling agents, carbon powder,
Dyes, pigments, organic colloids and inorganic colloids are chromium chloride, chromium sulfate, chromium nitrate, titanium sulfate, titanium sulfate, ammonium titanate, sodium vanadate, manganese chloride, ammonium molybdate, sodium chloride,
Potassium hydroxide, cobalt sulfate, sodium silicate, citric acid, malonic acid, oxalic acid, adipic acid, succinic acid,
Tartaric acid, ascorbic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, boric acid, glycine, sodium fluoride, ammonia water, dimethylamine, methanol, butanol, polyvinyl alcohol, polyacrylic amide, β-naphthol ethylene oxide adduct, colloidal alumina , Colloidal silica and the like, but the source is not limited. Also, the total amount is not limited.

Further, by contacting with an aqueous solution containing a silicon compound and / or a resin and / or an inorganic colloid or an aqueous solution having a pH of 7.5 or more after forming a film by each of the above methods, a protective film having further improved corrosion resistance can be obtained. It turned out to be obtained. As the silicon compound, sodium silicate, potassium silicate, lithium silicate, or a particle size of 50
Examples include colloidal silica having a particle size of 0 nm or less (also an inorganic colloid), and colloidal silica having a particle size of 50 nm or less tends to exhibit particularly stable performance. The appropriate amount of these is 0.01 to 500 g / L, preferably 10 to 150 g.
/ L. Examples of the resin include acrylic resins, epoxy resins, cellulose resins, polyvinyl alcohol resins, urethane resins, and fluorine resins, but the types and amounts thereof are not limited. Colloidal alumina as an inorganic colloid,
Examples thereof include antimony pentoxide sol.

The metal protective coating formed by the treatment method defined in the present invention has the same aqueous acidic liquid composition, but the conventional method, that is, the surface of the metal is coated with a layer formed from the aqueous acidic liquid composition. Since it has higher corrosion resistance than the film produced by the process of rinsing and then drying after the process, its industrial value exceeds that of the metal protective film produced by the conventional method. Although the film structure is unknown, it is clearly different from the metal protective film formed by the conventional method due to the difference in corrosion resistance.

By using the treatment method specified in the present invention, harmful hexavalent chromium is not used, and a highly corrosive fluoride is not an essential component, and the treatment facility and treatment conditions are almost the same as those of conventional chromate. It is possible to form a strong protective film on the surface of the metal substrate. This will not only affect general users who are concerned about the elution of hexavalent chromium from the treated products, but also the health effects of chromate manufacturers and chromate processors that have been exposed to the harmful effects of chromic acid, and the effects on wildlife. It is possible to solve the problem.

As a technique prior to the present invention, a chromate treatment method using hexavalent chromium, a reactive chromate using trivalent chromium which does not use hexavalent chromium and is less harmful, and an alternative treatment agent similar to that and chromium are used. Alternative anticorrosive agents that are not used at all are known. Reactive chromates using trivalent chromium, which does not use hexavalent chromium and is less harmful, are disclosed in JP-A-61-587, which has the highest corrosion resistance among reactive chromates using hexavalent chromium. It corresponds to low-grade gloss (blue) chromate, and cannot be used in parts requiring corrosion resistance exceeding it. As an alternative treating agent similar to that, JP-A-10-
Although there is 183364 gazette, etc., it has a corrosion resistance of practically practical level, but it is slightly inferior to the most common colored (yellow) chromate among the current reaction chromate using hexavalent chromium, so it is perfect. It is hard to say that it is an alternative treatment agent. Further, as an alternative rust preventive treatment agent which does not use chromium at all, there is JP-A-2000-199077 and the like, but the corrosion resistance thereof is not as high as that of the colored chromate, and particularly the corrosion resistance is remarkably lowered when the film is scratched. For the above reasons, none of the above-mentioned prior arts reach the present invention. Further, it has been found that the film obtained by the present invention has excellent heat resistance and corrosion resistance, and solves the problem of deterioration in corrosion resistance due to heat treatment, which is a drawback of conventional chromate films.

[0024]

EXAMPLES The present invention will be described below with reference to examples. In the test, the test pieces were subjected to appropriate treatments such as degreasing and dipping in nitric acid, and then the following treatments were performed. The evaluation was performed on the appearance and corrosion resistance, and the results of the examples of the present invention are shown in Table 1.
Table 2 shows the results of the comparative example.

