Chemical conversion agent

Abstract

A chemical conversion treatment agent forms a chemical conversion coating on or over a surface of a metallic material, which agent achieves excellent external appearance after chemical conversion treatment, as well as excellent corrosion resistance as evaluated by, for example, an exposure test or the VDA621-415 method after painting, and which agent can be used in a wide temperature range. The agent includes: a source of fluorine ions; a source A of ions containing zirconium; a source B of ions containing aluminum; and a water-soluble or water-dispersible polymer, or a salt thereof C, containing structural units represented by the following Formula (i) at not less than 90% by mole; the agent satisfying the following Formula (1): (Ac+Bc)×(pH−3)X≥0.38 . . . Formula (1), with the proviso that X=7.2×12(−1.6×(Ac+Bc)).

Description

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

[0001] This application is a U.S. National Phase Application under 35 U.S.C. § 371 of International Patent Application No. PCT / JP2023 / 042641 filed on Nov. 29, 2023, which claims the benefit of priority to Japanese Patent Application No. 2022-198622 filed on Dec. 13, 2022, the contents of all of which are incorporated herein by reference in their entireties. The International Application was published in Japanese on Jun. 20, 2024 as International Publication No. WO / 2024 / 127983 under PCT Article 21 (2).FIELD OF THE INVENTION

[0002] The present invention relates to a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material.BACKGROUND OF THE INVENTION

[0003] Conventionally, treatment liquids for treatment of metal surfaces, which treatment liquids enable application of surface treatment that achieves excellent corrosion resistance and favorable adhesiveness, have been developed. For example, WO 03 / 074761 discloses a surface treatment composition for aluminum, an aluminum alloy, magnesium, or a magnesium alloy, the composition comprising: Compound A, which contains at least one metallic element selected from Hf (IV), Ti (IV), and Zr (IV); a fluorine-containing compound in an amount sufficient to allow the presence, in the composition, of fluorine at least five times the total molar concentration of metals contained in the Compound A; at least one metal ion B, selected from the group of alkaline earth metals; at least one metal ion C, selected from Al, Zn, Mg, Mn, and Cu; and a nitrate ion.PRIOR ART DOCUMENTSPatent Documents[Patent Document 1] WO 03 / 074761Problems to be Solved by the Invention

[0005] However, for the surface treatment, not only adhesiveness and corrosion resistance, but also external appearance as a finishing performance have been considered to be important. Further, in recent years, exposure tests and corrosion tests have been considered to be important in corrosion resistance tests since exposure tests and corrosion tests provide environmental conditions closer to the actual conditions compared to salt spray tests (SST) and the JASO-M609 method, which have been commonly employed. Further, from the viewpoint of reducing the environmental load, lowering of the chemical conversion treatment temperature has also been considered to be important. On the other hand, none of the conventional surface treatment techniques has achieved both the external appearance and the corrosion resistance after chemical conversion treatment.

[0006] An object of the present invention is to provide a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material, which agent achieves excellent external appearance after chemical conversion treatment, as well as excellent corrosion resistance as evaluated by, for example, an exposure test or the VDA621-415 method after painting, and which agent can be used in a wide temperature range.SUMMARY OF THE INVENTIONMeans for Solving the Problems

[0007] In order to solve the above problem, the present inventors intensively studied to discover that a chemical conversion treatment agent comprising: a source of fluorine ions; a source A of ions containing zirconium; a source B of ions containing aluminum; and a specific water-soluble or water-dispersible polymer, or a salt thereof C; the agent satisfying specific parameters, is capable of forming a chemical conversion coating that achieves excellent corrosion resistance, and excellent external appearance after chemical conversion treatment, thereby completing the present invention.

[0008] The present invention includes, for example, the following:

[0009] [1] a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material, the agent comprising:

[0010] a source of fluorine ions;

[0011] a source A of ions containing zirconium;

[0012] a source B of ions containing aluminum; and

[0013] a water-soluble or water-dispersible polymer, or a salt thereof C, containing structural units represented by the following Formula (i):at not less than 90% by mole;

[0015] the agent satisfying the following Formula (1):(A⁢c+Bc) × (pH-3)X≥0.38Formula⁢ (1)with the proviso that X=7.2× 12(−1.6×(Ac+Bc)),

[0017] wherein in the Formula (1),

[0018] Ac is the concentration of zirconium element derived from the Source A in the chemical conversion treatment agent, and is 0.02 g / L to 2 g / L;

[0019] Bc is the concentration of aluminum element derived from the Source B in the chemical conversion treatment agent, and is 0.02 g / L to 2 g / L;

[0020] the ratio of Bc to Ac, Bc / Ac, is 0.03 to 10.0;

[0021] the concentration of the polymer or a salt thereof C, in the chemical conversion treatment agent is 0.0001 g / L to (0.16×Ac+0.23) g / L; and

[0022] pH is the pH of the chemical conversion treatment agent, and is 3.8 to 6.0; and

[0023] [2] the chemical conversion treatment agent according to [1], wherein the metallic material is at least one or more of iron materials, zinc or zinc-based plating materials, aluminum materials, aluminum alloy materials, aluminum-based plating materials, magnesium materials, and magnesium alloy materials.Effect of the Invention

[0024] The present invention can provide a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material, which agent achieves excellent external appearance after chemical conversion treatment, as well as excellent corrosion resistance as evaluated by, for example, an exposure test or the VDA621-415 method after painting, and which agent can be used in a wide temperature range.DETAILED DESCRIPTION OF THE INVENTION

[0025] In the present description, a numerical value range expressed using “to” means the range that includes the numerical values described before and after the “to” as the lower limit value and the upper limit value, respectively, and “A to B” means a value that is not less than A and not more than B.

[0026] A chemical conversion treatment agent according to one embodiment of the present invention is described below.(Chemical Conversion Treatment Agent)

[0027] The chemical conversion treatment agent according to the present embodiment comprises predetermined amounts of: a source of fluorine ions; a source A of ions containing zirconium; a source B of ions containing aluminum; and a water-soluble or water-dispersible polymer, or a salt thereof C, containing structural units represented by Formula (i) at not less than 90% by mole; in an aqueous medium. By using this chemical conversion treatment agent, a chemical conversion coating that achieves excellent corrosion resistance after painting, and excellent external appearance of the coating, can be formed for metallic materials.

[0028] In the chemical conversion treatment agent according to the present embodiment, only the source of fluorine ions; Source A; Source B; and the predetermined polymer or a salt thereof C; may be contained in the aqueous medium, or other components may also be contained therein.(Source of Fluorine Ions)

[0029] The chemical conversion treatment agent according to the present embodiment contains a source of fluorine ions. The source of fluorine ions is not limited as long as it is a compound capable of supplying fluorine ions (hereinafter referred to as “fluorine-containing compound”) when the source is included in the chemical conversion treatment agent. Examples of the fluorine-containing compound include, but are not limited to, zirconium ion hexafluorozirconic acid, hexafluorotitanic acid, hexafluorohafnic acid, hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, germanium fluoride, potassium fluoride, potassium hydrogen fluoride, iron fluoride, hydrofluosilicic acid, sodium fluoride, and sodium hydrogen fluoride. Compounds containing zirconium and fluorine, such as hexafluorozirconic acid, are capable of supplying both zirconium-containing ions and fluorine ions. Only one fluorine-containing compound may be included, or two or more fluorine-containing compounds may be included.

[0030] The amount of the fluorine-containing compound included is not limited as long as the formation of the chemical conversion coating is not affected. Specifically, the fluorine-containing compound is preferably included such that the fluorine ion concentration is the sum of four to eight times the molar concentration of zirconium element contained in the chemical conversion treatment agent and two to four times the molar concentration of aluminum element contained in the chemical conversion treatment agent. By including the fluorine-containing compound within such a range, the free fluorine ion concentration during the treatment becomes appropriate, so that a favorable reaction rate can be achieved between the metallic material and the chemical conversion treatment agent. Thus, a favorable amount of coating can be formed.(Source A)

[0031] Source A is included in the chemical conversion treatment agent according to the present embodiment. Source A is not limited as long as it is a compound capable of supplying ions containing zirconium (hereinafter referred to as “zirconium-containing ions”) when the source is included in the chemical conversion treatment agent. Therefore, the chemical conversion treatment agent according to the present embodiment contains zirconium-containing ions. Examples of the zirconium-containing ions include metal ions of zirconium; complex ions containing zirconium; and oxide ions of zirconium.

[0032] Specific examples of the source A of zirconium-containing ions include hexafluorozirconic acid, zirconium nitrate, zirconyl nitrate, zirconium carbonate, zirconium hydroxide, and zirconium oxide. Only one of these sources may be included, or two or more of these sources may be included.

[0033] The concentration of zirconium-containing ions in the chemical conversion treatment agent is not limited, but the zirconium element concentration Ac derived from Source A, in the chemical conversion treatment agent is usually not less than 0.02 g / L, preferably not less than 0.05 g / L, and is usually not more than 2 g / L, preferably not more than 1.5 g / L. In cases where two or more kinds of Sources A are included in the chemical conversion treatment agent, Ac means the total concentration of zirconium element derived from these.

[0034] In cases where the zirconium element concentration Ac is within the range described above, an effective amount of Zr can be achieved in the chemical conversion coating.(Source B)

[0035] Source B is included in the chemical conversion treatment agent according to the present embodiment. Source B is not limited as long as it is a compound capable of supplying ions containing aluminum (hereinafter referred to as “aluminum-containing ions”) when the source is included in the chemical conversion treatment agent. Therefore, the chemical conversion treatment agent according to the present embodiment contains aluminum-containing ions. Examples of the aluminum-containing ions include metal ions of aluminum; complex ions containing aluminum; and oxide ions of aluminum. Specific examples of the source of aluminum-containing ions, B, include, but are not limited to, aluminum hydroxide, aluminum nitrate, aluminum sulfate, aluminum carbonate, and aluminum oxide. In cases where these may be in the forms of salts, such salts may be used. Only one of these sources may be included, or two or more of these sources may be included.

[0036] The concentration of aluminum-containing ions in the chemical conversion treatment agent is not limited, but the aluminum element concentration Bc derived from Source B, in the chemical conversion treatment agent is usually not less than 0.02 g / L, preferably not less than 0.05 g / L, and is usually not more than 2 g / L, preferably not more than 1.5 g / L. In cases where two or more kinds of sources B are included in the chemical conversion treatment agent, Bc means the total concentration of aluminum element derived from these.

[0037] In cases where the aluminum element concentration Bc is within the range described above, an appropriate free fluorine ion concentration can be achieved in the chemical conversion treatment agent.(Ratio Between Sources A and B)

[0038] The ratio (Bc / Ac) of the aluminum element concentration Bc derived from Source B, to the zirconium element concentration Ac derived from Source A, in the chemical conversion treatment agent is usually not less than 0.03, and usually not more than 10.0.(Water-Soluble or Water-Dispersible Polymer, or Salt Thereof C)

[0039] The chemical conversion treatment agent according to the present embodiment comprises a water-soluble or water-dispersible polymer, or a salt thereof C (hereinafter simply referred to as “Polymer C”). Polymer C is not limited as long as it is a polymer containing structural units represented by the Formula (i) at not less than 90% by mole. Specific examples of Polymer C include polydiallylamines including: diallylamine polymers; and salts of diallylamine polymers such as diallylamine hydrochloride polymers, diallylamine sulfate polymers, and diallylamine acetate polymers.

[0040] The degree of polymerization of Polymer C is not limited. Its weight average molecular weight is usually not less than 1000, preferably not less than 5000. The weight average molecular weight is a value measured by GPC (gel permeation column chromatography) and calculated in terms of polystyrene.

[0041] The content (amount included) of Polymer C in the chemical conversion treatment agent is usually not less than 0.0001 g / L, preferably not less than 0.001 g / L, more preferably not less than 0.005 g / L, and is not more than (0.16×Ac+0.23) g / L, in terms of the solid content.

[0042] In cases where the content of Polymer C is within the range described above, adhesiveness and corrosion resistance of the chemical conversion coating can be improved.(Aqueous Medium)

[0043] The chemical conversion treatment agent according to the present embodiment may contain an aqueous medium. The aqueous medium is not limited as long as it is water, or a mixture of water and a water-miscible organic solvent (in which water is contained at not less than 50% by volume with respect to the volume of the aqueous medium). The water-miscible organic solvent is not limited as long as the solvent is miscible with water, and examples of the solvent include ketone-based solvents such as acetone and methyl ethyl ketone; amide-based solvents such as N,N′-dimethylformamide and dimethylacetamide; alcohol-based solvents such as methanol, ethanol, and isopropanol; ether-based solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone-based solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. One of these water-miscible organic solvents may be mixed with water, or two or more of these may be mixed with water.(Other Components)

[0044] The chemical conversion treatment agent according to the present embodiment may contain, as other components, additives normally used in chemical conversion treatment agents. Examples of the other components include organic acids; oxidizing agents; metal ions other than Sources A and B; organosilane compounds; metal alkoxides; water-soluble resins or water-dispersible resins other than Polymer C; surfactants; and pH-adjusting agents. Only one of these other components may be included, or two or more of these other components may be included. These other components may be included within ranges in which the effect of the present invention is not inhibited.(Organic Acids)

[0045] Examples of organic acids that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, organic sulfonic acids, organic phosphonic acids, organic phosphoric acids, aliphatic carboxylic acids, and aromatic carboxylic acids; specifically, methanesulfonic acid, ethanesulfonic acid, lactic acid, oxalic acid, and citric acid. Only one organic acid may be included, or two or more organic acids may be included.(Oxidizing Agents)

[0046] Examples of oxidizing agents that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, hydrogen peroxide, nitrate, nitrite, permanganate, chlorate, persulfate, nitro-containing compounds, hypochlorous acid, organic peroxide, and bromate; preferably, hydrogen peroxide, nitrate, and nitrite. Only one oxidizing agent may be included, or two or more oxidizing agents may be included. Sulfate ions may or may not be included.(Sources of Metal Ions Other than Sources A and B)

[0047] Examples of sources of metal ions other than Sources A and B that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, compounds containing copper, iron, manganese, magnesium, nickel, cobalt, zinc, tungsten, or the like. Only one source, or two or more sources, of metal ions other than Sources A and B may be included.(Organosilane Compounds)

