JP2013166979A - Chromium-free aqueous treatment liquid, treated coating, and metal product - Google Patents
Chromium-free aqueous treatment liquid, treated coating, and metal product Download PDFInfo
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本発明は、鉄−亜鉛合金メッキ層被覆用の水性クロムフリー処理液、該処理液で形成した処理被膜及び該処理被膜を備えた金属製品に関する。さらに詳しくは、鉄或いは鉄合金の各種金属製品、例えば、ボルト、ナット、スプリング、シャフト、ピストン、シリンダー、軸受けメタル等に、優れた耐食性を付与することができ、更には、潤滑性、耐摩耗性、或いは着色化された外観を付与しうる水性クロムフリー処理液、その処理被膜及び該処理被膜を備えた金属製品に関する。 The present invention relates to an aqueous chromium-free treatment solution for coating an iron-zinc alloy plating layer, a treatment coating formed with the treatment solution, and a metal product provided with the treatment coating. More specifically, it can provide excellent corrosion resistance to various metal products of iron or iron alloys, such as bolts, nuts, springs, shafts, pistons, cylinders, bearing metals, etc. The present invention relates to an aqueous chromium-free treatment solution capable of imparting a colored or colored appearance, a treatment coating thereof, and a metal product provided with the treatment coating.
従来から各種金属表面の防食処理として、亜鉛或いは亜鉛合金をメッキ処理することは良く知られているが、そのままでは白錆が出やすいため、さらに塗装による防錆処理が施されることが多い。
一方で各種金属表面に亜鉛或いは亜鉛合金皮膜を形成する方法として、従来の溶融亜鉛メッキ法、電気亜鉛メッキ法以外に乾式亜鉛メッキ法、具体的には、鉄又は鉄合金を核とし、この核周囲に鉄−亜鉛合金層を介して亜鉛又は亜鉛合金を被着してなる、独立した粒子の集合体からなるブラスト材料を、金属表面に投射して、多孔質の鉄−亜鉛合金メッキ層を形成する方法（Mechanical Plating法、以下、ＭＰ法と称す）が知られている（特許文献１参照）。
この方法は、エネルギー消費が少なく、環境汚染も少ない有意義な方法であるが、形成される鉄−亜鉛合金層が多孔質であるため、十分な耐食性を得るには、さらに何らかの処理が必要である。
Conventionally, it is well known that zinc or a zinc alloy is plated as an anticorrosion treatment for various metal surfaces, but since white rust is likely to occur as it is, it is often further subjected to a rust prevention treatment by painting.
On the other hand, as a method of forming a zinc or zinc alloy film on various metal surfaces, in addition to the conventional hot dip galvanizing method and electrogalvanizing method, a dry galvanizing method, specifically, iron or iron alloy as a core, this core A blasting material consisting of an aggregate of independent particles formed by depositing zinc or a zinc alloy around an iron-zinc alloy layer is projected onto the metal surface to form a porous iron-zinc alloy plating layer. A forming method (Mechanical Plating method, hereinafter referred to as MP method) is known (see Patent Document 1).
This method is a significant method with low energy consumption and low environmental pollution. However, since the formed iron-zinc alloy layer is porous, some treatment is necessary to obtain sufficient corrosion resistance. .
このような亜鉛又は亜鉛合金メッキへの防錆処理としては、従来はクロメート処理に代表されるクロム化合物による化成処理が主に行われ、優れた耐食性とともに、黒色、銀色等の外観も付与することもできる。
クロメート処理として、特許文献２には、上記ＭＰ法により形成された鉄−亜鉛合金メッキ層上に、無水クロム酸と３価クロムを含有し、鉱酸を含まない水性クロメート処理液により処理する方法が記載されている。また、特許文献３には、上記ＭＰ法により形成された鉄−亜鉛合金メッキ層上に、クロム酸化合物、黒色化剤、還元剤からなる焼付け型黒色クロメート処理液により、黒色化された処理鋼板を得ることが記載さている。
Conventionally, as a rust prevention treatment for such zinc or zinc alloy plating, chemical conversion treatment with a chromium compound typified by chromate treatment is mainly carried out, and an appearance such as black and silver color is imparted with excellent corrosion resistance. You can also.
As a chromate treatment, Patent Document 2 discloses a method of treating with an aqueous chromate treatment liquid containing chromic anhydride and trivalent chromium and not containing a mineral acid on the iron-zinc alloy plating layer formed by the MP method. Is described. Further, Patent Document 3 discloses a treated steel sheet blackened by a baking type black chromate treatment liquid comprising a chromic acid compound, a blackening agent, and a reducing agent on the iron-zinc alloy plating layer formed by the MP method. Is described.
しかし、クロメート処理については、近年６価クロムの有害性や環境規制の観点から、６価クロムの使用が制限されたため、６価クロムはもとより３価クロムも含まない、完全にクロムフリーのノンクロム化成処理が求められている。クロムフリー処理液としては、すでに溶剤系、水系を含め、各種公知のものが知られているが、優れた防食性を発揮させることは、実際のところ困難である。このクロムフリー処理液は、無公害又は低公害性の観点から、溶剤系等の非水系ではなく、実質的に有機溶剤を含まない水性の処理液が求められている。又、産業上の利用観点から、塗装箇所において長期間使用又は静置しても処理液の性状が変化せず、塗装作業性も一定であり、品質も安定していることが求められている。 However, with regard to chromate treatment, the use of hexavalent chromium has been restricted in recent years from the viewpoint of the harmfulness of hexavalent chromium and environmental regulations. Processing is required. As the chromium-free treatment liquid, various known ones including a solvent system and an aqueous system are already known, but it is actually difficult to exhibit excellent corrosion resistance. From the viewpoint of non-pollution or low pollution, this chromium-free treatment solution is not a non-aqueous solution such as a solvent type, and an aqueous treatment solution that does not substantially contain an organic solvent is required. In addition, from the viewpoint of industrial use, it is required that the properties of the treatment liquid do not change even when used or left standing for a long time in the coating location, the coating workability is constant, and the quality is stable. .
