JP2001049451A - Phosphate chemical conversion treating method for metallic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a coating film excellent in corrosion resistance after coating and adhesion for coating by bringing a metallic material into contact with a control agent contg. phosphate particles of specified particle size and saccharides as accelerating components and thereafter treating it with a chemically treating soln. which does not contain nickel. SOLUTION: A metallic material is brought into contact with a surface control soln. of one or more kinds of phosphate particles of <=5 μm particle size selected from phosphates contg. one or more kinds of bivalent and trivalent metals and accelerating components selected from one or more kinds selected from monosaccharides, sacccharides and the derivatives thereof. Next, it is brought into contact with a phosphoaric chemically treating soln. which does not contain nickel and contains 0.5 to 5 g/l zinc ions, 5 to 30 g/l phosphoric ions and a chemical conversion accelerator. Alternatively, as the accelerating components, one or more kinds among orthophosphoric acid, polyphosphoric acid and an organic phosphonic compd. or a water soluble high polymer compd. composed of a vinyl acetate polymer, the derivative thereof or a copolymer of a monomer capable of copolymerizing with vinyl acetate and vinyl acetate is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal film such as a steel plate, a galvanized steel plate, an aluminum alloy, and a magnesium alloy, which forms a uniform coating film having excellent coating adhesion and corrosion resistance after coating, and which is capable of forming nickel ions. The present invention relates to a method for phosphate conversion treatment of a metal material using a phosphate conversion treatment solution that does not contain the same.

[0001]

2. Description of the Related Art At present, a phosphate conversion treatment is applied to an automobile body as a pretreatment for coating in order to improve corrosion resistance and adhesion between a steel plate and a coating. This involves depositing a phosphate film on a metal by contacting the metal with a titanium colloid-based surface conditioning solution and then contacting it with an acidic solution containing phosphate, zinc, nickel and manganese ions. Is the way.

However, in recent years, with increasing awareness of environmental conservation, especially in Europe, the regulation of nickel drainage is becoming stricter, and there is a concern that the regulation of nickel drainage will become stricter in Japan in the future.

[0003] For the above-mentioned reasons, there is a demand for a nickel-free chemical conversion treatment solution used for zinc phosphate treatment.

However, if nickel is removed from the phosphating solution in the above-mentioned phosphating process, adverse effects such as coarsening of the crystals of the phosphate film, non-uniformity of the phosphate film, and deterioration of corrosion resistance after coating are caused. In addition, the secondary adhesion of the zinc-plated material is reduced, and satisfactory coating performance cannot be obtained.

[0005] In order to solve the above problems, a phosphate treatment method not containing nickel is disclosed in Japanese Patent Publication No. 7-505445. This means that zinc ions are 0.2 to 2 g /
L, copper ion 0.5-25mg / L, phosphate ion 5
This is a treatment method for forming a phosphate film containing no nickel by performing a phosphate chemical conversion treatment containing 30 g / L. Although this method uses copper as a nickel substitute metal, copper has an allowable amount of 0.5 to 25 mg in a chemical conversion treatment solution.
/ L, which is a trace amount, and it is difficult to control this concentration in an actual line, and there is a problem that electrolytic corrosion of an apparatus (equipment) due to copper plating is also concerned.

[0006] From such a background, it is desired to develop a phosphate conversion treatment method which has the same post-paint adhesion and post-paint corrosion resistance as the existing nickel-containing phosphate conversion treatment without containing nickel.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems associated with the non-nickel phosphate treatment of the above-mentioned prior art. An object of the present invention is to provide a phosphate conversion treatment method for forming a phosphate conversion coating film having excellent corrosion resistance and coating adhesion after coating by treating with a treatment liquid.

[0008]

Means for Solving the Problems The present inventors have intensively studied means for solving the problems associated with the non-nickelization of the phosphate treatment. The present inventors have newly found that the chemical conversion treatment can impart post-coating corrosion resistance and coating adhesion equivalent to those of the prior art even if the chemical conversion treatment solution does not contain nickel ions, and have completed the present invention.