[0048] Examples of organosilane compounds that may be included in the chemical conversion treatment agent according to the present embodiment include aminosilane compounds, epoxysilane compounds, and alkoxysilane compounds. Specific examples of the organosilane compounds include, but are not limited to, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyldimethylmethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyldiethylethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropylethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, and 3-glycidoxypropyltriethoxysilane. In the chemical conversion treatment agent, each organosilane compound may be present as it is, may be in the form of a hydrolysate derived by hydrolysis of an organosilane compound, may be in the form of a polycondensate derived by polycondensation of the hydrolysate, may be in the form of a copolymer (alternating copolymer, random copolymer, block copolymer, graft copolymer, or the like) derived by copolymerization of individual hydrolysates, or may be a mixture of a plurality of forms.(Metal Alkoxides)

[0049] Examples of metal alkoxides that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, zirconium tetrapropoxide, zirconium tetraisopropoxide, zirconium tetra-normal propoxide, zirconium tetranormal butoxide, titanium methoxide, titanium ethoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, triisopropoxide vanadium (v) oxide, vanadium butoxide, triethoxyvanadium (v) oxide, aluminum isopropoxide, and aluminum-tert-butoxide. One metal alkoxide may be included alone, or two or more metal alkoxides may be included. In the chemical conversion treatment agent, each metal alkoxide may be present as it is, may be in the form of a hydrolysate derived by hydrolysis of a metal alkoxide, may be in the form of a polycondensate derived by polycondensation of the hydrolysate, or of an organosilane compound hydrolysate, may be in the form of a copolymer (alternating copolymer, random copolymer, block copolymer, graft copolymer, or the like) derived by copolymerization of individual hydrolysates or organosilane compound hydrolysates, or may be a mixture of a plurality of forms. Metal alkoxides containing zirconium are also regarded as Source A, and metal alkoxides containing aluminum are also regarded as Source B.(Water-Soluble Resins or Water-Dispersible Resins Other than Polymer C)

[0050] Examples of water-soluble resins or water-dispersible resins other than Polymer C that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, poly(meth)acrylate resins, urethane resins, acrylic resins, epoxy resins, and phenol resins; and amine resins not containing a structural unit represented by Formula (i). One water-soluble resin or water-dispersible resin other than Polymer C may be included alone, or two or more water-soluble resins and / or water-dispersible resins other than Polymer C may be included.(Surfactants)

[0051] Examples of surfactants that may be included in the chemical conversion treatment agent according to the present embodiment include nonionic surfactants; and ionic surfactants such as cationic, anionic, or amphoteric surfactants. Examples of the nonionic surfactants include, but are not limited to, polyethylene glycol-type nonionic surfactants such as polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene-polyoxypropylene-block polymers; polyhydric alcohol-type nonionic surfactants such as sorbitan fatty acid esters; and amide-type nonionic surfactants such as fatty acid alkylolamides. Examples of the cationic surfactants include, but are not limited to, amine salt-type cationic surfactants such as higher alkyl amine salts and polyoxyethylene higher alkyl amines; and quaternary ammonium salt-type cationic surfactants such as alkyltrimethylammonium salts. Examples of the anionic surfactants include, but are not limited to, higher alkyl ether sulfuric acid ester salts to which ethylene oxide is added. The HLB value (as calculated by the Griffin's method) of the surfactants is not limited, and is preferably 6 to 18, more preferably 10 to 14. One of the surfactants may be included alone, or two or more of the above surfactants may be included, in the chemical conversion treatment agent of the present embodiment. By including the above surfactant(s) in the chemical conversion treatment agent of the present embodiment, chemical conversion treatment and degreasing treatment can be carried out at the same time in one step.(pH of Chemical Conversion Treatment Agent)

[0052] The pH of the chemical conversion treatment agent according to the present embodiment is usually in the acidic to neutral range. Specifically, the pH is within the range of 3.8 to 6.0, more preferably within the range of 4.1 to 5.1.

[0053] The pH value in the present description means a value measured at 40° C. using a pH meter.

[0054] The pH of the chemical conversion treatment agent may be adjusted using a pH-adjusting agent, such as an acid component, for example, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, or an organic acid; or an alkaline component, for example, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, an alkali metal salt, ammonia, an ammonium salt, or an amine. However, the components are not limited to these. One pH-adjusting agent, or two or more pH-adjusting agents may be used.(Values of Specific Parameters)

[0055] The value of the left-hand side of the following Formula (1) is usually 0.38 to 10, preferably 0.8 to 5. The effect of the present invention is produced by satisfying Formula (1).(A⁢c+Bc) × (pH-3)X≥0.38Formula⁢ (1)with the proviso that X=7.2× 12(−1.6×(Ac+Bc)).(Method of Producing Chemical Conversion Treatment Agent)The chemical conversion treatment agent according to the present embodiment can be produced by including predetermined amounts of a source of fluorine ions; Source A; Source B; and a predetermined polymer or a salt thereof C, as raw materials in an aqueous medium.(Method of Forming Chemical Conversion Coating)

[0057] A method of forming a chemical conversion coating using the chemical conversion treatment agent according to the present embodiment comprises a contact step of bringing the chemical conversion treatment agent according to the present embodiment into contact on or over a surface of a metallic material. By this, a chemical conversion coating is formed on or over the surface of the metallic material. Examples of the method of bringing the chemical conversion treatment agent into contact with the metallic material include, but are not limited to, conventional contact methods such as treatment methods including the immersion treatment method, the spray treatment method, the pouring treatment method, and combinations thereof.

[0058] The contact temperature in the above contact method is preferably within the range of 10° C. to 60° C., more preferably within the range of 20° C. to 50° C. In the present embodiment, the range of from 10° C. to 25° C. is regarded as “low temperature”, and the range of from more than 25° C. to not more than 50° C. is regarded as “high temperature”. The contact time is preferably within the range of 30 seconds to 300 seconds, more preferably within the range of 60 seconds to 180 seconds. However, the contact time is not limited thereto.

[0059] Further, a pretreatment step may be carried out before the step of contacting the chemical conversion treatment agent. Examples of the pretreatment step include an acid pickling step; a degreasing step; an alkali washing step; a chromate chemical conversion treatment step; a phosphate chemical conversion treatment step using a phosphate such as zinc phosphate or iron phosphate; a bismuth displacement plating step; a zirconium chemical conversion treatment step; a titanium chemical conversion treatment step; a hafnium chemical conversion treatment step; and a vanadium chemical conversion treatment step. One of these pretreatment steps may be carried out, or two or more of these pretreatment steps may be carried out sequentially in combination. Examples of the combination of two or more steps include the combination of a phosphate chemical conversion treatment step with a chromate chemical conversion treatment step, a bismuth displacement plating step, a zirconium chemical conversion treatment step, a titanium chemical conversion treatment step, a hafnium chemical conversion treatment step, or a vanadium chemical conversion treatment step. In the zirconium chemical conversion treatment step performed as a pretreatment step, the chemical conversion treatment agent according to the present embodiment may be used, or a chemical conversion treatment agent different from the chemical conversion treatment agent according to the present embodiment may be used. In cases where a pretreatment step(s) described above is / are carried out, a water washing treatment step may be carried out after the pretreatment step(s). In cases where a plurality of pretreatment steps is carried out, a water washing treatment step may be carried out after each step, or after some of the steps. In cases where the water washing treatment step is carried out, a drying step of drying the surface of the metallic material may be carried out thereafter.

[0060] In the method of forming a chemical conversion coating according to the present embodiment, the contact step may be followed by a post-treatment step such as an alkali washing step, a water washing step, chromate chemical conversion treatment, a zinc phosphate chemical conversion treatment step, a bismuth displacement plating step, an iron phosphate chemical conversion treatment step, a zirconium chemical conversion treatment step, a titanium chemical conversion treatment step, a hafnium chemical conversion treatment step, or a drying step. One of these post-treatment steps may be carried out alone, or two or more of these steps may be carried out sequentially in combination. In the zirconium chemical conversion treatment step performed as a post-treatment step, the chemical conversion treatment agent according to the present embodiment may be used, or a chemical conversion treatment agent different from the chemical conversion treatment agent according to the present embodiment may be used. In cases where a post-treatment step(s) described above is / are carried out, a water washing treatment step(s) may be carried out after the post-treatment step(s). In cases where a plurality of post-treatment steps is carried out, a water washing treatment step may be carried out after each step, or after some of the steps. In cases where the washing treatment step is carried out, a drying step of drying the surface of the metallic material may be carried out thereafter.

[0061] Further, a paint may be formed on a chemical conversion coating formed by the method of forming a chemical conversion coating described above, to produce a painted metallic material having the chemical conversion coating and the paint. In this case, the formation of the chemical conversion coating may be followed by a paint formation treatment for forming the paint, such as a painting step and a drying step of drying the paint material on the surface of the metallic material after the painting (which may include, for example, a baking step and a curing step).

[0062] Before the painting step, a water washing step may be carried out to wash, with water, the surface of the metallic material with which the chemical conversion treatment agent according to the present embodiment has been brought into contact. Further, a drying step of drying the surface of the metallic material with which the chemical conversion treatment agent has been brought into contact, or a drying step of drying the surface of the metallic material that has been subjected to the water washing treatment step, may be carried out. Further, one of, or two or more of the above post-treatment steps may be carried out after the contact step but before the painting step. In cases where a post-treatment step(s) described above is / are carried out, a water washing treatment step(s) may be carried out after the post-treatment step(s). In cases where a plurality of post-treatment steps is carried out, a water washing treatment step may be carried out after each step, or after some of the steps. In cases where the washing treatment step is carried out, a drying step of drying the surface of the metallic material may be carried out thereafter.

[0063] The painting step is carried out using a paint material, for the surface of the metallic material having the chemical conversion coating. The painting method is not limited, and a conventionally known method may be applied. Examples of the conventionally known method include roll painting, electrodeposition painting (for example, cationic electrodeposition painting and anionic electrodeposition painting), spray painting, hot spray painting, airless spray painting, electrostatic (powder) painting, roller coating, curtain flow coating, brush painting, bar coating, and the fluidized bed painting method.

[0064] Examples of the paint material include known paint materials such as oil-based paint materials, cellulose derivative paint materials, phenol resin paint materials, alkyd resin paint materials, amino-alkyd resin paint materials, urea resin paint materials, unsaturated resin paint materials, vinyl resin paint materials, acrylic resin paint materials, epoxy resin paint materials, polyurethane resin paint materials, silicone resin paint materials, fluorine resin paint materials, anticorrosive paints, antifouling paint materials, powder paint materials, cationic electrodeposition paint materials, anionic electrodeposition paint materials, aqueous paint materials, and solvent paint materials. In the painting step, a single paint may be formed, or two or more paints may be formed using the same or different paint material(s). The drying step is a step of drying the paint material after painting, to cure the paint material. Examples of the drying method include air drying, vacuum drying, convective heat drying (for example, natural convective heat drying or forced convective heat drying), radiation drying (for example, near-infrared drying or far-infrared drying), ultraviolet dry-curing, electron beam dry-curing, Vapocure, and bake drying. One of these drying methods may be carried out, or two or more of these drying methods may be carried out in combination.

[0065] As the cationic electrodeposition paint, a known method may be applied. Examples of the method include a method using a cationic electrodeposition paint material containing: an amine-added epoxy resin as a paint material; and a blocked polyisocyanate curing agent as a curing component; wherein the metallic material having the chemical conversion coating is immersed in this paint material. The cationic electrodeposition painting is carried out, for example, by application of a voltage using a rectifier, and using the metallic material having the chemical conversion coating as a cathode, while the paint material is kept at a predetermined temperature under stirring. For the metallic material that has been subjected to the cationic electrodeposition painting in this manner, water washing and baking may be carried out to form a paint on the chemical conversion coating. The baking is carried out within a predetermined temperature range for a predetermined length of time. For example, in one mode, the baking is carried out at 170° C. for 20 minutes. In cases where the cationic electrodeposition painting method using a cationic electrodeposition paint material is applied, the water washing treatment step is preferably carried out before the painting step, using water whose sodium ion concentration is less than 500 ppm by mass, in order to prevent aggregation of the paint material due to sodium ions.

[0066] In cases where a powder paint material is used, a known method may be applied as a painting method such as spray painting, electrostatic powder painting, or the fluidized bed painting method. Examples of the powder paint material include a material containing: a polyester resin; and a blocked polyisocyanate curing agent, a β-hydroxyalkylamide curing agent (see, for example, JP 2011-88083 A), or triglycidyl isocyanurate as a curing agent. The baking is carried out within a predetermined temperature range for a predetermined length of time. For example, in one mode, the baking is carried out at 130° C. to 250° C. for 20 minutes.

[0067] In cases where the solvent paint material is used, a known method may be applied as a painting method such as spray painting, electrostatic painting, or bar coating. Examples of the solvent paint material include a material containing: a resin such as a melamine resin, an acrylic resin, a urethane resin, or a polyester resin; and an organic solvent such as a thinner. The baking is carried out within a predetermined temperature range for a predetermined length of time. For example, in one mode, the baking is carried out at 130° C. for 20 minutes.

[0068] Examples of the drying method for curing the paint material after painting include air drying, vacuum drying, convective heat drying (for example, natural convective heat drying or forced convective heat drying), radiation drying (for example, near-infrared drying or far-infrared drying), ultraviolet dry-curing, electron beam dry-curing, and Vapocure. One of these drying methods may be carried out, or two or more of these drying methods may be carried out in combination.

[0069] The paint obtained by the painting step may have a single layer or a plurality of layers. In cases where the paint has a plurality of layers, the paint materials for forming the paints, the painting methods using the paint materials, the drying methods for the metallic material after painting, and the like may each be the same or different.

