WO2000055390A1

WO2000055390A1 - Method for producing surface treated steel sheet, surface treated steel sheet and surface treated steel sheet coated with resin comprising surface treated steel sheet and organic resin coated thereon

Info

Publication number: WO2000055390A1
Application number: PCT/JP2000/001403
Authority: WO
Inventors: Masao Komai; Masanori Yoshikawa
Original assignee: Toyo Kohan Co., Ltd.
Priority date: 1999-03-12
Filing date: 2000-03-08
Publication date: 2000-09-21
Also published as: AU2938900A; TW526283B; JP4179527B2

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 and a phosphorus compound, or in an aqueous solution further containing a significant amount of one or more of sulfates of Mg and Al; and a method for producing a surface treated steel sheet coated with a resin which comprises 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 to replace a surface treated steel sheet which has been treated with a chromate solution, and the surface treated steel sheet coated with a resin which is prepared by the above method has sufficient adhesiveness of steel with the resin to replace such a steel sheet produced by a method comprising treating with a chromate solution.

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-plated steel sheet or the like is coated with a protective film having excellent corrosion resistance and film adhesion, a surface-treated steel sheet, and coating the surface-treated steel sheet with an organic resin. And a resin-coated surface-treated steel sheet. 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 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 cause corrosion when not coated with a film or organic resin. Also, when coated with a coating film or an organic resin, the adhesion, especially during processing, is insufficient.

The chromate film is formed on the steel sheet by using methods such as immersion treatment, coating treatment, and electrolytic treatment that do not involve electrolysis. And 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. The electrolytic chromate coating by electrolysis is performed with a solution containing a harmful ^hexavalent chromium, chromic acid mist generated further in the electrolyte may adversely affect the working environment.

In this way, the steel sheet with the chromate film is excellent in corrosion resistance and processing adhesion. Therefore, it is likely to have an unfavorable effect on the human environment.Therefore, a treatment film is required to replace the chromate film, which has excellent protection and processing adhesion. Have been.

As an example, Japanese Patent Application Laid-Open No. H10-183833 discloses Mo, W, V, Nb, Ta, Ti, Zr, Ce, Sr, and trivalent chromium. Films mainly composed of at least one kind of metal element and phosphorus oxyacid, oxyacid salt or a substance derived from their anhydride, or a substance derived from oxidizing substance, alkaline earth metal, silicon, inorganic colloid Disclose coatings containing at least one substance derived from copper, Zn, Ni, Cu, Ag, Fe, Cd, A1, Mg or alloys thereof. It states that it is possible to produce a film having uniform and good appearance and corrosion resistance.

In the above-mentioned Japanese Patent Application Laid-Open No. H10-183833, as a source of the metal, molybdate ion, tungstate ion, vanadate ion, niobate ion, tantalate ion, trivalent chromium ion, etc. It further describes the use of soda molybdate, ammonium molybdate, ammonium tandastinate, ammonium vanadate, chromium acetate, chromium nitrate, etc. as sources of these ions. .

Furthermore, orthophosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, tripolyphosphoric acid, perphosphoric acid, etc. may be used as a substance derived from oxyacids, oxyacid salts or anhydrides of phosphorus. Has been described. The above metal source and the above oxyacid or oxyacid salt of phosphorus or their anhydrides are components constituting the skeleton of the film, and the oxidizing property ensures the stability of the solution, and the metal is etched smoothly. It contributes to the formation of a thin film.

However, even when a treatment film is formed on a metal plate such as a zinc-plated steel plate using the treatment bath described in the above-mentioned Japanese Patent Application Laid-Open No. 10-183334, the resulting surface-treated metal plate Characteristics, especially for organic resin-coated metal plate with surface treated metal plate coated with organic resin film The adhesion of the coating, especially the processing adhesion, is inferior to that of a surface-treated metal plate on which a conventional chromatized coating is formed. Also, when applied to a zinc-plated steel sheet, it has poor whiteness resistance.

