JP2013001959A - Treatment liquid of non-chromium black chemical film for zinc-iron alloy plating film, and treatment method therefor - Google Patents
Treatment liquid of non-chromium black chemical film for zinc-iron alloy plating film, and treatment method therefor Download PDFInfo
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Description
本発明は、亜鉛−鉄合金めっき皮膜上にノンクロム黒色化成皮膜処理施して黒色を発色させるための処理剤並びに処理方法に関する。 The present invention relates to a treatment agent and a treatment method for developing a black color by performing a non-chromium black chemical conversion film treatment on a zinc-iron alloy plating film.
亜鉛めっきの耐食性を向上する目的で亜鉛−鉄合金めっきなど亜鉛合金めっきが広く行われている。その中でも亜鉛−鉄合金めっきは自動車部品など、特に高い耐食性が要求される部品等に広範囲に使用されている。 Zinc alloy plating such as zinc-iron alloy plating is widely performed for the purpose of improving the corrosion resistance of zinc plating. Among them, zinc-iron alloy plating is widely used for parts such as automobile parts that require particularly high corrosion resistance.
亜鉛めっき皮膜に三価クロム黒色化成皮膜処理を施す方法として現在用いられている方法として硫黄化合物またはリンの酸素酸と金属を反応させる方法がある。例えば特開２００３−２１３４４６には三価クロム、亜硫酸イオン、硝酸等酸化性物質、リンの酸素酸を含む水溶液で処理し、黒色化成皮膜を形成する方法が、特開２００５−２０６８７２には三価クロム、無機酸イオン、硫黄化合物を含む処理液で処理し、黒色化成皮膜を形成する方法が記載され、前者には化成皮膜形成後にオーバーコートを施す方法が、後者には化成皮膜形成後に三価クロム、界面活性剤及びケイ素化合物よりなる群から選択された１種以上を含む第二処理液で処理する方法が開示されている。亜鉛−鉄合金めっき皮膜に対しても通常、亜鉛めっき皮膜と同様の三価クロム黒色化成皮膜処理を施すことが可能であることが知られている。 There is a method of reacting a sulfur compound or an oxygen acid of phosphorus with a metal as a method currently used as a method of performing a trivalent chromium black chemical conversion film treatment on a galvanized film. For example, Japanese Patent Application Laid-Open No. 2003-213446 discloses a method of forming a black chemical conversion film by treating with an aqueous solution containing an oxidizing substance such as trivalent chromium, sulfite ion, nitric acid, and phosphorus oxygen acid. A method of forming a black chemical conversion film by treating with a treatment liquid containing chromium, inorganic acid ions and sulfur compounds is described. The former is a method of applying an overcoat after the formation of a chemical conversion film, and the latter is trivalent after the formation of the chemical conversion film. A method of treating with a second treatment liquid containing one or more selected from the group consisting of chromium, a surfactant and a silicon compound is disclosed. It is known that the same trivalent chromium black chemical conversion film treatment as that of the zinc plating film can be usually applied to the zinc-iron alloy plating film.
ノンクロム黒色化成皮膜処理を施す方法は亜鉛系めっきにおいては例えば特開２００８−２１４７４４が挙げられる。これはアルミニウム、アンチモン、リン酸、チオ化合物を用いてノンクロム黒色化成皮膜を形成する方法であるが、実施例には亜鉛めっきの例しかなく、亜鉛合金めっきに適用可能かどうかが実験的に確認できていない上、既存の三価クロム黒色化成皮膜処理と手順に異なる部分があるため、既存の設備が利用できない現場が多く設備投資等のコストが大きくなる。 As a method of performing the non-chromium black chemical conversion film treatment, for example, JP 2008-214744 A can be cited in zinc-based plating. This is a method of forming a non-chromium black chemical conversion film using aluminum, antimony, phosphoric acid, and thio compounds. However, there are only examples of zinc plating in the examples, and it is experimentally confirmed whether it can be applied to zinc alloy plating. In addition, since there is a difference in the procedure from the existing trivalent chromium black chemical conversion film treatment, there are many sites where existing facilities cannot be used, and the cost of capital investment and the like increases.
