WO1993022481A1 - Phosphating process - Google Patents

Abstract

A process for producing a phosphate coating, wherein a sludge, which is an impurity component other than inevitable impurities contained in a phosphating bath, is removed and the object is electrolyzed in order to enhance the capability of chemical conversion coating and provide a high-quality conversion coating. This process serves to form a satisfactory phosphate coating on whatever metallic material and can provide a phosphate coating having a large thickness which has not been available in the prior art.

Description

 Description Phosphoric acid conversion treatment Technical field

 The present invention relates to a phosphoric acid conversion treatment method for forming a phosphoric acid conversion coating on a metal material surface, and more particularly, to a treatment method for forming a chemical conversion coating on a conductive metal material surface. .

Background technology

 Conventionally, the phosphoric acid conversion treatment method has been used in various fields such as pretreatment before coating and pretreatment before cold forging.

 For example, Japanese Patent Application Laid-Open No. 60-204847 discloses a method of subjecting iron, steel, zinc, and / or aluminum to acid phosphate conversion treatment on the surface thereof. I have.

 Japanese Patent Application Laid-Open No. 6-64881 discloses phosphoric acid for steel and zinc or zinc-plated steel, or metal composed of aluminum and steel and / or zinc-plated steel. A method of performing a chemical conversion treatment is disclosed.

Further, Japanese Patent Application Laid-Open No. 2-190478 discloses a chemical conversion treatment bath containing Fe ^{3+ ions} as a method for forming a phosphate film on an aluminum material surface. I have.

 In Japanese Patent Application Laid-Open No. HEI 4-120294, when a phosphoric acid conversion treatment film is formed on the surface of stainless steel as a coating base treatment, the phosphoric acid conversion treatment is performed. It is disclosed that a coating is formed by applying a PR pulse current to a stainless steel in a bath to perform electrolysis.

However, in the conventional phosphoric acid conversion treatment method, Japanese Patent Application Laid-Open Nos. 60-208479, Japanese Patent Application No. S64-68481, and Many methods for forming a phosphate conversion coating on a material other than iron have been known in the past, as disclosed in, for example, Japanese Patent Publication No. 1904478, but depending on the type of material to be treated, Various problems have arisen that the components of the phosphatization bath and the conditions for the treatment must be changed. Further, the components and conditions of such a phosphate chemical conversion treatment bath were extremely severe, and were not practical at all.

 Further, as disclosed in Japanese Patent Application Laid-Open No. H11-2012, stainless steel, which is a material to be treated other than iron and steel, is subjected to electrolysis in a phosphate chemical conversion treatment bath. It is known that it is possible to form a phosphoric acid conversion coating on the material to be treated as described above, but such a coating still has a very thin film thickness, such as a coating base. It was limited to formation.

 The present invention has been made in view of the above problems, and a phosphoric acid conversion coating film having a sufficient film thickness can be applied to the surface of any conductive metal material. It provides a phosphoric acid conversion treatment method that can be used. Disclosure of the invention

 Therefore, the present inventors argued that in the conventional phosphoric acid conversion treatment method, the above-described complicated conditions were required in the treatment other than iron, and furthermore, a sufficient film thickness was required. By diligently researching whether or not a processing method that can be obtained was obtained, we determined the cause and found a means to solve the cause.

That is, conventionally, in the phosphate chemical conversion treatment method, the method in which the material to be treated is used as a steel material is simply applied to other materials to be treated as it is. It seems that the treatment conditions of the forest to be treated became very severe, or that the phosphate conversion coating could be formed only with a composite material with a steel material. Therefore, in the present invention, first, the process of forming a phosphatized chemical conversion film and the phosphatized chemical conversion reaction were examined in detail from the following two aspects. First, analysis was performed from the chemical reaction side, because the chemical reaction of the formation of the phosphate chemical conversion coating can be understood as an electrochemical reaction. Second, we analyzed the phase transition phenomenon. This refers to the phenomenon in which the soluble component (liquid) undergoes a chemical reaction in the phosphatization reaction to form a film (solid).

 It should be noted that the first and second laws of thermodynamics play an important role in any of the above studies (analysis).

 The detailed examination results are described below.

 First, an analysis from the chemical reaction side is performed.

 Phosphoric acid conversion treatment is a type of so-called chemical conversion film treatment method in which a film is formed on a metal material substrate using a chemical reaction between a metal material and a chemical solution. In addition, a phosphate solution containing a film-forming metal ion such as iron, manganese, nickel, calcium, or zinc is used as the chemical conversion solution.

 The phosphoric acid conversion treatment method can be considered to include an etching reaction step for a steel material and a film formation reaction step for forming a film. Then, they are electrochemical reactions and reduction reactions of ion nitrate or the like as a force source reaction, for example,

 [Formula 1]

N 0 3 one + 3 H + + 2 e → HN 0 2 + H 2 .0

 [Formula 2]

 H N 0 2 + H + + e → N 0 + H 2 0

A metal dissolution (etching) reaction (Chem. 3) and a film formation reaction (Chem. 4) as anode reactions;

 [Formula 3]

F e → F e ^{2 +} + 2 e + AH (exothermic reaction) [Formula 4]

^{3 (Z n 2+, F e} 2+) + 2 H 2 P 0 4 - →

Consists (Z n, F e) ₃ and _{(P 0 4) 2 + 4} H + ( endothermic reaction).

 Then, in addition to the reactions of Chemical Formulas 1 to 4 above, the balance maintaining reaction of the chemical treatment bath is as follows:

 [Formula 5]

 [Formula 6] '

4 0 H- → 0 ₂ + 2 H ₂ 0 + 4 e

 [Formula 7]

Etc. .

 In the chemical conversion reaction of ordinary electroless steel materials, the reaction of chemical formula 3 acts as the main reaction, and the internal energy (mH) released into the solution by the reaction of yg 3 is converted to chemical formula 1, It is considered that the reactions of 2 and 4 occur on the surface of the metal material (solid), and a film is formed. Therefore, if no other energy such as heat is applied to the reaction system (that is, the chemical conversion bath), the formation of the chemical conversion film is reduced by the reduction of nitrogen-containing oxoacid ions such as nitric acid represented by chemical formulas 1 and 2. The reaction is carried out by an oxidation reaction comprising dissolution of iron and oxidation of phosphate ions as represented by Chemical Formulas 3 and 4.

 Thus, conventional electroless skin formation without supplying other energy is carried out using only the energy (ΔΗ) generated by the melting of the metal material, and is accompanied by the melting. No conversion coating is formed above the generated energy (ΔH).

 On the other hand, the dissolution resistance δ when using an iron metal such as aluminum or 鋦 as the metal material is as follows.

[Formula 8] M → M ^{n +} + ne

 However, even when aluminum is immersed in a phosphatization bath used for steel, for example, non-conductors are formed on the surface of aluminum, and aluminum is The compound is not dissolved in the acidification treatment bath, and the reaction of chemical formula 8 does not proceed. Therefore, energy that would otherwise be caused by dissolution of the aluminum surface is not generated.

 Conventionally, when aluminum is used as the metal material, it is preferable to introduce fluorine ion (F—) into the chemical conversion bath in order to promote the dissolution reaction of chemical formula 8. It was believed.

 Similarly, when copper (Cu) is used as the metal material, it is better to introduce halogen ions other than fluorine ions, for example, chlorine ions (CI-I) into the chemical treatment bath. Had been good.

 However, as described above, even if the metal material is dissolved, it is not possible to form a favorable phosphatized chemical conversion coating on these materials.

 As a reason, when the conventional electroless method is adopted in a treatment bath having a sludge, as described above, a metal material other than general steel (stainless steel, Copper, etc.) did not have the technical idea of using energy for the entire phosphoric acid conversion treatment system of Chemicals 1 to 8 above to effectively promote the entire reaction system. Therefore, no specific measures for controlling the entire reaction system have been implemented.

 That is, for example, in the case of aluminum material, the dissolution reaction instead of chemical conversion of steel 3

 [Formula 9]

A 1 → A 1 ^{3 +} + 3 e

 In Although,

In such a case, they found that it was not possible to supply sufficient energy for film formation for the following reasons. &

 (1) This chemical formula (9) is very slow when F— is not added, and the chemical energy generated by chemical formula (9) is also very small, so that the entire reaction system cannot be established.

(2) When F-is added, chemical reaction proceeds quickly enough, but the resulting complex of ^{A13 +} and F— ( ^A1F4- ) is formed, and this complex is stable in solution. Thus, a film formation reaction containing A 1, which is different from the chemical formula 4, cannot be performed.

 As described above, by regarding the chemical reaction of the formation of the phosphatized chemical conversion treatment film as an electrochemical reaction, the reaction of the chemical conversion is simply performed by adding the third component, as in the related art. It was discovered that mere mere promotion could not form a phosphate conversion coating on metallic or conductive materials other than steel.

 Next, we analyzed the phase transition phenomena of the phosphatization reaction. :

 That is, the inventor of the present invention concluded that the phosphoric acid conversion treatment reaction is basically a “liquid phase-solid phase” reaction in which soluble component ions (liquid) in the bath are converted into a film (solid) by a chemical reaction. However, we thought that it could be understood as a transfer phenomenon.

 However, in the past, phosphoric acid conversion treatment could not be regarded as a kind of phase transition phenomenon.

Because the chemical conversion reaction in the conventional treatment bath is not sufficiently controlled, the chemical conversion reaction in the phosphoric acid conversion treatment bath can cause multiple chemical reactions even on surfaces other than the surface of the material to be treated. Waking up inside at the same time. As described above, when a plurality of reactions occur at the same time, not only one kind of “liquid-solid-solid” reaction but also a plurality of “liquid-solid-solid J reactions” and “ A phase-to-liquid phase "reaction is occurring. As a result, the treatment bath will contain sludge. Therefore, the transfer of energy between these reactions is complicated, and the formation of a film on the metal surface is regarded as a phase transition phenomenon. It is impossible to capture.

 That is, thermodynamic analysis of the phase transition phenomenon can be easily understood in a single-component system such as water, for example, but not in a reaction in a phosphate chemical conversion treatment bath. In addition, complex systems involving complex chemical reactions can be very difficult to understand.

 Therefore, the present inventor can regard the reaction in the bath as a phase transition phenomenon by simplifying the reaction in the phosphate chemical conversion treatment bath as a physical phenomenon. I found this. That is, the state of the bath is controlled to include only liquid so that the reaction in the phosphatization bath is limited to the reaction of forming a film (solid) from the components (liquid) in the solution. The chemical reaction in the phosphatization bath is regarded as a single-phase (liquid) reaction, and as a result, a film (solid) is formed. It is regarded as a phase transition phenomenon. I thought that by using it concretely, it would be possible to find a more effective means of forming a chemical conversion film, which is fundamentally different from the conventional one. is there.

 The following is a description of the specific analysis based on the phase transition phenomenon.

