Title of Invention

"CHEMICAL CONVERSION TREATING SOLUTION FOR METAL AND TREATING METHOD"

Abstract

A chemical conversion treating solution for a metallic material, comprising a component (A) composed of at least one kind of a water-soluble trivalent chromium compound, a component (B) composed of at least one kind selected from a water-soluble titanium compound and a water-soluble zirconium compound, a component (C) composed of at least one kind of a water-soluble nitrate compound and a component (D) composed of at least one kind of a water-soluble aluminum compound, and further comprising a component (E) composed of at least one kind of a fluorine compound, wherein the content expressed in terms of metal chromium (CA) of the water-soluble trivalent chromium compound-containing component (A) is from 0.1 to 20 mmol/liter, the content expressed in terms of metallic titanium and metallic zirconium (CB) of the component (B) which is composed of at least one kind selected from the water-soluble titanium compound and zirconium compound is from 0.1 to 10 mmol/liter, the content expressed in terms of a cation (CC) of the water-soluble nitrate compound-containing component (C) is from 0.2 to 40 mmol/liter, the content expressed in terms of aluminum (CD) of the water-soluble aluminum component (D) is from 0.2 to 40 mmol/liter, the content expressed in terms of fluorine (CE) of the fluorine compound-containing component (E) satisfies the following expression: (CA x 2 + CB x 4 + CD x 2) ≤ CE ≤ (CA x 4 + CB x 7 + CD x 4) where CA, CB, CD and CE are as defined above, and a pH of the treating solution is controlled within a range from 2.3 to 5.0.

