WO2000061835A1

WO2000061835A1 - Method for production of surface treated steel sheet, surface treated steel sheet, and surface treated steel sheet coated with resin comprising surface treated steel sheet and organic resin coating the steel sheet

Info

Publication number: WO2000061835A1
Application number: PCT/JP2000/002356
Authority: WO
Inventors: Masao Komai; Masanori Yoshikawa; Jun-Ichi Fujimoto; Takao Nishimura
Original assignee: Toyo Kohan Co., Ltd.
Priority date: 1999-04-12
Filing date: 2000-04-11
Publication date: 2000-10-19
Also published as: JP4312391B2; AU3677000A; JP4845951B2; JP2009068115A

Abstract

A method for producing a surface treated steel sheet which comprises subjecting a steel sheet to a dipping treatment or an electrolysis treatment in an aqueous solution containing one or more of oxysulfates of Mo, Ti, V and Zr, a P compound and a Zn compound, or, in an aqueous solution further containing a significant amount of one or more of sulfates of Mg and Al and/or a phosphonate in addition to the above; a surface treated steel sheet; and a surface treated steel sheet coated with a resin comprising a surface treated steel sheet and a resin coating the steel sheet which is produced by coating the surface treated steel sheet produced by the above method with an organic resin. The surface treated steel sheet has sufficient resistance to corrosion and sufficient adhesiveness with a resin to replace a surface treated steel sheet which has been subjected to a chromate treatment.

Description

Description Manufacturing method of surface-treated steel sheet, surface-treated steel sheet, and resin-coated surface-treated steel sheet obtained by coating surface-treated steel sheet with organic resin

The present invention relates to a method for producing a surface-treated steel sheet in which a zinc-coated steel sheet or the like is coated with a protective film having excellent barrier properties and film adhesion, a surface-treated steel sheet, and the surface-treated steel sheet coated with an organic resin. And a resin-coated surface-treated steel sheet.

I D

Background art

Conventionally, in the field of steel sheets, especially Zn-plated steel sheets, phosphate-chromic acid has been used to improve the protection against corrosion and the adhesion to coating films and resin layers formed thereon. The surface is treated in a solution containing salt to form a protective is film such as a phosphate film or a chromate film. However, steel sheets on which a phosphate film has been formed have poor corrosion resistance, and are likely to produce 鲭 when not coated with a film or an organic resin. Also, when coated with a coating film or an organic resin, the adhesion, especially during processing, is insufficient.

A chromate film is formed on a steel sheet using a method such as immersion treatment, coating treatment, or electrolytic treatment that does not involve electrolysis, and is not coated with a coating film or organic resin rather than a phosphate film.

It has excellent water resistance, adhesion when coated with a coating film or organic resin, and adhesion during processing. However, harmful hexavalent chromium is contained in the chromate film formed by immersion treatment or coating treatment without electrolysis, which can have an undesired effect on the human body and environment. In addition, electrolytic chromate coating by electrolytic treatment is performed using a solution containing harmful hexavalent chromium, and chromate mist generated during electrolysis is reduced to the working environment.

May have an adverse effect on IS.

In this way, the steel sheet with the chromate film is excellent in corrosion resistance and processing adhesion. Although it is widely used in many fields, it has the potential to adversely affect the human body and the environment.Therefore, a treatment film is required to replace the chromate film, which has excellent corrosion resistance and processing adhesion. ing.

As an example, Japanese Patent Publication No. 62-30265 discloses phosphoric acid, zinc oxide as an acid-soluble zinc compound, heavy metal promoter and / or crystal refiner, and aminotris (phosphonate corrosion inhibitor). It discloses a composition comprising methylene monophosphonic acid) and water, and the coating of metal parts with the composition, and describes that corrosion resistance and paint adhesion are improved.

In the above-mentioned Japanese Patent Publication No. Sho 62-325, Vanaji Co., Ltd.

(Examples include titanium, titanium, zirconium, tungsten, and molybdenum compounds, and specifically, use of ammonium molybdate or ammonium metavanadate. Further, nickel, cobalt, An acid-soluble salt of magnesium or calcium is mentioned. Specifically, use of nickel nitrate, calcium nitrate, or cobalt nitrate is described. However, it is described in the above-mentioned Japanese Patent Publication No. Sho 62-302565. Even if a treated film is formed on a metal plate such as a galvanized steel plate using the composition thus prepared, the properties of the obtained surface-treated metal plate, especially the organic resin coating obtained by coating the surface-treated metal plate with an organic resin film The adhesion of the coating on the metal plate, especially the processing adhesion, was achieved by forming a conventional chromate-treated coating. Beyond the surface treated metal plate. The poor 耐白鲭性 when applied to zinc plated steel plate.

