JP2003247082A - Surface treated sheet having excellent press formability, suitability for adhesive and chemical convertibility and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an automobile steel sheet which has excellent pressing properties, suitability for adhesives and chemical convertibility in a simple process at a low cost by utilizing the particles of phosphates. <P>SOLUTION: In the surface treated sheet having excellent pressing formability, suitability for adhesives and chemical convertibility, a stacked film of phosphate particles is present on the surface of a galvanized steel sheet, a cold rolled steel sheet, an aluminum sheet or an aluminum alloy sheet. The phosphate particles have an arithmetic mean particle diameter of 0.1 to 2 μm, and contain at least one kind of bivalent or trivalent metal selected from Zn, Fe, Mn, Ni, Co, Ca, Mg and Al. An organic compound having a dispersion function such as a polymer of (metha)acrylic acid ester, monosaccharide, polysaccharide and the derivatives thereof is preferably present. The quantity of the stacked film of the phosphate particles is preferably 0.01 to 5 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent pressability,
The present invention relates to a surface-treated plate having adhesive compatibility and chemical conversion treatability, which is particularly suitable for automobile body production, and a method for producing the same.

[0002]

2. Description of the Related Art In order to improve the press formability of a metal material, there is a method of applying a highly lubricating press oil to the surface of the metal material, but this method has a problem of degreasing property in the next step. . Further, as a method for improving the press moldability of a metal material for automobiles, Japanese Patent Laid-Open No. 62-192597 discloses
A method of forming an alloy plating of zinc and iron on the surface of a zinc-containing metal-plated steel sheet by an electroplating method has been disclosed, but this method has drawbacks such as increased facility cost for electrolysis and electrical cost during manufacturing. There is.

Further, Japanese Patent Laid-Open No. 07-138764 discloses a zinc-containing metal-plated steel sheet composite having a zinc phosphate composite coating layer formed on the surface thereof and excellent in high-speed pressability. Since the activation treatment step, the composite coating treatment step, the water washing step, and the drying step are required for a long time, the facility cost is required, and the heating of the composite coating treatment step causes a problem of energy cost. There is a method of forming a zinc phosphate composite coating layer by coating or washing with water for the purpose of shortening the process, but there is a problem in adhesion compatibility and the like.

Further, in Japanese Unexamined Patent Publication No. 9-111473, a compound having a boundary lubrication action is formed on the surface of a plated layer of a zinc-based plated steel sheet (a tool which reacts with a lubricating oil or a steel sheet surface at a sliding interface during press forming). A method for improving press formability by forming a coating composition having an average thickness of 100 nm or more and 1000 nm or less, which contains a compound that produces a reaction product that acts to prevent contact between the steel sheet surface and As one of the methods, a method of forming a coating composition by applying a phosphorus compound or a zinc compound in a liquid form or a sol form on a steel sheet has been proposed, but it is not sufficient in press formability and adhesive compatibility. Hard to say.

[0005]

DISCLOSURE OF THE INVENTION The present invention uses a phosphate particle to produce an automobile steel sheet excellent in press formability, adhesive compatibility, and chemical conversion treatment in a simple process at low cost. The purpose is to provide.

[0006]

Means for Solving the Problems As a result of intensive studies made by the present inventors for improving the press formability of a metal plate, the particles of a specific metal phosphate having a specific size are obtained. It was found that the pressability, adhesive compatibility and chemical conversion treatability of the metal plate can be improved by laminating the particles on the surface of the metal plate to form a film, and completed the present invention.

That is, the present invention is a zinc-based plated steel sheet,
A surface-treated plate having a laminated coating of phosphate particles on the surface of a cold rolled steel plate, an aluminum plate or an aluminum alloy plate, wherein the phosphate particles have an arithmetic mean particle size of 0.1 to 2
μm, and Zn, Fe, Mn, Ni, Co, C
a surface excellent in press moldability, adhesive compatibility and chemical conversion treatment, characterized in that it is a phosphate particle containing at least one divalent or trivalent metal selected from a, Mg and Al. It is a processing plate. For a laminated coating of phosphate particles,
It is preferable that an organic compound having a dispersing function is present. This organic compound having a dispersing function has the following general formula (1):

[0008]

[Chemical 2]

(Wherein R ¹ is H or CH ₃ , R ² is H or an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms) and / or α, A polymer or copolymer of a β-unsaturated carboxylic acid monomer, or a copolymer of 50% by weight or more of the above monomer and 50% by weight or less of a copolymerizable monomer is preferable, and a monosaccharide. One or more saccharides selected from polysaccharides and their derivatives are preferable. Laminated coating amount of phosphate particles is 0.01 to 5 g / m ²
Is preferred.

