JP2005520047A - Aqueous surface treating agent and film forming method for metal surface treatment - Google Patents
Aqueous surface treating agent and film forming method for metal surface treatment Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
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Abstract
【課題】金属表面処理のための水性表面処理剤および金属表面への被膜（転化層）の形成方法を提供する。
【解決手段】
金属表面処理のための水性表面処理剤が、タングステン酸イオン供給源およびジルコニウム含有可溶性材料を含み、金属表面への被膜形成方法が、（ａ）タングステン酸イオン供給源と、（ｂ）ジルコニウム含有可溶性材料と、を含む水性表面処理剤による金属表面の処理工程と、当該表面処理後に、乾燥および／またはベーキング処理を実施するための処理工程と、を順次含む。An aqueous surface treating agent for metal surface treatment and a method for forming a coating (converted layer) on the metal surface are provided.
[Solution]
An aqueous surface treatment agent for metal surface treatment includes a tungstate ion source and a zirconium-containing soluble material, and a method of forming a film on the metal surface comprises (a) a tungstate ion source and (b) a zirconium-containing soluble material. A metal surface treatment step with an aqueous surface treatment agent containing the material, and a treatment step for performing a drying and / or baking treatment after the surface treatment.
Description
本発明は、金属表面処理のための水性表面処理剤および金属表面における被膜（転化層）形成方法に関する。
特に、一般にクロムを含んでおらず、当該被膜の表面と、防湿のための有機表面膜との間の密着性を改善するだけでなく、耐食性について改善された被膜が得られる金属表面処理のための水性表面処理剤および金属表面における被膜形成方法に関する。
The present invention relates to an aqueous surface treatment agent for metal surface treatment and a method for forming a coating (converted layer) on the metal surface.
In particular, for metal surface treatment that generally does not contain chromium and not only improves the adhesion between the surface of the coating and the organic surface film for moisture protection, but also provides a coating with improved corrosion resistance. The present invention relates to an aqueous surface treating agent and a film forming method on a metal surface.
金属表面を腐食から保護し、防湿のための有機表面膜との間の密着性が改善された基材を提供する為に、これまで、様々な金属表面への被膜が提案されてきた。すなわち、このような被膜は、様々な化学物質からなる水性表面処理剤で金属表面を処理することによって形成されており、金属表面と水性表面処理剤中の処理成分とが反応することによって被膜形成が行われている。
また、このような被膜形成に通常的に用いられる表面処理剤は、一般にリン酸塩とクロム酸塩を含んでいる。
Various coatings on metal surfaces have been proposed so far to provide a substrate that protects the metal surface from corrosion and has improved adhesion between the organic surface film for moisture protection. That is, such a film is formed by treating a metal surface with an aqueous surface treatment agent composed of various chemical substances, and a film is formed by a reaction between the metal surface and a treatment component in the aqueous surface treatment agent. Has been done.
Moreover, the surface treating agent normally used for such film formation generally contains phosphate and chromate.
もちろん、リン酸塩被膜は、これまで長い間、特に鋼に対して用いられてきた。また、リン酸塩被膜は、最も単純なリン酸塩水性表面処理剤であるアルカリ金属を含むリン酸塩と、鉄、アルミニウム、および亜鉛の少なくとも一つとが反応することにより形成される。このような被膜処理を行うことにより、被膜表面の耐食性が向上し、防湿のための有機表面膜との間の密着性を改善するのに必要となる。 Of course, phosphate coatings have long been used, especially for steel. The phosphate coating is formed by a reaction between a phosphate containing an alkali metal, which is the simplest phosphate aqueous surface treatment agent, and at least one of iron, aluminum, and zinc. By performing such a coating treatment, the corrosion resistance of the coating surface is improved, and it is necessary to improve the adhesion between the organic surface film for moisture prevention.
他方、クロム酸塩被膜は、リン酸塩被膜に比べ、耐食性と密着性に優れている。しかしながら、クロム酸塩被膜は温度が上昇した場合に、高い耐食性と密着性が得られない。また、クロム酸塩を含む水性表面処理剤は一般に、三価クロムおよび六価クロムの少なくとも一つのクロム化合物と、他の附加物とを含んでいる。
そして、これまでは、クロム酸塩被膜には六価クロムが最も適していたが、三価クロムによる方法が技術的に改良され、六価クロムの特性に匹敵してきた。より具体的には、典型的なクロム酸塩を含む表面処理剤は、米国特許公開番号５４０７７４９および米国特許公開番号４３４９３９２に、それぞれ示されている。いずれにしろクロム酸は有毒であり厳しく使用規制がなされている。そのため、クロム化合物を含まない被膜方法であって、クロム酸塩被膜に代替する方法が検討されてきたが、実現されていないというのが実情である。
On the other hand, the chromate coating is superior in corrosion resistance and adhesion compared to the phosphate coating. However, when the temperature of the chromate film rises, high corrosion resistance and adhesion cannot be obtained. Moreover, the aqueous surface treatment agent containing chromate generally contains at least one chromium compound of trivalent chromium and hexavalent chromium and another additive.
