CN109415835A

CN109415835A - Metal conditioner is used in electrolysis processing

Info

Publication number: CN109415835A
Application number: CN201780041176.3A
Authority: CN
Inventors: 上野圭; 上野圭一; 北村和也; 石和田碧
Original assignee: Nihon Parkerizing Co Ltd
Current assignee: Nihon Parkerizing Co Ltd
Priority date: 2016-07-21
Filing date: 2017-06-16
Publication date: 2019-03-01
Anticipated expiration: 2037-06-16
Also published as: JP6352987B2; TW201835390A; WO2018016251A1; JP2018012858A; CN109415835B; TWI733857B

Abstract

The present invention provides a kind of electrolysis processing metal conditioner, it can not only be to imparting tank processability processed, film adaptation, coating adhesion, corrosion resistance, resistance to vulcanization blackening etc. on Sn system plating material, the property of discoloration-resistant can also be assigned, and precipitation, the stability based on the mixed metal conditioner of Sn, the ageing stability of metal conditioner etc. of the Zr-P based coating in the short time are preferred in practical.A kind of electrolysis processing metal conditioner, contains: dissolution Zr ingredient；Dissolve F ingredient；Dissolve P ingredient；And selected from one or more of nitrate ion, chloride ion and sulfate ion anion, the reduced mass (P of the P element of above-mentioned dissolution P ingredient_w) reduced mass (Zr with the Zr element of above-mentioned dissolution Zr ingredient_w) the ratio between (P_w/Zr_w) in 0.04 or more and 0.5 or less range, the concentration of the hydrogen peroxide conversion ingredient calculated by redox titration is in the range of 100mg/L or more and 1500mg/L or less.

Description

Metal conditioner is used in electrolysis processing

Technical field

The present invention relates to electrolysis processing metal conditioners.

Background technique

Up to now, various metal materials are mentioned as the surface treatment method for improving the property of the metal material Various methods are gone out.

For example, tinplate material is material obtained by surface plating tin (stannum, Sn) to steel plate.The tin-coated steel Skin material is antirust, for moisture etc. also have corrosion resistance, be also adapted to welding, soldering, therefore be mainly as tank (welded tank, Be brazed tank) material, electric component etc. and widely used raw material.Herein, for the surface treatment of the tinplate material Can be classified as method is typical chemical conversion treatment (referring for example to patent document 1), electrolysis processing (referring for example to patent document 2), Application type handles (such as patent document 3).In turn, the type of the overlay film formed on the tinplate material is also varied (referring for example to Patent Documents 1 to 3).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 1-100281 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2009-280888 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2004-307923 bulletin

Summary of the invention

Problems to be solved by the invention

Herein, as described above, tinplate material is mainly used as the material of tank.If in view of making on the way in the use With then for the surface treated tinplate material requirements tank processability, film adaptation, coating adhesion (primary painting Expect adaptation, secondary coating adaptation), corrosion resistance (under film corrosion resistance, distillation resistance to rust), the properties such as resistance to vulcanization blackening.

The inventors of the present invention are directed to the overlay film type for meeting these properties and processing method has carried out various researchs, as a result send out It is existing: if making Sn by electrolysis processing using comprising dissolution Zr ingredient, dissolution F ingredient and the metal conditioner for dissolving P ingredient It is formation Zr-P based coating on coating, then can realizes above-mentioned property with previous chromic acid salt treatment peer-level.

However, on the other hand, the inventors of the present invention obtain following opinion: making Sn with using other overlay film types, processing method It is to be formed with the sample of overlay film on coating to compare, so that the sample for being formed with Zr-P based coating on Sn system coating is existed using electrolysis processing Discoloration-resistant when passing through long-time under moist environment is sometimes worse.

Thus, the subject of the invention is to provide a kind of electrolysis processing metal conditioners, can not only be to Sn system Assigned on plating material tank processability processed, film adaptation, coating adhesion (coating adhesion, secondary coating adaptation), Corrosion resistance (corrosion resistance, distillation resistance to rust under film), resistance to vulcanization blackening etc., additionally it is possible to the property of discoloration-resistant is assigned, and The precipitation (short time overlay film be precipitated property) of Zr-P based coating in short time, based on the steady of the mixed metal conditioner of Sn Qualitative (resistance to being mixed into property of Sn), ageing stability (inorganic agent ageing stability) of metal conditioner etc. are preferred in practical 's.

The method for solving problem

The present invention is as follows.

[1] a kind of electrolysis processing metal conditioner, contains: dissolution Zr ingredient；Dissolve F ingredient；Dissolve P at Point；And it is selected from one or more of nitrate ion, chloride ion and sulfate ion anion,

Reduced mass (the P of the P element of above-mentioned dissolution P ingredient_w) reduced mass with the Zr element of above-mentioned dissolution Zr ingredient (Zr_w) the ratio between (P_w/Zr_w) be 0.04 or more and 0.5 or less range in,

It is 100mg/L or more by the convert concentration of ingredient of the hydrogen peroxide that redox titration shown in following calculates And in the range of 1500mg/L or less.

[redox titration]: electrolysis processing metal conditioner 20ml is taken, deionized water 80ml is added.In turn 50% sulfuric acid (specific gravity 1.395) 10ml is added, potassium iodide 2.0g is added, is stood after five minutes in sombre place, it is thio with 0.1M The method that metabisulfite solution is titrated.Terminal is set as becoming from brown colourless point.

Concentration (mg/L)=titer (ml) × 85.0 of hydrogen peroxide conversion ingredient

[2] processing of the electrolysis according to above-mentioned [1] metal conditioner, wherein the F member of above-mentioned dissolution F ingredient Reduced mass (the F of element_w) reduced mass (Zr with the Zr element of above-mentioned dissolution Zr ingredient_w) the ratio between (F_w/Zr_w) be 1.3 or more and In 2.5 or less range.

[3] processing of the electrolysis according to above-mentioned [1] or [2] metal conditioner, wherein Zr concentration of element is In the range of 1000mg/L or more and 1950mg/L or less.

[4] electrolysis according to above-mentioned [1]~[3] processing use metal conditioner, wherein pH be 3.4 or more and In 4.8 or less range.

[5] processing of the electrolysis according to above-mentioned [1]~[4] metal conditioner, wherein above-mentioned hydrogen peroxide changes Be counted as being divided into be originated from selected from one or more of hydrogen peroxide, nitrous acid, persulfuric acid, organic peroxide and its salt substance at Point.

[6] processing of the electrolysis according to above-mentioned [1]~[5] metal conditioner, can be further containing choosing From dissolution Sn ingredient, dissolution Fe ingredient, dissolved ammonia state N ingredient, dissolution Na ingredient and at least one kind of ingredient in K ingredient is dissolved, this When, the reduced mass (Zr of the Zr element of above-mentioned dissolution Zr ingredient_w), above-mentioned hydrogen peroxide conversion ingredient quality (A_W), it is above-mentioned molten Solve the reduced mass (Sn of the Sn element of Sn ingredient_w), the reduced mass (Fe of the Fe element of above-mentioned dissolution Fe ingredient_w) and it is above-mentioned molten Solve the reduced mass (N of the N element of ammonia state N ingredient_w) total quality and above-mentioned dissolution Zr ingredient Zr element reduced mass (Zr_w), above-mentioned hydrogen peroxide conversion ingredient quality (A_W), the reduced mass (Sn of the Sn element of above-mentioned dissolution Sn ingredient_w), on State the reduced mass (Fe of the Fe element of dissolution Fe ingredient_w), the reduced mass (N of the N element of above-mentioned dissolved ammonia state N ingredient_w), on State the reduced mass (Na of the Na element of dissolution Na ingredient_w) and above-mentioned dissolution K ingredient K element reduced mass (K_w) it is total Mass ratio CA:{ (Zr_w+A_W+Sn_w+Fe_w+N_w)/(Zr_w+A_W+Sn_w+Fe_w+N_w+Na_w+K_w) it is 0.9 or more.

[7] processing of the electrolysis according to above-mentioned [1]~[6] metal conditioner, wherein conductivity 1.0S/m Above and in the range of 6.0S/m or less.

[8] processing of the electrolysis according to above-mentioned [1]~[7] metal conditioner, wherein dealing with objects metal is Sn system coating.

[9] electrolysis according to above-mentioned [8] processing use metal conditioner, wherein process object metal be Sn with The alloy layer of Fe.

[10] a kind of manufacturing method for being electrolysed processing metal conditioner, wherein metal watch is used in the electrolysis processing Surface treatment agent contains: dissolution Zr ingredient；Dissolve F ingredient；Dissolve P ingredient；And it is selected from nitrate ion, chloride ion and sulphur One or more of acid ion anion,

It is 100mg/L or more by the convert concentration of ingredient of the hydrogen peroxide that redox titration shown in following calculates And in the range of 1500mg/L or less,

The manufacturing method is characterized in that comprising:

Above-mentioned dissolution Zr ingredient, above-mentioned dissolution F ingredient, E will be become and state dissolution P ingredient, above-mentioned hydrogen peroxide conversion ingredient It is added in liquid medium with more than one raw materials of the supply source of above-mentioned anion, and mixed process.

[11] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [10], wherein above-mentioned molten Solve the reduced mass (F of the F element of F ingredient_w) reduced mass (Zr with the Zr element of above-mentioned dissolution Zr ingredient_w) the ratio between (F_w/ Zr_w) in 1.3 or more and 2.5 or less range.

[12] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [10] or [11], wherein Zr concentration of element is in 1000mg/L or more and the range of 1950mg/L or less.

[13] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [10]~[12], wherein In the range that pH is 3.4 or more and 4.8 or less.

[14] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [10]~[13], wherein Above-mentioned hydrogen peroxide is converted into 1 be divided into Yuan Zi in hydrogen peroxide, nitrous acid, persulfuric acid, organic peroxide and its salt Kind or more substance ingredient.

[15] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [10]~[14], it can be with Further contain in dissolution Sn ingredient, dissolution Fe ingredient, dissolved ammonia state N ingredient, dissolution Na ingredient and dissolution K ingredient extremely Few a kind of ingredient the, at this point, reduced mass (Zr of the Zr element of above-mentioned dissolution Zr ingredient_w), above-mentioned hydrogen peroxide conversion ingredient matter Measure (A_W), the reduced mass (Sn of the Sn element of above-mentioned dissolution Sn ingredient_w), the reduced mass of the Fe element of above-mentioned dissolution Fe ingredient (Fe_w) and dissolved ammonia state N ingredient N element reduced mass (N_w) total quality and the Zr element of above-mentioned dissolution Zr ingredient change Calculate quality (Zr_w), above-mentioned hydrogen peroxide conversion ingredient quality (A_W), the reduced mass of the Sn element of above-mentioned dissolution Sn ingredient (Sn_w), the reduced mass (Fe of the Fe element of above-mentioned dissolution Fe ingredient_w), the reduced mass of the N element of above-mentioned dissolved ammonia state N ingredient (N_w), the reduced mass (Na of the Na element of above-mentioned dissolution Na ingredient_w) and above-mentioned dissolution K ingredient K element reduced mass (K_w) Total mass ratio CA:{ (Zr_w+A_W+Sn_w+Fe_w+N_w)/(Zr_w+A_W+Sn_w+Fe_w+N_w+Na_w+K_w) it is 0.9 or more.