本発明の課題は、鉄−亜鉛合金メッキ層に対して、優れた被覆性能及び耐食性を有し、環境的にも良好で、品質の安定性に優れる水性クロムフリー処理液、該処理液により形成した処理被膜、及び該処理被膜を備えた各種金属製品を提供することにある。 An object of the present invention is to form an aqueous chromium-free treatment solution that has excellent coating performance and corrosion resistance with respect to an iron-zinc alloy plating layer, is environmentally good, and has excellent quality stability, and the treatment solution. Another object of the present invention is to provide a treated film and various metal products provided with the treated film.
本発明によれば、（Ａ）アクリル樹脂と、（Ｂ）アルカリ金属珪酸塩又はアンモニウム珪酸塩と、水とを含み、（Ａ）成分と（Ｂ）成分の含有割合が、（Ａ）成分１００質量部に対して、（Ｂ）成分２０〜９００質量部であることを特徴とする鉄−亜鉛合金メッキ層被覆用の水性クロムフリー処理液が提供される。
また本発明によれば、上記処理液を、鉄−亜鉛合金メッキ層上に被膜形成し、乾燥した処理被膜が提供される。
更に本発明によれば、上記処理被膜を備えた金属製品が提供される。
According to the present invention, (A) an acrylic resin, (B) an alkali metal silicate or ammonium silicate, and water, the content ratio of (A) component and (B) component is (A) component 100. An aqueous chromium-free treatment solution for coating an iron-zinc alloy plating layer, which is 20 to 900 parts by mass of component (B) with respect to parts by mass, is provided.
Moreover, according to this invention, the said process liquid is formed into a film on an iron-zinc alloy plating layer, and the dried process film is provided.
Furthermore, according to this invention, the metal product provided with the said process film is provided.
本発明の水性クロムフリー処理液（以下、本発明の処理液と略すことがある）は、（Ａ）成分、（Ｂ）成分を特定割合で含むクロムフリーの水系の処理液であるので、環境的に良好で、品質安定性に優れると共に、鉄−亜鉛合金メッキ層に対して、優れた被覆性能を示し、該処理液で形成した本発明の処理被膜は、特に優れた耐食性等を示す。 Since the aqueous chromium-free treatment liquid of the present invention (hereinafter sometimes abbreviated as the treatment liquid of the present invention) is a chromium-free aqueous treatment liquid containing a specific proportion of the component (A) and the component (B), The coating film of the present invention formed with the treatment solution exhibits particularly excellent corrosion resistance and the like.
以下に本発明を更に具体的に説明する。
本発明の処理液に用いる（Ａ）アクリル樹脂は、アクリル酸エステル、メタクリル酸エステルの少なくとも１種を含むビニル系モノマー混合物を、乳化重合、懸濁重合又は溶液重合によって得られ、必要に応じて中和、水性化した水性又は水分散性樹脂である。
本発明の処理液を調製する際には、後述の（Ｂ）成分との安定性が良い点で、乳化剤又は高分子量樹脂分散安定剤の存在下、水中にてビニル系モノマー混合物を乳化重合して得られる（Ａ）成分を含むアクリルエマルジョンが好ましく使用できる。このようなアクリルエマルジョンとしては、市販品を使用することができ、例えば、商品名「ボンコートＳＦＣ−６５」、「ボンコートＢＣ−２８０」（大日本インキ工業社製）、商品名「ポリゾールＡＰ−１０２０」、「ポリゾールＡＰ−１２７２」（昭和電工社製）、商品名「アクアブリッド４６３０」、「アクアブリッド４７９０」（ダイセル化学工業社製）、商品名「アクリセットＥＭＮ−２６０Ｅ」（日本触媒社製）が挙げられる。
本発明においては、上述のアクリルエマルジョンを用いる場合の（Ａ）成分の量は、アクリルエマルジョンの不揮発分量がそれに相当する。
The present invention will be described more specifically below.
The acrylic resin (A) used in the treatment liquid of the present invention is obtained by emulsion polymerization, suspension polymerization or solution polymerization of a vinyl monomer mixture containing at least one of acrylic acid ester and methacrylic acid ester. Neutralized, water-based aqueous or water-dispersible resin.
In preparing the treatment liquid of the present invention, a vinyl monomer mixture is emulsion-polymerized in water in the presence of an emulsifier or a high molecular weight resin dispersion stabilizer in view of good stability with the component (B) described later. An acrylic emulsion containing the component (A) obtained in this way can be preferably used. As such an acrylic emulsion, commercially available products can be used. For example, trade names “BONCOAT SFC-65”, “BONCOAT BC-280” (manufactured by Dainippon Ink Industries, Ltd.), trade names “Polysol AP-1020” ”,“ Polyzol AP-1272 ”(manufactured by Showa Denko KK), trade names“ Aquabrid 4630 ”,“ Aquabrid 4790 ”(manufactured by Daicel Chemical Industries, Ltd.), trade names“ Akreset EMN-260E ”(manufactured by Nippon Shokubai Co., Ltd.) ).
In the present invention, the amount of the component (A) when the above-mentioned acrylic emulsion is used corresponds to the nonvolatile content of the acrylic emulsion.
