TW201829850A - Metal surface treatment agent for electrolytic treatment - Google Patents

Abstract

An object of the present invention is to provide a metal surface treatment agent for electrolytic treatment which is possible to impart not only can processability, film adhesion property, paint adhesion property, corrosion resistance property, sulfide blackening resistance, but also color change resistance property to Sn type plating material, and is suitable for practical use such as precipitation property of Zr-P type coating film in a short time, stability of metal surface treating agent due to Sn incorporation, and stability of the metal surface treating agent over time. The metal surface treatment agent for electrolytic treatment comprises 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, and one or more anions selected from the group consisting of nitrate ions, chloride ions and sulfate ions, wherein the ratio (Pw/ Zrw) of the converted mass (Pw) of the P element of the dissolved P component to the converted mass (Zrw) of the Zr element of the dissolved Zr component is within the range of 0.04 or more and 0.5 or less; and the mass ratio (Mw/ Zrw) of the converted mass (Mw) of the metal element of the dissolved metal M component to the converted mass (Zrw) of the Zr element of the dissolved Zr component is within the range of 0.05 or more and 2.5 or less.

Description

 Metal surface treatment agent for electrolytic treatment  

The present invention relates to a metal surface treatment agent for electrolytic treatment.

Heretofore, various methods have been proposed for various metal materials in terms of surface treatment methods for improving the properties of the metal materials.

For example, the tinplate material is formed by plating tin (Sn) on the surface of the steel sheet. The tinplate material is resistant to rust and has corrosion resistance to moisture and the like, and is also suitable for welding or soldering. Therefore, it is mainly used as a material for a can (welding can or solder can) or as an electrical component. Here, the surface treatment method of the tinplate material is typically classified into a chemical conversion treatment (for example, refer to Patent Document 1), an electrolytic treatment (for example, refer to Patent Document 2), and a coating type treatment (for example, see Patent Document 3). Further, the types of the film formed on the tinplate material are also diverse (for example, refer to Patent Documents 1 to 3).

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Patent Laid-Open No. Hei 1-100281

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-280888

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2004-307923

Here, as previously mentioned, the tin plate material is mainly used as a material for the can. In consideration of the use in the application, the surface-treated tinplate material is required to have potability, film adhesion, paint adhesion (primary coating adhesion, secondary coating adhesion), and corrosion resistance. (corrosion resistance under coating film, heat sterilization and rust resistance), and properties such as resistance to sulfur blackening.

The present inventors conducted various investigations on the types of coatings and treatment methods satisfying these properties, and as a result, found that when a metal surface treatment agent containing a dissolved Zr component, a dissolved F component, and a dissolved P component is used, and the Sn plating is performed by electrolytic treatment. When the Zr-P-based film is formed on the surface, the above-mentioned properties equivalent to those of the conventional chromate treatment can be achieved.

On the other hand, the present inventors have also obtained the knowledge that the Zr-P film is formed on the Sn-based plating by electrolytic treatment, and is treated by other film types or treatment methods. Compared with the sample formed by forming the film on the Sn-based plating, the discoloration resistance in the case of a long-term passage in a humid environment is worse.

Therefore, an object of the present invention is to provide a metal surface treatment agent for electrolytic treatment which can not only be used for potability, film adhesion, paint adhesion (primary coating adhesion, secondary coating adhesion), Corrosion resistance (corrosion resistance under coating film, heat sterilization and rust resistance), sulfur black resistance, etc. are applied to the Sn-based plating material, and the property of discoloration resistance can be imparted to the Sn-based plating material, and Precipitability (short-time film deposition property) of Zr-P film for a short period of time, stability of metal surface treatment agent due to mixing of Sn (Sn mixed resistance), and stability of time of metal surface treatment agent (treatment) The agent is suitable for practical use such as stability over time.

The present invention is as follows.

[1] A metal surface treatment agent for electrolytic treatment, comprising: dissolving a Zr component; dissolving the F component; dissolving the P component; and selecting one or more selected from the group consisting of a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component. a dissolved metal M component; and one or more anions selected from the group consisting of nitrate ions, chloride ions, and sulfate ions, wherein the converted mass (P _w ) of the P element of the dissolved P component and the dissolved Zr component Conversion of the metal element (the total of the Zn element, the Mn element, and the Cu element) of the dissolved metal M component in the range of the ratio (P _w /Zr _w ) of the converted mass (Zr _w ) of the Zr element to be 0.04 or more and 0.5 or less. The mass ratio (M _w /Zr _w ) of the mass (M _w ) to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is in the range of 0.05 or more and 2.5 or less.

[2] according to [1], wherein the electrolytic treatment of a metal surface treatment agent, wherein the dissolved element in terms of mass F F component (F _W) and in terms of the mass of Zr was dissolved component of Zr (Zr _W) The mass ratio (F _w /Zr _w ) is in the range of 1.3 or more and 2.5 or less.

[3] The metal surface treatment agent for electrolytic treatment according to the above [1], wherein the Zr element concentration is in a range of from 1000 mg/L to 1950 mg/L.

[4] The metal surface treatment agent for electrolytic treatment according to any one of the above [1] to [3] wherein the pH is in the range of 3.4 or more and 4.8 or less.

[5] The metal surface treatment agent for electrolytic treatment according to any one of the above [1] to [4], which may further comprise a component selected from the group consisting of dissolved Sn, dissolved Fe, dissolved ammonium or ammonia N, dissolved Na At least one component of the group consisting of the component and the dissolved K component, in this case, the converted mass (Zr _w ) of the Zr element in which the Zr component is dissolved, and the metal element (Zn element, Mn element, Cu element of the dissolved metal M component) The converted mass (M _w ), the converted mass of the Sn element of the dissolved Sn component (Sn _w ), the converted mass of the Fe element of the dissolved Fe component (Fe _w ), and the N element of the dissolved ammonium or ammonia N component. The total mass of the converted mass (N _w ), the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal element of the dissolved metal M component, and the Sn element of the dissolved Sn component. The converted mass (Sn _w ), the converted mass (Fe _w ) of the Fe element in which the Fe component is dissolved, the converted mass (N _w ) of the N element of the dissolved ammonium or the ammonia N component, and the Na element of the dissolved Na component in terms of the total mass in terms of mass (Na _w) was dissolved and the elements of the K component of K (K _W) of Mass volume ratio of _{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 .

[6] The metal surface treatment agent for electrolytic treatment according to any one of [1] to [5] wherein the conductivity is in a range of 1.0 S/m or more and 6.0 S/m or less.

[7] The metal surface treatment agent for electrolytic treatment according to any one of [1] to [6] wherein the metal to be treated is Sn-based plating.

[8] The metal surface treatment agent for electrolytic treatment according to the above [7], wherein the metal to be treated is alloy plating of Sn and Fe.

[9] A method for producing a metal surface treatment agent for electrolytic treatment, comprising: dissolving a Zr component; dissolving the F component; dissolving the P component; and selecting a dissolved Zn component, dissolving the Mn component, and dissolving Cu. One or more kinds of dissolved metal M components of the group consisting of components; and one or more anions selected from the group consisting of nitrate ions, chloride ions, and sulfate ions, and the conversion quality of the P element of the dissolved P component (P _w ) and the mass ratio (P _w /Zr _w ) of the converted mass (Zr _w ) of the Zr element of the dissolved Zr component are in a range of 0.04 or more and 0.5 or less, and the metal element (Zn element, the dissolved metal M component) The ratio (M _w /Zr _w ) of the converted mass (M _w ) of the Mn element and the Cu element to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is in a range of 0.05 or more and 2.5 or less; the manufacturing method includes One or more raw materials of the dissolved Zr component, the dissolved F component, the dissolved P component, the dissolved metal M component, and the supply source of the anion are added to a liquid medium and mixed.