過去、ノンクロム黒色化成皮膜処理を施して現行の亜鉛めっき上、三価クロム黒色化成皮膜と同等以上の耐食性を発揮した実施例は、亜鉛めっきはもとより、いかなる亜鉛系合金めっきにおいても確認されていない。 In the past, the examples of non-chromium black conversion coating treatments that have exhibited corrosion resistance equivalent to or better than that of trivalent chromium black conversion coatings on the current zinc plating have not been confirmed in any zinc-based alloy plating as well as zinc plating. .
現在、三価クロム化成皮膜中の三価クロムが環境に対して有害性の高い六価クロムに変化し溶出する可能性があることが知られており、将来的には三価クロムの使用も規制される可能性がある。しかし、亜鉛−鉄合金めっきにおいては有効なノンクロム黒色化成皮膜処理の方法が確立されていないため、重要な課題である。 Currently, it is known that trivalent chromium in the trivalent chromium conversion coating may be transformed into hexavalent chromium, which is highly harmful to the environment, and may be eluted. May be regulated. However, in zinc-iron alloy plating, an effective non-chromium black conversion coating treatment method has not been established, which is an important issue.
本発明者が鋭意研究した結果、リンのオキソ酸イオン、窒素のオキソ酸イオン、スズ化合物と、バナジウム化合物とを溶解させた水溶液により化成処理を行うことで亜鉛めっき上の三価クロム黒色化成皮膜処理と同等以上の外観、耐食性を発揮する皮膜を形成する方法を見出した。窒素のオキソ酸イオンは亜鉛−鉄合金めっき皮膜をエッチングし、活性化する効果があり、リンのオキソ酸イオンは耐食性を有するリン酸塩皮膜を形成するとともに亜鉛−鉄合金めっき皮膜中の鉄と反応し、黒色化させる効果がある。 As a result of intensive studies by the present inventors, a trivalent chromium black chemical conversion coating on galvanizing by performing chemical conversion treatment with an aqueous solution in which phosphorus oxo acid ions, nitrogen oxo acid ions, tin compounds and vanadium compounds are dissolved. The present inventors have found a method of forming a film that exhibits an appearance and corrosion resistance equivalent to or better than those of the treatment. The oxo acid ions of nitrogen have the effect of etching and activating the zinc-iron alloy plating film, and the oxo acid ions of phosphorus form a phosphate film having corrosion resistance and the iron in the zinc-iron alloy plating film. It has the effect of reacting and blackening.
スズ化合物、バナジウム化合物はリン酸塩皮膜に入ることで皮膜の耐食性向上に寄与する効果がある。これらの成分は、上述の皮膜形成の基本成分と共に析出したり、皮膜をより緻密にしたりする作用があると考えられ、外観や耐食性に寄与する。また、スズ、バナジウムをそれぞれ単独で用いても効果があるが、両者を併用することで、より大きな効果を得られる。 Tin compounds and vanadium compounds have the effect of contributing to improvement of the corrosion resistance of the coating by entering the phosphate coating. These components are considered to have the effect of precipitating together with the above-mentioned basic components for film formation or making the film denser, and contribute to appearance and corrosion resistance. Moreover, although it is effective even if it uses tin and vanadium each independently, a bigger effect can be acquired by using both together.
以上の知見を基礎として本発明は、一実施形態において、前記ノンクロム黒色化成皮膜処理を施す処理液がリンのオキソ酸イオン、窒素のオキソ酸イオン、スズ化合物、バナジウム化合物を全て含有することを特徴とする前記ノンクロム黒色化成皮膜形成処理液及び処理方法を提供する。 Based on the above knowledge, in one embodiment, the present invention is characterized in that the treatment liquid for performing the non-chromium black chemical conversion film treatment contains all of oxo acid ions of phosphorus, oxo acid ions of nitrogen, tin compounds, and vanadium compounds. The non-chromium black chemical conversion film forming treatment liquid and the treatment method are provided.