The present invention provides a method for producing a surface-treated steel sheet having excellent corrosion resistance and excellent processing adhesion of an organic resin film, which is an alternative to the surface-treated steel sheet subjected to a chromate treatment, a surface-treated steel sheet, and an organic resin for the surface-treated steel sheet. It is an object of the present invention to provide a resin-coated surface-treated steel sheet coated. Disclosure of the invention

The method for producing a surface-treated steel sheet according to the present invention includes immersing or electrolytically immersing the steel sheet in an aqueous solution containing at least one of oxysulfates of Mo, Ti, V, and Zr, a P compound, and a Zn compound. Processing.

^ The method for producing a surface-treated steel sheet according to the present invention comprises the steps of: preparing a steel sheet in an aqueous solution containing at least one of oxysulfates of Mo, Ti, V, and Zr, a P compound, a Zn compound, and a phosphonate. Characterized by immersion or electrolytic treatment

The method for producing a surface-treated steel sheet of the present invention includes one or more of oxysulfates of Mo, Ti, V, and Zr, a P compound, a Zn compound, and one or more of sulfates of Mg and A1. The steel sheet is immersed or electrolytically treated in an aqueous solution having ίθ.

The method for producing a surface-treated steel sheet of the present invention comprises the steps of: at least one of oxysulfates of Mo, Ti, V, and Zr; a P compound; a Zn compound; and at least one of sulfates of Mg and A1; The steel sheet is subjected to immersion treatment or electrolytic treatment in an aqueous solution containing sulphonate.

In this case, it is preferable that the oxysulfate is molybdenum oxysulfate or vanadyl sulfate.

In this case, it is desirable that the P compound is composed of at least one of phosphoric acid, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, and aluminum biphosphate.

^ In this case, the phosphonate is preferably aminotri (methylene monophosphonic acid).

Further, the surface-treated steel sheet of the present invention is characterized in that a material containing at least one of Mo, Ti, V, and Zr, a substance containing P, and a substance containing Zn by using any one of the methods for producing a surface-treated steel sheet described above It is a surface-treated steel sheet obtained by coating a steel sheet with a protective film mainly composed of

In this case, a protective film containing at least one of Mg and A1 is coated on the steel sheet. It is desirable that the surface-treated steel sheet be composed of:

In this case, it is desirable that the steel sheet is a Zn-plated steel sheet or a steel sheet with an alloy containing Zn.

In this case, it is preferable that the steel plate is a steel plate plated by electrolytic treatment. In this case, it is desirable that the alloy-plated steel sheet containing Zn is a Zn-Co_Mo-plated steel sheet.

Further, the resin-coated surface-treated steel sheet of the present invention is a resin-coated surface-treated steel sheet obtained by coating any one of the above-mentioned surface-treated steel sheets with an organic resin.

In this case, the organic resin is desirably any one of a polyester resin, a urethane resin, an acrylic resin, a polyolefin resin, a polycarbonate resin, a polyamide resin, and a polyvinyl chloride resin.

In this case, it is preferable that the organic resin contains at least one of colloidal silica, polytetrafluoroethylene, polyethylene wax, a silane coupling agent, and a chromium-free antioxidant. BEST MODE FOR CARRYING OUT THE INVENTION

In the surface treatment bath of the present invention, oxysulfates of Mo, Ti, V, and Zr, a P compound, and a Zn compound are used as main components for forming a film. In addition, a surface treatment bath to which at least one of the sulfates of Mg and A1 and / or phosphonate is positively added is used. Furthermore, the oxysulfate is characterized by being molybdenum oxysulfate or vanadyl sulphate, and the P compound is phosphoric acid, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate , Characterized by comprising at least one of aluminum biphosphate.

Incorporation of metals such as Cr into phosphoric acid coatings has been practiced for the purpose of improving corrosion resistance.Cr has particularly excellent corrosion resistance and adhesion to coatings and other coatings. Has been harmful to the environment as shown above. Attempts have been made to use Mo, W, V, etc. as a metal instead of Cr. All of these metals are used in the form of metal oxide ions such as molybdate ion, tungstate ion, and vanadate ion added to the treatment bath, but the resulting surface treatment films all have Cr. The characteristics of the surface treatment film used

^ Did not show.