[10] The method for producing a metal surface treatment agent for electrolytic treatment according to the above [9], wherein the converted mass (F _w ) of the F element of the dissolved F component and the converted mass of the Zr element of the dissolved Zr component ( the Zr _w) ratio (F _w / Zr _w) is 1.3 to 2.5 range.

[11] The method for producing a metal surface treatment agent for electrolytic treatment according to the above [9], wherein the Zr element concentration is in a range of from 1000 mg/L to 1950 mg/L.

[12] The method for producing a metal surface treatment agent for electrolytic treatment according to any one of the above [9], wherein the pH is in a range of 3.4 or more and 4.8 or less.

[13] The method for producing a metal surface treatment agent for electrolytic treatment according to any one of the above [9], wherein the method further comprises: dissolving a Sn component, dissolving a Fe component, dissolving ammonium or an ammonia state. At least one component of the group consisting of the N component, the dissolved Na component, and the dissolved K component, in this case, the converted mass (Zr _w ) of the Zr component of the dissolved Zr component, and the metal element (Zn element of the dissolved metal component M) The converted mass (M _w ) of the Mn element and the Cu element, the converted mass of the Sn element of the dissolved Sn component (Sn _w ), the converted mass of the Fe element of the dissolved Fe component (Fe _w ), and the aforementioned dissolved ammonium or ammonia state The total mass of the converted mass (N _w ) of the N element of the N component, the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal element of the dissolved metal component M, and the dissolution The converted mass (Sn _w ) of the Sn element of the Sn component, the converted mass (Fe _w ) of the Fe element of the dissolved Fe component, the converted mass (N _w ) of the N element of the dissolved ammonium or the ammonia N component, and the dissolved Na Na element in terms of mass of component _(W Na) was dissolved and the elements of the K component K Operator mass (K _w) ratio of CA total mass _{of: {(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.

[14] The method for producing a metal surface treatment agent for electrolytic treatment according to any one of the above aspects, wherein the conductivity is in a range of 1.0 S/m or more and 6.0 S/m or less.

[15] The method for producing a metal surface treatment agent for electrolytic treatment according to any one of the above [9], 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 the above [15], wherein the metal to be treated is alloy plating of Sn and Fe.

[17] A surface treatment method for a metal material, comprising: a step of immersing a metal to be treated in a metal treatment agent for electrolytic treatment, and performing electrification using the metal to be treated as a cathode side; wherein the metal for electrolytic treatment The treatment agent contains: a dissolved Zr component; a dissolved F component; a dissolved P component; and one or more dissolved metal components M selected from the group consisting of a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component; and a nitrate ion selected from the group consisting of nitrate ions Ratio of one or more anions of the group consisting of chloride ions and sulfate ions, and the ratio 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 (P _w /Zr _w ) is a conversion mass (M _w ) of a metal element (Zn element, Mn element, Cu element) of the dissolved metal M component and a Zr element of the dissolved Zr component in a range of 0.04 or more and 0.5 or less. The ratio (M _w /Zr _w ) of the converted mass (Zr _w ) is in the range of 0.05 or more and 2.5 or less.

[18] The surface treatment method according to the above [17], wherein the conversion quality (F _w ) of the F element of the dissolved F component and the Zr element of the dissolved Zr component in the metal treatment agent for electrolytic treatment are converted. The ratio (F _w /Zr _w ) of the mass (Zr _w ) is in the range of 1.3 or more and 2.5 or less.

[19] The surface treatment method according to the above [17], wherein the metal treatment agent for electrolytic treatment has a Zr element concentration of from 1000 mg/L to 1950 mg/L.

[20] The surface treatment method according to any one of the above [17], wherein the pH of the metal treatment agent for electrolytic treatment is in a range of 3.4 or more and 4.8 or less.

[21] The surface treatment method according to any one of [17] to [20] wherein the metal treatment agent for electrolytic treatment may further comprise a component selected from the group consisting of dissolved Sn, dissolved Fe, dissolved ammonium or ammonia. At least one component of the group consisting of the N component, the dissolved Na component, and the dissolved K component, in this case, the converted mass (Zr _w ) of the Zr component of the dissolved Zr component, and the metal element (Zn element of the dissolved metal component M) The converted mass (M _w ) of the Mn element and the Cu element, the converted mass of the Sn element of the dissolved Sn component (Sn _w ), the converted mass of the Fe element of the dissolved Fe component (Fe _w ), and the aforementioned dissolved ammonium or ammonia state The total mass of the converted mass (N _w ) of the N element of the N component, the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal element of the dissolved metal component M, and the dissolution The converted mass (Sn _w ) of the Sn element of the Sn component, the converted mass (Fe _w ) of the Fe element of the dissolved Fe component, the converted mass (N _w ) of the N element of the dissolved ammonium or the ammonia N component, and the dissolved Na in terms of mass of the component elements of the Na (Na _W) and the K-K component element dissolved Mass in terms of mass (K _w) of the total mass ratio of _{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 surface treatment method according to any one of the above aspects, wherein the metal treatment agent for electrolytic treatment has a conductivity of 1.0 S/m or more and 6.0 S/m or less.

The surface treatment method according to any one of the above aspects, 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, it is possible to provide a metal surface treatment agent for electrolytic treatment which can not only be used for potability, film adhesion, paint adhesion (primary coating adhesion, secondary coating adhesion), and corrosion resistance. (corrosion resistance under coating film, heat sterilization and rust resistance), sulfur black resistance, etc. are applied to the Sn-based plating material, and the property of discoloration resistance can be imparted to the Sn-based plating material, and a short-time film is provided. It is practically suitable for precipitation, Sn-resistant incorporation, and stability of the treatment agent over time.

The present invention will be more specifically described in the following order.

 1. Metal surface treatment agent for electrolytic treatment    1-1. Components    1-2. Composition (content ratio, content)    1-3. Liquidity    2. Method for producing metal surface treatment agent for electrolytic treatment    2-1. Raw materials    2-2. Process    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: a dissolved Zr component; a dissolved F component; a dissolved P component; and one or more dissolved metals selected from the group consisting of a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component. An M component; and one or more anions selected from the group consisting of nitrate ions, chloride ions, and sulfate ions, wherein the converted mass (P _w ) of the P element of the dissolved P component and the Zr of the dissolved Zr component are The conversion mass (M _w of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component in the range of the ratio (P _w /Zr _w ) of the converted mass (Zr _w ) of the element is 0.04 or more and 0.5 or less. The ratio (M _w /Zr _w ) to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is in the range of 0.05 or more and 2.5 or less. Further, the metal surface treatment agent for electrolytic treatment of the present invention also includes any of a new liquid (liquid which has not been subjected to electrolytic treatment) and a load liquid (liquid which has been subjected to electrolytic treatment).

<1-1. Composition>

 {1-1-1. Dissolving Zr component}  

The dissolved Zr component refers to a component containing a Zr element which is dissolved in a solvent at 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⁺ ), it is also a combination of Zr and other components (for example, F) (ZrF ₆ ^2- , ZrF ₅ ^- , ZrF _{3 ).} Forms such as ⁺ , ZrF ₂ ²⁺ , ZrF ³⁺ ) or molecules (ZrF ₄ ), zirconia ions (ZrO ³⁺ or HZrO ₃ ^- ) exist. Further, in the metal surface treatment agent for electrolytic treatment of the present invention, it is preferable to contain F in an amount exceeding the bond of Zr, and it is presumed that most of the dissolved Zr component is ZrF ₆ ^2- (or a part of F is used in other parts). The form of a ligand substituent, in which the anion is electrically bonded to a cation, exists.

