TW201132802A - Metal plate coated with resin - Google Patents

Abstract

To provide a metal plate coated with a resin not only having corrosion resistance but also having capability of withstanding a roll molding process as well as coating film adhesion subsequent to a post-coating process. The metal plate coated with a resin includes a coating layer of a resin made from a surface treatment composition. The surface treatment composition includes an inorganic component constituted of plural species of colloidal silica each having a different area-averaged mean particle diameter; a resin component constituted of a copolymer of an olefin and an [alpha],[beta]-unsaturated carboxylic acid, a polymer of an [alpha],[beta]-unsaturated carboxylic acid, and an acrylic-modified epoxy resin; a silane coupling agent containing a glycidoxy group; and a metavanadate.

Description

[Technical Field] The present invention relates to a resin-coated metal sheet excellent in roll formability and coating film adhesion after post-coating. [Prior Art] The hot-dip galvanized steel sheet used for building materials has a hot-dip galvanized steel sheet (GI material) plated with pure zinc on the steel sheet, and an alloyed hot-dip galvanized steel sheet (G A material) which is alloyed. For the GI material, the GI material is continuously passed through a plurality of sets of rolls arranged in a row (forming speed is about 20 to 70 m/min), and the forming process is sequentially performed, and the flat product is processed into a desired cross-sectional shape (roll forming). After that, bare (not applied later) is used for decks and light steel keels. In addition, for the GA material, after the surface is coated with a calcium lead rust preventive paint, a lead-free paint or an electrodeposition paint, it is used for a door or a blind. Conventionally, chromate treatment has been carried out on the surface of a GI material or a GA material for the purpose of improving corrosion resistance. However, in recent years, due to the high environmental awareness, 'there is a treatment method that does not implement chromate treatment (no chromic acid. salt treatment)' has been developed so far to form chromate-free on molten galvanized steel sheets. The resin is coated with a metal plate. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Inorganic component and resin component containing olefin-α,β-unsaturated carboxylic acid copolymer and α,β-unsaturated carboxylic acid polymer and oxazoline group-containing copolymer, and further containing glycidyl group-containing decane coupling agent And partial-5-201132802 vanadate. The resin film described in the above document is suitable for a GI material. This is because the GI material is subjected to a severe surface pressure at the time of roll forming, and the resin film described in the above document has a large specific gravity (about 2) and can be formed into a film. Therefore, the roll for the resin film can be reduced in roll forming. In the damage, it is difficult to peel the resin film from the surface of the GI material due to sliding with the roller (the film residue is generated). In addition, when the roll is formed, the coolant is supplied to the surface of the GI material to ensure the lubricity and the processing heat is cooled, and the coolant is repeatedly used. However, even if the resin film (film residue) is peeled off from the GI material, it is mixed and cooled. In the liquid, the resin film described in the above document precipitates in the cooling liquid because of a large amount of inorganic components and a large specific gravity, and it is possible to prevent the film slag from floating in the coolant liquid accompanying the coolant liquid. As a result, it is possible to prevent the occurrence of a problem that the film slag is deposited on the surface of the water removing mat, and the deposited film slag and the forming are formed when the cooling liquid is wiped off from the surface of the GI material using the water removing mat (water removing step). Friction occurs between the surface of the product to generate noise, or the molded article cannot pass through the water-removing pad portion at a uniform moving speed, causing the shape or size of the product to be disordered and the yield to deteriorate. On the other hand, when the resin film is applied to the GA material, the coating film adhesion after the post-coating or the corrosion resistance may be insufficient. The reason why the coating film adhesion is insufficient is considered to be because the surface of the GA material is rough and uneven, and the anchoring effect is originally excellent in the coating film adhesion. However, the resin film is buried in the surface of the GA material, or only Covering the outermost layer of the GA material, resulting in the disappearance of the anchoring effect of the GA material. In addition, the reason why the corrosion resistance-6-201132802 is insufficient is considered to be because the above-mentioned resin film covers only the outermost layer of the GA material, and the film is not formed at the bottom of the concave portion, so that the zinc plating layer is exposed, thereby being post-painted. When a cross cut is cut on the coated surface, corrosion is caused under the coating film when the corrosion resistance test is performed. Further, there is a problem that foaming (coating material expansion) occurs around the cross-cut portion in the above-described corrosion resistance test due to the void generated in the bottom portion of the concave portion. There is also a problem that lithium hydroxide having water absorbing properties is used as the resin coating component. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a chromate-free surface treatment composition and a resin coating provided by the surface treatment composition. In the resin-coated metal sheet, the surface-treating composition not only has corrosion resistance, but also has the roll formability required for the GI material and the coating film adhesion after the post-coating required for the GA material. (Means for Solving the Problem) The resin-coated metal sheet of the present invention which can solve the above-mentioned problems is a resin-coated metal sheet obtained by providing a resin coating film obtained from a surface-treated composition, wherein the surface-treated composition contains 60 to 80 parts by mass of an inorganic component composed of a plurality of colloidal silica having a difference in surface area average particle diameter and 20 to 40 parts by mass of an olefin-α,β-unsaturated carboxylic acid copolymer, α, a resin component comprising a β-unsaturated carboxylic acid polymer and an acrylic acid-modified epoxy resin, and further comprising a propylene-containing propylene content of 5 to 15 parts by mass based on the total of the inorganic component and the resin component of the above-mentioned 201132802 An oxane coupling agent of oxy group and 0.5 to 3 parts by mass of metavanadate. In the present invention, the inorganic component contains colloidal cerium oxide (A) having a surface area average particle diameter of 4 to 6 nm and colloidal cerium oxide (B) having a surface area average particle diameter of 10 to 20 nm, and the above (A) and The mixing ratio of B) is 70: 3 0 to 40: 60 (mass ratio) is a preferred embodiment. Further, in the present specification, the colloidal cerium oxide having a surface area average particle diameter of 4 to 6 nm means colloidal cerium oxide having a colloidal cerium oxide having a surface area of 5 nm of 90% or more (more preferably 95%) or more. Further, the colloidal cerium oxide having a surface area average particle diameter of from 10 Å to 20 nm means that colloidal cerium oxide having a surface area of 12 nm has a colloidal cerium oxide of 90% or more (more preferably 95%) or more. The surface area average particle size can generally be determined by the Sears method or the BET method. In order to more accurately measure the surface area average particle diameter, an electron microscope capable of measuring a direct particle diameter is effective. Further, the resin component contains 2 to 15% by mass of the above-mentioned acrylic modified epoxy resin as a preferred embodiment. In addition, the surface tension of the surface treatment composition is 50 dyn/cm or less, and the adhesion amount of the resin film is 0.2 to lg/m 2 in terms of dry mass, or a metal plate-based hot-dip galvanized steel sheet having the resin film or alloyed melting. A bismuth zinc plate is a preferred embodiment. Since the resin-coated metal sheet of the present invention has a resin film obtained from a specific surface treatment composition, it is not only corrosion-resistant, but also can satisfy the roll formability required for the GI material and the post-coating required for the GA material. After the coating film adhesion. [Embodiment] The resin-coated metal sheet of the present invention is a resin-coated metal sheet having a resin film obtained by a surface-treated composition, wherein the surface-treated composition contains 60 to 80 parts by mass of an average surface area. Inorganic component composed of a plurality of colloidal ceria having different particle diameters and 20 to 40 parts by mass of an olefin-α,β-unsaturated carboxylic acid copolymer, an α,β-unsaturated carboxylic acid polymer, and an acrylic modified epoxy Further, the resin component of the resin is further contained in an amount of 5 to 15 parts by mass based on 100 parts by mass of the total of the inorganic component and the resin component, and a vanadium oxide-containing decane coupling agent and 0.5 to 3 parts by mass of vanadium Acid salt. Hereinafter, the resin-coated metal sheet of the present invention will be described in detail. Further, although the inorganic component contained in the film of the present invention is much more than the resin component, it is often referred to as a "resin film" in the field. Therefore, the term "resin film" is also used in the present invention. (Inorganic component) In the present invention, lithium niobate is not used as an inorganic component. Since lithium silicate which exhibits water absorption is not used, even after the surface of the resin-coated metal sheet is subjected to post-coating, cross-cutting, and a severe corrosion resistance test such as a salt water immersion test or a salt spray test, The adhesion of the coating film can be suppressed from being deteriorated. <Colloidal cerium oxide> One of the features of the present invention is to use a plurality of types of rubber -9-201132802 cerium oxide having different surface area average particle diameters as inorganic components. Thereby, the affinity (intimacy) of the binder resin (resin component) and the colloidal cerium oxide can be improved, and the film forming property of the formed resin film (the bonding force between the colloidal cerium oxide particles) can be improved and formed at the same time. Dense film. More specifically, as the inorganic component, colloidal cerium oxide (A) having a surface area average particle diameter of 4 to 6 nm and colloidal cerium oxide (B) having a surface area average particle diameter of 10 to 20 nm are preferably used. The composition is better composed of colloidal cerium oxide (A) and colloidal cerium oxide (B). The colloidal cerium oxide is presumed to be dissolved and dissolved in the film defect in a corrosive environment, thereby exerting a pH buffering effect or The passivation film forms a function to suppress dissolution/dissolution of the metal plate, thereby improving the corrosion resistance of the metal plate. In order to fully exert these effects, it is effective to use colloidal cerium oxide (A). On the other hand, since the surface activity of the colloidal cerium oxide (A) is high, if only the colloidal cerium oxide (A) is used, the liquid stability of the surface-treated composition deteriorates with time (at about 4). There is a problem that the dense film is not formed within 8 hours, and the content of the inorganic component in the resin film is not increased, but the specific gravity of the resin film is not increased. Therefore, the inventors of the present invention conducted an active investigation and found that if a colloidal cerium oxide (B) having a small surface activity and a surface area average particle diameter of 10 to 20 nm is used at the same time, the liquid of the surface treatment composition is not stabilized. The property is lowered and the content of the inorganic component can be increased. Further, the surface area average particle diameter of the colloidal cerium oxide in the present specification means that when the surface area average particle diameter is about 1 to 10 nm, the cerium measured by the Sears method is used; When 〇~1〇〇nm or so, the 测定 measured by the BET method is used, or the nominal 値 described in the manufacturer's hand -10- 201132802. The mixing ratio of the colloidal cerium oxide (A) to the colloidal cerium oxide (B) is preferably 70:3 0 to 40:60, more preferably 65:3 5 to 45:55 by mass ratio. When the mass ratio of the colloidal cerium oxide (A) exceeds 70, the affinity with the resin component is deteriorated, and the liquid stability of the surface-treated composition is deteriorated, and a uniform and dense film cannot be formed. Accordingly, the bare corrosion resistance of the resin-coated metal plate and the adhesion of the coating film after the post-coating are deteriorated. When the mass ratio of the colloidal cerium oxide (A) is less than 40, the amount of Si ions dissolved and eluted in the defect portion of the coating film in a corrosive environment is reduced, and the bare corrosion resistance is deteriorated. The colloidal cerium oxide is commercially available, and as the surface area average particle diameter of 4 to 6 nm, for example, "Snowtex (registered trademark) XS" manufactured by Nissan Chemical Industries, Ltd. is exemplified. In addition, as a commercially available product having a surface area average particle diameter of 10 to 20 nm, "Snowtex (registered trademark) 40", "Snowtex (registered trademark) N", and "Snowtex (", manufactured by Nissan Chemical Industries, Ltd.) are also exemplified. Registered trademark) SS ”, “

