JP5584922B2 - Trivalent chromium chemical conversion treatment solution for forming a trivalent chromium chemical conversion coating on zinc or zinc alloy plating - Google Patents

Trivalent chromium chemical conversion treatment solution for forming a trivalent chromium chemical conversion coating on zinc or zinc alloy plating Download PDF

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JP5584922B2
JP5584922B2 JP2007327051A JP2007327051A JP5584922B2 JP 5584922 B2 JP5584922 B2 JP 5584922B2 JP 2007327051 A JP2007327051 A JP 2007327051A JP 2007327051 A JP2007327051 A JP 2007327051A JP 5584922 B2 JP5584922 B2 JP 5584922B2
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trivalent chromium
chemical conversion
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zinc
chromium chemical
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JP2009149926A (en
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晴雄 花形
完昭 金野
茂実 田中
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Dipsol Chemicals Co Ltd
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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
    • C23C22/46—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 oxalates
    • 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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/53—Treatment of zinc or alloys based thereon
    • 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

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Description

本発明は、亜鉛又は亜鉛合金めっき上に３価クロム化成処理皮膜を形成させるための３価クロム化成処理液、それを用いて亜鉛又は亜鉛合金めっき上に３価クロム化成処理皮膜を形成させる方法及び亜鉛又は亜鉛合金めっき上に形成された３価クロム化成処理皮膜に関する。   The present invention relates to a trivalent chromium chemical conversion treatment liquid for forming a trivalent chromium chemical conversion treatment film on zinc or zinc alloy plating, and a method for forming a trivalent chromium chemical conversion treatment film on zinc or zinc alloy plating using the same. And a trivalent chromium chemical conversion coating formed on zinc or zinc alloy plating.

金属表面の防食方法として亜鉛又は亜鉛合金めっきを行なう方法があるが、めっき単独では耐食性が十分ではなく、めっき後６価を含むクロム酸処理、いわゆるクロメート処理が産業界で広範囲に採用されている。しかしながら、近年、６価クロムが人体や環境に悪い影響を与える事が指摘され、６価クロムの使用が規制されるようになった。その代替技術の１つとして３価クロムを使用した防錆皮膜がある。例えば、特開２０００−５０９４３４号公報や特開２００４−００３０１９号公報では、３価クロム塩と硝酸根、有機酸、コバルト等の金属塩を使用して処理する方法が開示されている。また、亜鉛合金めっき用３価クロム化成処理剤として特開２００１−３３５９５８号公報及び特開２００５−１２６７９７号公報で３価クロム塩と硝酸根、有機酸、コバルト等の金属塩を使用して処理する方法が開示されている。   Although there is a method of performing zinc or zinc alloy plating as a corrosion prevention method for metal surfaces, the plating alone is not sufficient in corrosion resistance, and chromic acid treatment including hexavalent after plating, so-called chromate treatment, is widely used in the industry. . However, in recent years, it has been pointed out that hexavalent chromium has a bad influence on the human body and the environment, and the use of hexavalent chromium has been regulated. As one of the alternative technologies, there is a rust preventive film using trivalent chromium. For example, Japanese Patent Application Laid-Open No. 2000-509434 and Japanese Patent Application Laid-Open No. 2004-003019 disclose a method of treatment using a trivalent chromium salt and a metal salt such as nitrate radical, organic acid, and cobalt. Further, as a trivalent chromium chemical conversion treatment agent for zinc alloy plating, a treatment using a trivalent chromium salt and a metal salt such as nitrate, organic acid, cobalt, etc. in JP-A No. 2001-335958 and JP-A No. 2005-126797 A method is disclosed.

特開２０００−５０９４３４号公報JP 2000-509434 A 特開２００４−００３０１９号公報JP 2004-003019 A 特開２００１−３３５９５８号公報JP 2001-335958 A 特開２００５−１２６７９７号公報Japanese Patent Laid-Open No. 2005-126797

従来、亜鉛めっき上に厚い３価クロム化成皮膜を形成するためには、処理温度を高くし、処理時間を長くする必要があり、亜鉛合金めっき上には、処理温度を高くし、処理時間を長くしても均一で厚い皮膜を形成することが極めて困難であった。
本発明は、従来の３価クロム化成処理液と比較して、低温、短時間で、亜鉛又は亜鉛合金めっき上に皮膜が厚く耐食性の良い３価クロム化成処理皮膜を提供することができる３価クロム化成処理液を提供することを目的とする。 Conventionally, in order to form a thick trivalent chromium conversion coating on zinc plating, it is necessary to increase the processing temperature and lengthen the processing time. On the zinc alloy plating, the processing temperature is increased and the processing time is reduced. Even if it was long, it was extremely difficult to form a uniform and thick film.
The present invention can provide a trivalent chromium chemical conversion treatment film having a high corrosion resistance and a thick film on zinc or zinc alloy plating at a low temperature and in a short time as compared with the conventional trivalent chromium chemical conversion treatment liquid. An object is to provide a chromium chemical conversion treatment liquid.

