JP2010209431A - Method of forming colored coating film using metallic material excellent in corrosion resistance, and colored metallic material - Google Patents
Method of forming colored coating film using metallic material excellent in corrosion resistance, and colored metallic material Download PDFInfo
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本発明は、亜鉛系めっき鋼材に代表されるような、表面に亜鉛含有層を有する金属材料の表面に、耐食性また意匠性に優れた着色皮膜を形成方法する方法および着色された金属材料に関するものである。 The present invention relates to a method for forming a colored film excellent in corrosion resistance and design on the surface of a metal material having a zinc-containing layer on the surface, as represented by a zinc-based plated steel material, and a colored metal material It is.
亜鉛は大気環境での耐食性が良好であり、特に鋼材の腐食を有効に抑制することから鋼材に対するめっきとして広く用いられている。しかしその表面外観は、白、灰、シルバーであり、意匠性に乏しい。塗装以外の方法で意匠性を実現した例は極めて限られている。 Zinc has good corrosion resistance in the atmospheric environment, and is particularly widely used as a plating for steel because it effectively suppresses corrosion of steel. However, the surface appearance is white, gray, or silver, and the design is poor. There are only a limited number of examples where designability is achieved by methods other than painting.
例えば特許文献１では、Ｚｎイオン、Ｎｉイオン、Ｆｅイオン、Ｖイオン等を含む水溶液中で亜鉛めっき鋼板をカソード電解することで着色亜鉛めっき鋼板を製造する方法が開示されている。しかし、この場合に得られる着色皮膜は、黒色に限られており意匠性に優れるとは言いがたい。 For example, Patent Document 1 discloses a method for producing a colored galvanized steel sheet by cathodic electrolysis of a galvanized steel sheet in an aqueous solution containing Zn ions, Ni ions, Fe ions, V ions, and the like. However, the colored film obtained in this case is limited to black and cannot be said to be excellent in design.
特許文献２では、ケイ酸塩、水酸化ナトリウム、Ｃｏ塩を含む水溶液中で亜鉛めっき鋼を交流電源にて電解することによって青色に着色する方法が示されている。またＣｏ塩の替わりにＭｎ，Ｃｒ、Ｆｅ、Ｓｎ塩にすることで、それぞれ、茶、緑、白、灰の着色が得られるとしている。しかし、この方法は火花放電を利用したもので大規模な電源が必要であるとともに、厚い皮膜を形成しないと着色性がよくなく、また皮膜の密着性も悪い。 Patent Document 2 discloses a method of coloring blue by electrolysis of galvanized steel with an AC power source in an aqueous solution containing silicate, sodium hydroxide, and Co salt. Moreover, it is said that coloring of tea, green, white, and ash can be obtained by using Mn, Cr, Fe, and Sn salts instead of Co salts, respectively. However, this method uses spark discharge and requires a large-scale power source. If a thick film is not formed, the coloring property is not good, and the adhesion of the film is also poor.
特許文献３では、リン酸イオン、窒素を含むオキソ酸イオンおよび化成皮膜形成金属イオンを含むリン酸塩化成処理液中で金属材料を電解処理することで、りん酸塩化成皮膜を形成する方法が開示されている。この技術は、塗装下地としての密着性、耐食性に優れたりん酸亜鉛系の皮膜を如何なる基材表面にもスラッジ発生少なく効率的に形成することを目的としたものであって、着色に関する記載も示唆も無い。 Patent Document 3 discloses a method for forming a phosphate chemical film by electrolytically treating a metal material in a phosphate chemical treatment solution containing phosphate ions, nitrogen-containing oxoacid ions, and chemical film-forming metal ions. It is disclosed. This technology aims to efficiently form a zinc phosphate-based film with excellent adhesion and corrosion resistance as a coating base on any substrate surface with little sludge generation. There is no suggestion.