Until now, hexavalent chromium has been most suitable for chromate coating, but the method using trivalent chromium has been technically improved and has been comparable to the characteristics of hexavalent chromium. More specifically, typical chromate-containing surface treatment agents are shown in US Patent Publication No. 54077749 and US Patent Publication No. 4349392, respectively. In any case, chromic acid is toxic and its use is strictly regulated. For this reason, a coating method that does not include a chromium compound and a method that replaces the chromate coating has been studied, but the actual situation is that it has not been realized.
そこで、本発明の目的は、金属表面のための表面処理剤および金属表面への被膜（転化層）形成方法を提供することにある。
すなわち、本発明によれば、優れた耐食性と、防湿のための有機表面膜との間で優れた密着性を有するとともに、クロム化合物を含まない被膜が得られる金属表面のための表面処理剤および金属表面への被膜（転化層）形成方法を提供することである。
また、本発明によれば、後処理として行われる熱処理およびベーキング処理の少なくとも一方の処理によって受ける影響を最小限に抑えることができる被膜が得られる金属表面のための表面処理剤および金属表面への被膜（転化層）形成方法を提供することである。
また、本発明によれば、亜鉛、亜鉛合金、アルミニウム、アルミニウム合金に対して用いることができる金属表面のための表面処理剤および被膜の形成方法を提供することである。
Accordingly, an object of the present invention is to provide a surface treating agent for a metal surface and a method for forming a coating (converting layer) on the metal surface.
That is, according to the present invention, a surface treatment agent for a metal surface having excellent corrosion resistance and excellent adhesion between an organic surface film for moisture prevention and a coating containing no chromium compound, and It is to provide a method for forming a coating (conversion layer) on a metal surface.
Further, according to the present invention, the surface treatment agent for the metal surface and the metal surface on which the coating film capable of minimizing the influence of the heat treatment and post-treatment performed as the post-treatment can be minimized. It is to provide a method for forming a coating (converting layer).
Moreover, according to this invention, it is providing the surface treatment agent for the metal surface which can be used with respect to zinc, a zinc alloy, aluminum, and an aluminum alloy, and the formation method of a film.
本発明によれば、金属表面における被膜形成方法であって、
（ａ）タングステン酸イオン供給源、および（ｂ）ジルコニウム含有可溶性材料を含む水性表面処理剤による金属表面処理工程と、
表面処理した金属表面に対して、乾燥処理および／またはベーキング処理（焼付け処理）を実施するための処理工程と、
を順次含むことを特徴とする被膜形成方法が提供され、上述した問題を解決することができる。
According to the present invention, there is provided a film forming method on a metal surface,
A metal surface treatment step with an aqueous surface treating agent comprising (a) a tungstate ion source, and (b) a zirconium-containing soluble material;
A treatment process for carrying out a drying treatment and / or a baking treatment (baking treatment) on the surface-treated metal surface;
Are sequentially provided, and the above-described problems can be solved.
また、本発明の水性表面処理剤は、アルミニウム表面およびアルミニウム合金表面だけでなく、亜鉛表面および亜鉛合金表面の処理にも適している。
また、その表面処理に用いる水性表面処理剤のｐＨを２．０〜７．０の範囲内の値に調整することが好ましい。
また、本発明の被膜形成方法を実施するにあたり、クロム化合物（クロムイオン）を含まない水性表面処理剤を使用することが好ましい。
Moreover, the aqueous surface treating agent of the present invention is suitable for treating not only aluminum surfaces and aluminum alloy surfaces, but also zinc surfaces and zinc alloy surfaces.
Moreover, it is preferable to adjust pH of the aqueous surface treating agent used for the surface treatment to a value within the range of 2.0 to 7.0.
In carrying out the film forming method of the present invention, it is preferable to use an aqueous surface treatment agent that does not contain a chromium compound (chromium ions).
また、本発明の水性表面処理剤および被膜形成方法の実施形態に関して、
（ａ）タングステン酸イオン供給源および、（ｂ）ジルコニウム含有可溶性材料と、を含む水性表面処理剤であって、当該水性表面処理剤による金属表面の処理工程と、当該表面処理後に、表面処理した金属表面に対して、乾燥処理および／またはベーキング処理を実施するための処理工程と、を順次含むことが好ましい。
Moreover, regarding the embodiment of the aqueous surface treating agent and the film forming method of the present invention,
An aqueous surface treatment agent comprising (a) a tungstate ion source and (b) a zirconium-containing soluble material, wherein the metal surface is treated with the aqueous surface treatment agent, and the surface treatment is performed after the surface treatment. It is preferable to sequentially include a treatment step for performing a drying treatment and / or a baking treatment on the metal surface.