Further, according to the present invention, a zinc-based plated steel sheet, a cold rolled steel sheet, an aluminum plate or an aluminum alloy plate has a surface with an arithmetic mean particle size of 0.1 to 2 μm and Zn,
Particles having an arithmetic mean particle size of 0.1 to 2 μm of a phosphate containing at least one divalent or trivalent metal selected from Fe, Mn, Ni, Co, Ca, Mg and Al were suspended. A method for producing a surface-treated plate excellent in press moldability, adhesive compatibility and chemical conversion treatment, characterized by applying a suspension and drying. It is preferable to add an organic compound having a dispersing function to this suspension. The organic compound having a dispersing function is a polymer or copolymer of the monomer represented by the general formula (1) and / or the α, β-unsaturated carboxylic acid monomer, or the monomer. A copolymer of 50% by weight or more and 50% by weight or less of a copolymerizable monomer is preferable, and one or more saccharides selected from monosaccharides, polysaccharides and derivatives thereof are preferable.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The metal plate to which the present invention is applied is a zinc-based plated steel plate, a cold-rolled steel plate, an aluminum plate, or an aluminum alloy plate. The galvanized steel sheet is zinc or an alloy of zinc and another metal (for example, at least one metal selected from nickel, iron, aluminum, manganese, chromium, magnesium, cobalt, lead and antimony),
Further, it is plated with inevitable impurities. The plating method is hot-dip plating, electroplating, vapor deposition plating or the like, and the plating method is not limited. Cold rolled steel sheet is JIS
SPCC, SPCD, S standardized by G 3141
Examples include PCE and high strength / high strength steel plates. The aluminum plate is a pure aluminum plate having an aluminum purity of 99% or more. The aluminum alloy plate is, for example, Al-Cu.
Alloy, Al-Mg-Si alloy, Al-Mg alloy, Al-
It is an alloy plate such as a Zn-Mg alloy.

In the present invention, the particles of the phosphate to be laminated on the surface of the metal plate to form a film are particles having an arithmetic average particle diameter of 0.1 to 2 μm, and Zn, Fe, Mn,
It is a phosphate particle containing at least one divalent or trivalent metal selected from Ni, Co, Ca, Mg and Al. This divalent or trivalent metal phosphate is, for example, Zn ₃ (PO ₄ ) ₂ , Zn ₂ Fe (PO ₄ ) ₂ or Zn ₂ N.
i (PO ₄ ) ₂ , Ni ₃ (PO ₄ ) ₂ , Zn ₂ Mn (P
O ₄ ) ₂ , Mn ₃ (PO ₄ ) ₂ , Mn ₂ Fe (PO ₄ ) ₂ , Ca
₃ (PO ₄ ) ₂ , Zn ₂ Ca (PO ₄ ) ₂ , FePO ₄ , Al
Examples thereof include PO ₄ , Co ₃ (PO ₄ ) ₂ and Mg ₃ (PO ₄ ) ₂ . These phosphate particles may be used in combination of two or more kinds. Incidentally, the divalent or trivalent metal phosphate usually exists as a hydrate such as a dihydrate or a tetrahydrate, but in the present invention, since the number of hydrated water does not affect the effect, anhydrous It is exemplified in the form of salt.

The size of the particles of the divalent or trivalent metal phosphate is 0.1 to 2 μm in terms of arithmetic mean particle size. If the arithmetic mean particle size is less than 0.1 μm, the carrier effect of the press oil (oil retaining effect due to surface roughening) will not be exhibited, so improvement in press formability cannot be expected.
That is, when a phosphate solution or a submicron-sized phosphate colloid is applied, the phosphate completely covers the metal surface and the carrier effect of the press oil disappears, resulting in improved press formability. I can't see it. In that case, the compatibility of the adhesive is also deteriorated. On the other hand, when the arithmetic mean particle size exceeds 2 μm, the coating property is deteriorated and the press formability is deteriorated, and when the suspension is prepared at the time of coating,
There is a problem that the stability of the suspension is lowered due to the high sedimentation property of the phosphate particles. The more preferable phosphate particle size is 0.1 to 1.5 μm in terms of arithmetic mean particle size.

The phosphate particles used in the present invention are, for example, Zn, Fe, Mn, Ni, Co, Ca, Mg and A.
After adding a phosphate aqueous solution such as sodium monohydrogen phosphate to an aqueous solution in which a salt such as a divalent or trivalent metal sulfate selected from 1 is dissolved to cause precipitation, and washing the precipitate, It is manufactured by drying, crushing to a predetermined particle size with a ball mill or the like. Then, the particles are suspended in water at an appropriate concentration to prepare a suspension, and the suspension is applied to the surface of the metal plate and dried to form a laminated film of phosphate particles. As a coating method at that time, a roll coater method, a dipping method, a shower squeeze method, a flow coating method, an electrostatic coating method or the like can be used. The coating amount is 0.01 when the laminated coating amount is dry.
It should be ~ 5 g / m ² . If it is 0.01 g / m ² or less, the surface of the zinc-containing plating layer cannot be sufficiently covered and the press moldability is not sufficiently improved. Also, 5 g /
Beyond m ^2, or cause powdering, since the adhesive compatible undesirably reduced. A more preferable laminated film amount is 0.1 to ² g / m ² .

In preparing the suspension of the divalent or trivalent metal phosphate, it is preferable to use an organic compound having a dispersing function in combination. Here, the organic compound having a dispersing function is a compound having an action of improving the dispersion stability of the phosphate particles in the suspension and preventing the precipitation of the particles. This organic compound is adsorbed on the surface of particles of a divalent or trivalent metal phosphate, and due to the repulsive force and steric hindrance action due to its charge, the divalent or trivalent metal phosphate in suspension is Prevents coagulation and sedimentation by preventing collision between salts. Therefore, by applying and drying the suspension, a more uniform laminated coating of divalent or trivalent metal phosphate particles can be obtained. Then, this improves press moldability, and even when the usual phosphate chemical conversion treatment is performed thereafter, a zinc phosphate film is deposited on the metal material without adversely affecting the zinc phosphate chemical conversion reaction. be able to.

