JP6352986B2 - Metal surface treatment agent for electrolytic treatment, method for producing metal surface treatment agent for electrolytic treatment, and surface treatment method for metal material - Google Patents

Description

The present invention relates to a metal surface treatment agent for electrolytic treatment, a method for producing a metal surface treatment agent for electrolytic treatment, and a surface treatment method for a metal material .

  To date, various techniques have been proposed for various metal materials as surface treatment techniques for improving the properties of the metal materials.

  For example, the tinplate material is obtained by plating tin (tin, Sn) on the surface of a steel plate. This tinplate material is resistant to rust, has corrosion resistance to moisture, etc., and is suitable for welding and soldering, so it is widely used mainly as a material for cans (welding cans and solder cans) and electrical parts. Material. Here, the surface treatment method for the tinplate material is typically chemical conversion treatment (for example, see Patent Document 1), electrolytic treatment (for example, see Patent Document 2), or coating type treatment (for example, Patent Document 3). Can be classified. Furthermore, there are a wide variety of types of coatings formed on the tinplate material (see, for example, Patent Documents 1 to 3).

Japanese Patent Laid-Open No. 1-100281 JP 2009-280888 A JP 2004-307923 A

  Here, as described above, the tinplate material is mainly used as a material for the can. In consideration of the use in this application, the surface-treated tinplate material can be processed into cans, film adhesion, paint adhesion (primary paint adhesion, secondary paint adhesion), corrosion resistance (under-coating corrosion resistance) , Retort rust resistance) and sulfur blackening resistance are required.

  The inventors of the present invention have made various studies on coating types and processing methods that satisfy these properties. As a result, Sn is electrolytically treated using a metal surface treatment agent containing a dissolved Zr component, a dissolved F component, and a dissolved P component. It has been found that when the Zr-P film is formed on the system plating, the above-described properties can be realized to the same level as the conventional chromate treatment.

  However, on the other hand, the inventors of the present invention have formed a Zr—P-based film on the Sn-based plating by electrolytic treatment and formed a film on the Sn-based plating by other film types and processing methods. It was found that the discoloration resistance when aged for a long time in a humid environment may be inferior to that of the sample.

  Therefore, the present invention is only for can manufacturing process, film adhesion, paint adhesion (primary paint adhesion, secondary paint adhesion), corrosion resistance (under-coating corrosion resistance, retort rust resistance), sulfur blackening resistance, etc. In addition, discoloration resistance can be imparted to the Sn-based plated material, and the Zr—P-based film deposition property (short-time film deposition property) in a short time, and the metal surface treatment agent by Sn mixing It is an object of the present invention to provide a metal surface treatment agent for electrolytic treatment that is practically suitable, such as stability (resistance to Sn contamination) and stability of the metal surface treatment agent over time (treatment agent stability over time).

The present invention is as follows.
[1] A dissolved Zr component, a dissolved F component, a dissolved P component, one or more dissolved metal M components selected from the group consisting of a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component, nitrate ions, chloride One or more anions selected from the group consisting of product ions and sulfate ions, and the converted mass (P _w ) of the P element of the dissolved P component and the converted mass of the Zr element of the dissolved Zr component ( Zr _w ) (P _w / Zr _w ) is in the range of 0.04 to 0.5, and the dissolved metal M component metal elements (total of Zn element, Mn element and Cu element) For the electrolytic treatment, the mass ratio (M _w / Zr _w ) of the converted mass (M _w ) and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is in the range of 0.05 to 2.5. Metal surface treatment agent.
[2] The mass ratio (F _w / Zr _w ) between the converted mass (F _w ) of the F element of the dissolved F component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is 1.3 or more. The metal surface treatment agent for electrolytic treatment according to [1], which is within a range of 5 or less.
[3] The metal surface treatment agent for electrolytic treatment according to [1] or [2], wherein the Zr element concentration is in a range of 1000 mg / L to 1950 mg / L.
[4] The metal surface treatment agent for electrolytic treatment according to the above [1] to [3], wherein the pH is in the range of 3.4 or more and 4.8 or less.
[5] Further, at least one component selected from the group consisting of a dissolved Sn component, a dissolved Fe component, a dissolved ammonia N component, a dissolved Na component and a dissolved K component may be contained. In this case, the dissolved Zr component Reduced mass of Zr element (Zr _w ), reduced mass (M _w ) of metal element (Zn element, Mn element, Cu element) of the dissolved metal M component, converted mass of Sn element of the dissolved Sn component (Sn _w ), the total mass and, in terms of the mass of Zr element in the dissolution Zr components of reduced mass of Fe element of the dissolved Fe component (Fe _w) and reduced mass of N elements of the dissolved ammonia state N component _{(N w)} (Zr _w), the molten metal M component metal equivalent weight _(M w), reduced mass _(Sn w of Sn element of the dissolution Sn component), reduced mass of Fe element of the dissolved Fe component _(Fe w), the dissolution Ammo N component Reduced mass of N elements _(N w), the dissolved Na weight ratio of the total mass of the reduced mass of the components of the Na element (Na _w) and reduced mass of K elements of the lysis K component _{(K w)} CA: {( _{Zr w + M w + Sn w} + Fe w + N w) / (Zr w + M w + Sn w + Fe w + N w + Na w + K w)} is 0.9 or more, wherein [1] electrolyzed metal to [4] Surface treatment agent.
[6] The metal surface treatment agent for electrolytic treatment according to the above [1] to [5], wherein the electrical conductivity is in the range of 1.0 S / m to 6.0 S / m.
[7] The metal surface treatment agent for electrolytic treatment according to [1] to [6], wherein the metal to be treated is Sn-based plating.
[8] The metal surface treatment agent for electrolytic treatment according to [7], wherein the metal to be treated is alloy plating of Sn and Fe.
[9] One or more dissolved metal M components selected from the group consisting of dissolved Zr component, dissolved F component, dissolved P component, dissolved Zn component, dissolved Mn component and dissolved Cu component, nitrate ion, chloride One or more anions selected from the group consisting of a product ion and a sulfate ion,
The mass ratio (P _w / Zr _w ) of the converted mass (P _w ) of the P element of the dissolved P component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is 0.04 or more and 0.5 or less. Is in range,
Ratio (M _w / Zr _w ) of reduced mass (M _w ) of metal element (Zn element, Mn element, Cu element) of dissolved metal M component and reduced mass (Zr _w ) of Zr element of dissolved Zr component Is in the range of 0.05 to 2.5,
A method for producing a metal surface treatment agent for electrolytic treatment,
It includes a step of adding and mixing one or more raw materials to be a supply source of the dissolved Zr component, the dissolved F component, the dissolved P component, the dissolved metal M component, and the anion to a liquid medium. Production method.
[10] A ratio (F _w / Zr _w ) of a converted mass (F _w ) of the F element of the dissolved F component to a converted mass (Zr _w ) of the Zr element of the dissolved Zr component is 1.3 or more and 2.5 [9] The method for producing a metal surface treatment agent for electrolytic treatment according to [9], which is within the following range.
[11] The method for producing a metal surface treatment agent for electrolytic treatment according to [9] or [10], wherein the Zr element concentration is in a range of 1000 mg / L to 1950 mg / L.
[12] The method for producing a metal surface treatment agent for electrolytic treatment according to the above [9] to [11], wherein the pH is in the range of 3.4 to 4.8.
[13] Further, at least one component selected from the group consisting of a dissolved Sn component, a dissolved Fe component, a dissolved ammonia N component, a dissolved Na component, and a dissolved K component may be contained. In this case, the dissolved Zr component Reduced mass of Zr element (Zr _w ), reduced mass (M _w ) of metal element (Zn element, Mn element, Cu element) of the dissolved metal M component, converted mass of Sn element of the dissolved Sn component (Sn _w ), The converted mass of Fe element of the dissolved Fe component (Fe _w ) and the total mass of N element converted mass (N _w ) of the dissolved ammonia N component, and the converted mass of Zr element of the dissolved Zr component (Zr _w ) the molten metal M component metal equivalent weight _(M w), reduced mass _(Sn w) of tin (Sn) element of the dissolution Sn component, in terms of mass _(Fe w) of Fe element of the dissolution Fe component, the dissolved ammonium status N component N Reduced mass of the element _(N w), the dissolved mass in terms (Na _w) of Na component as Na element and the ratio CA of the total mass of the reduced mass _{(K w)} of K elements of the dissolution K component: {(Zr _{w + M w + Sn w + Fe} w + N w) / (Zr w + M w + Sn w + Fe w + N w + Na w + K w)} is 0.9 or more, the [9] to electrolytic treatment for metal surface treatment [12] Manufacturing method.
[14] The method for producing a metal surface treatment agent for electrolytic treatment according to [9] to [13], wherein the electrical conductivity is in a range of 1.0 S / m to 6.0 S / m.
[15] The method for producing a metal surface treatment agent for electrolytic treatment according to [9] to [14], wherein the metal to be treated is Sn-based plating.
[16] The method for producing a metal surface treatment agent for electrolytic treatment according to [15], wherein the metal to be treated is alloy plating of Sn and Fe.
[17] In a surface treatment method for a metal material, including a step of energizing the metal to be treated as a cathode side in a state where the metal to be treated is immersed in a metal treatment agent for electrolytic treatment,
The metal treatment agent for electrolytic treatment is
One or more dissolved metal M components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component and a dissolved Cu component, nitrate ions, chloride ions and One or more anions selected from the group consisting of sulfate ions,
The ratio (P / Zr) of the converted mass (P _w ) of the P element of the dissolved P component to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is in the range of 0.04 or more and 0.5 or less. Yes,
The ratio (M / Zr) of the converted mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is 0. A surface treatment method characterized by being in the range of .05 to 2.5.
[18] Ratio (F _w / Zr _w ) of the converted mass (F _w ) of the F element of the dissolved F component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component in the metal treatment agent for electrolytic treatment ) Is within the range of 1.3 to 2.5, the surface treatment method according to the above [17].
[19] The surface treatment method according to [17] or [18], wherein the Zr element concentration in the metal treatment agent for electrolytic treatment is in a range of 1000 mg / L to 1950 mg / L.
[20] The surface treatment method according to any one of [17] to [19], wherein the pH of the metal treatment agent for electrolytic treatment is in the range of 3.4 to 4.8.
[21] The metal treatment agent for electrolytic treatment may further contain at least one component selected from the group consisting of a dissolved Sn component, a dissolved Fe component, a dissolved ammonia N component, a dissolved Na component, and a dissolved K component. Well, in this case, the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component, The total mass of the converted mass of Sn element (Sn _w ), the converted mass of Fe element of the dissolved Fe component (Fe _w ), and the converted mass of N element of the dissolved ammonia N component (N _w ), and the dissolved Zr component Equivalent mass of Zr element (Zr _w ), Equivalent mass of molten metal M component (M _w ), Equivalent mass of Sn element of Sn component (Sn _w ), Equivalent mass of Fe element of dissolved Fe component ( Fe _w), said Reduced mass of the N elements of solutions ammoxidation state N component _(N w), of the total weight of the reduced mass of the reduced mass (Na _w) and K elements in the dissolution K component of Na element of the dissolved Na component _{(K w)} mass ratio _{CA: {(Zr w + M} w + Sn w + Fe w + N w) / (Zr w + M w + Sn w + Fe w + N w + Na w + K w)} is 0.9 or more, the [17] - [20 ] The surface treatment method.
[22] The surface treatment method of [17] to [21], wherein the electrical conductivity of the metal treatment agent for electrolytic treatment is in the range of 1.0 S / m to 6.0 S / m.
[23] The surface treatment method of [17] to [22], wherein the metal to be treated is Sn-based plating.
[24] The surface treatment method according to [23], wherein the metal to be treated is alloy plating of Sn and Fe.