That is, in the first phosphate conversion treatment method for a metal material according to the present invention, the metal material is selected from phosphates containing at least one of divalent and / or trivalent metals having a particle size of 5 μm or less. After contacting with a surface conditioning liquid containing at least one kind of phosphate particles and at least one kind selected from monosaccharides, polysaccharides and derivatives thereof as an accelerating component, no zinc ion is contained and no zinc ion is added. 0.5 to 5 g / L, and phosphate ions are contacted with a phosphate conversion treatment solution containing 5 to 30 g / L and a chemical conversion accelerator.

In a second chemical conversion treatment method, the metal material is formed of at least one phosphate selected from phosphates containing at least one divalent and / or trivalent metal having a particle size of 5 μm or less. After contacting the particles with a surface conditioning solution containing at least one of orthophosphoric acid, polyphosphoric acid or an organic phosphonic acid compound as an accelerating component, nickel-free and zinc ions are added in an amount of 0.
5 to 5 g / L, phosphate ions are contacted with a phosphate conversion treatment solution containing 5 to 30 g / L and a chemical conversion accelerator.

[0011] The third chemical conversion treatment method is characterized in that the metal material comprises at least one phosphate selected from phosphates containing at least one divalent and / or trivalent metal having a particle size of 5 μm or less. A water-soluble polymer compound comprising particles and a vinyl acetate polymer or a derivative thereof as a promoting component or a copolymer of vinyl acetate and a monomer copolymerizable with vinyl acetate;
After contacting with a surface conditioning solution containing at least one species, a phosphorylation containing no nickel, 0.5 to 5 g / L of zinc ions, 5 to 30 g / L of phosphate ions and a chemical conversion promoter It is characterized by being brought into contact with a treatment solution.

Further, the fourth chemical conversion treatment method comprises the steps of: converting a metal material into a third- or third-valent metal having a particle size of 5 μm or less;
One or more phosphate particles selected from phosphate, and a monomer represented by the following chemical formula 1 or α,
a monomer 5 copolymerizable with at least one selected from β-unsaturated carboxylic acid monomers and a vinyl acetate monomer
0% by weight or less, after contact with a surface conditioning liquid containing at least one polymer or copolymer obtained by polymerization.
It is characterized by contacting with a phosphate chemical conversion treatment solution containing no nickel, containing 0.5 to 5 g / L of zinc ions, 5 to 30 g / L of phosphate ions, and containing a chemical conversion accelerator.

Embedded image H ₂ C ＝ C (R ¹ ) —COOR ² Formula 1 (wherein R ¹ is H or CH ₃ , R ² is H, and an alkyl group having 1 to 5 C or C is (1-5 hydroxyalkyl groups)

Further, at least one metal ion selected from the group consisting of magnesium ions, cobalt ions, manganese ions, calcium ions, tungstate ions and strontium ions is contained in the chemical conversion treatment solution in an amount of 0.1 to 3%. It is preferable to contain 0 g / L.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents of the present invention will be described below in detail. The metal subjected to the phosphating method of the present invention is:
Although there is no particular limitation, a steel sheet, a galvanized steel sheet, a zinc alloy-plated steel sheet, a magnesium alloy, and an aluminum alloy are preferable.

In the present invention, first, it is necessary to clean the surface of the metal material before the phosphate conversion treatment.
Therefore, if the surface of the metal material is clean in advance, it can be brought into contact with the surface conditioning liquid as it is, but when treating a metal material whose surface is contaminated by deposits such as iron powder, dust, and oil. It is necessary to remove contaminants adhering to the surface by a cleaning method such as aqueous alkaline degreasing, emulsion degreasing, and solvent degreasing. When an aqueous cleaning agent is used, it is preferable to provide a water washing step or the like after the cleaning to remove the cleaning liquid attached to the metal surface.

Next, the surface adjusting step of the present invention will be described in detail. The divalent or trivalent metal phosphate particles contained in the surface conditioning liquid of the present invention must have a particle size of 5 μm. Outside of this application, insoluble substances may not be stably present in the aqueous solution, which is not preferable. These phosphate particles not only serve as nuclei when phosphate crystals are precipitated, but also have the effect of promoting the precipitation reaction itself. That is, in the surface conditioning step, a part of the phosphate particles of the divalent or trivalent metal adsorbed on the metal surface is dissolved in the phosphate conversion treatment bath, so that phosphate crystals are formed very near the metal surface. Since the main component is supplied, the initial precipitation reaction of the phosphate crystals is remarkably promoted.