{1-1-2. Dissolved F component}

The dissolved F component refers to a component containing an F element which is dissolved in a solvent at normal temperature (20 ° C) and normal pressure (1 atm = 101325 Pa). The component of the dissolved F is not particularly limited. For example, in addition to the F ion, a dissociated ion (ZrF ₆ ^2- , ZrF ₅ ^- , ZrF ₃ ⁺ , ZrF ₂ ²⁺ ) in which F is combined with other components (for example, Zr, H) is also used. Forms such as ZrF ³⁺ , HF ₂ ^- ) or molecules (HF, ZrF ₄ ). Further, in the metal surface treatment agent for electrolytic treatment of the present invention, it is preferable to contain F in an amount exceeding the bond of Zr, and therefore it is presumed that most of the dissolved F component is ZrF ₆ ^2- (or a part of F is other The ligand is substituted in the form in which the anion is electrically bonded, and the rest is in the form of a combination of F ion, HF or other components. In addition, in the above, "ZrF ₆ ^2- " is exemplified as an example of "dissolved F component". However, since this component also contains Zr, this component also conforms to "dissolved Zr component" (other components are also similar). In other words, when a certain component is present in a dissolved state and the component contains two or more elements of Zr, F and metal (M) (for example, "X" and "Y"), the component is "Dissolve X component" and also "dissolve Y component".

{1-1-3. Dissolving P component}

The dissolved P component refers to a component containing a P element which is in a dissolved state at normal temperature (20 ° C) and normal pressure (1 atm = 101325 Pa). The dissolved P component is not particularly limited, and may be, for example, in the form of (1) orthophosphoric acid phosphorus, (2) polymeric phosphoric acid phosphorus, (3) soluble organic phosphoric acid phosphorus, or the like. Here, a more specific example of the (1) orthophosphoric acid phosphorus is a component containing a phosphate (PO ₄ ) which is in a dissolved state in the agent, and examples thereof include orthophosphoric acid (H ₃ PO ₄ ) and phosphate ion (H ₂ ). PO ₄ ^- , HPO ₄ ^2- , PO ₄ ^3- ), and the like, and combinations of these ions with other components. Further, (2) more specific examples of the phosphoric acid-containing phosphorus include pyrophosphoric acid, polyphosphoric acid, metafluoric acid, and the like which are dissolved in the agent, and combinations of the ions and other components. . Further, (3) the soluble organic phosphoric acid phosphorus is a component containing an organic phosphoric acid which is dissolved in the agent, and examples thereof include a phosphonic acid which is in a dissolved state in the agent, and the like, and the like. A combination of ions and other components. Here, the organic phosphoric acid is a compound containing a carbon element (C), a hydrogen element (H), an oxygen element (O), and a phosphorus element (P), and has a property as an oxo acid (phosphonic acid) of phosphorus. .

{1-1-4. Dissolved metal M component}

The dissolved metal M component is a metal selected from the group consisting of a Zn component, a Mn component, and a Cu component, which is dissolved in a solvent at normal temperature (20 ° C) and normal pressure (1 atm = 101,325 Pa). ingredient. The component of the dissolved metal M is not particularly limited, and examples thereof include metal ions (for example, Zn ²⁺ , Zn ^{+ ,} etc., Mn ²⁺ , Mn ^4+, etc., Cu ²⁺ , Cu ^{+ ,} etc.), and also metals (ions). The form of a combination with other components (for example, a complex) exists. Here, among these metal components, since the discoloration resistance is particularly excellent, a manganese component is preferable.

{1-1-5. Anion}

The metal surface treatment agent for electrolytic treatment of the present invention further contains one or more anions selected from the group consisting of nitric acid ions, chloride ions, and sulfate ions. When measures for reducing the amount of nitric acid (including nitrogen-free nitrogen) are taken as a countermeasure against drainage of the present treatment agent, all or a part of the nitrate ions as anions may be replaced with chloride ions and/or sulfate ions as a countermeasure. When countermeasures for reducing chloride (including chloride-free) are carried out as measures against corrosion of the electrolytic treatment apparatus, it is possible to replace all or part of the chloride ions as anions with nitrate ions and/or sulfate ions. When the countermeasure for the drainage of the treatment agent and the countermeasure against corrosion of the electrolytic treatment device are carried out, it is possible to replace all or part of the nitrate ions and chloride ions as anions with sulfate ions.

{1-1-6. Other ingredients}

The metal surface treatment agent for electrolytic treatment of the present invention may contain a known component used in the field as needed. For example, it may contain a dissolved Sn component, a dissolved Fe component, dissolved ammonium or an ammonia N component (that is, ammonium, ammonia), dissolved Na component, and dissolved K component. Here, the other component may be a component added at the time of preparation of the new liquid, or may be a component supplied from a material (steel plate) or the like at the stage of the load liquid. For example, it is not limited to dissolve the Sn component and dissolve the Fe component, and is typically a component supplied from a material (steel plate) during the treatment. Further, for example, the dissolved Na component and the dissolved K component are not limited, and are typically supplied in industrial water (well water, ground water, tap water) used as a liquid medium during the treatment, or during the treatment. A component that is attached to the surface of the material and supplied. However, the metal surface treatment agent for electrolytic treatment of the present invention preferably does not contain a dissolved K component (typically potassium ion) or a very small amount (also referred to as a trace amount) (K _w : 3 mg/L or less). . When the content of the dissolved K component is not contained or only a very small amount is contained, the film deposition property is particularly excellent in a short period of time. Further, the metal surface treatment agent for electrolytic treatment of the present invention preferably does not contain a dissolved Na component (typically sodium ion) or contains only a very small amount (Na _w : 3 mg/L or less). When the Na content is not contained or only a very small amount is contained, the appearance of the film is particularly excellent. From this, it is understood that the liquid medium of the treating agent is preferably deionized water.

{1-1-7. Liquid medium}

The liquid medium in the metal surface treatment agent for electrolytic treatment of the present invention is preferably a liquid medium (for example, deionized water or pure water) mainly composed of water. Here, "as a main body" means that the water is 51% by mass or more based on the total mass of the liquid medium (preferably 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more). , particularly suitable for 90% by mass or more). Therefore, the "dissolution" in each of the above components (dissolved Zr component, dissolved F component, dissolved P component, dissolved metal M component, etc.) means a state of being dissolved in a liquid medium (preferably water) mainly composed of water. For example, it can also be called "water-soluble type". Further, the metal surface treatment agent for electrolytic treatment of the present invention includes not only a form containing only the above-described dissolved component and liquid medium, but also an unmelted person in which a sludge such as an excessive amount of ions coexists (although the detailed form is unknown, However, for example, the morphology of FePO ₄ , SnF ₄ , SnO(OH) ₂ , Sn(OH) _{4 ,} etc. Further, a liquid medium other than water (for example, a water-mixable liquid medium such as an alcohol such as ethanol) may be contained as the liquid medium, but a small amount is preferably used for 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, and still more preferably 3% by mass or less, particularly preferably 1%, based on the total mass of the liquid medium. Below mass%. Further, the agent may be in a dry form or a concentrated form. At this time, it is used in the field by dissolving or diluting with water.

<1-2. Composition>

 {1-2-1. Contains ratio}   (1-2-1-1. P _w and the mass ratio of Zr _w)

The ratio (P _w /Zr _w ) 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 in the metal surface treatment agent for electrolytic treatment of the present invention is 0.04. In the range of 0.5 or more and more, it is preferably in the range of 0.06 or more and 0.4 or less, more preferably 0.08 or more and 0.3 or less. In the specific system of the metal surface treatment agent for electrolytic treatment of the present invention, the ratio is set within the range. {Correctly, in addition to the parameter, the ratio of M _w to Zr _w (M _w / Zr _w described later) is also used. The metal surface treatment agent for electrolytic treatment can be provided in the range of the following, which not only enables potability, film adhesion, and coating adhesion (primary coating adhesion, secondary coating adhesion) (sex), corrosion resistance (corrosion resistance under coating film, heat sterilization and rust resistance), resistance to sulfur blackening, etc., and the property of discoloration resistance can be imparted to the Sn-based plating material, and the film deposition property is short-time. It is suitable for practical use such as resistance to Sn incorporation and stability of the treatment agent over time. Especially when the P _w /Zr _{w is} less than 0.04, the resistance to sulfur blackening deteriorates. Further, when P _w /Zr _w exceeds 0.5, the film adhesion is deteriorated. Here, the mass measurement of the P element and the Zr element in the agent can be carried out by a known method such as an ICP emission spectroscopic analyzer (ICP-AES) according to JIS-K0116:2014.