  According to the present invention, can processability, film adhesion, paint adhesion (primary paint adhesion, secondary paint adhesion), corrosion resistance (under-coating corrosion resistance, retort rust resistance), sulfur blackening resistance, etc. only In addition, it is possible to impart discoloration-resistant properties to Sn-based plating materials, and practically preferred metal surface treatment agents for electrolytic treatment such as short-time film deposition, resistance to Sn contamination, and stability over time of treatment agents. Can be provided.

The present invention will be specifically described in the following order.
1. 1. Metal surface treatment agent for electrolytic treatment 1-1. Component 1-2. Composition (content ratio, content)
1-3. Liquid 2 2. Manufacturing method of metal surface treatment agent for electrolytic treatment 2-1. Raw material 2-2. Process 3. 3. Method of using metal surface treatment agent for electrolytic treatment 3-1. Target metal 3-2. process

<< 1. Metal surface treatment agent for electrolytic treatment >>
The metal surface treatment agent for electrolytic treatment according to the present invention comprises at least one selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component. Containing the dissolved metal M component and one or more anions selected from the group consisting of nitrate ion, chloride ion and sulfate ion, and the converted mass (P _w ) of the P element of the dissolved P component and the above The ratio (P _w / Zr _w ) of the dissolved Zr component to the reduced mass (Zr _w ) of the Zr element is in the range of 0.04 to 0.5, and the metal element (Zn element, The ratio (M _w / Zr _w ) of the converted mass (M _w ) of Mn element, Cu element) to the converted mass (Zr _w ) of Zr element of the dissolved Zr component is in the range of 0.05 to 2.5 It is. In addition, the metal surface treating agent for electrolytic treatment according to the present invention includes both a new liquid (liquid not subjected to electrolytic treatment) and a load liquid (liquid after electrolytic treatment is performed).

<1-1. Component>
{1-1-1. Dissolved Zr component}
The dissolved Zr component refers to a component containing a Zr element in a dissolved state in the agent under normal temperature (20 ° C.) and normal pressure (1 atm = 101325 Pa). The dissolved Zr component is not particularly limited. For example, in addition to Zr ions (for example, Zr ⁴⁺ ), complex ions (ZrF ₆ ²⁻ , ZrF ₅ ⁻ , ZrF) formed by bonding Zr and other components (for example, F) are used. ₃ ⁺ , ZrF ₂ ²⁺ , ZrF ³⁺ ), molecules (ZrF ₄ ), zirconium oxide ions (ZrO ³⁺ and HZrO ₃ ⁻ ) and the like. In addition, since the metal surface treatment agent for electrolytic treatment according to the present invention preferably contains F exceeding the amount that Zr can bind to, most of the dissolved Zr component is ZrF ₆ ²⁻ (or It is presumed that a part of F is substituted with another ligand, and a cation is electrically bonded to the anion).

{1-1-2. Dissolved F component}
The dissolved F component refers to a component containing an F element which is in a dissolved state in the agent under normal temperature (20 ° C.) and normal pressure (1 atm = 101325 Pa). The dissolved F component is not particularly limited. For example, in addition to F ions, complex ions (ZrF ₆ ²⁻ , ZrF ₅ ⁻ , ZrF ₃ ⁺ , ZrF) formed by bonding F and other components (for example, Zr, H) are combined. ₂ ²⁺ , ZrF ³⁺ , HF ₂ ⁻ ) and molecules (HF, ZrF ₄ ). In addition, since the metal surface treatment agent for electrolytic treatment according to the present invention preferably contains F exceeding the amount that Zr can bind to, most of the dissolved F component is ZrF ₆ ²⁻ (or , A part of F is substituted with another ligand, and a cation is electrically bonded to the anion), and the remainder is bound to F ions, HF or other components Presumed to exist as a body. In the above description, “ZrF ₆ ²⁻ ” is given as an example of “dissolved F component”. However, since the component also contains Zr, the component also corresponds to “dissolved Zr component” (others) The same applies to the other components). That is, when a component in the liquid exists in a dissolved state, and the certain component contains two or more elements of Zr, F and metal (M) (for example, “X” and In “Y”), the certain component is both “dissolved X component” and “dissolved Y component”.