The above-mentioned organic compound having a dispersing function not only enhances the dispersion stability of a suspension of divalent or trivalent metal phosphate particles, but also divalent or trivalent metal phosphorus. Those having a function of fixing the acid salt to the metal surface are preferable. That is, when this organic compound is used, the organic compound structurally has the ability to be adsorbed on the metal surface.
The fixation of the phosphate of trivalent or trivalent metal to the metal surface is improved, and by coating and drying on the surface of the material to be treated, it is possible to obtain more excellent pressability, adhesive compatibility, and chemical conversion treatability. become.

When the above-mentioned organic compound having a dispersing function has an extreme pressure effect, it chemically reacts on the metal surface during friction during press working to form an extreme pressure resistant film and the lubricating function is improved. When this extreme pressure resistant film is present on the metal surface, for example, the degreasing property is poor in the degreasing process of an automobile body,
As a result, there is a problem that the chemical conversion processability deteriorates. Therefore, in the present invention, as the organic compound having a dispersing function, one having an extreme pressure action is not used. Organic compounds having extreme pressure action are organic compounds containing sulfur, phosphorus, chlorine, etc.,
Typical examples include dibenzyl disulfide, tricresyl phosphate, and chlorinated paraffin wax.

The organic compound having a dispersing function used in the present invention is preferably a polymer of a monomer represented by the general formula (1) or a polymer of an α, β-unsaturated carboxylic acid monomer. A copolymer of a monomer represented by the general formula (1) and an α, β-unsaturated carboxylic acid monomer, and further, a monomer represented by the general formula (1) and / or α, β A monomer 50 copolymerizable with 50% by weight or more of the unsaturated carboxylic acid monomer
It is a copolymer with less than or equal to wt%. Examples of the monomer represented by the general formula (1) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate. ,
Pentyl methacrylate, hydroxymethyl acrylate,
Examples thereof include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxypentyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and hydroxypentyl methacrylate.

As the α, β-unsaturated carboxylic acid monomer, for example, acrylic acid, methacrylic acid, maleic acid or the like can be used. Further, examples of the monomer represented by the above general formula (1) or the monomer copolymerizable with the above α, β-unsaturated carboxylic acid monomer include vinyl acetate, styrene, vinyl chloride and vinyl. Sulfonic acid or the like can be used. Further, the above-mentioned polymers or copolymers may be used in combination of several kinds.

The preferred organic compound having a dispersing function of the present invention is a saccharide selected from monosaccharides, polysaccharides and derivatives thereof. Any combination of D-monosaccharide, L-monosaccharide and optical rotation (+,-) can be used. Monosaccharides used in the present invention, basic constituent saccharides of polysaccharides and derivatives thereof, for example, fructose, tagatose,
Psicose, sulboose, erythrose, threose,
Ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose or talose.

In the present invention, before using a monosaccharide,
The basic constituent sugar itself, the above when using a polysaccharide
Homopolysaccharides or heteropolysaccharides of basic constituent sugars,
As the derivatives thereof, the hydroxyl group of the basic constituent sugar is NO
₂, CH₃, C₂H_FourOH, CH ₂CH (OH) CH₃, CH₂
Monosaccharides obtained by etherification with a substituent such as COOH
Or a homopolysaccharide containing in its structure a monosaccharide substituted by the above substituents.
Sugars and heteropolysaccharides can be used, and several types of
Can be used in combination with sugars, polysaccharides and their derivatives.
I can do it. In addition, water of monosaccharides, polysaccharides and their derivatives
The above-mentioned monosaccharides, polysaccharides and derivatives thereof for enhancing solubility
It is also possible to use the alkali metal salt or ammonium salt of
it can. Furthermore, if water solubilization is difficult with the above structure,
It may be used after being dissolved in a compatible organic solvent.
Absent. When classifying sugars, the degree of hydrolysis
May be classified into monosaccharides, oligosaccharides and polysaccharides depending on
However, the present invention produces two or more monosaccharides by hydrolysis.
The trick is called a polysaccharide, a sugar that is not hydrolyzed any further.
The classes were called monosaccharides.

In the present invention, the concentration of particles of the divalent or trivalent metal phosphate in the suspension used for coating the metal surface is not particularly limited, but is 1 to 50% by mass. If this concentration is less than 1% by mass, the concentration is too low to form a sufficient amount of the film, and if it exceeds 50% by mass, the viscosity of the suspension increases and coating is difficult, and the appearance becomes poor. Further, the concentration of the organic compound having a dispersing function is 0.01 to 10% by mass. If this concentration is less than 0.01% by mass, the dispersing function will not be exerted depending on the concentration of the phosphate particles, and if it exceeds 10% by mass, the film performance such as adhesive compatibility will be unfavorable. Further, a leveling agent, a solvent and the like may be added to the suspension of the phosphate particles of the present invention for the purpose of improving liquid stability, coating property, drying property and the like.

