WO2014192082A1

WO2014192082A1 - Supplement, surface-treated metal material, and production method therefor

Info

Publication number: WO2014192082A1
Application number: PCT/JP2013/064801
Authority: WO
Inventors: 川井　智; 慶幸川出
Original assignee: 日本パーカライジング株式会社
Priority date: 2013-05-28
Filing date: 2013-05-28
Publication date: 2014-12-04
Also published as: CN105378144A; JPWO2014192082A1; KR101726536B1; CN105378144B; EP3006600A1; EP3006600B1; PH12015502678A1; KR20160003134A; EP3006600A4; JP6055915B2; US20160186351A1

Abstract

The purpose of the present invention is to provide a supplement that avoids an increase in the HF concentration in a surface-treatment liquid for metal materials, is capable of supplying zirconium ions at high concentration by using the metal material surface-treatment liquid, and has excellent long-term storage stability, in order to continuously chemically convert and/or electrolytically treat a metal material. This supplement contains prescribed amounts of: a zirconium compound (A) not containing fluorine and including at least one type selected from a group comprising zirconium basic carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate; a fluorine-containing matter (B) including at least one type selected from a group comprising hydrofluoric acid, a hydrofluoric acid salt, fluorozirconic acid, and a fluorozirconic acid salt; and an acid component (C) including at least one type selected from a group comprising nitric acid, hydrochloric acid, sulfuric acid, and acetic acid.

Description

Replenisher, surface-treated metal material and method for producing the same

The present invention relates to a replenisher, a surface-treated metal material, and a method for producing the same.

In order to impart functions such as paint adhesion, post-coating corrosion resistance, and bare corrosion resistance, the metal material product is subjected to chemical conversion treatment according to the application, for example, phosphate treatment or chromate treatment, etc. Is common.
However, in recent years, interest in reducing environmental impacts has been high, and studies have been made to reduce industrial waste such as phosphate sludge and regulations restricting the use of hexavalent chromium. A treatment film has been proposed as a new film treatment that replaces a phosphate or chromate treatment (Patent Document 1, Patent Document 2). More specifically, a chemical conversion treatment and / or an electrolytic treatment (for example, a cathode) of a metal material in a surface treatment solution for a metal material containing zirconium (hereinafter also referred to as Zr) ions and fluorine (hereinafter also referred to as F) ions. By performing electrolysis or the like, a zirconium-based chemical conversion coating (hereinafter simply referred to as a coating) can be obtained on the surface of the metal material, thereby imparting excellent performance to the surface of the metal material.

In the surface treatment for metal materials described above, if the coating is continuously manufactured, zirconium ions in the surface treatment liquid for metal materials become oxides and adhere as a film and are consumed. Zirconium ion concentration of the steel decreases. On the other hand, fluorine ions are less taken into the film than zirconium ions, and the amount of decrease in fluorine ion concentration per unit area in the surface treatment liquid for metal materials is less than that of zirconium ions.

More specifically, H ₂ ZrF ₆ is often used as the surface treatment liquid for metal material containing zirconium ions, and the reaction formula thereof is as follows.
H ₂ ZrF ₆ + 2H ₂ O → ZrO ₂ ↓ + 6HF Formula (1)
At the interface between the metal material and the surface treatment solution for the metal material, the pH in the vicinity of the metal material rises due to the consumption of acid by etching, the reduction of hydrogen ions in the vicinity of the cathode electrode, etc., and as shown in Equation (1) ₂ ZrF ₆ is hydrolyzed, and a zirconium-based film such as zirconium oxide is formed on the surface of the metal material.
On the other hand, with respect to fluorine ions, as shown in the formula (1), 6 mol of HF is theoretically generated as a by-product in the surface treatment liquid for metal material as 1 mol of ZrO ₂ is produced. Compared with Zr, which is the main component of the film, the amount of HF contained in the film is very small. Therefore, when metal surface treatment is performed continuously, HF accumulates in the surface treatment solution for metal materials and its concentration increases. To do. In Formula (1), since HF is on the right side, when the HF concentration increases, the film formation reaction is suppressed, and it becomes difficult to form a film of an appropriate zirconium compound. In addition, when the concentration of zirconium ions decreases, zirconium ions must be replenished. In that case, it is common to replenish H ₂ ZrF _{6. In} this replenishment of the ratio of zirconium ions to fluorine ions, Accumulation is not avoided. Therefore, conventionally, in order to avoid accumulation of HF, many techniques have been adopted in which the surface treatment liquid for metal material is automatically partially discarded (auto drain) while continuously operating to keep the HF concentration constant. . However, it is not preferable from the environmental and economic viewpoints to auto-drain a liquid containing a large amount of zirconium ions, HF, etc., and to flow it to the wastewater, despite the proposal of a film with reduced environmental impact. There is a need for improvement.

