JP2006336106A - Chromium-free surface treatment agent for metal, and surface-treated metallic material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a chromium-free surface treatment agent applied to various metals and having excellent adhesion with a raw material, corrosion resistance, the adhesion of a coating material, the corrosion resistance of a coating film, electrodeposition coating properties, the corrosion resistance of an electrodeposited coating film, lubricity, the rust preventability of an edge face and corrosion resistance in a worked part. <P>SOLUTION: The metal surface treatment agent is obtained by blending a zirconium compound, sol of SiO<SB>2</SB>, Al<SB>2</SB>O<SB>3</SB>, MgO and TiO<SB>2</SB>, and a phosphoric acid compound of Al in specified ratios. The metal surface treatment agent is obtained by blending an Mn compound, a Cu compound, an Ni compound and a Co compound, or further, an oxidizer, a polyethyleneglycol type surfactant, an acetylenic diol composition, water base organic resin emulsion and water soluble organic resin. The metallic material is obtained by being subjected to surface treatment with these surface treatment agents. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention is a metal such as aluminum or aluminum alloy plate, magnesium or magnesium alloy plate, titanium or titanium alloy plate, nickel or nickel alloy plate, copper or copper alloy plate, zinc or zinc alloy plate, tin or tin alloy plate, silicon steel plate , Stainless steel, etc., and also cold rolled steel sheets, black skin hot rolled steel sheets, pickled hot rolled steel sheets, thick plates, shaped steels, pipes, wire rods, etc., and Zn, Ni, Cu, Fe, Al, Co , Ti, Mg, Mn, Sn, etc., plated steel sheets plated on steel sheets, alloy plated steel sheets plated with two or more of these metals, etc. By coating and drying on the surface of metal bodies, etc., it shows excellent adhesion to the material, and also has extremely excellent corrosion resistance, paint adhesion, coating corrosion resistance, electrodeposition coating properties, electrodeposition coating film resistance. Sex, to a metallic material having a surface treatment agent and surface treatment film to form a chromium-free surface treatment film of showing an end face rust resistance and lubricity.

In order to improve corrosion resistance and paint adhesion, various metal materials such as various plated steel sheets including galvanized steel sheets and various metal sheets including aluminum are generally subjected to chromate treatment. In the chromate treatment, hexavalent chromium is present in the formed film, but hexavalent chromium has a strong oxidizing action, enters the body, destroys cells, and is also a carcinogen. Therefore, recently, regulations on chromium (especially hexavalent chromium) have been greatly strengthened on a global scale due to environmental and pollution problems.

Accordingly, so-called chromium-free surface treatment agents that do not use chromium have been developed, and various types of coating compositions have been known. As a composition containing an inorganic compound as a main component, for example, Japanese Patent Application Laid-Open No. 2000-345355 is composed of a mixture of silica and zirconia, and the amount ratio of silica and zirconia is SiO ₂ : 55 to 99 wt%, ZrO ₂ : 45 to 1 wt%. It is characterized by the fact that it is recommended to be used as a protective film on welded parts and machined surfaces of automotive aluminum parts, aluminum parts of heat exchangers, etc.

Japanese Patent Application Laid-Open No. 2000-282256 is a chromium-free rust-proofing agent for aluminum, characterized in that a zirconium compound and a zinc compound are blended in an amount of zinc / zirconium weight ratio of 0.01 to 1. Japanese Patent Laid-Open No. 2000-199077 is characterized in that it contains metal acetylacetonate and at least one compound selected from water-soluble inorganic titanium compounds and water-soluble inorganic zirconium compounds in a weight ratio of 1: 5000 to 5000: 1. . Japanese Patent Application Laid-Open No. 2001-355079 is a surface treatment agent for an aluminum material mainly composed of tannin or tannic acid and a chelating agent. Japanese Patent Application Laid-Open No. 2005-008948 includes a lithium compound and a carbonic acid compound, and an oxidizing agent that is at least one selected from lithium, sodium, potassium, and ammonium salt compounds of persulfuric acid, nitric acid, nitrous acid, and bromic acid. It is characterized by. JP-A-2004-183015 discloses a vanadium compound (A), a metal compound (B) containing a metal selected from cobalt, nickel, zinc, magnesium, aluminum, calcium, strontium, barium and lithium, and optionally zirconium and titanium. And a metal compound (C) containing a metal selected from molybdenum, tungsten, manganese and cerium. JP-A-2001-081392, JP-A-2000-204485, JP-A-2003-313681, and the like can be cited as combinations of organic resins and various inorganic compounds.

For example, in the production line of various plated steel sheets including galvanization or the production line of aluminum and aluminum alloy, the chromate is often dried in a short time of 5 to 15 seconds at 100 ° C. or less. When a chromium-free surface treatment agent is introduced instead of chromate, if it can be dried at a temperature of 100 ° C. or less for a short time, it is not necessary to make a new capital investment and the introduction is very easy. All of the above known techniques are dried at a low temperature (100 ° C. or less) and in a short time (1 to 15 seconds), thereby being able to adhere to the material, corrosion resistance, paint adhesion, coating corrosion resistance, electrodeposition coating property, A coating excellent in corrosion resistance, corrosion resistance at the end face, and lubricity cannot be formed, and there is no one that makes this possible, and none has been put into practical use.

On the other hand, the present invention solves the drawbacks of the above-mentioned conventional techniques, applies extremely thinly to a metal material, exhibits excellent adhesion to the material by drying at low temperature and in a short time, and has extremely excellent corrosion resistance, The primary purpose is to provide a chromium-free surface treatment agent that can ensure paint adhesion, paint film corrosion resistance, electrodeposition paintability, electrodeposition paint film corrosion resistance, end face rust resistance and lubricity, and The second object is to provide a metal material having these chromium-free surface-treated films.

Means for solving the problem

That is, the present invention includes (1) 10 to 2000 parts by weight of one or more sols (colloids) of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ with respect to 100 parts by weight of the zirconium compound. And 10 to 500 parts by weight of an Al phosphate compound per 100 parts by weight of the total amount of one or more of the sols of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ blended. (2) 1 of Mn compound, Cu compound, Ni compound and Co compound with respect to 100 parts by weight of the total solid content contained in the surface treatment agent in the surface treatment agent described in (1) above 1 to 100 parts by weight of seeds or two or more species, and (3) the surface treating agent according to (1) and (2) above. It is a metal surface treatment agent characterized by blending 0.1 to 100 parts by weight of one or more oxidizing agents with respect to 100 parts by weight of the total solid content, and (4) the above (1) In addition, 0.05% of one or two of a polyethylene glycol surfactant and an acetylene diol composition is added to 100 parts by weight of the total solid content in the surface treatment agent described in (2) and (3). The surface treatment agent is characterized by containing -5.0 parts by weight, and (5) the aqueous organic resin emulsion in the surface treatment agent according to (1), (2), (3) and (4) Or it is a surface treating agent characterized by mix | blending water-soluble resin 5 to 98% by weight density | concentration with respect to a total solid, Moreover, (6) On said metal material, (1) or (2) or (3) or (4) or (5) metal surface treatment It is a surface-treated metal material characterized by having a coating amount of 0.05 to 10.0 g / m ² formed by applying a chemical agent.

When one kind or two or more kinds of a sol (colloid) of a zirconium compound and SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ are blended in a specific ratio, paint adhesion and coating corrosion resistance are improved. Furthermore, when a specific proportion of Al phosphate compound is added, the corrosion resistance, paint adhesion, coating corrosion resistance, electrodeposition coating properties and electrodeposition coating corrosion resistance are improved, and adhesion to the material metal (for example, hot dip galvanized steel sheet) is improved. And a film excellent in lubricity is formed. In addition, these films can be formed by drying at a low temperature for a short time. Moreover, when 1 type, or 2 or more types of a Mn compound, Cu compound, Ni compound, and Co compound is mix | blended, corrosion resistance, coating-film corrosion resistance, and end surface rust prevention property will improve significantly. Further, when a specific amount of the oxidizing agent is blended, the corrosion resistance is further improved. Further, when a specific amount of one or two of a polyethylene glycol surfactant and an acetylene diol composition is blended, the corrosion resistance, paint adhesion, and coating film corrosion resistance are further improved. Further, when a water-based organic resin emulsion or a water-soluble resin is blended, the corrosion resistance of the processed part and the end face part is improved.

The inventors of the present application added ductility when a specific proportion of the zirconium compound and one or more of the sols of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ and the phosphoric acid compound of Al were blended. We discovered that there is a region where a dense and tough film can be formed. Moreover, it was found that the formed film has a property of strongly bonding with many organic substances including the coating film. In general, the adhesion of organic compounds to organic substances is considerably poor except for those that are limited, such as phosphate films (chemical conversion films). In the world of surface treatment, as a method for improving the adhesion to a coating film, it is usually performed by mixing an organic substance having an OH group and introducing the OH group into the film. Although the compound formed according to the present invention is an inorganic compound, it has a very strong binding force with organic substances such as a coating film, far exceeding that of a phosphate film, and bonds between OH group-introduced films and organic films. Is far surpassed and no other inorganic compound is found.