さらに本発明は、一実施形態において、前記処理液が、リンのオキソ酸イオンを１〜１００ｇ／Ｌ、及び窒素のオキソ酸イオンを０．１〜３０ｇ／Ｌ含有することを特徴とする前記のノンクロム黒色化成皮膜形成処理液及び方法である。 Furthermore, in one embodiment of the present invention, the treatment solution contains 1 to 100 g / L of phosphorus oxoacid ions and 0.1 to 30 g / L of nitrogen oxoacid ions. Non-chromium black chemical conversion film forming treatment liquid and method.
さらに本発明は、一実施形態において、前記処理液が、スズイオンを１０〜５５０ｍｇ／Ｌ、及び／又はバナジウムイオンを０．０１〜１０ｇ／Ｌ含有することを特徴とする前記の方法である。 Furthermore, in one embodiment, the present invention is the above-described method, wherein the treatment liquid contains 10 to 550 mg / L of tin ions and / or 0.01 to 10 g / L of vanadium ions.
さらに本発明は、一実施形態において、前記の方法を用いてノンクロム化成皮膜を形成した金属基材である。 Furthermore, in one embodiment, the present invention is a metal base material on which a non-chromic chemical conversion film is formed using the method described above.
さらに本発明は、一実施形態において、前記のめっき液でめっきした後に三価クロム黒色化成皮膜処理を施すことを特徴とする皮膜形成方法である。 Furthermore, in one embodiment, the present invention is a film forming method characterized by performing a trivalent chromium black chemical conversion film treatment after plating with the plating solution.
ノンクロム黒色化成皮膜形成反応はリンのオキソ酸イオン及び、窒素のオキソ酸イオンが関与する反応であることにより、クロムを含有しない金属表面処理液を用いることで可能となる。 The non-chromium black chemical conversion film forming reaction is a reaction involving phosphorus oxoacid ions and nitrogen oxoacid ions, and thus can be achieved by using a metal surface treatment solution that does not contain chromium.
リンのオキソ酸としてはリン酸、亜リン酸、次亜リン酸、ピロリン酸及びこれらの塩等が挙げられるがこれらに限定されるものではなく、１〜１００ｇ／Ｌ、より望ましくは１０〜４０ｇ／Ｌの範囲で用いることが望ましい。低濃度では黒色化が不十分となる上、十分な皮膜が形成されず耐食性が低くなる。高濃度では反応が過剰となり均一な黒色外観が得られない。また、黒色化効果の大きさを考慮すると亜リン酸が特に好ましい。 Examples of oxo acids of phosphorus include, but are not limited to, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid and salts thereof, and 1 to 100 g / L, more desirably 10 to 40 g. It is desirable to use within the range of / L. When the concentration is low, blackening is insufficient, and a sufficient film is not formed, resulting in low corrosion resistance. At high concentrations, the reaction is excessive and a uniform black appearance cannot be obtained. Further, phosphorous acid is particularly preferable in consideration of the magnitude of the blackening effect.
窒素のオキソ酸イオンの供給源は硝酸もしくは各種金属の硝酸塩、亜硝酸塩として供給される。窒素のオキソ酸イオンとしてとして０．１〜３０ｇ／Ｌ、より好ましくは２〜１０ｇ／Ｌの範囲で用いることが望ましい。低濃度では十分に反応が進まず良好な外観と耐食性を有する皮膜が形成されない。高濃度では反応過剰となり、やはり良好な皮膜が形成されない。 The source of nitrogen oxo acid ions is supplied as nitric acid or various metal nitrates and nitrites. The nitrogen oxo acid ion is preferably used in the range of 0.1 to 30 g / L, more preferably 2 to 10 g / L. At low concentrations, the reaction does not proceed sufficiently, and a film having good appearance and corrosion resistance is not formed. At a high concentration, the reaction becomes excessive and a good film is not formed.