Therefore, Patent Document 3 uses a zirconium compound containing fluorine and a replenisher containing a zirconium compound not containing fluorine, and an amount of zirconium ions in consideration of the balance with the replenishment amount of fluorine ions to the surface treatment liquid for metal materials. It is proposed that the above problem can be solved by replenishing. More specifically, in paragraph 0033 of Patent Document 3, a Zr ion concentration of 17 g / L of a Zr fluoride hydrofluoric acid and Zr nitrate mixed solution (fluorinated Zr hydroacid: Zr nitrate 55:45 by weight) is used. It is disclosed that Zr ions have been replenished.

JP 2008-202149 A JP 2010-90407 A Japanese Patent No. 4996409

On the other hand, replenishers used for replenishing zirconium ions to the surface treatment liquid for metal materials are usually used while being stored in a warehouse for a long time after purchase. For this reason, it is required to be usable even after being stored for a long period of time. In particular, when the replenisher is stored for a long period of time in a high temperature environment, it is necessary that no precipitation or the like occurs in the replenisher. The
The present inventors examined the storage stability of the replenisher specifically described in Patent Document 3, and as a result, the storage stability did not meet the recent required level, and further improvements were necessary. It was.

In recent years, it has been desired to reduce the cost of coating treatment, and accordingly, further improvement in production efficiency is desired. As means for improving the production efficiency, there are a method of suppressing auto drain as much as possible and a method of performing film processing while increasing the total processing load as compared with the conventional method. Note that the cumulative treatment load is the result of continuous operation of the coating treatment, and the cumulative treatment area (Sm ² ) of the metal material divided by the surface treatment liquid volume for metal material (VL) (S / V (m ² / L)), as a coating treatment technology for metal materials, it is necessary that the change in the component balance of the surface treatment liquid for metal materials is small and the processability does not deteriorate for a larger cumulative processing load. It is said. If the change in the component balance of the surface treatment liquid for metal materials is large or the processability is likely to deteriorate with respect to the total processing load, the surface treatment liquid for metal materials is partially or completely updated to ensure stable treatment. It is necessary to ensure sex. In that case, it is not preferable from the viewpoint of production efficiency, cost, and environment.
The inventors conducted continuous operation of the film treatment using the replenisher specifically described in Patent Document 3, and verified the film treatment property at the time of a larger cumulative treatment load. It has been found that the amount of the coating on the surface is reduced.

In view of the above circumstances, the present invention avoids an increase in the HF concentration in the surface treatment liquid for metal material so that chemical conversion treatment and / or electrolytic treatment can be continuously performed on the metal material, An object of the present invention is to provide a replenisher that can replenish the surface treatment solution for metal material with higher concentration of zirconium ions and has excellent long-term storage stability.
Another object of the present invention is to provide a method for producing a surface-treated metal material using the replenisher.

As a result of intensive studies, the present inventors have found that the above problem can be solved by using a replenisher having a high zirconium ion concentration obtained by using a predetermined compound.
That is, the configuration of the present invention for solving the above problems is as follows.

(1) Zirconium ions with respect to a surface treatment solution for metal materials containing zirconium ions and fluorine ions used for forming a chemical conversion treatment film containing zirconium on metal materials by chemical treatment and / or electrolytic treatment. A replenisher used to replenish
A fluorine-free zirconium compound (A) containing at least one selected from the group consisting of basic zirconium carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate, hydrofluoric acid, a salt of hydrofluoric acid, Fluorine-containing material (B) containing at least one selected from the group consisting of zirconium hydrofluoric acid and a salt of zirconium hydrofluoric acid, and selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid An acid component (C) containing at least one of
A replenisher that satisfies the following (I) to (III):
(I) The ratio (M _AC / M _F ) between the total molar amount (M _AC ) of the anion derived from the acid component (C) and the total molar amount (M _F ) of the fluorine ion derived from the fluorine-containing material (B) It is 0.35 or more and less than 2.00.
(II) The total concentration (g / L) of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing product (B) is 25 or more.
(III) Total molar amount (M _F ) of fluorine ions derived from fluorine-containing material (B) and total molar amount of zirconium ions derived from fluorine-free zirconium compound (A) and fluorine-containing material (B) (M _Zr ) (M _F / M _Zr ) is less than 2.00 and less than 6.00.
(2) The replenisher according to (1), wherein the ratio (M _AC / M _F ) is more than 0.50 and less than 2.00.
(3) The replenisher according to (1) or (2), wherein the ratio (M _AC / M _F ) is more than 0.50 and not more than 1.60.
(4) A chemical conversion treatment and / or an electrolytic treatment is continuously performed on the metal material in a surface treatment solution for the metal material containing zirconium ions and fluorine ions to form a chemical conversion treatment film containing zirconium on the metal material. A method of manufacturing a surface-treated metal material,
(1) A method for producing a surface-treated metal material, wherein the replenisher according to any one of (1) to (3) is added to a surface treatment solution for a metal material to replenish zirconium ions.
(5) A surface-treated metal material obtained from the method for producing a surface-treated metal material according to (4).

According to the present invention, for the metal material, the chemical conversion treatment and / or the electrolytic treatment can be continuously performed on the metal material, while avoiding an increase in the HF concentration in the surface treatment liquid for the metal material. Zirconium ions can be replenished to the surface treatment liquid at a higher concentration, and a replenisher that is superior in long-term storage stability can be provided.
Moreover, according to this invention, the manufacturing method of the surface treatment metal material which uses this replenisher can be provided.