The present invention provides a method for producing a surface-treated steel sheet having excellent corrosion resistance and excellent processing adhesion to an organic resin film, which is an alternative to a chromate-treated surface-treated steel sheet, a surface-treated steel sheet, and the use of 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 claim 1 includes immersing or electrolytically treating the steel sheet in an aqueous solution containing one or more oxysulfates of Mo, Ti, V, or Zr and a phosphorus compound. Features.

The method for producing a surface-treated steel sheet according to claim 2 is characterized in that the steel sheet is immersed or electrolytically treated in an aqueous solution to which one or more of Mg or A1 sulfate is positively added. In these methods, it is desirable that the oxysulfate is molybdenum oxysulfate or vanadyl sulfate.

And it is desirable that the phosphorus compound comprises one or more of ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, or aluminum biphosphate.

The surface-treated steel sheet according to claim 6 is characterized in that a protective film containing at least one of Mo, Ti, V or Zr and P as a main component is formed on the steel sheet by using any one of the above-described methods for producing a surface-treated steel sheet. The coated steel sheet is characterized by being coated with a protective film that positively contains at least one of Mg and A1.

These surface-treated steel sheets are desirably Zn-plated steel sheets, particularly electric Zn-plated steel sheets, and the Zn-plated steel sheets are Zn-based alloy-plated steel sheets containing Zn, particularly electric Zn-Co. It is desirable that the steel sheet be a Mo-plated steel sheet. The resin-coated surface-treated steel sheet according to claim 11 is characterized in that the surface-treated steel sheet is coated with an organic resin.

In this resin-coated surface-treated steel sheet, it is desirable that the organic resin is any one of a polyester resin, a urethane resin, an acrylic resin, a polyolefin resin, or a polyvinyl chloride resin. It is desirable to include 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 and a phosphorus 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 is positively added is used. Furthermore, the oxysulfate is characterized by being molybdenum oxysulfate or vanadyl sulphate, and the phosphorus compound is selected from the group consisting of ammonium biphosphate, sodium biphosphate, sodium biphosphate, and sodium biphosphate. It is characterized by comprising at least one of magnesium phosphate and aluminum biphosphate. Phosphoric acid or phosphate alone forms a film, but the film is porous, and when formed on a steel plate, has poor corrosion resistance. Metals such as chromium have been incorporated into phosphoric acid films for the purpose of improving corrosion resistance.Chromium, in particular, has been used extensively because of its excellent corrosion resistance and adhesion to coatings such as paints. However, as shown above, it may be harmful to the environment, and attempts have been made to use Mo, W, V, etc. as a metal instead of chromium. All of these metals are used in the form of metal oxide ions such as molybdate ion, tungstate ion, and vanadate ion, which are added to the treatment bath. The properties of the used surface treatment film were not shown.

In the present invention, one of Mo, Ti, V or Zr is used as a metal instead of chromium. The above is contained in the treatment solution together with the phosphorus compound in the form of an oxysulfate, and the oxysulfate of Mo, Ti, V or Zr and the phosphorus compound are contained in the treatment film formed using this treatment bath. It was found that by incorporating substances derived from chromium, film properties equivalent to or better than those of surface treatment films using chromium could be obtained. The reason for this is not clear, but by including the above Mo, Ti, V or Zr in the form of oxysulfate in the treatment bath, the Mo is trivalent, pentavalent and hexavalent. molybdenum oxygen i O emissions of (0 ² -) and sulfate ions (SO -) and associated compounds, and, T i, 4-valent T i for V or Z r, V or Z r is an oxygen ion (Omicron ^The substance derived from the compound linked to ² ) and sulfate ion (S o, ^2- ) becomes a component that forms the skeleton of the film formed on the steel plate together with P, and this film has excellent corrosion resistance. It is considered that In particular, when the steel sheet is a Zn-plated steel sheet or a steel sheet coated with a Zn-based alloy, the steel sheet is combined with one or more of Mo, Ti, V, or Zr in association with Zn or an alloy element in the plating film. P and Zn are mainly components that form the skeleton of the film, and it is considered that this film has excellent heat protection. In addition, it is considered that by positively containing one or more of Mg and A 1 in the above-mentioned film, the protection is further improved.

