Title of invention: Method for producing chemical conversion treatment alloy material and chemical conversion treatment liquid regenerator used for production method for chemical conversion treatment alloy material
Technical field
[0001]
　The present disclosure relates to a chemical conversion treatment alloy material manufacturing method and a chemical conversion treatment liquid regenerating apparatus used in the chemical conversion treatment alloy material manufacturing method.
Background technology
[0002]
　Chemical conversion treatment is carried out for the purpose of imparting properties such as corrosion resistance, seizure resistance, lubricity, and coating adhesion to the surface of the alloy material. The chemical conversion treatment includes, for example, phosphate treatment, oxalate treatment, and chromate treatment. Among the chemical conversion treatments, the oxalate treatment is carried out for the purpose of enhancing the lubricity and seizure resistance of the alloy material surface. The oxalate film formed on the surface of the alloy material by the oxalate treatment enhances the adhesion of the lubricating film formed thereon to the surface of the alloy material. As a result, the oxalate film enhances the lubricity and seizure resistance of the alloy material surface.
[0003]
　For example, Japanese Unexamined Patent Publication No. 2006-37933 (Patent Document 1) discloses a technique for forming a high Cr steel piston having excellent seizure resistance by forming an oxalate film on the surface of a piston for an internal combustion engine. Disclose.
[0004]
　The oxalate treatment is usually performed by immersing the alloy material in an oxalic acid treatment liquid containing oxalate ions and allowing the surface of the alloy material to react with the oxalic acid treatment liquid. When the oxalate treatment is performed on a plurality of alloy materials, the oxalic acid treatment liquid is usually used continuously. As the number of alloy materials continuously treated increases, the chemical conversion treatability decreases. If the chemical conversion processability is lowered, the oxalate film may be poorly formed. Further, it is known that when the alloy material is an alloy material containing a large amount of Cr, that is, a so-called difficult-to-form chemical material, the chemical conversion treatability is deteriorated even when the oxalic acid treatment liquid is used less frequently. In this case, defective formation of the oxalate film may occur. Therefore, various studies have been conducted in order to suppress deterioration of chemical conversion treatability.
[0005]
　JP-A-2003-171777 (Patent Document 2), JP-A-2-149677 (Patent Document 3) and JP-A-2014-43606 (Patent Document 4) disclose oxalic acid capable of suppressing deterioration of chemical conversion treatability. Propose treatment liquid. On the other hand, Japanese Unexamined Patent Publication No. 62-199778 (Patent Document 5) and Japanese Unexamined Patent Publication No. 6-220651 (Patent Document 6) propose a chemical conversion treatment method capable of suppressing a decrease in chemical conversion treatability.
[0006]
　The treatment solution for forming an oxalate film of Patent Document 2 contains 0.03 to 1.0 wt% of a polyoxyethylene polyoxypropylene block polymer obtained by adding 20 to 50 wt% of ethylene oxide to propylene glycol in the total molecular weight. It is characterized in that it is contained. It is described in Patent Document 2 that this makes it possible to reduce the defective rate of the product and suppress the decrease in the life of the oxalate coating solution in the method of cold drawing a stainless steel pipe.
[0007]
　The chemical conversion treatment liquid for cold working of stainless steel in Patent Document 3 contains oxalic acid, and phosphoric acid is contained so that the phosphate ion concentration in the treatment liquid is 0.03 to 0.6 g/L. Is characterized by. According to Patent Document 3, it is possible to obtain a chemical conversion treatment liquid capable of forming a chemical conversion coating capable of maintaining good baking resistance on the surface of stainless steel even if the composition balance of the chemical conversion treatment liquid is slightly disturbed. Has been done.
[0008]
　The oxalic acid conversion treatment method of Patent Document 4 is characterized in that a chemical conversion treatment is performed by adding sulfite as an accelerator to the oxalic acid conversion treatment solution. It is described in Patent Document 4 that this makes it possible to form an oxalate film on a material having high corrosion resistance, such as a highly corrosion-resistant stainless steel pipe.
[0009]
　The method for forming an oxalate film on Cr-Ni stainless steel in Patent Document 5 is characterized in that a sulfuric acid treatment is performed immediately before the oxalate film formation treatment. As a result, the reactivity between the raw material and the oxalate treatment liquid becomes high, and it is possible to efficiently perform the oxalate film formation treatment even on the high Ni steel, which was conventionally impossible to perform the oxalate film formation treatment, Is described in Patent Document 5.
[0010]
　In the lubrication method for a highly corrosion-resistant metal material of Patent Document 6, after performing shot blast treatment with steel grains on the surface of the metal material, an oxalate film is formed without performing pickling treatment, and then lubrication treatment is performed. It is characterized by According to this, Patent Document 6 describes that even with a highly corrosion-resistant metal material that is difficult to be subjected to chemical conversion treatment, a chemical conversion coating can be sufficiently formed and appropriate lubrication treatment can be performed. ..
Prior art documents
Patent literature
[0011]
Patent Document 1: Japanese Patent Laid-Open No. 2006-37933
Patent Document 2: Japanese Patent Laid-Open No. 2003-171777
Patent Document 3: Japanese Patent Laid-Open No. 2-149677
Patent Document 4: Japanese Patent Laid-Open No. 2014-43606
Patent Document 5: Japanese Patent Laid-Open No. 2004-43606 Akira 62-199778 JP
Patent Document 6: JP-A 6-220651 JP
Summary of the invention
Problems to be Solved by the Invention
[0012]
　By using the above-mentioned technique, it is possible to suppress deterioration of chemical conversion treatment property. On the other hand, the deterioration of the chemical conversion treatment may be suppressed by a method other than the above technique.
[0013]
　An object of the present disclosure is to suppress a decrease in chemical conversion treatability even when subjected to repeated chemical conversion treatment, a method for producing a chemical conversion treated alloy material, and to produce a chemical conversion treated alloy material using an oxalic acid treatment liquid subjected to repeated chemical conversion treatment. Even in such a case, it is an object of the present invention to provide a chemical conversion treatment liquid regenerator capable of suppressing a decrease in chemical conversion treatment of an alloy material.
Means for solving the problem
[0014]
　The chemical conversion treatment alloy material manufacturing method of the present disclosure includes a chemical conversion treatment step and a treatment liquid regeneration step. In the chemical conversion treatment step, the alloy material is immersed in an oxalic acid treatment liquid containing oxalate ions and fluorine ions for chemical conversion treatment. In the treatment liquid regeneration step, the oxalic acid treatment liquid during the chemical conversion treatment and/or the oxalic acid treatment liquid after the chemical conversion treatment is irradiated with light.
[0015]
　The chemical conversion treatment liquid regeneration device of the present disclosure includes a treatment liquid regeneration tank and a light irradiation device. The treatment liquid regenerating tank can store the oxalic acid treatment liquid during or after the chemical conversion treatment of the alloy material. The oxalic acid treatment liquid contains oxalate ions and fluorine ions. The light irradiation device includes one or a plurality of light source members. At least a part of the light source member is arranged inside or outside the treatment liquid regenerator. The light irradiation device can irradiate the oxalic acid treatment liquid during or after the chemical conversion treatment with light.
Effect of the invention
[0016]
　According to the method for producing a chemical conversion treatment alloy material of the present disclosure, deterioration of chemical conversion treatability is suppressed even when repeated chemical conversion treatment is performed. The chemical conversion treatment liquid regeneration device of the present disclosure can suppress the decrease in the chemical conversion treatment property of the alloy material even when the chemical conversion treatment alloy material is manufactured using the oxalic acid treatment liquid subjected to the repeated chemical conversion treatment.
Brief description of the drawings
[0017]
FIG. 1 is a diagram showing the content of trivalent iron ions in an oxalic acid treatment liquid after being used for chemical conversion treatment of an alloy material before and after irradiation with ultraviolet rays.
FIG. 2 is a diagram showing the potential of the surface of an alloy material when chemical conversion treatment is performed using an unused oxalic acid treatment liquid, a used oxalic acid treatment liquid, and a regeneration treatment liquid.
FIG. 3 is a schematic view of an example of a chemical conversion treatment liquid regenerator used in the method for producing a chemical conversion treatment alloy material according to the present embodiment.
FIG. 4 is a schematic diagram of a chemical conversion liquid regenerator according to another embodiment different from FIG.
FIG. 5 is a schematic diagram of a chemical conversion treatment liquid regenerator according to another embodiment different from FIGS. 3 and 4.
FIG. 6 is a schematic diagram of a chemical conversion liquid regenerator according to another embodiment different from those of FIGS. 3 to 5.
FIG. 7 is a schematic diagram of a chemical conversion liquid regenerator according to another embodiment different from those of FIGS. 3 to 6.
FIG. 8 is a schematic diagram of a chemical conversion treatment liquid regenerator according to another embodiment different from those of FIGS. 3 to 7.
FIG. 9 is a schematic diagram of a chemical conversion treatment liquid regenerator according to another embodiment different from those of FIGS. 3 to 8.
FIG. 10 is a schematic diagram showing an example of a treatment liquid regenerator tank whose bottom surface is inclined.
FIG. 11 is a schematic diagram showing an example of a treatment liquid regenerating tank different from that in FIG.
FIG. 12 is a schematic diagram showing an example of a treatment liquid regenerator that is different from FIGS. 10 and 11.
FIG. 13 is a schematic diagram of a chemical conversion liquid regenerator according to another embodiment different from those of FIGS. 3 to 12.
FIG. 14 is a schematic view of a chemical conversion treatment liquid regenerator according to another embodiment different from those of FIGS. 3 to 13.
FIG. 15 is a plan view of the treatment liquid regenerating tank, showing the arrangement of the flow direction changing members.
FIG. 16 is a plan view of the treatment liquid regenerator, showing an arrangement of flow direction changing members, which is different from that in FIG.
FIG. 17 is a schematic view of a chemical conversion treatment liquid regenerator according to another embodiment different from those of FIGS. 3 to 16.
FIG. 18 is a schematic diagram showing an example of arrangement of light source members.
FIG. 19 is a schematic diagram showing an example of the arrangement of light source members, which is different from FIG.
FIG. 20 is a schematic diagram showing an example of an arrangement of light source members, which is different from FIGS. 18 to 19.
FIG. 21 is a schematic diagram showing an example of the arrangement of light source members, which is different from FIGS. 18 to 20.
FIG. 22 is a schematic diagram showing an example of the shape of the treatment liquid regenerating tank.
FIG. 23 is a schematic diagram showing an example of the shape of the treatment liquid regenerator, which is different from FIG. 22.
FIG. 24 is a schematic diagram showing an example of the shape of the treatment liquid regenerator, which is different from FIGS. 22 to 23.
FIG. 25 is a schematic diagram showing an example of the shape of the treatment liquid regenerating tank, which is different from FIGS. 22 to 24.
FIG. 26 is a schematic diagram of a chemical conversion treatment liquid regenerator according to another embodiment, which is different from FIGS. 3 to 25.
FIG. 27 is a schematic diagram of a chemical conversion treatment liquid regenerator according to another embodiment, which is different from FIGS. 3 to 26.
MODE FOR CARRYING OUT THE INVENTION
[0018]
　The oxalate film is a film composed of iron (II) oxalate (chemical formula: Fe(COO) 2 ) and impurities. The oxalate film is formed by the reaction of iron ions eluted from the alloy material with oxalate ions in the oxalic acid treatment liquid on the surface of the alloy material. The production process of iron (II) oxalate in the chemical conversion treatment is specifically shown by the following reaction formula.
　￫ Fe Fe 2Tasu Tasu 2E - · · ·
　(1) (COOH) 2　￫ (COO) 2 2Tasu 2H Tasu · · ·
　(2) 2H Tasu Tasu 2E -　￫ H 2￪ · · ·
　(3) (COO) 2 2- + Fe 2+　→ Fe(COO) 2 (4)
[0019]
　Fluorine ions are added to the oxalic acid treatment liquid to accelerate the above reaction. Fluorine ions have an etching function. When fluorine ions are contained in the oxalic acid treatment liquid for chemical conversion treatment, the fluorine ions destroy the oxide film (passive film) formed on the surface of the base material during the manufacturing process of the alloy material. As a result, the formation of an oxalate film is promoted. Furthermore, an oxalate film can be formed even on a stainless alloy material having a passive film with high corrosion resistance.
[0020]
　Conventionally, it has been known that the oxalic acid treatment liquid is deteriorated by repeatedly using the oxalic acid treatment liquid containing oxalate ions and fluorine ions. If the oxalic acid treatment liquid deteriorates, the chemical conversion treatability will decrease. If the chemical conversion processability is lowered, the oxalate film may be poorly formed. Further, it is known that the alloy material containing a large amount of Cr, that is, the so-called difficult-to-form chemical material, has low chemical conversion treatability even when the oxalic acid treatment liquid is used less frequently.
[0021]
　Conventionally, these problems have been dealt with by adding an etching agent such as sodium hydrogen fluoride to the oxalic acid treatment liquid or raising the treatment temperature. In addition, when it is not possible to deal with these methods, the entire oxalic acid treatment liquid has been discarded and replaced. For difficult-to-form materials, measures have been taken to impart surface roughness to the alloy material surface or to impart iron content to the alloy material surface. On the other hand, the cause of the deterioration of the oxalic acid treatment liquid and the poor formation of the oxalate film has not been investigated in detail.
[0022]
　Therefore, the present inventors have investigated in detail the causes of the deterioration of the oxalic acid treatment liquid and the deterioration of the chemical conversion treatability. As a result, the following findings, which had not been known so far, were obtained.
[0023]
　During the chemical conversion treatment, iron is dissolved from the base material and iron ions are generated. At this time, a part of the iron of the base material is dissolved as divalent iron ions (Fe 2+ ) according to the above-mentioned formula (1) . The divalent iron ion reacts with the oxalate ion to produce iron (II) oxalate. Iron (II) oxalate is a sparingly soluble salt. Therefore, when iron is dissolved as divalent ions from the surface of the alloy material and reacts with oxalate ions, iron (II) oxalate is immediately deposited on the surface of the alloy material. The deposited iron(II) oxalate forms an oxalate film.