ここで、タングステン酸イオン供給源は、全てのタングステン酸塩を用いることができるが、主に、オルトタングステン酸塩類、メタタングステン酸塩類、パラタングステン酸塩類、ポリタングステン酸塩類、ヘテロポリタングステン酸塩類、イソポリタングステン酸塩類、ペルオキシタングステン酸塩類およびこれらの化合物を用いることが好ましい。中でも、メタタングステン酸塩供給源またはパラタングステン酸塩供給源が好ましい。
また、他に好ましいタングステン酸イオン供給源としては、タングステン酸カリウム塩類、タングステン酸ナトリウム塩類、タングステン酸リチウム塩類、タングステン酸カルシウム塩類、タングステン酸セシウム塩類、タングステン酸バリウム塩類、タングステン酸マグネシウム塩類、タングステン酸ストロンチウム塩類、タングステン酸類およびタングステン酸アンモニウム塩類、メタタングステン酸アンモニウム塩、メタタングステン酸カリウム塩、メタタングステン酸ナトリウム塩、タングステン酸塩、タングステン酸カリウム塩、タングステン酸ナトリウム塩およびタングステン酸アンモニウム塩などが挙げられる。
また、可溶性タングステン酸塩、例えば、タングステン酸アンモニウム塩やタングステン酸ナトリウム塩などは、濃縮液や処理液の扱いの点からより好ましいタングステン酸イオン供給源である。
また、水性表面処理剤中のタングステン酸塩濃度（タングステンにて測定）を０．０１〜１０ｇ/リットルの範囲内の値とすることが好ましく、０．１〜１．５ｇ/リットルの範囲内の値とすることがより好ましく、１．０ｇ/リットルとすることが更に好ましい。
Here, all tungstates can be used as the tungstate ion source. However, orthotungstates, metatungstates, paratungstates, polytungstates, heteropolytungstates, It is preferable to use isopolytungstates, peroxytungstates and their compounds. Among these, a metatungstate source or a paratungstate source is preferable.
Other preferable tungstate ion sources include potassium tungstate, sodium tungstate, lithium tungstate, calcium tungstate, cesium tungstate, barium tungstate, magnesium tungstate, tungstic acid. Examples include strontium salts, tungstic acids and ammonium tungstates, ammonium metatungstate, potassium metatungstate, sodium metatungstate, tungstate, potassium tungstate, sodium tungstate and ammonium tungstate It is done.
Soluble tungstates, such as ammonium tungstate and sodium tungstate, are more preferred tungstate ion sources in terms of handling concentrates and treatment solutions.
Further, the tungstate concentration (measured with tungsten) in the aqueous surface treatment agent is preferably set to a value within the range of 0.01 to 10 g / liter, and within the range of 0.1 to 1.5 g / liter. More preferably, the value is 1.0 g / liter.
一方、本発明で用いる水性表面処理剤にはジルコニウムと、好ましくはフッ素化合物と、からなる化合物を含むことが好ましい。
このような化合物の好適物質例としては、ジルコニウムが挙げられるが、これに限らず、フッ化アンモニウムジルコニウム、ヘキサフルオロジルコン酸、ヘキサフルオロジルコン酸カリウム、硫化ジルコニウム、炭化ジルコニウム、硝酸ジルコニウム、リン酸ジルコニウムなども好ましい。中でも、最適なジルコニウム化合物は、ヘキサフルオロジルコン酸である。
また、水性表面処理剤中のジルコニウム化合物の濃度は、０．０１〜２．０ｇ/リットルの範囲内の値とすることが好ましく、０．０５〜０．５ｇ/リットルの範囲内の値とすることがより好ましい。
On the other hand, the aqueous surface treating agent used in the present invention preferably contains a compound comprising zirconium and preferably a fluorine compound.
Suitable examples of such compounds include, but are not limited to, zirconium zirconium fluoride, hexafluorozirconic acid, potassium hexafluorozirconate, zirconium sulfide, zirconium carbide, zirconium nitrate, zirconium phosphate. Etc. are also preferable. Among them, the optimum zirconium compound is hexafluorozirconic acid.
The concentration of the zirconium compound in the aqueous surface treatment agent is preferably a value within the range of 0.01 to 2.0 g / liter, and a value within the range of 0.05 to 0.5 g / liter. It is more preferable.
