JP2019081940A - Chemical conversion coating agent, method for producing chemical coating, metallic material having chemical coating, and coating metallic material - Google Patents

Abstract

To provide a chemical conversion coating agent capable of forming a chemical coating having excellent corrosion resistance on a surface of a metallic material.SOLUTION: This invention relates to a chemical conversion coating agent for producing a chemical coating on a surface of a metallic material, containing an ion supply source containing a metal selected from titanium, zirconium and hafnium, a supply source of fluorine ions, a silane coupling agent (I) containing an amino group, a silane coupling agent (II) containing a glycidyl group, and a water-soluble or water-dispersible polymer having a constitutional unit represented by a formula (i), where, the polymer is a homopolymer, and a mass ratio in contents between the silane coupling agent (I) and the silane coupling agent (II) [(I)/(II)] is 0.10-9.00.SELECTED DRAWING: None

Description

  The present invention relates to a chemical conversion treatment agent for producing a chemical conversion film on the surface or surface of a metal material, a method for producing a chemical conversion film using the chemical conversion treatment agent, a metal material having a chemical conversion film produced by the production method, and The present invention relates to a coated metal material having a chemical conversion film and a coating film.

  Heretofore, a treatment liquid for metal surface treatment has been developed which is capable of giving a surface treatment which is excellent in corrosion resistance and favorable in electrodeposition coating-related rolling property. For example, Patent Document 1 discloses at least one metal (A) selected from the group consisting of copper, tin and cobalt, and at least one metal (B) selected from the group consisting of zirconium and titanium. There is disclosed a treatment liquid for metal surface treatment having a predetermined amount of a predetermined water-soluble polymer (C).

JP, 2010-163640, A

  An object of the present invention is to provide a chemical conversion treatment agent etc. which can manufacture a chemical conversion film excellent in corrosion resistance on the surface or surface of a metallic material.

  MEANS TO SOLVE THE PROBLEM As a result of repeating earnest research in order to solve the said subject, the present inventors contain the source of the ion containing the metal chosen from titanium, a zirconium, and hafnium, the source of a fluorine ion, and an amino group. A chemical conversion treatment agent containing a predetermined amount of a silane coupling agent (I), a glycidyl group-containing silane coupling agent (II), and a specific water-soluble or water-dispersible polymer has corrosion resistance It has been found that an excellent chemical conversion film can be produced, and the present invention has been completed.

The present invention includes the following.
[1] A chemical conversion treatment agent for producing a chemical conversion film on the surface or surface of a metal material,
Source of ion containing metal selected from titanium, zirconium and hafnium, source of fluorine ion, silane coupling agent (I) containing amino group, and silane coupling agent containing glycidyl group (II) And water-soluble or water-dispersible polymers having a structural unit represented by the following formula (i):
The polymer is a homopolymer,
The chemical conversion treatment agent whose compounding quantity of the said silane coupling agent (I) and silane coupling agent (II) is in the range of 0.10-9.00 in mass ratio [(I) / (II)].
[2] The chemical conversion treatment agent according to the above [1], further including a source of an ion containing a metal selected from aluminum, magnesium and zinc.
[3] The chemical conversion treatment agent according to the above [1] or [2], which further comprises a nitrate ion source.
[4] A method for producing a chemical conversion film on the surface or surface of a metal material, wherein the chemical conversion treatment agent according to any one of the above [1] to [3] is brought into contact with the surface or surface of the metal material A contacting step.
[5] A metal material having a chemical conversion film, which is obtained by the method described in [4] above.
[6] A coated metal material having a coating film on the surface of the metal material having a chemical conversion film according to the above [5].

ADVANTAGE OF THE INVENTION According to this invention, the chemical conversion treatment agent which can form the chemical conversion film excellent in corrosion resistance on the surface or surface of a metal material can be provided. Also, a method for producing a chemical conversion film on the surface or surface of a metal material using the chemical conversion treatment agent, a metal material having a chemical conversion film produced by the production method, and a coated metal having the chemical conversion film and a coating film Materials can also be provided.
In addition, the chemical conversion treatment agent provided in the present invention can form a favorable chemical conversion film regardless of the type of the target metal material, even if it is a metal material that has conventionally been considered difficult to form a chemical conversion film. Can.

The chemical conversion treatment agent according to the embodiment of the present invention comprises a source A of an ion containing a metal selected from titanium, zirconium and hafnium, a source B of a fluorine ion, and a silane coupling agent containing an amino group (I ), A silane coupling agent (II) containing a glycidyl group, and a water-soluble or water-dispersible polymer (monopolymer) having a structural unit represented by the following formula (i) It mixes it. By using such a chemical conversion treatment agent, a chemical conversion film excellent in corrosion resistance can be produced on the surface or surface of the metal material. The chemical conversion treatment agent according to the present embodiment is one in which only the aqueous medium, the supply source A, the supply source B, the silane coupling agent (I), the silane coupling agent (II) and the predetermined polymer are blended. It may be present or may be further blended with other components.