[0024]
　On the other hand, part of the iron eluted from the base material exists in the oxalic acid treatment liquid as trivalent iron ions (Fe 3+ ). Trivalent iron ions do not contribute to the formation of the oxalate film. That is, not all the iron ions eluted from the base material are consumed for forming the oxalate film. A part of the iron ions is not involved in the formation of the oxalate film and is present in the oxalic acid treatment liquid.
[0025]
　The trivalent iron ion reacts with the fluorine ion as in the following formula (5) to form a complex (chemical formula: [FeF 6 ] 3 − ). When the complex is generated, the etching action disappears and the destruction of the oxide film (passive film) is suppressed.
　Fe 3+ +6F -　→ [FeF 6 ] 3 -... (5)
[0026]
　If the oxalic acid treatment liquid is repeatedly used and a plurality of alloy materials are immersed in the same oxalic acid treatment liquid, the iron ion content of the oxalic acid treatment liquid increases. If the iron ion content of the oxalic acid treatment liquid increases, the complex formation of iron ions and fluorine ions will proceed. That is, if the oxalic acid treatment liquid is repeatedly used, the etching action is reduced. As a result, the destruction of the oxide film (passive film) is suppressed, and the chemical conversion treatability deteriorates. The present inventors have for the first time elucidated that this is the cause of deterioration of the oxalic acid treatment liquid.
[0027]
　Further, an alloy material containing a large amount of Cr, that is, a so-called chemical conversion material, has a passivation film having extremely high corrosion resistance on the surface. Therefore, when the oxalate treatment is performed on the difficult-to-form material, it is necessary to more actively maintain the function of etching fluorine ions. However, if iron is dissolved to form a complex with fluorine ions during the oxalate treatment, the number of fluorine ions is reduced, and the etching function is reduced, so that it becomes difficult to destroy the passive film. As a result, poor oxalate film formation occurs.
[0028]
　As described above, it was found that the cause of the decrease in chemical conversion treatability was a decrease in the function of etching fluorine ions. Therefore, the present inventors have studied a method for recovering and maintaining the function of etching fluorine ions in the oxalic acid treatment liquid. As a result, the following findings were obtained.
[0029]
　As described above, the iron ion in the oxalic acid treatment liquid reacts with the fluorine ion to form a complex. Here, the present inventors considered that if the iron ion content of the oxalic acid treatment liquid could be reduced, the reaction with fluorine ions (complex formation) could be suppressed. As a result of various studies, the present inventors have newly discovered that the iron ion content of the oxalic acid treatment liquid can be reduced by a simple method of irradiating the oxalic acid treatment liquid with light.
[0030]
　FIG. 1 shows an oxalic acid treatment liquid after being used for chemical conversion treatment of an alloy material before and after irradiation with ultraviolet rays (a chemical conversion treatment in which a stainless steel pipe is immersed in a treatment tank containing about 15000 L of the oxalic acid treatment liquid for about 2 hours) It is a figure which shows the trivalent iron ion content of the oxalic acid treatment liquid after a cumulative total of about 25,000 m 2 of surface area conversion . The vertical axis of FIG. 1 represents the trivalent iron ion content (g/L) of the oxalic acid-treated solution. The left side of FIG. 1 shows the trivalent iron ion content of the oxalic acid-treated solution before ultraviolet irradiation and the right side after ultraviolet irradiation, respectively. It can be seen from FIG. 1 that the trivalent iron ion content is reduced by irradiating the oxalic acid-treated solution after use with ultraviolet rays.
[0031]
　Subsequently, the present inventors performed a chemical conversion treatment on the alloy material using an oxalic acid treatment liquid after ultraviolet irradiation (hereinafter, simply referred to as a regeneration treatment liquid). FIG. 2 shows an unused oxalic acid treatment liquid (indicated as an unused liquid in FIG. 2), an oxalic acid treatment liquid after use (indicated as a post-use liquid in FIG. 2), and an oxalic acid treatment liquid after use. It is a figure which shows the electric potential of the alloy material surface at the time of a chemical conversion treatment using the oxalic acid treatment liquid (it is shown as the reproduction|regeneration treatment liquid in FIG. 2) which irradiated ultraviolet rays. The horizontal axis of FIG. 2 represents the reaction time (minutes). The vertical axis of FIG. 2 shows the potential (VvsSCE) of the surface of the alloy material. When the dissolution reaction of the oxide film on the surface of the alloy material is proceeding and when the dissolution reaction of the base material is proceeding, the surface potential of the alloy material becomes low (becomes base). That is, when the formation reaction of the oxalate film is in progress, the potential of the surface of the alloy material is kept low (base). On the contrary, when the formation reaction of the oxalate film is not progressing, the state where the potential of the alloy material surface is high (noble) is maintained.
[0032]
　With reference to FIG. 2, when an unused oxalic acid treatment liquid (unused liquid in FIG. 2) is used, the potential is high at the very early stage of the reaction. This is because the oxide film on the surface of the alloy material is dissolved. However, immediately after that, the potential drops and the low state of about −0.40 V is maintained for about 200 minutes. On the other hand, when the oxalic acid-treated solution after use (the solution after use in FIG. 2) was used, the potential remained relatively high at about 0.00 V from the initial reaction to the end of the test (about 200 minutes). Maintained. When the oxalic acid treatment liquid (regeneration treatment liquid) after irradiation with ultraviolet rays is used, the potential is relatively high at the very beginning of the reaction. However, immediately after that, the potential dropped and reached a potential equivalent to that of the unused oxalic acid treatment liquid in about 20 minutes. Then, the low potential state was maintained for about 200 minutes. From the above, by irradiating the used oxalic acid treatment liquid with ultraviolet rays, the chemical conversion treatability was restored to the same level as the unused oxalic acid treatment liquid, and high chemical conversion treatability was maintained.
[0033]
　It is considered that the reason why the chemical conversion treatment property is restored and maintained to the same level as the unused oxalic acid treatment liquid by irradiating the used oxalic acid treatment liquid with ultraviolet rays is as follows.
[0034]
　When the complex generated by the formula (5) is irradiated with ultraviolet rays, the trivalent iron ion is reduced to divalent as shown in the formula (6). At this time, fluorine ions are released from the complex. The released fluorine ions restore the function of etching and contribute to the destruction of the oxide film (passive film). As a result, the chemical conversion treatability of the oxalic acid treatment liquid after use is restored.
　[FeF 6 ] 3-　Tasu E -　￫ Fe 2Tasu Tasu 6F - · · · (6)
[0035]
　Further, the divalent iron ion reacts with the oxalate ion according to the formula (4) to form a sparingly soluble iron (II) oxalate. At this time, fluorine ions are further released from the complex. The released fluorine ions regain the function of etching. From the above, the fluorine ions are released by the reduction of trivalent iron ions by the irradiation of ultraviolet rays and the subsequent formation of the sparingly soluble salt. Therefore, by irradiating with ultraviolet rays, the chemical conversion treatability of the oxalic acid treatment liquid after use is restored to the same level as that of the unused oxalic acid treatment liquid.
[0036]
　On the other hand, trivalent iron ions eluted from the base material react with oxalate ions to produce iron (III) oxalate (chemical formula: Fe 2 (C 2 O 4 ) 3 ). Iron (III) oxalate has a property of being decomposed into lightly soluble iron (II) oxalate and carbon dioxide by light. This reduces the trivalent iron ion content of the oxalic acid treatment liquid. As a result, the reaction between fluorine ions and iron ions is suppressed. That is, the fluorine ion etching activity is maintained and high chemical conversion processability is maintained.
　2[Fe(C 2 O 4 ) 3 ] 3 -　> 2Fe(COO) 2 +2CO 2 +3(COO) 2 2 -... (7)
[0037]
　From these results, the present inventors have found a method for producing a chemical conversion treatment alloy material, which can maintain the function of etching fluorine ions by a simple method of irradiating light and suppress a decrease in chemical conversion treatment property. The manufacturing method of the present disclosure does not necessarily require addition of components of the oxalic acid treatment liquid (particularly, an etching agent such as sodium hydrogen fluoride), discarding and replacement of the oxalic acid treatment liquid. Further, even when a difficult-to-form material is used, additional steps such as surface roughness application are not always necessary.
[0038]
　Furthermore, the present inventors have proposed, for example, a treatment liquid regenerating tank capable of containing an oxalic acid treatment liquid during or after chemical conversion treatment of an alloy material and an oxalic acid treatment liquid during or after chemical conversion treatment. It was thought that any device provided with a light irradiation device capable of irradiating light could be used in the above manufacturing method.
[0039]
　The manufacturing method of the chemical conversion treatment alloy material of the present disclosure completed based on the above findings includes a chemical conversion treatment step and a treatment liquid regeneration step. In the chemical conversion treatment step, the alloy material is immersed in an oxalic acid treatment liquid containing oxalate ions and fluorine ions for chemical conversion treatment. In the treatment liquid regeneration step, the oxalic acid treatment liquid during the chemical conversion treatment and/or the oxalic acid treatment liquid after the chemical conversion treatment is irradiated with light.
[0040]
　The method for producing a chemical conversion treatment alloy material according to the present disclosure includes a treatment liquid regeneration step. The treatment liquid regeneration step restores the function of etching fluorine ions and reduces the iron ion content of the oxalic acid treatment liquid. If the iron ions in the oxalic acid treatment liquid are reduced, the function of fluorine ions in the oxalic acid treatment liquid is maintained more actively. As a result, it is possible to suppress deterioration of the chemical conversion treatability even when the chemical conversion treatment is repeated. In the present specification, a film composed of iron (II) oxalate and impurities is referred to as an oxalate film. In the present specification, an alloy material having an oxalate film on its surface is referred to as a chemical conversion treatment alloy material. In the present specification, the oxalate ion includes both an oxalate ion (chemical formula: C 2 O 4 2− ) and a hydrogen oxalate ion (chemical formula: HC 2 O 4 − ).
[0041]
　Preferably, in the treatment liquid regeneration step, the oxalic acid treatment liquid is irradiated with light while flowing the oxalic acid treatment liquid.
[0042]
　In this case, the oxalic acid treatment liquid can be more efficiently irradiated with light.
[0043]
　Preferably, in the treatment liquid regenerating step, the wavelength of light includes a wavelength in the ultraviolet range.
[0044]
　When the wavelength of the light emitted by the light source member has a short wavelength and high intensity, the decomposition reaction of iron (III) oxalate into iron (II) oxalate is further promoted. Therefore, it is preferable that the wavelength of light is in the ultraviolet range. Here, the wavelength in the ultraviolet range refers to the wavelength in the range of 10 to 400 nm.
[0045]
　Preferably, the method for producing a chemical conversion treatment alloy material further includes a step of adding oxalate ions to the oxalic acid treatment liquid.
[0046]
　Oxalate ions are consumed as the iron ion content of the oxalic acid treatment liquid is reduced. If the step of adding oxalate ions is provided, the consumed oxalate ions are replenished. Therefore, chemical conversion treatment is promoted.
[0047]
　Preferably, the oxalic acid treatment liquid further contains nitrate ions.
[0048]
　In this case, the chemical conversion treatment is promoted.
[0049]
　Preferably, the oxalic acid treatment liquid further contains thiosulfate ion.
[0050]
　In this case, the chemical conversion treatment is promoted.
[0051]
　The alloy material may contain 10.5% or more of Cr.
[0052]
　According to the method for producing a chemical conversion treatment alloy material of the present disclosure, even if the chemical conversion treatment is repeatedly performed using an alloy material containing a large amount of Cr, it is possible to suppress deterioration in chemical conversion treatability.
[0053]
　The chemical conversion treatment liquid regeneration device of the present disclosure is a chemical conversion treatment liquid regeneration device used for manufacturing a chemical conversion treatment alloy material. The chemical conversion treatment liquid regeneration device includes a treatment liquid regeneration tank and a light irradiation device. The treatment liquid regenerating tank can store the oxalic acid treatment liquid during or after the chemical conversion treatment of the alloy material. The oxalic acid treatment liquid contains oxalate ions and fluorine ions. The light irradiation device includes one or a plurality of light source members. At least a part of the light source member is arranged inside or outside the treatment liquid regenerator. The light irradiation device can irradiate the oxalic acid treatment liquid during or after the chemical conversion treatment with light.
[0054]
　The chemical conversion liquid regenerator of the present disclosure includes a light irradiation device. The light irradiation device can irradiate the oxalic acid treatment liquid during or after the chemical conversion treatment with light by one or a plurality of light source members. Thereby, the oxalic acid treatment liquid can be regenerated. As a result, it is possible to suppress deterioration of the chemical conversion treatability even when the chemical conversion treatment is repeated.
[0055]
　Preferably, at least a part of the light source member can be immersed in the oxalic acid treatment liquid in the treatment liquid regeneration tank.
[0056]
　The distance between the light source and the oxalic acid treatment liquid is shortened by immersing at least a part of the light source member in the oxalic acid treatment liquid in the treatment liquid regeneration tank. Therefore, the oxalic acid treatment liquid can be irradiated with intense light. As a result, the oxalic acid treatment liquid can be more efficiently regenerated.
[0057]
　Preferably, the chemical conversion treatment liquid regenerator is equipped with a flow mechanism that causes the oxalic acid treatment liquid in the treatment liquid regenerator to flow.
[0058]
　When the oxalic acid treatment liquid in the treatment liquid regeneration tank flows by the flow mechanism, the amount of the oxalic acid treatment liquid irradiated with light increases. As a result, the oxalic acid treatment liquid can be more efficiently regenerated.