{1-1-3. Dissolved P component}
The dissolved P component refers to a component containing a P element in a dissolved state at normal temperature (20 ° C.) and normal pressure (1 atm = 101325 Pa). The dissolved P component is not particularly limited. For example, it exists in the form of (1) orthophosphate phosphorus, (2) polymerized phosphate phosphorus, (3) soluble organophosphate phosphorus, and the like. Here, (1) orthophosphoric phosphorus is a component containing a phosphate radical (PO ₄ ) in a dissolved state in the agent, for example, for example, orthophosphoric acid (H ₃ PO ₄ ), phosphate ions (H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ , PO ₄ ³⁻ ) and the like, as well as conjugates of these ions with other components. In addition, (2) polymerized phosphorous phosphorus is, as a more specific example, pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid, their ions, etc., which are dissolved in the agent, and their A combination of an ion and another component can be mentioned. Further, (3) soluble organophosphorus phosphorus is a component containing organophosphoric acid dissolved in the agent, for example, phosphonic acid dissolved in the agent, and their ions, and A conjugate of these ions with other components can be mentioned. Here, the organic phosphoric acid is a composition containing carbon element (C), hydrogen element (H), oxygen element (O), and phosphorus element (P), and phosphorus oxygen acid (phosphonic acid). It has the following properties.

{1-1-4. Dissolved metal M component}
The dissolved metal M component is one or more selected from the group consisting of a Zn component, a Mn component, and a Cu component that are in a dissolved state in the agent under normal temperature (20 ° C.) and normal pressure (1 atm = 101325 Pa). Refers to the metal component. The dissolved metal M component is not particularly limited. For example, in addition to metal ions (for example, Zn ²⁺ and Zn ⁺ , Mn ²⁺ and Mn ⁴⁺ , Cu ²⁺ and Cu ^+, etc.), metal (ion) and other components In the form of a conjugate (for example, a complex). Here, among these metal components, the manganese component is preferable because of particularly excellent discoloration resistance.

{1-1-5. anion}
The metal surface treatment agent for electrolytic treatment according to the present invention further contains one or more anions selected from the group consisting of nitrate ions, chloride ions and sulfate ions. When taking measures to reduce nitrate nitrogen (including nitrate nitrogen free) as wastewater countermeasures for this treatment agent, replace all or part of nitrate ions with chloride ions and / or sulfate ions as anions. Measures can be taken. When taking measures to reduce chloride (including chloride-free) as an anti-corrosion measure for electrolytic treatment equipment, replace all or part of the chloride ions with nitrate ions and / or sulfate ions as anions. Can do. When taking countermeasures for drainage of this treating agent and preventing corrosion of the electrolytic treatment apparatus, it is possible to take countermeasures by replacing all or part of nitrate ions and chloride ions with sulfate ions as anions.

{1-1-6. Other ingredients}
The metal surface treatment agent for electrolytic treatment according to the present invention may contain a known component used in the field as necessary. For example, a dissolved Sn component, a dissolved Fe component, a dissolved ammonia N component (that is, ammonium or ammonia), a dissolved Na component, or a dissolved K component may be contained. Here, the other component may be a component added at the time of preparing the new solution, or a component supplied from a material (steel plate) or the like at the stage of the load solution. For example, the dissolved Sn component and the dissolved Fe component are not limited, but are typically components supplied from a material (steel plate) in the course of processing. In addition, for example, dissolved Na component and dissolved K component are not limited, but typically included in industrial water (well water, groundwater, tap water) used as a liquid medium in the treatment process. Or a component that is supplied to the surface of the material while being processed. However, it is desirable that the metal surface treatment agent for electrolytic treatment according to the present invention does not contain a dissolved K component (typically potassium ions) or contains only a trace amount (K _w : 3 mg / L or less). When the dissolved K component is not contained or only a trace amount is contained, the film deposition property is improved particularly for a short time. Moreover, it is desirable that the metal surface treatment agent for electrolytic treatment according to the present invention does not contain a dissolved Na component (typically sodium ion) or contains only a trace amount (Na _w : 3 mg / L or less). When the dissolved Na component is not contained or only a trace amount is contained, the film appearance is particularly improved. For this reason, it is preferable to use deionized water as the liquid medium of the treatment agent.

{1-1-7. Liquid medium}
The liquid medium in the metal surface treatment agent for electrolytic treatment according to the present invention is preferably a liquid medium mainly composed of water (for example, deionized water or pure water). Here, “mainly” means 51% by mass or more of water (preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass) based on the total mass of the liquid medium. As mentioned above, it means 90% by mass or more particularly preferably. Therefore, “dissolution” in the above-described components (dissolved Zr component, dissolved F component, dissolved P component, dissolved metal M component, etc.) is a state of being dissolved in a liquid medium (preferably water) mainly composed of water. This means, for example, “water-soluble type”. In addition, the metal surface treatment agent for electrolytic treatment according to the present invention is not only in the form containing only the above-described dissolved component and liquid medium, but also in which sludge, for example, an excessive amount of ions or the like is insolubilized {detailed form is unknown However, for example, a form in which FePO ₄ , SnF ₄ , SnO (OH) ₂ , Sn (OH) _{4 and the} like} coexist is also included. The liquid medium may contain a liquid medium other than water (for example, a water-miscible liquid medium, for example, an alcohol such as ethanol), but a smaller amount is preferable for performing the electrolytic treatment. . The liquid solvent other than water is 20% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably based on the total mass of the liquid medium. Is 1% by mass or less. The agent may be in a dry form or a concentrated form. In this case, dissolve or dilute with water on site.

<1-2. Composition>
{1-2-1. Content ratio}
(Mass ratio of 1-2-1-1.P _w and Zr _w)
The ratio (P _w / Zr _w ) of the converted mass (P _w ) of the P element of the dissolved P component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component in the metal surface treatment agent for electrolytic treatment according to the present invention is , 0.04 or more and 0.5 or less, preferably 0.06 or more and 0.4 or less, and more preferably 0.08 or more and 0.3 or less. . In the specific system of the metal surface treatment agent for electrolytic treatment according to the present invention, by setting the ratio within the range, {exactly, in addition to the parameter, the ratio of M _w and Zr _w described later (M _w / Zr _w ) within the range described below}, can processability, film adhesion, paint adhesion (primary paint adhesion, secondary paint adhesion), corrosion resistance (under-coating corrosion resistance, retort resistance Rustability), sulfur blackening resistance, etc., as well as discoloration resistance can be imparted to Sn-based plating materials, and practical use such as short-time film deposition, resistance to Sn contamination, and stability over time of processing agents. A metal surface treatment agent for electrolytic treatment that is suitable for the above can be provided. In particular, when P _w / Zr _w is less than 0.04, the resistance to sulfur blackening deteriorates. _Further, when P w / Zr _w is 0.5 greater than the film adhesion is deteriorated. Here, mass measurement of the P element and the Zr element in the agent can be performed by a known method such as an ICP emission spectroscopic analyzer (ICP-AES) according to JIS-K0116: 2014 standard.

(The ratio of the 1-2-1-2.M _w and Zr _w)
In the metal surface treatment agent for electrolytic treatment according to the present invention, {converted mass (M _w ) of metal element (Zn element, Mn element, Cu element) of dissolved metal M component and converted mass (Zr _{w of} dissolved Zr component) )} (M _w / Zr _w ) is in the range of 0.05 to 2.5, preferably in the range of 0.1 to 2.0, 0.15 More preferably, it is 1.5 or less. In addition, the said ratio is a ratio based on the total mass of all the said 2 types or more, when 2 or more types of metal M elements exist. Thus, in the specific system of the metal surface treatment agent for electrolytic treatment according to the present invention, by setting the ratio within the range, to be precise, in addition to the parameters, the above-described P _w and Zr _w By setting the ratio (P _w / Zr _w ) within the aforementioned range}, can manufacturing process, film adhesion, paint adhesion (primary paint adhesion, secondary paint adhesion), corrosion resistance (under coating) In addition to corrosion resistance, retort rust resistance), sulfur blackening resistance, resistance to Sn contamination, etc., it is possible to impart discoloration resistance properties to Sn-based plating materials as well as short-time film deposition and resistance to Sn contamination. In addition, it is possible to provide a metal surface treatment agent for electrolytic treatment that is suitable for practical use, such as treatment agent stability over time. In particular, when M _w / Zr _w is less than 0.05, discoloration resistance deteriorates. _Further, when the M w / Zr _w is 2.5 greater than can-workability is deteriorated. Here, the mass measurement of the metal M element in the agent can be performed by a known method such as an ICP emission spectroscopic analyzer (ICP-AES) according to JIS-K0116: 2014 standard.