[0023]

In the present invention, a divalent or trivalent metal phosphate having an arithmetic mean particle size of 0.1 to 2 μm is formed on the surface of a zinc-based plated steel sheet, a cold rolled steel sheet, an aluminum plate or an aluminum alloy plate. Although a laminated coating of the particles is present, the coating exhibits a carrier effect of the press oil (oil retaining effect by roughening) during press working, so that press formability is improved. When an organic compound having a dispersing function is present in a laminated film of particles of a divalent or trivalent metal phosphate, the bivalent or trivalent metal is adsorbed on the metal surface due to its adsorption ability. Has the function of fixing the phosphate of the above to the metal surface. Further, by adding an organic compound having a dispersing function to a suspension of a divalent or trivalent metal phosphate, the organic compound is added to the surface of particles of the divalent or trivalent metal phosphate. Stability of the phosphate particles because it prevents the coagulation and settling which prevents the collision of the divalent or trivalent metal phosphates in the suspension due to the repulsive force and the steric hindrance by the charge. And the sedimentation of the particles can be prevented.

Further, the divalent or trivalent metal phosphate used in the present invention not only becomes a nucleus when a phosphate crystal is precipitated when a usual phosphate chemical conversion treatment is carried out thereafter. It also has the effect of promoting the precipitation reaction itself. That is, in the surface-treated plate produced by the present invention, a part of the divalent or trivalent metal phosphate on the surface is dissolved in the phosphate chemical conversion treatment bath, so that the surface of the surface-treated plate becomes very close to the surface. Since the main component of the phosphate crystal is supplied, the initial precipitation reaction of the phosphate crystal is remarkably promoted and the chemical conversion treatability is improved.

Since the divalent or trivalent metal phosphate used in the present invention is a component similar to the phosphate chemical conversion treatment bath and the phosphate chemical conversion treatment film, even if the phosphate chemical conversion treatment is carried out. Even if a part of the film dissolves in the treatment bath, it does not adversely affect the chemical conversion treatment bath, and even if it is incorporated into the phosphate film as nuclei, it does not adversely affect the performance of the phosphate chemical conversion film. Have By using the surface-treated plate of the present invention, press formability (that is, suitability of the surface-treated plate to firmly bond other materials with various adhesives) is not deteriorated (that is, , It is possible to form a zinc phosphate film easily by a conventional zinc phosphate chemical conversion treatment, and to improve the smoothness of the surface-treated sheet by press molding with a die without the inconvenience of breaking. You can do it.

[0026]

EXAMPLES Next, the effects of the surface-treated plate of the present invention will be described in detail with reference to examples and comparative examples. However, the zinc phosphate chemical conversion treatment bath used as the post-treatment in Examples and Comparative Examples,
This is merely an example, and the combination with the surface treatment agent of the present invention and the method thereof are not limited.

[Test Plate] Abbreviations and breakdowns of the test plates used in Examples and Comparative Examples are shown below.・ EG (Double-sided electrogalvanized steel sheet: coating weight 20 g
/ M ² ) ・ GA (double-sided galvannealed steel sheet: coating weight of 45 g / m ² ) ・ Gl (double-sided galvanized steel sheet: coating weight of 60 g
/ M ² ) ・ Aluminum alloy (6022, ALCOA symbol) ・ Cold rolled steel plate (SPCC)

[Alkali degreasing liquid] In each of the examples and comparative examples, the test plate was degreased with an alkaline degreasing liquid before use. Alkaline degreasing liquid is 2% of Fine Cleaner L4460A (registered trademark: manufactured by Nippon Parkerizing Co., Ltd., abbreviation: FC-L4460A) for galvanized steel sheet, Fine Cleaner L4460B (registered trademark: manufactured by Nippon Parkerizing Co., Ltd., abbreviation) : FC-L4460B) was diluted to 1.4% with tap water and heated to 42 ° C. before use. For the aluminum alloy, Fine Cleaner 315 (registered trademark: manufactured by Nippon Parkerizing Co., Ltd., abbreviation: FC-315) was diluted to 3% with tap water and heated to 60 ° C. before use.

[Suspension of Phosphate Particles of the Present Invention] The compositions and treatment conditions of the suspensions of phosphate particles used in Examples 1 to 10 of the present invention are shown in Table 1 (1) and (2). ). In addition,
The effect of the present invention is not limited to the pH of the suspension, but the pH of the aqueous solution was previously adjusted to neutral with sodium hydroxide in order to prevent dissolution of the divalent or trivalent metal phosphate.

[0030]

[Table 1]

Example 1 0.5 mol / L iron (II) sulfate solution 1 heated to 50 ° C.
To L, 100 mL of 1 mol / L zinc sulfate solution and 1 mol / L
100 mL of sodium monohydrogen phosphate solution were alternately added to form a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to age the precipitated particles, and then gradient washing was repeated 10 times. Drying the precipitate obtained by filtration was was analyzed by X-ray diffraction, the precipitate is phosphophyllite _{[Zn 2 Fe (PO 4)} 2 · 4H 2 O] containing part third phosphate iron there were. Next, 100 g of the phosphophyllite was added to 1 kg of water, and then pulverized with a ball mill using zirconia beads having a diameter of 0.5 mm for about 1 hour. After crushing, the phosphophyllite concentration in the suspension was adjusted to 3% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering particle size distribution analyzer (LA-920:
As a result of measurement by HORIBA, Ltd., it was 0.5 μm. Next, the suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and was dried by setting a hot air oven so that the ultimate plate temperature was 100 ° C. The coating weight at this time was 0.3 g / m ² . About 1.5 g / m of press oil (NOXRUST550HN, manufactured by Parka Kosan) was added to this test plate.
^After applying ² oils, press workability and adhesive strength of the adhesive were investigated.