本発明が目的としたのは、亜鉛系めっき鋼材等の表面に、簡便で且つ耐食性、密着性の良好な着色皮膜を形成する方法と、その方法によって着色された耐食性の良好な金属材料を提供することである。
本発明は、従来技術の課題である、金属材料上に耐食性と意匠性を併せ持つ着色皮膜を形成する技術を提供することを目的とする。さらに、その技術を工業化させることも課題としており、そのため、通常の金属材料製造工程の延長上で、簡便な方法により製造できる着色皮膜形成方法の提供も、目的とする。
The object of the present invention is to provide a simple method of forming a colored film with good corrosion resistance and adhesion on the surface of a zinc-based plated steel material, etc., and a metal material with good corrosion resistance colored by the method It is to be.
An object of the present invention is to provide a technique for forming a colored film having both corrosion resistance and designability on a metal material, which is a problem of the prior art. Furthermore, it is also an object to industrialize the technology, and therefore, it is an object to provide a method for forming a colored film that can be produced by a simple method on the extension of a normal metal material production process.
本発明の要旨とするところは、以下の通りである。
（１）表面に亜鉛（Ｚｎ）を含有する層を有する金属材料を、ＮｉイオンもしくはＣｏイオンのどちらか1種又は両方、及び硝酸イオン、りん酸イオンを含む水溶液からなる電解処理浴中でカソード電解処理し、該Ｚｎ含有層の表面に着色皮膜を形成することを特徴とする、耐食性に優れた金属材料の着色皮膜の形成方法。
The gist of the present invention is as follows.
(1) Cathode in a electrolytic bath comprising a metal material having a layer containing zinc (Zn) on the surface, an aqueous solution containing one or both of Ni ions and Co ions, and nitrate ions and phosphate ions A method for forming a colored film of a metal material having excellent corrosion resistance, wherein the colored film is formed on the surface of the Zn-containing layer by electrolytic treatment.
（２）前記電解処理浴のＮｉイオンおよびＣｏイオンを合わせた濃度が０．０５〜１ｍｏｌ／ｌ、硝酸イオン濃度が０．１〜１ｍｏｌ／ｌ、りん酸イオン濃度が０．１〜１ｍｏｌ／ｌであることを特徴とする（１）に記載の耐食性に優れた金属材料の着色皮膜の形成方法。このとき、Ｎｉイオン又はＣｏイオンが含まれていなくてもよい。 (2) The combined concentration of Ni ions and Co ions in the electrolytic bath is 0.05 to 1 mol / l, the nitrate ion concentration is 0.1 to 1 mol / l, and the phosphate ion concentration is 0.1 to 1 mol / l. The method for forming a colored film of a metal material having excellent corrosion resistance according to (1), wherein At this time, Ni ions or Co ions may not be contained.
（３）前記電解処理浴のｐＨが２〜４であることを特徴とする、（１）又は（２）に記載の耐食性に優れた金属材料の着色皮膜の形成方法。 (3) The method for forming a colored film of a metal material having excellent corrosion resistance according to (1) or (2), wherein the pH of the electrolytic treatment bath is 2 to 4.
（４）前記電解処理浴のＺｎイオン濃度が、ゼロまたは０．０５ｍｏｌ／ｌ以下であることを特徴とする、（１）〜（３）に記載の耐食性に優れた金属材料の着色皮膜の形成方法。 (4) Formation of a colored film of a metal material having excellent corrosion resistance according to (1) to (3), wherein the Zn ion concentration in the electrolytic treatment bath is zero or 0.05 mol / l or less Method.
（５）前記Ｚｎ含有層表面にＮｉまたはＣｏを含むりん酸塩皮膜からなる着色皮膜層が形成されていることを特徴とする耐食性に優れた着色金属材料。 (5) A colored metallic material excellent in corrosion resistance, wherein a colored coating layer comprising a phosphate coating containing Ni or Co is formed on the surface of the Zn-containing layer.
（６）前記着色皮膜層において、ＮｉまたはＣｏを含むりん酸塩皮膜からなる着色皮膜層の付着量が０．５〜２０ｇ／ｍ２であることを特徴とする（５）に記載の耐食性に優れた着色金属材料。 (6) In the colored coating layer, the adhesion amount of the colored coating layer made of a phosphate coating containing Ni or Co is 0.5 to 20 g / m 2. Excellent colored metal material.
