JP2009270137A - Aqueous conversion treatment solution for forming chromium-free chemical conversion coating on plated film of zinc or zinc alloy, and chromium-free chemical conversion coating obtained from the same - Google Patents
Aqueous conversion treatment solution for forming chromium-free chemical conversion coating on plated film of zinc or zinc alloy, and chromium-free chemical conversion coating obtained from the same Download PDFInfo
- Publication number
- JP2009270137A JP2009270137A JP2008119778A JP2008119778A JP2009270137A JP 2009270137 A JP2009270137 A JP 2009270137A JP 2008119778 A JP2008119778 A JP 2008119778A JP 2008119778 A JP2008119778 A JP 2008119778A JP 2009270137 A JP2009270137 A JP 2009270137A
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- Prior art keywords
- chemical conversion
- zinc
- chromium
- zinc alloy
- aqueous solution
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- 239000000126 substance Substances 0.000 title claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 59
- 239000011701 zinc Substances 0.000 title claims abstract description 28
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000007739 conversion coating Methods 0.000 title abstract 3
- 150000003839 salts Chemical class 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- 238000007747 plating Methods 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 238000004381 surface treatment Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 16
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- 239000011651 chromium Substances 0.000 abstract description 14
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- 238000000576 coating method Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
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- 229910019142 PO4 Inorganic materials 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 4
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- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- NRKQBMOGOKEWPX-UHFFFAOYSA-N vanadyl nitrate Inorganic materials [O-][N+](=O)O[V](=O)(O[N+]([O-])=O)O[N+]([O-])=O NRKQBMOGOKEWPX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
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
- C23C22/46—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
- C23C22/47—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 containing also phosphates
Landscapes
- 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)
Abstract
【課題】本発明は、亜鉛又は亜鉛合金めっき上に、クロムを含有せず、従来の６価クロメートや３価クロム化成処理皮膜と同等以上の耐食性を有する皮膜を提供することを目的とする。
【解決手段】本発明は、（Ａ）Ｔｉ金属塩、（Ｂ）酸化性物質、（Ｃ）リンの酸素酸塩及び（Ｄ）錯化合物を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クロムフリー化成皮膜を形成するための化成処理水溶液を提供する。また、本発明は、基体上の亜鉛又は亜鉛合金めっき上に前記化成処理水溶液を接触させて形成されるクロムフリー化成皮膜を提供する。さらに、本発明は、前記クロムフリー化成皮膜上に、さらにオーバーコート処理を施すことを特徴とする亜鉛又は亜鉛合金めっき表面処理方法を提供する。
【選択図】なしAn object of the present invention is to provide a coating which does not contain chromium on zinc or zinc alloy plating and has a corrosion resistance equal to or higher than that of a conventional hexavalent chromate or trivalent chromium chemical conversion coating.
The present invention relates to a zinc or zinc alloy plating comprising (A) a Ti metal salt, (B) an oxidizing substance, (C) a phosphorus oxyacid salt and (D) a complex compound. A chemical conversion treatment aqueous solution for forming a chromium-free chemical conversion film is provided. Moreover, this invention provides the chromium free chemical conversion film formed by making the said chemical conversion treatment aqueous solution contact on the zinc or zinc alloy plating on a base | substrate. Furthermore, the present invention provides a surface treatment method for zinc or zinc alloy plating, characterized in that an overcoat treatment is further performed on the chromium-free chemical conversion film.
[Selection figure] None
Description
本発明は、亜鉛又は亜鉛合金めっき上にクロムフリー化成皮膜を形成するための化成処理水溶液及びそれより得られたクロムフリー化成皮膜に関するものである。 The present invention relates to a chemical conversion treatment aqueous solution for forming a chromium-free chemical conversion film on zinc or zinc alloy plating and a chromium-free chemical conversion film obtained therefrom.