Example 2 0.5 mol / L iron (II) sulfate solution 1 heated to 50 ° C.
To L, 100 mL of 1 mol / L zinc sulfate solution and 1 mol / L
100 mL of sodium monohydrogen phosphate solution were alternately added to form a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to age the precipitated particles, and then gradient washing was repeated 10 times. Drying the precipitate obtained by filtration was was analyzed by X-ray diffraction, the precipitate is phosphophyllite _{[Zn 2 Fe (PO 4)} 2 · 4H 2 O] containing part third phosphate iron there were. Table 1
50 g of the phosphophyllite was added to 1 kg of a solution prepared by previously diluting and dissolving the organic compound (A) having a dispersing function in water to 0.02% by weight, and then adding 0.5 g
It was crushed for about 1 hour by a ball mill using mm zirconia beads. After crushing, the concentration of phosphophyllite in the suspension was adjusted to 4% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering type particle size distribution analyzer (LA-920: Horiba, Ltd.), and it was 0.5 μm. Next, the suspension was applied onto the surface of the test material that had been cleaned by washing with water after degreasing, and was dried by setting a hot air oven so that the reached plate temperature was 80 ° C. The coating weight at this time was 0.3 g / m ² . A press oil of about 1.5 g / m ² was further applied to the test plate to examine the press workability and the adhesive strength of the adhesive.

Example 3 1 kg of a solution prepared by previously diluting and dissolving the organic compound (A) having a dispersing function shown in Table 1 with water to 0.05 wt% was used.
₃ (PO ₄₎ was added to ₂ · 4H ₂ O in 100 g, diameter 0.5mm
It was crushed for about 1 hour by a ball mill using the zirconia beads of. After milling, Zn ₃ (PO ₄₎ in suspension in tap water ₂ · 4H ₂ O concentration was adjusted to 6%. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering type particle size distribution measuring device (LA-920: Horiba, Ltd.),
It was 1.7 μm. Next, the suspension was applied to the surface of the test material that had been degreased and then washed with water, and the surface was dried by setting a hot air oven so that the reached plate temperature was 80 ° C.
The coating weight at this time was 0.9 g / m ² . A press oil of about 1.5 g / m ² was further applied to the test plate, and press workability and adhesive strength of the adhesive were investigated.

Example 4 0.5 mol / L iron (II) sulfate solution 1 heated to 50 ° C.
To L, 100 mL of 1 mol / L zinc sulfate solution and 1 mol / L
100 mL of sodium monohydrogen phosphate solution were alternately added to form a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to age the precipitated particles, and then gradient washing was repeated 10 times. Drying the precipitate obtained by filtration was was analyzed by X-ray diffraction, the precipitate is phosphophyllite _{[Zn 2 Fe (PO 4)} 2 · 4H 2 O] containing part third phosphate iron there were. Table 1
After adding 100 g of the phosphophyllite to 1 kg of a solution prepared by previously diluting the organic compound (A) having a dispersing function in water to 0.05% by weight and adding it, the diameter of 0.
It was crushed for about 1 hour by a ball mill using 5 mm zirconia beads. After crushing, the phosphophyllite concentration in the suspension was adjusted to 8% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering type particle size distribution analyzer (LA-920: Horiba, Ltd.), and it was 0.5 μm. Next, the suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and the hot air oven was set so that the reached plate temperature was 100 ° C. and drying was performed. The coating weight at this time was 1.6 g / m ² . About 1.5 g / m ^{2 of} press oil was further applied to this test plate.
After oiling, press workability and adhesive strength of the adhesive were investigated.

Example 5 To 1 L of a 0.1 mol / L calcium nitrate solution heated to 50 ° C., 200 mL of a 1 mol / L zinc nitrate solution was added, and further 200 mL of a 1 mol / L sodium monohydrogen phosphate solution was added for precipitation. Was generated. Aqueous solution containing precipitate at 90 ℃
After warming for a period of time to age the precipitated particles, gradient washing is performed for 10
Repeatedly repeated. The precipitate obtained by filtration was dried and analyzed by X-ray diffraction. As a result, the precipitate was found to be schortite [Zn ₂ Ca
Was _{(PO 4) 2 · 2H 2} O]. A ball mill using zirconia beads having a diameter of 0.5 mm after adding 100 g of Scholtite to 1 kg of a solution in which the organic compound (A) having a dispersing function shown in Table 1 was diluted and dissolved in water to 0.05% by weight in advance. It was crushed for about 1 hour. After the pulverization, the scholtite concentration in the suspension was adjusted to 4% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering particle size distribution analyzer (LA-920: Horiba, Ltd.).
It was 0.5 μm as a result of measurement by. Next, the suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and was dried by setting a hot air oven so that the reached plate temperature was 80 ° C. The coating weight at this time is 0.4 g /
It was set to m ² . About 1.5 g of press oil was further added to this test plate.
/ M ² oil was applied, and press workability and adhesive strength of the adhesive were investigated.