[16] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [10]~[15], wherein Be electrolysed processing metal conditioner conductivity be 1.0S/m or more and the range of 6.0S/m or less in.

[17] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [10]~[16], wherein Process object metal is Sn system coating.

[18] manufacturing method of processing metal conditioner is electrolysed according to above-mentioned [17], wherein processing pair As the alloy layer that metal is Sn and Fe.

[19] a kind of surface treatment method of metal material, characterized in that it comprises: process object metal impregnation in It is electrolysed in the state of processing metal conditioner, the process being powered using the process object metal as cathode side,

Above-mentioned electrolysis processing metal conditioner contains:

Dissolve Zr ingredient；Dissolve F ingredient；Dissolve P ingredient；And it is selected from nitrate ion, chloride ion and sulfate radical One or more of ion anion,

Reduced mass (the P of the P element of above-mentioned dissolution P ingredient_w) reduced mass with the Zr element of above-mentioned dissolution Zr ingredient (Zr_w) mass ratio (P_w/Zr_w) be 0.04 or more and 0.5 or less range in,

[20] surface treatment method according to above-mentioned [19], wherein in above-mentioned electrolysis processing metal conditioner Reduced mass (the F of the F element of above-mentioned dissolution F ingredient_w) reduced mass (Zr with the Zr element of above-mentioned dissolution Zr ingredient_wThe ratio between) (F_w/Zr_w) in 1.3 or more and 2.5 or less range.

[21] surface treatment method according to above-mentioned [19] or [20], wherein above-mentioned electrolysis processing is handled with metal Zr concentration of element in agent is in 1000mg/L or more and the range of 1950mg/L or less.

[22] surface treatment method according to above-mentioned [19]~[21], wherein above-mentioned electrolysis processing is handled with metal In the range that pH in agent is 3.4 or more and 4.8 or less.

[23] surface treatment method according to above-mentioned [19]~[22], wherein above-mentioned hydrogen peroxide, which is converted into, to be divided into From the ingredient selected from one or more of hydrogen peroxide, nitrous acid, persulfuric acid, organic peroxide and its salt substance.

[24] surface treatment method according to above-mentioned [19]~[23], wherein above-mentioned electrolysis processing is handled with metal Agent can be further containing selected from dissolution Sn ingredient, dissolution Fe ingredient, dissolved ammonia state N ingredient, dissolution Na ingredient and dissolution K ingredient In at least one kind of ingredient, at this point, the reduced mass (Zr of the Zr element of above-mentioned dissolution Zr ingredient_w), above-mentioned hydrogen peroxide is converted into Quality (the A divided_W), the reduced mass (Sn of the Sn element of above-mentioned Sn ingredient_w), the conversion matter of the Fe element of above-mentioned dissolution Fe ingredient Measure (Fe_w) and dissolved ammonia state N ingredient N element reduced mass (N_w) total quality and above-mentioned dissolution Zr ingredient Zr element Reduced mass (Zr_w), above-mentioned hydrogen peroxide conversion ingredient quality (A_W), the reduced mass of the Sn element of above-mentioned Sn ingredient (Sn_w), the reduced mass (Fe of the Fe element of above-mentioned dissolution Fe ingredient_w), the reduced mass of the N element of above-mentioned dissolved ammonia state N ingredient (N_w), the reduced mass (Na of the Na element of above-mentioned dissolution Na ingredient_w) and above-mentioned dissolution K ingredient K element reduced mass (K_w) Total quality mass ratio CA:{ (Zr_w+A_W+Sn_w+Fe_w+N_w)/(Zr_w+A_W+Sn_w+Fe_w+N_w+Na_w+K_w) it is 0.9 or more.

[25] surface treatment method according to above-mentioned [19]~[24], wherein above-mentioned electrolysis processing is handled with metal The conductivity of agent is in 1.0S/m or more and the range of 6.0S/m or less.

[26] surface treatment method according to above-mentioned [19]~[25], wherein above-mentioned process object metal is Sn system Coating.

[27] surface treatment method according to above-mentioned [26], wherein above-mentioned process object metal is the conjunction of Sn and Fe Gold plate.

The effect of invention

In accordance with the invention it is possible to a kind of electrolysis processing metal conditioner is provided, it can not only be to Sn system plating Tank processability processed, film adaptation, coating adhesion (coating adhesion, secondary coating adaptation), anti-corrosion is assigned on material Property (under film corrosion resistance, distillation resistance to rust), resistance to vulcanization blackening etc., additionally it is possible to assign the property of discoloration-resistant, and in short-term Between property is precipitated in overlay film, resistance to being mixed into property of Sn, inorganic agent ageing stability etc. are preferred in practical.

Specific embodiment

According to sequence below, the present invention is illustrated.

1. metal conditioner is used in electrolysis processing

1-1. constituent

1-2. composition (containing than, content)

1-3. fluidity

2. being electrolysed the manufacturing method of processing metal conditioner

2-1. raw material

2-2. technique

3. being electrolysed the application method of processing metal conditioner

3-1. object metal

3-2. technique

" 1. electrolysis processing metal conditioner "

Electrolysis processing metal conditioner of the invention contains dissolution Zr ingredient；Dissolve F ingredient；Dissolve P ingredient；With And selected from one or more of nitrate ion, chloride ion and sulfate ion anion, the P element of above-mentioned dissolution P ingredient Reduced mass (P_w) reduced mass (Zr with the Zr element of above-mentioned dissolution Zr ingredient_w) the ratio between (P_w/Zr_w) be 0.04 or more and In 0.5 or less range, the concentration of the hydrogen peroxide conversion ingredient calculated by following redox titrations shown is In the range of 100mg/L or more and 1500mg/L or less.In addition, electrolysis processing of the invention further includes with metal conditioner Any one of new liquid (not carrying out the liquid of electrolysis processing) and load liquid (carry out be electrolysed treated liquid).

[redox titration]: hold pipette entirely with 20ml and 20ml is taken to be electrolysed processing metal conditioner, investment In conical flask.Then, with the deionized water of 100ml graduated cylinder addition 80ml, (compared with 50% sulfuric acid of 10ml graduated cylinder addition 10ml Weight is 1.395), and after adding potassium iodide 2.0g, to stand 5 minutes in sombre place.Thereafter, 0.1M hypo solution is used Minimum scale is that the 25ml buret of 0.1ml is titrated.It should be noted that sombre place refer to temperature be 20 DEG C and not by The place of sun light direct beam.In addition, terminal is set as becoming from brown colourless point.

The hydrogen peroxide conversion ingredient being electrolysed in processing metal conditioner occurs under sulfuric acid with potassium iodide Redox reaction, and generate iodine.Hydrogen peroxide converts ingredient when being originated from hydrogen peroxide, 1 mole of hydrogen peroxide and 2 moles Redox reaction occurs for potassium iodide (KI, colourless), generates 1 mole of iodine (I₂).In the iodine (brown) and titrating solution of the generation Sodium thiosulfate occur redox reaction, become colourless sodium iodide (NaI).It should be noted that 2 moles of thio sulphur Redox reaction occurs for sour sodium and 1 mole of iodine.Based on the redox reaction, find out by the titration of 0.1M sodium thiosulfate When amount is converted into the formula of the concentration of hydrogen peroxide conversion ingredient, as follows.

Concentration (mg/L)=0.1M sodium thiosulfate titer (m1) × 85.0 of hydrogen peroxide conversion ingredient

<1-1. constituent>

{ 1-1-1. dissolves Zr ingredient }

Dissolution Zr ingredient refers under room temperature (20 DEG C) and normal pressure (1atm=101325Pa) in the formulation in dissolved form The ingredient containing Zr element of state.Dissolution Zr ingredient is not particularly limited, such as with Zr ion (such as Zr⁴⁺) and Zr and its Complex ion (ZrF made of the bonding of its ingredient (such as F)₆ ^2-、ZrF₅ ^-、ZrF₃ ⁺、ZrF₂ ²⁺、ZrF³⁺) or molecule (ZrF₄), oxidation Zirconium ion (ZrO³⁺、HZrO₃ ^-) etc. form exist.In addition, preferably containing in electrolysis processing metal conditioner of the invention The F for the amount that can be bonded with Zr is had more than, therefore, most dissolution Zr ingredient can be speculated with ZrF₆ ^2-(or one therein Point F form made of other ligand substitutings, cation electrodeposition are incorporated into form made of the anion) form exist.

{ 1-1-2. dissolves F ingredient }

Dissolution F ingredient refers under room temperature (20 DEG C) and normal pressure (latm=101325Pa) in the formulation in dissolved state The ingredient containing F element.Dissolution F ingredient is not particularly limited, such as with F ion and F and other ingredients (such as Zr, H) Complex ion (ZrF made of bonding₆ ^2-、ZrF₅ ^-、ZrF₃ ⁺、ZrF₂ ²⁺、ZrF³⁺、HF₂ ^-) or molecule (HF, ZrF₄) etc. form deposit ?.In addition, electrolysis processing of the invention is with the F for preferably containing more than the amount that can be bonded with Zr in metal conditioner, because This, can speculate most dissolution F ingredient with ZrF₆ ^2-(or a part of F form made of other ligand substitutings therein, Cation electrodeposition is incorporated into form made of the anion) form exist, it is remaining to be formed with F ion, HF or with other ingredients The form of bonding body exists.In addition, enumerating " ZrF above₆ ^2-" an example as " dissolution F ingredient ", but the ingredient also contains Zr, Therefore, which also belongs to " dissolution Zr ingredient " (also identical for other ingredients).That is, ingredient is present in liquid with dissolved form The form of state exists, and when the existing ingredient contains two or more element such as Zr and F (such as " X " and " Y "), this it is existing at Divide is both " dissolution X ingredient " and " dissolution Y ingredient ".

{ 1-1-3. dissolves P ingredient }

Dissolution P ingredient, which refers to, contains P in dissolved state under room temperature (20 DEG C) and normal pressure (1atm=101325Pa) The ingredient of element.Dissolution P ingredient is not particularly limited, such as with (1) orthophosphoric acid state phosphorus, (2) polymer phosphate state phosphorus, (3) dissolution Property organic phosphorus acid-state phosphorus etc. form exist.Herein, as a more specific example, (1) orthophosphoric acid state phosphorus is to be in the formulation Dissolved state contains phosphate radical (PO₄) ingredient, such as orthophosphoric acid (H can be enumerated₃PO₄), phosphate anion (H₂PO₄ ^-、 HPO₄ ^2-、PO₄ ^3-) etc. and the bonding body that is formed of these ions and other ingredients.In addition, as a more specific example, (2) are poly- Close phosphoric acid state phosphorus can enumerate in the formulation pyrophosphoric acid, polyphosphoric acid, metaphosphoric acid and their ion etc. in dissolved state, with And the bonding body that their ion and other ingredients are formed.In turn, the organic phosphorus acid-state phosphorus of (3) dissolubility is in the formulation in molten The ingredient containing organic phosphoric acid of solution state, can enumerate for example in the formulation in dissolved state phosphonic acids and they from The bonding body that son and their ion and other ingredients are formed.Herein, organic phosphoric acid is made comprising carbon (C), protium (H), the composition of oxygen element (O) and P elements (P) has the property of the oxyacid (phosphonic acids) as phosphorus.