[0070] Examples of the metallic material include iron (for example, cold-rolled steel sheets, hot-rolled steel sheets, high-tensile steel sheets, tool steels, alloy tool steels, spheroidal graphite cast irons, and gray cast iron); plated materials such as zinc and zinc-based plated materials (for example, zinc electroplated materials, zinc hot-dipped materials, zinc-aluminum-based hot-dipped materials, zinc-aluminum-magnesium-based hot-dipped materials, alloyed zinc hot-dipped materials, and zinc-based electroplated materials); aluminum and aluminum alloy materials (for example, 1000 series aluminum alloy materials, 2000 series aluminum alloy materials, 3000 series aluminum alloy materials, 4000 series aluminum alloy materials, 5000 series aluminum alloy materials, 6000 series aluminum alloy materials, 7000 series aluminum alloy materials, 8000 series aluminum alloy materials, aluminum casts, aluminum alloy casts, and die-cast materials); aluminum-based plated materials; and magnesium and magnesium alloy materials (for example, AZ91 and AZ61AZ31).

[0071] In the chemical conversion coating formed using the chemical conversion treatment agent according to the present embodiment, the total mass of titanium, zirconium, and hafnium contained is preferably not less than 5 mg / m2, more preferably not less than 10 mg / m2, still more preferably not less than 20 mg / m2 per unit area. Although there is no upper limit value, the total mass is preferably not more than 800 mg / m2. The mass of titanium, zirconium, and hafnium in this chemical conversion coating may be measured, for example, using an X-ray fluorescence analyzer.

[0072] The metallic material having the chemical conversion coating may have one of, or two or more of the above-described various coatings (for example, a chromate chemical conversion coating, a phosphate chemical conversion coating, or a bismuth displacement plating coating) on either side of the chemical conversion coating obtained by bringing the chemical conversion treatment agent according to the present embodiment into contact.

[0073] By painting the surface of a metallic material having a chemical conversion coating using a paint material, a paint can be formed to produce a painted metallic material having the chemical conversion coating and the paint. The painted metallic material may have the paint on the surface of the metallic material having the chemical conversion coating, or may have the paint on the surface of one or more of the above-described various coatings (for example, a chromate chemical conversion coating, a phosphate chemical conversion coating, a bismuth displacement plating coating, or a vanadium chemical conversion coating) additionally formed on the chemical conversion coating. The paint may have a single layer, or may have two or more layers. The thickness of the paint is not limited, and is set appropriately according to the use of the painted metallic material.EXAMPLES

[0074] The effects of the present invention are described below in detail by way of Examples. However, the present invention is not limited by the following Examples.<Metallic Materials>

[0075] As metallic materials, a cold-rolled mild steel sheet compatible with the JIS G3141:2011 standard (SPCC: thickness, 0.8 mm), an alloyed zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (GA: thickness, 0.8 mm), an aluminum alloy sheet compatible with the JIS H4000:2014 standard (A6061: thickness, 0.8 mm), a zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (SGCC: thickness, 0.8 mm), a magnesium alloy sheet compatible with the JIS H4201:2018 standard (MP-AZ31B: thickness, 0.8 mm), and a zinc-aluminum-magnesium-based hot-dipped material (ZM40 / 40: thickness, 0.8 mm) were used after cutting each of these to a size of 70 mm (length)×150 mm (width).<Components Used in Preparation of Chemical Conversion Treatment Agents>

[0076] Chemical conversion treatment agents were prepared using the following raw materials.(Source A)A1: Hexafluorozirconic acid

[0078] A2: Zirconium nitrate

[0079] A3: Zirconium hydroxide(Source B)B1: Aluminum nitrate

[0081] B2: Aluminum hydroxide(Polymer C)C1: Diallylamine polymer (PAS-21; Nittobo Medical Co., Ltd.; content ratio of Formula (i), 100%)

[0083] C2: Diallylamine hydrochloride polymer (PAS-21CL; Nittobo Medical Co., Ltd.; content ratio of Formula (i), 100%)

[0084] C3: Allylamine hydrochloride-diallylamine hydrochloride polymer (PAA-D11-HCL; Nittobo Medical Co., Ltd.; content ratio of Formula (i), 50%)

[0085] Hydrofluoric acid was used as a source of fluorine ions.

[0086] In addition, the following raw materials were used as other additives.(Organic Acid D)D1: Methanesulfonic acid

[0088] D2: Ethanesulfonic acid

[0089] D3: Succinic acid

[0090] D4: Citric acid(Oxidizing Agent E)E1: Nitric acid(Metals Other than Sources A and B (Metal F))

[0092] F1: Ferric sulfate

[0093] F2: Iron (III) nitrate

[0094] F3: Copper nitrate(Organosilane Compound G)G1:3-Aminopropyldimethylmethoxysilane

[0096] G2:3-Aminopropylmethyldimethoxysilane

[0097] G3:3-Aminopropyldiethylethoxysilane

[0098] G4:3-Aminopropylethyldiethoxysilane

[0099] G5:3-Aminopropyltriethoxysilane

[0100] G6:3-Aminopropyltrimethoxysilane

[0101] G7:3-Glycidoxypropyltrimethoxysilane

[0102] G8: Ethyltrimethoxysilane

[0103] G9: Ureidopropyltriethoxysilane

[0104] G10: Isocyanate propyltriethoxysilane(Metal Alkoxide H)H1: Titanium methoxide

[0106] H2: Vanadium propoxide

[0107] H3: Zirconium tetranormal propoxide

[0108] H4: Aluminum isopropoxide

[0109] H5: Vinyltrimethoxysilane(Other Components)I1: Hydroxylamine sulfate

[0111] I2: Ascorbic acid<Preparation of Chemical Conversion Treatment Agents>

[0112] As shown in Tables 1 and 2, predetermined amounts of the components were added, and then the pH was adjusted to a predetermined value with sodium hydroxide, to prepare chemical conversion treatment agents of Examples 1 to 48 and Comparative Examples 1 to 24.<Production of Metallic Materials Having Chemical Conversion Coating>

[0113] A degreasing agent (FC-E2093; Nihon Parkerizing Co., Ltd.; an aqueous solution in which Agent A and Agent B were dissolved at concentrations of 13 g / L and 11 g / L, respectively) was sprayed onto the surface of each metallic material at 43° C. for 120 seconds, to perform degreasing. Thereafter, the material was subjected to spray water washing at 25° C. for 30 seconds. Subsequently, the metallic material, which had been subjected to the degreasing and then the spray water washing, was immersed in various chemical conversion treatment agents (the chemical conversion treatment agents of Examples 1 to 48 and Comparative Examples 1 to 24) at 15° C. (low temperature) or 38° C. (high temperature) for 120 seconds, to form a chemical conversion coating on the surface of each metallic material. The surface of the resulting metallic material having the chemical conversion coating was washed at 25° C. with tap water, and then with deionized water. After the washing with water, a test piece for evaluation of the external appearance was dried at 40° C. for 10 minutes. A test piece for the corrosion resistance after painting was not dried before it was subjected to the painting described below.TABLE 1Chemical Conversion AgentFluorinePolymer (C)Other AdditiveConcen-Source (A)Source (B)Concen-Concen-trationAcBctration0.16*Ac +trationFormula[g / L]Material[g / L]Material[g / L]Bc / AcMaterial[g / L]0.23Material[g / L]pH(1)Example 10.46A10.20B10.100.50C20.20000.2620——4.20.45Example 20.46A10.20B10.100.50C20.20000.2620——4.20.45Example 30.46A10.20B10.100.50C20.20000.2620——4.20.45Example 40.46A20.20B20.100.50C10.20000.2620——4.20.45Example 50.46A30.20B20.100.50C20.20000.2620——4.20.45Example 60.45A30.02B20.2010.00C20.20000.2332——4.20.38Example 70.55A30.10B20.202.00C20.20000.2460——4.20.45Example 81.05A30.50B20.200.40C20.20000.3100——4.20.76Example 91.67A31.00B20.200.20C20.20000.3900——4.21.21Example 102.92A32.00B20.200.10C20.20000.5500——4.22.20Example 110.67A30.50B20.020.04C20.20000.3100——4.20.61Example 120.84A30.50B20.100.20C20.20000.3100——4.20.68Example 131.18A30.10B20.505.00C20.20000.2460——4.20.68Example 142.24A30.10B21.0010.00C20.20000.2460——4.21.12Example 154.48A30.20B22.0010.00C20.20000.2620——4.22.20Example 161.31A30.20B20.502.50C20.20000.2620——3.80.63Example 171.31A30.20B20.502.50C20.20000.2620——4.00.70Example 181.31A30.20B20.502.50C20.20000.2620——4.10.73Example 191.31A30.20B20.502.50C20.20000.2620——4.50.84Example 201.31A30.20B20.502.50C20.20000.2620——5.00.95Example 211.31A30.20B20.502.50C20.20000.2620——6.01.14Example 220.55A30.10B20.202.00C20.00010.2460——4.20.45Example 230.55A30.10B20.202.00C20.01000.2460——4.20.45Example 240.55A30.10B20.202.00C20.10000.2460——4.20.45Example 250.80A30.30B20.200.67C20.25000.2780——4.20.60Example 261.67A31.00B20.200.20C20.35000.3900——4.21.21Example 272.92A32.00B20.200.10C20.50000.5500——4.22.20Example 282.61A10.40B11.002.50C20.20000.2940D11.004.21.41Example 291.18A10.10B10.505.00C20.20000.2460D21.004.20.68Example 303.36A31.00B21.001.00C20.20000.3900F11.004.22.00Example 313.13A32.00B20.300.15C20.20000.5500F21.004.22.30Example 322.61A10.40B11.002.50C20.20000.2940F30.054.21.41Example 331.18A10.10B10.505.00C20.20000.2460G11.004.20.68Example 343.36A11.00B11.001.00C20.20000.3900G21.004.22.00Example 353.13A12.00B10.300.15C20.20000.5500G31.004.22.30Example 362.61A10.40B11.002.50C20.20000.2940G41.004.21.41Example 371.18A30.10B20.505.00C20.20000.2460G51.004.20.68Example 383.36A31.00B21.001.00C20.20000.3900G61.004.22.00TABLE 2Chemical Conversion AgentFluorinePolymer (C)Other AdditiveConcen-Source (A)Source (B)Concen-Concen-trationAcBctration0.16*Ac +trationFormula[g / L]Material[g / L]Materialg / L]Bc / AcMaterial[g / L]0.23Material[g / L]pH(1)Example 393.13A12.00B10.300.15C20.20000.5500E11.004.22.30Example 400.92A10.40B10.200.50C20.20000.2940H11.004.20.68Example 410.67A10.20B10.201.00C20.20000.2620H21.004.20.52Example 422.28A10.70B10.500.71C20.20000.3420H31.004.21.48Example 431.95A31.00B20.200.20C20.20000.3900H41.004.21.34Example 442.92A12.00B10.200.10C20.20000.5500G52.004.22.20H12.00Example 450.92A10.40B10.200.50C20.20000.2940G52.004.20.68H22.00Example 462.63A10.70B10.500.71C20.20000.3420G52.004.21.76H32.00Example 472.23A11.00B10.200.20C20.20000.3900G52.004.21.47H42.00Example 482.92A12.00B10.200.10C20.20000.5500G52.004.22.20G72.00Comparative0.62A20.50———C20.20000.3100——4.00.50Example 1Comparative4.23——B12.00—C20.20000.2300——4.02.00Example 2Comparative13.06A12.00B15.002.50C20.20000.5500——3.97.00Example 3Comparative10.47A15.00B12.000.40C20.20001.0300——3.97.00Example 4Comparative2.54A12.00B10.020.01C20.20000.5500——4.02.02Example 5Comparative0.49A10.02B10.2211.00C20.20000.2332——4.00.24Example 6Comparative1.12A10.05B10.5010.00——0.2380——4.00.55Example 7Comparative3.92A10.60B21.502.50C30.02000.3260——4.02.10Example 8Comparative3.92A10.60B21.502.50C20.40000.3260——4.02.10Example 9Comparative1.52A10.20B10.603.00——0.2620I10.054.00.80Example 10Comparative1.94A10.20B10.804.00——0.2620I20.104.01.00Example 11Comparative2.36A10.20B11.005.00——0.2620D40.304.01.20Example 12Comparative3.36A11.00B11.001.00——0.3900F10.024.02.00Example 13Comparative23.63A12.00B110.005.00——0.5500F20.504.012.00Example 14Comparative2.52A11.00B10.600.60——0.3900D31.004.01.60Example 15Comparative1.88A11.00B10.300.30——0.3900H50.604.01.30Example 16Comparative17.29A12.00B17.003.50——0.5500G62.004.09.00Example 17Comparative2.31A11.00B10.500.50——0.3900G70.204.01.50Example 18Comparative1.88A11.00B10.300.30——0.3900G81.504.01.30Example 19Comparative4.19A12.00B10.800.40——0.5500G90.054.02.80Example 20Comparative3.36A11.00B11.001.00——0.3900G101.004.02.00Example 21Comparative3.36A11.00B11.001.00——0.3900G101.003.52.00Example 22Comparative0.42A30.08B10.151.88C20.20000.2428——3.20.00Example 23Comparative0.49A30.35B20.0250.07C20.20000.2860——4.00.375Example 24<Measurement of Amount of Zirconium Element in Chemical Conversion Coating (Amount of Deposited Zr)>The amount of zirconium element in the chemical conversion coating formed on the surface of the metallic material was determined as the amount of deposited Zr, using X-ray fluorescence (a scanning X-ray fluorescence analyzer: ZSX Primus II, manufactured by Rigaku Corporation).<Production of Metallic Materials Having Paint>

[0115] The chemical conversion coating formed on the surface of each metallic material was painted, and then baking was carried out to prepare a metallic material having a paint. Details of the painting method, and the baking conditions are described below.(Cationic Electrodeposition Painting)

[0116] A painting was formed by electrolysis using, as a cathode, a metallic material having each type of chemical conversion coating, and using a cationic electrodeposition paint material (GT-100V; manufactured by Kansai Paint Co., Ltd.). The electrolysis was carried out at an applied voltage of 180 V and a temperature of 30.0±0.5° C. In the electrolysis, the quantity of electricity was adjusted to achieve a paint thickness of 15.0±1.0 μm. After the cationic electrodeposition, the surface of the paint was washed with deionized water, and baking was carried out at 170° C. for 26 minutes, to prepare a metallic material (each test piece) having the paint.<External Appearance of Chemical Conversion Coating>

[0117] For the test piece having a chemical conversion coating obtained in each of Examples and Comparative Examples, the external appearance of the coating was rated by visual observation.<Evaluation Criteria>

[0118] A: Unevenness was found neither on the planar section nor the edges when the test piece was viewed from the front side. Unevenness was found neither on the planar section nor the edges when the test piece was viewed at an angle of 20° with respect to the front side.