Full Text

DESCRIPTION CHEMICAL CONVERSION TREATING SOLUTION FOR METAL AND TREATING METHOD TECHNICAL FIELD The present invention relates to a novel chemical conversion treating solution of a metal surface and a novel surface chemical treating method, which are used for imparting excellent corrosion resistance and coating adhesion to a metal surface. The chemical conversion treating solution of the present invention does not contain harmful hexavalent chromium and can impart high corrosion resistance to a metal surface. Particularly, the chemical conversion treating solution of the present invention can impart high corrosion resistance to aluminum and an aluminum alloy material which are typified by an aluminum die casting material, zinc and a zinc alloy material typified by a zinc die casting material, and a zinc plated metallic material. Furthermore, sludge (precipitate) is less likely to be generated in the treating solution, resulting in less of a burden on the environment. BACKGROUND ART For the purpose of imparting corrosion resistance for a metal, and coating adhesion, a chemical treatment has been used for a long time. First, a chemical treatment of an aluminum-based material, which is a preferred object of the present invention, will be described. The surface treating solution for aluminum or an aluminum alloy material can be generally classified into chromate-type and non chromate-type treating solutions. Typical examples of the chromate-type treating solution include a chromic acid chromate chemical conversion treating solution and a chromate-phosphate chemical conversion treating solution. First, a chromic acid chromate chemical conversion treating solution will be described. Chromic acid chromate chemical conversion treating solution has been used since about 1950 and is now widely used for surface treatment of aircraft materials, building materials and automobile components. The chromic acid chromate chemical conversion treating solution contains chromic acid and a fluoride as a reaction accelerator as main components, and is capable of forming a chemical conversion coating containing hexavalent chromium on a metallic material surface. Also, a chromate-phosphate chemical conversion treating solution is proposed by an invention disclosed in U.S. Patent No. 2,438,877 (Patent Document 1) and contains chromic acid, phosphoric acid and hydrofluoric acid as main components, and is capable of forming a chemical conversion coating containing a hydrated chromium phosphate as a main component on a metallic material surface. The chemical conversion coating does not contain hexavalent chromium and therefore is now widely used as a primary coating treatment of a lid-forming material of a beverage can. The chemical conversion coating formed by the chromate type surface treating solution has excellent corrosion resistance and coating adhesion, but contains harmful hexavalent chromium in the treating solution. Therefore, it is desired to use a surface-treating solution free from containing no hexavalent chromium, to prevent environmental pollution. Many inventions have been proposed for surface treating solutions and surface treating methods containing no hexavalent chromium. However, the number of technigues which could be actually industrialized is not so many. A typical invention of a non-chromate type surface treating solution containing no chromium includes a treating solution disclosed in Japanese Unexamined Patent Publication (Kokai) No. 52-131937 (Patent Document 2). This surface treating solution is an aqueous acidic coating solution which contains zirconium or titanium, or a mixture thereof and phosphoric acid and fluoride, and has a pH of about 1.5 to 4.0. When a metallic material surface is treated using the surface treating solution, a chemical conversion coating containing an oxide of zirconium or titanium as a main component is formed on the metal surface. This non-chromate type surface treating solution has an advantage that it contains no hexavalent chromium, and is widely used for a surface treatment of an aluminum DI can which is used as a beverage can for beer, etc. In general, a non-chromate type surface treating solution belongs to the category of a non-chromium chemical conversion treating agent referred to as a zirconium-based or titanium-based treating agent. The treating method disclosed in Japanese Unexamined Patent Publication (Kokai) No. 57-41376 (Patent Document 3) is a method in which the surface of aluminum, magnesium and an alloy thereof is treated with an aqueous solution containing one or more kinds of titanium salts or zirconium salts, one or more kinds of imidazole derivatives, and an oxidizing agent such as nitric acid, hydrogen peroxide or potassium permanganate. The oxidizing agent accelerates precipitation of titanium and zirconium. The method belongs to the category of a technique for the improvement of a non-chromium chemical conversion treating agent referred to as the zirconium-based or titanium-based treating agent. The non-chromate type treating solutions further include those disclosed in the following patent publications. Japanese Unexamined Patent Publication (Kokai) No. 56-136978 (Patent Document 4) discloses a chemical conversion treating solution composed of an aqueous solution containing a vanadium compound and at least one kind of a compound selected from the group consisting of a titanium salt, a zirconium salt and a zinc salt. The treating solution contains a composition of a zirconium-based or titanium-based treating agent with vanadium. Japanese Unexamined Patent Publication (Kokai) No. 2000-199077 (Patent Document 5) discloses an acidic metal surface treating solution containing a metal acetylacetonate and at least one kind of a compound selected from a water-soluble inorganic titanium compound and a water-soluble inorganic zirconium compound. This treating solution is prepared using vanadyl acetate, zirconium acetate and zinc acetate, and contains a composition of a zirconium-based or titanium-based treating agent with a metal acetate. Japanese Unexamined Patent Publication (Kokai) No. 5-5185 (Patent Document 6) proposes a method for a surface treatment of aluminum, which comprises heating a chromate treating solution having a pH of 1.0 to 3.0, containing 0.1 to 3.0 g/1 of one or more kinds of ions selected from the group consisting of tungstate ions and molybdate ions, 0.5 to 4.0 g/1 of hexavalent chromium ion, 5.0 to 30.0 g/1 of phosphate ions and 0.05 to 2.0 g/1 of free fluorine ions to a temperature of 40 to 60°C and spraying over the surface of aluminum or an aluminum alloy having a clean surface for 0.5 to 3 seconds. The treating solution belongs to the category of a solution referred to as a tungsten-based or molybdenum-based solution. Japanese Unexamined Patent Publication (Kokai) No. 11-36082 (Patent Document 7) proposes a surface treating solution for a light metal or light alloy material having a pH of 1.0 to 7.0, containing 0.01 to 50 g/L of permanganic acid or a salt thereof, and 0.01 to 20 g/L of at least one kind of a compound selected from a water-soluble titanium compound and a water-soluble zirconium compound. The treating solution belongs to the category of a solution referred to as a manganese-titanium-based or manganese-zirconium-based solution. Japanese Unexamined Patent Publication (Kokai) No. 2004-232047 (Patent Document 8) describes a high corrosion resistant chromium-free chemical conversion coating treating agent for aluminum and an aluminum alloy, which contains hexacyanate ions and one or more kinds of ions of metals selected from the group consisting of Ti, V, Mn, Fe, Co, Zr, Mo and W and does not contain chromium ions. These elements are listed in the above inventions, except for cobalt. This invention lacks novelty over past inventions since the scope of the claims is wide. Japanese Unexamined Patent Publication (Kokai) No. 2001-247977 (Patent Document 9) proposes a chromium-free metal surface treating composition in which a coating formed by a surface treatment to the metal surface contains a plurality of metal elements and at least one of the metal elements has a plurality of valences. Actually, the metal surface treating composition is a chromium-free metal surface treating composition characterized in that the metal element comprises at least two or more kinds of Mg, Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Sr, Nb, Y, Zr, Mo, In, Sn, Ta and W. However, since the scope of the claims is too wide and also the actual treating method is unclear, this invention lacks novelty over past inventions. In this prior art, the scope of the conventional zirconium-based, titanium-based, vanadium-based, tungsten-based, molybdenum-based or manganese-based surface treating composition is considered to be expanded. Also, W003/074761 Al (Patent Document 10) proposes a composition for a surface treatment of aluminum, an aluminum alloy, magnesium or a magnesium alloy, containing (1) a compound containing at least one kind of a metal element selected from Hf (IV), Ti (IV) and Zr (IV), (2) a fluorine-containing component in an amount enough to allow fluorine in a molar concentration, which is at least 5 times greater than the total molar concentration of metal contained in the compound A, to exist in the composition, (3) at least one kind of a metal ion B selected from the group of alkali earth metals, (4) at least one kind of a metal ion C selected from Al, Zn, Mg, Mn and Cu, and (5) a nitric acid ion. This treating solution also belongs to the category of a zirconium-based or titanium-based solution in a broad sense. Furthermore, Japanese Unexamined Patent Publication (Kokai) No. 2003-313679 (Patent Document 11) proposes a method for a non-chromium metal surface treatment comprising a process (A) of treating a material to be treated with a non-chromium metal surface treating agent comprising a water-soluble zirconium compound and/or water-soluble titanium component (1) and an organic phosphonic acid component (2) and a process (B) of treating the material to be treated subjected to the process (A) with an aqueous solution of tannin (3), wherein the content of the water-soluble zirconium compound and/or the water-soluble titanium component (1) is from 40 to 1,000 ppm on a mass basis in terms of the amount of zirconium and/or titanium, the content of the organic phosphonic component (2) is from 20 to 500 ppm on a mass basis, the pH of the non-chromium metal surface treating agent is from 1.6 to 4.0, and the content of tannin (3) in the aqueous solution is from 400 to 10,000 ppm on a mass basis. This treating solution also belongs to the category of a zirconium-based or titanium-based solution in a broad sense. An invention of Japanese Unexamined Patent Publication (Kokai) No. 2003-313681 (Patent Document 12) proposes a method for a non-chromium metal surface treatment used in the production of a thermoplastic polyester-based resin coated metal plate, comprising a process (A) of treating a material to be treated with a non-chromium metal surface treating agent comprising a water-soluble zirconium compound and/or water-soluble titanium component (1) and an organic phosphonic acid component (2) and a process (B) of treating the material to be treated subjected to the process (A) with an aqueous solution of tannin (3), wherein the organic phosphonic acid component (2) is a component in which phosphorus atoms constituting a phosphone group are bonded with a carbon atom, the content of the water-soluble zirconium compound and/or the water-soluble titanium component (1) is from 20 to 800 ppm on a mass basis in terms of the amount of zirconium and/or titanium, the content of the organic phosphonic component (2) is from 10 to 500 ppm on a mass basis, the aqueous solution of tannin (3) has a concentration of tannin within a range from 300 to 8,000 ppm on a mass basis and the pH of the non-chromium metal surface treating agent is from 1.6 to 4.0. Similar to the above case, the treating solution also belongs to the category of a zirconium-based