JP2000248384A - Non-chromium type surface treated metallic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-chromium type surface treated metallic material which does not contain hexavalent chromium and is imparted with good corrosion resistance and galling resistance. SOLUTION: (1) The upper layer of a metallic material is provided with a film of 0.1 to 10 μm thickness contg. an organic resin of 100 pts.wt. as solid contents, a phosphoric compd. of 0.01 to 10 pts.wt. (as PO4) and 1 to 30 pts.wt. solid lubricant, (2) the upper layer of a metallic material is provided with a film of 0.1 to 10 μm thickness contg. an organic resin by 100 pts.wt. as solid contents, 0.1 to 50 pts.wt. thiocarbonyl group-contg. compd. and 1 to 30 pts.wt. solid lubricant, or (3) the upper layer of a metallic material is provided with a film of 0.1 to 10 μm thickness contg. an organic resin of 100 pts.wt. as solid contents, 0.1 to 20 pts.wt. vanadic acid compd. and 1 to 30 pts.wt. solid lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to home appliances, construction materials,
The present invention relates to a non-chromium type surface-treated metal material such as a non-chromium type surface-treated galvanized steel sheet which does not contain hexavalent chromium and has excellent corrosion resistance and is used for automobiles.

[0002]

2. Description of the Related Art Conventionally, when manufacturing parts for home appliances, building materials, automobiles, etc. using steel sheets, a method of applying press oil to the steel sheets and removing the oil after press forming has been adopted. . However, in recent years, in response to regulations on the use of degreasing solvents,
For the purpose of cost reduction, the need for lubricating performance that can omit press oil and for surface-treated steel sheets having excellent surface properties (appearance, corrosion resistance, paint adhesion, etc.) after pressing are increasing.

[0003] As a technology that meets such needs,
Japanese Patent Application Laid-Open No. Hei 3-16726 discloses a method in which a surface of a zinc-based or aluminum-based alloy-plated steel sheet is subjected to a chromate treatment and a resin film is formed thereon, and the resin film has a hydroxyl group and a carboxyl group. A resin having either or both, silica, and an average particle size of 1 to 7 μm;
m, which is obtained by applying a paint containing a polyolefin wax and baking it, and is used without being removed from the steel sheet surface after being pressed without using a breath oil (non-decoating type).

On the other hand, a galvanized steel sheet or a zinc alloy-plated steel sheet has a white rust on its surface in an atmosphere containing salt such as seawater or a high-temperature and high-humidity atmosphere, and significantly impairs its appearance. Or decrease.

[0005] For this purpose, chromate-based rust preventive agents have conventionally been used.
No. 0 describes a resin-based treating agent in which a water-dispersible chromium compound and water-dispersible silica are contained in an olefin-α, β-ethylenically unsaturated carboxylic acid copolymer resin dispersion.

[0006] Such a film made of a chromate-based treating agent is recognized as having the best corrosion resistance among known treating agents. Nevertheless, the film formed by the chromate treatment contains hexavalent chromium, which is known to be a harmful element, and there is an increasing demand for a surface-treated steel sheet containing no hexavalent chromium.

[0007] Non-chromium rust preventive agents containing no harmful chromium are disclosed in JP-A-8-239776 and JP-A-8-6-6.
No. 7834, which uses sulfide and sulfur. However, not only sulfur but also some sulfides give off a peculiar odor, and handling of these treating agents was not always easy.

A treating agent using a triazine thiol compound containing a sulfur atom but having no odor or toxicity has been proposed. For example, Japanese Patent Application Laid-Open No. 53-31737 discloses an aqueous solution containing a dithiol-S-triazine derivative. An anticorrosive paint is disclosed. However, this water-soluble anticorrosive paint
It is intended to prevent corrosion of mild steel, copper, brass, etc., and is particularly prepared so that the base material is more easily adhered to copper or brass. Therefore, it is not sufficient as a rust inhibitor for metal surfaces such as zinc.

JP-A-61-223062 describes a reactive emulsion of a metal obtained by mixing a thiocarbonyl group-containing compound with an organic compound that is hardly soluble or insoluble in water. However, this emulsion also
It reacts with copper, nickel, tin, cobalt, aluminum and the like and their alloys, and is still insufficient as a rust inhibitor for metal surfaces such as zinc.

[0010] The applicants of the present application have disclosed in Japanese Patent Application No. 9-2557 a triazinethiol-containing rust-preventive coating agent which is also effective for rust-prevention of galvanized steel sheets. However, triazine thiol is an expensive compound, so it would be beneficial to have a less expensive rust inhibitor.