The divalent or trivalent metal is not particularly limited, but is preferably at least one selected from Zn, Fe, Mn, Co, Ca, Mg and Al. In order to serve as a nucleus when phosphate crystals precipitate and to promote the initial precipitation reaction of the phosphate crystals, the phosphate particle concentration of the divalent or trivalent metal is 0.001 to 30 g / L is preferred. This is because if the concentration of the divalent or trivalent metal phosphate particles is less than 0.001 g / L, the amount of the divalent or trivalent metal phosphate particles adsorbed on the metal surface is small. The initial precipitation reaction of phosphate crystals cannot be promoted, and the precipitation reaction of crystals is not promoted because there are few divalent or trivalent metal phosphate particles serving as crystal nuclei. Even if the phosphate particle concentration of the divalent or trivalent metal is higher than 30 g / L, the effect of further promoting the phosphate conversion treatment reaction cannot be expected, and it is only economically disadvantageous.

The accelerating component essentially contained in the surface conditioning liquid of the present invention enhances the dispersion stability of divalent or trivalent metal phosphate particles and divalent or trivalent metal phosphate particles. Has the function of promoting the adsorption of metal on the metal surface. That is, the accelerating component is adsorbed on the surface of the phosphate particles of a divalent or trivalent metal, and the repulsive force and steric hindrance of the charge cause the divalent or trivalent metal in the surface conditioning liquid.
Agglomeration and sedimentation are prevented by preventing collisions between phosphate particles of the valent metal. In addition, since the accelerating component has an adsorbing ability on the metal surface due to its structure, it promotes the adsorption of divalent or trivalent metal phosphate particles on the metal surface and contacts the metal to be treated with the surface conditioning liquid. The surface adjustment effect can be obtained simply by doing so.

The concentration of the accelerating component is 1 to 2000 ppm.
It is desirable that If the concentration is less than 1 ppm, the surface conditioning effect is not exhibited only by bringing the metal to be treated into contact with the surface conditioning liquid, and if it exceeds 2000 ppm, no further effect can be expected, and excess polymer or copolymer may not be obtained. It may be adsorbed on the surface of the metal to be treated and interfere with the phosphate conversion treatment.

In the surface conditioning step in the first phosphate conversion treatment method of the present invention, at least one selected from monosaccharides, polysaccharides and derivatives thereof is contained as an accelerating component.
Examples of the basic constituent saccharides of the monosaccharides, polysaccharides and derivatives thereof used in the present invention include, for example, fructose, tagatose, psicose, sulose, erythose, threose, ribose, arabinose, xylose, lyxose, allose, artose, glucose, mannose,
It can be selected from growth, idose, galactose, and talose.

There is no problem even if sodium salts or ammonium salts of monosaccharides, polysaccharides and derivatives thereof are used.

In the surface conditioning step in the second phosphate conversion treatment method of the present invention, at least one of orthophosphoric acid, polyphosphoric acid and an organic phosphonic acid compound is contained as an accelerating component. Normal phosphoric acid is orthophosphoric acid, and as polyphosphoric acid, pyrophosphoric acid, triphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid or its sodium salt and ammonium salt can be used. Further, as the organic phosphonic acid compound, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid or its sodium salt can be used. Furthermore, it does not matter what kind of the above-mentioned orthophosphoric acid, polyphosphoric acid or organic phosphonic acid compound is used or which is used in combination.