or titanium-based solution. A surface treating solution and a treating method using a water-soluble resin, which have an object of imparting corrosion resistance and coating adhesion to an aluminum-containing metallic material, are disclosed in Japanese Unexamined Patent Publication (Kokai) No. 61-91369 (Patent Document 13), Japanese Unexamined Patent Publication (Kokai) No. 1-172406 (Patent Document 14), Japanese Unexamined Patent Publication (Kokai) No. 1-177379 (Patent Document 15), Japanese Unexamined Patent Publication (Kokai) No. 1-177380 (Patent Document 16), Japanese Unexamined Patent Publication (Kokai) No. 2-608 (Patent Document 17) and Japanese Unexamined Patent Publication (Kokai) No. 2-609 (Patent Document 18). In these surface treating solutions and surface treating methods of the prior art, the metal surface is treated with a solution containing a derivative of a polyhydric phenol compound. Also, Japanese Patent No. 2,771,110 (Patent Document 19) discloses a treating solution and a treating method containing a derivative of a polyhydric phenol compound. This treating solution belongs to the category of a resin-based or a resin-metal composite-based solution. Japanese Unexamined Patent Publication (Kokai) No. 2001-303267 (Patent Document 20) proposes a non-chromium rust-preventive treating agent for aluminum, containing a zirconium compound, a fluorine ion, a water-soluble resin and an aluminum salt, wherein the concentration of the zirconium compound is from 100 to 100,000 ppm expressed in terms of a zirconium ion, the concentration of the fluorine ion is from 125 to 125,000 ppm, the nonvolatile content of the water-soluble resin is from 100 to 100,000 ppm, and the concentration of the aluminum salt is from 10 to 10,000 ppm expressed in terms of the aluminum ion. This treating agent is prepared only by using a resin-based solution in combination with a zirconium-based solution. A chemical conversion treating agent, which is not completely a non-chromium agent but does not contain harmful hexavalent chromium, using trivalent chromium is proposed. Japanese Patent No. 3,333,611 (Patent Document 21) proposes a hexavalent chromium-free chemical surface treating agent for an aluminum and aluminum alloy, which contains an acid ion (A) having an acid group containing phosphorus, at least one kind of an ion (B) selected from a trivalent chromium ion and a compound ion containing trivalent chromium and at least one kind of a fluorine component (C) selected from fluoride and complex fluoride, and does not contain a hexavalent chromium ion. This treating agent belongs to the category of a trivalent chromium-based treating agent. Japanese Unexamined Patent Publication (Kokai) No. 2000-332575 (Patent Document 22) proposes a chemical treating agent used after treating a base material made of aluminum or an aluminum alloy with an aqueous acid solution at a temperature of 10 to 70°C for 5 seconds to 5 minutes, wherein the aqueous acid solution is an aqueous acid solution having a pH of 2 or lower, containing (a) at least one kind selected from the group consisting of salts and metal acid salts of metals selected from Fe, Ni, Co, Mo and Ce in the content of 0.01 to 5% by mass based on the aqueous acid solution and (b) an inorganic acid, and the chemical conversion treating agent contains (c) Zr and/or Ti in the content of 0.001 to 1% by mass based on the chemical conversion treating agent, (d) a trivalent chromium ion or a salt thereof in the content of 0.1 to 1,000 ppm based on the chemical conversion treating agent and (e) a fluoride. The chemical treating agent is moderated closely after the chemical treating agent disclosed in Japanese Patent No. 3,333,611 and lacks novelty, and belongs to the category of a trivalent chromium-based treating agent. Japanese Unexamined Patent Publication (Kokai) No. 2004-010937 (Patent Document 23) proposes a method for forming a colored rust-preventive coating on metal, which comprises forming a rust-preventive coating using a liquid composition containing (A) a trivalent chromium ion, (B) at least one kind selected from among the group consisting of Mo, W, Ti, Zr, Mn, Tc, Fe, Ru, Co, alkali earth metals, Ni, Pd, Pt, Sc, Y, V, Nb, Ta, Cu, Ag and Au, (C) at least one kind selected from among the group consisting of chlorine, fluorine, a sulfate ion and a nitrate ion and (D) at least one kind selected from among the group consisting of an oxyacid, an oxyacid salt and an anhydrides of phosphorus and a phosphorus compound. This invention is also moderated closely after the chemical treating agent disclosed in Japanese Patent No. 3,333,611 and lacks novelty, and belongs to the category of a trivalent chromium-based treating agent. Japanese Unexamined Patent Publication (Kokai) No. 2004-3019 (Patent Document 24) proposes a method for forming a chemical conversion coating containing no hexavalent chromium, which provides corrosion resistance to a yellow chromate treatment containing hexavalent chromium, wherein the metal surface is treated with a solution of at least one trivalent chromium chelate complex, trivalent chromium of the chelate complex exists in the concentration of 5 to 100 g/1 in the solution, and the trivalent chromium chelate complex has a ligand substitution rate, which is higher than a fluoride substitution rate in a trivalent chromium-fluoro complex. This invention also lacks novelty, and belongs to the category of a trivalent chromium-based treating agent. The same technique is sometimes used in zinc die casting. Japanese Patent No. 3,597,542 (Patent Document 25) discloses an invention relating to a conversion layer of trivalent chromium formed on zinc, which is substantially a coherent conversion layer that contains no hexavalent chromium and contains trivalent chromium formed on a zinc alloy, and provides corrosion protection for about 100 to 1,000 hours up to first erosion in accordance with DIN 50961 Chapter 10 in a salt spray test in accordance with DIN 50021 SS or ASTMB 117-73 in the absence of additional components such as a silicic acid salt, cerium, aluminum and a boric acid salt, and is also clear, transparent and basically colorless, and also has multi-colored gloss and a layer thickness of about 100 to 1,000 nm, and is also hard and has good adhesion and wiping resistance. The above prior art is roughly classified as (1) a zirconium- or titanium-based surface treating solution, and a technique derived therefrom, (2) a vanadium-, molybdenum-, tungsten- or cobalt-containing surface treating solution, (3) an organic surface treating solution containing tannic acid or a water-soluble resin, (4) a combined organic/inorganic surface treating solution in which zirconium and a resin are used in combination, or (5) a surface treating solution containing trivalent chromium. Of these surface treating solutions, the zirconium-based surface treating solution belonging to (1) is used in applications such as primary coating and cold rolling materials having a smooth surface made of an aluminum material. In applications in which corrosion resistance is not required, the surface treating solution exhibits sufficient performance and is actually industrialized. However, in applications in which a coating is formed on that having a non-uniform surface (many segregates formed on the surface, non-uniform and thick aluminum oxide film) typified by an aluminum die casting material and the aluminum die casting material is used in a non-coating specification, the corrosion resistance is inferior as compared with chromate coating. Even when using (2) a vanadium-, molybdenum-, tungsten-, or cobalt-containing surface treating solution, (3) an organic surface treating solution containing tannin acid and a water-soluble resin, and (4) a combined organic/inorganic surface treating solution in which zirconium and a resin are used in combination, when an aluminum die casting material is treated and corrosion resistance is evaluated in a non-coating specification, the corrosion resistance is not satisfactory. In the trivalent chromium-based surface treating solution (5) which is most excellent in corrosion resistance among the techniques classified roughly, sufficient corrosion resistance is sometimes obtained; however, there are some industrial problems. For example, in Japanese Patent No. 3,333,611 (Patent Document 21), acid ions having an acid group containing phosphorus are included. Therefore, when aluminum is incorporated into the treating solution while continuously treating to form a sludge of aluminum phosphate. To prevent generation of the sludge, the pH must be controlled to a slightly low value. Also, in the case of Japanese Unexamined Patent Publication (Kokai) No. 2000-332575 (Patent Document 22), the treating solution is an aqueous acid solution having a pH of 2 or lower and causes a very strong etching reaction when brought into contact with an aluminum material. Therefore, the coating thus formed becomes porous and corrosion resistance becomes insufficient, and a large amount of etched aluminum is accumulated in the treating solution, and thus sludge can be generated. Japanese Unexamined Patent Publication (Kokai) No. 2004-010937 (Patent Document 23) also has a problem such as generation of sludge because a phosphorus compound is included. Furthermore, in Japanese Patent No. 3,597,542 (Patent Document 25) or related Japanese Unexamined Patent Publication (Kokai) No. 2004-3019 (Patent Document 24), the concentration of trivalent chromium in the treating solution is adjusted to 5 to 100 g/1, which concentration is relatively high and when this treating solution is actually used in industry, a problem such that the cost increases and the load on the following washing water (removal of the treating solution used before the above process by rinsing) increase, occurs. Furthermore, coating is defined in the present invention and the thickness of the coating slightly increases to a value within a range from 100 to 1,000 nm. There is a problem that the corrosion resistance is improved, but coating adhesion becomes inferior when the thickness of the coating increases. Also, a thick film results in increased cost. As described above, there still remains a problem that, when the above conventional non-chromate type surface treating solution is used, the chemical conversion coating thus formed has insufficient corrosion resistance. Particularly when used in an aluminum die casting material which is used as a material of components for aircrafts, automobiles and household electrical appliances in a non-coating specification (only a chemical conversion coating is formed, no coating), there is a problem that sufficient corrosion resistance is not exhibited. Also, in the case of a trivalent chromium-based surface treating solution, there is a problem in industrial operations and treating costs. Therefore, there has never been established an chemical conversion treating solution and a treating method for aluminum or an aluminum alloy material, which does not contain hexavalent chromium in a treating solution and is excellent in operability and economical efficiency, and also can impart sufficient corrosion resistance to an aluminum die casting material in a non-coating specification. Patent Patent Publication Patent Publication Patent Publication Patent Publication Patent Publication Patent Publication Patent Publication Patent Publication Patent Patent Publication Patent Publication Patent Publication Patent Publication Patent Document 1 Document 2 (Kokai) No. Document 3 (Kokai) No. Document 4 (Kokai) No. Document 5 (Kokai) No. Document 6 (Kokai) No. Document 7 (Kokai) No. Document 8 (Kokai) No. Document 9 (Kokai) No. Document 10 Document 11 (Kokai) No. Document 12 (Kokai) No. Document 13 (Kokai) No. Document 14 (Kokai) No. Document 15 U.S. Patent No. 2,438,877 Japanese Unexamined Patent 52-131937 Japanese Unexamined Patent 57-41376 Japanese Unexamined Patent 56-136978 Japanese Unexamined Patent 2000-199077 Japanese Unexamined Patent 5-5185 Japanese Unexamined Patent 11-36082 Japanese