JP4492224B2 - Surface-treated metal material, surface treatment method thereof, and resin-coated metal material - Google Patents

Description

  The present invention relates to a surface-treated metal material and a surface treatment method thereof, and more specifically, it is non-chromium and has excellent environmental properties, and also has adhesion, adhesion, corrosion resistance, dent resistance, and wear resistance with an organic resin film. The present invention relates to a surface-treated metal material having excellent properties and the like, a surface treatment method for such a surface-treated metal material, and a resin-coated metal material obtained by coating the surface-treated metal material with a resin.

As a treatment for improving the adhesion between a metal material such as a steel plate, a zinc-based plated steel plate, an aluminum-based plated steel plate, a zinc alloy plate, a tin-based plated steel plate, an aluminum foil, an aluminum alloy plate, and a magnesium alloy plate, and an organic film, As treatments for bonding a metal material to the same or different metal materials using an adhesive, a chromate treatment, a phosphate treatment, a treatment with a silane coupling agent, an anodizing treatment, and the like are conventionally known.
Metal materials using these treatments are widely used for home appliances, building materials, vehicles, aircraft, containers, and the like, and among them, chromate treatment has been most widely used due to its excellent corrosion resistance and adhesion.
Chromate treatment can be broadly divided into treatment methods, and it can be classified into chemical molding (reaction type / coating type) and electrolytic type. It can be classified into a type in which hexavalent chromium remains and a type in which hexavalent chromium does not remain in the final product.

  As for the type in which a small amount of hexavalent chromium remains in the final product, it has been pointed out that it may elute into the environment such as soil at the time of disposal, and the use of chromate treatment is proceeding mainly in Europe. In addition, any type of chromate treatment has various environmental problems because the treatment liquid contains hexavalent chromium which is a harmful substance. In other words, it is essential that drainage and exhaust treatment of the hexavalent chromium-containing treatment liquid be performed completely and not to be discharged to the outside, and a large amount of cost is required for drainage and exhaust treatment facilities, disposal treatment costs, and the like. Furthermore, since regulations on the movement and exhaust of wastewater treatment sludge are becoming stronger, it is desired to develop a non-chromium surface treatment comparable to conventional chromate treatment.

  As a matter of course, a metal material for a metal container uses a chromate treatment of a type in which hexavalent chromium does not remain in the final product, and further, coating with an organic resin or the like is performed thereon. For example, cathodic electrolysis of a tin-plated steel plate in an aqueous solution of sodium dichromate, cathodic electrolysis treatment of a steel plate in a fluoride-containing chromic anhydride aqueous solution, or treatment of an aluminum alloy with phosphoric acid chromate and an organic resin thereon The one coated with is used.

  As a non-chromium-based surface treatment, zirconium, titanium, or a compound thereof, a phosphate and a fluoride are used, and an acidic treatment solution having a pH of about 1.0 to 4.0 is used to treat the surface of the aluminum-containing metal material. In fact, a film formed with a chemical conversion film mainly composed of an oxide of zirconium and / or titanium is actually used, and depending on the compatibility with an organic resin, a film without the chemical conversion film itself is also put into practical use (for example, patents). Reference 1).

  In recent years, a precoat material coated with a polyester resin has been widely used from the viewpoint of hygiene of metal containers and flavor retention of contents. However, when polyester resin is used, it has higher water permeability compared to epoxy phenolic paints and acrylic epoxy paints that have been widely used in the past. Otherwise, the contents may be restricted in terms of adhesion and corrosion resistance. Further, when such a polyester resin coated with aluminum is used as an aluminum lid member, there is a problem that the adhesion is not sufficient even in the chromate treatment.

  In other words, a can coated with a polyester resin, which is an example of a pre-coated material processed product, has the advantage that a pre-coated metal material can be used as a starting material. Corrosion from the crack part from the polyester resin caused by the impact of, and the deterioration of the adhesion at the time of retort sterilization, and even if there is no defect in the polyester coating itself, depending on the components of the contents, induction of corrosion by permeated ions, etc. There is a problem different from the conventional manufacturing method in which the surface treatment and the post-coating of the paint are carried out after the can molding.

  On the other hand, for can lids, a pre-coating material that has been conventionally formed by coil-coating a paint has been used, but from the viewpoint of flavor retention and hygiene of the contents, research has been conducted on the use of a pre-coating material coated with a polyester resin. It is actively performed. In easy open can lids coated with polyester resin, due to a decrease in adhesion to the polyester resin, the delamination of the resin and metal in the vicinity of the score opening and the elongation of the resin in the opening induced by the delamination, that is, the feather A phenomenon called a ring is likely to occur, and particularly in a can lid immediately after retort sterilization, there is a problem in that an opening defect is likely to occur due to a decrease in adhesion to the resin.

From such a point of view, a method of forming an organic-inorganic composite film containing an organic compound containing carbon as a main component, a phosphorus compound, zirconium or a titanium compound (Patent Document 2), or an inorganic substrate as a main component. A method for forming a surface treatment layer and an organic surface treatment layer mainly composed of an aqueous phenol resin on the surface treatment layer has been proposed (Patent Document 3). Also, the use of anodizing treatment has been proposed mainly from the viewpoint of a lid (Patent Documents 4 and 5).
In addition, treatment of an aluminum material with a polyacrylic acid-zirconium compound has also been proposed (see Patent Document 6 and Non-Patent Document 1).
On the other hand, as a method for obtaining a zirconium oxide film, attempts have been made to form ZrO ₂ or the like by PVD, CVD, or the like, or apply an organic zirconium compound by a wet method and then heat-dry to obtain an oxide film.
Furthermore, studies have been conducted to form zirconium oxide powder and films on graphite and titanium substrates by cathodic electrolysis in an aqueous solution containing zirconium ions (see Non-Patent Documents 2, 3 and 4).

JP 52-131937 A JP-A-11-229156 JP 2001-121648 A JP-A-11-91034 JP 2002-266099 A Japanese Patent Laid-Open No. 06-322552 "Light Metal" (1990) p298-p304 "Materials Research Society Symposium Proceedings" (1988) VOL.121 p111-p114 "Journal of Electrochemical Society" (1991) VOL.138 No.7 p1939-p1942 “Journal of Electrochemical Society” (1991) VOL.138 No.7 p1942-p1946

However, in the method of forming an organic-inorganic composite film containing an organic compound containing carbon as a main component, a phosphorus compound, and a zirconium or titanium compound, the adhesion is improved to some extent, but the corrosion resistance is not sufficient, and the surface of the aluminum substrate In the method of forming a surface treatment layer mainly composed of an inorganic substance and an organic surface treatment layer mainly composed of an aqueous phenol resin on the surface, adhesion and corrosion resistance are improved to some extent, but the number of steps is increased and the use of a chemical solution is increased. There has been a problem that waste liquid treatment becomes complicated.
In the method using anodizing treatment, the primary adhesion is good, but the retort sterilization treatment after filling the contents tends to lower the adhesion, and the processing equipment is also costly and the treatment However, there is a problem that the cost is high because large electric power is required.
Furthermore, when the thickness of the base material itself such as an aluminum foil is thin, the proportion of the anodized film having poor solubility and workability at the time of anodizing treatment is increased, and the flexibility of the foil is reduced. There was a problem.

In the treatment of an aluminum material with a polyacrylic acid-zirconium compound, the coating film to be formed is an organic-inorganic composite coating, and the treatment method is basically a coating type treatment. There is a problem in terms of adhesion.
Furthermore, in many of the above prior arts, the metal material used is limited to an aluminum alloy, and the problems of the entire metal material cannot be solved.
On the other hand, it is also well known that ZrO ₂ or the like is formed on the surface of a metal material by PVD or CVD. However, since a vacuum is required, equipment is expensive and high-speed processing is difficult. Cost increases. In addition, it is difficult to ensure adhesion between the metal material substrate and the treatment film and corrosion resistance after processing.
Similarly, in a method of obtaining an oxide film by applying an organic zirconium compound by a wet method and then drying by heating, it is difficult to ensure adhesion between the metal material substrate and the treatment film and corrosion resistance after processing.

  Furthermore, as means for forming an oxide powder or oxide film by cathodic electrolysis in an aqueous solution containing zirconium ions, it is continuously applied on a graphite or titanium substrate in a 0.1 mol / liter-zirconium oxynitrate aqueous solution at pH 2.3. A method of cathodic electrolysis has been proposed. According to this method, when used for aluminum plate, galvanized steel plate, tin-plated steel plate, etc., the pH is low, the base material is easily dissolved, the bath concentration is high, and local precipitation is likely to occur. Therefore, not only is the film easily removed during washing with water after electrolysis, but the gel-like material falls into the bath when there is a flow in the treatment liquid, so the continuous high-speed treatment of the band-shaped metal material that inevitably stirs the bath There were problems such as being difficult. Also, if you rub your finger immediately after electrolysis, almost all of the precipitates will fall off, and the adhesion to the substrate will be weak, and it will be difficult to maintain the surface state in a high-temperature and high-humidity environment in terms of characteristics, and corrosion resistance There were problems with various properties such as adhesion.

  In order to solve the above-mentioned problems, the present inventors already have a surface-treated metal material having an inorganic surface treatment layer containing Zr, O, and F as a main component and not containing phosphate ions, and a surface treatment method thereof. Proposed (Japanese Patent Application No. 2002-340293, etc.) According to such a surface-treated metal material, the above-mentioned problems have been solved. However, the surface-treated metal material is further provided with an organic resin coating, and strict processing and retort sterilization are performed. In addition, it is desired to have better adhesion and corrosion resistance.

Therefore, the object of the present invention is excellent in environmental characteristics by non-chromium surface treatment, and also has a processing adhesion with a polyester resin coating in a high-processed portion, adhesiveness, corrosion resistance, dent resistance, scratch resistance, abrasion resistance, etc. properties superior cans or can lids resin-coated surface-treated metal sheet, and to provide a surface treatment method of the cans or can lids resin-coated surface-treated metal sheet.
Another object of the present invention, Ru der to provide a surface treatment method of high-speed processing by easy manufacturing cost of the can or the can lid resin-coated surface-treated metal sheet from an aqueous solution.

According to the first aspect of the surface-treated metal plate of the present invention, an inorganic surface treatment layer (A) mainly composed of an inorganic component and an organic surface treatment layer (B) mainly composed of an organic component are formed on the surface of the metal plate. Further, a resin-coated surface-treated metal plate having an organic resin coating (C) formed on at least one surface, wherein the inorganic surface-treated layer (A) is formed by intermittently performing cathodic electrolysis, It consists of an oxide of Zr containing no acid ion and containing F and a hydroxyl group, and the atomic ratio of O and Zr contained in the outermost surface of the inorganic surface treatment layer is 1 <O / Zr <10, The atomic ratio of Zr is 0.1 <F / Zr <2.5, the weight film thickness of Zr is 5 to 300 mg / m ² , and the organic surface treatment layer (B) has an Si content of 0. the 8~30mg / ^{m 2} of the silane coupling agent treatment layer or phenolic water-soluble organic compound A layer for the body, the organic resin coating (C) is a resin-coated surface-treated metal sheet for cans or can lids, characterized in that it consists of a thermoplastic polyester is provided.
According to the first aspect of the surface-treated metal plate of the present invention, an inorganic surface treatment layer (A) mainly composed of an inorganic component and an organic surface treatment layer (B) mainly composed of an organic component are formed on the surface of the metal plate. And a resin-coated surface-treated metal plate on which at least one surface is formed with an organic resin coating (C), wherein the inorganic surface treatment layer (A) is formed by intermittently performing cathodic electrolysis, It consists of an oxide of Zr containing F and a hydroxyl group, and the atomic ratio of P and Zr contained in the outermost surface of the inorganic surface treatment layer is 0 ≦ P / Zr <0.6, and the atomic ratio of O and Zr 1 <O / Zr <10, the atomic ratio of F and Zr is 0.1 <F / Zr <2.5, the weight film thickness of Zr is 5 to 300 mg / m ² , and the organic surface treatment layer (B) is a silane of the Si content 0.8~30mg / ^{m 2} coupling agent treatment layer or off And a layer mainly composed of Knoll water-soluble organic compound, an organic resin coating (c) is a resin-coated surface-treated metal sheet for cans or can lids, characterized in that it consists of a thermoplastic polyester is provided.
In the resin-coated metal plate of the present invention,
1. The inorganic surface treatment layer (B) contains 20 to 80 mg / m ² of SiO ₂ particles in terms of Si ;
2. The organic surface treatment layer (B) is a layer mainly composed of a phenolic water-soluble organic compound having a content in the range of 6 to 30 mg / m ^{2 in} terms of carbon atoms , on which the inorganic surface treatment layer is formed. (A) is formed,
Is preferred.