本発明は、基体上に亜鉛めっきを析出させた後、特定の組成の３価クロム化成処理液を用いて３価クロム化成処理を行うことにより、上記課題を効率的に解決できるとの知見に基づいてなされたのである。本発明者の実験によれば、３価クロム化成処理液にニトロ基を有する芳香族化合物を添加すれば、従来の３価クロム化成処理皮膜と比較して皮膜が厚く耐食性の良い３価クロム化成処理皮膜が得られることを見出した。この理由については明らかでないが、ニトロ基を有する芳香族化合物を添加することによって反応が促進され、従来の３価クロム化成処理液と比較して、皮膜が厚くなるものと考えられる。
したがって、本発明は、ニトロ基を有する芳香族化合物を０．２〜１０ｇ／Ｌ含有することを特徴とする亜鉛又は亜鉛合金めっき上に３価クロム化成処理皮膜を形成させるための３価クロム化成処理液を提供する。
また、本発明は、亜鉛又は亜鉛合金めっきを前記３価クロム化成処理液に接触させることを特徴とする亜鉛又は亜鉛合金めっき上に３価クロム化成処理皮膜を形成させる方法を提供する。
さらに、本発明は、前記３価クロム化成処理液を用いて得られた亜鉛又は亜鉛合金めっき上に形成された３価クロム化成処理皮膜を提供する。 The present invention is based on the knowledge that the above-mentioned problems can be efficiently solved by depositing galvanizing on a substrate and then performing trivalent chromium chemical conversion treatment using a trivalent chromium chemical conversion treatment liquid having a specific composition. It was made on the basis. According to the experiment of the present inventor, if an aromatic compound having a nitro group is added to the trivalent chromium chemical conversion treatment solution, the film is thicker than the conventional trivalent chromium chemical conversion treatment film and has a good corrosion resistance. It was found that a treated film was obtained. Although the reason for this is not clear, it is considered that the reaction is promoted by adding an aromatic compound having a nitro group, and the film becomes thicker than the conventional trivalent chromium chemical conversion treatment solution.
Accordingly, the present invention provides a trivalent chromium chemical conversion coating for forming a trivalent chromium chemical conversion coating on zinc or zinc alloy plating characterized by containing 0.2 to 10 g / L of an aromatic compound having a nitro group. Provide a processing solution.
Moreover, this invention provides the method of forming a trivalent chromium chemical conversion treatment film on zinc or zinc alloy plating characterized by making zinc or a zinc alloy plating contact the said trivalent chromium chemical conversion treatment liquid.
Furthermore, this invention provides the trivalent chromium chemical conversion treatment film formed on the zinc or zinc alloy plating obtained using the said trivalent chromium chemical conversion treatment liquid.

本発明は、亜鉛又は亜鉛合金めっき上に、耐食性の良い３価クロム化成処理皮膜を得ることができる。
従来の亜鉛めっき用３価クロム化成処理液に比較して、低温、短時間で厚い３価クロム化成処理皮膜ができるだけでなく、特に、従来困難であった亜鉛合金めっきに対しても均一で厚膜の耐食性が良好な３価クロム化成処理皮膜が得られる。 The present invention can obtain a trivalent chromium chemical conversion coating having good corrosion resistance on zinc or zinc alloy plating.
Compared to the conventional trivalent chromium chemical conversion treatment solution for zinc plating, not only can a thick trivalent chromium chemical conversion treatment film be produced at a low temperature and in a short time, but also it is particularly uniform and thick even for zinc alloy plating, which has been difficult in the past. A trivalent chromium chemical conversion film having good film corrosion resistance is obtained.

本発明において、亜鉛又は亜鉛合金めっきは、鉄、ニッケル、銅などの各種金属、及びこれらの合金、あるいは亜鉛置換処理を施したアルミニウムなどの金属や合金の板状物、直方体、円柱、円筒、球状物など種々の形状の基体に施される。
亜鉛又は亜鉛合金めっきを、常法により前記基体上に析出させる。基体上に亜鉛又は亜鉛合金めっきを析出させるために用いるめっき浴として、硫酸浴、アンモン浴、カリ浴などの酸性浴、アルカリノーシアン浴、アルカリシアン浴等のアルカリ浴のいずれをもちいてもよい。基体上に析出させる亜鉛又は亜鉛合金めっきの厚みは任意とすることができるが、好ましくは１μｍ以上、より好ましくは５〜２５μｍである。
亜鉛合金めっきとしては、亜鉛−鉄合金めっき、ニッケル供析率５〜２０％の亜鉛−ニッケル合金めっき、亜鉛―コバルト合金めっき、錫―亜鉛合金めっき等が挙げられる。好ましくは、亜鉛合金めっきは、Ｚｎ−Ｆｅめっき（Ｆｅ含量０．４−２ｗｔ％）、Ｚｎ−Ｎｉめっき（Ｎｉ含量５−１８ｗｔ％）及びＳｎ−Ｚｎめっき（Ｚｎ含量５−６０ｗｔ％）であり、特に好ましくはＺｎ−Ｎｉめっき（Ｎｉ含量５−１８ｗｔ％）及びＳｎ−Ｚｎめっき（Ｚｎ含量５−６０ｗｔ％）である。
基体上に亜鉛及び亜鉛合金めっきを析出させた後、例えば水洗し、低濃度３価クロム、シュウ酸、マロン酸等の有機酸、コバルト塩及び無機酸イオン（例えば、塩酸、硫酸、硝酸、リン酸あるいはこれらの塩のうち１種又は２種以上）を含有する水溶液で浸漬処理を行う。 In the present invention, zinc or zinc alloy plating includes various metals such as iron, nickel, and copper, and alloys thereof, or a metal or alloy such as aluminum subjected to zinc substitution treatment, a rectangular parallelepiped, a cylinder, a cylinder, It is applied to substrates of various shapes such as spherical objects.
Zinc or zinc alloy plating is deposited on the substrate by a conventional method. As a plating bath used for depositing zinc or zinc alloy plating on the substrate, any of an acidic bath such as a sulfuric acid bath, an ammon bath, and a potassium bath, an alkaline bath such as an alkali non-cyan bath, and an alkali cyan bath may be used. . The thickness of the zinc or zinc alloy plating deposited on the substrate can be arbitrary, but is preferably 1 μm or more, more preferably 5 to 25 μm.
Examples of the zinc alloy plating include zinc-iron alloy plating, zinc-nickel alloy plating with a nickel deposition rate of 5 to 20%, zinc-cobalt alloy plating, and tin-zinc alloy plating. Preferably, the zinc alloy plating is Zn—Fe plating (Fe content 0.4-2 wt%), Zn—Ni plating (Ni content 5-18 wt%) and Sn—Zn plating (Zn content 5-60 wt%). Particularly preferred are Zn—Ni plating (Ni content 5-18 wt%) and Sn—Zn plating (Zn content 5-60 wt%).
After depositing zinc and zinc alloy plating on the substrate, it is washed with water, for example, low concentration trivalent chromium, oxalic acid, malonic acid and other organic acids, cobalt salts and inorganic acid ions (for example, hydrochloric acid, sulfuric acid, nitric acid, phosphorus Immersion treatment is carried out with an aqueous solution containing an acid or one or more of these salts).