Below, the replenisher of this invention and the manufacturing method of a surface treatment metal material are demonstrated.
The replenisher of the present invention contains a predetermined fluorine-free zirconium compound (A), a predetermined fluorine-containing material (B), and a predetermined acid component (C), and contains zirconium ions (Zr ions) at a high concentration. contains. Further, the replenisher of the present invention is a ratio (M _AC / M _F ) between the total molar amount (M _AC ) of the anion derived from the acid component (C) and the total molar amount (M _F ) of the fluorine ion (F ion). And the ratio (M _F / M _Zr ) of the total molar amount (M _Zr ) of zirconium ions and the total molar amount (M _F ) of fluorine ions is within a predetermined range. By satisfying the above components and the component amount ratio, long-term storage stability of the replenisher is achieved. Further, the replenisher contains zirconium ions at a higher concentration than fluorine ions. Therefore, in continuous chemical conversion coating production, when the replenisher is continuously replenished to the surface treatment liquid for metal material, a large amount of zirconium ions can be continuously supplied while avoiding an increase in HF. As a result, the chemical conversion treatment and / or the electrolytic treatment of the metal material can be continuously performed while suppressing the amount of auto drain. In particular, by adjusting the ratio (M _AC / M _F ) to a predetermined range, the replenisher is more excellent in long-term storage stability and can be continuously subjected to chemical conversion treatment and / or electrolytic treatment of metal materials. An agent can be provided.
First, an embodiment of the replenisher of the present invention will be described below, and then a method for producing a surface-treated metal material using the replenisher will be described.

[Replenisher]
The replenisher of the present invention is a surface treatment for a metal material containing zirconium ions and fluorine ions, which is used for forming a chemical conversion treatment film containing zirconium as a main component on the surface of the metal material by chemical conversion treatment and / or electrolytic treatment. It is mainly used to supply zirconium ions to the liquid. In addition, in continuous chemical conversion treatment film manufacture, implementation of an auto drain is not refused.
First, various materials contained in the replenisher will be described in detail, and then a method for producing the replenisher will be described in detail.

(Fluorine-free zirconium compound (A))
The fluorine-free zirconium compound (A) contained in the replenisher of the present invention is a compound containing no Z atom and no fluorine atom.
Examples of the fluorine-free zirconium compound (A) include at least one selected from the group consisting of basic zirconium carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate. Among these, basic zirconium carbonate or carbonic acid is preferred in that the storage stability of the replenisher is superior and the surface treatment can be carried out more continuously (hereinafter also referred to simply as “the effect of the present invention is more excellent”). Zirconium is more preferred.
In addition, as a fluorine-free zirconium compound (A), you may use the said compound in mixture of 2 or more types.

(Fluorine-containing material (B))
The fluorine-containing material (B) contained in the replenisher of the present invention is a compound containing a fluorine atom, and F ions are supplied into the replenisher by the compound. In addition, when using zirconium hydrofluoric acid or its salt as a fluorine containing material (B), Zr ion is also supplied in a replenisher.
Examples of the fluorine-containing material (B) include at least one selected from the group consisting of hydrofluoric acid, a hydrofluoric acid salt, zirconium hydrofluoric acid, and a zirconium hydrofluoric acid salt. Among these, hydrofluoric acid or zirconium hydrofluoric acid is more preferable in that the effect of the present invention is more excellent.
Examples of the salt of hydrofluoric acid include a salt of hydrofluoric acid and a base (for example, an amine compound), preferably a base containing no metal such as an ammonium salt. Examples of the salt of zirconium hydrofluoric acid include metal acid salts such as K ₂ ZrF ₆ (for example, sodium salt, potassium salt, lithium salt, ammonium salt, etc.).
Further, as the fluorine-containing material (B), two or more of the above compounds may be mixed and used.

(Acid component (C))
The acid component (C) contained in the replenisher of the present invention plays a role in adjusting the pH of the replenisher and other components (fluorine-free zirconium compound (A) and / or fluorine-containing material (B)). It plays a role in helping solubility.
Examples of the acid component (C) include at least one selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid. Among these, nitric acid or sulfuric acid is more preferable in that the effect of the present invention is more excellent.
In addition, as an acid component (C), you may mix and use the said acid component 2 or more types.

(Various contents)
Various components in the replenisher of the present invention satisfy the following relationships (I) to (III).
(I) The ratio (M _AC / M _F ) between the total molar amount (M _AC ) of the anion derived from the acid component (C) and the total molar amount (M _F ) of the fluorine ion derived from the fluorine-containing material (B) It is 0.35 or more and less than 2.00.
(II) The total concentration (g / L) of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing product (B) is 25 or more.
(III) Total molar amount (M _F ) of fluorine ions derived from fluorine-containing material (B) and total molar amount of zirconium ions derived from fluorine-free zirconium compound (A) and fluorine-containing material (B) (M _Zr ) (M _F / M _Zr ) is less than 2.00 and less than 6.00.
Below, each relationship is demonstrated.