[0119] B: Unevenness was found neither on the planar section nor the edges when the test piece was viewed from the front side. Unevenness was found on the planar section and the edges when the test piece was viewed at an angle of 20° with respect to the front side.

[0120] C: Unevenness was not found on the planar section, but was found on the edges when the test piece was viewed from the front side. Unevenness was found on the planar section and the edges when the test piece was viewed at an angle of 20° with respect to the front side.

[0121] D: Unevenness was found on the planar section and the edges when the test piece was viewed from the front side. Unevenness was found on the planar section and the edges when the test piece was viewed at an angle of 20° with respect to the front side.<Corrosion Resistance Test (Exposure Test)>

[0122] Using a cutter knife, an X-shaped scratch (cross-cut) was made on the painted surface of each test piece having a paint, such that the scratch reached the metal substrate. The test piece was then placed near the sea in Okinawa to perform the exposure for 2 years. Thereafter, the blister width (the maximum blister width on one side) of the paint from the scratched portion (cross-cut portion) on the test piece was measured. Corrosion resistance was evaluated according to the following evaluation criteria<Evaluation Criteria—Cross-Cut Portion>A: The blister width on one side was less than 5.0 mm.

[0124] B: The blister width on one side was not less than 5.0 mm, and less than 10.0 mm.

[0125] C: The blister width on one side was not less than 10.0 mm, and less than 15.0 mm.

[0126] D: The blister width on one side was not less than 15.0 mm.<Corrosion Resistance Test (VDA Method)>

[0127] Using a cutter knife, a single scratch was made at the center of the painted surface of each test piece having a paint, such that the scratch reached the metal substrate. Thereafter, six cycles of a corrosion cycle test were carried out using the VDA test according to 621-415 and DIN EN ISO 20567-1 (1982 version; method C).

[0128] The blister width (the maximum blister width on one side) of the paint from the scratched portion (cut portion) on the test piece was measured. Corrosion resistance was evaluated according to the following evaluation criteria.<Evaluation Criteria-Cut Portion>A: The blister width on one side was less than 5.0 mm.

[0130] B: The blister width on one side was not less than 5.0 mm, and less than 10.0 mm.

[0131] C: The blister width on one side was not less than 10.0 mm, and less than 15.0 mm.

[0132] D: The blister width on one side was not less than 15.0 mm.

[0133] The results of the evaluation tests are shown in Tables 3 to 6. In all evaluations, test pieces with rank A or B were judged as acceptable.TABLE 3SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBBBExample 2BBBBBBBBBBExample 3BBBBBBBBBBExample 4BBBBBBBBBBExample 5BBBBBBBBBBExample 6BBBBBBBBBBExample 7BBBBBBBBBBExample 8BBBBBBBBBBExample 9ABBABBABBAExample 10ABBABBABBAExample 11BBBBBBBBBBExample 12BBBBBBBBBBExample 13BBBBBBBBBBExample 14BBBABBBBBAExample 15ABBABBABBAExample 16BBBBBBBBBBExample 17BBBBBBBBBBExample 18BBBBBBBBBBExample 19BBBABBBBBAExample 20BBBABBBBBAExample 21BBBABBBBBAExample 22BBBBBBBBBBExample 23BBBBBBBBBBExample 24BBBBBBBBBBExample 25BBBBBBBBBBExample 26BBBABABBBAExample 27BBBABABBBAExample 28ABBABAABBAExample 29BBBABBBBBAExample 30ABBABAABBAExample 31ABBABAABBAExample 32ABBABAABBAExample 33BBBABBBBBAExample 34ABBABAABBAExample 35ABBABAABBAExample 36ABBABAABBAExample 37BBBABBBBBAExample 38ABBABAABBAGAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBExample 2BBBBBBBBExample 3BBBBBBBBExample 4BBBBBBBBExample 5BBBBBBBBExample 6BBBBBBBBExample 7BBBBBBBBExample 8BBBBBBBBExample 9BBABBABBExample 10BBABBABBExample 11BBBBBBBBExample 12BBBBBBBBExample 13BBBBBBBBExample 14BBBBBABBExample 15BBABBABBExample 16BBBBBBBBExample 17BBBBBBBBExample 18BBBBBBBBExample 19BBBBBABBExample 20BBBBBABBExample 21BBBBBABBExample 22BBBBBBBBExample 23BBBBBBBBExample 24BBBBBBBBExample 25BBBBBBBBExample 26BABBBABAExample 27BABBBABAExample 28BAABBABAExample 29BBBBBABBExample 30BAABBABAExample 31BAABBABAExample 32BAABBABAExample 33BBBBBABBExample 34BAABBABAExample 35BAABBABAExample 36BAABBABAExample 37BBBBBABBExample 38BAABBABATABLE 4SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.TempTemp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBBBExample 2BBBBBBBBBBExample 3BBBBBBBBBBExample 4BBBBBBBBBBExample 5BBBBBBBBBBExample 6BBBBBBBBBBExample 7BBBBBBBBBBExample 8BBBBBBBBBBExample 9ABBABBABBAExample 10ABBABBABBAExample 11BBBBBBBBBBExample 12BBBBBBBBBBExample 13BBBBBBBBBBExample 14BBBABBBBBAExample 15ABBABBABBAExample 16BBBBBBBBBBExample 17BBBBBBBBBBExample 18BBBBBBBBBBExample 19BBBABBBBBAExample 20BBBABBBBBAExample 21BBBABBBBBAExample 22BBBBBBBBBBExample 23BBBBBBBBBBExample 24BBBBBBBBBBExample 25BBBBBBBBBBExample 26BBBABABBBAExample 27BBBABABBBAExample 28ABBABAABBAExample 29BBBABBBBBAExample 30ABBABAABBAExample 31ABBABAABBAExample 32ABBABAABBAExample 33BBBABBBBBAExample 34ABBABAABBAExample 35ABBABAABBAExample 36ABBABAABBAExample 37BBBABBBBBAExample 38ABBABAABBAGAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBExample 2BBBBBBBBExample 3BBBBBBBBExample 4BBBBBBBBExample 5BBBBBBBBExample 6BBBBBBBBExample 7BBBBBBBBExample 8BBBBBBBBExample 9BBABBABBExample 10BBABBABBExample 11BBBBBBBBExample 12BBBBBBBBExample 13BBBBBBBBExample 14BBBBBABBExample 15BBABBABBExample 16BBBBBBBBExample 17BBBBBBBBExample 18BBBBBBBBExample 19BBBBBABBExample 20BBBBBABBExample 21BBBBBABBExample 22BBBBBBBBExample 23BBBBBBBBExample 24BBBBBBBBExample 25BBBBBBBBExample 26BABBBABAExample 27BABBBABAExample 28BAABBABAExample 29BBBBBABBExample 30BAABBABAExample 31BAABBABAExample 32BAABBABAExample 33BBBBBABBExample 34BAABBABAExample 35BAABBABAExample 36BAABBABAExample 37BBBBBABBExample 38BAABBABATABLE 5SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 39ABBABAABBAExample 40BBBABBBBBAExample 41BBBABBBBBAExample 42ABBABAABBAExample 43ABBABAABBAExample 44ABBABAABBAExample 45BBBABBBBBAExample 46ABBABAABBAExample 47ABBABAABBAExample 48ABBABAABBAComparativeCDDDDDCDDDExample 1ComparativeDDDDDDDDDDExample 2ComparativeDDDCDCDDDCExample 3ComparativeDDDCDCDDDCExample 4ComparativeDDDCDCDDDCExample 5ComparativeDDDCDCDDDCExample 6ComparativeDDDCDCDDDCExample 7ComparativeCCCCCCCCCCExample 8ComparativeCCCCCCCCCCExample 9ComparativeCCCCCCCCCCExample 10ComparativeCCCCCCCCCCExample 11ComparativeCCCCCCCCCCExample 12ComparativeCCCCCCCCCCExample 13ComparativeCCCCCCCCCCExample 14ComparativeCCCCCCCCCCExample 15ComparativeCCCCCCCCCCExample 16ComparativeCCCCCCCCCCExample 17ComparativeCCCCCCCCCCExample 18ComparativeCCCCCCCCCCExample 19ComparativeCCCCCCCCCCExample 20ComparativeCCCCCCCCCCExample 21ComparativeCCCCCCCCCCExample 22ComparativeDDDCDCDDDCExample 23ComparativeCDCDCDCDCDExample 24GAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 39BAABBABAExample 40BBBBBABBExample 41BBBBBABBExample 42BAABBABAExample 43BAABBABAExample 44BAABBABAExample 45BBBBBABBExample 46BAABBABAExample 47BAABBABAExample 48BAABBABAComparativeDDCDDDDDExample 1ComparativeDDDDDDDDExample 2ComparativeDCDDDCDCExample 3ComparativeDCDDDCDCExample 4ComparativeDCDDDCDCExample 5ComparativeDCDDDCDCExample 6ComparativeDCDDDCDCExample 7ComparativeCCCCCCCCExample 8ComparativeCCCCCCCCExample 9ComparativeCCCCCCCCExample 10ComparativeCCCCCCCCExample 11ComparativeCCCCCCCCExample 12ComparativeCCCCCCCCExample 13ComparativeCCCCCCCCExample 14ComparativeCCCCCCCCExample 15ComparativeCCCCCCCCExample 16ComparativeCCCCCCCCExample 17ComparativeCCCCCCCCExample 18ComparativeCCCCCCCCExample 19ComparativeCCCCCCCCExample 20ComparativeCCCCCCCCExample 21ComparativeCCCCCCCCExample 22ComparativeDCDDDCDCExample 23ComparativeCDCDCDCDExample 24TABLE 6SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 39ABBABAABBAExample 40BBBABBBBBAExample 41BBBABBBBBAExample 42ABBABAABBAExample 43ABBABAABBAExample 44ABBABAABBAExample 45BBBABBBBBAExample 46ABBABAABBAExample 47ABBABAABBAExample 48ABBABAABBAComparativeCDDDDDCDDDExample 1ComparativeDDDDDDDDDDExample 2ComparativeDDDCDCDDDCExample 3ComparativeDDDCDCDDDCExample 4ComparativeDDDCDCDDDCExample 5ComparativeDDDCDCDDDCExample 6ComparativeDDDCDCDDDCExample 7ComparativeCCCCCCCCCCExample 8ComparativeCCCCCCCCCCExample 9ComparativeCCCCCCCCCCExample 10ComparativeCCCCCCCCCCExample 11ComparativeCCCCCCCCCCExample 12ComparativeCCCCCCCCCCExample 13ComparativeCCCCCCCCCCExample 14ComparativeCCCCCCCCCCExample 15ComparativeCCCCCCCCCCExample 16ComparativeCCCCCCCCCCExample 17ComparativeCCCCCCCCCCExample 18ComparativeCCCCCCCCCCExample 19ComparativeCCCCCCCCCCExample 20ComparativeCCCCCCCCCCExample 21ComparativeCCCCCCCCCCExample 22ComparativeDDDCDCDDDCExample 23ComparativeCDCDCDCDCDExample 24GAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.TempExample 39BAABBABAExample 40BBBBBABBExample 41BBBBBABBExample 42BAABBABAExample 43BAABBABAExample 44BAABBABAExample 45BBBBBABBExample 46BAABBABAExample 47BAABBABAExample 48BAABBABAComparativeDDCDDDDDExample 1ComparativeDDDDDDDDExample 2ComparativeDCDDDCDCExample 3ComparativeDCDDDCDCExample 4ComparativeDCDDDCDCExample 5ComparativeDCDDDCDCExample 6ComparativeDCDDDCDCExample 7ComparativeCCCCCCCCExample 8ComparativeCCCCCCCCExample 9ComparativeCCCCCCCCExample 10ComparativeCCCCCCCCExample 11ComparativeCCCCCCCCExample 12ComparativeCCCCCCCCExample 13ComparativeCCCCCCCCExample 14ComparativeCCCCCCCCExample 15ComparativeCCCCCCCCExample 16ComparativeCCCCCCCCExample 17ComparativeCCCCCCCCExample 18ComparativeCCCCCCCCExample 19ComparativeCCCCCCCCExample 20ComparativeCCCCCCCCExample 21ComparativeCCCCCCCCExample 22ComparativeDCDDDCDCExample 23ComparativeCDCDCDCDExample 24Although the present invention is described in detail with reference to concrete examples, it is evident to those skilled in the art that various changes and modifications may be made without departing from the spirit and the scope of the present invention.

Examples

examples

[0074]The effects of the present invention are described below in detail by way of Examples. However, the present invention is not limited by the following Examples.

[0075]As metallic materials, a cold-rolled mild steel sheet compatible with the JIS G3141:2011 standard (SPCC: thickness, 0.8 mm), an alloyed zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (GA: thickness, 0.8 mm), an aluminum alloy sheet compatible with the JIS H4000:2014 standard (A6061: thickness, 0.8 mm), a zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (SGCC: thickness, 0.8 mm), a magnesium alloy sheet compatible with the JIS H4201:2018 standard (MP-AZ31B: thickness, 0.8 mm), and a zinc-aluminum-magnesium-based hot-dipped material (ZM40 / 40: thickness, 0.8 mm) were used after cutting each of these to a size of 70 mm (length)×150 mm (width).

[0076]Chemical conversion treatment agents were prepared using the following raw materials.

(Source A)

A1: Hexafluorozirconic acid[00...