Example 1 An electrogalvanized iron plate (50 × 100 × 1 mm) contains 20 g / L of titanium sulfate, 10 g / L of sodium vanadate, 10 g / L of phosphoric acid, and 5 g / L of nitric acid.
After dipping for 60 seconds in the treatment liquid adjusted to H2.3, it was dried without performing a rinsing step to prepare a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 2 An electrogalvanized iron plate (50 × 100 × 1 mm) contains 20 g / L of titanium sulfate, 10 g / L of sodium vanadate, 10 g / L of phosphoric acid and 5 g / L of nitric acid, and p is added with ammonia.
After immersing in a treatment liquid adjusted to H2.3 (the same composition as the treatment liquid described in Example 1) for 60 seconds, a rinsing step is performed, and then immersing in a treatment liquid having the same composition as the treatment liquid for 5 seconds to perform a rinsing step. Without drying, a test piece was prepared. The appearance was visually evaluated, and the corrosion resistance was 2 in the salt spray test (JIS Z 2371).
It was evaluated by the surface condition after 40 hours.

Example 3 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium nitrate 20 g / L, sodium tungstate 3 g / L,
Test pieces containing 1 g / L of sodium gluconate, 20 g / L of phosphoric acid and 2 g / L of calcium chloride, dipped in a treatment solution adjusted to pH 2.0 with caustic soda for 25 seconds, and then dried without a rinsing step Was produced. The appearance was visually evaluated, and the corrosion resistance was 24 in the salt spray test (JIS Z 2371).
The evaluation was made by the surface condition at the time of 0 hours.

Example 4 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium nitrate 20 g / L, sodium tungstate 3 g / L,
25 in a treatment liquid (same composition as the treatment liquid described in Example 3) containing 1 g / L of sodium gluconate, 20 g / L of phosphoric acid, 2 g / L of calcium chloride and adjusted to pH 2.0 with caustic soda.
After soaking for 2 seconds and after rinsing, chromium nitrate 10g /
After dipping for 5 seconds in a treatment solution containing L, sodium tungstate 1.5 g / L, sodium gluconate 0.5 g / L, phosphoric acid 10 g / L, calcium chloride 1 g / L and adjusted to pH 3.5 with caustic soda A test piece was prepared by drying without rinsing. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (J
It was evaluated by the surface condition after 240 hours in IS Z 2371).

Example 5 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium nitrate 20 g / L, sodium tungstate 3 g / L,
25 in a treatment liquid (same composition as the treatment liquid described in Example 3) containing 1 g / L of sodium gluconate, 20 g / L of phosphoric acid, 2 g / L of calcium chloride and adjusted to pH 2.0 with caustic soda.
After soaking for 2 seconds and drying without rinsing,
A test piece was prepared by immersing it in a 10.0 sodium hydroxide aqueous solution and drying it. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 6 An electrogalvanized iron plate (50 × 100 × 1 mm) was charged with ammonium molybdate (10 g / L) and phosphoric acid (10 g / L).
L, No. 3 sodium silicate 10g / L containing ammonia p
After dipping in the treatment liquid adjusted to H2.0 for 60 seconds, it was dried without performing a rinsing step to prepare a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition at the time of 240 hours in the salt spray test (JIS Z2371).

Example 7 An electrogalvanized iron plate (50 × 100 × 1 mm) was charged with ammonium molybdate 10 g / L and phosphoric acid 10 g / L.
L, No. 3 sodium silicate 10g / L containing ammonia p
After dipping for 60 seconds in a treatment liquid adjusted to H2.0 (the same composition as the treatment liquid described in Example 6), a rinsing step was performed by immersing the treatment liquid in a 2-fold diluted aqueous solution for 3 seconds without performing the rinsing step. Without performing, it dried and the test piece was produced. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 8 An electrogalvanized iron plate (50 × 100 × 1 mm) was added to a treatment liquid containing 30 g / L of chromium nitrate, 20 g / L of sodium nitrate and 5 g / L of manganese chloride and adjusted to pH 1.8 with ammonia. After soaking for a second, it was dried without performing a rinsing step to prepare a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 9 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 30 g / L of chromium nitrate, 20 g / L of sodium nitrate, and 5 g / L of manganese chloride and adjusted to pH 1.8 with ammonia was prepared. The same composition as the treatment solution described in Example 8) was soaked for 60 seconds, and then a rinsing step was performed, followed by soaking for 5 seconds in a treatment solution containing 5 g / L of chromium nitrate, and 3 g of chromium nitrate without rinsing.
A test piece was prepared by immersing in a treatment liquid containing / L for 5 seconds and drying without rinsing. The appearance was visually evaluated, and the corrosion resistance was 240 in a salt spray test (JIS Z 2371).
The evaluation was made by the surface condition at the time point.

