TW201936992A - Pretreatment agent, pretreatment method, metal material having chemical conversion coating and method for producing same, and coated metal material and method for producing same - Google Patents

Abstract

The present invention addresses the problem of providing a technology such as a pretreatment agent which is for chemical conversion treatment capable of forming a chemical conversion coating, and which can improve the corrosion resistance of a burr portion of an edge when a coating film is formed, and improve the adhesion to the coating film. The problem is solved by a pretreatment agent which is used for pretreatment in a chemical conversion treatment for forming a chemical conversion coating on the surface of or on top of the surface of the metal material, the pretreatment agent being formed by blending: (A) an organosilane compound having a primary amino group and alkoxysilyl group in a molecule; and (B) an organosilane compound having a glycidyl group and alkoxysilyl group in a molecule.

Description

Pretreatment agent, pretreatment method, metal material having chemical conversion film, method for producing the same, and coated metal material and method for producing the same

The present invention relates to a pretreatment method for forming a chemical conversion film on a surface or a surface of a metal material; a pretreatment agent for the pretreatment method; a metal material having the above chemical conversion film; and a method for producing the same; A metal material having a film and a coating film and a method for producing the same.

In order to improve the corrosion resistance of the metal material after painting, various chemical conversion treatment agents and substrate treatment agents have been developed. For example, Patent Document 1 proposes a technique relating to a solution composition of a metal surface treatment agent containing zirconium as a main component.

[Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-41077

[Summary of the Invention] [Problems to be Solved by the Invention] However, the metal material having the chemical conversion film obtained after the surface of the metal is treated with the solution composition described in Patent Document 1 is formed by coating. The film also does not exhibit sufficient corrosion resistance at the edge portion of the coated metal material; or the adhesion of the coating film is insufficient. Therefore, an object of the present invention is to provide a pretreatment agent capable of forming a chemical conversion treatment of a chemical conversion film, and a pretreatment method using a chemical conversion treatment using the pretreatment agent, which can improve the edge of the coating film. The burr is corrosion-resistant and can improve the adhesion between the film and the film.

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that it is possible to perform pretreatment by using a specific pretreatment agent before the chemical treatment on the surface or surface of the metal material. The burr portion in the edge of the metal material of the coating film formed after the chemical conversion treatment has good corrosion resistance, and has good adhesion to the coating film, thereby completing the present invention.

In other words, the present invention provides the following (I) to (VI). (I) A pretreatment agent for a metal material, which is a pretreatment for forming a chemical conversion film on a surface or a surface of a metal material, characterized in that the pretreatment agent is obtained by blending the following compounds The organic decane compound (A) having a primary amino group and an alkoxyalkyl group in the molecule; and an organodecane compound (B) having a glycidyl group and an alkoxyalkyl group in the molecule. (II) A method of pretreating a metal material, comprising: a pretreatment step of contacting a pretreatment agent as contained in the above (I) with a surface or a surface of a metal material. (III) A method for producing a metal material having a chemical conversion film, comprising: a pretreatment step of contacting a pretreatment agent as described in (I) above with a surface or a surface of a metal material; and forming a treatment The step of forming a chemical film on the surface of the metal material after the foregoing pretreatment step. (IV) A metal material having a chemical conversion film obtained by the production method as described in the above (III). (V) A method of producing a coated metal material, comprising: a coating step of coating a metal material as described in the above (IV). (VI) A coated metal material having a coating film on a surface of a metal material having a chemical conversion film as described in the above (IV).

[Effects of the Invention] According to the present invention, it is possible to provide a pretreatment agent capable of forming a chemical conversion treatment of a chemical conversion film, and a pretreatment method using a chemical conversion treatment using the pretreatment agent, and the techniques can improve the formation of the coating material. The burr of the edge of the film is corrosion-resistant, and the adhesion between the film and the coating film can be improved.

The pretreatment agent in the embodiment of the present invention is a pretreatment agent used for the treatment before the chemical conversion treatment, wherein the chemical conversion treatment forms a chemical conversion film on the surface or the surface of the metal material. The pretreatment agent is blended with an organodecane compound (A) having a primary amine group and an alkoxyalkyl group in the molecule; and an organodecane compound (B) having a glycidyl group and an alkyl group in the molecule. Oxyalkylene. Hereinafter, the pretreatment agent, the method for producing the same, the pretreatment method of the metal material based on the pretreatment agent, the chemical conversion treatment method after the pretreatment, and the metal material having the chemical conversion film formed by the chemical conversion treatment will be described in order. Wait. Further, the present invention can be arbitrarily changed within the scope of the invention, and is not limited to the following embodiments.

1. Pretreatment agent The pretreatment agent in the present embodiment is a mixture of an organic decane compound (A) having a primary amine group and an alkoxyalkyl group in a molecule as long as it is a liquid solvent; and an organic decane compound (B) is not particularly limited as long as it has a glycidyl group and an alkoxyalkyl group in the molecule, but other components may be further blended. Examples of the other components include an additive such as a pH adjuster, a ruthenium-containing compound to be described later, a surfactant which adjusts the wettability of the target, and a surfactant called an antifoaming agent.

Each of the organodecane compounds in the pretreatment agent may be in the form of the original form, or may be in the form of a hydrolyzed product obtained by hydrolyzing each organodecane compound. The hydrolyzed product may be in the form of a polycondensation polymer after condensation polymerization, or may be a copolymer of each hydrolyzate after copolymerization (alternating copolymer, random copolymer, block copolymer, graft copolymer) The form of (etc.) may also be mixed with a plurality of forms.