金属表面の防食方法として亜鉛及び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た。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価クロムの使用を規制する動きが活発になり、６価クロムの代替技術として３価クロムを使用した３価クロム化成処理防錆皮膜が使用されるようになってきた。しかし３価クロム化成処理はクロムを使用しているため６価クロム溶出等の懸念があり、次の防錆皮膜として完全クロムフリーの皮膜が求められている。特許第３５２３３８３号公報では、酸化性物質とＳｉ化合物、Ｔｉ塩、有機酸を混合して処理する方法が開示されている。この方法では、耐食性、液の安定性にやや劣る欠点がある。
さらに、特開２０００−１７４５１号公報には、Ｔｉ化合物とリンの酸素酸塩と酸化性物質からなる処理液で処理する方法が開示されているが、３価クロムも併用するため完全クロムフリーではないという問題がある。
特許第３３０２６７７号公報には、Ｍｎ化合物とＴｉ化合物、リン酸又はリン酸塩、フッ化物及び有機酸を含みｐＨ１〜６に調整された化成処理液が開示されている。水洗なしで乾燥する必要があるので液残り等に問題がある。
また、特表２００５−５２６９０２号公報には、Ｔｉ化合物と酸化剤とフッ化物と有機酸からなる処理液で処理する方法が提案されている。しかし、この方法では耐食性が充分でない。
Although there is a method of plating zinc and zinc alloy as a method for preventing corrosion of metal surfaces, the corrosion resistance is not sufficient with plating alone, and chromic acid treatment including hexavalent after plating, so-called chromate treatment, has been widely adopted in the industry. . However, in recent years, it has been pointed out that hexavalent chromium has an adverse effect on the human body and the environment, and there is an active movement to regulate the use of hexavalent chromium. Trivalent chromium using trivalent chromium as an alternative technology to hexavalent chromium Chromium chemical conversion rust preventive coatings have come to be used. However, since the trivalent chromium chemical conversion treatment uses chromium, there is a concern about elution of hexavalent chromium, and a completely chromium-free film is required as the next rust preventive film. Japanese Patent No. 3523383 discloses a method in which an oxidizing substance, a Si compound, a Ti salt, and an organic acid are mixed and processed. This method has the disadvantage that it is slightly inferior in corrosion resistance and liquid stability.
Furthermore, Japanese Patent Application Laid-Open No. 2000-17451 discloses a method of treating with a treatment liquid comprising a Ti compound, an oxyacid salt of phosphorus and an oxidizing substance. There is no problem.
Japanese Patent No. 3302677 discloses a chemical conversion treatment solution containing Mn compound and Ti compound, phosphoric acid or phosphate, fluoride and organic acid and adjusted to pH 1-6. Since it is necessary to dry without washing with water, there is a problem with the remaining liquid.
Japanese Patent Application Publication No. 2005-526902 proposes a method of treating with a treatment liquid comprising a Ti compound, an oxidizing agent, a fluoride and an organic acid. However, this method does not have sufficient corrosion resistance.
本発明は、亜鉛又は亜鉛合金めっき上に、クロムを含有せず、従来の６価クロメートや３価クロム化成処理皮膜と同等以上の耐食性を有する皮膜を提供することを目的とする。 An object of this invention is to provide the film | membrane which does not contain chromium on zinc or zinc alloy plating, and has corrosion resistance equivalent to or more than the conventional hexavalent chromate or trivalent chromium chemical conversion treatment film.
本発明は、基体上に亜鉛及び亜鉛合金めっきを析出させた後、特定の組成の処理液を用いて化成皮膜処理を行うと、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。すなわち、本発明は、（Ａ）Ｔｉ金属塩、（Ｂ）酸化性物質、（Ｃ）リンの酸素酸塩及び（Ｄ）錯化合物を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クロムフリー化成皮膜を形成するための化成処理水溶液を提供する。
また、本発明は、基体上の亜鉛又は亜鉛合金めっき上に前記化成処理水溶液を接触させて形成されるクロムフリー化成皮膜を提供する。
さらに、本発明は、前記クロムフリー化成皮膜上に、さらにオーバーコート処理を施すことを特徴とする亜鉛又は亜鉛合金めっき表面処理方法を提供する。
The present invention was made based on the knowledge that the above-mentioned problems can be efficiently solved by depositing zinc and zinc alloy plating on a substrate and then performing a chemical conversion film treatment using a treatment liquid having a specific composition. It is. That is, the present invention includes (A) a Ti metal salt, (B) an oxidizing substance, (C) a phosphorus oxyacid salt, and (D) a complex compound. A chemical conversion treatment aqueous solution for forming a free chemical conversion film is provided.