[0059]
　The chemical conversion treatment liquid regenerator may further include a chemical conversion treatment tank. The chemical conversion treatment tank can accommodate the oxalic acid treatment liquid after being irradiated with light by the light irradiation device in the treatment liquid regeneration tank. The chemical conversion treatment tank can perform the chemical conversion treatment by immersing the alloy material in the contained oxalic acid treatment liquid. When the chemical conversion treatment liquid regeneration device includes the chemical conversion treatment tank, the flow mechanism includes a first liquid supply path and a second liquid supply path. The first liquid feeding path conveys the oxalic acid treatment liquid in the treatment liquid regeneration tank to the chemical conversion treatment tank. The second liquid feeding path conveys the oxalic acid treatment liquid in the chemical conversion treatment tank to the treatment liquid regeneration tank.
[0060]
　By providing the chemical conversion treatment liquid regenerator further with the chemical conversion treatment tank, the chemical conversion treatment and the regeneration of the oxalic acid treatment liquid can be performed in separate tanks. Even if the chemical conversion treatment is continuously performed by circulating the oxalic acid treatment liquid between the chemical conversion treatment tank and the treatment liquid regeneration tank by the first liquid supply path and the second liquid supply path, the chemical conversion treatment is performed. It is possible to continue suppressing the decrease in processability.
[0061]
　The chemical conversion treatment tank may include a first chemical conversion treatment tank and a second chemical conversion treatment tank. In this case, the first liquid feeding passage includes the first liquid feeding passage main body, the first chemical conversion treatment tank side discharge port, and the second chemical conversion treatment tank side discharge port. The first liquid feeding passage body has two end portions on the chemical conversion treatment tank side. The first chemical conversion treatment tank side outlet is formed at one of the chemical conversion treatment tank side ends of the first liquid feeding passage main body, and the oxalic acid treatment liquid in the first liquid feeding passage main body is introduced into the first chemical conversion treatment tank. Discharge. The second chemical conversion treatment tank side outlet is formed at the other end of the first liquid supply passage body on the chemical conversion treatment tank side so that the oxalic acid treatment liquid in the first liquid supply passage body is introduced into the second chemical conversion treatment tank. Discharge. In addition, the second liquid feeding passage includes a second liquid feeding passage main body, a first chemical conversion treatment tank side inlet, and a second chemical conversion treatment tank side inlet. The second tank liquid channel body has two ends on the chemical conversion treatment tank side. The first chemical conversion treatment tank side inflow port is formed at one of the end portions on the chemical conversion treatment tank side of the second liquid feeding passage main body, and the oxalic acid treatment liquid in the first chemical conversion treatment tank is fed into the second liquid feeding passage main body. Inflow. The second chemical conversion treatment tank side inflow port is formed at the other end of the second liquid transmission passage body on the chemical conversion treatment tank side, and the oxalic acid treatment liquid in the second chemical conversion treatment tank flows into the second liquid transmission passage. Let In this case, the flow mechanism further includes an outlet switching mechanism and an inlet switching mechanism. The discharge port switching mechanism switches from which of the first chemical conversion treatment tank side discharge port and the second chemical conversion treatment tank side discharge port the oxalic acid treatment liquid in the first liquid feeding passage body is discharged. The inflow port switching mechanism switches from which of the first chemical conversion treatment tank side inflow port or the second chemical conversion treatment tank side inflow port the oxalic acid treatment liquid flows into the second liquid feeding passage body.
[0062]
　The chemical conversion treatment tank includes a first chemical conversion treatment tank and a second chemical conversion treatment tank, and which of the chemical conversion treatment tanks to circulate the oxalic acid treatment liquid is switched by using an outlet switching mechanism and an inlet switching mechanism. Is also good. In this case, the oxalic acid treatment liquid can be alternately circulated in the first chemical conversion treatment tank and the second chemical conversion treatment tank.
[0063]
　Preferably, the flow mechanism includes a during-regeneration treatment liquid circulation path for circulating the oxalic acid treatment liquid in the treatment liquid regeneration tank. The during-regeneration treatment liquid circulation passage includes a during-regeneration treatment liquid circulation passage main body, a during-regeneration treatment liquid inflow port, a during-regeneration treatment liquid discharge port, and a during-regeneration treatment liquid drive source. The during-regeneration treatment liquid circulation passage body can accommodate a part of the oxalic acid treatment liquid in the treatment liquid regeneration tank and has both ends. The during-regeneration treatment liquid inflow port is formed at one end of the during-regeneration treatment liquid circulation passage body and allows the oxalic acid treatment liquid in the treatment liquid regeneration tank to flow into the during-regeneration treatment liquid circulation passage body. The during-regeneration treatment liquid outlet is formed at the other end of the during-regeneration treatment liquid circulation passage body, and discharges the oxalic acid treatment liquid inside the during-regeneration treatment liquid circulation passage body into the treatment liquid regeneration tank. The during-regeneration treatment liquid circulation driving source moves the oxalic acid treatment liquid in the during-regeneration treatment liquid circulation passage body from the during-regeneration treatment liquid inflow port to the during-regeneration treatment liquid discharge port. At least one of the light source members is arranged between the in-regeneration treatment liquid inflow port and the in-regeneration treatment liquid discharge port.
[0064]
　The oxalic acid treatment liquid in the treatment liquid regeneration tank is repeatedly flown from the treatment liquid regeneration outlet to the treatment liquid inflow inlet during regeneration through the treatment liquid circulation passage. Since the light source member is arranged between the during-regeneration treatment liquid discharge port and the during-regeneration treatment liquid inflow port, more oxalic acid treatment liquid will be irradiated with light. As a result, the oxalic acid treatment liquid can be more efficiently regenerated.
[0065]
　Preferably, the bottom surface of the treatment liquid regeneration tank is inclined.
[0066]
　When the chemical conversion treatment liquid is irradiated with light, as described above, the sparingly soluble iron (II) oxalate is produced. Iron (II) oxalate becomes a precipitate and precipitates in the treatment liquid regeneration tank. If the bottom surface of the treatment liquid regenerator is slanted, the sediment will be accumulated at a lower portion of the slanted bottom surface. In this case, the precipitate can be easily collected.
[0067]
　The treatment liquid regenerating tank may be divided into a light irradiation chamber and a precipitation chamber by a partition member. The partition member has an opening that connects the light irradiation chamber and the precipitation chamber. In this case, one or more light source members are arranged in the light irradiation chamber.
[0068]
　If the treatment liquid regenerator is divided into a light irradiation chamber and a precipitation chamber, light irradiation and recovery of the precipitate can be performed in different partitions. In this case, the precipitate can be collected more efficiently.
[0069]
　Preferably, the bottom surface of the light irradiation chamber is lowered from the light irradiation chamber toward the precipitation chamber.
[0070]
　When the bottom of the light irradiation chamber is lowered from the light irradiation chamber toward the settling chamber, the precipitate generated in the light irradiation chamber is settled on the bottom of the light irradiation chamber and then moved to the settling chamber by its own weight. In this case, the precipitate can be collected more efficiently.
[0071]
　Preferably, the treatment liquid regeneration tank further includes a flow direction changing member. The flow direction changing member is arranged so that it can be immersed in the oxalic acid treatment liquid in the treatment liquid regeneration tank, and changes the flow direction of the oxalic acid treatment liquid in the treatment liquid regeneration tank.
[0072]
　If the treatment liquid regenerating tank is provided with the flow direction changing member, the flow direction of the oxalic acid treatment liquid in the treatment liquid regenerating tank is not aligned in a certain direction, and turbulent flow is likely to occur. If the turbulent flow occurs, the amount of the oxalic acid treatment liquid irradiated with light increases. Therefore, the oxalic acid treatment liquid can be more efficiently regenerated.
[0073]
　Preferably, the light irradiation device is an ultraviolet irradiation device.
[0074]
　The oxalic acid treatment liquid can be more efficiently regenerated by irradiating the ultraviolet irradiation device with light having a wavelength in the ultraviolet region. The wavelength in the ultraviolet range refers to the wavelength in the range of 10 to 400 nm.
[0075]
　Hereinafter, the present embodiment will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are designated by the same reference numerals and the description thereof will not be repeated.
[0076]
　[First Embodiment]
　[Method for producing chemical conversion treatment alloy material]
　The method for producing a chemical conversion treatment alloy material of the present embodiment includes a chemical conversion treatment step and a treatment liquid regeneration step. In the chemical conversion treatment step, the alloy material is immersed in an oxalic acid treatment liquid containing oxalate ions and fluorine ions for chemical conversion treatment. In the treatment liquid regeneration step, the oxalic acid treatment liquid during the chemical conversion treatment and/or the oxalic acid treatment liquid after the chemical conversion treatment is irradiated with light. In the method for producing a chemical conversion treatment alloy material of the present embodiment, for example, the following chemical conversion treatment liquid regenerator is used.
[0077]
　[Chemical conversion treatment liquid regenerator]
　FIG. 3 is a schematic view of an example of the chemical conversion treatment liquid regenerator 1 used in the method for manufacturing the chemical conversion treatment alloy material according to the present embodiment. Referring to FIG. 3, the chemical conversion treatment liquid regeneration device 1 includes a treatment liquid regeneration tank 2 and a light irradiation device 3.
[0078]
　[Treatment Liquid Regeneration Tank]
　Referring to FIG. 3, treatment liquid regeneration tank 2 can contain oxalic acid treatment liquid 4 during or after chemical conversion treatment of alloy material 6. In FIG. 3, the treatment liquid regeneration tank 2 is a housing. The upper surface of the treatment liquid regenerating tank 2 may be opened or a top plate may be provided. At least a part of the top plate or the side surface may be a member having translucency. The shape of the treatment liquid regenerating tank 2 is not particularly limited as long as it can accommodate the oxalic acid treatment liquid 4 during or after the chemical conversion treatment of the alloy material 6. The shape of the treatment liquid regenerating tank 2 may be a rectangular parallelepiped, a cube, or a tube.
[0079]
　The oxalic acid treatment liquid 4 contained in the treatment liquid regeneration tank 2 contains oxalate ions and fluorine ions. As will be described later, the alloy material 6 may be immersed in the treatment liquid regenerating tank 2 so that the oxalic acid treatment liquid 4 is regenerated and the alloy material 6 is subjected to chemical conversion treatment in the treatment liquid regenerating tank 2 at the same time. That is, the chemical conversion treatment liquid regeneration device 1 may function as a chemical conversion treatment device for performing the chemical conversion treatment on the alloy material 6. In this case, the treatment liquid regenerating tank 2 contains the oxalic acid treatment liquid 4 during the chemical conversion treatment of the alloy material 6. When the chemical conversion treatment is not performed in the treatment liquid regeneration tank 2, the treatment liquid regeneration tank 2 stores the oxalic acid treatment liquid 4 after the chemical conversion treatment of the alloy material 6. The oxalic acid treatment liquid 4 contained in the treatment liquid regeneration tank 2 may be a mixture of the oxalic acid treatment liquid 4 during the chemical conversion treatment of the alloy material 6 and the oxalic acid treatment liquid 4 after the chemical conversion treatment of the alloy material 6. Further, as will be described later, when the chemical conversion treatment is performed in the treatment liquid regeneration tank 2, the treatment liquid regeneration tank 2 can accommodate the alloy material 6 to be subjected to the chemical conversion treatment in addition to the oxalic acid treatment liquid 4.
[0080]
　[Light Irradiation Device] The
　light irradiation device 3 includes a light source member 31 and a power supply device (not shown). At least a part of the light source member 31 is arranged inside or outside the treatment liquid regenerating tank 2. The light source member 31 irradiates the oxalic acid treatment liquid 4 with light. The light irradiation device 3 irradiates the oxalic acid treatment liquid 4 during or after the chemical conversion treatment with light, whereby the oxalic acid treatment liquid 4 is regenerated.
[0081]
　The light irradiation device 3 is arranged so that the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 can be irradiated with light. As shown in FIG. 3, the light source member 31 of the light irradiation device 3 may be arranged inside the treatment liquid regenerating tank 2 or may be arranged outside thereof. When the light source member 31 is arranged inside the treatment liquid regeneration tank 2, the light source member 31 may be fixed without being immersed in the oxalic acid treatment liquid 4, but the oxalic acid treatment liquid in the treatment liquid regeneration tank 2 may be fixed. It is preferable that at least a part of the light source member 31 is disposed so that it can be immersed, and it is more preferable that the entire light source member 31 is immersed in the oxalic acid treatment liquid 4.
[0082]
　The light emitted from the light source member 31 is attenuated when propagating in the atmosphere or a member having a light transmitting property. However, if at least a part of the light source member 31 is immersed in the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2, the distance between the light source and the oxalic acid treatment liquid 4 becomes short. Therefore, the oxalic acid treatment liquid 4 can be irradiated with stronger light. As a result, the oxalic acid treatment liquid 4 can be regenerated more efficiently.
[0083]
　The method of immersing the light source member 31 in the oxalic acid treatment liquid 4 is not particularly limited. For example, even if the light source member 31 is fixed and at least a part of the light source member 31 is immersed in the oxalic acid treatment liquid 4 by filling the predetermined amount of the oxalic acid treatment liquid 4 into the treatment liquid regenerating tank 2. good. In addition, for example, the light irradiation device 3 further includes a drive source that moves the light source member 31 in the vertical and/or horizontal directions, and the processing liquid regeneration tank 2 is already filled by moving the light source member 31 by the drive source. The light source member 31 may be dipped in the oxalic acid treatment liquid 4.
[0084]
　When the light source member 31 is fixed without being immersed in the oxalic acid treatment liquid 4, the light source member 31 may be arranged inside the treatment liquid regeneration tank 2 and above the oxalic acid treatment liquid 4, for example. .. Specifically, when the top plate is attached to the treatment liquid regenerating tank 2, the top plate may be attached to the surface of the top plate on the oxalic acid treatment liquid 4 side. When the top plate is not attached to the treatment liquid regenerating tank 2, it may be arranged inside the side surface of the treatment liquid regenerating tank 2 and above the oxalic acid treatment liquid 4.