A compound formed by blending a zirconium compound according to the present invention, one or more of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ sols and an Al phosphate compound in a specific ratio and an organic substance The extremely strong binding force is born between the three substances according to the present invention by forming a specific coordination compound by coordinating and forming a strong van der Waals force. It seems to combine.

The compound formed according to the present invention forms a dense and tough film and has excellent properties of strongly bonding with organic matter, so when applied to metal, adhesion to the material, corrosion resistance, paint adhesion, coating film corrosion resistance Properties such as electrodeposition coating properties, electrodeposition coating corrosion resistance, and lubricity are imparted. The following shows how the characteristics of the formed film change depending on the blending ratio of the zirconium compound, SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ sol and Al phosphate compound used in the present invention.

A liquid in which the blending ratio of zirconia sol (zirconium compound) and silica sol was changed was prepared, and a liquid in which 25 parts by weight of primary aluminum phosphate was blended with respect to 100 parts by weight of the total solid content of the two was added to the hot dip galvanized steel sheet. Coating with 0.3 g / m ² (solid content after drying) and drying at 60 ° C. Adhesion with the material (hot dip galvanizing), corrosion resistance, paint adhesion, coating corrosion resistance, electrodeposition coating properties The corrosion resistance and lubricity of the electrodeposition coating film were examined.

When 10 to 2000 parts by weight of silica sol is blended with 100 parts by weight of zirconia sol, paint adhesion and coating film corrosion resistance are improved. Moreover, even if the blending ratio of both the zirconia sol and the silica sol is changed, the adhesion to the material, the corrosion resistance, the electrodeposition coating property, the electrodeposition coating film corrosion resistance and the lubricity are not greatly changed. Similar results were obtained when Al ₂ O ₃ , MgO and TiO ₂ sols were used instead of the SiO ₂ sol. In addition, almost the same results were obtained even when two or more of these compounds were blended.

From the above results, it is necessary to blend 10 to 2000 parts by weight of one or more sols of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ with respect to 100 parts by weight of the zirconia sol.

Next, 100 parts by weight of silica sol was blended with 100 parts by weight of zirconia sol, and liquids were prepared by blending primary aluminum phosphate in various proportions with respect to 100 parts by weight of the total amount of zirconia sol and silica sol. These surface treatment liquids were applied to a hot-dip galvanized steel sheet at 0.3 g / m ² (solid content after drying) and dried at 60 ° C. to form a film. The primary aluminum phosphate has a great influence on the characteristics of each film, and when it is added in an amount of 10 parts by weight or more with respect to 100 parts by weight of the total amount of zirconia sol and silica sol, the adhesion to the material and the corrosion resistance are improved. In addition, when 10 to 500 parts by weight of primary aluminum phosphate is blended, paint adhesion, coating corrosion resistance, electrodeposition coating property, electrodeposition coating corrosion resistance and lubricity are remarkably improved, and less than 10 parts by weight and more than 500 parts by weight. Decrease. Even if the sol of Al ₂ O ₃ , MgO and TiO ₂ is used in place of the SiO ₂ sol, or two or more of these compounds are used, the primary phosphorus is added to 100 parts by weight of the total amount of these compounds blended with the zirconia sol. Almost the same result was obtained when 10 to 500 parts by weight of aluminum oxide was blended. In addition, substantially the same result was obtained even when another Al phosphate compound was used in place of the primary aluminum phosphate.

In the above zirconia sol and _SiO 2 from the _result, Al ₂ O 3, MgO and one or a mixture blended with two or more of the TiO ₂ sol, Al weight per 100 parts by weight of all compounds in the liquid It is necessary to blend 10 to 500 parts by weight of the phosphoric acid compound.

Next, 100 parts by weight of silica sol was blended with 100 parts by weight of zirconia sol, and 80 parts by weight of primary aluminum phosphate was blended with respect to 100 parts by weight of the total amount of zirconia sol and silica sol. A surface treatment liquid containing Co phosphate in various proportions with respect to 100 parts by weight of the total solid content of this liquid was applied to a hot-dip galvanized steel sheet at 0.3 g / m ² (solid content after drying) and dried at 60 ° C. A film was formed. When 1.0 part by weight or more of Co phosphate is blended, the corrosion resistance, the coating film corrosion resistance, and the end face rust prevention property are further improved. On the other hand, when it exceeds 100 parts by weight, the corrosion resistance, the coating film corrosion resistance, the end face rust resistance and the paint adhesion are lowered. Electrodeposition paintability, electrodeposition coating corrosion resistance, and lubricity are not particularly affected by the addition of Co phosphate. Substantially similar results were obtained when using a Mn compound, Cu compound and Ni compound instead of the Co compound. In addition, almost the same results were obtained even when two or more of these compounds were blended.

As a result, 1.0 to 100 parts by weight of one or more of Mn compound, Cu compound, Ni compound and Co compound must be blended with respect to 100 parts by weight of the total solid content contained in the surface treatment agent according to the present invention. is there.

When one or more of Mn compound, Cu compound, Ni compound and Co compound is added to the surface treatment agent according to the present invention, the mechanism for further improving the corrosion resistance, coating film corrosion resistance and end face rust prevention property is as follows. is there. That is, the Mn compound, the Cu compound, the Ni compound, and the Co compound are determined by the _three compounds of the zirconium compound according to the present invention and one or more of the SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ sols, and the Al phosphate compound. It was found that only the formed compound functions as a modifying compound and has a network structure. On the other hand, it was found that other compounds than the present invention do not function as a modifying compound and therefore do not take a network structure. Here, when the network structure is taken, a tough and denser film is formed. Thus, even if a compound other than the Mn compound, Cu compound, Ni compound and Co compound coexists in the compound formed according to the present invention, or the compound other than the present invention includes Mn compound, Cu compound, Ni compound and Co compound. Even when coexisting, a network structure is not formed, and a network structure is formed only when Mn compound, Cu compound, Ni compound and Co compound coexist in the compound formed according to the present invention, and it is a tough and denser film. Found that formed. On the other hand, when placed in a corrosive environment, Mn, Cu, Ni, and Co have a strong bond with a corrosion factor (for example, Cl ⁻ ion), and therefore preferentially have Cl ⁻ ions diffused from the buttock or end face of the coating film. It binds to (forms a chloride) and suppresses the penetration of Cl ⁻ ions into the interior as much as possible. Thus, it is considered that the corrosion resistance, the coating film corrosion resistance, and the end face rust prevention properties are improved by densifying the corrosion factor into the film by densifying the film and capturing the corrosion factor. On the other hand, if the blending amount is too large, the film forming property and paint adhesion of the coating are inhibited, so that a large amount of corrosive factors are allowed to enter, and the corrosion resistance, coating film corrosion resistance and end face rust prevention property are adversely decreased.

Next, 100 parts by weight of silica sol was blended with 100 parts by weight of zirconia sol, and 80 parts by weight of primary aluminum phosphate was blended with respect to 100 parts by weight of the total amount of zirconia sol and silica sol. A surface treatment liquid containing nitric acid in various proportions with respect to 100 parts by weight of the total solid content of this liquid was applied to a hot-dip galvanized steel sheet at 0.3 g / m ² (solid content after drying) and dried at 60 ° C. A film was formed. When 0.1 parts by weight or more of nitric acid is blended, the corrosion resistance is further improved. Moreover, when it exceeds 100 weight part, corrosion resistance will fall. Paint adhesion, coating corrosion resistance, electrodeposition coating property, electrodeposition coating corrosion resistance and lubricity are not particularly affected by the addition of nitric acid. Similar results were obtained using an oxidizing agent other than nitric acid. In addition, almost the same result was obtained even when two or more kinds of oxidizing agents were used in combination. Further, when the Mn compound, Cu compound, Ni compound and Co compound have an oxidizing function, the total amount of these compounds and the newly added oxidizing agent may be 0.1 to 100 parts by weight.

As a result, the suitable blending amount of the oxidizing agent is 0.1 to 100 parts by weight with respect to 100 parts by weight of the total solid content contained in the surface treatment agent.

Here, when an oxidizing agent is blended with the present invention, the corrosion resistance is improved as follows. That is, when the zirconium compound, SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ sol and Al phosphate compound in the present invention are blended in specific ratios, these three substances adsorb or react to form a new compound. However, it is considered that when an oxidizing agent is added, it functions as a so-called reaction accelerator that promotes the reaction formed by the new compound in the present invention.

Next, 50 parts by weight of silica sol was blended with 100 parts by weight of zirconia sol, and 50 parts by weight of primary aluminum phosphate was blended with respect to 100 parts by weight of the total amount of zirconia sol and silica sol. Applying 0.4 g / m ² (solid content after drying) to a hot-dip galvanized steel sheet, a surface treatment liquid containing polyethylene glycol type surfactant in various proportions with respect to 100 parts by weight of the total solid content of this liquid, A film was formed by drying at 80 ° C. Addition of 0.05 part by weight or more of a polyethylene glycol type surfactant further improves the corrosion resistance, paint adhesion and coating film corrosion resistance. On the other hand, when it exceeds 5.0 parts by weight, both corrosion resistance, paint adhesion and coating film corrosion resistance are lowered. Moreover, even if it used the acetylene type diol composition instead of the polyethyleneglycol type surfactant, or used both together, the substantially same result was obtained. Further, the addition of the polyethylene glycol type surfactant or the acetylene diol composition does not greatly affect the electrodeposition coating property, the electrodeposition coating corrosion resistance and the lubricity.