本発明の処理液には、後述する（Ｂ）成分との混合安定性を損なわず、又耐食性に悪影響を与えない限り、（Ａ）成分以外の各種水溶性又は水分散性樹脂、例えば、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂等を配合することも可能であり、市販品を用いることもできる。但し、本発明の処理液に用いる後述の（Ｂ）成分であるアルカリ金属珪酸塩又はアンモニウム珪酸塩はｐＨ９〜１１であるため、得られる本発明の処理液は、通常アルカリ性になるため、この領域で安定な水溶性樹脂又は水分散性樹脂を使用することが好ましい。
前記ポリエステル樹脂の市販品としては、例えば、商品名「バイロナールＭＤ−１１００」、「バイロナールＭＤ−１３３５」、「バイロナールＭＤ−１５００」（東洋紡社製）が挙げられる。
The treatment liquid of the present invention contains various water-soluble or water-dispersible resins other than the component (A), for example, polyester, as long as the mixing stability with the component (B) described later is not impaired and the corrosion resistance is not adversely affected. Resins, polyurethane resins, epoxy resins and the like can be blended, and commercially available products can also be used. However, since the alkali metal silicate or ammonium silicate, which will be described later, used in the treatment liquid of the present invention has a pH of 9 to 11, the obtained treatment liquid of the present invention is usually alkaline, so this region. It is preferable to use a stable water-soluble resin or water-dispersible resin.
As a commercial item of the said polyester resin, a brand name "Vairnal MD-1100", "Vairnal MD-1335", "Vairnal MD-1500" (made by Toyobo Co., Ltd.) is mentioned, for example.
前記ポリウレタン樹脂としては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール等のポリオールとジイソシアネートとからなるポリウレタン樹脂を、樹脂中に含まれるカルボン酸基、水酸基、或いはポリエチレングリコール（ＰＥＧ）等の親水性を有する成分による自己乳化や、後添加乳化剤により水中に安定に分散させた公知のものが挙げられる。
前記ポリウレタン樹脂の市販品としては、例えば、商品名「ネオレッツＲ−９６６０」、「ネオレッツＲ−９８５」（ＤＳＭ社製）、商品名「レザミンＤ−６４５５」、「レザミンＤ−６３００」（大日精化社製）、商品名「スーパーフレックス１００」、商品名「スーパーフレックス１５０」（第一工業製薬社製）が挙げられる。
前記エポキシ樹脂としては、疎水性のエポキシ樹脂を乳化剤により強制乳化したエポキシ樹脂エマルジョンと、そのもの自身が水に溶解するエポキシ樹脂に分類され、後者の市販品としては、例えば、商品名「アデカレジンＥＭ−０４６０」、「アデカレジンＥＭ−１０７」（旭電化社製）、商品名「エポミックＷＲ−９４」（三井化学社製）が挙げられる。
Examples of the polyurethane resin include a polyurethane resin composed of a polyol and a diisocyanate such as polyester polyol, polyether polyol, and polycarbonate polyol, and a hydrophilic property such as a carboxylic acid group, a hydroxyl group, or polyethylene glycol (PEG) contained in the resin. Examples thereof include self-emulsification using a component having water content, and known products that are stably dispersed in water using a post-added emulsifier.
Commercially available products of the polyurethane resin include, for example, trade names “Neolet's R-9660”, “Neolet's R-985” (manufactured by DSM), trade names “Resamine D-6455”, “Resamine D-6300” Chemical brand), trade name “Superflex 100”, tradename “Superflex 150” (Daiichi Kogyo Seiyaku Co., Ltd.).
The epoxy resin is classified into an epoxy resin emulsion in which a hydrophobic epoxy resin is forcibly emulsified with an emulsifier, and an epoxy resin that itself dissolves in water. Examples of the latter commercially available products include, for example, trade name “Adeka Resin EM- 0460 "," ADEKA RESIN EM-107 "(manufactured by Asahi Denka Co., Ltd.), and trade name" Epomic WR-94 "(manufactured by Mitsui Chemicals, Inc.).
本発明の処理液に用いる（Ｂ）成分である、アルカリ金属珪酸塩又はアンモニウム珪酸塩としては、例えば、式（１）で示される化合物が挙げられる。
Ｍ2Ｏ・ｎＳｉＯ2・・・（１）
式中、ＭはＬｉ、Ｎａ、Ｋ又はアンモニウム基を示し、ｎは１〜２５の整数を表す。該ｎは、Ｍの種類によって異なり、ＭがＮａもしくはＫのときは、好ましくは２〜４である。ＭがＬｉのときは、好ましくは４〜９である。Ｍがアンモニウム塩のときは、好ましくは１２〜２３である。これらのうち、前述の（Ａ）成分との混合性に優れ、耐食性と処理液としての取り扱い易さから、ＭがＮａでｎ＝３の場合と、ＭがＬｉでｎ＝４〜５の場合が特に好ましい。
本発明の処理液を調製する際には、（Ｂ）成分の水溶液である市販品を用いることができる。本発明においては、市販品を用いる場合の（Ｂ）成分の量は、不揮発分量がそれに相当する。
Examples of the alkali metal silicate or ammonium silicate that is the component (B) used in the treatment liquid of the present invention include compounds represented by the formula (1).
M 2 O · nSiO 2 (1)
In formula, M shows Li, Na, K, or an ammonium group, n represents the integer of 1-25. The n varies depending on the type of M, and is preferably 2 to 4 when M is Na or K. When M is Li, it is preferably 4-9. When M is an ammonium salt, it is preferably 12-23. Among these, in the case where M is Na and n = 3 and M is Li and n = 4 to 5 because of excellent mixing with the component (A) described above, corrosion resistance and ease of handling as a treatment liquid Is particularly preferred.