 In the first place, phosphoric acid conversion treatment involves bringing a metal material (solid) to be treated into contact with a solution (liquid) containing a film-forming component. Therefore, the reaction related to chemical conversion treatment

 ①Reaction between metal material (solid phase) and solution (liquid phase) (solid-liquid reaction)

②Reaction between components in solution (liquid-liquid-liquid reaction),

 Are roughly divided into

According to thermodynamic studies, the phase transition phenomenon (liquid-solid) is more dependent on the action between solid and liquid phases (reaction) than on the action between liquid and liquid phases (reaction). It is recognized that it can happen easily. This is because, for example, the coagulation of water in the air is more easily performed on the surface of a solid (solid-gas phase) than in the same phase (gas-phase gas phase). Dew '' frost It seems that it can be easily understood from the result. · In other words, solids are precipitated by the “liquid-liquid” reaction in the solution when a larger amount of energy is added to the reaction system than in the “solid-liquid-liquid” reaction on the surface of the workpiece. It is limited.

 Therefore, based on the above, the inventor regards the reaction in the phosphatization bath as a phase transfer reaction, and thereby transfers the energy added to the chemical conversion reaction system between the liquid and the liquid. The chemical conversion reaction is a phase transition phenomenon between the “solid phase and liquid phase” (film formation) by controlling the reaction between the solid phase and the liquid phase (phase transition) within the range that does not occur. For the first time, we found the fact that it can be performed only on a limited basis.

 Also, considering the conventional method (method of heating the treatment bath) from the viewpoint of the phase transition phenomenon, it has been attempted to form a phosphate conversion coating on the material to be treated. When energy is applied to the treatment bath, the bath is not sufficiently controlled in terms of chemical reaction, and a reaction (phase transition) occurs due to excess energy even on the surface other than the surface of the material to be treated, and the slurry is added to the bath. An edge is formed. As a result, a plurality of solid-liquid phase transition effects occur in the processing bath. For this reason, external energy supply is far from controlling the thickness of the phosphatized chemical conversion coating, and simply promotes the generation of more sludge. It becomes difficult to form a good phosphoric acid conversion coating.

 As described above, the reaction in the phosphatization bath was analyzed from two aspects, namely, the chemical reaction and phase transition phenomena. For the first time, it was possible to understand whether a good phosphoric acid conversion treatment film with a well-controlled film thickness could be obtained.

Furthermore, according to the present invention, based on the analysis described above, the method of forming a phosphatized chemical treatment film having a sufficiently controlled film thickness on a metal material as a conductive material can be further improved. They found out if they could do it. From such a background, the present inventor has determined that the phosphoric acid conversion treatment reaction is essentially an electrochemical reaction system, and that control of the reaction should be considered based on this concept.

 That is, a conductive metal material is brought into contact with a phosphate phosphatization treatment solution containing at least ion phosphate, oxo acid ion containing nitrogen, and metal ion forming a chemical conversion film. A method for forming a phosphoric acid conversion coating on the surface of the metal material,

 The phosphoric acid conversion treatment bath is treated with a bath containing no solid component other than the unavoidable components, and the metal material is electrolytically treated in the phosphoric acid conversion treatment bath. We have found a completely new method of acidification.

 As concrete measures, (1) removal of solid components (sludge) from the chemical conversion bath and (2) utilization of external power supply for reaction.

 Here, that the phosphate chemical conversion treatment bath does not contain solid components other than the inevitable components means that there is no sludge which is energetically unstable in the bath, that is, the bath reacts. This means that the reaction activity involved in the reaction is clear.

The reaction by the electrolytic treatment of the present invention promotes the reactions of Chemical Formulas 1 to 8 by supplying the electric energy from the external power source. In this respect, the conventional electric plating and anodic oxidation are performed. In the positive electrode treatment, which is one of the reactions accompanying the supply of energy from an external power supply according to the present invention, the dissolution reaction (Chem. 3 and 8) of the material to be treated is caused by the thermodynamics in the solution. Under the typical conditions, when the reaction does not proceed naturally or when the progress is not sufficient, the dissolution reaction is promoted by applying electric energy, thereby forming a film on all the reaction systems of Chemical Formulas 1 to 8. It is something we can do. The anodic treatment promotes the dissolution reaction of the material to be treated, and is therefore effective in ensuring the adhesion of the formed chemical film. Cathodic treatment, which is another method of the reaction accompanying the supply of energy from an external power supply of the present invention, is a chemical conversion film formed by acting on the component ions in the solution phase and depositing them on the cathode. The thickness is to be ensured. Therefore, the cathodic treatment alone does not cause a dissolution reaction of the metal to be treated, so that the cathodic treatment is preferably performed after the anodizing treatment. In the cathodic treatment, a film-forming metal material such as zinc is used for the anode, which is dissolved and reacted with ion phosphate and ion in the solution phase to form a film on the surface of the cathode (material to be treated). I do.

 Therefore, if the material to be connected to the cathode is a conductive material, the cathode treatment should be carried out using a chemical containing a predetermined metal material and related chemical components such as phosphoric acid for the anode and the solution phase. Thus, it is possible to form a phosphoric acid conversion coating on a desired metal material to be treated. Then, it is preferable to carry out the cathodic treatment after the anodizing treatment, whereby the phosphate conversion film having excellent adhesion can be formed by using a stainless steel, a magnetic material, an aluminum, It can be formed into copper or the like.

 Here, the anodic treatment is effective for promoting film formation by ensuring that the material capable of forming a film undergoes a melting reaction. The application of only anodic treatment increases the adhesion of the coating, but is effective for the undercoating treatment of steel materials because it does not increase the film thickness. Further, by combining anodizing and cathodic treatment (anodic treatment-cathode treatment), the technology of the present invention provides a phosphoric acid chloride that ensures adhesion to any metal material. It is possible to form a sufficiently thick coating film.

 For example, use as an inorganic insulating film by increasing the thickness of a phosphate film, use of an insulating film on magnetic materials, prevention of aluminum materials, paint base, adhesion, lubrication base for plastic working, etc. Applications include lubricating bases for cold forging stainless steel, and coatings for stainless steel.

The present invention, the chemical treatment bath soluble components containing no slide Tsu di - Limited _{(H 3 P 0 4, N} 0 3, HN 0 2, Z n 2+ , etc. such as metal ions) only After that, put the object to be treated and the electrode in the treatment bath, connect an external power supply between them, and apply a current between the object to be treated (work) and the electrode.

 Then, the phosphate conversion treatment bath is controlled so as not to cause sludge in the treatment bath.

 Here, for example, the following method is used to control the phosphate conversion treatment bath.

 In other words, the control of the energy addition to the chemical conversion bath (pressure control of the liquid by controlling the temperature and the number of revolutions of the circulating pump, and alternately changing the state of the processing bath to the state not reacting). And stabilization of the energy state of the solution in the solution, and by employing means such as filtration to form and maintain a state in which sludge is not generated in the chemical conversion bath. It is preferable to limit the phase transition phenomenon in the treatment bath to only the formation of a film on the surface of the metal to be treated, and perform the phosphatization treatment.

 Then, in the present invention, it is preferable to install a filtration circulation pump and a filtration machine in the phosphate conversion treatment bath.

 The primary purpose of installing the filtration circulation pump and the filtration device is to stabilize the thermodynamic energy state in the solution phase of the reactive solution. If the treatment bath stays in a place where it always reacts (unless there is an alternating circulation of “reacting places J” and “reacting places”), the solution bath in the solution phase as the chemical conversion reaction progresses Thermodynamic energy accumulates. As a result, the stability of the treatment bath solution phase as a liquid is lost, and a solid (sludge) is formed in the solution phase. Filtration circulation pumps and filters are installed to prevent loss of thermodynamic stability of such solutions as liquids. Therefore, the filter itself has a certain volume, and not only a function of filtration but also a state in which the treatment bath is not reacting is maintained for a certain period of time or more. It contributes to the thermodynamic stability of.

The treatment bath is circulated alternately between the “non-reactive place” and the “reactive place” However, ensuring the thermodynamic stability of the solution phase should be considered for all the reaction systems (chemical formulas 1 to 8) in the phosphatization treatment bath. The equilibrium state of phosphoric acid will be described below.

 The phosphatization bath is a solution containing a large amount of phosphoric acid and having a pH of about 2 to 4. Phosphoric acid is in solution at pH 2-4 and is in equilibrium with Chemical Formula 5.

Then, with the chemical conversion (film formation) reaction, Chemical 5 proceeds to the right. This is because, the film formation is H 3 P 0 4 → HZP 0 4 - P 0 4 3 - and dehydrogenation was-phosphate ions and metal ions of Z n ^2+, etc. are bonded, Z n ₃ (P

0 4) 2 If the solution remains only in the treatment tank and does not circulate, the components of the solution change to a state where (Chem. 5) has shifted to the right. As a result, the solution-phase chemical conversion reaction system (Chem.

7) is in a state where sludge is easily generated.

 On the other hand, if the treatment bath is circulated, the phosphoric acid ion in the solution will return to the equilibrium state at the location away from the treatment tank (the direction of (Chem. 5) to the left). ) To stabilize the thermodynamic energy state in the solution.

 Therefore, sludge deposition in the solution phase is suppressed.

 It is preferable that the filtration circulation pump be operated by controlling its rotation speed. Operating the circulation pump at a high speed means applying a high pressure to the solution phase. As a result, the energy in the solution phase increases, and the solution phase cannot maintain its liquid state, and eventually precipitates a solid (sludge). However, if the rotation speed is low, a large capacity pump must be installed, which increases the cost. Therefore, when the circulating pump is an ordinary spiral-wound pump, it is preferable to appropriately control the pump rotation speed using an inverter or the like, suppress the pressure to the solution phase, and secure the circulating amount.

The second purpose of installing a filtration circulation pump and a filtration unit is to remove sludge generated in the treatment bath. If the sludge that has been generated, especially the sludge that is unstable in energy, is left untreated, Makes it easy to generate sludge. Therefore, it is preferable to remove sludge that has been generated quickly.

 In addition, it is preferable that the temperature of the chemical conversion reaction system is moderately adjusted.

 The temperature of the chemical conversion bath in the present invention is in the range of about 20 to 35 ° C. The temperature range is a range generally set to a normal room temperature, which is a normal temperature of an aqueous solution. However, in winter, heating is required to reach the required temperature. It is important to note that the present invention does not use heating to promote the reaction. In other words, the temperature range of 20 to 35 ° C related to the chemical conversion reaction system is a necessary condition for controlling the chemical conversion reaction, and if heat energy is directly used for the chemical conversion reaction, Absent. The current method of heating a phosphate chemical conversion bath heated to 40 ° C or higher is to use a steam or other heat source in the chemical conversion bath, insert a heat exchanger, and directly heat the chemical conversion bath. I have. In this method, the temperature becomes extremely high near the heat exchanger, so that decomposition of the components of the chemical conversion bath by heat is promoted near the heat exchanger and sludge is generated. In that respect, the meaning of the heating is clearly different.

 In the method of the present invention, suppression of sludge generation is considered first. Therefore, it is not preferable to directly input a heat source into the chemical conversion treatment bath. The chemical treatment bath should be warmed as slowly and indirectly as possible. Specifically, a method is preferred in which a heat exchanger is installed in the treatment bath circulation cycle of the electrolytic conversion treatment system, and the system is heated when the circulation pump is operating. It is also preferable to heat the entire treatment tank with water at about 30 to 40 ° C.