(About (I))
Ratio (M _AC ) of the total molar amount (M _AC ) of the anion derived from the acid component (C) and the total molar amount (M _F ) of the fluorine ion derived from the fluorine-containing material (B) in the replenisher of the present invention. / M _F ) is 0.35 or more and less than 2.00. Within the above range, the storage stability of the replenisher is excellent, and the chemical conversion coating can be manufactured stably and continuously without accumulating HF of the surface treatment liquid for metal material. Among them, as a range in which the effect of the present invention is more excellent, the ratio (M _AC / M _F ) is preferably more than 0.40 and less than 2.00, more preferably more than 0.50 and less than 2.00, and more than 0.50. .60 or less is more preferable, and 1.00 or more and 1.60 or less is particularly preferable.
When the ratio (M _AC / M _F ) is less than 0.35, the long-term storage stability of the replenisher is poor. Further, when the ratio (M _AC / M _F) is 2.00 or more, the amount of deposition of the film continued use of the replenisher is reduced, it is no longer possible to create the desired coating.
The anion derived from the acid component (C) (nitric acid, hydrochloric acid, sulfuric acid, and acetic acid) intends NO ₃ ⁻ , Cl ⁻ , SO ₄ ²⁻ , and CH ₃ COO ⁻ .

(About (II))
The total concentration (g / L) of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing material (B) in the replenisher of the present invention is 25 or more. If it is in the said range, a more economical chemical conversion treatment film can be manufactured. Among them, the total concentration (g / L) of zirconium ions is preferably 30 or more, and more preferably 35 or more, from the viewpoint that the amount of the replenisher used is small and the operation economy is more excellent. The upper limit is not particularly limited, but it is often 70 or less from the viewpoint of the solubility of the fluorine-free zirconium compound (A) and the fluorine-containing product (B).
When the total concentration of zirconium ions (g / L) is less than 25, the concentration of the replenisher is dilute, so that a large amount of the replenisher must be replenished to the surface treatment liquid for metal material, and supercharged water is accordingly added As a result, the volume of the surface treatment liquid for metal materials has increased, and as a result, it is necessary to increase the amount of auto drain of the surface treatment liquid for metal materials in order to perform continuous film treatment. Is not preferable.
Further, when zirconium hydrofluoric acid or a salt thereof is used as the fluorine-containing material (B), zirconium ions derived from the fluorine-containing material (B) are supplied.

(About (III))
The total molar amount (M _Zr ) of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing material (B) in the replenisher of the present invention, and the fluorine ions derived from the fluorine-containing material (B) The ratio (M _F / M _Zr ) to the total molar amount (M _F ) is 2.00 or more and less than 6.00. If it is in the said range, HF of the surface treatment liquid for metal materials will not accumulate | store, but manufacture of a chemical conversion treatment film can be performed stably stably. In particular, the ratio (M _F / M _Zr ) is preferably 2.50 to 5.50, more preferably 3.00 to 5.00, in which the effect of the present invention is more excellent.
When the ratio (M _F / M _Zr ) is less than 2.00, it is difficult to dissolve zirconium ions in the replenisher. In addition, when the ratio (M _F / M _Zr ) is 6.00 or more, if the replenisher is continuously used, accumulation of HF in the surface treatment liquid for metal material cannot be avoided. In the case of producing a treated film, it is necessary to increase the amount of auto drain, which is not preferable from an environmental and economic point of view.

The measurement of various ions described above can be performed using a known measuring instrument, atomic absorption, ICP, ion chromatography, or a fluorine ion meter.

The content of the fluorine-free zirconium compound (A) in the replenisher of the present invention is not particularly limited as long as the relations (I) to (III) are satisfied, but the deposition efficiency of the chemical conversion film is more excellent. The amount is preferably from 0.1 to 500 parts by weight, more preferably from 10 to 300 parts by weight, based on 100 parts by weight of the fluorine-containing material (B).

The pH of the replenisher of the present invention is not particularly limited, but is preferably less than 4.0 and more preferably more than 0 and 1.5 or less in terms of excellent stability of the replenisher. In addition, when adjusting pH, an alkali component can also be used. Alkali components include alkali metal oxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, organic substances such as ammonia, monoethanolamine, diethanolamine, and triethanolamine. Examples include amines. Among them, it is preferable to use ammonia from the viewpoint that there is no metal contamination and no organic solvent is contained.

The replenisher of the present invention may contain a solvent, if necessary. The kind in particular of solvent used is not restrict | limited, Usually, water and / or an organic solvent are used.
Examples of the organic solvent include alcohol solvents. Regarding the content of the organic solvent, it may be in a range that does not impair the stability of the replenisher and the stability of the surface treatment liquid for metal material replenished with the replenisher, but it should not be used from the viewpoint of the working environment. preferable.
When the replenisher contains a solvent, the total mass of the fluorine-free zirconium compound (A), the fluorine-containing material (B), and the acid component (C) is the replenisher in that the deposition efficiency of the chemical conversion coating is more excellent. 2 to 90% by mass is preferable with respect to the total amount, and 4 to 80% by mass is more preferable.