In the surface conditioning step in the third phosphate chemical conversion treatment method of the present invention, the copolymerization of vinyl acetate with a vinyl acetate polymer or a derivative thereof or a monomer copolymerizable with vinyl acetate and vinyl acetate as an accelerating component is carried out. One or more water-soluble polymer compounds composed of a union are incorporated. As the polymer of vinyl acetate or a derivative thereof in the present invention, polyvinyl alcohol which is a saponified product of vinyl acetate polymer, and further cyanoethylated polyvinyl alcohol obtained by cyanoethylation of polyvinyl alcohol with acrylonitrile, acetalization of polyvinyl alcohol with formalin Formalized polyvinyl alcohol obtained, urethanized polyvinyl alcohol obtained by urethanizing polyvinyl alcohol with urea, and a water-soluble polymer compound in which a carboxyl group, a sulfone group, or an amide group is introduced into polyvinyl alcohol can be used. In addition, acrylic acid, crotonic acid, maleic anhydride and the like can be used as the monomer copolymerizable with vinyl acetate in the present invention.

The vinyl acetate polymer or a derivative thereof or a copolymer of vinyl acetate and a monomer copolymerizable with vinyl acetate can sufficiently exhibit the effects of the present invention as long as it is water-soluble. . Therefore, the effect is not affected by the degree of polymerization and the rate of introduction of the functional group, and it does not matter what kind of the monomer or copolymer is used, or whether it is used in combination of several kinds. .

In the surface conditioning step in the fourth phosphate conversion treatment method of the present invention, at least one selected from monomers represented by the following chemical formula 1 and α, β unsaturated carboxylic acid monomers as the accelerating component: A polymer or copolymer obtained by polymerizing one or more kinds and 50% by weight or less of a monomer copolymerizable with the monomer is contained.

[0026]

Embedded image H ₂ C ＝ C (R ¹ ) —COOR ² Formula 1 (wherein R ¹ is H or CH ₃ , R ² is H, an alkyl group having 1 to 5 C or C is (1-5 hydroxyalkyl groups)

The monomers represented by the chemical formula 1 include methyl acrylate, ethyl acrylate, propyl acrylate,
Butyl acrylate, pentyl acrylate, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, methacrylic acid Hydroxybutyl, hydroxypentyl methacrylate and the like can be used.

As the α, β unsaturated carboxylic acid monomer, acrylic acid, methacrylic acid, maleic acid and the like can be used. As the monomer copolymerizable with the above monomer, vinyl acetate, styrene, vinyl chloride, vinyl sulfonic acid and the like can be used. In addition, one of the monomers
Even when using a polymer obtained by polymerizing various types of monomers,
A copolymer obtained by polymerizing a combination of several types of the above monomers may be used without any problem.

Further, the surface conditioning liquid used in the phosphating method of the present invention may contain an alkali metal salt or an ammonium salt or a mixture thereof. Alkali metal or ammonium salts include orthophosphate, metaphosphate, orthosilicate, metasilicate, carbonate, bicarbonate, nitrate, nitrite, sulfate, borate, and organic acid salts. There is no particular limitation as long as it is in the form of at least one salt selected from the group. Further, there is no problem even if two or more of the above alkali metal salts or ammonium salts are used in combination. The concentration is not particularly limited, but is preferably 0.5 to 20 g / L.

Next, the phosphate conversion treatment step of the present invention will be described in detail. The phosphate chemical conversion treatment solution used in the present invention is an acidic aqueous solution basically containing no nickel ions but containing zinc ions, phosphate ions, and a chemical conversion accelerator. It is preferable that the zinc ion concentration in this phosphate chemical conversion treatment liquid is 0.5 to 5.0 g / L. If the zinc ion content is less than 0.5 g / L, it may not be possible to form a sufficient amount of the coating, and the coverage of the phosphate crystals to be formed may decrease, resulting in insufficient corrosion resistance after coating. May be. If it exceeds 5.0 g / L, the crystal of the coating film may become coarse, and the adhesion after coating may be reduced.

The phosphate ion concentration in the phosphate conversion treatment solution is preferably from 5.0 to 30 g / L. If it is less than 5.0 g / L, it may be difficult to form a normal chemical conversion film, and if it exceeds 30.0 g / L, the effect may be saturated and economically disadvantageous. There is. Phosphate ions can be supplied by adding phosphoric acid or an aqueous solution thereof to a phosphate conversion treatment solution, or by dissolving a phosphate such as sodium, magnesium or zinc in the phosphate conversion treatment solution. it can.