According to the method of the present invention, the hydrogen ion concentration (PH), redox potential (ORP), electric conductivity (EC), temperature, etc. of the chemical conversion bath are measured, and a chemical is injected according to the fluctuation. In this way, it is preferable to keep each component ion of the chemical conversion treatment bath in a predetermined concentration range at all times. Also, PH, ORP, EC However, it is preferable that the temperature sensor is installed separately from the processing tank. In the present invention, an electrolytic reaction using an external power supply occurs in the processing tank. Therefore, a current flows in the processing tank, which affects the sensor and cannot display an accurate value.

 By controlling the above bath, it is most preferable that no sludge is deposited in the phosphatization bath. However, if the reaction active substance is an unavoidable component in the Even if the solid component reacts to an energy-stable state and then deposits on the bottom of the treatment tank, etc., it is sufficient if the bathing self-confidence is in a flat state without turbidity. The reason is that these stably deposited, energetically stable sludges have little effect on the ionic components in the solution in which the reaction actually takes place.

 Because, in the case of the present invention, since a current is applied to the treatment bath, the treatment bath is in an electric field (electric field), which means that electric energy is constantly applied and filled. Therefore, solidification generated in the solidification proceeds until the energy becomes stable, and the solidification remains in an incomplete state and does not float in the treatment bath. In other words, each component in the treatment bath becomes either an energy-stable solid component (sludge and film) or a soluble component in an energy-stable bath solution as a solution. If sludge is produced, the sludge will be stable and will remain at the bottom of the tank.

 Therefore, in the electrolysis method for the treatment bath of the transparent bath according to the present invention, the treatment bath can maintain a state that is always stable and does not contain an unstable (halfway in energy) sludge. can do.

 Next, the electrolysis method, which is a feature of the present invention, will be described in more detail. The electrolysis of the present invention is preferably DC electrolysis.

The electrolysis depends on the location (electrode) where the workpiece (work) is connected. It is divided into

 (1) Anode electrolysis · · · Performs electrolysis using the workpiece as the anode

 (2) Cathodic electrolysis · · · Performs electrolysis using the workpiece as the cathode

 ③Anodic electrolysis + cathodic electrolysis

 Further, any of the above-described electrolysis methods may be combined with the method of forming a film by electroless.

 Now, the method of the electrolytic conversion treatment system according to the present invention will be described with reference to FIGS.

 In the present invention, the electrolysis systems shown in FIGS. 1 to 4 can be considered.

 Here, in each of the figures, the electrolytic conversion treatment system is composed of a treatment tank 1, a circulation pump 2, a filter 3, a sensor 4, a power supply 5, an electrode 6, an object to be treated 7, and a temperature control system 8. ing. The electrolysis reaction system consists of one or more, and in the case of two or more, it is installed separately in main electrolysis (reaction) system A and sub electrolysis (reaction) system B. The secondary electrolysis (reaction) system B may be in the same tank or in a separate tank.

 Figure 1 shows a typical electrolytic treatment system. In this case, the electrode and the object may be interchanged.

 Figure 2 is composed of the main electrolysis system A and the sub electrolysis system B. Figure 2 shows an electrolytic treatment system that performs cathodic treatment.

 The configuration is such that voltage and current are applied to the main electrolytic system A, but voltage and current are not directly applied to the secondary electrolytic system. In the sub-electrolysis system B, current does not flow directly from the external circuit from the object 7 to the electrode 10, the electrode 11, etc. via the electric wires.

The current applied in the main electrolytic system A flows in the solution to the object 7 to be treated and the opposite electrodes 10 and 11 of the auxiliary electrolytic system. Then, the current flowing to the counter electrodes (electrodes 10 and 11) of the sub-electrolysis system B passes through the solution again and reaches the treated material 7. In addition, a portion of the sub-electrolysis system B where the current flows to the opposite electrode reaches the workpiece 7 via the diode D. Main electrolytic system A is directly used for chemical conversion film formation The secondary electrolytic system B acts to promote the main reaction satisfactorily, while the secondary electrolytic system B acts on the electrolytic reaction that is locally involved.

 The reason is as follows. In the electrolysis system connected in Fig. 2, the potential in the processing bath during electrolysis (current application) is: anode of main electrolysis system A> counter electrode of sub electrolysis system B> object 7 to be processed. By operating the main electrolytic system A, not only the metal ions of the main electrolytic system A but also the metal ions of the sub electrolytic system B can be precipitated on the surface of the workpiece in conjunction with the main electrolytic system A. It becomes possible.

 The main electrolytic system A is configured such that a main metal for forming a phosphate film such as zinc is used as the electrode 6 on the anode side, and the workpiece 7 is used as a cathode. The secondary electrolytic system B is constructed by immersing a metal material, such as iron and nickel, which constitutes a secondary component of the phosphate conversion coating in a treatment bath, and using this as an electrode. As a result, due to the action of the main electrolytic system A, iron and nickel are also dissolved in the treatment bath, and the dissolved ions are precipitated on the surface of the workpiece as lead and phosphate as phosphate. To form a film. :

 In addition, when metal materials such as iron and nickel are not connected as shown in Fig. 2 but simply immersed in a bath, iron is immersed and left in the electrolytic system, and as a result, iron The amount of dissolution / precipitation increases, the film becomes coarse, and its performance deteriorates. That is, in this case, the dissolution / precipitation of iron is less linked to the dissolution / precipitation of zinc as compared with the case of FIG.

 It is well known that iron ions play an important role in the formation of phosphate films, but too much is inconvenient.

As shown in Fig. 2, by connecting the wires, the current applied to the main electrolytic system. (Between the Zn electrode and the object to be processed) A is applied to the electrodes 10 and 11 in the same processing bath. Although the current is applied, the current is composed of a part discharged to the treatment bath and a part where the current flows to the object 7 through the external connection from iron or nickel. As a result, the dissolution of iron by electrolysis in the chemical conversion bath is suppressed as compared with the case where current flows directly from the iron electrode to the bath. The resulting conversion coating is based on the control of the iron component. In other words, it becomes elaborate.

 The electrodes 10 and 11 of the sub electrolytic system B may be used in combination with iron and nickel, may be used alone, or may be made of another metal. The direction of the diode D in FIG. 2 may be reversed.

 Figure 3 shows the main electrolysis system A and sub electrolysis system B performed in separate tanks.

In this case, when the object to be treated (iron) 7 is continuously anodized in the main electrolytic cell 13 at a voltage of 0.5 V or less, the excess ferrous ion (F e ²⁺ ) dissolves, but when the anodizing voltage is low, the dissolved F e ²⁺ is not oxidized until ferric ion (F e ³⁺ ). As a result, the electro-reduction potential (ORP) of the treatment bath decreases. To control the ORP of the treatment bath to 560 mV or more, it is necessary to change F e ²⁺ → F e ³⁺ as described later in detail.

The secondary electrolyzer 14 in Fig. 3 is installed for such a purpose. Chi words, the main electrolytic cell 1 excess F e ²⁺ is good Ri large voltage in secondary electrolytic cell 1 4 eluted by Ri reaction system to the electrolytic reaction at the 3, Ri by the electrolysis at a current, F e ^{2 +} → Fe ^3+, and the ORP of the treatment bath can be controlled to a predetermined range of 56 OmV or more.

 Figure 4 shows the installation of multiple main electrolytic systems A. The anode is an electrode 7 using zinc and an electrode 15 using other metals (such as iron), and the object 6 is connected as a cathode. Then, a plurality of metals are electrolytically treated at the same time to form a chemical conversion film.

 Next, the method of applying current and voltage will be described. The following methods can be used to apply the current and voltage to the bath by the power supply 5.

 Figures 5 (a) to (d) show the outline.

 (a) Constant current electrolysis, a method of applying a constant current (including pulse electrolysis)

(b) Constant voltage electrolysis · · · · A method of applying a constant voltage (including pulse electrolysis) (c) Current scanning electrolysis * · 'An electrolysis method in which the applied current is controlled (scanned) using a function generator or the like so that the current becomes a predetermined current after a predetermined time. It may be repeated n times.

 (d) Voltage-scanning electrolysis: An electrolysis method in which the applied voltage is controlled (scanned) using a function generator or the like so that the voltage becomes a predetermined voltage after a predetermined time, and the voltage is applied. It may be repeated n times.

 The electrolysis methods (a), (b), (c), and (d) can be performed with the anode and the cathode, and in fact, the eight methods shown in Table 1 are possible .

 Practically, one of the eight methods may be used alone, or a plurality of the eight methods may be combined into a series of steps. In addition, the electroless method and the above electrolysis methods may be used in combination.Table 1 Combinations of electrolysis methods

Note that the electrolytic treatment of the present invention produces sludge more than in the case of an electroless bath. Hard to occur. This is because the electrical energy supplied to the bath increased the electrochemical energy level of the entire bath and increased the stability of each component ion. That is, in a transparent electrolytic bath, the supply of electrons (e) to the solution phase contributes to stabilization of the presence of various ions in the solution phase. Therefore, the solution is thermodynamically stable, since various ions are stable in this transparent electrolytic bath. Therefore, in order to cause a phase transition such as film formation (corresponding to a “liquid-solid” reaction in this case), a large amount of electrochemical energy is required as compared with a transparent electroless bath. Therefore, the electrolytic treatment of the present invention is more stable as a solution than the electroless bath, and is less likely to generate sludge.

The voltage and current applied during the electrolytic treatment are 0.1 V or more: L 0 V, preferably 10 mk / dm 2 to 4 A dm ² . The preferred electrolysis is to ensure that a large amount of current is provided at as low a voltage as possible.

 The oxidation-reduction potential (indicated by the AgC1 electrode potential) of the phosphatization bath of the present invention is preferably from 250 to 65 mV. The 250-65 OmV of the present invention is preferably 450-86 OmV at the hydrogen standard electrode potential.

When the treatment is limited to steel materials, the oxidation-reduction potential of the chemical treatment bath reflects the whole of various equilibrium systems in the treatment bath, but in relation to Fe ²⁺ ion, Reflects Ehi 4. That is, if the amount of soluble metal ^ions , particularly Fe ^2+, is large, the oxidation-reduction potential is low. Conversely, if the amount of soluble metal ^ions , especially F e ²⁺ is small, the redox potential is high. Become. If there is no electrolysis and no energy supply such as heating, the oxidation-reduction potential does not exceed 560 mV. The reason is that the Ag C1 electrode potential of the present invention is the hydrogen standard electrode potential minus about 21 OmV, and the ORP 560 mV (AgC1 electrode potential) is the hydrogen standard electrode potential. At 77 OmV, and the potential is

[Formula 10] F e ²⁺ i F e ³⁺ + e + 0.7 7 V

 This is because it reflects the flat mouth.

That is, in order to obtain 0 RP 560 raV or more, it is necessary to further oxidize the ferrous ion (Fe ²⁺ ) dissolved from the iron material. However, when heating energy is not directly used for film formation in an electroless bath, the energy supplied to the treatment bath is only the energy associated with the dissolution (formula 3) of iron. And because of the energy alone, the flat mouth of (Chemical Formula 10) cannot be moved to the right.