As a result, the suitable blending amount of one or two of the polyethylene glycol type surfactant and the acetylene-based diol composition in the present invention is 0.05 to 5 with respect to 100 parts by weight of the total solid content contained in the surface treatment agent. It is necessary to add 0.0 part by weight.

Here, when a polyethylene glycol type surfactant and / or acetylene-based diol composition is added to the compound of the present invention, the mechanism of further improving the corrosion resistance, paint adhesion, and coating film corrosion resistance is not necessarily clear at present, but as follows. Conceivable. That is, when the zirconium compound, SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ sol and Al phosphate compound in the present invention are blended in specific ratios, these three substances adsorb or react to form a new compound. However, when a polyethylene glycol-type surfactant and / or acetylene-based diol composition coexists, the polyethylene glycol-type surfactant and / or acetylene-based diol composition exhibits a function as a catalyst, and a new compound by three parties. It is believed to promote the reaction that forms. Moreover, after a new compound is formed, it is adsorbed on the surface of the compound to improve the leveling property, and it is considered that it contributes to the formation of a film having no defect on any metal.

The surface treatment agent of the present invention is a component of the above inorganic compound and can significantly improve the corrosion resistance, paint adhesion, coating film corrosion resistance, electrodeposition coating property, electrodeposition coating film corrosion resistance and lubricity. By adding a specific amount of a water-based organic resin emulsion or a water-soluble resin having film-forming properties to the surface treatment agent, the corrosion resistance of the processed part and the end face part can be further improved.

Next, 80 parts by weight of silica sol was added to 100 parts by weight of zirconia sol, and 100 parts by weight of primary aluminum phosphate was added to 100 parts by weight of the total amount of zirconia sol and silica sol. A surface treatment liquid containing various proportions of an aqueous acrylic resin emulsion was applied to this liquid on a hot dip galvanized steel sheet at 0.3 g / m ² (solid content after drying) and dried at 100 ° C. to form a film. . When the ratio of the water-based acrylic resin emulsion to the total solid content is less than 5%, the corrosion resistance of the processed part and the end face rust resistance are lowered. If it exceeds 98.0%, both the corrosion resistance of the processed part and the rust resistance of the end face are significantly reduced. Similar results were obtained using a water-based organic resin emulsion or a water-soluble resin having a film forming property other than the water-based acrylic resin emulsion.

As a result, the blending ratio of the water-based organic resin emulsion or the water-soluble resin in the present invention is 5% or more and less than 98.0% by weight with respect to the total solid content contained in the surface treatment agent.

Here, when the surface treatment agent of the present invention is blended with a water-based organic resin emulsion having a film-forming property or a water-soluble resin, the corrosion resistance of the processed part and the end face part is greatly improved as follows. In general, when an inorganic compound is blended with an organic resin, the inorganic compound becomes an impurity, weakening the bond between the organic resins and reducing the film strength. Moreover, when it is more, it cannot form a film. On the other hand, the compound formed according to the present invention has a function of binding extremely strongly to an organic substance, and therefore strongly bonds to a coexisting organic resin. As a result, a tough film is formed, a film that can withstand severe processing is formed, and the corrosion resistance of the processed portion is improved. Further, since the film formed at the same time is densified, the corrosion resistance of the end face part is remarkably improved in order to suppress the invasion of the corrosion factor at the end face part as much as possible. Such a phenomenon is not recognized at all between the inorganic compound other than the present invention and the organic resin, but is a completely new phenomenon recognized for the first time by the compound formed by the present invention and the organic resin.

Examples of the zirconium compound in the present invention include zirconia sol, zirconium hydroxide, zirconium oxide, zirconium phosphate, zirconium nitrate, lead zirconate, calcium zirconate and strontium zirconate, but zirconia sol is preferred. .

Al phosphate compound referred to in the present invention means primary aluminum phosphate, aluminum hydrogen phosphate, aluminum dihydrogen phosphate, aluminum acetate, aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum bromide, aluminum fluoride, aluminum oxalate , Aluminum formate, aluminum nitrite, aluminum hydrogen sulfite, aluminum silicate, aluminum bisuccinate, aluminum bifluoride, aluminum bicarbonate, aluminum tripolyphosphate, aluminum hexamethylene acid, aluminum polymetaphosphate, aluminum phosphonate, etc. In particular, primary aluminum phosphate, aluminum hydrogen phosphate, and aluminum dihydrogen phosphate are preferable.

The Mn compound, Cu compound, Ni compound and Co compound referred to in the present invention are Mn phosphate, Cu phosphate, Ni phosphate, Co phosphate, Mn nitrate, Cu nitrate, Ni nitrate, Co nitrate, Mn sulfate, Cu sulfate Ni sulfate, Co sulfate, Mn carbonate, Cu carbonate, Ni carbonate, Co carbonate, Mn hydroxide, Cu hydroxide, Ni hydroxide, Co hydroxide and the like can be used. Further, compounds such as acetates, formates, lactates, oxalates, stearates of Mn, Cu, Ni and Co can also be used. Of these, nitrates are preferred.

The oxidizing agent referred to in the present invention is HNO ₃ , N ₂ O ₄ , N ₂ O ₃ , N ₂ O, Cu (NO ₃ ) ₂ , AgNO ₃ , NH ₄ NO ₃ , BaO ₂ , FeCl ₂ , CuSO ₄ , Cu (CH ₃ COO) ₂ , Hg (CH ₃ COO) ₂ , Bi (CH ₃ COO) ₃ , Ag ₂ O, CuO, Bi ₂ O ₃ , HMnO ₄ and MnO ₂ , especially HNO ₃ , HMnO ₄ and MnO ₂ is preferred. Moreover, you may use 1 type, or 2 or more types of these.

The polyethylene glycol type surfactant referred to in the present invention may be any of nonionic type, anionic type and cationic type, but the nonionic type is the best. The acetylene-based diol composition may be any acetylene-based diol compound.

Among the resins and / or their precursors used in the present invention, the resins include polyacrylates and copolymers thereof, polymetaphosphate esters and polymers thereof, polystyrene and copolymers thereof, polyvinyl acetate and copolymers thereof. Polymer, polyacrylonitrile and its copolymer, polyvinyl chloride and its copolymer, polyvinylpyrrolidone and its copolymer, polybutadiene and its copolymer resin, polyisoprene and its copolymer resin, polyoprene and its copolymer Polymers of double bond-containing compounds such as polymers, polyethylene and copolymers thereof, polypropylene and copolymers thereof, polyethylene oxide and copolymers thereof, polypropylene oxide and copolymers thereof, polytetramethylene oxide and copolymers thereof Union, polyethyleneimine and its Include ring-opening polymerization type resins such as polymers. These precursors include monomers and oligomers of these resins.

Polycondensation resins include polyesters, polyamides, polyimides, polycarbonates, copolymers thereof, and the like, and precursors include these monomers and oligomers. Examples of the addition polymerization resin include an epoxy resin, a urethane resin, and a polyether resin. Examples of the precursor include an epoxy compound, an isocyanate compound and a block body thereof. In addition, resin-modified products such as polyester polyamide, polyurethane-modified polyester, epoxy-modified polyester, and acrylic-modified polyurethane are listed.

In this invention, resin and / or its precursor are contained in the process liquid in the state melt | dissolved or disperse | distributed. Although the organic solvent or the aqueous solvent is not particularly selected as the solvent, since the aqueous solution is usually used as the treatment liquid, the resin is preferably dissolved or dispersed in water.

Among these resins and / or precursors thereof, the treatment liquid of the present invention includes acrylic resins, epoxy resins, polyester resins, urethane resins, polyester resins, acrylic modified polyester resins, epoxy modified polyester resins, urethane modified polyesters. Resins, acrylic modified polyurethane resins, and acrylic modified polyester polyurethane resins are preferred.

More relative to the zirconium compound 100 parts by weight _results, SiO _{2, Al} 2 O 3, MgO and TiO ₂ 1 or sol or two or more blending 10 to 2000 parts by weight, _SiO 2 was blended with a zirconium compound, A metal surface treating agent is prepared by blending 10 to 500 parts by weight of an Al phosphate compound with respect to 100 parts by weight of a total amount of one or more of Al ₂ O ₃ , MgO and TiO ₂ sols.

Further, in the surface treatment agent according to the present invention, one or more of Mn compound, Cu compound, Ni compound and Co compound is added to 1.0 to 100 with respect to 100 parts by weight of the total solid content contained in the surface treatment agent. A metal surface treatment agent to be blended by weight is used.