An oxidizing agent called a chemical conversion accelerator is contained in the chemical conversion treatment solution. The chemical conversion accelerator used in the phosphate chemical conversion treatment step in the present invention is a substance capable of generating water from hydrogen ions and electrons supplied from the surface of the metal to be processed at a cathode portion generated at the time of etching due to its oxidizing action. That is, there is no particular limitation as long as it has an action (depolarization action) that suppresses the generation of hydrogen during etching.

Further, in the present invention, the phosphate chemical conversion treatment solution contains at least one metal ion selected from the group consisting of magnesium ion, cobalt ion, manganese ion, calcium ion, tungstate ion and strontium ion. Alternatively, 0.1 g / L to 3.0 g / L of metal oxide ions can be contained. These components can be incorporated into the phosphate coating or precipitated in a form other than phosphate to provide additional performance improvements in post-coat corrosion resistance or post-coat adhesion. It is contained in the processing solution. The concentration of these metal ions or metal oxide ions is 0.1 g
If it is smaller than / L, no improvement effect on the coating performance can be expected and it is meaningless. When the concentration of these metal ions or metal oxide ions is higher than 3.0 g / L, the effect of improving the coating performance is saturated, which is not economically disadvantageous. May interfere with zinc deposition.

As the metal ion source, oxides, hydroxides, carbonates, sulfates, nitrates, phosphates and the like of each metal can be used. The metal oxide ion source includes:
Sodium salts, potassium salts and the like can be used.

The metal ion or metal oxide ion may contain one kind or a combination of several kinds.

An etching agent may be added to the phosphate chemical conversion treatment solution in order to uniformly etch the surface of the metal to be treated. As the etching agent, fluoride ions or complex fluoride ions such as silicofluoride ions can be used. As these fluorine compounds,
For example, hydrofluoric acid, hydrosilicofluoric acid, or their metal salts (sodium salt, potassium salt) can be used.

The phosphate conversion treatment can be performed by a dipping method, a spray method, or a combination thereof.
The treatment time may be about 1 to 5 minutes, whereby a practically sufficient conversion coating can be formed. Further, the temperature of the phosphate chemical conversion treatment liquid is preferably 30 to 60 ° C.

After the phosphate conversion treatment, it is preferable to wash with water and use deionized water for final washing.

When the present technology is used for a paint base,
It is necessary to form a dense phosphate conversion coating in a thin film having a coating weight of 1.5 to 5 g / m ² . However, after the conventional titanium colloid-based surface conditioning treatment, if a phosphate conversion treatment containing no nickel component is performed, it is difficult to obtain a dense phosphate conversion coating in a thin film, and the surface conditioning step in the present invention requires a thin film Is an essential condition for obtaining a dense phosphate conversion coating.

[0040]

Next, the effects of the present invention will be described in detail with reference to examples and comparative examples of actual processing. In addition, an Example only listed the application example of this invention, and the application of this invention,
It does not limit the corresponding materials.

1. Test materials Electrogalvanized steel sheet [EG] (sheet thickness: 0.8 mm, coating weight: 20 g / m ² ), alloyed hot-dip galvanized steel sheet [GA] (sheet thickness: 0.8 mm, coating weight: 45 g / m ² ), cold rolled steel sheet
[CRS] (plate thickness: 0.8 mm, SPCC-SD), the following Examples and Comparative Examples were processed.

The processing steps common to the examples and comparative examples are shown below. (1) Degreasing [Fine Cleaner L4460 (registered trademark: Alkaline degreasing agent manufactured by Nippon Parkerizing Co., Ltd.)]
Agent A 20 g / L, Agent B 12 g / L, 43 ° C., 120 seconds,
Immersion (2) Rinse [tap water] Room temperature, 30 seconds, spray (3) Surface adjustment The conditions are described in the following Examples and Comparative Examples. In addition, about the thing which performed the surface adjustment processing of the titanium colloid system,
Preparen ZN (manufactured by Nippon Bakery Liquid Co., Ltd.) was used. (4) Phosphate conversion treatment conditions are described in Examples and Comparative Examples below. However, all treatment times were set to 120 seconds. (5) Rinse [tap water] Room temperature, 30 seconds, spray (6) Deionized water [Deionized water (electric conductivity: 0.2μ
S / cm or less)] Normal temperature, 20 seconds, spray (7) Draining and drying 90 ° C hot air, 120 seconds

A method for testing the coating performance of the test materials treated according to the examples and comparative examples will be described.

