WO2023119827A1 - Chemical treatment liquid and method for chemical treatment of target metal material - Google Patents
Chemical treatment liquid and method for chemical treatment of target metal material Download PDFInfo
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- WO2023119827A1 WO2023119827A1 PCT/JP2022/039102 JP2022039102W WO2023119827A1 WO 2023119827 A1 WO2023119827 A1 WO 2023119827A1 JP 2022039102 W JP2022039102 W JP 2022039102W WO 2023119827 A1 WO2023119827 A1 WO 2023119827A1
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- chemical conversion
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
Definitions
- the present invention relates to a chemical conversion treatment solution and a method of chemically treating a target metal material, particularly to a chemical conversion treatment solution that does not require chromium and a method of chemical conversion treatment of a target metal material.
- Chemical treatment is performed to increase the corrosion resistance of metals.
- chemical conversion treatment solutions containing chromium and cobalt have been used for this treatment. become very high.
- a chromate treatment solution when used, hexavalent chromium, which is toxic to the human body, can be eluted. Therefore, a chromium-free chemical conversion treatment solution is desired in order to avoid environmental pollution and adverse effects on the human body.
- Patent Documents 1 to 4 describe a chromium-free chemical conversion treatment liquid containing titanium complex fluoride ions and vanadium compound ions containing pentavalent vanadium, and the chromium-free chemical conversion treatment liquid is used for aluminum or aluminum alloys. It is stated that However, Patent Documents 1 to 4 do not describe a chromium-free chemical conversion treatment solution containing an oxidizing agent at a specific concentration or higher.
- JP 2010-261058 A JP-A-2003-213458 JP-A-2002-60699 WO2003/074761
- an object of the present invention is to provide a chemical conversion treatment solution capable of forming a film having improved corrosion resistance.
- the present inventors have found that by adding a high-concentration oxidizing agent to a chemical conversion treatment solution containing water-soluble titanium complex ions and water-soluble vanadium-containing ions, it is possible to eliminate the use of chromium.
- the present inventors have found that a coating with good corrosion resistance can be formed even with a That is, the present invention provides a chemical conversion treatment solution and a method for chemically treating a target metal material, which will be described below.
- a high-concentration oxidizing agent to a chemical conversion treatment solution containing water-soluble titanium complex ions and water-soluble vanadium-containing ions, it is possible to form a film having good corrosion resistance on the surface of a target metal material. can. In this case, it is not necessary to add chromium to the chemical conversion treatment liquid, so it is possible to provide an environmentally friendly chemical conversion treatment liquid.
- the present invention relates to a chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent.
- water-soluble titanium complex ions those commonly used in the art can be employed without particular limitation.
- the water-soluble titanium complex ions are titanium complex fluoride ions.
- the water-soluble titanium complex ion is derived from at least one titanium compound selected from the group consisting of titanium hydrofluoric acid, sodium titanium fluoride, potassium titanium fluoride, and ammonium titanium fluoride. There may be.
- the concentration of the water-soluble titanium complex ion is not particularly limited as long as the chemical conversion treatment is possible.
- the water-soluble vanadium-containing ions include vanadium It may be a compound ion. More specifically, said water-soluble vanadium-containing ions are selected from the group consisting of sodium vanadate, potassium vanadate, ammonium vanadate, sodium metavanadate, potassium metavanadate, ammonium metavanadate, and vanadium oxytrichloride. It may be derived from at least one vanadium compound or the like.
- the concentration of the water-soluble vanadium-containing ions is not particularly limited as long as the chemical conversion treatment is possible. about 1.2 g/L.
- the chemical conversion treatment solution of the present invention contains the oxidizing agent at a high concentration, specifically at a concentration of about 0.03 mol/L or more or about 0.07 mol/L or more.
- concentration of the oxidizing agent is not particularly limited, it may be, for example, about 0.15 mol/L or less.
- the oxidizing agent those commonly used in the art can be employed without particular limitation.
- oxidizing agent examples include nitric acid, nitrite, sulfuric acid, sulfurous acid, persulfuric acid, At least one selected from the group consisting of acid, hydrochloric acid, bromic acid, chloric acid, hypochlorous acid, hydrogen peroxide, permanganic acid, metavanadic acid, tungstic acid, molybdic acid, and salts thereof.
- nitric acid nitrite
- sulfuric acid sulfurous acid
- persulfuric acid At least one selected from the group consisting of acid, hydrochloric acid, bromic acid, chloric acid, hypochlorous acid, hydrogen peroxide, permanganic acid, metavanadic acid, tungstic acid, molybdic acid, and salts thereof.
- the nitrate is not particularly limited, but is preferably water-soluble, and specifically includes ammonium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, chromium nitrate, aluminum nitrate, zirconyl nitrate, or cobalt nitrate.
- ammonium nitrate sodium nitrate, potassium nitrate, lithium nitrate, chromium nitrate, aluminum nitrate, zirconyl nitrate, or cobalt nitrate.
- the chemical conversion treatment solution of the present invention does not require chromium because it can form a film with improved corrosion resistance due to the presence of a high-concentration oxidizing agent. That is, in one aspect, the chemical conversion treatment solution does not contain hexavalent chromium ions and/or trivalent chromium ions.
- the chemical conversion treatment solution of the present invention does not substantially contain fluorine ions, specifically, the concentration of fluorine ions is 0 to about 0.3 g/L or 0 to about 0.1 g/L, Alternatively, no fluoride that liberates fluorine ions other than the fluoro complex is added.
- the fluorine ion is a free fluorine ion and can be clearly distinguished from a fluorine atom forming a complex ion with a metal.
- fluorides that release fluorine ions include sodium fluoride, sodium hydrogen fluoride, potassium fluoride, potassium hydrogen fluoride, ammonium fluoride, ammonium hydrogen fluoride, and hydrofluoric acid.
- the chemical conversion treatment solution of the present invention can be used for chemical conversion treatment of various target metal materials.
- the target metal material is not particularly limited, but for example, the target metal material is zinc, aluminum, iron, nickel, copper, or a material formed of zinc, aluminum, iron, nickel, copper, or an alloy thereof, or a material plated with these metals.
- a zinc-containing metal material (including zinc-plated products and zinc-alloy plated products) is also preferred.
- the conversion baths of the present invention contain at least one additional water-soluble metal salt (e.g., nitrate, chloride salts, or sulfates, etc.).
- said water-soluble metal salt comprises Zn, providing zinc ions to said conversion treatment solution.
- concentration of the water-soluble metal salt is not particularly limited as long as the chemical conversion treatment is possible. 0 g/L.
- the pH of the chemical conversion treatment solution of the present invention is not particularly limited, it may be, for example, about 2.0 to about 5.0, preferably about 3.0 to about 4.5.
- the chemical conversion treatment solution of the present invention may further contain any additives commonly used in the technical field as long as they do not impair the purpose of the present invention.