In the present invention, at least one of Mo, Ti, V, and Zr as a metal replacing Cr is contained in the treatment solution together with the P compound and the Zn compound in the form of oxysulfate, and the treatment bath is used. By incorporating Mo, Ti, V, and Zr oxysulfates and substances derived from P compounds and Zn compounds into the formed treated film,

! 0 Better film properties than a treated film formed using a treatment bath containing compounds such as ammonium molybdate, ammonium vanadate, ammonium tungstate, and ammonium titanate. It was found that film properties equivalent to or better than the surface treatment film used were obtained. Although the reason for this is not clear, Mo, Ti, V, and Zr should be contained in the treatment bath in the form of oxysulfate.

^, For Mo, compounds in which trivalent, pentavalent and hexavalent molybdenum are linked to oxygen ions (一 21) and sulfate ions (S 0 ₄ ² —), and to Ti, V, and Zr In other words, a substance derived from a compound in which tetravalent Ti, V, and Zr are linked to oxygen ions (O ² —) and sulfate ions (SO-I) together with P and Zn, form a film formed on the steel sheet. It becomes a component that forms the skeleton, and it is considered that this film has excellent heat resistance. In particular, when the steel sheet is a Zn-plated steel sheet or a steel sheet with a Zn-based alloy, P and P are combined with one or more of Mo, Ti, V, and Zr in association with Zn and alloy elements in the plating film. Zn is mainly a component of the skeleton of the film, and it is considered that this film has excellent protection properties. In addition, it is considered that by further positively containing one or more of Mg and A1 and / or phosphonate in the above-mentioned film, the heat resistance is further improved.

In addition, high valence states of Mo, Ti, V, and Zr are preferred in these films. It is considered to be oxidized to promote the formation of oxide film by oxidizing other substances and to be reduced to lower valence state. This reaction is considered to be similar to the oxidizing function of chromate ions, and is considered to exhibit excellent protection because the film has self-healing properties.

^ The contents of the present invention will be described below.

First, the treatment bath will be described. The treatment bath of the present invention comprises molybdenum oxysulfate, titanyl sulfate, vanadyl sulfate, zirconyl sulfate, and at least one of the oxysulfates of Mo, Ti, V, and Zr, and phosphoric acid and ammonium biphosphate. It consists of an aqueous solution containing P compounds such as ammonium dihydrogen phosphate, sodium biphosphate (sodium dihydrogen phosphate), and Zn compounds such as zinc oxide, and sulfuric acid that improves heat resistance. One or more of sulfate salts of Mg or A1, such as magnesium and aluminum sulfate, and / or a phosphonate salt such as aminotri (methylene monophosphonic acid) may be added. Furthermore, in order to improve the conductivity and stabilize the treatment bath, for example, salts such as sodium sulfate and ammonium sulfate may be added.

tS "The total content of molybdenum oxysulfate, titanyl sulfate, vanadyl sulfate, zirconyl sulfate, etc. is 3 to 150 gZl, preferably 5 to 50 gZl. Less than 50 gZ 1 The color tone of the film changes and the film's processing adhesion deteriorates.In addition to the expensive chemicals,付着 Increases the amount of 付着 adhered and removed, making it less economical.

Any of the above metal oxysulfates can be applied to the present invention. However, when molybdenum oxysulfate and vanadyl sulfate are used, a stable treatment bath can be obtained, which is preferable.

The content of the compound is 3 to 150 gZl, preferably 5 to 50 gZl. If it is less than 32 3gZl, the amount of film formed is small and good film properties cannot be obtained. If it exceeds 150 g / 1, the processing adhesion of the film will decrease. In addition, it adheres to the steel sheet during processing The amount taken out increases and it is not economical.

As the P compound, at least one kind of compounds such as orthophosphoric acid, condensed phosphoric acid, phosphorous acid, hypophosphorous acid, and other P-containing oxyacids and oxyacid salts can be applied. However, the use of ammonium biphosphate, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, or aluminum biphosphate, which is a biphosphate compound, is preferred because a stable treatment bath can be obtained.

The content of the Zn compound is 1 to 101, preferably 2 to 8 g / 1. If it is less than 1 g, the amount of film formed is small and good whiteness resistance cannot be obtained. If it exceeds 10 g / 1, the processing adhesion of the film will decrease. Furthermore, it adheres to the steel plate during processing and

| 0 The amount delivered is increased and becomes less economical.

The above-mentioned Zn compound may be any as long as it is soluble in an acid. However, when zinc oxide is used, a stable treatment bath can be obtained, which is preferable.