(Source A)
The chemical conversion treatment agent according to the present embodiment contains a supply source A. The source A is particularly limited as long as it is a compound capable of providing an ion containing a metal selected from titanium, zirconium and hafnium (hereinafter simply referred to as “ion A”) when mixed in an aqueous medium. It is not a thing. Therefore, the chemical conversion treatment agent according to the present embodiment contains the ion A. Examples of the ion A include metal ions such as titanium ions, zirconium ions and hafnium ions; complex ions containing titanium, zirconium or hafnium; oxide ions of titanium, zirconium or hafnium;
Specific examples of the source A capable of providing the ion A include hexafluorotitanic acid, titanium nitrate, titanyl nitrate, titanium hydroxide, titanium oxide, hexafluorozirconic acid, zirconium nitrate, zirconyl nitrate, zirconium carbonate, zirconium hydroxide, Examples thereof include zirconium oxide, hexafluorohafnium acid, hafnium nitrate, hafnium oxide and the like, and when they can be in the form of a salt, they may be salts thereof. Although these sources may mix only 1 type, you may mix 2 or more types.
The ion A concentration in the chemical conversion treatment agent is not particularly limited, but it is usually 5 mg / L or more as a metal equivalent mass concentration (when two or more types of supply sources are blended, it means a total metal equivalent mass concentration). Preferably, it is 10 mg / L or more, and usually 10000 mg / L or less, preferably 5000 mg / L or less. After forming a chemical conversion film using the chemical conversion treatment agent whose ion A concentration is in the above range, a film having better corrosion resistance can be formed by forming a coating film.

(Source B)
Supply source B is blended with the chemical conversion treatment agent according to the present embodiment. The source B is not particularly limited as long as it is a compound capable of providing a fluorine ion when mixed in an aqueous medium (hereinafter, referred to as "a fluorine-containing compound"). Therefore, the chemical conversion treatment agent according to the present embodiment contains a fluorine ion. Fluorine ions may be supplied by blending a source of ion A (which is also applicable to a fluorine-containing compound) such as hexafluorozirconate, hexafluorotitanate, hexafluorohafnate, etc. You may supply by mix | blending fluorine-containing compounds other than the source of A, and you may supply by mix | blending the source of ion A and other fluorine-containing compounds.
As the fluorine-containing compound, in addition to hexafluorozirconic acid, hexafluorotitanic acid, hexafluorohafnium acid and the like, for example, hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride, germanium fluoride, germanium fluoride, potassium fluoride, fluoride Examples thereof include, but are not limited to, hydrogen potassium, iron fluoride, sodium fluoride and sodium hydrogen fluoride. When a chemical conversion treatment agent is prepared using a compound containing fluorine, such as hexafluorozirconic acid, hexafluorotitanic acid, hexafluorohafnium acid, etc., from zirconium, titanium and hafnium, It is possible to provide ions containing the selected metal and fluorine ions. In addition, various fluorine-containing compounds may be blended alone or in combination of two or more.
The fluorine ion concentration in the chemical conversion treatment agent is not particularly limited, but the fluorine conversion molar concentration is preferably more than 4 times and more than 6 times the total of the metal conversion molar concentrations of titanium, zirconium and hafnium. Is more preferred.

(Silane coupling agent)
The chemical conversion treatment agent according to this embodiment contains a silane coupling agent (I) containing an amino group and a silane coupling agent (II) containing a glycidyl group. Each silane coupling agent in the chemical conversion treatment agent may be in the form as it is, or may be in the form of a hydrolyzate obtained by hydrolysis of the silane coupling agent, or the hydrolyzate is condensation-polymerized. It may be in the form of a polycondensation product, or in the form of a copolymer (an alternating copolymer, a random copolymer, a block copolymer, a graft copolymer, etc.) in which the respective hydrolysates are copolymerized. A plurality of forms may be mixed.
As a silane coupling agent (I) containing an amino group, for example, 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 Silane, 3-aminopropyldiethylethoxysilane, 3 Aminosilane compounds such as aminopropyl ethyl diethoxy silane.
Moreover, as a silane coupling agent (II) containing glycidyl group, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Epoxysilane compounds such as trimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylethyldiethoxysilane, 3-glycidoxypropyldiethylethoxysilane, 3-glycidoxypropyltriethoxysilane It can be mentioned.