Example 10 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium nitrate 20 g / L, tartaric acid 10 g / L, phosphoric acid 15 g.
/ L, sulfuric acid 2g / L, cobalt nitrate 10g / L, Snowtex C (Colloidal silica manufactured by Nissan Chemical Industries, Ltd.)
A test piece was prepared by immersing for 15 seconds in a treatment liquid containing 50 g / L and adjusted to pH 2.5 with caustic soda, and then dried without performing a rinsing step. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 11 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium sulfate 20 g / L, sodium nitrate 15 g / L, titanium sulfate 5 g / L, Snowtex 20 (Nissan Chemical Industry Co., Ltd.).
(Colloidal silica produced by the present invention) was immersed in an aqueous solution containing 100 g / L and adjusted to pH 2.0 with caustic soda for 20 seconds, and then dried without a rinsing step to prepare a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 237).
The evaluation was made based on the surface condition after 240 hours in 1).

Example 12 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 15 g / L of chromium chloride, 8 g / L of cobalt chloride, 5 g / L of oxalic acid, 5 g / L of nitric acid and 5 g / L of magnesium chloride, and ammonia. 40 to the treatment liquid adjusted to pH 2.2 with water
After soaking for a second, it was dried without performing a rinsing step to prepare a test piece. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (J
It was evaluated by the surface condition after 240 hours in IS Z 2371).

Example 13 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 15 g / L of chromium chloride, 8 g / L of cobalt chloride, 5 g / L of oxalic acid, 5 g / L of nitric acid and 5 g / L of magnesium chloride, and ammonia. After immersing in a treatment liquid adjusted to pH 2.2 with water (the same composition as the treatment liquid described in Example 12) for 40 seconds, a rinsing step was performed, and then chromium chloride 5 g / L, cobalt chloride 2 g / L, nitric acid 2 g / L, 1 g / L of magnesium chloride, and a solution adjusted to pH 4.0 with aqueous ammonia for 10 seconds and dried without a rinsing step to prepare a test piece. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (JI
SZ 2371) evaluated the surface condition after 240 hours.

Example 14 An electrogalvanized iron plate (50 × 100 × 1 mm) was applied to chromium chloride 10 g / L, cobalt chloride 10 g / L, malonic acid 5 g / L, nitric acid 5 g / L, magnesium acetate 5 g / L.
4 to the treatment liquid containing ammonia and adjusted to pH 2.2 with aqueous ammonia.
After soaking for 0 second, it was dried without performing a rinsing step to prepare a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 15 An electrogalvanized iron plate (50 × 100 × 1 mm) was applied to chromium chloride 10 g / L, cobalt chloride 10 g / L, malonic acid 5 g / L, nitric acid 5 g / L, magnesium acetate 5 g / L.
After dipping for 40 seconds in a treatment liquid (containing the same composition as the treatment liquid described in Example 14) containing ammonia and adjusted to pH 2.2 with ammonia water,
After performing the rinsing step, it is immersed for 10 seconds in a treatment solution containing 10 g / L of chromium chloride, 10 g / L of cobalt chloride, 5 g / L of malonic acid and 5 g / L of magnesium acetate and adjusted to pH 3.0 with ammonia water, and rinsed. A test piece was prepared by drying without any steps. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 16 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 30 g / L of chromium nitrate, 20 g / L of sodium nitrate and 5 g / L of manganese chloride and adjusted to pH 1.8 with ammonia was prepared. The same composition as the treatment solution described in Example 8) was soaked for 60 seconds, and then a rinsing step was performed, followed by soaking for 5 seconds in a treatment solution containing 5 g / L of chromium nitrate, and 3 g of chromium nitrate without rinsing.
/ L-containing treatment solution for 5 seconds, dried without rinsing, and then added to an aqueous solution containing Snowtex C (Nissan Chemical Co., Ltd. colloidal silica) 50 g / L and caustic soda 2 g / L. A test piece was prepared by immersing and drying. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 2
It was evaluated by the surface condition after the lapse of 240 hours in 371).

Example 17 An electrogalvanized iron plate (50 × 100 × 1 mm) was charged with ammonium molybdate (10 g / L) and phosphoric acid (10 g / L).
L, No. 3 sodium silicate 10g / L containing ammonia p
After dipping for 60 seconds in a treatment liquid adjusted to H2.0 (the same composition as the treatment liquid described in Example 6), a rinsing step was performed by immersing the treatment liquid in a 2-fold diluted aqueous solution for 3 seconds without performing the rinsing step. After drying without performing it, it was further dipped in an aqueous solution containing 50 g / L of Snowtex C (Colloidal silica manufactured by Nissan Chemical Industries, Ltd.) and 2 g / L of caustic soda and dried to prepare a test piece. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (JI
SZ 2371) evaluated the surface condition after 240 hours.