Unexamined Patent 2004-232047 Japanese Unexamined Patent 2001-247977 W003/074761 Al Japanese Unexamined Patent 2003-313679 Japanese Unexamined Patent 2003-313681 Japanese Unexamined Patent 61-91369 Japanese Unexamined Patent 1-172406 Japanese Unexamined Patent Publication (Kokai) No. 1-177379 Patent Document 16 Japanese Unexamined Patent Publication (Kokai) No. 1-177380 Patent Document 17 Japanese Unexamined Patent Publication (Kokai) No. 2-608 Patent Document 18 Japanese Unexamined Patent Publication (Kokai) No. 2-609 Patent Document 19 Japanese Patent No. 2,771,110 Patent Document 20 Japanese Unexamined Patent Publication (Kokai) No. 2001-303267 Patent Document 21 Japanese Patent No. 3,333,611 Patent Document 22 Japanese Unexamined Patent Publication (Kokai) No. 2000-332575 Patent Document 23 Japanese Unexamined Patent Publication (Kokai) No. 2004-010937 Patent Document 24 Japanese Unexamined Patent Publication (Kokai) No. 2004-3019 Patent Document 25 Japanese Patent No. 3,597,542 DISCLOSURE OF THE PRESENT INVENTION An object of the present invention is to solve the above problems of the prior art, and specifically, to impart excellent corrosion resistance to the metallic material surface. In particular, an object of the present invention is to provide an economically cheap chemical conversion treating solution and a chemical conversion treating method for a metallic material, which treating solution and method enable, when applied to a uncoated aluminum or zinc die-casting material, the resultant chemical conversion coating to have a corrosion resistance equivalent to that obtainable by the conventional chromate treatment and a high paint-adhesion; the generation of industrial wastes such as sludge to be prevented; and the treating procedures of the method to be easily controlled. The present inventors have studied the means for solving the above problems of the prior art. As a result, they have found an aqueous acidic solution, which contains at least one kind of a compound selected from a specific water-soluble trivalent chromium compound, a specific water-soluble titanium compound and a water-soluble zirconium compound, a specific water-soluble nitrate compound and a specific water-soluble aluminum compound and further contains a specific fluorine compound, and also has a pH controlled within a specific range, and a specific chemical conversion treating solution obtained by adding a specific oxidizing agent to the aqueous acidic solution. Furthermore, they found that a surface treating method capable of forming a chemical conversion coating having excellent corrosion resistance by bringing the specific chemical conversion treating solution into contact with the metallic material surface under specific conditions, and also found that generation of sludge due to a continuous operation can be suppressed by specifying the constitution, the compositions, and the treating conditions of the chemical conversion treating solution. The present invention was completed based on the above findings. The chemical conversion treating solution for a metallic material of the present invention is a treating solution including a component (A) composed of at least one kind of a water-soluble trivalent chromium compound, a component (B) composed of at least one kind selected from a water-soluble titanium compound and a water-soluble zirconium compound, a component (C) composed of at least one kind of a water-soluble nitrate compound and a component (D) composed of at least one kind of a water-soluble aluminum compound, and further comprising a component (E) composed of at least one kind of a fluorine compound, wherein the content expressed in terms of metal chromium (CA) of the water-soluble trivalent chromium compound- containing component (A) is from 0.1 to 20 mmol/liter, the content expressed in terms of metallic titanium and metallic zirconium (CB) of the water-soluble titanium compound and/or water-soluble zirconium compound-containing component (B) is from 0.1 to 10 mmol/liter, the content expressed in terms of a cation (CC) of the water-soluble nitrate compound-containing component (C) is from 0.2 to 40 mmol/liter, the content expressed in terms of fluorine (CE) of the fluorine compound-containing component (E) satisfies the following expression: (CA x2+CBx4+CDx2) where CA, CB, CD and CE are as defined above, and the pH of the treating solution is controlled within a range from 2.3 to 5.0. In the chemical conversion treating solution for a metallic material of the present invention, the surface treating solution further contains an oxidizing agent (F), preferably. In the chemical conversion treating solution for a metallic material of the present invention, the water-soluble trivalent chromium compound-containing component (A) preferably contains at least one kind selected from chromium nitrate, chromium sulfate and chromium fluoride. In the chemical conversion treating solution for a metallic material of the present invention, the component (B) composed of the water-soluble titanium compound and/or the water-soluble zirconium compound preferably contains at least one kind selected from titanium sulfate, titanium oxysulfate, ammonium titanium sulfate, titanium nitrate, titanium oxynitrate, ammonium titanium nitrate, fluorotitanic acid, a fluorotitanium complex salt, zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, ammonium zirconium nitrate, fluorozirconic acid, a fluorozirconium complex salt, titanium lactate, titanium acetylacetonate, titanium triethanolaminate, titanium octylglycolate, tetraisopropyl titanate, tetranormal butyltitanate, zirconyl acetate, zirconyl lactate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, tetranormalbutoxyzirconium and tetranormalpropoxyzirconium. In the chemical conversion treating solution for a metallic material of the present invention, the water-soluble nitrate compound-containing component (C) preferably contains at least one kind selected from magnesium nitrate, calcium nitrate, strontium nitrate, manganese nitrate and cerium nitrate. In the chemical conversion treating solution for a metallic material of the present invention, the water-soluble aluminum compound-containing component (D) preferably contains at least one kind selected from aluminum nitrate aluminum sulfate and aluminum fluoride. In the chemical conversion treating solution for a metallic material of the present invention, the fluorine compound-containing component (E) preferably contains at least one selected from hydrofluoric acid, ammonium fluoride, chromium fluoride, fluorotitanic acid, a fluorotitanium complex salt, fluorozirconic acid, a fluorozirconium complex salt, magnesium fluoride and aluminum fluoride. In the chemical conversion treating solution for a metallic material of the present invention, the oxidizing agent (F) preferably contains at least one kind selected from a peroxo acid compound and a nitrous acid compound and the content is preferably from 0.1 to 15 mmol/liter. In the chemical conversion treating solution for a metallic material according to the present invention, the metallic material is preferably selected from aluminum and an aluminum alloy material, zinc and a zinc alloy material, and a zinc plated metallic material. The method for a chemical conversion treatment of a metallic material surface of the present invention includes heating the above chemical conversion treating solution for a metallic material of the present invention to a temperature of 30 to 70°C; bringing the chemical conversion treating solution into contact with a clean metallic material surface for about 1 to 600 seconds; washing the metallic material surface with water; and drying the surface to form a chemical conversion coating containing 0.02 to 1 mmol/m2 of chromium and 0.02 to 1 mmol/m2 of titanium and/or zirconium and having a thickness of 1 to 100 mm on the metallic material surface. In the method for a chemical conversion treatment of a metallic material surface of the present invention, the metallic material surface washed with water is preferably washed with deionized water between washing with water and drying. In the method for a chemical conversion treatment of a metallic material surface of the present invention, the clean metallic material surface is preferably a surface in which an oxide has been removed by subjecting the surface of the metallic material to a deoxidizing treatment using an aqueous treating solution containing an acid or a redox agent. In the method for a chemical conversion treatment of a metallic material surface of the present invention, the clean metallic material is preferably selected from aluminum and an aluminum alloy material, zinc and a zinc alloy material and a zinc plated metallic material. The method for a chemical conversion treatment of a metallic material surface of the present invention includes heating an aqueous chemical conversion treating solution for a metallic material comprising a component (A) composed of at least one kind of a water-soluble trivalent chromium compound, a component (B) composed of at least one kind selected from a water-soluble titanium compound and a water-soluble zirconium compound, a component (C) composed of at least one kind of a water- soluble nitrate compound and a component (D) composed of at least one kind of a water-soluble aluminum compound, and further containing a component (E) composed of at least one kind of a fluorine compound, to a temperature of 30 to 70°C; bringing the chemical conversion treating solution into contact with a clean metallic material surface for about 1 to 600 seconds; controlling the composition of the chemical conversion treating solution as follows: the content expressed in terms of metal chromium (CA) of the water-soluble trivalent chromium compound-containing component (A) is from 0.1 to 20 mmol/liter, the content expressed in terms of metallic titanium and metallic zirconium (CB) of the water-soluble titanium compound and/or water-soluble zirconium compound-containing component (B) is from 0.1 to 10 mmol/liter, the content expressed in terms of a cation (CC) of the water-soluble nitrate compound-containing component (C) is from 0.2 to 40 mmol/liter, the content expressed in terms of aluminum (CD) of the water-soluble aluminum component (D) is from 0.2 to 40 mmol/liter, the content expressed in terms of fluorine (CE) of the fluorine compound-containing component (E) satisfies the following expression: (CA x2+CBx4+CDx2) where CA, CB, CD and CE are as defined above, and the pH of the treating solution is controlled within a range from 2.3 to 5.0, thereby to form a chemical conversion coating, which prevents generation of sludge in the chemical conversion treating solution and is also excellent in corrosion resistance, on the surface of the metallic material; washing the metallic material surface with water; and drying the surface to form a chemical conversion coating containing 0.02 to 1 mmol/m2 of chromium and 0.02 to 1 mmol/m2 of titanium and/or zirconium and having a thickness of I to 100 mm on the metallic material surface. In the method for a chemical conversion treatment of a metallic material surface of the present invention, the metallic material surface washed with water is preferably washed with deionized water between the water-washing step and the drying step. In the method for a chemical conversion treatment of a metallic material surface of the present invention, the clean metallic material surface is preferably a surface in which an oxide has been removed by subjecting the surface of the metallic material to a deoxidizing treatment using an aqueous treating solution containing an acid or a redox agent. In the method for a chemical conversion treatment of a metallic material surface of the present invention, the clean metallic material is preferably selected from aluminum and an aluminum alloy material zinc, a zinc alloy material and a zinc plated metallic material. EFFECT OF THE INVENTION According to the chemical conversion treating solution for a metallic material and the