The compounding amount of the silane coupling agent (I) and the silane coupling agent (II) in the chemical conversion treatment agent is not particularly limited, but the total mass concentration of these is usually 100 mg / L or more, preferably 200 mg / L or more And is usually 2000 mg / L or less, preferably 1000 mg / L or less. After forming a chemical conversion film using the chemical conversion treatment agent in which the total blending amount of these silane coupling agents falls within the above range, a film having better corrosion resistance can be formed by forming a coating film.
The compounding amount of the silane coupling agent (I) and the silane coupling agent (II) is usually in the range of 0.10 to 9.00 in mass ratio [(I) / (II)], and 0. 0. It is preferably in the range of 25 to 4.00, and more preferably in the range of 0.54 to 1.86.

(Water-soluble or water-dispersible polymer)
The chemical conversion treatment agent according to the present embodiment includes a water-soluble or water-dispersible polymer (hereinafter simply referred to as "polymer"). The polymer is not particularly limited as long as it is a homopolymer having a constitutional unit represented by the above formula (i). Specifically, a diallylamine polymer; a diallylamine hydrochloride polymer, a diallylamine sulfate Polydiallylamines such as polymers, salts of diallylamine polymers such as diallylamine acetate polymers, and the like; and the like.

The degree of polymerization of the polymer is not particularly limited, but the weight average molecular weight is usually 200 or more, preferably 500 or more, and usually 100,000 or less, preferably 50,000 or less. The weight average molecular weight is a value measured by GPC (gel permeation column chromatography) and converted to polystyrene.
The content (blending amount) of the polymer in the chemical conversion treatment agent is not particularly limited, but it is usually 1 mg / L or more, preferably 5 mg / L or more, and usually 500 mg / L or less, preferably 200 mg as solid content mass concentration. It is less than / L.

(Aqueous medium)
The aqueous medium is not particularly limited as long as it is water or a mixture of water and a water-miscible organic solvent (containing 50% by volume or more of water based on the volume of the aqueous medium). The water-miscible organic solvent is not particularly limited as long as it is miscible with water, and, for example, ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N'-dimethylformamide and dimethylacetamide Alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone Can be mentioned. One of these water-miscible organic solvents may be mixed with water, or two or more may be mixed with water.

(Other ingredients)
As other components, for example, known additives used for a chemical conversion treatment agent such as a source C of an ion containing a metal selected from aluminum, magnesium and zinc, a source D of a nitrate ion, and a pH adjuster Although it can mention, it is not limited to these. In addition, these other components may be included in the range which does not inhibit the effect of this invention.

(Source C)
The supply source C may be mix | blended with the chemical conversion treatment agent which concerns on this embodiment. The source C is particularly limited as long as it is a compound capable of providing an ion containing a metal selected from aluminum, magnesium and zinc (hereinafter simply referred to as “ion C”) when mixed in an aqueous medium. It is not a thing. Therefore, the chemical conversion treatment agent according to the present embodiment may further contain the ion C. Examples of the ion C include metal ions such as aluminum, magnesium and zinc; complex ions including aluminum, magnesium, zinc and the like; and the like. Specific examples of the source C include aluminum hydroxide, aluminum nitrate, aluminum sulfate, zinc oxide, zinc hydroxide, zinc sulfate, zinc nitrate, magnesium nitrate, magnesium hydroxide, magnesium oxide, magnesium chloride, magnesium sulfate and the like. Be Although these sources may mix only 1 type, you may mix 2 or more types. The combination of two or more species is not particularly limited. For example, a combination of aluminum ion and magnesium ion, a combination of aluminum ion and zinc ion, a combination of magnesium and zinc ion, aluminum ion and magnesium ion And combinations of zinc ions and zinc ions.
The ion C concentration in the chemical conversion treatment agent is not particularly limited, but it is usually 1 mg / L or more as a metal equivalent mass concentration (when two or more kinds of supply sources are blended, it means a total metal equivalent mass concentration). Preferably, it is 5 mg / L or more, and usually 50000 mg / L or less, preferably 10000 mg / L or less. After forming a chemical conversion film using the chemical conversion treatment agent whose ion C concentration is in the above range, a film having better corrosion resistance can be formed by forming a coating film.

(Source D)
The supply source D may be mix | blended with the chemical conversion treatment agent which concerns on this embodiment. The source D is not particularly limited as long as it is a compound capable of providing nitrate ions when mixed in an aqueous medium. Therefore, the chemical conversion treatment agent according to the present embodiment may contain a nitrate ion.
The nitrate ion may be supplied by blending a source of ion C such as aluminum nitrate, zinc nitrate, magnesium nitrate or the like, or a nitrate other than the source of the ion C, or nitric acid. It may be supplied by blending the source of the ion C and other nitrates, nitric acid and the like. One of these sources may be blended, or two or more thereof may be blended.
The nitrate ion concentration in the chemical conversion treatment agent is not particularly limited, but it is usually 500 mg / L or more as the nitric acid equivalent mass concentration (when two or more kinds of supply sources are blended, it means the total nitric acid equivalent mass concentration). Preferably, it is 1000 mg / L or more, and usually 50000 mg / L or less, preferably 30000 mg / L or less.