また、本発明で用いる水性表面処理剤のｐＨを２．０〜７．０の範囲内の値とすることが好ましく、２．８〜７．０の範囲内の値とすることがより好ましい。
この理由は、水性表面処理剤のｐＨが２．０〜７．０の範囲を外れると、耐食性が実質的に低下したり、当該水性表面処理剤としての水性表面処理剤の安定性が所望以下に低下したりする場合があるためである。
Moreover, it is preferable to make pH of the aqueous surface treating agent used by this invention into the value within the range of 2.0-7.0, and it is more preferable to set it as the value within the range of 2.8-7.0.
This is because, when the pH of the aqueous surface treatment agent is out of the range of 2.0 to 7.0, the corrosion resistance is substantially lowered, or the stability of the aqueous surface treatment agent as the aqueous surface treatment agent is less than desired. This is because it may decrease.
また、使用する処理槽には、濃縮物に対する中和剤である水酸化アンモニウムと、その濃縮物からなる水性表面処理剤とを含むことが好ましいことが確認されている。
すなわち、水酸化アンモニウムは、液状濃縮物のｐＨを調整するために添加されるが、仮に、水酸化アンモニウムによって濃縮物のｐＨを所定値に向上させることができないとすると、濃縮物が不安定になる場合がある。逆に言うと、水酸化アンモニウムによって濃縮物のｐＨを所定値に向上させることにより、濃縮物の不安定化を抑制することができる。
Further, it has been confirmed that the treatment tank to be used preferably contains ammonium hydroxide, which is a neutralizing agent for the concentrate, and an aqueous surface treatment agent comprising the concentrate.
That is, ammonium hydroxide is added to adjust the pH of the liquid concentrate, but if the pH of the concentrate cannot be increased to a predetermined value by ammonium hydroxide, the concentrate becomes unstable. There is a case. Conversely, destabilization of the concentrate can be suppressed by increasing the pH of the concentrate to a predetermined value with ammonium hydroxide.
また、アルミニウムが蓄積した槽で処理を行うと、処理槽の特性が活性化され、新規処理槽で行った場合に比べて耐食性が向上することが確認されている。
すなわち、耐食性スプレーテストにおいて、アルミニウムの蓄積した古い処理槽を用いた場合には、耐食時間が１０００時間に達することが確認されている。
Moreover, it has been confirmed that when the treatment is performed in a tank in which aluminum is accumulated, the characteristics of the treatment tank are activated and the corrosion resistance is improved as compared with the case where the treatment is performed in a new treatment tank.
That is, in the corrosion resistance spray test, it has been confirmed that when an old treatment tank in which aluminum is accumulated is used, the corrosion resistance time reaches 1000 hours.
また、本発明で扱う今まで説明した水性表面処理剤には、可溶性アルミニウム塩をさらに加えることが好ましい。
ここで、可溶性アンモニウム塩類として、塩化アンモニウムアルミニウム、硫化アンモニウムアルミニウム、窒化アルミニウム、硫化カリウムアルミニウム、硫化アルミニウムなどを用いることが好ましい。
また、水性表面処理剤に可溶性アルミニウム塩を使用する場合、当該可溶性アルミニウム塩の槽内濃度を、アルミニウム濃度にして５〜５００ｐｐｍの範囲内の値とすることが好ましく、１０〜２００ｐｐｍの範囲内の値とすることがより好ましい。
Moreover, it is preferable to further add a soluble aluminum salt to the aqueous surface treatment agent described so far treated in the present invention.
Here, as the soluble ammonium salt, it is preferable to use ammonium aluminum chloride, ammonium aluminum sulfide, aluminum nitride, potassium aluminum sulfide, aluminum sulfide, or the like.
Moreover, when using a soluble aluminum salt for an aqueous surface treating agent, it is preferable to set the concentration in the tank of the soluble aluminum salt to a value within a range of 5 to 500 ppm as an aluminum concentration, and within a range of 10 to 200 ppm. A value is more preferable.