When preparing the treatment liquid of the present invention, a commercially available product that is an aqueous solution of the component (B) can be used. In the present invention, the amount of the component (B) when using a commercially available product corresponds to the nonvolatile content.
本発明の処理液に用いる媒体である水は、クロムフリー処理液としての安定性を維持させるために、ｐＨ７の脱イオン水を使用することが好ましい。 In order to maintain the stability as the chromium-free treatment liquid, it is preferable to use deionized water having a pH of 7 as the medium used for the treatment liquid of the present invention.
本発明の処理液は、安定性の維持、得られる被膜の良好な耐食性や外観を得るために、（Ａ）成分と（Ｂ）成分との含有割合を、（Ａ）成分１００質量部に対し、（Ｂ）成分２０〜９００質量部とする必要がある。（Ｂ）成分が２０質量部未満の場合は、耐食性が十分でなく、一方、９００質量部を超えると、良好な皮膜外観（着色性など）や処理液の安定性が得られ難い。
本発明の処理液において水の割合は、（Ａ）成分及び（Ｂ）成分の合計が、処理液全体の好ましくは１０〜５０質量％、特に好ましくは１５〜４０質量％となるように適宜決定することが望ましい。（Ａ）成分及び（Ｂ）成分がこの範囲より少ない場合は、処理被膜形成時の塗着量が少なく十分な耐食性が得られないおそれがあり、又この範囲を超える場合は、処理液粘度が高くなり、処理被膜の形成操作が困難で均一な被膜が得られないおそれがある。
In order to maintain the stability and obtain good corrosion resistance and appearance of the coating film obtained, the treatment liquid of the present invention has a content ratio of the component (A) and the component (B) to 100 parts by mass of the component (A). (B) It is necessary to set it as 20-900 mass parts of components. When the component (B) is less than 20 parts by mass, the corrosion resistance is not sufficient. On the other hand, when it exceeds 900 parts by mass, it is difficult to obtain a good film appearance (colorability and the like) and stability of the treatment liquid.
In the treatment liquid of the present invention, the ratio of water is appropriately determined so that the total of the component (A) and the component (B) is preferably 10 to 50% by mass, particularly preferably 15 to 40% by mass of the entire treatment liquid. It is desirable to do. When the component (A) and the component (B) are less than this range, there is a possibility that the amount of coating at the time of forming the treated film is small and sufficient corrosion resistance may not be obtained. It becomes high, and there is a possibility that a uniform coating cannot be obtained due to the difficulty in forming the treated coating.
本発明の処理液は、上記（Ａ）成分、（Ｂ）成分及び水以外に、本発明の所望の効果を損なうことなく、また更に効果を向上もしくは他の効果を改善するために、例えば、シリカ粒子、潤滑剤、増粘剤、ｐＨ調整剤、消泡剤、表面調整剤、着色剤、防錆顔料、体質顔料、少量の有機溶剤等を含有させることも可能である。
前記シリカ粒子は、例えば、乾燥皮膜の粘着性を防ぐためや、処理液の粘性を調整するために含有させることができる。具体的にはコロイダルシリカ（水分散型）とヒュームドシリカ（気相シリカ）が挙げられる。コロイダルシリカの市販品としては、例えば商品名「スノーテックスＣ」、「スノーテックスＮ」、「スノーテックス３０」（日産化学社製）、商品名「アデライトＡＴ−２０Ａ」、「アデライトＡＴ−２０Ｎ」（旭電化社製）が挙げられる。ヒュームドシリカの市販品としては、例えば、商品名「アエロジル２００」、「アエロジル３００」（日本アエロジル社製）が挙げられる。
これらのシリカ粒子の平均粒子径（一次粒子径）は、使用効果及び処理液の安定性などの観点から、１０〜３００ｎｍの範囲が好ましい。シリカ粒子を含有させる場合の含有量は、目的に応じて適宜選択でき、得られる処理被膜の粘着防止と本発明の処理液の粘性調整をより良好にするために、０．１〜２０質量％の範囲が好ましい。
The treatment liquid of the present invention, in addition to the component (A), the component (B) and water, does not impair the desired effect of the present invention, and further improves the effect or improves other effects. Silica particles, lubricants, thickeners, pH adjusters, antifoaming agents, surface conditioners, colorants, rust preventive pigments, extender pigments, small amounts of organic solvents, and the like can also be included.
The silica particles can be contained, for example, in order to prevent the adhesion of the dry film or to adjust the viscosity of the treatment liquid. Specific examples include colloidal silica (water dispersion type) and fumed silica (vapor phase silica). Examples of commercially available colloidal silica include trade names “Snowtex C”, “Snowtex N”, “Snowtex 30” (manufactured by Nissan Chemical Co., Ltd.), trade names “Adelite AT-20A”, and “Adelite AT-20N”. (Asahi Denka Co., Ltd.). Examples of commercially available fumed silica include “Aerosil 200” and “Aerosil 300” (manufactured by Nippon Aerosil Co., Ltd.).
The average particle diameter (primary particle diameter) of these silica particles is preferably in the range of 10 to 300 nm from the viewpoints of the use effect and the stability of the treatment liquid. The content in the case of containing silica particles can be appropriately selected according to the purpose, and 0.1-20% by mass in order to prevent sticking of the resulting treatment film and adjust the viscosity of the treatment liquid of the present invention. The range of is preferable.
