JPH1046057A - Aqueous solution for rust prevention treatment, aqueous coating material composition, film formation, coated film formation, coating material and film treating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous solution for rust prevention, capable of preventing edge creep and standing severe press processing, having anticorrosive effects, comprising a specific water-soluble acetic acid metal salt, an additive and water. SOLUTION: This aqueous solution for rust prevention comprises at least one water-soluble acetic acid metal salt of a metal of the periods 4 and 5 of the group IIB of the periodic table, the periods 4 and 6 of the group IB, the periods 4-6 of the group IVA, VA, VIA, VIIA and VIII, the period 3-6 of the group IIA and the period 3 of the group IIIB, preferably a metal of the periods 4-6 of the group IIIA of the periodic table, an additive and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous rust preventive solution, an aqueous coating composition, a method for forming a film, a method for forming a coating, a coating material and a material for coating treatment, particularly an aqueous coating suitable for preventing edge creep (edge corrosion). The present invention relates to a composition, a method for forming a film, a method for forming a film, a coating material, and a film-treated material.

[0002]

2. Description of the Related Art In general, when a metal material or the like is coated, a method of forming a treated film by applying a rust preventive agent to the surface of the metal material as a pretreatment in order to prevent corrosion of the metal material or the like. Is used. Conventionally, as a rust preventive agent
A coating type rust preventive agent containing hexavalent chromium has been used. However, since hexavalent chromium itself is a harmful substance, there is a problem of environmental pollution. Therefore, in recent years, a zirconium (Zr) type coating type non-chromium rust preventive agent has been used, but the rust preventive effect has not been sufficient.

[0003] Before painting the surface of a metal material or the like,
In order to prevent corrosion on the surface, a coating base forming method of forming a coating base by applying a water-based primer for pre-coated metal (hereinafter referred to as PCM) containing a chromium rust preventive pigment is used. The PCM water-based primer containing the chromium rust preventive pigment is a yellow primer, although it has better corrosion resistance than other primers. For this reason, it is difficult to produce a primer of another color (for example, white) containing a chromium rust-preventive pigment. There was a tendency that the yellow base coat of the system primer hindered the film thickness of the top coat. Further, as mentioned above,
Since hexavalent chromium itself is a harmful substance, there is a problem that there is a risk of environmental pollution and edge creep (edge face corrosion) occurs.

[0004] As a base coat of a steel sheet to be pressed, an organic lubricating steel paint to which a lubricant is added is used. However, the conventional paint for a lubricating steel sheet has a composition that takes into account only the slipperiness of the surface of the organic film, and thus has a problem that cracks and cracks occur in the steel sheet during severe press working (lubricating drawing).

[0005] In view of the above, in recent years, a coating-type non-chrome rust preventive agent and a water-based primer for PCM having a high rust prevention effect have been desired. Further, there is a strong demand for a lubricating steel plate paint that prevents cracks in the base plating surface even in severe press working.

Japanese Patent Application Laid-Open No. 57-15876 discloses a coating method in which a synthetic resin emulsion and a coagulant and / or a crosslinking agent are mixed immediately before spray coating. ing. Here, as a coagulant, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; an alkali metal salt of an organic acid such as formic acid, acetic acid, oxalic acid, and citric acid; and alkaline earth salts such as beryllium, magnesium, calcium, strontium, and barium. Metal salts, transition metal salts such as scandium, titanium, vanadium, chromium, manganese, and iron; copper salts such as copper, zinc, aluminum, tin, and antimony; metal salts such as zinc, earth, tin, and antimony; Is disclosed. In the examples of the above publications, the adherends are paper balls and felt, paper balls and urethane foam, waterproof veneers and felts, and waterproof veneers and urethane foams.

[0007]

However, the adhesive disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 57-15876 has good drying properties after application to paper balls and felts, and good initial adhesiveness between adherends. However, the adhesiveness between the adhesive and the surface of the metal material was unknown.