(PH of chemical conversion treatment agent)
Although the pH of the chemical conversion treatment agent according to the present embodiment is not particularly limited, it is generally in the acidic to neutral range, and specifically, the pH is preferably in the range of 2.0 to 8.0, and 3. It is more preferably in the range of 0 to 6.0, and particularly preferably in the range of 3.5 to 4.5. Here, the pH value in the present specification means a value measured at 40 ° C. using a pH meter.
The pH of the chemical conversion treatment agent is, for example, an acid component such as hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, boric acid, organic acid, etc .; lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, Although it can adjust using pH adjusters, such as alkaline components, such as barium hydroxide, an alkali metal salt, ammonia, ammonium salt, amines, it is not restrict | limited to these components. In addition, you may use 1 type, or 2 or more types of pH adjusters.

(Method of producing chemical conversion treatment agent)
The chemical conversion treatment agent according to the present embodiment includes a source A, a source B, and a silane coupling agent (I
And the silane coupling agent (II) and a predetermined polymer as raw materials, and can be manufactured by blending a predetermined amount in an aqueous medium. The compounding of the silane coupling agents (I) and (II) is carried out by mixing them in water (5 to 35 ° C.) and reacting them, and then adding pure water to adjust the solid content concentration. It is preferred to do.

(Method of manufacturing chemical conversion film)
The manufacturing method of the chemical conversion film which concerns on this embodiment includes the contact process which contacts the chemical conversion treatment agent which concerns on this embodiment on the surface or surface of a metal material. Thereby, a chemical conversion film is formed on the surface or surface of the metal material. Examples of the method for contacting the chemical conversion treatment agent to the metal material include conventional contact methods such as immersion treatment, or treatment methods such as spray treatment, flow treatment, or a combination thereof. Is not limited to these.

  The contact is preferably performed for a fixed time within a predetermined temperature range. The contact temperature is preferably in the range of 10 ° C. to 60 ° C., and more preferably in the range of 20 ° C. to 50 ° C., but is not limited to these temperature ranges. The contact time is preferably in the range of 30 to 300 seconds, more preferably in the range of 60 to 180 seconds, but is not limited to these times.

  Moreover, you may perform a pre-processing process before a contact process. As the pretreatment step, for example, pickling step; degreasing step; alkali washing step; chromate conversion step; phosphate conversion step using phosphate such as zinc phosphate and iron phosphate; bismuth displacement plating step Zirconium conversion treatment step, titanium conversion treatment step, hafnium conversion treatment step, vanadium conversion treatment step and the like. In these pretreatment steps, one step may be performed, or two or more steps may be combined and sequentially performed. As a combination of two or more steps, a combination of a phosphate conversion treatment step, a chromate conversion treatment step, a bismuth substitution plating step, a zirconium conversion treatment step, a titanium conversion treatment step, a hafnium conversion treatment step or a vanadium conversion treatment step It can be mentioned. In the zirconium chemical conversion treatment step performed as the 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 addition, when performing said various pre-processing processes, you may perform a water washing process process after various pre-processing processes. When a plurality of various pretreatment processes are performed, the water washing process may be performed after each process or after some processes. When the water washing process is performed, a drying process may be performed to dry the surface of the metal material thereafter.

  Further, in the method for producing a chemical conversion film according to the present embodiment, after the contact step, for example, alkaline washing step, water washing step, chromate conversion treatment, zinc phosphate conversion treatment step, bismuth substitution plating step, phosphorus iron conversion treatment step, zirconium Post-treatment processes, such as a chemical conversion treatment process, a titanium chemical conversion treatment process, a hafnium chemical conversion treatment process, and a drying process, may be performed. As these post-processing steps, one step may be performed alone, or two or more steps may be combined and sequentially performed. In the zirconium chemical conversion treatment step performed as the 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 addition, when performing said various post-processing processes, you may perform a water washing process process after various post-processing processes. In the case where a plurality of post-treatment processes are performed, the water washing process may be performed after each process or after some processes. When the water washing process is performed, a drying process may be performed to dry the surface of the metal material thereafter.