In addition, the manufacturing method of the replenisher of the present invention is not particularly limited, and a known method is adopted. For example, a method in which a fluorine-free zirconium compound (A), a fluorine-containing material (B), and an acid component (C) are added and mixed in a solvent can be mentioned.

[Method for producing surface-treated metal material]
Below, the manufacturing method of the surface treatment metal material using the replenisher of this invention is demonstrated.
In the method for producing a surface-treated metal material according to the present invention, a metal material is continuously subjected to chemical conversion treatment and / or electrolytic treatment in a surface treatment solution for metal material containing zirconium ions and fluorine ions, and zirconium is contained on the metal material. This is a method of forming a chemical conversion treatment film.
When the method for producing the surface-treated metal material is continuously carried out, the concentration of zirconium ions in the surface treatment liquid for metal material is lowered accordingly, and it becomes difficult to form a film of the zirconium compound. In order to compensate for such a decrease in the concentration of zirconium ions, the above-described replenisher is replenished into the surface treatment liquid for metal material.
In general, it is preferable to add the replenisher so that the zirconium ion concentration does not decrease by 20% or more in order to obtain a predetermined chemical conversion coating on the metal material continuously and stably. The total fluorine ion amount replenished simultaneously with zirconium is determined from the total amount of total fluorine ions contained in the chemical treatment film and the total amount of fluorine ions contained in the surface treatment solution for metal materials taken out of the metal material. It is preferable to replenish the amount obtained by subtracting the amount of fluorine ions of HF produced as a by-product in the surface treatment solution for metal material when a zirconium compound film is formed.

The method of adding the replenisher of the present invention to the surface treatment solution for metal material is not particularly limited, and a method of adding the replenisher in small portions (Method A) or a predetermined amount of replenisher in a lump. (Method B). Especially, the method A is preferable from the point that the component fluctuation | variation in the surface treatment liquid for metal materials is small and can manufacture a surface treatment metal material stably continuously.
In addition, when adding the replenisher of the present invention to the surface treatment liquid for metal material, the method of adding the replenisher to the surface treatment liquid for metal material, and the surface without stopping production, Any method of adding a replenisher to the surface treatment liquid for metal material during the method for producing the treated metal material may be employed. In particular, the surface for metal materials during the manufacturing method of surface-treated metal materials is superior in that it is excellent in production efficiency especially at high-speed operation, and can continuously and stably produce the surface-treated metal materials. A method of adding a replenisher to the treatment liquid is preferred.
Hereinafter, the surface treatment liquid for metal material used in the method for producing a surface-treated metal material of the present invention will be described.

(Surface treatment solution for metal materials)
The surface treatment liquid for metal material used in the method for producing a surface-treated metal material of the present invention described above contains Zr ions and fluorine ions.
Examples of the supply source of zirconium ions in the surface treatment liquid for metal materials include the above-described fluorine-free zirconium compound (A), zirconium hydrofluoric acid, or a salt thereof.
As Zr ions in the surface treatment liquid for metal materials, as shown in (1) ZrF _n ^(4-n) , complex fluorination in which 1 to 6 mol of fluorine is coordinated to 1 mol of zirconium. It refers to both zirconium ions and (2) zirconium or zirconyl inorganic acids such as zirconium nitrate or zirconium sulfate, or zirconium or zirconyl ions generated from organic acid zirconium or zirconyl such as zirconium acetate or zirconyl acetate.
The content of zirconium ions in the surface treatment liquid for metal material is not particularly limited, but is 0.05 to 10.5 in that it is more excellent in stability of the surface treatment liquid for metal material and more excellent in deposition efficiency of the chemical conversion film. 00 g / L is preferable, and 0.10 to 2.00 g / L is more preferable.

In addition, a known fluorine-containing compound (fluorine-containing compound) is used as a supply source of fluorine ions in the surface treatment liquid for metal materials.
As the fluorine-containing compound, those having at least one element selected from the group consisting of Ti, Zr, Hf, Si, Al and B are preferably used. Specifically, for example, (TiF ₆ ) ²⁻ , (ZrF ₆ ) ²⁻ , (HfF ₆ ) ²⁻ , (SiF ₆ ) ²⁻ , (AlF ₆ ) ³⁻ , (BF ₄ OH) ^−, etc. A complex in which 1 to 3 hydrogen atoms are coordinated to an anion, an ammonium salt of these anions, a metal salt of these anions and the like can be mentioned.
In addition, examples of the fluorine-containing compound include hydrofluoric acid, its ammonium salt, its alkali metal salt, and metal fluoride (for example, aluminum fluoride, zinc fluoride, vanadium fluoride, tin fluoride, fluorine fluoride). Manganese fluoride, ferrous fluoride, ferric fluoride, etc.) and oxyfluorides (eg, fluorine oxide, acetyl fluoride, benzoyl fluoride, etc.).
Fluorine ions in the surface treatment liquid for metal materials are HF-derived fluorine ions (F ⁻ ) present in the surface treatment liquid for metal materials and fluorine-containing complex ions such as the above complex zirconium fluoride ions. It refers to both fluorine ions, and the total fluorine ion concentration described above and below refers to the total concentration of both. The free fluorine concentration refers to the concentration of fluorine ions (F ⁻ ) derived from HF.
The content of total fluorine ions in the surface treatment liquid for metal materials is not particularly limited, but the total fluorine ion concentration is superior in terms of the stability of the surface treatment liquid for metal materials and the deposition efficiency of the chemical conversion coating. 0.050 to 10.000 g / L is preferable, and 0.100 to 3.000 g / L is more preferable. The free fluorine ion concentration is preferably 5 mg / L to 400 mg / L, more preferably 10 to 250 mg / L.

