WO2007080849A1 - Method for chemical conversion treatment of the surface of aluminum material and aluminum material - Google Patents

Method for chemical conversion treatment of the surface of aluminum material and aluminum material Download PDF

Info

Publication number
WO2007080849A1
WO2007080849A1 PCT/JP2007/050077 JP2007050077W WO2007080849A1 WO 2007080849 A1 WO2007080849 A1 WO 2007080849A1 JP 2007050077 W JP2007050077 W JP 2007050077W WO 2007080849 A1 WO2007080849 A1 WO 2007080849A1
Authority
WO
WIPO (PCT)
Prior art keywords
concentration
chemical conversion
aluminum material
conversion treatment
aluminum
Prior art date
Application number
PCT/JP2007/050077
Other languages
French (fr)
Japanese (ja)
Inventor
Mitsuo Suzuki
Takeshi Ono
Original Assignee
Mitsui Mining & Smelting Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Mining & Smelting Co., Ltd. filed Critical Mitsui Mining & Smelting Co., Ltd.
Priority to CN2007800011381A priority Critical patent/CN101356300B/en
Priority to JP2007553897A priority patent/JPWO2007080849A1/en
Publication of WO2007080849A1 publication Critical patent/WO2007080849A1/en

Links

Classifications

    • 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
    • C23C22/44—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 containing also fluorides or complex fluorides
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/10—Use of solutions containing trivalent chromium but free of hexavalent chromium

Definitions

  • the present invention is formed by a surface chemical conversion treatment method for an aluminum material made of aluminum or an aluminum alloy (hereinafter collectively referred to as aluminum and aluminum alloy) and such a surface chemical conversion treatment. More specifically, the aluminum material having a surface that is formed by chemical conversion treatment of the surface of the aluminum material using a treatment liquid that does not contain hexavalent chromium but contains trivalent chromium.
  • the present invention relates to a chemical conversion treatment method and an aluminum material having a film formed by such surface chemical conversion treatment.
  • hexavalent chromium such as alkali chromate method, chromate method, phosphate chromate method, zinc phosphate method, non-chromate chemical conversion treatment method (tannic acid Method) and other various non-chromium systems (for example, see Non-Patent Document 1 and Patent Documents 1 to 6).
  • Non-Patent Document 1 Surface Technology Association, “Surface Technology Handbook”, Nikkan Kogyo Shimbun, February 1998, p. 691
  • Patent Document 1 JP-A-7-90614
  • Patent Document 2 Japanese Patent Laid-Open No. 10-237667
  • Patent Document 3 Japanese Patent Laid-Open No. 11 131254
  • Patent Document 4 Japanese Patent Laid-Open No. 2000-34577
  • Patent Document 5 Japanese Patent Laid-Open No. 2002-249886
  • Patent Document 6 Japanese Patent Laid-Open No. 2002-275649
  • Patent Document 7 Japanese Patent Laid-Open No. 2002-332575
  • Patent Document 8 Japanese Unexamined Patent Application Publication No. 2002-332581
  • Patent Document 9 Japanese Patent Laid-Open No. 2003-213446
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2005-281852
  • the surface of an aluminum material is treated using a treatment liquid containing trivalent chromium, but the chromate method containing hexavalent chromium is treated with the phosphate chromate method. It is an object of the present invention to provide a chemical conversion treatment method for the surface of an aluminum material that can achieve an effect equal to or higher than that, and an aluminum material having a film formed by such a surface chemical conversion treatment.
  • the present inventor has made the surface of the aluminum material anodized and then sealed the surface of the aluminum material with chromium nitrate and vanadine.
  • Aluminum with excellent corrosion resistance and coating adhesion by using a treatment solution containing acid ammonium, potassium titanium fluoride, lithium fluoride and nitric acid at specific temperatures for a specific time.
  • the present invention was completed by finding that a lumber product can be obtained.
  • the surface of the aluminum material has a chromium nitrate concentration of 3 to 12 gZL as Cr (NO),
  • the concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO
  • Liquid temperature is 40-50 ° C
  • a film is formed by performing chemical conversion treatment for 1 to 5 minutes with a treatment solution.
  • the surface of the aluminum material is subjected to a positive electrode oxidation treatment and then a sealing treatment,
  • Chromium nitrate concentration is 3-12gZL as Cr (NO),
  • the concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO
  • Liquid temperature is 40-50 ° C
  • a film is formed by performing chemical conversion treatment for 1 to 5 minutes with a treatment solution.
  • the aluminum material of the present invention the surface of the aluminum material,
  • Chromium nitrate concentration is 3-12gZL as Cr (NO),
  • Ammonium vanadate concentration is 0.5-7gZL as NH VO
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO
  • Liquid temperature is 40-50 ° C
  • It is characterized by having a film formed by performing chemical conversion treatment for 1 to 5 minutes with the treatment liquid.
  • the surface of the aluminum material is anodized, then sealed,
  • Chromium nitrate concentration is 3-12gZL as Cr (NO),
  • the concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
  • Titanium potassium fluoride concentration is 0.5-3gZL as K TiF
  • Lithium fluoride concentration is 0.5-3gZL as LiF
  • Nitric acid concentration is 0.5 ⁇ 1.8mLZL as HNO, Liquid temperature is 40-50 ° C
  • It is characterized by having a film formed by performing chemical conversion treatment for 1 to 5 minutes with the treatment liquid.
  • the surface of the aluminum material is subjected to chemical conversion treatment using a treatment liquid containing trivalent chromium without containing hexavalent chromium.
  • the chromate method containing hexavalent chromium can achieve the same or higher effect as compared with the case where the phosphoric acid chromate method is used.
  • FIG. 1 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Example 1.
  • FIG. 2 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Example 2.
  • FIG. 3 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 1.
  • FIG. 4 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 2.
  • FIG. 5 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 3.
  • FIG. 6 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 4.
  • FIG. 7 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 5.
  • FIG. 8 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 6.
  • FIG. 9 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 7.
  • the aluminum material subjected to the chemical conversion treatment by the surface chemical conversion treatment method of the present invention all aluminum and aluminum alloys that are practically used in various technical fields, for example, AC1A, AC1B defined in JIS H 5 202, AC2A, AC2B, AC3A, AC4A, AAC4B, AC4C, AC4CH, AC4D, AC5A AC7A AC8A AC8B, AC8C, AC9A, AC9B, etc.
  • Aluminum alloy wrought materials such as 7075 and 8021 are included.
  • the form of the aluminum material product subjected to surface chemical conversion treatment in the present invention examples thereof include a mold forging product, a sand mold forging product, a die casting, a wrought material, and the like.
  • the surface of the aluminum material is preferably pretreated.
  • the pretreatment can be performed by any of a mechanical method, a solvent method, an alkali method, and a pickling method, for example.
  • it can be carried out by immersing in an aqueous solution of Actan 70 (Meltex, ammonium acid fluoride) having a concentration of 5 gZL and a temperature of 40 ° C. for 1 minute, followed by washing with water.
  • the corrosion resistance is further improved by subjecting the surface of the aluminum material to anodic acid treatment, then sealing treatment, and then performing the surface chemical conversion treatment of the present invention.
  • the anodizing treatment and sealing treatment employed in the present invention are well known in the technical field, and well-known anodizing treatment technology and sealing treatment technology can be used as they are in the present invention.
  • anodic oxidation at a current density of 0.5 to 5 A / dm 2 and a bath temperature of 20 to 30 ° C for 10 to 30 minutes in a treatment solution having a sulfuric acid concentration of 1 to 5 molZL and a boric acid concentration of 0.1 to 0.3 mol / L is sealed by dipping in a treatment solution having a nickel acetate concentration of 1 to 5 gZL at a bath temperature of 85 ° C. for 2 to 10 minutes.
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains chromium nitrate as an essential component.
  • Chromium nitrate is available as a 9-hydrate salt, an anhydrous salt, or a 40% by mass aqueous solution. Any product can be used in the present invention.
  • the concentration of chromium nitrate in the treatment solution is Cr (NO)
  • It is preferably 3-12gZL in terms of 100%, and should be about 4-10OZZL.
  • the concentration of chromium nitrate 9 hydrate is preferably about 4.2 to 20.lgZL.
  • the concentration of chromium nitrate in the treatment liquid is Cr (NO)
  • the concentration of chromium nitrate in the treatment liquid is 12 gZL as Cr (NO).
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains ammonium vanadate as an essential component.
  • Ammonium vanadate - ⁇ beam is in a force present invention that are commercially available in as pure 98 mass 0/0 and 99 weight 0/0 can be used any product.
  • the concentration of ammonium vanadate in the treatment solution is 0.5-7 gZL in terms of NH VO 100%.
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains titanium fluoride-containing rhodium as an essential component.
  • Potassium titanium fluoride is commercially available with a purity of 98% by mass or higher Any product can be used in the present invention.
  • the concentration of potassium titanium fluoride in the treatment solution should be 0.5 to 3 gZL in terms of K TiF 100%.
  • the concentration of titanium fluoride in the treatment liquid is less than 0.5 gZL as K TiF, the aluminum after chemical conversion treatment
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains lithium fluoride as an essential component.
  • Lithium fluoride is commercially available with a purity of 99% by mass Any commercially available product can be used in the present invention.
  • the concentration of lithium fluoride in the treatment liquid is preferably about 0.5 to 3 gZL in terms of LiFl 00%, more preferably about 0.7 to 2.5 gZL.
  • concentration force SLiF of lithium fluoride in the treatment liquid is less than 0.5 gZL, the corrosion resistance of the surface of the aluminum material after the chemical conversion treatment tends to be insufficient.
  • the concentration of lithium fluoride in the treatment solution is higher than 3 gZL as LiF, no improvement in corrosion resistance is observed.
  • the treatment liquid used in the surface chemical conversion treatment method of the present invention contains nitric acid as an essential component.
  • Nitric acid is commercially available as an aqueous solution of 50% by volume, 62% by volume, 67.5% by volume, etc. Any product can be used in the present invention.
  • the concentration of nitric acid in the treatment solution is HNO 10
  • the treatment solution used in the surface chemical conversion treatment method of the present invention has the above-described yarn formation, its pH becomes weakly acidic.
  • the treatment liquid temperature is maintained at 40 to 50 ° C.
  • the liquid temperature is less than 40 ° C or when the liquid temperature exceeds 50 ° C, the corrosion resistance of the surface of the aluminum material after chemical conversion tends to be insufficient.
  • the chemical conversion treatment time is 1 to 5 minutes.
  • the corrosion resistance of the aluminum material surface after chemical conversion treatment tends to be insufficient.
  • the chemical conversion treatment time exceeds 5 minutes, no improvement in corrosion resistance can be seen.
  • the aluminum product having a coating film formed by the surface chemical conversion treatment method of the present invention is excellent in both corrosion resistance and adhesion of the coating film, and was treated by the chromate method and the phosphoric acid chromate method. Compared to the case, the same or better effect can be achieved.
  • test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds.
  • Actan 70 Meltex
  • the first table shows amounts of chromium nitrate-nonahydrate, 40 parts by mass 0/0 chromium sulfate (111), 99 mass 0/0 vanadate ammonium Yuumu, potassium 98 mass 0/0 titanium fluoride, 99 wt 0/0 lithium fluoride, 62 volume 0/0 processing solution 45 ° C containing nitrate ⁇ beauty 95 volume% sulfuric acid It was immersed in the solution for 3 minutes, followed by washing with tap water at room temperature for 30 seconds and then washing with pure water at room temperature for 30 seconds. Finally, drying was performed at 80 ° C for 20 minutes.
  • Example 1 and Example 2 show the results of performing twice under the same processing conditions.
  • Concentrations of essential components in the present invention shown in Table 1 are the molecular weight force S400 of chromium nitrate 9-hydrate, and the molecular weight of Cr (NO) is 238. Quantity lOgZL
  • the amount of ammonium phosphate 3gZL is 2.97gZL in terms of NH VO.
  • the amount of the amount 0/0 titanium fluoride Potassium lgZL is 0. 98GZL at concentrations as K TiF, 99
  • the mass% lithium fluoride concentration 2gZL is 1.89gZL as LiF, and the volume of 62vol% nitric acid 2mLZL is 1.24mLZL as HNO.
  • the corrosion resistance in the 96-hour salt spray test is 9.9 or higher in the rating number.
  • the corrosion resistance in the 24-hour salt spray test is 0.5 to 7.5 in the rating number.
  • the corrosion resistance in the 48 hour salt spray test was 6.0 as the rating number.
  • test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds.
  • Actan 70 Meltex
  • the sample was immersed in a 45 ° C treatment solution containing the concentrations shown in Table 3 for 3 minutes, and then washed with tap water at room temperature for 30 seconds, and then washed with pure water at room temperature for 30 seconds. Finally, drying was performed at 80 ° C for 20 minutes.
  • a large number of test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds. [0041] 95% by volume sulfuric acid was used as the sulfuric acid, 99.5% by weight boric acid was used as the boric acid, and 99% by weight nickel acetate tetrahydrate was used as the nickel acetate.
  • Specimens were anodized in a treatment solution with a sulfuric acid concentration of 2 molZL and boric acid concentration of 0.2 molZL for 20 minutes at a current density of 2AZ dm 2 and a bath temperature of 25 ° C. It was immersed and sealed at a bath temperature of 85 ° C for 5 minutes.
  • Example 2 The same conditions as in Example 1 were used, using six test pieces pretreated as described above and further subjected to anodizing treatment and sealing treatment as described above in each of Examples 26 and 27. Surface chemical conversion treatment was performed below.