Moreover, in the case of producing a coated metal material having a chemical conversion film and a coating film in which a coating film is formed on a chemical conversion film produced by the method for producing a chemical conversion film according to the present embodiment, after producing the chemical conversion film, A coating forming process such as a coating process and a drying process (including a baking process and a curing process) for drying the paint on the surface of the coated metal material may be performed to form a coating film. In addition, you may perform the water-washing treatment process which water-rinses the surface top of the metallic material which the chemical conversion treatment agent which concerns on this embodiment was made to contact before a coating process. In addition, a drying step may be performed to dry the surface of the metal material in contact with the chemical conversion treatment agent or the surface of the metal material subjected to the water-washing treatment step. Furthermore, one or more of the above-described post-treatment steps may be performed after the contact step and before the coating step. In addition, when performing said various post-processing processes, you may perform a water washing process process after various post-processing processes. In the case where a plurality of post-treatment processes are performed, the water washing process may be performed after each process or after some processes. When the water washing process is performed, a drying process may be performed to dry the surface of the metal material thereafter.

  The said coating process is performed on the surface of the metallic material which has the said conversion film using a coating material. The coating method is not particularly limited, and conventionally known methods, for example, roll coating, electrodeposition coating (for example, cationic electrodeposition coating, anion electrodeposition coating, etc.), spray coating, hot spray coating, airless spray coating, electrostatic ( Methods such as powder coating, roller coating, curtain flow coating, brush coating, bar coating, fluid immersion, etc. can be applied.

  Examples of the paint include oil paint, cellulose derivative paint, phenol resin paint, alkyd resin paint, amino alkyd resin paint, urea resin paint, unsaturated resin paint, vinyl resin paint, acrylic resin paint, epoxy resin paint, polyurethane Well-known paints, such as a resin paint, a silicone resin paint, a fluorine resin paint, an anticorrosion paint, an antifouling paint, a powder paint, a cationic electrodeposition paint, an anionic electrodeposition paint, a water-based paint, a solvent paint, etc. are mentioned. In the coating process, one or two or more coatings may be performed using the same or different various paints. The drying step is a process of drying and curing the coated paint. As a drying method, for example, natural drying, reduced pressure drying, convection heat drying (for example, natural convection heat drying, forced convection heat drying), radiation drying (for example, near infrared radiation drying, far infrared radiation drying), UV curing Drying methods such as drying, electron beam curing drying, vapor curing, baking drying and the like can be mentioned. In addition, one drying method may be implemented and you may implement combining two or more.

  A publicly known method can be applied as the above-mentioned cationic electrodeposition coating. For example, the method of immersing the metal material which has a chemical conversion film in this paint etc. is used, using a cationic electrodeposition paint containing an amine addition epoxy resin and blocking polyisocyanate curing agent as a hardening ingredient as paint. The cationic electrodeposition coating is performed, for example, by maintaining the temperature of the paint at a predetermined temperature and applying a voltage in the direction of the cathode to a metal material having a chemical conversion film using a rectifier while stirring the paint. A film can be formed on the chemical conversion film by carrying out water washing and baking on the metal material thus subjected to cationic electrodeposition coating. Baking is performed for a fixed time in a predetermined temperature range. Specifically, it is performed at 170 ° C. for 20 minutes. When a cationic electrodeposition coating method using a cationic electrodeposition paint is applied, the treatment agent used in various chemical conversion treatment steps including the degreasing step or the contact step of the present embodiment which is the pretreatment step It is preferable to control the concentration of sodium ion of less than 500 ppm by mass.

  A publicly known method can be applied as a coating method such as spray coating, electrostatic powder coating, or fluid immersion method using a powder coating. As a powder coating, for example, a polyester resin and, as a curing agent, one containing a blocked isocyanate curing agent, a β-hydroxyalkylamide curing agent (for example, see JP-A-2011-88083) or triglycidyl isocyanurate Can be mentioned. Baking is performed for a fixed time in a predetermined temperature range. Specifically, it is carried out at 150 to 250 ° C. for 20 minutes.

  A known method can be applied as a coating method such as spray coating, electrostatic coating, bar coating or the like using the above-mentioned solvent paint. Examples of the solvent paint include those containing a resin such as melamine resin, acrylic resin, urethane resin and polyester resin, and an organic solvent such as thinner. Baking is performed for a fixed time in a predetermined temperature range. Specifically, it is performed at 130 ° C. for 20 minutes.

  As a drying method for curing the coated paint, for example, natural drying, vacuum drying, convection heat drying (eg, natural convection heat drying, forced convection heat drying), radiation drying (eg, near infrared radiation drying) Drying methods such as far-infrared radiation drying, ultraviolet curing drying, electron beam curing drying, vapor curing and the like. These drying methods may be carried out alone or in combination of two or more.

  The coating film obtained by the coating process may be a single layer or multiple layers. When it is a multilayer, the paint for forming various coating films, the coating method using this paint, the drying method of the coated metal material, etc. may be same or different, respectively.