However, in the present invention, since electric energy is supplied by the electrolytic treatment, iron is dissolved and oxidized by the chemical formulas 3 and 10, and the treatment bath contains Fe ²⁺ and Fe ^3+. The ORP may be greater than 56 OmV. Then, the reaction of film formation (Chem. 4) proceeds, and a chemical conversion film is formed. F e ³⁺ is chemical conversion coating F e ²⁺ and the monitor,-phosphate containing also iron in the form of F e ³⁺ that form because it exists stably in the ORP 5 6 0 mV or more baths Probably a conversion coating.

 In addition, if it is less than 25 OmV ", the amount of soluble metal ions increases, and as a result, sludge is easily generated in the treatment bath, so that it is difficult to maintain the transparency of the chemical conversion treatment bath. It is not possible to form a chemical conversion film.

 Even when treating metal materials other than steel, the oxidation-reduction potential of the chemical conversion bath is generally in the range of 250 to 65 · mV. This is because the oxidation-reduction potential reflects the redox balance of the chemical baths 1, 2, 4, and 8 in the treatment bath. This is because the balance between oxidation and reduction of 2, 4 does not fluctuate significantly.

The phosphate ion in the chemical conversion coating bath according to the present invention is approximately 4 g Z £ (gram / liter) or more, the film-forming metal ion is approximately 1.5 gZ or more, and the nitrate ion is approximately. Preferably more than 3 gZi is required. Conversely, the upper limit for phosphate ions is approximately 150 g, the upper limit for film-forming metal ions is approximately 40 g Z ^, and the upper limit for nitrate ions is approximately Preferably, it is approximately 15 OgZ ^. In addition, the most preferable ion concentration is about 5 to 80 g / .beta. For phosphoric acid ion, about 2 to 3 Og / 1 for film forming metal ion, and about nitrate ion. In this case, it is preferable that the value be about 10 to 60 g Z ^.

 The control of the chemical conversion bath is based on the control of the oxidation-reduction potential. Therefore, it is desirable to add a base agent (an acidic chemical containing phosphoric acid, nitric acid, zinc, etc.) in response to fluctuations in the oxidation-reduction potential, but for more reliable control of the chemical treatment bath, It is preferable to use it in combination with other electrochemical parameters such as hydrogen ion concentration (PH) and electric conductivity (EC). The hydrogen ion concentration (P H) is preferably in the range of about 2.5 to 4.0.

 To raise the pH, inject a chemical such as caustic soda to transfer the treatment bath to the alkaline side. Conversely, pH can be reduced by injecting a base material that is an acidic chemical containing phosphoric acid, nitric acid, zinc, and the like.

The appropriate range of the electric conductivity varies depending on the type of the chemical treatment bath. It is preferable to set a higher value for a bath containing a large amount of active ions such as ion nitrate, but to set a lower value for a bath containing a small amount of nitrate ions and a large amount of phosphate ions. In general, it is preferable to add a base agent at the lower limit of the electric conductivity set value and control the electric conductivity of the chemical conversion treatment bath within a certain range. The electric conductivity varies depending on the structure of the ions in the chemical conversion treatment bath, and the conductivity decreases as the structure of the ions in the solution progresses, even if the composition is the same. In consideration of the above, it is preferable to control the electric conductivity of the chemical conversion treatment bath to about 10 to 200 ms-cm- ¹ .

According to the present invention, there is provided a phosphate conversion treatment method capable of applying a phosphoric acid conversion coating film having a sufficient film thickness to the surface of a metal material having any conductivity. be able to. BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 is a schematic diagram of the phosphatization electrolytic treatment system, Fig. 2 is a diagram of the phosphatization electrolytic treatment system, Fig. 3 is a diagram of the phosphatization electrolytic treatment system, and Fig. 4 is Fig. 5), (b), (c), (d) are characteristic diagrams showing the state of current and voltage application, and Fig. 6 is phosphoric acid obtained by the method of Example 1. SEM photograph of the crystal structure of the salt film, Fig. 7 is a fluorescence analysis diagram of the phosphoric acid film obtained by the method of Example 1, and Fig. 8 is X-ray image of the phosphoric acid film obtained by the method of Example 1. X-ray diffraction chart, FIG. 9 is an SEM photograph of the crystal structure of the phosphate film obtained by the method of Example 2, and FIG. 10 is the image of the phosphoric acid film obtained by the method of Example 2. X-ray fluorescence analysis diagram, Fig. 11 is the X-ray diffraction chart of the phosphoric acid film obtained by the method of Example 2, and Fig. 12 is the re- sult obtained by the method of Example 3. SEM photograph of the crystal structure of the phosphate film, Fig. 13 is an X-ray fluorescence analysis diagram of the phosphoric acid film obtained by the method of Example 3, and Fig. 14 is a photoreceptor obtained by the method of Example 3. X-ray diffraction chart of the phosphoric acid film, Fig. 15 is an SEM photograph of the crystalline structure of the phosphate film obtained by the method of Example 4, and Fig. 16 is the method of Example 4. X-ray fluorescence analysis diagram of the obtained phosphoric acid film, Fig. I7 is a fluorescence X-ray diffraction chart of the phosphoric acid film obtained by the method of Example 4, and Fig. 18 is the method of Example 5. SEM micrograph of the fine structure of the obtained phosphate film. Fig. 19 is an X-ray analysis chart of the phosphate film obtained by the method of Example 5, and Fig. 20 is Example 6 Fig. 21 is an X-ray analysis chart of the phosphate film obtained by the method of Example 6, and Fig. 21 is an SEM photograph of the structure of the phosphate film obtained by the method of Fig. 2. 2 is the ring obtained by the method of the comparative example. SEM photograph of the crystal structure of the phosphate film, Figure 23 is a schematic diagram of the parts used in Example 7, and Figure 24 is an SEM photograph of the crystal structure of the phosphate film obtained by the method of Example 8. Fig. 25 and Fig. 25 are X-ray X-ray charts of the phosphate film obtained by the method of Example 8, and Fig. 26 is the crystals of the phosphate film obtained by the method of Example 9. SEM micrograph of the structure, Fig. 27 is an X-ray analysis chart of the phosphate film obtained by the method of Example 9, and Fig. 2 & SEM micrograph of the crystal structure of the phosphate film obtained by the method of Example 10; Fig. 29 is an X-ray analysis chart of the phosphate film obtained by the method of Example 10 FIG. 30 is a schematic diagram of the segment used in Example 11, FIG. 31 is a schematic diagram showing the core of Example 11, and FIG. 32 is a valve made of the core of Example 11 FIG. 33 is a schematic diagram showing a conventional core, FIG. 34 is a cross-sectional view showing a valve made of a conventional core, FIG. 35 is a characteristic diagram showing the characteristics of Example 11, and FIG. FIG. 37 is a characteristic diagram showing characteristics of Example 12; FIGS. 38 (a) and (b) are front and side views of a core showing Example 13; FIG. 39 is a partially enlarged view of the core of Example 13; FIG. 40 is a partially enlarged view of the conventional core; and FIG. 41 is a characteristic diagram showing current and voltage characteristics of Example 14; is there. BEST MODE FOR CARRYING OUT THE INVENTION

 In Examples 1 to 6 and 8 to 10 of the present invention, the test agent was a plate-like test piece (A) of 15 cm, 7 cm, or 1 mm in length, width, or thickness, respectively. ) Test pieces of 7.5 cm, 3.5 cm, 1 mm were used, and the opposite electrode was a 2 Ocm, 5 cm, 1 to 2 mm plate-shaped one each in vertical, horizontal, and thickness directions. In Example 7, a clutch component of a compressor for an automobile air conditioner was used.

 In Example 11, a magnetic material (ILSS) and a component (core segment) forming a core for a solenoid for controlling a fuel injection pump for an automobile were used.

 In Example 12, a magnetic material (ILSS) having a length of 500 mm, a width of 28 mm, and a thickness of 2 mm before plastic working of the solenoid core segment used in Example 11 was used. Using.

Example 13 used a stator core of an automotive alternator. The volume of the treatment bath used for the treatment was about 20 liters. The tent pieces in each example are degreased, rinsed with water, rinsed with water and pickled (1-2% HN03 at room temperature for 1 to 2 minutes) → rinsed with water → rinsed with water (surface adjustment) (0.2%) → Phosphoric acid conversion treatment → Rinsing—Washing was performed in 2 minutes for each step except for the phosphoric acid conversion treatment. The treatment time of the phosphoric acid conversion treatment differs in each of Examples and Comparative Examples. After degreasing, after washing, fresh industrial water was sprayed to ensure reliable washing.

 In Examples 5 and 6, Examples 7 to 13 and Comparative Example, no pickling and subsequent water washing were performed.

 The outlines of the examples and comparative examples are shown in Tables 2 and 3. In addition, 0 R P (oxidation-reduction potential) shown in the examples is all Ag Cl electrode potentials. When replacing the Ag C 1 electrode potential with the hydrogen standard electrode potential, add about 2 l O mV.

 Also, SEM photographs of the phosphatized chemical conversion coating films obtained in the respective examples are shown in Figs. &, 9, 9, 12, 15, 18, 18, 20 and 22, 24, FIG. 26 and FIG. 28 are magnifications of 1000 times.

(Hereinafter the margin)

Table 2

 *-1 Conducted without electrolysis

*-2 Classification in Fig. 1-5 Table 3

 * -2 Classification in Figure 5

* 1 3 (Main) → Main electrolysis system, (Sub) sub electrolysis system (Example 1)

 A steel material (SPCC) was used as the treatment agent. In the phosphoric acid conversion treatment, first, an electroless chemical conversion treatment was performed for 2 minutes as the first step.

-Phosphate salt chemical treatment bath used was the ^{Z n 2+ 3. 0 g / 1} , H 3 P 0 4 to _{8 g / l, N 0 3} - a 3 2 g / l, the N i ²⁺ 0.8 g / l, F-one is for 0.1 lg Zl. The pH, ORP and temperature of the treatment bath are 3.20, 400-500 mV and 30 ° C, and the total acidity, free acidity and accelerator concentration are 16 pt, 0-0. They were 1 2 pt and 6 pt. Further, the transparency of the treatment bath was 30 cm or more, and the chemical conversion treatment bath did not contain sludge.

Next, electrolytic treatment was performed using the material to be treated as a cathode and the zinc plate as an anode. Li phosphate salt chemical treatment bath used was, Z n ²⁺ a 3. 0 g / 1, H 3 P 0 4 to 1 6 g raised to the power of N 0 ₃ -! The 1 7 g / l, 1 ^ 2+ Is 2 .. 4 2 1, F is 0.lg / l.Mn is 4.OgZl. The pH and RP of the treatment bath were 3.20, 400 to 5001 11 and 28, and the total acidity, free acidity and accelerator concentration were 16 pt, 0 to 0, 0.01 t and 6 pt. The transparency of the treatment bath was 30 cm or more.

霉解treatment was performed at a voltage 0.. 5 to 1. 5 V, the current 0. Z AZ dm ^2, time 4 0 min conditions. Table 2 shows the electrolysis method (electrolysis treatment system and current voltage application method). The contents of the electrolysis method are also shown in Tables 2 and 3 in the following examples.