Further, sulfuric acid, nitric acid,
Inorganic acids such as phosphoric acid, acetic acid, oxalic acid, organic acids such as citric acid,
It is well known that it generally has the action of corroding metallic materials. Therefore, it is usually difficult to add a metal salt of these acids to a rust preventive treatment aqueous solution or an aqueous paint in order to obtain a rust preventive effect on a metal material.

Therefore, there is still a need for a coating-type non-chromium rust preventive agent and a water-based primer for PCM which have a high rust-preventive effect. Further, there is a strong demand for a lubricating steel plate paint that prevents cracks in the base plating surface even in severe press working.

The present invention has been made in view of the above-mentioned conventional problems, and has as its object to provide a rust-preventing effect, in particular, a rust-preventing method capable of preventing edge creep and forming a film and a film which can be cut off by severe press working. An object of the present invention is to provide a treatment aqueous solution, an aqueous coating composition, a film forming method, and a film forming method, as well as a coating material and a film treatment material having a rust-preventive effect and capable of being cut off by strict press working.

[0011]

In order to achieve the above-mentioned object, an aqueous rust preventive treatment solution of the present invention contains a water-soluble metal acetate, an additive, and water. Metal salts of the salts include Periods 4 and 5 of Group IIB and Periods 4 and 6 of Group IB, Groups IVA, VA, VIA, V
Group IIA, Group VIII Period 4-6, and Group IIA Period 3 ~
6, at least one of Group 3B period 3 metals.

Further, the aqueous rust preventive treatment solution of the present invention contains a water-soluble metal acetate, an additive and water, and the metal salt of the water-soluble metal acetate is selected from the group IIIA of the periodic table. At least one of periods 4 to 6.

Further, the aqueous coating composition of the present invention contains an aqueous resin and a water-soluble metal acetate, and the metal salt of the water-soluble metal acetate is selected from the group consisting of groups 4 and 5 of group IIB of the periodic table. 5, and IB groups 4 and 6, IVA group, VA group, VIA
And at least one metal of group IIIA, group VIII of period 4-6 and group IIA of period 3-6, group IIIB of period 3 or of group IIIA of the periodic table, period 4-6. It is.

Further, the method of forming a film according to the present invention is a method in which the above-mentioned aqueous solution for rust prevention treatment is applied to a material and then baked.

The method for forming a coating film according to the present invention is a method in which the above-mentioned aqueous coating composition is applied to a material and then baked.

The film-forming material of the present invention has a film formed by the above-described film forming method.

Further, a coating film is formed from the coating material of the present invention by the above-described coating film forming method.

The above-mentioned metal salt of water-soluble acetate is a δ-binding compound, and is easily thermally decomposed by heat (for example, heat such as baking). Then, the water-soluble metal acetate metal salt is changed into a metal oxide by thermal decomposition, and easily becomes a nonstoichiometric oxide having a large number of metal atoms. Therefore, when the rust preventive treatment aqueous solution or the aqueous coating composition is applied to the metal material and then baked, the oxide film formed on the substrate interface of the metal material exhibits conductivity. Such a coating or coating prevents the formation of local anodes and cathodes in a corrosive atmosphere and is suitable for preventing edge creep (edge corrosion). Further, the above-mentioned film or coating film is very stable, and the above-mentioned rust-proofing aqueous solution is also effective for corrosion prevention of the underlying metal (plane portion corrosion). In addition, in the aqueous coating composition, the nonstoichiometric oxide coating film formed after baking is preferably bound to a metal base by having an aqueous resin coexist, and has a long-term anticorrosion property.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION A rust preventive treatment aqueous solution according to the present invention comprises a water-soluble metal acetate, an additive, and water, and the metal salt of the water-soluble metal acetate is: Periods 4 and 5 of group IIB and periods 4 and 6 of group IB of the periodic table, groups IVA, VA, VIA, VII
Group A, Group VIII Periods 4-6, and Group IIA Periods 3-6,
It is at least one metal of Group IIIB of Period 3 or at least one of Groups 4A to 6 of Group IIIA of the periodic table.