{ 1-1-4. anion }

Electrolysis processing of the invention with metal conditioner further include selected from nitrate ion, chloride ion and One or more of sulfate ion anion.As the strategy for Effluent Discharge of present treatment agent, implementing nitrate ammonia and reducing (including to disappear Except nitrate ammonia) in the case where countermeasure, as anion, all or part of of nitrate ion can be substituted for chloride Ion and/or sulfate ion are coped with.As the countermeasure for preventing electrolytic processing apparatus from corroding, (packet is reduced implementing chloride Include and eliminate chloride) in the case where countermeasure, as anion, all or part of of chloride ion can be substituted for nitric acid Radical ion and/or sulfate ion are coped with.Implement the strategy for Effluent Discharge of present treatment agent and prevents electrolytic processing apparatus from corroding In the case where countermeasure, as anion, all or part of of nitrate ion and chloride ion can be substituted for sulfuric acid Radical ion is coped with.

{ 1-1-5. hydrogen peroxide conversion ingredient }

Hydrogen peroxide conversion ingredient is to be electrolysed the oxidative components included in processing metal conditioner.In addition, mistake Hydrogen oxide conversion ingredient is not limited to hydrogen peroxide, refers in above-mentioned redox titration, it is assumed that oxidative components are all Hydrogen peroxide and the ingredient of concentration has been determined.Hydrogen peroxide conversion ingredient is derived from selected from such as hydrogen peroxide, nitrous acid, mistake The ingredient of sulfuric acid, organic peroxide and its oxidative components in salt (such as sodium salt, ammonium salt).Herein, as organic peroxy Compound can enumerate the water-soluble substances such as tert-butyl hydroperoxide, acetylacetone peroxide.Among these, it is originated from The hydrogen peroxide conversion ingredient of hydrogen peroxide is thinning from overlay film and overlay film densification can be made (to be formed blunt as chromic acid salt treatment Change film property overlay film) from the perspective of particularly preferably.

{ the other ingredients of 1-1-6. }

Electrolysis processing of the invention as needed can be containing known in this field using with metal conditioner Ingredient.For example, dissolution Sn ingredient can be contained, dissolution Fe ingredient, dissolved ammonia state N ingredient (i.e. ammonium, ammonia), Na ingredient is dissolved, is molten Solve K ingredient.Herein, which can be the ingredient added when preparing new liquid, be also possible to the stage in load liquid by original The ingredient of the supplies such as material (steel plate).For example, dissolution Sn ingredient, dissolution Fe ingredient do not limit, it is processed for typical The ingredient supplied in journey by raw material (steel plate).In addition, such as dissolution Na ingredient, dissolution K ingredient does not limit, for typical, It is included in the industrial water (well water, underground water, tap water) for being used as liquid medium in treatment process and is supplied to or is locating The ingredient for being attached to raw material surface during reason and being supplied to.Wherein, metal conditioner is used in electrolysis of the invention processing It is preferred that without K ingredient (being potassium ion for typical) or the only degree (K containing trace is dissolved_w: 3mg/L or less).It is being free of It dissolves K ingredient or only in the case where the degree containing trace, property, which is precipitated, in short time overlay film becomes especially good.In addition, this hair Bright electrolysis processing is preferably free of dissolution Na ingredient (being sodium ion for typical) with metal conditioner or only contains trace Degree (the Na of amount_w: 3mg/L or less).In the case where the degree without dissolution Na ingredient or only containing trace, overlay film appearance Property become especially good.It is preferable to use deionized waters for the liquid medium of inorganic agent as a result,.

{ 1-1-7. liquid medium }

It is preferably the liquid using water as main body that the liquid medium in metal conditioner is used in electrolysis processing of the invention Medium (such as deionized water, pure water).Herein, refer to " as main body ": using the gross mass of liquid medium as benchmark, water 51 Quality % or more (preferably 60 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, Particularly preferably 90 mass % or more).Therefore, above-mentioned each ingredient (dissolution Zr ingredient, dissolution F ingredient, dissolution P ingredient, peroxidating Hydroperoxide conversion ingredient etc.) in " dissolution " refer to: be dissolved in the state of the liquid medium (preferably water) using water as main body, such as It rephrases the statement and is properly termed as " water-soluble ".In addition, electrolysis processing metal conditioner of the invention not only includes only containing The form of above-mentioned solvent components, liquid medium, further include sludge has coexisted, such as excess amount of ions through product made of insoluble { detailed morphology is unknown, but for example, FePO₄、SnF₄、SnO(OH)₂、Sn(OH)₄Deng } form.In addition, as liquid medium, Can be containing other liquid mediums (such as liquid medium, alcohols such as ethyl alcohol of water Combination) in addition to water, but be Electrolysis processing is carried out, preferably its is less.Other liquid solvents in addition to water are using the gross mass of liquid medium as benchmark For 20 mass % or less, preferably 10 mass % or less, more preferably 5 mass % or less, further preferably 3 mass % with Under, particularly preferably 1 mass % or less.In addition, this preparation can be dry-form or concentration form.At this point, on the spot with water-soluble Solution or dilution reuse.

<1-2. composition>

{ 1-2-1. contains ratio }

(1-2-1-1.P_wWith Zr_wMass ratio)

Reduced mass (the P of the P element of dissolution P ingredient in electrolysis processing metal conditioner of the invention_w) with Dissolve the reduced mass (Zr of the Zr element of Zr ingredient_w) the ratio between (P_w/Zr_w) be 0.04 or more and 0.5 or less range in, preferably For in 0.06 or more and 0.4 or less range, more preferably 0.08 or more and 0.3 or less.In electrolysis processing gold of the invention In the specific system of metal surface inorganic agent, { for accurate, pass through the base in the parameter by the way that the ratio to be set as within the scope of this On plinth, the concentration of aftermentioned hydrogen peroxide conversion ingredient is set as in aftermentioned range, it is possible to provide it can not only be to Sn system plating material Imparting tank processability processed, film adaptation, coating adhesion (coating adhesion, secondary coating adaptation), corrosion resistance on material (corrosion resistance, distillation resistance to rust under film), resistance to vulcanization blackening etc., additionally it is possible to assign the property of discoloration-resistant, and the short time is covered Property, resistance to being mixed into property of Sn, inorganic agent ageing stability etc. preferred electrolysis processing metal conditioner in practical is precipitated in film. Especially, if P_w/Zr_wLess than 0.04, then resistance to vulcanization blackening is deteriorated.In addition, if P_w/Zr_wMore than 0.5, then film adaptation becomes Difference.Herein, the quality determination of the P element in preparation and Zr element shines using the ICP based on JIS-K0116:2014 standard The known methods such as spectroscopy apparatus (ICP-AES) carry out.

(1-2-1-2.F_wWith Zr_wMass ratio)

{ reduced mass (the F of the F element of dissolution F ingredient in electrolysis processing metal conditioner of the invention_w) with Dissolve the reduced mass (Zr of the Zr element of Zr ingredient_w) the ratio between (F_w/Zr_w) be preferably 1.3 or more and 2.5 or less range in, In more preferably 1.32 or more and 2.4 or less range, further preferably 1.36 or more and 2.3 or less.If F_wWith Zr_wThe ratio between For that in above range, then said effect can be made more excellent.Especially, if F_w/Zr_wReach 1.3 or more, then resistance to being mixed into property of Sn becomes It obtains better.If F_w/Zr_wFor 2.5 hereinafter, then secondary coating adaptation becomes better.Herein, the quality of the F element in preparation Measurement can be by will to what is recorded in the 34.1 of JIS-K0102:2014 standard based on lanthanum-alizarin aminoxatyl complex absorption photometry The solution that fluorine compounds distillation is isolated carries out quantitative analysis to carry out.

(1-2-1-3. is specified to be grouped mutual mass ratio)

It in turn, can be containing selected from dissolution Sn ingredient, dissolution Fe ingredient, dissolved ammonia state N ingredient, dissolution Na ingredient and dissolution At least one kind of ingredient in K ingredient, at this point, by the reduced mass (Zr of the Zr element of Zr ingredient_w), hydrogen peroxide conversion ingredient Quality (A_W), dissolution Sn ingredient Sn element reduced mass (Sn_w), dissolution Fe ingredient Fe element reduced mass (Fe_w) and Reduced mass (the N of the N element of dissolved ammonia state N ingredient_w) total quality and dissolution Zr ingredient Zr element reduced mass (Zr_w), hydrogen peroxide conversion ingredient quality (A_W), dissolution Sn ingredient Sn element reduced mass (Sn_w), dissolution Fe ingredient Fe element reduced mass (Fe_w), the reduced mass (N of the N element of dissolved ammonia state N ingredient_w), dissolution Na ingredient Na element Reduced mass (Na_w) and dissolution K ingredient K element reduced mass (K_w) total mass ratio when being denoted as CA, CA is preferably 0.9 or more, more preferably 0.92 or more.If the range, then overlay film appearance becomes good.Herein, the Sn element in preparation and The quality determination of Fe element can pass through the ICP emission spectrophotometer (ICP-AES) etc. based on JIS-K0116:2014 standard Known method carries out.In addition, the quality determination of the N element, Na element and K element of the dissolved ammonia state N ingredient in preparation can lead to It crosses based on known methods such as the ion chromatographic methods of JIS-K0102:2016 standard and carries out.In addition, A_WIt is hydrogen peroxide conversion The concentration of ingredient is worth multiplied by obtained by volume.

{ 1-2-2. content }

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

Electrolysis processing of the invention with the Zr concentration of element in metal conditioner be preferably 1000mg/L or more and In the range of 1950mg/L or less, in the range of more preferably 1100mg/L or more and 1850mg/L or less, further preferably In the range of 1200mg/L or more and 1750mg/L or less.If within the scope of this, even being then capable of providing common electrolysis item Part such as using material to be tested as cathode side, be powered with certain current density to material to be tested (such as it is being impregnated in rule While fixed 40 DEG C of metal conditioners, with 3.0A/dm²Current density keep 1 second) also have it is above-mentioned that effect The metal material of fruit.Especially, if Zr concentration reaches 1000mg/L or more, distilling resistance to rust becomes better.If Zr element Concentration is 1950mg/L hereinafter, then a coating adhesion becomes better.