（７）前記着色皮膜層の上層に有機あるいは無機の皮膜層を有することを特徴とする（５）又は（６）に記載の耐食性に優れた着色金属材料。 (7) The colored metal material having excellent corrosion resistance according to (5) or (6), wherein an organic or inorganic film layer is provided on the colored film layer.
（８）前記Ｚｎ含有層を有する金属材料が、亜鉛系めっき鋼材であることを特徴とする（５）〜（７）のいずれか1項に記載の耐食性に優れた着色皮膜の形成方法あるいは着色金属材料。 (8) The method for forming or coloring a colored film having excellent corrosion resistance according to any one of (5) to (7), wherein the metal material having the Zn-containing layer is a zinc-based plated steel material Metal material.
本発明によれば、表面に亜鉛を含有する層を有する金属材料、例えば亜鉛系めっき鋼材等の表面に、簡便な方法で、耐食性、密着性の良好な着色皮膜を形成することが出来る。そのため、従来では成し得なかった意匠性が高く、且つ耐食性の良好な着色皮膜層を有する金属材料を得ることが可能となる。 According to the present invention, a colored film having good corrosion resistance and adhesion can be formed by a simple method on the surface of a metal material having a zinc-containing layer, such as a zinc-based plated steel material. For this reason, it is possible to obtain a metal material having a colored coating layer having high designability and good corrosion resistance that could not be achieved conventionally.
本発明で言う表面が亜鉛（Ｚｎ）を含有する層を有する金属材料とは、亜鉛ダイカスト品、金属材料の亜鉛めっき品、若しくは亜鉛合金めっき品などその種類を問わず、最外層が亜鉛を含有する層を有する金属材料をさす。例えば、亜鉛合金めっき品は、Ｚｎ−Ｎｉ、Ｚｎ−Ｆｅ、Ｚｎ−Ｃｏ、Ｚｎ−Ｃｒ、Ｚｎ−Ｍｎ、Ｚｎ−Ａｌ（Ｚｎ−５％ＡｌあるいはＺｎ−１０％ＡｌあるいはＺｎ−５５％Ａｌなど）、Ｚｎ−Ａｌ−Ｍｇ、Ｚｎ−Ａｌ−Ｍｇ−Ｓｉ等Ｚｎ合金であれば限定無く適用可能である。また、めっき品の基材となる金属材料は、特に限定されない。一般的には、鋼材を基材としたＺｎめっき品が多いが、基材となる鋼材の種類も、もちろん限定されない。 The metal material having a layer containing zinc (Zn) on the surface in the present invention means that the outermost layer contains zinc regardless of the type such as zinc die-cast product, zinc-plated product of metal material, or zinc alloy-plated product. It refers to a metal material having a layer to be For example, zinc alloy plated products include Zn-Ni, Zn-Fe, Zn-Co, Zn-Cr, Zn-Mn, Zn-Al (Zn-5% Al, Zn-10% Al, Zn-55% Al, etc. ), Zn—Al—Mg, Zn—Al—Mg—Si, and other Zn alloys are applicable without limitation. Moreover, the metal material used as the base material of a plating product is not specifically limited. In general, there are many Zn-plated products using a steel material as a base material, but the type of steel material used as the base material is of course not limited.
上記の表面にＺｎ含有層を有する金属材料（特に断りがない限り、本願において基材とよぶ）を必要に応じてその表面清浄化を行った後、ＮｉイオンもしくはＣｏイオン又はそれら両イオン、及び硝酸イオン、りん酸イオンを含む水溶液からなる電解処理浴中でカソード電解処理することによって着色皮膜を形成する。
これは、硝酸イオンが還元される際に、OH-イオンが生成し、これとりん酸イオンとCoイオンやNiイオンが反応して着色皮膜が析出するためと推定される。
After performing the surface cleaning of the metal material having a Zn-containing layer on the surface (referred to as a base material in the present application unless otherwise specified) as necessary, Ni ions or Co ions or both ions, and A colored coating is formed by cathodic electrolysis in an electrolysis bath made of an aqueous solution containing nitrate ions and phosphate ions.