Moreover, this invention provides the chromium free chemical conversion film formed by making the said chemical conversion treatment aqueous solution contact on the zinc or zinc alloy plating on a base | substrate.
Furthermore, the present invention provides a surface treatment method for zinc or zinc alloy plating, characterized in that an overcoat treatment is further performed on the chromium-free chemical conversion film.
本発明によれば、亜鉛及び亜鉛合金めっき上に直接クロムフリー化成皮膜を生成することができる。この方法により得られためっき物は、亜鉛及び亜鉛合金めっき自体の耐食性に加え、更に本化成皮膜のもつ優れた耐食性を合わせもつ。さらに、クロムを使用していないため、環境にもやさしい。めっき上に本化成処理することにより得られる皮膜は、完全クロムフリーで耐食性に優れているために、今後いろいろな分野で幅広く利用されることが期待できる。
耐食性、安定性が向上する機構については明らかでないが、酸化性物質と錯化合物によってＴｉ金属塩が安定な水溶性金属錯体となり、化成皮膜を生成する際に適度な速度で沈着するために均一な皮膜が得られるものと考えられる。さらにリン酸化合物を添加することにより、Ｚｎとの密着性が高まり乾燥によってもクラックがない堅固な皮膜が得られるものと考えられる。
According to the present invention, a chromium-free chemical conversion film can be directly formed on zinc and zinc alloy plating. The plated product obtained by this method has not only the corrosion resistance of zinc and zinc alloy plating itself, but also the excellent corrosion resistance of the chemical conversion film. In addition, because it does not use chromium, it is environmentally friendly. Since the film obtained by this chemical conversion treatment on the plating is completely chromium free and excellent in corrosion resistance, it can be expected to be widely used in various fields in the future.
Although the mechanism for improving corrosion resistance and stability is not clear, the Ti metal salt becomes a stable water-soluble metal complex due to the oxidizing substance and the complex compound, and is uniform because it deposits at an appropriate rate when forming a chemical conversion film. It is thought that a film is obtained. Furthermore, it is considered that by adding a phosphoric acid compound, the adhesiveness with Zn is enhanced, and a firm film free from cracks upon drying can be obtained.
本発明の亜鉛又は亜鉛合金めっき上にクロムフリー化成皮膜を形成するための化成処理水溶液は、（Ａ）Ｔｉ金属塩、（Ｂ）酸化性物質、（Ｃ）リンの酸素酸塩及び（Ｄ）錯化合物を含有する。
本発明で用いる基体としては、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ものがあげられる。
本発明では、先ず基体上に、常法により亜鉛又は亜鉛合金めっきを析出させる。基体上に亜鉛めっきを析出させるには、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でも良い。基体上に析出する亜鉛めっきの厚みは任意とすることができるが、１μｍ以上、好ましくは５〜２５μｍ厚とするのがよい。また、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。基体上に析出する亜鉛合金めっきの厚みは任意とすることができるが、１μｍ以上、好ましくは５〜２５μｍ厚とするのがよい。
本発明では、このようにして基体上に亜鉛又は亜鉛合金めっきを析出させた後、例えば水洗して、本発明の化成処理水溶液を用いて浸漬処理を行なう。
The chemical conversion treatment aqueous solution for forming the chromium-free chemical conversion film on the zinc or zinc alloy plating of the present invention includes (A) Ti metal salt, (B) oxidizing substance, (C) phosphorus oxyacid salt, and (D) Contains complex compounds.
As the substrate used in the present invention, various metals such as iron, nickel, copper, and alloys thereof, or metal or alloys such as aluminum subjected to zinc substitution treatment, rectangular parallelepipeds, cylinders, cylinders, spherical objects, etc. There are various shapes.
In the present invention, zinc or zinc alloy plating is first deposited on the substrate by a conventional method. In order to deposit galvanizing 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 galvanizing deposited on the substrate can be arbitrary, but it is 1 μm or 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. The thickness of the zinc alloy plating deposited on the substrate can be arbitrary, but it is 1 μm or more, preferably 5 to 25 μm.