In the present invention, a surface-treated steel sheet is prepared using a treatment bath containing one or more of the above-mentioned metal oxysulfates, a P compound, and a Zn compound.

When ^ is coated, a resin-coated surface-treated steel sheet exhibiting good corrosion resistance and film adhesion is obtained. However, when this treatment bath is applied to a zinc-plated steel sheet and used without coating with an organic resin, it is quite difficult to completely suppress the occurrence of whitening. Therefore, the treatment bath further contains one or more Mg or A1 sulfates such as magnesium sulfate and aluminum sulfate, and phosphorus or phosphonate. M g or

The content of the sulfate of 20 A 1 is preferably 3 to 50 g Z 1 in total. If the content is less than 3 g Zl, no effect is obtained, and if the content exceeds 50 g Z1, a sufficient effect is obtained, and it is not necessary to contain more. The total content of phosphonate is preferably 1 to 80 g / 1.

In addition, when magnesium biphosphate or aluminum biphosphate containing Mg or A1 as the P compound is used, the same effect as when Mg or A1 sulfate is contained is obtained. Furthermore, in order to improve the conductivity and stabilize the treatment bath, salts such as sodium sulfate and ammonium sulfate may be contained in an amount of 50 g / 1 or less.

The pH of the treatment bath is preferably 1 to 5, more preferably 2 to 4. If the pH is less than 1, a non-uniform film is formed, and if the pH exceeds 5, the treatment bath becomes unstable and the corrosion resistance of the film decreases with S.

The pH is adjusted by adding an alkali such as ammonia or caustic soda and an acid such as sulfuric acid or phosphoric acid. The temperature of the treatment bath is preferably in the range of 20 to 50.

Using the treatment bath created as described above, a treatment film is formed on the steel sheet. As a treatment method, both immersion treatment and electrolytic treatment are possible. In the case of immersion treatment, a treatment film having a sufficient thickness can be obtained in 1 to 60 seconds, preferably 2 to 10 seconds. Even if immersed for 60 seconds or more, the thickness of the film does not increase so much.

In the case of electrolytic treatment, a thick film can be obtained in a short time, and either cathodic treatment or anodizing can be applied. In each case, it is preferable to apply a current at a current density of 0.5 to 30 A / dm ² , preferably 1 to 10 A Z dm ² for 0.1 to 10 seconds. If it is less than 0.5 A / dm ² , it takes too much time to grow the film, and a thick film cannot be obtained in a short time.If it exceeds 3 OA / dm ² , burns occur and a uniform film can be obtained. Absent. If a current is applied for more than 10 seconds, the film becomes too thick, and when a resin film such as an organic resin film is coated on the treated film, the processing adhesion of the resin film decreases.

Next, a steel sheet serving as a base for coating the surface treatment film will be described. Examples of the steel sheet 20 include a hot-rolled steel sheet obtained by removing the scale formed on the surface by hot-rolling a normal aluminum-killed continuous forged steel, a cold-rolled steel sheet obtained by cold-rolling and annealing a hot-rolled steel sheet, It is possible to use a single-layer plated steel sheet made of any one of Sn, Ni, Co, Mo, and Zn, or a plated steel sheet that has been subjected to multi-layer plating or alloy plating made of two or more kinds. Among them, the most versatile Zn-plated steel sheet is hot-dip Zn-plated steel sheet, hot-dip Zn alloyed steel sheet containing A ^ 1 or Mg, electric Zn-plated steel sheet, or Zn-one Ni, Zn-Fe, Zn-Co, etc. electric Zn-plated steel sheets, especially electric Zn -There are Co-Mo-plated steel sheets, all of which can be used in the present invention. The surface treatment of the present invention is performed as follows. That is, the hot-rolled steel sheet and the cold-rolled steel sheet are subjected to a pickling treatment and a degreasing treatment by a conventional method. Alternatively, after a pickling treatment and a degreasing treatment, any one of the above-mentioned platings is applied to obtain a plated steel sheet. Next, the steel sheet or the plated steel sheet is immersed or electrolytically treated in the above-mentioned treatment bath under the above-mentioned conditions to form a surface treatment film.

As described above, the surface-treated steel sheet of the present invention can be obtained.