Snowtex (registered trademark) 0", etc.; "ADELAIDE (registered trademark) AT-30", "ADELAIDE (registered trademark) AT-30A" manufactured by ADEKA, etc. When the surface treatment composition used to form the resin film is water system In order to disperse the colloidal cerium oxide well, it is preferable to select the type of colloidal cerium oxide in consideration of the pH of the surface treatment composition. 〇 For the inorganic component composed of the above-mentioned colloidal cerium oxide, it is in the same manner as the resin component described later. 60 to 80 parts by mass of the total of 100 parts by mass. Inorganic-11 - 201132802 The film formation property of the resin film formed by the surface treatment composition having a component amount within this range is good, so that peeling of the film is unlikely to occur, and resin coating can be improved. The roll formability of the metal plate is reduced, and the surface tension of the surface treatment composition is lowered (preferably 50 dyn/cm or less), and the surface treatment composition is immersed in the surface (concave portion) of the GA material having a rough surface and poor water wettability. The resin film is formed along the rough surface of the GA material, so that the corrosion resistance or the coating film adhesion can be improved. When the amount of the inorganic component exceeds 80 parts by mass, Since the resin component is insufficient, the formed film forming property is insufficient, and a normal film cannot be formed. As a result, the barrier effect in a corrosive environment is also lowered, and the corrosion resistance is deteriorated. It is hard and brittle, and cracks occur, and the film peeling easily occurs during roll forming. Further, since the colloidal cerium oxide (amorphous cerium oxide particles are dispersed in water to form a gel), the surface tension is high (about 66 to 73 dyn/ When the amount of the inorganic component exceeds 80 parts by mass, the surface tension of the surface treatment composition tends to be large, and the wettability of the metal sheet on which the resin film is formed is also deteriorated, and it is difficult to form the film film uniformly. In particular, it is difficult to form a uniform and extremely thin film on the uneven portion on the surface of the GA material, and therefore, the coating film adhesion and the bare corrosion resistance are lowered. When the amount of the inorganic component is less than 60 parts by mass, it may be obtained. The corrosion resistance of the resin-coated metal sheet is insufficient, and the hardness of the film is insufficient, and since the specific gravity of the film is not so large, it is difficult to thin the resin film. When the roll is formed, the film is likely to be peeled off. Further, since the specific gravity of the resin film is not increased, the film slag cannot be precipitated in the coolant receiving tank, and the effect of suppressing the deposition on the surface of the water removing mat is insufficient. Results -12 - 201132802 In the case where the surface of the surface-treated composition having an inorganic component of less than 60 parts by mass is used to form a resin film on a metal plate (particularly a GA material), the content of the resin component is used. Increasing the 'film-forming property improvement', but the amount of S i ions eluted by the corrosion is reduced, so that between the resin film and the surface of the metal plate (the plating layer interface), the rot is hungry (the film is rotted under the film). The coating film adhesion after mounting deteriorates. In the corrosion resistance test after the post-coating, foaming around the cross-cut portion occurs. In the present invention, the inorganic component is more preferably 65 to 75 parts by mass in 100 parts by mass of the inorganic component and the resin component. At this time, the mixing of the colloidal cerium oxide (A) and (B) is preferably 50:50 (mass ratio), and in particular, the bare corrosion resistance or the coating film adhesion of the GA material can be made good (resin composition) The surface treatment composition used in the present invention may contain, in addition to the above inorganic component, an olefin-α,β-unsaturated carboxylic acid copolymer (hereinafter sometimes referred to as "olefin-acid copolymer") and A resin component composed of an α,β-unsaturated carboxylic acid polymer (hereinafter sometimes referred to as "carboxylic acid polymer") and an acrylic modified epoxy resin. By forming a resin film from a surface treatment composition containing both an olefin-acid copolymer and a carboxylic acid polymer, the resistance to starvation of the obtained resin-coated metal sheet can be improved. The correct mechanism is not clear, but it is presumed that a dense resin film can be formed by using the two, and water and oxygen permeation can be effectively suppressed. Further, the "olefin-acid copolymer" of the present invention means a copolymer of an olefin and an α,β-unsaturated carboxylic acid, and a constituent unit derived from an olefin accounts for 50% by mass or more of the copolymer (i.e., The constituent unit derived from the α,β-unsaturated carboxylic acid is 50% by mass or less. Further, "carboxylic acid polymer" means a polymer (also including a copolymer) obtained by using an α,β-unsaturated carboxylic acid as a monomer, and a constituent unit derived from an α,β-unsaturated carboxylic acid is in a polymer. Among those who account for 90% or more. Further, the "α,β-unsaturated carboxylic acid" includes an "α,β-unsaturated carboxylate" in which a part of carboxyl groups are neutralized by a neutralizing agent described later. &lt;Olefin-acid copolymer&gt; The olefin-acid copolymer used in the present invention can be produced by copolymerizing an olefin with an α,β-unsaturated carboxylic acid by a known method, and is commercially available. In the present invention, one type or two or more types of olefin acid copolymers can be used. The olefin which can be used for the production of the olefin-acid copolymer is not particularly limited, but is preferably ethylene, propylene or the like, more preferably ethylene. As the olefin-acid copolymer, any one of a constituent unit derived from only one type of olefin or a constituent unit derived from two or more kinds of olefins can be used. The α,β-unsaturated carboxylic acid which can be used for the production of the olefin-acid copolymer is not particularly limited, and examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and methacrylic acid; maleic acid and rich Dicarboxylic acid such as horse acid or itaconic acid. Among these, acrylic acid is preferred. As the olefin-acid copolymer, a constituent unit of an α,β-unsaturated carboxylic acid can be used only from a constituent unit of an α,β-unsaturated carboxylic acid or a mixture of two or more α,β-unsaturated Any of the constituent units of the carboxylic acid. -14- 201132802 The olefin-acid copolymer ' used in the present invention may contain a constituent unit derived from another monomer in a range which does not adversely affect the corrosion resistance or the like which is an effect of the present invention. In the olefin-acid copolymer, the amount of the constituent unit derived from the other monomer is preferably 1% by mass or less, more preferably 5% by mass or less, and the most preferable olefin-acid copolymer is only olefin- and α. Composition of β-unsaturated carboxylic acid. As the preferred olefin-acid copolymer', an ethylene-acrylic acid copolymer can be exemplified. The α,β-unsaturated carboxylic acid in the olefin-acid copolymer is preferably 5% by mass in order to increase the adhesion between the resin film and the metal plate. Above, more preferably 1 〇 quality. /. the above. However, if the α,β-unsaturated carboxylic acid is excessive, the corrosion resistance is lowered. Therefore, the amount of the α,β-unsaturated carboxylic acid in the copolymer is preferably 30% by mass. /. The following is more preferably 25% by mass or less. The mass average molecular weight (Mw) of the olefin-acid copolymer used in the present invention is preferably from 1,000 to 100,000, more preferably from 3,000 to 70,000, still more preferably 5, in terms of polystyrene. Million. The Mw can be measured by GPC using polystyrene as a standard. &lt;Carboxylic acid polymer&gt; The tannic acid polymer used in the present invention may, for example, be a homopolymer or a copolymer of one or more kinds of α,β-unsaturated carboxylic acids, or further Copolymers obtained by copolymerization. These carboxylic acid polymers can be produced by known methods' and are also commercially available. In the present invention, one type or two or more types of carboxylic acid polymers can be used. -15- 201132802 For α,β-unsaturated carboxylic acids which can be used in the manufacture of carboxylic acid polymers, α,β-exemplified as α,β-unsaturated carboxylic acids which can be used for the synthesis of the above olefin-acid copolymers can be used. Any of the unsaturated carboxylic acids. Among them, acrylic acid and maleic acid are preferred, and maleic acid is more preferred. The carboxylic acid polymer may further contain a constituent unit derived from a monomer other than the α,β-unsaturated carboxylic acid, and the amount of the constituent unit derived from the other monomer is 10% by mass or less in the polymer, preferably 5% by mass. Hereinafter, a carboxylic acid polymer composed only of an α,β-unsaturated carboxylic acid is more preferable. The preferred carboxylic acid polymer may, for example, be polyacrylic acid, polymethacrylic acid, acrylic acid-maleic acid copolymer or polymaleic acid, etc., in which the coating film is adhered to the resin film. From the viewpoint of properties and corrosion resistance, polymaleic acid is more preferable. By using polymaleic acid, the particle size of the produced resin latex can be made small (20 to 60 nm), and the film obtained by film formation can be made dense, so that corrosion resistance and the like can be improved. In addition, since the amount of the carboxyl group is large, the adhesion between the resin film and the metal plate is improved, and the corrosion resistance is further improved. The Mw of the carboxylic acid polymer used in the present invention is preferably 500 in terms of polystyrene. ~ 30,000, better for 800 ~ 10,000, and better for 900 ~ 3,000, the best for 1, 00 0 ~ 2,000. The Mw can be measured by using polystyrene as a standard GPC. The content of the olefin-acid copolymer and the carboxylic acid polymer in the surface treatment composition is from 1,000:1 to 10:1, preferably from 200:1 to 2:0, more preferably from 100:1 to 1. 