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

[0001] This application is a U.S. National Phase Application under 35 U.S.C. § 371 of International Patent Application No. PCT / JP2023 / 042641 filed on Nov. 29, 2023, which claims the benefit of priority to Japanese Patent Application No. 2022-198622 filed on Dec. 13, 2022, the contents of all of which are incorporated herein by reference in their entireties. The International Application was published in Japanese on Jun. 20, 2024 as International Publication No. WO / 2024 / 127983 under PCT Article 21 (2).FIELD OF THE INVENTION

[0002] The present invention relates to a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material.BACKGROUND OF THE INVENTION

[0003] Conventionally, treatment liquids for treatment of metal surfaces, which treatment liquids enable application of surface treatment that achieves excellent corrosion resistance and favorable adhesiveness, have been developed. For example, WO 03 / 074761 discloses a surface treatment composition for aluminum, an aluminum alloy, magnesium, or a magnesium alloy, the composition comprising: Compound A, which contains at least one metallic element selected from Hf (IV), Ti (IV), and Zr (IV); a fluorine-containing compound in an amount sufficient to allow the presence, in the composition, of fluorine at least five times the total molar concentration of metals contained in the Compound A; at least one metal ion B, selected from the group of alkaline earth metals; at least one metal ion C, selected from Al, Zn, Mg, Mn, and Cu; and a nitrate ion.PRIOR ART DOCUMENTSPatent Documents[Patent Document 1] WO 03 / 074761Problems to be Solved by the Invention

[0005] However, for the surface treatment, not only adhesiveness and corrosion resistance, but also external appearance as a finishing performance have been considered to be important. Further, in recent years, exposure tests and corrosion tests have been considered to be important in corrosion resistance tests since exposure tests and corrosion tests provide environmental conditions closer to the actual conditions compared to salt spray tests (SST) and the JASO-M609 method, which have been commonly employed. Further, from the viewpoint of reducing the environmental load, lowering of the chemical conversion treatment temperature has also been considered to be important. On the other hand, none of the conventional surface treatment techniques has achieved both the external appearance and the corrosion resistance after chemical conversion treatment.

[0006] An object of the present invention is to provide a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material, which agent achieves excellent external appearance after chemical conversion treatment, as well as excellent corrosion resistance as evaluated by, for example, an exposure test or the VDA621-415 method after painting, and which agent can be used in a wide temperature range.SUMMARY OF THE INVENTIONMeans for Solving the Problems

[0007] In order to solve the above problem, the present inventors intensively studied to discover that a chemical conversion treatment agent comprising: a source of fluorine ions; a source A of ions containing zirconium; a source B of ions containing aluminum; and a specific water-soluble or water-dispersible polymer, or a salt thereof C; the agent satisfying specific parameters, is capable of forming a chemical conversion coating that achieves excellent corrosion resistance, and excellent external appearance after chemical conversion treatment, thereby completing the present invention.

[0008] The present invention includes, for example, the following:

[0009] [1] a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material, the agent comprising:

[0010] a source of fluorine ions;

[0011] a source A of ions containing zirconium;

[0012] a source B of ions containing aluminum; and

[0013] a water-soluble or water-dispersible polymer, or a salt thereof C, containing structural units represented by the following Formula (i):at not less than 90% by mole;

[0015] the agent satisfying the following Formula (1):(A⁢c+Bc) × (pH-3)X≥0.38Formula⁢ (1)with the proviso that X=7.2× 12(−1.6×(Ac+Bc)),

[0017] wherein in the Formula (1),

[0018] Ac is the concentration of zirconium element derived from the Source A in the chemical conversion treatment agent, and is 0.02 g / L to 2 g / L;

[0019] Bc is the concentration of aluminum element derived from the Source B in the chemical conversion treatment agent, and is 0.02 g / L to 2 g / L;

[0020] the ratio of Bc to Ac, Bc / Ac, is 0.03 to 10.0;

[0021] the concentration of the polymer or a salt thereof C, in the chemical conversion treatment agent is 0.0001 g / L to (0.16×Ac+0.23) g / L; and

[0022] pH is the pH of the chemical conversion treatment agent, and is 3.8 to 6.0; and

[0023] [2] the chemical conversion treatment agent according to [1], wherein the metallic material is at least one or more of iron materials, zinc or zinc-based plating materials, aluminum materials, aluminum alloy materials, aluminum-based plating materials, magnesium materials, and magnesium alloy materials.Effect of the Invention

[0024] The present invention can provide a chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material, which agent achieves excellent external appearance after chemical conversion treatment, as well as excellent corrosion resistance as evaluated by, for example, an exposure test or the VDA621-415 method after painting, and which agent can be used in a wide temperature range.DETAILED DESCRIPTION OF THE INVENTION

[0025] In the present description, a numerical value range expressed using “to” means the range that includes the numerical values described before and after the “to” as the lower limit value and the upper limit value, respectively, and “A to B” means a value that is not less than A and not more than B.

[0026] A chemical conversion treatment agent according to one embodiment of the present invention is described below.(Chemical Conversion Treatment Agent)

[0027] The chemical conversion treatment agent according to the present embodiment comprises predetermined amounts of: a source of fluorine ions; a source A of ions containing zirconium; a source B of ions containing aluminum; and a water-soluble or water-dispersible polymer, or a salt thereof C, containing structural units represented by Formula (i) at not less than 90% by mole; in an aqueous medium. By using this chemical conversion treatment agent, a chemical conversion coating that achieves excellent corrosion resistance after painting, and excellent external appearance of the coating, can be formed for metallic materials.

[0028] In the chemical conversion treatment agent according to the present embodiment, only the source of fluorine ions; Source A; Source B; and the predetermined polymer or a salt thereof C; may be contained in the aqueous medium, or other components may also be contained therein.(Source of Fluorine Ions)

[0029] The chemical conversion treatment agent according to the present embodiment contains a source of fluorine ions. The source of fluorine ions is not limited as long as it is a compound capable of supplying fluorine ions (hereinafter referred to as “fluorine-containing compound”) when the source is included in the chemical conversion treatment agent. Examples of the fluorine-containing compound include, but are not limited to, zirconium ion hexafluorozirconic acid, hexafluorotitanic acid, hexafluorohafnic acid, hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, germanium fluoride, potassium fluoride, potassium hydrogen fluoride, iron fluoride, hydrofluosilicic acid, sodium fluoride, and sodium hydrogen fluoride. Compounds containing zirconium and fluorine, such as hexafluorozirconic acid, are capable of supplying both zirconium-containing ions and fluorine ions. Only one fluorine-containing compound may be included, or two or more fluorine-containing compounds may be included.

[0030] The amount of the fluorine-containing compound included is not limited as long as the formation of the chemical conversion coating is not affected. Specifically, the fluorine-containing compound is preferably included such that the fluorine ion concentration is the sum of four to eight times the molar concentration of zirconium element contained in the chemical conversion treatment agent and two to four times the molar concentration of aluminum element contained in the chemical conversion treatment agent. By including the fluorine-containing compound within such a range, the free fluorine ion concentration during the treatment becomes appropriate, so that a favorable reaction rate can be achieved between the metallic material and the chemical conversion treatment agent. Thus, a favorable amount of coating can be formed.(Source A)

[0031] Source A is included in the chemical conversion treatment agent according to the present embodiment. Source A is not limited as long as it is a compound capable of supplying ions containing zirconium (hereinafter referred to as “zirconium-containing ions”) when the source is included in the chemical conversion treatment agent. Therefore, the chemical conversion treatment agent according to the present embodiment contains zirconium-containing ions. Examples of the zirconium-containing ions include metal ions of zirconium; complex ions containing zirconium; and oxide ions of zirconium.

[0032] Specific examples of the source A of zirconium-containing ions include hexafluorozirconic acid, zirconium nitrate, zirconyl nitrate, zirconium carbonate, zirconium hydroxide, and zirconium oxide. Only one of these sources may be included, or two or more of these sources may be included.

[0033] The concentration of zirconium-containing ions in the chemical conversion treatment agent is not limited, but the zirconium element concentration Ac derived from Source A, in the chemical conversion treatment agent is usually not less than 0.02 g / L, preferably not less than 0.05 g / L, and is usually not more than 2 g / L, preferably not more than 1.5 g / L. In cases where two or more kinds of Sources A are included in the chemical conversion treatment agent, Ac means the total concentration of zirconium element derived from these.

[0034] In cases where the zirconium element concentration Ac is within the range described above, an effective amount of Zr can be achieved in the chemical conversion coating.(Source B)

[0035] Source B is included in the chemical conversion treatment agent according to the present embodiment. Source B is not limited as long as it is a compound capable of supplying ions containing aluminum (hereinafter referred to as “aluminum-containing ions”) when the source is included in the chemical conversion treatment agent. Therefore, the chemical conversion treatment agent according to the present embodiment contains aluminum-containing ions. Examples of the aluminum-containing ions include metal ions of aluminum; complex ions containing aluminum; and oxide ions of aluminum. Specific examples of the source of aluminum-containing ions, B, include, but are not limited to, aluminum hydroxide, aluminum nitrate, aluminum sulfate, aluminum carbonate, and aluminum oxide. In cases where these may be in the forms of salts, such salts may be used. Only one of these sources may be included, or two or more of these sources may be included.

[0036] The concentration of aluminum-containing ions in the chemical conversion treatment agent is not limited, but the aluminum element concentration Bc derived from Source B, in the chemical conversion treatment agent is usually not less than 0.02 g / L, preferably not less than 0.05 g / L, and is usually not more than 2 g / L, preferably not more than 1.5 g / L. In cases where two or more kinds of sources B are included in the chemical conversion treatment agent, Bc means the total concentration of aluminum element derived from these.

[0037] In cases where the aluminum element concentration Bc is within the range described above, an appropriate free fluorine ion concentration can be achieved in the chemical conversion treatment agent.(Ratio Between Sources A and B)

[0038] The ratio (Bc / Ac) of the aluminum element concentration Bc derived from Source B, to the zirconium element concentration Ac derived from Source A, in the chemical conversion treatment agent is usually not less than 0.03, and usually not more than 10.0.(Water-Soluble or Water-Dispersible Polymer, or Salt Thereof C)

[0039] The chemical conversion treatment agent according to the present embodiment comprises a water-soluble or water-dispersible polymer, or a salt thereof C (hereinafter simply referred to as “Polymer C”). Polymer C is not limited as long as it is a polymer containing structural units represented by the Formula (i) at not less than 90% by mole. Specific examples of Polymer C include polydiallylamines including: diallylamine polymers; and salts of diallylamine polymers such as diallylamine hydrochloride polymers, diallylamine sulfate polymers, and diallylamine acetate polymers.

[0040] The degree of polymerization of Polymer C is not limited. Its weight average molecular weight is usually not less than 1000, preferably not less than 5000. The weight average molecular weight is a value measured by GPC (gel permeation column chromatography) and calculated in terms of polystyrene.

[0041] The content (amount included) of Polymer C in the chemical conversion treatment agent is usually not less than 0.0001 g / L, preferably not less than 0.001 g / L, more preferably not less than 0.005 g / L, and is not more than (0.16×Ac+0.23) g / L, in terms of the solid content.

[0042] In cases where the content of Polymer C is within the range described above, adhesiveness and corrosion resistance of the chemical conversion coating can be improved.(Aqueous Medium)

[0043] The chemical conversion treatment agent according to the present embodiment may contain an aqueous medium. The aqueous medium is not limited as long as it is water, or a mixture of water and a water-miscible organic solvent (in which water is contained at not less than 50% by volume with respect to the volume of the aqueous medium). The water-miscible organic solvent is not limited as long as the solvent is miscible with water, and examples of the solvent include ketone-based solvents such as acetone and methyl ethyl ketone; amide-based solvents such as N,N′-dimethylformamide and dimethylacetamide; alcohol-based solvents such as methanol, ethanol, and isopropanol; ether-based solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone-based solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone. One of these water-miscible organic solvents may be mixed with water, or two or more of these may be mixed with water.(Other Components)

[0044] The chemical conversion treatment agent according to the present embodiment may contain, as other components, additives normally used in chemical conversion treatment agents. Examples of the other components include organic acids; oxidizing agents; metal ions other than Sources A and B; organosilane compounds; metal alkoxides; water-soluble resins or water-dispersible resins other than Polymer C; surfactants; and pH-adjusting agents. Only one of these other components may be included, or two or more of these other components may be included. These other components may be included within ranges in which the effect of the present invention is not inhibited.(Organic Acids)

[0045] Examples of organic acids that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, organic sulfonic acids, organic phosphonic acids, organic phosphoric acids, aliphatic carboxylic acids, and aromatic carboxylic acids; specifically, methanesulfonic acid, ethanesulfonic acid, lactic acid, oxalic acid, and citric acid. Only one organic acid may be included, or two or more organic acids may be included.(Oxidizing Agents)

[0046] Examples of oxidizing agents that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, hydrogen peroxide, nitrate, nitrite, permanganate, chlorate, persulfate, nitro-containing compounds, hypochlorous acid, organic peroxide, and bromate; preferably, hydrogen peroxide, nitrate, and nitrite. Only one oxidizing agent may be included, or two or more oxidizing agents may be included. Sulfate ions may or may not be included.(Sources of Metal Ions Other than Sources A and B)

[0047] Examples of sources of metal ions other than Sources A and B that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, compounds containing copper, iron, manganese, magnesium, nickel, cobalt, zinc, tungsten, or the like. Only one source, or two or more sources, of metal ions other than Sources A and B may be included.(Organosilane Compounds)

[0048] Examples of organosilane compounds that may be included in the chemical conversion treatment agent according to the present embodiment include aminosilane compounds, epoxysilane compounds, and alkoxysilane compounds. Specific examples of the organosilane compounds include, but are not limited to, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyldimethylmethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyldiethylethoxysilane, N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropylethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, and 3-glycidoxypropyltriethoxysilane. In the chemical conversion treatment agent, each organosilane compound may be present as it is, may be in the form of a hydrolysate derived by hydrolysis of an organosilane compound, may be in the form of a polycondensate derived by polycondensation of the hydrolysate, may be in the form of a copolymer (alternating copolymer, random copolymer, block copolymer, graft copolymer, or the like) derived by copolymerization of individual hydrolysates, or may be a mixture of a plurality of forms.(Metal Alkoxides)