(1-2-1-2. Ratio of M _w to Zr _w )

In the metal surface treatment agent for electrolytic treatment of the present invention, the converted mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component and the converted mass of the Zr element of the dissolved Zr component (Zr _w The ratio (M _w /Zr _w ) of 0.05 to 2.5 or less is preferably in the range of 0.1 or more and 2.0 or less, more preferably 0.15 or more and 1.5 or less. Further, when two or more kinds of metal M elements are present, the ratio is a ratio based on the total mass of the two or more types. In the specific system of the metal surface treatment agent for electrolytic treatment of the present invention, the ratio is set within the range. {Correctly, in addition to the parameter, the ratio of P _w to Zr _w (P _{w ) is also used.} /Zr _w ) is set within the above range, whereby a metal surface treatment agent for electrolytic treatment can be provided, which not only has potability, film adhesion, and paint adhesion (primary coating adhesion, secondary) Coating adhesion), corrosion resistance (corrosion resistance under coating film, heat sterilization and rust resistance), resistance to sulfur blackening, Sn incorporation resistance, etc., and properties of discoloration resistance can be imparted to the Sn-based plating material. At the same time, there are practically suitable ones such as short-term film precipitation, Sn-resistant incorporation, and stability of the treatment agent over time. In particular, when the M _w /Zr _{w is} less than 0.05, the discoloration resistance is deteriorated. Further, when M _w /Zr _w exceeds 2.5, the potability of the can is deteriorated. Here, the mass of the metal M element in the agent can be measured by a known method such as an ICP emission spectroscopic analyzer (ICP-AES) according to JIS-K0116:2014.

(1-2-1-3. Mass ratio of F _w to Zr _w )

The ratio (F _w /Zr _w ) of the converted mass (F _w ) of the F element of the dissolved F component to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component in the metal surface treatment agent for electrolytic treatment of the present invention. It is preferably in the range of 1.3 or more and 2.5 or less, more preferably in the range of 1.32 or more and 2.4 or less, and still more preferably 1.36 or more and 2.3 or less. When the ratio of F _w to Zr _w is within the above range, the effects as described above can be further improved. In particular, when F _w /Zr _w is 1.3 or more, the Sn-resistant mixed property is excellently changed. When F _w /Zr _w is 2.5 or less, the secondary coating adhesiveness is excellently changed. Here, the mass of the F element in the agent can be measured by the lanthanum-alizarin complexone absorption method by a solution obtained by subjecting the fluorine compound described in JIS-K0102:2014 specification 34.1 to distillation. Perform quantitative analysis.

(1-2-1-4. Mass ratio of specific component groups to each other)

Further, at least one component selected from the group consisting of a dissolved Sn component, a dissolved Fe component, a dissolved ammonium or an ammonia N component, a dissolved Na component, and a dissolved K component may be further contained. In this case, the Zr component of the Zr component is converted. (Zr _w ), the converted mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component, the converted mass (Sn _w ) of the Sn element in which the Sn component is dissolved, and the Fe element in which the Fe component is dissolved The converted mass (Fe _w ) and the total mass of the converted mass (N _w ) of the N element in the dissolved ammonium or ammonia N component, and the converted mass (Zr _w ) of the Zr element in which the Zr component is dissolved, and the metal in which the metal component M is dissolved The converted mass of the element (M _w ), the converted mass of the Sn element in which the Sn component is dissolved (Sn _w ), the converted mass of the Fe element in which the Fe component is dissolved (Fe _w ), and the converted mass of the N element of the dissolved ammonium or the ammoniated N component (N _w ), the ratio of the converted mass of the Na element in the dissolved Na component (Na _w ) and the total mass of the converted mass (K _w ) of the K component of the dissolved K component is CA, and the CA is preferably 0.9 or more, and more preferably It is 0.92 or more. When it is in this range, the appearance of the film is good. Here, the mass of the Sn element and the Fe element in the agent can be measured by a known method such as an ICP emission spectroscopic analyzer (ICP-AES) according to JIS-K0116:2014. Further, the mass of the N element, the Na element, and the K element of the dissolved ammonium or the ammonia N component in the agent can be measured by a known method such as an ion chromatogram method according to JIS-K0102:2016.

{1-2-2. Content}

 (1-2-2-1. Zr element concentration)  

The Zr element concentration in the metal surface treatment agent for electrolytic treatment of the present invention is preferably in the range of 1000 mg/L or more and 1950 mg/L or less, more preferably 1100 mg/L or more and 1850 mg/L or less, and more preferably 1200 mg/liter. L is in the range of 1750 mg/L or less. When it is within this range, even in general electrolysis conditions (for example, the test material is set to the cathode side, the test material is energized at a constant current density (for example, immersed in a predetermined 40 ° C metal surface treatment agent, and at the same time 3.0) The current density of A/dm ² is maintained for 1 second)}, and a metal material having the effects as described above can also be provided. In particular, when the Zr concentration is 1000 mg/L or more, the heat sterilization and rust resistance are preferably changed. When the Zr element concentration is 1950 mg/L or less, the primary coating adhesion is preferably changed.

(1-2-2-2. Other ingredient concentrations)

First, the F element concentration, the P element concentration, and the metal M element concentration are preferably values calculated from the Zr element concentration described above and the mass ratio of each of the elements to the Zr element. In addition, the concentration of one or more kinds of anions selected from the group consisting of nitrate ions, chloride ions, and sulfate ions is preferably such that the conductivity is within a suitable numerical range (1.0 S/m or more and 6.0 S/m or less). The way within it is appropriately determined.

<1-3. Liquidity>

 {1-3-1. pH}  

The pH of the metal surface treatment agent for electrolytic treatment of 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, and still more preferably 3.6 or more and 4.5 or less. When the pH is 3.4 or more, the corrosion resistance under the coating film is preferably changed. When the pH is 4.8 or less, the treatment agent is excellent in stability over time. Further, this pH is a value measured at a electrolysis temperature (typically 40 ° C) in accordance with JIS-Z8802:2011 for a metal surface treatment agent for electrolytic treatment.

{1-3-2. Conductivity}

The electrical conductivity in the metal surface treatment agent for electrolytic treatment of the present invention is preferably in the range of 1.0 S/m or more and 6.0 S/m or less, more preferably 1.5 or more and 5.5 or less, and still more preferably 2.0 or more and 5.0 or less. When the conductivity is 1.0 or more, the film deposition property is preferably changed in a short period of time. When the conductivity is 6.0 or less, corrosion to the electrolytic treatment apparatus is less likely to occur. Further, even if the conductivity exceeds 6.0, the effect of the film deposition property in a short period of time is saturated. Further, the conductivity is a value measured at a electrolysis temperature (typically 40 ° C) in accordance with JIS-K0130:2008 for a metal surface treatment agent for electrolytic treatment.