Examples of metal materials include iron (for example, cold-rolled steel plate, hot-rolled steel plate, high-tensile steel plate, tool steel, alloy tool steel, spheroidized graphite cast iron, gray cast iron, etc.); plating material, eg, galvanized steel (Eg, galvanizing, galvanizing, galvanizing, galvanizing, galvanizing, etc.); aluminum material (eg, 1000 series, 2000 series, 3000 series, 4000 series, 4000 series, 5000 series, 6000 series, aluminum castings, Aluminum alloy castings, die cast materials etc.); magnesium materials; etc. may be mentioned.
In particular, the chemical conversion treatment agent of the present embodiment is preferable because a coating having good corrosion resistance can be obtained even if it is a metal material to which corrosion resistance is hardly imparted. Specifically, even a metal material such as a hot-rolled steel plate or a high-tensile steel plate can form a film having good corrosion resistance.

The metal material having a chemical conversion film according to the present embodiment is produced by bringing the chemical conversion treatment agent according to the present embodiment into contact with the surface or the surface of the metal material to produce the chemical conversion film on the surface or the surface of the metal material. It is obtained by In the produced chemical conversion film, the total mass of titanium, zirconium and hafnium contained in the chemical conversion film is preferably 5 mg / m ² or more per unit area, and more preferably 10 mg / m ² or more. And 20 mg / m ² or more. The upper limit value is not particularly limited, but is preferably 800 mg / m ² or less. The mass of titanium, zirconium and hafnium in this chemical conversion film can be measured, for example, by using a fluorescent X-ray analyzer.

  The metal material having a chemical conversion film according to the present embodiment is one or more of the above-mentioned various films (for example, chromate) on or under the chemical conversion film obtained by contacting the chemical conversion treatment agent according to the present embodiment. It may have a chemical conversion film, a phosphate conversion film, a bismuth displacement plating film, etc.).

  By forming a coating film on the surface of the metal material having a chemical conversion film according to this embodiment by using a paint, a coated metal material having a chemical conversion film and a coating film can be manufactured. The coated metal material may have a coating on the surface of the metal material having a chemical conversion film according to the present embodiment, or one or more of the above-described various types further formed on the chemical conversion film. It may have a coating on the surface of a coating (for example, a chromate conversion coating, a phosphate conversion coating, a bismuth substitution plating coating, a vanadium conversion coating, etc.). The coating film may be composed of one layer or two or more layers. The thickness of the coating film is not particularly limited, and is appropriately set in accordance with the application of the coated metal material.

Hereinafter, the effects of the present invention will be described in detail by way of examples, but the present invention is not limited by the following examples.
<Metal material>
Cold-rolled rolled mild steel sheet (SPCC: thickness 0.8 mm) standardized by JIS G3141: 2011, hot-dip galvanized steel sheet (SGCC: thickness 0.8 mm) standardized by JIS G3302: 2012, as metal materials Alloyed galvanized steel sheet (GA: thickness 0.8 mm) standardized by G3302: 2012, electrogalvanized steel sheet (SECC: thickness 0.8 mm) standardized by JIS G3313: 2010, JIS G3131: 2011 Standardized hot-rolled mild steel plates (SPHC: 1.8 mm thick) and aluminum alloy plates (A 6061: 0.8 mm thick) standardized according to JIS H4000: 2014 are each 70 mm long × 150 mm wide It cut | disconnected and made the evaluation surface the surface where the burr | flash produced at the time of cutting existed. The height of the burr was about 100 μm.

<Each ingredient used for preparation of a chemical conversion treatment agent>
In preparation of the chemical conversion treatment agent, hexafluorozirconic acid as the source A; hydrofluoric acid as the source B; N-2- (aminoethyl) -3-aminopropyltriol as the silane coupling agent (I) Methoxysilane (KBM-603; Shin-Etsu Chemical Co., Ltd.) or 3-aminopropyltriethoxysilane (KBE-903; Shin-Etsu Chemical Co., Ltd.); 3-glycidoxypropyl trimethoxy as a silane coupling agent (II) Silane (KBM-403; Shin-Etsu Chemical Co., Ltd.) or 3-glycidoxypropyltriethoxysilane (KBE-403; Shin-Etsu Chemical Co., Ltd.) as a polymer, allylamine hydrochloride polymer (PAA-HCl-01) Nitto Bo Medical Co., Ltd., diallylamine polymer (PAS-21; knit Bo Medical Co., Ltd.) or diallylamine hydrochloride polymer (PAS 21-HCL; Nitto Bo Medical Co., Ltd.); aluminum nitrate nonahydrate or aluminum sulfate hexahydrate as a source C; nitric acid as a source D; Using. The aluminum nitrate nonahydrate was used not only as the source C but also as the source D.