[0049] Examples of metal alkoxides that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, zirconium tetrapropoxide, zirconium tetraisopropoxide, zirconium tetra-normal propoxide, zirconium tetranormal butoxide, titanium methoxide, titanium ethoxide, titanium tetraisopropoxide, titanium tetranormal butoxide, titanium butoxide dimer, titanium tetra-2-ethylhexoxide, triisopropoxide vanadium (v) oxide, vanadium butoxide, triethoxyvanadium (v) oxide, aluminum isopropoxide, and aluminum-tert-butoxide. One metal alkoxide may be included alone, or two or more metal alkoxides may be included. In the chemical conversion treatment agent, each metal alkoxide may be present as it is, may be in the form of a hydrolysate derived by hydrolysis of a metal alkoxide, may be in the form of a polycondensate derived by polycondensation of the hydrolysate, or of an organosilane compound hydrolysate, may be in the form of a copolymer (alternating copolymer, random copolymer, block copolymer, graft copolymer, or the like) derived by copolymerization of individual hydrolysates or organosilane compound hydrolysates, or may be a mixture of a plurality of forms. Metal alkoxides containing zirconium are also regarded as Source A, and metal alkoxides containing aluminum are also regarded as Source B.(Water-Soluble Resins or Water-Dispersible Resins Other than Polymer C)

[0050] Examples of water-soluble resins or water-dispersible resins other than Polymer C that may be included in the chemical conversion treatment agent according to the present embodiment include, but are not limited to, poly(meth)acrylate resins, urethane resins, acrylic resins, epoxy resins, and phenol resins; and amine resins not containing a structural unit represented by Formula (i). One water-soluble resin or water-dispersible resin other than Polymer C may be included alone, or two or more water-soluble resins and / or water-dispersible resins other than Polymer C may be included.(Surfactants)

[0051] Examples of surfactants that may be included in the chemical conversion treatment agent according to the present embodiment include nonionic surfactants; and ionic surfactants such as cationic, anionic, or amphoteric surfactants. Examples of the nonionic surfactants include, but are not limited to, polyethylene glycol-type nonionic surfactants such as polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and polyoxyethylene-polyoxypropylene-block polymers; polyhydric alcohol-type nonionic surfactants such as sorbitan fatty acid esters; and amide-type nonionic surfactants such as fatty acid alkylolamides. Examples of the cationic surfactants include, but are not limited to, amine salt-type cationic surfactants such as higher alkyl amine salts and polyoxyethylene higher alkyl amines; and quaternary ammonium salt-type cationic surfactants such as alkyltrimethylammonium salts. Examples of the anionic surfactants include, but are not limited to, higher alkyl ether sulfuric acid ester salts to which ethylene oxide is added. The HLB value (as calculated by the Griffin's method) of the surfactants is not limited, and is preferably 6 to 18, more preferably 10 to 14. One of the surfactants may be included alone, or two or more of the above surfactants may be included, in the chemical conversion treatment agent of the present embodiment. By including the above surfactant(s) in the chemical conversion treatment agent of the present embodiment, chemical conversion treatment and degreasing treatment can be carried out at the same time in one step.(pH of Chemical Conversion Treatment Agent)

[0052] The pH of the chemical conversion treatment agent according to the present embodiment is usually in the acidic to neutral range. Specifically, the pH is within the range of 3.8 to 6.0, more preferably within the range of 4.1 to 5.1.

[0053] The pH value in the present description means a value measured at 40° C. using a pH meter.

[0054] The pH of the chemical conversion treatment agent may be adjusted using a pH-adjusting agent, such as an acid component, for example, hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, or an organic acid; or an alkaline component, for example, lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, an alkali metal salt, ammonia, an ammonium salt, or an amine. However, the components are not limited to these. One pH-adjusting agent, or two or more pH-adjusting agents may be used.(Values of Specific Parameters)

[0055] The value of the left-hand side of the following Formula (1) is usually 0.38 to 10, preferably 0.8 to 5. The effect of the present invention is produced by satisfying Formula (1).(A⁢c+Bc) × (pH-3)X≥0.38Formula⁢ (1)with the proviso that X=7.2× 12(−1.6×(Ac+Bc)).(Method of Producing Chemical Conversion Treatment Agent)The chemical conversion treatment agent according to the present embodiment can be produced by including predetermined amounts of a source of fluorine ions; Source A; Source B; and a predetermined polymer or a salt thereof C, as raw materials in an aqueous medium.(Method of Forming Chemical Conversion Coating)

[0057] A method of forming a chemical conversion coating using the chemical conversion treatment agent according to the present embodiment comprises a contact step of bringing the chemical conversion treatment agent according to the present embodiment into contact on or over a surface of a metallic material. By this, a chemical conversion coating is formed on or over the surface of the metallic material. Examples of the method of bringing the chemical conversion treatment agent into contact with the metallic material include, but are not limited to, conventional contact methods such as treatment methods including the immersion treatment method, the spray treatment method, the pouring treatment method, and combinations thereof.

[0058] The contact temperature in the above contact method is preferably within the range of 10° C. to 60° C., more preferably within the range of 20° C. to 50° C. In the present embodiment, the range of from 10° C. to 25° C. is regarded as “low temperature”, and the range of from more than 25° C. to not more than 50° C. is regarded as “high temperature”. The contact time is preferably within the range of 30 seconds to 300 seconds, more preferably within the range of 60 seconds to 180 seconds. However, the contact time is not limited thereto.

[0059] Further, a pretreatment step may be carried out before the step of contacting the chemical conversion treatment agent. Examples of the pretreatment step include an acid pickling step; a degreasing step; an alkali washing step; a chromate chemical conversion treatment step; a phosphate chemical conversion treatment step using a phosphate such as zinc phosphate or iron phosphate; a bismuth displacement plating step; a zirconium chemical conversion treatment step; a titanium chemical conversion treatment step; a hafnium chemical conversion treatment step; and a vanadium chemical conversion treatment step. One of these pretreatment steps may be carried out, or two or more of these pretreatment steps may be carried out sequentially in combination. Examples of the combination of two or more steps include the combination of a phosphate chemical conversion treatment step with a chromate chemical conversion treatment step, a bismuth displacement plating step, a zirconium chemical conversion treatment step, a titanium chemical conversion treatment step, a hafnium chemical conversion treatment step, or a vanadium chemical conversion treatment step. In the zirconium chemical conversion treatment step performed as a pretreatment step, the chemical conversion treatment agent according to the present embodiment may be used, or a chemical conversion treatment agent different from the chemical conversion treatment agent according to the present embodiment may be used. In cases where a pretreatment step(s) described above is / are carried out, a water washing treatment step may be carried out after the pretreatment step(s). In cases where a plurality of pretreatment steps is carried out, a water washing treatment step may be carried out after each step, or after some of the steps. In cases where the water washing treatment step is carried out, a drying step of drying the surface of the metallic material may be carried out thereafter.

[0060] In the method of forming a chemical conversion coating according to the present embodiment, the contact step may be followed by a post-treatment step such as an alkali washing step, a water washing step, chromate chemical conversion treatment, a zinc phosphate chemical conversion treatment step, a bismuth displacement plating step, an iron phosphate chemical conversion treatment step, a zirconium chemical conversion treatment step, a titanium chemical conversion treatment step, a hafnium chemical conversion treatment step, or a drying step. One of these post-treatment steps may be carried out alone, or two or more of these steps may be carried out sequentially in combination. In the zirconium chemical conversion treatment step performed as a post-treatment step, the chemical conversion treatment agent according to the present embodiment may be used, or a chemical conversion treatment agent different from the chemical conversion treatment agent according to the present embodiment may be used. In cases where a post-treatment step(s) described above is / are carried out, a water washing treatment step(s) may be carried out after the post-treatment step(s). In cases where a plurality of post-treatment steps is carried out, a water washing treatment step may be carried out after each step, or after some of the steps. In cases where the washing treatment step is carried out, a drying step of drying the surface of the metallic material may be carried out thereafter.

[0061] Further, a paint may be formed on a chemical conversion coating formed by the method of forming a chemical conversion coating described above, to produce a painted metallic material having the chemical conversion coating and the paint. In this case, the formation of the chemical conversion coating may be followed by a paint formation treatment for forming the paint, such as a painting step and a drying step of drying the paint material on the surface of the metallic material after the painting (which may include, for example, a baking step and a curing step).

[0062] Before the painting step, a water washing step may be carried out to wash, with water, the surface of the metallic material with which the chemical conversion treatment agent according to the present embodiment has been brought into contact. Further, a drying step of drying the surface of the metallic material with which the chemical conversion treatment agent has been brought into contact, or a drying step of drying the surface of the metallic material that has been subjected to the water washing treatment step, may be carried out. Further, one of, or two or more of the above post-treatment steps may be carried out after the contact step but before the painting step. In cases where a post-treatment step(s) described above is / are carried out, a water washing treatment step(s) may be carried out after the post-treatment step(s). In cases where a plurality of post-treatment steps is carried out, a water washing treatment step may be carried out after each step, or after some of the steps. In cases where the washing treatment step is carried out, a drying step of drying the surface of the metallic material may be carried out thereafter.

[0063] The painting step is carried out using a paint material, for the surface of the metallic material having the chemical conversion coating. The painting method is not limited, and a conventionally known method may be applied. Examples of the conventionally known method include roll painting, electrodeposition painting (for example, cationic electrodeposition painting and anionic electrodeposition painting), spray painting, hot spray painting, airless spray painting, electrostatic (powder) painting, roller coating, curtain flow coating, brush painting, bar coating, and the fluidized bed painting method.

[0064] Examples of the paint material include known paint materials such as oil-based paint materials, cellulose derivative paint materials, phenol resin paint materials, alkyd resin paint materials, amino-alkyd resin paint materials, urea resin paint materials, unsaturated resin paint materials, vinyl resin paint materials, acrylic resin paint materials, epoxy resin paint materials, polyurethane resin paint materials, silicone resin paint materials, fluorine resin paint materials, anticorrosive paints, antifouling paint materials, powder paint materials, cationic electrodeposition paint materials, anionic electrodeposition paint materials, aqueous paint materials, and solvent paint materials. In the painting step, a single paint may be formed, or two or more paints may be formed using the same or different paint material(s). The drying step is a step of drying the paint material after painting, to cure the paint material. Examples of the drying method include air drying, vacuum drying, convective heat drying (for example, natural convective heat drying or forced convective heat drying), radiation drying (for example, near-infrared drying or far-infrared drying), ultraviolet dry-curing, electron beam dry-curing, Vapocure, and bake drying. One of these drying methods may be carried out, or two or more of these drying methods may be carried out in combination.

[0065] As the cationic electrodeposition paint, a known method may be applied. Examples of the method include a method using a cationic electrodeposition paint material containing: an amine-added epoxy resin as a paint material; and a blocked polyisocyanate curing agent as a curing component; wherein the metallic material having the chemical conversion coating is immersed in this paint material. The cationic electrodeposition painting is carried out, for example, by application of a voltage using a rectifier, and using the metallic material having the chemical conversion coating as a cathode, while the paint material is kept at a predetermined temperature under stirring. For the metallic material that has been subjected to the cationic electrodeposition painting in this manner, water washing and baking may be carried out to form a paint on the chemical conversion coating. The baking is carried out within a predetermined temperature range for a predetermined length of time. For example, in one mode, the baking is carried out at 170° C. for 20 minutes. In cases where the cationic electrodeposition painting method using a cationic electrodeposition paint material is applied, the water washing treatment step is preferably carried out before the painting step, using water whose sodium ion concentration is less than 500 ppm by mass, in order to prevent aggregation of the paint material due to sodium ions.

[0066] In cases where a powder paint material is used, a known method may be applied as a painting method such as spray painting, electrostatic powder painting, or the fluidized bed painting method. Examples of the powder paint material include a material containing: a polyester resin; and a blocked polyisocyanate curing agent, a β-hydroxyalkylamide curing agent (see, for example, JP 2011-88083 A), or triglycidyl isocyanurate as a curing agent. The baking is carried out within a predetermined temperature range for a predetermined length of time. For example, in one mode, the baking is carried out at 130° C. to 250° C. for 20 minutes.

[0067] In cases where the solvent paint material is used, a known method may be applied as a painting method such as spray painting, electrostatic painting, or bar coating. Examples of the solvent paint material include a material containing: a resin such as a melamine resin, an acrylic resin, a urethane resin, or a polyester resin; and an organic solvent such as a thinner. The baking is carried out within a predetermined temperature range for a predetermined length of time. For example, in one mode, the baking is carried out at 130° C. for 20 minutes.

[0068] Examples of the drying method for curing the paint material after painting include air drying, vacuum drying, convective heat drying (for example, natural convective heat drying or forced convective heat drying), radiation drying (for example, near-infrared drying or far-infrared drying), ultraviolet dry-curing, electron beam dry-curing, and Vapocure. One of these drying methods may be carried out, or two or more of these drying methods may be carried out in combination.

[0069] The paint obtained by the painting step may have a single layer or a plurality of layers. In cases where the paint has a plurality of layers, the paint materials for forming the paints, the painting methods using the paint materials, the drying methods for the metallic material after painting, and the like may each be the same or different.

[0070] Examples of the metallic material include iron (for example, cold-rolled steel sheets, hot-rolled steel sheets, high-tensile steel sheets, tool steels, alloy tool steels, spheroidal graphite cast irons, and gray cast iron); plated materials such as zinc and zinc-based plated materials (for example, zinc electroplated materials, zinc hot-dipped materials, zinc-aluminum-based hot-dipped materials, zinc-aluminum-magnesium-based hot-dipped materials, alloyed zinc hot-dipped materials, and zinc-based electroplated materials); aluminum and aluminum alloy materials (for example, 1000 series aluminum alloy materials, 2000 series aluminum alloy materials, 3000 series aluminum alloy materials, 4000 series aluminum alloy materials, 5000 series aluminum alloy materials, 6000 series aluminum alloy materials, 7000 series aluminum alloy materials, 8000 series aluminum alloy materials, aluminum casts, aluminum alloy casts, and die-cast materials); aluminum-based plated materials; and magnesium and magnesium alloy materials (for example, AZ91 and AZ61AZ31).

[0071] In the chemical conversion coating formed using the chemical conversion treatment agent according to the present embodiment, the total mass of titanium, zirconium, and hafnium contained is preferably not less than 5 mg / m2, more preferably not less than 10 mg / m2, still more preferably not less than 20 mg / m2 per unit area. Although there is no upper limit value, the total mass is preferably not more than 800 mg / m2. The mass of titanium, zirconium, and hafnium in this chemical conversion coating may be measured, for example, using an X-ray fluorescence analyzer.

[0072] The metallic material having the chemical conversion coating may have one of, or two or more of the above-described various coatings (for example, a chromate chemical conversion coating, a phosphate chemical conversion coating, or a bismuth displacement plating coating) on either side of the chemical conversion coating obtained by bringing the chemical conversion treatment agent according to the present embodiment into contact.