本発明の３価クロム化成処理液は、３価クロムイオン及びニトロ基を有する芳香族化合物を含有する、亜鉛又は亜鉛合金めっき上に３価クロム化成処理皮膜を形成させるための３価クロム化成処理液である。
３価クロムイオンの供給源としては、３価クロムイオンを含むいずれのクロム化合物も使用することができるが、好ましくは塩化クロム、硫酸クロム、硝酸クロム、燐酸クロム、酢酸クロム等の３価クロム塩を使用することができる。上記３価クロムの供給源は、１種あるいは２種以上を使用することができる。処理液中の３価クロムの濃度に性能的な制限はないが、排水処理の観点からは可能な限り低濃度化するのが好ましい。よって、耐食性能等も考慮に入れると、処理液中の３価クロムイオンの濃度として０．５〜２０ｇ/Ｌの範囲が好ましく、より好ましくは０．２〜５ｇ/Ｌの範囲であり、さらに好ましくは１〜５ｇ／Ｌの範囲である。本発明においては、このような低濃度範囲で３価クロムを用いると、排水処理、経済的にも有利である。なお、本発明の３価クロム化成処理液は一般に６価クロムフリー３価クロム皮膜と呼ばれる皮膜を形成させるための３価クロム化成処理液である。 The trivalent chromium chemical conversion treatment liquid of the present invention contains a trivalent chromium ion and an aromatic compound having a nitro group, and forms a trivalent chromium chemical conversion coating on zinc or zinc alloy plating. It is a liquid.
As a supply source of trivalent chromium ions, any chromium compound containing trivalent chromium ions can be used, but trivalent chromium salts such as chromium chloride, chromium sulfate, chromium nitrate, chromium phosphate, and chromium acetate are preferable. Can be used. The said trivalent chromium supply source can use 1 type (s) or 2 or more types. Although there is no performance limitation on the concentration of trivalent chromium in the treatment liquid, it is preferable to reduce the concentration as much as possible from the viewpoint of wastewater treatment. Therefore, in consideration of corrosion resistance and the like, the concentration of trivalent chromium ions in the treatment liquid is preferably in the range of 0.5 to 20 g / L, more preferably in the range of 0.2 to 5 g / L, Preferably it is the range of 1-5 g / L. In the present invention, the use of trivalent chromium in such a low concentration range is advantageous in terms of waste water treatment and economy. In addition, the trivalent chromium chemical conversion treatment liquid of the present invention is a trivalent chromium chemical conversion liquid for forming a film generally called a hexavalent chromium-free trivalent chromium film.

ニトロ基を有する芳香族化合物としては、好ましくはニトロベンゼン誘導体類である。ここで、ニトロベンゼン誘導体類としては、具体的には、例えばニトロベンゼン、１，３−ジニトロベンゼンなどのニトロベンゼン類、ニトロベンゼンスルホン酸、ジニトロベンゼンスルホン酸、ニトロベンゼンスルホン酸ナトリウム、ニトロアニリンスルホン酸、アミノニトロベンゼンスルホン酸などのニトロベンゼンスルホン酸類又はそのアルカリ金属若しくはアルカリ土類金属塩、ニトロ安息香酸、ニトロ安息香酸ナトリウム、ニトロフタル酸などのニトロベンゼンカルボン酸類又はそのアルカリ金属若しくはアルカリ土類金属塩、ニトロフェノール、ニトロカテコールなどのニトロヒドロキシベンゼン類、ニトロベンジルアルコール、ジニトロベンジルアルコールなどのニトロフェニルアルコール類などが挙げられる。
このようなニトロベンゼン誘導体類としては、水に可溶性のものが好ましく、溶解度の程度としては非水溶性でなければ、溶解度が高く易水溶性でも、また溶解度が低く微若しくは難水溶性であってもよい。上記のうちでは、ニトロベンゼンスルホン酸類又はそのアルカリ金属若しくはアルカリ土類金属塩、ニトロベンゼンカルボン酸又はそのアルカリ金属若しくはアルカリ土類金属塩、ニトロヒドロキシベンゼン類が好ましく、とりわけニトロベンゼンスルホン酸、ニトロベンゼンスルホン酸ナトリウム、ニトロ安息香酸ナトリウム、ニトロアニリンスルホン酸、ニトロフェノールが好ましい。上記ニトロ基を有する芳香族化合物は、１種又は２種以上を使用することができる。処理溶液中のニトロ基を有する芳香族化合物の濃度は、０．２〜１０ｇ／Ｌの範囲であり、好ましくは０．５〜５ｇ／Ｌの範囲である。
なお、本発明の３価クロム化成処理液においては、３価クロムイオン及び及びニトロ基を有する芳香族化合物以外の成分として、本発明の目的を損なわない限り、従来公知の３価クロム化成処理液に用いられるいかなる成分も使用することができる。 The aromatic compound having a nitro group is preferably a nitrobenzene derivative. Here, specific examples of the nitrobenzene derivatives include nitrobenzenes such as nitrobenzene and 1,3-dinitrobenzene, nitrobenzene sulfonic acid, dinitrobenzene sulfonic acid, sodium nitrobenzene sulfonate, nitroaniline sulfonic acid, and aminonitrobenzene sulfone. Nitrobenzenesulfonic acid such as acid or alkali metal or alkaline earth metal salt thereof, nitrobenzoic acid, sodium nitrobenzoate, nitrobenzenecarboxylic acid such as nitrophthalic acid or alkali metal or alkaline earth metal salt thereof, nitrophenol, nitrocatechol, etc. And nitrophenyl alcohols such as nitrobenzylbenzene, nitrobenzyl alcohol and dinitrobenzyl alcohol.
Such nitrobenzene derivatives are preferably those that are soluble in water. If the degree of solubility is not water-insoluble, the solubility may be high and easily water-soluble, or the solubility may be low or slightly or poorly water-soluble. Good. Among the above, nitrobenzene sulfonic acids or alkali metal or alkaline earth metal salts thereof, nitrobenzene carboxylic acid or alkali metal or alkaline earth metal salts thereof, and nitrohydroxybenzenes are preferred, especially nitrobenzene sulfonic acid, sodium nitrobenzene sulfonate, Sodium nitrobenzoate, nitroaniline sulfonic acid and nitrophenol are preferred. The aromatic compound which has the said nitro group can use 1 type (s) or 2 or more types. The density | concentration of the aromatic compound which has a nitro group in a process solution is the range of 0.2-10 g / L, Preferably it is the range of 0.5-5 g / L.
In the trivalent chromium chemical conversion treatment liquid of the present invention, as a component other than the trivalent chromium ions and the aromatic compound having a nitro group, a conventionally known trivalent chromium chemical conversion liquid is used as long as the object of the present invention is not impaired. Any component used in can be used.