00: 3. When the content of the carboxylic acid polymer is too low, the effect of the composition of the olefinic acid copolymer and the carboxylic acid polymer cannot be sufficiently exerted, and conversely, when the content of the carboxylic acid polymer is excessive, in the surface treatment composition - 16-201132802 'There is a problem that the olefin-acid copolymer and the carboxylic acid polymer are phase-separated, and a uniform resin film cannot be formed. &lt;Acrylic Modified Epoxy Resin&gt; The above resin component also contains an acrylic modified epoxy resin. In the past, as a method of improving the adhesion of the coating film of the post-coating, it is known that the blocked isocyanate (thermosensitive crosslinking agent) as a resin component is present in the coating film, and the heat during sintering after the post-coating is used (sintering) Temperature) A technique in which a blocked isocyanate blocking agent is dissociated to regenerate a reactive isocyanate group to harden and crosslink the film and the coating film. However, the mainstream of lead-acid calcium anticorrosive paint used as a post-coating coating in the field of building materials is a normally-dry type which does not require thermal sintering (drying), and the above technique cannot be used. As a result of the above-mentioned problems, the present inventors have found that the coating film adhesion of the resin film can be improved by using an acrylic modified epoxy resin which can be formed at a low temperature as a resin component. The correct mechanism for improving the adhesion of the coating film by using an acrylic modified epoxy resin is not clear, but it is presumed that the acrylic modified epoxy resin does not act as a binder of the inorganic component (colloidal cerium oxide). Although film formation (dot-like streaks) on the outermost surface of the resin film does not contribute to the improvement of the bare corrosion resistance, it contributes to the improvement of the coating film adhesion after the post-coating. The reason why the acrylic modified epoxy resin forms a film on the outermost surface of the resin film is considered to be due to the latex particle size of the olefin-acid copolymer and the carboxylic acid polymer of 20 to 60 nm, and the acrylic modified epoxy resin. The latex has a larger particle size of about 100 nm or more. The acrylic modified epoxy resin used in the present invention can be produced by the following method -17-201132802, for example, a polymerizable unsaturated group-containing epoxy resin obtained by reacting an epoxy resin and an unsaturated fatty acid with (meth) The acrylic acid is copolymerized, or a polymerizable unsaturated group-containing epoxy resin obtained by reacting an epoxy resin and a glycidyl group-containing vinyl monomer with an amine is copolymerized with (meth)acrylic acid. In particular, the water-based acrylic acid-modified epoxy resin is commercially available, and, for example, "MODEPICS (registered trademark) 3 01&quot;, "MODEPICS (registered trademark) 3 02", "MODEPICS (registered trademark) manufactured by Arakawa Chemical Industries, Ltd.) ) 303 ”, “MODEPICS (registered trademark) 3 04 ”, etc. The above-mentioned acrylic modified epoxy resin may be used singly or in combination of two or more. In the resin component 1 〇〇% by mass, the acrylic modified epoxy resin The content of the acrylic acid-modified epoxy resin is preferably within 2% by mass or more (more preferably 3% by mass or more) and 15% by mass or less (more preferably 7% by mass or less). When the roll-to-roll formability and the bare corrosion resistance of the resin-coated metal sheet are impaired, the coating film adhesion after the coating is improved. When the content of the acrylic-modified epoxy resin is less than 2% by mass, In addition, when the content of the acrylic-modified epoxy resin exceeds 15% by mass, the corrosion resistance tends to be lowered, particularly in the case of the GA material. Its coating film is dense The properties are greatly deteriorated, and there is a case where foaming occurs. When the content of the acrylic-modified epoxy resin exceeds 15% by mass, the bare corrosion resistance is lowered, and the corrosion resistance of the post-coating and the coating film adhesion are lowered. It is not clear, but it is presumed that it is due to the excessive presence of the acrylic modified epoxy resin, which hinders the formation of the olefin-acid copolymer and the carboxylic acid polymer emulsion-18-201132802. Decane coupling agent&gt; The surface treatment composition of the present invention may comprise a glycidoxy coupling-containing decane coupling agent (more specifically, a decane coupling agent having a glycidoxy group at the terminal). In the case of a decane coupling agent of a glycidoxy group, the adhesion between the metal plate and the resin film can be improved, and the effect of improving the bonding strength between the inorganic component and the resin component in the resin film is also considered. And the effect of improving the bare corrosion resistance is large. Further, when a decane coupling agent containing a glycidoxy group is added, since the surface tension of the surface treatment composition is lowered, the wettability with the metal sheet can be improved, and the surface treatment composition can be improved. The coating property can form a uniform resin film. Further, when the surface treatment composition is spray-dried (the surface treatment composition is sprayed on the surface of the metal plate, and the coating method is squeezed by a squeeze roll), It also exhibits an effect of suppressing foaming caused by the surfactant in the composition. As the propylene oxide coupling-containing decane coupling agent, for example, γ-glycidoxypropylmethyldiethoxy group can be exemplified.矽, γ-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., ΚΒΜ403), γ-epoxy-propyl I-methyl-methoxy sand, etc. Total relative inorganic and resin components 100 parts by mass of the propylene oxide-containing decane coupling amount in the surface treatment composition is 5 parts by mass or more (preferably 7 parts by mass or more) and 15 parts by mass or less (preferably 13 parts by mass or less) . When the decane coupling dose is less than 5 parts by mass, the effect of improving the adhesion between the metal plate and the resin film is not observed. In addition, the bonding strength between the inorganic component and the resin component in the resin film -19-201132802 component is lowered, the film hardness is lowered, and the denseness of the film is deteriorated, and roll formability, coating film adhesion, and bare corrosion resistance are deteriorated. The situation. Even if the dose of the decane coupling agent containing a glycidoxy group exceeds 15 parts by mass, the effect of improving the adhesion between the metal plate and the resin film and the effect of improving the binding force between the inorganic component and the resin component in the resin film component have reached a peak. Become the main reason for the increase in costs. On the other hand, there are cases where the roll formability, the coating film adhesion, and the bare corrosion resistance are lowered, and the liquid enthalpy of the surface treatment composition is lowered to cause gelation or colloidal ruthenium dioxide precipitation. &lt;Transvanadate&gt; The surface treatment composition of the present invention further contains metavanadate. In the same manner as the colloidal ceria, the metavanadate suppresses dissolution and elution of the metal plate by elution, and has an effect of improving corrosion resistance. In particular, for GA materials, metavanadate has an effect of improving the bare corrosion resistance. In order to effectively exhibit this effect, the total amount of the inorganic component and the resin component may be 0.5 parts by mass or less, and the metavanadate may be used in an amount of 0.5 to 3 parts by mass. If it is less than 0.5 part by mass, the effect of improving the bare corrosion resistance is insufficient. Further, when the amount added exceeds 3 parts by mass, the tendency of the bare corrosion resistance to slightly decrease can be seen. This is presumably because an excessive amount of metavanadate suppresses the hydrolysis reaction of the decane coupling agent containing a glycidoxy group, and although it is only a little, it affects the binding force between the inorganic component and the resin component. Further, there is a tendency that the coating film adhesion is remarkably lowered and the liquid stability of the surface treatment composition is also deteriorated. The amount of metavanadate is more preferably 0.7 to 1.5 parts by mass. Further, the optimum amount of the metavanadate is the amount of the V element. -20- 201132802 As the metavanadate, for example, sodium metavanadate 'n-vanadate (nh4vo3) and potassium metavanadate (κνο3) vanadate may be used singly or in combination of two or more. Salt is commercially available and is readily available. &lt;Other components&gt; The surface treatment composition of the present invention may further contain an imine group compound. The reaction of the carbodiimide group with the carboxyl group in the olefin-acid polymer reduces the high alkali resistance in the resin film. In the present invention, one or two kinds of compounds of a diquinone imine group can be used. For the