そして、一般に、本発明の表面処理方法で使用対象とする被処理部材に関して、予め表面汚染物質を取り除くために洗浄しておくことが好ましい。その後、酸性溶液で還元することにより、表面酸化物は取り除かれ、最後にリンス洗浄を実施することが好ましい。
また、被処理部材として、精錬合金に適した酸性溶液としては、５０％硝酸溶液が好ましいが、他の溶液を使用することも可能である。
次いで、洗浄した被処理部材に対して、浸漬法もしくはスプレー法のいずれかにより、本発明で使用するタングステン酸ジルコニウムで、３０秒〜１０分間の条件で処理することが好ましい。また、酸性溶液の温度に関して言えば、１３〜８２°Ｃ（５５〜１８０°Ｆ）の範囲内の値とすることが好ましく、２１〜４９°Ｃ（７０〜１２０°Ｆ）の範囲内の値とすることがより好ましい。
その後、被処理部材は、着色その他の前処理として、乾燥処理およびベーキング（焼付け処理）の少なくともいずれか一方の処理を行うことが好ましい。
また、水性表面処理剤に選択的に添加出来るものとして、表面活性剤、反応促進剤、染料、有機高分子化合物、緩衝剤およびｐＨ調整剤等の少なくとも一つが挙げられる。
In general, it is preferable that the member to be used in the surface treatment method of the present invention is previously washed to remove surface contaminants. Thereafter, the surface oxide is removed by reduction with an acidic solution, and it is preferable to perform a rinse cleaning at the end.
In addition, as an acidic solution suitable for a refining alloy as a member to be treated, a 50% nitric acid solution is preferable, but other solutions can also be used.
Next, it is preferable to treat the cleaned member to be treated with the zirconium tungstate used in the present invention by either an immersion method or a spray method for 30 seconds to 10 minutes. In terms of the temperature of the acidic solution, a value within the range of 13 to 82 ° C (55 to 180 ° F) is preferable, and a value within the range of 21 to 49 ° C (70 to 120 ° F). More preferably.
Thereafter, the member to be treated is preferably subjected to at least one of drying treatment and baking (baking treatment) as pretreatment for coloring and the like.
In addition, examples of those that can be selectively added to the aqueous surface treatment agent include at least one of a surfactant, a reaction accelerator, a dye, an organic polymer compound, a buffer, and a pH adjuster.
次いで、以下に実施例を示し、本発明を詳細に説明するが、これらは単なる実施形態としての一例であって、本発明の実施態様をこれらに限定するものではない。 Next, the present invention will be described in detail with reference to the following examples. However, these are merely examples as embodiments, and embodiments of the present invention are not limited thereto.
[実施例１]
まず、被処理部材をアルカリ性洗浄液７７°Ｃ（１７０°Ｆ）の中に１０〜１５分浸漬させ、表面の汚染物質を取り除いた。なお、本実施例では、アルカリ性洗浄液として、マクダーミッド社製のＴＳ４０Ａ（濃度４５ｇ／リットル）を用いたが、他のアルカリ性洗浄液を使用することも可能である。
次に、この被処理部材に対して、２分間のリンス処理と、室温（２０℃）にて５０％硝酸水溶液での１分間の還元処理と、２回目のリンス処理とを順次実施した。
その後、被処理部材に対して、本発明による被膜形成を行った。その処理条件としては、温度が室温（２０℃）〜４８°Ｃ（１２５°Ｆ）であって、処理時間が２〜１０分間であった。
次いで、かかる表面処理が終了した後、最終的にリンス処理を行い、さらに乾燥あるいはベーキング処理の少なくともいずれか一方の処理を行った後、最後に、着色剤処理（下塗り液またはペンキ処理）を実施した。
なお、本発明で使用できる処理槽における水性表面処理剤の濃度の例を表１に示す。
[Example 1]
First, the member to be treated was immersed in an alkaline cleaning liquid 77 ° C. (170 ° F.) for 10 to 15 minutes to remove surface contaminants. In this example, TS40A (concentration: 45 g / liter) manufactured by McDermid was used as the alkaline cleaning liquid, but other alkaline cleaning liquids can also be used.
Next, a rinsing treatment for 2 minutes, a reduction treatment for 1 minute with a 50% aqueous nitric acid solution at room temperature (20 ° C.), and a second rinsing treatment were sequentially performed on the member to be treated.
Then, the film formation by this invention was performed with respect to the to-be-processed member. As the treatment conditions, the temperature was room temperature (20 ° C.) to 48 ° C. (125 ° F.), and the treatment time was 2 to 10 minutes.
Next, after the surface treatment is completed, a rinsing treatment is finally performed, and at least one of drying and baking treatment is performed, and finally, a colorant treatment (undercoat liquid or paint treatment) is performed. did.
Table 1 shows an example of the concentration of the aqueous surface treatment agent in the treatment tank that can be used in the present invention.
[実施例２]
実施例２では、被処理部材における被膜の耐食性効果をみるために、実施例１で示される水性表面処理剤に５分間浸漬させたパネルと、クロム酸被膜を行ったパネルとを、それぞれ１０分間、様々な温度でベーキング処理した後に、中性塩スプレーをして、さらに加熱処理することで比較した。得られた結果を表２に示す。
[Example 2]
In Example 2, in order to see the corrosion resistance effect of the coating on the member to be treated, the panel immersed in the aqueous surface treatment agent shown in Example 1 for 5 minutes and the panel on which the chromic acid coating was applied were each 10 minutes. After the baking treatment at various temperatures, neutral salt spray was performed, and the heat treatment was further compared. The results obtained are shown in Table 2.