(concentration of 1-2-2-2. hydrogen peroxide conversion ingredient)

The concentration of above-mentioned hydrogen peroxide conversion ingredient is in 100mg/L or more and the range of 1500mg/L or less, preferably In the range of 200mg/L or more and 1250mg/L or less, more preferably 300mg/L or more and 1000mg/L or less.In the present invention Electrolysis processing metal conditioner specific system in, by by hydrogen peroxide convert ingredient concentration be set as the rule Determine in range { for accurate, by the basis of the parameter, by the reduced mass (P of the P element of above-mentioned dissolution P ingredient_w) with Dissolve the reduced mass (Zr of the Zr element of Zr ingredient_w) the ratio between (P_w/Zr_w) be set as in above range, it is possible to provide it can be to Sn It is imparting tank processability processed on plating material, film adaptation, (coating adhesion, a secondary coating are closely sealed for coating adhesion Property), corrosion resistance (under film corrosion resistance, without coating corrosion resistance), the properties such as resistance to vulcanization blackening, also, Sn system can also be inhibited Metal conditioner is used in the electrolysis processing of the discoloration (xanthochromia) on plating material surface.Especially, the ingredient if hydrogen peroxide converts For 100mg/L or more, then discoloration-resistant becomes better.In addition, if hydrogen peroxide be converted into be divided into 1500mg/L hereinafter, if make Tank processability becomes good.

(the other constituent concentrations of 1-2-2-3.)

Firstly, F concentration of element, P element concentration are preferably based on above-mentioned Zr concentration of element and above-mentioned each element and Zr member The mass ratio of element and the value that calculates.In addition, negative selected from one or more of nitrate ion, chloride ion and sulfate ion It is suitable that the concentration of ion preferably reaches the mode in aftermentioned preferred value range (1.0S/m or more and 6.0S/m or less) with conductivity Work as decision.

<1-3. fluidity>

{1-3-1.pH}

Electrolysis processing of the invention is preferably 3.4 or more and 4.8 hereinafter, more preferably with the pH in metal conditioner In 3.5 or more and 4.7 or less range, further preferably 3.6 or more and 4.5 or less.If pH reaches 3.4 or more, film Lower corrosion resistance becomes better.If pH be 4.8 hereinafter, if inorganic agent ageing stability become better.In addition, the pH is to be directed to Electrolysis processing is based on what JIS-Z8802:2011 was measured under electrolysis temperature (being 40 DEG C for typical) with metal conditioner Value.

{ 1-3-2. conductivity }

The conductivity of electrolysis processing metal conditioner of the invention is preferably 1.0S/m or more and 6.0S/m or less In the range of, in more preferably 1.5 or more and 5.5 or less range, further preferably 2.0 or more and 5.0 or less.If conductance Rate reaches 1.0 or more, then short time overlay film precipitation property becomes better.If conductivity be 6.0 hereinafter, if be more difficult to occur to electricity Solve the corrosion of processing unit.In addition, the effect of short time overlay film precipitation property can be also saturated even if conductivity is more than 6.0.In addition, The conductivity is to be based on JIS-K0130:2008 in electrolysis temperature for electrolysis processing metal conditioner (to be for typical 40 DEG C) under the value that measures.

" manufacturing methods of 2. electrolysis processing metal conditioners "

The manufacturing method of electrolysis processing metal conditioner of the invention include: will become above-mentioned dissolution Zr ingredient, Above-mentioned dissolution F ingredient, above-mentioned dissolution P ingredient, above-mentioned hydrogen peroxide conversion ingredient and above-mentioned anion supply source it is a kind of with Upper raw material is added in liquid medium, and mixed process.Herein, can be a kind of raw material is the (choosing of a variety of mentioned components From dissolution Zr ingredient, dissolution F ingredient, dissolution P ingredient, hydrogen peroxide conversion ingredient and above-mentioned anion in it is any it is a variety of at Point) supply source (for example, a kind of fluorination zirconic acid as raw material is both the supply source for dissolving Zr ingredient, and dissolve F ingredient Supply source), being also possible to plurality of raw materials is a kind of mentioned component (selected from dissolution Zr ingredient, dissolution F ingredient, dissolution P ingredient, mistake Hydrogen oxide converts any one ingredient in ingredient and above-mentioned anion) supply source (such as the fluorine zirconic acid as different material With hydrofluoric acid be dissolve F ingredient supply source), can also be plurality of raw materials be a variety of mentioned components (selected from dissolution Zr ingredient, Dissolve F ingredient, dissolution P ingredient, hydrogen peroxide conversion ingredient and above-mentioned anion in any Multiple components) supply source (example It is such as ingredient different from each other as the phosphoric acid of different material and hydrofluoric acid, that is, dissolves P ingredient and dissolve the supply source of F ingredient). Hereinafter, each raw material and technique is described in detail.

<2-1. raw material>

(supply source of 2-1-1. dissolution Zr ingredient)

It as the supply source of dissolution Zr ingredient, is not particularly limited, e.g. includes the compound of zirconium atom, can enumerate Such as zirconium sulfate, zirconium oxysulfate, zirconium sulfate ammonium, zirconyl nitrate, zirconium nitrate ammonium, fluorine zirconic acid, fluorine zirconium complex salt etc., they can be single Solely it is used singly, or in combination of two or more kinds.

(supply source of 2-1-2. dissolution F ingredient)

It as the supply source of dissolution F ingredient, is not particularly limited, e.g. includes the compound of fluorine atom, can enumerate Such as fluorine zirconic acid, ammonium fluoride, ammonium acid fluoride, fluorination germanium, ferric flouride, sodium fluoride, sodium bifluoride etc., they can be used alone 1 Kind, two or more can also be applied in combination.In addition, the such fluorine zirconic acid as dissolution Zr ingredient supply source of above-mentioned illustration, fluorine zirconium Complex salt is also the supply source for dissolving F ingredient.

(supply source of 2-1-3. dissolution P ingredient)

As the supply source of dissolution P ingredient, it is not particularly limited.For example, (1) is used as orthophosphoric acid state phosphorus, (just comprising phosphoric acid Phosphoric acid) and its salt (ammonium orthophosphate etc.).(2) it is used as polymer phosphate state phosphorus, is the phosphoric acid condensation product of chain, including pyrophosphoric acid, three Polyphosphoric acid, four polyphosphoric acids etc. further include its salt (ammonium pyrophosphate, tripolyphosphate ammonium, four ammonium polyphosphate etc.).(3) as organic phosphorus Acid-state phosphorus, including nitrilo trimethylene phosphonic acids, nitrilo trimethylene propyl phosphonous acid, nitrilo- diethyl methylene phosphonic acid, methane- 1- hydroxyl -1,1- di 2 ethylhexyl phosphonic acid, ethane -1- hydroxyl -1,1- di 2 ethylhexyl phosphonic acid, propane -1- hydroxyl -1,1- di 2 ethylhexyl phosphonic acid, aminotrimethylene Phosphonic acids, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylenophosphonic acid etc. and its salt etc..In addition, the confession of dissolution P ingredient It can be a kind to source, or two or more.

(supply source of 2-1-4. hydrogen peroxide conversion ingredient)

As hydrogen peroxide conversion ingredient supply source, can enumerate such as hydrogen peroxide, nitrite (such as sodium salt, Ammonium salt), persulfate (such as sodium salt, ammonium salt), water-soluble organic peroxide etc., they can be used alone, can also be with Two or more is applied in combination.

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

It as the supply source of anion, is not particularly limited, inorganic acids can be enumerated, such as nitric acid, hydrochloric acid, sulfuric acid The water soluble salt of inorganic acid, inorganic acid.In addition, the supply source of anion can be a kind, or two or more.In addition, As above-mentioned other ingredients (such as dissolution Zr ingredient) supply source and the ingredient that uses contain the anion (i.e. nitrate anion from Son, chloride ion, sulfate ion) in the case where, which is also the supply source of anion.Anion (the i.e. nitrate anion Ion, chloride ion, sulfate ion) with the cation (preferably ammonium) of inorganic agent (i.e. neutral salt) is matched, as raising The supporting electrolyte of the conductivity of inorganic agent and work.

<2-2. technique>

Electrolysis processing metal conditioner of the invention can be for example, by that will become the supply source of above-mentioned each ingredient Raw material is added in the liquid medium (such as water) using water as main body, is stirred while heating and cooling down as needed to make It is standby.PH is adjusted to rule after being added to the raw material of supply source of above-mentioned each ingredient as the set-up procedure of pH and conductivity Fixed value.Later, anion (i.e. nitrate ion, chloride ion, the sulphur is added in the form of neutral salt (preferably ammonium salt) Acid ion), it adjusts to defined conductivity.The substance (neutral salt) added to adjust the conductivity is known as to support electricity Xie Zhi.Later, in the case where pH changes from specified value, implement micro-adjustment.In addition, the adjustment of pH using alkali, acid come into Row, but be not particularly limited.Preferably, alkali uses ammonia, and acid uses the acid for the anion of supporting electrolyte being identical component (inorganic acid).This is because: adjusting pH by using ammonia, it is formed by overlay film even if ammonia enters, ammonia also can be later It volatilizees in dry Shi Congqi overlay film, therefore does not almost end up in overlay film, as a result, not causing bad shadow to its overlay film performance It rings.In addition this is because: adjusting pH, energy by using with acid (inorganic acid) that the anion of supporting electrolyte is identical component Adverse effect caused by enough overlay film performances by the overlay film formation is limited to minimum limit.

" application methods of 3. electrolysis processing metal conditioners "

<3-1. object metal>

Maximum when making object metal form overlay film with metal conditioner using electrolysis processing of the invention is characterized in While ensuring the performances such as tank processability processed, discoloration-resistant can be assigned to surface treated object metal.From the viewpoint Set out, the object metal of electrolysis processing metal conditioner of the invention preferably with Sn system coating such as Sn coating, Coating (such as solder) containing Sn and other metals } metal material (such as tinplate steel plate).Herein, Sn system coating is Refer to: Sn content in coating take the gross mass of coating as 20 mass % or more (preferably 50 mass % or more, more excellent as benchmark Be selected as 70% or more, further preferably 90 mass % or more) coating.In addition, there may be in addition to Sn in Sn system coating Except one or more other metals (such as Fe), alloy can also be formed in the coating and { such as is attached to using electricity After Sn, heated the alloy of the Sn and Fe that are formed when (Reflow Soldering) }.In turn, Sn system coating is preferably as coating pair At least single side of the metal material of elephant includes 100~15000mg/m²Sn.In turn, Sn system coating is free of Zn, or even if packet Containing Zn, it is preferably also 3 mass % or less using the gross mass of coating as benchmark, is more preferably 2 mass % or less, is further excellent It is selected as 1 mass % or less.This is because: being just difficult to happen discoloration originally when containing Zn with amount to a certain degree.But as above Described, electrolysis processing metal conditioner of the invention can be to object metal imparting tank processability processed, film adaptation, painting Expect adaptation (coating adhesion, secondary coating adaptation), corrosion resistance (corrosion resistance, distillation resistance to rust under film), resistant to sulfur Change the properties such as blackening.Therefore, from this viewpoint, object metal is not limited to the metal material of subsidiary Sn system coating, can be with For metal materials such as aluminum-based metal, Ferrious material, zinc system metal, magnesium system metals.