The content (concentration) of Zr ions, total fluorine ions, and free fluorine ions in the surface treatment solution for metal materials can be quantified using atomic absorption, ICP, ion chromatography, or a fluorine ion meter.

The pH of the surface treatment solution for metal materials is adjusted as appropriate according to the target metal material and the conditions of chemical conversion treatment or electrolytic treatment, but it is superior in stability of the surface treatment solution for metal materials and deposits of the chemical conversion treatment film. From the viewpoint of more excellent properties, it is preferably about 2.5 to 5.0, more preferably 3.0 to 5.0. In addition, pH of the surface treatment liquid for metal materials can be measured using a pH meter.

Hereinafter, the metal material used in the method for producing the surface-treated metal material of the present invention, and the chemical conversion treatment and the electrolytic treatment will be described.

(Metal material)
The kind in particular of metal material to be used is not restrict | limited, A well-known metal material can be used. Examples thereof include iron-based materials, plating-based materials, zinc-based materials, aluminum-based materials, and magnesium-based materials.
The shape of the metal material is not particularly limited, and may be a plate shape or another shape. Other shapes include, for example, the body and parts of transportation equipment such as automobiles, agricultural equipment and parts, steel furniture, building materials, and the like.

(Chemical conversion treatment or electrolytic treatment)
The chemical conversion treatment using the above-described surface treatment solution for metal material can be carried out under known conditions using a known treatment facility. The chemical conversion treatment is a treatment for forming a film on the surface of the metal material by bringing a predetermined surface treatment liquid for the metal material into contact with the metal material at room temperature or warming (immersion, coating, or spraying). .
The time for contacting the metal material with the surface treatment liquid for the metal material is appropriately adjusted according to the material, shape, treatment method, application, and target coating amount of the target metal material. Usually, it is often about 0.1 to 600 seconds in terms of more excellent characteristics.
Moreover, as the electrolytic treatment (anodic electrolytic treatment, cathodic electrolytic treatment) using the surface treatment liquid for metal material, it can be carried out under known conditions using a known electrolytic treatment facility.
For example, the current density is preferably from 0.1 to 20.0 A / dm ^{2 and} more preferably from 0.5 to 10.0 A / dm ² from the viewpoint of more excellent deposition efficiency of the chemical conversion coating.
The amount of zirconium deposited on the formed chemical conversion coating is appropriately adjusted according to the material and application of the target metal material. However, either the chemical conversion treatment or the electrolytic treatment can be used because the properties as the chemical conversion coating are more excellent. In many cases, the amount is usually about 1 to 70 mg / m ² .

Hereinafter, the present invention will be described with specific examples. The present embodiment is merely a part for explaining the present invention, and does not limit the present invention.

(Test plate)
The following (1) to (3) were used as test plates used in Examples and Comparative Examples.
(1) Aluminum alloy plate (6000 series aluminum alloy plate thickness: 0.8mm)
(2) Cold rolled steel plate (SPC, plate thickness: 0.8 mm)
(3) Alloyed hot-dip galvanized steel sheet (GA, thickness: 0.8 mm)

(Supplement)
The fluorine-free zirconium compound (A), fluorine-containing product (B), and acid component (C) shown in Table 1 are mixed in water so as to have the composition shown in Table 1, and various replenishers are added. Prepared.

(Surface treatment method for metal materials)
The surface treatment method of the metal material of the Example and comparative example which are mentioned later was performed according to the following procedures.
(1) Degreasing (2) Washing with water (tap water)
(3) Chemical conversion treatment (4) Water washing (tap water)
(5) Water washing (ion exchange water)
(6) Draining and drying In addition, the degreasing | defatting in the above was performed using Nippon Parkerizing Co., Ltd. alkali degreasing agent fine cleaner L4460 (2.0%, 45 degreeC, 120 second, spray process).
Details of the chemical conversion treatment method will be described in the following continuous treatment test method. Moreover, in draining drying, after performing draining with a roll, it dried in 100 degreeC atmosphere oven.