This is presumably because OH- ions are generated when nitrate ions are reduced, and this reacts with phosphate ions, Co ions, and Ni ions to precipitate a colored film.
Ｎｉイオンを含む場合には緑色、Ｃｏイオンを含む場合には紫色の着色層が得られる。Ｎｉ及びＣｏの両イオンが共存する場合は、緑色と紫色の中間色となり、その濃度比により、色が変化する。好ましい濃度は、ＮｉイオンまたはＣｏイオンの両方合わせた濃度が０．０５〜１ｍｏｌ／ｌである。言うまでもなく、ＮｉイオンとＣｏイオンは共存する必要はなく、そのどちらか1種の濃度が０．０５〜１ｍｏｌ／ｌであってもよい。そして、硝酸イオン濃度は０．１〜１ｍｏｌ／ｌ、りん酸イオンは０．１〜１ｍｏｌ／ｌであることが好ましい。 A green colored layer is obtained when Ni ions are included, and a purple colored layer is obtained when Co ions are included. When both Ni and Co ions coexist, the color is intermediate between green and purple, and the color changes depending on the concentration ratio. A preferred concentration is 0.05 to 1 mol / l in the combined concentration of both Ni ions and Co ions. Needless to say, Ni ions and Co ions do not need to coexist, and the concentration of one of them may be 0.05 to 1 mol / l. The nitrate ion concentration is preferably 0.1 to 1 mol / l, and the phosphate ion is preferably 0.1 to 1 mol / l.
ＮｉイオンおよびＣｏイオンが０．０５ｍｏｌ／ｌ未満では、反応速度が遅くまた色ムラも出やすく、また１ｍｏｌ／ｌを超えても色ムラがでやすくまたコスト的にも不利である。 If the Ni ion and Co ion are less than 0.05 mol / l, the reaction rate is slow and color unevenness is likely to occur, and if it exceeds 1 mol / l, color unevenness is likely to occur and the cost is disadvantageous.
硝酸イオン濃度が０．１ｍｏｌ／ｌ未満では反応速度が遅くまた色ムラも出やすく、また１ｍｏｌ／ｌを超えても色ムラがで易い。 If the nitrate ion concentration is less than 0.1 mol / l, the reaction rate is slow and color unevenness is likely to occur, and if it exceeds 1 mol / l, color unevenness is likely to occur.
りん酸イオン濃度が０．１ｍｏｌ／ｌ未満では反応速度が遅くなり、色ムラも出易くなる。その濃度が１ｍｏｌ／ｌを超えても色ムラが出易く、密着性も悪化するため、色の安定性が低下する。 When the phosphate ion concentration is less than 0.1 mol / l, the reaction rate is slow and color unevenness is likely to occur. Even if the concentration exceeds 1 mol / l, color unevenness is likely to occur and the adhesion is deteriorated, so that the color stability is lowered.
また処理浴のｐＨは２〜４の範囲が望ましく、２未満ではムラが発生しやすく、４超では液の安定性が悪く液中に沈殿が発生しやすい。これは、低pHの場合、硝酸イオンが還元される際にOH-イオンが生成しても、これとH+が反応してH2Oになってしまうため、着色皮膜が形成されにくくなると考えられる。また、浴のｐＨが高いと、浴内でりん酸イオン、ＣｏまたはＮｉイオン等が反応して沈殿が生じてしまうためと考えられる。ｐＨ調整は、りん酸イオン若しくは硝酸イオンを含むものであればよく、りん酸、硝酸、ＮａＯＨ、りん酸二水素ナトリウム、りん酸水素二ナトリウム、等を用いて行うことが出来る。 Further, the pH of the treatment bath is preferably in the range of 2 to 4, and if it is less than 2, unevenness is likely to occur, and if it exceeds 4, the stability of the liquid is poor and precipitation is likely to occur in the liquid. This is thought to be because, at low pH, even if OH- ions are generated when nitrate ions are reduced, this reacts with H + and becomes H2O, so that it is difficult to form a colored film. In addition, it is considered that when the pH of the bath is high, phosphate ions, Co or Ni ions react in the bath to cause precipitation. The pH can be adjusted as long as it contains phosphate ions or nitrate ions, and can be adjusted using phosphoric acid, nitric acid, NaOH, sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like.