≪2. Method for manufacturing metal surface treatment agent for electrolytic treatment≫

The method for producing a metal surface treatment agent for electrolytic treatment according to the present invention includes adding one or more raw materials of the dissolved Zr component, the dissolved F component, the dissolved P component, the dissolved metal M component, and the supply source of the anion. The step of mixing in a liquid medium. Here, a raw material may be a supply source of a plurality of the above-mentioned components (a plurality of components selected from the group consisting of a dissolved Zr component, a dissolved F component, a dissolved P component, a dissolved metal M component, and the aforementioned anion) (for example, a fluorination of a raw material) Zirconic acid is a supply source for dissolving the Zr component and a supply source for dissolving the F component. The plurality of raw materials may be one of the above components (from dissolving the Zr component, dissolving the F component, dissolving the P component, dissolving the metal M component, and the anion described above). A supply source of any one of the selected components (for example, fluorozirconic acid and fluoric acid which are different raw materials are supply sources for dissolving the F component), and the plurality of materials may be a plurality of the above components (by dissolving the Zr component, dissolving F) a supply source of a component, a dissolved P component, a dissolved metal M component, and any of a plurality of components selected from the anions described above (for example, phosphoric acid and hydrofluoric acid which are different raw materials are dissolved P components and dissolved F components which are different components, respectively) Source of supply). Each raw material and process are detailed below.

<2-1. Raw materials>

 (2-1-1. Dissolving the supply source of Zr component)  

The supply source of the dissolved Zr component is not particularly limited, and examples thereof include a compound containing a zirconium atom, and examples thereof include zirconium sulfate, zirconyl sulfate, ammonium zirconium sulfate, zirconium nitrate, ammonium zirconium nitrate, fluorozirconic acid, and fluorozirconium salt. These may be used alone or in combination of two or more.

(2-1-2. Dissolving the supply source of F component)

The supply source of the dissolved F component is not particularly limited, and examples thereof include a fluorine atom-containing compound, and examples thereof include fluorozirconic acid, ammonium fluoride, ammonium hydrogen fluoride, cesium fluoride, iron fluoride, sodium fluoride, and sodium hydrogen fluoride. One type may be used alone or two or more types may be used in combination. Further, the fluorozirconic acid or the fluorozirconium salt which is a source of the dissolved Zr component exemplified above is also a supply source for dissolving the F component.

(2-1-3. Dissolving the supply source of P component)

The supply source for dissolving the P component is not particularly limited. For example, (1) in the case of orthophosphoric acid phosphorus, phosphoric acid (orthophosphoric acid) and a salt thereof (ammonium orthophosphate, etc.) are contained. (2) In the case of polymerized phosphoric acid phosphorus, it is a chain-shaped phosphoric acid condensate, and contains pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, etc., and also includes a salt thereof (ammonium pyrophosphate, ammonium tripolyphosphate, tetrapolyphosphoric acid) Ammonium, etc.). (3) In the case of organic phosphoric acid phosphorus, comprising nitrogen-based dimethylmethylene phosphonic acid, nitrogen-based propylphosphonic acid, nitrogen-based diethylmethylenephosphonic acid, methane-1-hydroxy-1,1 -diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, propane-1-hydroxy-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphine Acid, diethylenetriamine penta methylene phosphonic acid, and the like, and salts thereof. In addition, one type of the source of the dissolved P component may be used alone or two or more types may be used in combination.

(2-1-4. Supply 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. For example, the water-soluble zinc salt may, for example, be zinc nitrate (II), zinc (II) sulfate, zinc (II) sulfide, zinc (II) chloride, zinc (II) acetate, zinc (II) cyanide or zinc ammonium chloride. (II), zinc tartrate (II), zinc perchlorate (II), etc.; water-soluble manganese salts can be mentioned manganese (II) nitrate. 6 hydrate, manganese (II) acetate. 4 hydrate, manganese chloride (II). 4 hydrate, manganese (II) sulfate. 5 hydrate, manganese (II) sulfate. 6 hydrate or the like; the water-soluble copper salt may, for example, be copper (II) sulfate, copper (II) nitrate, copper (II) chloride, copper (II) acetate, copper (II) citrate, copper (II) tartrate, Copper (II) gluconate and the like. Further, the supply source of the dissolved metal (M) component may be one type or two or more types in combination.

(2-1-5. Supply source of anion)

The supply source of the anion is not particularly limited, and examples of the inorganic acid include inorganic acids such as nitric acid, hydrochloric acid, and sulfuric acid, and water-soluble salts of inorganic acids. Further, the supply of the anion may be one type or two or more types in combination. Further, when the component used as the supply source of the above-described other component (for example, the dissolved Zr component) contains the anion (that is, nitrate ion, chloride ion, and sulfate ion), the component is also a supply source of the anion. The anion (i.e., nitrate ion, chloride ion, sulfate ion) and the cation (preferably ammonium) of the treating agent are paired (i.e., neutral salt), and function as a supporting electrolyte for improving the conductivity of the treating agent. .

<2-2. Process>

The metal surface treatment agent for electrolytic treatment of the present invention can be added to a liquid medium (for example, water) mainly composed of water, and can be heated and cooled as needed, for example, by adding a raw material as a supply source of each of the above components. It is prepared by stirring. The order of adjustment of the pH and the conductivity is adjusted to a predetermined value after the raw material of the supply source of each component is added. Then, the anion (i.e., nitrate ion, chloride ion, sulfate ion) is added as a neutral salt (preferably an ammonium salt) to adjust to a predetermined conductivity. The substance (neutral salt) added to adjust the conductivity is referred to as a supporting electrolyte. Micro-adjustment is then performed as the pH changes from a predetermined value. Further, the pH adjustment is carried out using a base or an acid, but is not particularly limited. Preferably, ammonia is used as the base, and an acid (inorganic acid) having the same composition as the anion of the supporting electrolyte is used as the acid. By using ammonia during the adjustment of pH, even if ammonia is introduced into the formed film, ammonia is volatilized from the film during subsequent drying, and thus hardly remains in the film, and as a result, it does not adversely affect the film properties. The situation is completed. Further, by using an acid (inorganic acid) having the same composition as the anion of the supporting electrolyte at the time of pH adjustment, it is possible to minimize the adverse effect on the film properties of the formed film.

≪ 3. How to use metal surface treatment agent for electrolytic treatment≫

 <3-1. Object metal>  

When the film is formed on the target metal by using the metal surface treatment agent for electrolytic treatment of the present invention, it is possible to impart discoloration resistance to the surface-treated target metal while ensuring properties such as potability. From this point of view, the target metal of the metal surface treatment agent for electrolytic treatment of the present invention is preferably a metal material with Sn-based plating (for example, Sn plating, plating containing Sn and other metals (for example, solder)}. (for example, tinplate steel). Here, the Sn-based plating means that the content of Sn in the plating layer is 20% by mass or more based on the total mass of the plating layer (preferably 50% by mass or more, more preferably 70% or more). More preferably, it is 90% by mass or more. Further, in the Sn-based plating, in addition to Sn, one or a plurality of other metals (for example, Fe) may be present, and an alloy may be formed in the plating (for example, heat is applied to the Sn and then heat-treated (back) Alloy of Sn and Fe formed during soldering}. Further, the Sn-based plating layer preferably contains 100 to 15,000 mg/m ² of Sn on at least one side of the metal material to be plated. Further, the Sn-based plating system does not contain Zn, or even if Zn is contained, Zn is preferably 3% by mass or less, more preferably 2% by mass or less, and more preferably 1 based on the total mass of the plating layer. Below mass%. When a certain amount of Zn is contained, it is not easy to cause discoloration. However, as described above, the metal surface treatment agent for electrolytic treatment of the present invention can have potability, film adhesion, paint adhesion (primary coating adhesion, secondary coating adhesion), and corrosion resistance. Properties such as properties (corrosion resistance under coating film, heat sterilization and rust resistance) and resistance to sulfur blackening are imparted to the target metal. Therefore, from this viewpoint, the target metal is not limited to the metal material to which the Sn-based plating is applied, 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 of the present invention can form canning processability, film adhesion, and coating adhesion (primary coating adhesion, secondary coating adhesion) on a metal material by a general electrolytic method. Corrosion resistance (corrosion resistance under coating film, heat sterilization and rust resistance), and excellent properties such as resistance to sulfur blackening. In a specific example, when the metal material to be processed is a Sn-based plating metal material, the test material is a cathode side, and the metal surface treatment agent for electrolytic treatment is immersed at a predetermined temperature (typically 40 ° C). The test material is simultaneously (or after immersed) a method of energizing the test material at a predetermined current density (for example, 3.0 A/dm ² ) for a predetermined time (for example, 1 second). The electrolysis temperature is not particularly limited, but is preferably 10 ° C or more and 55 ° C or less. When the temperature is 10 ° C or more, it is easy to maintain the temperature. When the temperature is 55 ° C or less, corrosion to the electrolytic treatment apparatus is less likely to occur. The current density is not particularly limited, but a long electrolysis time is required in the case of a low current density. In the case of a high current density, although it can be treated with a short electrolysis time, the film deposition efficiency sometimes decreases.