In addition, these films contain Mo, Ti, V or Zr in a high valence state in a favorable form, oxidize other substances and promote oxide film formation, and It is considered that the valence is reduced and the state becomes lower in valence. This reaction is considered to be similar to the oxidizing function of chromate ions, and it is considered that the film has excellent heat resistance due to its self-healing properties.

Hereinafter, the content of the present invention will be described.

First, the treatment bath will be described. The treatment bath of the present invention comprises molybdenum oxysulfate, titanyl sulfate, vanadyl sulfate, zirconyl sulfate, at least one of the oxysulfates of Mo, Ti, V, and Zr, and ammonium biphosphate. It consists of an aqueous solution containing a phosphorus compound such as ammonium dihydrogen phosphate or sodium biphosphate (sodium dihydrogen phosphate), as well as magnesium sulfate and aluminum sulfate that improve heat resistance. One or more of sulfates of Mg or A1 may be added. Furthermore, salts such as sodium sulfate and ammonium sulfate may be added in order to improve the conductivity and stabilize the treatment bath.

The total content of molybdenum oxysulfate, titanyl sulfate, vanadyl sulfate, zirconyl sulfate and the like is 3 to 150 g / l, preferably 5 to 50 gZl. If it is less than 31, the amount of film formed is small and good film properties cannot be obtained. _If it exceeds 1 50 _g 1, the color tone of the film will change and the adhesion of the film will decrease. In addition to the high cost of chemicals, the amount of chemicals that adhere to the steel plate during processing increases and is not 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.

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

As the above phosphorus compound, one or more compounds such as orthophosphoric acid, condensed phosphoric acid, phosphorous acid, hypophosphorous acid, and other P-containing phosphorus oxyacids and oxyacid salts can be applied. When ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, or aluminum biphosphate, which is a biphosphate compound, is used, a stable treatment bath can be obtained, which is preferable.

In the present invention, when a surface-treated steel sheet is prepared using a treatment bath containing at least one kind of the above-mentioned oxysulfates of the metal and only the phosphorus compound, and coated with an organic resin, good corrosion resistance and film adhesion are obtained. Thus, a resin-coated surface-treated steel sheet having excellent properties can be obtained.

However, if this treatment bath is applied to a zinc-plated steel sheet and used without coating with an organic resin, whitening is likely to occur. Therefore, magnesium sulfate is added to the treatment bath. Contains one or more Mg or A1 sulfates such as aluminum and aluminum sulfate. The content is preferably 3 to 50 g Zl in total. If the content is less than 3 g Z1, no effect can be obtained. Even if the content exceeds 50 g / 1, a sufficient effect can be obtained, and it is not necessary to contain more. When magnesium or aluminum biphosphate containing Mg or A1 as the phosphorus compound is used, the same effect as when Mg or A1 sulfate is contained can be 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 gZ1 or less.

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

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

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 the 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, 0.5 to 30 A / dm ² , preferably 1 to 10 A! ! ^ At current density. It is preferable to energize for 1 to 10 seconds. If it is less than 0 · 5 AZ 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 30 AZ dm ² , burns occur and a uniform film cannot be obtained. If current is applied for more than 10 seconds, the film becomes too thick, and if 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. For the steel sheet, the scale formed on the surface by hot rolling normal aluminum-killed continuous steel is used. Removed hot-rolled steel sheet, cold-rolled steel sheet which has been cold-rolled and annealed, or a single layer made of any one of Sn, Ni, Co, Mo, and Zn It is possible to use a plated steel sheet which has been subjected to plating or multi-layer plating or alloy plating comprising two or more types. Among these, the most versatile Zn-plated steel sheets include hot-dip Zn-coated steel sheets, hot-dip Zn-coated alloy steel sheets containing A1 and Mg, electric Zn-coated steel sheets, and electric Zn-based alloy steel sheets. Although there are steel sheets having a thickness, particularly electric Zn-Co-Mo-plated steel sheets, any of them 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 subjected to immersion treatment or electrolytic treatment in the treatment bath under the above 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 be coated on 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 incorporating at least one of colloidal silica, polytetrafluoroethylene, polyethylene wax, a silane coupling agent, and a chromium-free antioxidant into the organic resin, lubricity, adhesion, and corrosion resistance are further improved. Can be done.