By this treatment, a phosphoric acid conversion coating film with a film thickness of 2 T rn and a dielectric breakdown voltage of 250 V or more according to JIS K 6911 was obtained. The film thickness is a value measured with a KET SCIENCE (manufactured) electromagnetic thick film meter LΕ-300. Hereinafter, the thicknesses of the steel materials are all measured by the same method as in Example 1. Figs. 6 and 7 show S-ray micrographs and X-ray fluorescence analysis diagrams of the obtained phosphoric acid chloride conversion coating. Fig. 8 shows the X-ray diffraction diagram. In Fig. 8, the symbol 〇 Shows a peak of Z n 3 (P 04) z · 4 H 2 0 and _{Z n 3 (P 0 4)} .

 It can be said that the film obtained in Example 1 is a thick film containing nickel, manganese, and zinc with excellent withstand voltage.

(Example 2)

An aluminum plate (Al100) was used as the material to be treated, and a steel plate was used as the counter electrode. As a-phosphate salt chemical treatment bath, the same Z n ²⁺ processing bath used in the electrolytic process of Example 1 3. 0 g / 1, H 3 P 0 4 to 1 6 gZ 1, 03 - ¾ 1.7 g / l, 2.4 g / l for Ni'2 ⁺ , 0.1 g for F, 4.0 g for Zl and ^{Mn2 ÷} did. The pH, ORP and temperature of the treatment bath were 3.00 to 3.40, 560 to 570 mV and 25 to 30 ° C, and the total acidity, free acidity and accelerator concentration were They were 18 pt, 0.1 pt and 6 pt. In addition, the treatment bath had a transparency of 30 cm or more, and the treatment bath was free of sludge.

In the electrolytic treatment, first, an aluminum plate, which is a material to be treated, is used as an anode and a steel plate is used as a cathode, and a voltage of 1 to 3 V and a current of 0.3 to 0.6 A / dm ² , 0.5 are used. For 1 minute, then using the same treatment bath, using the aluminum plate as the material to be treated as the cathode and the steel plate as the anode, voltage 1-3 V, current 0.3-0.6 AZ dm Treated with ² for 5 minutes.

By this treatment, a phosphate film having a coating weight of 6.12 g / dm ² was formed on the surface of the aluminum plate. .

Figures 9 and 10 show an SEM photograph and an X-ray fluorescence analysis of the resulting phosphoric acid chloride conversion coating. Figure 11 shows the X-ray diffraction diagram of the coating. Incidentally, .smallcircle in FIG. 1, similar to FIG. 8, a peak of _{Z n 3 (P 0 4)} 2 · 4 H 2 0 Contact and Z n ₃ (P 04), also厶印is The peak of A 1 is shown.

The coating obtained in Example 2 was a phosphor containing manganese, nickel and zinc. It can be said that this is an acid conversion coating.

 (Example 3)

A stainless steel plate ('SUS304) was used as the material to be treated, and a steel plate was used as the counter electrode. As a-phosphate salt chemical conversion treatment bath, Examples 2 and 3 the same ^{Z n 2+. 0 g / 1} , H 3 P 0 4 to 1 6 g / l, N 0 3 to 1 7 g / 1 the ^{n i 2+ 2. 4 g / 1} . F to 0. lg Z l, was used a M n ²⁺ of 4. O g Z l. The pH, ORP and temperature of the treatment bath are 3.00 to 3.40, 560 to 570 mV and 25 to 30 ° C, and the total acidity, free acidity and accelerator concentration Were .18 pt, 0.1 pt and 6 pt. Further, the transparency of the treatment bath was 30 cm or more, and the treatment bath did not contain sludge.

Electrolytic process, first, and stearyl down-less steel and an anode of the steel plate and shadow. Poles to be processed material, voltage 1 ~ 3 V, the current 0. 3~ 0. 6 AZ dm ^2, time 1 minute Then, using the same treatment bath, using a stainless steel plate as the material to be treated as a cathode, a voltage of 1 to 3 V and a current of 0.3 to 0.6 A / dm ² Treated for 0 minutes.

By this treatment, a phosphoric acid conversion coating film having a coating weight of 13.27 / dm ² was obtained on the surface of the stainless steel plate.

Figures 12 and 13 show SEM photographs and X-ray fluorescence analysis diagrams of the obtained phosphoric acid conversion coating. Fig. 14 shows the X-ray diffraction diagram of the film. Incidentally, .smallcircle in FIG. 4, similar to FIG. 8 shows a peak of _{Z n 3 (P 04) 2} · 4 H 2 0 and _{Z n 3 (P 0 4)} . .

 The film obtained in Example 3 was a zinc phosphate conversion film containing zinc. (Example 4)

Oxygen-free copper (C1020) copper plate was used as the material to be treated, and iron steel plate was used as the counter electrode. As a-phosphate salt chemical treatment bath, the same Z n ²⁺ as in Example 2 3. 0 g / 1, H 3 P 0 4 to 1 6 g Z l, N 0 3 to 1 7 g Z l , N i ²⁺ 2.4 g / 1, F 0 .lg Z l, M n ²⁺ 4.0 g / 1 Was used. The pH, ORP, and temperature of the treatment bath were 3.00 to 3-40, 560-570 mV and 25 to 30 ° C, and the total acidity, free acidity, and accelerator concentration were 1 They were 8 pt, 0.1 pt and 6 pt. The treatment bath had a transparency of 30 cm or more, and the treatment bath did not contain sludge.

Electrolytic process, first, a copper plate to be processed forest as an anode and the voltage. 1 to 3 V, the current ^{0. 3~ 0. 6 A / dm 2} , was treated at time 3 0 seconds, followed by the same treatment bath The substrate was treated for 10 minutes at a voltage of 1 to 3 V and a high current of 0.3 to 0.6 A dm ² using a copper plate as a material to be treated as a cathode.

By this treatment, a phosphoric acid conversion coating film with a coating weight of 6.67 gZm ² was obtained on the copper plate.

Figures 15 and 16 show SEM photographs and X-ray fluorescence analysis diagrams of the obtained phosphoric acid conversion coating. Fig. 17 shows the X-ray diffraction diagram of the coating. Incidentally, FIG - O mark in 1 7 shows a peak in the same manner as FIG. _{8, Z n 3 (P 04} ) 2 · 4 H 2 0 and _{Z n 3 (P 0 4)} ..

 The coating obtained in Example 4 is called a phosphoric acid conversion coating containing manganese and zinc.

 (Example 5)

Steel plate (SPCC) was used as the material to be treated, and steel plate was used as the counter electrode. As a-phosphate salt chemical conversion treatment bath, Z n ²⁺ to 4. 0 g / 1, H 3 P 0 4 to 1 2 g / l, the N 0 ₃ 4 0 g / a N i ²⁺ 6 g / l and F were 0.2 g / l and Μη ²⁺ were 5 g / l. PH, 0 RP and temperature of the treatment bath are 2.70, 300 to 400 mV and 22 ° C, total acidity and accelerator concentration are 15.8 pt, and 6 pt Met. The transparency of the treatment bath was 30 cm or more, and the treatment bath contained no sludge.

In the electrolytic treatment, first, a steel sheet, which is the material to be treated, was used as the anode, and a voltage of ^2.5 to 3.5 V, a current of 0. The process of maintaining the state where the power was turned off for 0 seconds was repeated once or twice, and the entire process was performed for about 8 minutes. Thereafter, the cathode treatment of the material to be treated was not performed. By this treatment, a dense phosphoric acid conversion coating film with a thickness of 2 to 3 m was obtained. Figures 18 and 19 show SEM photographs and X-ray diffraction charts of the obtained phosphoric acid conversion coating.

 The coating obtained in Example 5 is a dense phosphate coating.

 (Example 6)

The steel plate (SPCC) was used as the material to be treated, and the same steel plate was used for the counter electrode. As a-phosphate salt chemical conversion treatment bath 4 the same Z n ²⁺ as in Example 5. 0 g / 1, H 3 P 0 4 to 1 2 g Z l, N 0 3 a 4 0 g Z l , i 2 ⁺ was 6 g Zl, F was 0.2 g Z, and ¾ ^ 11 ²⁺ was 5 no 1. The pH, ORP and temperature of the treatment bath were 2.70, 300 to 400 m and 23 ° C, and the total acidity and accelerator concentration were 16 pt and 1.6 pt. Also, the transparency of the treatment bath was 30 cm or more, and the treatment bath did not contain sludge.

In the electrolytic treatment, first, a steel sheet, which is the material to be treated, was used as the anode, and a voltage of 1.5 to ^2.5 V, a current of 0.5 A / dm2 was applied for 30 seconds, and then the current was turned off for 10 seconds. The process of maintaining the state was repeated once or twice, and the entire process was performed for about 8 minutes. Then, using the same treatment bath, with the steel sheet to be treated as the cathode, a voltage of 1.5 to ^2.5 V and a current of 0.5 AZ dm2 were applied for 30 seconds, and thereafter, the current was applied for 10 seconds. The treatment was repeated 12.times. With the cut off, and the treatment was performed for about 8 minutes in total.

 By this treatment, a phosphoric acid conversion coating film with a thickness of 7 m and a dielectric breakdown voltage of 250 V or more with JIS K 6911 was obtained.

 S-ray micrographs and X-ray diffraction charts of the obtained phosphoric acid conversion coating are shown in FIGS. 20 and 21.

The coating obtained in Example 6 was a phosphate conversion coating having insulating properties. You.

 (Comparative example)

 An example in which no electrolytic treatment was performed is shown as a comparative example.

A steel sheet (SPCC) was used as the material to be treated. As a-phosphate salt chemical conversion treatment, 3 ^{Z n 2+. 2 g Z l} , H 3 PC to 8 g / l, N 0 ₃ scratch 3 2 g Z l, ^ 1 2+ a 0.8 g / 1, F— of 0.2 g Zl was used. PH, 0 RP and temperature of the treatment bath were 3.20, 510 to 54 in V and 28 ° C, and total acidity, free acidity and accelerator concentration were 16 pt, 0 to 0. lpt and 6 pt. The treatment bath had a transparency of 30 cm or more. The treatment bath contained no sludge. The material to be treated was immersed in this treatment bath for 8 minutes.

 As a result of this treatment, a phosphoric acid conversion coating with a dielectric breakdown voltage of 5.0 V with a thickness of 1 m and a JIS K 6911 was obtained.

 Figure 22 shows an SEM photograph of the resulting phosphoric acid chloride conversion coating.

 The phosphoric acid conversion coating obtained in the comparative example is generally obtained by an electroless method, and it can be said that even if the immersion time is lengthened, an increase in the film thickness and an improvement in the withstand voltage cannot be expected.