Example 18 An electrogalvanized iron plate (50 × 100 × 1 mm) was used for titanium sulfate 20 g / L, manganese chloride 10 g / L, phosphoric acid 10 g / L, nitric acid 5 g / L, magnesium nitrate 5 g / L.
3 in a treatment liquid containing ammonia and adjusted to pH 2.0 with ammonia
After soaking for 0 seconds and drying without performing a rinsing step, it was further dipped in an aqueous solution containing 50 g / L of Snowtex C (Colloidal silica manufactured by Nissan Chemical Industries, Ltd.) and 2 g / L of caustic soda to be dried and tested. Pieces were made. Visually evaluate the appearance,
The corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JISZ 2371).

Example 19 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 15 g / L of chromium nitrate, 1 g / L of sodium gluconate, 20 g / L of phosphoric acid and 3 g / L of sodium vanadate, and caustic soda After being dipped in the treatment solution adjusted to pH 2.3 with 25 seconds, dried without rinsing step, and then further treated with 5G018.
A test piece was prepared by immersing in (silicon surface-containing, organic-inorganic composite film forming agent manufactured by Japan Surface Chemical Co., Ltd.) and drying. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 23
The evaluation was carried out by the surface condition after the lapse of 240 hours in 71).

Example 20 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium nitrate 20 g / L, sodium tungstate 3 g / L,
25 in a treatment liquid (same composition as the treatment liquid described in Example 3) containing 1 g / L of sodium gluconate, 20 g / L of phosphoric acid, 2 g / L of calcium chloride and adjusted to pH 2.0 with caustic soda.
After soaking for 2 seconds and after rinsing, chromium nitrate 10g /
After dipping for 5 seconds in a treatment solution containing L, sodium tungstate 1.5 g / L, sodium gluconate 0.5 g / L, phosphoric acid 10 g / L, calcium chloride 1 g / L and adjusted to pH 3.5 with caustic soda After drying without rinsing, another 5G
018 (manufactured by Japan Surface Chemical Co., Ltd., silicon-containing, organic / inorganic composite film agent) was dipped and dried to prepare a test piece. The appearance is visually evaluated, and the corrosion resistance is determined by a salt spray test (JISZ
2371) and the surface state after 240 hours.

Example 21 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 15 g / L of chromium nitrate, 1 g / L of sodium gluconate, 20 g / L of phosphoric acid and 3 g / L of sodium vanadate, and caustic soda After being immersed for 25 seconds in a treatment liquid (same composition as the treatment liquid described in Example 19) adjusted to pH 2.3 with 5G018 (manufactured by Nippon Surface Chemical Co., Ltd., silicon). The test piece was prepared by immersing it in an organic / inorganic composite coating agent). The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 22 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium sulfate 10 g / L, cobalt nitrate 5 g / L, nitric acid 5 g.
/ L, ammonium tungstate 5 g / L and dipping for 15 seconds in a treatment solution adjusted to pH 1.7 with ammonia water, and then dried without a rinsing step, and then No. 3 sodium silicate 50 g / L and caustic soda A test piece was prepared by immersing in an aqueous solution containing 2 g / L for 30 seconds and drying. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 23 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium sulfate 20 g / L, sodium nitrate 10 g / L, and sulfuric acid 5 g.
/ L, titanium sulfate 5 g / L, Snowtex 20 (Colloidal silica manufactured by Nissan Chemical Industries, Ltd.) 100 g / L, and immersed in an aqueous solution adjusted to pH 2.0 with caustic soda for 20 seconds, followed by a rinsing step. Without drying, Snowtex C (Colloidal silica manufactured by Nissan Chemical Industries, Ltd.)
A test piece was prepared by immersing in an aqueous solution containing 50 g / L and 2 g / L of caustic soda and drying. The appearance was visually evaluated, and the corrosion resistance was 2 in the salt spray test (JIS Z 2371).
It was evaluated by the surface condition after 40 hours.