- the present invention also relates to a method of chemically treating a target metal material, the step of immersing the target metal material in the chemical conversion treatment solution of the present invention, or the step of subjecting the target metal material to the chemical conversion treatment solution of the present invention. includes a step of spraying a chemical conversion treatment solution.
- the type of target metal material to which the method of the present invention is applied is not particularly limited. It may be a material, preferably a zinc-containing metallic material (including zinc-plated and zinc-alloy plated materials).
- the treatment temperature and treatment time when the target metal is brought into contact with the chemical conversion treatment solution are not particularly limited. It may be about 45° C. and the treatment time may be about 20 to about 400 seconds, preferably about 30 to about 200 seconds. Moreover, the method of the present invention may further include any step commonly used in the technical field as long as it does not impair the purpose of the present invention.
- Test Example 2 The chemical conversion treatment was performed in the same manner as in Test Example 1 except that the chemical conversion treatment solution shown in Table 2 or 3 was used, and the corrosion resistance of the coating formed on the surface of the ZDC was evaluated. The results are shown in Tables 2 and 3.
- Test Example 3 Chemical conversion treatment was performed in the same manner as in Test Example 1 except that the pH of chemical conversion treatment solution 5 was changed as shown in Table 4, and the corrosion resistance of the coating formed on the surface of ZDC was evaluated. Table 4 shows the results.
- a film with good corrosion resistance was formed under any of the conditions listed in Table 4. It was found that even if the pH of the chemical conversion treatment solution was changed within the range shown in Table 4, a film with good corrosion resistance was formed as long as the nitrate ion (oxidizing agent) was sufficiently contained.
- Test Example 4 Chemical conversion treatment was performed in the same manner as in Test Example 1 except that chemical conversion treatment liquid 5 was used and the chemical conversion treatment was performed at the temperature and time shown in Table 5, and the corrosion resistance of the coating formed on the surface of ZDC was evaluated. Table 5 shows the results.
- a film with good corrosion resistance was formed under any of the conditions listed in Table 5. It was found that even if the temperature and time of chemical conversion treatment were varied within the ranges shown in Table 5, a film with good corrosion resistance was formed as long as nitrate ions (oxidizing agent) were sufficiently contained.
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Abstract
The objective of the present invention is to provide a chemical treatment liquid capable of forming a coating having improved corrosion resistance. The present invention relates to a chemical treatment liquid containing a water-soluble titanium complex ion, a water-soluble vanadium-containing ion, and 0.03 mol /L or more of an oxidizing agent, wherein the concentration of a fluorine ion is 0 to 0.3 g / L, or alternatively, a fluoride releasing a fluorine ion other than of a fluoro complex is not added.
Description
本発明は、化成処理液及び対象金属材料を化成処理する方法、特にクロムを必要としない化成処理液及び対象金属材料を化成処理する方法に関する。
The present invention relates to a chemical conversion treatment solution and a method of chemically treating a target metal material, particularly to a chemical conversion treatment solution that does not require chromium and a method of chemical conversion treatment of a target metal material.
金属の耐食性を高めるために化成処理が行われている。この処理のために、従来からクロム及びコバルトを含む化成処理液が使用されているが、排水に含まれるクロムやコバルトはスラッジとなるため、産業廃棄物処理を行う必要があり、排水処理コストが非常に高くなる。また、クロメート処理液を使用すると、人体に有毒な６価クロムが溶出され得るため、環境汚染や人体への悪影響を避けるために、クロムフリーの化成処理液が求められている。
Chemical treatment is performed to increase the corrosion resistance of metals. Conventionally, chemical conversion treatment solutions containing chromium and cobalt have been used for this treatment. become very high. In addition, when a chromate treatment solution is used, hexavalent chromium, which is toxic to the human body, can be eluted. Therefore, a chromium-free chemical conversion treatment solution is desired in order to avoid environmental pollution and adverse effects on the human body.
特許文献１～４には、チタン錯フッ化物イオンと５価のバナジウムを含むバナジウム化合物イオンとを含むクロムフリー化成処理液が記載されており、当該クロムフリー化成処理液はアルミニウム又はアルミニウム合金に用いられる旨が記載されている。しかしながら、特許文献１～４には、特定の濃度以上の酸化剤を含むクロムフリー化成処理液は記載されていない。
Patent Documents 1 to 4 describe a chromium-free chemical conversion treatment liquid containing titanium complex fluoride ions and vanadium compound ions containing pentavalent vanadium, and the chromium-free chemical conversion treatment liquid is used for aluminum or aluminum alloys. It is stated that However, Patent Documents 1 to 4 do not describe a chromium-free chemical conversion treatment solution containing an oxidizing agent at a specific concentration or higher.
従来のクロムフリー化成処理液により形成された皮膜の耐食性は十分なものではなく、耐食性がさらに向上した皮膜を形成することのできるクロムフリー化成処理液が求められていた。そこで、本発明は、耐食性が向上した皮膜を形成することのできる化成処理液を提供することを目的としている。
The corrosion resistance of the film formed by the conventional chromium-free chemical conversion treatment solution is not sufficient, and there has been a demand for a chromium-free chemical conversion treatment solution that can form a film with further improved corrosion resistance. SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a chemical conversion treatment solution capable of forming a film having improved corrosion resistance.
本発明者らは、上記課題を解決すべく鋭意検討した結果、水溶性チタン錯イオン及び水溶性バナジウム含有イオンを含む化成処理液に高濃度の酸化剤を配合することで、クロムを使用しなくても耐食性の良好な皮膜を形成できることを見出し、本発明を完成させた。すなわち、本発明は、以下に示す化成処理液及び対象金属材料を化成処理する方法を提供するものである。
〔１〕水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液であって、フッ素イオンの濃度が０～０．３ｇ／Ｌである、化成処理液。
〔２〕水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液であって、フルオロ錯体以外のフッ素イオンを遊離するフッ化物は添加されていない、化成処理液。
〔３〕ｐＨが２．０～５．０である、前記〔１〕又は〔２〕に記載の化成処理液。
〔４〕前記酸化剤が、硝酸及び／又は硝酸イオンを遊離する硝酸塩を含む、前記〔１〕～〔３〕のいずれか１項に記載の化成処理液。
〔５〕前記水溶性チタン錯イオンが、チタン錯フッ化物イオンである、前記〔１〕～〔４〕のいずれか１項に記載の化成処理液。
〔６〕前記水溶性チタン錯イオンのチタン換算濃度が、０．１５～１０ｇ／Ｌである、前記〔１〕～〔５〕のいずれか１項に記載の化成処理液。
〔７〕前記水溶性バナジウム含有イオンが、５価のバナジウムを含むバナジウム化合物イオンである、前記〔１〕～〔６〕のいずれか１項に記載の化成処理液。
〔８〕前記水溶性バナジウム含有イオンのバナジウム換算濃度が、０．４～１５ｇ／Ｌである、前記〔１〕～〔７〕のいずれか１項に記載の化成処理液。
〔９〕Ｚｎ、Ｃｏ、Ｗ、Ｚｒ、Ｍｎ、Ｍｏ、Ｔａ、Ｃｅ、Ｓｒ、又はＦｅを含む少なくとも１種の追加の水溶性金属塩をさらに含む、前記〔１〕～〔８〕のいずれか１項に記載の化成処理液。
〔１０〕６価クロムイオン及び／又は３価クロムイオンを含まない、前記〔１〕～〔９〕のいずれか１項に記載の化成処理液。
〔１１〕亜鉛含有金属材料に用いるための、前記〔１〕～〔１０〕のいずれか１項に記載の化成処理液。
〔１２〕対象金属材料を化成処理する方法であって、
前記対象金属材料を、前記〔１〕～〔１１〕のいずれか１項に記載の化成処理液に浸漬させる工程、又は、前記対象金属材料に、前記〔１〕～〔１１〕のいずれか１項に記載の化成処理液を噴霧する工程を含む、方法。
〔１３〕前記対象金属材料が、亜鉛含有金属材料である、前記〔１２〕に記載の方法。 As a result of intensive studies to solve the above problems, the present inventors have found that by adding a high-concentration oxidizing agent to a chemical conversion treatment solution containing water-soluble titanium complex ions and water-soluble vanadium-containing ions, it is possible to eliminate the use of chromium. The present inventors have found that a coating with good corrosion resistance can be formed even with a That is, the present invention provides a chemical conversion treatment solution and a method for chemically treating a target metal material, which will be described below.