 (Example)  

Hereinafter, the present invention will be described in more detail by way of examples. However, the invention is not limited to the following examples without departing from the scope of the invention. In addition, "%" means mass% unless otherwise noted.

<Test material>

The following materials were used as test materials.

 (1) Sn (tin) plated steel sheet (with reflow treatment) (ET)  

Plate thickness: 0.3mm

Sn-plated unit area weight: 2.8 g/m ²

 (2) Nickel plated steel sheet (NI)  

Plate thickness: 0.3mm

Ni-plated unit area weight: 0.8g/m ²

<Preparation of metal surface treatment agent for electrolytic treatment>

Addition to water: hydrofluoric acid as a raw material for dissolving a Zr component and a supply source for dissolving the F component, hydrofluoric acid as a raw material for dissolving a supply source of the F component, and orthophosphoric acid as a raw material of a supply source for dissolving the P component And set to the established F _w /Zr _w , P _w /Zr _w . Then, the substance type shown in Table 1 which is a raw material of the supply source of the dissolved metal (M) component is added in an amount as shown in Table 1, and then sufficiently mixed to form a dissolved metal (M) component under the naked eye. completely dissolved. Then, an acid (an acid having the same composition as the anion constituting the supporting electrolyte described in Table 1) or a base (ammonia) is added to adjust the pH. Further, after adjusting the conductivity by adding the supporting electrolyte described in Table 1, the pH was finely adjusted as needed. At this time, the acid and the alkali (ammonia and sodium hydroxide) are added so as to have a predetermined value of CA. In this way, each metal surface treatment chemical conversion treatment liquid is obtained. Further, when two or more kinds of supporting electrolytes are used and used, the mixing ratio is set to a mass ratio.

<Materials as a supply source for supporting electrolyte, anion and dissolved ammonium or ammonia N component>

E1: Ammonium nitrate

E2: ammonium sulfate

E3: ammonium chloride

<Materials as a supply source for dissolved metal (M) components and anions>

M1: zinc nitrate

M2: manganese sulfate

M3: Manganese nitrate

M4: Manganese chloride

M5: copper nitrate

M6: Cobalt nitrate

<pre-processing>

The pretreatment of the test material (pretreatment for electrolytic treatment) was carried out by immersion degreasing for 30 seconds in an alkali degreasing agent {Fine Cleaner-E6406 (manufactured by Nihon Parkerizing Co., Ltd.), 2% bath, 60 ° C}. The tap water is washed with water and washed with ion-exchanged water, and the water is removed by a water removal roller and dried by a dryer.

<Electrolysis treatment (standard electrolytic treatment)>

The test material which has been subjected to the pretreatment is supplied to the following electrolytic treatment (standard electrolytic treatment). The test material was used as a cathode, the carbon plate was set as a counter electrode, and the test material was immersed in a metal surface treatment agent for electrolytic treatment which was set to a predetermined temperature (40 ° C) while a current of 3.0 A/dm ^{2 was used} . Density electrolysis for 1 second. Then, the electrolytically treated test material was spray-washed with urban water at 25 ° C for 5 seconds, thereby cleaning the surface of the test material, and removing the water by roller extrusion, so that the surface of the test material reached a plate temperature of 50 ° C. Dry.

<Performance Evaluation>

The test materials which have been subjected to the above pretreatment and electrolytic treatment (standard electrolytic treatment) and the metal surface treatment agent for electrolytic treatment are evaluated for performance in accordance with the items (A) to (L) shown below. The test materials are shown in Table 2, and the results are shown in Table 3.

(A) Can processing capability

A PET film having a thickness of 20 μm was laminated on both sides of the test material at 200 ° C, and a blank having a diameter of 150 mm was punched out, and then stretched at a draw ratio of 1.67 to form a can diameter: 90 mm, and a can height: about 40 mm. Extension cans. Next, the above-mentioned extension can was re-extended and formed by a drawing ratio of 1.36, and a re-extension tank having a can diameter of 66 mm was produced, and the re-extension tank was used for three-stage retraction processing to obtain a plate thickness reduction rate: 50%. In the manner of performing the contraction forming process, the extension-contraction forming process was performed to produce an extension-contraction can having a can diameter of 66 mm and a can height of about 125 mm. Then, with respect to the extension-retracting can body, the flaw, the floating, and the peeling state of the film were evaluated in the following five stages. △ The above evaluation is a practical level.

◎: The total area ratio of the crotch portion, the floating portion, and the peeling portion of the film is 0%

○: The total area ratio of the crotch portion, the floating portion, and the peeling portion of the film is more than 0% and 0.5% or less.

○ Δ: The total area ratio of the crotch portion, the floating portion, and the peeling portion of the film is more than 0.5% and less than 5%.

△: The total area ratio of the crotch portion, the floating portion, and the peeling portion of the film is more than 5% and 15% or less.

×: The total area ratio of the crotch portion, the floating portion, and the peeling portion of the film is more than 15% or the test material is broken and cannot be formed.

(B) Film adhesion

A PET film having a thickness of 20 μm was laminated on both sides of the test material at 200 ° C, and a blank of 150 mm in diameter was punched out, and then stretched at a draw ratio of 1.67 to prepare an extension can having a can diameter of 90 mm and a can height of about 40 mm. Then, the extension can was subjected to heat sterilization treatment at 121 ° C for 30 minutes, and the peeling state of the film was evaluated in the following five stages. △ The above evaluation is a practical level.

◎: The area ratio of the peeling part is 0%

○: The area ratio of the peeling portion is more than 0% and 2% or less.

○ Δ: The area ratio of the peeling portion is more than 2% and less than 5%.

△: The area ratio of the peeling portion is more than 5% and less than 10%.

×: The area ratio of the peeling portion is over 10%

(C) primary coating adhesion

The epoxy-phenol resin was applied to the test material so as to have a dry film thickness of 6 g/m ² , and baked at 200 ° C for 10 minutes, and then cut into a checkerboard having a depth of 1 mm at an interval of 1 mm. Then, after the test material was attached to the cellophane tape, the tape was peeled off, and the peeling state of the coating film was evaluated in accordance with the following five stages. △ The above evaluation is a practical level.

◎: The area ratio of the peeling part is 0%

○: The area ratio of the peeling portion is more than 0% and less than 5%.

○ Δ: The area ratio of the peeling portion is more than 5% and 15% or less.

△: The area ratio of the peeling portion is more than 15% and 30% or less.

×: The area ratio of the peeling portion is over 30%

(D) secondary coating adhesion

The epoxy-phenol resin was applied to the test material so as to have a dry film thickness of 6 g/m ² , and baked at 200 ° C for 10 minutes, and then cut into a checkerboard having a depth of 1 mm at an interval of 1 mm. Then, the test material was subjected to heat sterilization treatment at 121 ° C for 30 minutes, and after drying, the tape was peeled off after the test material was bonded to the test material, and the peeling state of the coating film was evaluated in accordance with the following five stages. . △ The above evaluation is a practical level.

◎: The area ratio of the peeling part is 0%

○: The area ratio of the peeling portion is more than 0% and less than 5%.

○ Δ: The area ratio of the peeling portion is more than 5% and 15% or less.

△: The area ratio of the peeling portion is more than 15% and 30% or less.