The above metal salt of water-soluble acetate is represented by II in the periodic table.
Group B periods 4 and 5, and Group IB periods 4 and 6, IVA
Groups 4-6 of groups VA, VIA, VIA, VIIA, VIII
As shown in the periodic table of Table 1 below, metals of Group 3A and Period 3 to Group 6 and Group 3B of Period 3 are zinc (Z
n), cadmium (Cd) (periods 4 and 5 of group IIB),
Copper (Cu), gold (Au) (periods 4 and 6 of the IB group), titanium (Ti), zirconium (Zr), hafnium (H
f) (IVA group period 4 to 6), vanadium (V), niobium (Nb), tantalum (Ta) (VA group period 4 to 6)
6), chromium (Cr), molybdenum (Mo), tungsten (W) (VIA group period 4-6), manganese (M
n), technetium (Tc), rhenium (Re) (VII
Group A period 4-6), iron (Fe), cobalt (Co),
Nickel (Ni), ruthenium (Ru), rhodium (R
h), palladium (Pd), osmium (Os), iridium (Ir), platinum (Pt) (period 4 to group VIII)
6), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba) (IIA group period 3 to 6), and aluminum (Al) (IIIB group period 3). Preferably, they are Mg, Mn, Co, and Ni.

The periods 4 to 6 of group IIIA of the periodic table include scandium (Sc), yttrium (Y), lanthanoids (La, Ce, Pr, Nd, Pm, Sm, Em).
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u).

The metal is any of the 3d, 4d and 5d block elements. Although Zn and Cd are not d-block elements, they exhibit chemical properties similar to d-block elements when ionized, and are therefore included in the metal of the water-soluble metal acetate according to the present invention.

[0023]

[Table 1] Note that acetates of alkali metals (Na, K, Rb, Cs) are excluded from the present invention. This is because alkali metal ions adversely affect corrosion resistance. Further, the acetates of mercury (Hg), thallium (Tl), and lead (Pb) are all too toxic, and the silver (Ag) acetate is hardly soluble in water and cannot provide a corrosion-resistant effect. Therefore, they are excluded from the water-soluble metal acetate according to the present invention.

The additives include a surface tension adjuster, an antifoaming agent, and a lubricant.
Seeds are added to the rust preventive solution. The surface tension adjuster is used when the rust-proofing aqueous solution is poorly loaded by a metal and is used to improve uniform coating properties. For example, C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₄ H It is.
Further, the antifoaming agent is a roll coater, which suppresses foaming of the rust preventive treatment aqueous solution generated at the time of spraying or dipping, and suppresses abnormal occurrence of a film state due to foaming, such as foaming after forming a film, An example is an acrylic emulsion.
The lubricant imparts lubricity necessary for press working or the like, and is, for example, a polyethylene-based emulsion or a polyethylene oxide-based emulsion.

As the water, ion-exchanged water is mainly used. If there is a problem in the workability of coating, a water-soluble polar solvent may be added. Examples of the water-soluble polar solvent include N-methyl-2-pyrrolidone (NMP), butyl diglycol (BDG), and ethyl diglycol (ED
G), acetone, butyl cellosolve and the like.

The amount of the water-soluble metal acetate added to the rust-preventive treatment aqueous solution is preferably 5 to 50 solid parts by weight, more preferably 10 to 25 solids-weight, relative to 100 parts by weight of the rust preventive treatment aqueous solution. Department. If the amount of the water-soluble metal acetate is less than 5 parts by weight of solid content, the corrosion resistance becomes insufficient. On the other hand, when the amount of the water-soluble metal acetate was 5
If the amount exceeds 0 parts by weight, no further rust-preventing effect can be obtained, and it is not economical.

The amount of the additive to be added to the rust preventive treatment aqueous solution is 0.1 to 100 parts by weight of the rust preventive treatment aqueous solution.
5 to 5 parts by weight of solid content are preferred, and more preferably 1 to 3
It is a solid content part by weight. When the amount of the additive is less than 0.5 parts by weight of solid content, there are disadvantages such as foaming and poor coating. On the other hand, when the amount of the additive exceeds 5 parts by weight of the solid content, there are disadvantages such as adhesion of the coating film and poor film curing.