(Mass ratio of 1-2-1-3.F _w and Zr _w)
Ratio (F _w / Zr _w ) of {converted mass of F element of dissolved F component (F _w ) and converted mass of Zr element of dissolved Zr component (Zr _w )} in the metal surface treatment agent for electrolytic treatment according to the present invention. ) Is preferably in the range of 1.3 to 2.5, more preferably in the range of 1.32 to 2.4, and 1.36 to 2.3. It is further preferable that When the ratio of F _w to Zr _w is within the above range, the above-described effect can be further improved. In particular, when F _w / Zr _w is 1.3 or more, the resistance to Sn contamination is improved. When F _w / Zr _w is 2.5 or less, the secondary coating adherence becomes better. Here, mass measurement of F element in the agent can be performed by quantitatively analyzing a solution obtained by distilling and separating a fluorine compound described in JIS-K0102: 2014 standard 34.1 based on a lanthanum-alizarin complexone spectrophotometric method. .

(1-2-1-4. Mass ratio between specific component groups)
Further, it may contain at least one component selected from the group consisting of dissolved Sn component, dissolved Fe component, dissolved ammonia N component, dissolved Na component and dissolved K component. In this case, conversion of Zr element of Zr component Mass (Zr _w ), converted mass (M _w ) of metal element (Zn element, Mn element, Cu element) of dissolved metal M component, converted mass (Sn _w ) of Sn element of dissolved Sn component, Fe of dissolved Fe component Total mass of reduced mass of element (Fe _w ) and reduced mass of N element of dissolved ammonia N component (N _w ), reduced mass of Zr element of dissolved Zr component (Zr _w ), metal element of dissolved metal M component Converted mass (M _w ), converted Sn element mass of dissolved Sn component (Sn _w ), converted Fe element converted mass of Fe element (Fe _w ), dissolved ammonia N component converted mass of N element (N _w ), N of dissolved Na component When the ratio of the total mass of the reduced mass (Na _w) and reduced mass of K elements dissolution K component elements _{(K w)} was CA, CA is preferably made at least 0.9, 0 More preferably, it is .92 or more. Within this range, the appearance of the film becomes good. Here, the mass measurement of the Sn element and the Fe element in the agent can be performed by a known method such as an ICP emission spectroscopic analyzer (ICP-AES) according to JIS-K0116: 2014 standard. Further, mass measurement of N element, Na element and K element of the dissolved ammonia N component in the agent can be performed by a known method such as an ion chromatogram method according to JIS-K0102: 2016 standard.

{1-2-2. Content}
(1-2-2-1. Zr element concentration)
The Zr element concentration in the metal surface treatment agent for electrolytic treatment according to the present invention is preferably in the range of 1000 mg / L to 1950 mg / L, and in the range of 1100 mg / L to 1850 mg / L. Is more preferable, and it is still more preferable that it is in the range of 1200 mg / L or more and 1750 mg / L or less. Within the range, normal electrolytic conditions {for example, the test material is on the cathode side, and the test material is energized with a constant current density (for example, immersed in a predetermined 40 ° C. metal surface treatment agent at the same time. Even if it is held at a current density of 0 A / dm ² for 1 second)}, a metal material having the above-described effects can be provided. In particular, when the Zr concentration is 1000 mg / L or more, the retort rust resistance is improved. When the Zr element concentration is 1950 mg / L or less, the primary paint adhesion is improved.

(1-2-2-2. Other component concentrations)
First, the F element concentration, the P element concentration, and the metal M element concentration are preferably values calculated based on the aforementioned Zr element concentration and the aforementioned mass ratio of each element to the Zr element. Is preferred. The concentration of one or more anions selected from the group consisting of nitrate ion, chloride ion and sulfate ion is a suitable numerical range (1.0 S / m or more and 6.0 S / m or more) described later. It is preferable to determine appropriately within the following.

<1-3. Liquidity>
{1-3-1. pH}
The pH of the metal surface treatment agent for electrolytic treatment according to the present invention is preferably 3.4 or more and 4.8 or less, more preferably 3.5 or more and 4.7 or less. More preferably, it is 3.6 or more and 4.5 or less. When the pH is 3.4 or more, the corrosion resistance under the coating film becomes better. When the pH is 4.8 or less, the treatment agent stability over time is improved. In addition, this pH is the value measured at the electrolysis temperature (typically 40 degreeC) by JIS-Z8802: 2011 about the metal surface treating agent for electrolytic treatment.

{1-3-2. Electrical conductivity}
The electric conductivity in the metal surface treatment agent for electrolytic treatment according to the present invention is preferably in the range of 1.0 S / m or more and 6.0 S / m or less, and in the range of 1.5 or more and 5.5 or less. It is more preferable that it is in the range of 2.0 to 5.0. When the electric conductivity is 1.0 or more, the film deposition property is improved for a short time. When the electrical conductivity is 6.0 or less, corrosion to the electrolytic treatment apparatus is less likely to occur. Even if the electric conductivity exceeds 6.0, the effect of film deposition for a short time is saturated. In addition, this electrical conductivity is the value measured at the electrolysis temperature (typically 40 degreeC) by JIS-K0130: 2008 about the metal surface treating agent for electrolytic treatment.

≪2. Method for producing metal surface treatment agent for electrolytic treatment >>
The method for producing a metal surface treatment agent for electrolytic treatment according to the present invention comprises one or more raw materials serving as a supply source of the dissolved Zr component, the dissolved F component, the dissolved P component, the dissolved metal M component, and the anion. Adding to the liquid medium and mixing. Here, even if one raw material is a supply source of a plurality of the components (a plurality of components selected from a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved metal M component, and the anion) ( For example, fluorinated zirconic acid, which is one raw material, is also a source of dissolved Zr component and a source of dissolved F component), and a plurality of raw materials are one component (dissolved Zr component, dissolved F component, dissolved) Even if it is a supply source of P component, dissolved metal M component and any one component selected from the anions) (for example, different raw materials such as fluorozirconic acid and hydrofluoric acid supply dissolved F component) A plurality of raw materials are sources of a plurality of the components (a plurality of components selected from a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved metal M component, and the anion) (E.g. different raw materials There phosphoric acid and hydrofluoric acid is a source of soluble P component and dissolving F component are different components, respectively). Hereinafter, each raw material and process will be described in detail.

<2-1. Raw material>
(2-1-1. Supply Source of Dissolved Zr Component)
The source of the dissolved Zr component is not particularly limited, and is, for example, a compound containing a zirconium atom. For example, zirconium sulfate, zirconium oxysulfate, zirconium ammonium sulfate, zirconium oxynitrate, zirconium ammonium nitrate, fluorozirconic acid , Fluorozirconium complex salts, and the like. These may be used alone or in combination of two or more.

(2-1-2. Source of dissolved F component)
The source of the dissolved F component is not particularly limited, and is, for example, a compound containing a fluorine atom. For example, fluorozirconic acid, ammonium fluoride, ammonium hydrogen fluoride, germanium fluoride, iron fluoride, sodium fluoride. Sodium hydrogen fluoride and the like, and these may be used alone or in combination of two or more. In addition, the fluorozirconic acid and the fluorozirconium complex salt which are the supply sources of the dissolved Zr component as exemplified above are also the supply sources of the dissolved F component.