前記潤滑剤は、通常、後述する本発明の処理被膜に潤滑性を与える目的で使用することができ、用途によっては潤滑性が不必要な場合もあり、その場合は使用されない。また、潤滑性が必要な用途でも、本発明の処理液により形成した処理被膜上に、別の潤滑性を付与する目的の上塗り塗料が使用されることもあり、この場合も本発明の処理液には潤滑剤は通常使用されない。
潤滑剤としては、例えば、４フッ化エチレン樹脂、４フッ化エチレン−エチレン共重合樹脂、３フッ化エチレン塩化エチレン樹脂、フッ化ビニリデン樹脂等の微粉末であるフッ素樹脂粉末や、ポリエチレンワックス、ポリプロピレンワックス等のポリオレフィンワックスが挙げられる。
潤滑剤の平均粒径は、０．３〜５．０μｍの範囲であることが、潤滑性を与えるために好ましく、その含有量は、潤滑性の指標である摩擦係数の大小によって適宜選択することができる。
The lubricant can be used usually for the purpose of imparting lubricity to the treated film of the present invention, which will be described later. Depending on the application, the lubricity may be unnecessary and is not used in that case. Further, even in applications requiring lubricity, an overcoating paint for the purpose of imparting another lubricity may be used on the treatment film formed by the treatment liquid of the present invention. In this case, the treatment liquid of the present invention is also used. In general, no lubricant is used.
As the lubricant, for example, fluororesin powder which is fine powder such as tetrafluoroethylene resin, tetrafluoroethylene-ethylene copolymer resin, trifluoride ethylene chloride resin, vinylidene fluoride resin, polyethylene wax, polypropylene Examples thereof include polyolefin waxes such as wax.
The average particle diameter of the lubricant is preferably in the range of 0.3 to 5.0 μm in order to give lubricity, and the content thereof is appropriately selected depending on the size of the coefficient of friction that is an index of lubricity. Can do.
上記以外のその他の添加剤としての、前記増粘剤としては、例えば、ヒドロキシセルロース、カルボキシメチルセルロース、ベントナイト、ラポナイトが挙げられる。前記ｐＨ調剤剤としては、例えば、アンモニア、アミンが挙げられる。前記消泡剤としては、例えば、アクリル系、シリコーン系、鉱油系が挙げられる。前記表面調整剤としては、例えば、アクリル系、シリコーン系が挙げられる。前記着色剤としては、酸化チタン、酸化鉄、カーボンブラック、アゾ系有機顔料、フタロシアニン系有機顔料等の着色顔料；塩基性染料、酸性染料等の染料、又はこれらを樹脂又は界面活性剤で分散した着色ペースト；リン酸塩系、縮合リン酸塩系等の防錆顔料；炭酸カルシウム、硫酸バリウム、タルク、カオリン等の体質顔料が挙げられる。これらの含有割合は、その目的に応じて適宜選択することができる。
本発明の処理液は水性であるが、上記各種添加剤を混合するため、ごく少量の水に溶解する、例えば、アルコール系、セロソルブ系等の有機溶剤を含むことは差し支えない。
Examples of the thickener as other additives other than the above include hydroxycellulose, carboxymethylcellulose, bentonite, and laponite. Examples of the pH preparation agent include ammonia and amine. Examples of the antifoaming agent include acrylics, silicones, and mineral oils. Examples of the surface conditioner include acrylic and silicone. Examples of the colorant include color pigments such as titanium oxide, iron oxide, carbon black, azo organic pigments, and phthalocyanine organic pigments; dyes such as basic dyes and acid dyes, or these dispersed with a resin or a surfactant. Examples include coloring pastes; anticorrosive pigments such as phosphates and condensed phosphates; extender pigments such as calcium carbonate, barium sulfate, talc, and kaolin. These content ratios can be appropriately selected according to the purpose.
Although the treatment liquid of the present invention is aqueous, it may contain an organic solvent such as alcohol or cellosolve that dissolves in a very small amount of water in order to mix the various additives.
本発明の処理液の製造法は、各成分が溶解又は分散した水溶液又は水分散液の形態にすることが可能であれば特に限定されず、例えば、脱イオン水等の水に、（Ａ）成分と（Ｂ）成分とを攪拌しながら混合し、さらにその他に必要に応じ上記の各種添加剤を攪拌しながら加えて得ることができる。 The method for producing the treatment liquid of the present invention is not particularly limited as long as it can be in the form of an aqueous solution or an aqueous dispersion in which each component is dissolved or dispersed. For example, in a water such as deionized water, (A) The component and the component (B) can be mixed with stirring, and the above-mentioned various additives can be added with stirring as necessary.
本発明の処理液は、鉄−亜鉛合金メッキ層被覆用に使用することによって、上述の効果を有する処理被膜を得ることができる。
鉄−亜鉛合金メッキ層としては、鉄又は鉄合金の表面に、例えば、電気亜鉛メッキ、電気亜鉛合金メッキ、溶融亜鉛メッキ、溶融亜鉛合金メッキのような湿式亜鉛メッキ、或いは塗装による亜鉛系皮膜処理、例えば、ＮＯＦメタルコーティングス社製のジオメット処理等により形成される鉄−亜鉛合金メッキ層が挙げられる。しかし、本発明の効果をより高レベルで得るためには、例えば、上記特許文献１に記載される方法により得られる鉄−亜鉛合金メッキ層がより好ましい。即ち、鉄又は鉄合金を核とし、その核の周囲に鉄−亜鉛合金を介して亜鉛又は亜鉛合金を被覆した、複層被覆粒子の集合体からなるブラスト材料を、鉄又は鉄合金の表面を有する処理物表面に投射して形成した（ＭＰ法）鉄−亜鉛メッキ層が挙げられる。このようにして得られる鉄−亜鉛メッキ層は、通常、上記複層被覆粒子が処理物表面上に幾重にも積層し、多孔質形態を形成する。その表面被覆量は、７ｇ／ｍ2以上が好ましく、特に１０〜３０ｇ／ｍ2が好ましい。被覆量が７ｇ／ｍ2未満であると十分な耐食性が得られない恐れがあり、被覆量が多くなると、処理時間が長くなり不経済である。このようなＭＰ法は、例えば、メカニカルプレーティング用投射機器（ＮＣＺ社製、商品名「ＺコーターＤＺ−１００型」）を用いて行うことができる。
When the treatment liquid of the present invention is used for coating an iron-zinc alloy plating layer, a treatment film having the above-described effects can be obtained.