The amount of water added to the rust preventive treatment aqueous solution is the remaining parts by weight after the addition of the water-soluble metal acetate and additives.

The above rust preventive solution is used mainly as a coating type non-chromium rust preventive agent. As described later, 6
Rust prevention effect is higher than chromium-containing coating type rust prevention agent.

Aqueous paint composition The aqueous paint composition according to the present invention contains an aqueous resin and a water-soluble metal acetate. Further, the aqueous coating composition may contain an additive and water as required. still,
The water-soluble metal acetate metal salt, additives, and water are the same as those used in the above-described rust-preventive treatment aqueous solution, and therefore, the description thereof is omitted.

The water-based resin is intended to include a water-soluble resin, a water-dispersible resin, and an emulsion resin, and includes, for example, a polycarbonate urethane resin, an epoxy-modified acrylic resin, an amine-modified epoxy resin, and other modified acrylic resins. But not limited to this. More preferably, the aqueous resin is an epoxy-modified acrylic emulsion, a polycarbonate urethane emulsion, or an amine-modified epoxy emulsion. Good storage stability and easy to use.

The particle size of the emulsion is 2 as a diameter.
00 nm or less, more preferably 30 to 100
nm.

The aqueous coating composition may contain a curing agent. As the curing agent, an amino resin, a blocked polyisocyanate compound, a polysilane compound, or the like can be used, and a polysilane compound is preferable.

The water-soluble metal acetate is contained in an amount of 10 to 40 solid parts by weight, preferably 15 to 30 solid parts by weight, based on the solid content (100 parts by weight) of the aqueous coating composition. If the amount of the water-soluble metal acetate is less than 5 parts by weight of solid content, the corrosion resistance becomes insufficient. On the other hand, even if the addition amount of the water-soluble metal acetate exceeds 100 parts by weight of solid content, no further rust preventive effect can be obtained, and the economy is lacking.

The above aqueous resin is contained in an amount of 60 to 90 solid parts by weight, preferably 70 to 85 solid parts by weight, based on the solid content (100 parts by weight) of the aqueous coating composition. When the amount of the aqueous resin is less than 60 parts by weight, there is a disadvantage that the film forming property is not good. On the other hand, when the amount of the aqueous resin exceeds 90 parts by weight, a uniform film is obtained. There is a disadvantage that there is no.

The above-mentioned additives (for example, a surface tension modifier, a defoaming agent,
Lubricant, etc.).

The above aqueous coating composition can be used mainly as a high workability lubricating coating material and an aqueous primer for PCM (clear, white, green, red, brown, etc.). In the case of a highly workable lubricating paint, a lubricant is particularly added as an additive. Further, in the case of a water-based primer for PCM excluding the clear primer, a pigment is included.
For example, in the case of a white primer, an appropriate amount of a white pigment such as titanium dioxide (TiO ₂ ), zinc white, lithopone, zinc sulfide, and antimony trioxide is added. Similarly, various coloring pigments are selected and added according to each color. An extender pigment may be added as needed. In recent years, it is useful as a primer (undercoat) for a topcoat that requires a high degree of whiteness and has become increasingly required.

The method of forming a film according to the present invention is a method of applying the above-mentioned rust-proofing aqueous solution to a material and then baking the material.

Although the base treatment of the material is not particularly necessary, if the material is a metal plate, oil or the like may adhere to the surface. If the oil is conspicuous, perform alkali degreasing. Or trichlene degreasing.

The coating can be performed by a roll coater, spray, or dipping. 2-7μm thickness after baking
m.

The baking conditions were as follows: the maximum baking temperature reached 80.
To 250 ° C., and the baking time at that time is 5 seconds to 30 minutes. When the temperature is high, baking is performed in a short time.