表２に示す結果から容易に理解できるように、本発明で用いている水性表面処理剤で処理したパネルは、クロム酸被膜を行ったパネルよりも、温度が上がるに従い、耐食性が向上していると言える。 As can be easily understood from the results shown in Table 2, the panel treated with the aqueous surface treating agent used in the present invention has improved corrosion resistance as the temperature rises, compared to the panel coated with chromic acid. It can be said.
[実施例３]
ジルコニウム溶液およびタングステン溶液で処理したパネルと、クロム酸被膜パネルとを隣接させた状態で、ＭＩＣ−Ｃ−８１７０６およびＭＩＣ−Ｃ−５５４１の適合テストを行った。
また、比較のために、このテストにおいては、被膜を有しないアルミニウムパネルも同時に処理した。
すなわち、上記表面処理を行って被膜を形成したパネル（被膜を有しないアルミニウムパネルも含む）について、スプレー法もしくはパウダーコート法により、下塗り液またはペンキを塗布した。その後、標準的なＡＳＴＭ Ｄ ３３５９−８７ Ｍｅｔｈｏｄ Ｂに従い、２ｍｍのクロスハッチテスト／テープ剥がしテストを行った。なお、このクロスハッチテスト／テープ剥がしテストは、テープを使った密着性の測定方法としては標準的な手法である。
その結果、予想通りではあったが、被膜を有しないアルミニウムパネルは、確実に密着不良が発生した。一方、密着性が促進されたタングステン酸ジルコニウムによる被膜パネルは、クロム酸被膜パネルと同等もしくはそれ以上の密着性を示すことが確認された。
[Example 3]
The conformity test of MIC-C-81706 and MIC-C-5541 was performed in a state where the panel treated with the zirconium solution and the tungsten solution and the chromic acid coated panel were adjacent to each other.
For comparison, in this test, an aluminum panel having no coating was also processed at the same time.
That is, for the panel (including an aluminum panel having no coating) on which the surface treatment was performed, an undercoat liquid or paint was applied by a spray method or a powder coating method. A 2 mm cross-hatch test / tape peel test was then performed according to standard ASTM D 3359-87 Method B. This cross-hatch test / tape peeling test is a standard method for measuring adhesion using tape.
As a result, although it was as expected, the aluminum panel having no coating surely had poor adhesion. On the other hand, it was confirmed that the coated panel made of zirconium tungstate whose adhesion was promoted showed the same or better adhesion than the chromic acid coated panel.
[実施例４]
タングステン酸ジルコニウム被膜パネルと、ＭＩＣ−Ｃ−８１７０６／ＭＩＣ−Ｃ−５５４１に適合するクロム酸被膜パネルと、熱処理もしくはベーキング処理した被膜を有しないアルミニウムパネルと、を互いに隣接させた状態で、加熱処理テストを行った。
[Example 4]
Heat treatment in a state where a zirconium tungstate-coated panel, a chromic acid-coated panel conforming to MIC-C-81706 / MIC-C-5541, and an aluminum panel having no heat-treated or baked film are adjacent to each other. Tested.
次いで、上記の処理を行ったアルミニウムパネル（および比較としての被膜を有しないアルミニウムパネル）は、１５０°Ｃ、２００°Ｃ、２５０°Ｃ、３００°Ｃ、３５０°Ｃ、２０分間の条件で、着色前に加熱処理を行い、その後、スプレー法にて下塗り液（またはペンキ）を用いて着色した。 Next, the aluminum panel subjected to the above treatment (and an aluminum panel without a coating as a comparison) was subjected to conditions of 150 ° C, 200 ° C, 250 ° C, 300 ° C, 350 ° C, 20 minutes Heating was performed before coloring, and then coloring was performed using an undercoat liquid (or paint) by a spray method.
その後、これらのパネルについて、標準的なＡＳＴＭ Ｄ ３３５９−８７ Ｍｅｔｈｏｄ Ｂに従い、２ｍｍのクロスハッチテスト／テープ剥がしテストを行った。その結果、密着性を促進させたタングステン酸ジルコニウム処理したパネルは、被膜を有しないアルミニウムパネルもしくはクロム酸被膜パネルよりも遥かに良い密着性に関する結果となった。 These panels were then subjected to a 2 mm crosshatch test / tape peel test in accordance with standard ASTM D 3359-87 Method B. As a result, the panel treated with zirconium tungstate with enhanced adhesion resulted in much better adhesion than the aluminum or chromic acid coated panel without the coating.