(2-1-3. Source of dissolved P component)
The supply source of the dissolved P component is not particularly limited. For example, (1) orthophosphoric phosphorus includes phosphoric acid (orthophosphoric acid) and salts thereof (such as ammonium orthophosphate). (2) Polymerized phosphoric acid phosphorus is a chain phosphoric acid condensate, including pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, etc., and salts thereof (ammonium pyrophosphate, ammonium tripolyphosphate, tetrapolyphosphoric acid). Including ammonium phosphate). (3) Examples of organophosphate phosphorus include nitrilotrismethylenephosphonic acid, nitrilotrispropylenephosphonic acid, nitrilodiethylmethylenephosphonic acid, methane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1, 1-diphosphonic acid, propane-1-hydroxy-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and the like and salts thereof. The supply source of the dissolved P component may be one kind or a combination of two or more kinds.

(2-1-4. Source of dissolved metal M component)
The supply source of the dissolved metal M component is not particularly limited, and is, for example, a water-soluble metal M salt. Examples of water-soluble zinc salts include zinc nitrate (II), zinc sulfate (II), zinc sulfide (II), zinc chloride (II), zinc acetate (II), zinc cyanide (II), ammonium zinc chloride ( II), zinc tartrate (II), zinc perchlorate (II) and the like; water-soluble manganese salts include manganese nitrate (II) hexahydrate, manganese acetate (II) tetrahydrate , Manganese (II) chloride tetrahydrate, manganese sulfate (II) pentahydrate, manganese sulfate (II) ammonium hexahydrate and the like; , Copper sulfate (II), copper nitrate (II), copper chloride (II), copper acetate (II), copper citrate (II), copper tartrate (II), copper gluconate (II) and the like. . In addition, the supply source of a melt | dissolved metal (M) component may be 1 type, or may use 2 or more types together.

(2-1-5. Source of anion)
The anion supply source is not particularly limited, and examples thereof include inorganic acids, for example, inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid, and water-soluble salts of inorganic acids. The anion supply source may be one kind or a combination of two or more kinds. In addition, when a component used as a supply source of the above-described other components (for example, dissolved Zr component) contains the anion (that is, nitrate ion, chloride ion, sulfate ion), the component is also an anion. A source of ions. The anion (ie, nitrate ion, chloride ion, sulfate ion) is paired (ie, neutral salt) with the cation (preferably ammonium) of the treatment agent, and serves as a supporting electrolyte that increases the electrical conductivity of the treatment agent. Works.

<2-2. Process>
In the metal surface treatment agent for electrolytic treatment according to the present invention, for example, the above-mentioned raw material serving as a supply source of each component is added to a liquid medium mainly composed of water (for example, water), and heated and cooled as necessary. It can be prepared by stirring with stirring. As a procedure for adjusting the pH and electrical conductivity, the pH is adjusted to a predetermined value after adding the raw materials serving as the supply sources of the aforementioned components. Next, the anion (ie, nitrate ion, chloride ion, sulfate ion) is added as a neutral salt (preferably an ammonium salt) to adjust to a predetermined electrical conductivity. A substance (neutral salt) added to adjust the electrical conductivity is called a supporting electrolyte. Thereafter, when the pH changes from a predetermined value, fine adjustment is performed. In addition, although adjustment of pH is performed using an alkali and an acid, there is no restriction | limiting in particular. Preferably, the alkali is ammonia, and the acid is an acid (inorganic acid) that is the same component as the anion of the supporting electrolyte. By using ammonia to adjust the pH, even if ammonia is incorporated into the formed film, the ammonia is volatilized from the film during subsequent drying, and as a result, the film performance is adversely affected. It is not necessary. Further, by using an acid (inorganic acid) of the same component as the anion of the supporting electrolyte for adjusting the pH, adverse effects on the film performance of the formed film can be minimized.

≪3. How to use metal surface treatment agent for electrolytic treatment >>
<3-1. Target metal>
The greatest feature when a film is formed on a target metal using the metal surface treatment agent for electrolytic treatment according to the present invention is that the surface-treated target metal is secured while ensuring performance such as canning processability. It is a point which can provide discoloration resistance. From this viewpoint, the target metal of the metal surface treatment agent for electrolytic treatment according to the present invention is preferably provided with Sn-based plating {for example, Sn plating, plating containing Sn and other metals (for example, solder)}. It is a metal material (for example, a tin steel plate). Here, the Sn-based plating means that the Sn content in the plating layer is 20% by mass or more (preferably 50% by mass or more, more preferably 70% or more, based on the total mass of the plating layer, The term “plating” is preferably 90% by mass or more. In addition, in Sn-based plating, one or more kinds of other metals (for example, Fe) may be present in addition to Sn, and an alloy may be formed in the plating {for example, Sn is electrically applied An alloy of Sn and Fe formed when heat treatment (reflow) is performed later}. Further, it is preferable that the Sn-based plating contains Sn in an amount of 100 to 15000 mg / m ² on at least one surface of the metal material to be plated. Furthermore, even if Sn type plating does not contain Zn or contains Zn, it is suitable that it is 3 mass% or less on the basis of the total mass of a plating layer, and it is 2 mass% or less. More preferred is 1% by mass or less. This is because when a certain amount of Zn is contained, discoloration hardly occurs in the first place. However, the metal surface treatment agent for electrolytic treatment according to the present invention, as described above, can be made, film adhesion, paint adhesion (primary paint adhesion, secondary paint adhesion), corrosion resistance (under the coating) It is possible to impart properties such as corrosion resistance, retort rust resistance) and resistance to sulfur blackening to the target metal. Therefore, from this viewpoint, the target metal is not limited to the Sn-based plated metal material, and may be a metal material such as an aluminum-based metal, an iron-based metal, a zinc-based metal, or a magnesium-based metal.

<3-2. Process>
The metal surface treatment agent for electrolytic treatment according to the present invention can be processed on a metal material by a normal electrolysis method, film adhesion, paint adhesion (primary paint adhesion, secondary paint adhesion), corrosion resistance. It is possible to form a film excellent in properties such as (under-coating corrosion resistance, retort rust resistance) and sulfur blackening resistance. As a specific example, when the metal material to be processed is a Sn-based plated metal material, the test material is the cathode side, and the test material is applied to the metal surface treatment agent for electrolytic treatment at a predetermined temperature (typically 40 ° C.). A method of energizing the test material at a predetermined current density (for example, 3.0 A / dm ² ) at the same time (or after the immersion) and holding the sample for a predetermined time (for example, 1 second). Although electrolysis temperature is not specifically limited, 10 degreeC or more and 55 degrees C or less are preferable. When the temperature is 10 ° C. or higher, the temperature can be easily maintained. When the temperature is 55 ° C. or lower, corrosion to the electrolytic treatment apparatus is less likely to occur. The current density is not particularly limited, but a lower current density requires a longer electrolysis time. A high current density can be dealt with in a short electrolysis time, but the film deposition efficiency may decrease.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. Unless otherwise specified, “%” means mass%.

<Test material>
The following materials were used as test materials.
(1) Electric Sn (tin) plated steel sheet (with reflow treatment) (ET)
Plate thickness: 0.3mm
Sn plating weight per unit area: 2.8 g / m ²
(2) Electro nickel-plated steel sheet (NI)
Plate thickness: 0.3mm
Ni plating basis weight: 0.8 g / m ²

<Preparation of metal surface treatment agent for electrolytic treatment>
Zirconium hydrofluoric acid as a source for supplying dissolved Zr component and dissolved F component in water, orthophosphoric acid as a source for supplying hydrofluoric acid and dissolved P component as a source for supplying dissolved F component An acid was added to obtain predetermined F _W / Zr _W and P _W / Zr _W. Next, after adding the substance types listed in Table 1 as raw materials to be the source of the dissolved metal (M) component and adding the amounts listed in Table 1, they are mixed thoroughly to completely dissolve the dissolved metal (M) component with the naked eye. It was. Thereafter, acid (acid of the same component as the anion constituting the supporting electrolyte shown in Table 1) or alkali (ammonia) was added to adjust pH. Furthermore, after adjusting the electrical conductivity by adding the supporting electrolyte shown in Table 1, the pH was finely adjusted as necessary. At this time, the acid and the alkali (ammonia and sodium hydroxide) were added and adjusted so that the CA also had a predetermined value. Thus, each metal surface treatment chemical conversion treatment liquid was obtained. When two or more electrolytes are mixed and used, when two or more supporting electrolytes are mixed and used, the mixing ratio is a mass ratio.