[1] A chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent, wherein the fluorine ion concentration is 0 to 0.3 g/L. , chemical conversion treatment liquid.
[2] A chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent, in which a fluoride other than a fluoro complex that liberates fluorine ions is not added. Not chemical conversion solution.
[3] The chemical conversion treatment solution according to [1] or [2] above, which has a pH of 2.0 to 5.0.
[4] The chemical conversion treatment solution according to any one of [1] to [3], wherein the oxidizing agent contains nitric acid and/or a nitrate that liberates nitrate ions.
[5] The chemical conversion treatment solution according to any one of [1] to [4], wherein the water-soluble titanium complex ion is a titanium complex fluoride ion.
[6] The chemical conversion treatment solution according to any one of [1] to [5], wherein the concentration of the water-soluble titanium complex ions in terms of titanium is 0.15 to 10 g/L.
[7] The chemical conversion treatment solution according to any one of [1] to [6], wherein the water-soluble vanadium-containing ions are vanadium compound ions containing pentavalent vanadium.
[8] The chemical conversion treatment solution according to any one of [1] to [7], wherein the water-soluble vanadium-containing ions have a vanadium-equivalent concentration of 0.4 to 15 g/L.
[9] Any of the above [1] to [8], further comprising at least one additional water-soluble metal salt containing Zn, Co, W, Zr, Mn, Mo, Ta, Ce, Sr, or Fe 2. The chemical conversion treatment liquid according to item 1.
[10] The chemical conversion treatment solution according to any one of [1] to [9], which does not contain hexavalent chromium ions and/or trivalent chromium ions.
[11] The chemical conversion treatment solution according to any one of [1] to [10] above, which is used for a zinc-containing metal material.
[12] A method for chemical conversion treatment of a target metal material,
A step of immersing the target metal material in the chemical conversion treatment solution according to any one of [1] to [11], or immersing the target metal material in any one of [1] to [11] A method, comprising the step of spraying the chemical conversion treatment solution according to Item.
[13] The method according to [12] above, wherein the target metallic material is a zinc-containing metallic material.
〔１〕水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液であって、フッ素イオンの濃度が０～０．３ｇ／Ｌである、化成処理液。
〔２〕水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液であって、フルオロ錯体以外のフッ素イオンを遊離するフッ化物は添加されていない、化成処理液。
〔３〕ｐＨが２．０～５．０である、前記〔１〕又は〔２〕に記載の化成処理液。
〔４〕前記酸化剤が、硝酸及び／又は硝酸イオンを遊離する硝酸塩を含む、前記〔１〕～〔３〕のいずれか１項に記載の化成処理液。
〔５〕前記水溶性チタン錯イオンが、チタン錯フッ化物イオンである、前記〔１〕～〔４〕のいずれか１項に記載の化成処理液。
〔６〕前記水溶性チタン錯イオンのチタン換算濃度が、０．１５～１０ｇ／Ｌである、前記〔１〕～〔５〕のいずれか１項に記載の化成処理液。
〔７〕前記水溶性バナジウム含有イオンが、５価のバナジウムを含むバナジウム化合物イオンである、前記〔１〕～〔６〕のいずれか１項に記載の化成処理液。
〔８〕前記水溶性バナジウム含有イオンのバナジウム換算濃度が、０．４～１５ｇ／Ｌである、前記〔１〕～〔７〕のいずれか１項に記載の化成処理液。
〔９〕Ｚｎ、Ｃｏ、Ｗ、Ｚｒ、Ｍｎ、Ｍｏ、Ｔａ、Ｃｅ、Ｓｒ、又はＦｅを含む少なくとも１種の追加の水溶性金属塩をさらに含む、前記〔１〕～〔８〕のいずれか１項に記載の化成処理液。
〔１０〕６価クロムイオン及び／又は３価クロムイオンを含まない、前記〔１〕～〔９〕のいずれか１項に記載の化成処理液。
〔１１〕亜鉛含有金属材料に用いるための、前記〔１〕～〔１０〕のいずれか１項に記載の化成処理液。
〔１２〕対象金属材料を化成処理する方法であって、
前記対象金属材料を、前記〔１〕～〔１１〕のいずれか１項に記載の化成処理液に浸漬させる工程、又は、前記対象金属材料に、前記〔１〕～〔１１〕のいずれか１項に記載の化成処理液を噴霧する工程を含む、方法。
〔１３〕前記対象金属材料が、亜鉛含有金属材料である、前記〔１２〕に記載の方法。 As a result of intensive studies to solve the above problems, the present inventors have found that by adding a high-concentration oxidizing agent to a chemical conversion treatment solution containing water-soluble titanium complex ions and water-soluble vanadium-containing ions, it is possible to eliminate the use of chromium. The present inventors have found that a coating with good corrosion resistance can be formed even with a That is, the present invention provides a chemical conversion treatment solution and a method for chemically treating a target metal material, which will be described below.
[1] A chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent, wherein the fluorine ion concentration is 0 to 0.3 g/L. , chemical conversion treatment liquid.
[2] A chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent, in which a fluoride other than a fluoro complex that liberates fluorine ions is not added. Not chemical conversion solution.
[3] The chemical conversion treatment solution according to [1] or [2] above, which has a pH of 2.0 to 5.0.
[4] The chemical conversion treatment solution according to any one of [1] to [3], wherein the oxidizing agent contains nitric acid and/or a nitrate that liberates nitrate ions.
[5] The chemical conversion treatment solution according to any one of [1] to [4], wherein the water-soluble titanium complex ion is a titanium complex fluoride ion.