<3-2. technique>

Electrolysis processing metal conditioner of the invention can utilize common electrolytic method shape on the metal material At tank processability processed, film adaptation, coating adhesion (coating adhesion, secondary coating adaptation), corrosion resistance (under film Corrosion resistance, distillation resistance to rust), the overlay films of the resistance to vulcanization excellents such as blackening.As concrete example, in the metal material of process object Material be Sn system coated metal material in the case where, following methods can be enumerated: using material to be tested as cathode side, by this for try While (or after dipping) metal conditioner is used in the electrolysis processing that material is impregnated in predetermined temperature (being 40 DEG C for typical), With current density (such as 3.0A/dm as defined in advising²) be powered to the material to be tested, and kept for the stipulated time (such as 1 second) Method.Electrolysis temperature is not particularly limited, and preferably 10 DEG C or more and 55 DEG C or less.If temperature reaches 10 DEG C or more, it is easy Maintain temperature.If temperature be 55 DEG C hereinafter, if be more difficult to that the corrosion to electrolytic processing apparatus occurs.Current density does not limit especially It is fixed, longer electrolysis time is needed under low current density.At higher current densities, it can be carried out with short electrolysis time pair It answers, overlay film precipitation efficiency reduces sometimes.

Embodiment

Hereinafter, the present invention is described in more detail by embodiment, but the present invention is unlimited in the range of being no more than its purport Due to embodiment below.In addition, " % " refers to quality % in the case where no especially record.

As test material, materials described below is used.

(1) Sn (tin) steel plate (there are reflow process) (ET) is electroplated

Plate thickness: 0.3mm

The weight per unit area of Sn coating: 2.8g/m²

(2) electronickelling steel plate (NI)

Plate thickness: 0.3mm

The weight per unit area of Ni coating: 0.8g/m²

Xiang Shuizhong addition as become dissolution Zr ingredient and dissolution F ingredient supply source raw material hydrofluoric acid zirconium, as at Hydrofluoric acid for the raw material of dissolution F ingredient supply source and the orthophosphoric acid as the raw material for becoming dissolution P ingredient supply source, are made rule Fixed F_W/Zr_W、P_W/Zr_W.Then, as the raw material for becoming hydrogen peroxide conversion ingredient supply source, to reach recorded in table 1 The mode of additive amount adds substance classes recorded in table 1, is sufficiently mixed, and keeps hydrogen peroxide conversion ingredient completely molten under naked eyes Solution.Thereafter, acid (acid with the anion identical component for constituting supporting electrolyte recorded in table 1) or alkali (ammonia) are added to adjust pH.In turn, supporting electrolyte recorded in table 1 is added to be finely adjusted as needed to pH after adjusting conductivity.At this point, with CA also reaches the mode of specified value, adds above-mentioned sour, above-mentioned alkali (ammonia and sodium hydroxide) to be adjusted.Operation obtains in this way Each Treatment of Metal Surface medicament chemical synthesis treatment liquid.It should be noted that when electrolyte of more than two kinds is used in mixed way, by 2 kinds with On supporting electrolyte when being used in mixed way, mixing ratio is mass ratio.

E1: ammonium nitrate

E2: ammonium sulfate

E3: ammonium chloride

M1: ammonium nilrite

M2: tert-butyl hydroperoxide

M3: hydrogen peroxide

M4: ammonium persulfate

<pre-treatment>

The pre-treatment (electrolysis processing pre-treatment) of test material is implemented as follows: with alkali cleaner { FINE CLEANER- E6406 (Japanese pa card rapids smart (PARKERIZING) Co. Ltd. system), 2% build bath, 60 DEG C } dipping degreasing of progress 30 seconds Afterwards, wash and washed using ion exchange water using tap water, remove moisture with damping roller is removed, make it using drier It is dry.

The test material for implementing pre-treatment is handled into (standard electrolytic processing) for electrolysis below.With the test material As cathode, handle using carbon plate as the test material to electrode, to be impregnated in the electrolysis for being set as predetermined temperature (40 DEG C) with gold Metal surface inorganic agent, while with 3.0A/dm²Current density carry out electrolysis in 1 second.Thereafter, by the test through electrolysis processing Material is washed 5 seconds by spraying with 25 DEG C of tap water, thus cleans the surface of the test material, is removed water using roller extruding, will The surface of the test material reaches plate temperature and is set as 50 DEG C to be dried.

For the test material and electrolysis processing gold for having carried out above-mentioned pre-treatment and electrolysis processing (standard electrolytic processing) Metal surface inorganic agent itself carries out performance evaluation about projects of (A) described below~(L).Table 2 shows test material, Table 3 shows result.

(A) tank processability processed

The PET film for being 20 μm with 200 DEG C of laminate thickness on the two sides of test material, after being punched into the blank of diameter 150mm, With drawing ratio: 1.67 carry out drawing and forming, make tank diameter: 90mm, tank height: the ironed can of about 40mm.Then, by above-mentioned drawing Deep tank is with drawing ratio: 1.36 carry out drawing and forming again, make tank diameter: after the re-drawing tank of 66mm, using the re-drawing tank, By the thinned stretch process in 3 stages, implements that stretch forming processing is thinned in such a way that thickness reduction reaches 50%, drawn Deep-stretch forming processing is thinned, make tank diameter: stretching tank is thinned in the drawing-of 66mm, tank height: about 125mm.Thereafter, for The drawing-, which is thinned, stretches tank body, and the flaw of point following 5 grade evaluated for film floats, removing situation.△'s or more is evaluated as reality With level.

◎: the flaw portion of film, float portion, stripping portion total the area ratio be 0%

Zero: the flaw portion of film, float portion, total the area ratio of stripping portion is more than 0% and for 0.5% or less

Zero △: the flaw portion of film, float portion, total the area ratio of stripping portion is more than 0.5% and for 5% or less

△: the flaw portion of film, float portion, total the area ratio of stripping portion is more than 5% and for 15% or less

×: the flaw portion of film, float portion, total the area ratio of stripping portion be more than 15% or test material fracture and can not Forming

(B) film adaptation

The PET film for being 20 μm with 200 DEG C of laminate thickness on the two sides of test material, after being punched into the blank of diameter 150mm, With drawing ratio: 1.67 carry out drawing and forming, make tank diameter: 90mm, tank height: the ironed can of about 40mm.Thereafter, for the drawing Deep tank body carries out the distillation processing of 121 DEG C, 30 minutes, the removing situation of point 5 following grade evaluated for film.The evaluation of △ or more For realistic scale.

◎: the area ratio of stripping portion is 0%

Zero: the area ratio of stripping portion is more than 0% and is 2% or less

Zero △: the area ratio of stripping portion is more than 2% and is 5% or less

△: the area ratio of stripping portion is more than 5% and is 10% or less

×: the area ratio of stripping portion is more than 10%

(C) coating adhesion

To form dry film thickness as 6g/m on test material²The mode of film be coated with epoxy-phenolic resin, with 200 DEG C drying after ten minutes, is divided into the gridiron pattern as deep as substrate steel with the interval of 1mm.Thereafter, glass is attached on the test material After paper self-adhesive tape, the adhesive tape is peeled off, the removing situation of point following 5 grades evaluation films.△'s or more is evaluated as realistic scale.

◎: the area ratio of stripping portion is 0%

Zero: the area ratio of stripping portion is more than 0% and is 5% or less

Zero △: the area ratio of stripping portion is more than 5% and is 15% or less

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

×: the area ratio of stripping portion is more than 30%

(D) secondary coating adaptation

To form dry film thickness as 6g/m on test material²The mode of film be coated with epoxy-phenolic resin, with 200 DEG C drying after ten minutes, is divided into the gridiron pattern as deep as substrate steel with the interval of 1mm.Thereafter, to the test material carry out 121 DEG C, Distillation processing in 30 minutes, after dry, after attaching cellophane tape on the test material, peels the adhesive tape off, divides following 5 etc. The removing situation of grade evaluation film.△'s or more is evaluated as realistic scale.

◎: the area ratio of stripping portion is 0%

Zero: the area ratio of stripping portion is more than 0% and is 5% or less

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

×: the area ratio of stripping portion is more than 30%

(E) corrosion resistance under film

To form dry film thickness as 6g/m on test material²The mode of film be coated with epoxy-phenolic resin, with 200 DEG C drying after ten minutes, be divided into as deep as substrate steel intersection cut mark.Thereafter, which is being included into 1.5% citric acid- It is impregnated 72 hours in the experimental liquid of 1.5% salt mixed liquor with 45 DEG C.After followed by cleaning, being dry, on the test material After attaching cellophane tape, the adhesive tape is peeled off, the corrosion of erodable section under the film in point following 5 grades evaluation intersection cut mark portions The area ratio (%) of the erodable section of width (mm) and flat part.△'s or more is evaluated as realistic scale.

◎: the Erosion Width for intersecting erodable section under the film in cut mark portion is less than 0.2mm and the erodable section of flat part The area ratio is 0%

Zero: the Erosion Width for intersecting erodable section under the film in cut mark portion is less than 0.3mm and the erodable section of flat part The area ratio was 1% or less (not including the case where wherein being evaluated as ◎)

Zero △: the Erosion Width for intersecting erodable section under the film in cut mark portion is less than the erodable section of 0.4mm and flat part The area ratio be 3% or less (not including the case where wherein being evaluated as ◎, zero)

△: the Erosion Width for intersecting erodable section under the film in cut mark portion is less than 0.5mm and the erodable section of flat part The area ratio was 5% or less (not including the case where wherein being evaluated as the △ of ◎, zero, zero)

×: the Erosion Width for intersecting erodable section under the film in cut mark portion is the erodable section of 0.5mm or more or flat part The area ratio be more than 5%

(F) resistance to rust is distilled

Test material is carried out with 121 DEG C to distillation processing in 30 minutes, observation is got rusty situation, point following 5 grades according to The area ratio (%) in portion of getting rusty is evaluated.△'s or more is evaluated as realistic scale.

◎: the area ratio in portion of getting rusty is 0%

Zero: the area ratio in portion of getting rusty is more than 0% and is 1% or less

Zero △: the area ratio in portion of getting rusty is more than 1% and is 3% or less

△: the area ratio in portion of getting rusty is more than 3% and is 5% or less

×: the area ratio in portion of getting rusty is more than 5%

(G) blackening of resistance to vulcanization

To form dry film thickness as 6g/m on test material²The mode of film be coated with epoxy-phenolic resin, with 200 DEG C drying 10 minutes.Thereafter, in experimental liquid (0.056% cysteine hydrochloride, 0.4% potassium dihydrogen phosphate, 0.81% phosphoric acid Sodium) in impregnated 1 hour with 121 DEG C after, the color difference (△ E value) of point following 5 grades evaluation dipping front and backs.△'s or more is evaluated as Realistic scale.Valuator device: the SD7000 (SCI mode: total reflection measurement) of Nippon Denshoku Industries Co., Ltd.