[0073] By painting the surface of a metallic material having a chemical conversion coating using a paint material, a paint can be formed to produce a painted metallic material having the chemical conversion coating and the paint. The painted metallic material may have the paint on the surface of the metallic material having the chemical conversion coating, or may have the paint on the surface of one or more of the above-described various coatings (for example, a chromate chemical conversion coating, a phosphate chemical conversion coating, a bismuth displacement plating coating, or a vanadium chemical conversion coating) additionally formed on the chemical conversion coating. The paint may have a single layer, or may have two or more layers. The thickness of the paint is not limited, and is set appropriately according to the use of the painted metallic material.EXAMPLES

[0074] The effects of the present invention are described below in detail by way of Examples. However, the present invention is not limited by the following Examples.<Metallic Materials>

[0075] As metallic materials, a cold-rolled mild steel sheet compatible with the JIS G3141:2011 standard (SPCC: thickness, 0.8 mm), an alloyed zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (GA: thickness, 0.8 mm), an aluminum alloy sheet compatible with the JIS H4000:2014 standard (A6061: thickness, 0.8 mm), a zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (SGCC: thickness, 0.8 mm), a magnesium alloy sheet compatible with the JIS H4201:2018 standard (MP-AZ31B: thickness, 0.8 mm), and a zinc-aluminum-magnesium-based hot-dipped material (ZM40 / 40: thickness, 0.8 mm) were used after cutting each of these to a size of 70 mm (length)×150 mm (width).<Components Used in Preparation of Chemical Conversion Treatment Agents>

[0076] Chemical conversion treatment agents were prepared using the following raw materials.(Source A)A1: Hexafluorozirconic acid

[0078] A2: Zirconium nitrate

[0079] A3: Zirconium hydroxide(Source B)B1: Aluminum nitrate

[0081] B2: Aluminum hydroxide(Polymer C)C1: Diallylamine polymer (PAS-21; Nittobo Medical Co., Ltd.; content ratio of Formula (i), 100%)

[0083] C2: Diallylamine hydrochloride polymer (PAS-21CL; Nittobo Medical Co., Ltd.; content ratio of Formula (i), 100%)

[0084] C3: Allylamine hydrochloride-diallylamine hydrochloride polymer (PAA-D11-HCL; Nittobo Medical Co., Ltd.; content ratio of Formula (i), 50%)

[0085] Hydrofluoric acid was used as a source of fluorine ions.

[0086] In addition, the following raw materials were used as other additives.(Organic Acid D)D1: Methanesulfonic acid

[0088] D2: Ethanesulfonic acid

[0089] D3: Succinic acid

[0090] D4: Citric acid(Oxidizing Agent E)E1: Nitric acid(Metals Other than Sources A and B (Metal F))

[0092] F1: Ferric sulfate

[0093] F2: Iron (III) nitrate

[0094] F3: Copper nitrate(Organosilane Compound G)G1:3-Aminopropyldimethylmethoxysilane

[0096] G2:3-Aminopropylmethyldimethoxysilane

[0097] G3:3-Aminopropyldiethylethoxysilane

[0098] G4:3-Aminopropylethyldiethoxysilane

[0099] G5:3-Aminopropyltriethoxysilane

[0100] G6:3-Aminopropyltrimethoxysilane

[0101] G7:3-Glycidoxypropyltrimethoxysilane

[0102] G8: Ethyltrimethoxysilane

[0103] G9: Ureidopropyltriethoxysilane

[0104] G10: Isocyanate propyltriethoxysilane(Metal Alkoxide H)H1: Titanium methoxide

[0106] H2: Vanadium propoxide

[0107] H3: Zirconium tetranormal propoxide

[0108] H4: Aluminum isopropoxide

[0109] H5: Vinyltrimethoxysilane(Other Components)I1: Hydroxylamine sulfate

[0111] I2: Ascorbic acid<Preparation of Chemical Conversion Treatment Agents>

[0112] As shown in Tables 1 and 2, predetermined amounts of the components were added, and then the pH was adjusted to a predetermined value with sodium hydroxide, to prepare chemical conversion treatment agents of Examples 1 to 48 and Comparative Examples 1 to 24.<Production of Metallic Materials Having Chemical Conversion Coating>

[0113] A degreasing agent (FC-E2093; Nihon Parkerizing Co., Ltd.; an aqueous solution in which Agent A and Agent B were dissolved at concentrations of 13 g / L and 11 g / L, respectively) was sprayed onto the surface of each metallic material at 43° C. for 120 seconds, to perform degreasing. Thereafter, the material was subjected to spray water washing at 25° C. for 30 seconds. Subsequently, the metallic material, which had been subjected to the degreasing and then the spray water washing, was immersed in various chemical conversion treatment agents (the chemical conversion treatment agents of Examples 1 to 48 and Comparative Examples 1 to 24) at 15° C. (low temperature) or 38° C. (high temperature) for 120 seconds, to form a chemical conversion coating on the surface of each metallic material. The surface of the resulting metallic material having the chemical conversion coating was washed at 25° C. with tap water, and then with deionized water. After the washing with water, a test piece for evaluation of the external appearance was dried at 40° C. for 10 minutes. A test piece for the corrosion resistance after painting was not dried before it was subjected to the painting described below.TABLE 1Chemical Conversion AgentFluorinePolymer (C)Other AdditiveConcen-Source (A)Source (B)Concen-Concen-trationAcBctration0.16*Ac +trationFormula[g / L]Material[g / L]Material[g / L]Bc / AcMaterial[g / L]0.23Material[g / L]pH(1)Example 10.46A10.20B10.100.50C20.20000.2620——4.20.45Example 20.46A10.20B10.100.50C20.20000.2620——4.20.45Example 30.46A10.20B10.100.50C20.20000.2620——4.20.45Example 40.46A20.20B20.100.50C10.20000.2620——4.20.45Example 50.46A30.20B20.100.50C20.20000.2620——4.20.45Example 60.45A30.02B20.2010.00C20.20000.2332——4.20.38Example 70.55A30.10B20.202.00C20.20000.2460——4.20.45Example 81.05A30.50B20.200.40C20.20000.3100——4.20.76Example 91.67A31.00B20.200.20C20.20000.3900——4.21.21Example 102.92A32.00B20.200.10C20.20000.5500——4.22.20Example 110.67A30.50B20.020.04C20.20000.3100——4.20.61Example 120.84A30.50B20.100.20C20.20000.3100——4.20.68Example 131.18A30.10B20.505.00C20.20000.2460——4.20.68Example 142.24A30.10B21.0010.00C20.20000.2460——4.21.12Example 154.48A30.20B22.0010.00C20.20000.2620——4.22.20Example 161.31A30.20B20.502.50C20.20000.2620——3.80.63Example 171.31A30.20B20.502.50C20.20000.2620——4.00.70Example 181.31A30.20B20.502.50C20.20000.2620——4.10.73Example 191.31A30.20B20.502.50C20.20000.2620——4.50.84Example 201.31A30.20B20.502.50C20.20000.2620——5.00.95Example 211.31A30.20B20.502.50C20.20000.2620——6.01.14Example 220.55A30.10B20.202.00C20.00010.2460——4.20.45Example 230.55A30.10B20.202.00C20.01000.2460——4.20.45Example 240.55A30.10B20.202.00C20.10000.2460——4.20.45Example 250.80A30.30B20.200.67C20.25000.2780——4.20.60Example 261.67A31.00B20.200.20C20.35000.3900——4.21.21Example 272.92A32.00B20.200.10C20.50000.5500——4.22.20Example 282.61A10.40B11.002.50C20.20000.2940D11.004.21.41Example 291.18A10.10B10.505.00C20.20000.2460D21.004.20.68Example 303.36A31.00B21.001.00C20.20000.3900F11.004.22.00Example 313.13A32.00B20.300.15C20.20000.5500F21.004.22.30Example 322.61A10.40B11.002.50C20.20000.2940F30.054.21.41Example 331.18A10.10B10.505.00C20.20000.2460G11.004.20.68Example 343.36A11.00B11.001.00C20.20000.3900G21.004.22.00Example 353.13A12.00B10.300.15C20.20000.5500G31.004.22.30Example 362.61A10.40B11.002.50C20.20000.2940G41.004.21.41Example 371.18A30.10B20.505.00C20.20000.2460G51.004.20.68Example 383.36A31.00B21.001.00C20.20000.3900G61.004.22.00TABLE 2Chemical Conversion AgentFluorinePolymer (C)Other AdditiveConcen-Source (A)Source (B)Concen-Concen-trationAcBctration0.16*Ac +trationFormula[g / L]Material[g / L]Materialg / L]Bc / AcMaterial[g / L]0.23Material[g / L]pH(1)Example 393.13A12.00B10.300.15C20.20000.5500E11.004.22.30Example 400.92A10.40B10.200.50C20.20000.2940H11.004.20.68Example 410.67A10.20B10.201.00C20.20000.2620H21.004.20.52Example 422.28A10.70B10.500.71C20.20000.3420H31.004.21.48Example 431.95A31.00B20.200.20C20.20000.3900H41.004.21.34Example 442.92A12.00B10.200.10C20.20000.5500G52.004.22.20H12.00Example 450.92A10.40B10.200.50C20.20000.2940G52.004.20.68H22.00Example 462.63A10.70B10.500.71C20.20000.3420G52.004.21.76H32.00Example 472.23A11.00B10.200.20C20.20000.3900G52.004.21.47H42.00Example 482.92A12.00B10.200.10C20.20000.5500G52.004.22.20G72.00Comparative0.62A20.50———C20.20000.3100——4.00.50Example 1Comparative4.23——B12.00—C20.20000.2300——4.02.00Example 2Comparative13.06A12.00B15.002.50C20.20000.5500——3.97.00Example 3Comparative10.47A15.00B12.000.40C20.20001.0300——3.97.00Example 4Comparative2.54A12.00B10.020.01C20.20000.5500——4.02.02Example 5Comparative0.49A10.02B10.2211.00C20.20000.2332——4.00.24Example 6Comparative1.12A10.05B10.5010.00——0.2380——4.00.55Example 7Comparative3.92A10.60B21.502.50C30.02000.3260——4.02.10Example 8Comparative3.92A10.60B21.502.50C20.40000.3260——4.02.10Example 9Comparative1.52A10.20B10.603.00——0.2620I10.054.00.80Example 10Comparative1.94A10.20B10.804.00——0.2620I20.104.01.00Example 11Comparative2.36A10.20B11.005.00——0.2620D40.304.01.20Example 12Comparative3.36A11.00B11.001.00——0.3900F10.024.02.00Example 13Comparative23.63A12.00B110.005.00——0.5500F20.504.012.00Example 14Comparative2.52A11.00B10.600.60——0.3900D31.004.01.60Example 15Comparative1.88A11.00B10.300.30——0.3900H50.604.01.30Example 16Comparative17.29A12.00B17.003.50——0.5500G62.004.09.00Example 17Comparative2.31A11.00B10.500.50——0.3900G70.204.01.50Example 18Comparative1.88A11.00B10.300.30——0.3900G81.504.01.30Example 19Comparative4.19A12.00B10.800.40——0.5500G90.054.02.80Example 20Comparative3.36A11.00B11.001.00——0.3900G101.004.02.00Example 21Comparative3.36A11.00B11.001.00——0.3900G101.003.52.00Example 22Comparative0.42A30.08B10.151.88C20.20000.2428——3.20.00Example 23Comparative0.49A30.35B20.0250.07C20.20000.2860——4.00.375Example 24<Measurement of Amount of Zirconium Element in Chemical Conversion Coating (Amount of Deposited Zr)>The amount of zirconium element in the chemical conversion coating formed on the surface of the metallic material was determined as the amount of deposited Zr, using X-ray fluorescence (a scanning X-ray fluorescence analyzer: ZSX Primus II, manufactured by Rigaku Corporation).<Production of Metallic Materials Having Paint>

[0115] The chemical conversion coating formed on the surface of each metallic material was painted, and then baking was carried out to prepare a metallic material having a paint. Details of the painting method, and the baking conditions are described below.(Cationic Electrodeposition Painting)

[0116] A painting was formed by electrolysis using, as a cathode, a metallic material having each type of chemical conversion coating, and using a cationic electrodeposition paint material (GT-100V; manufactured by Kansai Paint Co., Ltd.). The electrolysis was carried out at an applied voltage of 180 V and a temperature of 30.0±0.5° C. In the electrolysis, the quantity of electricity was adjusted to achieve a paint thickness of 15.0±1.0 μm. After the cationic electrodeposition, the surface of the paint was washed with deionized water, and baking was carried out at 170° C. for 26 minutes, to prepare a metallic material (each test piece) having the paint.<External Appearance of Chemical Conversion Coating>

[0117] For the test piece having a chemical conversion coating obtained in each of Examples and Comparative Examples, the external appearance of the coating was rated by visual observation.<Evaluation Criteria>

[0118] A: Unevenness was found neither on the planar section nor the edges when the test piece was viewed from the front side. Unevenness was found neither on the planar section nor the edges when the test piece was viewed at an angle of 20° with respect to the front side.

[0119] B: Unevenness was found neither on the planar section nor the edges when the test piece was viewed from the front side. Unevenness was found on the planar section and the edges when the test piece was viewed at an angle of 20° with respect to the front side.

[0120] C: Unevenness was not found on the planar section, but was found on the edges when the test piece was viewed from the front side. Unevenness was found on the planar section and the edges when the test piece was viewed at an angle of 20° with respect to the front side.

[0121] D: Unevenness was found on the planar section and the edges when the test piece was viewed from the front side. Unevenness was found on the planar section and the edges when the test piece was viewed at an angle of 20° with respect to the front side.<Corrosion Resistance Test (Exposure Test)>

[0122] Using a cutter knife, an X-shaped scratch (cross-cut) was made on the painted surface of each test piece having a paint, such that the scratch reached the metal substrate. The test piece was then placed near the sea in Okinawa to perform the exposure for 2 years. Thereafter, the blister width (the maximum blister width on one side) of the paint from the scratched portion (cross-cut portion) on the test piece was measured. Corrosion resistance was evaluated according to the following evaluation criteria<Evaluation Criteria—Cross-Cut Portion>A: The blister width on one side was less than 5.0 mm.