[6] The chemical conversion treatment solution according to any one of [1] to [5], wherein the concentration of the water-soluble titanium complex ions in terms of titanium is 0.15 to 10 g/L.
[7] The chemical conversion treatment solution according to any one of [1] to [6], wherein the water-soluble vanadium-containing ions are vanadium compound ions containing pentavalent vanadium.
[8] The chemical conversion treatment solution according to any one of [1] to [7], wherein the water-soluble vanadium-containing ions have a vanadium-equivalent concentration of 0.4 to 15 g/L.
[9] Any of the above [1] to [8], further comprising at least one additional water-soluble metal salt containing Zn, Co, W, Zr, Mn, Mo, Ta, Ce, Sr, or Fe 2. The chemical conversion treatment liquid according to item 1.
[10] The chemical conversion treatment solution according to any one of [1] to [9], which does not contain hexavalent chromium ions and/or trivalent chromium ions.
[11] The chemical conversion treatment solution according to any one of [1] to [10] above, which is used for a zinc-containing metal material.
[12] A method for chemical conversion treatment of a target metal material,
A step of immersing the target metal material in the chemical conversion treatment solution according to any one of [1] to [11], or immersing the target metal material in any one of [1] to [11] A method, comprising the step of spraying the chemical conversion treatment solution according to Item.
[13] The method according to [12] above, wherein the target metallic material is a zinc-containing metallic material.
本発明に従えば、水溶性チタン錯イオン及び水溶性バナジウム含有イオンを含む化成処理液に高濃度の酸化剤を配合することにより、対象金属材料の表面に耐食性の良好な皮膜を形成することができる。この場合、化成処理液中にクロムを配合する必要がないため、環境にやさしい化成処理液を提供することが可能となる。
According to the present invention, by adding a high-concentration oxidizing agent to a chemical conversion treatment solution containing water-soluble titanium complex ions and water-soluble vanadium-containing ions, it is possible to form a film having good corrosion resistance on the surface of a target metal material. can. In this case, it is not necessary to add chromium to the chemical conversion treatment liquid, so it is possible to provide an environmentally friendly chemical conversion treatment liquid.
以下、本発明をさらに詳細に説明する。
本発明は、水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液に関している。前記水溶性チタン錯イオンとしては、当技術分野で通常使用されているものを特に制限されることなく採用することができるが、例えば、前記水溶性チタン錯イオンは、チタン錯フッ化物イオンであってもよい。より具体的には、前記水溶性チタン錯イオンは、チタンフッ化水素酸、チタンフッ化ナトリウム、チタンフッ化カリウム、及びチタンフッ化アンモニウムからなる群から選択される少なくとも１種のチタン化合物などに由来するものであってもよい。前記水溶性チタン錯イオンの濃度は、化成処理が可能である限り特に制限されないが、例えば、チタン換算濃度で約０．１５～約１０ｇ／Ｌであってもよく、好ましくは約０．３～約１ｇ／Ｌである。なお、前記チタン錯フッ化物イオンのようなフルオロ錯体からは、フッ素イオンは遊離されにくいため、通常の濃度範囲で化成処理液に使用している限りは、当該フルオロ錯体に由来するフッ素イオンの濃度は０．３ｇ／Ｌを下回る。 The present invention will now be described in more detail.
The present invention relates to a chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent. As the water-soluble titanium complex ions, those commonly used in the art can be employed without particular limitation. For example, the water-soluble titanium complex ions are titanium complex fluoride ions. may More specifically, the water-soluble titanium complex ion is derived from at least one titanium compound selected from the group consisting of titanium hydrofluoric acid, sodium titanium fluoride, potassium titanium fluoride, and ammonium titanium fluoride. There may be. The concentration of the water-soluble titanium complex ion is not particularly limited as long as the chemical conversion treatment is possible. about 1 g/L. Since fluorine ions are difficult to liberate from fluoro complexes such as the titanium complex fluoride ions, as long as the chemical conversion treatment solution is used in the normal concentration range, the concentration of fluorine ions derived from the fluoro complexes is is below 0.3 g/L.
本発明は、水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液に関している。前記水溶性チタン錯イオンとしては、当技術分野で通常使用されているものを特に制限されることなく採用することができるが、例えば、前記水溶性チタン錯イオンは、チタン錯フッ化物イオンであってもよい。より具体的には、前記水溶性チタン錯イオンは、チタンフッ化水素酸、チタンフッ化ナトリウム、チタンフッ化カリウム、及びチタンフッ化アンモニウムからなる群から選択される少なくとも１種のチタン化合物などに由来するものであってもよい。前記水溶性チタン錯イオンの濃度は、化成処理が可能である限り特に制限されないが、例えば、チタン換算濃度で約０．１５～約１０ｇ／Ｌであってもよく、好ましくは約０．３～約１ｇ／Ｌである。なお、前記チタン錯フッ化物イオンのようなフルオロ錯体からは、フッ素イオンは遊離されにくいため、通常の濃度範囲で化成処理液に使用している限りは、当該フルオロ錯体に由来するフッ素イオンの濃度は０．３ｇ／Ｌを下回る。 The present invention will now be described in more detail.
The present invention relates to a chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent. As the water-soluble titanium complex ions, those commonly used in the art can be employed without particular limitation. For example, the water-soluble titanium complex ions are titanium complex fluoride ions. may More specifically, the water-soluble titanium complex ion is derived from at least one titanium compound selected from the group consisting of titanium hydrofluoric acid, sodium titanium fluoride, potassium titanium fluoride, and ammonium titanium fluoride. There may be. The concentration of the water-soluble titanium complex ion is not particularly limited as long as the chemical conversion treatment is possible. about 1 g/L. Since fluorine ions are difficult to liberate from fluoro complexes such as the titanium complex fluoride ions, as long as the chemical conversion treatment solution is used in the normal concentration range, the concentration of fluorine ions derived from the fluoro complexes is is below 0.3 g/L.
前記水溶性バナジウム含有イオンとしては、当技術分野で通常使用されているものを特に制限されることなく採用することができるが、例えば、前記水溶性バナジウム含有イオンは、５価のバナジウムを含むバナジウム化合物イオンであってもよい。より具体的には、前記水溶性バナジウム含有イオンは、バナジン酸ナトリウム、バナジン酸カリウム、バナジン酸アンモニウム、メタバナジン酸ナトリウム、メタバナジン酸カリウム、メタバナジン酸アンモニウム、及びオキシ三塩化バナジウムからなる群から選択される少なくとも１種のバナジウム化合物などに由来するものであってもよい。前記水溶性バナジウム含有イオンの濃度は、化成処理が可能である限り特に制限されないが、例えば、バナジウム換算濃度で約０．４～約１５ｇ／Ｌであってもよく、好ましくは約０．５～約１．２ｇ／Ｌである。
As the water-soluble vanadium-containing ions, those commonly used in the art can be employed without particular limitation. For example, the water-soluble vanadium-containing ions include vanadium It may be a compound ion. More specifically, said water-soluble vanadium-containing ions are selected from the group consisting of sodium vanadate, potassium vanadate, ammonium vanadate, sodium metavanadate, potassium metavanadate, ammonium metavanadate, and vanadium oxytrichloride. It may be derived from at least one vanadium compound or the like. The concentration of the water-soluble vanadium-containing ions is not particularly limited as long as the chemical conversion treatment is possible. about 1.2 g/L.