[0085]
　The number, size and shape of the light source members 31 are not particularly limited. The number of the light source members 31 may be one as shown in FIG. 3 or plural.
[0086]
　For example, a method of manufacturing the chemical conversion treatment alloy material according to the present embodiment using the chemical conversion treatment liquid regeneration device 1 will be described.
[0087]
　[Chemical conversion treatment step] In the
　chemical conversion treatment step, the alloy material 6 is immersed in the oxalic acid treatment liquid 4 containing oxalate ions and fluorine ions for chemical conversion treatment. First, the oxalic acid treatment liquid 4 is prepared and placed in the treatment liquid regeneration tank 2.
[0088]
　[Oxalic Acid Treatment Liquid]
　Oxalic acid treatment liquid 4 contains oxalate ions and fluorine ions. The oxalic acid treatment liquid 4 is produced by dissolving a salt having oxalic acid or oxalate ion as an anion and a salt having fluoride ion as an anion in a solvent. The salt having an oxalate ion as an anion is, for example, one or more selected from the group consisting of sodium oxalate, ammonium oxalate, potassium oxalate and iron (III) oxalate. The salt having a fluoride ion as an anion is, for example, one selected from the group consisting of sodium hydrogen fluoride, sodium fluoride, ammonium fluoride, potassium fluoride, hydrogen fluoride, hydrofluoric acid and nitrogen fluoride, or There are two or more types. The solvent may be, for example, water or a mixed solution of water and an organic solvent. The organic solvent is, for example, an organic solvent compatible with water.
[0089]
　The oxalate ion content of the oxalic acid treatment liquid 4 is, for example, 1.0 to 50 g/L. The lower limit of the oxalate ion content of the oxalic acid treatment liquid 4 is preferably 5.0 g/L. The upper limit of the oxalate ion content of the oxalic acid treatment liquid 4 is preferably 30 g/L. The fluorine ion content of the oxalic acid treatment liquid 4 is, for example, 0.1 to 10 g/L. The lower limit of the fluorine ion content of the oxalic acid treatment liquid 4 is preferably 1.0 g/L. The upper limit of the fluorine ion content of the oxalic acid treatment liquid 4 is preferably 5.0 g/L. Next, the alloy material 6 is immersed in the oxalic acid treatment liquid 4.
[0090]
　As described above, the oxalic acid treatment liquid 4 contains oxalate ions, fluorine ions and a solvent. The oxalic acid treatment liquid 4 may further contain other components. Preferably, the oxalic acid treatment liquid 4 further contains an oxidizing agent. The oxidizing agent is, for example, nitrate ion. The nitrate ion promotes the hydrogen oxidation reaction. The oxidized hydrogen is dispersed in the oxalic acid treatment liquid 4 as water. By dissolving nitric acid or a salt having nitric acid as an anion in the oxalic acid treatment liquid 4, the oxalic acid treatment liquid 4 can contain nitrate ions. The salt having a nitrate ion as an anion is, for example, one or more selected from the group consisting of ammonium nitrate, potassium nitrate, calcium nitrate, iron nitrate, copper nitrate, and sodium nitrate. The oxidant may further contain one or more selected from the group consisting of permanganate and peroxide. The content of the oxidizing agent in the oxalic acid treatment liquid 4 is, for example, 0.1 to 20 g/L. The upper limit of the content of the oxidizing agent in the oxalic acid treatment liquid 4 is preferably 10 g/L.
[0091]
　Preferably, the oxalic acid treatment liquid 4 further contains a promoter. The accelerator is, for example, thiosulfate ion. The thiosulfate ion reacts with the dissolved oxygen in the oxalic acid treatment liquid 4 and decomposes into sulfuric acid. As a result, the amount of dissolved oxygen in the oxalic acid treatment liquid 4 is reduced and the chemical conversion treatment is promoted. By dissolving a salt having thiosulfate ion as an anion in oxalic acid treatment liquid 4, thiosulfate ion can be contained in oxalic acid treatment liquid 4. The salt having a thiosulfate ion as an anion is, for example, one or more selected from the group consisting of sodium thiosulfate, ammonium thiosulfate, potassium thiosulfate, and calcium thiosulfate. The content of the accelerator in the oxalic acid treatment liquid 4 is, for example, 1.0 to 50 g/L. The lower limit of the content of the accelerator in the oxalic acid treatment liquid 4 is preferably 10 g/L. The upper limit of the content of the accelerator in the oxalic acid treatment liquid 4 is preferably 40 g/L.
[0092]
　The chemical conversion treatment is a well-known chemical conversion treatment. The temperature and time of the chemical conversion treatment can be set appropriately. For example, the temperature of the chemical conversion treatment is 40 to 100°C. The lower limit of the temperature of the chemical conversion treatment is preferably 80°C. The upper limit of the chemical conversion treatment temperature is preferably 95°C. For example, the chemical conversion treatment time is 1 to 200 minutes. The lower limit of the chemical conversion treatment time is preferably 5 minutes. The upper limit of the chemical conversion treatment time is preferably 20 minutes. The inside of the treatment liquid regenerating tank 2 may or may not be stirred during the chemical conversion treatment. The temperature of the chemical conversion treatment may be adjusted by heating the treatment liquid regenerating tank 2 or by immersing a heat source in the treatment liquid regenerating tank 2. The temperature of the chemical conversion treatment may be adjusted by adding the oxalic acid treatment liquid 4 heated using a heating device (not shown) into the treatment liquid regeneration tank 2.
[0093]
　[Treatment Liquid Regeneration Step] In the
　treatment liquid regeneration step, the light irradiation device 3 is used to irradiate the oxalic acid treatment liquid 4 during the chemical conversion treatment and/or the oxalic acid treatment liquid 4 after the chemical conversion treatment with light. The oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 contains iron ions, oxalate ions, and fluorine ions. When the oxalic acid treatment liquid 4 is irradiated with light, iron ions are reduced and fluorine ions are released. As a result, the function of etching fluorine ions is restored. When the oxalic acid treatment liquid 4 is irradiated with light, the production of iron (II) oxalate is further promoted. Iron (II) oxalate produced by light irradiation precipitates. Thereby, the iron ion content of the oxalic acid treatment liquid 4 is reduced. If the iron ion content is reduced, it becomes difficult for iron ions and fluorine ions to form a complex. Therefore, the function of fluoride ions is maintained more actively. As a result, it is possible to suppress deterioration of the chemical conversion treatability even when the chemical conversion treatment is repeated.
[0094]
　In the case of the manufacturing method based on the above steps, it is possible to suppress deterioration of chemical conversion treatability even when repeated chemical conversion treatment is performed.
[0095]
　[Oxalate Ion Addition Step]
　The manufacturing method may further include an oxalate ion addition step. In the treatment liquid regeneration step, oxalate ions are consumed as the iron ion content of the oxalic acid treatment liquid 4 is reduced. If the manufacturing method includes a step of adding oxalate ions, the consumed oxalate ions are replenished. The addition of oxalate ion is performed by dissolving oxalic acid or a salt having oxalate ion as an anion in the oxalic acid treatment liquid 4. Alternatively, addition of oxalate ions is performed by adding a solution in which oxalate ions are dissolved to the oxalic acid treatment liquid 4. The salt having an oxalate ion as an anion is, for example, one or more selected from the group consisting of sodium oxalate, ammonium oxalate, potassium oxalate and iron (III) oxalate. As a result, the oxalate ion content of the oxalic acid treatment liquid 4 increases. As a result, the oxalate ions easily react with the iron (divalent iron ions) dissolved on the surface of the alloy material 6, and the chemical conversion treatment is promoted. The concentration of the added oxalate ion can be set appropriately.
[0096]
　The time point when the oxalate ion addition step is performed is not particularly limited. The oxalate ion addition step may be performed before the chemical conversion treatment step, may be performed during the chemical conversion treatment step, or may be performed after the chemical conversion treatment. The oxalate ion addition step may be performed after the chemical conversion treatment and before the treatment liquid regeneration step, may be performed during the treatment liquid regeneration step, or may be performed after the treatment liquid regeneration step. ..
[0097]
　[Other Steps]
　The manufacturing method may include a pretreatment step for the alloy material 6 before the chemical conversion treatment step. The pretreatment is, for example, shot blasting, pickling, degreasing and the like. A lubricating coating may be formed on the surface of the chemical conversion treatment alloy material manufactured by the above manufacturing method. The lubricating coating is, for example, metallic soap.
[0098]
　[Wavelength of Light] When the wavelength of light in the
　treatment liquid regeneration step is a short wavelength and high intensity, the decomposition reaction of iron (III) oxalate into iron (II) oxalate is further promoted. Therefore, it is preferable that the wavelength of light includes a wavelength in the ultraviolet region. When the wavelength of light includes the wavelength in the ultraviolet region, the function of etching fluorine ions can be recovered more efficiently, and the iron ion content of the oxalic acid treatment liquid 4 can be reduced more efficiently. Here, the wavelength in the ultraviolet range refers to the wavelength in the range of 10 to 400 nm.
[0099]
　[Alloy Material]
　The shape of the alloy material 6 is not particularly limited as long as it forms an oxalate film. The shape of the alloy material 6 is, for example, a plate, a pipe, a rod, a wire, a ball, a shaped steel, other building alloy materials and machine structural parts, gears, connecting rods, crankshafts, pistons, and other automobile parts. The chemical conversion treatment alloy material manufacturing method of the present embodiment can be suitably applied when the shape of the alloy material 6 is a tube.
[0100]
　The chemical composition of the alloy material 6 contains Fe. The chemical composition of the alloy material 6 should just contain Fe. That is, the alloy material 6 may be a steel material containing 50% or more of Fe. In this case, the alloy material 6 may contain 10.5% or more of Cr. On the surface of the alloy material 6 containing 10.5% or more of Cr, an oxide film having high corrosion resistance is formed. According to the method for producing a chemical conversion treatment alloy material of the present embodiment, the function of fluorine ions is actively maintained. Therefore, the chemical conversion treatment alloy material can be manufactured even by using the alloy material 6 having the oxide film formed on the surface. The method for producing a chemical conversion treatment alloy material of the present embodiment can be suitably used for the alloy material 6 containing 10.5% or more of Cr. In addition, the alloy material 6 may be, for example, a Ni-based alloy or a Ni-Cr-Fe alloy. The method for producing a chemical conversion treatment alloy material of the present embodiment is also suitably used for an alloy material 6 having a total Cr and/or Ni content of more than 50% (that is, an alloy material 6 having an Fe content of less than 50%). be able to.
[0101]
　[Second Embodiment]
　[Method for producing chemical conversion treatment alloy material]
　Preferably, in the above-mentioned treatment liquid regenerating step, while the oxalic acid treatment liquid 4 in the treatment liquid regenerating tank 2 is flowed, the oxalic acid treatment liquid 4 is formed. Irradiate with light. By flowing the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2, the amount of the oxalic acid treatment liquid 4 irradiated with light is increased. As a result, since the oxalic acid treatment liquid 4 can be more efficiently regenerated, the deterioration of the chemical conversion treatability can be suppressed more efficiently. For example, if the following chemical conversion treatment liquid regenerator 1 is used, the treatment liquid regenerating step can be carried out while the oxalic acid treatment liquid 4 is flowing.
[0102]
　[Chemical conversion treatment liquid regenerator]
　Preferably, the chemical conversion treatment liquid regenerator 1 further includes a flow mechanism that causes the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 to flow.
[0103]
　[Flow Mechanism] The
　flow mechanism is not particularly limited as long as the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 can flow. FIG. 4 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from FIG. Referring to FIG. 4, the chemical conversion treatment liquid regenerator 1 includes a flow mechanism 7 in addition to the treatment liquid regenerator 2 and the light irradiation device 3. The flow mechanism 7 is, for example, as shown in FIG. 4, a device that is attached to a rotating shaft and generates a flow in the rotating shaft direction by rotating a wing having a spiral surface around the rotating shaft. The flow mechanism 7 is, for example, a screw or a propeller.
[0104]
　However, the flow mechanism 7 may be another mechanism. The flow mechanism 7 may be a mechanism for circulating the oxalic acid treatment liquid 4, for example. For example, the flow mechanism 7 pumps up a part of the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 using a pump, and the pumped oxalic acid treatment liquid 4 uses the height difference to treat the treatment liquid regeneration tank 2 It may be a mechanism for returning the inside. The flow mechanism 7 may be, for example, a mechanism that includes a heating device in the treatment liquid regeneration tank 2 and causes the oxalic acid treatment liquid 4 heated by the heating device to flow by convection.
[0105]
　The number and arrangement of the flow mechanisms 7 are not particularly limited. The number of the flow mechanisms 7 may be one or plural. The flowing direction of the oxalic acid treatment liquid 4 by the flow mechanism 7 may be horizontal, vertical from top to bottom, vertical from bottom to top, or inclined with respect to the horizontal direction. . The flow mechanism 7 may cause the oxalic acid treatment liquid 4 to flow in one direction, or the flow mechanisms 7 in different directions may generate flows in different directions. The point is that it is only necessary to increase the amount of the oxalic acid treatment liquid 4 irradiated with the light from the light source member 31. Therefore, the flow direction of the oxalic acid treatment liquid 4 by the flow mechanism 7 includes at least the flow direction toward the light source member 31.
[0106]
　For example, a method of manufacturing a chemical conversion treatment alloy material using the chemical conversion treatment liquid regeneration device 1 described above will be described.
[0107]
　[Chemical conversion treatment step] The
　chemical conversion treatment step is the same as in the first embodiment.