carbodiimide-containing compound, the isocyanate can be heated by the imidization catalyst, and the isocyanate includes, for example, hexamethylene diisocyanate (XDI), hydrogenated benzene. Methyl diHXDI), 4,4-diphenylmethane diisocyanate (1^01) or acid ester (TDI), etc., may also be modified to be water, water emulsifiable or water dispersible). The surface treatment composition is preferably a water-containing carbodiimide-based compound. Further, the compound contains a plurality of compounds of a carbodiimide group. When a plurality of carbodiimide groups are present, the cross-linking reaction with the resin component can further improve the bare corrosion resistance and the like. As a commercially available carbodiimide group-containing compound, for example, ruthenium, osmium-dicyclohexylcarbodiimide, ruthenium, osmium-diisopropyl (NaV03) and the like. The bias. These vanadium-containing carbonized diterpene copolymers and carboxy carboxyl groups, and the above-mentioned carbonaceous carbon are produced in bismuth carbide, the HDI) and phenyl isocyanate (toluene diisocyanate (more preferably 1 point in water-soluble water system) Examples of the carboxyl group contained in one molecule include an example of a carbonized dioxime-21 - 201132802 imine; a polycarbodiimide (a polymer containing a plurality of carbodiimide groups in one molecule) manufactured by Nisshinbo Co., Ltd. "Carbodilite (registered trademark)" series. As a grade of "Carbodilite (registered trademark)", there are water-soluble "SV-02", "V-02", "V-02-L2", "V-04" Or latex type "E-01", "E-02", etc. The amount of the carbodiimide group-containing compound can be set according to the amount of the olefin-acid copolymer and the carboxylic acid polymer to be cross-linked. In other words, the total amount of the olefin-acid copolymer and the carboxylic acid polymer is 100 parts by mass, preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 8 parts by mass or more. When the amount of the compound containing a carbodiimide group exceeds fi, the ene is obtained. The effect of the combination of the acid copolymer and the carboxylic acid polymer is lowered, and when the aqueous carbodiimide group-containing compound is excessively used in the aqueous surface treatment composition, the water resistance and the corrosion resistance are adversely affected. In view of the above, the amount of the carbodiimide group-containing compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the total of the olefin-acid copolymer and the carboxylic acid polymer. It is preferably 16 parts by mass or less. The surface treatment composition of the present invention may contain paraffin, a crosslinking agent, a diluent, an anti-skinning agent, a surfactant, an emulsifier, and dispersion, within a range not inhibiting the effects of the present invention. Agent, leveling agent, antifoaming agent, penetrating agent, film forming aid, dye, pigment, tackifier, lubricant, etc. &lt;Surface tension of surface treatment composition&gt; Surface treatment composition used in the present invention It is preferred to reduce the surface of the surface treatment composition by appropriately adjusting the mixing ratio of the inorganic component to the resin component (specifically, inorganic component: resin component = 60: 40 to 80: 20). The tension is specifically 50 dyn/cm or less, more preferably 48 dyn/cm or less. Thus, even if the surface of the GA material having a rough surface and poor water wettability (concave portion) can be invaded, the GA material can be improved. The method of measuring the surface tension of the surface treatment composition will be described later. The surface treatment composition used in the present invention has been described in detail above, and the method for producing the surface treatment composition is as follows. <Method for Producing Surface Treatment Composition> The surface treatment composition of the present invention is any one of a solvent-based composition or a water-based composition which can be applied to the surface of a metal plate, but it is considered from the viewpoint of environmental problems. Jia is a water system composition. The surface treatment composition can be polymerized by using an organic solvent (in the case of a solvent-based composition) or water, preferably deionized water (in the case of a water-based composition), colloidal cerium oxide, an olefin-acid copolymer, or a carboxylic acid. The compound, the acrylic modified epoxy resin, the propylene oxide coupling broth coupling agent, the partial fL acid salt, the optional carbodiimide group-containing compound or other components are mixed and stirred in a predetermined amount. In the preparation of the surface treatment composition, it is preferred to add a part of the propylene oxide-containing decane coupling agent and the carbodiimide group in the olefin-acid copolymer and the emulsifier (latex) of the carboxylic acid polymer. a compound, after preparing a mixture of the substances, sequentially adding colloidal cerium oxide (preferably added sequentially from the surface area average particle diameter), and remaining decane coupling agent containing propylene-propylene-23-201132802 oxy group , metavanadate, acrylic modified epoxy resin. If vanadate is added before the addition of the glycidoxy coupling-containing decane coupling agent, there is a possibility that the hydrolysis reaction of the decane coupling agent is inhibited to hinder the decane coupling agent. Further, it is preferred to add a glycidyloxy group-containing decane coupling agent twice as described above. This is because the decane coupling agent added first makes the latex particles finer, and as a result, the resin film is densely formed, which contributes to improvement of corrosion resistance, and the decane coupling agent added later contributes to ensuring adhesion to the metal plate and improvement. Film properties. In addition, the amount of the decane coupling agent to be added is preferably 0.1 part by mass or more (more preferably 2 parts by mass or more) and 10 parts by mass or less based on 100 parts by mass of the total of the olefin-acid copolymer and the carboxylic acid polymer. Good for 7 parts by mass or less). Further, the amount of the post-added decane coupling agent was as described above. Heating can be carried out while stirring the above ingredients. Particularly, when the olefin-acid copolymer is emulsified in the presence of a carboxylic acid polymer, heating is preferably carried out. When a water-based surface treatment composition is produced, it is preferred to emulsify an olefin-acid copolymer which is a main component of the resin component. For the olefin-acid copolymer, it can be emulsified by using an emulsifier or neutralizing a carboxyl group in the copolymer. When an emulsifier is used, the average particle diameter of the aqueous emulsion of the olefin-acid copolymer can be made small, the film formability can be improved, and the density of the resin film can be increased accordingly. Among them, a method of emulsification by neutralizing a carboxyl group in an olefin-acid copolymer is preferred. This is because the emulsification by neutralizing the carboxyl group can reduce the amount of the emulsifier or the absence of the emulsifier, thereby reducing or eliminating the adverse effect of the emulsifier on the water resistance and corrosion resistance of the resin film. When neutralizing the carboxyl group in the olefin-acid copolymer, it is preferred to use a base of preferably about 0.5 to 0.95 equivalents, more preferably about 0.6 to 0.8 equivalents, relative to the carboxylate. When the degree of neutralization is too small, the emulsification -24-201132802 does not substantially improve. On the other hand, when the degree of neutralization is too large, the viscosity of the composition containing the olefin-acid copolymer may become too high. The base to be neutralized may, for example, be a group consisting of a hydroxide composed of an alkali metal and an alkaline earth metal (for example, NaOH, KOH, Ca(〇H) 2 or the like, preferably NaOH). Alkali, aqueous ammonia, primary amine, secondary amine, tertiary amine (preferably triethylamine). When a strong base such as NaOH is used, although the emulsifying property is improved, the excessively large amount may lower the corrosion resistance of the resin film. On the other hand, a low-boiling amine (preferably an amine having a boiling point of 1 〇〇 ° C or less at atmospheric pressure; for example, triethylamine) does not substantially lower the corrosion resistance of the resin film. The reason for this is considered to be that the low-boiling amine is volatilized when the surface of the composition is coated and then dried by heating to form a resin film. However, since the effect of improving the emulsifying property of the amine is small, it is preferred to neutralize the above-mentioned strong base and amine. The best combination is the combination of NaOH and triethylamine. When a strong base and an amine are used in combination, the amount of the carboxyl group of the olefin-acid copolymer is preferably from 0.01 to 0.3 equivalents, and the amount of the amine is from about 0.4 to about 0.8 equivalents. When the composition is treated with a water-based surface, a small amount of an organic solvent may be mixed in order to lower the surface tension and improve the wettability to the metal plate. The organic solvent to be used herein may, for example, be methanol, ethanol, isopropanol, butanol, hexanol, 2-ethylhexanol, ethylene glycol diethyl ether, ethylene glycol butyl ether or diethylene glycol. , propylene glycol and the like. &lt;Solid content of surface treatment composition&gt; The solid content of the surface treatment composition used in the present invention is not particularly limited to -25 to 201132802, and may be adjusted by a method of applying a surface treatment composition to a metal sheet. The solid content of the surface treatment composition is generally about 5 to 20% by mass, for example, when it is applied by a spray