Example 24 An electrogalvanized iron plate (50 × 100 × 1 mm) was applied to chromium chloride 10 g / L, cobalt chloride 10 g / L, malonic acid 5 g / L, nitric acid 5 g / L, magnesium acetate 5 g / L.
After dipping for 40 seconds in a treatment solution (containing the same composition as the treatment solution described in Example 15) containing ammonia and adjusted to pH 2.2 with ammonia water, it was dried without a rinsing step, and further, 5G018 (manufactured by Nippon Surface Chemical Co., Ltd.). , A silicon-containing organic / inorganic composite coating agent) and dried to prepare a test piece. Visually evaluate the appearance,
The corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JISZ 2371).

Example 25 Zinc-iron alloy plated iron plate (50 × 100 × 1 mm)
20 g / L of chromium chloride, 5 g / L of citric acid, 5 g of nitric acid
/ L, ammonium titanate 5 g / L, and magnesium acetate 5 g / L were immersed for 40 seconds in a treatment liquid adjusted to pH 2.2 with aqueous ammonia, and then dried without a rinsing step to prepare test pieces. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 26 Zinc-iron alloy plated iron plate (50 × 100 × 1 mm)
20 g / L of chromium chloride, 5 g / L of citric acid, 5 g of nitric acid
/ L, 5 g / L of ammonium titanate, 5 g / L of magnesium acetate and a pH of 2.2 adjusted with ammonia water (the same composition as the treatment liquid described in Example 25) for 40 seconds, followed by a rinsing step. After drying without performing, it was dipped in an aqueous solution containing 30 g / L of No. 3 sodium silicate and 1 g / L of caustic soda for 40 seconds and dried to obtain a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 2
It was evaluated by the surface condition after the lapse of 240 hours in 371).

Example 27 Zinc-nickel alloy plated iron plate (50 × 100 × 1)
mm) chromium chloride 20 g / L, cobalt chloride 10 g / L
L, 5 g / L of citric acid, 5 g / L of nitric acid, 5 g / L of calcium acetate and 5 g / L of calcium acetate soaked in a treatment solution adjusted to pH 1.5 with caustic soda for 40 seconds, and then dried without rinsing to give test pieces. It was made. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Example 28 Zinc-nickel alloy-plated iron plate (50 × 100 × 1)
mm) chromium chloride 20 g / L, cobalt chloride 10 g / L
L, 5 g / L citric acid, 5 g / L nitric acid, 5 g / L calcium acetate and 5 g / L calcium acetate and adjusted to pH 1.5 with caustic soda (the same composition as the treatment liquid described in Example 27), after dipping for 40 seconds, It was dried without performing a rinsing step, further dipped in 5G018 (manufactured by Nippon Surface Chemical Co., Ltd., silicon-containing, organic / inorganic composite film agent) and dried to prepare a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 237).
The evaluation was made based on the surface condition after 240 hours in 1).

Example 29 An electrogalvanized iron plate (50 × 100 × 1 mm) was added to a treatment liquid containing 30 g / L of chromium nitrate, 20 g / L of sodium nitrate and 5 g / L of manganese chloride and adjusted to pH 1.8 with ammonia. After soaking for a second and then dried without a rinsing step, the dried one was left in a constant temperature bath at 200 ° C. for 1 hour to obtain a test piece. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (JI
It was evaluated by the surface condition of SZ2371) after 240 hours.

Comparative Example 1 A galvanized iron plate (50 × 100 × 1 mm) was subjected to no treatment to obtain a test piece, and a salt spray test (JIS Z 2
The time until the occurrence of white rust in 371) was investigated.

Comparative Example 2 A galvanized iron plate (50 × 100 × 1 mm) containing a commercially available hexavalent chromium chromate treatment solution (Romate 6) was used.
2. Immersed in Nihon Surface Chemical Co., Ltd. for 15 seconds, formed a film, washed with water, and dried to obtain a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 237).
The evaluation was made based on the surface condition after 240 hours in 1).

Comparative Example 3 A galvanized iron plate (50 × 100 × 1 mm) containing a commercially available hexavalent chromium chromate treatment solution (Romate 6) was used.
2. A test piece was obtained by immersing the film in Nihon Surface Chemical Co., Ltd. for 15 seconds and drying it without rinsing after film formation. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 2
It was evaluated by the surface condition after the lapse of 240 hours in 371).

Comparative Example 4 A galvanized iron plate (50 × 100 × 1 mm) was used as a reaction type chromate treatment liquid (4K0) using commercially available trivalent chromium.
49, manufactured by Nippon Surface Chemical Co., Ltd.) for 40 seconds, washed with water after forming a film, and dried to obtain a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 237).
The time until the occurrence of white rust in 1) was evaluated.