(Organic decane compound (A)) The organic decane compound (A) has a primary amino group and an alkoxyalkyl group in the molecule. The alkoxyalkyl group of the organodecane compound (A) is a group having a deuterium atom and an alkoxy group directly bonded to the deuterium atom, and preferably has a deuterium atom and at least two directly bonded to the deuterium atom. The alkoxy group is more preferably a group having a deuterium atom and at least 3 alkoxy groups directly bonded to the deuterium atom. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably a methoxy group or an ethoxy group. The alkoxyalkylene group may, for example, be dimethylmethoxydecylalkyl, methyldimethoxydecylalkyl, trimethoxydecylalkyl, diethylethoxycarbinyl or ethyl. Diethoxymethoxyalkyl, triethoxyalkyl, etc., but are not limited thereto.

The primary amine group may be directly bonded to the alkoxyalkyl group, or may be bonded to the alkoxyalkyl group by a carbon chain, an ether or a secondary amine group. Further, the organodecane compound (A) may have two or more primary amine groups in the molecule.

The organodecane compound (A) may, for example, be N-2-(aminoethyl)-3-aminopropyldimethylmethoxydecane or N-2-(aminoethyl)-3- Aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyldiethyl Oxydecane, N-2-(aminoethyl)-3-aminopropylethyldiethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3- Aminopropyl dimethyl methoxy decane, 3-aminopropyl methyl dimethoxy decane, 3-aminopropyl trimethoxy decane, 3-aminopropyl diethyl ethoxy decane, 3-amino Propyl ethyl diethoxy decane, 3-aminopropyl triethoxy decane, and the like. These compounds may be used alone or in combination of two or more. In the case of a combination of two or more kinds, for example, N-2-(aminoethyl)-3-aminopropyldimethylmethoxydecane and N-2-(aminoethyl)-3- can be mentioned. Aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyldimethylmethoxydecane and N-2-(aminoethyl)-3-aminopropyltrimethyl Oxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane and N-2-(aminoethyl)-3-aminopropyldiethylethoxydecane, N-2 -(aminoethyl)-3-aminopropyldiethylethoxydecane with N-2-(aminoethyl)-3-aminopropylethyldiethoxydecane, N-2-(aminoethyl) 3-aminopropylethyldiethoxydecane with N-2-(aminoethyl)-3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-amino Propyltriethoxydecane with 3-aminopropyldimethylmethoxydecane, 3-aminopropyldimethylmethoxydecane and 3-aminopropylmethyldimethoxydecane, 3-amino Propylmethyldimethoxydecane with 3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane and 3-aminopropyldiethylethoxydecane, 3-aminopropyldiethyl Ethyloxy Alkyl with 3-aminopropyl diethoxy silane-ethyl, 3-aminopropyl silane-diethoxy-ethyl and 3-aminopropyl triethoxysilane Silane;

N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane with N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl) 3-aminopropylmethyldimethoxydecane with N-2-(aminoethyl)-3-aminopropyldiethylethoxydecane, N-2-(aminoethyl)-3 -aminopropylmethyldimethoxydecane with N-2-(aminoethyl)-3-aminopropylethyldiethoxydecane, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxydecane with N-2-(aminoethyl)-3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Decane with 3-aminopropyldimethylmethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane and 3-aminopropylmethyldimethoxydecane , N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane with 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyl Dimethoxy decane with 3-aminopropyldiethyl ethoxy decane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane and 3-aminopropylethyl Diethoxydecane, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxydecane with 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane and N-2-(aminoethyl)-3 -aminopropyldiethylethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane and N-2-(aminoethyl)-3-aminopropylethyldi Ethoxy decane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane and N-2-(aminoethyl)-3-aminopropyltriethoxydecane, N-2- (Aminoethyl)-3-aminopropyltrimethoxydecane with 3-aminopropyldimethylmethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane and 3 -aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane with 3-aminopropyltrimethoxydecane, N-2-(aminoethyl -3-aminopropyltrimethoxydecane with 3-aminopropyldiethylethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane and 3-aminopropyl Ethyldiethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane and 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3 -aminopropyldiethyl Oxydecane with N-2-(aminoethyl)-3-aminopropylethyldiethoxydecane, N-2-(aminoethyl)-3-aminopropyldiethylethoxynonane N-2-(aminoethyl)-3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyldiethylethoxydecane and 3-aminopropyldi Methylmethoxydecane, N-2-(aminoethyl)-3-aminopropyldiethylethoxydecane and 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl) 3-aminopropyldiethylethoxydecane with 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyldiethylethoxydecane and 3 -aminopropyldiethylethoxydecane, N-2-(aminoethyl)-3-aminopropyldiethylethoxydecane and 3-aminopropylethyldiethoxydecane, N- 2-(Aminoethyl)-3-aminopropyldiethylethoxydecane with 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropylethyldi Ethoxy decane with N-2-(aminoethyl)-3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropylethyldiethoxydecane and 3 -aminopropyldimethylmethoxydecane, N 2-(Aminoethyl)-3-aminopropylethyldiethoxydecane with 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyl Ethyldiethoxydecane with 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylethyldiethoxydecane and 3-aminopropyldiethyl Oxydecane, N-2-(aminoethyl)-3-aminopropylethyldiethoxydecane and 3-aminopropylethyldiethoxydecane, N-2-(aminoethyl)- 3-aminopropylethyldiethoxydecane with 3-aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane and 3-aminopropyl Dimethylmethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane and 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl -3-aminopropyltriethoxydecane with 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane and 3-aminopropyldi Ethyl ethoxy decane, N-2-(aminoethyl)-3-aminopropyltriethoxy decane and 3-aminopropylethyldiethoxy decane, N-2-(aminoethyl) -3-aminopropyl triethyl Oxydecane and 3-aminopropyltriethoxydecane;