×: The area ratio of the peeling portion is over 30%

(E) Corrosion resistance under the coating film

The epoxy-phenol resin was applied to the test material so as to have a dry film thickness of 6 g/m ² , and baked at 200 ° C for 10 minutes, and then subjected to cross-cutting to the base metal. Then, the test material was immersed in a test liquid composed of a 1.5% citric acid-1.5% salt mixture at 45 ° C for 72 hours. After washing and drying, after the test material is bonded to the celluloid tape, the tape is peeled off, and the etching width (mm) of the corrosion portion under the coating film of the cross-cut portion and the area ratio of the corroded portion of the flat plate portion are removed. (%) Based on the 5-stage evaluation described below. △ The above evaluation is a practical level.

◎: The corrosion width of the corrosion portion under the coating film of the cross-cut portion is less than 0.2 mm and the area ratio of the corroded portion of the flat portion is 0%.

○: The corrosion width of the corrosion portion under the coating film of the cross-cut portion is less than 0.3 mm and the area ratio of the corrosion portion of the flat portion is 1% or less (except when evaluated as ◎)

○ △: The corrosion width of the corrosion portion of the coating film in the cross-cut portion is less than 0.4 mm and the area ratio of the corrosion portion of the flat portion is 3% or less (except when evaluated as ◎ or ○)

△: The corrosion width of the corrosion portion under the coating film of the cross-cut portion is less than 0.5 mm and the area ratio of the corrosion portion of the flat portion is 5% or less (except when evaluated as ◎, ○, ○△)

×: The corrosion width of the corrosion portion under the coating film of the cross-cut portion is 0.5 mm or more or the area ratio of the corrosion portion of the flat portion is more than 5%.

(F) Heat sterilization and rust resistance

The test material was subjected to heat sterilization at 121 ° C for 30 minutes, and the occurrence of corrosion was observed. The area ratio (%) of the rust-generating portion was evaluated in the following five stages. △ The above evaluation is a practical level.

◎: The area ratio of the rust generating portion is 0%

○: The area ratio of the rust generating portion is more than 0% and less than 1%.

○ Δ: The area ratio of the rust generating portion is more than 1% and less than 3%.

△: The area ratio of the rust generating portion is more than 3% and less than 5%.

×: The area ratio of the rust generating portion is over 5%

(G) anti-sulfidation black denaturation

The epoxy-phenol resin was applied to the test material in such a manner as to be 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% cysteamine hydrochloride, 0.4% potassium dihydrogen phosphate, 0.81% sodium phosphate) at 121 ° C for 1 hour, the color difference (ΔE value) before and after the immersion was determined according to the following 5 Stage evaluation. △ The above evaluation is a practical level. Evaluation machine: Japan Electric Color Industrial SD7000 (SCI method: total reflection measurement)

◎: △E value is less than 3.0

○: △E value is 3.0 or more and less than 5.5

○△: △E value is 5.5 or more and less than 8.0

△: △ E value is 8.0 or more and less than 10.5

×: △E value is 10.5 or more

(H) Sn-resistant incorporation

To 100 ml of the metal surface treatment agent for electrolytic treatment, 350 mg/L of tin (II) chloride was added as Sn, and the mixture was allowed to stand in a thermostat 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 above evaluation is a practical level. Evaluation apparatus: a known method such as ICP-AES, which is a JIS-K0116:2014 specification ICP emission spectroscopic analyzer (ICP-AES)

◎: The dissolution rate of Sn is 80% or more

○: The Sn dissolution rate is 70% or more and less than 80%.

○△: The Sn dissolution rate is 60% or more and less than 70%.

△: The Sn dissolution rate is 50% or more and less than 60%.

×: The Sn dissolution rate is 40% or more and less than 50%.

(I) Discoloration resistance

The test materials were allowed to stand in a thermostat at 70 ° C and 80% RH for 72 hours. The color difference (ΔE value) before and after standing in the test material was evaluated in accordance with the following five stages. △ The above evaluation is a practical level. Evaluation machine: Japan Electric Color Industrial SD7000 (SCI method: total reflection measurement)

◎: △E value is less than 2.0

○: △E value is 2.0 or more and less than 4.0

○△: △E value is 4.0 or more and less than 6.0

△: △E value is 6.0 or more and less than 8.0

×: △ E value is 8.0 or more

(J) Short-term film precipitation

The test material (in the case of the evaluation, the test material which was not subjected to the standard electrolytic treatment, that is, the test material after the pretreatment) was used as a cathode, and the carbon plate was set as a counter electrode, and the test material was immersed in the predetermined In the metal surface treatment agent at a temperature (40 ° C), it was simultaneously electrolyzed at a current density of 10.0 A/dm ² for 0.3 seconds. Then, the electrolytically treated test material was spray-washed with urban water at 25 ° C for 5 seconds, thereby cleaning the surface of the test material, removing water by roller extrusion, and allowing the surface of the test material to reach a plate temperature of 50 ° C. dry. Then, the Zr adhesion amount of the test material was measured by a fluorescent X-ray analyzer, and the Zr adhesion amount (mg/m ² ) was evaluated in accordance with the following five stages. △ The above evaluation is a practical level.

◎: 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

△: 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) Treatment agent stability over time

100 mL of a metal surface treatment agent for electrolytic treatment was allowed to stand in a thermostat at 40 ° C for one month. The appearance (solution property) of the treatment agent after standing for one month and the mass (mg) of the residue of the treatment agent remaining on the filter paper after filtration of 100 mL of the treatment agent (No. 5C) are in accordance with the following five stages. Evaluation. △ The above evaluation is a practical level.

◎: 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 0 mg.

○ △: The treatment agent is turbid, and the mass of the residue is more than 0 mg and less than 10 mg.

△: The treatment agent is turbid, and the mass of the residue is more than 10 mg and less than 20 mg.

×: The treatment agent is turbid, and the mass of the residue is 20 mg or more.

(L) film appearance

The color difference (ΔE value) before and after the electrolytic treatment (standard electrolytic treatment) in the test material (in the evaluation material which is not subjected to standard electrolytic treatment, that is, the test material after pretreatment) is as follows. Stage evaluation. △ The above evaluation is a practical level. Evaluation machine: Japan Electric Color Industrial SD7000 (SCI method: total reflection measurement)

◎: △E value is less than 5.0

○: △E value is 5.0 or more and less than 7.0

○△: △E value is 7.0 or more and less than 9.0

△: △ E value is 9.0 or more and less than 11.0

×: △E value is 11.0 or more

Claims (24)