Example 6 0.5 mol / L iron (II) sulfate solution 1 heated to 50 ° C.
To L, 100 mL of 1 mol / L zinc sulfate solution and 1 mol / L
100 mL of sodium monohydrogen phosphate solution were alternately added to form a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to age the precipitated particles, and then gradient washing was repeated 10 times. Drying the precipitate obtained by filtration was was analyzed by X-ray diffraction, the precipitate is phosphophyllite _{[Zn 2 Fe (PO 4)} 2 · 4H 2 O] containing part third phosphate iron there were. Table 1
100 g of the phosphophyllite is added to 1 kg of a solution prepared by previously diluting and dissolving the organic compound (A) having a dispersing function in 0.05 wt% with isopropyl alcohol and water.
Was added, and the mixture was pulverized with a ball mill using zirconia beads having a diameter of 0.5 mm for about 1 hour. After crushing, the phosphophyllite concentration in the suspension was adjusted to 6% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering particle size distribution analyzer (LA-920:
It was 1.1 μm as a result of measurement by Horiba, Ltd. Next, the suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and was dried by setting a hot air oven so that the reached plate temperature was 80 ° C. The coating weight at this time was 0.8 g / m ² . A press oil of about 1.5 g / m ² was further applied to the test plate, and press workability and adhesive strength of the adhesive were investigated.

Example 7 0.5 mol / L iron (II) sulfate solution 1 heated to 50 ° C.
To L, 100 mL of 1 mol / L zinc sulfate solution and 1 mol / L
100 mL of sodium monohydrogen phosphate solution were alternately added to form a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to age the precipitated particles, and then gradient washing was repeated 10 times. Drying the precipitate obtained by filtration was was analyzed by X-ray diffraction, the precipitate is phosphophyllite _{[Zn 2 Fe (PO 4)} 2 · 4H 2 O] containing part third phosphate iron there were. Table 1
After adding 100 g of the phosphophyllite to 1 kg of a solution prepared by previously diluting the organic compound (A) having a dispersing function in water to 0.05% by weight and adding it, the diameter of 0.
It was crushed for about 1 hour by a ball mill using 5 mm zirconia beads. After crushing, the phosphophyllite concentration in the suspension was adjusted to 3% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering type particle size distribution analyzer (LA-920: Horiba, Ltd.), and it was 0.5 μm. Next, the suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and was dried by setting a hot air oven so that the reached plate temperature was 80 ° C. The coating weight at this time was 0.5 g / m ² . Pressing oil is further applied to this test plate to about 1.5 g / m ²
After oiling, the press workability and the adhesive strength of the adhesive were investigated.

Example 8 0.5 mol / L iron (II) sulfate solution 1 heated to 50 ° C.
To L, 100 mL of 1 mol / L zinc sulfate solution and 1 mol / L
100 mL of sodium monohydrogen phosphate solution were alternately added to form a precipitate. The aqueous solution containing the precipitate was heated at 90 ° C. for 1 hour to age the precipitated particles, and then gradient washing was repeated 10 times. Drying the precipitate obtained by filtration was was analyzed by X-ray diffraction, the precipitate is phosphophyllite _{[Zn 2 Fe (PO 4)} 2 · 4H 2 O] containing part third phosphate iron there were. Table 1
After adding 100 g of the phosphophyllite to 1 kg of a solution prepared by previously diluting the organic compound (A) having a dispersing function in water to 0.05% by weight and adding it, the diameter of 0.
It was crushed for about 1 hour by a ball mill using 5 mm zirconia beads. After crushing, the phosphophyllite concentration in the suspension was adjusted to 6% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering type particle size distribution measuring device (LA-920: Horiba, Ltd.), and it was found to be 1.2 μm. Next, the suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and was dried by setting a hot air oven so that the reached plate temperature was 80 ° C. The coating weight at this time was 0.8 g / m ² . A press oil of about 1.5 g / m ² was further applied to this test plate, and press workability and adhesive strength of the adhesive were investigated.

Example 9 An organic compound (A) having a dispersion function shown in Table 1 was dissolved in water to a concentration of 0.05% by weight and dissolved in 1 kg,
Zn ₃ (PO ₄₎ was added to ₂ · 4H ₂ O in 100 g, diameter 0.5m
Milled for about 1 hour with a ball mill using m zirconia beads. After pulverization, the concentration of Zn ₃ (PO ₄ ) ₂ .4H ₂ O in the suspension was adjusted to 3% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering type particle size distribution measuring device (LA-920: Horiba, Ltd.),
It was 0.6 μm. Next, the suspension was applied to the surface of the test material that had been degreased and then washed with water to clean it, and the surface temperature was 8
A hot air oven was set so that the temperature was 0 ° C., and drying was performed. The coating weight at this time was 0.2 g / m ² . A press oil of about 1.5 g / m ² was further applied to the test plate, and press workability and adhesive strength of the adhesive were investigated.