スズ化合物の供給源としては、水溶性の化合物であれば制限はないが、硝酸塩、硫酸塩または塩化物とするのが好ましく特に硫酸スズが好ましい。スズの濃度は１０ｍｇ／Ｌ〜５５０ｍｇ／Ｌ、より望ましくは１００ｍｇ／Ｌ〜３００ｍｇ／Ｌの範囲で加えることが望ましい。添加量が過小だとスズの効果を示さず、過剰に添加すると正常な皮膜の形成を妨げることがある。 The source of the tin compound is not particularly limited as long as it is a water-soluble compound, but nitrate, sulfate or chloride is preferable, and tin sulfate is particularly preferable. The tin concentration is preferably 10 mg / L to 550 mg / L, more preferably 100 mg / L to 300 mg / L. If the addition amount is too small, the effect of tin is not exhibited, and if it is added excessively, the formation of a normal film may be hindered.
バナジウム化合物の供給源は限定的ではなく、例えば塩化バナジウム（ＶＣｌ2、ＶＣｌ3、及びＶＣｌ4）、二塩化バナジル（ＶＯＣｌ2）、臭化バナジウム（ＶＢｒ2、ＶＢｒ3）、ヨウ化バナジウム（ＶＩ2、ＶＩ3）、硫酸バナジウム（ＶＳＯ4、Ｖ2（ＳＯ4）3）、硫酸バナジル（ＶＯＳＯ4）、硝酸バナジウム（Ｖ（ＮＯ3）2、 Ｖ（ＮＯ3）3）、五酸化バナジウム(Ｖ2Ｏ5)、バナジン酸（Ｈ3ＶＯ4）、オルトバナジン酸カリウム(Ｋ3ＶＯ4)、オルトバナジン酸ナトリウム(Ｎａ3ＶＯ4)、オルトバナジン酸リチウム（Ｌｉ3ＶＯ4）メタバナジン酸カリウム(ＫＶＯ3)、メタバナジン酸ナトリウム(ＮａＶＯ3)、メタバナジン酸リチウム（ＬｉＶＯ3）、メタバナジン酸アンモニウム(ＮＨ4ＶＯ3)、等が挙げられ、特にバナジン酸が好ましいが限定的ではない。バナジウムの濃度は０．０１ｇ／Ｌ〜１０ｇ／Ｌ、より望ましくは０．１〜２ｇ／Ｌの範囲で加えることが望ましい。添加量が過小だとバナジウムの効果を示さず、過剰に添加しても効果は頭打ちであり、経済性を損なう。 The source of vanadium compound is not critical, for example, vanadium chloride (VCl 2, VCl 3, and VCl 4), dichloride vanadyl (VOCl 2), vanadium bromide (VBr 2, VBr 3), iodide vanadium (VI 2 , VI 3 ), vanadium sulfate (VSO 4 , V 2 (SO 4 ) 3 ), vanadyl sulfate (VOSO 4 ), vanadium nitrate (V (NO 3 ) 2 , V (NO 3 ) 3 ), vanadium pentoxide ( V 2 O 5 ), vanadate (H 3 VO 4 ), potassium orthovanadate (K 3 VO 4 ), sodium orthovanadate (Na 3 VO 4 ), lithium orthovanadate (Li 3 VO 4 ) potassium metavanadate (KVO 3 ), sodium metavanadate (NaVO 3 ), lithium metavanadate (LiVO 3 ), ammonium metavanadate (NH 4 VO 3 ), etc. In particular, vanadic acid is preferable but not limited. The concentration of vanadium is preferably 0.01 to 10 g / L, more preferably 0.1 to 2 g / L. If the addition amount is too small, the effect of vanadium will not be exhibited, and even if it is added excessively, the effect will reach its peak and the economic efficiency will be impaired.