As a surface treatment method for zinc or zinc alloy which does not contain chromium and does not use triazine thiol,
JP-A-54-71734 and JP-A-3-2265.
No. 84 is disclosed. JP-A-54-
No. 71734 discloses a treatment method comprising 2 to 6 bonded phosphate esters of myo-inositol or salts thereof, at least one of titanium fluoride and zirconium fluoride, and thiourea or a derivative thereof. In aqueous solution,
The surface treatment of zinc or zinc alloy. This method requires titanium fluoride or zirconium fluoride to form a passivation film as a protective layer on the zinc surface. JP-A-3-226584 discloses that Ni ²⁺ and C 2
A surface treatment agent that is an aqueous solution having a pH of 5 to 10 containing one or both of o ²⁺ and at least one of ammonia and a compound having a primary amine group is used. This treatment agent imparts coating adhesion and corrosion resistance after coating by depositing cobalt or nickel.
One or both of ²⁺ and Co ²⁺ are required. The treating agents containing these metal ions have disadvantages such as an increase in load during wastewater treatment.

[0012]

As described above, the conventional lubricated zinc-based plated steel sheet that can be used without removing the film after forming without using press oil is a chromate-based steel sheet containing harmful hexavalent chromium. Corrosion resistance is imparted by performing the treatment, and there is no practical measure for improving the corrosion resistance.

In view of such circumstances, the present invention can be used without removing the film after press working without using breath oil, and has good corrosion resistance without containing hexavalent chromium. An object of the present invention is to provide an inexpensive, non-chromium rust-proofed metal material having excellent corrosion resistance and galling resistance.

[0014]

The non-chromium type surface-treated metal material of the present invention comprises 100 parts by weight of an organic resin as solids and 0.01 to 20 parts by weight of a phosphoric acid compound (P) in an upper layer of the metal material.
O ₄ ), and has a thickness of 0.1 to 5 μm. The above rust-preventive coating is furthermore 1-5
Optionally, 00 parts by weight of finely divided silica can be included.

[0015] In another embodiment, the non-chromium type surface-treated metal material of the present invention comprises 100 parts by weight of an organic resin as a solid content, 0.1 to 50 parts by weight of a thiocarbonyl group-containing compound, It is characterized by having a coating containing 0.1 to 10 parts by weight of a lubricant and a thickness of 0.1 to 10 μm. The anticorrosive coating may further contain at least one or more of the phosphate compound 0.01 to 20 parts by weight as solid content as the (PO ₄₎ and fine silica 1-500 parts by weight.

In still another embodiment, the non-chromium type surface-treated metal material of the present invention comprises, as an upper layer of the metal material, 100 parts by weight of an organic resin as a solid content and 0.1% of a vanadate compound.
It is characterized by having a coating having a thickness of from 0.1 to 10 μm, containing 〜20 parts by weight and 1-30 parts by weight of a solid lubricant. The rust-preventive film further contains 0.1 to 50 parts by weight of a thiocarbonyl group-containing compound as a solid content, and a phosphoric acid compound of 0.1 to 50 parts by weight.
01 to 20 parts by weight (as PO ₄ ) and fine silica 1
At least one of 500 parts by weight can be contained.

The non-chromium type surface-treated metal material of the present invention has a coating based on an organic resin as an upper coating on a base coating. The organic resin is obtained by applying a composition containing an aqueous resin in water and other components of the upper layer film and then drying the composition. The term "aqueous resin" used herein includes not only a water-soluble resin but also a resin (a water-dispersible resin) which is originally water-insoluble but can be in a finely dispersed state in water, such as an emulsion or a suspension.

Examples of the resin usable as the aqueous resin in the present invention include polyolefin resins, acrylic olefin resins, polyurethane resins, acrylic resins, polycarbonate resins, epoxy resins, polyester resins, alkyd resins, Phenolic resin,
Other heat-curable resins can be exemplified, and a crosslinkable resin is more preferable. Particularly preferred resins are
An acrylic olefin resin, a polyurethane resin, and a mixed resin of both. The aqueous resin may be used as a mixture of two or more or copolymerization.

The thiocarbonyl group-containing compound used in the upper film is a sulfide, and is easily adsorbed on the metal surface.
In addition, since it has excellent oxidizing power, the metal surface is passivated to exhibit a rust-preventive effect. In particular, it is considered that thiol group ions in the thiocarbonyl group-containing compound are adsorbed to active sites on the metal surface and exhibit a rust-preventive effect.