A metal surface treatment agent for electrolytic treatment, comprising: dissolving a Zr component; dissolving the F component; dissolving the P component; and dissolving the molten metal M of one or more selected from the group consisting of a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component. And an anion selected from the group consisting of a nitrate ion, a chloride ion, and a sulfate ion, wherein the converted mass (P _w ) of the P element of the dissolved P component and the Zr element of the dissolved Zr component are The conversion mass (M _w ) of the metal element (Zn element, Mn element, Cu element) of the dissolved metal M component in the range of the converted mass (Zr _w ) (P _w /Zr _w ) is 0.04 or more and 0.5 or less. The ratio (M _w /Zr _w ) to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is in the range of 0.05 or more and 2.5 or less. The metal surface treatment agent for electrolytic treatment according to claim 1, wherein 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 are used. The ratio (F _w /Zr _w ) is in the range of 1.3 or more and 2.5 or less.  The metal surface treatment agent for electrolytic treatment according to claim 1 or 2, wherein the Zr element concentration is in the range of 1000 mg/L or more and 1950 mg/L or less.    The metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 3, wherein the pH is in the range of 3.4 or more and 4.8 or less.   The metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 4, which may further comprise a component selected from the group consisting of dissolved Sn, dissolved Fe, dissolved ammonium or ammonia N, dissolved Na, and dissolved. At least one component of the group consisting of the K component, in this case, the conversion mass (Zr _w ) of the Zr element in which the Zr component is dissolved, and the conversion of the metal element (Zn element, Mn element, and Cu element) of the dissolved metal component M Mass (M _w ), converted mass of Sn element of the dissolved Sn component (Sn _w ), converted mass of Fe element of the dissolved Fe component (Fe _w ), and converted mass of N element of the dissolved ammonium or ammonia N component The total mass of (N _w ), the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal of the dissolved metal M component, and the converted mass of the Sn element of the dissolved Sn component ( Sn _w ), the converted mass (Fe _w ) of the Fe element in which the Fe component is dissolved, the converted mass (N _w ) of the N element of the dissolved ammonium or the ammonia N component, and the converted mass of the Na element of the dissolved Na component (Na) in terms of mass _w) was dissolved and the elements of the K component of K (K _w) a Ratio of CA Total _{mass: {(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 metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 5, which has a conductivity of 1.0 S/m or more and 6.0 S/m or less.    The metal surface treatment agent for electrolytic treatment according to any one of claims 1 to 6, wherein the metal to be treated is Sn-based plating.    The metal surface treatment agent for electrolytic treatment according to claim 7, wherein the metal to be treated is alloyed with Sn and Fe.   A method for producing a metal surface treatment agent for electrolytic treatment, the metal surface treatment agent for electrolytic treatment comprising: dissolving a Zr component; dissolving the F component; dissolving the P component; and selecting a component consisting of a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component. One or more kinds of dissolved metal M components in the group; and one or more anions selected from the group consisting of nitrate ions, chloride ions, and sulfate ions, and the converted mass of the P element of the dissolved P component (P _w The ratio (P _w /Zr _w ) to the converted mass (Zr _w ) of the Zr element in the dissolved Zr component is 0.04 or more and 0.5 or less, and the metal element (Zn element, Mn element, Cu) of the dissolved metal M component. The ratio (M _w /Zr _w ) of the converted mass (M _w ) of the element) to the converted mass (Zr _w ) of the Zr element of the dissolved Zr component is in a range of 0.05 or more and 2.5 or less; the manufacturing method includes: One or more raw materials which dissolve the Zr component, the dissolved F component, the dissolved P component, the dissolved metal M component, and the supply source of the anion are added to a liquid medium and mixed. The method for producing a metal surface treatment agent for electrolytic treatment according to claim 9, wherein the conversion quality (F _w ) of the F element of the dissolved F component and the conversion quality of the Zr element of the dissolved Zr component (Zr) within _w) ratio (F _w / Zr _w) is 1.3 to 2.5 range.  The method for producing a metal surface treatment agent for electrolytic treatment according to claim 9 or 10, wherein the Zr element concentration is in a range of from 1000 mg/L to 1950 mg/L.    The method for producing a metal surface treatment agent for electrolytic treatment according to any one of claims 9 to 11, wherein the pH is in the range of 3.4 or more and 4.8 or less.   The method for producing a metal surface treatment agent for electrolytic treatment according to any one of claims 9 to 12, further comprising a component selected from the group consisting of a dissolved Sn component, a dissolved Fe component, a dissolved ammonium or an ammoniated N component, At least one component of the group consisting of the dissolved Na component and the dissolved K component, in which case the Zr element of the dissolved Zr component is converted into a mass (Zr _w ), and the metal element of the dissolved metal M component (Zn element, Mn element, or The converted mass (M _w ) of the Cu element, the converted mass of the Sn element of the dissolved Sn component (Sn _w ), the converted mass of the Fe element of the dissolved Fe component (Fe _w ), and the dissolved ammonium or ammonia N component The total mass of the converted mass (N _w ) of the N element, the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal element of the dissolved metal M component, and the dissolved Sn component The converted mass (Sn _w ) of the Sn element, the converted mass (Fe _w ) of the Fe element in which the Fe component is dissolved, the converted mass (N _w ) of the N element of the dissolved ammonium or the ammonia N component, and the Na dissolved in the Na component in terms of mass elements (Na _w), and dissolving the ingredients K K Converted mass element of (K _w) ratio of CA total mass _{of: {(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 method for producing a metal surface treatment agent for electrolytic treatment according to any one of claims 9 to 13, wherein the conductivity is in a range of 1.0 S/m or more and 6.0 S/m or less.    The method for producing a metal surface treatment agent for electrolytic treatment according to any one of claims 9 to 14, wherein the metal to be treated is Sn-based plating.    The method for producing a metal surface treatment agent for electrolytic treatment according to claim 15, wherein the metal to be treated is alloy plating of Sn and Fe.   A surface treatment method for a metal material, comprising: a step of immersing a metal to be treated in a metal treatment agent for electrolytic treatment with a metal side of the treatment target as a cathode side; wherein the metal treatment agent for electrolytic treatment is The method further comprises: dissolving a Zr component; dissolving the F component; dissolving the P component; and selecting at least one dissolved metal component M selected from the group consisting of a dissolved Zn component, a dissolved Mn component, and a dissolved Cu component; and is selected from the group consisting of nitrate ions and chlorides One or more anions of the group consisting of ions and sulfate ions, and the mass ratio of the converted mass (P _w ) of the P element of the dissolved P component to the converted mass of the Zr element of the dissolved Zr component (Zr _w ) (P _w /Zr _w ) is a conversion mass (M _w ) of a metal element (Zn element, Mn element, Cu element) of the dissolved metal M component and a conversion mass of the Zr element of the dissolved Zr component in a range of 0.04 or more and 0.5 or less. the (Zr _w) ratio (M _w / Zr _w) is 0.05 to 2.5 range. The surface treatment method according to claim 17, wherein the conversion quality (F _w ) of the F element of the dissolved F component in the metal treatment agent for electrolytic treatment and the conversion quality of the Zr element of the dissolved Zr component are the (Zr _w) ratio (F _w / Zr _w) is 1.3 to 2.5 range.  The surface treatment method according to the above-mentioned item, wherein the metal treatment agent for electrolytic treatment has a Zr element concentration of from 1000 mg/L to 1950 mg/L.    The surface treatment method according to any one of the above-mentioned claims, wherein the pH of the metal treatment agent for electrolytic treatment is in a range of 3.4 or more and 4.8 or less.   The surface treatment method according to any one of the preceding claims, wherein the metal treatment agent for electrolytic treatment may further contain a component selected from the group consisting of a dissolved Sn component, a dissolved Fe component, a dissolved ammonium or an ammoniated N component, At least one component of the group consisting of the dissolved Na component and the dissolved K component, in which case the Zr element of the dissolved Zr component is converted into a mass (Zr _w ), and the metal element of the dissolved metal M component (Zn element, Mn element, or The converted mass (Mw) of the Cu element), the converted mass of the Sn element of the Sn component (Sn _w ), the converted mass of the Fe element of the dissolved Fe component (Fe _w ), and the N element of the dissolved ammonium or ammonia N component The total mass of the converted mass (N _w ), the converted mass (Zr _w ) of the Zr element of the dissolved Zr component, the converted mass (M _w ) of the metal of the dissolved metal component M, and the conversion of the Sn element of the Sn component Mass (Sn _w ), conversion mass (Fe _w ) of the Fe element in which the Fe component is dissolved, conversion mass (N _w ) of the N element of the dissolved ammonium or ammonia N component, and conversion quality of the Na element of the dissolved Na component Conversions (Na _w) was dissolved and the elements of the K component K Mass of the total mass amount (K _w) ratio of _{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 surface treatment method according to any one of the aspects of the present invention, wherein the metal treatment agent for electrolytic treatment has a conductivity of 1.0 S/m or more and 6.0 S/m or less.    The surface treatment method according to any one of claims 17 to 22, wherein the metal to be treated is Sn-based plating.    The surface treatment method according to Item 23, wherein the metal to be treated is an alloy plating of Sn and Fe.