As the iron-zinc alloy plating layer, for example, electrogalvanizing, electrogalvanizing plating, hot dip galvanizing, wet galvanizing such as hot dip zinc alloy plating, or zinc-based coating treatment by painting. For example, the iron-zinc alloy plating layer formed by the geomet process etc. by NOF metal coatings company etc. is mentioned. However, in order to obtain the effect of the present invention at a higher level, for example, an iron-zinc alloy plating layer obtained by the method described in Patent Document 1 is more preferable. That is, a blast material comprising an aggregate of multi-layer coated particles in which iron or an iron alloy is used as a core and zinc or a zinc alloy is coated around the core via an iron-zinc alloy, and the surface of the iron or iron alloy is used. (MP method) iron-zinc plating layer formed by projecting on the surface of the treated product. In the iron-zinc plating layer thus obtained, the multi-layer coated particles are usually laminated on the surface of the processed material several times to form a porous form. The surface coating amount is preferably from 7 g / m 2 or more, in particular 10 to 30 g / m 2 is preferred. If the coating amount is less than 7 g / m 2 , sufficient corrosion resistance may not be obtained, and if the coating amount is large, the treatment time becomes long and uneconomical. Such MP method can be performed using, for example, a projection device for mechanical plating (manufactured by NCZ, trade name “Z coater DZ-100 type”).
本発明の処理被膜は、本発明の処理液を、上述した鉄−亜鉛合金メッキ層上に被膜形成し、乾燥したものである。
前記被膜形成は、本発明の処理液を、例えば、刷毛塗り、ロール塗り、スプレー塗り、流し塗り、浸漬法により処理物表面を処理することで得ることができるが、通常、スプレー塗装又は遠心振り切りを伴う浸漬法が用いられる。
被膜形成する際の本発明の処理液の付着量は、１０００ｍｇ／ｍ2以上が好ましく、特に良好な耐食性を得るには、３０００ｍｇ／ｍ2以上が好ましい。しかし、１００００ｍｇ／ｍ2を超えると、得られる被膜の付着性が損なわれるおそれがある。このような付着量に調整し易い本発明の処理液の固形分（不揮発分）濃度は、通常１０〜５０質量％である。
前記乾燥は、通常、常温〜２００℃で行うことができる。
The treatment film of the present invention is obtained by forming the treatment liquid of the present invention on the above-described iron-zinc alloy plating layer and drying it.
The film formation can be obtained by treating the surface of the treatment with the treatment liquid of the present invention by, for example, brush coating, roll coating, spray coating, flow coating, or dipping. Usually, spray coating or centrifugal shaking off is performed. A dipping method with is used.
The adhesion amount of the treatment liquid of the present invention when forming a film is preferably 1000 mg / m 2 or more, and preferably 3000 mg / m 2 or more in order to obtain particularly good corrosion resistance. However, if it exceeds 10,000 mg / m 2 , the adhesion of the resulting film may be impaired. The solid content (nonvolatile content) concentration of the treatment liquid of the present invention that can be easily adjusted to such an adhesion amount is usually 10 to 50% by mass.
The drying can usually be performed at room temperature to 200 ° C.
本発明の処理被膜が、前記ＭＰ法により得られる鉄−亜鉛合金メッキ層上に形成されることにより、特に良好な耐食性等を発揮する理由は、以下のように考えられる。
まず、鉄又は鉄合金の表面を有する処理物表面に形成される、上記鉄−亜鉛合金メッキ層が鉄素地より電気的に卑なため、擬制的に溶出することにより鉄素地を保護する。又、溶出した亜鉛合金は酸化物として析出して、鉄素地及び亜鉛合金メッキ層を保護する。しかし、これらの鉄−亜鉛合金メッキ層は多孔質かつ電気的に活性なため、腐食環境下ではそのままは溶出してしまう。しかし、本発明の処理液により更に被膜を形成することで、多孔質の鉄−亜鉛合金メッキ層に樹脂及び珪酸塩成分が入り込み、均一な被膜形成がされることで、腐食環境から保護し防錆効果が発揮される。
また、本発明の処理液で形成された被膜中には、珪酸塩が含まれ、この成分の弱アルカリ性により鉄−亜鉛合金メッキ層が不動態化され溶出が抑えられる。それに珪酸塩は、溶出してきた鉄−亜鉛合金の各イオンなどと結びつき難溶性の塩を形成し、さらに防錆に寄与すると考えられる。
The reason why the treated coating of the present invention exhibits particularly good corrosion resistance and the like by being formed on the iron-zinc alloy plating layer obtained by the MP method is considered as follows.
First, since the iron-zinc alloy plating layer formed on the surface of the processed material having the surface of iron or iron alloy is electrically lower than the iron substrate, the iron substrate is protected by elution in a pseudo manner. Further, the eluted zinc alloy is deposited as an oxide to protect the iron base and the zinc alloy plating layer. However, since these iron-zinc alloy plating layers are porous and electrically active, they are eluted as they are in a corrosive environment. However, by forming a coating with the treatment liquid of the present invention, the resin and silicate components enter the porous iron-zinc alloy plating layer, and a uniform coating is formed, thereby protecting and preventing corrosion environment. Rust effect is demonstrated.