The thiocarbonyl group-containing compound also acts as a crosslinking accelerator for the resin film, reduces the micropores in the resin film, and has the effect of efficiently blocking harmful ions such as water and chloride ions. Is also considered to contribute to the rust prevention effect.

In the present invention, the thiocarbonyl group-containing compound is a thiocarbonyl group represented by the following formula:

[0022]

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A compound having the formula Typically,

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Thiourea and its derivatives, for example, methylthiourea, dimethylthiourea, ethylthiourea, diethylthiourea, diphenylthiourea, thiopental, thiocarbazide, thiocarbazones, thiocyanuric acids, thiohydantoin, 2-thiouramil,
Such as thiourazole,

[0025]

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(Wherein R is, for example, H, CH ₃ , C ₂ H ₅ , C ₆ H ₅ , C ₈ H ₅ ,
C ₅ H ₃ SO, etc.), for example, thioformamide, thioacetamide, thiopropionamide, thiobenzamide, thiocarbostyril, thiosaccharin and the like;

[0027]

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(Wherein R represents, for example, H or CH ₃ ), for example, thioformaldehyde, thioacetaldehyde, etc.

[0029]

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(Wherein R represents, for example, CH ₃ , C ₆ H _5, etc.), for example, thioacetic acid, thiobenzoic acid, dithioacetic acid and the like;

[0031]

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Thiocarbonates represented by the following formulas and other compounds having the structure of the formula (1), for example, thiocoumazone,
Thiocmotiazone, thionin blue J, thiopyrone, thiopyrine, thiabenzophenone and the like are exemplified.

When the thiocarbonyl group-containing compound is contained in the upper layer film, its content is preferably 0.1 to 50 parts by weight as solids relative to 100 parts by weight of the organic resin. When the content of the thiocarbonyl group-containing compound is less than 0.1 part by weight, the above-mentioned effects become inconspicuous, and when the content is more than 50 parts by weight, an effect corresponding to an increase in cost associated therewith cannot be expected.

In the case where the upper layer film in the present invention contains a thiocarbonyl group-containing compound as an essential component, the rust prevention effect is remarkably improved by further containing a phosphoric acid compound. As described above, the thiocarbonyl group-containing compound is adsorbed on the active site on the metal surface and exhibits a rust-preventive effect, but phosphoric acid acts on the inactive site on the metal surface to form the active surface. It is considered that the thiocarbonyl group-containing compound is formed and the thiocarbonyl group-containing compound is adsorbed thereon, so that the rust-preventing effect is exerted on the entire metal surface and the rust-preventing effect is improved. Phosphoric acid compounds also act as a cross-linking accelerator for the resin film, reducing the micropores in the resin film and effectively blocking harmful ions such as water and chloride ions, which also contributes to the rust prevention effect. It is thought that. Therefore, the phosphate compound can be included in the upper layer film as an optional component even when the upper layer film contains a vanadate compound instead of the thiocarbonyl group-containing compound as an essential component.

The phosphate compound may be any compound containing a phosphate ion. For example, ammonium phosphate, sodium phosphate, potassium phosphate and the like can be used.

The content of the phosphoric acid compound is 100
It is in the range of 0.01 to 20 parts by weight as phosphate ion with respect to parts by weight. If the amount of the phosphate compound is less than 0.01 parts by weight, the rust-preventing effect is not sufficiently exerted. On the other hand, if the amount exceeds 20 parts by weight, the rust-preventing effect is reduced or the resin is gelled in the state of the coating solution. May occur.

The upper layer film in the present invention can contain fine silica. When the upper film contains fine silica,
Its rust preventive action (corrosion resistance) is remarkably promoted. Moreover, in addition to the corrosion resistance, the drying property at the time of film formation, the abrasion resistance and adhesion of the formed film can be improved.

In the present invention, the term "fine silica" refers to silica having such a property that when it is dispersed in water, it can maintain a stable water-dispersed state and has no permanent sedimentation when dispersed in water. It is a generic term. The finely divided silica is not particularly limited as long as it has a small amount of impurities such as sodium and is weakly alkaline. For example, commercially available silica sols such as "Snowtex N" (manufactured by Nissan Chemical Industries, Ltd.) and "Adelite AT-20N" (manufactured by Asahi Denka Kogyo Co., Ltd.), or commercially available Aerosil powdered silica can be used.