In the present invention, after depositing zinc or zinc alloy plating on the substrate in this manner, the substrate is washed with water, for example, and immersion treatment is performed using the chemical conversion treatment aqueous solution of the present invention.
本発明の化成処理水溶液で使用する（Ａ）Ｔｉ金属塩としては、塩化チタン、硫酸チタンなどが挙げられる。これらのＴｉ金属塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。
本発明の化成処理水溶液には、さらに（Ｅ）Ｚｒ、Ｓｒ、Ｖ、Ｗ、Ｍｏ及びこれらの組み合わせからなる群より選ばれる金属の金属塩を含有させてもよい。Ｚｒ金属塩としては、硫酸ジルコニル、オキシ塩化ジルコニウムなどのジルコニル塩；Ｚｒ（ＳＯ4）2、Ｚｒ（ＮＯ3）2などのジルコニウム塩などが挙げられる。これらのＺｒ金属塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。Ｃｅ金属塩としては、塩化セリウム、硫酸セリウム、過塩素酸セリウム、リン酸セリウム、硝酸セリウムなどが挙げられる。これらのＣｅ金属塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。Ｓｒ金属塩としては、塩化ストロンチウム、過酸化ストロンチウム、硝酸ストロンチウムなどが挙げられる。これらのＳｒ金属塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。Ｖ金属塩としては、バナジン酸アンモン、バナジン酸ナトリウムなどのバナジン酸塩；オキシ硝酸バナジウムなどのオキシバナジン酸塩などが挙げられる。これらのＶ金属塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。Ｗ金属塩としては、タングステン酸アンモン、タングステン酸ナトリウムなどのタングステン酸塩などが挙げられる。これらのＷ金属塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。Ｍｏ金属塩としては、モリブデン酸アンモン、モリブデン酸ナトリウムなどのモリブデン酸塩；リンモリブデン酸ナトリウムなどのリンモリブデン酸塩などが挙げられる。これらのＭｏ金属塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。本発明の化成処理水溶液中のＴｉ金属塩の濃度又は（Ｅ）金属塩を含む場合には金属塩の合計濃度は、金属イオン濃度で、好ましくは０．０５〜２５ｇ／Ｌであり、より好ましくは０．１〜１０ｇ／Ｌであり、最も好ましくは０．３〜５ｇ／Ｌである。
Examples of the (A) Ti metal salt used in the chemical conversion treatment aqueous solution of the present invention include titanium chloride and titanium sulfate. These Ti metal salts may be used alone or as a mixture of two or more.
The chemical conversion treatment aqueous solution of the present invention may further contain (E) a metal salt of a metal selected from the group consisting of Zr, Sr, V, W, Mo, and combinations thereof. Zr metal salts include zirconyl salts such as zirconyl sulfate and zirconium oxychloride; zirconium salts such as Zr (SO 4 ) 2 and Zr (NO 3 ) 2 . These Zr metal salts may be used alone or as a mixture of two or more. Examples of the Ce metal salt include cerium chloride, cerium sulfate, cerium perchlorate, cerium phosphate, and cerium nitrate. These Ce metal salts may be used alone or as a mixture of two or more. Examples of the Sr metal salt include strontium chloride, strontium peroxide, and strontium nitrate. These Sr metal salts may be used alone or as a mixture of two or more. Examples of the V metal salt include vanadates such as ammonium vanadate and sodium vanadate; and oxyvanadates such as vanadium oxynitrate. These V metal salts may be used singly or as a mixture of two or more. Examples of the W metal salt include tungstates such as ammonium tungstate and sodium tungstate. These W metal salts may be used singly or as a mixture of two or more. Examples of the Mo metal salt include molybdates such as ammonium molybdate and sodium molybdate; and phosphomolybdates such as sodium phosphomolybdate. These Mo metal salts may be used alone or as a mixture of two or more. When the concentration of Ti metal salt in the chemical conversion aqueous solution of the present invention or (E) the metal salt is included, the total concentration of the metal salt is a metal ion concentration, preferably 0.05 to 25 g / L, more preferably. Is 0.1 to 10 g / L, most preferably 0.3 to 5 g / L.