As the polyester resin, polyethylene terephthalate, polybutylene terephthalate, a copolymerized polyester resin in which a part of the polyhydric acid component and Z or polyhydric alcohol component of these resins are replaced with other components, and a unit of butylene terephthalate are mainly used. Polyester resin, blended polyester resin Examples of the resin include:

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 / acrylic acid. Copolymers such as an ethyl copolymer and an olefin polymer can be mentioned.

Use polyvinyl chloride resin containing 10 to 50 parts by weight of a plasticizer such as di- (2-ethylhexyl) phthalate, dibutyl phthalate or dioctyl 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 more preferable than an organic solvent resin from the viewpoint of environmental protection.In addition to the urethane resin, urethane modified with acrylic, olefin, polyester, fluorine, or the like is used. Resins are suitable. As the acrylic resin, an aqueous resin is preferable, and 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. Further, a lubricant powder such as polytetrafluoroethylene or polyethylene may be contained for the purpose of improving lubricity.

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.

As a method for forming the organic resin on the surface-treated steel sheet of the present invention, Known coating methods such as laminating methods such as coating, extrusion laminating, powder coating method, roll coating method, spraying method and electrostatic coating method can be applied. 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. Further, the resin may be heated and melted, and may be directly extruded and laminated on the surface-treated steel sheet. Furthermore, 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. As a drying method, any method such as hot air drying, a gas oven, an electric oven, and 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.

Example

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

A 0.3 mm thick cold-rolled steel sheet is subjected to a sulfuric acid pickling treatment and an alkaline electrolytic degreasing treatment using a standard method, and then subjected to Zn plating, Zn—Co—Mo plating, or Zn-Ni alloy plating was performed to produce Zn-plated steel sheets, Zn-Co-Mo plating sales sheets, or Zn-Ni alloy-plated steel sheets. [Zn plating conditions]

Bath composition

(NH ₂ SO ₄ 30 g / 1 Bath temperature 40.C Current density 20 A / dm: Plating weight 5 g / m ²

[Zn—Co—Mo plating conditions]

Bath composition

Z n S 0 ₄ 7 Η ₂ 0 250 g / 1

_{_{_{(NH4) 6 Mo 7 0 2}}} 4 · 4 H 2 0 0. 2 g / 1 (NH 4) 2 so 4 30 g / 1 Brightener hydrochloride Dochijimigobutsu)

4 m '1

Bath temperature 40 ° C Current density 20 A / dm ^: Coating weight 5 g / m ² [ZnN i alloy plating condition]

Bath composition

Z n S_〇 _{_{4 · 7 H 2 0 250 g}} / 1

Polyvinyl alcohol 2 g / 1 Bath temperature 50. C Current density 25 A / dm ^: Coating weight: 5 g / m ² Table 1 to Table 4 for Zn plated steel sheet, Zn—Co—Mo plated steel sheet, or Zn—Ni alloy plated steel sheet prepared as described above. A surface-treated steel sheet was prepared by performing a surface treatment under the conditions of a surface treatment bath having the bath composition shown below. table 1

Two

Sample surface treatment Cortical membrane formation condition No.

Processing conditions Bath temperature H Processing method Current density Processing time

\ No, no

1 3 5 Yin processing 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 Dip treatment 3

7 30 3 Anodizing 1 5

Sample surface treatment Cortical membrane formation condition No.

Processing conditions Bath temperature PH Processing method Current density Processing time

(A / dm (seconds)

8 40 3 Cathode treatment 5 1

9 40 3.5 Dip treatment 5

10 40 3 Cathode treatment 20 1

11 40 3 Cathode treatment 1 1

12 40 3 Cathode treatment 5 1

13 40 3 Anodizing 5 1

14 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 a comparative material 1, 25 g of chromic anhydride: Z 1 and 0.1 g of sulfuric acid: 0.1 g / 1 were subjected to electrolytic chromate treatment as a treatment bath, and the total amount of chromium on the electric Zn-Co—Mo plated steel sheet electrical Z n- C o- M o-plated steel sheet to form a 3 O mg chromium hydrous oxide film of Zm ² as were used. An electric Zri-Co-Mo-plated steel sheet without chromate treatment was also used as comparative material 2.