If the maximum baking temperature is less than 80 ° C., there is a disadvantage that the oxide film is insufficiently formed.
When the temperature exceeds 0 ° C., the resin is thermally decomposed, and there is an inconvenience of poor film formation. If the baking time is less than 5 seconds, there is a disadvantage that the oxide film is insufficiently formed.
If the amount exceeds minutes, there is a disadvantage that the resin is yellowed.

The method for forming a film of the present invention is effective as a pretreatment for electrodeposition coating, since the water-soluble metal acetate is thermally decomposed to form a conductive oxide film on the surface of the material.

Further, another method for forming a film according to the present invention comprises:
This is a method in which the above-mentioned rust-preventive treatment aqueous solution is applied to a material, baked, and then an undercoat film, an intermediate coat film, and an overcoat film are formed as necessary. Note that the conditions for coating and baking are the same as described above, and will not be described.

The formation of the undercoat, intermediate coat, and top coat after baking may be electrodeposition coating, coating using a roll coater, spraying, or the like.

As in the above-described method for forming a coating film, the method for forming a coating film according to the present invention is a method in which a material is coated with the above-described aqueous coating composition and then baked. Note that the conditions for coating and baking are the same as described above, and will not be described.

Material for forming a film The material for forming a film according to the present invention is a material having a film formed by the above-described method for forming a film. Since the method of forming the film is the same as described above, the description is omitted.

As a material, a metal plate, for example, a hot-dip galvanized plate, an electrogalvanized plate, a zinc alloy-plated plate (Zn-
Al, Zn-Ni, etc.), alloyed galvanized plate (Zn-F
e), aluminum plate, aluminum alloy plated plate (A
1-Mg, etc.), stainless steel, cold-rolled steel plate and the like.

Coating Material The coating material according to the present invention is a material having a coating film formed by the above-described coating film forming method. In addition, since the coating method and the material are the same as described above, the description is omitted.

Next, another preferred embodiment of the present invention will be described below.

1. The metal salt of the water-soluble metal acetate contained in the rust preventive treatment aqueous solution is preferably Mg, Mn, Co, N
i.

2. The metal salt of the water-soluble metal acetate contained in the aqueous coating composition is preferably Mg, Mn, Co, N
i.

3. Additives contained in the rust prevention solution
It is at least one of a surface conditioner, an antifoaming agent, and a lubricant.

4. The aqueous coating composition further comprises additives and / or
Or contains a pigment.

5. The additive described in the above “4.” is at least one of a surface conditioner, an antifoaming agent, and a lubricant.

6. The pigment described in the above “4.” is TiO.
₂

7. The surface conditioner described in the above “3.” and “5.” is C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₄ H.

8. The antifoaming agents described in the above “3.” and “5.” are acrylic emulsions.

9. The lubricant described in the above “3.” and “5.” is a polyethylene oxide emulsion.

10. The rust preventive treatment aqueous solution contains a water-soluble polar solvent in addition to water.

11. The aqueous coating composition contains a water-soluble polar solvent in addition to water.

12. The water-soluble polar solvents described in the above “10.” and “11.” are N-methyl-2-pyrrolidone, butyldiglycol, ethyldiglycol, acetone and butylcellosolve.

13. The resin of the aqueous coating composition is an amine-modified epoxy emulsion, a polycarbonate urethane emulsion, or an epoxy-modified acrylic emulsion.

14. The resin of the aqueous coating composition is an epoxy-modified acrylic emulsion.

15. The particle size of the emulsion used for the resin of the aqueous coating composition is 200 nm or less.

16. The aqueous coating composition further contains a curing agent.

17. The curing agent according to the above “16.”
γ-glycidoxypropyltrimethoxysilane.

18. The rust preventive treatment aqueous solution contains 5 to 50 solid parts by weight of a water-soluble metal acetate salt per 100 parts by weight of the rust preventive treatment aqueous solution.

19. The aqueous solution for rust prevention treatment preferably contains 10 to 25 solid parts by weight of a water-soluble metal acetate in 100 parts by weight of the aqueous solution for rust prevention treatment.

20. In the aqueous coating composition, the soluble metal acetate is 10 to 40 solid parts by weight based on the solid content (100 parts by weight) of the aqueous coating composition.

