Treating solution and treating method for forming protective coating films on metals

Abstract

A metallic surface treating solution characterized in that it is an aqueous solution at pH 0.1 to 6.5 comprising a source of at least one selected from the group consisting of Mo, W, V, Nb, Ta, Ti, Zr, Ce, Sr, and trivalent chromium, an oxidizing substance source, and an oxyacid or oxyacid salt of phosphorus or its anhydride, a surface treating method using the treating solution, and metals thereby treated on the surface.

What is claimed is:  
     
       1. A protectively coated metal substrate of Cu, Ag, Fe, Cd, Al, Mg, and alloy thereof, Zn, Ni, or Zn-Fe alloy, wherein the metal substrate is coated with a protective film which is a reaction product on the metal substrate of a solution substantially free of fluoride ions and containing (i) a source of metallic cations of at least one metal element selected from the group consisting of Mo, W, V, Ta, Ti, Zr, Ce, Sr and trivalent chromium, (ii) at least one oxyacid of phosphorus, oxyacid salt of phosphorus, or anhydride of an oxyacid of phosphorus, said oxyacid being selected from the group consisting of orthophosphoric acid, hypophosphorous acid, pyrophoshorous acid, tripolyphosphoric acid and perphosphoric acid, and (iii) at least one oxidizing substance selected from the group consisting of peroxide, hydrochloric chloric acid, hydrobromic bromic acid, nitric acid, and salts thereof. 
     
     
       2. The protectively coated metal substrate of  claim 1 , wherein the protective film is overcoated with an organic, inorganic, or composite corrosion-preventive coating film. 
     
     
       3. The protectively coated metal substrate of  claim 1 , wherein said solution further contains at least one substance selected from the group consisting of alkaline earth metals, an inorganic colloid, and silane coupling agents. 
     
     
       4. The protectively coated metal substrate of  claim 2 , wherein the inorganic colloid is selected from the group consisting of silica sol, alumina sol, titania sol, and zirconia sol. 
     
     
       5. The protectively coated metal substrate of  claim 1 , wherein said solution is substantially free of hexavalent chromium ions. 
     
     
       6. A protectively coated metal substrate of Zn, Ni, Cu, Ag, Fe, Cd, Al, Mg, or an alloy thereof, wherein the metal substrate is coated with a protective film which is a reaction product on the metal substrate of a solution substantially free of fluoride ions and containing (i) a source of metallic cations of at least one metal element selected from the group consisting of Mo, W, V, Ta, Ti, Zr, Ce, Sr and trivalent chromium, (ii) at least one oxyacid of phosphorus, oxyacid salt of phosphorus, or anhydride of an oxyacid of phosphorus, said oxyacid being selected from the group consisting of orthophosphoric acid, hypophosphorous acid, pyrophoshorous acid, tripolyphosphoric acid and perphosphoric acid, (iii) at least one oxidizing substance selected from the group consisting of peroxide, hydrochloric chloric acid, hydrobromic bromic acid, nitric acid, and salts thereof; and (iv) at least one substance selected from the group consisting of alkaline earth metals, an inorganic colloid, and silane coupling agents.