本発明の化成処理水溶液で使用する（Ｂ）酸化性物質としては、過酸化物や硝酸などが挙げられる。過酸化物としては、過酸化水素、過酸化ナトリウム、過酸化バリウムなどが挙げられる。また、過ギ酸、過酢酸、過安息香酸、過硫酸アンモニウム、過ホウ酸ナトリウムなどのペルオキシ酸及びその塩なども使用できる。中でも過酸化水素が好ましく、３５％過酸化水素を使用するのが実用上好適である。これらの酸化性物質は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。本発明の化成処理水溶液中の酸化性物質の濃度は、好ましくは０．０５〜１００ｇ／Ｌであり、より好ましくは０．５〜５０ｇ／Ｌであり、最も好ましくは１〜３０ｇ／Ｌである。
本発明の化成処理水溶液で使用する（Ｃ）リンの酸素酸塩としては、正リン酸塩、縮合リン酸塩、 次亜リン酸塩、 亜リン酸塩などが挙げられる。中でも正リン酸塩が好ましい。また、これらのリンの酸素酸塩を形成する金属イオンなどとしては、Ｋ+、Ｎａ+、Ｌｉ+、Ｃａ2+、Ｍｇ2+、Ａｌ3+、ＮＨ4+などが挙げられる。中でも、Ｎａ+及びＫ+が好ましい。これらのリンの酸素酸塩は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。本発明の化成処理水溶液中のリンの酸素酸塩の濃度は、好ましくは０．１〜５０ｇ／Ｌであり、より好ましくは０．５〜３０ｇ／Ｌであり、最も好ましくは１〜１５ｇ／Ｌである。
本発明の化成処理水溶液で使用する（Ｄ）錯化合物としては、エチレンジアミン、テトラメチレンジアミン、ジエチレントリアミンなどの脂肪族アミン、トリエタノールアミンなどのアミノアルコール類、ＥＤＴＡ、ＮＴＡ、グリシン、アスパラギン酸などのアミノカルボン酸；グリコール酸、乳酸、酒石酸、リンゴ酸、クエン酸、酒石酸グルコン酸などのヒドロキシカルボン酸；ギ酸、酢酸、プロピオン酸などのモノカルボン酸；シュウ酸、マロン酸、コハク酸、マレイン酸、ジグリコール酸などの多価カルボン酸などの酸並びにこれらのアルカリ金属塩やアンモニウム塩などが挙げられる。これらの錯化合物は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。錯化合物の種類及び濃度は、使用する金属イオンの種類及び濃度を考慮して選択するのがよい。本発明の化成処理水溶液中の錯化合物の濃度は、好ましくは０．０５〜５０ｇ／Ｌであり、より好ましくは０．５〜３０ｇ／Ｌであり、最も好ましくは０．５〜１０ｇ／Ｌである。特に、使用する錯化合物の総使用濃度は、使用する金属イオンの濃度との比率（モル）で決定するのが好ましい。前記比率は、好ましくは０．１〜２０であり、より好ましくは０．３〜１５であり、最も好ましくは０．５〜１０である。また、安定性の点からは、（Ｄ）錯化合物としてシュウ酸又はその塩を用いるのが最も好ましい。
Examples of the oxidizing substance (B) used in the chemical conversion aqueous solution of the present invention include peroxide and nitric acid. Examples of the peroxide include hydrogen peroxide, sodium peroxide, and barium peroxide. In addition, peroxy acids such as performic acid, peracetic acid, perbenzoic acid, ammonium persulfate, and sodium perborate, and salts thereof can also be used. Among these, hydrogen peroxide is preferable, and it is practically preferable to use 35% hydrogen peroxide. These oxidizing substances may be used alone or as a mixture of two or more. The concentration of the oxidizing substance in the chemical conversion aqueous solution of the present invention is preferably 0.05 to 100 g / L, more preferably 0.5 to 50 g / L, and most preferably 1 to 30 g / L. .