Abstract

Disclosed is a method for chemical conversion treatment of the surface of an aluminum material comprising aluminum or an aluminum alloy. The method comprises performing a chemical conversion treatment of the surface of the aluminum material with a treatment solution for 1 to 5 minutes to form a coating film having excellent corrosion resistance and coating film adhesion property, wherein the treatment solution contains a trivalent chromium, and has a chromium nitrate content of 3 to 12 g/L in terms of Cr(NO3)3, a ammonium vanadate content of 0.5 to 7 g/L in terms of NH4VO3, a potassium fluorotitanate content of 0.5 to 3 g/L in terms of K2TiF6, a lithium fluoride content of 0.5 to 3 g/L in terms of LiF, a nitric acid content of 0.5 to 1.8 mL/L in terms of HNO3, and a liquid temperature of 40 to 50ºC. Also disclosed is an aluminum material having a coating film formed by the method.

Description

明 細 書  Specification
アルミニウム材表面の化成処理方法及びアルミニウム材  Chemical conversion treatment method for aluminum material surface and aluminum material
技術分野  Technical field
[0001] 本発明はアルミニウム又はアルミニウム合金からなるアルミニウム材（以下、アルミ- ゥム及びアルミニウム合金を総称してアルミニウム材と記載する）の表面の化成処理 方法及びそのような表面化成処理で形成される皮膜を有するアルミニウム材に関し、 より詳しくは、 6価のクロムを含有せず、 3価のクロムを含有する処理液を使用してァ ルミ二ゥム材の表面を化成処理するアルミニウム材表面の化成処理方法及びそのよ うな表面化成処理で形成される皮膜を有するアルミニウム材に関する。  [0001] The present invention is formed by a surface chemical conversion treatment method for an aluminum material made of aluminum or an aluminum alloy (hereinafter collectively referred to as aluminum and aluminum alloy) and such a surface chemical conversion treatment. More specifically, the aluminum material having a surface that is formed by chemical conversion treatment of the surface of the aluminum material using a treatment liquid that does not contain hexavalent chromium but contains trivalent chromium. The present invention relates to a chemical conversion treatment method and an aluminum material having a film formed by such surface chemical conversion treatment.
背景技術  Background art
[0002] アルミニウム材表面の化成処理方法として、アルカリ クロム酸塩法、クロム酸塩法 、リン酸 クロム酸塩法等の 6価クロム系や、リン酸亜鉛法、ノンクロメート化成処理法 (タンニン酸法）、その他の種々の非クロム系が知られている（例えば、非特許文献 1、 特許文献 1〜6参照。）。  [0002] As a chemical conversion treatment method on the surface of aluminum material, hexavalent chromium such as alkali chromate method, chromate method, phosphate chromate method, zinc phosphate method, non-chromate chemical conversion treatment method (tannic acid Method) and other various non-chromium systems (for example, see Non-Patent Document 1 and Patent Documents 1 to 6).
[0003] 6価クロム系であるクロム酸塩法やリン酸 クロム酸塩法でアルミニウム材の表面を 化成処理した場合には、良好な耐食性及び塗膜の良好な密着性が得られるが、 6価 のクロム酸塩を使用するので環境問題が生じる。ノンクロメート法であるリン酸亜鉛法 やタンニン酸法でアルミニウム材の表面をィ匕成処理した場合には、環境問題が生じ ることはなく、塗膜の密着性は良好であるが、耐食性がクロム酸塩法と比較し劣るとい う問題があった。  [0003] When the surface of an aluminum material is subjected to a chemical conversion treatment using a hexavalent chromium-based chromate method or phosphoric acid chromate method, good corrosion resistance and good adhesion of the coating film can be obtained. Because of the use of valent chromate, environmental problems arise. When the surface of an aluminum material is subjected to a non-chromate zinc phosphate method or tannic acid method, environmental problems do not occur and the adhesion of the coating is good, but the corrosion resistance is good. There was a problem that it was inferior to the chromate method.
[0004] 環境問題が生じることがなぐ耐食性も改善されるアルミニウム材表面の化成処理と して、 3価のクロムを含む種々の処理液を用いる表面化成処理方法も提案されており (例えば、特許文献 7〜10参照。）、 3価のクロムを含む処理液の更なる開発が続けら れている。  [0004] Surface conversion treatment methods using various treatment liquids containing trivalent chromium have been proposed as a chemical conversion treatment for an aluminum material surface that can improve corrosion resistance without causing environmental problems (for example, patents). References 7 to 10)), and further development of treatment solutions containing trivalent chromium continues.
[0005] 非特許文献 1 : (社)表面技術協会編、「表面技術便覧」、 日刊工業新聞社、 1998年 2月、 p. 691  [0005] Non-Patent Document 1: Surface Technology Association, “Surface Technology Handbook”, Nikkan Kogyo Shimbun, February 1998, p. 691
特許文献 1 :特開平 7— 90614号公報 特許文献 2：特開平 10— 237667号公報 Patent Document 1: JP-A-7-90614 Patent Document 2: Japanese Patent Laid-Open No. 10-237667
特許文献 3：特開平 11 131254号公報  Patent Document 3: Japanese Patent Laid-Open No. 11 131254
特許文献 4：特開 2000 - 34577号公報  Patent Document 4: Japanese Patent Laid-Open No. 2000-34577
特許文献 5：特開 2002— 249886号公報  Patent Document 5: Japanese Patent Laid-Open No. 2002-249886
特許文献 6：特開 2002— 275649号公報  Patent Document 6: Japanese Patent Laid-Open No. 2002-275649
特許文献 7：特開 2002— 332575号公報  Patent Document 7: Japanese Patent Laid-Open No. 2002-332575
特許文献 8：特開 2002— 332581号公報  Patent Document 8: Japanese Unexamined Patent Application Publication No. 2002-332581
特許文献 9：特開 2003— 213446号公報  Patent Document 9: Japanese Patent Laid-Open No. 2003-213446
特許文献 10：特開 2005 - 281852号公報  Patent Document 10: Japanese Patent Application Laid-Open No. 2005-281852
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0006] 本発明は、 3価のクロムを含有する処理液を使用してアルミニウム材の表面を処理 するが、 6価のクロムを含むクロム酸塩法ゃリン酸 クロム酸塩法で処理した場合と比 較して同等以上の効果を達成できるアルミニウム材表面の化成処理方法及びそのよ うな表面化成処理で形成される皮膜を有するアルミニウム材を提供することを目的と している。 [0006] In the present invention, the surface of an aluminum material is treated using a treatment liquid containing trivalent chromium, but the chromate method containing hexavalent chromium is treated with the phosphate chromate method. It is an object of the present invention to provide a chemical conversion treatment method for the surface of an aluminum material that can achieve an effect equal to or higher than that, and an aluminum material having a film formed by such a surface chemical conversion treatment.
課題を解決するための手段  Means for solving the problem
[0007] 本発明者は上記の課題を達成するために鋭意検討した結果、アルミニウム材の表 面又は表面を陽極酸化処理し次 、で封孔処理したアルミニウム材の表面を、硝酸ク ロム、バナジン酸アンモニゥム、フッ化チタンカリウム、フッ化リチウム及び硝酸を特定 の濃度で含有する処理液を特定の温度で用いて特定の時間化成処理することにより 耐食性及び塗膜の密着性の両方に優れたアルミニウム材製品が得られることを見出 し、本発明を完成した。 [0007] As a result of intensive studies to achieve the above-mentioned problems, the present inventor has made the surface of the aluminum material anodized and then sealed the surface of the aluminum material with chromium nitrate and vanadine. Aluminum with excellent corrosion resistance and coating adhesion by using a treatment solution containing acid ammonium, potassium titanium fluoride, lithium fluoride and nitric acid at specific temperatures for a specific time. The present invention was completed by finding that a lumber product can be obtained.