squeezing method (a coating method in which a surface treatment composition is sprayed on a surface of a metal plate and then squeezed by a squeeze roll). It is preferably about 1 to 18% by mass. &lt;Method of Forming Resin Film&gt; In the present invention, the method and conditions for forming the resin film on the metal plate are not particularly limited, and a surface coating composition may be applied to the surface of the metal plate by a known coating method. A resin coated metal plate is produced by heating and drying on one or both sides. The coating method of the surface treatment composition may, for example, be a bar coating method, a curtain flow coating method, a roll coating method, a spray method, a spray squeezing method, etc., and it is preferably from the viewpoint of cost and the like. Bar coating method and spray squeezing method. Further, the heating and drying conditions are not particularly limited, and examples thereof include a heating and drying temperature of usually about 50 to 120 ° C, preferably about 70 to 100 ° C. Too high a heating and drying temperature may deteriorate the resin film, which is not preferable. &lt;Amount of adhesion of the resin film&gt; The amount of adhesion of the resin film in the resin-coated metal sheet is preferably from 0.2 to lg/m2, more preferably from 0.3 to 0.7 g/m2, in terms of dry mass. When the amount of adhesion is less than 0.2 g/m2, it is difficult to cover the surface of the metal sheet, which greatly impairs the roll formability, the coating film adhesion, and the bare corrosion resistance. On the other hand, when the amount of adhesion exceeds 1 g/m2, the corrosion resistance is good, but the amount of film -26-201132802 peeled off during roll forming increases, so the amount of film slag deposited on the water removal mat increases. The cause of the failure is not good. Moreover, it will greatly damage the adhesion of the film. Further, the resin film of the present invention contains a large amount of inorganic components and has a large specific gravity. Therefore, compared with the conventional resin film having a large amount of resin components, it is possible to successfully thin the film when the amount of adhesion is the same. This also helps to reduce the film slag. &lt;Metal Sheet&gt; The metal sheet used in the present invention is not particularly limited, and examples thereof include a non-plated cold-rolled steel sheet, a hot-dip galvanized steel sheet (GI), an alloyed hot-dip galvanized steel sheet (GA), and an electrogalvanized steel. Steel plate (EG) 'Aluminum plate and titanium plate, etc. Among them, in the present invention, it is preferred to use a hot-dip galvanized steel sheet (GI) and an alloyed molten ore steel sheet (GA) which are not subjected to chromate treatment. EXAMPLES Hereinafter, the present invention will be described in detail based on examples. It is to be understood that the following embodiments are not intended to limit the invention, and that modifications may be made without departing from the spirit and scope of the invention. First, the evaluation methods used in the experimental examples are explained below. (Rolling Formability) A sample of 40 mm x 300 mm was cut out from the resin-coated metal plate and fixed vertically on a tensile tester so that the back surface of the sample abutted against the flat mold (material: SKD 1 1 ). Next, the opposite surface (front surface) of the sample abutting on the flat mold is brought into contact with a jig (the -27-201132802 semi-cylindrical mold, material: SKD 1 1 ) having a convex portion having a tip radius R = 9.1 mm. A load of 4900 N (500 kgf) was applied to the jig in the horizontal direction, and the jig was stretched downward at a speed of 300 mm/min while the back surface of the sample abutted against the flat mold. Thereafter, after the semi-cylindrical mold was separated from the sample and returned to the position before the sliding, the same sliding operation as above was repeated 9 times (total 1 time). Then, the coating amount of the portion (W· ) and the unsliding portion (WQ) which repeatedly slide the semi-cylindrical mold was analyzed by an X-ray fluorescence analyzer, and the residual ratio of the film was calculated by the following formula 1 and evaluated by the following criteria. Film Residual Rate (%) = &amp; X100 (Formula 1) ◎: The film residual ratio is 95% or more 〇: The film residual ratio is 90% or more and less than 95% Δ: The film residual ratio is 80% or more and less than 90%. % X: less than 80% The film adhesion amount is obtained by analyzing the Si element of the colloidal cerium oxide (Si〇2) contained in the film, and is calculated from the ratio of the Si element contained in the film based on the following formula 2. Film adhesion m (g/m2) = 5V(mg/w2)x(^^)x(~^~) + 1000 (Formula 2) C: Proportion of colloidal cerium oxide (SiO 2 ) in the film (exposed resist (SST plate)) Based on J1S Z2371, salt spray test -28-201132802 was applied to the resin coated metal plate to determine the incidence of white rust (10 〇X area of white rust/total area of resin coated metal plate) ) 5% of the time. Further, for the bare corrosion resistance of the building materials, whether it is a GI material or a GA material, as long as the white rust generated by the chromatographic treatment S S T within a period of 48 hours is within 5%, there is no problem in practical use. Further, in other applications, there is no problem as long as the GI material is 96 hours or more and the G A material is 72 hours or more. (Exposed corrosion resistance (plate) in J A S 0 cycle test) JASO cycle test was performed based on JIS H8502. 1 cycle is salt water spray (temperature 3 5 °C X2 hours) - dry (temperature 3 5 °CX humidity 3 0% or less 乂 4 hours) - wet (temperature 50 艽 parent humidity 95% or more > < 2 hours) (both travel time). After 20 cycles, the white rust occurrence rate (the area where white rust occurred at 100 X/the total area of the resin-coated metal plate) was evaluated by the following criteria. ◎: The incidence of white rust is less than 5%. 〇: The incidence of white rust is more than 5%~ less than 10% △: The incidence of white rust is more than 10%~ less than 20% X: The incidence of white rust is 20% In the above (surface tension), a 23% aqueous solution of the surface treatment composition was prepared by using ion-exchanged water in accordance with JIS K2241, and a surface tension measuring device (manufactured by Shimadzu Corporation) and a metal ring as a sensor were used at room temperature. The surface tension of the aqueous solution was determined by Dunone. -29- 201132802 (Coating film adhesion) First, 'Determination of calcium sulphate anticorrosive paint (manufactured by Nippon Paint Co., Ltd., HERGOM CP light gray) with thinner (manufactured by Nippon Paint Co., Ltd., paint thinner ') to adjust the viscosity ( After 2 sec. in 4# Ford Cup, spray-coating the resin-coated metal plate at a spray pressure of 39 Ν (4 kgf) 'after 12 hours of aging' and drying at a temperature of 8 〇〇c for 6 , minutes to prepare a coating. A coating material with a thickness of 35 to 40 μm. &lt;Salt spray test&gt; Next, after the back surface and the edge of the coating material were sealed, the cross cut was cut with a cutter 'Brine spray test (SS Τ ) according to JIS Ζ 2 371' after 1600 hours The one-side maximum expansion width from the cross-cut portion was measured and evaluated by the following criteria. ◎: The expansion width is less than 1.0 mm. 〇: The expansion width is 1.0 mm or more and less than 1.5 mm. Δ: The expansion width is 1.5 mm or more and less than 2.0 mm. X: The expansion width is 2.0 mm or more. &lt;Salt-resistant impregnation test&gt; After sealing the back surface and the edge of the coating material, the cross cut was cut with a cutter, and immersed in an aqueous solution of sodium chloride (30 g/L) at a liquid temperature of 23 ° C ± 2 ° C for 96 hours, and then washed with water. Then, the moisture on the surface was wiped off. Immediately, the tape peeling test of the cross-cut portion was carried out. For the coating material after the peeling test, the one-side maximum peeling width from the cross-cut portion was measured, and -30-201132802 was evaluated by the following criteria. ◎: peeling width is less than 1.0 mm Ο : peeling width is 1.0 mm or more and less than κ5 Δ: peeling width is 1.5 mm or more and less than 2. 〇 mm X: brake width is 2.0 mm or more (olefin-acid Preparation of an emulsion (latex) of a copolymer and a carboxylic acid polymer) In an autoclave having an emulsification apparatus provided with a scrambler, a temperature, and a temperature controller, an ethylene-acrylic acid copolymer as an olefin-acid copolymer is added. (Manufactured by Japan Dow Chemical Co., Ltd., Primacor (registered trademark) 59901, constituent unit derived from acrylic acid: 20% by mass, mass average molecular weight (M w ) · · 2 0, 0 0 0, melt index: 1 3 0 0, Acid value·· 1 5 0 ) 200.0 parts by mass of a polymaleic acid aqueous solution as a carboxylic acid polymer ("nonpol (registered trademark) PMA-50W" manufactured by Nippon Oil & Fats Co., Ltd. 'Mw: about 1,100 (polystyrene) 8.0 parts by mass, 35.5 parts by mass of triethylamine (〇.63 equivalent to the carboxyl group of the ethylene-acrylic acid copolymer), and 8.9 parts by mass of the aqueous solution of 4 8 % of the aqueous solution (relatively ethylene) - the carboxyl group of the acrylic copolymer is 0.15 equivalent), tall oil fatty acid (ha Ma of manufactured into, HARTALL FA3) 3.5 parts by mass of ion-exchanged water 792.6 parts by mass and sealed, high speed stirring for 3 hours and 150 ° C for 5 atmospheres, followed by cooling to 30 〇C. Next, a glycopropoxy group-containing chopping coupling agent (made by Momentive Advanced Materials (formerly GE Toshiba Organic Co., Ltd.), 'TSL8350, y-glycidoxypropyltrimethoxydecane, 1 〇·4 parts by mass) was added. -31 - 201132802, a compound containing a carbodiimide group (Carbodilite (registered trademark) SV - 0 2" manufactured by Nisshinbo Co., Ltd., polycarbodiimide,