 (Example 7)

As shown in Fig. 23, the steel material used for the compressor clutch of the car air conditioner was used as the material to be treated, and the same steel plate was used for the counter electrode. -. The steel parts, as a-phosphate salt chemical conversion treatment bath in a substantially hollow shape having a diameter of 9 6 mm, thickness 2 7 mm, 4 to ^{Z n 2+ 2 g / \,} H a P 0 4 8 gl, N 0 ₃ — was 24.1 g / l, Ni ²⁺ was 2.6 g / l, and F− was 0.1 g. The pH, ORP and temperature of the treatment bath are 2.93, 580-590 mV and 27 ° C, total acidity, accelerator The concentrations were 20 pt and 6.0 pt. The transparency of the treatment bath was 30 cm or more, and it did not contain sludge.

 Electrolytic treatment is performed using the method shown in Fig. 3, with the part to be treated as the anode and the iron plate as the cathode, with a voltage of 0.3 V to 1.0 V and a current of 0.01 A to 0.14 A in the main electrolytic system. This was performed for 2 minutes using the treated material as shown in Fig. 5 (a).

When the 0 RP of the processing bath drops to about 560 mV, the secondary electrolytic system B performs current scanning electrolysis according to the method shown in Fig. 5 (c), and removes Fe ²⁺ dissolved in the processing bath from the bath. Removed and performed to increase ORP. After this, Kao-tin electrodeposition coating (Nippon Paint Co., Ltd., Wartop U56) was performed, and baking was performed at 190 ° C for about 25 minutes. After leaving the coated material for 24 Hr or more, scratch the flat surface 20 and the outer peripheral portion 21 with a cutter knife until the base material is reached, and then add 5% sodium chloride at 55 ° C. A saltwater immersion test was performed by immersion in water for 240 Hr. The treated material that had passed 24 OH r was washed with water and left in the air for about 2 H r, and then an adhesive tape was applied to the coating surface damaged with a cutter knife and strongly peeled off. When the width of the coating film separated by the tape was measured, it was found that both the flat surface portion 20 and the outer peripheral surface 21 were 5 mm or less.

 Using the same bath (however, 0 RP value is less than 560 mV) in electroless treatment, immersion for 2 minutes, chemical conversion treatment and the same coating were performed, and the same coating film evaluation test was performed. At this time, the flat portion 20 was 5 mm or less, or the outer peripheral surface 21 was peeled off by about 8 to 12 mm.

 From the above evaluation, it can be said that the method of the present invention has good corrosion resistance after coating in the outer peripheral portion 21. The outer peripheral surface 21 is a portion that is greatly deformed when this part is formed by press working, and it is considered that the chemical conversion treatment is difficult with the conventional electroless method. Therefore, the corrosion resistance of the coating is poor in the electroless chemical conversion treatment.However, in Example 7, the anodic electrolysis is performed to dissolve the material even in a portion where it was conventionally difficult to dissolve the material, and the chemical conversion treatment is performed. And improved coating corrosion resistance.

Electrolysis using the same parts in the same treatment bath and the same electrolytic treatment system Only the processing method was changed to the method shown in Fig. 5 (c), and the current ^: OA → 0.01 A was started in 30 seconds, and the current was held for 30 seconds. Electrolysis was performed for 2 minutes in a manner of changing from 0 A to 0 A. Thereafter, it was painted and subjected to the same salt water immersion test as described above. As a result, the tape peeling width was 5 mm or less for both the flat portion 20 and the outer peripheral surface 21, and the coating corrosion resistance was better than that of the non-electrolytic one.

 In Example 7 described above, the material was dissolved by using the sub-electrolysis system, but it may not be necessary depending on the anodic treatment conditions (current, voltage composition, etc.). .

 (Example 8).

 A steel sheet (SPCC) was used as the material to be treated. Iron was used for the anodizing on the counter electrode, iron was used for the secondary electrolytic system for the cathodic treatment, and zinc was used for the main electrolytic system.

As a-phosphate salt chemical conversion treatment bath Z n ²⁺ to completion. 6 gZ and H a P 0 _4. The 2 8. 3 g X 1, N 0 3 a 2 7. 1/1, N i 2+ 1.44 g / l and F 0.1 g Z 1 were used. The pH, OR temperature, and temperature of the treatment bath were 3.03, 573 mV and 27 ° C, respectively, and the total acidity, free acidity, and accelerator concentration were 38.4 pt and 1.6, respectively. pt and 5. Opt. The transparency of the treatment bath was 30 cm or more, and the treatment bath did not contain sludge.

Electrolytic process, first the workpiece as the anode, of如rather 1, iron as a cathode, Figure 5 current constant current electrolysis of (a) 0. 0 5 A / dm 2 ( voltage 0.1 3 min) for 1 minute. Subsequently, a main electrolytic system is formed using the same bath, using the material to be treated as a cathode and zinc as an anode.

 In addition, wiring is performed between the workpiece and the iron electrode, and the wiring is made so that current flows only in the direction from the iron electrode to the workpiece. The route between the material to be treated and iron is a secondary electrolytic system.

Cathode process in the main electrolysis system A in FIG. 2 performs a current scanning electrolysis, over 5 minutes to a ^{0 AZ dm 2 → 1. 5 A} / ά m 2 between the electrodes of the main electrolysis system A The application was performed gradually. The maximum applied voltage at that time was 4.5 V. Then, the same operation was repeated for six cycles, and the cathode treatment was performed for a total of 30 minutes.

 By this treatment, a 15- to 30-m-thick phosphoric acid conversion coating was formed on the steel sheet surface. (The film thickness is the value measured with an electromagnetic film thickness meter LE-300 manufactured by Ket Kagaku Corporation.) The insulation resistance of this film was measured by a super-insulation meter SM-8210 manufactured by Toa Denpa Co., Ltd. Measured at The measurement was performed by lightly contacting the rod-shaped probe (positive electrode, negative electrode) of the super insulation meter with the surface. As a result, both the flat surface and the edge of the steel sheet had an insulation resistance of 500 V DC or more.

Figs. 24 and 25 show SEM photographs and X-ray diffraction charts of the obtained phosphoric acid chloride conversion coating. Incidentally, .smallcircle in FIG. 5, similar to FIG. 8 shows a peak of _{Z n 3 (P 04) 2} · 4 H 2 0 and Z n ₃ (P 04).

 (Example 9)

 A steel plate (SPCC) was used as the material to be treated. Iron was used for the anodizing process on the counter electrode, zinc was used for the main electrolytic system A for the cathodic treatment, and iron and nigel were used for the sub electrolytic system B.

. 7 Z n ²⁺ as a-phosphate salt chemical conversion treatment bath 0 g / and H a P 04 of 4 5 0 g / 1, N 0 3 -.. A 2 6 0 g / 1, N i 2 ⁺ Was used in 1.4 g and F was used in 0.1 g Zl. The pH, ORP and temperature of the treatment bath were 3.02, 565 mV and 24.5 ° C, respectively, and the total acidity, free acidity and accelerator concentration were 51.8 pt and 2.4, respectively. pt and 5.6 pt. Also, the transparency of the treatment bath was 30 cm or more, and the treatment bath did not contain sludge.

Electrolysis treatment, the first device of Figure 1, the workpiece as the anode, iron as a cathode, the current constant current electrolysis in Fig. 5 (a) 0. 0 5 A Roh dm ² (voltage 0. 3 min) for 1 minute.

Subsequently, the same treatment bath is used, and the apparatus shown in Fig. 2 is used. That is, the main electrolytic system A is formed using the material to be treated 7 as a cathode and zinc as an anode. Also The wiring is made between the physical material 7 and the electrodes 10 and 11, which are iron and nickel. The wiring is made so that current flows only from the iron and nickel electrodes to the object to be processed. The path between the object 7 and the electrodes 10 and 11 is the auxiliary electrolytic system B.

Its to the cathode process in the main electrolysis system A is carried out at a current scanning electrolysis, primarily between electrodes in the electrolytic system A 0 AZ dm ² - applying s ordinal over 5 minutes to a 2. 0 A / dm ² I went to work. The maximum applied voltage at that time was 4.9 V. Then, the same operation was performed for 6 cycles, and a total of 30 minutes of cathode treatment was performed. ―

 By this treatment, a 15- to 30-m-thick phosphoric acid conversion coating was formed on the steel sheet surface. (The film thickness is a value measured by an electromagnetic film thickness meter LE-300 manufactured by Chit Kagaku Corporation.) The insulation resistance of this film was measured by a super-insulation meter SM-8210 manufactured by Toa Denpa Co., Ltd. did.

 The measurement was performed by lightly touching the probe (positive electrode, negative electrode) of the super insulation meter to the surface.

 As a result, both the flat part and the edge part of the steel sheet had an insulation resistance of 500 V DC or more.

SEM photographs and X-ray diffraction charts of the obtained phosphoric acid chloride conversion coating are shown in Figs. 26 and 27. Incidentally, .smallcircle in FIG. 7, similarly to FIG. 8 shows a peak of _{Z n 3 (P 0 4)} 2 · 4 H 2 0 and Z n ₃ (P 04). (Example 10)

 A steel plate (SPCC) was used as the material to be treated. Iron was used for the anodizing process on the counter electrode, and zinc was used for the cathodic process.

Then, the iron electrode plate was removed from the power supply and the wire was immersed in the bath. As a-phosphate salt chemical conversion treatment bath, Z n ²⁺ to _{7. 0 g / 1, H 3} P 0 4 to 4 5. 0 g / 1, N 0 3 a 2 6. 0 g Z 1, N ^1.4 g / 1 for i ²⁺ and 0. lg Z l for F— were used. The pH, ORP and temperature of the treatment bath were 3.02, 569 mV and 2 ° C, respectively, and the total acidity was , Free acidity and accelerator concentration were 51.8 pt, 2.4 pt and 5.6 pt, respectively. Also, the transparency of the treatment bath was 30 cm or more, and the treatment bath did not contain sludge.

In the electrolytic treatment, first, as in the apparatus shown in Fig. 1, the material to be treated is used as the anode, iron is used as the cathode, and the constant current electrolysis shown in Fig. 5 (a) is performed with a current of 0.05 A A dm ² (voltage 0.5 min) for 1 minute.

Subsequently, the same treatment bath is used to form an electrolytic system using the material to be treated 7 as a cathode and zinc as an anode. At that time, steel sheets were often immersed in them. If the steel sheet is immersed in the treatment bath, the steel sheet exists in the electrolytic reaction system. That is, iron is easily dissolved from the steel sheet, and the dissolved Fe ^{2 +} adheres to the surface of the workpiece as a chemical conversion film. For this reason, the film thickness of the chemical conversion film is significantly increased as compared with Examples 8 and 9. The cathodic treatment of the main electrolytic system A is performed by current scanning electrolysis, and it is applied gradually over 5 minutes to make 0 A dm 2 → 2.0 A / dm ² between the electrodes of the main electrolytic system A. I went there. The maximum applied voltage at that time was 5.8 V. Then, the same operation was performed for 6 cycles, and the cathode treatment was performed for a total of 30 minutes.

 By this treatment, a phosphoric acid chloride film with a thickness of 50 to 60 m was formed on the steel sheet surface. (The film thickness is a value measured with an electromagnetic film thickness meter LE-300, manufactured by Chit Kagaku Corporation.) The insulation resistance of this film was measured by Toa Denpa Co., Ltd., a super-insulation meter SM-8210. Was measured. The measurement was performed by lightly contacting the probe (positive electrode, negative electrode) of the super insulation meter with the surface. As a result, the flat part of the steel sheet had an insulation resistance of DC 500 V or more. The pressure resistance was about 250 V in the edge part. Further, the adhesion of the film to the base was also inferior to those of Examples 8 and 9. From these facts, it can be said that it is necessary to control the Fe ions in the chemical conversion bath in order to form a thick type insulating chemical conversion film.