When fine silica is contained in the upper film, the content thereof is 1 to 500 parts by weight based on 100 parts by weight of the organic resin.
It is preferably in parts by weight. If the amount is less than 1 part by weight, the effect of addition is small, and if it is 500 parts by weight or more, the effect of improving corrosion resistance is saturated and uneconomical. In addition, the film becomes too hard and cracks, peeling, etc. occur, and the corrosion resistance may decrease. is there.

When the upper layer film contains a vanadate compound, it has the same rust-preventing action as the chromic acid compound.
That is, the vanadate compound forms a passivation film on the surface of the steel plate (here, the base film) when the composition for forming the upper layer film is applied, and exhibits a rust prevention effect. Furthermore, it is considered that the vanadate compound has the effect of suppressing the corrosion reaction by the vanadate ions present in the film acting on the corrosion site even when a corrosion site occurs on the metal surface (particularly the galvanized surface). Can be

As the vanadate compound, for example, ammonium vanadate, sodium vanadate, potassium vanadate and the like can be used.

The amount of the vanadate compound is 0.1 to 20 parts by weight based on 50 to 100 parts by weight of the organic resin as solids.
The range of parts by weight is good. If the amount is less than 0.1 part by weight, the rust preventing effect is not sufficient, and if it is more than 20 parts by weight, the rust preventing effect is saturated and uneconomical.

When the vanadate compound is used in combination with the fine silica particles, the vanadate compound is adsorbed on the surface of the fine silica particles, and the rust-preventive effect is synergistically exhibited. In this sense, when the fine silica particles are of the ammonium adsorption type or the aluminum oxide coating type, the silica particles are easily adsorbed and the rust prevention effect is improved, which is preferable.

As the solid lubricant, an emulsion obtained by emulsion polymerization of the following lubricant having hydrophilic carboxyl groups and hydroxyl groups is used. Specifically, low-density polyethylene (density 0.9 to 0.95, softening temperature 90 to 120 ° C),
High density polyethylene (density 0.95 to 1.2, softening temperature 100 to 130 ° C), polypropylene (density 0.95 to
1.2, polyolefin-based wax such as softening temperature 150-190 ° C, Teflon-based lubricant (density 1.0-1.
2, a softening temperature of 300 to 400 ° C.) is desirable. Although these lubricants are selected according to the purpose, in particular, a polyolefin wax dispersion having an average particle size described below of 0.1 to 7 μm, preferably 0.5 to 5 μm exhibits the best lubrication performance.

The polyethylene and polypropylene dispersions are those in which the concentration of the emulsifier is as low as 5% or less, preferably aqueous without using an emulsifier. That is, a molecular weight of 1000 to 400 having substantially no polar group
A modified polyolefin having a polar group containing a base polyolefin of 0 and an ethylenically unsaturated carboxylic acid or an anhydride thereof, or a carboxyl group-containing derivative as a binding component, preferably having an acid value of 10 to 150 and a molecular weight of 1000 to 4000, This is a dispersion of a lubricant having a shape close to a true sphere and having a high melting point, which is obtained by dispersing in a water or aqueous solution from the molten state of melt mixing. The acid value of the polyolefin wax after melt mixing is preferably in the range of 1 to 20.

A rust-preventive film is constituted by each of these components, and the resulting film undergoes layer separation during the baking process after application,
The structure is such that part of the lubricant is concentrated on the surface.

The rust preventive film of the present invention may further contain other components. For example, pigments, surfactants and the like can be mentioned. Further, a silane coupling agent or a hydrolyzed condensate thereof to improve the affinity between the organic resin and the silica particles, the pigment, and further improve the adhesion between the aqueous resin and the zinc or iron phosphate layer, or Both of them may be blended. Here, the “hydrolysis condensate of a silane coupling agent” refers to an oligomer of a silane coupling agent obtained by subjecting a silane coupling agent to a raw material and hydrolyzing and polymerizing the same.

As the pigment, for example, titanium oxide (TiO 2)
₂ ), zinc oxide (ZnO), zirconium oxide (Zr
O), calcium carbonate (CaCO ₃ ), barium sulfate (BaSO ₄ ), alumina (Al ₂ O ₃ ), kaolin clay, carbon black, iron oxide (Fe ₂ O ₃ , Fe ₃
Inorganic pigments such as O ₄ ) and various coloring pigments such as organic pigments can be used.