[0008] 即ち、本発明のアルミニウム材表面の化成処理方法は、アルミニウム材の表面を、 硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  [0008] That is, in the method for chemical conversion treatment of the aluminum material surface of the present invention, the surface of the aluminum material has a chromium nitrate concentration of 3 to 12 gZL as Cr (NO),
3 3  3 3
バナジン酸アンモニゥム濃度が NH VOとして 0. 5〜7gZLであり、  The concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、 硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、 Lithium fluoride concentration is 0.5-3gZL as LiF, Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO,
3  Three
液温が 40〜50°Cである  Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施して皮膜を形成することを特徴とする。  A film is formed by performing chemical conversion treatment for 1 to 5 minutes with a treatment solution.
[0009] また、本発明のアルミニウム材表面の化成処理方法は、アルミニウム材の表面を陽 極酸化処理し、次いで封孔処理し、その後、 [0009] Further, in the chemical conversion treatment method for the surface of an aluminum material of the present invention, the surface of the aluminum material is subjected to a positive electrode oxidation treatment and then a sealing treatment,
硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  Chromium nitrate concentration is 3-12gZL as Cr (NO),
3 3  3 3
バナジン酸アンモニゥム濃度が NH VOとして 0. 5〜7gZLであり、  The concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、  Lithium fluoride concentration is 0.5-3gZL as LiF,
硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、  Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO,
3  Three
液温が 40〜50°Cである  Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施して皮膜を形成することを特徴とする。  A film is formed by performing chemical conversion treatment for 1 to 5 minutes with a treatment solution.
[0010] 更に、本発明のアルミニウム材は、アルミニウム材の表面を、 [0010] Further, the aluminum material of the present invention, the surface of the aluminum material,
硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  Chromium nitrate concentration is 3-12gZL as Cr (NO),
3 3  3 3
バナジン酸アンモ-ゥム濃度が NH VOとして 0. 5〜7gZLであり、  Ammonium vanadate concentration is 0.5-7gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、  Lithium fluoride concentration is 0.5-3gZL as LiF,
硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、  Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO,
3  Three
液温が 40〜50°Cである  Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施することにより形成される皮膜を有することを特 徴とする。  It is characterized by having a film formed by performing chemical conversion treatment for 1 to 5 minutes with the treatment liquid.
[0011] また、本発明のアルミニウム材は、アルミニウム材の表面を陽極酸ィ匕処理し、次いで 封孔処理し、その後、  [0011] Further, in the aluminum material of the present invention, the surface of the aluminum material is anodized, then sealed,
硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  Chromium nitrate concentration is 3-12gZL as Cr (NO),
3 3  3 3
バナジン酸アンモニゥム濃度が NH VOとして 0. 5〜7gZLであり、  The concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、  Lithium fluoride concentration is 0.5-3gZL as LiF,
硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、 液温が 40〜50°Cである Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO, Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施することにより形成される皮膜を有することを特 徴とする。  It is characterized by having a film formed by performing chemical conversion treatment for 1 to 5 minutes with the treatment liquid.
発明の効果  The invention's effect
[0012] 本発明のアルミニウム材表面の化成処理方法及びアルミニウム材においては、 6価 のクロムを含有せず、 3価のクロムを含有する処理液を使用してアルミニウム材の表 面を化成処理するが、 6価のクロムを含むクロム酸塩法ゃリン酸 クロム酸塩法でィ匕 成処理した場合と比較して同等以上の効果を達成できる。  [0012] In the chemical conversion treatment method and aluminum material of the aluminum material surface of the present invention, the surface of the aluminum material is subjected to chemical conversion treatment using a treatment liquid containing trivalent chromium without containing hexavalent chromium. However, the chromate method containing hexavalent chromium can achieve the same or higher effect as compared with the case where the phosphoric acid chromate method is used.
図面の簡単な説明  Brief Description of Drawings
[0013] [図 1]実施例 1の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 1 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Example 1.
[図 2]実施例 2の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 2 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Example 2.
[図 3]比較例 1の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 3 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 1.
[図 4]比較例 2の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 4 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 2.
[図 5]比較例 3の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 5 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 3.
[図 6]比較例 4の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 6 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 4.
[図 7]比較例 5の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 7 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 5.
[図 8]比較例 6の化成処理を施した試験片の耐食試験後の状態を示す写真である。  FIG. 8 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment in Comparative Example 6.
[図 9]比較例 7の化成処理を施した試験片の耐食試験後の状態を示す写真である。 発明を実施するための最良の形態  FIG. 9 is a photograph showing a state after a corrosion resistance test of a test piece subjected to chemical conversion treatment of Comparative Example 7. BEST MODE FOR CARRYING OUT THE INVENTION
[0014] 本発明の表面化成処理方法で化成処理するアルミニウム材としては、種々の技術 分野で実用されている全てのアルミニウム及びアルミニウム合金、例えば、 JIS H 5 202で規定されている AC1A、 AC1B、 AC2A、 AC2B、 AC3A、 AC4A、 AAC4B 、 AC4C、 AC4CH、 AC4D、 AC5Aゝ AC7Aゝ AC8Aゝ AC8B、 AC8C、 AC9A、 AC9B等のアルミニウム合金铸物、 JIS H 5302で規定されている ADC1、 ADC3 、 ADC5、 ADC6、 ADC10、 ADC10Z、 ADC 12, ADC12Z、 ADC14等のアルミ -ゥム合金ダイカスト、 JIS H 4000で規定されている合金番号 2017、 2219、 300 3、 3104、 4032、 5005、 5154、 6101、 6061、 7075、 8021等のアルミニウム合金 展伸材が包含される。また、本発明で表面化成処理するアルミニウム材製品の形態 としては、金型铸造品、砂型铸造品、ダイカスト、展伸材等を例示することができる。 [0014] As the aluminum material subjected to the chemical conversion treatment by the surface chemical conversion treatment method of the present invention, all aluminum and aluminum alloys that are practically used in various technical fields, for example, AC1A, AC1B defined in JIS H 5 202, AC2A, AC2B, AC3A, AC4A, AAC4B, AC4C, AC4CH, AC4D, AC5A AC7A AC8A AC8B, AC8C, AC9A, AC9B, etc. ADC6, ADC10, ADC10Z, ADC 12, ADC12Z, ADC14, etc. Aluminum alloy wrought materials such as 7075 and 8021 are included. In addition, the form of the aluminum material product subjected to surface chemical conversion treatment in the present invention Examples thereof include a mold forging product, a sand mold forging product, a die casting, a wrought material, and the like.