Moreover, the silicate is contained in the film formed with the processing liquid of the present invention, and the iron-zinc alloy plating layer is passivated by the weak alkalinity of this component, and elution is suppressed. In addition, silicate is considered to contribute to rust prevention by forming a slightly soluble salt by combining with each ion of the iron-zinc alloy that has eluted.
本発明の金属製品は、上記本発明の処理被膜を備えるものであって、各種金属製品、例えば、ボルト、ナット、スプリング、シャフト、ピストン、シリンダー、軸受けメタルが挙げられる。 The metal product of the present invention comprises the above-described treated coating of the present invention, and various metal products such as bolts, nuts, springs, shafts, pistons, cylinders, and bearing metals are exemplified.
次に本発明を実施例により、さらに具体的に説明するが、本発明はこれらに限定されない。尚、例中「部」及び「％」はいずれも質量基準である。
実施例１
ヒュームドシリカ（商品名：アエロジル３００、日本アエロジル社製）１部を、脱イオン水２９．５部で３時間ディスパー攪拌して分散させた。次いで、水分散性樹脂（商品名：アクアブリッド４７９０、ダイセル新井ケミカル社製）３０部を攪拌しながら加え、更に、消泡剤（商品名：Ｂｙｋ−０２２、ビックケミージャパン）０．５部を加えた。最後にＪＩＳ珪酸ソーダ（日本化学工業社製）３９部を加え、１時間攪拌して水性クロムフリー処理液を調製した。
EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these. In the examples, “part” and “%” are based on mass.
Example 1
One part of fumed silica (trade name: Aerosil 300, manufactured by Nippon Aerosil Co., Ltd.) was dispersed with 29.5 parts of deionized water for 3 hours with disper stirring. Next, 30 parts of water dispersible resin (trade name: Aquabrid 4790, manufactured by Daicel Arai Chemical Co., Ltd.) was added with stirring, and 0.5 part of antifoaming agent (trade name: Byk-022, Big Chemie Japan) was further added. added. Finally, 39 parts of JIS sodium silicate (manufactured by Nippon Chemical Industry Co., Ltd.) was added and stirred for 1 hour to prepare an aqueous chromium-free treatment solution.
次に、トリクロロエタンによる蒸気脱脂及びショットブラスト処理したＭ１０の６角ボルト（全長４６ｍｍ、ねじ部長さ２１ｍｍ、頭部長さ７ｍｍ）に対し、鉄又は鉄合金を核とし、この核の周囲に鉄亜鉛合金層を介して亜鉛又は亜鉛合金を被着してなる独立した粒子の複合体からなるブラスト材料（ＤＯＷＡ ＩＰ社製、商品名「Ｚアイアン、ＺＺ＃４８Ｅ」）を、メカニカルプレーティング用投射機器（ＮＣＺ社製、商品名「ＺコーターＤＺ−１００型」）により投射処理（ＭＰ法）を行って、当該ボルト上に多孔質の鉄−亜鉛合金メッキ層を形成した。この層の被覆量は１４ｇ／ｍ2であった。次に、上記により得られた水性クロムフリー処理液を使用し、当該ボルトを、遠心振り切りを伴う浸漬法(ディップスピン法)で塗装した。塗布後、電気炉で１６０℃、２０分間乾燥し、第一次の試験材を得た。この水性クロムフリー処理液の被膜付着量は４ｇ／ｍ2であった。 Next, for M10 hexagon bolts (total length 46 mm, thread length 21 mm, head length 7 mm) subjected to steam degreasing and shot blasting with trichloroethane, iron or an iron alloy is used as a core, and iron zinc is surrounded around this core. A blasting material (made by DOWA IP, trade name “Z Iron, ZZ # 48E”) made of a composite of independent particles formed by depositing zinc or zinc alloy through an alloy layer is used as a projection device for mechanical plating. Projection treatment (MP method) was performed using a product name (“Z coater DZ-100 type”, manufactured by NCZ) to form a porous iron-zinc alloy plating layer on the bolt. The coverage of this layer was 14 g / m 2 . Next, using the aqueous chromium-free treatment solution obtained as described above, the bolt was coated by a dipping method (dip spin method) with centrifugal shaking off. After the application, it was dried in an electric furnace at 160 ° C. for 20 minutes to obtain a first test material. The coating amount of this aqueous chromium-free treatment solution was 4 g / m 2 .
更に処理液の経時安定性を見るため、常温で３０日間保管した処理液を、上記と同様にディップスピン法で塗装し、第二次の試験材を得た。
得られた第一次及び第二次の試験材について、耐食性試験（塩水噴霧試験：ＪＩＳ Ｚ−２３７１）を行った。その結果及び水性クロムフリー処理液の組成、及び処理液の状態の経時変化を表１に示す。
尚、処理液の状態の評価及び耐食性試験結果の評価は、以下の基準により行った。
処理液の状態の評価基準
○：液の状態に変化なし、△：液の粘度が少し上昇している、×：液の粘度が著しく上昇している。
耐食性試験結果の評価基準
○：赤錆が全く認められない、△：赤錆が５％未満の面積に認められる、×：赤錆が５％以上の面積に認められる。
Further, in order to check the temporal stability of the treatment liquid, the treatment liquid stored at room temperature for 30 days was coated by the dip spin method in the same manner as described above to obtain a second test material.