3-aminopropyldimethylmethoxydecane with 3-aminopropylmethyldimethoxydecane, 3-aminopropyldimethylmethoxydecane and 3-aminopropyltrimethoxydecane, 3 -aminopropyl dimethyl methoxy decane with 3-aminopropyl diethyl ethoxy decane, 3-aminopropyl dimethyl methoxy decane and 3-aminopropyl ethyl diethoxy decane 3-aminopropyldimethylmethoxydecane with 3-aminopropyltriethoxydecane, 3-aminopropylmethyldimethoxydecane and 3-aminopropyltrimethoxydecane, 3- Aminopropylmethyldimethoxydecane with 3-aminopropyldiethylethoxydecane, 3-aminopropylmethyldimethoxydecane and 3-aminopropylethyldiethoxydecane, 3-aminopropylmethyldimethoxydecane with 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane and 3-aminopropyldiethylethoxydecane, 3-amino Propyltrimethoxydecane with 3-aminopropylethyldiethoxydecane, 3-aminopropyltrimethoxydecane and 3-aminopropyltriethoxydecane, 3-aminopropyldiethylethyl Oxydecane and 3-aminopropylethyl Ethoxy decane, 3-aminopropyl diethyl ethoxy decane and 3-aminopropyl triethoxy decane, 3-aminopropyl ethyl diethoxy decane and 3-aminopropyl triethoxy Base decane, etc., but is not limited thereto.

(Organic decane compound (B)) The organic decane compound (B) has a glycidyl group and an alkoxyalkyl group in the molecule. The alkoxyalkyl group of the organodecane compound (B) is the same as the alkoxyalkyl group of the above organodecane compound (A).

The glycidyl group may be directly bonded to the alkoxyalkyl group, or may be bonded to the alkoxyalkyl group by a carbon chain, a cyclic carbon compound or an ether. Further, the organodecane compound (B) may have two or more glycidyl groups in the molecule.

The organodecane compound (B) may, for example, be 3-glycidylpropylmethyldimethoxydecane, 3-glycidylpropyldimethylmethoxydecane or 3-glycidyl group. Propyltrimethoxydecane, 3-glycidylpropylethyldiethoxydecane, 3-glycidylpropyldiethylethoxydecane, 3-glycidylpropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like. These compounds may be used alone or in combination of two or more. In the case of a combination of two or more kinds, for example, 3-glycidylpropylmethyldimethoxydecane and 3-glycidylpropyldimethylmethoxydecane, 3-glycidyl group are mentioned. Propylmethyldimethoxydecane with 3-glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane and 3-glycidylpropylethyldiethoxy Decane, 3-glycidylpropylmethyldimethoxydecane with 3-glycidylpropyldiethylethoxydecane, 3-glycidylpropylmethyldimethoxydecane and 3-shrinkage Glycerylpropyltriethoxydecane, 3-glycidylpropylmethyldimethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidylpropyl Dimethyl methoxy decane with 3-glycidyl propyl trimethoxy decane, 3-glycidyl propyl dimethyl methoxy decane and 3-glycidyl propyl ethyl diethoxy decane , 3-glycidylpropyl dimethyl methoxy decane with 3-glycidyl propyl diethyl ethoxy decane, 3-glycidyl propyl dimethyl methoxy decane and 3-glycol Propyltriethoxydecane, 3-glycidylpropyldimethylmethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidylpropyl Trimethoxy decane with 3-glycidyl propyl ethyl diethoxy decane, 3-glycidyl propyl trimethoxy decane and 3-glycidyl propyl diethyl ethoxy decane, 3-shrinkage Glycerylpropyltrimethoxydecane with 3-glycidylpropyltriethoxydecane, 3-glycidylpropyltrimethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 3-glycidylpropylethyldiethoxydecane with 3-glycidylpropyl diethylethoxydecane, 3-glycidylpropylethyldiethoxydecane and 3- Glycidylpropyltriethoxydecane, 3-glycidylpropylethyldiethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidyl Propyl diethyl ethoxy decane with 3-glycidylpropyl triethoxy decane, 3-glycidyl propyl diethyl ethoxy decane and 2-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane, 3-condensed Ole propyl triethoxy decane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, etc., but are not limited thereto.

In the pretreatment agent of the present embodiment, the blend ratio of the organodecane compound (A) to the organodecane compound (B) is not particularly limited, but the ratio of the primary amine group to the molar concentration of the glycidyl group is Preferably, it is blended in the range of 1.0: 9.0 to 9.0: 1.0, more preferably in the range of 2.0: 8.0 to 8.0: 2.0.