Examples of (C) phosphorus oxyacid salt used in the chemical conversion treatment aqueous solution of the present invention include normal phosphate, condensed phosphate, hypophosphite, and phosphite. Of these, orthophosphate is preferable. Examples of the metal ions that form these phosphorus oxyacid salts include K + , Na + , Li + , Ca 2+ , Mg 2+ , Al 3+ , and NH 4+ . Of these, Na + and K + are preferable. These phosphorus oxyacid salts may be used alone or as a mixture of two or more. The concentration of phosphorus oxyacid salt in the chemical conversion aqueous solution of the present invention is preferably 0.1 to 50 g / L, more preferably 0.5 to 30 g / L, and most preferably 1 to 15 g / L. It is.
Examples of the (D) complex compound used in the chemical conversion aqueous solution of the present invention include aliphatic amines such as ethylenediamine, tetramethylenediamine and diethylenetriamine, amino alcohols such as triethanolamine, and aminoalcohols such as EDTA, NTA, glycine and aspartic acid. Carboxylic acid; Hydroxy carboxylic acid such as glycolic acid, lactic acid, tartaric acid, malic acid, citric acid, tartaric acid gluconic acid; monocarboxylic acid such as formic acid, acetic acid, propionic acid; oxalic acid, malonic acid, succinic acid, maleic acid, di Examples thereof include acids such as polyvalent carboxylic acids such as glycolic acid, and alkali metal salts and ammonium salts thereof. These complex compounds may be used alone or as a mixture of two or more. The type and concentration of the complex compound are preferably selected in consideration of the type and concentration of the metal ion to be used. The concentration of the complex compound in the chemical conversion aqueous solution of the present invention is preferably 0.05 to 50 g / L, more preferably 0.5 to 30 g / L, and most preferably 0.5 to 10 g / L. is there. In particular, the total use concentration of the complex compound to be used is preferably determined by the ratio (mol) to the concentration of the metal ion to be used. The ratio is preferably from 0.1 to 20, more preferably from 0.3 to 15, and most preferably from 0.5 to 10. From the viewpoint of stability, it is most preferable to use oxalic acid or a salt thereof as the (D) complex compound.
本発明の化成処理水溶液には、さらに（Ｆ）シリカ及び／又はシリケートを含有させてもよい。シリカ（二酸化珪素）としては、コロイダルシリカなどが挙げられる。また、シリケート（珪酸塩）としては、珪酸リチウム、珪酸ナトリウム、珪酸カリウムなどのアルカリ金属塩やアンモニウム塩などが挙げられる。これらの化合物は、単独で用いてもよいし、又は２種以上の混合物として用いてもよい。本発明の化成処理水溶液中のシリカ及び／又はシリケートの濃度は、好ましくは１〜１００ｇ／Ｌであり、より好ましくは１０〜８０ｇ／Ｌである。
本発明の化成処理水溶液のｐＨは、好ましくは０．５〜６であり、より好ましくは１〜３である。この範囲にｐＨを調整するために、硫酸、塩酸、硝酸などの無機酸イオンを用いてもよく、又は水酸化アルカリ、アンモニア水などのアルカリ剤を用いてもよい。
本発明の化成処理水溶液における上記成分以外の残分は水である。
最も好ましい本発明の化成処理水溶液は、チタン化合物、過酸化水素、正リン酸塩、シュウ酸を含有する。
The chemical conversion treatment aqueous solution of the present invention may further contain (F) silica and / or silicate. Examples of silica (silicon dioxide) include colloidal silica. Examples of the silicate (silicate) include alkali metal salts and ammonium salts such as lithium silicate, sodium silicate, and potassium silicate. These compounds may be used alone or as a mixture of two or more. The concentration of silica and / or silicate in the chemical conversion aqueous solution of the present invention is preferably 1 to 100 g / L, more preferably 10 to 80 g / L.
The pH of the chemical conversion treatment aqueous solution of the present invention is preferably 0.5 to 6, and more preferably 1 to 3. In order to adjust the pH within this range, inorganic acid ions such as sulfuric acid, hydrochloric acid, and nitric acid may be used, or alkaline agents such as alkali hydroxide and aqueous ammonia may be used.
The remainder other than the above components in the chemical conversion aqueous solution of the present invention is water.
The most preferable chemical conversion treatment aqueous solution of the present invention contains a titanium compound, hydrogen peroxide, orthophosphate, and oxalic acid.