Mw: 2,700, solid content: 40% by mass) 31.2 parts by mass, 72.8 parts by mass of ion-exchanged water, and stirred for 10 minutes to prepare an emulsion (latex) of an olefin-acid copolymer and a carboxylic acid polymer (solid content concentration of about 20 mass) %, measured according to JIS K6833). (Experimental Example 1-1~1 -1 〇) &lt;Preparation of Surface Treatment Composition&gt; In the above emulsion, colloidal cerium oxide (A) having a surface area average particle diameter of 4 to 6 nm (nominal enthalpy) was sequentially added. (Manufactured by Nissan Chemical Industries, Inc., Snowtex (registered trademark) XS (solid content concentration: 20%)) and colloidal cerium oxide (B) having a surface area average particle diameter of 1 〇 to 20 nm (nominal 値) (manufactured by Nissan Chemical Industries, Ltd. Snowtex (registered trademark) 40 (solid content concentration: 40%), and after mixing the two together, 'add a glycidyloxy-containing decane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM403 (solid content concentration: 100%)), Next, sodium metavanadate (manufactured by Emerging Chemical Industry Co., Ltd., 'sodium vanadate (solid content concentration: about 66%)) was added as metavanadate. Further, an acrylic modified epoxy resin (manufactured by Arakawa Chemical Industries, Ltd., M0DEPICS (registered trademark) 302 (solid content concentration: 33.5%)) was added to the mixture to prepare a surface treatment composition. Moreover, the mixing amount (or mixing ratio) of each component in the preparation of the surface treatment composition is as follows. -32- 201132802 Mass ratio of colloidal cerium oxide (A) and (B): 50: 50 Inorganic component and resin component (the amount of all solid components in the above emulsion and the acrylic modified epoxy resin, the same applies hereinafter) The mass ratio of 3 〇 70 to 95: 5 The amount of the acrylic acid-modified epoxy resin is 5 parts by mass based on 95 parts by mass of all the solid components in the emulsion (5% by mass in the resin component). The blending amount of the decane coupling agent is 10 parts by mass based on 100 parts by mass of the total of the inorganic component and the resin component, and the total amount of the inorganic component and the resin component is 1 part by mass based on 100 parts by mass. &lt;Production of resin-coated metal sheet &gt; As a metal plate, an alkali degreased hot-dip galvanized steel sheet GI material (Zn adhesion amount: 45 g/m 2 ) or alloyed hot-dip galvanized steel sheet GA material (Zn adhesion amount: 45 g/m 2 ) was used as a bar coater (Νο·3) The surface-treated composition was applied to the surface of the steel sheet by a bar or a crucible, and dried at a plate temperature of 90 ° C for about 12 seconds to obtain a resin-coated metal plate having a resin film adhesion amount of 0.5 g/m 2 . The evaluation results of the obtained resin-coated metal sheets are shown in Table 1. (Experimental Example 1 - 1 1 ) &lt;Preparation of surface-treated composition&gt; Lithium niobate having a SiO 2 / Li 20 molar ratio of 4.5 ("Niobium Niobate 45" manufactured by Nissan Chemical Industries, Ltd.) and surface area average particle diameter (No. 値-33-201132802) A colloidal cerium oxide (Nissan Chemical Industry Snowtex (registered trademark) XS) of 4 to 6 nm is mixed in a mass ratio of 90: to prepare an inorganic component. In the above emulsion, the obtained inorganic component is added and mixed, and then a glycidoxy coupling-containing decane coupling agent (manufactured by Konica Minolta Co., Ltd., KBM403, γ-glycidoxypropyl III) is added, followed by the addition of vanadium Sodium (sodium produced by Xinxing Chemical Industry Co., Ltd.). In the mixture, a oxazoline-based Nippon Catalyst Co., Ltd. product, Epocros (registered trademark) solid content (40% by mass) was further added to prepare a surface-treated composition. Further, each component or mixing ratio in the production of the above surface treatment composition is as follows. The mixing ratio of the mixture of the inorganic component and the copolymer of all the solid component groups in the above-mentioned emulsion is 70:30. The blending amount of the oxazoline group-containing copolymer is 95 parts by mass of the total solid content, and 5 parts by mass of the epoxy group. a mixed amount of a propoxy coupling agent of a propoxy group and a total of 1 part by mass of a total of 15 parts by mass of sodium metavanadate in a mixture of all solid components and an oxazoline-containing mixture in the above emulsion, 11 relative inorganic components and The mixed mass parts of all the solid components and the oxazoline group-containing copolymer were 5 parts by mass. &lt;Preparation of resin-coated metal sheets&gt; The company manufactured, 10, and the two were charged with the chemical ethoxy decane. The amount of the copolymer of meta-vanadic acid (K-2030E, and the copolymer of the above-mentioned oxazoline-containing emulsifier-inorganic-based emulsifier) 1 〇〇-34- 201132802 except the use of Experimental Example 1 A resin-coated metal plate was produced in the same manner as in Experimental Example 1-1 except for the surface-treated composition prepared in the above paragraph 1. The evaluation results of the obtained resin-coated metal plate are shown in Table 1. -35- 201132802 GA substrate bare Corrosive (flat) 1 JASO Ο ◎ ◎ ◎ ◎ &lt; X &lt; XX SST § (N VO Os 1 § &lt; 24 &lt; 24 臓 难 ® Ο Ο ◎ ◎ ◎ 〇 X &X; X • XXX SST Ο ◎ ◎ ◎ ◎ 0 &lt;1 1 &lt;1 XX GI substrate surface tension (dyn/cm) 5 oo v〇1 *n Ό m Exposed corrosion resistance (flat plate) JASO 0 ◎ ◎ ◎ ◎ &lt;] XX 1 X ◎ SST 5 § § § § oo 00 Ό • &lt;24 00 V 〇 S roll formability 〇 ◎ ◎ 〇 〇 &lt;3 XX 1 X o Attach S (g/m2) *n ο 1» 菡趦蘅- Epoxy propoxy decane coupling agent ο »n Resin component Acrylic modified is Oxygen resin emulsion: Acrylic modified epoxy resin = 95:5 ο fS sg Ο «r> oxazoline group-containing copolymer emulsion : Chewable thiol-containing copolymer = 95:5 1 1 1 fig 3 1 i ||l K sg SI® Inorganic component colloidal cerium oxide (B) Average particle size 10 〜20 nm 〇m WJ SO o in g 00 s «η σν Lithium niobate colloidal cerium oxide: lithium niobate = 丨0:90 〇 colloidal cerium oxide (A) average particle size 4~6nm colloidal cerium oxide average particle size 4-^nm experimental example 1-1 Experimental Example 1-2 Experimental Example 1_3 Experimental Example 1*4 Experimental Example 1-5 Experimental Example K Experimental Example 1-7 Experimental Example 8 Experimental Example 1-9 Experimental Example Μ〇 Experimental Example 11 -36-201132802 (Experimental Example 2-1 to 2-10) &lt;Preparation of surface-treated composition&gt; The same as in the experimental example 1·3 except that the mass ratio of the colloidal cerium oxide (A) to the colloidal cerium oxide (B) was changed by 1 〇〇: 〜: 1 0 0 Operation, making a surface treatment composition. &lt;Production of Resin-Coated Metal Sheet&gt; A resin-coated metal sheet was produced in the same manner as in Experimental Example 1-3 except that the surface-treated composition prepared in Experimental Example 2·1 to 2 -1 使用 was used. The evaluation results of the obtained resin-coated metal sheets are shown in Table 2. (Experimental Example 2-1 1 to 2-12) In addition to the use of colloidal cerium oxide (manufactured by Nissan Chemical Industries, Inc., 'Snowtex (registered trademark) 50) or surface area average granules having an average surface area of 20 to 3 Onm (nominal 値) A colloidal cerium oxide having a diameter of 40 to 5 Onm (nominal 値) (made by Nissan Chemical Industries Co., Ltd. 'Snowt ex (registered trademark) 20 L) was used in the same manner as in Experimental Example 2-1 except for the colloidal cerium oxide (B). , making a surface treatment composition. &lt;Production of Resin-Coated Metal Sheet&gt; A resin-coated metal sheet was produced in the same manner as in Experimental Example 2-1 except that the surface-treated composition prepared in Experimental Example 2-1 1 to 2-2 was used. The evaluation results of the obtained resin-coated metal sheets are shown in Table 2. -37- 201132802 GA substrate bare corrosion resistance (flat plate) JASO ◎ ◎ ◎ ◎ ◎ ◎ &lt; XXXXXI SST § S Art &lt;24 &lt;24 &lt;24 Coating film adhesion salt water resistance 〇 ◎ ◎ ◎ ◎ 〇 〇 ;] XXXXX SST ◎ ◎ ◎ ◎ ◎ 〇〇 〇〇 &lt;] &lt;1 XXX GI substrate bare corrosion resistance (flat) JASO 〇 ◎ ◎ ◎ ◎ 〇 &lt;1 XXX &lt;1 X SST § § § § Μ oo &lt 24 Η light formability ◎ ◎ ◎ ◎ ◎ ◎ &lt;] ◎ ◎ &lt;] XX Attach a (Caf 2) i 1 1_ *n 〇 - Glyoxyloxy-containing decane coupling agent O Resin component Inorganic component: Resin composition = 70:30 Acrylic modified epoxy resin emulsion: Acrylic modified epoxy tree sg=95:5 ill 11^ K 1 IS Xia g Inorganic ingredient £ | 7 ¥ 2 * ® u & 叆ST S ο *Λ *τί %nso tn &lt;N Ο o ε 〇S 7 i contains II H m moose gull ST E ^ 2 ii m 豳& S &lt;屋ο s V*» oo jn *nmo O ο 2-1 Test Example 2-2 Experimental Example 2-3 Experimental Example 24 Experimental Example 2-5 Experimental Example 2·6 Experimental Example 2-7 Experimental Example 2-8 Experimental Example 2-9 Experimental Example 2-10 Experimental Example 2 -11 Experimental Example 2-12 - 38-201132802 (Experimental Example 3-1 to 3-1 1 ) &lt;Preparation of surface-treated composition&gt; In addition to making the amount of the acrylic-modified epoxy resin mixed with the total solid content of the above-mentioned emulsion 80-100 00 The surface treatment composition was produced in the same manner as in Experimental Example 1 to 3 except that the amount was 〇2 to 2 parts by mass (0 to 20 mass% in the resin component). &lt;Production of Resin-Coated Metal Sheet&gt; A resin-coated metal sheet was produced in the same manner as in Experimental Example 1-3 except that the surface-treated composition prepared in Experimental Example 3-1 to 3-1 was used. The evaluation results of the obtained resin-coated metal sheets are shown in Table 3.