[0108]
　[Treatment Liquid Regeneration Step] When the
　chemical conversion treatment liquid regeneration device 1 includes the flow mechanism 7, the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 is caused to flow by the flow mechanism 7 during the treatment liquid regeneration process. As the amount of the oxalic acid treatment liquid 4 to be fluidized increases, the amount of the oxalic acid treatment liquid 4 irradiated with light can be increased. Therefore, the oxalic acid treatment liquid 4 can be regenerated more efficiently. For example, by increasing the flow rate by the flow mechanism 7, more oxalic acid treatment liquid 4 can be irradiated with light. Besides, by arranging a plurality of flow mechanisms 7 and operating them at the same time, the amount of the oxalic acid treatment liquid 4 that flows at one time is increased, so that more oxalic acid treatment liquid 4 can be irradiated with light.
[0109]
　According to the above method, in the treatment liquid regenerating step, the oxalic acid treatment liquid 4 can be irradiated with light while the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 is made to flow.
[0110]
　The method for producing a chemical conversion treatment alloy material according to the present disclosure can be realized by an apparatus other than those shown in FIGS. 3 and 4. Hereinafter, an example of the chemical conversion treatment liquid regeneration device 1 that can realize the method of manufacturing the chemical conversion treatment alloy material of the present disclosure will be described.
[0111]
　[Third Embodiment] The
　chemical conversion treatment liquid regenerator 1 may have a chemical conversion treatment bath 5 in addition to the treatment liquid regeneration bath 2. In this case, the chemical conversion treatment of the alloy material 6 and the regeneration treatment of the oxalic acid treatment liquid 4 are performed in separate tanks. When the chemical conversion treatment liquid regeneration device 1 includes the chemical conversion treatment tank 5 in addition to the treatment liquid regeneration tank 2, the flow mechanism 7 may include a first liquid feeding passage and a second liquid feeding passage. FIG. 5 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 4. The arrow in FIG. 5 indicates the direction in which the oxalic acid treatment liquid 4 circulates. With reference to FIG. 5, the chemical conversion treatment liquid regeneration device 1 includes a treatment liquid regeneration tank 2, a light irradiation device 3, a chemical conversion treatment tank 5, and a flow mechanism 7. The flow mechanism 7 includes a first liquid feed path 71 for conveying the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 to the chemical conversion treatment tank 5, and the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 5 for the treatment liquid regeneration tank 2. And a second liquid feeding path 72 for transporting to the. The chemical conversion treatment liquid regenerator 1 circulates the oxalic acid treatment liquid 4 between the chemical conversion treatment tank 5 and the treatment liquid regeneration tank 2 via the first liquid feeding passage 71 and the second liquid feeding passage 72. As a result, even if the chemical conversion treatment is performed continuously, it is possible to suppress deterioration of the chemical conversion treatment property.
[0112]
　[Chemical conversion treatment tank] The
　chemical conversion treatment tank 5 can accommodate the oxalic acid treatment liquid 4 after being irradiated with light by the light irradiation device 3 in the treatment liquid regeneration tank 2. The chemical conversion treatment tank 5 can perform the chemical conversion treatment by immersing the alloy material 6 in the contained oxalic acid treatment liquid 4. In FIG. 5, the chemical conversion treatment tank 5 is a rectangular parallelepiped casing. The upper surface of the chemical conversion treatment tank 5 may be opened, or a top plate may be provided. The chemical conversion treatment tank 5 may have a rectangular parallelepiped shape, a cubic shape, or a casing having a circular bottom surface such as a trough. The number of chemical conversion treatment tanks 5 is not particularly limited.
[0113]
　[First
　Liquid Feeding Path] The first liquid feeding path 71 connects the treatment liquid regenerating tank 2 and the chemical conversion treatment tank 5, and conveys the oxalic acid treatment liquid 4 from the treatment liquid regenerating tank 2 to the chemical conversion treatment tank 5. The first liquid feed passage 71 includes a first liquid feed passage main body 710, a treatment liquid regeneration tank side inlet 711 formed at one end of the first liquid feed passage main body 710, and a first liquid feed passage main body 710. And a chemical conversion treatment tank side discharge port 712 formed at the other end of the. The first liquid supply path 71 may further include a first liquid supply path drive source 713.
[0114]
　[First Liquid Feeding Channel Body]
　The shape of the first liquid feeding channel body 710 is, for example, tubular. A filter for collecting the precipitate and a valve for suppressing the reverse flow of the oxalic acid treatment liquid 4 may be provided in the first liquid feeding passage body 710.
[0115]
　[Treatment liquid regeneration tank side inlet] The
　treatment liquid regeneration tank side inlet 711 is formed at the end of the first liquid supply passage body 710 on the treatment liquid regeneration tank 2 side. The treatment liquid regeneration tank side inflow port 711 allows the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 to flow into the first liquid feeding passage body 710. The treatment liquid regeneration tank side inflow port 711 is preferably arranged downstream from the central position of the treatment liquid regeneration tank 2. The treatment liquid regeneration tank side inflow port 711 may be provided with a filter for suppressing the inflow of precipitates and other foreign substances into the first liquid feeding passage body 710.
[0116]
　[Chemical conversion treatment tank side discharge port] The
　chemical conversion treatment tank side discharge port 712 is formed at the end of the first liquid feeding passage body 710 on the chemical conversion treatment tank 5 side. The chemical conversion treatment tank side outlet 712 discharges the oxalic acid treatment liquid 4 in the first liquid feeding passage body 710 into the chemical conversion treatment tank 5. The chemical conversion treatment tank side outlet 712 is preferably arranged upstream of the central position of the chemical conversion treatment tank 5. In this case, the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 5 can be circulated more efficiently.
[0117]
　[First
　Liquid Supply Path Driving Source] The first liquid supply path driving source 713 supplies the oxalic acid treatment liquid 4 in the first liquid supply passage body 710 from the treatment liquid regeneration tank side inflow port 711 to the chemical conversion treatment tank side discharge port. Move to 712. The first liquid feed path drive source 713 is not particularly limited as long as it can move the oxalic acid treatment liquid 4. The first liquid supply path drive source 713 is, for example, a pump.
[0118]
　[Second liquid feeding path]
　The second liquid feeding path 72 connects the chemical conversion treatment tank 5 and the treatment liquid regenerating tank 2 and conveys the oxalic acid treatment liquid 4 from the chemical conversion treatment tank 5 to the treatment liquid regenerating tank 2. The second liquid feeding passage 72 includes a second liquid feeding passage main body 720, a chemical conversion treatment tank side inlet 721 formed at one end of the second liquid feeding passage main body 720, and a second liquid feeding passage main body 720. And a processing liquid regeneration tank side discharge port 722 formed at the other end. The second liquid supply path 72 may further include a second liquid supply path drive source 723.
[0119]
　[Second Liquid Supply Path Main Body]
　The shape of the second liquid supply path main body 720 is, for example, tubular. A filter for collecting precipitates and other foreign substances and a valve for suppressing backflow of the oxalic acid treatment liquid 4 may be provided in the second liquid feeding passage body 720.
[0120]
　[Chemical conversion treatment tank side inlet] The
　chemical conversion treatment tank side inlet 721 is formed at the end of the second liquid feeding passage body 720 on the chemical conversion treatment tank 5 side. The chemical conversion treatment tank side inflow port 721 allows the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 5 to flow into the second liquid feeding passage body 720. The chemical conversion treatment tank side inflow port 721 is preferably arranged downstream from the central position of the chemical conversion treatment tank 5. In this case, the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 5 can be circulated more efficiently.
[0121]
　[Treatment liquid regeneration tank side outlet] The
　treatment liquid regeneration tank side outlet 722 is formed at the end portion of the second liquid supply path main body 720 on the treatment liquid regeneration tank 2 side. The treatment liquid regeneration tank side outlet 722 discharges the oxalic acid treatment liquid 4 in the second liquid supply passage body 720 into the treatment liquid regeneration tank 2. The treatment liquid regeneration tank side outlet 722 is preferably arranged upstream of the central position of the treatment liquid regeneration tank 2.
[0122]
　[Second
　Liquid Feeding Path Driving Source] The second liquid feeding path driving source 723 supplies the oxalic acid treatment liquid 4 in the second liquid feeding passage body 720 from the chemical conversion treatment tank side inflow port 721 to the treatment liquid regenerating tank side discharge port. Move to 722. The second liquid feed path drive source 723 is not particularly limited as long as the oxalic acid treatment liquid 4 can be moved. The second liquid supply path drive source 723 is, for example, a pump.
[0123]
　When the chemical conversion treatment liquid regeneration device 1 includes a plurality of chemical conversion treatment tanks 5, the plurality of chemical conversion treatment tanks 5 are respectively connected to the first liquid feeding paths 71, and the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 is connected to the respective chemical conversion treatment tanks 5. It may be transported to the chemical conversion treatment tank 5. Alternatively, as will be described later, one first liquid feeding path 71 connected to the treatment liquid regenerating tank 2 may be branched from the middle to carry the oxalic acid treatment liquid 4 to each chemical conversion treatment tank 5. The same applies to the second liquid supply path 72. The second liquid feeding path 72 may be connected to each chemical conversion treatment tank 5, and the oxalic acid treatment liquid 4 may be conveyed from each chemical conversion treatment tank 5 to the same treatment liquid regeneration tank 2. The second liquid feeding passages 72 connected to the respective chemical conversion treatment tanks 5 may join together on the way.
[0124]
　In FIG. 5, the first liquid feed passage drive source 713 is arranged on the first liquid feed passage 71, and the second liquid feed passage drive source 723 is arranged on the second liquid feed passage 72. However, the number and arrangement of the first liquid feed path drive source 713 and the second liquid feed path drive source 723 are not limited to those in FIG. For example, one of the first liquid feed path drive source 713 and the second liquid feed path drive source 723 may be omitted. For example, when there is a height difference between the installation location of the chemical conversion treatment tank 5 and the installation location of the treatment liquid regeneration tank 2, and the oxalic acid treatment liquid 4 is flowed by utilizing the difference in height, the first liquid feeding path The first liquid feed path drive source 713 or the second liquid feed path drive source 723 may be arranged only on the liquid feed path having the lowest portion of the entire 71 or the second liquid feed path 72.
[0125]
　The oxalic acid treatment liquid 4 irradiated with light in the treatment liquid regeneration tank 2 is conveyed to the chemical conversion treatment tank 5 through the first liquid feeding path 71. As a result, the chemical conversion treatment can be performed in the chemical conversion treatment tank 5 using the regenerated oxalic acid treatment liquid 4. The oxalic acid treatment liquid 4 deteriorated in the chemical conversion treatment tank 5 is carried to the treatment liquid regeneration tank 2 through the second liquid feeding path 72. In the treatment liquid regeneration tank 2, the oxalic acid treatment liquid 4 is regenerated by light irradiation. The regenerated oxalic acid treatment liquid 4 is again conveyed to the chemical conversion treatment tank 5 through the first liquid feeding path 71. In this way, by circulating the oxalic acid treatment liquid 4 between the treatment liquid regenerating tank 2 and the chemical conversion treatment tank 5, it is possible to suppress deterioration of chemical conversion treatability even when the chemical conversion treatment is continuously performed.
[0126]
　The arrangement of the treatment liquid regenerating tank 2, the light irradiation device 3, the chemical conversion treatment tank 5, the first liquid feeding passage 71, and the second liquid feeding passage 72 is not limited to that shown in FIG. FIG. 6 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 5. In FIG. 5, the light source member 31 of the light irradiation device 3 is arranged at a position where a part of the light source member 31 is immersed in the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2, but in FIG. It is arranged near the outside of the liquid regeneration tank 2.
[0127]
　As described above, even when the chemical conversion treatment liquid regenerating apparatus 1 including the chemical conversion treatment tank 5, the first liquid feeding path 71, and the second liquid feeding path 72 is used, the method for manufacturing the chemical conversion treatment alloy material according to the present disclosure is performed. it can. In this case, in the treatment liquid regenerating step, the oxalic acid treatment liquid 4 is circulated between the treatment liquid regenerating tank 2 and the chemical conversion treatment tank 5 using the first liquid feeding passage 71 and the second liquid feeding passage 72.
[0128]
　[Fourth Embodiment]
　As described above, a plurality of chemical conversion treatment tanks 5 may be provided. For example, the chemical conversion treatment tank 5 may include a first chemical conversion treatment tank 51 and a second chemical conversion treatment tank 52. Further, which of the chemical conversion treatment tanks to circulate the oxalic acid treatment liquid 4 may be switched by using an outlet switching mechanism and an inlet switching mechanism. In this case, the first chemical conversion treatment tank 51 and the second chemical conversion treatment tank 52 can be alternately circulated.
[0129]
　FIG. 7 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 6. When the chemical conversion treatment tank 5 includes the first chemical conversion treatment tank 51 and the second chemical conversion treatment tank 52, the first liquid feeding passage body 710 may include two ends on the chemical conversion treatment tank 5 side. A discharge port is formed at each of two end portions of the first liquid feeding passage body 710 on the chemical conversion treatment tank 5 side. Specifically, the first liquid feed passage 71 includes a first liquid feed passage main body 710, a first chemical conversion treatment tank side discharge port 714, and a second chemical conversion treatment tank side discharge port 715. The first chemical conversion treatment tank side discharge port 714 is formed at one of the end portions of the first liquid feeding passage main body 710 on the chemical conversion treatment tank 5 side so that the oxalic acid treatment liquid 4 in the first liquid feeding passage main body 710 can be discharged first. It is discharged into the chemical conversion treatment tank 51. The second chemical conversion treatment tank side discharge port 715 is formed at the other end of the first liquid feeding passage main body 710 on the chemical conversion treatment tank 5 side so that the oxalic acid treatment liquid 4 in the first liquid feeding passage main body 710 is discharged to the second end. It is discharged into the chemical conversion treatment tank 52. The two ends of the first liquid feeding passage 71 on the chemical conversion treatment tank 5 side may be formed by branching the first liquid feeding passage main body 710 in the middle as shown in FIG. Two passages 71 may be arranged and may be an end portion of each of the two first liquid feeding passages 71.