chemical treating method of the present invention, excellent corrosion resistance can be imparted to a metal surface, for example, the surface of aluminum and an aluminum alloy material without using harmful hexavalent chromium. Furthermore, the chemical conversion treating solution exerts an excellent effect such that it imparts corrosion resistance equivalent to that of the conventional chromate treatment when applied to an aluminum die casting material or a zinc die casting material; the resultant chemical conversion coating has a good paint-adhesion; and generation of industrial wastes such as sludge can be simply controlled. BEST MODE FOR CARRYING OUT THE INVENTION The chemical conversion treating solution for a metallic material of the present invention is an aqueous acidic solution which contains a component (A) containing a water-soluble trivalent chromium compound, a component (B) containing a water-soluble titanium compound and a water-soluble zirconium compound, a component (C) containing a water-soluble nitrate compound and a component (D) containing a water-soluble aluminum compound, and further contains a component (E) containing a fluorine compound, and also has a pH controlled within a range from 2.3 to 5.0. Furthermore, the chemical conversion treating solution of the present invention may contain an oxidizing agent component (F). Operations of the respective components will now be described. The water-soluble trivalent chromium compound-containing component (A) of the chemical conversion treating solution for metal of the present invention is an essential component and exerts a large influence on corrosion resistance of the resulting chemically-treated metallic material. In the case of mixing with a trivalent chromium compound-containing component (A), at least one kind selected from chromium nitrate, chromium sulfate and chromium fluoride can be used. The content expressed in terms of chromium of the component (A) is within a range from 0.1 to 20 mmol/liter, and preferably from 0.4 to 4 mmol/liter. When the content of the component (A) is less than 0.1 mmol/liter, the content of chromium in the resulting chemical conversion coating becomes insufficient. In contrast, when the content is more than 20 mmol/liter, the cost increases, resulting in economical disadvantages. The component (B) composed of at least one kind selected from a water-soluble titanium compound and a water-soluble zirconium compound in the chemical conversion treating solution for metal of the present invention is also an essential component and exerts a large influence on the corrosion resistance of the chemically-treated metallic material. In the case of mixing the water-soluble titanium compound and/or the water-soluble zirconium component (B), it is possible to use at least one kind selected from water-soluble inorganic titanium compounds and water-soluble inorganic zirconium compounds, such as titanium sulfate, titanium oxysulfate, ammonium titanium sulfate, titanium nitrate, titanium oxynitrate, ammonium titanium nitrate, fluorotitanic acid, fluorotitanium complex salt, zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, ammonium zirconium nitrate, fluorozirconic acid, and a fluorozirconium complex salt; and water-soluble organic titanium compounds and water-soluble organic zirconium compounds, such as titanium lactate, titanium acetylacetonate, titanium triethanolaminate, titanium octylglycolate, tetraisopropyl titanate, tetranormal butyltitanate, zirconyl acetate, zirconyl lactate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, tetranormalbutoxyzirconium, and tetranormalpropoxyzirconium. The content expressed in terms of titanium or zirconium of the component (B) must be within a range from 0.1 to 10 mmol/liter, and preferably from 0.4 to 4 mmol/liter. If the content expressed in terms of Ti and/or Zr of the component (B) is less than 0.1 mmol/liter, adhesion of zirconium or titanium becomes insufficient. In contrast, when the content is more than 10 mmol/liter, the concentration in the chemical conversion treating agent is high and the cost increases, resulting in economical disadvantages. The water-soluble nitrate compound-containing component (C) in the chemical treating solution for metal of the present invention is also an essential component and controls uniformity of the coating to be formed and therefore influence is corrosion resistance. The component (C) has the effect of suppressing excess etching at the interface between the chemical conversion treating agent and the material during a treating process, and therefore it is considered that the resultant coating is uniform. In case of mixing the water-soluble nitrate compound-containing component (C), at least one kind of magnesium nitrate, calcium nitrate, strontium nitrate, manganese nitrate and cerium nitrate can be used. The content CC expressed in terms of a cation of the water-soluble nitrate compound-containing component (C) must be within a range from 0.2 to 40 mmol/liter, and preferably from 4 to 30 mmol/liter, in terms of a cation of a nitric acid salt, for example, a magnesium cation and/or a calcium cation. When the content of the component (C) is less than 0.2 mmol/liter, the effect of making the coating uniform becomes insufficient. In contrast, when the content is more than 40 mmol/liter, the concentration of the component in the chemical conversion treating agent is high, and thus sludge may be generated. The water-soluble aluminum compound-containing component (D) in the chemical conversion treating solution for metal of the present invention is also an essential component and has the effect of preventing excess etching of the metallic material surface with the chemical conversion treating agent, similar to the magnesium calcium cation. In the case of mixing the water-soluble aluminum compound-containing component (D), aluminum nitrate, aluminum sulfate and aluminum fluoride can be used. Also, when aluminum or an aluminum alloy material is continuously treated, metallic aluminum of the material is eluted in the chemical conversion treating agent through etching involved in a chemical reaction. Therefore, if the treating solution is fully controlled, an aluminum compound may not be forcibly added (supplied) upon continuous operation. The content expressed in terms of aluminum of the component (D) must be within a range from 0.2 to 40 mmol/liter, and preferably from 4 to 20 mmol/liter. When the content of the component (D) is less than 0.2 mmol/liter, the resultant coating-uniformizing effect becomes insufficient. In contrast, when the content is more than 40 mmol/liter, the concentration of the component in the chemical conversion treating agent is high, and thus sludge may be generated. The fluorine compound-containing component (E) in the chemical conversion treating solution of the present invention for metal is a very important essential component. It has been found that the fluorine compound exerts an influence on etching of the material and the component (E) also exerts a influence on corrosion resistance of the resulting chemically-treated metallic material in the present invention. Also, it has been found that generation of sludge upon a continuous operation can be suppressed by properly controlling the amount of the component (E). Some prior art treating liquid contains a fluorine compound, but mainly reports an etching action thereof. In the case of mixing the fluorine compound synthetic component (E), at least one kind of hydrofluoric acid, ammonium fluoride, chromium fluoride, fluorotitanic acid, a fluorotitanium complex salt, fluorozirconic acid, a fluorozirconium complex salt, magnesium fluoride and aluminum fluoride can be used. Of these fluorine compounds, hydrofluoric acid and ammonium fluoride are very important and the content is adjusted by these fluorine compounds. The content expressed in terms of fluorine (CE) of the component (E) in the chemical conversion treating solution, namely, the total fluorine content is preferably within a concentration range of the following expression. Namely, the concentration CA of a water-soluble trivalent chromium compound component, the concentration CB of at least one kind of a compound component (B) selected from a water-soluble titanium compound and a water-soluble zirconium compound and the concentration CD of a water-soluble aluminum compound component (D) have a close relationship and must be controlled so as to satisfy the following expression. (CA x2+CBx4+CDx2) When CE is less than the minimum concentration shown in the expression, corrosion resistance of the chemical conversion coating to be formed becomes insufficient and sludge is often generated upon a continuous operation. In contrast, when CE exceeds the maximum CE value, the resulting chemical conversion treating solution has a strong etching power and the deposition rate of the coating becomes inferior. Also, the CE value is preferably within the following range. (CA x 3 + CB x 6 + CD x 2) The pH of the chemical conversion treating solution for metal of the present invention is very important and there is a proper range. In the chemical conversion treating solution of the present invention, it is important that the pH be controlled within a range of 2.3 to 5.0. When the pH is lower than 2.3, the resulting chemical conversion treating solution has strong etching power and the deposition rate of the coating becomes inferior. In contrast, when the pH is higher than 5.0, sludge is often generated upon continuous operation. The pH is more preferably within a range from 3.0 to 4.0. The method for adjusting the pH is not specifically limited and the pH is preferably adjusted using nitric acid, hydrofluoric acid, ammonium hydrogen carbonate or ammonia water. To the chemical treating solution for metal of the present invention, an oxidizing agent (F) may be further added. The oxidizing agent has the effect of promoting a chemical conversion coating forming reaction, thereby increasing coating formation efficiency, densifying the coating and improving the corrosion resistance. As the oxidizing agent, a peroxo acid compound and/or a nitrous acid compound are preferably used. Also, the content is preferably from 0.1 to 15 mmol/liter. When the content is 0.1 mmol/liter or more, the effect for accelerating chemical conversion coating formation is exerted. Although the content may be more than 15 mmol/liter, when the concentration increases, the cost increases and a economical disadvantages occur. The method for a chemical treatment of a metallic material surface of the present invention includes heating the above chemical conversion treating solution for metal to a temperature of 30 to 70°C; bringing the chemical conversion treating solution into contact with a clean metallic material surface for about 1 to 600 seconds; washing the metallic material surface with water; washing the metallic material surface with deionized water as required; and drying the surface to form a chemical conversion coating containing 0.02 to 1 mmol/m2 of chromium and 0.02 to 1 mmol/m2 of titanium and/or zirconium and having a controlled thickness of 1 to 100 nm on the metallic material surface. The treatment temperature is an important factor which influences reactivity. When the treatment temperature is lower than 30°C, it is not suited for industrialization because of poor reactivity. In contrast, the treatment temperature is not preferably higher than 70°C because stability of the treating solution deteriorates. The surface of the material to be brought into contact with the chemical conversion treating solution must be clean. When oil is adhered to the surface, uniform coating cannot be achieved. A pretreatment before cleaning is not specifically limited and the surface may be cleaned by subjecting to a pretreatment such as conventional solvent degreasing, alkali degreasing, acidic degreasing, alkali etching, followed by acid desmutting and shotblasting. However, it is preferred that an oxide of the surface be removed using a water-soluble