The silane coupling agent that can be used in the present invention is not particularly limited, but preferred examples include the following: vinylmethoxysilane, vinyltrimethoxysilane, vinylethoxysilane, Vinyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) ) -3-
(Triethoxysilyl) -1-propanamine, N,
N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,
N- [2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane.

Particularly preferred silane coupling agents are vinyltrimethoxysilane, vinylethoxysilane, 3-
Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene)
-3- (triethoxysilyl) -1-propanamine,
N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine. One of these silane coupling agents may be used alone, or two or more thereof may be used in combination.

In the present invention, the silane compound is used as a solid component in an amount of 0.01 to 2 parts by weight per 100 parts by weight of the organic resin.
It is preferably 0 parts by weight. When the addition amount of the silane compound is less than 0.01 part by weight, the effect of the addition is reduced, and the effect of improving the corrosion resistance and the adhesion of the top coat is insufficient.
If the amount is more than the weight part, the resin may gel in the state of the coating solution or cause a problem.

In order to form the rust-preventive film of the present invention, a coating composition containing predetermined components (aqueous resin as an organic resin, an inhibitor component, and other optional components) in water is prepared. Apply to the metal material of
dry. The coating composition may be adjusted at any temperature. Generally, solid content (components other than water)
From 1 to 80 parts by weight and 20 to 99 parts by weight of water are preferred from the viewpoint of application and subsequent heating and drying. The method of applying the coating composition is not particularly limited, and generally known application methods such as roll coating, air spray, airless spray, and immersion can be employed.

By heating the coating film, the resin is cured in the case of a curable resin, and the resin is crosslinked in the case of a crosslinkable resin.
Heating and drying (baking) of the coating film is performed by a hot blast stove, induction heating furnace,
A known method using a near-infrared furnace, a direct fire furnace, or the like, or a method combining these methods may be used. Alternatively, air drying may be performed without using the forced drying, or the metal material may be preheated, and the coating composition may be air-dried after being applied thereto. In addition, depending on the type of the aqueous resin used, the resin can be cured by energy rays such as ultraviolet rays and electron beams. The heating temperature is 50-25
0 ° C is good. If the temperature is less than 50 ° C., the evaporation rate of water is too slow to obtain a sufficient film-forming property, so that the rust-preventing ability is insufficient. On the other hand 2
If the temperature exceeds 50 ° C., thermal decomposition of the organic resin or the like occurs, and thus there is a problem that rust prevention and water resistance are reduced and the appearance is yellowed. 70-200 degreeC is more preferable. In addition, heating
Cooling after drying is a known method such as water cooling, air cooling, natural cooling,
Alternatively, it may be performed by a method combining these.

The thickness of the rust preventive film to be formed is 0.1 to 10
It is in the range of μm. If it is less than 0.1 μm, the rust-preventing ability is insufficient. On the other hand, if it exceeds 10 μm, the effect is saturated and uneconomical.

[0055]

Next, the present invention will be further described with reference to examples.

A galvanized steel sheet having a coating weight of 20 g / m ² per side and a thickness of 0.8 mm was used as a material.
A rust-preventive coating agent containing 20% by weight as a total solid content of the surface treatment agent having the rust-preventive film composition shown in Nos. 3 to 3 was applied by a roll coater, dried in a hot-air drying furnace, and cooled. The thickness (μm) of the rust preventive film and the drying / cooling conditions are shown in Tables 1 to 3. The stability of the treatment liquid was good, and after leaving at room temperature for 3 months, the quality was almost the same as the initial one. The compared chromate-containing type resin-based rust preventive agent was obtained by drying a treatment agent obtained by adding 5% of strontium chromate and 28% of Snowtex N as a rust preventive agent to 67% by weight of an olefin-based resin in terms of solid content. A coating material was applied by a roll coater so that the amount of adhesion was 1.0 g / m ^2, and dried at a reaching plate temperature of 150 ° C. (Comparative Example 7). In addition, the chromate treatment is performed by adding a silica (Snowtex O,
Nissan Chemical Industry Co., Ltd.) (chromic acid / silica = 1/3 (weight ratio of solid content)) was added to the treating agent, and the adhesion amount as Cr was adjusted to 50 mg / m ² with an air knife. What was dried at a temperature of 60 ° C. was used (Comparative Example 8).