Comparative Example 5 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 20 g / L of titanium sulfate, 10 g / L of sodium vanadate, 10 g / L of phosphoric acid, and 5 g / L of nitric acid was added.
A test piece was dipped in a treatment liquid adjusted to H2.3 (same composition as the treatment liquid described in Example 1) for 60 seconds, washed with water for film formation, and dried. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Comparative Example 6 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium nitrate 20 g / L, sodium tungstate 3 g / L,
25 in a treatment liquid containing sodium gluconate 1 g / L, phosphoric acid 20 g / L, calcium chloride 2 g / L and adjusted to pH 2.0 with caustic soda (same composition as the treatment liquid described in Example 2).
The test piece was dipped for 2 seconds, washed with water for film formation, and dried. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (JI
S Z2371) was evaluated by the surface condition after 240 hours.

Comparative Example 7 An electrogalvanized iron plate (50 × 100 × 1 mm) containing 30 g / L of chromium nitrate, 20 g / L of sodium nitrate, 5 g / L of manganese chloride and adjusted to pH 1.8 with ammonia was prepared. The test piece was dipped in the same composition as the treatment solution described in Example 5) for 60 seconds, washed with water after forming a film, and dried. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (JI
It was evaluated by the surface condition of SZ2371) after 240 hours.

Comparative Example 8 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium nitrate 20 g / L, cobalt nitrate 10 g / L, tartaric acid 10 g / L, nitric acid 3 g / L, sulfuric acid 2 g / L, Snowtex C ( Nissan Chemical Industries colloidal silica) 50
A test piece was dipped in a treatment liquid containing g / L and adjusted to pH 2.5 with caustic soda for 15 seconds, washed with water after forming a film, and dried. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Comparative Example 9 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed on chromium sulfate 10 g / L, cobalt nitrate 5 g / L, nitric acid 5 g.
/ L, 5 g / L ammonium tungstate and adjusted to pH 1.7 with ammonia water (the same composition as the treatment solution described in Example 12) for 15 seconds, washed with water after film formation and dried, A test piece was prepared by immersing in an aqueous solution containing 50 g / L of No. 3 sodium silicate and 2 g / L of caustic soda and drying. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

Comparative Example 10 An electrogalvanized iron plate (50 × 100 × 1 mm) was placed in chromium chloride 10 g / L, cobalt chloride 10 g / L, malonic acid 5 g / L, nitric acid 5 g / L, magnesium acetate 5 g / L.
After dipping for 40 seconds in a treatment solution (containing the same composition as the treatment solutions described in Examples 9 and 14) containing ammonia and adjusted to pH 2.2 with ammonia water, washed with water after film formation and dried, and then 5G018.
A test piece was prepared by immersing in (silicon surface-containing, organic-inorganic composite film forming agent manufactured by Japan Surface Chemical Co., Ltd.) and drying. The appearance was visually evaluated, and the corrosion resistance was evaluated by a salt spray test (JIS Z 23
The evaluation was carried out by the surface condition after the lapse of 240 hours in 71).

Comparative Example 11 Zinc-iron alloy plated iron plate (50 × 100 × 1 mm)
Chromium chloride 20 g / L, ammonium titanate 5 g /
L, 5 g / L of citric acid, 5 g / L of nitric acid, 5 g / L of magnesium acetate and a pH of 2.2 with ammonia water (the same composition as that of the treatment liquid described in Example 15) for 40 seconds to form a film. After generation, it was washed with water and dried to prepare a test piece. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (JI
It was evaluated by the surface condition of SZ2371) after 240 hours.

Comparative Example 12 Zinc-nickel alloy plated iron plate (50 × 100 × 1)
mm) chromium chloride 20 g / L, cobalt chloride 10 g / L
L, citric acid 5 g / L, nitric acid 5 g / L, calcium acetate 5 g / L and a pH of 1.5 adjusted with caustic soda (the same composition as the treatment solutions described in Examples 17 and 18).
It was immersed for 2 seconds, washed with water after forming a film, and dried to prepare a test piece. The appearance is visually evaluated, and the corrosion resistance is evaluated by a salt spray test (J
It was evaluated according to the surface condition after 240 hours in IS Z2371).