According to the present invention , cathodic electrolysis is also carried out in an aqueous solution containing Zr, F and water-dispersible silica having a particle size of 4 to 80 nm and having a phosphate ion concentration of less than 0.003 mol / liter as PO _4. After an inorganic film is formed on the surface of the metal plate at high speed by intermittently conducting 2 to 10 cycles in the range of energization time of 0.1 to 0.8 seconds, a phenolic water-soluble organic compound or a silane coupling agent is applied. There is provided a surface treatment method for a resin-coated surface-treated metal sheet for cans or can lids, which comprises drying to form an organic film, and further coating a thermoplastic polyester on the organic film .

According to the second aspect of the surface-treated metal plate of the present invention, an inorganic surface-treated layer (A) mainly composed of an inorganic component on the surface of the metal plate and an organic resin coating (C) on at least one surface of the inorganic surface-treated layer. A resin-coated surface-treated metal plate in which the inorganic surface-treated layer (A) is formed by intermittently performing cathodic electrolysis, does not contain phosphate ions, and contains Zr and Fr. The atomic ratio of O and Zr contained in the outermost surface of the inorganic surface treatment layer is 1 <O / Zr <10, and the atomic ratio of F and Zr is 0.1 <F / Resin-coated surface treatment for cans or can lids, wherein Zr <2.5, the weight film thickness of Zr is 5 to 300 mg / m ² , and the organic resin coating (C) is made of thermoplastic polyester A metal plate is provided.
According to the second aspect of the surface-treated metal plate of the present invention, an inorganic surface-treated layer (A) mainly composed of an inorganic component on the surface of the metal plate and an organic resin coating (C) on at least one surface of the inorganic surface-treated layer. ) Is a resin-coated surface-treated metal plate, wherein the inorganic surface-treated layer (A) is formed by intermittently performing cathodic electrolysis, and is made of an oxide of Zr containing F and a hydroxyl group, The atomic ratio of P and Zr contained in the outermost surface of the inorganic surface treatment layer is 0 ≦ P / Zr <0.6, the atomic ratio of O and Zr is 1 <O / Zr <10, F the atomic ratio of Zr is a 0.1 <F / Zr <2.5, the weight film thickness of Zr is 5 to 300 mg / ^{m 2,} said organic resin coating (C) consists of a thermoplastic polyester A resin-coated surface-treated metal plate for cans or can lids is provided.
According to the present invention , cathodic electrolysis is also carried out in an aqueous solution containing Zr, F and water-dispersible silica having a particle size of 4 to 80 nm and having a phosphate ion concentration of less than 0.003 mol / liter as PO _4. The inorganic film is formed on the surface of the metal plate at high speed by intermittently conducting 2 to 10 cycles in the range of energization time of 0.1 to 0.8 seconds, and further the thermoplastic polyester is coated on the inorganic film. A surface treatment method for a resin-coated surface-treated metal plate for cans or can lids is provided.

According to the present invention, an inorganic surface treatment layer (A) containing Zr, O, F as a main component and not containing phosphate ions is formed on a metal surface by cathodic electrolysis. By forming an organic surface treatment layer (B) mainly composed of organic components on the surface, or alternatively, at least Zr, O, and F as main components on the metal surface, and atoms of P and Zr contained in the outermost surface Surface with excellent high-speed productivity, environmental conservation, scratch resistance, adhesion, workability, and adhesion by forming an inorganic surface treatment layer with a ratio of 0 ≦ P / Zr <0.6 by cathodic electrolysis It is possible to provide a treated metal material at low cost, and by further forming an organic resin coating on this organic surface treatment layer, it is possible to further improve the processing adhesion and corrosion resistance with the organic resin coating And this resin coating In forming the metal cans and can lids from a metallic material, even in the portion where high machining of the neck portion and the like are attached, is that obtained and the excellent processability adhesion and corrosion resistance. Further, by forming a can lid from a metal material coated with this polyester resin, excellent openability can be obtained even after heat sterilization.
In the surface-treated metal material and resin-coated metal material of the present invention, it can be used effectively for metal lids such as metal cans and can lids, but it can also be used effectively for applications such as automobiles, home appliances, and building materials. can do.

In the surface-treated metal material of the present invention, the inorganic surface-treated layer (A) containing Zr, O, F as a main component and not containing phosphate ions, or the ratio of P to Zr being suppressed as much as possible, and It is an important feature that the organic surface treatment layer (B) mainly composed of organic components is formed on the metal material on the inorganic surface treatment layer (A).
In chemical conversion treatment and anodization treatment, which are conventional surface treatment methods for metal materials, sulfate ions and phosphate ions are easily contained in the film due to the film formation mechanism, and are component components in chemical conversion treatment. It is known that anions with large ionic radii such as anions in these membranes, especially phosphate ions, are likely to elute under high temperature and high humidity such as retort sterilization treatment. The adhesiveness and adhesiveness of the resin film provided on the surface-treated metal material will be reduced.
In the present invention, by controlling the amount of anion in the inorganic surface treatment layer, particularly phosphate ions or P / Zr, even when subjected to retort sterilization or storage over time under high temperature and high humidity conditions, Since the elution of the anion from is effectively suppressed, it is effectively prevented that the adhesiveness or adhesiveness of the resin film is lowered.

Further, in the surface-treated metal material of the present invention, the inorganic surface-treated layer contains Zr, O, and F as main components, so that the state of the outermost surface of the treated layer is maintained and stable even in a high-temperature and high-humidity environment. It is possible to maintain the surface, and as a result, it is possible to maintain the corrosion resistance and suppress the decrease in the adhesion or adhesiveness of the resin film.
That is, when the inorganic surface treatment layer contains Zr, O as main components and does not contain F, the structure of the treatment film is expected to be a structure such as ZrO _X (OH) _Y.
However, the hydroxyl group may be hydrated in a high-temperature and high-humidity environment to induce structural changes in the treatment layer and adversely affect various properties. By including a suitable amount of F, at least part of the hydroxyl groups substituted with F, by taking a stabilizing structure, such as _{ZrO X (OH) Y-Z} F Z, the processing layer under high temperature and high humidity environment It is possible to suppress structural changes and maintain a more stable surface.

Furthermore, in the surface-treated metal material of the present invention, on the inorganic surface-treated layer, an organic surface-treated layer mainly composed of a phenol-based water-soluble organic compound, or a silane having a Si amount of 0.8 to 30 mg / m ² It is also important that a coupling agent treatment layer is formed.
While the inorganic surface treatment layer described above mainly contributes to the corrosion resistance of the metal material, the organic surface treatment layer mainly contributes to adhesion with an organic coating such as a polyester resin. By laminating in order, even when subjected to high-level processing, it is possible to exhibit excellent processing adhesion and corrosion resistance with the organic resin coating.
Furthermore, in the surface-treated metal material of the present invention, the inorganic surface-treated layer may be formed on an organic surface-treated layer mainly composed of a phenol-based water-soluble organic compound.
In this case, the outermost surface is an inorganic surface treatment layer, but the inner part of the surface treatment layer close to the metal substrate is also an inorganic treatment layer that is electrolytically deposited on the thin film thickness portion of the organic surface treatment layer. It exists and it is thought that the part where organic and inorganic were mixed was formed. Therefore, the inorganic surface treatment covers the defects of the organic surface treatment layer, contributing to the corrosion resistance of the metal material. When the outermost inorganic surface treatment layer is cracked by processing, the underlying organic surface treatment layer Contributes to adhesion with organic coatings such as polyester resin, so even when subjected to severe processing such as neck processing in metal cans and rivet processing in can lids, excellent processing adhesion with organic resin coatings In addition, the excellent corrosion resistance of the inorganic treatment layer can be expressed.

Particularly in metal cans or can lids made from the surface-treated metal material of the present invention and a resin-coated metal material obtained by coating the surface-treated metal material with an organic resin, in particular, a polyester resin, it has excellent work adhesion and corrosion resistance. Since the above-mentioned resin-coated metal material is used, the processing adhesion of the polyester resin film at the high-processed part, the corrosion resistance (dent resistance) from the cracked part of the polyester resin film caused by impact, and further during retort sterilization It is possible to improve the adhesion of the glass, and the corrosion due to the amount of permeated ions is suppressed, and the openability of the easy open can lid can be improved. This is the result of the examples described later. It is clear from
That is, a metal lid and a metal can (Comparative Examples 1, 8, 11, and 18) made of a resin-coated metal material in which a polyester film is directly formed on an inorganic surface treatment layer formed on a metal material surface are untreated metal. Forming a polyester film on a metal can (Comparative Example 12) made of a resin-coated metal material that directly forms a polyester film on the material surface, or on a silane coupling agent layer or a phenolic organic film formed on the metal material surface Compared with metal lids and metal cans (Comparative Examples 2, 3, 9, 10, 16, 17) made of resin-coated metal material, the processing adhesion in high-processed parts, and the adhesion and corrosion resistance after retort sterilization In Comparative Example 1, 8, 11, 18 the results obtained in practical use were obtained in the surface treated metal material provided with a combination of the inorganic surface treatment layer and the organic surface treatment layer. Compared with metal lids and metal cans (Examples 1 to 18) made of the resin-coated metal material of the present invention with a coating formed thereon, the processing adhesion at the high processing portion on the outer surface of the metal can, the adhesion after retort sterilization, and It is clear that the corrosion resistance is inferior, and it is understood that the surface-treated metal material and the resin-coated metal material of the present invention have extremely excellent work adhesion and corrosion resistance.
The most remarkable effect of molding a resin-coated metal material with a polyester film on the silane coupling agent layer or phenolic organic surface treatment layer formed on the surface of the metal material is a container after molding. In the heat setting step, a re-adhesion effect is obtained by the silane coupling agent layer and the phenol-based organic surface treatment layer being again compatible with the polyester. In other words, the adhesion at the polyester-metal interface is reduced by molding, but the silane coupling agent layer and the phenolic organic surface treatment layer are compatible with the polyester without heating to the melting point of the polyester or higher in the heat setting process. This will restore the adhesion.
If the inorganic surface treatment layer is not present, it is difficult to suppress the change in the surface of the metal substrate during retort, which is not preferable from the viewpoint of corrosion resistance. On the other hand, since the adhesion force is restored by the mechanism as described above, the inorganic surface treatment layer does not necessarily have to be under the organic surface treatment layer. That is, when there is an inorganic surface treatment layer on the organic surface treatment layer, the organic surface treatment layer appears from the portion where the inorganic surface treatment layer is cracked in the molding process, and it is considered that the same effect is exhibited during heat setting. However, when an inorganic surface treatment layer is formed on the organic surface treatment layer, it is necessary to form an inorganic surface treatment layer having excellent adhesion under wet conditions by electrolysis, so that the organic surface treatment as a base is used. The conductivity of the layer is an important issue. In this regard, the phenol-based organic surface treatment layer can be easily secured by forming a thin film by treating it from a chemical conversion treatment agent using phosphoric acid or hydrofluoric acid, but the silane coupling agent layer is However, it is difficult to control the film thickness, and it is difficult to achieve sufficient performance with a thin film. Therefore, as the organic surface treatment layer when the inorganic surface treatment layer is formed thereon, an organic coating mainly composed of a phenol-based water-soluble organic compound can be suitably used.

Furthermore, in the surface treatment method for a metal material of the present invention, when forming the inorganic surface treatment layer (A), Zr and F are contained, and the phosphate ion concentration is less than 0.003 mol / liter as PO _4. More preferably, it is an important feature that the cathodic electrolysis is carried out in an aqueous solution not containing phosphate ions.
According to the cathodic electrolysis treatment, the control range of the Zr weight film thickness per unit time can be greatly expanded as compared with the conventional chemical conversion treatment film, and a film can be generated according to the application.
On the other hand, in the conventional chemical conversion treatment, the film formation rate is limited because it depends on the chemical reaction depending on the composition of the treatment solution. For this reason, the film thickness is limited in the high-speed treatment, whereas the cathode electrolytic treatment. Then, since an electrolytic reaction is utilized, high-speed processing of film formation becomes possible. In addition, in the chemical conversion treatment and anodizing treatment, sulfate ions and phosphate ions are easily contained in the film due to the film formation mechanism, and the chemical conversion treatment becomes a constituent component, so it is difficult to control the amount of anion as described above. is there. On the other hand, since cathodic electrolysis uses an aqueous solution of fluoride, it is possible to form a film in which the amount of anions having a large ionic radius such as sulfate ions and phosphate ions is controlled. It is.
In the metal material surface treatment method of the present invention, it is particularly preferable to intermittently perform the cathodic electrolysis treatment. That is, by providing a stop time in the middle of electrolysis instead of continuously performing electrolysis, the O / Zr ratio of the surface treatment layer can be controlled, and the deposition efficiency can be increased as compared to continuous electrolysis. High-quality and high-speed processing becomes possible.