Further, in the pretreatment agent, the content of the organodecane compound (A) and the organodecane compound (B) is preferably 0.1 mmol/L or more, more preferably 0.5 mmol/%, based on the total of the oxime-converted Mohr concentration. L or more. Although the upper limit is not particularly limited, it is preferably 100 mmol/L or less from the viewpoint of cost.

(Other components) The other components include an antimony compound other than the organodecane compound (A) and the organodecane compound (B), and a surfactant which adjusts the wettability of the material to be treated, and is called defoaming. Surfactant and the like. Examples of the ruthenium-containing compound include tetramethyl ortho-nonanoate, tetraethyl ortho-decanoate, methyltrimethoxydecane, dimethyldimethoxydecane, trimethylmethoxydecane, and the like. Methyl ethoxy decane, dimethyl diethoxy decane, ethyl triethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, dimethyl ethoxy vinyl decane, two Ethoxymethyl vinyl decane, vinyl tris(2-methoxyethoxy) decane, dimethyl vinyl methoxy decane, vinyl iso propylene oxy decane, trimethoxy phenyl decane, three Ethoxyphenyl decane, dimethoxymethyl phenyl decane, dimethyl ethoxy phenyl decane, methyl phenyl diethoxy decane, diphenyl dimethoxy decane, diphenyl phenyl Oxymethyl decane, diphenyl diethoxy decane, and the like. These compounds may be used alone or in combination of two or more.

Although the pH of the treatment agent before the present embodiment is not particularly limited, it is usually 2.0 or more, preferably 3.0 or more, and is usually 12.0 or less, preferably 8.0 or less, more preferably 5.0 or less. When the pH is within this range, a chemical conversion film having more excellent corrosion resistance can be formed in the chemical conversion treatment step described later. Here, the pH of the present invention is a value measured for a pretreatment agent at 25 ° C using a pH meter. In order to adjust the pH of the pretreatment agent to this range, a pH adjuster can also be used. The pH adjusting agent which can be used when the pH is to be raised is not particularly limited, and examples thereof include an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, and ammonia water. On the other hand, the pH adjusting agent which can be used when the pH is lowered is not particularly limited, and examples thereof include carbonic acid gas, phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, lactic acid, formic acid, acetic acid, and citric acid. An acid such as tartaric acid or an alkane sulfonic acid; or an acid containing a metal component such as zirconium hydride or fluorinated titanium hydride. Further, these pH adjusting agents may be used alone or in combination of two or more.

The alkanesulfonic acid may, for example, be R-SO ₃ H (wherein R is an alkyl group or a hydroxyalkyl group). The alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkane sulfonic acid is not particularly limited, and examples thereof include methanesulfonic acid and ethanesulfonic acid.

The liquid solvent is not particularly limited, and is preferably water (deionized water or distilled water), but may be a water-miscible organic solvent containing less than 50% by weight of a lower alcohol.

Further, when the pretreatment of the metal material is carried out using the pretreatment agent of the present embodiment, the metal material may be dissolved and the metal component may be mixed into the pretreatment agent. Further, the pretreatment agent may contain a metal component containing iron (Fe), zinc (Zn), aluminum (Al), magnesium (Mg) or the like. Further, for example, zirconium (Zr), phosphorus (P) or the like may be mixed in the same manner, and it is a component which is inevitably mixed in the operation of the machine. These components may be inevitably incorporated into the pretreatment agent, or may be intentionally included in the pretreatment agent.

The method for producing the pretreatment agent is not particularly limited, and for example, the organodecane compound (A) and the organodecane compound (B) can be used as a raw material and blended into a liquid solvent. Make modulation.

(Pretreatment Method of Metal Material) Another embodiment of the present invention relates to a pretreatment method in which the pretreatment agent is brought into contact with a metal material. The pretreatment method comprises a pretreatment step of contacting the pretreatment agent of the embodiment of the present invention with the surface or surface of the metal material. In addition, the pretreatment method may also include water washing of the metal material performed after the pretreatment step. In addition, a degreasing treatment step may be included, which is performed before the pretreatment step, and is referred to as a degreasing treatment, that is, removing oil and deposits on the surface of the metal material. The degreasing treatment step is not particularly limited, and a conventional method can be applied. The water may be washed after the degreasing treatment step or may not be washed with water.

The contact method of the pretreatment agent may be a conventional contact method, and examples thereof include an immersion treatment method, a spray coating treatment method, a flow coating treatment method, or a treatment method in which these methods are combined. The contact of the pretreatment agent is preferably carried out at a specific temperature for a specific period of time. Although the contact temperature is usually 5° C. or higher and 60° C. or lower, preferably 10° C. or higher and 50° C. or lower, it is not limited thereto. Further, the contact time is usually 5 to 600 seconds, preferably 10 to 300 seconds, but is not limited thereto.