本発明の３価クロム化成処理液は、さらに無機酸イオンを含んでいてもよい。無機酸イオンの供給源としては、塩酸、硝酸、硫酸又はそれらの塩などが挙げられる。上記無機酸は、１種又は２種以上を使用することができる。処理液中の無機酸イオンの濃度は、好ましくは１〜５０ｇ/Ｌの範囲であり、より好ましくは５〜２０ｇ/Ｌの範囲である。
本発明の３価クロム化成処理液はキレート剤を含まなくてもよい。しかしながら、キレート剤を含んでいるとより均一な化成皮膜が得られるので好ましい。キレート剤としては、キレート形成能のある有機カルボン酸などが挙げられる。また、有機カルボン酸の中でも、シュウ酸、マロン酸、コハク酸、クエン酸、アジピン酸などのジカルボン酸、クエン酸、酒石酸、リンゴ酸などのオキシカルボン酸及びトリカルバリル酸などの多価カルボン酸が好ましく、これらは塩（例えば、ナトリウム、カリウム、アンモニウム等の塩）の形態であってもよい。上記キレート剤は、１種又は２種以上を使用することができる。処理液中のキレート剤の濃度は、好ましくは１〜４０ｇ／Ｌの範囲であり、より好ましくは２〜１０ｇ／Ｌの範囲である。
本発明の３価クロム化成処理液は、さらにＣｏ、Ｖ、Ｔｉ、Ｗ、Ｚｒ、Ｍｎ、Ｍｏ、Ｔａ、Ｃｅ、Ｓｒ、Ｆｅ及びＡｌからなる群より選ばれる金属イオンを含んでもよい。金属イオンの供給源としては、金属イオンの塩化物、硝酸塩、硫酸塩、酢酸塩、酸素酸塩などが挙げられる。上記金属イオンは、１種又は２種以上を使用することができる。処理液中の金属イオンの濃度は、好ましくは０．１〜５ｇ/Ｌの範囲であり、より好ましくは０．５〜３ｇ/Ｌの範囲である。
上記の他に、リン酸、亜リン酸などのリンの酸素酸及びそれらのアルカリ塩などから選ばれた１種以上を添加してもよい。この場合、処理液中の濃度は、０．１〜５０ｇ／Ｌであるのが好ましく、より好ましくは０．５〜２０ｇ／Ｌである。
本発明の３価クロム化成処理液の好ましい態様は、３価クロムイオン濃度として０．５〜２０ｇ／Ｌ、無機酸イオンとして１〜５０ｇ／Ｌ、有機カルボン酸又はその塩として１〜４０ｇ／Ｌ、及びＣｏ、Ｖ、Ｔｉ、Ｗ、Ｚｒ、Ｍｎ、Ｍｏ、Ｔａ、Ｃｅ、Ｓｒ、Ｆｅ及びＡｌからなる群より選ばれる金属イオンとして０．１〜５ｇ／Ｌを含有する３価クロム化成処理液である。 The trivalent chromium chemical conversion treatment liquid of the present invention may further contain inorganic acid ions. Examples of the supply source of inorganic acid ions include hydrochloric acid, nitric acid, sulfuric acid, and salts thereof. The said inorganic acid can use 1 type (s) or 2 or more types. The concentration of inorganic acid ions in the treatment liquid is preferably in the range of 1 to 50 g / L, more preferably in the range of 5 to 20 g / L.
The trivalent chromium chemical conversion treatment liquid of the present invention may not contain a chelating agent. However, it is preferable to contain a chelating agent because a more uniform chemical conversion film can be obtained. Examples of chelating agents include chelate-forming organic carboxylic acids. Among organic carboxylic acids, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, citric acid and adipic acid, oxycarboxylic acids such as citric acid, tartaric acid and malic acid, and polyvalent carboxylic acids such as tricarbaric acid are included. Preferably, these may be in the form of a salt (for example, a salt of sodium, potassium, ammonium, etc.). The chelating agent can use 1 type (s) or 2 or more types. The concentration of the chelating agent in the treatment liquid is preferably in the range of 1 to 40 g / L, more preferably in the range of 2 to 10 g / L.
The trivalent chromium chemical conversion treatment liquid of the present invention may further contain a metal ion selected from the group consisting of Co, V, Ti, W, Zr, Mn, Mo, Ta, Ce, Sr, Fe and Al. Examples of the metal ion supply source include metal ion chlorides, nitrates, sulfates, acetates, and oxyacid salts. The said metal ion can use 1 type (s) or 2 or more types. The concentration of metal ions in the treatment liquid is preferably in the range of 0.1 to 5 g / L, more preferably in the range of 0.5 to 3 g / L.
In addition to the above, one or more selected from phosphorus oxyacids such as phosphoric acid and phosphorous acid and alkali salts thereof may be added. In this case, the concentration in the treatment liquid is preferably 0.1 to 50 g / L, and more preferably 0.5 to 20 g / L.
The preferable aspect of the trivalent chromium chemical conversion treatment liquid of the present invention is 0.5 to 20 g / L as a trivalent chromium ion concentration, 1 to 50 g / L as an inorganic acid ion, and 1 to 40 g / L as an organic carboxylic acid or a salt thereof. And a trivalent chromium chemical conversion treatment containing 0.1 to 5 g / L as a metal ion selected from the group consisting of Co, V, Ti, W, Zr, Mn, Mo, Ta, Ce, Sr, Fe and Al It is.