Next, the resin-coated surface-treated steel sheet of the present invention will be described. The resin-coated surface-treated steel sheet of the present invention is obtained by coating the surface-treated steel sheet prepared as described above with an organic resin. As the organic resin, any resin can be applied as long as it can coat the surface-treated steel sheet, but any of polyester resin, polyolefin resin, polyvinyl chloride resin, polycarbonate resin, urethane resin, and acrylic resin can be used. It is preferable to use Further, by including at least one of colloidal silica, polytetrafluoroethylene, polyethylene wax, a silane coupling agent, and a chromium-free antioxidant in the organic resin, lubricity, adhesion, and corrosion resistance are improved. It can be further improved.

Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, a copolymerized polyester resin in which part of the polyhydric acid component and / or polyhydric alcohol component of these resins is replaced with another component, and butylene terephthalate monolithic resin.

Examples thereof include copolymerized polyester resins mainly composed of two units, and resins obtained by blending these polyester resins.

Examples of polyolefin resins include homopolymers such as polyethylene, polypropylene, polybutene, and polymethylpentene, ethylene / propylene copolymer, ethylene / propylene / gen copolymer, ethylene / vinyl acetate copolymer, and ethylene / propylene copolymer. Copolymers such as ethyl acrylate copolymer and olefin polymer can be used. Use a polyvinyl chloride resin containing 10 to 50 parts by weight of a plasticizer such as di- (2-ethylhexyl) phthalate, dibutyl phthalate, and octyl adipate. Is preferred.

As the polycarbonate resin, bisphenol A-polycarbonate resin is preferable. Examples of the polyamide resin include 6-nylon, 6,6-nylon, 6,10-nylon, and 12-nylon.

As the urethane resin, an aqueous resin that can be dissolved or dispersed in water is preferable to an organic solvent resin from the viewpoint of environmental protection. In addition to the urethane resin, a urethane resin modified with acryl, olefin, polyester, fluorine, or the like is used. Is appropriate. As the acrylic resin, an aqueous resin is preferable. In addition to the acrylic resin, an acrylic resin modified with urethane, olefin, polyester, fluorine or the like is suitable.

In addition, colloidal silica may be contained in the organic resin for the purpose of increasing the hardness of the entire resin layer, and improving scratch resistance, abrasion resistance, and corrosion resistance. Lubricant powder such as a mixture may be contained.

Further, by adding a chromium-free anti-oxidant, the corrosion resistance is further improved. Further, providing an organic resin layer containing a silane coupling agent further improves corrosion resistance and adhesion.

Known methods for forming an organic resin on the surface-treated steel sheet of the present invention include lamination methods such as film lamination and extrusion lamination, powder coating methods, roll coating methods, spraying methods, and electrostatic coating methods. The method is applicable. In the case of the laminating method, these resins may be formed into a stretched film or an unstretched film, and the resin film may be laminated on the surface-treated steel sheet of the present invention by a heat bonding method, or a polyester or acrylic resin. It may be bonded to the surface-treated steel sheet by using an adhesive such as a base, urethane, epoxy or melamine. Furthermore, heat and melt the resin, and directly onto the surface It may be extruded and laminated on a treated steel sheet.

Further, a polymer and a plasticizer dissolved in a solvent and made into a sol, such as a polyvinyl chloride resin, may be applied to a surface-treated steel sheet, and then heated to gel.

Above all, from the viewpoint of environmental protection, an aqueous resin that is more soluble or dispersible in water than an organic solvent-based resin is used, and the thickness of the organic resin layer may be relatively thin. Therefore, it is preferable to adopt a method in which the surface-treated steel sheet of the present invention is immersed in an aqueous solution in which a resin is dissolved, excess resin solution is removed using a squeezing roll or the like, and then dried. Drying method is hot air drying, gas oven, electric oven,

| ϋ Either means such as an induction heating furnace may be used, and the most advantageous method may be adopted from the viewpoint of the throughput and economy. After the coating film is formed, UV irradiation or electron beam irradiation may be used in combination.

As described above, the resin-coated surface-treated steel sheet of the present invention of the present invention can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples.

(Example)

Creation of surface-treated steel sheet

A 0.3 mm thick cold-rolled steel sheet is subjected to alkaline electrolytic degreasing and sulfuric acid pickling using a standard method, and then Zn plating, Ζη—Co—Mo plating, or 00Zn—N under the following conditions. An i-alloy plating was performed to prepare a zinc-plated steel sheet, a Zn_Co-Mo-plated steel sheet, or a Zn-Ni alloy-plated steel sheet.