◎: △ E value is less than 3.0

Zero: △ E value is 3.0 more than and less than 5.5

Zero △: △ E value is 5.5 more than and less than 8.0

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

×: △ E value is 10.5 or more

(H) resistance to being mixed into property of Sn

It is used in metal conditioner 100ml to electrolysis processing and adds the stannous chloride of 350mg/L as Sn, at 40 DEG C Thermostat in stand 24 hours.Dissolution Sn concentration in the supernatant of inorganic agent after measurement standing, point following 5 grades are commented Valence Sn is molten to deposit rate (%).△'s or more is evaluated as realistic scale.Valuator device: the ICP based on JIS-K0116: 2014 standards is sent out The known methods such as light spectroscopy apparatus (ICP-AES)

◎: Sn molten rate of depositing is 80% or more

Zero: Sn molten rate of depositing is 70% more than and less than 80%

Zero △: Sn molten rate of depositing is 60% more than and less than 70%

△: Sn molten rate of depositing is 50% more than and less than 60%

×: the molten rate of depositing of Sn is 40% more than and less than 50%

(I) discoloration-resistant

Test material is stood 72 hours in 70 DEG C, the thermostat of 80%RH.Divide following 5 grades evaluation test materials Standing before and after color difference (△ E value).△'s or more is evaluated as realistic scale.Valuator device: Nippon Denshoku Industries Co., Ltd. The SD7000 (SCI mode: total reflection measurement) of system

◎: △ E value is less than 2.0

Zero: △ E value is 2.0 more than and less than 4.0

Zero △: △ E value is 4.0 more than and less than 6.0

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

×: △ E value is 8.0 or more

(J) short time overlay film precipitation property

By test material (in the evaluation, the test material, the test material i.e. after pre-treatment that do not carry out standard electrolytic processing Material) test material is impregnated at the metal surface for being set as predetermined temperature (40 DEG C) as cathode using carbon plate as to electrode Agent is managed, meanwhile, with 10.0A/dm²Current density electrolysis 0.3 second.Thereafter, by the test material through electrolysis processing with 25 DEG C Tap water wash by spraying 5 seconds, thus clean the surface of the test material, using roller extruding removed water, by the test material The surface of material reaches plate temperature and is set as 50 DEG C to be dried.Thereafter, the test material is measured using fluorescent x-ray analyzer Zr adhesion amount, point following 5 grades evaluate Zr adhesion amount (mg/m²).△'s or more is evaluated as realistic scale.

◎: Zr adhesion amount is 6mg/m²More than

Zero: Zr adhesion amount is 5mg/m²More than and less than 6mg/m²

Zero △: Zr adhesion amount is 4mg/m²More than and less than 5mg/m²

△: Zr adhesion amount is 3mg/m²More than and less than 4mg/m²

×: Zr adhesion amount is less than 3mg/m²

(K) inorganic agent ageing stability

Electrolysis processing is stood 1 month in 40 DEG C of thermostat with metal conditioner 100mL.1 month will be stood The liquid appearance (liquid character) of inorganic agent afterwards and its inorganic agent 100mL are filtered with filter paper (No5C), for hereafter remaining on The residue quality (mg) of the inorganic agent of filter paper, point following 5 grades evaluations.△'s or more is evaluated as realistic scale.

◎: inorganic agent is without muddiness, and the quality of residue is 0mg

Zero: there is muddiness in inorganic agent, and the quality of residue is 0mg

Zero △: there is muddiness in inorganic agent, and the quality of residue is more than 0mg and is 10mg or less

△: there is muddiness in inorganic agent, and the quality of residue is more than 10mg and is less than 20mg

×: there is muddiness in inorganic agent, and the quality of residue is 20mg or more

(L) overlay film appearance

Point following 5 grade evaluation tests materials (in the evaluation, do not carry out standard electrolytic processing test material, i.e. before Treated test material) in electrolysis processing (standard electrolytic processing) before and after color difference (△ E value).△'s or more is evaluated as reality With level.Valuator device: the SD7000 (SCI mode: total reflection measurement) of Nippon Denshoku Industries Co., Ltd.

◎: △ E value is less than 5.0

Zero: △ E value is 5.0 more than and less than 7.0

Zero △: △ E value is 7.0 more than and less than 9.0

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

×: △ E value is 11.0 or more

[table 1A]

Table 1A (embodiment)

[table 1B]

Table 1B

[table 1C]

Table 1C (embodiment)

[table 1D]

Table 1D (embodiment)

[table 1E]

Table 1E (embodiment)

[table 2A]

Table 2A (embodiment)

Embodiment	Treatment fluid	Raw material
			Embodiment 1	S1	ET
Embodiment 2	S2	ET
			Embodiment 3	S3	ET
Embodiment 4	S4	ET
			Embodiment 5	S5	ET
Embodiment 6	S6	ET
			Embodiment 7	S7	ET
Embodiment 8	S8	ET
			Embodiment 9	S9	ET
Embodiment 10	S10	ET
			Embodiment 11	S11	ET
Embodiment 12	S12	ET
			Embodiment 13	S13	ET
Embodiment 14	S14	ET
			Embodiment 15	S15	ET
Embodiment 16	S16	ET
			Embodiment 17	S17	ET
Embodiment 18	S18	ET
			Embodiment 19	S19	ET
Embodiment 20	S20	ET
			Embodiment 21	S21	ET
Embodiment 22	S22	ET
			Embodiment 23	S23	ET
Embodiment 24	S24	ET
			Embodiment 25	S25	ET
Embodiment 26	S26	ET
			Embodiment 27	S27	ET
Embodiment 28	S28	ET
			Embodiment 29	S29	ET
Embodiment 30	S30	ET
			Embodiment 31	S31	ET
Embodiment 32	S32	ET
			Embodiment 33	S33	ET
Embodiment 34	S34	ET
			Embodiment 35	S35	ET
Embodiment 36	S36	ET
			Embodiment 37	S37	ET
Embodiment 38	S38	ET
			Embodiment 39	S39	ET
Embodiment 40	S40	ET
			Embodiment 41	S41	ET
Embodiment 42	S42	ET
			Embodiment 43	S43	ET
Embodiment 44	S44	ET
			Embodiment 45	S45	ET
Embodiment 46	S46	ET
			Embodiment 47	S47	ET
Embodiment 48	S48	ET
			Embodiment 49	S49	ET
Embodiment 50	S50	ET
			Embodiment 51	S51	ET
Embodiment 52	S52	ET
			Embodiment 53	S53	ET
Embodiment 54	S54	ET
			Embodiment 55	S55	ET
Embodiment A	S3	NI

[table 2B]

Table 2B

Comparative example	Treatment fluid	Raw material
			Comparative example 1	H1	ET
Comparative example 2	H2	ET
			Comparative example 3	H3	ET
Comparative example 4	H4	ET
			Comparative example 5	H5	ET
Comparative example 6	H6	ET
			Comparative example 7	H7	ET
Comparative example 8	H8	ET
			Comparative example 9	H9	ET
Comparative example 10	H10	ET
			Comparative example 11	H11	ET
Comparative example 12	H12	ET
			Comparative example 13	H13	ET
Comparative example 14	H14	ET
			Comparative example 15	H15	ET
Comparative example 16	H16	ET
			Comparative example 17	H17	ET
Comparative example 18	H18	ET
			Comparative example 19	H19	ET
Comparative example 20	H20	ET
			Comparative example 21	H21	ET
Comparative example 22	H22	ET
			Comparative example 23	H23	ET
Comparative example 24	H24	ET

[table 2C]

Table 2C (embodiment)

Embodiment	Treatment fluid	Raw material
			Embodiment 56	S56	ET
Embodiment 57	S57	ET
			Embodiment 58	S58	ET
Embodiment 59	S59	ET
			Embodiment 60	S60	ET
Embodiment 61	S61	ET
			Embodiment 62	S62	ET
Embodiment 63	S63	ET
			Embodiment 64	S64	ET
Embodiment 65	S65	ET
			Embodiment 66	S66	ET
Embodiment 67	S67	ET
			Embodiment 68	S68	ET
Embodiment 69	S69	ET
			Embodiment 70	S70	ET
Embodiment 71	S71	ET
			Embodiment 72	S72	ET
Embodiment 73	S73	ET
			Embodiment 74	S74	ET
Embodiment 75	S75	ET
			Embodiment 76	S76	ET
Embodiment 77	S77	ET
			Embodiment 78	S78	ET
Embodiment 79	S79	ET
			Embodiment 80	S80	ET
Embodiment 81	S81	ET
			Embodiment 82	S82	ET
Embodiment 83	S83	ET
			Embodiment 84	S84	ET
Embodiment 85	S85	ET
			Embodiment 86	S86	ET
Embodiment 87	S87	ET
			Embodiment 88	S88	ET
Embodiment 89	S89	ET
			Embodiment 90	S90	ET
Embodiment 91	S91	ET
			Embodiment 92	S92	ET
Embodiment 93	S93	ET
			Embodiment 94	S94	ET
Embodiment 95	S95	ET
			Embodiment 96	S96	ET
Embodiment 97	S97	ET
			Embodiment 98	S98	ET
Embodiment 99	S99	ET
			Embodiment 100	S100	ET
Embodiment 101	S101	ET
			Embodiment 102	S102	ET
Embodiment 103	S103	ET
			Embodiment 104	S104	ET
Embodiment 105	S105	ET
			Embodiment 106	S106	ET
Embodiment 107	S107	ET
			Embodiment 108	S108	ET
Embodiment 109	S109	ET
			Embodiment 110	S110	ET

[table 2D]

Table 2D (embodiment)

Embodiment	Treatment fluid	Raw material
			Embodiment 111	S111	ET
Embodiment 112	S112	ET
			Embodiment 113	S113	ET
Embodiment 114	S114	ET
			Embodiment 115	S115	ET
Embodiment 116	S116	ET
			Embodiment 117	S117	ET
Embodiment 118	S118	ET
			Embodiment 119	S119	ET
Embodiment 120	S120	ET
			Embodiment 121	S121	ET
Embodiment 122	S122	ET
			Embodiment 123	S123	ET
Embodiment 124	S124	ET
			Embodiment 125	S125	ET
Embodiment 126	S126	ET
			Embodiment 127	S127	ET
Embodiment 128	S128	ET
			Embodiment 129	S129	ET
Embodiment 130	S130	ET
			Embodiment 131	S131	ET
Embodiment 132	S132	ET
			Embodiment 133	S133	ET
Embodiment 134	S134	ET
			Embodiment 135	S135	ET
Embodiment 136	S136	ET
			Embodiment 137	S137	ET
Embodiment 138	S138	ET
			Embodiment 139	S139	ET
Embodiment 140	S140	ET
			Embodiment 141	S141	ET
Embodiment 142	S142	ET
			Embodiment 143	S143	ET
Embodiment 144	S144	ET
			Embodiment 145	S145	ET
Embodiment 146	S146	ET
			Embodiment 147	S147	ET
Embodiment 148	S148	ET
			Embodiment 149	S149	ET
Embodiment 150	S150	ET
			Embodiment 151	S151	ET
Embodiment 152	S152	ET
			Embodiment 153	S153	ET
Embodiment 154	S154	ET
			Embodiment 155	S155	ET
Embodiment 156	S156	ET
			Embodiment 157	S157	ET
Embodiment 158	S158	ET
			Embodiment 159	S159	ET
Embodiment 160	S160	ET
			Embodiment 161	S161	ET
Embodiment 162	S162	ET
			Embodiment 163	S163	ET
Embodiment 164	S164	ET
			Embodiment 165	S165	ET

[table 2E]

Table 2E (embodiment)