Another embodiment of the present invention relates to a method for producing a metal material having a chemical conversion film, which is characterized in that after the pretreatment agent is brought into contact with a surface or a surface of a metal material, a chemical conversion treatment step is further included. The metal material is formed into a film. Further, the present invention also relates to a metal material having a chemical conversion film obtained by the method. The chemical conversion treatment step is not particularly limited as long as it is a treatment for forming a chemical conversion film, and examples thereof include a zirconation treatment step, a titanation treatment step, a hydrazine formation treatment step, a vanadium formation treatment step, a ferric phosphate formation treatment step, and phosphoric acid. Zinc formation process steps and the like. The above various chemical conversion treatment steps may be performed in only one step, or may be performed in combination of two or more steps. Further, when two or more steps are combined, the water washing may be performed after various subsequent steps, or the water washing may not be performed, or a part of the water washing may be omitted. In addition, in the chemical conversion treatment step, when the zinc phosphate formation treatment step is performed, a surface adjustment treatment step may be applied to the metal material between the pre-treatment step and the zinc phosphate treatment step, the purpose of which is to increase zinc phosphate formation. The reactivity of the treatment. As the surface conditioning treatment method, a conventional method can be used. The treatment temperature or the contact time in the chemical conversion treatment step can be appropriately set according to the type of the chemical conversion treatment step, the concentration of the chemical conversion treatment agent, and the like.

According to still another aspect of the invention, there is provided a method of producing a coated metal material, comprising: a coating step of coating a surface of a metal material having the chemical conversion film. Further, the present invention relates to a coated metal material having a coating film which has a coating film on the surface of a metal material having a chemical conversion film obtained by the above-described production method. The coating method is not particularly limited and can be applied, for example, to roll coating, electroplating (for example, cationic plating coating), spray coating, thermal spray coating, airless spray coating, electrostatic coating (for example, electrostatic powder coating). Conventional methods such as roll coating, curtain coating, brush coating, bar coating, and flow impregnation. Further, after the coating step, a drying step (including a baking step and/or a curing step) may be performed to dry the coating on the surface of the coated metal material. Further, before the coating step, the surface of the metal material having the chemical conversion film may be washed or not washed with water. Further, the surface of the metal material after washing or not washing may be dried or not dried before the coating step.

Examples of the coating material include an oil-based paint, a cellulose-inducing paint, a phenol resin paint, an alkyd resin, an amino alkyd resin, a urea resin paint, an unsaturated resin paint, a vinyl paint, an acrylic paint, Conventional coatings such as epoxy resin coatings, polyurethane resin coatings, enamel resin coatings, fluororesin coatings, rust-proof coatings, antifouling coatings, powder coatings, cationic plating coatings, anionic coatings, waterborne coatings, solvent coatings, and the like . Further, the coating step may be the same or different coating materials, and may be applied once or twice or more. Further, the drying step is a treatment for drying and curing the coated paint. Examples of the drying method include natural drying, reduced-pressure drying, and convection type thermal drying (for example, natural convection type heat drying, forced convection type heat drying), and radiation type drying (for example, near-infrared drying, far infrared ray). Drying method, ultraviolet curing drying, electron beam curing drying, vapocure type, baking drying, and the like. In addition, one type of these drying methods may be used, or two or more types may be combined.

For the above cation plating coating, a conventional method can be applied. For example, a method of immersing a metal material having a chemical conversion film in a coating material, and the like, and a cationic plating coating material containing an amine addition epoxy resin and a blocked polyisocyanate curing agent as a curing component can be used as the coating material. The cation plating coating is performed, for example, by maintaining the temperature of the coating material at a specific temperature and stirring the coating material, and applying a voltage to the metal material having the chemical conversion film in the cathode direction by using a rectifier. The metal material which is subjected to cationic plating in this manner can be formed into a coating film by chemical washing and baking. Baking is performed for a specific time within a specific temperature range. Specifically, it was carried out at 170 ° C for 20 minutes. Further, in the case where a cation plating coating method using a cation plating coating is applied, the sodium ion concentration is based on the sodium ion concentration in the treating agent used in the degreasing step, the pretreatment step, various chemical conversion treatment steps, and the like as a quality standard. And preferably controlled to less than 500 ppm.

A conventional method can be applied to a coating method using a spray coating, an electrostatic powder coating, a flow impregnation method, or the like of a powder coating material. The powder coating material includes, for example, a polyester resin, a blocked isocyanate curing agent as a curing agent, and a β-hydroxyalkylguanamine-based curing agent (for example, refer to Japanese Patent Laid-Open Publication No. 2011-88083), or It is a tri-epoxypropyl isocyanurate. Baking is performed at a specific temperature range for a specific period of time. Specifically, for example, it is carried out at 150 to 250 ° C for 20 minutes.

A conventional method can be applied to a coating method such as spray coating, electrostatic coating, or roller coating using the solvent coating. The solvent coating material may, for example, be a resin such as a melamine resin, an acrylic resin, an amino resin or a polyester resin; or an organic solvent such as a diluent. Baking can be performed for a specific time in a specific temperature range. Specifically, for example, it is carried out at 130 ° C for 20 minutes.

The coating film obtained by the coating step may be a single layer or a plurality of layers. In the case of a plurality of layers, the coating materials used for forming various coating films, the coating method using the coating materials, and the drying method of the metal material after coating may be the same or different.

In the present embodiment, the type of the metal material that can be used as the object of the pretreatment step is not particularly limited. Examples thereof may include: steel materials (for example, cold rolled steel sheets, hot rolled steel sheets, high tensile steel sheets, tool steels, alloy tool steels, spheroidized black lead irons, gray iron, etc.); plating materials such as galvanized materials. (Example: electro-galvanized, galvanized, etc.), galvanized alloy materials (for example: alloyed melt galvanized, galvanized (Zn)-aluminum (Al) alloy, galvanized (Zn)-aluminum (Al)-magnesium ( Mg) alloy, electrogalvanized alloy), aluminized material, etc.; aluminum material or aluminum alloy material (for example: 1000 type, 2000 type, 3000 type, 4000 type, 5000 type, 6000 type, aluminum casting, aluminum alloy casting, die casting) Materials, etc.); magnesium materials or magnesium alloy materials.