SEM photographs and X-ray diffraction charts of the obtained phosphoric acid chloride conversion coating are shown in Figs. Note that the symbol 〇 in FIG. 29 indicates Z n ₃ (P 04) shows a peak of 2 · 4 H 2 0 and Z n ₃ (P 04). (Example 11)

 As the material to be treated: As shown in Fig. 30, a magnetic material (containing 1 L S S, 1% Si) and a segment 30 for a solenoid core used for a fuel injection pump of an automobile were used.

At the counter electrode, iron was used for anodizing, and iron and zinc were used for cathodic processing. As a-phosphate salt chemical conversion treatment bath was甩I a a Z n ²⁺ 1 2 g Z to the N i ²⁺ 1. 6 g Z l including-phosphate salt chemical conversion treatment bath. (In addition, N 03-, H 3 P 04 one,

F-1 is used but not measured. ) The pH and temperature of the treatment bath were 2.96 to 3.02, 5777 to 581 mV and 26 to 28 ° C, respectively, and the total acidity and accelerator concentration were respectively It was 40 pt and 3.0 t. (The free acidity was not measured.) The treatment bath had a transparency of 30 cm or more and contained no sludge.

 The chemical conversion treatment was performed by putting 200 segments 30 shown in Fig. 30 into a small barrel made of acrylic resin and performing electrolytic treatment inside the barrel.

 Processing was performed for a total of 4 barrels, for a total of 800 parts. The barrel is rotated at 2 RPM and has many 5 mXm holes on the sides to facilitate bath flow.

 In the electrolytic treatment, the material to be treated was first used as the anode, and iron was used as the cathode, and the constant current electrolysis shown in Fig. 5 (a) was performed using the connection system shown in Fig. 1.

The current at that time was 0.06 A barrel and the voltage was between 1.2 V force and 3.5 V. Incidentally surface area per barrel corresponds to 6 2 dm ^2. Anodizing was performed for 5 minutes, and then the power was turned off for 2.5 minutes.Cathode processing was performed using iron and zinc as anodes and the barrel containing the object to be treated as the cathode to form the electrolysis system in Fig. 4. The current scanning electrolysis method shown in Fig. 5 (c) was used.

The iron electrode at that time is 0 A (ampere) barrel → 0.06 A ~ 0.1 The A-barrel is applied sequentially in 90 seconds, and the zinc electrode is applied in 0-barrel 0.5-1.0 A novar in 90 seconds, and the same. The operation was performed for 15 cycles.

 By this treatment, a conversion film of 3 to 10 m was formed on the surface of the magnetic material, which is the surface of the segment 30. (The film thickness was measured with an electromagnetic film thickness meter manufactured by Ket Kagaku.)

 The insulation resistance of this film was measured with a super insulation meter manufactured by Toa Denpa Co., Ltd. The measurement method was the same as in Examples 8 to 10. As a result, an insulation resistance of 100 V (D C) or more was obtained in the plane portion.

0 The core 30 of the solenoid stay core used in Example 11 of FIG. 30 was laminated to form the stay core 31 of FIG. 31.

 Then, as shown in Fig. 32, winding and assembling are performed on the core 31, and a valve 32 for controlling the injection amount of the automotive fuel (light oil) injection pump is created. did.

5 Figure 33 shows a conventional solenoid stator core segment 35 and a stationary core 36 using the same.

 The conventional segment 35 is an F-type segment (material G09) that has already been insulated.

 Conventional insulation processing of magnetic materials cannot plastically deform (deform) the material, so the conventional steel core 36 has a shape in which punched sheet materials are laminated.

 Using the core 36, a fuel injection pump valve 37 was created as shown in FIG. .

 At this time, the size (dimensions) of the valve 32 related to the embodiment 11 in FIG. 32 and the conventional valve 37 in FIG. 34 are the same.

5 Figure 35 shows a comparison of the performance of each valve 32 and 34.

~ As a result of the evaluation based on the static suction force with respect to the drive current (A), the valve 32 (solid line in Fig. 35) is of the same type as the valve 37 (dashed line in Fig. 35). And that it has excellent solenoid (suction) capability. I was able to confirm.

 (Example 12)

 As a material to be processed, a magnetic material (ILSS) having a length of 500 mm, a width of 28 mm, and a thickness of 2 mm before plastic working of the solenoid core segment 30 used in Example 11 was used. ) Was used.

Anodizing and then cathodic treatment were performed using iron as the counter electrode. Using Z n ²⁺ to 6 g / 1, N i ²⁺ to 6 g Z 1 comprises a bath with a-phosphate salt chemical conversion treatment bath. The treatment bath had an FH of 3.03, an ORP of 576 mV, a temperature of 25 to 30 ° C, a total acidity of 44 pt, and a promoter concentration of 5.2 pt. (The free acidity was not measured.) The transparency of the treatment bath was 30 cm or more and did not contain sludge.

 In the electrolytic conversion treatment, first, the agent to be treated was used as the anode and iron was used as the cathode, and the constant current electrolysis shown in Fig. 5 (a) was performed for 1 minute using the electrolysis system shown in Fig. 1. The current at that time was 0.4 AZ to be treated, and the voltage was 2.4 V.

 The cathodic treatment was performed for 3 minutes in the same bath, using the object to be treated as the cathode and iron as the anode, using the same electrolytic system current application method as for the anodizing. The current at that time was 0.4 A / treatment agent, and the voltage was 2.4 V. The treated agent with the film formed is washed with water and dried, then immersed in a solution of 5% sodium stearate at 80 ° C for 10 minutes, and a metal seggen film of zinc stearate is applied on the surface. I got

 As shown in Fig. 36, this material was rolled in the direction of reducing the thickness at the center. >

 Rolling is performed with a press of 200 tons, applying a load of 60 tons and 70 tons at a time, and moving by 1 mm per turn, reaching a total of 6 times of rolling. The thin plate thickness (ti) was measured.

 Figure 37 shows the results.

(A) in FIG. 37 shows the result of the chemical conversion treatment of the present invention. As a comparative example of rolling, no conversion coating was formed and processing oil (Sugimura Chemical Co., Ltd.) The case where only 0 0 — A) was used is shown in (B) of FIG. · From Fig. 37, it was found that the use of the chemical conversion coating of the present invention for the rolling of magnetic materials is superior to the conventional processing oil alone.

 (Example 13)

 As a material to be treated, a stator core 40 of an automotive alterna- ble shown in Fig. 38 was used.

 The core 40 is formed by laminating a plurality of segments 41 each having a thickness of 0.5 mm.

During processing of the core 4 0,-phosphate salt chemical conversion treatment ^{bath, Z n 2+ 5 g / 1} , H 2 P 0 -. 4 2 5 g / 1, N i 0 8 g / 1, N 0 A composition having a composition of _{3 to} 16 g / 1 and F-0. Lg Zl was used.

 The pH of the treatment bath is 3.30, the ORP is 540 to 550 mV, the temperature is 28 ° C, the total acidity is 35 pt, the free acidity is 0.2 pt, and the accelerator concentration : Was 4-6 pt. Further, the transparency of the treatment bath was 30 cm or more, and the treatment bath did not contain sludge.

 In the electrolysis treatment, the treatment agent is first used as the anode, iron is used as the cathode, and the constant current electrolysis shown in Fig. 1 and Fig. Run for 5 minutes. Subsequently, using the same treatment bath, a main electrolytic system is formed using zinc and iron as anodes with the material to be treated as a cathode.

 Then, as in the apparatus shown in FIG. 4, an electrolytic treatment system is formed, and a cathodic treatment is performed. The cathodic treatment is performed by current scanning electrolysis, and 0 A-* 1.25 A is applied between the electrodes of the zinc electrolytic system for 40 seconds to produce the object to be treated. And went. In addition, it was gradually applied for 40 seconds to make the object to be treated 0 A → 0.4 A between the electrodes of the iron electrolytic system. The electrolysis of zinc and iron was carried out simultaneously. Then, the same operation was performed for 20 to 30 cycles, and the cathode treatment was performed for a total of 13 to 20 minutes.

By this treatment, a phosphate conversion film having a thickness of 20 to 25 m was formed on the surface of the object to be treated. (The film thickness is manufactured by Chit Kagaku Corporation, electromagnetic film thickness meter LE — It is a value measured at 300. ) The insulation resistance of this film was measured with a super insulation meter SM-8219 manufactured by Toa Denpa Co., Ltd. The measurement was performed by bringing the probe (positive electrode, negative electrode) of the super insulation meter into contact with the light surface. As a result, the surface of the workpiece had an insulation resistance of 500 V DC or more.

 The workpiece was then electrocoated with Nippon Paint @ Power TOP, U-600E so that the thickness of the organic film was 40 to 50 μm. The baking was performed at 180 ° C for 30 minutes.

 In this way, an alternator stator core 40 having a total insulation thickness of 50 to 70 in was obtained.

 Using the stay core 40 of the embodiment 13, mechanical winding was performed on the slot section 44.

 The winding 42 automatically winds 12 windings of 1.4 mm in diameter per Z slot.

 Figure 39 shows the inside of the slot part 44 after the winding 42 is processed.

 After the winding 42 was machined, a page 43 was provided to prevent the winding 42 from falling off.

 After that, apply AC 600 V to check the ground (breakage of insulation) between the winding part 42 and the stay core core 40 body, or apply this product to withstand voltage 600 V (AC). It was able to withstand the mechanical winding process described above.

 The conventional electroless chemical conversion treatment, which was not the chemical conversion treatment of Example 13, and was subjected to the same electroplating coating as in Example 13 resulted in the destruction of the entire insulation by the mechanical winding process described above. The AC 600 V could not be maintained. Thus, it can be said that the inorganic insulating film of the present invention is effective for alternator insulating treatment.

Further, as shown in FIG. 40, the conventional alternator stator core 45 is provided with a paper insulator (organic insulating paper) 47 between the core 45 and the winding 46. Thereafter, the winding 46 is sealed with a page 48. However, the thickness of the paper insulation was 2 0 zm, which hinders downsizing of the core 40. In addition, there is a problem that the paper insulation breaks at less than 200 m due to mechanical winding.

 Therefore, the insulation treatment of Example 13 can be made thinner than the conventional method, with a film thickness of 50 to 70 im, and the insulation effect is sufficient.

 Therefore, by adopting the phosphate conversion treatment method of the present invention in a place requiring insulation, such as the core 40, it is possible to abolish the conventional insulation member. It can be used for various applications.

 'Finally, Table 4 summarizes the electrochemical differences between the electrolytic treatment in the transparent treatment bath of the present invention and the conventional electroless treatment.