Example 10 To 1 L of a 0.1 mol / L calcium nitrate solution heated to 50 ° C., 200 mL of a 1 mol / L zinc nitrate solution was added, and further 200 mL of a 1 mol / L sodium monohydrogen phosphate solution was added to cause precipitation. Was generated. Aqueous solution containing precipitate at 90 ℃
After warming for a period of time to age the precipitated particles, gradient washing is performed for 10
Repeatedly repeated. The precipitate obtained by filtration was dried and analyzed by X-ray diffraction. As a result, the precipitate was found to be schortite [Zn ₂ Ca
Was _{(PO 4) 2 · 2H 2} O]. After adding 100 g of Scholtite to 1 kg of a solution in which the organic compound (A) having the dispersing function shown in Table 1 was diluted and dissolved in water to 0.05% by weight in advance, zirconia beads having a diameter of 0.5 mm were used. It was crushed with a ball mill for about 1 hour. After crushing, the phosphophyllite concentration in the suspension was adjusted to 3% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering type particle size distribution analyzer (LA-920: Horiba, Ltd.), and it was 0.5 μm. Next, the suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and was dried by setting a hot air oven so that the reached plate temperature was 80 ° C. The coating weight at this time was 0.3 g / m ² . A press oil of about 1.5 g / m ² was further applied to the test plate, and press workability and adhesive strength of the adhesive were investigated.

Comparative Examples 1 to 4 Table 2 shows the composition and treatment conditions of the suspensions of the phosphate particles used in Comparative Examples 1 to 4. 100 g of Zn ₃ (PO ₄ ) ₂ .4H ₂ O was added to 1 kg of a solution prepared by previously diluting the organic compound (A) having a dispersing function shown in Table 2 to 0.05% by weight with water.
After the addition, pulverization was performed with a ball mill using zirconia beads having a diameter of 10 mm at different times. After pulverization, the concentration of Zn ₃ (PO ₄ ) ₂ .4H ₂ O in the suspension was adjusted to 3% with tap water. The average particle size of the fine particles in this suspension was measured by a laser diffraction / scattering particle size distribution analyzer (LA-920:
As a result of measurement by HORIBA, Ltd., Comparative Examples 1, 2, 3
And 4 are 0.05 μm, 6.5 μm, and 8.5, respectively.
μm and 0.05 μm. The suspension was applied to the surface of the test material that had been cleaned by washing with water after degreasing, and the hot air oven was set so that the ultimate plate temperature was 80 ° C. and drying was performed. Further, the coating weights at this time were 0.
3 g / m ² , and Comparative Example 4 was 7.0 g / m ² . The test piece produced by using the water-based composition shown in Table 4 was prepared by using the press oil of about 1.5 g / m as in the case of the example.
^After applying ² oils, press workability and adhesive strength of the adhesive were investigated.

[0042]

[Table 2]

The conditions of the series of processing steps in the above-mentioned Examples and Comparative Examples are as follows. (1) Alkaline degreasing ………… 42 ° C, 120 seconds spray (2) Rinsing ………………………… Room temperature, 30 seconds spray (3) Drying …………………… Draining dry ( 4) Application of suspension …………. Refer to the examples and comparative examples. (5) Drying ……………………. Reached plate temperature 100 ℃ (4) Zinc phosphate treatment …………. See Comparative Example (5) Washing with water …………………… Room temperature, spray for 30 seconds (6) Rinse with water …………… Spraying at room temperature for 30 seconds

[Evaluation Method of Press Moldability and Adhesive Compatibility] (1) Press Moldability The press moldability was evaluated by a draw bead test. The test pieces produced in Examples and Comparative Examples were
Cut into test pieces of mm x 300 mm and press oil (NOXR
UST550HN, manufactured by Parka Kosan) with a roll coater for about 1.5
g / m ² coating, pressurizing load 1000 to 1600 kgf
Up to 2.0mmR / 5.
The maximum load until breakage was measured at 0 mmR and a drawing speed of 260 mm / min. <Evaluation criteria> ◎: Maximum load exceeds 1500 kgf ○: Maximum load exceeds 1400 kgf and 1500 kgf
Below Δ: Maximum load exceeds 1200 kgf and 1400 kgf
Below x: Maximum load is 1200 kgf or less

(2) Adhesive compatibility The test pieces prepared in the examples and the comparative examples were set to 25 mm.
Prepare two pieces cut into test pieces of × 200 mm,
Press oil (NOXRUST550HN, manufactured by Parka Kosan Co., Ltd.) was applied by a roll coater at about 1.5 g / m ² and a commercially available sealer for automobile parts was applied to a thickness of 1.0 mm and an area of 625 mm ² .
It was sandwiched and bonded between the test pieces. This was held and adhered under a predetermined baking condition. Then, a shear tensile test was carried out at a speed of 50 mm / min, and the maximum load at that time and the cohesive failure area ratio were evaluated. <Evaluation Criteria> ◎: Maximum load exceeds 17 kgf and cohesive failure area ratio exceeds 90% ○: Maximum load is 15 or more and 17 kgf or less, cohesive failure area ratio is 80% to 90% △: Maximum load is 15 kgf If the value is less than, the cohesive failure area ratio is 60% to 80% x: The maximum load is less than 15 kgf and the cohesive failure area ratio is 60% or less.