Further, in the two types of surface treatment agents according to the present invention, 0.1 to 100 parts by weight of an oxidizing agent is blended with respect to 100 parts by weight of the total solid content contained in the surface treatment agent. And

Furthermore, in the above three types of surface treatment agents according to the present invention, one or two of a polyethylene glycol type surfactant and an acetylenic diol composition is added to the total solid content of 100 parts by weight contained in the surface treatment agent. It is set as the metal surface treating agent characterized by mix | blending 05-5.0 weight part.

Further, in the above four kinds of surface treatment agents according to the present invention, a surface treatment agent is formed by blending a water-based organic resin emulsion or a water-soluble resin having film-forming properties with a weight concentration of 5 to 98% based on the total solid content.

The surface treatment agent of the present invention is more effective when it is acidic, and a film having better adhesion to the material, corrosion resistance, paint adhesion and coating film corrosion resistance is formed. In particular, good results are obtained at a pH of 1.5 to 6.0.

The surface treatment agent of the present invention can be used in combination with a leveling agent, an antifoaming agent, a lubricant, a thickener, etc., if necessary. Various water-based resins and water-based emulsion resins can also be blended.

The coating amount of the surface treatment agent of the present invention is 0.05 g / m ² or more and has excellent adhesion to materials, corrosion resistance, paint adhesion, coating corrosion resistance, electrodeposition coating properties, electrodeposition coating corrosion resistance and lubricity. can get. The upper limit is not particularly limited, but is 10.0 g / m ² from an economic viewpoint.

In order to apply the surface treating agent according to the present invention to various metals, any coating method such as roll coater, spray coating, brush coating, dip coating, curtain flow, etc. may be used.

The surface treating agent in the present invention can be dried at a low temperature of 100 ° C. or lower. Here, the drying temperature of the conventional chromate is generally 100 ° C. or less, but the present invention is processed in the chromate section in the conventional aluminum production line or various plated steel sheet production lines, and the chromate drying apparatus can be used as it is. Easy to install. Therefore, the economic effect when the present invention is generalized is extremely large.

On the other hand, the surface treating agent in the present invention can be dried at a high temperature of 100 ° C. or higher. If the drying temperature is increased, the corrosion resistance is improved accordingly. For example, if it is dried at 230 ° C., the adhesion and corrosion resistance with a considerably excellent material can be obtained even if the adhesion amount is reduced, and the paint adhesion, coating corrosion resistance, electrodeposition coating property, electrodeposition coating corrosion resistance and lubricity Thus, it is possible to obtain an ultra-high corrosion resistance chromium-free surface-treated metal material in which is maintained as it is.

The present invention has so far mainly described the case where it is processed into a hot dip galvanized steel sheet. However, the present invention is a metal such as aluminum or aluminum alloy plate, magnesium or magnesium alloy plate, titanium or titanium alloy plate, nickel or nickel alloy plate, copper or copper alloy plate, zinc or zinc alloy plate, tin or tin alloy plate, Silicon steel plates, stainless steel, etc., and steel materials can also be applied to cold-rolled steel plates, black-skin hot-rolled steel plates, pickled hot-rolled steel plates, thick plates, shaped steels, pipes, wires, and the like. In addition, a plated steel plate in which one type of metal such as Zn, Ni, Cu, Fe, Al, Co, Ti, Mg, Mn, Sn is plated on a steel plate, or alloy plating in which two or more types of these metals are plated. Applicable to steel plate. In addition, a metal having a chromium-free surface-treated film that exhibits excellent adhesion to the material and exhibits extremely excellent corrosion resistance, paint adhesion, and coating film corrosion resistance by applying and drying to these metal objects. Can provide material.

As an application of the present invention, since it is a pollution-free surface treatment agent that does not use chromium, it can be used for container materials such as beverage cans, food cans and miscellaneous cans and toys. In addition, home appliance parts such as electric washing machines, televisions, personal computers, word processors, etc. or office parts, roof / wall materials, guardrails, various parts of building materials such as various iron pillars, etc. . In addition, because it is excellent in electrodeposition paintability, electrodeposition coating corrosion resistance and lubricity, it can be processed into hot-dip galvanized steel sheet (GI) and alloyed hot-dip galvanized steel sheet (GA). ) Can be easily manufactured. In addition, since the formed film exhibits excellent insulation and exhibits excellent adhesion to the material before and after annealing, it can also be used as a coating agent for electrical steel sheets (silicon steel sheets), especially non-oriented electrical steel sheets. I can do it. Furthermore, ship building members, bridge shapes formed from thick plates and shaped steel, wire ropes formed from wire rods, various transport pipes formed from pipes, steel furniture formed from cold rolled steel plates, or Containers including drums formed from black skin hot-rolled steel sheets, pickled hot-rolled steel sheets, boxes including containers, members for vehicles, and the like.

Examples will be described in detail below.
The evaluation method is as follows.
(1) Adhesiveness of the film with the material: The metal material treated with the surface treatment agent of the present invention is bent 0T, the bent part is peeled off with cellophane tape, and the peeled state of the film at the bent part is observed with a 10 times loupe. ◎: No peeling, ○: Peeling part over 0% to 2%, △: Peeling part over 2% to 10%, X: Peeling part over 10% to 50%, XX: Peeling part over 50% (2) Corrosion resistance : Corrosion test shows rusting by salt spray test in accordance with JIS-Z-2371 standard (salt water concentration 5%, tank temperature 35 ° C., spray pressure 20 PSI), ◎, ○, Δ, ×, XX Evaluation was made in 5 stages. ◎: Rust occurrence rate 0%, ○: Rust occurrence rate 0% to 1%, △: Rust occurrence rate 1% to 10%, X: Rust occurrence rate 10% to 50%, XX: Rust occurrence rate More than 50%.

(3) Paint adhesion: Adhesion with the paint is spray-coated with a melamine-based low-temperature baking paint (baking temperature: 110 ° C.) on the obtained surface-treated film so as to be 20 μm, and then 5 times in boiling water. The film was immersed for a period of time, and after removal, the coated film was cut at 1 mm size and peeled off to evaluate the peeled area of the coated film. A: Coating film peeling area 0%, B: Coating film peeling area 0% to 1%, Δ: Coating film peeling area 1% to 10%, X: Coating film peeling area 10% to 50%, XX : Coating film peeling area> 50% (4) Coating film corrosion resistance: Coating film corrosion resistance was spray-coated with a melamine-based low-temperature baking paint (baking temperature: 110 ° C) on the obtained surface-treated film so as to be 20 µ after baking. Thereafter, the coating film was crushed in a cross shape with a cutter and subjected to a corrosion test. For the corrosion test, a salt spray test based on the JIS-Z-2371 standard was carried out for 500 hours, the crosscut portion was peeled off with tape, and the peel width of the coating film was measured. A: Peel width 0 mm, O: Peel width 0 mm to 2 mm, Δ: Peel width 2 mm to 5 mm, X: Peel width 5 mm to 10 mm, XX: Peel width 10 mm.

(5) End face rust prevention: End face rust prevention is performed by spray-coating a melamine-based low-temperature baking paint (baking temperature: 110 ° C.) on the obtained surface-treated film to 20 μm after baking, and then applying the coated sample. Shear was sheared and a corrosion test was performed. For the corrosion test, a salt spray test based on JIS-Z-2371 standard was carried out for 500 hours, and the maximum swollen width of the coating film from the sheared portion was measured. A: Swelling width 0 to 1.0 mm, O: Swelling width 1 mm to 2 mm, Δ: Swelling width 2 mm to 5 mm, X: Swelling width 5 mm to 10 mm, XX: Swelling width 10 mm or more.
(6) Bending part corrosion resistance: Bending part corrosion resistance is obtained by spray-coating a melamine-based low-temperature baking paint (baking temperature: 110 ° C.) on the obtained surface-treated film to 20 μm after baking, and then applying the coated sample. 0T bending was performed and a corrosion test was performed. For the corrosion test, a salt spray test based on the JIS-Z-2371 standard was carried out for 500 hours, and the corrosion area in the bent portion was measured. ◎: Corrosion area 0 to 5.0%, ○: Corrosion area more than 5.0% to 10%, △: Corrosion area more than 10% to 20%, X: Corrosion area more than 20% to 50%, XX: Corrosion Over 50% area.

(7) Electrodeposition coating property: Cationic electrodeposition paint (electrodeposition voltage: 230 V, baking temperature: 170 ° C.) is electrodeposited on the surface treatment film thus obtained so that it becomes 20 μm after baking. The appearance of the coated film was visually observed. A: Good sharpness, no surface defects (rough skin, pinholes, etc.) ○: Good visibility and slight surface defects. Δ: Slightly good image quality, some surface defects occurred, x: poor image quality, surface defect occurred. XX: Vividness defect and many surface defects occur.
(8) Electrodeposition coating corrosion resistance: The electrodeposition coating film obtained by cation electrodeposition under the same conditions as in (7) on the obtained surface-treated coating was wrinkled in a cross shape with a cutter and subjected to a corrosion test. In the corrosion test, the cloth was immersed in 5% saline solution at 50 ° C. for 10 days, the crosscut part was peeled off with tape, and the peel width of the electrodeposition coating film was measured. A: Peel width 1 mm or less, O: Peel width 1 mm to 2 mm, Δ: Peel width 2 mm to 5 mm, X: Peel width 5 mm to 10 mm, XX: Peel width 10 mm.