21. The aqueous coating composition preferably contains 15 to 30 solid parts by weight of the soluble metal acetate based on the solid content (100 parts by weight) of the aqueous coating composition.

22. The film forming method and the film forming method are:
It is applied so that the film thickness after baking becomes 2 to 7 μm.

23. The film forming method and the film forming method are:
The maximum baking sheet temperature is 80 to 250 ° C.

24. The film forming method and the film forming method are:
The baking time is 5 seconds to 30 minutes.

[0075]

Next, the present invention will be described in detail with reference to examples and comparative examples. Note that the present invention is not limited by these examples.

Examples 1 to 44 and Comparative Examples 1 to 20 (1) Metal sheet: 0.8 mm galvanized untreated steel sheet (only tricline degreasing) (2) Production method of rust preventive treatment aqueous solution An additive and ion-exchanged water are added to the metal salt to form an aqueous solution.

The electrogalvanized plate of the above (1), which has been degreased by trichlene, is immersed in an aqueous rust preventive solution having the following composition. Thereafter, the film is baked at a maximum temperature of 150 ° C. for 15 seconds to make the dry film thickness 2 μm. Next, a cationic electrodeposition coating material “Power Top U-600” (manufactured by Nippon Paint Co., Ltd.) is electrodeposited, and dried at 165 ° C. to a dry film thickness of 20 μm.
Bake separately.

The aqueous rust preventive treatment solution contained 15 parts by weight of a soluble metal acetate, 1 part by weight of a surface tension modifier, 1 part by weight of a defoamer, and 83 parts by weight of ion-exchanged water. Department.

Soluble metal acetate A: Co (CH ₃ COO) ₂ .4H ₂ O B: Ni (CH ₃ COO) ₂ .4H ₂ O C: Mn (CH ₃ COO) ₂ .4H ₂ O It is as follows.

(A) Finish of electrodeposited coating: Appearance was visually evaluated.: No pinhole (gas pin) ×: Pinhole (gas pin) present (b) Secondary adhesion test with hot water: 50 days in hot water at 50 ° C. After immersion, then pull up and leave for 1 hour, JIS K54
Evaluation was performed based on the adhesion (cross-cut tape method) of 8.00 (1991) 8.5.2 (100 square cells of 2 mm square) ○: No peeling ×: With peeling (3) Method for producing water-based coating composition Table Ion-exchange water is added to the water-soluble metal acetate metal salts, resins and additives shown in 3 to 7 to prepare an aqueous coating composition.

In the case of Table 7 containing the pigment, T
Water is added with iO ₂ , the aqueous resin and water dispersed therein while stirring. Thereby, a white primer for PCM is generated.

(4) Coating conditions and baking conditions Coating conditions: In the case of a coating type non-chromium rust preventive agent (a rust preventive treatment aqueous solution: Table 2) and an aqueous coating composition (Tables 3 to 6), the film after baking In the case of a white primer for PCM (Table 7), apply so that the film thickness after baking is 3 μm. Baking conditions: The maximum baking temperature is 150 ° C. The baking time is 15 seconds.

(5) Evaluation method: Corrosion test (i) CCT-I: Using a combined cycle corrosion tester,
First, the applied test piece is sprayed with a 5% saline solution at 35 ° C. for 4 hours. Thereafter, it is dried at 60 ° C. for 2 hours and then left at 50 ° C. in a 95% wet state for 2 hours. This 3
A cycle test is performed with one process as one cycle, and the flat portion is checked for the whole rust state, and the edge portion is checked for the creep width from the edge.

(Ii) CCT-III: Using a combined cycle corrosion tester, first, the applied test piece is immersed in a 5% saline solution and an aqueous solution containing iron rust at 50 ° C. for 7 minutes. Then 5
Leave at 0 ° C. in a 95% wet state for 15 minutes, then
Dry at 8 ° C. for 8 minutes. With these three steps as one cycle, a cycle test is performed, the flat part is checked for the state of the entire rust, and the edge part is checked for the creep width from the edge.