処理浴中にＺｎイオンが存在すると、色調が黒ずみやすくなる。そのため、Ｚｎイオン濃度はゼロとすることが望ましいが、基材表面からの溶出もあるため、完全にゼロとすることは難しい。従って、可能な限り０．０５ｍｏｌ／ｌ以下に抑えることが好ましい。 When Zn ions are present in the treatment bath, the color tone tends to darken. For this reason, it is desirable that the Zn ion concentration be zero, but it is difficult to completely eliminate it because there is also elution from the substrate surface. Therefore, it is preferable to suppress to 0.05 mol / l or less as much as possible.
処理浴には硫酸イオン、亜硝酸イオン、酢酸イオン、亜硫酸イオン、チオ硫酸イオン、亜硝酸イオン、ピロリン酸イオン、チオシアン酸イオン、酢酸イオン、クエン酸イオン、酒石酸イオン等の無機酸あるいは有機酸のイオンが含まれても良いが、ホウ酸イオンが含まれると外観が悪化しやすいので好ましくない。処理浴温度は常温〜１００℃程度が適用できる。また処理の電流密度は、０．１Ａ／ｄｍ２〜５０Ａ／ｄｍ２程度が適用できる。処理時間は、必要な着色層の付着量によるが、数秒から数十分程度で０．５〜２０ｇ／ｍ２の付着量が得られる。 The treatment bath contains inorganic or organic acids such as sulfate, nitrite, acetate, sulfite, thiosulfate, nitrite, pyrophosphate, thiocyanate, acetate, citrate, and tartrate. Ions may be included, but borate ions are not preferable because the appearance tends to deteriorate. The treatment bath temperature can be from room temperature to about 100 ° C. Further, the current density of the treatment can be about 0.1 A / dm2 to 50 A / dm2. The treatment time depends on the required amount of the colored layer deposited, but an amount of 0.5 to 20 g / m 2 can be obtained in several seconds to several tens of minutes.
前記方法でＮｉまたはＣｏ含有りん酸塩皮膜からなる着色層が得られるが、その構造は必ずしも明らかでなく、りん酸塩だけでなく、酸化物、水酸化物等も含有している可能性がある。しかし、りん酸塩皮膜中にＮｉが存在することにより緑色が、Ｃｏが存在することにより紫色が発色する。処理浴中にＺｎイオンが存在しない場合でもＮｉまたはＣｏ含有リン酸塩皮膜に微量のＺｎが含まれる場合があるが、めっき層のＺｎがエッチングされつつ取り込まれたものと思われる。また、基材のＺｎ層と着色層の界面にはＮｉまたはＣｏの濃化層が存在している。 A colored layer composed of a Ni- or Co-containing phosphate film can be obtained by the above method, but the structure is not always clear, and it may contain not only phosphate but also oxide, hydroxide and the like. is there. However, the presence of Ni in the phosphate film produces a green color, and the presence of Co produces a purple color. Even when Zn ions are not present in the treatment bath, a trace amount of Zn may be contained in the Ni- or Co-containing phosphate film, but it is considered that Zn in the plating layer was taken in while being etched. In addition, a concentrated layer of Ni or Co exists at the interface between the Zn layer and the colored layer of the base material.
着色層の付着量としては、０．５〜２０ｇ／ｍ２程度が好ましく、０．５ｇ／ｍ２未満では着色が薄すぎ、２０ｇ／ｍ２を超えると密着性が悪化しやすくなる。 The coating weight of the colored layer, about 0.5 to 20 g / m 2 are preferred, with less than 0.5 g / m 2 coloring is too thin, adhesion exceeds 20 g / m 2 tends to deteriorate.