S -39- 201132802 m GA substrate bare corrosion resistance (Ping® JASO ◎ • ◎ ◎ ◎ Ο 〇〇〇 0 X SST • s〇〇v Ν | N s M &lt; 24 Coating adhesion H salt ◎ - ◎ ◎ ◎ ◎ Ο XX &lt;1 X SST ◎ • ◎ ◎ ◎ ◎ 〇 &lt;&lt;1&lt;1 X GI substrate bareness saturation (flat) JASO ◎ ◎ 1 ◎ ◎ Ο Ο 0 0 XX SST § § t § § § § &lt;24 Sweet roll formability ◎ 1 ◎ ◎ ◎ ◎ ◎ ◎ 〇 adhesion amount (g/m2) 菡 chain 蘅 - epoxidizer containing propylene oxide oxime resin component inorganic component: Resin composition = 70:30 Acrylic modified epoxy resin dip VJ o a r- s shock 8 00 On On SO *Tl ON On s Wi 00 o 00 g Inorganic component ω 1 &amp; 7 ^ 〇f, m ® (A): (B)=50:50 &lt; | e ^ mg ϋ 1 豳η- Experimental Example 3·1 Experimental Example 3-2 Experimental Example 3-3 Experimental Example 34 Experimental Example 3-5 Experimental Example 3-6 Experimental Example 3-7 Experimental Example 3-8 Experimental Example 3-9 Experimental Example 3-10 Experimental Example 3-11 • 40-201132802 (Experimental Examples 4-1 to 4-9) &lt;Preparation of Surface Treatment Composition&gt; In addition to the glycosyloxy-containing broth ingredients In the same manner as in the first example, the same procedure was carried out to prepare the surface-coated metal sheet. The same procedure as in the experimental example 1-3 was carried out except that the experimental example 4-1 to 4_9 m ' was used. As a result of evaluation of the resin-coated metal sheet, the amount of the coupling agent to be mixed was equal to that of the inorganic r, and the composition was mixed with a resin-coated metal sheet other than the surface-treated composition. -41 - 201132802 m &lt; ο 1 Ι 辕s Although o —» 〇 ◎ ◎ ◎ ◎ XX 〇 XC/3 JN SV pi (N 艺 V 掏 m 1 翻 V 〇 ◎ ◎ ◎ 〇 XXXX Η 〇 ◎ ◎ ◎ ◎ X &lt;] &lt;] X m R hundred sk | BI « 3 (N mm If 踺&amp; m Ο V3 &lt; 〇 ◎ ◎ ◎ ◎ X &lt;3 &lt;1 X (- C/3 ί/5 § § s § TJ* V s V 11^ O ◎ ◎ ◎ ◎ X &lt;&lt;1 X _ Ί U&quot;i — K 蘅 蘅 13⁄4 S &lt;0 mmm Φ3 « ss «Λ&gt; 〇 〇 W~io 卜Sg m 碧am 1 I r •Λ) I OZI Jg bribe m i i KK 辜云 S SI1 1 m I ι i ff 1 7 ̄ο ffl o 1 ® E « 1 J a mm Ά (N s tt 乐 κ Sm 舾vp m M SO-smur*pmmm 00 mm K On Interest u -42- 201132802 (Experimental Examples 5-1 to 5-10) &lt;Preparation of surface treatment composition&gt; In addition to the amount of metavanadate mixed with inorganic components and In the same manner as in Experimental Example 丨3, a surface treatment composition was prepared in the same manner as in Experimental Example 丨3. &lt;Preparation of Resin-Coated Metal Sheet&gt; A resin-coated metal sheet was produced in the same manner as in Experimental Example 1-3 except that the surface-treated composition prepared in the following Examples 5-1 to 5 -1 was used. The evaluation results of the obtained resin-coated metal sheets are shown in Table 5.