Regarding the evaluation of the appearance of the coating film, the evaluation was made by
The grade was evaluated. ：: Uniform coating ×: Coating with marked unevenness

The water-resistant secondary adhesion test conditions and evaluation method will be described. The temperature was maintained at 40 ° C., and the three-coated plate was immersed in a hot water bath subjected to air bubbling for 240 hours. After being lifted from the warm water bath, it was left for 2 hours, cut in a 2 mm grid, and the peeling state was evaluated by tape peeling. (Evaluation method) The peeling state was evaluated by three grades of ○ ××. ◎: No peeling was observed. ○: Slight peeling was observed at the cross cut edge. ×: Marked peeling was observed.

The conditions of the hot salt water immersion test and the evaluation method will be described. The temperature was kept at 55 ° C., and the electrodeposited single membrane plate cross-cut with an acrylic cutter was immersed for 240 hours in a 5 wt% salt water bath provided with air bubbling. After pulling up from the salt water bath and leaving it for 1 hour, the cross cut portion was peeled off from the tape, and evaluated by the width of peeling from the cut portion. (Evaluation method) The peeling state was evaluated by three grades of ○ ××.

The salt spray test conditions and evaluation method will be described. The temperature was maintained at 35 ° C., and the electrodeposited single membrane plate cross-cut by an acrylic cutter was tested using a salt spray tester using 5 wt% salt water. (JIS Z 2
371), taken out after a specified time, washed with water, and evaluated for the corrosion state of the cross cut portion. (Evaluation method) The corrosion state was evaluated by three grades of ○ ××. CRS (salt spray test time: 960 hours) ：: Maximum rust width of both sides less than 4 mm ○: Maximum rust width of both sides 4 mm or more and less than 5 mm ×: Maximum rust width of both sides 5 mm or more Zn plating (salt water spray test time: 480 hours) ：: One side Maximum rust width less than 4mm ○: Maximum rust width of 4mm or more and less than 5mm on one side ×: Maximum rust width of 5mm or more on both sides

[0048]

Examples 1 to 25 Tables 1, 2, 7, 12, and 17 show the surface conditioning methods of Examples 1 to 25.

[0049]

[Comparative Examples 1 to 40] Tables 3, 4, 8, 9, 13, 14, 18, and 19 show the methods for surface preparation and phosphating treatment of Comparative Examples 1 to 40.

The chemical appearance and the coating performance test results of the test materials treated according to each of the examples and comparative examples are shown in Tables 5, 6, 10, 11, and 12.
Shown at 15,16,20,21.

[0051]

Table 1 Examples 1 to 5

[0052]

[Table 2] Examples 6 to 10

[0053]

[Table 3] Comparative Examples 1 to 5

[0054]

Table 4 Comparative Examples 6 to 10

[0055]

[Table 5] Chemical conversion film appearance and coating performance test results of Examples 1 to 10

[0056]

[Table 6] Chemical conversion film appearance and coating performance test results of Comparative Examples 1 to 10

[0057]

[Table 7] Examples 11 to 15

[0058]

Table 8 Comparative Examples 11 to 15

[0059]

Table 9 Comparative Examples 16 to 20

[0060]

[Table 10] Chemical conversion film appearance and coating performance test results of Examples 11 to 15

[0061]

[Table 11] Chemical conversion film appearance and coating performance test results of Comparative Examples 11 to 20

[0062]

[Table 12] Examples 16 to 20

[0063]

Table 13 Comparative Examples 21 to 25

[0064]

Table 14 Comparative Examples 26 to 30

[0065]

[Table 15] Chemical conversion film appearance and coating performance test results of Examples 16 to 20

[0066]

[Table 16] Chemical conversion film appearance and coating performance test results of Comparative Examples 21 to 30

[0067]