本発明において、亜鉛又は亜鉛合金めっき上に化成皮膜を形成する処理方法としては、上記化成処理水溶液に亜鉛又は亜鉛合金めっきした物を接触させればよい。接触方法としては、浸漬するのが一般的である。例えば、１０〜４０℃の液温で５〜３００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、亜鉛めっきではクロメート皮膜の光沢を増すために、通常、クロメート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行ってもよいし、行わなくてもよい。
上記以外の条件や処理操作は、従来のクロメートや３価クロム化成処理方法に準じて行うことができる。
このようにして、本発明のクロムフリー化成処理水溶液から、耐食性に優れたクロムフリー化成皮膜が得られる。
In the present invention, as a treatment method for forming a chemical conversion film on zinc or zinc alloy plating, a product plated with zinc or zinc alloy may be brought into contact with the chemical conversion treatment aqueous solution. As a contact method, it is common to immerse. For example, the immersion is preferably performed at a liquid temperature of 10 to 40 ° C. for 5 to 300 seconds, and more preferably 15 to 120 seconds.
In galvanization, in order to increase the gloss of the chromate film, the object to be treated is usually immersed in a dilute nitric acid solution before the chromate treatment. In the present invention, such pretreatment may be performed. It does not have to be done.
Conditions and processing operations other than those described above can be performed in accordance with conventional chromate or trivalent chromium chemical conversion treatment methods.
In this way, a chromium-free chemical conversion film having excellent corrosion resistance can be obtained from the chromium-free chemical conversion treatment aqueous solution of the present invention.
また、前記化成皮膜上にオーバーコート処理を施すことにより、さらに耐食性を向上させることが出来、より耐食性を持たせるには、大変有効な手段である。例えば、まず、亜鉛又は亜鉛合金めっき上に上記化成処理を行い、水洗後オーバーコート処理液で浸漬処理して乾燥する。また、化成処理して乾燥後、新たにオーバーコート処理液で浸漬処理した後、乾燥することも出来る。ここで、オーバーコートとは、珪酸塩、リン酸塩などの無機皮膜は勿論の事、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、メタクリル樹脂、ポリカーボネート、ポリアミド、ポリアセタール、フッ素樹脂、尿素樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリウレタン、アルキド樹脂、エポキシ樹脂、メラミン樹脂などの有機皮膜も有効である。
このようなオーバーコートを施すためのオーバーコート処理液としては、例えばディップソール（株）製のディップコートＷ、ディップコートＣＣなどを用いることができる。オーバーコート皮膜の厚みは任意とすることができるが、０．１〜３０μｍとするのがよい。
さらに、着色するために本処理液に染料を添加することや、一度本処理液で処理した後、染料を含有した液で処理することもできる。
次に実施例により本発明を説明するが、本発明はこれらによって限定されるものではない。
Further, by applying an overcoat treatment to the chemical conversion film, the corrosion resistance can be further improved, and this is a very effective means for imparting more corrosion resistance. For example, first, the above-mentioned chemical conversion treatment is performed on zinc or zinc alloy plating, followed by rinsing with an overcoat treatment solution and drying. Moreover, after chemical conversion treatment and drying, it is also possible to dry after further immersion treatment with an overcoat treatment solution. Here, the overcoat is not only an inorganic film such as silicate and phosphate, but also polyethylene, polyvinyl chloride, polystyrene, polypropylene, methacrylic resin, polycarbonate, polyamide, polyacetal, fluorine resin, urea resin, phenol resin. Organic films such as unsaturated polyester resins, polyurethanes, alkyd resins, epoxy resins and melamine resins are also effective.
As an overcoat treatment liquid for applying such an overcoat, for example, Dipcoat W, Dipcoat CC manufactured by Dipsol Co., Ltd. can be used. The thickness of the overcoat film can be arbitrarily set, but is preferably 0.1 to 30 μm.
Further, a dye may be added to the treatment liquid for coloring, or after treatment with the treatment liquid once, treatment with a liquid containing the dye may be performed.
EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited thereto.