(9) Lubricity (workability): The obtained surface-treated steel sheet was evaluated for lubricity (workability) by a draw bead test (sliding test). Test conditions are as follows: (1) Die shape: R = 5R (2) Pulling conditions: Distance 100 mm, width 30 mm, speed 20 mm / min (3) Pressure: 250 kgf (4) Number of sliding times: 1 time. A: Sliding resistance 0.25 μ or less, ○: Over 0.25 μ to 0.29 μ Δ: Over 0.29 to 0.40 μ ××: Over 0.40 to 0.50 μ ××: Over 0.50 μ

(10) Interlayer resistance: The obtained surface-treated steel sheet was measured according to the second term of JIS2550. The measurement was performed before and after annealing. The annealing conditions are (1) Atmosphere: high purity N _{2 (} 2) Temperature: 750 ° C. ± 20 ° C. (3) Cooling condition: Cool from 750 ° C. to 200 ° C. over 2 hours.

(11) Adhesiveness of the film before and after annealing: The obtained surface-treated steel sheet was bent to 10, 20, and 30 mmφ before and after annealing, and the peeled portion was subjected to a peeling test with a cellophane scotch tape, and the peeling state of the film was visually observed. . ◎: No peeling ○: Slight peeling △: Partial peeling ×: Pretty peeling ××: Whole peeling

Aluminum phosphate (commercially available) in a bath containing 50 g / l of zirconia sol (product of the first rare element chemical industry, product name: ZSL20N) and 50 g / l of silica sol (product of the Nissan Chemical Industry, product name: STO-UP) Product) A surface treatment agent blended at 37.5 g / l was applied to a hot-dip galvanized steel sheet and dried at 80 ° C., and a film was formed so that the film after drying was 0.4 g / m ² .

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 10 g / l, silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) 50 g / l, alumina sol (product of the Nissan Chemical Industry, trade name) : Surface treatment agent containing 100 g / l of aluminum dihydrogen phosphate (commercial product) in a bath containing 100 g / l of alumina sol 100), 20 g / l of MgO sol (commercial product) and 30 g / l of TiO ₂ sol (commercial product) It apply | coated to the hot dip galvanized steel plate, it dried at 90 degreeC, and the membrane | film | coat was formed so that the membrane | film | coat after drying might be 0.3 g / m < ² >.

Zirconia sol (product of the first rare element chemical industry, product name: ZSL20N) 100 g / l and silica sol (product of the Nissan Chemical Industry, product name: ST-O) 10 g / l are mixed, and the primary aluminum phosphate (commercially available) Product) A surface treatment agent blended at 50 g / l was applied to a hot-dip galvanized steel sheet and dried at 80 ° C., and a film was formed so that the film after drying was 0.4 g / m ² .

Zirconia sol (product of 1st rare element chemical industry, trade name: ZSL20N) 10 g / l, silica sol (product of Nissan Chemical Industry, trade name: ST-OUP) 10 g / l, alumina sol (product of Nissan Chemical Industries, trade name) : Surface treatment agent containing 30 g / l of alumina sol 520), 30 g / l of MgO sol (commercial product) and 30 g / l of TiO ₂ sol (commercial product) and 300 g / l of aluminum dihydrogen phosphate (commercial product) in a bath It apply | coated to the aluminum alloy plate (Mg: 4.2%), it dried at 90 degreeC, and the membrane | film | coat was formed so that the membrane | film | coat after drying might be set to 0.4 g / m < ² >.

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 10 g / l, silica sol (product of Nissan Chemical Industries, trade name: ST-OUP) 9 g / l and alumina sol (product of Nissan Chemical Industries, Product name: Alumina sol 100) A surface treatment agent containing 3.9 g / l of aluminum hydrogen phosphate (commercially available) in a bath containing 20 g / l is applied to a hot-dip galvanized steel sheet, dried at 70 ° C., and dried film Was formed to be 0.5 g / m ² .

Zirconia sol (1st rare element chemical industry product, product name: ZSL20N) 10 g / l, silica sol (Nissan Chemical Industry product, product name: ST-O) 9 g / l and alumina sol (Nissan Chemical Industry product, product name) : Alumina sol 200) A surface treatment agent blended with 245 g / l of aluminum hydrogen phosphate (commercial product) in a bath blended with 30 g / l was applied to a hot-dip galvanized steel sheet, dried at 70 ° C., and the dried film was 0.3 g. A film was formed so as to be / m ² .

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 10 g / l and alumina sol (Nissan chemical industry product, trade name) : Alumina sol 200) An alloyed hot-dip galvanized steel sheet (Fe 12.5%) containing a surface treatment agent containing 20 g / l of aluminum dihydrogen phosphate (commercial product) and 20 g / l of nitric acid Co (commercial product) in a bath containing 20 g / l -Zn 87.5%) and dried at 80 ° C., and the film was formed so that the film after drying was 0.3 g / m ² .

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 10 g / l and alumina sol (Nissan chemical industry product, trade name) : Alumina sol 200) A surface treatment agent containing 20 g / l of aluminum dihydrogen phosphate (commercial product) and 40 g / l of nitric acid nitric acid (commercial product) was applied to a hot-dip galvanized steel sheet (GI). It dried at 80 degreeC and formed the membrane | film | coat so that the membrane | film | coat after drying might be 0.3 g / m < ² >.

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 10 g / l and alumina sol (Nissan chemical industry product, trade name) : Alumina sol 200) A surface treatment agent containing 20 g / l aluminum dihydrogen phosphate (commercial product), 20 g / l Cu nitrate (commercial product) and 10 g / l Mn nitrate was applied to the cold rolled steel sheet. The film was dried at 230 ° C., and the film was formed so that the film after drying was 0.3 g / m ² .

Zirconium oxide (commercial product) 50 g / l, MgO sol (commercial product) 10 g / l and TiO ₂ sol (commercial product) 40 g / l compounded in a bath containing 37.5 g / l aluminum hydrogen phosphate (commercial product), Furthermore, a surface treatment agent containing 0.15 g / l of nitric acid (commercially available product) was applied to a copper plate, dried at 70 ° C., and a film was formed so that the film after drying was 1.0 g / m ² .

Zirconium oxide (commercial product) 50 g / l, MgO sol (commercial product) 10 g / l and TiO ₂ sol (commercial product) 40 g / l compounded in a bath containing 37.5 g / l aluminum hydrogen phosphate (commercial product), Furthermore, the surface treating agent which mix | blended nitric acid (commercial item) 13.75g / l was apply | coated to the copper plate, it dried at 70 degreeC, and the membrane | film | coat was formed so that the membrane | film | coat after drying might be 1.0 g / m < ² >.

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 10 g / l and alumina sol (Nissan chemical industry product, trade name) : Alumina sol 200) 20 g / l of aluminum dihydrogen phosphate (commercial product) 20 g / l, Ni phosphate (commercial product) 40 g / l, nitric acid (commercial product) 5 g / l surface treatment agent was melted It apply | coated to the galvanized steel plate (GI), it dried at 80 degreeC, and the membrane | film | coat was formed so that the membrane | film | coat after drying might be 0.3 g / m < ² >.

Zirconia sol (product of 1st rare element chemical industry, trade name: ZSL20N) 50 g / l, silica sol (product of Nissan Chemical Industries, trade name: ST-OUP) 45 g / l, primary aluminum phosphate (commercial product) 40 g A surface treatment agent containing 0.07 g / l of a polyethylene glycol type surfactant (Sannobuco product, product name: SNW366) is further applied to a hot dip galvanized steel sheet, dried at 80 ° C., and dried. The film was formed so that the later film was 0.3 g / m ² .

Zirconia sol (product of 1st rare element chemical industry, trade name: ZSL20N) 50 g / l, silica sol (product of Nissan Chemical Industries, trade name: ST-OUP) 35 g / l, primary aluminum phosphate (commercial product) 42 Further, a surface treatment agent containing 1.27 g / l of an acetylene-based diol composition (product of Air Products Japan, trade name: Surfinol S-SE) was applied to a hot-dip galvanized steel sheet in a bath containing 0.5 g / l. dried at 90 ° C., coating after drying to form a film so that 0.4 g / ^{m 2.}

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 50 g / l, silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) 30 g / l and alumina sol (product of the Nissan Chemical Industry, trade name) : Alumina sol 100) 20 g / l and primary aluminum phosphate (commercial product) 37.5 g / l, and a polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 1.37 g / l The surface treatment agent which mix | blended 5.5 g / l of acetylene type diol composition (a product of Air Products Japan, brand name: Surfynol S-SE) was apply | coated to the hot dip galvanized steel plate, it dried at 70 degreeC, and after drying The film was formed so that the film was 0.4 g / m ² .