A metal material having a chemical conversion film can be produced by a method for producing a metal material having the above-described chemical conversion film. The chemical conversion film may, for example, be a zirconium-forming film, a titaniumized film, a bismuth film, a vanadium-forming film, a ferric phosphate film, or a zinc phosphate film. The chemical conversion film may be one layer or more than two layers. Here, in the formation of a zirconium-forming film, a titaniumized film, a bismuth film, and/or a vanadium film, the zirconium in the film is formed in accordance with the unit area of the surface of the metal material in terms of the quality of the formed film. The mass of titanium, niobium or vanadium is preferably 5 mg/m ² or more and 500 mg/m ² or less, more preferably 10 mg/m ² or more and 250 mg/m ² or less, but is not limited by this range. When the chemical conversion film contains two or more metal elements, the total amount thereof is preferably within the above range. On the other hand, when the iron phosphate is formed into a film, the quality of the film is preferably 0.1 g/m ² in terms of phosphorus in terms of the conversion per unit area of the surface of the metal material to phosphorus in the film. The above is 2.0 g/m ² or less, more preferably 0.2 g/m ² or more and 1.5 g/m ² or less, but is not limited to this range. When the zinc phosphate is formed into a film, the mass of the film is preferably 0.5 g/m ² or more and 10 g/m ² or less, more preferably 1.0 g/m ² with respect to the surface area per unit area of the metal material. The above is 7.0 g/m ² or less, but is not limited by this range.

The content of zirconium, titanium, hafnium or vanadium in the chemical conversion film formed by zirconization into a film, a titaniumized film, a bismuth film, a vanadium film, or the like can be obtained by inductively coupling plasma after being dissolved into a film by concentrated nitric acid ( Inductively Coupled Plasma (ICP) luminescence spectroscopic analysis was performed. On the other hand, in the case where the phosphoric acid is ferro-formed into a film or zinc phosphate is formed into a film or the like, it can be calculated by using only a chromic acid aqueous solution to dissolve the film into a film, and the difference in weight per unit area before and after the dissolution. Further, a metal material having a chemical conversion film can be measured by a fluorescent X-ray method and analyzed.

The coated metal material can be produced by the above-described method of producing a coated metal material. Here, the coating film formed on the coated metal material may be a single layer or a plurality of layers. When it is a plurality of layers, the conditions of the coating, the coating method, and the drying method of each layer may be the same or different. Further, the thickness of the coating film may be as thick as more than 100 μm, or may be thinner than 5 μm. For example, in the case of electroplating, although the coating is generally about 10 to 30 μm thick, it may be thickened to 100 μm or may be thinned to 3 μm.

[Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. Further, the present invention is not limited to the following embodiments.

[Production of coated metal material] <Metal material> As the metal material, a cold-rolled soft steel sheet (SPCC: thickness: 0.8 mm) specified in JIS G3141 and a molten galvanized steel sheet (SGCC: thickness: 0.8 mm) specified in JIS G3302 are used. The same is the alloyed molten galvanized steel sheet (GA: thickness: 0.8 mm) specified in JIS G3302; the electrogalvanized steel sheet (SECC: thickness: 0.8 mm) specified in JIS G3313; and the hot-rolled soft steel sheet specified by JIS G3131 (SPHC: The aluminum alloy plate (A6061: thickness: 0.8 mm) specified in JIS H4000 and the alloyed molten galvanized steel sheet (SCGA: thickness: 0.8 mm) specified in JIS G3302, respectively, are cut to a length of 70 mm × 150mm wide. At this time, a burr is generated at the edge portion of the metal material. The surface on which the burrs were raised was used as the surface for evaluation. The height of the burrs is approximately 100 μm.

<Degreasing treatment for metal material> The above metal material was immersed in a 24 g/L aqueous solution of an alkaline degreaser (trade name: Fine Cleaner E2093, manufactured by Nihon Parkerizing Co., Ltd.) at 45 ° C for 2 minutes to remove the metal. Oil and dirt on the surface of the material. Thereafter, the surface of the metal material is washed with pure water.

<Preparation of Pretreatment Agent> As shown in Table 1, after each component is added to water so that each component has a specific molar concentration, it is adjusted to a specific pH value by using methanesulfonic acid or an aqueous sodium hydroxide solution. The pretreatment agents of Examples 1 to 25 and Comparative Examples 1 and 2 were prepared. Further, as the organodecane compounds (A) and (B) blended in the pretreatment agent, the following seven components were used. Further, the following ingredients were used as the ingredients to be mixed. Further, the unit of the addition amount described in Table 1 is mmol/L. A1: N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane (Shin-Etsu Chemical Co., Ltd. KBM-602) A2: N-2-(aminoethyl)-3-amino Propyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd. KBM-603) A3: 3-Aminopropyltrimethoxydecane (Shin-Etsu Chemical Co., Ltd. KBM-903) A4: 3-Aminopropyltriethoxy Decane (Shin-Etsu Chemical Co., Ltd. KBE-903) B1: 3-glycidylpropylmethyldimethoxydecane (Shin-Etsu Chemical Co., Ltd. KBM-402) B2: 3-glycidylpropyltrimethoxy Base decane (Shin-Etsu Chemical Co., Ltd. KBM-403) B3: 3-glycidylpropyl triethoxy decane (Shin-Etsu Chemical Co., Ltd. KBE-403) Mixed iron (Fe): ferric nitrate (III) Nine Hydrate (Pure Chemical Co., Ltd., reagent, specification grade, iron oxidation number is 3) Aluminum (Al) mixed with components: aluminum nitrate nonahydrate (Pure Chemical Co., Ltd., reagent, specification level 1) Zinc (Zn) mixed with components: zinc nitrate hexahydrate (Pure Chemical Co., Ltd., reagent, specification level 1)