本発明の化成処理液は、前記酸化剤を高濃度で含んでおり、具体的には約０．０３ｍｏｌ／Ｌ以上又は約０．０７ｍｏｌ／Ｌ以上の濃度で含んでいる。前記酸化剤の濃度の上限値は、特に制限されないが、例えば、約０．１５ｍｏｌ／Ｌ以下であってもよい。前記酸化剤としては、当技術分野で通常使用されているものを特に制限されることなく採用することができるが、例えば、前記酸化剤は、硝酸、亜硝酸、硫酸、亜硫酸、過硫酸、リン酸、塩酸、臭素酸、塩素酸、次亜塩素酸、過酸化水素、過マンガン酸、メタバナジン酸、タングステン酸、モリブデン酸、及びそれらの塩などからなる群から選択される少なくとも１種を含んでもよく、好ましくは、硝酸及び／又は硝酸イオンを遊離する硝酸塩を含む。前記硝酸塩は、特に限定されないが、水溶性であることが好ましく、具体的には、硝酸アンモニウム、硝酸ナトリウム、硝酸カリウム、硝酸リチウム、硝酸クロム、硝酸アルミニウム、硝酸ジルコニル、又は硝酸コバルトなどを含んでもよい。前記酸化剤を化成処理液に含ませることで化成皮膜の形成を促進することができ、より優れた外観と耐食性を達成することができる。
The chemical conversion treatment solution of the present invention contains the oxidizing agent at a high concentration, specifically at a concentration of about 0.03 mol/L or more or about 0.07 mol/L or more. Although the upper limit of the concentration of the oxidizing agent is not particularly limited, it may be, for example, about 0.15 mol/L or less. As the oxidizing agent, those commonly used in the art can be employed without particular limitation. Examples of the oxidizing agent include nitric acid, nitrite, sulfuric acid, sulfurous acid, persulfuric acid, At least one selected from the group consisting of acid, hydrochloric acid, bromic acid, chloric acid, hypochlorous acid, hydrogen peroxide, permanganic acid, metavanadic acid, tungstic acid, molybdic acid, and salts thereof. Well, preferably, it contains nitric acid and/or a nitrate that liberates nitrate ions. The nitrate is not particularly limited, but is preferably water-soluble, and specifically includes ammonium nitrate, sodium nitrate, potassium nitrate, lithium nitrate, chromium nitrate, aluminum nitrate, zirconyl nitrate, or cobalt nitrate. By including the oxidizing agent in the chemical conversion treatment liquid, the formation of the chemical conversion film can be promoted, and better appearance and corrosion resistance can be achieved.
本発明の化成処理液は、高濃度の酸化剤の存在により耐食性が向上した皮膜を形成できるため、クロムを必要としない。すなわち、ある態様では、前記化成処理液は、６価クロムイオン及び／又は３価クロムイオンを含まない。
The chemical conversion treatment solution of the present invention does not require chromium because it can form a film with improved corrosion resistance due to the presence of a high-concentration oxidizing agent. That is, in one aspect, the chemical conversion treatment solution does not contain hexavalent chromium ions and/or trivalent chromium ions.
本発明の化成処理液は、フッ素イオンを実質的に含んでおらず、具体的には、フッ素イオンの濃度が０～約０．３ｇ／Ｌ又は０～約０．１ｇ／Ｌであるか、又は、フルオロ錯体以外のフッ素イオンを遊離するフッ化物は添加されていない。前記フッ素イオンは、遊離のフッ素イオンであり、金属との錯イオンを形成しているフッ素原子とは明確に区別され得る。前記フッ素イオンを遊離するフッ化物としては、例えば、フッ化ナトリウム、フッ化水素ナトリウム、フッ化カリウム、フッ化水素カリウム、フッ化アンモニウム、フッ化水素アンモニウム、及びフッ化水素酸などが挙げられる。本発明の化成処理液においては、フッ素イオンの濃度を低くすることで過剰なエッチングを避けることができ、対象金属材料（特に亜鉛含有金属材料）の外観を良好に保ちつつ、耐食性の優れた皮膜を形成することができると考えられる。
The chemical conversion treatment solution of the present invention does not substantially contain fluorine ions, specifically, the concentration of fluorine ions is 0 to about 0.3 g/L or 0 to about 0.1 g/L, Alternatively, no fluoride that liberates fluorine ions other than the fluoro complex is added. The fluorine ion is a free fluorine ion and can be clearly distinguished from a fluorine atom forming a complex ion with a metal. Examples of fluorides that release fluorine ions include sodium fluoride, sodium hydrogen fluoride, potassium fluoride, potassium hydrogen fluoride, ammonium fluoride, ammonium hydrogen fluoride, and hydrofluoric acid. In the chemical conversion treatment solution of the present invention, excessive etching can be avoided by reducing the concentration of fluorine ions, and a film with excellent corrosion resistance can be obtained while maintaining a good appearance of the target metal material (especially zinc-containing metal material). can be formed.
本発明の化成処理液は、種々の対象金属材料の化成処理を行うために使用することができる。前記対象金属材料は、特に制限されないが、例えば、前記対象金属材料は、亜鉛、アルミニウム、鉄、ニッケル、銅、又はそれらの合金から形成された材料又はそれらの金属でめっきされた材料であってもよく、好ましくは、亜鉛含有金属材料（亜鉛めっき物及び亜鉛合金めっき物を含む）である。
The chemical conversion treatment solution of the present invention can be used for chemical conversion treatment of various target metal materials. The target metal material is not particularly limited, but for example, the target metal material is zinc, aluminum, iron, nickel, copper, or a material formed of zinc, aluminum, iron, nickel, copper, or an alloy thereof, or a material plated with these metals. A zinc-containing metal material (including zinc-plated products and zinc-alloy plated products) is also preferred.
ある態様では、本発明の化成処理液は、Ｚｎ、Ｃｏ、Ｗ、Ｚｒ、Ｍｎ、Ｍｏ、Ｔａ、Ｃｅ、Ｓｒ、又はＦｅを含む少なくとも１種の追加の水溶性金属塩（例えば、硝酸塩、塩化物塩、又は硫酸塩など）をさらに含む。好ましくは、前記水溶性金属塩は、Ｚｎを含むものであり、前記化成処理液に亜鉛イオンがもたらされる。このような水溶性金属塩が含まれていると、形成される皮膜の耐食性がさらに向上し得る。前記水溶性金属塩の濃度は、化成処理が可能である限り特に制限されないが、例えば、約０．４～約３０．０ｇ／Ｌであってもよく、好ましくは約０．８～約３．０ｇ／Ｌである。
In some embodiments, the conversion baths of the present invention contain at least one additional water-soluble metal salt (e.g., nitrate, chloride salts, or sulfates, etc.). Preferably, said water-soluble metal salt comprises Zn, providing zinc ions to said conversion treatment solution. When such a water-soluble metal salt is contained, the corrosion resistance of the formed film can be further improved. The concentration of the water-soluble metal salt is not particularly limited as long as the chemical conversion treatment is possible. 0 g/L.