Embodiment	Treatment fluid	Raw material
			Embodiment 166	S166	ET
Embodiment 167	S167	ET
			Embodiment 168	S168	ET
Embodiment 169	S169	ET
			Embodiment 170	S170	ET
Embodiment 171	S171	ET
			Embodiment 172	S172	ET
Embodiment 173	S173	ET
			Embodiment 174	S174	ET
Embodiment 175	S175	ET
			Embodiment 176	S176	ET
Embodiment 177	S177	ET
			Embodiment 178	S178	ET
Embodiment 179	S179	ET
			Embodiment 180	S180	ET
Embodiment 181	S181	ET
			Embodiment 182	S182	ET
Embodiment 183	S183	ET
			Embodiment 184	S184	ET
Embodiment 185	S1a5	ET
			Embodiment 186	S186	ET
Embodiment 187	S187	ET
			Embodiment 188	S188	ET
Embodiment 189	S189	ET
			Embodiment 190	S190	ET
Embodiment 191	S191	ET
			Embodiment 192	S192	ET
Embodiment 193	S193	ET
			Embodiment 194	S194	ET
Embodiment 195	S195	ET
			Embodiment 196	S196	ET
Embodiment 197	S197	ET
			Embodiment 198	S198	ET
Embodiment 199	S199	ET
			Embodiment 200	S200	ET
Embodiment 201	S201	ET
			Embodiment 202	S202	ET
Embodiment 203	S203	ET
			Embodiment 204	S204	ET
Embodiment 205	S205	ET
			Embodiment 206	S206	ET
Embodiment 207	S207	ET
			Embodiment 208	S208	ET
Embodiment 209	S209	ET
			Embodiment 210	S210	ET
Embodiment 211	S211	ET
			Embodiment 212	S212	ET
Embodiment 213	S213	ET
			Embodiment 214	S214	ET
Embodiment 215	S215	ET
			Embodiment 216	S216	ET
Embodiment 217	S217	ET
			Embodiment 218	S218	ET
Embodiment 219	S219	ET
			Embodiment 220	S220	ET

[table 3A]

Table 3A (embodiment)

Embodiment

(A)

(B)

(C)

(D)

(E)

(F)

(G)

(H)

(I)

(J)

(K)

(L)

Embodiment 1

◎

○

◎

Embodiment 2

◎

○

◎

Embodiment 3

◎

Embodiment 4

◎

○

◎

Embodiment 5

◎

Embodiment 6

◎

Embodiment 7

◎

△

◎

Embodiment 8

◎

△

◎

Embodiment 9

◎

○

◎

Embodiment 10

◎

○

◎

Embodiment 11

◎

Embodiment 12

◎

Embodiment 13

◎

Embodiment 14

◎

Embodiment 15

◎

△

◎

Embodiment 16

△

◎

Embodiment 17

◎

○

◎

Embodiment 18

○

◎

Embodiment 19

◎

Embodiment 20

◎

Embodiment 21

◎

○△

◎

Embodiment 22

◎

○△

◎

Embodiment 23

◎

○

◎

Embodiment 24

◎

○

◎

Embodiment 25

◎

Embodiment 26

◎

Embodiment 27

◎

△

◎

Embodiment 28

◎

△

◎

Embodiment 29

◎

○△

◎

Embodiment 30

◎

○△

◎

Embodiment 31

◎

○

◎

Embodiment 32

◎

○

◎

Embodiment 33

◎

Embodiment 34

◎

Embodiment 35

◎

△

◎

Embodiment 36

◎

△

◎

Embodiment 37

◎

○△

◎

Embodiment 38

◎

Embodiment 39

◎

○

◎

Embodiment 40

◎

Embodiment 41

◎

Embodiment 42

◎

Embodiment 43

◎

△

◎

Embodiment 44

◎

Embodiment 45

◎

○△

◎

Embodiment 46

◎

○△

◎

Embodiment 47

◎

○

◎

Embodiment 48

◎

○

◎

Embodiment 49

◎

Embodiment 50

◎

Embodiment 51

◎

△

◎

Embodiment 52

◎

△

◎

Embodiment 53

◎

Embodiment 54

◎

○

Embodiment 55

◎

△

Embodiment A

◎

[table 3B]

Table 3B (comparative example)

Comparative example

(A)

(B)

(C)

(D)

(E)

(F)

(G)

(H)

(I)

(J)

(K)

(L)

Comparative example 1

◎

×

◎

Comparative example 2

×

◎

Comparative example 3

◎

×

◎

Comparative example 4

◎

×

◎

Comparative example 5

◎

×

◎

Comparative example 6

◎

×

◎

Comparative example 7

◎

×

◎

Comparative example 8

×

◎

Comparative example 9

◎

×

◎

Comparative example 10

◎

×

◎

Comparative example 11

◎

×

◎

Comparative example 12

◎

×

◎

Comparative example 13

◎

×

◎

Comparative example 14

×

◎

Comparative example 15

◎

×

◎

Comparative example 16

◎

×

◎

Comparative example 17

◎

×

◎

Comparative example 18

◎

×

◎

Comparative example 19

◎

×

◎

Comparative example 20

×

◎

Comparative example 21

◎

×

◎

Comparative example 22

◎

×

◎

Comparative example 23

◎

×

◎

Comparative example 24

◎

×

◎

[table 3C]

Table 3C (embodiment)

Embodiment

(A)

(B)

(C)

(D)

(E)

(F)

(G)

(H)

(I)

(J)

(K)

(L)

Embodiment 56

◎

○

◎

Embodiment 57

◎

○

◎

Embodiment 58

◎

Embodiment 59

◎

○

◎

Embodiment 60

◎

Embodiment 61

◎

Embodiment 62

◎

△

◎

Embodiment 63

◎

△

◎

Embodiment 64

◎

○

◎

Embodiment 65

◎

○

◎

Embodiment 66

◎

Embodiment 67

◎

Embodiment 68

◎

Embodiment 69

◎

Embodiment 70

◎

△

◎

Embodiment 71

△

◎

Embodiment 72

◎

○

◎

Embodiment 73

○

◎

Embodiment 74

◎

Embodiment 75

◎

Embodiment 76

◎

○△

◎

Embodiment 77

◎

○△

◎

Embodiment 78

◎

○

◎

Embodiment 79

◎

○

◎

Embodiment 80

◎

Embodiment 81

◎

Embodiment 82

◎

△

◎

Embodiment 83

◎

△

◎

Embodiment 84

◎

○△

◎

Embodiment 84

◎

○△

◎

Embodiment 86

◎

○

◎

Embodiment 87

◎

○

◎

Embodiment 88

◎

Embodiment 89

◎

Embodiment 90

◎

△

◎

Embodiment 91

◎

△

◎

Embodiment 92

◎

○△

◎

Embodiment 93

◎

Embodiment 94

◎

○

◎

Embodiment 95

◎

Embodiment 96

◎

Embodiment 97

◎

Embodiment 98

◎

△

◎

Embodiment 99

◎

Embodiment 100

◎

○△

◎

Embodiment 101

◎

○△

◎

Embodiment 102

◎

○

◎

Embodiment 103

◎

○

◎

Embodiment 104

◎

Embodiment 105

◎

Embodiment 106

◎

△

◎

Embodiment 107

◎

△

◎

Embodiment 108

◎

Embodiment 109

◎

○

Embodiment 110

◎

△

[table 3D]

Table 3D (embodiment)

Embodiment

(A)

(B)

(C)

(D)

(E)

(F)

(G)

(H)

(I)

(J)

(K)

(L)

Embodiment 111

◎

○

◎

Embodiment 112

◎

○

◎

Embodiment 113

◎

Embodiment 114

◎

○

◎

Embodiment 115

◎

Embodiment 116

◎

Embodiment 117

◎

△

◎

Embodiment 118

◎

△

◎

Embodiment 119

◎

○

◎

Embodiment 120

◎

○

◎

Embodiment 121

◎

Embodiment 122

◎

Embodiment 123

◎

Embodiment 124

◎

Embodiment 125

◎

△

◎

Embodiment 128

△

◎

Embodiment 127

◎

○

◎

Embodiment 128

○

◎

Embodiment 129

◎

Embodiment 130

◎

Embodiment 131

◎

○△

◎

Embodiment 132

◎

○△

◎

Embodiment 133

◎

○

◎

Embodiment 134

◎

○

◎

Embodiment 135

◎

Embodiment 136

◎

Embodiment 137

◎

△

◎

Embodiment 138

◎

△

◎

Embodiment 139

◎

○△

◎

Embodiment 140

◎

○△

◎

Embodiment 141

◎

○

◎

Embodiment 142

◎

○

◎

Embodiment 143

◎

Embodiment 144

◎

Embodiment 145

◎

△

◎

Embodiment 146

◎

△

◎

Embodiment 147

◎

○△

◎

Embodiment 148

◎

Embodiment 149

◎

○

◎

Embodiment 150

◎

Embodiment 151

◎

Embodiment 152

◎

Embodiment 153

◎

△

◎

Embodiment 154

◎

Embodiment 155

◎

○△

◎

Embodiment 156

◎

○△

◎

Embodiment 157

◎

○

◎

Embodiment 158

◎

○

◎

Embodiment 159

◎

Embodiment 160

◎

Embodiment 161

◎

△

◎

Embodiment 162

◎

△

◎

Embodiment 163

◎

Embodiment 164

◎

○

Embodiment 165

◎

△

[table 3E]

Table 3E (embodiment)

Embodiment

(A)

(B)

(C)

(D)

(E)

(F)

(G)

(H)

(I)

(J)

(K)

(L)

Embodiment 166

◎

Embodiment 167

◎

Embodiment 168

◎

Embodiment 169

◎

Embodiment 170

◎

Embodiment 171

◎

Embodiment 172

◎

△

◎

Embodiment 173

◎

△

◎

Embodiment 174

◎

○

◎

Embodiment 175

◎

○

◎

Embodiment 176

◎

Embodiment 177

◎

Embodiment 178

◎

Embodiment 179

◎

Embodiment 180

◎

○△

◎

Embodiment 181

△

◎

Embodiment 182

◎

○

◎

Embodiment 183

○

◎

Embodiment 184

◎

Embodiment 185

◎

Embodiment 186

◎

○△

◎

Embodiment 187

◎

○△

◎

Embodiment 188

◎

○

◎

Embodiment 189

◎

○

◎

Embodiment 190

◎

Embodiment 191

◎

Embodiment 192

◎

△

◎

Embodiment 193

◎

△

◎

Embodiment 194

◎

○△

◎

Embodiment 195

◎

○△

◎

Embodiment 196

◎

○

◎

Embodiment 197

◎

○

◎

Embodiment 198

◎

Embodiment 199

◎

Embodiment 200

◎

△

◎

Embodiment 201

◎

△

◎

Embodiment 202

◎

○△

◎

Embodiment 203

◎

Embodiment 204

◎

○

◎

Embodiment 205

◎

Embodiment 206

◎

Embodiment 207

◎

Embodiment 208

◎

△

◎

Embodiment 209

◎

Embodiment 210

◎

○△

◎

Embodiment 211

◎

○△

◎

Embodiment 212

◎

○

◎

Embodiment 213

◎

○

◎

Embodiment 214

◎

Embodiment 215

◎

Embodiment 216

◎

△

◎

Embodiment 217

◎

△

◎

Embodiment 218

◎

Embodiment 219

◎

○

Embodiment 220

◎

△

Claims

1. a kind of electrolysis processing metal conditioner, contains:

Dissolve Zr ingredient；

Dissolve F ingredient；

Dissolve P ingredient；And

Selected from one or more of nitrate ion, chloride ion and sulfate ion anion,

The reduced mass P of the P element of the dissolution P ingredient_wWith the reduced mass Zr of the Zr element of the dissolution Zr ingredient_wThe ratio between, That is P_w/Zr_wFor in 0.04 or more and 0.5 or less range,

The hydrogen peroxide calculated by following redox titrations shown convert ingredient concentration be 100mg/L or more and In the range of 1500mg/L or less,

Redox titration: taking electrolysis processing metal conditioner 20ml, adds deionized water 80ml respectively, specific gravity is 1.395 50% sulfuric acid 10ml, potassium iodide 2.0g stands after five minutes in sombre place, is carried out with 0.1M hypo solution Redox titration, terminal are set as becoming from brown colourless point,

Concentration=0.1M hypo solution titer × 85.0 of hydrogen peroxide conversion ingredient, wherein the concentration Unit is mg/L, and the unit of the titer is ml.