[Zn plating conditions]

Bath composition

Z n S〇 ₄ 7H ₂ 〇: 250 g / 1

_{_{_{2Τ (NH 4) 2 S0 4}}} : 30 g / 1

Bath temperature: 40 in : 20 A / dm ²

Plating weight: 5 g / m ²

[Zn-Co-Mo plating conditions]

Bath composition

_{Z n S 0 4 · 7 H} 2 0: 250 g 1

C o S0 ₄ · 7 H2O: 50 g / 1

(NH ₄ ) 6M07O24 · 4H ₂ 0: 0.2 g / 1

Brightener (Hydrochloride of dicyandiamide formaldehyde condensate) 4m 1/1

10 Bath temperature: 40 ° C

Current density: 20 A / dm ²

Plating weight: 5 g / m ²

[Zn-Ni alloy plating conditions]

Bath composition

Polyvinyl alcohol: 2 S / 1

Bath temperature 50 V,

0 Current density 25 A / dm ²

Plating weight 5 g / m ²

The Zn-coated steel sheet, Zn-Co-Mo-plated steel sheet, or Zn-Ni alloy-plated steel sheet prepared as described above was treated with a surface treatment bath having the bath composition shown in Tables 1 to 4, Surface treatment was performed under the conditions to create a surface-treated steel sheet. 1

Trial surface treatment Skin formation conditions

Processing conditions

Number

Bath H Technical method Lightning current density Processing time

CC) (A / da ⁸ ) (seconds)

1 20 3.5 Cathode treatment 5 1

2 40 2.5 Cathode treatment 5 0.5

3 50 2 Cathode treatment 5 1

4 40 4 Dip treatment 10

5 30 3 Cathode treatment 10 1

6 30 3 Beach treatment 3

7 30 3 »Polar treatment 1 5

Three

Surface treatment skin formation conditions Treatment conditions Bath temperature ΡΗ Treatment method Electron density Treatment time

VC) (A / di ² ) (seconds)

40 3 Cathode treatment 5 1

40 3.5 Beach treatment 5

40 3 Cathode treatment 20 1

40 3 Cathode treatment 1 1

40 3 Processing 5 1

40 3 Depolarization 5 1

30 3 Cathode treatment 1 5

The corrosion resistance of the surface-treated steel sheet prepared as described above was evaluated in the following manner. As comparative material 1, chromic acid anhydride: 25 1, sulfate: 0. 1 gZ 1 and electrolytic chromate treatment as a treatment bath, electric Z n-C o-Mo-plated steel sheet on the total chromium content and to 30MgZm ² chromium An electrical Zn—Co—Mo metal sheet having a hydrated oxide film formed thereon was used. An electrical Zn—Co—Mo plated steel plate without chromate treatment was also used as Comparative Material 2. Evaluation of corrosion resistance of surface treated steel sheet

Corrosion resistance

10 For the surface-treated steel sheet of the present invention shown in Tables 1 to 4 and the comparative materials 1 and 2, a salt spray test based on JIS-Z 2371 was conducted for 24 hours using test pieces that were bent at 90 degrees. After that, the surface was visually observed, and the flat portion and the 90-degree bent portion were evaluated according to the following five grades.

Rating 5: No change is observed on the surface.

^ Rating 4: Slight whiteness that does not cause a practical problem is observed on the surface. Rating 3: Whiteness that causes a practical problem is observed on the surface.

Rating 2: Considerable whiteness is observed on the surface.

Rating 1: White tinge is observed on the entire surface.

Table 5 shows the iJD results. Sample No.Corrosion resistance classification Flat plate part

1 5 5 The present invention

2 5 5 The present invention

3 5 5 The present invention

4 5 4 The present invention

5 5 5 The present invention

6 4 4 The present invention

7 5 5 The present invention

8 5 5 The present invention

9 4 4 The present invention

1 0 5 5 The present invention

1 1 5 5 The present invention

1 2 5 5 The present invention

1 3 5 5 The present invention

1 4 5 5 Present invention Comparative material 1 5 3 Comparative material Comparative material 2 1 1 Comparative material Next, the resins shown in Tables 6 and 7 were laminated on the surface-treated steel sheets selected from Tables 1 to 4 under the respective conditions to prepare resin-coated surface-treated steel sheets. Furthermore, Comparative Material 4 was prepared by coating an organic resin on an electrical Zn—Co—Mo plated steel sheet (Comparative Material 2) without chromate treatment. In addition, a conventional electrolytic chromate treatment was performed to form an electrical Zn—Co—Mo plated steel sheet with a chromium hydrated oxide film with a total chromium content of 3 OmgZm ² formed on an electrolytic Zn—Co—Mo plated steel sheet (comparative material 1). A comparative material 3 in which an organic resin was coated on was prepared.