[Table 1]: Preparation of pretreatment agent

As shown in Table 2, various metal materials to which the above-described degreasing treatment was applied were subjected to the following pretreatments, various chemical conversion treatments, plating treatments, and the like, and various coating metal materials were produced. The details are as follows. <Pretreatment for Metal Material> Various metal materials (SPCC, SGCC, GA, SECC, SPHC, A6061, and SCGA) to which the above degreasing treatment was applied were immersed in the conditions shown in Table 1 at 25 ° C for 30 seconds. Various pretreatment agents (pretreatment agents of Examples 1 to 25 and Comparative Examples 1 and 2) were pretreated.

<Preparation of Chemical Treatment Treatment Agent> For the chemical conversion treatment agent, a general zirconation treatment agent, a titanium chemical conversion treatment agent, a hydrazine chemical conversion treatment agent, a vanadium chemical conversion treatment agent, a ferric phosphate chemical conversion treatment agent, and a zinc phosphate chemical conversion treatment agent are used.

<Zirconium formation treatment: Zr> Various metal materials which have been pretreated or various metal materials which have only been subjected to degreasing treatment are immersed in a zirconium forming treatment liquid at 40 ° C for 120 seconds (Pallcid 1500, Nihon Parkerizing Limited Co., Ltd. A 50 g/L aqueous solution prepared by the company was used to produce a metal material having a zirconium formed film.

<Titanization Treatment: Ti> The SPCC treated before the treatment agent before the use of Example 6 or the SPCC which was only subjected to the degreasing treatment was immersed in titanium hexafluorotitanate at 40 ° C for 120 seconds. A chemical conversion treatment agent prepared by mass concentration of 0.1 g/kg was used to prepare a metal material having a titaniumized film.

<铪化化处理:Hf> The SPCC which was treated before the treatment agent before the use of Example 6 or the SPCC which was only subjected to the degreasing treatment was immersed in the ruthenium hexafluoroantimonate in terms of metal ruthenium at 40 ° C for 120 seconds. A chemical conversion treatment agent prepared by mass concentration of 0.1 g/kg was used to prepare a metal material having a deuterated film.

<Vanadium Chemical Treatment: V> The SPCC treated before the treatment agent before the use of Example 6 or the SPCC which was only subjected to the degreasing treatment was immersed in Ammonium metavanadate at 40 ° C for 120 seconds. A chemical conversion treatment agent prepared by converting a metal vanadium into a mass concentration of 0.1 g/kg to prepare a metal material having a vanadium chemical conversion film.

<Iron Phosphate Formation Treatment: P-Fe> 50 g/L was sprayed on the surface of SPCC treated before the treatment agent before Example 6 or SPCC which was only subjected to degreasing treatment at 50 ° C for 120 seconds. An aqueous solution of a ferric phosphate-forming treatment liquid (Parhos 1077, manufactured by Nihon Parkerizing Co., Ltd.) was prepared to prepare a metal material having a ferrite phosphate film.

<Zinc Phosphate Formation Treatment: P-Zn> The SPCC which was treated before the treatment agent before the use of Example 6 or the SPCC which was only subjected to the degreasing treatment was immersed in a surface of 3 g/L at 25 ° C for 30 seconds. After the aqueous solution of the treatment liquid (prepalene-X, manufactured by Nihon Parkerizing Co., Ltd.) was immersed in a 50 g/L zinc phosphate chemical conversion treatment solution (Palbond X; manufactured by Nihon Parkerizing Co., Ltd.) at 35 ° C for 120 seconds. An aqueous solution to produce a metal material having zinc phosphated into a film.

<Electroplating coating treatment for a metal material having a chemical conversion film> Water-washing with pure water After various chemical treatments, a metal material having a chemical conversion film is used, and various metal materials are used as a cathode, and a cationic plating coating is used (GT-100, Kansai) Paint Co., Ltd.) was subjected to constant voltage cathodic electrolysis for 180 seconds to analyze the coating film to the entire surface of the metal material. Thereafter, the mixture was washed with pure water and baked at 170 ° C (PMT: the highest temperature of the metal material at the time of baking) for 20 minutes to prepare coated metal materials No. 1 to No. 49, and the following evaluations were carried out. Further, the coating film thickness of the coated metal material was adjusted to 20 μm.