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 10 g / l and alumina sol (Nissan chemical industry product, trade name) : Alumina sol 200) 20 g / l of aluminum dihydrogen phosphate (commercial product) 20 g / l, Co phosphate (commercial product) 40 g / l and nitric acid (commercial product) 5 g / l, and polyethylene glycol type Surfactant (Sannobuco product, trade name: SNW366) 1.5 g / l of a surface treatment agent was applied to a hot dip galvanized steel sheet (GI), dried at 80 ° C., and the dried film was 0.3 g / l. A film was formed so as to be m ² .

Zirconia sol (product of 1st rare element chemical industry, trade name: ZSL20N) 50 g / l, silica sol (product of Nissan Chemical Industries, trade name: ST-OUP) 50 g / l, aluminum hydrogen phosphate (commercial product) 75 g / l l The surface treatment agent blended was applied to a stainless steel plate (SUS304) and dried at 230 ° C. to form a film so that the film after drying was 0.4 g / m ² .

Surface treatment agent containing 50 g / l of zirconium hydroxide (commercial product), 25 g / l of MgO sol (commercial product) and 25 g / l of TiO ₂ sol (commercial product), 17.5 g / l of aluminum hydrogen phosphate (commercial product) Was applied to a magnesium alloy plate and dried at 70 ° C., and a film was formed so that the film after drying was 1.0 g / m ² .

A surface treatment agent containing 35 g / l of zirconium nitrate (commercial product), 65 g / l of TiO ₂ sol (commercial product) and 75 g / l of aluminum dihydrogen phosphate (commercial product) was applied to a nickel plate and dried at 70 ° C. The film was formed such that the film after drying was 0.5 g / m ² .

Zirconium nitrate (commercial product) 50 g / l, Alumina sol (product of Nissan Chemical Industries, trade name: Alumina sol 100) 20 g / l, TiO ₂ sol (commercial product) 30 g / l, and aluminum monohydrogenate (commercial product) 95 g / l A surface treatment agent containing 19.5 g / l of nitric acid (commercial product) was further applied to the titanium plate, dried at 250 ° C., and the film was formed so that the dried film was 0.2 g / m ^2. Formed.

Zirconia sol (product of 1st rare element chemical industry, trade name: ZSL20N) 45 g / l, silica sol (product of Nissan Chemical Industries, trade name: ST-OUP) 55 g / l and primary aluminum phosphate (commercial product) 40 A surface treatment agent blended with 0.0 g / l was applied to a tin-plated steel sheet (tinplate) and dried at 80 ° C., and a film was formed so that the film after drying was 0, 3 g / m ² .

Zirconia sol (product of the rare element chemical industry, trade name: ZSL20N) 55 g / l, silica sol (product of Nissan Chemical Industry, trade name: ST-OUP) 45 g / l, alumina sol (product of Nissan Chemical Industry, trade name) A surface treatment agent containing 100 g / l of dialumina sol 100) and 125 g / l of primary aluminum phosphate (commercially available product) was applied to an electrogalvanized steel sheet, dried at 70 ° C., and the dried film was 0.5 g / m. ^A film was formed to be ² .

Zirconia sol (product of the first rare element chemical industry, product name: ZSL20N) 55 g / l, silica sol (product of the Nissan Chemical Industry, product name: ST-O) 45 g / l and primary aluminum phosphate (commercial product) 30 g A surface treatment agent containing 0.5 g / l of a polyethylene glycol type surfactant (product of Sannobuco, product name: SNW366) is further applied to a Zn-Al alloy plated steel sheet (Al55% -Zn45%), dried at 90 ° C., coating after drying to form a film so that 0.2 g / ^{m 2.}

Zirconia sol (product of 1st rare element chemical industry, trade name: ZSL20N) 10 g / l, silica sol (product of Nissan Chemical Industries, trade name: ST-OUP) 20 g / l and TiO ₂ sol (commercial product) 20 g / l A surface treatment agent blended with 250 g / l of primary aluminum phosphate (commercially available product) is applied to a pickled hot-rolled steel sheet and dried at 50 ° C., so that the film after drying is 0.7 g / m ^2. Formed.

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 35 g / l, silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) 35 g / l and alumina sol (product of Nissan Chemical Industries, trade name) : Alumina sol 100) 30 g / l and primary aluminum phosphate (commercial product) 125 g / l, nitric acid (commercial product) 2.25 g / l and polyethylene glycol type surfactant (Sannobco product, trade name: SNW366) ) The surface treatment agent blended at 0.8 g / l was applied to stainless steel (SUS304) and dried at 300 ° C. to form a film so that the dried film was 0.2 g / m ² .

Zirconia sol (product of 1st rare element chemical industry, trade name: ZSL20N) 50 g / l, silica sol (product of Nissan Chemical Industries, trade name: ST-OUP) 50 g / l and TiO ₂ sol (commercial product) 35 g / l And primary aluminum phosphate (commercial product) 135 g / l, nitric acid (commercial product) 27 g / l and acetylene-based diol composition (product of Air Products Japan, trade name: Surfanol S-SE) A surface treatment agent blended with 95 g / l was applied to stainless steel (SUS304) and dried at 250 ° C., and a film was formed so that the film after drying was 0.2 g / m ² .

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 50 g / l, silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) 35 g / l and alumina sol (product of Nissan Chemical Industries, trade name) : Alumina sol 100) 15 g / l and primary aluminum phosphate (commercial product) 37.5 g / l, nitric acid (commercial product) 0.5 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name) : SNW366) 0.8 g / l and an acetylene-based diol composition (Air Products Japan, product name: Surfinol S-SE) 5.5 g / l of a surface treatment agent was applied to an aluminum plate, and 90 ° C. And the film was formed so that the film after drying was 0.4 g / m ² .

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 5.5 g / l, silica sol (Nissan Chemical Industry product, trade name: ST-OUP) 4.5 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product and trade name: Alumina sol 100) 40.0 g / l and primary aluminum phosphate (commercial product) 10.0 g / l in a water-based acrylic resin emulsion (Dainippon Ink Chemical Co., Ltd. product, trade name: Boncoat CQ8690) ) Is applied to a Zn-Al alloy-plated steel sheet (Al55% -Zn45%) and dried at 90 ° C. so that the dried film becomes 0.1 g / m ^2. A film was formed on.

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 1.0 g / l, silica sol (Nissan Chemical Industry product, trade name: ST-OUP) 0.75 g / l and alumina sol (Nissan chemical industry company) Product, product name: Alumina sol 100) Surface treatment with 200.0 g / l of water-based acrylic resin emulsion (commercial product) in a bath containing 5.25 g / l of primary aluminum phosphate (commercial product) and 1.75 g / l The agent was applied to an aluminum plate and dried at 90 ° C., and a film was formed so that the film after drying was 0.3 g / m ² .

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 2.75 g / l, silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) 2.25 g / l and monoaluminum phosphate ( (Commercially available product) 1.0 g / l, Ni nitrate 1.0 g / l, Cu nitrate 1.0 g / l and polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 0.2 g / l, and water-based acrylic A surface treatment agent containing 135.0 g / l of resin (commercially available product) was applied to a Zn-Al alloy plated steel sheet (Al55% -Zn45%), dried at 80 ° C., and the dried film was 0.7 g / m. ^A film was formed to be ² .

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 2.75 g / l, silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) 2.25 g / l and monoaluminum phosphate ( (Commercially available product) 2.0 g / l, Co nitrate 1.0 g / l and polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 0.2 g / l are blended, and further, an aqueous acrylic resin (commercially available product) is 138. A surface treatment agent blended with 0.7 g / l was applied to an aluminum plate and dried at 80 ° C., and a film was formed so that the dried film was 0.7 g / m ² .

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 27.5 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 22.5 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product, trade name: Alumina sol 100) 50.0 g / l and primary aluminum phosphate (commercial product) 42.5 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 8g / l compounded surface treatment agent is applied to an alloyed hot-dip galvanized steel sheet (Fe 12.5% -Zn 87.5%) and dried at 80 ° C. so that the dried film becomes 0.2 g / m ^2. A film was formed on.

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 27.5 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 22.5 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product, trade name: Alumina sol 100) 100.0 g / l and primary aluminum phosphate (commercial product) 42.5 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) A surface treatment agent blended at 8 g / l was applied to a hot dip galvanized steel sheet and dried at 80 ° C., and a film was formed so that the film after drying was 0.3 g / m ² .

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 27.5 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 22.5 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product, trade name: Alumina sol 100) 50.0 g / l, monoaluminum phosphate (commercial product) 42.5 g / l and Co nitrate (commercial product) 37.5 g / l, and polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) A 0.8 g / l compounded surface treatment agent was applied to an alloyed hot-dip galvanized steel sheet (Fe 12.5% -Zn 87.5%), dried at 80 ° C, and dried. The film was formed so that the film thickness was 0.3 g / m ² .

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 25.0 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 25.0 g / l, and alumina sol (Nissan chemical industry company) Product, trade name: Alumina sol 100) 75.0 g / l, monoaluminum phosphate (commercial product) 100.0 g / l and Ni nitrate (commercial product) 50.0 g / l, polyethylene glycol type surfactant (Sannobuco product, product name: SNW366) 0.8 g / l of the surface treatment agent was applied to a hot dip galvanized steel sheet and dried at 80 ° C. so that the dried film was 0.3 g / m ^2. A film was formed.