Comparative Example 13 Zinc-nickel alloy plated iron plate (50 × 100 × 1)
mm) chromium chloride 20 g / L, cobalt chloride 10 g / L
L, citric acid 5 g / L, nitric acid 5 g / L, calcium acetate 5 g / L and a pH of 1.5 adjusted with caustic soda (the same composition as the treatment solutions described in Examples 17 and 18).
It was immersed for 2 seconds, washed with water, dried, and further immersed in 5G018 (manufactured by Japan Surface Chemical Co., Ltd., organic / inorganic composite film agent) and dried to prepare a test piece. The appearance was visually evaluated, and the corrosion resistance was 240 in a salt spray test (JIS Z 2371).
The evaluation was made by the surface condition at the time point.

Comparative Example 14 A galvanized iron plate (50 × 100 × 1 mm) containing a commercially available chromate treatment solution containing hexavalent chromium (Romate 6)
2. Immersed in Nihon Surface Chemical Co., Ltd. for 15 seconds, formed a film, washed with water, dried and left in a constant temperature bath at 200 ° C. for 1 hour to obtain a test piece. The appearance was visually evaluated, and the corrosion resistance was evaluated by the surface condition after 240 hours in a salt spray test (JIS Z 2371).

[0068]

[Table 1]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23C 22/22 C23C 22/22 22/34 22/34 22/36 22/36 22/40 22/40 22 / 42 22/42 22/44 22/44 22/50 22/50 22/52 22/52 22/56 22/56 22/57 22/57 22/58 22/58 22/83 22/83 (72) Inventor Hidekazu Horie 1136 Hagizono, Chigasaki-shi, Kanagawa Japan Surface Chemicals Co., Ltd. F-term inside Chigasaki Plant (reference) 4D075 AB01 AE03 BB24Z BB73Y BB91Y CA33 CB04 DA06 DB01 DB02 DB05 DB06 DB33 DB07 DB22 DB16 DB07 DB07 DB02 DB16 DB07 DB07 DB22 EC07 EC35 EC45 EC53 EC54 4K026 AA01 AA02 AA06 AA07 AA09 AA11 BA01 BA02 BA12 BB08 CA18 CA19 CA23 CA26 CA28 CA29 CA30 CA31 CA32 CA33 CA37 CA38 CA39 CA41 DA02 DA11 EB02 EB08

Claims (11)