Further, the coating weight per one side was 60 g /
galvanized steel sheet having a thickness of 0.8mm in m ^2, galvannealed steel sheet amount plating adhesion thickness 0.8mm of per side 40 g / m ^2, coating weight is per side 20
A surface-treated steel sheet using a zinc / nickel alloy-plated steel sheet (nickel content: 11% by weight) having a thickness of 0.8 mm of g / m ^{2 as} a base plate was also evaluated by the same method. Tables 1 to 3 show plating types. EG is an electrogalvanized steel sheet, GI is a hot-dip galvanized steel sheet, GA is an alloyed hot-dip galvanized steel sheet, and ZN is a zinc-nickel alloy-plated steel sheet. The contents of the surface treatment agents shown in Tables 1 to 3 are as follows.

1. Aqueous resin Olefin: "HI-TECH S-7024" (Toho Chemical) Urethane: "Bon Titer HUX-320" (Asahi Denka) Acrylic: "AP-1058 (12)" (Toa Gosei) Epoxy System: "Polysol 8500" (manufactured by Showa Polymer Co., Ltd.) Polyester system: "Pesresin A-124G" (manufactured by Takamatsu Yushi) Urethane olefin system: A mixture of the above olefin system and urethane system at a solid content of 1: 1.

2. Colloidal silica ST-N: "Snowtex N" (manufactured by Nissan Chemical Industries, Ltd.)

3. Phosphate ion Ammonium phosphate: Diammonium hydrogen phosphate primary grade (manufactured by Kanto Chemical Co., Ltd.) was dissolved in a rust preventive coating agent to a predetermined amount.

4. Thiocarbonyl group-containing compound Thiourea: Thiourea primary (manufactured by Kanto Chemical Co.) 1,3-diethyl-2-thiourea: 1,3-diethyl-
2-thiourea first grade (manufactured by Kanto Chemical Co., Ltd.) Dimethyl xanthogen disulfide: dimethyl xanthogen disulfide first grade (manufactured by Kanto Chemical Co., Ltd.)

[0062] 5. Vanadate compound Ammonium vanadate: Ammonium vanadate first class (manufactured by Kanto Kagaku) Strontium vanadate: first class strontium vanadate (manufactured by Kanto Kagaku) Potassium vanadate: potassium first class vanadate (manufactured by Kanto Kagaku)

6. Solid lubricant J: Low density polyethylene (density 0.92, particle size 0.6) K: Low density polyethylene (density 0.92, particle size 2.5) L: Low density polyethylene (density 0.96, particle size) 0.6) M: polypropylene (density 0.95, particle size 2.5) N: tetrafluoroethylene (density 1.2, particle size 0.4)
5) 7. Silane compound A: γ-glycidoxypropyltriethoxysilane “K
BE-403 "(manufactured by Shin-Etsu Chemical Co., Ltd.) B: γ-glycidoxypropyltrimethoxysilane" K
BM-403 "(Shin-Etsu Chemical Co., Ltd.) C: Vinyltrimethoxysilane" KBM-1003 "
(Manufactured by Shin-Etsu Chemical Co., Ltd.) D: N-β (aminoethyl) γ-aminopropyltriethoxysilane “KBE-603” (manufactured by Shin-Etsu Chemical Co., Ltd.) E: γ-mercaptopropyltrimethoxysilane “KB”
M-803 "(Shin-Etsu Chemical Co., Ltd.)

The following evaluation was performed on the produced surface-treated steel sheet. 1. Finished Appearance The appearance of the treated film was judged visually and scored. The rating was 5: uniform, 4: extremely slight unevenness, 3: partial unevenness, 2: overall unevenness, 1: severe unevenness over the entire surface.

2. Adhesion of rust-preventive film The flat plate adhesion was determined by the cross-cut tape method (gap 1 mm) described in 8.5.2 of JIS K 5400. The evaluation was made according to the criteria shown below. The corrosion resistance of the processed portion was determined by extruding with an Erichsen tester specified in 8.2 of JIS K 5400, peeling the extruded portion with a tape, and visually determining the peeling of the film. It was rated according to the following criteria.

10 points: No peeling 9 points: Peeling area of 3% or less 8 points: Peeling area of more than 3% and 5% or less 7 points: Peeling area of more than 5% and 8% or less 6 points: More than 8% and 10% or less 5 points: Peeling area of more than 10% and 15% or less 4 points: Peeling area of more than 15% and 30% or less 3 points: Peeling area of more than 30% and 50% or less 2 points: Peeling more than 50% and 75% or less Area 1 point: Exfoliation area of more than 75%

When it is difficult to judge by visual observation, the film is dyed with a 0.1% acetone solution of methyl violet, and the film exists in the stained portion, and the film does not exist in the unstained portion. The adhesiveness of the film was determined as The same applies to the appearance evaluation of the treated film.