<Supporting electrolyte, raw material to be a source of anion and dissolved ammonium N component>
E1: Ammonium nitrate E2: Ammonium sulfate E3: Ammonium chloride

<Raw metal (M) component and raw material as anion source>
M1: Zinc nitrate M2: Manganese sulfate M3: Manganese nitrate M4: Manganese chloride M5: Copper nitrate M6: Cobalt nitrate

<Pretreatment>
The pretreatment of the test material (electrolytic treatment pretreatment) was performed by degreasing 30 seconds with an alkaline degreasing agent {Fine Cleaner-E6406 (Nihon Parkerizing Co., Ltd.), 2% building bath, 60 ° C}, and then tap water. This was carried out by washing with water and water with ion-exchanged water, removing water with a draining roll, and drying with a dryer.

<Electrolytic treatment (standard electrolytic treatment)>
The test material subjected to the pretreatment was subjected to the following electrolytic treatment (standard electrolytic treatment). The test material is used as a cathode, the carbon plate is used as a counter electrode, and the test material is immersed in a metal surface treatment agent for electrolytic treatment at a predetermined temperature (40 ° C.). At the same time, at a current density of 3.0 A / dm ² for 1 second. Electrolyzed. Thereafter, the surface of the test material is cleaned by spray-washing the electrolyzed test material with 25 ° C. city water for 5 seconds, drained using a roll squeeze, and the surface temperature of the test material reached 50 is reached. Drying was performed at ° C.

<Performance evaluation>
About the test material which performed said pre-processing and electrolytic treatment (standard electrolytic treatment), and the metal surface treating agent for electrolytic treatment itself, performance evaluation was performed about each item of (A)-(L) shown below. Table 2 shows the test materials, and Table 3 shows the results.

(A) Can manufacturing process A PET film having a thickness of 20 μm is laminated on both surfaces of a test material at 200 ° C., punched into a blank having a diameter of 150 mm, and then drawn with a drawing ratio of 1.67, and a can diameter of 90 mm. Can height: A can of about 40 mm was produced. Next, the drawn can was redrawn at a drawing ratio of 1.36 to produce a drawn can with a can diameter of 66 mm, and then the thickness reduction rate was obtained by three-stage ironing using the drawn can. A squeeze forming process was performed by applying a squeeze forming process to 50%, and a squeezed-ironing can having a can diameter of 66 mm and a can height of about 125 mm was produced. Then, the wrinkle, float, and peeling state of the film were evaluated in the following five stages with respect to the drawn and ironed can body. The evaluation above Δ is a practical level.
A: The total area ratio of the ridge part, the floating part, and the peeling part of the film is 0%.
○: The total area ratio of the ridge part, the floating part, and the peeling part of the film is more than 0% and 0.5% or less. △: The total area ratio of the ridge part, the floating part and the peeling part of the film exceeds 5% and 15% or less. X: The total area ratio of the ridge part, the floating part and the peeling part of the film exceeds 15% or the test material breaks. Unable to mold

(B) Film adhesion A PET film having a thickness of 20 μm was laminated at 200 ° C. on both sides of the test material, punched into a blank having a diameter of 150 mm, and then drawn at a drawing ratio of 1.67, and a can diameter of 90 mm. Can height: A can of about 40 mm was produced. Thereafter, the drawn can body was subjected to a retort treatment at 121 ° C. for 30 minutes, and the peeling state of the film was evaluated in the following five stages. The evaluation above Δ is a practical level.
A: Area ratio of peeled portion is 0%
○: Area ratio of peeled portion is more than 0% and not more than 2% ○ △: Area ratio of peeled portion is more than 2% and not more than 5% Δ: Area ratio of peeled portion is more than 5% and not more than 10% Is over 10%

(C) Primary paint adhesion Adhesiveness of epoxy-phenolic resin to the test material so as to form a coating film having a dry film thickness of 6 g / m ² , baking at 200 ° C. for 10 minutes, and depth reaching the base iron at intervals of 1 mm I put my eyes on. Then, after attaching a cellophane tape to the test material, the tape was peeled off, and the peeling state of the coating film was evaluated in the following five stages. The evaluation above Δ is a practical level.
A: Area ratio of peeled portion is 0%
○: Area ratio of peeled portion is more than 0% and not more than 5% ○ △: Area ratio of peeled portion is more than 5% and not more than 15% Δ: Area ratio of peeled portion is more than 15% and not more than 30% ×: Area ratio of peeled portion Is over 30%

(D) Secondary paint adhesion Depth reaching the base iron at intervals of 1 mm after applying an epoxy-phenol resin to the test material to form a coating film with a dry film thickness of 6 g / m ² and baking at 200 ° C. for 10 min. I put the eyes of that. Thereafter, the test material was subjected to a retort treatment at 121 ° C. for 30 minutes, and after drying, the cellophane tape was applied to the test material, and then the tape was peeled off. . The evaluation above Δ is a practical level.
A: Area ratio of peeled portion is 0%
○: Area ratio of peeled portion is more than 0% and not more than 5% ○ △: Area ratio of peeled portion is more than 5% and not more than 15% Δ: Area ratio of peeled portion is more than 15% and not more than 30% ×: Area ratio of peeled portion Is over 30%

(E) Corrosion resistance under coating film After applying epoxy-phenol resin to the test material so as to form a coating film with a dry film thickness of 6 g / m ² and baking at 200 ° C. for 10 minutes, cross-cut with a depth reaching the base iron Put. Thereafter, the test material was immersed in a test solution composed of a 1.5% citric acid-1.5% salt solution at 45 ° C. for 72 hours. Then, after washing and drying, the cellophane tape is applied to the test material, and then the tape is peeled off. The corrosion width (mm) of the corroded portion under the coating film in the crosscut portion and the area ratio (%) of the corroded portion of the flat plate portion Was evaluated according to the following five levels. The evaluation above Δ is a practical level.
A: The corrosion width of the corroded portion under the coating film of the crosscut portion is less than 0.2 mm, and the area ratio of the corroded portion of the flat plate portion is 0%.
○: Corrosion width of the corroded portion under the coating of the cross-cut portion is less than 0.3 mm and the area ratio of the corroded portion of the flat plate portion is 1% or less (except when the evaluation is ◎)
○ △: Corrosion width of the corroded portion under the coating of the cross-cut portion is less than 0.4 mm and the area ratio of the corroded portion of the flat plate portion is 3% or less (excluding cases where the evaluation is ◎, ○)
Δ: Corrosion width of the corroded portion under the coating of the cross-cut portion is less than 0.5 mm and the area ratio of the corroded portion of the flat plate portion is 5% or less (excluding cases where the evaluation is ◎, ○, ○ △)
×: Corrosion width of the corroded portion under the coating of the crosscut portion is 0.5 mm or more, or the area ratio of the corroded portion of the flat plate portion exceeds 5%

(F) Retort Rust Resistance The test material was subjected to retort treatment at 121 ° C. for 30 minutes, the state of occurrence of rust was observed, and the following five stages were evaluated from the area ratio (%) of the rust generation part. The evaluation above Δ is a practical level.
A: The area ratio of the rust generation part is 0%
○: The area ratio of the rust generation part is more than 0% to 1% or less. △: The area ratio of the rust generation part is more than 1% to 3% or less. △: The area ratio of the rust generation part is more than 3% to 5% or less. Part area ratio is over 5%