treating solution containing an acid or a redox agent and then the material is subjected to chemical conversion treatment. The treatment time in which the material is brought into contact with the chemical conversion treating solution is within a range from 1 to 600 seconds. The treatment time is the time required to obtain the following coating weight through combination with the treatment temperature and the concentration. When the treatment time is less than one second, the reaction is not completely conducted and the coating is not completely formed. If the treatment time is more than 600 seconds, noticeable advantage is not obtained and industrial productivity decreases. As the method of bringing the material into contact with the treating solution, an immersion method, a spray method and a flow coat method can be employed. Then, the material is washed with water so as to remove the unreacted component. Also, when the chemically-treated surface is used as a primer coat, a hardness component in the washing liquid sometimes exerts a bad influence. In this case, the material is preferably washed with deionized water. Furthermore, the material is dried. Drying is conducted so as to vaporize moisture, and the drying and the drying temperature are not specifically limited. Warm air drying is conducted the drying temperature is preferably from 80 to 140°C from an industrial point of view. On the surface of the treated material, a chemical conversion coating containing 0.02 to 1 mmol/m2 of chromium, 0.02 to 1 mmol/m2 of titanium and/or zirconium must be formed. When the content of chromium is less than 0.02 mmol/m2 and the content of titanium and/or zirconium is less than 0.02 mmol/m2, the weight of the chemical conversion coating is insufficient and corrosion resistance becomes insufficient. When the content of chromium is more than 1 mmol/m2 and the content of titanium and/or zirconium is more than 1 mmol/m2, the chemical conversion coating is not inferior in corrosion resistance, but cost increases, and economical disadvantages occur. It is important that the thickness of the chemical conversion coating is within a range from 1 to 100 nm. The metallic material to be brought into contact with the chemical conversion treating solution for metal is not specifically limited and is preferably aluminum or an aluminum alloy material, namely, an aluminum containing metallic material. Moreover, a material, to which sufficient corrosion resistance is not easily imparted by the other inventions and can be effectively imparted by the present invention, is an aluminum die casting material. When an aluminum die casting material used widely in a component material, for example, JIS-ADC-12, very high validity is exhibited. Also, the present invention is suited for zinc, a zinc alloy material and a zinc-plated metallic material. In particular, excellent effect is exerted in a zinc die casting material. Finally, the coating forming reaction mechanism of the present invention and the coating to be formed will be described. Description will be made by way of a preferred aluminum-containing material as an example. The chemical conversion treating solution of the present invention is an aqueous acid solution. Aluminum and an aluminum alloy are amphoteric metals, and when they are brought into contact with an acidic solution, an etching (dissolution) reaction of aluminum arises. In the etching reaction, aluminum is converted into ions, resulting in emission of electrons. Hydrogen ions receive electrons to evolve hydrogen, and a decrease in hydrogen ions arises in the vicinity of the interface of the material, and thus the pH increases. It is assumed that the eluted aluminum reacts with hydrogen fluoride existing in the chemical conversion treating agent of the present invention to obtain aluminum fluoride. The zirconium compound and/or the titanium compound as essential components of the present invention exist in the form of a complex fluoride in the scope of the present invention. The equilibrium reaction of the complex fluoride varies according to consumption of hydrogen ions and dissociation of hydrofluoric acid involved in the etching reaction, and as a result, zirconium and/or titanium oxide (including hydroxide and hydrate) are deposited on the coating. Consequently, a coating is formed in a state where the oxide serves as a main component of the coating and a coexisting trivalent chromium component (which is considered as a chromium fluoride in the chemical conversion treating solution of the present invention) is incorporated in the coating. Therefore, the coating is composed of zirconium oxide or titanium oxide, or a composite of a mixed oxide and a trivalent chromium compound. It is assumed that the trivalent chromium compound limited in the present invention exerts a particularly large influence on impartion of corrosion resistance. EXAMPLES With respect to a chemical conversion treating solution for metal and a method for a surface treatment of the metal according to the present invention, Examples and Comparative Examples will be shown below and the novelty and validity will be described. The following materials and testing methods were used. The composition and the treating method of the chemical conversion treating solution are described in the Examples. (1) Aluminum Die Casting Material (JIS-ADC12) An aluminum diecast panel (manufactured by Paltec Test Panels Co., Ltd.) was used. (2) Zinc Die Casting Material (JIS-ZDC2): used only in Examples 9 and 10, and Comparative Example 9 A zinc diecast panel (manufactured by Paltec Test Panels Co., Ltd.) was used. A test metallic material was cleaned by immersing in an aqueous 2% solution of an alkali degreasing agent (Fine Cleaner® 315 manufactured by Nihon Parkerizing Co., Ltd.) at 60°C for 2 minutes, and rinsing the surface with running tap water. A test metallic material was cleaned by immersing in an aqueous 2% solution of an alkali degreasing agent (Deoxidizer® 7 manufactured by Nihon Parkerizing Co., Ltd.) at 40°C for one minute, and rinsing the surface with running tap water. Deoxidizing was carried out only in Example 7. The weight of chromium and zirconium and/or titanium coated by a chemical conversion treatment was determined using an X-ray fluorescence spectrometer (System 3270E manufactured by Rigaku Corporation). Each test sample was sputtered using a surface analysis device (ESCA-850M manufactured by Shimadzu Corporation) and the thickness of the chemical conversion coating was calculated from the time required for completion of sputtering. Each test sample was subjected to a salt spray test (JIS-Z2371) and the ratio of the area where white rust was generated was measured after 96 hours and then evaluated. The ratio of the area where white rust was generated should preferably be 10% or less, and particularly preferably 5% or less. A solvent-based paint (melamine alkyd-based paint) was applied to the surface of a test sample in a thickness of 30 jam and cross-cut lines were formed so as to form squares. After immersing in boiling water for one hour, the test sample was wiped to remove water, and an adhesive tape was adhered to the surface of the test sample and then removed. The state of the squares was observed. The number of squares was 100 and the number of squares left without being peeled away was measured. The number of the non-peeled squares was from 100 (best) to 0 (worst). With respect to the test examples which showed good results in evaluating corrosion resistance, a sludge generation test was carried out for the purpose of evaluating operability of industrialization. 1 liter of a chemical conversion treating solution was prepared and the test metallic material (area to be treated: 10 m2) was continuously treated using the treating solution. Each component was supplied so as to maintain an initial concentration of each component without causing variation in the concentration due to liquid loss (carrying out) by the coating and the treatment. After the treatment, the treating solution was allowed to stand at 40°C for 48 hours and the state of the solution was observed. Precipitate (sludge) and the state of the solution (turbidity) were observed. Preferably, no sludge is generated. Example 1 The following chemical conversion treating solution 1 was prepared and a cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 1. (A): Chromium fluoride: 10 mmol/liter (B): Fluorotitanic acid: 5 mmol/liter (C): Magnesium nitrate: 10 mmol/liter (D): Aluminum nitrate: 0.4 mmol/liter (E): Hydrogen fluoride and fluorotitanic acid added in (B) (total fluorine): 65 mmol/liter (F): None pH: 4.0 adjusted with ammonia water Treating temperature: 40°C Treating time: 120 seconds Contact method: Immersion Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Example 2 The following chemical conversion treating solution 2 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 2. (A): Chromium nitrate: 5 mmol/liter (B): Fluorotitanic acid: 2 mmol/liter Fluorozirconic acid: 3 mmol/liter (C): Magnesium nitrate: 5 mmol/liter (D): Aluminum nitrate: 0.4 mmol/liter (E): Hydrogen fluoride and fluoro acid added in (B) (total fluorine): 60 mmol/liter (F): None pH: 3.0 adjusted with ammonia water Treating temperature: 60°C Treating time: 60 seconds Contact method: Spraying treatment Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Example 3 The following chemical conversion treating solution 3 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 3. Ourface Treating Solution 3> (A): Chromium nitrate: 1 mmol/liter (B): Ammonium zirconium nitrate 1 mmol/liter (C): Magnesium nitrate: 1 mmol/liter (D): Aluminum nitrate: 1 mmol/liter (E): Hydrogen fluoride (total fluorine): 15 mmol/liter (F): Hydrogen peroxide 1 mmol/liter pH: 4.0 adjusted with ammonium hydrogen carbonate Treating temperature: 60°C Treating time: 480 seconds Contact method: Immersion Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Example 4 The following chemical conversion treating solution 4 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 4. (A): Chromium nitrate: 5 mmol/liter (B): Fluorotitanic acid: 2 mmol/liter Fluorozirconic acid: 3 mmol/liter (C): Calcium nitrate: 5 mmol/liter Magnesium sulfate: 1 mmol/liter (D): Aluminum fluoride: 10 mmol/liter (E): Hydrogen fluoride and fluoro acid added in (B) (total fluorine): 80 mmol/liter (F): None pH: 3.5 adjusted with ammonia water Treating temperature: 50°C Treating time: 180 seconds Contact method: Immersion treatment Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Example 5 The following chemical conversion treating solution 5 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 5. (A): Chromium fluoride: 15 mmol/liter (B): Ammonium zirconium fluoride: 8 mmol/liter (C): Magnesium fluoride: 0.2 mmol/liter (D): Aluminum fluoride: 0.2 mmol/liter (E): Fluoride added in (A) and (B) (total fluorine): 93 mmol/liter (F): None pH: 2.6 adjusted with nitric acid Treating temperature: 50°C Treating time: 300 seconds Contact method: Immersion treatment Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Example 6 The following chemical conversion treating solution 6 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 6. (A) : Chromium nitrate: 15 itimol/liter (B): Fluorotitanic acid: 1 mmol/liter Fluorozirconic acid: 1 mmol/liter (C): Magnesium nitrate: 20 mmol/liter (D): Aluminum nitrate: 0.4 mmol/liter (E): Hydrogen fluoride and fluoro acid added in (B) (total fluorine): 45 mmol/liter (F): None pH: 3.5 adjusted with ammonia water Treating temperature: 35°C Treating time: 480 seconds Contact method: Immersion treatment Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Example 7 The following chemical conversion treating solution 7 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 7. (A): Chromium nitrate: 15 mmol/liter (B): Fluorotitanic acid: 1 mmol/liter Fluorozirconic acid: 1 mmol/liter (C): Magnesium nitrate: 10 mmol/liter Cerium nitrate: 1 mmol/liter (D): Aluminum nitrate: 0.4 mmol/liter (E): Hydrogen fluoride and fluorotitanic acid added in (B) (total fluorine): 