In the second aspect of the surface-treated metal material of the present invention, the above-described inorganic surface treatment layer has Si.
It is an important feature that O ₂ particles are contained.
Conventionally, silica is known to have a function of delaying the corrosion rate of a steel sheet or the like by maintaining a barrier coating on the alkali side and the corrosion environment against the ingress of corrosion factors. By including water-dispersible silica in the aqueous solution used for the treatment, the water-dispersible silica bonds with oxygen atoms present in the inorganic surface treatment layer, and exists as chemically stable amorphous silicon oxide, resulting in siloxane bonds. It is possible to form a dense network structure composed of an inorganic surface treatment layer, and it is also possible to obtain an effect of forming a stable film, processing adhesion in a high processing part, adhesion after retort sterilization, and corrosion resistance In Example 11, it is clear that practically satisfactory results are obtained (Example 11). Further, in the surface-treated metal material formed by forming an organic surface treatment layer on the SiO ₂ particle-containing inorganic surface treatment layer, particularly excellent results are obtained in processing adhesion at a high processing portion, adhesion after retort sterilization, and corrosion resistance. It is clear that it is obtained (Examples 6, 10, 13, and 17).
Furthermore, in the surface treatment method for a metal material of the present invention, in particular, cathodic electrolysis in an aqueous solution containing Zr, F and water-dispersible silica and having a phosphate ion concentration of less than 0.003 mol / liter as PO _4. It is an important feature to form an inorganic coating containing SiO ₂ particles by treatment. Conventionally, when performing galvanization or the like, there has been known a method for improving the corrosion resistance as a galvanized steel sheet by subjecting zinc and silica to composite plating by electrolysis using a treatment liquid in which silica particles are dispersed ( JP-A-7-278892). However, as a method of forming a dense coating mainly composed of silica particles with good corrosion resistance on the surface-treated metal plate, (1) silica is added to a processing agent such as a silane coupling agent or an aqueous resin to form an organic coating. (2) A method of treating in an aqueous solution containing inorganic metal ions (JP-A 2000-167482, JP-A 2001-240979, 2001-316845, etc.) JP-A-63-50484, JP-A-4-176875, JP-A-11-335862, etc.).
However, the method (1) has a problem in terms of the stability of the treatment liquid, and further, since a film mainly composed of organic components is formed, the film forming property of silica itself can be sufficiently exhibited. In addition, sufficient effects were not obtained with respect to corrosion resistance. On the other hand, in the method (2), it is difficult to obtain a film having good adhesion to the surface-treated metal plate, and the use of Al ions (Japanese Patent Laid-Open No. 11-335862) improves the film-forming property of silica. However, depending on the adsorption action of silica particles, it is difficult to form a film containing a sufficient concentration of silica, and as a result, a sufficient effect on corrosion resistance was not obtained.
According to the present invention, it is possible to arbitrarily disperse silica in a zirconium inorganic coating mainly composed of oxide by cathodic electrolysis, and not only galvanized steel sheet but also mainly composed of silica particles on various metal plate surfaces. Thus, it becomes possible to form a dense film having good corrosion resistance. Moreover, a silane coupling agent layer is formed on the silica-dispersed inorganic surface treatment coating and further coated with a polyester resin, whereby a siloxane bond is formed between the inorganic coating and the silane coupling agent layer. A compatible action occurs between the film and the silane coupling agent layer, and an unprecedented effect of improving adhesion can be obtained.

(Surface-treated metal material)
<Inorganic surface treatment layer>
In the surface-treated metal material of the present invention, as described above, it is one important feature that the inorganic surface-treated layer of the surface-treated metal material does not contain phosphoric acid. It is clear from
That is, in FIG. 1, a zirconium phosphate chemical conversion treatment 1, which is a representative example of a surface treatment film containing phosphate ions, and an inorganic surface treatment 2 containing Zr, O, and F not containing phosphate ions according to the present invention, X An example was shown in which the P2p peak was measured and compared with a line photoelectron spectrometer (hereinafter referred to as XPS). The chemical conversion surface 1 contains phosphoric acid in the treatment solution, so that the peak of P2p is clearly recognized, whereas the peak of P2p is not recognized in the inorganic surface treatment 2 according to the present invention. It is clear from FIG.

  On the other hand, FIG.2 and FIG.3 is a figure which shows the O1s peak which performed the depth direction analysis which used sputtering together from the surface about the said zirconium phosphate chemical conversion treatment 1 and the inorganic surface treatment 2 of this invention. In FIGS. 2 and 3, the peak obtained from the outermost surface is located at the bottom, and the peak closer to the metal substrate away from the surface is shown on the upper side. 2 and 3, since there is O derived from surface contamination on the outermost surface, it cannot be determined from the energy position, but by performing depth direction analysis, a chemical compound having an O1s peak derived from phosphate ions is obtained. The binding energy position 11 of the O1s peak of the treatment 1 appears on the higher energy side as compared to the binding energy position 21 of the O1s peak of the inorganic surface treatment film 2 containing Zr, O, and F not containing phosphate ions according to the present invention. ing. From this, in the surface-treated metal material of the present invention, it is clear that the surface-treated layer does not contain phosphoric acid.

Furthermore, in the surface-treated metal material of the present invention, the atomic ratio of P and Zr contained in the outermost surface of the inorganic surface-treated layer of the surface-treated metal material is more preferably in the range of 0 ≦ P / Zr <0.6. Is an important feature in the range of 0 ≦ P / Zr <0.1. When P / Zr is larger than the above range, a large amount of phosphoric acid or P as an impurity component is present in the coating, and sufficient adhesion cannot be obtained.
The inorganic surface-treated layer of the surface-treated metal material of the present invention contains Zr, O, and F as main components, and particularly the outermost surface layer has an O / Zr value in the range of 1 to 10, particularly in the atomic ratio. It is desirable to be in the range of 1-5. This is because when O / Zr is smaller than the above range, it is difficult to form a film, whereas when O / Zr is larger than the above range, sufficient adhesion cannot be obtained.
Furthermore, in the surface-treated metal material of the present invention, the value of F / Zr contained in the outermost surface of the inorganic surface-treated layer of the surface-treated metal material is in the range of 0.1 to 2.5 in terms of atomic ratio. It is desirable to be in the range of 5 to 2.0. When F / Zr is smaller than the above range, the adhesive structure in a high-temperature and high-humidity environment tends to be lowered without taking the stabilizing structure like ZrO _X (OH) _YZ F _Z described above, while F Even when / Zr is larger than the above range, although the ionic radius is small, the amount of anion with respect to Zr becomes excessive, and the adhesion is also lowered.

As a method for measuring the atomic ratio of P / Zr, O / Zr, and F / Zr, the peak of P2p, O1s, F1s, and Zr3d is measured by XPS, and the atomic concentration is obtained from the value obtained by analysis software. it can. However, the silica-dispersed samples, since a dense silica film is formed on the outermost surface, when the seek O / Zr, peaks of Si2p be measured beforehand at the same time, from the atomic concentration of Si of O corresponding to SiO ₂ It is necessary to obtain the concentration, recalculate the atomic concentration of each element excluding SiO ₂ from the whole, and obtain the atomic ratio of O / Zr again.
If the surface-treated metal material used for measurement is in a clean state, the surface is analyzed as it is. After the organic resin is bonded or fused, it is necessary to first remove the organic resin layer by immersing it in a boiled hydrogen peroxide solution for several minutes.
Samples that are not clean and samples after removal of the organic resin coating layer described above, when the sum of major elements such as C, O, F, Zr, and base metal elements is 100% in the C layer derived from organic matter, The P / Zr, O / Zr, and F / Zr ratios at the time when the contaminated layer is lightly removed by Ar sputtering until C becomes 10% or less in atomic concentration can be obtained. Also, after obtaining the peak area after background removal for each element of P, O, F, and Zr by a regular method, the atomic concentration of each element is obtained using the relative sensitivity coefficient of the measuring device, and P / Zr, O The / Zr and F / Zr ratios may be determined by calculation.
FIG. 4 shows an example of the Zr3d peak 3. A range surrounded by the reference line 4 and the peak 3 of the background is a peak area 5. Needless to say, since the atomic ratio varies depending on how the background is drawn, attention should be paid to how the background is drawn.
In addition, the peak of P2p is easily confused with the plasmon loss peak of Al2s, so care must be taken. In particular, when the peak considered to be P2p increases monotonously with the Al2s peak as sputtering is performed in the depth direction, the presence of P element is confirmed by other methods such as characteristic X-ray analysis after surface coating isolation. There is a need to.

As the film thickness, the weight film thickness of Zr, is preferably between the 5 to 300 mg / ^{m 2,} not sufficient homogeneous product is difficult coverage of the coating is less than 5 mg / ^{m 2,} If it exceeds 300 mg / m ² , the adhesiveness is lowered by processing, which is not preferable.
As a measuring method of Zr film thickness, it quantifies with a commercially available fluorescent X-ray analyzer. First, a calibration curve indicating the relationship between the Zr film thickness and the X-ray intensity of Zr is created from a plurality of samples with known Zr weight film thickness, and then the X-ray intensity of Zr measured using an unknown sample is used as the calibration curve. Based on the weight film thickness.

When SiO ₂ particles are included in the inorganic surface treatment layer, the surface coverage of Si contained in the outermost surface of the inorganic surface treatment layer of the surface treatment metal material is 10 to 30%, particularly 15 to 30% in terms of atomic ratio. It is desirable to be in range. When the surface coverage of Si is smaller than the above range, it is difficult to form a film. On the other hand, when the atomic concentration of Si is larger than the above range, the effect of forming a stable film by blending water-dispersible silica is difficult. This is because you cannot get enough.
As for the surface coverage of Si, the main elements as constituent components were measured by XPS in the same way as the measurement of the atomic ratio described above, and the atomic concentration of Si2p when the whole was defined as 100% was defined as the surface coverage. . However, as in the measurement of the atomic ratio, it is necessary to obtain the concentration at the time when the contaminated layer is lightly removed by Ar sputtering until C becomes 10% or less in atomic concentration.

  Further, in the surface-treated metal material of the present invention, when the metal material substrate to be treated is made of an easily damaged metal such as an aluminum alloy or an aluminum-coated steel plate, fine particles having a particle size of 10 to 100 nm are precipitated on the surface, The metal material surface can be coated. This is considered to be oxide fine particles mainly composed of Zr, and the effect of improving the scratch resistance, wear resistance, etc. is obtained by modifying the aluminum surface by cathodic electrolysis without performing a special pretreatment.

<Organic surface treatment layer>
In the surface-treated metal material of the present invention, the organic surface treatment layer is present together with the inorganic surface-treating layer is an organic coating mainly composed of organic components, particularly (i) Si amount 0.8~30mg / m ² A silane coupling agent-treated layer, or (ii) a layer mainly composed of a phenol-based water-soluble organic compound.
(I) Silane coupling agent treatment layer In the surface-treated metal material of the present invention, a silane coupling agent treatment layer having an Si amount of 5030 mg / m ² or less is further formed on the inorganic surface treatment layer. Is particularly preferred.
The silane coupling agent that forms the silane coupling agent treatment layer has a reactive group that chemically bonds to the thermoplastic polyester resin and a reactive group that chemically bonds to the inorganic surface treatment layer, and includes an amino group, an epoxy group, a methacryloxy group. Containing hydrosilanes with organic substituents such as methyl groups, phenyl groups, epoxy groups, mercapto groups, and the like, and reactive groups such as mercapto groups and hydrolyzable alkoxy groups such as methoxy groups and ethoxy groups Silanes containing alkoxy groups can be used.
Specific examples of silane coupling agents that can be suitably used in the present invention include γ-APS (γ-aminopropyltrimethoxysilane), γ-GPS (γ-glycidoxypropyltrimethoxysilane), BTSPA ( Bistrimethoxysilylpropylaminosilane), N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and the like.
The silane coupling agent treatment layer is preferably formed so that the Si amount is 0.8 to 30 mg / m ² , particularly 3 to 15 mg / m ² . If the Si amount is less than the above range, the work adhesion is inferior. If the Si amount is more than the above range, the unreacted silane coupling agent self-condenses, so that satisfactory work adhesion and corrosion resistance can be obtained. Can not.

The organic surface treatment layer composed of a silane coupling agent treatment layer is particularly preferably formed on an inorganic surface treatment layer containing SiO ₂ particles. In this case, the weight-thickness ratio M / Si of the inorganic surface treatment layer is more preferably 0.3 to 3.5, and when M / Si is smaller than the above range, the cohesive force of the coating itself is reduced. This is because it is difficult to form a stable film, and when M / Si is larger than the above range, the dispersion of SiO ₂ particles becomes insufficient.