<Preparation of a chemical conversion treatment agent>
As shown in Table 1, after blending each component in a predetermined amount, the chemical conversion treatment agents of Examples 1 to 25 and Comparative Examples 1 to 5 were prepared by adjusting to a predetermined pH with sodium hydroxide. In addition, when mix | blending a silane coupling agent in preparation of a chemical conversion treatment agent, it is made to react by mix | blending 1 type or 2 types of silane coupling agents in water (5-35 degreeC) by the mass ratio shown in Table 1 Then, pure water was added to use a reaction solution adjusted to have a solid content of 10%.

<Manufacture of metal material having a chemical conversion film>
A degreasing agent (FC-E 2086; Nihon Parkerizing Co., Ltd .; using an aqueous solution dissolved in water to a concentration of 20 g / L) on the surface of various metal materials (SPCC, SGCC, GA, SECC, SPHC and A6061) It was degreased by spraying at 43 ° C. for 120 seconds. Then, it spray-washed for 30 seconds. Subsequently, various chemical conversion agents (chemical conversion agents of Examples 1 to 25 and Comparative Examples 1 to 5) were sprayed on the surface of the metal material at 38 ° C. for 120 seconds to produce a chemical conversion film on the surface of the metal material. . The surface of the obtained metal material having a chemical conversion film was washed with tap water and then with deionized water and dried at 40 ° C.

<Measurement of the amount of zirconium (Zr adhesion amount) in the chemical conversion film>
The amount of zirconium in the chemical conversion film produced on the surface of the metal material was determined as the amount of attached Zr using a fluorescent X-ray (scanning fluorescent X-ray analyzer manufactured by Rigaku Corporation: ZSX Primus II). The results are shown in Table 2.

<Manufacture of a metal material (test piece) having a coating film>
As shown in Table 2, after coating was performed by various coating methods on the chemical conversion film produced on the surface of various metal materials, baking was performed to prepare a metal material (test piece) having a coating film. The details of the various coating methods and the conditions of baking are shown below.

(Cation electrodeposition coating)
A metal material having various chemical conversion films was used as a cathode, and a film was formed by cathodic electrolysis using a cationic electrodeposition paint (GT-100V; manufactured by Kansai Paint Co., Ltd.). The cathodic electrolysis was performed at an applied voltage of 180 V and a paint temperature of 30.0 ± 0.5 ° C. In addition, the cathodic electrolysis was performed by adjusting the amount of electricity so that the coating film thickness was 15.0 ± 1.0 μm. After the cathodic electrodeposition, the surface of the coated film was washed with deionized water and baked at 170 ° C. for 26 minutes to prepare a metal material (each test piece) having the coated film.

(Powder coating I)
Electrostatic powder coating was performed on the surface of a metal material having a chemical conversion film using a powder coating (Innovax P series standard type manufactured by Shinto Paint Co., Ltd.). After the electrostatic powder coating, baking was performed at 180 ° C. for 20 minutes to produce a metal material (test piece) having a coating film. The coating film thickness was adjusted to 60 ± 5 μm.
(Powder coating II)
As a powder coating, using Innovax P series low-temperature type manufactured by Kamito Paint Co., Ltd. and performing baking at 165 ° C. for 20 minutes, coating is performed in the same manner as powder coating I, and a metal material having a coating (test piece ) Was produced.
(Powder coating III)
As a powder coating, it is coated using the same method as powder coating I except that baking is performed at 150 ° C. for 20 minutes using Everclad harvest (standard product) manufactured by Kansai Paint Co., Ltd. ) Was produced.

(Solvent coating)
A solvent-based paint (AMILAC 1000 manufactured by Kansai Paint Co., Ltd.) was applied by a bar coat method on the surface of the metal material having a chemical conversion film. After coating, baking was performed at 130 ° C. for 20 minutes to produce a metal material (test piece) having a coating film. The coating film thickness was adjusted to be 30 ± 5 μm.