本発明の化成処理液のｐＨは、特に制限されないが、例えば、約２．０～約５．０であってもよく、好ましくは約３．０～約４．５である。また、本発明の化成処理液は、本発明の目的を損なわない限り、当技術分野で通常使用される任意の添加剤をさらに含んでもよい。
Although the pH of the chemical conversion treatment solution of the present invention is not particularly limited, it may be, for example, about 2.0 to about 5.0, preferably about 3.0 to about 4.5. In addition, the chemical conversion treatment solution of the present invention may further contain any additives commonly used in the technical field as long as they do not impair the purpose of the present invention.
別の態様では、本発明は、対象金属材料を化成処理する方法にも関しており、前記対象金属材料を、本発明の化成処理液に浸漬させる工程、又は、前記対象金属材料に、本発明の化成処理液を噴霧する工程を含んでいる。本発明の方法が適用される対象金属材料の種類は特に制限されず、例えば、前記対象金属材料は、亜鉛、アルミニウム、鉄、又はそれらの合金から形成された材料又はそれらの金属でめっきされた材料であってもよく、好ましくは、亜鉛含有金属材料（亜鉛めっき物及び亜鉛合金めっき物を含む）である。
In another aspect, the present invention also relates to a method of chemically treating a target metal material, the step of immersing the target metal material in the chemical conversion treatment solution of the present invention, or the step of subjecting the target metal material to the chemical conversion treatment solution of the present invention. includes a step of spraying a chemical conversion treatment solution. The type of target metal material to which the method of the present invention is applied is not particularly limited. It may be a material, preferably a zinc-containing metallic material (including zinc-plated and zinc-alloy plated materials).
本発明の方法において、前記対象金属を前記化成処理液に接触させるときの処理温度及び処理時間は、特に制限されないが、例えば、前記処理温度は、約１５～約５５℃、好ましくは約２５～約４５℃であってもよく、前記処理時間は、約２０～約４００秒、好ましくは約３０～約２００秒であってもよい。また、本発明の方法は、本発明の目的を損なわない限り、当技術分野で通常使用される任意の工程をさらに含んでもよい。
In the method of the present invention, the treatment temperature and treatment time when the target metal is brought into contact with the chemical conversion treatment solution are not particularly limited. It may be about 45° C. and the treatment time may be about 20 to about 400 seconds, preferably about 30 to about 200 seconds. Moreover, the method of the present invention may further include any step commonly used in the technical field as long as it does not impair the purpose of the present invention.
以下、実施例により本発明を具体的に説明するが、本発明の範囲はこれら実施例に限定されるものではない。
The present invention will be specifically described below with reference to examples, but the scope of the present invention is not limited to these examples.
〔試験例１〕
チタンフッ化アンモニウム、メタバナジン酸ナトリウム、硝酸アンモニウム、及び硫酸亜鉛を混合し、水酸化ナトリウム又は硫酸でｐＨを４．００に調整して、後述の表１に記載の組成（ＮＯ3 -、ＴｉＦ6 2-、ＶＯ3 -、及びＺｎ2+の濃度は、それぞれ硝酸アンモニウム、チタンフッ化アンモニウム、メタバナジン酸ナトリウム、及び硫酸亜鉛の配合量に基づくものであり、これらの化合物はすべて電離するがＴｉＦ6 2-からＦ-は生じず、Ｆ-の濃度は０ｇ／Ｌに近いとみなした。）の化成処理液１～６を常法により調製した。亜鉛合金ダイカストであるＺＤＣ２（日本テストパネル株式会社製）に対して前処理の脱脂を行い、水洗した後、各化成処理液を用いて４０℃、６０秒の条件で化成処理を施した。処理後の亜鉛合金ダイカストを水洗し、６０℃で１０分以上乾燥させた。そして、塩水噴霧試験方法（ＪＩＳ Ｚ ２３７１）の中性塩水噴霧試験（ＮＳＳ）を行い、形成された皮膜の耐食性（白色生成物が付着している面積の対象金属材料の表面積に対する割合）を塩水噴霧試験機に投入してから経時的に観察し、以下の基準で評価した。結果を表１に示す。
（皮膜の耐食性）
○：白色生成物なし
△：白色生成物５％未満
×：白色生成物５％以上 [Test Example 1]
Ammonium titanium fluoride, sodium metavanadate, ammonium nitrate, and zinc sulfate were mixed, the pH was adjusted to 4.00 with sodium hydroxide or sulfuric acid, and the composition (NO 3 - , TiF 6 2- , VO 3 − , and Zn 2+ are based on the loadings of ammonium nitrate, ammonium titanium fluoride, sodium metavanadate, and zinc sulfate, respectively, all of which ionize, but TiF 6 2− to F − was not generated and the concentration of F − was considered to be close to 0 g/L.) Chemical conversion solutions 1 to 6 were prepared by a conventional method. ZDC2 (manufactured by Nippon Test Panel Co., Ltd.), which is a zinc alloy die cast, was subjected to pretreatment degreasing, washing with water, and then chemical conversion treatment using each chemical conversion treatment solution under the conditions of 40 ° C. and 60 seconds. The treated zinc alloy die casting was washed with water and dried at 60° C. for 10 minutes or longer. Then, the neutral salt spray test (NSS) of the salt spray test method (JIS Z 2371) is performed, and the corrosion resistance of the formed film (the ratio of the area to which the white product is attached to the surface area of the target metal material) is evaluated. After being put into the spray tester, it was observed over time and evaluated according to the following criteria. Table 1 shows the results.