(Ii) Layer mainly composed of phenol-based water-soluble organic compound In the surface-treated metal material of the present invention, it is particularly preferable that the inorganic surface-treated layer and a layer mainly composed of phenol-based water-soluble organic compound exist. The inorganic surface treatment layer may be on or below the organic or organic inorganic surface treatment layer mainly composed of the phenol-based water-soluble organic compound layer.
Here, the case where the inorganic surface treatment layer is present on the phenolic water-soluble organic compound layer refers to the case where the inorganic surface treatment layer is formed after the formation of the layer mainly composed of the phenolic water-soluble organic compound. ing. In this case, the outermost surface is an inorganic surface treatment layer, but the inner part of the surface treatment layer close to the metal substrate is also an inorganic treatment layer that is electrolytically deposited on the thin film thickness portion of the organic surface treatment layer. It exists and it is thought that the part where organic and inorganic were mixed was formed.
As a phenol type water-soluble organic compound, following formula (1)
OH
｜
− Φ −CH ₂ − (1)
｜
X
In the formula, φ represents a benzene ring, X represents a hydrogen atom or the following formula (2)
Z = —CH ₂ —N—R ₁ (2)
｜
R ₂
In the formula, each of R ₁ and R ₂ represents Z represented by: an alkyl group having 10 or less carbon atoms, an alkyl group having 10 or less carbon atoms, or a hydroxyalkyl group having 10 or less carbon atoms; The rate shall be 0.2-1.0 per benzene ring,
It is preferable that it is a phenol resin which consists of a repeating unit represented by these.
Moreover, a tannin can be mentioned as another example of a phenol-type water-soluble organic compound. Tannin, also called tannic acid, is a general term for aromatic compounds having a complex structure having a phenolic hydroxyl group.
Examples of tannins include hameli tannins, oyster tannins, chatannins, pentaploid tannins, gallic tannins, milovalan tannins, dibidi tannins, argarovira tannins, valonia tannins, catechin tannins and the like. Tannin preferably has a number average molecular weight of 200 or more.
In the organic surface treatment layer mainly composed of the above-mentioned phenol-based water-soluble organic compound, the organic surface treatment layer has a phenol content of ^{3 to} 75 mg / m ² , particularly 6 to 30 mg / m ^{2 in} terms of carbon atoms. It is desirable to contain a water-soluble organic compound. When the amount is less than the above range, the adhesion of the organic surface treatment film is inferior. On the other hand, when the amount is more than the above range, the film thickness of the organic surface treatment film becomes larger than necessary and the adhesion and corrosion resistance are lowered.
The organic surface treatment layer mainly composed of the phenol-based water-soluble organic compound is an organic-inorganic layer formed by using an organic compound mainly composed of carbon and a surface treatment agent containing a phosphorus compound and a zirconium or titanium compound. It may be a composite layer.

5 to 7 are cross-sectional views showing examples of the surface-treated metal material of the present invention. The surface-treated metal material 31 shown in FIG. 5 includes a metal material base 32, an inorganic surface treatment layer 33 having Zr, O, and F as main components provided on the surface of the base, and an organic component on the inorganic surface treatment layer 33. An organic surface treatment layer 34 mainly composed of is formed.
The surface-treated metal material 31 shown in FIG. 6 is the same as FIG. 5 in that it has an inorganic surface-treated layer 33 and an organic surface-treated layer 34 containing Zr, O, and F as main components. The base 32 is composed of a metal material 32a and a metal plating layer 32b. As the metal plating layer 32b covered with the metal material 32a occupying most of the base 32, a layer having a role of enhancing the corrosion resistance of the metal material 32a is used as will be described later.
In the surface-treated metal material 31 shown in FIG. 7, an inorganic surface treatment layer 33 containing Zr, O, and F as main components is formed on a metal material substrate 32, and SiO ₂ particles are contained in the inorganic surface treatment layer 33. 35 is contained.

(Metal material substrate)
As the metal material substrate used in the present invention, various surface-treated steel plates and light metal materials such as aluminum are used. As the surface-treated steel sheet, the cold-rolled steel sheet is annealed and then secondarily cold-rolled, and galvanized, tin-plated, nickel-plated, aluminum-plated, or the like can be used as a surface-treated steel sheet. In addition, an aluminum clad steel plate or the like can also be used. The metal formed by plating or cladding on the surface side of the metal material base is attached for the purpose of improving various properties such as the corrosion resistance, wear resistance, and electrical conductivity of the metal located on the center side. Specifically, it is almost always given for the purpose of improving the corrosion resistance. As the light metal material, an aluminum alloy is used in addition to so-called pure aluminum. The original thickness of the metal material is not particularly limited and varies depending on the type of metal and the use or size of the container, but the metal plate generally has a thickness of 0.10 to 0.50 mm, and among these, the surface In the case of a treated steel plate, the thickness may be 0.10 to 0.30 mm, and in the case of a light metal plate, the thickness may be 0.15 to 0.40 mm.

(Surface treatment method)
In the surface treatment method for a metal material of the present invention, cathodic electrolysis is performed in an aqueous solution containing Zr and F and having a phosphate ion concentration of less than 0.003 mol / liter as PO ₄ , and more preferably not containing phosphoric acid. This is an important feature.
As described above, according to the cathodic electrolysis treatment, the control range of the Zr weight film thickness per unit time can be greatly expanded as compared with the conventional chemical conversion treatment coating, and the coating can be generated according to the application. .

Further, in the surface treatment method of the present invention, the cathodic electrolysis treatment is intermittently performed, that is, the electrolysis is performed by providing a stop time in the middle of electrolysis and repeating the energization and stop cycles a plurality of times in the stirred aqueous solution. It is preferable to perform intermittent electrolysis. FIG. 8 shows the relationship between the total electrolysis time, which is the sum of the energization time and the stop time, and the Zr weight film thickness. As is apparent from FIG. 8, it is more intermittent than when the cathode electrolysis is performed continuously. It is understood that the rate of formation of the Zr heavy film thickness is faster when the cathode electrolysis is performed.
This is because, when electrolysis is performed continuously, concentration polarization occurs in the vicinity of the cathode and precipitation is inhibited. On the other hand, by intermittent electrolysis, Zr, Ions such as O, OH, and F are supplied, and a loose film formed on the cathode, that is, a film having a large O / Zr ratio is removed. As a result, the formation rate of the Zr weight film thickness is high and higher. It will provide a quality film.
The energization and stop cycle is not limited to this, but the energization time is 0.1 to 0.8 seconds and the stop time is 0.3 to 1.5 seconds. Is preferred.

  The aqueous solution used in the surface treatment method of the present invention preferably has a bath concentration in the range of 0.010 to 0.050 mol / liter, particularly 0.015 to 0.035 mol / liter as Zr. In the cathodic electrolysis treatment, it is difficult to form a uniform film due to local electrolysis concentration on the metal plate with a dense oxide film formed on the surface, and a special pretreatment is required. However, in the present invention, electrolytic treatment is performed in a low concentration bath in order to produce a surface treatment film that is as uniform as possible without performing any special pretreatment. That is, if the bath concentration is higher than the above range, nucleation occurs locally, and electrolysis concentrates preferentially in that portion, resulting in the formation of a non-uniform film, while the bath concentration is higher than the above range. Is low, the electric conductivity of the bath is low, which causes an increase in power required for the treatment, which is not preferable.

  The aqueous solution used in the surface treatment method of the present invention preferably has a bath concentration in the range of 0.010 to 0.050 mol / liter, particularly 0.015 to 0.035 mol / liter as Zr. In the cathodic electrolysis treatment, it is difficult to form a uniform film due to local electrolysis concentration on the metal plate with a dense oxide film formed on the surface, and a special pretreatment is required. However, in the present invention, electrolytic treatment is performed in a low-concentration bath in order to produce a surface treatment film that is as uniform as possible without performing any special pretreatment. That is, if the bath concentration is higher than the above range, nucleation occurs locally, and electrolysis concentrates preferentially in that portion, resulting in the formation of a non-uniform film, while the bath concentration is higher than the above range. Is low, the electric conductivity of the bath is low, which causes an increase in power required for the treatment, which is not preferable.

The aqueous solution used for the surface treatment is preferably an aqueous solution having a pH of 3.0 to 8.0, more preferably a pH of 3.5 to 6.5. Examples of the Zr agent used for the treatment liquid include potassium zirconium fluoride KZrF ₆ and fluoride. Zirconium ammonium (NH ₄ ) ₂ ZrF ₆ , zirconium ammonium carbonate solution (NH ₄ ) ₂ ZrO (CO ₃ ) _{2 and the} like can be used. Zirconium ions and fluorine ions can also be supplied from separate agents, such as zirconium oxynitrate ZrO (NO ₃ ) ₂ and zirconium oxyacetate ZrO (CH ₃ COO) ₂ as Zr agents, and sodium fluoride NaF as F agents. , Potassium fluoride KF, ammonium fluoride NH ₄ F, or the like can be used.
The F concentration in the bath is preferably in the range of 0.03 mol / liter to 0.35 mol / liter as F. If the fluorine ion concentration is lower than the above range, a gel-like substance is formed on the metal surface that is the cathode, which hinders handling during continuous production and is unstable over time in a high-temperature and high-humidity environment. Since it becomes a surface, it is not preferable, and when the bath concentration is higher than the above range, it is not preferable because precipitation efficiency tends to be inhibited and precipitates are easily generated in the bath.

It is particularly preferable to add water-dispersible silica to the aqueous solution used for the surface treatment. The water-dispersible silica improves the corrosion resistance and the film-forming property as described above, and is not particularly limited, but examples thereof include spherical silica, chain silica, aluminum modified silica, and the like. May include colloidal silica such as SNOWTEX N and SNOWTEX UP (both manufactured by Nissan Chemical Industries) and fumed silica such as Aerosil (manufactured by Nippon Aerosil Co., Ltd.). Commercially available silica gel such as Adelite AT-20A (Asahi Denka Kogyo Co., Ltd.) can be used as silica gel such as Snowtex PS (Nissan Chemical Co., Ltd.) and aluminum modified silica. The particle size of silica to be blended in the treatment liquid is preferably in the range of 4 to 80 nm, particularly 4 to 30 nm. Particles below this range are difficult to obtain, and above this range, cracks are likely to occur during processing, which is not preferable. The amount of silica in the coating is, 3 to 100 mg / ^{m 2} in the amount of Si, it is desirable in particular in the range of 20 to 80 mg / ^{m 2.} Below this range, the effect of compounding silica is poor, and above this range, the film itself is insufficient in cohesive strength, which is not preferable.

  Furthermore, nitrate ions, peroxides, and complexing agents may be added to the aqueous solution used for the surface treatment, if necessary. Nitrate ions have the effect of maintaining the stability of the deposited state during electrolysis over a long period of time, and nitric acid, sodium nitrate, potassium nitrate, ammonium nitrate, and the like can be used as an ion source. The peroxide has the effect of generating oxygen in an aqueous solution and suppressing concentration polarization near the cathode surface, and is particularly useful when the bath is poorly stirred. As the peroxide, for example, hydrogen peroxide, ammonium peroxodisulfate, potassium peroxodisulfate, sodium peroxoborate, sodium peroxocarbonate, sodium peroxodisulfate and the like can be used. Further, the complexing agent has a function of suppressing the formation of precipitates in the bath, such as ethylenediaminetetraacetic acid, sodium ethylenediaminetetraacetate, citric acid, sodium citrate, boric acid, nitrilotriacetic acid, sodium nitrilotriacetate, Cyclohexanediaminetetraacetic acid, glycine, or the like can be used. If the concentration of nitrate ion, peroxide, and complexing agent is too high, the precipitation efficiency tends to be inhibited. The concentration of nitrate ion, peroxide, and complexing agent is 0.2 mol / liter. The following is preferable.

As the pretreatment of the metal material substrate, degreasing, washing with water, if necessary, pickling and washing with water, cleaning the surface, and stirring the aqueous solution at a temperature of 30 to 65 ° C. while stirring the current density Is 0.5 to 100 A / dm ² , and a cathodic electrolysis with a total electrolysis time of 0.3 to 20 seconds by a discontinuous electrolysis method in which a cycle of energization and stop is repeated, and finally, a suitable surface structure is obtained by washing with water. be able to.
As the counter electrode plate corresponding to the anode side, a titanium plate coated with iridium oxide is preferably used. As a condition of the counter electrode plate, it is desirable that the counter electrode material is an insoluble anode having a small oxygen overvoltage without being dissolved in the treatment liquid during electrolysis.

In the surface treatment method of the present invention, after the inorganic surface treatment layer is formed, an organic component, particularly (i) a silane coupling agent or (ii) a phenol-based water-soluble organic compound is applied and dried. It is particularly preferred to form an organic coating.
In order to form the organic coating on the inorganic surface treatment layer, the above-described phenol-based water-soluble organic compound or silane coupling agent solution is applied on the inorganic surface treatment layer, or the phenol-based water-soluble organic compound or silane coupling agent solution. It can be formed by immersing the surface-treated metal material on which the inorganic surface-treated layer is formed, removing the excess solution with a squeeze roll, and then drying by heating under a temperature condition of 80 to 180 ° C. it can.