(Iii) SST; JIS5400 9.1
(1991) (saline spray test): 35% 5% saline solution
While keeping the temperature at 0 ° C, it was placed in a state where it was sprayed in a closed box, taken out after a certain period of time, and the flat part was checked for the whole rust state, and the edge was checked for the creep width from the edge.

Workability test (i) Bead workability: An extruded bead having a height of 5 mm and a width of 5 mm is formed by a roll, and the plate at the bead forming portion is visually evaluated for scratches, cracks, and peelings.

：: No flaws, cracks, and peeling ×: Generation of scratches, cracks, and peeling The coating-type non-chrome rust preventive agent, the aqueous coating composition, and the white primer for PCM are shown in Tables 2 to 7 below.
Shows the evaluation results. Table 2 shows the evaluation results of the coating type non-chrome rust preventive agent, Tables 3 to 6 show the evaluation results of the aqueous coating composition, and Table 7 shows the evaluation results of the white primer for PCM.

[0088]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7] From these results, since the coating film and the coating film of the present invention have conductivity, the local anode and the cathode in a corrosive atmosphere are immediately neutralized and disappear, so that little progress of rust is observed from the edge portion. . Further, the oxide coating film of the present invention has high hardness (Mohs hardness of 4 or more) and lubricity, and thus has an effect of preventing cracks and scratches on the plated surface.

[0089]

As described above, according to the aqueous rust preventive treatment solution, aqueous coating composition, coating film forming method and coating film forming method of the present invention, it has a rust preventing effect, in particular, prevents edge creep, and Ended severe press processing. Further, the coating material and the film-treated material also have a rust-preventive effect and can be subjected to severe press working.

Further, if a white pigment is added to the water-based coating composition of the present invention to form a white primer, since the base is white, the hue of the overcoat is not limited, and any color can be applied.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Naotaka Yamamoto 4-1-1, Minamishinagawa, Shinagawa-ku, Tokyo Inside Japan Paint Co., Ltd. Tokyo Office

Claims (9)

[Claims] 1. A metal salt of a water-soluble metal acetate, an additive, and water, wherein the metal salt of the water-soluble metal acetate is selected from the groups 4 and 5 of Group IIB and Group IB of the periodic table. Period 4 and 6, group IVA,
Periods 4-6 of groups VA, VIA, VIIA, VIII, and
An aqueous rust preventive treatment solution, characterized in that it is at least one metal selected from the group IIIA period 3-6 and the group IIIB period 3 metal. 2. A metal salt of a water-soluble metal acetate, an additive, and water, wherein the metal salt of the water-soluble metal acetate is selected from the group consisting of IIIA of the periodic table.
A rust preventive treatment aqueous solution, which is at least one member of group 4 to 6 of the group. 3. An aqueous resin, and a water-soluble metal acetate metal salt, wherein the metal salt of the water-soluble metal acetate is selected from the group IIB periods 4 and 5 and the group IB period 4 and 5 of the periodic table. 6,
Period 4 of group IVA, group VA, group VIA, group VIIA, group VIII
An aqueous coating composition, characterized in that it is at least one metal of Group 6 and Group IIA period 3 to 6 and Group IIIB period 3 metal. 4. The aqueous coating composition according to claim 3, wherein the metal salt of the water-soluble metal acetate is IIIA of the periodic table.
An aqueous coating composition comprising at least one member selected from the group consisting of groups 4 to 6. 5. A method for forming a film, characterized in that the material is coated with the rust preventive treatment aqueous solution according to claim 1 or 2, followed by baking. 6. A method for forming a coating film, comprising baking after coating the aqueous coating composition according to claim 3 on a material. 7. A method for forming a film, comprising applying the rust preventive treatment aqueous solution according to claim 1 to a material, baking the material, and then forming a coating film. 8. A material for forming a film, wherein a film is formed by the method for forming a film according to claim 5. Description: 9. A coating material, wherein a coating film is formed by the coating film forming method according to claim 6.