The obtained primary and secondary test materials were subjected to a corrosion resistance test (salt spray test: JIS Z-2371). Table 1 shows the results, the composition of the aqueous chromium-free treatment liquid, and the change over time of the state of the treatment liquid.
In addition, evaluation of the state of the treatment liquid and evaluation of the corrosion resistance test result were performed according to the following criteria.
Evaluation criteria for the state of the treatment liquid ○: No change in the state of the liquid, Δ: The viscosity of the liquid is slightly increased, ×: The viscosity of the liquid is remarkably increased.
Evaluation criteria for corrosion resistance test results ○: No red rust is observed, Δ: Red rust is observed in an area of less than 5%, ×: Red rust is observed in an area of 5% or more.
実施例２〜５及び比較例１、２
表１に示す配合組成により水性クロムフリー処理液を作成した以外は、実施例１と同様の手順でボルトを処理した。試験結果を表１に示す。
Examples 2 to 5 and Comparative Examples 1 and 2
Bolts were treated in the same procedure as in Example 1 except that an aqueous chromium-free treatment solution was prepared with the composition shown in Table 1. The test results are shown in Table 1.
実施例６
ＭＰ法による鉄−亜鉛合金メッキ層を形成する代わりに、電気亜鉛メッキ処理（メッキ厚８μｍ）を行った以外は、実施例１と同様に処理を行った。試験結果を表１に示す。
Example 6
The treatment was performed in the same manner as in Example 1 except that an electrogalvanizing treatment (plating thickness: 8 μm) was performed instead of forming the iron-zinc alloy plating layer by the MP method. The test results are shown in Table 1.
実施例１〜５から明らかなように、特定のブラスト材料を投射した鉄−亜鉛合金メッキ層の上に、本発明の処理液による処理を施すことで、被塗物は優れた耐食性を発揮し、処理液としても安定なため、広範囲な各種金属部品に使用できることが期待できる。
一方、比較例１のように、（Ａ）成分に対する（Ｂ）成分の割合が本発明の範囲より少ない場合は、耐食性が不足し、逆に比較例２のように（Ｂ）成分の割合が本発明の範囲より多い場合は、処理液の安定性が好ましくなく、耐食性の安定性も損なわれるので、広範囲な金属部品に使用することが困難であることがわかる。また、実施例６においても、実施例１〜５より劣るが、比較例１及び２より優れた効果が得られることがわかる。
As is clear from Examples 1 to 5, the object to be coated exhibits excellent corrosion resistance by performing the treatment with the treatment liquid of the present invention on the iron-zinc alloy plating layer onto which a specific blast material is projected. Since it is stable as a treatment liquid, it can be expected that it can be used for a wide variety of metal parts.
On the other hand, when the ratio of the component (B) to the component (A) is smaller than the range of the present invention as in Comparative Example 1, the corrosion resistance is insufficient, and conversely, the ratio of the component (B) is as in Comparative Example 2. When the amount is larger than the range of the present invention, the stability of the treatment liquid is not preferable, and the stability of the corrosion resistance is also impaired, so that it is difficult to use for a wide range of metal parts. Moreover, in Example 6, although it is inferior to Examples 1-5, it turns out that the effect superior to Comparative Examples 1 and 2 is acquired.
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| JP2016191013A (en) * | 2015-03-31 | 2016-11-10 | 日本表面化学株式会社 | Water-soluble coating composition |
| WO2018091669A1 (en) * | 2016-11-18 | 2018-05-24 | Fastech S.R.L. | Process for the anti-corrosion coating of small metal parts. |
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| JPS5182325A (en) * | 1975-01-17 | 1976-07-19 | Nippon Steel Corp | AENNOFUSHOKUYOKUSEIHOHO |
| JPS6293383A (en) * | 1985-10-17 | 1987-04-28 | Sumitomo Metal Ind Ltd | Surface treated steel material having superior corrosion resistance and its manufacture |
| JP2002129356A (en) * | 2000-10-25 | 2002-05-09 | Nittetsu Corrosion Prevention Co Ltd | Durable hot-dip galvanized steel and coating method therefor |
| JP2007126699A (en) * | 2005-11-02 | 2007-05-24 | Kobe Steel Ltd | Surface treated galvanized steel plate having excellent corrosion resistance and abrasion resistance, and its manufacturing method |
| WO2007069783A1 (en) * | 2005-12-15 | 2007-06-21 | Nihon Parkerizing Co., Ltd. | Surface treatment for metal materials, surface treatment process, and surface-treated metal materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5182325A (en) * | 1975-01-17 | 1976-07-19 | Nippon Steel Corp | AENNOFUSHOKUYOKUSEIHOHO |
| JPS6293383A (en) * | 1985-10-17 | 1987-04-28 | Sumitomo Metal Ind Ltd | Surface treated steel material having superior corrosion resistance and its manufacture |
| JP2002129356A (en) * | 2000-10-25 | 2002-05-09 | Nittetsu Corrosion Prevention Co Ltd | Durable hot-dip galvanized steel and coating method therefor |
| JP2007126699A (en) * | 2005-11-02 | 2007-05-24 | Kobe Steel Ltd | Surface treated galvanized steel plate having excellent corrosion resistance and abrasion resistance, and its manufacturing method |
| WO2007069783A1 (en) * | 2005-12-15 | 2007-06-21 | Nihon Parkerizing Co., Ltd. | Surface treatment for metal materials, surface treatment process, and surface-treated metal materials |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016191013A (en) * | 2015-03-31 | 2016-11-10 | 日本表面化学株式会社 | Water-soluble coating composition |
| WO2018091669A1 (en) * | 2016-11-18 | 2018-05-24 | Fastech S.R.L. | Process for the anti-corrosion coating of small metal parts. |
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