(Resin-coated metal material)
The resin-coated metal material of the present invention is formed by coating at least one surface of the surface-treated metal material with a layer made of an organic resin, particularly a polyester resin. Therefore, it has excellent corrosion resistance and dent resistance.
In FIG. 9 which shows sectional drawing of an example of the resin-coated metal material of the present invention, the resin-coated metal material 41 is formed on the metal material base 42 and the base surface when viewed from the inner surface side (right side in the figure) when used as a container. The provided inorganic surface treatment layer 43 containing Zr, O, and F as main components, the organic surface treatment layer 44 provided on the inorganic surface treatment layer 43, and the polyester resin coating layer 45 provided thereon. It has a multilayer structure. In the example of FIG. 9, an outer surface resin protective layer 46 is provided on the outer surface side (left side in the figure) when used as a container through the inorganic surface treatment layer 43, and the outer surface resin protective layer 46 is formed of the polyester resin. Even if it is the same polyester resin as the coating layer 45, it may consist of a different polyester resin, and may consist of a different resin.

  In FIG. 10 showing another example of the resin-coated metal material, the resin-coated metal material 41 is formed on the inorganic surface treatment layer 43 containing Zr, O, and F as main components, and on the side of the substrate 42 that is the inner surface of the container. Although it is the same as that of FIG. 9 in that it includes an applied organic surface treatment layer 44, a polyester resin layer 45, and an outer surface resin protective layer 46 provided on the outer surface side, the substrate 42 is made of a metal material 42a. Further, the polyester resin layer 45 has a laminated structure of a polyester resin surface layer 45a and a polyester resin lower layer 45b. As described above, the metal plating layer 42b covered with the metal material 42a occupying most of the base 42 has a role of enhancing the corrosion resistance of the metal material 42a. As described above, the polyester resin lower layer 45b is excellent in adhesion to the metal substrate, while the polyester resin surface layer 45a is excellent in content resistance.

In FIG. 11 showing another example of the resin-coated metal material, the resin-coated metal material 41 has an inorganic surface treatment layer 43 mainly composed of Zr, O, and F formed on the base 42. Are the same, but the inorganic surface treatment layer 43 contains SiO ₂ particles 47, and the polyester resin layer 45 applied to the container inner surface side of the substrate 42 and the outer surface resin applied to the outer surface side. A protective layer 46 is formed.

(Organic resin coating layer)
In the resin-coated metal material of the present invention, the organic resin provided on the metal material is not particularly limited, and examples thereof include various thermoplastic resins and thermosetting or thermoplastic resins.
As the organic resin, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, olefin resin film such as ionomer, or polyester film such as polybutylene terephthalate, or A non-stretched or biaxially stretched thermoplastic resin film such as a nylon film such as nylon 6, nylon 6, 6, nylon 11 or nylon 12, a polyvinyl chloride film or a polyvinylidene chloride film may be used. When an adhesive is used in the lamination, a urethane adhesive, an epoxy adhesive, an acid-modified olefin resin adhesive, a copolyamide adhesive, a copolyester adhesive (thickness: 0.1 to 5. 0 μm) is preferably used. Further, a thermosetting paint may be applied to the surface-treated metal plate side or the film side in a thickness range of 0.05 to 2 μm, and this may be used as an adhesive.

Further, as organic resins, modified epoxy paints such as phenol epoxy and amino-epoxy, vinyl chloride-vinyl acetate copolymer, saponified vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer , Epoxy-modified-, epoxy-amino-modified, epoxy-phenol-modified-vinyl paint or modified vinyl paint, acrylic paint, thermoplastic or thermosetting paint, such as synthetic rubber paint such as styrene-butadiene copolymer, alone or 2 It may be a combination of more than one species.
Among these, a polyester resin is most preferably used as a container material. Examples of the polyester resin include thermoplastic polyesters derived from an alcohol component mainly composed of ethylene glycol or butylene glycol and an acid component such as an aromatic dibasic acid such as terephthalic acid, isophthalic acid, or naphthalenedicarboxylic acid.
Of course, polyethylene terephthalate itself can be used as the polyester, but lowering the maximum crystallinity that the film can reach is desirable in terms of impact resistance and processability. It is preferable to introduce a copolymer ester unit of It is particularly preferable to use a copolyester having a melting point of 210 to 252 ° C. mainly composed of ethylene terephthalate units or butylene terephthalate units and containing a small amount of other ester units. The melting point of homopolyethylene terephthalate is generally 255 to 265 ° C.

Generally, 70 mol% or more, particularly 75 mol% or more of the dibasic acid component in the copolyester is composed of a terephthalic acid component, and 70 mol% or more, particularly 75 mol% or more of the diol component is composed of ethylene glycol or butylene glycol, It is preferable that 1 to 30 mol%, particularly 5 to 25 mol% of the dibasic acid component is composed of a dibasic acid component other than terephthalic acid.
Dibasic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid: alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid: succinic acid, adipic acid, sebacic acid, dodecanedioic acid, etc. Or a combination of two or more of the aliphatic dicarboxylic acids: As the diol component other than ethylene glycol or butylene glycol, propylene glycol, diethylene glycol, 1,6-hexylene glycol, cyclohexane dimethanol, bisphenol A 1 type, or 2 or more types, such as an ethylene oxide adduct. Of course, the combination of these comonomers is preferably such that the melting point of the copolyester falls within the above range.

Further, the polyester may contain at least one branching or crosslinking component selected from the group consisting of a tribasic or higher polybasic acid and a polyhydric alcohol in order to improve the melt flow characteristics during molding. . These branching or crosslinking components should be in the range of 3.0 mol% or less, preferably 0.05 to 3.0 mol%.
Examples of the trifunctional or higher polybasic acid and polyhydric alcohol include trimellitic acid, pyromellitic acid, hemimellitic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1 , 3,5-pentanetricarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, polybasic acids such as biphenyl-3,4,3 ′, 4′-tetracarboxylic acid, pentaerythritol, glycerol, Examples thereof include polyhydric alcohols such as trimethylolpropane, 1,2,6-hexanetriol, sorbitol, 1,1,4,4-tetrakis (hydroxymethyl) cyclohexane.

In the resin-coated metal material of the present invention, polyethylene terephthalate / isophthalate containing 5 to 25 mol% of isophthalic acid component and 1 cyclohexanedimethanol component are particularly suitable as a polyester resin that can be used for a can-making or lid-making material. Examples thereof include polyethylene / cyclohexylene dimethylene terephthalate containing 10 to 10 mol%.
The homopolyester or copolymerized polyester should have a molecular weight in the film forming range, and the intrinsic viscosity [η] measured using a phenol / tetrachloroethane mixed solvent as the solvent is 0.5 to 1.5, especially 0. It may be in the range of 6 to 1.5.

  The polyester resin layer used in the present invention may be formed from the above-described polyester or copolyester alone, or a blend of two or more of polyester or copolyester, or a blend of polyester or copolyester and another thermoplastic resin. It may be formed from an object. Examples of blends of two or more of polyester or copolyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate / isophthalate, and combinations of two or more of polyethylene / cyclohexylene dimethylene terephthalate. It is not limited to.

Examples of other thermoplastic resins that can be blended in the polyester include ethylene polymers, thermoplastic elastomers, polyarylate, and polycarbonate. At least one of these modified resin components can be further contained to further improve high-temperature wet heat resistance and impact resistance. This modified resin component is generally used in an amount of up to 50 parts by weight, particularly preferably 5 to 35 parts by weight, per 100 parts by weight of polyester.
Examples of the ethylene polymer include low-, medium- or high-density polyethylene, linear low density polyethylene, linear ultra-low density polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene- Examples include propylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ion-crosslinked olefin copolymer (ionomer), and ethylene-acrylic acid ester copolymer. Among these, ionomers are preferable, and as the base polymer of ionomer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, ion As the seed, Na, K, Zn or the like is used. Examples of thermoplastic elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated styrene-butadiene-styrene block copolymers, and hydrogenated styrene-isoprene-styrene block copolymers. Etc. are used.

Polyarylate is defined as a polyester derived from a dihydric phenol and a dibasic acid. As the dihydric phenol, 2,2′-bis (4-hydroxyphenyl) propane (bisphenol A), 2 , 2′-bis (4-hydroxyphenyl) butane (bisphenol B), 1,1′-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane (bisphenol F), 4-hydroxyphenyl ether, p- (4-hydroxy) phenol or the like is used, but bisphenol A and bisphenol B are preferred. As the dibasic acid, terephthalic acid, isophthalic acid, 2,2- (4-carboxyphenyl) propane, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxybenzophenone, or the like is used. The polyarylate may be a homopolymer derived from the monomer component or a copolymer.
Further, it may be a copolymer of ester units derived from an aliphatic glycol and a dibasic acid as long as the essence is not impaired. These polyarylates are available as Unitika U polymer U series or AX series, UCC Ardel D-100, Bayer APE, Hoechst Durel, DuPont Arylon, Kaneka Chemical NAP resin, etc. it can.

  Polycarbonate is a carbonate resin derived from bicyclic dihydric phenols and phosgene, and is characterized by having a high glass transition point and heat resistance. Examples of the polycarbonate include bisphenols such as 2,2′-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2′-bis (4-hydroxyphenyl) butane (bisphenol B), 1,1′- Bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) methane (bisphenol F), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, , 1-bis (4-hydroxyphenyl) -1-phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,2-bis (4-hydroxyphenyl) ethane, etc. Polycarbonate is preferred.

The polyester resin layer used in the present invention may be a single resin layer or a multilayer resin layer formed by coextrusion or the like. When a multilayer polyester resin layer is used, a polyester resin having an excellent adhesive property is selected for the base layer, that is, the surface-treated metal material side, and the surface layer is made resistant to contents, that is, extraction resistance and non-adsorption of flavor components. This is advantageous because a polyester resin having an excellent composition can be selected.
Examples of multilayer polyester resin layers are shown as surface layer / lower layer, polyethylene terephthalate / polyethylene terephthalate / isophthalate, polyethylene terephthalate / polyethylene / cyclohexylene dimethylene / terephthalate, polyethylene terephthalate / isolated with low isophthalate content. Polyethylene terephthalate / isophthalate having a high phthalate / isophthalate content, polyethylene terephthalate / isophthalate / [blend of polyethylene terephthalate / isophthalate and polybutylene terephthalate / adipate] and the like are of course not limited thereto. The thickness ratio of the surface layer to the lower layer is preferably in the range of 5:95 to 95: 5.

In the polyester resin layer, known compounding agents for resins, for example, antiblocking agents such as amorphous silica, inorganic fillers, various antistatic agents, lubricants, antioxidants, ultraviolet absorbers, etc., according to known formulations Can be blended.
Of these, tocopherol (vitamin E) or polyphenol is preferably used. Tocopherols or polyphenols are conventionally known as anti-oxidants that prevent the decrease in molecular weight due to degradation during heat treatment of polyester resins and improve dent resistance. When this tocopherol or polyphenol is blended with a polyester composition blended with an ethylene-based polymer as a modified resin component, it is subjected not only to dent resistance but also to severe conditions such as retort sterilization and hot bender, resulting in cracks in the coating. Even in such a case, the corrosion can be prevented from proceeding from the cracks, and the effect that the corrosion resistance can be remarkably improved can be obtained.
Tocopherol or polyphenol is preferably blended in an amount of 0.05 to 3% by weight, particularly 0.1 to 2% by weight.

  In the present invention, the thickness of the organic resin layer is generally in the range of 3 to 50 μm, particularly 5 to 40 μm. That is, when the thickness is less than the above range, the corrosion resistance becomes insufficient, and when the thickness exceeds the above range, a problem is likely to occur in terms of workability.

(Manufacture of resin-coated metal materials)
In the present invention, the polyester coating layer can be formed on the surface-treated metal material by any means, for example, extrusion coating, cast film thermal bonding, biaxially stretched film thermal bonding, or the like. . In the case of the extrusion coating method, a polyester resin can be extrusion coated on a surface-treated metal material in a molten state and thermally bonded. That is, after melt-kneading the polyester resin with an extruder, it is extruded from a T-die into a thin film, and the extruded molten resin film is passed through a pair of laminating rolls together with a surface-treated metal material and is pressed and integrated under cooling. Then quench rapidly. When extrusion coating a multilayer polyester resin layer, an extruder for surface layer resin and an extruder for lower layer resin are used, and the resin flow from each extruder is merged in a multiple multilayer die, and thereafter a single layer Extrusion coating may be performed as in the case of resin. Further, by passing a surface-treated metal material vertically between a pair of laminate rolls and supplying a molten resin web on both sides thereof, a polyester resin coating layer can be formed on both sides of the substrate.