本発明の３価クロム化成処理液のｐＨは、好ましくは１．０〜５であり、より好ましくは２〜４である。ｐＨの調整には、上記無機酸を用いてもよく、また水酸化アルカリ、アンモニア水などのアルカリ剤を用いてもよい。本発明の３価クロム化成処理液における上記成分の残分は水である。
本発明の亜鉛又は亜鉛合金めっき上に６価クロムフリー３価クロム化成処理皮膜を形成させる方法は、亜鉛又は亜鉛合金めっきを前記３価クロム化成処理液に接触させることを特徴とする。亜鉛又は亜鉛合金めっきを前記３価クロム化成処理液に接触させる方法としては、上記３価クロム化成処理液に亜鉛又は亜鉛合金めっきした基体を浸漬するのが一般的である。例えば１０〜４０℃の液温で５〜６００秒浸漬するのが好ましく、より好ましくは１５〜１２０秒浸漬する。なお、亜鉛めっきでは３価クロム化成処理皮膜の光沢を増すために、通常３価クロム化成処理前に被処理物を希硝酸溶液に浸漬させることが行われるが、本発明ではこのような前処理を用いてもよいし、用いなくともよい。上記以外の条件や処理操作は、従来のクロメート処理方法に準じて行うことができる。
次に、実施例および比較例を示して本発明を説明する。 The pH of the trivalent chromium chemical conversion treatment liquid of the present invention is preferably 1.0 to 5, and more preferably 2 to 4. In adjusting the pH, the above-mentioned inorganic acid may be used, or an alkali agent such as alkali hydroxide or aqueous ammonia may be used. The remainder of the above components in the trivalent chromium chemical conversion treatment liquid of the present invention is water.
The method of forming a hexavalent chromium-free trivalent chromium chemical conversion treatment film on zinc or zinc alloy plating according to the present invention is characterized in that zinc or zinc alloy plating is brought into contact with the trivalent chromium chemical conversion treatment solution. As a method for bringing zinc or zinc alloy plating into contact with the trivalent chromium chemical conversion treatment liquid, it is common to immerse a zinc or zinc alloy plated substrate in the trivalent chromium chemical conversion treatment liquid. For example, it is preferable to immerse at a liquid temperature of 10 to 40 ° C. for 5 to 600 seconds, and more preferably for 15 to 120 seconds. In galvanization, in order to increase the gloss of the trivalent chromium chemical conversion treatment film, the object to be treated is usually immersed in a dilute nitric acid solution before the trivalent chromium chemical conversion treatment. In the present invention, such pretreatment is performed. May or may not be used. Conditions and processing operations other than those described above can be performed in accordance with conventional chromate processing methods.
Next, an Example and a comparative example are shown and this invention is demonstrated.

（実施例１）
ディップソール（株）製ＮＺ−９８浴を使用し、鋼板にジンケートＺｎめっきを厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
硝酸クロムを使用しＣｒ3+として３ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として８ｇ／Ｌ、ＨＮＯ3及びＮａＮＯ3を使用しＮＯ3 -としては１５ｇ／Ｌ、硝酸コバルトを使用しＣｏ2+としては１ｇ／Ｌ、ニトロベンゼンスルホン酸２ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 Example 1
A NZ-98 bath manufactured by Dipsol Co., Ltd. was used, and a steel sheet with zincate zinc plating applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (with stirring). The processing temperature is 30 ° C. and the processing time is 60 seconds.
Using chromium nitrate 3 g / L as Cr 3+, oxalic acid using 8g / L, HNO 3 and NaNO 3 as oxalic acid using dihydrate NO 3 - The 15 g / L, using a cobalt nitrate Then, a treatment solution of 1 g / L as Co 2+ and 2 g / L of nitrobenzenesulfonic acid was erected. The pH was adjusted to pH 2 with NaOH.