<Corrosion resistance test (SST)>
Using a cutter knife, the coated film surface of various test pieces (the test pieces No. 1 to 30) is scratched in an X-shape reaching the metal base, and based on the salt spray test method (JIS-Z2371: 2015) Neutral salt spray was performed. Neutral salt spray was performed for 1000 hours on the test pieces subjected to cationic electrodeposition coating. A neutral salt spray was applied to the powder coated test piece for 500 hours. The solvent-coated test pieces were sprayed with neutral salt water for 72 hours. After neutral salt spray, the coating film bulging width (one-side maximum bulging width) from the flaw (cross-cut portion) of the test piece was measured, and the corrosion resistance was evaluated according to the following evaluation criteria. In addition, the film blister width (maximum blister width) from the edge of the test piece (the test piece of No. 1 to 10 and No. 15 to 30) subjected to cationic electrodeposition coating is measured, and the following evaluation criteria Corrosion resistance was evaluated. The results are shown in Table 3.
<Evaluation criteria-cross cut part>
AA: One-side swelling width is less than 1.0 mm A: One-side swelling width is 1.0 mm or more and less than 1.5 mm B: One-side blister width is 1.5 mm or more and less than 2.5 mm C: One-side blister width is 2.5 mm or more Less than 5 mm D: One-side swelling width is 3.5 mm or more <Evaluation criteria-edge portion>
A: Maximum bulging width less than 1.5 mm B: Maximum bulging width less than 1.5 mm and less than 2.5 mm C: Maximum bulging width less than 2.5 mm and less than 5.0 mm D: Maximum bulging width more than 5.0 mm

<Rotation test with electrodeposition coating>
The above test strip No. 1 to 5 and No. 1 Instead of the cationic electrodeposition coating in 15 to 30, the following coating property coating property was carried out to form a coating film, and the obtained test pieces were used to evaluate the coating property coating property.
Using four metal materials having various chemical conversion coatings, electrodeposition coating is performed according to a method for testing the conductivity with electrodeposition coating using a four-sheet box (for example, see paragraphs 0085 to 0090 of JP-A-2010-90409) A flexibility test was performed. At the time of implementation, a 70 × 150 × 0.5 mm stainless steel plate (SUS 304) in which one side (the opposite side of the side facing the four-sheet box) was sealed with an insulating tape was used as the counter electrode. In addition, the liquid surface of the cationic electrodeposition paint was adjusted so that the evaluation surface of the metal material having the chemical conversion film and the current-carrying surface of the counter electrode of the four-sheet box were immersed. The temperature of the cationic electrodeposition paint was maintained at 30 ° C., and the cationic electrodeposition paint was stirred by a stirrer.
In such a state, the coating film was electrolytically deposited on the surface of the four box metal material having the chemical conversion film by the cathodic electrolysis method using the counter electrode as the anode. Specific electrolytic conditions were cathodic electrolysis for 180 seconds at a predetermined voltage using a rectifier. The voltage was adjusted so that the coating thickness of the surface of the metal material having a chemical conversion film closest to the counter electrode of the four sheets and facing the counter electrode was 15 μm. Subsequently, each test piece was washed with water, and then baked at 170 ° C. for 26 minutes to form a coated film, whereby a test piece was manufactured.
And the film thickness of the coating film formed in the counter-electrode surface side of the metallic material which has a chemical conversion film most distant from the counter electrode was measured using the electromagnetic type film thickness meter. The thickness of the coating film was determined by measuring the film thickness of 10 randomly selected spots on the test piece and calculating the average value thereof. After that, the electrodeposition coating curling property has the chemical conversion film most distant from the counter electrode with respect to the thickness (T ₁ ) of the coating film formed on the opposite side of the metal material having the chemical conversion film closest to the counter electrode. The ratio (T ₂ / T ₁ ) of the thickness (T ₂ ) of the coating film formed on the counter electrode side of the metal material was calculated, and the electrodeposition coating adhesion was evaluated based on the following evaluation criteria. The results are shown in Table 3.
<Evaluation criteria>
A: 0.65 or more B: 0.50 or more and less than 0.65 C: less than 0.50

  In all evaluation results, B or more was taken as the pass level.

Claims (6)

A chemical conversion treatment agent for producing a chemical conversion film on the surface or surface of a metal material,
A source of ions containing a metal selected from titanium, zirconium and hafnium;
A source of fluoride ions,
A silane coupling agent (I) containing an amino group,
A silane coupling agent (II) containing a glycidyl group,
A water-soluble or water-dispersible polymer having a structural unit represented by the following formula (i):
Mix
The polymer is a homopolymer,
The chemical conversion treatment agent whose compounding quantity of the said silane coupling agent (I) and silane coupling agent (II) is in the range of 0.10-9.00 in mass ratio [(I) / (II)].
  The chemical conversion treatment agent according to claim 1, further comprising a source of ions containing a metal selected from aluminum, magnesium and zinc.   The chemical conversion treatment agent according to claim 1 or 2, further comprising a source of nitrate ion.   A method of producing a chemical conversion film on a surface of a metallic material, comprising the step of contacting the chemical conversion treatment agent according to any one of claims 1 to 3 on the surface or surface of a metallic material. .   The metal material which has a conversion film obtained by the method of Claim 4.   The coated metal material which has a coating film on the surface of the metal material which has a conversion film of Claim 5.