また、さらに各種金属を添加することも可能である。各種金属として例えばＦｅ、Ｍｇ、Ｃａ、Ｎｉ、Ｃｏ、Ｚｎ、Ｍｏ、Ｗ、Ｔｉ、Ａｌ、Ｚｒ、Ｍｎ、Ｃｅ、Ｙ、Ｌａ、Ｎｄ、Ｇｄ、Ｄｙ、Ｈｏ、Ｅｒ、Ｌｕが挙げられるがこれに限定されない。供給源は、水溶性の化合物であれば制限はないが、硝酸塩、硫酸塩または塩化物とするのが好ましい。 It is also possible to add various metals. Examples of various metals include Fe, Mg, Ca, Ni, Co, Zn, Mo, W, Ti, Al, Zr, Mn, Ce, Y, La, Nd, Gd, Dy, Ho, Er, and Lu. It is not limited to. The supply source is not particularly limited as long as it is a water-soluble compound, but is preferably nitrate, sulfate or chloride.
ノンクロム黒色化成皮膜形成のための浸漬条件としては、温度１０〜５０℃、ｐＨ１.０〜３．０の範囲であることが好ましく、より好ましくは温度２０〜４０℃、ｐＨ１．５〜２．５の範囲である。低温では十分な皮膜が形成せず、高温では外観が曇りがちになる上、作業の容易性を損なう。低ｐＨでは過剰反応となり十分な皮膜が形成しない。高ｐＨでは反応不足で皮膜が形成しづらい。浸漬時間は２０〜１２０秒、好ましくは３０秒〜９０秒の範囲であることが好ましい。浸漬時間が２０秒以下では十分な膜厚が得られない可能性が高い。１２０秒以上の浸漬は過剰反応による外観並びに耐食性の悪化を招く。また、均一に皮膜を形成させる為には、撹拌があることが好ましく、化成処理後は、被処理物を水洗することが好ましい。 As immersion conditions for forming the non-chromium black conversion coating, it is preferable that the temperature is in the range of 10 to 50 ° C. and pH of 1.0 to 3.0, more preferably 20 to 40 ° C. and pH of 1.5 to 2.5. Range. At low temperatures, a sufficient film is not formed, and at high temperatures, the appearance tends to become cloudy and the workability is impaired. At low pH, excessive reaction occurs and a sufficient film is not formed. At high pH, it is difficult to form a film due to insufficient reaction. The dipping time is 20 to 120 seconds, preferably 30 to 90 seconds. If the immersion time is 20 seconds or less, there is a high possibility that a sufficient film thickness cannot be obtained. Soaking for 120 seconds or more leads to deterioration of appearance and corrosion resistance due to excessive reaction. Moreover, in order to form a film | membrane uniformly, it is preferable that there is stirring, and it is preferable to wash a to-be-processed object after chemical conversion treatment.
上述化成処理後、水洗した後に無機、有機若しくは有機無機複合のコーティングを行うと耐食性さらに向上する。無機系のオーバーコートとしては、シリカ系、リン酸系のオーバーコートが挙げられるがそれ以外のオーバーコートも可能である。有機系のオーバーコートとしては、塗料、樹脂種も特に限定をせず水系あるいは水系以外でも適用可能である。例えばポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、アクリル樹脂、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、メラミン樹脂等の有機皮膜が挙げられるが、これらに限定されるものではない。また、オーバーコートは本発明による表面処理後すぐに行っても良いが乾燥後、プレスや折り曲げ等の加工後に行っても有効であり、複数回実施することも有効である。オーバーコートの方法は特に限定せず、塗布塗装、浸漬塗装、静電塗装、電着塗装、粉体塗装など種々の方法が可能である。 After the above chemical conversion treatment, after washing with water, coating with an inorganic, organic or organic-inorganic composite will further improve the corrosion resistance. Examples of inorganic overcoats include silica-based and phosphoric acid-based overcoats, but other overcoats are also possible. The organic overcoat is not particularly limited with respect to the coating material and the resin type, and can be applied to an aqueous overcoat or other than an aqueous overcoat. For example, polyethylene, polyvinyl chloride, polystyrene, polypropylene, acrylic resin, methacrylic resin, polycarbonate, polyamide, polyacetal, fluororesin, urea resin, phenol resin, unsaturated polyester resin, polyurethane, alkyd resin, epoxy resin, melamine resin, etc. Although a film | membrane is mentioned, it is not limited to these. Further, overcoating may be performed immediately after the surface treatment according to the present invention, but it is also effective if it is performed after drying and after processing such as pressing and bending, and it is also effective to perform the coating several times. The method of overcoat is not particularly limited, and various methods such as coating, immersion coating, electrostatic coating, electrodeposition coating, and powder coating are possible.