[0015] 本発明の表面化成処理方法で処理する前に、アルミニウム材の表面を前処理する ことが好ましい。前処理は、例えば、機械的方法、溶剤法、アルカリ法、酸洗法の何 れでも実施できる。例えば、ァクタン 70 (メルテックス社製、酸性フッ化アンモ-ゥム） の濃度が 5gZLで温度が 40°Cの水溶液中に 1分間浸漬し、その後水洗することによ つて実施でさる。  [0015] Prior to the treatment by the surface chemical conversion treatment method of the present invention, the surface of the aluminum material is preferably pretreated. The pretreatment can be performed by any of a mechanical method, a solvent method, an alkali method, and a pickling method, for example. For example, it can be carried out by immersing in an aqueous solution of Actan 70 (Meltex, ammonium acid fluoride) having a concentration of 5 gZL and a temperature of 40 ° C. for 1 minute, followed by washing with water.
[0016] 本発明の表面化成処理方法においては、アルミニウム材の表面を陽極酸ィ匕処理し 、次いで封孔処理し、その後に本発明の表面化成処理を実施することにより耐食性 が更に改善される。本発明で採用する陽極酸化処理及び封孔処理は当該技術分野 で周知であり、本発明においては周知の陽極酸ィヒ処理技術及び封孔処理技術をそ のまま利用することができる。例えば、硫酸濃度 l〜5molZL、ホウ酸濃度 0. 1〜0. 3mol/Lの処理液中で電流密度 0. 5〜5A/dm2、浴温 20〜30°Cで 10〜30分間 陽極酸化処理し、次いで、酢酸ニッケル濃度 l〜5gZLの処理液中に浴温 85°Cで 2 〜10分間浸漬して封孔処理する。 In the surface chemical conversion treatment method of the present invention, the corrosion resistance is further improved by subjecting the surface of the aluminum material to anodic acid treatment, then sealing treatment, and then performing the surface chemical conversion treatment of the present invention. . The anodizing treatment and sealing treatment employed in the present invention are well known in the technical field, and well-known anodizing treatment technology and sealing treatment technology can be used as they are in the present invention. For example, anodic oxidation at a current density of 0.5 to 5 A / dm 2 and a bath temperature of 20 to 30 ° C for 10 to 30 minutes in a treatment solution having a sulfuric acid concentration of 1 to 5 molZL and a boric acid concentration of 0.1 to 0.3 mol / L Then, it is sealed by dipping in a treatment solution having a nickel acetate concentration of 1 to 5 gZL at a bath temperature of 85 ° C. for 2 to 10 minutes.
[0017] 本発明の表面化成処理方法で用いる処理液は必須成分として硝酸クロムを含有す る。硝酸クロムは 9水塩や無水塩や 40質量％水溶液として入手できる力 本発明に おいては何れの製品も用いることができる。処理液中の硝酸クロムの濃度は Cr(NO )  [0017] The treatment liquid used in the surface chemical conversion treatment method of the present invention contains chromium nitrate as an essential component. Chromium nitrate is available as a 9-hydrate salt, an anhydrous salt, or a 40% by mass aqueous solution. Any product can be used in the present invention. The concentration of chromium nitrate in the treatment solution is Cr (NO)
3 Three
100%に換算して 3〜 12gZLであることが好ましく、 4〜 lOgZL程度であることがよIt is preferably 3-12gZL in terms of 100%, and should be about 4-10OZZL.
3 Three
り好ましい。従って、硝酸クロム 9水塩を用いる場合には、硝酸クロム 9水塩の濃度が 約 4. 2〜20. lgZLであることが好ましい。処理液中の硝酸クロムの濃度が Cr(NO )  More preferable. Therefore, when chromium nitrate 9 hydrate is used, the concentration of chromium nitrate 9 hydrate is preferably about 4.2 to 20.lgZL. The concentration of chromium nitrate in the treatment liquid is Cr (NO)
3 として 3gZL未満の場合には、化成処理後のアルミニウム材表面の耐食性が不十分 If less than 3gZL as 3, the corrosion resistance of the surface of the aluminum material after chemical conversion is insufficient
3 Three
となる傾向がある。また、処理液中の硝酸クロムの濃度が Cr(NO )として 12gZLを  Tend to be. In addition, the concentration of chromium nitrate in the treatment liquid is 12 gZL as Cr (NO).
3 3  3 3
超えて高くなつてもそれに見合った耐食性の向上は見られない。  Even if it exceeds this level, no improvement in corrosion resistance can be seen.
[0018] 本発明の表面化成処理方法で用いる処理液は必須成分としてバナジン酸アンモ -ゥムを含有する。バナジン酸アンモ-ゥムは純度 98質量0 /0や 99質量0 /0のものとし て市販されている力 本発明においては何れの製品も用いることができる。処理液中 のバナジン酸アンモ-ゥムの濃度は NH VO 100%に換算して 0. 5〜7gZLである [0018] The treatment liquid used in the surface chemical conversion treatment method of the present invention contains ammonium vanadate as an essential component. Ammonium vanadate - © beam is in a force present invention that are commercially available in as pure 98 mass 0/0 and 99 weight 0/0 can be used any product. The concentration of ammonium vanadate in the treatment solution is 0.5-7 gZL in terms of NH VO 100%.
4 3  4 3
ことが好ましぐ 1. 5〜5gZL程度であることがより好ましい。処理液中のバナジン酸 アンモ-ゥムの濃度が NH VOとして 0. 5gZL未満の場合には、化成処理後のアル 1. It is more preferably about 5 to 5 gZL. Vanadic acid in processing solution If the ammonia concentration is less than 0.5 gZL as NH VO,
4 3  4 3
ミニゥム材表面の耐食性が不十分となる傾向がある。また、処理液中のバナジン酸ァ ンモ-ゥムの濃度が NH VOとして 7g/Lを超えて高くなつてもそれに見合った耐食  There is a tendency that the corrosion resistance of the surface of the minium material becomes insufficient. In addition, even if the concentration of vanadate ammonium in the processing solution exceeds 7 g / L as NH VO, corrosion resistance is commensurate with it.
4 3  4 3
性の向上は見られない。  There is no improvement in sex.
[0019] 本発明の表面化成処理方法で用いる処理液は必須成分としてフッ化チタン力リウ ムを含有する。フッ化チタンカリウムは純度 98質量％のもの又はそれ以上のものとし て市販されている力 本発明においては何れの製品も用いることができる。処理液中 のフッ化チタンカリウムの濃度は K TiF 100%に換算して 0. 5〜3gZLであることが [0019] The treatment liquid used in the surface chemical conversion treatment method of the present invention contains titanium fluoride-containing rhodium as an essential component. Potassium titanium fluoride is commercially available with a purity of 98% by mass or higher Any product can be used in the present invention. The concentration of potassium titanium fluoride in the treatment solution should be 0.5 to 3 gZL in terms of K TiF 100%.
2 6  2 6
好ましぐ 0. 7〜2. 5gZL程度であることがより好ましい。処理液中のフッ化チタン力 リウムの濃度が K TiFとして 0. 5gZL未満の場合には、化成処理後のアルミニウム  It is more preferably about 0.7 to 2.5 gZL. If the concentration of titanium fluoride in the treatment liquid is less than 0.5 gZL as K TiF, the aluminum after chemical conversion treatment
2 6  2 6
材表面の耐食性が不十分となる傾向がある。また、処理液中のフッ化チタンカリウム の濃度が K TiFとして 3gZLを超えて高くなつてもそれに見合った耐食性の向上は  There is a tendency that the corrosion resistance of the material surface is insufficient. In addition, even if the concentration of potassium titanium fluoride in the treatment liquid exceeds 3 gZL as K TiF, the corrosion resistance will not be improved.
2 6  2 6
見られない。  can not see.
[0020] 本発明の表面化成処理方法で用いる処理液は必須成分としてフッ化リチウムを含 有する。フッ化リチウムは純度 99質量％のものとして市販されている力 本発明にお いては何れの市販品も用いることができる。処理液中のフッ化リチウムの濃度は LiFl 00%に換算して 0. 5〜3gZLであることが好ましぐ 0. 7〜2. 5gZL程度であること 力 り好ましい。処理液中のフッ化リチウムの濃度力 SLiFとして 0. 5gZL未満の場合 には、化成処理後のアルミニウム材表面の耐食性が不十分となる傾向がある。また、 処理液中のフッ化リチウムの濃度が LiFとして 3gZLを超えて高くなつてもそれに見 合った耐食性の向上は見られない。  [0020] The treatment liquid used in the surface chemical conversion treatment method of the present invention contains lithium fluoride as an essential component. Lithium fluoride is commercially available with a purity of 99% by mass Any commercially available product can be used in the present invention. The concentration of lithium fluoride in the treatment liquid is preferably about 0.5 to 3 gZL in terms of LiFl 00%, more preferably about 0.7 to 2.5 gZL. When the concentration force SLiF of lithium fluoride in the treatment liquid is less than 0.5 gZL, the corrosion resistance of the surface of the aluminum material after the chemical conversion treatment tends to be insufficient. In addition, even if the concentration of lithium fluoride in the treatment solution is higher than 3 gZL as LiF, no improvement in corrosion resistance is observed.