（実施例１〜１２）
ＳＰＣＣ磨き鋼板（板厚：０．３ｍｍ：１００ｍｍ×６５ｍｍ）に８〜１０μｍの亜鉛又は亜鉛合金めっき（Ｚｎ／Ｓｎ：７０／３０Ｗｔ％、Ｚｎ／Ｆｅ：９９．６／０．４Ｗｔ％、Ｚｎ／Ｎｉ：８５／１５Ｗｔ％）をおこなった試験片を、表１及び２に記載の本発明の化成処理水溶液に２５℃で６０秒浸漬した後、試験片を引き上げ、水洗、乾燥した。上記処理した各試験片について、その耐食性を評価するためにＪＩＳＺ２３７１に準拠する塩水噴霧試験をおこなった。評価方法は、試験片に発生した白錆の量（試験片の面積に対する、白錆の発生した部分の合計の面積の割合）が５％を越えるまでの時間で行った。結果をまとめて表３に示す。
(Examples 1-12)
SPCC polished steel plate (thickness: 0.3 mm: 100 mm × 65 mm) with 8-10 μm zinc or zinc alloy plating (Zn / Sn: 70/30 Wt%, Zn / Fe: 99.6 / 0.4 Wt%, Zn / After the test piece subjected to Ni: 85/15 Wt%) was immersed in the chemical conversion treatment aqueous solution of the present invention described in Tables 1 and 2 at 25 ° C. for 60 seconds, the test piece was pulled up, washed with water and dried. Each of the treated specimens was subjected to a salt spray test in accordance with JISZ2371 in order to evaluate its corrosion resistance. The evaluation method was performed until the amount of white rust generated on the test piece (the ratio of the total area of the white rust generated portion to the area of the test piece) exceeded 5%. The results are summarized in Table 3.
（比較例１〜６）
実施例１〜１２と同様に調製した試験片を表４に記載の比較例１〜６の処理液に２５℃で６０秒浸漬した後、試験片を引き上げ、水洗、乾燥した。上記処理した各試験片の耐食性を実施例１と同様にして評価した。結果をまとめて表５に示す。
(Comparative Examples 1-6)
After the test pieces prepared in the same manner as in Examples 1 to 12 were immersed in the treatment liquids of Comparative Examples 1 to 6 shown in Table 4 at 25 ° C. for 60 seconds, the test pieces were pulled up, washed with water, and dried. The corrosion resistance of each of the treated specimens was evaluated in the same manner as in Example 1. The results are summarized in Table 5.
（実施例１３）
ＳＰＣＣ磨き鋼板（板厚：０．３ｍｍ：１００ｍｍ×６５ｍｍ）に８〜１０ミクロンの亜鉛めっきをおこなった試験片を表１に記載の実施例１の化成処理水溶液を用いて２５℃で６０秒浸漬した後、試験片を引き上げ、水洗し、さらに有機樹脂系のオーバーコートとしてディップソール株式会社製「ディップコートＷ（有機・無機併用タイプ）」（１〜２μｍ）又は「ディップコートＣＣ（無機タイプ）」（０．３〜１μｍ）を施した。上記処理した各試験片の耐食性を実施例１と同様にして評価した。結果をまとめて表６に示す。
(Example 13)
SPCC polished steel plate (thickness: 0.3 mm: 100 mm × 65 mm) was immersed for 60 seconds at 25 ° C. using the chemical conversion treatment aqueous solution of Example 1 shown in Table 1 by galvanizing a test piece of 8 to 10 microns. After that, the test piece is pulled up, washed with water, and “Dip Coat W (organic / inorganic combination type)” (1-2 μm) or “Dip Coat CC (inorganic type) manufactured by Dipsol Co., Ltd. as an organic resin overcoat. (0.3-1 μm). The corrosion resistance of each of the treated specimens was evaluated in the same manner as in Example 1. The results are summarized in Table 6.
（浴の安定性試験）
下記表７に記載した化成処理水溶液について、錯化合物の違いによる浴の安定性を調査した。試験液を４５℃で放置沈殿を生じるまでの時間で安定性を評価した。結果をまとめて表８に示す。
(Bath stability test)
Regarding the chemical conversion treatment aqueous solution described in Table 7 below, the stability of the bath due to the difference in the complex compound was investigated. The stability was evaluated by the time until the test solution was allowed to stand at 45 ° C. until precipitation occurred. The results are summarized in Table 8.
Claims (6)
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