(Continuous processing test method (running test))
As the chemical conversion treatment, any one of the following continuous treatment methods 1 to 3 was performed.
<Continuous processing method 1>
A treatment solution having the following component concentrations was bathed for 10 L, adjusted to pH 4.0, and heated to 40 ° C. to obtain a surface treatment solution for metal materials. The treatment liquid was stirred, and the test plate (1) was immersed for 180 seconds to perform a surface treatment with a target Zr adhesion amount of 13 mg / m ² . This was treated as a single treatment, and thereafter a surface treatment (continuous treatment test) was repeatedly performed using a new test plate (1). At this time, since the amount of the processing liquid (take-out liquid) adhering to the test plate (1) and taking out was 75 mL / m ² , the liquid level and the processing liquid in the processing liquid every 0.5 m ² / L processing load. Replenishment of the Zr concentration drop was performed with water and the replenisher shown in Table 1, and the Zr concentration was adjusted simultaneously with the liquid level. The pH of the treatment liquid was also adjusted with ammonia water as necessary every 0.5 m ² / L. The above-mentioned continuous test was performed until 10 L of the total amount of the processing solution was replaced with 100% by the carry-out solution. That is, the test was performed until the treatment load reached 13.3 m ² / L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount during the 13.3 m ² / L treatment were measured. In addition, the Zr adhesion amount on the treatment material surface was quantified using XRF (fluorescence X-ray analysis method).

(Processing liquid components)
The concentration of each component was Zr ion: 100 mg / L, total F ion: 150 mg / L, free F ion: 25 mg / L, NO ₃ ion: 190 mg / L.

<Continuous processing method 2>
A treatment solution having the following component concentrations was bathed for 10 L, adjusted to pH 4.0, and heated to 40 ° C. to obtain a surface treatment solution for metal materials. This treatment liquid was stirred, and the test plate (2) was immersed for 120 seconds to perform a surface treatment with a target Zr deposition amount of 20 mg / m ² . This was treated as one time, and then a new surface treatment (continuous treatment test) was performed using a new test plate (2). At this time, since the amount of the processing liquid (take-out liquid) adhering to the test plate (2) and taken out was 60 mL / m ² , the liquid surface and the processing liquid in every 0.5 m ² / L of processing load Replenishment of the Zr concentration drop was performed with water and the replenisher shown in Table 1, and the Zr concentration was adjusted simultaneously with the liquid level. The pH of the treatment liquid was also adjusted with ammonia water as necessary every 0.5 m ² / L. The above-mentioned continuous test was performed until 10 L of the total amount of the processing solution was replaced with 100% by the carry-out solution. That is, the test was performed until the treatment load reached 16.7 m ² / L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount at the time of 16.7 m ² / L treatment were measured. In addition, the Zr adhesion amount on the treatment material surface was quantified using XRF (fluorescence X-ray analysis method).

(Processing liquid components)
The concentrations of the various components were Zr ions: 500 mg / L, total F ions: 680 mg / L, free F ions: 36 mg / L, NO ₃ ions: 750 mg / L.

<Continuous processing method 3>
A treatment solution having the following component concentrations was bathed for 10 L, adjusted to pH 3.7, and heated to 40 ° C. as a surface treatment solution for metal materials. The treatment liquid was stirred, and the test plate (3) was immersed for 30 seconds to perform a surface treatment with a target Zr deposition amount of 10 mg / m ² . This was treated as a single treatment, and thereafter a surface treatment (continuous treatment test) was repeatedly performed using a new test plate (3). At this time, the amount of the treatment liquid (take-out liquid) adhering to the test plate (3) and taken out was 22 mL / m ² , so the liquid level and the amount of the treatment liquid in the treatment liquid were increased every 0.5 m ² / L. Replenishment of the Zr concentration drop was performed with water and the replenisher shown in Table 1, and the Zr concentration was adjusted simultaneously with the liquid level. The pH of the treatment liquid was also adjusted with ammonia water as necessary every 0.5 m ² / L. The above-mentioned continuous test was performed until 10 L of the total amount of the processing solution was replaced with 100% by the carry-out solution. That is, the test was performed until the treatment load reached 45.5 m ² / L, and the Zr adhesion amount at the initial stage of the continuous test and the Zr adhesion amount at the time of 45.5 m ² / L treatment were measured. In addition, the Zr adhesion amount on the treatment material surface was quantified using XRF (fluorescence X-ray analysis method).

(Processing liquid components)
The concentration of each component was Zr ion: 1500 mg / L, total F ion: 2010 mg / L, free F ion: 95 mg / L, NO ₃ ion: 2190 mg / L.

(Evaluation test)
Using the replenishers shown in Table 1, the following (A) and (B) were evaluated.
(A) Replenisher storage stability test (long-term storage)
The replenishers shown in Table 1 were sealed in a plastic container and stored for up to 6 months in a 35 ° C. environment immediately after production to evaluate the liquid appearance. The evaluation criteria are as follows. Practically, “◯” or “◎” is preferable.
◎: No change in appearance after 6 months ○: Change in appearance between 3 months and less than 6 months △: Change in appearance between 2 weeks and less than 3 months ×: Precipitation or precipitation within 2 weeks Turbidity or gelation is confirmed. “No change in appearance” means that all of precipitates, turbidity and gelation are not confirmed, and the state is colorless and transparent.