前記着色層の上層に、有機物あるいは無機物、若しくは両者の混合物を被覆することも可能である。これによって耐食性をいっそう良好にし、摺動性や耐指紋性といった機能を付加することができる。 It is also possible to coat the colored layer with an organic substance, an inorganic substance, or a mixture of both. As a result, the corrosion resistance can be further improved, and functions such as slidability and fingerprint resistance can be added.
＜実施例１〜１６および比較例１〜４＞
以下、本発明を実施例に基づき、説明する。表１には、本実施例の処理条件及び性能評価結果を示す。
Ｚｎ20g/m2のめっき層を有する電気亜鉛めっき鋼板を用い、表１に示す処理浴条件にて、浴温40℃、電流密度１Ａ／ｄｍ２、処理時間5〜500secの範囲でカソード電解を行い、種々の付着量の皮膜を形成した。処理浴は、硝酸Ｎｉ（または硝酸Ｃｏ）、第一りん酸Ｎｉ（または第一りん酸Ｃｏ）を混合し、更に硝酸、りん酸、りん酸二水素Ｎａによって所定濃度、所定ｐＨに調整した。一部水準では硝酸Ｚｎも添加した。比較例３では硝酸Ｎｉに代えて硫酸Ｎｉを使用した。なお、比較例１は上記処理を行わない電気亜鉛めっき鋼板の原板のサンプルである。外観の目視観察、皮膜の付着量測定（クロム酸溶解法による重量法）、皮膜組成解析、および下記の耐食性、密着性評価を行った。
<Examples 1-16 and Comparative Examples 1-4>
Hereinafter, the present invention will be described based on examples. Table 1 shows the processing conditions and performance evaluation results of this example.
Cathodic electrolysis was performed using an electrogalvanized steel sheet with a Zn20g / m 2 plating layer under the treatment bath conditions shown in Table 1 at a bath temperature of 40 ° C, a current density of 1 A / dm 2 , and a treatment time of 5 to 500 seconds. Films with various adhesion amounts were formed. The treatment bath was mixed with Ni nitrate (or Co nitrate) and primary phosphate Ni (or primary phosphate Co), and further adjusted to a predetermined concentration and a predetermined pH with nitric acid, phosphoric acid, and dihydrogen phosphate Na. In some levels, Zn nitrate was also added. In Comparative Example 3, Ni sulfate was used instead of Ni nitrate. In addition, the comparative example 1 is the sample of the original plate of the electrogalvanized steel plate which does not perform the said process. The appearance was visually observed, the coating amount was measured (gravimetric method by chromic acid dissolution method), the coating composition analysis, and the following corrosion resistance and adhesion evaluation were performed.
＜耐食性＞
試験片の端面と裏面をシールして５％ＮａＣｌ溶液による塩水噴霧試験（ＳＳＴ）を行い、赤錆それぞれの発生時間を観察し以下のように評価した。
◎：赤錆発生時間＞１２０時間
○：７２時間＜赤錆発生時間≦１２０時間
△：２４時間＜赤錆発生時間≦７２時間
×：赤錆発生時間≦２４時間
<Corrosion resistance>
The end face and the back face of the test piece were sealed, a salt spray test (SST) with a 5% NaCl solution was performed, and the occurrence time of each red rust was observed and evaluated as follows.
◎: Red rust occurrence time> 120 hours ○: 72 hours <Red rust occurrence time ≦ 120 hours Δ: 24 hours <Red rust occurrence time ≦ 72 hours ×: Red rust occurrence time ≦ 24 hours
＜密着性＞
エリクセン７ｍｍ押し出し加工を行った後、テープ剥離をして剥離有無を目視評価した。
◎：剥離皆無
○：一部剥離（1mm未満の微小点状剥離）
△：一部剥離（1mm以上の点状剥離）
×：全面剥離
なお、着色層の付着量及び成分組成については、ＥＤＳ，ＧＤＳにて分析を行った。
<Adhesion>
After the Erichsen 7 mm extrusion process, the tape was peeled and the presence or absence of peeling was visually evaluated.