3. Olga Select 100 which is a melamine alkyd paint
(Nippon Paint Co., Ltd.) was applied by spraying so as to have a dry film thickness of 25 μm, and dried and baked in a hot air oven at 150 ° C. for 20 minutes, and then the adhesion was evaluated. Evaluation is JIS for flat plate adhesion
It was determined by the crosscut tape method (clearance interval 1 mm) described in 8.5.2 of K5400. The corrosion resistance of the processed part is
The extruded portion was extruded with a tape of 7 mm using an Erichsen tester specified in 8.2 of JIS K 5400, and the extruded portion was peeled off with a tape to visually determine the peeling of the film. It was rated according to the following criteria.

10 points: no peeling 9 points: peeling area of 3% or less 8 points: peeling area of more than 3% and 5% or less 7 points: peeling area of more than 5% and 8% or less 6 points: more than 8% and 10% or less 5 points: Peeling area of more than 10% and 15% or less 4 points: Peeling area of more than 15% and 30% or less 3 points: Peeling area of more than 30% and 50% or less 2 points: Peeling more than 50% and 75% or less Area 1 point: Exfoliation area of more than 75%

Further, as secondary adhesion, after the surface-treated steel sheet was immersed in boiling water for 30 minutes and allowed to stand for 24 hours, the adhesion of the coating film after Olgaselect 100 was applied by the above-described method was examined.

4. Fingerprint resistance Fingerprints were adhered to the film of the surface-treated steel sheet, and the visibility of the fingerprints was visually judged and scored. The rating was 5: no fingerprint trace was visible, 4: very slight fingerprint trace was visible, 3: fingerprint trace was visible, 2: fingerprint trace was noticeable, 1: fingerprint trace was very noticeable.

5. Ethanol resistance Press oil was impregnated with gauze and applied onto the film of the surface-treated steel sheet. This oil was wiped off with gauze impregnated with ethanol, and the remaining traces of the film were visually judged and scored. In order to clean oil stains and the like, an operation of wiping with ethanol is sometimes performed. At this time, the test is performed to evaluate whether or not the film is damaged. The score was 5: no trace, 4: very slight trace, 3:
There were traces, 2: traces were noticeable, 1: traces were very noticeable.

6. Corrosion resistance (SST) Flat plate (sealed end and back of steel plate as cut)
And a salt spray test (specified in JIS Z 2371) for a 7 mm processed part of Erichsen (sealed end and back of a steel plate extruded 7 mm by Erichsen).
Performed for 68 hours. The evaluation criteria were as follows.

10 points: no abnormality 9 points: between 10 points and 8 points 8 points: slight white rust generation 7 to 6 points: between 8 points and 5 points 5 points: white rust generation in half the area 4 to 2 points: Between 5 points and 1 point 1 point: White rust generated on the entire surface

7. Galling resistance (7-1) High-speed galling resistance Using a blank plate with a diameter of 115 mmφ, punch diameter =
50mmφ, die diameter 52mmφ, wrinkle pressure 1To
n, a high-speed cylindrical deep drawing test was performed under the conditions of a deep drawing speed of 30 m / min. The aperture ratio at this time is 2.30. The evaluation criteria were as follows. ◎ = drawing ratio = 2.40, drawing-out, good appearance ○ = drawing ratio = drawing-out to 2.40, poor appearance △ = drawing ratio = 2.35, drawing-out × = drawing-down ratio = 2.30

(7-2) Low-speed galling resistance A test plate was cut into a width of 30 mm, the tip radius was 0.5 mm, the molding height was 4 mm, the compression load was 0.5 ton, and the drawing speed was 2
A draw bead test was performed at 40 mm / min, and the appearance was evaluated. The evaluation criteria were as follows. ◎ = No film damage ○ = The film damaged part is less than 5% of the whole sliding part △ = The film damaged part is 5% or more and 20% of the whole sliding part
Less than × = Damaged part of film is 20% or more of the entire sliding part

The evaluation results are shown in Tables 4 to 6.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

[Table 4]

[0082]

[Table 5]

[0083]

[Table 6]

In the examples, in Example 7, in which no silica was added to the rust preventive film, the corrosion resistance and galling resistance were slightly inferior.
In Examples 13 and 19 where addition of a lubricant was small in the rust-preventive film, galling resistance was slightly inferior. In Examples 22 and 25 in which the thickness of the rust-preventive film was thin, fingerprint resistance, corrosion resistance and galling resistance were slightly inferior. Example 41, in which the baked plate temperature of the rust-preventive film is low, is slightly inferior in ethanol resistance, but all of them are practically usable.