(Corrosion resistance of film)
○: no white product △: less than 5% white product ×: 5% or more white product
チタンフッ化アンモニウム、メタバナジン酸ナトリウム、硝酸アンモニウム、及び硫酸亜鉛を混合し、水酸化ナトリウム又は硫酸でｐＨを４．００に調整して、後述の表１に記載の組成（ＮＯ3 -、ＴｉＦ6 2-、ＶＯ3 -、及びＺｎ2+の濃度は、それぞれ硝酸アンモニウム、チタンフッ化アンモニウム、メタバナジン酸ナトリウム、及び硫酸亜鉛の配合量に基づくものであり、これらの化合物はすべて電離するがＴｉＦ6 2-からＦ-は生じず、Ｆ-の濃度は０ｇ／Ｌに近いとみなした。）の化成処理液１～６を常法により調製した。亜鉛合金ダイカストであるＺＤＣ２（日本テストパネル株式会社製）に対して前処理の脱脂を行い、水洗した後、各化成処理液を用いて４０℃、６０秒の条件で化成処理を施した。処理後の亜鉛合金ダイカストを水洗し、６０℃で１０分以上乾燥させた。そして、塩水噴霧試験方法（ＪＩＳ Ｚ ２３７１）の中性塩水噴霧試験（ＮＳＳ）を行い、形成された皮膜の耐食性（白色生成物が付着している面積の対象金属材料の表面積に対する割合）を塩水噴霧試験機に投入してから経時的に観察し、以下の基準で評価した。結果を表１に示す。
（皮膜の耐食性）
○：白色生成物なし
△：白色生成物５％未満
×：白色生成物５％以上 [Test Example 1]
Ammonium titanium fluoride, sodium metavanadate, ammonium nitrate, and zinc sulfate were mixed, the pH was adjusted to 4.00 with sodium hydroxide or sulfuric acid, and the composition (NO 3 - , TiF 6 2- , VO 3 − , and Zn 2+ are based on the loadings of ammonium nitrate, ammonium titanium fluoride, sodium metavanadate, and zinc sulfate, respectively, all of which ionize, but TiF 6 2− to F − was not generated and the concentration of F − was considered to be close to 0 g/L.) Chemical conversion solutions 1 to 6 were prepared by a conventional method. ZDC2 (manufactured by Nippon Test Panel Co., Ltd.), which is a zinc alloy die cast, was subjected to pretreatment degreasing, washing with water, and then chemical conversion treatment using each chemical conversion treatment solution under the conditions of 40 ° C. and 60 seconds. The treated zinc alloy die casting was washed with water and dried at 60° C. for 10 minutes or longer. Then, the neutral salt spray test (NSS) of the salt spray test method (JIS Z 2371) is performed, and the corrosion resistance of the formed film (the ratio of the area to which the white product is attached to the surface area of the target metal material) is evaluated. After being put into the spray tester, it was observed over time and evaluated according to the following criteria. Table 1 shows the results.
(Corrosion resistance of film)
○: no white product △: less than 5% white product ×: 5% or more white product
水溶性チタン錯イオン（ＴｉＦ6
2-）及び水溶性バナジウム含有イオン（ＶＯ3
-）を含む化成処理液において、硝酸イオン（酸化剤）の濃度を従来よりも高くすると、前記合金の表面に耐食性の高い皮膜を形成することができた（特に化成処理液３～５参照）。
In a chemical conversion treatment solution containing water-soluble titanium complex ions (TiF 6 2− ) and water-soluble vanadium-containing ions (VO 3 − ), if the concentration of nitrate ions (oxidizing agent) is higher than before, the surface of the alloy becomes corrosion resistant. It was possible to form a film with a high concentration (especially see chemical conversion treatment liquids 3 to 5).
〔試験例２〕
表２又は３に記載の化成処理液を使用した以外は試験例１と同様にして化成処理を行い、ＺＤＣの表面上に形成された皮膜の耐食性を評価した。結果を表２及び表３に示す。 [Test Example 2]
The chemical conversion treatment was performed in the same manner as in Test Example 1 except that the chemical conversion treatment solution shown in Table 2 or 3 was used, and the corrosion resistance of the coating formed on the surface of the ZDC was evaluated. The results are shown in Tables 2 and 3.
表２又は３に記載の化成処理液を使用した以外は試験例１と同様にして化成処理を行い、ＺＤＣの表面上に形成された皮膜の耐食性を評価した。結果を表２及び表３に示す。 [Test Example 2]
The chemical conversion treatment was performed in the same manner as in Test Example 1 except that the chemical conversion treatment solution shown in Table 2 or 3 was used, and the corrosion resistance of the coating formed on the surface of the ZDC was evaluated. The results are shown in Tables 2 and 3.
表２及び表３に記載のいずれの条件でも、耐食性の良好な皮膜が形成された。硝酸イオン（酸化剤）を十分に含んでいる限り、化成処理液中の水溶性チタン錯イオン（ＴｉＦ6
2-）、水溶性バナジウム含有イオン（ＶＯ3
-）、及び亜鉛イオンの濃度を表２及び表３の範囲で変化させても、耐食性の良好な皮膜が形成されることが分かった。
Under any of the conditions shown in Tables 2 and 3, films with good corrosion resistance were formed. The concentrations of water-soluble titanium complex ions (TiF 6 2− ), water-soluble vanadium-containing ions (VO 3 − ), and zinc ions in the chemical conversion treatment solution as long as the nitrate ions (oxidizing agent) are sufficiently contained are shown in Table 2. , and it was found that a coating with good corrosion resistance was formed even when the content was varied within the ranges shown in Table 3.
〔試験例３〕
化成処理液５のｐＨを表４に記載のように変更した以外は試験例１と同様にして化成処理を行い、ＺＤＣの表面上に形成された皮膜の耐食性を評価した。結果を表４に示す。 [Test Example 3]
Chemical conversion treatment was performed in the same manner as in Test Example 1 except that the pH of chemical conversion treatment solution 5 was changed as shown in Table 4, and the corrosion resistance of the coating formed on the surface of ZDC was evaluated. Table 4 shows the results.
化成処理液５のｐＨを表４に記載のように変更した以外は試験例１と同様にして化成処理を行い、ＺＤＣの表面上に形成された皮膜の耐食性を評価した。結果を表４に示す。 [Test Example 3]
Chemical conversion treatment was performed in the same manner as in Test Example 1 except that the pH of chemical conversion treatment solution 5 was changed as shown in Table 4, and the corrosion resistance of the coating formed on the surface of ZDC was evaluated. Table 4 shows the results.
表４に記載のいずれの条件でも、耐食性の良好な皮膜が形成された。硝酸イオン（酸化剤）を十分に含んでいる限り、化成処理液のｐＨを表４の範囲で変化させても、耐食性の良好な皮膜が形成されることが分かった。
A film with good corrosion resistance was formed under any of the conditions listed in Table 4. It was found that even if the pH of the chemical conversion treatment solution was changed within the range shown in Table 4, a film with good corrosion resistance was formed as long as the nitrate ion (oxidizing agent) was sufficiently contained.
〔試験例４〕
化成処理液５を用い、表５に記載の温度及び時間で化成処理を行った以外は試験例１と同様にして化成処理を行い、ＺＤＣの表面上に形成された皮膜の耐食性を評価した。結果を表５に示す。 [Test Example 4]
Chemical conversion treatment was performed in the same manner as in Test Example 1 except that chemical conversion treatment liquid 5 was used and the chemical conversion treatment was performed at the temperature and time shown in Table 5, and the corrosion resistance of the coating formed on the surface of ZDC was evaluated. Table 5 shows the results.
化成処理液５を用い、表５に記載の温度及び時間で化成処理を行った以外は試験例１と同様にして化成処理を行い、ＺＤＣの表面上に形成された皮膜の耐食性を評価した。結果を表５に示す。 [Test Example 4]
Chemical conversion treatment was performed in the same manner as in Test Example 1 except that chemical conversion treatment liquid 5 was used and the chemical conversion treatment was performed at the temperature and time shown in Table 5, and the corrosion resistance of the coating formed on the surface of ZDC was evaluated. Table 5 shows the results.
