Composition for Metal Surface Treatment, Treating Liquid for Surface Treatment, Method of Surface Treatment, and Surface-Treated Metal Material

Abstract

A surface-treating composition which is a treating liquid containing no ingredients harmful to the environment; such a treating liquid has been difficult to obtain with any conventional technique. The composition enables a coating film having excellent corrosion resistance after coating to be deposited through surface treatment on a surface of a metallic material, e.g., an iron-based metallic material. The composition, which is for the surface treatment of a metal comprising iron and/or zinc, comprises the following ingredients (A), (B), and (C): (A) a compound containing at least one element selected from the group consisting of titanium, zirconium, hafnium, and silicon; (B) a compound containing yttrium and/or a lanthanide element; and (C) nitric acid and/or a nitric acid compound. In the composition, the ratio of the total mass concentration B of the yttrium and/or lanthanide element in the ingredient (B) to the total mass concentration A of the element(s) in the ingredient (A), K1=B/A, is 0.05≦K1≦50 and the ratio of the total mass concentration C of nitrogen atoms in the ingredient (C) in terms of NO 3 concentration to the total mass concentration A, K2=C/A, is 0.01≦K2≦200.

1 . A composition for the surface treatment of metals that comprises: 
 (A) a compound containing at least one element selected from the group consisting of Ti, Zr, Hf, and Si;    (B) a compound containing yttrium and/or a lanthanide element;    (C) nitric acid and/or a nitric acid compound; and    (D) an optional component of at least one fluorine-containing compound.    
     
     
         2 . The composition for surface treatment as claimed in  claim 1 , having a ratio “K1” of total mass concentration “B” of the yttrium and/or lanthanide element of Component (B) to total mass concentration “A” of the at least one element of Component (A) in the range of 0.05≦K1≦50 and a ratio “K2“of the total mass concentration “C” of the nitrogen atoms contained in Component (C), in terms of the NO 3  concentration, to the total mass concentration “A”, in the range of 0.01≦K2≦200.  
     
     
         3 . The composition for surface treatment as claimed in  claim 1  comprising a treatment liquid that contains Component (D), at least one fluorine-containing compound, in an amount such that the free fluorine ion concentration “D” is in the range of 0.001 ppm<D<300 ppm.  
     
     
         4 . The treatment liquid for surface treatment as claimed in  claim 3  having a pH value no greater than 6.0.  
     
     
         5 . The treatment liquid for surface treatment as claimed in  claim 3  further comprising at least one compound selected from a group consisting of HCl, H 2 SO 4 , HClO 3 , HBrO 3 , HNO 2 , HMnO 4 , HVO 3 , H 2 O 2 , H 2 WO 4 , H 2 MoO 4 , and their salts in a concentration in the range of 10-20,000 ppm.  
     
     
         6 . The treatment liquid for surface treatment as claimed in  claim 3  further comprising at least one compound selected from a group consisting of ethylenediamine tetraacetic acid, gluconic acid, heptogluconic acid, glycolic acid, citric acid, succinic acid, fumaric acid, aspartic acid, tartaric acid, malonic acid, malic acid, salicylic acid, and their salts in a concentration in the range of 1-10,000 ppm.  
     
     
         7 . The treatment liquid for surface treatment as claimed in  claim 3  further comprising at least one water-soluble polymer compound and/or a water-dispersible polymer compound.  
     
     
         8 . The treatment liquid for surface treatment as claimed in  claim 3  further comprising at least one surfactant selected from a group consisting of nonionic surfactants, anionic surfactants, and cationic surfactants.  
     
     
         9 . A treatment method for metal material comprising iron and/or zinc comprising: 
 contacting a metal material comprising iron and/or zinc with an acidic treatment liquid that comprises: 
 (A) a compound containing at least one element selected from the group consisting of Ti, Zr, Hf, and Si;  
 (B) a compound containing yttrium and/or a lanthanide element present in an amount such that ratio “K1” of total mass concentration “B” of the yttrium and/or lanthanide element of Component (B) to total mass concentration “A” of the at least one element of Component (A) is in the range of 0.05≦K1≦50;  
   (C) nitric acid and/or a nitric acid compound present in an amount such that ratio “K2” of the total mass concentration “C” of the nitrogen atoms contained in Component (C), in terms of the N0 3  concentration, to the total mass concentration “A”, is in the range of 0.01≦K2≦200; and    (D) at least one fluorine-containing compound in an amount such that the free fluorine ion concentration “D” in the treatment liquid is in the range of 0.001 ppm≦D≦300 ppm.    
     
     
         10 . The surface treatment method as claimed in  claim 9  in which the metal material containing iron and/or zinc is contacted with the treatment liquid thereby simultaneously carry out a degreasing treatment and a film formation treatment of said metal material.  
     
     
         11 . The surface treatment method as claimed in  claim 9  in which the metal material containing iron and/or zinc is a metal material that has been cleansed by a degreasing treatment.  
     
     
         12 . The surface treatment method as claimed in  claim 9  in which the treatment liquid contact process comprises an electrolytic treatment using the metal material containing iron and/or zinc as the cathode.  
     
     
         13 . The surface treatment method as claimed in  claim 9  further comprising a step of contacting the metal material with an aqueous solution containing at least one element selected from a group consisting of cobalt, nickel, tin, copper, titanium, and zirconium after the treatment liquid contact process.  
     
     
         14 . The surface treatment method as claimed in  claim 9  further comprising a step of contacting the metal material with an aqueous solution containing a water-soluble polymer compound or a water-dispersible polymer compound after the treatment liquid contact process.  
     
     
         15 . An iron-containing metal material having a surface coating film layer, that is formed on the surface of the iron-containing metal material by a surface treatment method as claimed in  claim 9 , said surface coating film layer comprising at least one element of Component (A) in an amount of greater than 20 mg/cm 2 .  
     
     
         16 . A zinc-containing metal material having a surface coating film layer, that is formed on the surface of the zinc-containing metal material by a surface treatment method as claimed in  claim 9 , said surface coating film layer comprising at least one element of Component (A) in an amount of greater than 15 mg/cm 2 .  
     
     
         17 . A surface treatment method comprising contacting a metal material containing iron and/or zinc with the treatment liquid for surface treatment as claimed in  claim 3.