On the other hand, as an example out of the scope of the present invention, in Comparative Example 1 in which the thickness of the rust-preventive film is thin, fingerprint resistance, corrosion resistance, and galling resistance are inferior, and Comparative Example 2 in which the amount of the phosphoric acid compound added is small. In Comparative Example 3 in which the addition amount of the phosphoric acid compound was not good, the adhesion and corrosion resistance were significantly poor.
In Comparative Example 4 in which no lubricant was added to the rust-preventive film, galling resistance was poor. In Comparative Example 5 in which the amount of thiourea added was too large, ethanol resistance and corrosion resistance were poor. In Comparative Example 6 in which the addition amount was too large, the coating gelled and could not be applied. Further, Comparative Examples 7 and 8 are both chromium-containing treated steel sheets and have chromium toxicity. According to the present invention, even when the plating of the original plate and the lubricant added to the film are changed, according to the present invention, a surface treatment excellent in corrosion resistance, topcoat adhesion, fingerprint resistance, ethanol resistance, and galling resistance A steel plate was obtained.

[0086]

As described above, according to the present invention,
The use of non-chrome type treated lubricated galvanized steel sheet which can be used without removing the film after press working without using breath oil and which does not contain hexavalent chromium and has good corrosion resistance and galling resistance Will be possible. This makes it possible to manufacture various parts using galvanized steel sheets for household appliances, building materials, automobiles and the like more easily and avoiding the problem of harmful hexavalent chromium.

 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Yujiro Miyauchi 1 Kimitsu, Kimitsu-shi, Chiba Nippon Steel Co., Ltd. (72) Inventor Akira Takahashi 1 Kimitsu, Kimitsu-shi, Chiba Nippon Steel Co., Ltd. (72) Inventor Toshiaki Shimakura 4-1-1-15 Minamishinagawa, Shinagawa-ku, Tokyo Japan Paint Co., Ltd. (72) Katsuyoshi Yamazoe 4-1-1-15 Minamishinagawa, Shinagawa-ku, Tokyo Japan Paint F term in reference (reference) 4K044 AA02 AB02 BA10 BA12 BA14 BA17 BA21 BB03 BB11 BC02 BC05 CA11 CA18 CA53 CA62

Claims (6)

[Claims] 1. An upper layer of a metal material, in which 100 parts by weight of an organic resin and 0.01 to 20 parts by weight of a phosphoric acid compound (P
O as ₄₎ and the solid comprises a lubricant 1-30 parts by weight, chromium-type surface-treated metal material characterized by having a 0.1~10μm of coating thickness. 2. The non-chromium type surface-treated metal material according to claim 1, wherein the upper layer film further contains 1 to 500 parts by weight of fine silica as a solid content. 3. An upper layer of a metal material comprising 100 parts by weight of an organic resin as a solid content and 0.1 to 5 parts of a thiocarbonyl group-containing compound.
A non-chromium type surface-treated metal material comprising 0 part by weight and 1 to 30 parts by weight of a solid lubricant, and having a coating having a thickness of 0.1 to 10 μm. 4. The method according to claim 1, wherein the upper coating further contains at least one of 0.01 to 20 parts by weight (as PO ₄ ) of a phosphoric acid compound and 1 to 500 parts by weight of fine silica as solids. The non-chromium type surface treated metal material according to claim 3. 5. An upper layer of a metal material containing 100 parts by weight of an organic resin as solids, 0.1 to 20 parts by weight of a vanadate compound and 1 to 30 parts by weight of a solid lubricant and having a thickness of 0.1 to 30 parts by weight.
A non-chromium type surface-treated metal material having a coating of 10 μm. 6. An upper layer coating comprising 0.1 to 50 parts by weight of a thiocarbonyl group-containing compound, 0.01 to 20 parts by weight of phosphoric acid compound (as PO ₄ ) and 1 to 500 parts by weight of fine silica as solids. The non-chromium type surface-treated metal material according to claim 5, further comprising at least one or more thereof.