[0021] 本発明の表面化成処理方法で用いる処理液は必須成分として硝酸を含有する。硝 酸は 50容量％、 62容量％、 67. 5容量％等の水溶液として市販されている力 本発 明においては何れの製品も用いることができる。処理液中の硝酸の濃度は HNO 10  [0021] The treatment liquid used in the surface chemical conversion treatment method of the present invention contains nitric acid as an essential component. Nitric acid is commercially available as an aqueous solution of 50% by volume, 62% by volume, 67.5% by volume, etc. Any product can be used in the present invention. The concentration of nitric acid in the treatment solution is HNO 10
3 Three
0%に換算して 0. 5〜1. 8mL/Lであることが好ましぐ 0. 7〜1. 7mLZLであるこ とがより好ましい。処理液中の硝酸の濃度が HNOとして 0. 5mLZL未満の場合に It is preferably 0.5 to 1.8 mL / L in terms of 0%, more preferably 0.7 to 1.7 mLZL. When the concentration of nitric acid in the treatment solution is less than 0.5 mLZL as HNO
3  Three
は、化成処理後のアルミニウム材表面の耐食性が不十分となる傾向がある。また、処 理液中の硝酸の濃度が HNOとして 1. 8mLZLを超えて高くなつてもそれに見合つ た耐食性の向上は見られな ヽ。 Tends to have insufficient corrosion resistance on the surface of the aluminum material after the chemical conversion treatment. In addition, even if the concentration of nitric acid in the processing solution is higher than 1.8 mLZL as HNO, it will be commensurate with it. There has been no improvement in corrosion resistance.
[0022] 本発明の表面化成処理方法で用いる処理液は上記の糸且成を有するので、その pH は弱酸性となる。  [0022] Since the treatment solution used in the surface chemical conversion treatment method of the present invention has the above-described yarn formation, its pH becomes weakly acidic.
[0023] 本発明の表面化成処理方法においては、処理液の液温を 40〜50°Cに維持して 実施する。液温が 40°C未満の場合や、液温が 50°Cを超える場合には、化成処理後 のアルミニウム材表面の耐食性が不十分となる傾向がある。  [0023] In the surface chemical conversion treatment method of the present invention, the treatment liquid temperature is maintained at 40 to 50 ° C. When the liquid temperature is less than 40 ° C or when the liquid temperature exceeds 50 ° C, the corrosion resistance of the surface of the aluminum material after chemical conversion tends to be insufficient.
[0024] 本発明の表面化成処理方法においては、化成処理時間は 1〜5分間である。化成 処理時間が 1分間未満の場合には、化成処理後のアルミニウム材表面の耐食性が 不十分となる傾向がある。また、化成処理時間が 5分間を超えて長くなつてもそれに 見合った耐食性の向上は見られない。  [0024] In the surface chemical conversion treatment method of the present invention, the chemical conversion treatment time is 1 to 5 minutes. When the chemical conversion treatment time is less than 1 minute, the corrosion resistance of the aluminum material surface after chemical conversion treatment tends to be insufficient. Moreover, even if the chemical conversion treatment time exceeds 5 minutes, no improvement in corrosion resistance can be seen.
[0025] 上記の条件下で化成処理した後、水洗及び純水洗浄を行 、、次 、で乾燥する。乾 燥については一般的には室温〜 90°C程度で 10〜120分間実施する。  [0025] After the chemical conversion treatment under the above conditions, washing with water and pure water are performed, and then drying is performed. Drying is generally performed at room temperature to about 90 ° C for 10 to 120 minutes.
[0026] 本発明の表面化成処理方法で形成される皮膜を有するアルミニウム材製品は耐食 性及び塗膜の密着性の両方に優れており、クロム酸塩法ゃリン酸 クロム酸塩法で 処理した場合と比較して同等以上の効果を達成できる。  [0026] The aluminum product having a coating film formed by the surface chemical conversion treatment method of the present invention is excellent in both corrosion resistance and adhesion of the coating film, and was treated by the chromate method and the phosphoric acid chromate method. Compared to the case, the same or better effect can be achieved.
実施例  Example
[0027] 以下に、実施例及び比較例に基づいて本発明を具体的に説明する。  Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples.
[0028] 実施例 1〜2及び比較例 1〜7  [0028] Examples 1-2 and Comparative Examples 1-7
ADC— 12合金を用いてダイカスト铸造して得た多数の試験片を、液温 40°Cで濃 度 5gZLのァクタン 70 (メルテックス社製)の水溶液中に 1分間浸漬し、その後室温で の水道水洗浄を 30秒間実施し、次 、で室温での純水洗浄を 30秒間実施した。  A large number of test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds.
[0029] 上記のように前処理した試験片を各々の実施例及び比較例で 2個用い、第 1表に 示す量で硝酸クロム · 9水塩、 40質量0 /0硫酸クロム (111)、 99質量0 /0バナジン酸アンモ ユウム、 98質量0 /0フッ化チタンカリウム、 99質量0 /0フッ化リチウム、 62容量0 /0硝酸及 び 95容量％硫酸を含有する 45°Cの処理液中に 3分間浸漬し、その後室温での水道 水洗浄を 30秒間実施し、次いで室温での純水洗浄を 30秒間実施した。最後に 80°C で 20分間乾燥を実施した。なお、実施例 1及び実施例 2は同一の処理条件で 2回実 施したそれぞれの結果を示して!/ヽる。 [0030] 第 1表に示す本発明で必須成分の濃度については、硝酸クロム · 9水塩の分子量 力 S400であり、 Cr(NO )の分子量が 238であるので、硝酸クロム · 9水塩の量 lOgZL [0029] using two in Examples and Comparative Examples of each test piece was pre-treated as described above, the first table shows amounts of chromium nitrate-nonahydrate, 40 parts by mass 0/0 chromium sulfate (111), 99 mass 0/0 vanadate ammonium Yuumu, potassium 98 mass 0/0 titanium fluoride, 99 wt 0/0 lithium fluoride, 62 volume 0/0 processing solution 45 ° C containing nitrate及beauty 95 volume% sulfuric acid It was immersed in the solution for 3 minutes, followed by washing with tap water at room temperature for 30 seconds and then washing with pure water at room temperature for 30 seconds. Finally, drying was performed at 80 ° C for 20 minutes. In addition, Example 1 and Example 2 show the results of performing twice under the same processing conditions. [0030] Concentrations of essential components in the present invention shown in Table 1 are the molecular weight force S400 of chromium nitrate 9-hydrate, and the molecular weight of Cr (NO) is 238. Quantity lOgZL
3 3  3 3
は Cr(NO )としての濃度で 5. 95g/L{ 10 X (238/400) }であり、 99質量0 /0バナ Is the Cr concentration of the (NO) 5. 95g / L { 10 X (238/400)}, 99 mass 0/0 nosed
3 3  3 3
ジン酸アンモ-ゥムの量 3gZLは NH VOとしての濃度で 2. 97gZLであり、 98質  The amount of ammonium phosphate 3gZL is 2.97gZL in terms of NH VO.
4 3  4 3
量0 /0フッ化チタンカリウムの量 lgZLは K TiFとしての濃度で 0. 98gZLであり、 99 The amount of the amount 0/0 titanium fluoride Potassium lgZL is 0. 98GZL at concentrations as K TiF, 99
2 6  2 6
質量％フッ化リチウム濃度 2gZLは LiFとしての濃度で 1. 89gZLであり、 62容量％ 硝酸の量 2mLZLは HNOとしての濃度で 1. 24mLZLである。  The mass% lithium fluoride concentration 2gZL is 1.89gZL as LiF, and the volume of 62vol% nitric acid 2mLZL is 1.24mLZL as HNO.
3  Three
[0031] 次に、 JIS Z 2371に準拠した耐塩水噴霧試験法による耐食性試験を実施し、レ ィティングナンバーを測定した。実施例 1及び 2につ ヽては塩水噴霧時間は 96時間 であり、比較例 1〜5については塩水噴霧時間は 24時間であり、比較例 6及び 7につ いては塩水噴霧時間は 48時間であった。それらの結果は第 1表に示す通りであった 。また、それらの耐食性試験後の各試験片の写真は図 1〜9に示す通りであった。  [0031] Next, a corrosion resistance test by a salt spray resistance test method based on JIS Z 2371 was performed, and the rating number was measured. For Examples 1 and 2, the salt spray time was 96 hours, for Comparative Examples 1-5, the salt spray time was 24 hours, and for Comparative Examples 6 and 7, the salt spray time was 48 hours. Met. The results are shown in Table 1. In addition, photographs of each test piece after the corrosion resistance test were as shown in FIGS.