以上の本発明の処理は、金属基材に用いられる。金属基材とは金属表面を有する基材のことであり、具体的には金属板、ボルトなどが挙げられるがこれに限定されない。 The above-described treatment of the present invention is used for a metal substrate. The metal substrate is a substrate having a metal surface, and specifically includes, but is not limited to, a metal plate and a bolt.
以下、実施例及び比較例により本発明を説明する。
ノンクロム黒色化成皮膜試験
亜鉛鉄合金めっき品に対してノンクロム黒色化成皮膜処理試験を行った。
以下、特に断りのない限り、リンのオキソ酸として亜リン酸を、スズ源として硫酸スズを、バナジウム源としてバナジン酸を用いた。また、処理条件はｐＨ１．８、温度３０℃、処理時間４０秒である。化成処理、水洗後に後処理剤として日本表面化学（株）製ＦＴ−１７０を標準条件で使用した。尚、処理液のｐＨ調整は硝酸（比較例３は硫酸）と水酸化ナトリウムを用いて行った。外観の評価は目視にて行い、均一で光沢のある外観を○、ややムラや曇りのあるか黒色が不足した外観を△、ムラや曇りがひどい、または黒色がほとんどない外観を×とした。耐食性の評価は、ＪＩＳ Ｚ ２３７１に従う塩水噴霧試験を行い白錆が５％発生した時間を試験結果に示した。
Hereinafter, the present invention will be described with reference to examples and comparative examples.
Non-chromium black conversion coating test A non-chromium black conversion coating treatment test was conducted on zinc-iron alloy plated products.
Unless otherwise specified, phosphorous acid was used as the phosphorus oxo acid, tin sulfate was used as the tin source, and vanadic acid was used as the vanadium source. The processing conditions are pH 1.8, temperature 30 ° C., and processing time 40 seconds. After chemical conversion treatment and washing with water, FT-170 manufactured by Nippon Surface Chemical Co., Ltd. was used as a post-treatment agent under standard conditions. In addition, pH adjustment of the process liquid was performed using nitric acid (Comparative Example 3 is sulfuric acid) and sodium hydroxide. The appearance was evaluated visually, with a uniform and glossy appearance as ◯, an appearance with some unevenness, cloudiness or lack of black, and an appearance with poor unevenness or cloudiness or almost no black. For the evaluation of corrosion resistance, a salt spray test according to JIS Z 2371 was performed, and the time when white rust was generated by 5% was shown in the test results.
結果は下表１の通りである。
実施例１の浴組成のノンクロム黒色化成皮膜処理液に浸漬する条件を変更して試験を行った。結果を以下の表２に示す。
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011134268A JP2013001959A (en) | 2011-06-16 | 2011-06-16 | Treatment liquid of non-chromium black chemical film for zinc-iron alloy plating film, and treatment method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011134268A JP2013001959A (en) | 2011-06-16 | 2011-06-16 | Treatment liquid of non-chromium black chemical film for zinc-iron alloy plating film, and treatment method therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2013001959A true JP2013001959A (en) | 2013-01-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011134268A Withdrawn JP2013001959A (en) | 2011-06-16 | 2011-06-16 | Treatment liquid of non-chromium black chemical film for zinc-iron alloy plating film, and treatment method therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2013001959A (en) |
-
2011
- 2011-06-16 JP JP2011134268A patent/JP2013001959A/en not_active Withdrawn
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| Date | Code | Title | Description |
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| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20140902 |