(G) Antisulfuration blackening resistance An epoxy-phenol resin was applied to the test material so as to form a coating film having a dry film thickness of 6 g / m ² and baked at 200 ° C. for 10 minutes. Then, after immersing in a test solution (0.056% cysteine hydrochloride, 0.4% potassium dihydrogen phosphate, 0.81% sodium phosphate) at 121 ° C. for 1 hour, the color difference (ΔE value) before and after immersion was determined. Evaluation was made in the following five stages. The evaluation above Δ is a practical level. Evaluation equipment: Nippon Denshoku Industries SD7000 (SCI method: total reflection measurement)
◎: ΔE value is less than 3.0 ○: ΔE value is 3.0 or more and less than 5.5 ○ Δ: ΔE value is 5.5 or more and less than 8.0 Δ: ΔE value is 8.0 or more and less than 10.5 × : ΔE value is 10.5 or more

(H) Sn mixing resistance 350 mg / L of stannous chloride as Sn was added to 100 ml of the metal surface treatment agent for electrolytic treatment, and the plate was allowed to stand in a constant temperature bath at 40 ° C for 24 hours. The dissolved Sn concentration in the supernatant of the treatment agent after standing was measured, and the Sn dissolution rate (%) was evaluated in the following five stages. The evaluation above Δ is a practical level. Evaluation equipment: Known methods such as ICP emission spectroscopic analyzer (ICP-AES) according to JIS-K0116: 2014 standard ◎: Sn dissolution rate is 80% or more ○: Sn dissolution rate is 70% or more and less than 80% ○ △: Sn dissolution Rate is 60% or more and less than 70% Δ: Sn dissolution rate is 50% or more and less than 60% ×: Sn dissolution rate is 40% or more and less than 50%

(I) Discoloration resistance The test material was allowed to stand for 72 hours in a thermostat at 70 ° C. and 80% RH. The color difference (ΔE value) before and after standing in the test material was evaluated in the following five stages. The evaluation above Δ is a practical level. Evaluation equipment: SD7000 manufactured by Nippon Denshoku Industries Co., Ltd. (SCI method: total reflection measurement)
◎: ΔE value is less than 2.0 ○: ΔE value is 2.0 or more and less than 4.0 ○ △: ΔE value is 4.0 or more and less than 6.0 Δ: ΔE value is 6.0 or more and less than 8.0 × : ΔE value is 8.0 or more

(J) Short-time film deposition property The test material (in this evaluation, the test material that has not been subjected to standard electrolytic treatment, that is, the pre-treated test material) is the cathode, the carbon plate is the counter electrode, and the test material is at a predetermined temperature. It was immersed in a metal surface treatment agent (40 ° C.) and simultaneously electrolyzed at a current density of 10.0 A / dm ² for 0.3 seconds. Thereafter, the surface of the test material is cleaned by spray-washing the test material subjected to electrolytic treatment with city water at 25 ° C. for 5 seconds, drained using a roll squeeze, and the surface temperature of the test material reached is reached. Dried at 50 ° C. Thereafter, the Zr adhesion amount of the test material was measured with a fluorescent X-ray analyzer, and the Zr adhesion amount (mg / m ² ) was evaluated in the following five stages. The evaluation above Δ is a practical level.
A: Zr adhesion amount is 6 mg / m ² or more ○: Zr adhesion amount is 5 mg / m ² or more and less than 6 mg / m ² ○ Δ: Zr adhesion amount is 4 mg / m ² or more and less than 5 mg / m ² Δ: Zr adhesion amount is 3 mg / m ² or more and less than 4 mg / m ² ×: Zr adhesion amount is less than 3 mg / m ²

(K) Stability of treatment agent over time 100 mL of a metal surface treatment agent for electrolytic treatment was left in a constant temperature bath at 40 ° C. for one month. The liquid appearance (liquid property) of the treatment agent after standing in January and the mass (mg) of the residue of the treatment agent remaining on the filter paper after filtering 100 mL of the treatment agent with a filter paper (No5C) are as follows. Evaluation was made in 5 stages. The evaluation above Δ is a practical level.
A: The treatment agent is not turbid and the mass of the residue is 0 mg
○: The treatment agent is turbid and the mass of the residue is 0 mg
○: The treatment agent is turbid and the mass of the residue is more than 0 mg to 10 mg or less. Δ: The treatment agent is turbid and the mass of the residue is more than 10 mg and less than 20 mg. X: The treatment agent is turbid and the residue. The mass of the object is 20mg or more

(L) Film appearance Color difference (ΔE value) before and after electrolytic treatment (standard electrolytic treatment) in a test material (in this evaluation, a test material that has not been subjected to standard electrolytic treatment, that is, a test material after pretreatment) Rated by stage. The evaluation above Δ is a practical level. Evaluation equipment: SD7000 manufactured by Nippon Denshoku Industries Co., Ltd. (SCI method: total reflection measurement)
◎: ΔE value is less than 5.0 ○: ΔE value is 5.0 or more and less than 7.0 ○ Δ: ΔE value is 7.0 or more and less than 9.0 Δ: ΔE value is 9.0 or more and less than 11.0 × : ΔE value is 11.0 or more

Claims (24)