（実施例２）
ディップソール（株）製ＮＺ−９８浴を使用し、鋼板にジンケートＺｎめっきを厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は４０℃であり、処理時間は３０秒である。
塩化クロムを使用しＣｒ3+として２ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として４ｇ／Ｌ、マロン酸６ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては９ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては１ｇ／Ｌ、ニトロアニリンスルホン酸４ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 (Example 2)
A NZ-98 bath manufactured by Dipsol Co., Ltd. was used, and a steel sheet with zincate zinc plating applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (with stirring). The processing temperature is 40 ° C. and the processing time is 30 seconds.
2 g / L as Cr 3+ using chromium chloride, oxalate 4g / L as oxalic acid using dihydrate, malonic acid 6 g / L, using HCl and NaCl Cl - The 9 g / L, chloride Cobalt was used and a treatment solution of 1 g / L as Co 2+ and 4 g / L of nitroaniline sulfonic acid was erected. The pH was adjusted to pH 2 with NaOH.

（実施例３）
ディップソール（株）製ＩＺ−２５０Ｙ浴を使用し、鋼板にＺｎ−Ｎｉめっき（Ｎｉ含量１５ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は４０℃であり、処理時間は６０秒である。
塩化クロムを使用しＣｒ3+として１０ｇ／Ｌ、酒石酸８ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては２０ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては１ｇ／Ｌ、ニトロフェノール１ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ３に調整した。 (Example 3)
A dip sole Co., Ltd. IZ-250Y bath was used, and a steel sheet coated with Zn-Ni plating (Ni content 15 wt%) to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 40 ° C. and the processing time is 60 seconds.
Chromium chloride is used as Cr 3+ 10 g / L, tartaric acid 8 g / L, HCl and NaCl are used as Cl − , 20 g / L, cobalt chloride is used as Co 2+ 1 g / L, nitrophenol 1 g / L L treatment solution was erected. The pH was adjusted to pH 3 with NaOH.

（実施例４）
ディップソール（株）製ＩＺ−２５０Ｙ浴を使用し、鋼板にＺｎ−Ｎｉめっき（Ｎｉ含量１５ｗｔ％）を厚さ５μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
硝酸クロムを使用しＣｒ3+として４ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として４ｇ／Ｌ、マロン酸９ｇ／Ｌ、ＨＮＯ3及びＮａＮＯ3を使用しＮＯ3 -としては２０ｇ／Ｌ、硝酸コバルトを使用しＣｏ2+としては３ｇ／Ｌ、ニトロ安息香酸ソーダ１ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ４に調整した。 Example 4
A dip sole Co., Ltd. IZ-250Y bath was used, and a steel sheet coated with Zn—Ni plating (Ni content: 15 wt%) to a thickness of 5 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 30 ° C. and the processing time is 60 seconds.
Chromium nitrate is used as Cr 3+ 4 g / L, oxalic acid is used as dihydrate, oxalic acid is used as 4 g / L, malonic acid 9 g / L, HNO 3 and NaNO 3 are used as NO 3 − as 20 g / L L and cobalt nitrate were used, and a treatment solution of 3 g / L as Co 2+ and 1 g / L of sodium nitrobenzoate was erected. The pH was adjusted to pH 4 with NaOH.

（実施例５）
ディップソール（株）製ＳＺ−２４０浴を使用し、鋼板にＳｎ−Ｚｎめっき（Ｚｎ含量３０ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は４０℃であり、処理時間は４０秒である。
塩化クロムを使用しＣｒ3+として４ｇ／Ｌ、酒石酸１０ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては１５ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては１ｇ／Ｌ、ニトロベンゼンスルホン酸ソーダ４ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 (Example 5)
A dip sole Co., Ltd. SZ-240 bath was used, and a steel plate with Sn—Zn plating (Zn content 30 wt%) applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 40 ° C. and the processing time is 40 seconds.
Chromium chloride is used as Cr 3+ 4 g / L, tartaric acid 10 g / L, HCl and NaCl are used as Cl − , 15 g / L, cobalt chloride is used as Co 2+ 1 g / L, sodium nitrobenzenesulfonate A treatment solution of 4 g / L was erected. The pH was adjusted to pH 2 with NaOH.

（実施例６）
ディップソール（株）製ＳＺ−２４０浴を使用し、鋼板にＳｎ−Ｚｎめっき（Ｚｎ含量３０ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
塩化クロムを使用しＣｒ3+として２ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として５ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては９ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては２ｇ／Ｌ、ニトロ安息香酸ソーダ０．５ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ３に調整した。 (Example 6)
A dip sole Co., Ltd. SZ-240 bath was used, and a steel plate with Sn—Zn plating (Zn content 30 wt%) applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 30 ° C. and the processing time is 60 seconds.
2 g / L as Cr 3+ using chromium chloride, oxalic acid using 5 g / L, HCl and NaCl as oxalic acid using dihydrate Cl - The 9 g / L, using the cobalt chloride Co 2 As a + , a treatment solution of 2 g / L and sodium nitrobenzoate 0.5 g / L was erected. The pH was adjusted to pH 3 with NaOH.

（実施例７）
ディップソール（株）製ＦＺ−２７０浴を使用し、鋼板にＺｎ−Ｆｅめっき（Ｆｅ含量０．４ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
硝酸クロムを使用しＣｒ3+として３ｇ／Ｌ、酒石酸１０ｇ／Ｌ、マロン酸４ｇ／Ｌ、ＨＮＯ3及びＮａＮＯ3を使用しＮＯ3 -としては１５ｇ／Ｌ、硝酸コバルトを使用しＣｏ2+としては１ｇ／Ｌ、ニトロアニリンスルホン酸２ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 (Example 7)
A dip sole FZ-270 bath was used, and a steel sheet coated with Zn-Fe plating (Fe content 0.4 wt%) to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution. (With stirring). The processing temperature is 30 ° C. and the processing time is 60 seconds.
Chromium nitrate is used as Cr 3+ , 3 g / L, tartaric acid 10 g / L, malonic acid 4 g / L, HNO 3 and NaNO 3 are used as NO 3 − , 15 g / L, cobalt nitrate is used as Co 2+ Prepared a treatment solution of 1 g / L and nitroanilinesulfonic acid 2 g / L. The pH was adjusted to pH 2 with NaOH.