S -43- 201132802 π *

GA substrate bare corrosion resistance (flat plate) JASO 〇 ◎ ◎ ◎ ◎ ◎ X &lt; 3 Ο Ο SST (N s &lt; 24 μ &lt; Ν Ν Ν 涂 film adhesion water resistance © ◎ ◎ © 〇〇 ◎ ◎ XX SST ◎ ◎ ◎ ◎ 〇〇 ◎ ◎ XX GI substrate bare corrosion resistance (flat plate) JASO ◎ ◎ ◎ ◎ ◎ ◎ 〇〇 & & § § § § § § § § § § § § § Μ Roller formability ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 adhesion amount (g/m2) »r&gt; 〇 銮趦蟊 n*n ο ο ο ρ Ο (Ν s ο »Λ» Ο wS mmm ts &&lt;n 〇&lt;f0 E s Chain Sg

I

mI I K S ^ ^ ώ § K s g K) ^ ® £ m II 歴 歴 m | m ^ 兹! f} ^ 鹚 κ 〇 (N rn 1 »r&gt; v〇r- 1 oo as smgm 匡 fun fun mmmm 锴mmmm tt K Λ u KK u *Λ 舾-44- 201132802 (Experimental Example 6-1~ 6-8) &lt;Production of Resin-Coated Metal Sheet&gt; A resin-coated metal sheet was produced in the same manner as in Experimental Example 1-3 except that the amount of the resin film adhered was 0.1 to 1.5 g/m2. The evaluation results of the obtained resin-coated metal sheets are shown in Table 6. -45 - 201132802

Co * GA substrate bare corrosion resistance (plate) JAS0 〇 ◎ © ◎ ◎ X ◎ ◎ SST (N § &lt; 24 § coating film adhesion salt water 〇 ◎ ◎ ◎ 0 XXX SST 〇 ◎ ◎ ◎ ◎ XXX CH substrate Exposed corrosion resistance (flat plate) JASO 〇 ◎ ◎ ◎ ◎ X ◎ ◎ SST § § § &lt; 24 00 Ό Light resistance 〇 ◎ ◎ ◎ 〇 X &lt; 3 X Adhesion (g/m2) (N d Bu · ρ 5 y/-) A propylene oxide coupling-containing enamel coupling agent 〇 resin component acrylic modified epoxy resin emulsion: acrylic modified epoxy tree 11=95:5 ^ ^ ^ chain ώ 2 S Section SES g S 1 i Inorganic component m % mb ff 1 7 II ΚΙ-2 Acid (A): (B) = 50:50 〇 Colloidal cerium oxide (A) Average particle size 4 to 6 nm Experimental example 6-1 Experimental Example 6-2 Experimental Example 6-3 Experimental Example 64 Experimental Example 6-5 Experimental Example 6-6 Experimental Example 6-7 Experimental Example 6-8 - 46 - 201132802 Industrial Applicability The present invention can provide a not only satisfaction A resin-coated metal sheet which is resistant to the GI material and which satisfies the roll formability of the GI material and the coating film adhesion after the post-coating required by the GA material.

S -47-

Claims (1)

201132802 VII. Patent application scope: 1. A resin coated metal plate having a resin film obtained by a surface treatment composition, characterized in that the surface treatment composition contains: 60 to 80 parts by mass of surface area average particles An inorganic component composed of a plurality of colloidal cerium oxides having a diameter different from each other, and 20 to 40 parts by mass of an olefin-α,β-unsaturated carboxylic acid copolymer, an α,β-unsaturated carboxylic acid polymer, and an acrylic acid modified a resin component composed of an epoxy resin, and a propylene oxide coupling agent containing 5 to 15 parts by mass based on 100 parts by mass of the total of the inorganic component and the resin component, and 〇. 5 to 3 Metavanadate. 2. The resin-coated metal plate according to claim 1, wherein the inorganic component contains colloidal cerium oxide (A) having a surface area average particle diameter of 4 to 6 nm and colloidal cerium oxide having a surface area average particle diameter of 10 to 20 nm. (B), the mixing ratio of the above (A) and (B) is 70: 30 to 40: 60 by mass ratio. 3. The resin-coated metal sheet according to claim 1 or 2, wherein the resin component contains 2 to 15% by mass of the acrylic modified epoxy resin. 4. The resin-coated metal sheet according to claim 1 or 2, wherein the surface treatment composition has a surface tension of 50 dyn/cm or less. 5. The resin-coated metal sheet according to claim 1 or 2, wherein the amount of the resin film adhered is 0.2 to lg/m2 in terms of dryness. 6. The resin-coated metal sheet according to claim 1 or 2, wherein the metal sheet having the resin film is a molten plated steel plate or an alloyed hot-dip galvanized steel sheet. -48- 201132802 IV. Designated representative map: (1) The representative representative of the case is: None. (2) Simple description of the symbol of the representative figure: None 201132802 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none