[Claims] 1. A method for forming a protective metal film, comprising the steps of coating the surface of a metal with a layer formed from an aqueous acidic liquid composition and drying the aqueous acidic liquid composition without rinsing. The aqueous acidic liquid composition is (A) Ti, V, Mn,
At least one selected from the group consisting of Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd and W, and (B) selected from the group consisting of an organic acid and / or an inorganic acid and / or a salt thereof. A method of forming a metal protective film, which comprises at least one and (C) fluorine as an optional component. 2. A method for forming a protective metal film comprising the steps of coating the surface of a metal with a layer formed from an aqueous acidic liquid composition and drying the aqueous acidic liquid composition without rinsing. The aqueous acidic liquid composition is (A) trivalent chromium, Ti,
V, Mn, Y, Zr, Nb, Mo, Tc, Ru, Rh,
At least one selected from the group consisting of Pd and W,
(B) at least one selected from the group consisting of organic acids and / or inorganic acids and / or salts thereof, (C) Li,
Na, K, Be, Co, Mg, Ca, Al, Ni, Si
A method for forming a protective film of a metal, which comprises at least one selected from the group consisting of: and (D) fluorine as an optional component. 3. A method for forming a protective metal film, comprising the steps of coating the surface of a metal with a layer formed from an aqueous acidic liquid composition and drying the aqueous acidic liquid composition without rinsing. Aqueous acidic liquid composition has (A) 0.01-150 g
/ L trivalent chromium and / or cobalt, (B) at least one selected from the group consisting of organic acids and / or nitric acid and / or salts thereof, (C) 0.1 to 300 g / L Ti, V , Mn, Y, Zr, Nb, Mo, Tc, Ru,
Rh, Pd, W, Li, Na, K, Be, Mg, Ca,
A method of forming a metal protective film, which comprises at least one selected from the group consisting of Al, Ni, and Si, and (D) fluorine as an optional component. 4. The surface of a metal is coated with a layer formed from an aqueous acidic liquid composition, and then immersed once or a plurality of times in an aqueous liquid composition having the same composition and / or a different composition from the aqueous acidic liquid composition. A method for forming a metal protective film, which comprises a step of drying after the final immersion without rinsing, wherein the aqueous acidic liquid composition comprises (A) Ti, V, Mn,
At least one selected from the group consisting of Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd and W, and (B) selected from the group consisting of an organic acid and / or an inorganic acid and / or a salt thereof. At least one and (C) fluorine as an optional component, wherein the aqueous liquid composition is trivalent chromium, Ti, V, Mn,
Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, W,
Li, Na, K, Be, Mg, Ca, Al, Fe, N
i, Co, Si, Sr, In, Ag, Zn, Cu, S
c, organic acid, inorganic acid, organic acid salt, inorganic acid salt, amino acid,
Those containing at least one or more selected from the group consisting of amino acid salts, fluorine, amines, alcohols, water-soluble polymers, surfactants, silane coupling agents, carbon powders, dyes, pigments, organic colloids and inorganic colloids. A method for forming a protective film of a metal. 5. The surface of a metal is coated with a layer formed from an aqueous acidic liquid composition, and then immersed once or a plurality of times in an aqueous liquid composition having the same composition and / or a different composition from the aqueous acidic liquid composition. A method for forming a metal protective film, which comprises a step of drying without rinsing after the final immersion, wherein the aqueous acidic liquid composition comprises (A) trivalent chromium, Ti,
V, Mn, Y, Zr, Nb, Mo, Tc, Ru, Rh,
At least one selected from the group consisting of Pd and W,
(B) at least one selected from the group consisting of organic acids and / or inorganic acids and / or salts thereof, (C) Li,
Na, K, Be, Co, Mg, Ca, Al, Ni, Si
At least one selected from the group consisting of, and (D) fluorine as an optional component, wherein the aqueous liquid composition is trivalent chromium, Ti, V, Mn,
Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, W,
Li, Na, K, Be, Mg, Ca, Al, Fe, N
i, Co, Si, Sr, In, Ag, Zn, Cu, S
c, organic acid, inorganic acid, organic acid salt, inorganic acid salt, amino acid,
Those containing at least one or more selected from the group consisting of amino acid salts, fluorine, amines, alcohols, water-soluble polymers, surfactants, silane coupling agents, carbon powders, dyes, pigments, organic colloids and inorganic colloids. A method for forming a protective film of a metal. 6. The surface of a metal is coated with a layer formed from an aqueous acidic liquid composition, and then dipped once or a plurality of times in an aqueous liquid composition having the same composition and / or a different composition from the aqueous acidic liquid composition. A method for forming a protective metal film comprising a step of drying after the final immersion without rinsing, wherein the aqueous acidic liquid composition comprises (A) 0.01 to 150 g.
/ L trivalent chromium and / or cobalt, (B) at least one selected from the group consisting of organic acids and / or nitric acid and / or salts thereof, (C) 0.1 to 300 g / L Ti, V , Mn, Y, Zr, Nb, Mo, Tc, Ru,
Rh, Pd, W, Li, Na, K, Be, Mg, Ca,
At least one selected from the group consisting of Al, Ni and Si, and (D) fluorine as an optional component, wherein the aqueous liquid composition is trivalent chromium, Ti, V, Mn,
Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, W,
Li, Na, K, Be, Mg, Ca, Al, Fe, N
i, Co, Si, Sr, In, Ag, Zn, Cu, S
c, organic acid, inorganic acid, organic acid salt, inorganic acid salt, amino acid,
Those containing at least one or more selected from the group consisting of amino acid salts, fluorine, amines, alcohols, water-soluble polymers, surfactants, silane coupling agents, carbon powders, dyes, pigments, organic colloids and inorganic colloids. A method for forming a protective film of a metal. 7. The surface of a metal is coated with a layer formed from an aqueous acidic liquid composition, and then immersed once or a plurality of times in an aqueous liquid composition having the same composition and / or a different composition from the aqueous acidic liquid composition. A method for forming a metal protective film, which comprises a step of drying without rinsing after the final dipping, a step of coating with a layer formed from the aqueous acidic liquid composition and the last step of adding the aqueous liquid composition. The method for forming a metal protective film according to any one of claims 4 to 6, wherein rinsing is performed or is not performed between arbitrary immersion steps up to the immersion step. 8. After forming a protective film on the metal surface by the method according to claim 1, an aqueous solution further containing a silicon compound and / or a resin and / or an inorganic colloid, or having a pH of A method for forming a metal protective film, which comprises contacting an aqueous solution of 7.5 or more. 9. The method for forming a metal protective film according to claim 8, wherein the silicon compound is sodium silicate, potassium silicate, lithium silicate, or colloidal silica having a particle size of 500 nm or less. 10. The metal is Zn, Ni, Cu, Ag,
The method for forming a metal protective film according to any one of claims 1 to 9, which is Fe, Cd, Al, Mg or an alloy thereof. 11. A metal protective film formed by the method for forming a metal protective film according to any one of claims 1 to 10.