6

Note) ΡΕΤ-Β0 ·: ** Refill: άRephtalate biaxially stretched 7 ΡΕ-Β0 ·: * 'Re1 chilled two-wheeled roll #F PYC *: Refill ::, DBP *: 'F' chill phthalate Test surface treatment β condition of organic resin

Steel sheet (Table

No. 1 or 2 * h machine tti grease Thickness Stacking method Stacking conditions

No. sample number () indicates weight X

No.)

22 7 Urethane 1. -*]-((1) The water-soluble urethane ttfffi was D-treated on a surface-treated steel plate, and then dried to form a layer with a predetermined thickness.

23 9 扑 Change 2 -Water soluble on modified surface treated steel plate Modified product Ϊ »榭 bil (75)« ο-f

Acrylic dull silica (20) + FlT (4.5) + silane force 7 Prink 'agent (0.5) was D-W-trained, dried and dried to form an organic resin layer with a predetermined J length.

24 10 Water-modified 0.5 S acting Water-soluble water-modified 7 WttlB Soak the surface ffi board in acrylic solution, and use the squeezing Π- »to remove the excess ffi solution. After removing the organic layer, it was dried to form an organic layer having a predetermined thickness.

25 11 Fak 'J * 0.3 g Hama method Water soluble 7 chestnuts> Tree 90 (90) + PTFE (10) Soak the surface treated ff plate in a solution, and use the After removing the resin solution, a shoe with a predetermined thickness was formed.

26 12 Urethane 1 S Clear water-soluble urethane tree K (55) + 3D ida silica (44) + 7 + '7Α ring agent

(1) A so-called surface treatment was immersed in the surf, and the excess Tree II solution was removed using a squeeze D- », followed by drying to form 11 layers of organic trees of a predetermined thickness. ,

27 14 Urethane 0.5 S Sama method Water-soluble urethane «ΜΒ (60) + PTFE (5)« D idal silica (34) + silane

<)> 9 'agent (1) Soak the surface-treated steel sheet in the solution, remove excess resin solution using a squeeze D-, dry JK, and dry to a predetermined thickness. The «4 material 3 urethane 0.5 immersion method was applied on specific drawn material 1 under the same circumferential conditions as ttff number 27. Comparative material 4 urethane 0.5 immersion method sample number 27 Coated on comparative material 2 under the same hiring conditions as

PTFB: ** Litetraf WDI Chin, PI: ** R The film adhesion of the resin-coated surface-treated steel sheet thus obtained was evaluated in accordance with the following procedure together with the corrosion resistance described above.

Film adhesion

The resin-coated surface-treated steel sheet was drawn into a cylindrical cup shape with a drawing ratio of 2.2, the film on the side of the cup was forcibly peeled off with adhesive tape, and the degree of film peeling was visually observed. evaluated.

Rating 5: No peeling was observed.

Rating 4: Slight peeling is observed, which is not a problem in practical use. Rating 3: Peeling to a degree that is problematic in practical use is recognized.

Rating 2: considerable peeling is observed.

Rating 1: Peeling is observed on the entire side surface.

Table 8 shows the results of the above characteristic evaluations.

Characteristic Evaluation Result Category Sample No.

Flat plate corrosion resistance Machining part corrosion resistance Film adhesion

1 5 5 5 5 Invention

1 6 5 5 5 The present invention

1 7 5 5 5 The present invention

1 8 5 5 5 The present invention

1 9 5 5 5 The present invention

2 0 5 5 5 The present invention

2 1 5 5 5 The present invention

2 2 5 5 5 The present invention

2 3 5 5 5 The present invention

2 4 5 5 5 The present invention

2 5 5 5 5 The present invention

2 6 5 5 5 The present invention

2 7 5 5 5 Present invention Comparative material 3 5 5 5 Comparative material Comparative material 4 4 2 4 Comparative material As shown in Table 5, the surface-treated steel sheet of the present invention exhibited superior characteristics as compared with Comparative Material 2, and had the same or higher corrosion resistance as compared with Comparative Material 1 which had been subjected to conventional electrolytic chromating. have.