[Evaluation Method of Zinc Phosphate Chemical Conversion Treatment] The surface-treated plate of the present invention was subjected to zinc phosphate chemical conversion treatment using the zinc phosphate chemical conversion treatment liquid shown in Table 3 to obtain zinc phosphate chemical conversion treatment. Was evaluated. The evaluation was performed by measuring the film appearance and film amount shown below. Here, the phosphatization solution B was used for the aluminum alloy, and the phosphating solution A was used for the other materials.

[0047]

[Table 3]

(1) Appearance of the film The presence or absence of scale or unevenness of the zinc phosphate film was confirmed by visual observation. The evaluation was as follows. <Evaluation criteria> ◎: Uniform and good appearance ○: Partially uneven Δ: Uneven and scaled ×: Many scaled × ×: No conversion film

(2) Coating amount The weight of the treated plate after chemical conversion treatment is measured (W1 [g]), and then the chemical conversion treatment plate is subjected to film peeling treatment under the following peeling liquid and peeling conditions. Measure the weight (W2
[G]) and equation (I). Stripping solution: Ammonium dichromate 2% by weight + 28% Ammonia water 49% by weight + Pure water 49% by weight Stripping conditions: Room temperature, 15 minutes, immersion peeling coating weight [g / m ² ] = (W1-W2) / treated plate Surface area of (m ² ) Formula (I)

The results of the evaluation of the press moldability of the examples and the comparative examples, the results of the evaluation of the compatibility of the adhesive, and the results of the appearance and the amount of the film obtained by the zinc phosphate chemical conversion treatment are shown together. 4 shows.

[0051]

[Table 4]

From Table 4, it is clear that the surface-treated steel sheet produced by the treatment method of the present invention has excellent press workability and adhesive compatibility as compared with the comparative examples. Further, it can be seen that the surface-treated steel sheet using the surface treatment method of the present invention has good chemical conversion treatability.

[0053]

As described above, the surface-treated plate of the present invention is
It has excellent press formability and adhesive compatibility due to the presence of a layered film of particles of a specific size of a divalent or trivalent metal phosphate on its surface, and is usually performed thereafter. Even if the zinc phosphate chemical conversion treatment is carried out, very dense and good zinc phosphate crystals can be deposited on the surface of the metal material, so that the industrial utility value is very large. In addition, the above-mentioned laminated film of divalent or trivalent metal phosphate particles is
Since the suspension of the phosphate particles can be formed simply by applying it to the surface of the metal plate and drying it, it can be obtained at low cost and with a simple process.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiyuki Aijima             1-15-1 Nihonbashi, Chuo-ku, Tokyo Japan Par             Within Colorizing Co., Ltd. F term (reference) 4D075 BB24Z CA03 CA13 DA06                       DB02 DB05 DB07 DC12 EA06                       EA10 EB22 EB46 EC02 EC53                 4K044 AA02 AA06 AB02 BA04 BA06                       BA10 BA17 BA21 BB01 BB02                       BB03 BB11 BC04 BC05 CA04                       CA11 CA53 CA62

Claims (7)

[Claims] 1. A surface-treated plate having a laminated coating of phosphate particles on the surface of a zinc-based plated steel sheet, a cold-rolled steel sheet, an aluminum plate or an aluminum alloy plate, wherein the phosphate particles have an arithmetic mean. The particle size is 0.1 to 2 μm, and Z
Press moldability and adhesive characterized in that it is a phosphate particle containing at least one divalent or trivalent metal selected from n, Fe, Mn, Ni, Co, Ca, Mg and Al. Surface treated plate with excellent compatibility and chemical conversion treatment. 2. A surface-treated plate excellent in press moldability, adhesive compatibility and chemical conversion treatment according to claim 1, wherein an organic compound having a dispersing function is present in the laminated film of phosphate particles. 3. An organic compound having a dispersing function is represented by the following general formula (1): (In the formula, R ¹ is H or CH ₃ , R ² is H or an alkyl group having 1 to 5 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms)
Or a polymer or copolymer of an α, β-unsaturated carboxylic acid monomer represented by
The surface-treated plate excellent in press moldability, adhesive compatibility and chemical conversion treatment according to claim 2, which is a copolymer of 0% by weight or more and 50% by weight or less of a copolymerizable monomer. 4. An organic compound having a dispersing function is a monosaccharide,
The surface-treated plate excellent in press moldability, adhesive compatibility, and chemical conversion treatability according to claim 2, which is one or more selected from polysaccharides and derivatives thereof. 5. The laminated coating amount of phosphate particles is 0.01 to.
It is 5 g / m ² , and the surface-treated plate excellent in press moldability, adhesive compatibility and chemical conversion treatment according to any one of claims 1 to 4. 6. A zinc-based plated steel sheet, a cold-rolled steel sheet, an aluminum plate or an aluminum alloy plate having an arithmetic mean particle size of 0.1 to 2 μm and Zn, Fe, Mn, N.
divalent or trivalent selected from i, Co, Ca, Mg and Al
A surface excellent in press moldability, adhesive compatibility and chemical conversion treatment characterized by applying a suspension in which particles of phosphate containing at least one valent metal are suspended and drying. Processed plate manufacturing method. 7. The press moldability according to claim 6, wherein an organic compound having a dispersing function is added to the suspension as an additional component.
A method for producing a surface-treated plate having excellent adhesive compatibility and chemical conversion treatability.