  Specifically, the resin-coated metal material is manufactured by the extrusion coating method as follows. A surface-treated metal material (hereinafter sometimes simply referred to as a metal material) is preheated by a heating device as necessary, and supplied to a nip position between a pair of laminate rolls. On the other hand, the polyester resin is extruded in the form of a thin film through a die head of an extruder, supplied between the laminate roll and the metal material, and pressed onto the metal material by the laminate roll. The laminating roll is maintained at a constant temperature, and a thin film made of a thermoplastic resin such as polyester is pressure-bonded to the metal material to thermally bond both of them and cooled from both sides to obtain a resin-coated metal material. In general, the formed resin-coated metal material is further cooled in order to guide it to a cooling water tank or the like to prevent thermal crystallization.

In this extrusion coating method, the polyester resin layer has a low crystallinity level and the difference from the amorphous density is suppressed to 0.05 g / cm ³ or less due to selection of the resin composition and rapid cooling with a roll or cooling bath. Therefore, sufficient workability is ensured for canning, lid processing, and the like. Of course, the rapid cooling operation is not limited to the above example, and the laminate plate can be rapidly cooled by spraying cooling water onto the resin-coated metal material to be formed.

The thermal adhesion of the polyester resin to the metal material is performed by the amount of heat that the molten resin layer has and the amount of heat that the metal material has. The heating temperature (T1) of the metal material is generally 90 ° C. to 290 ° C., particularly 100 ° C. to 280 ° C., while the temperature of the laminate roll is suitably 10 ° C. to 150 ° C.
The resin-coated metal material of the present invention can also be produced by thermally bonding a polyester resin film previously formed by a T-die method or an inflation film forming method to the metal material. As the film, an unstretched film formed by a cast molding method in which the extruded film is rapidly cooled can be used, and this film is biaxially stretched sequentially or simultaneously at the stretching temperature, and the stretched film is heat-set. It is also possible to use a biaxially stretched film produced by the above method.

  In the present invention, various configurations other than the above-described layer configurations can be adopted, and in the case of forming an organic surface treatment layer, it is not particularly necessary. However, a conventionally known adhesion between the surface treatment metal material and the polyester layer is not necessary. It is of course possible to provide a primer. This adhesion primer exhibits excellent adhesion to both the metal material and the film. Primer paints with excellent adhesion and corrosion resistance are phenol epoxy paints composed of resol type phenol aldehyde resins derived from various phenols and formaldehyde and bisphenol type epoxy resins, especially phenol resins and epoxy. It is a paint containing a resin in a weight ratio of 50:50 to 1:99, in particular 40:60 to 5:95. The adhesive primer layer is generally preferably provided with a thickness of 0.01 to 10 μm. The adhesion primer layer may be provided in advance on a metal material, or may be provided on a polyester film.

(Use)
The surface-treated metal material and resin double metal material of the present invention are not limited to this, but can be effectively used for metal cans and can lids.
As long as the metal can is formed from a resin-coated metal material, it can be formed by any conventionally known can-making method, and can be a three-piece can having a side seam, but generally a seamless can (two-piece can) It is preferable that This seamless can is drawn and re-squeezed, bent and stretched by drawing and re-drawing (stretching), and bent and drawn by drawing and re-drawing so that the coated surface of the surface-treated metal material polyester resin faces the inner surface of the can. -It is manufactured by attaching to a conventionally known means such as ironing or drawing / ironing.
Moreover, as long as it is formed from the resin-coated metal material, the can lid may be formed by any conventionally known lid-making method. In general, the present invention can be applied to a stay-on-tab type easy open can lid and a full open type easy open can lid.

Next, an Example and a comparative example are shown, this invention is demonstrated concretely, and an effect is clarified.
Since the metal container is placed in the most severe environment in terms of workability and corrosion resistance of the surface-treated metal material or resin-coated metal material, the examples are shown as metal cans and can lids. However, the present invention is not limited to the examples.

  The concentration of zirconium ions and fluorine ions was adjusted to be aqueous solutions having molar concentrations shown in Table 1 as Zr and F, respectively, to obtain a treatment bath. However, zirconium zirconium fluoride was used for treatment baths A and B, zirconium oxynitrate was used for treatment baths C and D, and zirconium ammonium fluoride was used for treatment bath E as zirconium chemicals. Moreover, sodium fluoride was used for a part of the processing bath B and all of the processing baths C and D as a fluorine chemical.

式中、Ｘは、水素原子または下記式（II）に示すＺ基であり、Ｚ基がベンゼン環１個あたり０．３の割合で導入された反復単位からなる水性フェノール樹脂

で表される反復単位から成る水溶性重合体。 [Phenolic water-soluble organic compounds]
As the phenol water-soluble organic compound, a water-soluble polymer represented by the following formula (I) was used.

In the formula, X is a hydrogen atom or a Z group represented by the following formula (II), and the aqueous phenol resin comprising a repeating unit in which the Z group is introduced at a ratio of 0.3 per benzene ring

A water-soluble polymer comprising repeating units represented by

[Production of polyester film]
A polyester resin having the composition shown in Table 2 is melt-extruded from two extruders via a two-layer T-die, and then a film obtained by cooling with a cooling roll is wound up. I obtained (b), (b), (c), (d), and (e).

[Measurement of surface atomic ratio]
In measuring the surface atomic ratio, when an organic treatment such as a silane coupling agent treatment or a phenolic organic compound treatment was performed after the inorganic surface treatment, an inorganic surface-treated metal plate before the organic treatment was used for the measurement. The P2p, O1s, F1s, and Zr3d peaks were measured on the metal material after the inorganic surface treatment with an X-ray photoelectron spectrometer (XPS) under the following conditions. , F / Zr atomic ratio was determined. However, the silica-dispersed samples, since a dense silica film is formed on the outermost surface, when the seek O / Zr, peaks of Si2p be measured beforehand at the same time, from the atomic concentration of Si of O corresponding to SiO ₂ The concentration was determined, the atomic concentration of each element excluding the SiO _{2 component} from the whole was recalculated, and the atomic ratio of O / Zr was determined. In the case of a main element contained on the substrate surface, for example, an aluminum alloy substrate, Al2p is also measured simultaneously with P2p, O1s, F1s, Zr3d, and Si2p, and Ar sputtering is performed until C1s becomes 10% or less in atomic concentration. The surface concentration was defined as the atomic concentration of Si2p at the time when the contaminated layer was lightly removed.
Equipment QuantuZr 2000 manufactured by PHI
Excitation X-ray source Al monochromator 75W-17kV
Measurement diameter φ100μm
Photoelectron extraction angle 90 ° (0 ° with respect to sample normal)
Analysis software; MultiPak

[Adhesion evaluation]
The surface-treated metal material was cut into strips having a width of 5 mm and a length of 80 mm, and the cast films shown in Table 3 (b) were cut into strips having a width of 5 mm and a length of 80 mm. The polyester film section was sandwiched between the obtained two surface-treated strip sections and heated at 250 ° C. for 3 seconds under a pressure of 2.0 kg / cm ² to obtain a T peel test piece. Thereafter, a retort treatment was performed at 110 ° C. for 60 minutes, and the film was immersed in water immediately after the completion, pulled up from the water just before measurement by a tensile tester, and measured for adhesive strength at a tensile speed of 10 mm / min.

Example 1
1. Preparation of surface-treated metal plate JIS 5021H18 aluminum alloy plate with a thickness of 0.25 mm was used as the metal plate, and degreasing agent 322N8 (manufactured by Nippon Paint Co., Ltd.) was used and treated in a 70 ° C. bath for 10 seconds, followed by water washing. The sample was immersed in 1% sulfuric acid at 40 ° C. for 5 seconds, washed with water and washed with pure water, and pretreated. Then, in the treatment bath shown in A of Table 1 at a bath temperature of 45 ° C., with stirring, the iridium oxide-coated titanium plate placed at a position of the distance between the electrodes of 17 mm was used as the anode at a current density of 5 A / dm ² and 0. Cathodic electrolysis was performed intermittently by repeating energization for 6 seconds and stopping for 0.4 seconds three times, and immediately thereafter, washing with running water, washing with pure water, and drying were performed. Subsequently, dip in a 3% aqueous solution of γ-aminopropyltrimethoxysilane (product name KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.), roll squeeze and dry at 120 ° C. for 1 minute, and a silane coupling agent on the inorganic treatment layer. A surface-treated metal plate having a layer was obtained.
2. Production of Resin-Coated Metal Plate Using the obtained surface-treated metal plate, a resin-coated metal plate for lid making was produced by the following method. First, water-cooling immediately after thermocompression bonding through a laminating roll so that the lower layer side of the cast film of (a) in Table 3 is in contact with one surface of a surface-treated metal plate heated to a plate temperature of 250 ° C. in advance. Thus, a film was coated on one side. Next, an epoxy acrylic coating was applied by roll coating on the other side of the metal plate, which was the outer surface of the lid, and baked at 185 ° C. for 10 minutes.
3. Evaluation of surface-treated metal plate Part of the obtained surface-treated metal plate was subjected to weight film thickness measurement such as Zr, surface atomic ratio measurement, and adhesion evaluation.
The results are shown in Table 4. In the table, the evaluation of adhesiveness is that the maximum tensile strength after peeling a test piece by 10 mm or more with a tensile tester is 1.0 kg / 5 mm or more, ◎, 0.4 kg / 5 mm or more and less than 1.0 kg / 5 mm The sample was marked with ◯, and the sample with less than 0.4 kg / 5 mm was marked with ×.
4). Evaluation of opening of can lid Using the obtained resin-coated metal plate, after preparing a 301-diameter full-open can lid by a conventional method, after winding the can body with water filled in the can body, 110 ° C. for 60 minutes A retort sterilization treatment was performed, and immediately after cooling, the resin was peeled off at the periphery of the score portion and the opening of the can lid was evaluated. The results are shown in Table 4. In the table, the evaluation of the openability of the can lid is for observing the feathering around the opening, ◎ if no feathering is observed, ○ if there is no resin peeling less than 0.5 mm, and feathering is 0 . × 5 mm or more.

(Example 2)
The current density was set to 7 A / dm ² using the bath shown in B of Table 1 as the treatment bath, and 0.6 second energization-0.4 second stop was repeated four times, and the silane coupling agent treatment was not performed. An inorganic coating was prepared in the same manner as in Example 1. Thereafter, it is dipped in a 1 g / liter aqueous solution of the solid content of the phenolic water-soluble polymer represented by the formula (I), squeezed by roll and dried at 120 ° C. for 1 minute, and the phenolic organic surface treatment layer on the inorganic treatment layer. A surface-treated metal plate having the following was obtained. Resin coating, lid making and evaluation were carried out in the same manner as in Example 1.

(Example 3)
0.4 g / liter of a solid content of phenol-based water-soluble polymer represented by the aforementioned formula (I),
Hydrofluoric acid (HF) 0.01 g / liter,
75% phosphoric acid (H ₃ PO ₄ ) 0.20 g / liter,
An aqueous solution containing 20% zirconium hydrofluoric acid (H ₂ ZrF ₆ ) 1.3 g / liter was prepared and used as a surface treating agent.
After pre-treating the metal plate in the same manner as in Example 1, the surface treatment agent was sprayed at 40 ° C. for 20 seconds, followed by washing with water and pure water. Subsequently, an inorganic surface treatment was performed in the same manner as in Example 1 except that the pretreatment and the silane coupling agent treatment were not performed, and the resin coating, the lid making, and the evaluation were performed.

Example 4
0.001 mol / liter of potassium dihydrogen phosphate was added to the bath shown in A of Table 1, and an inorganic surface treatment was performed by repeating the energization for 0.6 seconds and the stop for 0.4 seconds at a current density of 10 A / dm ² four times. Except for the above, in the same manner as in Example 1, treatment with a silane coupling agent, resin coating, lid formation, and evaluation were performed.

(Example 5)
The silane was treated in the same manner as in Example 1 except that the bath shown in D of Table 1 was used as the treatment bath and the inorganic surface treatment was repeated 4 times with a current density of 10 A / dm ² and a 0.6 second energization-0.4 second stop. Coupling agent treatment, resin coating, lid making and evaluation were performed.

(Example 6)
In the same manner as in Example 1 except that a bath obtained by adding 60 g / liter of Snowtex C (Nissan Chemical Industry Co., Ltd.) to the bath shown in A of Table 1 was used, inorganic surface treatment, silane coupling agent treatment, resin coating, Lid making and evaluation were performed.

(Comparative Example 1)
An inorganic surface treatment was conducted in the same manner as in Example 1 except that 0.6 sec energization and 0.4 sec stop at a current density of 2.5 A / dm ² were repeated 5 times to perform inorganic surface treatment and no silane coupling agent treatment was performed. Surface treatment, resin coating, lid making and evaluation were performed.

(Comparative Example 2)
After the pretreatment of the metal plate in the same manner as in Example 1, the silane coupling agent treatment, the resin coating, the lid making, and the evaluation were performed in the same manner as in Example 1 except that the inorganic surface treatment was not performed. .