(Evaluation of corrosion resistance of surface-treated steel sheet)

(Corrosion resistance)

For the surface-treated steel sheet of the present invention shown in Tables 1 to 4 and the comparative materials 1 and 2, salt water spray tests based on JIS-Z2371 were performed using test pieces that were bent 90 degrees. After 24 hours, the surface was visually observed, and the flat plate 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: A slight whiteness is observed on the surface that does not cause any practical problem.

Rating 3: Whiteness is recognized on the surface to the extent that it poses a practical problem.

Rating 2: Considerable whiteness is observed on the surface.

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

Table 5 shows the results.

Sample No.IHU property Classification Flat plate processing 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 a chromium hydrate oxide film with a total chromium content of 3 Omg / m ² on a galvanized Zn-Co-Mo steel sheet. Comparative material 3 was prepared by coating an organic resin on a plated copper plate (comparative material 1).

Specimen surface treatment Condition of resin coating

No.Copper plate (Table

Material 1 Organic resin Thickness Laminating method Laminating condition

Number) (D)

15 1 ΡΕΤ-Β0 »film 20 Heat adhesion Surface treatment Heat the ίΗ plate to 290, abut PET-B0, sandwich the two with a pair of laminates 0, crimp and immediately cool in water.

16 2 ΡΕ-Β0 · Film 20 Adhesive Apply urethane adhesive to one side of PE-B0 and abut the adhesive-applied surface to the surface treatment. Insert a pair of laminate n-re Crimp

17 3 PET-B film 15 Heat bonding The surface-treated copper plate is heated to 29 (TC, abuts PET-B0, and a pair of laminates D-metal is detected. & Do

18 4 PE-B0 film 15 Heat bonding Heat the surface-treated copper plate to 290 "C, abut PET-BO, sandwich a pair of laminate D-C, press down, and immediately quench in water.

19 5 PVC * film 50 sol coating PVC: 80 parts by weight and DB on surface treated copper plate coated with urethane adhesive

P ⁺ : Apply 10 parts by weight of a mixture of 10 parts by weight of I-Tilce D'M-F, and heat to 200 * C to make it into a gel.

20 5 PET-BO film 30 Heat bonding Heat the surface-treated copper plate to 290 * c, abut PET-BO, sandwich a pair of laminates ne and e, and immediately press down and immediately cool in water.

21 5 PET-BO film 20 Heat bonding The surface-treated steel sheet is heated to 29ITC, PET-B0 is abutted, the two are sandwiched by a pair of laminates, pressed, and immediately quenched into water, Note) ΡΕΤ -Β0 · ： Polyethylene biphthalate biaxially stretched film. PE-B0 ′ Polyethylene biaxially stretchable film,

PVC »: Polyvinyl chloride, DBP + Siphyl phthalate

Specimen surface treatment Organic resin covering condition "1 No.

Sample 1 Organic resin Thickness «Layer method Laminating condition

(Number) Numbers in () are weight! 8

7,

22 7 Reno 1 u-Luco-[> Our IB¾i Sl Jt Ν¾ · ヮヮ / Noso JIg¾. Kotoshi / Kokoshi, Joshi, Society

An organic resin layer having a constant thickness was formed.

23 9-year-old reflex Modified 2D-Ruco-coated surface treatment »! Water-soluble olefin modified resin (75)

Acrylic 0) + PW (4.5) + y Dough force, D-coating of flinoc agent (0.5), then drying and prescribed

A thick organic spore layer was formed.

24 10-year-old denatured refining 0.5 Immersion m method Water-soluble Olef denaturation 7 chestnut

After removing the excess resin solution using acrylic resin, dry it to a specified thickness.

Formed an organic resin layer,

25 1 1 Acrylic 0.3 Dipping method Water-soluble Atari W »Fat (90) + PTFE (10)

After removing excess tree K solution using a squeezer, dry,

An organic resin layer of a certain thickness was formed,

ZD 1 9 Urethane 1 Immersion method Water-soluble urethane resin (55) + Coidal silica (44) + Silane Kakfu 'link' agent (1) in solution

Dip the surface-treated veneer into the sand and remove excess resin solution using a squeezer.