表５に記載のいずれの条件でも、耐食性の良好な皮膜が形成された。硝酸イオン（酸化剤）を十分に含んでいる限り、化成処理の温度及び時間を表５の範囲で変化させても、耐食性の良好な皮膜が形成されることが分かった。
A film with good corrosion resistance was formed under any of the conditions listed in Table 5. It was found that even if the temperature and time of chemical conversion treatment were varied within the ranges shown in Table 5, a film with good corrosion resistance was formed as long as nitrate ions (oxidizing agent) were sufficiently contained.
以上より、水溶性チタン錯イオン及び水溶性バナジウム含有イオンを含む化成処理液に高濃度の酸化剤を配合することで、対象金属の表面に耐食性の良好な皮膜を形成できることが分かった。この場合、化成処理液中にクロムを配合する必要がないため、環境にやさしい化成処理液を提供することが可能となる。
From the above, it was found that by adding a high-concentration oxidizing agent to a chemical conversion treatment solution containing water-soluble titanium complex ions and water-soluble vanadium-containing ions, it was possible to form a film with good corrosion resistance on the surface of the target metal. In this case, it is not necessary to add chromium to the chemical conversion treatment liquid, so it is possible to provide an environmentally friendly chemical conversion treatment liquid.
Claims (13)
- 水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液であって、フッ素イオンの濃度が０～０．３ｇ／Ｌである、化成処理液。 A chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and an oxidizing agent of 0.03 mol/L or more, wherein the concentration of fluorine ions is 0 to 0.3 g/L. liquid.
- 水溶性チタン錯イオンと、水溶性バナジウム含有イオンと、０．０３ｍｏｌ／Ｌ以上の酸化剤とを含む化成処理液であって、フルオロ錯体以外のフッ素イオンを遊離するフッ化物は添加されていない、化成処理液。 A chemical conversion treatment solution containing water-soluble titanium complex ions, water-soluble vanadium-containing ions, and 0.03 mol/L or more of an oxidizing agent, wherein no fluorides other than fluoro complexes that release fluorine ions are added. Chemical treatment liquid.
- ｐＨが２．０～５．０である、請求項１又は２に記載の化成処理液。 The chemical conversion treatment solution according to claim 1 or 2, which has a pH of 2.0 to 5.0.
- 前記酸化剤が、硝酸及び／又は硝酸イオンを遊離する硝酸塩を含む、請求項１～３のいずれか１項に記載の化成処理液。 The chemical conversion treatment solution according to any one of claims 1 to 3, wherein the oxidizing agent contains nitric acid and/or a nitrate that liberates nitrate ions.
- 前記水溶性チタン錯イオンが、チタン錯フッ化物イオンである、請求項１～４のいずれか１項に記載の化成処理液。 The chemical conversion treatment solution according to any one of claims 1 to 4, wherein the water-soluble titanium complex ions are titanium complex fluoride ions.
- 前記水溶性チタン錯イオンのチタン換算濃度が、０．１５～１０ｇ／Ｌである、請求項１～５のいずれか１項に記載の化成処理液。 The chemical conversion treatment solution according to any one of claims 1 to 5, wherein the concentration of the water-soluble titanium complex ions in terms of titanium is 0.15 to 10 g/L.
- 前記水溶性バナジウム含有イオンが、５価のバナジウムを含むバナジウム化合物イオンである、請求項１～６のいずれか１項に記載の化成処理液。 The chemical conversion treatment solution according to any one of claims 1 to 6, wherein the water-soluble vanadium-containing ions are vanadium compound ions containing pentavalent vanadium.
- 前記水溶性バナジウム含有イオンのバナジウム換算濃度が、０．４～１５ｇ／Ｌである、請求項１～７のいずれか１項に記載の化成処理液。 The chemical conversion treatment solution according to any one of claims 1 to 7, wherein the vanadium-equivalent concentration of the water-soluble vanadium-containing ions is 0.4 to 15 g/L.
- Ｚｎ、Ｃｏ、Ｗ、Ｚｒ、Ｍｎ、Ｍｏ、Ｔａ、Ｃｅ、Ｓｒ、又はＦｅを含む少なくとも１種の追加の水溶性金属塩をさらに含む、請求項１～８のいずれか１項に記載の化成処理液。 The formation of any one of claims 1-8, further comprising at least one additional water-soluble metal salt comprising Zn, Co, W, Zr, Mn, Mo, Ta, Ce, Sr, or Fe. processing liquid.
- ６価クロムイオン及び／又は３価クロムイオンを含まない、請求項１～９のいずれか１項に記載の化成処理液。 The chemical conversion treatment solution according to any one of claims 1 to 9, which does not contain hexavalent chromium ions and/or trivalent chromium ions.
- 亜鉛含有金属材料に用いるための、請求項１～１０のいずれか１項に記載の化成処理液。 The chemical conversion treatment solution according to any one of claims 1 to 10, for use with zinc-containing metal materials.
- 対象金属材料を化成処理する方法であって、
前記対象金属材料を、請求項１～１１のいずれか１項に記載の化成処理液に浸漬させる工程、又は、前記対象金属材料に、請求項１～１１のいずれか１項に記載の化成処理液を噴霧する工程を含む、方法。 A method for chemical conversion treatment of a target metal material,
The step of immersing the target metal material in the chemical conversion treatment solution according to any one of claims 1 to 11, or the target metal material is subjected to the chemical conversion treatment according to any one of claims 1 to 11. A method comprising the step of spraying a liquid. - 前記対象金属材料が、亜鉛含有金属材料である、請求項１２に記載の方法。 The method according to claim 12, wherein the target metallic material is a zinc-containing metallic material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003213458A (en) * | 2002-01-24 | 2003-07-30 | Nisshin Steel Co Ltd | Cr-FREE CHEMICAL CONVERSION-TREATED ALUMINUM-BASED PLATED STEEL SHEET |
| JP2010261058A (en) * | 2009-04-30 | 2010-11-18 | Nippon Parkerizing Co Ltd | Chromium-free solution for chemical conversion treatment, and method and article for chemical conversion treatment |
| JP2012012668A (en) * | 2010-07-01 | 2012-01-19 | Sambix:Kk | Composition for forming rust preventive film and method for forming rust preventive film using the same and rust prevention-treated metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003213458A (en) * | 2002-01-24 | 2003-07-30 | Nisshin Steel Co Ltd | Cr-FREE CHEMICAL CONVERSION-TREATED ALUMINUM-BASED PLATED STEEL SHEET |
| JP2010261058A (en) * | 2009-04-30 | 2010-11-18 | Nippon Parkerizing Co Ltd | Chromium-free solution for chemical conversion treatment, and method and article for chemical conversion treatment |
| JP2012012668A (en) * | 2010-07-01 | 2012-01-19 | Sambix:Kk | Composition for forming rust preventive film and method for forming rust preventive film using the same and rust prevention-treated metal |
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