(Comparative Example 3)
After performing the pretreatment of the metal plate in the same manner as in Example 1, the phenolic organic surface treatment was performed, and the subsequent inorganic surface treatment was not performed. Evaluation was performed.

(Comparative Example 4)
After pre-treating the metal plate in the same manner as in Example 1, a bath was prepared by a conventional method using a commercially available zirconium-based chemical conversion treatment liquid (Allodin 404, manufactured by Nihon Parkerizing Co., Ltd.), and the liquid temperature was 40 ° C. for 15 seconds. After spraying, immediately after that, washing with water, washing with pure water and drying were performed. Subsequently, in the same manner as in Example 1, treatment with a silane coupling agent, resin coating, lid formation, and evaluation were performed.

(Comparative Example 5)
Pretreatment and inorganic surface treatment were performed in the same manner as in Comparative Example 4 except that the spray treatment was performed for 18 seconds using a commercially available zirconium-based chemical conversion treatment liquid (Allodin 404, manufactured by Nihon Parkerizing Co., Ltd.). Subsequently, in the same manner as in Example 2, phenolic organic surface treatment, resin coating, lid-making, and evaluation were performed.

(Comparative Example 6)
Using the bath shown in Table 1 C as the treatment bath, the same treatment as in Example 1 was conducted except that the inorganic surface treatment was performed by repeating the current flow of 0.6 seconds at the current density of 10 A / dm ² and the stop of 0.4 seconds four times. Silane coupling agent treatment, resin coating, lid making and evaluation were performed. However, since the film obtained by the inorganic surface treatment was removed by washing with running water, after electrolysis, the film was gently immersed in accumulated water and then dried.

(Comparative Example 7)
Example 1 except that 0.005 mol / liter of potassium dihydrogen phosphate was added to the bath shown in A of Table 1 and cathodic electrolysis was repeated 4 times of 0.6 second energization-0.4 second stop. Inorganic surface treatment, silane coupling agent treatment, resin coating, lid making and evaluation were performed.

(Example 7)
1. Preparation of surface-treated metal plate and resin-coated metal plate A JIS3104H19 aluminum alloy plate with a thickness of 0.28 mm was used as the metal plate, and the lower layers of the cast films in Table 3 (f) and Table 3 (e) were respectively metal on both sides. Coating was performed so as to contact the surface, and pretreatment, inorganic surface treatment, silane coupling agent treatment, and resin coating were performed in the same manner as in Example 1.
Both sides of the resulting resin-coated metal plate are electrostatically oiled with paraffin wax on both sides, then punched out into a circle with a diameter of 166 mm, and according to a conventional method, the surface coated with the film (e) in Table 3 is the inner surface side. A shallow squeezed cup was created. Next, this shallow drawn cup was redrawn and ironed, and a can was obtained by deep drawing and ironing. Various characteristics of the can thus obtained were as follows.
Can body diameter 66mm,
Can body height 128mm,
The thickness of the can wall relative to the original plate thickness -63%
This can body was subjected to heat treatment at 220 ° C. for 60 seconds after doming molding in accordance with a conventional method, followed by trimming of the end of the opening, curved surface printing, neck-in to 206 diameter, flange The 350g seamless can was created by processing and re-flange processing.
2. Evaluation of retort adhesion of metal cans 5mm below the open end of the can after the re-flanging process, scratches reaching the substrate over the entire circumference of the inner surface of the can and the outer surface of the can, and in hot steam at 125 ° C in the state of an empty can For 30 minutes, and the degree of peeling of the coating resin around the inner and outer surface side scratches of the can was observed to evaluate the retort adhesion. The results are shown in Table 4. In the table, the evaluation of retort adhesion of metal cans is when there are no peeled cans in 20 cans, and there are 2 cans with no peel on the inner surface side of the 20 cans and part of the peel on the outer surface side of the can. The case where the inside of the can is peeled off, or the case where there is peeling on the inner surface side of the can or there are 3 or more cans on the outer surface side of the can was marked as x.
3. Corrosion resistance evaluation of metal cans After storing a metal can packed with carbonated water so that the internal pressure at 25 ° C is 3.5 kg / cm ² at 37 ° C for one week, the can temperature is lowered to 5 ° C, then the metal can From an upright state, the bottom radius portion was deformed by dropping from a height of 50 cm onto a steel plate having a thickness of 10 mm inclined 15 ° with respect to the horizontal direction. Thereafter, the bottom of the can including the bottom radius portion was cut in the circumferential direction, and the corrosion state around the bottom radius deformed portion after aging for 2 weeks at 50 ° C. in a 0.1% sodium chloride aqueous solution was observed to evaluate the corrosion resistance. The results are shown in Table 4. In the table, the corrosion resistance of metal cans was evaluated by observing the periphery of the deformed portion of the bottom radius with a stereomicroscope, and ◯ when no corrosion was observed and x when slightly corroded.

(Example 8)
Except that the same surface treatment as in Example 2 was performed, the same resin-coated metal sheet as in Example 7 was prepared, the retort adhesion evaluation of the can, and the corrosion resistance evaluation.

Example 9
Except that the same surface treatment as in Example 3 was performed, the same resin-coated metal plate as in Example 7 was prepared, the retort adhesion evaluation of the can, and the corrosion resistance evaluation.

(Example 10)
Except that the same surface treatment as in Example 6 was performed, the same resin-coated metal sheet as in Example 7 was prepared, the retort adhesion evaluation of the can, and the corrosion resistance evaluation.

(Example 11)
Using a bath obtained by adding 60 g / liter of Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) to the bath shown in A of Table 1, 0.6 seconds energization-0.4 second stop at a current density of 1 A / dm ² was repeated three times. Then, except that the inorganic surface treatment was performed and the organic treatment was not performed, the same resin-coated metal plate as that of Example 7 was prepared, the retort adhesion evaluation of the can, and the corrosion resistance evaluation.

(Comparative Example 8)
Except that the same surface treatment as in Comparative Example 1 was performed, the same resin-coated metal plate as in Example 7 was prepared, the retort adhesion evaluation of the can, and the corrosion resistance evaluation.

(Comparative Example 9)
Except that the same surface treatment as in Comparative Example 2 was performed, the same resin-coated metal plate as in Example 7 was prepared, the retort adhesion evaluation of the can, and the corrosion resistance evaluation.

(Comparative Example 10)
Except that the same surface treatment as in Comparative Example 3 was performed, the same resin-coated metal plate as in Example 7 was prepared, the retort adhesion evaluation of the can, and the corrosion resistance evaluation.

(Example 12)
1. Preparation of surface-treated metal plate Cold rolled steel sheet having a thickness of 0.195 mm and a tempering degree T3 as a metal plate is subjected to electrolytic degreasing, acid washing, water washing, pure water washing, pretreatment, and 1.0 g / m of tin per side. After plating to ² , the current density was set to 0.6 A / dm ^{2 in} the treatment bath of E in Table 1. In the same manner as in No. 1, an inorganic surface treatment and a silane coupling agent treatment were performed to obtain a surface-treated metal plate.
2. Preparation of resin-coated metal plate The obtained surface-treated metal plate is heated to a plate temperature of 250 ° C. in advance, and the lower layer side of the cast film of (d) in Table 3 is in contact with and coated on one side to become the outer surface side. A resin-coated metal plate was obtained by water-cooling immediately after thermocompression bonding through a laminate roll so that the cast film of (c) in Table 3 was coated on one side.
3. Preparation of can body After applying paraffin wax electrostatically on both sides of the resin-coated metal plate, it was punched into a circle having a diameter of 140 mm, and a shallow drawn cup was prepared according to a conventional method. The drawn cup was then redrawn and ironed twice to obtain a deep drawn ironing cup having a small diameter and a large height. Various characteristics of the cup thus obtained were as follows.
Cup diameter 52mm,
Cup height 138mm,
-50% of can wall thickness with respect to original plate thickness
This cup is heat-treated at 220 ° C. for 60 seconds after doming to remove the distortion of the resin film, followed by trimming of the end of the opening, curved surface printing, neck-in to 200 diameters, flange processing, and re-flange processing. A 250g seamless can was made.
4). Evaluation of surface-treated metal plate In the same manner as in Example 1, weight film thickness measurement and surface atomic ratio measurement were performed.
5). Evaluation of adhesion during molding After molding the shallow drawn cup, the follow-up state of the resin at the tip of the cup was observed. The case where the resin was lowered from the cup tip by 0.5 mm or more was evaluated as x, the case where the resin was lowered from the cup tip by 0.5 mm or less, and the case where the resin was lowered from 0.1 mm was evaluated as Δ, and the case where the resin was less than 0.1 mm was evaluated as ◯.
6). Retort adhesion evaluation A flaw that reaches the substrate over the entire circumference of the outer surface of the can is placed 5mm below the open end of the can after re-flanging, and kept in 125 ° C hot steam for 30 minutes in an empty can. The degree of peeling of the coating resin around the outer surface side wound periphery was observed to evaluate the retort adhesion. The results are shown in Table 4. In the table, the evaluation of the retort adhesion of the metal can was evaluated as ◯ when there was no peeling, Δ when the peeling was a part, and x when the peeling occurred over the entire circumference.

(Example 13)
After plating tin on the steel plate in the same manner as in Example 12, the current density was 1 A / dm ² using a bath obtained by adding 60 g / liter of Snowtex C (manufactured by Nissan Chemical Industries) to the bath shown in E of Table 1. Then, 0.6 seconds energization-0.4 second stop was repeated three times for inorganic surface treatment, and then, in the same manner as in Example 12, silane coupling agent treatment, resin coating, can manufacturing, and evaluation were performed.

(Example 14)
After plating tin on the steel plate and carrying out the inorganic surface treatment by cathodic electrolysis in the same manner as in Example 12, the same phenolic organic surface treatment layer as in Example 2 is applied, and the organic surface treatment is performed on the inorganic surface treatment. A surface-treated metal plate having the following was obtained. Subsequently, in the same manner as in Example 12, resin coating, can making, and evaluation were performed.

(Comparative Example 11)
Surface treatment, resin coating, canning and evaluation were performed in the same manner as in Example 12 except that the silane coupling agent treatment was not performed.

(Comparative Example 12)
After tin plating, surface treatment, resin coating, canning and evaluation were carried out in the same manner as in Example 12 except that the inorganic surface treatment and the silane coupling agent treatment were not performed and the tin plating was directly resin-coated.

(Comparative Example 13)
After plating tin on the steel plate in the same manner as in Example 12, cathodic electrolysis was performed in an aqueous solution of sodium dichromate 30 g / liter to produce an inorganic coating of chromium oxide 5 mg / m ² to prepare a surface-treated metal plate. Obtained. Subsequently, resin coating, can making and evaluation were performed in the same manner as in Example 12.

(Comparative Example 14)
After performing tin plating and inorganic surface treatment on the steel sheet in the same manner as in Example 12, it was dipped into a 30% aqueous solution of γ-aminopropyltrimethoxysilane (product name KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) and rolled. Then, it was dried at 120 ° C. for 1 minute to obtain a surface-treated metal plate having a silane coupling agent layer corresponding to a film thickness of 50 mg / m ^{2 in} terms of Si on the inorganic treatment layer. Subsequently, resin coating, can making and evaluation were performed in the same manner as in Example 12.

(Comparative Example 15)
After performing tin plating and inorganic surface treatment on the steel sheet in the same manner as in Example 12, it was dipped in a 0.5% aqueous solution of γ-aminopropyltrimethoxysilane (product name KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.). After roll drawing, drying was performed at 120 ° C. for 1 minute to obtain a surface-treated metal plate having a silane coupling agent layer corresponding to a film thickness of 0.3 mg / m ^{2 in} terms of Si on the inorganic treatment layer. Subsequently, resin coating, can making and evaluation were performed in the same manner as in Example 12.

(Comparative Example 16)
After tin plating was performed on the steel sheet in the same manner as in Example 12, the same phenol-based organic surface treatment layer as in Example 14 was performed without performing inorganic surface treatment to obtain a surface-treated metal plate. Subsequently, resin coating, resin coating, can making and evaluation were performed in the same manner as in Example 12.