45 mmol/liter (F): None pH : 3.5 adjusted with ammonia water Treating temperature: 45°C Treating time: 240 seconds Contact method: Immersion treatment Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Example 8 The cleaned metallic material (1) was subjected to deoxidizing treatment and then subjected to chemical conversion treatment in the same manner as in Example 7. Example 9 A cleaned metallic material (2) (zinc die casting material) was subjected to chemical conversion treatment in the same manner as in Example 1. Example 10 The cleaned metallic material (2) (zinc die casting material) was subjected to chemical conversion treatment in the same manner as in Example 7. Comparative Example I The following chemical conversion treating solution 7 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 7. Ourface Treating Solution 7> (A): Chromium nitrate: 15 mmol/liter (B): Fluorotitanic acid: 1 mmol/liter (C): Magnesium nitrate: 20 mmol/liter (D): Aluminum nitrate: 0.4 mmol/liter (E): Fluoro acid added in (B) (total fluorine): 6 mmol/liter (F): None pH : 3.5 adjusted with ammonia water Treating temperature: 30°C Treating time: 30 seconds Contact method: Immersion treatment Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Comparative Example 2 The following chemical conversion treating solution 8 was prepared and the cleaned metallic material (1) was subjected to a chemical conversion treatment using following treating method 8. (A) : None (B): Fluorotitanic acid: 1 mmol/liter (C): None (D): Aluminum nitrate: 0.4 mmol/liter (E): Fluoro acid added in (B) (total fluorine): 6 mmol/liter (F): None pH : 2.3 adjusted with nitric acid Treating temperature: 40°C Treating time: 30 seconds Contact method: Immersion treatment Processes: Washing with running tap water (at room temperature for 30 seconds) + washing with deionized water (at room temperature for 30 seconds) after treatment Drying (at 100°C for 3 minutes) in an electric oven Comparative Example 3 Using a commercially available non-chromate chemical conversion treating agent (aqueous 2% solution of ALODINE™ 404 corresponding to Japanese Unexamined Patent Publication (Kokai) No. 52-131937), the cleaned metallic material (1) was subjected to a spraying treatment at 40°C for 30 seconds. In the same manner as in treating method l, the cleaned metallic material (1) was washed with water, washed with deionized water and then dried. Comparative Example 4 An aqueous treating solution 8 (corresponding to Japanese Unexamined Patent Publication (Kokai) No. 2004-232047) containing 2 g/liter of iron hexacyanate, 1 g/liter of fluorotitanic acid and 1 g/liter of cobalt nitrate was trially prepared and the cleaned metallic material (1) was subjected to an immersion treatment at 40°C for 60 seconds. In the same manner as in treating method 1, the cleaned metallic material (1) was washed with water, washed with deionized water and then dried. Comparative Example 5 A surface treating solution (corresponding to W003/074761 Al) containing (1) 1 mmol/liter of titanium sulfate, (2) an amount of hydrofluoric acid corresponding to a 6-fold amount of the amount of titanium sulfate, (3) 0.2 mmol/liter of calcium nitrate and (4) 0.2 mmol/liter of aluminum nitrate (which emits nitrate ions) was trially prepared and the cleaned metallic material (1) was subjected to an immersion treatment at 40°C for 60 seconds. In the same manner as in treating method 1, the cleaned metallic material (1) was washed with water, washed with deionized water and then dried. Comparative Example 6 An aqueous surface treating solution (corresponding to Japanese Patent No. 3,333,611) containing 10 mmol/liter of phosphoric acid, 10 mmol/liter of chromium phosphate and 1 mmol/liter of fluorozirconic acid was trially prepared and the cleaned metallic material (1) was subjected to an immersion treatment at 40°C for 60 seconds. In the same manner as in treating method 1, the cleaned metallic material (1) was washed with water, washed with deionized water and then dried. Comparative Example 7 A surface treating solution (corresponding to Japanese Unexamined Patent Publication (Kokai) No. 2000-332575) containing 10 g/liter of cerium nitrate, 100 ppm of chromium nitrate and 100 ppm of hydrofluoric acid and having the pH thereof adjusted to 2 with nitric acid was treated at 50°C for 2 seconds. Using the surface treating solution thus obtained, cleaned metallic material (1) was subjected to an immersion treatment at 40°C for 60 seconds. In the same manner as in treating method 1, cleaned metallic material (1) was washed with water, washed with deionized water and then dried. Comparative Example 8 Using an aqueous 5% solution (containing hexavalent chromium) of a chromate chemical conversion treating agent (Alchrome™ 713, make-up agent), cleaned metallic material (1) was subjected to an immersion treatment at 40°C for 20 seconds. In the same manner as in the treating method 1, the cleaned metallic material was washed with water, washed with deionized water and then dried. Comparative Example 9 The following treating solution (in conformity with Japanese Patent No. 3,597,542) was prepared. Namely, the pH of an aqueous solution prepared by dissolving 100 g/liter of CrCl3-6H20 (trivalent chromium salt), 100 g/liter of NaN03, 15.75 g/liter of NaF and 26.5 g/liter of citric acid 1H20 was adjusted to 2.5 using a sodium hydroxide solution. In a boiling state, the cleaned metallic material (2) was subjected to an immersion treatment for 30 seconds, washed with water, washed with deionized water and then dried. (Table Removed)The test results of Examples 1 to 10 and Comparative Examples 1 to 9 are shown in Table 1. The test results revealed that almost all existing chemical treating agents and methods do not provide sufficient corrosion resistance. In Comparative Example 6 and Comparative Example 9 which have relatively high corrosion resistance, when a sludge generation test is carried out, a precipitate was generated and there was a problem in industrial operability (productivity). The test results also revealed that the chemical conversion treating solution and method of the present invention can impart excellent corrosion resistance, excellent paint adhesion to a coated metal surface and excellent operability. INDUSTRIAL APPLICABILITY The chemical conversion treating solution and chemical conversion treating method of a metallic material of the present invention provide excellent corrosion resistance, coating adhesion and sludge prevention properties to a metallic material without using a hexavalent chromium compound, and have high industrial applicability. We Claim: 1. A chemical conversion treating solution for a metallic material, comprising a component (A) composed of at least one kind of a water-soluble trivalent chromium compound, a component (B) composed of at least one kind selected from a water- soluble titanium compound and a water-soluble zirconium compound, a component (C) composed of at least one kind of a water-soluble nitrate compound and a component (D) composed of at least one kind of a water-soluble aluminum compound, and further comprising a component (E) composed of at least one kind of a fluorine compound, wherein the content expressed in terms of metal chromium (CA) of the water-soluble trivalent chromium compound-containing component (A) is from 0.1 to 20 mmol/liter, the content expressed in terms of metallic titanium and metallic zirconium (CB) of the component (B) which is composed of at least one kind selected from the water-soluble titanium compound and zirconium compound is from 0.1 to 10 mmol/liter, the content expressed in terms of a cation (CC) of the water- soluble nitrate compound-containing component (C) is from 0.2 to 40 mmol/liter, the content expressed in terms of aluminum (CD) of the water-soluble aluminum component (D) is from 0.2 to 40 mmol/liter, the content expressed in terms of fluorine (CE) of the fluorine compound-containing component (E) satisfies the following expression: (CA x 2 + CB x 4 + CD x 2) ≤ CE ≤ (CA x 4 + CB x 7 + CD x 4) where CA, CB, CD and CE are as defined above, and a pH of the treating solution is controlled within a range from 2.3 to 5.0. 2. The chemical conversion treating solution for a metallic material as claimed in claim 1, wherein the surface treating solution further contains an oxidizing agent (F). 3. The chemical conversion treating solution for a metallic material as claimed in claim 1 or 2, wherein the water—soluble trivalent chromium compound-containing component (A) contains at least one kind selected from chromium nitrate, chromium sulfate and chromium fluoride. 4. The chemical conversion treating solution for a metallic material as claimed in claim 1 or 2, wherein the component (B) composed of at least one kind selected from the water-soluble titanium compound and the water—soluble zirconium compound contains at least one kind selected from titanium sulfate, titanium oxysulfate, ammonium titanium sulfate, titanium nitrate, titanium oxynitrate, ammonium titanium nitrate, fluorotitanic acid, a fluorotitanium complex salt, zirconium sulfate, zirconium oxysulfate, ammonium zirconium sulfate, zirconium nitrate, zirconium oxynitrate, ammonium zirconium nitrate, fluorozirconic acid, a fluorozirconiurn complex salt, titanium lactate, titanium acetylacetonate, titanium triethanolaminate, titanium octyiglycolate, tetraisopropyl titanate, tetranormal butyltitanate, zirconyl acetate, zirconyl lactate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, tetranormalbutoxyzirconium and tetranormalpropoxyzirconium. 5. The chemical conversion treating solution for a metallic material as claimed in claim 1 or 2, wherein the water—soluble nitrate compound-containing component (C) contains at least one kind selected from magnesium nitrate, calcium nitrate, strontium nitrate, manganese nitrate and cerium nitrate. 6. The chemical conversion treating solution for a metallic material as claimed in claim 1 or 2, wherein the water—soluble aluminum compound-containing component (D) contains at least one kind selected from aluminum nitrate aluminum sulfate and aluminum fluoride. 7. The chemical conversion treating solution for a metallic material as claimed in claim 1 or 2, wherein the fluorine compound-containing component (E) contains at least one selected from hydrofluoric acid, ammonium fluoride, chromium fluoride, fluorotitanic acid, a fluorotitanium complex salt, fluorozirconic acid, a fluorozirconium complex salt, magnesium fluoride and aluminum fluoride. 8. The chemical conversion treating solution for a metallic material as claimed in claim 2, wherein the oxidizing agent (F) contains at least one kind selected from a peroxo acid compound and a nitrous acid compound and the content is from 0.1 to 15 mmol/liter. 9. The chemical conversion treating solution for a metallic material as claimed in any one of claims 1 to 8, wherein the metallic material is selected from aluminum and an aluminum alloy material, zinc and a zinc alloy material, and a zinc plated metallic material. 10. A method for a chemical conversion treatment of a metallic material surface with the chemical conversion treating solution as claimed in claim 1, comprising steps of: (1) heating the chemical conversion treating solution to a temperature of 30 to 70°C; (2) bringing the chemical conversion treating solution into contact with a clean metallic material surface for a time of 1 to 600 seconds; (3) washing the treated metallic material surface with water; and (4) drying the water washed metallic material surface, to form a chemical conversion coating containing 0.02 to 1 mmol/m2 of chromium and 0.02 to 1 mmol/m2 of at least one member of titanium and zirconium and having a thickness of 1 to 100 nm on the metallic material surface. 11. The method for a chemical conversion treatment of a metallic material surface as claimed in claim 10, wherein the clean metallic material is selected from aluminum and an aluminum alloy material, zinc and a zinc alloy material and a zinc plated metallic material.