[0130]
　When the chemical conversion treatment tank 5 includes the first chemical conversion treatment tank 51 and the second chemical conversion treatment tank 52, the second liquid feeding passage body 720 may include two ends on the chemical conversion treatment tank 5 side. An inflow port is formed at each of two ends of the second liquid supply path body 720 on the chemical conversion treatment tank 5 side. Specifically, the second liquid feed passage 72 includes a second liquid feed passage main body 720, a first chemical conversion treatment tank side inlet 724, and a second chemical conversion treatment tank side inlet 725. The first chemical conversion treatment tank side inflow port 724 is formed at one of the ends of the second liquid feeding passage main body 720 on the chemical conversion treatment tank 5 side, and the oxalic acid treatment liquid 4 in the first chemical conversion treatment tank 51 is sent to the second end. It is made to flow into the liquid channel body 720. The second chemical conversion treatment tank side inflow port 725 is formed at the other end of the second liquid feeding passage main body 720 on the chemical conversion treatment tank 5 side, and the oxalic acid treatment liquid 4 in the second chemical conversion treatment tank 52 is secondarily fed. It is made to flow into the liquid channel body 720. The two end portions of the second liquid feeding passage 72 may be formed by the second liquid feeding passage main body 720 branching in the middle as shown in FIG. 7, or two second liquid feeding passages 72 are arranged. Alternatively, the ends of the two second liquid supply paths 72 may be provided.
[0131]
　With reference to FIG. 7, the flow mechanism 7 preferably further includes an outlet switching mechanism 716 and an inlet switching mechanism 726. The discharge port switching mechanism 716 switches from which of the first chemical conversion treatment tank side discharge port 714 and the second chemical conversion treatment tank side discharge port 715 to discharge the oxalic acid treatment liquid 4 in the first liquid feeding passage body 710. The inflow port switching mechanism 726 switches which of the first chemical conversion treatment tank side inflow port 724 or the second chemical conversion treatment tank side inflow port 725 causes the oxalic acid treatment liquid 4 to flow into the second liquid feeding passage body 720.
[0132]
　The outlet switching mechanism 716 and the inlet switching mechanism 726 are not particularly limited as long as the flow of the oxalic acid treatment liquid 4 can be switched. The outlet switching mechanism 716 is, for example, a valve. Referring to FIG. 7, two valves are arranged on the branched first liquid feed passage body 710 on the side of the first chemical conversion treatment tank 51 and on the side of the second chemical conversion treatment tank 52. Alternatively, the discharge port switching mechanism 716 may be a pump. In this case, the first liquid feed path drive source 713 (pump) is unnecessary.
[0133]
　The inlet switching mechanism 726 is, for example, a valve. With reference to FIG. 7, two valves are arranged on the branched second liquid feeding passage body 720 on the first chemical conversion treatment tank 51 side and the second chemical conversion treatment tank 52 side. Alternatively, the inlet switching mechanism 726 may be a pump. In this case, the second liquid feed path drive source 723 (pump) is unnecessary.
[0134]
　[Fifth Embodiment] In
　the third and fourth embodiments, the chemical conversion treatment liquid regeneration device 1 includes a chemical conversion treatment tank 5, and the flow mechanism 7 is provided between the chemical conversion treatment tank 5 and the treatment liquid regeneration tank 2. Then, the oxalic acid treatment liquid 4 was circulated as a whole. On the other hand, the flow mechanism 7 may circulate the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2.
[0135]
　FIG. 8 is a schematic view of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 7. Referring to FIG. 8, the chemical conversion treatment liquid regeneration device 1 includes a treatment liquid regeneration tank 2, a light irradiation device 3, and a flow mechanism 7. The flow mechanism 7 includes a during-regeneration treatment liquid circulation passage 73 that circulates the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2.
[0136]
　[Regeneration Treatment Liquid Circulation Path] The
　regeneration treatment liquid circulation passage 73 includes a regeneration treatment liquid circulation body 730, a regeneration treatment liquid inlet 731, and a regeneration treatment liquid discharge port 732. At least one of the light source members 31 is disposed between the processing liquid inflow port 731 during regeneration and the processing liquid discharge port 732 during regeneration. The during-regeneration treatment liquid circulation path 73 further includes a during-regeneration treatment liquid circulation drive source 733.
[0137]
　Through the during-regeneration treatment liquid circulation path 73, the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 is repeatedly flown from the during-regeneration treatment liquid discharge port 732 toward the during-regeneration treatment liquid inlet 731. Therefore, the oxalic acid treatment liquid 4 is more likely to be irradiated with light from the light source member 31 arranged between the during-regeneration treatment liquid outlet 732 and the during-regeneration treatment liquid inlet 731. As a result, the oxalic acid treatment liquid 4 can be regenerated more efficiently.
[0138]
　[Main body of processing liquid circulation passage
　during regeneration ] The shape of the processing liquid circulation passage main body 730 during regeneration is not particularly limited. The shape of the processing liquid circulation passage body 730 during regeneration is, for example, tubular. A filter for collecting precipitates and other foreign substances, and a valve for suppressing backflow of the oxalic acid treatment liquid 4 may be provided in the treatment liquid circulation passage main body 730 during regeneration.
[0139]
　[Treatment liquid inlet during regeneration] The
　treatment liquid inlet during regeneration 731 is formed at one end of the treatment liquid circulation main body 730 during regeneration, and the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 is treated during regeneration. It is made to flow into the liquid circulation path main body 730. The during-regeneration treatment liquid inlet 731 may be provided with a filter for suppressing the inflow of a precipitate into the during-regeneration treatment liquid circulation passage body 730 and a valve for suppressing the backflow of the oxalic acid treatment liquid 4. ..
[0140]
　[Treatment Liquid Discharge Port
　During Regeneration ] The treatment liquid discharge port 732 during regeneration is formed at the other end of the treatment liquid circulation passage body 730 during regeneration, and the oxalic acid treatment liquid 4 in the treatment liquid circulation passage body 730 during regeneration is discharged. Discharge. The during-regeneration treatment liquid discharge port 732 may be disposed so that it can be immersed in the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 as shown in FIG. It may be provided and connected to the hole, or may be provided above the treatment liquid regenerating tank 2. The treatment liquid discharge port 732 during regeneration may be provided with an injection nozzle for increasing the discharge speed of the oxalic acid treatment liquid 4, as shown in FIG.
[0141]
　[Regeneration Treatment Liquid Driving Source] The
　regeneration treatment liquid circulation drive source 733 supplies the oxalic acid treatment liquid 4 in the regeneration treatment liquid circulating passage body 730 from the regeneration treatment liquid inlet 731 to the regeneration treatment liquid discharge port 732. To move. The during-regeneration treatment liquid circulation drive source 733 is, for example, a pump.
[0142]
　At least one of the light source members 31 is disposed between the during-regeneration treatment liquid discharge port 732 and the during-regeneration treatment liquid inlet 731. When a plurality of light source members 31 are arranged, all the light source members 31 are preferably arranged between the processing liquid discharge port 732 during regeneration and the processing liquid flow inlet 731 during regeneration. In this case, the amount of the oxalic acid treatment liquid 4 irradiated with light increases while the oxalic acid treatment liquid 4 flows from the regeneration treatment liquid discharge port 732 to the regeneration treatment liquid inflow port 731.
[0143]
　The number of processing liquid circulation paths 73 during regeneration is not particularly limited. As shown in FIG. 8, the number of the processing liquid circulation paths 73 during regeneration may be one or plural. When a plurality of in-regeneration treatment liquid circulation passages 73 are arranged, the directions in which the oxalic acid treatment liquid 4 is circulated by the during-regeneration treatment liquid circulation passages 73 may be the same or different. When a plurality of processing liquid circulation paths 73 during regeneration are arranged, each processing liquid circulation path 73 during regeneration may operate simultaneously, or may operate separately.
[0144]
　[Sixth Embodiment] Even when the
　flow mechanism 7 is provided with the processing liquid circulation passage 73 during regeneration, the chemical conversion treatment liquid regenerating apparatus 1 is provided with the chemical conversion treatment tank 5 in addition to the processing liquid regeneration tank 2 and the alloy material 6 The chemical conversion treatment and the regeneration treatment of the oxalic acid treatment liquid 4 may be separately performed. In this case, the chemical conversion treatment liquid regenerator 1 has a regenerating treatment liquid circulation path 73 for circulating the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 and the entire oxalic acid treatment liquid 4 including the chemical conversion treatment tank 5. It is preferable to provide a first liquid supply passage 71 and a second liquid supply passage 72 that circulate.
[0145]
　FIG. 9 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 8. With reference to FIG. 9, the chemical conversion treatment liquid regeneration device 1 includes a treatment liquid regeneration tank 2, a light irradiation device 3, a chemical conversion treatment tank 5, and a flow mechanism 7. The flow mechanism 7 includes a first liquid feeding passage 71, a second liquid feeding passage 72, and a processing liquid circulation passage 73 during regeneration.
[0146]
　When the chemical conversion treatment liquid regenerator 1 includes the chemical conversion treatment tank 5, and the flow mechanism 7 includes the in-regeneration treatment liquid circulation passage 73 in addition to the first liquid feed passage 71 and the second liquid feed passage 72, the treatment liquid regeneration The oxalic acid treatment liquid 4 repeatedly irradiated with light in the bath 2 can be circulated in the chemical conversion treatment bath 5. In this case, the chance that the oxalic acid treatment liquid 4 is irradiated with the light from the light source member 31 increases, and the amount of the oxalic acid treatment liquid 4 that is irradiated with the light increases, so that the deterioration of the chemical conversion treatability can be further suppressed.
[0147]
　The flow velocities of the first liquid feed passage 71 and the second liquid feed passage 72 and the flow velocity of the processing liquid circulation passage 73 during regeneration may be the same or different. By providing the treatment liquid circulation path 73 during regeneration, the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 is repeatedly irradiated with light. Therefore, the oxalic acid treatment liquid 4 can be efficiently regenerated even when the flow rates of the first liquid feeding passage 71 and the second liquid feeding passage 72 are low. Further, by increasing the flow velocity of the first liquid feeding path 71, the second liquid feeding path 72 and/or the treatment liquid circulating passage 73 during regeneration, the amount of the oxalic acid treatment liquid 4 irradiated with light is increased, and the efficiency is improved. Thus, the oxalic acid treatment liquid 4 can be regenerated. For example, when the flow rate of the processing liquid circulation path 73 during regeneration is increased, the oxalic acid processing solution 4 can be efficiently regenerated even when the flow rates of the first liquid feeding path 71 and the second liquid feeding path 72 are low.
[0148]
　[Seventh Embodiment]
　The bottom surface of the treatment liquid regeneration tank 2 may be inclined. When the oxalic acid treatment liquid 4 is irradiated with light, the sparingly soluble iron (II) oxalate is produced as described above. Iron (II) oxalate becomes a precipitate and precipitates in the treatment liquid regeneration tank 2. If the bottom surface of the treatment liquid regenerating tank 2 is inclined, the precipitate is accumulated at a lower portion of the inclined bottom surface. In this case, the precipitate can be easily collected.
[0149]
　10 to 12 are schematic views showing an example of the treatment liquid regenerating tank 2 having a bottom inclined. Referring to FIG. 10, the bottom surface 21 of the treatment liquid regeneration tank 2 is linearly inclined downward from both ends toward the center. In this case, the precipitate accumulates in the central portion of the treatment liquid regenerating tank 2.
[0150]
　The inclination of the bottom surface 21 of the treatment liquid regeneration tank 2 is not limited to that shown in FIG. The bottom surface 21 of the treatment liquid regeneration tank 2 may be linearly inclined downward from one end to the other end as shown in FIG. 11, for example. The direction of inclination may be opposite to that in FIG. The bottom surface 21 of the treatment liquid regeneration tank 2 may be linearly inclined downward from the center toward both ends so that the center is convex. The bottom surface 21 of the treatment liquid regeneration tank 2 may not be linearly inclined, but may be curved and inclined as shown in FIG. 12, for example.
[0151]
　[Eighth Embodiment] The
　treatment liquid regenerating tank 2 may be divided into a light irradiation chamber and a precipitation chamber by a partition member. FIG. 13 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 12. With reference to FIG. 13, the treatment liquid regenerating tank 2 is divided into a light irradiation chamber 23 and a precipitation chamber 24 by a partition member 22. The partition member 22 has an opening 220 that connects the light irradiation chamber 23 and the precipitation chamber 24. One or more light source members 31 are arranged in the light irradiation chamber 23.
[0152]
　If the treatment liquid regenerating tank 2 is divided into the light irradiation chamber 23 and the precipitation chamber 24, the light irradiation and the recovery of the precipitate can be performed in different partitions. In this case, the precipitate can be collected more efficiently.
[0153]
　The size, shape and position of the partition member 22 are not particularly limited. The partition member 22 may be a plate-shaped member that extends downward from the upper surface of the treatment liquid regeneration tank 2. Moreover, the direction of the partition member 22 may be a vertical direction or may be inclined with respect to the vertical direction.
[0154]
　The opening 220 connecting the light irradiation chamber 23 and the precipitation chamber 24 is preferably arranged at the lower end of the partition member 22. The opening 220 may be arranged only at the lower end of the partition member 22, or may be arranged at a position other than the lower end of the partition member 22 in addition to the lower end. The size, number, and position of the openings 220 can be appropriately adjusted within a range in which a desired flow rate of the oxalic acid treatment liquid 4 can be obtained and a range in which precipitates do not block the flow of the oxalic acid treatment liquid 4.