(Example 15)
1. Preparation of surface-treated metal sheet Cold-rolled steel sheet with a thickness of 0.17 mm and a tempering degree of DR8 was subjected to pre-treatment as a metal sheet by electrolytic degreasing, pickling, washing with water, pure water, and 0.3 g / m of nickel per side. After plating on ² , tin was plated to 0.6 g / m ² on one side and subjected to reflow treatment to form a nickel-tin-iron alloy layer. Subsequently, in the same manner as in Example 12, cathodic electrolysis and silane coupling agent treatment were performed in the treatment bath E in Table 1 to obtain a surface-treated metal plate.
2. Preparation of resin-coated metal plate The obtained surface-treated metal plate is roll-coated on both sides using an epoxy acrylic water-based paint so that the coating thickness after baking is 10 μm and subjected to baking treatment at 200 ° C. for 10 minutes. As a result, a resin-coated metal plate was obtained.
3. Preparation of can body and can lid After applying a processing lubricant to the obtained resin-coated metal plate, it was subjected to drawing (drawing ratio 1.3) to prepare a can body having an inner diameter of 83.3 mm. Subsequently, trimming processing and flange processing were performed on the end portion of the opening to produce a drawn can having a height of 45.5 mm. On the other hand, a part of the obtained resin-coated metal plate was molded into a 307-diameter full-open lid by a conventional method.
4). Contents filling test Using the can body and can lid prepared in this way, the can body was filled with tuna oil, and then the full open lid was wound twice and subjected to retort sterilization at 115 ° C for 60 minutes. .
5). Sulfur resistance evaluation Contents filled and retort sterilized, stored at 37 ° C for 6 months, then opened, and examined for sulfur discoloration on the inner surface of the can body and can lid. The results are shown in Table 5, and the results are shown in Table 5.

(Comparative Example 17)
After forming a nickel-tin-iron alloy layer by nickel plating, tin plating, and reflow treatment in the same manner as in Example 15, performing the same silane coupling agent treatment as in Example 15 without performing inorganic surface treatment, A surface-treated metal plate was obtained. Subsequently, the resin coating, the can body and the can lid were prepared and evaluated in the same manner as in Example 15.

(Example 16)
1. Preparation of surface-treated metal plate A cold-rolled steel plate having a thickness of 0.22 mm and a tempering degree T4 as a metal plate is subjected to electrolytic degreasing, acid washing, water washing, pure water washing, pretreatment, and nickel per one side of 0.03 g / m. After plating to ² , after plating tin to 1.3 g / m ² per side, reflow treatment is performed, followed by inorganic surface treatment and silane coupling agent treatment to obtain a surface-treated metal plate for can bodies. It was.
On the other hand, a cold-rolled steel sheet having a tempering degree T4 of 0.21 mm was treated in the same manner as described above to obtain a surface-treated metal sheet for can lids.
2. Preparation of resin-coated metal plate, can body and can lid Using the surface-treated metal plate for can body, the film thickness after baking is 5 μm on the inner surface side except for the place where the epoxy phenol solvent type paint is applied to the joint part of the can body Margin coating was performed so as to be 3 μm on the outer surface side, and baked and cured in a hot air drying furnace at 200 ° C. for 10 minutes to obtain a resin-coated metal plate. The prepared resin-coated metal plate is cut into a blank shape, and the blank is welded in a cylindrical shape with a commercially available electric resistance welder using a wire electrode. Next, on the inner and outer surfaces of the weld seam of the can body After spray-coating a solvent-type epoxy urea-based repair coating so that the dry coating thickness is 40 μm, it is baked for 3 minutes in a hot air drying oven at 250 ° C., and the seam portion is coated to form a welded can body (can diameter 65.4 mm, A can body height of 122 mm) was created.
On the other hand, an epoxyphenol solvent-type paint is roll-coated on both surfaces so that the coating thickness after baking is 10 μm on the surface-treated metal plate for can lids, and subjected to baking treatment at 200 ° C. for 10 minutes. , 209 diameter shell lid.
One opening end of the can body was subjected to flange processing and neck-in processing. After the 209-diameter lid was wound, the other opening end was subjected to triple neck-in processing and flange processing.
3. Content product filling test After hot-packing orange juice at 93 ° C., a commercially available 206-diameter aluminum SOT lid was double-wrapped and sealed.
4). Corrosion resistance evaluation After filling the contents, the cans were opened after storage at 37 ° C for 6 months, and the iron elution amount after the cans were also measured. The results are shown in Table 5 where x is an elution amount of 0.2 ppm or more, ○ is 0.1 ppm or more and less than 0.2 ppm, and ◎ is less than 0.1 ppm.

(Example 17)
In the same manner as in Example 16, after nickel plating, tin plating, and reflow treatment, a current density of 5 A / dm ² was used using a bath in which 60 g / liter of Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) was added to the bath shown in E of Table 1. Then, 0.6 seconds energization-0.4 second stop was repeated three times to perform inorganic surface treatment, and then, in the same manner as in Example 16, silane coupling agent treatment, resin coating, can making and lid making were evaluated. .

(Comparative Example 18)
In the same manner as in Example 16, after nickel plating, tin plating, and reflow treatment, using a bath indicated by E in Table 1 was repeated 8 times with a current density of 0.6 A / dm ² for 0.6 seconds and a stop for 0.4 seconds. In the same manner as in Example 16, except for the inorganic surface treatment and no silane coupling agent treatment, resin coating, can making and lid making, and evaluation were performed.

(Example 18)
1. Preparation of surface-treated metal plate A cold-rolled steel sheet having a thickness of 0.22 mm and a tempering degree DR8 was subjected to electrolytic degreasing, pickling, water washing, and pure water washing as a metal board, and pretreatment was performed. Then, the inorganic surface was the same as in Example 1 except that the current density was 0.6 A / dm ^{2 in} the treatment bath E in Table 1 and the cathodic electrolysis was repeated 8 times for 0.6 second energization-0.4 second stop. Treatment and silane coupling agent treatment were performed.
2. Preparation of resin-coated metal plate The obtained surface-treated metal plate was heated in advance to a plate temperature of 250 ° C., and the lower layer side of the cast film of (a) in Table 3 was in contact with and coated on one side. A resin-coated metal plate was obtained by water-cooling immediately after thermocompression bonding through a laminate roll so that the cast film of (c) in Table 3 was coated on one side.
3. Preparation of can body and can lid After applying a processing lubricant to the obtained resin-coated metal plate, redrawing (drawing ratio 2.5) was performed to prepare a can body having an inner diameter of 65.3 mm. Subsequently, in order to remove the distortion of the resin film, heat treatment was performed at 220 ° C. for 60 seconds, and the end of the opening end was trimmed and flanged to produce a deep drawn can with a height of 101.1 mm. On the other hand, a part of the obtained resin-coated metal plate was molded into a 211-diameter full-open lid by a conventional method.
4). Content Product Filling Test Using the can body and can lid thus prepared, the can body was filled with meat sauce, and then the full open lid was double-wrapped and subjected to retort sterilization treatment at 120 ° C. for 30 minutes.
5). Container inner surface state evaluation The state of the organic coating after container molding was examined and observed for abnormalities such as peeling and perforation. Further, after filling the contents, the container was opened after storage at 37 ° C. for 6 months, and it was examined whether corrosion on the inner surface side of the container or floating of the organic coating occurred, and the results are shown in Table 5.

It is the figure which measured the peak of P2p by XPS about the surface treatment metal material of this invention, and the surface treatment metal material by a zirconium phosphate chemical conversion treatment. It is a figure which shows the O1s peak which performed the depth direction analysis which used sputtering together about the surface treatment metal material by a zirconium phosphate chemical conversion treatment. It is a figure which shows the O1s peak which performed the depth direction analysis which used sputtering together about the surface treatment metal material of this invention. It is a figure which shows a Zr3d peak about the surface treatment metal material of this invention. It is sectional drawing which shows an example of the surface treatment metal material of this invention. It is sectional drawing which shows another example of the surface treatment metal material of this invention. It is sectional drawing which shows another example of the surface treatment metal material of this invention. It is a figure which shows the relationship between total electrolysis time and Zr weight film thickness. It is a figure which shows an example of the resin coating metal material of this invention. It is a figure which shows another example of the resin coating metal material of this invention. It is a figure which shows another example of the resin coating metal material of this invention.

Claims (8)

An inorganic surface treatment layer (A) mainly composed of an inorganic component and an organic surface treatment layer (B) mainly composed of an organic component are formed on the surface of the metal plate , and further an organic resin coating (C) is formed on at least one surface. A resin-coated surface-treated metal plate , wherein the inorganic surface-treated layer (A) is formed by intermittently performing cathodic electrolysis, and does not contain phosphate ions and contains an oxide of Fr and a hydroxyl group. The atomic ratio of O and Zr contained in the outermost surface of the inorganic surface treatment layer is 1 <O / Zr <10, and the atomic ratio of F and Zr is 0.1 <F / Zr <2. 5, and the weight film thickness of Zr is 5 to 300 mg / ^{m 2,} wherein the organic surface treatment layer (B) is a silane coupling agent Si content 0.8~30mg / ^{m 2} treated layer or phenolic It is a layer mainly composed of water-soluble organic compounds, and the organic resin coating (C) is heatable. Resin-coated surface-treated metal sheet for cans or can lids, characterized in that it consists of sexual polyester. An inorganic surface treatment layer (A) mainly composed of an inorganic component and an organic surface treatment layer (B) mainly composed of an organic component are formed on the surface of the metal plate, and further an organic resin coating (C) is formed on at least one surface. A resin-coated surface-treated metal plate, wherein the inorganic surface-treated layer (A) is formed by intermittently performing cathodic electrolysis and is made of an oxide of Zr containing F and a hydroxyl group. The atomic ratio of P and Zr contained in the outermost surface of is 0 ≦ P / Zr <0.6, the atomic ratio of O and Zr is 1 <O / Zr <10, and the atomic ratio of F and Zr However, 0.1 <F / Zr <2.5, the weight film thickness of Zr is 5 to 300 mg / m ² , and the organic surface treatment layer (B) has an Si content of 0.8 to 30 mg / m ^2. the m ² of the silane coupling agent treatment layer or phenolic water-soluble organic compound is a layer mainly composed, Machine resin coating (C) can or can lid resin-coated surface-treated metal sheet, characterized in that it consists of a thermoplastic polyester. It said inorganic surface-treating layer (B) is, Si content containing SiO ₂ particles of 20 to 80 mg / ^{m 2} in claim 1 or 2 cans or can lids resin-coated surface-treated metal sheet according to. The organic surface treatment layer (B) is a layer mainly composed of a phenolic water-soluble organic compound having a content in the range of 6 to 30 mg / m ^{2 in} terms of carbon atoms , on which the inorganic surface treatment layer is formed. The resin-coated surface-treated metal plate for cans or can lids according to any one of claims 1 to 3, wherein (A) is formed . Cathodic electrolysis is intermittently conducted in an aqueous solution containing Zr, F and water-dispersible silica having a particle size of 4 to 80 nm and having a phosphate ion concentration of less than 0.003 mol / liter as PO _4. After forming an inorganic coating on the surface of the metal plate at a high speed by performing 2 to 10 cycles in the range of 0.1 to 0.8 seconds, an organic coating is formed by applying and drying a phenolic water-soluble organic compound or silane coupling agent. Further, a thermoplastic polyester is coated on the organic coating, and the method for surface treatment of a resin-coated surface-treated metal plate for cans or can lids is provided . An inorganic surface treatment layer (A) mainly comprising an inorganic component on the surface of the metal plate, and a resin-coated surface-treated metal plate in which an organic resin coating (C) is formed on at least one surface of the inorganic surface treatment layer, The inorganic surface treatment layer (A) is formed by intermittently performing cathodic electrolysis, is composed of an oxide of Zr containing F and hydroxyl groups without containing phosphate ions, and is contained on the outermost surface of the inorganic surface treatment layer The atomic ratio of O and Zr is 1 <O / Zr <10, the atomic ratio of F and Zr is 0.1 <F / Zr <2.5, and the weight film thickness of Zr is 5 to 5. A resin-coated surface-treated metal plate for cans or can lids, which is 300 mg / m ² and the organic resin coating (C) is made of a thermoplastic polyester . An inorganic surface treatment layer (A) mainly comprising an inorganic component on the surface of the metal plate, and a resin-coated surface-treated metal plate in which an organic resin coating (C) is formed on at least one surface of the inorganic surface treatment layer, The inorganic surface treatment layer (A) is formed by intermittently performing cathodic electrolysis, is composed of a Zr oxide containing F and a hydroxyl group, and is contained in the outermost surface of the inorganic surface treatment layer. The atomic ratio is 0 ≦ P / Zr <0.6, the atomic ratio of O and Zr is 1 <O / Zr <10, and the atomic ratio of F and Zr is 0.1 <F / Zr <2. A resin-coated surface-treated metal plate for cans or can lids, wherein the weight film thickness of Zr is 5 to 300 mg / m ² and the organic resin coating (C) is made of a thermoplastic polyester . Cathodic electrolysis is intermittently conducted in an aqueous solution containing Zr, F and water-dispersible silica having a particle size of 4 to 80 nm and having a phosphate ion concentration of less than 0.003 mol / liter as PO _4. A can or can characterized by forming an inorganic coating on the surface of a metal plate at a high speed by performing 2 to 10 cycles in a range of 0.1 to 0.8 seconds, and further coating a thermoplastic polyester on the inorganic coating Surface treatment method for resin-coated surface-treated metal plate for lids .

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