Documents:

9005-DELNP-2007-Abstract-(23-09-2011).pdf

9005-delnp-2007-abstract.pdf

9005-DELNP-2007-Claims-(23-09-2011).pdf

9005-delnp-2007-claims.pdf

9005-delnp-2007-Correspondence Others-(18-05-2012).pdf

9005-delnp-2007-Correspondence Others-(19-04-2012).pdf

9005-DELNP-2007-Correspondence Others-(23-09-2011).pdf

9005-delnp-2007-correspondence-others-1.pdf

9005-delnp-2007-correspondence-others.pdf

9005-delnp-2007-description (complete).pdf

9005-delnp-2007-form-1.pdf

9005-delnp-2007-form-18.pdf

9005-DELNP-2007-Form-2-(23-09-2011).pdf

9005-delnp-2007-form-2.pdf

9005-delnp-2007-form-26.pdf

9005-delnp-2007-Form-3-(19-04-2012).pdf

9005-DELNP-2007-Form-3-(23-09-2011).pdf

9005-delnp-2007-form-3.pdf

9005-DELNP-2007-Form-5.pdf

9005-DELNP-2007-GPA-(23-09-2011).pdf

9005-delnp-2007-pct-210.pdf

9005-delnp-2007-pct-304.pdf

9005-delnp-2007-pct-308.pdf