[0155]
　[Ninth Embodiment]
　Preferably, the bottom surface of the light irradiation chamber 23 is lowered from the light irradiation chamber 23 toward the precipitation chamber 24. FIG. 14 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 13. The chemical conversion treatment liquid regenerator 1 of FIG. 14 further includes a during-regeneration treatment liquid circulation path 73 as compared with the chemical conversion treatment liquid regenerator 1 of FIG. The bottom surface 230 of the light irradiation chamber 23 of the treatment liquid regeneration tank 2 of the chemical conversion treatment liquid regeneration device 1 of FIG. 14 is linearly inclined downward from the light irradiation chamber 23 toward the precipitation chamber 24.
[0156]
　When the bottom surface 230 of the light irradiation chamber 23 is lowered from the light irradiation chamber 23 toward the settling chamber 24, the precipitate generated in the light irradiation chamber 23 is settled on the bottom surface 230 of the light irradiation chamber 23 and then self-weighted. Moves toward the settling chamber 24. The sediment accumulates in the sedimentation chamber 24 through the opening 220 of the partition member 22. Therefore, the precipitate can be collected more efficiently.
[0157]
　In FIG. 14, the bottom surface 240 of the precipitation chamber 24 is also inclined. As a result, the precipitate that has moved into the settling chamber 24 moves by its own weight according to the inclination of the bottom surface 240 of the settling chamber 24 and accumulates at a lower position. In this case, the recovery of the precipitate becomes easier. However, the bottom surface 240 of the precipitation chamber 24 does not have to be inclined.
[0158]
　[Tenth Embodiment]
　Preferably, the treatment liquid regenerating tank 2 further includes a flow direction changing member. The flow direction changing member is arranged so that it can be immersed in the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2, and changes the flow direction of the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2.
[0159]
　FIG. 15 is a plan view of the treatment liquid regenerating tank 2 showing the arrangement of the flow direction changing member 25. The arrow in FIG. 15 indicates the direction in which the oxalic acid treatment liquid 4 flows. With reference to FIG. 15, the treatment liquid regeneration tank 2 includes a flow direction changing member 25. If the treatment liquid regenerating tank 2 is provided with the flow direction changing member 25, the flow directions of the oxalic acid treatment liquid 4 in the treatment liquid regenerating tank 2 are not aligned in a fixed direction, and a turbulent flow is likely to occur. If a turbulent flow occurs, the amount of the oxalic acid treatment liquid 4 irradiated with light increases. Therefore, the oxalic acid treatment liquid 4 can be regenerated more efficiently.
[0160]
　The number, shape, and size of the flow direction changing member 25 are not particularly limited as long as the flow direction changing member 25 can change the flow direction of the oxalic acid treatment liquid 4. The flow direction changing member 25 may be one, two, or three or more as shown in FIG. The flow direction changing member 25 may have a plate shape, a rod shape, a spherical shape, a box shape, or a tubular shape. For example, when the flow direction changing member 25 has a plate shape, the flow direction changing member 25 may be curved or may not be curved.
[0161]
　The arrangement of the flow direction changing member 25 can be appropriately adjusted within a range in which the flow of the oxalic acid treatment liquid 4 is not completely blocked. The flow direction changing member 25 is preferably arranged between the plurality of light source members 31 as shown in FIG. In this case, more oxalic acid treatment liquid 4 passes near more light source members 31. Therefore, the amount of the oxalic acid treatment liquid 4 irradiated with light increases. As the flow direction changing member 25, for example, as shown in FIG. 16, a plurality of plate-like flow direction changing members 25 may be arranged with regularity or may be arranged irregularly.
[0162]
　[Eleventh Embodiment] The
　chemical conversion liquid regenerator 1 may have the features of the above-described embodiments in combination. FIG. 17 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment different from those of FIGS. 3 to 16. Referring to FIG. 17, the chemical conversion treatment liquid regeneration device 1 includes a treatment liquid regeneration tank 2, a light irradiation device 3, a first chemical conversion treatment tank 51 and a second chemical conversion treatment tank 52. The oxalic acid treatment liquid 4 is wholly circulated between the 51 and the second chemical conversion treatment tank 52 and the treatment liquid regeneration tank 2, and further the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 is circulated.
[0163]
　The chemical conversion treatment liquid regeneration device 1 includes a treatment liquid regeneration tank 2, a first chemical conversion treatment tank 51 and a second chemical conversion treatment tank 52, a light irradiation device 3, and a flow mechanism 7. The treatment liquid regenerating tank 2 is divided into a light irradiation chamber 23 and a precipitation chamber 24 by a partition member 22. Both the bottom surface 230 of the light irradiation chamber 23 and the bottom surface 240 of the precipitation chamber 24 are inclined so as to decrease from the upstream side to the downstream side of the flow of the oxalic acid treatment liquid 4. The light source member 31 of the light irradiation device 3 is arranged so that it can be immersed in the oxalic acid treatment liquid 4 in the light irradiation chamber 23.
[0164]
　The flow mechanism 7 includes a first liquid feeding passage 71, a second liquid feeding passage 72, and a processing liquid circulation passage 73 during regeneration. The first liquid feed path 71 conveys the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2 to the first chemical conversion treatment tank 51 and the second chemical conversion treatment tank 52. The chemical conversion treatment tank 5 side of the first liquid supply passage main body 710 of the first liquid supply passage 71 is branched into two, and the first chemical conversion treatment tank side discharge port is provided at each of two ends of the first liquid supply passage main body 710. 714 and the second chemical conversion treatment tank side discharge port 715 are formed. The second liquid feeding path 72 conveys the oxalic acid treatment liquid 4 in the first chemical conversion treatment tank 51 and the second chemical conversion treatment tank 52 to the treatment liquid regeneration tank 2. The chemical conversion treatment tank 5 side of the second liquid supply passage main body 720 of the second liquid supply passage 72 is branched into two, and the first chemical conversion treatment tank side inlet is provided at each of two ends of the second liquid supply passage main body 720. 724 and the second chemical conversion treatment tank side inflow port 725 are formed. The flow mechanism 7 further includes an outlet switching mechanism 716 and an inlet switching mechanism 726. Thereby, it is possible to circulate or adjust the oxalic acid treatment liquid 4 in the first chemical conversion treatment tank 51 and/or the second chemical conversion treatment tank 52.
[0165]
　The during-regeneration treatment liquid circulation path 73 circulates the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2. As a result, the amount of the oxalic acid treatment liquid 4 irradiated with light can be increased, and the oxalic acid treatment liquid 4 is efficiently regenerated. In FIG. 17, the during-regeneration treatment liquid circulation path 73 conveys the oxalic acid treatment liquid 4 in the precipitation chamber 24 to the light irradiation chamber 23.
[0166]
　The oxalic acid treatment liquid 4 after the treatment liquid regeneration step is carried to the chemical conversion treatment tank 5. In the chemical conversion treatment tank 5, the chemical conversion treatment is performed again using the oxalic acid treatment liquid 4 after the treatment liquid regeneration step. The oxalic acid treatment liquid 4 in the chemical conversion treatment tank 5 after being transferred to the chemical conversion treatment tank 5 is the oxalic acid treatment liquid 4 after the treatment liquid regeneration step, and the unused oxalic acid treatment liquid 4 and the treatment liquid regeneration step It may be a mixture with the oxalic acid treatment liquid 4. That is, the oxalic acid treatment liquid 4 containing the oxalic acid treatment liquid 4 after the treatment liquid regeneration step may be used.
[0167]
[Other Embodiments]
　The method of manufacturing the chemical conversion treatment alloy material of the present disclosure is not limited to the above-described manufacturing method. An example of development is shown below.
[0168]
　[Position of
　Light Source Member ] The light source member 31 is preferably arranged in the treatment liquid regenerating tank 2 so that it can be immersed in the oxalic acid treatment liquid 4. The arrangement of the light source member 31 can be changed as appropriate.
[0169]
　FIG. 18 is a schematic diagram showing an example of the arrangement of the light source members 31. As shown in FIG. 18, the light source member 31 may be arranged near the outside of the treatment liquid regenerating tank 2. For example, the light source member 31 may be arranged above the treatment liquid regeneration tank 2. In this case, the top surface of the treatment liquid regenerating tank 2 is open, or a top plate made of a translucent member is attached to a portion facing the light source member 31. When the light source member 31 is arranged above the treatment liquid regenerating tank 2, the light source member 31 is preferably arranged as close as possible to the liquid surface of the treatment liquid in order to suppress attenuation of light when propagating in the atmosphere.
[0170]
　Alternatively, a light-transmitting member may be used on a part of the side surface of the treatment liquid regenerating tank 2 and the light source member 31 may be arranged laterally of the treatment liquid regenerating tank 2. FIG. 19 is a schematic view showing an example of the arrangement of the light source members 31, which is different from FIG. For example, as shown in FIG. 19, a cylindrical light source member 31 may be arranged along the long side of the outer side surface of the treatment liquid regeneration tank 2 in the axial direction of the plurality of light source members 31.
[0171]
　When the light source member 31 is arranged above the processing liquid regenerating tank 2, the light source member 31 is preferably within a range of 200 mm from the liquid surface of the processing liquid contained in the processing liquid regenerating tank 2, and more preferably 100 mm. It is arranged so as to be located within the range, more preferably within the range of 50 mm. Further, when the light source member 31 is arranged laterally of the treatment liquid regenerating tank 2, it is preferable that the light source member 31 is within a range of 100 mm from the surface of the translucent member on the side surface of the treatment liquid regenerating tank 2, More preferably, it is attached to the surface of the translucent member.
[0172]
　FIG. 20 is a schematic diagram showing an example of the arrangement of the light source members 31, which is different from FIGS. 18 to 19. With reference to FIG. 20, the light source member 31 having a cylindrical shape is arranged such that the entire light source member 31 is arranged inside the treatment liquid regenerating tank 2 with the axial direction of the light source member 31 aligned with the width direction of the treatment liquid regenerating tank 2. Good.
[0173]
　FIG. 21 is a schematic view showing an example of the arrangement of the light source members 31, which is different from FIGS. 18 to 20. FIG. 21 is a view of the treatment liquid regenerating tank 2 seen from above. The arrow in FIG. 21 indicates the flow direction of the oxalic acid treatment liquid 4. When the oxalic acid treatment liquid 4 flows and a plurality of light source members 31 are provided in the treatment liquid regeneration tank, as shown in FIG. 21, the oxalic acid treatment liquid 4 is connected in series in a direction orthogonal to the flow direction of the oxalic acid treatment liquid 4. Or may be arranged randomly with respect to the flow direction of the oxalic acid treatment liquid 4.
[0174]
　[Shape of
　Treatment Liquid Regenerating Tank ] The shape of the treatment liquid regenerating tank 2 is not particularly limited as long as it can irradiate the oxalic acid treatment liquid 4 with light, and can be appropriately changed.
[0175]
　FIG. 22 is a schematic diagram showing an example of the shape of the treatment liquid regeneration tank 2. The arrow in FIG. 22 indicates the direction of flow of the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2. Referring to FIG. 22, the treatment liquid regeneration tank 2 may have a box shape in which one of the side surfaces is formed in a step shape. In this case, for example, a plurality of columnar light source members 31 may be arranged in the axial direction along the width direction of the treatment liquid regenerating tank 2 in steps of side surfaces having a step shape. In this case, the area which can be irradiated with light by the light source member 31 increases. As a result, the oxalic acid treatment liquid 4 can be regenerated more efficiently.
[0176]
　FIG. 23 is a schematic view showing an example of the shape of the treatment liquid regenerating tank 2 different from FIG. The treatment liquid regenerating tank 2 may be a part of the liquid feeding passage. The processing liquid regenerating tank 2 in FIG. 23 is a part of the liquid feeding passage main body 720. In FIG. 23, the light source member 31 is arranged near the outside of the treatment liquid regenerating tank 2. In this case, at least the surface of the treatment liquid regenerating tank 2 facing the light source member 31 is made of a translucent member. As shown in FIG. 23, the light source member 31 may be arranged above and below the treatment liquid regeneration tank 2, or may be arranged so as to surround the outside of the treatment liquid regeneration tank 2 which is a liquid feeding path. In FIG. 23, the precipitation tank 8 is arranged downstream of the treatment liquid regeneration tank 2, but it may be omitted.
[0177]
　FIG. 24 is a schematic diagram showing an example of the shape of the treatment liquid regenerating tank 2 different from FIGS. 22 to 23. With reference to FIG. 24, the treatment liquid regeneration tank 2 may be, for example, a tower type. Specifically, the treatment liquid regenerating tank 2 has a rectangular parallelepiped shape having long sides extending in the vertical direction, and the light source member 31 is arranged inside. The light source members 31 have a cylindrical shape, and a plurality of light source members 31 are arranged such that the longitudinal direction thereof is perpendicular to the direction of the flow of the oxalic acid treatment liquid 4 in the treatment liquid regeneration tank 2. The oxalic acid treatment liquid 4 flows into the treatment liquid regeneration tank 2 from the lower portion of the treatment liquid regeneration tank 2, and flows from the lower portion to the upper portion of the treatment liquid regeneration tank 2. The oxalic acid treatment liquid 4 discharged from the upper portion of the treatment liquid regeneration tank 2 passes through the liquid supply path 82 and is discharged into the settling tank 8 provided at the tip of the liquid supply path 82. The lower part of the settling tank 8 can be opened, and a collecting device 81 for collecting the precipitate is arranged below the settling tank 8. The side surface of the precipitation tank 8 has a hole, and the oxalic acid treatment liquid 4 in the precipitation tank 8 is discharged from the hole on the side surface of the precipitation tank 8.
[0178]
　FIG. 25 is a schematic diagram showing an example of the shape of the treatment liquid regenerating tank 2 different from FIGS. 22 to 24. Referring to FIG. 25, the treatment liquid regeneration tank 2 may be a tower type in which the oxalic acid treatment liquid 4 flows from the upper portion to the lower portion. In this case, the treatment liquid regenerating tank 2 has an opening at which the oxalic acid treatment liquid 4 flows in and an opening at which the oxalic acid treatment liquid 4 is discharged at the bottom. A drive source 83 for feeding a liquid may be arranged on the liquid feeding path 82 between the treatment liquid regenerating tank 2 and the precipitation tank 8. The other configuration of FIG. 25 is the same as that of FIG.