[Table 2]: Production of coated metal materials

[Evaluation of Coating Metallic Material] <Corrosion Resistance> In order to confirm the corrosion resistance of the burrs at the edges of the respective coated metal materials No. 1 to No. 49 prepared above, each of the coated metal materials was placed in a composite cycle. The test machine was subjected to a compound cycle test of 100 cycles in accordance with the standard of JASO-M609-91. After 100 cycles, the maximum expansion width from the burrs generated at the time of cutting was measured, and the edge burr resistance was evaluated in accordance with the following evaluation criteria. Further, since the burrs of the edges were evaluated, the edges and the inner sides of the various painted metal materials were not sealed with tape. The results are shown in Table 3. (Evaluation Criteria) S: Maximum expansion width is less than 1.5 mm (optimal) A: Maximum expansion width is 1.5 mm or more and less than 2.5 mm B: Maximum expansion width is 2.5 mm or more and less than 5.0 mm C: Maximum expansion width is 5.0 Above mm

<Coating film adhesion> In order to confirm the coating film adhesion of each of the coated metal materials No. 1 to No. 49, a checkerboard-shaped cut mark (10 × 10 = 100) was applied to each of the coated metal materials at intervals of 1 mm. Thereafter, it was immersed in boiling water for 1 hour. Next, the moisture on the surface was wiped off, and after the cellophane tape was attached to the checker-shaped cut mark, the cellophane tape was peeled off, and the number of the coating film of the 1 mm square which was not peeled off from the coated metal material was measured, and evaluated according to the following evaluation criteria. Adhesion of the coating film. The results are shown in Table 3. In addition, the missing edge referred to herein means that the coating film of the 1 mm square is not completely peeled off, but a part is peeled off. (Evaluation criteria) S: The number of uncoated films is 100 (no missing edges) (optimal) A: The number of uncoated films is 100 (with missing edges) B: The number of uncoated films is 90 99 (without missing edges) C: The number of uncoated films is less than 90 (no missing edges)

<Electroplating and Coating Plating Force> As an alternative to the plating coating treatment in the above-mentioned coating metal materials No. 1 to No. 30 and No. 37 to No. 44, the following plating coatings were subjected to the plating force test to form a coating film. And the obtained coated metal material was used to evaluate the plating force of the plating coating. Four kinds of metal materials having various chemical conversion films are used, and electroplating coating is carried out in accordance with a four-box-based electroplating coating method (for example, refer to paragraphs 0085 to 0090 of JP-A-2010-90409). All plating test. In the implementation, as the counter electrode, a 70×150×0.5 mm stainless steel plate (SUS304) which was sealed with an insulating tape on one side (the reverse side of the opposing faces of the four sheets) was used. Further, the liquid level of the plating coating was adjusted to a four-piece cassette, and the evaluation surface of the metal material which formed the film and the position which the surface of the opposite electrode was immersed were immersed. The temperature of the plating coating was maintained at 30 ° C, and the plating coating was stirred with a mixer.

In this state, the coating film was electrically analyzed on the surface of the metal material having the chemical conversion film in the four-piece cassette by the cathodic electrolysis method using the opposite electrode as the anode. The specific electrolysis conditions were: using a rectifier and performing cathodic electrolysis for 180 seconds at a specific voltage. The voltage system was adjusted so that the thickness of the coating film on the surface facing the counter electrode was 15 μm in the metal material having the closest film from the opposite electrode of the four-piece cassette. Next, after washing each of the metal materials, the baking film was baked for 20 minutes under conditions of a PMT of 170 ° C to form a coating film to produce a coated metal material.

Next, an electromagnetic film thickness meter was used to measure the thickness of the coating film formed on the opposite electrode side of the metal material having the film formation farthest from the counter electrode. The film thickness is measured by measuring the thickness of the coated metal material at any of 10 places and calculating the average value of the film thickness. Thereafter, the uniform plating force of the electroplating coating is a coating film thickness (T ₁ ) formed on the opposite electrode side of the metal material having the chemical conversion film closest to the opposite electrode; and the chemical film having the farthest distance from the opposite electrode The ratio (T ₂ /T ₁ ) of the coating film thickness (T ₂ ) formed on the thickness of the coating film formed on the side opposite to the electrode surface of the metal material was calculated as a percentage. The plating plating was evaluated for the plating rate in accordance with the following evaluation criteria. The results are shown in Table 3. (Evaluation criteria) A: Electroplating uniformity is 65% or more (optimal) B: Electroplating uniformity is 50% or more and less than 65% C: Electroplating uniformity is less than 50%

Further, among all the evaluations, the evaluation criteria are B or more and are actually usable ranges.

[Table 3]: Evaluation of coated metal materials

Claims (6)

A pretreatment agent for a metal material for pre-treatment for forming a chemical conversion film on a surface or a surface of a metal material, characterized in that the pretreatment agent is obtained by blending the following compounds: The organodecane compound (A) having a primary amino group and an alkoxyalkyl group in the molecule; and an organodecane compound (B) having a glycidyl group and an alkoxyalkyl group in the molecule. A method of pretreating a metal material, comprising: a pretreatment step of contacting a pretreatment agent as claimed in claim 1 with a surface or a surface of a metal material. A method for producing a metal material having a chemical conversion film, comprising: a pretreatment step of contacting a pretreatment agent as claimed in claim 1 with a surface or a surface of a metal material; and a chemical conversion treatment step After the aforementioned pretreatment step, a chemical conversion film is formed on the surface of the metal material. A metal material having a chemical conversion film obtained by the production method according to claim 3. A method of producing a coated metal material, comprising: a coating step of coating a metal material as claimed in claim 4; A coated metal material having a coating film on a surface of a metal material having a chemical conversion film as described in claim 4.