Zirconia sol (1st rare element chemical industry product, product name: ZSL20N) 10.0 g / l, silica sol (Nissan Chemical Industry product, product name: ST-OUP) 5.0 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product, trade name: Alumina sol 100) 100.0 g / l, monoaluminum phosphate (commercial product) 150.0 g / l, Co nitrate (commercial product) 50.0 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 0.5 g / l of a surface treatment agent is applied to a non-oriented electrical steel sheet and dried at 150 ° C. so that the dried film becomes 1.0 g / m ^2. A film was formed on.

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 25.0 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 25.0 g / l, and alumina sol (Nissan chemical industry company) Product, trade name: Alumina sol 100) 125.0 g / l and primary aluminum phosphate (commercial product) 50.0 g / l, Co nitrate (commercial product) 37.5 g / l, polyethylene glycol type surfactant (Sannobuco) Product, trade name: SNW366) 0.8 g / l blended with a surface treatment agent containing 47.9 g / l of water-based acrylic resin (Dainippon Ink Chemical Co., Ltd., trade name: Boncoat CQ8690) It apply | coated to the steel plate, it dried at 150 degreeC, and the membrane | film | coat was formed so that the membrane | film | coat after drying might be 1.0 g / m < ² >.

Comparative Example 1

Zirconia sol (product of the first rare element chemical industry, product name: ZSL20N) 100 g / l and silica sol (product of the Nissan Chemical Industry, product name: ST-OUP) 5 g / l compounded with monophosphate aluminum (commercially available) Product) A surface treatment agent blended at 40 g / l was applied to a hot-dip galvanized steel sheet and dried at 70 ° C., and a film was formed so that the dried film was 0.5 g / m ² .

Comparative Example 2

Aluminum phosphate monobasic in a bath containing 1.0 g / l of zirconia sol (product of the first rare element chemical industry, product name: ZSL20N) and 210 g / l of silica sol (product of the Nissan Chemical Industry, product name: ST-OUP) (Commercially available product) A surface treatment agent blended at 60 g / l was applied to a hot-dip galvanized steel sheet and dried at 70 ° C., and a film was formed so that the film after drying was 0.5 g / m ² .

Comparative Example 3

Aluminum phosphate (commercially available) in a bath containing 50 g / l of zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) and 50 g / l of silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) Product) A surface treatment agent blended at 5 g / l was applied to a hot-dip galvanized steel sheet and dried at 70 ° C., and a film was formed so that the dried film was 0.5 g / m ² .

Comparative Example 4

Aluminum phosphate (commercially available) in a bath containing 50 g / l of zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) and 50 g / l of silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) Product) A surface treatment agent blended at 550 g / l was applied to a hot-dip galvanized steel sheet and dried at 70 ° C., and a film was formed so that the dried film was 0.5 g / m ² .

Comparative Example 5

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 10 g / l and alumina sol (Nissan chemical industry product, trade name) : Alumina sol 200) A surface treatment agent containing 20 g / l of aluminum dihydrogen phosphate (commercial product) and 0.4 g / l of nitric acid Co (commercial product) was applied to a cold-rolled steel sheet at a temperature of 130 ° C. And the film was formed so that the film after drying was 0.3 g / m ² .

Comparative Example 6

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 10 g / l and alumina sol (Nissan chemical industry product, trade name) : Alumina sol 200) A surface treatment agent containing 20 g / l of aluminum dihydrogen phosphate (commercial product) and 110 g / l of nitric acid Co (commercial product) was applied to a cold-rolled steel sheet and dried at 130 ° C. Then, the film was formed so that the film after drying was 0.3 g / m ² .

Comparative Example 7

Zirconium oxide (commercial product) 50 g / l, MgO sol (commercial product) 10 g / l and TiO ₂ sol (commercial product) 40 g / l blended in a bath containing aluminum hydrogen phosphate (commercial product) 37.5 g / l, Further, a surface treatment agent containing 0.03 g / l of nitric acid (commercial product) was applied to a copper plate and dried at 70 ° C., and a film was formed so that the film after drying was 1.0 g / m ² .

Comparative Example 8

Zirconium oxide (commercial product) 50 g / l, MgO sol (commercial product) 10 g / l and TiO ₂ sol (commercial product) 40 g / l blended in a bath containing aluminum hydrogen phosphate (commercial product) 37.5 g / l, Furthermore, a surface treatment agent containing 150 g / l of nitric acid (commercial product) was applied to a copper plate and dried at 70 ° C., and a film was formed so that the film after drying was 1.0 g / m ² .

Comparative Example 9

Zirconia sol (product of the first rare element chemical industry, trade name: ZSL20N) 55 g / l, silica sol (product of the Nissan Chemical Industry, trade name: ST-OUP) 45 g / l blended bath with primary aluminum phosphate (commercially available) Product) 40 g / l blended, and a polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 0.025 g / l blended surface treatment agent was applied to a hot dip galvanized steel sheet and dried at 80 ° C., The film was formed so that the film after drying was 0.3 g / m ² .

Comparative Example 10

Zirconia sol (product of the first rare element chemical industry, product name: ZSL20N) 30 g / l, silica sol (product of the Nissan Chemical Industry Co., product name: ST-OUP) 27.5 g / l mixed bath with primary aluminum phosphate (Commercially available product) 40 g / l blended, and polyethylene glycol surfactant (Sannobuco product, trade name: SNW366) 5.0 g / l and acetylene diol composition (Air Products Japan product, trade name: Surfino) (S-SE) 2.5 g / l of a surface treatment agent was applied to a hot-dip galvanized steel sheet, dried at 80 ° C., and a film was formed so that the film after drying was 0.3 g / m ² .

Comparative Example 11

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 5.5 g / l, silica sol (Nissan Chemical Industry product, trade name: ST-OUP) 4.5 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product and trade name: Alumina sol 100) 40.0 g / l and primary aluminum phosphate (commercial product) 10.0 g / l in a water-based acrylic resin emulsion (Dainippon Ink Chemical Co., Ltd. product, trade name: Boncoat CQ8690) ) Is applied to a Zn-Al alloy-plated steel sheet (Al55% -Zn45%) and dried at 90 ° C. so that the dried film becomes 0.1 g / m ^2. A film was formed on.

Comparative Example 12

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 1.0 g / l, silica sol (Nissan Chemical Industry product, trade name: ST-OUP) 0.75 g / l and alumina sol (Nissan chemical industry company) Product, trade name: Alumina sol 100) 1.25 g / l and primary aluminum phosphate (commercial product) 1.75 g / l in a water-based acrylic resin emulsion (Dainippon Ink Chemical Co., Ltd., trade name: Boncoat CQ8690) ) Was applied to an aluminum plate and dried at 90 ° C. to form a film such that the dried film was 0.3 g / m ² .

Comparative Example 13

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 55.0 g / l, silica sol (Nissan Chemical Industry product, trade name: ST-OUP) 1.0 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product, trade name: Alumina sol 100) 2.0 g / l and monoaluminum phosphate (commercial product) 400.0 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 8g / l compounded surface treatment agent is applied to an alloyed hot-dip galvanized steel sheet (Fe 12.5% -Zn 87.5%) and dried at 80 ° C. so that the dried film becomes 0.2 g / m ^2. A film was formed on.

Comparative Example 14

Zirconia sol (1st rare element chemical industry product, product name: ZSL20N) 10.0 g / l, silica sol (Nissan Chemical Industry product, product name: ST-OUP) 100.0 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product, trade name: Alumina sol 100) 200.0 g / l and primary aluminum phosphate (commercial product) 25.0 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) A surface treatment agent blended at 8 g / l was applied to a hot dip galvanized steel sheet and dried at 80 ° C., and a film was formed so that the film after drying was 0.3 g / m ² .

Comparative Example 15

Zirconia sol (1st rare element chemical industry product, product name: ZSL20N) 10.0 g / l, silica sol (Nissan Chemical Industry product, product name: ST-OUP) 100.0 g / l and alumina sol (Nissan Chemical Industry Co., Ltd.) Product, trade name: Alumina sol 100) 300.0 g / l and primary aluminum phosphate (commercial product) 10.0 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 0.8 g / l The compounded surface treatment agent was applied to a non-oriented electrical steel sheet and dried at 150 ° C., and a film was formed so that the film after drying was 1.0 g / m ² .

Comparative Example 16

Zirconia sol (1st rare element chemical industry product, trade name: ZSL20N) 10.0 g / l, silica sol (Nissan chemical industry product, trade name: ST-OUP) 100.0 g / l, and alumina sol (Nissan chemical industry company) Product, trade name: Alumina sol 100) 200.0 g / l and primary aluminum phosphate (commercial product) 15.0 g / l, polyethylene glycol type surfactant (Sannobuco product, trade name: SNW366) 0.8 g / l Further, a surface treatment agent containing 69.11 g / l of a water-based acrylic resin emulsion (commercial product) was applied to a non-oriented electrical steel sheet, dried at 150 ° C., and the dried film was 1.0 g / m ^2. A film was formed so that

Comparative Example 17

The aluminum plate was treated with commercially available phosphate chromate and dried at 90 ° C. The amount of phosphoric acid chromate deposited after drying was 0.25 g / m ² .