[0179]
　[Other Examples of Arrangement] When the
　chemical conversion treatment liquid regeneration device 1 includes the chemical conversion treatment tank 5, the arrangements of the treatment liquid regeneration tank 2 and the chemical conversion treatment tank 5 can be appropriately changed.
[0180]
　FIG. 26 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment, which is different from FIGS. 3 to 25. Referring to FIG. 26, the chemical conversion treatment liquid regeneration device 1 includes a treatment liquid regeneration tank 2 and a chemical conversion treatment tank 5. The treatment liquid regeneration tank 2 and the chemical conversion treatment tank 5 are not connected. The light source member 31 is arranged in the treatment liquid regenerating tank 2.
[0181]
　When the chemical conversion liquid regenerator 1 of FIG. 26 is used, the regenerated oxalic acid treatment liquid 4 is returned to the chemical conversion treatment tank 5 by the transportation means and the chemical conversion treatment is performed again. The transportation means is transportation by a container, for example. In this case, the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 5 is the oxalic acid treatment liquid 4 after the treatment liquid regeneration process, or the unused oxalic acid treatment liquid 4 and the oxalic acid treatment liquid 4 after the treatment liquid regeneration process. Is a mixture of.
[0182]
　FIG. 27 is a schematic diagram of a chemical conversion liquid regenerator 1 according to another embodiment, which is different from FIGS. 3 to 26. Referring to FIG. 27, oxalic acid treatment liquid 4 regenerated in treatment liquid regeneration tank 2 does not necessarily have to return to the same chemical conversion treatment tank 5. In FIG. 27, the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 5 is regenerated in the treatment liquid regeneration tank 2 and then discharged into a chemical conversion treatment tank 53 different from the chemical conversion treatment tank 5. For example, the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 53 may be returned to the chemical conversion treatment tank 5 by a liquid feeding path (not shown). In this case, the chemical conversion treatment liquid is in a form of being regenerated after being used in both the chemical conversion treatment tank 53 and the chemical conversion treatment tank 5. As a result, in the chemical conversion treatment tank 5 and the chemical conversion treatment tank 53, deterioration of chemical conversion treatability is suppressed even when the chemical conversion treatment is repeated. Alternatively, the unused oxalic acid treatment liquid 4 may be replenished to the chemical conversion treatment tank 5, and the oxalic acid treatment liquid 4 in the chemical conversion treatment tank 53 may be discarded after the chemical conversion treatment. In this case, even if the oxalic acid treatment liquid 4 after the chemical conversion treatment in the chemical conversion treatment tank 5 is used, the deterioration of the chemical conversion treatment property in the chemical conversion treatment tank 53 is suppressed.
Example
[0183]
　As an example, an iron ion reduction test by light irradiation was performed. An oxalic acid treatment liquid having the following composition was prepared.
　Felbond 3819A (manufactured by Nippon Parkerizing Co., Ltd.)
　oxalic acid: 92%
　sodium hydrogen fluoride: 1-8%
　Felbond 3819B (manufactured by Nippon Parkerizing Co., Ltd.)
　sodium nitrate: 40-50%
　Felbond 3819A for the test : Felbond 3819B=Oxalic acid treatment liquid mixed at a mass ratio of 4:1 was used.
[0184]
　Using the prepared oxalic acid treatment liquid, a chemical conversion treatment was carried out on a duplex stainless steel material (ASTM UNS S39274) containing 25% of Cr, 7% of Ni, 3% of Mo and 2% of W. The conditions for the chemical conversion treatment were 90° C. and 20 minutes.
[0185]
　[Light irradiation test]
　The oxalic acid-treated solution after the chemical conversion treatment was irradiated with ultraviolet rays to measure the iron ion content of the oxalic acid-treated solution before and after. The ultraviolet irradiation conditions were a wavelength of 365 nm and an irradiation time of 6 minutes. The oxalic acid treatment liquid before ultraviolet irradiation and the oxalic acid treatment liquid after ultraviolet irradiation were analyzed using an emission spectroscopic analyzer (ICP-OES) PS7800 manufactured by Hitachi High-Tech Science Co., Ltd., respectively. The measurement results are shown in FIG.
[0186]
　[Chemical conversion treatment test] A
　chemical conversion treatment test was carried out using an unused oxalic acid treatment liquid, a used oxalic acid treatment liquid, and a used oxalic acid treatment liquid after ultraviolet irradiation. The alloy material subjected to the chemical conversion treatment was an alloy material having a Cr content of 25%. The conditions for chemical conversion treatment were 90° C. and 20 minutes. The potential on the surface of the alloy material during the chemical conversion treatment was measured using a potentiostat with a saturated calomel electrode as a reference electrode. The results are shown in Figure 2.
[0187]
　[Test Results]
　Referring to FIG. 1, when the oxalic acid-treated solution after use was irradiated with ultraviolet rays, the iron ion content decreased. Further, referring to FIG. 2, by irradiating the oxalic acid treatment liquid after use with ultraviolet rays (regeneration treatment liquid in FIG. 2), it is equivalent to an unused oxalic acid treatment liquid (unused liquid in FIG. 2). The chemical conversion treatability has recovered.
[0188]
　The embodiments of the present invention have been described above. However, the embodiments described above are merely examples for carrying out the present invention. Therefore, the present invention is not limited to the above-described embodiments, and can be implemented by appropriately modifying the above-described embodiments without departing from the spirit thereof.
Explanation of symbols
[0189]
　1 Chemical conversion treatment liquid regeneration device
　2 Treatment liquid regeneration tank
　3 Light irradiation device
　4 Oxalic acid treatment liquid
　6 Alloy material
　31 Light source member
The scope of the claims
[Claim 1]
　A method for producing a chemical conversion treatment alloy material,
　the step of dipping an alloy material in an oxalic acid treatment liquid containing oxalate ions and fluorine ions to perform a chemical
　conversion treatment, and the oxalic acid treatment liquid during the chemical conversion treatment and/or Or a treatment liquid regenerating step of irradiating the oxalic acid treatment liquid after the chemical conversion treatment with light.
[Claim 2]
　The method for producing a chemical conversion treatment alloy material according to claim 1,
　wherein in the treatment liquid regenerating step, the
　oxalic acid treatment liquid is irradiated with light while flowing the oxalic acid treatment liquid. Method.
[Claim 3]
　It is a manufacturing method of the chemical conversion treatment alloy material of Claim 1 or Claim 2, Comprising: In the
　said process liquid reproduction|regeneration process,
　the wavelength of the said light contains the wavelength of an ultraviolet range, The manufacturing method of a chemical conversion treatment alloy material.
[Claim 4]
　The method for producing a chemical conversion treatment alloy material according to any one of claims 1 to 3, further
　comprising a step of adding oxalate ions to the oxalic acid treatment liquid.
[Claim 5]
　The method for producing a chemical conversion treatment alloy material according to any one of claims 1 to 4,
　wherein the oxalic acid treatment liquid further contains nitrate ions.
[Claim 6]
　The method for producing a chemical conversion treatment alloy material according to any one of claims 1 to 5,
　wherein the oxalic acid treatment liquid further contains thiosulfate ions.
[Claim 7]
　The method for producing a chemical conversion treatment alloy material according to any one of claims 1 to 6,
　wherein the alloy material contains 10.5% or more of Cr.
[Claim 8]
　1. A chemical conversion treatment liquid regenerator, which
　contains an oxalate ion and a fluorine ion and is capable of accommodating an oxalic acid treatment liquid during chemical conversion treatment of an alloy material or after the chemical conversion treatment, and
　one or more light sources. A light irradiating device including a member, wherein at least a part of the light source member is disposed inside or near the outside of the treatment liquid regeneration tank, and is capable of irradiating the oxalic acid treatment liquid during or after the chemical conversion treatment with light. And a chemical conversion liquid regenerator.
[Claim 9]
　The chemical conversion treatment liquid regeneration device according to claim 8
　, wherein at least a part of the light source member of the light source member is dipable in the oxalic acid treatment liquid in the treatment liquid regeneration tank. Playback device.
[Claim 10]
　The chemical conversion treatment liquid regenerator according to claim 8 or 9, further
　comprising a flow mechanism that causes the oxalic acid treatment liquid in the treatment liquid regeneration tank to flow.
[Claim 11]
　The chemical conversion treatment liquid regenerator according to claim 10, further
　capable of accommodating the oxalic acid treatment liquid after being irradiated with the light by the light irradiation device in the treatment liquid regeneration tank, The chemical conversion treatment tank capable of performing the chemical conversion treatment by immersing the alloy material in the oxalic acid treatment liquid, the
　flow mechanism, the
　oxalic acid treatment liquid in the treatment liquid regeneration tank to the chemical conversion treatment tank A
　chemical conversion treatment liquid regenerator comprising: a first liquid feed path for transporting; and a second liquid feed path for transporting the oxalic acid treatment liquid in the chemical conversion treatment tank to the treatment liquid regenerating tank.
[Claim 12]
　The chemical conversion treatment liquid regenerator according to claim 11,
　wherein the chemical conversion treatment tank includes a
　first chemical conversion treatment tank and a second chemical conversion treatment tank, and
　the first liquid feeding
　path is provided on the chemical conversion treatment tank side. A first liquid feeding passage main body having two end portions and one of the end portions of the first liquid feeding passage main body on the chemical conversion treatment tank side, and the oxalic acid treatment in the first liquid feeding passage main body A first chemical conversion treatment tank side discharge port for discharging a liquid into the first chemical conversion treatment tank, and the other end of the chemical conversion treatment tank side of the first liquid feeding passage body, A second chemical conversion treatment tank side discharge port for discharging the oxalic acid treatment liquid in the channel body into the second chemical conversion treatment tank, and
　the second liquid feeding passage has
　two end portions on the chemical conversion treatment tank side. Is formed on one of the end of the second liquid feed path body on the chemical conversion treatment tank side of the second liquid feed path main body, and the oxalic acid treatment liquid in the first chemical conversion treatment tank is fed to the second feed liquid body. The oxalic acid in the second chemical conversion treatment tank, which is formed at the other one of the first chemical conversion treatment tank side inlet for flowing into the liquid channel body and the other end of the second liquid feeding channel body on the chemical conversion treatment tank side. A second chemical conversion treatment tank side inlet for allowing a treatment liquid to flow into the second liquid supply path,
　wherein the flow mechanism further includes
　the first chemical conversion treatment tank side outlet or the second chemical conversion treatment tank side outlet. From which of the discharge port switching mechanism for switching whether to discharge the oxalic acid treatment liquid in the first liquid feeding passage main body,
　the first chemical conversion treatment tank side inlet or the second chemical conversion treatment tank side inlet A chemical conversion treatment liquid regenerator, comprising: an inflow port switching mechanism that switches whether the oxalic acid treatment liquid is allowed to flow into the second liquid supply passage body.
[Claim 13]
　The chemical conversion treatment liquid regenerator according to any one of claims 10 to 12,
　wherein the flow mechanism
　circulates the during-regeneration treatment liquid circulation path for circulating the oxalic acid treatment liquid in the treatment liquid regeneration tank. The
　processing liquid circulation passage during regeneration is
　capable of accommodating a part of the oxalic acid treatment liquid in the treatment liquid regeneration tank, and has a main body of a treatment liquid circulation passage during regeneration having both ends, and the treatment
　during regeneration treatment. A processing liquid in-regeneration inlet that is formed at one end of the liquid circulation path body and that allows the oxalic acid processing liquid in the processing liquid regeneration tank to flow into the processing liquid circulation body during
　regeneration, and the processing liquid during regeneration. is formed on the other end of the circulation passage body, said the processing liquid outlet port reproduced for discharging the oxalic acid treatment solution of the reproduction in the treatment liquid circulation path body in the processing liquid regeneration tank,
　the reproduction processing solution A regenerating treatment liquid circulating drive source for moving the oxalic acid treatment liquid in the circulation path main body from the regenerating treatment liquid inflow port to the regenerating treatment liquid discharge port, and the
　regenerating treatment liquid inlet and the regeneration A chemical conversion treatment liquid regenerator in which at least one of the light source members is disposed between the intermediate treatment liquid discharge port and the medium treatment liquid discharge port.
[Claim 14]
　The chemical conversion treatment liquid regenerator according to any one of claims 8 to 13,
　wherein at least a part of a bottom surface of the treatment liquid regeneration tank is inclined.
[Claim 15]
　The chemical conversion treatment liquid regenerator according to any one of claims 8 to 14,
　wherein the treatment liquid regeneration tank is divided into a light irradiation chamber and a precipitation chamber by a
　partition member, and the partition member is The
　chemical conversion liquid regenerator having an opening that connects the light irradiation chamber and the precipitation chamber, and the one or more light source members are arranged in the light irradiation chamber.
[Claim 16]
　The chemical conversion treatment liquid regeneration device according to claim 15,
　wherein the bottom surface of the light irradiation chamber is lowered from the light irradiation chamber toward the precipitation chamber.
[Claim 17]
　The chemical conversion treatment liquid regenerating apparatus according to any one of claims 10 to 16,
　wherein the treatment liquid regenerating tank is further arranged so that it can be immersed in the oxalic acid treatment liquid in the treatment liquid regenerating tank. A chemical conversion treatment liquid regenerator comprising a flow direction changing member that changes the direction of the flow of the oxalic acid treatment liquid in the treatment liquid regeneration tank.
[Claim 18]
　The chemical conversion treatment liquid regenerator according to any one of claims 8 to 17,
　wherein the light irradiation device is an ultraviolet irradiation device.