[0032] [表 1] [0032] [Table 1]
第 1 表 Table 1
Figure imgf000010_0001
Figure imgf000010_0001
[0033] 第 1表に示すデータから明らかなように、本発明の化成処理方法である実施例 1及 び 2では 96時間の塩水噴霧試験での耐食性はレイティングナンバーで 9. 9以上で あるが、これに対して、本発明で用いる処理液力 何れ力 1成分を除いた比較例 1〜 5の場合には 24時間の塩水噴霧試験での耐食性でもレイティングナンバーで 0. 5〜 7. 5であり、本発明で用いる処理液の硝酸クロムを硫酸クロムに変更した比較例 6の 場合には 48時間の塩水噴霧試験での耐食性でもレイティングナンバーで 6. 0であり 、本発明で用いる処理液の硝酸を硫酸に変更した比較例 7の場合には 48時間の塩 水噴霧試験での耐食性でもレイティングナンバーで 7. 5であった。なお、本発明で用 いる処理液に更にリン酸をカ卩えた場合には、アルミニウムダイカストの処理において 耐食性の向上は認められないだけでなぐその化成処理中に沈殿が発生し、処理液 の管理が難しくなる。 [0033] As is apparent from the data shown in Table 1, in Examples 1 and 2 which are the chemical conversion treatment methods of the present invention, the corrosion resistance in the 96-hour salt spray test is 9.9 or higher in the rating number. On the other hand, in the case of Comparative Examples 1 to 5 except for one component of the treatment liquid force used in the present invention, the corrosion resistance in the 24-hour salt spray test is 0.5 to 7.5 in the rating number. In the case of Comparative Example 6 in which the chromium nitrate of the treatment solution used in the present invention was changed to chromium sulfate, the corrosion resistance in the 48 hour salt spray test was 6.0 as the rating number. In the case of Comparative Example 7 in which nitric acid was changed to sulfuric acid, the corrosion resistance in the 48 hour salt spray test was 7.5 as the rating number. In addition, when phosphoric acid is further added to the treatment liquid used in the present invention, no improvement in corrosion resistance is observed in the aluminum die casting treatment, and precipitation occurs during the chemical conversion treatment. Becomes difficult.
[0034] 実施例 3〜25及び比較例 8〜19  [0034] Examples 3 to 25 and Comparative Examples 8 to 19
ADC— 12合金を用いてダイカスト铸造して得た多数の試験片を、液温 40°Cで濃 度 5gZLのァクタン 70 (メルテックス社製)の水溶液中に 1分間浸漬し、その後室温で の水道水洗浄を 30秒間実施し、次 、で室温での純水洗浄を 30秒間実施した。  A large number of test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds.
[0035] 上記のように前処理した試験片を各々の実施例 3〜25及び比較例 8〜19で 2個又 は 3個用い、硝酸クロム、バナジン酸アンモ-ゥム、フッ化チタンカリウム、フッ化リチウ ム及び硝酸をそれぞれ Cr(NO )、 NH VO、 K TiF、 LiF及び HNOとして第 2表  [0035] Two or three test pieces pretreated as described above were used in each of Examples 3 to 25 and Comparative Examples 8 to 19, and chromium nitrate, ammonium vanadate, potassium titanium fluoride, Table 2 lists lithium fluoride and nitric acid as Cr (NO), NH VO, K TiF, LiF, and HNO, respectively.
3 3 4 3 2 6 3  3 3 4 3 2 6 3
及び第 3表に示す濃度で含有する 45°Cの処理液中に 3分間浸漬し、その後室温で の水道水洗浄を 30秒間実施し、次いで室温での純水洗浄を 30秒間実施した。最後 に 80°Cで 20分間乾燥を実施した。  The sample was immersed in a 45 ° C treatment solution containing the concentrations shown in Table 3 for 3 minutes, and then washed with tap water at room temperature for 30 seconds, and then washed with pure water at room temperature for 30 seconds. Finally, drying was performed at 80 ° C for 20 minutes.
[0036] 次に、 JIS Z 2371に準拠した耐塩水噴霧試験法により、塩水噴霧時間 96時間 で耐食性試験を実施し、レイティングナンバーを測定した。なお、レイティングナンパ 一の測定値範囲を下記のように区分し、各々の実施例及び比較例で 2個又は 3個の 試験片の全てが同一の区分に入る場合にはその区分の記号を第 2表及び第 3表に 示し、 2つの区分にまたがる場合にはその両方の区分の記号の間に「〜」を入れて第 2表及び第 3表に示した。  [0036] Next, a corrosion resistance test was performed with a salt spray time of 96 hours according to a salt spray resistance test method based on JIS Z 2371, and the rating number was measured. The measured value range of the rating picker is divided as follows. If all of the two or three test pieces are in the same category in each example and comparative example, the symbol of that category is These are shown in Tables 2 and 3, and in cases where they extend over two categories, “~” is inserted between the symbols of both categories and shown in Tables 2 and 3.
[0037] ◎: レイティングナンバー 10〜9. 5、 〇： レイティングナンバー 9. 4 9. 0 Δ: レイティングナンバー 8. 9 8. 4 X： レイティングナンバー 8. 3以下。 2] [0037] ◎: Rating number 10 ~ 9.5, ○: Rating number 9.4 9. 0 Δ: Rating number 8.9 8. 4 X: Rating number 8.3 or less. 2]
Figure imgf000012_0001
[0039] [表 3]
Figure imgf000012_0001
[0039] [Table 3]
娘 Daughter
Figure imgf000013_0001
Figure imgf000013_0001
[0040] 実施例 26〜27  [0040] Examples 26-27
ADC— 12合金を用いてダイカスト铸造して得た多数の試験片を、液温 40°Cで濃 度 5gZLのァクタン 70 (メルテックス社製)の水溶液中に 1分間浸漬し、その後室温で の水道水洗浄を 30秒間実施し、次 、で室温での純水洗浄を 30秒間実施した。 [0041] 硫酸として 95容量％硫酸を用い、ホウ酸として 99. 5質量％ホウ酸を用い、酢酸二 ッケルとして 99質量％酢酸ニッケル四水和物を用いて、上記のように前処理した試 験片を、硫酸濃度 2molZL、ホウ酸濃度 0. 2molZLの処理液中で電流密度 2AZ dm2,浴温 25°Cで 20分間陽極酸化処理し、次いで、酢酸ニッケル濃度 2gZLの処 理液中に浴温 85°Cで 5分間浸漬して封孔処理した。 A large number of test pieces obtained by die casting using ADC-12 alloy were immersed in an aqueous solution of Actan 70 (Meltex) at a liquid temperature of 40 ° C for 1 minute, and then at room temperature. Washing with tap water was performed for 30 seconds, followed by washing with pure water at room temperature for 30 seconds. [0041] 95% by volume sulfuric acid was used as the sulfuric acid, 99.5% by weight boric acid was used as the boric acid, and 99% by weight nickel acetate tetrahydrate was used as the nickel acetate. Specimens were anodized in a treatment solution with a sulfuric acid concentration of 2 molZL and boric acid concentration of 0.2 molZL for 20 minutes at a current density of 2AZ dm 2 and a bath temperature of 25 ° C. It was immersed and sealed at a bath temperature of 85 ° C for 5 minutes.
[0042] 上記のように前処理した試験片及び更に上記のように陽極酸化処理及び封孔処理 を実施した試験片を各々の実施例 26及び 27で 6個用い、実施例 1と同一の条件下 で表面化成処理を実施した。  [0042] The same conditions as in Example 1 were used, using six test pieces pretreated as described above and further subjected to anodizing treatment and sealing treatment as described above in each of Examples 26 and 27. Surface chemical conversion treatment was performed below.
[0043] 次に、 JIS Z 2371に準拠した耐塩水噴霧試験法により、塩水噴霧時間 96時間、 120時間又は 240時間の耐食性試験をそれぞれ 2個の試験片で実施し、レイティン グナンバーを測定した。 2個の試験片のレイティングナンバーの平均値は第 4表に示 す通りであった。  [0043] Next, according to the salt spray resistance test method in accordance with JIS Z 2371, a corrosion resistance test was performed with a salt spray time of 96 hours, 120 hours, or 240 hours, respectively, and the rating number was measured. The average rating numbers of the two specimens were as shown in Table 4.
[0044] [表 4] 第 4 表
Figure imgf000014_0001
第 4表に示すデータから明らかなように、アルミニウム材の表面を陽極酸ィ匕処理し、 次いで封孔処理し、その後に本発明の表面化成処理を実施することにより耐食性が 更に改善される。 [0044] [Table 4] Table 4
Figure imgf000014_0001
As is apparent from the data shown in Table 4, the corrosion resistance is further improved by subjecting the surface of the aluminum material to an anodizing treatment, followed by a sealing treatment, followed by the surface chemical conversion treatment of the present invention.