[Table 17] Examples 21 to 25

[0068]

[Table 18] Comparative Examples 31 to 35

[0069]

Table 19 Comparative Examples 36 to 40

[0070]

[Table 20] Chemical conversion film appearance and coating performance test results of Examples 21 to 25

[0071]

[Table 21] Chemical conversion film appearance and coating performance test results of Comparative Examples 31 to 40

[0072]

As described above, the method for phosphating metal materials of the present invention does not contain nickel and is excellent in terms of environmental protection, and is sufficiently applicable to various metal material surfaces such as steel and zinc plating. This is very useful in that a uniform phosphate coating can be obtained and the coating adhesion and the corrosion resistance after coating are excellent.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takaomi Nakayama 1-15-1 Nihonbashi, Chuo-ku, Tokyo F-term in Japan Parkerizing Co., Ltd. 4D075 BB75X CA47 DA06 DB05 DB07 DC12 EA02 EB19 EB22 EC01 EC53 EC54 4K026 AA02 AA09 AA11 BA03 BB06 BB08 CA23 CA37 CA38 CA39 EA08

Claims (5)

[Claims] 1. A metal material comprising: at least one phosphate particle selected from phosphates containing at least one divalent and / or trivalent metal having a particle size of 5 μm or less; After being brought into contact with a surface conditioning liquid containing at least one selected from saccharides, polysaccharides and derivatives thereof, nickel is not contained, zinc ions are contained at 0.5 to 5 g / L, and phosphate ions are added at 5
A phosphate conversion treatment method for a metal material, which comprises contacting a phosphate conversion treatment solution containing up to 30 g / L and a conversion promoter. 2. The method according to claim 1, wherein the metal material comprises at least one phosphate particle selected from phosphates containing at least one divalent and / or trivalent metal having a particle size of 5 μm or less, and a positive component as an accelerating component. After being brought into contact with a surface conditioning solution containing at least one of phosphoric acid, polyphosphoric acid and an organic phosphonic acid compound, no nickel is contained, zinc ions are 0.5 to 5 g / L, and phosphate ions are 5 to 5 g / L. A method for phosphate conversion treatment of a metal material, comprising contacting a phosphate conversion treatment solution containing 30 g / L and a conversion promoter. 3. A metal material comprising at least one phosphate particle selected from phosphates containing at least one divalent and / or trivalent metal having a particle size of 5 μm or less, and acetate as an accelerating component. After contacting with a surface conditioning liquid containing at least one of a vinyl polymer or a derivative thereof or a monomer copolymerizable with vinyl acetate and a copolymer of vinyl acetate and at least one water-soluble polymer compound, Phosphorus of a metal material, which does not contain nickel and is brought into contact with a phosphate chemical conversion treatment solution containing 0.5 to 5 g / L of zinc ions, 5 to 30 g / L of phosphate ions and a chemical conversion accelerator. Acid conversion treatment method. 4. A metal material comprising: at least one phosphate particle selected from phosphates containing at least one divalent and / or trivalent metal having a particle size of 5 μm or less; At least one or more monomers selected from monomers represented by Chemical Formula 1 and α, β unsaturated carboxylic acid monomers;
After contacting with a surface conditioning liquid containing a polymer or at least one copolymer obtained by polymerizing a vinyl acetate monomer and 50% by weight or less of a copolymerizable monomer, nickel is contained. A phosphate conversion treatment solution containing 0.5 to 5 g / L of zinc ions, 5 to 30 g / L of phosphate ions and a chemical conversion accelerator. Processing method. [Image Omitted] H ₂ CＲC (R ¹ ) —COOR ² Chemical Formula 1 (wherein R ¹ is H or CH ₃ , R ² is H, an alkyl group having 1 to 5 C or C) Is 1 to 5 hydroxyalkyl group) 5. The method according to claim 1, wherein at least one metal ion selected from the group consisting of magnesium ion, cobalt ion, manganese ion, calcium ion, tungstate ion and strontium ion is added to the phosphate conversion treatment solution. The phosphate conversion treatment method for a metal material according to any one of claims 1 to 4, wherein the content is from 1 to 3.0 g / L.