（比較例１）
ディップソール（株）製ＮＺ−９８浴を使用し、鋼板にジンケートＺｎめっきを厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
硝酸クロムを使用しＣｒ3+として３ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として８ｇ／Ｌ、ＨＮＯ3及びＮａＮＯ3を使用しＮＯ3 -としては１５ｇ／Ｌ、硝酸コバルトを使用しＣｏ2+としては１ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 (Comparative Example 1)
A NZ-98 bath manufactured by Dipsol Co., Ltd. was used, and a steel sheet with zincate zinc plating applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (with stirring). The processing temperature is 30 ° C. and the processing time is 60 seconds.
Using chromium nitrate 3 g / L as Cr 3+, oxalic acid using 8g / L, HNO 3 and NaNO 3 as oxalic acid using dihydrate NO 3 - The 15 g / L, using a cobalt nitrate Then, a treatment solution of 1 g / L was used as Co 2+ . The pH was adjusted to pH 2 with NaOH.

（比較例２）
ディップソール（株）製ＮＺ−９８浴を使用し、鋼板にジンケートＺｎめっきを厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は４０℃であり、処理時間は３０秒である。
塩化クロムを使用しＣｒ3+として２ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として４ｇ／Ｌ、マロン酸６ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては９ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては１ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 (Comparative Example 2)
A NZ-98 bath manufactured by Dipsol Co., Ltd. was used, and a steel sheet with zincate zinc plating applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (with stirring). The processing temperature is 40 ° C. and the processing time is 30 seconds.
2 g / L as Cr 3+ using chromium chloride, oxalate 4g / L as oxalic acid using dihydrate, malonic acid 6 g / L, using HCl and NaCl Cl - The 9 g / L, chloride Cobalt was used and a treatment solution of 1 g / L was prepared as Co 2+ . The pH was adjusted to pH 2 with NaOH.

（比較例３）
ディップソール（株）製ＩＺ−２５０Ｙ浴を使用し、鋼板にＺｎ−Ｎｉめっき（Ｎｉ含量１５ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は４０℃であり、処理時間は６０秒である。
塩化クロムを使用しＣｒ3+として１０ｇ／Ｌ、酒石酸８ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては２０ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては１ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ３に調整した。 (Comparative Example 3)
A dip sole Co., Ltd. IZ-250Y bath was used, and a steel sheet coated with Zn-Ni plating (Ni content 15 wt%) to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 40 ° C. and the processing time is 60 seconds.
Using chromium chloride, a treatment solution of 10 g / L as Cr 3+ , 8 g / L tartaric acid, 20 g / L as Cl − using HCl and NaCl, and 1 g / L as Co 2+ using Co 2 + I took a bath. The pH was adjusted to pH 3 with NaOH.

（比較例４）
ディップソール（株）製ＩＺ−２５０Ｙ浴を使用し、鋼板にＺｎ−Ｎｉめっき（Ｎｉ含量１５ｗｔ％）を厚さ５μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
硝酸クロムを使用しＣｒ3+として４ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として４ｇ／Ｌ、マロン酸９ｇ／Ｌ、ＨＮＯ3及びＮａＮＯ3を使用しＮＯ3 -としては２０ｇ／Ｌ、硝酸コバルトを使用しＣｏ2+としては３ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ４に調整した。 (Comparative Example 4)
A dip sole Co., Ltd. IZ-250Y bath was used, and a steel sheet coated with Zn—Ni plating (Ni content: 15 wt%) to a thickness of 5 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 30 ° C. and the processing time is 60 seconds.
Chromium nitrate is used as Cr 3+ 4 g / L, oxalic acid is used as dihydrate, oxalic acid is used as 4 g / L, malonic acid 9 g / L, HNO 3 and NaNO 3 are used as NO 3 − as 20 g / L L and cobalt nitrate were used, and a treatment solution of 3 g / L was prepared as Co 2+ . The pH was adjusted to pH 4 with NaOH.

（比較例５）
ディップソール（株）製ＳＺ−２４０浴を使用し、鋼板にＳｎ−Ｚｎめっき（Ｚｎ含量３０ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は４０℃であり、処理時間は４０秒である。
塩化クロムを使用しＣｒ3+として４ｇ／Ｌ、酒石酸１０ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては１５ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては１ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 (Comparative Example 5)
A dip sole Co., Ltd. SZ-240 bath was used, and a steel plate with Sn—Zn plating (Zn content 30 wt%) applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 40 ° C. and the processing time is 40 seconds.
Using chromium chloride, a treatment solution of 4 g / L as Cr 3+ , 10 g / L of tartaric acid, 15 g / L as Cl − using HCl and NaCl, and 1 g / L as Co 2+ using cobalt chloride I took a bath. The pH was adjusted to pH 2 with NaOH.

（比較例６）
ディップソール（株）製ＳＺ−２４０浴を使用し、鋼板にＳｎ−Ｚｎめっき（Ｚｎ含量３０ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
塩化クロムを使用しＣｒ3+として２ｇ／Ｌ、シュウ酸は２水塩を使用しシュウ酸として５ｇ／Ｌ、ＨＣｌ及びＮａＣｌを使用しＣｌ-としては９ｇ／Ｌ、塩化コバルトを使用しＣｏ2+としては２ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ３に調整した。 (Comparative Example 6)
A dip sole Co., Ltd. SZ-240 bath was used, and a steel plate with Sn—Zn plating (Zn content 30 wt%) applied to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution (stirring) Yes). The processing temperature is 30 ° C. and the processing time is 60 seconds.
2 g / L as Cr 3+ using chromium chloride, oxalic acid using 5 g / L, HCl and NaCl as oxalic acid using dihydrate Cl - The 9 g / L, using the cobalt chloride Co 2 As for + , a treatment solution of 2 g / L was constructed. The pH was adjusted to pH 3 with NaOH.