本発明の水性表面処理剤および被膜形成方法によって得られる被膜は、一般にクロムを含んでおらず、当該被膜の表面と、防湿のための有機表面膜との間の密着性を改善するだけでなく、耐食性もまた改善されている。
さらに、後処理として行われる、熱処理あるいはベーキング処理の少なくとも一方の処理で受ける影響を最小限に抑えることができる。
したがって、本発明の水性表面処理剤および被膜形成方法は、特に、亜鉛、亜鉛合金、アルミニウムおよびアルミニウム合金の表面処理に適しているが、鋼等、他の金属における表面処理にも適用可能である。
The film obtained by the aqueous surface treating agent and the film forming method of the present invention generally does not contain chromium, and not only improves the adhesion between the surface of the film and the organic surface film for moisture prevention. Corrosion resistance has also been improved.
Furthermore, it is possible to minimize the influence of at least one of the heat treatment and the baking treatment performed as a post-treatment.
Therefore, the aqueous surface treatment agent and the film forming method of the present invention are particularly suitable for surface treatment of zinc, zinc alloy, aluminum and aluminum alloy, but can also be applied to surface treatment of other metals such as steel. .
Claims (43)
（ａ）タングステン酸イオン供給源、および（ｂ）ジルコニウム含有可溶性材料を含む水性表面処理剤による金属表面処理工程と、
表面処理した金属表面に対して、乾燥処理および／またはベーキング処理を実施するための処理工程と、
を順次含むことを特徴とする被膜形成方法。 A method of forming a film on a metal surface,
A metal surface treatment step with an aqueous surface treating agent comprising (a) a tungstate ion source and (b) a zirconium-containing soluble material;
A treatment step for performing a drying treatment and / or a baking treatment on the surface-treated metal surface;
The film formation method characterized by including sequentially.
25. The aqueous surface treatment agent according to claim 24, comprising at least one compound selected from the group consisting of a surfactant, a reaction accelerator, a dye, an organic polymer compound, a buffering agent, and a pH adjusting agent. The aqueous surface treating agent as described.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/099,769 US20030172998A1 (en) | 2002-03-14 | 2002-03-14 | Composition and process for the treatment of metal surfaces |
| PCT/US2003/003610 WO2003078682A1 (en) | 2002-03-14 | 2003-02-07 | Composition and process for the treatment of metal surfaces |
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| Publication Number | Publication Date |
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| JP2005520047A true JP2005520047A (en) | 2005-07-07 |
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| US (1) | US20030172998A1 (en) |
| EP (1) | EP1492902A4 (en) |
| JP (1) | JP2005520047A (en) |
| CN (1) | CN100378246C (en) |
| AU (1) | AU2003212949A1 (en) |
| TW (1) | TWI255863B (en) |
| WO (1) | WO2003078682A1 (en) |
Cited By (3)
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|---|---|---|---|---|
| JP2011503897A (en) * | 2007-11-13 | 2011-01-27 | マクダーミッド インコーポレーテッド | Compositions and methods for controlling galvanic corrosion in printed circuit boards |
| JP2011515587A (en) * | 2008-03-26 | 2011-05-19 | マクダーミッド インコーポレーテッド | Aluminum treatment composition |
| US8980016B2 (en) | 2007-01-19 | 2015-03-17 | Nihon Hyomen Kagaku Kabushiki Kaisha | Chromium-free solution for treating metal surfaces |
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| CA2662514C (en) * | 2006-09-19 | 2014-06-17 | Valspar Sourcing, Inc. | Food and beverage containers and methods of coating |
| US20100243108A1 (en) * | 2009-03-31 | 2010-09-30 | Ppg Industries Ohio, Inc. | Method for treating and/or coating a substrate with non-chrome materials |
| US9347134B2 (en) | 2010-06-04 | 2016-05-24 | Prc-Desoto International, Inc. | Corrosion resistant metallate compositions |
| CN102312233B (en) * | 2010-06-29 | 2013-10-30 | 株式会社神户制钢所 | Aluminum alloy plate after surface treatment and manufacturing method thereof |
| CN102529202B (en) * | 2010-10-18 | 2015-02-25 | 株式会社神户制钢所 | Aluminium alloy plate, bonded body using the same and vehicular member |
| CN102586730A (en) | 2011-01-17 | 2012-07-18 | 鸿富锦精密工业（深圳）有限公司 | Film-coated part and preparation method thereof |
| TWI426153B (en) * | 2011-01-19 | 2014-02-11 | Hon Hai Prec Ind Co Ltd | Coated article and method for making the same |