Comparative Example 18

An aluminum alloy plate (Mg: 4.2%) was treated with commercially available phosphoric acid chromate and dried at 90 ° C. The amount of phosphoric acid chromate deposited after drying was 0.18 g / m ² .

Comparative Example 19

A stainless steel plate (SUS304) was treated with commercially available chromate and dried at 90 ° C. The amount of chromate deposited after drying was 120 mg / m ² in terms of Cr.

Comparative Example 20

The magnesium alloy plate was treated with commercially available chromate and dried at 70 ° C. The amount of chromate deposited after drying was 80 mg / m ² in terms of Cr.

Comparative Example 21

A nickel plate was treated with commercially available chromate and dried at 120 ° C. The amount of chromate deposited after drying was 45 mg / m ² in terms of Cr.

Comparative Example 22

The copper plate was treated with commercially available chromate and dried at 80 ° C. The amount of chromate deposited after drying was 35 mg / m ² in terms of Cr.

Comparative Example 23

A titanium plate was treated with commercially available chromate and dried at 80 ° C. The amount of chromate deposited after drying was 55 mg / m ² in terms of Cr.

Comparative Example 24

The cold rolled steel sheet was treated with commercially available chromate and dried at 250 ° C. The amount of chromate deposited after drying was 25 mg / m ² in terms of Cr.

Comparative Example 25

The tin-plated steel sheet was electrolytically treated in a potassium dichromate bath and dried at 80 ° C. The amount of chromate deposited after drying was 5 mg / m ² in terms of Cr.

Comparative Example 26

The electrogalvanized steel sheet was treated with a commercially available coating type chromate and dried at 80 ° C. The amount of chromate deposited after drying was 35 mg / m ² in terms of Cr.

Comparative Example 27

The hot-dip galvanized steel sheet was treated with a commercially available coating type chromate and dried at 80 ° C. The amount of chromate deposited after drying was 25 mg / m ² in terms of Cr.

Comparative Example 28

A Zn-Al alloy-plated steel sheet (Al55% -Zn45%) was treated with a commercially available resin-type chromate and dried at 80 ° C. The adhesion amount of the chromate film after drying was 1.8 g / m ² .

Comparative Example 29

A non-oriented electrical steel sheet was treated with a commercially available resin-type chromate (resin 17.5%) and dried at 320 ° C. The adhesion amount of the resin-type chromate film after drying was 1.0 g / m ² .

As is clear from the comparison between Examples 1, 2, and 3 and Comparative Examples 1 and 2, one or more sols of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ with respect to 100 parts by weight of zirconia sol are used. The appropriate blending ratio is 10 to 2000 parts by weight, and if it is less than 10 parts by weight or more than 2000 parts by weight, the corrosion resistance, film adhesion, paint adhesion, and coating film corrosion resistance are significantly lowered.

From a comparison between Examples 5 and 6 and Comparative Examples 3 and 4, Al was added to 100 parts by weight of one or more of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ sols blended with zirconia sol. The suitable blending ratio of the phosphoric acid compound is 10 to 500 parts by weight, and if it is less than 10 parts by weight or more than 500 parts by weight, the corrosion resistance, film adhesion, paint adhesion and coating film corrosion resistance are significantly lowered.

From a comparison between Example 9 and Comparative Examples 5 and 6, the suitable blending ratio of one or more of Mn compound, Cu compound, Ni compound and Co compound is 1 to 100 parts by weight, and the total amount of the metal surface treatment agent is By blending 1 to 100 parts by weight of one or more of a Mn compound, Cu compound, Ni compound and Co compound with respect to 100 parts by weight of the solid content, the corrosion resistance, coating film corrosion resistance and end face rust resistance are remarkably improved.

From a comparison between Examples 10 and 11 and Comparative Examples 7 and 8, the appropriate blending ratio of nitric acid is 0.1 to 100 parts by weight, and the nitric acid is 0.1 to 100 parts by weight of the total solid content of the metal surface treatment agent. By adding 100 parts by weight, the corrosion resistance is improved.

From a comparison between Examples 13, 14 and 15 and Comparative Examples 9 and 10, the suitable blending ratio of one or two of the polyethylene glycol type surfactant and the acetylenic diol composition is 0.05 to 5.0 parts by weight. Yes, formed by blending 0.05 to 5.0 parts by weight of one or two of polyethylene glycol type surfactant and acetylenic diol composition with respect to 100 parts by weight of the total solid content of the metal surface treatment agent Corrosion resistance of the film, paint adhesion, and coating film corrosion resistance are further improved.

From a comparison between Examples 28, 29, 30 and 31 and Comparative Examples 11 and 12, the appropriate blending ratio of the water-based acrylic resin emulsion is 5 to 98%, and the end face protection is obtained by blending 5 to 98% with respect to the total solid content. Rust and corrosion resistance of the processed part are improved.

As is clear from the comparison between Examples 7, 8, 32, 33, 34 and 35 and Comparative Examples 13 and 14, the metal surface treatment agent according to the present invention has significantly improved electrodeposition coating properties, electrodeposition coating corrosion resistance and lubricity. To improve.

As is apparent from the comparison between Examples 36 and 37 and Comparative Examples 15 and 16, the metal surface treatment agent according to the present invention greatly improves the interlaminar resistance and the film adhesion to the material both before and after annealing.

Examples 1, 4, 7, 9, 10, 17, 18, 19, 20, 21, 22, 23, 27, and 36 are examples in which the present invention is applied to various general-purpose metals, and Comparative Example 17 -29 are examples in which commercially available chromate is applied to various metals that have been widely used. The present invention can be applied to any metal that has been widely used, and a film formed on any metal exhibits corrosion resistance, film adhesion, paint adhesion, and coating film corrosion resistance that surpass chromate. Further, in the case of a non-oriented electrical steel sheet, the formed film exhibits an interlayer resistance that surpasses chromate and adhesion to the material.

The invention's effect

As described above, the surface treatment agent according to the present invention is a so-called chromium-free surface treatment agent that does not use chromium, and the coated film can be dried at a low temperature of 100 ° C. or lower. Therefore, the chromate section in the conventional production line for aluminum and various plated steel sheets can be used as it is, and it is easy to put to practical use. In addition, the formed film does not contain any toxic substances such as chromium compounds, and it has excellent adhesion to materials, corrosion resistance, paint adhesion, coating corrosion resistance and lubricity, so it can be treated with aluminum and tinplate. And can be used for container materials such as beverage cans, food cans and miscellaneous cans. In addition, by applying to various metals or plated steel sheets, it is possible to provide a surface-treated metal material excellent in corrosion resistance, paint adhesion, coating film corrosion resistance, electrodeposition coating property, electrodeposition coating film corrosion resistance and lubricity. Applications are greatly expanded to industries, home appliances / building materials industry, civil engineering / architecture industry, pipe industry, toy industry, indoor building materials industry. In addition, since it exhibits high interlayer resistance and excellent adhesion to materials, it can be applied to electrical steel sheets.

Claims (6)

10 to 2000 parts by weight of one or more sols (colloids) of SiO ₂ , Al ₂ O ₃ , MgO and TiO ₂ are blended with 100 parts by weight of the zirconium compound, and SiO ₂ , Al blended with the zirconium compound A metal surface treatment agent comprising 10 to 500 parts by weight of an Al phosphate compound based on 100 parts by weight of a total amount of one or more of ₂ O ₃ , MgO and TiO ₂ sols.   The metal surface treatment agent according to claim 1, wherein one or more of Mn compound, Cu compound, Ni compound and Co compound is 1 to 2 parts per 100 parts by weight of the total solid content contained in the metal surface treatment agent. A metal surface treatment agent, characterized by containing 100 parts by weight.   With respect to the metal surface treatment agent according to claim 1 and claim 2, 0.1 to 100 parts by weight of one or more oxidizing agents with respect to 100 parts by weight of the total solid content contained in the metal surface treatment agent. A metal surface treatment agent characterized by being blended.   With respect to the metal surface treatment agent according to claim 1, claim 2, and claim 3, the polyethylene glycol type surfactant and the acetylene-based diol composition are used with respect to 100 parts by weight of the total solid content contained in the metal surface treatment agent. A metal surface treating agent characterized in that one or two kinds are mixed in an amount of 0.05 to 5.0 parts by weight.   With respect to the metal surface treatment agent according to claim 1, claim 2, claim 3, and claim 4, the water-based organic resin emulsion or water-soluble resin having film-forming properties is 5 to 98 by weight concentration with respect to the total solid content. A metal surface treatment agent characterized by comprising The metal surface treatment agent according to any one of claims 1, 2, 3, 4, and 5 is applied on a metal material, and the amount of the formed coating is 0.05 to 10 A surface-treated metal material having 0.0 g / m ² .