◎: No peeling ○: Partial peeling (small point peeling less than 1mm)
Δ: Partial peeling (dot peel of 1mm or more)
X: Exfoliation of the entire surface In addition, about the adhesion amount and component composition of a colored layer, it analyzed by EDS and GDS.
＜実施例１７〜３２＞
先の実施例１〜１６の各サンプルに、更に、アクリルオレフィン樹脂水性ディスパージョンとコロイダルシリカを固形分で７０：３０になるように混合した液を塗布して、乾燥し、皮膜量１ｇ／ｍ２のクリア皮膜を形成した。
その後、実施例１〜１６と同様、試験片の端面と裏面をシールして５％ＮａＣｌ溶液による塩水噴霧試験（ＳＳＴ）を行い、赤錆の発生状況を観察した。
<Examples 17 to 32>
Further, a liquid prepared by mixing aqueous dispersion of acrylic olefin resin and colloidal silica so as to have a solid content of 70:30 was applied to each sample of Examples 1 to 16, dried, and the coating amount was 1 g / m 2. The clear film was formed.
Then, like Examples 1-16, the end surface and the back surface of the test piece were sealed, a salt spray test (SST) with a 5% NaCl solution was performed, and the occurrence of red rust was observed.
この結果、外観は、実施例１〜１６の各サンプルと同様であるが、耐食性においては、赤錆のみならず白錆も１２０時間で発生が無かった。またクリア皮膜の密着性も剥離皆無で良好であった。以上のように、本発明による着色層の表面に有機物や無機物を被覆することにより、密着性もよく、耐食性を著しく向上させる皮膜が得られることもわかった。 As a result, the appearance was the same as that of each sample of Examples 1 to 16, but in corrosion resistance, not only red rust but also white rust did not occur in 120 hours. Also, the adhesion of the clear film was good with no peeling. As described above, it has also been found that by coating the surface of the colored layer according to the present invention with an organic substance or an inorganic substance, it is possible to obtain a film having good adhesion and significantly improving corrosion resistance.
本発明によれば、表面に亜鉛を含有する層を有する金属材料、例えば亜鉛系めっき鋼材等の表面に、簡便な方法で、耐食性、密着性の良好な着色皮膜を形成することが出来る。そのため、従来では成し得なかった意匠性が高く、且つ耐食性の良好な着色皮膜層を有する金属材料を得ることが可能となる。現在広く普及使用されている耐食性構造材料である亜鉛めっき鋼材の着色化が容易となるだけでなく、耐食性や密着性も向上することから、意匠性、耐久性が要求される構造材料として、建築材料のみならず産業機械や、自動車等での適用が進むことと確信する。 According to the present invention, a colored film having good corrosion resistance and adhesion can be formed by a simple method on the surface of a metal material having a zinc-containing layer, such as a zinc-based plated steel material. For this reason, it is possible to obtain a metal material having a colored coating layer having high designability and good corrosion resistance that could not be achieved conventionally. In addition to facilitating the coloring of galvanized steel, which is a corrosion-resistant structural material that is widely used today, it also improves corrosion resistance and adhesion. I am convinced that not only materials but also industrial machines and automobiles will be applied.
Claims (8)
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| JP2009058576A JP2010209431A (en) | 2009-03-11 | 2009-03-11 | Method of forming colored coating film using metallic material excellent in corrosion resistance, and colored metallic material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719872A (en) * | 2012-06-08 | 2012-10-10 | 南京派诺金属表面处理技术有限公司 | Slag-free low-temperature rapid electrolytic phosphorizing liquid and phosphorizing process thereof |
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2009
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102719872A (en) * | 2012-06-08 | 2012-10-10 | 南京派诺金属表面处理技术有限公司 | Slag-free low-temperature rapid electrolytic phosphorizing liquid and phosphorizing process thereof |
| CN102719872B (en) * | 2012-06-08 | 2018-04-27 | 南京派诺金属表面处理技术有限公司 | A kind of Slag-free low-temperature rapid electrolytic phosphorizing liquid and phosphorizing process thereof |
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