| US20140041764A1 (en) * | 2012-08-07 | 2014-02-13 | Roberto Zoboli | Steel Pre-Paint Treatment Composition |
| JP6143431B2 (en) * | 2012-09-20 | 2017-06-07 | 株式会社神戸製鋼所 | Aluminum alloy plate, joined body and automobile member using the same |
| ITMI20122229A1 (en) * | 2012-12-21 | 2014-06-22 | Campagnolo Srl | BICYCLE COMPONENT INCLUDING AN ALUMINUM BODY AND A COMPOSITE BODY, AND METHOD OF MANUFACTURING SUCH A COMPONENT |
| US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
| CN109317382B (en) * | 2018-11-22 | 2021-10-19 | 安徽安铝铝业有限公司 | Surface treatment process for aluminum alloy section |
| CN114836745A (en) * | 2022-03-21 | 2022-08-02 | 华南理工大学 | Aluminum alloy neutral zirconium-tungsten conversion solution and preparation method of zirconium-tungsten conversion film on surface of aluminum alloy |
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| US3963568A (en) * | 1973-05-30 | 1976-06-15 | Kansai Paint Company, Ltd. | Process for coating aluminum or aluminum alloy |
| DE2905535A1 (en) * | 1979-02-14 | 1980-09-04 | Metallgesellschaft Ag | METHOD FOR SURFACE TREATMENT OF METALS |
| US5143562A (en) * | 1991-11-01 | 1992-09-01 | Henkel Corporation | Broadly applicable phosphate conversion coating composition and process |
| JPH05214266A (en) * | 1992-01-31 | 1993-08-24 | Nippon Parkerizing Co Ltd | Self-depositing water-based coating composition |
| US5449415A (en) * | 1993-07-30 | 1995-09-12 | Henkel Corporation | Composition and process for treating metals |
| US5902767A (en) * | 1993-08-03 | 1999-05-11 | Mobil Oil Corporation | Catalyst having an acidic solid oxide component and a group IB metal or metal oxide component |
| US5441580A (en) * | 1993-10-15 | 1995-08-15 | Circle-Prosco, Inc. | Hydrophilic coatings for aluminum |
| DE4417965A1 (en) * | 1994-05-21 | 1995-11-23 | Henkel Kgaa | Iron phosphating using substituted monocarboxylic acids |
| US6193815B1 (en) * | 1995-06-30 | 2001-02-27 | Henkel Corporation | Composition and process for treating the surface of aluminiferous metals |
| US6027580A (en) * | 1995-12-13 | 2000-02-22 | Henkel Corporation | Hydrophilicizing post-treatment over chromate conversion coating |
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| JP4099307B2 (en) * | 2000-04-20 | 2008-06-11 | 日本ペイント株式会社 | Non-chromium anti-rust treatment agent for aluminum, anti-rust treatment method and anti-rust treated aluminum products |
| CA2408675A1 (en) * | 2000-05-11 | 2001-11-15 | Henkel Corporation | Metal surface treatment agent |
-
2002
- 2002-03-14 US US10/099,769 patent/US20030172998A1/en not_active Abandoned
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2003
- 2003-02-07 JP JP2003576672A patent/JP2005520047A/en active Pending
- 2003-02-07 WO PCT/US2003/003610 patent/WO2003078682A1/en not_active Application Discontinuation
- 2003-02-07 AU AU2003212949A patent/AU2003212949A1/en not_active Abandoned
- 2003-02-07 EP EP03708992A patent/EP1492902A4/en not_active Withdrawn
- 2003-02-07 CN CNB038058278A patent/CN100378246C/en not_active Expired - Fee Related
- 2003-02-13 TW TW092102988A patent/TWI255863B/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8980016B2 (en) | 2007-01-19 | 2015-03-17 | Nihon Hyomen Kagaku Kabushiki Kaisha | Chromium-free solution for treating metal surfaces |
| JP2011503897A (en) * | 2007-11-13 | 2011-01-27 | マクダーミッド インコーポレーテッド | Compositions and methods for controlling galvanic corrosion in printed circuit boards |
| JP2011515587A (en) * | 2008-03-26 | 2011-05-19 | マクダーミッド インコーポレーテッド | Aluminum treatment composition |
Also Published As
| Publication number | Publication date |
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| EP1492902A1 (en) | 2005-01-05 |
| TWI255863B (en) | 2006-06-01 |
| CN100378246C (en) | 2008-04-02 |
| AU2003212949A1 (en) | 2003-09-29 |
| EP1492902A4 (en) | 2005-06-15 |
| CN1643181A (en) | 2005-07-20 |
| TW200303934A (en) | 2003-09-16 |
| WO2003078682A1 (en) | 2003-09-25 |
| US20030172998A1 (en) | 2003-09-18 |
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