[0124] B: The blister width on one side was not less than 5.0 mm, and less than 10.0 mm.

[0125] C: The blister width on one side was not less than 10.0 mm, and less than 15.0 mm.

[0126] D: The blister width on one side was not less than 15.0 mm.<Corrosion Resistance Test (VDA Method)>

[0127] Using a cutter knife, a single scratch was made at the center of the painted surface of each test piece having a paint, such that the scratch reached the metal substrate. Thereafter, six cycles of a corrosion cycle test were carried out using the VDA test according to 621-415 and DIN EN ISO 20567-1 (1982 version; method C).

[0128] The blister width (the maximum blister width on one side) of the paint from the scratched portion (cut portion) on the test piece was measured. Corrosion resistance was evaluated according to the following evaluation criteria.<Evaluation Criteria-Cut Portion>A: The blister width on one side was less than 5.0 mm.

[0130] B: The blister width on one side was not less than 5.0 mm, and less than 10.0 mm.

[0131] C: The blister width on one side was not less than 10.0 mm, and less than 15.0 mm.

[0132] D: The blister width on one side was not less than 15.0 mm.

[0133] The results of the evaluation tests are shown in Tables 3 to 6. In all evaluations, test pieces with rank A or B were judged as acceptable.TABLE 3SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBBBExample 2BBBBBBBBBBExample 3BBBBBBBBBBExample 4BBBBBBBBBBExample 5BBBBBBBBBBExample 6BBBBBBBBBBExample 7BBBBBBBBBBExample 8BBBBBBBBBBExample 9ABBABBABBAExample 10ABBABBABBAExample 11BBBBBBBBBBExample 12BBBBBBBBBBExample 13BBBBBBBBBBExample 14BBBABBBBBAExample 15ABBABBABBAExample 16BBBBBBBBBBExample 17BBBBBBBBBBExample 18BBBBBBBBBBExample 19BBBABBBBBAExample 20BBBABBBBBAExample 21BBBABBBBBAExample 22BBBBBBBBBBExample 23BBBBBBBBBBExample 24BBBBBBBBBBExample 25BBBBBBBBBBExample 26BBBABABBBAExample 27BBBABABBBAExample 28ABBABAABBAExample 29BBBABBBBBAExample 30ABBABAABBAExample 31ABBABAABBAExample 32ABBABAABBAExample 33BBBABBBBBAExample 34ABBABAABBAExample 35ABBABAABBAExample 36ABBABAABBAExample 37BBBABBBBBAExample 38ABBABAABBAGAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBExample 2BBBBBBBBExample 3BBBBBBBBExample 4BBBBBBBBExample 5BBBBBBBBExample 6BBBBBBBBExample 7BBBBBBBBExample 8BBBBBBBBExample 9BBABBABBExample 10BBABBABBExample 11BBBBBBBBExample 12BBBBBBBBExample 13BBBBBBBBExample 14BBBBBABBExample 15BBABBABBExample 16BBBBBBBBExample 17BBBBBBBBExample 18BBBBBBBBExample 19BBBBBABBExample 20BBBBBABBExample 21BBBBBABBExample 22BBBBBBBBExample 23BBBBBBBBExample 24BBBBBBBBExample 25BBBBBBBBExample 26BABBBABAExample 27BABBBABAExample 28BAABBABAExample 29BBBBBABBExample 30BAABBABAExample 31BAABBABAExample 32BAABBABAExample 33BBBBBABBExample 34BAABBABAExample 35BAABBABAExample 36BAABBABAExample 37BBBBBABBExample 38BAABBABATABLE 4SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.TempTemp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBBBExample 2BBBBBBBBBBExample 3BBBBBBBBBBExample 4BBBBBBBBBBExample 5BBBBBBBBBBExample 6BBBBBBBBBBExample 7BBBBBBBBBBExample 8BBBBBBBBBBExample 9ABBABBABBAExample 10ABBABBABBAExample 11BBBBBBBBBBExample 12BBBBBBBBBBExample 13BBBBBBBBBBExample 14BBBABBBBBAExample 15ABBABBABBAExample 16BBBBBBBBBBExample 17BBBBBBBBBBExample 18BBBBBBBBBBExample 19BBBABBBBBAExample 20BBBABBBBBAExample 21BBBABBBBBAExample 22BBBBBBBBBBExample 23BBBBBBBBBBExample 24BBBBBBBBBBExample 25BBBBBBBBBBExample 26BBBABABBBAExample 27BBBABABBBAExample 28ABBABAABBAExample 29BBBABBBBBAExample 30ABBABAABBAExample 31ABBABAABBAExample 32ABBABAABBAExample 33BBBABBBBBAExample 34ABBABAABBAExample 35ABBABAABBAExample 36ABBABAABBAExample 37BBBABBBBBAExample 38ABBABAABBAGAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 1BBBBBBBBExample 2BBBBBBBBExample 3BBBBBBBBExample 4BBBBBBBBExample 5BBBBBBBBExample 6BBBBBBBBExample 7BBBBBBBBExample 8BBBBBBBBExample 9BBABBABBExample 10BBABBABBExample 11BBBBBBBBExample 12BBBBBBBBExample 13BBBBBBBBExample 14BBBBBABBExample 15BBABBABBExample 16BBBBBBBBExample 17BBBBBBBBExample 18BBBBBBBBExample 19BBBBBABBExample 20BBBBBABBExample 21BBBBBABBExample 22BBBBBBBBExample 23BBBBBBBBExample 24BBBBBBBBExample 25BBBBBBBBExample 26BABBBABAExample 27BABBBABAExample 28BAABBABAExample 29BBBBBABBExample 30BAABBABAExample 31BAABBABAExample 32BAABBABAExample 33BBBBBABBExample 34BAABBABAExample 35BAABBABAExample 36BAABBABAExample 37BBBBBABBExample 38BAABBABATABLE 5SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 39ABBABAABBAExample 40BBBABBBBBAExample 41BBBABBBBBAExample 42ABBABAABBAExample 43ABBABAABBAExample 44ABBABAABBAExample 45BBBABBBBBAExample 46ABBABAABBAExample 47ABBABAABBAExample 48ABBABAABBAComparativeCDDDDDCDDDExample 1ComparativeDDDDDDDDDDExample 2ComparativeDDDCDCDDDCExample 3ComparativeDDDCDCDDDCExample 4ComparativeDDDCDCDDDCExample 5ComparativeDDDCDCDDDCExample 6ComparativeDDDCDCDDDCExample 7ComparativeCCCCCCCCCCExample 8ComparativeCCCCCCCCCCExample 9ComparativeCCCCCCCCCCExample 10ComparativeCCCCCCCCCCExample 11ComparativeCCCCCCCCCCExample 12ComparativeCCCCCCCCCCExample 13ComparativeCCCCCCCCCCExample 14ComparativeCCCCCCCCCCExample 15ComparativeCCCCCCCCCCExample 16ComparativeCCCCCCCCCCExample 17ComparativeCCCCCCCCCCExample 18ComparativeCCCCCCCCCCExample 19ComparativeCCCCCCCCCCExample 20ComparativeCCCCCCCCCCExample 21ComparativeCCCCCCCCCCExample 22ComparativeDDDCDCDDDCExample 23ComparativeCDCDCDCDCDExample 24GAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 39BAABBABAExample 40BBBBBABBExample 41BBBBBABBExample 42BAABBABAExample 43BAABBABAExample 44BAABBABAExample 45BBBBBABBExample 46BAABBABAExample 47BAABBABAExample 48BAABBABAComparativeDDCDDDDDExample 1ComparativeDDDDDDDDExample 2ComparativeDCDDDCDCExample 3ComparativeDCDDDCDCExample 4ComparativeDCDDDCDCExample 5ComparativeDCDDDCDCExample 6ComparativeDCDDDCDCExample 7ComparativeCCCCCCCCExample 8ComparativeCCCCCCCCExample 9ComparativeCCCCCCCCExample 10ComparativeCCCCCCCCExample 11ComparativeCCCCCCCCExample 12ComparativeCCCCCCCCExample 13ComparativeCCCCCCCCExample 14ComparativeCCCCCCCCExample 15ComparativeCCCCCCCCExample 16ComparativeCCCCCCCCExample 17ComparativeCCCCCCCCExample 18ComparativeCCCCCCCCExample 19ComparativeCCCCCCCCExample 20ComparativeCCCCCCCCExample 21ComparativeCCCCCCCCExample 22ComparativeDCDDDCDCExample 23ComparativeCDCDCDCDExample 24TABLE 6SPCCGACorrosionCorrosionExpernalResistanceExpernalResistanceAppearanceExposureVDAAppearanceExposureof CoatingTestmethodof CoatingTestLowHighLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Temp.Example 39ABBABAABBAExample 40BBBABBBBBAExample 41BBBABBBBBAExample 42ABBABAABBAExample 43ABBABAABBAExample 44ABBABAABBAExample 45BBBABBBBBAExample 46ABBABAABBAExample 47ABBABAABBAExample 48ABBABAABBAComparativeCDDDDDCDDDExample 1ComparativeDDDDDDDDDDExample 2ComparativeDDDCDCDDDCExample 3ComparativeDDDCDCDDDCExample 4ComparativeDDDCDCDDDCExample 5ComparativeDDDCDCDDDCExample 6ComparativeDDDCDCDDDCExample 7ComparativeCCCCCCCCCCExample 8ComparativeCCCCCCCCCCExample 9ComparativeCCCCCCCCCCExample 10ComparativeCCCCCCCCCCExample 11ComparativeCCCCCCCCCCExample 12ComparativeCCCCCCCCCCExample 13ComparativeCCCCCCCCCCExample 14ComparativeCCCCCCCCCCExample 15ComparativeCCCCCCCCCCExample 16ComparativeCCCCCCCCCCExample 17ComparativeCCCCCCCCCCExample 18ComparativeCCCCCCCCCCExample 19ComparativeCCCCCCCCCCExample 20ComparativeCCCCCCCCCCExample 21ComparativeCCCCCCCCCCExample 22ComparativeDDDCDCDDDCExample 23ComparativeCDCDCDCDCDExample 24GAA6061CorrosionCorrosionResistanceExpernalResistanceVDAAppearanceExposureVDAmethodof CoatingTestmethodLowHighLowHighLowHighLowHighTemp.Temp.Temp.Temp.Temp.Temp.Temp.TempExample 39BAABBABAExample 40BBBBBABBExample 41BBBBBABBExample 42BAABBABAExample 43BAABBABAExample 44BAABBABAExample 45BBBBBABBExample 46BAABBABAExample 47BAABBABAExample 48BAABBABAComparativeDDCDDDDDExample 1ComparativeDDDDDDDDExample 2ComparativeDCDDDCDCExample 3ComparativeDCDDDCDCExample 4ComparativeDCDDDCDCExample 5ComparativeDCDDDCDCExample 6ComparativeDCDDDCDCExample 7ComparativeCCCCCCCCExample 8ComparativeCCCCCCCCExample 9ComparativeCCCCCCCCExample 10ComparativeCCCCCCCCExample 11ComparativeCCCCCCCCExample 12ComparativeCCCCCCCCExample 13ComparativeCCCCCCCCExample 14ComparativeCCCCCCCCExample 15ComparativeCCCCCCCCExample 16ComparativeCCCCCCCCExample 17ComparativeCCCCCCCCExample 18ComparativeCCCCCCCCExample 19ComparativeCCCCCCCCExample 20ComparativeCCCCCCCCExample 21ComparativeCCCCCCCCExample 22ComparativeDCDDDCDCExample 23ComparativeCDCDCDCDExample 24Although the present invention is described in detail with reference to concrete examples, it is evident to those skilled in the art that various changes and modifications may be made without departing from the spirit and the scope of the present invention.

Examples

examples

[0074]The effects of the present invention are described below in detail by way of Examples. However, the present invention is not limited by the following Examples.

[0075]As metallic materials, a cold-rolled mild steel sheet compatible with the JIS G3141:2011 standard (SPCC: thickness, 0.8 mm), an alloyed zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (GA: thickness, 0.8 mm), an aluminum alloy sheet compatible with the JIS H4000:2014 standard (A6061: thickness, 0.8 mm), a zinc hot-dipped steel sheet compatible with the JIS G3302:2012 standard (SGCC: thickness, 0.8 mm), a magnesium alloy sheet compatible with the JIS H4201:2018 standard (MP-AZ31B: thickness, 0.8 mm), and a zinc-aluminum-magnesium-based hot-dipped material (ZM40 / 40: thickness, 0.8 mm) were used after cutting each of these to a size of 70 mm (length)×150 mm (width).

[0076]Chemical conversion treatment agents were prepared using the following raw materials.

(Source A)

A1: Hexafluorozirconic acid[00...

Claims

1. A chemical conversion treatment agent that forms a chemical conversion coating on or over a surface of a metallic material, the agent comprising:a source of fluorine ions;a source A of ions containing zirconium;a source B of ions containing aluminum; anda water-soluble or water-dispersible polymer, or a salt thereof C, containing structural units represented by the following Formula (i):at not less than 90% by mole;the agent satisfying the following Formula (1):(A⁢c+Bc) × (pH-3)X≥0.38Formula⁢ (1)with the proviso that X=7.2×12(−1.6×(Ac+Bc)),wherein in the Formula (1),Ac is the concentration of zirconium element derived from the Source A in the chemical conversion treatment agent, and is 0.02 g / L to 2 g / L;Bc is the concentration of aluminum element derived from the Source B in the chemical conversion treatment agent, and is 0.02 g / L to 2 g / L;the ratio of Bc to Ac, Bc / Ac, is 0.03 to 10.0;the concentration of the polymer or a salt thereof C, in the chemical conversion treatment agent is 0.0001 g / L to (0.16×Ac+0.23) g / L; andpH is the pH of the chemical conversion treatment agent, and is 3.8 to 6.0.

2. The chemical conversion treatment agent according to claim 1, wherein the metallic material is at least one or more of iron materials, zinc or zinc-based plating materials, aluminum materials, aluminum alloy materials, aluminum-based plating materials, magnesium materials, and magnesium alloy materials.

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