(Hereinafter the margin)

Table 4 Electrolytic treatment method Electroless treatment method Electrification of treatment bath High Low

Electron energy from an external power supply Electron is supplied only at the level of dissolution of iron Only with iron ion Fe ³⁺ with Fe without F e ^{3 +} without Form Fe ^{z +} with Fe ²⁺ with F e ^{2 +} with Treatment Bath redox 5 δ 0 m V 5 6 0 m V

Original potential (Ag C or more and below 560 mV or less 1 electrode potential)

As shown in Table 4 above, in the electrolytic treatment method (transparent bath), there are cases where the pressure is 0 RP 560 mV or more and cases where it is 56 OmV or less.

In order to secure a processing bath of ORP 56 OmV or higher, since the processing bath contains paramagnetic ions (Fe ³⁺ ) at ORP 56 OmV or higher, Care must be taken.

That is, the magnetic field does not affect the circulation path. When a magnetic field acts on the treatment baths, it acts on the paramagnetic component (F e ³⁺ ), such that F e ³⁺ dissolves and cannot be present in each treatment bath, and It does not contain ^{Fe 3+} . Therefore, 0 RP is necessarily less than 560 mV c

0 and a this RP 5 6 O m V or more baths containing the F e ^3+, compared with conventional electroless bath (F e ³⁺ containing no bath), electrolytic qualitative tendency is strong. It is considered that the property facilitates the formation of a chemical conversion film on a metal material having a passivation film on the surface such as aluminum or stainless steel. In other words, it is considered that the electrolyte has a strong tendency to act on the passive film on the surface by the electrolytic treatment, so that dissolution and film formation can be performed. The film formed from a bath of 56 OmV or less does not contain ^{Fe3 +} and has the same properties as conventional electroless chemical conversion films. However, the film thickness can be controlled by the method of the present invention.

 In addition, the following is a description of the essential points of the electrolysis treatment according to the present invention. The point about the electrolysis of the present invention is

 ① Electrolytic reaction between the “main electrolytic system” and the “sub-electrolytic system”. Separating the systems and controlling the Fe content involved in film formation.

 ② Performing current scanning electrolysis

 The reason is described again below.

 Reason for ①

It is necessary to control the Fe ion involved in the electrolytic reaction, and the “sub-electrolyte system j plays the role. In particular, in the cathodic treatment, the object to be treated is a cathode. It is important how the Fe ions are dissolved and precipitated on the surface of the workpiece. When using Fe as an electrode material, it is important how to apply current and voltage to the Fe electrode specifically. The secondary electrolytic system is effective mainly for controlling the dissolution and precipitation of iron ions and for forming a good film in combination with the main electrolytic system.

 Reason for ②

 This is a necessary condition for thickening the coating.

 An example of current scanning electrolysis is shown in FIG.

 Fig. 41 shows the voltage change I of the "main electrolytic system" between the material 7 to be treated and the electrode 6 when the current shown in Fig. 5 (c) is applied in the device of Fig. 2 (from the electrode 6 to the Voltage change in the “sub-electrolysis system” between the material 7 and the electrodes 10 and 11 (the direction from the material 7 to the electrodes 10 and 11 is positive). ).

 Here, Fig. 41 shows that the current applied from the external power supply to the main electrolytic system is 0 A → 4.0 AZ cnM sequentially over 300 seconds, as shown in Fig. 5 (c). Under such conditions, as in 41, during the first 90 to 100 seconds of the application of the current for 300 seconds, the current is applied from the outside, The voltage change I indicates a negative voltage, and the voltage change H indicates a value of almost zero.

 This means that if no current is applied, or if the current is applied but is small, the potential of the electrode in the chemical conversion bath is

 Object to be processed ^ Counter electrode of secondary electrolytic system (F e · Ni)> Counter electrode of main electrolytic system (Z n)

 It indicates that

That is, since the chemical conversion bath itself is an electrolytic bath, a potential difference is generated between the electrodes (materials) immersed in the bath. And apply a current It can be said that the state of the bath that reflects the potential difference when it is not present is the most stable state as a chemical conversion bath.

 During the period in which the voltage change I in Fig. 41 indicates the negative potential, the anode (Zn) and the cathode (coated) of the main electrolysis system A regardless of the input of current from the external power supply. No current flows between the processed products. However, the current can be considered to be acting on the components in the solution. Such action on the components in the solution is very important for forming a dense film. Voltage change I in Fig. 41 indicates that the current flows through the main electrolytic system and a film is formed through such a course.

 Then, at the same time as the current flows through the voltage change I, the voltage of the voltage change II in FIG. 41 becomes negative, but the current from the anode of the electrode 6 in FIG. This shows that it acts on the counter electrode of electrodes 10 and 11 in Fig. 2 of B.

 That is, the current flowing from the anode of the electrode 6 in FIG. 2 passes through the electrodes 11 and 12 in FIG. 2, passes through the diode D, and flows to the object to be processed, indicating a negative potential. . Thus, the voltage changes I and H are linked.

 This indicates that the electrolysis of Zn in the main electrolysis system A controls the electrolysis of Fe and Ni in the sub electrolysis system B. Then, a film is formed by these repetitions.

 As described above, in the apparatus of Fig. 2, by performing the cathodic current-scanning electrolysis in the main electrolysis system as shown in Fig. 5 (c), the bath always returns to an energy stable state. Starting from that state, the film can be formed, and the dissolution of the electrodes 10 and 11 of the secondary electrolytic system B can be controlled by the electrolysis of the electrode 6 of the main electrolytic system A. In addition, excessive dissolution of the electrodes 10 and 11 can be controlled. Therefore, it is possible to form a dense film on the material to be treated.

When comparing the electrolysis method with the constant current electrolysis shown in Fig. 5 (a), This is clear.

 In the method shown in Fig. 5 (a), the current immediately reaches the predetermined set voltage. Then, the electrolysis reaction is performed, but it is the same as that of the formation of a good conductor film such as electroplating, which is clearly different from the method of Fig. 5 (c). In the method of Fig. 5 (a), the energy breakdown associated with electrolysis always shows the maximum voltage of the voltage change I in Fig. 41. Therefore, the solution is always in a state where a strong current is applied. Then, a large amount of current flows to a predetermined place on the object to be processed (for example, an edge portion), and as a result, the adhesiveness of such a place is deteriorated.

 In the current scanning electrolysis of the present invention, in the film form or in relation to the components in the solution, the electrolytic film forming reaction of always starting from an initial state in which the solution is not electrolyzed is performed by repeating and carrying out the reaction. Are very different. In addition, such measures greatly affect the adhesion of the coating.

 As described above, the phosphoric acid conversion treatment method according to the present invention is a phosphoric acid conversion treatment method used as a pretreatment before cold forging a metal material such as a steel plate.

Claims

The scope of the claims

 1. Bring a conductive metal material into contact with a phosphoric acid conversion treatment solution containing at least ion phosphate, oxo acid ion containing nitrogen, and metal ion forming a chemical conversion film. A method for forming a phosphate conversion film on the surface of the metal material, comprising:

 The phosphatization bath is a bath that does not contain solid components other than inevitable components, and the metal material is subjected to electrolytic treatment in the phosphatization bath. Characteristic phosphoric acid conversion treatment method.

 2. The phosphoric acid conversion treatment method according to claim 1, wherein the metal material is used as an anode for electrolytic treatment.

 3. The phosphoric acid conversion treatment method according to claim 1, wherein the metal material is used as a cathode and the film-forming metal is used as an anode for electrolytic treatment.

 4. The method according to claim 1, wherein first, the metal material is subjected to an electrolytic treatment using an anode, and then the electrolytic treatment is performed using the metal material as a cathode.

15 Phosphoric acid conversion treatment method.

 5. The phosphoric acid conversion treatment method according to claim 1, wherein the electrolytic treatment is a method of applying a current.

 6. The phosphate conversion treatment according to claim 1, wherein the oxidation-reduction potential of the chemical conversion bath is in the range of 250 to 65OmV (silver-silver chloride electrode potential). Method.

 7. The phosphoric acid conversion treatment method according to claim 1, wherein the metal material is at least one of copper, aluminum, and iron.

 8. At least one of steel, copper, and aluminum materials should be added to the phosphatization bath containing ion phosphate, ion nitrate, conversion film forming metal ion, and oxidizing agent.

25. A method for forming a phosphoric acid conversion coating on the metal surface by contacting 25 components to cause a coating formation reaction,

The stabilizing means for thermodynamically stabilizing the energy state of the phosphatization bath as a liquid as a whole of the phosphatization bath, A phosphoric acid conversion treatment method, wherein the metal material is electrolytically treated in the phosphoric acid conversion treatment bath while the energy state is stably maintained.

 9. The phosphoric acid conversion treatment bath is obtained by taking out a part of the phosphoric acid conversion treatment bath from a bath having the phosphoric acid conversion treatment bath, 9. The phosphatization treatment according to claim 8, wherein the energy state as a liquid is thermodynamically stabilized, and the energy state is stabilized by a stabilizing means, and then the liquid state is returned to the bathtub. Method.

 10. The stabilizing means is characterized in that the phosphate chemical conversion treatment bath thermodynamically stabilizes the internal energy of the liquid while maintaining the state of only the liquid. The phosphoric acid liquid conversion treatment method according to claim 8.

11. The phosphoric acid conversion treatment method according to claim 8, wherein the electrolytic treatment is a method of applying a current. 12. The phosphate conversion chemical according to claim 8, wherein the oxidation-reduction potential of the chemical conversion treatment bath is in the range of 250 to 65OmV (silver-silver chloride electrode potential). Processing method.

 13 3. Iron, steel, copper, and aluminum were added to a phosphatization bath maintained at 40 ° C or less containing ion phosphate, ion nitrate, metal ions forming a chemical film, and an oxidizing agent. A method for forming a phosphoric acid chemical conversion treatment film on the surface of steel, copper, and aluminum by contacting and causing a film formation reaction between the phosphoric acid chemical treatment bath and the iron-based material;

A part of the phosphatization bath is taken out, and a circulating route is provided to return the taken-out phosphating bath again. 0 _2, a 1 ₂ 0 ₃ and the provision of the full I filter consisting of inorganic material having as a basic structure compound and Moni,-phosphate salt chemical conversion treatment method of the Toku徵that you electrolytically treating the metal material.

1. The electrolytic treatment is a method of applying a current. 14. The phosphoric acid conversion treatment method according to claim 13.

 15. The phosphate chemical conversion according to claim 13, wherein the oxidation-reduction potential of the chemical conversion treatment bath is in the range of 250-650 mV (silver-silver chloride electrode potential). Processing method.

16. At least one of steel, copper, and aluminum is added to a phosphatization bath containing ion phosphate, ion nitrate, conversion film forming metal ion, and an oxidizing agent. A method of forming a phosphoric acid conversion coating film on the metal surface by causing the film to undergo a film forming reaction.

 The phosphoric acid conversion treatment (film formation) reaction in the phosphoric acid conversion treatment bath is performed by a solid-liquid interphase electrochemical (oxidation-reduction) on the metal surface accompanied by a phase transition only on the metal surface. ) A phosphoric acid conversion treatment method characterized in that only a reaction and an electrochemical reaction between a liquid phase and a liquid phase without phase transition in the phosphoric acid conversion treatment bath.