After leaving, it was dried to form an organic resin calendar of a predetermined thickness,

27 14 Urethane 0.5 Immersing method Water-soluble urethane resin (60) + PTFE (5) + ^] D-idal silica (34) + silane force 7 Frink's agent

(1) Immerse the surface-treated copper plate in the solution ».

After removing the solution, it is dried to form an organic resin layer of a predetermined thickness.

T

Comparative material 3 Urethane 0.5 Immersion method Coated on Comparative material 1 under the same lamination conditions as Sample No. 27.

Comparative material 4 Urethane 0.5 Immersion method Coated on Comparative material 2 under the same lamination conditions as Sample No. 27.

The film adhesion of the resin-coated surface-treated steel sheet obtained in this manner was evaluated together with the above-described corrosion resistance in the following manner.

(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.

8

Characteristic Evaluation Result Category Sample No.

Flat section corrosion resistance Processing section »Corrosion Film adhesion

1 5 5 5 5 The present 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 Industrial applicability

The surface-treated steel sheet of the present invention exhibits excellent characteristics as compared with Comparative Material 2, and has corrosion resistance equal to or higher than that of Comparative Material 1 which has been subjected to conventional electrochromation. In addition, the resin-coated surface-treated steel sheet in which the surface-treated steel sheet of the present invention is coated with an organic resin is a comparative material 4 in which an organic resin is coated on a Zn—Co—Mo-plated steel sheet without an electrolytic pore mate. It also has excellent properties, and has excellent corrosion resistance and film adhesion equal to or better than that of Comparative Material 3 in which organic resin is coated on conventional electrolytic chromate. In addition, the method for producing a surface-treated steel sheet of the present invention is excellent in the preservation of working environment, the surface-treated steel sheet obtained by using the production method is excellent in corrosion resistance, and the surface-treated steel sheet is coated with an organic resin. The surface-treated steel sheet is excellent not only in corrosion resistance but also in film adhesion.

Claims

The scope of the claims

1. A method for producing a surface-treated steel sheet, comprising immersing or electrolytically treating a steel sheet in an aqueous solution containing at least one of oxysulfates of Mo, Ti, V or Zr and a phosphorus compound.

2. Immersion or electrolytic treatment of the steel sheet in an aqueous solution containing one or more oxysulfates of Mo, Ti, V or Zr, a phosphorus compound, and one or more sulfates of Mg or A1. A method for producing a surface-treated steel sheet.

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

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

5. The method for producing a surface-treated steel sheet according to claim 1, wherein the phosphorus compound comprises at least one of ammonium biphosphate, sodium biphosphate, calcium biphosphate, magnesium biphosphate, and aluminum biphosphate. .

6. A surface-treated steel sheet in which a protective film mainly composed of one or more of Mo, Ti, V or Zr and a substance containing P is coated on the steel sheet.

7. A steel plate is coated with a protective coating mainly composed of one or more of Mo, Ti, V or Zr, a substance containing P, and a substance containing one or more of Mg or A1. Surface treated steel sheet.

8. The surface-treated steel sheet according to claim 6, wherein the steel sheet is a Zn-plated steel sheet or an alloy-plated steel sheet containing Zn.

9. The surface-treated steel sheet according to claim 8, wherein the Zn-plated steel sheet or the alloy-coated steel sheet containing Zn is formed by electrolytic treatment.

10. The surface-treated steel sheet according to claim 9, wherein the alloy-coated steel sheet containing Zn is a Zn-Co-Mo plated steel sheet.

1 1. A resin-coated surface-treated steel sheet obtained by coating the surface-treated steel sheet according to any one of claims 6 to 10 with an organic resin.

1 2. The organic resin is a polyester resin, a urethane resin, an acrylic resin, a polyolefin resin or a polychlorinated vinyl resin.

The resin-coated surface-treated steel sheet according to item 11).

13. The organic resin according to claim 11, wherein the organic resin includes at least one of colloidal silica, polytetrafluoroethylene, polyethylene oxide, a silane coupling agent, and a chromium-free protective agent. 13. Resin coated surface treated steel sheet.