Claims

請求の範囲 The scope of the claims
[1] アルミニウム又はアルミニウム合金力 なるアルミニウム材の表面を、  [1] Aluminum or aluminum alloy force
硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  Chromium nitrate concentration is 3-12gZL as Cr (NO),
3 3  3 3
バナジン酸アンモ-ゥム濃度が NH VOとして 0. 5〜7gZLであり、  Ammonium vanadate concentration is 0.5-7gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、  Lithium fluoride concentration is 0.5-3gZL as LiF,
硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、  Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO,
3  Three
液温が 40〜50°Cである  Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施して皮膜を形成することを特徴とするアルミニゥ ム材表面の化成処理方法。  A method for chemical conversion treatment of an aluminum material surface, wherein a film is formed by chemical conversion treatment with a treatment liquid for 1 to 5 minutes.
[2] アルミニウム又はアルミニウム合金力もなるアルミニウム材の表面を陽極酸ィ匕処理し 、次いで封孔処理し、その後、 [2] The surface of an aluminum material that also has aluminum or aluminum alloy strength is anodized, then sealed, and then
硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  Chromium nitrate concentration is 3-12gZL as Cr (NO),
3 3  3 3
バナジン酸アンモニゥム濃度が NH VOとして 0. 5〜7gZLであり、  The concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、  Lithium fluoride concentration is 0.5-3gZL as LiF,
硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、  Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO,
3  Three
液温が 40〜50°Cである  Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施して皮膜を形成することを特徴とするアルミニゥ ム材表面の化成処理方法。  A method for chemical conversion treatment of an aluminum material surface, wherein a film is formed by chemical conversion treatment with a treatment liquid for 1 to 5 minutes.
[3] アルミニウム又はアルミニウム合金力 なるアルミニウム材の表面を、 [3] Aluminum or aluminum alloy strength
硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  Chromium nitrate concentration is 3-12gZL as Cr (NO),
3 3  3 3
バナジン酸アンモニゥム濃度が NH VOとして 0. 5〜7gZLであり、  The concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、  Lithium fluoride concentration is 0.5-3gZL as LiF,
硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、  Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO,
3  Three
液温が 40〜50°Cである  Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施することにより形成される皮膜を有することを特 徴とするアルミニウム材。 It has a film formed by performing chemical conversion treatment for 1 to 5 minutes with the treatment liquid. Aluminum material to be collected.
[4] アルミニウム又はアルミニウム合金力もなるアルミニウム材の表面を陽極酸ィ匕処理し 、次いで封孔処理し、その後、  [4] The surface of an aluminum material that also has aluminum or aluminum alloy strength is anodized, then sealed, and then
硝酸クロム濃度が Cr(NO )として 3〜12gZLであり、  Chromium nitrate concentration is 3-12gZL as Cr (NO),
3 3  3 3
バナジン酸アンモニゥム濃度が NH VOとして 0. 5〜7gZLであり、  The concentration of ammonium vanadate is 0.5-7 gZL as NH VO,
4 3  4 3
フッ化チタンカリウム濃度が K TiFとして 0. 5〜3gZLであり、  Titanium potassium fluoride concentration is 0.5-3gZL as K TiF,
2 6  2 6
フッ化リチウム濃度が LiFとして 0. 5〜3gZLであり、  Lithium fluoride concentration is 0.5-3gZL as LiF,
硝酸濃度が HNOとして 0. 5〜1. 8mLZLであり、  Nitric acid concentration is 0.5 ~ 1.8mLZL as HNO,
3  Three
液温が 40〜50°Cである  Liquid temperature is 40-50 ° C
処理液で 1〜5分間化成処理を実施することにより形成される皮膜を有することを特 徴とするアルミニウム材。  An aluminum material characterized by having a film formed by performing chemical conversion treatment with a treatment liquid for 1 to 5 minutes.
[5] アルミニウム材がアルミニウム合金ダイカスト製品である請求項 3又は 4記載のアルミ ユウム材。 [5] The aluminum material according to claim 3 or 4, wherein the aluminum material is an aluminum alloy die-cast product.
PCT/JP2007/050077 2006-01-10 2007-01-09 Method for chemical conversion treatment of the surface of aluminum material and aluminum material WO2007080849A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN2007800011381A CN101356300B (en) 2006-01-10 2007-01-09 Method for chemical conversion treatment of the surface of aluminum material and aluminum material
JP2007553897A JPWO2007080849A1 (en) 2006-01-10 2007-01-09 Chemical conversion treatment method for aluminum material surface and aluminum material