（比較例７）
ディップソール（株）製ＦＺ−２７０浴を使用し、鋼板にＺｎ−Ｆｅめっき（Ｆｅ含量０．４ｗｔ％）を厚さ８μｍに施したものを、次に示す３価クロム化成処理液に浸漬した（攪拌あり）。処理温度は３０℃であり、処理時間は６０秒である。
硝酸クロムを使用しＣｒ3+として３ｇ／Ｌ、酒石酸１０ｇ／Ｌ、マロン酸４ｇ／Ｌ、ＨＮＯ3及びＮａＮＯ3を使用しＮＯ3 -としては１５ｇ／Ｌ、硝酸コバルトを使用しＣｏ2+としては１ｇ／Ｌの処理液を建浴した。ｐＨはＮａＯＨでｐＨ２に調整した。 (Comparative Example 7)
A dip sole FZ-270 bath was used, and a steel sheet coated with Zn-Fe plating (Fe content 0.4 wt%) to a thickness of 8 μm was immersed in the following trivalent chromium chemical conversion treatment solution. (With stirring). The processing temperature is 30 ° C. and the processing time is 60 seconds.
Chromium nitrate is used as Cr 3+ , 3 g / L, tartaric acid 10 g / L, malonic acid 4 g / L, HNO 3 and NaNO 3 are used as NO 3 − , 15 g / L, cobalt nitrate is used as Co 2+ Prepared a 1 g / L treatment solution. The pH was adjusted to pH 2 with NaOH.

（耐食性塩水噴霧試験）
実施例１〜７及び比較例１〜７について、耐食性を塩水噴霧試験（ＪＩＳ−Ｚ−２３７１）により評価した。結果を表１に示す。

Figure 0005584922
(Corrosion resistant salt spray test)
About Examples 1-7 and Comparative Examples 1-7, corrosion resistance was evaluated by the salt spray test (JIS-Z-2371). The results are shown in Table 1.
Figure 0005584922

Claims (5)

ニトロ基を有する芳香族化合物を０．２〜１０ｇ／Ｌ含有することを特徴とする亜鉛又は亜鉛合金めっき上に３価クロム化成処理皮膜を形成させるための３価クロム化成処理液であって、ニトロ基を有する芳香族化合物がニトロベンゼン類、ニトロベンゼンスルホン酸類又はそのアルカリ金属若しくはアルカリ土類金属塩、ニトロベンゼンカルボン酸類又はそのアルカリ金属若しくはアルカリ土類金属塩、ニトロヒドロキシベンゼン類、又はニトロフェニルアルコール類である、前記３価クロム化成処理液。 A trivalent chromium chemical conversion treatment solution for forming a trivalent chromium chemical conversion treatment film on zinc or zinc alloy plating, characterized by containing 0.2 to 10 g / L of an aromatic compound having a nitro group , Aromatic compounds having a nitro group are nitrobenzenes, nitrobenzenesulfonic acids or alkali metal or alkaline earth metal salts thereof, nitrobenzenecarboxylic acids or alkali metal or alkaline earth metal salts thereof, nitrohydroxybenzenes, or nitrophenyl alcohols. The trivalent chromium chemical conversion treatment liquid . キレート剤を含有する請求項１記載の３価クロム化成処理液。   The trivalent chromium chemical conversion treatment liquid according to claim 1 containing a chelating agent. ３価クロムイオンを０．５〜２０ｇ／Ｌ、無機酸イオンを１〜５０ｇ／Ｌ、キレート形成能のある有機カルボン酸又はその塩を１〜４０ｇ／Ｌ、Ｃｏ、Ｖ、Ｔｉ、Ｗ、Ｚｒ、Ｍｎ、Ｍｏ、Ｔａ、Ｃｅ、Ｓｒ、Ｆｅ及びＡｌからなる群より選ばれる１種以上の金属イオンを０．１〜５ｇ／Ｌ含有する請求項１又は２記載の３価クロム化成処理液。 0.5 to 20 g / L of trivalent chromium ion, 1 to 50 g / L of inorganic acid ion, 1 to 40 g / L of organic carboxylic acid or salt thereof capable of chelate formation, Co, V, Ti, W, Zr The trivalent chromium chemical conversion treatment solution according to claim 1 or 2, containing 0.1 to 5 g / L of one or more metal ions selected from the group consisting of Mn, Mo, Ta, Ce, Sr, Fe and Al. 亜鉛又は亜鉛合金めっきを請求項１〜３のいずれか１項記載の３価クロム化成処理液に接触させることを特徴とする亜鉛又は亜鉛合金めっき上に３価クロム化成処理皮膜を形成させる方法。 A method of forming a trivalent chromium chemical conversion treatment film on zinc or zinc alloy plating, wherein the zinc or zinc alloy plating is brought into contact with the trivalent chromium chemical conversion treatment solution according to any one of claims 1 to 3 . 請求項１〜３のいずれか１項記載の３価クロム化成処理液を用いて得られた亜鉛又は亜鉛合金めっき上に形成された３価クロム化成処理皮膜。 The trivalent chromium chemical conversion treatment film formed on the zinc or zinc alloy plating obtained using the trivalent chromium chemical conversion treatment liquid according to any one of claims 1 to 3 .
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