2. electrolysis processing metal conditioner according to claim 1, wherein the F element of the dissolution F ingredient Reduced mass F_wWith the reduced mass Zr of the Zr element of the dissolution Zr ingredient_wThe ratio between, i.e. F_w/Zr_wIt is 1.3 or more and 2.5 or less In the range of.

3. electrolysis processing metal conditioner according to claim 1 or 2, wherein Zr concentration of element is 1000mg/ In the range of L or more and 1950mg/L or less.

4. electrolysis processing metal conditioner described in any one of claim 1 to 3, wherein pH is 3.4 or more And in 4.8 or less range.

5. electrolysis processing metal conditioner according to any one of claims 1 to 4, wherein the peroxidating Hydroperoxide conversion ingredient is from selected from one or more of hydrogen peroxide, nitrous acid, persulfuric acid, organic peroxide and its salt substance Ingredient.

6. electrolysis processing metal conditioner according to any one of claims 1 to 5, can further contain Selected from dissolution Sn ingredient, dissolution Fe ingredient, dissolved ammonia state N ingredient, dissolution Na ingredient and at least one kind of ingredient in K ingredient is dissolved,

At this point, the reduced mass Zr of the Zr element of the dissolution Zr ingredient_w, hydrogen peroxide conversion ingredient quality A_W, it is described Dissolve the reduced mass Sn of the Sn element of Sn ingredient_w, it is described dissolution Fe ingredient Fe element reduced mass Fe_wWith the dissolution The reduced mass N of the N element of ammonia state N ingredient_wTotal quality and it is described dissolution Zr ingredient Zr element reduced mass Zr_w, institute State the quality A of hydrogen peroxide conversion ingredient_W, it is described dissolution Sn ingredient Sn element reduced mass Sn_w, the dissolution Fe ingredient Fe element reduced mass Fe_w, the dissolved ammonia state N ingredient N element reduced mass N_w, it is described dissolution Na ingredient Na The reduced mass Na of element_wWith the reduced mass K of the K element of the dissolution K ingredient_wTotal mass ratio CA:{ (Zr_w+A_w+ Sn_w+Fe_w+N_w)/(Zr_w+A_W+Sn_w+Fe_w+N_w+Na_w+K_w) it is 0.9 or more.

7. the processing metal conditioner of electrolysis described according to claim 1~any one of 6, wherein conductivity is In the range of 1.0S/m or more and 6.0S/m or less.

8. electrolysis processing metal conditioner according to any one of claims 1 to 7, wherein process object gold Belonging to is Sn system coating.

9. electrolysis processing metal conditioner according to claim 8, wherein process object metal is Sn's and Fe Alloy layer.

10. a kind of manufacturing method for being electrolysed processing metal conditioner, wherein Treatment of Metal Surface is used in the electrolysis processing Agent contains:

Dissolve Zr ingredient；

Dissolve F ingredient；

Dissolve P ingredient；And

Selected from one or more of nitrate ion, chloride ion and sulfate ion anion,

By the hydrogen peroxide that redox titration shown in following calculates convert ingredient concentration be 100mg/L or more and In the range of 1500mg/L or less,

The manufacturing method is characterized in that comprising:

The dissolution Zr ingredient, the dissolution F ingredient, the dissolution P ingredient, hydrogen peroxide conversion ingredient and institute will be become More than one raw materials for stating the supply source of anion are added in liquid medium, and mixed process,

Redox titration: taking electrolysis processing metal conditioner 20ml, adds deionized water 80ml, and then add ratio The 50% sulfuric acid 10ml that weight is 1.395 adds potassium iodide 2.0g, stands in sombre place after five minutes, with 0.1M sodium thiosulfate The method that solution is titrated, terminal are set as becoming from brown colourless point,

Concentration=titer × 85.0 of hydrogen peroxide conversion ingredient, wherein the unit of the concentration is mg/L, the titer Unit be ml.

11. the manufacturing method of electrolysis processing metal conditioner according to claim 10, wherein the dissolution F The reduced mass F of the F element of ingredient_wWith the reduced mass Zr of the Zr element of the dissolution Zr ingredient_wThe ratio between, i.e. F_w/Zr_wIt is 1.3 Above and in 2.5 or less range.

12. the manufacturing method of processing metal conditioner is electrolysed described in 0 or 11 according to claim 1, wherein Zr element Concentration is in 1000mg/L or more and the range of 1950mg/L or less.

13. the manufacturing method of processing metal conditioner is electrolysed described in any one of 0~12 according to claim 1, In, in the range that pH is 3.4 or more and 4.8 or less.

14. the manufacturing method of processing metal conditioner is electrolysed described in any one of 0~13 according to claim 1, In, the hydrogen peroxide is converted into be divided into and be originated from hydrogen peroxide, nitrous acid, persulfuric acid, organic peroxide and its salt 1 kind or more substance ingredient.

15. the manufacturing method of processing metal conditioner is electrolysed described in any one of 0~14 according to claim 1, It can be further containing in dissolution Sn ingredient, dissolution Fe ingredient, dissolved ammonia state N ingredient, dissolution Na ingredient and dissolution K ingredient At least one kind of ingredient,

At this point, the reduced mass Zr of the Zr element of the dissolution Zr ingredient_w, hydrogen peroxide conversion ingredient quality A_W, it is described Dissolve the reduced mass Sn of the Sn element of Sn ingredient_w, it is described dissolution Fe ingredient Fe element reduced mass Fe_wWith dissolved ammonia state N The N element reduced mass N of ingredient_wTotal quality and it is described dissolution Zr ingredient Zr element reduced mass Zr_w, the peroxide Change the quality A of hydroperoxide conversion ingredient_W, it is described dissolution Sn ingredient Sn element reduced mass Sn_w, it is described dissolution Fe ingredient Fe member The reduced mass Fe of element_w, the dissolved ammonia state N ingredient N element reduced mass N_w, the dissolution Na ingredient Na element Reduced mass Na_wWith the reduced mass K of the K element of the dissolution K ingredient_wTotal mass ratio CA:{ (Zr_w+A_W+Sn_w+Fe_w+ N_w)/(Zr_w+A_W+Sn_w+Fe_w+N_w+Na_w+K_w) it is 0.9 or more.

16. the manufacturing method of processing metal conditioner is electrolysed described in any one of 0~15 according to claim 1, In, electrolysis processing metal conditioner conductivity be 1.0S/m or more and the range of 6.0S/m or less in.

17. the manufacturing method of processing metal conditioner is electrolysed described in any one of 0~16 according to claim 1, In, process object metal is Sn system coating.

18. the manufacturing method of electrolysis processing metal conditioner according to claim 17, wherein process object gold Belong to the alloy layer for being Sn and Fe.

19. a kind of surface treatment method of metal material, characterized in that it comprises: in process object metal impregnation in electrolysis In the state of processing metal conditioner, the process being powered using the process object metal as cathode side,

The electrolysis processing metal conditioner contains:

Dissolve Zr ingredient；

Dissolve F ingredient；

Dissolve P ingredient；And

Selected from one or more of nitrate ion, chloride ion and sulfate ion anion,

The reduced mass P of the P element of the dissolution P ingredient_wWith the reduced mass Zr of the Zr element of the dissolution Zr ingredient_wMatter Amount ratio, i.e. P_w/Zr_wFor in 0.04 or more and 0.5 or less range,

20. surface treatment method according to claim 19, wherein described in the electrolysis processing metal conditioner Dissolve the reduced mass F of the F element of F ingredient_wWith the reduced mass Zr of the Zr element of the dissolution Zr ingredient_wThe ratio between, i.e. F_w/Zr_w For in 1.3 or more and 2.5 or less range.

21. surface treatment method described in 9 or 20 according to claim 1, wherein in the electrolysis processing metal conditioner Zr concentration of element is in 1000mg/L or more and the range of 1950mg/L or less.

22. surface treatment method described in any one of 9~21 according to claim 1, wherein at the electrolysis processing metal It manages in the range that the pH in agent is 3.4 or more and 4.8 or less.

23. surface treatment method described in any one of 9~22 according to claim 1, wherein the hydrogen peroxide conversion ingredient For from the ingredient selected from one or more of hydrogen peroxide, nitrous acid, persulfuric acid, organic peroxide and its salt substance.

24. surface treatment method described in any one of 9~23 according to claim 1, wherein at the electrolysis processing metal Manage agent can further containing selected from dissolution Sn ingredient, dissolution Fe ingredient, dissolved ammonia state N ingredient, dissolution Na ingredient and dissolution K at At least one kind of ingredient in point,

At this point, the reduced mass Zr of the Zr element of the dissolution Zr ingredient_w, hydrogen peroxide conversion ingredient quality A_W, it is described The reduced mass Sn of the Sn element of Sn ingredient_w, it is described dissolution Fe ingredient Fe element reduced mass Fe_wWith dissolved ammonia state N ingredient N element reduced mass N_wTotal quality and it is described dissolution Zr ingredient Zr element reduced mass Zr_w, the peroxidating The quality A of hydroperoxide conversion ingredient_W, the Sn ingredient Sn element reduced mass Sn_w, the dissolution Fe ingredient Fe element change Calculate quality Fe_w, the dissolved ammonia state N ingredient N element reduced mass N_w, it is described dissolution Na ingredient Na element conversion matter Measure Na_wWith the reduced mass K of the K element of the dissolution K ingredient_wTotal quality mass ratio CA:{ (Zr_w+A_W+Sn_w+Fe_w+ N_w)/(Zr_w+A_W+Sn_w+Fe_w+N_w+Na_w+K_w) it is 0.9 or more.

25. surface treatment method described in any one of 9~24 according to claim 1, wherein at the electrolysis processing metal The conductivity for managing agent is in 1.0S/m or more and the range of 6.0S/m or less.

26. surface treatment method described in any one of 9~25 according to claim 1, wherein the process object metal is Sn It is coating.

27. surface treatment method according to claim 26, wherein the Alloy Plating that the process object metal is Sn and Fe Layer.