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-003058 2006-01-10
JP2006003058 2006-01-10
JP2006265778 2006-09-28
JP2006-265778 2006-09-28

Publications (1)

Publication Number Publication Date
WO2007080849A1 true WO2007080849A1 (en) 2007-07-19

Family

ID=38256255

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/050077 WO2007080849A1 (en) 2006-01-10 2007-01-09 Method for chemical conversion treatment of the surface of aluminum material and aluminum material

Country Status (3)

Country Link
JP (1) JPWO2007080849A1 (en)
CN (1) CN101356300B (en)
WO (1) WO2007080849A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2492371A1 (en) * 2011-02-24 2012-08-29 Dr.Ing. Max Schlötter GmbH & Co. KG Cobalt-free passivation solution and method for depositing cobalt-free passivation coatings on zinc and zinc alloy surfaces
WO2014035690A1 (en) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
CN112725811A (en) * 2020-11-27 2021-04-30 上海宏挺紧固件制造有限公司 Big flat-head screw and processing method thereof
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
WO2023119826A1 (en) * 2021-12-22 2023-06-29 ディップソール株式会社 Chemical treatment liquid and method for chemical treatment of target metal material

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102776500B (en) * 2012-07-11 2014-07-16 东莞市闻誉实业有限公司 Aluminum or aluminum alloy surface chemical conversion treatment method
CN105420714A (en) * 2015-11-25 2016-03-23 广东致卓精密金属科技有限公司 Method for preparing high-corrosion-resistance aluminum alloy trivalent chromium composite conversion coating
CN105543833A (en) * 2015-12-31 2016-05-04 芜湖市金宇石化设备有限公司 Phosphating method for aluminum alloy surface
CN105463432A (en) * 2015-12-31 2016-04-06 芜湖市金宇石化设备有限公司 Preparing method for treating fluid used for phosphating aluminum alloy surfaces
CN105463433A (en) * 2015-12-31 2016-04-06 芜湖市金宇石化设备有限公司 Treating fluid for phosphating aluminum alloy surfaces
CN110691862A (en) * 2017-05-27 2020-01-14 深圳市恒兆智科技有限公司 Coating agent, metal piece and surface coating treatment method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5337550A (en) * 1976-09-20 1978-04-06 Nippon Paint Co Ltd Surface treating agents for aluminum or aluminum alloy and surface treating process
JPH03104633A (en) * 1989-09-18 1991-05-01 Sumitomo Metal Ind Ltd Surface-treated steel stock excellent in corrosion resistance
JP2003171778A (en) * 2001-12-06 2003-06-20 Nippon Hyomen Kagaku Kk Method for forming protective film of metal, and protective film of metal
JP2004183015A (en) * 2002-11-29 2004-07-02 Nippon Parkerizing Co Ltd Metal surface treating agent, metal surface treating method and surface treated metallic material
JP2005264230A (en) * 2004-03-18 2005-09-29 Nippon Parkerizing Co Ltd Surface treatment composition for metal, surface treatment liquid for metal, surface treatment method for metal, and metallic material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0790614A (en) * 1993-09-22 1995-04-04 Elna Co Ltd Aluminum or aluminum alloys and their chemical conversion treatment
JP4628726B2 (en) * 2004-03-02 2011-02-09 日本表面化学株式会社 Aluminum member, method for producing the same, and chemical for production

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5337550A (en) * 1976-09-20 1978-04-06 Nippon Paint Co Ltd Surface treating agents for aluminum or aluminum alloy and surface treating process
JPH03104633A (en) * 1989-09-18 1991-05-01 Sumitomo Metal Ind Ltd Surface-treated steel stock excellent in corrosion resistance
JP2003171778A (en) * 2001-12-06 2003-06-20 Nippon Hyomen Kagaku Kk Method for forming protective film of metal, and protective film of metal
JP2004183015A (en) * 2002-11-29 2004-07-02 Nippon Parkerizing Co Ltd Metal surface treating agent, metal surface treating method and surface treated metallic material
JP2005264230A (en) * 2004-03-18 2005-09-29 Nippon Parkerizing Co Ltd Surface treatment composition for metal, surface treatment liquid for metal, surface treatment method for metal, and metallic material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2492371A1 (en) * 2011-02-24 2012-08-29 Dr.Ing. Max Schlötter GmbH & Co. KG Cobalt-free passivation solution and method for depositing cobalt-free passivation coatings on zinc and zinc alloy surfaces
WO2014035690A1 (en) * 2012-08-29 2014-03-06 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
RU2609585C2 (en) * 2012-08-29 2017-02-02 Ппг Индастриз Огайо, Инк. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition
CN112725811A (en) * 2020-11-27 2021-04-30 上海宏挺紧固件制造有限公司 Big flat-head screw and processing method thereof
CN112725811B (en) * 2020-11-27 2023-02-28 上海宏挺紧固件制造有限公司 Big flat-head screw and processing method thereof
WO2023119826A1 (en) * 2021-12-22 2023-06-29 ディップソール株式会社 Chemical treatment liquid and method for chemical treatment of target metal material

Also Published As

Publication number Publication date
CN101356300A (en) 2009-01-28
CN101356300B (en) 2010-11-03
JPWO2007080849A1 (en) 2009-06-11

Similar Documents

Publication Publication Date Title
WO2007080849A1 (en) Method for chemical conversion treatment of the surface of aluminum material and aluminum material
JP5213308B2 (en) Metal surface treatment agent
US9328423B2 (en) Liquid trivalent chromate for aluminium or aluminium alloy and method for forming corrosion-resistant film over surface of aluminium or aluminium alloy by using same
BRPI0708467B1 (en) COMPOSITION FOR METAL SURFACE TREATMENT, METAL SURFACE TREATMENT METHOD, AND METAL MATERIAL
JPH10183364A (en) Protective film forming agent for metal and treatment thereof
TW200417420A (en) Chemical conversion coating agent and surface-treated metal
AU2004202524A1 (en) Method of surface treating metal and metal surface treated thereby
HUE035892T2 (en) Surface treatment liquid for zinc-based metal material and method for surface-treating zinc-based metal material
BR112013028734B1 (en) chemical conversion treatment agent for surface treatment of metal substrate and method for surface treatment of metal substrate using the same
JP4508634B2 (en) Metal surface treatment agent, metal surface treatment liquid, corrosion-resistant colored film formed thereby, corrosion-resistant colored part having this corrosion-resistant colored film, and method for producing this corrosion-resistant colored part
US6471788B1 (en) Ferrate conversion coatings for metal substrates
JP4112219B2 (en) Surface treatment method for lithium-based magnesium alloy material
US6432224B1 (en) Isomolybdate conversion coatings
JP2001123274A (en) High corrosion resistance surface treated magnesium alloy product and producing method therefor
US2795518A (en) Process for treating steel, zinc, and aluminum to increase corrosion resistance
JP3903381B2 (en) How to paint aluminum alloy
JP5648245B2 (en) Method for forming chromium-free metal protective film and treatment agent for forming chromium-free metal protective film
JP4865139B2 (en) Method for forming chromium-free corrosion-resistant film on Sn-Zn alloy plating
CN102776500B (en) Aluminum or aluminum alloy surface chemical conversion treatment method
CN114351131B (en) Aluminum alloy radiator and preparation method thereof
KR102605141B1 (en) Plating processing method for surface treatment of metal
JP2001335958A (en) METHOD FOR FORMING HEXAVALENT CHROMIUM-FREE CORROSION RESISTANT FILM ON Sn-Zn ALLOY PLATING
JP2001123294A (en) Method for surface treatment of magnesium or magnesium alloy
JP2005325403A (en) Surface treatment method for aluminum die-cast material
JP2007100186A (en) Chemical conversion treatment method

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780001138.1

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2007553897

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07706424

Country of ref document: EP

Kind code of ref document: A1