As shown in Table 8, the resin-coated surface-treated steel sheet in which the surface-treated steel sheet of the present invention was coated with an organic resin was coated with an organic resin on a Zn—Co—Mo plated steel sheet without electrolytic chromate. Compared to the comparative material 3 in which the organic resin is coated on the conventional electrolytic chromate, it has the same or better corrosion resistance and film adhesion than the comparative material 3 in which the organic resin is coated on the conventional electrolytic chromate.

| ϋ Industrial applicability

The present invention is characterized by immersing or electrolytically treating a steel sheet in an aqueous solution containing at least one of oxysulfates of Mo, Ti, V, and Zr, a P compound, and a Zn compound. A method of producing a surface-treated steel sheet, which is further immersed in an aqueous solution to which Mg, one or more of sulfates of A1 and / or phosphonate is positively added.

\ S Features treatment or electrolytic treatment. Still further, the oxysulfate is molybdenum oxysulfate or vanadyl sulfate. A method for producing a surface-treated steel sheet, wherein the P compound comprises at least one of phosphoric acid, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, and aluminum biphosphate. .

Further, the present invention relates to a surface-treated steel sheet obtained by using the production method, and a resin-coated surface-treated steel sheet obtained by coating the surface-treated steel sheet with an organic resin. The method for producing the surface-treated steel sheet of the present invention is excellent in the preservation of the working environment, and the surface-treated steel sheet obtained by using the production method has excellent corrosion resistance. The treated steel sheet is excellent not only in corrosion resistance but also in film adhesion.

Claims

Range of request

1. characterized in that the steel sheet is immersed or electrolytically treated in an aqueous solution containing one or more oxysulfates of Mo, Ti, V, and Zr, a P compound, and a Zn compound. Manufacturing method of surface treated steel sheet.

2. The steel sheet is immersed or electrolytically treated in an aqueous solution containing one or more of oxysulfates of Mo, TV, and Zr, a P compound, a Zn compound, and a phosphonate. The method of manufacturing surface treated steel sheet.

3. A steel sheet in an aqueous solution containing at least one of oxysulfates of Mo, Ti, V, and Zr, a P compound, a Zn compound, and at least one of sulfates of Mg and A1. A method for producing a surface-treated steel sheet, comprising subjecting a steel sheet to immersion or electrolytic treatment.

4. An aqueous solution containing at least one of oxysulfates of Mo, Ti, V, and Zr, a P compound, a Zn compound, at least one of sulfates of Mg and A1, and a phosphonate. 5. A method for producing a surface-treated steel sheet, wherein the steel sheet is subjected to immersion treatment or electrolytic treatment.

5. The method for producing a surface-treated steel sheet according to claim 1, wherein the oxysulfate is molybdenum oxysulfate.

6. The method for producing a surface-treated steel sheet according to claim 1, wherein the oxysulfate is vanadyl sulfate.

0 7. The surface according to any one of claims 1 to 4, wherein the P compound comprises at least one of phosphoric acid, ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, and aluminum biphosphate. Manufacturing method of treated steel sheet.

8. The method for producing a surface-treated steel sheet according to claim 2, wherein the phosphonate is aminotri (methylene-phosphonic acid).

9. The method according to any one of claims 1, 2, 5, 6, 7, and 8, wherein at least one of Mo, Ti, V, and Zr, a substance containing P, n-containing substances A surface-treated steel sheet obtained by coating a steel sheet with a protective film mainly composed of:

10. Using the manufacturing method according to any one of claims 3, 4, 5, 6, 7, 8, and 8, one or more of Mo, Ti, V, and Zr, a substance containing P, and Zn Steel and a protective coating mainly composed of a substance containing at least one of Mg and A1

^ Surface treated steel sheet coated on top.

1 1. The surface-treated steel sheet according to claim 9 or 10, wherein the steel sheet is a zinc-plated steel sheet or a steel sheet plated with Zn.

12. The surface-treated steel sheet according to claim 11, wherein the Zn-plated steel sheet or the alloy-plated steel sheet containing Zn is manufactured by an electrolytic treatment method.

IC 13. The surface-treated steel sheet according to claim 11 or 12, wherein the alloy-coated steel sheet containing Zn is a Zn—Co—Mo plated steel sheet.

14. A resin-coated surface-treated steel sheet obtained by coating the surface-treated steel sheet according to any one of claims 9 to 13 with an organic resin.

15. The organic resin according to claim 14, wherein the organic resin is any of a polyester resin, a urethane resin, an acrylic resin 1ST resin, a polyolefin resin, a polycarbonate resin, a polyamide resin, or a polyvinyl chloride resin. The resin-coated surface-treated steel sheet described in the above.

16. The resin-coated surface according to claim 14 or 15, wherein the organic resin contains at least one of colloidal silica, polytetrafluoroethylene, polyethylene wax, a silane coupling agent, and a chromium-free antioxidant. Treated steel sheet.