(B) Running test (continuous process test)
A continuous treatment test was conducted by the treatment method shown in Table 1, and the Zr adhesion amount of the test piece (test plate) at the initial stage of the test (first time) and when the treatment solution substitution rate was 100% was measured, and the values were compared. The evaluation criteria are as follows. Practically, “◯” or “◎” is preferable.
A: Zr adhesion amount after 100% substitution is 95% or more and less than 105% with respect to the Zr adhesion amount at the initial stage of the continuous treatment test. O: Zr adhesion amount after 100% substitution with respect to the Zr adhesion amount at the initial stage of the continuous treatment test. 85% or more and less than 95% Δ: Zr adhesion amount after 100% substitution is 50% or more and less than 85% with respect to the Zr adhesion amount at the initial stage of the continuous treatment test. The amount of Zr adhesion after is less than 50%

In Table 1, “Zr carbonate” represents zirconium carbonate, “basic carbonate Zr” represents basic zirconium carbonate, and “Zr concentration” represents zirconium ion concentration (g / L).

* 1) H ₂ ZrF ₆ : HF = 4.6: 1 (weight ratio)
* 2) In Comparative Examples 1 to 3, the long-term storage of the replenisher itself was poor, and precipitation was confirmed within one week in an environment of 35 ° C. Not performed.

As shown in Table 1, in the examples using the replenisher of the present invention, it was confirmed that the long-term storage property of the replenisher was excellent and the continuous processability (continuous operability) of the treatment was also excellent.
Among them, as can be seen from the comparison between Examples 2-3 and Examples 1 and 4 to 9, when M _AC / M _F is less than 0.50 ultra 2.00, more excellent long-term storage of the replenisher It was confirmed.
As it can be seen from a comparison of Examples 2 to 3, 7 to 9 and Examples 1 and 4 to 6, when M _AC / M _F is 0.50 ultra 1.60, the running property (continuous operation of ) Was confirmed to be better.

On the other hand, the ratio (M _AC / M _F) is in the predetermined range is smaller than Comparative Example 1-3, was inferior storage stability of the replenisher.
In addition, the mixed replenisher for Zr hydrofluoric acid and Zr nitrate described in paragraph [0033] of Patent Document 3 (Patent No. 4996409) has M _AC / M _F = 0.33, and Comparative Examples 1 to As shown in FIG. 3, the replenisher did not provide the desired effect.
In Comparative Examples 4 to 6, it is presumed that the ratio of the anion derived from the acid component (C) is higher than the fluorine derived from the fluorine-containing material (B) as an anion for stabilizing zirconium in the replenisher. After adding the replenishers of Comparative Examples 4 to 6 to the surface treatment liquid for materials, the coordination between zirconium and other anions is stronger than the coordination of Zr—F in the treatment liquid, and the film formation reaction is increased. It becomes difficult to stabilize. This is presumably because the coordination state of zirconium ions and F ions affected the hydrolysis of H ₂ ZrF ₆ as a film-forming reaction.

Claims

Zirconium ions are replenished to the surface treatment solution for metal materials containing zirconium ions and fluorine ions, which is used to form a chemical conversion treatment film containing zirconium on metal materials by chemical treatment and / or electrolytic treatment. A replenisher used to
A fluorine-free zirconium compound (A) containing at least one selected from the group consisting of basic zirconium carbonate, zirconium carbonate, zirconium hydroxide, and ammonium zirconium carbonate, hydrofluoric acid, a salt of hydrofluoric acid, Fluorine-containing material (B) containing at least one selected from the group consisting of zirconium hydrofluoric acid and a salt of zirconium hydrofluoric acid, and selected from the group consisting of nitric acid, hydrochloric acid, sulfuric acid, and acetic acid An acid component (C) containing at least one of
A replenisher that satisfies the following (I) to (III):
(I) Ratio (M AC / M F ) between the total molar amount (M AC ) of the anion derived from the acid component (C) and the total molar amount (M F ) of the fluorine ion derived from the fluorine-containing material (B) ) Is 0.35 or more and less than 2.00.
(II) The total concentration (g / L) of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing product (B) is 25 or more.
(III) The total molar amount (M F ) of fluorine ions derived from the fluorine-containing material (B) and the total molar amount of zirconium ions derived from the fluorine-free zirconium compound (A) and the fluorine-containing material (B) (M Zr) and the ratio of (M F / M Zr) is less than 6.00 2.00 or more.
The replenisher according to claim 1, wherein the ratio (M AC / M F ) is more than 0.50 and less than 2.00.
The replenisher according to claim 1 or 2, wherein the ratio (M AC / M F ) is more than 0.50 and not more than 1.60.
Surface treatment in which a metal material is continuously subjected to chemical conversion treatment and / or electrolytic treatment in a surface treatment solution for metal material containing zirconium ions and fluorine ions to form a chemical conversion treatment film containing zirconium on the metal material. A method for producing a metal material,
A method for producing a surface-treated metal material, wherein the replenisher according to any one of claims 1 to 3 is added to the surface treatment liquid for metal material to replenish zirconium ions.
A surface-treated metal material obtained from the method for producing a surface-treated metal material according to claim 4.