One or more dissolved metal M components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component and a dissolved Cu component, nitrate ions, chloride ions and One or more anions selected from the group consisting of sulfate ions,
The ratio (P _w / Zr _w ) of the converted mass (P _w ) of P element of the dissolved P component to the converted mass (Zr _w ) of Zr element of the dissolved Zr component is in the range of 0.04 or more and 0.5 or less. Within
Ratio (M _w / Zr _w ) of reduced mass (M _w ) of metal element (Zn element, Mn element, Cu element) of dissolved metal M component and reduced mass (Zr _w ) of Zr element of dissolved Zr component There Ri der range of 0.05 to 2.5,
The metal to be treated is Sn-based plating.
Metal surface treatment agent for electrolytic treatment. The metal surface treatment agent for electrolytic treatment according to claim 1 , wherein the metal to be treated is alloy plating of Sn and Fe.   One or more dissolved metal M components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component and a dissolved Cu component, nitrate ions, chloride ions and One or more anions selected from the group consisting of sulfate ions,
  Reduced mass of P element of the dissolved P component (P _w ) And the converted mass of Zr element of the dissolved Zr component (Zr _w ) (P) _w / Zr _w ) Is in the range of 0.04 to 0.5,
  Converted mass (M of metal element (Zn element, Mn element, Cu element) of the dissolved metal M component _w ) And the converted mass of Zr element of the dissolved Zr component (Zr _w ) And ratio (M _w / Zr _w ) Is in the range of 0.05 to 2.5,
  The metal to be treated is nickel plating.
Metal surface treatment agent for electrolytic treatment. The ratio (F _w / Zr _w ) of the converted mass (F _w ) of the F element of the dissolved F component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is 1.3 to 2.5 The metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 3, wherein the metal surface treatment agent is electrolytic. The metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 4, wherein the Zr element concentration is in the range of 1000 mg / L to 1950 mg / L. The metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 5 , wherein the pH is in the range of 3.4 or more and 4.8 or less. Furthermore, it may contain at least one component selected from the group consisting of dissolved Sn component, dissolved Fe component, dissolved ammonia N component, dissolved Na component and dissolved K component. In this case, the Zr element of the dissolved Zr component Converted mass (Zr _w ), converted mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component, converted mass (Sn _w ) of the Sn element of the dissolved Sn component, The total mass of the converted Fe element of the dissolved Fe component (Fe _w ) and the converted mass of the N element of the dissolved ammonia-type N component (N _w ), and the converted mass of the Zr element of the dissolved Zr component (Zr _w ), the molten metal M component metal equivalent weight _(M w), reduced mass of Sn element of the dissolved Sn component _(Sn w), in terms of mass of Fe element of the dissolved Fe component _(Fe w), the dissolved ammonia state N N elements of ingredients Conversion Weight _(N w), the melting mass in terms of Na component as Na element (Na _w) and the ratio CA of the total mass of the reduced mass _{(K w)} of K elements of the dissolution K component: _{(Zr w + M _{w + Sn w + Fe w +} N w) / (Zr w + M w + Sn w + Fe w + N w + Na w + K w)} is 0.9 or more, for the electrolytic treatment according to any one of claims 1 to 6 Metal surface treatment agent. The metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 7 , wherein the electric conductivity is in a range of 1.0 S / m or more and 6.0 S / m or less. One or more dissolved metal M components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component and a dissolved Cu component, nitrate ions, chloride ions and One or more anions selected from the group consisting of sulfate ions,
The ratio (P _w / Zr _w ) of the converted mass (P _w ) of P element of the dissolved P component to the converted mass (Zr _w ) of Zr element of the dissolved Zr component is in the range of 0.04 or more and 0.5 or less. Within
Ratio (M _w / Zr _w ) of reduced mass (M _w ) of metal element (Zn element, Mn element, Cu element) of dissolved metal M component and reduced mass (Zr _w ) of Zr element of dissolved Zr component There Ri der range of 0.05 to 2.5,
The metal to be treated is Sn-based plating.
A method for producing a metal surface treatment agent for electrolytic treatment,
It includes a step of adding and mixing one or more raw materials to be a supply source of the dissolved Zr component, the dissolved F component, the dissolved P component, the dissolved metal M component, and the anion to a liquid medium. Production method. The method for producing a metal surface treatment agent for electrolytic treatment according to claim 9 , wherein the metal to be treated is alloy plating of Sn and Fe.   One or more dissolved metal M components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component and a dissolved Cu component, nitrate ions, chloride ions and One or more anions selected from the group consisting of sulfate ions,
  Reduced mass of P element of the dissolved P component (P _w ) And the converted mass of Zr element of the dissolved Zr component (Zr _w ) (P) _w / Zr _w ) Is in the range of 0.04 to 0.5,
  Converted mass (M of metal element (Zn element, Mn element, Cu element) of the dissolved metal M component _w ) And the converted mass of Zr element of the dissolved Zr component (Zr _w ) And ratio (M _w / Zr _w ) Is in the range of 0.05 to 2.5,
  The metal to be treated is nickel plating.
A method for producing a metal surface treatment agent for electrolytic treatment,
  A step of adding and mixing one or more raw materials serving as a supply source of the dissolved Zr component, the dissolved F component, the dissolved P component, the dissolved metal M component, and the anion to a liquid medium.
The manufacturing method characterized by the above-mentioned. The ratio (F _w / Zr _w ) of the converted mass (F _w ) of the F element of the dissolved F component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is 1.3 to 2.5 The manufacturing method of the metal surface treating agent for electrolytic treatment as described in any one of Claims 9-11 which is inside. The method for producing a metal surface treatment agent for electrolytic treatment according to claims 9 to 12 , wherein the Zr element concentration is in the range of 1000 mg / L or more and 1950 mg / L or less. pH is in the range of 3.4 to 4.8 or less, the production method of electrolytic treatment for metal surface treatment agent according to any one of claims 9-1 3. Furthermore, it may contain at least one component selected from the group consisting of dissolved Sn component, dissolved Fe component, dissolved ammonia N component, dissolved Na component and dissolved K component. In this case, the Zr element of the dissolved Zr component Converted mass (Zr _w ), converted mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component, converted mass (Sn _w ) of the Sn element of the dissolved Sn component, The total mass of the converted Fe element of the dissolved Fe component (Fe _w ) and the converted N element converted mass (N _w ) of the dissolved ammonia N component, the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, and the dissolution Converted mass (M _w ) of metal element of metal M component, converted mass of Sn element of dissolved Sn component (Sn _w ), converted mass of Fe element of dissolved Fe component (Fe _w ), dissolved dissolved N component N element Reduced mass _(N w), the melting mass in terms of Na component as Na element (Na _w) and the ratio CA of the total mass of the reduced mass _{(K w)} of K elements of the dissolution K component: _{{(Zr w} + _M w _{+ Sn w + Fe w + N} w) / (Zr w + M w + Sn w + Fe w + N w + Na w + K w)} is 0.9 or more, for the electrolytic treatment according to any one of claims 9-1 4 A method for producing a metal surface treatment agent. Electrical conductivity in the range of less than 1.0 S / m or more 6.0 s / m, method of manufacturing an electrolytic process for metal surface treatment agent according to any one of claims 9-1 5. In the surface treatment method of a metal material, including a step of energizing the treatment target metal as a cathode side in a state where the treatment target metal is immersed in the metal treatment agent for electrolytic treatment,
The metal treatment agent for electrolytic treatment is
One or more dissolved metal M components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component and a dissolved Cu component, nitrate ions, chloride ions and One or more anions selected from the group consisting of sulfate ions,
The mass ratio (P _w / Zr _w ) of the converted mass (P _w ) of the P element of the dissolved P component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is 0.04 or more and 0.5 or less. Is in range,
Ratio (M _w / Zr _w ) of reduced mass (M _w ) of metal element (Zn element, Mn element, Cu element) of dissolved metal M component and reduced mass (Zr _w ) of Zr element of dissolved Zr component There Ri der range of 0.05 to 2.5,
The metal to be treated is Sn-based plating.
A surface treatment method characterized by the above. The surface treatment method according to claim 17 , wherein the metal to be treated is alloy plating of Sn and Fe.   In the surface treatment method of a metal material, including a step of energizing the treatment target metal as a cathode side in a state where the treatment target metal is immersed in the metal treatment agent for electrolytic treatment,
  The metal treatment agent for electrolytic treatment is
  One or more dissolved metal M components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved Zn component, a dissolved Mn component and a dissolved Cu component, nitrate ions, chloride ions and One or more anions selected from the group consisting of sulfate ions,
  Reduced mass of P element of the dissolved P component (P _w ) And the converted mass of Zr element of the dissolved Zr component (Zr _w ) And mass ratio (P _w / Zr _w ) Is in the range of 0.04 to 0.5,
  Converted mass (M of metal element (Zn element, Mn element, Cu element) of the dissolved metal M component _w ) And the converted mass of Zr element of the dissolved Zr component (Zr _w ) And ratio (M _w / Zr _w ) Is in the range of 0.05 to 2.5,
  The metal to be treated is nickel plating.
A surface treatment method characterized by the above. In the metal treatment agent for electrolytic treatment, the ratio (F _w / Zr _w ) between the converted mass (F _w ) of the F element of the dissolved F component and the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is The surface treatment method according to any one of claims 17 to 19 , which is within a range of 1.3 or more and 2.5 or less. The surface treatment method according to any one of claims 17 to 20, wherein the Zr element concentration in the metal treatment agent for electrolytic treatment is in a range of 1000 mg / L or more and 1950 mg / L or less. The surface treatment method according to any one of claims 17 to 21 , wherein a pH of the metal treatment agent for electrolytic treatment is in a range of 3.4 or more and 4.8 or less. The metal treatment agent for electrolytic treatment may further contain at least one component selected from the group consisting of a dissolved Sn component, a dissolved Fe component, a dissolved ammonia N component, a dissolved Na component, and a dissolved K component. In this case, the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component, the Sn element of the Sn component The total mass of the converted mass (Sn _w ), the converted mass of the Fe element of the dissolved Fe component (Fe _w ), and the converted mass (N _w ) of the N element of the dissolved ammonia N component, and the Zr element of the dissolved Zr component Conversion mass (Zr _w ), conversion mass of metal of the dissolved metal M component (M _w ), conversion mass of Sn element of the Sn component (Sn _w ), conversion mass of Fe element of the dissolution Fe component (Fe _w ) The dissolution ann Weight ratio of the total mass of the reduced mass of the N elements of the state N components _(N w), in terms of mass of Na element of the dissolved Na component (Na _w) and reduced mass of K elements of the lysis K component _{(K w) CA: {(Zr w + M} w + Sn w + Fe w + N w) / (Zr w + M w + Sn w + Fe w + N w + Na w + K w)} is 0.9 or more, claim 17-2 2 The surface treatment method according to one item. The electrical conductivity of the electrolytic treatment for metal treatment agent is in the range of less than 1.0 S / m or more 6.0 s / m, the surface treatment method according to any one of claims 17 to 2 3.